JPH01105941A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the title material which has the high quality and the high contrast and is suitable for roomlight handling by incorporating a prescribed amount of silver chloride, a water soluble rhodium salt and a specified hydrazide compd. in a silver halide emulsion layer. CONSTITUTION:The silver halide photographic sensitive material contains at least 80mol.% silver chloride and 1X10<-8>-1.0X10<-4>mol. of the water soluble rhodium salt per 1mol. of silver halide and provides with at least one layer of the silver halide emulsion layer contg. at least one kind of the hydrazide compd. shown by the formula wherein R1 and R2 are each aryl or a heterocyclic ring group, R is a divalent org. group, (n) and (m) are each 0 or 1. The usable silver halide may be any one selected from the group comprising silver chloride, silver chlorobromide, silver chloroiodide and silver chlorobromoidide, but contains >=80mol.% silver chloride. The water soluble rhodium salt is preferably exemplified by a complex compd. of a trivalent rhodium halide such as hexachlororhodiumic acid or its salt. The compounding amount of the compd. shown by the formula is preferably in a range of 1X10-8-1X10<-4>mol., more preferably a range of 1X10<-7>-1X10<-8>mol. per 1mol. of silver halide.

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, the use of a bright room in 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 so-called lithographic processing and are made to be of high quality. is insufficient.

On the other hand, as a technique for obtaining a high-contrast image comparable to the "lithographic development process," patents can be found regarding several attempts. In addition, Japanese Patent Application Laid-Open No. 53-1 discloses a technique for obtaining high-contrast images using hydranone compounds.
No. 6623, No. 53-20921, No. 53-2092
No. 2, No. 53-49429, No. 53-66731,
No. 53-66732, No. 53-77616, No. 53
-84714, 53-137133, 54-3
No. 7732, No. 54-40629, No. 55-5205
No. 0, 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 No. 56-106244, by containing a hydrazine compound and a development-promoting amount of a 7-mino compound during image formation, high-contrast images can be produced at a relatively low pH.
(11 to 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 have succeeded in establishing the technical applicability of high contrast enhancement technology using these useful hydranone compounds to light-sensitive light-sensitive materials, which currently have the highest demand for high quality.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a silver halide photographic light-sensitive material for use in a bright room, which provides high-quality, high-contrast images. A second purpose is to make it possible to apply the high contrast enhancement technology using a hydranode 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 80 mol% silver chloride, and
lXl0− of water-soluble rhodium salt per mole of silver halide
This was achieved by a silver halide photographic light-sensitive material containing at least one hydrazide compound represented by the symbol [+] below.

-Momona CI) In the formula, R and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, and n and 1 each represent O or 1.

Hereinafter, the configuration 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 light emission distribution of commonly used bright indoor lights is on the longer wavelength side than 400 nn. 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.

The water-soluble lonotum salt used in the present invention includes:
Examples include rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, etc., but preferred is a halogen complex compound of trivalent rhodium, such as hexachlororhodic acid (ill) acid or a salt thereof.

In the present invention, the amount of the water-soluble rhodium salt added is 1.0% per mole of silver halide. OX 10-1′ mol ~ 1.0×1
It is 0-4 mol. When the amount of water-soluble rhodium salt is less than 1.times.10@-1 mol, the sensitivity will not be reduced to the level required for a light-sensitive material, which is the object of the present invention.

In the present invention, the water-soluble rhodium salt is preferably present at the time of preparing the silver halide emulsion, but the time of preparation refers to the process of emulsification and physical ripening, and the water-soluble rhodium salt may be added at any time during this process and by any method. A good but preferred addition time is during emulsification, and a particularly preferred method is a method in which the water-soluble lonorum salt is added to the halide solution. This is because, in order to maximize the desensitizing effect of rhodium, rhodium atoms must be uniformly distributed from the interior to the surface of silver halide grains, and for this reason, it is preferable to add rhodium atoms to the halide solution.

