JPS5814666B2 - Direct positive silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a direct positive silver halide photographic light-sensitive material, and more specifically, after imagewise exposure, the material is exposed entirely or developed in the presence of a fogging agent to directly form a positive image. The present invention relates to an internal latent image type silver halide photographic material containing a novel development-promoting compound.

The present invention is a technology that can be applied to color diffusion transfer as well as ordinary black-and-white photography and color photography.

It is well known that silver halide photographic materials can be used to directly form positive photographic images without the need for intermediate processing steps or negative photographic images.

Conventionally, the methods used to create positive images using known direct positive silver halide photographic materials are mainly divided into two types in consideration of practical usefulness, excluding special methods. be able to.

One type uses a silver halide emulsion that has been fogged in advance and uses solarization or the Persiel effect to destroy fog nuclei (latent images) in exposed areas to obtain a positive image after development. .

The other type uses an unfogged internal latent image type silver halide emulsion and performs surface development after image exposure and/or while performing fogging treatment to obtain a positive image. be.

Here, the fogging treatment may be performed by exposing the entire surface to light, using a fogging agent, using a strong developer, heat treatment, etc., but usually using light or a fogging agent. The method used is adopted.

The term "internal latent image type silver halide photographic emulsion" refers to a silver halide photographic emulsion which has photosensitive nuclei mainly inside the silver halide grains and forms a latent image inside the grains upon exposure.

This latter type of method is generally more sensitive than the former type of method and is suitable for applications requiring high sensitivity, and the present invention is particularly concerned with this latter type of method.

Various techniques are known to date in this technical field.

For example, U.S. Patent Nos. 2,592,250 and 24,669.
The main ones are those described in No. 57, No. 2497875, No. 2588982, No. 3761266, No. 3761276, No. 3796577, and British Patent No. 1151363.

By using these known methods, it is possible to produce direct positive type photographic materials with relatively high sensitivity.

Furthermore, although it cannot be said that a clear explanation has been given regarding the details of the direct positive image formation mechanism, for example, in ``The Theory of the
Photographic Process” (The Theor
y of the Photographic pro
The process by which a positive image is formed can be understood to some extent by the ``desensitizing effect of an internal latent image'' as discussed on page 161 of the 3rd edition.

In other words, fog nuclei are selectively generated 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 created inside the silver halide grains by the initial image exposure. It is believed that a photographic image is formed in the unexposed areas by normal development.

In order to selectively fog in this manner, it is known to uniformly expose the entire surface or to use a hydrazine compound or a heterocyclic quaternary nitrogen salt compound as a fogging agent.

However, in order to apply these methods of directly forming positive images using light or fogging agents to various photographic fields, there remain technical problems that must be further improved.

For example, in such fog development, a fog reaction caused by light or a fogging agent must occur in advance of the development reaction in order to generate cuff nuclei for inducing development. Compared to the development of image silver, the induction period before development is initiated is long and the development rate is therefore considerably retarded.

Therefore, especially when applied to a multilayer color photographic material, there are problems such as non-uniformity in sensitometric properties between layers.

Also, the maximum concentration that can be finally obtained is also relatively low.

As a method for increasing the maximum density in color diffusion transfer using direct positive silver halide emulsions, U.S. Pat.
No. 227552 describes the use of hydroquinone sulfonic acid derivatives.

However, when such compounds are used together, it has been found that there are the following drawbacks.

That is, when the hydroquinone sulfonic acid derivative described above is used in combination with a fogging agent to form a positive image, although the maximum density of the final image is increased, the background area is significantly discolored and contaminated. It turned out that it was.

The occurrence of such contamination not only damages the background portion of a photographic image, but also significantly degrades the color image quality when applied to color photographs, resulting in a fatal drawback.

An object of the present invention is to provide an excellent internal latent image type silver halide photographic light-sensitive material for direct positive image formation that solves the problems in the prior art described above.

Another object of the present invention is to provide an internal latent image type silver halide photographic light-sensitive material for direct positive image formation in which fog development progresses quickly and is free from contamination.

