JP3444642B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide light-sensitive material, and more particularly to a silver halide light-sensitive material capable of obtaining a high contrast negative image useful in a photomechanical process.

[0002]

Various additives have been proposed for the purpose of improving the photographic characteristics (sensitivity, fog, rapid developability, etc.) of silver halide light-sensitive materials. The addition of hydrazine compounds to silver halide photographic emulsions and developers is described in US Pat.
No. 30,727, No. 3,227,552, No. 3,38
No. 6,831, No. 2,419,975 and Mees (Me
es) The Theory of Photographic Process 3rd Edition (1)
966), page 281 etc. In addition, amines, onium salts, etc. are known as compounds (nucleation accelerators) that accelerate the infectious development action of hydrazine compounds, and when these are used in combination with hydrazine compounds, high activation and good photographic performance are obtained. What can be done is JP-A-60-140340, JP-A-61-47945, JP-A-61-47924, JP-A-61-167939, JP-A-62-250439, JP-A-62-280733 and JP-A-1-27943. 179930, JP-A-2-2542, JP-A-4-62544 and the like. However, some problems are caused by highly activating the hydrazine compound by using an additive. In recent years, due to the speeding up of processes and the speeding up of processing, the chances of high-speed transport of photosensitive materials have increased, but as a result, when the surface resistance of silver halide photographic light-sensitive materials is high, it is Black spots have started to occur. In particular, it has been known that the occurrence frequency of a super-high-contrast sensitive material in which a hydrazine compound is highly activated and used is significantly increased. Further, high activation with a combination of a hydrazine compound and an onium compound makes it possible to obtain good photographic performance, but sensitivity variation in the manufacturing process becomes large, and quality control thereof becomes difficult.

[0003]

[Problem to be Solved by the Invention] Generation of black spots due to static electricity is suppressed in a silver halide light-sensitive material which is highly activated by using a hydrazine compound and a nucleation accelerator, and stability in the manufacturing process is suppressed. Secure.

[0004]

The above-mentioned objects have been achieved by the following inventions. That is, (1) at least one silver halide emulsion layer is provided on a support, and at least one hydrazine derivative represented by the following general formula (I) is present in at least one of the emulsion layer and other hydrophilic colloid layers. And the following general formulas (II), (III), (IV),
A silver halide photographic light-sensitive material comprising at least one type of an onium salt compound represented by (V) and having one layer containing a conductive metal oxide in the light-sensitive material.

[0005]

[Chemical 6]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. Representation (of which R ₂ is
Represents an elementary-substituted alkyl group or a fluorine-substituted aryl group
Claim only in case) , G ₁ is —CO— group, —SO ₂
-Group, -SO- group,

[0007]

[Chemical 7]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

[0009]

[Chemical 8]

In the formula, R ₁ , R ₂ and R ₃ are alkyl groups,
It represents a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. m represents an integer of 1 to 4, L represents an m-valent organic group bonded to the P atom by its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X represents May be linked to L.

[0011]

[Chemical 9]

In the formula, A represents an organic group for completing the heterocycle. B and C each represent a divalent group. R ₁ , R
₂ represents an alkyl group or an aryl group, and R ₃ and R
₄ represents a hydrogen atom or a substituent. R ₅ represents an alkyl group. X represents an anion group, but X is not necessary in the case of an inner salt. (2) A support having at least one silver halide emulsion layer, and at least one of the emulsion layer and other hydrophilic colloid layers containing a compound represented by the general formula (VI). The silver halide photographic light-sensitive material according to claim 1.

[0013]

[Chemical 10]

Where R₁Is an aliphatic group, an alicyclic compound group,
Represents an aromatic group or a heterocycle, R ₂Is an aliphatic group, alicyclic
Represented by a formula compound group, an aromatic group, a heterocycle or -LZ
Represents a group represented by Q₁, Q₂And Q₃Is a single
, Oxygen atom, sulfur atom, -N (R₃)-Or -N
(R₃) A group represented by —CO— (R₃Is a hydrogen atom or
R ₂Represents a group). L represents a divalent linking group.
Z represents an ionic group. (3) R of the hydrazine derivative represented by the general formula (I)₂But
(1) or (2) characterized by being other than a hydrogen atom
Silver halide photographic light-sensitive material. (4) The layer containing the conductive metal oxide supports the photosensitive layer.
C of (1) or (2) characterized by being between the bodies
Silver halide photo-sensitive material. (5) The layer containing the conductive metal oxide supports the photosensitive layer.
Characterized by being on the other side of the body (1)
Is the silver halide photographic light-sensitive material of (2).

The general formula (I) will be described in detail.

[0016]

[Chemical 11]

In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. And G ₁ is a —CO— group,
-SO ₂ - group, -SO- group,

[0018]

[Chemical 12]

Represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, wherein both A ₁ and A ₂ are hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted Alternatively, it represents an unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the groups defined in R _2, may be different from R _2.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. The branched alkyl groups herein may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Moreover, this alkyl group may have a substituent. In the general formula (I),
The aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group-containing group, a pyridinium group and a hydroxy group. Group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamido group,
Sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, group having hydrazide structure, group having quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group , Carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group, phosphoramide group, diacylamino group, imide group, group having acylurea structure, selenium atom or Examples thereof include a group containing a tellurium atom, a group having a tertiary sulfonium structure or a group having a quaternary sulfonium structure, and a preferable substituent is a linear, branched or cyclic alkyl group (preferably having a carbon number of 1).
~ 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group (preferably Amino group substituted with alkyl group having 1 to 20 carbon atoms, acylamino group (preferably having 2 carbon atoms)
To 30), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Stuff).

In the general formula (I), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example, benzene. It contains a ring. At least one nitrogen as the unsaturated heterocyclic group,
A 5- or 6-membered ring compound containing oxygen and a sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group,
Examples include a tetrazolyl group, a pyridyl group, a pyridinium group, a quinolinium group, and a quinolinyl group. A pyridyl group or a pyridinium group is particularly preferable. The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic group, the amino group is an unsubstituted amino group, and an alkylamino group having 1 to 10 carbon atoms, aryl Amino groups are preferred. R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable. Preferred among the groups represented by R ₂ is when G ₁ is a —CO— group,
Hydrogen atom, alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc.), aralkyl group (eg, o-hydroxybenzyl group, etc.), Aryl groups (eg phenyl groups, 3,5
-Dichlorophenyl group, o-methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group and the like), and a hydrogen atom and trifluoromethyl group are particularly preferable. Also, G ₁ is -S
In the case of an O ₂ — group, R ₂ is an alkyl group (eg, methyl group), an aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group) or a substituted amino group (eg, , Dimethylamino group, etc.) are preferred. When G ₁ is a —COCO— group, an alkoxy group, an aryloxy group and an amino group are preferable.
As G in the general formula (I), a -CO- group and a -COCO- group are preferable, and a -CO- group is most preferable. Also, R ₂ is G
The part of _1- R ₂ is split from the residual molecule, and -G ₁ -R ₂
It may be one that causes a cyclization reaction to form a cyclic structure containing a partial atom, and examples thereof include those described in JP-A-63-29751.

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
Phenylsulfonyl group substituted to be 0.5 or more), acyl group having 20 or less carbon atoms (preferably benzoyl group, or substituted so that the sum of Hammett's substituent constants is -0.5 or more) A benzoyl group, or a linear, branched, or cyclic unsubstituted or substituted aliphatic acyl group (as a substituent, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group Can be mentioned)). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (I) may be further substituted, and preferred examples thereof include those exemplified as the substituent of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent ...
., May be multiply substituted, and preferred examples are also those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from aralkyl group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group and the like. Examples of the polymer include those described in JP-A No. 1-100530.

R ₁ or R ₂ of the general formula (I) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in U.S. Pat. Nos. 4,385,108 and 4,459,34.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048.
No. 59-201049, JP-A-61-17073.
No. 3, No. 61-270744, No. 62-948, No. 63-234244, No. 63-234245, No. 6
The groups described in 3-234246 are mentioned.

Particularly preferred hydrazine derivatives in the present invention are those in which R ₁ is a group having a quaternary ammonium structure, a ballast group, a group which promotes adsorption to the surface of a silver halide grain through a sulfonamide group, an acylamino group or a ureido group. , Or a phenyl group having an alkylthio group, G is a —CO— group, R ₂ is a hydrogen atom, a substituted alkyl group or a substituted aryl group (as a substituent, an electron-withdrawing group or a hydroxymethyl group at the 2-position). Is preferred)
Is a hydrazine derivative. Note that any combination of the above R ₁ and R ₂ options is possible and preferred.

Specific examples of the compound represented by formula (I) are shown below. However, the present invention is not limited to the following compounds.

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

[0035]

[Chemical 20]

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

[0038]

[Chemical formula 23]

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, No. 4,269,929, No. 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016 No. 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, 2-198441, 2-198442.
No. 2-220042, No. 2-221953, No. 2-221954, No. 2-285342, No. 2-2.
85343, 2-289843, 2-3027.
No. 50, No. 2-304550, No. 3-37642,
No. 3-54549, No. 3-125134, No. 3-1
No. 84039, No. 3-240036, No. 3-2400.
No. 37, No. 3-259240, No. 3-280038.
No. 3, No. 3-228536, No. 4-51143, No. 4
-56842, 4-84134, 2-2302
No. 33, No. 4-96053, No. 4-216544,
No. 5-45761, No. 5-45762, No. 5-45
No. 763, No. 5-45764, No. 5-45765,
What was described in Unexamined-Japanese-Patent No. 6-289524 can be used.

The addition amount of the hydrazine derivative in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide, particularly 1 × 1.
The preferable addition amount is in the range of 0 ^-5 mol to 2 × 10 ^-2 mol.

The hydrazine derivative of the present invention is a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve. It can be used by dissolving it in Further, by a well-known emulsification dispersion method, it is dissolved by using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be produced and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The general formula (II) will be described in detail.

[0043]

[Chemical formula 24]

In the formula, R ₁ , R ₂ and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group or a heterocyclic residue, which may further have a substituent. . m represents an integer, L represents an m-valent organic group which is bonded to a P atom and its carbon atom, n represents an integer of 1 to 3, X represents an n-valent anion, and X is linked to L. You may have.

Examples of the groups represented by R ₁ , R ₂ and R ₃ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group and tert group.
-A straight-chain or branched alkyl group such as a butyl group, an octyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group; an aralkyl group such as a substituted or unsubstituted benzyl group; a cyclopropyl group, a cyclopen Cycloalkyl groups such as teal and cyclohexyl, aryl groups such as phenyl, naphthyl and phenanthryl; alkenyl groups such as allyl, vinyl and 5-hexenyl; cyclopentenyl, cyclohexenyl and other cyclo groups Alkenyl group; pyridyl group, quinolyl group,
Furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzotriazolyl group, benzothiazolyl group,
Heterocyclic residues such as a morpholyl group, a pyrimidyl group and a pyrrolidyl group are mentioned. Examples of the substituents substituted on these groups include, in addition to the groups represented by R ₁ , R ₂ and R ₃ , halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, 1 2, a tertiary amino group, an alkyl or aryl ether group, an alkyl or aryl thioether group, a carbonamido group, a carbamoyl group,
Examples thereof include sulfonamide group, sulfamoyl group, hydroxyl group, sulfoxy group, sulfonyl group, carboxyl group, sulfonic acid group, cyano group and carbonyl group. Examples of the group represented by L include a group having the same meaning as R ₁ , R ₂ and R ₃ , as well as a trimethylene group, a tetramethylene group,
Polymethylene group such as hexamethylene group, pentamethylene group, octamethylene group and dodecamethylene group, divalent aromatic group such as phenylene group, biphenylene group and naphthylene group, polyvalent fat such as trimethylenemethyl group and tetramethylenemethyl group Examples thereof include polyvalent aromatic groups such as group groups, phenylene-1,3,5-toluyl group, and phenylene-1,2,4,5-tetrayl group. Examples of the anion represented by X include halogen ions such as chlorine ion, bromine ion and iodine ion, acetate ion, oxalate ion, fumarate ion, carboxylate ion such as benzoate ion, p-toluene sulfonate and methane sulfonate. Examples thereof include sulfonate ion such as butane sulfonate and benzene sulfonate, sulfate ion, perchlorate ion, carbonate ion and nitrate ion.

