JPS6337347A - Direct positive color image forming method - Google Patents

Abstract

PURPOSE:To rapidly and stably form a direct positive color image small in drop of color development density by incorporating a tetrazaindene derivative having no SH group in a color developing solution. CONSTITUTION:Development processing is carried out with the developing solution having a pH of <=11.5 and containing a tetrazaindene derivative having no SH group, and substantially containing no benzyl alcohol. A color coupler itself is substantially nondiffusive, and it is a compound to be allowed to release or produce a substantially nondiffusive dye by the coupling reaction with the oxidation product of an aromatic primary amine color developing agent. The various kinds of known tetrazaindene derivatives except ones having the SH group can be used, and a combination of >=2 such compounds may be used. Especially preferably tetrazaindene derivatives are represented by formulae I and II in which each of R' and R'' is H, an aliphatic group, or an aromatic group, and n is 1 or 2. An internal latent image type silver halide emulsion is not fogged on the surfaces of the silver halide grains in advance, and the latent image is formed in the insides of the silver halide grains of the emulsion. Further, as for inner latent image type silver halide emulsion, the surface of silver halide particle is not coated beforehand and it is an emulsion containing silver halide forming essentially a latent image at the inside of particle.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an image forming method for directly obtaining a positive color image by subjecting a positive silver halide photographic light-sensitive material to imagewise exposure and color development processing.

(Prior art) Directly, without the need for a reversal process or negative film?
Photographic methods for obtaining digital images are well known.

The method used to create a positive image using a conventionally known direct positive silver dihalide photographic material is as follows:
Excluding special cases, they can be mainly divided into two types in consideration of their practical usefulness.

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 is the unfogged internal latent image type.
・Using a silver halogenide emulsion, a positive image is directly obtained 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.

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

Various techniques are known to date in this technical field. For example, U.S. Patent Nos. 2,592,250, 2,466,957, 2,497,875,
No. 2,588,982, No. 3,317,322, No. 3,761,266, No. 3,761,276
No. 3,796,577 and British Patent No. 1.1
No. 51,363, 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
“Theory of the Photographic Ink Process” by T. H. James (Th@Theory
of The Photographic Process
ss) 4th edition, Chapter 7, pages 182-193 and US Patent 3.
It is described in No. 761,276, etc.

In other words, the so-called internal latent image (Po5itive hole) created inside the silver halide by the initial imagewise exposure.
), capri nuclei are selectively generated only on the surface of silver halide grains in unexposed areas,
It is believed that a photographic image (direct positive image) is then formed in the unexposed area by subjecting it to a conventional so-called surface development process.

As mentioned above, as a means for selectively generating capri 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 el@ILting agent) is known. This latter method is discussed, for example, in ``Research Disclosure'' (Re5search D).
isclosure), Volume 151, Volume 15162 (19
Published in November 1976), pages 76-78.

K, which directly forms a positive color image, is an internal latent image type - a silver halide sensitive material is subjected to a fogging process, then subjected to a surface color development process while being subjected to a fogging process, and then bleached and fixed (or bleach-fixed). It can be achieved by After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

(Problems to be Solved by the Invention) In direct positive image formation using such a light fogging 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. , the technology to increase the development speed is desired ≦.

In this case, it is not preferable to lower the pH of the developer because it takes longer to process. Therefore, using a low pH developer, the maximum image density is high, and the minimum image density is low. It is difficult to obtain a digital image, and the conventional method has been to increase the pH and/or temperature of the developer to shorten the processing time.

However, there is a problem that the minimum image density of the direct positive image obtained generally increases when the pH is high. Also high pH
Under these conditions, the developing agent is likely to deteriorate due to air oxidation, and there is a problem in that its imaging activity is significantly reduced.

In order to solve these problems, compounds that exhibit a nucleating effect even at pH 12 or lower have been proposed in IJJ Kaisho 52-69613, U.S. Patent No. 3,615,615, and U.S. Pat. There is a problem of increased image density, and in addition, these nucleating agents act on silver halide during storage of the sensitive material before processing, or the nucleating agent itself decomposes, resulting in a loss of density after processing. It has the disadvantage of reducing maximum image density.

Other means for increasing the development speed in direct positive image formation include the following.

US Pat. No. 3,227,552 describes the use of hydroquinone derivatives to increase the development rate of medium densities.

Further, JP-A-60-170843 describes adding a mercapto compound having a carzene acid group or a sulfonic acid group to increase the maximum image density.

However, even with the addition of these compounds, the development speed is still not sufficient. Moreover, the pH of the developer is 12.0, and lowering of the pH of the developer is still insufficient.

On the other hand, various methods have been conventionally used to increase the development speed and coloring speed of color developers. Among these, in order for the color developing agent to finally compile with the coupler to form a dye, it is necessary for the color developing agent itself to be incorporated into the coupler-dispersed oil droplets. Various additives are known as additives that promote color development. Benzyl alcohol is known to have a particularly strong effect on promoting color development.
Conventionally, it has been used to process various color photographic materials.

Even today, it is widely used as an almost essential ingredient.

Quadrindyl alcohol is soluble in water to some extent, but its solubility is poor, and diethylene glycol, triethylene glycol or alkanolamines are widely used to increase solubility.

However, these compounds and benzyl alcohol itself have a large pollution load when treated as wastewater, resulting in high ROD and COD values, and despite the advantages of improved color development and solubility as mentioned above, figure,
From the point of view of wastewater treatment, it has been desired to reduce or eliminate benzyl alcohol.

Furthermore, what about the aforementioned diethylene glycol? Even with the use of agent I, the solubility of benzyl alcohol is still insufficient, resulting in a burden on the effort and time required to prepare a developer. Additionally, if benzyl alcohol is carried into the subsequent bleaching bath or bleach-fixing bath with the developer and accumulates, it may cause the formation of leuco bodies depending on the type of cyan dye, and may reduce the color density. I was awake. It has also been found that the accumulation of these components makes it insufficient to wash out developer components, particularly color developing agents, in the water washing step, resulting in deterioration of image storage stability due to their remaining.

From these points of view, it is of great significance to reduce or eliminate benzyl alcohol from color developing solutions.

While Chikararaj is currently facing these problems, there is also a need to shorten the processing time for print finishing due to the trend toward shorter delivery times.

However, these requirements cannot be simultaneously met by conventional techniques, and it is obvious that if benzyl alcohol is removed from the color developer and the development time is shortened, the color density will be significantly reduced.

Therefore, using any of the prior art methods or any combination thereof, sufficiently high maximum image densities can be achieved using low pH and substantially benzyl alcohol-free color developers. Until now, no technology has been found to stably obtain direct positive color images with a short processing time.

