JPS63128337A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain reproducibility of faithful tone against an original image at from a low photographic density range to a high photographic density range by specifying the means value of point gamma in each points within the exposure range corresponding to the value de the specific condition in the characteristic curve of the titled material. CONSTITUTION:The mean value of the point gamme in each points within the exposure range corresponding to the value of 0.3-0.7 in the characteristic curve of the titled material is 1-3. Said value of 0.3-0.7 is calculated by dividing the photographic density value which is substracted with min. photographic density value from the developing density value by the max. photographic density value in the characteristic curve of the titled material. The variation range of said mean value of the point gamma is specified so as to be within + or -15% with respect to the mean value of the point gamma at each point within the exposure range. And, the mean value of the point gamma at each points within the exposure range corresponding to from >=0.05 to <0.1 of the photographic density value substracted the min. photographic density from the development density value is specified to >=0.2. Further, the mean value of the point gamma at each points within the exposure range corresponding to 0.1-0.2 of the photographic density value substracted the min. photographic density value from the development density is specified to >=0.3. Thus, the reproducibility of the faithful tone against the original picture at the broad range from the low photographic density range to the high photographic range is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention is directed to a positive viewing device that can be viewed in reflection, semi-transmission, and transmission.
This invention relates to positive silver halide photographic materials.

More specifically, the present invention relates to a silver halide photographic material for directly obtaining a positive image with excellent tone reproducibility from a transmission or reflection original having a positive image.

(Prior Art and Problems to be Solved by the Invention) Conventionally, there are many methods for obtaining a reflective, semi-transmissive or transmissive positive image (copy) from a reflective or transmissive positive image (original). method is known. For example, there are commonly used PPC copying methods, CCP copying methods, color copying methods using electrophotographic sound, thermal transfer methods, etc. Also, examples using silver halide photoreceptors include black and white reversal paper, white 8 Dubrid John Film,
Black and white autopositive paper, black and white autopositive film, color reversal paper, color autopositive paper, color reversal film, color autopositive film, color diffusion transfer paper (film), silver dye bleaching method (film/
Paper) Dry silver color paper (film)
and so on. These are referred to as positive-positive types in this patent.

By using these methods and materials, a positive image can be directly obtained without using an intermediate medium such as an internegative film.

These methods are easier to work with than methods that use intermediate media such as internegatives.
Since only seven printings are required, there is little deterioration in image sharpness, and theoretically it is possible to obtain a copy image with good surface quality.

However, although these conventionally known methods are suitable for copying images such as text, they do not have sufficient performance to obtain copies of continuous-tone pictorial images such as photographs and paintings. Didn't show everything.

In other words, the obtained positive image may lose its whiteness when compared to the positive image of the original, or it may not be possible to obtain a sufficiently high density black, or the result may be sharper than the original. It had seven or several defects.

Various attempts have been made to obtain faithful reproductions of transparencies and reflective positives. For example, optical flare in printers (or copy machines) has been found to be a factor causing image quality deterioration, and attempts have been made to reduce this flare as much as possible. For example, making the optical system matte black or designing mirrors and lenses with less flare. Also, for photosensitive materials, the HD curve is
In order to compensate for rare occurrences, efforts were made to design the high-density side with a high gamma.

However, there are only a few proposals for realizing faithful reproduction in positive-positive photosensitive materials. For example, West German patent/
, /, 2/ , I/170, U.S. Patent λ.

6gg, jj No. 31, British Patent 1/3, 6g No. 7, 73
2.1. In the ≠ issue, etc., a method is described in which two or more emulsions are used in two layers in order to widen the photosensitive area, thereby obtaining gradations with a wide linear area (wide latitude).

In addition, U.S. Patent No. 30/, 2≠λ describes a method for using two types of emulsions with a narrow grain size distribution and almost the same average grain size in a color reversal reflective photosensitive material by changing the desensitization level of each emulsion. is stated.

By applying the techniques described in these publications to other positive-positive type photosensitive materials, it is possible to produce photosensitive materials that faithfully reproduce a wide density range of an original. However, although these techniques can reproduce a wide density range, they are unable to depict the highlights of an image or reproduce the white background, which are most important for copying. That is, the density of the white background has increased to completely white gray, and the contrast of the original image in the highlight area has been compressed, resulting in low contrast.

To improve the tone reproducibility of highlighted areas in copying,
In JP-A No. 6-/0.2, two emulsions with different sensitivities are used, and the low-sensitivity emulsion layer is placed closer to the support, and the outer shell of the silver halide grains of the low-sensitivity emulsion is further coated. It has been proposed to use all reversal photosensitive materials, which are characterized by not containing A g and I . In this proposal, these aspects will reduce fI.
The purpose is to reduce the contrast in the k degree area. This is contrary to the purpose of the present invention, which will be described later, and if it is used with other positive-positive type W# source materials, the tone reproducibility of white backgrounds and highlights will be impaired. Furthermore, regarding the tone reproducibility of highlights, JP-A-1. /-30/33, a color reversal reflective material with a color density of 0.3 to θ0.2 and an absolute value of point gamma of 0°3 or more at each point within the M light range is used for transmission positive originals and reflective positives. It is stated that it is suitable for printing from both sides of the original picture.

