JPH01304450A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable an exposing process using an argon laser scanner to be operated in a light room by incorporating silver halide grains composed of silver chloride formed in the presence of a specified compound, and another specified compound in a silver halide emulsion layer formed on a support. CONSTITUTION:At least one silver halide emulsion layer formed on a support contains the silver halide grains composed of >=50mol% silver chloride formed in the presence of the compound represented by formula I and the compound represented by formula II, and in formulae I and II, Z is a nonmetallic atomic group necessary to form a hetero ring; X is H or the like; R1 is alkyl; each of Z1 and Q is a nonmetallic atomic group; and m is 1 or 2, thus permitting the exposure process using the argon laser scanner to be operated in the light room, and the obtained photosensitive material to be enhanced in sensitivity to the argon laser beams.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material suitable for use in an argon laser scanner.

[Background of the invention]

In recent years, in the field of printing and plate making, in response to demands for labor savings, rationalization, and improvement of the working environment, various companies have developed combinations of photosensitive materials for printing that can be handled in a bright room and exposure equipment that uses a light source rich in ultraviolet light. For this reason, the use of bright rooms has progressed considerably in the turning process, that is, the process of applying photographic paper to the original and reversing it after exposure, but in other processes there are problems such as the sharing of light source wavelengths, light source output, and work processes. Since then, no attempt has been made to make the room brighter.

However, recently, argon laser light (wavelength 488 nm)
) With the spread of scanners using scanners, there has been a demand for a bright room during the exposure process.

Conventionally, scanners that use an argon laser as a light source use blue-green sensitive photosensitive materials. However, since blue-green sensitive photosensitive materials are exposed under yellow safety lights, it is difficult to use them in a bright room. Recently, instead of blue-green sensitive materials, blue-sensitive materials, which are less sensitive to light even under yellow safety lights, have been developed.
The safety time under yellow safety lights is still short. Furthermore, when a blue-sensitive sensitizing dye is used, the emulsion sensitivity is generally low, and an attempt to increase the emulsion sensitivity to the required level increases fog. Therefore, it is desired to develop a photosensitive material that can perform the exposure process using an argon laser scanner in a bright room, has high sensitivity to argon laser light, and has less fog.

[Object of the Invention] The present invention has been made to solve the above problems, and the purpose of the present invention is to provide a device that can be handled under a yellow safety light, has little fog, and is highly resistant to argon laser light. An object of the present invention is to provide a silver halide photographic material having high sensitivity.

Another object of the present invention is to provide a silver halide photographic light-sensitive material that has excellent high contrast and sharpness, which are necessary photographic performances as a light-sensitive material for printing.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer contains a compound represented by the following general formula [■]. This is achieved by a silver halide photographic material containing silver halide grains containing 50 mol % or more of silver chloride and a compound represented by the following general formula [I[].

General formula (1) % formula % In the formula, Z represents a nonmetallic atomic group necessary to form a 5- or 6-membered heterocycle. However, the heterocycle does not contain a sulfo group or a carboxyl group as a substituent. Or represents a hydrogen atom, an alkali metal atom, an ammonium group, or an organic amine residue.

General formula CI'l] In the formula, R1 is an alkyl group, Zl is a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, and Q is a nonmetallic atom necessary to form a 5-membered heterocycle. The group m represents an integer of 1 or 2.

The present invention will be explained in more detail below.

In the general formula (I), the 5- or 6-membered heterocycle formed by Z is preferably imidazole, thiazole, oxazole, penzimitazole, benzothiazole, benzoxazole, oxadiazole,
Thiadiazole, triazole, tetrazole, pyrimidine, triazine, te!・Razindene etc. can be mentioned.

These heterocycles may have substituents, such as halogen atoms and groups such as alkyl, amino, hydroxyl, aryl, acylamino, and sulfonamide.

Next, typical examples of the compound represented by the general formula [■] will be listed, but the invention is not limited thereto.

(Exemplary compound) C2115C2[(5 1τ1 convex 1 (9) (1,0) CO.

