JPH08179484A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide color photographic sensitive material improved in occurrence of color stains and exhibiting stable photographic performances for a long period without changing color staining prevention function during manufacture and storage. CONSTITUTION: The silver halide color photographic sensitive material has photographic constituent layers has on a support photographic constituent layers comprising at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, and at least one blue-sensitive silver halide emulsion layer containing a cyan coupler can a support, and at least one of nonphotosensitive hydrophilic colloidal layers between the emulsion layers different in color sensitivity contains a colloidal silica having an average particle diameter of <=0.10μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material which has improved color stain generation and shows stable photographic performance for a long period without changing the color stain prevention ability during storage. is there.

[0002]

When a multi-layer color photographic light-sensitive material containing a color-forming coupler in a silver halide photographic light-sensitive material is developed with a color-developing agent such as para-phenylenediamine, a color-developing agent oxide produced during development. However, it is well known that a so-called "color turbidity (color mixing)" phenomenon occurs in which an undesired dye is transferred to an adjacent image forming layer.

As a means for preventing the undesired color turbidity, it is usually used to introduce a non-photosensitive hydrophilic colloid layer (so-called intermediate layer) between the image forming layers. However, in order to sufficiently prevent color turbidity only with this intermediate layer, it is necessary to make the film thickness of the intermediate layer considerably large, which is very disadvantageous in terms of suitability for rapid processing and sharpness, so that the color of this intermediate layer is reduced. The method of adding an anti-turbidity agent is common. For example, various methods using a hydroquinone compound have been proposed, and although these compounds certainly have some effect in preventing color turbidity, the effect is small, and oxidation during production and storage of a light-sensitive material However, there are drawbacks such that it is easy to be processed and that the photographic performance of other layers is changed due to diffusion to layers not added.

Further, Japanese Laid-Open Patent Publication No. 1-147455 proposes a hydrazide compound, but its effect is not sufficient and there is a problem that photographic performance is changed during storage.

Therefore, it has been desired to develop a technique for improving color turbidity while keeping photographic performance stable for a long period of time.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to improve the occurrence of color stains and to provide halogenated halides which show stable photographic performance for a long period without changing the ability to prevent color stains during production and storage. It is to provide a silver color photographic light-sensitive material.

[0007]

The above object of the present invention is to:
It was achieved by a silver halide color photographic light-sensitive material having the following constitution.

A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler on a support. A silver halide color photographic light-sensitive material having a photographic constituent layer containing a non-photosensitive hydrophilic colloid layer containing colloidal silica having an average particle size of 0.10 μm or less in at least one of the emulsion layers having different color sensitivities. A silver halide color photographic light-sensitive material comprising:

The present invention will be described in detail below.

As an example of applying colloidal silica to a silver halide photographic light-sensitive material, JP-A-5-88285 discloses that colloidal silica having an average particle size of 0.10 μm or less is added to an emulsion layer. However, the purpose of the patent is to improve the pressure resistance of the monochrome photosensitive material, and the average particle size is 0.10 μm.
When the following colloidal silica was used in the constitution of the present invention in a color photographic light-sensitive material, it was an unexpected and surprising effect that a color turbidity improving effect was obtained. Therefore, the structure and effect are different from those of the patent.

The colloidal silica having an average particle size of 0.01 μm or less used in the present invention may contain alumina, sodium aluminate or the like with silicon dioxide as a main component. Preferred stabilizers include potassium hydroxide, ammonium hydroxide and the like.

Specific examples of the colloidal silica used in the present invention include Snowtex 20 manufactured by Nissan Chemical Co., Ltd.
C, N, O, Monsanto Cyton C-30, C-40, Zo
o, Santo Sale 62, FRC, Nalco Gom 1030, 1034A, 1060, ID21-64, EIDu Pont de
Lemox-AM, AS, LS, TM, HS, etc. of Nemouvs, Cab-O-S11, EH-5H-5, etc. of Cabo, Syroid Ova 20 grades made by Davison Dive Grace, Aerosil-130 made by Decassa, Examples include commercial products such as 200 and 300.

