JPS63121842A - Direct positive image forming method - Google Patents

Abstract

PURPOSE:To rapidly and stably form a direct positive image by imagewise exposing a photosensitive material having an internal latent image type photographic silver halide emulsion layer for direct positive on the support, subjecting the material to fogging exposure before or during development and developing it in the presence of a specified compd. CONSTITUTION:A photosensitive material having an internal latent image type photographic silver halide emulsion layer for direct positive on the support is imagewise exposed and subjected to fogging exposure before or during development and the material is developed in the presence of a compd. represented by the formula. In the formula, M is H, an alkali metal atom, ammonium or a group which cleaves under alkali conditions, X is (, S or Se, and each of R5-R8 is H, optionally substd. alkyl or the like. A light source emitting light within the photosensitive wavelength range of the photosensitive material may be used as a light source for the fogging exposure and a fluorescent lamp, a tungsten lamp, a xenon lamp or sunbeams are generally used. Thus, a direct positive color image hardly undergoing deterioration by air oxidation and having stable performance over a long period can be formed.

Description

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

[Conventional technology]

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

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

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

The other type uses an internal latent image type silver halide emulsion that is not fogged, and directly obtains a positive image by performing surface development either after image exposure and fogging treatment, or while performing fogging treatment. . The above-mentioned internal latent image type silver halide photographic emulsion is a type of 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. Refers to emulsion.

This latter type of method generally has higher sensitivity than the former type of method and is suitable for applications requiring high sensitivity, and the present invention relates to this latter type of method.

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2,592,250;
No. 466957, No. 2497875, No. 2588
No. 982, No. 3317322, No. 3761266
No. 3761276, No. 3796577, and British Patent No. 1151363, No. 115 (155
The main ones are those described in the specifications of No. 3 and No. 1011062.

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 Ink Process by T. H. James
of Th'e Photographic Proc
ess ) 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276. According to it, the initial imagewise exposure creates an internal latent image (Posit
Fog nuclei are selectively generated only on the surface of silver halide grains in unexposed areas due to the surface desensitization effect caused by ivholes, and then a photographic image is formed in the unexposed areas by performing a normal so-called surface development process. It is believed that a (direct positive image) is formed.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the angry light layer, which is generally called "light fogging method" (for example, British Patent No. 1,151,3
63) and a nucleating agent (nu
creating agent) is known. This latter method is discussed, for example, in ``Research Disclosure''.
losure) Magazine Volume 151 1tl 5162 (1
Published in November 1976), pages 76-78.

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

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

As described above, with the conventional fogging method, it is difficult to obtain a stable and good direct positive image. As a means to solve this problem, compounds that exhibit a nucleating effect even at a pH of 12 or lower have been proposed in Japanese Patent Application Laid-open No. 52-69613 and U.S. Patent No. 3,615.
, No. 615 and No. 3,850,638, these nucleating agents act on the silver halide during storage of the sensitive material before processing, or the nucleating agent itself decomposes. However, there is a drawback that the maximum image density after processing is reduced.

U.S. Pat. No. 3,227,552 describes the use of hydroquinone derivatives to increase the development rate of medium densities. However, even when this is used, the development speed is not sufficient, and in particular, an insufficient development speed can be obtained with a developer having a pH of 1.2 or less.

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

JP-A-55-134848 discloses a treatment solution containing a tetrazaindene compound (pH 12.0) in which a nucleating agent was present.
) to reduce the density of the small image and prevent the formation of a negative image. However, this method does not increase the maximum image density or increase the development speed.

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

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

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

[Problem that the invention seeks to solve]

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

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

Furthermore, even if the temperature and pit of a color developing solution change, the maximum image density and minimum image density do not easily change from the optimum values, and the brown color reproducibility does not change (to provide a method for directly forming a positive color image. It is in.

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

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

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

(Means for Solving the Problems) The above object of the present invention is to prepare a photosensitive material having at least one internal latent image type direct positive silver halide photographic emulsion layer on a support after imagewise exposure, before development processing, or This is achieved by providing fog exposure during the development process and performing the development process in the presence of the compound of general formula (1).

