JPH0289048A - Direct positive image forming device - Google Patents

Abstract

PURPOSE:To form a direct positive image having the high max. image density and the low min. image density by executing development processing in the presence of at least one kind of specific compds. and at least one kind of other specific compds. CONSTITUTION:The development processing is executed in the co-presence of at least one kind of the compds. expressed by formula I or II and at least one kind of the compds. expressed by formula III or IV. In formulas I, II, Q denotes the atom group necessary for forming a 5- or 6-membered heterocycle; Q' denotes an atom group necessary for forming the 5- or 6-membered heterocycle. In formula III, IV, R1 to R4 denote a hydrogen atom or <=8C alkyl group, etc.; R5 denotes a hydrogen atom or <=11C alkyl group; total of the carbon atoms of R1 and R2 is >=5 and <=12; the total of carbon atoms of R3 to R5 is >=8 to <=22. The direct positive image having the high max. image density and the low min. image density is formed in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for forming photographic images, and more particularly to a method for forming direct positive images.

[Prior Art] A well-known method is to directly obtain a positive image by using an internal latent image type silver halide emulsion that has not been fogged in advance and subjecting it to a fogging treatment after image exposure, or performing surface development while performing a fogging treatment. It is being

Here, the internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. Refers to emulsion.

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2,592.250, U.S. Pat.
, No. 588,982, No. 3゜317.322, No. 3,
761.266, 3.761.276, 3.7
The main ones are those described in British Patent No. 96,577 and the specifications of British Patent Nos. 1,151,363, 1.150.553, and 1.011,062.

By using these known methods, it is possible to produce a relatively highly sensitive photographic window optical material as a direct positive type.

For details on the above direct positive image formation mechanism, see, for example:
The Theory of the Photographic Ink Process by T. H. James
of the Photographic Proc
ess), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276.

In other words, capri nuclei are selectively generated only on the surface of silver halide grains in unexposed areas by a surface desensitization effect based on a so-called internal latent image generated inside silver halide by the initial imagewise exposure. It is believed that a photographic image (direct positive image) is then formed in the unexposed area by subjecting it to a conventional so-called surface development process.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called a "photofogging method" (for example, British Patent No. 1,151), is used.
363) and a nucleating agent (n
A method using a nucleating agent is known. Regarding this latter method, for example, ``Research Disclosure J''
Disclosure) Magazine, Volume 151) 15162
(published November 1976), pages 76-78.

In order to directly form a positive (color) image, after fogging the internal latent image type silver halide photosensitive material, or surface development treatment while performing fogging treatment, then (bleaching), fixing (or ( This can be achieved by bleaching) fixing) processing. (
Bleaching) After the fixing process, washing with water and/or stabilizing process are usually performed.

[Problem B to be Solved by the Invention] A hydrazine compound is well known as a nucleating agent used in the above-mentioned "chemical fogging method."

The above hydrazine nucleating agent generally has a maximum image density (Dma
x) and the minimum image density (Dmin) is large,
Although it is the best in terms of discrimination,
It has the disadvantage of requiring high pH (pH>12) for processing.

Heterocyclic quaternary ammonium salts are known as nucleating agents that act even at low processing pH (pH≦12); for example, U.S. Pat. Nos. 3,615,615 and 3,719.49
No. 4, No. 3,734,738, No. 3,759,901
No. 3. 854. No. 956, 4,094,68
No. 3, 4. No. 306°016, British Patent No. 1,283
, No. 835, JP-A-52-3.426 and JP-A No. 52-3.426
No. 69,613. Especially US Patent 4,1
The propargyl- or butynyl-substituted heterocyclic quaternary ammonium gold chloride described in No. 15-122 is a nucleating agent with excellent discrimination in direct positive silver halide emulsions.

However, when a sensitizing dye is added to the silver halide emulsion for the purpose of spectral sensitization, for example, between the sensitizing dye and the heterocyclic quaternary ammonium nucleating agent, the silver halide emulsion Because competitive adsorption occurs, it is necessary to add a large amount of quaternary base nucleating agents with weak adsorption properties.Especially in the case of multilayer color sensitive materials, uneven density and loss of color balance may occur, and sufficient performance cannot be achieved. It could not be said that it shows.

It should be noted that this tendency tends to increase even more when exposed to high temperature and high humidity conditions.

For the purpose of solving the above problem, U.S. Patent No. 4,471.04
No. 4 reports an example of a quaternary base nucleating agent having a thioamide AgX adsorption promoting group. Here, it is said that the introduction of adsorption groups reduces the amount added to obtain a sufficient Dmax and improves the decrease in Dmax over time at high temperatures, but this effect was not at a fully satisfactory level.

In order to improve this point, Japanese Patent Application Laid-open Nos. 63-8740, 63-106656, 63121842, 63
-40148, 63-60449, 63-80
No. 255, No. 63-81344, etc. disclose a direct positive photographic light-sensitive material that uses a compound adsorbed to silver halide to provide a high maximum image density and a low minimum image density. However, although these inventions were effective, they did not reach a sufficiently practical level. In particular, it is essential for positive photographic light-sensitive materials to have a low minimum image density, but if the compounds of the invention are added in large amounts to sufficiently lower the minimum image density, they have the disadvantage of lowering the maximum image density.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for forming direct positive images that has a high maximum image density and a low minimum image density.

[Means for Solving the Problems] The above object of the present invention is to imagewise expose a photographic light-sensitive material having on a support at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance. After that, in the method of directly forming a positive image by carrying out a fogging process or a developing process while carrying out a fogging process, the developing process is performed using at least one compound represented by the following general formula (I) or (II). is achieved by a direct positive image forming method characterized in that it is carried out in the presence of at least one compound represented by the following general formula (III) or (IV).

General Formula (I) General Formula (II) M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions.

General formula (I) General formula (TV)s General formula (I), (In I, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle. This heterocycle is a carbon aromatic ring. Alternatively, it may be fused with a heteroaromatic ring.

Q' represents an atomic group necessary to form a 5- or 6-membered heterocycle capable of forming iminosilver.