More specifically, the purpose of the present invention is to shorten the development induction period, produce a good direct positive image with relatively short fog development, no contamination of the background area, high maximum density, and small minimum density. An object of the present invention is to provide an internal latent image type silver halide photographic light-sensitive material.

As a result of various studies, the present inventor found the following general formula CI) or (1
It has been found that the above object can be achieved by an internal latent image type silver halide photographic light-sensitive material for direct positive image formation containing the compound represented by (hereinafter referred to as the compound of the present invention).

General formula CI) General formula CI) In the formula, R1 is a hydrogen atom, -Co-R7 or -SO2-R
7. R2 represents a halogen atom, an alkyl group, or an alkoxy group, and R3 to R6 represent a hydrogen atom or a substituted or unsubstituted alkyl group.

However, R7 represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkoxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group.

Z represents an alkylene chain necessary to form a 5- to 7-membered carbon ring, and each of these alkylene chains may be substituted with a substituted or unsubstituted alkyl group or aryl group.

m represents an integer of 0, 1 or 2, and n represents an integer of 2 or 3.

In the general formula [■] and (I), the halogen atom may be, for example, fluorine, chlorine, bromine or iodine; the alkyl group may be linear or branched;
Preferably it has 1 to 32 carbon atoms, such as methyl, ethyl, n-butyl, t-butyl, 2-ethylhexyl, 3.5.5-trimethylhexyl, 2.2
-dimethylpentyl, n-octyl, t-octyl, n
-dodecyl, sec-dodecyl, n-hexatecyl, n
-octadecyl or eicosyl; examples of alkoxy groups include methoxy, ethoxy, n-propoxy, n-
Examples of the -butoxy, t-butoxy, n-hexoxy, n-dodecoxy, and n-octatecosialyl groups include phenyl and naphthyl.

Aralkyl groups include, for example, benzyl and phenethyl. Aryloxy groups include, for example, phenoxy, α-naphthoxy, p-methylphenoxy, p-methoxyphenoxy, p-acetamidophenoxy, 0-chlorophenoxy, m-dichlorophenoxy, etc. Examples of aralkoxy groups include penzyloxy and phenethyloxy; alkyloxycarbonyl groups include ethoxycarbonyl, tert-butoxycarbonyl, and octatecylcarbonyl; and aryloxycarbonyl groups include phenoxycarbonyl and p- Examples include methylphenoxycarbonyl, p-methoxyphenoxycarbonyl, p-acetamidophenoxycarbonyl, and o-chlorophenoxycarbonyl.

Furthermore, each of these groups may have a substituent.

Examples of these substituents include halogen atoms, hydroxy groups, carboxy groups, and alkyl groups (especially those with 1 carbon atom).
~32), alkenyl groups (particularly those with 2 to 3 carbon atoms),
2), an alkoxy group, an aryl group, an aryloxy group, an arylamino group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and the like.

These substituents may be further substituted with the above-mentioned substituents.

To explain the general formula CI), [l) in more detail,
R2 is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, and R3 to R6 are each a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. Alkyl groups are preferred.

More preferably, R1 is a hydrogen atom, R3 and R4 are methyl groups, and R5 and R6 are hydrogen atoms.

Further, the (0-R')n groups substituted on the aromatic ring are preferably located at positions adjacent to each other.

Specific examples of the compounds represented by the general formulas [■] and [I] used in the present invention are shown below.

However, the present invention is not limited to these.

These compounds are, for example, European polymers.
Journal (European Polymer Jo
urnal) Vol. 7, pp. 255-261 (1971), Journal of Chemical Society (J
Internal of Chemical Society
y) It can be easily synthesized according to the method described in pages 1678 to 1681 (1934) and pages 2511 to 2524 (1930).

The compound of the present invention can be contained in any layer constituting the internal latent image type silver halide photographic light-sensitive material, but preferably in the silver halide emulsion layer and/or the photographic constituent layer present on the emulsion layer side of the support. It is contained in at least one layer, more preferably in the silver halide emulsion layer and/or its adjacent layer, particularly preferably in the silver halide emulsion layer.

