JPH08146544A - Applying method of silver halide compound photosensitive material - Google Patents

Abstract

PURPOSE: To improve handling safety under bright room light by holding the temperature under a specified value, during a stand-by time of a solution before applying it. CONSTITUTION: In a method applying negative type halide silver compound photosensitive material in which over 90mol percent containing an organic desensitizer having the sum of polarograph anode potential and polarograph cathode potential to be positive is silver chloride, the temperature of the applying liquid before applying is put on the alert under 42 deg.C. This organic desensitizer is featured by oxidation/reduction potential decided by polarography. In a useful desensitizer, the sum of polarograph anode potential and polarograph cathode potential is positive. The halide silver compound emulsion is favorably halide silver compound emulsion containing silver chloride over 95mol percent, and safe light property becomes bad in case of silver chloride under 90mol percent. In addition when the stand-by temperature becomes 44 deg.C, the safe light property becomes bad as a time passes, and Dmin increase. This is a common phenomenon regardless of the sort of organic desensitizer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material for a bright room.

[0002]

2. Description of the Related Art In recent years, in the field of printing, due to the complexity of printed materials and the development of scanners, it has been desired to improve the capability of the returning work process. Therefore, a photographic film having a low sensitivity of about 10 ^-2 to 10 ^-5 has been developed as compared with the conventionally used return film, and has been put to practical use as a return film that can be handled in a bright room, that is, a light room photosensitive material. Is coming. The performance required for such a light-sensitive material for a bright room has a high contrast and a sufficient maximum density, can be handled for a long time in a bright room, and has a high sensitivity to a printer light source. That is the case. However, it cannot be said that the light-sensitive materials for bright rooms so far have sufficiently satisfied the above-mentioned performance,
In particular, it is desired to develop a light-sensitive material for a bright room, which is highly safe.

Generally, a safelight used for a light-sensitive material for a bright room is not a normal fluorescent lamp but a special fluorescent lamp called an anti-fading fluorescent lamp in which ultraviolet rays are cut. The safelight described below indicates a case where the safelight is exposed to the fading prevention fluorescent lamp.

In order to ensure the safety of safelight, the sensitivity of silver halide emulsion grains is extremely lowered. As this method, 1) a method using an organic desensitizer 2) an inorganic desensitizer rhodium There are two known methods.

For example, a method using a large amount of rhodium is described in JP-A-56-125734.
A method using an organic desensitizer is disclosed in JP-A-59-157.
633, 59-157630 and 59-1576.
No. 31, No. 59-177536, No. 59-17753.
No. 7, No. 60-123837, No. 60-217355.
No. 61-26040, No. 61-26041, and the like.

When the organic desensitizer is used, the present inventor has discovered that the desired safelight property cannot be obtained without strictly controlling the temperature of the coating solution containing the organic desensitizer before coating. This phenomenon is a unique phenomenon that appears only in emulsions containing an organic desensitizer, and there is no such phenomenon in emulsions containing only rhodium.

In order to clarify the state of the coating liquid before coating, some explanation of the coating process will be given here.

When a silver halide emulsion is coated with a coater, considering the efficiency, a large amount of emulsion is made at a time, and the coating solution is gradually coated, but coating is performed for tens of thousands or hundreds of thousands of meters. Therefore, it usually takes several tens of hours (hereinafter, waiting time) from the start of coating to the end of coating. This is because it is inefficient to make several batches of coating solution for one application.

At this time, the photographic property of the light-sensitive material immediately after the start of coating,
If the photographic properties of the light-sensitive material immediately after coating are very different from each other, stable quality products cannot be supplied to users, which is a serious problem for manufacturers.

Further, the temperature of the coating liquid during the standby time (hereinafter referred to as standby temperature) is strictly controlled. If the standby temperature is too low, the coating solution will gel and become clogged in the hose or tube. If the standby temperature is too high, not only photographic characteristics but also the settability will be affected and coating unevenness will occur.

As described above, there is a considerably long waiting time before coating, and it has been known so far that the waiting temperature at that time is closely related to the safelight property of a photographic emulsion containing an organic desensitizer. Didn't.

