JPH023032A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the high image quality and the high contrast of a picture by incorporating a specified amount of silver chloride and a ruthenium salt respectively, and at least one kind of specified comds. in the photosensitive material. CONSTITUTION:The photosensitive material contains at least 60mol% of silver chloride and the ruthenium salt in an amount of 1X10<-9>-1.0X10<-5>mol per 1mol of silver halide. At least one kind of the compds. shown by the formula R1 NHNHCOR2 is incorporated in the photosensitive material. In the formula, R1 is aryl or pyridyl group which may be substd., R2 is hydrogen atom or phenyl or 1-25C alkyl group which may be substd. Thus, the picture having the high image quality and the high contrast as the reverse photosensitive material for a daylight room, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a light-sensitive material for photolithography for printing.

[Conventional technology]

In recent years, in the field of printing photolithography, the colorization and complexity of printed matter has increased, and color scanners have been developed, and there is a strong demand for improved efficiency in the turning process in particular. In particular, using a bright room during the turning process greatly contributes to improving work efficiency, and the ratio of using a bright room is increasing year by year. The shift to a brighter room for the turning process is a result of both improvements in equipment such as printers and improvements in photosensitive materials.

In terms of photosensitive materials, silver halide photosensitive materials called light-sensitive materials have been developed that have ultra-low sensitivity and can be handled in bright rooms. The photosensitive materials are made suitable for the so-called "lithographic development" process, and efforts are being made to improve their quality. Not enough.

On the other hand, as a technique for obtaining a high-contrast image comparable to the "lithographic development" process, patent disclosures can be found regarding several attempts. For example, there are Japanese Patent Application Publication No. 52-18317 and Japanese Patent Publication No. 53-40899. In addition, a technique for obtaining high-contrast images using a hydrazine compound was disclosed in Japanese Patent Application Laid-Open No. 53-16.
No. 623, No. 53-20921, No. 53-20922
No. 53-49429, No. 53-66731, No. 53-66732, No. 53-77616, No. 53-
No. 84714, No. 53-137133, No. 54-37
No. 732, No. 54-40629, No. 55-52050
No. 55-90940, No. 56-67843, etc. are disclosed. In the processing methods in these series of image forming methods using hydrazine compounds, the pH value of the developer containing the hydrazine compound or the pH value of the developer for processing photographic materials containing the hydrazine compound is at a relatively high level. However, it has the disadvantage of reducing the useful life of the developer.

On the other hand, in JP-A-56-106244, by containing a hydrazine compound and a development-promoting amount of an amino compound during image formation, a high-contrast image can be produced at a relatively low pH.
(11"11.5).

However, there have been no examples of the application of high-contrast image forming methods using these hydrazine compounds to so-called "bright room photosensitive materials" in the art disclosed so far. As a result of intensive research, the inventors of the present invention were able to establish a technical application method for high-contrast contrast enhancement technology using these useful hydrazine compounds to light-sensitive light-sensitive materials, which are currently in abundance and in high demand for high quality.

[Problem that the invention seeks to solve]

The first object of the present invention is to provide a silver halide photographic light-sensitive material for bright room printing which provides high-quality, high-contrast images. A second purpose is to make it possible to apply high contrast enhancement technology using a hydrazide compound to a silver halide photographic light-sensitive material for bright room reversal.

[Means for solving problems]

The above objects can be achieved by the present invention as described below. That is, it contains at least 60 mol% silver chloride, and
l of ruthenium salt per mole of silver halide
This can be achieved by using a silver halide photographic light-sensitive material which contains 'mol-1, OX 10-'-T-' and at least one compound represented by the following general formula [I].

General formula [1] %Formula% (In the formula, R represents an aryl group or a pyridyl group, including those having a substituent. R2 is a hydrogen atom, a phenyl group that may have a substituent, or a carbon Number 1~
25 represents an alkyl group. ) Hereinafter, the structure of the present invention will be specifically explained in detail.

The silver halide used in the present invention may be silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide, but the amount of silver chloride depends on the composition ratio of silver halide. The silver chloride content is preferably 80 mol% or more, more preferably 90 mol% or more.