These colloidal silicas used in the present invention have an average particle size of 0.10 μm or less, and preferably 0.1.
It is in the range of 005 to 0.08 μm. The average particle diameter in the present invention means a weight average.

The amount of colloidal silica used is in the range of 0.05 to 3.0 g dry weight per 1 m ^{2 in} one added layer.

The silver halide color photographic light-sensitive material of the present invention can be, for example, color negative and positive films, and color photographic paper.

The silver halide photographic light-sensitive material of the present invention comprises a silver halide emulsion layer containing magenta, yellow and cyan couplers as couplers and a non-photosensitive layer on a support in an appropriate number and layer order. Although it has a laminated structure, the number of layers and the layer order may be appropriately changed depending on the priority performance and the purpose of use.

The coupler may be 4-equivalent or 2-equivalent.

Further a coupler having the effect of color correction,
Development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners, fog agents, antifoggants, chemical sensitizers, spectra by coupling with competing couplers and oxidants of developing agents. Compounds that release photographically useful fragments such as sensitizers and desensitizers can also be used.

A colorless coupler which does not form a dye can be used in combination, though a coupling reaction with an oxidized product of an aromatic primary amine developing agent is carried out.

Preferred yellow couplers include benzoylacetanilide type and pivaloylacetanilide type couplers, magenta couplers include 5-pyrazolone type, pyrazoloazole type and indazolone type couplers, and cyan dye forming couplers include There are phenol type, naphthol type, pyrazoloquinazolone type, pyrazolopyrimidine type, pyrazolotriazole type and imidazole type couplers.

Next, typical examples of yellow couplers will be given.

[0022]

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[0023]

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[0024]

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[0025]

[Chemical 4]

In addition to these, as a yellow coupler,
For example, OLS 2,163,812, JP-A-47-26133, 48-29432
No. 50, No. 50-65321, No. 51-3631, No. 51-50734, No. 51-
102636, 48-66835, 48-94432, 49-1229,
The compounds described in JP-B-49-10736, JP-B-51-33410, JP-B-52-25733 and the like can be mentioned, and the compounds can be synthesized according to the methods described therein.

Next, typical examples of magenta couplers will be given.

[0028]

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[0029]

[Chemical 6]

[0030]

[Chemical 7]

[0031]

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[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

In addition to these, as a magenta coupler,
For example, U.S. Patent No. 3,684,514, British Patent No. 1,183,515, Japanese Patent Publication Nos. 40-6031, 40-6035, 44-15754, 45-407.
57, 46-19032, JP-A-50-13041, 53-129035
No. 51-37646, No. 55-62454, U.S. Patent 3,725,067
No., British Patents 1,252,418, 1,334,515, JP 59-1.
71956, 59-162548, 60-43659, 60-33552
No., Research Disclosure No.24626 (1984), Japanese Patent Application Nos. 59-243007, 59-243008, 59-243009, 5
The compounds described in 9-243012, 60-70197, 60-70198 and the like can be mentioned, and the compounds can be synthesized according to the methods described therein.

Typical examples of cyan couplers will be given below.

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

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[0040]

[Chemical 15]

[0041]

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Other cyan couplers include, for example, US Pat. Nos. 2,423,730 and 2,801,171, and JP-A-50-112.
038, 50-134644, 53-109630, 54-55380,
56-65134, 56-80045, 57-155538, 57-2
The compounds described in 04545, 58-98731, 59-31953 and the like can be mentioned, and the compounds can be synthesized according to the methods described therein.

As the silver halide emulsion used in the light-sensitive material of the present invention, any of ordinary silver halide emulsions can be used.

The emulsion can be chemically sensitized by a conventional method, and it is optically sensitized in the respective wavelength regions of blue sensitivity, green sensitivity and red sensitivity by using a sensitizing dye. The emulsion sensitized to each color sensitivity is combined with each coupler of yellow, magenta and cyan to form each light-sensitive silver halide emulsion.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained.

