JPH1180134A - Silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photosensitive material for a color photograph, having improved inter-image effect and improved sharpness by including a specific triazole derivative. SOLUTION: This silver halide photosensitive material for a color photograph contains at least one kind of a compound of formula I (M is H, an alkali metal or ammonia; L is an alkylene; Z is OH, an alkoxy, cyano, an acyl, a carbamoyl, a ureido, carboxy or a heterocycle). Especially, compounds of formulas II (X is OH, formula III, formula IV or the like) and V (Y is OH, OCH3 , formula IV or the like) are preferable in the compounds of the formula I. The photosensitive material has at least one layer of a silver halide emulsion layer on a supporter, and the compound of the formula I is preferably included in the layer and/or a non-photosensitive layer.

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. In particular, the present invention relates to a silver halide color photographic material having an improved interimage effect and improved sharpness.

[0002]

2. Description of the Related Art Oxidized aromatic primary amine color developing agents react with couplers by color development of silver halide color photographic materials to develop indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and the like. It is known that a similar dye is formed and a color image is formed. In this method, a color reduction method is usually used for color reproduction, and a silver halide emulsion selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image forming agents that are complementary to each other. And are used. To form a yellow image, for example, an acylacetanilide or bezonzoylmethane coupler is used, and to form a magenta image, mainly pyrazolone, pyrazolotriazole, pyrazorobenzimidazole, pyrazolopyrazole, cyano Acetophenone or indazolone couplers are used, and phenol or naphthols are mainly used to form a cyan image. By the way, the dyes produced from these couplers are not ideal spectral absorption spectra.Magenta and cyan dyes in particular have broad absorption spectra and have side absorption in the short wavelength region, and color It is not preferable for the color reproduction of the photographic material. In particular, side absorption in a short wavelength region tends to cause a decrease in saturation. As a means for improving this, it can be improved to some extent by expressing the inter-image effect.

The inter-image effect is described in, for example, Hanson et al., Journal of
The Optical Society of America (Ja
urnal of the Optical Society of America) ”, No. 42
Volume, pp. 663-669, and A. Tiles (AT
heils), “Zeitschrift fur Wissens
chaftliche Photographie, Photophysique und Photo-
Chemie), Vol. 47, pp. 106-118 and 246-255. US Patent 3,536,4
Nos. 86 and 3,536,487 and JP-B-48-3
No. 4169, JP-A-3-163443 and the like describe that an interimage effect can be obtained by using a specific heterocyclic thiol compound. Further, obtaining an interimage effect by providing a colloidal silver-containing layer between a cyan layer and a magenta layer of a color reversal photographic element is disclosed in Research Disclosure (Rese.
arch Disclosure), No131, 1st
It is described in 3116 (1975). Further, U.S. Pat. No. 4,082,533 discloses a color reversal photosensitive material having a layer structure capable of moving iodine ions during development, which contains silver iodide particles capable of forming a latent image on one of the layers. A silver halide grain capable of forming a latent image on another layer,
A method for obtaining an interimage effect by incorporating silver halide grains whose surface is covered so as to be developable independently of image exposure is described.

[0004] However, in the above-mentioned method, in many cases, a sufficient interimage effect cannot be obtained, and the use of a colloidal silver-containing layer and the introduction of covered silver halide grains are often carried out in color reversal photosensitive materials. This may lead to a reduction in color density. In addition to the above, for example, in a color development step, a coupler capable of releasing a development inhibitory substance such as a benzotriazole derivative or a mercapto compound during a coupling reaction with an oxidized form of a color developing agent (D
It is also known to use an IR coupler) or a hydroquinone compound capable of releasing a development-inhibiting substance such as a mercapto compound during development to produce an interimage effect. The use of the compounds (1) and (2) causes desensitization or lowers the color density, so that their use is limited, and alternative means have been required.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material which gives excellent sharpness without impairing other photographic properties.

[0006]

The above object has been attained by the following (1) to (3). (1) A silver halide photographic light-sensitive material comprising at least one compound represented by the following general formula (I).

