JPS58190949A - Image forming method on silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain good dot quality even through operation using an automatic developing machine, by developing a silver halide photosensitive material contg. >=50mol% silver chloride based on the total silver halide in the presence of a specified compd. CONSTITUTION:The used photosensitive material has a support and at least one silver halide emulsion layer contg. >=50mol% silver chloride based on the total silver halide. This photosensitive material is developed in the presence of a compd. represented by the general formula ( I ) in which R<1> is 2-4 C alkyl; R<2> is 2-4 C alkylene; l is 0-5, m1+m2 is 2-20, and n1+n2 is 5-50.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material that is developed with a Lithium developer, and more specifically, it is a silver halide photographic material that is subjected to continuous running processing in large quantities, such as running processing using an automatic developing machine. Good halftone dot quality can be obtained, the optimum development time between the halftone dot and the flash point is close (there is little deviation in the optimum development time), and the development time range is wide enough to obtain excellent halftone dot quality. The present invention relates to an image forming method for a silver halide photographic material which allows a preferable lithographic development process.

It is known that certain silver halide photosensitive materials can be used to form extremely high contrast photographic images.

For example, a photosensitive material made of a silver chlorobromide emulsion with fine grains (average grain size of about 0.2 μ), narrow grain size distribution, uniform grain shape, and high silver chloride content (at least 50 mol% or more). Methods for obtaining halftone images with low sulfite ion concentrations are known.

This type of silver halide light-sensitive material is known as a silver halide photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material) which is developed using a Lith developer.

Typical additives (halftone quality improvers) that are commonly used to improve the photographic properties of light-sensitive materials include, for example, those described in Journal of the Seven Photographic Sciences (Journal of th@Photo' grap
hieScience) No. 12S, page 5 (1964)
There are polyalkylene oxide compounds described in, etc.

In addition, in order to exhibit the photographic properties of such light-sensitive materials, a special ultra-high contrast developer called Lith developer, which uses a dihydroxybenzene compound as a developing agent and has an extremely low concentration of free sulfite ions, is used. It is used in combination with development processing.

However, the halftone image obtained by developing the conventional photosensitive material with the above-mentioned Lith developer is particularly sensitive to low halftone dot areas (hereinafter referred to as small dots, represented by 10% halftone dots) and high halftone dots. In the dot area area (hereinafter referred to as ambition, represented by 95% halftone dots), it is still difficult to say that a fully satisfactory halftone quality has been obtained.

Furthermore, between small dots and large dots, the development time that provides the best halftone dot quality (hereinafter referred to as the optimum development time) generally tends to be faster for small dots. Therefore, the development time width that provides halftone dot quality that exceeds the practical limit (hereinafter referred to as the allowable halftone dot quality width).
It is well known that not only is it inherently narrow, but also that the optimum development times for the small dot and the aspiration are different, making it extremely narrow, and that strict development time management is required. There is.

In recent years, in the photolithography industry, the development of photosensitive materials using automatic processors has rapidly become widespread, and now accounts for the majority of the development.

In the conventional so-called dish development method, the lithium developer has poor air oxidation resistance, so it is necessary to always use a fresh lithium developer, and it must be discarded only at that time, which saves time and cost. It could not be said that it was reasonable in that respect.

On the other hand, in processing using an automatic developing machine, it is possible to continue running for a long period of time while automatically replenishing the replenisher depending on the amount of photosensitive material processed, simplifying the developing process, reducing costs, It has the advantage of not requiring any skill.

However, in running processing using an automatic developing machine,
The performance of Lith developer solutions gradually differs from the initial performance due to complex effects such as oxidation during development processing, oxidation due to oxygen in the air, effects of replenishers, and leakage of additives from photosensitive materials. As a result, various photographic properties of light-sensitive materials are gradually adversely affected, for example, the halftone dot quality deteriorates, and the development time range in which excellent halftone dot quality can be obtained becomes narrower. It is well known that it eventually becomes unusable.

