JPS63261360A - Method for forming direct positive color picture image - Google Patents

Abstract

PURPOSE:To improve color reproducibility and density of a photosensitive material by forming a layer contg. <=1.0g silver per 1m<2> photosensitive material contg. also colloidal silver on the photosensitive material, and incorporating a specified compd. after adjusting the pH of a developing liquid to <=11.5. CONSTITUTION:A compd. which is substantially nondiffusive and forms or liberates a dye by the oxidation coupling with a developing agent is used as a color picture image forming coupler. Also, a layer contg. <=1.0g Ag per 1m<2> photosensitive material and contg. colloidal silver is formed on the photosensitive material. Moreover, a compd. having <=11.5 pH and being expressed by formula I is incorporated into a developing liquid. In formula I, each R<1> and R<2> is an alkyl or alkenyl group, or R<1> and R<2> may be bonded to each other forming a heterocyclic ring together with N atom. By this constitution, formation of tar materials derived from aged developing liquid is retarded, moreover, a direct positive color picture image having sufficiently high maximum density is obtd. in a short bleach-fix treating time even if the amt. of coated Ag of the photosensitive material is so low as <=1.0g/m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for forming direct positive color images using internal latent image type silver halide emulsions.

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

Various techniques are known to date for directly forming positive images using internal latent image type silver halide emulsions; for example, U.S. Pat. No. 2,592,250;
No. 466.957, No. 2゜497.875, No. 2
, No. 588,982, No. 3,317,322, No. 3. 761. No. 266, No. 3,761.276, No. 3,796.577 and British Patent No. 1. 1
51. No. 363, No. 1,150.553 (No. 1,
No. 011.062), and those described in each specification etc. are the main ones.

Direct positive color light-sensitive materials containing an internal latent image type silver halide emulsion layer that has not been fogged in advance are generally subjected to aromatic exposure after imagewise exposure, prior to or during the development process, during fogging exposure and/or in the presence of a nucleating agent. It is developed, bleached, and fixed using a surface color developer containing a group primary amine color developer.

(Problems to be Solved by the Invention) In recent years, there has been a strong demand in the industry for speeding up processing, that is, shortening the time required for processing. Shortening (shortening the desilvering process) is a major issue.

However, if the bleaching/fixing treatment time is shortened, desilvering becomes insufficient, resulting in an increase in the amount of residual silver and a problem in that color reproducibility deteriorates.

In order to reduce the amount of residual silver due to the shortening of the desilvering process, it is possible to reduce the amount of silver coated in the photosensitive material, but it is said that reducing the amount of silver coated reduces the maximum density of the image obtained. A new problem arises. Direct positive emulsions such as those described above have a lower development rate (ratio of developed silver to coated silver amount) than negative emulsions, and therefore it is particularly difficult to reduce the coated silver amount.

Further, in silver halide photographic materials using such internal latent image type silver halide emulsions, for example, 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 marks on the image, but reducing the amount of colloidal silver causes problems such as color mixing and deterioration of color reproducibility, which is not preferable. Therefore, the presence of the colloidal silver-containing layer in direct positive-working light-sensitive materials makes it even more difficult to shorten the bleaching and fixing processing times mentioned above.

In addition, if a surface color developing solution is used for a long time, tar-like substances will float in the developing solution due to air oxidation, which may contaminate the photosensitive material being processed, or if an automatic developing machine is used. There was a problem that the rollers of the machine could be contaminated.

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

Accordingly, it is an object of the present invention to provide a direct positive color image forming method capable of rapidly obtaining images 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 formation 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 at least one unfogged internal latent image type silver halide emulsion layer and a color image forming coupler on a support. After imagewise exposure of the photosensitive material, prior to or during the development process, fog exposure and/or in the presence of a nucleating agent, the photosensitive material is developed and bleached with a surface color developer containing an aromatic primary amine color developer. - in a method of forming a positive color image directly by fixing, the color image-forming coupler is a compound that is substantially non-diffusible and generates or releases a dye upon oxidative coupling with the developer; The photosensitive material is photosensitive material 1
The amount of silver contained per M is 1.0 g or less and has a layer containing colloidal silver, and the developer has a pH value of 11.5 or less and contains a compound represented by the following general formula (1). This is achieved by a direct positive color image forming method characterized by:

General formula (1) %Formula% (In the formula, R1 and R2 represent an alkyl group or an alkenyl group. Alternatively, R' and R2 may be linked together to form a heterocycle with a nitrogen atom.) According to the present invention Surprisingly, by using substituted hydroxylamine in place of hydroxylamine, which is normally contained as a preservative in developing solutions, the formation of tar-like substances that occur in aged developing solutions was surprisingly suppressed, and the photosensitive It has been discovered that direct positive color images with sufficiently high maximum density can be obtained in short bleaching and fixing processing times even though the material has an unprecedentedly low coated silver amount of less than 1.0 g/Po. It was done.

