JPS6340148A - Direct positive image forming method - Google Patents

Abstract

PURPOSE:To permit quick and stable formation of a direct positive image having a high max. image density and low min. image density by executing a developing process in the presence of a nucleation accelerator selected from compds. having a group to be adsorbed to silver halide and org. group contg. at least one thioether group, etc. CONSTITUTION:The developing process is executed in the presence of the nucleation accelerator contg. the group to be adsorbed to the silver halide and the org. group contg. at least one of the thioether group, amino group, ammonium group, ether group or heterocyclic group. A nucleating agent is a material which acts to form a direct positive image when acted at the time of subjecting an unfogged internal latent image type halogenated emulsion to a preliminary surface developing process. Said agent is usable in combination of >=2 kinds. The nucleation accelerator is a material which has substantially no function as the nucleating agent but acts to increase the max. density of the direct positive image and/or to shorten the developing time necessary for obtaining the specified direct positive image density by accelerating the effect of the nucleating agent. Said agent is usable in combination of >=2 kinds.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an image forming method for directly developing a positive silver halide photographic light-sensitive material to directly obtain a positive image.

[Conventional technology]

Photographic methods that provide direct positive images without the need for reversal processing steps or negative film are well known.

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. can.

One type uses a silver halide emulsion that has been fogged in advance and obtains a positive image directly after development by destroying fog nuclei (latent images) in exposed areas using solarization or the Burschel effect. be.

The other type uses an internal latent image type silver halide emulsion that is not fogged, and directly obtains a positive image by performing surface development either after image exposure and fogging treatment, or while performing fogging treatment. . The above-mentioned internal latent image type silver halide photographic emulsion is a type of halogenated silver halide emulsion that has photosensitive nuclei mainly inside the silver halide grains and forms latent particles (elements) inside the grains upon exposure. A silver photographic emulsion.

This latter type of method is more sensitive to boat fishing than the former type of method, and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type of method.

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2,592,250;
No. 466957, No. 2497875, No. 2588
No. 982, No. 3317322, No. 3761266
British Patent No. 3761276, British Patent No. 3796577, and British Patent No. 1151363, British Patent No. 1150553
No. 1011062, No. 1011062, etc. The main ones are listed in the specifications.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

For details on the formation mechanism of the direct positive image, see, for example, "The Theory of the Photographic 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. According to it, the initial imagewise exposure creates an internal latent image (Posit
Fog nuclei are selectively generated only on the surface of silver halide grains in unexposed areas by the surface desensitization effect caused by ivhole), and then a photographic image is formed in the unexposed areas by performing a normal so-called surface development process. It is believed that a (direct positive image) is formed.

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 "light fogging method" (for example, British Patent No. 1.151.3
63) and a nucleating agent (nu
creating agent) is known. This latter method is discussed, for example, in Research Disclosure.
Losure ) Magazine Volume 151 No. 15162 (
Published in November 1976), pages 76-78.

The disadvantage of the light fogging method is that the performance of the finished photosensitive material tends to change due to changes in the exposure amount, development time, developer composition, processing temperature, etc., and it also takes a long development time, making it difficult to increase the maximum image density. There is.

On the other hand, in the chemical fogging method, if the pH of the developer is low, development will be slow, so the pH must be raised;
If it is high, deterioration of the developing agent is likely to occur due to air oxidation,
This has the disadvantage that the fogging effect is reduced.

As described above, with the conventional fogging method, it is difficult to obtain a stable and good direct positive image. As a means to solve this problem, compounds that exhibit a nucleating effect even at I) 812 or less have been proposed in Japanese Patent Application Laid-Open No. 52-69613 and U.S. Patent No. 3.61.
No. 5.615 and No. 3.850.638, these nucleating agents act on silver halide during storage of the sensitive material before processing, or the nucleating agent itself decomposes. This has the disadvantage that the maximum image density after processing is reduced.

U.S. Pat. No. 3,227,552 describes the use of hydroquinone derivatives to increase the development rate of medium densities. However, even if this was used, the development speed was not sufficient, and in particular, an insufficient development speed was obtained with a developer having a pH of 12 or less.

Further, JP-A-60-170843 describes adding a mercapto compound having a carboxylic acid group or a sulfonic acid group to increase the maximum image density. However, even when these compounds are added, the maximum image density does not improve sufficiently. Moreover, the pH of the developer is 12.0, and the stability of the developer is insufficient.

JP-A-55-134848 discloses a treatment solution (pl(12,
0) to lower the re-small image density and prevent the formation of re-inverted negative images. However, this method does not increase the maximum image density or increase the development speed.

Further, Japanese Patent Publication No. 12709/1983 describes the addition of triazoline-thione and tetrasoline-thione type compounds as antifogging agents to sensitive materials on which positive images are directly formed by the photofogging method. However, even with these methods, high maximum image density and fast development speed could not be achieved.

As described above, there has never been a technique to stably obtain a direct positive color image having a high maximum color image density and a low minimum image density in a short processing time using a color developer having a low pH (pH less than 12).

Furthermore, direct positive emulsions with high sensitivity generally have the problem of frequently generating re-inversion negative images upon high-intensity exposure.

[Problem that the invention seeks to solve]

Therefore, it is an object of the present invention to fog an internal latent image type silver halide sensitive material which has not been fogged in advance to produce a low-p film in the presence of light exposure.
The object of the present invention is to provide a method for rapidly and stably forming a direct positive image having a high maximum image density and a low minimum image density by processing with a H color developer.

Another object of the present invention is to provide a method for forming direct positive images with less generation of re-inverted negative images during high-intensity exposure.

Also, to provide a method for directly forming a positive color image in which the maximum image density and minimum image density do not vary from the optimum value even if the temperature or pH of a color developing solution changes, and the brown color reproducibility does not change easily. It is in.

Furthermore, it is an object of the present invention to provide a direct positive color image forming method in which the maximum image density and the minimum image density do not easily vary from the optimum values even if the color development time varies with respect to the standard time, and the brown color reproducibility does not easily change.

Another object of the present invention is to provide a method for directly forming a positive image in which the maximum image density is less likely to decrease and the minimum image density is less likely to increase when a photosensitive material is stored for a long period of time.

Another object of the present invention is to provide a method for directly forming positive color images in which the developer is less likely to deteriorate due to air oxidation and has stable performance.

[A means of saving to solve problems]

The present inventors have discovered that the object of the present invention is to develop a photosensitive material in which at least one photographic emulsion layer containing internal latent image type silver halide grains which is not fogged in advance is formed on a support after imagewise exposure. In a method of directly forming a positive image by performing photofogging treatment before processing or during development treatment and developing treatment with a surface developer, the development treatment is performed on groups that adsorb to silver halide, thioether groups, and amino groups. , an organic group containing at least one ammonium group, an ether group, or a heterocyclic group. I found out that it can be done.

