JPH041632A - Silver halide color photosensitive material and formation of color proof by using this material - Google Patents

Abstract

PURPOSE:To obtain the halftone image of the formed color proof approximate to printed images by consisting image forming layers of 4 kins of layers; yellow, magenta, cyan, and black and varying the color sensitivities of the respective layers. CONSTITUTION:The silver halide photographic sensitive material is a photosensitive material which forms positive images from positive black and white halftone images; for example, a photosensitive material formed by using direct positive silver halide emulsions, a reversal photosensitive material, and a photosensitive material formed by using a silver dye bleaching method, among which the photosensitive material formed by using the direct positive silver halide emulsions is most preferable. At least the image forming layers consist of 4 kinds of the layers; yellow, magenta, cyan, and black, and the color sensitivities of the respective layers vary. The hues of the images of the color proof formed in such a manner are approximate to the hues of the color proof obtd. by printing.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a halogenated color image used to create a color image for proofing (color proof) from a black and white halftone image separated by color in a color plate making/printing process. This invention relates to silver color photographic materials.

(Prior Art) Conventionally, in the process of color plate making and printing, a method using color paper has been known as a method of obtaining a color image for proofing on a single sheet from a color-separated black and white halftone image. ing.

In this method, color-separated black-and-white halftone images consisting of multiple sheets of color-separated and converted dot images from a color original are sequentially printed onto sheets of color paper using a method such as contact printing, and subjected to color-forming image processing. , a color image formed by the dye imagewise produced from the coupler by the chromogenic original image is used as the proofing image. (For example, see Japanese Patent Publication No. 1-50898.) In such a method, the color vapor used has a color vapor that is similar in hue to the color blue image formed by the dye produced from the coupler to the hue of the color image obtained by printing. However, it cannot be said that these techniques are currently fully satisfied.

At the same time, in printing, yellow, magenta, cyan, and black inks are often used, but conventional silver halide photographic color proofs only use three types of pigments: yellow, magenta, and cyan; An image equivalent to a printed image could not be obtained.

In addition, with conventional silver halide photography color proofing, when creating a blueprint from a positive halftone image, it is necessary to overlap the corner (black) plate with another plate when exposing any plate, which causes bleeding when using n-light. occurred, resulting in a decline in image quality.

(Problems to be Solved by the Invention) Therefore, the present invention has been developed by sequentially contacting and exposing a color photographic material from a black-and-white halftone image obtained by separating the component colors from a color original, and performing a process including a color development process. It is possible to obtain a halftone image whose created color proof is more similar to the printed image. The object of the present invention is to create a color proof of a photosensitive material and thereby a halftone image that approximates a printed image.

(Means for Solving the Problems) The problems of the present invention were achieved by the following (11 to (3)).

(1) In a silver halide color photographic material for forming a positive C image for creating a color proof from a color-separated black and white halftone image, at least the image forming layer is yellow;
A silver halide color photosensitive material consisting of four layers: magenta, cyan, and black, each layer having a different color sensitivity.

(λmax of the spectral sensitivity of the image forming layer is 430n)
m~520nm, 525nm~590nl+
, 600nm to 670nn+ and 680nI
The silver halide color photosensitive material described in the above fil is characterized in that it consists of four types of silver halide light-sensitive materials of 1 to 800 nm.

(3) A plurality of black-and-white halftone images obtained by component color separation and halftone image conversion from a color original are created, and the image forming layer consists of at least four types of layers: yellow, magenta, cyan, and black, and each layer has a Silver halide color light-sensitive materials having different color properties are sequentially closely exposed to light, and photographic processing including a color development process is performed to obtain at least one of the component color separations.
A method for creating a color proof, characterized in that the average gradation of two images between the minimum density (Dmin) +Q, 3 and the minimum density (Dmin) of 11°0 is 1.7 or more.

The present invention provides that the silver halide color photographic light-sensitive material according to the present invention is a light-sensitive material that forms a positive image from a positive black-and-white halftone image, such as a light-sensitive material using a direct positive silver halide emulsion, a reversal light-sensitive material, and a silver halide color photographic light-sensitive material. It is preferable to use a photosensitive material using a bare bleaching method because the effects of the present invention are particularly large.

Among these photosensitive materials, there is a photosensitive material that uses a dye produced by the coupling of a coupler added to the photosensitive material and an oxidized product of a barafine diamine derivative main ingredient in a developer as a color proof image. , is preferable from the viewpoint that the effect of the present invention is greater, and a light-sensitive material using a direct positive silver halide emulsion is most preferable from the viewpoint that the effect of the present invention is the greatest.

As the yellow, magenta, cyan, and black couplers used in the present invention, known couplers can be used.

In addition, the spectral sensitivity λmax is 43on11 to 520n1
1.525r++s~590ne, 600nm~670
The spectral sensitizing dye having a wavelength of nIl, 6 B0ne to 800 nm can be appropriately selected from known spectral sensitizing dyes.

In the present invention, in order to set λmax in the range of 680 nm to 800 ns, the sensitizing dye may be used, for example, by
), (■) and (Ill) may be used.

General formula (II) General formula (+) z'= -z4-1N -C=
L'-(L"=L outside 7-C= N0R1pz(x(E
)).

(Zl in the formula represents an atomic group necessary to form a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, or a naphthoselenazole ring.

21 represents an atomic group necessary to form a benzothiazole ring, a naphthothiazole ring, a hendioxazole ring, and a naphthoxazole ring.

Rl = RZ represents an alkyl group or a substituted alkyl group which may be the same or different.

Ll, r-1 and R3 represent a methine group or a substituted methine group. XO represents an anion, n represents O or 1) RlX(ρ)n (Zl+ in the formula represents an atomic group necessary to form a pyridine ring or a quinoline ring.

Z'' represents an atomic group necessary to form a thiazole ring, benzothiazole ring, or naphthothiazole ring.

ZIff represents a sulfur atom or an oxygen atom, R11, RI
2 and RI3 each represent an alkyl group or a substituted alkyl group which may be the same or different.

Lll, Ll and Ll3 represent a methine group or a substituted methine group, XC represents an anion, and n represents O or l.

General formula ((1)) (xO). p! ! (22+ in the formula represents an atomic group necessary to form a pyridine ring or a quinoline ring, and 22 is a benzothiazole ring,
Represents the atomic groups necessary to form a naphthothiazole ring, benzoselenazole ring, and naphthoselenazole ring. R21
, Ro represent an alkyl group or a substituted alkyl group, which may be the same or different, and 1-XI, L! 2, I, and '3 represent a methine group or a substituted methine group. XC
) is an anion, and n represents 0 or I.

In the above general formulas (1), (II) and (Ill),
z', z'', z'', Z I++, Z 13, z
The benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, pyridine ring, and quinoline ring represented by zI, zzzte may all have a substituent, and a typical substituent is a halogen atom. (e.g. chloro) Alkyl group (e.g. 1 carbon number)
~6 carbon atoms such as methyl group, ethyl group, butyl group), alkoxy groups (for example, carbon atoms having 1 to 4 carbon atoms such as methoxy group,
such as ethoxy groups. ) RI, R1, R11, R12, R1
1, Rfl, R11 (r.

The alkyl group and substituted alkyl group may be linear, branched, or cyclic, and are preferably 1 to 6 alkyl groups.

Examples of unsubstituted alkyl groups include methyl, ethyl, propyl, butyl, etc. Substituted alkyl groups include hydroxy, phenyl, alkoxycarbonyl, acyl, carboxy, etc.
sulfo group, etc.).

Particularly preferred R1, R1, R11, RlX, R+'R1
Substituents for I and RlX include an alkyl group, a carboxyalkyl group, and a sulfoalkyl group.

L', L", Lko, Ll, LIE
, Llko, L! L! ! , Lo may be an alkyl group having 1 to 2 carbon atoms, or may form a 4- to 6-membered ring on the methine chain.

X is an anion, for example CI, Br.

1 etc. Ru.

Next, representative examples of compounds used in the present invention, represented by general formula (1) % formula % general formula (II), include general formula ([) % formula % Br○ C,l+.

All of the above are known as red-sensitizing dyes.
For example, “Heterocycle” by M. Ilamer.
iccompounds-Cyan4nedyes
and relaLed compoundsJoh
n Wiley & 5ons (New York,
It can be obtained according to the synthesis method described in 1964, published by Co., Ltd., London.

Also, the sensitizing dye described in JP-A-63-128341 can be used.

The coupler used in the black image layer may be a mixture of the cyan, magenta, and yellow couplers described above, but it is preferable to use a black coupler having approximately the same level of absorption in the wavelength range of 400 to 700 nm.