The content of the compound of the present invention may be sufficient to promote fog development when the internal latent image type silver halide photographic light-sensitive material is subjected to full exposure or development processing in the presence of a fogging agent. .

The actual amount added can vary widely depending on the characteristics of the silver halide photographic light-sensitive material used and development conditions, but when contained in a silver halide emulsion, it is 0 per mole of silver halide.

001 to 1 mol is preferable, and 0.001 to 0.5 mol is particularly preferable.

When it is contained in a layer adjacent to an emulsion layer, the amount may be the same as when it is contained in the silver halide emulsion layer.

Further, in the case of a silver halide emulsion layer, it is added at an appropriate time from the end of ripening of the emulsion to before coating, and in the case of other layers, it is added at an appropriate time from the time of preparing the coating liquid to before coating.

The compounds of the invention are added dissolved in a suitable solvent such as water, alcohol, acetone, benzene or dioxane.

Among the compounds of the present invention, oil-soluble compounds are generally disclosed in U.S. Pat. No. 2,322,027, U.S. Pat.
2191 and No. 2304940, it is preferable to dissolve in a high boiling point solvent, if necessary in combination with a low boiling point solvent, disperse and add to the hydrophilic colloid solution. Depending on the situation, it may be dispersed together with lipophilic photographic additives such as couplers and incorporated into photographic constituent layers such as silver halide emulsion layers.

Furthermore, the compounds of the present invention are disclosed in U.S. Patent No. 2,269,158, U.S. Pat.
No. 2168, No. 3619195 and No. 2801
It can also be easily dispersed by a dispersion method using a latex solution such as that described in the specification of No. 170.

Further, among the compounds of the present invention, those which are alkali-soluble (or water-soluble) can be made into an alkaline solution (or an aqueous solution) and added to the hydrophilic colloid solution.

In the present invention, the main step of directly creating a positive image is to use an unfogged internal latent image type silver halide photosensitive material after image exposure and/or after subjecting it to a fogging process. It consists of performing surface development while applying.

The fogging process can be performed by exposing the entire surface to light or using 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.

The light source used here may be any light within the sensitive wavelength range of the photosensitive material, and 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 photosensitive 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 the fogging agent only needs to be present during the development process, for example, in an internal latent image type silver halide photographic light-sensitive material such as a silver halide emulsion layer. It may be contained in a developing solution or a processing solution prior to development, but it is preferably contained in a silver halide photographic light-sensitive material.

(Among these, the inside of the silver halide emulsion layer is particularly good.)

The amount used can be varied over a wide range depending on the purpose, and the preferable amount is 1 to 1,500 m per mole of silver halide when added to a silver halide emulsion layer.
9, particularly preferably 10 to IO00 mg.

Also, the preferred amount of addition when added to a processing solution such as a developer is 0.01 to 5? /l, particularly preferably 0.05-1
g/l.

As the fogging agent used in the present invention, for example, US Pat.
563785, hydrazines described in 2588982, or US Pat. No. 32275
hydrazide or hydrazone compounds described in US Pat. No. 52; also US Pat.
Heterocyclic quaternary nitrogen salt compounds described in US Pat. No. 3,719,494, US No. 3,734,738, US Pat. be done.

It can also be used in combination with these fogging agents.

For example, research closure (Research)
h Disclosure) No. 15162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent.

