JPH0527348A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material small in variation of sensitivity due to storage by incorporating a specified compound in an emulsion layer or another hydrophilic colloidal layer. CONSTITUTION:The photosensitive material contains in an emulsion layer, negative type nonspectrally sensitized silver halide grains containing silver chloride in an amount of at least 70mol% of the silver halide, and rhodium salt in an amount of 1X10<-8>-1X10<-4> per one mole of silver halide, and these grains has an average grain diameter of 0.05-0.30mum, and this emulsion layer or another hydrophilic colloidal layer contains at least one of the compounds represented by formula I in which each of R1 and R2 is H or optionally substituted alkyl; each of R3-R7 is H, alkyl, alkoxy, halogen, or the like or each of (R1 and R7) and (R2 and R3) may combine with each other to form a 5-or 6-membered ring, thus permitting the obtained photosensitive material to be high in sensitivity and small in variation of sensitivity during storage and to be handled for a long time in the light.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material for a bright room.

[0002]

2. Description of the Related Art In recent years, in the field of printing and plate making, in order to save labor, rationalize, and improve the working environment, it has become possible to perform film making, which is conventionally performed in a dark room, so-called reversing process work in a bright room. There is a demand for a technology for improving the light-sensitive materials and printers.

As a light-sensitive material which can be handled in such a bright room, a silver halide light-sensitive material which is sensitive to a light source rich in ultraviolet light, for example, an ultrahigh pressure mercury lamp, a metal halide light source, a xenon lamp, a halogen lamp, a quartz lamp or the like. Can be given.

As a method for producing a silver halide photographic light-sensitive material (hereinafter referred to as a light-room material) that can be handled in a bright room, an inorganic material such as rhodium salt or bismuth salt described in JP-A-56-125734 is used. A method of adding a desensitizer to an emulsion mainly composed of silver chloride, a method of adding an organic desensitizer to an emulsion mainly composed of silver chloride, which is described in JP-A-45-17273. 59-157633 and 61-26041, a method of adding a rhodium salt and an organic desensitizer to an emulsion mainly composed of silver chloride, the method described in JP-B-63-316042, A method of adding a rhodium salt, a desensitizing dye, a tetrazolium compound, a hydrazine compound to an emulsion layer mainly composed of silver, and a dye to the backing layer so that the absorbance at the maximum wavelength of the spectral sensitivity of the desensitizing dye becomes 0.5 or more. Are known.

The present inventors have confirmed that the method of adding an inorganic desensitizer to an emulsion mainly composed of silver chloride is effective, but there has been a problem in that the sensitivity varies depending on the storage of the light-sensitive material.
In particular, recently, there has been an increasing demand for a bright room light-sensitive material to prolong the handling time in a bright room, and the above effects have not sufficiently satisfied the recent requirements.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a negative-working silver halide photographic light-sensitive material which has high sensitivity and can be handled in a bright room for a long time.

Another object of the present invention is to provide a silver halide photographic light-sensitive material which is less sensitive in sensitivity during storage.

[0008]

The objects of the present invention are achieved by the following. That is, (1) in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, the light-sensitive material is
Contains negative type non-spectral sensitized silver halide grains having an average grain size of 0.05 to 0.30 μm, containing at least 70 mol% of silver chloride and 1.0 × 10 ⁻⁸ to 10 ⁻⁴ mol of rhodium salt per mol of silver halide. And a hydrophilic colloid layer containing at least one compound represented by the general formula [I] in the emulsion layer and / or the other hydrophilic colloid layer.

[0009]

[Chemical 4]

In the formula, R ₁ and R ₂ each represent a hydrogen atom or an optionally substituted alkyl group, and R ₁ and R ₂ may be bonded to each other to form a 5-membered ring or a 6-membered ring. Good. R ₃ , R ₄ ,
R ₅ , R ₆ and R ₇ are each a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acylamino group, a formyl group, a hydroxyl group, a carboxyl group, a sulfo group,
It represents a sulfonamide group or a halogen atom. R ₃ and R ₇ are
R ₁ and R ₇ or R ₂ and R ₃ represent a non-metal atomic group necessary for forming a 5-membered ring or a 6-membered ring.

(2) The hydrophilic colloid layer adjacent to the emulsion layer contains at least one compound represented by the general formula [II] and / or a compound represented by the general formula [III]. A silver halide photographic light-sensitive material as described in (1) above.

[0012]

[Chemical 5]

In the general formula [II], R ₈ , R ₉ , R ₁₀ ,
R ₁₁ represents a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, and X ₁ and X ₂ represent an oxygen atom or a sulfur atom.
L ₁ , L ₂ and L ₃ represent a methine group, and n ₁ represents 0, 1 or 2.

In the general formula [III], R ₁₂ and R ₁₃ are each a hydrogen atom, a halogen atom, an alkylcarbonyl group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a sulfonamide group, a substituted or unsubstituted alkyl group or aryl. It represents a group, and R ₁₂ and R ₁₃ may form a ring. Y ₁
And Y ₂ are each —O—, —S—, —Se—, —Te—, —CO—,
_{-SO 2 -, - N (R} 14) - represents, Y ₁ and Y ₂ may be the same or different.