General formula (1) "In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. X represents an oxygen atom, a sulfur atom, or a selenium atom. S II II o O II II or -N-, R3, R2, R3, R4, R7, R6, R7 and R8 each represent a hydrogen atom, a substituted or unsubstituted alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc)
, substituted or unsubstituted aryl group (e.g. phenyl group, 2-methylphenyl group, etc.), substituted or unsubstituted alkenyl group (e.g. propenyl group, 1-methylvinyl group, etc.), or substituted or unsubstituted alkenyl group represents an aralkyl group (eg, benzyl group, phenethyl group, etc.). R is a linear or branched alkylene group (e.g., methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.), a linear or branched alkenylene group (e.g., vinylene group, 1-methylvinylene group, etc.), linear or branched aralkylene group (
For example, it represents a benzylidene group, etc.), an arylene group (for example, phenylene, naphthylene, etc.). The above group represented by R may be further substituted.

Z is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a nitro group, a cyano group, a substituted or unsubstituted sulfonyl group (for example, a methanesulfonyl group, an ethanesulfonyl group, a p-toluenesulfonyl group, ), carbamoyl group (e.g., unsubstituted carbamoyl group,
methylcarbamoyl group, etc.), sulfamoyl group (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, etc.), carbonamide group (e.g., acetamido group,
benzamide group, etc.), sulfonamide group (e.g., methanesulfonamide group, benzenesulfonamide group, etc.), acyloxy group (e.g., acetyloxy group, benzoyloxy group, etc.), ureido group (e.g., unsubstituted ureido group), group, methylureido group, ethylureido group, etc.), acyl group (e.g., acetyl group, benzoyl group, etc.), thioureido group (e.g., unsubstituted thioureido group,
methylthioureido group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, p-)luenesulfonyloxy group, etc.), oxycarbonyl group (e.g., methoxycarbonyl group, phenoxycarbonyl group, etc.),
Oxysulfonyl group (e.g. methoxysulfonyl group,
phenoxysulfonyl group, ethoxysulfonyl group, etc.)
, represents an oxycarbonylamino group (for example, an ethoxycarbonylamino group, a phenoxycarbonylamino group, etc.) or a mercapto group.

n represents O or 1.

In the above method, a nucleation accelerator represented by general formula (1) and a nucleating agent may coexist.

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

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

Specific examples of the compound represented by general formula [I] are shown below.

However, the present invention is not limited to this.

1.2゜3.4゜11゜The compound of general formula (1) used in the present invention is a compound of general formula (1) used in the present invention.
emischen Ge5ellschaft) 2
8.77 (1875), JP-A No. 50-37436, JP-A No. 51-3231, U.S. Patent No. 3,295,976,
U.S. Pat. No. 3,376.310, Herichte der Deutschen Hemischen Gesellschaft (Beric
hte der Deutschen Chemisch
en Ge5ellschaft ) 22.568 (
1889), ``Kame, 2483 (1'896), Journal of the Chemical Society (J.

Chem, Soc, ) 1932.1806, Journal of the American Chemical Society (J, Am, Chem, Soc, ) 7, 400
0 (1949), U.S. Patent No. 2,585,388,
No. 2,541,924, Advances in Heterocyclic Chemistry
n Heterocyclic Chemistry
) 9.165 (1968), Organic Synthesis IV
, 569 (1963), Journal of the American Chemical Society (J, Am, Che
m, Soc, ) 45.2390 (1923), Chemische Berichte
) 9.465 (1876), Special Publication Showa 4°-284
No. 96, JP-A-50-89034, U.S. Patent No. 3,10
No. 6,467, No. 3,420,670, No. 2.271
, No. 229, No. 3,137,578, No. 3,148,
No. 066, No. 3.51L663, No. 3,060,02
No. 8, No. 3,271,154, No. 3.25L691, No. 3,598,599, No. 3, 148.066,
Special Publication No. 43-4135, U.S. Patent No. 3,615,616
No. 3.420.664, No. 3,071,465, No. 2,444.605, No. 2,444.606, No. 2,444,607, No. 2,935,404, etc. according to the method described.

can be easily synthesized.

The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but especially in the internal latent image type silver halide emulsion and other hydrophilic colloid layers (intermediate layer, protective layer, etc.). It is preferable to contain it. Particularly preferred is a layer in or adjacent to a silver halide emulsion layer.

