JP2525600B2 - Direct positive image forming method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a direct positive color image forming method using an internal latent image type silver halide emulsion.

BACKGROUND OF THE INVENTION Photographic methods of obtaining a positive image directly without the need for a reversal step or a negative film are well known.

As a method of forming a positive image directly using an internal latent image type silver halide emulsion, various techniques have been known so far, for example, U.S. Patent Nos. 2,592,250 and 2,466,957
No. 2, No. 2,497,875, No. 2,588,982, No. 3,317,32
No. 2, No. 3,761,266, No. 3,761,276, No. 3,796,5
No. 77, British Patent Nos. 1,151,363 and 1,150,553 (No. 1,011,062), and those described in the respective specifications are the main ones.

Direct positive color photographic materials containing an internal latent image type silver halide emulsion layer which have not been previously fogged are generally subjected to imagewise exposure followed by fog exposure and / or prior to development or during the development process.
Alternatively, in the presence of a nucleating agent, development, bleaching / fixing treatment is performed with a surface color developing solution containing an aromatic primary amine color developing agent.

(Problems to be Solved by the Invention) In recent years, there has been a strong demand in the industry for faster processing, that is, shorter processing time. In particular, the bleaching / fixing processing time, which occupies nearly half of the processing time, is Shortening (shortening of desilvering process) has become a major issue.

However, if the bleaching / fixing processing time is shortened, desilvering becomes insufficient, so that there arises a problem that the amount of residual silver increases and the color reproducibility deteriorates.

In order to reduce the residual silver amount due to the shortening of the desilvering process, it is conceivable to reduce the coating silver amount in the light-sensitive material.
When the amount of coated silver is reduced, a new problem arises that the maximum density of the obtained image is lowered. The direct positive type emulsion as described above has a lower developing rate (ratio of developed silver to coated silver amount) than the negative type emulsion, and therefore it is particularly difficult to reduce the coated silver amount.

Further, in a silver halide photographic light-sensitive material using such an internal latent image type silver halide emulsion, a yellow colloidal silver-containing layer is usually used as a yellow filter layer in order to improve color reproducibility. This colloidal silver can also leave unnecessary silver in the image, but if the amount of the colloidal silver is reduced, color mixing occurs, which causes problems such as deterioration of color reproducibility, which is not preferable. Therefore, the presence of the colloidal silver-containing layer in the direct positive type light-sensitive material makes it more difficult to shorten the bleaching / fixing processing time.

In addition, if a surface color developer is used for a long time, tar-like substances float in the developer due to air oxidation, so if the photosensitive material being processed is contaminated or if an automatic processor is used, automatic development is performed. There was a problem of contaminating the rollers of the machine.

The present invention solves the above-mentioned problems that occur when a direct positive type color light-sensitive material using an internal latent image type emulsion which has not been fogged in advance is developed.

Therefore, an object of the present invention is to provide a direct positive color image forming method capable of rapidly obtaining an image having good color reproducibility and excellent maximum density.

A further object of the present invention is to provide a direct positive color image forming method in which the generation of tar-like substances generated when a developer is used is suppressed.

(Means for Solving the Problems) The above object of the present invention is to provide a photosensitive material containing on a support at least one pre-fogged internal latent image type silver halide emulsion layer and a color image forming coupler. After imagewise exposure of the material, it is developed, bleached and fixed with a surface color developing solution containing an aromatic primary amine color developing agent in the presence of fog exposure and / or in the presence of a nucleating agent prior to development or during the development process. In the method of processing directly to form a positive color image, said color image-forming coupler is a compound which is substantially non-diffusible and which produces or releases a dye upon oxidative coupling with said developing agent. The material has a silver content of 1.0 g or less per 1 m ² of the light-sensitive material and has a layer containing colloidal silver, and the developer has a pH value of 11.5 or less and is represented by the following general formula (I). Compound Contain, be achieved by direct positive color image forming method, wherein the further development temperature is 33-43 ° C. and the development time is not more than 120 seconds.

General formula (I) (In the formula, R ¹ and R ² represent an alkyl group or an alkenyl group. Alternatively, R ¹ and R ² may be linked to form a hetero ring together with a nitrogen atom.) Surprisingly, the use of substituted hydroxylamine in place of hydroxylamine, which is usually contained as a preservative, suppresses the generation of tar-like substances generated in the developing solution over time, and the light-sensitive material is 1.0 g. It has been found that a direct positive color image having a sufficiently high maximum density can be obtained in a short bleaching / fixing processing time despite the unprecedented low coating amount of / m ² or less.

