JPH0311337A - Direct positive type silver halide photographic sensitive material and processing method for same - Google Patents

Abstract

PURPOSE:To obtain a high sensitivity and less reversal fogging and to obviate the change in the sensitivity and reversal fogging even if the stagnation time for coating is long by incorporating specific compds. and electron receptive org. compd. into the above-mentioned material. CONSTITUTION:Silver halide emulsion layers contain the electron receptive org. compd. and contain at least one selected from the compds. expressed by formula I and/or II in at least one layer on the side where the silver halide emulsion layers exist. In the formulas I, II, R1 to R4 respectively denote a hydrogen atom, lower alkyl group, alkoxy group, carboxy group, alkoxycarbonyl group, sulfo group, halogen atom, or nitro group. The electron receptive org. compd. having the preferable spectral sensitization characteristic is the compd. with which the 2-arom. substd. indole nucleus is combined with the methine chain combined with the org. heterocyclic nucleus through the carbon atom of the 3rd position. The prescribed sensitivity and max. density are obtd. and the fogging of the min. density is lowered. The generation of the fluctuation in the sensitivity or the increase of the fogging generated at the time of the stagnation for holding of the emulsion is prevented.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a direct positive type halogen emulsion that has a predetermined maximum density even when kept at a temperature for a long period of time and has less fog and dye staining. The present invention relates to a silver oxide photographic light-sensitive material and a method for rapidly processing the same.

[Background of the invention]

Traditionally, in the production of silver halide photographic materials,
When coating a silver halide emulsion onto a support, two methods are commonly used: the so-called continuous method, in which the emulsion is coated continuously, and the badge method, in which the emulsion is kept warm in a molten state and coated in fixed amounts. known to.

The continuous method has the advantage that there is no stagnation step of the emulsion, but has the disadvantage that, in the case of continuous coating over a long period of time, variations in photographic performance are likely to occur within the same lot.

Therefore, the addition flow rate of various additives and its control are important, and process control and maintenance of complicated and precise control equipment or in-line addition equipment is extremely difficult.

On the other hand, in the batch method, a certain amount of emulsion is melted all at once, the required amount of additives are added, and the emulsion is stagnated under heat-retaining stirring to be applied sequentially.Therefore, there is little variation between the same lot, and the photosensitive material is of uniform quality. It has the advantage that it can be obtained.

However, in the badge method, the emulsion remains in a molten state for a long time, resulting in considerable fluctuation and deterioration of photographic properties.

For example, they tend to increase or desensitize, and also tend to cause fog, and these phenomena are especially noticeable in high-speed emulsions.

In the case of the direct positive silver halide emulsion according to the present invention,
This results in extremely disadvantageous phenomena such as a decrease in the maximum density and an increase in the minimum density (fog).

Under these circumstances, many techniques such as various stabilizers and antifoggants have been reported for the purpose of preventing changes in photographic properties during the emulsion manufacturing process.

For example, JP-A No. 58-217928, JP-A No. 63-103
Although conventional techniques such as No. 233 and No. 62-61046 are known, the improved technology of the present invention, which includes ultra-rapid processability for the direct positive silver halide photographic light-sensitive material, is as follows.
It's hard to say that it's enough.

On the other hand, rapid development of silver halide photographic materials has been rapidly progressing in recent years, and there is a constant demand for an increase in the amount of processing within the same amount of time.

Such a tendency can also be seen in the field of X-ray photosensitive materials, such as medical X-ray films.

In other words, the number of medical examinations has increased sharply due to the enforcement of regular health checkups, and the number of examination items has also increased in order to make diagnoses more accurate, resulting in an increase in the number of photographs taken. be.

Automation of diagnosis (photography/transportation) for rapid processing of photosensitive materials
At the same time, it is necessary to make photosensitive materials more suitable for rapid processing.

However, direct positive silver halide photographic light-sensitive materials in the field to which the present invention relates are not necessarily as simple as other silver halide photographic light-sensitive materials, and have certain drawbacks. .

For example, after imagewise exposure, the total processing time is 2 minutes using an automatic processor.
Ultra-rapid processing, which takes more than 0 seconds and less than 60 seconds, causes problems such as a decrease in sensitivity and maximum density, and also increases the likelihood of uneven development.

In order to obtain the required sensitivity and density, this can be avoided by increasing the amount of coating, that is, the amount of silver halide emulsion, but this results in going against the direction of rapid processing.

That is, if rapid processing is performed, (a) the fixing time becomes insufficient, resulting in insufficient fixing. (b) Washing of the film becomes insufficient. (c) Drying of the film becomes insufficient.

This causes problems such as: One way to solve the problems (a) to (c) above is to reduce the amount of silver halide.As mentioned above, reducing the amount of silver halide without deteriorating photographic properties improves suitability for rapid processing. This is an essential requirement for granting.

Examples of the technology for the direct positive photosensitive material according to the present invention include JP-A-64-29835 or JP-A-63-148.
Although a technique using a specific ionic surfactant is known, such as in Japanese Patent No. 257, it cannot be said to be sufficient in terms of ultra-rapid processability, including the above-mentioned emulsion stagnation stability.

[Purpose of the invention]

Therefore, the first object of the present invention is to provide a direct positive type silver halide photographic light-sensitive material that has a predetermined sensitivity and maximum density, has a low minimum density (fog), and is capable of rapid processing without uneven development. The goal is to provide the following.

A second object of the present invention is to provide a direct positive type silver halide photographic light-sensitive material that prevents fluctuations in sensitivity or increases in minimum density (fog) that occur when emulsion stagnates during heat retention, and has stable photographic performance. It is.

