JPH02183249A - Color photograph image forming method - Google Patents

Abstract

PURPOSE:To form the images exhibiting the color reproducibility with which red shades are liable to be formed and which has a stereoscopic feel by setting the sensitivity of the long wavelength of the max. sensitivity wavelength of a red-sensitive silver halide at the value below the max. spectral sensitivity. CONSTITUTION:The following requirements are provided in the color image forming method for printing the color original picture obtd. by using a color photosensitive material for photographing provided with a silver halide blue- color sensitive layer (BL), a silver halide green-color sensitive layer (GR) and a silver halide red-sensitive layer (RL) on a substrate to a silver halide color photosensitive material for printing provided with a yellow color forming layer (YL), a magenta color forming layer (ML) and a cyan color forming layer (CL) on a substrate: The max. value of the spectral sensitivity distribution S (lambda) of the RL is applied so that the wavelength (lambdaRmax. is in a 595 to 645<nm> wavelength region and the spectral sensitivity at 650<nm> is <=50% of the max. value of S(lambda). The silver chloride or silver chlorobromide emulsions of >=90mol% silver chloride content as the layer average are respectively used for the ML and the CL. The reproducibility of higher red shades is easily obtd., in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Small industrial application fields) The present invention uses gold as a color photosensitive material for high-silver chloride printing, which is suitable for rapid and stable development processing, and has excellent color reproducibility and color gradation reproduction. This technology relates to the method of forming color photographic images, in which printing is performed from a color negative film obtained using a color negative photosensitive material devised to reproduce color gradation on color photographic paper that has excellent color separation and saturation and is suitable for rapid processing. This invention relates to a color photographic image forming method.

(Prior Art) Recently, a wide variety of systems for forming color images have become widespread, and the color photographic image forming method using a silver halide color light-sensitive material is known for its high sensitivity and high sensitivity. It has become popular due to its excellent graininess and color reproducibility, and there is an increasing demand for color reproducibility and tone reproducibility that cannot be achieved with other systems. On the other hand, there has been a growing demand for improvements to these deficiencies, such as speeding up and simplifying the development process and reducing the amount of processing liquid used. Particularly in markets such as color photosensitive materials for printing, where there is a strong demand for large quantities of prints to be completed in a short period of time, silver halide grains with a low or high silver chloride content are used to speed up the development process. So-called high silver chloride type color photosensitive materials for printing are being used. For example, %E, Co., Ltd.'s Ko00/type color photographic paper and its RA-Kotype development processing, and Konica's Q
A system and Fuji Photo Film's FA system have also been announced. It is also used as a silver halide emulsion useful in high silver chloride type color photosensitive materials for printing.
Emulsions containing vertex-developable grains and high silver chloride/decagenide grains having a localized phase on the grain surface as described in EP-277,122, EP-J73, and Ge30 are known. There is.

In order to improve the color reproducibility of color negative photosensitive materials, a method of providing a multilayer effect donor layer having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL is disclosed in US Patent No. 447. Core No. 1, Dohiro, 70j, 714, Doda, 707. No. 3, No. 3, No. 6, No. 23, No. 6, No. 23! It is described in specifications such as No. 11. If these methods give a large single-layer effect to the red-sensitive layer, it becomes difficult to faithfully reproduce, for example, shadows that occur in a red subject. JP-A-4/-≠37-3 describes a method for overcoming this problem by placing a limit on the spectral sensitivity distribution of a red-sensitive silver halide emulsion layer.

(Line order to be solved by the invention) When a high-silver chloride color photosensitive material for printing is used, the saturation of the three primary colors is increased, but the drawback is that the shading of the three primary colors at high color density, that is, the inability to produce other color gradations. be. For example, when reproducing a crimson rose flower, although the vivid crimson color is reproduced, there are important defects such as the gradation of the shading of the crimson rose not appearing, and therefore the texture of the rose flower being unable to be reproduced. It turns out.

Furthermore, it has been found that this defect becomes even more noticeable when used in combination with a color negative light-sensitive material provided with the above-mentioned multilayer effect donor layer.

The present invention aims to eliminate these defects while taking advantage of their respective advantages. The seventh object of the present invention is to take advantage of the essential features of high-silver chloride color photosensitive materials for printing, which are suitable for rapid processing, to improve color reproducibility and to improve color gradation in other color gradations within high color densities. An object of the present invention is to provide a color photographic imaging method that improves reproducibility. Other objects will be apparent from the description.

The present inventors have determined the sensitivity at long wavelengths, which is the maximum sensitivity wavelength of red-sensitive silver halide in RL, and especially the sensitivity at lhj It has been found that by lowering the maximum spectral sensitivity to a value below !0, it is possible to reproduce shadows with a high red density, and it has been found that the object of the present invention can be achieved by this.

(Means for solving the problem) (1) Photography in which a silver halide blue-sensitive layer (BL), a silver halide green-sensitive layer (GL), and a silver halide red-sensitive layer (RJ) are provided on a support. A silver-genide-free color photosensitive material for printing, in which a color original image obtained using a color photosensitive material for printing is provided with a yellow coloring layer (YL), a magenta coloring layer (ML), and a cyan coloring layer (CL) on a support. A color photographic image forming method for printing a color photographic image, characterized in that the following requirements (A) and (B) are satisfied.

(A) Give the maximum value of the spectral sensitivity distribution 5(1) of RLff
The wavelength (J) is 1aX! It is in the Tata to J4Lj O wavelength range, and has a maximum spectral sensitivity of 8 (yo) at tzonm! Q% or less.

(B) For ML and CL, silver chloride or silver chlorobromide emulsions each having a silver chloride content of O mol Llb or more as N average are used.

(2) The color photographic image forming method according to item 1 above, which uses a silver halide color photosensitive material for printing containing a maze/li coupler selected from compounds represented by the general formula (summer) in ML. .

General formula (1) In the formula, RFi hydrogen atom or substituent, Y is a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent, Za, Zb%Zc are methine, substituted, respectively A methine group represents =N--NH-, and one of the Za-Zb bond and the Zb-Zc bond is a double bond. R5 The above-mentioned substituted methine group or FiX may form a multimer of λ-mer or higher.

The features of the present invention will be explained below with reference to the photosensitive materials used and the main elements.

Color photosensitive material for printing (silver halide emulsion 1) The first feature of the present invention is that the magenta coloring layer (GL) and cyan coloring layer (RL) of the color photosensitive material for printing have a halogen composition as a layer average. The method is to use a photosensitive silver chloride or silver chlorobromide emulsion with a silver chloride content of more than 10%.

Furthermore, it is preferable to use this high silver chloride type emulsion in a yellow coloring layer (BLJ), and the high silver chloride is more preferably silver chlorobromide grains in which 2 moles to 2 moles are silver chloride. It is preferable to use grains with a silver iodide content of 7.0 molt or less or no silver iodide.

More preferably, these grains are heterostructured grains with "localized" regions having different silver bromide content from adjacent regions. The localized particles may be present inside or on the surface of the silver halide grain, or may be unevenly distributed on the surface or discontinuously isolated. Among these, it is particularly preferable that the surface of the silver halide grains is non-uniform or isolated. The silver bromide content for localization is preferably at least ! Morti, more preferably io molti or more, and 4C is preferably 207 ruti or more, and the upper limit thereof is preferably 707 ruti. If the silver bromide content is too high, desensitization occurs when pressure is applied, and sensitivity and gradation tend to fluctuate during continuous development. The silver bromide content for localization and the substrate (the degree of difference between the silver bromide content for grain part 1 other than localization and the silver bromide content for localization is determined by the molar ratio of silver bromide or bromide used to the total silver halide used) It depends on the rate at which water-soluble bromide is supplied to the substrate particles, the pAg and pH of the reaction solution, etc. In order to form a layer of localized bromide on the helog/silver oxide particles, it is necessary to , pAg
It can be formed by adding a silver nitrate solution and a halogen ion at a predetermined rate while controlling the JP pH, or it can be formed by replacing chloride salt on the grain surface with silver bromide by halogen. Non-uniform or isolated localizations which are particularly useful in the present invention include, for example, European Patent EP-J7J$Kota;
, No. 2714I30, Japanese Patent Application No. 11421λ, No. 7000! No. 4 of the same Showa era. Z-/! r, 2330
It can be formed by adding water-soluble bromide and silver nitrate or by adding fine silver bromide particles and physically ripening using the so-called CR-compound described in No.

The silver bromide content for localization in the present invention is determined by X-ray diffraction method (for example, as described in Nippon Kagaku Gokushu "New Experimental Kagakuzat, Structural Analysis" published by Maruzen, J or XPS method (for example, surface Analysis; "Applications of IMA, Auger electron, and photoelectron spectroscopy"#!4 Published by Dansha Dansan Can be measured by any method.

In particular, the EDX method (Energy Dispersive) is used to determine the localized silver bromide content on the surface of silver halide grains, especially at edges and corners.
X-ray analysis) (for example, "Electron Beam Microanalysis" by Hiroyoshi Soejima, published by Nikkan Kogyo Shimbunsha/Rir.
Using an EDX spectrometer equipped with a transmission electron microscope, approximately O
Approximately in a, l-char with a diameter of 0/ to 012 μm!
Can be measured with precision of a mortar.

Silver halide grains used in the present invention, cubic or t-hedral grains having (100) planes or l-parthedral grains,
They may be normal crystal grains such as t-hedrons having (///) faces, or tabular grains. The pAg and pH of the reaction solution for forming silver halide grains can be adjusted, and the horizontal Vc (
Halogenation with a localized silver bromide phase can be achieved by using a CR-compound (see above) or other organic compound having the property of adsorbing on the /00) or <1ii) planes. Can move around silver particles. Especially <
1oo) t-hedron with faces or /4! It is preferable to have a localized layer on a corner part of the surface of a hedral grain or a localized layer on a corner part or edge part of a tabular grain surface.

In the present invention, it is preferable that iridium ions or complex ions of 7 are contained in either the halogenated @sheet substrate or the localized layer.

Emulsions mainly composed of silver chloride often have undesirably soft tones in the legs, and the exposure time is as short as about 10 seconds. It is easy to cause so-called reciprocity failure, and in practical terms,
It was a big problem.

The addition of compounds that provide iridium ions is particularly effective in solving these dose lines. Many of the Group 1 elements of the Periodic Table of Elements are preferable from the above points, and iridium is a particularly preferable Group 4i element from these points of view.

The iridium ion-providing compound is usually preferably a trivalent salt or a complex salt. For example, potassium hexachloroiridate,
Sodium 70 moiridate, ammonium hexachloroiridate, etc. are used. Its use t is 1
The amount is about 10 to 70 moles per mole.

Localized layer of silver halide grains of the present invention or its substrate IC
Further, a different metal ion selected from metal ions or a complex ion thereof can be contained together with iridium. For example, the localized layer VC mainly contains loridium ions, and the substrate mainly contains osmium, iridium, etc.
Metal ions selected from platinum, ruthenium, palladium, iron, cobalt, nickel, etc. or their complex ions can be used in combination, and the type and concentration of metal ions can be changed between the localized layer and the substrate. A plurality of these metals may be used.

Furthermore, metal ions such as cadmium, zinc, lead, mercury, and thallium can also be used.

Preferred additives of these metal ions or complex ions that can be used in combination are 10 to 1 mole of silver halide.
-8 to 10-'' moles.

The average size of the grains of the silver halide emulsion used in Kinei 8Aic (average diameter by volume equivalent method) is 0.7 below λμ.
μ or more is preferable. Particularly preferred is 1, ≠ μ or less 0.
7! μ or more.

The narrower the grain size distribution, the preferable is a monodisperse emulsion. In particular, monodisperse emulsions with regular shapes are preferred for the present invention.
of all particles within! ! Emulsions that contain more than 500 yen, and especially emulsions that contain more than 200 yen are preferred.

The silver chlorobromide emulsion used in the present invention is P, Glaf-kide.
[Chimie et PhysiquePh
otographiqueJ (Paul Monte
, published by 1, 1967), G., F., Duffin, “P.
photographic Emulsion Cbe
Published by mistryJFocal Press, luri4
4th year), V, L.

Zelikman et a1 arrival [Making
andCoating Photographic E
mulsionJ (published by Focal Press, 1
It can be prepared using the method described in (Yta) et al. That is, any of the acid method, neutral method, ammonia method, etc. may be used, but the acid method is particularly preferred. Further, as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. A simultaneous mixing method is preferred to obtain monodisperse particles. A method of forming particles under conditions of excess silver ions (
A so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the silver ion concentration in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, it is possible to obtain a monodispersed silver 710 emulsion suitable for the present invention, which has a regular crystal shape and a narrow grain size distribution. The above-mentioned particles preferably used in the present invention are preferably prepared based on a simultaneous mixing method.