Further, according to the present invention, even though the photosensitive material has a layer containing colloidal silver, a positive color image can be directly formed by rapid bleaching and fixing processing.

The photosensitive material of the present invention is 1.0 g or less per IM of the photosensitive material,
Preferably it contains 0.50-0.95 g of silver. This amount of silver contained means the total amount when there are two or more silver halide emulsion layers, and is also understood to include the amount of silver in the colloidal silver-containing layer.

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

The colloidal silver used in the present invention may be yellow, brown, blue, black, or the like.

Preferably, the colloidal silver-containing layer is a yellow colloidal silver-containing layer below the blue-sensitive layer in the exposure direction.

A yellow filter layer is usually provided between 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 010001 to 0.4 g/bo, more preferably o, oo.

It is 3 to 0.3 g/bo.

The preparation of various types of colloidal silver is e.g.
5ons+ New York+ Published 1933, W
Co11oidal Element by eiser
ts (yellow colloidal silver by Carey Lea's dextrin reduction method) or German Patent No. 1096193
(brown and black colloidal silver) or US Pat. No. 2,688,601 (blue colloidal silver).

The compound of general formula (1) used in the present invention will be explained in detail.

General formula (T) R'-N-R" CH (wherein R1 and R2 represent an unsubstituted or substituted alkyl group or an unsubstituted or substituted alkenyl group.

Alternatively, R1 and R2 may be linked together with the nitrogen atom to form a heterocycle. ) As the dialkylhydroxylamine used in the present invention,
In the general formula (I), the number of carbon atoms in R' and R'' is preferably 1 to 5, particularly preferably 1 to 3. In the nitrogen-containing heterocycle formed by connecting R' and R2, a piperidyl group , pyrrolysilyl group, N-alkylpiperazyl group, morpholyl group, indolinyl group, benztriazolyl group, and the like.

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

(I-1) CH ■ C,H,-N-C,H.

CH C,R7-N-C3Hr CH C,H,-N-C,H.

(I-4) CH ■ CH, -N-C,H.

CH CH30CzH4N Ct H40CH3(I-6
) CH CzHsOCzHa-N-Cz H,OC,H5OH CH:lOCz H40Cz H4N Cz H40
C2Ha OCH3OH C,H,0C2H,N-CzH5 OH CzHsOCZI(4NCHz CH=CHzOH CHy N CzH4CONHz N (I-15) OH CH3-N-C,H,SO□C2H,.

(I-17) OH C, H1SO□Cz H-N Cz H4S Oz
Cz H5 (I-18) Chang (+-22) These compounds can be used alone or in combination of two or more. Among the above compounds, in the present invention, (1) (2)
)(5)(6) are particularly preferably used. The compound represented by the general formula (1) can be synthesized by the following known methods, such as U.S. Pat. No. 3,661,996, U.S. Pat.
No. 362,961, No. 3,293,034, Japanese Patent Publication No. 42-2794, U.S. Patent No. 3,491,151,
Same No. 3,655,764, Same No. 3. 467, 71
No. 1, No. 3.455.9i6, No. 3,287.1
No. 25, No. 3,287. It can be synthesized by a method such as '124.

In the present invention, 0.05 to 20 g of dialkylhydroxyamine represented by the above general formula (1) is added to the developer solution.
2, preferably 0.5-10g/I! .

It is preferable to include it.

The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are P-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

(D-1) N,N-diethyl-p-phenylenediamine (D-2) 2-amino-5-diethylaminotoluene (D-3) 2-amino-5-(N-ethyl-N=nilaurylaminotoluene (D-4) 4-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline (D-5) 2-methyl-4-[N-ethyl-N-(
β-hydroxyethyl)aminocoaniline (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
) can be used preferably because it provides a sufficient maximum density and a low minimum density, and also has good desilvering properties.

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

In the developer of the present invention, one type or a mixture of two or more of conventionally used alkanolamines can be used in combination. Examples of such alkanolamines include those represented by general formula (n).

General formula (II) (wherein, R3 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R4 and R6 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxy group having 2 to 6 carbon atoms, where n is an integer of 1 to 6, and X and Z each represent a hydrogen atom or a hydroxyl group having 1 to 6 carbon atoms.
-6 alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms. ) Specifically, ethanolamine, jetanolamine,
triethanolamine, di-isopropanolamine,
2-methylaminoethanol, 2-ethylaminoethanol, dimethylaminoethanol, 2-diethylaminoethanol, ■-diethylamino-2-propanol,
Examples include, but are not limited to, benzylethanolamine and isopropylaminoethanol.

The above 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 the preservation performance, and are suitable for color developer II! , 0゜01g~
It is preferable to use 20 g, preferably 0.1 g to 10 g, more preferably 1 g to 8 g.