The amount of nucleation accelerator added is 10-6 per mole of silver halide.
~10-'' mol is preferred, more preferably 10-5~
It is 104 moles.

In addition, if the nucleation accelerator is added after processing, that is, to the developer or its pre-bath, the 1jl! 10-” to 1 per hit
0-3 mol is preferable, more preferably 10-7 to 10
-4 moles.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, a certain amount of silver halide emulsion is coated on a transparent support, and this is exposed to light for a fixed time of 0.01 to 10 seconds, using the following developer A (internal type developer). The maximum density measured by the usual photographic density measurement method when developed at 18°C for 5 minutes was determined by the following developer liquid) in 20
Preferred are those having densities that are at least 5 times greater, more preferably at least 10 times greater, than the maximum density obtained when developed for 6 minutes at °C.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-hydrate) 5
2.5 g KBr 5g K I
Add 0.5 g water
11 Surface type image solution Metol 2.5g! -Alcorbic acid 10gNa BO2・4H203
5g KBr 1g water added Specific examples of 1β internal latent type emulsions include the conversion type silver halide emulsion described in the specification of US Patent No. 2,592,250,
U.S. Patent No. 3,761,276, U.S. Patent No. 3,850,637
No. 3,923,513, No. 4,035,185, No. 4,395,478, No. 4,504,570,
JP 51-156614, JP 55-127549, JP 53-60222, JP 56-22681, JP 5
No. 9-208540, No. 60-107641, No. 61
Examples include core/shell type silver halide emulsions described in patents such as No. 3137, Japanese Patent Application No. 3642/1982, and Research Disclosure Magazine 1, 23510 (published November 1983), p. 236.

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

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

The average grain size of silver halide grains is 2 μ or less 0.1
μ or more is preferred, but particularly preferred is 1μ or less 0.1
It is 5μ or more. The particle size distribution may be narrow or wide, but in order to improve granularity and sharpness, the number or weight of all particles should be within ±40% of the average particle size, preferably within ±20%. So-called "monodisperse" silver halide emulsions having a narrow grain size distribution of 90% or more are preferably used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. 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 Research Disclosure magazine Nu17643-III (published December 1978, p. 23).

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. For detailed specific examples, see Research Disclosure Magazine 11kl17643-IV (December 1978).
It is in the patent described on pages 23-24 (published in May).

The photographic emulsion used in the present invention may contain an anti-fogging agent or stabilizer for the purpose of preventing fog during the manufacturing process, storage or photographic processing of the light-sensitive material, or to stabilize photographic performance. . For detailed specific examples, see Research Disclosure Magazine No. 17643-V.
I (published December 1978) and E, J. Bin (
“Stabilization of photographic silver halide emulsions” (Binn)
Focal Press) C”5tabilizati
on of PhotographicSilver
Halide Emulsions” (Foca
1, Press), published in 1974.

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

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

These specific methods are described, for example, in British patent L15L36.
No. 3, Special Publication No. 45-12710, No. 45-12709
No. 58-6936, JP-A-48-9727, JP-A No. 56-137350, JP-A No. 57-129438, JP-A No. 5
No. 8-62652, No. 58-60739, No. 58-7
No. 0223 (corresponding U.S. Pat. No. 4'440851), No. 5
B-120248 (corresponding European Patent No. 8910182). For photosensitive materials that are sensitive to all wavelengths, such as color photosensitive materials, Japanese Patent Application Laid-Open No. 56-13735
A light source with high color rendering properties (as close to white as possible) such as those described in No. 0 and No. 58-70223 is preferable. The illuminance of the light is 0.01 to 2000 lux, preferably 0.05
-30 lux, more preferably 0.05-5 lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferred. To adjust the illuminance,
The luminous intensity of the light source may be changed, the light may be attenuated by various filters, the distance between the photosensitive material and the light source, and the angle between the photosensitive material and the light source may be changed. Using weak light at the beginning of exposure,
Exposure times can then be shortened by using stronger light.

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

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

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

In the present invention, a nucleating agent may be used in addition to the nucleating accelerator. As such a nucleating agent, all compounds conventionally developed for the purpose of nucleating latent silver halide can be used. Two or more types of nucleating agents may be used in combination. To explain in more detail, the nucleating agent is, for example, Research Disclosure Magazine 22,534 (1
(Published in January 1983, pp. 50-54), and these are broadly classified into three types: hydrazine compounds, quaternary heterocyclic compounds, and other compounds.