Known silver halide solvents (for example, ammonia, potassium thiocyanate, or U.S. Pat.
No. r, JP-A No. 13-/11413/R, No. J-4'
-1007/7 issue or Tokukai Sho! Hiro-/! jlrJt
When physical ripening is performed in the presence of thioethers and thione compounds described in
A monodisperse silver halide emulsion with a narrow grain size distribution can be obtained, which is preferable.

To remove soluble silver salts from the emulsion after physical ripening, washing with water, flocculation sedimentation, ultrafiltration, or the like can be used.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. That is, active gelatin, a sulfur sensitization method using a compound containing sulfur that can react with silver ions (such as thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.), or a sulfur sensitization method using a reducing substance (
For example, reduction sensitization using stannous salts, amines, hydrazine conductors, formamidine sulfinic acid, 72y compounds, etc.), and metal compounds (such as total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals of group (1) of the periodic table such as r, Pd, Rh%Fe, etc.) can be used alone or in combination. In the (monodisperse) high silver chloride emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and it is also preferable to have a hydroxyazaindene compound present during this sensitization.

Chemical sensitization in the present invention can be carried out by a conventional method (in particular) as described in Moeki. When the chemical sensitization is localized on the surface or subsurface of silver halide grains, chemical sensitization is carried out on the substrate grains. It is important to control the balance between localization and localization. For this control, European Time 1WEP-27310≠, same EP-, 27
311. The method described in EP-273≠30, particularly the method using the above-mentioned CR compound, is preferred.

The high silver chloride emulsion according to the present invention is from Hiro 00 to San 101m.
It has a characteristic of low spectral absorption in the blue-sensitive wavelength range (substantially no blue sensitivity).When such an emulsion is used for GL and RL,
Since the spectral sensitivity of GL and RL is low or virtually absent in the BLQWg wavelength range, BL and GL-? BL! : The separation of RL spectral sensitivities is significantly improved.

In the present invention, the use of spectral sensitizing dyes is important. As the spectral sensitizing dye used in the present invention, cyanine dyes, merocyanine dyes, composite merocyanine dyes, etc. are used.

In addition, complex cyanine dyes, holobolanine dyes, hemicyanine dyes, steryl dyes, and hemioquinnol dyes are used. As cyanine dyes, simple quanine dyes, carboanine dyes, and dicarbocyanine dyes are preferably used.

The spectral sensitizing dye is preferably added when forming the substrate particles. It is also preferable to add it before or during chemical sensitization.

Examples of sensitizing dyes include, for example, EP-1EP-λ73 Hirokota, EP-Core 11I30, EP-Core 3HiroO.
You can choose from those listed in the specification of Kogo. It is preferable to use these spectral sensitizing dyes to impart blue sensitivity to YLK, green sensitivity to ML, and red sensitivity to CL.

The high silver chloride silver halide emulsion with localization according to the present invention has excellent rapid developability equivalent to that of a silver chloride emulsion, and has a silver bromide content equivalent to that of a silver chlorobromide emulsion with a silver bromide content of 2Q or higher. In addition to providing sensitivity, the occurrence of fog can be practically effectively stopped by using the following antifoggant in combination. The antifoggant can be added to any layer in the silver halide color photographic light-sensitive material or to the color developer.

Preferred antifoggants include mercaptotetrazoles, mercaptotriazoles, benzotriazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotriazoles, nucleic acid decomposition products (for example, Abdi), and the like. These anti-capri agents are adsorbed in large quantities on particle surfaces other than the development start point, and do not reduce the speed of development start (fogging that occurs during the development process can be suppressed).

(Coupler) It is preferable to use a color coupler, especially a magenta coupler, which gives a spectral absorption curve close to a rectangular shape and a curve with a short end to the bottom of the color light-sensitive material for printing. When used in conjunction with the high silver chloride type halide chain emulsion of the present invention, it is possible to receive recording information of various colored images of RL, GL and BL, resulting in improved color separation (color prints with high chroma). The magenta coupler horizontal plate is particularly important for color photosensitive materials for printing.

The pyrazoloazole coupler represented by the general formula (N) used in the present invention is described in U.S. Patent WJ3.7,
Pyrazolo (, t, / c
) (/-Je4')) Liazoles can be mentioned, and among them, U.S. Pat.
The imidazo(/,,2-b)pyrazoles described in No. 100,430 are preferred;
Pyrazolo (z, tb) (/, co, g) triazoles described in Gj Hiro issue are particularly preferred.

Others, Tokukai Showa 4/-4! , 2 Hiro! A pyrazolotriazole coupler in which a branched alkyl group as described in the No. Pyrazoloazole coupler containing a sulfonamide group, #!
! Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in 1974/-74 (Publication No. 7) and European Time #f (Publication No.
It is preferable to use a pyrazolotriazole coupler having four alkoxy groups or aryloxy groups at the 3-position as described in RP No.

Typical examples of pyrazoloazole couplers used in the present invention are listed below.

Yoichi pyrazolone couplers can be used along with pyrazoloazole couplers. ! As the -pyrazolo/type coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the color-forming dye, and typical examples thereof include the inverted position, U.S. Patent No. 3//, Or, z issue, same number, 2.3μ3.703,
Same No. ko, too, yet, same No.-, 901,173, same No. 1. O62,611, same No. 3. / Octopus, T-Ribu and the same No. 3. i6. It is written in the oiz issue etc. As a leaving group for a pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat.
The arylthio group described in It10≠72j is preferred. It also has a ballast group as described in European Patent Section 73, /s3! - Pyrazolone couplers provide high color density.

In the present invention, pivaloylacetanilide-based yellow couplers, benzoylacetanilide-based yellow couplers, and the like are preferably used as the yellow coupler.

For details on pivaloylacetanilide yellow couplers, see column 3 of US Pat. No. 6, No. 217. It is described in the 7th≠column 10th line to the 75th column 1st line of the 7th≠column 10th line to the 1st column 3rd line and the 7th≠column 10th line to the 75th column 1st line of the Meiji book written by Dohiro, 6th Column, and tit No.

US patent, for more information on benzoylacetanilide yarn yellow coupler? , 4I01, No. 1917, Mukai 31ri 33. Jr., No. 1, Douhiro, Q.6. tough! No., II, /33. the law of nature! No., sameμ, 4Aoi.

There is a description in 7th issue etc.

An example of a pivaloylacetanilide yellow coupler is the above-mentioned U.S. Pat.

Compound examples described in columns 37 to yμ of specification No. 217 (
y-i) to (Y-32), among which (
Y-/), (Y-pi), (Y-4), (Y-77, (Y
-11), (Y-,2/), (Y-2J), (Y-23
), (Y-J4), (Y-3!), (Y-jA), (Y
-37), (Y-3t), (Y-3tan, etc.) are preferred.

Also, the aforementioned US special Ff4I, Ako! Compound examples (Y-/) to (Y
-JJ), among which (Y-, 2), (
Y-7J, (yr), (Y-/J), (Y-, 20)
, (Y--l), (Y-23), (Y-kota), etc. are preferred.

Other preferred examples include U.S. patent 3゜daO1;
/ Typical example of X-ray body described in No. 6m of Specification No. 911
IIL), 3.9! ! ,! Compound examples (16) and (l?2, same reference, 0146.1, described in column r of the specification of No. oi)
Compound examples (ri) described in columns 7 to r of Specification No. 71, Direction II, /33. No. 51 specification! Compound example (1) described in columns ~6, Direction V.

440/, 7! Compounds described in column j of the specification of item No.-- can be mentioned. Particularly preferred are coequivalent couplers having a nitrogen atom as the leaving atom.

In the present invention, phenolic cyan couplers and naphthol cyan couplers are preferably used as the cyan couplers.

As a phenolic cyan coupler, US Patent 2.3
6ri, octopus 2, same p, sir, try, same a, zi
It has an acylamino group at the 2-position of the phenol nucleus, as described in i, t≠7 and 3.77.2.00λ, and!
Items with an alkyl group in position (including polymer couplers)
A typical example of this is the Canadian patent book.
, r, z, coupler of Example λ described in No. 2, Compound (1) described in U.S. Pat. No. 3,772.002, ibid., h1°! Compounds described in No. 90 (I-Reference) and (1-1
, Japanese Patent Publication No. 67-3 ri Q≠! Compound (1), (
Examples include the compound (C-2) described in No. 2), (3), (2 Hiromu), and Mukai 6 Co. 701r Hiro.

As a phenolic cyan coupler, there is also a US patent.
,77,2,/l,, No. 2, 2,191. r, 2J issue, 4A, 334I, 0// issue, same reference, 200゜1hj
J issue and Tokukai Sho! 2. l-
There are diacylaminophenol couplers, a typical example of which is disclosed in the US patent λ.

Compound (V) described in No. trz, rλ, Dohiro.

j! 7. Compound fin described in the Tack issue, same≠,! 6j,
Compound (2) described in No. 777, αhondoshi, lλda, 3
Compound (4) described in the same reference, No. 413゜741, and the like can be mentioned.

As a phenolic cyan coupler, there is also a US patent≠
, 327. /73 issue, same reference, jjp, jrt issue, same u,
There are compounds in which a nitrogen-containing heterocycle is fused to a phenol nucleus, as described in UZO, UJZ, JP-A-1/-1YOA-DA 1, and JP-A-Sho, Zzz'yizr. See U.S. Patent No. J, Z7. Coupler (1) and (3) described in No. /7J, compound (3) and coupler described in No. Compounds (1) and (3) described in ≠No. 23 can be mentioned.

As a phenolic cyan coupler, see other US patents, 33! , Tatata issue, same fellow, ≠! l.

+52 issue, same reference, 171117.17λ issue, same concern, reference 2
7.747, 4A, j7ri, 273, European Patent (
EP) No. 067.41981, KIi[+7] ureido couplers are used as typical examples.
7), same 1. The coupler (1) described in μzi, try issue
), the coupler described in the same reference, Kol/-da, T72, the coupler (3) described in the same reference, Ko 27,747, the coupler described in the open-, tori, j/ri issue (6) Yar24
), coupler (1) and αυ described in fiiJ'1.179.113, European Patent No. (EP) 047,4r5'B
Coupler (45) and (50) described in / issue, JP-A No. 4
Examples include coupler (3) described in No. 7-u2tzr.

Examples of naphthol-based cyan couplers include those having an N-alkyl-N-arylcarbamoyl group at the 2-position of the 7-tole nucleus (for example, those disclosed in US Pat.

zts, rrt No. 1, those having an alkylcarbamoyl group at the - position (for example, those having an arylcarbamoyl group at the J1 co-position (for example, Special Public Show!o-1azJJ No.
Those having a carbonamide or sulfonamide group in the 1-position (for example, JP-A-6O-217444AI, t/-/
No. 4!1117, j/-/13≦4AO], and those having an aryloquine leaving group (for example, U.S. Patent J, No. 4!
74. j43), those with a substituted alkoxy leaving group (
For example, US patent data 4. /Tata), those with a glycolic acid leaving group (e.g. Japanese Patent Publication No. 217, March 1983)
and so on.

The standard usage of color couplers is 1,10,00/rj L1 mole per mole of light-sensitive silver halide, preferably 06°Q3 to 0.3 mole for the magenta coupler, and 0.3 mole for the yellow color coupler. For couplers, o, oi to 005 moles and for cyan couplers, from 0.002 to 17. It is J mole. The preferred coating amount of silver halide is from 0.797 m2 to 0.797 m2 when a reflective support is used.
, 097m2. 0 if using a transparent support
, 2 Jil 7m2 to 79/m.

These couplers are preferably dispersed and contained in the emulsion layer in the presence of at least one type of high-boiling organic solvent. A solvent is used.

General formula (AJ General formula (BJ wl -coo-w2 General formula (C) General formula (DJ General formula (E) w, -o-w2 (wherein, wl, w2 and W3 are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W4 is wl, o
wt represents t or 5-Wi, n is an integer equal to or less than l, and when n is 2 or more, W4 u may be the same or different from each other <, - In the general formula (E), Wl and W2
may form a fused ring. ) For details of these high boiling point organic solvents, see JP-A-4.2-. 2/l, published specification No. 272, page 137, lower right column to Hirohiro page 1, upper right column.

