JPH01100531A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the surface sensitivity and high hardness at the time of high illuminance exposing by allowing a water soluble iridium to exist in the silver halide emulsion of a silver halide emulsion layer at the time of forming the silver halide particles, then subjecting said emulsion to sulfur sensitization. CONSTITUTION:The silver halide emulsion of the silver halide emulsion of a silver halide photographic sensitive material contg. the compd. expressed by formula I in at least one layer of hydrophilic colloid layers is the silver halide emulsion formed by allowing the water soluble iridium compd. to exist therein at 10<-8>-10<-5>mol. in 1mol. of the silver halide at the time of forming the silver halide particles then subjecting the emulsion to the sulfur sensitization. In formula I, R1 and R2 denote an aryl group or heterocyclic group; R denotes a divalent org. group; (n) and (m) respectively denote 0 or 1. Among the compds. expressed by formula I, the compd. In which R1 and R2 denote a substd. or unsubstd. phenyl group, n=m=1 and R denotes an alkylene group, is more preferable. The surface sensitivity and high contract at the time of high illuminance exposing are thereby improved.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to silver halide photographic materials, and in particular, to materials that can obtain extremely sharp gradations using a relatively stable developer during high-intensity exposure. The present invention relates to a silver halide photographic material with increased surface sensitivity, and a sensitization method for increasing the surface sensitivity of the material during high-intensity exposure.

[Conventional technology]

BACKGROUND ART In recent years, in the field of printing photolithography, color printing is rapidly becoming more common. Conventionally, in color printing, three-color separation (yellow, magenta, cyan) or four-color separation (yellow, magenta, cyan, black) of a color original is separated into blue, blue,
This has been done with a camera using green and red color filters.

However, in recent years, due to the desire for colorization and the development of electronics, color separation scanners have become popular and are used by many photoengraving companies. The light source of the Chi-Ra decomposition scanner is a kinocene lamp, a He-Ne laser,
^rA variety of flash lights such as lasers, GaAs light emitting diodes, laser lights, LED lights, etc. are installed, but all of them require flash light exposure (10-' seconds or less).
Therefore, short-time high-intensity exposure is performed, and the silver halide photographic material used therein must have sufficient characteristics for such short-time, high-intensity exposure.

On the other hand, the image to be formed requires sharp edges at the critical interface with the non-image area, and to achieve this purpose, printing photosensitive materials used for such purposes are subject to so-called "lith development". Processing suitability has been added to improve quality.

However, in lithographic development, it is mechanically impossible to contain sulfite ions, which are preservatives, in high concentrations in the developing solution, and it is natural that the stability of the developing solution is extremely poor. This is a well-known fact among businessmen.

There are several techniques for solving the instability of Paris development and obtaining high-contrast images comparable to those of Paris development, and patent documents disclose disclosures of such attempts. For example, a technique for obtaining a high-contrast image using a hydrazine compound is disclosed in JP-A-53-16623, JP-A No. 5:'-20.
No. 921, No. 53-20922, No. 53-49429
No. 5166731, No. 53-66732, No. 5
No. 3-77616, No. 53-84714, No. 53-1
No. 37133, No. 54-37732, No. 54-406
No. 29, No. 55-52050, No. 55-90940, No. 56-67843, No. 56-106244, etc.

The high-contrast image forming method using these hydrazine compounds requires that the silver halide grains contained in the silver halide photographic emulsion are substantially of the surface latent image type, as disclosed in the above-mentioned literature. . However, in the short-time high-intensity exposure mentioned above, due to the high-intensity exposure, it is essentially a surface latent image type, and high-contrast image forming methods using hydrazine compounds have problems in terms of sensitivity and high-contrast contrast. There's a problem. As a result of intensive research, the inventors of the present invention have discovered a method of increasing only the surface sensitivity of surface latent image type silver halide grains, which support high contrast technology using these useful hydrazine compounds, during short-term, high-intensity exposure. This discovery led to the present invention.

[Purpose of the invention]

A first object of the present invention is to provide a silver halide photographic material with improved surface sensitivity during high-intensity exposure using a high contrast technique using a hydrazide compound. The second object is to provide a silver halide photographic material that can produce extremely high-contrast images even when exposed to high illuminance.

A third object of the present invention is to provide a sensitization method that uses a high contrast technique using a hydrazide compound to improve surface sensitivity and high contrast level during high-intensity exposure.

