EP0543576A1

EP0543576A1 - A developer composition and a method for forming an image which uses the same

Info

Publication number: EP0543576A1
Application number: EP92310374A
Authority: EP
Inventors: Yasuhiko c/o Konica Corporation Muramatsu; Akira c/o Konica Corporation Kobayashi; Junichi C/O Konica Corporation Fukawa
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1991-11-21
Filing date: 1992-11-13
Publication date: 1993-05-26

Abstract

Disclosed is a developer composition for a silver halide photographic light-sensitive material, which comprises a dihydroxybenzene type developing agent, at least one of a auxiliary developing agent selected from 1-phenyl-3-pyrazolidone and p-aminophenol, a sulfite, wherein the amount of said sulfite is not less than 0.3 mol per liter of a developing solution, and an amine compound represented by Formula I;

wherein R₁ is an alkyl group or a carbonyl group, R₂ is an alkyl group, R₃, R₄, R₅ and R₆ each represent an alkyl group, and n is an integer of 1 to 5.

A developer solution containing the developer composition is capable of providing a ultra high-contrast photographic characteristics without failing a sensitivity of a silver halide photographic light-sensitive material.

Description

FIELD OF THE INVENTION

The present invention relates to a developer composition capable of forming a ultra high-contrast photographic image and a method for the formation of an image which uses the developer composition.

BACKGROUND OF THE INVENTION

A photomechanical process includes a process of transforming an original continuous-tone image into a halftone-dot image; i.e., transforming the continuous tone's density changes into a gathering of dots in different sizes corresponding to the densities.
This process employs a ultra high-contrast-image-reproducible photographic technique, in which a graphic arts film is exposed through a contact screen to an original image and then subjected to an infectious development to form a halftone-dot image.
A lithographic silver halide light-sensitive material for use in the infectious development must be processed in an infectious developer (lith developer) for obtaining a sufficiently contrasty image; for example, if it is processed in a MQ or PQ developer, its gamma value comes to 5 or 6 at the most and produces much fringe that must be avoided in the halftone image formation, and thus it is essential to process the light-sensitive material in an infectious developer, which is not preservable.
Accordingly, there have been developed techniques which employ a developer solution having a high sulfite ion concentration, being well preservable and applicable to rapid processing to thereby enable ultra high-contrast image formation comparable to the infectious development. As one of the developed techniques there is known a technique disclosed in JP O.P.I. No. 106244/1981. This technique is characterized by making a specific compound called a contrast-increasing agent, such as a hydrazine derivative or a tetrazolium compound, present in a silver halide photographic light-sensitive material and using specific silver halide grains in combination with other photographic additives in the light-sensitive material in order to make the most of the contrast-increasing characteristic of the compound.
The above silver halide photographic light-sensitive material makes it possible to obtain a ultra high-contrast photographic image even when processed in a developer well-preservable and suitable for rapid processing. This silver halide light-sensitive material, however, has the disadvantage that sandy dots, so-called black spots, appear among the half-tone dots in the halftone image formation to impair the half-tone image quality.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a developer composition which, when used to process a light-sensitive material, enables it to have a ultra high-contrast photographic characteristic without impairing its sensitivity and at the same time inhibits the generation of black spots in its unexposed area, and also provide a method for forming an image which uses the developer composition.
The above object of the invention is accomplished by a developer composition comprising

(1) a dihydroxybenzene-type developing agent,
(2) a 1-phenyl-3-pyrazolidone and/or p-aminophenol auxiliary developing agent,
(3) a sulfite in a concentration of not less than 0.3 mol per liter of a developing solution, and
(4) an amine compound represented by the following Formula [1], and also by a method for forming an image which comprises processing a silver halide photographic light-sensitive material in a developer solution according to the above developer composition, said silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer, in which said silver halide emulsion layer and other hydrophilic colloid layers contain a hydrazine derivative,
wherein R₁ is a substituted or unsubstituted alkyl group, an aryl group or a carbonyl group; R₂ is a substituted or unsubstituted alkyl group; R₃, R₄, R₅ and R₆ each represent an alkyl group; and n is an integer of 1 to 5.