Although this method is certainly superior to other conventionally known methods as a method for achieving faithful reproduction of original images in positive-positive photosensitive materials, it is insufficient for the purpose of the present invention. It wasn't.

That is, the object of the present invention is, firstly, to provide a positive-positive type halogen that can produce reflective, semi-transmissive, or transmissive reproductions that are more faithful to the original, regardless of whether the original is a transparency or a reflective original. An object of the present invention is to provide a silver oxide photographic material.

A second object of the present invention is to provide a positive-positive type silver halide photographic light-sensitive material that achieves faithful reproduction of tone from two original images from a low density region to a high density region.

A third object is to provide a photographic material that achieves improved whiteness when a reflective, semi-transmissive or transmissive copy is made from an original image having a white background.

(Means for Solving the Problems) The object of the present invention is to provide a positive-positive silver halide photographic material comprising seven or more photosensitive layers coated on an opaque, translucent or transparent support. 1) In the characteristic curve, the average value of point gamma (5 ) is 1. θ~3.0
, and the variation width is within ±lj% of the average value of point gamma within the exposure range, and 11) The density value obtained by subtracting the lowest density from the developed density corresponds to 0.0t or more o, less than i The average value (B) of point gamma at each point within the exposure range is 002 or more, and 1ii) The point at each point within the exposure range corresponds to a density value of 0.1 to O7λ by subtracting the lowest density from the developed density. Average value of gamma (
This was effectively achieved using a silver halide photographic material characterized by C) of 0.3 or more. Further, in the photosensitive material of the present invention, it is preferable that the value of the relational expression between A and C: (A 2 ×C) is O1g to IO.

The "% curve" as used herein means, as shown in the solid line graph in Figure 1, the horizontal axis is JltogE (E is the exposure amount)
It is the so-called D-4ogE curve plotted with D (concentration) on the vertical axis, for example, T, H, Ja
mes edition, “The Theory, of t
he Photographic Pror.
s'' edition, pages 301-30.

Also, "point gamma"
a) J is defined on page 30.2 of the above publication, point-gamma=dD/dj! og
E, which represents the differential value at any point on the characteristic curve. For the meaning of this value, see R8 Luther,
Traus, FaradaySoc, /ri.

3170% (/ri,!3), L, A, Jones,
J.

It is discussed in Franklin In 5t, No. 227, page 7 (/ri3ri).

dD/dj! on the same graph as the D-flogE curve! og
The broken line graph in FIG. 1 shows the E-AOgE curve. As you can see from this graph, D-It o
The point gamma is 0 in the exposure range corresponding to Dmax (i large density) and Dmin of the gE curve, and the gradation part has values other than 0 at each point.

Here, D (!! degree) to obtain D-1,ogB curve
- As a light source, a color temperature of 3.2000 Kf was used, and R
, G%B respectively A#4tnm, j4'Anm, 4136n
The monochrome three-color density determined using a metal interference filter having an absorption peak at m was used. In the case of black and white photosensitive materials, density values obtained using a J-Hiro Anm filter were used.

[Average value of point gamma J()n trust] in the present invention can be calculated as follows.

Since point gamma is a function of fl, og E,
dD/dJ! When expressed as ogB = f(AogE),
[Average value of point gamma in the region where ogE is from a to b (a<b)" is given by:

The exposure schedule in the present invention is defined as the two log H values at which the point gamma is essentially O, namely Dmax and D.
Difference in AogE value given by mini Δ11. It can be expressed as ogE. A large exposure radius indicates that the material is sensitive to light that can be identified over a wide range of light intensity.

Here, the grain size of silver halide is the grain diameter when the grain is a sphere or a shape that can be approximated to a sphere, and when the grain is cubic, it is expressed as principal x f [Σ, and the projection of each individual grain. This is a value calculated from the area. C, E for details on particle size measurements.

Mees and T. H. James 1'-The Th
eory of the Photographic
Pror, ess J 3rd edition 3A ~ 4L3 pages C/
5' Oto Oto Year) Published by MeMi l a n, edited by the Photographic Society of Japan [Fundamentals of Photographic Engineering (Silver Halide Photography Edition) J, 27
7~. 27g page (1997) Published by Corona Publishing, etc.
The report in Vol. 7, pages 330-33f of IJ may be referred to.

Below, the configuration of the present invention will be explained in more detail.

The conditions for achieving the purpose of the present invention can be summarized in the following three points.

(a) In order to faithfully copy the positive original picture, the intermediate density region of the characteristic curve should be as close to the ItjM line as possible, and its slope (contrast) should be 1 to 3.

(In order to improve white blur on the q copy image, the contrast ratio in the low density region of the characteristic curve should be set to a value based on a theorem.

(c) More preferably, there is a certain relationship between the contrast of the intermediate density area and the low density area, and the lower/closer the contrast of the intermediate density area is, the higher the contrast of the low density area is.