As the black coupler, compounds of the following general formula (K-1) are preferred.
There is a description in No. 46029 (p. 206-220). ] General formula (K-1) H 3g (In the formula, R33 and Bsa each represent a hydrogen atom, a halogen atom, or a monovalent group selected from a monovalent organic group, and z
31, zMt each represents a monovalent group selected from a hydrogen atom, a halogen atom, a sulfo group, a mercapto group, or a monovalent organic group, provided that R1R1ff1, R33, R34
, Z3+ and zMt are groups containing an alkyl group having 8 or more carbon atoms or an aryl group having an alkyl group having 4 or more carbon atoms, and at least one of z3+ and 23 is an aromatic primary amine group. It is this group that leaves during the cambling reaction with the color developing agent. ) To describe the general formula (K~1) in more detail, R31 and R32 in the above atomic group are each a hydrogen atom,
Alkyl group, alkenyl group (e.g. methyl group, ethyl group, t-butyl group, octyl group, decyl group, dodecyl group,
octadecyl group, octadecenyl group, terpenyl group, norbornyl group, etc.) + zta alkyl group, substituted alkenyl group (for example, one or more hydrogen atoms in the above alkyl group or alkenyl group is a hydroxy group, carboxyl group,
Those substituted with a group such as a sulfonic acid group, or those whose skeleton carbon in the above alkyl group or alkenyl group is substituted with an ether bond, thioether bond -N (bond, etc.), and those whose hydrogen atom is a hydroxy group or carboxyl group. directly or by other alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, etc. or 0- -Nζ, -CONH--NHCO
-3S Oz N HN HSO A group substituted with - etc., such as a 4-lauroylamidophenethyl group,
m-pentadecylphenoxyethyl group, α-dodecylcarbamoyl-ethyl group, etc.), substituted or unsubstituted aryl groups, or substituted or unsubstituted heterocyclic groups (e.g. 4
- represents a group selected from (2,4-di-tert-amylphenoxyacetamido)phenyl group, etc.), and Rf
fIRlf may be different groups (or may be the same).

Ro and R'' each represent a hydrogen atom, a halogen atom, or a monovalent group selected from a -valent organic group (e.g., a hydroxy group, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group, etc.), and zllZSX is Hydrogen atom, halogen atom, sulfo group, mercapto group or monovalent organic group (e.g. hydroxy group, monosubstituted or unsubstituted alkoxy group, allyloxy group, acyloxy group, arylthio group, iri-luceleno group, amino group) , a cyclic imide group, a carbamoyloxy group, a phenylsulfonyloxy group, an ori-ruazo group, etc.).
f, :I, R", R", R", R1, Z3 and z2
At least one of t is a group containing an alkyl group having 8 or more carbon atoms or a group containing an aryl group having an alkyl group having 4 or more carbon atoms, and at least one of Zffl and z3 is an aromatic primary amine group. It is a group that can be separated during a coupling reaction with a color developing agent. ) According to a preferred embodiment of the present invention, Z in the general formula
At least one of ffl and Zlz contains a monovalent group other than a hydrogen atom (for example, a halogen atom, a sulfo group, an alkoxy group, or roxy group,
acyloxy group, benzenesulfonyloxy group, etc.) is a compound in which both zjI and zo are hydrogen atoms, or ZIl, Z
To obtain an excellent black dye image with an even smaller amount of silver than a compound in which one of 31 is a hydrogen atom and the other is a group that cannot be separated during a camping reaction (for example, an amino group, an alkyl group, etc.) I can do it.

Typical specific examples of the compounds represented by the above general formula are shown below, but the compounds used in the present invention are not limited thereto.

(1) N-decyl-m-aminophenol (2) N-dodecyl-m-aminophenol (3) N-octadecenyl-m-aminophenol-41 N-octadecyl-m-aminophenol (
513-(p-dodecylbenzylamino)phenol A case in which an internal latent image type emulsion which is not previously fogged is used as the color light-sensitive material of the present invention will be described in detail.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, a silver halide emulsion is placed on a transparent support! (0,5～
3g10f), exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer A (internal type developer) at 18°C for 5 minutes. The maximum density measured was determined by applying the following developer B to a silver halide emulsion coated in the same amount and exposed in the same manner as above.
Those having a density at least 5 times greater than the maximum density obtained when developed for 6 minutes at 20° C. in a surface type developer are preferred, and more preferably less (both 10 times greater).

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKIO,
Add 5g water If surface developer B Metol 2.5g L-ascorbic acid 10g NaBO+・4Ht0
35 gKBr
Add 1g water
Specific examples of internal type emulsions include, for example, U.S. Pat.
, 592,250, U.S. Pat. No. 3,761,27.
No. 6, No. 3,850.637, No. 3.923,513
No. 4,035.185, No. 4.395.478, No. 4. 504. No. 570, Japanese Patent Publication No. 52-1566
No. 14, No. 55-127549, No. 53-50222
No. 56-22681, No. 59-208540,
Patents disclosed in No. 60-107641, No. 61-3137, JP-A-62-215272, Research Disclosure Magazine 23510 (published November 1983), page 236, and a U.S. patent having a silver chloride shell. 4789627, JP-A-63-10160 and JP-A-63-47766 regarding silver chlorobromide core-shell emulsions,
Japanese Patent Application No. 1-2467, JP-A No. 63-191145 concerning emulsions doped with metal ions, JP-A No. 1-521
The core/shell type silver halide emulsion described in No. 46 can be mentioned.

The core-to-shell silver halide molar ratio of the internal latent image type core-shell silver halide emulsion is particularly preferably 20/1 or less and 1/100 or more.

In the present invention, Mn, CuSZn, and Cd are added to internal latent image type silver halide grains that have not been fogged in advance.

At least one member selected from the group consisting of Pd, Bi, or metals belonging to Group 1 of the periodic table may be incorporated.

Mn, Cu, Zn, Cd, Pd, Bi contained in the non-fogged internal smoothing type silver halide grains of the present invention
Alternatively, the amount of the metal belonging to Group Ⅰ of the periodic table is preferably 10-9 to 10'' mole per 1 mole of silver halide,
More preferably 10-' to 104 moles.

Among the metals mentioned above, particular preference is given to using lead, iridium and bismuth and rhodium.

When these metals are mixed with a silver ion solution and an aqueous halogen solution to form silver halide particles, the metal ions can be made to coexist in the form of an aqueous solution or an organic solvent solution and incorporated into the particles. Alternatively, after the grains are formed, metal ions may be added in the form of an aqueous or organic solvent solution and then further coated with silver halide.

The method of incorporating these metals is described in U.S. Patent Nos. 3 and 7.
No. 61,276, No. 4,395.478 and JP-A No. 5
No. 9-216136, etc.

The shapes of the silver halide grains used in the present invention include regular crystal bodies such as cubes, octahedrons, dodecahedrons, and dodecahedrons (Japanese Patent Application No. 1-43125), and irregular shapes such as spherical shapes. crystal form,
Furthermore, emulsions in which tabular grains with a length/thickness ratio of 5 or more, particularly 8 or more, account for 50% or more of the total projected area of the grains, as described in JP-A-1-131547 and JP-A-1-158429, are used. Alternatively, an emulsion having a composite form of these various crystal forms or a mixture thereof may be used.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or contains less than 3 mol% of salt (
(iodine) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the length is taken as the grain size, respectively, and expressed as an average based on the projected surface) is 1.5 μm or less. The particle size distribution is preferably 0.1 μm or more, but particularly preferably 1.2 μm or less and 0.2 μm or more.The particle size distribution may be narrow or wide, but the particle size distribution may be narrow or wide, but in order to improve graininess, sharpness, etc. Within ±40% of the average particle size by number or weight, preferably 30%
%, most preferably within ±20% of the total particles
As mentioned above, it is particularly preferable to use a so-called RI-dispersed silver halide emulsion having a narrow grain size distribution of 95% or more in the present invention.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. As a chemical aggravation method for core particles, Japanese Patent Application No. 1-1748
The method described in No. 8, No. 1-17487 can be used. In the presence of a mercapto compound as described in JP-A No. 1-197742, thiosulfinic acid, sulfinic acid, sulfite as described in JP-A No. 1-254946, Japanese Patent Application No. 63-221483, and Japanese Patent Application No. 1-95394. Salt may be added. A detailed example can be found in the patent described in, for example, Research Disclosure Magazine & 1764111 (published December 1978), page 23.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and others. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, henzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, henzthiazole nucleus, naphthothiazole nucleus, penduselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxapridine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbic acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral enhancement effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, a nitrogen-containing heteroartic ring. Substituted aminostilbenzene compounds (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635.7)
No. 21), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, etc., U.S. Pat. No. 3,615; No. 613, same 3,
No. 615.641, No. 3,617,295, No. 3.
635. The combinations described in No. 721 are particularly useful.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed examples, see Research Disclosure magazine NQ17641-V.
l (published December 1978) and E. J. Birr.
Written by “5tabiliaution ofPhotogr”
aphic 5ilver Hailde Emuls
ion' (Focal Press), published in 1974.

Various color couplers can be used in combination in the present invention. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds.Specific examples of these cyan, magenta and yellow couplers that can be used in conjunction with the present invention teeth"
Research Disclosure” magazine 1k17643 (
(Published December 1978) Page 25, Section ■-D, Same as 187
17 (published in November 1979) and JP-A-62-
No. 215,272 and the patents cited therein.

Among them, 5-pyrazolone-based magenta couplers preferably used in the present invention include 5-pyrazolone-based couplers in which the 3-position is substituted with an arylamino group or an acylamino group (especially, sulfur atom-eliminating type two-equivalent couplers). It is.

More preferred are pyrazoloazole couplers, particularly pyrazolo[5,1-c)(1,2,4) triazoles described in U.S. Pat. No. 3,725,067, but coloring dyes The imidazo[1°2-b]pyrazoles described in U.S. Pat. No. 4,500,630 are more preferred in terms of low yellow side absorption and light fastness; The pyrazolo(1,5-b)(1,2,4) triazoles described are particularly preferred.

