JPS59201048A - Silver halide photographic element - Google Patents

Abstract

PURPOSE:To prevent an image from being damaged and stained due to gaseous nitrogen even during a processing stage and to obtain a positive image high in the max. density by using a specified compd. as a fogging agent in a silver halide photographic element for forming a positive type image. CONSTITUTION:A compd. to be incorporated as a fogging agent in a hydrophilic colloid layer is represented by the formula shown here in which R1-R3 are each H, alkyl, cycloalkyl, or aryl, and R2 may combine with R3 to form a 5- or 6- membered ring. A preferable amt. of said fogging agent to be used is about 10<-6>-10<-2> mole per mole of an internal latent image type silver halide.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a direct positive silver halide photographic element using an internal latent image/halogenated emulsion, and more particularly to a direct positive silver halide photographic element containing a novel fogging agent. Directly related to Bosino silver halogenide photographic elements.

PRIOR ART It is well known that silver halide photographic elements can be used to directly form positive images without the need for reversal processing or negative x-ray imaging.

Conventionally known methods for producing fully positive images using direct positive silver halogenide photographic elements, excluding special cases, are mainly divided into two types, considering their practical usefulness. It can be divided into

One type uses a pre-coupled silver halide emulsion and uses solarization or the Burschel effect to destroy the capri nucleus (MF elephant) in the exposed area, thereby obtaining a positive image after development. It is.

The other type uses an uncoupled internal latent image type silver halide emulsion, and performs surface development after exposure of image 1# and/or while performing capri processing, resulting in positive image 9J? It's something you get.

Here, the capri treatment may be performed by exposing the entire surface to light, using a fogging agent, using a strong liquid coating, or by heat treatment, but usually a capri agent is not used. It is carried out using The internal latent image type silver halide emulsion is a silver halide emulsion in which a photosensitive nucleus is mainly formed inside the silver halide grains, and a latent image is formed inside the grains upon exposure.

This latter type of method for directly obtaining a positive image using a silver halide emulsion is, compared to the former type, as follows:
It generally has high sensitivity and is suitable for applications that require high sensitivity.

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2,592,250, U.S. Patent No. 2,456.957, U.S. Pat.
No. 3, Special Publication No. 43-29405, Japanese Patent Publication No. 47-943
No. 4, No. 47-9677, No. 47-32813, No. 47-32814, No. 48-9727, No. 48-9
No. 717, U.S. Patent No. 3,761.266, U.S. Patent No. 3,7
No. 96.577, JP-A No. 50-8524, No. 5 o-
=-38525 etc. are the main ones.

Using these known methods, relatively high sensitivity photographic elements can be made for direct positive working.

For details on the mechanism of direct positive image formation, see, for example, Mies and James [The Theory of
The Photographic Process J
hoory of the Photographic
The process of forming a positive image can be understood to some extent by the ``desensitization effect by the inner layer 1 phenomenon'' as discussed in section 6).

In other words, fog nuclei are selectively created only on the surface of unexposed silver halide grains in non-image areas due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide grains by the first image@exposure. It is believed that the photographic image is formed in the unexposed areas by normal phenomena.

Hydrazine compounds and thiocarbazide derivatives are known as useful fogging agents that exhibit such selective capriactivity.

For example, U.S. Patent No. 2,563.785;
88,982, naphthylhydrazine sulfonic acid as described in U.S. Pat. No. 2,604,700, or British Patent No. 1.4.
Sulfophthylhydrazines described in No. 03.018 are used as fogging agents. In addition, the special public sector Showa 4
No. 1-17184 describes that a color positive image can be obtained by using hydrazide or hydrazone compound vIJ. 1-thiocarbazide derivatives include US Pat. No. 4, i39. '387 Research Disclosure
No. 15750.

However, in order to apply the method of directly forming positive images using these compounds as fogging agents to various photographic fields, technical problems remain that must be further improved.

For example, in such capri development, the capri reaction by the fogging agent must occur prior to the development reaction, so compared to the development of ordinary latent image silver, it takes longer for the fermentation to begin to develop. The lead-up period is long, so the current one is delayed considerably. Therefore, when applied to a multilayer color photographic element, there are problems such as non-uniformity of properties between the layers.

