JPH03113436A - Color reversal photosensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility over the range from white or neutral gray to black by regulating all the max. reflection densities of yellow, magenta and cyan to a specified value or above and making the min. reflection density of yellow highest and that of cyan lowest. CONSTITUTION:All the max. reflection densities of yellow, magenta and cyan are regulated to >=2.5 and the min. reflection density of yellow is made highest and that of cyan lowest. When a color reversal photosensitive material is exposed with white light and subjected to prescribed color reversal processing and the characteristic curve of the resulting sample is formed, the max. and min. reflection densities can be obtd. Color reproducibility over the range from white or neutral gray to black can be improved.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a color reversal photosensitive material, and in particular, the present invention is suitable as a color reversal photographic paper with improved reproduction of white, neutral gray to black. It can be used for.

[Prior art]

There are two main types of use for color reversal paper: to obtain prints from slides obtained from color reversal film, and to obtain further prints from prints. These are usually called direct prints, which are separate from systems that make prints from negative film.

Conventionally, in the case of this direct printing, color reversal photographic paper having different performances has been used for two types of printing. However, without using separate photographic papers, if the same color reversal photographic paper can produce prints with satisfactory finishing performance for both of the above two types, it can be used in both cases. It is advantageous and therefore such a photosensitive material is desired.

Originally, it was thought that it would be extremely difficult to obtain satisfactory finishing performance using the same color reversal photographic paper, since the performance of the two types of original images, slides and prints, differed from each other.

For example, in order to satisfy the finishing performance of a print from a slide, a soft gradation performance is required because the slide has a hard gradation, and conversely, to satisfy the finishing performance of a print from a print, it is necessary to print the original image. Since the contrast is softer than that of slide, high contrast performance is required.

Furthermore, in printing from prints, the original image is often a monochrome print, and there is a restriction that color deviations from white, neutral gray to black are not allowed.

Furthermore, since it is a color photographic paper, it is naturally required to have sufficient performance in terms of color reproduction.

Under these circumstances, a color reversal photosensitive material that can be used satisfactorily in both of the above two types has not yet been realized, and its development has not necessarily been sufficiently attempted.

Therefore, by solving the above-mentioned conventional difficulties, printing from slides and printing from prints can be done well on the same color photographic paper, and the reproducibility is improved, especially for white, neutral gray to black. It is strongly desired to develop a photosensitive material with good color reversal.

[Problems to be solved by the present invention]

As mentioned above, with the conventional technology, printing from slides and printing from prints can be done on the same color photographic paper, and the reproducibility from white, neutral gray to black can be satisfied. The technology has not yet been developed.

In order to solve the problems of the prior art, it is an object of the present invention to print from slides and print from slides on the same color photographic paper.
It is an object of the present invention to provide a color photographic material which can be constructed so that printing can be performed satisfactorily and which has improved reproducibility from white and neutral gray to black.

[Means to solve problems]

The object of the present invention is to provide a silver halide color reversal light-sensitive material having at least one each of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer and at least one colloidal silver-containing layer on a reflective support. Achieved by a silver halide color reversal photosensitive material, which has a maximum reflection density of 265 or more for yellow, magenta, and cyan, and a minimum reflection density of 265 or higher for yellow and the lowest for cyan. We were able to.

In the present invention, the maximum reflection density and the minimum reflection density can be obtained as follows. That is,
A color reversal photosensitive material is exposed to white light (white exposure performed using a photographic step wedge at 3200°), and a predetermined color reversal process, that is, a development process described in the Examples described later, is obtained. A characteristic curve can be created for the sample obtained from the maximum reflection density to the minimum reflection density.

In the above, the characteristic curve refers to the so-called D-1 layer gE curve often used in the photographic industry, in which the horizontal axis is log E (E is the exposure amount) and the vertical axis is D 1 degree).

In the color reversal light-sensitive material having a reflective support of the present invention, the measurement of the reflection density of a sample obtained by color reversal processing is described in "Fundamentals of Photographic Engineering (edited by the Photographic Society of Japan, Corona Publishing), J page 386."'45° annular incidence, normal direction observation method is used.

Furthermore, as a spectroscopic requirement for reflection density measurement, 5ta
A tusA filter is used.

In the color reversal photosensitive material of the present invention, the unexposed area corresponds to the maximum reflection density, and the exposed area corresponds to the minimum reflection density.

In the present invention, in a preferred embodiment to make the effects of the present invention more remarkable, the maximum reflection density is 2.5 or more and 2.5 or more.
It must be 8 or less. Also available are yellow, magenta,
The maximum reflection densities of the three cyan layers may be the same or different. However, if they are different, it is preferable that the difference between the layer with the highest concentration and the layer with the second highest concentration is within 0.1, and the difference between the layer with the lowest concentration is within 0.2. .