The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

In general formula (I[I), (IV), R,, R, RJ%R
4 represents a hydrogen atom or an alkyl group having 8 or less carbon atoms, an alkoxy group, an alkylthio group, or an amide group, and R represents a hydrogen atom or an alkyl group having 11 or less carbon atoms. R
The total number of carbon atoms in ,,R, is 5 or more and 12 or less, and R3
, R+, and R, the total number of carbon atoms is 8 or more and 22 or less.

The compounds represented by general formulas (I) and (II) will be explained in detail below.

-S In formula (I), Q is preferably a carbon atom, a nitrogen atom,
Represents a group of atoms necessary to form a 5- or 6-membered heterocycle composed of at least one of oxygen, sulfur, and selenium atoms.

The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring.

Examples of the heterocycle include tetrazole, triazole, imidazole, thiadiazole, oxadiazole, selenadiazole, oxazole, thiazole, benzoxazole, benzthiazole, benzimidazole, pyrimidine, triazaindene, tetraazaindene, pentaazaindene, etc. It will be done.

M is a hydrogen atom, an alkali metal atom (e.g. sodium,
potassium), ammonium groups (e.g. trimethylammonium, dimethylbenzylammonium), groups that can become M=H or alkali metal atoms under alkaline conditions (
For example, acetyl, cyanoethyl, methanesulfonylethyl).

In addition, these heterocycles include nitro groups, halogen atoms (e.g. chlorine, bromine), mercapto groups, cyano groups, substituted or unsubstituted alkyl groups (e.g. methyl, ethyl, propyl, t-butyl, methoxyethyl, methylthio ethyl, dimethylaminoethyl, morpholinoethyl,
dimethylaminoethylthioethyl, diethylaminoethyl, dimethylaminopropyl, dibrobruaminoethyl, dimethylaminohexyl, methylthiomethyl, methoxyethoxyethoxyethyl, trinotylammonioethyl, cyanoethyl), aryl groups (e.g. phenyl, 4
-methanesulfonamidophenyl, 4-methylphenyl, 3-methoxyphenyl, 4-dimethylaminophenyl, 3,4-dichlorophenyl, naphthyl), alkenyl M (e.g. allyl), aralkyl group (e.g. benzyl,
4-methylbenzyl, phenethyl, 4-methoxybenzyl), alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, methylthioethoxy, dimethylaminoethoxy), aryloxy groups (e.g. phenoxy, 4-methoxybenzyl),
methoxyphenoxy), alkylthio groups (e.g. methylthio, ethylthio, propylthio, methylthioethyl,
Dimethylaminoethylthio, methoxyethylthio, morpholinoethylthio, dimethylaminopropylthio, piperidinoethylthio, pyrrolidinoethylthio, morpholinoethylthioethylthio, imidazolylethylthio, 2-
pyridylmethylthi, diethylaminoethylthio), arylthio groups (e.g. phenylthio, 4-dimethylaminophenylthio), heterocyclic oxy groups (e.g. 2-pyridyloxy, 2-imidazolyloxy), heterocyclic oxy groups (e.g. 2- benzthiazolylthio, 4-virazolylthio), sulfonyl groups (e.g. methanesulfonyl, ethanesulfonyl, p-toluenesulfonyl, methoxyethylsulfonyl, dimethylaminoethylsulfonyl), carbamoyl groups (e.g. unsubstituted carbamoyl, methylcarbamoyl, dimethylaminoethylcarbamoyl) , methoxyedylcarbamoyl, morpholinoethylcarbamoyl, methylthioethylcarbamoyl, phenylcarbamoyl), sulfamoyl groups (e.g. unsubstituted sulfamoyl, methylsulfamoyl, imidazolylethylsulfamoyl, phenylsulfamoyl), carbonamide groups (e.g. acetamide, benzamide) , methoxypropionamide, dimethylaminopropionamide), sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), acyloxy groups (e.g. acetyloxy, benzoyloxy), sulfonyloxy groups (e.g. methanesulfonyloxy) ), ureido groups (e.g. unsubstituted ureido, methylureido, ethylureido, methoxyethylureido groups,
dimethylaminopropylureido, methylthioethylureido, morpholinoethylureido, phenylureido), thiourido groups (e.g. unsubstituted thioureido, methylthioureido, methoxyethylthioureido), acyl groups (e.g. acetyl, benzoyl, 4-methoxybenzoyl), hetero cyclic groups (e.g. 1-morpholino, l-
piperidino, 2-pyridyl, 4-pyridyl, 2-thienyl, nipyrazolyl, niimidazolyl, 2-tetrahydrofuryl, tetrahydrothienyl), oxycarbonyl groups (e.g. methoxycarbonyl, phenoxycarbonyl, methoxyethoxycarbonyl, methylthioethoxycarbonyl, methoxyethoxy ethoxyethoxycarbonyl, dimethylaminoethoxycarbonyl, morpholinoethoxycarbonyl), oxycarbonylamino groups (e.g. methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino)
, an amino group (for example, unsubstituted amino, dimethylamino, methoxyethylamino, anilino), a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a hydroxyl group, or the like.

In the general formula (II), Q' is preferably 5 or 6 which is capable of forming iminosilver and is composed of at least one of carbon atom, nitrogen atom, oxygen atom, sulfur atom and selenium atom.
Represents the atomic group necessary to form the heterocycle of R. Further, this heterocycle may be a carbon aromatic ring or a heteroaromatic ring, and may be fused.

Examples of the heterocycle formed by Q' include indazole, benzimidazole, benzotriazole, benzoxazole, benzthiazole, imidazole,
Thiazole, oxazole, triazole, tetrazole, doriazaindene, pentaazaindene, diazaindene, pyrazole, indole, etc. are mentioned, and OM has the same meaning as that in general formula (I).

These heterocycles may be substituted with the substituents applicable to the heterocycles of general formula (I).

Among the compounds represented by general formulas (I) and (II), compounds represented by general formula (I) are preferred, and compounds represented by the following general formula (V) or general formula (I) are more preferred. These are compounds in which Q is triazaindene, tetraazaindene, or pentaazaindene.