Furthermore, one type or two or more types of condensed cyclic amines can be used in combination.

As the condensed cyclic amines, the following are preferred.

In the general formula (II [) kR formula, X represents a trivalent atomic group necessary to complete the condensed ring, R6 and R7 are an alkylene group, an arylene group,
Represents an alkenylene group or an aralkylene group.

Here, Rh and R' may be the same or different.

Among general formulas (III), particularly preferred ones are general formulas (
These are compounds represented by I[[-a) and (I[r-b).

In the formula, xl represents >N or )CH. Rh, R7 are defined as in general formula (In), R8 is R6,
Represents a group similar to R' or -CH, C-.

In the general formula (I[-a), X" is preferably →N. The number of carbon atoms in R6, R7, and R8 is preferably 6 or less, more preferably 3 or less, and 2. The case is most preferred.

R6, R7, and R11 are preferably alkylene groups or arylene groups, and most preferably alkylene groups.

In the formula, R1, and R'7 are defined in the same manner as in the general formula (I[l).

In the general formula (I[[-b), Rh, R? The number of carbon atoms in is preferably 6 or less. R6, R? is preferably an alkylene group or an arylene group, most preferably an alkylene group.

Among the compounds represented by the general formulas ([-a) and (I[I-b), the compound represented by the general formula (III-a) is particularly preferred.

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

(II[-2) (III-3) (II[-4) (I[l-5) (III-6) (I[-7) (I[[-8) (III-9) O (I [l-10) (III-11) (I[l-12) (I[[-13) (III-15) (III-16) (III-17) (III-18) General formula ([[) Many of these compounds are easily available commercially.

It is preferable to contain sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts.

The amount of these added is Og ~ 20 g/l, preferably Og ~
5g/i! , and if the stability of the color developer is maintained, the smaller the number, the better.

Among these, addition of a compound that generates sulfite ions and/or bisulfite ions improves storage stability and effectively suppresses discoloration of the color developer over time. Therefore, especially so, "- is 2゜5X10-" ~ 2.5X1
It is best to add it in a range of 0-”mol/l,
More preferably, 2.5X10-' to 1.25XIO
-”Mole/2 is good.

Other preservatives include JP-A Nos. 52-49828, 56-47038, 56-32140, and 59-
Aromatic polyhydroxy compounds described in US Pat. No. 160142 and US Pat. No. 3,746,544; hydroxyacetones described in US Pat. No. 3,615,503 and British Patent No. 1,306,176;
α-aminocarbonyl compound described in No. 25, JP-A-57
Various metals described in JP-A-144148 and JP-A-57-53749, various saccharides as described in JP-A-52-102727, hydroxamic acids as described in JP-A-52-2-27638, α as described in JP-A-59-160141.

α'-dicarbonyl compounds, salicylic acids described in No. 59-180588, alkanolamines described in No. 54-3532, poly(alkyleneimines) described in No. 56-94349, glucones described in No. 56-75647. Examples include acid derivatives. Two or more of these preservatives may be used in combination, if necessary.

The pH of the color developer is preferably pH 9 to 11, 5
, more preferably 9 to 11.0, and the pH
In order to maintain this, it is preferable to use various buffering agents.

Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt, N,N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxy Phenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,
3-propanediol salt, valine salt, proline salt, trishydrodiaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are highly soluble and have a high pH of 9.0 or higher.
It is particularly preferable to use these buffering agents because they have excellent buffering ability in the IF range, have no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and are 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, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2=hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0. 1 mole/
I! , or more, particularly 0.1 mol/2
It is particularly preferable that the amount is 0.4 mol/2.

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

The chelating agent is preferably an organic acid compound, such as the aminopolycarboxylic acids described in Japanese Patent Publication No. 4B-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347, Japanese Patent Publication No. 56-39359, and West German Patent No. 222763.
Organic phosphonic acids described in No. 9, JP-A-52-10272
No. 6, No. 53-42730, No. 54121127,
Phosphonocarboxylic acids described in No. 55-126241 and No. 55-65956, etc., and other JP-A-58-19
No. 5845, No. 58-203440 and Special Publication No. 53-
Examples thereof include compounds described in No. 40900 and the like.

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

・Nitrilotriacetic acid・Diethylenetriaminepentaacetic acid・Triethylenetetraminehexaacetic acid・Cyclohexyldiaminetetraacetic acid・N, N, N-trimethylenephosphonic acid・Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid・1,3-diamino-2-propanol-tetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilopiprobionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylene diamine triacetic acid Acetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-)licarboxylic acid, J-hydroxyethylidene~1. 1-diphosphonic acid, ethylenediaminetetraacetic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid Two or more of these chelating agents may be used in combination as necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 12
It is about 0.1g to Log per unit.