In the above method, a nucleation accelerator and a nucleating agent may coexist.

Here, the "nucleating agent" is a substance that acts to directly form a positive image during surface development of an internal latent image type halogenated emulsion that has not been fogged in advance. Two or more types of nucleating agents can be used in combination.

In addition, "nucleation accelerator" refers to a nucleating agent that does not substantially have the function of the nucleating agent described above, but promotes the action of the nucleating agent to increase the maximum density of a direct positive image and/or to increase the maximum density of a direct positive image. A substance that speeds up the development time required to obtain image density. Two or more kinds of nucleating accelerators can be used in combination.

Nucleation accelerators useful in the present invention have the following general formulas (I), (I
I) or (I[).

-Rituals (I) A -f-< Y wR] In the formula, A represents a group adsorbed to silver halide.

Examples of groups that adsorb to silver halide include heterocyclic groups having a mercapto group, heterocyclic groups capable of producing iminosilver, and hydrocarbon groups having a mercapto group. Examples of heterocyclic groups having a mercapto group include, for example, substituted or unsubstituted mercaptoazoles (e.g. 5-mercaptotetrazoles, 3-mercapto-1,2,4-
Triazole, 2-mercabutoimidazole, 2-
Mercapto-1゜3,4-thiadiazoles, 5-mercapto-1゜2.4-thiacyazoles, 2-mercapto-1゜3.4-oxadiazoles, 2-mercapto-1,,3,4- In order of selenadiazole, 2-mercaptooxazoles, 2-mercaptothiazoles, 2-mercaptobenzoxasoles, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles,
etc.), substituted or unsubstituted mercaptopyrimidines (eg, 2-mercaptopyrimidines, etc.), and the like.

Examples of heterocyclic groups capable of forming iminosilver include substituted or unsubstituted indazole, benzimidazole, benzotriazole, benzoxazole, benzthiazole, imidazole, thiazole, oxazole, triazole, and tetrazole. , azaindenes, pyrazole necks, and indoles.

Examples of the hydrocarbon group having a mercapto group include residues of alkylmercaptans, arylmercaptans, alkenylmercaptans, and aralkylmercaptans.

Y represents a divalent linking group consisting of an atom or a group of atoms selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of divalent linking groups include -3-1-〇-1-N-1 11II II IIOS
O II II 11-
N -S O2-1-N-C-N-1-N-C-N-
1-N-C○-1R= Rs R
7Ra Rs Rt.

○ ○ 0 13○2-1-C-1-3○-1-○S- etc. R1, R2, R3, R4, R5, R6, RT, R
e, R9 and RIQ are each a hydrogen atom, a substituted or unsubstituted alkyl group (e.g. methyl group, ethyl group, propyl group, n-butyl group, etc.), a substituted or unsubstituted aryl group (e.g. eva, phenyl group, etc.) , 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (e.g., flobenyl group, 1-methylvinyl group, etc.), or substituted or unsubstituted aralkyl group (e.g., benzyl group, phenethyl group, etc.).

R represents an organic group containing at least one thioether group, amino group (including salt form), ammonium group, ether group, or heterocyclic group (including salt form). Such organic groups include substituted or unsubstituted alkyl groups,
Examples include combinations of groups selected from alkenyl groups, aralkyl groups, or aryl groups and the above groups, but combinations of these groups may also be used. For example, hydrochloride of dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group, dimethylaminopropyl group, dimethylaminoethylthioethyl group, 4-dimethylaminophenyl group, 4-dimethylaminobenzyl group, methylthioethyl group. group, ethylthiopropyl group, 4-
Methylthio-3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group, methoxyethylthioethyl group, 3,4-dimethoxyphenyl group, 3-chloro-4-methoxyphenyl group, morpholinoethyl group,
1-imidazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, piperidinopropyl group, 2
-pyridylmethyl group, 2-(1-imidazolyl)ethylthioethyl group, pyrazolylethyl group, triazolylethyl group, methoxyethoxyethoxyethoxyethoxyethoxylponylaminoethyl group, and the like. n represents O or 1; m represents 1 or 2;

In general formula (II), Q is an atomic group necessary to form a 5- or 6-membered heterocycle, preferably consisting of at least one type of carbon atom, nitrogen atom, oxygen atom, sulfur atom, and selenium atom. represents.

Further, this heterocycle may be fused with a heteroaromatic ring.

Examples of heterocycles include tetrazoles, triazoles, imidazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxazoles, thiazole necks, benzoxazoles, benzthiazoles, benzimidazoles, and pyrimidines. It will be done.

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

In addition, these heterocycles include a nitro group, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a mercapto group, a cyan group,
Substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group, t-butyl group, cyanoethyl group, etc.), aryl groups (e.g., phenyl group, 4-
methanesulfonamidophenyl group, 4-methylphenyl L3゜4-dichlorophenyl group, naphthyl group, etc.), alkenyl group (e.g. allyl group, etc.), aralkyl group (e.g. benzyl group, 4-methylbenzyl group, phenethyl group) , etc.), sulfonyl groups (e.g. methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.),
Carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.)
, carbonamide group (e.g. acetamide group, benzamide group, etc.), sulfonamide group (e.g. methanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, etc.), acyloxy group (e.g. acetyloxy group, benzoyloxy group) , etc.), sulfonyloxy groups (e.g. methanesulfonyloxy groups, etc.), ureido groups (e.g. unsubstituted ureido groups, methylureido groups, ethylureido groups, phenylureido groups, etc.), thioureido groups (e.g. unsubstituted thioureido groups) group, methylthioureido group, etc.), acyl group (e.g. acetyl group,
benzoyl group, etc.), oxycarbonyl group (e.g. methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (e.g. methoxycarbonylamino group, phenoxyerbonylamino group, 2-ethylhexyloxycarbonylamino group, etc.) ), carboxylic acid or its salt, sulfonic acid or its salt, hydroxyl group, etc., but the nucleation promoting effect is better if it is not substituted with carboxylic acid or its salt, sulfonic acid or its salt, or hydroxyl group. This is preferable in this respect.

Preferred examples of the heterocycle represented by Q include tetrazoles, triazoles, imidazole necks, thiadiazoles, and oxadiazoles.

Y, RSm, and n are each synonymous with that of -ritual (I).

General formula (I) In the formula, Y, R, mSn, Q and M have the same meanings as those in general formula (I), and the heterocycle formed by Q is:
For example, indazoles, benzimidazole necks, benzotriazoles, benzoxazole necks, benzthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, tetraazaindene necks, triazaindenes, diazaindene necks, pyrazole necks. , indoles, etc.

