JPH028835A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To suppress the deterioration of image quality and particularly the degradation of sensitivity and the increase of fogging by incorporating a compd. having a specific compsn. into the above material and processing the material under specific conditions. CONSTITUTION:One kind of the compd. expressed by formula I is incorporated into the layer on the side having a silver halide particle-contg. layer and the silver halide photographic sensitive material is processed under the conditions expressed by equation II. In formula I, X denotes an atom selected from an oxygen atom, sulfur atom and selenium atom; R denotes an alkyl group direct or via a divalent combination group or aryl group via a divalent combination group; M denotes a hydrogen atom or alkali metal. In equation II, l denotes the length (m) of the transporting line from the position A of, for example, an insertion port, of a roller transportation type automatic developing machine to the position B of a drying outlet thereof; T is the tie (second) used for passage at l. The high-speed processability is improved and the high sensitivity and low fogging are obtd. in this way.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a silver halide photographic material.

In particular, it is a photosensitive material that is processed at high speed and has high sensitivity.
The present invention relates to a silver halide photographic window optical material that can produce images with low fog.

[Background of the invention]

In the field of silver halide photographic materials, higher sensitivity is desired. This can be said in any field of photosensitive materials, but in the case of X-ray photosensitive materials, for example, there is a desire to develop a photographic technique with low radiation exposure and high precision, that is, a photographic technique with even higher sensitivity.

For this reason, various enhancement techniques have been proposed in the field of various silver halide photographic materials, such as methods of supersensitizing with dyes, and techniques for improving optical sensitizers. However, it cannot be said that these methods are necessarily versatile for high-sensitivity silver halide photographic materials. In other words, in various conventional technologies, when the sensitivity is increased,
There is a problem in that fogging is more likely to occur.

On the other hand, in recent years, it has been desired to further speed up the processing of silver halide photographic materials. In order to meet this demand, various high-speed processing devices have been proposed, but speeding up the processing has an impact on the image quality, especially a decrease in sensitivity and
The problem arises of increased fog.

That is, there is a demand for a photosensitive material that can be rapidly processed and that does not cause problems in terms of sensitivity or fog, but it is currently difficult to obtain a photosensitive material that satisfies these conditions.

[Purpose of the invention]

The present invention aims to solve the above-mentioned problems and provide a silver halide photographic material in which deterioration in image quality, particularly a decrease in sensitivity and an increase in fog, is suppressed when processed at high speed.

[Structure and operation of the invention]

In order to solve the above-mentioned problems, the present invention provides a silver halide photographic material having at least one photosensitive silver halide grain-containing layer on a support. In either layer, apply the following general formula (
The silver halide photographic light-sensitive material containing at least one of the compounds represented by 1) is processed using a Rosy Ill feeding type automatic developing machine which processes under conditions corresponding to the following formula (II). Make it a certain structure.

General formula [I] In the general formula (-I), X represents an atom selected from an oxygen atom, a sulfur atom, and a selenium atom, and R is a substituted or unsubstituted alkyl group directly or via a divalent linking group, or represents a substituted or unsubstituted aryl group via a divalent linking group.

Formula (n) 10.7SxT=50~124 0.7 < 1 < 3.1 In formula (n), l is the distance from the core of the 10th roller at the insertion port of the roller conveyance automatic developing machine to the final stage at the drying outlet. It is the length of the conveyance line to the core of the roller (unit: 2 m), and T is the above 2.
This is the time (unit: seconds) used to pass through.

The condition of the present invention that the value given by the above formula (n) is 50 or more and 124 or less is a condition for high-speed processing.

Conventional general roller conveyance type automatic developing machines are of this type ([
The value determined in parentheses was usually 125 or more.