In the general formula (II), R₁, R₂, R₃Is
It is preferably a group having 20 or less carbon atoms, and 15 or less carbon atoms
The aryl group of is particularly preferable. m is preferably 1 or 2.
When m represents 1, L preferably has 20 or less carbon atoms.
An alkyl group having 15 or less total carbon atoms or an ant
Group is particularly preferred. When m is 2, it is represented by L
The divalent organic group is preferably an alkylene group or aryle group.
Group or a divalent group formed by combining these groups,
Furthermore, these groups and -CO- group, -O- group, -NR_Four
-Group (however R_FourIs a hydrogen atom or R₁, R₂, R₃When
Represents a synonymous group, and has a plurality of R's in the molecule._FourWhen exists,
These can be the same or different, and
They may be bonded to each other), a -S- group, a -SO- group,
-SO₂A divalent group formed by combining groups
It When m represents 2, L is bonded to the P atom at its carbon atom.
Particularly preferred is a divalent group having a total carbon number of 20 or less.
Good When m represents an integer of 2 or more, R in the molecule₁, R
₂, R₃There are multiple Rs,₁,
R₂, R₃Can be the same or different
Yes. n is preferably 1 or 2 and m is preferably 1 or 2.
Good X is R₁, R₂, R ₃, Or a molecule bound to L
Inner salts may be formed.

Many of the compounds represented by the general formula (II) of the present invention are known and commercially available as reagents. As a general synthetic method, there is a method of reacting a phosphinic acid with an alkylating agent such as an alkyl halide or a sulfonate: or a method of exchanging a counter anion of a phosphonium salt by a conventional method.

Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to the following compounds.

[0049]

[Chemical 25]

[0050]

[Chemical formula 26]

[0051]

[Chemical 27]

[0052]

[Chemical 28]

[0053]

[Chemical 29]

[0054]

[Chemical 30]

[0055]

[Chemical 31]

[0056]

[Chemical 32]

[0057]

[Chemical 33]

Next, the general formula (III), the general formula (IV) and the general formula
(V) will be described in more detail.

[0059]

[Chemical 34]

In the formula, A represents an organic group for completing the heterocycle, which may contain a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom or a sulfur atom, and the benzene ring may be condensed. . As a preferred example, A is a 5- to 6-membered ring, and a more preferred example is a pyridine ring,
Examples thereof include a quinoline ring and an isoquinoline ring. A may be substituted, and a preferable substituent is:
Halogen atom (eg, chlorine atom, bromine atom), substituted or unsubstituted alkyl group (eg, methyl group, hydroxyethyl group, etc.), substituted or unsubstituted aralkyl group (eg, benzyl group, p-methoxyphenethyl group, etc.),
Substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-chlorophenyl group, furyl group, thienyl group, naphthyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group) , Acetyl group, etc.), sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino Represents a group, a cyano group, a nitro group, an alkylthio group, and an arylthio group. Particularly preferable examples of the substituent include an aryl group, a sulfo group, a carboxy group and a hydroxy group. B, 2 divalent group represented by C is an alkylene, arylene, alkenylene, -SO ₂ -,
It is preferable that -SO-, -O-, -S-, and -N (R ₆ )-are used alone or in combination. However, R ₆ represents an alkyl group, an aryl group, or a hydrogen atom. Particularly preferred examples of B and C include alkylene, arylene, -O-, and -S-, which may be formed alone or in combination. R ₁ and R ₂ are preferably alkyl groups having 1 to 20 carbon atoms and may be the same or different. The alkyl group may be substituted with a substituent, and examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), a substituted or unsubstituted aryl group (eg, phenyl group, tolyl group, p-
Chlorophenyl group, furyl group, thienyl group, naphthyl group, etc.), substituted or unsubstituted acyl group (eg, benzoyl group, p-bromobenzoyl group, acetyl group, etc.),
Sulfo group, carboxy group, hydroxy group, alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido group, unsubstituted or alkyl-substituted amino group, cyano group, nitro group Represents a group, an alkylthio group, and an arylthio group. Particularly, as a preferred example, R ₁ and R ₂ each represent an alkyl group having 1 to 10 carbon atoms. Examples of preferred substituents include an aryl group, a sulfo group, a carboxy group, and a hydroxy group.

R ₃ and R ₄ represent a hydrogen atom or a substituent, and examples of the substituent are selected from the above-mentioned substituents of the alkyl group of R ₁ and R ₂ . As preferred examples, R ₃ and R ₄ have 0 to 10 carbon atoms, and specific examples thereof include an aryl-substituted alkyl group and a substituted or unsubstituted aryl group. R ₅ has 1 to 2 carbon atoms
An alkyl group of 0 is preferable, and whether it is linear or branched,
Further, it may be a cyclic alkyl group. The alkyl group may be substituted with a substituent, and examples of the substituent are selected from the substituents mentioned above as the substituents of the alkyl group of R ₁ and R ₂ . X represents an anion group, but X is not necessary in the case of an inner salt. Examples of X are chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

The compounds represented by the general formula (III), the general formula (IV) and the general formula (V) of the present invention can be easily synthesized by a well-known method. Can be used as a reference. (Reference, Quart.Rev., 16,16
3 (1962).)

Specific examples of the compounds represented by the general formula (III), the general formula (IV) and the general formula (V) are shown below. However, the present invention is not limited to the following compounds.

[0064]

[Chemical 35]

[0065]

[Chemical 36]

[0066]

[Chemical 37]

[0067]

[Chemical 38]

[0068]

[Chemical Formula 39]

[0069]

[Chemical 40]

[0070]

[Chemical 41]

[0071]

[Chemical 42]

The amount of the compound of the general formula (II), the general formula (III), the general formula (IV) or the general formula (V) of the present invention is not particularly limited, but is 1 per mol of silver halide. It is preferably contained in an amount of ^{x10 -5} to ^{2x10 -2} , particularly 2x1.
The preferred addition amount is in the range of 0 ⁻⁵ to 1 × 10 ⁻² mol.

Further, the general formula (II) and the general formula (III) of the present invention
When the compound of the general formula (IV) or the general formula (V) is contained in the photographic light-sensitive material, if it is water-soluble, as an aqueous solution,
If water-insoluble, alcohols (eg methanol,
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as ethanol), esters (eg ethyl acetate), ketones (eg acetone). Further, by a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, it can be used as a fine dispersion by a method known as a solid dispersion method.

Next, the compound of the general formula (VI) will be described in detail.

[0075]

[Chemical 43]

In the formula, the aliphatic group represented by R ₁ is a linear or branched C ₁ to C 40 unsubstituted alkyl group (eg, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group,
n-amyl group, tert-amyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n-dodecyl group, cetyl group,
Hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2-decyltetradecyl group, tricosyl group, etc.), linear or branched carbon number 1 to 40 A substituted alkyl group (as a substituent, an alkoxyl group, an aryl group, a halogen atom, a carbon ester group, a carbonamide group, a carbamoyl group, an oxycarbonyl group, a phosphoric acid ester group, etc.) (for example, a benzyl group, a β-phenethyl group, 2 -Methoxyethyl group, 4-phenylbutyl group, 4-acetoxyethyl group, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18-phenyloctadecyl group, heptadecylfluorooctyl group, 12- (p-chlorophenyl) dodecyl group , 2- (diphenylphosphate) ethyl group, etc.), straight-chain or branched carbon 2 to 40 unsubstituted alkenyl groups (eg vinyl group, allyl group, 3-butenyl group, 2-methyl-2-butenyl group, 4-pentenyl group, 3-pentenyl group, 3-methyl-3-pentenyl group, 5-hexenyl group, 4-hexenyl group, 3-hexenyl group, 2-hexenyl group, 7-octenyl group, 9-decenyl group, oleyl group, linoleyl group, linolenyl group, etc.), linear or branched carbon number 2 To 40 substituted alkenyl groups (eg, 2-phenylvinyl group, 4-acetyl-2-butenyl group, 13-methoxy-9)
-Octadecenyl group, 9,10-dibromo-12-octadecenyl group), straight-chain or branched C2-C40 unsubstituted alkynyl group (for example, acetylene group, propargyl group, 3-butynyl group, 4-pentynyl group) Group, 5-hexynyl group,
4-hexynyl group, 3-hexynyl group, 2-hexynyl group, etc.), linear or branched substituted alkynyl group having 2 to 40 carbon atoms (alkoxyl group, aryl group, etc. as substituents) (eg, 2-phenyl (Acetylene group, 3-phenylpropargyl group, etc.) and the like are preferable.

The alicyclic compound group is a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms (eg, cyclopropyl group, cyclohexyl group, 2,6-dimethylcyclohexyl group, 4-tert-butylcyclohexyl group, 4-phenylcyclohexyl group, 3-methoxycyclohexyl group, cycloheptyl group, etc.), substituted or unsubstituted cycloalkenyl group having 4 to 40 carbon atoms (for example, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexyl group) Hexenyl group, 2,6-dimethyl-3-cyclohexenyl group, 4-ter
t-butyl-2-cyclohexenyl group, 2-cycloheptenyl group, 3-methyl-3-cycloheptenyl group, etc.) as a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms (as a substituent) Is an alkyl group, an alkoxyl group, an aryl group, a halogen atom, etc.) (for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthranyl group, an o-cresyl group, an m-cresyl group, a p-cresyl group, a p- Ethylphenyl group, p-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, p-n-amylphenyl group, p-tert-amylphenyl group, 2,6-dimethyl-4-tert- Butylphenyl group, p-cyclohexylphenyl group, octylphenyl group, p-tert-octylphenyl group, nonylphenyl group, p-n-dodecylphenyl group, m-methoxyphenyl group, p-butane group Kishifeniru group, m - octyloxyphenyl group, a biphenyl group, m - chlorophenyl group, pentachlorophenyl group, 2 - (5 - methylnaphthyl group) etc.) and the like are preferable.

As the hetero ring, a substituted or unsubstituted cyclic ether having 4 to 40 carbon atoms (eg, furyl group, 4-
Butyl-3-furyl group, pyranyl group, 5-octyl-2H-pyran-3-yl group, isobenzofuranyl group, chromenyl group, etc.), a substituted or unsubstituted nitrogen-containing ring having 4 to 40 carbon atoms (eg, , 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, indolizinyl group, morpholyl group, etc.) can be mentioned as preferred examples.