[0007]

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In the formula, M represents a hydrogen atom, an alkali metal, or an ammonia group, L represents an alkylene group, Z represents a hydroxy group, an alkoxy group, a cyano group, an acyl group, an alkyl-substituted carbamoyl group, or an unsubstituted carbamoyl group. , A ureido group, a carboxy group, or a heterocyclic group. (2) In a silver halide color photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer and / or the non-light-sensitive layer is represented by the following general formula (I). (1) The silver halide photographic material as described in (1), which contains at least one compound. (3) Compounds represented by the following general formulas (IX) and (IY).

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The silver halide photographic material of the present invention is preferably a color photographic material, more preferably a color reversal photographic material.

[0011]

Next, the compound represented by formula (I) will be described in detail.

In the general formula (I), M represents a hydrogen atom, an alkali metal, or an ammonium group. As the alkali metal, lithium, sodium, and potassium are used. As the ammonium group, an ammonium group, a tetramethylammonio group,
Examples include an ethyltrimethylammonio group, a benzyltrimethylammonio group, and a tetrabutylammonio group. L represents an alkylene group (methylene, ethylene, propylene, etc.) and may be further substituted with an alkyl group (methyl group, ethyl group, propyl group) or an aryl group (phenyl group, naphthyl group). Z is a hydroxy group, an alkoxy group (eg, methoxy group, ethoxy group, butyloxy group, etc.), a cyano group, an acyl group (eg, acetyl group, benzoyl group, formyl group, pivaloyl group, etc.),
Alkyl-substituted carbamoyl group (for example, N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-
Ethylcarbamoyl group), unsubstituted carbamoyl group, ureido group (eg, unsubstituted ureido group, N-methylureido group, N-phenylureido group, etc.), carboxy group, heterocyclic group (eg, pyridyl group, furyl group, Imidazolyl group, piperidyl group, pyrrolidyl group, thienyl group, morpholino group, etc.).

In the general formula (I), preferably, M is a hydrogen atom or an alkali metal, L is an alkylene group having 1 to 10 carbon atoms (more preferably, a methylene group, an ethylene group or a propylene group); Is a hydroxy group, an alkoxy group, an alkyl-substituted carbamoyl group, an unsubstituted carbamoyl group, a ureido group, a carboxy group, or a heterocyclic group.

Hereinafter, specific examples of the compound represented by formula (I) of the present invention are shown, but the compound of the present invention is not limited thereto.

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Compounds represented by the general formula (I) can be obtained from known literature such as, for example, Temple, et al., "The Chemistry of Heterocyclic.
Campounds (THE CHEMISTRY OF H
Vol. 37, pp. 404-474, Katorisky (Kat)
ritzky) et al., “Comprehensive heterocyclic chemistry (COMPREHENSIVE)
HETEROCYCLIC CHEMISTR
Y) ", Volume 5, pages 761 to 784, C. Aint
hworth et al., "Journal of American
Chemical Society (Journalof Am
erican Chemical Society ",
The compound can be synthesized according to the method described in Vol. 77, pp. 1538-1540, and the like. Specific synthesis examples of typical compounds are shown below, but the synthesis method of the compound of the present invention is not limited thereto.

