JPS5915240A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To inhibit deterioration in the quality of an image even in case of increased sensitivity and/or a reduced amount of gelatin basing on the amount of silver halide or rapid processing at high pH and temp. under the requirements of high sensitivity and rapid processing. CONSTITUTION:At least one kind of compound represented by the formula is incorporated into a constituent element of a photosensitive silver halide material, preferably a hydrophilic layer which is on the same side as an emulsion layer forming the silver halide material with respect to the support, especially preferably the emulsion layer. In the formula, A is a group of nonmetallic atoms forming a heterocyclic ring such as carbon atoms, X is an anion such as Br<->, ClO<4-> or CH3SO3<->, and R is an aliphatic group, an aromatic group or a heterocyclic group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material with improved image quality for photo art dealers.

In recent years, there has been an increasingly complex and wide range of challenges in silver halide photographic sensitization, and in particular, photographic sensitization methods with stable photographic performance, high sensitivity, low fog, and high image quality have been made. A fee is charged. In particular, in the case of X-ray photosensitive materials, etc., in order to reduce the exposure of the human body to X-rays, it is possible to obtain more information with fewer X-rays, resulting in higher sensitivity and higher image quality. , to get information quickly,
Photographic materials suitable for rapid processing are in demand.

Conventionally, methods for increasing the sensitivity of silver halide photographic materials include, for example, incorporating a compound called a sensitizer (for example, an organic thioether compound) into the silver halide photographic material, or increasing the grain size of silver halide. It is known that the sensitivity of silver halide photographic materials can be increased by fully containing a sensitizer or an accelerator in the development processing solution to increase the phenomenon effect.

In addition, for rapid processing of silver halide photographic light-sensitive materials, the amount of gelatin (binder) relative to silver halide in the silver halide photographic light-sensitive material may be reduced, or
Currently, there is a known method for treating urine with a high PU value and at a high temperature of 30 to 40°G.

On the other hand, the method of increasing the sensitivity of the monohalogenated Akisha A photosensitive dye described above and the method of immediately adapting it to the rapid F process are as follows:
Although it achieves its purpose, it is known that it significantly deteriorates the image quality of the photographic image. This is the internal aspect of the photographic story of silver halide photosensitive forest materials (hereinafter simply referred to as image quality).

), there are many ways to prevent the deterioration of YK
A notice has been issued.

For example, a method has been adopted in which a compound called an antifoggant or a stabilizer is contained in a silver halide emulsion to suppress deterioration in image quality caused by coarsening of silver grains. As another method, it is known to use 441 herbal medicine to harden gelatin (binder) of photographic light-sensitive materials. [+lJ, inorganic compounds such as chromium alum, formamide redehyde, greeta? rare! Aldehyde formation such as redehyde; 1 product, U.S. Pat. No. 3,288.
7'', > No. 5 MeiY+lI Compounds having active halogens as described in U.S. Patent No. 3.
Compounds having reactive ethylenically unsaturated bonds such as those described in US Pat. No. 3,091. ．． The 1° halogen power of mucochloric acid, an epoxidized compound as described in the specification of No. 537! By incorporating organic compounds such as levoquina I redehyde into silver halide gamma staining agent layers, protective layers, etc., the gelatin (binder) is hardened so that it can withstand harsh processing conditions such as high-temperature rapid processing. There are known ways to do this. However, in either method, until the photographic performance (for example, !1&degree, contrast, maximum density tL, etc.) of the silver halide photosensitive forest material can be sufficiently improved without impairing the image quality, The current situation is that this has not been achieved.

Therefore, even if we add a sensitizer to the silver halide emulsion, reduce the amount of gelatin (binder) to the silver halide emulsion, or perform high-temperature rapid processing, it is not possible to obtain a high-quality silver halide photographic material. There is a strong demand for the emergence of this technology.

The first object of the present invention is to improve the sensitivity of silver halide photographic materials and/or to reduce the amount of gelatin used for silver halide while maintaining high sensitivity and rapid processing costs.
It is an object of the present invention to provide a silver halide photographic material capable of completely suppressing the deterioration of fIi.

