JPH03127056A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color and tone reproduction performances by forming 2 green sensitive layers different in sensitivity from each other on a reflective support and incorporating specified silver halide grains in a layer lowest in sensitivity. CONSTITUTION:A red sensitive layer, the 2 green sensitive layers different in sensitivity, a blue sensitive layer, and a layer containing colloidal silver are laminated on the reflective support. The layer lowest in sensitivity comprises a polydispersion emulsion containing silver halide grains having a fluctuation coefficient of >=30% and their average particle diameter is smallest than those of all the photosensitive layer, thus permitting the obtained silver halide color photographic sensitive material to satisfy both of the color and tone reproduction performances at the same time.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and in particular, a silver halide color photograph with improved color reproducibility and tone reproducibility. It relates to photosensitive materials.

[Conventional technology]

Silver halide color photographic materials are required to have various performances, and with the recent trend towards higher image quality, improved color reproducibility is desired. Many methods have been proposed for improving color reproducibility, but among silver halide color photographic materials, reversal halogen,
When improving the color reproducibility of silver chloride photographic materials, it is generally not possible to use a technology to correct the secondary absorption of the coloring material using a colored coupler as used in color negative materials, so in general, the development effect is the main focus. is used. That is, the interimage effect (hereinafter referred to as 11E) in which the development of silver halide in one emulsion layer suppresses the development of other layers.
This has been done by using.

For example, the most common development inhibiting substance is a marginal ion, so it is possible to use this to control the critical content in a silver halide emulsion for each layer, and to control the silver iodide content on the surface and inside of silver halide grains. A technique is known that attempts to strengthen IIE by adjusting.

Also, Special Publication No. 59.35011 or Japanese Patent Publication No. 62.9
No. 1946 discloses a technique using a fogging emulsion or an internal fogging emulsion. Furthermore, JP-A-51-51941
The issue describes a technique that utilizes halide quinone derivatives that release organic inhibitors.

All of the above techniques attempt to control IIE in the first development in the development process of reversal photosensitive materials. However, the above-mentioned means for increasing the TIE in the first development in color reversal processing, that is, in black and white development, is generally ineffective and, for example, when the silver iodide content is increased, desilvering defects and staining in the second development tend to occur. Various adverse effects such as outbreaks were a problem, and the results were not necessarily great.

On the other hand, attempts to obtain a multilayer effect in color development, that is, in the second development in reversal processing, are also known. For example, JP-A-61-84646 discloses a technique for obtaining 11E by diffusing an oxidized color developing agent scavenger into other layers to control the color density of the other layers. This technique has many favorable points because it does not have a large adverse effect on the first development, but it also has a greater effect, and a technique that increases IIE has been desired more than ever.

On the other hand, tone reproducibility is also an important element, and there are many points that need to be improved for those who desire satisfactory photographs.

Normally, the extent to which the tone reproducibility of low-density areas (hereinafter referred to as highlights) and high-density areas (hereinafter referred to as shadows) in a print is expanded is determined by the lace pattern on a white blouse, for example. In addition to determining whether the photo will be photographed properly or whether the creases in a black suit are visible, overexposed or underexposed photographs will also affect how well the photograph is worth looking at.

Furthermore, although it is natural for colors to appear clearly, there is a constant demand for performance in terms of how faithfully or softly facial expressions can be expressed.

Several proposals have been made in the past regarding methods for improving these performances, but none of them have been able to fully satisfy skin tone and skin tone reproducibility. Therefore, there has been a strong desire to develop a silver halide color photographic material that satisfies both color reproducibility and tone reproducibility.

[Problems to be solved by the present invention]

As described above, in the prior art, it has been desired to improve color reproducibility, especially improvement in skin color reproducibility and improvement in tone reproducibility, but a technology that satisfies this requirement has not yet been developed.

In order to solve the problems of the prior art, an object of the present invention is to provide a silver halide color photographic material with improved color reproducibility and tone reproducibility.

[Means to solve problems]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having, on a reflective support, at least one layer each of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, and a colloidal silver-containing layer. The green light-sensitive layer consists of at least two layers with different sensitivities, and the silver halide grains contained in the lowest sensitivity layer are polydisperse emulsions with a coefficient of variation of 30% or more, and the average grain size is larger than that of all other light-sensitive layers. This is achieved by using a silver halide color photographic light-sensitive material which is characterized by its small size.