General formula (V) In the formula, M has the same meaning as in general formula (I).

X represents an oxygen atom, a sulfur atom or a selenium atom.

or -N-, Rh, L, R@, R9, R11
1, R11, R, □, and R11 are each a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, propyl, 2-dimethylaminoethyl), a substituted or unsubstituted aryl group (e.g., Jf1 phenyl, 2-
methylphenyl), substituted or unsubstituted alkenyl groups (e.g. propenyl, 1-methylvinyl), or substituted or unsubstituted aralkyl groups (e.g. benzyl,
R represents a straight-chain or branched alkylene group (e.g., methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene), a straight-chain or branched alkenylene group (e.g., vinylene, 1-methylvinylene) ), linear or branched aralkylene groups (eg benzylidene), arylene groups (eg phenylene, naphthylene), the above groups represented by R may be further substituted.

Z is a hydrogen atom, a halogen atom (e.g. chlorine, bromine),
Nitro group, cyano group, each substituted or unsubstituted amino group (including salt form, for example, amino, hydrochloride of amino group, methylamino, dimethylamino, hydrochloride of dimethylamino group, dibutylamino, dipropylamino) , N-
dimethylaminoethyl-N-methylamino), quaternary ammonio groups (e.g. trimethylammonio, dimethylbenzylammonio), alkoxy groups (e.g. methoxy, ethoxy, 2-methoxyethoxy), aryloxy groups (e.g. phenoxy) , alkylthio groups (e.g.
methylthio, butylthio, 3-dimethylaminopropylthio), arylthio groups (e.g. phenylthio), heterocyclic oxy groups (e.g. 2-pyridyloxy, 2-imidazolyloxy), heterocyclic thio groups (e.g. 2-benzthiazoli (e.g., t, methanesulfonyl, ethanesulfonyl, p-)luenesulfonyl), carbamoyl group (e.g., unsubstituted carbamoyl, methylcarbamoyl), sulfamoyl group (e.g., unsubstituted sulfamoyl, methylsulfamoyl), carbonamide groups (e.g. acetamide, benzamide), sulfonamide groups (e.g. methanesulfonamide, benzenesulfonamide),
Acyloxy groups (e.g. acetyloxy, benzoyloxy), ureido groups (e.g. unsubstituted ureido, methylureido, ethylureido), acyl groups (e.g.
acetyl, benzoyl), thioureido groups (e.g., unsubstituted thioureido, methylthioureido), sulfonyloxy groups (e.g., methanesulfonyloxy, p-toluenesulfonyloxy), heterocyclic groups (e.g., 1-morpholino, 1-piperidino, 2 -pyridyl, 4-pyridyl, 2-thienyl, l-pyrazolyl, 1-imidazolyl, 2-tetrahydrofuryl, 2-tetrahydrothienyl), oxycarbonyl group (e.g. methoxycarbonyl, methylthiomethoxycarbonyl, phenoxycarbonyl), oxysulfonyl group (for example, methoxysulfonyl, phenoxysulfonyl, ethoxysulfonyl), an oxycarbonylamino group (for example, ethoxycarbonylamino, phenoxycarbonylamino, 4-dimethylaminophenoxycarbonylamino), or a mercapto group.

n represents 0 or l.

The compounds represented by the general formulas (I) and (II) used in the present invention are available from Berichte der Deutschen Hemitschen Gesellschaft.
utschen Chea+1schen Ge5el
lschaft) 28.77 (I895L Unexamined Japanese Patent Application 1973
-37436, 51-3231, U.S. Patent No. 3,2
No. 95,976, U.S. Pat. No. 3,376.310, Berichte der Deutschen Hemitschen Gesellschaft.
Chemischen Gesellschaft)
-11-1568 (I889), same? -■, 2483
(I896), Journal of Chemical Society (J, Chet Soc,) 112S 18
06, Journal of the American Chemistry Society (J, Aa+, Che-, Soc,
) 11.4000 (I949), U.S. Patent No. 2,585
．． No. 388, No. 2,541,924, Advances in Heterocyclic Chemistry (Adva
nceo in Heterocyclic Chem
istry) 9.165 (I968L Organic 5synthesis)
IV, 569 (I963), Journal of the American Chemical Society (J, Am.
Chem, Soc, ) 45.2390 (I923)
, Chemische Beric
hte) 9.465 (I876), Special Publication 1976-2
No. 8496, JP-A-50-89034, U.S. Patent No. 3,
No. 106,467, 3. 420. No. 670, same 2
, No. 271, 229, 3. 137゜578, same 3
, No. 148.066, No. 3,511.663, No. 3,
No. 060,028, No. 3゜271.154, No. 3,2
No. 51,691, No. 3.598,599, No. 3.14
No. 8,066, Japanese Patent Publication No. 43-4135, U.S. Patent No. 3,
615゜616, 3,420,564, 3,0
No. 71.465, No. 2,444,605, No. 2゜44
No. 4.606, No. 2,444,607, No. 2.935
．． 404, The Journal of Org 1-7 Rechemistry
anic Chemistry), 2nd Saturday 779~
801 (I959), same magazine 25, 361-366 (
I960), U.S. Patent Nos. 2,152,460, 2.713.541, 2.743,181, 2.7
43.180, 2,887,378, 2,93
No. 5,404, No. 2,444,609, No. 2,933
, No. 388, 2. 891. No. 862, 2,86
No. 1.076, same 2. It can be easily synthesized by referring to the method described in No. 735゜769.

Specific compounds used in the present invention are shown below, but the compounds of the present invention are not limited thereto.

H (I H The compound represented by the general formula → and (II) can be contained in a photosensitive material or processing solution, but it can also be contained in internal latent image type silver halide emulsions and other types of light-sensitive materials. It is preferably contained in a hydrophilic colloid layer (such as an intermediate layer or a protective layer), and particularly preferably in a silver halide emulsion or in a layer adjacent thereto.

The amount added is 10-6 to 10-1 per mole of silver halide.
"Molar is preferred, more preferably 10-5 to 10-"
It is a mole.