Synthesis Example 1 (Exemplified Compound I-1) Thiosemicarbazide (1.82 g, 0.02 mol) was added to 40 ml of pyridine, and the mixture was stirred while being cooled to 0 ° C. or lower, and methoxyacetic chloride (2.17 g, 0.1 g) was added. 02mo
l) was added dropwise. After stirring at 0 ° C. for 30 minutes, the mixture was stirred at room temperature for 1 hour to obtain a yellow solution. Under reduced pressure, pyridine was distilled off, 20 ml of methanol was added thereto, and sodium methylate (28% methanol solution, 7.71 g, 0.04%) was added.
mol) was added dropwise. After stirring for 1 hour under heating reflux,
After cooling to room temperature, 220 ml of 0.1 N hydrochloric acid was added, and the mixture was extracted twice with ethyl acetate (250 ml). The organic layer was dried over sodium sulfate, concentrated under reduced pressure, and the precipitated solid was filtered under reduced pressure to obtain I-1 (2.1 g, yield 72%). Synthesis Example 2 (Exemplified Compound I-2) Ethyl 3-methoxy-propionate (3.17 g, 0.1.
024 mol), thiosemicarbazide (1.82 g,
0.02 mol) was added to 10 ml of isopropyl alcohol, and the mixture was stirred while being cooled to 5 ° C. or lower, and sodium methylate (28% methanol solution, 4.24 g, 0.02 mol) was added.
2 mol) was added dropwise. After stirring at room temperature for 3 hours, the mixture was stirred under heating and reflux for 1 hour, cooled to room temperature, and concentrated hydrochloric acid (2 ml).
Was added, and the precipitated solid was filtered under reduced pressure to obtain 3.1 g of crude crystals. The obtained crude crystals were recrystallized from methanol to give I-
2 (2.74 g, 86% yield) was obtained.

Table 1 shows the physical properties of the compounds synthesized by the same synthesis method as in Synthesis Example 2.

[0025]

[Table 1]

Synthesis Example 3 (Exemplified Compound I-44) 5-Carboxymethyl-2-mercapto-thiazole (3.54 g, 20 mmol) was added to 20 m of acetonitrile.
, N, N'-diisopropylcarbodiimide (2.52 g, 20 mmol) while cooling to 5 ° C or lower.
Was added dropwise and stirred at room temperature for 2 hours. While cooling to 5 ° C. or lower, morpholine (1.92 g, 22 mol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and 1N was added to the residue.
An aqueous NaOH solution (25 ml) was added, the mixture was stirred well, and the insoluble matter was filtered by filtration under reduced pressure. Further, 200 ml of a saturated NaCl aqueous solution and 200 ml of ethyl acetate were added for extraction, and the organic layer was concentrated under reduced pressure.
The residue was purified by silica gel column chromatography (eluent: dichloromethane / methanol = 10/1) to give the desired I-44.
(2.58 g, 53%). Melting point 151-3 [deg.] C. The structure was confirmed from various spectra and elemental analysis values.

The color photographic light-sensitive material preferably used in the present invention comprises, on a support, a red-sensitive silver halide emulsion layer,
It has a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a non-light-sensitive intermediate layer. At least one non-photosensitive intermediate layer exists between the color-sensitive layers, but it is preferable that two non-photosensitive layers exist. Further, each color-sensitive layer is preferably composed of three or more layers having different sensitivities. Preferred specific examples of the layer constitution of the light-sensitive material of the present invention are shown below, but the present invention is not limited thereto. That is, from the support side: first layer: antihalation layer second layer: intermediate layer third layer: intermediate layer (containing colloidal silver or fogged fine silver halide) fourth layer: low-sensitivity red-sensitive emulsion layer fifth layer : Medium sensitivity red photosensitive emulsion layer 6th layer: High sensitivity red photosensitive emulsion layer 7th layer: Intermediate layer 8th layer: Intermediate layer (containing colloidal silver or fogged fine grain silver halide) 9th layer: Low sensitivity green Photosensitive emulsion layer 10th layer: Medium-speed green photosensitive emulsion layer 11th layer: High-speed green photosensitive emulsion layer 12th layer: Intermediate layer 13th layer: Yellow filter layer 14th layer: Low-sensitivity blue-sensitive emulsion layer 15th layer: medium-sensitivity blue-sensitive emulsion layer 16th layer: high-speed blue-sensitive emulsion layer 17th layer: first protective layer 18th layer: second protective layer 19th layer: third protective layer Same color sensitivity Of the silver coating amount of each sub-layer when three or more sub-layers with different In the case where the total silver content of the color-sensitive layer is 100%, it is desirable that the high-sensitivity layer is 15 to 40%, the medium-sensitivity layer is 20 to 50%, and the low-sensitivity layer is 20 to 50%. . It is desirable that the coated silver amount of the high-sensitivity layer is smaller than that of the middle and low-sensitive layers.

