JPH0611792A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an ultrahigh-contrast image restrained in rise of fog and small in scratches and resistant to pressure by incorporating specified 2 kinds of compounds in at least one of emulsion layers and other hydrophilic colloidal layers. CONSTITUTION:At least one of the emulsion layers and the hydrophilic colloidal layers contains each one of the compounds represented by formula I; (Cf)-(Y), and the compounds represented by formula II; Rf'-L<->X<+>Z<->. In the formulae I and II, Cf is an n-valent group having 3 F atoms and 2 C atoms: Y is-COON, -SO3M, -O-SO3M, or -P(=0)(OM)2; M is H or an alkali metal atom or a quaternary ammonium salt; n is 1 or 2; Rf' is a 1-20C hydrocarbon group, and at least one of H is substituted by F; L is a simple chemical bond or a divalent group; X<+> is a cation; and Z<-> is a counter anion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultrahigh contrast silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved photographic characteristics and physical characteristics.

[0002]

BACKGROUND OF THE INVENTION The photomechanical process involves the conversion of continuous-tone originals into halftone images. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle size of about 0.2 μm, a narrow particle distribution and a well-defined particle shape, and a high silver chloride content (at least 50). Mol% or more) consisting of silver chlorobromide emulsion. By processing the lith-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, an image having high contrast, high sharpness and high resolution can be obtained.

However, since the squirrel-type developing solution is apt to undergo air oxidation and thus has extremely poor preservability, it is difficult to keep the developing quality constant during continuous use.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as disclosed in JP-A-56-106244, a silver halide photographic light-sensitive material contains a hydrazine derivative. According to these methods, it is possible to obtain a high-contrast image even by processing with a developing solution having good preservative property and capable of rapid processing.

However, it has been found that scratches and pressure fog tend to occur with increasing contrast due to the hydrazine derivative, and at the same time fog also increases. Therefore, photographic performance (fogging over time,
There is a demand for development of a technology that does not deteriorate the pressure fog) and the physical characteristics (scratch resistance).

[0007]

The object of the present invention is to suppress the increase of fog,
An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a super-high contrast image with little scratches and high pressure resistance.

[0008]

The above object of the present invention is to provide a silver halide photographic light-sensitive material containing a hydrazine derivative in at least one silver halide emulsion layer or a layer adjacent to the emulsion layer, the emulsion layer or other layers. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (FA) and at least one compound represented by the following general formula (FK) in at least one hydrophilic colloid layer. It

In the general formula (FA) (Cf)-(Y) _n , Cf is at least 3 fluorine atoms and at least 2
Represented by an n-valent group containing carbon atoms, Y is --COOM, --SO
₃ M, -OSO ₃ M or -P (= O) (OM) ₂ . M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2.

General formula (FK) Rf'-L-X ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom is substituted with a fluorine atom. L
Represents a chemical bond or a divalent group. X ⁺ represents a cation and Z ⁻ represents a counter anion.

In the present invention, the photosensitive silver halide emulsion layer is preferably located between the support and the hydrophilic colloid layer.

The iodine content of the silver halide used in the present invention is preferably 4 mol%.

The present invention will be specifically described below.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula [H].

[0015]

[Chemical 1]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents-.
(CO) n- group, sulfonyl group, sulfoxy group, -P (R) (= O)
Represents a group or an iminomethylene group, n represents an integer of 1 or 2, 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 alkylsulfonyl group. Represents a substituted acyl group, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, an oxycarbonyl group or an —OR ₂ group, and R ₂ represents an alkyl group or a saturated heterocyclic group. Represents a ring group.

In the present invention, among these, the following general formulas [H-a], [H-b], [H-c] or [H-
The compound represented by d] is preferred.

[0018]

[Chemical 2]

In the general formula [Ha], R ₃ and R ₄ are respectively
Hydrogen atom, substituted or unsubstituted alkyl (eg methyl, ethyl, butyl, dodecyl, 2-hydroxypropyl, 2-cyanoethyl, 2-chloroethyl, etc.), substituted or unsubstituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group , A pyrrolidyl group (eg phenyl, p-methylphenyl, naphthyl, α-hydroxynaphthyl, cyclohexyl, p-methylcyclohexyl, pyridyl, 4-
Propyl-2-pyridyl, pyrrolidyl, 4-methyl-2-pyrrolidyl, etc., and R ₅ is a hydrogen atom, a substituted or unsubstituted benzyl group, an alkoxy group or an alkyl group (eg, benzyl, p-methylbenzyl, methoxy). , Ethoxy,
Ethyl, butyl, etc.).

