JPH0810322B2 - Silver halide color photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for color photographic paper.

[Background of the Invention]

In the industry, high-quality silver halide color photographic light-sensitive materials are desired, and in particular, silver halide photographic light-sensitive materials for color negatives are used for photography, and printed on silver halide photographic light-sensitive materials for color photographic paper, and finally printed. Get the image,
In the so-called color negative / positive system, there is a problem that the image quality of the silver halide photographic light-sensitive material for color photographic paper, especially the image sharpness, is lower than that of the silver halide photographic light-sensitive material for color negative. As an improved technology,
British Patents 584,609 and 1,277,429, JP-A-48-85130
No. 49-99620, 49-114420, 49-129537
No. 52-108115, No. 59-25845, U.S. Pat.
82, 2,533,472, 2,956,879, 3,125,448
No. 3,148,187, 3,177,078, 3,247,127,
3,540,887, 3,575,704, 3,653,905, 3,7
No. 18,472, No. 4,071,312, No. 4,070,352, etc., a technique for incorporating a water-soluble dye into a photographic element, and an antihalation layer made of colloidal silver on the emulsion layer side of the reflection support or on the emulsion layer. Techniques and the like provided on the opposite side are known.

On the other hand, in recent years, there has been an increasing demand from users for rich tone reproduction that gives a more natural impression when actually printing various scenes on color photographic paper.

However, the conventional color photographic paper has a hard tone, and the tone reproduction of the highlight part (for example, the face of a person) and the shadow part is insufficient, and the subtle shadow disappears (so-called “tonda”). There is often To improve this, softening the gradation of the photosensitive material improves the tone reproduction of the highlights and shadows, but it is a so-called "sleepy" print that does not blur and become clear as a visual impression. It is not desirable.

In addition, as described above, in order to improve the image sharpness, which is a problem in color photographic paper, when a technique such as the one described above in which a large amount of water-soluble dye is contained or an antihalation layer is provided, sharpness is improved. However, it has become clear that when the various scenes are actually printed, it gives a visually unnatural impression and the "skips" become noticeable.

[Object of the Invention]

The present invention has been made in view of the above circumstances, and an object of the present invention is to have excellent image sharpness, have improved color reproducibility, and have a high texture that gives a visually natural impression. It is to provide a silver halide color photographic light-sensitive material for obtaining an image.

[Structure of Invention]

The above object of the present invention is to provide a silver halide color photograph having on a reflective support a photographic constituent layer comprising a blue light sensitive silver halide emulsion layer, a green light sensitive silver halide emulsion layer and a red light sensitive silver halide emulsion layer. In the light-sensitive material, each of the silver halide emulsion layers contains silver halide grains having a silver chloride content of 90 mol% or more, and at least the optical reflection density at 550 nm or 680 nm of the silver halide color photographic light-sensitive material. One is 0.5 or more, and the color density of each of the green and red photosensitive emulsion layers is 0.3 to 1.8.
The average gamma in the exposure area corresponding to is 1.8 or more 2.5
Achieved with a silver halide color photographic light sensitive material which is less than.

Here, the reason why the object of the present invention has been achieved is speculated, but it is only speculation and the essence is not clear.

Generally, for color photographic paper, etc., spatial frequency 1 to 10 lines / m
It is said that sharpness of about m greatly contributes to image quality (Applied Physics, Volume 41, No. 1 (1972), pages 27-36, Journal of the Television Society, Volume 33, No. 12 (1979). , 1000 to 1008
Pages etc.). Considering the tone reproduction of such a minute part,
It seems that it is necessary to consider the contribution of the sharpness deterioration to the macro gradation (normal gradation that is not affected by the density fluctuations of minute portions) obtained by normal sensitometry. That is, in conventional color photographic paper,
If the gradation is softened to widen the tone reproduction exposure area, the gradation of a minute portion will be softened more than necessary, and as described above, the "sleepy" print will result.
Further, even if the macro gradation is the same, it is considered that the sharpness is improved and the gradation of a minute portion becomes hard, resulting in an image that gives a stiff and unnatural impression. Therefore, in a photographic light-sensitive material with improved sharpness, by appropriately softening the tone reproduction range, the exposure range is expanded and a rich tone reproduction that gives a natural impression without "drowsiness" or "sleepiness". As a result of intensive research conducted on the idea that a silver halide photographic light-sensitive material can be obtained, the present invention has been accomplished.