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent No. 2,474,293, 4°052.21
naphthol-based and phenol-based couplers described in US Pat. ,5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

As a yellow coupler, for example, U.S. Patent Nos. 3 and 9
No. 33,501, same No. 4. 022. 620, 4,326.024, 4,401.752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425.020
No. 1,476.760 and the like are preferred.

Colored couplers for correcting unnecessary effects in the short wavelength range of the generated dyes, couplers whose coloring dyes have appropriate diffusivity, non-coloring couplers, and DIR couplers that release a development inhibitor upon coupling reaction. or polymerized couplers can also be used.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the patents described in Research Disclosure Magazine 11h17643, sections ① to F, and JP-A-57-151944 and JP-A-57-15423.
4, No. 60-184248, U.S. Patent No. 4,248,9
What is described in No. 62 and JP-A No. 63-14603
Those described in No. 5 are preferred.

Couplers that release a nucleating agent or a development accelerator image-wise during development include British Patent No. 2,097.140, British Patent No. 2,131,188, and JP-A-59-15763.
8, 59-170840, International Application Publication (WO) 8g
The one described in No. 101402 is preferred.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitive silver halide;
Preferably from 0.01 to 0.5 for yellow couplers.
moles, for magenta couplers, from 0.03 moles to 0.03 moles.
5 mol, and for cyan couplers 0.002 to 1.
It is 0 mole.

As the binding 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.

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Representative examples of these are JP-A-62-215272 No. 185~
It is described on page 193.

Compounds that release photographically useful groups include JP-A-63-
No. 153540, No. 63-259555, Patent Application No. 1983
-212080, Japanese Patent Application No. 1-64715, 1-1
Examples include the compounds described in No. 30986.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 121 to 125.

The light-sensitive material of the present invention includes radiation, halage 5,
Dyes that prevent the formation of oxidation (for example, Japanese Patent Applications No. 63-237985 and No. 63-240393 may be used; solid microcrystal dispersion may also be used as the dye dispersion method);
Ultraviolet absorbers, plasticizers, fluorescent whitening agents, matte rules, air antifogging agents, coating aids, hardeners, antistatic agents, slip property improvers, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine NCL1764.
Sections 3 - xm (published December 1978) pages 25-27,
and 18716 (issued November 1979) 647
It is described on pages 651 to 651.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Furthermore, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-light-sensitive layer may be present between two or more emulsion layers having the same color sensitivity. Normally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but in some cases, the green-sensitive layer contains a yellow coupler and a magenta-forming coupler. Different combinations of couplers can also be used.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, Haley silane inhibitor,
It is preferable to appropriately provide auxiliary layers such as a bank layer and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure Magazine, Section 17643 (■■).
Published in December 1978) on page 28, European Patent No. 0.102,253, and JP-A-61-9765.
It is coated on the support described in No. 5. Further, the application method described in Research Disclosure, No. 17643, Section XV, pages 28-29 can be used.

The fogging treatment of the present invention is carried out by the following "photofogging method" and/or "chemical fogging method". In the "light fogging method", full-scale exposure, that is, fogging exposure, is performed after imagewise exposure, after color development treatment, or after color development. This is done during the development process. That is, the imagewise exposed photosensitive material is immersed in a color developer or a pre-bath of a color developer, or is taken out from these solutions and exposed before drying. is most preferred.

As a light source for fogging exposure, for example, JP-A-56-1
A light source with high color rendering properties (as close to white as possible) such as those described in No. 37350 and No. 58-70223 is preferable. The illuminance of the light is 0°O1 to 2000 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5
Lux is suitable. For photosensitive materials that use emulsions with higher sensitivity, exposure at low illuminance is preferable. Adjustment of illuminance can be done by changing the luminous intensity of the light source, or by changing the exposure using various filters or by adjusting the exposure between the photosensitive material and the light source. The distance between the photosensitive material and the light source may be changed, and the illuminance of the fogging light may be increased continuously or stepwise from low illuminance to high illuminance.

It is preferable that the light-sensitive material is immersed in a color developing solution or its pre-bath solution, and that the solution is sufficiently penetrated into the emulsion layer of the light-sensitive material before irradiation with light. The time from penetration into the liquid to photofogging exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.01 seconds to 2 minutes,
Preferably 0°1 second to 1 minute, more preferably 1 second to 4
It is 0 seconds.

In the present invention, the nucleating agent used when carrying out the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it can be contained in the light-sensitive material.

Here, ``Nucleating agent J'' is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. It is particularly preferable to carry out fogging treatment using a nucleating agent.

When it is added to a light-sensitive material, it is preferably added to the internal slip type silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers. For example, it may be added to an intermediate layer, undercoat layer or back layer.

When adding a nucleating agent to the processing solution, use a developing solution or a low pH
It may be included in the pre-bath.

Furthermore, two or more types of nucleating agents may be used in combination.

Nucleating agents that can be used in the present invention include, for example:
"Research Disclosure" magazine, circle 22534
(January 1983) pp. 50-54, same magazine, 15162
(November 1976) pp. 76-77, same magazine, ? ! 12
3510 (November 1983), pages 346-352, quaternary heterocyclic compounds, hydrazine compounds, and the like.

As quaternary heterocyclic nucleating agents, for example, U.S. Patent No. 3.61
No. 5,615, No. 3,719,494, No. 3,734
．． No. 738, No. 3,759.901, No. 3,854.
No. 956, 4. 094. No. 683, 4.306
．． No. 016, British Patent No. 1283.835, Special Publication No. 1973
-38.164, 52-19,452, 52-
No. 47,326, JP-A No. 52-69.6I3, No. 52
-3426, 55-138,742, 60-1
No. 1.837, and the aforementioned “Research Disclosure” No. 11 &122534;
(published in August 1983, pp. 267-270), etc. Furthermore, highly active quaternary salt compounds include those described in JP-A No. 6
Those described in Japanese Patent Application Publication No. 3-121042, Japanese Patent Application Publication No. 63-301942, Japanese Patent Application Laid-open No. 1991-191132, Japanese Patent Application No. 63-255360, Japanese Patent Application No. 63-230589, and Japanese Patent Application No. 63-255361 can be used.

In particular, a quaternary heterocyclic nucleating agent represented by the following general formula (C) is preferred.

General formula (C) ,,,2-.

(In the formula, Z represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocycle, and Z may be substituted with a substituent. R1 is an aliphatic group, R2 is a hydrogen atom, It is an aliphatic group or an aromatic group.

R1 and R2 may be optionally substituted with a t substituent.

Further, R2 may further combine with the heterocycle completed by Z to form a ring, provided that at least one of the groups represented by R1, RZ and Z is an alkynyl group, an acyl group, a hydrazine group, etc. group or hydrazone group, or R
1 and R2 form a 6-membered ring to form a dihydropyridinium skeleton.

Furthermore, at least one of the W substituents of R1, R2 and Z may have an adsorption promoting group to silver halide, Y is a counter ion for tJij balance, and n is O or 1. be. ) Examples of heterocycles completed with Z include quinolinium,
Included are benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium.

Substituents for Z include alkyl groups, alkenyl groups, aralkyl groups, aryol groups, alkynyl groups, hydroquine groups,
Alkoxy group, aryloxo group, halogen atom, amino group, alkylthio group, arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group,
Examples include a carbamoyl group, a sulfamoyl group, a sulfo group, an ano group, a ureido group, a urethane group, a carbonate group, a hydrazine group, a hydrazone group, and an imino group.

The substituent of Z may be provided via a suitable linking group.

The aliphatic groups of R1 and R2 preferably have 1 to 18 carbon atoms.
unsubstituted alkyl groups and alkyl moieties have 1 carbon number
-18 substituted alkyl groups.

The aromatic group represented by R1 preferably has 6 to 20 carbon atoms.
For example, phenyl group, naphthyl group, etc.

Examples of adsorption-promoting groups to silver halide that R', R'' and Z substituents may have include thioamide groups, mercapto groups, and 5- or 6-membered nitrogen-containing heterocyclic groups.

The thioamide group is preferably an acyclic thioamide group (
For example, thiourethane group, thioureido group, etc.).

Examples of mercapto groups include, in particular, heterocyclic mercapto groups (e.g. 5-mercaptotetrazole, 3-mercapto-1
, 2,4-triazole, 2-mercapto-1,3,4
-thiadiazole, 2-mercapto-1,3,4-oxadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing heterocycle is one consisting of a combination of nitrogen, oxygen, sulfur, and carbon, and preferably one that produces iminosilver, such as benzotriazole and aminothiatriazole.

These adsorption-promoting groups to silver halide may be via a linking group. Examples of the linking group include an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -0--3-
-NH--N- -co--5ot- N HCN HN HS OtNH-.

R1 is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group, or a case in which it is bonded to a heterocycle further completed by Z to form a ring.

At least one of the substituents to the group or ring represented by R', R'' and Z is an alkynyl group or an acyl group, or R1 and R2 are linked to form a dihydropyridinium core. Preferably, it further contains at least one alkynyl group, most preferably a propargyl group.

Counter ions Y for charge balance include, for example, bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, and tetrafluoride. Examples include boron ions and phosphorus hexafluoride ions.