Regarding the silver halide photographic emulsion of the present invention and various techniques and inorganic and organic materials which can be used for silver halide photographic light-sensitive materials using the same, generally, Research Disclosure No. 308119 (19)
89) can be used.

In addition to this, more specifically, for example,
The techniques and inorganic / organic materials which can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following portions of European Patent 436,938A2 and the patents cited below. I have.

Item The relevant point 1) Layer structure Page 146, line 34 to page 147, line 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler Page 137, line 35 to page 146, line 33, page 149, lines 21 to 23 4) Magenta coupler, page 149, lines 24 to 28; EP 421,453A1 Page 3, line 5 to page 25, line 55 5) Cyan coupler, page 149, lines 29 to 33; EP 432, 804A2, page 3, line 28 to page 40, line 6) Polymer coupler, page 149, lines 34 to 38; EP 113,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler, page 53, line 42 to page 137, line 34 Eye, page 149, lines 39-45 8) Other functionalities, page 7, line 1 to page 53, line 41, page 149, line 46 to puller, page 150, line 3; EP 435, 334A2, page 3, line 1 9 to 50 on page 29 9) Antiseptic and fungicide page 150, lines 25 to 28 10) Formalin page 149, lines 15 to 17 Scavenger 11) Other additives page 153, line 38 Line 47 to page 47; page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 of EP 421,453A1 12) Line 150, line 4 Lines 24 to 13 13) Support page 150, lines 32 to 34 14) Film thickness and film properties Page 150 lines 35 to 49 15) Color development / black and white development Page 150 lines 50 to 50 Page 151, line 47; European special ・ Fogging process, page 34, line 11 to 5 of No. 442,323A2 Line, page 35, lines 14 to 22 16) Desilvering step, page 151, line 48 to page 152, line 53 17) Automatic developing machine, page 152, line 54 to page 153, line 2 18 ) Washing and stabilization process Page 153, lines 3 to 37

[0031]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Preparation of Sample 101 A multilayer color light-sensitive material Sample 101 consisting of the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver Silver amount 0.30 g Gelatin 2.20 g Ultraviolet absorber U-1 0.08 g Ultraviolet absorber U-3 0.04 g Ultraviolet absorber U-4 0.08 g High boiling organic solvent Oil- 1 0.11 g Microcrystalline solid dispersion of dye E-1 0.25 g Microcrystalline solid dispersion of dye E-2 0.10 g

Second layer: Intermediate layer Gelatin 0.50 g Compound Cpd-A 5.0 mg Compound Cpd-E 1.0 mg High boiling organic solvent Oil-3 0.10 g Dye D-4 8.0 mg Dye D-5 4.0 mg

Third layer: Intermediate layer Yellow colloidal silver Amount of silver 0.010 g Gelatin 0.40 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.35 g Emulsion B silver amount 0.15 g gelatin 0.80 g coupler C-1 0.10 g coupler C-2 0.04 g coupler C-6 0.05 g compound Cpd- A 5.0mg High boiling organic solvent Oil-2 0.10g

Fifth layer: middle-sensitivity red-sensitive emulsion layer Emulsion B Silver content 0.22 g Emulsion C silver content 0.30 g Gelatin 0.80 g Coupler C-1 0.13 g Coupler C-2 0.06 g Coupler C-6 0.01 g High boiling organic Solvent Oil-2 0.10g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.70 g Coupler C-3 0.70 g Coupler C-6 0.02 g Additive P-1 0.20 g High boiling organic solvent Oil-2 0.04 g

Seventh layer: Intermediate layer Gelatin 0.90 g Compound Cpd-D 0.04 g Compound Cpd-G 0.16 g

Eighth layer: Intermediate layer Gelatin 1.10 g Compound Cpd-A 0.10 g Compound Cpd-B 0.10 g Compound Cpd-C 0.17 g High boiling organic solvent Oil-3 0.15 g

