JP2821797B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material capable of rapid processing, having good processing stability, and having a wide exposure latitude. And a silver halide color photographic material using a silver chlorobromide emulsion.

(Prior art)

In recent years, in photosensitive materials for color photography and printing, the printing process and the developing process have been shortened and speeded up, and stability in processing has been increasingly required. At present, the so-called negative-positive method of taking a color photograph by using a color negative film, enlarging it on a color paper, and making a color print is widely used. One reason for this is that color negative films are set to a relatively low gamma, have a very wide exposure latitude (latitude), have a very low probability of failing when shooting, and can be easily used by ordinary users without specialized knowledge. The point is that you can take pictures.

Generally, a silver iodobromide emulsion containing 2 to 25 mol% of silver iodide is used for a high-sensitivity color light-sensitive material for photography, and the gamma of the blue, green and red light-sensitive layers is used. Is 0.4 to 0.8
It has been adjusted to be.

However, such a photosensitive material has a remarkable development suppressing effect due to iodine ions and bromine ions released during the development processing, so that the development time cannot be shortened, and since they are accumulated in the processing solution, It is recognized that it is important to increase the variation in photographic characteristics and to deteriorate color reproducibility and tone reproducibility. This is considered to be attributable in part to the fact that the response to the above-described variation differs for each grain having a different grain size or for each different photosensitive emulsion layer.

Japanese Patent Application Laid-Open No. 60-156059 discloses silver halide grains having substantially no photosensitivity (hereinafter referred to as "non-photosensitive") between two emulsion layers having different photosensitivity in order to improve the development progress of a color photographic light-sensitive material. A technique of providing a layer containing photosensitive silver halide grains) is disclosed, and JP-A-60-128429 discloses a technique for reducing the influence of processing solution fluctuation during development. A technique is disclosed in which photosensitive silver halide grains are contained in a layer outside the photosensitive silver halide emulsion layer farthest from the support.

Such techniques improve the stability of the photographic characteristic curve against processing variations, but are still not at a satisfactory level.

In addition, a negative film for photography using a silver iodobromide emulsion,
Although the advantages including silver iodide such as high sensitivity and interlayer effect are utilized to the maximum, it is also difficult to shorten the development process due to silver iodide. That is, it is also known that iodine ions accumulated in the desilvering solution remarkably delay the bleaching and fixing of silver, and hinder the rapid and low replenishment.

On the other hand, an emulsion having a high silver chloride content is considered to be advantageous for shortening the development and bleach-fixing processes and for minimizing a change in photographic characteristics due to a change in processing conditions.

However, silver chloride has high developability and has the disadvantage that the gradation becomes too hard.

Furthermore, in order to maintain sensitivity and image quality, a color negative for photography requires an amount of silver of 2.0 g / m ² or more.However, if an emulsion containing high silver chloride is used as it is, the latitude of the latitude remains unchanged at this amount of silver. Thus, the processing variability is rapidly deteriorated.

Accordingly, high silver chloride-containing emulsions have been used for color papers which use a small amount of silver, but have been difficult to use in negative-working photosensitive materials.

The present inventors have conducted intensive studies on silver chlorobromide emulsions having a high silver chloride content having various silver bromide contents, and as a result, have accomplished the present invention.

(Object of the present invention)

SUMMARY OF THE INVENTION An object of the present invention is to provide a color photographic light-sensitive material for photography, which has rapid processing suitability, has improved processing variability in development processing, and has a wide exposure latitude.

(Configuration of the present invention)

An object of the present invention is to provide a silver halide color photographic material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer on a transparent support. The total amount of silver contained in the light-sensitive material is 2.0 g / m ² or more, and silver chlorobromide is contained, and substantially the same color-sensitive layers in the light-sensitive material have different sensitivities. This is achieved by a color photographic light-sensitive material comprising at least two silver halide emulsion layers, each of which comprises two or more silver chlorobromide emulsions having different bromine contents.

 Hereinafter, the present invention will be described in more detail.