A second object of the present invention is to provide a high-quality silver halide photosensitive material that can suppress deterioration of image quality even when processed quickly at high PHS temperatures. .

The object of the present invention is to contain at least one compound represented by the following general formula in the silver saponide photographic photosensitive material containing at least one compound represented by the following general formula. Achieved by photographic photosensitive dyes.

The enhancing compound is preferably contained in the hydrophilic layer which is on the same side of the support as the emulsion layer constituting the No. Roke/Silver Cide photographic light-sensitive material I, and is particularly preferably contained in the grain layer.

In the general formula, V represents a necessary group of nonmetallic atoms (β and 0 are carbon atoms) forming the Atd heterocycle, and - etc. 1.R represents an aliphatic group, an aromatic group, or a group.

Preferred heterocycles represented by A are 5- to 6-membered substituents, such as alkoxy groups (methoxy, impropoxy, etc.), aryl groups (), etc. Eni r, trill, etc.),
Ali-・Shiogish group (phenyt-reoxy, tolyl-oxyp, etc.), amino group, sia-I-rex-I-reamino group (
(dimethylamino, dimethylamino, etc.), Fl sterile group (N-morpho IJ /, N-piperidino, etc.), /・rogen atom (chlor, ).

ROM), nitro group, hydroquine group, Levoxyl group, Leho group, Ashikokinka! It may also have levonyl M%l.

Specific examples of the heterocycle represented by A include (eg).

I
u% JIIH may be ・11 shi. As Takemamoto, [+ Sue((] Alkogi/(Methoki 7, Isopropylsi 'l'!'), Aryl; ((Pheni 117)
, tolyl, etc.), aryloxy (fuconyl, tril-reoxy, etc.), 'γ-amino dialkyl-amino group (dimethylamine, dieglyl-amino, etc.), heterocyclic group (N-morpholino, N-piperidino), etc.), norogen atoms (chlor, bromine, etc.), nitro group, hydroxy7
group, force l lebokin I group, su11/ho group -j' I+
/Koki/Carbony group (methoquinolyl sulfonyl, inopropoxycarbonyl, etc.) Masu is cited as a representative example.

If ↓
, even if each has a substituent (1 pseudo 1! JC child 1
~18 alkyl groups
Buti 11/, J, %, n-dogunl group), a! Lekyl group (for example, antyl group, futhinyl group, octenyl group), cycloalkyl group (I+!1iid
Examples include 'cyclopentylene group, / Cloheyan method).

[)l] The aromatic group i17 may be attached with a substituent, and examples of the substituent include an alkyl group (methyl, isopropyl, etc.), an alkoxy group (methoxy, isopropoxy, etc.), a hydroxyl group, ...Rogen atoms (chlor, brome, etc.), anruamino groups (acetylamino, benz).

ylamino, methanesulfo-convex ruamino, etc.), arekoxycarbonyl groups (methoxycarbonyl, inopropoxycarbonyl, etc.), succinimide groups, carbamoyl groups,
A typical example is a nitro group.

The aromatic group represented by RK is preferably 1
Examples include a phenyl group and a naphthyl group which may have 6 substituents.

The heterocyclic group may have a substituent, and the substituent can be arbitrarily selected from those listed above as substituents for the aliphatic group and aromatic group.

The heterocyclic group represented by R is preferably a 5- or 6-chain heterocyclic group having at least one of nitrogen atom, @atomic atom, and sulfur atom (for example, pyrrolyl group, pyrroloni group, (pyridyl group, diazuryl group, moI lephorino group, furani group, etc.).

A detailed explanation of the Itchogi invention will now be given.

First, as a typical example of the compounds represented by the above general formula according to the present invention, metal compounds of F are mentioned.

[Exemplary compounds]

CH.