When the compounds represented by formulas (I) and (II) are added to a processing solution, that is, a developer or a pre-bath thereof, the amount is preferably 10-" to 10-3 mol per 11, more preferably to -' to 1O-4 mol.

Two or more compounds represented by formulas (I) and (fl) may be used in combination.

Next, the compounds represented by the general formulas (I[[) and (IV)] will be explained in detail.

In general formulas (III) and (IV), R2, R,, Rs, R
4 is a hydrogen atom or an alkyl group having 8 or less carbon atoms (e.g. methyl, ethyl, t-butyl, 5eC-hexyl, t-
octyl), alkoxy groups (e.g. methoxy, ethoxy, butoxy, 2-ethylhexyloxy), alkylthio groups (e.g. methylthio, butylthio, octylthio),
Amide groups (e.g. acetylamino, butanoylamino,
2-ethylhexanoylamino), and R1 represents a hydrogen atom or an alkyl group having 11 or less carbon atoms (eg, methyl, n-propyl, 1so-propyl, heptyl, undecyl, 1-ethylpentyl). The total number of carbon atoms in R, , R is 5 or more and 12 or less, and R3, R4, R
, the total number of carbon atoms is 8 or more and 22 or less.

R,, R,, R,, R, is preferably an alkyl group having 6 or less carbon atoms.

R is preferably an alkyl group having 7 or less carbon atoms.

In general formula (III), the total number of carbon atoms in Rt and R2 is preferably 5 or more and 9 or less.

In general formula (IV), the total number of carbon atoms of Rs, R4, and Rt is preferably 8 or more and 17 or less.

-i The synthesis of compounds represented by formulas (■) and (IV) is described in JP-A No. 52-146235 and Japanese Patent Publication No. 56-21.1.
45, Japanese Patent Publication No. 59-37497, and the like.

Specific examples of compounds represented by the general formulas (I[[) and (IV)] are listed below, but the present invention is not limited thereto.

Shiri.

II3 l11 The amount of the compound represented by general formula (I) υ゛(■) is I
O-"-F-le/vol, preferably lXl0-' mole/
n? -IX 10-3 mol/bo, most preferably lX
It ranges from 10-6 mol/bo to 1X10-' mol/bo.

The compound represented by the general formula (III) and (IV) is added to the emulsion layer, intermediate layer, or protective layer, and even to the back layer, but is preferably added to the emulsion layer or the intermediate layer adjacent thereto. be done.

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 deposited on a transparent support in a certain amount (0.5~
3g/bo) and exposed to light for a fixed time of 0.01 to 10 seconds, as shown below in developer A (internal developer).
The maximum density measured by a normal photographic density measurement method when developed at 18°C for 5 minutes was determined by using the following developer B for a silver halide emulsion coated in the same amount and exposed in the same manner as above.
Preferred are those having a density that is at least 5 times greater, more preferably at least 10 times greater than the maximum density obtained when developed for 6 minutes at 20'C in a surface developer.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKI O,5
g Add water 12 Surface type image solution Metol 2.5 g L-ascorbic acid 10 g Na Box ・4
Hzo 35 gKBr
Add 1g water
Specific examples of internal type emulsions include conversion type silver halide emulsions described in the specification of U.S. Pat. No. 2,592,250, and U.S. Pat. No. 3.76.
No. 1,276, No. 3,850,637, No. 3,923
, No. 513, No. 4,035,185, No. 4,395,
No. 478, 4. 504. No. 570, Japanese Unexamined Patent Publication No. 52-
No. 156614, No. 55127549, No. 53-60
No. 222, No. 56-22681, No. 59-20854
No. 0, No. 60-107641, No. 61-3137,
Patent Application No. 61-32462, Research Disclosure Magazine Na23510 (published in November 1983) P2
Mention may be made of the core/shell type silver halide emulsions described in the patent disclosed in No. S5.

The shapes of the silver halide grains used in the present invention include regular crystal shapes such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/ Tabular particles having a thickness ratio of 5 or more may be used. Further, 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 is 2 μm or less.
．． The thickness is preferably 1 μm or more, and particularly preferably 0.15 μm or more below lum. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight should be ±40% of the average particle size.
So-called "monodisperse" particle size distribution with a narrow particle size distribution in which 90% or more of all particles fall within ±20%, preferably within ±20%.
Preferably, silver halide emulsions are used 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. A detailed example can be found in the patent described in, for example, Research Disclosure magazine N1117643III (published December 1978), P23.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. Detailed examples can be found in patents such as those described in Research Disclosure magazine Nα17643-IV (published December 1978), pages 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog 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 Na17643-V.
l (published December 1978) and E, J, B: rr
Author: 5tabiliaution of Photog
rapic 5ilver tralideEmul
sin (Imaocal Press), 1974
It is listed in annual publications.

A variety of color couplers can be used to form direct positive color images in the present invention. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are given in "Research Disclosure" magazine No. 17643 (published December 1978) P25
, No. 18717 (published in November 1979) and Japanese Patent Application No. 61-32462, and the patents cited therein.

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

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

In the light-sensitive material of the present invention, a color antifogging agent or an anti-mixing agent can be used.

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

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 photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, fluorescent whitening agents, matting agents, air fog preventive agents, coating aids, hardeners, antistatic agents, and A slippery improver, etc. can be added. Representative examples of these additives are found in Research Disclosure magazine Nα17643■-XI (published in December 1978), pages 25-27, and 1B716 (published in January 1979).
Published in January), pages 647-651.

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,
Each has a small number of green-sensitive emulsion layers and a blue-sensitive emulsion layer. Or, from the support side, they are green sensitive, red sensitive, and blue sensitive.Furthermore, each of the above emulsion layers may be made up of two or more emulsion layers with different sensitivities, or two or more emulsion layers with the same color sensitivity. A non-light-sensitive layer may be present between the layers.Usually, 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. However, different combinations may be used depending on the case.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are those described in Research Disclosure Magazine Nα17643V■ Section 228 (published in December 1978), European Patent No. 0,102,253, and JP-A-61-9765.
It is coated on the support described in No. 5. Further, the coating method described in Research Disclosure magazine Nα17643XV, pages 28 to 29 can be used.