[Specific configuration of the invention]

In the present invention, 550 nm of silver halide photographic light-sensitive material
Or at least one of the optical reflection densities at 680 nm
It is 0.5 or more, preferably 0.7 or more. The optical reflection density in the present invention is measured by a reflection densitometer generally used in the art and is defined as follows.

Optical reflection density = log ₁₀ (Fo / F) Fo: Reflected light flux of standard white plate F: Reflected light flux of sample As a concrete means to increase the optical reflection density, as mentioned above, the antihalation layer made of colloidal silver is supported by reflection. It is preferably provided on the emulsion layer side of the body or on the side opposite to the emulsion layer and / or a water-soluble dye is contained in the photographic constituent layer.

The colloidal silver used in the present invention can be prepared mainly by reducing silver nitrate in the presence of gelatin with a phenol such as hydroquinone or pyrogallol, a reducing sugar or tannin.

Colloidal silver is usually used together with a hydrophilic polymer such as gelatin.

As the colloidal silver, black is preferable from the viewpoint of the antihalation effect, and the particle size of the colloidal silver is 0.
It is preferably 40 μm or less, and particularly preferably 0.20 to 0.010 μm.

The amount of colloidal silver applied is 0.25 g /
It is preferably m ² or less, and more preferably 0.2 g / m ² or less. On the other hand, it is preferably 0.01 g / m ² or more from the sharpness of the viewpoints such, 0.05 g / m ² or more is more preferable.

Examples of the water-soluble dye contained in the photographic constituent layer include well-known water-soluble dyes such as those described in the patents mentioned in the above [Background of the Invention].

Preferred water-soluble dyes used in the present invention include those represented by the following general formulas (I) to (III).

General formula (I) In the formula, R, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom,
A halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an -SO ₃ M or -NHCH ₂ SO ₃ M. M is a cation, an alkali metal cation, an ammonium cation,
Represents an organic ammonium cation (eg, pyridinium, piperidinium, triethylammonium, triethanolamine, etc.).

General formula (II) In the formula, R ₆ and R ₆ ′ each represent an alkyl group, an aryl group or a heterocyclic group containing at least one sulfo group or a carboxy group, and these groups may further have other substituents.

Each of the alkyl groups represented by R ₆ and R ₆ ′ may be linear or branched, and preferably has 1 to 4 carbon atoms. R ₆ ,
The aryl group represented by R ₆ ′ is preferably a phenyl group substituted with a sulfo group or a carboxy group.

The sulfo group and carboxy group contained in R ₆ and R ₆ ′ may be directly substituted on the alkyl group, the aryl group and the heterocyclic group, or may be bonded via a divalent organic group.

The substituents on the alkyl group, aryl group and heterocyclic group represented by R ₆ and R ₆ ′ other than the sulfo group or the carboxy group include a halogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group and an aryloxy group. Groups and the like.

Each R _7, R ₇ 'is an alkyl group, a cyano group, a trifluoromethyl _{group, -OR 8, -COOR 8, -CONHR} 8, -NHCOR 8, (R ₈ and R ₉ represent a hydrogen atom, an alkyl group or an aryl group. The alkyl group preferably has 1 to 4 carbon atoms.
The alkyl group and aryl group of are preferably a phenyl group, a halogen atom, an alkoxy group, a sulfo group,
It may have a substituent such as a carboxy group and a hydroxy group. ) Or (Wherein p, q is an integer of 1 or 2, X is a carbon atom, a sulfur atom, -CH ₂ - represents a group) represents a cyclic amino group represented by (e.g., morpholino, piperidino, piperazino, etc.) .

The methine group represented by L may be substituted with an alkyl group having 1 to 4 carbon atoms or an aryl group.

Further, at least one of the sulfo group and the carboxy group of the compound represented by the general formula (II) is an alkali metal, an alkaline earth metal, ammonia or an organic base (for example, diethylamine, triethylamine, morpholine, pyridine, piperidine, etc.). May form a salt with. n represents 0, 1 or 2.

General formula (III) In the formula, R ₉ represents an alkyl group, a carboxylalkyl group or a sulfoalkyl group, Z is a benzoxazole-based nucleus (including benzoxazole and substituted benzoxazole, the substituents are, for example, methyl, ethyl, phenyl, methoxy, ethoxy). , Chlorine, bromine, etc.) or a benzoxazole-based nucleus having a sulfo group on the benzene ring, provided that one or more of the above-mentioned substituents are present together with the sulfo group.
If R ₉ is an alkyl group, Z represents a sulfo-substituted benzoxazole nucleus, and if R ₉ is a carboxyalkyl group or a sulfoalkyl group, Z is a benzoalkyl group. It represents a group of non-metal atoms necessary for completing the oxazole nucleus. Q represents a nonmetallic atom group necessary for completing a sulfophenylpyrazolinone-based heterocyclic nucleus, and n represents 0, 1 or 2.