Any development accelerator can be added to the color developer if necessary. Specifically, Special Publication No. 37-16088, No. 37-
5987, 38-7826, 44-12380
No. 45-9019 and U.S. Patent No. 3813247
Thioether compounds represented by No. 1, etc.,
p-phenylenediamine compounds shown in No. 49829 and No. 50-15554, JP-A-50-437
No. 726, Japanese Patent Publication No. 1973-30074, Japanese Patent Publication No. 1987-1
56826 and 52-43429, P-amine phenols described in U.S. Patent No. 2610122 and 4119462, U.S. Patent No. 2494903, 3128182
No. 4230796, No. 3253919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2482546
amine compounds described in Japanese Patent Publication No. 37-16088,
No. 42-25201, U.S. Patent No. 3128183,
Polyalkylene oxides shown in Japanese Patent Publications No. 41-11431, No. 42-23883, U.S. Patent No. 3532501, etc., 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

In the present invention, an arbitrary antifoggant can be added to the color developer, if necessary. As antifoggants, alkali metal halides such as potassium bromide, sodium chloride, potassium iodide, and organic antifoggants can be used.

Examples of organic antifoggants include henctriazole, 6-nidrohenzimidazole, 5-nitroisoindazole, 5-methylhencitriazole, 5-nitrohencitriazole, 5-chloropenzotriazole, 2-thiazolyl- Nitrogen-containing heterocyclic compounds such as benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and 1-phenyl-
Mercapto-substituted heterocyclic compounds such as 5-mercaptotetrazole, 2-mercaptobenzimidazole, 2-mercaptobenzthiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are nitrogen-containing heterocyclic compounds. These antifoggants may be eluted from the color photosensitive material during processing and may accumulate in the color developer.

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

Various surfactants such as alkylsulfonic acids, arylphosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The color developer of the present invention is preferably processed at a temperature of 30 to 50
It is preferably used at a temperature of 33 to 43°C rather than 1°C. The treatment is preferably carried out for 20 seconds to 2.5 minutes, preferably 30 seconds to 2 minutes. Furthermore, it is preferable that the development time be within 150 seconds, particularly within 120 seconds, from the viewpoint of rapid processing.

The amount of replenishment is preferably small, but is 20 to 600 m4 and preferably 50 to 300 rrl per photosensitive material.

More preferably 100 mj2 to 200 mI! , it is desirable to do so.

In a preferred embodiment of the direct positive light-sensitive material of the present invention, the support has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer, and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Further, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. To form a direct positive color image, the red-sensitive emulsion layer contains a non-diffusible cyan-forming coupler, the green-sensitive emulsion layer contains a non-diffusible magenta-forming coupler, and the blue-sensitive emulsion layer contains a non-diffusible yellow-forming coupler. However, different combinations may be used depending on the situation. Regarding non-diffusive cyan, magenta and yellow couplers, for example, Japanese Patent Application No. 1986-2
Those described in the specification of No. 86367, 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 do not substantially contain 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 which do not contain any silver iodide.

Regarding the internal latent image type emulsion that can be used in the present invention, Japanese Patent Application No. 1983-253716 filed October 27, 1985 (Applicant: Fuji Photo Film Co., Ltd.), page 28, No. 14
From line 3 to page 31, line 2 of the same specification, regarding 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.
Details of the color couplers that can be used in the present invention are described on page 33, line 18 to page 40 of the same specification.

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 using a core/shell type emulsion, 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 may be higher in the shell or the halogen composition of the core and shell may be the same. is preferable.

In the present invention, after imagewise exposure using a light-sensitive material, after or while performing fogging treatment with light or a nucleating agent, surface development is performed at a pH of 11.5 or less using 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
More preferably, it is in the range of 11.0 to 10.0.

The fogging treatment in the present invention is the so-called "light fogging method".
Either of a method called "chemical fogging method" in which the entire surface of the photosensitive layer is exposed to second light, and a method called "chemical fogging method" in which development is performed in the presence of a nucleating agent may be used. Development may be carried out in the presence of a nucleating agent and fogging light. Further, a photosensitive material containing a nucleating agent may be fog-exposed.

Regarding the light fogging method, the above-mentioned patent application No. 61-25371
It is described in the specification of No. 6, page 47, line 4 to page 49, line 5. The nucleating agent that can be used in the present invention is described in the same specification from page 49, line 6 to page 67, line 2, and especially the general formula (N-
Preference is given to using compounds represented by 1) and (N-2).