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

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to “Research Disclosure” magazine Nα17123
It can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers, such as those described in J.D. (published in July 1978).

Furthermore, the present invention can also be applied to black and white photographic materials.

Examples of black-and-white (B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-260.
B/W direct positive photographic materials described in No. 039 (for example, X-ray photosensitive materials, duplex photosensitive materials, micro photosensitive materials,
photosensitive materials, printing photosensitive materials), etc.

The fogging treatment of the present invention is carried out by the following "photofogging method" and/or "chemical fogging method". The entire surface exposure, that is, the fogging exposure in the "light fogging method" of the present invention is carried out after the imagewise exposure and/or during the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed before drying, but it is most preferable to expose the material in the developer solution.

As a light source for fogging exposure, a light source within the wavelength range to which the photosensitive material is sensitive may be used, and generally any of fluorescent lamps, tungsten lamps, xenon lamps, sunlight, etc. can be used.

These specific methods are described, for example, in British Patent No. 1,151,
No. 363, Special Publication No. 45-12710, No. 45-127
No. 09, No. 58-6936, JP-A No. 48-9727, No. 56-137350, No. 57-129438,
No. 5B-62652, No. 5B-60739, No. 5B
-70223 (corresponding U.S. Patent No. 4,440°851)
, No. 58-120248 (corresponding European Patent No. 89101A
2) etc.

Photosensitive materials sensitive to all wavelength ranges, such as color photosensitive materials, are disclosed in Japanese Patent Application Laid-open No. 56-137350 and No. 58-702.
A light source with high color rendering properties (as close to white as possible) as described in No. 23 is preferable. The illuminance of the light is 0.01-200
0 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferable. The illuminance may be adjusted by changing the luminous intensity of the light source, by reducing the light using various filters, by changing the distance between the photosensitive material and the light source, or by changing the angle between the photosensitive material and the light source. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

It is preferable to immerse the light-sensitive material in a developer solution or a pre-bath solution, and to irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. 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
It is 40 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 incorporated into the photosensitive material.

Here, the "nucleating agent" 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. In the present invention, fogging using a nucleating agent is particularly preferred.

When incorporated into a light-sensitive material, it is preferably added to a smooth 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 such as , an intermediate layer, an undercoat layer or a back layer.

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

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

Regarding the nucleating agent used in the present invention, the general formula (N-1
) and [N-■] are preferably used.

General formula (N-1) -・2- C-RIf-Yll (wherein, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and Z is substituted with a substituent. R1+ is an aliphatic group, and R+s is a hydrogen atom, an aliphatic group, or an aromatic group.

RI4 and R+r may be substituted with a substituent.

Furthermore, Ruff may be further combined with a heterocycle completed by Z to form a ring. However, at least one of the groups represented by R+4, R+y and Z is an alkynyl group,
Contains an acyl group, hydrazine group or hydrazone group,
Alternatively, R1 and R+y form a 6-membered ring to form a dihydropyridinium skeleton.

Furthermore, at least one of the substituents R1+, Rδ and Z may have a group promoting adsorption to silver halide. Y
is a counterion for charge balance, and n is 0 or 1.

Specific examples of the compound represented by general formula (N-1) are shown below.

(Nl-1) 5-ethoxy-2-methyl-1 propargylquinolinium bromide (N-1-2) 2.4-dimethyl-1-propargylquinolinium bromide (N-1-3) 3.4- Dimethyl-dihydropyride (2
, 1-b) Benzothiazolium bromide (N-1-4) 6-nitoxythiocarponylamino-2
-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-5) 6- (5-benzotriazolecarboxamide)-2-methyl-l Propargylquinolinium trifluoromethanesulfonate (N-■-6) 6- (5-mercaptotetrazole-
1-yl)-2-methyl-l propargylquinolinium iosito(N-I-7)6-nitoxythiocarbonylamino-2
-(2-Methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate (N-1-8) 10-propargyl-1,2,3゜4-
Tetrahydroacridinium trifluoromethanesulfonate (N-T~9) 7-nitoxythiocarponylamino 1
0-propargyl-1,2゜3.4-tetrahydroacridinium trifluoromethanesulfonate (N-1-10)7-(I(5-mercaptotetrazol-1-yl)henzamide)-10-propargyl-1, 2゜3.4-Tetrahydroacridinium perchlorate (N-111) 7- (5-mercaptotetrazole-
1-yl)-9-methyl-1 0-propargyl-1,2,3,4°tetrahydroacridinium furomide (N-1-12)7-nitoxythiocarponylamino-10-propargyl-12 dihydroacridinium Nitrifluoromethanesulfonate (N-I-13) 10-propargyl-7-[3-(I
,2,3,4-thiatriazol-5-ylamino)henzamide)-1,2,3,4-tetrahydroacridinium perchlorate (Nl-14)7-(3-cyclohexylmethoxythioluponylaminohenzamide) (amide)-10-propargyl-1゜2.3.4-tetrahydroacridinium trifluoromethanesulfonate (N□l-15)7- (3-ethoxythiocarbonylaminobenzamide)-10 propargyl-1,2,3 ,4-tetrahydroacridinium trifluoromethanesulfonate (N-1-16)7-(i(3-ethoxythiocarbonylaminophenyl)ureido]-10-propargyl-1,2゜3.4-tetrahydroacridinium Trifluoromethanesulfonate (N-1-17) 7- (3-ethoxythiocarbonylaminobenzenesulfonamide) 10-propargyl-1,2,3゜4-tetrahydride acridinium trifluoromethanesulfonate (N-1- 18) 7-(3-(3-[3-(5-mercaptotetrazol-1-yl)phenyl]ureido)benzamide]-10-propargyl-1,2,3°4-tetrahydroacridinium trifluoromethanesulfonate (N-1-19)7- (3-(5-mercapto 1.3
．． 4-thiadiazole-l ylamino)benzamide]-10 = propargyl-1,2,3,4 tetrahydroacridinium trifluoromethanesulfonate (N-1-20)7- (3-(3-butylthioureido)benzamide) -10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate General formula (N-II) R2+ N N G I?>aRD RJ4 (wherein, R21 is an aliphatic group, an aromatic group , or a heterocyclic group; R12 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or Represents an iminomethylene group (HN=C); R)3 and Ri are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.However, G , Ru, R8 and hydrazine nitrogen to form a hydrazone structure (>N-N=C).The above-mentioned groups may be substituted with a substituent if possible. ) Next, specific examples of the compound represented by the general formula (Nn) will be shown.