(El) (1
2-CHs NH2 These compounds represented by the general 2 [■] that can be used in the present invention are described, for example, in U.S. Pat.
, 324,123, 2,384.593, 2゜496.940, 3. ], No. 37.578, same 2,
No. 496,940, No. 3゜082.088, No. 3,4
No. 73,924, No. 3, No. 575, No. 699, No. 3゜687.660, No. 2.27], No. 229, No. 2,4
No. 96,940, British Patent No. 1,141.773, No. 1
, 376.600, etc., or can be easily synthesized according to the method described therein. Also, edited by Munio Kotake,
Great Organic Chemistry (Asakura Shoten, 1971 edition) or Ni.
Weissber: The Chemistry of Heterocyclic Compounds (A, Weissber)
ger：The Chemistry of Heter
cocyclic compounds N, Y, In
terscience.

1950-1964), or according to the method described therein.

The amount of the compound represented by the general formula [I] according to the present invention added is I x 10 per mole of silver halide.
-5 to IX 10-3 moles are preferred. If the amount added is less than the above amount, it will not be effective in preventing fog or under a safety light, and if the amount added is more than the above amount, the sensitivity will be greatly reduced.

Next, the blue-sensitive sensitizing dye represented by the general formula CU] will be explained.

In the general formula [II], examples of the heterocycle formed by zl include deazole, selenazole, oxazole, benzothiazole, benzoselenazole, benzoxazole, naphthothiazole, naphthoselenazole, naphthoxazole, hiricine, gynoline ring, etc. Further, these heterocycles may have a substituent, and these 1n substituents include, for example, a halogen atom (e.g., chlorine, bromine, etc.), an alkyl group, preferably a carbon number 1
~4 alkyl groups (e.g. methyl, ethyl, propyl)
, a halogenated alkyl group (for example, trifluoromethyl, etc.), an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, propyloxy, etc.)
, a hydroxyl group, an aryl group (eg, phenyl, etc.), and the like.

Examples of the heterocycle formed by Q include rhodanine, thiohydantoin, dioxazolidinedione, thioselenazolidinedione rings, etc. These heterocycles may have a substituent, and these substituents The group is preferably an alkyl group having 1 to 8 carbon atoms (e.g. methyl, ethyl, propyl, 2-hydroxyethyl, 2-hydroxyethyloxyethyl, 2-methyl-xyethyl, 2-acetoquinethyl, carboxymethyl, 2- Carboxyethyl, 3-carboxypropylbutyl, 2-sulfoethyl, 3-sulfopropyl, 3-
sulfobutyl, 4-sulfobutyl, benzyl, phenethyl, butyl, etc.), aryl groups (eg, phenyl, p-sulfophenyl, etc.), or pyridyl groups (eg, 2-pyridyl, 3-pyridyl, methyl-2=pyridyl, etc.).

R is an alkyl group, specifically, for example, one having 1 to 8 carbon atoms.
alkyl groups such as methyl, ethyl, 2-hydroxyethyl, 2-meth!・Xyethyl, 2-aceI・xyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-
Sulfobutyl, vinylmethyl, benzyl, phenethyl,
Propyl, isopropyl, butyl groups, etc. are preferred.

Next, specific examples of the compound represented by the general formula (II) used in the silver halide photographic material of the present invention are as follows.
″ (Exemplary compound) I[-4 C112CIl.So, ni ■ - 5 ■-8 It-9 ■ -10 II-II r[-13 ■ -16 l-17 1+-18 -i9 l-21 ■ -23 ■ -24 "-25 ■ -26 ■ -27 ■ -28 The compound represented by the above general formula [II] used in the present invention is US Pat. No. 2,161.331 and West German Patent No. 9.
It can be easily synthesized based on the method described in No. 36071 and the like.

To use the above compound in a silver halide emulsion, it can be added and dissolved in a coating solution, or dissolved in water or an organic solvent such as methanol, ethanol, acetone, etc. alone or in a mixture thereof and added to the coating solution. It's fine. However, if necessary, it can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, to the extent that it does not affect photographic performance.

The amount of the compound represented by the above general formula [II] added to a silver halide emulsion varies depending on the type of silver halide emulsion and the type of compound, but it is usually per mole of silver halide. The range is from 5n+g to 100OB.

The compound represented by the above general formula [) according to the present invention may be added to the silver halide emulsion at any time, but usually at any time during ripening or immediately before coating after completion of ripening. It is preferable to add it at this time.

In the present invention, as a means for adjusting the pH after chemical ripening, -C may be an acid or an alkali, and may be any one such as a strong acid, a strong alkali, a weak acid, or a weak alkali. Examples include, but are not limited to, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, citric acid, potassium hydroxide, aqueous ammonia, sodium carbonate, and sodium acetate.