The general formula (I), (I[) or (I[) of the present invention is shown below.
Although specific compounds represented by are shown below, the present invention is not limited to these compounds.

1N ■ CH2CH2S CH3 COOCH2CH25CH3 CON HCH2CH20CH3 2N CH2C82NHC○(CH2CH-0)3 CH3
\CH3 , N CH2SCH3 \C3H7 (.) \CH3 ・H (1 0 5-CH3 92CH2X ., 7NCH ・CH25H'HC'2/CH3 CH3/ S CH2CH2CH2N CH2CH2CH2N \CH3 Nuclei used in the present invention The accelerator is , Berichte der Deutschen Hemischen Gesellschaft (Beri
chemist der Deutschen Chemis
chenGesellschaft) 28.77 (
1875), JP-A-50-37436, JP-A No. 51-3
No. 231, U.S. Pat. No. 3.295.976, U.S. Pat.
．． 376, 310, Berichte der Deutschechen.
Berichte d
er DeutschenChemischen Ge
5ellschaft) 22.568 (1889)
, 29.2483 (1896), Journal of the Chemical Society (J.

Chem, Soc,) 1932.1806, Journal of the American Chemical Society (
J, Am, Chem, Sac, ) 71.4000
(1949), U.S. Pat. No. 2.585.388, 2.
No. 541.924, Advances in Heterocyclic Chemistry
eterocyclic chemistry)
9.165 (1968), Organic 5ynthesis
TV, 569 (1963), Journal of the American Chemical Society (J.A.
m, Chem, Soc, ) 45.2390 (1923
), Chemische Beri
9.465 (1876)
No. 28496, JP-A-50-89034, U.S. Patent No. 3
．． No. 106.467, No. 3.420.670, No. 2,
271.229, 3.137.578, 3.1
No. 48.066, No. 3.511.663, No. 3.06
No. 0.028, No. 3.271.154, No. 3.251
．． No. 691, No. 3.598.599, No. 3, 148.
No. 066, Japanese Patent Publication No. 43-4135, U.S. Patent No. 3.61
No. 5.616, No. 3.420.664, No. 3.07
1.465, 2.444.605, 2.444.
No. 606, No. 2.444.607, No. 2.935.4
It can be synthesized according to the method described in No. 04 etc. or the typical synthesis examples shown below.

Synthesis Example 1 Synthesis method of Exemplary Compound (1) 2.5-dimercapto-1,3,4-thiadiazole 7
．． 5g, 3-dimethylaminopropyl chloride hydrochloride 7.9g, pyridine 4g and n-butanol 60+nj!
and heated under reflux for 2 hours. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from ethanol.

Yield: 11 g Melting point: 149-152°C Synthesis Example 2 Synthesis of Exemplary Compound (13) 2. 7.5 g of 5-dimercapto-1,3,4-thiadiazole, 5.8 g of 2-aminoethyl chloride hydrochloride, and 4 g of pyridine were added to n - It was added to 60 ml of butanol and heated under reflux for 2 hours.

The reaction solution was ice-cooled, the precipitated crystals were collected by filtration, and methanol/
Recrystallized from water.

Yield 7.1g Melting point 228-229℃ (decomposition) Synthesis Example 3
Synthesis method of exemplified compound (6) 2.5-dimercapto-1,3,4-thiadiazole 7
．． 5g, 2-dimethylaminoethyl chloride hydrochloride 7
．． 3g, pyridine 4g n-butanol 60+nj! and heated under reflux for 2 hours. The reaction solution was ice-cooled, and the precipitated crystals were collected by filtration and recrystallized from ethanol.

Yield: 7.9g Melting point: 161-163°C Synthesis Example 4 Synthesis of Exemplary Compound (7) 2.5-dimercapto-1,3,4-thiadiazole 1
5.0 g, l-(2-chloroethyl)imidazole hydrochloride 20.0 g, and pyridine 9.5 g in acetonitrile 1
00ml and heated under reflux for 4 hours. After the reaction, the reaction solution was cooled, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of dimethylformamide and methanol to obtain one compound (7).

Yield: 11.2 g Melting point: 226-228°C Synthesis Example 5
Synthesis method of exemplified compound (89) 2-Mercapto-5-phenoxycarbonylamino 1,3,4-thiadiazole 1
Add 200 mA of acetonitrile to 2.7 g at room temperature.
6.2 g of -N,N-dimethylaminopropylamino was added dropwise.

After the dropwise addition, the mixture was heated and stirred at 50° C. for 1.5 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (89).

Yield: 10.7 g Melting point: 228-230°C Synthesis Example 6
Synthesis method of exemplified compound (90) 13.3 g of 2-amino-5-mercapto-1,3,4-thiadiazole was mixed with 100 rIIβ of acetonitrile, 40 g of dimethylacetamide.
m, II! 15.9 g of 3-(N,N-dimethylamino)probylthiocyanate was added dropwise at room temperature. After the dropwise addition, the mixture was heated and stirred at 50° C. for 2 hours, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of methanol and concentrated hydrochloric acid to obtain compound (90).

Yield: 12.6 g Melting point: 146-148°C Synthesis Example 7
Synthesis method of exemplified compound (62) 36.6 g of 5-amino-2-mercaptobenzimidazole and 17.1 g of pyridine
+t+j7 N,N-dimethylacetamide 250+n
jl! and phenylchloroforme at room temperature) 34
．． 4 g was added dropwise. The mixture was stirred at room temperature for 1.5 hours and then added to water-cooled 1.5β to precipitate crystals. The obtained crystals were collected by filtration and recrystallized from acetonitrile to give 2-
47.7 g of mercapto-5-phenoxycarbonylaminobenzimidazole was obtained.

To 8.6 g of the obtained 2-mercapto-5-phenoxycarbonylaminobenzimidazole was added acetonate)
00mf was added thereto, the mixture was stirred and heated to 45°C, and 14.5 g of N,N-dimethylaminoethylenediamino was added dropwise. 45
After stirring at ℃ for 1.5 hours and filtering the precipitated crystals, N
The product was recrystallized from a mixed solvent of N-dimethylformamide and methyl alcohol, yielding 6.2 g (yield 74%) of the desired product.

Melting point 240°C (decomposition) Synthesis Example 3 Synthesis method of exemplified compound (95) p-(2-N,
N-dimethylaminoethoxy〉-〇-phenylenediamino (7.8 g) was added to a solution of 2.4 g of potassium hydroxide in 1120 mβ of ethyl alcohol, and 12 m of carbon disulfide was added at 40°C.
1 was added dropwise. After dropping, heat under reflux for 5 hours and add 6+n of concentrated hydrochloric acid.
j! was added, and the solvent was distilled off under real pressure. The obtained oily residue was fitful with a silica gel column, and then recrystallized from acetonitrile to obtain 3.8 g (yield: 40%) of the desired product.

