JPS58207045A - Developing agent used for silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To suppress fog, to raise developing speed and sensitivity, and to improve Dmax remarkably, by adding a specified novel thioether type compd. to a developing agent. CONSTITUTION:A developing soln. contains a compd. represented by formula I in which A is 1-3C alkylene, -(CH2CH2O)P-, or -(CH2CH2O)P-CH2CH2-, or a group represented by formula II, and a polyalkylene ether group not linking through O to B; A' is 1-3C alkylene, -(CH2CH2O)P-CH2CH2-, or a group represented by formula III, A and A' do not simultaneously polyalkylene ether group; p is 2-30; B, B' are each -NH- or -O- but they are not simultaneously -O-; R is 1- 3C alkyl; phenyl, aralkyl, -(CH2)q-COOR', q being 1-3; R' is 1-3C alkyl; and X is -S-, -O-, -CH2-, phenylene, or the like. As a result, increase of fog is prevented even in high temp rapid development, and high sensitivity and high gamma value are obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer for silver halide photographic light-sensitive materials, and more particularly to a developer that accelerates development and increases sensitivity during development processing.

In the development process of silver halide photographic light-sensitive materials, it is desired to accelerate the development speed and increase the sensitivity without deteriorating the graininess of the light-sensitive material. Many development acceleration methods have been proposed for this purpose. Polyalkylene oxide compounds are added to the developer to accelerate development, such as U.S. Pat.
No. 832, No. 2,950,970, No. 3,291
, No. 607, No. 3,495,981, No. 3,67
No. 1,247, No. 3,915,710, No. 3,9
Compounds described in each specification of No. 96,054, thioether compounds, such as U.S. Pat. Nos. 3,046,129 and 3
．． 20'1.242, British Patent No. 3,271,157, British Patent No. 1,129.085, British Patent No. 1,129,08
The compounds described in each specification of No. 6, as well as ammonium, phosphonium or sulfonium type compounds, polyionium compounds and polyionium compounds are well known. However, many of these development accelerators tend to increase fog in photographic materials and also tend to coarsen graininess. Furthermore, it has poor solubility in alkaline developers,
In addition, some of them have the disadvantage of poor storage stability in a developer, and at present, very few of these have been put into practical use.

On the other hand, there is a method of increasing the sensitivity by incorporating these development accelerators into silver halide photographic materials, but in that case, the storage stability of the silver halide photographic materials deteriorates, especially over time. The problem was an increase in fog.

A first object of the present invention is to provide a developer for silver halide photographic light-sensitive materials using a new development accelerator that causes less increase in fog, increases development speed, and increases sensitivity.

A second object of the present invention is to provide a developer for silver halide photographic light-sensitive materials, which can increase retention sensitivity without causing deterioration of grains.

This object of the present invention is achieved by a developer for silver halide photographic light-sensitive materials containing a compound represented by the following general formula (hereinafter referred to as the compound of the present invention).

General formula CI) In the formula, A is a lower alkylene group having 1 to 3 carbon atoms, or -(CH2CH20)-1-(CH-2CH20)
F-CH2-CH2-.

represents a polyalkylene ether group that is not bonded with

A1 represents a lower alkylene group having 1 to 3 carbon atoms, or a polyalkylene ether group represented by .

However, A and 81 do not become polyalkylene ether groups at the same time. Moreover, P is an integer of 2 to 30.

BIB' is -NH- or -〇,, but B and B-
and cannot be 10- at the same time.

R represents a lower alkyl group having 1 to 3 carbon atoms, a phenyl group, an aralkyl group, or -(CH2)q-COOR. However, q represents an integer of 1 to 3. R. represents a lower alkyl group having 1 to 3 carbon atoms.

It is a divalent group selected from lower alkyl groups).

Next, typical specific examples of the compounds of the present invention are shown.
It is not limited to these.