R ₆ and R ₇ each represent a divalent aromatic group (eg, phenylene or naphthylene), Y represents a sulfur atom or an oxygen atom, and L represents a divalent linking group (eg, —SO ₂ CH _{2
CH 2 NH -, - SO 2} NH -, - OCH 2 SO 2 NH -, - O -, - CH = N
-) Is shown.

R ₈ represents -NR'R "or -OR ₉ ,
R ′, R ″ and R ₉ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, methyl, ethyl, dodecyl), a phenyl group (eg, phenyl, p-methylphenyl, p-methoxyphenyl), a naphthyl group ( For example, α-naphthyl, β-naphthyl) or a heterocyclic group (for example, an unsaturated heterocyclic group such as pyridine, thiophene, furan or a saturated heterocyclic group such as tetrahydrofuran or sulfolane), and R ′ and R ″ are nitrogen. A ring (for example, piperidine, piperazine, morpholine, etc.) may be formed with the atom.

M and n each represent 0 or 1. R ₈ is -O
When R ₉ is represented, Y is preferably a sulfur atom.

In the general formula [Hb], R ₁₀ , R ₁₁ and R ₁₂
Is a hydrogen atom, an alkyl group (eg, methyl, ethyl, butyl, 3-aryloxypropyl, etc.), a substituted or unsubstituted phenyl group, a naphthyl group, a cyclohexyl group, a pyridyl group, a pyrrolidyl group, a substituted or unsubstituted alkoxy group. Represents a group (eg, methoxy, ethoxy, butoxy etc.) or a substituted or unsubstituted aryloxy group (eg, phenoxy, 4-methylphenoxy etc.).

R ₁₂ is preferably a hydrogen atom or an alkyl group.

R ₁₃ represents a divalent aromatic group (for example, phenylene or naphthylene), and Z represents a sulfur atom or an oxygen atom.

R ₁₄ is a substituted or unsubstituted alkyl group,
It represents an alkoxy group or an amino group, and examples of the substituent include an alkoxy group, a cyano group, and an aryl group.

The hydrazine derivative can be easily synthesized by a known method. For example, JP-A-2-214850.
No. 2, No. 2-47646, No. 2-12237 and the like.

Typical compounds represented by the above general formulas [Ha] and [Hb] are, for example, Japanese Patent Application No. 4-39673.
No., a-1 to a-11 described in paragraph numbers 0024 to 0030,
b-1 to b-17 can be mentioned.

In the general formulas [Hc] and [Hd],
A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group. Alternatively, it represents a heterocyclic oxy group, and R ₁₅ and R ₁₆ may form a ring together with a nitrogen atom. When n = 2, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxyl group,
It represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic oxy group. However, when n = 2, at least one of R ₁₅ and R ₁₆ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic oxy group. Shall be represented. R ₁₇ represents an alkynyl group or a saturated heterocyclic group.

The compound represented by the general formula [Hc] or [Hd] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A represents an aryl group (eg, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.).

R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl, etc.). ), Alkynyl groups (eg, propargyl, butynyl, pentynyl, etc.), aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, pyridine, thiophene, unsaturated heterocyclic groups such as furan and tetrahydrofuran) , Saturated heterocyclic groups such as sulfolane), hydroxyl groups, alkoxy groups (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy groups (eg, allyloxy, butenyloxy, etc.), alkynyloxy groups (eg, Parugiruokishi, butynyloxy), an aryloxy group (e.g., phenoxy, represents the naphthyloxy) or a heterocyclic oxy group (e.g. pyridyloxy, pyrimidyloxy, etc.), when n = 1, the ring with R ₁₅ and R ₁₆ is a nitrogen atom ( For example, piperidine, piperazine, morpholine, etc.) may be formed.

However, when n = 2, at least one of R ₁₅ and R ₁₆ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic group. It represents a ring oxy group.

Specific examples of the alkynyl group and saturated heterocyclic group represented by R ₁₇ include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. As the substituent that can be introduced,
For example, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, alkylthio group, arylthio group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, acyl group, amino group, Examples thereof include an alkylamino group, an arylamino group, an acylamino group, a sulfonamide group, an arylaminothiocarbonylamino group, a hydroxyl group, a carboxyl group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

In the formula, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in non-moving photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercaptoheterocyclic group and triazole group.