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

(N-1-1) 5-ethoxy-2-methyl-1-propargylquinolinium bromide (N-1-2) 2.4-dimethyl-1-propargylquinolinium bromide (N-1-3) 2-methyl-1-(3-(2-(4
-methylphenyl)hydrazonocobutyl)quinolinium iosito(N-1-4) 3,4-dimethyl-dihydropyrido(2,1-b)benzothiazolium bromide(N-1-5) 6-nitoxythio Carponylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-6) 2-Methyl-6-(3-phenylthioureido)-1-propargylquinolinium promide (N-1- 7) 6-(5-penzotriazolecarboxamide)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-8) 6-(3-(2-mercaptoethyl)ureido]-2- Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-1-9) 6-(3-(3-(5-mercapto-thiadiazol-2-ylthio)propyl]ureido)-2-methyl-1-propargylquinolinium Norinium trifluoromethanesulfonate (N-1-10) 6-(5-mercaptotetrazol-1-yl)-2-methyl-1-propargylquinolinium iosito (N-1-11) 1-propargyl-2- (1-propenyl)quinolinium trifluoromethanesulfonate (N-1-12) 6-nitoxythiocarponylamino-2-(2-methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate (N-I-13) 10-propargyl-1,2,3° 4-tetrahydroacridinium trifluoromethanesulfonate (N-1-14) 7-nitoxythiocarponylamino-10-propargyl-1,2° 3.4-Tetrahydroacridinium trifluoromethanesulfonate (N-1-15χ 6-nitoxythiocarponylamino-1-propargyl-2,3-pentamethylenequinolinium trifluoromethanesulfonate (N-I-16) 7-(3-(5-mercaptotetrazol-1-yl)benzamido)-10-propargyl = 1.2°3.4-tetrahydroacridinium perchlorate (N-I-17) 6-(3-(5- Mercaptotetrazol-1-yl)benzamide]-1-propargyl-2,3-pentamethylenequinolinium bromide (N-1-18) 7- (5-mercaptotetrazol-1-yl)-9-methyl-1 0 -Propargyl-1,2,3,4-tetrahydroacridinium promide (N-1-19) 7-[3-(N-(2-(5-
Mercapto 1,3.4-thianzol-2-yl)ethyl]carbamoyl)propanamide]-10-propargyl-1,2,3,4-tetrahydroacridinium imide (N-1-20) 6- (5- Specific examples of the compound represented by the general formula (N-n) of mercaptotetrazol-1-yl)-4-methyl-1-brobargyl-2,3-pentamethylenequinolinium bromide are shown below.

(N-n-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-pentylphenoxy)propyl]ureido)phenylmashonylamino]phenyl)hydrazine (N-11-3) 1-formyl-2-(4-(3
-(5-mercaptotetrazol-1-yl)benzamido]phenyl) hydrazine (N-11-4) 1-formyl-2-(4-[3
-(3-(3-(5-mercaptotetrazol-1-yl)]phenyl) ureido)phenyl]hydrazine (N-If-5) 1-formyl-2-(4-(3
-(N-(5-mercapto-4-methyl-1,2,4-triazol-3-yl)carbamoyl)propanamido)phenyl]hydrazine (N-11-6) 1-formyl-2-(4-( 3
-(N-(4-(3-mercapto-1,2,4-1lyazol-4-yl)phenyl)carbamoyl)propanamido)phenyl]hydrazine(N-I[-7) 1-formyl-2-( 4-(3-
(N-(5-mercapto-1,3゜4-thiadiazol-2-yl)carbamoyl]propanamido)phenyl]-hydrazine (N-n-8) 2 (4-benzotriazole-5
-carboxamido)phenyl] = 1-formylhydrazine (N-11-9) 2-(4-(3-(N-(benzotriazole-5-carboxamide)carbamoylphenyl) 1-formylhydrazine (N-n-10) 1-formyl-2- (4-
(1-(N-phenylcarbamoyl)thiosemicarbamide]phenyl]hydrazine (N-If-11) 1-formyl-2- (4-
C3-[3-phenylthioureido)benzamido]phenyl]-hydrazine (N-n-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-n-14) 1-formyl-2- (4-
(3- (3- (3- (5-Mercaptotetrazol-1-yl) phenylthioureido) benzenesulfonamido] phenyl) hydrazine Regarding the nucleation accelerator that can be used in the present invention, Japanese Patent Application No.
No. 286367, page 68, line 11 to page 71, line 3, and as a specific example,
It is preferable to use (A-1) to (A-13) described on page 1.

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

The bleaching/fixing treatment applied to the present invention is not limited to a mode in which bleaching and fixing are performed simultaneously in one bath bleach-fixing,
This term is used to include modes in which image processing is performed 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 fixing is followed by bleach-fixing. Aminopolycarboxylic acid iron complex salts are usually used as bleaching agents in bleaching solutions or bleach-fixing solutions.

As additives used in the bleaching solution or 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), treatments such as water washing and/or stabilization are performed.