On the other hand, a technique has been disclosed in which a tetrazaindene derivative is added to a developer to suppress negative images in low-density areas in the photofogging method and to prevent discoloration of background areas that appears in fog development in the chemical fogging method ( Japanese Patent Publication No. 55-1348
No. 48). However, this method does not allow a sufficiently high maximum image density and does not teach anything about accelerating the development time and therefore does not give any indication of the possibility of removing benzyl alcohol.

Therefore, it is an object of the present invention to reduce the color density even when an internal latent image type silver halide photosensitive material that has not been fogged in advance is processed for a short time with a color developing solution that has a low pH and does not substantially contain benzyl alcohol. It is an object of the present invention to provide a method for quickly and stably forming a direct positive color image with less turbulence.

Another object of the present invention is to provide a direct positive color image forming method that is less susceptible to changes in pH and composition of a developing solution and has stably low minimum image density and high maximum color density.

Another object of the present invention is to provide a direct color image forming method that prevents staining that occurs when high-temperature running color development is performed using a color developer that does not substantially contain benzyl alcohol.

Another object of the present invention is to provide a direct I-color image forming method in which the developer is less susceptible to air oxidation and the performance is less likely to fluctuate even when used for a long time.

(Means for Solving the Problems) The present inventors have discovered that the object of the present invention is to support at least one layer of a photographic emulsion layer containing internal latent image type silver halide grains and a color image forming coupler that have not been fogged in advance. After imagewise exposure of the photosensitive material held on the body, prior to development or during the development process, fog exposure and/or in the presence of a nucleating agent,
18 rt7. In the method of directly forming a positive color image by developing, bleaching and fixing M -k'< with a surface developer containing an amine-based color developer, the development process is carried out at pH 1.
1.5 or less, containing a tetrazaindene derivative having no SH group, and using a developer containing substantially no benzyl alcohol, and the color cazoler itself being substantially non-diffusible. and which is characterized in that it is a compound that produces or releases a substantially non-diffusible dye by oxidative camping with an aromatic amine color developer. I found out what can be achieved.

By incorporating a tetrazaindene derivative that does not have an SH group into a color developing solution, the present invention achieves maximum color development even when processed with a developing solution that has a low pH of 11.5 or less and does not substantially contain benzyl alcohol. This method is based on the discovery of the unexpected effect of obtaining direct positive color images with virtually no decrease in density and with suppressed staining even after long-term running processing at high temperatures.

In the present invention, it is only when a pH range lower than the normal pH value, which is generally considered to reduce the color density, that a sufficient amount of benzyl alcohol, which is a color development accelerator, is not included in the developer solution can be obtained. It is possible to obtain color density,
Moreover, the use of tetrazaindene derivatives has achieved an effect that is completely inconceivable based on common knowledge, such as suppressing the occurrence of staining even after long-term running treatment at high temperatures. It was impossible to predict.

Here, "color developing solution that does not substantially contain benzyl alcohol" means that the concentration of benzyl alcohol is 21111/i
t or less, preferably 0.5 ml/l or less, and more preferably no benzyl alcohol at all.

In the present invention, various known tetrazaindene derivatives (excluding those having an SH group) can be used. Two or more types of tetrazaindene derivatives may be used in combination. Particular preference is given to tetrazaindene derivatives of the formulas (I) and (n) below.

General formula [■] General formula [II] In the formula, R' and R'' each represent a hydrogen atom, an aliphatic group, or an aromatic group. n represents 1 or 2.

Specific examples of tetrazaindene derivatives that can be effectively used in the present invention are as follows. However, the tetrazaindene conductor of the present invention is not limited to these.

1) 4-hydroxy-6-methyl-1+ 3.3a, 7
-Chitrazaindene 2) 4-methyl-6-hydroxy-1+3+3a+7-
Tetrazaindene 3) 4-hydroxy-6-methyl-1,2+3a+7-
Chitrazaindene 4) 4-hydroxy-1,3,3a,7-chitrazaindene 5) 2-ethyl-4-hydroxy-6-7 enyl 1
+ 3 e 3 & + 7-chitrazaindene 6) 2
．． 6-dimethyl-4-hydroxy-1°3.3a, 7-
Citrazaindene 7) 2,6-dimethyl-4-hydroxy-5-ethyl-
1+ 3 + 38 + 7-chitrazaindene 8) 2
-phenyl-4-hydroxy-6-methyl-1+ 3
+ 3 a + 7-chitrazaindene 9) 4-hydroxy-5-ethyl-6-methyl-1+3+3a+7-chitrazaindene 1(Y) 4-hydroxy-6-7enyl-1.3゜3a, 7-chitrazaindene 1]) 2- Benzyl-4-hydroxy-6-7enyl-1+3.3ae7-chitrazaindene 12) 2-methylmercapto-4-hydroxy-6-methyl-1,3,3
a, 7-chitrazaindene 13) 4-methyl-6-hydroxy-1,2゜3a, 7-chitrazaindene 14) 4-hydroxy-6-phenyl-], 2゜3a,
7-Chitrazaindene 15) 4-hydroxy-1+ 2 + 3 m + 7
-Titrazaindene 16) 3-carboxymethylthio-4-methyl-6-hydroxy-1,2,3m,7-thitrazaindene These compounds are classified as
It can be synthesized by referring to the description in Japanese Patent No. 2533 and the like. These compounds represented by formulas [I] and (Il) are preferably contained in the developer solution in an amount of 0.01 to 20.?, more preferably 0.01 to 519. .

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 the silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, a certain amount of silver halide emulsion is coated on a transparent support, and this is exposed to light for a fixed time of 0.01 to 10 seconds using the following developer tA (internal type developer). liquid) at 18℃
The maximum density measured by a normal photographic density measurement method when developed for 5 minutes at It is preferred that the density is at least 5 times greater than the maximum temperature obtained when developed for 6 minutes at
More preferably, it has a lower concentration (both 10 times greater).

Internal developer A Metol 2I Sodium sulfite (
anhydrous) 90 g hydroquinone
8y Soda carbonate (-water salt) 52.51 KBr S & KI
O, 51! Add water and 2.5g of 11 surface type image solution Metol! -As;
Lupic acid 10. 9NaBO2・4H
2O351 KBr 1 1 Water is added to form an internal type emulsion.Specific examples include the converter silver halide emulsion described in U.S. Pat. No. 2,592,250, and U.S. Pat. No. 3,761,276. No. 3,85
No. 0,637, No. 3,923,513, No. 4.0
No. 35,185, No. 4,395,478, No. 4,
No. 504,570, JP-A No. 52-156614, No. 5
No. 5-127549, No. 53-60222, No. 56-
No. 22681, No. 59-208540, No. 50-10
No. 7641, No. 61-3137, Patent Application No. 61-364
No. 2, Research Disclosure Magazine 423510 (1
The core/shell type silver halide emulsion described in the patent disclosed in No. 236 (November 1983) can be mentioned.