In the silver halide color photographic light-sensitive material of the present invention,
Red-sensitive silver halide emulsion layer (hereinafter abbreviated as red-sensitive layer)
And is a emulsion layer having a maximum sensitivity wavelength (lambda _R ^max) to 570～650Nm, green-sensitive silver halide emulsion layer (hereinafter, referred to as a green-sensitive layer) and a maximum sensitivity wavelength (lambda _G ^max) The 520-580
The blue-sensitive silver halide emulsion layer (hereinafter abbreviated as blue-sensitive layer) is an emulsion layer having a maximum sensitivity wavelength (λ _B ^max ) of 406 to 480 nm.

In the present invention, at least one of the silver halide emulsion layers having substantially the same color sensitivity has a plurality of emulsion layers having different photographic speeds. The "substantially the same silver halide emulsion layer having the same color sensitivity" as used herein may be the same in terms of the red light sensitivity, green light sensitivity, and blue light sensitivity,
The spectral sensitivity characteristics need not be exactly the same.

In the present invention, a preferred layer configuration is one in which a red photosensitive layer, a green photosensitive layer, and a blue photosensitive layer are applied in this order from the side close to the support.

In the present invention, sensitivity, total silver amount in order to maintain the image quality requires a 2.0 g / m ² or more, preferably 2.0 to 12.0
a g / m ^2, more preferably from 2.0~8.0g / m ^2.

In the silver halide color photographic light-sensitive material of the present invention, at least one of all silver halide emulsion layers constituting the light-sensitive material contains at least two kinds of silver chlorobromide having different silver bromide contents. Of the at least two types of silver chlorobromide, one has a silver bromide content of 99 to 20 mol%, and the other preferably has a silver bromide content of 1 to 80 mol%. .

The difference between the silver bromide contents of the at least two silver chlorobromide emulsions is preferably 10 to 80 mol%, more preferably 20 to 70 mol%. In this case, a difference in silver bromide content of the two silver chlorobromide emulsions of less than 2 mol% is regarded as an emulsion having substantially the same silver bromide content.

In the present invention, in addition to the silver chlorobromide, for example, silver iodide may be contained as long as the effects of the present invention are not impaired, but silver iodide is preferably not contained.

The average silver chloride content of silver halide can be determined by a fluorescent X-ray method.

The grain size of the silver halide used in the present invention is not particularly limited, but from the viewpoint of processing suitability due to differences in image properties such as graininess and developability depending on the grain size of the grains, preferably 0.1 to 0.1.
To 3 μm, more preferably 0.2 to 2 μm.
The structure of the silver halide grains is preferably a core / shell type silver halide grain. The core / shell type refers to a silver halide grain in which the silver halide composition differs between the inside and the surface.

Further, monodisperse particles are preferable, and as the degree thereof,
The ratio S / S of the standard deviation (S) of the grain size to the average grain size () of the entire silver halide grains contained in each silver halide emulsion layer.
Is preferably 0.4 or less, more preferably 0.33 or less, further preferably 0.25 or less, and particularly preferably 0.20 or less.

The average grain size () is the grain size (in the case of cubic silver halide grains, the length of one side thereof, and in the case of grains having a shape outside the cube, one side when converted to a cube having the same volume. Is defined by the following equation when the number of particles of length ri is ni.

The monodisperse core / shell type silver halide emulsion preferably used in the present invention as described above is described in JP-A-59-177353.
Nos. 60-138538, 59-52238, 60-143331
No. 60-357526 and No. 60-258536.

 In the present invention, tabular grains can also be used.

The silver halide emulsion according to the present invention is used to produce and grow silver halide grains, by controlling pAg, pH, temperature, stirring and the like in a predetermined pattern in a predetermined pattern, such as sodium chloride, potassium bromide or potassium iodide. It is manufactured by a double jet type emulsion manufacturing apparatus which controls the addition of halide and silver nitrate.

