EP0302251A2

EP0302251A2 - Silver halide photographic light-sensitive material

Info

Publication number: EP0302251A2
Application number: EP88110826A
Authority: EP
Inventors: Shigeo Tanaka; Takaaki Kojima; Nobuaki Kagawa; Yasuhiko Kawashima
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1987-07-09
Filing date: 1988-07-07
Publication date: 1989-02-08
Also published as: JPH01105237A; EP0302251A3

Abstract

A silver halide photographic light-sensitive material is disclosed, which is improved in increased light-sensitivity and lowered fog. The photographic material has at least one silver halide emulsion layer containing a silver halide chemically sensitized in the presence of a compound represented by the followinf formula 1.
Formula (I)
(X)n - Q - (S - Y)m
wherein X represents a water-soluble group; Q represents an organic m+n valent group; Y represents a hydrogen atom, an amidino group, or an atom or a group of atoms capable of forming a monovalent cation, and m and n each represent an integer of 1 or 2.

Description

FIELD OF THE INVENTION

The present invention relates to a high-speed silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having low minimum density and high speed, and having superior storage stability.

BACKGROUND OF THE INVENTION

Because of high speed and excellent gradation, silver halide photographic light-sensitive materials have nowadays been very widely used. Moreover, printers and automatic processing machines have been so improved that it has become possible to continuously carry out development processing of silver halide photographic light-sensitive materials in a large quantity, bringing about high productivity and also very great practical value together with the above-mentioned excellent performances.
If a silver halide emulsion has a high speed, the light-sensitive material for photography does not require any special illumination even in the dark, becomes feasible for photographying with illumination existing there, and becomes feasible for photographying at a higher shutter speed or becomes feasible for more stopped-down photographying, thus enlarging the degree of freedom of photographying. In the case of light-sensitive materials for printing, it can also be achieved to shorten the printing time. Besides these side views, making smaller the grain size of silver halide emulsions can also improve the graininess. In other instances, increasing the quantities of anti-halation dyes and anti-irradiation dyes makes it possible to improve the sharpness and to achieve higher image quality.
Thus, the techniques for achieving higher speed are important techniques not only in the sense that there can be provided high speed light-sensitive materials but also in the sense that a way is opened toward high image quality light-sensitive materials and the development thereof has been sought after. Most of sensitization techniques hitherto known have had disadvantages such that fog increases with improvement in sensitization or that fog increases during storage even if fog is low at the time of the preparation of light-sensitive materials.
In the course of researches on the chemical ripening of silver halide emulsions, the present inventors have discovered that a certain type of compound can favorably control the chemical ripening reaction to achieve high speed and low fog simultaneously, and thus accomplished the present invention.
Japanese Patent Examined Publication No. 9939/1983 discloses a silver halide photographic light-sensitive material containing at least one of magenta or yellow two equivalent coupler or a 3-arylamino-5-pyrazolone derivative, and a heterocyclic compound having at least one of a sulfo group, a carboxyl group, a hydroxyl group and an amino group and a mercapto group, and states that it is superior in the suppression of fog at the time when developed at temperatures of 30°C or more and the storage stability. However, as is apparent from its specification, this technique does not refer to the time when they are added in the silver halide emulsion, and only discloses an example where they are added in the course of preparing a coating solution, without any teaching as to the effect obtainable when added in the course of chemical ripening.
European Patent No. 226,184 discloses that a silver halide photographic light-sensitive material containing a certain type of mercapto compound may be developed in the presence of a fogging agent to obtain high contrast and low fog. However, as stated in its specification, this is a technique for making adjustment of fog development, and has taught nothing as to the influence that may be given to the chemical ripening.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a silver halide photographic light-sensitive material having low fog and high speed, and also suffering only small increase in fog during storage.
The above object can be achieved by a silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer containing a silver halide emulsion having subjected to chemical ripening in the presence of a compound represented by Formula (I) shown below.
Formula (1):
(X
Q
S-Y)_m
wherein X represents a hydrophilic group; Q represents an organic m+n valent group; Y represents a hydrogen atom, an amidino group, or an atom or a group of atoms that forms a monovalent cation; and m and n each represent 1 or 2.