The above (a), (b), and (/'l) will be explained in more detail.

(a) The intermediate density region of the characteristic curve refers to the density region where the value obtained by subtracting the minimum density from the developed density of the characteristic curve and dividing it by the maximum density corresponds to 0.3 to 067. Making the characteristic curve in the intermediate density region a straight line with a total slope of / to 3 means that the contrast in the intermediate density region of the original image is amplified at a constant rate and reproduced. This amplification is necessary to faithfully reproduce the original painting. This is because the optical flare of various printers, the absorption peak of the coloring material used in the original image, and the difference between the spectral sensitivity of the light-sensitive material, etc.
This is because the contrast on the print is completely reduced, and it is necessary to correct this for faithful reproduction.

(The contrast in the low density region of the E% concave curve is as follows: the density value is θ from the lowest density, OJ or more and less than 0./, and from 0°/ to 0.
．． It has been found that it is good to define the point gamma value in one region of 2. The reason why we specified two regions is that firstly, the low concentration region is more important, and secondly, the low concentration region is more important.
This is because it is insufficient to specify one area. Tokukai Show 1
Specifying contrast in a single density range of 0.3 to 0.2, such as r/-30/3j, and in a higher density range than that of the present invention is insufficient to demonstrate the effects of the present invention. It turned out to be.

(／→Furthermore, we have found that faithful reproduction requires a certain relationship between the contrast of the medium-density region and the low-density region. That is, the contrast of the medium-density region is close to /, which is closer to the contrast of the original image. In such a design, in order to faithfully reproduce the tone in the highlight area, the contrast of the highlight must also be close to This is because a rule has been found that it is better to set the contrast of highlights to a slightly lower level in order not to lose the tone reproduction of the area.In order to fully satisfy this relationship, the average value of point gamma, A formula consisting of A and C: The value of A 2 × C is O0
It is preferable to design the sensitive material so that it falls within the range of g to IO.

These requirements can be achieved using several methods, including but not limited to:

First, this can be achieved by using a polydisperse silver halide emulsion in the same color-sensitive layer, or by using two or more silver halide emulsions mixed in the same layer or separately in separate layers. Here, the polydisperse silver halide emulsion refers to an emulsion in which the grain size of 3% or more of the grains is ±30 inches or more of the average size.

Second, when the above-mentioned polydisperse silver halide emulsion or two or more emulsions are all used, specific heavy metals are added during grain formation or physical ripening of the silver halide emulsion that shares the low concentration side of the characteristic curve. This is achieved by incorporating

Thirdly, this can be achieved by containing a specific organic compound described below in the photosensitive layer containing the silver halide emulsion. When there are two or more layers having the same color sensitivity, this can be achieved by containing a small amount of this compound (both in the low concentration layer of the characteristic curve).

≠ As a silver halide emulsion, if the grain size of the silver halide grains is J% or more of the average grain size, 20%
This is achieved by using monodisperse emulsions that are within When using more than λ of the same color-sensitive emulsions, this can be achieved by using this monodisperse emulsion in a layer that shares at least the low density side of the characteristic curve.

The above 1 to <zy may be combined in any combination.

The specific heavy metals mentioned above are rhodium, cadmium, lead, thallium, iridium, copper, iron, and zinc.

These metals can be contained in the form of metal salts by coexisting them during the formation of silver halide grains or during physical ripening. These heavy metals may be used alone or in combination of two or more. The amount used is 10-2 to 10 mol based on silver halide. More preferably, the amount is 10" to 10 mol. Particularly preferred heavy metals are rhodium, cadmium, lead, and thallium.

The above-mentioned specific organic compound is a compound represented by the following general formula (]).

Xl, X2, X3, X4, and X5 are hydrogen atoms, substituted or unsubstituted alkyl groups (preferably 1 to 20 carbon atoms, such as methyl group, t-amyl group, t-octyl group, octadecyl group, etc.), alkylthio Group (preferably 1 to 1 carbon atoms)
, 201 (e.g. methylthio group nato), sulfo group, sulfoalkyl group (preferably 1 to 1 carbon atoms, !01 e.g. sulfopropyl group), amide group, hydroxyl group, sulfonamide group, carbamide group, carbonyl group (acyl group, ester group, etc.).

These compounds are described in US Pat.
JP-A No. 60-/72.0≠θ, JJ-G3Jλ/, No. 3-10-10, J7-. It is described in No. 22237, etc.

Particularly preferred among these compounds are those represented by the general formula (]a
) can be shown.

Here, R1 and R2 are a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a carbon number of 1 to 20, for example, a methyl group,
(1)-octyl group), sulfo group. Furthermore, R□ and R
The total number of carbon atoms of 2 is preferably 7 to λO.

Specific examples of preferred compounds of general formula (1) are listed below, but the invention is not limited thereto.

H -/za- 0H Ul'i -, 2/- 〇H -2λ- These compounds may be dissolved in an alkaline aqueous solution and incorporated into a photosensitive material, or they may be dissolved in a high boiling point oil and made into an emulsified dispersion. It may be included.