In general, when processing photosensitive materials with an automatic processor with a value calculated by the above formula (n) of 125 or more, it is possible to take a relatively long time for development, fixing, washing, and drying. Drying was possible even with the use of a fairly large amount of hydrophilic colloid such as gelatin to protect the silver, so it was not difficult to maintain the sensitivity and fog of the resulting photographic images. Under the above-mentioned high-speed processing conditions of the present invention, conventional techniques would have problems with sensitivity and fog, as described above. However, in the present invention, by using a compound represented by the formula ([), these problems can be solved, although it was unexpected, and images with high sensitivity and low fog can be obtained under high-speed processing conditions. This had the effect of making people feel better.

When processed in an automatic processor under conventional conditions where the value given by the formula (I) is 125 or more, the granularity of silver halide grains after development did not deteriorate significantly, but the above Under high-speed processing conditions, there is generally a tendency for graininess to deteriorate.However, according to the present invention, an additional effect of preventing the graininess from deteriorating is obtained.

The present invention will be explained in more detail below.

First, the compound represented by the general formula [I] used in the present invention (hereinafter also referred to as "compound of the present invention" etc.) will be explained.

At least one of the compounds of the present invention is contained in at least one layer on the side having the photosensitive silver halide grain-containing layer.

Since the light-sensitive material of the present invention has at least one photosensitive silver halide grain-containing layer on at least one side of the support, only one silver halide grain-containing layer is formed on one side of the support. When the compound of the present invention is contained in one layer of either side of the support. It is sufficient that the compound of the present invention is contained in at least one layer of the silver halide-containing layer ( It is preferable to include it in the photosensitive emulsion layer).

The content of the compound of the invention is preferably from 0.01 g to 5 g, particularly preferably from <0.1 g to 0.8 g, per mole of photosensitive silver halide grains in the layer contained.

The compound of the present invention may be incorporated into any layer on the side having a silver halide-containing layer.For example, when the compound is incorporated into an emulsion layer, it may be added to the emulsion at any time and by any method during emulsion preparation. It can be contained by adding the compound of the present invention to. The time point (position of addition) at which the compound is added is arbitrary, and may be at any point during physical ripening, chemical ripening, or before coating.

The composition of the photosensitive silver halide in the layer containing the compound of the present invention is arbitrary. Preferably, as the silver halide composition, silver iodobromide or silver chloroiodobromide having a silver iodide content of 5 mol % or less is used.

Next, the compound of the present invention will be explained in detail. The compound of the present invention is represented by the above general formula [I], where in the general formula (I), X represents an atom selected from an oxygen atom, a sulfur atom, and a selenium atom, and R represents a direct or The divalent linking group representing a substituted or unsubstituted alkyl group via a divalent linking group, or a substituted or unsubstituted alkyl group via a divalent linking group is optional, but for example, amide bond,
Examples include sulfonamide bond, ureido bond, ether bond, thioether bond, sulfonyl bond, carbonyl bond, urethane bond, and the like.

Substituted or unsubstituted alkyl groups include substituted or unsubstituted linear alkyl groups (methyl group, ethyl group, n-
pentyl group, n-octyl group, etc.), substituted or unsubstituted branched alkyl group (isopropyl group, isobutyl group, etc.)
t-butyl group, 2-ethylhexyl group, etc.) and substituted or unsubstituted cycloalkyl groups (cyclopentyl group, cyclohexyl group, etc.).

Examples of the substituted or unsubstituted aryl group include a substituted or unsubstituted phenyl group or naphthyl group, and examples of the substituent include a halogen atom, a nitro group,
Amino group, amide group, hydroxy group, cyano group, alkoxy group, carboxy group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfo group, sulfonamide group, sulfonyl group, sulfinyl group, sulfenyl group, mercapto group, ureido group , an aminocarbonyloxy group, an alkoxycarbonylamino group, an aryl group, a heterocycle, and the like. Formerly represents a hydrogen atom or an alkali metal.

Specific examples of the compound represented by the general formula (1) used in the present invention are shown below, but the compounds that can be used in the present invention are not limited to these specific examples.