--NH in the general formulas [Hc] and [Hd]
H of NH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, toluenesulfonyl, etc.),
It may be substituted with a substituent such as an acyl group (eg, acetyl, trifluoroacetyl, ethoxycarbonyl, etc.), an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.), and is represented by the general formulas [Hc] and [Hd]. The compounds represented also include such.

More preferred compounds are represented by the general formula [Hc]
In the case of n = 2, and the compound of the general formula [Hd].

In the compound of the general formula [Hc] with n = 2, R ₁₅ and R ₁₆ are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, saturated or unsaturated heterocyclic group, hydroxyl group or An alkoxy group and R ₃₁
Further, a compound in which at least one of R ₃₂ and R ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group, or an alkoxy group is more preferable.

Representative compounds represented by the above general formulas [Hc] and [Hd] include c-1 to c- described in Japanese Patent Application No. 4-39673, paragraphs 0046 to 0049. 8, d-1 to d-
5 can be mentioned.

Specific compounds other than the above are disclosed in
2-841 542 (4) to 546 (8) compound examples
There are (1) to (61) and (65) to (75).

The hydrazine derivative in the present invention is disclosed in
It can be synthesized by the method described in No. 2-841, pages 546 (8) to 550 (12). The addition position of the hydrazine derivative of the present invention is the silver halide emulsion layer and / or the adjacent layer. The addition amount is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol per mol of silver.

Further, when [Hc] or [Hd] is contained as the hydrazine derivative, the nucleation promoting compound described in Japanese Patent Application No. 2-234203, page 68, line 1 to page 144, line 12 It is preferable that at least one of the above is contained in the silver halide emulsion layer and / or the non-photosensitive layer on the side of the silver halide emulsion layer on the support.

The following are typical examples of the nucleation accelerator.

[0046]

[Chemical 3]

[0047]

[Chemical 4]

Yet another specific example is Japanese Patent Application No. 2-234203.
Nos. 69 to 72, compounds I-1 to I-26, 73 to 78, compounds II to II-29, 80 to 83
Compounds III-1 to III-25 described on page, Compounds IV-1 to IV-41 described on pages 84 to 90, Compounds VI-1 to VI described on pages 92 to 96 -27, compounds V-II-1 to V-II-30 described on pages 98 to 103, compounds V-III-1 to pages 113 to 121 described on pages 105 to 111 Compounds VI-I-1 to VI-I-44, compounds VI-II-1 to VI-II-68 described on pages 123 to 135 and compounds described on pages 137 to 143 Among VI-III-1 to VI-III-35, there are those other than the above representative examples.

Next, the compounds represented by the general formula (FA) and the general formula (FK) used in at least one of the emulsion layer and other hydrophilic colloid layers in the present invention will be described.

Among the fluorine-based anion activators represented by the general formula (FA), those particularly preferably used are the compounds represented by the following general formula (FA ').

General formula (FA ') Rf- (D) _t -Y In the formula, Rf represents a fluorine-substituted alkyl group having 3 to 30 carbon atoms or an aryl group, and D represents -O-, -COO-,-. CON (R ₁ )
- or -SO ₂ N (R ₁₎ - represents a composed combine at least one divalent group having 1 to 12 carbon atoms. R ₁ has _{1 to 1} carbon atoms
5 represents an alkyl group, t is 1 or 2, and Y is -CO.
OM -, - SO ₃ M, represents an -OSO ₃ M or -P (= O) (OM) 2, M represents such cation hydrogen atom or an alkali metal or a quaternary ammonium salt.

Specific examples of the compound represented by formula (FA) are shown below, but the invention is not limited thereto.

[0053]

[Chemical 5]

[0054]

[Chemical 6]

[0055]

[Chemical 7]

[0056]

[Chemical 8]

[0057]

[Chemical 9]

It is particularly preferable to use a fluorinated anion activator containing at least one bond of —SO ₂ N (R ₁ ) —.

Next, the fluorinated cationic activator represented by the general formula (FK) will be described.