In the present invention, the colloidal silver-containing layer is a layer containing black colloidal silver, red colloidal silver, yellow colloidal silver, etc.
/m”, preferably 0.05g/m” to 0.5g/m”
contains. The position of the colloidal silver-containing layer is not particularly important, but 1
．． In the case of a black colloidal silver-containing layer, it may be coated as an antihalation layer close to the reflective support, and in the case of a yellow colloidal silver-containing layer, it may be coated as a blue-sensitive layer and a green-sensitive layer, or a green-sensitive layer as a filter layer. It may be applied between the layer and the red-sensitive layer.

The present invention is effective in silver halide color reversal light-sensitive materials having a layer containing colloidal silver.

The amount of silver in the photographic constituent layers of the silver halide color light-sensitive material of the present invention is preferably 2.0 g/l or less in terms of metallic silver, and more preferably in the range of 0.7 to 1.5 g/m''. It is.

In the present invention, the amount of silver in a photographic constituent layer is the total amount of silver including the amount of photosensitive silver in the silver halide emulsion layer and the amount of other colloidal silver and non-photosensitive fine grain silver halide. .

If the silver halide emulsion used in the silver halide color light-sensitive material of the present invention has a coefficient of variation of 30% or more, even if it is a mixture of two or more monodisperse emulsions with different grain sizes, It may be one type of polydisperse emulsion or a mixture of two or more types.

In order to bring out the effects of the present invention more effectively, it is better to use a monodispersed emulsion that is a mixture of two or more types of emulsions having different particle sizes. Here, the monodisperse silver halide emulsion means an average grain size d
It is preferable that the weight of silver halide contained within a grain size range of ±20% around , is 60% or more of the total silver halide grain weight, more preferably 70% or more, still more preferably 80% or more. It is something. Here, the average particle diameter d is
The product niX of the frequency ni of particles with particle size di and di3
The grain size di is defined as the grain size di when di3 is the maximum (three significant digits, the minimum number of digits is 4 to 5 digits). The grain size here is the diameter of the silver halide grains.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the diameter of the particles on the print or the area at the time of photographing (the number of particles measured is negligible). There must be more than 1,000 discrimination items)
.

Particularly preferred highly monodisperse emulsions have a distribution width of 20% or less when defined by the following. Here, the average particle diameter and standard deviation shall be determined from the above definition di.

A method for obtaining a monodispersed emulsion is to add a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed particles.
It can be obtained by adding Ag and I)H by controlled double jet method. Particularly preferred manufacturing methods include JP-A-58-49938 and JP-A No. 6
No. 0-122935, No. 59-46640, etc. can be referred to.

As the silver halide emulsion used in the silver halide color light-sensitive material of the present invention, any conventional silver halide emulsion can be used. The effect is particularly remarkable in the case of silver iodobromide emulsions.

The legal content of the silver iodobromide emulsion used in the present invention is preferably in the range of 2 to 6 mol%, more preferably 2 to 4 mol%.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for 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.

Each light-sensitive emulsion layer in the silver halide color light-sensitive material of the present invention may contain an appropriate color-forming coupler.

Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, a fogging agent, Antifoggants, chemical sensitizers, spectral sensitizers,
Compounds that release photographically useful fragments such as desensitizers and desensitizers can be used.

Furthermore, the silver halide color light-sensitive material of the present invention may be provided with auxiliary layers such as a protective layer, a subbing layer, an intermediate layer, a color mixture prevention layer, an ultraviolet absorbing layer, and an irradiation prevention layer.

The silver halide color light-sensitive material of the present invention includes a formalin scavenger, a fluorescent brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retardant, and a bleach accelerator. agent can be added.

To obtain a dye image using the silver halide color light-sensitive material of the present invention, commonly known color photographic processing may be performed after exposure.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example-1 (Preparation of Sample-1) Color reversal photosensitive material sample-1 was prepared by providing the following 1st to 11th layers on a paper support coated with polyethylene on both sides.
It was created. The coating amount of each component is expressed in g/m''. However, for silver halide, the coating amount is expressed in terms of silver.

