JPS61172140A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material safe in handling under the yellow safelight, and yet, high in sensitivity to Ar laser beams by incorporating at least one of specified compds. having arranged plural hetero rings, and at least one of arranged plural aromatic rings. CONSTITUTION:The silver halide photographic sensitive material high in contrast, safe in handling under the yellow safelight and yet high in sensitivity to Ar laser beams can be obtained by incorporating at least one of compds. represented by general formula I and at least one of compds. represented by general formula II, and in formulae I and II, Z1 is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring; Q is a nonmetallic atomic group necessary to form a 5-membered hetero ring; Z2 is an aromatic group having unsatd. side chains; at least one of side chains R3-R6 is a sulfonic group; and n is 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material. The photographic light-sensitive material of the present invention can be used, for example, as a silver halide photographic light-sensitive material for Ar laser scanners, which can be handled under a yellow safety light.

(Prior Art) In recent years, as plate-making processes have become more brightly lit, silver halide photographic materials that can be handled under white fluorescent printing or yellow safety lights have become widely used.

The performance required of a photosensitive material used in a bright room is that it has high contrast, sufficient maximum density, and can be handled for a long time in a bright room (under white fluorescent light or yellow safety lights). , and has high sensitivity to printer and scanner light sources.

On the other hand, it has become common to use scanners. Scanners are used for color separation of color originals and layout of printed originals. A laser beam is generally used as a light source for a scanner, and an Ar laser is particularly often used.

A bright room is also required in the process of using this type of scanner. However, in this case, the reality is that a photosensitive material that is safe to handle in a bright room has not yet been sufficiently developed.

(Objective of the Invention) An object of the present invention is to provide a silver halide photographic material that is safe to handle under a yellow safety light, has high sensitivity to an Ar laser light source, and has high contrast. be.

Other objects of the invention will become apparent from the description.

[Structure and operation of the invention]

The above purpose is to use at least one compound selected from the compounds represented by the following general formula (1) and the following general formula (II).
This can be achieved by producing a silver halide photographic material containing at least one compound selected from the following compounds.

υ [However, 81 in general formula (1) is an alkyl group, specifically an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, and a 2-acetoxy Ethyl group, carboxymethyl group, 2-
Carboxyethyl group, 3-carboxyethyl group, 4-carboxybutyl group, 1-sulfoethyl group, 3-sulfopropyl group, a-sulfobutyl group, 4-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, D-propyl group, Inpropyl group, n-butyl group, etc. are preferred. Z
l is a nonmetallic atomic group necessary to form a 5-membered or 6-membered heterocycle, and examples of the heterocycle include a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring, Examples include a benzoxazole ring, a naphthothiazole ring, a naphthoselenazole ring, a naphthoxazole ring, a pyridine ring, a quinoline ring, etc. Furthermore, these heterocycles may have a substituent, and these substituents include, for example, halogen. atoms (e.g. chlorine atom, bromine atom, etc.), e.g. alkyl groups, preferably alkyl groups having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, etc.), halogenated alkyl groups (e.g. trifluoromethyl group) etc.), an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group,
Examples include ethoxy a, n-propyloxy groups, etc.), hydroxy groups, and aryl groups (eg, phenyl groups, etc.).

