JPH01211747A - Direct positive silver halide emulsion and silver halide sensitive material using same - Google Patents

Abstract

PURPOSE:To improve the reciprocity law failure of the sensitive material at a low illuminance, and to attain the excellent graininess and the development progress of the sensitive material by constituting the emulsion of an inner nucleus composed of a silver iodobromide particle contg. 1-12mol.% of silver iodide and an external nucleus composed of a silver halide contg. 0-2mol.% of silver iodide. CONSTITUTION:The inner nucleus of a core/shell type silver halide particle is composed of the silver iodobromide particle which is chemically sensitized in the presence of an org. silver halide solvent and contains 1-12mol.% of silver iodide. The external nucleus coating the photosensitive site of a core is composed of the silver halide contg. 0-2mol.%. Namely, the emulsion comprises a part (A) having a high interstitial silver ion concn. in the inner part of the silver halide particle, and as the inner nucleus is chemically sensitized in the presence of the org. silver halide solvent, the part (B) having the high interstitial silver ion concn. is effectively and chemically sensitized. The emulsion has the synergetic effect due to the parts (A) and (B). Thus, the reciprocity law failure of the sensitive material at the low illuminance, and the graininess and the development characteristic of the sensitive material are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a direct positive silver halide emulsion and a silver halide photosensitive material using the same.

<Prior art> Photography using silver halide has superior sensitivity and gradation characteristics compared to other photographic methods, such as electrophotography and diazo photography, and has traditionally been the most widely used method. .

Among these methods, a method of directly forming a positive image is known. This is, for example, U.S. Patent Section 3.761,276
As disclosed in Japanese Patent Publication No. 60-55821, using an internal latent image type emulsion, silver halide grains on which an internal latent image has been formed are treated with a surface developer (on the side where the latent image is formed inside the silver halide grains). A positive image is obtained by giving uniform exposure or using a nucleating agent when developing with a developing solution (which is left undeveloped after actual purchase).

Such a direct positive silver halide emulsion is superior to a negative emulsion in that a positive image can be obtained in -1 processing.

U.S. Patent No. 3.850.637, U.S. Patent No. 3.761.2
No. 76 describes examples of internal latent image type wheel dispersed silver iodobromide core/shell emulsions.

The silver iodide content of the silver halide shell portion constituting such an emulsion is 25 mol %.

Furthermore, U.S. Patent No. 4.504.570, JP-A-58
No.-108528 describes a tabular internal latent image type silver iodobromide core/shell emulsion, in which:
It is said that it is desirable that the silver iodide content of the silver halide constituting the emulsion be higher on the surface of the shell portion than on the core portion.

<Problem to be solved by the invention> However, the emulsions described in the above-mentioned U.S. Pat.
The disadvantage is that when the degree of exposure becomes strong, re-inversion occurs, so there is a limit to the degree of freedom of exposure allowed. For this reason, photographic photosensitive materials using the above-mentioned emulsions have problems in that the photographable area (latitude) is restricted and the degree of freedom in exposure is restricted.

In addition, the emulsion described in U.S. Pat. No. 3,850,637 is composed of a relatively high silver iodide content in the shell portion of silver halide, resulting in poor graininess and poor development. There are problems such as the induction period becomes longer and initial development is delayed.

In these specifications, there is no mention of low illuminance reciprocity rules.

An object of the present invention is to provide a direct positive silver halide emulsion that improves low-illuminance reciprocity failure, has good graininess, and has excellent development characteristics, and a silver halide photosensitive material using the same.

<Means for Solving Problem n> In order to achieve the above object, the direct positive silver halide emulsion of the present invention is chemically sensitized in the presence of an organic silver halide solvent to reduce the silver iodide content. An inner core composed of silver iodobromide grains having a silver iodide content of 1 to 12 mol %, and an outer core composed of silver halide having a silver iodide content of 0 to 2 mol %, which covers at least the photosensitive sites of this inner core. It contains core/shell type silver halide grains having a shell.

The silver halide photosensitive material of the present invention has at least one emulsion layer containing the above-mentioned direct positive silver halide emulsion.

Hereinafter, the configuration of the present invention will be explained in detail.

The inner core of the core/shell type silver halide grains in the present invention is chemically sensitized in the presence of an organic silver halide solvent to have a silver iodide content of 1 to 12 mol%, preferably 1 to 12 mol%. It is composed of silver iodobromide grains having a content of 8 mol %.

Furthermore, the outer shell covering at least the photosensitive site of the core (the site that produces photodecomposed silver upon exposure to light) is made of silver halide with a silver iodide content of 0 to 2 mol%, preferably 0 to 1 mol%. It is composed of

By configuring the silver halide grains in this way, the effects of the present invention can be obtained because of the presence of a portion with a high interstitial silver ion concentration inside the silver halide grains and the presence of an organic silver halide solvent. This is expected to be due to a synergistic effect with the above-mentioned ability to efficiently chemically sensitize the area with a high interstitial silver ion concentration since the lower part is chemically sensitized.

As mentioned above, the reason why the silver iodide content in the shell is made smaller than the conventional one is that if the silver iodide content in the shell is increased, the graininess worsens, the induction period of development becomes longer, and the initial development is delayed. This is because the effects of the present invention cannot be obtained, such as the delay.

The core/shell type silver halide grains constituting the direct positive silver halide emulsion of the present invention are made of It is obtained by preparing a silver halide core having the above composition which has been chemically sensitized in the presence of a silver halide solvent, and then coating its surface with a silver halide shell having the above composition.

In this case, it is not necessary to cover the entire particle surface of the core with the shell, and it is sufficient to cover at least the photosensitive sites of the core.

A useful organic silver halide solvent used in the present invention is an organic silver halide solvent present in water or water and an organic solvent (for example, water/methanol - 1/1) at a concentration of 0.02 mol. It is capable of dissolving more than twice the weight of silver chloride that can be dissolved in water at a temperature of .degree.

Specific examples of particularly preferred organic silver halide solvents include:
These include sulfur-containing organic silver halide solvents, organic thioether compounds, thione compounds, mercapto compounds, etc. More specifically, organic thioether derivatives described in Japanese Patent Publication No. 11386/1986 and Japanese Patent Application No. 58/232069, page 8 Compounds described on pages 23 to 23, compounds described on pages 195 to 196 of JP-A-55-77737, or thione compounds and thioether compounds described in JP-A-53-824008 and JP-A-53-144319. can be mentioned.

Specific examples of the organic silver halide solvent in the present invention are listed below, but the invention is not limited thereto.

(1), (2)HO(
CH2)2-S-(CH2)2-3- (CH2)20
HHO(CH2)3-S-(CH2)2-S-(C
H2) 30HNO(C)l2) 3-5-(CH
2) 2-5-(CH2) 2-5-(C)12)
20H(HO(CH2)2-S-(CH2)2-0-
CH2-)2(HO(CH2)5-S-(CH2)s
-0-(CH2)2-) 2(Hs C2-0-(C
H2)2-S-(CH2)2-) 25(H3CO-
(CH2)4-S -(CH2)4-) 25■ (H5C2-NH-C-(C)12)3S -(
CH2)3-)20[NH2Co (CH2)2-S
=(CH2)2C0NH-CH2-)2HOOC-C
H2-3-(CH2)2-5-CH2-COOHun
Llt1CH3
SO2CH25OCH3CH3SO2CH2SO2CH
3 The concentration of organic silver halide solvent during chemical sensitization is:
10' to 10-' per mole of silver halide in the core
Mold is preferred.

Chemical sensitization of the silver halide core may be performed using one or more of a noble metal sensitizer, a sulfur sensitizer, and a reduction sensitizer.
In particular, sensitivity increases when gold sensitization and sulfur sensitization are performed.

Chemical sensitization can be carried out using activated gelatin as described in T. H. JaIIles, The Theory of the Photographic Process, 4th Edition, Macramin, 1977, p. 6 Fu 76. Yes, Research Disclosure Volume 120, April 1974, Item 12008, Research Disclosure, 1
34, June 1975, Item 13452, U.S. Patent Nos. 1,623,499, 1.673.522, 2,399,083, 2. ．． 642.36
No. 1, No. 3,297.447, No. 3,297,4
No. 46, No. 3.7.72,031, No. 3,761
゜267, same No. 3,857,711, same No. 3.56
No. 5,633, No. 3.901.714 and No. 3
, 904.415 and British Patent No. 1,315,75
pAgs ~10, pH 5-8 and temperature 30-80°C as described in No. 5 and No. 1°396.696.
can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium, osmium, rhodium, rhenium or phosphorus sensitizers or combinations of these sensitizers.

Chemical sensitization is optimally carried out in the presence of thiocyanate compounds as described in U.S. Pat. No. 2,642,361;
Also, U.S. Patent No. 2.521.926, U.S. Patent No. 3,021
, No. 215 and No. 4. ．． No. 854,457 in the presence of sulfur-containing compounds of the type described.

It can also be chemically sensitized in the presence of finishing (chemical sensitization) modifiers. Finish modifiers used include:
Azaindene, azapyridazine, azapyrimidine, benzothiazolium salts, and sensitizers having one or more heterocyclic nuclei are known to suppress fog and increase sensitivity in the process of chemical sensitization. Compounds are used.

Examples of finish modifiers include U.S. Pat.
No. 3,565,631 and No. 3,901,
No. 714, Canadian Patent No. 778,723 and Duffin, Photographic Emulsion Chemistry Focal Press (1966).
, New York, pp. 138-143.

Also, U.S. Patent Nos. 3,891,446 and 3.9.
For example, reduction sensitization can be performed using hydrogen, as described in U.S. Pat.
No. 83,609, ofteda-rl
et al., Research Disclosure, Vol. 136, 197.
August 5, Item 13654, U.S. Patent No. 2.518
．． No. 698, No. 2,739,060, No. 2,74
No. 3,182, No. 2.743.183, No. 3.0
26.203 and 3.361,564, or with reducing agents such as stannous chloride, thiourea dioxide, polyamines and amineporanes, or with low pAg (e.g. less than 5) and/or Reduction sensitization can be achieved by high pH (eg higher than 8) treatment. U.S. Patent No. 3,917°485 and U.S. Patent No. 3,917
Surface chemical sensitization can be performed, including subsurface sensitization as described in No. 66.476.

