JPS62291636A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having high sensitivity against an argon laser source by composing silver halide of silver chlorobromide or silver chloroiodobromide contg. silver chloride which has a specific mean particle size and a degree of monodispersion, and by incorporating a specific compd. to a photographic constituting layer and a hydrophilic colloid layer of the silver halide emulsion layer. CONSTITUTION:The silver halide contained at least one layer of the silver halide emulsion layer has 0.05-0.5mum mean particle size and <=20 degree of the monodispersion, and is composed of silver chlorobromide or silver chloroiodide containing at least 50mol% silver chloride. The photographic constituting layer contains at least one kind of the compd. selected from the compds. shown by formula I. At least one kind of the compd. selected from the compds. shown by formula II is incorporated to the hydrophilic colloid layer which presents on an opposite side of the silver halide emulsion layer. In the formula, Z is a non-metal atom group necessary for forming 5 or 6 membered heterocyclic ring, Q is a non-metal atom group necessary for forming a 5-membered heterocyclic ring, R is alkyl group, R2, R4 and R5 are each alkyl group, etc., R3 is aryl group substd. with one or more than one of sulfone groups, (m) and (n) are each 1 or 2.

Description

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

[Conventional technology]

In recent years, the use of bright rooms in the plate-making process has progressed, and silver halide photographic materials that can be handled under white fluorescent lamps or yellow safety lamps have come into wide use.

The performance required of a photosensitive material used in such a bright room is that it has high contrast and sufficient maximum density, and can be handled for a long time in a bright room (under white fluorescent light or yellow safety light). It also 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. Laser light is generally used as a light source for scanners, and argon lasers are particularly often used.

Even in processes using such scanners, a bright room is required. 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.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material that has a long safety time under a yellow safety light, has high sensitivity to the argon laser light source, and has high contrast, in a scanner system using an argon laser as a light source. It is to provide.

[Structure of the invention]

The object of the present invention is to comprise a photographic constituent layer having at least one silver halide photographic light-sensitive layer on one side of a hydrophobic support and a hydrophilic colloid layer coated on the opposite side of the support. In the silver halide photographic light-sensitive material, the silver halide contained in at least one of the silver halide emulsion layers has an average grain size of 0.05 to 0.5 μm, monodispersity of 20
In the following, at least one compound selected from the compounds represented by the following general formula (I) is included in the photographic constituent layer, which is made of silver chlorobromide or silver chloroiodobromide containing at least 50 mol% of silver chloride. This is achieved by a silver halide photographic material containing at least one compound selected from the compounds represented by the following general formula (II) in the hydrophilic colloid layer on the opposite side of the silver halide emulsion layer. .

General formula (I) ---+-Z-+-2 [However, in the formula, Z is a group of nonmetallic atoms necessary to form a 5-membered or 6-membered heterocycle; Examples include a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring, a benzoxazole ring, a naphthothiazole ring, a naphthoselenazole ring, a naphthoxazole ring, a pyridine ring, a quinoline ring, and the like. These heterocycles may have a substituent, and these substituents include, for example, a halogen atom (e.g., chlorine atom, bromine atom, etc.), an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (e.g., a methyl group). , ethyl group, n-propyl group), halogenated alkyl group (e.g., trifluoromethyl group, etc.), alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms (e.g., methquine group, ethoxy group, n-propyloxy group, etc.) , a hydroxy group, an aryl group (eg, a phenyl group, etc.), and the like.

Q represents a nonmetallic atomic group necessary to form a 5-membered heterocycle. Examples of this heterocycle include rhodanine ring, thiohydantoin ring, thioxazolidinedione ring, thioselenazolidinedione ring, etc. These heterocycles may have a substituent, and these substituents Preferably, an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, engineered tyl group, n-propyl group, 2-hydroxyethyl group, 2-hydroxyethyloxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group) , carboxynemethyl group, 2-carboxyneethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group,
3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, benzyl group, phenethyl group, n-butyl group, etc.), aryl group (e.g. phenyl group, p-sulfophenyl group, etc.) or pyridyl group (e.g. 2- Pyridyl group, 3
-pyridyl group, methyl-2-pyridyl group, etc.).