Melting point: 233-235°C (decomposed) Synthesis Example 9 Synthesis of Exemplified Compound (99) Ethyl alcohol was added to 17.2 g of 2-mercapto-6-fethoxycarbonylaminobenzoxazole synthesized in the same manner as Synthesis Example 7. Then, 6.2 g of N,N-diethylethylenediamino was added dropwise at room temperature. After the dropwise addition, the mixture was stirred at 50° C. for 30 minutes and then cooled to room temperature to precipitate crystals. The precipitated crystals were collected by filtration and recrystallized from a mixed solution of N,N-dimethylformamide and acetonyl.
(yield 79%).

Melting point: 280°C or higher (decomposition) Synthesis example 10 Synthesis method of exemplified compound (3) 10.5 g
2,5-dimercapto-1,3,4-thiadiazole was added with 100 mf of ethyl alcohol, and then 141
'nl of 28% sodium methoxide solution was added and dissolved by heating. 7.7 ml of 2-methylthioethyl chloride was added dropwise to this solution, and the mixture was refluxed for 3 hours. After the reaction, the reaction solution was allowed to cool to room temperature, poured into ice water 11, and the precipitated crystals were collected by filtration and recrystallized from a mixed solvent of ethyl acetate and n-hexane to obtain 10.8 g of the desired product (yield: $68. 8%).

Melting point: 75-76°C Synthesis Example 11 Synthesis of Exemplified Compound (26) To a solution of 7.5 mj2 of hydrazine hydrate and 30 mβ of ethanol, 8°6 g of 2-(N-morpholino)ethyl inthiocyanate was added dropwise under water cooling, and then Stirred for 2 hours. 50 ml of formic acid was added to 9.5 g of crystals obtained by filtering the generated precipitate, and the mixture was heated under reflux for 8 hours. The residue obtained by distilling the reaction solution under reduced pressure was
After neutralization with an aqueous sodium hexahydroxide solution, the product was purified by column chromatography (stationary phase alumina, developing solvent, ethyl acetate/methanol), and further recrystallized from chloroform to obtain 4.9 g of the desired product.

Melting point: 146-147°C Synthesis Example 12 Synthesis of Exemplified Compound (28) 6.5 g of 2-dimethylaminoethyl inthiocyanate was gradually added to a solution of 7.5 ml of hydrazine hydrate and 30 ml of ethanol under water cooling, and the mixture was stirred for an additional 3 hours. Stirred. Add the reaction solution to 100ml of water.
The organic layer was washed with saturated brine, and then the solvent was distilled off under pressure. (Formic acid 36rnR was added to 17.2 g of the residue and heated under reflux for 8 hours. The reaction solution was distilled off under reduced pressure, the resulting residue was neutralized with a 5% aqueous sodium hydroxide solution, and then subjected to column chromatography (with an eye to fixation). Alumina, long-term solvent, ethyl acetate/methanol) and recrystallized from ethyl acetate/n-hexane to obtain the desired product 3.8.
I got g.

Melting point: 103-104°C Synthesis Example 13 Synthesis of Exemplified Compound (103) Add 7.2 g of 3-dimethylaminopropyl thiocyanate to a solution of 7.5 mβ of hydrazine hydrate and 30 mf of ethanol under water cooling.
The mixture was added dropwise and further stirred for 3 hours. Add the reaction solution to 100 mjl of water.
! After extracting with ether and washing the ether layer with saturated brine, the solvent was distilled off under reduced pressure. 7,8 g of residue given
40 mf of formic acid was added to the mixture, and the mixture was heated under reflux for 8 hours. The reaction solution was distilled off under reduced pressure, and the resulting residue was 5% hydroxylated.) After neutralization with an aqueous IJ solution, it was purified by column chromatography (stationary phase alumina, developing solvent, ethyl acetate/methanol),
Further, recrystallize with isopropyl alcohol to obtain the target product 4.5.
I got g.

Melting point: 161-163°C Synthesis Example 14 Synthesis of Exemplified Compound (42) To a solution of 13.3 g of aminoacetaldehyde diethylacecure added to 100 mA of carbon tetrachloride, 13 g of 2-dimethylaminoethyl isothiocyanate was gradually added under water cooling. . After stirring at room temperature for 2 hours, the solvent was distilled off under reduced pressure. To the resulting residue was added 110 ml of 35% sulfuric acid while cooling with water, and the mixture was further heated under reflux for 3 hours. The reaction solution was neutralized in a 30% aqueous sodium hydroxide solution and extracted with chloroform. The organic layer was dried over anhydrous sulfuric acid and the solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from ethyl acetate to obtain 6.8 g of the desired product.

Melting point: 130-131°C Synthesis Example 15 Synthesis of Exemplified Compound (43) To a solution of 13.3 g of aminoacetaldehyde diethylacecure in 100 mf of carbon tetrachloride was added 2-(N-morpholino)ethyl inthiocyanate 17 under water cooling. 2 g of the solution was added dropwise. After stirring at room temperature for 2.5 hours, the solvent was distilled off under reduced pressure. To the resulting residue was added 110 mf of 35% sulfuric acid while cooling with water, and the mixture was further heated under reflux for 4 hours. The reaction solution was neutralized in a 30% aqueous sodium hydroxide solution and extracted with chloroform. After drying the organic layer over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was recrystallized from isopropyl alcohol to obtain the desired product 7.
Around 5g.

Melting point: 154-156°C Synthesis Example 16 Synthesis of Exemplified Compound (56) 7.2 g of sodium azide was dissolved in 50 ml of water, and 17.2 g of 2-(N-morpholino)ethyl isothiocyanate was heated to 80°C. A mixed solution of g and dioxane (20 ml) was added dropwise thereto, and the mixture was stirred at 80° C. for 1 hour. After the reaction, insoluble matter was removed by filtration, 8.8 ml of concentrated hydrochloric acid was added, and the precipitated crystals were collected by filtration.
Recrystallized from a mixed solvent of methyl alcohol and water to yield 1 g of target compound 14.

Melting point: 139-141°C Synthesis Example 17 Synthesis of Exemplary Compound (83) 5-phenoxycarbonylbenzotriazole 11.2 g, N,
1 part benzene to 4.4 g N-dimethylethylenediamino
50ml of the mixture was added and heated under reflux for 4 hours. After cooling to room temperature, the precipitated crystals were collected by filtration and recrystallized from methyl alcohol to obtain 7.9 g of the desired product.