When using an intermediate chalcogen sensitizer (sulfur, selenium, tellurium) for chemical sensitization of the core, the amount is 0.05 to 1 mole of silver.
When a gold sensitizer is used, it is preferably used in a concentration range of 0.5 to 5 times the concentration of the intermediate chalcogen sensitizer.

Adjustment of contrast (gradation) by adjusting the ratio of intermediate chalcogen to gold sensitizer is disclosed in U.S. Patent No. 4,0
35.185.

In addition, in chemical sensitization of the core, chemical sensitization is carried out in the presence of nitrogen-containing heterocyclic compounds described in JP-A-50-63914, JP-A-51-77223, JP-A-58-126526, JP-A-58-215644, etc. It is also useful to

Conditions for the chemical sensitization step may be arbitrarily determined, but it is generally desirable to carry out the chemical sensitization step at a pH of 9 or lower, a pAglo or lower, and a temperature of 40° C. or higher.

Such a method of treating silver halide for the core and coating the surface of the silver halide grains constituting the core with silver halide that will become the shell is known, for example, as described in U.S. Pat.
, No. 206,316, No. 3,317,322, No. 3,367.778 (excluding the step of fogging the particle surface), and No. 3,761,276. The method described can be advantageously applied.

Furthermore, it is preferable to use sulfur sensitization, reduction sensitization, noble metal sensitization using gold or other noble metals, etc. alone or in combination on the shell surface.

It is also useful to carry out these chemical sensitizations in the presence of a polymer such as polyvinylpyrrolidone disclosed in JP-A-57-136641. It is also useful to perform surface chemical sensitization in the presence of known finish modifiers such as azaindenes, benzothiazolium salts, mercaptotetrazoles, mercaptoimidazoles, and the like. Among these chemical sensitizations, sulfur sensitization using a sulfur sensitizer and a combination of sulfur sensitization and gold sensitization are preferred.

Conditions for the chemical sensitization step may be determined arbitrarily, but as in the case of the core, it is generally desirable to carry out the chemical sensitization step at a pH of 9 or lower, a PA of 810 or lower, and a temperature of 40° C. or higher.

In combination with either or both of the above techniques,
or independently of these, as a third technique, silver thiocyanate, silver phosphate, silver carbonate, etc., which may form a precipitate on the particle surface immediately before or during chemical sensitization. salts, as well as soluble silver salts such as silver acetate, silver trifluoroacetate, and silver nitrate, as well as finely divided silver halides (i.e., silver bromide,
Silver iodide and/or silver chloride) grains can be introduced. For example, Lippmann emulsions can be introduced during the chemical sensitization process.

In the present invention, core/shell type silver halide grains may be doped with metal ions.

By doping with metal ions in this manner, it is possible to increase the amount of overexposure without causing re-inversion.

In addition, the minimum concentration (D m1n
) (hereinafter, the metal ions to be doped are referred to as metal dopants).

Divalent and trivalent cationic metal dopants are useful for such purposes. Preferred metal dopants include iridium, manganese, copper, cadmium, zinc, lead, bismuth and lanthanides. These metal dopants, punts, are 7 X' 1 per mole of silver.
It is desirable to use it in the range of 0-4 mol to 1 x 10-6 mol.

The metal dopant may be added to the silver halide core, shell, or both.

Furthermore, the timing of doping the metal ions may be at the same time as the chemical sensitization, or before or after the chemical sensitization, within a period until the shell formation is completed.

The production of core/shell type silver halide grains and the chemical sensitization of the grain surfaces are preferably carried out in the presence of a protective colloid. Gelatin is advantageous as a protective colloid, but
Other hydrophilic colloids may also be used.

Among the protective colloids used in preparing the emulsion of the present invention, gelatin is preferably lime-treated bone gelatin or skin gelatin having a molecular weight of 30,000 to 300,000.

Gel filtration chromatography is useful for determining molecular weight in this case.

Gelatin contains many impurity ions,
In some cases, a highly sensitive emulsion can be obtained by using gelatin which has been subjected to ion exchange treatment to reduce the amount of inorganic impurity ions.

Pork skin gelatin, which is acid-treated gelatin, can also be used, as well as gelatin derivatives such as acetylated gelatin and phthalated gelatin.

5 to 100 per mole of silver halide during emulsion preparation
g of gelatin is used. Also, the gelatin concentration is 0.
2 to 10% by weight is suitable.

Regarding gelatin useful for preparing the emulsion of the present invention, see "Fundamentals of Photographic Engineering" Silver Salt Photography Edition (Corona Publishing, 1978), P1.
16-150.

Regarding gelatin and non-gelatin vehicles, see Research Disclosure (RD), Vol.
Volume 76, December 1978, Item 17843 Section ■''.

The ratio of silver halide in the core and ffl halide in the shell is arbitrary, but usually the latter is 1 to 1 mole of the former.
20 moles are used.

In the present invention, core/shell type silver halide grains having various grain sizes are used, and the average grain diameter is approximately 0.
．． 1-4 microns, preferably about 0.2-3 microns,
Particularly preferred are core/shell type silver halide grains of about 0.2 to 2.2 microns giving good results.

Core/shell type silver halide grains may have regular crystal bodies such as cubic or octahedral, or irregular crystal bodies such as spherical or plate-like.
ular), a composite of these crystal forms, or even a mixture of particles of various crystal forms.

Further, in recent years, development of internal latent image type emulsions using tabular grains has become active.

For example, U.S. Patent No. 4,504,570, JP-A-58-
No. 108528 requires at least 50% of the total projected area of silver halide grains or a thickness of less than 0.5 μm and a diameter of 0.6 μm.
As described above, internal latent image type silver halide grains characterized by being dominated by tabular grains having an average aspect ratio of 8.1 or more have been disclosed. Also, JP-A-62-26
No. 0139 discloses a plate-like silver halide emulsion having a layered structure, in which the coefficient of variation of the crystal size of the nuclei of the silver halide grains is less than 20%, and the nuclei have an average aspect ratio of at least 5.1. An internal latent image type tabular silver halide emulsion having the following characteristics is described.

Furthermore, Japanese Patent Application No. 62-208241, No. 62-219
No. 173 states that in tabular internal latent image type silver halide grains, 70% or more of the total projected area of all grains is determined by the ratio of the length of the side having the maximum length to the length of the side having the minimum length. 2 or less, and is occupied by hexagonal tabular silver halide grains having two parallel surfaces as outer surfaces, and the hexagonal tabular silver halide grains are monodispersed. Shown for emulsions.

These tabular internal latent image type emulsions are excellent in that they have good sharpness, rapid development, and provide direct positive images with little development temperature dependence, but they still have the drawback of large low-light reciprocity law failure. .

The average aspect ratio of the tabular silver halide grains useful in the present invention is not necessarily 8 or more as described in JP-A-5113-108528, but may be 4 or more. The degree of dispersion of tabular grains is determined by the patent application No. 61-2991.
No. 55, No. 62-20824, No. 62-219173
It is preferable that the monodispersity is high as described in No. It is preferable that the coefficient of variation (the value obtained by dividing the variation (standard deviation) of the particle size expressed by the circular diameter of its projected area by the average particle size) is 30% or less and monodisperse, and more preferably the coefficient of variation is 20. % or less, particularly preferably a coefficient of variation of 15% or less. This is because in preparing an internal latent image type emulsion, it is important to cover the chemically sensitized core as uniformly and completely as possible in order to obtain a direct positive image with a low minimum density (D m1n). The average grain size (diameter equivalent to an average projected area circle) of such tabular silver halide grains is preferably 02 to 25 μm, more preferably 02 to 2 μm.
,0 μm.

Such silver halide grains can be produced by undergoing nucleation, Ostwald ripening, and grain growth, and details thereof can be found in Japanese Patent Application No. 61-299.155, Japanese Patent Application Laid-Open No. 55-142329, According to the description in 1982-18556.

The method of shelling such silver halide grains is described in Example 13 of Japanese Patent Application No. 61-299155, and U.S. Pat.
No. 927 and No. 3.367.778 may be referred to.

In this case, the shell-forming silver halide includes silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. In this case, the core/shell molar ratio (silver ratio) is 1/30 to 5/1
The ratio is preferably 1/20 to 2/1, and even more preferably 1/20 to 1/1.

Further, the silver halide grains may be grains in which guest grains having various halogen compositions are epitaxially grown using tabular grains as host grains.

Regarding the epitaxial growth of guest particles, please refer to Japanese Patent Application Laid-open No. 58-108526, Japanese Patent Application Laid-open No. 57-133540,
JP-A No. 62-32443 may be referred to.

In addition, in the process of forming or physically ripening silver halide grains, cadmium, zinc, lead, thallium, copper,
Metal compounds such as bismuth, gold and iridium may also be present. Such compounds may be present in the reactor initially or may be added during particle formation.

Regarding this, U.S. Pat.
No. 3,737,313, No. 3,772,031 and No. 4.269,927 and RD Volume 134,
Reference may be made to the description in Item 13462, June 1975.

Moiser et al., Journal Cub Photographic Science Vol. 25, 1977P, 1
As described in Nos. 9 to 27, tabular grains can be sensitized by internal reduction during the precipitate formation process.

The tabular grains may have dislocation lines inside. The presence or absence of dislocation lines and their number can be determined at low temperatures (
Liquid He temperature) can be determined by observing with a transmission electron microscope.

Tabular grains containing dislocation lines can be formed by adding iodide salt during the crystal growth period or by using such tabular grains as seed crystals and adding iodide salt during a certain period of the crystal growth period during crystal growth. Ru.

It is particularly preferable to add a sensitizing dye, an antifoggant, and a stabilizer because chemical sensitizing nuclei are formed only in the edge portions of the tabular grains. In general, the above-mentioned additives are preferentially adsorbed on the crystal surfaces forming the main surfaces of the tabular grains, so that chemical sensitization nuclei are generated on different crystal surfaces of the tabular grains.

