JPH0285845A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress fogging due to a yellow filter layer by regulating the average silver iodide content of a silver halide emulsion to below specific of and forming a hydrophilic colloidal layer of yellow colloidal silver so that the layer has absorption at specified wavelengths. CONSTITUTION:When at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, at least one blue- sensitive silver halide emulsion layer and a yellow filter layer contg. yellow colloidal silver are formed on a support to obtain a silver halide color photographic sensitive material, the average silver iodide content of a silver halide emulsion contained in at least one of the emulsion layers is regulated to <=4mol% and a hydrophilic colloidal layer of yellow colloidal silver is formed so that the layer has its absorption max. at 430-450nm wavelength and 1/4 of the max. on the longer wavelength side at 500-560nm wavelength. Fogging due to the yellow filter layer can be suppressed.

Description

DETAILED DESCRIPTION OF THE INVENTION However, the present invention is not limited to these examples.

Preparation of yellow colloidal silver A: Dissolve dextrin in distilled water at 40°C, add NaO
After adjusting the pH to 12.0 with H and adding silver nitrate solution, gelatin was added and desalted to obtain a yellow colloid.
I got it.

Preparation of yellow colloidal silver B N a OHT: pH adjusted to 12.0 at 40″C
Dissolve dextrin in water, add hydrogen peroxide solution, and then add silver nitrate solution. Furthermore, gelatin was added and desalted to obtain yellow colloid B.

Preparation of yellow colloidal silver C In the preparation method of yellow colloidal silver B, the water temperature is set to 40°C.
Yellow colloidal silver C was prepared in the same manner as yellow colloidal silver B except that the temperature was changed from to 60°C.

Preparation of yellow colloidal silver silver nitrate solution was adjusted to pH 11.0 with NaOH, and hydroquinone and Naz SO3 were added thereto to prepare yellow colloidal silver silver.

Spectral absorption maximum absorption wavelength of yellow colloidal silver A-D (λ, □) Wavelength on the long wave side giving absorption of 2 of the maximum absorption value (λD/4
) Example 1 Preparation of Sample 101 A multilayer color photosensitive material consisting of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 101.

1st layer: Anti-halation layer Black colloid 0.25g/Ultraviolet absorber U-10.04g/Ultraviolet absorber U-
20.1g/B Ultraviolet absorber U-30.1g/M High boiling point organic solvent 0-1 0.1 cc/rr
Gelatin layer containing f (dry film W-2μ) 2N second intermediate layer A-142.5mg/rrf Compound H-10.05g/emulsion A Silver amount 0.05g/bo High-boiling organic solvent 0 2 0.05cc Gelatin layer containing /rrf (dry film thickness 1μ) 3rd layer: 1st red-sensitive emulsion layer sensitizing dye S-1 (0.47mg/rrr) and S-2 (
Monodisperse silver iodobromide emulsion spectrally sensitized at 0.02 mol %/e) Silver amount: 0.15 g/e (iodine content 4 mol%, average grain size 0.20 μ, grain size The coefficient of variation (hereinafter simply referred to as coefficient of variation) 12%) Sensitizing dyes S-1 (0,51 cm/bo) and S-2 (0,0
Monodisperse internal latent image type silver iodobromide emulsion spectrally sensitized with 3■/E) Silver amount: 0.20 g/V (Iodine content: 4 mol%, average grain size: 0.40μ, The distance from the latent image to the particle surface is 100 people.