Furthermore, according to the present invention, a positive color image can be directly formed by a rapid bleaching / fixing process even though the light-sensitive material has a layer containing colloidal silver.

The light-sensitive material of the present invention contains 1.0 g or less, preferably 0.50 to 0.95 g of silver per 1 m ^{2 of} light-sensitive material. When the number of silver halide emulsion layers is two or more, the content of silver means the total amount thereof, and is further understood to include the amount of silver in the colloidal silver-containing layer.

Examples of the colloidal silver-containing layer contained in the light-sensitive material used in the present invention include a yellow filter layer containing a yellow colloid layer widely used in this field, but other layers such as gray colloidal silver are used. It also includes an intermediate layer to be contained and a colloidal silver-containing layer for improving graininess.

Colloidal silver used in the present invention is yellow, brown,
Any of blue, black and the like may be used.

Preferably, the colloidal silver-containing layer uses a yellow colloidal silver-containing layer below the blue-sensitive layer in the exposure direction. The yellow filter layer is usually provided in at least one of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer. The amount of colloidal silver added is preferably 0.0001 to 0.4 g / m ² , more preferably 0.000.
It is 3 to 0.3 g / m ² .

The preparation of various types of colloidal silver is described, for example, by Wiley & Son.
s, New York, 1933, Weiser's Colloidal Elements
(Yellow colloidal silver by the Carey Lea dextrin reduction method) or DE 1096193 (brown and black colloidal silver) or US Pat. No. 2688601 (blue colloidal silver).

The compound of the general formula (I) used in the present invention will be described in detail.

General formula (I) (Wherein, R ^1, R ² represents an unsubstituted or substituted alkyl group or an unsubstituted or substituted alkenyl group. Alternatively, R ¹
And R ² may be linked together to form a heterocycle together with the nitrogen atom. As the dialkylhydroxylamine used in the present invention, in the general formula (I), R ¹ and R ² preferably have 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. Examples of the nitrogen-containing heterocycle formed by linking R ¹ and R ² include a piperidyl group, a pyrrolidylyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group and a benztriazolyl group.

Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

These compounds can be used alone or in combination of two or more. Among the above compounds, in the present invention (1)
It is particularly preferable to use (2), (5) and (6). The compound represented by the general formula (I) can be synthesized by the following known method, for example, US Pat. Nos. 3,661,996 and 3,362,961.
No. 3,293,034, JP-B-42-2794, U.S. Pat.
No. 491, 151, No. 3,655,764, No. 3,467,711, No.
It can be synthesized by methods such as 3,455,916, 3,287,125, and 3,287,124.

In the present invention, the dialkylhydroxyamine represented by the general formula (I) is preferably contained in the developer in an amount of 0.05 to 20 g / l, preferably 0.5 to 10 g / l.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and representative examples thereof are shown below, but the invention is not limited thereto.

(D-1) N, N-diethyl-p-phenylenediamine (D-2) 2-amino-5-diethylaminotoluene (D-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene (D-4) 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline (D-5) 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline (D-6) N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline (D-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide ( D-8) N, N-Dimethyl-p-phenylenediamine (D-9) 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline (D-10) 4-Amino-3-methyl-N -Ethyl-N-β
-Ethoxyethylaniline (D-11) 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among these exemplified compounds, (D-5) and (D-6) have a sufficiently high maximum concentration and a low minimum concentration, and desilvering is also good, and thus they can be preferably used.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is about 0.1 g to about 20 g, and more preferably about 0.5 g to about 10 g per developing solution.

The developer of the present invention may be used in combination with one kind or a mixture of two or more kinds of conventionally used alkanolamines. Examples of such alkanolamines include those represented by the general formula (II).

General formula (II) (In the formula, R ₃ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₄
And R ₅ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula Where n is an integer of 1 to 6, X and Z are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Specifically, ethanolamine, diethanolamine, triethanolamine, di-isopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, benzyl. It is not limited to ethanolamine, isopropylaminoethanol and the like.

The alkanolamines may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid.

These alkanolamines are preferable because they improve preservative performance, and it is preferable to use 0.01 g to 20 g, preferably 0.1 g to 10 g, and more preferably 1 g to 8 g per 1 color developing solution.