When the silver chloride content decreases, the safety under bright indoor lighting, which is important as a bright room light-sensitive material, deteriorates. This reduces the workability of the light-sensitive material (hereinafter referred to as "photosensitive material"), and the material cannot be put to practical use. The emission distribution of a commonly used bright indoor light is on the longer wavelength side than the wavelength of 400n. As the silver chloride content decreases, the overlap between the emission wavelength of a bright indoor light and the specific sensitivity of silver halide particles increases, and therefore the safety of bright indoor lights deteriorates. Conceivable.

In the present invention, the amount of ruthenium salt added is silver halide 1
1 per mole. OX 10-s mol-1, OX 10-
'It's a mole. If the amount of ruthenium salt is less than I x 1 G-' moles, the sensitivity will not be reduced to the level required for a photosensitive material, which is the object of the present invention.

In the present invention, in addition to using a ruthenium salt, a desensitizer can also be used as a sensitivity regulator. Specific desensitizers that can be used in combination include inorganic desensitizers such as cupric chloride and iridium chloride, and mg sensitizers such as pinacryptol yellow phenosafranine. Further, an organic dye having absorption at a wavelength of 350 to 450n+n, such as tartrazine, may be used in combination. If the ruthenium salt alone is to desensitize to the required limit, preferably 10-'mol/
It is preferable to add 1 mol or more of AgX.

On the other hand, the amount of ruthenium salt added is l x 10-' mol/A
If it exceeds gXI mol, the contrast enhancement effect of the hydrazine compound generally decreases significantly, which is not preferable. That is, 1
．． The desired effect can be achieved by adding ruthenium salts in amounts up to 10-' mol OX/1 mol AgX.

For the emulsion, the amount of hydrazine compound added in order to obtain a high-quality light-sensitive material that can achieve the purpose of the present invention is as follows:
lX 10-' to lX 1 per mole of silver halide
Addition in an amount of 0-'' molar is preferred.

In the present invention, the ruthenium salt is preferably present during the preparation of the silver halide emulsion, but the time of preparation refers to the process of emulsification and physical ripening, and the ruthenium salt may be added at any time during this process and by any method.

However, the preferred addition time is during emulsification, and a particularly preferred method is a method in which the ruthenium salt is added to the halide solution. This is because in order to maximize the desensitizing effect of ruthenium, ruthenium atoms must be uniformly distributed from the interior to the surface of the silver halide grains, and for this reason it is preferable to add them to the halide solution.

Next, the compound represented by general formula (1) according to the present invention will be explained. This is a hydrazine compound and is represented by the following formula.

General formula [■] R, -NHNHCOR2 R, represents an aryl group or a pyridyl group. The electronic characteristic derived from the /guma value of the special program Nihamet is +0.30
A phenyl nucleus that is smaller is better. The value of HAME/T can be obtained relatively easily from literature, etc.

One of the preferred groups is an unsubstituted phenyl group.

Furthermore, preferred substituents for the aryl group include halogen groups (e.g. fluoro group, chloro group), alkyl groups (e.g. methyl group, ethyl group, n-propyl group, isobutyl group, n-butyl group, isobutyl group, n-hexynyl group, n-
Octyl group, 16rt-octyl group, n-decyl group, n
-dodecyl group), alconyl group, and acylamino group (eg, acetylamino group, p[cobanoylamino group, benzoylamino group).

Particularly preferred are those having a ballast group for photographic additives. The ballast group generally contains 8 or more carbon atoms, and for example, when an m-tert pentylphenoxy group is substituted with butylamide, etc., it is effective in suppressing the diffusivity in the film layer after coating the emulsion. work.

R2 represents a hydrogen atom, a phenyl group which may have a substituent, or an alkyl group having 1 to 3 carbon atoms, and is particularly preferably a hydrogen atom. Examples of hydrazine compounds that can be particularly preferably used in carrying out the present invention are listed below, but the present invention is not limited to the following examples.

I-I I-2■ ■ (L)C5H+ + ■ One! 6. The compound represented by the general formula [N can generally be synthesized by the reaction of hydrazines and formic acid, or the reaction of hydrazines and aryl halide.

The compound represented by the general formula [■l is used in an amount of l x 10-' mol - lXl 0-1 mol per mol of silver halide, particularly preferably s
In order to add the compound represented by the general formula [11] to the emulsion, a conventional method for adding additives in photographic emulsions can be used. For example, a water-soluble compound can be used as an aqueous solution with an appropriate concentration, and a water-insoluble or sparingly soluble compound can be dissolved in a suitable organic solvent that is miscible with water, and the solution can be added to the emulsion.

