JPH0240645A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the color reproducibility of the title material, even at the tie of rapidly processing it, and the gradation balance of the photosensitive material respectively by incorporating a specified compd. in a silver halide emulsion layer and by specifying the swelling degree of a photographic constituting layer contg. the silver halide emulsion layer to a specified value. CONSTITUTION:In the case that a direct positive picture is formed, using the silver halide emulsion layer contg. an inner latent type silver halide particle which is not fogged, at least one kind of a compd. capable of scavenging an oxidant obtd. by allowing the compd. to react with the oxidant of a developing main agent or a compd. capable of releasing its precursor is incorporated in the silver halide emulsion layer. And, the swelling degree of the photographic constituting layer contg. the silver halide emulsion layer is specified to 100-170%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive silver halide photographic light-sensitive material, and more particularly to an internal latent image type direct positive silver halide photographic light-sensitive material.

[Background of the invention]

Conventionally known methods for obtaining direct positive images are mainly divided into two types. One type is to obtain a positive image after development by using a silver halide emulsion that has fog nuclei in advance and destroying the fog nuclei or latent image in exposed areas using solarization or the Burschel effect. It is. Another type is
Using an internal latent image type silver halide emulsion that does not produce fog (generally surface fog) until image exposure, fogging treatment (nucleation treatment) is performed after image exposure, and then surface development is performed, or after image exposure A positive image can be obtained by performing surface development while performing fogging treatment.

The above-mentioned fogging treatment may be performed by exposing the entire surface to light, chemically using a fogging agent, using a strong developer, or by rough heat treatment. The internal latent image type silver halide emulsion is a silver halide photographic emulsion that has photosensitive nuclei mainly inside silver halide crystal grains and forms a latent image inside the grains upon exposure.

Of the above two methods for forming a positive image, the latter type of method has -
It has high numerical sensitivity and is suitable for applications that require high sensitivity.

Various techniques are known in this technical field. For example, U.S. Patent Nos. 2,592.250, 2,466.957, 2,497,875, and 2
, No. 588,982, No. 3,761.266, No. 3,
The methods described in No. 761.276, No. 3,796,577 and British Patent No. 1,151.363 are known.

Regarding the formation mechanism of positive images, for example, Photographic Science and Engineering (Ph.D.
otographic 5science and en
gineering) vol. 20, p. 158 (1976)
As stated in , it is considered as follows. Photoelectrons generated within the silver halide crystal grains by imagewise exposure are selectively captured inside the grains, forming an internal latent image.

This internal latent image acts as an effective capture center for electrons in the conductive band, so in exposed particles, electrons injected during the subsequent fogging and development process are captured internally and strengthen the latent image. become. In this case, the latent image is all internal and is not developed. - For particles that have not undergone image exposure, at least some of the injected electrons are captured on the particle surface and the particle is developed by surface development.

Although it is possible to produce photographic materials that form positive images by using the above-mentioned known techniques, further improvement in photographic performance is desired in order to apply these photographic materials to various photographic fields. There is.

For example, in recent years, it has become possible to directly obtain a positive image on the internal latent image type silver halide color photographic paper or color film using a copying machine using a printed original or a versatile film as the original. In order for such photocopying apparatuses to become widely used for various purposes, it is strongly desired to shorten the processing time of photosensitive materials and improve image quality.

Various methods have been used to shorten the processing time of color photographic materials.

Among these, it is useful to variously change the type of silver halide, especially the halide composition, in the light-sensitive material. As is well known, silver chloride has higher ionicity and is more soluble than silver bromide and silver iodide, so the development speed is faster.
Furthermore, the subsequent bleaching and fixing treatments can be performed more quickly. Therefore, using silver halide with a high silver chloride content is advantageous in terms of shortening the processing time.

On the other hand, silver chloride-containing internal latent image type silver halide grains having a core/shell laminated structure are well known. For example, JP-A-47-32820 discloses a structure in which a core of silver bromide (or silver iodobromide) is coated with a shell of silver chloride, and a structure in which a layer with a high content of silver chloride is localized. Japanese Patent Application Publication No. 5
It is disclosed in No. 0-8524 and No. 50-38525.

Regarding improvement of image quality, it is known to use a so-called DIR coupler, for example, to improve color reproducibility due to the glabellar effect.

As a DIR coupler, for example, British patent 953,45
No. 4, U.S. Pat. No. 3,227.554, U.S. Pat. No. 3,615.
No. 506, No. 4゜286.054, JP-A-52-90
Compounds described in No. 932, No. 56-116029, etc.
U.S. Patent No. 4,248,962, JP 59-2068
Timing DIR couplers described in Japanese Patent No. 34 and No. 59-210440 are known, but their effects cannot be fully demonstrated in rapid processing.

On the other hand, it has been found that when the compound described in JP-A-57-138636 is used, the above-mentioned drawbacks in rapid processing are improved, but when used directly in positive light-sensitive materials, the following drawbacks occur. That is, it is difficult to adjust the tone balance between two layers of a light-sensitive material having at least two layers of internal latent image type direct positive silver halide emulsion layers with mutually different color sensitivities, and slight processing solution fluctuations and processing time It has been difficult to put this compound into practical use because it is greatly affected by fluctuations.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a direct positive silver halide photographic light-sensitive material that has good color reproducibility even when rapidly processed and can produce positive images with excellent tone balance.

