JPS59157630A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To enable handling in the light room by incorporating an org. desensitizing agent and a specified heterocyclic compd. in an emulsion. CONSTITUTION:A negative type fine grain silver halide photographic emulsion contg. at least 80mol% silver chloride contains an org. desensitizing agent positive in the total of both anode potential and cathode potential in the polarograph, and a heterocyclic compd. represented by formula I , II, or III in which Z is an atomic group necessary to form a 5- or 6-membered hetero ring; A is a group forming C-NH- bond, such as amino; B is a group forming C=N- bond, such as imino, and each of A and B may be substd.; and R is H, alkyl, aryl, aralkyl, or aryl. As a result, this emulsion is stable for a long time in the light room, and it can be exposed to light from a light source emitting light rich in UV rays.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion of light-sensitive material K11ii for bright room use.

In recent years, in the printing field, due to the complexity of printed materials and the development of scanners, there has been a demand for improved efficiency in the return process. For this purpose, a photographic film with an ultra-low sensitivity of IC-10-8 grade was developed compared to the conventional film for turning, and was used as a turning film that could be handled in a bright room, that is, a photosensitive material for a bright room. It has begun to be put into practice.

The performance required of such light-sensitive materials for use in bright rooms is that they have high contrast and sufficient maximum density, can be handled for long periods of time in bright rooms, and have high sensitivity to printer light sources. There is such a thing as being there. However, it cannot be said that photosensitive materials for use in bright rooms up to t''L fully satisfy the above-mentioned performance, and there is a desire for the development of improved photosensitive materials for use in bright rooms.

As a silver halide emulsion for light-sensitive materials, JP-A-5
A large amount of rhodium salt as an inorganic desensitizer in silver halide mainly composed of silver chloride as described in Publication No. 6-125734? It can be produced by a method using a direct method or a method using an organic desensitizer such as pinacryptol yellow, which is commonly used in silver halide emulsions for positive use. However, the present inventors have discovered that emulsions produced by any of the above methods have a serious drawback in that they are insufficiently safe to handle as light-sensitive materials in bright rooms. It was confirmed. Emulsions using rhodium salts cause significant fogging under bright room light. Emulsions using organic desensitizers such as rhodium salts
It is possible to handle it under bright room light for a long time without causing any problems. It would have caused

Of course, it is sufficient to develop the image immediately after exposure, but for reasons such as stale printing, it is recommended to place it under bright room light after image exposure (1), which improves handling safety. It is requested.

Accordingly, an object of the present invention is to provide a silver halide emulsion for bright room light-sensitive materials which is free from the above-mentioned drawbacks that occur when organic desensitizers are used.

Other objects of the invention will be apparent from the following description.

The inventors 1. To achieve the above objective, as a result of extensive research, we have found that a NECA-type fine grain silver halide emulsion containing at least 80 mol% of silver chloride superiors, an organic desensitizer 2 and 0 atoms adjacent to the N atom in the ring. On the other hand, it has been found that the above object can be achieved by a silver halide emulsion containing t% of at least one of each of the heterocyclic compounds having a group bonded through an N atom.

A structural feature of the above heterocyclic compound is that the ON atom of a group such as an amino group or an imino group is directly bonded to the 0 atom adjacent to the N atom in the heterocyclic ring.

The above-mentioned heterocyclic compound is preferably represented by the following general formula (Il or No.

General Formula (I) In the formula (I, value), 2 represents all the remaining atomic groups necessary to form a 5- or 6-membered nitrogen-containing complex. People can use substituted or unsubstituted amino groups such as amino groups, methylamino groups, hydroxyamino groups, acetamido groups, hydrazino groups, ureido groups, amidinoamino groups, guanidino groups, etc.

-NH-Kui@Represents the total formation fund. B represents a group forming a 1O-N-bond, such as a substituted or unsubstituted 1f-substituted imino group (for example, an imino group, a hydrazino group, a hydroxyimino group, etc.). R is a hydrogen atom, an alkyl group (preferably 0.-0. alkyl), an aryl group, an aralkyl group,
Allyl group etc. represent gold.

Examples of specific compounds are shown below.

N Oh.

Oh.

(16)H If the comparative compounds (El, (Gl), (Gl and (Jl) described later do not have a sulfo group, a nitro group, or a carboxyl group, it is possible to achieve the object of the present invention, therefore, the present invention The said compounds of the invention must also be free of such substances.

The compounds used for comparison are shown below.

W 8] ( ■ N, □N Φ) cf(.

0H.

diameter ■ NH.