Further, it can be incorporated into the photosensitive emulsion layer by using a polymer dispersion using a water-insoluble polymer, such as a butyl acrylate methacrylate polymer or an acrylate N-butylacrylamide polymer, or by using the above-mentioned oil dispersion method. . Preferably international publication number WOr
Homopolymers or copolymers described on pages 1 and 2 to 30 of Specification No. 1700723 are used, and the use of acrylamide polymers is particularly preferred from the viewpoint of color image stabilization.

(Anti-fading agent, anti-color mixing agent) The photosensitive material used in the present invention contains a monohydroquinone derivative, an amine phenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative as a color anti-capri agent or an anti-color mixing agent. , colorless coupler,
It may also contain sulfonamide phenol derivatives and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Examples of organic antifading agents include 1-hydroquinones, t-hydroxychromans, 2-hydroxycoumarans, spirochromans, p-1 lucoxyphenols,
Typical examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylene dioxybenzene/s, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Can be mentioned. Further, metal complexes such as (bissalitelaldokikumatosi nickel complex) and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 3, Cotr., No. 3,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. In addition, in order to prevent deterioration of maze/red dye images, especially deterioration due to light, spiroindans described in JP-A-74-/J-6-gu and JP-A-1! Hydroquinone diether or monoether substituted chromans described in No. 19131 give preferable results.

Tokukai Akira again! Tar No. 1-1732 and JP-A-Sho t.

The image stabilizer described in No.-26/If and the like is particularly advantageous for stabilizing a magenta image formed using a pyrazolotriazole type magenta coupler.

In the present invention, it is preferable to use the following compounds together with the above-mentioned couplers. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound that chemically bonds with the aromatic amine developing agent remaining after the color development process to produce a chemically inert and substantially colorless compound (QJ and/or the aromatic amine developer remaining after the color development process). For example, the use of a compound (R) that chemically bonds with the oxidized form of an amine-based color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly, for example, for film preservation after processing. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the remaining color developing agent or its oxidized product and the coupler.

A preferable compound (Q) has a second-order reaction rate constant with p-aningine where 1 in trioctyl phosphate of rO'c is /, Ol /mol·see ~/
It is a compound that reacts in the range of
r-see! It can be measured by the method described in No.

When kJ is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if kJ is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, it may not be possible to prevent the side effects of the remaining aromatic amine developing agent, which is the objective of the present invention.

Such compounds (more preferable ones of Ql) can be represented by the following general formula (Ql) or (Qll).

General formula (Ql) R1-(A) n-X General formula (Qu) R2-C=Y In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n is/or Q is the front child. A represents a group that reacts with an aromatic amine developer to form a chemical bond, and X represents a group that reacts with an aromatic amine developer and leaves the group. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (Qn). The group to be used is the front child. Here, R1 and X, Y and R2, or e-r and B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by the general formulas (Qlj, (Qn)), see JP-A-47-/11!uj and AJ-21.
No. 13111, %! Preferred are those described in specifications such as JU81z-irls Hiroλ No. 277jr, European Patent Publication No. 277jr.

On the other hand, compounds that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound (a more preferable example of 1 is the following general formula (R1)) It can be expressed as

General formula (R1) -Z In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. 2 represents a group that decomposes in a nucleophilic crystal or photosensitive material to release a nucleophilic group. Compound Fi represented by general formula (R1), z is pearson's nucleophilic nCH31
Value (R,G,Pearson,etal,,
J, Am, Chem, 8oc,, Rio, 1iy (/1
4r) J! The above groups or groups derived therefrom are preferred.

Regarding shell examples of the compound represented by the general formula (R1), European Patent Publication Nos. 1j722 and 277! T? issue,
Tokukai Showa Tx-iasoar issue, same JJ-ko λri l reference! No., special request 1986-/! 67λ≠ issue, 6.2-ko/416
Those described in No. 1/, No. 1, No. 2-izr3, and No. 2-izr3 are preferred.

Further, details of the combination of the above-mentioned compound (R) and compound (Q) are described in European Patent Publication No. 277322.

In order to improve the storage stability of the cyan image, especially its original fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied may be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferable that Ixlo mol/m −2
Mol/m ~/.

It is set in the range of zxio-3 mol/m2.

In a typical color photosensitive material having a one-percent layer structure, an ultraviolet absorber is contained in either layer on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. This protective layer can contain a mixture of matting agents of arbitrary particle sizes and latexes of different particle sizes.

(Support) The reflective support that can be used in the present invention is preferably one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clear. A support coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and a support using vinyl chloride resin containing a dispersed light-reflecting substance. Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyethylene terephthalate,
Examples include polyester films such as cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, and polystyrene films, and these supports can be appropriately selected depending on the purpose of use. In addition, JP-A-60-10J issue, A3-tirizu issue, same t
3--I item No. 7, 43-J4C Kota I or t3-
2 reference λ! ! A support having a specular reflection surface or a type 2 diffuse reflection surface as described in the above specification is used. A transparent support is also used in the present invention.

As the above-mentioned light-reflecting substance, it is preferable to thoroughly knead a white pigment in the presence of a surfactant, and it is preferable to use pigment particles whose surfaces have been treated with dihydric to dihydric alcohol.

The occupied area ratio of white pigment fine particles per specified unit area (Chino divides the observed area into adjoining unit areas of 6 μm x 4 μm, and calculates the occupied area ratio of fine particles projected onto that unit area. Area ratio (%) (Ri) can be determined by t = measurement.The coefficient of variation of the occupied area ratio (%1) is determined by the ratio s/FL of the standard deviation S of Ri to the average value of Ri (1-LJ) The number of target unit areas a(n) is preferably 6 or more. Therefore, the coefficient of variation s/R can be determined by:

In the present invention, the occupied area ratio of fine pigment particles (the coefficient of variation of l is O6) is particularly less than or equal to 0. /, 2 or less is preferable. In the case of o, or or less, the dispersibility of the particles can be said to be "substantially uniform."

(Layer structure) As mentioned above, color photosensitive materials for printing usually have a small number of red-sensitive emulsion layers, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of the layers can be arbitrarily selected depending on the comfort.Furthermore, each emulsion layer may be a mixture of λ or more emulsions having different sensitivities.
Alternatively, it may be composed of one or more independent layers, and a non-light-sensitive layer may be present between λ or more emulsion layers having the same color sensitivity.

In the color light-sensitive material according to the present invention, in addition to the silver halide emulsion layer, auxiliary layers such as a protective layer, an intermediate layer, a film pm, a halide prevention layer, and a back layer are preferably provided on the support. .

(Binder) As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin spindles, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxyl methyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch-containing conductors;
A wide variety of synthetic hydrophilic materials such as single or copolymers of polyvinyl alcohol, (ho+)vinyl alcohol partial acetal, (bo+)-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Polymeric substances can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, 8ci, and Phot.

Enzyme-treated gelatin as described in Japan, 4/t, p. 30 (l. 66) may be used (alternatively, gelatin hydrolysates and enzymatically decomposed products may also be used).

(Other Additives) In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developing agents or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Typical examples of these additives are Research Disclosure Magazine/I6
/76 Ko 3 (Iri 7 on December 2, 2013 and 1t716 (
It is written in 1997//month).

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-soluble brighteners may also be used in the form of dispersions.

Color/Negative Photosensitive Materials for Photography> The second feature of the present invention is that the above-mentioned high silver chloride type color photosensitive materials for printing can be used to eliminate defects using their excellent development processing characteristics and color reproducibility. The objective is to eliminate this problem by improving the spectral sensitivity characteristics of the color and negative photosensitive materials used in combination.

(Layer structure and spectral sensitivity distribution) A blue-sensitive layer (BL), a green-sensitive layer (GL), and a red-sensitive layer (RLJ) are provided on the support.The BL, OL, or RL
may be a single layer, but each of these photosensitive layers is preferably composed of two, three or more unit photosensitive layers. Furthermore, BL, GL, or RL have different sensitivities and different spectral sensitivity distributions (for example, the ratio of the amount of multiple types of sensitizing dyes used in each photosensitive layer is different, etc.) good.

Generally, the unit photosensitive layers are arranged in this order from the support side: a red sensitive layer, a green sensitive layer, and a blue sensitive layer. However, depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, /%/7bu≠3 on page 21, and on the same shoulder /17/l, 4 layers, page 7, right column to tar page left column.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 22 μm or less, preferably about 1 μm.
and the membrane swelling rate T1/2 is preferably 3 layers or less. The film thickness is under J90C relative humidity 22 humidity control (2
(day), and the membrane swelling rate T1/2 is:
It can be measured according to techniques known in the art.

For example, "Photographic Science and Engineering J (Photogr, Sci, Eng.)" by A-Green J et al.

It can be measured by using a swellometer (swelling membrane) of the type described in Volume IP, No. 2, pages /2u to 7.2F,
T 1/2 is the saturated film thickness, which is 20 - of the maximum swelling film thickness reached when treated with a color developer at 30°C for J minutes it seconds.
This is defined as the time required to reach the film thickness of Tl/2.

The membrane swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate F
into-4Aoo@ is preferred.

The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula = (maximum swollen film thickness - film thickness; / film thickness).

In the color negative photosensitive material according to the present invention, the characteristic of the RL spectral sensitivity distribution (S(λ)) is that the wavelength (λ) giving the maximum value of S(λ) is ! Tar to 44cj
``17) wavelength range, and the spectral sensitivity at (nit!0''-K) is less than 50% of the maximum value of 8(J).The spectral sensitivity distribution of GL (S(yo)1 #i, oL 8
．． , o maximum value t-give t6[&(J7.”) is s, 27
The wavelength (J,) that gives 10% of the maximum value of S (yo) is in the wavelength range of 100 to t.
It is preferable that the wavelength is in the oo'''' wavelength range.

Furthermore, BL(7)S(yo) is the wavelength m which gives the maximum value of S(λ)
Wavelength that gives the maximum toqb value in the wavelength range "C1" (It is preferable that λBJ is lQO or tOOnrn. Furthermore, x': "+iZ" - (D wavelength H has RL and It is preferable that the BL(D sensitivity is sufficiently low. For example, in the above wavelength range, it is Log
With a value of 8 (□), the sensitivity of RL is lower than 2.0, and the sensitivity of BL is lower than 2.0.
It is preferable that the sensitivity is also as low as 765 or more.

In addition, the above-mentioned essential requirement (A)j-satisfy 4 of the present invention.
By using a photographic color light-sensitive material having a spectral sensitivity of j Onm, it is surprisingly possible to obtain a print with a high color S degree, for example l.

The reproduction of cyan color gradation, in other words, the reproduction of shading in magenta or red color concentration of 0 or more, is significantly improved along with the excellent color reproducibility (saturation and brightness) of yellow and red. .

In silver halide color negative films, it is necessary to have a wide exposure latitude, and it is undesirable for color reproducibility to change depending on the amount of exposure, so it is desirable that the spectral sensitivity distribution of the same coloring layer be the same. but,
The spectral sensitivity distribution may differ slightly depending on the halogen composition of the emulsion, the adsorption state of the sensitizing dye, or the absorption of diffusion-resistant dyes, colored cazolers, etc. in the coating composition. Therefore, there are cases where the maximum sensitivity wavelength changes depending on the color density. There are also cases where the spectral sensitivity distribution is intentionally changed. For example, if the high-sensitivity emulsion layer of the red-sensitive layer is set to a longer wavelength than the spectral sensitivity distribution of the low-sensitivity emulsion layer, if the region that contributes significantly to the color density is the low-sensitivity layer, the spectral sensitivity distribution of the low-sensitivity emulsion will be 8 degrees. The wavelength that gives the maximum value of the distribution (λmax greatly contributes to color reproducibility.The above λmax, maximum spectral sensitivity, and spectral sensitivity at tzonmyc are determined using a spectral sensitive needle and the equal-energy spectral sensitivity distribution defined by I80. It is preferable to measure the spectral sensitivity at the base concentration + 〇, 4I.The spectral sensitivity is also measured at the base concentration + 0.1. It may be the same value.

The spectral sensitivity distribution obtained by the above method is shown in FIG.

(Silver halide emulsion 1 The photographic emulsion layer of the color negative light-sensitive material used in the present invention contains any of the following halides: silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to about 30 mole of silver iodide.Particularly preferred are silver iodobromide and silver iodochlorobromide containing about 30 mole of silver iodide or less.
About 2 from Morchi! Silver iodobromide containing #iodide in moles qht.

Silver halide grains in photographic emulsions may be so-called regular grains with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons (and also grains with irregular crystal shapes such as spherical shapes). , tabular grains, grains with crystal defects such as twin planes, or composites thereof.