First, as a hydrazine compound, for example, the above-mentioned Research Disclosure Journal 11h15, 162 (197
Published in November 2016, pp. 76-77) and the same magazine, 23,510
(Published November 1983, pages 346-352).

More specifically, those described in the following patent specifications can be mentioned. First, as an example of a hydrazine-based nucleating agent having a silver halide adsorption group, for example, U.S. Patent No. 4,03
No. 0,925, No. 4,080,207, No. 4,0
No. 31,127, No. 3,718,470, No. 4.
No. 269,929, No. 4,276.364, No. 4
, 278,748, 4,385.108, 4,459,347, British Patent No. 2,011,391
No. B, JP-A-54-74,729, JP-A No. 55-163
, No. 533, No. 55-74, 536, No. 59-195
, No. 233, No. 59-200, No. 231, No. 59-20
No. 1,045, No. 59-201,046, No. 59-2
No. 01,047, No. 59-201,048, No. 59-
No. 201,049, No. 60-170,843, No. 60
Examples include those described in No. 179,734 and Research Disclosure Magazine No. 15,750 (Page 54, published May 1977).

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
Examples include compounds described in US Pat. No. 7-86,829, US Pat. No. 4,560.638, US Pat. No. 4.478, US Pat.

Next, examples of quaternary heterocyclic compounds include the aforementioned Research Disclosure Magazine 11h22,534, Japanese Patent Publications No. 49-38,164, No. 52-19,452, No. 5
2-47,326, JP-A No. 52-69,163, JP-A No. 52-3.426, JP-A No. 55-138,742, JP-A No. 6
No. 0-11,837, U.S. Patent No. 4,306,016, and Research Disclosure Magazine, Floor 23.
213 (published August 1983, pages 267-270).

The nucleating agent used in the present invention can be contained in the sensitive material or in the processing solution for the sensitive material, preferably in the sensitive material.

When incorporated into a sensitive material, it is preferably added to the latent 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 other layers. For example, an intermediate layer and an undercoat layer may also be added to the bank 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 mol of silver halide;
More preferably, it is 10-7 to 10-3 mol.

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

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

Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. These cyans that can be used in the present invention,
Specific examples of magenta and yellow couplers are ``Research Disclosure'' magazine No. 17643 (1978
Published in December 2017) p25 ■-D section, gap 18717 (1
(published in November 1979) and Japanese Patent Application No. 61-32462, and the patents cited therein.

Among them, representative examples of yellow couplers that can be used in the present invention include oxygen atom elimination type and nitrogen atom elimination type yellow m:equivalent couplers. Especially α−
Pivaloylacetanilide couplers are preferred because they provide excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

In addition, as the 5-pyrazolone magenta coupler that can be preferably used in the present invention, a 5-pyrazolone coupler in which the 3-position is substituted with a -ruamino group or an acylamino group (especially a sulfur atom-eliminating two-equivalent coupler) is preferred. be.

More preferred are pyrazoloazole couplers, and among them, pyrazolo (5,1-c) (1,2,4)) liazoles described in U.S. Pat. No. 3,725,067 are preferred; The imidazo[1,2-b)pyrazoles described in U.S. Pat. No. 4,500;630 are more preferable in terms of the low yellow side absorption of the dye and the light fastness, and the compounds described in U.S. Pat. No. 4,540,654 are more preferable. Pyrazolo CI, 5-b) C1,2,4) triazoles are particularly preferred.

Cyan couplers that can be preferably used in the present invention include:
U.S. Patent Nos. 2,474,293 and 4,052,21
naphthol-based and phenol-based couplers described in US Pat. .5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness.

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

The standard amount of color coupler used is photosensitive Haloken (
The range is from 0.001 to 1 mole per mole of 11, preferably from 0.01 to 0 for yellow couplers.
．． 5 mole, 0.003 to 0.00 for magenta coupler.
3 mol, and for cyan couplers 0.002 to 0.
It is 3 moles.