[Structure of the invention]

The above object of the present invention is to provide at least one silver halide grain containing an internal latent image type silver halide grain whose grain surface is not fogged in advance.
In a photographic light-sensitive material having a silver halide emulsion layer as a layer, and obtaining a positive image directly by surface development after image exposure, after fogging treatment and/or while performing fogging treatment, the silver halide emulsion layer is a compound capable of reacting with and scavenging oxidation products of the developing agent in the layer;
or at least one compound capable of releasing its precursor.
This was achieved using a direct positive silver halide photographic light-sensitive material containing seeds and having a swelling degree of 100 to 170% in the photographic constituent layers including the silver halide emulsion layer.

The present invention will be explained in detail below.

First, a compound capable of scavenging an oxidation product of a developing agent or a compound capable of releasing its precursor (hereinafter referred to as "rDSR compound") by reaction with the oxidation product of a developing agent used in the present invention will be explained. .

The DSR compound is, for example, represented by formula (1).

General formula CI) Coup-(T I ME)g SC Above-Formula (
In I), Coup is a coupler residue that can cause a coupling reaction with the oxidation product of the aromatic primary amine developing agent, and TIME is the timing at which SC is further released after being separated from Coup by the coupling reaction. The base,
a represents O or l, SC is a group that is separated from Coup during the coupling reaction when Q is O, and when Q is 1
is a group released from TIME, and represents a scavenger or its precursor that can scavenge the oxidation product of a color developing agent by oxidation reaction, coupling reaction, etc.

More specifically, the coupler residue represented by Coup is, for example, a yellow coupler residue, a magenta coupler residue, a cyan coupler residue, or a coupler residue whose product is substantially colorless, and is preferably Below - Formula (n
) or II).

General formula (II) - Formula (I[[)
General formula CIV) General formula (V) General formula [■] - Formula (ff) above -
R in formula (If) represents an alkyl group, an aryl group, or an arylamino group, and R2 represents an aryl group or an alkyl group.

In the above formula (III), R1 represents an alkyl group or an aryl group, and R4 represents an alkyl group, an acylamino group, an arylamino group, an arylureido group, or an alkylureido group.

In the above formula (IV), R1 has the same meaning as R4 in general formula (I[), and R6 represents an acylamino group, a sulfonamide group, an alkyl group, an alkoxy group, or a halogen atom.

Further above - substituent R7 in the formulas CVI and (Vl)
represents an alkyl group, an aryl group, an acylamino group, an arylamino group, an alkoxy group, an arylureido group, or an alkylureido group, and R6 represents an alkyl group or an aryl group.

R9 in the above formula [■] represents an acylamino group, a carbamoyl group, an arylureido group, and R6 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group,
Represents a sulfonamide group.

In the above formula [■], R9 has the same meaning as the general formula [■], and is Ro. represents an amino group, a carbonate amide group, a sulfonamide group, or a hydroxyl group.

In the above formula ([), R11 represents a nitro group, an acylamino group, a succinimide group, a sulfonamide group, an alkoxy group, an alkyl group, a halogen atom, or a cyan group.

In addition, p in the above-mentioned formula [■] and 14) represents an integer from O to 2, and q in the above-mentioned formula [■] is 0.
Represents an integer from 1 to 1.

Furthermore, each of the above groups includes those having a substituent, and preferable substituents include a halogen atom, a nitro group, a cyano group,
Sulfonamide group, hydroxyl group, carboxyl group,
An alkyl group, an alkoxy group, a carbonyloxy group, an anrulamino group, and an aryl group are arbitrarily selected.

The lipophilicity exhibited by R1 to R11 in each of the above formulas can be arbitrarily selected depending on the purpose, and in the case of a normal image forming coupler, the total number of carbon atoms of R1 to R1□ is preferably IO to 60, and Preferably it is 15 to 30. On the other hand, the dye produced by color development is
In the case of a mobile dye-forming coupler that moves appropriately in a light-sensitive material, the total number of carbon atoms in R to R1 is preferably 15 or less. When the product is a substantially colorless coupler, the number is preferably 15 or less, and it is further preferred that R1 to Rlo have at least one carboxyl group, arylsulfonamide group, or alkylsulfonamide group as a substituent.

Note that coupler residues whose products are substantially colorless include those whose product concentration is 0.3 or less, those in which the generated dye flows out from the light-sensitive material into the processing solution, or the components in the processing solution. These are known as Weiss couplers, run-off dye-forming couplers, and bleachable dye-forming couplers, respectively.

In the above formula CI), the timing group represented by TIME is preferably represented by the following formula (X), (XI) or (XI[).

In the formula, B represents an atomic group necessary to complete the benzene ring or naphthalene ring, Y represents 10-S- or -N-, and is bonded to the active point of Coup of the formula CI). Rdz, R13 and R1 are each substituted with a hydrogen atom, an alkyl group or an aryl group at the distal position, and are bonded to SC.

- Formula (XI) In the formula, Y, R, 2, R1, each have the same meaning as in the above-mentioned formula (X), and RI6 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group, an alkoxycarbonyl group, or represents a heterocyclic residue, R16 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amine group,
Displays acid amide group, sulfonamide group, carboxy group, alkoxycarbonyl group, carbamoyl group or cyan group.

In addition, the timing group represented by the above-mentioned formula [r] is similar to the above-mentioned formula [X], where Y is R12 of Coup. Then, the timing group represented by the above-mentioned formula [r] is TIME, which releases SC by an intramolecular nucleophilic substitution reaction.
Examples of the group include those represented by the following formula (XI[).

General formula (III) -Nu-D-E-Z In the formula, Nu represents a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, and is bonded to the coupling position of Coup, E represents an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group, this electrophilic group E is bonded to the heteroatom of SC, and D is A bond that sterically associates Nu and E and, after Nu is released from Coup, can break the intramolecular nucleophilic substitution accompanied by the formation of a 3- to 7-membered ring, and thereby release SC. represents a group.