Ninth layer: low-sensitivity green light-sensitive emulsion layer Emulsion E silver amount 0.10 g Emulsion F silver amount 0.20 g Emulsion G silver amount 0.20 g gelatin 0.50 g Coupler C-7 0.03 g Coupler C-8 0.09 g Coupler C- 10 0.04 g Coupler C-11 0.04 g Compound Cpd-A 0.01 g Compound Cpd-F 0.3 mg High boiling organic solvent Oil-2 0.10 g

Tenth layer: Medium-speed green photosensitive emulsion layer Emulsion G silver amount 0.30 g Emulsion H silver amount 0.10 g gelatin 0.50 g coupler C-4 0.12 g coupler C-10 0.06 g coupler C-11 0.06 g compound Cpd- F 0.03g High boiling organic solvent Oil-2 0.01g

Eleventh layer: High-sensitivity green photosensitive emulsion layer Emulsion I Silver amount 0.50 g Gelatin 0.50 g Coupler C-4 0.18 g Coupler C-10 0.09 g Coupler C-11 0.09 g Compound Cpd-F 0.08 g High boiling organic Solvent Oil-2 0.020g

12th layer: intermediate layer gelatin 0.30 g

Layer 13: Yellow filter layer Yellow colloidal silver Amount of silver 0.01 g Microcrystalline solid dispersion of dye E-3 0.25 g Gelatin 0.50 g Compound Cpd-B 0.02 g Compound Cpd-D 0.03 g Compound Cpd-G 0.10 g

Fourteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J silver amount 0.20 g emulsion K silver amount 0.30 g gelatin 0.80 g coupler C-5 0.30 g coupler C-6 5.0 mg coupler C-9 0.03 g

Fifteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.30 g Emulsion M silver amount 0.30 g gelatin 0.60 g Coupler C-5 0.30 g Coupler C-6 5.0 mg Coupler C-9 0.03 g

Sixteenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N silver amount 0.20 g Emulsion O silver amount 0.20 g gelatin 2.60 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-9 1.00 g High boiling organic Solvent Oil-2 0.40g

17th layer: 1st protective layer Gelatin 1.10 g UV absorber U-1 0.08 g UV absorber U-2 0.03 g UV absorber U-5 0.15 g Dye D-1 0.03 g Dye D-2 0.050 g Dye D-3 0.10 g Dye D-4 0.03 g Compound Cpd-H 0.40 g High boiling organic solvent Oil-2 0.30 g

18th layer: 2nd protective layer Yellow colloidal silver Silver content 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.10 g Gelatin 0.70 g Ultraviolet absorber U-1 0.06 g UV absorber U-2 0.02 g UV absorber U-5 0.10 g High boiling organic solvent Oil-2 0.07 g

Nineteenth layer: Third protective layer Gelatin 1.40 g Polymethyl methacrylate (average particle size 1.5 μ) 5.0 mg Copolymer of methyl methacrylate and methacrylic acid 6: 4 (average particle size 1.5 μ) 0.10 g Silicone oil SO-1 0.03g Cpd-S 0.030g

The photosensitive silver halide emulsions used are shown in Table 2.

[0053]

[Table 2]

Further, in addition to the above composition, additives F-1 to F
-8, surfactants W-1 to W-6, gelatin hardener H-
1 was added. Phenol as an antiseptic and fungicide,
1,2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added. The swelling ratio (ratio of swelled film thickness to dry film thickness) of this sample 101 was 1.8.

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Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, water and 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF were added to 1430 g of a wet cake of a dye containing 30% of methanol, followed by stirring to obtain a slurry having a dye concentration of 6%. Next, 1700 ml of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd.
The slurry was pulverized for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min. The beads were removed by filtration, diluted with water by adding water to a dye concentration of 3%, and heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained fine dye particles was 0.60 μm, and the width of the particle size distribution (particle size standard deviation × 100 / average particle size) was 18%. Similarly, solid dispersions of dyes E-2 and E-3 were obtained. The average particle sizes were 0.54 μm and 0.56 μm. (Preparation of Samples 102 to 116)
The coating amount of the comparative compound A per 1 m ^{2 on the} 10, 16, and 18 layers was 8 × 10 ⁻⁴ mmol, 5 × 10 ⁻³ mmol, 1 × 10 ⁻³ mmol, 3 × 10 ⁻³ mmol, 6 × 1
0 addition to added to a ^-3 millimoles so that exactly the same as Sample 101, to form Sample 102. The comparative compound A used in the sample 102 was compared with the comparative compound B, the comparative compounds C, I-1, I-2, I-3, I-4, I-6, I
-7, I-9, I-10, I-11, I-16, I-2
Samples 103 to 116 were prepared in exactly the same manner as in Sample 102 except that Equivalents 6 and I-27 were used, respectively.