＼ (9) (11) Compound σ) used in the present invention 111% (・, 1.
/・Rogenation'iJ4 ]-LIL/Per Q, ]
mg ~ l QQQ, riy no fiii4 are preferred. In particular, it is preferably 9 to 100 rrrg, and is usually used by dissolving it in water or a stimulant such as methanol to a concentration of 0.1 to 1. The manufacturing process of the material, the coating and drying process, and the light if Ail.
Add 1 scale of samurai. Halotaffy 1' and Iro emulsion layers are particularly suitable for the addition of halothafine 11, but the object 1i74 of the present invention can also be achieved by adding it to intermediate layers, protection layers and subbing layers.

Generally speaking, the f'81 compound of the present invention can be easily synthesized from a malecaptotetrazole compound. The example compound (3) is synthesized using 1-phenyl-5-mercaptotetrazole and 3-chloro-1
-Synthesize 5-(2-hydroxypropizole from propatool, dissolve the compound and triethylamine in dry methylene chloride, add ice salt cooling to this, and add a solution of methane I lephonyl chloride dissolved in dry methylene chloride. It can be completed by adding.

Examples of silver halide that can be applied to the silver halide photographic emulsion constituting the photographic light-sensitive material of the present invention include 1n silver, silver bromide,
Silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and these? It is a 1-mo compound, and silver iodobromide is also desirable.

The binder or hydrophilic colloid used in the present invention is most preferably gelatin, but other materials may also be used as necessary, such as wire conductor gelatin, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives, acrylic rare ζ-de, imido-ibipolymer. Acrylic+17 amide, casein, vinyl 1-7 lunyl polymer, polyvinyl alcohol, polyhinylpyrrolitone, hydrolyzed polyvinyl acetate-1
It can be used in combination with the polymer of 1-.

The silver halogenide photographic emulsion used in the present invention contains various known chemical sensitizers, spectral sensitizers, antifoggants, contrast enhancers, gelatin hardeners, surfactants, and physical property improvers. agent,
It may contain additives such as a bleaching agent and a dot improving agent. When the various additives mentioned above are excluded, chemical sensitizers include:
For example, activated gelatin, water-soluble! raw gold salt, water-soluble platinum salt,
Chemical sensitizers (such as noble metal sensitizers such as radium salts, water-soluble rhodium salts, and water-soluble iridium salts; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as polyamines and stannous chloride) Chemical type sensitization can be achieved by using a sensitizing agent alone or in combination.

There are no particular restrictions on the spectral sensitizer, and spectral sensitizers such as cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or merocyanine dyes can be used alone or in combination to optically sensitize. I can do it.

These techniques are described in U.S. Patent No. 2,688,545.
No. 2,912,329, No. 3, :39
7, No. 060, No. 3,615.635, No. 3, 628, 964, Part 1, British Time ft”@
1, No. 195,302, No. 1,242,588,
Specification No. 1,293,862, West German patent (OLS)
No. 2,030,326, Specification No. 2.121,780, I Machiko Sho No. 43-4936, No. 44-14030
It is also stated in the publication number etc.

The selection can be arbitrarily determined depending on the wavelength range to be used, sensitivity, etc., and the purpose and use of the photosensitive phase material.

The emulsions used in the present invention may contain additives. , for example, azaingans, triazoles, tetrazoles, imidazolium salts, tetrazolium salts,
Stabilizers such as polyhydroxy compounds and antifogging + L agents; ardehyde, aziridine, inoxazole, vinyl-free! Rehon type, Acryloi I type, A? Levodiimide, maleimide, methanesulfonate esthetics! Side threads such as triazine threads, bisfuenol, and phosphoric acid esters I; Wanx, glycerides of higher fatty acids, higher alcohol esters of higher fatty acids I
There are lubricants, etc. We also use anionic, cationic, and nonionic coating aids as surfactant injection agents, permeability improvers for processing solutions, antifoaming agents, and additives for controlling various physical properties of photosensitive materials. A variety of types or bisexual types can be used.