Further, there are a redox type which is produced from a scavenger of an oxidized color developing agent represented by SC or its precursor, and a coupling type.

When the scavenger scavenges the oxidized color developing agent by a redox reaction, the scavenger is a group capable of reducing the p-form of the color developing agent, such as ^nge.
w, Chap, Int, Ed,, 17875~
886 (1978), The Theory of
Reducing agents described in the Photographic Process, 4th edition (Mac Millan 1977), Chapter 11, JP-A-59-5247, and the like are preferred, and precursors that can release such reducing agents during development may also be used. Specifically, when reacting with an oxidized color developing agent, -OH group, -NH30□R group, -NH, group, -NHR
An aryl group or a heterocyclic group having at least two groups (representing multiple groups such as group, kyl, alkenyl, or aryl) is preferable;
Among them, an aryl group is preferable, and a phenyl group is more preferable. The lipophilicity of SC can be arbitrarily selected depending on the purpose, similar to the above-mentioned couplers represented by formulas (II) to CI, but when using the compound of the present invention, it can be selected mainly in order to exhibit an intralayer effect. The total number of carbon atoms in SC is 6 to 50, preferably 10 to 45, more preferably 15 to 45. In order to mainly produce the glabellar effect, the total number of carbon atoms in SC is 6 to 30. Preferably it is 6-20.

When the SC is a scavenger that scavenges oxidized color developing agent through a coupling reaction, the product is a substantially colorless coupler residue.

Specific examples of DSR compounds include, for example, British Patent No. 1546837, Japanese Patent Application Laid-open No. 150631/1983,
No. 7-111536, No. 57-11537, No. 57-
No. 138636, No. 60-185950, No. 60-2
No. 03943, No. 60-213944, No. 60-21
No. 4358, No. 61-53643, No. 61-8464
No. 6, No. 61-86751, No. 61-102646, No. 61-102647, No. 61-107245,
No. 61-113060, No. 61-231553, No. 61-233741, No. 61-236550, No. 6
No. 1-236551, No. 61-238057, No. 61
There are those described in No. -240240, No. 61-249052, etc.

As the scavenger, a redox type scavenger can be preferably used.

Next, DSR compounds will be illustrated, but the present invention is not limited to the exemplified compounds below.

SR-1 5R-2 5R-3 C.I.

n SR-4 S Hs O CH.

rθ rθ S H 5R-28 rihbu2t, ;ahs DSR-29 NH3O□N(CHs)z 5R-3O NH5OzN(C)Is)2 5R-35 5R-36 NH3O,N(C4H9)z 5R-32 5R-33 5R-34 5R-38 The DSR compound of the present invention can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer. preferable.

Two or more types of DSR compounds of the present invention can be contained in the same layer. The same DSR compound may also be included in two or more different layers.

These DSR compounds are generally preferably used in amounts of 2 X 10-' to 5 X 30-' moles, more preferably I X 10-' to I X 10-' moles per mole of silver in the emulsion layer.
Use moles.

In order to incorporate these DSR compounds into the silver halide emulsion according to the present invention or other photographic constituent layer coating solutions, if the DSR compounds are alkali-soluble, they may be added as an alkaline solution. If it is oil-soluble, for example, US Pat. No. 2,322,027, US Pat.
．． No. 170, No. 2,801.171, No. 2,272.
According to the method described in No. 191, No. 2,304.940, etc., the DSR compound is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, and dispersed in the form of fine particles to form a silver halide emulsion. It is preferable to add

The above DSR compound is disclosed in Japanese Patent Application Laid-Open No. 57-138638,
No. 57-155537, No. 57-171334, No. 58-11941, No. 61-53643, No. 61-
No. 84646, No. 61-86751, No. 611026
No. 46, No. 61-102647, No. 61-10724
It can be synthesized by the method described in No. 5, No. 61-113060, etc.

The compound or its precursor that undergoes a coupling reaction or redox reaction with the oxidized developing agent released from the DSR compound of the present invention in accordance with the density of the image during development is as follows:
Within the light-sensitive emulsion layer, the dye-forming reaction (coupling reaction) is suppressed in accordance with the image density, producing so-called intra-image effects such as improving image sharpness, and on the other hand, in other layers where it has diffused. It is possible to obtain two types of image effects, such as a so-called inter-image effect, such as a masking effect that inhibits the dye-forming reaction of that layer in accordance with the density of the image of the layer of the diffusion source.

Next, the degree of swelling will be explained.

In the present invention, the swelling degree is defined by the following formula.

Swelling degree (%) - Mokari 00 Q In the formula, Wa represents the weight per unit area of the photographic constituent layer to be measured when dry, and Wω represents the photographic light-sensitive material having the photographic constituent layer described above in purified water at 38°C. It represents the weight per unit area of pure water impregnated into the photographic constituent layer when immersed in water for 3 minutes. In other words, the degree of swelling indicates the amount of penetration of a processing solution such as a color developer into the photographic constituent layer.

The degree of swelling of the photographic constituent layers of the photographic light-sensitive material of the present invention is 100 to
It needs to be 170%, more preferably 1
It is 10 to 160%, more preferably 110 to 150%.

The silver halide used in the present invention preferably contains silver chloride from the viewpoint of rapid processability, and examples thereof include silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, etc. In the case of core/shell type silver halide grains, silver bromide or silver iodobromide may be used for the core. The silver chloride content based on the total silver halide is preferably 10 mol% or more, more preferably 20 mol% or more.