Further, one kind or two or more kinds of condensed ring amines can be used in combination.

 The following compounds are preferable as the condensed ring amines.

General formula (III) In the formula, X represents a trivalent atom group necessary for completing the condensed ring, and R ⁶ and R ⁷ represent an alkylene group, an arylene group, an alkenylene group or an aralkylene group.

Here, R ⁶ and R ⁷ may be the same or different.

Of the general formula (III), the particularly preferred one is the general formula (I
II-a) and (III-b).

In the formula, X ¹ represents N or CH. R ⁶ and R ⁷ are represented by the general formula (I
II) as defined above, R ⁸ is a group similar to R ⁶ , R ⁷ , or Represents

In the general formula (III-a), X ¹ is preferably N. The carbon number of R ⁶ , R ⁷ and R ⁸ is preferably 6 or less,
The case of 3 or less is more preferable, and the case of 2 is most preferable.

R ⁶ , R ⁷ and R ⁸ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ⁶ and R ⁷ are defined as in the general formula (III).

In the general formula (III-b), it is preferable that R ⁶ and R ⁷ have 6 or less carbon atoms. R ⁶ and R ⁷ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds represented by formulas (III-a) and (III-b), the compound represented by formula (III-a) is particularly preferable.

 Specific examples of the compound represented by the formula (III) are shown below.

Many compounds of general formula (III) can be easily obtained as commercial products.

It is preferable to contain a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, and potassium metasulfite, and a carbonyl sulfite adduct. The addition amount of these is 0 g to 20
g / l is preferably from 0 g to 5 g / l, and a smaller amount is preferable as long as the stability of the color developing solution is maintained.

Among these, especially by adding a compound that generates sulfite ion and / or bisulfite ion, the homeostasis is improved,
It is possible to effectively suppress coloring of the color developing solution with time.
Therefore, it is particularly preferable that SO ₃ ²⁻ is added so as to be in the range of 2.5 × 10 ^{−3 to} 2.5 × 10 ⁻² mol / l, and more preferably,
2.5 × 10 ^{-3 to} 1.25 × 10 ^-2 mol / l is good.

Other preservatives include JP-A Nos. 52-49828 and 56-470.
38, 56-32140, 59-160142 and U.S. Patent 37465.
Aromatic polyhydroxy compound described in US Pat. No. 3615
503 and hydroxyacetones described in British Patent 1306176, α-aminocarbonyl compounds described in JP-A-52-143020 and 53-89425, JP-A-57-44148 and 57-537.
Various metals described in No. 49, various saccharides described in JP-A No. 52-102727, hydroxamic acids described in No. 52-27638, 59
-160141, α, α'-dicarbonyl compounds, 59-
Examples thereof include salicylic acids described in No. 180588, alkanolamines described in No. 54-3532, poly (alkyleneimines) described in No. 56-94349, and gluconic acid derivatives described in No. 56-75647. Two or more kinds of these preservatives may be used in combination, if necessary.

The pH of the color developing solution is preferably pH 9 to 11.5, more preferably 9 to 11.0, and various buffer agents are preferably used to maintain the pH.

As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N, N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy salt Phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-
Propanediol salt, valine salt, proline salt, trishydrocyaminomethane salt, lysine salt and the like can be used. Particularly, carbonate, phosphate, tetraborate, and hydroxybenzoate are excellent in solubility and buffer capacity in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they are effective for photographic performance. It is particularly preferable to use these buffers, since they have the advantages of being free from adverse effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate,
Potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), tetraborate Potassium acid, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

Various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

As the chelating agent, organic acid compounds are preferable, for example, aminopolycarboxylic acids described in JP-B-48-30496 and 44-30232, JP-A-56-97347, JP-B-56-39359, and West German Patent 2227639. Organic phosphonic acids, JP-A-52-
102726, 53-42730, 54-121127, 55-126241
No. and 55-65956 and the like phosphonocarboxylic acids,
Others JP-A-58-195845, JP-A-58-203440 and JP-B-53
-40900 and the like can be mentioned. Specific examples are shown below, but the present invention is not limited thereto.