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(Evaluation of Samples) Samples 101 to 116 were exposed to white light through a continuous wedge, and then subjected to the following development treatment, and the obtained image densities were measured. The ratio (relative sensitivity), S (R), S (G), and S (B) of the reciprocal of the exposure amount that gives a density of 1.0 for the cyan, magenta, and yellow image densities to the sample 101 are calculated, and each of the red and red values is calculated. It was expressed as a photosensitive sensitivity, a green photosensitive sensitivity, and a blue photosensitive sensitivity.

Next, the samples 101 to 116 were exposed to red light of the same exposure amount as that of the above-described white light exposure through the same continuous wedge as that of the white exposure, and were subjected to the following development processing. This white and red exposure has a cyan density of 1.0.
And the difference (△ logE (R)) of the logarithm of the exposure was determined as a measure of the interimage effect on the red-sensitive layer.
Similarly, the scales ΔlogE (G) and ΔlogE (B) of the interimage effect on the green and blue photosensitive layers were determined.

Further, Sample 10 was obtained through the MTF pattern.
Exposures Nos. 1 to 116 were exposed to white light and developed as described below. Then, the sharpness was compared at an MTF value of 10 cycles / mm. Table 3 shows a list of the manufactured samples and the evaluation results.

[0075]

[Table 3]

From Table 3, it can be seen that the comparative compound has an insufficient interimage effect or causes a large decrease in sensitivity, whereas the sample using the compound of the present invention exhibits an interimage effect without undesired decrease in sensitivity. It can be seen that the film has improved sharpness.

(Processing) Processing Step Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C. 12 liters 2200 ml / m ² First water washing 2 minutes 38 ° C. 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C. 4 liters 1100 ml / m ² Color development 6 minutes 38 ° C 12 liters 2200 ml / m ² Pre-bleaching 2 minutes 38 ° C 4 liters 1100 ml / m ² Bleaching 6 minutes 38 ° C 2 liters 220 ml / m ² Fixed 4 minutes 38 ° C 8 liters 1100 ml / m ² Second washing 4 minutes 38 ° C 8 liters 7500 ml / m ² Final rinse 1 minute 25 ° C 2 liters 1100 ml / m ²

The composition of each processing solution was as follows. [First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0mg-Diethylene glycol 13g 15g Water was added to 1000ml 1000ml pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank solution Stannous chloride dihydrate 1.0 g p-amino acid Phenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 mL Water was added to 1000 mL pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 hydrate 36g 36g Potassium bromide 1.0g-Potassium iodide 90mg-Sodium hydroxide 3.0g 3.0g Citrazinic acid 1.5g 1.5g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Water was added to 1000 ml 1000 ml pH 11.80 12.00 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] [Tank liquid] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g sodium formaldehyde sodium bisulfite adduct 30g 35g Water was added to 1000ml 1000ml pH 6.30 6.10 pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium dihydrate 120 g 240 g potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 ml 1000 ml pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenishment solution] Ammonium thiosulfate 80 g Same sodium sulfite 5.0 g ナ ト リ ウ ム Sodium bisulfite 5.0 g タ ン ク Add water and add 1000 ml 1000 ml pH 6.60 pH with acetic acid or aqueous ammonia It was adjusted

[Stabilizing solution] [Tank solution] [Replenishing solution] 1,2-benzisothiazolin-3-one 0.02 g 0.03 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g 0.3 g polymaleic acid ( (Average molecular weight 2,000) 0.1 g 0.15 g Add water 1000 ml 1000 ml pH 7.0 7.0

