JPS6280648A - Image forming method - Google Patents

Abstract

PURPOSE:To form a developed image with an increase of effective sensitivity and no increase of fog by easy handling at an increased developing speed by using a cyclic amine compound as a development accelerator. CONSTITUTION:Development is carried out with a developing soln. or the preceding bath contg. a compound represented by formula I or a salt thereof. A concrete example of the compound used is represented by formula I-1. The proper amount of the compound added to the developing soln. or the preceding bath is bout 1X10<-4>-2X10<-2> mol/l. By the addition of the amine compound, development is accelerated and rapid development can be attained at the conventional developing temp. as well as at an increased developing temp.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method of forming an image from a silver halide photographic material. More specifically, it relates to a method for forming photographic images with increased sensitivity without significant fogging by processing silver halide photographic materials with a developing solution containing a specific amine compound. be.

(Prior Art) In the development process of silver halide photographic light-sensitive materials, it is desired to accelerate the development speed and increase the effective sensitivity of the developed light-sensitive materials. For this purpose, it has been known to add an amine compound as a development accelerator. Examples of such amine compounds include alkylamines (US Pat. No. 2,196,037) and aralkylamines (US Pat. No. 2,496,903 and US Pat. No. 2,515,147).
fp12482546), heterocyclic alkylamines (US Patent No. 2605)
183), morpholine, piperidine, etc. (US Pat. No. 2,304,025), xylylene diamines (British Patent No. 1,086,618), and the like.

(Problems to be Solved by the Invention) However, these amines generally have a bad odor, are volatile, are difficult to handle because it is difficult to maintain a constant concentration in the processing solution, and cannot be added to the developer solution. Although it has the effect of accelerating development, the effective effect of increasing sensitivity is small and an increase in fog is observed.

An object of the present invention is to develop a development accelerator that is easy to handle, increases the development speed, increases effective sensitivity, and does not increase fog, and provides an image forming method using the same.

(Means for Solving the Problems) The present inventors have conducted various studies in order to overcome the problems associated with the conventional development processing of photographic light-sensitive materials, and as a result, the present inventors have found that a certain type of cyclic amine compound is used as a development accelerator. By this,
We have found a way to achieve this objective, and based on this knowledge, we have completed the present invention.

That is, the present invention provides an image forming method characterized in that a silver halide photographic light-sensitive material is developed with a developer or a pre-bath thereof containing a compound represented by the following general formula CI) or a salt thereof. It is.

General formula CI) The group may have a fused monocyclic or bicyclic heptaryl group,
Further, R represents a group consisting of a combination of two or more selected from hydrogen, carbon, oxygen, sulfur, or halogen atoms, or represents a hydrogen atom or a halogen atom.) The present invention will be described in detail below.

Examples of the unsaturated heterocycle represented by formula (I) include virole, pyrazole, imidazole, triazole, tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, and azepine.

Examples include diazepines and hydrogen adducts thereof.

Examples of the aryl group condensed to these unsaturated heterocycles include benzene and naphthalene.