Melting point: 182-184°C A nucleation accelerator can be contained in a light-sensitive material or a processing solution. or a protective layer). Particularly preferred is a silver halide emulsion layer or a layer adjacent thereto.

The amount of nucleation accelerator added is 10-6 per mole of silver halide.
~10-2 mol is preferred, more preferably 10-5~
It is 10-2 mol.

In addition, when the nucleating accelerator is added after processing, that is, to the developer or its pre-bath, 10-8 to 10-'
It is preferably mol, more preferably 10-7 to 10-4 mol.

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 certain amount of silver halide emulsion is coated on a transparent support, and this is exposed to light for a fixed time of 0.01 to 10 seconds using the following developer Δ (internal type developer). The maximum density measured by a normal photographic density measuring method when developed at 18°C for 5 minutes was determined by the following developer B (surface type developer ) at 20℃
Preferred are those having a density that is at least 5 times greater, more preferably at least 10 times greater than the maximum density given by 1 when developed for 6 minutes.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5 gKBr 5
gK I O, 5g Add water 1μ surface developer B Metol 2.5g! -Alcorbic acid LogN a B 02 ・4
H2035gKBr
Add 1g water
Specific examples of internal type emulsions include those described in U.S. Patent No. 2.
Conversion silver halide emulsion as described in US Pat. No. 592.250, U.S. Pat. No. 3.761.276
No. 3.850.637, No. 3.923.513, No. 4, 035.185, No. 4.395.478,
No. 4.504.570, No. 52-156614, No. 55-127549, No. 53-60222, No. 56-22681, No. 59-208540, No. 60
-No. 107641, No. 61-3137, Patent Application No. 1983-
No. 3642, Research Disclosure Magazine No. 2
3510 (issued November 1983) p. 236, a core/shell type silver halide emulsion can be mentioned.

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 grains having a thickness ratio value 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 is one that does not contain silver iodide or contains less than 3% mole of silver iodide. A salt containing (iodine) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The average grain size of silver halide grains is 2 μ or less 0.1
μ or more is preferred, but particularly preferred is 1μ or less 0.1
It is 5μ or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the number or weight of all particles should be within ±40% of the average particle size, preferably within ±20%. So-called "monodisperse" silver halide emulsions having a narrow grain size distribution of 90% or more are preferably 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. of particles are mixed in the same layer or in a separate layer.
Can be applied. 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 No. 17643-I (published December 1978), p. 23.

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. A detailed example can be found in the patent described in Research Disclosure Magazine No. 17643-IV (published December 1978), pages 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of Sensitivity III, and/or stabilizing photographic performance. Can be done. For detailed concrete examples,
For example, Research Disclosure Magazine No. 176
43-VI (issued December 1978) and E, J.
“Stabilization of photographic silver halide emulsions” by Bin (3inn) (Focal War Press) [5tabilizati
on of PhotographicSilver
Halide Emulsions” (Foca
I Press) '), published in 1974, etc.

The entire surface exposure, that is, the fogging exposure in the present invention is performed after the imagewise exposure, before the development process, 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. 58-62652, No. 58-60739, No. 58
-70223 (corresponding U.S. Patent No. 4440851), No. 58-120248 (corresponding European Patent No. 89101A2)
etc. are listed. For photosensitive materials that are sensitive to all wavelengths, such as color photosensitive materials, Japanese Patent Application Laid-Open No. 56-1373
A light source with high color rendering properties (as close to white as possible) such as those described in No. 50 and No. 58-70223 is preferable. The illuminance of the light is 0.01 to 2000 lux, preferably 0.0
5 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 preferred. 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. Exposure time can also be shortened by using weaker light at the beginning of exposure and then using stronger light.

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 immersion in the liquid to the light fog 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 seconds to 1 minute, more preferably 1 second to 4 minutes
It is 0 seconds.

A photosensitive material containing a nucleating agent may be fog-exposed.

In the present invention, a nucleating agent may be used in addition to the nucleating accelerator. As such a nucleating agent, all compounds conventionally developed for the purpose of nucleating internal type silver halide can be used. Two or more types of nucleating agents may be used in combination. To explain in more detail, examples of the nucleating agent include Research Disclosure Magazine No. 22,534.
(Published January 1983, pages 50-54), these are broadly classified into three types: hydrazine compounds, quaternary heterocyclic compounds, and other compounds.

First, as a hydrazine compound, for example, the above-mentioned Research Disclosure magazine Nα15.162 (1976
Published in November, pp. 76-77) and the same magazine No. 23, 51
0 (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. 4.03
0.925, 4.080.207, 4.0
No. 31.127, No. 3.718.470, No. 4,
No. 269.929, No. 4.276, No. 364, No. 4
．． No. 278.748, No. 4.385.108, No. 4.459.347, British Patent No. 2,011,391
B, JP-A-54-74.729, JP-A No. 55-163
, No. 533, No. 55-74.536, No. 59-195.
．． No. 233, No. 59-200.231, No. 59-20
No. 1,045, No. 59-201.046, No. 59-2
No. 01,047, No. 59-201.048, No. 59-
No. 201,049, No. 60-170.843, No. 60
- No. 179.734, and Research Disclosure Magazine No. 15.750 (Published May 1977, p. 54)
Examples include those listed in .

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86.829, U.S. Pat. No. 4.560.638, U.S. Pat. No. 4.478, and U.S. Pat.

Next, examples of quaternary heterocyclic compounds include the aforementioned Research Disclosure magazine Nα22,534 and the Japanese Patent Publication No. 4
No. 9-38.164, No. 52-19.452, No. 52
-47,326, JP-A-52-69,163, same 5
No. 2-3.426, No. 55-138.742, No. 60
-11,837, U.S. Patent No. 4.306.016;
and “Research Disclosure Magazine” Nα23.2
13 (published August 1983, pages 267-270).

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.

When incorporated into a sensitive material, it is preferably added to the Utsumi-type silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, other nucleating agents may be added. Layers such as interlayers and subbing layers may also be added to the backing layer. When the 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 a nucleating agent is contained in the sensitive material, the amount used is preferably 10-'' to 10-2 mol per mol of silver halide.
More preferably, it is 10-7 to 10-3 mol.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
1 f is preferably from 10-' to 10-1 mol, more preferably from 10''4 to 10-2 mol.

A variety of color couplers can be used to form direct positive color images. Useful color couplers are
A compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of a p-phinidine diamino color developer, and is itself a substantially non-diffusible compound. .

Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. These cyans that can be used in the present invention,
Specific examples of magenta and yellow couplers can be found in Research Disclosure, No. 17643 (1978).
Published in December 2016) p25■-ri section, same No. 18717 (
Issued in November 1979) and patent application No. 61-32462
and the patents cited therein.