That is, the silver halide grains used in the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

Even though the method of creating and growing seed particles is the same,
May be different. A silver halide emulsion containing the silver halide grains may be prepared by simultaneously mixing halide ions and silver ions, or by mixing one of them in a solution in which the other is present.

Also, while considering the critical growth rate of silver halide crystals,
pH and pA of halide ion and silver ion mixing pot
It may also be produced by controlling the amount of g and adding them simultaneously. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

Conversion methods can also be used to change the halogen composition of the particles after growth.

The silver halide grains according to the present invention may be composed of at least two types of layers, that is, at least two types of layers having different halogen compositions, and the outermost shell layer is at least a part of the inner core layer. It may be sufficient to just cover it. It may have a so-called core/shell structure in which the inner core layer forms the core and the outer shell layer covers the core as a shell, or it may have a structure in which the first layer covers a portion of the second layer.

The silver halide grains according to the present invention may be composed of three or more types of layers. For example, the first core, which is the most central
Silver halide grains may have a three-layer structure consisting of a layer, an inner core layer covering the layer, and an outer shell layer further covering the inner core layer. Hereinafter, in order to simplify the explanation, a particle with a two-layer structure will be taken up, and the first layer located on the outermost side will be assumed to be an outer shell layer, and the second layer adjacent to it will be assumed to be an inner core layer, but the present invention The silver halide grains are not limited to grains having a two-layer structure.

The inner core layer of the silver halide grains according to the present invention preferably contains less silver chloride than the silver chloride contained in the outer shell layer.

The inner core layer preferably mainly consists of silver bromide and may further contain silver chloride and/or silver iodobromide. The shape of the silver halide grains forming the inner core layer may be any shape, for example, cubic, octahedral, dodecahedral,
The particles may be tetradecahedral or a mixture thereof, or may be spherical, tabular, irregularly shaped particles, or an appropriate mixture of these. In carrying out the present invention,
The average particle size and particle size distribution of the silver halide grains constituting the inner core layer can vary widely depending on the desired photographic performance, but a narrower particle size distribution is more preferable. Specifically, it is preferable that 90% by weight of the 710 silver germide grains constituting the inner core layer is 40% or more from the average grain diameter, and more preferably, the grains have diameters that are no more than 30% apart from the average grain diameter.

That is, the silver halide grains constituting the inner core layer are preferably substantially monodisperse.

Here, silver halide grains with a monodisperse inner core layer mean that the weight of silver halide grains included within a grain size range of ±20% around the average grain size T in the silver halide grains constituting the inner core layer. It is 60% or more of the total silver halide weight, preferably 70% or more, particularly preferably 80% or more.

Here, the average grain 1r is the frequency ni of grains having a grain size ri
The product of n1Xri3 and ri3 means the particle size ri that is the maximum (3 significant figures, minimum number of digits is 4 to the nearest 5).
In addition, the grain size here refers to the diameter in the case of spherical silver halide grains, and in the case of grains with shapes other than spherical, the diameter when the projected image is converted into a circular image of the same area. It is the diameter.

Examples of the method for producing the monodisperse core emulsion include, for example, Japanese Patent Publication No. 48-36890, Japanese Patent Application Laid-Open No. 54-48520,
The double jet method disclosed in Japanese Patent No. 54-65521 and the like can be used. In addition, JP-A-54-158220
The premix method described in No. 1, etc. can also be used.

The inner core layer preferably has few lattice defects and is disclosed, for example, in US Pat. No. 2,592,250. Emulsions produced by conversion methods are not suitable as inner core layers. Particles produced by the above-mentioned double jet method while controlling pn and I)Ag during production have fewer lattice defects and are preferable as the inner core layer.

The inner core layer can be prepared in the presence of a silver halide solvent. Thioethers shown in US Pat. No. 3,574.628, thiourea derivatives shown in JP-A-55-77737, imidazoles shown in JP-A-54-100717, etc. can be used. In a preferred embodiment of the present invention, ammonia is preferably used as the silver halide solvent.

In the silver halide grains according to the present invention, the outer shell layer preferably covers 50% or more of the surface area of the grains constituting the inner core layer. The outer shell layer can contain silver bromide or silver iodide to the extent that photographic performance is not adversely affected. A portion of the outer shell layer can be converted into silver bromide or silver iodide using a trace amount of water-soluble bromide or iodide.

The outer shell layer can completely cover the inner core layer or can selectively cover a part of the inner core layer, but preferably covers 50% or more of the surface area of the particles constituting the inner core layer. is preferred. More preferably, the inner core layer is completely covered.

As a method for forming the outer shell layer, the above-mentioned double jet method, premix method, etc. can be used. It is also possible to mix fine grains of silver halide into an emulsion containing grains constituting the inner core layer and form it by Ostwald ripening.

In practicing the present invention, the inner core layer of the silver halide grains is chemically sensitized, doped with metal ions, or both, or not at all. It may be something.

As the chemical sensitization, sulfur sensitization, gold sensitization, reduction sensitization, noble metal sensitization, and a combination of these sensitization methods can be employed. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used. Such a method is described, for example, in US Pat.
No. 574.944, No. 1.623.499, No. 2, 4
No. 10.689, No. 3,656.955, etc.

The inner core layer of the silver halide grains used in carrying out the present invention is, for example, US Pat. No. 2,399.083;
As described in No. 597,856 and No. 2,642,361, sensitization can be carried out with a water-soluble gold compound or with a reduction sensitizer.

Such methods are described, for example, in U.S. Pat.
．． No. 850, No. 2,518.698, No. 2,983.
Reference can be made to the description in No. 610 and the like.