As antistatic agents, Diaceti I Rece J Rerose, Styrene Barf! Effective examples include Leoroa J Relicin tau-maleate copolymer and alkali salts of synthetic products of styrene-maleic anhydride copolymer and p-aminebenzene I lephonic acid. Examples of latexes added to improve the physical properties of the film include copolymers of acrylic acid esters, vinylic acid esters, etc., and monomers having ethylene esters. Examples of gelatin plasticizers include glycerin and glycol compounds, and examples of thickeners include styrene-sodium maleate copolymer, alkylphinyl ether-maleic acid copolymer, and the like.

The silver halide photographic light-sensitive phase material of the present invention is produced by applying silver halide '5' hardness to baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass paper, etc. through a F rust layer, an intermediate layer, etc., if necessary. , cellulose acetate, cellulose butrade, or polyvinyl acetate, and coated on a support such as polypropylene, a polyester film such as polyethylene terephthalate, or polystyrene by a known method.

The silver halide photographic material of the present invention may be either a black-and-white photographic material or a color photographic material, and can be used for various purposes such as general use, printing, X-ray use, and radiation use. ,
In particular, it exhibits remarkable effects as a high-sensitivity silver iodobromide photographic light-sensitive material.

The silver halide photographic light-sensitive material of the present invention can be exposed not only to ordinary light but also to short-time to flash light, and has good -C properties, and can be photographically processed by the usual -5 method. 21. I. The two unsuitable dazzling processing steps are a developing step and a fixing step, and these two steps may be performed at the same time.

The present invention will be described below with reference to the implementation sequence (1'114E -4-,'
The embodiments of the present invention are not limited thereto.

Example emulsion i: silver iodobromide (containing 3,0 mole silver iodide) in ky
100,! i'r had 40m of gelatin,
YL for high R, ☆ degree negatives with sulfur sensitization and gold sensitization
After saponin was added to the preparation as a coating aid, the compounds shown in Table 1 were added to J5 in the amount shown in Table 1 in the amount shown in the same table, and the mixture was coated on a polyethylene terephthalate film I rem base. In history, one layer of gelatin solution containing a coating aid and a hardening agent was added as a protective layer to the seventh layer of this silver halide emulsion layer.
．． It was coated and dried to 5Fr/rrj. Based on the TTS method, the sample thus obtained was exposed to white light using a KS-1 type sensitometer (Konishi Roku Photo Industry Co., Ltd.), and then developed, fixed, washed with water, and dried. It was processed using a continuous conveyance type automatic phenol machine that can be used.

Sensitometry was carried out on each sample prepared in this manner (indication time: 35° C., 30 seconds), and the photographic properties obtained are shown in Table 1. Note that the sensitivity shown in the table is a relative sensitivity value with the sensitivity of the comparative sample (sample number -1) being 100.

Further, the image quality shown in Table 1 is determined by visual judgment of the degree of roughness of the present silver grains at a density of 0.8.

In addition, (,tan, L good, △辷L-?!i・市, is the middle N'F 1+ of each symbol
Indicates Il.

As is clear from Table 1, <*Invention: Trial (numbers 4-11)
) improves 1...1j6 without impairing photographic performance.
1. However, CA'] represents gelatin. Agent Kanhara J-Ran Beautiful Procedures Amendment 1, 'if I'1 No. 6, Showa 5, 1q, 'j f+Application No. 124741 Li2 Title of the Invention Silver halide photographic light-sensitive material 3 Auxiliary illumination needle - 4゛ru8 1 (Relationship with I'I) Address of patent applicant: Tokyo Riki "Shuku-ku Nishi-Shinjuku 1 i' 1F12
G 2 names in total (+271 Rokuji Konishi Geshin Yugyo Co., Ltd.
l! lft1lj' sa < ”J mr I ilr
p6, "Detailed Description of the Invention" column 7 of the specification to be amended Contents of the amendment The detailed description of the invention is amended as follows.

Claims (1)

[Scope of Claims] A silver halide photographic photosensitive material, comprising at least one compound or product represented by the following general formula. [General formula] [In the formula, A represents a non-metallic group necessary to form a compound, X represents an anion, and J represents an aliphatic group, an aromatic group, or an aliphatic group. . ]