R is an alkyl group, specifically, for example, one having 1 to 8 carbon atoms.
Alkyl groups such as methyl group, ethyl group, 2-hydroxyethyl 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, vinylmethyl group, benzyl group, phenethyl group, n-propyl group, isopropyl group, n-butyl group and the like are preferred.

Further, m represents 1 or 2.

General formula (n) ■ R1 [However, in the formula, Rt represents an alkyl group, a carboxyl group, an alkoxycarbonyl group, a carbamide group, a nitrile group, a trifluoromethyl group, or an acylamino group, and R8 is substituted with one or more sulfone groups. represents an aryl group. R
4, R6 represents an alkyl group which may be different from each other or an alkyl group having a substituent, and n is 1 or 2.

] Next, specific examples of the compound represented by the above general formula (I) used in the silver halide photographic light-sensitive material of 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 the compounds represented by the above general formula (I) -I slltUHtLUOll ■ -10 sll*LHtSLLHtbOiNa ■ -25 I -26 ■ -27 ■ -28 ''' CHtCHtOH Note that the above general formula used in the present invention ( The compound represented by I) can be easily synthesized based on the methods described in US Pat. No. 2,161,331 and West German Patent No. 936,071.

In order to use the compound represented by the above general formula (I) in a silver halide emulsion, it can be added and dissolved in a coating solution, or mixed with water or an organic solvent such as methanol, ethanol, acetone, etc. alone or in a mixture thereof. It may be dissolved and added to the coating solution. 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 general formula (I) contained in the silver halide photographic material of the present invention when added to the silver halide emulsion depends on the type of silver halide emulsion,
Although it varies depending on the type of compound, usually silver halide 1
A range of 5m9 to 1000mg per mole is preferred.

The compound represented by the general formula (I) 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 the appropriate time.

Next, specific examples of the compound represented by the general formula (II) used in the present invention will be shown.

bυ Colla The compound represented by the above general formula (II) is added to the side of the hydrophobic support that does not have the silver halide photographic material, that is, the backing layer. The solvent used was water and the amount added was IL-50.
Set to 0 mg/m'.

The backing layer is composed of a compound represented by the general formula (II) dispersed in a hydrophilic colloid, such as gelatin, and a hardening agent, which is usually used in silver halide photographic light-sensitive materials.
Surfactants, thickeners, matting agents, polymer latexes, and, if necessary, stabilizers, antifoggants, development inhibitors, dyes, heavy metals, and ultraviolet absorbers may be added. The layer structure of this photographic light-sensitive material may be a single layer or a multilayer structure including an intermediate layer and a protective layer.

When handling the silver halide photographic material of the present invention indoors, a yellow light can be used as a safety light. Yellow lights include yellow fluorescent lights, white fluorescent lights wrapped in yellow film, and sodium lights. And the safe light can be used at any illuminance, but preferably 1 to 1
It is 50 lux.

The silver halide in the surface emulsion layer of the silver halide photographic light-sensitive material of the present invention is silver chlorobromide containing substantially no silver iodide. The presence of silver iodide does not improve safelight properties and is not preferred. Note that "substantially not containing" means that the present invention includes those containing such a small amount that they do not exhibit such undesirable effects on safelight properties.

The grain size of the silver halide in the silver halide photographic light-sensitive material of the present invention is 0.05 to 0.5 μm.

If the particle size is smaller than 0.05 μm, sensitivity as a photosensitive material for argon laser cannot be obtained, and
If it is larger than m, the required image density cannot be obtained, which is not preferable.

Further, the silver halide grains used may be used as is, or two or more types having different average grain sizes may be blended at any time after grain formation to obtain a predetermined gradation. It's okay.

The monodispersity of silver halide grains in the light-sensitive material of the present invention can be defined by the following formula.

In the present invention, the grain size of silver halide grains is conveniently expressed as the edge length of cubic grains, or in the case of grains other than cubic grains, the diameter of the projected area converted into a circle, and the average value is defined as the average grain size (r). do.

The degree of monodispersity is expressed as a value obtained by dividing the @Q deviation of the particle size by the average particle size (r) times 100.