Specific examples of the compound represented by general formula (C) are listed below, but the invention is not limited thereto.

(C-1) 5-ethoxy-2-methyl-1-propargylquinolinium bromide (C-2) 2.4-dimethyl-1-propargylquinolinium bromide 3.4-dimethyl-dihydropyride (2,1- b) Benzothiazolium bromide 6-ethoxythiocarbonylamino-2-methyl-■-propargylquinolinium trifluoromethanesulfonate 6-(5-benzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoro lomethanesulfonate 6-(5-mercaptotetrazol-1-yl)-2-methyl-1-propargylquinolinium iosito6-nitoxythiocarponylamino-2-(2-methyl-1-propenyl)l-propargylquinolinium Norinium trifluoromethanesulfonate (C-8) 10-propargyl-1,2,3° (
C-6) (C-3) (C-4) (C (C-7) (C-9) (C-10) (C-11) (C-12) (C-13) 4-Tetrahydroacrylate Zinium trifluoromethanesulfonate 7-nitoxythiocarbonylamino-10-propargyl-1,2,3 4-tetrahydroacridinium trifluoromethanesulfonate?-(3-(5-mercaptotetrazol-1-yl)benzamide go 10-propargyl-1,2,3,4-tetrahydroacridinium benchlorate 7-(5-mercaptotetrazol-1-yl)-9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium Promide 7-nitoxythiocarponylamino-10-propargyl-1,2-dihydroacridinium trifluoromethanesulfonate 10-propargyl-7-(3- (1,2,3,4-thiatriazol-5-ylamino)benzamide ] = 1.2.3.4-tetrahydroacridinium perchlorate 7-(3-cyclohequinylmethoxythioluponylaminobenzamide) 10-propargyl-1,2,3 4-tetrahydroacridinium trifluoromethanesulfonate Trifluoromethanesulfonate 7-(3-(3-ethoxythiocarbonylaminophenyl)ureido) lO -Propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (C-17) 7- (3-Ethoxythiocarbonyl (C-14) (C-15) (C-i6) (C- 18) (C-19) (C-20) Aminobenzenesulfonamide)-1 0-propargyl-1,2,3,4- Tetrahydroacridinium trifluoromethanesulfonate 7- (3-+3- (3-( 5-Mercaptotetrazol-1-yl)phenylthureido)benzamidego 1 0-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 7-(3-(5-mercapto-1°3. 4-thiadiazol-1-ylamino)benzamidego 1O-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate 7- (3-(3-butylthioureido)benzamidego 10-propargyl-1, 2,3,4-tetrahydroacridinium trifluoromethanesulfonate (C-21) 6-(3-ethoxythiocarbonylaminobenzamide)-1-propargyl-2,3-trimethylenequinolinium trifluoromethanesulfonate hydrazine type As a compound, for example, the above-mentioned glue search
Disclosure i=mts, x62 (1976 1
Published in January, pages 76-77) and V: Floor 23,510
(Published November 1983, pages 346-352). More specifically, those described in the following patent specifications can be mentioned. First, as an example of a hydrazine-based nucleating agent having a silver halide adsorption group,
For example, U.S. Patent No. 4,030,925;
80.207, 4,031.127, 3.
No. 718,470, No. 4.269.929, No. 4
, No. 276.364, No. 4.278.748, No. 4,385,108, No. 4,459.347, British Patent No. 2,011°391B, Japanese Unexamined Patent Publication No. 1986-74,
No. 729, No. 55-163.533, No. 55-74.
No. 536, and No. 60-179.734, No. 63-2.
Examples include those described in No. 31441.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86,829, U.S. Pat. No. 4,560.638,
4,478.928, and 2,563,7
Examples include the compounds described in No. 85 and No. 2,588°982.

As a highly active hydrazine compound, JP-A-63-23
No. 1441, No. 234244, No. 234245, No. 234246, No. 204256, Patent Application No. 1983-16
Examples include compounds described in No. 7773 and No. 63-200189.

Representative hydrazine-based nucleating agents are shown below.

CB-1) 1-formyl-2-(4-(3-(2-
methoxyphenyl)ureido) -phenyl)hydrazine (B-2> 1-formyl-2~+4-(3-(5-
Mercaptotetrazol-1-yl)benzamido]phenyl)hydrazine (B-3) l-formyl-2-(4-+3-(3-
(5-Mercaptotetrazol-1-yl)phenyl[ureido)phenyl]hydrazine As the nucleating agent, quaternary heterocyclic compounds are preferable because they greatly exhibit the effects of the present invention, and quaternary heterocyclic compounds and hydrazine compounds are preferred. Compounds may be used in combination.

When a nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH prebath as described in JP-A-58-178350.

When adding a nucleating agent to the treatment liquid, the amount used is preferably 101 to 10-3 mol per 11, more preferably 1
It is 0-7 to 10-1 mol.

In the present invention, the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, but is preferably contained in the silver halide emulsion layer.

The amount added varies depending on the properties of the silver halide pores actually used, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range, but per mole of silver in the silver halide emulsion. from about 1X10-” mole to about 1X10-
A range of moles is useful in practice, with the preferred range being from about IXIO-7 moles to about IX10-' moles per mole of silver.

When using a nucleating agent, it is preferable to use a nucleating promoter to promote the action of the nucleating agent.

A nucleation accelerator is a substance that does not substantially function as a nucleating agent, but is necessary to promote the action of the nucleating agent to increase the maximum density of a direct positive image and/or to obtain a constant direct positive image density. A substance that works to speed up the development time.

Such nucleation accelerators include tetrazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group;
Mention may be made of triazaindenes, pentazaindenes, and the compounds described in JP-A-63-106656, pages 5 to 16. Also, JP-A-63-226652
No. 63-106656 and No. 63-8740.

Specific examples of nucleation accelerators are given below.

S-9 (CHz)z N(CJq(n))z (clz N(CHs)z Nucleation accelerator can be contained in the photosensitive material or in the processing solution, but it can be added to the internal latent in the photosensitive material. It is preferably contained in an image-type silver halide emulsion or other hydrophilic colloid layers (interlayer, protective layer, etc.).Particularly preferred is a silver halide emulsion or a layer adjacent thereto.

The amount of nucleation accelerator added is 10 per mole of halogenated tM.
-' to 10-'' mol is preferred, more preferably 10-''
s~10-! It is a mole.

In addition, when adding a nucleation accelerator to a processing solution, that is, a developer or its pre-bath, io-11 to 101 per 11 is added.
It is preferably mol, more preferably 1O-7 to 104 mol.

Moreover, two or more kinds of nucleation accelerators can also be used together.

Known photographic additives that can be used in the present invention are described in the aforementioned Research Disclosure No. 11h17643 (December 1978) and Research Disclosure No. 18716 (November 1979), and the relevant sections are summarized in the table below. Ta.

2 Sensitivity enhancer Same as above 4 Brightener 24 pages 7 Anti-stinting agent 25 pages Right MA 650 pages Left to right column 8 Dye image stabilizer 25 pages 9 Hardening film 10 Binder 26 pages 651 Left column 26 pages Same as above 11 Plasticizer, Lubricant Page 27 Page 650 Right column In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are made of a flexible support such as plastic film, paper, or cloth, or glass, ceramic, or metal, which is commonly used in photographic light-sensitive materials. It is applied to rigid supports such as. Useful flexible supports include cellulose nitrate, cellulose acetate, and vinegar.
X1. Films made of semi-synthetic or synthetic polymers such as fiM acid cellulose, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers) etc. are coated or It is laminated paper, etc.

The support may be colored using dyes or pigments.

For coating the silver halide photographic emulsion layer and other hydrophilic colloid layers, various known methods such as dip coating, wash coating, curtain coating, and extrusion coating can be used.

In addition, as necessary, US Patent Nos. 2,681,294, 2,761,791, 3,526,528,
Multiple layers may be applied simultaneously by methods such as those described in No. 08947.

The latent type emulsion-containing light-sensitive material of the present invention can directly obtain a positive image by developing it with a surface developer. This is caused by latent images or fog nuclei present in the image.

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

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

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene-IQ 2-amino-5-(N-ethyl-N-laurylamino)
Toluene 4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N -ethyl-N-(β-(methanesulfonamido)ethyl)-aniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide N,N-dimethyl-p-phenylenediamine 4-amino-3-methyl -N-ethyl-N-methoxyethylaniline 4-amino-3-methyl-N~ethyl-N-β-ethoxyethylaniline 4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline above p - Among the phenylenediamine Fslll forms, particularly preferred are exemplary compounds D-2, D-4, D-5 and D-6.
It is.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per 11 ml of developer solution.
More preferably a concentration of about 0.5 g-log.

In addition, the color developer requires sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and the carbonyl compound sulfite adduct of the present invention as a preservative. It can be added depending on the situation.

A preferable addition amount is 0 per 11 color developing solutions.