Specific examples of useful fogging agents include hydrazine hydrochloride,
Phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, p-methylsulfonamidoethylphenylhydrazine, ■-formyl-2-phenylhydrazine,
■-acetyl-2-phenylhydrazine, ■-acetyl-2-(4-methylphenyl)hydrazine, ■-acetyl-2-(4-acetamidophenyl)hydrazine, ■
= Methylsulfonyl-2-phenylhydrazine 1-penzoyl-2-phenylhytracine, 1-lauroyl-2-phenylhydrazine, ■-Methylsulfonyl-
2-(3-Phenylsulfonamidophenyl)hydrazine, formaldehyde phenylhydrazine, acetone-4-methylphenylhydrazine, ■-sulfomethyl-2-phenylhydrazine, ■-sulfomethylamino-2-phenylhydrazine Hydrazine compounds such as enylhydrazine; 3
-(2-formylethyl)-2-methylbenzothiazolium bromide, 3-(2-acetylethyl)-2-ethylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benzylbenzothiazo Bromide, 3-(2-formylethyl)-2-probylbenzothiazolium bromide, 5-chloro-3-(2-formylethyl)-2-methylbenzothiazolium bromide, 3-(2-acetyl) ethyl)-2-penzylbenzoselenazolium bromide, 3-(2-acetylethyl-2-benzyl-5-phenyl-benzoxazolium bromide, 2-methyl-3-(3-(phenylhydrazono)propyl) ] Penzothiazolium bromide, 2-
Methyl-3-(3-(p-tolylhydrazono)probyl)penzothiazolium bromide, 2-methyl-3-(
3-(p-sulfophenylhydrazono)probyl]penzothiazolium bromide, 2-methyl-3-[3-
(p-toluenesulfonylhydrazono)pentyl]naphtho[2.1-b)thiazolium iotide, 2-methyl-3-(3-(p-toluenesulfonylhydrazono)pentyl]penzothiazo Lium iodide, 1,2-dihydro-3-methyl-4-phenylhylide [2,1-b) Penzothiazolium bromide, ■, 2-dihydro-3-methyl-4-phenylpyride [2,1- b) -5-phenylbenzoxazolium bromide, ■, 2-dihydro-3, 4-dimethylpyrido [2, 1-b] penzothiazolium bromide, 4, 4'-ethylenebis (1, 2-
N- such as dihydro-3-methylpyrid [2,1-b] penzothiazolium bromide), l,2-dihydro-3-methyl-4-phenylpyrid [2,1-b] penzoselenazolium bromide, etc. Substituted quaternary cycloammonium salt; 5-CI-ethylnanth(1,2-b)thiazolin-2-yriteneethythene]-1-(2-phenylcarhazoyl)methyl-3-(4-sulfamo ylphenyl)-2-thiohydantoin, 5-(3=ethyl-2-penzothiazolinylidene)-3-[4-(2-formylhydrazino)phenyl]rhodanine, 1-C4-(2 −
These include formylhydrazino)phenyl]-3-phenylthiourea, 1,3-bis(4-(2-formylhydrazino)phenyl)thiourea, and the like.

The internal latent image type silver halide photographic light-sensitive material containing the compound of the present invention directly forms a positive image by exposing the entire surface after imagewise exposure or developing in the presence of a fogging agent. Although any development processing method can be adopted as the development processing method for the silver halide photographic light-sensitive material, a surface development processing method is preferable.

This surface development processing method means processing with a developer substantially free of silver halide solvent.

Common silver halide developers that can be used in the developer of the present invention include polyhydroxybenzenes such as hydroquinone, aminephenols, 3-virazolidos, ascorbic acid and its derivatives, reductones,
Contains phenylenediamines and mixtures thereof.

Specifically, hydroquinone, aminephenol, N-methylaminephenol, 1-phenyl-3-virazolidone, ■-phenyl-4,4-dimethyl-3-virasoliton, ■-phenyl-4-methyl-4-hydroxymethyl-3 -Vyrazolidone, ascorbic acid, N-N-diethyl-p-phenylenediamine, diethylamine-0-toluidine, 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)aniline, 4-
Examples include amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline.

These developers 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 the present invention may further contain specific antifoggants and development inhibitors, or these developer additives may be optionally incorporated into the layers of the silver halide photographic light-sensitive material. is also possible.

Commonly useful antifoggants include, for example, penzotriazoles, penzothiazoles such as 5-methylbenzothiazole; 1-phenyl-5-mercaptotetrazoles, 5-methylbenzotriazole, etc.;
Heterocyclic thiones such as -tetrazoline-5-thione; aromatic and aliphatic mercapto compounds, and the like.