It is preferable to use softened water as the washing water or stabilizing liquid. As a method of water softening treatment,
Examples include a method using an ion exchange resin or a reverse osmosis device described in Japanese Patent No. 131,632. As a specific method for these, it is preferable to use the method described in Japanese Patent Application No. 131632/1982.

Further, 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) The invention will now be illustrated by examples.

Example 1 Preparation of Emulsion C-1 An aqueous solution of potassium bromide and silver nitrate was prepared at a concentration of 0.3 per mole of Ag.
g of 3,4-dimethyl-1,3-thiazoline-2,000 ions was added simultaneously to an aqueous gelatin solution with vigorous stirring and at 75°C for about 20 minutes, until the average particle size was about 0. A monodisperse silver bromide emulsion of 40 μm octahedrons was obtained. To this emulsion were added 6 μm of sodium thiosulfate per mole of silver and 7 m
Chemical sensitization treatment was performed by adding g of chloroauric acid (tetrahydrate) and heating at 75° C. for 80 minutes. Using the thus obtained silver bromide grains as cores, they were further grown in the same precipitation environment as the first time, and the final average grain size was about 0. A monodisperse core/shell silver bromide emulsion of 7 μm octahedrons was obtained. The coefficient of variation in particle size was approximately 10%.

To this emulsion was added 1.5 μm of sodium thiosulfate per mole of silver. Chemical sensitization was performed by adding 51 ug of chloroauric acid (tetrahydrate) and heating at 60° C. for 60 minutes to obtain an internal latent image type halogenated emulsion C-1.

A multilayer color photosensitive material (10) having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

(Layer structure) The composition of each layer is shown below. The number is the amount of coating per hole in g.
It is expressed as For silver halide emulsions and colloids, the coated amount in terms of silver is expressed in grams, and for spectral sensitizing dyes, the amount added per mole of silver halide is expressed in moles.

Support polyethylene laminate paper (?4E1 layer side polyethylene with white pigment (TiOh)
and bluish dye (ulmarine blue)] E1 layer silver halide emulsion (C-1) 0.23 Spectral enhancement dye (ExSS-1) 1. oxto-' spectral sensitizing dye (
ExSS-2) 6.1xto-5 gelatin
0.90 cyan coupler (ExCC-1)
0.19 cyan coupler (ExCC-2)
0.24 Ultraviolet absorber (ExUV-1) 0.17
? Container (ExS-1) 0.
21 Development regulator (ExGC-1) 0.02 Stabilizer (ExA-1) 0.006 Nucleation accelerator (E
xZS-1) 3. oxlo-' nucleating agent (ExZK-
1) 8. oxto-” E2 layer gelatin 1.41 Color mixture prevention agent (ExKB-1) 0.09?Volume
(ExS -1) 0. 10 solvent
(ExS-2) 0.10 E3 layer silver halide emulsion (C-1) 0.21 Spectral enhancement dye (ExSS-3) 3.0XIO-' gelatin
0.90 magenta coupler (ExM
C-1) 0.14 color image stabilizer (ExSA-1)
0.18 Solvent (ExS-3) 0.
22 Development control agent (ExGC-1) 0.02 Stable agent (ExA-1) 0.006 Nucleation accelerator (E
xZS-1) 2.7X10-' nucleating agent (ExZK-
1) 1.4X10-' E4 layer gelatin 0.47 Color mixing inhibitor (ExKB-1) 0.03 Solvent (E
xS-1) 0.03 liter capacity (
ExS-2) 0. 03 E5th layer Colloid i 0.09 Gelatin 0.49 Color mixing prevention agent (E
xKB-1) 0.03) Capacity (E
xS -1) 0. 03) Container
(ExS-2) 0. 03th E6
Layer E7 same as layer 84 Silver halide emulsion (C1) 0.36 spectral sensitizing dye (ExSS-4) 1.2X10-' gelatin
1.90 yellow coupler ('ExY
C-1) 0.461 volume medium (BxS-2)
0. 18 Melt (ExS-4
) 0. 18 Development regulator (ExGC-1)
0.06 Stabilizer (ExA-1) 0.001 Nucleation accelerator (ExZS-1)5. oxto-' Nucleating agent (ExZK-1) 1.2X10-6 E8 layer gelatin 0.54 Ultraviolet absorber (ExUV-2) O,' 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 polymethyl methacrylate (average particle size 2.8 μm) 0.05 81st layer gelatin 8.70 82nd layer The same layer as 89th layer contains gelatin hardening agent ExGK-1 in addition to the above composition.
and surfactant were added.

Compound used to prepare the sample (ExCC-1) Cyan coupler (ExCC-2) Cyan coupler (ExMC-1) Magenta coupler CeHlq (t) (ExYC-1) Yellow cabler (ExSS-1) Spectral sensitizing dye (ExSS-2) Spectral enhancement dye (ExSS-3) Spectral sensitizing dye (ExSS-4) Spectral enhancement dye or (ExS-1) Solvent (ExS-2) Solvent (EMS-3) Volume medium l:1 mixture (volume ratio) of (ExS-4H capacity medium (ExUV-1) Ultraviolet absorber c 4 H9(t).