The amount is 5 g to 10 g, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines described in No. 61-170756, hydrazines, No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-ruminoketones described in No. 61-188741, and/or No. 61-18
It is preferable to add various saccharides described in No. 0616. In addition, in combination with the above compounds, Japanese Patent Application Nos. 61-147823, 61-166574, 61-165621,
Monoamines described in No. 61-164515, No. 61-170789, No. 61-168159, etc., No. 61-173595, No. 61-164515, No. 6
Diamines described in No. 1-186560, etc., No. 6 1-
1 65621, polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, 61-186561, and 61-19741
It is preferable to use alcohols described in No. 9, oximes described in No. 61-198987, and tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-L5
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746.544 may be contained as necessary, and it is particularly preferable to add an aromatic polyhydroxo compound, but in particular, the following general formula (A)
It is preferable to add a compound represented by:

General formula (A) RA (wherein, L represents an optionally substituted alkylene group, and A
, is a hydrogen atom, a carboxy group, a sulfo group, a phosphono group,
phosphinic acid residue, hydroxy group, amino group which may be substituted with alkyl, ammonio group which may be substituted with alkyl,
Carbamoyl group which may be substituted with alkyl: represents a sulfamoyl group which may be substituted with alkyl, R represents a hydrogen atom or an alkyl group which may be substituted.) Formula -119 (A) will be explained in detail below. do.

In the formula, L represents a linear or branched optionally substituted alkylene group having 1 to 1 carbon atoms, preferably 1 to 5 carbon atoms, specifically, methylene, ethylene, trimethylene,
Propylene is mentioned as a preferred example. Examples of substituents include carboxy groups, sulfo groups, phosphono groups, phosphinic acid residues, hydroxy groups, and ammonio groups which may be substituted with alkyl (preferably 1 to 5 carbon atoms). Preferred examples include a group and a hydroxy group. AI is a hydrogen atom, a carboxy group,
Sulfo group, phosphono group, bosphine flI residue, hydroxy group, alkyl (preferably 1 to 5 carbon atoms) optionally substituted amino group, alkyl (preferably 1 to 5 carbon atoms)
It represents an optionally substituted ammonio group, an optionally substituted alkyl (preferably 1 to 5 carbon atoms) carbamoyl group, an optionally substituted alkyl (preferably 1 to 5 carbon atoms) sulfamoyl group, an ethyl group, a carboxy group, sulfo group,
Preferred examples include a hydroxy group, a phosphono group, and a carbamoyl group which may be substituted with alkyl. -L-A
Preferred examples include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group. Particularly preferred examples include ethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, and phosphonoethyl group. aRA represents a hydrogen atom, a linear or branched optionally substituted alkyl group having 1 to 10 carbon atoms; ,
The W substituent, which preferably has 1 to 5 carbon atoms, includes a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group that may be substituted with alkyl, an ammonio group that may be substituted with alkyl, and an alkyl group. Represents a carbamoyl group that may be substituted, a sulfamoyl group that may be substituted with alkyl, there may be two or more substituents, RA is a hydrogen atom, ethyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group , sulfoethyl group,
Preferred examples include a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group, and a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group are particularly preferred. This can be cited as a preferable example. L and RA may be linked to form a ring.

Specific examples of the compounds of the present invention are listed below, but the present invention is not limited thereto.

(A-1) (A-2) (A-3) Hs (A-4) zos tHs (A-9) (A-10) (A-11) (A-12) lI C8゜ (A-13) (A C4H* C,H.

(A-6) C.R.

L (A-7) (A-8) (A-14) (A-15) (A-16) (A-17) Φ Φ (A-18) H Φ (A 19) 80 NHC)IICo□H
(A-20) HO-Nll-CIICH2CO,
) I (A 21 ) 80 NHCLCLSO
JThe content of these compounds in the color developer is as follows:
Color developer 1jl! Preferably 0.5g to 50g
, more preferably from 1.0 g to 30 g, particularly preferably from 1.5 g to 20 g.

These compounds may be present in the light-sensitive material, and may be present not only in the color developer, but also in bleach and bleach-fix solutions, and water washing or water washing substitute stabilizing solutions. It can act on color developing agents (such as those brought in from color developing solutions) and their oxidized products to provide good performance.

The compound represented by the general formula (A) can be obtained by converting commercially available hydroxylamines into alkylation reactions (nucleophilic substitution reactions,
addition reaction, Mannich reaction). West German Patent No. 1159634 "Inorganic Force/Chemical Acta J"
a Chimica Acta), 93 (1984)
It can be synthesized according to the synthesis method of 101-108, etc.
The specific method is described below.

Synthesis Example Synthesis of Exemplified Compound (A-7) 11.5 g of sodium hydroxide and 96 g of sodium chloroethanesulfonate were added to 200 ml of an aqueous solution of 20 g of hydroxylamine hydrochloride, and the mixture was kept at 60°C. I added it slowly. Further, the temperature was kept at 60°C for 3 hours, and the reaction solution was heated under reduced pressure.
The mixture was concentrated, 200 d of concentrated hydrochloric acid was added, and the mixture was heated to 50°C. Insoluble matter was filtered, and 500 d of methanol was added to the filtrate to obtain a macroscopic compound (Exemplified Compound (A-7)) as crystals of monosodium salt.

41g (yield 53%) The color developer used in the present invention preferably has a pH of 9.
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium satylylate), potassium 〇-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
4 moles/! It is particularly preferable that

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

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-1-rimethylenephosphonic acid, ethylenediamine-N,N.

N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2,4-
) Ricarboxylic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester the metal ions in the color developer. For example, 12
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention is polluting, tl! From the viewpoint of liquid properties and prevention of color staining, it is preferable that it does not substantially contain benzyl alcohol.
Here, "substantially" means no more than 2 i per developer 11, preferably no content at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho. 44- 30074, JP-A-56-156826 and JP-A-52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2,
No. 494,903, No. 3.128182, No. 4,23
No. 0,796, No. 3,253.919, Special Publication No. 1977-
No. 11431, U.S. Patent No. 2,482,546, U.S. Pat.
, 596,926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, 4
No. 2-25201, U.S. Pat. No. 3,128,183,
Polyalkylene oxides disclosed in Japanese Patent Publications No. 41-11431, No. 42-23883, U.S. Patent No. 3,532,501, and others! -Phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightening agent, 4゜4'-diamino-2,2'-disulfostilbene compounds are preferred. , the amount added is 0 to 5 g/l, preferably 0.1 g to 4 g/l
It is.

Furthermore, various surface active substances such as alkyl sulfonic acids, ary-phosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added depending on necessity.

The processing temperature of the color developer of the present invention is 20-50°C, preferably 30-40°C. Processing time is 20 seconds to 5 minutes.
Preferably it is 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 100 to 1500 d per $41 rrf of photosensitive material.
, preferably 100 to 800 d. More preferably, it is 100d to 400d.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing steps for the silver halide color light-sensitive material of the present invention will be explained.

After exposure, the color photosensitive material of the present invention is subjected to a color development process, an am process, and a water washing process.

In the Ni silver process, instead of the bleaching process using a bleach solution and the process using a fixing solution, a bleach-fixing process may be performed using a bleach-fixing solution, or a bleaching process, a fixing process, The bleach-fixing treatment steps may be combined arbitrarily.

Examples of the desilvering step of the present invention include, but are not limited to, the following steps.

■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-washing constant-fixing ■ Bleach-constant fixing ■ Bleach-fixing ■ Bleach-fixing - bleach-fixing The color photosensitive material of the present invention is subjected to bleaching treatment or bleaching treatment after color development. Bleach-fixing processing is performed, but these processings may be performed immediately after color development without going through other processing steps, or
In order to prevent unnecessary post-development and air fog, and to reduce the carry-over of color developer into the desilvering process, it is also impregnated into sensitive material components such as sensitizing dyes and dyes contained in photographic light-sensitive materials and in photographic light-sensitive materials. In order to wash out the color developing agent and render it harmless, the color developing agent may be subjected to processing steps such as stopping, adjusting, and washing with water, and then subjected to a bleaching treatment or a bleach-fixing treatment.

A stabilization treatment step may be performed after the water washing step as necessary, or a stabilization treatment step may be performed in place of the water washing step.In combination with these treatment steps, a pre-hardening treatment step, A neutralization step, a stop-fixing treatment step, etc. may be performed, and a water washing step and a rinsing step may be optionally provided between these steps.

In addition, as a replenishment method for the desilvering step, it is common to replenish each processing bath with the corresponding replenisher and discard the overflow liquid as waste. A forward replenishment system or a countercurrent replenishment system in which the overflow liquid of the subsequent bath is led to the prebath can also be used. For example, the overflow liquid of the washing water or the stabilizing bath can be led to the fixing bath or the bleach-fixing bath.

In the present invention, the bleach-fix solution or the fix solution contains thiosulfate and carbonyl bisulfite adduct.

It may be contained in both the bleach-fix solution and the fix solution.

Thiosulfate is used as a fixing agent.

Examples of thiosulfates that can be used in the present invention include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate, and magnesium thiosulfate. Ammonium thiosulfate is preferred, and the amount of thiosulfate added is 0.1 mol/l-3 mol/l, preferably 0.3 mol/l-2 mol/2.

In addition to the above-mentioned thiosulfate, thiocyanic acid compounds (particularly ammonium salts), thiourea, thioether, urea, etc. can be used as a fixing agent or a fixing accelerator for the bleach-fixing solution and/or fixing solution of the present invention. The concentration of these auxiliary fixing agents or fixing accelerators, including the thiosulfate, is 1.11 to 3.0 mol/2, preferably 1.4 to 2.8 mol/l.

Next, the carbonyl compound bisulfite adduct of the present invention will be explained.