If photographic performance changes as a result of running processing using an automatic processor, exposure and development conditions must be changed in order to use the photosensitive material at its maximum performance, making photolithography extremely complicated. I end up. Therefore, maintaining photographic performance (for example, halftone quality, etc.) at the start of running is extremely important in running processing using an automatic developing machine.

On the other hand, the lithium developer used in the development process of photosensitive materials, including the running process with these automatic developing machines, is
＋Nee Ni C Unilou Journal Op the.
Franklin Institute) (J,
A, C, Yulet J, Franklin
In5t, ) Volume 239, Page 221 (194
As described in detail in 5), it refers to a developer in which hydroquinone is substantially the only developing agent and the concentration of sulfite ions is low. This lithium developer can be roughly divided into powder type and liquid type. The main difference between the two is the alkaline agent and the solvent for the developing agent.Generally, the liquid type is prepared as a concentrated liquid, so potassium carbonate, which has high solubility, is mainly used as the alkaline agent, while the powder type uses sodium carbonate. is used. In addition, in the liquid type, a solvent such as triethylene glycol must be used because the solubility of the dihydroxybenzene compound, which is a developing agent, is low.

It is well known that these differences in developer composition cause large differences in various photographic properties (eg, sensitivity, halftone dot quality, optimum development time, etc.) of the light-sensitive materials. For this reason, there is a strong demand for photosensitive materials to have almost the same photographic properties whether they are powder type or liquid type.

In order to meet these demands, there is a method using a new additive (halftone quality improver)! #Described in the specification of Japanese Patent Publication No. 1983-30124.

According to this method, there is little deterioration in halftone dot quality and little change in halftone gradation even in running conditions using an automatic developing machine, and even if the composition of the lithium developer changes, the sensitivity, halftone dot quality, and
Although photographic properties such as halftone gradation can be obtained almost constant, and the development time range for obtaining excellent halftone dot quality has been widened, it has become possible to carry out preferable lithographic processing, but all of the compounds in the claims are However, it cannot be said that all of these points can be fully satisfied, especially when viewed from the viewpoint of the optimum development time between small and large halftone dots and the allowable range of halftone dot quality, as will be described later. It has been found that only a very limited range of compounds can be used.

Therefore, a first object of the present invention is to provide an image forming method for a silver halide photographic light-sensitive material that can exhibit good halftone dot quality even in a running state using an automatic processor.

The second object of the present invention is to ensure that the optimum development times for the small halftone dots and the large fish are close to each other (there is little deviation in the optimum development time), and to improve the management of the squirrel development process in order to obtain excellent halftone dot quality. An object of the present invention is to provide an easy method for forming an image on a silver halide photographic material.

A third object of the present invention is to provide a silver halide photograph which has a wide dot quality tolerance range between small dots and large dots, and which facilitates management of squirrel development processing to obtain excellent halftone dot quality. An object of the present invention is to provide a method for forming an image on a photosensitive material.

A fourth object of the present invention is to obtain good halftone dot quality even if the composition of the Lith developer is different, such as the difference between a liquid type and a powder type, and to improve the quality of halftone dots and large fish. It is an object of the present invention to provide an image forming method for a silver halide photographic light-sensitive material, which has an optimum development time close to that of a silver halide photographic material and which has a wide range of dot quality tolerance.

A fifth object of the present invention is to form an image of a silver halide photographic light-sensitive material that can obtain good halftone dot quality even in the case of different running processes using a lithographic development replenishment method and has a wide tolerance for halftone dot quality. The purpose is to provide a method.

Other objects of the present invention will become clear from the following description of the specification. This is achieved by developing a photographic material having a silver halide emulsion layer in the presence of a compound represented by the following general formula CI).

General formula [■] [In the formula, R1 is an alkyl group having 2 to 4 carbon atoms, R2 is an alkylene group having 2 to 4 carbon atoms, l is 0 to 5, ml
-)-m2 represents 2 to +, and n1+n2 represents 5 to 50. ] In the above - general formula I), the alkyl group having 2 to 4 carbon atoms represented by R1 is, for example, -cH, cH
4°CH8 Typical specific examples of compounds in which R2 represents an alkyl group having 2 to 4 carbon atoms are shown below. However, these are representative examples and are not limited to these.