``Also, with conventional fogging agents, the final maximum value obtained is relatively low.

Therefore, with conventional fogging agents, relatively high concentrations of fogging agents are required to achieve the desired capri effect within a relatively short period of time; however, when using fogging agents at such high concentrations, For example, when a fogging agent is contained in an emulsion, a large amount of the fogging agent is eluted into the developing solution, resulting in undesirable non-uniformity of the current iM. In addition, air bubbles of accumulated gas created by the decomposition of the fogging agent can become trapped in the binder of the photographic element, significantly impairing the quality of the image. (When performing color development, there is a tendency to cause discoloration in the background due to contamination with fogging agents. Also, when performing color development, the fogging agent competes with the coloring agent and reacts with the oxidized form of the color developing agent. , the use of high concentrations of capri agents significantly reduces the color dye concentration.

In order to solve these problems, several capri agents have been proposed which adsorb onto the surface of silver halide grains and, as a result, only require a small amount of addition. For example, JP-A-47-9677
No. 47-9434 and U.S. Patent No. 3,615,
Examples include capri agents comprising heterocyclic quaternary salt compounds described in No. 615 and the like.

These can be added in very small quantities, so the above-mentioned drawbacks are eliminated. On the other hand, these compounds had the major drawback of absorbing light in the visible spectrum range. Furthermore, when these compounds are included in the emulsion,
It was observed that the storage stability of the fL solution and photographic elements was significantly deteriorated.

For example, if a photographic element is stored in a relatively hot or humid environment, the minimum density will increase significantly and the maximum density will also decrease, resulting in a significant loss of positive image quality. Also, in U.S. Patent No. 4,139.387,
It has been disclosed that thiocarbohydrazide compounds have effective carbohydric effects and are also relatively highly water soluble. However, it has been recognized that these compounds also have the following practical drawbacks.

That is, it has been found that because the gradations of the highlights and tones of the obtained positive image, that is, the tones on the photographic characteristic curve, are significantly softened, the so-called toe-cutting tends to become worse. Such characteristics have a high contrast with background parts such as letters and scrap paintings, and are extremely disadvantageous when creating a photographic photograph with clear limbus. A number of different capri agents have been proposed, but all of them have drawbacks such as lack of ability as a capri agent and deterioration of performance due to heat, humidity, etc. during storage. The development of new agents is desired.

(Objective of the Invention) The first object of the present invention is to exhibit a sufficient Capri effect, to avoid image damage or image contamination caused by nitrogen gas even during the processing process, and to produce a direct image that does not disturb a positive image with high maximum yield. An object of the present invention is to provide a silver halide photographic element for forming a single positive image (referred to as a direct positive photographic element).

A second object of the present invention is to provide a direct positive photographic element that provides high contrast and sharp, sharp images.

(Structure of the Invention) The present invention provides a silver halide photographic element for forming positive images, which comprises a hydrophilic colloid layer and contains internal latent image type silver halide grains and a capri agent. It is constructed by using a compound represented by the general formula.

In the formula, R, , R2 and R3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

It may also combine with R and FiR3 to form a 5- or 6-membered monkey.

The above-mentioned alkyl group preferably refers to a linear or branched saturated aliphatic group having 181 carbon atoms or less, and these include an alkoxy group, a )-rogen atom, a carboxyl group, a phenyl group, and a) IJ group. etc. may be replaced,
For example, methyl group, ethyl group, n-butyl group, inglovir group, trifluoromethyl group, ω-glomoptyl group, β
-methoxyethyl group, benzyl group, phenethyl group, 4β
-7anoethyl group, β-ethoxylponylethyl group, and the like.

An example of the above-mentioned 7-chloroalkyl group is a cyclohexyl group.

The above aryl group refers to a phenyl group, a naphthyl group,
These may be substituted with an alkyl group, an alkoxy group, a halogen, an amine group, a nitrile group, a carboxy group, or the like. Examples include phenyl group, tolyl group, methoxyphenyl group, chlorophenyl group, propylphenyl group, acetyl, aminophenyl group, dimethylaminophenyl group, methoxycarbonylphenyl group, and the like.