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

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

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols, mainly 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, and bisphenols;
Typical examples include gallic M derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or etesur derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)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.
Compounds having a hindered amine and a hindered phenol fractional structure in the same molecule as described in US Pat. No. 4,268,593 give good results. In addition, in order to prevent deterioration of magenta dye images, especially deterioration caused by light, spiroindanes described in JP-A-56-159644, hydroquinone diethers or monoethers as described in JP-A-55-89835, Substituted chromans give favorable results.

Representative examples of these anti-fading agents are disclosed in Japanese Patent Application No. 32462/1986.
No., pp. 401-440. These compounds are usually 5% for their respective color couplers.
The purpose can be achieved by co-emulsifying with the coupler and adding it to the photosensitive layer in an amount of from 100% by weight. In order to prevent 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 compounds are listed in Japanese Patent Application No. 61-32462, 391-40.
It is written on page 0.

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

The photosensitive material of the present invention includes dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, capping agents, air fog prevention agents, coating aids, hardeners, antistatic agents, etc. A slippery improver, etc. can be added. Typical examples of these additives are “Research Disclosure Magazine Na17643tI-XI [1 (December 1978 issue) p.
Published in January) p'647-651.

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

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
At least one green-sensitive emulsion layer and one blue-sensitive emulsion layer each.
have one. The order of these layers can be arbitrarily selected as necessary. The preferred 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. 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.

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with auxiliary layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer, a bank layer, and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are provided in Research Disclosure Journal, Section 17643
Published in December 1978) on page 28, European Patent No. 0,182,253, and JP-A-61-97655.
It is coated on the support described in No. Also, the same magazine No. 176
The coating method described in Section 43XV, pages 28 to 29 can be used.

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

For example, typical examples include color reversal film for slides or television, and color reversal paper. It can also be used for full-color multifunction machines and color hard copies for saving images on CRTs. The present invention can also be applied to a black-and-white light-sensitive material using a three-color coupler mixture described in Research Disclosure magazine Nα17123 (published July 1978).

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is
Examples include those described in No. 1-32462, pages 374-391.

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

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

The color developing solution used in the development of the light-sensitive material of the present invention does not substantially contain a silver halide solvent, and is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Examples of additives used in the color developing solution of the present invention include JP-A-60-144739, pages 14-22, JP-A-1-262161, pages 45-50, and Japanese Patent Application No. 1-262161, pages 45-50. Various compounds described on pages 11 to 22 of Specification No. 32462 can be used.

Furthermore, the color developing solution of the present invention contains antifogging agents such as tetrazaindenes, benzindazoles, benzotriazoles, benzimidazoles, benzothiazoles, benzoxazoles, and 1-phenyl-5-mercaptotetrazole. 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 treatment may be carried out simultaneously with the fixing treatment in a one-bath bleach-fixing process, or may be carried out separately. Furthermore, in order to speed up the processing, a method may be employed in which bleaching is followed by bleach-fixing, or a method in which bleaching and fixing is carried out after fixing. An aminopolycarboxylic acid iron complex salt is usually used as a bleaching agent in the bleaching solution or bleach-fixing solution of the present invention.

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

As additives used in the water washing and stabilization steps, various compounds described in Japanese Patent Application No. 32462/1983, pages 30 to 36, can be used.

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

〔Example〕

Emulsion A: An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution containing 0.3 g of 3.4-dimethyl-1,3-thiazoline-2-thione per mole of Ag at about 75°C with vigorous stirring. They were added simultaneously over a period of 20 minutes to obtain an octahedral monodisperse silver bromide emulsion with an average grain size of 0.4 μm. To this emulsion were added 6 mg of sodium thiosulfate and potassium chloroaurate (tetrahydrate) per mole of silver at 75°C.
Chemical sensitization treatment was performed by heating at C for 80 minutes.

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

After washing with water and desalting, this emulsion contains 1.5 μm per mole of silver.
Chemical sensitization was carried out by adding sodium thiosulfate and chloroauric acid (tetrahydrate) and heating at 60°C for 60 minutes to obtain internal latent image type silver halide emulsion A.

Emulsion B Add 30 g of gelatin to mixture 11 with a concentration of 5 mol of KBrO, 0.2 mol of NaCn, and 15 mol of K per IIl and dissolve it, then add 700 cc of a solution containing 1 mol/l of silver nitrate to the above mixed solution at 60°C. was added over a period of 20 minutes, and was further physically aged for 20 minutes.