Exemplary compound', HO(CH,CM,0)nl(CMtCIO)m
(CH1CH*0)n2HCH1QC,H.

m:12+al+aji! :3J 7:1. ml-4 koku*2: 15 e 3 k+-2:
301: 1 + mx10ai2: 12+ nl+
n2: 251' 1 + ml + R2: 16
+ n1+ R2"406.1TO(CHtCI'
l,0)n1+cHtcHo)m (CHtCM,O)
! 12HC1%0CsHy(II) / : 1 + ml +m2 : 8 + n1+
R2! 201: 1 * ml+m2: 14
T! Il+II2:359, HO(CM, CM,
(c1(CHtCHO)m(CHtCTItO)n2H
CB, 0CBHI (Iso) m:8+nl+n2:20 10, HO(CH,CH,0)nl(CH,CCl0
) (CH,CH,0)n2HCH10C3H7(ig
o) 7:1+ml+m! :8+w+1+ron 2:201:
5 + ml + m! : 10+n
l+a2: 201 = 1 +'flal-1
-fi2i 101113=+wt2: 2514
, N0CCH,CH,0)n1ccH,CHO)mc
cH, CTI, O) Donation HC1% OCA bird (21) m: 5 + fix + R2: 1
515, R0(CI'l, CM, 0)nL (CH,
CI'IO)m (CHtCHtO)n2HCH,QC
, Bird (!1) 18, No (fl H,CH,0)nl(C)It
CHO)m (CHaCI'ltO)II2"( CH,QC,H,1(3ec) Can be synthesized.

Next, these compounds represented by the general formula [■] used in the present invention are hereinafter referred to as compounds according to the present invention. ), the amount and place of addition, etc.

The addition site may be any of the constituent layers of the light-sensitive material, but preferably the silver halide emulsion layer and/or the layer adjacent to the silver halide emulsion layer. These compounds according to the present invention are dissolved in water, an organic solvent miscible with water, or a mixture thereof to form a silver halide emulsion. It is preferably added to a coating solution for forming the layer and/or its adjacent layer, particularly preferably in a silver halide emulsion layer.

The amount of the compound according to the present invention added is preferably 10119 to 5 g, particularly 10011 p to 2 g per mole of silver halide.
I is preferred. Further, the timing of adding the compound according to the present invention can be selected at any time during the process of producing a light-sensitive material, but for example, when adding it to a silver halide emulsion layer! It is preferable to add it after completing the 112 ripening.

The compound according to the present invention is also effective when added to the liquid solution**, and in this case, the compound according to the present invention is effective when added to the liquid solution.
109 (・.In addition, in order to make the compound of the present invention contained in the liquid preparation agent, if it is a powder type, add it at any time during the preparation process of the preparation liquid.* (1) may be blended in advance with the current Japanese drug, etc. If it is a liquid type, it may be added and dissolved in a concentrated liquid in advance. In case,
The replenisher should also contain an amount necessary to maintain the concentration of the compound according to the present invention in the current solution (ゝO) In terms of the composition, in order to wake up an explosive priest like Risu Genrin, it is necessary to have a fast priest speed, so it should contain more silver chloride than the father moruti compared to the halogenide. More preferably, silver chlorobromide or silver chloroiodobromide containing less than ω mol of silver chloride, less than 5 mol of silver bromide, and less than 5 mol of silver iodide is used.

In addition, these silver halides are described by Jam@-author H.T.
theory of the Photogr*phie
Documents such as "Proesss" M 4th edition Maemllan Publishing (L977) pages 88-104 (described neutral method, acidic method, ammonia method, forward mixing method, back mixing method, single jet method, double jet method, Contour a-Rubi double jet method, convergence method, core method
It can be manufactured by a method such as a shell method. Furthermore, there are no particular restrictions on the grain size, grain size distribution, crystal habit, morphology (normal crystal, twin crystal, etc.) of the silver halide grains to be used, but silver halide grains with relatively uniform grain sizes of 1μ or less are preferred. preferable. Further, these halide grains or silver halide emulsions may contain iridium salts and/or rhodium salts in order to improve flashlight characteristics.