The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains up to about io microns in projected area diameter, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, as described in Research Disclosure (
RD) magazine, 4/744Aj (/ri7, July 2, 2017 voice, 2
pp. 1-23, “1. Emulsion production (Emulsion pr
eparation and types, etc.
It is possible to follow the method described in 17/17/Ail 7/2/2/2011, page 1, ap1.

Also, as a monodispersed emulsion, silver halide grains having an average grain diameter larger than about 0.11 microns, and at least about 2! An emulsion whose weight is within the range of average grain diameter + tQ is typical. Silver halide grains having an average grain diameter of about Q, coj-J microns and having a small number (both about 2! by weight) or at least about 2!
Emulsions such as those within the range of 0% can be used in the present invention.

Also, tabular grains having an aspect ratio of about 1 or more can be used in the present invention. Tabular grains are described by Gutof, Photographic Science and Engineering.
Science and Engineering J, Vol. IA, p. 1!7 (1970); U.S. Patent No. ≠.

≠3 Hiro, Koko wo issue, same p, pie, sio issue, same 1. Thank you! No. 0 and British Patent No. 1, //, 2. /! It can be easily prepared by the method described in No. 17. When tabular grains are used, there are advantages such as improved color sensitization efficiency by sensitizing dyes, improved graininess, and increased sharpness, as disclosed in the above-cited US patent.

It is described in detail in Ko 3, Ko λ 6, etc.

The crystal structure may be --like, or it may be one in which the inside and outside have different halogen compositions (in particular, those with a layered structure are preferred. These emulsion grains are described in British Patent No. 1.Q
Core, / Reference No. 4, U.S. Patent No. 3. IO! , No. 0411,
Room clerk, r77 to 411 and JP-A-40-/≠333
It is disclosed in No. 7, etc. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

It is also possible to use mixtures of particles of various crystalline forms.

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 listed in Search Disclosure Magazine/16/7Aas and 4/r7i cited above.
The relevant parts are summarized in the table below.

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.

l Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Anti-fogging agents and stabilizers 6 Primary absorbers, filter dyes UV absorbers 7 Anti-stinting agents dye image stabilizers Hardener binder plasticizer, lubricant coating aid, surface 23 page 23-Cog page λμ page Kohiro-Koj page 25-26, 2! Page right column 2, page 26, page 17, page 126. 27 page Hiro Same as above column Same as above t ≠ r Page right column ~ tμ → Same as above column In order to prevent the deterioration of photographic performance due to
．． ≠31. ! It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 01.

In particular, the silver halide emulsion used in the present invention contains at least one silver halide grain that has been developed using a typical color developer for color negative light-sensitive materials or a practical color developer. 10% in number are a) particles controlled so that development starts at or near the apex of the grain edge (apex development type particles: CDGJ and/or b) development starts at or near the apex of the particle Particles controlled as such (edge development type particles: EDG)
It is preferable that This CDG and/or ED
The G emulsion is extremely suitable for the present invention because it exhibits development progress, particularly rapid gradation, and shows parallel-moving pattern progression, and sensitivity, with little variation in relation to the designed reciprocity law characteristics and stable finish quality. It has an advantageous photographic quality.

CDG and/or #-tEDG emulsions are
7000! No. 6, No. 1, No. 1, No. 1
! 2330 and Jj-/1r70 by the method described in the specifications.

In particular, CDG and/or EDG emulsion type tabular grains are preferably used. In particular, it is easy to determine the characteristic spectral sensitivity distribution of the present invention by selecting the OCR compound described in the above specification.

(Sensitized color mixture for RL) For the color negative light-sensitive material according to the present invention, it is possible to select from among the same sensitizing dyes as described in the section of the light-sensitive material for printing. General formula (II), (I[J and (IVJ
It is possible to select and use the sensitizing dye represented by the sensitizing dye represented by or the sensitizing dye as a CR- compound represented by the general formula (N, (...) and (fit) described in specification number 47-/31704). In particular, when carbocyanine dyes that do not form J aggregates are combined with other cyanine dyes (particularly when combined with tabular multistructured silver halide grains), a sharp spectral sensitivity distribution can be obtained. Spectral sensitization advantageous to the invention can be performed.

Next, examples of particularly preferred RL sensitizing dyes will be shown.

S-see -t 8-! S-ta -t s-i.

8031-1・N(C2)15)B2Hs(CH2)3803-8-/Co5-is S-no-1t C2)(5(CH2)4SOs-(CH273803-CI-12C)120H 8-/ 5O3H'N (C2H5)3 (CH2) 3803- (C)12) 38 (J3H 8-col 2HIS (CH2)<5Oa- (CH2) 4803Na S-2! S-27 2H5 in tro In order to reduce the spectral sensitivity, it is also possible to use a dye that absorbs in the wavelength range of t4Io to 700 nm.Preferably, a colored layer that is washed out or decolored by color development processing is provided on the photographing light source side of the RL. You can also do it.

It is also possible to use a mordant layer with a polymer providing cation sites or a layer containing a solid fine particle dispersion of dye.

(There are many color couplers that can be used with color photosensitive materials for color coupler printing.

Various color couplers can be used in the photographic color photosensitive material of the present invention, examples of which include the aforementioned Research Disk A-Jar (RD) 4774 $7. ■−
It is described in the patents listed in C to G.

As a yellow coupler, for example, U.S. Patent No. J, P3! ,! No. 0/, No. 0, No. 6-0, No. 326.01, No. 0/, No. 0/, 7! Ko No., Mukai no.
oJQ No. 1゜≠74.76Q, U.S. Patent No. 3.
273. R TR No., same No. 3, IIA, Oko No. 3, same No. DA,! Preferred are those described in European Patent No. 2≠≠73A, etc.

As the magenta coupler, Fi, j-pyrazolone type and pyrazoloazole type compounds are preferable, and are disclosed in US Patent WJ Hiromu, Zio, TI, No. 311°r27, European Patent No. 73,1AST, US Patent No. 3.06/, ≠3
- issue, 3.7th issue, otei issue, Research Disclosure ill, 16ko4IλλO (/?ff 33112 issue), Research Disclosure magazine 4.24Eko30 (The years have passed since J1 JP-A No. 36! 2, No. 61-72231, No. 6
O-317IO, zz-iiroi hiro, 60-
/r! No. 11, U.S. Patent No. 1,500,630, U.S. Pat. Particularly preferred.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat.

0! Ko, No. 272, Dou-tai, l≠A, J Riwo No., Ko No. 1, λ Ko r, Ko No. 33, Same wIJ, Kota T, No. 200,
Same No. 1, 34th, Octopus No. 2, Same No. 2. rO/, No. 171, No. 772. /No. 62, No. J, riz, tt, @J, No. 77, No. 00, No. J, 7! I,
No. 101, No. 33, Hiroshi 0//, No. μ, 3 Core, No. 173, West German Patent Publication No. 3, 3? , No. 7.2,
European Patent No. 1.2/, 36! No. 2, No. 2≠ri, ≠zz
No. h, U.S. Patent No. 3, 1, 6λ Co., No. 3, 3!3
゜P2 No., No. 77j, No. 4/4, same flute.

4Iat, TT No., No. J7,767, No. 41.4 Rio, No. TR, No. 1. Jj4', 272
No., same No. ≠, 2F Otsu, / Tade No., JP-A-61-P Kotr
Those described in No. y etc. are preferable.

Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Research Disclosure Magazine/74 Ko 3, section ■-G, U.S. Pat.
7-3 Tada IJ No., U.S. Patent No. 3, oohiro, Takota No.
No. p, i3r, zzt, British Patent Department i, iμ4.
The one described in No. 3tr is preferred. Also, U.S. Patent No.
, 774 (.

No. 721, a coupler that corrects unnecessary absorption of a coloring dye by the fluorescent dye released during coupling, and a coupler that reacts with a developing agent to form a dye, as described in U.S. Pat. No. 4', 777, /JO. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 744.237, British Patent Division 2. /2r
,! No. 170, European Patent No. 370, West German Patent (
Publication 2 No. 3.234I, j-3! Preferably, those described in No.

Typical examples of polymerized dye-forming couplers are U.S. Pat. JrJ issue, same issue! IO? ,lJ
No. O, same No. 77. ri No. 10, British Special FF Co., io
It is described in Ko, No. 773, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD/74FJ,
■Patent described in ~F section, Jikai F! rf! 17-/
! I? $lI issue, same j7-/! r4c23 reference number, direction 6
0-/r Guhari No. 6, Mukai JJ-373 No. 6, U.S. Patent≠
1.2 Hirot, Ri6ko, Dohiro.

7j Co., No. 014 is preferred.

As a coupler that releases a nucleating agent or a development accelerator in an imagewise manner during development, British Patent Department 2. Qri 7, / Hiro O issue,
Same No.-, TII, IRR No., JP-A-Shojter/! 7411
No. 19-/701 (the one described in No. 70 is preferred).

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in US Pat.

213, riff No. 2, same No. 3, 31r, lli No. 3, same No. 1
I, 310,611, etc., JP-A No. 4O-111I10, JP-A No. 4.2-2U2! DIR redox compound releasing coupler described in No. λ etc., DI
R coupler-releasing couplers DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers releasing dyes that recolor after separation as described in European Patent No. 173,30JA 1 (, D, 4/ / uu
the law of nature.

Kohiro J-7% Bleach accelerator releasing coupler described in JP-A-47-0/2 Ko-7, etc., US Percentage No. 3.

113.4I77, etc., leuco dye-releasing couplers described in JP-A-43-777I7, US #f#f No. 1.77≠.

Examples include couplers that emit fluorescent dyes as described in No. 111.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods as in color photosensitive materials for printing.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat.

Furthermore, the same details as described in connection with the printing coupler apply.

Color development processing method> A feature of the present invention is rapid stabilization of color development processing.

Color photosensitive materials for printing, which require high productivity, can be produced in less than 3 minutes, preferably 2 minutes, by using devised silver halide emulsions, color couplers, anti-fogging A11, etc. Prints can be made stably in less than 30 minutes.

Ability 2: Color photosensitive materials for printing can be color-developed by the same processing or common processing as negative photosensitive materials.

The processing of color photosensitive materials for printing will be explained in detail below.

The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately rather than in one bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing crude drug.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited to these.

f) -iN, N-diethyl-p-phenylenediamine D-Co-amino-j-diethyla ξnotriene D-J -mono-amino-z-(N-ethyl-N-laurylamino)toluene D-Sanhiro-[N- Ethyl-N-(β-hydroxyethylnoamino)aniline D-! Comethyl-[N-ethyl-N-[β-hydroxyethyl)amino]aniline D-J Guamino-3-methyl-N-ethyl-N-
[β-(methanesulfonamitonethyl]-aniline D-7N-(coamino-dimethylaminophenylethyl methanesulfonamide 1)-I N,N-dimethyl-p-phenylenediamine D-taguamino-3-methyl -N-ethyl-N-methoxyethylaniline D-10guamino-3-methyl-ethyl-N-β
-Ethoxyethylaniline 1)-// Hiro-amino-3-methyl-N-ethyl-
Among p-phenylenediamine derivatives, l-amino-3-methyl-N-ethyl-N-[β-
(methanesulfonamide J ethyl)-aniline (exemplified compound D-6).

Further, salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates may be used with these p-phenylenediamine derivatives. The IL used for the aromatic-grade amine developing agent is preferably about 0.05 IL per liter of developer solution. /9 to approx., 2
0g, more preferably from about 0°zg to about iog.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Preferably, it does not contain substantially -ml/
The benzyl alcohol concentration is less than 1, more preferably less than O0!171m, and most preferably it contains no benzyl alcohol.

More preferably, the developer used in the present invention does not substantially contain sub@L#R ions. Sulfite ion removal,
In addition to functioning as a preservative for the developing agent, it also has the effect of dissolving silver halide and reacting with the oxidized developing drug to reduce dye formation efficiency.