DETAILED DESCRIPTION OF THE INVENTION

The hydrazine derivative used in the invention is preferable to be of a structure having the following Formula H, described in Japanese Patent Application No. 327402/1990, pp.13 to 72.

wherein A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom; G is a

group, a sulfonyl group, a sulfoxy group, a

group or an iminomethylene group; n is an integer of 1 or 2; A₁ and A₂ each represent a hydrogen atom, or either one of them is a hydrogen atom, while the other is a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group; and R is 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 a -O-R₃ group, wherein R₃ is an alkyl group or a saturated heterocyclic group.
The hydrazine derivative used in the invention is further preferred to be of structures of the following Formulas A and B:

wherein A is an aryl group or a heterocyclic group containing at least one sulfur or oxygen atom; n is an integer of 1 or 2, provided that when n is equal to 1, R₁ and R₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocycloxy group, and R₁ and R₂ together with a nitrogen atom may form a ring, while when n is equal to 2, R₁ and R₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a saturated or unsaturated heterocyclic ring, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocycloxy group, provided that when n is 2, at least one of R₁ and R₂ represents analkenyl group, an alkinyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocycloxy group; and R₃ is an alkenyl group or a saturated heterocylic group.
Compounds represented by Formulas [A] and [B] include those in which at least either one of the hydrogen atoms of the -NHNH- group thereof is substituted by a substituent.
To be more precise, A represents an aryl group, such as phenyl or naphthyl, or a heterocyclic group containing a sulfur or oxygen atom, such as thiophene, furan, benzothiophene, pyrane or the like.
R₁ and R₂ each represent a hydrogen atom, an alkyl group such as methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl or trifluoroethyl, an alkenyl group such as allyl, butenyl, pentenyl or pentadienyl, an alkynyl group such as propargyl, butynyl or pentynyl, an aryl group such as phenyl, naphthyl, cyanophenyl or methoxyphenyl, a heterocyclic group including a saturated heterocyclic group such as pyridine, thiophene or furan and a unsaturated heterocyclic group such as tetrahydrofuran or sulforan, a hydroxy group, an alkoxy group such as methoxy, ethoxy, benzyloxy or cyanomethoxy, an alkenyloxy group such as allyloxy or butenyloxy, alkynyloxy group such as propargyloxy or butynyloxy, an aryloxy group such as phenoxy or naphthyloxy, or a heterocycloxy group such as pyrydyloxy or pyrimidyloxy. When n is 1, R₁ and R₂ together with a nitrogen atom may form a ring such as piperidine, piperazine or morpholine.
When n is 2, at least either one of R₁ and R₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocycloxy group. Examples of the alkynyl group and saturated heterocyclic group represented by R₃ include what have been described earlier.
Any of various substituents may be introduced to the aryl group or heterocyclic group having at least one sulfur or oxygen atom represented by A. Examples of the introducible substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acyl group, an amino group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamido group, an arylaminothiocarbonylamino group, a hydroxy group, a carboxy group, a sulfo group and a cyano group. The preferred among these is a sulfonamido group.
In each of the above formulas, the group represented by A is preferable to contain at least one nondiffusible group or silver halide adsorption-accelerating group. Preferred as the nondiffusible group is a ballast group that is usually used in stationary photographic additives such as couplers. The ballast group is a group which has not less than eight carbon atoms and which is relatively inert photographically, and may be selected from the group consisting of an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group.
Preferred as the silver halide adsorption-accelerating group are those groups described in U.S. Patent No. 4,385,1098, such as thiourea, thiourethane, heterocyclic thioamido, mercaptoheterocyclic and triazole groups.
In Formulas [A] and [B], the hydrogen atoms for the hydrazine group -NHNH- may be replaced by a substituent such as a sulfonyl group such as methanesulfonyl or toluenesulfonyl, an acyl group such as acetyl, trifluoroacetyl or ethoxycarbonyl, an oxalyl group such as ethoxalyl or pyruvoyl.
More preferred in the invention are compounds of Formula [A] in the case of n=2 and compounds of Formula [B].
Further preferred are compounds of Formula [A] in n=2 wherein R₁ and R₂ each are a hydrogen atom, an alkyl, alkenyl, alkynyl, aryl, saturated or unsaturated heterocyclic, hydroxy or alkoxy group, provided at least either one of R₁ and R₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxyl group or an alkoxy group.
The following are typical examples of the compounds represented by Formulas [A] and [B], but it goes without saying that the invention is not limited by the examples.