As a result of pursuing the relationship between the standby temperature and the safelight property, the present invention has led to the discovery of a simple method for stable production.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material which is highly safe to handle in bright room light. Another object of the present invention is to provide a coating method capable of maintaining stable quality.

[0014]

The present invention comprises an organic desensitizer in which the sum of polarographic anodic potential and polarographic cathodic potential is positive in a silver halide emulsion, and during the waiting time before coating the solution. By keeping the temperature at 42 ° C. or lower, it is to provide a bright room silver halide light-sensitive material having a high safelight safety.

The organic desensitizer used in the present invention is generally known to be used in a direct positive silver halide emulsion. That is, the organic desensitizer used in the present invention is characterized by its polarographic half-wave potential, ie its redox potential determined by polarography. Organic desensitizers useful in the present invention are those in which the sum of the polarographic anode potential and the polarographic cathode potential is positive. Regarding the method of measuring these redox potentials,
For example, it is described in US Pat. No. 3,501,307. Specific examples of such organic desensitizers are described in numerous patent specifications and documents, and all of them have the same action in the present invention,
For example, Japanese Patent Publications No. 36-17595 and No. 39-202.
No. 61, No. 40-26751, No. 43-1316
7, No. 45-8833, No. 47-8746,
47-10197, 50-37530, 48-24734, 49-84639, 56-142525, and US Pat. No. 2,272,22.
No. 9, No. 2,541,472, No. 3,035,9
No. 17, No. 3,062, 651, No. 3,124,
No. 458, No. 3,326,687, No. 3,67.
Compounds described in the specification such as 1,254 can be used.
An example is shown below.

(D-1) 1,3-diethyl-1'-methyl-2'-phenylimidazo [4,5-b] quinoxalino-3'-indolocarbocyanine iodide (D-2) pinacryptol yellow (D-3) 1,1 ′, 3,3,3 ′, 3′-hexamethyl-5,5′-dinitroindocarbocyanine / P-toluenesulfonate (D-4) 5,5-dichloro-3,3 '-Diethyl-
6,6'-Dinitrothiacarbocyanine iodide (D-5) 1,1'-dimethyl-2,2'-diphenyl-3,3'-indolocarbocyanine bromide (D-6) 1,1 ' , 3,3'-Tetraethylimidazo [4,5-b] quinoxalinocarbocyanine chloride (D-7) 5-m-nitrobenzylidene rhodanine (D-8) 6-chloro-4-nitro-nitrobenzo Triazole (D-9) 1,1'-dibutyl-4,4'-dipyridinium dipromide (D-10) 1,1'-ethylene-2,2'-dipyridinium dibromide (D-11) 4 -(P-n-amyloxyphenyl)-
2,6-Di (P-ethylphenyl) -thiapyridinium perchlorate (D-12) 2-mercapto-4-methyl-5-nitrothiazole (D-13) 2- (O-nitrostyryl) -3- Ethylbenzothiazolium-P-toluenesulfonate (D-14) 2- (P-nitrostyryl) quinoline-P
-Sulfenesulfonate (D-15) Phenosafranine (D-16) Pinacryptol Green (D-17) 2,3-Dimethyl-6-nitro-benzothiazolium P-toluenesulfonate

The amount of the organic desensitizer used is 3 × 10 ^-4 mol or less, preferably 1.5 × 10 ^-4 mol, per 1 mol of silver halide.
It is from 1 to 10 × ⁷ mol. If it exceeds 3 × 10 ^-4 mol, the sensitivity becomes too low and it is not practical. The organic desensitizer is preferably added as early as possible.

It has not been known until now that a silver halide emulsion containing an organic desensitizer largely depends on its standby temperature for its safelight property. It is probably related to the adsorption and desorption of the organic desensitizer on the surface of the silver halide crystal, but the mechanism is not clear.

