JPS6183532A - Silver halide photographic material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (5) Industrial Application Field The present invention relates to a photographic material containing a silver halide emulsion layer which is stabilized against overdevelopment fog.

However, prior art and its problems: Halogen ratio silver photographic material is suitable for processing under strong conditions, for example, at relatively high temperatures or highly active developers (developers with high temperature and high p)lk). Then, if the development process is done in an extremely short period of time, what about latent image nuclei? There is also a risk that silver halide grains that are not Mated at all may be reduced.

Capri, which is formed by undesired reduction of unexposed silver halide grains under the above conditions, appears particularly strongly at the end of the normal development process and is referred to as overdevelopment capri.

Anti-capri agents known to be effective against over-developed capri include mercury compounds and heterocyclic mercapto compounds.

These anti-capri agents reduce the fog IJ2 during normal development processing and even during over-development, but the above-mentioned fog? Enough amount to reduce it? When added, there is also the disadvantage that the sensitivity of the silver halide photographic light-sensitive material is also significantly reduced.

As such, a heterocyclic mercapto compound that is particularly active against overdeveloped capri? The fundamental disadvantage of adding halogen f directly to arsenic emulsions is that they are fully active from the time of addition.

i.e. during the manufacturing process and the shelf life of the photographic material.

and that it is already fully active during the development stage.

Therefore, undesirable desensitization effects occur during the manufacturing process and storage of photographic materials.

In order to solve this problem, the mercapto group of these 16 compounds was protected with an appropriate hydrolyzable group, and their effects could be improved. Attempts have already been made to regenerate their active ff1k by alkaline hydrolysis during the development process, which is inactive during an undesired period (the entire period before the development process, including the manufacturing process). Such substituents are usually thioesters or thioethers of the mercaptocapric inhibitor. The substituents of thioester, /L/FJ, are thioesters of carbo/acid, sulfonic acid, and carbonic acid derivatives, as described in many patents 1, for example, German Patent No. 1,597,5.
No. 03 Specification, U.S. Patent No. 3,260,597 and German Patent Application Publication No. 2,061,972
It is disclosed in the specification of No. However, although these thioesters are hydrolyzed in the alkaline medium of the developer, they have the disadvantage that partial hydrolysis proceeds gradually even in a neutral or slightly acidic pH range.

Therefore, these thioester type anti-capri agents can be incorporated into emulsions in an inactive form.

□ If the emulsion preparation process and the storage period of the photographic material are long enough, partial hydrolysis can cause undesirable desensitizing effects.

In contrast to this, leteoether type substituents! anti-capri agents - e.g. U.S. Pat. No. 2,981,624;
Specification No. 3,260,597 and German Patent No. 1
, 173,796, which is stable in neutral or weakly acidic media, but does not regenerate the original mercaptocapri inhibitor at all or regenerates it very gradually during the development process. Since it is only regenerated, over-development capri cannot be effectively prevented.

Further, as disclosed in U.S. Pat. No. 3,674,478, i.e., kino/
Compounds capable of releasing a mercapto-anticapric agent with a -methide or a 7-toquinone-methide can certainly release the anticapric agent quickly in the presence of an alkali, but they are somewhat unstable in a weakly acidic medium and gradually The capri has the disadvantage of preventing chipping and release.

Therefore, if the time from emulsion preparation to coating is sufficiently long (the pH of the emulsion is weakly acidic), the anti-capri agent will be released into the emulsion, resulting in undesirable desensitization.

C) Purpose of the present invention The purpose of the present invention is to:
An anticapri agent that is completely stable but active to the desired extent in the alkaline pH range (during processing)? The object of the present invention is to provide an anticaprylic agent (hereinafter referred to as an anticaprylic acid breaker) having a deactivated mercapto group such that it can be released.

p) Structure of the present invention The present inventors have intensively investigated the above problems and have discovered that the thioether-type anti-capri agent precursor represented by the following general formula (1) or (It) satisfies the above conditions. did.

In particular, we have found unexpectedly effective anticapri precursors in compounds such as those shown in US Pat. No. 3,674,478.

That is, the precursor of the present invention is sufficiently stable even in a weakly acidic medium, is extremely effective against over-developed capri, and has extremely low sensitivity loss (compared to the case where no anti-capri agent is added). Is it a completely new compound that has similar characteristics and cannot be easily inferred from the compounds shown in the above patent? discovered.