Coefficient of variation 14%) Emulsion B Silver amount 0.05
g/Awakening A 1 0.60
mg/rrr compound H-60,01g/bo coupler -10,13g/rrr coupler C2
0,033g/rrr coupler C-100,1g/
M High boiling point organic solvent 0 2 0.08 cc/rr
Gelatin layer containing r (dry film thickness 0.7μ) 4th layer: 2nd layer
Red-light emulsion layer sensitizing dyes S-1 (1,1 cm/bo) and S-2 (0,04
Monodisperse silver iodobromide emulsion spectrally sensitized with ■/e)
Silver content: 0.53 g/bo (Iodine content: 3 mol%)
, average particle size 0.55μ, coefficient of variation 16%) Gelatin layer containing 0.22 cc/a (dry film thickness 1.7μ) 5th layer: 3rd red-sensitive emulsion layer containing sensitizing dyes s-1 (1.1 mg/rrr) and S-2 (0
Monodisperse silver iodobromide emulsion spectrally sensitized with silver content: 0.53 g/bo (iodine content: 2 mol%, average grain size: 0.07 μ, coefficient of variation: 17 %) A-71,2 u/m Coupler C-60, 35 g/Bokabu'y-C-80, 20 g/n (gelatin layer containing high boiling point organic solvent 0-2 0.24 cc/bo (dry film thickness 1. 8μ) 6th layer: Intermediate layer A-1010mg/r+ (A-115mg/rr? Compound H10, 1g/M Gelatin N containing high boiling point organic solvent 0-20.1cc/bo (dry film thickness lμ) 7th layer : First green emulsion layer sensitizing dye S-3 (2.2 mg/rrr) and S-4 (1
, 0 ■/rrf) Monodisperse silver iodobromide emulsion spectrally sensitized Silver amount: 0.5 g/rrf (Iodine content: 3 mol %, average grain size: 0.35 μ, coefficient of variation: 19
%) Emulsion B Silver amount...0.05g/
Bo A-5 0.12■/B Compound H60,01 g/rrr Compound H-50,005 g/Bo Coupler C-30.27 g/B High-boiling organic solvent 0 2 0.17 cc/Gelatin layer containing B (dry film thickness 0.7μ) 8th M: 2nd green-sensitive emulsion layer enhancing dye S-3 (0.29g/bo) and S-4 (0.3g/bo)
■ Monodisperse internal latent image type silver iodobromide emulsion spectrally sensitized with /rrf) Silver amount...0.5 g/rrr (iodine content 2
．． 5 mol%, average particle size 0.5μ, coefficient of variation 18%
, distance from the latent image to the particle surface (100 persons) A-60,2■/Bo compound H-60,01g/Bocoupler C-30,2g/Bo High boiling point organic solvent 0-2 0.13cc/Gelatin containing Bo Layer (dry film thickness 1.7μ) 9th layer: 3rd glaucoma emulsion layer
/E) Tabular silver iodobromide emulsion spectrally sensitized with
Silver content: 0.5 g/bo (Iodine content: 2 mol%, particles with a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all particles. Average thickness of particles: 0.5 g/bo). 10μ) A-21,5■/Bocoupler C-40,2g/Bo High boiling point organic solvent 0-2Q,03cc/r+
Gelatin layer containing f (dry film thickness 1.7 μ) 10th layer: Intermediate layer compound H-40, 1 g/a Gelatin N containing high boiling point organic solvent 0-20.1 cc/a (dry film thickness 0.05 μ) 11th layer: yellow filter layer yellow colloid i 艮 A! Jilffi 0.
12g/rrr Compound A-150,22g/rrr Compound H-10,02g/Bo compound H-20,03g/M High boiling point organic solvent 0-2 0.04cc/rr?
Gelatin layer containing (dry film w-1μ) 12th layer: 1st blue emulsion layer Tabular silver iodobromide emulsion i Nagaya spectrally sensitized with sensitizing dye S-5 (1.0 g/%) ...0.6 g/rrf (particles with an iodine content of 3 mol% and a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all particles. Average thickness of particles 0.1
0μ) Emulsion A Silver amount o, ig/bo A -7
Gelatin N containing 0.5 cc/bo coupler C-50.5 g/a high-boiling organic solvent 0 2 0.1 cc/bo (dry film thickness 1.5 μ) 13th layer: 2nd blue emulsion layer sensitizing dye Silver amount of tabular silver iodobromide emulsion spectrally sensitized with S-5 (2.0 g/rrf)...1. tg/bo (particles with an iodine content of 2.5 mol% and a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all particles. Average thickness of particles 0.15 μ) A-1210■/bo coupler ( , -71,2g/Bo Coupler C-80,2g/bo Gelatin layer containing high boiling point organic solvent 0-2 0.23cc/bo (dry film thickness 3μ) 14th layer: First protective layer A-130,10■ /B Ultraviolet absorber U-10,02g/B Ultraviolet absorber U-20,03g/B Ultraviolet absorber U-30,03g/B Ultraviolet absorber U-40,29g/B High-boiling organic solvent 0-2 0 .28cc/n(
gelatin layer (dry film thickness 2μ) 15th layer: Fine grain silver iodobromide emulsion covered with the surface of the second protective layer tk---0.1g/rrf (N1 mol% iodine content, average grain Size 0.06μ) A
-810■/bopolymethyl methacrylate particles 0.1 g/m (average particle 1.5μ) A-30,2g/bo A-91,0■/gelatin layer containing (dry film thickness 0.8μ) each layer In addition to the above composition, an antifoggant A-16, a gelatin hardener H-3, and a surfactant were added.