A third object of the present invention is to use the above-mentioned photosensitive material after imagewise exposure.
An object of the present invention is to provide a method for processing a direct positive type silver halide photographic material, which is developed in a total processing time of 20 seconds or more and less than 60 seconds.

Other objects will become apparent from the description below.

[Structure of the invention]

As a result of extensive studies, the inventors of the present invention have found that these objects can be achieved by the following method, and have completed the present invention. That is, (1) in a silver halide photographic light-sensitive material having at least one direct positive silver halide photographic emulsion layer on at least one side of the support, the silver halide emulsion layer is made of an electron-accepting organic compound; and in at least one layer on the side where the silver halide emulsion layer is present, the following general formula [1]
and/or a direct positive type/SC7 silver genide photographic light-sensitive material containing at least one compound selected from the compounds represented by [II] and (2)/) all This is achieved by the method for processing a direct positive silver halogenide photographic material according to item (1), in which the processing time is 20 seconds or more and less than 60 seconds.

General formula CI) In the general formula, R, R3 and R4 each represent a hydrogen atom, a lower alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a halogen atom, or a nido O group. .

However, at least one of Rr and Rx is a carboxy group, an alkoxycarbonyl group, or a sulfo group.

The present invention will be explained in detail below.

The direct positive silver halide photographic emulsion constituting the present invention is a silver halide containing silver iodide, and may be any of silver iodochloride, silver iodobromide, and silver iodochlorobromide. Silver iodobromide is particularly preferred since high sensitivity can be obtained.

The average silver iodide content in such silver halide grains is 0.
．． There may be localized areas of high concentration of silver iodide of at least 20 mol % in the interior of the grains, preferably 0.5 to 8 mol %.

The particles may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have a tabular or potato-like crystal shape.

The silver halide photographic emulsion constituting the present invention may be of a monodisperse type, or may be a single dispersion emulsion or a mixture of at least two types.

Invention I This silver halide photographic emulsion may contain an inorganic desensitizer inside the crystal, and as the inorganic desensitizer, a soluble metal salt of group (I), such as a soluble rhodium salt or a soluble iridium salt, may be added. You may do so.

The amount added is 10-” to 10-” per mole of silver halide.
It may be in the molar range, more preferably from 10-1 to 10-
'moles are preferably added to the emulsion in aqueous solution.

In the present invention, an electron-accepting organic compound is used in order to obtain a good positive image. This helps prevent the reaction between photoelectrons and silver ions in which silver nuclei form and grow.

Next, the electron-accepting organic compound according to the present invention will be explained in detail.

Compounds used as electron acceptors in the practice of this invention include organic compounds for which the sum of the cathodic polarographic half-wave potential (Ea) and the anodic polarographic potential (Ec) is positive. Preferably, such compounds are those which spectrally sensitize the photographic silver halide emulsion to light having a wavelength of at least about 480 sμ or greater, and generally about 480 sμ.
It is spectrally sensitized to light having a wavelength in the range of 1 μm to 800 μm. These compounds include dimethine No. 16 and No.
, 35+ 38A 7 (can be spectrally sensitized such that the ratio of minus blue light relative velocity to blue light relative velocity is greater than 7, preferably greater than lO, when exposed to a tungsten light source through a Luther, Sensitized electron acceptor
It is called.

Particularly useful electron-accepting organic compounds that can be used in the direct positive silver halide emulsions of the present invention are cyanine dyes, particularly those described in Bruker et al. Belgian Patent No. 660,253, published March 15, 1965. It is an imidazoquinoxaline dye as described above. Very good results are obtained when using cyanine dyes containing an indole nucleus with an aromatic substituent in the 2-position. In addition to indole nuclei, the dyes which are advantageously used also contain desensitizing nuclei.

The electron-accepting organic compound with preferable spectral sensitization used in the present invention is represented by the following general formula CI).

General formula (Ill) in the formula represents a methine chain having 2 to 3 carbon atoms, and Y is 2
- Represents an aromatic substituted indole nucleus bonded to the methine chain through its 3rd carbon atom, Q is an organic heterocyclic nucleus, and when L is a methine chain with 2 carbon atoms, an asymmetrical - Q represents the desensitizing nucleus that should give the dimethine cyan dye, and when the chain is a methine chain with 3 carbon atoms, Q is
Represents an aromatic substituted indole nucleus bonded to the methine chain via its 3rd carbon atom, where L has 2 carbon atoms
A particularly useful desensitizing nucleus is the methine chain of imidazo-
The (4,5b)-quinoxaline nucleus is bonded to the methine chain via its 2nd-position carbon atom.