The silver halide emulsion used in the present invention is
A negative emulsion containing at least 90 mol% silver chloride. The negative emulsion is a normal type silver halide emulsion that forms a negative image on a positive document, which is distinguished from a direct positive silver halide emulsion. It is preferably a silver halide emulsion containing 95 mol% or more of silver chloride. 9 silver chloride
If it is less than 0 mol%, the safelight property is poor and it is inconvenient for achieving the object of the present invention. It is preferable that silver iodide is not substantially contained, but a very small amount, for example, about 0.2 mol% can be contained if necessary.

The silver halide emulsion used in the present invention is
Fine grain silver halide, preferably having an average grain size of 0.05 to
It is about 0.3 μm. Further, it is preferable that 90% or more of all particles have a particle diameter within the range of ± 10% of the average particle diameter. The preparation method of the silver halide emulsion includes forward mixing, back mixing,
Any known method such as simultaneous mixing may be used.

The silver halide emulsion used in the present invention is
It may or may not contain rhodium. It is important to include an organic desensitizer. Rhodium is produced by adding a water-soluble rhodium salt during the production or physical ripening of silver halide. As the water-soluble rhodium salt, conventionally well known ones such as rhodium monochloride, rhodium dichloride, rhodium trichloride and rhodium ammonium chloride can be used.

[0022]

【Example】

Example 1 100 mg of adenine was used per 100 mol of silver chlorobromide containing 95 mol% of silver chloride to precipitate silver halide by a conventional method and physical ripening was performed to obtain a grain size distribution with an average grain size of 0.15 μm. A narrow emulsion was obtained. After desalting and re-dissolving this emulsion, the various organic desensitizers described above were added at 5 mg per mole of silver halide, 4-hydroxy-6-methyl-1,3,3a, 7.
-Tetrazaindene (7 mg), 1-phenyl-5-mercaptotetrazole (2 mg), a surfactant and a hardener were added to give 3.0 g / m ² as silver on the polyester film.
Was applied together with the gelatin solution for the protective layer and dried. However, the waiting time of each solution before coating is 0,
It was changed to 2, 4, 6, 8, 10, 12 hours, and the temperature at that time was also changed to 36, 38, 40, 42, 44, 46 ° C.

The concentrations of these samples were measured and the sensitivity was determined at the concentration of 3.0. For the sake of convenience, the sensitivity was 100 when the organic desensitizer (D-1) was used. Sensitivity was determined only for samples with a standby time of 0.

Next, in order to test the safelight property,
Dmin was measured. The safelight property is 200 lux under an anti-fading fluorescent lamp, and the emulsion is facing upward for 1 hour. The processing conditions are the same as the above conditions. Table 1 shows the results.

[0025]

[Table 1]

Although the photographic sensitivity and Dmin have some variations due to the constant addition of the organic desensitizer, it can be seen that when the standby temperature reaches 44 ° C., the safelight property deteriorates with time and Dmin increases. This was a common phenomenon regardless of the type of organic desensitizer.

Example 2 Next, a silver halide emulsion containing 5 × 10 ^-5 mol of Rh per 1 mol of silver halide was prepared and its safelight property was compared with that of an emulsion containing an organic desensitizer.

The method for preparing the emulsion is the same as in Example 1 except that it contains Rh, and the other test methods are the same as in Example 1. As the organic desensitizer, D-2 was used, and the addition amount was changed to 0, 1, 3, 10 mg. These results are shown in Table 2.
Shown in

[0029]

[Table 2] As shown in Table 2, emulsions containing only Rh had almost constant Dmin when irradiated with safelight regardless of standby temperature, but emulsions containing even a small amount of organic desensitizer had a large safelight property at standby temperature. Therefore, it can be seen that the safelight property deteriorates even though the sensitivity is lowered.

[0030]

EFFECT OF THE INVENTION A light-sensitive material for a bright room is obtained which has high safety in handling in a bright room light and can maintain stable quality.

Claims (1)

[Claims] 1. A method of coating a negative type silver halide photographic light-sensitive material containing 90% by mole or more of silver chloride containing an organic desensitizer having a positive sum of polarographic anode potential and polarographic cathode potential. A method for coating a silver halide photographic light-sensitive material, characterized in that the temperature of the coating solution before coating is kept at 42 ° C. or lower and kept in standby.