DETAILED DESCRIPTION OF THE INVENTION

Preferred as X are -OPO(OH)₂ (including salts thereof), -SO₃H (including salts thereof), -COOH (including salts thereof), -OH, and -NHR (R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
Of the compounds represented by Formula (I), a preferable group is represented by Formula (S).
Formula (S):
(Y-S)-L₁-(J₁)_k-(L₂)₁-(Z)_m-(L₃)_n-(J₂L₄)_p(X′)
In the formula, L₁ to L₄ each represent a polyvalent hydrocarbon group, J₁ and J₂ each represent -O-, -COO-, -OCO-, -CONR¹-, -NR¹CO-, -SO₂NR¹, -NR¹SO₂-, -NR¹-CO-NR², -SO₂- -N=N-, -NR′- or -CO-; Y represents a hydrogen atom, an amidino group or a atom or a group of atoms that forms a monovalent cation; Z represents a heterocyclic group; X′ represents a sulfonic acid group, a carboxyl group or a phosphoric acid group: R¹ and R² each represent a hydrogen atom, an alkyl group or an aryl Group: k, l, m, and n each represent an integer of 0 to 2 that represents the repeating number; and p represents an integer of 0 to 4.
Provided that when X′ represents a carboxyl group, m represents an integer of 1 or 2. Also, when L₁ to L₄ and Z represent a trivalent or more group, an adjacent group may be bonded in the number necessary only for satisfying the valence.
In Formula (S), the polyvalent hydrocarbon group represented by L₁ to L₄ may include, for example, an alkylene group, a cycloalkylene group, an arylene group, an aralkylene group, and preferred as the alkylene group is the group having 1 to 15 carbon atoms, including, for example, methylene, ethylene, propylene, pentamethylene and dodecamethylene, and the cycloalkylene group may include 1,6-cyclohexylene.
The arylene group represented by L₁ and L₂ may include, for example, 1,4-phenylene, 1,3-phenylene, 1,4-naphthylene and 1,4-anthraquinolylene, and the aralkylene group may include benzylene and phenethylene.
The amidino group represented by Y includes those having a substituent, and the substituent may include, for example, an alkyl group (such as methyl, ethyl and benzyl), an aryl group (such as phenyl, p-tolyl and naphthyl), a heterocyclic group (such as 2-thiazolyl, 2-pyridyl and 4-imidazolyl).
The heterocyclic group represented by Z may preferably include a cyclic group of 5 members to 7 members, including those condensed with a benzene ring, a naphthalene ring, a heterocyclic ring of 5 or 6 members or an aliphatic ring of 5 or 6 members, specifically including heterocyclic rings such as, furan, thiophene, benzo[b]thiophene, imidazole, benzimidazole, pyrol, s-triazine, pyrimidine, quinoline, indole, benzoxazole and benzothiazole.
The alkyl group represented by by R¹ and R² may include, for example, methyl, ethyl and propyl; and the aryl group, for example, phenyl and naphthyl.
The polyvalent hydrocarbon group represented by L₁ to L₄, the aryl group and the alkyl group represented by by R¹ and R², the heterocyclic group represented by Z include those having a substituent, and the substituent may include, for example, an alkyl group such as methyl, ethyl and sec-propyl, and alkoxy group such as methoxy, ethoxy, sec-propyloxy and t-octyloxy, an amino group such as methylamino, N,N-dimethylamino and butylamino, an aryl group such as tolyl and phenyl, an aryloxy group such as phenoxy and naphthoxy, a mercapto group, a sulfonic acid group, a carboxyl group, a cyano group, a carbamoyl group, a sulfamoyl group, an amido group such as acetylamino and benzoyl amino, a sulfonyl group such as methanesulfonyl and benzenesulfonyl an alkoxycarbonyl group such as ethoxycarbonyl group, an aryloxycarbonyl group such as phenyloxycarbonyl, an acyl group such as acetyl, benzoyl and propionyl, and a heterocyclic group such as thienyl, oxazolyl and cinnolyl, as well as, for example, -J₂L₄X′, -J₁-L₁-SH (J₁, J₂, L₁ and L₄ have the same definition as above).
The carboxyl group, sulfonic acid group and phosphoric acid group represented by X′ may be free acid groups or may form a salt, and the salt includes inorganic cations such as alkali metals (such as Na, K, Li), alkaline earth metals (such as Ca, Mg) and ammonium, or organic ammoniums such as pyridinium, triethyl ammonium, triethanol ammonium, and guanidium. They may also form a intramolecular salt.
The compounds represented by Formula (S) used in the present invention can be grouped into a mercapto-substituted anion derivative (S-I) and a pseudothiuronium intramolecular slat derivative (S-II) depending on how Y is selected. Typical examples regarding these are shown below. The present invention is by no means limited to these, however.
The compound represented by by Formula (S) can be readily synthesized, for example, by making reference to papers such as J. Am. Chem. Soc., 77, 6231 (1955), J. Heterocycl. Chem., 1968, 5(3) 319-22, and Arm. Khim. Zh., 1967, 20(10), 832-5.
Of the compounds represented by Formula (I), another preferred group is represented by Formula (Ib).
Z represents a group of atoms necessary for completing a nucleus of a nitrogen-containing heterocyclic ring of 5 or 6 members (including condensed rings with other heterocyclic ring, benzene ring or naphthalene ring); M, a hydrogen atom, or an atom or a group of atoms that can form a monovalent cation. The heterocyclic group represented by Z may include, for example, an oxazole ring, a thiazole ring, an imidazole ring, a selenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a pentazole ring, a pyrimidine ring, a thiazine ring, a triazine ring and a thiadiazine, or rings condensed with other carbon ring or heterocyclic ring, including, for example, a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthoxazole ring, a triazaindolidine ring, a diazaindolidine ring and a tetrazaindolidine ring.
X represents the same groups as X in Formula (I), more preferably an -SO₃H group including salts thereof and a -COOH group including salts thereof.
L represents a simple bond or a divalent linking group. Preferable divalent linking group includes an alkylene group, an arylene group. n′ represents 1 or 2.
Examples of the compound represented by Formula (Ib) are shown below.
Steps for preparing silver halide photographic emulsions include, for example, a step of forming silver halide grains by mixing an aqueous silver salt solution and an aqueous silver halide salt to prepare silver halide, a desalting-redispersion step of subsequently removing excess soluble salts and optionally adding a hydrophilic binder to disperse silver halide grains, a chemical ripening step of carrying out ripening in the presence of a suitable sensitizer, and a chemical ripening stopping step of terminating chemical ripening by adding a suitable stabilizer or so.
The silver halide emulsion according to the present invention is subjected to the chemical ripening in the presence of the compound of Formula (I), and therefore must be added in a step preceding the chemical ripening step or a step during the chemical ripening.
