JPH0329943A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a high sensitivity, good developability and excellent preservable property by forming a silver halide photographic emulsion layer which has a silver halide photographic emulsion contg. two kinds of specific compds. as well as a calcium salt at >=10mg per 1mol silver halide. CONSTITUTION:The silver halide photographic emulsion layer has the silver halide photographic emulsion contg. at least one kind of the compds. expressed by formula I, at least one kind of the compd. expressed by formula II, and the calcium salt at >=10mg per 1mol silver halide. In the formulas I, II, R1 denotes a hydrogen atom, alkyl group, etc.; R2 to R5 denote ann alkyl group; A1 to A6 denote a hydrogen atom, alkyl group, etc.; and the adjacent groups thereof my form a ring. A7 to N12 denote a hydrogen atom, alkyl group, etc. and the adjacent groups thereof may form a ring. However, any one of A3 or A11 or both thereof need be a phenyl group. The photosensitive material having the high sensitivity, the good developability, and the excellent preservable property is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive silver halide light-sensitive material with improved sensitivity, storage stability, and developability. be.

"Prior Art" In recent years, demands for silver halide photosensitive abrasion (hereinafter also simply referred to as photosensitive abrasive) have become increasingly strict, and there has been a strong demand for the development of photosensitive materials with particularly high sensitivity and excellent image characteristics. It is requested.

The technology of adding photosensitive dyes to silver halide emulsions to achieve spectral sensitization has been well known for the purpose of increasing sensitivity.
Furthermore, research on so-called supersensitization, in which even higher sensitivity can be obtained by combining photosensitive dyes or special combinations of photosensitive dyes and certain additives, has been actively promoted in the art.

There are descriptions regarding supersensitization in Japanese Patent Publication Nos. 54-34535, 56-38936, and JP-A-58-153826.

However, although the spectral sensitivity is improved by these combinations, the practical sensitivity is not improved due to development inhibition, and there are many cases where the Con1~Las1~ is lowered, making it difficult to achieve high sensitivity and high performance. This required further research.

Furthermore, in recent years, processing processes for photosensitive materials have become faster and at the same time, process management has become simpler.

This is to reduce the labor and expense required for maintenance and management of the treatment process, reduce the amount of replenishment of treatment liquid, extend the period for renewing the treatment liquid, and change the photosensitive forest materials that were previously treated under different conditions to the same conditions. This includes movements such as processing.

With such speeding up and simplification of processing steps, measures have been taken for photosensitive materials to reduce the dependence of photographic properties on development processing.

For example, addition of hydroquinones as described in JP-A-50-39928, JP-A-57-1973;
Addition of 1-phenyl-3-virazolidones as described in No. 9 is known. All of these compounds are used as developing agents in ordinary photographic developers. By incorporating this developing agent into the photosensitive material format in advance, it becomes less susceptible to fluctuations in developing conditions.

However, J.J. ! If an image agent is contained in a silver halide photographic emulsion layer or another layer on the same side of the support as the silver halide, there is a drawback that performance deterioration, especially fog, is likely to occur during storage of the photosensitive material. It had

[Problems to be solved by the invention] The present invention has been made to solve the conventional problems, and its purpose is to provide a halogenated compound with high sensitivity, good developability, and excellent storage stability. Our objective is to provide a silver photosensitive material format.

[Means for Solving the Problems] The above object of the present invention is to provide at least one silver halide photographic emulsion layer on a support in a silver halide photographic photosensitive layer 331, The halogen agent layer contains at least one compound represented by the general formula [I], at least one compound represented by the general formula [11], and 10 n+o or more of calcium salt per mole of the halogen salt. This is achieved by a silver halide photographic light-sensitive material 1 characterized by having a silver halide photographic emulsion.

General formula [■] In the formula, R1 represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group, and R2 to R5 represent a substituted or unsubstituted alkyl group.

A1-86 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but they may form a ring when placed next to each other.

A7 to A12 are hydrogen atoms, alkyl groups, alkoxy groups,
Although it does not represent a halogen atom or a phenyl group, they may form a ring by adjoining each other. However, either A8 or A++,
Or both must be fennel bases.

The present invention will be explained in more detail below.

The silver halide emulsion used in the present invention has the following general formula [
I] or [I[], each containing at least one type of compound.

