JPH03235941A - Direct positive image forming method - Google Patents

Abstract

PURPOSE:To obtain the sufficiently low min. image density, a hard contrast, excellent white ground characteristic, and good color tones by incorporating a specific compd. into a surface developing liquid. CONSTITUTION:The surface developing liquid contains the compd. expressed by formula I. In the formula, R<1> to R<3> denote an alkyl group and may be further substd. with a substituent; R<1> and R<2>, R<2> and R<3> may cooperatively form a heterocycle. R<4> denotes 1 to 3C alkylene group. X denotes a hydroxyl group, amino group, amide group, sulfone amide group, alkoxy group, carboxyl group, sulfo group, alkyl thio group, alkoxycarbonylamino group, ureide group, carbamoyl group, alkoxycarbonyl group, suslfamoyl group, acyl group, sulfonyl group; m denotes 0 to 2; n denotes 1 to 2. The preferable and excellent images having the low min. density, the high contrast, the yellow color tones of a short wave are obtd. in this way.

Description

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

[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, 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. I can do it.

One type uses a silver halide emulsion that has been fogged in advance and uses solarization or the Burschel effect to destroy fog nuclei (latent images) in exposed areas, thereby obtaining a positive image directly after development. be.

The other type uses an unfogged internal latent image type silver halide emulsion and directly obtains a positive image by performing surface development after or while performing fogging treatment after image exposure. .

The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains and a latent image is mainly formed inside the grains upon exposure. means.

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
A method using a creating agent is known. This latter method is discussed, for example, in ``Research Disclosure''.
Closure) Magazine, Volume 151, No. 15162 (
Published in November 1976), pages 76-78.

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.

Various techniques are known to date in this technical field. For example, U.S. Patent Nos. 2,592.250, 2,466.957, 2.497.875,
Same No. 2,588,982, Same No. 3,317,322, Same No. 3. 761. No. 266, No. 3,761,2
No. 76, No. 3,796.577 and British Patent No. 1
, No. 151,363, No. 1,150,553 (No. 1
, No. 011.062) The main ones are those described in each specification etc.

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

For details on the direct positive image formation mechanism, see
The Theory of the Photographic Process by T. H. James
of the Photographic Process
ss), 4th edition, Chapter 7, pages 182-193, and US Pat. No. 3,761.276.

[Problem to be solved by the invention]

In direct positive image formation using such a photofogging method or a chemical fogging method, the development speed is slower and processing time is longer than in the case of a normal negative type. Or shorten the processing time by increasing the liquid temperature (
A method has been adopted to do so. However, there is a problem that the minimum image density of the direct positive image obtained generally increases when the pH is high. Further, under high pH conditions, the developing agent is likely to deteriorate due to air oxidation, and there is a problem in that the imaging activity thereof is significantly reduced.

In addition to increasing the pH, there are other ways to increase the development speed for direct positive image formation, such as using hydroquinone derivatives (US Pat. No. 3,227,552) and using mercapto compounds having carboxylic acid groups or sulfonic acid groups (especially However, the effects of using these compounds are still small, and it is difficult to reduce the minimum image density satisfactorily without directly reducing the maximum density of positive images. It hasn't arrived yet. Furthermore, Japanese Patent Application No. 61210809 describes that increasing the maximum density and decreasing the minimum density can be obtained by making a mercapto compound exist during core ripening of a core/shell type internal latent image emulsion. In this case, a sufficient level of white background and broken legs had not yet been reached, and a solution was desired.

Further, when a direct positive image is used for plate inspection, the photographic dyes used so far do not necessarily match the color tone of the printing ink, which is not preferable. Among these, there was a strong desire to improve the color tone of the yellow dye (shorter wavelength).

Therefore, the object of the present invention is to obtain the minimum image density (Dmin)
It is an object of the present invention to provide a direct positive image forming method which provides sufficiently low contrast, high contrast, excellent whiteness and good color tone.

[Means to solve the problem]

The object of the present invention is to provide an image forming method in which a direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance is processed using a surface developer. This was achieved by a direct positive image forming method characterized in that the surface developer contains at least one compound represented by the following formula (I).

General formula (I) N.H.

In the formula, R1, R2, and R3 represent an alkyl group, which may be further substituted with a substituent. Also, R1 and R2
, R2 and R'' may jointly form a heterocycle.