Typical examples of compounds represented by the above general formula (hereinafter referred to as capri agents of the present invention) useful as capri agents in the present invention are illustrated, but the present invention is not limited thereto.

Next, the method for synthesizing the Capri curve of the present invention will be described.

Synthesis Example: Synthesis of Exemplary Capri Agent (2) 4.2 g of 4-phenyl-3-thiosemicarbazide was suspended in methanol 301a, and 2 rrL of concentrated hydrochloric acid was added thereto. This mixture was published in Pharmaceutical Journal, 870 (1951).
), a potassium dithioformate aqueous solution (0.03 mol 1 minute) was added, and the mixture was allowed to stand overnight at room temperature. Then 4 ml of glacial acetic acid
and 30 ml of water were added, methanol was distilled off under reduced pressure, and the resulting crystals were collected by filtration (yield: 3.1 g, mp; 1
32℃).

Synthesis Example 2 Synthesis of Exemplary Capric Agent (10) Kai Arn
e, carboxymethyl-p-methoxydithiobenzoic acid was synthesized by the method of Rensen et al. (
Acta Ohmica 5caninavica
Vol 15.

1087 (1965)). Thiosemi Rubazide 3
．． 7g Carboxymethyl dithiobenzoate 109 as described above
was dispersed in 30 m of methanol and 70 mJ/l of water, and while stirring, 1.9 g of sodium hydroxide was dissolved in 20 mJ of water.
It was then dripped. After further reacting at room temperature for 2 hours, the precipitated crystals were collected by filtration (yield: 9.8 ji m
p ; 142-145° C.)6 The capri agents of the present invention can be used in direct positive photographic elements having at least one silver halide emulsion layer containing internally latent image type silver halide grains. At least one hydrophilic colloid layer, preferably an internal latent image type silver halide photographic emulsion layer and/or an adjacent hydrophilic colloid layer (e.g. silver halide photosensitive layer, interlayer, filter layer, protective layer) , antihalation layer).

When two or more types of fogging agents of the present invention are used in combination, it is preferable that they coexist in the same layer in the silver halide emulsion layer or in the layer A adjacent to it, but they may be contained in large amounts in separate layers.

The usage number of the fogging agent of the present invention can vary widely depending on the characteristics of the silver halogenide emulsion used, the type of fogging agent, and the development conditions, but it may be After exposing the element to 19 images, the surface of the element is treated with a body fluid to produce a positive image (as long as the amount of fogging is sufficient to obtain a positive image), and after the development process, the surface is treated with a body fluid for a sufficient amount of time (for example, 1. 5 or more).Usually, the amount of the fogging agent is preferably about 10-6 mol to 10-2 mol, more preferably 10-6 mol, per 1 mol of internal latent image type silver halide. ~10-s mol.

In addition, when applied to color diffusion transfer method,
It can be mixed into the target I* or the sheet. In this case, the violet contained in the fogging agent may be the same powder as in the case where it is contained in the silver halide emulsion layer.

Further, the fogging agent of the present invention can also be used in combination with the conventionally known fogging agents mentioned above. Specific examples of useful known fogging agents include hydrazine hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-(4-1tylphenyl)hydrazine, 1-
Acetyl-2-phenylhydrazine, 1-acetyl-2
-(4-acetamidophenyl)hydrazine, 1-methylsulfonyl-2-7enylhydrazine, 1-benzoyl-2-phenylhydrazine, 1-methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine, formaldehyde phenylhydrazine hydrazine compounds such as; 3-(2-formylethyl)-2-
Methylbenzothiazolium bromide, 3-(2-formylethyl)-2-propylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benzylbenzoselenazolium bromide, 3-(2-acetylethyl) -2-benzyl-5-phenyl-benzoxacilium bromide, 2-methyl-3-[3-(phenylhydrazono)propyl]pentthiazolium bromide, 2
-Mef-3-(3-(p-tolylhydrazino)propyl)benzthiazolium bromide, 2-methyl-3-
[:3-(p-sulfophenylhydrazono]propyl]benzothiazolium bromide, 2-methyl-3(3
1. 2-dihydro-3-:methyl-4-7enylpyrido [2,1-b] -5-phenylhenedioxasolirum bromide, 4,4-ethylenebis(1,2-dihydro-3-methylpyrido[,2, ，
1-b] benzothiazolium bromide), 1,2-dihydro-3-methyl-4-phenylpyrido [2,2-b
]N-! such as benzoselenazolium bromide! Exchange 4th
class cycloammonium i; 5-[1-ethy lunaft[
1,2-b]thiazolin-2-ylideneethythelene)-
1-(2-phenylcarpanyl)methyl-3-(4-sulfamoylphenyl)-2-thiohydantoin, 5-
(3-ethyl-2-penzothiazolilini'methane)-3
-C4-(2-formylhydrazino)phenyl]rhodanine, 1-(4-(2-formylhydrazino)phenyl]3-7enylthiourea, 1,3-bis[4-(2
-formylhydrazino) phenylcothiourea and the like.