These compounds are preferably used in a coating weight of 10<-4 >/y/m<2>.

The 710 silver emulsion of the present invention, which is characterized in that the grain size of 3% or more of the silver halide grains is within ±30% of the average grain size, is prepared, for example, by the following method. Ru.

Seven of them are methods using the so-called Chondrold double jet method, in which a simultaneous mixing method is used during the reaction of soluble silver salt and soluble halide, and the pAg'r in the liquid phase in which /% silver halide is produced is constant. This is the way to keep it. By keeping the value of pAg constant during this process, it is possible to obtain the required regular crystalline form and to achieve a particle size distribution with uniform particle size (monodisperse).

Another effective method for achieving the above-mentioned silver halide grain size distribution of the present invention is a method using a silver halide solvent during the formation of all grains.

For example, ammonia, rhodanpotash, rhodanammonium, thioether compounds (e.g., U.S. Patent No. 3゜j7/, 1
No. 37, No. 3, 3; 711L, No. 62g, No. 3, 7
0 μ, No. 730, same No. ≠, 2 7. 3rd issue, 3rd issue,
, 271.3717, etc.), thione compounds (for example, JP-A-Sho!; 3-/IIμ3/ri, JP-A-Sho!; 3-/IIμ3/ri, j3-OtsuμOg,
Same 3! ;-77737, etc.), amine compounds (for example, %Kaishoj≠-1007/7, etc.).

For the purpose of the present invention, particularly preferably used solvents are those described in JP-A-33-G No. Of, pages 3 to ≠, and JP-A-J, S-77737, Hiroshi. Thiourea compounds; US Pat. No. 3. ．． 27/.

No. 137, page 77, No. ≠, λri 7. ≠No. 37, page 3,
4≠,,297. ≠No. 37, pages 3-6, same≠.

276.37, pages 2-3; JP-A-Sho! ;3-/≠≠It is a thione compound described on page 3 of No. 3-2.

The amount of silver halide solvent used in the present invention can vary widely depending on the desired effect, the nature of the compound utilized, etc. Generally silver halide 1 and a half mol ~ 10 mol ~ λ, Ex
70 mol is particularly preferred.

In the present invention, the silver halide solvent is added at least/in a step selected from the formation of precipitation of silver halide grains and the subsequent physical ripening during emulsion production.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing less than about 30 moles of silver iodide. Particularly preferred is silver iodobromide containing from about 0.3 mole percent to about 70 mole percent silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. Also, mixtures of particles of various crystal forms may be used.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of up to about 10 microns.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method. '1. Emulsion manufacturing
Preparation and Types)'
It is possible to follow the method described in vol. 7, p. 6≠d.

Further, tabular grains having a spectral ratio of 3 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (
Gutoff, PhotographyC8CienC
e and Engineering), Volume 1≠, 2
41g~, 2j7 pages (/70 years); US Patent No. ≠, ≠
3≠,,2.2A issue, same≠,≠/ll, 310 issue, same t
, μ33, 0 Hiro♂ issue, same≠,≠39. ．． S-, 26-20 and British Patent No. 2. //2. /3; It can be easily prepared by the method described in No. 7.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

These emulsions include European patent (EP) 076≠76OA
Also included are direct positive reversal emulsions such as those described in 2.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization.

Additives used in such processes are described in the aforementioned Research Disclosure magazine, /16/71g3 and /16/17/6, and the relevant parts are summarized in the table below. Ta.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

-, 27- / Chemical sensitizer page 23 A≠g page right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23-2I/ 6I7tg page right column ~
Super sensitizer Right column on page 2 Brightener 2μ Page j Anti-fogging agent 2μ~2! Page 6 Pig Page Right Column and Stabilizer 6 Light Absorber, F, 2! -Page 26 6μ right column~
Ilter dye tSO left column UV absorber 7 Anti-stain agent 2! Page right column Otsu SO page left to right column ♂ Dye image stabilizer, 2! Page hardener, page 26 Otsu, 5! Page left column 10 Binders, page 26 Same as above // Plasticizers, lubricants, page 27 6JO right column/, 2 Coating aids, Tables 26-. Page 27 Same surface activator / 3 Static prevention - Page 7 Same as above Stop agent Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure magazine, 16/764t3. -C-G. As dye-forming couplers, the three subtractive primary colors (i.e., yellow-magenta and cyan)
Couplers provided by color development are important, and specific examples of diffusion-resistant, hydrophobic, g-equivalent or 2-equivalent couplers are given in the above-mentioned ``Research Disclosure'' magazine /l61
In addition to the couplers described in the patents described in Sections 1-C and D of 76≠3, the following can be preferably used without invention.

The present invention also includes research disclosure magazine /16/
Colored couplers described in Items 76≠3, ■ to G, 477
DII-t couplers described in items ① to F, where 6≠3, can also be used.