The emulsion preparation method in the present invention may be a single jet method such as a forward mixing method or a back mixing method, or a double jet method using a simultaneous mixing method.

If the emulsion preparation method using the simultaneous mixing method shown in Japanese Patent Application No. 58-88186, No. 58-88220, and No. 58-200685 is followed, monodisperse particles can be obtained, which is effective against the effects of the present invention. However, the present invention is not only effective for these monodisperse particles. Further, any method such as an ammonia method, a neutral method, an acid method, or a modified ammonia method disclosed in Japanese Patent Publication No. 58-3532 may be used. The crystal habit of the silver halide grains may be cubic, tetradecahedral or octahedral, or may be the doublet type grains disclosed in JP-A-58-108525. The particle size is preferably 0.5 μm or less, but is not particularly limited. In addition, in order to impart high illuminance characteristics to the grains, iridium metal is doped in the range of IX10-' to lXl06 per mole of silver halide, and rhodium metal is doped in the range of lX10 to impart high contrast.
-' to lXl0-' or rare earth metals such as scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, polonium, yttribium, lutetium, terbium, thurilam to adjust the sensitivity. 1O-' to 1O per mole of silver halide
-5 molar doping is optional. Doping these metals as halides into silver halide grains in order to impart desirable properties is a good method for exerting the effects of the present invention. When doping particles, it may be localized on the surface of the particles or localized inside the particles.

The emulsion thus prepared can also be chemically sensitized using a chemical sensitizer (for example, sulfur sensitization, gold sensitization, reduction sensitization, etc., or a combination thereof). However, the object of the present invention can be achieved without any chemical sensitization.

Furthermore, the emulsion prepared in this manner may contain stabilizers such as tetrazaindenes, antifoggants such as triazoles and tetrazoles, covering power improvers, and irradiation inhibitors such as oxanol dyes and dialkylaminos. It is possible to add benzylidene dyes, etc., polymer latexes as wetting agents, and other additives used in general photographic emulsions, such as spreading agents and hardening agents.

Further, in addition to organic antistatic agents, fine particles of metal oxides can be contained as inorganic antistatic agents. As preferred metal oxides, fine particles of tin or indium, or fine metal particles doped with antimony or the like are included in the protective layer or emulsion layer to impart conductivity.
The antistatic effect can be improved. These metal oxides contain IX 10-' to lX per mole of silver halide.
It is preferable to use the metal oxide in the range of 10", preferably in the range of 10-' to 10-1. It can also be included in the subbing layer below the emulsion layer. The metal oxide may be spherical or amorphous. The choice of metal oxide depends on its conductivity and its transmittance (
haze), but it is optional to obtain the desired performance depending on the amount used.

As the support for the silver halide photographic material of the present invention, commonly used supports such as polyester base, TAC base, baryta paper, laminated paper, glass plate, etc. are used.

As a light source for exposing the silver halide photographic material of the present invention, a light source rich in ultraviolet rays used mainly in the printing field, such as a xenon, metal halide, mercury lamp, or ultra-high pressure mercury lamp, is used.

As the developer used in the silver halide photographic material of the present invention, either a developer used in a -shell silver halide photographic material or a lithium developer can be used. The developing agents of these developers include dihydroxybenzenes such as Teha, hydroquinone, chlorohydroquinone, and catechol, I-phenyl-3-pyrazolidone, l-phenyl-4,4dimethyl-3-pyrazolidone, and l-phenyl-4-methyl. 3-pyrazolidones such as -4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, Zaraanimata, N-methyl-p-aminophenol, 19
-(4-hydroxyphenyl)glycine-like aminophenols, β-methanesulfonamide esters,
Examples include p-7 enylene diamines such as ethylaminotoluidine, N,N-diethyl-p-phenylene diamine, and ascorbic acids.
It is used as an aqueous solution containing more than one. Other developer solutions include preservatives such as sodium sulfite, potassium sulfite, formaldehyde sodium bisulfite, hydroxylamine, ethylene urea, and development inhibitors such as inorganic salts such as sodium bromide, potassium bromide, potassium iodide, etc. , l-7enyl-5-mercaptotetrazole, 5-nitropentzimidazole, 5-nitropenttriazole, 5-nitrointasole, 5-methyl-benztriazole, 4
- one or more organic inhibitors such as thiazoline-2-thione, alkaline agents such as sodium hydroxide, potassium hydroxide, jetanolamine, triethanolamine, 3-diethylamino l-propanol, 2-methylamino -I
- Alkanolamines with a development accelerating effect such as ethanol, 3-diethylamino-1,2-propanediol, diisopropylamine, 5-amino-1-pentanol, 6-amino-1-hexanol, sodium carbonate, sodium phosphate , buffering agents that have a buffer effect in developing solutions such as aqueous carbonate and phosphoric acid solutions, salts such as sodium sulfate, sodium acetate, and sodium citrate, sodium ethylenediaminetetraacetate, sodium nitrotriacetate, sodium hydroxydiaminetriacetate, etc. Water softeners due to their chelating effect, developer hardeners such as glutaraldehyde, solvents for developing agents and organic inhibitors such as diethylene glycol, dimethyl formaldehyde, ethyl alcohol, benzyl alcohol, methyl imidacillin, methyl imidazole, polyethylene Grifur,
It is constructed by adding a development regulator such as dodecylpyridinium bromide.