Among these, straight chain, cyclic or branched unsubstituted alkyl groups having 1 to 24 carbon atoms (eg, methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n- Hexyl group, cyclohexyl group, n-heptyl group,
n-octyl group, 2-ethylhexyl group, n-nonyl group, 1,1,3-trimethylhexyl group, n-decyl group, n
-Dodecyl group, cetyl group, hexadecyl group, 2-hexyldecyl group, octadecyl group, eicosyl group, 2-octyldodecyl group, docosyl group, tetracosyl group, 2-
Decyltetradecyl group, etc.), a straight-chain, cyclic or branched substituted alkyl group having 1 to 24 carbon atoms excluding the carbon number of the substituent (for example, 6-phenoxyhexyl group, 12-phenyldodecyl group, 18- Phenyl octadecyl group, heptadecyl fluorooctyl group, 12- (p-chlorophenyl) dodecyl group, 4-tert-butylcyclohexyl group, etc.), straight-chain, cyclic or branched unsubstituted alkenyl group having 2 to 24 carbon atoms (eg, , Vinyl group, allyl group, 2-methyl-2-butenyl group, 4-pentenyl group, 5-hexenyl group, 3-hexenyl group, 3-cyclohexenyl group, 7-octenyl group, 9-decenyl group, oleyl group, Linoleyl group, linolenyl group, etc.), a linear, cyclic or branched substituted alkenyl group having 2 to 24 carbon atoms (eg, 2-phenylvinyl group, 9,10-dibromo-12-octadecenyl group) ), Substituted or unsubstituted aryl group having 6 to 30 carbon atoms (e.g., phenyl group, 1 - naphthyl, 2 - naphthyl, p-
Cresyl group, p-ethylphenyl group, p-tert-butylphenyl group, p-tert-amylphenyl group, octylphenyl group, p-tert-octylphenyl group, nonylphenyl group, p-n-dodecylphenyl group, m-octyloxyphenyl group, biphenyl group, etc.) are particularly preferable.

Q ₁ , Q ₂ and Q ₃ are each independently a single bond, an oxygen atom, a sulfur atom, -N (R ₃ )-or -N.
(R ₃₎ -CO-, a group represented by (R ₃ represents R ₂ as defined hydrogen atom or above) selected from the. Of these, a single bond, an oxygen atom or —N (R ₃ ) — is preferable, and it is particularly preferable that at least two of Q ₁ , Q ₂ and Q ₃ are oxygen atoms. A single bond is the absence of an element.

L represents a divalent linking group, preferably
It is a group represented by the general formula (VII) .

[0082]

[Chemical 44]

In the formula, Y ₁ , Y ₂ and Y ₃ may be the same or different and are a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms and 6 to 4 carbon atoms.
0 represents a substituted or unsubstituted arylene group (the substituent is the same as that shown in the definition of R ₁ ), and the alkylene group is a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, Pentamethylene group, hexamethylene group, 1,4-cyclohexylene group,
Octamethylene group, decamethylene group, 2-methoxy-1,
As the arylene group such as 3-propylene group, o-phenylene group, m-phenylene group, p-phenylene group, 3-chloro-1,4-phenylene group, 1,4-naphthylene group, 1,5-
A naphthylene group and the like are preferable. Of these, particularly preferred are ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group,
1,4-cyclohexylene group, octamethylene group, decamethylene group, m-phenylene group and p-phenylene group.

J₁, J₂And J₃Are the same
Represents a divalent binding unit, which may be different or different,
Single bond, -O-, -S-, -CO-, -COO-, -O
CO-, -CON (R_Four)-(R_FourIs hydrogen atom, carbon number
1 to 6 carbon atoms of the unsubstituted alkyl group or the substituent
Substituted alkyl group having 1 to 6 carbon atoms (excluding the substituent)
Is an aryl group, alkoxyl group, halogen atom, etc.)
Represents ), -N (R _Four) CO- (R_FourIs shown above
Same as the above), -CON (R_Four) CO- (R_FourIs above
Same as shown), -N (R_Four) CON (R_Five) −
(R_Four, R_FiveMay be the same or different
Well, above R_FourSame as the one defined above), -OCON
(R_Four)-(R_FourIs the same as that shown above), -N
(R_Four) COO- (R_FourIs the same as shown above),
-SO₂-, -SO₂N (R_Four)-(R _FourIs shown above
Same as the above), -N (R_Four) SO₂-(R_FourIs above
Same as shown), -N (COR_Four)-(R_FourIs above
Same as the one shown in the above), -OP (= O) (OR₁) O-
(R₁Is the same as defined above) and the like. This
Among them, single bond, -O-, -S-, -CO-,-
COO-, -OCO-, -CON (R_Four)-(R_FourIs water
Represents an elementary atom, a methyl group, an ethyl group and a propyl group. -N
(R_Four) CO- (R_FourIs the same as shown above), −
SO₂N (R_Four)-(R_FourIs the same as shown above
Same), -N (R_Four) SO₂-(R_FourIs the one shown above
Are the same as the above) and the like are particularly preferable.

P, q and r are each independently an integer of 0 to 5. Preferably, p, q, and r are each independently an integer value of 0 to 3, and it is particularly preferable that p, q, and r are each independently an integer value of 0 or 1. s is an integer value of 1 to 10, preferably 1 to 5, and particularly preferably 1 to 3. a
And b are each independently an integer value of 0 to 50. Of these, a and b are independently 0 to 2
It is preferable to take an integer value of 0, and a and b are 0 to 1
The case of taking an integer value of 0 is particularly preferable.

Z is preferably a hydrophilic anion, cation
Ionic or amphoteric ionic group, which is particularly favorable for photographic performance.
Preferred is an anionic group. As an anionic group
-COOM, -SO₃M, -OSO₃M, -PO (O
M)₂, -OPO (OM)₂(M represents a counter cation,
Preferably an alkali metal ion (eg, lithium ion
Ion, sodium ion, potassium ion, etc.), alkali
Earth metal ions (eg magnesium ion, calci)
And an ammonium ion). In particular
Preferred are sodium ion and potassium ion.
It ) Is preferred, and the cationic group is —NH.₃+ ・ X
-, -NH₂(R₆) + * X-, -NH (R ₆)₂+ ・ X
-, -N (R₆)₃+ ・ X- (R₆Has 1 to 3 carbon atoms
Alkyl groups (eg methyl, ethyl, 2-hydroxy)
Ciethyl group, n-propyl group, iso-propyl group, etc.)
Of these, a methyl group and a 2-hydroxyethyl group are preferable.
X represents a counter anion, preferably a halogen ion (fluorine
Fluorine ion, chlorine ion, bromine ion, etc.), composite inorganic acid
Nion (hydroxide ion, sulfate ion, nitrate ion, phosphorus
Acid ion) and organic compound anion (oxalate ion)
Ion, formate ion, acetate ion, propionate ion,
Tan sulfonate ion, p-toluene sulfonate ion
Etc.), and particularly preferred are chlorine ion and sulfur sulfate.
Ion, nitrate ion, and acetate ion.

Preferred zwitterionic groups are the following general
The thing of the structure represented by Formula (VIII) can be mentioned.

[0088]

[Chemical formula 45]

In the formula, D represents a nitrogen atom or a phosphorus atom. R ₇ and R ₈ represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a 2-hydroxyethyl group, an iso-propyl group, etc.), a methyl group, a 2
The -hydroxyethyl group is particularly preferred. L is the above general formula
Same as the divalent linking group defined in (VII) . A-represents an anionic group, and preferable groups are -COO- and -SO.
3 -, - OSO3 -, - PO (OR 9) O -, - OPO (O
R ₉ ) O- (R ₉ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group, 2-hydroxyethyl group, iso-propyl group, etc.)). is there.

R ₂ is a monovalent group selected from the group defined by R ₁ or the group defined by -LZ, and when selected from the definition range of R ₁ , the same molecule is selected. The structure may be the same as or different from that of R ₁ present inside. Even when selected from the definition range of -LZ, the structure may be the same as or different from -LZ existing in the same molecule. It is particularly preferable that R ₂ is selected from the definition range of R ₁ . Further, the total carbon number of R ₁ and R ₂ is preferably 6 or more and 80 or less, and particularly preferably 8 or more and 50 or less.

Further, any two or more groups of R ₁ , R ₂ and L defined above may be bonded to each other to form a ring structure. In this case, the ring structure to be formed is not particularly limited, but preferably the ring structure formed has 4 to 7 ring members, particularly preferably a 5-membered ring, from the viewpoint of stability of the ring structure. Alternatively, it has a 6-membered ring structure.

Specific examples of preferable surface-active compounds used in the present invention are shown below, but the present invention is not limited to these specific examples.

[0093]

[Chemical formula 46]

[0094]

[Chemical 47]

[0095]

[Chemical 48]

[0096]

[Chemical 49]

[0097]

[Chemical 50]

[0098]

[Chemical 51]

[0099]

[Chemical 52]

[0100]

[Chemical 53]

[0101]

[Chemical 54]

[0102]

[Chemical 55]

The surface-active compound represented by the above general formula (VI) of the present invention can be prepared by a general synthetic method. Examples of typical synthetic methods are shown below, but the present invention is not limited to these specific synthetic examples.

[0104] Synthesis Example 1 Compound PW-3 of Synthesis 1) di-2-ethylhexyl phosphoryl Rukuro in 200ml three-necked flask fitted with a synthetic cooling tube and a stirring device rides 2-ethylhexyl alcohol 26.0 g (0.2
Mol) was added, and the mixture was ice-cooled with stirring and cooled to 5 ° C. Phosphorus oxychloride (15.3 g, 0.1 mol) was added dropwise to the flask over 30 minutes so that the internal temperature did not exceed 10 ° C., and the mixture was stirred as it was for 20 minutes after the completion of the addition. The temperature of this reaction liquid was raised to 25 ° C., the temperature was reduced to 80 to 120 mmHg for 1 hour, and the temperature was further raised to 50 ° C., and the reaction was performed for 4 hours under the reduced pressure. The reaction solution was cooled to room temperature and the clear liquid was 33.7.
g was obtained (yield 98.8%).

[0105] 2) 4-hydroxybutyl - di-2-ethylhexyl phosphate in 200ml three-necked flask fitted with a synthetic cooling tube and a stirring apparatus Fate 1,4 - butanediol 18.8 g (0.2 mol) and triethylamine 15 0.2 g (0.15 mol) was added, and 33.7 g (0.099 mol) of di-2-ethylhexylphosphoryl chloride synthesized above was stirred for 30 minutes under water cooling so that the internal temperature did not exceed 30 ° C. It dripped over, and it stirred for 1 hour after the completion of dropping. This reaction liquid was heated to 50 ° C. and reacted for 3 hours. The reaction solution was cooled to room temperature, 200 ml of ethyl acetate was added, the precipitate was filtered, and the filtrate was concentrated under reduced pressure, followed by column chromatography using silica gel as a carrier (eluent: ethyl acetate / hexane =
2/1) separated and purified to give 16.8 g of the target compound (yield 4
3.0%) was obtained.

[0106] 3) Compound PW-3 4-hydroxybutyl synthesized above in Synthesis condenser and a 200ml three-neck flask fitted with a stirrer device - di-2-ethylhexyl phosphate 15.8 g (40 mmol)
And 10 ml of chloroform are added, and 9.3 g (80 mmol) of chlorosulfonic acid is added to the inside temperature of 1 while stirring under ice cooling.
The mixture was added dropwise over 30 minutes so that the temperature did not exceed 5 ° C, and after completion of the addition, the mixture was stirred at room temperature for 2 hours as it was. Water of this reaction solution 20
ml was slowly added, and 50 ml of ethanol was further added to form a solution, and then the pH was adjusted to 7.1 with a 1 mol / liter sodium hydroxide solution. To the reaction solution, 300 ml of toluene was added and azeotropic dehydration was repeated 5 times, then the solution was once concentrated, 300 ml of ethyl acetate was added to dissolve it, and the mixture was allowed to stand and dehydrate overnight using 80 g of anhydrous sodium sulfate. The insoluble matter was filtered off from this solution, and the filtrate was concentrated under reduced pressure to obtain 19.3 g (yield 97.1%) of the desired compound PW-4 of the present invention in the form of a waxy compound. The compound was identified by IR spectrum, ¹ H-NMR spectrum and elemental analysis.

