JPH04321024A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide color photographic sensitive material having a high sensitivity, low fogging and excellent reciprocity law failure characteristic. CONSTITUTION:The silver halide particles of the silver halide photographic sensitive material which has at least one layer of silver halide emulsion layers on a base and is constituted by incorporating the silver halide particles contg. a complex having at least one SnX3 (where X denote Cl, Br, F, OH) ligands are produced by forming the above-mentioned silver halide particles in the presence of the complex having at least one SnX3 (where X denote Cl, Br, F, OH) ligands.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material which has high sensitivity and improved reciprocity failure.

0002

BACKGROUND OF THE INVENTION In recent years, rapid processability has been desired for photosensitive materials for color photographic paper in order to finish large quantities of prints in a short delivery time.

As one method, it is known to speed up color development by using a silver chloride emulsion or a silver chlorobromide emulsion with a high silver chloride content as a silver halide emulsion. For example, U.S. Pat.
No. 756, No. 4,225,666, JP-A-55-26
No. 589, No. 58-91444, No. 58-95339
No. 58-94340, No. 58-95736, No. 58-106538, No. 58-107531, No. 5
No. 8-107532, No. 58-107533, No. 58
There are descriptions regarding the above technology in No. 108533, No. 58-125612, and the like.

However, silver chloride emulsions or silver chlorobromide emulsions with a high silver chloride content have high fog, low sensitivity, and reciprocity failure characteristics, that is, large changes in sensitivity and gradation depending on the exposure illuminance. It has its drawbacks.

Various attempts have been made to solve the above drawbacks. For example, JP-A-51-139323 and JP-A-59-171947 describe that processing stability and reciprocity law failure characteristics are improved by incorporating a group VIII metal compound of the periodic table.

However, the disclosed techniques are not sufficient to solve the problems with silver chloride or silver halide with high silver chloride content. Furthermore, in JP-A-1-183647, high sensitivity is achieved by incorporating iron ions into silver halide with a high silver bromide content and a silver bromide-containing phase with a high silver bromide content, and reciprocity failure characteristics are improved. It is described that improvements can be made in sensitivity and gradation changes due to temperature changes during exposure.

However, although the above-mentioned problems have been almost solved, there is a problem in that sensitivity changes (latent image stability) are large depending on the time interval between exposure and processing. Japanese Patent Publication No. 55-135
No. 832 states that a high-sensitivity emulsion can be obtained by doping with cadmium, lead, copper, and zinc, but the inventors' research has shown that no emulsion can simultaneously satisfy high sensitivity and improved reciprocity. There wasn't. JP-A-2-20852 describes a silver halide emulsion containing a transition metal complex having a nitrosyl or thionitrosyl ligand, but does not specifically mention high sensitivity. Also, in JP-A-2-20853 and JP-A-2-20855,
There are descriptions of complexes having cyano ligands that increase sensitivity, but cyano ligands are highly toxic and pose major environmental problems when used. It was also found that the requirements for high sensitivity and reciprocity failure improvement were not satisfied at the same time.

[0008]

OBJECTS OF THE INVENTION An object of the present invention is to provide a silver halide photographic material that has high sensitivity, low fog, and excellent reciprocity failure characteristics.

[0009]

[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer is SnX.
3 (wherein, X represents Cl, Br, F, OH) A silver halide photographic light-sensitive material and silver halide characterized by containing silver halide grains containing a complex having at least one ligand In the method for producing particles, SnX
3 (where X represents Cl, Br, F, OH) Achieved by a method for producing silver halide grains, characterized in that the silver halide grains are produced in the presence of a complex having at least one ligand. be done.

The details of the present invention will be explained below.

[0011] Forming silver halide grains in the presence of the complex of the present invention means that the complex may be present in the production vessel before grain formation, or may be present continuously or temporarily during the production process. Show good.

In the silver halide photographic light-sensitive material of the present invention, preferred grains for the effect of the present invention are grains containing substantially no iodine, and the silver chloride content of the preferred grains of the present invention is 95 mol%. Above, particularly preferably 98 to 99.5
It is mole%.

In the present invention, the silver bromide content is 0.1
~2 mol% silver chlorobromide is preferably used. Further, grains having only a uniform composition may be used, or other silver halide grains having different compositions may be used.

In addition, in a silver halide emulsion layer containing silver halide grains having a silver chlorobromide content of 90 mol % or more, the silver chloride proportion to the total silver halide grains contained in the emulsion layer is The proportion of silver halide grains having a content of 90 mol% or more is preferably 60 mol% or more, more preferably 80 mol% or more.