General formula []f] General formula [I] Specific examples of compounds represented by general formula [I] will be given below.Of course, this is general formula [II]. R2 to R5L represent a straight line or an unsubstituted alkyl group.

A1 to 86 each represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but they may be placed next to each other to form a ring.

A7 to A+2 are hydrogen atoms, argyl groups, alkoxy groups,
It represents a halogen atom or a phenyl group, but adjacent atoms may form a ring. However, either A8 or A++,
Or both must be phenyl groups.

Below, compound examples represented by general formula [I] or general formula [II] I-5 1-1 1-2 1-6 1-3 I-7 4 11-1 [-6 11-2 ■-7 It-3 n-4 I1-5 11 Sat2 The compound represented by the above general formula [I] or [n] can be synthesized by a conventionally known method.

In the present invention, at least one compound represented by the above general formula [I] is preferably added at a concentration of 50 m! ]~500mg, particularly preferably 80mo
~250 mg is used, and the above general formula [I[
] At least 61 kinds of compounds represented by the following are preferably used in an amount of 30 mo to 300 mg, particularly preferably 50 mo to 150 mg, per mole of silver halide.

Further, in the present invention, it is preferable to add one or more of each of the compounds represented by the above general formula [I] or [II] before the chemical ripening is completed.

The silver halide emulsion related to the present invention has the above general formula [I]
or at least one of each of the compounds represented by [I[]
Contains calcium salts along with seeds.

Specific examples of calcium salts used in the present invention include water-soluble calcium chloride, calcium bromide, calcium iodide, calcium nitrate, and canolecium nitrate. Among these, water-soluble calcium chloride or water-soluble calcium bromide is most preferred in view of their influence on photographic performance. In the present invention, the calcium salt is added in an amount of 10 mfl or more per mole of silver halide, and the preferred amount is 10 mfl per mole of silver halide.
0 mg to ioomg.

However, although generally used photographic gelatin may already contain calcium ions, the amount of calcium ions already contained is not included in the calcium salt addition base in the present invention. do.

It is preferable that the calcium salt is added before the chemical ripening of the silver halide grains is completed.

In the present invention, the above-mentioned calcium salt may be in any form possible in various crystals in a hydrated state.

In the present invention, the composition of the silver halide grains may be selected from any group of 14 depending on the use of various photosensitive materials such as silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide, and silver iodobromide. You can choose one.

The shape of the silver halide grains may be regular such as cubes or octahedrons, or may be of a mixed shape, but in order to obtain high contrast and sharp photographic characteristics, a relatively large size distribution is required. Narrow, with an average noise of 0.2 μm to 1
．． Preferably, the thickness is in the range of 0 μm.

Further, the temperature at the time of silver halide grain formation and/or physical ripening may be set arbitrarily, but it is more effective if the temperature is kept at 50° C. or lower. If the temperature is higher than 50° C., the effects of the present invention may not be sufficiently obtained.

Although the silver halide emulsion used in the present invention is not particularly limited, the effects of the present invention are particularly noticeable when the average silver iodide content is 5 mol % or less.

Various methods can be used to prepare the silver halide emulsion used in the present invention. For example, acidic method, neutral method,
Either an alkali method or an ammonia method may be used, and a forward mixing method, a back mixing method, a simultaneous mixing method, a pAg controlled double jet method, a conversion method, etc. can be used.

The silver halide emulsion used in the present invention contains cadmium salt,
A zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a famous salt thereof, an iron salt or an iron salt, etc. may be present together.

Gelatin is usually used as a binder or protective colloid for the silver halide emulsion used in the present invention, but other than gelatin, for example, gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; Cellulose derivatives such as hydroxyethynolecellulose and canoleboxymethyl cellulose; Sugar derivatives such as agar, sodium alginate, and starch derivatives; Borivinyl alcohol, polyester, etc. N-vinylpyrrolidone, polyacrylic acid, polyacrylamide,
Various types of 15-16 polymeric or hydrophilic polymeric substances such as single or copolymerized polyvinylimidazole, polyvinylpyrazole, etc. can be used.