(Exemplary compound) ~□N Next, in the present invention, the compound of the present invention is contained,
Silver halide grains and additives that can be used in a photosensitive silver halide grain-containing layer formed without the addition of silver halide grains will be described.

The grain shape and structure of the silver halide grains used are not limited in any way, but preferably JP-A-63-2
No. 3154, particles described in Japanese Patent Application No. 62-6890 (page 24, line 2 to page 42, line 5), and JP-A-58-113.
No. 927, No. 58-113928, No. 59-1056
Tabular graininess as disclosed in No. 36 and No. 60-147727 is preferred.

Furthermore, regarding emulsion and grain structure, JP-A-62-14744
No. 9, No. 62-169149, and JP-A No. 1983-
No. 136738, No. 60-147727, No. 60-2
No. 54032, No. 60-215540, No. 61-23
No. 2445, No. 62-3247, No. 62-7040, No. 62-54249, No. 62-123446, No. 62-123447, No. 62-124550, No. 6
No. 2-124551, No. 62-124552, No. 62
It is preferable to use the technique disclosed in Japanese Patent No.-151840.

In addition, as for processing agents and other processing-related technologies,
No. 0-52848, No. 60-136741, No. 61-
The technology disclosed in No. 36744, "Photographic Ink Processing Chemistry CPhoto" by Mason,
graphic Processrng Chemis
try), Focal Press
s) It is preferable to use the technique described in the company publication.

The amount of silver and the amount of woody colloid in the photographic light-sensitive material of the present invention, regardless of whether it is a single-sided emulsion light-sensitive material or a double-sided emulsion light-sensitive material, are as follows:
-i The amount of silver on one side containing the compound of the present invention represented by formula [I] is 1.0 to 4.5 Cg/M], and the amount of hydrophilic colloid is 1.8 to 4. It is preferably in the range of O(g/rd).

The hydrophilic colloid layer of the photographic material of the present invention is preferably hardened so that it will not dissolve within 5 minutes in an aqueous solution of 1.5% by weight of sodium hydroxide at 50°C. Various dura techniques can be used for the dura mater.
For example, a technique using a known hardening agent can be applied.

It is preferable to add an aggravating dye to the photographic light-sensitive material of the present invention between the time of silver halide grain formation and the time of coating.
The amount of the sensitizing dye used is preferably 3 mg/m or more, particularly 5 mg/m or more.
~30 ■/bo is preferable.

As an exacerbating dye and chemical sensitization method, JP-A-61-802
It is preferable to use the one described in Publication No. 37.

In addition, as additives and means, JP-A No. 63-23154,
It is preferable to use the method described in Japanese Patent Application No. 62-6890 (page 77, line 18 to page 117, line 9). In addition, as a processing agent, from page 117, line 10 to page 123, line 12
It is preferable to use the one described in the row. As other additives, Research Disclosure No. 176, 22
31 (RD 17643.1978) is preferably used.

That is, the photosensitive material may contain arbitrary additives, and these are described in Research Disclosure Vol. 176, No. 17643 (December 1978) and Research Disclosure Vol. 187, No. 1B716 (November 1976). Ori,
The relevant sections are summarized in the table below.

Known photographic additives that can be used in preparing the emulsion of the light-sensitive material to which the present invention is applied are also described in the above two Research Disclosures, and the descriptions are shown in the following table.

〔Example〕

Examples of the present invention will be described below. However, it goes without saying that the present invention is not limited to the examples described below.