Cd(q(t) (1): (2): (3) 5:8:9 mixture (weight ratio) (ExUV-2) Ultraviolet absorber (1): (2): (3)-2 :9:8 mixture (weight ratio) (ExSA-1) Color image stabilizer (ExKB-1) Color mixing inhibitor (ExGC-1) Development regulator (ExA-1) Stabilizer 4-hydroxy-5,6-trimethylene- 1°3.3a
, 7-titrazaindene (ExZS-1) Nucleation promoter 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (ExZK-1) Nucleating agent 6-nitoxythio Carponylamino-2-methyl-1-
Propargyl quinolinium trifluoromethanesulfonate (ExGK-1) Gelatin hardener 1-oxy-3,5-dichloro-S-triazine sodium salt Direct positive silver halide color photographic light-sensitive material 101 (total Photosensitive material 102 (total silver amount: 1 .21 g/n () was imagewise exposed and 50 consecutive shots were performed in the following Process A. At the start and end of the process, a similar light-sensitive material that had been wedge exposed at 250 CMS was processed, and the density was measured. Dm by fluorescent X-ray
The amount of silver in the ax portion was measured.

Processing step A Color development 2 minutes 00 seconds 35°C 300mff1/nf
541! Bleach fixing 45 seconds 35℃200
mj2/rd 2〃■ 30 seconds 35℃1,3
〃■ 30 seconds 35℃- ■ 30 seconds 35℃200mff1/rd 〃
The washing bath replenishment method was a so-called countercurrent replenishment method in which the washing bath (1) was replenished, the overflow liquid from the washing bath (2) was led to the washing bath (2), and the overflow liquid from the washing bath (2) was led to the washing bath (2).

[Color developer] A Mother solution Replenisher Ion exchange water 800m! ! , +30
0mj! Diethylenetriaminepentaacetic acid 2.0g
2.0g benzyl alcohol 12.8g
14.0g diethylene glycol 3.4g
4.0g Sodium sulfite 0.
7g 0.9g Sodium Bromide 0
．． 7g - 2X10 compounds from Table 1
-2 moles 2.5X10-2 moles sodium chloride
3.20g -3-methyl-4-amino-N-4,25g 6. 25g ethyl-N-(β
-methanesulfonamidoethyl)-aniline sulfate triethylenediamine (1,4-diazabicyclo(2,2゜2]octane) 5.0g 5.
0g potassium carbonate 30.0g 2
5.0g fluorescent brightener (stilbene type) 1. Og
Add 1.5g ion exchange water to 1000
rr+4 1000mf100O10,2010,40 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution] A Mother solution Replenisher Tap water 700rrl Ammonium thiosulfate I Log Same as mother liquor Sodium bisulfite 10g Diethylenetriamine 56g Iron pentaacetate (I [[) Ammonium monohydrate Ethylenediaminetetraacetic acid 2 5g Sodium.
Add dihydrate tap water and make 1000ml! pH
6,5 pH was adjusted with aqueous ammonia or hydrochloric acid.

Compound Φ [Water solution] Mother solution and replenisher Common tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water is passed through the packed hotbed column to bring the concentration of calcium and magnesium ions to 3/i! , below.

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

These results are shown in Table 1.

Example 2 500 mj of 5 types of color developing solutions after continuous processing in columns 1 to 5 in Example 1! 200m1 in a beaker! ,
and left at 35°C for 10 days. This liquid was filtered using filter paper, and its coloring and tar generation were compared.

Table 2 The color developer using the compound of the present invention generates less tar and is superior to the comparative example.

Example 3 In Example 1, the following emulsion C-1 was used instead of emulsion C-1.
A photosensitive material 103 (total silver amount: 0.89 g/, n()) was produced in exactly the same manner as the photosensitive material 101 except that No. 2 was used. The photosensitive material 103 was exposed in the same manner as in Example-1, The following treatment B was used for 50 consecutive treatments.