These silver halides are generally sulfur sensitizers, such as sodium thiosulfate, thiourea, etc.; noble metal sensitizers, such as gold sensitizers, specifically gold chloride, □sanyang gold, etc.; Palladium sensitizers, such as palladium chloride, palladium chloride sensitizers, brass compounds, iridium compounds I
s: Selenium sensitizers, such as selenite, selenite, etc.;
Reduction sensitizers, such as chloride #! [It can be chemically sensitized by combining tin, diethylenetriamine, polyamine, sulfite, silver nitrate, and other chemical sensitizers. It is possible to optically sensitize to a desired wavelength range by using optical sensitizers such as - alone or in combination.

In addition, the compound according to the present invention, which contains an electron-capturing compound such as a metal dopant, can also be added to a direct positive photographic silver halide emulsion of more than 7p-applied silver halide emulsion. can be done. Furthermore, as the vehicle for the halogenated steel, gelatin, gelatin derivatives, synthetic hydrophilic Vorifu, etc. can be used.

can. For example, azaindenes as anti-capri agents,
Specifically, 4-hydroxy-6-methyl-1,3,3a
, 7-thitrazaindene, chiazoles, triazoles, tetrazoles, and any other anti-capri agent known in the art can be used. As the hardening agent, aldehyde compounds, ketone compounds, halogen-substituted acids such as mugochloric acid, triazine compounds, epoxy compounds, diamine imine compounds, vinyl sulfone compounds, and cryoyl compounds may be used. I can do it. As the spreading agent, saponin, lauryl or oleyl monoether of polyethylene glycol, etc. are used. There are no particular restrictions on the current situation accelerator, but for example, JP-A-49
Compounds such as those described in No. 24427, quaternary ammonium salts, etc. can be used. The silver halide emulsion layer or other constituent layers of the light-sensitive material according to the present invention include, for example, Japanese Patent Publication Nos. 45-5331 and 46-22.
No. 506, JP-A-49-74538, JP-A-55-2
No. 5077, U.S. Patent No. 2.852,386, U.S. Patent No. 3,0
No. 62,674, No. 3,411,911, No. 3.41
No. 1.912, No. 3,142,568, No. 3,325
, No. 286, No. 3,547,650! S&: Acrylic esters as described (e.g. evamethyl acrylate, ethyl acrylate, butyl acrylate,
1so-) methyl acrylate, t@rt-butyl acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, etc.), methacrylic layer esters (such as methyl methacrylate, butyl methacrylate, 2-
Hydroxyethyl methacrylate, glycidyl methacrylate #), acrylamides (e.g. acrylamide, N-butyl acrylamide #), methacrylamides (e.g. methacrylamide, N-butyl methacrylamide, etc.), vinyl esters (e.g. vinyl acetate, butyric acid) vinyl, etc.), vinyl halides (e.g. vinyl chloride, etc.)
, vinylidene halides (e.g. vinylidene chloride, etc.)
, vinyl ether (vinyl methyl ether), styrenes (e.g., t-styrene, α-methylstyrene, p-hydroxystyrene, etc.), ethylene,
Contains polymer latex, etc. consisting of homo- or copolymers of propylene, butylene, butadiene, tribrene, acrylonitrile, methacrylate trile, acrylic acid, methacrylic acid, itaconic acid, etc., for the purpose of improving the dimensional stability of photosensitive materials and improving film properties. You can apply it. Also, for example, Il! # It is possible to add an antistatic agent as described in the specifications of JP-A-49-46733, JP-A-51-56220, JP-A-54-48520, JP-A-55-25077, etc. can.

Examples of the support used in the photosensitive material according to the present invention include any support such as polyethylene terephthalate film, polycarbonate film, polystyrene film, and cellulose acetate film.