Finishing (Chemical Sensitization) Can be chemically sensitized in the presence of modifiers. Finishing modifiers used include chemical sensitizers such as azaindene, azapyridazine, azapyrimidine benzothiazolium salts, mercaptotetrazoles, mercaptoimidazoles, and sensitizers having one or more heterocyclic nuclei. In the process, compounds known to suppress fog and increase sensitivity are used. Examples of finish modifiers are U.S. Pat. No. 3,411,91.
No. 4, No. 3.554.757, No. 3,565,6
No. 31 and No. 3,901,714.

In addition to or in place of chemical sensitization, U.S. Pat.
No. 91,446 and U.S. Pat. No. 3,984,249, reduction sensitization can be performed, for example with hydrogen, and U.S. Pat. 3° 361.564, or using reducing agents such as stannous chloride, thiourea dioxide, polyamines and amineboranes, or with low pAg (e.g. less than 6) and/or high pl (e.g. 8) can be reduced sensitized by treatment.

In combination with or independently of the above techniques in the case of chemical sensitization of the shell surface, thiocyanic acid can form a precipitate on the particle surface immediately before or during chemical sensitization as an alternative technique. silver, silver salts such as silver phosphate, silver carbonate,
and soluble silver salts such as silver acetate, silver trifluoroacetate, and silver nitrate, and finely divided silver halides (i.e., silver bromide, silver iodide, and/or silver chloride) capable of Ostwald ripening on the tabular grain surfaces. Particles can be introduced. For example, Lippmann emulsions can be introduced during the chemical sensitization process.

The core/shell type silver halide emulsion of the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and forms a latent image mainly inside the grains. To do this, a fixed amount (0.5 to 3 g/m2) of a 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). A silver halide emulsion coated in the same amount and exposed in the same manner as described above has a maximum density measured by a normal photographic density measurement method when developed for 5 minutes at 18°C in developer B (developer B) (surface development). 6 at 20℃ in liquid)
of the maximum density obtained when developed for at least 5 minutes.
Preferably those have a concentration that is twice as large, more preferably those that have a concentration that is at least 10 times greater.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Soda carbonate (-hydrate) 52.5gKBr
5gKI
Add 0.5g water and add if1 surface developer 2.5g L-ascorbic acid 10g NaBO2・4H2035g KBr 1g water
1f1 Spectral sensitizing dyes, antifoggants, stabilizers, dispersion media, stabilizers, curing agents, dimensional stability improvers, antistatic agents, coating aids, dyes added to the silver halide emulsion used in the present invention , color couplers, adhesion prevention, improving photographic properties (e.g. development acceleration, high contrast, sensitization), etc., and how to use them can be found in, for example, Research Disclosure, Vol. 176, December 1978 issue (
Reference may be made to the descriptions in JP-A-58-113926, JP-A-58-113927, JP-A-58-113928, and JP-A-59-90842.

In particular, the spectral sensitizing dye, antifoggant, and stabilizer can be used in any step of the photographic emulsion manufacturing process, or can be present at any stage after manufacturing until immediately before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process. In other words, in addition to their original functions, spectral sensitizing dyes, antifoggants, and stabilizers are used to limit the formation position of chemical sensitization by utilizing other properties such as strong adsorption to emulsions, or to use different halogen It is also used for the purpose of stopping excessive halogen conversion and maintaining a hetero-halogen junction structure when obtaining particles with a bonded structure of different compositions.

Regarding these, please refer to JP-A-55-26589, JP-A-58-111935, JP-A-58-28738, JP-A-62-7040, and U.S. Patent No. 3,628.960.
No. 4,225.666.

If some or all of the spectral sensitizing dye, antifoggant, and stabilizer are added before adding the chemical sensitizer, and then the chemical sensitizer is added and chemical ripening is performed, the chemical sensitization pattern will be Since the position formed on the silver halide grain is limited to the area where the sensitizing dye, antifoggant, and the stabilized state are not adsorbed, latent image dispersion is prevented and photographic properties are improved, which is particularly desirable. . In particular, when sensitizing dyes, antifoggants, and stabilizers that selectively adsorb to the (Ill) plane of silver halide grains are added, chemical sensitization is limited only to the edges of hexagonal tabular grains. Particularly preferred for forming. In general, the above-mentioned additives are preferentially adsorbed on the crystal surfaces forming the main surfaces of the tabular grains, so that chemical sensitization occurs on different crystal surfaces of the tabular grains.

Dyes used for spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

Specifically, U.S. Pat.
17029 (1978), pages 12-13, and the like.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat.゜615.641, patent application 1986-22
6294 etc.).

Further, the silver halide emulsion used in the present invention may be a system that is spectrally sensitized with an antenna dye. Regarding spectral sensitization using antenna dyes, reference can be made to the descriptions in Japanese Patent Application Nos. 61-51396, 61-284271, and 61-284272.

The silver halide emulsion of the present invention is coated on a support in one or more layers (for example, two or three layers) together with other emulsions if necessary.
can be provided. Moreover, it can be provided not only on one side of the support but also on both sides. Furthermore, they can be layered as emulsions with different color sensitivities.

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 at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support.

The order of these layers can be arbitrarily selected as required. A preferred order of arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Further, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Furthermore, two or more types of emulsions having different sensitivities may be mixed and used in the same emulsion layer.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure Magazine No. 17643XV.
11 (issued December 1978) 928, European Patent No. 0,182.253, and JP-A-61-9
No. 7655. Also, Research Disclosure Magazine No.17643XV p2B
The coating methods described in items 1 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 applied to full-color copying machines and color hard copies for storing CR and T images.

In this case, the red-sensitive emulsion/layer usually 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. You can also do it.

The present invention can also be applied to black-and-white light-sensitive materials using a three-color coupler mixture as described in Research Discrow 9 Liger 1 Magazine No. 17123 (published July 1978).

Details of the color couplers that can be used in the present invention can be found in Japanese Patent Application No. 1982-226292, pages 19 to 27, and various compounds that can be included in the light-sensitive materials of the present invention (e.g., color anticaprilants, anti-fading agents, dyes, etc.)
are described on pages 28 to 30 of the same specification.

Furthermore, the present invention can also be applied to black and white photographic materials.

Examples of black and white (B/W) photographic materials to which the present invention can be applied include JP-A-59-208540 and JP-A-60-26003.
B/W direct positive photographic material described in No. 9 (
Examples include X-ray photosensitive materials, duplex photosensitive materials, micro photosensitive materials, phototypesetting photosensitive materials, and printing photosensitive materials.

The present invention can also be applied to light-sensitive materials for color diffusion transfer. In this case, the colorants used are preferably diffusible dye-releasing redox compounds. Diffusible dye-releasing redox compound (hereinafter referred to as rDRR compound)
can be expressed by the following general formula.

(Ballast + - + Redox cleavage group + D In the formula, D represents a dye (or its precursor) moiety. This dye moiety may be bonded to the redox cleavage group via a linking group. As for the dye moiety represented by D, those described in the following documents are effective.

Example of yellow dye - U.S. Patent No. 3,597,200, U.S. Patent No. 3゜309.1
No. 99, No. 4,013,633, No. 4.245.
No. 028, No. 4,156.609, No. 4,139
, No. 383, No. 4.195.992, No. 4,14
No. 8,641, No. 4,148. ．． No. 643, No. 4゜336.322: JP-A-51-114930, No. 5
No. 6-71072, Research Disclosure Magazine 1
7630 (1978) issue, same magazine 16475 (197
7) Items listed in item 7).

Example of magenta dye U.S. Pat. No. 3.453.107, U.S. Pat. No. 3.544.5
No. 45, No. 3,932,380, No. 3.931.
No. 144, No. 3,932.308, No. 3,954
, No. 476, No. 4,233.237, No. 4,25
No. 5,509, No. 4,250,246, No. 4゜1
No. 42.891, No. 4,207,104, No. 4,
No. 287,292: JP-A No. 52-106727, No. 5
No. 3-23628, No. 55-36804, No. 56-7
Those described in No. 3057, No. 56-71060, and No. 55-134.

Examples of cyan dyes: U.S. Patent Nos. 3,482.972 and 3.929.7
No. 60, No. 4,013,635, No. 4.268.
No. 625, No. 4.171.220, No. 4,242
, No. 435, No. 4.142.891, No. 4,19
No. 5,994, No. 4,147,544, No. 4゜1
48.642, British Patent No. 1,551,138: JP-A-54-99431, JP-A-52-8827, JP-A-53
-47823, 53-143323, 54-9
No. 9431, No. 56-71061; :l-'O Tsuba Patent (EPC) No. 53,037, No. 53,040:
Research Disclosure Magazine 17630 (1978
), issue 16475 (1977) of the same magazine.

The application amount of these compounds is generally about I x 10-4 to 1
Xl0-2 mol/rn' is suitable, preferably 2
X10-4 to 2X10-2 mol/rn'.

In the present invention, the coloring material may be contained in the silver halide emulsion layer combined therewith, or may be contained in a layer adjacent to the emulsion layer on the exposed side or on the opposite side.

When the light-sensitive material of the present invention is used in a color diffusion transfer method, the photographic emulsion may be coated integrally on the same support on which the image-receiving layer is coated, or it may be coated on a separate support. may be coated on. Further, the silver halide photographic emulsion layer (light-sensitive element) and the image-receiving layer (image-receiving element) may be provided in a combined form as a film knit, or may be provided as separate and independent photographic materials. Furthermore, the form of the film unit may be one that is integrated throughout the process of exposure, development, and viewing of the transferred image, or may be one that is peeled off after development, but the latter type is preferred for the present invention. is more effective. Particularly preferred is the configuration described in Japanese Patent Application No. 1983-231374.

The present invention can also be applied to so-called heat-developable photosensitive materials.

A heat-developable photosensitive material basically has a photosensitive silver halide, a binder, a dye-providing compound, and a reducing agent (the dye-providing compound may also serve as a reducing agent) on a support. Organic silver salts and other additives can be included as needed. In the case of transferring a diffusible dye to the image receiving element, this transfer may occur simultaneously with the thermal development, or may occur consecutively or at intervals after the thermal development. Thermal development may be carried out in the presence of a very small amount of water.