The spectrally sensitized electron-accepting organic compound preferably used in the present invention has the following general formula (IV): where A is an aromatic nucleus, such as a phenyl nucleus, and various substituents For example, alkyl (e.g. methyl, ethyl,
propyl, butyl, etc.), alkoxy (e.g. methoxy,
ethoxy, propoxy, butoxy), halogen (e.g. B', CI2 or F), aryl (e.g. phenyl)
or A is a heteroaromatic liquid; preferably has 5 to 6 carbon atoms, and the petro atom is preferably nitrogen, sulfur or oxygen; R8 and R3 are each a hydrogen atom; , represents a halogen atom (e.g. Cr2, Br or F) or an alkyl or alkoxy substituent (e.g. methyl, ethyl, propyl, butyl, methoxy, propoxy, hydroxyethyl, etc.); or R2 and R1 jointly have 6 carbon atoms. Represents the atomic group necessary to complete the closed aromatic ring; R2 represents an alcohol residue, such as alkyl preferably containing 1 to 8 carbon atoms (e.g. methyl, ethyl, propyl, butyl, octyl), sulfonalkyl (for example sulfopropyl or sulfobutyl), sulfatoalkyl (for example sulfatopropyl or sulfatobutyl), carboxyalkyl (for example carboxyethyl or carboxybutyl), etc.; Preferably those having 1 to 18 carbon atoms (e.g. methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, hexyl, dodecyl, octadecyl, benzyl, beta-phenylethyl, etc.), sulfoalkyl (e.g. sulfopropyl or sulfobutyl) sulfatoalkyl (e.g. sulfatopropyl and sulfatobutyl), carboxyalkyl (e.g. carboxyethyl, carboxybutyl), hydroxyalkyl (e.g. hydroxyethyl, hydroxypropyl, hydroxybutyl), allyl, alkenyl (
(e.g. propenyl, butenyl), alkynyl (e.g. propargyl), cycloalkyl (e.g. cyclobutyl,
cyclohexyl), dialkylaminoalkyl (e.g. dimethylaminoethyl), and aryl (e.g. phenyl, P-tolyl, 0-tolyl, 3,4-dichlorophenyl), etc.; R1 is the same as R2 or jointly with R, e.g. trimethine or i R7 representing alkylene such as dimethine
is halogen or No! , n is 0 or an integer of 1 to 3, X is an anion, preferably an acid anion such as chloride, bromide, iodite, P-1-luenesulfonate,
thiocyanate, sulfonate, methyl sulfate,
Represents ethyl sulfate, barchlorate, etc.

One particularly useful group of spectrally sensitized electron acceptors has the general formula:

General formula (IVa) where R, , R, , R, each represent an alkyl group (for example methyl, ethyl, propyl or butyl) or an aryl group (for example phenyl), and X is as described above, Q
is (1) -CD-01 where Ql is the detracting nucleus from which the trimethine cyanine dye is to be made, such as 6-nitomepenzthiazole nucleus, 5-nitroindolenine nucleus, imidazo(4,5-b)quinoxaline nucleus or pyrrolo(2,3b)-pyrido nucleus (e.g. 11 where Rls+R+s, R17 is R1□, R, ,R,
(same as 4)) and represents the atomic group necessary to complete the dimethine cyanine dye, and a desensitizing nucleus for making a dimethine cyanine dye, such as a pyrazole nucleus or a 2-aromatically substituted indole nucleus, through its 3rd carbon atom. In the formula, A, Rr, Rx, Rs, and R, which are bonded to the chain, represent a substituent consisting of the atomic group necessary to complete (as described above).

Another useful group of spectrally sensitized electron acceptors is represented by general formula (V) below.

Phosphortrimethine cyanine dyes of general formula (V) in which each nucleus is attached to the methine chain via the carbon atom at the 2-position are useful electron acceptors in the practice of this invention.

A typical such dye is represented by the following general formula (Vl).

General formula (VI) where X, A, Rr, R!, Rs and R
ac As mentioned above; A IRa, RIRIs and R11
are respectively A, R,,R! +Same meaning as R1 and R; Y is a hydrogen atom, an aryl group (e.g. phenyl, alkyl (e.g. methyl, ethyl, propyl, butyl), substituted or alkoxy (e.g. methoxy, ethoxy, propoxy) substituted phenyl), or hetero Represents a cyclic aromatic group (eg thiophene).

In the symmetrical imidazo(4,5-b)quinoxa formula,
X' R, and R1 are the same as above, R1, and R1!
is the same as R4 and R3, each X' is a halogen (e.g. Br,
C(1 or F), n is O or an integer of 1 to 3.

Yet another group of electron acceptors is represented by the following general formula [■].

General formula [■]
As described in , R3 and Ras are hydrogen atoms, alkyl groups (preferably those having 1 to 18 carbon atoms, examples being methyl, butyl, octyl, dodenyl, octadecyl), aryl (e.g. phenyl, P -Trill, 3
, 4-dichlorophenyl). R
1, is the same as R6. Dyes of this type are advantageously produced by conventional methods suitable for producing such materials. 2-Alkylimidazo (:
4,5b) Prepared by refluxing quinoxalinium salt and pyrazole-4-carboxaldehyde. A typical dye of this type is 1,3-diallyl-2-(
2-(3,5-dimethyl-1-phenyl-4-pyrazolyl)hinyl]imidazo-[4,5-b)-quinoxalinium iodite.

This dye is 1,3-diallyl-2-methylimidazo[4
゜5'b) Quinoxalinium P-toluenesulfonate and 3,5-dimethyl-1-phenyl-pyrazole-4
- Ruboxyaldehyde is refluxed in anhydrous W and acetic acid for a suitable period of time, for example, 10 minutes.

Still other useful spectrally sensitized electron acceptors are cyanine and merocyanine dyes having desensitizing substituents such as NO8 on at least one nucleus, preferably two nuclei.

Other specific electron acceptors of significant benefit in the practice of this invention are cyanine dyes containing at least one total molar equivalent of halogens having an atomic weight in the range of about 35 to about 127. Preferred cyanine dyes of this type have at least one methine group, the hydrogen atoms having an atomic weight of about 35 to about 1
It is replaced with 27 halogen atoms, ie chlorine, bromine, or iodo atoms.

Suitable halogen-containing cyanine dyes have the following general formula:
■〕 ,...zl-・.