Color reversal film (or translucent film,
) has at least 7 or more blue, red, and green photosensitive layers,
In addition, auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, and a back layer are provided as appropriate. Color reversal film (or translucent film, paper) is available in "Research Dinu Closure" magazine, Volume 776 /16/76μ3 (/7
Pages 2g to 2ri of 72/F) and the same, Volume 17/16
Development processing can be carried out by the usual method described in the left column to right column of page Otsuj/page of /17/6 (/7/year/month).

A direct positive type photosensitive material can directly obtain a positive image by performing black and white development or color development seven times without the need for a reversal (second) development process as in a reversal processing type photosensitive material. Silver halide emulsions suitable for direct positive light-sensitive materials typically include emulsions in which silver halide grain surfaces are prefogged and internal latent image emulsions, the latter of which are photofogged emulsions and emulsions that use a nucleating agent. type is known. Particularly excellent in sensitivity are internal latent image type silver halide emulsions. In the case of a black-and-white photosensitive material, the direct development process for a positive type photosensitive material generally includes a process of development, washing, washing, and drying. In the case of color sensitive materials, the process basically consists of color development, washing with water, bleaching, fixing, washing with water, stabilization, and drying. Some of these steps can be omitted or replaced with rinsing. Also, several steps may be performed simultaneously in the same step, such as bleaching footwear. Furthermore, fogging exposure can be applied immediately before or during the development process (color development process) in order to improve the reversal characteristics.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, a silver halide emulsion of 005 to 39
7m", exposed to light for a fixed time of 0.0 to 70 seconds, and developed in the following developer A (internal type developer) at /℃ for 3 minutes. Normal photographic density measurement. The maximum density measured by the method is the maximum density obtained when all silver halide emulsions coated in the same amount as above and exposed in the same manner are developed in developer B (surface type developer) shown below at 20°C for 6 minutes. Preferably, the concentration is at least 5 times greater, more preferably at least 70 times greater.

Internal developer A Metol 2y Sodium sulfite (anhydrous) Ta01 Hydroquinone and 1 Sodium carbonate (-water salt) 32, 39KBr
3 jEKI
O, add 3y water
/L surface developer B Metol, z, ;yL-ascorbic acid 10 fN a B O-
4' H20J J FKBr
/ P Add water
/ As a specific example of a λ internal emulsion, for example,
U.S. Patent No. 1. Jri 2, 2! ;No. 0, Special Public Show 3; Do-j
≠No. 37, same! ;I-3! ;36, 60-331
No. 2, Tokukai Sho J, No. 2-/jAg/No. 4, No. 7-7 Tatag θ, No. 4! Conversion type silver halide emulsion described in the specification of No. 1-70λ27 and an emulsion with a shell attached thereto, US Pat. No. 3,76/, 271. No. 3, 1. ! ;No. 0.637, 3゜223,,!
j/No. 3, same ψ, 03! ; ,/do3, same≠, 3rij
, ≠7g, same amount, ≠3/ , 730, same amount, 301
7-,! ; No. 70, JP-A No. 33-602.22, same J
A-226g No. 1, same! ? -, 34t0 on 20th, 6th
0-10';/Otsu≠/ issue, 6/-3/37, special application in 1937. /-36≠λ issue, Research Disclosure magazine scraps! 3310C/Rido 3rd year//month issue) P, 23 Otsu,
Same/16/g/jj! ;(Published in July, 2016) lz6
Mention may be made of the internally metal-doped core/shell type halogenated scissor emulsions described in the patents disclosed in US Pat.

Heat-developable photosensitive materials are well known in this technical field, and for information on heat-developable photosensitive materials and their processes, see, for example, pages 333 to 33 of Basics of the Photographic Industry (published by Corona Publishing Co., Ltd., 1977); Information page, Nebretsu, ``
Handbook for Photography Professionals”
7th edition (Nebletts, Handbook o
f Photography and eprograp
hy 7 th Ed, ) Van C Nostrand
Reinhold Company (VanINostran)
32-3 of d Re1nhold Company)
Page 3, U.S. Patent No. 3. /, S2. riO≠ No. 3゜30
1.67g No. 3, 3 Octopus, 020 No. 3, ≠, 5
No. 7.07.3, British Patent No. 1, /3/.

No. 101, No. 1. /1.7.777 issue and Research Disclosure magazine /ri7g June issue~/j page (RD-/70.27), European Patent Publication No. 76, ≠7!
No. 7, No. 036, Tokukai Shojdo, 2gri No. 2g,
It is disclosed in the same issue No. 3g-26oog.

Further, regarding the method of forming a positive color image by the photosensitive silver dye bleaching method, for example, see Research Disclosure magazine / 1976 issue, pp. 30-32 (Kuri-hari 33), 1976 / 2 Monthly issue/≠~7.5 pages (
R, D-/j, z, z7), 34t- Useful dyes and bleaching methods are described, such as in U.S. Pat.

In addition, methods for forming positive images using the diffusion transfer method include the silver salt diffusion transfer method, which forms a complete black and white image, and the color diffusion transfer method, which forms a color image.The latter further uses a surface latent image type silver halide emulsion. There are two main types: those using direct positive silver halide emulsions (internal latent image type emulsions). Furthermore, the color image forming materials (coloring materials) used in combination with these emulsions may be dye developers, U.S. Pat.
As disclosed in No. 377, positive coloring materials represented by END compounds and negative coloring materials represented by couplers and redox compounds that release diffusible dyes can be used.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (e.g. polyethylene, polypropylene, ethylene/butene copolymer), gold-coated or laminated paper, etc.