Preferable amount of the compound of Formula (I) to be added to the silver halide emulsion is within the range of from 5 x 10⁻⁶ to 5 x 10⁻ mol per mol of silver halide.
Various sensitizing methods can be used in the silver halide emulsion of the present invention. More specifically, there can be used alone or in combination, sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization using gold or other noble metal compounds.
It is also preferable to carry out the sensitization by using the chemical sensitizers or sensitizing methods described, for example, in British Patents No. 618,061, No. 1,315,755 and No. 1,396,696, Japanese Patent Examined Publication No. 15748/1969, U.S. Patents No. 1,574,944, No. 1,623,499, No. 1,673,522, No. 2,278,947, No. 2,399,083, No. 2,410,689, No. 2,419,974 No. 2,448,060, No. 2,487,850, No. 2,518,698, No. 2,521,926, No. 2,642,361, No. 2,694,637, No. 2,728,668, No. 2,739,060, No. 2,743,182, No. 2,743,183, No. 2,983,609, No. 2,983,610, No. 3,021,215, No. 3,026,203, No. 3,297,446, No. 3,297,447, No. 3,361,564, No. 3,411,914, No. 3,554,767, No. 3,565,631, No. 3,565,633, No. 3,591,385, No. 3,656,955, No. 3,761,267, No. 3,772,031, No. 3,857,711, No. 3,891,446, No. 3,901,714, No. 3,904,415, No. 3,930,867, No. 3,984,249, No. 4,054,457 and No. 4,067,740, Research Disclosures No. 12008, No. 13452 and No. 13564, and T.H. James, The Theory of the Photographic Process (Fourth Ed. Macmillan. 1977) pp.67-76.
In particular, the compound of the present invention can exhibit great effect to the gold sensitization, desirably. Usable as gold sensitizers are chloroauric acid, gold thiocyanate, gold thiosulfate, gold sulfide, etc. The gold sensitizer may be added in an amount of from 5 x 10⁻⁷ mol to 5 x 10⁻⁴ mol, particularly preferably from 1 x 10⁻⁶ to 5 x 10⁻⁵.
Silver halide may be of any composition, including silver bromide, silver iodobromide, silver chloroiodobromide, silver iodochloride, silver chlorobromide and silver chloride, provided that silver iodide may preferably comprise 1 mol % or less, more preferably 0.5 mol % or less. Silver chlorobromide containing 80 mol % or more of silver chloride is advantageous as greatly bringing about the effect of the present invention and also from the viewpoint of rapid processing.
Methods for preparing silver halide grains include an acidic method, a neutral method and an ammoniacal method, any of which can be preferably used. There may be also used silver halide solvents other than ammonia. The grains may be brought to grow at one time or to grow after making seed grains. The method for making the seed grains and the method for bringing them to grow may be the same or different.
The silver halide emulsion may be prepared by simultaneously mixing silver halide ions and silver ions, or by mixing any one of them into a solution in which the other of them is present.
The silver halide emulsion according to the present invention may be used by mixing two or more kinds of silver halide emulsions separately formed.
The silver halide grains used in the present invention may have a polydispersed grain size distribution or a monodispersed one.
In the silver halide grains used in the silver halide emulsion of the present invention, metal ions can be added in the course of the formation of grains and/or in the course of the growth thereof by using at least one selected from cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts containing the same, rhodium salts or complex salts containing the same or iron salts or complex salts containing the same to incorporate these metalic elements into the inside and/or surfaces of grains, or reduction sensitization nuclei may be imparted to the inside and/or surface of grains by placing them in a suitable reducing atmosphere.
In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after growth of silver halide grains, or they may be kept to remain. When the salts are removed, it can be carried out on the basis of the method described in Research Disclosure No. 17643.
The silver halide grains of the present invention may preferably have an average grain size (the grain size indicates the diameter of a circle having the area equal to the projected area) of 5 µm or less, but particularly preferably 1 µm or less.
Sensitization effect can be more preferable in regard to the compound of Formula (S), particularly preferably the compound represented by Formula (S′).
Formula (S′)
MS -R³ -X˝
wherein R³ represents a divalent hydrocarbon group; X˝ represents a carboxyl group or a salt thereof, or a sulfonic acid group or a salt thereof; and M represents a hydrogen atom, or an atom or a group of atoms capable of froming a monovalent cation.
A compound having an alkylene group as the group represented by R³ is more preferable.
Among Formula (Ib), a compound represented by Formula (Ib′) is particularly preferable.
wherein Y′ represents an oxygen atom, a sulfur atom, a selenium atom or an -NR′ group, in which R′ represents an alkyl group; and M and X˝ each are the same as M and X˝ defined in Formula S′.
The silver halide emulsion can be optically sensitized to a desired wavelength region by using sensitizing dyes according to conventional methods.
In the silver halide emulsion, antifoggants, stabilizers or the like can be added. As binders for said emulsions, it is advantageous to use gelatin.
Emulsion layers and other hydrophilic colloid layers can be hardened, and there can be contained plasticizers, or dispersions of water-soluble or slightly water-soluble synthetic polymers (i.e., latexes).
Couplers are used in the emulsion layers.
There can be further used competing couplers, and a compound capable of splitting off photographically useful fragments such as a development accelerator, a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer through coupling with an oxidized product of a developing agent.
The light-sensitive material can be provided with auxiliary layers such as filter layers, anti-halation layers and anti-irradiation layers. Dyes that are flowed out from the light-sensitive material, or bleached, in the course of development processing may be contained in these layers and/or the emulsion layers.
In the light-sensitive material, it is possible to add formalin scavengers, optical brightening agents, matting agents, lubricants, image stabilizers, surface active agents, anti-color-fogging agent, development accelerators, development retardants and bleach accelerators.
As supports, usable are papers laminated with polyethylene or the like, polyethylene terephthalate films, baryta paper, cellulose triacetate, etc.
To obtain a dye image by using the light-sensitive material of the present invention, commonly known color photographic processing can be carried out after exposure to light.