General formula (1) General formula (n) [The middle person in the formula represents a heterocyclic group of a mercagutocapric inhibitor, and R1, R1, RIR5, R6, and R are hydrogen atoms.

Halogen atom, alkyl group (preferably 1 to 10 carbon atoms)
alkyl group), phenyl group, alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms).

Water represents a group, a nitro group-carboxyl group, or an alkoxycarbonyl group. R1 and R2, PN2 and shame.

The island and R may be combined to form a ring. The island represents a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), or a phenyl group. Q is a hydrogen atom-alkyl group, a-substituted alkyl group, phenyl group, substituted phenyl group, alkenyl group, hydroxyl group, heteroaryl group, or alkylene/
, phenine/, ether, thioether, disulfide, sulfonyl group is represented in purple.

n represents 0 or 1-m represents 1 or 2. The mercagto-capri inhibitor may be any compound having a capri effect, but 5- or 6-membered nitrogen-containing heterocyclic compounds having a sulfur atom on the carbon atom adjacent to the nitrogen atom in the ring are particularly preferred. .

Typical examples of petero rings include tetrazole rings,
1.2.4-triazole ring, penzoxazole ring,
pentthiazole ring, pentzimidazole ring, pyridi/
ring, pyrimidine ring, etc.

Examples of typical anti-capri agent precursors according to the present invention corresponding to the above general formulas (1) and (II) are listed below, but the compounds of the present invention are not limited thereto in any way.

(Compound 1) (Compound 2) ((Higoshu 3) (Compound qMusu 4) (Compound 5) (fIS@-Shigoku 6) (Compound 7) (Compound 8) (fHigojuriki 9) (f Compound 10) Cfls Group #11) (Compound 13) (Compound 14) (Compound 16) (Compound 17) (Compound 18) (Compound 19) (Compound 20) 22) The following is a synthesis example of a typical anti-capri agent precursor of the present invention. show.

Synthesis Example 1> (Synthesis of Exemplified Compound (1)) (a) Intermediate: Synthesis of 1-phenyl-3-(3-formyl-4-hydroxybenzylthio)tetrasol.

5-chloromethylsalicylaldehyde 25.6? and 1-
Phenyl-5-mercagutotetrazole 26.7f'f
After dissolving in Nidioxa/250-, bring the internal temperature to 20℃ with ice water.
Triethylamine 20.8 while stirring.
Drop onto d'. After dropping, stir at M temperature for 2 hours.

After reaction - precipitated salt? Distill under reduced pressure at the door. The residue was soaked in 500% of ethyl acetate and then washed with water.

The Yuki layer was dried with anhydrous sodium sulfate. After drying.

Separate the sodium sulfate, distill off the hexasol under reduced pressure, and recrystallize from a mixed hexasol of ethyl acetate and 7 chlorohexane.

Yield: 37.2F Melting point: 121-122℃ Original cumulative analysis calculation [e: 57.68% H: 3.87% N: 17.
94% measurement value C: 57.70cm H: 3.85%N: 1
7.93 (b) Synthesis of compound (1) n-butylamine 1.12 and fC1-phenyl-3-(3-formyl-4-hydroxypencylthio)tetrazole 4.68t'C ethanol 25 In addition to -, the mixture was stirred at room temperature for 4 hours and left overnight to obtain crystals. Wash with ethanol and dry.

Yield 73.5f Melting point = 58-59°C Elemental analysis calculated value C: 62.10% H: 5.76chi N:
19.06% measured value C: 62.11% H: 5.78%
N: 19.04% (Synthesis Example 2) [Base of Exemplified Compound (14)] 2.2'-dithioani IJN 2.48F and (a) of Synthesis Example 1 were used to obtain 1-phenyl-3-( 3-formyl-
4-Hydroxybenzylthio)tetrazole 6.24?
The mixture was added to 30% of ethanol and refluxed for 2 hours.

Crystals precipitate when left to cool. After harvesting, recrystallize with ethanol.

Futaba: 8. Of melting point: 80-81℃ Elemental analysis: Calculated value C: 60.27%H: 3.85%N: 16.7
3% measurement value C: 60.27% H: 3.86 Chi N: 16
．． 71% Other anti-capri precursors can be easily synthesized in a similar manner.