In addition, a support having a surface provided with a metal foil film or a packed layer of metal light splitting particles to provide specular reflection or second type diffuse reflection (for example, Japanese Patent Application No. A/-/1.Dog00) 61-/6
g10/, etc.). The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

(Example/) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Color photographic materials 101 to 103 were prepared by applying the following first to g layers onto a polyethylene terephthalate film having a thickness of ♂O microns. The layer structure and the materials on each layer are shown below.

Color photographic materials 1011-//3 were prepared by coating the following 1st layer to 1st/layer on the same support.

The layer structure is shown below.

Here, the specific compound names of the materials represented by (*) in the above layer structure are as follows. These are samples 101~/
Commonly used in /3.

Oil-soluble components such as couplers and anti-fading agents used in each layer are dissolved in the coupler solvent shown in the table and an auxiliary solvent such as ethyl acetate, and then mixed with a gelatin solution in the presence of an emulsifier such as sodium alkylbenzenesulfonate. The mixture was mixed, mechanically mixed and emulsified using a mixer, and added to the coating solution.

*/! ;-Chloro-λ-(2-hydroxy-3-t-butyl-j-octyl) *λ Trinonyl phosphate*3 2. ,! ;-Disendary octylhydroquinone*t Triethylammonium 3-[λ-(3-benzylrhodanine-j-ylidene) -3-benzoxazonyl]propanesulfonate*j α-pivaloyl-α-[2,t-dioxo −／
-benzyl-3-ethoxyhydantoin-3-yl)-2-chloro-3-[α-2,≠-di-milphenoxy]butane-mido]acetanilide*4. 2. J-Ditertiary octylhydroquinone *7 Phosphoric acid-〇-cresyl ester *3;
! ;'-diphenylterethyl-3゜3'-disulfopropyloxacarbocyanine sodium salt *ta /-C2,II, 6-1-lichlorophenyl)
-3-[λ-chloro-3-tetradecanamide]anilino-2-pyrazolino-j-one*10 3,3.3',3'-tetramethyl-sub.

Otsu 4/,,;/-Tetrapropoxy-/,/'-bisspiroindan*// Di[l-hydroxy-3-t-butyl-j
-Methylphenylcomethane*/2 2.3-ditertiary-hexylhydroquinone*/3 Phosphoric acid-trioctyl ester*/≠ Polyethyl acrylate*/3 Triethylammonium 3-[:,2-(,2
-C3-(3-sulfonatopropyl) naphtho(/,,2-d) thiryozoline! -ylidenemethyl]-/-butenyl) -3-nat(/,,!-d)thiolino]propanesulfonate*/6! ;、! ;'-dichloro-3,3'-di(3
-Sulfobutyl)-terethylthiacarpodianine sodium salt*/7. 2-(d-(2,≠-di-t-acylphenoxy)butaneromido]-hiro,6-cycloj-methylphenol*/I 2-(2-hydroxy-3-8ee-butyl-,5-t -)-y-ruphenyl)benzotrizolezole*/tadioctyl phthalate In addition to these, each coating solution contains surfactants, thickeners, -t≠
- Contains hardeners.

The silver halide emulsions used in each subtractive color layer are mixed in two stages on one side, two stages on both sides, and have the characteristics shown in Table 1.
Silver potential control for mixed sound on both sides (to prepare) 14'j-,'tb- Each sample obtained was exposed to light using a continuous wedge of % silver evaporation, and subjected to the color reversal process described below. did.

Processing process first development (black and white development) 3g℃ 73 seconds water washing
3g℃ TaQ second inversion exposure
1001ux color development
3g℃ 133 seconds water washing 3g
℃ lA 3 seconds bleach fixing 3g0C/
, 20 seconds washing with water 3g℃ /33
Second drying Processing solution composition (first developer) Nitrilo-hetrimethylenephosphonic acid hexasodium salt 3.0 anhydrous potassium sulfite, 2o, oy sodium thiocyanate /, 2fl/-phenyl-coumethyl- ≠-Hydroxymethyl-3 -≠7--Virazolidone 2.0y Anhydrous sodium carbonate 30, Ojl Hydroquinone monosulfonate potassium salt 30.0 No Potassium bromide Co, Sy Potassium iodide (007% aqueous solution) λ- Add water Take 1000rd pH and adjust to 7.

(Color developer) Benzyl alcohol it, oy ethylene glycol /, 2. Otd nitrilo-to-N-trimethylenephosphonic acid hexasodium salt 3. Of potassium carbonate 2A, Of sodium sulfite λ・Oyl, 2-di(,2'-
hydroxyethyl) mercaptoethane
o, Ay-≠g- Hydroxylamine sulfate 3.0y 3-Methyl, ethyl, β-methanesulfonamide ethyl niline sulfate s, oy Sodium bromide o, sy Potassium iodide (007% aqueous solution) o, add swtt water and 1000rdpn to 10
．． Adjust to 3.