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

To 300 cc of this emulsion, 500 cc of a 1 mol/β aqueous silver nitrate solution and 500 cc of a 2 mol/j2 aqueous sodium chloride solution were simultaneously added at 60° C. 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 Using core/shell type internal latent image type emulsion A, a full multilayer color photographic paper having the layer structure shown in Table 1 was prepared on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

First layer coating solution preparation Nidian coupler + a) 10 g and color image stabilizer (BL 2.3 g and ethyl acetate 10 mj)
2 and solvent (C) 4mj2, and this solution was diluted to 10%
The mixture was emulsified and dispersed in 90 ml of a 10% aqueous gelatin solution containing 5 ml of sodium dodecylbenzenesulfonate.

On the other hand, the above silver halide emulsion (Ag 70 g/kg
A red-sensitive emulsion was prepared by adding 2.0 x 10-' mol of the red malignant dye shown below per mol of silver halide to the red-sensitive emulsion.
I made g. The emulsified dispersion, the emulsion, and the development accelerator + dl were mixed and dissolved, the concentration was adjusted with gelatin so that the composition shown in Table 1 was obtained, and the nucleation accelerator of the present invention was mixed with Ag as shown in Table 2.
A coating solution for the first layer was prepared by adding 1.8 x 10-' moles per mole.

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

The following spectral sensitizers were used in each emulsion.

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

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

e, ○■
ω Otsu ゝ＼−−／′ τ 疋J cX.

Δ ○ i: Brother ○'s engineer Q-C) 4+1
〜ノ巳＼−−／ cの２２連 ω め τ = し；−り＝）C〜に＋； ２し−１１１１１１１ノ' Color photographic paper made in this way Wedge exposure (
1/10 seconds, 10 CMS), the following processing steps A and B were performed, and the magenta color image density was measured. At that time, fogging exposure for 10 seconds from 15 seconds after the start of development during color development (0.5 Lux on the photosensitive film, color temperature 5400K)
was applied.

The results obtained are shown in Table 2.

Processing step A Toki Tsukasa 2 days Light color development 2 minutes 30 seconds 33℃ bleach fixing 1
Minute 30 seconds 33℃ stable ■ 1 minute
Stable at 33°C ■ 1 minute 33°C
Stable ■ 1 minute The replenishment method for the 33℃ stable bath is so-called countercurrent replenishment, in which the stable bath ■ is replenished, the overflow liquid from the stable bath ■ is led to the stable bath ■, and the overflow liquid from the stable bath ■ is led to the stable bath ■. method.

Processing step B Be E-□□-2''-Takaichi color development 1 minute 30 seconds 37℃ bleach fixing
40 seconds 37℃ stable ■ 20
Seconds Stable at 37℃ ■ 20 seconds 37
Stable at °C ■ 20 seconds at 37 °C Other conditions are the same as processing step A [Color developer] Mother liquor Diethylenetriaminepentaacetic acid 2.0g Benzyl alcohol 12.8g Diethylene glycol 3.4g Sodium sulfite
2.0g Sodium Bromide 0.26
g Hydroxylamine sulfate 2.60 g Sodium chloride 3.20 g 3-Methyl-4-amino-N-4,25 g Ethyl-N-(β-methanesulfonamidoethyl)-aniline Potassium carbonate 30.0 g Optical brightener ( Stilbene type) 1.0g Add water to 10100O! pH10
, 209H was prepared with potassium hydroxide or hydrochloric acid.

[Bleach-fix solution] Mother ammonium thiosulfate 110g Sodium bisulfite Log diethylenetriaminepentaacetic acid iron 56g (I [[) Ammonium monohydrate ethylenediaminetetraacetic acid 2 5g Sodium dihydrate 2-mercapto-1,3,4- 0.5 g of triazole water was added to 1000 ml of 100 O.5' pH was adjusted with aqueous ammonia or hydrochloric acid.