Furthermore, noble metal sensitization can also be carried out using noble metal compounds such as platinum, iridium, palladium, and the like. Such methods are described, for example, in U.S. Pat.
Reference may also be made to the descriptions in No. 8,060 and British Patent No. 618.061.

Additionally, the inner core layer of the silver halide grains can be doped with metal ions. To dope the inner core layer with metal ions, the metal ions can be added as water-soluble salts, for example, during any process of forming particles of the inner core layer. Preferred specific examples of metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, osmium, and rhodium. These metal ions are preferably used in concentrations of 1X10-'' to 1X10 moles per mole of silver.

However, those used as the inner core layer of silver halide grains are
The material may not be subjected to the above-mentioned chemical sensitization treatment or metal ion doping.

In this case, it is thought that photosensitive centers are generated by forming crystal strain at the interface between the inner core layer and the outer shell layer during the process of covering the particles in the inner core layer with the outer shell layer. U.S. Patent No. 3°935.014, No. 3
, 957,488.

The silver halide emulsion used in the present invention can be chemically sensitized by a conventional method at any stage of production. Furthermore, the silver halide grains of the present invention can store polyvalent metal ions inside the grains. Preferred specific examples of polyvalent metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, platinum, osmium, and rhodium.

In the silver halide grains according to the present invention, it is preferable that the grain surface is not chemically sensitized, or even if it is sensitized, it is only to a small extent.

In the present invention, the meaning that the particle surface is not prefogged means that the emulsion used in the present invention is coated on a transparent film support at a concentration of 35 mgAg/ell, and the surface is developed as described below without exposure. 1 at 20°C with solution A
This means that the density obtained when developing for 0 minutes does not exceed 0.6, preferably 0.4.

Surface developer A Metol 2.5 g Toascorbic acid lθ8 Sodium metaborate (tetrahydrate) 35 g Potassium bromide 1 g Add water Iff Also, the silver halide emulsion according to the present invention was tested as described above. After exposing the strip, it provides sufficient density when developed with internal developer B having the following formulation.

Internal developer B Metol ゛ 2g Sodium sulfite (anhydrous) 90g Hydroquinone 8g Sodium carbonate (l
water salt) 52.5g potassium bromide
5g potassium iodide
Add 0.5g water
112 More specifically, if a portion of the specimen is exposed to a light intensity scale for a defined period of time up to about 1 second and developed in internal developer B at 20'O for 10 min. exhibiting a maximum density that is at least 5 times, preferably at least 10 times, that obtained when another portion of the specimen exposed under the same conditions is developed in surface developer A for 10 minutes at 20'O. It is something.

The silver halide emulsion according to the present invention can be optically sensitized using commonly used sensitizing dyes. Combinations of sensitizing dyes used for supersensitization of internal latent image type silver halide emulsions, negative-working silver halide emulsions, etc. are also useful for the silver halide emulsions of the present invention. RD for sensitizing dyes
Reference may be made to No. 15162 and No. 17643.

Alternatively, chemical sensitization may be carried out, and can be carried out by ordinary sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, or a combination thereof. Useful surface chemical sensitization is described in US Pat. No. 3,761,276.

The photographic light-sensitive material of the present invention is image exposed (photographed) by a conventional method.
After that, a positive image can be easily obtained directly by surface development. That is, the main step of directly creating a positive image is to remove fogging nuclei by chemical or optical action after image exposure of the photographic light-sensitive material having an internal latent image type silver halide emulsion layer that has not been fogged in advance. It consists of performing surface development after and/or while performing a process to generate a fog, that is, a fog process. Here, the fogging treatment can be carried out using a compound that provides full exposure or generates fogging nuclei, that is, a fogging agent.

In the present invention, the entire surface exposure is carried out by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface to light. The light source used here may be any light within the wavelength range to which the photographic light-sensitive material is sensitive; high-intensity light such as flash light may be applied for a short period of time, or weak light may be applied for a long period of time. . Further, the total exposure time can be varied over a wide range depending on the photographic material, development processing conditions, type of light source used, etc. so as to ultimately obtain the best positive image.

A wide variety of compounds can be used as the fogging agent used in the present invention, and it is sufficient that the fogging agent is present during the development process. (preferably in the silver oxide emulsion layer), or may be contained in the developer or the processing solution prior to development. The amount used can vary widely depending on the purpose, and the preferred amount is 1 to 1,500 mg per mole of silver halide when added to a silver halide emulsion layer, preferably 1 to 500 mg per mole of silver halide.
It is 1.000111Ig. Further, when added to a processing solution such as a developer, the preferable amount is 0. O1~5g/Q
s is particularly preferably 0.05 to Ig/Q.

Fogging agents used in the present invention include, for example, U.S. Pat.
563,785, hydrazines described in 2.588,982, or U.S. Pat. No. 3,227.5
Hydrazide or hydrazone compounds described in US Pat. No. 52; US Pat. No. 3,615.615, US Pat.
No. 9, No. 3,719.494, No. 3,734,738
Heterocyclic quaternary nitrogen salt compounds described in No. 3,759.9 and old No. 3,759.9; and acylhydrazinophenylthioureas described in U.S. Pat. Examples include compounds having an adsorption group. Moreover, these fogging agents can also be used in combination.

For example, RD No. 15162 describes the use of a non-adsorbent fogging agent in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention.

As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, and they can also be used in combination.