[Exemplary compounds]

dH2CH2NHCoOCH2CH2SCH2CH2C
ooC2H5(7) CH2C1(2NHCO○(C
H2CH20)6CH2CH2SC4H91 CH2CH2NHCoO(CH2CH20)6CH2C
H2SC4H9(8)[(CH2CH2O)29CH2
CH20CoNHCH2CH2SC2H5[(CH2C
H20) 29CH2CH20CONHCH2CH2SC
2H5 (9)〒H2CH2OC0NHCH2CH25C
2H5CH2CH20CONHCH2CH2SC2H5
Next, synthesis examples of typical compounds of the present invention are listed.

Synthesis Example 1 Synthesis method of Exemplified Compound (1) In 100 cc of dry benzene, HOCH2CH2SCH2CH2C00C2H517.
Melt 8g of 1S(CH2CH2Nco)28.
Add 6g. After refluxing for 2 hours, the solvent is distilled off under reduced pressure, and 200 cc of ether is added to dissolve, cool, and recrystallize to obtain Exemplary Compound (1) (melting point: 45-466C).

Synthesis Example 2 Synthesis of Exemplified Compound (5) 27.39 of CH3-N(CH2CH2CH2NH2) was dissolved in dry benzene, 13.1 g of C2H55CH2CH2NCO was added thereto, refluxed in a water bath for 2 hours, and then cooled to crystallize. When this is recrystallized from benzene, Exemplified Compound (5) is obtained (melting point: 82-83°C).

Synthesis example 3 Synthesis method of exemplified compound (6) Then, the exemplified compound (6) was 5 Obtained (nD 14873).

Synthesis Example 4 Synthesis method of Exemplified Compound (12) Dissolve the dried product in benzene, c2H5scH2cH2Nc
.

After gradually adding 26.29 and cooling under reflux for 3 hours, the obtained crystals are collected by filtration and recrystallized from methanol to obtain Exemplified Compound (12) (melting point 207-208"C).
/).

Further, other compounds of the present invention can also be synthesized according to the above synthesis examples.

In the present invention, when the compound of the present invention is added to the developer, the amount of addition is preferably o,oooi to 2 g, particularly 0.001 to 1 g per 11 of the developer. If the amount is less than 0.0001 g, there will be no effect of addition, and if the amount exceeds 2 g, it will induce the generation of capri, which is not appropriate.

The developer according to the present invention is used as a liquid developer, that is, a developer. The black and white developing agents used in the developer include dihydroxybenzenes (e.g., hydroquinone, chlorohydroquinone, isopropylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc.), 3-pyrazolidone (e.g., 1- Phenyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, etc.)
, aminophenols (e.g. O-aminophenol,
P-aminophenol, N-methyl-P-aminophenol, etc.), pyrogallol, ascorbic acid, and 1-aryl-3-virapritone can be used.

The color developing agent used in the solder retaining solution of the present invention is an aromatic @1 hardening amine compound, and particularly preferably P-
Phenyldiamine-based color developing agents, such as 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline , 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-
β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-amino-N, N-diethylaniline, 3- Methoxy-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-
Methoxyethylaniline, 3-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,N
-dimethylaniline, N-ethyl-N-β-[β-(β
-methoxyethoxy)ethoxy]ethyl-3-methyl-
4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof, such as T sulfate, hydrochloride, sulfite, P-toluenesulfonic acid Salt, etc.

In addition to the above-mentioned black-and-white developing agents and color developing agents, the black-and-white and color developing solutions according to the present invention include alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, and carbonic acid. It can contain potassium, tertiary formate, secondary ferronate, sodium sulfate, sodium metaborate, langsan, etc., and may further contain alkali metal halides, such as potassium bromide, or development regulators, such as citradinic acid. Preservatives such as sulfite, chelating agents include phosphates such as polyphosphates, aminopolycarboxylic acids such as nitrilotriacetic acid, 1,3-diamino-2-furopanol tetraacetic acid,
It may contain oxycarboxylic acids such as citric acid and gluconic acid, and organic phosphonic acids such as 1-hydroxyethylidene-1,1-disulfonic acid and aminotri(methylenephosphonic acid).