The pH of the developer is not particularly limited, but is preferably in the range of 9 to 13.

An example of the composition of a preferable developer for developing the silver halide sensitive material of the present invention is as follows. Hydroquinone 20-60y/Q and H-phenyl-4 as developing agents
-Methyl-4-hydroxymethyl-3-pyrazolidone 0
．． 1 to 29/12 or l-phenyl-4,4-dimethyl-3-pyrazolidone 0.1 to 29/Q, sodium sulfite 10 to 200 g/Q or potassium sulfite lO to 2009/12 as a developer preservative. Sodium bromide and potassium bromide 1-109/Q as development inhibitors for inorganic salts,
Alkanolamines 1-509/ having development accelerating effect
Q. As an organic inhibitor, for example, 5-methylbenztriazole 0.05-29/ (1, or 5-nitroindazole 0.2-29/ Acid aqueous solution (
1 mol/Q) 10-8001112/Q, add 0.1-10 g/Q of ethylenediaminetetraacetic acid disodium salt as a chelating agent, and add an appropriate alkaline agent (
Adjust the pH to 11.0-12 using e.g. potassium hydroxide).
．． It is a developer adjusted to No. 5.

The silver halide photographic material of the present invention is developed with the developer described above, and then undergoes the processes of fixing, washing with water, and drying to fix the image. At this time, there are no particular restrictions on the developing temperature and developing time in the developing process, but the developing temperature is 20°C.
~45°C1 The development time is preferably in the range of 15 seconds to 200 seconds.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but is not limited thereto.

Example 1 Silver chlorobromide emulsions 1 to 5 were prepared using the following solutions A, B and C. The amounts of sodium chloride and potassium bromide used in solution C are shown in Table 1 together with the silver halide grain composition of the prepared emulsion.

<Solution A> Ossein gelatin 179 polyisopropylene-polyethyleneoxydisuccinate sodium salt 1O% ethanol solution 5aQ
Distilled water 1280cc Solution B> Silver nitrate 170g Distilled water
410mQ <Solution C> Sodium chloride Potassium bromide in the amount listed in Table 1
Ossein gelatin in the amount listed in Table 1
Rhodium chloride trihydrate 5B polyisopropylene-polyethyleneoxydisuccinate sodium salt lO% ethanol solution
Solution B and solution C were added to 311Q solution A by a simultaneous mixing method. At this time, the insulating temperature during addition, the addition time of solutions B and C, the Ostwald ripening time after the addition, and the insulating temperature at that time are such that the average grain size of the silver halide grains after preparation is 0.20 μm. Conditions were appropriately selected so that the distribution of 90% or more of the particles fell within the range of ±0.05 μm of the average particle size. The conditions are shown in Table 2.

The mixture was dispersed by stirring to obtain emulsions 1 to 5. These emulsions are known to be monodisperse grains with an average grain size of 0.2 μm.
This was revealed by observation using a GI microscope.

Next, 6-methyl-4-hydroxy-1,33
a, 7-chitrazaindene was added in an amount of 1 g/AgX 1 mol, and the above hydrazide compound 1-formyl-[
24-(2-(2,4-di-t-pentylphenoxy)
butylamide) phenyl]hydrazide 1.09/A
Added 1 mol of polyethylene glycol
0119/ Added 1 mole of A9X. 2 g/Im" of ethyl acrylate latex polymer, and 85+a9/m" of dyes (a) to (c) with the following structure as a safety measure.
, a desensitizing dye (d) with the following structure was added at 50 mg/s.
;.