EXAMPLES

The present invention will be specifically described below by giving Examples.

Example 1

In an aqueous gelatin solution, 2 mol/lit. of an aqueous silver nitrate solution and 2 mol/lit. of an aqueous mixed silver halide salts solution (potassium bromide: 50 mol %; sodium chloride: 50 mol %) were added, stirred and mixed to prepare a silver chlorobromide emulsion comprising cubic grains of 0.65 µm in one side length (Em-1).
Em-1 was divided and the divided emulsions were adjusted to have a temperature of 50°C, to each of which a comparative Compound A or a compound of the present invention was added, and after 3 minutes 1 x 10⁻⁵ mol of sodium thiosulfate per mol of silver halide was added to carry out chemical ripening. At the time when the chemical ripening was completed, a stabilizer (STB-1) was added in an amount of 1 x 10⁻³ mol per mol of silver halide.
Subsequently, on paper supports coated with polyethylene, the layers described below were coated to prepare silver halide photographic light-sensitive materials. Here, the coating amount for each compound was indicated by the value per 1 m².

(Layer 1):

A silver halide emulsion layer containing 0.3 g of dinonyl phthalate in which 0.8 g of a yellow coupler (YC-1) and 0.02 g of color-contamination preventive agent (HQ-1) were dissolved, a blue-sensitive silver chlorobromide emulsion (0.35 g in terms of silver; silver bromide content: 50 mol %) and 3.5 g of gelatin.

(Layer 2):

A protective layer containing 2 g of gelatin.

Color photographic paper thus prepared was exposed to light according to a conventional method, and subjected to development processing as shown below to obtain a yellow dye image. This was measured using a PDA-65 densitometer (manufactured by Konica Corporation) to measure the speed and fog. The speed was indicated as a relative value assuming that of Sample 101 as 100.

Table 1

Sample No.	Additive	Amount mol/molAgX	Fog	Speed
101	Comparative Comp. A	5 x 10⁻⁵	0.14	100
102	Exemplary S-I-1	5 x 10⁻⁵	0.10	130
103	Exemplary S-I-9	5 x 10⁻⁵	0.10	122
104	Exemplary S-I-11	5 x 10⁻⁵	0.08	150
105	Exemplary S-I-20	5 x 10⁻⁵	0.10	132
106	Exemplary S-I-27	5 x 10⁻⁵	0.08	138
107	Exemplary S-II-6	5 x 10⁻⁵	0.11	118
108	Exemplary S-II-14	5 x 10⁻⁵	0.10	110
109	Exemplary Ib-1	5 x 10⁻⁵	0.10	135
110	Exemplary Ib-5	5 x 10⁻⁵	0.12	115
111	Exemplary Ib-9	5 x 10⁻⁵	0.10	128
112	Exemplary Ib-15	5 x 10⁻⁵	0.10	125
113	Exemplary Ib-19	5 x 10⁻⁵	0.12	108
114	-		0.18	115