R1-N(LL), -, -C-CX-(CI(-C1
-, (-CH-CXI-), z1 and 2. are heterocyclic nuclei of the type used in anine dyes, such as benzothiazole-based nuclei (e.g. benzothiazole, 4-
Chloropentthiazole, 5-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 5-bromobenzothiazole, 4-7enylbenzothiazole, 5-phenylbenzothiazole, 6-y enylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 5-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, 5-hydroxybenzothiazole, etc.), naphthothiazole-based nuclei (e.g. σ -naphthiazole, β-naphthothiazole, 5-methoxy-β-naphthothiazole, 5-ethyl-β-naphthothiazole, 8-methoxy-σ-naphthothiazole, 7-methoxyl α-naphthothiazole, etc.), benzoxazole-based core (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methyl-benzoxazole%5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole,
5-hydroxybenzoxazole, etc.), naphthoxazole-based nuclei (e.g. a-su7toxazole, β-naphthoxazole, etc.), benzoselenazole-based nuclei (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-
methylbenzoselenazole, 5-hydroxybenzoselenazole, etc.), naphthoselenazole-based nuclei (e.g. q-
naphthoselenazole, β-naphthoselenazole, etc.), 2
- Quinoline-based nuclei, including quinolines (e.g. quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-medoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-
Quinolines (e.g. quinoline, 6-methoxyquinoline,
7-methoxyquinoline, 8-methoxyquinoline, etc.) Represents the nonmetallic atomic group necessary to complete the inquinoline type nucleus (e.g. 1-inquinolines, 3-inquinolines, etc.): X and X.

are each selected from the group consisting of a hydrogen atom, chlorine, bromine, and iodo, and at least one of X and Xl is chlorine, bromine, or iodo. lower alkyl such as , secondary butyl, tertiary butyl; sulfoalkyl having 1 to 4 carbon atoms (e.g. sulfomethyl, sulfoethyl,
A is an acid anion (e.g. chloride, bromide, iodite, p-toluenesulfonate); , thiocyanate, methyl sulfate, ethyl sulfate, verchlorate, etc.); d, rn, n and p each represent a positive integer of 1 to 2.

Other examples include phenosafranine, donacryptol yellow 5-11-ditropenzylidenerhodanine, 51-nitrobenzylidene-3-phenyl-rhodanine, 3-ethyl-5-■nitrobenzylidenerhodanine, 3-ethyl -5'-(2.4 dinitrobenzylidene) rhodanine, 5-o-nitrobenzylidene-3-7
Enylrhodanine, 1'. 3-diethyl-6-nitrothia-2'-cyanine iodite, 4-nitro-6-chlorobenzotriazole, 3,3'-diethyl-6,6
'-Dinitro-9-phenylthiacarbocyanine iodite, 2-(p-dimethylaminophenyliminomethyl)benzothiazole ethoethyl sulfate, crystal violet, 3.3'-diethyl-6,6'-
dinitrothiacarbocyanin ethylsal 7x h,
1',3-diethyl-6-nitrothia-2'-cyanine iodite, ■. 3-diamino-5-methyl-7enadinium chloride, 4-nitro-6-chlorobenzotriazole, 3.3'-di-p-nitrobenzylthiacarbonanine bromide, 3.3'-di-p-nitrophenylthia Carbocyanine iodite, 3.3'
C-o-nitrophenylthiacarbocyanine verchlorate, 3.3'-dimethyl-9-trifluoromethylthiacarbocyanine iodite, 9-(2.

4-dinitrophenylmercapto 13,3'-ethylthiacarbonanine iodide, bis(4,6
-diphenylpyryl-2)) rimethine cyanine verchlorate, anhydro-2-p-dimethylaminophenyliminomethyl-6-nitro-3-(4-sulfobutyl)
Benzothiazolim hydroxide, l-(2-benzothiazolyl)-2-(p-dimethylaminostyryl)-4
, 6-diphenylpyridinium iodite, 1,3-
Diethyl-5-(1.3-neobenthrene-6-(1.
3.34limethyl-2-indolinylidene)2,4-
Hexadienylidene]-2-thiobarbital acid, 2.
3.5-) Diphenyl-2H-tetrazolium chloride, 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-phenyl-tetrazolium chloride, l-methyl-8-nitroquinolium methylsulfate, 3 .6-bis(4-(3ethyl-2-penzothiazolinylidene)-2-butenylidene) -1,2
, 4,5-cyclohexanetetron, 1,3-diallyl-2-[2-(3,5-dimethyl-l-7enyl-4
-pyrazolyl)vinyl]imidazo(4.,5b'lquinoxalinium iodite, 6-amino-1-methyl-
2-((1'-methyl-6'-quinolinium)vinyl]
Quinolinium dichloride, 4-Cp-amyloxyphenyl)-2,6-di(p-ethylphenyl)thiapyrylium, verchlorate, and the like are included.

Incidentally, these desensitizing dyes described above are disclosed in, for example, U.S. Pat.
30.694, Belgian Patent No. 660.253, Japanese Patent Publication No. 50-3938, etc.

Furthermore, F. M. “The Cyanine” by Hamer
Dyes and Related Compound
ds"Wiley (1964), and can be understood by those skilled in the art as known compounds.

The electron-accepting compound present in the direct positive silver halide emulsion of the present invention is not limited to the external electron acceptors mentioned above, but may be other external electron acceptors.

Further, it may be used in combination with an internal electron acceptor such as a rhodium compound.

These electron-accepting compounds of the present invention are present in an amount of about 10 mg to 2 g per mole of silver halide in a direct positive silver halide emulsion.
Used within the range of

Particularly preferably, the amount of Agx in the range of 50 mg to 1 g and 1 mol of Agx is added by the above-mentioned addition method.

Next, specific examples of the electron-accepting organic compound according to the present invention are shown below, but the present invention is not limited thereto.