Example 1 Iodide 11 with an average particle size of 0.2 μm! 2. Monodisperse grains of silver iodobromide containing 0 mol% are used as nuclei, and silver iodobromide containing 30 mol% of vA iodide is prepared at pH 9.1, pA g7
．． 7, then pH 8.0, I) A g9
-1, potassium bromide and silver nitrate were added in equal moles to obtain silver iodobromide grains with an average silver iodide content of 2.1 mole, with average grain sizes of 1.02 μm, 0.58 μm, and 0.45 μm. Monodisperse emulsion grains were prepared. The emulsion was desalted to remove excess salts using a conventional flocculation method. That is, the temperature was maintained at 40° C., and an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to cause aggregation. After removing the supernatant,
Furthermore, pure water up to 40° C. was added, and an aqueous magnesium sulfate solution was added again to cause coagulation, and the supernatant liquid was removed. These particles were mixed with 1.9 x 10-' mol per mol of ammonium thiocyanate salt, respectively, and appropriate amounts of chloroauric acid and hypo and spectral sensitizing dyes A and B described below in a total weight ratio of 200:1. Chemical ripening was carried out by adding 800 μm per mole of silver halide, and 15 minutes before completion, 200 μm of potassium iodide was added per mole of silver halide. Stabilized with 3X10-2 moles of 3a,7-chitrazaindene, three types of emulsion grains were mixed in a ratio of 15%, 60%, and 25% in descending order of size, and the following additives and lime-treated gelatin were added to form emulsion coating solution ■. did.

Further, as shown in Tables 1 and 2, a compound represented by the general formula (1) was added to the emulsion coating solution (1) before coating to prepare a compound.

Samples were prepared using the emulsion coating solution as described above, and the Capri values and relative sensitivities were compared.

In addition, the following emulsion coating solution (2) was prepared.

That is, 30 g of gelatin, 10 g of potassium bromide in 11 g of water.
5 g, thioether (HO(CIl□hS(CIl
□)zs(CHg)zS(CHz)zOH) 0.5
10 m of wt% aqueous solution was added and dissolved in the solution kept at 63°C (p A g = 9.1. pH = 6.5
), add 30ml of 0.88M silver nitrate solution with stirring.
After simultaneously adding 30 ml of It and 0.88 mol of a mixed solution of potassium iodide and potassium bromide (molar ratio 97:3) in 15 seconds, 00 ml of a 1 mol SI nitric acid warm solution was added.
2 and 600 ml of a 1 mol mixed solution of potassium bromide and potassium iodide in a molar ratio of 96.5:3.5.
They were simultaneously added over 0 minutes to prepare a tabular silver iodobromide emulsion. The obtained tabular silver halide grains had an average grain size of 1.
15 μm, thickness 0.10 μm, silver iodide content 3.
It was 0 mol%. This emulsion was desalted by a precipitation method, and then chemically sensitized using gold and sulfur amplification, followed by a sensitizing dye (
Sodium 3-[5-chloro-2-(2-[5-chloro0
-3-(3-sulfonatepropyl)benzoxazoline-2-indenemethylcou-1-butene)-3-penzooxazolio]propanesulfnate) 160 μ/1 mole of silver halide was added, and then 4 -Hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added.

The grains were optimally chemically sensitized in the same manner as described above, and the same stabilizers, additives, and lime-treated gelatin were added to prepare an emulsion coating solution (2).

Furthermore, as shown in Tables 1 and 2, the compound represented by the general formula (I) was added to the emulsion coating solution (■) before coating. did.

Samples were prepared using the above, and fog values and relative sensitivities were compared.

In addition to the additives listed below, the coating solution contains the following compound (1) (
2) was added in the following amount per mole of silver halide.

200 ff1r (2) 0.6 g of tricresyl phosphate, that is, compound (1), was added to an oil consisting of compound (2) according to the method described in Example 1 (3) of JP-A-61-285445. The dissolved and dispersed hydrophilic colloid solution was added in the above amount.

The protective layer liquid was prepared with the composition shown below.