The internal latent image type silver halide photographic element of the present invention, which forms a positive image directly by imagewise exposure and processing in the presence of a capri agent, is also a subject of the present invention.

Although any development processing method can be adopted as the development processing method for the silver halide photographic element, a surface treatment method is preferred. This surface development treatment method means processing with a developer that does not substantially contain a silver halide acid agent. These include polyhydroxybenzenes such as hydroquinone, amine phenols, 3-pyrazolidones, ascorbic fiill derivatives, reductones, phenylenediamines, etc., or mixtures thereof. Ru. Specifically, hydroquinone, aminephenol, N-methylaminephenol, 1-phenyl-3-
Pyrazolidone, 1-phenyl-4,4-dimethyl-3-
5-pyrazolidone, 1-phenyl-4-methyl-4? -Hydroxymethyl-3-pyrazolidone, ascorbine II
, N* N-diethyl-p-phenyne/diamine, diethylamine-〇toluy, gin, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, 4-amino-3- Examples include methyl-N-ethyl-N-(β-hydroxyethyl)aniline. These developing agents may 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 this invention may further contain certain antifoggants and development inhibitors, or these developer additives may optionally be incorporated into the layers of the silver halide photographic element. It is also possible. Commonly useful antifoggants include, for example, benzotriazoles such as 5-methylbenzotriazole; benzothiazoles:
Included are heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole; aromatic and aliphatic mercapto compounds, and the like. Furthermore, a phenomenon promoter such as a polyalkylene oxide derivative or a quaternary ammonium salt compound can also be contained in the phenomenon liquid.

The internal latent image type silver halide photographic element of the present invention comprises at least one layer of internal latent image type silver halide emulsion.

The internal latent image type silver halide emulsion in the present invention is an emulsion having silver halide grains in which latent ('J'f-) is formed mainly inside the silver halide grains and most of the photosensitive nuclei are inside the grains. This includes any silver halide, such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like.

Particularly preferably, the emulsion is prepared by exposing a portion of a sample coated on a transparent support to a light intensity school for a defined period of time up to about 1 second so that only the surface edges of the grains are substantially free of silver halide solvent. The following surface developer A to develop
Another part of the same emulsion sample was similarly exposed and developed for 4 minutes at 20'C with internal developer B described below to develop an image of the interior of the grains. It shows a maximum density not greater than 115.0% of the maximum density obtained when developing for 1 minute.Preferably, surface developer solution A
The maximum concentration obtained using the internal reaction solution B is not greater than 1/10 of the maximum concentration obtained with the internal reaction solution B.

Surface developer A metric
2.5IL-ascorbic acid
10 pNaEO2・4H2035F KBr 1 g Add water ] l Internal reaction I! ! Liquid B Metol 2.0J9 Sodium sulfite (
anhydrous) 90. O,! 9' Hydroquinone
s, o, p carbonate hydrate salt 52.
5FKBr 5.0. ! ? 0.5.9 Add water
The internal latent image type silver halide emulsion according to the present invention includes those prepared by various methods.

