JPH026943A - Photographic recording material - Google Patents

Abstract

PURPOSE: To improve the stabilities of a stock soln. and a latent image by forming a layer/contg. a high-chloride silver halide emulsion and a stock soln.- latent image stabilizing reducing agent on a substrate. CONSTITUTION: A recording material having at least one high-chloride silver halide emulsion layer on the substrate and contg. a reducing agent capable of improving the stabilities of a stock soln. and a latent image is developed with a rapid access developer compsn. not practically contg. benzyl alcohol. The reducing agent is, e.g. an arom. polyhydroxy compd. such as a reductone compd., hydroquinone, catechol or amiophenol and the arom. hydroxy compd. preferably has at least two hydroxy groups on the arom. ring at the o-positions. Stock soln. and latent image preserving characteristics can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to improved photographic recording materials for development in rapid access methods.

The formation of color photographic images by imagewise coupling of oxidized aromatic amino color developing agents and color forming compounds to form indoaniline, indophenol, and azomethine dyes is well known. In such color image formation, a subtractive method of color formation is usually used. The image dyes commonly formed are cyan, magenta, and yellow, which are complementary colors to the primary colors red, green, and blue, respectively. Generally, a phenol or naphthol coupler is used to form a cyan dye image, a pyrazolone or cyanoacetyl derivative coupler is used to form a magenta dye image, and an acylacetamide coupler is used to form a yellow dye image.

In these color photographic systems, the color-forming couplers are either in the developer solution or incorporated into the photographic recording material. Using the latter technique, the coupler is available within the emulsion layer during development and reacts with the color developing agent which is oxidized by silver image development.

[Conventional technology]

Color photographic recording materials often contain silver bromide, silver bromoiodide,
and high bromide silver halide emulsions including silver chlorobromide emulsions. However, U.S. Patent No. 4,269
．． High chloride silver halide photographic elements, i.e., halogenated i? ? Elements whose grains are at least 90 mole percent silver chloride exhibit a number of highly advantageous properties. For example, chloride root wall, ′i than silver bromide
The inherent low sensitivity in the '+J viewing region allows the yellow filter layer to be omitted from multicolor photographic elements. Furthermore, high chloride silver halide is more soluble than high bromide silver halide, allowing development to be accomplished in a shorter time.

[Problem that the invention attempts to solve]

However, problems with high chloride emulsions include a tendency to reduce stock storage stability and a tendency to reduce latent image stability.

Another problem that has been recognized with high chloride emulsions containing sulfonated catechol compounds as sequestering agents is processing difficulties. These difficulties relate to reduced developability and speed losses for developer compositions containing benzyl alcohol.

Accordingly, there is a need to provide a color photographic recording material 11 that exhibits improved stock and latent image storage properties.

[One Step to Solve the Problems] The present invention provides a support, at least one high chloride silver halide emulsion layer supported on its stomach, and a stock solution (ra
h 5tock) - Development in a rapid access developer solution characterized by having a reducing agent capable of increasing latent image stability and substantially free of benzyl alcohol -? ! :Based on providing photographic material for the purpose.

High chloride silver halide emulsion stock solution - latent image stabilization attached 1
Compounds that can do this are reducing agents which exhibit a high degree of compatibility with high chloride silver halide emulsions and which do not adversely affect the emulsion layer or photographic recording material in which they are contained. Furthermore, the reducing agent must be able to be incorporated into alkaline processing compositions without causing adverse effects on either the photographic material or the developer formulation in which it is included. It won't happen.

Typical reducing agents include monodactone compounds, hydroquinone, and I-koxy aromatic compounds such as catechol and aminophenols. Particularly preferred polyhydroxyaromatic compounds are polyhydroxyaromatic compounds in mutually ortho positions on the aromatic ring. The group of polyhydroxy aromatic compounds useful in the present invention includes benzene and naphthalene compounds that can be represented by the following formula: where X is benzene Alternatively, it represents the carbon atoms necessary to complete the naphthalene ring structure.