``Anti-capri precursors also used in accordance with the present invention include
It can be added to a silver halide emulsion layer of a photographic light-sensitive material, or to a colloid layer 1 having a water-permeable relationship with the emulsion layer, such as a top coat or subcoat layer 9 for the emulsion layer.

The anti-capri precursor of the present invention is a water-miscible 6
Medium 1 For example, the silver halide emulsion or the colloid can be prepared by bath dissolving it in DMF, methanol-ethanol, etc., and adding it to the above-mentioned No. Rogge/silver oxide emulsion or the above-mentioned colloidal dispersion and mixing it before coating. Can be added to the dispersion.

Furthermore, the anti-capri agent of the present invention can be dispersed using a breaker tex and added to the above silver halide emulsion or the above colloidal dispersion using a method as shown in JP-A-53-137131. is also possible.

When the anti-capri breaker according to the invention is incorporated into a halogen/silveride emulsion, a solution of the breaker can be added at any step of the emulsion preparation, but it is preferably added just before coating the emulsion.

The concentration of the anticaprilant precursor according to the present invention depends on the type of compound and
Changes depending on the position of □.

When added to a silver halide emulsion, the i of the anticapriform precursor according to the invention per mole of arsenic halide is generally from 0.1 to 100 mmol - preferably from 0.5 to 50,417 moles.

Slightly higher concentrations can be used when added to another colloid layer that contacts or comes into contact with the silver halide emulsion layer during development.

The photographic material containing the anti-capri compound according to the present invention can be developed with a suitable developer after exposure.

The photographic material developed according to the present invention can be stabilized by conventional fixing or stabilizing methods.

The silver halide emulsions applicable to the present invention may be of any type, including spectrally sensitized and unsensitized emulsions, X-ray emulsions, infrared-sensitive emulsions, etc.;
It may be a high-sensitivity negative emulsion or a low-sensitivity positive emulsion;
The emulsions may be of the orthochrome or banchrome type.

Various silver salts can be used as the photosensitive silver salt.

For example, silver bromide-silver iodide, silver chloride or mixed halogen 1
There are silver arsenals (silver chlorobromide, silver iodobromide, etc.).

Silver halides are common hydrophilic colloids, such as gelatin, casein/polyvinyl alcohol.

It can be dispersed in carboxymethylcellulose, etc., but gelatin is advantageous.

Silver halide emulsions can be sensitized (both chemically and optically) by ripening in the presence of small amounts of sulfur-containing compounds (e.g. allyl thiocyanate, allyl thiourea, thiosorpha soda, etc.). Can be chemically sensitized.

The emulsion may also contain reducing agents (e.g. French Patent No. 1.14).
6,955, and tin compounds such as those described in U.S. Pat. No. 2,487,850.

imino-aminomethane sulfine oxides such as those described in GB 789,823) and small amounts of precious metals (eg gold, platinum).

(such as palladium, iridium, ruthenium, and rhodium).

They can also be optically sensitized with cyanine and merocyanine dyes.

Other additives 1 such as development accelerators, sensitizers, antioxidants -
Kaglar and the like can also be added to the silver halide emulsion layer or other water permeable colloid layer.

Furthermore, the antifoggant precursor according to the present invention can be used in combination with one other antifoggant or other antifoggant precursor.

Hereinafter, the present invention will be explained in detail with reference to Examples.

(g) Example 1> Composition of silver bromide 65.5 mol, silver chloride 34.0 mol % - iodine [H] [0.5 mol kW, average grain size 0.45 μ
A silver iodobromide gelatin emulsion of m was prepared by the neutral single-jet method. After physical ripening, gelatin was desalted for 7 times by washing with water, and then chemical sensitization was performed using sodium thiosulfate KTS, followed by sensitizing dyes, stabilizers, surfactants,
A hardener was added to finish the emulsion.

The resulting gelatin-silver halide emulsion? Divided into 22 parts, -1 to 16 parts were each added with the above-mentioned antifoggant precursor exemplified compound at a concentration of 2 mmol per mole of silver halide, and the remaining 3 parts were added with l-phenyl-5 as a comparison.
-mercagutotetrazole (comparison A), 2-mercaptobenzthiazole (comparison B), 2-mercagutopenzimidazole (comparison C) each added at a concentration of 2 mmol per mole of silver halide.

Two further parts contain the following antifoggant precursors (Comparison E) as disclosed in U.S. Pat. No. 3,674,478, each at a concentration of 2 mmol per mole of silver halide. added.