For example, the conversion silver halide emulsion described in U.S. Pat. No. 2,592,250, Amatake U.S. Pat. or U.S. Pat. No. 3,271,157, U.S. Pat.
447,927 and 3,531.291, or silver halide emulsions having silver halide grains incorporating polyvalent metal ions, or U.S. Pat.
, 761.276, or a silver halide emulsion in which the grain surface of silver halide grains containing a doping agent is weakly chemically sensitized, or JP-A-50-8524, JP-A-50-8524;
-A silver halide emulsion consisting of grains having a layered structure described in No. 38525 and No. 53-2408;
Sonoike JP-A No. 52-156614 and JP-A No. 5
These include silver halide emulsions described in No. 5-127549.

Furthermore, the internal latent image type silver halide emulsion according to the present invention includes:
Commonly used stabilizers, such as compounds with an azain ring and nitrogen-containing heterogeneous compounds with a mercapto group (typically 4-hydroxy-6-methyl, respectively, + 3 + 3a + 7-titrazain and 1-phenyl) -5-mercaptotetrazole), etc., in an amount of 1 m9 to 10 g per mole of silver halide, more stable results with a lower minimum concentration can be obtained.

According to Genmei Yamoto, as the anti-capri agent or stabilizer 1, mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds, zinc compounds, etc. can be used.

Various photographic additives may optionally be added to the internal latent single-family silver halide emulsion according to the present invention.

For example, optical sensitizers that can be used in the present invention include:
Cyanines, merodiazids 1, trinuclear mani, include sclerotial merocyanines, trinuclear or 7'c include sclerotial cyanines, styryls, holoporacyanines, hemicyanines, oxonols and hemioquinols, These optical sensitizers contain a basic group such as naazoline or thiazole or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, thiobarbylic acid, or pyrazolone as part of their structure as a nitrogen-containing heterocyclic nucleus. Preferred are alkyl, hydroxyalkyl,
Sulfoalkyl, carboxyalkyl, halogen, phenyl, cyanogen, alkoxy can be substituted and optionally fused with a carbocyclic or hydrogen ring.

The internal latent image type silver silver emulsion according to the present invention can be supersensitized. For the method of supersensitization, see, for example, [Review of the mechanism of supersensitization J (ReviθWof 5up
ersensitizalon l (Photogr
aphicScience and Engineer
ing) (PSE I Vol 18, No. 441
8 pages (1'974).

In the pond water invention, the additives used depending on the purpose include, for example, dihydroxyalkane as a wetting agent, and further as a film property improver, for example, alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylate. Water-dispersible particulate polymers obtained by emulsion polymerization such as copolymers with acrylic acid, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc. are suitable. Auxiliary agents include saponin, polyethylene glycol lauryl ether, etc. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pHrA regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and It is optional to use a platoon speed regulator, a matting agent, etc.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, anti-nolation layer, filter layer, etc., if necessary, to obtain an internal storage type silver halide photographic element.

It is useful to use the silver halide photographic elements of this invention for color applications, in which case silver halide photo-X IP
It is preferable to include cyan, magenta and yellow dyes f-stage forming kaglar in the L agent.

Yellow-purple-forming couplers include benzoylacetanilide type, piparoylacetanilide type, or two-equivalent type yellow couplers in which the carbon atom at the coupling position is substituted with a so-called tinnitoff group, which can be detached during the coupling reaction. is useful. As the magenta dye-forming coupler, pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indasilone type, or divalent magenta coupler having a split-off group is useful. As a cyan spontaneously forming coupler, phenolic type 1. Useful are naphthol type, virashanasilone type, or two-benefits type cyan couplers having a split-off group.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent fading of dye-1 due to short-wavelength actinic rays.
It is advantageous to use 0', 326, 327, and 328 (all manufactured by Ciba Geigy) alone or in combination.

Although any support can be used for the silver halide photographic element of the present invention, typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, which has been undercoated as necessary. Film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc.

In the silver halide photographic element of the present invention, the gelatin pond can contain a suitable gelatin derivative depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carpamylated gelatin, cyanethanolated gelatin, and esterified gelatin.