The compound used in the present invention can be dissolved in water, an organic solvent miscible with water, or a mixture thereof, and then added to a silver halide emulsion. Alternatively, it may be added to the coating solution of the layer adjacent to the emulsion layer and diffused into the emulsion layer. The time of addition may be any time during the emulsion manufacturing process, and the amount of addition can generally be appropriately selected within the range of about 20 mg to about 5 g per mole of silver halide. Of course, other antifouling agents or stabilizers 2 can also be used if necessary.

The organic desensitizer used in the present invention is one that is generally known to be used in direct positive silver halide emulsions. That is, the organic desensitizer used in the present invention is
It is characterized by its polarographic half-wave potential, ie its redox potential determined polarographically. Organic desensitizers useful in the present invention are those in which the sum of polarographic anode potential and polarographic cathode potential is positive. These methods for measuring redox potential are described, for example, in US Pat. No. 3,501,307.

Specific examples of such organic desensitizers are described in many patent specifications and documents, all of which have the same effect in the present invention. Showa 39-20261, Showa 40
-26751, Showa 43-13167, Showa 45-88
33, 1974-8746, 1977-10197, 1977-375301, JP-A-48-24734, 1974
9-84639, U.S. Patent No. 56-142525, U.S. Patent No. 2,271,229, U.S. Patent No. 2.541.472, U.S. Pat.
Compounds described in specifications such as JP 3,124,458, JP 3,326,687, and JP 3,671,254 can be used.

An example is shown below.

(D-1')1,3-diethyl-1r-methyl-2F-
Phenylimidazo (4,5-b:] -] chimexano 31-indolocarbocyanine iodide (D-2) Pinacryptol Yellow (D-3) 1
．． 11.3.3. 3', 3'-hexamethylene #-5
, 5'-dinitroindocarbocyanine-P-) luenesulfonate (D-4) 5,5-dichloro-3,3-diethyl-6,
6I-dinitrotheacarbocyanine-iodide (D-5)1. 1'-Dimethyl-2,2'--2phenyl-3,3'-(androcarbocyanine O bromide (D-6) 1,1',3,3-tetraethelimidazo[
4,5-b) Quinoxalinolupocyanine chloride (D-7) 5-m-nitrobenzene rotor.

Dimine (D-8) 6-chloro-4-nitrobenzotriazole (D-9) 1.1'-dibutyl-4,41-bipyrinodinium red dipromide (D-10) 1.1'- Ethylene-2,2-bibi-1nodinium-dibromide (D-11) 4- (p n-amyloxyphenyl)
-2,'6-di(P-etherphenyl)thiapyrylium nono-chlorate (D-12) 2-mercapto-4-methyl-5-nitrothiazole (D-13) 2- (0-nitrosteryl)-3 −
Ethylbenzothiazolium p-) Luenesulfonate CD-14) 2-(P-nitroste 1-nor)-quinoline-p-4 Luenesulfonate (D-15) Phenosacranine (D-16) Pinacryptol Green (D -1
7) The amount of 2,3-dimethyl-6-nitro-benzothiazolium p-toluene, sulfonate organic desensitizer used is 50% per mole of silver chloride.
mg to 5g, preferably 100mg to 3g. Generally, it is added after ripening.

The silver chloride emulsion used in the present invention is a silver emulsion containing at least 80 mole percent silver chloride. A negative emulsion is a normal type of silver halide emulsion that forms a negative image on a positive original, which is distinguished from a direct positive silver halide emulsion. Preferably, it is a silver halide emulsion containing 90 mol% or more of silver chloride. 80 mol% silver chloride
If it is less than that, it will be inconvenient to achieve the purpose of the present invention.

Although it is preferable that silver iodide is not substantially contained, a very small amount, for example, about 0.2 mol %, may be contained if necessary.

The silver halide emulsion used in the present invention is a fine grain silver halide, preferably one having an average grain size of about 0.05 to 0.3 .mu.m. Further, it is preferable that 90% or more of the total number of particles have a particle size within ±10% of the average particle size. The silver halide emulsion may be prepared by any known method such as forward mixing, back mixing, and simultaneous mixing.

In order to preferably achieve the object of the present invention, chemical ripening 2
It is better not to apply it. Is chemical ripening physical ripening? This step is obvious to those skilled in the art, and is a process of sensitizing at a predetermined temperature and time in the presence of a chemical sensitizer (for example, sodium thiosulfate, etc.) after desalting and desalting treatment.