In addition, as a developer hardening agent, glutaraldehyde, α-methylglutaraldehyde, maleic dialdehyde, succinic aldehyde, methylmaleic aldehyde, α,
It may contain α-dimethylglutaraldehyde and their sodium bisulfite salts. Furthermore, a conventionally known development accelerator may be used in combination.

The developer according to the present invention accelerates the development speed and increases sensitivity while minimizing the increase in fog in normal development processing, compared to developers containing thioether compounds that have been commonly used in the past. can do. The reason why the compounds of the present invention are superior to conventional thioether compounds is not clear, but the electron affinity of each group in its characteristic structure is not clear.
This is thought to be due to the

The photosensitive material to which the developer according to the present invention can be applied may be any type of silver halide photographic material.

Next, additional remarks will be made regarding such silver halide photographic materials.

A silver halide photosensitive material consists of a support (for example, a glass plate, polyethylene terephthalate film, cellulose acetate film, baryta paper, polymer-coated paper, etc.) and at least one silver halide emulsion layer coated thereon.

Silver halide emulsion layers can be coated and grown on both sides of the support.

Silver halide emulsions are made by combining silver halide such as silver chloride, silver chloride, silver bromide, silver chlorobromide, silver chlorobromide, silver chloride bromide, etc. with a hydrophilic colloid (e.g. gelatin or modified gelatin). (combined with casein, carboxymethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, etc.)
It is dispersed in

The halogenated emulsion layer is formed by a method commonly used in the industry (for example, single jet method, double jet method, etc.)
A water-soluble silver salt (for example, silver nitrate) and a water-soluble halide salt are mixed in the presence of water and a hydrophilic colloid, followed by physical ripening and, if necessary, chemical ripening with a sulfur compound, a gold compound, etc. to form H. be done.

Spectral sensitizers (cyanine dyes, merocyanine dyes, etc.) and stabilizers (e.g. 4-hydroxy-6-methyl-1,3,3a, 7 - thitrazaindene, benzotriazole, 5-nitropenzimidazole, etc.), hardening agents (e.g. formalin, glyoxal, 2-hydroxy-4,6-dichloro-5-triazine-mucochloric acid, etc.), coating aids (e.g. saponin, (dium lauryl sulfate, polyethylene oxide, etc.), color couplers, polymer latex, etc. can be added.

Other methods for producing developing solutions and silver halide photographic materials;
Regarding additives, etc., see Product, Licensing Index, Vol. 92, pp. 107-110 (December 1971).
You can refer to the description of month).

Examples of black-and-white photosensitive materials to which the developer containing the compound of the present invention can be applied include: black-and-white photosensitive materials for general photography, photosensitive materials for X-rays, photosensitive materials for printing, photosensitive materials for medical use, photosensitive materials for movies, and photosensitive materials for aviation. Photosensitive materials, TV photosensitive materials, color photosensitive materials include color negative film, color paper, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, color X-ray film for medical use, etc. Any of the general silver halide photographic materials may be used.

The present invention will be explained in detail below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A high-sensitivity direct X-ray film coated on both sides with a silver bromide gelatin emulsion (containing 2 mol% silver iodide) was exposed according to conventional sensimetry, and heated at 20°C using a developer having the following composition. , it lasted for 4 minutes.

[Developer (A)]

[Developer (B)] It was prepared in the same manner as in (A) above. However, H was adjusted by adding 0.0511/It of the Exemplified Compound (2), which is a compound of the present invention.

[Developer (C)]

It was created in the same manner as in (A) above. However, the above-mentioned exemplified compounds (
9) was adjusted by adding 0.05.9#.

The results obtained by sensimetry are shown in Table 1 below. However, the sensitivity values are expressed as relative sensitivities, with the sensitivity obtained with the reaction solution (A) not containing the compound of the present invention being taken as 100.