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

The composition of silver halide includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide, or even if it contains silver iodide, the salt content (
(iodine) silver bromide, (iodine) silver chloride or (iodine) silver bromide.

The average grain size of the silver halide grains is 2μ or less and 0.
It is preferably 1 μ or more, but particularly preferably 1 μ or less and 0.
It is 15μ or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the number or weight of particles should be within ±40% of the average particle size, preferably within ±20% of the total particle size. It is preferable to use a so-called "monodisperse" silver halogenide emulsion in the present invention, which has a narrow grain size distribution of more than %. In addition, in order to satisfy the target gradation of a light-sensitive material, two emulsion layers having substantially the same color sensitivity have two different grain sizes.
More than one type of monodisperse silver halide emulsion or a plurality of grains of the same size but different in sensitivity 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 used in a layered manner.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the surface of each grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. For detailed examples, see Research Disclosure Magazine 417643-III (published December 1978).
It is in the patent described on page 23 etc.

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, detailed examples of the combination of the above dyes and supersensitizers can be found in, for example, Research Disclosure Magazine No. 17643-IV (published December 1978).
It is in the patent described on 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, please refer to Research Disclosure magazine 17643-VI.
(published December 1978) and “5tabilization of Photogr” by E. J. Birr.
aphic 5llver Halide Emulsi
ons'' (Focal Press), published in 1974.

A variety of color couplers can be used to form direct positive color images. Useful color couplers are
A compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized product of an aromatic primary amine color developer, and is itself a substantially non-diffusible compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are:
Research Disclosure” Magazineyo 17643 (197
(Published in December 2008) P25■-D section, same f'&L1871
7 (issued in November 1979) and patent application No. 1983-324
No. 62 and the patents cited therein.

Among them, typical yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type yellow m=equivalent couplers. Especially α−
Biparoylacetanili P-based couplers have excellent color fastness, particularly light fastness, while α-penzoylacetanili R-based couplers are preferred because they provide high color density.

In addition, 5-pyrazolone series that can be preferably used in the present invention→
The zenta coupler is a 5-pyrazolone coupler in which the 3-position is substituted with an arylamino group or an acylamino group (particularly a sulfur atom separation type two-equivalent coupler).

More preferred are pyrazoloazole couplers, among which pyrazolo (s, x-e) (:1.2.41 triazoles) described in U.S. Pat. The imidazo[1°2-b]pyrazoles described in U.S. Pat. No. 4,500,630 are more preferred in terms of low yellow side absorption and light fastness; Particular preference is given to the pyrazolo[,5-b)Ct,2.4])riazoles mentioned.

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent No. 2,474,293, 4°052.21
Naphthol-based and phenol-based couplers described in U.S. Pat. ,5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

A color coupler for correcting unnecessary absorption in the short wavelength range of the generated dye, a coupler in which the coloring dye has an appropriate diffusivity, a colorless coupler, a DIR coupler that releases a development inhibitor upon coupling reaction, or Couplers that release development accelerators and polymerized couplers can also be used. Typical amounts of color couplers used range from 0.001 to 1 mole per mole of light-sensitive silver halide, preferably 0.01 to 0.01 for yellow couplers.
5 mole, 0.003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

In the present invention, a coloring enhancer can be used for the purpose of improving the coloring property of the coupler. Representative examples of compounds are as follows:
Examples include those described in No. 1-32462, pages 374-391.

The coupler of the present invention is dissolved in an organic solvent with a high boiling point and/or a low boiling point, and added to an aqueous solution of gelatin or other hydrophilic colloid by high-speed stirring using a homogenizer or Kneizer, mechanical pulverization using a colloid mill, or by ultrasonication. Emulsification and dispersion is carried out using a technique utilizing
It is preferable to use the compounds described on page.

The coupler of the present invention is disclosed in Japanese Patent Application No. 61-32462-468.
475-77, it can be dispersed in hydrophilic colloids.

The photosensitive material produced using the present invention uses no-hydroquinone derivatives, aminophenol derivatives, and amines as one-color capri-preventing agents or color-mixing preventive agents.

Contains gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, etc., and has a good temperature at °C.

Typical examples of color capri-preventing agents and color-mixing preventive agents are disclosed in Japanese Patent Application 1986-3.
No. 2462, pages 600-630.

One mole of anti-fading agent can be used in the light-sensitive material of the present invention. Organic anti-fading agents include no-idokuquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, amine phenols, hindered amines, and silylated or alkylated ether or ester derivatives of the phenolic hydroxyl group of each of these compounds. Can be mentioned. Further, metal complexes such as (bissalicylaldoximato)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds having a hindered amine and a hindered phenol structure in the same molecule give good results. Also, the magenta dye image deteriorates.

In particular, in order to prevent deterioration due to light, JP-A-56-1
Spiroindanes described in No. 59644.

and chromans substituted with hydroquinone diethers or monoethers described in JP-A-55-89835 give preferable results.

A typical example of these anti-fading agents is 1% Gansho 61-3246.
No. 2, pages 401-440.

The purpose of these compounds can be achieved by co-emulsifying the corresponding color coupler with usually 5 to 100 times Ji[] with the coupler and adding it to the photosensitive layer. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is effective to introduce an ultraviolet absorber into the layers on both sides adjacent to the cyan coloring layer. Further, an ultraviolet absorber can also be added to a hydrophilic colloid layer such as a protective layer. Representative examples of the compounds are described in Japanese Patent Application No. 61-32462, pages 391-400.

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 includes:

Although gelatin is advantageously used, other hydrophilic colloids can also be used.

The light-sensitive material of the present invention includes a dye that prevents irradiation and halation, an ultraviolet absorber, a plasticizer, a fluorescent whitening agent, a matting agent, and an air capritic inhibitor.

Coating aids, hardeners, antistatic agents, slipperiness improvers, etc. can be added. Representative examples of these additives are [Research Disclosure]
sclosure) Magazine Na17643■～■(19
Published December 1978) P25-27. and same 18716
(published November 1979), pages 647-651.

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

Multilayer natural color photographic materials usually consist of 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 adjusted as desired. 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. Furthermore, each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, or two or more emulsion layers having the same sensitivity.
A non-light sensitive layer may be present between the two or more emulsion layers. A cyan-forming coupler in the red-sensitive emulsion layer and a magenta-forming coupler in the green-sensitive emulsion layer? Usually, the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

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

In the photographic light-sensitive material of the present invention, other layers on the photographic emulsion layer are published in Research Disclosure Magazine 17643XVI [
(1978, line 12J1) P28, European Patent No. 0,182,253, and JP-A-61-976
Coated Sarel on the support described in No. 55. l? , - same magazine kl
The coating method described in Section 7643XV P28-29 can be used.