Q represents a group of nonmetallic atoms necessary to form a 5-membered heterocycle, and these heterocycles include, for example, rhodanine ring,
Examples include thiohydantoin ring, thioxazolidinedione ring, thioselenazolidinedione ring, etc. These heterocycles may have a substituent, and these substituents are an alkyl group, preferably having 1 to 8 carbon atoms. Alkyl group (
For example, methyl group, ethyl group, n-propyl group, 2-hydroxyethyl group, 2-hydroxyethyloxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3- Carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, benzyl group, phenethyl group,
n-7'robyl group, n-butyl group, etc.), aryl group (e.g. phenyl group, p-sulfophenyl group, etc.) %? "lJ
Zyl group (e.g. 2-pyridyl group, 3-pyridyl group, 4-pyridyl group)
Pyridyl group, 4-methyl-2-pyridyl T4). Makum represents 1 or 2. ] General formula (It) [However, in general formula (II), R is a hydrogen atom, a lower alkyl group, an amino group, an aclaramino group, an alkylamino group,
Represents a group selected from a carboxyl group, an alkoxycarbonyl group, a hydroxyl group, an alkoxyl group, or an aryl group, and RI represents a group selected from a norogen atom, a lower alkyl group, an alkoxyl group, a hydroxyl group, a carboxyl group, or a sulfonic acid group. When n is 2 or more, RJ may be different, and z represents a group. (R4m RgOkobi 几･ is a hydrogen atom, a halogen atom, a lower alkyl group, an alkoxyl group, a carboxyl group, respectively. an alkyl group, a substituted alkyl group such as a group selected from a hydroxyalkyl group, a chloroalkyl group, a sulfoalkyl group, and a cyanoalkyl group). Tomodashi FLs e ”4e
RI e represents at least the 5b sulfone group of RI s. ] That is, it is possible to achieve the above objective by containing at least one compound selected from the compounds represented by the above general formula (1) and at least one compound selected from the compounds represented by the above general formula [II]. A novel silver halide photographic material of the present invention which achieves r+ is obtained.

Next, specific examples of the compound represented by the above general formula (1) used in the present invention will be shown. However, as a matter of course, the compounds used in the present invention are not limited to these.

Examples of compounds represented by the above general formula (1) 0H OH,
OII Goose 80. 0H.

N OHz OHz 803 N &0
H.

02H.

■-11 C Goose H.

C! Hs 0, H, C, H.

0 [H, c, H.

0H.

0, H, O, H.

■-22 (OH,), i! 30. H ■-24 0H Goose OH Goose 80. to ■-25 0H! 0H300H.

The compound represented by the above general formula (1) used in the present invention is:
For example, it can be easily synthesized based on the methods described in US Pat. No. 2,161,331 and West German Patent No. 936,071. The above general formula (1
) To use the compound represented by ``halogen'' in a silver oxide 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 then prepared at any time. It can be added to the coating solution at any time.Usually, it can be added at any time from the end of ripening to just before coating.It is preferably added to the silver halide emulsion layer.However, if necessary, it may be necessary to adjust the photographic performance. It can also be added to layers adjacent to the silver halide emulsion layer, such as a protective layer and an intermediate layer, as long as it does not have any adverse effect.

Furthermore, the amount used when adding the compound represented by the above general formula (1) used in the present invention to a silver halide emulsion varies depending on the type of silver halide emulsion and the type of compound, but usually halogen From 511P to 5 per mole of silveride
00'q, and the optimum amount for obtaining appropriate effects can be arbitrarily selected.

Next, specific examples of the compound represented by the above general formula (II) used in the present invention will be shown. However, as a matter of course, the compounds used in the present invention are not limited to these.

Examples of compounds represented by the above general formula (U) 03Na [-2 80g N a 01Na 0INa 038a ■-15 03Na ■-16 The above general formula Cl)α Hi hook used in the present invention is derived from Bob Bob.
Th@0yanins Dyes and R
ElatedCompounds: John Wl
ley & 5ons, published 1964 1, [The Chemistry of Synthetic Dice J (
The Ochemistry of 8ynth@ti
eDy@s ; Academic Press 19
It can be easily produced by using the 1.9 synthesis method described in "Dye Handbook (Maruzen, published in 1970)". can do.

The compound represented by the general formula [II] can be dissolved in a suitable solvent such as water, methanol, ethanol, etc., and added to the constituent elements of the silver halide photographic light-sensitive material according to the present invention. The compound represented by the general formula (II) is
Preferably, it can be added to the silver halide emulsion layer. 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. Further, the compounds represented by the general formula [■] can be added to the constituent elements of the photosensitive material at any time during the production process of the silver halide photosensitive material.

When added to a silver halide emulsion layer, it is preferably added after chemical ripening or before coating.

The amount of the compound represented by the general formula (II) used at this time depends on various factors such as the type of compound, the type of silver halide, the emulsion, and the type or amount of the six other additives used. Although it varies depending on the situation, it is generally 0.1 to 511 per mole of silver halide. Preferably 0.5~
Use in a range of 2.5g.