L ₄ is --CH ₂ CH _2- , --C (R ₁₅ ) H--CH _2- , --C
_{(R 16) H-CH 2} -, it represents, L ₅ is = CH -, = C (R 17) - represents a. n ₂ represents an integer of 0 to 6, Z is a hydroxyl group,
It represents a carboxyl group, a sulfo group, an amino group, an alkylcarbonyl group, a halogen atom, an alkoxy group, an alkylthio group, an aminosulfonyl group, a substituted or unsubstituted alkyl group or an aryl group. m ₁ represents an integer of 0 to 3, R
₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each an alkyl group, an aryl group,
It represents an alkoxy group, an alkylthio group, a trialkylsiloxy group, a halogen atom or a tertiary amino group. M ₁ and M ₂ represent an alkali metal, and M ₁ and M ₂ may be the same or different.

(3) The silver halide photographic light-sensitive material according to (1), wherein the hydrophilic colloid layer adjacent to the emulsion layer contains at least one compound represented by the general formula [IV]. material.

[0017]

[Chemical 6]

In the formula, G represents a hydrogen atom or a halogen atom, and R ₁₈ represents a monovalent group having a Hammett δp value of less than -0.05. R ₁₉ represents an aryl group having at least one sulfonic acid group, and R ₂₀ represents a lower alkyl group, a halogen atom, a hydroxyl group or an alkoxy group. R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group, and R ₂₁ and R ₂₂ may combine with each other to form a 5-membered ring or a 6-membered ring. L ₆ , L ₇ , and L ₈ represent a methine group, and m ₂ is 1, ₂ , 3
Or 4, and n ₃ represents 1 or 2.

The present invention will be described in detail below.

In the general formula [I], examples of the alkyl group represented by R ₁ and R ₂ include groups such as methyl, ethyl, propyl and cyclohexyl. The alkyl group may have a substituent, and examples of the substituent include halogen atom, hydroxyl, alkoxy, carboxyl, alkoxycarbonyl, alkylsulfonyl, sulfonamide, cyano, sulfo, acylamino, carbamoyl, sulfamoyl and the like. Can be mentioned.

Further, R ₁ and R ₂ may combine to form a 5- or 6-membered nitrogen-containing heterocycle (eg, morpholine ring).

Preferable alkyl groups as R _{3 to} R ₇ include groups such as methyl, ethyl, propyl, butyl and pentyl.

Preferred alkoxy groups as R _{3 to} R ₇ include groups such as methoxy, ethoxy, propoxy, butoxy and the like.

The alkoxycarbonyl group includes, for example, each group such as ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, and the acylamino group includes, for example, each group such as acetamide, propioamide, butanamide. Examples of the sulfonamide group include methanesulfonamide, ethanesulfonamide, butanesulfonamide and the like.

R ₃ and R ₇ represent a group of non-metal atoms necessary for R ₁ and R ₇ or R ₂ and R ₃ to combine to form a nitrogen-containing heterocycle.

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

The compound represented by the general formula [I] can be easily obtained as a commercial product, or can be synthesized by a method known in the art.

The compound represented by the general formula [I] used in the present invention may be added at any stage such as during the formation of silver halide grains, after the grain formation and after desalting.

The amount of addition is preferably 0.005 to 100 g / mol Ag, more preferably 0.01 to 50 g / mol Ag.

The compound represented by the general formula [I] is dissolved in a suitable solvent such as water or alcohols (for example, methanol, ethanol, propanol, etc.) to prepare a silver halide emulsion layer and / or another hydrophilic colloid layer. Can be added to.

In the compound represented by the general formula [II],
Examples of the alkyl group represented by R _{8 to} R ₁₁ include methyl, ethyl, propyl, i-propyl, t-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, dodecyl, pentadecyl, eicosyl and the like. To be
The alkyl group includes those having a substituent, and examples of the substituent include a halogen atom (for example, each atom of chlorine, bromine, iodine, fluorine, etc.), an aryl group (for example, phenyl,
Naphthyl etc.), heterocyclic group (eg pyrrolidyl, pyridyl etc.), sulfinic acid group, carboxyl group, nitro group,
Hydroxyl group, mercapto group, amino group (eg amino, diethylamino etc.), alkoxy group (eg methoxy, ethoxy, butoxy, octyloxy, i-propoxy etc.), aryloxy group (phenoxy, naphthyloxy etc.), carbamoyl group (eg Aminocarbonyl, methylcarbamoyl, pentylcarbamoyl, morpholinocarbonyl, phenylcarbamoyl etc.), amide group (eg methylamide, benzamide, octylamide etc.), sulfamoyl group (eg sulfamoyl, methylsulfamoyl, phenylsulfamoyl, morpholinosulfonyl, butyl) Sulfamoyl etc.), sulfonamide group (eg methane sulfonamide, heptane sulfonamide, benzene sulfonamide etc.), sulfinyl group (eg methylsulfur) Iniru, ethylsulfinyl,
Alkylsulfinyl groups such as octylsulfinyl, arylsulfinyl represented by phenylsulfinyl), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, 2-hydroxyethoxycarbonyl, octyloxycarbonyl, etc.), aryloxycarbonyl groups (eg phenoxycarbonyl). , Naphthyloxycarbonyl etc.), alkylthio groups (eg methylthio, ethylthio, hexylthio etc.), arylthio groups (eg phenylthio, naphthylthio etc.), alkylcarbonyl groups (eg acetyl, ethylcarbonyl, butylcarbonyl, octylcarbonyl etc.), arylcarbonyl groups (Eg benzoyl, p-methanesulfonamidobenzoyl, p-carboxybenzoyl, naphthoyl etc.), cyano group, urei Group (for example methylureido,
Phenylureido etc.), thioureido group (eg methylthioureido, phenylthioureido etc.) and the like.