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

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

The fogging process used in the direct positive color image forming method of the present invention may be by fogging exposure, which is the so-called "light fogging method," or by the so-called "chemical fogging method."
Any method may be used, even if it is carried out in the presence of a nucleating agent. A photosensitive material containing a nucleating agent may be fog-exposed.

Full-surface exposure, that is, fogging exposure in the present invention.

This is done after imagewise exposure, before and/or during development. A photosensitive material that has been imagewise exposed is placed in a developer.

Alternatively, the film may be exposed to light by immersing it in a pre-bath of a developer, or by taking it out from this solution and exposing it to light before it dries, but it is most preferable to expose it in a developer.

As a light source for fogging exposure, a light source within the sensitivity wavelength of the photosensitive material may be used, and is generally a fluorescent lamp, tungsten lamp, xenon lamp, sunlight, etc.

Either can be used. What are these specific methods?

For example, British Patent No. 1,151,363, Special Publication No. 45-1
No. 2710, No. 45-12709, No. 58-6936
No. 48-9727, No. 56-137350, No. 57-129438, No. 58-62652, No. 58-60739, No. 58-70223 (corresponding U.S. Pat. No. 4,440,851).

No. 58-120248 (corresponding European patent 89101A2
) etc. For photosensitive materials that are sensitive to all wavelengths, such as color photosensitive materials, Japanese Patent Application Laid-Open No. 56-137
A light source with high color rendering properties (as close to white as possible) such as those described in No. 350 and No. 58-70223 is preferable. The original illuminance is 0.01-2000 lux, preferably 0.
0.05-30 lux, more preferably 0.05-5 lux.

Which photosensitive materials use emulsions with higher sensitivity?

Low-intensity exposure is preferred. The illuminance may be adjusted by changing the luminous intensity of the light source, by reducing the light using various filters, by changing the distance between the photosensitive material and the light source, or by changing the angle between the photosensitive material and the light source. Exposure time can also be shortened by using weak light at the beginning of exposure and then using stronger light.

The photosensitive material is immersed in a developer solution or a 70-day bath solution.

It is preferable to irradiate the photosensitive material after the liquid has sufficiently penetrated into the emulsion layer of the photosensitive material. The time from immersion in the liquid to the light fog exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, and more preferably 10 seconds to 30 seconds.

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

~ Nucleating agents that can be used in the present invention include conventional ones.

All compounds developed for the purpose of nucleating endothermic silver halide can be applied. Two or more types of nucleating agents may be used in combination. Let me explain in more detail.

As a nucleating agent, for example, [Research Disclosure]
Magazine N (122534 (Published January 1983, pages 50-54), Identification 15162 (Published November 1976, pp. 76-77)
page) and the same magazine 23510 (November 1983 issue 34
6-352).

These are quaternary heterocyclic compounds (-compounds represented by formula (N-I)), hydrazine compounds (-formula 1: N-n
) and other compounds.

General formula (N-I) (In the formula, 2 represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and 2 may be substituted with a substituent. R1 is an aliphatic group and R2 is a hydrogen atom, an aliphatic group, or an aromatic group. R1 and R may be substituted with a substituent. However, R2 is a hydrogen atom, an aliphatic group, or an aromatic group.

At least one of the groups represented by R1, R2 and 2 contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R1 and 82 form a 6-membered ring to form a dihydropyridinium skeleton. do. Sara KR
', one of the substituents of R2 and 2 is X'
(-L'+ may be present. Here, X is a group promoting adsorption to silver halide, and L is a divalent linking group.

Y is a counter ion for charge balance, n is 0 or l, and 1m is O or 1. ) To explain in more detail, the heterocycle completed by 2 is 1, for example, quinolinicum, penzothiazolicum.

Benzimidazolium, pyridinium, thiazolinium, thiazolicum, naphthothiazolium, selenacylitam, penzoselenazolicum, imidazolicum, tetrazolium, indolenium, vilorinicum, acridinium, phenanthridinium, isoquinolinicum, oxazolicum, 7-oxazolicum and benzoxasicum Liumium nucleus is mentioned. As the substituent of 2, an alkyl group,
alkenyl group, aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryloxy group,
Halogen atom, amino group, alkyloxy group, arylthio group, acyloxy group, acylamino group, sulfonyl group, sulfonyloxy group.

Sulfonylamino group, carxyl group, acyl group.

Carbamoyl group, sulfamoyl group, sulfo group.

Cyano group, ureido group, urethane group, carbonate ester group,
Examples include hydrazine group, hydrazone group, and imino group. As the substituent 2, for example, at least one is selected from the above substituents, but in the case of two or more substituents, they may be the same or different. Moreover, the above-mentioned substituents may be further substituted with these substituents.

Furthermore, as a substituent for 2, a heterocyclic quaternary ammonium group completed with 2 via a suitable linking group may be included. In this case, it takes a so-called dimer structure.

Preferable examples of the heterocycle completed by 2 include quinolinium, benzothiazolium, benzimidazolium, pyridinicum, acridinium, phenanthridinium, and inquinolinium nuclei. More preferred are quinolinium and benzothiazolium, and most preferred is quinolinium.

The aliphatic groups of R1 and R2 are an unsubstituted alkyl group having 1 to 18 carbon atoms and a substituted alkyl group having 1 to 18 carbon atoms in the alkyl portion. Examples of the substituent include those described as substituent 2.

The aromatic group represented by R2 has 6 to 20 carbon atoms, and examples include phenyl group and naphthyl group. Examples of the substituent include those described as substituent 2. R2 is preferably an aliphatic group, most preferably a methyl group or a substituted methyl group.

At least one of the groups represented by R, R and 2 is an alkyl group, an acyl group, or a hydrazine group.

Alternatively, a dorasin group may be M, or R1 and R2 may form a 6-membered ring to form a dihydropyridinium core, which is substituted with the group described above as a substituent for the group represented by 2. may have been done.

It is preferable that at least one of the groups or substituents on the ring represented by R, R and 2 is an alkynyl group or an acyl group, or that R and R are linked to form a dihydropyridinium core, and Most preferably, it contains at least one alkynyl group.

Preferred examples of the adsorption promoting group to silver halide represented by Xl include a thioamide group, a mercapto group, and a 5- or 6-membered nitrogen-containing heterocyclic group.

These may be substituted with the substituents mentioned above. The thioamide group is preferably an acyclic thioamide group (for example, a thiourethane group).

thioureido group, etc.).