1st layer (antihalation layer) Black colloidal silver 0.10 High boiling point solvent 0-1 0.90 Gelatin
1.5 Second layer (first red-sensitive layer) Cyan coupler C-10,20 Cyan coupler C-2 (LIO Anti-fading agent A-10,15 Anti-fading agent A-20,075 Color mixing inhibitor
A N -10,0059 High boiling point solvent 0-
1 0.22 red sensitizing dye (S-1,5-2
) spectrally sensitized silver iodobromide emulsion (Ag14.0 mol%
, particles with an average particle size of 0.9mm, Agl 4.0 mol%, and particles with an average particle size of 0.4μm are mixed at a molar ratio of 3 nia)
0.23 Gelatin 0
．． 81vg3 layer (second red-sensitive layer) Cyan coupler C-10,11 Cyan coupler C-20゜056 Anti-fading agent A-10,085 Anti-fading agent A-20,043 Color mixing inhibitor
A N -10,0034 High boiling point solvent 0-
10.13 Silver iodobromide emulsion spectrally sensitized with red sensitizing dye (S-1, 5-2) (Ag I 4.0 mol%, average grain size 0.9
μm) 0.13 Gelatin 0.90 4th layer (first intermediate layer) Color mixing prevention agent A N -10,020 Color mixing prevention agent A N -20, (160 High boiling point solvent
0-2 0.13 gelatin
0.90 5th layer (first green sensitive layer) Magenta coupler 〇-3,0,12 Fade t)j stop M A-30,034 Anti-fade agent A -40,0056 Anti-fade agent A
-50,071 Color mixing prevention agent A N -10,0
046 High boiling point solvent 0-2 0.09
Silver iodobromide emulsion spectrally sensitized with 2 green sensitizing dye (S-3) (grains with Ag I 4.0 mol%, average grain size 0.4 μm and Agl 2.0 mol%, average grain size 0) .25μ particles mixed in a molar ratio of 8:2') 0.
17 Gelatin 0.93 6th layer (second green-sensitive layer) Magenta coupler C-30,18 Anti-fading agent A-30,052 Anti-fading agent
A-40,0085 Anti-fading agent A-
50,11 Color mixing inhibitor A N -10,0070 High boiling point solvent 0-2 0.14 Green sensitizing dye (
A silver iodobromide emulsion (Ag I
4.0 mol%, average particle size 0.9 μm) 0.24 Gelatin 0.92 7th layer (second intermediate layer) Yellow colloidal silver Color mixing inhibitor Color mixing inhibitor High boiling point solvent Gelatin 8th layer (1st blue sensitivity Layer) Yellow coupler C-40,28 Anti-fading agent A-10,11 Anti-fading agent
A-60,057 Color mixing inhibitor A N
-10,0085 High boiling point solvent 0-3
Silver iodobromide emulsion spectrally sensitized with 0.055 blue sensitizing dye (S-4) (Ag 12.0 mol%, average grain size 0.9
μm particles and heg 14.0 mol%, average particle size 0.4 μm
particles in a molar ratio of 2:8)
0.15 gelatin 0.9
5 9th layer (second blue sensitive layer) Yellow coupler anti-fading agent 0.53 N-2 0,15 0,011 0,034 0,070 0,90 0,21 N-1 -2 -4 -1 Fading Inhibitor A-60,11 color mixing inhibitor
AN-10,016 high boiling point solvent 0-3
0.11 Silver iodobromide emulsion spectrally sensitized with blue sensitizing dye (S-4) (Ag I 2.0 mol%, average grain size 0.9 μm) 0.24 1.06 Gelatin 10th layer ( Ultraviolet absorbing layer) Ultraviolet absorber Ultraviolet absorber Color mixing inhibitor High boiling point solvent Gelatin 11th layer (protective layer) Gelatin However, in addition to the above, it also contains a surfactant and a knee-jerk dye.

-I -2 AN- -3 0,45 0,15 10,033 0,36 1,74 0,50 Hardener, irradiation U -3 -4 -1 -2 -4 -5 -6 H N- 2 0H Di-2-ethylhexyl phthalate diisodecyl phthalate- dinonyl phthalate-1 -2 -1 -2 -3 Used in each photosensitive layer.
It was prepared by the method of Example 1 of No. 178447.