R4 represents an alkylene group having 1 to 3 carbon atoms; Represents an alkoxycarbonyl group, sulfamoyl group, acyl group, or sulfonyl group. m is 0 to 2, n is 1
is an integer from 2 to 2.

Formula (I) will be explained in more detail below. RR2 and R3 are substituted or unsubstituted alkyl groups (1 to 6 carbon atoms, such as methyl, ethyl, butyl, β-methanesulfonamidoethyl, β-hydroxyethyl, β-methoxyethyl, γ
-hydroxypropyl), and R1 and R2, and R2 and R3 may jointly form a heterocycle. R4 represents an alkylene group having 1 to 3 carbon atoms (for example, methylene, ethylene, propylene, l-methylethylene), and X represents a hydroxyl group, an amino group (0 to 6 carbon atoms, for example, amino, N,
N-dimethylamino, N-propylamino), amide groups (2 to 6 carbon atoms, e.g. acetylamino, butanamide), sulfonamide groups (1 to 6 carbon atoms, e.g. methanesulfonamide, ethanesulfonamide), alkoxy groups ( 1 to 6 carbon atoms, e.g. methoxy, butoxy), carboxyl group, sulfo group, alkylthio group (1 to 6 carbon atoms, e.g. methylthio, propylthio), alkoxycarbonylamino group (2 to 6 carbon atoms, e.g. methoxycarbonylamino, butoxy) carbonylamino), ureido group (
Carbon number 1-6゜For example, N, N-dimethylureido, N-
propyl ureido), carbamoyl group (1 to 6 carbon atoms, e.g. carbamoyl, N-butylcarbamoyl N.

N-diethylcarbamoyl), alkoxycarbonyl group (2-6 carbon atoms, e.g. methoxycarbonyl, isopropoxycarbonyl), sulfamoyl group (0-6 carbon atoms)
゜For example, sulfamoyl, N-butylsulfamoyl),
It represents an acyl group (having 2 to 6 carbon atoms, such as acetyl and butanoyl), and a sulfonyl group (having 1 to 6 carbon atoms, such as methanesulfonyl and butanesulfonyl). m is 0 to 2, n
is an integer between 1 and 2.

In the formula, R1, R2, and R3 preferably have 1 to 3 carbon atoms. Further, X is preferably a hydroxyl group, an amide group, a sulfonamido group, an alkoxy group, a ureido group, or a carbamoyl group, m is preferably O to l, and n is l.

The compound represented by formula (I) is very unstable to air oxidation when stored as a free amine, so it is generally produced and stored as a salt of an inorganic or organic acid, and when added to a processing solution. In many cases, amines are first handled as free amines. Examples of inorganic and organic acids for forming salts of the compound of formula (I) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid.

Specific examples of the color developing agent (compound of formula (I)) used in the present invention are listed below, but the present invention is not limited thereto.

NH2 N.H.

NH2 N.H.

3- NH2 NH2 NH2 NH2 4 Nl2 Nl2 Nl2 Nl2 17- Nl2 Ht Nl2 tS H2 NH2 (27) The color developing agent of the present invention is described in "Journal of the American Chemical Society"
of the American Chemical
! ;ocity).

It can be easily synthesized by the method described in Vol. 73, p. 3100 (1951) or a method analogous thereto.

The color developing agent of the present invention is 1 g to 1 g per 11 of the processing solution.
It is preferable to use in the range of 00g, 3g to 30g
The range is more preferable.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, a silver halide emulsion is deposited on a transparent support in a certain amount (0.5~
3g/rr? ), exposed to light for a fixed time of 0.01 to 10 seconds, and developed in the following developer A (internal developer) at 18°C for 5 minutes. The maximum density obtained is at least the maximum density obtained when a silver halide emulsion coated in the same amount and exposed in the same manner as above is developed in the following developer B (surface type developer) at 20°C for 6 minutes. Preferably those have a concentration that is 5 times greater, more preferably those that have a concentration that is at least 10 times greater.