In addition to the orthohydroxyl W7A group, this aromatic ring structure can be substituted with groups such as sulfo groups, carboxy groups, halogen atoms or additional hydroxy groups.

Typical examples of borich 1'roxy aromatic compounds useful in the present invention include: pyrocatechol, 4,5-dihydroxy-m-disulfonic acid disodium salt, tera'bromopyrocatechol /shi, birogal 17-gal, gallic acid, methyl gallate, gallic acid methyl, 2,3-dihydroxynaphthalene-6-sulfonic acid and 2,3,8-monotrihydroxynaphthalene-〇-sulfonic acid.

In a preferred embodiment of the invention, the t'roxy aromatic compound is dihydroxybenzene sulfate, such as 4,5-dihydroxy-m-disulfonic acid, dipotassium salt, and the like.

Polyoxyaromatic compounds have traditionally been used in photographic color developing compositions. For example, they are combined with aminopolycarboxylic acid metal ion t.l sedatives as disclosed in U.S. Pat. No. 3,746,544;
and U.S. Pat. No. 4,264,716, aminopoly, is described in combination with a red sulfonic acid sequestering agent.

In U.S. Pat. No. 4,269,927, these polyhydroxy aromatic compounds are used as sequestering agents in silver halide emulsions to prevent fog and desensitization caused by metal ion contamination. explained. However, these compounds have not been used for that purpose due to the loss of developability associated with the use of developer compositions containing benzyl alcohol; The ability to overcome instability has not been previously recognized.

The term "reductone" refers to a group of unsaturated di- or poly-enolic organic compounds that are strong reducing agents, and which are derived from hexoses, especially glucose.

Typical reductones include piperidinohexose reductone, di-n-butylaminohexose reductone, morpholinohexose reductone, and the like. The preparation of these compounds is described in U.S. Patent No. 2.936.3.
It is described in the specification of No. 08.

Hydroquinones and catechol compounds other than those mentioned above include compounds having various substituents, such as mono- or di-alkyl groups having 1 to 12 carbon atoms.

Aminophenols useful as reducing agents to reduce or eliminate neat solution or latent image instability include monomethyl-p-aminophenol and its sulfuric acid and hydrochloride salts, and p-hydroxy-phenylaminoacetic acid.

In a preferred embodiment of the invention, the photographic recording material also comprises a chromogenic coupler compound.

The reducing agent can be introduced into the silver chloride layer or into a layer adjacent thereto. The amount of reducing agent that can be used is from 0.05 to 50 g per mole of silver. The preferred concentration is 0
．． 25-30 g of reducing agent/mole of silver.

Color image-forming compounds that can be used in the photographic recording materials and methods of the invention include the subtractive primaries (i.e. yellow,
open-chain ketomethylenes, pyrazolones, pyrazolotriazoles, hydrophobically ballasted for introduction into non-diffusible, colorless couplers such as magenta and cyan) image dyes, and for introduction into high-boiling organic (coupler) solvents. , pyrazolobenzimidazole, 2- and 4-equivalent couplers of the phenol and naphthol type.