Exemplary compound N.

OMe Meo e tse e 0 C3H 蓼 In the general formulas CI) and [■), R,,R,.

The number of carbon atoms in the alkyl group in the lower alkyl group, alkoxy group, and alkoxycarbonyl group represented by R3 and R is 1 to 4.

Next, typical examples of the compound represented by (a) or (b) of general formula (1) will be given. Note that the present invention is not limited to this.

(II-1) (■ 2) (n-3) (II-4) cn-s> (I[-6) (u-7) (I[-8) (II-9) (I[ 10) Next, typical examples of the compound represented by (C) or (d) of the general formula [■] will be given. Note that the present invention is not limited to this.

(ff-11) (II-12) (Issue 3) (II-14) These exemplary compounds can be easily obtained by a known method, for example, by reacting a diamine compound with carbon dioxide. The Chemist IJ- of Heterocyclic Conno (Unz Imidazole'Andyu Derivatives
erocyclic co+mounds 1m1d
azole and Der+vat-ives) V
ol, 1. Ann, 325. i
, 53 (1902), JAC5, 71, 1436 (+9
49), JAC576, 4935 (1954), Ber
ich te, 26, 545, 2737 (
1893), J, Pract, che+m, 125,
466, (1930), etc. The method described therein can be referred to.

At least one selected from the compounds represented by the above general formula [I] and/or (1) according to the present invention is added to at least one layer on the side where the direct positive type silver halogenide emulsion layer of the present invention is present. By doing so, the object of the present invention is obtained.

The layer on the emulsion layer side refers to various hydrophilic siloid layers adjacent to the photosensitive emulsion layer, such as a photosensitive emulsion layer, a non-photosensitive emulsion layer, a protective layer, an intermediate layer, a filter layer, and a dye layer. Such a direct positive type/% silver halide emulsion is chemically ripened, various additives are added thereto, prepared as a coating liquid, and then kept at a temperature. In the present invention, the temperature during the stagnation of heat retention is 3
5°C to 60°C, and the residence time varies depending on the manufacturing conditions, but it is possible for at least 12 hours, and usually 3 hours.
hours to 8 hours.

The general formula (1) and the general formula (I[
) The compound represented by ) may be added before or after various additives are added in the case of an emulsion, and the order of addition does not matter in the case of coating.

Although the amount added varies depending on the type of silver halide emulsion,
Generally 0.001g per mole of silver halide -
The amount may be in the range of 10 g, preferably 0.005 g to 2 g. For layers other than silver halide emulsion layers, the amount added can be determined according to the emulsion layer. When added, it may be added after being dissolved in water or a hydrophilic organic solvent such as methanol or ethanol.

The compounds of general formula (I) and NH according to the present invention may be used singly or in combination, and may be used in different layers for each layer. Furthermore, it can also be used in combination with other additives.

By incorporating at least one fluorine-containing surfactant into the constituent layers of the direct positive silver halide photographic light-sensitive material according to the present invention, the desired effects of the present invention can be favorably achieved.

The fluorine-containing surfactant to be added and contained in at least one layer of the silver halide photographic light-sensitive material of the present invention includes those having a nonionic, anionic, cationic or betaine structure, preferably having 4 carbon atoms. It has the above fluoroalkyl group.

Examples of ionic groups include anionic surfactants such as sulfonic acid or its salts, carboxylic acids or its salts, and phosphoric acid or its salts, or amine salts, ammonium salts, sulfonium salts, phosphonium salts, and aromatic amine salts. Examples include cationic or betaine type surfactants, and nonionic surfactants having polyalkylene oxide groups, polyglyceryl groups, and the like.

These fluorine-containing surfactants are disclosed in U.S. Pat. No. 4,335
．． No. 201, No. 4,347,308, British Patent No. 1, 4
No. 17,915, No. 1,439,402, Special Publication No. 1972
・No. 26687, No. 57-26719, No. 59-38
No. 573, JP-A-55-149938, JP-A No. 54-48
No. 520, No. 54-14224, No. 58-20023
No. 5, No. 57-146248, No. 58-196544
Examples include compounds described in the specification of No. 1, etc.

Preferred specific examples of these are shown below, but the present invention is not limited thereto.

F　　　　　　CsF+ySOJ F2　C7F+5COONa F 3 CsF+yCJ12CH20SO3Na4 C,) IT C,F,　,So,N-C)I,C00KC,H.

C@F 1ysO1N (C)11cH10)7(CH
I) ISO3NaC3H,0 Hot CaF++5OJCHxCH2OP ONaCH 0 H(CFt)'1cHtof)C-C)l! HCCFx
hCHsOIX CH5OsNa-11 CsF+yCHzCHtα)C-CH.

C,H,0OC-CO 5o, Na 8 CH.

0 Goods.

-22 CM.

-12 CH.

CH3 3 L CHl -14 C11°εH3 -15 L CH 7 CHl 4 -26 C,F, ,Coo(C)I,CH,0 sho. H-27 C+ oFx +C(X) [CJC)120)To'
;IH-29 CH.

c, p, 7SO! N(CHIC)1.0),)l-3
0 C,,)! □ C, F, a cut tN(C)I, CHzO)ri]H-31 F-32 Cki01 -34 CJ+tC1lxCHtO(CH*CHzO stone 1H-3
7 C9F+eO (CHtCHzOhCHs) The above-mentioned 7-containing surfactant according to the present invention may be added to any of the constituent layers of the silver halide photographic light-sensitive material, for example, the surface protective layer, intermediate layer, and undercoat. It is added to non-light sensitive layers such as layers or backing layers or silver halide emulsion layers.