δ Riri Statue Exhibition Metol 2g Sodium Sulfite (Anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
Add 5g KI O, 5g water 11 Surface type image solution Metol 2.5g L-ascorbic acid 10g NaBOz・4H203
5g KBr Add 1g water lll Specific examples of internal type emulsions include the conversion type silver halide emulsion described in the specification of US Patent No. 2,592,250, and US Patent No. 3,761,276. , 3,850,63
No. 7, No. 3,923,513, No. 4. 035. 1
No. 85, No. 4,395,478, No. 4,504゜57
No. 0, JP-A-52-156614, JP-A No. 5512754
No. 9, No. 53-60222, No. 56-22681,
The core/shell described in the patents disclosed in No. 59-208540, No. 60-107641, No. 61-3137, No. 62-215272, and Research Disclosure magazine Nα23510 (published November 1983), page 236. type silver halide emulsions.

The shapes of the silver halide grains used in the present invention include regular crystal shapes such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/ Tabular particles having a thickness ratio of 5 or more may be used. Further, an emulsion having a composite form of these various crystal forms or a mixture thereof may be used.

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

The average grain size of silver halide grains is 2 μm or less.
．． The thickness is preferably 1 μm or more, and particularly preferably 1 μm or less and 0.15 μm or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the particle number or weight should be ±40% of the average particle size.
So-called "monodisperse" particle size distribution with a narrow particle size distribution in which 90% or more of all particles fall within ±20%, preferably within ±20%.
Preferably, silver halide emulsions are used in the present invention.

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

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. A detailed example can be found in the patent described in, for example, Research Disclosure Magazine N (L17643-II [(issued 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, for example, 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 a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed examples, see Research Disclosure Magazine No. 17643-
VI (published December 1978) and [Stabilization of Photographic Silver Halide Emulsion J (E, J. Birr, “5tabi
lization of Photo.

graphic 5ilver Halide Emu
lsion” (Focal Press), 1974
It is listed in annual publications.

A variety of color couplers can be used to form direct positive color images in the present invention. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention are given in "Research Disclosure" magazine Nα17643 (published in December 1978), p. It is described in the compounds described in JP-A-62-215272 and the patents cited therein.

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

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

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

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

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

The photosensitive material of the present invention includes a beam side for preventing irradiation and halation, an ultraviolet absorber, a plasticizer, a fluorescent whitening agent, a matting agent, an air fog prevention agent, a coating aid, a hardening agent, and an antistatic agent. It is possible to add additives such as additives and slip property improvers. Representative examples of these additives are described in Research Disclosure Magazine No. 17643, pages 25-27 (published in December 1978), and pages 647-651, published in 18716 (published in November 1979). There is.

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

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. . 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 agent,
It is preferable to appropriately provide auxiliary layers such as a back layer and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are disclosed in Research Disclosure Magazine No. 17643V.
Items listed in section (■) (published in December 1978), page 28, European Patent No. 0,102,253, and JP-A-61-97
No. 655. Also, research
Disclosure magazine Nα17643XV items 28-29
The application method described on page 1 can be used.

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

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to "Research Disclosure" magazine No. 1712.
It can also be applied to black-and-white photosensitive materials using the three-color coupler mixture described in No. 3 (published July 1978).

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

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

These specific methods are described, for example, in British Patent No. 1,151,
No. 363, Special Publication No. 45-12710, No. 45-127
No. 09, No. 58-6936, JP-A-4119727, No. 56-137350, No. 57-129438,
No. 5111-62652, No. 58-60739, No. 58-70223 (corresponding U.S. Pat. No. 4,440°851)
No. 58-120248 (corresponding European Patent No. 8910)
1A2) etc.

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

It is preferable to immerse the light-sensitive material in a developer solution or a pre-bath solution, and to irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. The time from penetration into the liquid to photofogging exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.01 seconds to 2 minutes.
Preferably 0.1 seconds to 1 minute, more preferably 1 second to 4 minutes
It is 0 seconds.

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

Here, the "nucleating agent" is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. In the present invention, fogging using a nucleating agent is particularly preferred.

When incorporated into a light-sensitive material, it is preferably added to 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, it may be added to the Utsumi-type silver halide emulsion layer, for example, in the Kudzu layer. , an intermediate layer, an undercoat layer or a back layer.

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

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

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

General formula (N-I) 11 (In the formula, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-shell heterocycle, and Z may be substituted with a substituent. R" is a fatty acid is a group group, and R'! is a hydrogen atom, an aliphatic group, or an aromatic group.