Example 2 1) Support The support used in Example 2 was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, 300 parts by weight were dried.
After being melted at ℃, extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-set at 250 ° C for 6 seconds to form a 90 μm thick PEN
A film was obtained. The PEN film has a blue dye, a magenta dye and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I- 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment on both surfaces, and then gelatin 0.1 g / m ² and sodium α-sulfodine were applied to each surface. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Drying is 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle size of 0.005 μm
Has a specific resistance of 5 Ω · cm (a secondary agglomerated particle)
(Diameter of 0.08μm) to 0.2g / m^Two, Gelatin 0.05g / m^Two, (C
H_Two= CHSO_TwoCH_TwoCH_TwoNHCO)_TwoCH_Two0.02g / m^Two, Poly (degree of polymerization 10)
Oxyethylene-p-nonylphenol 0.005 g / m^Twoas well as
Coated with resorcinol. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization 15) oxyethylene-propyloxy
Edge coated with trimethoxysilane (15% by weight)
Ruto-γ-iron oxide (specific surface area 43m^Two/ g, major axis 0.14μm, single
Axis 0.03μm, saturation magnetization 89emu / g, Fe⁺²/ Fe⁺³= 6/94, table
The surface is treated with 2% by weight of iron oxide with aluminum oxide silicon oxide
0.06g / m^TwoThe diacetyl cellulose 1.2g / m^Two(Oxidation
(Iron dispersion was performed with an open kneader and a sand mill.)
 , C as curing agent_TwoH_FiveC (CH_TwoOCONH-C₆H_Three(CH_Three) NCO)_Three0.3g /
m^TwoWith acetone, methyl ethyl ketone,
Coat with a bar coater using clohexanone,
A magnetic recording layer of 1.2 μm was obtained. Silica particles as matting agent
(0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene
Treated with propyloxytrimethoxysilane (15% by weight)
Each coated aluminum oxide (0.15 μm)
0mg / m^TwoWas added so that Drying is performed at 115 ° C for 6 minutes
(All rollers and conveyors in the drying zone are 115
° C). Magnetic recording layer with X-light (blue filter)
D^BColor density increase of about 0.1 and saturation of the magnetic recording layer
Magnetization moment is 4.2 emu / g, coercive force is 7.3 × 10 ^FourA / m, square
The ratio was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
(Compound b, 9 mg / m ² ) A mixture was applied. In addition, this mixture is xylene / propylene monomethyl ether (1/1)
The mixture was melted at 105 ° C. in water and dispersed by pouring into propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone (average particle size: 0.01 μm) and then added. As a matting agent, 15 mg / m ² of silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide (0.15 μm) coated with 15% by weight) as an abrasive were used. And dried at 115.
For 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer had excellent dynamic friction coefficient of 0.06 (stainless steel ball of 5 mmφ, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clip method), and also had a dynamic friction coefficient of 0.12 between the emulsion surface and the sliding layer described later. . Samples 201 to 216 were prepared and evaluated in the same manner as in Example 1 except that the supports of Samples 101 to 116 of Example 1 were changed to the above-mentioned supports. As a result, the same results as in Example 1 were obtained.

[0089]

According to the present invention, a silver halide photographic light-sensitive material having an improved interimage effect and improved sharpness can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/392 G03C 7/392 A

Claims (3)

[Claims] 1. A silver halide photographic material comprising at least one compound represented by the following general formula (I). Embedded image In the formula, M represents a hydrogen atom, an alkali metal, an ammonia group, L represents an alkylene group, Z is a hydroxy group, an alkoxy group, a cyano group, an acyl group, an alkyl-substituted carbamoyl group, an unsubstituted carbamoyl group, or a ureide group. , A carboxy group or a heterocyclic group. 2. A silver halide color photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer and / or the non-photosensitive layer is represented by the following general formula (I). 2. The silver halide photographic light-sensitive material according to claim 1, comprising at least one compound to be used. 3. The following general formulas (IX) and (IY)
A compound represented by the formula: Embedded image