More preferred are the emulsion layer and its surface protective layer, and the backing layer and its surface protective layer. These may be used not only in one-sided layers but also in both-sided layers at the same time.

The fluorine-containing surfactants according to the present invention may be used in combination of two types or in combination with other synthetic surfactants.

The silver halide emulsion used in the present invention is given a suitable fog by using a reducing agent and a gold compound for the silver halide emulsion. At least one compound selected from thiosulfate and/or thiocyanate is allowed to coexist and fogged, or after fogging is performed with a reducing agent and a gold compound, chisai sulfate and/or thiocyanate is added. Even better fogging can be imparted by containing at least one compound selected from an acid salt.

In the present invention, fogging is imparted by the above method, but by adding water-soluble iodide to the silver halide emulsion before fogging is imparted, good removal can be obtained. Water-soluble iodides include ammonium, potassium, lithium,
Sodium iodide is mentioned, and the amount added is 1 to 10 mmol of water-soluble iodide per mole of silver halide. If the amount added is less than this, the removal will be poor. If the amount is more than this, a sufficient maximum concentration cannot be obtained and the concentration decreases during storage. The conditions for heating the silver halide can vary widely, but the pH is generally 5.
The pH is within the range of 5 to 9, preferably 6 to 7. Moreover, pAg is generally within the range of 6.5 to 8.5, and the temperature is generally 40°C to 100°C, preferably 5000 to 70°C.
is within the range of

A hydrophilic protective colloid such as gelatin, which suspends the silver halide grains during coating, has a
Preferably, it is used in a proportion of 30 to 200 grams.

Reducing agents used in the present invention include aldehyde compounds such as formalin, hydrazine, triethylenetetramine,
Organic reducing agents such as organic amine compounds such as thiozukadine dioxide and imino-amino-methanesulfinic acid, inorganic reducing agents such as stannous chloride, or reducing agents such as amineporan are preferably used.

The concentration of the reducing agent used varies depending on the silver halide grains, application purpose, etc., and varies depending on the type of reducing agent, but is generally 0.00 per mole of silver halide.
It is within the range of 1-t,oo mmol.

Further, the gold compounds used in the present invention are monovalent and trivalent soluble gold salts, such as chloroauric acid, thiocyan M gold, chlorfinancial sodium, chlorfinancial potassium, brominefinancial potassium, iodofinancial potassium, gold cyanide potassium, Potassium gold thiocyanide, sodium gold thiomaleate,
Gold thioglufus etc. are used.

The amount of this gold compound to be used varies depending on the size composition of the silver halide particles, the application purpose, etc., but it is within the range of 0.0001 to 0.1 mmol per mol of silver halide, preferably o, Good results are obtained when used at low concentrations within the range of oos to 0.05 mmol.

Further, as specific examples of thiogt salts and thiocyanates used in the present invention, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, ammonium thiocyanate, or complex salts thereof are used in the shed, and these compounds is generally 0.0003 per mole of silver halide
It is used in a range of 10.0 mmol, preferably 0.0 mmol.
0.005 to 0.5 mmol is used. And when to use these thiosulfate and thiocyanate salts,
It may be used before, during or after the formation of fog with the reducing agent and gold, but the required amount varies depending on the time of use, and especially when added after the formation of fog, the amount must be increased.

Other photographic additives can also be added to the direct positive silver halide emulsion according to the present invention. As stabilizers, for example, those described in Japanese Patent Publication Nos. 49-16053, 49-12651, 48-66828, etc., azaindenes, benzothiazolium compounds, mercapto compounds, or cadmium, cobalt, niakel, etc. , manganese, zinc, and other water-soluble inorganic salts. Further, as a hardening agent, for example, formalin, glyoxal, aldehydes such as mucochloric acid, S-triazines, epoxies,
Aziridines, vinyl sulfonic acid, etc., and sensitizers such as Japanese Patent Publications No. 42-25203, No. 43-10245, No. 43-13822, No. 43-17926, No. 4
No. 3-17927, No. 46-21186, No. 49-8
It may also contain polyalkylene oxides and derivatives thereof selected from those described in No. 102, No. 49-8332, and the like.

Furthermore, for example, Japanese Patent Publication No. 45-24910, No. 45-298
It is also possible to contain a color coupler selected from those described in No. 78 and the like. In addition, brighteners, thickeners, preservatives, matting agents, antistatic agents, etc. can also be contained as necessary.

The silver halide emulsion of the present invention is grafted with protective colloids such as gelatin, gelatin derivatives, polyvinyl alcohol, polyvinyl acrylate, polyvinyl bialidone, cellulose ethers, partially hydrolyzed cellulose acetate, and ethylene oxide as described in Japanese Patent Publication No. 4920530. Hydrophilic polymers such as poly(N-hydroxylalkyl) β-alanine derivatives can be included.

Furthermore, a dispersion polymerized vinyl compound may also be contained as a binder for emulsion. For example, it is described in Japanese Patent Publication No. 49-32344; Polymer latex of unsaturated ethylene-linked polymer emulsion polymerized in the presence of an activator, Japanese Patent Publication No. 49-209
It is preferable to use the ceric salt described in No. 64 to contain a polymer latex etc. in which a polymer compound having a hydroxyl group is grafted with an unsaturated ethylene 7th polymer from the viewpoint of improving the physical properties of the film. It is.

Also, from the point of view of emulsion technology, Japanese Patent Publication No. 44-2523, No. 44
As described in No. 9499, the developer is protected and contained, higher fats such as liquid paraffin and higher unsaturated fatty acids such as stearyl acetoglyceride are protected and contained to improve film properties, and color couplers and stabilizers are added depending on the purpose. etc. can also be protected and contained.