Next, the hydrazide compound represented by the general formula (1) according to the present invention is shown as follows.

- Monana [I] In the formula, R and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, and n and I each represent 0 or 1.

Here, examples of the 7-aryl group represented by R1 and R2 include a phenyl group, a naphthyl group, etc., and examples of the heterocyclic group include a pyridyl group, a benzothiazolyl group, a quinolyl group, a thienyl group, etc.; Preferred is an aryl group.

Various substituents can be introduced into the aryl group or heterocyclic group represented by R1 and R2. Examples of substituents include halogen atoms (e.g., chlorine, fluorine, etc.), alkyl groups (e.g., methyl, ethyl, dodecyl, etc.), alkoxy groups (e.g., methoxy, ethoxy, impropoxy, butoxy, octyloxy, dodecyloxy, etc.), and acylamine 7 groups (e.g. acetylamino, piperylamino, benzoylamino, tetradeca/ylami/, α-(2,
4-not-t-amylphenoxy)butyrylamine 7, etc.)
, sulfonyl amine 7 groups (e.g., methanesulfonyl amine/, butanesulfonyl amine/, tricansulfonylamino, benzenesulfonyl amine 7, etc.), urea groups (e.g., phenyl urea, ethyl urea, etc.), thiourea groups (e.g., phenyl thio thurea, ethylthiourea, etc.), hydroxy group, 7 ami groups, 7 alkyl ami groups (
Examples include methylamino, dimethylamino, etc.), carboxy groups, alkoxycarbonyl groups (eg, ethoxycarbonyl), carbamoyl groups, and sulfo groups. Examples of the divalent organic group represented by R include alkylene groups (e.g., methylene, ethylene, trimethylene, tetramethylene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.), aralkylene groups, etc. The bond may contain an oxy group, thio group, seleno group, carbonialyl group), sulfonyl group, etc. Various substituents can be introduced into the group represented by R″C″.

Examples of substituents include C0N11NIIR4(R4
has the same meaning as R1 and R2 described above), an alkyl group, an alkoxy group, a halogen atom, a hydroxy group, a carboxy group, an acyl group, an aryl group, and the like.

R is preferably an alkylene group.

- Of the compounds represented by Monna [■], preferably R3
and R2 is a substituted or unsubstituted phenyl group, and n''
+a=1 and R represents a fullkylene group.

Specific compound The compound represented by the general formula (1) is used in an amount of 1X10-'mol-1X10-'' mol per 1 mol of silver halide, particularly preferably in an amount of 1X10-7 mol-1×to-' mol. Good addition.

In order to add the compound represented by the general formula (11) into the emulsion, the usual method of adding additives in photographic emulsions can be used. For example, water-soluble compounds can be added to an aqueous solution with an appropriate concentration and are insoluble or insoluble in water. A poorly soluble compound can be used by dissolving it in a suitable organic solvent that is miscible with water and adding it to the emulsion as a solution.

The method for producing emulsion 71i in the present invention includes a forward mixing method,
Either a single jet method such as a back mixing method or a double jet method such as a simultaneous mixing method may be used.

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 a goblet type grain as disclosed in JP-A-58-108525. The particle size is preferably 0.5μ or less, but is not particularly limited.

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 thus prepared may contain stabilizers such as tetrazaindenes, anti-capri agents such as triazoles and tetrazoles, covering power improvers, and irradiation inhibitors such as oxanol dyes and sialkyl amines. /Benzylidene dyes, etc., polymer latexes as wetting agents, and other additives used in general photographic emulsions such as spreading agents, hardening agents, etc. can be added.

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 Canon, 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 commercial silver halide photographic material or a Lithium developer can be used.