The compound represented by the general formula (1) or (If) is
It may be added separately, or it may be added after mixing both ingredients. The compounds represented by the general formulas (1) and (II) may be at least one selected from the group of compounds represented by the general formulas CD and Cl), respectively.

In practicing the invention, a yellow light can be used as a safety light. Yellow lights include yellow fluorescent lights, white fluorescent lights with a hole wrapped in yellow film, and sodium lights.

The safety light can be used at any illuminance, but is preferably between 1 and 150 lux.

When practicing the present invention, the photographic emulsion is, for example,
G. F. Duffin, “Photography, Emulsion Chemistry J.
cEmulsion Chemistry: The
Published by Focal Press, 196, 966, L
, "Making and Coating Photo Emulsion J" by Zellkman at al.
graphic emulsion: The F
ocal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided synthesis method, simultaneous mixing method, or a combination thereof. .

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and nearly uniform grain and particle sizes can be obtained.

It is also possible to use a mixture of two or more silver halide emulsions formed separately.

Silver halides that can be used in the present invention include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, silver chloroiodobromide, etc., which are commonly used in silver halide photographic emulsions. It is optional.

Silver halide grain formation occurs during the physical ripening process.
Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts and their complex salts, iron salts and their complex salts, etc. may also coexist.

To remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelatinization, may be used. A flocculation method may be used using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.).

The silver halide emulsion may be used after being chemically sensitized as usual. For chemical sensitization, e.g. pages 675-734)
The method described in can be used.

The silver halide grains used in the present invention can be subjected to reduction sensitization at any point in the manufacturing process.

Reduction sensitization may be carried out by stirring the emulsion under low pAg conditions, ie, by silver ripening, or by using a suitable reducing agent such as tin chloride dimethylamine borane, hydrazine, or thiourea dioxide.

As a binder for photographic emulsions, gelatin is advantageously used as a protective colloid, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugars such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated and enzyme-treated gelatin can be used, and gelatin hydrolysates and enzymatically decomposed products can also be used.

Gelatin derivatives include various compounds such as gelatin K, such as halide halide, acid anhydride, incyanates, bromoacetic acid, alkanesultones, vinyl sulfo/amides, maleimide compounds, polyalkylene oxides, and epoxy compounds. Those obtained by reaction can be used.

In carrying out the present invention, the photographic emulsion contains various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing the photographic performance. be able to. Namely, azoles such as penzotidezolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted); hetero-mercapto compounds analogs such as mercaptothiazoles, mercaptobenzothiazoles , mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines: The above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group: Thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (particularly 4-hydroxy substituted (1,3°3m, 7
Many compounds known as anti-capri agents or stabilizers can be added, such as (tetraazaindenes); benzenethiosulfonic acids: benzenesulfinic acids;

Examples of the support in the silver halide photographic material of the present invention include cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polio such as polyethylene, reflexine, polystyrene, baryta paper,
Paper coated with polyolefin, glass, metal, etc. are used. These supports are subjected to surface treatment if necessary.

In addition to chemical sensitizers, the silver halogenide photographic emulsion used in the present invention contains stabilizers, toning agents, hardeners, anti-capri agents, surfactants, thickeners, plasticizers, slipping agents, and developing agents. Inhibitors, ultraviolet absorbers, irradiation inhibitors, dyes, heavy metals, matting agents, and the like can be further incorporated in various ways.

Also, a polymer latex may be contained in the silver halogenide photographic emulsion used in the present invention. As the polymer latex, an aqueous dispersion of a homo or copolymer of methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. is used.

The particle size of the silver norogenide grains that can be used in the present invention is not particularly limited, and is preferably 0.1 to 3.0 μm.

After exposure, the silver halide photographic light-sensitive material according to the present invention can be developed by a commonly used known method.

The black-and-white developer is an alkaline solution containing challenge agents such as droxybenzenes, aminephenols, and aminobenzenes, and other alkali metal salts such as sulfites, carbonates, and
It can contain bisulfites, bromides, iodides, etc.

[Embodiments of the invention]

Next, the present invention will be specifically explained using an example. However, as a matter of course, the present invention is not limited to this.

