JPS58200232A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the quality of a photographic image by incorporating a specified compound into a silver halide emulsion layer, an intermediate layer, a protective layer, an underlayer or other layer. CONSTITUTION:At least 1 kind of compound represented by formula I is incorporated into a constituent layer of a photosensitive silver halide material. By the treatment the quality of an image can be inhibited from deterioration even when the sensitivity of the silver halide material is increased or the weight ratio of gelatin to silver halide is reduced so as to enable rapid processing. In the formula, R is an aliphatic group, an aromatic group or a heterocyclic residue, the groups of the residue may have a substituent, n is 0 or 1. A is -CO- or -SO2-, the aliphatic group represented by R is 1-18C alkyl, 1-18C alkenyl or cycloalkyl, the aromatic group is phenyl or naphthyl, and the heterocyclic residue is a 5- or 6-membered heterocyclic residue having at least one among N, O and S, such as pyrrolyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material containing a novel compound. More specifically, it relates to a /%O silver halide photographic light-sensitive material in which the image quality of photographic images is improved by incorporating a certain compound into a silver halide emulsion layer and/or its intermediate layer, protective layer, subbing layer, etc. . □ In recent years, demands have become increasingly complex and diverse for silver halide photographic materials.In particular, there is a demand for photographic materials with stable photographic performance, high sensitivity, low fog, and high image quality. has been done. In particular, in order to reduce the amount of X-rays the human body is exposed to, χ-ray photosensitive materials have high sensitivity, high image quality, and can provide information quickly. In order to achieve this goal, there is a need for photographic materials that are compatible with rapid development processing.

Conventionally, as a method for increasing the sharpness of silver halide photographic light-sensitive materials, for example, a sensitizer (
For example, by adding a compound called an organic thioether compound (organic thioether compound), by increasing the grain size of silver halide, or by adding a sensitizer or accelerator to the development solution, the development effect is enhanced and the halogenated It is known that the sensitivity of silver photographic light-sensitive materials can be increased; Reduce the amount (or use the developing solution at a high pH value of 30 to 40)
It is known that the development process is carried out by sieving at a high temperature.

On the other hand, while the above-described methods of increasing the sensitivity of iron halide photographic materials and methods of making them suitable for rapid development processing achieve their objectives, they have the drawback of significantly deteriorating the quality of photographic images. Ta. In this respect, the image quality of photographic images of silver halide photographic materials (hereinafter simply referred to as image quality) is important.

) Many reports have been made in the past regarding methods for compensating for the deterioration of For example, a method is known in which a silver halide emulsion contains a compound called an antifoggant or a stabilizer to suppress deterioration in image quality due to coarsening of developed silver grains. Another method is to harden the gelatin (binder) of the photographic material. The use of m-cutting is known. For example, inorganic compounds such as chromium alum, aldehyde adducts such as formaldehyde and curcuraldehyde, 3- Compounds having active halogens as described in U.S. Pat. No. 3,288,755, etc.; Compounds having reactive ethylenically unsaturated bonds such as those described in U.S. Pat. No. 3,635,718 Specification V, epoxy compounds such as those described in U.S. Pat. No. 3,091,537; The gelatin (binder) is hardened by incorporating an organic compound such as carpogicular dehyde such as mucochloric acid into the silver halide emulsion layer, protective layer, etc., and can be used under harsh processing conditions such as high-temperature rapid development processing. There are known methods to make it durable. However, in any of the rapid processing methods, it is not possible to sufficiently improve the image quality without impairing the three true performances (such as d1 sensitivity, contrast, and maximum processing speed) of silver halide photographic materials. The current situation is that this has not been achieved.

Therefore, we used sensitized cutting for silver halide emulsions), reduced the amount of 9-gelatin (binder) relative to iron halide, and halogenated emulsions that can obtain high image quality even when high-temperature and rapid development processing is performed. There is a strong demand for the emergence of silver photographic materials.

41 The first object of the present invention is to provide high sensitivity and rapid processing,
Even if the sensitivity of silver chloride photographic light-sensitive materials is increased, and/or
Another object of the present invention is to provide a silver halide photographic material that can suppress deterioration of image quality even when the amount of gelatin relative to silver gunnide is reduced.

The second object of the present invention is to produce high-quality images that can suppress deterioration of image quality even during rapid development processing using high pH 1 crystals.
'% CI silver gunkide photographic light-sensitive material.