R'' and RIt may be substituted with a substituent.

Furthermore, R" may be further combined with the heterocycle completed by 2 to form a ring. However, among the groups represented by Rl, RI2 and Z, at least - is an alkynyl group, an acyl group, It contains a hydrazine group or a hydrazone group, or forms a 6-membered ring with Rl l and R'' to form a dihydropyridinium skeleton. Furthermore, at least one of the substituents in R1%R'' and 2 may have a group that promotes adsorption to silver halide.Y is a counter ion for charge balance, and n is 0 or l. be.

Specific examples of the compound represented by formula (N-I) of the present invention are shown below.

(N-I-1) 5-ethoxy-2-methyl=1 propargylquinolinium bromide 2,4-dimethyl-2-propargylquinolinium bromide 3,4-dimethyl-dihydropyride [2,1-b) Benzothiazolium bromide CN-1-4> 6-nitoxythiocarbonyla (
N-I-2) (N-I-3) (N-I (N-I Mino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate 6-(5-benzotriazolecarboxamide)-2-methyl 1-propargylquinolinium trifluoromethanesulfonate 6-(5-mercaptotetrazol-1-yl)-2-methyl 1-propargylquinolinium iomide 7) 6-nitoxythiocarbonylamino-2-(2
-Methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate lO-propargyl-1,2゜3.4-tetrahydroacridinium trifluoromethanesulfonate 5) 6) 8) (N-I-9 ) 7-nitoxythiocarbonylamino-10-propargyl-1゜2.3.4-tetrahydroacridinium trifluoromethanesulfonate 7-[3-(5-mercaptotitrazol-1-yl)benzamide]-1O- Propargyl-1゜2.3.4-tetrahydroacridinium perchlorate 7-(5-mercaptotetrazol-1-yl)-9-methyl-10-propargyl-1,2,3゜4-tetrahydroacridinium Bromid 7-ethoxythiocarponylamino-10-propargyl-1゜2-dihydroacridinium trifluoromethanesulfonate (N-l-13) 10-propargyl-7-(3
(N-I-11) (N-I-10) (N-I-12) (N-I (N-I -(1,2,3,4-thiatriazol-5-ylamino)benzamide)-1 , 2,3,4-tetrahydroacridinium perchloride 14) 7-(3-cyclohexylmethoxythiocarbonylaminobenzamide)-10-propargyl 1, 2. 3. 4-tetrahydroacridinium trifluoromethanesulfonate 7-(3-ethoxythiocarbonylaminobenzamide)-10 monopropargyl 1. 2. 3. 4-tetrahydroacridinium trifluoromethanesulfonate 7-[:3-(3-ethoxythiocarbonylaminophenyl)ureido]-10-propargyl-1゜2.3.4-tetrahydroacrylate 16) 15) Dinium trifluoromethane Sulfonate 7-(3-ethoxythiocarbonylaminobenzenesulfonamide)-10-propargyl-1゜2.3.4-tetrahydroacridinium trifluoromethanesulfonate (N-I-18) 7- (3-+3- (1-(5-mercaptotetrazol-1-yl)phenylthourido)benzamide]-10-propargyl 1, 2. 3. 4-tetrahydroacridinium trifluoromethanesulfonate 7-[3-(5-mercapto 1.3 .4-thiadiazole-1ylamino)benzamide] = 10-propargyl-1,2,3゜4-tetrahydroacridinium (N-I-17) (N-I-19) Trifluoromethanesulfonate (N-I- 20) 7-[3-(3-butylthioureido)benzamide]-10 propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate General formula (N-n) R”-N-N- G-R" RQ &Rt" (wherein R" represents an aliphatic group, aromatic group, or heterocyclic group; R12 is a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group) , or an amino group; G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (HN=C(); R" and R" are both hydrogen atoms, or one of them is a hydrogen atom and the other one represents any one of an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.However, a hydrazone structure (〉N-N=Cg) is formed by including G, R'', R14, and hydrazine nitrogen. (The above-mentioned groups may be substituted with a substituent if possible.) Next, specific examples of the compound represented by the general formula (N-n) will be shown.