In the general formula (FK), as an example of the hydrocarbon group having 1 to 20 carbon atoms represented by Rf '(at least one hydrogen atom is replaced by a fluorine atom), -C _k F _{2k + 1}
(K = 1 to 20, particularly preferably 3 to 12), −C _m F _2m−1 , −C
_m F _2m-3 (m = 2 to 20, particularly preferably 3 to 12) and the like can be mentioned.

Examples of the divalent group represented by L include -SO ₂ N (R ¹ )
(CH ₂ ) _p −, −CON (R ¹ ) (CH ₂ ) _p −, −OASO ₂ N (R ¹ ) (CH ₂ )
^{_{p -, - OACON (R 1}} ) (CH 2) p -, - OAO (CH 2) p -, - OA (CH 2)
_p −, −O (CH ₂ CH ₂ O) _q (CH ₂ ) _p −, −O (CH ₂ ) p −, −N (R ¹ ) (C
H ₂ ) _p −, −SO ₂ N (R ¹ ) (CH ₂ ) _p O (CH ₂ ) _r −, −CON (R ¹ ) (CH ₂ ) _p
O (CH ₂ ) _r −, −OASO ₂ N (R ¹ ) (CHR ¹ ) _p OA−, − (CH ₂ ) _p (CHOH)
_s (CH ₂ ) _r − and the like can be mentioned.

Examples of the cation represented by X ⁺ include -N
_{^{+ (R 1) 3, -N}} + (CH 2 CH 2 OCH 3) 3, -N + C 4 H 8 O (R 1). −N ⁺ (R ¹ )
(R ² ) (CH ₂ CH ₂ OCH ₃ ), −N ⁺ C ₅ H ₅ , −N ⁺ (R ¹ ) (R ² ) (CH ₂ ) _p C
^{_{6 H 5, -N + (R}} 1) (R 2) (R 2) , and the like. Here, R ¹ and R ² each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent), and p, r, s
Is 0 to 6 and q is 1 to 20, respectively. A represents an alkylene group or an arylene group.

[0063] Y ^- Examples of the counter anion represented by ^{the, I -, Cl -, Br} -, CH 3 SO 3 -, CH 3 -C 6 H 4 -SO 3 - , and the like.

Specific examples of the compound represented by formula (FK) preferably used in the present invention are shown below, but the invention is not limited thereto.

[0065]

[Chemical 10]

[0066]

[Chemical 11]

In the present invention, it is more preferable to use a fluorinated cation activator containing at least one bond of —SO ₂ N (R ¹ ) — which is hardly soluble. Here, the term “poorly soluble” means that 2.0 g of the activator was added to 100 cc of pure water at 23 ° C., and the mixture was stirred for 1 hour at 23 ° C.
It is insoluble when it forms a precipitate after standing for 24 hours or when a floating substance is observed. For example, FK-1, FK-8,
FK-15, FK-16 and the like correspond, but are not limited to these and can be divided by the above test.

The fluorinated anion activator or fluorinated cation activator according to the present invention is described in, for example, US Pat. No. 2,559,751.
No., No. 2,567,011, No. 2,732,398, No. 2,764,602,
No. 2,806,866, No. 2,809,998, No. 2,915,376, No. 2,9
15,528, 2,918,501, 2,934,450, 2,937,098
No. 2, No. 2,957,031, No. 3,472,894, No. 3,555,089, British Patent Nos. 1,143,927, No. 1,130,822, Japanese Patent Publication No. 45-37304
JP-A-47-9613, 49-134614, 50-117705,
50-117727, 50-121243, 52-41182, 51-1
2392, Journal of the British Chemical Society (J. Chem. Soc.), 1950, page 2789,
1957, pages 2574 and 2640, Journal of the American Chemical Society (J. Amer. Ch.
em.Soc.) Volume 79, page 2549 (1957), Oil Chemistry (J. Japan Oil Ch
emists Soc.) 12: 653, Journal of the Society of Organic Chemistry (J.Org.Che)
m.) Vol. 30, p. 3524 (1965) and the like. Of these fluorine-based activators,
One is the trade name of Megafac F from Dainippon Ink and Chemicals, and the trade name of Fluorad FC from Minnesota Mining and Manufacturing Company, Imperial Chemical Industry. Under the trade name Monflor, from E.I.Dupont Nemeras & Company, Inc., Zonyls
And Falbeberke Hoechst under the name Licowet VPF.