The internal latent image type silver halide photographic light-sensitive material according to 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 which form a latent image mainly inside the silver halide grains and have most of the photosensitive nuclei inside the grains, and which has arbitrary Silver halides such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like are included.

Particularly preferably, the emulsion is prepared by exposing a portion of a sample coated on a transparent support to a light intensity scale for a defined period of time up to about 1 second to obtain surface images of grains substantially free of silver halide solvent. The following surface developer A to develop
Another part of the same emulsion sample is exposed in the same way and developed for 4 minutes at 20°C with internal developer B, which develops the image inside the grains. The maximum concentration obtained is 1/5 of the maximum concentration obtained.

Preferably, the maximum density obtained with surface developer A is not more than 1/10 of the maximum density obtained with internal developer B.

Surface developer A Metol 25g L-ascorbic acid 1Og NaBO2・4H20
35g KBr
l? add water
1l internal developer B Metol 2.0g Sodium sulfite (anhydrous) 900g Hydroquinone
8.02 Sodium carbonate water salt
52.5PKBr
5. Qgu KI
O. Adding 5P water l1 Further, the internal latent image type silver halide emulsion according to the present invention includes those prepared by various methods.

For example, converted silver halide emulsions as described in U.S. Pat. No. 2,592,250, or internally chemically sensitized halogen emulsions as described in U.S. Pat. a silver halide emulsion having silveride grains;
or U.S. Patent No. 3271157, U.S. Patent No. 344792
Silver halide emulsions having silver halide grains containing polyvalent metal ions as described in No. 7 and No. 3,531,291, or US Pat. No. 3,761,27
A silver halide emulsion in which the grain surface of silver halide grains containing a dopant is weakly chemically sensitized as described in Specification No. 6, or a laminated structure as described in JP-A-50-8524. silver halide emulsion consisting of grains,
Or a silver halide emulsion containing silver iodide prepared by the ammonia method described in JP-A-52-156614.

Furthermore, the internal latent image type silver halide emulsion according to the present invention includes:
By containing a compound having an azaindene ring, a nitrogen-containing heterocyclic compound having a mercapto group, etc. in an amount of 1 mg to 10 g per mole of silver halide, a more stable result with a lower minimum concentration can be obtained.

As the compound having an azaintene ring, 4-hydroxy-6-methyl-1.3.3a.7-tetrazaindene is preferable.

Examples of nitrogen-containing heterocyclic compounds having a mercapto group include pyrazole ring, ■・2,4-triazole ring, ■・2,3
-triazole ring, ■・3,4-thiadiazole ring, 1
・2,3-thiadiazole ring, ■・2,4-thiadiazole ring, 1,2,5-thiadiazole ring, ■・2,3・
4-tetrazole ring, pyridazine ring, ■2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring, rings in which 2 to 3 of these rings are condensed, such as triazolo There are triazole rings, diazaindene rings, triazaindene rings, tetrazaindene rings, pentazaindene rings, and phthalazinone rings, indazole rings, etc., and -phenyl-5-mercaptotetrazole is preferred.

In addition, in the present invention, as antifoggants or stabilizers, for example, mercury compounds, triazole compounds, azainthene compounds, penzothiazolium compounds, zinc compounds, etc. may be used.

Various photographic additives may optionally be added to the internal latent image type silver halide emulsion according to the present invention.

For example, optical sensitizers that can be used in the present invention include dianines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holoporacyanines, hemicyanines, and oxonols. These optical sensitizers contain basic groups such as thiazoline and thiazole, or rhodanine, thiohydantoin, oxazolidinedione, barbituric acid, and thiobarbituric acid as part of their structure as a nitrogen-containing heterocyclic nucleus. Those containing nuclei such as acids and vilazolone are preferred;
Such nuclei can be alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl, cyano, alkoxy substituted and optionally fused with carbocycles or heterocycles.

The internal latent image type silver halide emulsion according to the present invention can be supersensitized.