(N-n-1) 1-formyl-2-(4-(3(
2-methoxyphenyl)ureido]-phenyl)hydrazine1-formyl-2-[4-(3-[3-(3-(2,4-di-tert-pentylphenoxy)propylthourido)phenylsulfonylaminoco-phenyl ) Hydrazine l-formyl-2-[4-[3-(5-mercaptotetrazol-1-yl)benzamido]phenyl l Hydrazine (N-n-4) 1-formyl-2-[4-[3-
(3-(5-mercaptotetrazol-1-yl)phenyl](N-n-2) (N-n-3) laid) phenyl]hydrazine(N-n-5) 1-formyl-2-1: 4- [
3-(N-(5-mercapto-4-methyl-1,2,4-triazol-3-yl)carbamoyl]propanamide) phenyl] hydrazine l-formyl-2-+4- (3 (N-(4- (3-mercapto-1,2,4-)lyazol-4-yl)phenyl]carbamoyl]-propanamido]phenyl) hydrazine 1-formyl-2-[4-[3 (N-(5-mercapto-l).

3.4-thiadiazol-2-yl)carbamoyl]propanamido)phenyl]-hydrazine 2- C4-(benzotriazole-5-carboxamide)pheni(N-n-8) (N-n-7) (N-n -6) L]-1-formylhydrazine (N-n-9) 2-(4-[3-(N-(benzotriazole-5-carboxamido)carbamoyl]propanamido)phenyl]-1-formylhydrazine 1- Formyl-2-(4-(1-(N-phenylcarbamoyl) thiosemicarbazido]phenyl) Hydrazine l-formyl-2-[4-(3-(3-phenylthioureido) benzamido]phenyl) Hydrazine l-formyl- 2-[4-(3 hexylureido)phenyl] hydrazine ■-formyl-2-[4-[3-(5-mercaptotetrazol-1-yl)benzenesulfona(N-n-13) (N-It-12 ) (N-n-11) (N-n-10) mido]phenyl) hydrazine (N-IF-14) 1-formyl-2-[4-(
3[3-(3-(5-mercaptotetrazol-1-yl)phenyl]ureido)benzenesulfonamido)phenyl)hydrazine (N-n-15) 1-formyl-1-[4-[3
[3-(2,4-di-tert-pentylphenoxy)propyl]ureido)phenyl]hydrazine The nucleating agent used in the present invention can be contained in the sensitive material or in the processing solution for the sensitive material, and is preferably incorporated into the sensitive material. It can be contained inside.

When incorporated into a sensitive material, it is preferably added to the internal temperature silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers. For example, it may be added to an intermediate layer, undercoat layer or back layer. When adding a nucleating agent to the processing solution, it should be added to the developer solution or a low p
It may be contained in the H pre-bath.

When a nucleating agent is contained in the sensitive material, the amount used is preferably 10-8 to 10-2 mol per 1 mol of silver halide.
More preferably, it is 10-' to 10-3 mol.

In addition, when adding a nucleating agent to the processing solution, the amount used is 1
It is preferably lo-5 to 10-1 mol, more preferably 10-4 to 10-2 mol.

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

Nucleation accelerators include tetrazaindenes, triazaindenes, and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, and JP-A-63-Sho. 10
Compounds described in Publication No. 6656 (pages 6 to 16) can be added.

Specific examples of the nucleation accelerator are listed below, but the invention is not limited thereto.

3-mercapto-1,2,4-1-riazolo(4,5-a)pyridine (A-2) 3-mercapto-1,2,4-triazolo(4,5-a) Pyrimidine 5-mercapto-1 ,2,4-triazolo[1,5-a]pyrimidine 7-(2-dimethylaminoethyl) -5-mercapto-1,2,4-triazoloC1,5-a)pyrimidine 3-mercapto-7-methyl- 1゜2.44 Riazolo(4,5-a) Pyrimidine 3.6-dimerkabuto 1.2.4 Triazolo[4,5-b) Pyridashi(A-5) (A-6) (A-1) (A -3) (A-4) (A-7) 2-mercapto-5-methylthio-1,
3,4-thiadiazole 3-mercapto-4-methyl-1゜2,4-)riazole (3-dimethylaminopropyl (A-8) (A-9) thio)-5-mercapto-1,3,4 thiadiazole Hydrochloride (A-10) 2-(2-morpholinoethylthio)5-mercapto-1,3,4-thiadiazole hydrochloride The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, It is preferably contained in the internal latent image type silver halide emulsion layer and other hydrophilic colloid layers (intermediate layer, protective layer, etc.) in the light-sensitive material. Particularly preferred is a silver halide emulsion layer or a layer adjacent thereto.