Examples of the aryl group represented by R _{8 to} R ₁₁ include a phenyl group and a naphthyl group. The aryl group includes those having a substituent, examples of the substituent group, e.g., exemplified as the substituent for the alkyl group represented by R ₈ to R _11, and alkyl groups represented by R ₈ to R ₁₁ And the above-mentioned groups.

Examples of the alkenyl group as a substituent represented by R _{8 to} R ₁₁ include a vinyl group, an allyl group, a 1-propenyl group, a 1,3-butadienyl group and a 2-pentenyl group. The group includes those having a substituent, and examples of the substituent include those mentioned as the substituent of the alkyl group represented by R _{8 to} R ₁₁ .

The heterocyclic group represented by R _{8 to} R ₁₁ includes
For example, a pyridyl group (eg, 2-pyridyl, 3-pyridyl, 4-
Pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2-
Pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-
Pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, 3-nitro-2-pyridyl, etc.), an oxazolyl group (for example, 5-carboxy-2-benzoxazolyl, 2-benzoxazolyl, 2 -Oxazolyl etc.), thiazolyl group (eg 5-sulfamoyl-2-benzothiazolyl, 2-benzothiazolyl, 2-thiazolyl etc.), imidazolyl group (eg 1-methyl-2-imidazolyl, 1-methyl-5-carboxy-2-benzimidazolyl) Etc.), furyl group (eg 3-furyl), pyrrolyl group (eg 3-pyrrolyl), thienyl group (eg 2-
Thienyl), pyrazinyl group (eg 2-pyrazinyl), pyrimidinyl group (eg 2-pyrimidinyl, 4-chloro-2-pyrimidinyl etc.), pyridazinyl group (eg 2-pyridazinyl), purinyl group (eg 8-purinyl), isoxazolyl group (Eg 3-isoxazolyl), selenazolyl group (eg 5-carboxy-2-selenazolyl), sulforanyl group (eg 3-sulfolanyl), piperidyl group (eg
1-methyl-3-piperidyl), a pyrazolyl group (for example, 3-pyrazolyl), a tetrazolyl group (for example, 1-methyl-5-tetrazolyl), and the like, and the heterocyclic group includes those having a substituent. Examples of the group include those exemplified as the substituents for the alkyl group represented by an alkyl group and R ₈ to R ₁₁ represented by the R ₈ to R _11.

Examples of the cycloalkyl group represented by R _{8 to} R ₁₁ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.
The cycloalkyl group include those having a substituent, and examples of the substituent exemplified as the substituents for the alkyl group represented by an alkyl group and R ₈ to R ₁₁ is represented by R ₈ to R ₁₁ described above There are things.

When R _{8 to} R ₁₁ are alkyl groups,
It is particularly preferable that the carbon number is 6 or less.

In the general formula [II], the methine groups represented by L _{1 to} L ₃ include those having a substituent, and the substituent includes, for example, an alkyl group (eg, methyl, ethyl, i-propyl, t). -Butyl, 3-hydroxypropyl etc.), aralkyl group (eg benzyl), aryl group (eg phenyl), halogen atom (eg chlorine, bromine, iodine, fluorine etc.), alkoxy group (eg methoxy, ethoxy etc.),
An aryloxy group (for example, phenoxy), an acyloxy group (for example, methylcarbonyloxy, phenylcarbonyloxy, etc.) and the like can be mentioned.

Specific compound examples of the present invention are shown below.
The present invention is not limited to these.

[0041]

[Chemical 9]

[0042]

[Chemical 10]

In addition to the above compounds, Japanese Patent Application No. 2-19474-1
Compounds No. 1 to No. 22 and No. 24 to No. 104 described on pages 3 to 28
Is also mentioned as a specific compound.

The compounds of the present invention are described, for example, in US Pat.
No. 127, No. 4,042,397 and Japanese Patent Application No. 2-19474, pages 29 to 32, can be easily synthesized according to the synthetic method.

The compound of the present invention is preferably used in a silver halide photographic light-sensitive material so as to have an optical density of 0.05 to 3.0 depending on the purpose.

The addition amount of the compound is ^{1 × 10 -3 g / m 2} ~1g / m 2 are preferred, especially ^{10 -3 g / m 2 ~0.5g /} m 2 is preferred.