Furthermore, these unsaturated heterocycles and the aryl groups condensed thereto may be substituted with one or more suitable substituents. Examples of substituents include alkyl groups (preferably those having 1 to 20 carbon atoms). For example, methyl group, ethyl group, 5ec-octyl group, etc.), aryl group (carbon number 6 to
20, such as phenyl group, naphthyl group, etc.)
Alkoxy group (preferably one with 1 to 20 carbon atoms, e.g. methoxy group, hexadecyl group, etc.), aryloxy group (preferably one with 6 to 20 carbon atoms, e.g.
phenoxy group, naphthyloxy group, etc.), alkylthio group (preferably one with 1 to 20 carbon atoms, such as methylthio group, dodecylthio group, etc.), arylthio group (preferably one with 6 to 20 carbon atoms, such as phenylthio group), groups), halogen atoms (e.g., fluorine, chlorine, bromine, iodine, etc.), acylamino groups (preferably carbon atoms
to 20 carbon atoms, such as acetamido group, penzamide group, etc.), sulfonamide group (preferably 1 to 20 carbon atoms)
(e.g., methanesulfonamide group, benzenesulfonamide group, etc.), ureido group (preferably one with 1 to 20 carbon atoms, e.g., methylureido group, hexylureido group, phenylureido group, etc.), cyanide group , carboxyl group, carbamoyl group (preferably one having 1 to 20 carbon atoms, such as carbamoyl group, N-methylcarbamoyl group, N-phenylcarbamoyl group, etc.)
, sulfamoyl group (preferably one with 1 to 20 carbon atoms, such as sulfamoyl group, N-methylsulfamoyl group, N-phenylsulfamoyl group, etc.), acyloxy group (preferably one with 1 to 20 carbon atoms) ,for example,
acetoxy group, benzoxy group, etc.), alkoxycarbonyl group (preferably one with 1 to 20 carbon atoms, such as methoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (preferably one with 7 to 20 carbon atoms),
20, such as phenoxycarbonyl group)
, an acyl group (preferably one having 1 to 20 carbon atoms, for example 1).

formyl group, acetyl group, benzoyl group, etc.).

Amine group (preferably one having 0 to 20 carbon atoms, such as an amino group, an N-methylamine group, and an N-methylamine group.

N-dimethylamino group, N-propylamino group, N-phenylamino group, etc.), imino group (preferably carbon@O
-20, for example, imino group, N-methylimino group, N-phenylimino group, nitrone group, alkenyl group (preferably one with 2 to 20 carbon atoms, for example,
allyl group), alkynyl group (preferably 2 to 2 carbon atoms)
20 (for example, propargyl group, etc.), sulfonyl group (preferably one with 1 to 20 carbon atoms, side-lighting),
(methanesulfonyl group, benzenesulfonyl group, etc.), hydroxyl group, etc. These substituents may be further substituted with the substituents described above.

, z=="-1 °'・11..-h~ ■ The unsaturated heterocycle represented by is preferably a 6-membered ring, and more preferably one derived from a pyridine ring or a pyridazine ring. Particularly preferred is the case where a benzene ring is fused to the pyridine ring or pyridazine ring.

Examples of R in the general formula (I) include the following. Here, R21 to R23 may be the same or different and represent a hydrogen atom, an aliphatic group or an aromatic group.

The aliphatic group represented by R21 to R23 includes a straight chain or branched alkyl group, alkenyl group, alkynyl group, or cycloalkyl group. The alkyl group has 1 to 18 carbon atoms, and includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, an isopropyl group, a t-butyl group, and a 2-ethylhexyl group.

Examples of alkenyl groups include those having 2 to 20 carbon atoms; 1. For example, allyl group; 2. -butenyl group, etc.

Examples of the alkynyl group include those having 2 to 20 carbon atoms, such as propargyl group and 2-butynyl group.

The cycloalkyl group has 3 to 12 carbon atoms, and includes, for example, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. The aromatic group represented by R21 to R23 has 6 to 20 carbon atoms, such as phenyl group and naphthyl group.

H to R23 may be substituted with one or more suitable substituents, examples of which are the above-mentioned 2.

These are listed as substituents. These substituents may be further substituted with the substituents mentioned therein.

Examples of the halogen atom of H include fluorine, chlorine, bromine, and iodine.

In the present invention, the salt of the compound represented by the general formula (I) is a salt formed with organic acid, mineral acid, etc. Here, the acid includes hydrochloric acid, sulfuric acid, bromic acid, oxalic acid, acetic acid, etc. can be mentioned.

Next, specific examples of compounds used in the present invention will be given, but the present invention is not limited to these.
N[-7l-8 1-ts I-19 General formula C
Some of the compounds listed as specific examples of I) are available as commercial products. Other derivatives can also be easily synthesized by referring to the method described in 1 literature. (A. R. Katlitsky and C. W. Reese° “Comprehensive Heterocyclic Chemistry - Structure, Reaction, Synthesis and Utilization of Heterocyclic Compounds” (“Coa+
prehensive Hetero-c7clic
Chemistry7-The 5structure,
Reactions.