・ Nitrilotriacetic acid ・ Diethylenetriamine pentaacetic acid ・ Triethylenetetramine hexaacetic acid ・ Cyclohexyldiamine tetraacetic acid ・ N, N, N-trimethylenephosphonic acid ・ Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid ・ 1, 3-Diamino-2-propanol-4acetic acid-Transcyclohexanediaminetetraacetic acid-Nitriropipropionic acid-1,2-Diaminopropanetetraacetic acid-Hydroxyethyliminodiacetic acid-Glycol etherdiaminetetraacetic acid-Hydroxyethylenediaminetriacetic acid-Ethylenediamineortho Hydroxyphenylacetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethylidene-1,1-diphosphonic acid ethylenediaminetetraacetic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N ′ -Diacetic acid Agent may be used in combination of two or more if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g per unit.

Any development accelerator can be added to the color developing solution if necessary. Specifically, Japanese Patent Publication No. 37-16088, 37-5987,
Thioether compounds represented by U.S. Pat. Nos. 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247, and p-represented in JP-A-52-49829 and 50-15554. Phenylenediamine compounds, JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429,
And the like, quaternary ammonium salts, US Pat. No. 2610
122 and 4119462, p-aminophenols, U.S. Pat. Nos. 2,494,903, 3,128,182, 423,079.
6, No. 3253919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 24
No. 82546, No. 2596926 and No. 3582346, amine compounds described in JP-B-37-16088, JP-B-42-25201, U.S. Pat.No. 3128183, JP-B-41-11431, 42-23883 No. and U.S. Pat. No. 3,352,501, and other polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary. .

In the present invention, an optional antifoggant can be added to the color developer as required. As antifoggants, alkali metal halides such as potassium bromide, sodium chloride and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Of nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole and hydroxyazaindolidine and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzthiazole, and further of thiosalicylic acid Such mercapto-substituted aromatic compounds can be used. Particularly preferred are nitrogen-containing heterocyclic compounds.
These antifoggants may elute from the color photographic material during processing and accumulate in the color developer.

The color developer of the present invention preferably contains a fluorescent whitening agent. As a fluorescent whitening agent, 4,4'-diamino-
2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 5 g / l, preferably 0.1 g to 2 g / l.

If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The color developing solution of the present invention is used at a processing temperature of 33 to 43 ° C., and the developing time is within 120 seconds. 20 seconds or more,
It is preferable that the time is 30 seconds or more. The replenishment amount is preferably small, but is 20 to 600 ml, preferably 50 to 300 ml per 1 m ^{2 of} the light-sensitive material. More preferably, the amount is 100 to 200 ml.

In a preferred embodiment of the direct positive light-sensitive material of the present invention, at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer are provided on a support. The order of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red-sensitive, green-sensitive, blue-sensitive from the support side or green-sensitive, red-sensitive and blue-sensitive from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. To directly form a positive color image, a non-diffusing cyan type coupler is used in the red-sensitive emulsion layer and a non-diffusing magenta forming coupler is used in the green-sensitive emulsion layer.
It is usual to include a non-diffusible yellow-forming coupler in each of the blue-sensitive emulsion layers, although different combinations may be used in some cases. Regarding the non-diffusible cyan, magenta and yellow couplers, for example, Japanese Patent Application No. 61-286.
Those described in No. 367, page 48, line 14 to page 57 can be used.

The internal latent image type silver halide used in the present invention is particularly preferably silver chlorobromide and silver bromide which are substantially free of silver iodide.
"Substantially free of silver iodide" means that the silver iodide content is 0 to 1
Mol%, preferably 0 to 0.5 mol%.
More preferred are silver chlorobromide and silver bromide containing no silver iodide.

The internal latent image type emulsion which can be used in the present invention is 1986.
Japanese Patent Application No. 61-253716 filed on Oct. 27 (Applicant Fuji Photo Film Co., Ltd.), page 28, line 14 to page 31, line 2
In line with the silver halide grains that can be used in the present invention,
See page 31, line 3 to page 32, line 11 of the same specification, for details of the color couplers usable in the present invention, see page 33, line 18 to 40 of the same specification.
It is described at the end of each page.

The internal latent image type emulsion may be a conversion type emulsion or a core / shell type emulsion, but a core / shell type emulsion is preferred. When a core / shell type emulsion is used, the silver chloride content in the silver chlorobromide grains may be higher in the core or higher in the shell, but the silver chloride content in the shell is higher or the halogen composition of the core and the shell is the same. Is preferred.