The compounds used to prepare the samples are shown in Table 3 below.

Preparation of Emulsions A and B A silver bromide cubic emulsion with an average grain size of 0115 μm was prepared by the Chondrald double jet method and fogged with hydrazine and a total complex salt under low pAg (referred to as emulsion A).

Emulsion B was obtained by shelling silver bromide to a thickness of 250 mm on the surface of emulsion A thus prepared.

Preparation of Sample 102 Sample 101/4 was prepared in exactly the same manner as Sample 101 except that the silver iodide content of the photosensitive silver halide emulsion of Sample 101 was all set to 5 mol %.

Explosion of Sample 103 Sample 103 was prepared in exactly the same manner as Sample 101 except that potassium iodide was added to the 117I yellow filter layer of Sample 101 at a rate of 0.6 x 10-2 g/rrf.

Preparation of Sample 104 Sample 104 was prepared in exactly the same manner as Sample 102 except that colloidal silver B was used instead of colloidal silver A in the 111J of sample 102.

Preparation of Samples 105 to 107 Samples 105 to 107 were prepared in the same manner as Sample 101 except that colloidal silver shown in Table 1 was used in place of Colloidal Silver A in the 11th layer of Sample 101.

Preparation of sample 108 Add potassium bromide to the 11th layer of sample 105 at 0.6 x 10-
Sample 108 was prepared in exactly the same manner as Sample 105 except that ``g/rrr was added.

Samples 101 to 108 prepared in this way were exposed to white light through a continuous wedge, subjected to the following development process, and the respective cyan, magenta, and yellow densities were measured.
The relative sensitivity of cyan, magenta, and yellow at a density of 1.0 and the maximum density (D□X) were determined. In addition, the amount of residual silver in the lowest density portion was measured and the desilvering speeds were compared.

In the case of color reversal photosensitive materials, it can be said that the higher the D wax, the lower the fog.

The method for measuring the interimage effect of the present invention is shown below.

For each of Samples 101 to 108, a portion was subjected to red wedge exposure, and another portion was subjected to white wedge exposure (red+green+blue light). The exposure amount during red exposure during white exposure and during red exposure was equivalent.

These exposed samples were subjected to the following development treatment. Comparing cyan exposed to red and cyan exposed to white, it can be said that the greater the exposure amount difference Δlog E at a density of 1.0, the greater the interimage effect on the red-sensitive emulsion layer.

In addition, the interimage effect on the green emulsion layer was determined in the same manner.

The above results are shown in Table 1.

Samples 101 to 108 exposed as described above were developed as follows.