Among them, representative examples of yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type yellow m:equivalent couplers. Especially α−
Pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers are preferred because they provide high color density, and 5-pyrazolone is preferably used in the present invention. Examples of magenta couplers include 5-pyrazolone couplers substituted at the 3-position with an arylamino group or an acylamino group (especially sulfur atom separation type two-equivalent couplers).

More preferred are pyrazoloazole couplers, among which pyrazolo C5,1-c] [l, 2.4F triazole neck, etc. described in U.S. Pat. U.S. Patent No. 4,500.630 in terms of low side absorption and light fastness
Even more preferred are the imidazo CI, 2-b) pyrazoles described in U.S. Pat. J azoles are particularly preferred.

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent No. 2.474.293, U.S. Patent No. 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.

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

Typical amounts used for color couplers range from 9,0.001 to 1 mole per mole of photosensitive silver halide, preferably 0, Ol to 0 for yellow couplers.
．． 0.003 to 0.5 for monobeta magenta couplers.
3 mono or cyan coupler is 0.002 to 0.
It is 3 moles.

The light-sensitive material used in the present invention contains hydroquinone derivatives, aminophenol derivatives, aminos, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, etc. as color antifogging agents or color mixing prevention agents. May contain.

Typical examples of color antifogging agents and color mixing prevention agents are disclosed in Japanese Patent Application No. 61-3.
No. 2462, pages 600-630.

Various anti-fading agents can be used in the photosensitive material of the invention. Organic anti-fading agents include hydroquinones,
Hindered phenol necks, mainly 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, bisphenol necks,
Typical examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered aminos, and ether or etesur derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoquinamide)nickel and (bis-N,N-dialkyldithiocarbamado)nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
Compounds having a hindered amino and a hindered phenol fraction structure in the same molecule as described in US Pat. No. 4,268,593 give good results. In addition, in order to prevent the deterioration of magenta dye images, especially the deterioration caused by light, the substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

Representative examples of these anti-fading agents are disclosed in Japanese Patent Application No. 32462/1986.
No., pp. 401-440. These compounds are usually 5% for their respective color couplers.
The purpose can be achieved by co-emulsifying with the coupler and adding it to the photosensitive layer in an amount of from 100% by weight. In order to prevent cyan dye from deterioration due to heat and especially light, it is effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer. UV absorbers can also be added.

Representative examples of compounds are disclosed in Japanese Patent Application No. 61-32462, 391-4.
It is described on page 00.

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.

The photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air fog preventive agents, coating aids, hardeners, antistatic agents, etc. A slippery improver, etc. can be added. Representative examples of these additives are [Research Disclosure]
) Magazine No., 1 7 6 4 3 ■~XI (19
Published in December 1978) p25-27 and p.18716
(Published in November 1979) It is described on 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,
At least one green-sensitive emulsion layer and one blue-sensitive emulsion layer each.
have one. The order of these layers can be arbitrarily selected as necessary. The preferred arrangement order 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 emulsion layers may be composed of two or more emulsion layers having different sensitivities, or two or more emulsion layers having the same sensitivity.
A non-light sensitive layer may be present between the two or more emulsion 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, but 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 layer,
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 described in Research Disclosure Magazine N.

17643X (published in December 1978), p. 28, and the supports described in European Patent No. 0.182.253 and JP-A-61-97655. Further, the coating method described in the same magazine No. 17643XV, 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, and color reversal paper. It can also be used for full-color copying machines and color hard copies for storing images on CRTs. The present invention has also been published in "Research Disclosure" magazine no.

17123 (published in July 1978), etc., and which utilizes a mixture of three color couplers.

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
Examples include those described in No. 1-32462, pages 374-391.

The coupler used in the present invention is dissolved in an organic solvent with a high boiling point and/or a low boiling point, and added to an aqueous solution of gelatin or other hydrophilic colloid by high-speed stirring using a homogenizer, mechanical pulverization using a colloid mill, or It is emulsified and dispersed using a technique that uses sound waves, and then added to the emulsion layer. In this case, it is not necessary to use a high boiling point organic solvent, but
It is preferable to use the compounds described on pages 1 to 467.

The coupler used in the present invention is disclosed in Japanese Patent Application No. 61-32462.
It can be dispersed in a hydrophilic colloid by the method described in Nos. 468-475.

The color developing solution used in the development of the light-sensitive material of the present invention does not substantially contain a silver halide solvent, and is preferably an alkaline aqueous solution containing an aromatic primary amino color developing agent as a main component. Examples of additives used in the color developing solution of the present invention include JP-A-60-144739, pages 14-22, JP-A-60-262161, pages 45-50,
Various compounds described on pages 11 to 22 of Japanese Patent Application No. 61-32462 can be used.

Furthermore, the color developing solution of the present invention contains antifogging agents such as tetrazaindenes, benzindazoles, benzotriazoles, benzimidazoles, benzothiazoles, benzoxazoles, and 1-7enyl-5-mercaptotetrazoles. Particular preference is given to using repeating cyclothiones, aromatic and aliphatic mercapto compounds.

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

The bleaching process may be carried out simultaneously with the fixing process in a single bath bleach-fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is followed by bleach-fixing, or a method in which bleaching and fixing is carried out after fixing. An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention.

Additives used in the bleaching solution or bleach-fixing solution of the present invention include Japanese Patent Application No. 61-32462, page 22 -
Various compounds described on page 30 can be used. After the desilvering process (bleach-fixing or fixing), water washing and/or
Or perform processing such as stabilization.

As additives used in the water washing and stabilization steps, various compounds described on pages 30 to 36 of Japanese Patent Application No. 61-32462 can be used.

The smaller the amount of replenisher in each treatment step, the better. The amount of replenisher is preferably 0.1 to 50 times, more preferably 3 times, the amount of prebath brought in per unit area of the photosensitive material.
~30 times.

〔Example〕

Emulsion A: An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 0.4 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mole of Ag at 75°C for about 20 min with vigorous stirring. They were added simultaneously over several minutes to obtain an octahedral monodispersed silver bromide emulsion with an average grain size of 0.4 μm. To this emulsion were added 9 mg of thiosulfate (IJ) and potassium chloroaurate (tetrahydrate) per mole of silver.
Chemical sensitization treatment was performed by heating at °C for 80 minutes.

Using the thus obtained silver bromide grains as cores, they were further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and the final octahedral monodisperse core/shell silver bromide grains had an average particle diameter of 0.7 μm. An emulsion was obtained.