(N-11-1)1-formyl-2-(4-(3-(2
-methoxyphenyl)ureido] -phenyl)hydrazine (N-If-2) 1-formyl-2-[4-(3(3-
(3-(2,4-di-tert-pentylphenoxy)
propyl]ureido)phenylsulfonylamine] -phenyl)hydrazine (N-■-3) 1-formyl-2-[4-(3(5-mercaptotetrazol-1 -yl)benzamido]phenyl) hydrazine (N-11- 4) 1-formyl-2-(4-(3-(3
-(5-mercaptotetrazol-1-yl)phenyl]ureido) phenyl]hydrazine (N-■-5)1-formyl-2-[4-(3(N-(
5-Mercapto-4-methyl-1,2,4-triazol-3-yl)carbamoyl]propanamido)phenyl]hydrazine (N-■-6)1-formyl-2-(4-(3-(N-
(4-(3-mercapto-1゜2.4-triazol-4-yl) phenyl]carbamoyl]-propanamido]phenyl)hydrazine (N-■-7) 1-formyl-2-(4-(3- (N-
(5-mercapto-1,3゜4-thiadiazol-2-yl)carbamoyl]propanamido)phenyl]-hydrazine(N-11-8)2-(4-(benzotriazole5
-carboxamido)phenyl] l-formylhydrazine(N-11-9)2- (4-(3-[N-(benzotriazole-5-carboxamide)carbamoyl]propanamido)phenyl]-1-formylhydrazine(N- 11-10) 1-formyl-2-(4-(I(N
-phenylcarbamoyl)thiosemicarbazido]phenyl)hydrazine (N-11-11)1-formyl-2-(4-(3(3
-phenylthioureido)benzamide]phenyl)hydrazine (N-n-12) 1-formyl-2-(4-(3hexylureido)phenyl]hydrazine (N-■-13) l-formyl-2-(4- (3-(5
-mercaptotetrazol 1-yl)benzenesulfonamide] phenyl)hydrazine (N-11-14) 1-formyl-2-(4-(3-(
3-(3-(5-mercaptotetrazol-1-yl)phenyl] ureido)benzenesulfonamide] phenyl)hydrazine (N-11-15) 1-formyl-2-(4-(3(3
-(2,4-di-tert-pentylphenoxy)propyl]ureido)phenyl]hydrazine The nucleating agent used in the present invention can be contained in the sensitive material or in the processing solution for the sensitive material, preferably in the sensitive material. can be contained in

When incorporated into a light-sensitive material, it is preferably added to the smooth 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, e.g. , an intermediate layer, an undercoat layer, and a back layer.When adding a nucleating agent to a processing solution, it can be added to a developing solution or a low-p solution as described in JP-A-58-178350.
It may be contained in the HO pre-bath.

When a nucleating agent is contained in the sensitive material, the amount used is preferably 10-10-'' mol, more preferably 10-7 to 10-3 mol, per 1 mol of halogenated vA.

In addition, when adding a nucleating agent to the processing solution, the amount used is 1
10-' to 10-' mol per liter is preferred, more preferably 10-' to 10-' mol.

In the present invention, in order to further promote the action of the nucleating agent, the following nucleating promoters can be used.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, 3-diethylaniline, and Methyl-4-amino-N-ethyl-Nβ-hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides or p-1-luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developing solutions is 9 to 12, preferably 9.5 to 11.5.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose.

It is preferable that the silver halide color photographic light-sensitive material of the present invention undergoes a water washing and/or stabilization step after the desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a wappler), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of M
tion Picture and Televisi
on Engineers Volume 64, p24B-253
(May 1955 issue).

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent.

On the other hand, various known developing agents can be used to develop the black and white light-sensitive material in the present invention. i.e. polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol, etc.; aminophenols such as p-aminophenol, N-methyl-p
-aminophenol, 2,4-diaminophenol, etc.; 3-pyrazolidones, such as l-phenyl-3-pyrazolidones, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-
Phenyl-3-pyrazolidone and the like; ascorbic acids and the like can be used alone or in combination. Further, the developer described in JP-A No. 58-55928 can also be used.

For detailed examples of developers, preservatives, buffers, and development methods for black and white photosensitive materials, and how to use them, see
Research Disclosure” magazine N017643 (
(Issued in December 1978) Sections XIX to XX1, etc.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these Examples.

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

(Photosensitive layer composition) The components and coating amount (g/rd unit) are shown below. Regarding silver halide, the coating amount is shown in terms of silver.

The emulsion used in each layer was prepared according to the manufacturing method of emulsion EMI. However, the emulsion for the 14th layer was a Lippmann emulsion that was not surface chemically sensitized.