The mercapto group of Xl is particularly a heterocyclic mercapto group (eg 5-mercaptotetrazole).

3-mercapto-1,2,4-triazole, 2-mercapto-1,3,4-thiadiazole, etc.) are preferred.

The 5- to 6-membered nitrogen-containing heterocycle represented by Xl is composed of a combination of nitrogen, oxygen, sulfur, and carbon,
Preferred are those that produce imino scissors, such as benzotriazole.

The divalent linking group represented by Ll includes C1N-S,
An atom or atomic group containing at least one type of O.

Specifically, 9, for example, alkylene/group.

Alkenylene group, alkynylene group, arylene group.

-0-1-3-, -NH-1-N=, -Co-.

-5O2- (These groups may have a substituent)
1, etc. alone or in combination.

Examples of the counter ion Y for charge balance include bromide ion, chloride ion, iodide ion, p-toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfone ion, thiocyanate ion, etc. It will be done.

Examples of these compounds and their synthesis methods can be found in, for example, Research Disclosure (Research Dig-e).
Losurs) magazine Na22534 (published January 1983.

50-54), and Nα23213 (1983.8
Patents cited in 2013, pp. 267-270).

Special Publications No. 49-38164 and No. 52-19452.

JP-A No. 52-47326, JP-A No. 52-69613, JP-A No. 52-3426, JP-A No. 55-138742, JP-A No. 60-
No. 11837, U.S. Pat. No. 4,306.016, and U.S. Pat. No. 4,471,044.

Specific examples of the compound represented by the general formula (N-I) are listed below, but the invention is not limited thereto.

(N-I-1) (N-I-2) (N-I-3) (N-I-4) (N-I-5) CH2CH2CHO (N-I-6) H5 (N-I-7 ) (N-I-8) S cu2c=cu (N-I-9) (N-I-10) (N-I-11) (N-I -12) (N-I -13) (N- I-14) CH2CmiC)l General formula (N-II) R"R" (wherein R represents an aliphatic group, aromatic group, or heterocyclic group, R is a hydrogen atom, an alkyl group, Aralkyl group, aryl group, alkoxy group, aryloxy group, father represents amino group; G is carzenyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (HN=
C), and R and R are both hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group.

Represents either an arylsulfonyl group or an acyl group. However, a hydrazone structure ('>NN=C) may be formed by including G, R, R, and hydrazine nitrogen. Further, the groups described above may be substituted with a substituent if possible. To explain in more detail, R may be substituted with a substituent, and examples of the substituent include the following. These groups may be further substituted. For example, an alkyl group, an aralkyl group, an alkoxy group, an alkyl or aryl group, a substituted amino group, an acylamino group, a sulfonylamino group.

Freid group, cretane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group.

Alkylthio group, arylthio group, sulfonyl group.

Sulfinyl group, hydroxy group, halokea atom.

These include a cyano group, a sulfo group, and a carxyl group.

Among these, ureido groups are particularly preferred.

These groups may be linked to each other to form a ring when possible.

R21 is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group (eg, phenyl group, naphthyl group, etc.).

Among the groups represented by R22, preferred are a hydrogen atom, an alkyl group (e.g., methyl group), or an aralkyl group (e.g., 0-hydroxybenzyl group, etc.),
Particularly preferred is a hydrogen atom.

As the substituent for R22, in addition to the substituents listed for R, for example, an acyl group, an acyloxy group, an alkyl or aryloxycarginyl group, an alkenyl group, an alkynyl group, a yanitro group, etc. are applicable.

These substituents may be further substituted with these substituents. Further, if possible, these groups may be linked to each other to form a ring.

R21 or R, especially R, may contain a diffusion-resistant group such as a coupler, a so-called palast group, and is particularly preferably linked with a ureido group).

Group X+ that promotes adsorption to the surface of silver halide grains
It may have L+n1I2. Here, X is the general formula (
Represents the same meaning as X in N-I).

Preferably, it is a thioamide group (excluding thiosemicarbazide and its substituted products), a mercapto group, or a 5- or 6-membered nitrogen-containing heterocyclic group. L represents a divalent linking group and has the same meaning as - in formula (N-I). m2 is 0 or 1.

More preferably, X2 is an acyclic thioamide group (e.g., thioureido group, thiourethane group, etc.), a cyclic thioamide group (i.e., a mercapto-substituted nitrogen-containing heterocycle, such as a 2-mercaptothiadiazole group, a 3-mercapto-1
, 2,4-1 lyazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzoxazole group, etc.), or nitrogen-containing heterocyclic group (e.g., benzo Triazole group.

(benzimidazole group, indazole group, etc.).

The most preferable X2 varies depending on the photosensitive material used. For example, when using a color material (so-called coupler) that forms a dye through a coupling reaction with an oxidized form of a p-7 22-diamine-based developer in a color sensitive material, X is a mercapto-substituted nitrogen-containing hetero The ring is preferably a nitrogen-containing heterocycle that forms iminosilver. Also in color sensitive materials.

When using a coloring material (so-called DRR compound) that generates a diffusible dye by cross-oxidizing an oxidized developer
X and X are acyclic thioamide groups.

Or a mercapto-substituted nitrogen-containing heterocycle is preferred.

Further, in a black-and-white sensitive material, X is preferably a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver.

Hydrogen atoms are most preferred as R2S and R24.

-G in formula (N-II) is most preferably a carzenyl group. .

Further, as the formula (N-I[), those having an adsorption group to silver halogenide or those having a ureido group are more preferable.

Examples of these compounds and their synthesis methods are as follows: 1.
For example, U.S. Patent No. 4,030,925;
No. 80,207, No. 4,031,127, No. 3,
No. 718,470, No. 4,269,929, No. 4
, 276,364, 4,278,748, 4,385,108, 4,459,347, 4,478,928, 4,560,638 ,
British Patent No. 2,011,391B, 1983-1974
No. 729, No. 55-163533, No. 55-7453
No. 6, and No. 60-179734.

Other hydrazine-based nucleating agents include 1, for example, JP-A No. 5
No. 7-86829, U.S. Patent No. 4,560°638,
No. 4,478, as well as No. 2,563.785 and No. 2,588,982.

Specific examples of the compound represented by general formula (N-II) are shown below. However, the present invention is not limited to the following compounds.

(N-II-1) (N-n-2) (N-II-3) (N-II-4) (N-n-6) (N-ll-7) (N-n-8) h3 (N-II-9) (N-n-10) (N-If-11) (N-n-12) (N-n-13) (N-II-14) (N-II-15) ■ CH2CH25H (N-n-17) (N-n-21) (N-n-22) (N-n-23) (t)c5H41 (N-II-24) The nucleating agent used in the present invention is It can be contained in the photosensitive material or in the processing solution for the photosensitive material, preferably in the photosensitive material.