(Bleach-fix solution) Ethylenediamine-to, helN'1 8'-Iron(II) glacetate ammonium (cohydrate) go, oy Sodium metabisulfite /,! Ammonium thiosulfate (5g% aqueous solution) / 2b, 6d Nomercapto / 3, 3-Trisulfate o, zoy Add water and adjust the pH to 1000 g.

The yellow, magenta, and cyan dye densities of the dye image after processing were all determined by the method described above and plotted against the logarithm of the exposure dose, Itog E, to determine the characteristic curves of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer, respectively. Obtained. Further, the dD/dAogE value (point gamma) was determined from this curve (Dx o gE curve).

For photosensitive materials 101 to //3, the types of emulsions used and characteristic values related to the present invention obtained from the characteristic curves of the respective green sensitive layers are listed. (Table 2) Sample 10λ~103.10.5~107,10 in this example as described in the second coating
9 to //3 are related to the present invention, while sample 1
0/, 1041.10f does not meet the requirements of the present invention.

In order to compare the tone reproducibility for a transmission original and a reflection original all around these samples, printing was performed from the same transmission and reflection originals, respectively.

The transparent original used color slides obtained from Fujichrome Professional Reversal Film (RDP) (manufactured by Fuji Photo Film), and the reflective original used color slides obtained from Fuji Color Paper (High Tech Color Paper 72) (manufactured by Fuji Photo Film). Using print 〇 For each manuscript, the density O0,2 point and 0.3 on the manuscript
Density difference △D (0°2-0.3) indicated by the dot on the print
And so. Similarly, the density difference between the density 1.30 point on the original and the point / and point B on the print was defined as ΔD(/, 3-/i). It is preferable that these points showing a density difference of 0°7 on the original are reproduced close to Oo/ on the print. Sample 10
These values are listed in Table 2 for 1 to //3.

Also shown is the lowest density on each print. The minimum density of the original was 0.05j for the transparent original and 0,/, 2 for the reflective original.

Table 1 shows only the data regarding magenta (green sensitive layer), but exactly the same results were obtained for cyan (red N & layer) and yellow (blue sensitive layer).

As is clear from Table 2, in the comparative examples, the minimum density is high and the density of the highlight area increases, making it look dark, whereas the sample according to the present invention impairs the whiteness of the original. There aren't many things.

Furthermore, when comparing samples 101 to 103, in sample 10/, which is a comparative example, △DCO,,2-0,3> is O0O/and the gradation of the highlight of the original is compressed and expressed. Samples 102 and 103 of the present invention have relatively low values, closer to the original density difference of 0, /, and more faithfully reproduce the entire tone of the original. These things are the same for samples 1041~//3,
In samples /10 to /3, prints that were even closer to the original were obtained.

On the other hand, even when a reflective original image is used, according to the present invention, a minimum density and density difference closer to the original image can be obtained. In particular, with reflective originals, it is difficult to obtain a sufficient amount of reflected light even in the brightest part of the original, so in contrast to the comparative examples where the minimum density is high, according to the present invention, the lower minimum density is closer to the original. I can see that it has been achieved. In order to obtain a minimum density that is faithful to the original using the light-sensitive material of the comparative example, it is necessary to increase the exposure amount, and in this case, a problem arises in that high density cannot be reproduced satisfactorily.

Example λ Emulsion A and Emulsion B2 were produced as follows.

Emulsion A An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were mixed in o per mole of Ag! ;Ay's 3. 'I-dimethyl-hachihe-chiryozorin-! - Thione was added simultaneously to the gelatin aqueous solution with vigorous stirring at 7 J°C over about 20 minutes, and the average particle size was 0. ．． An octahedral monodispersed silver bromide emulsion of 2/μm was obtained. To this emulsion, add 1 mol of scissors each of sodium thiosulfate and chloroauric acid (as hydrated salt) to make 7
,! ;Chemical sensitization treatment was performed by heating at °C for gθ minutes.

The silver bromide grains thus obtained were further grown by further treatment for 70 minutes in the same precipitation environment as the first time, and finally octahedral monodisperse core/shell silver bromide grains with an average particle diameter of O0≠jμm were obtained. An emulsion was obtained. After washing with water and desalting, this emulsion was mixed with 3.0 ml of silver per mole of silver. A chemical sensitization treatment was performed by adding sulfur thiosulfate and auric acid chloride (glucose salt) and heating at 60°C for 60 minutes to obtain an internal m-image type silver halide emulsion. .

Emulsion B Aqueous solution of potassium bromide and silver nitrate 3.11. -Dimethyl-3-thiazoline-2-thione was added simultaneously to an aqueous gelatin solution with vigorous stirring at 7 J'C over about 20 minutes to obtain a monodispersed octahedral odor with an average particle size of O1≠-μm. A silver oxide emulsion was obtained. This emulsion contains pof per mole of silver.
A chemical sensitization treatment was performed by adding sodium thiosulfate and chloroauric acid (dihydrate) and heating at 7 J° C. for 0 minutes.