Nothing was added to the other part. (Comparison F) These antifoggant precursors (or anticapriants) were added just before coating.

The 22 types of emulsions obtained? A photographic base coated with a double-sided polyethylene V7 layer was coated with 2.5 ml of silver nitrate and 6 ml of gelatin.
．． 0? It was applied and dried to give ~. Obtained sample r5
It was heated at 0°C for 1 day. One portion of each sample was exposed through a 7-step source wedge and then exposed to light with the following composition: 177! 'Q k use 2
Develop at 0°C for 90 seconds, stop, fix, and dry without washing to determine photographic properties. I was looking for it.

<Developer> Water 7507
! Metol 1.0? Hydrokinono 4.0? Sodium sulfite 15. Or sodium carbonate (1
water salt) 26.7S'potassium bromide
Add 0.72 r water
Adjust to 1,000dpHk 10.5.

Next, another portion of each sample was coated with the above developer for 3 minutes without exposure.
Developed at 0° C. for 6 minutes, then developed with another portion of each sample without exposure to the developer solution raised to pH 12.0, and then added another portion of each sample with the developer solution without exposure. pH'z1
I increased it to 3.0, developed it, and examined it with Capri.

The obtained results are shown in Figure 7.

(The following is a blank space) Table 1〉〈Example 2〉 In the same manner as in Example 1, an arsenic gelatin emulsion with an iodine salt odor was subjected to 7 cycles of sensitization, and then a sensitizing dye was obtained.

Emulsion by adding stabilizers, surfactants, and hardeners? Finished.

The resulting gelatin-halogen ratio silver emulsion was divided into 7 parts and 1
~4 parts of each of the anti-capri breaker exemplified adducts were added at a concentration of 2 mmol per mole of silver halide.

For comparison, the remaining part contained 1-phenyl-5-mercaptotetrazole (Comparison A) - and another part contained the following capri-prevention agent disclosed in U.S. Pat. No. 3,674,478. (Comparative B) Each compound was added at a level of 2 mmol per mole of silver halide.

Furthermore, there was nothing in the other part. (Comparison C) These anti-capri agent precursors (or anti-capri agents) were added immediately before application and then.

The remaining emulsion after coating was kept warm at 40°C and coated at regular intervals to examine the emulsion stability of the anti-capri agent over time. These emulsions were coated in the same manner as in Example 1.

The resulting sample was heated at 40°C for 5 days and examined for photographic properties in the same manner as in Example 1.

Next, each sample was developed for 6 minutes at 30°C without exposure using the same developer as in Example 1 at pH 10.5 to obtain Turnip IJ =
,Examined. The obtained results are shown in Table ■.

(Left below) (F) As is clear from Table I of Effects of the Invention, the compound of the present invention can be compared with Comparison A based on the data of sensitivity ratio (comparison of sensitivity in the case of 7'C with i o o, o in the sensitivity of Comparison A). , B, C1D, and E do not cause an undesirable decrease in sensitivity.

Furthermore, the soft tone ratio (decrease in gamma value) was extremely small, indicating that there was no adverse effect on photographic properties.

Furthermore, since the capri is extremely low, reaching the level of capri in Comparative A, it can be seen that water is effectively decomposed in the developer and the capri inhibitor is released.

Furthermore, as is clear from Table 2, the anti-capri precursor of the present invention is superior in emulsion stability over time compared to Comparatives A and B.

Claims (1)

[Claims] (1) At least one silver halide emulsion layer and/or a colloid layer having a water-permeable relationship with the emulsion layer must contain at least one compound represented by the following general formula (I) or (II). Characteristic silver halide photographic material. 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, A represents the heterocyclic group of the mercapto antifoggant. R_1, R_2 , R_3, R_5, R_6, R_7
is a hydrogen atom, a halogen atom, an alkyl group, a phenyl group, an alkoxy group, a hydroxyl group, a nitro group, a carboxyl group,
Or, it represents an alkoxycarbonyl group, and R_1 and R_
2. R_5 and R_6, R_6 and R_7 may be combined to form a ring. R_4 represents a hydrogen atom, an alkyl group, or a phenyl group. Q represents a hydrogen atom, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group, an alkenyl group, a hydroxyl group, a heterocyclic group, an alkylene, a phenylene, an ether, a thioether, a disulfide, or a sulfonyl group. n represents 0 or 1, and m represents 1 or 2. )