[Structure of the invention]

The above-mentioned object of the present invention is to have at least one silver halide emulsion layer on a support, and at least one hydrophilic colloid layer on the side of the upper layer of the support has the following general formula: In a silver halide photographic light-sensitive material containing at least one compound represented by CI), the silver halide emulsion in the silver halide emulsion layer has a concentration of 10-8 to 1 mole of silver halide when forming silver halide grains. This can be achieved by using a silver halide photographic light-sensitive material, which is a silver halide emulsion prepared by containing 10@-5 mol of a water-soluble iridium compound and then sensitizing it with sulfur.

General formula CI) \(CO)m NHNHR2 In the formula, R and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, and n and m each represent 0 or 1.

Hereinafter, the configuration of the present invention will be specifically explained in detail.

The silver halide used in the silver halide emulsion layer of the present invention may be any of silver bromide, silver chloroiobromide, silver chlorobromide, silver chlorobromide, and silver chloride, but preferably contains 10 mol%. It is silver iodobromide or silver bromide containing not more than silver iodide. The average grain size of the silver halide grains in this silver halide emulsion layer is preferably smaller than 0.5 μm, and 90% or more of the total number of grains are so-called monodisperse, within ±40% of the average grain size. Preferably they are particles. The crystal habit of the silver halide grains may be cubic, tetradecahedral or octahedral, or may be tablet-shaped grains as disclosed in JP-A-58-108525.

The method for preparing the silver halide emulsion of the silver halide emulsion layer of 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. In addition, the ammonia method, neutral method, acid method, and
Any method such as the modified ammonia method disclosed in No. 3532 may be used.

In the present invention, a water-soluble iridium compound is added during the formation of silver halide grains in the silver halide emulsion. The water-soluble iridium compound must be present in the reaction system when silver halide grains are formed. In other words, the three processes that silver halide grains generally go through to form are "grain formation,""graingrowth," and "Ostwald ripening."
In a preferred embodiment, a water-soluble iridium compound must be present in at least one of these two processes (when particle growth and Ostwald ripening are referred to as "physical ripening" processes). A method for preparing by adding a compound can be mentioned.

The water-soluble iridium compound used in the present invention is a water-soluble iridium salt or an iridium complex compound, and specifically, iridium trihalide, iridium tetrahalide, hexahalogenoiridium (I[l) acid or its salt, hexahalogenoiridium Iridium-halogen compounds such as halogenoiridium (R') acid or a salt thereof are preferred.

The amount of the water-soluble iridium compound used in the present invention is in the range of 10-8 to 10-5 mol per mol of silver halide. If the amount of water-soluble iridium compound added is less than 10-8 mol per mol of silver halide,
If the object of the present invention is not fully achieved, and if the amount exceeds 10@-5 mol, it exhibits a desensitizing effect and a softening effect and cannot be put to practical use.

Examples of using water-soluble iridium compounds in silver halide photographic light-sensitive materials include Japanese Patent Publication Nos. 4935-1986 and 3rd Edition of Japanese Patent Publication No. 45-3.
It is described in several documents including No. 2738 and Japanese Patent Publication No. 49-33781. However, studies to date have shown that silver halide grains obtained by adding water-soluble iridium compounds only increase their internal sensitivity;
It was not known to increase surface sensitivity. However, through research conducted by the inventors of the present invention, a layer of a silver halide emulsion was obtained by sulfur-sensitizing silver halide grains produced by allowing the above-mentioned amount of a water-soluble iridium compound to be present during the formation of silver halide grains. And general formula (1)
It has been found that only the silver halide photographic emulsion layer containing the hydrazide compound represented by the following shows an increase in surface sensitivity.

In the present invention, the surface sensitivity is the sensitivity obtained by developing with a surface developer, and the sensitivity is defined as the amount of exposure necessary to reach the maximum density of 172.

An example of the surface developer is shown below.

Surface developer: Develop at a temperature of 20° C. for 10 minutes in a developer with the following formulation.

N-Methyl-P-aminophenol 2.5g Ascorbic acid 10g Sodium metaborate trihydrate 35fI Potassium bromide
Add 1g water 1
1 In the present invention, sulfur sensitization refers to sulfur sensitization as chemical sensitization. In addition to sulfur sensitization, reduction sensitization and noble metal sensitization are known as chemical sensitization methods for silver halide photographic emulsions, but reduction sensitization and/or noble metal sensitization are used in combination with sulfur sensitization. Embodiments are included in the sulfur sensitization of the present invention. In the present invention, it is preferable to perform chemical sensitization using sulfur sensitization alone. As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used. , 574,944, 2,410,689, 2,728,668, Japanese Patent Publication No. 59-11892, etc. can be applied.