(a) Solutions (B) and (C) were added under the conditions shown in Table 2, and after Ostwald ripening, desalting and washing with water were carried out by a conventional method. (containing 30g) was added and stirred at 50° for 30 minutes (b) Compounds (e) and (f) having the following structures were added as ultraviolet absorbers at 1100 III/Otori 2.

(e) Hydroquinone, gallic acid butyl ester, and 5-nitroindazole as antifoggants.

Tetraphenylphosphonium chloride and promethacin hydrochloride each at 5 mg/l12, l-phenyl-3-pyrazolidone and diethylamino-propane1 as development accelerators.
．． 2-diol and methoxyborane, respectively 71191
01" was added.

Gelatin is 2.59/■2, A9X particles are 3 in terms of silver content.
．． The saponin solution was applied as a spreading agent onto the PUT base at a ratio of 5./II2. This emulsion layer is made into a hardening overcoat layer in which a saponin solution and 50g of mucochloric acid and 2,4-dichloro-6-triazine sodium salt as a hardening agent are added per duram gelatin so that the gelatin ratio is 1.5g/11". protected by.

The samples thus obtained were exposed to wedge light using a light room printer (Oak Seisaku Shin Co., Ltd. + (MW-215)), and then developed with the developer shown in Table 3 below at 38°C for 30 seconds, followed by fixing, washing with water, and drying. .

Table 3 Composition of developer (Developer 112) Hydroquinone 34g
1-7 enyl-4,4-dimethyl-3-pyrazolidone
0.23 g ethylenediaminetetraacetic acid disodium salt 1 g 3-diethylamino-1,2-propanediol
15g 5-methylbenzotriazole
0.4g Na, 5o376g KBr
6 g1mol/Q phosphoric acid solution
400a+Q NaOH required to make pH 11.4
Add water and remove water to obtain 1a.

Table 4 shows the results obtained through the development process.

Sensitivity at concentration 2.5, Emulsion 1 was set as 100 Expressed as relative sensitivity value.

*2 Toshiba FL40SW-NU anti-fading gold approx. 200
When irradiated under lux, it showed the best time without fogging at the end exposed area. Normal plate-making work requires at least 20 minutes. If the application is limited, it is possible to use it for about 10 minutes, but if it is not longer than 30 minutes, it will interfere with the work.

*3 ◎, ○, △ than those with higher gamma obtained by connecting density 0.3 to 3.0 points on the photographic characteristic curve.

Indicated by X. Normally, △ indicates necessary, and ◎ indicates high quality.

From Table 4, sample 1-1.1-2 using comparative emulsion 1.2 with a silver chloride content of less than 60 mol% has a light room safety time of 1 minute or less, or 5 minutes. It is short, the plate-making process is unfavorable, and the quality is not satisfactory in terms of high contrast. Sample 1-3 using comparative emulsion 3 containing a rhodium compound instead of a ruthenium compound also had a short light room safe time of 3 minutes, had poor contrast, and did not necessarily have sufficient sensitivity. On the other hand, sample 1-4.1 of the present invention using emulsion 4.5 according to the present invention having a silver chloride content of 60 mol % and containing a ruthenium compound.
-5 has good quality with sufficient contrast enhancement, which is thought to be due to the hydrazine compound, and also has a sufficient bright room safety time.

〔Effect of the invention〕

According to the present invention, the high contrast that is thought to be caused by the hydrazine compound can be sufficiently achieved in a photosensitive material that provides high quality images, and when applied to a photosensitive material for printing, the brightness that provides high quality and high contrast images can be achieved. It can be embodied as a silver halide photographic light-sensitive material for use in printing.

Claims (1)

[Claims] Contains at least 60 mol % of silver chloride, and contains from 1×10^-^9 mol of ruthenium salt per mol of silver halide.
It contains 1.0×10^-^6 moles and has the following general formula [
A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer containing at least one compound represented by I. General formula [I] R_1NHNHCOR_2 (In the formula, R_1 represents an aryl group or a pyridyl group, and this includes those having a substituent. Also, R_2 is a hydrogen atom, a phenyl group which may have a substituent, or a carbon number 1
~25 alkyl group. )