¹ H-NMR (CDCL ₃ , δ) 0.8-
1.1 (hydrocarbon chain CH ₃ , 12H), 1, 2 to 1.
5 (hydrocarbon chain CH ₂ , 16H), 1.5 to 1.7
(Hydrocarbon chain CH, 2H), 1.7~1.9 (tetramethylene chain CH _2, 4H), 3.8~4.0 (hydrocarbon chain -CH ₂ O-, 4H), 4.0~ 4.4 (tetramethylene chain —CH ₂ O—, 4H) IR 1320 cm ⁻¹ (phosphate ester) 1230 cm ⁻¹ (sulfate ester)

[0108] Synthesis of Synthesis Example 2 Compound PW-16 1) di - dodecyl phosphoryl Rukuro a one-liter, three-neck dodecyl alcohol 223.6g (1.2 mol flask fitted with a synthetic cooling tube and a stirring device rides),
Add 500 ml of methylene chloride, cool with ice with stirring, and add 55.8 g (0.6 mol) of phosphorus oxychloride to the inside temperature of 10 ° C.
The mixture was added dropwise over 30 minutes so as not to exceed 10 minutes, and the mixture was stirred for 20 minutes after the completion of the addition. The temperature of this reaction solution is raised to room temperature, and then 80
The mixture was heated under reduced pressure of 120 mmHg for 1 hour, further heated to 50 ° C., and reacted under normal pressure for 3 hours. The reaction liquid was cooled to room temperature to obtain 246.6 g of a transparent liquid (yield 87.
6%).

[0109] 2) Compound PW-16 previously dehydrated p- phenolsulfonic acid 87.1g in a one-liter, three-neck flask fitted with a synthetic cooling tube and a stirring apparatus
(0.5 mol) and 50.1 g (0.5 mol) of triethylami were added, and 216.81 g (0.5 mol) of the didodecylphosphoryl chloride synthesized above was stirred while cooling with water. The mixture was added dropwise over 30 minutes so as not to exceed the value , and the mixture was stirred as it was for 1 hour after the completion of the addition. This reaction liquid was heated to 50 ° C. and reacted for 3 hours. The reaction solution was cooled to room temperature, 200 ml of ethyl acetate was added, the precipitate was filtered, and the filtrate was concentrated under reduced pressure, followed by column chromatography using silica gel as a carrier (eluent: ethyl acetate / hexane =
The substance obtained by separation and purification in 4/1) is methanol 15
It was dissolved in 0 ml and 21.0 g (0.5
(5 mol) was added and the mixture was stirred at room temperature for 8 hours. To this reaction solution, 500 ml of toluene was added and azeotropic dehydration was repeated 5 times.
ml was added and dissolved, and the mixture was allowed to stand and dehydrate overnight using 80 g of anhydrous sodium sulfate. The insoluble matter was filtered off from this solution, and the filtrate was concentrated under reduced pressure to obtain the desired compound PW-22 12 of the present invention.
5.6 g (41.1% yield) were obtained in the form of a waxy compound. The compound was identified by IR spectrum, ¹ H-NMR spectrum and elemental analysis.

¹ H-NMR (CDCL ₃ , δ) 0.8-
1.1 (hydrocarbon chain CH ₃ , 6H), 1, 2 to 1.5
(Hydrocarbon chain CH _2, 20H), 3.8~4.0 (hydrocarbon chain _{-CH 2 O-, 4H), 7.3~8.1} ( aromatic ring CH, 4H) IR 1320cm ^-1 ( Phosphate ester) 1230cm ^-1 (Sulfate ester)

Synthesis Example 3 Synthesis of Compound PW-36 1) Synthesis of di-2-ethylhexylphosphoryl chloride Di-2-ethylhexylphosphoryl chloride was prepared in the same formulation as in Synthesis Example 1 above.
Ethylhexyl phosphoryl chloride was synthesized.

[0112] 2) 2-dimethylaminoethyl over di 2-ethylhexyl phosphate 200ml three-necked flask fitted with a synthetic cooling tube and a stirring device 2-dimethylaminoethanol 17.8 g (0.2
Mol) and 15.2 g (0.15 mol) of triethylamine were added, and 33.7 g (0.0) of di-2-ethylhexylphosphoryl chloride synthesized above while stirring under water cooling.
99 mol) was added dropwise over 30 minutes so that the internal temperature did not exceed 30 ° C., and the mixture was stirred as it was for 1 hour after the completion of the addition. This reaction liquid was heated to 50 ° C. and reacted for 3 hours. The reaction solution was cooled to room temperature, 200 ml of ethyl acetate was added, the precipitate was filtered, the filtrate was concentrated under reduced pressure, and then separated and purified by column chromatography using silica gel as a carrier (eluent: ethyl acetate / hexane = 5/1). Thus, 12.4 g (yield 31.5%) of the target compound was obtained.

[0113] 3) Compound PW-36 synthetic cooling tube and a stirring device to 200ml three-necked flask fitted of the above-synthesized 2-dimethylaminoethyl phosphate 11.8g (30 mmol) was placed in toluene 30 ml, stirred under water-cooling While 4.1g of butanesalton
(33 mmol) was added dropwise over 10 minutes, and after completion of the addition 1
The temperature was raised to 50 ° C. and the mixture was stirred as it was for 6 hours. The reaction solution was cooled to room temperature, added to 300 ml of acetone, and the precipitate was collected by filtration to obtain the desired compound PW-36 of the present invention.
12.3 g (yield 77.4%) was obtained in the form of a light brown powder. The compound was identified by IR spectrum, 1 H-NMR spectrum and elemental analysis.

Synthesis Example 4 Synthesis of compound PW-42 1) Synthesis of tartaric acid di-dodecyl ester 372.7 g (2 mol) of dodecanol and 15 g of tartaric acid were placed in a 2-liter three-necked flask equipped with a cooling tube and a stirrer.
0.1 g (1 mol), 500 ml of toluene and 17.2 g (0.1 mol) of p-toluenesulfonic acid were added, and 1
Raise the temperature to 50 ° C and perform azeotropic dehydration under toluene distillation 1
The reaction was carried out for 2 hours. The reaction liquid was cooled to room temperature, and the oily compound obtained by distilling off toluene under reduced pressure was separated and purified by column chromatography using silica gel as a carrier (eluent: ethyl acetate / hexane = 1/1) to obtain colorless. As a result, 377.7 g of the target product was obtained as a transparent liquid (yield: 77.6%).

[0115] 2) Compound PW-42 tartaric didodecyl ester 3 synthesized newly synthesized condenser and a 3 l three-neck flask fitted with a stirrer in the above was the
40.7 g (0.7 mol) and 500 ml of methylene chloride were added, and the mixture was cooled with ice while stirring to give 65.1 g of phosphorus oxychloride.
(0.7 mol) was added dropwise over 30 minutes so that the internal temperature did not exceed 10 ° C, and the mixture was stirred as it was for 20 minutes after the completion of the addition. The reaction solution was heated to room temperature, heated under reduced pressure of 80 to 120 mmHg for 1 hour, further heated to 50 ° C., reacted under normal pressure for 3 hours, and then cooled to room temperature. Prepare 3 liters three neck flask newly fitted with a condenser and a stirring device,
1 liter of ethyl acetate, 525.6 g (3.5 mol) of triethylene guticol and 10 parts of triethylamine were added.
Add 1.2 g (1 mol), and stir under water cooling so that the internal temperature does not exceed 30 ° C. with the total amount of the reaction solution synthesized above.
The mixture was added dropwise over 0 minutes, and the mixture was stirred for 1 hour after the completion of the addition. This reaction liquid was heated to 50 ° C. and reacted for 3 hours.
The reaction liquid was cooled to room temperature, the precipitate was filtered, the filtrate was concentrated under reduced pressure, and then separated and purified by column chromatography using silica gel as a carrier (eluent: ethyl acetate / hexane = 3/1) to obtain the purpose of the liquid. The compound was obtained. The solution was dissolved by adding chloroform 300ml thereto, placed 200ml three-neck flask fitted with a condenser and a stirring device, stirring under ice-cooling while 81.5g of chlorosulfonic acid (0.
(7 mol) was added dropwise over 60 minutes so that the internal temperature did not exceed 15 ° C, and after completion of the addition, the mixture was stirred at room temperature for 2 hours as it was. Was added the reaction mixture to slowly water 100 ml, after the solution was added further ethanol 500 ml, 1 mol / Li
The pH was adjusted to 6.9 with sodium hydroxide solution. After adding 500 ml of toluene to this reaction solution and repeating azeotropic dehydration 5 times, the solution was once concentrated,
500 ml of ethyl acetate was added and dissolved, and 100 g of anhydrous sodium sulfate was used to stand and dehydrate overnight. The insoluble matter was filtered off from this solution, and the filtrate was concentrated under reduced pressure to obtain 74.5 g (yield 13.6%) of the desired compound PW-42 of the present invention in the form of a wax-like compound. Compound is IR spectrum, ¹
It was identified by 1 H-NMR spectrum and elemental analysis.

The addition amount of the compound of the general formula (VI) of the present invention is not particularly limited, but it is 1 per 1 mol of silver halide.
It is preferably contained in an amount of ^{x10 -5} to 2 x 10 ^-2 mol, and particularly preferably in the range of 5 x 10 ^-4 to 5 x 10 ^-3 mol. When the compound of the general formula (VI) of the present invention is contained in a photographic light-sensitive material, it is an aqueous solution when it is water-soluble, and alcohols (eg methanol, ethanol) and esters (eg when it is water-insoluble). It may be added to the silver halide emulsion solution or the hydrophilic colloid solution as a solution of a water-miscible organic solvent such as ethyl acetate) and ketones (eg acetone).

In the present invention, the general formula (I) and the general formula (I
I), general formula (III), general formula (IV), general formula (V) and general formula
When the compound represented by (VI) is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (for example, protective layer, intermediate layer, filter). Layer, antihalation layer, etc.)
You may make it contain in. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. In particular, it is preferable to add it to the coating solution prepared for coating.

As the conductive metal oxide of the present invention, crystalline metal oxide particles are used, but those containing oxygen defects and those containing a small amount of different atoms forming donors with respect to the metal oxide used. Is generally preferable because it has high conductivity, and the latter is particularly preferable because it does not cause fog in the silver halide emulsion. Zn as an example of a metal oxide
O ₂ , TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO,
MoO ₃ , V ₂ O _5, etc. or their composite oxides are preferable, especially
ZnO, TiO ₂ and SnO ₂ are preferred. Examples of containing different atoms include, for example, addition of Al, In, etc. to ZnO, addition of Sb, Nb, halogen element, etc. to SnO ₂ , and addition of Nb, Ta etc. to TiO ₂ . Is effective. However, the present invention is not limited to these examples.