Here, if we express the degree of monodispersity in the formula, becomes.

In the present invention, it is important to prepare silver halide grains so that this value is 20 or less; if the monodispersity exceeds 20, high contrast is impaired and sharpness is deteriorated, which is not preferable.

The silver halide photographic emulsion of the present invention is described, for example, in "Chimie et Physique Photo" by P. Glafkides, published by Paul Montel.
graphique; published by Paul Mante1) 1
967, G.F. Duffin
in), “Photographic Emulsion Chemistry”, published by The Focal Press (Photogra
Phic Emulsion Chemistry:
Published by The Foe-al Press) 1966,
V, L, Zelikman, et al.
"Making and Coating Photographic Emulsions" by N, ee, al, ), published by The Focal Press.
Photograp-hic Emulsion; T
Published by he Focal Press') 1964,
It can be prepared using the method described in et al.

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 a one-sided synthesis method, a 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 having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a compound containing a metal belonging to Group 8 can be allowed to coexist.

These compounds are added, preferably as an aqueous solution, during or after grain formation, physical ripening or chemical ripening of the silver halide emulsion, in an amount of generally 10-@ per mole of silver halide.
It is sufficient to add up to 10-f' moles, but especially when desensitization or reversal is likely to occur due to the type of metal in the compound used, the emulsion preparation method, or the development method, it is sufficient to add 10-8 to 10-f' moles per mole of silver halide. -7 mol is preferably used before the end of physical ripening.

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

The silver halide emulsion of the light-sensitive material of the present invention may be chemically sensitized before use. For chemical sensitization, for example, ``Die Grundlagen der Photografsien Brotzes Mits Silber Halogennieden'' edited by H, Fr1eser, Akademissie Verlags and Gesellschaft (Die G.
Rundlagen der Photography
schen Prozesse mit Silver
halogcniden: (Akademische
Veralags Ge5ellschaft) 1
968. The method described on pages 675-734 can be used.

Gelatin is advantageously used as the binder or protective colloid in the photographic emulsion and the hydrophilic colloid in the backing layer, but other hydrophilic colloids can also be used.

In addition to lime-processed gelatin, this gelatin includes acid-processed gelatin and Plutin of Society of Science of Photography of Japan (B
ull, Soc, Sci, Phot, Japan).

Enzyme-treated gelatin as described in No. 16, page 30 (I-66) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used.

The silver halide photographic emulsion and packing layer of the present invention include:
For the purpose of preventing fog during the manufacturing process, storage, or photographic processing of photosensitive materials, or to stabilize photographic performance,
It can contain various compounds. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted)
; Heteromercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; carboxyl groups, sulfone groups, etc.; The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinthione, azaindenes such as tetraazaindene (particularly 4-hydroxy substituted (I, 3, 3a, 7
), benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as anti-capri agents or stabilizers can be added.

The silver halide photographic emulsion and backing layer used in the present invention include various chemical sensitizers, toning agents, hardeners, surfactants, binders, plasticizers, slip agents, development inhibitors, ultraviolet absorbers, Irradiation inhibitors, dyes, heavy metals, matting agents, etc. can be further incorporated in various ways.

Further, it is possible to avoid containing polymer latex in the silver halide photographic emulsion and banking layer of the present invention.

As the polymer latex, an aqueous dispersion of a homo or copolymer of methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, cricidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. is used.

Supports that can be used in the silver halide photographic material of the present invention include cellulose acetate, cellulose nitrate,
Examples include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass, metal, and the like. These supports are subjected to surface treatment if necessary.

The silver halide photographic material according to the present invention can be used for various purposes such as black and white general use, X-ray use, color use, infrared use, micro use, silver dye bleaching method, reversal use, and diffusion transfer method use. It can be effectively applied to materials.

After exposure, the silver halide photographic material according to the present invention can be developed by a conventional method, for example, by a conventional method.

Black and white developer is an alkaline solution containing developing agents such as hydroxybenzenes, aminophenols, and aminobenzenes, and also contains other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides. be able to.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

However, it goes without saying that the present invention is not limited to these.