Example 1 A silver chlorobromide gelatin emulsion containing 35 moles of silver bromide was prepared by the simultaneous mixing method at 45°C for 35 minutes.

The emulsion thus prepared was desalted and redispersed to obtain a monodispersed emulsion with an average grain size of 0.2 μm. This emulsion contains AgX
Add 8 mg of sodium thiosulfate to 1 mole of chloroauric acid and chemically sensitize at 60°C for 70 minutes. This chemically sensitized emulsion was divided into 10 equal parts, and 4.619/- of the compound 1-1 shown in Table 1 and belonging to the above general formula (1) was added to each of these to give sample A2 in Table 1. ~4
4 includes the above-mentioned 1-1 belonging to the general formula (If), respectively.
The compound of 2 cape/? F/, 4wq/rr? , 7q/- was added, and samples 45 to 7 in Table 1 each had the general formula (
Compound 1-3 belonging to If) t 2 my/rr
? , 4 vq/rr? , 7 capes/- were added to sample A3-410 in Table 1, and the compounds 1-10 belonging to the general formula (n) were added at °s my/i, 12 w9/, respectively.
TI? , ts++y/m' were added. Furthermore, in Samples 41 to 410 in Table 1, 6-methyl-4-
Hydroxy-t, 3.3m, ? -Tetrazaindene, saponin, and formalinyt were added, and each of these was placed on a film support with a silver content of 3.51//W? Next, apply it to the sea urchin.

Using this method, each of the nine types of films obtained was exposed to Ar and laser, and processed using the Sakusa automatic processor Q8-25.
;N621 solution was applied for 20 seconds at 38°C. Also, unexposed samples of the 10 samples mentioned above? A yellow filter film was wrapped around a 40 W fluorescent lamp, and the sample was placed at a distance of 2 m under a yellow light, left for 0 minutes and 5 minutes, and the Capri concentration was measured by a conventional method.

The measurement results in Table 1 are shown in Table 2. Sample A2 containing both compounds belonging to the general formulas (1) and (n) according to the present invention'
-Ban 10 has a sensitivity of 246 to 2501. Capri under a yellow safety light leaves it for 0 minutes and leaves it for 0.01 to 0.02.5 minutes.
03 to 0.15, which is good. On the other hand, a sample containing only compounds belonging to the general formula CI) has a sensitivity of 250 and a capri of 0.0 after being left for 0 minutes under a yellow safety light
It was good at 1, but the capri left for 5 minutes was inferior at 0.21.

Table 2 Example 2 Example 1, the compound 1-11-1-13 in Table 1, the compound 1-1 in Table 1 to 1-11, the compound 1 in Table 1 -3 to [[-12, the above [[ in Table 1]
Sample Al1-20 was prepared in the same manner as in Example 1, except that -10 was changed to 11-13, and the sensitivity and capri were measured.

The measurement results are shown in Table 3. It is clear from Table 3 that the general formula (1), (II
) Samples 12 to A20 containing compounds belonging to
．． After being left for 0.02 to 0.04.5 minutes, the result was 0.07 to 0.17, which was good. On the other hand, sample All containing only the compound belonging to the general formula (1) has a good sensitivity of 3101, with a capri under a yellow safety light of 0.02 after being left for 0 minutes;
Capri left for 5 minutes was inferior at 0.26.

Example 3 The following emulsion prepared in the same manner as in Example 1 was divided into 10 equal parts, and only compound 1-6 belonging to the general formula (1) was added to 3.01Hf.
/rr? (sample 421), and further compound 11-12'112q belonging to the general formula (II)
/rr? Added (Sample A22)% General formula (1)
Only compounds 1-16 belonging to 3.0 cape/rr? (Sample 423), and further the above general formula (II) K
Compound ll-12 belonging to 12 Wq/rl? Added (sample A24), a compound belonging to the above general formula (1)! -23 alone was added at 3.0 my/- (sample &251) and compound ■-15 belonging to the general formula (II) was added to it at '``I/m', i 2η/?F/'' (sample &251). (Sample 428) % compound belonging to the above general formula (1) l-2417) t3.019 /- added (sample 29), compound l-24 belonging to the above general formula (1)
3.0IIp/yr? and a compound belonging to the general formula CII) K -12t-1211F/- (Sample 430
) was added. Furthermore, a stabilizer was added to these samples in the same manner as in Example 1, and each of these was coated on a film support in the same manner as in Example 1.