The carbonyl compound is preferably an aliphatic carbonyl compound having 8 or less carbon atoms and containing 1 to 3 carbonyl groups in the aliphatic carbonyl compound.

Specifically, the following compounds or salts thereof are preferable as the carbonyl bisulfite adduct of the present invention.

(1) Acetaldehyde bisulfite adduct Butyraldehyde bisulfite adduct nm Butyraldehyde bisulfite adduct 1so-Butyraldehyde bisulfite adduct Glutaraldehyde bisulfite adduct Succinic aldehyde bisulfite adduct Malonic acid aldehyde bis Bisulfite adduct Maleic aldehyde Bisulfite adduct Beta Methylglutaraldehyde Bisulfite adduct Glycolaldehyde Bisulfite adduct/Glyoxylic acid Bisulfite adduct Pyruvaldehyde Bisulfite adduct D- Glycerin Aldehyde Bisulfite adduct L- Glycerin aldehyde bisulfite adduct Formic acid bisulfite M adduct Chloroacetaldehyde bisulfite adduct Bromoacetaldehyde bisulfite adduct Acetone bisulfite adduct Dihydroxyacetone bisulfite adduct Hydroxyacetone bisulfite adduct (21) Pyruvate bisulfite adduct Product (22) N-acetylaminoacetic acid bisulfite adduct (2
3) 3-acetylpropionic acid binitrous [acid adduct (2
4) 4-acetylpropyl bisulfite adduct (2
5) 4-acetylbutyric acid bisulfite adduct (26) Methyl acetoacetate methyl bisulfite adduct (27) Ethyl acetoacetate bisulfite adduct (28) Methyl ethyl ketone bisulfite adduct (29) Acetylacetone bisulfite adduct (
30) Ethyl acetoacetate ethyl bisulfite adduct These compounds may be added as a carbonyl compound and bisulfite or sulfite separately to the bleach-fix solution or fixer solution, or in the form of the above-mentioned bisulfite adduct. May be added.

When the carbonyl compound bisulfite adduct is added to the bleach-fix solution or fixing solution of the present invention, the molar ratio of the carbonyl compound and bisulfite or sulfite is 30:l.
to 1:30, preferably 5:1 to 1:10, particularly preferably 1:1 to 1:5, and the carbonyl ratio in the bleach-fixer to fixer solution of the present invention. The addition amount of the compound bisulfite adduct can be used in the range of txio-' mol - 10 mol/2 per 11 of the bleach-fixing solution or fixing solution, preferably from lXl0-' mol/l to 5 mol/2. lXl0-” mol/l-1 mol/l
It is preferable that

All of these carbonyl compounds are commercially available,
It can be easily obtained.

As the bleaching agent used in the bleach solution and/or bleach-fix solution, ferric complex salts of aminopolycarboxylic acids, peroxides (e.g., sodium persulfate), etc. can be used, but ferric complex salts of aminopolycarboxylic acids can be used. preferable.

As the above-mentioned aminopolycarboxylic acid, it is preferable to use a compound represented by the following general formula (Ill) in addition to ethylenediaminetetraacetic acid.

General Formula (B) In the formula, represents an oxygen atom, a sulfur atom, an alkylene group, or a group represented by -CH-. R21, ffff Ro, R33, R2a each represent a hydrogen atom or an alkyl group, but R31 and Ro or R, s and Ro may be linked to each other to form a cycloalkylene ring, ni, l, mSn each represents an integer from 0 to 4, and a is 1
It represents an integer of ~3, but the sum of k, f, m, and n is 2 or more. However, if a is 1 and LISR2Zs
R12s Rsa are each hydrogen atoms, k, /,
The sum of m and n is never 2.

General formula (B) will be explained in more detail.

In general formula (B), is an oxygen atom, a sulfur atom,
Alkylene groups having 6 or less carbon atoms are preferred, and in the case of alkylene groups, particularly methylene groups, ethylene groups, propylene groups,
Butylene group is preferred, R Ro, R33% R34
For , hydrogen atoms and alkyl groups having 6 or less carbon atoms are preferable, but in the case of alkyl groups, methyl groups, ethyl groups,
nm propyl group and 1so-propyl group are preferred.

Specific examples of the aminopolycarboxylic acid compound represented by the -S formula (B) are shown below, but the invention is not limited thereto.

B-1: 1,3-diaminopropanetetraacetic acid B-2 nigericol ether diamine tetraacetic acid B-3 = cyclohexanediaminetetraacetic acid B-4: 1,4-diaminobutanetetraacetic acid B-5: 1,2-propylene Diaminetetraacetic acid B-6:
Thioglycol ether diamine tetraacetic acid E-7:1,3
-Butylenediaminetetraacetic acid The amount of the bleaching agent of the present invention added is:
The amount is from 0.05 mol to 1 mol, preferably from 0.1 mol to 0.5 mol, per 11 mol of bleach or bleach-fix solution. Further, the above ferric aminopolycarboxylic acid complex salt and the ferric ethylenediaminetetraacetic acid complex salt can be used in combination as a bleaching agent. In this case, the mixing ratio of both is l:lO~10:
1 is preferable, and the total concentration of both iron complex salts is equal to the treatment liquid Ijl! per mole, preferably 0.05 mol to 1 mol.
It is 1 to 0.5 mol.

In addition to the above-mentioned aminopolycarboxylic acid iron (I[[) complex, an aminopolycarboxylic acid or a salt thereof may be added to the bleaching solution and/or bleach-fixing solution of the present invention.

The preferable addition amount is o, ooot mol to 0.1 mol/l, more preferably 0.003 to 0.05 mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

Further, the bleach solution and/or bleach-fix solution containing the above-mentioned ferric complex salt may contain complex salts of metal ions other than iron, such as cobalt and copper.

Various cleanliness promoters can be added to the bleach solution and/or bleach-fix solution of the present invention.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1.290.
, 812, British Patent No. 1.138.842, JP-A-53-9563O, Research Disclosure No. 17129 (July 1978 issue). Compounds, thiazolidine derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German patents Polyethylene oxides described in specification No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferably British Patent No. 1,138,
Mercapto compounds such as those described in '842 are preferred.

The amount of bleach accelerator added is 0.0 per 11 liquids with bleaching ability.
The amount is 1 g to 20 g, preferably 0.1 g to 10 g.

In addition to bleaching agents and the above-mentioned compounds, the bleaching solution and/or bleach-fixing solution constituting the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide or chlorides such as potassium chloride, sodium chloride, Rehalogenating agents such as ammonium chloride can be included. The concentration of the rehalogenating agent is between 0.1 and 5 moles, preferably between 0.5 and 3 moles per 11 parts of the bleaching solution. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid,
Known additives commonly used in bleaching solutions can be added, such as one or more inorganic acids, organic acids, and salts thereof that enhance pH buffering capacity, such as sodium citrate and tartaric acid.

The bleach-fix solution and/or fix solution of the present invention may contain sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, hydroxylamine, hydrazine, and the like. Furthermore, various optical brighteners, antifoaming agents, surfactants, organic solvents such as polyvinylpyrrolidone, methanol, etc. can be contained, but in particular, as a preservative, Japanese Patent Application No. 60-28383
It is preferable to use the sulfinic acid compounds described in Specification No. 1.

Furthermore, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids, and 1-hydroxyethylidene-1,I-diphosphonic acid is particularly effective. The amount of these added is 0.01 to 0.3 mol/2
, preferably 0.05 to 0.2 mol/2, and is particularly effective in fixing solutions.

The pH of the bleaching solution and/or bleach-fixing solution of the present invention is generally 9 to 1, preferably 7.5 to 15, and most preferably 7.0 to 2.0. 5. Especially in bleaching solutions.
In the preferred pH range, preferably 0 to 2.0, there is little bleaching fog and the desilvering performance is excellent.

The pH of the fixer of the present invention is generally 9.0 to 5.0, particularly preferably 7.5 to 5.5.

The amount of replenishment of the bleaching solution and/or bleach-fixing solution of the present invention is 50d to 3000ad, preferably 100af per liter of light-sensitive material.
~1000d.

The fixer replenishment amount is from 300 m to 300 m (ld is preferred, but more preferably 300 m
d to 1000d.

However, the above-mentioned replenishment amount can be reduced to a smaller amount if, for example, a regeneration treatment is performed, such as oxidation regeneration of the processing solution and silver recovery treatment.

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 10 minutes, more preferably 1 minute to 6 minutes. Also, the processing temperature is 25°C.
~50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, U.S. Patent No. 4.758
, 858, a method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, a method of increasing the stirring effect using a rotating means of JP-A-62-183461, and a method of increasing the stirring effect by using a rotating means provided in the liquid. Examples include a method of moving the photosensitive material while bringing the wiper blade into contact with the emulsion surface to create turbulent flow on the hole-side surface to improve the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. This means for improving fit agitation is effective for any of the white liquor, bleach-fix solution, and fixer solution. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the acceleration results and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
No. 59, Re5earch DisclosureIt
e■ Seed 2911B (July 1978), preferably having the photosensitive material conveying means described in U.S. Patent No. 4,758,858,
As described in No. 257, such a conveyance means can significantly reduce the carry-over of the processing liquid from the front bath to the after bath, and is highly effective in preventing deterioration of the performance of the processing liquid.The means described in the above RD is also preferable. Such an effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

It is desirable that these agitation strengthening means are effective in addition to the desilvering process and can be used in the water washing process and the developing process to shorten the processing time and reduce the amount of replenishment.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing process may contain known additives as required.3 For example, hard water softening agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Disinfectants and fungicides (for example, intiazolone, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E,
West.