Regarding the method of supersensitization, for example, [Review of the mechanism of supersensitization]
(Photographic Science)
e and Engineering) (PSE) Vo
1 18, p. 418 (1974).

Other additives used depending on the purpose in the present invention include wetting agents such as dihydroxyalkanes, and film property improvers such as alkyl acrylates or alkyl methacrylates and acrylic acid. Alternatively, water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as copolymers with methacrylic acid, styrene-maleic acid copolymers, and styrene-maleic anhydride hafalkyl ester copolymers are suitable. Examples of coating aids include saponin and polyethylene glycol lauryl ether.

Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speed. The use of conditioning agents, matting agents, etc. is optional.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc., if necessary, to directly obtain a positive silver halide photographic light-sensitive material.

It is useful to use the internal latent image type silver halide photographic light-sensitive material according to the present invention for color purposes, and in this case, it is preferable to include cyan, magenta, and yellow dye image-forming couplers in the silver halide photographic emulsion. .

Among these, yellow dye image-forming couplers are of the penzoylacetanilide type, pivaloylacetanilide type, or those in which the carbon atom at the coupling position is substituted with a substituent that can be removed during the coupling reaction (so-called split-off group). It is an equivalent type yellow dye image-forming coupler, and as a magenta dye image-forming coupler,
It is a 2-equivalent type magenta dye image-forming coupler having a 5-pyrazolone type, birazolotriazole type, birazolinobenzimidazole type, indazolone type or a split-off group, and cyan dye image-forming couplers include phenol type, naphthol type, It is a birazoquinazolone type or two-equivalent type cyan dye image-forming coupler having a split-off group.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, penzotriazole, acrylonitrile, and penzophenone compounds to prevent browning of dye images caused by short-wavelength actinic rays.
, 326, 327, and 328 (all manufactured by Ciba Geigy) may be used alone or in combination.

Any support can be used for the internal latent image type silver halide photographic light-sensitive material according to the present invention, but typical supports include a polyethylene terephthalate film, a polycarbonate film, and a polycarbonate film, if necessary. Includes polystyrene film, polypropylene film, cellulose acetate film, glass, baryta paper, polyethylene laminated paper, etc.

In addition to gelatin, the internal latent image type silver halide photographic light-sensitive material according to the present invention may contain a suitable gelatin derivative depending on the purpose.

Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanethanolated gelatin, and esterified gelatin.

In addition, in the present invention, other hydrophilic binders can be included depending on the purpose, and examples of suitable binders include colloidal albumin, agar, in addition to gelatin.
Cellulose derivatives such as gum arabic, tegistran, alginic acid, cellulose acetate hydrolyzed to 19-20% acetyl content, polyacrylamide, imidized polyacrylamide, casein, urethane carboxylic acid groups such as vinyl alcohol-vinylamino acetate copolymer, or , vinyl alcohol polymer containing one cyanoacetyl group, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymer obtained by polymerization of protein or saturated acylated protein with a monomer having a vinyl group, polyvinylpyridine, polyvinylamine, polyaminoethyl Metaacrylate,
The hydrophilic binder contains polyethylene amine, etc., and can be added to constituent layers of silver halide photographic materials such as emulsion layers, intermediate layers, protective layers, filter layers, backing layers, etc., depending on the purpose. Appropriate plasticizers, lubricants, etc. can be contained depending on the purpose.

Further, the constituent layers of the silver halide photographic light-sensitive material according to the present invention can be hardened with any suitable hardening agent.

These hardeners include chromium salts, zirconium salts,
Examples include altehyde hardeners such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners.

Further, the silver halide photographic light-sensitive material according to the present invention has a number of various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer on a support. It is possible to install

The silver halide photographic light-sensitive material according to the present invention can be used for general black and white purposes, for X-ray purposes, for color purposes, for false color purposes, for printing purposes, for infrared purposes,
It can be effectively applied to various uses such as micro-use and silver dye bleaching, and it can also be applied to colloid transfer method, silver salt diffusion transfer method, Rogers U.S. Pat.
No. 185,567 and No. 2983606, U.S. Patent No. 3,253,915 to Weyertz et al., U.S. Patent No. 3,227,550 to Whymore et al.
No. 227551, Whitemore U.S. Patent No. 32275
The present invention can also be applied to color single image transfer methods, color diffusion transfer methods, absorption transfer methods, etc. as described in US Pat. No. 52 and Land, US Pat.