There are various methods of transferring diffusible dyes, such as a method of transferring to an image receiving element using an aqueous solvent such as water, a method of transferring to an image receiving element using a high boiling point organic solvent, a method of transferring to an image receiving element using a hydrophilic thermal solvent, Methods have been proposed in which the thermal diffusivity or sublimation of a diffusible dye is used to transfer the image to an image receiving element having a dye-receiving polymer, and the present invention is applicable to any of these methods.

The following are heat-developable photosensitive elements and image receiving elements that can be used in the present invention.
References that specifically describe elements (dye fixation) are listed. U.S. Patent Nos. 4,463,079 and 4,474,86
No. 7, No. 4.478.927, No. 4.507, 3
No. 80, No. 4,500,626, No. 4,483゜914, JP-A-58-149046, No. 58-14
No. 9047, No. 59-152440, No. 59-154
No. 445, No. 59-165054, No. 59-1805
No. 48, No. 59-168439, No. 59-17483
No. 2, No. 59-174833, No. 59-174834
No. 59-174835, No. 62-65038,
61-23245, 62-253159, European Patent Publication No. 210.66OA2, 220,746A2
No. 62-26488, No. 62-53126, No. 62-61056, No. 62-97088, etc.

The fogging treatment in the present invention is performed as described above.
Either of a method called "photofogging method" in which the entire surface of the photosensitive layer is exposed to second light, and a method called "chemical fogging method" in which development is performed in the presence of a nucleating agent may be used. Development may be carried out in the presence of a nucleating agent and fogging light. Further, a photosensitive material containing a nucleating agent may be subjected to fog exposure. Preferably, a chemical fogging method is used in which the lower right portion where the nucleating agent is present is subjected to development.

Regarding the optical fog method, the above-mentioned patent application No. 61-22629
It is described in the specification of No. 2, page 33, line 17 to page 35, last line.

As the nucleating agent that can be used in the present invention, all compounds conventionally developed for the purpose of nucleating endogenous 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 (Research Disclosure).
Disclosure) Magazine No. 22, 534 (1
Published in January 1983) pages 50-54, same magazine No. 15.16
2 (published in November 1976) pages 76-77 and the same magazine No. 23, 510 (published in November 1983) 346-
There are compounds described on page 352, and these are quaternary heterocyclic compounds (compounds represented by the following general formula (N-■))
, hydrazine compounds (compounds represented by the following general formula (N-11)), and other compounds.

General formula (N-1) (wherein, Z represents a group of nonmetallic atoms necessary to form a 5- to 6-membered heterocycle, and Z 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 R2 may be substituted with a substituent. However, R1, R2 and Z
At least one of the groups represented by contains an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and R2 form a 6-membered ring to form a dihydropyridinium skeleton. At least one of the substituents of R1, R2 and Z is % Xi (-Ll
It may have +□. Here, Xl is a group that promotes adsorption to silver halide, and Ll is a divalent linking group.

Y is a counter ion for charge balance, n is 0 or 1, and m is O or 1. ) To explain in more detail, the heterocycle completed by 2 is, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium. , indolenium, pyrrolinium, acridinium, phenanthridinium, inquinolinium, oxacillium, naphthoxacillium, naphtopyridinium and benzoxacillium nuclei. As a substituent for Z,
Alkyl group, alkenyl group, aralkyl group, aryl group, alkynyl group, hydroxy group, alkoxy group, aryloxy group, halogen atom, amino group, alkylthio group, arylthio group, acyloxy group, acylamino group,
Sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate group, hydrazine group, hydrazone group, or imino group, etc. can give. As the substituent for Z, for example, at least one substituent 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 Z, a heterocyclic quaternary ammonium group completed with Z via a suitable linking group may be included.

In this case, it takes a so-called dimer structure.

The heterocycle completed by Z preferably includes quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridinium, naphthopyridinium and inquinolinium nuclei. More preferred are quinolinium, benzothiazolium, and naphtopyridinium nuclei, 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 moiety. Examples of the substituent include those mentioned above as the substituent for Z.

The aromatic group represented by R2 has 6 to 20 carbon atoms, and includes, for example, a phenyl group and a naphthyl group.
Examples of the substituent include those mentioned above as the substituent for Z.

R2 is preferably an aliphatic group, most preferably a methyl group or a substituted methyl group.

At least one of the groups represented by R1, R2 and Z has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or R1 and R2 form a 6-membered ring, and a dihydropyridinium core is formed. However, these may be substituted with the groups described above as substituents for the group represented by Z. The hydrazine group preferably has an acyl group or a sulfonyl group as a substituent. The hydrazone group preferably has an aliphatic group or an aromatic group as a substituent. As the acyl group, for example, a formyl group and an aliphatic or aromatic ketone are preferred.

At least one of the substituents on the group or ring represented by R1, R2 and Z is preferably an alkynyl group or an acyl group, or R1 and R2 are preferably linked to form a dihydropyridinium core, Furthermore, it is most preferable that it contains at least one alkynyl group.

Preferred examples of the adsorption promoter to silver halide represented by Xl include a thioamide group, a mercapto group, and a 5- or 6-membered nitrogen-containing heterocyclic group. These are Z
may be substituted with the substituents mentioned above.
The thioamide group is preferably an acyclic thioamide group (eg, thiourethane group, thiourido group, etc.).

As the mercapto group,
, 4-thiadiazole) are preferred.

The 5- to 6-membered nitrogen-containing heterocycle represented by xl is one consisting of a combination of nitrogen, oxygen, sulfur, and carbon, and preferably produces iminosilver, such as hensitriazole.

The divalent linking group represented by Ll includes C, N, S,
It is an atom or atomic group containing at least one kind of 0. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -〇-1-S-1 -NH-1-N=, -CO-1-so2- (these groups have a substituent) ), 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, trifluoromethanesulfonate ion, thiocyanate ion, etc. It will be done.

These compounds and their synthesis methods are available for example in research and
Disclosure Magazine No. 22.

534 (published in January 1983) pages 50-54, and the same magazine No. 23.213 (published in August 1983) 267
Patent cited on page ~270, Japanese Patent Publication No. 49-38164
No. 52-19452, No. 52-47326, JP-A No. 52-69613, No. 52-3426, No. 55
-138742, US Patent No. 60-11837, US Patent No. 4,306,016, and US Patent No. 4.471.044.
It is stated in the number.

Specific examples of the compound represented by general formula (N-1) are listed below, but the compound is not limited thereto.

(N-I-1) 5-ethoxy-2-methyl-1-propargylquinolinium bromide (N-1-2) 2.4-dimethyl-propargylquinolinium bromide (N-1-3) 2-methyl -1-(3-(2-(4)
-methylphenyl)hydrazino)butyl)quinolinium iosito (N-1-4) 3,4-dimethyl-dihydrobyrito(2,1-b)benzothiazolium bromide (N-I-5) 6-nitoxythio Carbonylamino-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-6) 2-Methyl-6-(3-phenylthioureido)-1-propargylquinolinium promide (N-1- 7) 6-(5-penzotriazolecarboxamito)-2-methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-8) 6-(3-(2-mercaptoethyl)ureido)-2 -Methyl-1=propargylquinolinium trifluoromethanesulfonate (N-1-9) 6-(3-(3-(5-mercapto-1,3,4-thiadiazol-2-ylthio)propyl)ureido)- 2-Methyl-1-propargylquinolinium trifluoromethanesulfonate (N-I-1
0) 6-(5-mercaptotetrazol-1-yl)-2-methyl-1-propargylquinolinium iosito (N-1-11) 1-propargyl-2=(1-propenyl)quinolinium trifluoromethanesulfonate (N-I-12) 6-nitoxythiocarponylamino-2-(2-methyl-1-propenyl)-1-propargylquinolinium trifluoromethanesulfonate (N-1-13) 10-propargyl-1° 2.3
．． 4-Tetrahydroacridinium trifluoromethanesulfonate (N-I-14) 7-Nitoxythiocarbonylamino-10-propargyl-1゜2.3.4-Tetrahydroacridinium trifluoromethanesulfonate (N-1- 15) 6-Nitoxythiocarbonylamino-1-propargyl-2,3-pentamethylenequinolinium trifluoromethanesulfonate (N-I-16) 7-(3-(5-mercaptotetrazol-1-yl)benzamide )-10-proparkyl-1,2゜3.4-tetrahydroacridinium verchlorate (N-I-17) 6-(3-(5-mercaptotetrazol-1-yl)benzamide)-1-propargyl-2 ,3-pentamethylenequinolinium promide (N-1-18) 7-(5-mercaptotetrazol-1-yl)-9-methyl-10-propargyl-
1,2,3,4-Tetrahydroacridinium bromide (N-1-19) 7- (3-(N-(2-(5-
mercapto-1,3,4-thiadiazol-2-yl)
thioethyl)carbamoyl)propanamide) -10
-Propargyl-1,2,3,4-tetrahydroacridinium tetrafluoroborate (N-I-20) 6-(5-mercaptotetrazol-1-yl)-4-methyl-1-propargyl-2,
3-Pentamethylenequinolinium promide (N-1-21) 7-nitoxythiocarbonylamino-10-propargyl-1,2-dihydroacridinium trifluoromethanesulfonate (N-I-22) 7- (5 -mercaptotetrazol-1-yl)-9-methyl-10-propargyl-1,2-dihydroacridinium hexafluorophosphate (N-I-23) 7-(3-(5-mercaptotetrazol-1- yl)benzamido)-io-propargyl-1,2-dihydroacridinium bromide general formula (N-II) (wherein, R21 represents an aliphatic group, aromatic group, or heterocyclic group, 2R22 represents a hydrogen atom, represents an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group; G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, or an iminomethylene group (HN=C'); R23 and R24 are both hydrogen atoms, or one hydrogen atom and the other one of an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.

However, a hydrazone structure (>N-N=C) may be formed by including G, R2111, R24, and hydrazine nitrogen. Furthermore, the groups described above may be substituted with a substituent, if possible. ) To explain in more detail, R21 may be substituted with a substituent, and examples of the substituent include the following. These groups may be further substituted. For example, alkyl groups, aralkyl groups, alkoxy groups,
Alkyl or aryl substituted amine group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group,
These include aryl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, and carboxyl 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 (for example, a methyl group), or an aralkyl group (for example, an 0-hydroxypencyl group), and a hydrogen atom is particularly preferred.