Processing process time temperature The composition of each treatment liquid was as follows.

potassium sulfite potassium thiocyanate potassium carbonate of potassium bromide potassium iodide add water H 30.0g 30.0g 1.2g 1.2g 35.0g 35.0g 0°, 5g 5.0mg 1000n/! 100100 O,60 9,70 pH was adjusted with hydrochloric acid or potassium hydroxide.

Nisui Takaoka Mother Liquor Replenisher Ethylenediamine 10.0mj2 12.
Add 0 ml disodium phosphate 5.0 g water to 1000++1p H7,
00 pH was adjusted with hydrochloric acid or potassium hydroxide.

12, On/! 14.0 mj! Potassium bromide 0.5 g Potassium iodide
Add 1.0'mg water to 1000
n/! 1000 mlp H10,6011,00 pH was adjusted with hydrochloric acid or potassium hydroxide.

Drifting-” [-Tatsuna] Mother liquor Replenisher sodium sulfite hydroxylamine sulfate 2.0g 3.0g 2.5g 3.6g ammonium bromide ammonium nitrate add water pH 00g 0 g 000m1 6.30 The pH was adjusted with acetic acid or aqueous ammonia.

Replenishment solution was treated to below 3 mg/l, followed by 20 mg/f of sodium isocyanurate dichloride and 1.5 g of sodium sulfate.
/f was added. The pH of this liquid is in the range of 7.5.

6.5~ Sodium sulfite 15.0g Add water 1000ml pH6,
50 pH was adjusted with acetic acid or aqueous ammonia.

Second water IL Both mother liquor and replenisher are filled with tap water and H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) From the results of calcium and magnesium ion concentration in Table 1 when water was passed through the mixed bed column, the present invention showed that compared to the comparative example,
It is clear that Capri is low (Do is high) without any deterioration in interimage effect, sensitivity or desilvering properties.

Example 2 Sample 201 was prepared by applying the following 1st to 12th layers on a paper support laminated on both sides with polyethylene. The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) The components and coating amounts in g/rrr are shown below.

For silver halide and colloidal silver, coating amounts are shown in terms of silver.

1st N (gelatin N) Gelatin... 1.30 2nd layer (
Antihalation N) Black colloidal silver ... 0.10 Gelatin ... 0.70 3rd layer (low-sensitivity red-sensitive layer) Gelatin cyan color (*3) Cyan color (*4) ・ ・ ・ 1.00 ・・ ・ 0.14 ・ ・ ・ 0.07 Coupler solvent [*8 and *9)... 4th layer (highly sensitive red sensitive layer) 0.06 Gelatin cyan color (*3) Cyan color (*4) ・・ ・ 1.00 ・ ・ ・ 0.20 ・ ・ ・ 0.10 Coupler solvent (*8 and *9) ・ 5th layer (intermediate layer) Black colloidal silver 0.10 0.02 Gelatin color mixing inhibitor (*lO ) Polymer latex (*13) 6th layer (low sensitivity green sensitive layer) Gelatin magenta coupler (*15) Anti-fading agent (*16) Anti-stain agent (*17) Anti-stain agent (*18) 0.02 0.08 0.10 0.80 0.10 0.10 0.01 0.001 Anti-fading agent (*16) ... 0.10 anti-stain agent (*17) ... 0.01 anti-stain agent (*18) ... 0.001 No. 875 (
Yellow filter layer) Yellow colloidal silver A ... 0.20 Gelatin ... 1.00 Color mixing prevention agent (*1
0) ... 0.06 bolimar latex (
*13) 9th layer (low sensitivity blue sensitivity layer) 0.10 7th layer (high sensitivity green sensitivity layer) Gelatin 0.80 magenta coupler (*15) 0.10 gelatin yellow Coupler (*21) Stain inhibitor (*18) Coupler solvent (*9) 0.50 0.20 0,00 1 0.05 10th layer (high-frequency blue layer) Gelatin yellow coupler (*21) Stain Inhibitor (*18) Coupler solvent (*9) 11th layer (UV absorption N) Gelatin 1.00 0.40 0, OO2 0.10 1,50 Color mixing inhibitor (*23) Color mixing inhibitor solvent (*9 ) 0.06 0.15 12th layer (protective layer) *8 *9 *lO *11 *12 Di(2-ethylhexyl) phthalate trinonyl phosphate 2.5-di-octylhydroquinone tricresyl phosphate dibutyl phthalate *13 Polyethyl acrylate *23 2.5 -5ec-octylhydroquinone *19 Preparation of trioctyl phosphate tofecne sample 202 Other than setting the silver iodide content of the total photosensitive silver halide emulsion of sample 201 to 5 mol% Sample 201/4 was prepared in exactly the same manner as sample 201.