“-ater Quality Cr1teria”,
Phot, Sci, and Eng.

vol, 9, tk6. Pages 344-359 (1
965) and the like can also be used.

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used.
A liquid that increases the ability of the skin, a liquid containing an aldehyde (for example, geltal aldehyde), etc. can be used. Formalin is undesirable from a pollution standpoint, and the stabilizing solution may contain ammonium compounds, Bi, Aj!, if necessary. metal compounds such as, optical brighteners, chelating agents (e.g. EDTA 1-
Hydroxyethylidene-1,1-diphosphonic acid), bactericides, fungicides, hardeners, surfactants, and the like can be used. As a fungicide, 5-chloro-2-methyl-
Thiazolone compounds such as inthiazolin-3-one and 1°2-benzisothiazolin-3-one are effective.

Further, as the surfactant, a silicone compound represented by the following general formula is preferable because it has an effect of preventing water droplet unevenness and defoaming.

(CHI) c-0+CHxCHOh-+CI(xcl
Ito) -R where a, b, d, , e are integers of 5 to 30, C is an integer of 2 to 5, or R is an alkyl group having 3 to 6 carbon atoms.

Further, it is preferable to add an alkanolamine to the stabilizing solution in order to prevent sulfurization of thiosulfate ions introduced by the photosensitive material. The use of alkanolamine is described in US Pat. No. 4,786,583.

In addition, the stabilizing liquid inside the shell contains formalin,
It is preferable not to use it in the present invention.

The pH of the stabilizer of the present invention is 3-8, preferably 5-7.

The temperature of the stabilizing liquid is preferably 5°C to 45°C, more preferably 10°C to 40°C.

In addition, the water washing step and the stabilization step are preferably carried out in a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. Two or more types of stabilizing solutions may be used in multiple stages, and the replenishment amount is from the pre-bath per unit area. The amount is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in.

The shorter the processing time of the water washing and stabilization steps, the more effective the present invention will be.From the viewpoint of rapid processing, the total processing time of the water washing and stabilization steps is preferably 10 to 50 seconds, and the effect is particularly remarkable when the processing time is 10 to 30 seconds.

Further, the smaller the amount of replenishment in the water washing and stabilization steps, the greater the effect of the present invention, and it is preferably 50 to 400 d per photosensitive material, particularly preferably 50 to 200 d to 200 d.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have a Mg concentration of 11 degrees or less than 5 .mu./l, water that has been sterilized with halogen, an ultraviolet germicidal lamp, or the like.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, a portion of the processing liquid due to evaporation is
1i1 may occur, especially when the processing amount is small or the opening area of the processing liquid is large. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step flows into a pre-bath having a fixing ability.

The present invention can be applied to various color photographic materials.

For example, the present invention can be applied to color reversal film for slides or television, color reversal paper, instant color film, color hard copy for storing images of full color copiers and CRTs. Disclosure” magazine 171
23 (published July 1978), etc., which utilize a mixture of three color couplers can also be applied to black and white photosensitive materials.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-burning flash pulp are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, linear or planar arrays can be applied to micro-screens using fluorescent screens (such as CRTs), liquid crystals (LCDs), and lanthanum-doped lead titanium zirconate (PLZT), which are emitted from phosphors excited by electron beams. It is also possible to use an exposure means that combines two light sources. If necessary, the spectral distribution used for exposure can be adjusted using color filters. Also, Fuji Photo Film Co., Ltd.'s color copy machine AP-
The scanning n-light method used in the 5000 can be used.

The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example-1 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material was prepared in which the following 1st to 14th layers were coated on the front side of the film (0 micron), and 15th to 16th layers were coated on the back side. The polyethylene on the first layer coating side contains titanium oxide (4 g/po) as a white pigment, and a trace amount (0
,003g/rrl) as a dye (the chromaticity of the surface of the support is 88.0 in Lm, a*, bm system).
, -0.20. -0.75. ).

(Photosensitive layer composition) The components and coating amount (g/rd unit) are shown below, however,
The amount of sensitizing dye added is shown in moles per 111 moles. For silver halide, the amount of coating is shown in terms of silver. The emulsion used for each layer was prepared at different temperatures according to the manufacturing method of emulsion EM-1 described later. Made by changing the particle size. However, the first
A Lippmann emulsion without surface chemical sensitization was used as the four-layer emulsion.

1st layer (Antihalation N) Black colloidal silver...0.10 Gelatin...0.70 Color mixing inhibitor (Cpd-7)...0.03 Color mixing inhibitor solvent (Solv-4, 5 equivalents) ...0.10 second
Layer (middle layer) Gelatin...1.00 Color mixing prevention agent (Cpd-7)...0.08 Ultraviolet absorber (Cpd-2, 4, 16 each equivalent amount)...0.50 Color mixing prevention agent Solvent (Equivalent amounts of Solv-4 and 5)...0.16 polymer latex (Cpd-8)...0.10 gelatin
...0.70 3rd layer (redness N
) Red sensitizing dye (Equivalent amounts of each ExS-1, 2, 3, total 3.8X
Silver bromide (average grain size 0) spectrally sensitized with
．． 25μ, particle size distribution [coefficient of variation] 8%, octahedral)
...0.12 gelatin...
・0.80 yellow coupler (ExY-1, 2, 3 each equal position) ...0.35 anti-fading (Cpd-14) ...0.10 anti-fading (Cpd-30>...0 .05 Stain inhibitor (Cpd-5,15 in 1:5 ratio) ...0.007 4th layer (intermediate layer) 5th layer (infrared sensitive layer) same as 2nd layer Infrared sensitizing dye Silver bromide (average grain size 0.30μ, grain size distribution 15%, octahedral) spectrally sensitized with (E x S -7,8 each equivalent, total 2°5XIO-')
...0.14 gelatin
...1. 00 cyan coupler (ExC-
1,2,3 (11:0.2)...0,30 anti-fading agent (Cpd-1, 2, 3, 4,30 each in equal amounts)...0.18 anti-stain agent (Cpd-5 )...0.003 Force puller dispersion medium (Cpd-6)...0.03 Coupler solvent (Equivalent amounts of Solv-1, 2, and 3)...0.12 6th layer (middle N) 71st El (green sensitive layer) same as 2nd layer Green sensitizing dye (Ex S -4,3,6X10-')
Silver bromide spectrally sensitized with (average grain size 0°25μ,
Particle size distribution 8%, octahedral)...0.10 Gelatin...0.80 Coupler (ExM-1, ExY-3, molar ratio 3:1)...0.15 Antifading agent (Cpd- 0.025 Coupler dispersion medium (Cpd -6) ...0.05 coupler solvent (Solv-1-4, 6 each equal amount) ...0.15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 2nd layer Yellow colloidal silver (particle size 100) ...0.12 Gelatin ...0.70 Color mixing prevention agent (Cpd-7) ...0゜03 Color mixing prevention agent solvent (Solv-4, 5 each equivalent amount) ...0.10 Polymer latex (Cpd-8) ...0.07 10th layer (
Intermediate layer) 11th layer (blue sensitive layer) same as the 2nd layer Blue sensitizing dye (Equivalent amount of each ExS-5, 6, total 3゜6xlO
-') spectrally sensitized silver bromide (average grain size 0.4
0μ, particle size distribution 8%, octahedral)
...0,12 gelatin
...1.00 Coupler (ExK-1, 2, 3 each equivalent M)...0.15 Anti-fading agent (Cpd-1, 2, 3, 4, 30 each equivalent) Coupler dispersion medium (Cpd- 5) Coupler solvent (Solv-1, 2, 3 each in equal amounts) 12th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (Cpd-2, 4, 16 each in equal amounts) Color mixing prevention agent (Cpd-7, 17 each) (equivalent amount) Dispersion medium (Cpd-6) Ultraviolet 1 absorber solvent (Solv-2, 7 each equivalent amount) Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 at 10:10:13:15 :20 ...0.18 ...0.03 ...0.12 ...1.00 ...0.50 ...0.03 ...0.02 ...0.08 (in ratio)...0.05 1st
3N (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1 μ) ...0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50,000) ...0.01 Poly Equivalent amounts of methyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ)) ...0.05 Gelatin ...1.80 Gelatin hardening agent (H-1, H-2, etc.) amount) ...0.18 No. 14
Layer (M layer) Gelatin...2.50 Ultraviolet absorber (Cpd-2, 4, 16 each equivalent amount)...0.50 Dye (
Cpd-18, 19, 20, 21, 27 in equal amounts)...0.06 1st
5 layers (back layer protection N) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
...0.05 gelatin
...2.00 Gelatin hardening agent (equal amounts of H-1 and H-2) ...0.14 How to make emulsion EM-1 Add an aqueous solution of potassium bromide and silver nitrate to an aqueous gelatin solution at 75°C while stirring vigorously. They were simultaneously added over a period of 15 minutes to obtain octahedral silver bromide particles with an average particle size of 0.35 μm. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of 1 m
-Thiazoline-2-thione was added. For this emulsion! !
Chemical sensitization was carried out by sequentially adding 6 μ of sodium thiosulfate and 7 μ per mole of chloroauric acid (tetrahydrate) and heating at 75° C. for 80 minutes. Using the thus obtained grains as cores, they were further grown in the same precipitation environment as the first time, and finally an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7μ was obtained. The coefficient of variation is approximately 10
%Met. To this emulsion, 1.5 μ of sodium thiosulfate and 1.5 μ of chloroauric acid (tetrahydrate) were added per mole of silver.
Chemical sensitization was performed by heating at 60° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