Among the grains in the emulsion layer, the grains of the present invention account for 50
It is preferably mol% or more, more preferably 80 mol% or more.

More preferred metals for the complex contained in the silver halide grains of the present invention are osmium, ruthenium, iron, and platinum.

[0017] In the complex compound doped into the silver halide grains of the present invention, the salt thereof dissociates in an aqueous solution, and therefore does not play any important role in achieving the object of the present invention. Examples of the complex compound (I) of the present invention to be doped into the silver halide grains of the present invention are shown below, but the invention is not limited thereto.

Compound (I) (1) [RuCl2(CO)2(SnCl3)2]2-
(2) [RuCl2(SnCl3)2]2-(3)
[RuBr2(CO)2(SnBr3)2]2- (
4) [RuBr2(SnBr3)2]2-(5)[Ru
Cl(SnCl3)5]4-(6)[
RuBr(SnBr3)5]4-(7)[Ru(SnC
l3)6]4-(8)[Ru(S
nBr3)6]4-(9)[RuCl(Sn(OH)3
)5]4-(10)[RuBr(Sn(O
H)3)5]4-(11)[Ru(SnCl3)5(M
eCN)]3- (12)[Ru(SnF3)6]
4-(13) [OSCl(SnCl3)5]4-
(14) [OS(SnCl3)6]4-(15
) [OSBr(SnBr3)5]4- (
16) [OS(SnF3)6]4-(17)[IrCl
(SnCl3)5]4- (18)[Ir
(SnCl3)6]4-(19)[IrBr(SnBr
3)5]4- (20)[Ir(SnF3
)6]4-(21)[RhCl(SnCl3)5]4-
(22) [Rh(SnCl3)6]4-
(23) [RhBr(SnBr3)5]4-
(24) [Rh(SnF3)6]4-(25)[P
t(SnCl3)5]3- (26)
[Fe(SnCl3)5Cl]4- The amount of these complex compounds used is 1 x 10 per mole of silver.
-9 to 1 x 10-2 mol, preferably 1 x 10-7 to 1
x10-3 mol is more preferable since the effect of the present invention is large.

The particles of the present invention are preferably subjected to the commonly known gold sensitization.

The silver halide emulsion used in the present invention is not particularly limited and can be prepared by various known techniques.

The silver halide photographic light-sensitive material according to the present invention contains a sensitizing dye, a water-soluble dye, a color fog preventive agent, an image stabilizer, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, and a formalin scavenger. , mordant, development accelerator, development retardant, optical brightener, matting agent, lubricant, antistatic agent,
Surfactants and the like can be optionally used.

The photographic constituent layer of the silver halide photographic light-sensitive material according to the present invention is made of baryta paper or paper laminated with an α-olefin polymer, a paper support from which the α-olefin layer can be easily separated from the paper support, or synthetic paper. Reflective supports containing or coated with white pigments on films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. It can be applied to rigid bodies such as metals, ceramics, etc. Alternatively, a thin reflective support of 120 to 160 μm can also be used.

In the present invention, the development of the silver halide photographic light-sensitive material includes known methods widely used in various color photographic processes.

[0024]

[Examples] Examples of the present invention are shown below, but the present invention is not limited thereto.

Example 1 The following (solution A) and (solution B) were added in 1000 ml of a 2% gelatin aqueous solution kept at 40°C with pAg=6.5 and pH=3.
．． 0 over 30 minutes, and then added the following (
Solution C) and Solution D were simultaneously added over 120 minutes while controlling pAg=7.3 and pH=5.5.

[0026] At this time, the control of pAg is as described in JP-A-59-4
The method described in No. 5437 was used to control the pH using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) Sodium chloride
3.42g potassium bromide
Add 0.03g water
200ml (solution B) silver nitrate
Add 10g water
200ml (Liquid C) Sodium chloride 1
02.7g potassium bromide
Add 1.0g water
600ml (Liquid D) Silver nitrate
Add 300g water
After adding 600 ml, desalination was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.45 μm and a coefficient of variation (particle size). standard deviation/average particle size) = 0.07, silver chloride content 99
．． A 5 mol % monodisperse cubic emulsion EMP-1 was obtained.

EMP-1 was optimally sensitized at 65°C using the following compound, and green-sensitive silver halide emulsion E was obtained.
m-1 was obtained.

Sodium thiosulfate 1.5 mg/mol AgX stabilizer SB-5 6
×10-4 mol/AgX sensitizing dye GS-6
3 x 10-4 mol/AgX Next, Em-1 is a solution (solution C) containing (I-7) at 1.1 x
An emulsion was prepared which differed only in the addition of 10@-5 mol, and was designated as Em-2.