As the substituent for R22, in addition to the substituents listed for R21, for example, an acyl group, an acyloxy group,
Alkyl or aryloxycarbonyl groups, alkenyl groups, alkynyl groups and nitro groups are also applicable.

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

R21 or R22, especially R21, may contain a diffusion-resistant group such as a coupler, a so-called ballast group (especially preferred when linked via a ureido group), a group that promotes adsorption to the surface of silver halide grains. X2(-L2+
m2. Here x2 is the general formula (N-I:
It has the same meaning as xl in 1, and is preferably a thioamide group (excluding thiosemicarbazide and its substituted products), a mercapto group, or a 5- to 6-membered nitrogen-containing heterocyclic group. L2 represents a divalent linking group and has the same meaning as Ll in general formula (N-r). 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 mercabuto-substituted nitrogen-containing heterocycle, e.g., a 2-mercap-1--1.3.4-thiadiazole group, 3
-mercapto-1,2,4-1-lyazole group, 5-mercapto-tetrasol group, 2-mercapto-1,3,4
-oxadiazole group, 2-mercabutohendoxazole group, etc.), or a nitrogen-containing heterocyclic group (eg, benzotriazole group, henzimidazole group, indazole group, etc.).

The most preferable x2 varies depending on the photosensitive material used. For example, in a color sensitive material, when using a coloring material (so-called coupler) that forms a dye by a coupling reaction with an oxidized product of a p-phenylenecyamine developer, x2
As such, a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver is preferable.

In addition, in color sensitive materials, coloring materials that generate diffusible dyes by cross-oxidizing oxidized developer (so-called DR
R compound), x2 is preferably an acyclic thioamide group or a mercapto-substituted nitrogen-containing heterocycle.

Further, in a black-and-white sensitive material, x2 is preferably a mercapto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle forming iminosilver.

Hydrogen atoms are most preferred as R23 and R24.

G in the general formula (N-I+) is most preferably a carbonyl group.

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

Examples of these compounds and their synthesis methods are as follows: Examples of hydrazine-based nucleating agents having a silver halide adsorption group include, for example, U.S. Pat.
No. 0,207, No. 4,031,127, No. 3.7
No. 18.470, No. 4,269,929, No. 4,
No. 276.364, No. 4.278゜748, No. 4
．． No. 385.108, No. 4.459,347, No. 4.478.928, No. 4.560.638, British Patent No. 2.011,391B, JP-A-54-747
No. 29, No. 55-163533, No. 55-74536
No. 60-179734.

Other hydrazine-based nucleating agents include, for example, JP-A No. 5
No. 7-86829, U.S. Pat. No. 4,560,638;
No. 4.478.928, and even No. 2.563.
No. 785 and No. 2,588,982.

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

(N-11-1) 1-formyl-2-(4-(3-
(2-methoxyphenyl)ureido]phenyl)hydrazine (N-II-2) 1-formyl-2-(4-[
3-(3-(3-(2,4-di-tert-pentylphenoxy)propyl]ureido)phenylsulfonylamino)phenyl)hydrazine (N-II-3) 1-formyl-2-(4-(
3-(5-mercaptotetrazol-1-yl)benzamido)phenyl)hydrazine (N-II-4) 1-formyl-2-(4-(
3-(3-(5-mercaptotetrazol-1-yl)phenyl)ureido)phenyl]hydrazine(N-II-5) 1-formyl-2-(4-(
3-(N-(5-mercapto-4-methyl-1,2,4-1-riazol-3-yl)carbamoyl)propanamido)phenyl]hydrazine(N-II-6) 1-formyl-2-( 4-(
3-(N-(4-(3-mercapto-1,2,4-triazol-4-yl)phenyl)carbamoyl)propanamido]phenyl)hydrazine (N -11-7) 1-formyl-2-[4 −(3
-(N-(5-mercapto-1°3.4-thiadiazol-2-yl)carbamoylmoyl)propanamido)phenyl)hydrazine (N-11-8) 2-(4-(benzotriazole-5-carboxamide) Phenyl]-1-formylhydrazine (N-11-9) 2-[4-(3-(N-(benzotriazole-5-carboxamido)carbamoyl)propanamide) Phenyl]-1-formylhydrazine (N-11- 10) 1-formyl-2-(4-(1
-(N-phenylcarbamoylcothiosemicarbazido)phenyl]hydrazine (N-11-11) 1-formyl-2-(4-(3
-(3-phenylthioureido) henzamido]phenyl)-hydrazine (N-11-12) 1-formyl-2-(4-(3
-hexylureido)phenyl) hydrazine (N-11-13) 1-formyl-2-(4-(3
-(5-mercaptotetrazol-1-yl)benzenesulfonamido)phenyl)hydrazine (N-+1-14) 1-formyl-2-(4-(3
-(3-(3-(s-mercaptotetrazol-1-yl)phenyl)ureido)benzenesulfonamide)phenyl)hydrazine The nucleating agent particularly preferably used in the present invention is a nucleating agent having an adsorption group to silver halide. It is a drug.

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 it may be added to other layers as long as it is diffused during coating or processing and adsorbed to the nucleating agent or silver halide. For example, it may be added to an intermediate layer, an undercoat layer or a back layer. When the nucleating agent is added to the processing solution, it may be included in the developer solution or a low pH precursor as described in JP-A-58-178350.

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 10-? ~10-3 mol.

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

The following compounds may be added for the purpose of increasing the maximum image density, lowering the minimum image density, improving the storage stability of the photosensitive material, or speeding up development.

Hydroquinones (e.g. U.S. Pat. No. 3.227.55)
No. 2, Compounds described in No. 4.279.987), chromans (for example, U.S. Pat. Monthly issue) 333~
Compounds described on page 334), quinones (for example, compounds described in Research Disclosure Magazine N.

No. 21206 (December 1981), pages 433-434), amines (e.g., U.S. Pat. No. 4,150)
．． 993 and JP-A No. 58-174757), oxidizing agents (for example, JP-A No. 60-260039, Research Disclosure Magazine No. 16936 (No. 19)
Compounds described on pages 10 to 11 (published in May 1978)
5944), compounds that release nucleating agents during development (e.g. compounds described in JP-A No. 60-107029), thioureas (e.g. compounds described in JP-A-60-95533), spirobis Indans (for example, JP-A No. 5
5-65944).

Examples of nucleation accelerators that can be used in the present invention include tetrasaintines, triacaindenes, and pentazain, which have at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group. and Japanese Patent Application Publication No. 61-136948 (pages 2-6 and pages 16-43), Japanese Patent Application No. 136949/1982 (
12-43) and No. 61-15348 (pages 10-29).

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

(A-1) 3-mercapto-1,2,4-triazolo(
4,5-a) Pyridine (A-2) 3-mercapto-1,2,4-triazolo(
4,5-a) pyrimidine (A-3) 5-mercapto-1,2,4-1-riazolo(1,5-a) pyrimidine (A-4) 7- (2-dimethylaminoethyl)-5-
Mercapto-1,2,4-triazolo(1,5-a)pyrimidine (A-5) 3-mercapto-7-methyl-1°2.4-
Triazolo (4,5-a) Pyrimidine (A-6) 3,6-di□mercapto-1,2゜4-triazolo (4,5-b:l) Pyridazine (A-7) 2-mercapto-5-methylthio -1,3,
4-thiadiazole (A-8) 3-mercapto-4-methyl-1°2.4-
Triazole (A-9) 2- (3-dimethylaminopropylthio)
-5-mercapto-1,3,4-thiadiazole hydrochloride (A-10) 2-(2-morpholinoethylthio)-5-
Mercapto-1,3,4-deadiazole hydrochloride (A-11) 2-mercapto-5-methylthiomethylthio-1,3,4-thiadiazole sodium salt (A-12) 4- (2-morpholinoethyl)-3- Mercapto-1,2,4-triazole (A-13) 2- (2-(2-dimethylaminoethylthio)ethylthio-2-5-mercapto-1,3,4-thiadiazole hydrochloride (A-14) 2- (6 -dimethylaminohexylthio)-5-mercapto-1,3゜4-thiadiazole hydrochloride (A-15) 2- (3-(2-methyl-1-(1,4
, 5,6-titrahydropyridinyl))propylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride The nucleation promoter is preferably added to the silver halide emulsion or to a layer adjacent thereto.

In this case, the amount of the nucleation accelerator added is preferably 10-6 to 1o-2 mol, more preferably 10-5 to 1o-2 mol, per mol of silver halide.

In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, 10 -8 to 10 -
3 mol is preferred, more preferably 10-7 to 10-
It is 4 moles.

Moreover, two or more kinds of nucleation accelerators can also be used together.

The color developing solution used in the development of the light-sensitive material used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, amine phenol compounds are also useful, or p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N,N
-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl- Mention may be made of 4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or I)-toluenesulfonates.

Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, hendithiazoles or mercapto compounds are generally included. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo(2,2,2)
various preservatives such as octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers,
Competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids. Various chelating agents such as
Ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine- N.

Representative examples include N,N',N'-tetramethylenephosphonic acid, ethylene glycol (O-hydroxyphenylacetic acid) and salts thereof.

The pH of these color developing solutions is 9 to 12.

Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally 1 ft or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 300 m 1 or less. You can also do it. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment.

Treatment with a two-phase continuous bleach-fix bath, fixing before bleach-fixing, or bleaching after bleach-fixing can be carried out as desired depending on the purpose.
Examples of bleaching agents include iron (Ill), cobalt (
Compounds of polyvalent metals such as Ill), chromium (■), and copper (n), peracids, quinones, nitro compounds, and the like are used. A typical bleaching agent is ferricyanide compound 1.
dichromate, iron (Ill) or cobalt (Ill)
II) organic complex salts, such as ethylenediaminetetraacetic acid,
Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, persulfate monobromine Acid acid 2 permanganate; nitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complexes and persulfates, including ethylenediaminetetraacetic acid iron(Ill) complexes, are preferred from the viewpoint of rapid processing and prevention of environmental pollution.