Formalin scavengers, fluorescent whitening agents, matting agents, lubricants, image stabilizers, surfactants, development accelerators, development retarders and bleaching accelerators can be added to the light-sensitive material. If necessary, a color turbidity preventing agent may be used in combination.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

To obtain a dye image using the light-sensitive material of the present invention, a color development process including a color development (preferably using an aromatic primary amine color developing agent) step can be carried out after exposure.

[0051]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to obtain a multicolor silver halide photosensitive material sample 101.

First layer: blue-sensitive silver halide emulsion layer Yellow coupler (Y-9) 6.8 mg / 100 cm ² , blue-sensitive silver chlorobromide emulsion (containing 99.5 mol% of silver chloride) 3.2 m in terms of silver
The coating amount was g / 100 cm ² , dibutyl phthalate 3.5 mg / 100 cm ² , and gelatin 13.5 mg / 100 cm ² .

Second layer: intermediate layer The following comparative compound (a) was coated so as to have a concentration of 0.75 mg / 100 cm ² , dibutyl phthalate 0.5 mg / 100 cm ² and gelatin 9.0 mg / 100 cm ² .

Third layer: green-sensitive silver halide emulsion layer Magenta coupler (M-17) 3.5 mg / 100 cm ² , green-sensitive silver chlorobromide emulsion (containing 99.5 mol% of silver chloride) 2.5 m in terms of silver
g / 100 cm ^2, dibutyl phthalate 3.0 mg / 100 cm ^2, was coated so that the gelatin 12.0 mg / 100 cm ^2.

[0056] Fourth layer: intermediate layer UV absorbent (UV-1) 0.7mg / 100cm 2, dibutyl phthalate 6.0mg / 100cm ^2, 2,5- di -t- octylhydroquinone (HQ-1) 0.5mg / 100cm ² , gelatin 12.0mg / 100cm ²
It was painted so that

Fifth layer: Red-sensitive silver halide emulsion layer Cyan coupler (C-6) 4.2 mg / 100 cm ² , red-sensitive silver chlorobromide emulsion (containing 99.5 mol% of silver chloride) 3.0 mg in terms of silver.
/ 100cm ² , tricresyl phosphate 3.5mg / 100cm ² ,
It was coated so that the amount of gelatin was 11.5 mg / 100 cm ² .

Sixth layer: protective layer It was coated so as to have a gelatin content of 8.0 mg / 100 cm ² . In addition, the comparative compound (a) of the second layer of the sample 101 was replaced with the comparative compound (b).
Change to the color contamination inhibitor shown in (added equimolar amount) and
2 was produced.

Next, the comparative compound (a) of the second layer of sample 101
And dibutyl phthalate were changed to the colloidal silica shown in Table 1 to prepare samples 103 to 116.

Each of the samples obtained above was imagewise exposed to blue light and processed in the following steps.

Treatment process Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleach fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying at room temperature (25 ° C) Color developer Pure water 800ml Triethanolamine 10g N, N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-disulfonic acid Disodium salt 1.0 g N-Ethyl-N-β-methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water is added to bring the total volume to 1 l, and the pH is adjusted to 10.10.

Bleach-fix solution Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, potassium carbonate or With glacial acetic acid
Adjust to pH = 6.2.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20 % Aqueous solution) 3.0 g ammonium sulfite 3.0 g fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.5 g Add water to bring the total volume to 1 liter and add sulfuric acid or potassium hydroxide.
Adjust to pH = 7.0.

[0064]

[Chemical 17]

A densitometer (manufactured by Konica Corporation)
The color mixture value (D _G / D _B ) obtained from the maximum blue density (D _B ) and the maximum green density (D _G ) measured using the PDA-65 type) was measured for Sample 10.
Table 1 shows 1 as 100.

Next, each sample was left under high temperature and high humidity of 60 ° C. and 80% relative humidity for 3 days, and then exposed and processed by the same method. Fog was measured by a conventional method. Also, the increase in D _G / D _B due to standing was determined in order to see the change in color mixing. The results are shown in Table 1.

The above test is a forced deterioration test for checking the storage stability of each sample, and the results generally obtained by this method correlate with the long-term storage stability of each sample under normal conditions. .