The developing agents of these developers include dihydroquinone, chlorohydroquinone, dihydrobenzenes such as catechol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-tumethyl-3-pyrazolidone, 1-phenyl- Examples include 3-pyrazolidones such as 4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and also N-methyl-p-amino Phenol, paraamino 7-ethers such as N-(4-hydroxyphenyl)glycine, β-methanesulfonamide ester, ethyl alcohol, N,N-diethyl-p
Examples include p-phenylenediamines such as -phenylenediamine and ascorbic acids, and are used as an aqueous solution containing one or more of such herbal medicines. Other developer solutions include sodium sulfite, potassium sulfite, formaldehyde sodium bisulfite, hydroxylamine, preservatives such as ethylene urea, sodium bromide, potassium bromide,
Development inhibitors of inorganic salts such as potassium iodide, 1-phenyl-5-merca7'') te)razole, 5-nitropentzimiguzole, 5-nitrobenztriazole, 5-
one or more organic inhibitors such as nitroingzole, 5-methyl-benztriazole, 4-thiazoline-2,000, etc., alkaline agents such as potassium hydroxide, noethanolamine, Triethanolamine, 3-diethylamino/-1-propanol, 2-methylamino-1-ethanol, 3-diethylamino-1,2
- Alkali-amiso compounds having a development accelerating effect such as propantool, noisobrobylamine, 5-amino-1-pentanol, 6-7minor-1-hexanol, sodium carbonate, sodium phosphate, aqueous carbonate solution, phosphorus Chelation of buffering agents with buffing effect in developing solutions such as acid aqueous solutions, salts such as sodium sulfate, sodium acetate, sodium citrate, sodium ethylenediaminetetraacetate, sodium nitrotriacetate, sodium hydroxydiaminetriacetate, etc. Water softeners, developer hardeners like glutaraldehyde, diethylene glycol,
It is composed of additives such as developing agents such as dimethyl formaldehyde, ethyl alcohol, and benzyl alcohol, solvents for organic inhibitors, and development regulators such as methyl amigzolin, methyl amigsol, polyethylene glycol, and dodecylpyridinium bromide. do.

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 20-60g/Z and 1-phenyl-4 as developing agent
-Methyl-4-hydroxymethyl-3-pyrazolidone 0
．． 1-2 g/Il or 1-phenyl-4,4-tumethyl-3-pyrazolidone 0.1-2 g/l, sodium sulfite 10-200 g/l or potassium sulfite 10-200 g/l as a developer preservative, Sodium bromide and potassium bromide 1 to Log/l as development inhibitors for inorganic salts, and alcamel amines having a development accelerating effect 1 to 50 g/l
1. As an organic inhibitor, for example, 0.05 to 2 g/l of 5-methylbenztriazole or 0.01 to 2 g/l of 5-nitroingzole, 1 to 50 g/l of sodium carbonate or an aqueous phosphoric acid solution as a buffer agent ( 1mol/
ff1) 10-800z1/1, ethylenediaminetetraacetic acid disodium salt as chelating agent 0.1~
1 (h/l) and the pH is adjusted to 11.0 to 12.5 using an appropriate alkaline agent (for example, potassium hydroxide).

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°C and development time 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 17g polyisopropylene-polyethylene oxynosuccinate sodium salt 10% ethanol solution 'eL
5nl distilled water 1280c
Solution B〉 Silver nitrate 170g Distilled water
410xl Solution C> Sodium chloride Potassium bromide in the amount listed in Table 1
Ossein gelatin in the amount listed in Table 1
l1g rhodium trichloride trihydrate 5II1
g Polyisopropylene-polyethylene oxydifusuccinate sodium salt 10% ethanol solution
3x1 distilled water 41
2zi' Table 1 Silver halide composition and amount of added sodium chloride and potassium bromide 9 Water-soluble rhodium salt was added to solution C Rhc/, 311□0
As a result, 1.9X10-' mole/ΔgX1 mole is added.

Solution B and solution C were added to the solution by a simultaneous mixing method. Insulation temperature during addition and solution B and solution C at this time
The addition time, 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, and the grain size distribution is within the range of ±0.05 μm of the average grain size. Conditions were appropriately selected so that 90% or more of the particles were contained. The conditions are shown in Table 2.