The silver halide emulsion used in the present invention can be chemically sensitized with various sensitizers. For example, sulfur sensitizers (e.g., hybo, thiourea, activated gelatin, etc.), metal sensitizers (e.g., gold sensitizers such as gold chloride, gold rhodan, platinum salts, palladium, iridium salts, rhodium salts, ruthenium salts, etc.) , reduction sensitizers (e.g., stannous chloride, thiourea dioxide, hydrazine derivatives, etc.), U.S. Pat. No. 3,297,
Selenium sensitizer described in US Pat. No. 446, US Pat.
It is possible to use the polyalkylenebolyamine compounds described in No. 518,698, etc., alone or in combination.

As the hardening agent used in the present invention, for example, one or two types of organic hardening agents such as vinyl sulfone type, cyanuric chloride type, acryloyl type, ethyleneimine type, etc. or inorganic hardening agents such as chromium alum and potassium alum are used. The above can be used in combination.

Furthermore, various surfactants can be used in the photographic material of the present invention. For example, nonionic surfactants such as sabonin and polyalkylene glycol ether, alkylbenzene sulfonates, alkyl sulfates,
Anionic surfactants such as sulfosuccinates can be used.

Various other photographic additives may be used in the photographic material of the present invention, if necessary.

For example, stabilizers, coating aids, film property improvers, ultraviolet absorbers, optical brighteners, antioxidants, stain inhibitors, sequestering agents, thickeners, matting agents, antihalation dyes, antiirradiation dyes. , etc. can be used.

Supports used in the photographic material of the present invention include supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, and polypropylene; ) can be used, such as a laminate of two or more substrates.

As the developing agent used in developing the silver halide photographic abrasive of the present invention, various arbitrary ones can be specifically mentioned depending on the produced photosensitive material.

For example, 0-(Cl-{)n-Of-1 type (e.g. hydroquinone, etc.) or 40-(CI1=CH)nNH
Type 2 (e.g. ortho and para amine phenols or aminopyrazolones, etc.) and 2N-(C port-C port) 1 m-N
Type 2 (Example 4-amino-2-methyl N,N-diethylaniline, etc.) can be mentioned.

Others, T. H. The Theory of the Photographic Process, 4th Edition, by James
theory of the Photoqraphtc
Process, Fourth [:dition)
pp. 291-334 and Journal of the American Chemistry Society
r the AmericanCI+emical S
73, No. 3, page 100 (19
51) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjustment of PL1 and buffer function with caustic alkali, alkali carbonate, or amine used in general black and white developers, inorganic development inhibitors such as brompotali, organic development inhibitors such as benzotriazole, ethylenediaminetetraacetic acid, etc. metal ion scavenger, methanol, ethanol, benzyl alcohol, development accelerator such as polyalkyleneoxy 1~, sodium alkylarylsulfonate, natural sabonin,
It is optional to add surfactants such as saccharides or alkyl esters of the aforementioned compounds, hardening agents such as glutaraldehyde, formalin, glyoxazole, and ionic strength 19 20 adjusters such as sodium sulfate.

The developer used in the present invention may contain alkanolamines or glycols as an organic solvent.

The I) l-1 value of the developer having the above composition is preferably 9 to 13, but from the viewpoint of storage stability and photographic properties, the o L{value should be 10 to 13.
A range of 12 is preferred.

The silver halide photographic material of the present invention can be processed under various conditions. The processing temperature is, for example, a developing temperature of 50
℃ or less, particularly preferably in the range of 30''C to 40℃, and the development time is generally completed within 2 minutes, but particularly preferably within 30 seconds brings about a good effect. There are many things.

Furthermore, it is optional to employ processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, pre-hardening, neutralizing, etc., and these can also be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as lip-color development or hanger development.

[Example] The present invention will be specifically explained below with reference to Examples, but of course the present invention is not limited thereto.

Example 1 Preparation of silver halide photographic emulsion 1 mol% of silver iodide, silver iodobromide containing iridium and rhodium, ammonium thiocyanate, chloroauric acid,
Chemical sensitization was performed by adding sodium thiosulfate. A calcium salt was added at the start of chemical sensitization, and a compound represented by general formula [I] or general formula [II] or a comparative compound was combined as shown in Table 1 10 minutes before the end of chemical sensitization. Table-1
The mice shown in . Thereafter, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptote-1herazole were used as stabilizers, and isoprobylnaphthalenesulfonic acid was used as a surfactant. Polyethyl acrylate as a physical property improver,
A fluorescent brightener prepared by the following method and a processability improver 1-phenyl-3-pyrazolidone were added.