The color developing solution used in the development of the photosensitive material of the present invention is an alkaline aqueous solution containing the compound of formula (1) as a main component.

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

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

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

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a wappler), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in [Journal of the Society of Motion Picture and Television Engineers J
(Journal of the 5ociety
of MotionPicture and Te1e
Vision Engineers) Volume 64, 248
It can be determined by the method described on page 253 (May 1955 issue).

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

〔Example〕

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

Example-1 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material was prepared in which the following 1st to 14th layers were coated on the front side of the film (0 micron), and 15th to 16th layers were coated on the back side. The polyethylene on the first layer coating side contains titanium oxide as a white pigment, and a small amount (0,003g/
ni') ultramarine blue is included as a material (the chromaticity of the surface of the support is 88.0, -0.20 for L*, a*, b* systems.
It was ゜-0.75. ).

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

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

1st layer (antihalation layer) Black colloidal silver 0.10 gelatin
0.70 Second layer (intermediate layer) Gelatin 0.70 Third layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (Ext-12,3) (average grain size 0.70) 25 μ, size distribution [coefficient of variation] 8%, octahedral) 0.04 Silver chlorobromide spectrally sensitized with a red sensitizing dye (Ext-12,3) (silver chloride 5 mol%, average grain size 0.04). 40μ,
Size distribution 10%, octahedral)
0.08 gelatin 1.0
0 cyan coupler (ExC-12,3 to 1=1:0.2
) 0.30 Anti-fading agent (Cp
d-12,3,4 equivalent) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-12,3 equivalent) 0,12 4th layer (high sensitivity red sensitive layer) Red enhancement Silver bromide spectrally sensitized with sensitive dyes (ExS-1, 2, 3) (average grain size 0.60μ, size distribution 15%)
, octahedron) 0.14 gelatin
1.00 cyan coupler (ExC-1, 2, 3 in 1
=1:0. 2) 0. 30 Anti-fading agent (Cpd-1, 2, 3, 4 equivalents) 0.18 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12 5th layer (Interlayer) Gelatin 1.00 Color mixing prevention agent (Cpd-7) 0.08 Color fading prevention agent solvent (S
olv-4,5 equivalent) 0.16 Polymer latex (Cpd-8) O1IO 6th layer (low sensitivity green sensitive layer) Silver bromide (spectral sensitized with green sensitizing dye (ExS-4)
Average particle size 0.25μ, size distribution 8%, octahedral)
0.04 Silver chlorobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver chloride 5 mol%, average grain size 0.40 μ, size distribution 10%, octahedral) 0.06 Gelatin 0. 80 Magenta coupler (ExM-1, 2, 3 equivalent) 0.11 Anti-fade agent (equal amount of Cpd-5, 9) 0.15 Anti-stain agent (1.4: Cpd-10, 11, 12)
0.025 force puller dispersion medium (Cpd-6) 0.05 coupler solvent (SOLv
-4,6 equivalent) 0.15 7th layer (high sensitivity green sensitive layer) Silver bromide (
Average particle size 0.65μ, size distribution 16%, octahedral>0.10 gelatin
0.80 magenta coupler (ExM-1, 2, 3
equivalent) 0.11 Anti-fading agent (Cpd-5,9 equivalent) 0.15 Anti-stain agent (Cpd-to, 11.12 in 1.4 + 1:1 ratio) 0.025 Force puller dispersion medium (Cpd −
6) 0.05 coupler solvent (SOIV-4,6 equivalent) 0.15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver gelatin color mixing inhibitor (Cpd-7 ) Color mixing inhibitor solvent (SOLv-4, 0, 12 0, 07 0, 03 5 equivalents) 0.10 0.07 Polymer latex (Cpd-8) 10th layer (intermediate layer) 11th layer same as the 5th layer Layer (Low sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.40μ, size distribution 8%, octahedral) 0.07 blue sensitization Dye (ExS-5,6
) spectrally sensitized silver chlorobromide (silver chloride 8 mol%, average grain size 0.60 μ, size distribution 11%, octahedral) 0,
14 Gelatin 0.80 Yellow coupler (ExY-112 equivalent) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-stain agent (Cpd-15) 0.007 Power puller dispersion medium (Cpd-6) 0. 05 coupler solvent (Solv
-2) 0.10 12th layer (high sensitivity blue sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, size distribution 18%, Face piece) 0.15 gelatin
0.60 yellow coupler (ExY-1,2 equivalent)
0.30 0.10 0.007 0.05 0.10 Anti-fading agent (Cpd-14) Anti-stinting agent (Cpd-15) Coupler dispersion medium (Cpd-6) Coupler solvent (Solv-2) 13th layer ( Ultraviolet absorbing layer) Gelatin 1.00 Ultraviolet absorber (Cpd-2, 4, 16 equivalent) 0.50 Color mixing inhibitor (Cp d-7, 17 equivalent) 0.03 Dispersion medium (Cpd-6) 0. 02 UV absorber solvent (Solv-2, 7 equivalent) 0.08 Anti-irradiation dye (Cpd-13, 19, 20
, 2113 in a 10:10:13:15:20 ratio)
0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) 0.03 Acrylic modified copolymer of polyvinyl alcohol 0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
0.05 gelatin
1.80 gelatin hardener (H-1, H-2 equivalent) 0.
18 15th layer (back layer) Gelatin 2.50 Ultraviolet absorber (Cpd-2, 4, 16 equivalent) 0.50 Dye (Cpd-18, 19, 20, 21, 13 equivalent)
0.06 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
0.05 gelatin
2.00 Gelatin hardening agent (H-1, H-2 equivalent) 0.1
4. How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75°C over 15 minutes with vigorous stirring.
Octahedral silver bromide grains with an average grain size of 0.40 μm were obtained. To this emulsion was added 0.3 g of 3,4-dimethyl-1 per mole of silver.
, 3-thiazoline-2-thione, 6■ sodium thiosulfate, and 'Img of chloroauric acid (tetrahydrate) were added in sequence at 75°C.
Chemical sensitization treatment was carried out by heating for 80 minutes. The grains thus obtained were used as cores and further grown in the same precipitation environment as the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 μm. The coefficient of variation in particle size was approximately 10%. To this emulsion, 1.5 μ of sodium thiosulfate and 1.5 μ of chloroauric acid (tetrahydrate) were added per mole of silver and heated at 60°C for 60 minutes to perform chemical sensitization treatment. A silver oxide emulsion was obtained.

Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
Cpd-22 was used in an amount of 10-2% by weight based on silver halide, and Cpd-22 was used in an amount of 10-2% by weight as a nucleation accelerator.Alkanol
C (Dupon) and sodium alkylbenzenesulfonate, succinate ester and Ma as coating aids.
gefac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. (cpci-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number 101. The compounds used in the examples are shown below.

ExS ■ (CH2)3 (CH2)3 pd 40 pct pd-3 pd 1 ExS O3 O3H ExS ExS pd-5 pd-6 pd Song H pd (-CH2 CH+ff1 COOC, H 2 pd 10 pd-11 Js 0 1 pd 6 pd-17 H H pd-18 65- pd-12 pd 3 C)ItCOOK CH2COOK pd-14 pa 5 H pd-19 pd-20 O3K O3K pd 1 SO, K SO, ni 6 Cpd Cpd Cpd-25 xC- 1 xM Cpd xC xM xY olv olv-2 olv-3 olv olv olv olv -1 -2 H Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methylhexyl) phthalate tricresyl phosphate dibutyl phthalate trioctyl phosphate Di(2-ethylhexyl)phthalate 1.2-bis(vinylsulfonylacetamido)ethane 4.6-dichloro-2-hydroxy-1,3,5-1-riazine Na 70 ExZK-17-(3-ethoxythiocarbonylamino benzamide)-9-methyl-10-prohagylu, 2°3.4-tetrahydroacridinilam trifluoromethanesulfonateExZK-22-C4-(3-(3-(3-[5-(3
-[2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl)phenylrubamoyl]-4-hydroxy- 1-naphthylthio)tetrazol-1-yl]phenyl ureido] benzenesulfonamido)phenyl)-1-formyl A sample prepared as above for hydrazine was exposed to normal wedge exposure (3
200, 0.1 seconds, IOCMS), and then the treatment step A shown below was performed. Processing step B is the same as processing step A except that the color developing agent is replaced in equal molar amounts.
-K was applied.