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 An internal latent image type silver chloroiodobromide emulsion was prepared by the conversion method according to the method described in Example 1 of US Pat. No. 2,592,250.

Next, 5 of compounds (1), (10), and (l3) of the present invention
% methanol solution to 1 liter of the above emulsion (silver chloroiodobromide 0.35
2,4-dichloro- as a hardening agent.
After adding 30 ml of a 4% aqueous solution of sodium 6-hydroxy-5-triazine, the amount of coated silver was 35 mg/100 cm.
2 on a cellulose acetate support,
Dry (Samples 2-4).

Separately, a comparative sample without the addition of the compound of the present invention was prepared in the same manner (Sample 1).

These samples were exposed to light through an optical wedge for sensitometry (hereinafter referred to as wedge exposure) using a sensitometer.
Developing was carried out at 20° C. for 6 minutes using a developer having the following formulation, followed by fixation, washing with water, and drying in the usual manner.

Meal 2.57l-ascorbic acid 10g NaB02/2H20
35? KBr
Add 1g water
However, the entire surface was uniformly exposed to 5 lux light from 30 seconds after the start of development until the end of development.

The results of the obtained positive images are shown in Table 1.

From the results in Table 1, samples 2 and 3 containing the compound of the present invention
It can be seen that samples 4 and 4 have a high maximum density and a good positive image can be obtained.

Example 2 Samples 1 to 4 prepared in Example 1 were exposed to wedge light, developed with a developer having the following formulation at 20° C. for 1, 3, and 4 minutes, then fixed, washed with water, and dried.

The results of the obtained positive images are shown in Table 2.

From the results in Table 2, it can be seen that samples 2, 3, and 4 containing the compound of the present invention were
It can be seen that the maximum density is significantly increased compared to Comparative Sample 1, and a good positive image with a low minimum density is formed more quickly.

Example 3 As a magenta coupler, 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone 392 was added to 39 ml of dibutyl phthalate and 75 ml of ethyl acetate. Each dissolved solution was added to 500 ml of a 5% aqueous gelatin solution containing sodium dotecylbenzenesulfonate,
Emulsified and dispersed.

Next, 1 liter of the same internal latent image type silver halide emulsion (silver chloroiodobromide 0.0.
35 mol), and then mixed with the compounds (1), (3), (10), (■3), (14), (1) of the present invention.
9) and 5% methanol solutions of (20) were added, respectively.

Further, 25 ml of a 5% acetone solution of tetrakis(vinylsulfonylmethyl)methane was added as a hardening agent, and the mixture was coated and dried on a cellulose triacetate support so that the coated silver amount was 20 mg/100 cm2 (Samples 6 to 12).

Separately, as a comparative sample, one without the addition of the compound of the present invention was prepared in the same manner (Sample 5).

After these samples were exposed to wedge light, a developer with the following formulation was applied. The film was developed at 20°C for 5 minutes.

However, the entire surface was uniformly exposed to 1 lux light for 3 minutes from 30 seconds after the start of development.

It was then bleached, fixed, washed with water and dried in the usual manner.

The results of positive images obtained for each sample are shown in Table 1-3.

As is clear from these results, Samples 6 to 12 containing the compound of the present invention were able to obtain good color positive images with increased maximum density due to accelerated fog development and low minimum density.

Example 4 In Example 3, the compounds of the present invention were replaced with U.S. Pat.
Potassium 2-octatecylhydroquinone-5-sulfonate (compound A) described in No. 227552
(Sample-13) was prepared in the same manner.

After exposing samples 5 to 12 prepared in Example 3 and this sample 13 with a wedge, they were developed with a developer having the following formulation at 20°C for 5 minutes, and then bleached and fixed in the usual manner. , washed with water and dried.