Further, as a means for adjusting pAg after chemical ripening, sodium chloride, potassium chloride, sodium bromide, potassium bromide, potassium iodide, silver nitrate, etc. may be used.

Each layer of the photographic material of the present invention may contain various matting agents known in the photosensitive material industry.

The average particle size of the matting agent is preferably 10 μm to 1 μm. If the particle size of the agent is 10 μm or more, moiré will occur, which is not preferable. Moreover, if the thickness is less than 1 μm, the slipperiness and static property will be poor, which is not preferable. The amount used is 0.05 to 1.0, more preferably 0.05 to 0.5, based on the dry weight ratio to the binder of the layer to which it is added.

The silver halide used in the present invention is silver chlorobromide or silver chloroiodobromide, and contains at least 50 mol % of silver chloride. If the silver chloride content is less than 50 mol %, high contrast is impaired and good halftone dot quality cannot be obtained. In order to obtain good halftone quality especially in rapid development processing, it is preferable to use one containing 50 mol % of silver chloride.

Various methods known in the photosensitive materials industry can be used to prepare photographic emulsions for carrying out the present invention.

In order to produce the silver halide grains used in the present invention, for example, in the step of mixing a water-soluble silver salt solution and a water-soluble halogen compound in the presence of a protective colloid to form silver halide grains, the grains are grown in the step. The pAg of the emulsion in which this formation is carried out is controlled within the range of 50 to 9.5, preferably 6 to 8, while at least 30 mol % of the total silver halide is formed.

Generally, in silver halide photographic emulsions,
High-intensity short exposure characteristics can be improved by using a compound containing a group metal, and in the present invention, the addition of a water-soluble iridium salt and/or a water-soluble rhodium salt is particularly effective. Specific examples thereof include rhodium chloride, ammonium hexachlororhodate, sodium hexachlororhodate, potassium hexabromorhodate, iridium chloride (IrCff, and IrC(24), potassium hexachloroiridate, ammonium hexachloroiridate, etc. These compounds can be added in an amount of generally 10-8 per mole of silver halide during or after grain formation, physical or chemical ripening of the silver halide emulsion, preferably as an aqueous solution.
It is sufficient to add up to 10-' mol, but especially when desensitization or reversal is likely to occur depending on the type of metal in the compound used, emulsion preparation method, development method, etc., add 10-8 to 1 O- per 1 mol of silver halide. It is preferable to use 7 mol before the end of physical ripening. The silver halide photographic emulsion used in the present invention contains hydrophilic colloids such as gelatin, chemical sensitizers, stabilizers, which are known and commonly used in the photosensitive materials industry, Color toning agents, hardeners for polymer latex, antifoggants, surfactants, thickeners, plasticizers, slip agents, development inhibitors, ultraviolet absorbers, anti-irradiation dyes, heavy metals, matting agents, etc. It can be incorporated by conventional methods.

The silver halide photographic emulsion used in the present invention is usually applied to a suitable support, such as glass, a cellulose derivative film such as cellulose triacetate, a synthetic resin film such as polyethylene terephthalate, baryta paper, resin coated paper, synthetic paper, etc. It can be applied by the following method.

After exposure, the silver halide photographic material according to the present invention can be developed by various commonly used methods.

The black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, ■-phenyl-3-birasolitons, aminophenols, and aminebenzenes, as well as sulfites, carbonates, and bisulfites of alkali metals. , bromide, iodide, and the like.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited by these examples.

Example 1 (Preparation of emulsion) Solution A Water
9.7Q thorium chloride 20 g
Gelatin 105 g Solution B Water
3,8Q sodium chloride 94 g
Gelatin 365g Potassium bromide 450g to 0.0% of potassium chloroiridate salt. Old% aqueous solution 28 mQ 0.01% aqueous solution of potassium hexabromorodate salt 1.0+n solution C Water
3.8 Q Silver nitrate 1700
g In the above solution A kept at 40°C, pt(3, p
The above solution B and solution C were simultaneously added functionally over 60 minutes while maintaining the Ag at 7.7, and after continued stirring for an additional 10 minutes, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, and a 2Q aqueous solution of 20% magnesium sulfate was added. and 2.55 Q of a 5% aqueous solution of polynaphthalene sulfonic acid were added to flocculate the emulsion at 40°C, followed by decantation and washing with water to remove excess salts from the aqueous solution. Next, 3.7Q of water was added to it to disperse it, and again a 20% aqueous magnesium sulfate solution was added. 'l is added to remove excess salt from the aqueous solution in the same manner. In addition, 3.7Q of water and 141g
of gelatin and disperse for 30 minutes at 55°C.