Iron aminopolycarboxylic acid (Ill) complexes are particularly useful both in bleaching solutions and in white fixing. The pH of the bleaching solution or bleach-fixing using these aminopolycarboxylic acid iron(III) complexes is usually 55.
~8, but for faster processing, lower pH
It can also be processed.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Patent No. 1,290.
No. 812, JP-A-53-95630, Research Disclosure Magazine No. 17,129 (July 1978)
Compounds having a mercapto group or disulfide bond described in JP-A-50-140129, thiourea conductors described in U.S. Patent No. 3,706,561, JP-A-58- Iodide salts described in No. 16235, polyoxyethylene compounds described in West German Patent No. 2,748.430, Japanese Patent Publication No. 1988-883
Polyamine compounds, bromide ions, etc. described in No. 6 can be used. Among them, compounds having a mercapto group or a disulfide bond are preferable from the viewpoint of having a large promoting effect.
In particular, U.S. Patent No. 3,893,858 and West German Patent No. 1.
Compounds described in No. 290.812 and JP-A-53-95630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552.834. These bleach accelerators may be added to the photosensitive material.

These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most commonly used. Can be used widely. Preservatives for the bleach-fix solution are preferably sulfites, bisulfites, or carbonyl bisulfite adducts.

The silver halide photographic material used in the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the intended use, the temperature of the washing water, the number of washing tanks (number of stages), and the replenishment method such as countercurrent or forward flow.
It can be set in a wide range depending on various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the 5ociety
f Motion Picture and Telev
ision Er+gineers Volume 64, p 24
8-253 (May 1955 issue).

The multi-stage countercurrent method described in the above-mentioned document can significantly reduce the amount of water used for washing, but due to the increased residence time of water in the tank, grouper terriers breed, and the resulting floating matter adheres to the photosensitive material. The problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method of reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1988 can be used very effectively. Also, JP-A-57-8542
Chlorine-based disinfectants such as inchiazolone compounds, cyabendazoles, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" written by Hiroshi Horiguchi, "Microbial It is also possible to use the fungicides described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Antibacterial and Antifungal Society.

The pH of the washing water used in the processing of the photosensitive material used in the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally they are in the range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C. selected. Furthermore, the photosensitive material of the present invention can also be processed directly with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open Nos. 57-8543 and 57-8543
All known methods described in No. B-14834 and No. 60-220345 can be used.

Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide light-sensitive material used in the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.

In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342
．． Indoaniline compounds described in No. 597, No. 3.3
No. 42,599, Research Disclosure Magazine 14
．． Schiff base type compounds described in No. 850 and No. 15,159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat. Examples include type compounds.

The silver halide photosensitive material used in the present invention may contain various types of 1-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A Nos. 56-64339, 57-144547, and 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

The smaller the amount of replenishment in each treatment step, the better. The amount of replenisher is preferably 01 to 50 times, more preferably 3 to 50 times, the amount of prebath brought in per unit area of the photosensitive material.
It is 30 times more.

On the other hand, various known developing agents can be used to develop the black and white light-sensitive material in the present invention. i.e. polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylpytroquinone, catechol, pyrogallol, etc.; aminophenols such as p-aminophenol, N-methyl-p
-Aminophenol, 2,4-diaminophenol, etc., 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 5゜5-dimethyl-1-
Phenyl-3-pyrazolidone and the like, ascorbic acids and the like can be used alone or in combination. Also,
The developer described in JP-A No. 5111-55928 can also be used. Such a developer may be included in the alkaline processing composition (processing element) or in an appropriate layer of the light-sensitive material.

The developer may contain preservatives such as sodium sulfite, potassium sulfite, ascorbic acid, and reductones (eg, piperidinohexose reductone).

Further, when a DRR compound is used in the present invention, any silver halide developer or electron donor can be used as the developer as long as it can cross-oxidize the DRR compound.

Such a developer may be included in the alkaline processing solution (processing element) or in a suitable layer of the photographic material.

Examples of the developer used in the present invention are as follows.

Hydroquinone, aminophenol, such as N-methylaminophenol, 1-phenyl-3-pyrazolidinone, 1-phenyl-4゜4-dimethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-oxymethyl-
3-pyrazolidinone, N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine, 3-methoxy-N-ethoxy-p-phenylenediamine, and the like.

Among those listed here, black and white developers are particularly preferred, as in the case of the above-mentioned alkaline processing solutions, the image-receiving layer (mordant layer) generally has the property of reducing stain formation.

When the photosensitive material of the present invention is used for a film unit for diffusion transfer method, it is preferably processed with a viscous developer.

This viscous developer is a liquid composition containing processing components necessary for developing a silver halide emulsion (and forming a diffusion transfer dye image), and the solvent is mainly water, and other solvents include methanol, methyl cellosolve, etc. It may also contain hydrophilic solvents such as. Preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers are preferably used to give the treatment composition a viscosity of 1 void or more, preferably about 500 to 1000 voids, at room temperature.

The above treatment compositions are disclosed in U.S. Pat. No. 2,543,181, U.S. Pat.
No. 2,723゜051, No. 3,056,49
No. 1, No. 3.056,492, No. 3,152.5
It is preferable to use the container by filling it into a container that can be ruptured by pressure, such as those described in No. 15.

(Example〕 Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 40 g of deionized osseinized bone gelatin in 600 mj2 of water, 5 g of KBro, 4.5 c of 25% N83 water
300 cc of a silver nitrate aqueous solution containing 100 g of 8g NO3 was added over 30 minutes to the aqueous solution that had been maintained at 50°C. At that time, simultaneously with the addition of the silver nitrate aqueous solution, a halogen aqueous solution containing 90 g of KBr was added using the Chondrald double jet method to keep the pAg constant. The resulting emulsion is 0
．． It was a monodispersed emulsion consisting of 45μ octahedral crystals. After desalting and washing with water, add gelatin to adjust the pH to 65 and pAg to 9.
Adjusted to 2. The yield was 500g and the amount of gelatin contained was 50g. This core emulsion is referred to as emulsion A.

A silver iodobromide core emulsion consisting of octahedral crystals of 0.45 μm and having a sonic content of 2 mol % and uniformly doped with sonic ions was prepared in the same manner as in Emulsion A. This core emulsion is referred to as B emulsion.

To the thus obtained core emulsion A were added 136 mg of sodium thiosulfate pentahydrate and 3.4 mg of potassium chloroaurate per mole of silver, and chemically ripened at 75°C for 60 minutes.
chemical sensitization). This emulsion is designated as emulsion A-1.

Next, in core emulsion A, silver halide solvent HO-CH2C)+ 2-5- CH2C)+2-5- was added per mole of silver.
CH2CH2011 (exemplified compound (13)) at 0.3
After adding g, sodium thiosulfate and potassium chloroaurate in the same amount as emulsion A-1 were added and chemically aged at 75°C for 60 minutes (
chemical sensitization). This emulsion is designated as emulsion A-2.

Next, emulsion B was used as a core emulsion, and the core emulsion was chemically sensitized under exactly the same conditions as emulsion A-1 to obtain emulsion B-1.

Furthermore, emulsion B was used as a core emulsion and the core emulsion was chemically sensitized under exactly the same conditions as emulsion A-2 to obtain emulsion B-2.

These four types of core emulsions A-1, A-2, B-1, B-2
A silver nitrate aqueous solution and a potassium bromide aqueous solution were simultaneously added to the emulsion by a Chondral double jet method to obtain 057μ octahedral emulsions X-1 to X-4.

After desalting and washing with water, adjust the pH to 64 and pAg to 85 to obtain silver 1.
Sodium thiosulfate pentahydrate 2mg and poly(
20 mg of N-vinylpyrrolidone) was added and chemically aged at 60°C for 60 minutes.

These emulsion samples were prepared by adding 12 mg of the nucleating agent shown below per mole of silver and depositing 4 oomg/ft2 of silver on a cellulose acetate film support. Gelatin 656mg/
A coating sample was prepared by coating at a ratio of ft2.

Nucleating agent Each coated sample was exposed to 100 lux tungsten light for 1/100 seconds or 1 lux tungsten light for 1 second through an optical wedge, and then exposed to 1/100 second tungsten light of 1 lux through an optical wedge.
It was developed for 8 minutes at ℃. Table 1 shows the maximum density (Dmax) and minimum density (Dmin) of the reversed image of each developed coated sample, and the sensitivity determined from (Dmax + Dm1n)/2.

Developer solution sulfite sorter 30 g Hydroquinone 10 g l-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 075 g Trisodium phosphate 40 g Sodium hydroxide 107 g 5-Methylhensitriazole 0.02 g Add water
(Dmax + Dmin) of iIL*x-1
The sensitivity point of /2 was set as 100.

From the surface finish, it can be seen that the coating sample using emulsion X-4 of the present invention has high Dmax<low Dmin and high low-light exposure sensitivity.

Example 2 Emulsion Adjustment 60 μl of deionized ossein-treated bone gelatin in 800 mu of water
g, KBr8 1g, silver halide solvent HOC) +2
CH2S CH2CH2S CH2CH2011 [Exemplary compound (13)] 11.5 g Lead acetate 8 x 10-5 g
Add 2% to the aqueous solution kept at 75℃ without stirring well.
135 mfl of silver nitrate aqueous solution was added instantly. 32
After the mixture was left as it was for 15 minutes, 180 mu (1-a) of an aqueous solution containing 35 g of AgN and 180 mfl (I-b) of an aqueous solution containing 4.8 g of KBr were added at a uniform addition rate over 15 minutes. After leaving it for 10 minutes, Ag
210 mft of an aqueous solution containing 335 g of NO (II-a) and 210 mA of an aqueous solution containing 27.5 g of KBr (II-b)
were added at a uniform addition rate over 30 minutes.