Next, typical specific examples of the water-soluble dye used in the present invention are shown, but the invention is not limited thereto.

[Exemplified compound] The water-soluble dye used in the present invention can be added to a light-sensitive silver halide emulsion layer and / or a non-light-sensitive photographic constituent layer.

Two or more kinds of the water-soluble dye of the present invention may be contained in the same layer. The same water-soluble dye may be contained in two or more different layers.

Generally, these water-soluble dyes of the present invention are preferably used in an amount of 2 × 10 ^{−4 to} 5 × 10 ² mol, and more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² mol per mol of silver in all emulsion layers. .

Photographic elements containing the water-soluble dyes of this invention are 550 nm or 6
The optical reflection density of 80 nm shows 0.5 or more, the water-soluble dye of the present invention is a water-soluble or a dye that is decolorized by a developing solution,
When the optical reflection density is less than 0.5, the effect of improving the image sharpness is not sufficiently observed. Although the upper limit of the optical reflection density is not limited, it is preferably 2.0 or less in terms of sensitivity, decolorization property and the like.

The silver halide color photographic light-sensitive material of the present invention has an average gamma in the exposure region for the color densities of the green and red light-sensitive layers in the sensitometric curve of 0.3 to 1.8, and both are 1.8 or more and less than 2.5. It is necessary to be, and preferably 2.0 or more and less than 2.4. Any of the techniques well known in the art can be used to control the tone of the sensitometric curve, for example with respect to silver halide, grain formation, crystal habit grain size, halogen composition,
Regarding physical ripening, chemical ripening, sensitizing dyes, inhibitors, sensitizers, and other oils, couplers, high-boiling organic solvents, various additives, dispersion states, DIR compounds, etc., or supports, gelatin hardened , Surface active agents, water-soluble dyes, etc., and the film thickness of each photographic constituent layer, the amount of silver halide or oil agent, the layer constitution and the like.

The silver halide photographic light-sensitive material of the present invention effectively exhibits the effects of the present invention when applied to negative-positive type and positive-positive type color printing papers which are directly provided for viewing.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, is a multi-color silver halide photographic light-sensitive material, and is usually used as a photographic coupler in order to perform color reduction method color reproduction. , And a cyanide silver halide emulsion layer containing a cyan coupler and a non-photosensitive layer are laminated on a support in an appropriate number and order of layers, but the number and order of layers are important. You may change suitably according to a performance and a purpose of use.

The dye image forming coupler used in the present invention is not particularly limited, and various couplers can be used.

Examples of the yellow dye image-forming coupler include acylacetamide type and benzoylmethane type 4-equivalent or 2-equivalent couplers.

Examples of magenta dye image forming couplers include 5-
Examples include pyrazolone-based, pyrazoloazole-based, pyrazolinobenzimidazole-based, indazolone-based, and cyanoacetyl-based 4-equivalent or 2-equivalent magenta dye image-forming couplers.

Examples of the cyan dye image-forming coupler include phenol-based and naphthol-based 4-equivalent or 2-equivalent cyan dye image-forming couplers.

Hydrophobic compounds such as these couplers can be added to the silver halide photographic light-sensitive material using various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method. For example, the oil-in-water emulsion dispersion method, a hydrophobic additive such as a coupler is usually used in combination with a high boiling organic solvent having a boiling point of about 150 ° C. or higher, and optionally a low boiling point, and / or a water-soluble organic solvent. It may be dissolved, emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and then added to the desired hydrophilic colloid layer.

The silver halide used in ordinary photographic light-sensitive materials includes any halogen such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and silver chloroiodobromide. Although a composition having a composition is used, silver halide grains having a silver chloride content of 90 mol% or more are desirable in the photographic light-sensitive material of the present invention, which is required to have a particularly fast developing property such as color photographic paper.

The silver halide emulsion grains in this case have a silver chloride content of 90 mol% or more, a silver bromide content of 10 mol% or less, and a silver iodide content of 0.5 mol% or less. Is preferred. More preferably, the silver bromide content is 0.01 to 5 mol%.
Of silver chlorobromide.