The total amount of the fluorinated cation activator and the fluorinated anion activator used in the present invention is 0.1 per 1 m ^2.
˜1000 mg is preferable, 0.5 to 300 mg is preferable, and 1.0 to 150 mg is more preferable. When used in combination, two or more of each may be used in combination. In addition, a fluorine-based nonionic activator, a fluorine-based betaine activator, and a hydrocarbon-based activator may be used in combination.

The addition ratio of the fluorine-based anion activator and the fluorine-based cation activator of the present invention is preferably 1:10 to 10: 1 and more preferably 3: 7 to 7: 3 in terms of molar ratio.

The places where the fluorine-based anionic activator and the fluorine-based cationic activator of the present invention are added are not particularly limited.
It is preferably an emulsion layer surface protective layer of a light-sensitive material.
The surface of the emulsion protective layer may be further overcoated with the fluorine-based activator according to the present invention.

In order to exert the effects of the present invention most remarkably, it is preferable to add the fluorine-based activator according to the present invention to the surface protective layer, the back surface layer or the overcoat layer.

[0073]

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

Example 1 (Preparation of Silver Halide Emulsion A) A mixed aqueous solution of potassium iodide and potassium bromide and an aqueous silver nitrate solution were adjusted to 50 ° C., pAg 7.8 and pH 2.0 in a gelatin aqueous solution. The mixture was mixed while controlling the stirring conditions and the addition flow rate. During this mixing, K ₂ lrCl ₆ was added at 8 × 10 ^-7 mol per mol of silver. After adding 6.5 cc. Of 1% potassium iodide aqueous solution per mol of silver to this emulsion, modified gelatin (Japanese Patent Application No. 1-180787).
Compound G-8) of No. 1) was added, and the mixture was washed with water and desalted in the same manner as in Example 1 of Japanese Patent Application No. 1-1890787. 40 ℃ after desalting
The pAg at was 8.0.

Further, at the time of redispersion, the following compound [A],
The mixture of [B] and [C] was added.

The finally obtained emulsion had an average grain size of 0.20 μm.
Silver iodobromide emulsion consisting of cubic grains of m (silver iodide content 2
Mol%).

[0077]

[Chemical 12]

(Preparation of Photosensitive Material) Thickness of 0.1 μm on Both Sides
A silver halide emulsion layer having the following formula (1) was gelatin-coated on one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm and having an undercoat layer (see Example 1 of JP-A-59-19941). The amount of silver is 2.0 g / m ² , the amount of silver is 3.3 g / m ^2, and a protective layer of the following formulation (2) is applied on it so that the amount of gelatin is 1.0 g / m ^2. On the other undercoat layer on the opposite side, a backing layer was applied according to the following prescription (3) so that the gelatin layer would be 2.4 g / m ² , and further the following prescription (4 Samples 1 to 10 were obtained by coating the protective layer of 1) so that the amount of gelatin would be 1.0 g / m ² . The amount of each material added is shown in g per 1 m ² of the coated sample.

Formulation (1) [Silver Halide Emulsion Layer Composition] Gelatin 2.0 g Silver iodobromide emulsion (silver amount) 3.3 g Antifoggant (adenine) 10 mg Stabilizer (4-methyl-6-hydroxy-1,3) , 3a, 7-Tetrazaindene) 30mg Surfactant (saponin) 0.1g Surfactant Hydrazine derivative shown in Table 1 Amount shown in Table 1 Polyethylene glycol (Molecular weight 4000) 0.1g Latex polymer (Lx-1) 0.1g increase Dye-sensitizing agent (S-1) 8 mg Hardener (H-1) 60 mg Formulation (2) [Emulsion protective layer composition] Gelatin 0.9 g Matting agent (silica having an average particle size of 3.5 μm) 3 mg Hardener (H-2) 50 mg Hardener (formalin) 30 mg Surfactant Amount shown in Table 1 Formulation (3) (Backing layer composition) Dye (AI-1) 100 mg Dye (AI-2) 75 mg Dye (AI-3) 40 mg Gelatin 2.4 g Interface Activator (Su-1) 6.0 mg Formulation (4) [Backing protective layer set] ] Gelatin 1g Matting agent (polymethylmethacrylate having an average particle size of 3.0 to 5.0 µm) 50mg Surfactant (Su-2) 10mg Hardener (glyoxal) 25mg Hardener (H-1) 35mg Prescription (1) ~ ( The structures of the materials used in 4) are summarized below.