Preparation of sample 203 Add 0.7 x 10-" potassium iodide to the 8th N of sample 201.
Sample 203 was prepared in exactly the same manner as Sample 201 except that "g/m" was added.

Preparation of sample 204 Colloid j was used instead of colloid silver A in the eighth layer of sample 202.
Sample 1 was prepared in exactly the same manner as sample 202 except that 1B was used.
04 was produced.

Preparation of Samples 205 to 207 Samples 205 to 207 were prepared in exactly the same manner as Sample 201 except that the 8N yellow colloidal silver A of Sample 201 was changed to the yellow colloidal silver shown in Table 2.

Preparation of sample 208 Potassium bromide was added to the 8th layer of sample 204 at a concentration of 0.7
Sample 208 was prepared in exactly the same manner as sample 204 except that 'g/m' was added.

Regarding Samples 201 to 208 prepared in this manner, relative sensitivity, D#111X, residual silver amount, and interimage effect were determined as in Example 1.

However, the development process in this case was performed as follows.

[Processing process] First development (black and white development) 38°C 1'15" water washing
38°C1'30" inversion exposure
100 Lux or more 1° or more color development 3
8°C2° 15”Wash 38
℃ 45pa bleach fixing 38℃
2'OO''Wash 38°C2°
15'' [Treatment liquid composition] Potassium sulfite 30.0 g Potassium thiocyanate Potassium carbonate Diethylene glycol 1.2 g 35.0 g 15.0 mf Add potassium bromide potassium iodide water, add potassium bromide potassium iodide water te 2 left: Go old elephant jo.

benzyl alcohol diethylene glycol 0.5g 5,0■ (pH9,70) 15.0mff1 12.001A sodium sulfite glacial acetic acid add water sodium sulfite potassium carbonate hydroxylamine sulfate 2.0g 25.0g 3.0g 0.5g 1.0 ■ (p H10,40) 15.0g 5.0mj2 (pH 6°50) From the results in Table 2, Compared to the comparative example, the present invention has No. table Decrease in interimage effect, decreased sensitivity, Desilvering property Low fog without any deterioration (D...

is high stomach) The thing is clear.

0 ■ 10C) Iz C → 3-1 earth CHz CH + π ding H \ tcsH.

H 1'l)l t-CJ, + I H C1l□:CHSO□CH□C0NHCtlzC)I,
=CH3O□CHzCONHCHzUt+ H 0■ I H H H S'2 2H5 C! H.

CHzCH=CI(z CsF+tSOtNCHzCOOK C3H.

A-9 A-10 alls C, H5 Engraving of the statement (no changes to the contents) υi

Claims (1)

[Claims] A silver halide color photographic light-sensitive material having on a support at least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, one blue-sensitive silver halide emulsion layer, and a yellow filter layer containing yellow colloidal silver. ,
The average silver iodide content of the silver halide emulsion contained in the at least one emulsion layer is 4 mol% or less, and the maximum absorption wavelength of the yellow colloidal silver in the hydrophilic colloid layer is in the range of 430 to 450 nm, and 1/ of the maximum absorption value
A silver halide color photographic light-sensitive material characterized in that the long wavelength side giving a wavelength of 4 is in the range of 500 to 560 nm.