Specific examples of useful fogging agents include phenylhydrazine hydrochloride, l-formyl-2-(4-methylphenyl)hydrazine, l-acetyl-2-phenylhydrazine,
- Hydrazine compounds such as methylsulfonyl-2-(3-phenylsulfamidophenyl)hydrazine; 3-(
N-substituted quaternary cycloammonium salts such as 2-formylethyl)-2-methylbenzothiazolium bromide, 2-methyl-3-(3-(phenylhydrazino)propyl)benzothiazolium bromide; 5-(1-ethylnaphtho[1,2-b]thiazolin-2-ylideneethylidene]-1-(2-phenylcarbazoyl)methyl-3
-(4-sulfamoylphenyl)-2-thiohydantoin, 5-(3-ethyl-2-penzothiazolinylidene)-3-(4-(2-formylhydrazino)phenyl]
rhodanine, i (4-(2-formylhydrazino)phenyl]-3-phenylthiourea, 1,3-bis(4-
(2-formylhydrazino)phenylcothiourea and the like.

After image exposure, the photographic light-sensitive material having a silver halide emulsion layer according to the present invention is subjected to full-surface exposure or surface development treatment in the presence of a fogging agent to directly form a positive image. This surface development processing method means processing with a developer substantially free of silver halide solvent.

Developers that can be used in the surface developer used for developing the photographic light-sensitive material of the present invention include common silver halide developers, such as polyhydroxybenzenes such as hydroquinone, amide/phenols, 3-11m
"It includes lanridones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc., or mixtures thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, l-7enyl-3-
Pyrazolidone, l-phenyl-4,4-dimethyl-3-
Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, ascorbic acid, N,
N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 4-amino-3-methyl-N-ethyl −N−(β
-hydroxyethyl)aniline and the like. These developers can also be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution.

The developer used in the present invention can further contain specific antifoggants and development inhibitors, or these developer additives can be optionally incorporated into the constituent layers of the photographic material. It is.

Depending on the purpose, various photographic additives such as wetting agents, film property improvers, and coating aids may be added to the silver halide emulsion according to the present invention.

Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and developers. Speed modifiers, matting agents, etc. may also be used.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc. as required, and the internal latent image of the present invention is transferred to a silver halide photographic light-sensitive material. obtain.

It is useful to apply the photographic light-sensitive material according to the present invention to color applications, and in this case it is preferable to include cyan, magenta and yellow dye image-forming couplers in the silver halide emulsion. As the coupler, commonly used couplers can be used, and a specific example thereof is RD-17643 (197
(December 1979) and No. 18717 (November 1979).

Furthermore, it is useful to use an ultraviolet absorber to prevent the dye image from fading due to short-wavelength actinic rays.

Examples of the support for the photographic light-sensitive material according to the present invention include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc., which have been subjected to undercoating as necessary. It will be done.

In addition to gelatin, suitable gelatin derivatives can be used as protective colloids or binders in the silver halide emulsion layer according to the present invention, depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

In addition, in the present invention, other hydrophilic binders (binders) can be included depending on the purpose, and include polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, etc. The hydrophilic binder can be added to constituent layers of photographic light-sensitive materials such as layers, filter layers, backing layers, etc., depending on the purpose, and the hydrophilic binder can also contain suitable plasticizers, lubricants, etc. depending on the purpose. can.

Further, the constituent layers of the photographic light-sensitive material according to the present invention can be hardened with any suitable hardening agent. Examples of these hardeners include chromium salts, zirconiums, aldehyde hardeners such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners.

Further, the photographic light-sensitive material according to the present invention has, on a support, at least one photosensitive emulsion layer containing the internal latent image type silver halide grains according to the present invention, as well as a filter layer, an intermediate layer,
It is possible to provide a large number of various photographic constituent layers such as protective layers, subbing layers, backing layers, antihalation layers, etc.

When the photographic material of the present invention is used for full color use, at least one red-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one blue-sensitive silver halide emulsion layer are coated on the support. be done. At this time, at least one light-sensitive silver halide emulsion layer may contain internal latent image type silver halide grains according to the present invention, but all light-sensitive silver halide emulsion layers contain internal latent image type silver halide grains according to the present invention. Preferably, it contains latent image type silver halide grains. Furthermore, each light-sensitive silver halide emulsion layer may be the same color-sensitive layer or may be separated into two or more layers having different sensitivities; in this case, at least one layer may have different sensitivities. The same color-sensitive layer may contain the internal latent image type silver halide grains of the present invention, but it is preferable that all emulsion layers contain the internal latent image type silver halide grains of the present invention. .

The color development time when processing a color direct positive light-sensitive material is preferably within 2 minutes for the purpose of rapid processing, more preferably within 1 minute and 30 seconds, particularly preferably within 1 minute.

The photographic light-sensitive material according to the present invention is suitable for general black and white use, for X-ray use,
It can be effectively applied to a variety of applications such as color, false color, printing, infrared, magenta, micro, and silver dye bleaching. Patent No. 3,087,817, Patent No. 3,185.5
No. 67 and No. 2,983.606, U.S. Pat. No. 3,253.915 to Waishets et al., U.S. Pat.
No. 27.551, U.S. Pat. No. 3,227 to Whitemore et al.
．． No. 552 and U.S. Pat. No. 3,415.644 to Rand et al.
No. 3,415゜645 and No. 3,415.646
It can also be applied to a color image transfer method, a color diffusion transfer method, etc. as described in No.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example I (Preparation of emulsion A) A monodisperse silver bromide emulsion was prepared as follows.

While controlling an aqueous solution containing ossein gelatin at 70°C and stirring vigorously, a silver nitrate aqueous solution and a potassium bromide aqueous solution were simultaneously added to the solution using the Chondrold double jet method. An emulsion was obtained.