One minute after the addition was completed, 1.8 mg of sodium thiosulfate and 0.45 mg of potassium chloroaurate were added, and chemical ripening was performed for 70 minutes. After chemical ripening, 18g of KBr was added, and immediately 585cc of an aqueous solution containing 390g of AgNO and 45 KBr were added.
．． 585 cc of an aqueous solution containing 5 g was added at a uniform addition rate over 65 minutes. After addition, add 0.2g of hydrogen peroxide.
Added and left for 8 minutes.

Thereafter, a sedimentation agent was added to sediment the emulsion, followed by washing with water and desalting. After adding deionized gelatin the pH was adjusted to 6.4.
pAg was adjusted to 82. Then sodium thiosulfate 0.7 mg y poly(N-vinylpyrrolidone) 10
mg was added and heated at 60°C for 70 minutes. The internal latent image type emulsion thus obtained is designated as Emulsion X-5. The emulsion obtained was a monodisperse octahedral emulsion with a size of 15 μm, and the yield was 1.2 kg, and the amount of gelatin contained was 65 g.

Next, an aqueous solution 210 containing 27.5 g of KBr and 6 g of KIo as a halogen solution (n-b) added to the second stage.
Internal latent image type emulsion X-6 was prepared in exactly the same manner as internal latent image type emulsion X-5 except that mρ was used. Note that the size was 15μ. The core size of both emulsions was 105μ.

Preparation of Photosensitive Material Photosensitive material I was prepared by coating the following layers in the listed order on a 150μ transparent polyethylene terephthalate film support.

(1) Copoly[styrene-N-vinylbenzyl-N,N
, N-trihexylammonium chloride] 4.0 g
Image receiving layer (2) containing 22 g/m2 of titanium dioxide and 4.0 g/m2 of gelatin and 2.75 g of gelatin.
/m2 white reflective layer (3) carbon black 1.7g/m2 and gelatin 1
．． Opaque layer (4) containing 7 g/m2 cyan dye-releasing redox compound 1.0 g/m2, N,N-diethyl laurylamide 0.50 g/m2.2-bentadecylhydroquinone-5-sodium sulfonate 0.5
g, and a layer containing 1.5 g/rn2 of gelatin LL 29 l Arashi Kanjojo 2 l λ Fugaku 1 l-1 (5) Titanium dioxide 0.5 g/m2 and gelatin 0.5
(6) Internal latent image type direct positive emulsion A layer containing sodium pentadecylhydroquinone-5-sulfonate 80 mg/m2.4-hydroxy-6-methyl-1°3.3a, 7-titrazaindene 6 mg/m2, and gelatin 1.2 g/m2 (
7) Gelatin (1,0 g/m2), 2,5-di-t-pentadecylhydroquinone (1,0 g/m2), and tricresyl phosphate (0
, 5 g/m2) (8) A dye-releasing redox compound migration prevention layer containing gelatin (0,03 g/m2) (9) A magenta dye-releasing redox compound having the following structure (
layer (10) containing titanium dioxide (0.15 g/m2) and gelatin (0.80 g/m2), N,N-diethyl laurylamide (0.20 g/m2) and gelatin (1.0 g/m2); Separating layer (11) containing internal latent image emulsion x-5 (silver 10 g/m2) and green sensitizing dye (1 mg/m2); The same nucleating agent (0.04 mg/m
2), sodium 2-pentadecylnohydroquinone-5-sulfonate (8 (1 mg/m2), 4-hydroxy-6-methyl-1°3.3a,7-chitrazaindene (6 mg/m2), gelatin ( Layer (12) having the same composition as layer (7) (13) having the same composition as layer (8) (14) containing a yellow dye-releasing redox compound (1.0 g/m2) having the following structure: /m2), N,N-diethyl laurylamide (0.25g/m2), and gelatin (1.0g/m2).
) containing ULIG+1331nJ (15) Separating layer containing titanium dioxide (0.10 g/m2) and gelatin (0.15 g/m2) (16) Internal latent image emulsion x-5 (12 g/m2 silver) and blue enhancement Sensitive dye (0.5mg/m2), (1.omg/m2) and the same nucleating agent used for layer (6) (0.09mg/m2).
2) and 4-hydroxy-6-methyl-1,3,3a,
Hoochtlinden (7 mg/m2) and gelatin (1
, 2 g) layer (17) gelatin (0,7 g/m'
) and an ultraviolet absorber with the following structure (4X10-' each)
Ultraviolet absorbing layer containing UV absorber (18) polymethyl methacrylate latex (average particle 25μ: 0.10 g/m2) and gelatin (0,
8g/m2) and hardener CH2= CHS 02 CH
2CON HCH2CH2N HCOCH2SO2CH
Layer (8), (11) containing latent image type emulsion X-5 inside the protective layer containing =CH2 (0.05 g/m2),
The pH of the preparation solution for (16) was adjusted to 57.

In addition, a surfactant in an amount necessary for coating was added to the liquid forming each layer to adjust the surface tension.

Next, a photosensitive material II was obtained in exactly the same manner as in the photosensitive material process except that emulsion X-6 was used instead of emulsion X-5.

Processing was carried out by combining the above photosensitive materials (I) and (II) with each of the elements shown below.

Treatment liquid 1-phenyl-4-methyl-4 monohydroxymethyl-3-pyrazolidone 10 g Methylhydroquinone 0.18 g 5-Methylbenzotriazole 40 g Sodium sulfite (anhydrous)
1.08 Carboxymethylcellulose Na salt 40.0g Carbon black 150
g Potassium hydroxide (28% aqueous solution) 200cc water
550 cc of the treatment solution having the above composition was filled in 0.8 g each into a pressure-destructible container J.

Preparation of cover sheet: On a 100μ polyethylene terephthalate support, a 10% by weight aqueous solution of polyacrylic acid (viscosity approximately 11,000 cp) 15/rn' is applied as an acidic polymer layer (neutralization layer), and acetylcellulose is added as a neutralization timing layer on top of this. (Hydrolyze 100g of acetylcellulose to form 3 acetyl groups.
copolymer of styrene and maleic anhydride (composition (mole) ratio, styrene maleic anhydride = approximately 6040, molecular weight approximately 50,000) 0.
A cover sheet coated with 2 g/m' was prepared.

Processing process The photosensitive materials (I) and (II) are exposed to tungsten light converted to 4800K through a color temperature conversion filter through an optical wedge for 1/100 seconds at a light intensity of 100 lux or for 1 second at a light intensity of 1 lux, and then covered. The sheet and the photosensitive material (sheet) were overlapped, and the above processing liquid was spread between the two sheets to a thickness of 75 μm (spreading was carried out with the help of a pressure roller). Processing at 25℃
I went there. After processing, the image density formed on the image-receiving layer is measured through the transparent support of the photosensitive material, and is calculated as (Dmax + Dm
Sensitivity was determined as the reciprocal of the exposure amount required to provide a density of in)/2.

Note that relative sensitivity was determined by setting the sensitivity of sensitive material (1) at 1/100 second exposure as 100.

The results are shown in Table I+.

Table II The results in Table II show that the photosensitive material 11 of the present invention has high low-light exposure sensitivity.

Example 3 Preparation of emulsion (I-a) and 0.
30 mfl of 7M/j2 potassium bromide solution (Ib)
Each addition took 15 seconds.

After this, the temperature was raised to 75°C, and 40% of the 10% by weight gelatin solution was added.
0 mA was added.

After the first addition as described above was completed, 80 mu of 0.6 M/fl silver nitrate solution (II-a) was added over 30 minutes. Then 1.47 M/fl silver nitrate solution (m-a
) and 1.47M/J2 potassium bromide solution (+n −b
) were added at an accelerated flow rate (end flow rate or 19 times the start flow rate) using a double jet method at an accelerated flow rate of 200 mfl each.
At that time, pBr was maintained at 28. This emulsion is washed by the usual flocculation method, dispersed gelatin is added,
400 g of core emulsion was obtained.

90% of the tabular grains obtained have a [ratio of the length of the side with the maximum length to the length of the side with the minimum length] of 2.
It is dominated by hexagonal tabular silver halide having the following hexagonal shape and two parallel surfaces as outer surfaces, and its coefficient of variation is 18%. In addition, the average projected area circle equivalent diameter of these particles is 04μ, and the average thickness is 0.
It was 08μ.

800 mJ2 of H2O and 30 g of gelatin were added to 200 g of the above core emulsion, and after dissolving, the temperature was raised to 75°C.

Furthermore, as a silver halide solvent, 3,4-dimethyl-1,
Add 30 mg of 3-thiazoline-2-thione [exemplified compound (38)], and further add 3 m of sodium thiosulfate.
Chemical sensitization was performed by adding 1 mg of potassium chloroaurate and 1 mg of potassium chloroaurate and heating at 70° C. for 70 minutes.

To the core emulsion chemically sensitized in this way, a 1.47M/ρ silver nitrate aqueous solution (IV-a) and 1.0% of the 1.47M/ρ silver nitrate aqueous solution (IV-a) were added in the same manner as in the core preparation.
47M/fl potassium bromide solution (+v-b) at 70℃
While maintaining the pBr at 28, each addition was carried out at an accelerated flow rate (5 times the flow rate at the end or the flow rate at the beginning) using a double jet method at an accelerated flow rate of 520 m2 each. This emulsion was washed by the usual flocculation method, 50g of dispersed gelatin was added, and 1
500 g of core/shell emulsion was obtained. The obtained tabular grains had an average projected area circular equivalent diameter of 08 μm and an average grain thickness of 0.13 μm.

In addition, 85% of the obtained tabular grains (ratio of the length of the side with the maximum length to the length of the side with the minimum length)
It is a hexagonal shape having a diameter of 2 or less, and is dominated by hexagonal tabular silver halide having two parallel surfaces as outer surfaces, and its coefficient of variation was 17%.

Next, this core/shell emulsion was added with 1.0% sodium thiosulfate.
5 mg of poly(N-vinylpyrrolidone) and 1.2 mg of chloroauric acid (tetrahydrate) were added and heated at 60° C. for 40 minutes to chemically sensitize the particle surface.

Preparation of Emulsion X-8 Halogen solution (m-b) in the preparation method of Emulsion X-7
Emulsion X-8 was prepared in exactly the same manner as X-7, except that the emulsion was changed to a halogen solution containing 142 M potassium bromide and 0.05 M potassium iodide at 1 DEG C.