As is shown in Table 1, the light-sensitive materials employing the silver halide emulsion having been subjected to the chemical ripening by adding the compound of the present invention are seen to be decreased in any fog and able to achieve high speed. In particular, as in Samples 104 and 106, the compound wherein a sulfo group and a mercapto group are linked with an alkylene group can achieve great improvement in the fog and speed. The compound having a amidino group, though small in the effect as compared with the compound having a mercapto group, showed superior performance as compared with the comparative compound.
In addition thereto, among the compounds wherein a mercapto group is directly bonded to a nitrogen-containing heterocyclic nucleus, there are compounds showing superior performance as having high speed and low fog as in Samples 109, 111 and 112. Comparison of Sample 103 with Sample 111 can tell that the compound wherein a mercapto group is directly bonded to the 2-position of benzothiazole brings about greater effect. Comparison of Comparative Sample 101 with Samples 110 and 113 can tell that, though there is only the difference whether or not a water-soluble group is bonded to the phenyl group bonded to a tetrazole ring, the compound wherein the water-soluble group is bonded brings about better sensitization and lowering of fog. Between a sulfo group and a carboxyl group, the sulfo group is seen to have superiority in respect of the sensitizing effect.

(Processing steps)

	Temperature	Time
Color developing	33°C	3 min 30 sec
Bleach-fixing	33°C	1 min 30 sec
Washing	30 to 34°C	3 min
Drying

(Color developing solution)

Water 800 ml
Ethylene glycol 15 ml
Benzyl alcohol 18 ml
Hydroxylamine sulfate 2.0 g
Potassium carbonic anhydride 30.0 g
Potassium bromide 0.5 g
Sodium chloride 1.5 g
Potassium sulfite anhydride 2.0 g
N-ethyl-N-beta-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g
Made up to 1 liter by adding water and adjusted to pH = 10.2 with potassium hydroxide or sulfuric acid.

(Bleach-fixing solution)

Water 750 ml
Ferric (III) sodium ethylenediaminetetraacetate 50 g
Ammonium thiosulfate 85 g
Sodium bisulfite 10 g
Sodium metabisulfite 2 g
Disodium ethylenediaminetetraacetate 20 g
Sodium bromide 3.0 g
Made up to 1 liter by adding pure water and adjusted to pH = 7.0 with ammonia water or sulfuric acid.

Example 2

Example 1 was repeated except that the aqueous mixed silver halide salts solution was made to comprise a mixture of 0.5 mol % of potassium bromide and 99.5 mol % of sodium chloride, and the mixing rate was adjusted corresponding to the rate of growth of silver halide grains, thus preparing a silver chlorobromide emulsion comprising cubic grains of 0.65 µm in one side length (Em-2).

Chemical ripening was carried out in the same manner as in Example 1, and the speed and fog were evaluated. Results obtained are shown in Table 2. The speed was indicated by a relative value assuming that of Sample 201 as 100.

Table 2

Sample No.	Additive	Amount mol/molAgX	Fog	Speed
201	Comparative Comp. A	5 x 10⁻⁵	0.18	100
202	Exemplary S-I-1	5 x 10⁻⁵	0.11	130
203	Exemplary S-I-9	5 x 10⁻⁵	0.11	125
204	Exemplary S-I-11	5 x 10⁻⁵	0.08	189
205	Exemplary S-I-20	5 x 10⁻⁵	0.10	131
206	Exemplary S-I-27	5 x 10⁻⁵	0.08	152
207	Exemplary S-II-6	5 x 10⁻⁵	0.10	118
208	Exemplary S-II-14	5 x 10⁻⁵	0.10	112
209	Exemplary Ib-1	5 x 10⁻⁵	0.10	140
210	Exemplary Ib-5	5 x 10⁻⁵	0.13	110
211	Exemplary Ib-9	5 x 10⁻⁵	0.11	132
212	Exemplary Ib-15	5 x 10⁻⁵	0.10	130
213	Exemplary Ib-19	5 x 10⁻⁵	0.12	106
214	-		0.18	103

As is shown in Table 2, even when the emulsions having the silver chloride content of 99.5 mol % are used, the light-sensitive materials employing the silver halide emulsion having been subjected to the chemical ripening by adding the compound of the present invention are all seen to show low fog and able to achieve high speed. As in Samples 204 and 206, the oompound wherein a sulfo group and a mercapto group are linked with an alkylene group is seen to bring about greater sensitizing effect as compared with the emulsion having the silver chloride content of 50 mol %. Comparison of Comparative Sample 201 with Samples 210 and 213 can clearly tell the effect attributable to the hydrophilic group, but, on the contrary to the precedent examples, the effect is somewhat small as compared with the emulsions having the silver chloride content of 50 mol %, thus suggesting a mutual action between the structure of the compound and the composition of the silver halide. The compound wherein a mercapto group is directly bonded to the 2-position of benzimidazole, benzoxazole or benzothiazole and a sulfo group is substituted on a condensed benzene nucleus is also seen to have preferable performance.