Using the thus obtained silver bromide grains as cores, they were further grown by further treatment for 4 tO in the same precipitation environment as the first time, and finally the octahedral monodisperse core/shell silver bromide grains had an average grain size of 0.7 μm. After washing and desalting with 0 water to obtain an emulsion, sodium thiosulfate and chloroauric acid (gluate) were added to the emulsion in amounts of 2.3Tn and 9 amounts each per mole of silver, and the emulsion was heated at 60°C for 60 minutes to complete the chemical sensitization process. An internal latent image type silver halide emulsion By was obtained.

Emulsion C In emulsion A, when forming silver bromide core grains, 10
-4 moles of lead chloride was added, chemical sensitization was carried out in the same manner as in Emulsion A, and an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0 μj μm, which was shell plated, was obtained. Emulsion C was obtained by processing.

Using core/shell type internal latent image type emulsion A and By in a ratio of 2:3, double-sided lamination with polyethylene was carried out on a paper support, and a full multilayer color photographic paper (20 /)It was created.

As a gelatin hardening agent for each layer, /-oxy-3<j-dichloro-5-1-riazine sodium salt was used17).

The following compounds were used as the spectral sensitizing dyes for the jth and 3.7th layers.

Blue-sensitive milk pigments: Red-sensitive milk pigments: Green-sensitive milk pigments (*/) to (*/ri) in Table 3 are the compounds described in Examples -/, and (*a) to (*e) are respectively The compound is shown below.

(*a) (*b) α -A / - (*e) (C8H170→-P=0 /:, 2:, 2 mixture (weight ratio) Replace emulsion Ai of sample (20/) with emulsion C , sample C202) were all prepared.

The color photographic paper thus prepared was subjected to wedge exposure (1710 seconds, /OCMS) and then subjected to the following treatment and its density was measured.

Color development 3 minutes 30 seconds 33℃ bleach fixing
7 minutes 30 seconds 33℃ stable ■ 7 minutes
Stable at 33°C ■ 7 minutes Stable at 33°C ■ 7 minutes The replenishment method for the 33°C stabilizing bath is to replenish the stabilizing bath ■, guide the overflow liquid from the stabilizing bath ■ to the stabilizing bath ■, and stabilize the overflow liquid from the stabilizing bath ■. Bath■
A so-called countercurrent replenishment method was adopted, which leads to

Diethylenetriaminepentaacetic acid λ, Oy benzyl alcohol i, 2. gy-1,2-diethylene glycol 3. ≠ 1 Sodium sulfite λ, o y Sodium bromide 0. ．． 26P hydroxylamine sulfate 2.6 (#sodium chloride
3.2013-methyl-≠-aminohe
Gu,, 2! ; P ethyl-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30. Add water and add 1000 dp)i
to 2° pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Ammonium thiosulfate 110y Sodium bisulfite io y Diethylenetriaminepentaacetic acid, 56 P acid iron (1) ammonium/hydrate ethylenediaminetetraacetic acid, 2. 59 sodium dihydrate l-mercapto-/, 3. Add water and adjust pH to 4,j with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

/-hydroxyethylidene 7.6--/,
/'-diphonufonic acid (60clI) Bismuth chloride 0.33F polyvinylpyrrolidone 0.2! ;9 Ammonia water λ, J d Nitrilotriacetic acid.
3a/, Ofj-chloro-1-methyl-
Koichi Inch Ryozorin-3-on jO■No Octyl-
Gooisothiazolin-3-one 30 tny
Add optical brightener (v, Hiro'-Shea water) to 1000dpH7
, 3 pH is adjusted with potassium hydroxide or hydrochloric acid.

The results are shown in the puffer fish table.

Procedural amendment 0・

Claims (3)

[Claims] (1) In a positive-positive type silver halide photographic light-sensitive material formed by coating one or more photosensitive layers on an opaque, translucent or transparent support, i) the characteristic curve ranges from the developed density to the lowest density; The value obtained by subtracting the concentration value divided by the maximum concentration is 0.3
The average value (A) of point gamma at each point within the exposure range corresponding to ~0.7 is 1 to 3, and the variation range is within ±15% of the average value of point gamma within the exposure range. , and further ii) the average value (B) of point gamma at each point within the exposure range corresponding to a density value of 0.05 or more and less than 0.1 is 0.2 or more, and iii) ) Halogenation characterized in that the average value (C) of point gamma at each point within the exposure range corresponding to 0.1 to 0.2 as a density value obtained by subtracting the lowest density from the developed density is 0.3 or more. Silver photosensitive material. (2) The relational expression between A and C: The value of (A^2×C) is 0.
The silver halide photographic material according to claim 1, wherein the silver halide photosensitive material has a molecular weight of 8 to 10. (3) A positive-positive type silver halide color photographic light-sensitive material having at least one layer each of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support, and all characteristic curves of these light-sensitive layers are patented. A silver halide color photographic material that satisfies the conditions set forth in claim 1.