Example 1 A hydrophilic colloid coating solution having the following composition was coated on both sides of a polyethylene terephthalate film as a hydrophobic support.

(Preparation of backing layer) Inert gelatin 509 dissolved in 10100O water, 29% of polymethyl methacrylate having an average particle size of 5μ as a matting agent, and 20% of a 20% saponin aqueous solution as a spreading agent.
mQ, 10 mR of 3% formalin aqueous solution as hardening agent
, and sodium 2,6-dichloro-1 as a hardening agent.
, 1.0 g of 3,5-triazine-4-olate were added, and 409 g of a high molecular weight latex polymer of ethyl acrylate was added. This was divided into 10 equal parts, and the compound belonging to the general formula (n) was added so that the types and coating amounts listed in Table 1 were included, and 4.59% of the gelatin was applied to each film support.
/m".

(Preparation of Emulsion Layer) A silver chlorobromide gelatin emulsion containing 35 mol % of silver bromide was prepared by a 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 A g
X 8B of sodium thiosulfate and 101 in 1 mole
11 g of chloroauric acid was added and chemically aged at 60° C. for 70 minutes. The compound [-9] belonging to the general formula (I) was added to this chemically ripened emulsion in an amount of 4.0 m97 m''.

Additionally, 6 mg of a 0.5% solution of 1-phenyl-5-mercaptotetrazole as an antifoggant, 130 ml of a 1% solution of 6-methyl-4-hydroxy-1,3,3a, 7-titrazaindene as a stabilizer, and others. 15 mQ of 20% saponin aqueous solution as a spreading agent, 3% as a hardening agent
5 mQ of formalin aqueous solution and further as a hardening agent,
0.69 of sodium-2,6-dichloro-1,3,5-)riazine-4-olate was added, and further 30 g of a high molecular weight latex polymer of ethyl acrylate was added.

This emulsion was placed on a film support with an already prepared backing layer so that the silver surface area was 3.597 m2, and as a protective layer, 5% formalin was added to an aqueous solution of inert gelatin 5009 with an average grain size of 80-1. 15g of amorphous silica with a diameter of 2μm is added to gelatin of 1.1
The emulsion layer and this protective layer were simultaneously coated in such a manner that the coating composition had a coating weight of 1.5 g/m''.

The 10 types of films thus obtained were each exposed to an argon laser and developed for 20 seconds at 38 DEG C. using the following developer and fixer using a Sakura automatic developing machine GR-27.

Unexposed samples of the 10 films 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 prescription) Pure water (ion exchange water) approximately 800 mQL
Potassium carbonate 159 Pure water (
Add ion-exchanged water) to make 1.00On+i7.

When using the developer, the entire amount of the developer was dissolved in pure water (ion-exchanged water) 312.

The pH of the developer before dilution with water was about I1.4, and the pH of the developer p) after dilution with water was about 10.8.

<Fixer formulation> (Composition A) "Ammonium thiosulfate L acetic acid (90% V/W aqueous solution) 13
, 6m12 (composition) "Pure water (ion exchange water) 17m
cL 8.1% w/w aqueous solution) When using the 26.59 fixer, the above composition A was dissolved in 50QmQ of water in that order, and the composition was finished to 112 and used.

The pH of this fixer was about 4.3.

The measurement results are shown in Table 2. Note that the sensitivity is fog density +
It was expressed as the reciprocal of the exposure amount at 3.0. Sample N containing both compounds belonging to the general formulas (I) and (I[) according to the present invention
o, 2 to No, 10 has a sensitivity of 246 to 250,
Fog under the yellow safety light is 0.01 to 0.02 after 0 minutes of standing.
．． After being left for 5 minutes, it was 0.04 to 0.12, which was good. On the other hand, sample No. 1 containing only the compound belonging to the general formula (I) had a good sensitivity of 250 and a fog of 0.01 after being left for 0 minutes under a yellow safety light, but it was good when left for 5 minutes. The fog was inferior at 0.23.

Table 2 Example-2 Example! , the compound 1-9 in Table 1 to 1-7, the compound 11-3 in Table 1 to ll-1, the compound n-4 in Table 1 to ll-5, The above I[-
Sample No. 8, ll= No. 20 was prepared in the same manner as in Example 1, except that Sample No. 8 was changed to ll-7, and this is shown in Table 3. Sensitivity and fog were measured for these in the same manner as in Example 1 and Example 1.