In the present invention, after imagewise exposure using a light-sensitive material, after performing a fogging treatment with light or a nucleating agent, or while performing, surface development of pH 11.5 or less containing an aromatic primary amine color developing agent. A positive color image is directly formed by color development, bleaching and fixing with a liquid. The pH of this developer is 11.0-
More preferably, it is in the range of 10.0.

The fogging treatment in the present invention includes a so-called "light fogging method" for giving a second exposure to the entire surface of the photosensitive layer and a "chemical fogging method" for developing in the presence of a nucleating agent. Either may be used. You may develop in the presence of a nucleating agent and fog light. Further, a light-sensitive material containing a nucleating agent may be fog-exposed.

The light fogging method is described on page 47, line 4 to page 49, line 5 of the aforementioned Japanese Patent Application No. 61-253716. Regarding the nucleating agent usable in the present invention, the same specification, p. 49, line 6 to p. 67, 2
The use of compounds represented by the formulas [N-1] and [N-2] is particularly preferable.

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

(NI-1) 5-Ethoxy-2-methyl-1-propargylquinolinium bromide (NI-2) 2,4-Dimethyl-1-propargylquinolinium bromide (NI-3) 2-Methyl-1- {3- [2- (4-Methylphenyl) hydrazono] butyl} quinolinium iodide (NI-4) 3,4-dimethyl-dihydropyrido [2,1-b]
Benzothiazolium bromide (NI-5) 6-ethoxythiocarbonylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-6) 2-methyl-6- (3-phenylthioureido)- 1-propargylquinolinium bromide (NI-7) 6- (5-benzotriazolecarboxamide) -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-8) 6- [3- (2-mercapto Ethyl) ureido] -2-methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-9) 6- {3- [3- (5-mercapto-thiadiazol-2-ylthio) propyl] ureido} -2-
Methyl-1-propargylquinolinium trifluoromethanesulfonate (NI-10) 6- (5-mercaptotetrazol-1-yl) -2-methyl-1-propargylquinolinium iodide (NI-11) 1-propargyl- 2- (1-propenyl)
Quinolinium trifluoromethanesulfonate (NI-12) 6-ethoxythiocarbonylamino-2-
(2-Methyl-1-propenyl) -1-propargylquinolinium trifluoromethanesulfonate (NI-13) 10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate (NI-14) 7-ethoxythiocarbonylamino-10-propargyl-1,2,3,4-tetrahydroacridinium
Trifluoromethanesulfonate (NI-15) 6-ethoxythiocarbonylamino-1-propargyl-2,3-pentamethylethylenequinolinium trifluoromethanesulfonate (NI-16) 7- [3- (5-mercaptotetrazole-
1-yl) benzamide] -10-propargyl-1,2,3,
4-Tetrahydroacridinium perchlorate (NI-17) 6- [3- (5-mercaptotetrazole-
1-yl) benzamido] -1-propargyl-2,3-
Pentamethylenequinolinium bromide (NI-18) 7- (5-mercaptotetrazol-1-yl) -9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium bromide (NI-19) 7- [3- {N- [2- (5-mercapto 1,
3,4-Thiadizol-2-yl) ethyl] carbamoyl} propanamide] -10-propargyl-1,2,3,4-
Tetrahydroacridinium imide (NI-20) 6- (5-mercaptotetrazol-1-yl) -4-methyl-1-propargyl-2,3-pentamethylenequinolinium bromide General formula (N-II) Specific examples of the compound are shown below.