In addition, in the present invention, a hydrophilic binder can be included depending on the purpose, and suitable binders include colloidal albumin, agar, in addition to gelatin.
Gum arabic, dextran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to 10-20% acetyl content, polyacrylamide, imidized polyacrylamide, casein, urethane carbonic acid groups such as vinyl alcohol-vinylamine acetate copolymer, or , cyanoacetate #, vinyl alcohol polymer containing t'r, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate,
Polymers obtained by polymerizing protein "f" or saturated acylated proteins with monomers having a vinyl group, including polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethylene amine, etc., and include fL agent layer or intermediate layer, C can be added to the layers constituting a silver halide photographic element such as a protective layer, a filter layer, a backing layer, etc. according to the purpose, and C can be added to the hydrophilic binder with a suitable plasticizer, lubricant, etc. according to the purpose. It can be made to contain.

Additionally, the constituent layers of the silver halide photographic elements of this invention can be hardened with any suitable hardener. These hardening agents include chromium salts, zirconium salts, aldehyde threads such as formaldehyde and yamcohalogen acids, halotriazine type, polyepoxy compounds, ethyleneimine type, vinyl sulfone type, and acryloyl type hardeners. Ail
Examples include l.

The silver halide photographic element of the present invention also has a number of various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a medical protection layer, a subbing layer, a backing layer, and an antihalation layer on a support. It is possible to install

The silver halide photographic element according to the present invention can be used for various purposes such as the aforementioned color, black and white general use, melay use, false color use, printing use, infrared use, micro use, silver dye bleaching use, color diffusion transfer photography, etc. It can be used for other purposes.

Among these, for diffusion transfer photography, it is particularly effective for systems using DRR compounds. DRR compound (Dye Relθasing Redo
x Compound,) means, for example, the O or l''tp position VC of phenol (or naphthol) with ballast.
These are products in which a dye is bonded via a sulfonamide, or a dye is bonded to the 3-position of indole via a sulfonamide, and these react with the oxidized form of the phenidone visiting conductor to cause cross-oxidation. It is then hydrolyzed to release a diffusible dye.

(JP-A-48-33826, JP-A No. 51-104343, JP-A No. 54-130122, 1nJ57-85055) These compounds are used in the summer, and the dyes released during field work are received in the image receiving section, and then the image is created. If the mound-covering method is used, a color image will be obtained only where silver development has occurred. In other words, a negative image can be obtained with a commonly used silver halide emulsion having a surface density, and a positive image can be obtained with an internal latent image type direct positive tL agent as shown in the present invention.

EXAMPLES Hereinafter, the present invention will be illustrated by examples, but the embodiments of the present invention are not limited thereto.

EXAMPLE Silver chloroiodobromide in internal single-image form by conversion method according to the method described in Example 1 of U.S. Pat. No. 2,592,250. A formulation L was prepared. Separately magenta coupler 1-(
2,4,6-)lichlorophenyl)-3-(2-”70
Rho 5-octa, decyl succinimide anilino)-5
-pyrazolone 40F, 2.5-di-tart -octylhydroquino 711I, dioctyl phthalate-1
- 75 g and 30 g of ethyl acetate were mixed and dissolved, and added to a gelatin bath solution containing sodium inglovirnaphthalene sulfonate to form vL.

This dispersion was spectrally sensitized in advance by the emulsion 11 (silver chloride 0.3
5 mol), and further contains 4-hydroxy-6-methyl-1+ 3,3a+ 7-chitrazaindene],!
i', 2,5-dihydroxy-4-5ec-octadecylbenzene sulfone agent was prepared.

Among the capri agents of the present invention, the above-mentioned exemplified fog agents (
2), (3), and (10) were added, and methanol i! was added with the addition conditions shown in Table 1. 1t! Ic was added to the emulsion, coated on a resin-coated paper support, and dried.

In addition, as a comparative fogging agent, a compound (A) having a structure similar to that of the caprying agent of the present invention and U.S. Pat. No. 4,134,1
A sample was prepared in which the compound (B) described in No. 39,387 was added.

Compound (A) Compound (B) These samples were stored at a temperature of 23°C and a relative humidity of 55% for 1 day (condition-1) and for 2 days at a temperature of 55°C and without humidity control (condition-2). After that, 1 image S exposure was carried out for 4 times, and the following processing was performed.