Measure the magenta density of the obtained image and find the minimum density Dmi
n, concentration Dmin+0. Average gradations between 1 and Dmin+0.6 were obtained and are shown in Table 1.

Tori Kobi A Processing process Time Temperature color development 135 seconds 38℃ Bleach fixing 40〃33〃 Washing with water (1) 40〃33〃 Washing with water (2) 40"33" Drying
30〃80/The composition of each treatment liquid was as follows.

Uomeisei Eijika D-Sorbit 0.15g Natriram naphthalene sulfonate/formalin condensate 0.15g Ethylenediaminetetrakismethylenephosphonic acid 1.5g Diethylene glycol 12.01d Benzyl alcohol 13.5m/Potassium bromide benzotriazole sodium sulfite N, N -Bis(carboxymethyl)hydrazine D-glucose triethanolamine Shown in Table 1 Color developer Potassium carbonate Fluorescent brightener (diaminostilbene type) pH (25°C) Hoshipage Sadahoka Ethylenediamine 4-acetic acid 2 Sodium Dihydrate ethylenediaminetetraacetic acid, Fe(II), ammonium, dihydrate ammonium thiosulfate 0.70g 0.003g 2.4g 4.0g 2.0g 6.0g 0.015 Moles 30.0g 1.0g 10.25 2,0g 70.0g (700g, #) 180dp-
Sodium toluenesulfinate 45.0g Sodium bisulfite 35.0g 5-mercapto-
1,3,4-Triazole 0.5g Ammonium nitrate 10.0gpH (25°C'
) 6.10 Mixed bed type tap water filled 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 was passed through the column to reduce the concentration of calcium and magnesium ions to 3/l or less, and then sodium dichloride isocyanurate 20/l and sodium nitrate 1. 5 g/l was added. The pH of this solution is 6.5~
It was in the range of 7°5.

Processing step B- was also carried out in the same manner as processing step A, except that the color developing agent was replaced in equimolar amounts with those shown in Table 1.

Table 1 Color developer for comparison H2 H2 H2 5- = 76 Direct positive photographic light-sensitive materials treated with a color developer containing the compound (I) of the present invention have excellent whiteness and average gradation. It was nice and hard.

Example 2 The sample obtained in Example 1 was subjected to normal wedge exposure (3200, 0.1 seconds, 10 CMS) in the same manner as in Example 1, and then subjected to the processing steps shown in Table 2. The minimum yellow density Dmin and the maximum absorption wavelength λmax in the high density region of the resulting image were measured.

A direct positive photographic light-sensitive material treated with a color developing solution containing the compound (I) of the present invention had excellent white background properties and a yellow tone that was preferable at short wavelengths.

Example 3 Nucleating agent E added to each photosensitive layer of the sample prepared in Example 1
xZK-L A sample prepared in the same manner as in Example 1 was prepared except that ExZK-2 was removed.

After this sample was exposed to light in the same manner as in Example 1, it was subjected to the processing steps A to K of Example 1 while being photofogged, and the same results as in Example 1 were obtained.

〔Effect of the invention〕

By using a processing solution containing the color developing agent of the present invention, it is possible to obtain an excellent direct positive color image with a low minimum density (Dmin), a hard gradation, and a favorable yellow tone at short wavelengths.

Claims (1)

[Scope of Claims] An image forming method in which a direct positive photographic light-sensitive material having at least one photographic emulsion layer containing internal latent image type silver halide grains which have not been fogged in advance is processed using a surface developer, A direct positive image forming method, characterized in that the surface developer contains at least one compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1, R^2, R^3 represent an alkyl group,
R^1 and R^2, R^2 and R^3 may jointly form a heterocycle. R^4 represents an alkylene group having 1 to 3 carbon atoms;
Represents a ureido group, carbamoyl group, alkoxycarbonyl group, sulfamoyl group, acyl group, and sulfonyl group. m is an integer from 0 to 2, and n is an integer from 1 to 2.