Preparation of Emulsion C-2 A mixed aqueous solution of potassium bromide and sodium chloride and an aqueous solution of silver nitrate were vigorously stirred into an aqueous gelatin solution containing 0.07 g of 3.4-dimethyl-1,3-thiazoline-2-thione per mole of Ag. They were simultaneously added at 65° C. over a period of about 14 minutes to obtain a monodisperse silver chlorobromide emulsion with an average grain size of about 0.23 μm (silver bromide content: 80 mol %). This emulsion contains 61 μm of sodium thiosulfate per mole of silver and 42 μm of sodium thiosulfate per mole of silver.
Chemical sensitization treatment was carried out by adding chloroauric acid (tetrahydrate) and heating at 65°C for 60 minutes. Using the thus obtained silver chlorobromide particles as cores, they were further grown in the same precipitation environment as the first time, and finally monodisperse cores with an average particle size of about 0.65 μm (silver bromide content 70 mol%) were obtained. A shell silver chlorobromide emulsion was obtained. The coefficient of variation in particle size was approximately 12%. To this emulsion, 1.5 μg of sodium thiosulfate and 1.5 g of chloroauric acid (tetrahydrate) per mole of silver were added and heated at 60° C. for 60 minutes to perform chemical sensitization treatment. Halogenated emulsion C-2 was obtained.

Processing step B Time Temperature Replenishment amount Color development 1 minute 30 seconds 38”C300m1/rd
Bleach fixing 40 seconds 38℃ 200mf/rrr
Stable ■ 20 seconds 38℃□■ 20 seconds 38℃□ ■ 20 seconds 38℃200m1/r+ A so-called countercurrent replenishment system was adopted in which the overflow liquid from bath (1) was introduced into stable bath (2).

[Color developer] B Mother solution Replenisher ethylenediaminetetra 2. Og 2.0 g Benzyl alcohol phosphonate 8.0 g 9.0 g Diethylene glycol 3.4 g 4.0 g Sodium sulfite 2.0 g 2.9 g Sodium bromide 0.5 g - Compounds of Table 3 2X10-" moles 2.5X10-2 moles 3
-Methyl-4-amino-4,25g 6.25gN=
Ethyl-N-(β-methanesulfonamidoethyl)-anilinetriethanolamine 8.0g 10.0g Dipotassium hydrogen phosphate 25. 0g 20.0g Fluorescent brightener (stilbene type) 1. 0g 1. 5g
Add water 10100O1000rne
pH 11,5011,70 The pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fixing solution] B Mother solution Replenisher ammonium thiosulfate 110g Ammonium sulfite same as the mother liquor 10g Ammonium bromide 30g Ethylenediaminetetraacetic acid 40g Ammonium iron(III) acetate/l hydrate ethylenediaminetetraacetic acid 5g Bleach accelerator (compound O below) 5xlO- 3 mol water was added to give a pH of 1000 mn, and the pH was adjusted to 6.5 with aqueous ammonia.

Compound 0 N=N [Stabilizing liquid] B liquid mother liquid Replenisher l-hydroxyethyl 1.6 g Same as the mother liquid Thene-1,1'-diphosphonic acid (60%) Bismuth chloride 0.35 g Polyvinylpyrrolidone 0.25 g Ammonia water 2
．． 5ml1 Nitrilotriacetic acid/3Na1.0g 5-chloro-2-methyl 50 ■ -4-isothiazolin-3-one 2-methyl-4-isothionate 5 ■ Azoline-3-one optical brightener (4,4'-di 1.0g aminostilbene type) Add water to 1000m4 pH 7.5 Adjust the pH with potassium hydroxide or hydrochloric acid.

The results are shown in Table 3.

Example 4 In Example 1, photosensitive material 101 was used, and the color developing agent shown in Table 4 was used for processing.

Table 4 *1 Color developing agents (D-5) and (D-6) added in equimolar amounts with D-6 are (D-1) and (
D-2) and (D-9) were preferred because they had a smaller amount of residual silver.

Example 5 In Example 3, 200 ml of 5 types of color developing solutions after continuous treatment at Nα11 to 15 were placed in a 500 mf beaker.
It was then left at 35°C for 10 days. This liquid was filtered using filter paper, and its coloring and tar order were compared.

Table 5 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 quickly obtained.

Furthermore, the formation of tar-like substances that occur when the developer is used over time can be effectively suppressed.

Claims (2)

[Claims] (1) A light-sensitive material containing at least one unfogged internal latent image type silver halide emulsion layer and a color image-forming coupler on a support after imagewise exposure, prior to development, or during the development process. In a method of directly forming a positive color image by developing, bleaching and fixing with a surface color developer containing an aromatic primary amine color developer in the presence of fogging light and/or a nucleating agent, the color image The forming coupler is a compound that is substantially non-diffusible and generates or releases a dye upon oxidative coupling with the developer, and the light-sensitive material has a dye density of 1.0 per m^2 of the light-sensitive material.
g or less and has a layer containing colloidal silver, and the developing solution has a pH value of 11.5 or less and contains a compound of the following general formula (I). Direct positive color imaging method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 represent an alkyl group or an alkenyl group.Or R^1 and R^2 are connected together with a nitrogen atom. may form a heterocycle.) (2) The development temperature is 30°C or higher and the development time is 1
Claim No. 1, characterized in that the time is within 50 seconds (
Direct positive color image forming method described in section 1).