Processing steps:

Color developing 35°C 45 seconds

Bleach-fixing 32°C 45 seconds

Washing 30 to 35°C 90 seconds

Drying 60 to 68°C 60 seconds
The color developing solution and bleach-fixing solution had the following make-up (per 1 liter).

(Color developing solution)

Water 800 ml
Triethanol amine 12 ml
N.N-diethylhydroxylamine (an aqueous 85 % solution) 12 ml
Potassium carbonic anhydride 30.0 g
Potassium chloride 2.2 g
Potassium sulfite 0.2 g
N-ethyl-N-(beta-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g
1-Hydroxyethylidene-1,1-diphosphonic acid 1 g
Ethylenediaminetetraacetic acid 2 g
Diaminostilbene type water-soluble brightening agent 2 g
Made up to 1 liter by adding pure water and adjusted to pH = 10.1.

(Bleach-fixing solution)

Water 800 ml
Feric (III) ammonium ethylenediaminetetraacetate 65 g
Disodium ethylenediaminetetraacetate 5 g
Ammonium thiosulfate 85 g
Sodium hydrogensulfite 10 g
Sodium metabisulfite 2 g
Sodium chloride 10 g
Made up to 1 liter by adding water and adjusted to pH 5.5 with diluted sulfuric acid.

Example 3

Taking the silver halide emulsions Em-1 and Em-2 prepared in Examples 1 and 2, which were adjusted to a temperature of 50°C, and thereafter Comparative Compound A or Compound S-I-11 was added, and after 3 minutes 1 x 10⁻⁵ mol of sodium thiosulfate and 7 x 10⁻⁶ mol of chloroauric acid, per mol of silver halide, were added to carry out chemical ripening. At the time when the chemical ripening was completed, a stabilizer (STB-1) was added in an amount of 1 x 10⁻³ mol per mol of silver halide. The speed was compared for each same emulsion, and indicated by assuming that of Samples 301 and 307 each as 100.

Table 3

Sample. No.	Additive	Amount mol/AgX	Emulsion	Fog	Speed	Sensitization
301	Comparative Compound A	2x10⁻⁵	Em-1	0.16	100	Gold/sulfur
302	Comparative Compound A	5x10⁻⁵	Em-1	0.14	97	Gold/sulfur
303	Comparative Compound A	1x10⁻⁴	Em-1	0.14	81	Gold/sulfur
304	S-I-11	2x10⁻⁵	Em-1	0.08	153	Gold/sulfur
305	S-I-11	5x10⁻⁵	Em-1	0.08	150	Gold/sulfur
306	S-I-11	1x10⁻⁴	Em-1	0.07	142	Gold/sulfur
307	Comparative Compound A	2x10⁻⁵	Em-2	0.21	100	Gold/sulfur
308	Comparative Compound A	5x10⁻⁵	Em-2	0.20	93	Gold/sulfur
309	Comparative Compound A	1x10⁻⁴	Em-2	0.19	76	Gold/sulfur
310	S-I-11	2x10⁻⁵	Em-2	0.08	201	Gold/sulfur
311	S-I-11	5x10⁻⁵	Em-2	0.08	210	Gold/sulfur
312	S-I-11	1x10⁻⁴	Em-2	0.06	206	Gold/sulfur
101	Comparative Compound A	5x10⁻⁵	Em-1	0.14	78	Sulfur
104	S-I-11	5x10⁻⁵	Em-1	0.08	117	Sulfur
201	Comparative Compound A	5x10⁻⁵	Em-2	0.18	82	Sulfur
204	S-I-11	5x10⁻⁵	Em-2	0.08	155	Sulfur
* Em-1 and Em-2 : development processing in Example 1 and Example 2, respectively.

In the case of Comparative Compound A, fog somewhat decreases with increase in the amount for its addition, but the effect thereof is insufficient. Moreover, decrease in speed occurs by increasing the amount. In contrast therewith, S-I-11 is seen to be able to achieve high speed with stability even of the amount changes by the factor of 5 times. Comparison of Samples 101, 104, 201 and 204 with Samples 301 to 312 can tell that sensitization is remarkably effected by gold sensitization and also the sensitizing effect is greatly brought about according the present invention. The effect of adding the additive of the present invention becomes more remarkable in the case of the combination with gold sensitization.

Example 4

The samples used in Example 3 were stored for 1 week at 60°C under 40 % RH, and differences in performance between them and samples stored in a freezer for that time were evaluated.

Fog was indicated by taking difference, and speed was indicated by a relative value assuming that of the freeze-stored ones as 100.