Furthermore, emulsions containing the same moles of (I-13) and (I-25) in place of the compound (I-7) added to Em-2 were designated as Em-3 and Em-4.

[0031] Also, as a comparative sample, (I-7) of Em-2
Instead, emulsions containing the same moles of (IR-1) and (IR-2) were designated as Em-5 and Em-6.

IR-1 K2 [NiCl4]IR-2
K3 [CrCl6] Each layer shown below is coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side (the side on which the photographic constituent layer is coated),
Sample 101 was created.

[0033]

[Table 1]

As a hardening agent, H-1 was added to the second layer.

[0035]

[Chemical formula 1]

[0036]

[Case 2]

[0037] Instead of Em-1 of sample 101, Em-2
~ Samples 102 to 1 were prepared in the same manner except that Em-6 was used.
06 was produced.

The performance of the sample thus obtained was evaluated by the following method, and the results are shown in Table 1.

(1) Sensitometry After wedge exposure with green light for 0.05 seconds and color development according to the following processing steps, an optical densitometer (PDA-6 manufactured by Konica) was used.
The density was measured using a camera (Model 5), and the sensitivity was expressed as the logarithm of the reciprocal of the exposure amount required to obtain a density 0.8 higher than the fog density.

(2) Reciprocity law failure characteristic In green light,
Wedge exposure was performed for 10 seconds to obtain the same exposure amount as in the above sensitometry, and sensitometry was performed in the same manner as above. Sensitivity when exposed for 0.05 seconds to 100
It is expressed as the relative sensitivity of the sample exposed for 10 seconds.

(3) Fog Density The unexposed sample was subjected to color development treatment, and an optical densitometer (manufactured by Konica;
The concentration was measured using PDA-65 type).

The processing conditions used for evaluation are as follows.

Processing process Temperature Time Color development 35.0 ±0.3°C
45 seconds bleach fixing 35.0 ±0.5
℃ 45 seconds stabilization 30
Dry at ~34℃ for 90 seconds
60 to 80℃ 60 seconds Color developer Pure water

800 ml triethanolamine

10g N,N-diethylhydroxylamine
5g potassium bromide

0.02g potassium chloride
2g potassium sulfite
0.3
g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid
1.0g
Catechol-3,5-diphosphonate disodium
1.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate
4.5g optical brightener (
4,4'-diaminostilbenzsulfonic acid derivative)
1.0g potassium carbonate

Add 27g water to make a total volume of 1l, p
Adjust to H=10.10.

Bleach-fix solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid
3g ammonium thiosulfate (
70% aqueous solution)
100ml ammonium sulfite (40% aqueous solution)
Add 27.5 ml of water to bring the total volume to 1 liter, and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid. Stabilizing liquid 5-chloro-2-methyl-4-isothiazoline-3
-one 1.0g ethylene glycol
1.0g
1-hydroxyethylidene 1,1-diphosphonic acid
2.0g ethylenediaminetetraacetic acid
1.0g ammonium hydroxide (20% aqueous solution)
3.0g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.5g Add water to make a total volume of 1 liter, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

[0045]

[Table 2]

As can be seen from Table 1, the samples of the present invention were
High sensitivity and improved reciprocity law failure characteristics.

Example 2 Em-1 and Em-2 except that sodium thiosulfate, sodium chloroaurate and SB-5 were used during chemical sensitization.
Emulsions prepared in the same manner were designated as Em-7 and Em-8, respectively.

Samples coated with Em-7 and Em-8 in the same manner as Em-1 were designated Samples 107 and 108, respectively. These samples were evaluated in the same manner as in Example 1.

The results are shown in Table 2.

[0050]

[Table 3]

From the comparison of samples 107 and 108 and samples 102 and 101, the sensitization effect of the present invention is particularly excellent in the case of sodium chloraurate sensitization.

Furthermore, samples 101 and 102 and 107 and 1
From the comparison of No. 08, it can be seen that sodium chloraurate sensitization is particularly effective in improving the reciprocity failure according to the present invention. That is, it was found that the sensitization and reciprocity law failure improving effects of compound [I] are especially excellent in emulsions that have been sensitized with sodium chloraurate.

Example 3 In the preparation of EMP-1 in Example 1, (Liquid A) and (B
By changing the addition time of liquid) and the addition time of (liquid C) and (liquid D), the average particle size was 0.71 μm (length of one side of the cube),
A monodisperse cubic emulsion with a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol% was prepared. For this emulsion, sodium thiosulfate; 0.8 mg/mol AgX, SB-5;
6×10 −4 mol/mol AgX and sensitizing dye BS-3;
Optimally sensitized at 65°C using 4 x 10-4 mol/mol AgX. The obtained emulsion is designated as Em-9.