The compound represented by the general formula [II] is dissolved in a suitable solvent such as water, alcohols (eg methanol, ethanol, propanol etc.), acetone, methyl cellosolve etc., or a mixed solvent thereof, It is usually added to the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

As the solvent for the compound represented by the general formula [II], water containing 30 mol% to 100 mol% of a trialkylamine (eg, triethylamine) of the compound can be selected.

In addition, a dispersion of solid particles described in JP-A-2-110453 and JP-A-2-91942 can be added to a hydrophilic colloid layer adjacent to a silver halide emulsion layer.

In the general formula [III], R ₁₂ and R ₁₃ are each a hydrogen atom, a halogen atom (eg chlorine, bromine etc.), an alkylcarbonyl group (eg methylcarbonyl, ethylerbornyl etc.), a hydroxycarbonyl group, an alkoxy. Carbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, etc.), sulfonic acid group, aminosulfenyl group,
Represents a substituted or unsubstituted alkyl group (eg, methyl, ethyl, etc.) or aryl group (eg, phenyl), R
₁₂ and R ₁₃ may form a ring (for example, a 5- or 6-membered ring).

Y ₁ and Y ₂ are -O-, -S-, -Se-,-, respectively.
Te -, - CO -, - SO 2 -, - N (R 14) - represents, Y _1, Y ₂
May be the same or different.

L ₄ is --CH ₂ CH _2- , --C (R ₁₅ ) H--CH _2- , --C
Represents (R ₁₆ ) H—CH ₂ —.

L ₅ represents = CH-, = C (R ₁₇ )-.

N ₂ represents an integer of 0 to 6.

Z is a hydroxyl group, a sulfo group, an amino group, a carboxyl group, an alkylcarbonyl group (eg methylcarbonyl, ethylcarbonyl etc.), a halogen atom (eg chlorine, bromine etc.) alkoxy group, an alkylthio group (eg methylthio), a sulfone. It represents an amide group, a substituted or unsubstituted alkyl group (eg, thimel, ethyl, etc.) or an aryl group (eg, phenyl).

Examples of the substituents on the alkyl group and the aryl group include those exemplified as the substituents on the alkyl group represented by R _{8 to} R ₁₁ in the general formula [II].

M ₁ represents an integer of 0 to 3.

R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each an alkyl group (eg methyl, ethyl etc.), an aryl group (eg phenyl), an alkoxy group (eg methoxy, ethoxy etc.), an alkylthio group (eg methylthio), It represents a trialkylsiloxy group (eg trimethylsiloxy), a halogen atom (eg chlorine, bromine etc.) and a tertiary amino group.

M ₁ and M ₂ are alkali metals (eg sodium, potassium, etc.), and M ₁ and M ₂ may be the same or different.

Specific examples of the compound represented by the general formula [III] are shown below, but the invention is not limited thereto.

[0061]

[Chemical 11]

[0062]

[Chemical 12]

[0063]

[Chemical 13]

In addition to the above compounds, Japanese Patent Application No. 2-106806
Nos. 8-9, compounds 4-9, 11, 13-15, 18-2
0, 23, 24, 26, and 28-30 can also be mentioned as specific compounds.

The compound represented by the general formula [III] is a suitable solvent such as water, alcohols (for example, methanol,
It can be dissolved in ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof, and added to the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

In addition, it can be added to the hydrophilic colloid layer adjacent to the silver halide emulsion layer as a dispersion of solid particles described in JP-A-2-110453 and JP-A-2-91942.

Further, these compounds may be mordanted with a cationic polymer or the like.

The amount of the compound added is 1 × 10 ⁻³ g / m ^{2 to} 1.5 g / m ^2.
2 is preferable, and 5 × 10 ⁻³ g / m ^{2 to} 1.0 g / m ² is particularly preferable.

The compounds represented by the above general formula [III] may be used alone or in combination of two or more kinds. Further, the compound represented by the general formula [I] may be combined with other known compounds.

In the present invention, the compound represented by the above-mentioned general formula [III] contained in the silver halide photographic light-sensitive material may be contained in the silver halide emulsion layer or may have hydrophilicity other than that. It may be contained in a photographic constituent layer including a colloid layer.

In the general formula [IV], examples of the halogen atom represented by G include fluorine, chlorine, bromine and iodine.

Examples of the monovalent group represented by R ₁₈ having a Hammett δp value of less than -0.05 include alkyl groups having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, tert-butyl, etc.). These may have a substituent.

The substituted alkyl group is, for example, carboxymethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, benzyl group and phenethyl group. Furthermore, R ₁₈ is
It represents a cycloalkyl group (eg, cyclopentyl, diclohexyl), a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, n-butoxy, etc.), and may have a substituent, for example, 2-methoxyethoxy, ethoxymethoxy, 2-hydroxy. For example, ethoxy. Further, as R ₁₈ , an amino group (for example, amino, methylamino, dimethylamino, ethylamino, diethylamino, anilino, etc.), a ureido group (for example, ureido, methylureido,
Ethyl ureido) and the like are preferred. The Hammett's δp value is the “Structure-Activity Relationship of Drugs” (Nankodo) 96th.
Page (1979), the substituents can be selected based on this table.