Table 4

Sample. No.	Additive	Amount mol/AgX	Emulsion	Fog	Speed	Sensitization
301	Comparative Compound A	2x10⁻⁵	Em-1	+0.04	105	Gold/sulfur
302	Comparative Compound A	5x10⁻⁵	Em-1	+0.03	105	Gold/sulfur
303	Comparative Compound A	1x10⁻⁴	Em-1	+0.03	104	Gold/sulfur
304	S-I-11	2x10⁻⁵	Em-1	+0.04	103	Gold/sulfur
305	S-I-11	5x10⁻⁵	Em-1	+0.03	103	Gold/sulfur
306	S-I-11	1x10⁻⁴	Em-1	+0.03	104	Gold/sulfur
307	Comparative Compound A	2x10⁻⁵	Em-2	+0.08	115	Gold/sulfur
308	Comparative Compound A	5x10⁻⁵	Em-2	+0.07	115	Gold/sulfur
309	Comparative Compound A	1x10⁻⁴	Em-2	+0.07	117	Gold/sulfur
310	S-I-11	2x10⁻⁵	Em-2	+0.04	103	Gold/sulfur
311	S-I-11	5x10⁻⁵	Em-2	+0.02	104	Gold/sulfur
312	S-I-11	1x10⁻⁴	Em-2	+0.02	103	Gold/sulfur
101	Comparative Compound A	5x10⁻⁵	Em-1	+0.03	103	Sulfur
104	S-I-11	5x10⁻⁵	Em-1	+0.03	103	Sulfur
201	Comparative Compound A	5x10⁻⁵	Em-2	+0.04	110	Sulfur
204	S-I-11	5x10⁻⁵	Em-2	+0.02	102	Sulfur
* Em-1 and Em-2 : development processing in Example 1 and Example 2, respectively.

It is understood that the silver halide photographic light-sensitive material according to the present invention can bring about great effect of suppressing the increase in fog and increase in speed caused by the storage at high temperatures. The increase in fog and speed during the storage has been a great disadvantage in the silver halide emulsions containing silver chloride in a high content. However, the present invention brings about the effect that can not have too highly compensated this disadvantage, and thus can be said to be a technique which is very important in putting into practice the emulsions containing silver chloride in a high content.
The light-sensitive material employing the silver halide emulsion having been gold/sulfur sensitized and having a high silver chloride content has excellent rapid processing performance, and is a preferred form of the present invention

Example 5

A silver chlorobromide emulsion, Em-3. (silver bromide content: 0.5 mol %) of 0.4 µm in grain size was prepared in the same manner as in Example 2. Using Em-3, a green-sensitive emulsion and a red-sensitive emulsion were prepared, and using Em-2, a blue-sensitive emulsion was prepared. On a paper support whose both surfaces were coated with polyethylene, the following seven layers were multi-layer coated in succession to prepare silver halide photographic light-sensitive material. Here, the amount of each compound was indicated by a value per 1 m² of the silver halide photograph!c light-sensitive material.

(Layer 1):

A silver halide emulsion laver containing 0.3 g of dinonyl phthalate dispersion in which 0.8 g of a yellow coupler and 0.02 g of color-contamination preventive agent were dissolved, a blue-sensitive silver chlorobromide emulsion (0.3 g in terms of silver) and 2 g of gelatin.

(Layer 2):

An intermediate laver containing 0.04 g of diisodecyl phthalate dispersion in which 0.07 g of color-contamination preventive agent were dissolved, and 1 g of gelatin.

(Layer 3):

A silver halide emulsion laver containing 0.25 g of tricresyl phosphate dispersion in which 0.4 g of a magenta coupler and 0.01 g of color-contamination preventive agent were dissolved, a green-sensitive silver chlorobromide emulsion (0.4 g in terms of silver) and 1.5 g of gelatin.

(Layer 4):

An intermediate layer containing 0.2 g of dinonyl phthalate dispersion in which 0.7 g of an ultraviolet absorbent and 0.03 g of color-contamination preventive agent were dissolved, and 1.5 g of gelatin.

(Layer 5):

A silver halide emulsion layer containing 0.2 g of di(2-ethylhexyl)phthalate dispersion in which 0.35 g of a cyan coupler and 0.01 g of color-contamination preventive agent were dissolved, a red-sensitive silver halide emulsion (0.25 g in terms of silver) and 1.2 g of gelatin.

(Layer 6):

An intermediate layer containing 0.2 g of dinonyl phthalate dispersion in which 0.3 g of an ultraviolet absorbent and 0.02 g of a color-contamination preventive agent were dissolved and 1.0 g of gelatin.

(Layer 7):

A protective layer containing 1 g of gelatin.