[- As is clear from Table 1, the developer (B) 1 (C) to which the compound of the present invention was added was 1 in comparison with the comparative developer (A) by 2
It can be seen that an increase in speed of 0 to 30% or more was obtained, and there was no decrease in D max, which is seen with conventional development accelerators, and there was little increase in fog.

Implementation@2 This example is an example in which the present invention was applied to a high temperature rapid developer containing glutaraldehyde.

[Developer (D)]

Glutaraldehyde 15.9 [Developer (E)] Prepared in the same manner as in (rl) above. However, the exemplified compound (5
) was adjusted by adding 0.029/l.

[Elephant liquid (F)]

It was created in the same manner as (+)) above. However, the exemplified compound (1
2) was adjusted by adding 0.0211/l of the same X-ray film as in Example 1 using three types of developers (I) L (E L (F)) adjusted as described above. Exposure according to l-Mary, temperature 35 °C for 30
A second development process was performed.

The results obtained by Sensitomery are shown in Table 2 below. However, the sensitivity is expressed as a relative value with the sensitivity of the sample obtained by processing with the developer (rl) as 100.

As is clear from Table 2, it can be seen that the developer according to the present invention can significantly improve sensitivity and DmaX without increasing fog even when used as a high-temperature rapid developer.

Example 3 This example shows the case where the compound of the present invention was added to the developer solution, and
This illustrates the difference between the addition of silver halide to a silver halide photographic emulsion.

Exemplary compound (2) was added to a polydisperse twinned silver bromide gelatin emulsion with an average grain size of 1.3μ and containing 2.0 mol% of glazed silver.
．． 06■, one with and without 1 mol of /AgX added was coated on a subbed polyethylene terephthalate film by a conventional method and dried.
A) l(B). This sample (A) was treated with the developer (A) of Example 1, and the sample (B) was treated with the developer (B) to perform sensitometry.

The results obtained are shown in Table 3.

Table 3 As is clear from Table 3, when the compound of the present invention is added to a silver halide emulsion? In comparison, it can be seen that fogging is lower and higher sensitivity can be obtained by adding it to the developing solution to make the present invention.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Patent attorney Nobuaki Sakaguchi (and 7 others) Procedural amendments signed) July 1, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi 1 Indication of the case 1988 Patent application No. 89449 2 Name of the invention Developer for silver halide photographic light-sensitive materials 3 Relationship with the person making the amendment Applicant name (127) Roku Konishi Photo Industry Co., Ltd. 4 Agent 105 6 Number of inventions increased by amendment 7. The description of the amendment to be made (Japanese Patent Application No. 57-89449) shall be amended as follows.

l On page 17, line 10, the phrase "silver bromide gelatin emulsion" is corrected to "silver iodobromide gelatin emulsion."

2 Correct rO, 05g J in the 4th and 7th lines of page 18 to rO, 02g J, respectively.

3. On page 21, line 7, it says rO, 08 mgJ.

Correct as ro, 08g J.

that's all

Claims (1)

[Scope of Claims] A developer for a silver halide photographic light-sensitive material, comprising a compound represented by the following general formula ['I]. General formula CI'] In formula C, A is a lower alkylene group having 1 to 3 carbon atoms, or -(CH2CH20), -. -(CH2CH20), -CH2-CH2-. In the group represented by, B represents a polyalkylene ether group not bonded with O. AI is a carbon atom □Number 1~
3 lower alkylene group or -(CH2CH20)P'-CH2-CH2-. represents a polyalkylene ether group represented by However, A and A1 do not simultaneously become polyalkylene ether groups. Moreover, P is an integer of 2 to 30. B+B' is -NH- or 10-, but B and B1 cannot be 10- at the same time. R represents a lower alkyl group having 1 to 3 carbon atoms, a phenyl group, an aralkyl group or -(CH2)q-COOR'. However, q is an integer of 1 to 3, and 6R' represents a lower alkyl group having 1 to 3 carbon atoms. It is a divalent group selected from lower alkyl groups having 1 to 3 X atoms. ]