Processing: Color development (3 minutes 30 seconds) - Stop (30 seconds) - Whitening fixation (
1 minute (capital) seconds] - Water washing (1 minute papermaking) The treatment temperature was 30° C. in each treatment step, and the composition of each treatment solution is shown.

Color boundary IJ! liquid: Stop liquid: Bleach-fix solution: The results obtained are shown in Table-1.

Table 1 below From the results shown in Table 1, it is clear that the capri agent of the present invention provides a good positive photographic element, and that it is possible to obtain a positive photographic element with excellent viability under high temperature conditions. be.

Comparative compounds (A) and (B) both show remarkable effects in small amounts, but the minimum concentration ('
Dmin) increases sharply.

Example 2 The method of forming a positive image using a capri agent according to the present invention can also be applied to a diffusion transfer method.

A photosensitive sheet was prepared by sequentially coating the following layers on a transparent film made of polyethylene terephthalate.

(1) A gelatin layer containing the following magenta dye image-forming compound.

(2) Green-sensitive internal submerged direct positive, silver bromide emulsion layer (prepared similarly to Emulsion C described in Example-1 of U.S. Pat. No. 3,761,276 and spectrally sensitized with sensitizing dyes). 2,5-dihydroxy-4-s
Potassium ec-octadecylbenzenesulfonate and the capri agent of the present invention (Compound Example 2) in the amount shown in Table 2
Contains 1f.

In addition to the sample, in place of the capri agent of layer (2) above, among the capri agents of the present invention, exemplary capri agents (3), (10)
A sample was prepared in which the above compound (-) (B) and a non-adsorption type capriagent (C) were added.

Compound (C) A dye image-receiving sheet was then prepared by coating the following layers in the order listed on an opaque paper support.

(1) Styrene! : N,N-dimethyl-N-benzyl-N-p-(methacroylaminophenyl) methylammonium chloride and divinylbenzene copolymer,
Gelatin and 1-7enyl-4-hydroxymethyl-
A substratum consisting of 4-methyl-3-pyrano and lysinone.

(2) A gelatin interlayer containing a UV absorber.

(3) Gelatin protective layer.

The above-mentioned photosensitive sheet was subjected to quadrant-like cross-lighting, immersed in an activator solution having the composition shown below for a few seconds, and then passed between a pair of pressure rollers and superimposed on the above-mentioned image-receiving sheet. Processing is u
It was carried out at ℃.

(Activator composition) Potassium hydroxide 56.2 g/15-methylbenzotriazole r,2&/1j11-aminoundecanoic acid 2.0i/1 potassium bromide
After 2.01171310 minutes, the photosensitive sheet and image receiving sheet were peeled off.

Table 2 shows the maximum density of the magenta dye transfer image obtained on the receptor layer.

Table 2 In Table 2, γI is the concentration on the characteristic curve of 0.5 and 1.5.
The straight line part γ is expressed by the tangent value of the slope of the straight line connecting the two points, and γ is the minimum density 10.05 and the minimum density 100.3.
The leg γ on the characteristic curve is expressed as the tangent value of the slope of the straight line connecting the two points of 5.

From the above results, it can be seen that the capri agent of the present invention can degrade a good positive image even in a light-sensitive material produced by the diffusion transfer method. Comparative compounds (A) and (B) had a soft tone with poor sharpness, especially at the bottom, and compound (0) had a relatively good tone, but bubbles and uneven development were observed.

(Effects of the Invention) The objects of the present invention have been achieved and the practicality of the single-house type photographic element with a single-sided interior has been improved.

Agent Yoshimi Kurihara

Claims (1)

[Scope of Claims] A silver halide photographic element for forming a single positive-tone surface, comprising a hydrophilic colloid layer and containing internal latent image type silver halide grains and a capri agent, wherein the fogging agent is A silver halide photographic element characterized by being a compound represented by the following general formula. [In the formula, R1, R2 and R3 each represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. Further, Rt may be combined with R8 to form a 5- or 6-membered ring. ]