Soluble a(B) and (C) were added under the conditions shown in Table 2, and after Ostwald ripening, desalination and water washing were carried out in the usual manner, and then 600L of an aqueous solution of ossein gelatin! (containing ossein gelatin 309) was added and dispersed by stirring at 55° C. for 30 minutes to obtain emulsions 1 to 5. Observation with an electron microscope revealed that these emulsions were monodisperse grains with an average grain size of 0.2 μm.

Next, 1g/8gX1 mol of 6-methyl-4-hydroxy-1,3゜3a,7-chitrazaindene was added to this emulsion, and 1.0g/^gX1 of the hydrazide compound 10 of general formula [I] was added. In addition, polyethylene glycol was added at 250 ag/^gX1 mole, ethyl acrylate latex polymer was added at 2 g/112, gelatin Z was added at 5 g/m', and gx particles were added at 3.5 g/m in terms of silver amount.
m2 and PE using the saponin solution as a spreading agent.
Coated on T base. This emulsion no gelatin 1.5
It was protected by a hardening overcoat layer containing a saponin solution and mucochloric acid as a hardening agent to give a concentration of 112 g/l.

The thus obtained sample was exposed to wedge light using a light room printer (Oak Seisakushin Co., Ltd. +1H-215), and then developed for 130 seconds at 38 DEG C. with the developer shown in Table 3 below, followed by fixing, washing with water, and drying. Margin below -1 Table 3 Composition of developer (Developer 11) Hydroquinone 34 g
l-phenyl-4,4-dimethyl-3-pyrazolidone
0.23g ethylenediaminetetraacetic acid disodium salt 1g 3-diethylamino-1,2-propanediol
15F15-methylbenzotriazole
0.4g Na25O:+
76 gNa8r
3 ET1+aol//phosphoric acid solution 400+n1pHl
11 with condensed water added with Na0II necessary to make 1,4
shall be.

Table 4 shows the results of the development process.

Margin Table 4: Photographic Performance Book 1 of Each Sample Sensitivity at a density of 2.5 is shown below as a relative sensitivity value with Emulsion 5 set as 100.

Book 2 Next Summer! Approximately 20 FL40S A/NU anti-fading lights
When irradiated under 0 lux, it showed the best time without fogging in the exposed area. At least 20 for normal plate-making work
minutes are necessary. If the application is limited, about 10 minutes is possible, but if it is not longer than 30 minutes, the work will be hindered.

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

Indicated by ×. Usually Δ is necessary, and ◎ indicates high quality.

From the results shown in Table 4, the following can be said.

The higher the ratio of ^gCQ in the silver halide grain composition of the sample, the lower the sensitivity and the better the light room safety time. Regarding the degree of detuning, all samples have very high contrast and are of high quality, but (1) light room safe time 2
Samples (1-1) and (1-2) with a diameter of less than 100 yen cannot be used for normal plate-making work.

(2) From the above, the performance required as a light-sensitive material can be obtained by samples (1-3), (1-4), and (1-5) of the present invention.

Example 2 Emulsion 5 shown in Example 1 was used to evaluate the hydrazide species to be added. Among the sample preparation methods shown in Example 1, only the hydranode compound to be added was changed to the following compounds, and the others were the same. Furthermore, the same developer as in Example 1 was used.

After performing wedge exposure in the same manner as in Example 1, a sample was obtained through the processes of development, fixing, washing with water, and drying.

(Comparison) All hydrazide compounds are approximately 2X10-'mol/^g
XI moles were added.

From the results shown in Table 5, the following can be said.

1. Sample without addition of hydrazide compound (2-1)
Although the sensitivity is low, the tone is very soft and cannot be put to practical use.

2. The hydrazide compound of the present invention has practical utility, but it is difficult for hydrazine compounds other than the present invention to achieve the purpose of the present invention.