Further, in the above general formula [IV], R ₁₉
The aryl group having a sulfo group represented by represents other substituents in addition to the sulfo group, for example, a halogen atom (eg, fluorine, chlorine, bromine, etc.), a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, n-propoxy, etc.). ), Aryloxy groups (eg phenoxy), alkyl groups having 1 to 4 carbon atoms (eg methyl, ethyl, propyl, butyl etc.), carboxyl groups, alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl etc.) nitro groups, alkylsulfonyl A group (eg, methylsulfonyl,
Ethylsulfonyl, butylsulfonyl etc.), carbamoyl group (eg carbamoyl, methylcarbamoyl, ethylcarbamoyl etc.), sulfamoyl group (eg sulfamoyl, methylsulfamoyl, ethylsulfamoyl etc.), sulfonamide group (eg methylsulfonamide, ethyl) Sulfonamide, etc.) and the like.

Specific examples thereof include 3-sulfophenyl, 4-sulfophenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2- Chloro-5-sulfophenyl, 2-methoxy-4-
Sulfophenyl, 2-hydroxy-4-sulfophenyl, 2,5
-Dichloro-4-sulfophenyl, 2,6-dimethyl-4-sulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-
6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 3,6-disulfo-2-naphthyl, 8- Examples thereof include hydroxy-3,6-disulfo-2-naphthyl, 5-hydroxy-7-sulfo-2-naphthyl, and 6,8-disulfo-2-naphthyl.

Next, as the monovalent group represented by R ₂₀ , an alkyl group having 1 to 4 carbon atoms (eg methyl, ethyl, butyl etc.), a halogen atom (eg fluorine, chlorine, bromine etc.),
A hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, etc.), a nitro group and the like can be preferably mentioned.

The alkyl group represented by R ₂₁ and R ₂₂ is preferably an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, butyl, tert-butyl, etc.). Further as a substituent,
For example, cyano group, halogen atom (for example, fluorine, chlorine,
Bromine etc.), hydroxyl group, alkoxy group (eg methoxy, ethoxy, propoxy etc.), carboxyl group, alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl etc.), acyl group (eg acetyl, propionyl etc.), acyloxy group (eg acetyl) Oxy, propionyloxy etc.), an aryloxy group (eg phenoxy), an amino group (eg amino, methylamino, dimethylamino, diethylamino, anilino etc.),
An alkylthio group (eg, methylthio, ethylthio, etc.),
Examples thereof include an alkylsulfonyl group (eg methylsulfonyl, ethylsulfonyl etc.), an acylamino group (eg acetamide), an alkylsulfonylamino group (eg methylsulfonylamino, ethylsulfonylamino etc.), an aryl group (eg phenyl) and a sulfo group.

Further, examples of the 5-membered ring or 6-membered ring formed by combining R ₂₁ and R ₂₂ with each other include a pyrrolidino group, a piperidino group and a morpholino group.

Further, the methine group represented by L ₆ , L ₇ and L ₈ is an alkyl group having 1 to 4 carbon atoms (eg methyl, ethyl, butyl etc.) or an aryl group (eg phenyl).
May be replaced with.

As the compound represented by the general formula [IV], an aldehyde compound represented by the following general formula [V] and a pyrazolone compound represented by the following general formula [VI] are disclosed in JP-A-59-206.
It can be synthesized by the method described in No. 829, page 4, upper right, line 12 from the top to lower right, line 11 of the same page.

[0081]

[Chemical 14]

In the formula, R ₁₈ , R ₁₉ , R ₂₀ , X ₃ , Y ₃ , G, L
₆ , L ₇ , L ₈ and m ₂ , m ₃ have the same meanings as described in the general formula [IV]. p and q represent an integer of 1 or 2. However, p and q cannot be 2 at the same time.

Next, the general formula [I
Examples of the compound represented by V] are shown below, but the present invention is not limited thereto.

[0084]

[Chemical 15]

[0085]

[Chemical 16]

Compounds (3) to (12), (15), (17), (18), which are described in JP-A-59-206829, pages 4 to 6,
(20) to (26) and (28), (29) can also be mentioned as an exemplary compound.

[0087] preferably ^{1 × 10 -3 g / m 2} ~1g / m 2 is an appropriate amount of the compound represented by formula (IV), particularly 4 × 10 ^-3
g / m ² ~0.5g / m ² is preferred.

The compound represented by the general formula [IV] is dissolved in a suitable solvent such as water, alcohols (eg methanol, ethanol, propanol etc.), acetone, methyl cellosolve etc., or a mixed solvent thereof, It can be added to the hydrophilic colloid layer adjacent to the silver halide emulsion layer.

In addition, a dispersion of solid particles described in JP-A-2-110453 and JP-A-2-91942 can be added to a hydrophilic colloid layer adjacent to a silver halide emulsion layer.