When it is contained in a sensitive material, it is preferably added to the internal temperature type silver halogenide emulsion layer during coating.

Alternatively, it may be added to other layers, such as intermediate layers, undercoat layers, and pack layers, as long as the nucleating agent diffuses during processing and adsorbs to the silver halide. When adding a nucleating agent to the processing solution,
It may be contained in a developing solution or a low-〇 pre-bath as described in JP-A-58-178350.

If a nucleating agent is included in the sensitive material, how much should it be used?

The amount of halokene (tJj is preferably 10 to 10 mol, more preferably 10 to 10 mol per 1 mol of tJj).

In addition, when adding a nucleating agent to the processing solution, its use i is as follows:
It is preferably 10 to 10 mol, more preferably 10 to 10 mol per liter.

Increase maximum image density. Lower the minimum image density.

Improves the storage stability of photosensitive materials. Alternatively, the following compounds can be added for the purpose of speeding up development.

Hydroquinones (e.g. U.S. Pat. No. 3,227°55)
No. 2, No. 4,279,987): Chromans (eg, US Pat. No. 4,268,621).

JP-A-54-103031, Research Disclosure Journal 18264 (published June 1979) 333~
Compounds described on page 334); Quinones (e.g. Research Disclosure Magazine 21206 (December 1981)
Compounds described on pages 433-434); Amines (for example, U.S. Pat. No. 4,150,993 and JP-A-58-17
4757); oxidizing agents (e.g., compounds described in JP-A-60-260039, Research Disclosure magazine Nα16936 (published May 1978), pages 10-11); catechols (e.g., JP-A-60-260039, Research Disclosure magazine Nα16936 (published May 1978), pages 10-11);
No. 21013 and No. 55-65944.

Compounds that release nucleating agents during development (e.g. compounds described in JP-A-60-107029); Thioureas (e.g. compounds described in JP-A-60-95533); Spirobis ingens ( For example, layer opening 55-
65944).

Nucleation accelerators for speeding up nucleation include tetrazaindenes, triazaindenes, and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. Seindens and Japanese Patent Application No. 136948/1983 (pages 2-6 and 16
~43 pages).

Compounds described in Japanese Patent Application No. 61-136949 (pages 12 to 43) K can be added.

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

(Mu-1) (Mu-2) S■ (A-3) C person-4) R (A-5) 1fl (A-6) (Mu-7) Sl'l CH38IN (Mu-8) (Mu-8) -9) (Mu-10
) (Mu-U) (Mu-12) (Mu-13) (A-14) CM.

(A-15) (A-16) (A-17) (A-18) (A-19) (A-20) (A-21) (A-22) (A-Z3) (Mu-24) (A-25) (A-26) (A-27) (A-28) (A-29) (A-30) (A-31) The nucleation accelerator is contained in the photosensitive material or in the processing solution. However, it is preferable to include it in the internal latent image type silver halide emulsion or other hydrophilic colloid layers (intermediate layer, protective layer, etc.) in the photographic material. Particularly preferred is a layer in or adjacent to a silver halide emulsion.

The amount of nucleation accelerator added is 10-7 per mole of silver halide.
-10 mol is preferable, more preferably 10-10 mol
It is a mole.

In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, 10-8 to 10-s per 11
It is preferably mol, more preferably 10-7 to 10 mol.

Further, two or more types of nucleation accelerators may be used in combination.The color developing solution used in the development of the light-sensitive material of the present invention does not substantially contain a silver halide solvent, and preferably contains an aromatic primary amine. It is an alkaline aqueous solution containing a color developing agent as a main component, and - of the color developing solution is 11.5 or less, preferably 9.5 or more, and more preferably 11.2 to 9.8.

Further, the color developing solution of the present invention does not substantially contain benzyl alcohol. When preparing a low-replenishment type color developer replenisher, if it contains benzyl alcohol, the dissolution rate is slow, so it may take a long time to dissolve or a tar-like substance may be generated. On the other hand, a color developing solution that does not contain benzyl alcohol has the advantage that even if it is a low replenishment type, it has a short dissolution time and does not generate tar-like substances, making it easy to prepare a low replenishment type developer replenisher. In addition, when performing continuous processing using a color developing solution that does not contain benzyl alcohol, by preventing fluctuations in the solution composition, the replenishment amount can be reduced to less than half of the standard replenishment amount (165 m/m or less).
However, a consistent finish is obtained with no tar-like substance formation and no change in stain.

Additives used in the color developing solution of the present invention include Japanese Patent Application No. 59-1667, pages 14 to 22;
No. 9-118418 Specification 1! Various compounds described on pages 45 to 50 and pages 11 to 22 of Japanese Patent Application No. 61-32462 can be used. Furthermore, the color developing solution of the present invention may contain antifoggants such as tetrazaindenes, benzindazoles, benzotriazoles, benzimidazoles, benzothiazoles, hendioxazoles, and 1-phenyl-5-mercaptotetrazoles. Particular preference is given to using heterocyclic thiones, aromatic and aliphatic mercapto compounds.

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

The bleaching process may be carried out simultaneously with the fixing process in a single bath bleach-fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is followed by bleach-fixing, or a method in which bleaching and fixing is carried out after fixing. Aminopolycarzenate iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention. Additives used in the bleaching solution or bleach-fixing solution of the present invention include those described in Japanese Patent Application No. 22-32-32462.
Various compounds described on page 0 can be used. If the color developing solution does not contain benzyl alcohol, the leucoization reaction of the cyan dye will occur in the bleach-fixing solution.
Therefore, the amount of bleach-fix solution or oxidizing agent can be lowered.

The replenishment amount of bleach-fix solution is usually about 330 d/m,
When the color developer does not contain benzyl alcohol, it is possible to lower the replenishment amount to 69 ml/yj or less.

After the desilvering step (bleach-fixing or fixing), treatments such as water washing and/or stabilization are performed. 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 to 30 times, the amount of prebath brought in per unit area of the photosensitive material.

The above-mentioned formula [
Preferred embodiments of the nucleating agent of formula (N-I) and [:N-I[] are as follows. (1) In the nucleating agent of formula (N-I), the complex completed by 2 When the ring is a quinolium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, and inquinolinium nucleus.

(2) In the nucleating agent of formula (N-I), when the adsorption promoting group to silver halide represented by Xl is composed of a thioamide group, a peterocyclic mercapto group, or a nitrogen-containing heterocycle that forms iminosilver.

(3) In the nucleating agent of formula (N-I), when the heterocycle to which 2 is completed is quinolinium, benzothiazolium or benzimidazolium.