After washing with water and desalting, this emulsion contains 1 and 5 per mole of silver, respectively.
Add Jum and chloroauric acid (tetrahydrate) and heat at 60°C for 60 minutes to perform chemical sensitization.
Internal latent image type silver halide emulsion A was obtained with a coefficient of variation of q grain size of 10%.

Emulsion B 11 KBrQ, 5 mol, NaCj! After adding 30 g of gelatin to a mixed solution 1β with a concentration of 0.2 mol and 15 mol of KIO,0O and dissolving it, 1 mol of silver nitrate/1β was added at 60°C.
700 cc of liquid No. 1 was added to the above mixed solution over 20 minutes, and physical ripening was further performed for 20 minutes.

Next, after washing with water to remove water-soluble halides, 20g of gelatin was added, and the total volume was made up to 1200cc with water.
It was prepared as follows. A silver halide emulsion with an average grain size of 0.4 μm was obtained.

To 300 cc of this emulsion, 500 cc of a 1 mol/β aqueous silver nitrate solution and 500 cc of an aqueous solution containing 0.6 mol of potassium bromide and 0.7 mol of sodium chloride per 11
After simultaneous addition of CC to precipitate a silver chloride shell,
Washed with water. Silver halide emulsion B with an average grain size of 0.7 μm
I got it.

Example 1 Using core/shell type internal latent image type emulsion A, a full multilayer color photographic paper having the layer structure shown in Table 1 was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating solution prepared: 10 g of nitrogen coupler (a), 2.3 g of color image stabilizer (b), and 10 m of ethyl acetate! and solvent (c) 4+++j! Dissolve this solution in a solution containing 5 ml of 10% sodium dodecylbenzenesulfonate.
% gelatin aqueous solution 9Qmj2.

On the other hand, the following red-sensitive dye was added to the silver halide emulsion (containing 7Qg/kg of Ag) at a concentration of 2% per mole of silver halide.
．． 0x10-'mol plus red-sensitive emulsion and 90'g of soybean
The emulsified dispersion, the emulsion, and the development accelerator (d) were mixed and dissolved, the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained, and the addition of the present invention was carried out as shown in Table 2. Ag nuclear promoter
A coating solution for the first layer was prepared by adding 1.5 x 10-' mol per mol.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. 1-oxy-3 as gelatin hardening agent in each layer
, 5-dichloro-5-)riazinna) IJum salt was used.

The following spectral sensitizers were used in each emulsion.

red sensitive emulsion layer Green sensitive emulsion layer The following dye was used as the anti-irradiation dye.

Anti-irradiation dye 5o3KSO for green-sensitive emulsion layer
3: anti-irradiation dye 5O3K for red-sensitive emulsion layer
The structural formula of the compound used for SO2 in this example is as follows.

(') Magenta coupler (h) Solvent (1) Ultraviolet absorber (g) Color image stabilizer 'L Shili3:, H,, (t) 1 mixture (weight ratio)
shin2LJIILIJU
L, sl'l+i ('') color mixture prevention agent
(k) Solvent (m) Color image stabilizer.

(1) Yellow coupler - Wedge exposure (
1/lo second, IOCMS), the following processing steps A and B were performed, and the magenta color image density was measured. During color development, fog exposure (0.5 lux on the sensitive material film, color temperature 5400K) was applied for 10 seconds from 15 seconds after the start of development.

The results obtained are shown in Table 2.

Processing step A Time Temperature color development 2 minutes 30 seconds 33℃ bleach fixing
1 minute 30 seconds 33℃ stable ■ 1 minute
Stable at 33℃ ■ 1 minute 33
℃ stable ■ 1 minute 33℃ The replenishment method for the stable bath is to replenish the stable bath ■, lead the overflow liquid from the stable bath ■ to the stable bath ■, and lead the overflow liquid from the stable bath ■ to the stable bath ■, which is the so-called countercurrent flow. It was a supplementary method.

Processing step B Time Temperature color development 1 minute 30 seconds 37℃ bleach fixing
40 seconds Stable at 37℃ 0 20 seconds Stable at 37℃ ■ 20 seconds 37℃
Stable ■ 20 seconds 37℃ Other conditions are the same as processing step A [Color developer] Mother liquor Diethylenetriaminopentaacetic acid 2.0g Benzyl alcohol 12.8g Diethylene glycol 3.4g Sodium sulfite
2.0g Sodium Bromide 0.26
g Hydroxylamino sulfate 2.60 g Sodium chloride 3.20 g 3-Methyl-4-amino-N-4,251 g Ethyl-N-(β-
Methanesulfonamidoethyl)-aniline Potassium carbonate 30.0g Water was added to the mixture and 1000100O10.20 The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Mother liquor Ammonium thiosulfate 110g Sodium bisulfite 10g Iron diethylenetriaminopentaacetate 56g (II hand
1000ml 100O6,5 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother liquor 1-hydroxyethylidene 1.6mβ-1,l
'-Diphosphonic acid (60%) Bismuth chloride 0.35 g Polyvinylpyrrolidone 0.25 g Aqueous ammonia 2.5mβmβnitriloic acid Acetic acid
N a L, Og5-chloro-2-methyl-450mg -inthiazolin-3-one 2-octyl-4-isothia 50mg zolin-3
-ON optical brightener (4,4'-Sia 1,0g minostilbene type) Add water to 10100O! pH 7.5 pH was adjusted with potassium hydroxide or hydrochloric acid.

Table 2 Comparative Compounds □ CH2CH2S C)13H Samples No. L to 17 to which the compound of the present invention was added had a lower minimum image density (D, .) and a lower maximum image density than the comparative examples Nα18 to 22. (D,...'') was high and preferred. Similar results were obtained when cyan and yellow densities were measured. Also, a similar tendency was observed even when the processing steps were changed.

Furthermore, samples No. 1 to 17 are comparative sample No.
.

There were fewer re-inversion negative images compared to Nos. 18-22.

Example 2 Emulsion B and the following yellow coupler were used, the composition of the third layer was as shown in Table 3, and the nucleation accelerator of the present invention was added at 2.1% per mole of Ag as shown in Table 4. Color photographic paper was prepared in the same manner as in Example 1 except that x10-4 mol was added.

(n) Yellow coupler Table 3, (0) Magenta coupler (1:1.5 mixture ratio) (q) Solvent This color photographic paper was imagewise exposed in the same manner as in Example 1, and 37
A positive color image was obtained by fogging exposure processing in the same manner as in Example 1, except that processing step B was performed using a color developing solution that had been run for 16 hours at °C. The cyan color density of this image was measured.

Table 4 Samples Nos. 23 to 27 containing the compound of the present invention were less susceptible to running deterioration of the color developer than No. 28 containing no additives.