[Stabilizing liquid]

Mother 2 1-hydroxyethylidene 1.6ml-1.1
'-Diphosphonic acid (60%) Bismuth chloride 0.35 g Polyvinylpyrrolidone 0.25 g Aqueous ammonia 2.5 mf Nitrilotriacetic acid 3N
a 1.0g5-chloro-2-methyl-45
0■ -isothiazolin-3-one 2-octyl-4-isothia 50■zolin-3-
On optical brightener (4,4'-Sia 1.0g minostilbene type) Add water and 1000m7! p)l
7.5pt+ was adjusted with potassium hydroxide or hydrochloric acid.

Table 2 Comparative Compounds Zanbru Compound 1 containing the compound of general formula (1) of the present invention
~4 has a minimum image density (D,
in) was low and the maximum image density (DffiaX) was high. Cyan, yellow? Similar results were obtained when measuring the M degree. Furthermore, a similar tendency was observed even when the treatment steps were changed.

Example 2 Emulsion B and the following yellow coupler were used, the composition of the third layer was as shown in Table 3, and the nucleation accelerator of the present invention was added as shown in Table 4 at a concentration of 4.7% per mole of Ag. Color photographic paper was prepared in the same manner as in Example 1 except that x10-4 mol was added.

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

Table 4 Samples N118 to 10 containing the compound of the present invention were less susceptible to running deterioration of the color developer than NcLll without additives.

Example-3 The positions of the first layer (red-sensitive layer) and the third layer (green-sensitive layer) were swapped, the cyan coupler was changed to the one below, and -a formula (1)
Color photographic paper was prepared in the same manner as in Example 2, except that the compounds shown in Table 5 were used, and samples were obtained by performing exposure, light, and processing step B in the same manner as in Example 2. The graininess of this positive color image was visually evaluated. The results are shown in Table 5.

Table 5 Comparative compound-3 (Cyan coupler) Graininess evaluation 5...Excellent 4...Slightly excellent 3...Fair 2... ... Slightly inferior 1 ... Inferior Samples No. i 2 to 15 containing the compound of the present invention have superior graininess (roughness of the screen) compared to comparative samples Arashi 16 to 17. This difference was particularly noticeable when a color developer degraded by running was used.

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

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

The same results as in Example-1 were obtained with the sample using the N-1 CHCmiCH nucleating agent. Cyan density and magenta density were also measured and similar results were obtained.

Example 5 The following green-sensitive dyes were added to emulsion A, and 1-oxy-3,5-dichloro-3-) riazine sodium salt was used as a gelatin hardening agent, and the composition of the present invention was prepared as shown in Table 7. After adding 3.0XIO-' moles of nucleation promoter per mole of Ag, an amount of 3.0XIO-' moles of silver was deposited on the polyethylene terephthalate support.
A gelatin protective layer was simultaneously applied thereon to prepare a direct positive photographic light-sensitive material.

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

Green-sensitive dye replenisher A Sodium sulfite 100g Potassium carbonate 20g 1-phenyl-4-methyl-4-3g Hydroxymethyl-3-pyrazolidone hydroquinone 45g 5-methylbenzotriazole 40■ Add water
17! pH with potassium hydroxide
Adjust to 11.2 Starter B Sodium Bromide 175g Glacial Acetic Acid
Add 63n+77 water
11 Table 7 Even in the black-and-white light-sensitive materials, sample rows 25 to 26 containing the compound of the general formula [I] of the present invention are different from sample rows 27 to 26 of the comparative example.
The maximum image density (D, aX) was higher than that of No. 28.

Example 6 Color photographic paper was prepared in the same manner as in Example 1 except that the nucleation accelerator was omitted. After imagewise exposure, this was exposed and processed in the same manner as in Example 1, except that a color developing solution containing 3.5 x 10-6 mol/l of the nucleation accelerator shown in Table 8 was used, resulting in a positive color image. I got it. The magenta density measurement results are
Shown in the table.

Table 8 Sample No. using the compound of general formula [1] of the present invention,
29-30 are compared to sample floors 31-32 of the comparative example,
D i and X were high, and D ff1i n was low. Similar results were obtained for cyan and yellow densities.

Example-7 Samples 1 to 22 of Example-1 were tested at 1/100 seconds for 10
After CMS exposure, process steps A and B were carried out in the same manner as in Example-1.
was applied. These samples are also No. 1 to 17 are No. 1.
There were fewer re-inverted negative images compared to 8-22.