The addition amount of these hetero atoms is 0.01 mol% to 30%.
The range of mol% is preferable, and the range of 0.1 mol% to 10 mol% is particularly preferable. The metal oxide fine particles of the present invention have conductivity, and their volume resistivity is preferably 10 ⁷ Ω- ^cm or less, and particularly preferably 10 ⁵ Ω- ^cm or less. These oxides are described in JP-A-56-143431 and JP-A-56-1.
20519, 58-62647 and the like. Furthermore, as described in JP-B-59-6235, a conductive material in which the above metal oxide is adhered to other crystalline metal oxide particles or fibrous substances (for example, titanium oxide) is used. You may. Available particle size is 10 μ
m or less is preferable, but if it is 2 μm or less, stability after dispersion is good and it is easy to use. Further, in order to make the light scattering property as small as possible, it is very preferable to use conductive particles of 0.5 μm or less because a transparent photosensitive material can be formed. If the conductive material is needle-shaped or fibrous,
The length is 30 μm or less and the diameter is preferably 2 μm or less, and particularly preferably, the length is 25 μm or less and the diameter is 0.5 μm or less.
μm or less, and the length / diameter ratio is 3 or more. In the present invention, these conductive metal oxides are preferably added to the antihalation layer, back layer and undercoat layer.
The amount of the conductive metal oxide used in the present invention is not particularly limited, but preferably 0.0005 to 5 g / m ² , particularly 0.00
It is from 09 to ² g / m ² , more preferably from 0.001 to 1 g / m ² .

The silver halide emulsion used in the present invention may have a composition of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochlorobromide or the like. As a method for preparing the silver halide emulsion used in the present invention, various methods known in the field of silver halide photographic light-sensitive materials are used. For example, P. Glafkides "Chimie et Physique Photographique" (Paul Mantel, 1967), GF Duffinu "GFDuffinu" Photographic E chemistry chemistry
mulsion Chemistry) (The Focal Press) (TheF
Ocal Press), 1966) by VLZelikman et al., "Making and
Coating Photographic Emulsion (Ma
kig and Coating Photographic Emulsion ”(published by The Focal Press, 1964) and the like. The emulsion of the present invention is preferably a monodisperse emulsion and has a coefficient of variation of 2
It is 0% or less, particularly preferably 15% or less. Here, the coefficient of variation is {(standard deviation of particle size) / (average particle size)} × 1
It is a numerical value represented by 00.

The average grain size of the grains in the monodisperse silver halide emulsion is 0.5 μm or less, particularly preferably 0.
It is 1 μm to 0.4 μm. As a method for reacting the water-soluble silver salt (silver nitrate aqueous solution) with the water-soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. Further, it is preferable to form grains using a so-called silver halide emulsion such as ammonia, thioether, substituted thiourea. Substituted thiourea compounds are more preferred, and JP-A Nos. 53-82408 and 55-7773 are preferred.
No. 7, etc. Preferred thiourea compounds are
Tetramethylthiourea and 1,3-dimethyl-2-imidazolidinethione. The control double jet method and the grain formation method using a silver halide solvent make it easy to form a silver halide emulsion having a regular crystal form and a narrow grain size distribution. It is a useful tool. Monodisperse emulsion is a cube,
It preferably has a regular crystal form such as an octahedron or a tetradecahedron, and a cube is particularly preferable. The silver halide grains may have a uniform phase in the inside and the surface layer or may have different phases.

In the present invention, a silver halide emulsion particularly suitable as a light-sensitive material for line drawing and halftone dot formation is silver 1
It is an emulsion produced in the presence of 10 ⁻⁸ to 10 ⁻⁵ mol of iridium salt or its complex salt per mol. In the present invention, a silver halide emulsion which is particularly suitable as a reversal light-sensitive material is a silver halide containing 90 mol% or more, and more preferably 95% mol or more of silver chloride.
It is 0 mol% silver chlorobromide or silver chloroiodobromide. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

The silver halide emulsion of the present invention may be chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method and a noble metal sensitization method can be used, and they are used alone or in combination. When used in combination, for example,
The sulfur sensitizing method and gold sensitizing method, the sulfur sensitizing method, selenium sensitizing method and gold sensitizing method, the sulfur sensitizing method, tellurium sensitizing method and gold sensitizing method are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. As the sulfur sensitizer, known compounds can be used. For example, in addition to the sulfur compound contained in gelatin, various sulfur compounds, for example, thiosulfates, thioureas, thiazoles, rhodanins, etc. Can be used. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The amount of the sulfur sensitizer added varies depending on various conditions such as pH, temperature and size of silver halide grains during chemical ripening, but it is 10 ^-7 to 10 ^-2 mol per mol of silver halide. And more preferably 10 ⁻⁵ to 10 ⁻³ mol.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or unstable selenium compound and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Unstable selenium compounds are disclosed in JP-B-44-15748 and JP-B-43-1.
3489, JP-A-4-25832, and 4-1092.
No. 40, No. 4-324855, etc. can be used. In particular, it is preferable to use the compounds represented by the general formulas (VIII) and (IX) in JP-A-4-324855.

The tellurium sensitizer used in the present invention is a compound capable of producing silver telluride presumed to serve as a sensitizing nucleus on the surface or inside of the silver halide grain. Regarding the formation rate of silver telluride in a silver halide emulsion, the method disclosed in JP-A-5-187
It can be tested by the method described in No.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496.
No. 1, No. 1,295,462, No. 1,396,69
6, Canadian Patent No. 800,958, Japanese Patent Laid-Open No. 4-20
No. 4640, No. 4-271341, No. 4-33304
No. 3, No. 4-129787, J. Chem. Soc. Chem. Commu
n., 635 (1980), ibid. 1102 (1979), ibid. 645 (1979), J. Chem.
Soc.Perkin.Trans., 1,2191 (1980), edited by S. Patai, The C
hemistry of Organic Serenium and Tellurium Compoun
The compounds described in ds. Vo11 (1986) and Vo12 (1987) can be used. In particular, the compounds represented by formulas (II), (III) and (IV) in JP-A-5-313284 are preferable.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains used, the chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. , Preferably 10 ⁻⁷ to 10 ⁻³
Use molar amounts. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to. It is 85 ° C.

Examples of the noble metal sensitizer used in the present invention include gold, platinum and palladium, with gold sensitization being particularly preferred. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide. About 10 ^-7 to 10 ^-2 mol per mol of silver halide is used. Can be used.

In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite salt, a lead salt, a thallium salt and the like may coexist in the process of formation of silver halide grains or physical ripening. Reduction sensitization can be used in the present invention. As the reduction sensitizer, stannous salt, amines, formamidinesulfinic acid, silane compound and the like can be used. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method shown in EP 293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, different halogen compositions, different crystal habits, chemically sensitized ones). (Under different conditions) may be used together.

The silver halide photographic light-sensitive material of the present invention may contain a rhodium compound in order to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a halogen, an amine, oxalate, etc. as a ligand, for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaamminerhodium ( III) Complex salt, Trizalatrodium (I
II) Complex salts and the like. These rhodium compounds are
It is used by dissolving it in water or a suitable solvent, but it is generally used to stabilize the solution of the rhodium compound, that is, an aqueous solution of hydrogen halide (eg hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.), or halogenation. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve another silver halide grain which has been previously doped with rhodium when preparing the silver halide.

The total addition amount of the rhodium compound is 1 × 10 ^{-8 to} 5 × 1 per mol of the finally formed silver halide.
0 ^-6 mol is suitable, and preferably 5 x 10 ^-8 to 1 x 1
It is 0 ^-6 mol. The addition of these compounds can be appropriately carried out at the time of producing silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to be incorporated in the silver halide grains. preferable.

The silver halide photographic light-sensitive material of the present invention may contain an iridium compound in order to achieve high sensitivity and high contrast. As the iridium compound used in the present invention, various compounds can be used, and examples thereof include hexachloroiridium, hexaammineiridium, trioxalatoiridium, hexacyanoiridium and the like. These iridium compounds are used by dissolving them in water or a suitable solvent, and a method that is generally performed to stabilize the solution of the iridium compound,
That is, a method of adding an aqueous solution of hydrogen halide (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (for example, KCl, NaCl, KBr, NaBr, etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide.

The total amount of iridium compound added is
1 × 10 per mol of silver halide formed^-8~ 5x
10^-6Moles are suitable, preferably 1 x 10^-8~ 1x
10 ^-6It is a mole. The addition of these compounds is
Steps during the production of silver halide emulsion grains and before coating the emulsion
Can be carried out as appropriate, especially when the emulsion is formed.
In addition, it is preferable that it is incorporated into the silver halide grain.
Yes.

The silver halide grains used in the present invention include
It may contain metal atoms such as iron, cobalt, nickel, ruthenium, palladium, platinum, gold, thallium, copper, lead and osmium. The metal is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁴ mol per mol of silver halide. Further, in order to contain the above metal, a metal salt in the form of a single salt, a double salt or a complex salt can be added and added at the time of preparation of particles.

The silver halide grains used in the silver halide photographic light-sensitive material of the present invention may contain at least one metal selected from rhenium, ruthenium and osmium. This content is 1 × 10 ⁻⁹ to 1 mol of silver.
The range of 1 × 10 ^-5 mol is preferable, and further 1 × 10 ^-8
The range of 1 × 10 ⁻⁶ mol is preferable. These metals are 2
You may use together 1 or more types. These metals can be contained uniformly in the silver halide grains, and JP-A-63-
29603, JP-A-2-306236, 3-16.
No. 7545, No. 4-76534, and Japanese Patent Laid-Open No. 5-2722.
No. 03, No. 6-110146, etc., it is also possible to allow the particles to have a distribution. Rhenium, ruthenium and osmium are disclosed in JP-A-63-20.
No. 42, JP-A Nos. 1-285941 and 2-20852.
No. 2-20855, etc., and is added in the form of a water-soluble complex salt. Particularly preferred are hexacoordinated complexes represented by the following formulas. [ML ₆ ] ^n- Here, M represents Ru, Re, or Os, and n represents 0, 1, 2, 3, or 4. In this case, the counterion has no significance and ammonium or alkali metal ions are used. Examples of preferred ligands include halide ligands, cyanide ligands, cyan oxide ligands, nitrosyl ligands and thionitrosyl ligands. Examples of specific complexes used in the present invention are shown below, but the present invention is not limited thereto.

[ReCl ₆ ] ^3- [ReBr ₆ ] ^3- [ReCl ₅ (NO)] ^2- [Re (NS) Br ₅ ] ^2- [Re (NO) (CN) ₅ ] ^2- [Re (O) 2 (NO) ₄ ] ^3- [RuCl ₆ ] ^3- [RuCl ₄ (H ₂ O) ₂ ] ^1- [RuCl ₅ (NO)] ^2- [RuBr ₅ (NS)] ^2- [Ru (CN) ₆ ] ^4- [Ru (CO) 3Cl3] ^2- [Ru (CO) Cl ₅ ] ^2- [Ru (CO) Br ₅ ] ^2- (OsCl ₆ ) ^3- (OsCl ₅ (NO)) ^2- (Os (NO) (CN) ₅ ) ^2- (Os (NS) Br ₅ ) ^2- (Os (CN) ₆ ) ^4- [Os (O ) ₂ (CN) ₄ ) ^4-

The addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion grains and at each stage before coating the emulsion.
It is preferably incorporated into silver halide grains. To incorporate these compounds into the silver halide grains by adding them during the formation of silver halide grains, a powder of a metal complex or an aqueous solution dissolved together with NaCl or KCl is used to form a water-soluble salt or a water-soluble salt during grain formation. Method in which a silver halide grain is prepared by adding it into a water-soluble halide solution, or by adding as a third solution when a silver salt and a halide solution are mixed at the same time, and a three-liquid simultaneous mixing method, or grain formation There is a method in which a necessary amount of an aqueous solution of a metal complex is charged into a reaction vessel. Especially powder or NaCl, KCl
A method in which an aqueous solution dissolved together with is added to the water-soluble halide solution is preferable. To add to the surface of the particles, a necessary amount of the aqueous solution of the metal complex can be added to the reaction vessel immediately after the particles are formed, during or after the physical ripening, or during the chemical ripening. The silver halide grain in the present invention may be doped with another heavy metal salt. In particular, K ₄ [Fe (C
Doping with Fe salts, such as N) ₆ ], is advantageous. Further, in the present invention, other metals included in Group VIII, namely, cobalt, nickel, iridium, palladium,
You may use platinum etc. together. In particular, the combined use with iridium salts such as iridium chloride and ammonium hexachloroiridium (III) is advantageous because a high-sensitivity and high-contrast emulsion can be obtained.