Further, as a preferable embodiment of the minimum reflection density, when a reflection support coated with a polyolefin containing a white pigment is used, the minimum reflection density excluding the support density is as follows:
Yellow is 0.05~0.11, magenta is 0.03~
0.07, cyan is in the range of 0.02 to 0.06, and the density difference between the three layers is 0.07 for yellow than magenta. It is preferable that O1 to 0.04 higher and cyan lower than magenta by 0.01 to 0.03.

In the present invention, the reflective support refers to an opaque to translucent support, such as paper, baryta paper, synthetic paper, laminated paper, coated paper, polyolefin coated paper, or a support containing white pigment. There are translucent and opaque plastic films. Particularly useful are paper supports coated on both sides with polyethylene containing white pigments and polyethylene terephthalate film supports containing white pigments. These supports may have a subbing layer on the photosensitive logging coating side and a backing layer on the opposite side.

In the present invention, the colloidal silver-containing layer is a layer containing colloidal silver such as black colloidal silver, red colloidal silver, yellow colloidal silver, etc., and the colloidal silver is usually preferably 0.
01g/rrr ~1. Og/n (, more preferably 0
．． 05 g/rrf to 0.5 g/rrf. The position of the colloidal silver-containing layer is not particularly limited, but in the case of a black colloidal silver-containing layer, it may be applied as an antihalation layer close to the reflective support, and in the case of a yellow colloidal silver-containing layer, it may be applied as a filter layer. It may be applied between a blue-sensitive layer and a green-sensitive layer, or between a green-sensitive layer and a red-sensitive layer.

In the present invention, it is preferable that the red-sensitive layer, green-sensitive layer, and blue-sensitive layer each consist of two layers having different sensitivities, and it is preferable that the high-sensitivity layer is located on the side far from the support. Further, it is preferable that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in order from the support side.

In the present invention, each photosensitive layer preferably contains a silver iodobromide emulsion. The coating amount of the silver halide emulsion is preferably within the following range in terms of silver. The unit is g/rr
It is f.

Low sensitivity red sensitive layer 0.19~0.26 High sensitivity red sensitive layer 0.10~0.14 Low sensitivity green sensitive layer 0.14~0.19 High sensitivity green sensitive layer 0.20~0.27 low Sensitivity blue sensitive layer
0.12-0.17 high sensitivity blue sensitive layer
0.20 to 0.27 Therefore, the total silver halide coating amount is preferably in the range of 0.95 to 1.3 g/n.

In the present invention, when a structure is adopted having a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer, each having a high sensitivity and a low sensitivity, the preferable configuration of silver halide used in each layer is as follows. For each layer, average particle size (um)/average legality content (
(mol%).

High sensitivity blue sensitive layer: 0.76-1.04/1.
7-2.3 Low sensitivity blue sensitive layer: 0.44-0.59
/3.1-4.2 High sensitivity green sensitive layer: 0.76-1.
04 /3.4-4.6 Low sensitivity green sensitive layer: 0.3
3-0.45 /3.1-4.2 High sensitivity red sensitive layer:
0.76-1.04 /3.4-4.6 Low anger red sensitivity layer: 0.38-0.58 / 3.4-4.6
The amount of silver in the photographic structure of the color reversal light-sensitive material of the present invention is preferably 2.0 g/rrf or less, more preferably 0.7 to 1.5 g/n (in terms of metallic silver). Here, the amount of silver in the photographic constituent layer refers to the total amount of photosensitive silver in the silver halide emulsion layer, as well as the amount of colloidal silver and non-photosensitive fine grain silver halide, if any. It is the amount of silver.

The silver halide emulsion used in the color reversal light-sensitive material of the present invention may be a monodisperse emulsion or a polydisperse emulsion.

In order to bring out the effects of the present invention more effectively, it is better to use a monodispersed emulsion. Here, the monodisperse silver halide emulsion is preferably one in which the weight of silver halide contained within a grain size range of ±20% around the average grain size d is 60% or more of the weight of all silver halide grains. , more preferably 70% or more,
More preferably, it is 80% or more. Here, the average particle diameter d is the frequency ni and di'' of particles having particle diameter di.
It is defined as the particle diameter di when the product n1Xdi' is the maximum (3 significant figures, minimum number of digits is 4 to 5).

The grain size referred to here is the diameter of 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 particle diameter or projected area on the print (the number of particles measured is negligible). (Assume that there are more than 1,000 discrimination items).

A particularly preferred highly monodispersed emulsion is one in which the standard deviation x 100 - breadth of distribution (%) When the breadth of distribution is defined by the average grain size, it is 20% or less. 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 by double jet method under control of Ag and pH. Particularly preferred manufacturing methods include JP-A-58-49938 and JP-A No. 6
Publications such as No. 0-122935 and No. 5946640 can be referred to.