H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium salt H-2: tetrakis (vinylsulfonyl) methane taurine potassium salt adduct Su-1: sulfosuccinate-i-amyl・ Decyl ester ・
Sodium salt Su-2: sulfosuccinic acid di (2-ethylhexyl) ester / sodium salt Su-3: sulfosuccinic acid di (2,2,3,3,4,4,5,5,6,6,7, 7-
Dodecyl fluoroheptyl) ester sodium salt

[0081]

[Chemical 13]

[0082]

[Chemical 14]

The obtained sample was processed in an undeveloped state under the following conditions in an automatic processor for rapid processing in which a developing solution and a fixing solution having the compositions shown below were added.

Developer Formulation Ethylenediaminetetraacetic acid disodium salt 1 g Sodium sulfite 60 g Tripotassium phosphate 30 g Hydroquinone 22.5 g Sodium hydroxide 8.0 g N, N-diethylethanolamine 15 g Sodium bromide 3.0 g 5-Methylbenzotriazole 0.25 g 1- Phenyl-5-mercaptotetrazole 0.08g N-methyl-p-aminophenol-sulfate 0.25g Add water to make 1 liter and adjust to pH with sodium hydroxide.
To 11.7.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240cc. Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid 6g Sodium oxalate dihydrate 2g (Composition B) Pure water (Ion-exchanged water) 17 cc. Sulfuric acid (150% w / w aqueous solution) 4.7 g Aluminum sulfate (8.0% w / w aqueous solution in terms of Al ₂ O ₃ content) 26.5 g The above composition A in 500 cc. Then, the composition B was melted in this order and finished to 1 liter for use. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

(Development Processing Conditions) Process Temperature Time Development 40 ° C. 15 seconds Fixing 35 ° C. 15 seconds Washing with water 30 ° C. 10 seconds Drying 50 ° C. 10 seconds The fog density was measured from the treated sample. Further, two samples before development were rubbed so that the emulsion surface and the base surface were in contact with each other, and after processing under the above conditions, the degree of scratch generation was evaluated on a scale of 5 (5 is the best and 1 is the worst). Similarly, the pressure fog was evaluated in 5 grades (good 5 to 1).
evil).

The results are shown in Table 1 together.

[0088]

[Table 1]

[0089]

[Chemical 15]

It can be seen from Table 1 that the samples of the present invention each containing one type of fluorine-based anion activator and one type of cation activator suppressed fogging, scratches and pressure fogging.

Example 2 Samples 11 to 18 prepared in the same manner as in Example 1 were processed and evaluated in exactly the same manner except that the developing solution was changed to the following formulation while being unexposed.

Developer formulation Hydroquinone 35 g N-methyl-p-aminophenol / sulfate 0.25 g Ethylenediaminetetraacetic acid 1.0 g Sodium sulfite 60.0
g Sodium hydroxide 8.0g 3- (Diethylamino) -1,2-propanediol 30g Sodium bromide 3.0g 5-Methylbenzotriazole 0.1g 1-Phenyl-5-mercaptotetrazole 0.08g 1-Phenyl-4,4- Dimethyl-3-pyrazolidone 0.2 g Phenylpicolinium bromide 2.5 g Water was added to make 1 liter, and the pH was adjusted to 10.8.

[0093]

[Table 2]

As is clear from Table 2, the sample according to the present invention effectively suppressed all of fog, scratches and pressure fog.

[0095]

According to the present invention, it is possible to obtain a super-high contrast image with less fog and scratches and strong against pressure.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuji Aritomi Konica Co., Ltd. 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing a hydrazine derivative in at least one silver halide emulsion layer or a layer adjacent to the emulsion layer, and at least one of the emulsion layer and other hydrophilic colloid layers. A silver halide photographic light-sensitive material, wherein the layer contains at least one compound represented by the following general formula (FA) and at least one compound represented by the general formula (FK). Formula (FA) (Cf)-(Y) _n [In the formula, Cf is an n-valent group containing at least 3 fluorine atoms and at least 2 carbon atoms, and Y is -COOM,-
SO ₃ M, represents an -OSO ₃ M or -P (= O) (OM) 2. M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt, and n is 1 or 2. ] Formula (FK) Rf'-L-X + Z - wherein, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, at least one hydrogen atom is substituted with fluorine atoms.
L represents a chemical bond or a divalent group. X ⁺ is a cation, Z ⁻
Represents a counter anion. ]