1st layer (antihalation layer) Black colloidal silver 0.10
Gelatin ・・・・・・ 0.70 2nd layer (intermediate layer) Gelatin ・・・・・・ 0.70 3rd layer (low sensitivity red layer) Red sensitizing dye (ExS-1, 2, 3) Silver bromide spectrally sensitized with (average grain size 0.25μ, size distribution [coefficient of variation 18%, octahedral)...0°04 Red sensitizing dye (ExS-1, 2, 3) Silver chlorobromide (silver chloride 5 mol%, average grain size 0.40μ) spectrally sensitized with
, size distribution 10%, octahedral)...0.08 Gelatin...1.00 Cyan coupler (ExC-1, 2, 3 1:1:0.2)
... 0.30 anti-fading agent (
Cpd-1, 2, 3, 4 equivalents) 0.18 Stin inhibitor (Cpd-15)... 0.003 Coupler dispersion medium (Cpd-6)... 0.03 Coupler solvent (Solv-1, 2,3 equivalents)...0.
12 Polymer latex (Cpd-8) ・・・・・・ 0.10 4th layer (high sensitivity red anger M) Silver bromide ( Average particle size 0.60μ, size distribution 15%
, octahedron) ...0.14 gelatin
・・・・・・ 1.00 cyan coupler (
ExC-1, 2, 3 as l=l:0.2)
・・・・・・ 0.30 Anti-fading agent (cpa-t
, 2.3.4 equivalents)... 0.18 Coupler dispersion medium (Cpd-6)... 0.03 Coupler solvent (Solv-1, 2, 3 equivalents)...・0
．． 12 5th layer (middle N) Gelatin... I, 00 color mixing inhibitor (Cpd-7)... 0.08 color mixing inhibitor solvent (Solv-4, 5 equivalent)...・・・・・・
0.16 No. 61ij (low sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4)
Average particle size 0.25μ, size distribution 8%, octahedral)
・・・・・・ 0.04 green sensitizing dye (
ExS-4) spectrally sensitized chlorobromide i! (Silver chloride 5 mol%, average grain size 0°40μ, size distribution 10%,
Octahedron) ・・・・・・ 0.06 Gelatin ・・・・・・ 0.80 Magenta coupler (ExM-1, 2, 3 equivalent) ・・・・・・
・ 0.11 Anti-fading agent (equal amounts of Cpd-9 and 26)...
0.15 Anti-staining agent (Cpd-10, 11, 12°I3)
near: 7:1 ratio)...0.025 force puller dispersion medium (Cpd-6)...0.05 coupler solvent (
Solv-4, 6 equivalent) 0.15 7th layer C high-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4)
Average particle size 0.65 μ, size distribution 16%, octahedral) ・・・・・・ 0. IO gelatin
・・・・・・ 0.80 Magenta coupler (°ExM-1, 2, 3 equivalent) ・・・・・・ 0.11 Anti-fading agent (Cpd-9, 26 equivalent) ・・・・・・0.15 Stin inhibitor (Cpd-10, 11, 12゜13 in l)
0.025 force puller dispersion medium (Cpd-6)... 0.05 coupler solvent (Solv-4, 6 equivalent)... 0.15 Color mixing prevention agent solvent (Solv4, 5 equivalent)...
0.10 Polymer latex (Cpd-8) ・・・・・・ 0.07 8th layer (intermediate layer) 9th layer same as 5th layer (yellow filter IW) Yellow colloid l'1ffl ・・・・・・
0.12 Gelatin ・・・・・・ 0
．． 07 Color mixing prevention agent (Cpd-7) ・・・・・・ 0
．． 03 1st O layer (intermediate layer) 11th layer (low-frequency blue layer) same as 5th layer Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0. 40μ, size distribution 8%, octahedral) ...0.07 blue sensitizing dye (
Silver chlorobromide (silver chloride 8) spectrally sensitized with ExS-5,6)
Mol%, average particle size 0.60μ, size distribution 11%
, octahedron)...0.14 Gelatin...0.80 Yellow coupler (ExY-1,2 equivalent)...
0.35 Anti-fading agent (CPd-14) 0.10 Anti-staining agent (Cpdi5) 0.007 Coupler dispersion medium (Cpd-6) 0.05 Coupler Solvent (So 1v-2) = 0. 10 12th layer (high sensitivity blue sensitivity 71) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, size distribution 18%, octahedron)... ... 0.15 gelatin
・・・・・・ 0.60 Yellow coupler (ExY-1, 2 etc. It) 0.30 Anti-fading agent (Cpd-14) 0.10 Anti-stain agent (cpa 0.007 Coupler dispersion) Medium (Cpd-6)... 0.05 Coupler solvent (Solv-2)... 0.10 13th layer (ultraviolet absorption N) Gelatin... 1.00 Ultraviolet absorber (cpa~2 .4. 16 equivalents)...
・ 0.50 Color mixing prevention agent (Cpd-7, 17 equivalent) 0.03 Dispersion medium (Cpd-6) 0.02
Ultraviolet absorber solvent (Solv-2, 7 etc. M)...
・0.08 Anti-irradiation dye (Cpd-18, t9.20
, 21.27 in a 10:10:13:15:20 ratio)
・・・・・・ 0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size O01
μ) ...0.03 Acrylic modified copolymer of polyvinyl alcohol ...0.
01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
・・・・・・ 0.05 gelatin
1.80 Gelatin hardening agent (H-1, H-2 equivalent) 0.18 15th layer (back layer) Gelatin 2.50 Ultraviolet light Absorbent (Cpd-2, 4, 16 equivalent)...
0.50 Dye (equal amounts of Cpd-18, 19, 20, 27)...
... 0.06 No. 161m (back side 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 (H-1, H-2 equivalent) ・・・・・・ 0.14 How to make emulsion EM-1 Vigorously mix an aqueous solution of potassium bromide and silver nitrate into an aqueous gelatin solution Added simultaneously over 15 minutes at 75°C with stirring,
Octahedral silver bromide grains with an average grain size of 0.40 μm were obtained. To this emulsion, 0.3 g of 3,4-dimethyl-
1,3-thiazoline-2-thione, 6 wg of sodium thiosulfate, and 7 μg of chloroauric acid (tetrahydrate) were added sequentially to 75%
Chemical sensitization treatment was performed by heating at °C for 80 minutes. The particles obtained in this way are used as cores and further grown in the same precipitation environment as the first time, until the average particle size is 0.
A 7μ octahedral monodisperse core/shell silver bromide emulsion was obtained. The coefficient of variation in particle size was approximately 10%. This emulsion contains 1.0% per mole of silver. 5 mg of sodium thiosulfate and 1.
A chemical sensitization process was carried out by adding 5 parts of chloroauric acid (tetrahydrate) and 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.
2 to silver halide, respectively 1O-310-ffi
Furthermore, in each layer, Alkanol
Agefac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (Cpd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number 101. The compounds used in the examples are shown below.