As the silver halide emulsion used in the color reversal 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 emulsion can be chemically sensitized by conventional methods and optically enhanced to a desired wavelength range using an enhancement 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.

The color reversal light-sensitive material of the present invention has at least one green-sensitive layer, one blue-sensitive layer, and one red-sensitive layer, and each light-sensitive emulsion layer may contain a color-forming coupler as appropriate.

The preferred amount of the color-forming coupler added is, per square meter of the color reversal light-sensitive material, the blue-sensitive layer contains, for example, a pivaloyl-type yellow coupler of 0.91 to 1.24 mmol, and the green-sensitive layer contains, for example, a pivaloyl-type yellow coupler, for example, a pyrazolone-type or pyrazoloazole coupler. Type magenta coupler is 0.35-0.5
It is preferable that the red photosensitive layer contains, for example, a phenolic cyan coupler in an amount of 0.66 to 0.90 mmol.

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 and sterilizing agents, can be used.

Furthermore, the color reversal photosensitive material of the present invention can 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 color reversal photosensitive material of the present invention includes a formalin scavenger, a fluorescent brightener, a matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retardant, and a bleach accelerator. can be added.

To obtain a dye image using the color reversal photosensitive material of the present invention, after image exposure, for example, commonly known processing for color reversal photographic paper can be used, such as Ectochrome R-3 manufactured by Eastman Kodak Company. Processing can be used.

〔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 shown in g/po. 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-20,10 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 color enhancer (S-1,5-2)
Silver iodobromide emulsion spectrally sensitized with (AgI4.Q mol%,
Particles with an average particle size of 0.42μ and particles with 13.9 mol% Ag and an average particle size of 0.27μ are mixed at a molar ratio of 8:2)
0.23 Gelatin third layer (second red-sensitive layer) Cyan coupler C- Cyan coupler C- Anti-fading agent A- Anti-fading agent A- Color mixing inhibitor AN High boiling point solvent O- Red sensitizing dye (S-1゜Silver iodobromide emulsion (Ag diameter 0.9μ) Gelatin No. 4N < 1st intermediate N) 0.81 1 0.11 2 0.056 1 0.0B5 2 0.043 1 0.0034 1 0, 13 Spectral sensitization with S-2)! 4.0 mol%, average particle 0.13 0.90 Color mixing inhibitor AN-10,020 Color mixing inhibitor
A N -20,060 High boiling point solvent 0-2
0.13 gelatin
0.90 5th layer (first green sensitive layer) Magenta coupler C-30,12 Anti-fading agent A-30,034 Anti-fading agent
A-40,0056 Five-color anti-fade agent A-5
0,071 Color mixture prevention agent A N -10,004
6 High boiling point solvent 0-2 0.092 Silver iodobromide emulsion (A
gI 4.0 mol%, particles with an average particle size of 0.42μ, and Ag
12.0 mol% particles with an average particle size of 0.27μ mixed at a molar ratio of 8:2) 0.17 Gelatin 0.93 6th layer (
2nd glaucoma 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 (S
-3) Silver iodobromide emulsion spectrally sensitized (Ag 14.0 mol%, average grain size 0.9μ) 0.24 Gelatin 0.92 Seventh layer (
2nd intermediate layer) Yellow colloidal silver o, 15 Color mixing inhibitor AN-10,011 Color mixing inhibitor A
N -20,034 High boiling point solvent 0-2
0.070 Gelatin 0
．． 90 8th layer (first blue sensitive 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! 2.0 mol%, grains with an average grain size of 0.9μ, and AgT 4.0 mol%, average Particle size 0
．． 42μ particles mixed at a molar ratio of 2:8) 0.15 Gelatin 0.95 9th layer (
2nd blue sensitive layer) Yellow coupler C-40,53 Anti-fading agent A-10,21 Anti-fading agent A-60,11 Color mixing inhibitor AN-10,016 High boiling point solvent
0-3 0.11 Blue sensitizing dye (S-4)
Silver iodobromide emulsion spectrally sensitized with (Ag! 2.0 mol%,
Average particle size: 0.9μ) 0.24 Gelatin 1.06 10th layer (ultraviolet absorption layer) Ultraviolet absorber U-1,0,45 Ultraviolet absorber U-20,15 Color mixture prevention agent AN-10,033 Boiling point solvent
0-3 0.36 gelatin
1.74 Eleventh layer (protective layer) Gelatin 0.50 However, in addition to the above, it contains a surfactant, a hardening agent, and an anti-irradiation dye.