The silver halide emulsion obtained according to the present invention contains stabilizers, anti-capri agents, covering power improvers, anti-irradiation agents, film property improvers, surfactants, hardeners, matting agents, developing agents, etc. It can contain additives commonly used in photographic emulsions, and is coated on a known support. It may have other hydrophilic colloid layers such as a protective layer and an undercoat layer.

The light-sensitive material for bright room use obtained by the present invention can be used mainly from light sources rich in ultraviolet light, such as mercury lamps, used in the printing field.
Exposure to ultra-high pressure mercury lamps, metal rides, etc.

The photosensitive material for bright room use obtained by the present invention can be safely handled for a long time under bright room light, whether before or after the above-mentioned exposure. can.

Example 1 Silver halide was precipitated in a conventional manner using 1 mol of silver chlorobromide containing 95 mol % of silver chloride, 1100 mg of adenine and 1 mol of rhodium chloride salt, followed by physical ripening. A monodisperse emulsion with an average grain size of 0.2 μm was obtained.This emulsion was desalted and redissolved, and pinacryptol-ixo (D-2>t-O'y' silver oxide) was added as an organic desensitizer. 5o per mole.

In addition, a hardening agent and a surfactant were added, and a total of 517 m'' of silver nitrate was coated on a polyester film together with a gelatin solution for a protective layer, and dried (blank sample).

This sample was exposed to light for sensitometry using a brightroom printer, developed with a D-85 developer at 20° C. for 2 minutes, fixed, and dried. It had good characteristics with a gradation gamma (1) of 8.7 and a capri value of 0.02. Also,
When this sample was irradiated with approximately 500 lux of ultraviolet light for 3 hours in a bright room with a total cant of ultraviolet light, and then exposed and developed in the same manner as above, no changes were observed in the sensitivity, gradation, or capri characteristics. . It is clear that this emulsion has extremely long-term photostability under bright room light, and produces excellent high contrast and low capri. After straining, the film was left in the bright room light for 30 minutes and developed in the same manner, resulting in desensitization to 12% of the original sensitivity.

Except that 400 mg of Compound 2 of the present invention and the comparative compound were added per mole of halogenated scissors to the emulsion of the blank sample.
The sensitivity when prepared in exactly the same manner as the comparative sample and left under bright room light for 30 minutes after the above sensitometric exposure is expressed as relative sensitivity, with the sensitivity of the sample without being left standing as 100. It is shown in Table-1K below.

Table-1 Compound sensitivity Blank without compound sensitivity) 12 (B)
28(2) 98 (
0) 25(3) 97
(D) 9(4) 94
(B) 8(5) 9
7 (F) 5 (7)
98 (G) 8t 1
^X O^ 1--
- - The results in Table 1 show that the compounds of the present invention significantly improve desensitization under bright room light as described above after exposure.

Example 2 Rhodium chloride 15X10~1 mol was used per mol of silver chlorobromide containing 98 mol% of silver chloride, and the average particle size was 0.15 μm.
A monodisperse emulsion was obtained. Thereafter, Example 1 was followed except that the compounds of the present invention and organic desensitizers were combined as shown in Table 2.

Table 2 The results in Table 2 show that all organic desensitizers cause significant desensitization in the test where they are left in the bright room light after image exposure, but
It can be seen that both conditions are significantly improved by the compounds of the present invention.

Example 3 A silver chlorobromide emulsion containing 87 mol % of silver chloride was prepared by the simultaneous mixing method (I). This silver halogenide has an average grain size of 0.
It was cubic and monodisperse with a diameter of 18 μm.

Thereafter, in accordance with the method described in Example 1, 300 mg of organic desensitizers (D-10) and (D-12) were added per mole of silver halide to prepare all blank samples. This sample, like the blank sample of Example 1, had the drawback that the desensitization under bright room light after image exposure was up to 1/10 of the original sensitivity immediately after image exposure.

All samples were prepared in the same manner except that 500 mg of the compound of the present invention used in Example 1 was added per mole of silver halide to the emulsion of this sample.

These samples had the above-mentioned defects of the blank sample significantly improved, and each maintained a total sensitivity of 95% to 98%.

Claims (1)

[Claims] 1. A negative-working fine-grain silver halide photographic emulsion containing at least 80 mol % of silver chloride is coated with an organic desensitizer in which the sum of the polarographic anodic potential and cathodic potential is positive; A halogen characterized by containing at least one of each of the following: a heterocyclic compound having a group bonded to the C atom at θ with an N atom (however, it does not have a sulfo group, a carboquine group, or a nitro group) Silver chemical photographic emulsion.