The additive and its amount in each emulsion at the time of chemical ripening were as follows:

Table 5

No.	Stabilizer	Red-sensitive layer	Green-sensitive layer	Blue-sensitive layer
501	Comparative Compound A	5 x 10⁻⁵	5 x 10⁻⁵	5 x 10⁻⁵	mol/molAgX
502	S-I-4	5 x 10⁻⁵	5 x 10⁻⁵	5 x 10⁻⁵	mol/molAgX

The speed was measured to reveal that Sample 502 had a speed of about 1.7 times in every layer on the basis of Sample 501. Each sample was divided, one of which was stored for 1 week at 60°C under 40 % RH and the other of which was stored in a freezer, and evaluation was made at the same time. In the case of freezer storage, good color prints were obtained in any cases. Sample 502, in the sample stored at 60°C under 40 % RH, showed slightly poor clearity at white areas, but was able to be printed under the conditions substantially unchabged. In Sample 501, however, the color turned thick as a whole, and the printing had to be carried out again by changing the exposure time. Even after the conditions were changed, there was also shown poor clearity at white areas, which further turned yellowish.

Claims

1. A silver halide photographic light-sensitive material comprising a support having thereon at least one silver halide emulsion layer containing a silver halide emulsion chemically sensitized in the presence of a compound represented by the following Formula (I);
Formula (I)
(X)n - Q - (S - Y)m
wherein X represents a hydrophilic group, Q represents an organic m+n valent group, Y represents a hydrogen atom, an amidino group or an atom or a group of atoms capable of forming a monovalent cation, and m and n each represent an integer of 1 or 2.

2. The material of claim 1, wherein said X in Formula (I) represents an -OPO(OH)₂ group or a salt thereof, an -SO₃H group or a salt thereof, a -COOH group or a salt thereof, a -OH group or an -NHR group, in which R represents a hydrogen atom or an alkyl group having one to four carbon atoms.

3. The material of claim 1, wherein said compound represented by Formula (I) is a compound represented by the following Formula (S);
Formula (S)
(Y-S)-L₁-(J₁)k-(L₂)ℓ-(Z)m-(L₃)n-(J₂L₄)p-X′
wherein L₁ to L₄ each represent a polyvalent hydrocarbon group; J₁ and J₂ each represent an -O-, a COO- group, an -OCO- group, a -CONR′- group, an -NR′CO- group, an -SO₂NR¹- group, an -NR¹SO₂- group, an -NR¹-CO-NR²- group, an -SO₂- group, an -N=N- group, an -NR¹- group or a -CO- group, in which R¹ and R² each represent a hydrogen atom, an alkyl group or an aryl group; Y represents a hydrogen atom, an amidino group or an atom or a group of atoms capable of forming a cation; Z represents a heterocyclic group; X′ represents a sulfonic acid group or salt thereof, a carboxyl group or salt thereof, or a phosphoric acid group or salt thereof; k, ℓ, m, and n each represent an integer of from 0 to 2 which represent the repeating number, provided that when X′ represents a carboxyl group represents an integer of 1 or 2; and p represents an integer of from 0 to 4.

4. The material of claim 3, wherein said compound represented by Formula (S) is a compound represented by the following Formula (S′);
Formula (S′)
MS - R³ - X˝
wherein R³ represents a divalent hydrocarbon group; X˝ represents a carboxy group or a salt thereof, or a sulfonic acid group or a salt thereof; and M represents a hydrogen atom; or an atom or a group of atoms capable of forming a monovalent cation.

5 The material of claim 4, wherein said X˝ represents a sulfonic acid group or a salt thereof.

6. The material of claim 1, wherein said compound represented by Formula (I) is a compound represented by the following Formula (Ib);

wherein Z represents a group of atoms necessary for completing a five- or six-member heterocyclic ring; M and X each are the same as M and X defined in Formula (I), respectively; L represents a simple bond or a divalent bonding group; and n′ represent an integer of 1 or 2.

7. The material of claim 6, wherein said X is a sulfonic acid group or a salt thereof.

8. The material of claim 6, wherein said compound represented by Formula (Ib) is a compound represented by the following Formula (Ib′);

wherein Y′ represents an oxygen atom, a sulfur atom, a selenium atom or an -NR′ group, in which R′ represents an alkyl group; and M and X˝ each are the same as M and X˝ defined in Formula (Ib).

9. The material of claim 8, wherein said X′ in Formula Ib′ is a sulfonic acid group or a salt thereof.

10. The material of any of claims 1 to 9, wherein said silver halide emulsion is chemically sensitized in the presence of said compound represented by Formula (I) in an amount of from 5x 10⁻⁶ mol to 5x 10⁻⁴ mole per mol of silver halide.

11. The material of any of claims 1 to 10, wherein said silver halide emulsion comprises silver clorobromide containing not less than 80 mol% of silver chloride.

12. The material of any of claims 1 to 10 wherein said silver halide emulsion comprises silver halide containing silver iodide in an amount of not more than 1 mol%.

13. The material of claim 12, wherein said silver halide emulsion comprises silver halide containing silver iodide in an amount of not less than 0.5 mol%.

14. The material of any of claims 1 to 13, wherein said silver halide emulsion is chemically sensitized in the presence of a gold compound.