(4) In the nucleating agent of formula (N-I), when the heterocycle completed by 2 is quinolinium or benzothiazolium.

(5) In the nucleating agent of formula (N-I), when the heterocycle completed by 2 is quinonium.

(6) In the nucleating agent of formula (N-I), when R, R or 2 has an alkynyl group as a substituent (7) In the nucleating agent of (6), a heterocycle completed by 2 If is a quinolium.

(8) The nucleating agent of (7) has a silver halide adsorption promoting group represented by Xl.

(9) When the adsorption-promoting group to silver halide in (8) is composed of a thioamide group, a heterocyclic mercapto group, or a nitrogen-containing heterocycle that produces iminosilver, in the nucleating agent of formula (N-I): , when the group represented by G -R22 is a formyl group.

al) in the nucleating agent of formula (N-If), dan and 12
When 4 is a hydrogen atom and the group represented by G-122 is a formyl group.

(L■ In the nucleating agent of formula (N-If), R21 is an aromatic group and has a ureido group as a substituent.

0 In the nucleating agent of formula (N-If), R21 is an aromatic group, and the substituent is a heterocyclic mercapto group.

When it has an adsorption promoting group to silver halide consisting of an aryl mercapto group, an aliphatic mercapto group, or a nitrogen-containing heterocycle that forms imino silver.

In the nucleating agent for α4 ell), R is an aromatic group, and the substituent is a heterocyclic mercapto group, a group that promotes adsorption to silver halide consisting of a nitrogen-containing heterocycle that forms imino silver, or a ureido group. If you have.

EXAMPLES The present invention is illustrated by the following examples, but the present invention is not limited in any way by these examples. In carrying out the examples, the following emulsions A and B were prepared.

Emulsion A: An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per 1 mole of A1, while stirring vigorously at 75°C for about 20 min. They were added simultaneously over several minutes to obtain an octahedral monodispersed silver bromide emulsion with an average grain size of 0.4 μm. To this emulsion were added sodium thiosulfate and potassium chloroaurate (tetrahydrate) each having a content of 12 jlP per mole of silver.
Chemical sensitization treatment was performed by heating at 5° C. for minutes.

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

After washing with water and desalting, sodium thiosulfate and chloroauric acid (tetrahydrate) were added to this emulsion in an amount of 4 molar per mole of silver.
A chemical sensitization treatment was performed by heating at 0° C. for 60 minutes to obtain an internal latent film type silver halide emulsion A.

Emulsion B per 11 KBro, 5 mol, Naα 0.2 mol and K
Io, 3 gelatin in a mixture IJ with a concentration of 0015 molar
After adding 09 and melting, add 1 mol/J of silver nitrate at 60°C.
A solution of 700 Ce was added to the above mixture over 20 minutes, and physical ripening was further performed for 20 minutes.6 Next, after washing with water to remove water-soluble Harai P, 20 g of gelatin was added, and further water was added. The total volume is 1200cc.
It was prepared as follows. A silver halide emulsion with an average grain size of 0.4 μm was obtained.

To 300 CC of this emulsion, 500 CC of a 1 mol/J silver nitrate aqueous solution and 50 CC of an aqueous solution containing 6 mol of sodium chloride and 0.7 mol of potassium bromide per IJ at 60°C.
0 cc was added at the same time to precipitate a silver chloride shell, which was then washed with water. Silver halide emulsion B having an average grain size of 0.7 μm was obtained.

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

The coating solution was prepared as follows.

Preparation of first layer coating solution Add and dissolve ethyl acetate 10 and 4 m of solvent (c) to 2.3 J of nitrogen coupler (a) 101 and color image stabilizer (b), and dissolve this solution in 10% dodecylbenzenesulfonic acid. 1 containing sodium 5TILl
It was emulsified and dispersed in 90% 0% gelatin aqueous solution. On the other hand, the following red-sensitive dye was added to the silver halide emulsion (containing 70 Jil/Kg of Ag) at a concentration of 2.0 per mole of silver halide.
90 g of a red-sensitive emulsion was prepared by adding X10-' moles. The emulsified dispersion, the emulsion, and the development accelerator (d) were mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained, thereby preparing a coating solution for the first layer.

The coating solutions for the second to seventh layers were also prepared in the same manner as the fa1 layer coating solution. 1-oxy- as gelatin hardening agent in each layer
3,5-dichloro-8-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Red-sensitive emulsion layer; Green-sensitive emulsion layer: ↑Sensitive emulsion layer; Anti-irradiation dye for the green-sensitive emulsion layer; Anti-irradiation dye coupler for the red-sensitive emulsion layer; etc. The structural formulas of the compounds used in this example are as follows: ).

The following dyes were used as anti-irradiation dyes.

Engineering 0 use ＾

^-J3-,
,
w (1) Yellow coupler (c) Color image stabilizer The color photographic paper thus prepared is subjected to wedge exposure (1/10 seconds, 1 OCMS) and then subjected to the following processing step A or B to produce magenta. Color image density was measured. At that time, during color development, from 15 seconds after the start of development, to 910 seconds of overlay exposure (0.5 lux on the photosensitive material film, color temperature 54
00K) was applied.

The results obtained are shown in Table 3.

Processing step A Time Temperature Color development 2 minutes 37℃ Bleach fixing 40 seconds 37℃ Stable ■ 20 seconds 37℃ Stable ■ 20 seconds 37℃ Stable ■ 20 seconds 37℃ The stabilization bath replenishment method is as follows: A so-called counter-current replenishment system was adopted in which the overflow liquid of stable bath (1) was introduced into stable bath (2), and the over-70 liquid of stable bath (2) was introduced into stable bath (2).

[Color developer]

Mother liquid diethylenetriaminepentaacetic acid 2. OI benzyl alcohol 12.8.9 diethylene glycol 3.41 sodium sulfite 2.0 p sodium bromide 0.26 g sulfuric acid and p-roxylamine z-6=9 sodium chloride
3.20p3-Methyl-4-amino-N-4,25g Ethyl-N-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30.09 Fluorescent brightener (stilbene type) i, o, y
Tetrazaindene derivative 50 ■ (Those listed in Table 3) Add water 1000 11j
PH10,20- was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution]

Ammonium thiosulfate 110 9 Sodium bisulfite 10 9 Diethylenetriaminepentaacetic acid 56 Ammonium 9ate iron (■) monohydrate Ethylenediaminetetraacetic acid 2 5J Sodium dihydrate 2-mercapto-1,3,Q,5,1it4-triazole water Add 1ooo yPH6
, 5- were adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother liquor l-hydroxyethylidene 1.6 1Lt
-1,1'-Diphosphonic acid (60) Bismuth chloride 0.35,9 PolyvinylpyrroliP 0.25p Aqueous ammonia 2.5゜Nitrilotriacetic acid, 3Na 1095-Chloro-2-methyl-450Gisothiazoline -3-one 2-octyl-4-isothia 50 ■Sily/-3-one fluorescent brightener (4,4'-cya 1.0g minostilbene type) Add water to 1000 ml pH
7,5- was adjusted with potassium hydroxide or hydrochloric acid.