Such couplers are described by Salminen et al.
net al) U.S. Pat. No. 2,423,730, 2
．． 772.162, 2.895,826, 2,71
No. 0,803, No. 2.407.207, No. 3.737.3
16 and 2,367.531, Loria et al.
U.S. Patent No. 2,772.1 to Roria at al.
62, 2.600.788, 3,006,759, 3,214,437 and 3.253,924, McCro-ssen et al.
al), U.S. Pat. No. 2,875,057; Bush et al., U.S. Pat. No. 2.9.
No. 08.573 1, Gledh et al.
U.S. Patent No. 3.034.892 to ill et al.
No. specification, Weissberger et al.
et al. U.S. Pat. No. 2,474,293, 2
．． No. 407.210, No. 3,062,653, 3.26
5.506 and 3.384.657, U.S. Patent No. 2.3 to Porter et al.
No. 43.703, Greenhalgh et al.
U.S. Patent No. 3,127,2 to Halgh et al.
No. 69, Feniak et al.
al) U.S. Patent No. 2.865.748, 2,933
．． 391 and 2,865.751, U.S. Pat. Nos. 3 and 7 of Bailey et al.
No. 25.067, Beavers et al.
et al) U.S. Patent No. 3,758,308, Lau U.S. Patent No. 3,779,763, Fernandez U.S. Patent No. 3,785,829, British Patent No. 969.
921, GB 1.241,069, GB 1.011.940, Vanden Eynde et at U.S. Pat. 3,762,921, Beavers Bea-
νers) U.S. Pat. No. 2,983,608,
Loria U.S. Patent No. 3,311.476
No. 3,408,194, No. 3,408.194, 3
, 458,315, 3,447,928, 3.47
6.563 specifications, Cressman et al.
U.S. Pat. No. 3,419,390 to Young, U.S. Pat. No. 3,419.3 to Young
No. 91, U.S. Patent No. 3,519,429 to Lestina, British Patent No. 975.9
Specification No. 28, British Patent No. 1.11L554 Specification,
Jaeken U.S. Patent No. 3.222.1
No. 76 Specification and Canadian Patent No. 26.251 Specification,
6 Sehulte et al., UK Patent No. 1,248,924 and Whitmore et al., U.S. Pat.
No. 227,550.

The photographic recording material of the present invention is disclosed in U.S. Pat. No. 3,716,36
Alkali soluble ballasted couplers such as those shown in US Pat. Nos. 8 and 2,772,163 can be incorporated. These photographic elements can be made to form non-diffusible characteristic dyes using dye-forming couplers in a developer solution as shown in British Patent No. 478.
．． No. 984, Jager et al.
al) U.S. Pat. No. 3,113.864, Vittullet et al. U.S. Pat.
No. 362,598, Schwann et al.
U.S. Patent No. 2,950,970 to Car+Roml et al., U.S. Patent No. 2,592,243 to Porter et al.
U.S. Patent No. 2.343.7 to Porter et al.
No. 03, No. 2,376.380 and 2.3G9.489
British Patent No. 88 for Spath
6,723 and U.S. Pat. No. 2,899.306, Tuite U.S. Pat. No. 3.152.
．． No. 896 and Mannes et al.
al) U.S. Pat. No. 2.05.394, 2,252.
718 and 2.108.602, Research Disclosure
osure), 1978: 'f December, item 2, the disclosure content thereof applies mutatis mutandis to the present invention.

Supports that can be used in the photographic recording material of the present invention
7. Polymer films, wood fibers with one or more underlayers to enhance adhesion, antistatic, dimensional, abrasion, hardness, visibility, antihalation and/or other properties of the support surface. metal sheets and foils, glass and ceramic support elements, and the like.

Typical of useful polymeric membrane supports are nitric acid cell V course and cellulose triacetate and diacetate l-
Cellulose esters such as polystyrene, polyamides, homo and copolymers of vinyl chloride, poly(vinyl acetals), polycarbonates, homopolymers and copolymers of o!/fins, such as polyethylene and polypropylene, and dibasic aromatics. It is a film of polyesters of carboxylic acid and dihydric alcohols, such as poly(ethylene terephthalate).

Typical of useful paper supports include partially acetylated or baryta and/or polyolefins, especially polymers of α-olefins containing from 2 to 10 carbon atoms, such as polyethylene, polypropylene and It is coated with a copolymer of ethylene and propylene.

Polyolefins, such as polyethylene, polypropylene and polyaromer-1, such as Hagemeyer et al. () Ia
Gemeyer et al. U.S. Patent No. 3.478
．． 128, copolymers of ethylene and polypropylene are described by Crawford et al.
et al., U.S. Pat. No. 3,411,908 and Ioseph et al., U.S. Pat.
．． 630.740, as a resin coating on paper, as shown in Crawford et al.
al), or as coatings on polystyrene and polyester film supports, as shown by U.S. Pat. No. 3,630,742 of
No. 3,973,963 to U.S. Pat.