The silver halide composition used in the present invention contains at least 70% silver chloride. In particular, its composition is preferably silver chloride or silver chlorobromide.
Further, the emulsion preferably contains silver halide grains having an average grain size of 0.05 to 0.3 μm. The silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method, but the acidic method of pH 1 to 4 is more preferable. Further, adenine, benzyladenine, a nucleic acid degradation product represented by adenosine, a tetrazaindene compound or a mercapto compound is adsorbed on the silver halide in the reaction vessel to reduce the solubility of the silver halide particles to form silver halide particles. The method of preparation is also a preferred embodiment for particle formation according to the present invention.

In the present specification, the grain size of silver halide grains is represented by the edge length of cubic grains having the same volume for convenience.

To add a rhodium salt to the emulsion, various salts may be added. For example, the water-soluble rhodium salt used in the present invention may be any conventionally known one. , Typically [Na ₃ RhCl ₆ ], [K ₃
RhCl ₆ ], rhodium chloride chloride complex, rhodium trichloride and the like are used.

The amount of water-soluble rhodium contained is 10 ^-8 to 10 ^-4 mol, and more preferably 10 ^-7 to 10 ^-5 mol, per mol of silver halide.

The water-soluble rhodium salt to be used is particularly preferably used at the time of producing silver halide, but it can be used at any time thereafter or can be used by dividing it.

The rhodium salt is contained in the above emulsion,
It may be contained in a layer other than the emulsion layer formed by this emulsion, for example, in an arbitrary hydrophilic colloid layer on the side coated with the silver halide emulsion layer. It may be divided and added to two or more layers.

When the rhodium salt is used, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt and gold salt may be used in combination.

The monodispersity of the silver halide grains in the above emulsion is optional, but it is preferably adjusted to 5 to 60%, more preferably 8 to 30%.

Here, the monodispersity is represented by a value obtained by multiplying a value obtained by dividing the standard deviation of the above-defined particle diameter by the average particle diameter by 100 times.

As the silver halide in the above emulsion, grains of a type having a multilayer laminated structure of at least two layers can be used. For example, it is possible to use silver chlorobromide grains in which the core portion is silver chloride and the shell portion is silver bromide, and conversely, the core portion is silver bromide and the shell portion is silver chloride. In all cases, it is essential that the content of silver chloride in the emulsion is 50 mol% or more. In this case, iodine may be contained in any layer,
It is preferably within 5 mol% in each layer.

The silver halide emulsion used in the present invention is
For example, U.S. Patents 2,444,607, 2,716,862, 3,512,
No. 982, West German application publication No. 1,189,380, No. 2,058,626,
No. 2,118,411, Japanese Examined Patent Publication No. 43-4133, U.S. Patent 3,342,596.
Japanese Patent Publication No. 47-4417, West German Application Publication No. 2,149,789, Japanese Patent Publication No. 39-2825, Japanese Patent Publication No. 49-13566, Japanese Patent Publication No. 40-40665.
JP-A-61-198147 and the like, preferably, for example, 5,6-trimethylene-7-hydroxy-s-triazolo (1,5-a) pyridine, 5,6-tetramethylene-7. -Hydroxy-s-triazolo (1,2-a) pyrimidine, 5-methyl-7-hydroxy-s-triazolo (1,5-a) pyrimidine, 7-hydroxy-s-triazolo (1,5-a) pyrimidine , 5-methyl-6-promo-7-hydroxy-s-triazolo (1,5-a) pyrimidine, gallic acid ester (eg isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate),
Mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole), benzotriazoles (5-bromobenzotriazole, 5-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole), disulfides, etc. It can be stabilized by using a quaternary salt compound or the like.

For the hydrophilic colloid used in the present invention, the support and the treatment, materials and methods known in the photographic art can be used.

As the developer, TH James, The.
Theory of the Photographic Process 4
Edition (The Theory of the Photographic Process Fourth
Edition) pages 291-334 and the Journal of the American Chemical Society (Journal of the Ame
rican Chemical Society) Vol. 73, p. 3,100 (1951)
The developers described in 1) can be effectively used in the present invention. Even if these developers are used alone, 2
One or more kinds may be combined, but it is preferable to use two or more kinds in combination. The effect of the present invention is not impaired even if a sulfite such as sodium sulfite, potassium sulfite, etc. is used as a preservative in the developer used for developing the light-sensitive material of the present invention. Can be mentioned as one of the features.

[0103]

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

Example 1 Preparation of Sample [Solution B] in [Solution A] below while maintaining the silver potential (EAg) at 170 mV under a nitric acid acidic atmosphere of pH 3.0.
At the addition flow rate shown in Fig. 1, EAg was controlled by 1N NaCl and mixed by the controlled double jet method.
[Solution C] is added at the same reaction temperature and the same addition flow rate as [Solution B] until the addition time of 2 minutes, and then EAg of [Solution B] is set to IN.
While controlling with NaCl, add at a flow rate of 0.99 times the addition flow rate,
The silver halide emulsions a, b, c, d, e and f of the present invention in Table 1
Was prepared.