To this emulsion were added 5 mg of sodium thiosulfate and 6 mg of chloroauric acid (tetrahydrate) per mole of silver, and
Chemical ripening was performed by heating for a minute to obtain a silver bromide core emulsion.

The core emulsion thus obtained was further grown by adding a silver nitrate aqueous solution and a potassium bromide aqueous solution, and the average grain size was 0.7.
An octahedral monodispersed core/shell silver bromide emulsion of μm was obtained. After washing and desalting, this emulsion contains 1.3
mg of sodium thiosulfate and chloroauric acid (tetrahydrate) were added and chemically sensitized by heating at 60° C. for 70 minutes to obtain an internal latent image type silver halide emulsion.

(Preparation of emulsion B) A silver bromide core emulsion obtained in exactly the same manner as emulsion A was grown by adding an aqueous silver nitrate solution and an aqueous solution containing potassium bromide and sodium chloride (40:60 in molar ratio) to obtain an average grain size. A monodispersed octahedral core/shell silver chlorobromide emulsion with a diameter of 0.7 μm was obtained. After washing with water and desalting, this emulsion contains 1.3 mg each of sodium thiosulfate and chloroauric acid (4 mg) per mole of silver.
water salt) was added thereto and heated at 60°C for 70 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion.

A color photographic material (Sample 1) having the following layer structure was prepared on a paper support laminated on both sides with polyethylene.

Note that the numbers indicate the amount of coating (a+g/dm").

7th layer (protective layer) Gelatin 12.3 6th layer (
Ultraviolet absorption layer) Gelatin 5.4 Ultraviolet absorber (UV-1) 1.0 Ultraviolet absorber (U
V-2) 2.8 solvent (SO-3)
1.2 Fifth layer (blue-sensitive layer) Blue-sensitive emulsion (silver equivalent), which is color-sensitized by adding a blue-sensitive sensitizing dye (BD-1) to emulsion A. Gelatin yellow coupler (YC- Image stabilizer (A O -2) Solvent (So-1) Fogging agent (FA-1) 4th layer (yellow filter layer) Gelatin yellow colloidal silver ultraviolet absorber (UV-1) 5, O 13,5 1) 8.4 3.0 5.2 15.0 mg 1 mol Silver 4.2 1.0 0.5 Ultraviolet absorber (UV-2) 1.4 Color mixing inhibitor (A S-1) 0.4 Solvent (S
O-3) 0.8 3rd layer (green photosensitive layer) Green-sensitive emulsion (silver equivalent) sensitized by adding green-sensitive sensitizing dye (GD-1) to emulsion A 2.7 Gelatin 13.0 Magenta Coupler (MC-1) 2.4 Image stabilizer (
A O-1) 2.0 solvent (S O-4
) 3.15 Fogging agent (F A -1) 15.0 mg 1 mol Silver 2nd layer (color mixing prevention layer) Gelatin 7.5 Color mixing prevention agent (A s -1) 0.55 Solvent (so
-2) 0.72 1st layer (red-sensitive layer) Red-sensitive emulsion (silver equivalent) obtained by adding red-sensitive sensitizing dyes (RD-1 and RD-2) to emulsion A to sensitize the color (in terms of silver) 4.0 Gelatin 13 .8 cyan coupler (CC-1) 2.1 cyan coupler (
CC-2) 2.1 Image stabilizer (A O-2
) 2.2 Solvent (So-1) 3.3 Fogging agent (FA-1) 15.0 mg 1 mol silver Note that 5A-1 and 5A-2 were used as coating aids, and HA-1 was used as a hardening agent. Coating was performed by adding 6 mg of gelatin per Ig of gelatin.

(Additives used) BD-1 BD-1 BD-1 FA-1 C-1 BD-2 MC-1 So-4 M.C. S-1 H So-1 O-2 O-1 O-2 Su11 O-3 A-1 V-1 Table 1 V-2 A-1 C2H.

Blind CHzCOOCHzCHC+Hs A As shown in Table 1, coupler YC-1, MC-
Also, a hardening agent in which the DSR compound of the present invention was added in place of 1 and CC-1! (Photosensitive materials (samples 2 to 12) were prepared in which the amount of A-1 added was varied.

Each sample obtained was exposed to light using a light-sensitive needle through an optical wedge and a color correction filter with the sensitivity adjusted so that D = 1.0 and approximately gray, and the processing steps shown below were performed. processed.

[Processing=1] Processing process Time Temperature color development
2 minutes 33℃ bleach fixing 4
0 seconds Stable at 33°C Dry at 33°C 3 times for 20 seconds each
30 seconds 60-80℃ Color developer formulation Diethylenetriaminepentaacetic acid 2.0g Benzyl alcohol diethylene glycol 3.4g Sodium sulfite 2.0g Sodium bromide 0.5g Hydroxylamine sulfate 2.6g Sodium chloride
3.2g 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline sulfate 4.25g potassium carbonate 30.0g fluorescence enhancer 4.4' diaminostilbendisulfonic acid derivative)
Add 1.0 g water
ig (pi with potassium hydroxide or sulfuric acid)
Adjusted to 10.5. ) Bleach-fix solution formulation Ammonium thiosulfate (54wt%) 150m
ff Sodium sulfite 15g Iron ethylenediaminetetraacetate (I[[) Ammonium 55g Sodium ethylenediaminetetraacetate (dihydrate) 4g Glacial acetic acid
Add 8.61g water
lQ (adjusted to pH 5.4 with aqueous ammonia or hydrochloric acid) Stable liquid formulation l-hydroxyethylidene-1.1-diphosphonic acid (60%) 1.6mf
f Bismuth chloride 0.35g Polyvinylpyrrolidone 0.25g Aqueous ammonia 2.5m12 Nitrilotriacetic acid/3Na 1. O g5-chloro-2-methyl-4-inthiazolin-3-one 50mg2-
Octyl-4-isothiazolin-3-one 50mg
Optical brightener (4.4'-diaminostilbendisulfonic acid derivative) Add 1.0 g of water
11 (Adjusted to pH 7.5 with potassium hydroxide or hydrochloric acid.) [Processing-2] Processing-2 except that the pH of the color developer was adjusted to 11.0.
Same as 1.