Photosensitive material 111. Preparation of IV A photosensitive material Ill was prepared using emulsion X-7 as the internal latent image type emulsion in photosensitive material I of Example 2, and emulsion X-8
Photosensitive material 1■ was prepared using the following.

Exposure and development were performed using the same cover sheet and processing solution as in Example 2, and the sensitivities at 1/100 second exposure and 1 second exposure were determined.

Note that relative sensitivity was determined with the sensitivity of photosensitive material I11 exposed for 17,100 seconds as 100.

The results are shown in Table Il+.

From the results in Table II+Table III, it can be seen that the photosensitive material IV of the present invention has high low-light exposure sensitivity.

Example 4 On a paper support laminated on both sides with polyethylene, a color light-sensitive material having a multilayer structure shown in Table 1 below was prepared using emulsions X-7 and X-8 of Example 3.

The material using emulsion X-7 is called a light-sensitive material (2), and the one using emulsion X-8 is called a light-sensitive material (2).

Table IV (Layer composition) The composition of each layer is shown below. The numbers represent the coating amount per m' in g. For silver halide emulsions and colloidal silver, the coated amount in terms of silver is expressed in grams, and for spectral sensitizing dyes, the amount added per mole of silver halide is expressed in moles.

Support polyethylene laminate paper (thickness 105 μm) [White pigment (Ti02) in the polyethylene on the E1 layer side
and bluish dye (ulmarine)] E1 layer silver halide emulsion (Emulsion X-7 or Emulsion X-8) 0.26 Spectral sensitizing dye (ExSS-1) 1. OX10
-'Spectral sensitizing dye (ExSS-2) 1. O
x 10-5 gelatin 11
1 cyan coupler (ExCC-1) 0.
21 Cyan coupler (ExCC-2) 0
．． 26 Ultraviolet absorber (ExllV-1)
0.17 solvent (ExS-1
) 0.23 Development regulator (E
xGC-1) 0.02 stabilizer (
ExA-1) 0.006 nucleation accelerator
(ExZS-1) 3. Ox 10-' nucleating agent
(ExZK-1) 8. Ox 10'E
Double-layer gelatin 1.41 Color mixing prevention agent (ExKB-1) 0.09 solution
Medium (ExS-1)
0.10 solvent (ExS
-2) 0.10 E3 layer silver halide emulsion (Emulsion X-7 or Emulsion X-8) 0.23 Spectral sensitizing dye (ExSS-3) 3. Ox to
-' Gelatin 1.05 Magenta coupler (ExMC-1) 0.16 Color image stabilizer (ExSA-1) 0.20
Solvent (ExS-3)
0.25 Development control agent (ExGC-1
) 0.02 stabilizer (ExAi)
0.006 Nucleation accelerator (ExZS-
1) 2.7x 10-4 nucleating agent (E
xZK-1) 1.4X 10-5 E4 layer gelatin 047 Color mixing prevention agent (ExKB-1) 0.03 Irradiation prevention dye (EXIS-1) 0.012 Irradiation prevention dye (ExlS-2) 0.018
Solvent (ExS-1)
0.03 solvent (
ExS-2) 0.03 E5 layer colloidal silver 009 gelatin
0.49 Color mixing prevention agent
(EXKB-1) 0.03 solvent
(ExS-1) 0
．． 03 solvent (ExS-2)
0.03 E6 layer Same as E4 layer E7 layer Silver halide emulsion (Emulsion X-7 or Emulsion X-8) 0.40 Spectral sensitizing dye (ExSS-3) 4.2x 10
-' Gelatin 21 Yellow Cobbler (EXYC-1) 0.51 Solvent (ExS-2)
0.20 solvent (Ex
S-4) 0.20 development regulator
(ExGC-1) 0.06 stabilizer
(ExA-1) 0.001 nucleation accelerator
(ExZS-1) 5. Ox 10-' nucleating agent (ExZK-1) 1.2x 1o
-sE8th layer gelatin 054 ultraviolet absorber (ExUV-2) 0.21 solvent (ExS-4)
0.08 E9 layer gelatin 128 Polyvinyl alcohol acrylic 017 Modified copolymer (denaturation degree 17%) Liquid paraffin 003 Polymethyl methacrylate 0605 latex particles (average particle size 28 μm) 81st layer gelatin 870 B2 layer E9 In addition to the above composition, each layer contains a gelatin hardener ExGK -
1 and a surfactant were added.

Compounds used to prepare photosensitive materials (EXCC-1) Cyan coupler Shibu (ExCC-2) Cyan coupler (ExMC-1) Magenta coupler BM+71u
ノ (ExYC-1) Yellow coupler (ExSS-1
) Spectral sensitizing dye (ExSS-2) Spectral sensitizing dye (ExSS-3) Spectral sensitizing dye (ExSS-4) Spectral sensitizing dye (CH2)4 (CH2)a SO3H-N
(C2H5)3e (ExS-1) Solvent (ExS-2) Solvent (ExS-4) Solvent (ExlS-1) Anti-irradiation dye, l)
Su3 N Sari3 艮(ExlS
-2) Anti-irradiation dye (ExLIV-1
) 5+8+9 mixture (weight ratio) of ultraviolet absorbers (1) (2) (3) (E
xllV-2) Ultraviolet absorber 2:98 mixture (weight ratio) of the above (1), (2), and (3) (ExSA-1) Color image stabilizer (ExKB-1) Color mixing prevention agent Ut+ (ExGC-1 ) Development regulator (EXA-1) Stabilizer 4-hydroxy-5,6-drimethylene-1.3.3a
, 7-titrazaindene (ExZS-1) nucleating agent 2-(3-dimethylaminopropylthio)-5-mercapto-1,3,4-thiadiazole hydrochloride (Ex2-1) nucleating agent 7- (3 -(5-mercaptotetrazol-1-yl)henzamito)-10-propargyl-1,2,32
, 4-tetrahydroacridinium velchlorate (ExGK-1) gelatin hardener 1-oxy-3,5-cycloS-triazine sodium salt The color photographic paper thus prepared was subjected to wedge exposure (
After giving 1 second and 1/100 second exposures (10 CMS), the following processing step A was performed.

Processing step A: Time Temperature Replenishment amount Color development 90 seconds 38℃ 290mu/m
'Bleach fixing 45 seconds 35℃ 290mfl
/m'Wash ■ 30 seconds 35℃ -
Wash with water ■ 30 seconds 35℃ - water
Wash ■ 30 seconds 35℃ 320mu/m
'The washing water replenishment method was a so-called countercurrent replenishment method in which the washing bath (■) was replenished, the overflow liquid from the washing bath (■) was led to the washing bath (■), and the overflow liquid from the washing bath (■) was led to the washing bath (■). At this time, the carry-in of the photosensitive material from the prebath is 35mρ/
m', the replenishment magnification was 9.1 times.

The composition of the treatment liquid used is as follows.

(Color developer) Mother solution Additive diethylenetriaminepentaacetic acid 0.5g 0.5g1
-Hydroxyethylidene-1,1-0,5g 0.
5g diethylene glycol diphosphonate 8.0g 13.0
g Benzyl alcohol 12.0g 18.
5g Sodium bromide 07g - Sodium chloride 0.5g - Sodium sulfite 2.0g 2.5gN,N
-Diethylhydroxyl 3.5g 4.5g
Amine triethylenediamine (1,4-3,5g 4.5
gDiazabicyclo(2,2,2)octane) 3-methyl-4-amino-N-ethyl 5.5g
8.0g RuN-(β-methanesulfonamidoethyl)-aniline potassium carbonate 30.0g 30.
0g Fluorescent brightener (Stilhen type) 1.0g
Add IJg pure water 1000+nl
11000m, QpH10,5010,90 pH was adjusted with potassium hydroxide or hydrochloric acid.

[Bleach fixer]

Mother solution = Replenisher ammonium thiosulfate 100 g Sodium hydrogen sulfite 21.0 g Iron (II+) ethylenediaminetetraacetate 50.0 g Ammonium dihydrate ethylenediaminetetraacetic acid 250 g Add sodium dihydrate pure water to 1000 mρpH
6,3 pH was adjusted with aqueous ammonia or hydrochloric acid.

[Washing water]

Pure water was used (mother solution = replenisher).

Here, pure water is water in which the concentrations of all cations other than hydrogen ions and all anions other than hydroxide ions in tap water have been removed to below ippm by ion exchange treatment.

After performing the above processing, the sensitivity at each exposure time was determined.

Sensitivity is determined by measuring the image density, (Dmax + Dmin
')/2.

In addition, the relative sensitivity was determined based on the sensitivity of 1/100 second exposure of photosensitive material (1) as 100.

The results are shown in Table V.

Table 2 From the results in Table 2, it can be seen that the photosensitive material 2 of the present invention has high low-light exposure sensitivity.

Example 5 Emulsion X-4 in which the halogen composition of the shell was changed to silver iodobromide with an iodine content of 15 mol % in the preparation method of Emulsion X-4 in Example 1.
9. Emulsion X-10 with an iodine content of 3 mol % was prepared.

When the same coating, exposure and development as in Example 1 was performed,
Emulsion X-9 gave the same good photographic properties as emulsion X-4, but emulsion X-10 had very coarse grain. In addition, the maximum density of this product at 20 DEG C. and 1 minute was less than 1/2 of that using emulsions X-4 and X-9, and the progress of development was slow.

〔Effect of the invention〕

As described in detail above, according to the present invention, low-illuminance reciprocity failure is improved. In addition, it has excellent graininess and progresses well in development.

Claims (2)

[Claims] (1) Chemically sensitized in the presence of an organic silver halide solvent to form an inner core composed of silver iodobromide grains with a silver iodide content of 1 to 12 mol%, and at least the sensitization of this inner core. A direct positive silver halide emulsion characterized by containing core/shell type silver halide grains having an outer shell composed of silver halide with a silver iodide content of 0 to 2 mol% covering the sites. . (2) A silver halide photosensitive material comprising at least one emulsion layer containing the direct positive silver halide emulsion according to claim (1).