Exemplified compounds

The photographic light-sensitive material according to the invention contains a hydrazine derivative in an amount of preferably 5x10⁻⁷ to 5x10⁻¹ mol and more preferably 5x10⁻⁶ to 1x10⁻² mol per mol of silver halide.
The following are examples of the amine compound represented by Formula [1], used for the developer composition of the invention.

Exemplified compounds

(1) H₂N-CH₂-O-CH₂-NH₂
(2) H₂N-CH₂-CH₂-O-CH₂-NH₂
(3) H₂N-CH(CH₃)-CH₂-O-CH₂-NH₂
(4) H₂N-CH₂-(O-CH₂)₂-NH₂
(5) H₂N-CH₂-CH₂-(O-CH₂-CH₂)₃-NH₂
(6) H₂N-C(CH₃)=CH-(O-CH₂)₅-NH₂
(7) H₂N-CH(CH₃)-CH₂-(O-CH₂-CH₂)₂-NH₂
(8) H₂N-CH(CH₃)-CH₂-[O-CH₂-CH(CH₃)]₃-NH₂
(9) H₂N-CH(CH₃)-CH(CH₃)-(O-CH(CH₃)-CH(CH₃))₂-NH₂
(10) CH₃-NH-CH₂-(O-CH₂)₄-NH-CH₃
(11) CH₃-NH-CH₂-CH₂-(O-CH₂-CH₂)₂-NH-CH₃
(12) CH₃-NH-CH(CH₃)-CH₂-(O-CH₂-CH(CH₃))₄-NH-CH₃
(13) (CH₃)₂N-CH₂-(O-CH₂-CH₂)₂-N(CH₃)₂
(14) (CH₃)₂N-C(CH₃)₂-CH₂-O-CH₂-C(CH₃)-N(CH₃)₂
(15) (CH₃)₂ N-CH(CH₃)-CH₂-(O-CH₂-CH(CH₃)₂-N(CH₃)₂

These compounds are available from Texaco Chemical Company.
The adding amount of the above compound depends on the type of an object into which it is to be incorporated and on its kind, but is usually in the range of from 0.1 to 100g, and preferably from 0.5 to 20g per liter of a developer.
The hydroxybenzene developing agent used in the developer of the invention is, e.g., hydroquinone, chlorohydroquinone, methylhydroquinone, or the like, but is preferably hydroquinone.
Those suitable as the 1-phenyl-3-pyrazolidone-type developing agent used in the invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4--hydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone. Of these the most preferred is the 1-phenyl-3-pyrazolidone.
As the p-aminophenol-type developing agent used in the invention there are N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol and p-benzylaminophenol. Of these the most preferred is the N-methyl-p-aminophenol.
Regarding the using amount of these developing agents, the dihydroxybenzene is used preferably in a concentration of 0.05 mol to 0.5 mol per liter, while the 1-phenyl-3-pyrazolidone and/or the p-aminophenol preferably in a concentration of not more than 0.06 mol per liter of a developer solution.
The sulfite to be used in the invention can be any sulfite as long as it liberates sulfurous acid ions (SO₃²⁻) in a developer solution; e.g., sodium sulfite, potassium sulfite or potassium hydrogensulfite. The sulfurous acid ion concentration in a developer solution is preferably not less than 0.3 mol per liter of a developer solution, but exceeding 1.2 moles per liter is impractical for manufacture. The suitable concentration range for manufacture is 0.4 to 0.7 mol per liter.
The pH range of the developer solution of the invention is preferably from 10 to about 13, and more preferably 10 to 12. If the pH value is less than 10, the developer solution is unable to provide any sufficiently contrasty image.
A preferred embodiment of the invention is such that the foregoing developer solution contains a phosphate in a concentration of preferably not less than 0.05 mol, more preferably 0.2 to 1 mol per liter of the developer solution. A more preferred embodiment is the processing being made in the presence of an organic antifoggant. Still another preferred embodiment is the use of an antioxidant in addition to the sulfite. And a still further preferred embodiment is the use of a developer solution whose sodium ion concentration is higher than potassium ion concentration.
In the invention, where an acid hardening fixer solution is used as a fixer, the developer solution should contain a carbonate as a pH buffer in a concentration of preferably not less than 0.05 mol, more preferably not less than 0.2 mol per liter.
The silver halide for the silver halide emulsion used in the invention (hereinafter sometimes called 'the silver halide emulsion' or merely 'the emulsion') may be any discretionary silver halide for ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, or the like, but is preferably silver chlorobromide, silver bromide, or silver iodobromide containing silver iodide below 2 mol%.
The silver halide is preferably of monodisperse grains having a variation coefficient of not more than 15%, which is defined by $\frac{Standard deviation of grain diameters}{Average value of grain diameters} x 100$
A large variety of techniques and additives known to those skilled in the art may apply to the silver halide emulsion of the invention.
For example, into the silver halide photographic emulsion and backing layer of the invention there may be incorporated various additives such as chemical sensitizers, toning agents, hardeners, surfactants, viscosity increasing agents, plasticizers, lubricants, development restrainers, UV absorbents, antiirradation agents, heavy metals, matting agents and the like, in accordance with various methods. Further, the silver halide photographic emulsion and backing layer of the invention may also contain a polymer latex.
Materials usable as the support of the silver halide photographic light-sensitive material of the invention include cellulose acetate, cellulose nitrate, a polyester such as polyethylene terephthalate, a polyolefin such as polyethylene, polystyrene, baryta paper, polyolefin-coated paper, glass and metals. The support may be subjected to subbing treatment if necessary.