The emulsion side has a silver equivalent value of 2.0 g/rrr per side,
The amount of hydrophilic colloid is 2.0g/r! So that
Ho 31! The layer is coated with gelatin at a rate of 1.0 g/n (60 g/min with two slide hopper type cokes).
m speed, glycidyl methacrylate 50-t%
A copolymer aqueous dispersion obtained by diluting a copolymer consisting of three monomers, 10-t% of methyl acrylate, and 40 ht% of butyl methacrylate to a concentration of ICht%, was applied as an undercoat liquid. Both sides were simultaneously coated on a 175 μm polyethylene terephthalate film base, and dried in 2 minutes and 15 seconds to obtain a sample.

The obtained sample was sandwiched between fluorescent intensifying screens KO-250 (Konica Co., Ltd.), and the tube voltage was set to 130 νP and 20 mA.
Irradiate X-rays for 0.05 seconds and use a penetrometer type B (
After exposure through an aluminum staircase (sold by Konica Medical), the processing time was varied using the prototype automatic developing machine shown in Figures 1 or 2 and the processing agents (developer and fixer) shown below. , Samples 1 to 36 were prepared.

In FIGS. 1 and 2, 1 is the 10th roller at the photosensitive material insertion port, 2 is the final roller at the drying outlet, 3a is the developer tank, and 3b
3c is a fixing tank, 3c is a washing tank, 4 is a photosensitive material to be processed, 5 is a squeeze section, 6 is a drying section, and 7 is a drying air outlet.

The spectral sensitizing dyes used for sample preparation are as follows.

(CL) zsO3Na (CHz) zs
O3(C)Ifノ, 50. Na 1, Hz) t5υ3 The additives used in the emulsion solution (photosensitive silver halide coating solution) are as follows. The amount added is expressed per mole of silver halide.

The additives used in the protective layer solution are as follows. The amount added is expressed per 11 coating liquids.

1.3.5-Triazine sodium salt fixer> The developer and fixer are Developer solution The following were used:

(Glacial acetic acid 5g 11 was made into an aqueous solution and glacial acetic acid was added to make a solution with a pH of 4.0.

Washing water for the automatic developing machine was supplied at a temperature of 18° C. at a rate of 1.51 per minute.

Sensitivity was measured for each sample.

The sensitivity was expressed as a relative sensitivity, with the reciprocal of the X-ray dose giving a blackening density of Capri+1.0 for sample size 1 in Table 1 as 100.

As shown in Tables 1 and 2, the samples according to the present invention were
It can be seen that samples with high sensitivity and low fog values were obtained. That is, a sample that does not contain the compound of the present invention is
The overall tendency is for high fog, but in particular, as the value given by formula (If) decreases, the degree of anger decreases, and conversely, as the value increases, fog tends to increase. Both are small, and both provide images with high frequency and low fog. Therefore, it can be seen that according to the present invention, a photosensitive material suitable for high-speed processing can be obtained.

〔Effect of the invention〕

As mentioned above, the silver halide photographic light-sensitive material of the present invention has good suitability for high-speed processing, and can produce images of high quality with high frequency range and low fog.

[Brief explanation of the drawing]

FIGS. 1 and 2 are block diagrams of an automatic developing machine used in an embodiment of the present invention. ■...Roller 2...Final roller 3 at the drying outlet
a...Developing tank, 3b...Fixing tank, 3c...Washing tank, 4...Photosensitive material, 5...Squeezing section, 6...Drying section, 7...Dry air blowing Exit.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide grain-containing layer on a support,
At least one of the compounds represented by the following general formula [I] is added to any layer on the side having the silver halide grain-containing layer.
A silver halide photographic light-sensitive material containing seeds, and characterized in that the silver halide photographic light-sensitive material is processed using a roller conveyance type automatic developing machine which performs processing under conditions corresponding to the following formula [II]. material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [I], represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group via a divalent linking group. Formula [II] l^0^. ^7^5×T=50~124 0.7<l<3.1 In formula [II], l is the distance from the core of the first roller at the insertion port of the roller conveyance automatic developing machine to the final roller at the drying exit. It is the length of the conveyance line (unit: m) to the core, and T is the above l
This is the time (unit: seconds) used to pass through.