Each photosensitive layer contains ExZK 1 and ExZK as nucleating agents.
104,104% by weight of each of -2 and silver halide
, 1 each of Cpd-22, 28, and 29 as nucleation promoters.
01% by weight was used. Further, in each layer, Alkanol XC (manufactured by Du Pont) and sodium hyalkylbenzenesulfonate were used as emulsification and dispersion aids, and succinate ester and Magefac F-120 (manufactured by Dainippon Ink Co., Ltd.) were used as coating aids. (Equivalent amounts of Cpd-23, 24, and 25) were used as stabilizers in the silver halide and colloidal silver containing layers. This sample was designated as No. 1. The compounds used in the examples are shown below.

xS xS xS (CHx)JOsO xS xS-7 Exemplary compound 1 xS-8 Exemplary compound I p d-t XX5- 5(t)CaH Cpd-2 xS-6 (t)C18w Cpd-3 S.O.H. N(CJs)3 (, pct pa CH +CH1-'C8+, 1 COOC! HI CHxCHzCOCsH+.

Cpd-9 Cpd-5 CH CH Cpd-6 (-CI!-CI　-)-11 (n 100-1000) CONHCaHw(t) Cpd-7 CH (t) ShiSHI+ Cpd C.HS Cpd CH Cpd CH Cpd-13 CH CH CH Cpd-18 Cpd -14 CH.

SO,K SO, to pc1 pc1 Cp d -21 SO,K pd p d p d pd-29 So, K pd pd pd-24 pd xC 0 ■ H H H aHq ExM-1 ExM-2 xY-2 xY-3 xK-1 N-decyl m-aminophenol xK-2 N-dodecyl m-aminophenol ExM CH.

xY-1 xK-3 N-octadecenyl-m-aminephenol olv-1 Di(2-ethylhexyl) sebacate 5olv-'1 Trinonylphosphate olv-3 Di(3-methylhexyl)phthalate olv-4 Trinonylphosphate olv- 5 Dibutyl phthalate olv-6 Trioctyl phosphate olv-7 Di(2-ethylhexyl) phthalate 1,2-bis(vinylsulfonylacetamide) Ethane H-2 4,6-dichloro-2-hydroxy-1,3゜5-triazine Na salt xZK-1 7-(3-ethoxythiocarbonylaminobenzamido)-9-methyl-10-propargyl-1,2,3,4
-Tetrahydroacridinium trifluoromethanesulfonate xZK-2 2-(4-(3-(3-(3-C5-(3[2-chloro-5-(1-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl]- 4-hydroxy-1-
Naphthylthio)tetrazol-1-yl]phenyl)ureido]benzenesulfonamido)phenyl]-1-formylhydrazine (Comparative Sample A) Sample 1 except for the 5.6th layer and the 11th layer was changed to the following: In the same manner as above, an internal latent image type direct positive silver halide color photographic light-sensitive material was prepared.

11th layer (blue-sensitive layer) Blue sensitizing dye (E x S -5, 6 equivalent each, total 3゜6
Silver bromide (average grain size 0.40μ, grain size distribution 8%, octahedral) spectrally sensitized with
...0.25 gelatin
...0.80 cyan coupler (ExC
-1, 2, 3 in 1:1:0.2> ...0.30 anti-fading agent (Equivalent amounts of Cpd-1, 2, 3, 4, 30) ...0.18 anti-staining agent ( Cpd-5) ...0.003 Force puller dispersion medium (Cpd-6) ...0.03 Coupler solvent (Equivalent amounts of Solv-1, 2, and 3) ...0.12 (Comparative sample B) 3.7.11 An internal latent image type direct positive silver halide color photographic material was prepared in the same manner as Sample A except that the coating amount of each layer was increased by 20%.

[Processing step A]

Processing process 亙■ Direct color development 135 seconds 38℃ Bleach-fixing 40〃 33#Water wash +ll 40#33-Water wash (2)
40〃 33#Drying 30
〃80-The composition of each treatment liquid was as follows.

Departure store Egyo D-Sorbit Naphthalene sulfonic acid Natrirum formalin condensate Ethylene diamine Tetrakis methylene phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Benzotriazole Sodium sulfite N,N-bis(carpoxime 0.15g 1.5g 0.15g 12.0d 13 .5d 0.70g 0.003g 2,4g 4,0g Chill) hydrazine D-glucose triethanolamine N-ethyl-N-hydroxyethyl-3-methyl-4 Aminoaniline sulfate N-ethyl-N-hydroxyethyl- 4-Aminoaniline sulfate Potassium carbonate optical brightener (diaminostilbene) system 2,0g 6,0g 0,6g 5,6g 30.0g 1,0g pH (25℃) Keishi Aki ethylene diamine 4 acetic acid 2 Sodium dihydrate ethylenediaminetetraacetic acid Fe (I[l) Ammonium dihydrate 10.25 2,0g 00g Ammonium thiosulfate 180M! (700
g/1) p-) Luenesulfinic acid 45.0g Sodium thorium bisulfite 35.0g 5-mercapto-1,3,40,5g -triazole ammonium nitrate 10.0gpH (2
5℃) 6.50, Wooden Notes 2 Tap water was filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite JR-400, manufactured by Rohm and Haas). The concentration of calcium and magnesium ions was reduced to below 3/1 by passing water through the mixed bed column, and then sodium dichloride isocyanurate 20/1 and sodium sulfate 0/1 were added. 15 g/l was added. The pH of this solution is 6.5
It was in the range of ~7°5.

The dot scale (0
~100%) through infrared light (Fuji Filter 5C-6
8), infrared (BPN-60), green light (BPB-55)
), and four exposures to blue light (BPB-45) were performed.

The position of the halftone scale was shifted during each exposure. However, the halftone scale used for blue light exposure was used at the same position for all exposures. Each exposure amount was selected so that 5% of the dots on the original would be 5% of the dots.

Similarly, comparative samples NaA and NIB were exposed to the same red, green, and blue light three times through the halftone dot scale. Two halftone dot scales were used, one shifted in position during each exposure and one in constant position.

This post-processing step A was performed to obtain halftone dot images in four colors: cyan, magenta, yellow, and black.

Print proofs were obtained using the same dot scale.

Four types of halftone scale images were obtained, including cyan, magenta, yellow, and a mixture of these three colors with black.

The image density of the 100% portion of each color was measured and shown in Table 1.

In Table 2, the density of sample lkA black is lower than that of printed matter, and the density of cyan, magenta, and yellow of lkB of sample lkB is higher than that of printed matter, which is undesirable.

Sample-1 of the present invention was preferable because it provided the same image density as the printed matter.

Also, observe the halftone image with an area of 30% with a 20x magnifying glass,
I looked at the quality of the halftone dots. The results are shown in Table 2.

The quality of black dots was better than that of sample level 1 of the present invention and lkA and B of comparative examples.

Example 2 Sample No. 2 was prepared in the same manner as Example 1, except that the smooth emulsion in each layer was changed to a grain size polydisperse type (the temperature and time during silver halide grain formation were increased and shortened). Created.

The same exposure (however, continuous tone gray scale was also used) and development were performed as in Example-1. The results are shown in Table 3.

Table 3 Table 4 Continuation vtUfJ Gray scale image density Dmin+0°3 to D++in + 1. Average gradation between 0.

The sample ml with hard gradation had a high maximum density and was more preferable.

Example 3 Sample C was prepared in the same manner as Sample Ceramic 1 of Example 1, except that the sensitizing dye in the smooth emulsion of the fifth layer was ExS-1j#.

Exposure and development were carried out in the same manner as in Example-1.

The results are shown in Table 4.

Sample NQl of the present invention had a higher maximum image temperature than Comparative Example Sample Area C and was preferable.

Claims (3)

[Claims] (1) In a silver halide color photographic light-sensitive material for forming a positive image for creating a color proof from a color-separated black and white halftone image, at least the image forming layer is yellow;
A silver halide color photosensitive material consisting of four layers: magenta, cyan, and black, each layer having a different color sensitivity. (2) The spectral sensitivity λmax of the image forming layer is 430 nm or more
520nm, 525nm~590nm, 600nm~6
The silver halide color photosensitive material according to claim 1, characterized in that it consists of four types: 70 nm and 680 nm to 800 nm. (3) A plurality of black-and-white halftone images obtained by component color separation and halftone image conversion from a color original are created, and the image forming layer consists of at least four types of layers: yellow, magenta, cyan, and black, and each layer has a Silver halide color light-sensitive materials having different color properties are sequentially closely exposed to light, and photographic processing including a color development process is performed to obtain at least one of the component color separations.
A method for creating a color proof, characterized in that processing is performed so that the average gradation between the minimum density (Dmin) +0.3 and the minimum density +1.0 of two images is 1.7 or more.