[0105]

[Table 1]

[Solution A] Gelatin 5.6 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% ethanol solution 0.56 ml Sodium chloride 0.12 g Benzyladenine 1.00 g Concentrated nitric acid 0.43 ml Distilled water 445 ml [Solution B] Silver nitrate 60 g Concentrated nitric acid 0.21 ml Distilled water 83.3 ml [Solution C] Gelatin 3.0 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% ethanol solution 0.3 ml Potassium bromide 4.2 g Sodium chloride 18.8 g Na ₃ RhCl ₅ 0.01% aqueous solution 4.00 ml Distilled water 83.6 ml [Solution D] Gelatin 1.4 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% methanol solution 0.14 ml Distilled water 48.8 ml Average silver halide grains of each silver halide emulsion obtained. The diameters are shown in Table 1.

Emulsion No. f was prepared by changing the composition of [Solution C] as follows under the conditions for preparing Emulsion No. c [Solution E].
Was prepared using.

[Solution E] Gelatin 3.0 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% ethanol solution 0.3 ml Potassium bromide 4.2 g Sodium chloride 18.8 g Distilled water 84 ml Each silver halide grain contains silver chloride The ratio is 90 mol%, the rhodium content is 2 × 10 ^-6 mol per mol of silver halide,
The monodispersity was 8 to 15%.

A metal silver electrode and a double junction type saturated Ag / AgCl reference electrode were used for measuring the EAg value. (The double junction disclosed in JP-A-57-197534 was used for the structure of the electrode.) A variable flow rate roller tube metering pump was used for adding [Solution B] and [Solution C]. .

During addition, it was confirmed by an electron microscope that no new grains were generated due to sampling of the emulsion, and it was confirmed that the addition amount did not exceed the critical growth rate in the system.

To the thus prepared emulsions a to f, 200 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added per mol of silver halide, and the pH was adjusted with sodium carbonate. Adjusted to 5.7 and then added [solution D]. After that, each silver halide emulsion was washed with water and desalted in accordance with a conventional method, and 2-methyl-3-oxoisothiazole, 5
A mixture of -chloro-2-methyl-3-oxoisothiazole, 4,5-dichloro-2-methyl-3-oxoisothiazole was added. Furthermore, the following additives were added to prepare a coating solution for emulsion layer, which was subjected to latex undercoating treatment according to Example 1 of Japanese Patent Application No. 2-226971, and a backing layer and a backing protective layer having the following compositions were laminated. The sample of Table 2 was applied to the applied polyethylene terephthalate film having a thickness of 100 μm.
Nos. 1 to 25 were obtained. The amount of silver attached was 2.5 g / m ² in all cases.

[0112]

[Table 2]

An emulsion layer, an emulsion protective layer, a backing layer,
The amount of the additive to each coating solution such as the backing protective layer is shown in mg per 1 m ² .

[0114] [Emulsion layer coating liquid additive]   Saponin 90   Compound [I] of the present invention (added as a 5% solution in methanol).   5-phenyl-1-mercaptotetrazole 11   Ethyl acrylate-methacrylic acid copolymer latex 2   Citric acid 4   Styrene-maleic acid copolymer 50   (i) -Amyl- (n) decyl sulfosuccinate sodium salt 5   Glio Kizar 35   Formaldehyde 45 [Emulsion protective layer composition]   Gelatin 1.14   Di (2-ethylhexyl) sulfosuccinate sodium salt 12   Amorphous silica 20   Sodium chloride 11   Compound [I] of the present invention (added as a 5% methanol solution).         〃 [II] (added as a 5% water-triethylamine solution) 〃         〃 [III] (added as a 5% aqueous solution) 〃         〃 [IV] (added as a 1% aqueous solution) 〃   2-methyl-3-oxoisothiazole   5-chloro-2-methyl-3-oxoisothiazole mixture 0.5   4,5-dichloro-2-methyl-3-oxoisothiazole   Citric acid 4   Cyanur chloride 30 [Backing layer]   Butyl acrylate-styrene copolymer latex 0.5   Saponin 200   Backing dye A 100   Backing dye B 70   Backing dye C 50   Ossein gelatin 2000

[0115]

[Chemical 17]

[Backing Protective Layer] Dioctylsulfosuccinate sodium salt 300 Matting agent: Methyl methacrylate (average particle size 4.0 μm) 100 Ocein gelatin (isoelectric point 4.9) 1100 Sodium fluorinated dodecylbenzenesulfonate 50 [Relative sensitivity , Evaluation of storability and safelight property] Relative sensitivity and storability were measured by exposing the samples stored under the storage conditions A and B below with FF Shinmei room printer type FA-Q manufactured by Ushio Utex Co. ) Developer CDM-62
1.Development condition 3 using fixer CFL-851 and automatic processor GR-26
It was treated at 8 ° C. for 20 seconds, and indicated as the relative value of the reciprocal of the exposure amount that gives a density of 3.0.