Table 4 shows the positive image results obtained for each sample.

As is clear from these results, the samples containing the compounds of the present invention (samples 6 to 12) promote fog development and increase the maximum density, and a comparison of the blue contamination density in the minimum density region shows that the samples containing the compounds of the present invention (samples 6 to 12) have an increased maximum density. It can be seen that a good positive image with a higher maximum density can be obtained with no contamination compared to -13).

Example 5 A photosensitive element was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate support (Sample No. 14).
).

(1) 1:1 copolymer of styrene and N-vinylbenzyl-N-N-N-trihexylammonium chloride (22 m9/100 cm2) and gelatin (22 m9/100 cm2)
100 cm2).

(2) A light-reflecting layer comprising titanium dioxide 7 (220 m9/100 cm2) and gelatin 22 m97100 cm).

(3) Carbon black (23 m9/100 cm2) and gelatin (IBm9/100 cm2) opaque layer.

(4) Magenta image dye-releasing compound, l-hydroxy-4-(3-1α-(2-(2-methoxy-5-sulfamoyl l-azo)-4-hydroxy-1-naphthoxy)ethylcarbamoyl}phenyls rufuonamide)
-N-(δ-2・4-di-tert-amylphenoxybutyl)-2-naphthamide (17m9/100cm2
), N・N-diethyl laurylamide (11■/100
cm2) and gelatin (25~/100 cm2).

(5) The same internal latent image type silver chloroiodobromide emulsion used in Example 1 (14 m9/100 cm2 in terms of silver), compound (13) of the present invention (1 m9/100 cm2), DB
Emulsion layer with P (2 mg/100 cm2), l-formyl-2-phenylhydradi7 (0.13 mp/100 cm2) and gelatin (16.5 mp/100 cm2).

(6) Protective layer with mucochloric acid (1.0 mg/100 cm2) and gelatin (10.0 m9/100 cm2).

For comparison, the compound of the present invention (1) was added to the photosensitive emulsion layer (5).
3) was prepared in the same manner (sample-1).
5).

Next, the following layers were sequentially coated on a transparent polyethylene terephthalate film support having a thickness of 100 μm to prepare a treated sheet.

(1) Copolymer of acrylic acid and ethyl acrylate (7
5/25% by weight) (220 m9/100 cm2) with a dry film thickness of 22.0 μm.

(2) Cellulose diacetate (acetic acid 40%) (50mg/
100 cm2) with a dry film thickness of 5.0 μm.

Next, the above-mentioned photosensitive element was subjected to wedge exposure, and then the above-mentioned processing sheets were superimposed, and a pound containing a processing composition having the following composition in an amount of about 10 ml was attached therebetween to form a film unit.

Next, the film units are placed in a pair of pressurized juxtaposed about 3
The pond was ruptured by passing between rollers having a gap of 40 μm, and its contents were spread between the photosensitive element and the processing sheet.

The composition of the treatment composition used here was as follows.

Benzyl alcohol 15 ml distilled water was added and after 1000.0 m 73 minutes a dye image was observed through the transparent support of the photosensitive element.

The results of the magenta dye image obtained are shown in Table 3.

These results show that by using the compound of the present invention, a good diffusion transfer positive image with a high maximum density and a low minimum density can be formed.

Claims (1)

[Scope of Claims] 1. An internal latent image type silver halide photographic light-sensitive material for direct positive image formation, characterized by containing a compound represented by the following general formula CI) or [l). General formula (I) [wherein R1 is a hydrogen atom, -CO-R7, or -So2
-R7 and R2 represent a halogen atom, an alkyl group, or an alkoxy group, and R3 to R6 represent a hydrogen atom or a substituted or unsubstituted alkyl group. However, R7 represents an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an aralkoxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group. Z represents an alkylene chain necessary to form a 5- to 7-membered carbon ring, and each of these alkylene chains may be substituted or << may be substituted with an unsubstituted alkyl group or aryl group. m represents an integer of 0, l or 2, and n represents an integer of 2 or 3. ]