The above object of the present invention is achieved by (no) containing at least one compound represented by the following general formula [■] (hereinafter referred to as the compound of the present invention) in the constituent layers of the silver rogonide photographic light-sensitive material. .

General formula (1) where R represents an aliphatic group, an aromatic group, or a heterocyclic residue which may each have a substituent, n represents an integer of 0 or 1, and A represents 100- or -5o2-.

The aliphatic group formed by R preferably includes branched, m-shaped, and linear groups, each having a carbon atom number of 1.
~18 alkyl groups (e.g. methyl, n-butyl &
n-dodecyl group), alkenyl group (e.g. allyl ° group,
butenyl group, octenyl group), and cycloalkyl groups (eg, cyclopentyl group, cyclohexyl group). The aliphatic group also includes an aliphatic group having one or more substituents (including fIt substitution atoms, the same applies hereinafter). These substituents include, for example, an alkoxy group, an aryl group, an aryloxy group, an amine/group, a dialkylamino group, and a hetero group.
3]1 (for example, N-morpholino group, N-piperidi7 group), halogen atom, nido a group, hydroxy group, carboxyl group, sulfo group, alkoxycarbonyl group, etc. are representative examples.

The aromatic group represented by R above preferably includes a phenyl group and a naphthyl group.

The aromatic group also includes an aromatic group having one or more substituents. Examples of these substituents include alkyl groups, alkoxy groups, hydroxyl groups, norogen atoms, acylamino groups,
Typical examples include an alkoxycarbonyl group, a succinimide group, a carbamoyl group, and a nitro group.

The heterocyclic residue represented by R is preferably at least one of nitrogen atom, oxygen atom, and sulfur atom.
5- or 6-membered heterocyclic residues having
morpholino group, 7ranyl group, etc.). The heterocyclic residue may have a substituent, and these substituents can be arbitrarily selected from the substituents for the aliphatic groups and aromatic groups described above.

Next, typical examples of the compounds of the present invention will be listed, but the compounds of the present invention are not limited thereto.

[Illustrative material] :”:'□9- (11) 10- -11- The amount of the uninvented compound added is /・a per mole of silver saponide, !l) 0.1y to 100 The range of (1) to 7 (2) is preferable, and in particular, 1 vq to 100 q.・Creation of the present invention
.

The compound is usually added to a solvent such as water or methanol at a concentration of 0.1 to
It is used by dissolving it so that it becomes part 1. The addition time 12- can be added at any step before the coating and drying steps of the manufacturing process of the photographic light-sensitive material. The addition site may be any of the constituent layers of the light-sensitive material, but the silver emulsion layer is particularly preferred. Even when added to intermediate layers, protective layers, and subbing layers other than the emulsion layer, sufficient effects are observed.

The compounds of the present invention are published, for example, in the Journal of the Chemica Society.
5ociety), 1951,
pp. 2123-2125, Journal of the Organic Φ Chemistry
Organic Chemistry)') Volume 27,
It can be easily synthesized by the method described on page 3140 ('1962), and can also be purchased from the general market.

Silver halides that can be applied to the silver halide photographic emulsion constituting the photographic light-sensitive material according to the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide, and Among these mixtures, silver iodobromide is the most preferred.

The binder or hydrophilic colloid used in the present invention is most preferably gelatin, but other materials may also be used if necessary, such as derivatized gelatin, colloidal albumin, agar, gum arabic, alginic acid, cellulose derivatives, acrylamide, imidized polyacrylamide, casein, It can be used in combination with polymers such as vinyl alcohol polymers, polyvinyl alcohol, polyvinylpyrrolidone, and hydrolyzed polyvinyl acetate.

The silver halide photographic emulsion used in the present invention includes various known chemical sensitizers, spectral sensitizers, anti-capri agents, high contrast agents,
Gelatin hard hood, surfactant, film property improver, thickener,
It may contain additives such as halftone dot improvers. Listing the various additives mentioned above, examples of chemical sensitizers include:
Noble metal sensitizers such as activated gelatin, water-soluble gold salts, water-soluble platinum salts, water-soluble baradium salts, water-soluble rhodium salts, water-soluble iridium salts: sulfur sensitization: selenium sensitization; polyamines, stannous chloride Chemical sensitization can be carried out using chemical sensitizers such as reduction sensitizers such as, alone or in combination.

There are no particular restrictions on the spectral sensitizer; for example, spectral sensitizers such as cyanine dyes such as xeromethine dyes, mo/methine dyes, dimethine dyes, trimethene dyes, or merocyanine dyes may be used alone or in combination for optical sensitization. be able to.