Such effects are estimated to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means a sulfite ion concentration of J2,0XIO-3 mol/l or less, and most preferably no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

The expression "substantially not containing hydroxylamine" as used herein means preferably a hydroxylamine concentration of z, oXio-3 mol/l or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

Here, organic preservatives refer to all organic compounds that reduce the rate of deterioration of aromatic primary amine color developing agents by adding them to processing solutions for color photographic materials. That is, they are organic compounds that have the function of preventing the oxidation of color developing agents by air, etc. Among them, hydroxylamine derivatives (excluding hydroxylamine; the same shall apply hereinafter) are acids, hydrazines, Hydrazides, phenols, α-hydroxyketones, α-amictones a, s, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed Cyclic amines are particularly effective organic preservatives. Hiroda 6j! issue, same j
j-jlj / issue, 63-Ko 37th issue Q, 6! −j
A4j$ issue, tl-jr1311 issue, 43-4A
3/It issue, same at-ipto4ci issue, same 63-1 bow! No. 7, No. 47-1 Hiroshi No. 464, U.S. Patent No. j, 4iz
, zos issue, Muko, $Pμ, 203 issue, Tokukaisho! It is disclosed in Kono Hiro No. 3020, Special Publication No. 4/Lt-3o4A-4, etc.

Other preservatives include JP-A Showa Tough-uuiur and JP-A-77-! ! Various metals described in No. 7442, JP-A-Sho If
-/1F0111 salicylic acids, JP-A-Sho re-
Alkanolamines described in Jta No. 3.2, JP-A No. 4
If necessary, the polyethyleneimine compound described in US Pat. No. 7.74L4 etc. 14417 may be contained. Alkanolamines, especially triethanolamine,
The addition of dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Among the organic preservatives mentioned above, hydroxylamine self-conductor and hydrazine derivatives (hydrazines and hydrazides) are particularly preferable.
6 pieces in one! ! Core No. 0, same≦3-2713, same 63
- Tough/No. 4A, same ts-iii.

It is written in No. 0, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines such as those described in Japanese Patent Application No. Shobu/-, 2jj/, and
Examples thereof include amines such as those described in Japanese Patent Application No. 391/1999, and other amines such as those described in Japanese Patent Application No. 3-27/J and Japanese Patent Application No. 2003/1999 tz-//100.

In the present invention, 1,! of chlorine ion is added to the color developer! X
10 ~/, jX10 mol/l is preferably contained. Particularly preferably %riX10-2~/x10-'
%tv/l. The chloride ion concentration is /, jXlo
If it is more than mol/l, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Also, s, rxio-2 mol/1
If it is less than that, it is not preferable in terms of preventing fogging.

In the present invention, 3.0% bromine ion is added to the color developer.
It is preferable to contain /l-/, 0x10"-3 mol/l in X10 mo. More preferably, z, oxio
~rxio moh71. If the bromide ion concentration is more than Ixlo mol/l, the development will be delayed and the maximum density and sensitivity will be reduced, and if it is less than J,0X10 mol/1, fogging cannot be sufficiently prevented.

Here, the chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the photosensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from a 9It base brightener added to the developer.

As a supply material for bromide ions, sodium bromide, potassium bromide, a/-T:nium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, bromide Examples include cerium and thallium bromide, of which potassium bromide and
Sodium bromide.

When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

The color developer used in the present invention preferably has a pH of 2
˜lλ, more preferably ˜//, 0, and the color developer may contain other known developing component compounds.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt,
N,N-dimethylglycine salt, Leukune salt, /Leoishi/salt, guanine salt, 7,4'-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, co-amino-λ
-Methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble at pH 9.
, has excellent buffering ability in the high pH range of 0 or higher, has the advantage of not having any negative effects on photographic performance (such as fog) even when added to color developers, and is inexpensive. It is particularly preferable to use

Examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax J, potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate J, potassium o-hydroxy7benzoate, sodium ter-sulfo-4-hydroxybenzoate (!-sodium sulfosalicylate) , !-potassium sulfo-cohydroxybenzoate (1-potassium sulfosalicylate), etc. However, the BA of the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is o, imol/1
or more, particularly o, imol/l-0,
It is particularly preferable that the amount is 100 mol/no.

In addition, various chelating agents can be used in the color developing solution as an anti-settling agent for calcium or magnesium, or to improve the stability of the developing solution.

Nitrilo three loa! , diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N/he'-tetramethylenesulfonic acid, transcyclohexanediaminetetraacetic acid, /, J-diaminopropanetetraacetic acid , glycol ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, cophosphonobutane/, 2. -tricarboxylic acid, l-hydroxyethylidene-1,/-diphosphonic acid, N,N/-bis(cohydroxybenzyl)ethylenediamine-N,N/-diacetic acid.One or more of these chelating agents may be used in combination as necessary. It's okay.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
90. It is about /9/1077.

Any development accelerator can be added to the color developer if necessary.

As the development accelerator, Japanese Patent Publication No. 37-itorr, No. 3
7-! t7, 1t-7r coro, 4c4A-i
xzro, at-yoi, and U.S. Patents I and T
ii, thioether compounds represented by Kosan No. 7, etc.
p-7-dienediamine compounds shown in JP-A No. 1Pt22 and Mukai 10-/11141, JP-A No. 7777,26, JP-A No. 4Iφ-3007, JP-A No. 4Iφ-3007, JP-A No. ! a-iztt coro issue and same t, 2-4! J
Grade ammonium salts represented by Hirokota, etc., US Patent No. x, 4c9u, P03, US Pat. /ko r, /12
No. 4c, Jj7, 72≦ No. 3.2j3. ri12
No., Special Publication Showμ/-//uj/No., U.S. Patent No. J, 44r
ko, j san otsugo, ko, jri t, octopus and 2.21
2.3 Amine compounds described in Reference No. 6, etc.,
/601 issue, same ≠ Coco! λ0/, U.S. Patent No. 1.
/λr, its issue, Special Publication No. 41/-114131, same! , 2-airri and U.S. Patent No. 3. j3, 10
Polyalkylene oxides represented by No. 1 etc., other l-phenyl-3-pyrazolidones, imidazoles,
etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. Antifoggants include alkali metals such as sodium chloride, potassium bromide, and potassium iodide.
Logenides and organic antifoggants can be used. Organic antifoggants such as benzotriazole, t-
Nitrobenzimidazole! -Nitroindazole! -Methylbenztriazole,! -Nitrobenzit Q7/-! Typical examples include nitrogen-containing heterocyclic compounds such as -chlorobenzotriazole, corchiazolyl-benzimidazole, λ-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer applicable to the present invention preferably contains a fluorescent brightener. As fluorescent brighteners, Hiroshi, San'
-diaminoco, λ'-disulfostilbene type compounds are preferred. The amount added is 0-. 11/l preferably 0.79
~ Reference &/l.

Moreover, various elliptical surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer that can be applied to the present invention is 10-
j00c is preferably 3O-IIooC. Processing time Kiko Q seconds~! minutes, preferably 30 seconds to λ minutes. It is preferable to have a small number of replenishing machines, but 2 per m2 of photosensitive material is required.
o-tou is suitable, preferably jO~1ooy
It is a. More preferably, toxa~ko00ml. Most preferred are torttt to izom.

Next, a desilvering process that can be applied to the present invention will be explained.

Generally, any process such as a bleaching process-fixing process, a fixing process-bleach-fixing process, a bleaching process-bleach-fixing process, a bleach-fixing process, etc. may be used for the iron removal process.

The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below.

As the bleaching agent used in the bleaching solution or the Fi bleach-fixing solution, any bleaching agent can be used, but in particular organic complex salts of iron (In) such as ethylenediaminetetraacetic acid,
Complex salts with aminopolycarboxylic acids such as diethylenetriaminepentaacid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acids, or organic acids such as citric acid, tartaric acid, and malic acid; persulfates; hydrogen peroxide etc. are preferable.

Among these, organic complex salts of iron (nl;) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Phosphone rR or salts thereof are listed as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 7,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid,
Examples include cyclohexanediaminetetrah'toic acid, metheriminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid, and the like. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and the iron (mJ) complex salt of methyliminodiacetic acid are preferred because they have a high bleaching edge.

These ferric ion/complex salts can also be used in the form of iron salts, such as ferrous sulfate, ferrous chloride, ferric nitrate, ferrous ammonium sulfate, ferrous phosphate, etc. A ferric ion complex salt may be formed in a solution using 1 iron or the like and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. Further, the chelating agent may be used in excess of the amount required to form the ferrous ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the addition amount curve o, oi-i, o mol/l, preferably 0.0! ~O,jO mol/l.

Various compounds can be used as bleach accelerators in the bleach, bleach-fix solution and/or their pre-bath. For example, US Pat. Koto, rtJ specification, JP-A-Sho! 3-ta!
Publication No. 630, Research Disclosure No. 1712
Compounds having a mercapto group or disulfide bond described in the July issue of 7R, and the
O6, JP-A No. 7.2-20132, JP-A No. 3-327
No. 11, U.S. iiJ, 706. Thiourea-based compounds or halides such as iodine and bromide ions described in No. t4/ etc. are preferred because they have excellent bleaching properties.In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention includes: Bromides (e.g. potassium bromide, sodium bromide,
Ammonium bromide or chlorides (e.g. potassium chloride, sodium chloride, ammonium chloride; or iodides (e.g. ammonium iodide) or iodides (e.g.
A rehalogenating agent such as anthonium iodide J may be included.

If necessary, one or more inorganic substances having a pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and phosphoric acid. Acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agent used in the bleach-fixing solution or fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thionanate and ammonium thiocyanate; ethylene bisthioglycolic acid. , 3. Water-soluble silver halide solubilizers such as thioether compounds such as rougethia-/, l-octanediol and thioureas, which can be used alone or in combination of two or more species. .

Further, a special bleach-fixing solution consisting of a combination of a fixing agent and a halide such as a polydisperse of potassium iodide as described in JP-A-5R-IZZSZA may also be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per /l is
0.3 to 2 mol is preferable, more preferably o, zi
, o mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3 to 10, and particularly preferably 3 to 10.

The bleach-fix solution may also contain other fluorescent brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain preservatives such as bisulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium monobisulfite, sodium bisulfite).

potassium bisulfite, etc.], metabisulfite (e.g.
It is preferred to contain a sulfite ion releasing compound such as potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

These compounds are about 06O-~ in terms of sulfite ions.
0.0! The content is preferably 0 mol/l, more preferably 0, 0 to 00 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, fluorescent brighteners, chelating agents, antifoaming agents, antifungal agents, and the like may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, the number of materials used such as couplers, the application, the temperature of the washing water, the number of stages in the washing tank), the replenishment method such as countercurrent or forward flow, and other conditions. Can be set to . Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of Motion Picture and Television Engineers.
alof the 5ociety of Mo eyes on
Picture and Television En
Gineers) 4th Counselor, P, Koda T-2! ! (/
Rit! Year! You can request it using the method described in Monthly Issue J. Usually, the number of stages in the multi-stage countercurrent system is preferably from 1 to t, particularly preferably from λ to t.

According to the multi-stage countercurrent method, the amount of washing water 1 can be greatly reduced, for example, to 90.11 -/l or less per m2 of photosensitive material, and the effect of the present invention is remarkable. The increased residence time of water causes problems such as bacteria propagation and the resulting floating matter adhering to the photosensitive material.

As a solution to this kind of problem,
The method for reducing calcium and magnesium described in No. t can be used very effectively. In addition, chlorine-based disinfectants such as inthiazolone compounds and thiabendazole described in JP-A No. 77-414c, chlorinated sodium incyanurate described in JP-A No. 4/-/KOIU,
Benzotriazole, copper ion, etc. described in Japanese Patent Application No. 1011717/1973, “Chemistry of Antibacterial and Antifungal J” written by Hiroshi Horiguchi.
2011] Sankyo Publishing, Hygiene Technology Society, ed. "Sterilization, sterilization, and anti-mildew technology of microorganisms" (/r, 2011, 2nd year 2 Industrial Technology Society, Japan Antibacterial and Mildew Society ed. [Encyclopedia of Antibacterial and Mildew Agents J (/ It is also possible to use the fungicides described in R.R.T.

Further, in the washing water, a surfactant as a draining agent and a chelating agent such as EDTAK as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound that has an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound represented by formalin, or an IP compound suitable for dye stabilization.
)11CiM! Buffers and ammonium compounds for manufacturing can be used. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, a surfactant, a fluorescent brightener, and a hardening agent can also be added. In the processing of the photosensitive material of the present invention, when stabilization is achieved directly without going through a water washing process,
No. 41uj, II-/No. 44134L, Bu0-JJO3
≠! Any of the known methods described in No. 1, etc. can be used.