The direct positive silver halide emulsion thus obtained can be applied to any suitable photographic support such as glass, wood, metal, film, e.g. cellulose acetate, cellulose acetate butyrate, cellulose nitrate, polyester, polyamide, polystyrene, etc. , paper, baryta-coated paper, polyolefin-coated paper such as polyethylene or polypropylene-coated paper, and the polyolefin-coated paper can be subjected to electron bombardment treatment to improve the adhesion of the emulsion.

The total processing time according to the present invention means that after the photosensitive material of the present invention is imagewise exposed, it is inserted into the roller which is the photosensitive material insertion port of an automatic processor, passes through a developing tank, a fixing tank and a washing tank, and then exits the drying section. The time it takes to reach the final roller.

The total drying process time is less than 60 seconds, more preferably 20 to 60 seconds, particularly preferably 50 seconds or less.

Also, the treatment temperature is 60"C or less, preferably 20 to 45"C.
It is ℃.

An example of the breakdown of the total processing time is shown below.

Processing process Processing temperature (℃) Processing time (seconds) Insert
1.2 Development + crossing 3514°6 Fixer crossing 33 8.2 Water washing ten crossing 25 7.2 Slide a
40
5.7 Drying 45
8.1 total
45.0 Various photographic additives can be used in the emulsion according to the present invention in Step I: after physical ripening or chemical ripening. Examples of known additives include Research Disclosure No.
-17643 (December 1978) and No.18
716 (November 1979).

The types of compounds and locations listed in these two research disclosures should be listed in the memorial service.

AdditivesChemical sensitizersSensitizing dye development acceleratorsAntifoggantsStabilizing agentsColor stain inhibitorsImage stabilizersUV absorbersFiltersDye brightenersHardening agentsCoating aidsSurfactantsPlasticizersSlip agentsStatic inhibitors Matting agent binder 1.7643 Classification ■ ■ xl ■ // 25 ■ 25 ■ 25-26 ■ /1 4 V 6 Right - 649 Left 648 - Upper right 649 - Upper right 650 Left - Right 649 Right ~ 650 Left // 651 Right 650 Right 650 Right〃 650 Right 26 II 651 Right The photosensitive material according to the present invention is the above-mentioned RD-17643-2
The usual developers described on page 9 or on the left column of page 651 of RD-18716 can be used as a base.

Supports that can be used in the photosensitive material of the present invention include, for example, the above-mentioned RD-17643, page 28 and R
Examples include those described in the left column of page 647 of D-18716. Suitable supports include plastic films, and the surfaces of these supports may generally be provided with an undercoat layer or may be irradiated with ultraviolet light to improve the adhesion of the coating layer. The emulsion according to the present invention can then be coated on one or both sides of the support thus treated.

〔Example〕

The present invention will be explained in more detail below by showing examples of the present invention. However, as a matter of course, the present invention is not limited to the examples described below.

Example-1 A monodisperse emulsion was prepared according to the following formulation.

Note that in the following description, AgX represents silver halide.

b) Gelatin 8g/AgX 1 mol Hexachloroiridium(III) potassium acid 42mg/AgX 1 mol Water 500+m12/AgX
l molar ratio) Silver nitrate 170g/A
gX l Mol ammonia water (28%) equivalent water 210mQ/AgX l
Morha) Potassium bromide” 120g/Ag
X l -r: potassium iodide 3.5
g/^gX1 mole water 21 (l
eg/AgX l -T-runi)acetic acid
p)! The amount to be neutralized to 6.0. First, at 40°C, put liquid (b) and liquid (c) into a reaction vessel of liquid (a) using a double jet method.
They were added simultaneously over a period of 15 minutes.

The above is the particle formation step, and then a desalting step is started in which excess salt is removed.

The silver halide emulsion formed in the above step-3 was kept at 40°C, and 100 cc of a 5% aqueous solution of formalin condensate (average degree of polymerization 2) of naphthalene sulfonic acid formalin condensate (average degree of polymerization 2) was added with 1 mol of AgX and 20% Mg5O, and 40 ce of an aqueous solution of 1 mol of Ag Stir for a minute and then let stand. Then drain the supernatant and
The liquid volume was set at 200 cc per mol of halogenide. Next, 40°C pure water was added to 1.8Q1 mol AgX, and the mixture was stirred for 5 minutes. (Step-4) Next, 20 g of Mg5O, 1 mol of AgX was added, stirred and left to stand in the same manner as above, and the supernatant liquid was removed to perform desalting.

This solution was then stirred. (Step-5) After stirring, ^gX
After redispersing the mixture, gelatin and phenol were added and dispersed at 55°C.

After adjusting the pH to 6.8, an appropriate amount of potassium iodide was added to the resulting emulsion. (Step-6) Thiourea dioxide 0.5 g 1 mol AgX, thiosulfate f at 60°C
-T'J'7 M2. lImg 1 mol AgX and 2.7+mg 1 mol AgX of chloroauric acid were added and aged until proper fog was obtained. (Step-7) Exemplary electron-accepting organic compounds according to the present invention and compounds represented by general formulas (1) and [) are added to the ripened emulsion.
Add as shown in 1 and further add the additives shown below to create an emulsion coating solution. While keeping the temperature at 40℃, samples were taken at each dwell time of 0 minutes, 3 hours, and 8 hours, and the emulsion was coated. The amount of silver per side of the support is 2
g/m", and then apply the following protective layer liquid on top of it.
(2) was simultaneously coated with a gelatin amount of 1.20 g/m 2 and dried to obtain a sample.