The silver halide used in the present invention may be a polydisperse emulsion having an average grain size distributed in a wide range, but a monodisperse emulsion is preferable.

These silver halide emulsions may be chemically sensitized with active gelatin, sulfur sensitizers, selenium sensitizers, reduction sensitizers, noble metal sensitizers and the like.

The silver halide used in the present invention may be optically sensitized by adding an appropriate sensitizing dye in order to impart photosensitivity to a desired light-sensitive wavelength region.

The silver halide photographic light-sensitive material of the present invention includes a color antifoggant, an image stabilizer, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a mordant, a development accelerator, a development retarder, and a fluorescence enhancer. Whitening agent, matting agent,
Lubricants, antistatic agents, surfactants and the like can be optionally used.

For the development processing of the silver halide photographic light-sensitive material of the present invention,
Various color development processes can be applied.

[Effect of the Invention] According to the silver halide color photographic light-sensitive material of the present invention,
Not only is the image sharpness improved, the tone reproduction of highlights and shadows is improved, but there is no so-called "sleepiness" or "dullness" visually. An image with tone reproduction can be obtained.

〔Example〕

Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

Example-1 (Preparation of silver halide emulsion) Five kinds of silver halide emulsions shown in Table-1 were prepared by a neutral method and a simultaneous mixing method.

After the chemical sensitization of each silver halide emulsion, STB-1 shown below as an emulsion stabilizer was added at 1 × 10 ^-4 mol per mol of silver halide.

Then, the following layers 0 to 7 were sequentially coated (simultaneous coating) on a paper support whose both surfaces were coated with polyethylene to prepare silver halide color photographic light-sensitive materials 1 to 32. In addition, in the following examples, the addition amount is shown as an amount per 1 m ² of the light-sensitive material.

Layer 0: An antihalation layer containing 0.8 g of gelatin and the black colloidal silver shown in Table 2.

Layer 1 ... Blue-sensitive silver halide emulsion (Em-1) containing 1.2 g and 0.29 g (equivalent to silver) of gelatin, 0.75 g yellow coupler (Y-1), and 0.3 g light stabilizer ST- 1 and 0.015 g of 2,5-dioctylhydroquinone (HQ-1)
A layer containing 0.3 g of dinonyl phthalate (DNP) dissolved in.

Layer 2: 0.2g of 0.9g gelatin and 0.04g HQ-1 dissolved
A layer containing dioctyl phthalate (DOP).

Layer 3 ... 1.4 g of gelatin, 0.2 g of green light-sensitive silver halide emulsion (Em-2 or Em-3) shown in Table-2, 0.5 g of magenta coupler (M-1) and 0.25 g of light stabilizer. ST-2 and
A layer containing 0.5 g of DOP in which 0.01 g of HQ-1 was dissolved and the water-soluble dyes shown in Table 2.

Layer 4: Gelatin 1.2g and 0.6g UV absorber UV-
Layer containing 0.3 g DNP with 1 and 0.05 g HQ-1 dissolved.

Layer 5: 1.4 g of gelatin and 0.20 g of red-sensitive silver halide emulsion (Em-4 or Em-5) shown in Table 2 and 0.
54 g of cyan coupler (C-1), 0.01 g of HQ-1 and
A layer containing 0.3 g DOP with 0.3 g ST-1 dissolved.

Layer 6 ... 0.2 g of gelatin dissolved in 1.1 g and 0.2 g of UV-1
A layer containing DOP and the water-soluble dyes shown in Table 2.

Layer 7: A layer containing 1.0 g of gelatin and 0.05 g of sodium 2,4-dichloro-6-hydroxy-s-triazine.

The obtained sample was subjected to sensitometry by using a sensitometer KS-7 type (manufactured by Konishi Rokusha Kogyo KK), after wedge exposure, and following the color development processing steps described below.

Also, after exposing the above sample with green light and red light through a wedge for measuring MTF value, the same processing is performed,
For each of the obtained samples, the green photosensitive layer and the red photosensitive layer
The MTF (Modulation Trnsfer Function) was obtained with a microdensitometer, and the MTF values at a spatial frequency of 5 lines / mm were compared. It should be noted that the determination of image sharpness by MTF is well known to those skilled in the art, but "The theory of the shot"
"graphic process 3rd edition".