Others: l-hydroxy-7 etheridene-1. It is also a preferred embodiment to use a chelating agent such as l-diphosphonic acid, ethylene/diami/tetramethylenephosphonic acid, or a magnesium or bismuth compound.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

Preferred pHFi in the water washing step or stabilization step is more preferably one! ~l. The temperature can be set in various ways depending on the use and characteristics of the photosensitive material, but generally it is l! ~Hiroshi!
QC is preferably Chichiko O to San000. Although the time can be set arbitrarily, a short time is desirable from the viewpoint of reducing processing time. Preferably l! Seconds to 1 minute! more preferably 30 seconds
seconds to 1 minute and 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

Preferred replenishment 1 includes photosensitive material, 0.1 to 10 times the amount brought in from the prebath per unit area, preferably 3
It is 2 times to aO times. Or it is less than /l per m2 of photosensitive material, preferably less than roost. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. As an example of this, a multi-stage countercurrent method is used to reduce the overflow of washing water and flow it into the bleach-fixing bath, which is the previous bath, and replenishing the bleach-fixing bath with concentrated solution to reduce the amount of waste solution. It will be done.

To develop color photosensitive materials for photography, normal color negative processing and color reversal processing are applied.

As additives to the color developing solution, processing solution additives that are used to process color sensitive materials for printing first are used, but other additives include organic solvents such as ethylene glycol and dienalene glycol, polyethylene glycol, and quaternary Development accelerators such as ammonium salts, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone and its derivatives, and thickeners are also added. can.

In addition, the color development time is usually 2 to 3 minutes, but
By increasing the pH or color developing agent concentration,
It can be done in less than 2 minutes. The 94Fi is not only a color negative photosensitive material for photography/color photographic paper and a printing system, but also a color negative photosensitive material for photography/color positive film,
Applicable to printing systems and photographic reversal color sensitive materials/positive color photographic paper (such as those using direct positive emulsion and those using reversal color processing); and printing systems, etc.

Reference Example: Preparation of magenta coloring layer of color light-sensitive material for printing (silver halide emulsion!!14m) To iooow, a 3% aqueous solution of lime-treated gelatin, 4 cg of sodium chloride was added, and N,N/-dimethylimidazolidine- Corchion (30.2 g of 1% aqueous solution was added to the tube. In this solution, an aqueous solution containing 0.02 mol of silver nitrate, O, Oa mol of potassium bromide and 0./l of sodium chloride were added.
The aqueous solution containing mol A/W was added and mixed at jλ''C with vigorous stirring. Subsequently, the aqueous solution containing o, r mol of silver nitrate, 0.11 mol of potassium bromide, and 0.411 mol of sodium chloride were added. Do not vigorously stir the aqueous solution containing
, and mixed at 2°C. Seven minutes after the addition of the silver nitrate aqueous solution and the alkali halide aqueous solution was completed, no [! −
Phenyl, z-(J-(z-)J-(J-sulfonatoethyl)benzooxazoline-noylidenemethyl)-/-butenyl)-3-penzooxazolio]ethanesulfonic acid pyridinium salt, 2J '/;, 7■ was added. After being kept at 0C for 11 minutes, it was desalted and washed with water. Furthermore, 0.09 g of lime-treated gelatenta was added, triethylthiourea was added, and chemical sensitization was carried out optimally so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 7% emulsion) was emulsion A-/.

In emulsion A-/, the molar ratio of potassium bromide and sodium chloride used was changed, and emulsion B-1% C-/ was obtained in the same manner.

Next, 3.3 g of sodium chloride was added to 70001 3% aqueous solution of lime-treated gelatin, and 3.3 g of N,N/-dimethylimidasilidine-corchion (1% aqueous solution) was added. λ1 was added. While vigorously stirring an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride in this solution! The mixture was added and mixed at 0C. Next, add silver nitrate to Q,
7! An aqueous solution containing moles of sodium chloride Q, 7! While vigorously stirring the aqueous solution containing moles! Added and mixed at λoC. Seven minutes after the addition of the silver nitrate aqueous solution and the sodium chloride aqueous solution was completed, 2-Cj-722-(-1[!-Phenyl-J-(,2-sulponatoeternonepenzooxazoline-noylidenemethyl)] was added. -Norbutenyl)-3-penzooxazolio]ethanesulfonic acid pyridinium salt 2r6.7~ was added. After sorting at 2"C, an aqueous solution containing 0.05 mol of silver nitrate and potassium bromide were added. 0.02 mol and sodium chloride 0.03
#ooc was added and mixed with an aqueous solution containing moles while stirring vigorously. Thereafter, it was desalted and washed with water. Further, lime-treated gelatin W0.01f and triethylthiourea were added to carry out optimal chemical sensitization so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 2 mol S) emulsion was finished as emulsion 1).

For emulsion D-/, potassium hexacyanoferrate (II) trihydrate was added to the sodium chloride aqueous solution added at the λth time.
0■, and 1.0% of hexachloroiridium (■ potassium phosphate) to the aqueous alkali halide solution to be added for the third time.
An emulsion was prepared with the only change being the addition of No. 19, and Emulsion D
-I made it.

In this way, i14 was manufactured. Grain shapes, grain sizes, and grain size distributions of four types of silver halide emulsions A-/ to D-, 2 were determined from electron micrographs.

The silver halide grains contained in the emulsions A-/ to D-co were all cubic. The particle size was expressed as the average value of the diameter of a circle equivalent to the projected area of the particles, and the particle size distribution was calculated using the value obtained by dividing the standard deviation of the particle size by the average particle size.

Next, the halogen composition of the emulsion grains was determined by measuring X-ray diffraction from silver halide crystals. Using monochromatic CuKa radiation as a radiation source, the diffraction angle of the diffraction line from the <JOO) plane was measured in detail. While a diffraction line from a crystal with a uniform halogen composition gives a single peak, emulsions DI and D2 used in the present invention give a main peak and shoulders corresponding to their compositions. By calculating the lattice constant from the measured diffraction angles of the main peak and shoulders, the halogen composition of the silver halide constituting the crystal can be determined. The results are summarized in Table 7.

(Preparation of emulsion of magenta coupler) Magenta coupler (a) Kota, 4g and color image stabilizers (b3t, ry,
ic) //, ethyl acetate io, ow and solvent (d
) 3 If, add and dissolve this solution, io@sodium dodecylbenzenesulfonate 2
An emulsified dispersion (in) was prepared by emulsifying and dispersing the gelatin in an aqueous gelatin solution containing 0 df θ% (3 JOyd).

Next, magenta coupler (e) 3/,! 9. Color image stabilizer (c)/3.7g, stain inhibitor (fJco, 79,
(gJ-2,-9, ethyl acetate and solvent<b)i
i, 1ynt, (1) Coλ, t1 are added and dissolved, and this solution f10% sodium dodecylbenzenesulfonate J
The mixture was emulsified and dispersed in three 0% seratin aqueous solutions Q1 to prepare an emulsified dispersion (b).

The silver halide emulsion thus obtained and the emulsified dispersion of magenta coupler were combined to prepare a coating solution having the composition shown in Table 2, and the coating solution was coated on a paper support laminated on both sides with polyethylene. Ten types of photosensitive materials were prepared by coating with the layer configurations shown in Table 2.

The gelanan hardening agent for each layer is l-oxy-3°! −
Dichloro s-triazine sodium salt was used.

<11) Magenta coupler (bJ color image stabilizer (e) magenta coupler (invention) (03 color image stabilizer (f) stain inhibitor (d) solvent (g) stain inhibitor (h) solvent (11 solvent ( CB H170tTP = 0 (j) Antifoggant The performance of the 70 coated samples thus obtained was tested.

Each coated sample was exposed to light for 0.1 seconds <20ocMs) through an optical wedge and a green filter, and color development was performed using the development process and developer shown below.

The reflection density of the obtained treated sample was measured and a so-called characteristic curve was determined. Sensitivity is the reciprocal of the exposure amount that gives a density 0.2 higher than the overlapping density, and the coating liquid t-
The sensitivity of the sample applied 30 minutes after preparation was expressed as a relative value with ioo. Also, from the amount of light a that calculated the sensitivity, 0.2
The difference between the density corresponding to the increased exposure amount and the density at the point where the sensitivity was calculated was determined and used as the contrast.

These results are shown in the table below.

Color development processing S Processing process Temperature Time Color development See Jj'C! Bleach and fix for seconds 30~Jj'C4Ij seconds rinse ■ 3Q~jj"c 20 seconds rinse ■
30~Ij0C217 seconds rinse 0 30~! ! 0
C Rinse for 20 seconds ■ goNzz Dry for 0 seconds
7O-II °CtO seconds (μ tank countercurrent method from rinsing ■ to ■) The composition of each treatment solution is as follows.

Color developer water 100r
d ethylenediamine-N, N, N.

N-tetramethylenephosphonic acid triethylenediamine (/, diazabicyclo (J, CO, CO) octane) Sodium chloride potassium carbonate N-ethyl-he-(β-methanesulfonamide ether)-J-methyl-Hiroshi-aminoaniline sulfate N,N-diethylhydroxylamine firefly-X increase 11J (UVITEX CK/, j9!, 09 i, ug, 2! 9!, OI reference, J9 Ammonium thiosulfate (70%3 sodium sulfite ethylenediaminetetraacetic acid uni) Ammonium ethylenediaminetetraacetic acid uni) Disodium acetate ammonium bromide / 001LI /Ill rg 3g Hiroog Add water 10g0nlpH
(Coj'cJ j,! Rinse liquid ion exchange water (calcium and magnesium are each jpp
m or less, add water and pH (lt'c) Bleach-fix water 000n1 10.10 00ml
, io''''4 moles were added.

The relative sensitivity and contrast results obtained are shown in Table 1.

Figure 4 shows the spectral sensitivity distributions obtained for sample roll 1 and sample roll 1.

In addition, the spectral reflectance curves of the various color images obtained with the samples Ehiro and Rosan are shown in Figure 2.

It can be seen from Table 1, FIG. 7, and FIG. 2 that the GL according to the present invention has suitability for rapid development, and has good color separation in terms of spectral sensitivity distribution and spectral absorption characteristics of various colored images.

Example 1 (Preparation of color photosensitive material samples I to J for printing) A multilayer photographic paper having the layer structure shown below (
Sample -/) was prepared. Apply the coating liquid as follows.
Lalli! did.

(Yellow coupler (ExY-/) i, /l and color image stabilizer (cpa-/J Hiroshi, Part 9, #acid ethyl core, λc
c and high boiling point solvent (8o1v-J)y,'raa<t
, og) t- was added and dissolved, and this solution was emulsified and dispersed in a 10% gelatin aqueous solution trzac containing 10% sodium dodecylbenzenesulfonate rCC. This emulsified dispersion and emulsions EM/and EM were mixed and dissolved, sulfur sensitized, and then the gelatin concentration was adjusted to have the following composition to prepare a first layer coating solution.

The coating liquids for the second to seventh layer phases were also prepared in the same manner as the coating liquid for the first layer. Fi/-oxy-2,2-dichloro-3-triazine sodium salt was used as the gelatin hardening agent for each layer.

Moreover, Cpd-741 was used as a thickener.

(Layer structure) The composition of each layer is shown below. Numbers are coating*<9/m2)
It represents Ding. The silver halide emulsion was coated in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (Ti02) and a bluish dye. ] th layer (blue-sensitive layer) Monodispersed silver chlorobromide emulsion (EM/) spectrally sensitized with a sensitizing dye (Exa-/)... 0.02 Spectrally sensitized with a sensitizing dye (Exa-/) Sensitized monodisperse silver chlorobromide emulsion (EM Co) ... 0.2 l Gelatin ... /, rbu yellow coupler (ExY-/) ... O, rλ Color image stabilizer (Cpd- /) ... 0. /ri(C
pd-ta) ... o, ot solvent (8o1v-z
) ...-o, is second layer (color mixing prevention layer gelatin ... O, Tata solvent (
8o1v-1) -・-o, or color mixing inhibitor (
Cpd-4) ... o, or solvent (8o1v-
/) ... 0. lt tertiary N (green sensitive layer i Monodisperse silver chlorobromide emulsion spectrally sensitized with a sensitizing dye (ExS-2,31) (EMjJ...0.01 with a sensitizing dye (Exa-1,3) Spectrally sensitized monodisperse silver chlorobromide emulsion (EM457 0.11 gelatin... /, J reference magenta cazolar (ExM-/) 0.32 color image stabilizer (cpct-J)... o, iz color image stabilizer (Cpd-4C)... o, i co-solvent (Solv-JJ--6, co! 4th layer (ultraviolet absorption layer low gelatin)... i, rr ultraviolet absorber (cpa- ta/Cp d-4/cpa-7=ko/
Reference/Hiroshi weight ratio] 0.70 Color mixture prevention agent (cpct-r)... 0.0! Solvent (8o1v-jn... 0. Cog fifth layer (
Red-sensitive layer) Monodisperse silver chlorobromide emulsion (EMj) spectrally sensitized with a sensitizing dye (ExS-Hiroshi, 2) ... 0.02 Spectrally sensitized with a sensitizing dye (ExS-41, 2) Monodisperse silver chlorobromide emulsion (EMj) 06 CoQ Gelatin... /, J-san cyankazol (ExC)... 0.3" Color image stabilizer (Cpd-/Red color image stabilizer (cpct-y) ) (Cpd-/G) Solvent (Solv-6) Sixth layer (ultraviolet absorbing layer) 1+!2 Chin...Q,!3 UV absorber (Cpd-j/Cpd-A/Cpd-7=Co / San / Hiroshi: weight ratio) ... 0.76 Color mixing prevention agent (Cpd-r) ... 0.02 Solvent (8o1v-z) - o, or seventh layer (protective layer) Gelatin ... Polyvinyl Acrylic modified copolymer of alcohol (degree of modification 17%; ... O, /7 Liquid paraffin ... o, oi,
At this time, Cpd-
/ 0. cpct-// was used.