A spectral sensitizing dye selected according to the exposure wavelength can be added to the silver halide emulsion layer used in the present invention. Useful sensitizing dyes used in the present invention are, for example, RESEARCH DISCLOSURE Item 17643 IV-
Item A (p.23, December 1978), Item 183
It is described in the literature described or cited in Section 1X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) Argon laser light sources are described in JP-A-60-162247, JP-A-2-48653, US Pat. No. 2,161,331, West German Patent 936,071, and JP-A-5-11389. For simple merocyanines and B) helium-neon laser light sources, JP-A-50-62425 and JP-A-50-42525.
For the trinuclear cyanine dyes shown in Nos. 4-18726 and 59-102229, C) LED light source and red semiconductor laser, Japanese Examined Patent Publication No. 48-42172 and 51-
No. 9609, 55-39818, JP-A-62-28
4343, the thiacarbocyanines described in JP-A-2-105135, and D) infrared semiconductor laser light source, JP-A-59-191032 and JP-A-60-80.
Tricarbocyanines described in Japanese Patent No. 841.
9-192242 and the general formula of JP-A-3-67242
(IIIa), dicarbocyanines containing the 4-quinoline nucleus described in the general formula (IIIb), etc. are advantageously selected. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 17
Volume 6, 17643 (published December 1978), page 23, IV, section J. The content of the sensitizing dye of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, the type of antifoggant compound, and the like. It is desirable to select the optimum amount accordingly, and the test method for the selection is well known to those skilled in the art. Usually, it is preferably used in the range of 10 ^-7 to 1 × 10 ^-2 mol, particularly 10 ^-6 to 5 × 10 ^-3 mol per mol of silver halide.

Protective colloid of photographic emulsion or emulsion layer or other hydrophilic colloid layer (including conductive metal oxide-containing layer)
As the binder, it is advantageous to use gelatin, 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 hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used. In addition to lime-processed gelatin as gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,
Mercaptothiadiazoles, aminotriazoles,
Benzothiazoles, nitrobenzotriazoles, etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Hydroquinone and its derivatives; Disulfides, such as thioctic acid; Antifoggants such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Alternatively, many compounds known as stabilizers can be added. Among these, preferred are benzotriazoles (eg, 5
-Methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Also,
These compounds may be contained in the treatment liquid.

The light-sensitive material of the present invention may contain an organic desensitizer. Preferred organic desensitizers have at least one water-soluble group or alkali-labile group. These preferred organic desensitizers are exemplified in US Pat. No. 4,908,293. When an organic desensitizer is used, 1.0 × 10 ^{−8 to} 1.0 × 10 ⁻⁴ mol / m ² , preferably 1.0 × 10 ^{−7 to} 1.0 × 10 ^{− in the} silver halide emulsion layer. ^It is suitable that ⁵ mol / m ^{2 is} present.

The emulsion layer or other hydrophilic colloid layer of the present invention may contain a dye as a filter dye or for various purposes such as prevention of irradiation. As a filter dye, a dye for further lowering photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the intrinsic sensitivity region of silver halide, and safety against safelight light when handled as a light-sensitive room light material A dye having substantial light absorption mainly in the region of 310 nm to 600 nm is used for enhancing the light emission. These dyes are added to the emulsion layer depending on the purpose, or added together with a mordant to the upper portion of the silver halide emulsion layer, that is, to the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support. It is preferable to fix it before use. It depends on the molar absorption coefficient of the dye, but usually 10 ^-3 g / m ^{2 -1}
It is added in the range of g / m ² . Preferably 10 mg to 500
It is mg / m ² . The above dye can be added to the coating solution after being dissolved or dispersed in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof]. These dyes can be used in combination of two or more kinds. Specific examples of these dyes are described in US Pat. No. 4,908,293. Other,
US Pat. Nos. 3,533,794 and 3,314,794
No. 3,352,681, JP-A-46-2784
U.S. Pat. Nos. 3,705,805 and 3,707,3.
No. 75, No. 4,045,229, No. 3,700,45
5, 3,499,762, West German patent application publication 1,
Ultraviolet absorbing dyes described in, for example, No. 547,863 are also used. In addition, pyrazolone oxonol dyes described in US Pat. No. 2,274,782, US Pat.
956,879, diarylazo dyes, U.S. Pat. Nos. 3,423,207 and 3,384,487, styryl dyes and butadienyl dyes, and U.S. Pat. No. 2,527,583. Merocyanine dyes, US Pat. Nos. 3,486,897 and 3,652,284
No. 3,718,472, merocyanine dyes and oxonol dyes, and US Pat. No. 3,976,661.
No. 584,609, No. 1,177,429, JP-A Nos. 48-85130, 49-99620, 49-49, and 49-
114420, US Pat. Nos. 2,533,472, 3,148,187, and 3,177,078,
No. 3,247,127, No. 3,540,887
No. 3,575,704, No. 3,653,90
The dye described in No. 5 can also be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium yoban, chromium acetate, etc.), aldehydes (formaquedehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3- Dihydroxydioxane, etc., active vinyl compounds (1, 3,
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid) , Mucophenoxycyclo acid, etc.), an epoxy compound (tetramethylene glycol diglycidyl ether, etc.), an isocyanate compound (hexamethylene diisocyanate, etc.), etc. can be used alone or in combination. Also, JP-A-56-66841
U.S. Pat. No. 1,322,971 and U.S. Pat. No. 3,67
The polymer hardeners described in No. 1,256 can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced according to the present invention has a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example, development acceleration). , Contrast enhancement, sensitization), and various other surfactants may be included. For example, saponin (steroidal), alkylene oxide derivative (eg polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts), glycidol derivatives ( Nonionic surfactants such as alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyls Naphthalene sulfonate, alkyl sulfates, alkyl phosphates, N-acyl-N-alk Such as taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids or phosphoric acid esters, alkyl betaines, amine oxides; alkylamine hydrochloric acid, aliphatic or aromatic primary surfactants. Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Particularly, the surfactant preferably used in the present invention has a molecular weight of 60 described in JP-B-58-9412.
It is 0 or more polyalkylene oxides. Also, a polymer latex such as a polyalkyl acrylate may be incorporated for dimensional stability.

The developing agent used in the developing solution used in the present invention is not particularly limited, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and dihydroxybenzenes and 1-phenyl are preferable. A combination of -3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols may be used. Also,
Ascorbic acids are also preferably used as a developing agent. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,
Although there are 5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferable. 1 used in the present invention
Examples of the developing agent for -phenyl-3-pyrazolidone or a derivative thereof include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone and the like. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p
-Aminophenol is preferred. Developing agent is usually 0.0
It is preferably used in an amount of 5 mol / liter to 0.8 mol / liter. Also, dihydroxybenzenes and 1
When using a combination with -phenyl-3-pyrazolidones or p-aminophenols, the former is 0.05 mol / l to 0.5 mol / l and the latter is 0.06.
It is preferably used in an amount of not more than mol / liter. As a preservative of sulfite used in the present invention, sodium sulfite,
Examples include potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite content is preferably 0.3 mol / liter or more, and particularly preferably 0.4 mol / liter or more. Further, the upper limit is preferably up to 2.0 mol / liter, particularly up to 1.2. Also, when using the dihydroxybenzenes as developing agent, preservative
Ascorbic acids are preferably used, the addition amount is in the range of 0.03 to 0.12 in molar ratio to the developing agent preferred agent. Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
It contains a pH adjusting agent and a buffering agent such as potassium carbonate, sodium triphosphate, potassium triphosphate, sodium silicate and potassium silicate. The pH of the developer used in the developing treatment of the present invention is preferably in the range of 9.0 to 11.0. When the pH is 11 or more, the change with time of the developer becomes large, which is not preferable. Further, when the pH is 9.0 or less, sufficient contrast cannot be obtained. The range of pH 9.8 to 10.8 is more preferable. As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve , Organic solvents such as hexylene glycol, ethanol, methanol: 1-phenyl-5-mercaptotetrazole,
2-mercaptobenzimidazole-5-mercapto compounds such as sodium salt of sulfonic acid, indazole compounds such as 5-nitroindazole, and antifoggants such as benztriazole compounds such as 5-methylbenztriazole may be further contained. If necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, a film hardener, a stabilizer and the like may be contained. In particular, the amino compounds described in JP-A-56-106244 and the imidazole compounds described in JP-B-48-35493 are preferable in that they accelerate development or increase sensitivity. In the developer used in the present invention, a silver stain preventing agent is disclosed in JP-A-56-24347 and JP-A-HEI-4.
-362942, the compound described in JP-A-62-212651 as a development unevenness preventing agent, the compound described in JP-A-61-267759 as a dissolution aid, and the ascorbic acid as a stabilizer. Can be used. In the developing solution used in the present invention, boric acid described in JP-A-62-186259 and JP-A-60
A sugar described in No. 93433 (for example, sucrose),
Oximes (eg acetoxime), phenols (eg 5-sulfosalicylic acid), tertiary phosphates (eg sodium salt, potassium salt) and the like are used, and boric acid is preferably used.

The fixing solution is an aqueous solution containing a hardening agent (eg, water-soluble aluminum compound), acetic acid and dibasic acid (eg, tartaric acid, citric acid or salts thereof), if necessary, in addition to the fixing agent, and preferably It has a pH of 3.8 or higher, more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed, generally about 0.1.
Is about 5 mol / liter. The water-soluble aluminum salt, which mainly acts as a hardening agent in the fixing solution, is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds are contained in an amount of 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like can be given. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. If desired, the fixer may contain preservatives (eg, sulfite, bisulfite),
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image storage improving agent (eg, potassium iodide), and a chelating agent can be included. Here, since the pH of the developing solution is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter. The fixing temperature and time are the same as in the case of development, and about 2
0 seconds to about 50 ° C and 10 seconds to 1 minute are preferred.

For washing water, an antifungal agent (see, for example, Horiguchi, "Bacterial and Antifungal Chemistry", JP-A-62-115154).
Compound described in the specification), a water washing accelerator (such as sulfite), and a chelating agent. According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and it is carried out at about 20 ° C to about 50 ° C for 10 seconds to 3 seconds.
Minutes are preferred. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 minutes and 3 seconds.

Regarding the roller transport type automatic developing machine, US Pat. Nos. 3,025,779 and 3,54 are applicable.
5,971 and the like, and is simply referred to as a roller conveyance type processor in this specification. The roller conveyance type processor comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. Here, the water washing step is 2 to
Water saving can be achieved by using a three-stage countercurrent washing method.