(N-II-1) 1-formyl-2- {4- [3- (2-methoxyphenyl) ureido] -phenyl} hydrazine (N-II-2) 1-formyl-2- {4- [3- {3- [3
-(2,4-di-tert-bentylphenoxy) propyl]
Ureido} phenylsumaphonylamino] phenyl} hydrazine (N-II-3) 1-formyl-2- {4- [3- (5-mercaptotetrazol-1-yl) benzamido] phenyl} hydrazine (N-II-4 ) 1-formyl-2- {4- [3- {3- [3
-(5-Mercaptotetrazol-1-yl)] phenyl] ureido} phenyl] hydrazine (N-II-5) 1-formyl-2- [4- {3- [N- (5
-Mercapto-4-methyl-1,2,4-triazole-3
-Yl) carbamoyl) propanamide} phenyl] hydrazine (N-II-6) 1-formyl-2- {4- [3- {N- [4
-(3-Mercapto-1,2,4-triazol-4-yl) phenyl] carbamoyl} propanamide} phenyl] hydrazine (N-II-7) 1-formyl-2- [4- {3- [N- (5
-Mercapto-1,3,4-thiadiazol-2-yl) carbamoyl] propanamide} phenyl] -hydrazine (N-II-8) 2 [4-benzotriazole-5-carboxamido) phenyl] -1-formylhydrazine ( N-II-9) 2- [4- {3- (N- (benzotriazole-5-carboxamido) carbamoyl] propanamide} phenyl] -1-formylhydrazine (N-II-10) 1-formyl-2- {4- [1- [N-phenylcarbamoyl) thiosemicarbamido] phenyl]
Hydrazine (N-II-11) 1-formyl-2- {4- [3- [3-phenylthioureido) benzamido] phenyl] -hydrazine (N-II-12) 1-formyl-2- [4- ( 3-hexylureido) phenyl] hydrazine (N-II-13) 1-formyl-2- {4- [3- (5-mercaptotetrazol-1-yl) benzenesulfonamide] phenyl} hydrazine (N-II-14 ) 1-formyl-2- {4- [3- {3-
[3- (5-Mercaptotetrazol-1-yl) phenyl] -ureido} benzenesulfonamide] phenyl} hydrazine Regarding the nucleation accelerator that can be used in the present invention, Japanese Patent Application No. 61-2 is available.
No. 86367, page 68, line 11 to page 71, line 3, and a specific example of this is described on pages 69 to 70 (A-
The use of 1) to (A-13) is preferable.

The photographic emulsion layer of the color developing solution is usually bleached. The bleaching / fixing treatment applied to the present invention is meant to include not only a mode in which the bleaching process and the fixing process are simultaneously carried out by one-bath bleach-fixing, but also a mode in which both processes are carried out separately. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after bleaching processing or a method of performing bleach-fixing processing after fixing processing may be used. Aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in a bleaching solution or a bleach-fixing solution.
As the additives used in the bleaching solution or the bleach-fixing solution, various compounds described on pages 22 to 30 of Japanese Patent Application No. 61-32462 can be used. After the desilvering process (bleach-fixing or fixing), a treatment such as washing with water and / or stabilization is performed. It is preferable to use softened water as the washing water or the stabilizing solution. As a method of water softening,
Examples thereof include a method using an ion exchange resin or a reverse osmosis device described in Japanese Patent Application No. 61-131632. As a concrete method of these, it is preferable to carry out the method described in Japanese Patent Application No. 61-131632.

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

It is preferable that the amount of replenisher in each processing step is small.
The amount of the replenisher is preferably 0.1 to 50 times, more preferably 3 to 3 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.
It is 0 times.

(Example) Hereinafter, the present invention will be illustrated by examples.

Example 1 Preparation of Emulsion C-1 0.3 g of an aqueous solution of potassium bromide and silver nitrate was added per mol of Ag.
Approximately 20 ° C at 75 ° C with vigorous stirring in an aqueous gelatin solution containing 3,4-dimethyl-1,3-thiazoline-2-thione.
The addition was carried out at the same time, to obtain a monodisperse silver bromide emulsion having an average grain size of 0.40 μm octahedron. 6m per mole of silver in this emulsion
Chemical sensitization was performed by adding g of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) and heating at 75 ° C. for 80 minutes. The silver bromide grains thus obtained were used as cores for further growth in the same precipitation environment as the first time, and finally the average grain size was about
A 0.7 μm octahedral monodisperse core / shell silver bromide emulsion was obtained. The coefficient of variation of particle size was about 10%.

To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver were added, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization treatment, and internal latent image type halogenated emulsion C was used. -
Got one.

A multilayer color light-sensitive material 101 having the following layer structure was prepared on a paper support laminated on both sides with polyethylene.

The composition of each layer is shown below. The numbers represent the coating amount per m ² in g. The silver halide emulsion and colloidal silver are expressed in terms of silver, and the spectral sensitizing dye is expressed in terms of mol per mol of silver halide.