[Processing-3] Same as Processing-1 except that the pH of the color developer was adjusted to 11.51.

Sensitometry was performed on the obtained image, and the ratio of the gamma of the cyan image to the gamma of the magenta image (referred to as gamma balance C/M) was measured. Here, the gamma value is the density point of (minimum density factor 0, 5) on the characteristic curve.
It is expressed by the slope of the straight line connecting the points of (minimum concentration + 1.5).

That is, the degree of swelling of each sample was also measured, and the results are shown in Table 2.

Table 2 From the results shown in Table 2, Samples 1 to 3 containing no DSR compound according to the present invention exhibit stable processability with little change in gamma balance even when the process changes. It is also seen that the stability is not affected by the degree of swelling of the constituent layers.

On the other hand, in Samples 4 to 12 containing the DSR compound, the processing stability was affected by the degree of swelling of the constituent layers, and only Samples 5.8 and 11, whose swelling degree was within the range of the present invention, showed good processing stability. shows.

Further, using Samples 2.5.8 and 11, color specimens of yellow magenta, cyan, blue green, red, and neutral gray were photographed, respectively, and color processing was performed using Process-2 method. However, the photo was taken with color correction so that some of the neutral gray was reproduced as neutral gray. Figure 1 shows the results of color measurement of each of the obtained colors using the L*a''b display system.Compared to sample 2, samples 5, 8 and 11 have poor color reproducibility for at least some of the colors. You can see that it has been improved.

Example 2 Sample 1 was prepared in the same manner as in Example 1, except that Emulsion B was used in place of Emulsion A in Sample 1-12 of Example 1, and the capping agent was omitted.
3 to 24 were created.

Each sample obtained was subjected to wedge exposure in the same manner as in Example 1, and then processed in the processing steps shown below.

[Processing-4] Processing process Time Temperature color development
1 minute to 3 minutes 20 seconds 33°C (in 10 second increments) Bleach fixing 40 seconds Stable at 33°C 3 times for 20 seconds each Dry at 33°C
30 seconds 60-80
°C However, after the start of color development, the entire surface was exposed to white light of 1.2 lux for 10 seconds from 20 seconds to 30 seconds.

The composition of the processing solution used was the same as in Process-1 in Example 1, except that the pH of the color developing solution was adjusted to lO12.

[Processing-5] Processing-4 except that the processing temperature for color development was 36°C.
is the same as

[Processing-6] Processing = 4 except that the processing temperature for color development was 39°C.
is the same as

Sensitometric evaluation was performed on the obtained color images. For each sample and processing combination, the minimum density value (DminB, Dmin
G, DminR) were determined.

The results are shown in Table 3. In addition, the degree of swelling of Samples 13 to 24 is determined from the results in Table 3.
3, it can be seen that the longer the processing time, the better the minimum density value when a certain maximum density is obtained, which is a disadvantage when processing quickly.

On the other hand, for Samples 4 to 12 containing DSR compounds, it can be seen that the shorter the processing time, the smaller the minimum concentration value when a certain maximum concentration is obtained, which makes them suitable for rapid processing.

Furthermore, it can be seen that among samples having different degrees of swelling, when the degrees of swelling are larger than the range of the present invention, the above-mentioned minimum concentration value increases. Moreover, if the degree of swelling is smaller than the range of the present invention, the progress of development will be delayed, which is undesirable.

Example 3 Samples 1 to 24 prepared in Examples 1 and 2 were cut into rolls and loaded into a cassette that could be handled in a bright room.

Color copier "Konica Color 7" (manufactured by Konica Corporation)
The cassettes containing Samples 1 to 24 were set in the cassettes, and a portrait made with Konica color paper was used as a manuscript to copy under optimal conditions for evaluation.

The replenisher and starter used were as follows.

Developer solution FCC-IS-IN (manufactured by Konica)
Development starter FCC-IR-IN (// )
Bleach-fix solution PCC-2R-IN (//) Stabilizer solution FCC-32-IN (//
) The evaluation was made using the same sample at A-4 size with 800
This was done after processing the sheets.

As a result, good image quality was obtained for samples 5, 8, 11, 17, 20, and 23 of the present invention, but for samples other than the present invention, the gamma balance was significantly larger than the preferred 100. 100, and good image quality could not be obtained.

[Brief explanation of the drawing]

FIG. 1 shows color images taken using Samples 2.5.8 and 11 in Example 1, and developed color images as L*
FIG. 3 is a distribution diagram showing the results of color measurement using a"b. FIG.

Claims (1)

[Claims] It has at least one silver halide emulsion layer containing internal latent image type silver halide grains on which the grain surface is not fogged in advance, and after image exposure, after being subjected to fogging treatment, and/or after being subjected to fogging treatment. In a photographic light-sensitive material in which a positive image is obtained directly by surface development, a compound capable of reacting with an oxidation product of a developing agent and scavenging the oxidation product, or a precursor thereof, is released into the silver halide emulsion layer. The degree of swelling of the photographic constituent layer containing the silver halide emulsion layer is 100 to 1.
70% direct positive silver halide photographic material.