The measurement results are shown in Table 4.

Table 4 As is clear from Table 4, the general formula (I
), sample No. 12 containing compounds belonging to (ff)
~No. 20 had a good sensitivity of 305 to 309 and fog under a yellow safety light of 0.02 to 0.03.5 minutes after being left for 0 minutes, which was good, being 0.06 to 0.17. On the contrary, sample No. 11 containing only the compound belonging to the general formula (I)
The sensitivity is 310, and the fog is 0 when left under the yellow safety light for 0 minutes.
．． 02 White knee f-thickness fortune-telling ζmu can oath Koyama I 1
1 fortune 7^snL was low.

Example 3 An emulsion prepared in the same manner as in Example 1 was divided into 10 equal parts, and as shown in Table 5, compounds 11-6 and If shown in general formula (II) were divided into 10 equal parts.
-4, If-1, I[-2, the presence or absence in the backing layer and the presence or absence of the compound l-
16, If-5, ■-17, l-19 in combination,
It was coated on a film support in the same manner as in Example 1.

The 10 types of films shown in Table 5 thus obtained were each exposed to argon laser, and Sakura automatic processor G
R-27 was developed using the following developer and the fixer used in Example 1 at 28° C. for 30 seconds, followed by fixing, washing with water, and drying.

<Developer formulation> (Composition A) L potassium bromide 2g (composition) Pure water (ion exchange water) 3ml
2L-1-7E-L-3-pyrazolidone 500+119
When using a developer, the above composition A was dissolved in 500 mσ of water in that order, and the final amount was 1 g.

Table 5 The measurement results are shown in Table 6. The general formula (
Sample No. 2 containing both compounds belonging to I) and (It)
2. No. 24. No. 26. No, 27. N
o, 28. No.

30 has a sensitivity of 206 to 232, and a fog of 0.02 to 0.03.5 minutes when left under a yellow safety light for 0 minutes.
It was good at ~0.14. On the other hand, the general formula (
Sample No. 21, No. 21, containing only compounds belonging to I)
23, No.

25, No. 29 had a sensitivity of 208 to 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 0.23 to 0.31. and was inferior.

Table 6 Example-4 Example! The sample prepared above was exposed to an argon laser to form halftone dots. The process was carried out in the same manner as in Example 1, and the shape of the halftone dots was observed with a 100x magnifying glass.
) A sample with a backing layer containing a compound belonging to
No, 2 to No, lO) is a sample that does not contain (N
o, I), it can be seen that the contrast is excellent and the contrast is high.

〔Effect of the invention〕

As described above, according to the present invention, it is possible to obtain a silver halide photographic material that is safe to handle under a yellow safety light, has high sensitivity to an argon laser light source, and has high contrast.

Claims (1)

[Claims] Consisting of a photographic constituent layer having at least one silver halide photographic light-sensitive layer on one side of a hydrophobic support and a hydrophilic colloid layer coated on the opposite side of the support. In the silver halide photographic light-sensitive material, the silver halide contained in at least one of the silver halide emulsion layers has an average grain size of 0.
05 to 0.5 μm, monodispersity is 20 or less, and is made of silver chlorobromide or silver chloroiodobromide containing at least 50 mol% of silver chloride, and the photographic constituent layer has the following general formula (I). The hydrophilic colloid layer on the opposite side of the silver halide emulsion layer contains at least one compound selected from the compounds represented by the following general formula (II). A silver halide photographic material characterized by: General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [However, in the formula, R1 is an alkyl group, Z_1 is a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocycle, and Q is 5
Nonmetallic atomic group necessary to form a membered heterocycle, m
represents 1 or 2. ]General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the formula, R_2 represents an alkyl group, carboxyl group, alkoxycarbonyl group, carbamide group, nitrile group, trifluoromethyl group, acylamino group, represents an aryl group substituted with one or more sulfone groups. R_4 and R_5 represent alkyl groups which may be different from each other. n is 1 or 2. ]