In the preparation of Em-9, (
An emulsion was prepared that differed only in that I-7) was added at 1×10 −5 mol/mol AgX, and this was named Em-10.

Emulsions were prepared that differed only in the addition of 1.5 mg/mol AgX of sodium chloraurate in the sensitization of Em-9 and Em-10, and these were used as emulsions for Em-11 and Em-10, respectively.
It was named Em-12.

Regarding the preparation of EMP-1 in Example 1 (A
By changing the addition times of liquids) and (liquids B) and the addition times of liquids C and (d), the average particle size was 0.52 μm (1 cube).
(as side length) coefficient of variation = 0.07, silver chloride content 99.
A 5 mol % monodispersed cubic emulsion was prepared. Sodium thiosulfate; 2.0 mg/mol AgX,S for this emulsion;
Using B-5; 7 x 10-4 mol/mol AgX and sensitizing dye RS-7; 7 x 10-5 mol/mol AgX,
Optimal sensitization was achieved at 67°C. The obtained emulsion is designated as Em-13.

In the preparation of Em-13, (liquid C) was added (
An emulsion was prepared that differed from I-7) in that 1.4×10 −5 mol/mol AgX was added, and this was designated as Em-14.

In the sensitization of Em-13 and Em-14, emulsions were prepared that differed only in the addition of 0.3 mg/mol AgX of sodium chloroaurate;
5, Em-16.

[0059] Next, each layer having the structure shown below was laminated onto a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the other side (the side on which the photographic constituent layer was coated). A multilayer silver halide color photographic light-sensitive material sample 201 was prepared. The coating solution was prepared as follows.

First layer coating liquid Yellow coupler YY-1; 26.7 g, dye image stabilizer ST-1; 10.0 g, ST-2; 6.67 g, additive HQ-1; 0.67 g and high boiling point organic solvent DNP;
6.67 g was dissolved in 60 ml of ethyl acetate, and this solution was mixed with 100 g containing 7 ml of 20% surfactant SU-1.
% gelatin aqueous solution using an ultrasonic homogenizer to prepare a yellow coupler dispersion. Furthermore, an antifungal agent (B-1) was added to the dispersion. A blue-sensitive silver halide emulsion (
(containing 10 g of silver) to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution.

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

[Table 6]

Note that water-soluble dyes AI-1, AI-2, and AI-3 were added to the coating solutions for the first, third, and sixth layers, respectively. The structure of the additive used is as follows.

[0066]

[Chemical formula 3]

[0067]

[C4]

[0068]

[C5]

[0069]

[C6]

[0070]

[C7]

As hardeners, H-2 was added to the second and fourth layers, and H-1 was added to the seventh layer.

H-2C(CH2SO2CH=CH2)4
Samples 202 to 204 were prepared in the same manner as the 0.07 g/m2 sample 201 except that the emulsion used in the photosensitive silver halide layer was changed as shown in Table 3.

[0073]

[Table 7]

Using the sample thus obtained, exposure and processing were carried out in the same manner as in Example 1, except that the filters used during exposure were changed to blue, green, and red, and evaluation was conducted in the same manner as in Example 1. was carried out. Note that the sensitivity is compared to sample 2.
It is expressed as a relative sensitivity when the sensitivity of 01 is taken as 100. The fog density was measured using an optical densitometer (Konica PDA-65), and the fog value of each color-sensitive layer of sample 201 was set to 0.0.
Relative evaluation was given as 0. The results obtained are shown in Table 4.

[0075]

[Table 8]

From Table 4, the great effects of the present invention can be seen in multilayer silver halide color light-sensitive materials. In particular, sample 204 chemically sensitized with sodium chloroaurate had a remarkable effect of improving reciprocity law failure compared to comparative sample 203, which was sensitized in the same way, and a highly sensitive emulsion was obtained.

In other words, it was found that the present invention was highly effective in improving reciprocity law failure characteristics in samples chemically sensitized with sodium chloroaurate, and a highly sensitive sample could be obtained.

[0078]

According to the present invention, it was possible to provide a silver halide color photographic light-sensitive material which has high sensitivity, low fog, and excellent reciprocity law failure characteristics.

Claims (2)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, comprising:
The silver halide emulsion layer is SnX3 (where X is Cl,
1. A silver halide photographic light-sensitive material comprising silver halide grains containing a complex having at least one ligand (representing Br, F, OH). [Claim 2] In a method for producing silver halide grains, S
A method for producing silver halide grains, comprising producing the silver halide grains in the presence of a complex having at least one nX3 (where X represents Cl, Br, F, or OH) ligand.