The 10 types of films thus obtained were exposed and developed in the same manner as in Example 1. The capri density of the 10 sample films was measured in the same manner as in Example 1.

The measurement results in Table 4 are shown in Table 5. The general formula (
Sample 422 containing both compounds belonging to 1) and (n)
．． 424.426.427.428.430 has a sensitivity of 207 to 232, and a fog of 0 minutes when left under a yellow safety light.
．． 0.02 to 0.03, and 0.09 to 0.17 after 5 minutes of standing, which was good. On the other hand, samples 421 + 23e & 25. containing only compounds belonging to the general formula (1) were used. &
29 had a sensitivity of 210-235, and the fog under the yellow safety light was good at 0.01 to 0.02 when left for 0 minutes, but the fog when left for 5 minutes was poor at 0.23 to 0.28. .

Table 5 [Effects of the Invention] As described above, according to the present invention, a silver halide that is safe to handle under a yellow safety light, has high sensitivity to an Ar laser light source, and has a high contrast Photographic material is obtained.

Patent applicant Konishiroku Photo Industry Co., Ltd. Agent Patent attorney Takatsuki Hirate Tsuzuki (Ho
True form (method) % formula % 1. Indication of the case 1985 Patent Application No. 13046 2. Name of the invention Silver halide photographic light-sensitive material 3. Person making the amendment Relationship to the case Patent applicant address Shinjuku-ku, Tokyo Nishi-Shinjuku 1-26-2 Name
(127) Roku Konishi Photo Industry Co., Ltd. 4, Agent (1) In the specification, 'P' in the 25th true line 11-13
, Chimie et Phys by GIafkides
iquePhotographique (Paul
Chimie et Phy Photography, by P. Glafkides, published by Paul Montel, 1967.
Paul
Published by Monte 1) 1967,” is corrected.

(2) Same, page 27, line 6 from the bottom - line 3 from the bottom 'F
r1eserkIiDie Grundlagen d
er Photography-ischen proz
esse wit Silberhalogenide
n(＾kade糟1sche Verlagsgese
(1968) pp. 675-734) J.
phischen Prozesse IIitSil
berhalogeniden: Akademis
Verlagsgesellschaft)
(1968) 675-734 True”.

(3) Same, page 29, line 2, 'Bull % Soc, Sci 5Photo
, Japan J r Bulletin of the Society of Science of Photography of Japan (Bull, Soc, Sci, Phot, Ja
pan) Correct as J.

that's all

Claims (1)

[Scope of Claims] The claim contains at least one compound selected from the compounds represented by the following general formula [I] and at least one compound selected from the compounds represented by the following general formula [II]. Characteristic silver halide photographic material. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the general formula [I], R_1 is an alkyl group, Z_1 is a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, Q represents a nonmetallic atomic group necessary to form a 5-membered heterocycle, and m represents 1 or 2. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, n = 0 to 3
) [However, in general formula [II], R_2 is a hydrogen atom, a lower alkyl group, an amino group, an acylamino group, an alkylamino group,
Represents a group selected from carboxyl group, alkoxycarbonyl group, hydroxyl group, alkoxyl group, or aryl group, and R_3 represents a group selected from halogen atom, lower alkyl group, alkoxyl group, hydroxyl group, carboxyl group, or sulfonic acid group. When n is 2 or more, R_5 may be different from each other. Z_2 represents a ▲ group with mathematical formulas, chemical formulas, tables, etc. or ▼ groups with mathematical formulas, chemical formulas, tables, etc. (R_5, R_6 and R_7 are each a hydrogen atom,
represents a group selected from a halogen atom, a lower alkyl group, an alkoxyl group, a carboxyl group or a sulfone group,
R_8 and R_9 each represent a hydrogen atom, a lower alkyl group, or a group selected from substitution. ) However, R_3, R
At least one of _4, R_5, R_6, and R_7 represents a sulfone group. ]