After desalting and washing with water, each emulsion was subjected to optimal chemical maturation in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and the sensitizing dye, 4-hydroxy-6-methyl-1.3.3a ．． Chemical ripening was carried out by adding 7-chitrazaindene and l-phenyl-5-mercaptoterrasil.

(Preparation of Samples-2 to 7) In the same manner as Sample-1 above, the grain sizes of the silver iodobromide emulsions in the second, fifth, and eighth layers were changed to the values shown in Table-1. -2 to 8 were created. The legal content of the silver iodobromide emulsion used was the same as that of Sample-1.The coefficient of variation of the silver iodobromide emulsion used in this example was around 20%, and it was a monodisperse silver bromine emulsion. A mixture of two types of monodispersed silver halide emulsions has a dispersion coefficient of 30% or more.

The above sample was cut into three copies each with a size of 127 x 178 mm (a print size usually referred to as a two-copy size). Each of the samples was exposed to light from three types of color slides using a printer to achieve the appropriate density.

The color slide used here is Etafrom 64, a color reversal film made by East Lantac.
Created by photographing one photograph of the photographer himself, a close-up of the face of a German woman, and one of an American woman's face at appropriate exposure, and processing it using Eastman Kodak's specified development process (named E-6). did.

Each exposed sample is developed in the following development process.
.

(Development process) First development (monochrome development) 1 minute 15 seconds (38℃) Water
Washing 1 minute 30 seconds Light fog 100 ffux or more 1 second or more Second development (color development) 2 minutes 15 seconds (38°C) Washing with water
45 seconds bleach fixing
Wash with water for 2 minutes (38℃)
2 minutes 15 seconds <1st developer> Potassium sulfite 30.0g Sodium thiocyanate 1.0g Sodium bromide 2.4g Potassium iodide
8.0mg potassium hydroxide (48%)
5.2mQ potassium carbonate
14g Sodium bicarbonate 12g
l-phenyl-4-methyl-4-hydroxymethyl-3
- Pyrazolidone 1.5g Hydroquinone monosulfonate 23.3g Add water to 1.012 (pH = 9.
65) <Color developer> Benzyl alcohol 14.6 mff Ethylene glycol 12.6 m 12 Potassium carbonate (anhydrous) 26 g Potassium hydroxide 1.4 g Sodium sulfite 1.6 g 3,6-diF7t
9”/-1.8-diol 0.24g Hydroxylamine sulfate 2.6g 4-N-ethyl-N-
β-(methanesulfonamidoethyl)-2-methyl-p
-phenylenediamine sesquisulfate
Add 5.0g water
1.012 (pH- 10.30) <Bleach-fix solution> 1.56 molar solution of ammonium salt of ferric ethylenediaminetetraacetic acid complex 115+wff Sodium metabisulfite 15.4g Ammonium thiosulfate (58%) 126mm 5-mercapto-1 .2.4- Triazole 0.4g Add water 1.00.

(pH - 6.5) For each developed sample, the density of the Japanese woman's print was measured at a predetermined location using a reflection densitometer, and at the same time visual evaluation by 10 people was conducted along with the other two types of prints. I went to The results are shown in Table-2.

Regarding the density measurement points in Table 2, there are three points B, G, the cheek area where the light hits (highlight area), the cheek area (appropriate density area), and the throat area (part of the shadow).
The density of each R color was measured and the ratio to the G density was displayed.

In addition, the symbol evaluation is based on a 5-level evaluation, with the most desirable skin color being ◎
, the most unhealthy skin tone (e.g. pale sick skin tone)
and the middle is ○. △． We asked them to rank the 10 subjects using ×, and the overall rank of the 10 subjects was (Good)■. ○、△、x
, xx (Bad) As is clear from the results in Table 2, Samples 1, 4, 5 and 6 according to the present invention have improved skin color reproducibility and are suitable for faces with changes in exposure. It can be seen that the skin color reproduction in each part of the image is extremely well reproduced with few color breakdowns, indicating that the effect of the present invention is remarkable.

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material comprising, on a reflective support, at least one layer each of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, and a colloidal silver-containing layer, the green-sensitive layer has a high sensitivity. The silver halide grains contained in the lowest sensitivity layer are polydisperse emulsions with a coefficient of variation of 30% or more, and the average grain size is smaller than that of all other photosensitive layers. Silver halide color photographic material.