Regarding general formula [I]\(CO)m-N)INH-82 In the formula, R1 and R2 represent an aryl group or a heterocyclic group, R represents a divalent organic group, and n and m are each 0 Or represents 1.

Here, examples of the aryl group represented by R1 and R2 include phenyl group, naphthyl group, etc., and examples of the heterocyclic group include pyridyl group, benzothiazolyl group, quinolyl group, thienyl group, etc. is preferably 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.), acylamino groups (e.g., acetylamino, pivallylamino, benzoylamino, tetradecanoylamino, ,4
-di-t-amylphenoxy)butyrylamino, etc.),
Sulfonylamino groups (for example, methanesulfonylamino, butanesulfonylamino, dodecanesulfonylamino, benzenesulfonylamino, etc.), urea groups (for example, phenylurea, ethylurea, etc.), thiourea groups (for example, phenylthiourea, ethylthiourea, etc.), hydroxy group, an amine group, an alkylamino group (eg, methylamino, dimethylamino, etc.), a carboxy group, an alkoxycarbonyl group (eg, ethoxycarbonyl), a carbamoyl group, a sulfo group, and the like.

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, carbonyl group, -N- group (R3 represents a hydrogen atom, an alkyl group, or an aryl group), a sulfonyl group, or the like. Various substituents can be introduced into the group represented by R.

Examples of the substituent include -CONHNHR, (R represents the same meaning as R 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, etc. It will be done.

R is preferably an alkylene group.

-8 Among the compounds represented by formula (1), preferably R1
and R2 is a substituted or unsubstituted phenyl group = n
Specific compounds in which R represents an alkylene group in m-1 = 15- The compound represented by the general formula CI) is used in an amount of 1X10-'mol-1X10-' per mol of silver halide, particularly preferably 5X10 -'Mole-1 x To add the compound represented by the general formula (1) to a composition for a hydrophilic colloid layer (including a silver halide emulsion), use the usual method of adding additives to photographic emulsions. Can be done. For example, a water-soluble compound can be used as an aqueous solution of an appropriate concentration, and a water-insoluble or sparingly soluble compound can be dissolved in an appropriate water-miscible organic solvent and added to the emulsion as a solution.

The compound represented by general formula [I] is not added to the silver halide emulsion, but is added to the coating composition for a hydrophilic colloid layer other than the silver halide emulsion layer and diffused into the silver halide emulsion layer after the layer is formed. It may be moved.

Silver halide emulsions to which the above-mentioned sensitization method according to the present invention is applied are provided with photosensitivity in desired wavelength ranges.
Optical sensitization may be performed using one or more sensitizing dyes. Various sensitizing dyes can be used, but optical sensitizing dyes that can be advantageously used in the present invention include cyanines, carbocyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or These optical sensitizing dyes include tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols, hemioxonols, etc., and these optical sensitizing dyes contain thiazoline as part of their structure as a nitrogen-containing heterocyclic nucleus. , a basic group such as thiazole, or a nucleus such as rogenine, thiohyguntoin, oxazolidinedione, barbylic acid, thiobarbital acid, pyrazolone, etc., and such a nucleus may be substituted with alkyl, hydroxyalkylhalogen, phenyl, cyano, or alkoxy. These optical sensitizing dyes may also be fused with a carbocyclic or heterocyclic ring.

The silver halide emulsion to which the sensitization method of the present invention has been applied includes stabilizers such as tetrazaindenes, antifoggants such as triazoles and tetrazoles, covering power improvers, and irradiation inhibitors such as oxanol dyes. , dialkylaminobenzylidene dyes, etc., polymer latexes as wetting agents, and other additives such as spreading agents, hardening agents, etc., which are incorporated in common photographic emulsions, 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. can be used.