As a result, particles of 35 mol % of silver bromide, 65 mol % of silver chloride, and an average particle size of 0.25 μm and a monodispersity of 9 were obtained.

The above emulsion is designated as N001.

(Preparation of emulsion No. 2.3.4.5) In solution B, compound 4.9.1 represented by general formula [I]
4.22, each dissolved in methanol, are added in an amount of 1 x 10-' mol per mol of silver halide. Emulsion N
Additions were made in the same manner as in 1 to obtain emulsion No. 2.3.4.5.

To each emulsion was added 12 m of a 1% citric acid aqueous solution (2, 12 mff of a 5% potassium bromide aqueous solution to pH 5.5,
Sodium thiosulfate 0.1 was added to the emulsion adjusted to pAg 7.
% aqueous solution is added with 120mα and 0.2% chloroauric acid aqueous solution 801IIQ and aged at 60°C to achieve maximum sensitivity.

To each of the above emulsions, 25% of a 0.5% solution of 1-phenyl-5-mercaptotetrazole was added as an antifoggant.
mρ, 4-hydroxy-6-methyl-1, as a stabilizer
180ml of 1% solution of 3,3a,7-tetrazaindene
Q. After adding 400ml of a lO% aqueous solution of gelatin (2) to stop the ripening, add the sensitizing dye shown in ■-24, adjust the pH and pAg, and then add a 10% solution of hydroquinone as an antifoggant. 50 mff, 19 mQ of 20% Zabonin aqueous solution as a spreading agent, 50 mQ of 4% aqueous solution of styrene-maleic acid polymer as a thickener,
, 30% of high molecular weight polymer latex of ethyl acrylate
g and stirred, adding l-hydroxy-3,5- as a hardening agent.
Dichlorotriazine sodium salt and formalin were added, and the above emulsion was placed on a subbed polyethylene terephthalate support at a silver density of 4.2 g/m2, and as a protective layer, 10% potassium bromide was added to an aqueous solution of 500 g of gelatin. Add an aqueous solution of 100+++Q and use 1 as a spreading agent.
-decyl-2-(3-isopentyl) salanate-2
- Add 400 mQ of 1% sodium sulfonate aqueous solution, and further add 100 mQ of amorphous silica with an average particle size of 3.5 μm.
The emulsion layer and the protective layer were coated at the same time by adding and dispersing gelatin to give a gelatin content of 1.1 g/m2. The sample thus obtained was designated as sample no.

1 to 5.

<Preparation of Samples No. 5 to 9> Emulsion No. 1 was treated as described above, and immediately before coating, a compound represented by the general formula (1) was added in an amount of I x 10 −' mol per mol of silver halide. did. Next, an emulsion layer and a protective layer were simultaneously coated to obtain samples Nos. 6 to 9.

The nine types of films thus obtained were each exposed to an argon laser and developed for 20 seconds at 38°C using a Konica automatic processor GR-27 using the following developer and fixer.

Unexposed samples of the nine film samples were placed at a distance of 2 m under a 40 W fluorescent lamp with a yellow filter film wrapped around them, and left for 0 and 5 minutes, and the fog density was measured by a conventional method.

Developer solution Thermal pure water (ion exchange water) Approximately 800+n+
2 Potassium sulfite 1. 60g
Ethylenediaminetetraacetic acid disodium salt 2g Potassium hydroxide 10.5g 5-methylbenzotriazole 300mg Diethylene glycol 25g l-7enyl-4,4-dimethyl-3-pyrazolidinone 300mg
1-phenyl-5-mercaptotetrasol 60mg
Potassium bromide 3.5g Hydroquinone 20g Potassium carbonate 15g Add pure water (ion exchange water) and finish.

The developer pi was about 1008.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% w/w aqueous solution) 24
0mQ sodium sulfite 17g
Sodium acetate trihydrate 6.5g Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (90% v/w
Aqueous solution) 13.6mc (composition) Pure water (ion exchange water) 17mQ.

Sulfuric acid (50% v/w aqueous solution) 4.7
g Aluminum sulfate (Al220. equivalent content 8.1%
When using a 26.5 g fixer (w/w aqueous solution), it was dissolved in 500 mQ of water in the order of the above composition A and the composition, and the solution was finished to 1.12.