[0068]

[Table 1]

From Table 1, colloidal silica having an average particle size of 0.20 μm has less fog and variation in color mixing value in the forced deterioration test than the comparative sample, and has good storage stability, but the effect of improving color mixing is insufficient. Is. On the other hand, it is understood that the sample of the present invention is equal to or more than the effect of improving the color mixture as compared with the comparative sample, and is excellent in storage stability.

Example 2 A multilayer color film sample 201 having the layer structure shown below was prepared on a support coated with an antihalation layer.

Layer structure: Pro layer, BH layer, BL layer, YF layer, GH
Layer, GL layer, IL layer, RH layer, RL layer, support Next RL layer, RH layer,
The GL layer, GH layer, BL layer, BH layer, IL layer, YF layer, and Pro layer will be described. The addition amount is shown per 1 m ² . The amounts of silver halide and colloidal silver are shown in terms of silver.

RL Layer (Low-Sensitivity Red-Sensitive Silver Halide Emulsion Layer) An emulsion (Emulsion I) made of AgBrI containing an average grain size (r) of 0.47 μm, a coefficient of variation (S / r) of 0.12, and an average AgI of 8 mol%. 1.0 g of red-sensitized color, average grain size of 0.31 μm, coefficient of variation of 0.10, emulsion of AgBrI containing 8 mol% of average AgI (emulsion II) 1.0 g and 0.07 g of 1-hydroxy-4- [4 -(1
-Hydroxy-8-acetamido-3,6-disulfo-2-naphthylazo) phenoxy] -N- [δ- (2,4-di-t-amylphenoxy) butyl] -2,7-naphthamide disodium (CC -1), 0.4 g of cyan coupler (C-23) and 0.06 g of
DIR compound (D-1) was added to 1.0 g of tricresyl phosphate
A layer which is dissolved in (called TCP) and is emulsified and dispersed in an aqueous solution containing 2.4 g of gelatin.

RH layer (high-sensitivity red-sensitive silver halide emulsion layer) An emulsion (Emulsion III) made of AgBrI containing an average grain size of 0.7 μm, a coefficient of variation of 0.12 and an average AgI of 6 mol%, which has been red-sensitized. 0.23 g of 2.0 g and 0.20 g of cyan coupler (C-23) and 0.03 g of colored cyan coupler (CC-1)
A layer containing a dispersion prepared by dissolving it in TCP, and emulsifying and dispersing this in an aqueous solution containing 1.2 g of gelatin.

GL layer (low-sensitivity green-sensitive silver halide emulsion layer) 1.5 g of emulsion I sensitized to green sensitivity, 1.5 g of emulsion II sensitized to green sensitivity and 1.5 g and 0.35 g of magenta coupler ( M-26), 0.10 g of 1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octadecenylsuccinimidoanilino) -5-pyrazolone 0.68 g (referred to as CM-1) and 0.04 g of DIR compound (D-1) dissolved
And a dispersion containing TCP emulsified and dispersed in an aqueous solution containing 2.4 g of gelatin.

GH layer (high-sensitivity green-sensitive silver halide emulsion layer) Emulsion III color-sensitized to green sensitivity 2.0 g and 0.14 g of magenta coupler (M-26) and 0.45 g of colored magenta coupler (CM- 1) and a dispersion containing 0.27 g of TCP dissolved in and emulsified in an aqueous solution containing 2.4 g of gelatin.

BL layer (low-sensitivity blue-sensitive silver halide emulsion layer) 0.5 g of emulsion I sensitized to blue sensitivity, 0.5 g of emulsion II sensitized to blue sensitivity and 0.5 g and 0.7 g of yellow coupler ( Y-13) and 0.02 g of a DIR compound (D-1) dissolved in 0.68 g of TCP in an aqueous solution containing 1.8 g of gelatin.