These techniques are described in U.S. Patent No. 2.688.545.
No. 2,912,329, No. 3,397.06
No. 0, No. 3,615.635M, No. 3.628.9
64-volume specification, British Patent No. 1.195,302, British Patent No. 1.242.588, British Patent No. 1,293,862-j!
Specification, West German Patent (OLS) No. 2,030,326,
Specification No. 2.121.780, Japanese Patent Publication No. 43-493
6 and No. 44-14030, etc. The selection can be arbitrarily determined depending on the wavelength range to be sensitized, sensitivity, etc., and the purpose and use of the photosensitive material.

-i Milk jlJ used in the present invention can contain other additives. For example, azaindenes, triazoles,
Stabilizers and anti-capri agents such as tetrazoles, imidazolium salts, tetrazolium salts, polyhydroxy compounds; aldehyde-based, aziridine-based, inoxazole-based, vinylsulfone-based, acryloyl-based, albodiimide-based, maleimide-based, meta/sulfonic acid esters hard @l1iIl such as triazine-based, benzyl alcohol, polyoxyethylene-based compounds; image stabilization of chroman-based, claman-based, bisphenol-based, phosphite-based 44: waxes, glycerides of higher fatty acids, There are @ erasures of higher alcohol esters of higher fatty acids, etc. In addition, anionic, cationic, nonionic, or A variety of both sexes can be used.

As the antistatic agent, diacetyl cellulose, styrene perfluor fcI alkyl rhidium maleate copolymer, alkali salts of reaction products of styrene]maleic anhydride copolymer and p-aminobenzenesulfonic acid, etc. are effective. Also, examples of the latex added to improve the physical properties of the film include copolymers of acrylic acid esters, vinyl esters, etc., and other enalene group-containing monomers. Examples of gelatin plasticizers include glycerin and glycol thread compounds, and examples of thickeners include styrene-sodium maleate copolymers and alkyl vinyl ether-maleic acid copolymers.

The silver halide photographic light-sensitive material according to the present invention contains a silver halide photographic emulsion, if necessary, through a subbing layer, an intermediate layer, etc.
Baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass paper, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, polyester film such as polyethylene terephthalate, polystyrene, etc. (by known methods)
Constructed by coating.

The silver halide photographic material according to the 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, direct and indirect X-ray use, and radiation use. However, it is particularly effective as a highly hair-sensitive silver iodobromide photographic material.

The silver halide photographic material according to the present invention may be exposed to short-time or flash light in addition to normal fog light exposure, and can be photographically processed by normal methods. The basic photographic processing steps are a developing step and a fixing step, and these two steps may be performed simultaneously.

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 Silver iodobromide (containing 3.0 molar width silver iodide) 100 g% gelatin 40 g was contained in silver halide emulsion IKf,
A high-sensitivity negative cup with sulfur sensitization and gold sensitization,
After adding saponin as a coating aid, the mixture was divided into 15 equal parts, the compounds shown in Table 1 below were added in the amounts shown in the same table, and the mixture was coated on a polyethylene terephthalate film base. Furthermore, on top of this silver halide emulsion layer, a coating aid and lii! are applied as a protective layer. 1.5g/rr of gelatin coating liquid containing film removal? I applied it and let it dry. Based on the JIg method, the sample thus obtained was exposed to white light using a KS-1 type centometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and then developed, fixed, washed with water, and dried. Processed using a continuous conveyance type automatic developing machine capable of processing. The developing solution used was as follows.

Developer formulation (Development time: 35° C., 30 seconds) IJ- was performed on each sample thus obtained, 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 developed silver particles at a density of 0.8.

Similarly, ◯ indicates good, ∆ indicates fair, and × indicates poor enough to be unusable, and two of these arrangements shown together indicate the intermediate evaluation of each symbol.

The following margin C1-C-C0OH However, [A'3 represents a hardening agent, 11Ct-C-C
Indicates a compound of HO.

As is clear from Table 1, it can be seen that the non-inventive samples effectively improve image quality without deteriorating photographic performance.

Patent applicant: Konishiroku Photo Industry Co., Ltd. 22- 181-

Claims (1)

[Scope of Claims] A silver oxide photographic light-sensitive material containing at least one compound represented by the following general formula [T]. General formula (1) [In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic residue which may each have a substituent, and A is -co- or -
It represents 5o2-, and represents n扛O or 1. ]