EXAMPLES

The following are examples of the invention, but the embodiment of the invention is not limited by the examples.

Example 1

Preparation of Silver Halide Emulsion A

A silver iodobromide emulsion (containing 2 mol% silver iodide per mol of silver) was prepared in accordance with a double-jet process. In the course of the preparation, K₂IrCl₆ was added in an amount of 8x10⁻⁷ mol per mol of silver. The obtained emulsion was an emulsion of cubic monodisperse silver halide grains (variation coefficient: 9%) having an average grain diameter of 0.20µm. This emulsion, after adding thereto a denatured gelatin (exemplified compound G-8 in Japanese Patent Application no. 180787/1989), was washed to be desalted in the same manner as in Example 1 described in Japanese Patent Application No. 180787/1989. The emulsion showed a pAg of 8.0 at 40°C after the desalting. Subsequently, 0.1 mol% per mol of silver of an aqueous potassium iodide solution was added to the emulsion to subject its grains to surface conversion treatment, and then a mixture of the following compounds [A], [B] and [C] was added, whereby Emulsion A was obtained.

Preparation of a silver halide light-sensitive material

On one side of a 100µm-thick polyethylene terephthalate film having both sides thereof coated with subbing layers each having a thickness of 0.1µm was coated a silver halide emulsion layer of the following prescription (1) so as to have a gelatin coating weight of 2.0g/m² and a silver coating weight of 3.2g/m², and further coated on the emulsion layer an emulsion protective layer of the following prescription (2) so as to have a gelatin coating weight of 1.0g/m², and on the other side of the support was coated a backing layer of the following prescription (3) so as to have a gelatin coating weight of 2.4g/m², and further thereon coated a backing protective layer of the following prescription (4) so as to have a gelatin coating weight of 1g/m², whereby a sample was obtained.

The obtained sample was exposed through an optical step-wedge in close contact therewith to a 3200K tungsten light for 5 seconds, and then processed under the following conditions in a rapid processing automatic processor GR-26SR, manufactured by KONICA Corp, using developer and fixer solutions of the following compositions:

Developer
Sodium hydrogensulfite	40 g
EDTA	1.0g
Potassium hydroxide (45%)	0.07ml
Sodium chloride	4.7g
Potassium bromide	1.2h
Potassium phosphate	27g
5-Methylbenzotriazole	0.25g
2-Mercaptobenzotriazole	23mg
Benzotriazole	83mg
Hydroquinone	29g
1-Phenyl-3-pyrazolidone	0.5g
Diisopropylaminoethanol	2.25ml
Invention's Compound [1]	1g
Water to make 1 liter

pH was adjusted to 11.6 with potassium hydroxide.

For use, Compositions A and B were dissolved in the described order into 500ml of water, and then water was added to make the whole 1 liter. pH of the fixer bath was adjusted to 4.8 with acetic acid.