In addition, color negative film (Sakura Color SRV-100:
Konishi Roku Photo Industry Co., Ltd.] and camera [Konica FT-1MOTO]
R: Konishi Rokusha Kogyo Co., Ltd.] was used to shoot various scenes indoors and outdoors with an 18% standard reflector. Subsequently, color negative development processing [CNK-4: manufactured by Konishi Rokusha Kogyo Co., Ltd.] was performed, and the obtained negative image was subjected to the above sample using a Sakura Color Printer CL-P2000 [manufactured by Konishi Rokusho Kogyo Co., Ltd.]. It was printed on 82mm x 117mm, and got a practical print. Printer conditions for printing are 18
The settings were made for each sample so that the% standard reflector became gray on the print. Next, this practical print was visually evaluated by 10 panelists involved in color print evaluation. The results are shown in Table-2.

[Treatment process]

Temperature Time Color development 34.7 ± 0.3 ℃ 45 seconds Bleach fixing 34.7 ± 0.5 ℃ 50 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds [Color developer] Pure water 800ml Triethanolamine 8g N, N- Diethylhydroxylamine 5g Potassium chloride 2g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate 30g Potassium sulfite 0.2g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1g Add pure water to make the total amount 1 and pH 10. Adjust to 2.

[Bleaching fixer]

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 bring the total volume to 1 and add pH 5.7 with potassium carbonate or glacial acetic acid. Adjust to.

[Stabilizing liquid]

5-Chloro-2-methyl-4-isothiazolin-3-one 1g 1-Hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make the total 1 and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide. .

In the visual evaluation column, "richness of tone" means "richness of highlight and shadow parts", and "naturalness of reproduction" means "naturalness of overall tone reproduction". Is an abbreviation.

As is clear from Table 2, in any of the samples, an anti-halation layer (layer 0) containing black colloidal silver was provided, or the amount of the water-soluble dyes in layers 3 and 6 was increased to obtain optical reflection. When the concentration is 0.5 or more, the MTF value of the corresponding layer increases, and the sharpness is significantly improved.
However, in samples No. 1 to No. 7 using Em-2 and Em-4 having high gamma values in the green and red light-sensitive emulsions,
Samples with higher MTF values tend to be visually stiffer and more flashy, and the "richness in highlights and shadows" and "naturalness of overall tone reproduction" in visual evaluation tend to deteriorate. Therefore, it can be seen that the improvement in sharpness is not utilized for the improvement in image quality (for example, samples No. 4, No. 6, No. 7).

In addition, Em-
No. 8 to No. 14 using No. 3 and No. 15 to No. 21 using Em-5 having a gamma value of less than 2.5 in the red photosensitive emulsion.
In visual evaluation, "richness of tone in highlights and shadows" was slightly improved, but "sleepiness" was noticeable, and the impression that the hues were disproportionate The "naturalness" tends to deteriorate rather than the "high texture". Among samples No. 22 to No. 32 using Em-3 and Em-5 having a gamma value of less than 2.5 in the green-sensitive emulsion and the red-sensitive emulsion, the optical reflection densities were 550 nm and 680.
Sample No. 22 and N that are 0.5 or less in any of nm
Regarding o.26, in the visual evaluation, the "richness of the highlight part and shadow part" was significantly improved, but the "sleepiness"
However, there is no noticeable improvement in "naturalness of overall tone reproduction" or "high texture".

On the other hand, Em-3 and Em-5 were used, and 55
Optical reflection density of 0.5 for at least one of 0 nm and 680 nm
The samples No. 23 to No. 25 and No. 27 to No. of the present invention as described above.
In the case of 32, the sharpness was improved in all cases, and the tones in the highlight part and shadow part were rich in visual evaluation, and the image with high texture that gives a natural impression in the overall tone reproduction. It can be seen that the obtained excellent silver halide color photographic light-sensitive material.

[Brief description of drawings]

FIG. 1 is a rational curve for explaining the definition of “gamma” used in this specification, where the horizontal axis represents the exposure amount logE, the vertical axis represents the color density D, and gamma (γ) is b / a. It is represented by.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a reflective support. In any of the silver halide emulsion layers containing silver halide grains having a silver chloride content of 90 mol% or more, and 55% of the silver halide color photographic light-sensitive material.
At least one of the optical reflection densities at 0 nm or 680 nm is 0.5 or more, and further, the average gamma in the exposure area corresponding to the color densities of the green photosensitive emulsion layer and the red photosensitive emulsion layer is 0.3 to 1.8, respectively. A silver halide color photographic light-sensitive material characterized by being at least 2.5.