〔Effect of the invention〕

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

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

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

Furthermore, even if the color development time varies with respect to the standard time, the maximum image density and minimum image density do not vary from the optimum values (it is possible to form a direct positive color image in which the brownish reproducibility does not change easily). can.

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

Furthermore, since the pn of the developer is low, it is less likely to deteriorate due to air oxidation, etc., and direct positive color images with stable performance can be formed over a long period of time.

Procedural amendment 62.7.13 Showa year, month, day 1, Indication of the case 1986 Patent Application No. 268819 2, Title of the invention Direct positive image forming method 3, Person making the amendment Relationship with the case Applicant name Title (520 ) Fuji Photo Film Co., Ltd. 4, Agent 6, Subject of amendment Claims of the specification and detailed description of the invention 7. Contents of amendment (1) Specification No. “Brome atom, etc.)” on page 13, line 6.
Insert a ``hydroxy group'' after.

(2) “Running is ``over time'' in the second line of page 59 of the same book.
and correct it.

(3) “Running processing” (2 locations) in Table 4 on the same page of the same book
is corrected to "37℃ aging".

(4) “Running Pa” in lines 5-4 from the bottom of the same page in the same book.
Corrected as ``high temperature aging''.

(5) ``Running process'' (2) in Table 5, page 60 of the same book.
) is corrected to "37℃ aging".

(6) N-1 and N-2 on page 64 of the same book [ ” and correct it.

(7) Insert the following after line 10 of page 68 of the same book.

Example 8 The same procedure as in Example 1 was carried out except that the stabilizing liquid was replaced with the following washing water, and the same results as in Example 1 were obtained.

<Washing water> Tap water was washed with H-type strongly acidic cation exchange resin (manufactured by Mitsubishi Kasei).
The water was passed through a mixed-bed column packed with Diaion 5K-IB) and an OH-type strong basic anion exchange resin (Diaion 5A-10A) to obtain the following water quality, and then treated with incyanuric acid dichloride as a disinfectant. Sodium 20mg/
l was added.

Calcium ion 1.1 mg/1 Magnesium ion 0.5 mg/lp8
6.9 Claims (1) After imagewise exposure of a photosensitive material having at least one internal latent image type direct positive silver halide photographic emulsion layer on a support,
1. A method for forming a direct positive image, which is characterized in that fogging exposure is applied before or during the development process, and the development process is carried out in the presence of a compound represented by the following general formula.

General Formula (I) In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that is cleaved under alkaline conditions. X represents an oxygen atom, a sulfur atom or a selenium atom.

S 11] I Y is -8-1-N-(, N-1-N-C-N-1111
l Represents R1R2R3R4 or -N-, Ro, R2, R3, R4, Rs
,Rs,R? and R8 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group.

R is a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group,
Or represents an arylene group.

Z is a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a substituted or unsubstituted sulfonyl group, a carbamoyl group, a sulfamoyl group, a carbonamide group, a sulfonamide group, an acyloxy group, a sulfonyloxy group, a ureido group, Represents a thioureido group, acyl group, oxycarbonyl group, oxysulfonyl group, oxycarbonylamino group or mercapto group. n represents 0 or 1.

Claims (1)

[Claims] (1) After imagewise exposure of a photosensitive material having at least one internal latent image type direct positive silver halide photographic emulsion layer on a support,
1. A method for forming a direct positive image, which is characterized in that fogging exposure is applied before or during the development process, and the development process is carried out in the presence of a compound represented by the following general formula. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. X represents an oxygen atom, a sulfur atom or a selenium atom. Y is -S-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents R
_1, R_2, R_3, R_4, R_5, R_6, R_
7 and R_8 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group or aralkyl group. R is a linear or branched alkylene group, a linear or branched alkenylene group, a linear or branched aralkylene group,
Or represents an arylene group. Z is a hydrogen atom, a halogen atom, a nitro group, a cyano group, a substituted or unsubstituted sulfonyl group, a carbamoyl group, a sulfamoyl group, a carbonamide group, a sulfonamide group, an acyloxy group, a sulfonyloxy group, a ureido group, a thioureido group, It represents an acyl group, oxycarbonyl group, oxysulfonyl group, oxycarbonylamino group or mercapto group. n represents 0 or 1.