The photographic material according to the present invention is a type of photographic material that is processed using the above-mentioned lithium chloride solution, and has at least one silver halide emulsion layer containing a chloride content of at least 100% on the above-mentioned support. If necessary, other hydrophilic colloid layers (subbing layer, intermediate layer, anti-rage layer, protective layer) may be applied.

Exposure of the photosensitive material according to the present invention can be carried out using tungsten, fluorescent lamp, mercury lamp, xenon, arc lamp, xenon flash,
It is performed using various light sources such as cathode ray tube flying spot and laser light, and the exposure time is 1. In addition to regular exposures of 3 to LOO seconds, xenon flash, cathode ray tube, and laser light are used for buttocks. 4-Hot. A brief 9 second fog light will be performed. Furthermore, the spectral distribution of the light source can be adjusted using a color filter if necessary. The temperature of the immersion treatment with the squirrel solution is preferably from 0.degree. C. to 40.degree. C., but the treatment may be performed at even higher temperatures. The immersion time varies depending on the current temperature, but is preferably 180 seconds to 180 seconds. Although a so-called dish dipping method can be used as the dipping method, the effect of the present invention is great when running a large amount continuously using an automatic cash dispensing machine. There are no restrictions on the conveyance method for the automatic dispensing machine, such as roller conveyance or belt conveyance, and any conveyance-type automatic dispensing machine used in the industry can be used.

The liquid replenisher, replenisher, replenishment method, and equipment used are chemically distinct and each has a different halide ion concentration. Method of keeping
No. 6), a method using a replenisher prepared from at least two stable solution concentrates (Japanese Patent Application Laid-Open No. 49-68725)
, an apparatus comprising a replenisher storage tank, a metering means associated with the storage tank for transferring a portion of the replenisher from the carcass storage tank to a photographic processing machine, and means for controlling the metering means (No. 49-69141), a method of adding two different types of replenisher (Japanese Patent Application Laid-Open No. 51-110329), a method that automatically adds an amount of replenisher that is predetermined based on the stop time of the automatic toilet machine and the tank liquid temperature. Addition method when the Genrin machine is in operation (Japanese Patent Publication No. 5
No. 3-23631), in a method of adding a replenisher for processing fatigue and a replenisher for aging fatigue, a fixed amount of the replenisher for aging fatigue is added at fixed time intervals during operation of an automatic dispensing machine. It is possible to refer to the method described in JP-A-53-100232, in which a predetermined amount is added based on the downtime and room temperature when the system is stopped and then restarted. 'Next, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

The compositions of the squirrel liquid and replenisher used in the following examples are as shown in Table Mi.

Table 1 Example-1 A lithium-type silver chlorobromide emulsion containing 1 mole of bromide chain addition and 0.1 mole of silver iodide was gold-sensitized and sulfur-sensitized. It was divided into 13 parts. Incidentally, the average particle size of the rogenated bale particles used was 0.28μ.

As shown in Table 2, the compounds according to the present invention (indicated by the numbers of the above-mentioned exemplified compounds) or the comparative compounds A to E described later were added to these emulsions to form 1-carboxymethyl-5-(
Optically sensitized using (3-ethyl-2-benzoxazolidine)-ethylidene]-3-phenyl-2-thousandohydantoin, stabilized with 4-hydroxy-1,3,3m,7-titrazaindene, and further hardened the membrane. Polyethylene terephthalate 1 that has been subbed after adding general photographic additives such as additives, spreading agents, and physical property improvers (Bojlmar Latex).
．． A photosensitive material sample (AI-13) was prepared by coating and drying on a film base using a conventional method.

Sensitometry was performed on these samples. That is, a negative contour screen (150 lines/inch) was attached to a portion of the step wedge, the sample was brought into close contact with the screen, and the sample was exposed to light from a tungsten light source for 10 seconds.

This sample is shown in Table 1.
Then, dipping treatment was carried out using a Sakura automatic dipping machine GQ-25 (Konishi Roku Photo Industry Co., Ltd.! 1) at 27"C and varying the erosion time to obtain halftone dots.