The pH of this fixer was about 4.3.

The measurement results are shown in Table 1. The sensitivity is fog density +3
．． It is expressed as the reciprocal of the exposure amount at 0.

Table 1 Samples No. 2 to 5 according to the present invention have a sensitivity of 248 to 25o
1 Fog under the yellow safety light is 0.01-0.0 after being left for 0 minutes
It was 0.03 to 0.04 after being left for 2.5 minutes, which was good. On the other hand, sample No. 1 had a good sensitivity of 250 and a fog of 0.01 after being left for 0 minutes under a yellow safety light.
The fog after being left for a minute was 0.23, which was poor. In addition, sample No. 1 added the compound represented by general formula [I] immediately before coating.
, 6 to 9 showed a significant decrease in sensitivity compared to samples Nos. 12 to 5, which were added during particle formation.

Example 2 A sample similar to that prepared in Example 1 was exposed to argon laser light and processed under the same conditions using the same automatic processor as in Example 1 and the developer and fixer described in Example 1.

Further, the unexposed sample was developed and fixed using the same developing solution and fixing solution at 40° C. for 60 seconds using the above-mentioned automatic processor. This is called the degree of overdevelopment fog.

The sensitivity was expressed as the reciprocal of the exposure amount of fog density + 3.0.

Furthermore, this sample was heated to 50% by helium neon laser light.
% halftone dot formation, and 38° in the same manner as above.
After developing with Cl2O for seconds and fixing, the quality of the halftone dots was evaluated.

The quality of the halftone dots was evaluated by visually determining the state of fringes (blurring) occurring around the halftone dots, and using a 5-level scale with 5 indicating the smallest fringe. In other words, "5" means excellent;
"1" means extremely poor. Generally, if the evaluation of 50% of halftone dots is "3" or less, it is unacceptable.

The results of these measurements are shown in Table 2.

Table 2 Sample Nos. 2 to 5 according to the present invention have a sensitivity of 246 to 250
The overdevelopment fog is 0.04 to 0.09, and the halftone quality is 4.
．． It was good at 0 to 4.75. On the other hand, comparative sample No. 1 had an overdevelopment fog of 0.27 and a halftone dot quality of 2.
0, which was inferior to the present invention. In addition, sample No. 6 to 9
Ha No.

The results showed a significant decrease in sensitivity compared to samples 2 to 5.

That is, the present invention showed significantly superior results.

Example 3 Emulsion No. 5 in Example 1 was divided into six, and comparative compounds a and b and the sensitizing dye ll-23, ll-24, It-27, ll- 28 were each added to the emulsion at 7 x 10-' moles per mole of silver halide, and the emulsion layer and protective layer were coated simultaneously. The samples obtained in this manner are designated as sample Nos. 10 to 15, respectively.

Further, a sample obtained by adding a comparative compound to the emulsion of emulsion No. 1 and coating it was designated as No. 16.

The seven types of films described above were developed by the method shown in Example 1. In addition, unexposed samples of the seven film samples were placed at a distance of 1 m under a red safe light using a 60W incandescent bulb and a Konica No. 8A filter, and were left for 0 and 5 minutes, and the fog density was measured by a conventional method. .

The measurement results are shown in Table 3.

Comparative Compound Table 3 Samples Nos. 12 to 15 according to the present invention have a sensitivity of 247 to 2.
50, fogging under red safety light is 0.01 to 0.01 after being left for 0 minutes
After being left for 0.02.5 minutes, it was 0.02 to 0.03, which was good. On the contrary, sample No. 1.1.12 has a sensitivity of 21
The fog after being left for 0 minutes was as low as 5 to 220, and the fog after being left for 0.02.5 minutes was inferior to that of 0.41 to 0.47. Sample No. 16 had a low sensitivity of 222 and a poor fog of 0.42 after being left for 5 minutes. That is, the present invention showed significantly superior results.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer is formed in the presence of a compound represented by the following general formula [I]. 1. A silver halide photographic material comprising silver halide grains containing 50 mol % or more of silver chloride and a compound represented by the following general formula [II]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle. However, the heterocycle does not contain a sulfo group or a carboxyl group as a substituent. X represents a hydrogen atom, an alkali metal atom, an ammonium group, or an organic amine residue. ] General formula [II] ▲ Contains mathematical formulas, chemical formulas, tables, etc. A group of nonmetallic atoms necessary to form a ring, m represents an integer of 1 or 2. ]