Next, samples 102 to 105 were prepared in which the compounds shown in Table 1 were added to the sixth and seventh layers.

ExS-3 ExS-1 ExS-4 ExS-2 ExS-5 pd-1 pd ExS-6 S(J3: bu*n°N (tn%) x pd-3 pd pd-6 pd pd Cz Hs pd- 7 pd-8 pd-9 113 pd pd-13 H pd Cpd-15 0H Cpd Cpd-17 H Cpd-20 pct Cpd-18 Cpd-19 S u, K Cpd-23 cp d-24 pct Cpd-26 Cpd -27 EXC-1 EXC XM XM OC,H, (n) \ H3 CsH+t(t) EXC-3 XM-1 Phosphate 5olv-3 di(3-methylhexyl)phthalate 5olv-4) lycresyl phosphate 5olv-5
Dibutyl phthalate 5olv-6 Trioctyl phosphate 5olv-7
di(2-ethylhexyl)phthalate)(-11,2-bis(vinylsulfonylacetamido)ethane H-24,6-dichloro-2-hydroxy-1,3,5
-) Lyazine Na salt ExZK-17-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10-prohagiru 1゜2.3.4-tetrahydroacridinium trifluoromethanesulfonateExZK-22(4-(3 -(3-(3-(5-(3-
(2-chloro-5-(l-dodecyloxycarbonylethoxycarbonyl)phenylrubamoyl]-4-hydroxy-1-naphthylthio)tetrazol-1-yl]phenyl)ureido]benzenesulfonamido)phenyl]-1-formylhydrazine After imagewise exposing samples 101 to 125 of the silver halide color photographic light-sensitive materials prepared as described above, using an automatic processor, the cumulative replenishment amount of the solution was 3 times the tank capacity. Continued processing until doubled.

Bleach fixing 40〃 33〃 3〃Washing (I)
40〃 33〃 3〃Washing (2) 40〃
33〃 3〃The method of replenishing the flush water is the flush bath (2)
The overflow liquid from the washing bath (2) is refilled to the washing bath (2).
A so-called countercurrent replenishment method was adopted, which leads to I). At this time, the amount of bleach-fix solution brought into the washing bath (I) from the bleach-fix bath for photosensitive materials is 35. d/rrr, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

Color developer D-sorbitol Sodium naphthalene sulfonate/formalin condensate Ethylene diamine Tetrakis methylene phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Hensitriazole Sodium sulfite Mother solution Replenisher 0.15g 0.20g 0.15g 0.20g 1.5g 1.5g 12, Ori 13.5#d! 0.80g 0.003g 0.004g 2.4g 3.2g 16.0Id 18.0id N, N-bis(carboxymethyl)hydrazine D-glucosetriethanolamine N-ethyl-N-(β-methanesulfonamidoethyl )-3-Methyl-4-aminoaniline sulfate Potassium carbonate Fluorescent brightener (diaminostilbene type) pH (25°C) Concentrated fixer Ethylenediaminetetraacetic acid, disodium, dihydrate Ethylenediaminetetraacetic acid, Fe (III ) ・Ammonium dihydrate ammonium thiosulfate (700g 6.0g 2.0g 6.0g 6,4g 2,4g 8.0g 8.5g 30.0g 25.Og 1.0g 1.2g 10.25 10゜Mother liquor Replenisher 4.0g Same as mother liquor 70.0g 180 relatives/1) Sodium p-toluenesulfinate 20. Ogium sodium bisulfite 20.0g5-mercapto-1,3,4-) 0.5g lyazole ammonium nitrate 10.0g Add water to 1o00dpH (25
°C) ranged from 6.20 to 7.5.

Table 1 shows the results of measuring the magenta color image density.

Both the washing water mother liquor and the replenisher are tap water, and H-type strongly acidic cation exchange resin (Amberlite IR-1, 20B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas) are used.
Water was passed through a mixed bed column packed with water to reduce the concentration of calcium and magnesium ions to 3 mg/1 or less, and then 20/2 sodium isotheaterate dichloride and 1.5 g/f of sodium sulfate were added. . The pH of this solution is 6.5 [Effects of the Invention] According to the present invention, a direct positive image having a high maximum image density and a low minimum image density can be formed.

In particular, the present invention can maintain a high maximum image density and form a direct positive image with a low minimum image density without reducing it. Although it is possible to increase the maximum image density and lower the minimum image density to a certain extent of the direct positive image formed by using only the compound represented by the general formula (I) or (■), the minimum image density can be further reduced. If the amount of the above-mentioned compound added is increased in an attempt to decrease the maximum image density, the maximum image density will decrease.However, according to the present invention, if a compound represented by the general formula (I By increasing the amount of the compound represented by I) or (II), the minimum image density can be reduced without reducing the maximum image density.

hand Continued (Ho Positive book

Claims (1)

[Scope of Claims] A photographic light-sensitive material having on a support at least one photographic emulsion layer containing internal latent image type silver halide grains which has not been fogged in advance is fogged or subjected to fogging treatment after imagewise exposure. In the method of directly forming a positive image by developing while applying, the developing is performed according to the following general formulas (I) and (
II) and at least one compound represented by the following general formula (
A direct positive image forming method characterized in that it is carried out in the presence of at least one of the compounds represented by III) and (IV). General formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In general formulas (I) and (II), Q is a 5- or 6-membered heterocycle represents the atomic group necessary to form . The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. Q' represents an atomic group necessary to form a 5- or 6-membered heterocycle capable of forming iminosilver. The heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. General formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In general formulas (III) and (IV), R_1, R_2, R_3,
R_4 represents a hydrogen atom or an alkyl group, alkoxy group, alkylthio group, or amide group having 8 or less carbon atoms;
5 represents a hydrogen atom or an alkyl group having 11 or less carbon atoms. The total number of carbon atoms in R_1 and R_2 is 5 or more and 12 or less, and the total number of carbon atoms in R_3, R_4 and R_5 is 8 or more and 22 or less.