Processing step B is the same as processing step A except for removing benzyl alcohol and diethylene glycol from the color developer.
I made it the same as

As can be seen by comparing magenta density processing step A in Table 3 and processing step B, which differs only in that it does not contain benzyl alcohol or its solvent, in the Hikari Kabushi method, a developer containing the tetrazaindene derivative of the present invention is used. It can be seen that direct positive color images with sufficiently high maximum image densities (omax) can be obtained without adversely affecting the minimum image density (Dmln) even when benzyl alcohol is excluded.

Similar results were obtained when cyan and yellow densities were measured.

Example 2 In Example 1, when producing color photographic paper, the nucleating agent of the exemplified compound (N-i-17) was added to 9 mol of silver per mole of silver.
3.0X10 mol and the nucleation accelerator of the above-mentioned exemplary compound (A-2) were added in the amount of 4.0XlO-4 mol per mol of silver.
Exactly the same as Example 1 except that the cyan coupler (&) used in the first layer was changed to the cyan coupler (a') shown below. Color photographic paper was created.

Cyan coupler (a') (black and then the turnip applied in Example 1) was exposed to light and the color development processing time was set to 1 minute and 50 seconds, and the tetrazaindene derivatives shown in Table 4 were added to the developer solution. The color photographic paper was subjected to post-exposure development treatment (processing step A or B) in exactly the same manner as in Example 1 except for the following, and the magenta color image density was measured.

The results obtained are shown in Table 4.

It can be seen from Table 4 that the same results as in Example 1 can be obtained even when the magenta density chemical Kabushi method is applied.

Similar results were obtained when cyan and yellow densities were measured.

Example 3 In place of the nucleating agent and nucleating accelerator used in Example 2, the nucleating agent shown in Table 5 was added at a concentration of 4.5 x 10 per mole of silver.
-5 mol Examples Except for changing the yellow coupler (A) shown in Table 1 to the 1.3 and 5 layers and used in the 5th layer to the yellow coupler (t') shown below. Then, in place of the tetrazaindene derivative shown in Table 4, 50119/l of the tetrazaindene derivative of the above-mentioned exemplary compound (2) was added to the color developer, and -11.2/l of the tetrazaindene derivative shown in Table 4 was added. Color photographic paper was subjected to post-exposure and development processing (processing steps C and D) in the same manner as in Example 2, except that the following steps were taken:

Processing steps C and D were the same as processing steps A and B of Example 2, except that the temperature was 35°C, the -1 of the color developer was set to 11.2, and the development time was 2 minutes and 50 seconds. The yellow color density was measured and the results are shown in Table 5.

Table 5 Yellow density As can be seen from the results in Table 5, the formula [N-11,C
The use of nucleating agents of the formula N-n) proves to be advantageous, as direct positive color images with particularly good maximum image densities are obtained.

Similar results were obtained for magenta and cyan densities.

Example 4 Using the following cyan, magenta, and yellow couplers, an emulsion prepared in the same manner as Emulsion 2-1 described in Example 2 of JP-A-55-127549 was used, as shown in Table 6. Color photographic paper was prepared in the same manner as in Example 1 except that a nucleating agent was used (cyan coupler) 1:l (molar ratio) mixture (yellow coupler) (t) C5H11 (magenta coupler) α This color print The paper was subjected to a running color development process at 37° C. for 16 hours and examined for cyan stain.

The results are shown in Table 6.

Processing step E was as follows, except that the color development time was 2 minutes and 30 seconds.
The treatment step B is the same as that of Example 2, and the treatment step E' is the same as the treatment step B of Example 2.
The process is the same as process E except that it is included.

Processing steps F and F' had a color development time of 1 minute and 30 seconds and - was set to 11.5, and processing steps G and G' had a color development time of 1 minute and 30 seconds and - was set to 12.0. It is the same as each can treatment process E and E'.

Treatment step E/ comprising the tetrazaindene derivative of the present invention
, F/ had almost no increase in stain due to high-temperature running compared to processing steps E and FK.

However, in treatment steps G and G' at pH 12.0, no effect of reducing stain by the tetrazaindene derivative was observed.

Example 5 Same as Example 4 except that nucleating agent 2.5 X 10-5 mol/Ag mol and nucleation accelerator 3.5 X IO'' mol/Ag mol were used as shown in Table 7. Color photographic paper was prepared in the same manner, exposed and developed in the same way as processing E and E/ in Example 4 (however, no fogging light was applied) to obtain a positive color image, and the cyan stay/ was measured. The results are shown in Table 7.

Table 7 Results similar to those of processing steps E and E' of Example 4 were obtained in a system in which a nucleating agent and a nucleating accelerator were used together.

Example 6 Color photographic paper was prepared in the same manner as in Example 4, except that emulsion B was used, and after exposure (17100 seconds, 10 CMS), processing steps E and E' of Example 4 were applied. All of the samples subjected to treatment step E' containing the tetrazaindene derivative of the present invention (Exemplary Compound-2) had less negative reversion.

(Effects of the Invention) According to the present invention, even if an internal latent image type silver halide photosensitive material that has not been fogged in advance is processed for a short time with a low-density color developer that does not substantially contain benzyl alcohol, Direct positive color images with little decrease in color density can be formed quickly and stably.

In addition, in the present invention, it is possible to form a direct positive color image stably having a low minimum image density and a high maximum color density even though changes in the developer and composition thereof are not affected.

In addition, it is possible to effectively prevent staining that occurs when high-temperature running color development is performed using a color developer that does not substantially contain benzyl alcohol.

Furthermore, the developer of the present invention is less susceptible to air oxidation, and its performance is less likely to fluctuate when used for a long period of time.

r (3 others) ---

Claims (1)

[Claims] 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 is subjected to fogging exposure after imagewise exposure, prior to development, or during the processing step. and/or in the method of directly forming a positive color image by developing, bleaching and fixing with a surface developer containing an aromatic primary amine color developer in the presence of a nucleating agent, the color coupler itself is substantially It is a compound that is non-diffusible in nature, and that generates or releases a dye by oxidative coupling with an aromatic primary amine color developer, and that does not undergo the above development treatment.
1. A direct positive color image forming method, characterized in that it is carried out using a developer containing a tetrazaindene derivative having H11.5 or less, substantially not containing benzyl alcohol, and having no SH group.