As the developer used in the silver halide photographic material of the present invention, either a developer used in general silver halide photographic materials or a lithium developer can be used. The developing agents of these developers include dihydroxybenzenes such as hydroquinone, chlorohydroquinone, and catechol, 1-phenyl-3-pyrazolidone, 1-phenyl-4.4-dimethyl-3-pyrazolidone, and 1-phenyl-4. 3-pyrazolidones such as -methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and also N-methyl-p-aminophenol. , N-(4-h droxyphenyl)glycine-like naparamino-7-ols, β-methanesulfonamide ester, ethylaminotoluidine, N,N-diethyl-p-
Examples include p-phenylene diamines such as phenylene diamine, and ascorbic acids, and are used as an aqueous solution containing one or more of such developing agents. In addition, the developer contains preservatives such as sodium sulfite, potassium sulfite, formaldehyde sodium bisulfite, hydroxylamine, ethylene urea, and inorganic salts such as sodium bromide, potassium bromide, potassium iodide, etc. to inhibit development. agent, 1-phenyl-5-mercaptotetrazole, 5-nitrobencyimiguzole, 5-nitrobenzotriazole, 5-
one or more organic inhibitors such as nitroingzole, 5-methyl-benzotriazole, 4-thiazoline-2-thione, etc., alkaline agents such as sodium hydroxide, potassium hydroxide, jetanolamine, triethanolamine, 3
-diethylamino-1-propatol, 2-methylamino-1-ethanol, 3-diethylamino-1,2-propanediol, diisopropylamine, 5-amino-
Alkanolamines that have a development accelerating effect such as 1-pentanol and 6-amino-1-hexanol; buffer agents that have a buffering effect in developing solutions such as sodium carbonate, sodium phosphate, aqueous carbonate solutions, and aqueous phosphoric acid solutions; sulfuric acid; salts such as sodium, sodium acetate, and sodium citrate, water softeners with chelating effects such as sodium ethylenediaminetetraacetate, sodium nitrotriacetate, sodium hydroxydiaminetriacetate, developer hardeners such as glutaraldehyde, diethylene glycol, Use a product made by adding a developing agent such as dimethyl formaldehyde, ethyl alcohol, benzyl alcohol, a solvent for an organic inhibitor, a development regulator such as methyl imidacillin, methyl imidazole, polyethylene glycol, dodecylpyridinium bromide, etc. be able to.

The pH of the developer is not particularly limited, but is preferably in the range of p) 19 to 13.

An example of the composition of a preferable developer for developing the silver halide photographic material of the present invention is as follows. Hydroquinone 20-60 g/l and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0.1-2 g/l or 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.1 as developing agent. ~2g/It, sulfite as developer preservative) 17um 10-200g/l or potassium sulfite 10-200. /I, sodium bromide or potassium bromide 1-10-5 as an inorganic salt development inhibitor
0 g/12, organic inhibitors such as 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 phosphoric acid as buffering agents. Aqueous solution (II
Ilof/i') 1010-8O0/l, noethylenediaminetetraacetic acid disodium salt as chelating agent 0.
1~10 g/jl! and a suitable alkaline agent (
For example, use potassium hydroxide to adjust the pH to 11.0-12.
．． 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 a process of fixing, washing with water, and drying to fix an image. At this time, there are no particular restrictions on the development temperature and development time in the development process, but the development temperature is preferably in the range of 20 to 45°C and the development time is in the range of 15 seconds to 200 seconds.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

(Example) Silver nitrate aqueous solution and halide aqueous solution (KBr 98 llol%, KI2m
o1%) at the same time for 50 minutes, during which pAg was increased to 7.
．． 5, four types of monodisperse silver iodobromide emulsions having an average grain size of 0.25 μm and having different amounts of added iridium compounds shown in Table 1 below were prepared. Using potassium hexachloroiridate (■) as a water-soluble iridium compound,
Each was added to an aqueous halide solution.

After these emulsions were desalted and washed with water in a conventional manner, 15 B of sodium thioshironate was added per mole of silver iodobromide, and chemical ripening was performed at 60° C. for 60 minutes.

Next, this emulsion was added to 6-methyl-4-hydroxy-1,3
゜1g/^Bx1 mol of 3a-tetrazaindene was added, and 1 g of KBr was added per mol of silver as a fog suppressant.
Nnall, 5g, 5-methylbenzotriazole 10
0mg, 1-phenyl-5-mercaptotetrazole 100mg, anhydro-5,5-dichloro-9-ethyl-3°3'-bis(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt as a sensitizing dye 200B/ 1 mol of ^gX and a dye having the following structure were added.

Add 30 mg/^g x 1 mole or 250 mg/^g x 1 mole of polyethylene glycol, and then add samples N011 to N004 as shown in Table-2.
is a hydrazide compound of general formula 1-(10), and 1
．． 0g/^gX1 mole was added.