The halftone dot surface density thus obtained was observed with a 100x magnifying glass, and the halftone dot quality of 10% and 95 dots, the optimum immersion time, and the allowable range of halftone dot quality were determined. The results are shown in Table 2. In addition, when evaluating the quality of halftone dots, there are few and sharp fringes around the halftone dots (so-called...dots).
was graded as 10th grade, those with very many fringes were graded as 1st grade, the in-between grades were classified into 10th grade to 1st grade, and the practical limit was graded as 5th grade.

In addition, as a method for evaluating sensitivity, 95
Based on the reciprocal of the exposure amount giving % halftone dot, the sensitivity was expressed as a relative sensitivity, with the sensitivity in the case of the sample layer 1 using the current solution -2 being 100. Sensitivity is expressed in the same manner in the following examples.

As is clear from Table W42, the samples according to the present invention containing the compound according to the present invention all have excellent halftone dot quality and halftone quality tolerance, and have an optimal small dot and flash point. It can be seen that the bond time for 11 is very small.

Example-2 Lith-type chloriobromide containing 1 (1" mole of iridium salt per mole of silver halide in the silver halide grains, 29.7 mole of bromide and 0.3 mole of iodide) The chain emulsion was gold-sensitized and sulfur-sensitized and then divided into 13 parts each containing 1 mole of silver halide.The average grain size of the silver halide grains used was 0.32 .mu.m.

As shown in Table 1113, the compounds according to the present invention (indicated by the numbers of the above-mentioned exemplified compounds) or comparative compounds A and D, and comparative compounds F-H described below were added to these emulsions, and the mixture was prepared as in Example-1. Optically sensitized and coated with other additives
It was dried to produce light-sensitive material samples (414-S).

These samples were treated with Lithium liquid solution (liquid type) shown in Table 3, and then measured as in Example I. The results are shown in Table 3.

2.: m-v 1 As is clear from Table 3, the samples according to the present invention containing the compound of the present invention all had excellent halftone dots even if the Liss liquid was liquid type. It can be seen that the quality and halftone dot quality are within the acceptable range, and the difference in the time for collecting waste for small dots and large fish is also very small.

Example-3 After image processing (new solution performance), replenisher 1. shown in Table 1 was used. Using TI, cleaning treatment was carried out at 27° C. by the following two replenishment methods.

[Method -■]

Running treatment was performed using replenisher I for only 7 hours during the day. After stopping for 17 hours, the sensitivity of the 95% halftone dot was adjusted to the new solution level using a certain amount of replenisher 11, and the beam: post-running process was continued. During this period, a constant amount of replenisher solution (■) was added every hour during running, weight testing, and restarting. After 10 days of this cycle, sensitometry was performed.

Therefore, = f responsibility [Method - ■] One sheet of film (large paper size) for 7 hours a day
After each treatment, running treatment was performed while replenishing with replenisher I, and then rested for 17 hours. At the time of restarting, replenisher I was used to adjust the sensitivity of the 95% halftone dot to the new solution level, and then replenisher I was used again to continue the running process. After 10 days of this cycle, sensitometry was performed.

The above evaluation was conducted as in Example-1 and is shown in Table 4. Note that 95 halftone dots are shown for the highest halftone dot quality and the acceptable halftone dot quality.

As is clear from Table 4, the samples according to the present invention containing the compounds according to the present invention not only have excellent halftone dot quality and halftone dot quality tolerance width in the new solution. , it can be seen that there is little deterioration in halftone dot quality and halftone dot quality tolerance width even with running liquids with different replenishment methods.

Agent Yoshimi Kuwahara

Claims (1)

[Scope of Claims] A photographic light-sensitive material having a support and at least one silver halide emulsion layer in which 50 molar or more of silver halide is silver chloride is prepared in the presence of a compound represented by the following general formula CI). 1. A method for forming an image on a silver halide photographic light-sensitive material, the method comprising developing a silver halide photographic material. General formula CI) [In the formula, R1 is an alkyl group having 2 to 4 carbon atoms, R2 is an alkylene group having 2 to 4 carbon atoms,! is 0-5, ma
+ mQ represents 2-20% nl 4m represents 5-50. ]