Support Polyethylene laminated paper [Polyethylene on the E1 layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] E1 layer Silver halide emulsion (C-1) 0.23 Spectral sensitizing dye (ExSS-1 ) 1.0 × 10 ^-4 Spectral sensitizing dye (ExSS-2) 6.1 × 10 ^-5 Gelatin 0.90 Cyan coupler (ExCC-1) 0.19 Cyan coupler (ExCC-2) 0.24 Ultraviolet absorber (ExUV-1) 0.17 Solvent (ExS -1) 0.21 Development control agent (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nucleation accelerator (ExZS-1) 3.0 × 10 ^-4 Nucleation agent (ExZK-1) 8.0 × 10 ^-6 E2 Layer Gelatin 1.41 Anti-color mixing agent (ExKB-1) 0.09 Solvent (ExS-1) 0.10 Solvent (ExS-2) 0.10 E3 layer Silver halide emulsion (C-1) 0.21 Spectral sensitizing dye (ExSS-3) 3.0 × 10 ^-4 Gelatin 0.90 Magenta coupler (ExMC-1) 0.14 Color image stabilizer (ExSA-1) 0.18 Solvent (ExS-3) 0.22 Development modifier (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nucleation acceleration Agent (ExZS-1) 2.7 × 10 ^-4 Nucleating agent (ExZK-1) 1.4 × 10 ^-5 Layer E4 Gelatin 0.47 Anti-color mixing agent (ExKB-1) 0.03 Solvent (ExS-1) 0.03 Solvent (ExS-2) 0.03 Layer E5 Colloidal silver 0.09 Gelatin 0.49 Anti-color mixing agent (ExKB-1) 0.03 Solvent ( ExS-1) 0.03 Solvent (ExS-2) 0.03 E6 layer Same as E4 layer E7 silver halide emulsion (C-1) 0.36 Spectral sensitizing dye (ExSS-4) 1.2 × 10 ^-4 gelatin 1.90 Yellow Coupler (ExYC-1) 0.46 Solvent (ExS-2) 0.18 Solvent (ExS-4) 0.18 Development regulator (ExGC-1) 0.06 Stabilizer (ExA-1) 0.001 Nucleation accelerator (ExZS-1) 5.0 × 10 ^-4 Nucleating agent (ExZK-1) 1.2 × 10 ^-6 E8 layer gelatin 0.54 UV absorber (ExUV-2) 0.21 Solvent (ExS-4) 0.08 E9 layer gelatin 1.28 Acrylic modified copolymer of polyvinyl alcohol ( Degree of modification 17%) 0.17 Liquid paraffin 0.03 Latex particles of polymethylmethacrylate (average particle size 2.8 μm) 0.05 Layer B1 gelatin 8.70 Layer B2 Same as layer E9 In addition to the above composition A gelatin hardener ExGK-1 and a surfactant were added.

Compound used to make the sample (ExUV-2) UV absorber 2: 9: 8 mixture of (1) :( 2) :( 3) above (weight ratio) (ExA-1) Stabilizer 4-Hydroxy-5,6-trimethylene-1,3,3a, 7-tetrazaindene (ExZS-1) Nucleation accelerator 2- (3-Dimethylaminopropylthio) -5- Mercapto-1,3,4-thiadiazole hydrochloride (ExZK-1) nucleating agent 6-ethoxythiocarbonylamino-2-methyl-1
-Propargyl quinolinium trifluoromethane sulfonate (ExGK-1) gelatin hardening agent 1-oxy-3,5-dichloro-S-triazine sodium salt Direct positive type silver halide color photographic light-sensitive material 101 ( Total silver amount 0.89g / m ² ) and photosensitive material 101
A light-sensitive material 102 (total silver amount 1.2%) prepared by increasing the coating silver amount of each silver halide emulsion (C-1) in the E1, E3 and E7 layers by 40%
1 g / m ² ) was exposed imagewise and 50 m ² continuous treatment was carried out by the following treatment A. The same light-sensitive material which was wedge-exposed with 250 CMS was processed at the start and end of the process, and the density was measured and the amount of silver in the Dmax part was measured by fluorescent X-ray.

The replenishment method of the washing bath was a so-called countercurrent replenishment method in which the washing bath was replenished, the overflow solution of the washing bath was introduced into the washing bath, and the overflow solution of the washing bath was introduced into the washing bath.

[Washing solution] Mother liquor and replenisher common tap water mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400) Water was passed through the floor column to reduce the concentration of calcium and magnesium ions to 3 mg / l or less.

 The pH of this solution is in the range 6.5-7.5.

 Table 1 shows the results.