Processing conditions

Step Temperature Time

Developing 38°C 20 seconds

Fixing 35°C 20 seconds

Washing 30°C 15 seconds

Drying 50°C 15 seconds
Each of the obtained samples was subjected to density measurement by means of an optical densitometer KONICA PDA-65 to thereby provide photographic characteristics, wherein the sensitivity of each sample is shown in terms of a relative speed to the speed at a density of 2.5 of Sample No.1 set at 100, while the gamma is given at a tangential slope formed between the points at densities of 0.1 and 2.5. A gamma value of less than 6 is totally unacceptable, that of more than 6 and less than 10.0 is still insufficient for high-contrast characteristic and that of 10 or more can form a ultra high-contrast image which is considered practically usable.
Black spots in unexposed areas were examined for evaluation by being observed through a 40-power magnifying glass. An unexposed area with no black spots at all was ranked top '5', followed by being ranked down as '4', '3', '2' and '1' as the number of black spots increases. Those ranked '1' and '2' are on undesirable black spot levels.

The results are shown in Table 1.

Table 1

Sample N°.	Hydrazine derivative [H]	Compound [I] of invention	Gamma	Black spots	Remarks
1	-	-	5.5	3	Comparative
2	-	3	6.2	3	''
3	1	-	8.7	1	''
4	''	3	13.9	4	Invention
5	''	4	12.7	4	''
6	''	8	13.3	5	''
7	''	12	14.1	5	''
8	4	2	15.3	4	''
9	''	5	16.1	4	''
10	''	8	14.8	5	''
11	''	13	16.6	4	''
12	''	14	15.5	4	''
13	12	2	11.4	4	''
14	''	8	12.2	4	''
15	''	14	11.9	5	''

As is apparent from Table 1, samples No.4 to 15 for the invention show much higher gamma values and better black spots evalution than the comparative samples.

Example 2

Experiments were made in the same manner as in Example 1 except that the developer was replaced by one prepared in accordance with the following developer prescription 2.

Developer prescription 2
Sodium hydrogensulfite	40g
EDTA	1.0g
Potassium hydroxide (45%)	0.05ml
Sodium chloride	4.7g
Potassium bromide	1.2g
Potassium phosphate	27g
Sodium Phosphate	20g
5-Methylbenzotriazole	0.25g
2-Mercaptobenzotriazole	23mg
Benzotriazole	83mg
Hydroquinone	29g
N-methyl-p-aminophenol	0.5g
Diisopropylaminoethanol	2.25ml
Invention's Compound [1]	1g
Water to make 1 liter.

pH was adjusted to 11.6 with potassium hydroxide.

The results are shown in Table 2.

Table 2

Sample No.	Hydrazine derivative [H]	Compound [I] of the invention	Gamma	Black spots	Remarks
1	-	-	5.5	3	Comparative
2	-	3	6.9	3	''
3	1	-	8.7	1	''
4	''	3	13.9	4	Invention
5	''	4	13.8	5	''
6	''	8	13.3	5	''
7	''	12	14.1	5	''
8	4	2	15.4	4	''
9	''	5	16.1	4	''
10	''	8	14.7	4	''
11	''	13	16.6	5	''
12	''	14	15.6	5	''
13	12	2	12.4	4	''
14	''	8	12.5	4	''
15	''	14	11.9	4	''

As is apparent from Table 2, samples No.4 to 15 for the invention show much higher gamma values and better black spots evalution than the comparative samples.

Example 3

Experiments were made in the same manner as in Example 1 except that the developer solution used in Example 1 was replaced by a developer solution according to the following prescription 3:

Developer prescription 3
Sodium hydrogen sulfite	40 g
EDTA	1.0g
Potassium hydroxide (45%)	0.07ml
Sodium chloride	4.7g
Potassium bromide	1.2g
Potassium phosphate	27g
5-Methylbenzotriazole	0.25g
2-Mercaptobenzothiazole	23 mg
Benzotriazole	83 mg
Hydroquinone	29 g
N-methyl-p-aminophenol	0.5g
Diisopropylaminoethanol	2.25ml
Invention's Compound [1]	1g
Water to make 1 liter

pH was adjusted to 10.6 with potassium hydroxide.

The results are shown in Table 3.