It is preferable that two or more kinds of silver chlorobromide emulsions having different bromine contents used in the present invention have different grain sizes.

For silver halide grains having different grain sizes, the average grain size is
A combination of silver halide grains having a maximum average grain size of 0.2 to 2.0 μm and silver halide grains having a minimum average grain size of 0.05 to 1.0 μm is preferred.

In the present invention, the dry film thickness of the entire photographic constituent layer is 20
μm or less is preferable, but the dry film thickness should be 10 to 18 to exhibit the processing stability and rapid processing suitability most effectively.
It is particularly preferable to set it to μm.

When the dry film thickness is larger than 20 μm, a sufficient effect on rapid processing suitability aimed at by the present invention cannot be obtained. On the other hand, when the dry film thickness is 10 μm or less, it is difficult to control the processing stability, and it is difficult to obtain a photographic density necessary for a color negative film for photography, which is not preferable.

As the support of the silver halide photographic light-sensitive material in the present invention, a transparent cellulose acetate film having a thickness of 10 to 200 μm, a polyethylene terephthalate film, or the like may be used.

In the present invention, as the silver halide emulsion, those described in Research Disclosure 308119 (hereinafter abbreviated as RD308119) can be used.

 The following table shows the locations.

In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. Additives used in such a process are Research Disclosure No. 17643, No. 18716 and No. 308119 (hereinafter referred to as RD, respectively).
17643, RD18716 and RD308119).

 The following table shows the locations.

Known photographic additives that can be used in the present invention are also described in the above-mentioned Research Disclosure. The following table shows the relevant descriptions.

Various couplers can be used in the present invention, and specific examples are described in the above-mentioned Research Disclosure. The following table shows the relevant descriptions.

The additives used in the present invention can be added by the dispersion method described in RD308119X IV and the like.

The light-sensitive material of the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD308119VII-K.

The light-sensitive material of the present invention can have various layer constitutions such as a normal layer, a reverse layer, and a unit constitution described in the aforementioned RD308119VII-K.

INDUSTRIAL APPLICABILITY The present invention can be applied to general-purpose or movie color negative films.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

In all examples below, the addition amount of the silver halide photographic light-sensitive material particularly shows the number of grams per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye was represented by the number of moles per mole of silver.