-1 m2 Shit I 5 -6 Su■ Di-2-ethylhexyl phthalate-2 Di-isodecyl phthalate-3 Di-nonyl phthalate-1 H 0■ aHw(t) SO, Na used in each photosensitive layer The silver halide emulsion is prepared by mixing a silver sulfate solution and a halide solution by a so-called double jet method, and is a potato-shaped polydisperse emulsion. After desalting and washing with water, each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate, and was then subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid, and ammonium thiocyanate. , 7-chitrazaindene, and 1-phenyl-5-mercaptotetrazole were added to perform chemical ripening.

(Development process) First development (monochrome development) 1 minute 15 seconds (38°C) washing with water 1 minute 30 seconds Light fog 100 eux or more 1 second or more Second development (color development) 2 minutes 15 seconds (38°C) washing with water
45 seconds bleach fixing 2 minutes (38°C) washing with water 2 minutes 15 seconds 1st stage (! & solution) Potassium sulfite 30.0g Sodium thiocyanate 1.0g Sodium bromide 2.4g Potassium iodide
8.0 ■ Potassium hydroxide (48%)
6.2mf potassium carbonate
14g sodium bicarbonate 12
g1-phenyl-4-methyl-4-hydroxymethyl-
3-Pyrazolidone 1.5g Hydroquinone monosulfonate 23.3g Add water
1.0i (pH 9,65) <Color developer> Benzyl alcohol 14.6ml Ethylene glycol 12. Potassium carbonate (anhydrous) 26g Potassium hydroxide
164g sodium sulfite
1.6g36-cythiaoctane-1.8-
Diol 0.24g Hydroxylamine sulfate 2.6g4-N-
Ethyl-N-β-(methanesulfonamidoethyl)-2
-Methyl-p-phenylenediamine sesquisulfate Add 5.0g water
1.01 (p Hlo, 30) <Bleach-fix solution> 1.56 molar solution of ammonium salt of ethylenediaminetetraacetate diiron complex 115 mff1 Sodium metabisulfite 15.4 g Ammonium thiosulfate (58%) 126 mj2 Mercapto 1°2° Triazole 0.4g Add water to 1.0! (pH=6.5) Sample-1 thus obtained was passed through an optical wedge, exposed to white light, and subjected to the reversal development process described above.

The maximum reflection density (hereinafter referred to as D max) and the minimum reflection density (hereinafter referred to as Dmin) of the obtained color image were measured using a reflection density system (Status A).

However, the density of the reflective support is subtracted.

Various Dmax shown in Table 1 were obtained in the same manner as Sample-1, except that the coating silver amount and coupler content of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were changed as shown in Table-1.
, Dmin color reversal image samples (sample-2~
Sample-8) was obtained.

Moreover, the above-mentioned samples 1 to 8 were exposed to light using a color slide in a printer so as to obtain an appropriate density. The color slides used here were taken with Eastman Kodak's Eftafrom 64 Professional Film, a color reversal film, and Macbeth's Macbeth Color Checker and multiple black and white charts with different reflectances. Specified development process (name E-6)
It was created by processing. These samples were subjected to the reversal development process described above, and the resulting color images were visually evaluated for reproducibility from highlights to shadows under a genuine color fluorescent lamp for color evaluation. ×(
We ranked them as follows: "inferior".

The results obtained are shown in Table-1.

Note that these evaluations are average ranks evaluated by multiple people.

As shown in Table 1, sample 5, which is a comparative example, lacked shadow tightness and was ranked low. Samples 6 to 8, which are also comparative examples, had an unpleasant cyan-magenta color tone, especially in the highlighted areas, and were ranked extremely low.

On the other hand, Samples 1 to 4 according to the present invention had excellent depiction of highlights to shadows and were ranked as good.

Example 2 Samples 1 to 8 obtained in Example 1 were exposed to light using a reflective original using a copy printer so as to achieve proper density.

The reflective originals used here are various photographic originals printed on commercially available monochrome photographic paper.

These were subjected to the above-mentioned reversal development process, and the resulting color images were visually evaluated in the same manner as in Example-1.

As a result, as in the case of the slide manuscript of Example-1,
In the case of reflective originals, Sample-1 to Sample-4 according to the present invention had excellent ability to depict highlights to shadows, but Samples-5 to Sample-8, which are comparative examples, had excellent ability to depict highlights and shadows. It was ranked extremely low due to its unpleasant color tone and poor shadow depiction.

As is clear from the above, the present invention makes it possible to obtain images with excellent descriptive power for both slides and reflective originals.

〔Effect of the invention〕

As described above, according to the present invention, there is provided a color photographic photosensitive material which can be configured to be able to print from slides and from prints well, and which has improved reproducibility from white, neutral gray to black. material can be provided.

Claims (1)

[Claims] 1. A silver halide color reversal photosensitive material having at least one each of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer and at least one colloidal silver-containing layer on a reflective support. , the maximum reflection density of yellow, magenta, and cyan is all 2.
．． 5 or more, and has the highest minimum reflection density for yellow and the lowest for cyan.