BH layer (high-sensitivity blue-sensitive silver halide emulsion layer) 0.9 g emulsion sensitized to blue sensitivity with an emulsion composed of AgBrI having an average grain size of 0.80 μm, a coefficient of variation of 0.14, and an average AgI content of 6 mol%. 0.25 g of yellow coupler (Y-13) was dissolved
A layer containing 0.25 g of TCP emulsified and dispersed in an aqueous solution containing 2.0 g of gelatin.

IL layer (intermediate layer) A layer containing 0.07 g of dibutyl phthalate (referred to as DBP) in which 0.07 g of HQ-1 was dissolved and 0.70 g of gelatin.

YF layer (yellow filter layer) A layer containing 0.15 g of yellow colloidal silver, 0.11 g of DBP in which 0.3 g of the comparative compound (a) was dissolved, and 1.0 g of gelatin.

Pro layer (protective layer) A layer made of 2.3 g of gelatin.

[0081]

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Samples 202 to 209 which were exactly the same as sample 201 except that the comparative compound (a) and DBP of the YF layer of sample 201 thus prepared were replaced with colloidal silica shown in Table 2.

Next, in the sample 207, the comparative compound (a) used in the sample 201 and DBP were added to the YF layer in ½ amounts to prepare a sample 210.

After each sample was subjected to wedge exposure using blue light, color development processing was performed according to the following processing steps.

[Processing step] Processing time Color development 38 ° C 3 minutes 15 seconds Bleach 38 ° C 6 minutes 30 seconds Water washing 25-30 ° C 3 minutes 15 seconds Fixing 38 ° C 6 minutes 30 seconds Water washing 25-30 ° C 3 Min 15 sec Stabilized 25-30 ° C 1 min 30 sec Dry 75-80 ° C The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid / trisodium (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water was added to make 1 liter, and sodium hydroxide was used to adjust the pH to 1
Adjust to 0.6.

[Bleach] Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to make 1 liter, and pH is adjusted to 8.0 using ammonia water. .

[Fixing Solution] Ammonium thiosulfate 175.0 g Anhydrous ammonium sulfite 8.6 g Sodium metasulfite 2.3 g Water was added to make 1 liter, and pH was adjusted to 6.0 using acetic acid.

[Stabilizer] Formalin (37% by weight) 1.5 ml Conidax (Konica Corporation) 7.5 ml Water is added to make 1 liter.

For each of the samples treated as described above, the color mixture value (D _G / D _B ) was determined in the same manner as in Example 1 and
The relative values of 00 are shown in Table 2.

Immediately after exposure to white light, the sample which had been subjected to the above-mentioned development treatment and, after exposure, in the dark at 40 ° C. and 80% relative humidity
After leaving it for 14 days for forced deterioration, the samples subjected to the above development treatment were prepared, and the sensitivity of the green-sensitive layer of these two types of samples (fog of magenta density + exposure amount at a density of 0.25) The change in the inverse logarithm of is shown in Table 2 as the change in sensitivity under the condition of forced deterioration.

[0092]

[Table 2]

As can be seen from Table 2, the sample of the present invention has an effect of preventing color mixing that is equal to or more than that of the comparative sample (201), and the change in sensitivity upon forced deterioration is small and the storage stability is excellent.

Further, the sample (210) in which the conventional color stain inhibitor and the colloidal silica are combined is superior to the sample (207) in which colloidal silica alone is stored, but it is superior to the comparative sample, and the color mixture is prevented. The effect is also excellent.

[0095]

EFFECT OF THE INVENTION Due to the constitution of the present invention, there is little color contamination,
In addition, it was possible to provide a silver halide photographic light-sensitive material having little change in photographic performance during storage.

Claims (1)

[Claims] 1. A blue-sensitive silver halide emulsion layer containing on each support at least one yellow coupler,
In a silver halide color photographic light-sensitive material having a photographic constituent layer including a green-sensitive silver halide emulsion layer containing a magenta coupler and a red-sensitive silver halide emulsion layer containing a cyan coupler, between the emulsion layers having different color sensitivities. A silver halide color photographic light-sensitive material comprising at least one non-photosensitive hydrophilic colloid layer containing colloidal silica having an average particle size of 0.10 μm or less.