Furthermore, each layer contains an emulsifying dispersant and a coating aid such as 5,/7, 3, o4/L, 7! , 33 Alkanol XC (Dupont), sodium alkylbenzene sulfonate, succinate ester and Meg
afac F-/co0 (manufactured by Dainippon Ink Co., Ltd.) was used. As a stabilizer for silver halide, cpct-l, c
pct-/j was used.

In sample-7, the composition of the third layer was changed as follows,
A sample was prepared in the same manner as above.

Monodispersed silver chlorobromide emulsion (EM-J) spectrally sensitized with third layer sensitizing dye (Exa-J, 33)...0.03 Spectral sensitization with sensitizing dye (Exa-J, J) Monodispersed silver chlorobromide emulsion (EM-1)...0.02 Gelatin...i, t.

Magenta coupler (ExM-co) O, J red color image stabilizer (cpa-3)...0. /! (C
pd-/7) ... 0.03(Cpd-/r)
... 0.0 lv-λ, ko!xC (8°! molar ratio) Ex8-/ Ex M-/ 5o3HN (C2H5) 3 and xS-j xS-2 803) iN(C2H5)3 Ex8-1 cpa-/ pct-2 H pct-J Cpd- pct- t Cpd-4 Cpd-// Cpd-/CoCpd-/j (:pd-/A 8o1v-/: 5olv-Coni8o1v-j: 8o1v-Hiroshi; 8o1v-Conidigitylphthalatetrioctylphosphatetrinonylphosphatetri Cresyl phosphate C00Cs)i,? (CH2) 8 Coocs) 11 fo1v-6: Average particle diameter "I B, content Cpd-1! cpa-/ λ of Ta: II: 4A mixture (weight ratio) EM/ Cubic o, rr o, a o , or
EM cube 0.70 0. Ko o, i.

EMj Cube o, zr o, t o, t.

EM Hiro Cube o, iy o, t o, ot
EMj Cube 0.11 O,t O,0
2EMU cube O1≠! 0. Bu 0. //＋
l In this case, the principal is expressed as an average based on the projected area.

Tatami 2 It is expressed as the ratio (8/d) between the statistical standard deviation (S) and the average particle diameter (d).

ExM-ko (body example M-j) (' p d -/ 7 Emulsion layer shape Particle size Br content variation coefficient C3H
11(t) (: p d −/If α In sample-7 or sample-2, the silver chlorobromide emulsion to be used was changed as shown below and used in sample-1, and in the same manner as in sample-3 (sample-2). -7)' or Sample-Reference (Sample-7)
2) was prepared.

(μm) (mo1%) EM-7 cube o, rl 10 0. ot(E
M-/alternative) to, yo to
o,i.

(EM-ko substitute) Ta o, zz
xi o, t.

(EM-j alternative J 10 o, iy xi
o, or (EM-reference substitute)] / 0.rlr 77 0.0
? (EM-j alternative) lko O1≠1 73 0.
//(EM-bu alternative (preparation of color photosensitive material sample 1oi-iop for photography) Sample IO! (for comparison) On an undercoated cellulose triacetate film support,
Sample IO/ (for comparison), which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the optical layer) Coating amounts are expressed in units of 97m of silver for silver halide and colloidal silver, and ILt-1 is expressed in units of !//m2 for couplers, additives and gelatin.
The sensitizing dye is expressed in terms of the number of moles per mole of silver halide in the same layer.

The symbols indicating additives are shown below. However, if it had multiple effects, it could fight on behalf of one of them.

Uv; ultraviolet absorber, 8o1v; high boiling point ■organic solvent, Ex
F; dye, ExS; sensitizing dye, Ex C; tan coupler, ExM; magenta coupler ExY; yellow coupler, Cpd; additive tube 11 (Hareshicon Fjll
) Black colloidal silver...0. /! gelatin
...2.2UV-/
-0,0jUV-J...0.0
≦Uv-s-o, 07Sol
v-co-・o, orExF-/
・0.0/ExF-2・
・・o, oi λth layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag I Hiromorch uniform sphere equivalent diameter O1≠μ
Fluctuation system of equivalent sphere diameter: 37 yen, plate-like particle diameter/thickness ratio: 3.
0) Application amount...O0 gelatin...o, rEx x 8-
/ ,,,ko,zxio-'Ex
a-2-3,7X10'ExS-7・#,O×10' ExC-/ -0,/7Ex C-J
-0,01ExC-3---0,/
3 3rd layer (medium-sensitivity red-sensitive emulsion layer) Minor silver iodobromide emulsion (AgI 4 molti, core-shell ratio 2:l, internal height Ag1 sphere equivalent diameter 0.61μ, variation system of sphere equivalent diameter 2!chi, plate-like grains , diameter/thickness ratio, 0) coating saw machine...
・O,tS silver iodobromide emulsion (Ag14' morti, homogeneous-Ag
l type, equivalent sphere diameter Q, reference μ, fluctuation system of equivalent sphere diameter 37 yen,
Platy particles, diameter/thickness ratio 3. O) Coated silver amount...θ, l Gelatin.../, 0Ex8-/-
KOX10-' Ex8-J -j, KOXio
'Ex&-7-7X/ 0-6 ExC-/ ・0.3/ExC-co ・o, oiExC-J
・=0. OA third layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Aglj moltimol ashel ratio λ:l internal high Agl type, equivalent sphere diameter 0.7μ, variable series of equivalent sphere diameter Ko! 俤, Plate-shaped particles, diameter/thickness ratio, !1 coated silver amount・
...O, tazelatin ...01rE
X8-/-.../, AX/
0""-'E x 8- J...
・KO, 4X/ 0″″4Exa-7-AX/ 0″-’ ExC-/ ExC-Hiroshi8o1v-/ Solv-i pct-7 5th layer (intermediate layer J Gelatin...0.tUV-≠
... o, oiUV-z
...0.0 Cpd-/ ・
...Q, /Polyether acrylate latex...0.0r Solv-/-=0. Oj 6th layer (
Low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag14' morti uniform type. Equivalent sphere diameter 0.
vμ, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 37%,
Platy particles, diameter/thickness ratio, o) Application II &
Amount...0. /r gelatin...Q,
vE x 8-7 -=koX10-'・
...0.07 ...0.0! ...0.07 ...0. JO... Reference, 4X/)-'ExS-1...7X10-' Ex8-r -zxio-'ExM-
j ・・・0, //ExM
-7・ 0.03 ExY-r...-o, oi
Solv-/...0.0ri8o1v
−# = 0.0/7th layer (medium-sensitivity green-sensitive emulsion layer)
:/ surface height Agl type, equivalent sphere diameter o, rμ, coefficient of variation of equivalent sphere diameter 2!忤, plate-shaped particles, diameter/thickness ratio, 0) Coated silver amount...0.27 Gelatin...
0.4'Exa-j-JXlo-'
Ex8-1 ・7X/ 0"-'
Ex8-z -txto-'ExM
-r -0, 77ExM-7-0,0
44 ExY-t ・0.028o1v-
/ =0. /418 o l v -1
---0, 02 Layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Aglf, 7 molar ratio, multilayer structure grains with a silver content ratio of 3:3:0, from the Agl-containing world to 7 moles) , 0 moles, 3 moles, equivalent sphere diameter 0°7μ, coefficient of variation of equivalent sphere diameter 2s%, plate-like particles, diameter/thickness ratio/, 4) 1 coat of coating...0.7 Gelatin...o , rEX 8-
!・j, λX10-'Ex8-j
・・・-/x/Q″′″4Ex 8-
t ・o, J X t o-'E
x M −j ...0. /ExM
-a・0, OJExY-r
・ o, o, 2ExC-/
・0.02ExCu・
o,oiSolv-/...O,ko!
8o1v-2-0,01 Solv-4-0,0/ cpcl-7/X10-' 2nd layer (middle layer) Gelatin...01tCpd-/
...θ, OU polyethyl acrylate latex...Q, 112 8o1v-/ ...0.0.2th io
layer (donor layer for interlayer effect on red-sensitive layer) silver iodobromide emulsion (AglJ molar range, core-shell ratio conyl internal height Agl
Type, equivalent sphere diameter 0.7μ, fluctuation coefficient of equivalent sphere diameter/1r%,
Monodisperse, plate-like grains, diameter/thickness ratio 2.0) Coating @ amount... o, tr Silver iodobromide emulsion (Ag14' molar average type, equivalent sphere diameter 0.
2μ, fluctuation coefficient of equivalent sphere diameter, ? 7%, plate-like particles, diameter/
Thickness ratio 3.0) Coating sil...0. lf Gelatin.../, QExS-s
-4xto-'ExM-/0
-0, /ri5olv-/
---0, CoO 11th layer (yellow filter layer - yellow colloidal silver...0.01 gelatin
...00tCpd-ko
...0. /38o1v-/ ・-・
0. /ICpd-/ =0.07Cp
d-4...0.00 coH-/...o, is 1st λ layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag14t, z morch, uniform-Aglff
1. Equivalent sphere diameter: 0.7μ, variation of equivalent sphere diameter: 1, plate-like grains, diameter/thickness ratio: 7.0) Coated silver amount: 0.3 Silver iodobromide emulsion (Aglj molar coefficient, uniformity) -Agl type, ball equivalent diameter 0.3μ, ball equivalent diameter variable number of threads 3°, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount...0. lf Gelatin...1. tExS-t
...R Silver bromide emulsion (Ag110% ruti, internal high Agl type, equivalent sphere diameter i, oμ, variation series of equivalent sphere diameter -2!Rice, multi-twinned plate-like grains, diameter/thickness & ratio -0) 111 cloth Silver amount...0. ! Gelatin...0
．． 2Ex8-4 ・1xio-'E
xY-ta-0,0/ExY-//
-0, JOExC-/
-0,02Solv-/...0.
10...0.20...0.7...0.01...0.03...O, l 3rd/life/O8tri...o, 4I...0. 3 Tei@/j layer (first protective layer) Fine grain silver bromide emulsion (Aglλ Mortimol Agl type, equivalent sphere diameter 0.07 μm Coated silver amount...o, i Cogelatin...o, y UV-Hiroshi
...0. //UV-z
...0. /68o1v-1---0,0J H-)...0. /Jcp
a-t...0.10 Polyethyl acrylate latex...Q, Ota 76th layer (second protective skin) Fine grain silver bromide emulsion fAglλ morch, uniform A.

1 m, equivalent sphere diameter 0.7 μm Coated silver amount...0.36 Gelatin...o, sr polymethyl methacrylate particle diameter/, jμ...0.2 H-t...0. /7 In addition to the above components, each layer contains an emulsion stabilizer cpct-J (0,
0711/m ) surfactant Cpd-≠(0,039
/m2) was added as a coating aid.

Sample 10.2 (Comparative 2) Sample ioλ (comparative) was prepared in the same manner except that the sensitizing dyes 2.3 and m1 of Sample 10/ were changed as shown below.

2nd layer E
-'Ex8-co-J, 4X10-'Ex8-1
---/, KoXノ(t -4Ex8-7
-1r, 0X10 3rd layer EXS-/Exa-koExS-t ExS-7...ko...ko...l...7 0x10-'Ax10"oxio"-' X10- 6 Layer E
・4, QX/0-'Sample 103 (
Invention J Sample 103 (Invention 1) was prepared by changing the sensitizing dyes No. 2.3 and m1 of Sample /Q/ as shown below, and otherwise using the same procedure.