Example 3 Eleven types of silver chlorobromide emulsions were prepared using the following solutions A, B, and C. At this time, the amount of rhodium chloride trihydrate in solution C was added as shown in Table 6.

[Solution A]

Ossein gelatin 17g polyisopropylene-polyethyleneoxysuccinic acid ester sodium salt 10% ethanol solution
5mN distilled water 128
0cc [Solution B] Silver nitrate 170g Distilled water
410ml [Solution C] Sodium chloride 74.81g Potassium bromide 2.38g Ossein gelatin 11g Polyisopropylene-polyethylene oxydisuccinate sodium salt 1
0% ethanol solution 5Illll
Rhodium trichloride trihydrate Table 6: Distilled water
Solution B and solution C were added to 412mj' solution A by simultaneous mixing method over 40'040 minutes. After the addition was completed, Ostwald ripening was performed for 40'010 minutes, and then desalination and water washing were carried out in the usual manner. Then, 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) was added and stirred at 55°C for 30 minutes to perform dispersion and obtain each emulsion.The emulsion consisted of monodisperse particles with an average particle size of 0.20 μm. Met.

A coating emulsion was prepared using the same hydrazide compound as in Example 1, coated, and dried to obtain a sample. At this time, the sample (3-1
For 2), add 1 mole of sodium thiosulfate Gokisalt to the same emulsion as (3-10) at 55°C and 40°C.
After chemical aging for a minute, 6-methyl-4 was added as a stabilizer.
-Hydroxy-1t3t3at7-titrazaindene was added to Ig/8g x 1 mol. For this sample only,
No hydrazide compound was added and other additives were used in sample (3).
-1) to (3-11), and samples were obtained after coating and drying in the same manner.

After the samples obtained in this way were subjected to wedge exposure under the same exposure conditions as in Example 1, samples (3-1) to (3-11) were
was processed with the developer shown in Example 1. For sample (3-12), developer CD manufactured by Konishiroku Photo Industry was used.
It was developed with M-621 at 38°C for 20 seconds.

The samples thus obtained were evaluated for photographic characteristics such as sensitivity, degree of detuning, and light room safety time, and the results are summarized in Table 6. The sensitivity is expressed as a relative sensitivity when (3-12), which is a sample of a commonly used bright room photosensitive material processed with a common rapid access developer, is taken as 100. Other evaluation methods were based on Example 1.

Below/bottom margin Table 6 Added Rh amount and photographic performance of each sample From the results shown in Table 6, the following can be said.

1, RhCl, -31120 (7) addition jl b
' I It cannot be put to practical use.

2. The amount of RhCf3・3H20 added is 1. OX1
Those in the range of 0-' to 1.0 x 101 mol/^gX1 mol have slightly higher sensitivity and shorter light room safety time, but are considered to be practical.

3. The amount of RhC1,・3■20 added is 5. OX1
0-'~1. Those in the range of O x 10 -S mol/^g

4, RhC4,-3uzonomkaJlkaL,O
If the ratio exceeds X 10-' mol/AgX 1 mol, no contrast enhancement effect due to the hydrazide compound is observed, and there are problems in terms of photographic performance and quality, and it is considered that they cannot be put to practical use.

5. From the above, the amount of RhCl3・3H20 added is 1
．． Within the range of 0 x 10-s mol - lXl0-' mol/^gX 1 mol, it was possible to obtain a high-quality light-sensitive material with high contrast and a long light-room safe time.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic light-sensitive material for bright room reversal that gives high-quality, high-contrast images.

Applicant: Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] Contains at least 80 mol% silver chloride, and contains 1 x 10^-^8 mol to 1.0 x 10^-^4 mol of water-soluble rhodium salt per mol of silver halide. , and at least one silver halide emulsion layer containing at least one hydrazide compound represented by the following general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 and R_2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, and n and m each represent 0 or 1. represent.