The developing solution used in the present invention is described in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. The replenishing system described in JP-A-62-91939 can be preferably used as the developer used in the present invention.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4, and JP-A-2-103536, page 16, lower right column, line 3 See page 17, lower left column, line 20, and further JP-A Nos. 1-112235, 2-48653, 2-105135, 2-124560, 3-7928, and 3-67242. No. 5-11389, JP-A- 6-230496 , and spectral sensitizing dyes. 2) Nucleation accelerator A compound represented by formula (I), (II), (III), (IV), (V) or (VI) described in JP-A-6-82943 . JP-A No. 2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compounds II-1 to II-22, The compounds described in Kaihei 1-179939. 3) Surfactant, antistatic JP-A-2-12236, page 9, upper right column, line 7 to agent, same as lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 to same Page 4, lower right column 18, line 18. 4) Antifoggant and Stabilizer JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, line 1 to line 5. Furthermore, the thiosulfinic acid compounds described in JP-A-1-237538. 5) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compounds having an acid group JP-A-2-103536, page 8, lower right column, line 5 to page 19, upper left column, line 1 and page 2-55349, page 8 lower right column, line 13 To page 11, upper left column, line 8. 7) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column, line 15 Plasticizer to page 19, upper right column, line 15 8) Hardeners, JP-A-2-103536, page 18, upper right column, lines 5 to 17; 9) Dyes, JP-A-2-103536, page 17, lower right column, lines 1 to 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5. Furthermore, the solid dyes described in JP-A-2-294638 and JP-A-5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 11) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compounds Compounds represented by formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), and general formula (R in pages 3 to 20 of JP-A 3-174143). -1), (R-2) , (R -3), to no compound example 1 75, further JP-a No. 5 -257239, the compounds described in JP-a-4-278939. 13) Monomethine compound A compound of the general formula (II) described in JP-A-2-287532 (particularly compound examples 11-1 to II-26). 14) Dihydroxybenzene Compounds described in JP-A-3-39948, page 11, upper left column, type 12, page 12 lower left column, and European Patent No. 452,772A.

[0151]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion A was prepared by the following method. [Emulsion A] Aqueous silver nitrate solution, potassium bromide, sodium chloride, and K corresponding to 3.5 × 10 ^-7 mol per mol of silver
₃ IrCl ₆ and K ₂ Rh equivalent to 2.0 × 10 ⁻⁷ mol
Halogen salt aqueous solution containing (H ₂ O) Cl ₅ , sodium chloride and gelatin aqueous solution containing 1,3-dimethyl-2-imidazolidinethione were added by a double jet method with stirring to obtain an average particle size of 0.25 μm. Silver chlorobromide grains having a silver chloride content of 70 mol% were prepared.

After that, the product was washed with flocculation according to a conventional method, 40 g of gelatin was added per mol of silver, 7 mg of sodium benzenethiosulfonate and 2 mg of benzenesulfinic acid were added per mol of silver, and then the pH was adjusted to 6.0. The pAg was adjusted to 7.5, and 2 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. Thereafter, 150 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer, and 100 mg of proxel was added as a preservative. The obtained particles each have an average particle size of 0.25μ.
m and a silver chlorobromide cubic grain having a silver chloride content of 70 mol%. (Variation coefficient 10%)

Preparation of Coating Sample On a polyethylene terephthalate film support having a moisture-proof undercoat containing vinylidene chloride, from the support side,
A UL layer, an EM layer, a PC layer, and an OC layer were applied in this order to form a sample, and a sample was prepared. The preparation method and coating amount of each layer are shown below.

(UL layer) A dispersion of 30 % by mass of polyethyl acrylate in gelatin was added to an aqueous gelatin solution to give 0.5 g of gelatin.
It was applied so as to be / m ² .

[0156] in (EM layer) above emulsions A, the following compound as a sensitizing dye (S-1) per mole of silver 5 × 10 ^-4 mol, the 5 × 10 ^-4 mol was added (S-2), further 3 × 10 ^-4 mol of mercapto compound represented by the following (a), 4 × 10 ^-4 mol of mercapto compound represented by (b), and 4 × 10 ^-4 mol of (c) per 1 mol of silver The triazine compound, 2 × 10 ⁻³ mol of 5-chloro-8-hydroxyquinoline, the surface active compounds shown in Tables 1 and 2 and the onium salt compound of the present invention were added in the amounts shown in Tables 1 and 2. Furthermore, hydroquinone 100 mg, N-oleyl-N-
Methyltaurine sodium salt was added to be coated at 30 mg / m ² . Next, the hydrazine derivative of the present invention was added as shown in Tables 1 and 2, the water-soluble latex shown in (d) was 200 mg / m ² , the dispersion of polyethyl acrylate was 200 mg / m ² , methyl acrylate. And 2-
200m of latex copolymer of acrylamido-2-methylpropanesulfonic acid sodium salt and 2-acetoacetoxyethylmethacrylate (weight ratio 88: 5: 7)
² g of colloidal silica with an average particle size of 0.02 μm
00mg / m ^2, 1,3-vinylsulfonyl-2-propanol further as a hardening agent were added 200 mg / m ^2. The pH of the solution was adjusted to 5.65 with acetic acid. They were coated such that the coated silver amount was 3.5 g / m ² .

[0157] Dispersion of 50% by weight of ethyl acrylate with respect to gelatin (PC layer) aqueous gelatin solution and sodium ethyl sulfonate 5 mg / m ^2, 1,5-dihydroxy-2-benzaldoxime is 10 mg / m ² Add as applied,
It was coated so that gelatin was 0.5 g / m ² .

(OC layer) Gelatin 0.5 g / m ² , amorphous SiO ₂ matting agent 40 having an average particle size of about 3.5 μm
mg / m ² , methanol silica 0.1 g / m ² , polyacrylamide 100 mg / m ² and silicone oil 20 mg /
m ² and 5 mg / m ^{2 of} a fluorosurfactant represented by the following structural formula (e) as a coating aid and 100 mg / m ² of sodium dodecylbenzenesulfonate were coated.

[0159]

[Chemical 56]

[0160]

[Chemical 57]

These coated samples have a back layer and a back protective layer having the following compositions. [Back layer formulation-1] Gelatin 3 g / m ² latex Polyethyl acrylate 2 g / m ² Surfactant sodium p-dodecylbenzenesulfonate 40 mg / m ²

[0162]

[Chemical 58]

Dye Mixture of Dye [a], Dye [b], Dye [c] Dye [a] 70 mg / m ² Dye [b] 70 mg / m ² Dye [c] 90 mg / m ²

[0164]

[Chemical 59]

[Back Layer Formulation-2] SnO ₂ / Sb (weight ratio 90/10, average particle size 0.20)
μm) Back layer formulation except that 200 mg / m ² was added-
Same as 1. [Back protective layer] Gelatin 0.8 mg / m ² Polymethylmethacrylate fine particles (average particle size 4.5 μm) 30 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ²
Sodium p-dodecylbenzenesulfonate 15 mg
/ M ² Sodium acetate 40mg / m ²

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was passed through an interference filter having a peak at 488 nm and a light emission time of 10 ⁻⁵ se through a step wedge.
After being exposed to the xenon flash light of c, and developed with a developing solution A having the following composition at 35 ° C. for 30 seconds, fixing, washing with water and drying were performed. A fixing solution having the following composition was used as the fixing solution.

Developer A Potassium hydroxide 35.0 g Diethylenetriamine-pentaacetic acid 2.0 g Potassium carbonate 12.0 g Sodium metabisulfite 40.0 g Potassium bromide 3.0 g Hydroquinone 25.0 g 5-Methylbenzotriazole 0.08 g 4 -Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.45 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) -quinazolinone 0.04 g 2-mercaptobenz Sodium imidazole-5-sulfonate 0.15 g Sodium erythorbate 3.0 g Potassium hydroxide and water are added to make 1 liter and pH is 1
Adjust to 0.5.

Fixing solution Ammonium thiosulfate 359.1 ml Ethylenediaminetetraacetic acid 2Na dihydrate 2.26 g Sodium thiosulfate pentahydrate 32.8 g Sodium sulfite 64.8 g NaOH 37.2 g Glacial acetic acid 87.3 g Tartaric acid 8.76 g Sodium gluconate 6.6 g Aluminum sulphate 25.3 g pH (adjusted with sulfuric acid or sodium hydroxide) 4.85 Add water 1 liter (2) Evaluation of image contrast As an index (gamma) indicating the contrast of the image, the characteristic curve From the point of fog + concentration 0.3, fog + concentration 3.
The point of 0 was connected by a straight line, and the slope of this straight line was expressed as a gamma value. That is, gamma = (3.0-0.3) / [l
og (exposure amount that gives a density of 3.0)-(exposure amount that gives a density of 0.3)], and the larger the gamma value, the harder the photographic characteristics. (3) Evaluation of halftone dot quality (DQ) The halftone dots of the light-sensitive material exposed through the contact screen were observed with a magnifying glass, and the sharpness and smoothness were evaluated on a 5-point scale.
"5" represents the best level for both sharpness and smoothness, and "1" represents the lowest level. When the level is "3" or more, the sharpness and smoothness of the on / off portion of the image when the scanner is actually exposed is practically acceptable. (4) Evaluation of black spots A light-sensitive material which has not been exposed to light is developed using developer A at 90 ° C.
After development for 2 seconds, fixing, washing with water and drying were performed, and then the light-sensitive material was observed with a magnifying glass, and the generation level was evaluated on a 5-point scale. "5" represents the level that has not occurred at all, "1"
Represents the lowest level. A level of "3" or higher is practically acceptable. (4) Dissolution Stability Test of Coating Liquid Emulsion Layer (EM Layer) In order to investigate the effect of hydrazine derivative on the dissolution stability of coating liquid, the amount of hydrazine derivative in the coating liquid was adjusted to that of the coating liquid immediately after the adjustment. The coating liquid after 12 hours was quantified using HPLC (high performance liquid chromatography). The residual ratio of the hydrazine derivative was calculated based on the following formula. Residual rate (%) = [(amount of hydrazine derivative in coating solution after 12 hours from adjustment) / (amount of hydrazine derivative in coating solution immediately after adjustment)] × 100

[0169]

[Table 1]

[0170]

[Table 2]

<Results> From Tables 1 and 2, it can be seen that by providing the layer containing the conductive metal oxide of the present invention, generation of black spots derived from static electricity is suppressed. Furthermore, the surface-active compound of the present invention can suppress the decomposition of the hydrazine derivative and can also suppress the softening of the characteristic curve. According to the method of the present invention, it is possible to obtain a hard photographic performance A
r It has become possible to stably manufacture sensitive materials for laser scanners.

Example 2 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion B was prepared by the following method. [Emulsion B] Except that 1 mg of selenium sensitizer having the following structural formula, 1 mg of sodium thiosulfate and 4 mg of chloroauric acid were added per 1 mol of silver, and chemical sensitization was performed at 60 ° C. to obtain optimum sensitivity. It was adjusted in the same manner as Emulsion A.

[0173]

[Chemical 60]

Preparation of Coating Sample Instead of the sensitizing dye in the EM layer of Example 1, 2.1 × 10 ⁻⁴ mol of the following compound (S-3) was added per 1 mol of silver to prepare an emulsion for the EM layer. Emulsion A described in Example 1,
A sample was prepared in the same manner as in Example 1 except that any of the emulsions B prepared according to the above formulation was used. Table 2 shows the types of hydrazine derivatives, onium salt compounds and surface-active compounds added to the EM layer, and the amounts added.