2nd layer ExS-/-,2,jXlo-'Ex
S-ko...ko, i×io-'Exa-t
-/ , AX/ 0-'Ex8-7 -r
, oxio-'Third layer EX,-/Exa-λ Exa-! ExS-7 ...Co--L ...I...7, oXio-', rxio-', X10-', QX/ 0-6 Third layer EX8-/ ExS-CoEx x 8 - j ExS-7 N-7 .../ ...O ...t txto-' yxio '7X10"-' 0x10-6 Sample io Hiro (unexploded F!A) Sample 10/No. Sample ioμ (invention J) was prepared in the same manner except that the sensitizing dyes of 3 and m1 were changed as shown below.

2nd layer E x 8- / ..., Ix10
-'ExS-1・1.4! X10-'E x 8-! -2,3XIQ-4Ex8
-7 -r, OX/ 0''-'V IV-2 3rd layer Exa-/ExS-koEx8-j ExS-7 3rd layer Exa-/Exa-koExS-j ExS-7 ・...ko, oxio"-' ...1. Koxio-' ...ko, Ox10-' ...7.0X10-6 ...l ...l Parable...l ...t, Todoroki xio-', 4X10-', oxto- ', oxio-' V-3 H II route;-tl13 嘗C1l.

UV-4 UV-5 olv-4 CI(.

C1l.

olv-5 xF-1 H, C, /\CJS olv-1 olv-2 xF-2 MS-1 ExS-2 ExS-3 ExS-4 ExS-7 ExS-8 ExS-5 Snake xs-6 xC-1 xC-2 ErC-3 ExC-4 xM-7 xM-10 xM-5 xM-6 C1l.

xY-8 xY-9 ExY-11 ExY-12 Pd-2 Pd-6 pd-7 pd-1 pd-5 pd-3 pd-4 Samples 1O1 to ioa were exposed using an equal energy spectrophotometer. Thereafter, it was developed using the color development process A described below. Measure the density of the cyan color image and find the sensitivity at each wavelength at the base density + 0.1, obtain the highest sensitivity wavelength, the relative sensitivity at tzo"', and the spectral sensitivity distribution as shown in Figure 3, and use the results. The following are summarized in the table.

In addition, for samples ioi to 104I-, the gray chart and Motoki ratio 1. A red chart divided into two (with spectral reflectance as shown in Figure 1) was photographed under the light source of trooo, and color development processing A was carried out.
It was developed and processed.

Here, the part with the light quantity ratio l is named "Cs", and the part with the light quantity ratio '/ is named "D part". Using the color negative original image obtained in this way, the above-mentioned samples 1 to 1 (color sensitive material for printing) were printed using a Fuji Photo Film Co., Ltd. FAP-3! After that, Fuji Photo Film Company 1i! FPRPJO,
It was processed by the following color development process B or C using a Z-type automatic processor. That is, Samples -7 and -2 were rapidly processed by Processing B, while Samples -3 and mm were processed by Processing Ct because their developing speed and desilvering speed were slow.

In addition, samples lQl to 104! When printing from a color negative original image obtained using a sample 1 to sample 1, make sure that the densities of cyan, magenta, and yellow images at the base a of the gray chart are the same color as the gray of the gray chart under the fluorescent eaves for color evaluation. The baking conditions were adjusted to 1114.

<Color development processing NA> Color development bleaching bleaching fixing washing with water ■ washing with water ■ stable drying <10 Jr'C 3 minutes 75 seconds 31 r'C 7 minutes jr'c 7 minutes 75 seconds Kohiro C da O seconds jloc 1 minute jloc 440 seconds QC) /min/j seconds In the above treatment steps, water washing (■) and (2) were performed using a countercurrent water washing method from (■) to (■). Next, determine the composition of each treatment solution.

The replenishment amount of each processing solution is 11 times the amount of color development per 1 m 2 of color photosensitive material! is 1200m1, everything else is Ro
I made it otttt. Further, the amount of the pre-bath carried into the water washing step was 1.5 oat per 1 m 2 of color photosensitive material.

Color developer> Mother solution Replenisher diethylene triamine/pentaacetic acid l-hydroquine ethylidene-t, i-diminor sulfonate sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate i, og i, ip 2. 0g Hiro, 0g 30.09 1, Hirog no, 39 λ1.2y ≠, Hiro9 3λ, OI o, 7g λ, dy J, 4,9 Hiro-(N-ethyl-N-β-hydroxyethylamino Add Foucault methylaniline sulfate solution to ψ,!y/,Ql!,og/,0l pH10,010,Oj Disodium tetraacetate 10.01/Ammonium nitrate 10.09 Amthonium bromide too, og bleach accelerator
Add 10 mol of ammonia water and add water. Bleach-fix solution> Mother solution/replenisher common pH 4, 3 /, O1 Ethylenediaminetetraacetic acid ferric ammonium salt to, og ethylenediaminetetraacetic acid disodium salt! , 09 Sodium sulfite l, OI ammonium thiosulfate aqueous solution (70%) Add ammonia water, pH 7.3 Add water
/1. Washing water> Calcium ion 3.2/1. magnesium ion 7
．． Tap water containing 3■/l was passed through a column filled with H-type strongly acidic cation exchange resin and OH-type strongly basic anion exchange resin, and calcium ion/, 2W/l, magnesium ion y 0 , 4'Jl11i Add sodium incyanurate dichloride to the water treated to
It was added and used.

Stabilizing solution> Mother solution/replenisher common A/W phosphorus (37% w/v) OI polyoxyethylene-p-monononylphenyl ether (average degree of polymerization io) Add ethylenediaminetetraacetic acid di-sodium salt water pH <Color development processing B> Processing process Temperature Time Replenisher color development f
i Jj'C4/-5 seconds /l/Inl bleach fixing
30~jj'c 4 (5 seconds 2/rrttl rinse■ 30~3yo'JC20 second rinse■ 30~3!r0c, 20 seconds -rinse■
30~110CJO seconds 3! (HrLl drying
The replenishment amount for 70 to 0 cto seconds is per meter of photosensitive material (the 3-tank countercurrent flow method from rinsing ■ to ■ and the composition of each processing solution are as follows).

Color developer Tank liquid water 100N ethylenediamine-N, /, 190.3I.

Replenishment fluid oovt λ, oI! o, ory /1 z, r Tank capacity /71 /71 N,N,N-tetramethylenephosphonic acid triethanolamine r,og Sodium chloride i,pg Potassium carbonate Ko! 9 N=ethyl-N-(β r, og -methanesulfonamidoethyl)-3-methyl-zhen-amine aniline sulfate N,N-bis(carboj,!9 xymethyl)hydrazine fluorescent brightener i, og water'! lot tooorrtpH(λ
, t'c) io, or bleach-fix solution (tank solution and replenishment g, are the same) ammonium thiosulfate i70%) lco, 0g 2g1 7.09 Sodium sulfite /717 ethylenediaminetetraacetic acid iron (IIN!!I / ammonium ethylenediaminetetraacetic acid disodium jylium 7, Ofl add water / 000 gop) 1
(,2j'C) t, 0 rinse liquid (
Tank fluid and refill fluid are the same) Ion exchange water (calcium and magnesium are each 31)
pm or less color development processing C> Ko, Og oooom io, 4! r Reference 00vtl Color development 37°C 3 minutes 30 seconds Bleach fixing JJ''C/min 3o seconds Water washing Cog~34!'CJ revolution Drying 70-40°C/min The composition of each processing solution is as follows. .

Color developer water 100m
l diethylenetriamine pentaacetic acid nitric a triacetic acid benzyl alcohol diethylene glycol sodium sulfite potassium bromide potassium carbonate N-ethyl-N-(β-methanesulfonamide ether)-3 monomethyl-sulfur-aminoaniline sulfate hydroxylamine sulfate fluorescent whitening Agent (WHITEX Part B.

Add water to pH (ko! 0C) Bleach-fix solution water Ammonium thiosulfate (70%) Sodium sulfite/, Og Ko, 0I /Zxt 0m Ko, Ogi, ol ≠, Even 9! ,0g i,og ood to,,zz 300g pH
, 2j 'C) Measure the cyan density of the portions corresponding to section C and section D of the printed photograph taken from 6.70 sample l or reference. I got the value from the table. These results show that the printed photographs obtained by the negative/positive system of the present invention can be obtained in a short time due to rapid processing, and have excellent gradation reproduction of shadows in high red density. .

The points I would like to pay particular attention to are experiment return, io, 13, and lμ.
In Experiment 7I61. Koya! , D part and C compared to B
The difference in cyan density between parts is abnormally high. Also,
Experiment/Experiment 4 at 16F, 10, 13, and Hiro
Even when compared with %/, 2 and /j1/l, the difference in cyan density between portions D and C is quite high. This shows that the use of the high silver chloride color light-sensitive materials for photographing and printing of the present invention improves the reproducibility of shadows, particularly in red images.

(Effect of invention) The following can be seen from the results in Table 1.

1. Colors that can be processed quickly -Par (Sample/Ya, 2) can be used with conventional color negative photosensitive materials (Sample 10/Ya, 10λ) in areas with a low amount of red light (DJ's cyan density is low). The tendency is to have a shading.

2. Color Eno (sample 1, 3) using a pyrazoloazole type magenta coupler! -Pyrazolone type maze/
Compared to Samples λ and 3 using Tacoupler, the cyan density tends to decrease regardless of the amount of red light, and when used in combination with conventional color negative photosensitive materials (Sample 10/ and IO Co. 1), the bright areas do not have vivid color reproduction. However, it is difficult to cast shadows.

3. For color negatives, tjO for the peak sensitivity of the red-sensitive layer
As the ratio of sensitivity in nm decreases, the difference in cyan density between areas with less red light and areas with more red light increases (4-), and shading is more likely to occur.

In the end, experiments were carried out to realize the color image forming method of the present invention.
10. /j and /jin have the speed of processing of color ENO and exhibit color reproducibility with a three-dimensional effect that is prone to red shading, especially when using a pyrazoloazole type magenta coupler. Experimental Rotation No. 13 showed excellent color reproduction and gradation reproducibility, with bright red vividly reproduced and rich shadows.

By the way, real! The fact that bright red is vividly reproduced in A/I6 and 73 is due to the cyan S degree in part 0 in Table 5! - Experiment A610 using pyrazolone type magenta coupler. This can be seen from the fact that it is lower than /44. The lower the cyan density, the higher the density of red, which is a complementary color to cyan, and the more vivid red will be reproduced.

[Brief explanation of the drawing]

FIG. 7 is a diagram showing the spectral sensitivity distribution curve of the magenta coloring green-sensitive layer of the color photosensitive material for printing according to the present invention, and shows the actual f! 1 is for sample roll 1 of the reference example, and the broken line is for sample roll 1. The m-diagram is a diagram showing the spectral reflection 111jI curve of a magenta color image obtained using a magenta coupler, where the solid line is that of sample RO of the reference example and the broken line is that of sample E. FIG. 3 is a diagram showing the spectral sensitivity distribution of a color photosensitive material for photographing. The solid line is that of sample iop of Example 1, and the broken line is that of sample ioi. The second figure shows the spectral reflection overlap 1ts'lr of the red chart used in Example-1.

Claims (2)

[Claims] (1) A color original image obtained using a color photosensitive material for photography, which has a silver halide blue-sensitive layer (BL), a silver halide green-sensitive layer (GL), and a silver halide red-sensitive layer (RL) on a support. In a color photographic image forming method in which the following ( A color photographic image forming method characterized by meeting the requirements of A) and (B). (A) The wavelength (λ^m^a^x_R) that gives the maximum value of the spectral sensitivity distribution S_(_λ_) of RL is 595 to 645
It is in the wavelength range of ^n^m, and the spectral sensitivity at 650^n^m is 50% or less of the maximum value of S_(_λ_). (B) For ML and CL, silver chloride or silver chlorobromide emulsions each having a silver chloride content of 90 mol % or more as a layer average are used. (2) A silver halide color photosensitive material for printing containing a magenta coupler selected from compounds represented by the general formula (I) in ML is used, claim 1
Color photographic image formation method described in Section 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R is a hydrogen atom or a substituent, Y is a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent, Za , Zb, and Zc represent a methine group, a substituted methine group, =N-, and -NH-, respectively, and one of the Za-Zb bond and the Zb-Zc bond is a double bond. R, the above-mentioned substituted methine group, or X may form a dimer or more multimer.