Example-3 Emulsion-2 of Example-2 of JP-A-55-127549
Color application was carried out in the same manner as in Example 2, except that the emulsion prepared in the same manner as in Example 1 was used, the nucleation accelerator shown in Table 5 was used at 5 x 10-5 mol per 1 mol of Ag, and the following coupler was used. Created a paper.

(Cyan coupler) Cβ (Yellow coupler) This color printing A paper was exposed and processed in the same manner as in Example-2, and the graininess of the obtained positive color image was visually evaluated. The results are shown in Table 5.

Table 5 Comparative Compound-5 Graininess Evaluation 5...Excellent 4...Slightly Excellent 3...Fair 2...Slightly Poor 1...Inferior Samples No. 29 to 32 containing the compounds of the present invention have superior graininess compared to comparative samples No. 33 to 35 (
This difference was particularly noticeable when a color developer that had deteriorated due to running was used.

Example 4 A sample was prepared in the same manner as in Example 3, except that a nucleating accelerator and a nucleating agent were used in the first, third and fifth layers as shown in Table 6, and exposed and After processing, a positive color image was obtained.

The yellow density of the positive color image was measured and shown in Table 6.

1 ] □ CH (jCH The same results as in Example-1 were obtained with the sample using the nucleating agent. The cyan density and magenta density were also measured and similar results were obtained.

Example 5 The following green-sensitive dyes were added to emulsion A, and 1-oxy-3,5-dichloro-3-1-riazine sodium salt was used as a gelatin hardening agent, and the composition of the present invention was prepared as shown in Table 7. After adding 5.2X 10-' moles of nucleation accelerator per mole of Ag, silver!
A gelatin protective layer was simultaneously coated thereon to prepare a direct positive photosensitive material.

These samples were exposed to an IKW tungsten lamp with a color temperature of 2854° for 1 second through a step wedge, and developed at 33°C for 1 minute using a developer solution containing the following replenisher Alf and starter 820mβ. I did it. At that time, fog exposure was performed in the same manner as in Example-1. Next, the film was stopped, fixed, washed with water, and dried in a conventional manner. The maximum concentration (D□) and sensitivity of each sample were measured.゛The results are shown in Table 7.

Green-sensitive dye solution A Sodium sulfite 100g Potassium carbonate 20g 1-phenyl-4-methyl-4-3g Hydroxymethyl-3-pyrazolidone hydroquinone 45g 5-methylbenzotriazole 40mg Add water
1 ppH with potassium hydroxide
11.2 Toshu Sei Starter B Sodium Bromide 175g Glacial Acetic Acid
Add 63+nβ water
11 Table 7 Sample No. 7 containing the compound of the present invention even in black and white photosensitive materials,
Samples Nos. 50 to 54 had higher maximum image densities (D, , , ) than No. 5.5, which had no additives.

Example 6 Color photographic paper was prepared in the same manner as in Example 1 except that the nucleating accelerator was omitted. After imagewise exposure, the nucleation accelerator shown in Table 8 was added at 3.5X10-6 mol/f! A positive color image was obtained by exposure and processing in the same manner as in Example 1, except that the added color developing solution was used. The measurement results of magenta density are shown in Table 8.

Table 8 Even when the nucleation accelerator was added to the color developing solution, samples Nos. 49 to 53 using the compounds of the present invention had higher I)+aax and Dm
lh was low. Similar results were obtained for cyan and yellow densities.

Example-7 Samples Nα1 to 22 of Example-1 were heated for 1/100 seconds, 1
Exposure was carried out at 0CI/Is, and processing steps A and B were performed in the same manner as in Example-1. These samples are also No. 1-17
There were fewer re-inverted negative images compared to No. 18-22.

〔Effect of the invention〕

According to the present invention, a high maximum image density and a low minimum image density can be obtained by processing an internal latent image type silver halide photosensitive material that has not been fogged in advance with a low pH color developing solution in the presence of fog exposure. Direct positive images can be formed quickly and stably.

Further, it is possible to form a direct positive image with less generation of re-inverted negative images during high-intensity exposure.

Furthermore, even if the temperature or pH of the color developer changes, the maximum image density and minimum image density do not easily vary from their optimum values.
It is possible to directly form a positive color image with little change in brown color reproducibility.

Furthermore, even if the color development time changes with respect to the standard time, the maximum image density and the minimum image density do not easily change from the optimum 1st, and the color reproducibility does not change by <1. ) can directly form positive color images.

Further, even when the photosensitive material is stored for a long period of time, it is possible to form a direct positive image in which the maximum image density is less likely to decrease and the minimum image density is less likely to increase.

Furthermore, since the pH of the developing solution is low, it is less susceptible to deterioration due to air oxidation, etc., and direct positive color images with stable performance can be formed over a long period of time.

Procedures - City Registrar and Patent Office Director Kunio Ogawa 1, Indication of Case Patent Application No. 184499 of 1985
No. 2, Title of the invention Direct positive image forming method 3, Relationship with the person making the amendment Applicant name (520) Fuji Photo Film Co., Ltd. 4, Agent cr + 4υ 5, Date of amendment order Voluntary (1) Details Book 4 due east lines 10-1.1” (Po
``sitivehole)''.

(2) Formula 72 on page 36 of the same book is corrected as follows.

(3) The "certain amount" on page 55, line 19 of the same book is corrected to "0.5 to 3.0 g/m'J as silver."

(4) Insert the following sentence after "Halogen...particle size" on page 58, line 8 of the same book.

“(For spherical or near-spherical particles, the particle size is the particle diameter, and for cubic particles, the particle size is the particle size, and it is the average based on the projected area.)” (5) Same book, page 74, line 14. Correct “test solution” to “test solution”.

(6) "(a) 10 g" on page 78, line 8 of the same book is corrected to [(a) 6, 2 g J.

(7) Insert the following sentence after “Sodium salt was used” in the fourth line of page 79 of the same book.

"4-hydroxy-6-methyl 1,3°3a in each emulsion layer.
, 4 mg/m' of 7-chitrazaindene was added. (8) In the table on page 80 of the same book, the usage amount in the column of anti-curling layer "2.7 g/m" was changed to r5.5 g/m.
'Correct to J.

Claims (1)

[Claims] A photosensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which has not been fogged in advance on a support is subjected to a photofogging treatment after imagewise exposure, before or during development processing, In the method of directly forming a positive image by developing with a surface developer, at least one group adsorbing to silver halide, a thioether group, an amino group, an ammonium group, an ether group, or a heterocyclic group is used in the development process. 1. A direct positive image forming method characterized in that the method is carried out in the presence of a nucleation accelerator selected from compounds having an organic group.