Example 1 On a triacetyl cellulose film support, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample 1.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Colored coupler (CC-1) 0.02 g High boiling solvent (Oil-1) 0.20 g 〃 (Oil-2) 0.20 g gelatin 1.6 g Second layer: Intermediate layer (IL-1) Gelatin 1.3 g Third layer: Low-sensitivity red-sensitive emulsion layer (RL) Silver bromide emulsion (Em-1) 0.4 g〃 (Em-2) 0.3 g Sensitizing dye (S-1) 1.5 × 10 ^-4 〃 (S-2) 1.5 × 10 ^-4 〃 (S-3) 0.09 × 10 ^-4 Cyan coupler (C-1) 0.50 g 〃 (C- 2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g Additive (SC-1) 0.003 g High boiling solvent (Oil-1) 0.5 g Gelatin 1.0 g Fourth layer: high-sensitivity red-sensitive emulsion layer (RH) Silver bromide emulsion (Em-3) 0.9 g Sensitizing dye (S-1) 1.1 × 10 ^-4 〃 (S-2) 1.0 × ^10-4 〃 (S-3) 0.06 × 10 -4 cyan coupler (C 2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling solvent (Oil-1) 0.25 g Additive (SC-1) 0.003 g Gelatin 1.0 g Fifth layer: intermediate Layer (IL-2) Gelatin 0.8 g Sixth layer: low-sensitivity green-sensitive emulsion layer (GL) Silver bromide emulsion (Em-1) 1.0 g g (Em-2) 0.2 g Sensitizing dye (S-4) 3.4 × 10 ^-4 〃 (S-5) 0.4 × 10 ^-4 Magenta coupler (M-1) 0.5 g 〃 (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling solvent (Oil-2) 0.7 g Additive (SC-1) 0.003 g Gelatin 1.0 g Seventh layer: High-sensitivity green photosensitive emulsion layer (GH) Silver bromide emulsion (Em-3) 0.9 g increase Sensitizing dye (S-6) 1.0 × 10 ^-4 〃 (S-7) 1.8 × 10 ^-4 〃 (S-8) 0.26 × 10 ^-4 Magenta coupler (M-1) 0.03 g〃 (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04g D IR compound (D-3) 0.004 g High boiling solvent (Oil-2) 0.35 g Additive (SC-1) 0.003 g Gelatin 1.0 g Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS -1) 0.07 g 〃 (HS-2) 0.07 g 〃 (SC-2) 0.12 g High boiling solvent (Oil-2) 0.15 g Gelatin 1.0 g 9th layer: low-sensitivity blue-sensitive emulsion layer (BL) bromide Silver emulsion (Em-1) 0.25 g 〃 (Em-2) 0.25 g Sensitizing dye (S-9) 2.1 × 10 ^-4 Yellow coupler (Y-1) 0.6 g 〃 (Y-2) 0.32 g DIR compound ( D-1) 0.003 g 〃 (D-2) 0.006 g High boiling solvent (Oil-2) 0.18 g Additive (SC-1) 0.004 g Gelatin 1.3 g 10th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver bromide emulsion (Em-4) 0.5 g Sensitizing dye (S-10) 0.9 × 10 ^-4 〃 (S-11) 0.4 × 10 ^-4 Yellow coupler (Y-1) 0.18 g 〃 (Y-2) 0.10 g High boiling solvent (Oil-2) 0.05 g Additive (SC-1) 0. 002 g gelatin 1.1 g 11th layer; first protective layer (PRO-1) silver bromide emulsion (Em-5) 0.3 g UV absorber (UV-1) 0.07 g 〃 (UV-2) 0.10 g high boiling point solvent ( Oil-1) 0.07 g 〃 (Oil-3) 0.07 g Formalin scavenger (HS-1) 0.2 g 〃 (HS-2) 0.1 g Gelatin 0.8 g 12th layer; 2nd protective layer (PRO-2) Surfactant (SU-1) 0.004 g 〃 (SU-2) 0.02 g Alkali-soluble matting agent (average particle size 2 μm) 0.13 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Cyan dye (AI-1) 0.005 g Magenta dye (AI-2) 0.01 g Slip agent (WAX-1) 0.04 g Gelatin 0.5 g In addition to the above-mentioned composition, coating aid SU-4, dispersing aid SU-3, and hardener H- 1, H-2, H-3, stabilizer
ST-1, preservative DI-1, dyes AI-1, AI-2, antifoggants AF-1, AF-2 were added as needed.

The emulsions used in the above samples are as follows.
All are monodisperse emulsions of pure silver bromide.

 Em-1: Octahedron 0.55μm Em-2: Octahedron 0.36μm Em-3: Octahedron 0.84μm Em-4: Octahedron 1.02μm Em-5: Octahedron 0.08μm The compounds used for sample 1 are shown below. .

Next, the third layer, the fourth layer, the sixth layer, the seventh layer,
Samples 2 to 8 shown in Table 2 were prepared by using emulsions having the same distribution and different halide compositions as shown in Table 1 instead of the silver halide emulsions of the ninth and tenth layers.

In Table 1, for example, EmA is 80 mol% of AgCl and 2% of AgBr.
The silver halide composition is 0 mol%.

For example, in Table 2, H / K = 0.4 / 0.3 means that EmH 0.4 g / m ² and Em
Mixed K0.3g / m ² indicates that the use.

The silver halide emulsions (EmA) to (EmL) were prepared as follows.