Table 3

Sample No.	Hydrazine derivative [H]	Compound [I] of invention	Gamma	Black spots	Remarks
1	-	-	5.6	3	Comparative
2	-	3	6.5	3	''
3	1	-	8.8	1	''
4	''	3	14.1	5	Invention
5	''	4	13.5	4	''
6	''	8	14.2	4	''
7	''	12	13.8	5	''
8	4	2	16.1	5	''
9	''	5	15.7	4	''
10	''	8	14.9	5	''
11	''	13	16.2	4	''
12	''	14	14.5	4	''
13	12	2	13.8	5	''
14	''	8	14.4	4	''
15	''	14	12.2	5	''

As is apparent from Table 3, samples No.4 to 15 for the invention show much higher gamma values and better black spots evalution than the comparative samples.

Claims

A developer composition for a silver halide photographic light-sensitive material, which comprises a dihydroxybenzene type developing agent, at least one of a auxiliary developing agent selected from 1-phenyl-3-pyrazolidone and p-aminophenol, a sulfite, wherein the amount of said sulfite is not less than 0.3 mol per liter of a developing solution, and an amine compound represented by Formula I:
wherein R₁ is an alkyl group or a carbonyl group, R₂ is an alkyl group, R₃, R₄, R₅ and R₆ each represent an alkyl group, and n is an integer of 1 to 5.
The material of claim 1, wherein said dihydroxybenzene type developing agent is selected from the group consisting of a hydroquinone, a chlorohydroquinone and a methylhydroquinone.
the material of claim 1, wherein said sulfite is a compound selected from the group consisting of sodium thiosulfite, potassium thiosulfite, sodium bisulfite and potassium bisulfite; and the amount of said sulfite is not less than 0.3 mol per liter of the developing solution.
A method for forming an image comprising a step of processing a silver halide photographic light-sensitive material by a developing solution, which comprises a developing composition comprising a dihydroxybenzene type developing agent, at least one of a auxiliary developing agent selected from 1-phenyl-3-pyrazolidone and p-aminophenol, a sulfite, wherein the amount of said sulfite is not less than 0.3 mol per liter of a developing solution, and an amine compound represented by Formula I;
wherein R₁ is an alkyl group or a carbonyl group, R₂ is an alkyl group, R₃, R₄, R₅ and R₆ each represent an alkyl group, and n is an integer of 1 to 5.
The material of claim 4, wherein said silver halide photographic material comprises a support having thereon a silver halide emulsion layer and a hydrazine compound.
The material of claim 5, wherein said hydrazine compound is represented by Formula H:
wherein A represents an aryl group or a heterocyclic group containing at least one sulfur atom or an oxygen atom, G represents a
group, a sulfonyl group, a sulfoxy group, a
group or an iminomethylene group, n is an integer of 1 or 2, A₁ and A₂ each represent a hydrogen atom or either one of them is a hydrogen atom, while the other is an alkyl group or an acyl group, R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an amino group, a carbamoyl group, an oxycarbonyl group or a -O-R₃ group, wherein R₃ represents an alkyl group or a saturated heterocyclic group.
The material of claim 6, wherein said hydrazine compound is represented by Formula A of Formula B:

wherein A represents an aryl group or a heterocyclic group containing at least one sulfur or an oxygen atom, n is an integer of 1 or 2, provided that when n is 1, R₁ and R₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, a hydroxyl group, an alkoxyl group, an alkenyloxy group, an alkinyloxy group, an aryloxy group, a heterocyclicoxy group, and R₁ and R₂ together with a nitrogen atom may form a ring: while when n is 2, R₁ and R₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic ring, a hydroxyl group, an alkoxyl group or a heterocyclicoxy group, provided that when n is 2, at less one of R₁ and R₂ represent an alkenyl group, an alkinyl group, a saturated heterocyclic group, a hydroxyl group, an alkoxyl group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclicoxy group, and R₃ represents an alkinyl group or a saturated heterocyclic group.
A developer composition for a silver halide photographic light-sensitive material, which comprises a hydroquinone as a developing agent, at least one of a auxiliary developing agent selected from 1-phenyl-3-pyrazolidone and p-aminophenol, a sulfite, wherein the amount of said sulfite is within the range of 0.4 mol to 0.7 mol per liter of a developing solution, and an amine compound represented by Formula I:
wherein R₁ is an alkyl group or a carbonyl group, R₂ is an alkyl group, R₃, R₄, R₅ and R₆ each represent an alkyl group, and n is an integer of 1 to 5