Example 2 In Example 1, 200 ml of 5 kinds of color developing solutions after continuous processing in Nos. 1 to 5 were put in a 500 ml beaker and the mixture was heated at 35 ° C. for 10 minutes.
Leave for days. This liquid was filtered using filter paper to compare the coloring and the generation of tar.

Generation of tar in the color developing solution using the compound of the present invention is small, which is superior to the comparative examples.

Example 3 A photographic material 103 (total silver amount: 0.89 g / m ² ) was prepared in the same manner as the photographic material 101 except that the following emulsion C-2 was used in place of the emulsion C-1. did. The photosensitive material 103
Was exposed to light in the same manner as in Example-1 and was continuously treated with 50 m ^{2 of the} following treatment B.

Preparation of Emulsion C-2 A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were added at 0.07 g of 3,4-dimethyl-1,3-
Mono-dispersed salty odor with an average particle size of about 0.23 μm (silver bromide content 80 mol%), which was added simultaneously to an aqueous gelatin solution containing thiazoline-2-thione with vigorous stirring at 65 ° C for about 14 minutes. A silver halide emulsion was obtained. 61 mg per mole of silver in this emulsion
Chemical sensitization treatment was carried out by adding sodium thiosulfate of 4 and 42 mg of chloroauric acid (tetrahydrate) and heating at 65 ° C. for 60 minutes. The silver chlorobromide grains thus obtained were used as cores for further growth in the same precipitation environment as the first time, and finally a monodisperse core / shell having an average grain size of about 0.65 μm (silver bromide content 70 mol%). A silver chlorobromide emulsion was obtained. Coefficient of variation of particle size is about 12
%Met. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was mixed at 60 ° C for 6 hours.
A chemical sensitization treatment was performed by heating for 0 minutes to obtain an internal latent image type halogenated emulsion C-2.

The stabilizing bath was replenished into the stabilizing bath, the overflow liquid of the stabilizing bath was introduced into the stabilizing bath, and the overflow liquid of the stabilizing bath was introduced into the stabilizing bath, that is, a so-called countercurrent replenishing system.

The pH is adjusted with potassium hydroxide or hydrochloric acid.

 The results are shown in Table 3.

Example 4 In Example 1, the light-sensitive material 101 was used, and the color developing agents shown in Table 4 were used.

The color developing agents (D-5) and (D-6) were preferable because they had less residual silver amount than (D-1), (D-2) and (D-9).

Example 5 In Example 3, 5 kinds of color developing solutions after continuous processing in Nos. 11 to 15 were placed in a 500 ml beaker (200 ml) at 35 ° C. for 10 minutes.
Left for days. This liquid was filtered using a filter paper to compare the coloring with the generation of tar.

It can be seen that the treatment liquid of the present invention is preferable.

(Effects of the Invention) According to the present invention, a direct positive color image having good color reproducibility and excellent maximum density can be rapidly obtained.

Furthermore, it is possible to effectively suppress the generation of tar-like substances that occur when the developer is used over time.

 ─────────────────────────────────────────────────── --- Continuation of the front page (56) Reference JP-A-57-86829 (JP, A) JP-A-58-55928 (JP, A) JP-A-59-216136 (JP, A) JP-A-54- 3532 (JP, A) JP-A-57-185434 (JP, A) JP-A-56-94349 (JP, A) JP-A-63-43142 (JP, A) JP-A-63-32548 (JP, A) JP-A-63-5341 (JP, A) JP-A-63-74056 (JP, A)

Claims (1)

(57) [Claims] 1. A light-sensitive material containing at least one pre-fogged internal latent image type silver halide emulsion layer and a color image-forming coupler on a support after imagewise exposure, prior to or before development. In the method of forming a positive color image directly by developing, bleaching and fixing treatment with a surface color developing solution containing an aromatic primary amine color developing agent in the presence of fog exposure and / or nucleating agent during the step, The color image-forming coupler is a compound which is substantially non-diffusible and produces or releases a dye by oxidative coupling with the developing agent, and the light-sensitive material has a silver content of 1.0 g or less per 1 m ² . And a layer containing colloidal silver, wherein the developer has a pH value of 11.5 or less and the following general formula (I)
And a developing temperature of 33 to 43 ° C. and a developing time of 120 seconds or less. General formula (I) (In the formula, R ¹ and R ² represent an alkyl group or an alkenyl group. Alternatively, R ¹ and R ² may be linked together to form a hetero ring together with the nitrogen atom.)