EmD production method The following (Solution A) and (Solution B) were controlled in pAg = 6.5 and pH = 3.0 in 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C.
Simultaneous addition over 30 minutes, and the following (Solution C) and (Solution D)
Was added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 2.75 g Potassium bromide 1.40 g Add water 200 ml (Solution B) Silver nitrate 10 g Add water 200 ml (Solution C) Sodium chloride 82.6 g Potassium bromide 42 g Add water 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to obtain an average particle diameter of 0.84 μm.
A monodisperse octahedral emulsion Em-D having a coefficient of variation (S /) = 0.07 and a silver chloride content of 80 mol% was obtained.

Further, the other method for producing Em is A than the method for preparing Em-D described above.
Change the halide composition of Solution C and Solution C arbitrarily, and arbitrarily change the pAg, pH, and mixing time at the time of addition of Solution C and Solution D to EmB ~
EmK was produced.

Each of the silver halide emulsions (EmA) to (EmL) used in Samples Nos. 2 to 8 was optimized optimally using the same type of sensitizing dye and sensitizer as (Em-1 to 4). Chemical sensitization.

50CMS using white light on the sample thus prepared
After exposure to sensitometry was performed so that the exposure amount was the following, the following development processes A and B were performed.

Processing A Temperature Time Color development 38 ° C 1 minute 10 seconds Bleaching and fixing 33 ° C 1 minute 30 seconds Washing 25-30 ° C 3 minutes Drying 75-80 ° C Approx. 2 minutes Color developing solution Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 4-Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 3.9 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Add water to make the total amount 1 and adjust to pH 10.20.

Bleaching-fixing solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Add water to make the total volume 1 and add potassium carbonate or glacial acetic acid so
Adjust to pH 7.1.

Processing B Temperature Time Color development 40.0 ± 0.3 ° C 20 seconds Bleaching and fixing 35.5 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonate disodium 1.0 g 4 -Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 7.1 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Adjust the pH to 1.10.

Bleaching-fixing solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% solution) 27.5ml Add water to make the total volume 1 and add potassium carbonate or glacial acetic acid.
Adjust to pH 5.7.

Stabilizing solution 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 Fluorescent whitening agent (4,4'-diaminostilbenedisulfonic acid derivative) 1.5 g Add water to make the total amount 1 and add sulfuric acid or potassium hydroxide
Adjust to pH 7.0.

Also, using the developing processes A and B, the color developing time was changed to 1 minute 3 seconds and 1 minute 17 seconds in the developing process A, and the color developing time was changed to 18 seconds and 22 seconds in the developing process B. The variation of γ with respect to the change in color development time was examined, where γ is the point (A) giving a density of Dmin + 0.3 in sensitometry.
When the density (B) when an exposure amount higher by 1.0 as ΔlogE is set with respect to the logarithm logE of the exposure amount,
This is a value indicating the slope of a straight line connecting the two points (A) and (B).

The concentration of each sample obtained by each treatment was measured using blue light, green light, and red light, and the length of the linear portion of the sensitometric characteristic curve was represented by ΔlogE, and is shown in Table 3. Further, a γ value was determined from the measured value and is shown in Table 3. Furthermore,
The γ variation rate is shown for each sample, with the γ variation width of Sample 1 being 100%.

As is evident from Table 3, when two types of silver chlorobromide emulsions having different silver bromide contents are used, the exposure latitude greatly increases.

Also, it is clear that the γ value of the sample of the present invention is very small with respect to the change in the development processing time, while the γ value of the sample of the present invention is similar to that of the comparative sample.

Further, it is clear that the γ fluctuation is very small even in the rapid processing.

〔The invention's effect〕

According to the present invention, a silver halide color photographic material having a wide exposure latitude, a small gamma variation with respect to a change in development processing, and excellent rapid processing suitability can be obtained.

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer on a transparent support, The total amount of silver contained in the photosensitive material is 2.0 g / m ²
As described above, and containing silver chlorobromide, substantially the same color-sensitive layer in the light-sensitive material is composed of two or more layers having different sensitivities, and one of the silver halide emulsion layers has a bromine content ratio of A color photographic light-sensitive material comprising two or more different silver chlorobromide emulsions.