The above combination! 10g of li to cresyl diphenylbosphene
1-200 d of a 10% gelatin aqueous solution containing 5 g of isobrobylnaphthalene sulfonic acid dissolved in ethyl acetate (and 10 ml of ethyl acetate)
After mixing and dispersing using Bomodinai 1f-, the mixture was finished to 3000-mm with pure water. The amount added was 1,000 d per mole of silver halide.

Preparation of test slopes 1 to 2/l To each of the prepared silver halide photographic emulsions, bonoremarin and Tera:1 varnish (bylsulfonyl mediyl) methane were added as hard IFJ agents. It was coated on a paper support coated with polyethylene that had been drawn, and then a gelatin layer containing a surfactant and a pine agent was simultaneously coated and dried as a protective layer so that the gelatin content was L7g/TI+. I created trial 1'jl. A (+ speed is 1)
．． 4 (1/1ll', 2 layers of geladine spots total 3.8
g/i'.

(Evaluation of sensitivity and developability) The thus prepared sample was exposed to light for 10-6 seconds from a Kihinon flash light source through an optical wedge, and then a developer of the following composition was applied using an automatic processor GR-26 (Konica The development process was carried out using a commercially available commercially available product, followed by fixing, washing with water, and drying.The development temperature was 38°C, and the development time was 2.
It was carried out for 0 seconds and 40 seconds.

(Developer) Diethylene glycol 40 (1 Sodium sulfite 50 Q Sodium hydroxide 1
Helium 10g 1-phenyl-3
-Vyrazolidone 10 Hydroquinone
25 g Sodium carbonate
200 potassium bromide
Add 3g of water to make 12.

For each sample after processing with a development time of 20 seconds or 40 seconds, the defective density was determined using Konica Digital Fuchidam PD A6.
The photographic characteristics were evaluated by measuring with Model 5 (manufactured by Konica) and drawing a 1-yen sensitivity curve. The results obtained are shown in Table-1. Sensitivity represents phase 4 sensitivity, and the reciprocal of the exposure required to obtain a photographic depth of 1o is calculated, and the sample rate No. The value obtained when the development time of No. 1 was 20 seconds was multiplied by 100, and the value was expressed as a relative value.

The developed bamboo was evaluated by taking the sensitivity ratio (S2/81) between the 20-second development sensitivity S1 and the 40-second development sensitivity S2.

Regarding storage stability, the obtained sample was stored at 23°CR. 55
After adjusting the humidity to
It was left to stand for several days, and forced deterioration tests 1 to 1 were conducted.

After that, the forced deterioration test product and the 23℃R. l-1.55
A sample (for comparison in the forced deterioration test) that had been left under conditions of 10% was subjected to the treatment described above without being exposed to light, and the degree of increase in fog density was evaluated using a depth meter.

The results are shown in Table-1.

As is clear from Table 1, increasing the amount of the sensitizing dye represented by the general formula [I] does not significantly increase the sensitivity;
It was found that when the compound represented by formula [I] and the compound represented by general formula [II] were used together, the sensitivity at a developing time of 40 seconds tended to increase.

However, unless calcium salt was added, the developability would be delayed, so the sensitivity at a development time of 20 seconds was rather desensitized.

When the compound represented by the general formula [I] and calcium salt were used together, the developability was significantly improved, but the development time was 4.
The sensitivity at 0 seconds has decreased.

That is, the calcium salt in the present invention, general formula [I]
Only when the compound represented by the above formula and the compound represented by the general formula [II] were added, good results were obtained, with excellent sensitivity and developability, and fog caused by forced deterioration was also improved.

[Effects of the Invention] According to the present invention, it was possible to provide a silver halide photographic material having high sensitivity, good developability, and excellent storage stability.

28

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the silver halide photographic emulsion layer contains at least one compound represented by the general formula [I]. species, at least one compound represented by the general formula [II], and 10 per mole of silver halide.
A silver halide photographic material comprising a silver halide photographic emulsion containing mg or more of calcium salt. 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 represents a hydrogen atom, an alkyl group, a phenyl group, an aralkyl group, and R_2 ~R_5 represents a substituted or unsubstituted alkyl group. A_1 to A_6 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but may form a ring by adjoining each other. A_7 to A_1_2 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but they may be placed next to each other to form a ring. However, either one or both of A_8 and A_1_1 must be a phenyl group.