Storage condition A: 23 ° C., 55% RH, 2 days Storage condition B: 23 ° C., 55% RH After humidity control for 3 hours, sealed in a moisture-proof bag and evaluated at 55 ° C. for 3 days for safelight property. 50% halftone originals
The time required for the halftone dot area to decrease by 2% was measured under a 300 lux light intensity of a UV-cut fluorescent lamp for the sample which was contact-exposed so as to be converted into 50% halftone dot, and the evaluation was carried out in 5 grades.

[0118] Hours (minutes) 0-10 1 11 ~ 30 2 31-40 3 41 ~ 50 4 51 or more 5 Table 3 shows the evaluation results.

[0119]

[Table 3]

From Table 3, the compound [I] was used for the emulsion layer containing no rhodium salt and the compound [I] was used for the non-photosensitive hydrophilic colloid layer.
I] or the compound [IV] is contained in the sample Nos. 2 and 3 and the emulsion layer containing the rhodium salt is compared with the comparative sample such as the sample No. 1 in which only the compound [I] is contained. Sample N
It can be seen that from o.4 to No.25, there is little decrease in sensitivity due to storage, and the resistance to safe light is remarkably excellent.

[0121]

According to the present invention, it is possible to provide a negative type silver halide photographic light-sensitive material which is highly advanced, has little fluctuation in sensitivity due to storage, and can be handled in a bright room for a long time.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, the light-sensitive material containing at least silver chloride. An emulsion layer containing negative type non-spectral sensitized silver halide grains having an average grain size of 0.05 to 0.30 μm, containing 70 mol% and a rhodium salt of 1.0 × 10 ⁻⁸ to 10 ⁻⁴ mol per mol of silver halide. A silver halide photographic light-sensitive material, characterized in that the emulsion layer and / or the other hydrophilic colloid layer contains at least one compound represented by the general formula [I]. [Chemical 1] [In the formula, R ₁ and R ₂ each represent a hydrogen atom or an optionally substituted alkyl group, and R ₁ and R ₂ are bonded to each other to form 5
A member ring or a 6-membered ring may be formed. R ₃ , R ₄ , R ₅ ,
R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acylamino group, a formyl group, a hydroxyl group, a carboxyl group, a sulfo group, a sulfonamide group, or a halogen atom. R ₃ and R ₇ are R
₁ and R ₇ or R ₂ and R ₃ represent a group of non-metallic atoms necessary for forming a 5-membered ring or a 6-membered ring by bonding. ] 2. The hydrophilic colloid layer adjacent to the emulsion layer contains at least one compound represented by the general formula [II] and / or a compound represented by the general formula [III]. The silver halide photographic light-sensitive material according to claim 1. [Chemical 2] [In the general formula [II], R ₈ , R ₉ , R ₁₀ , and R ₁₁ each represent a hydrogen atom, a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group;
₁ , X ₂ represents an oxygen atom or a sulfur atom. L ₁ , L ₂ , L ₃
Represents a methine group, and n ₁ represents 0, 1 or 2. In the general formula [III], R ₁₂ and R ₁₃ each represent a hydrogen atom, a halogen atom, an alkylcarbonyl group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a sulfonamide group, a substituted or unsubstituted alkyl group or an aryl group. , R ₁₂
And R ₁₃ may form a ring. Y ₁ and Y ₂ are each -O-,
-S -, - Se -, - Te -, - CO -, - SO 2 -, - N (R 14) -
And Y ₁ and Y ₂ may be the same or different. L ₄
Is _{-CH 2 CH 2 -, - C} (R 15) H-CH 2 -, - C (R 16) H-CH 2 -,
The stands, L ₅ is = CH -, = C (R 17) - represents a. n ₂ is 0 to 6
Represents an integer of, Z is a hydroxyl group, a carboxyl group,
It represents a sulfo group, an amino group, an alkylcarbonyl group, a halogen atom, an alkoxy group, an alkylthio group, an aminosulfonyl group, or a substituted or unsubstituted alkyl group or aryl group. m ₁ represents an integer of 0 to 3, R ₁₄ , R ₁₅ , R ₁₆ ,
R ₁₇ represents an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a trialkylsiloxy group, a halogen atom or a tertiary amino group. M ₁ and M ₂ represent an alkali metal, and M ₁ and M ₂ may be the same or different. ] 3. A silver halide photographic light-sensitive material according to claim 1, wherein the hydrophilic colloid layer adjacent to the emulsion layer contains at least one compound represented by the general formula [IV]. . [Chemical 3] [In the formula, G represents a hydrogen atom or a halogen atom, and R ₁₈ represents a monovalent group having a Hammett δp value of less than -0.05. R
₁₉ represents an aryl group having at least one sulfonic acid group, and R ₂₀ represents a lower alkyl group, a halogen atom, a hydroxyl group or an alkoxy group. R ₂₁ and R ₂₂ each represent a hydrogen atom or an alkyl group, and R ₂₁ and R ₂₂ may combine with each other to form a 5-membered ring or a 6-membered ring. L ₆ ,
L ₇ and L ₈ each represent a methine group, and m ₂ is 1, ₂ , 3
Or 4, and n ₃ represents 1 or 2. ]