(Composition of emulsion coating solution) Lime-treated ossein gelatin 51 g per coating solution IQ Silver halide grains 0.6 mol l-phenyl-
5-Metsushi Captotetrasol 0.015g Nitron
0.05 g Copolymer of styrene and maleic acid 1.5 g 2.2-dihydroxymethyl-1-butanol 8 g p-nitrophenyl-triphenylphosphonium chloride 2 g 1.1-
Dimethylol-I-bromo-1-nitromethane 30mg (
Protective layer solution) Lime-treated inert gelatin 68g acid-treated gelatin g Ludox AM (colloidal silica, DuPont!!) 30g per 1Q of coating solution
Polymethyl methacrylate particles (projected area average particle size 3.5 am) 1.2
g2.4-dichloro-6-hydroxy-1,3,5-triazine sodium salt aqueous solution (2%) 5m12 glyoxal (40%) l+m12
Furthermore, exemplary fluorine-containing surfactants and comparative active agents are listed below.
Added as in 1.

The samples obtained in this way were each exposed using a sensitometry wedge, and then exposed using an automatic processor S.
Processing was performed using RX-501 (manufactured by Konica Corp.) using a developer and a fixer (the compositions of which are shown below) for a total processing time of 45 seconds.

In addition, regarding processing unevenness, the entire surface of the eight-cut sample was exposed with the same amount of light, and the same processing was performed.

After development, each sample was evaluated for sensitivity, maximum density, fog (representing the minimum density at the time of reversal), and processing unevenness according to the following five levels. Regarding sensitivity, fog +1.0
The reciprocal of the exposure amount required to give the density of the sample -■, l
It is shown as a relative value with OO.

Evaluation of processing unevenness 5: Very good with no unevenness.

4: Good.

3: Normal.

2: Inferior.

l: Very poor.

The results obtained are shown in Table-1.

Composition of developer and fixer Developer solution-1 Potassium sulfite 55.0 g Hydroquinone 25.0 g 1-phenyl 3-birasoliton 1.2 g Boric acid 10.0 g Sodium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Nitropenzimidazole 0. lOg glutaraldehyde binitite its salt 15.0g glacial acetic acid
16.0g potassium bromide
Add 4.0 g of triethylenetetramine hexavinegar M 2 and 5 g of water to make up to 1Q.

Fixer-1 Ammonium thiosulfate 130.9g Anhydrous sodium sulfite 7.3g Boric acid 7.0g Acetic acid (90 carbonate L%)
5.5g disodium ethylenediaminetetraacetate 3.0g sodium acetate trihydrate 2
5.8g Aluminum sulfate 18 hydrate 14
．． 6g sulfuric acid (50w (%)
Add 6.77g of water to make 1Q.

Example-2 The sample prepared in Example 1 with a retention time of 2 hours was
The film was exposed in the same manner as above and processed using an automatic processor S RX-501 so that the total processing time was 45 seconds.

<Developer composition> Potassium hydroxide 24g Sodium sulfite 40g Potassium sulfite
50g diethylenetriaminepentaacetic acid 2.4g boric acid
10g hydroquinone
35g diethylene glycol 1
1-2g4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.0g5-
Methylbenzotriazole 0.06g B
r 2g1-7enyl-3-pyrazolidone I in 0.5g water
Q (adjust to pH 10.5).

<Fixer composition> Ammonium thiosulfate 140g 40g
Sodium sulfite 15g Disodium ethylenediaminetetraacetate 0.025g Sodium hydroxide 6g Adjust to 1Q with water (adjust to pH 5, 10 with acetic acid) For each sample after development, perform sensitivity, maximum density, fog, and processing in the same manner as in Example 1. The unevenness was evaluated.

As is clear from Table 1, the samples containing the compound according to the present invention and the electron-accepting organic compound have high sensitivity and little reverse fog, and even if the coating stagnation time is long, the sensitivity and reverse fog change. It turns out that you can't see it.

Furthermore, it can be seen that by using a fluorine-containing surfactant, there is no unevenness in the treatment even in rapid treatment, and the processability is excellent.

As is clear from Table 2, the sample of the present invention exhibited the same effects as Example 1 when treated with the developer and fixer having the above compositions, and in particular exhibited excellent effects on sensitivity. Recognize.

〔Effect of the invention〕

According to the present invention, a direct positive type silver halide photographic light-sensitive material having stable photographic performance without fluctuations in sensitivity and increase in minimum density (reversal fog) that occur when the emulsion stagnates while being kept warm has been obtained.

In addition to the effects of the present invention, it is also possible to obtain a processing method for direct positive-working silver halide photographic materials that can suppress the occurrence of uneven development during rapid processing and obtain images with excellent photographic properties. did it.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one direct positive silver halide photographic emulsion layer on at least one side of the support, the silver halide emulsion layer contains an electron-accepting organic compound. , and containing at least one compound selected from the following general formulas [I] and/or [II] in at least one layer on the side where the silver halide emulsion layer is present. type silver halide photographic material. (2) Direct positive type halogen according to claim (1), characterized in that the total processing time when developing the silver halide photographic light-sensitive material is 20 seconds or more and less than 60 seconds. Processing method for silver chemical photographic materials. Below is the blank general formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2, R_3 and R_4 are hydrogen atoms, lower alkyl group, alkoxy group, carboxy group, alkoxycarbonyl group, sulfo group, halogen atom, or nitro group. However, at least one of R_1 and R_2 is a carboxy group, an alkoxycarbonyl group, or a sulfo group.)