[0175]

[Chemical formula 61]

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The above sample was exposed to xenon flash light with an emission time of 10 ⁻⁶ sec through a step wedge through an interference filter having a peak at 633 nm.
I did . The developer A described in Example 1 was used for 30 at 35 ° C.
After developing for a second, fixing, washing with water and drying were performed. The fixer described in Example 1 was used as the fixer. (2) Evaluation of sensitivity The sensitivity is indicated by the reciprocal of the logarithmic value of the exposure amount that gives a density of 1.5. (3) Evaluation of Image Contrast The same evaluation as in Example 1 was performed. (4) Dissolution temporal stability test of coating solution In order to examine the dissolution temporal stability of the emulsion layer (EM layer) coating solution, a sample which was applied immediately after the emulsion layer coating solution was prepared,
12 hours after adjusting the coating solution, a sample coated with the same formulation was prepared, and the change in sensitivity (ΔS) was examined. Δ
If S is 0.05 or less, stable production is possible. ΔS = (sensitivity of sample applied 12 hours after adjustment of coating liquid) − (sensitivity of sample applied immediately after adjustment of coating liquid)

[0177]

[Table 3]

[0178]

[Table 4]

<Results> From Tables 3 and 4 , it can be seen that by providing the layer containing the conductive metal oxide of the present invention, generation of black spots derived from static electricity is suppressed. Further, by using a selenium-sensitized emulsion, ultra-high contrast can be obtained with a small amount of hydrazine derivative, but the sensitization due to the dissolution of the coating solution over time becomes large and stable production becomes impossible. However, sensitization was suppressed by using the surface-active compound of the present invention. According to the method of the present invention, it is possible to stably produce a light-sensitive material for a helium neon laser scanner capable of obtaining a high-contrast photographic performance even if the amount of a small amount of a hydrazine derivative used is further reduced or even if it is processed with a developer having a pH of less than 11. Became.

Example 3 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 2 except that the sensitizing dye in the EM layer of Example 2 was changed to the following compound (S-4). Created.

[0181]

[Chemical formula 62]

<Evaluation of Photographic Performance> The above sample was passed through an interference filter having a peak at 780 nm and a light emission time of 10 ⁻⁶ se through a step wedge.
It was exposed in a xenon flash light c. After developing with the developer A described in Example 1 at 35 ° C. for 30 seconds, fixing, washing with water and drying were performed. Example 1 for the fixer
The fixing solution described in 1. was used. Image contrast evaluation,
The dissolution temporal stability test of the coating liquid was performed in the same manner as in Example 2. <Results> As in Example 2, the surfactant compound of the present invention suppressed the sensitization caused by the dissolution of the coating solution. According to the method of the present invention, it has become possible to stably produce a light-sensitive material for a semiconductor laser scanner capable of obtaining a hard photographic performance even when treated with a developer having a pH of less than 11.

Example 4 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 2 except that the sensitizing dye in the EM layer of Example 2 was changed to the following compound (S-5). Created.

[0184]

[Chemical formula 63]

<Evaluation of Photographic Performance> The above sample was exposed to 3200 ° K. tungsten light through a step wedge. Developer A described in Example 1
After developing for 30 seconds at 35 ° C., fixing, washing with water,
It was dried. The fixer described in Example 1 was used as the fixer. The evaluation of image contrast and the stability test of dissolution of the coating solution with time were performed in the same manner as in Example 2. <Results> As in Example 2, the surfactant compound of the present invention suppressed the sensitization caused by the dissolution of the coating solution. According to the method of the present invention, it has become possible to stably produce a photographic light-sensitive material capable of obtaining a high contrast photographic performance.

Example 5 Based on the photosensitive material formulation of Example 5 of JP-A-7-43867 , the hydrazine derivative of the present invention and the surface active compound of the present invention were added, and a stability test of dissolution of the coating solution with time was conducted. went. As in Examples 2 to 4 of the present specification, the surface-active compound of the present invention suppressed the sensitization caused by the aging of the coating solution.

Example 6 <Preparation of silver halide photographic light-sensitive material> A sample was prepared in the same manner as in Example 1.

<Evaluation of Photographic Performance> The same procedure as in Example 1 was carried out except that Developer B having the following composition was used instead of Developer A used in Example 1.

Developer B Sodium hydroxide 10.0 g Diethylenetriamine-pentaacetic acid 1.5 g Potassium carbonate 15.0 g Potassium bromide 3.0 g 5-Methylbenzotriazole 0.10 g 1-Phenyl-5-mercaptotetrazole 0.02 g Sulfurous acid Potassium 10.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.15 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 0.40 g Sodium erythorbate 30.0 g Potassium hydroxide is added, Add water to make 1 liter p
Adjust H to 10.7.

Image contrast and halftone dot quality (D
In Example 1, the evaluation of Q) and the stability test of dissolution of the coating solution over time were performed.
I went the same way.

<Results> As in Example 1, the surface active compound of the present invention suppressed the decomposition of the hydrazine derivative and suppressed the softening of the characteristic curve.

Example 7 <Preparation of silver halide photographic light-sensitive material> Emulsion preparation Emulsion C was prepared by the following method. [Emulsion C] 5.0 × per mol of silver in a gelatin aqueous solution kept at 40 ° C.
An aqueous solution of silver nitrate and an aqueous solution of sodium chloride were simultaneously mixed in the presence of 10 ^-6 mol of NH 4 RhCl ^6, and then soluble salts were removed by a method well known in the art and gelatin was added to the solution without chemical ripening. 2-Methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. This emulsion has an average grain size of 0.2 μ
It was a monodisperse emulsion having a cubic crystal form of m .

Preparation of Coating Sample As shown in Tables 5 and 6, the hydrazine derivative of the present invention, the onium salt compound and the surface active compound were added to this emulsion. Furthermore, the polyethyl acrylate latex is used in terms of solid content to gelatin 30 % by mass.
In addition, 1,3-di-vinylsulfonyl-2-propanol was added as a hardening agent and coated on a polyester support so as to have an Ag amount of 3.8 g / m ^2. Gelatin was 1.8 g / m ^2. It was m ² . As a protective layer, a layer of 1.5 g / m ² of gelatin and 0.3 g / m ² of polymethylmethacrylate having a particle size of 2.5 μm was applied thereon.

The base used in this example has a back layer and a back protective layer having the following compositions. Here, the swelling ratio on the back side is 110%. (Back Layer Formulation -1) Gelatin 170 mg / m ² Sodium dodecylbenzenesulfonate 32 mg / m ² dihexyl -α- sulfo succinate inert sodium 35 mg / m ² (Back Layer Formulation -2) SnO ₂ / Sb (9/1 weight ratio , Average particle size 0.25 μm) Same as Back Layer Formulation 1 except that 318 mg / m ² was added. (Back protective layer formulation) Gelatin 2.7 g Silicon dioxide matting agent (average particle size 3.5 μm) 26 mg / m ² Dihexyl-α-sulfosuccinate sodium 20 mg / m ² Sodium dodecylbenzenesulfonate 67 mg / m ²

[0195]

[Chemical 64]

[0196]

[Chemical 65]

Ethyl acrylate latex (average particle size 0.05 μm) 260 mg / m ² 1,3-divinylsulfonyl-2-propanol 149 mg / m ²

<Evaluation of Photographic Performance> (1) Exposure and Development Treatment The obtained sample was exposed through a step wedge with a bright room printer P-627FM manufactured by Dainippon Screen Co., Ltd. Develop with the developer A described in Example 1 at 38 ° C. for 20 seconds with an automatic processor FG10NH,
It was fixed with the fixing solution described in Example 1, washed with water and dried. (2) Evaluation of image contrast The same evaluation as in Example 1 was performed. (3) Dissolution temporal stability test of coating solution Emulsion layer (EM layer) In order to investigate the influence of hydrazine derivative on the temporal stability of coating solution dissolution, the amount of hydrazine derivative in the coating solution was adjusted to that of the coating solution immediately after the adjustment. The coating solution that had been left for 6 hours was quantified using HPLC (high performance liquid chromatography), and the residual ratio of the hydrazine derivative was calculated in the same manner as in Example 1.

[0199]

[Table 5]

[0200]

[Table 6]

<Results> From Tables 5 and 6, it is understood that by providing the layer containing the conductive metal oxide of the present invention, generation of black spots derived from static electricity is suppressed. Furthermore, the surface-active compound of the present invention can suppress the decomposition of the hydrazine derivative and can also suppress the softening of the characteristic curve. According to the method of the present invention, it is possible to stably produce a bright-room reversal light-sensitive material capable of obtaining a hard photographic performance even if it is processed with a developer having a pH of less than 11.

Continuation of front page (56) References JP-A-62-280733 (JP, A) JP-A-4-76530 (JP, A) JP-A-4-253051 (JP, A) JP-A-4-107444 (JP , A) JP-A-7-56267 (JP, A) JP-A-1-260436 (JP, A) JP-A-57-11341 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB) Name) G03C 1/06 501 G03C 1/295 G03C 1/38 G03C 1/85

Claims (3)

(57) [Claims] 1. A support having at least one silver halide emulsion layer, and at least one hydrazine derivative represented by the following general formula (I) in at least one of the emulsion layer and other hydrophilic colloid layers. One of the following general formulas (II) and (II
I), (IV), at least one of the onium salt compounds represented by (V), and at least the compound represented by the general formula (VI)
A silver halide photographic light-sensitive material comprising at least one layer containing one kind and containing a conductive metal oxide. [Chemical 1] (In the formula, R ₁ represents an aliphatic group or an aromatic group, and R ₂
Represents a fluorine-substituted alkyl group or a fluorine-substituted aryl group, G ₁ represents —CO— group, —SO ₂ — group, —SO—
Group, —CO— group, —SO ₂ — group, —SO— group, Represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group, and A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted Represents an arylsulfonyl group or a substituted or unsubstituted acyl group. R ₃ is selected from the same range as the group defined for R ₂ ,
It may be different from R ₂ . ) [Chemical 3] (In the formula, R ₁ , R ₂ , and R ₃ represent an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, a cycloalkenyl group, or a heterocyclic residue, which may further have a substituent. M is an integer of 1 to 4, and L is P
Represents an m-valent organic group that is bonded to an atom and its carbon atom,
n represents an integer of 1 to 3, X represents an n-valent anion, and X may be linked to L. ) [Chemical 4] (In the formula, A represents an organic group for completing a heterocycle. B and C each represent a divalent group. R ₁ and R ₂ each represent an alkyl group or an aryl group, and R ₃ and R ₄ Represents a hydrogen atom or a substituent, and R ₅ represents an alkyl group.
X represents an anion group, but X is not necessary in the case of an inner salt. ) [Chemical 5] (In the formula, R ₁ is an aliphatic group, an alicyclic compound group, or an aromatic group.
Or a heterocycle, R ₂ is an aliphatic group, an alicyclic compound
A group, an aromatic group, a heterocycle or a group represented by -LZ
Represent Q ₁ , Q ₂ and Q ₃ are a single bond and oxygen source, respectively.
Child, sulfur atom, -N (R ₃₎ - or -N (R ₃₎ -C
Group (R ₃ represented by O- is represented by hydrogen atom or R ₂
Group). L represents a divalent linking group. Z is ionic
Represents the group of. ) 2. The silver halide photographic light-sensitive material according to claim 1, wherein the layer containing a conductive metal oxide is provided between the light-sensitive layer and the support. 3. A silver halide photographic light-sensitive material according to claim 1, wherein the layer containing a conductive metal oxide is on the opposite side of the support from the light-sensitive layer.