To the emulsion thus obtained, 2 g/m2 of ethyl acrylate latex polymer and 25 g/m2 of gelatin were added.
The saponin solution was added as a spreading agent and coated on a polyethylene terephthalate base so that the amount of heg×particles was 3.5 g/m 2 in terms of silver amount. This emulsion layer is coated with gelatin 1
．． It was protected by a hardening overcoat layer containing a sodium dodecylbenzenesulfonate solution and mucochloric acid and formalin as hardeners to give a concentration of 5 g/m2.

For the sample obtained in this way, the output is 10III+1^
Exposure was carried out using r laser light (emission wave ftE, 488 nm) for an exposure time of 10-6 seconds, and while changing the light intensity stepwise.

Next, development using the surface developer shown in Table 3 and Table 4
Two types of development treatments were performed: development using an internal developer shown in .

Table 3 Surface development: N-
Methyl-p-aminophenol 2.5g Ascorbic acid 10g Sodium metaborate.
Industrial hydrochloric acid 35g Potassium bromide
1g=32- Table-4 Internally developed red blood salt 3g7N and phenosafranin 0.0125g#
! After processing for 10 minutes at 20°C in a bleaching solution containing
N-methyl-p-aminophenol 2.5 Piascorbic acid tog Sodium metaborate trihydrate 358 Potassium bromide
1g sodium thiosulfate 3
gThe results are summarized in Table-5.

Expressed as relative sensitivity.

From Table 5, the following can be said.

(1) Samples based on the present invention have significantly higher surface sensitivity in high-intensity exposure than samples outside the present invention.

(2) Based on the fact mentioned in the previous section and the fact that the sample of the present invention is not particularly sensitized in terms of internal sensitivity under high-intensity exposure,
The sensitization method of the present invention is extremely effective as a means for increasing surface sensitivity during high-intensity exposure.

Next, exposed samples similarly exposed to laser light are shown in Table 6 below. The film was developed with a developer for 30 seconds at 38°C, followed by fixing, washing with water, and drying.

Table 6 Composition of developer (Developer IN) Hydroquinone 34 g 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.23 g Ethylenediaminetetraacetic acid disodium salt g 3-diethylamino-1,2-propanediol 5 g 5-methyl Benzotriazole 0.4gNa2
S0,76g NaBr
3 gNILCI
1.31?1 mol, #
Phosphoric acid solution 400mNpn 11.4
14 with condensed water to which NaOH is added.

Table 7 shows the results of the development process.

relative sensitivity.

**Gamma of the straight line connecting density 0.3 to 3.0 points on the characteristic curve.

Indicated by ◎, ○, △, and × in descending order of gamma.

Normally, the ○ level is required.

As is clear from the results in Table 7, sample No. 002 contains a small amount of iridium salt even though it contains a hydrazide compound.
Sample No. 1 has the same high contrast as sample No. 1 without the addition of iridium salt, but the sensitivity (surface sensitivity) is significantly lower. Sample No. 3 in the present invention has high sensitivity by adding a specific amount of iridium salt. and ultra-high contrast have been achieved. Considering this together with the results of i-5, it is presumed that the higher sensitivity was brought about by the increased surface sensitivity.

Also, instead of laser light, infrared semiconductor laser light (
It was confirmed that the same effect could be obtained even when exposed to light with an emission wavelength of 780 μm).

In addition, when samples No. 1 and No. 3 were exposed to light using a tungsten lamp (exposure time 10 seconds) and treated with the developer shown in Table 6, the sensitivities were almost the same. As a result of performing the surface development and internal development shown in -4, no difference was observed in the surface sensitivity and internal sensitivity.

〔Effect of the invention〕

Surface sensitivity and high contrast level during high-intensity exposure of a silver halide photographic material using high contrast technology using a hydrazide compound are improved.

Applicant: Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Scope of Claims] It has at least one silver halide emulsion layer on a support, and in this layer and/or at least one hydrophilic colloid layer on the side of the layer on the support, the following general formula [ In a silver halide photographic light-sensitive material containing at least one compound represented by I], the silver halide emulsion in the silver halide emulsion layer has a concentration of 10^-^ per mole of silver halide when silver halide grains are formed. 1. A silver halide photographic light-sensitive material, characterized in that it is a silver halide emulsion prepared by sulfur sensitization in the presence of 8 to 10^-^5 moles of a water-soluble iridium compound. 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.