5ynthesis and Use of He't
eroc7clic Compounds”) Vol.
5 Pergamon Press, Oxford (1984)
) pp847-904)].

British Patent No. 868.787 describes that the compound of the present invention is used as an antifoggant by adding it to a photographic material. However, it was completely unexpected that images with high sensitivity could be obtained without significant generation of capri when used in a developer.

The photographic processing method of the present invention can be carried out according to known methods, except for using the compound represented by the general formula (I) or its salt (hereinafter simply referred to as the compound of the present invention). A known treatment liquid can be used. The processing temperature is usually selected between 18°C and 50°C, but temperatures lower than 18°C or above 50°C may also be used, depending on the purpose. Any color photographic process consisting of a development process to form an image can be applied.

For details, see Research Disclosure Volume 176N
o, 17643, pages 28-29, Volume 187, No. 1
Development processing can be carried out by the method described in the left column and right column of page 651 of 8716.

The developer used in black-and-white photographic processing can contain known developing agents. As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-
Pyrazolidones (e.g. 1-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p
-aminephenol), l-phenyl-3-pyrazolines, ascorbic acid, and U.S. Pat. No. 4,067.872
Heterocyclic compounds in which a 1,2,3,4-tetrahydroquinoline ring and an intrene ring are condensed as described in the above can be used alone or in combination.

On the other hand, the color developing agent is generally an alkaline aqueous solution containing a color developing agent. -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-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.)
can be used.

In addition, "Photographic Processing Chemistry" by F. A. Mason (P.
photographic processing Ch.
emiStr2) (Published by Focal Press, 1966
226-229 of U.S. Patent No. 2,193,015
No. 2゜592.364, Japanese Unexamined Patent Publication No. 48-64933
You may use those listed in the No.

Black and white or color developers may also contain antioxidants such as sodium sulfite, ascorbic acid, salts such as sodium sulfate, and pH additives such as boric acid, borax, sodium hydroxide, sodium carbonate, and sodium triphosphate. Conditioners, buffers, development inhibitors such as potassium bromide and potassium iodide, and organic antifoggants such as 6-nitrobenzimidazole and benzotriazole can be added. In addition, aldehydes such as formalin and geltaraldehyde may be added.

The pH of the developer is preferably 9 to 12.5.

Furthermore, to explain in detail the embodiment in the case of black and white development processing, the black and white developer generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc., and if necessary, a dissolution aid. , a toning agent, a development accelerator, a surfactant, an antifoaming agent, a water softener, a hardening agent, a viscosity imparting agent, and the like.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

In addition, to explain in detail the embodiments in the case of color development processing, the color developer may include alkali metal sulfite,
PH buffering agents such as carbonates, borates and phosphates, development inhibitors or antifoggants such as bromides, iodides and organic antifoggants can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, Fogging agents such as sodium polyhydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid type chelating agents as described in U.S. Pat. No. 4,083,723, OLS 2
It may also contain antioxidants such as those described in No. 622.950.

Although the present invention can be applied to both a black and white developer and a color developer as described above, the effect is particularly remarkable in the case of a black and white developer.

The amount of the compound of the present invention to be used is effective even if it is added to the developer solution or added to the pre-bath before development. When added to the developer or its bath, it varies depending on the composition of the developer or pre-bath, but generally 2 x 10 to 1Xl0' per liter of processing solution.
Effective in the molar range, lXl0' to 2X10-2
A molar level is more appropriate.

The photosensitive materials to which the method of the present invention is applied include silver halide agents, dye-forming couplers, sensitizers, sensitizing dyes, antifoggants, coating DP agents, stabilizers, slip property improvers, binders,
Desensitizer, brightener.

Hardeners, plasticizers, anti-slip agents, matting agents, high-boiling organic solvents, development accelerators, antistatic agents, anti-stain +1 agents, dyes, and the like can be used.

Regarding the aforementioned additives and these additives, please refer to Research Disclosure (R65earch Disclosure).
ure) Volume 176, No. 17643 (December issue, 1
978), Items 1 to Reference (pages 22 to 28) can be used.

The photosensitive material used in the present invention may contain an ultraviolet absorber such as a benzotriazole compound substituted with an aryl group in the hydrophilic colloid layer.

The photographic emulsion of the present invention can be applied to flexible supports such as plastic films, (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), paper, etc., which are commonly used in photographic light-sensitive materials, or glass.

applied to a rigid support such as

The method of the present invention can be applied to various silver halide photographic materials for color and black-and-white photosensitive materials. In addition to photosensitive materials (especially materials for direct and indirect photography using screens), silver salt diffusion transfer process, die transfer M-process, S-color GA
Used for white method, printout sensitive materials, heat development sensitive materials, etc.

(Effects of the Invention) According to the method of the present invention, it is possible to prevent the volatilization of the development accelerator in the processing solution and the resulting odor, and to maintain the composition of the processing solution constant. Furthermore, according to the method of the present invention, it is possible to form photographic images with less fog and a marked increase in sensitivity. Furthermore, according to the method of the present invention, development can be stopped quickly by adding an amine compound, and rapid processing can be carried out without increasing the development temperature. Of course, it goes without saying that if the developing temperature is raised, processing can be done more quickly.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 6 To a silver iodobromide gelatin emulsion (grain size 0.751 L) containing mol % of silver iodide, sodium 100sulfate, potassium chloroaurate, and rhodan ammonium were added.
It was aged for 50 minutes at 0°C.

A hardener (2,4-dichloro-6-hydroxy-1,3,5-)riazine sodium salt) and a coating aid (sodium dodecylbenzenesulfonate) were added to this emulsion.
This emulsion was applied onto a triacetate film and dried. From the films obtained in this way, sample No.
I cut out 1 to 8.

Further, as shown in Table 1, a film was prepared in the same manner as above using an emulsion obtained by adding an exemplary compound of the present invention to the above emulsion to prepare sample No. 9.10.11.

These films were given a 1/100 second exposure through an optical wedge.

These samples Nos. 1 to 8 were mixed with developer CI of the following formulation.
Sample No. 9.10.
No. 11 was developed with developer CI) at 20° C. for 4 minutes, respectively.

Subsequently, the sample was fixed, washed with water, and dried in a conventional manner, and the photographic properties of the obtained sample were measured. The results are shown in Table 1.

Developer (I) Sodium sulfite 67g Hydroquinone 23g 1-phenyl-3-pyrazolidone 0.4g Sodium hydroxide ttg Sodium carbonate (-hydrate) 11g Potassium bromide
3g 5-Methyl-benzotriazole Add 0.08g water to make one sentence pi (' 10.65 From the results in Table 1, the presence of the exemplified compound of the present invention in the processing solution indicates that sensitization is achieved. Furthermore, a comparison with Comparative Compound (A) shows that the method of the present invention causes almost no increase in fog.

Further, from a comparison of Samples No. 2 and 9, it can be seen that when the exemplified compound of the present invention is added to the emulsion, the sensitivity decreases, but when it is added to the developer and processed by the method of the present invention, it is sensitized.

Furthermore, when the method of the present invention was applied, the volatility of the developer was lower than that of the conventional developer, and there was no bad odor at all.

Note that the relative sensitivity in Table 1 is the relative value of the reciprocal of the exposure amount that provides an optical density of fog + 0.2 for sample No.

The value of l was expressed as 100.

Claims (1)

[Scope of Claims] An image forming method characterized by developing a silver halide photographic material with a developer or a pre-bath thereof containing a compound represented by the following general formula (I) or a salt thereof. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. and the unsaturated heterocyclic residue may have a fused monocyclic or bicyclic aryl group. In addition, R is two or more selected from hydrogen, carbon, oxygen, sulfur, or halogen atoms. (represents a group consisting of a combination of hydrogen atoms or halogen atoms)