A preferred cellulose ester support is US Pat. No. 2.49 of Fordyce et al.
No. 2,977, No. 2,492,978 and No. 2,739.
No. 069, as well as cellulose triacetate supports such as those shown in Fordyce et al.
al) mixed cellulose ester supports such as cellulose acetate propionate tobutyrate as shown in US Pat. No. 2,739,070.

A preferred polyester film support is disclosed in U.S. Pat. No. 2,627,0 by Ares et al.
No. 88, Welman U.S. Pat. No. 2,720.503, Ares U.S. Pat. No. 2,779,684 and Kibler et al.
Polyester films made of linear polyesters, such as those shown in U.S. Pat. No. 2,901.466 by AIles et al.
663.683 and Williams et al.
3,504,075 to Van Stappen.
), U.S. Patent No. 3,227,576, Nato et al.
adeau et al) U.S. Patent No. 3.501,3
No. 01, U.S. Pat. No. 3,589,905 to Reedy et al., Babbi et al.
U.S. Patent No. 3,850,640 to T.T.
U.S. Pat. No. 3,888.678 to Beiley et al., U.S. Pat. No. 3,904.420 to Hunter and Malyn et al.
llinson eLa's U.S. patent cylinder 3.928.
No. 697, it can be modified for use as a photographic film support.

These photographic elements can employ supports that are resistant to dimensional changes at elevated temperatures.

Such a support is approximately 190°C, preferably 220°
Linear condensation polymers with a glass transition temperature above C, such as polycarbonates, as shown in
Can consist of polycarboxylic esters, polyamides, polysulfonamides, polyethers, polyimides, polysulfonates and copolymer variants: Han+
b) U.S. Patent No. 3,634.089 and 3.772
．． No. 405, U.S. Pat. No. 3,725.070 and 3,793,249 to Ilamb et al., Research Disclosure to Wilson
), Vol, 118. February 1974, Item 1183
3 and νo1.120. April 1974, item 1183
3 and Vol. 120. April 1974, Item 1204
6, Conklin et al., Research Disclosure, Vol. 120.19
1974 Item 12012, Prog 9205 and 920
7. Research Disclosure Vo1.101.1
September 972, Items 10119 and 10148, Research Disclosure Vol. 1.106. 1973 2
Month Item 10613, Research Disclosure,
Vol, 117. January 1974, Item 11709 and Research Disclosure, Vol, 134.19
June 1975, Item 13455, Research Disclosure December 1978, Item X■, these disclosures apply mutatis mutandis to the present invention.

Other features, including chemical or spectroscopic sensitization, additives such as anti-capri agents or stabilizers, vehicles and vehicle extenders, coating aids, hardeners, use of antistatic layers, and processing techniques are subject to research. Disclosure, December 1978, No. 17643, the disclosure of which applies mutatis mutandis to the present invention.

〔Example〕

The exposed photographic recording material is processed in three steps: color development (45 seconds, 35°C), bleaching and fixation (45 seconds, 35°C).
) and stabilization or water washing (90 seconds, 35°C) and then drying (60 seconds, 60°C).

The formulation of the above solution is as follows: 1) Lithium salt of sulfonated polystyrene 0.25d Triethanolamine potassium sulfite (45%) Stilbene compound dye reducing agent Lithium sulfate Potassium chloride Potassium bromide Sequestering agent Potassium carbonate (add water to total volume 12, pH to 2) Yingwajiden pentathiosulfate ammonium sodium sulfite 11.0d 0.5- 2.3g 2.7g 2.3g 0.025g 0.8 d 25.0 g Adjusted to 10.12) 58° 8.7 g Acetic acid 9. Od (Add water to total volume 11, adjust pH to 6.2) 3) 9
JLi Shizuki - 1 g of sodium citrate (total water added to 1°C, pH adjusted to 7.2) This developing composition had a total wetting time of only 3 minutes, but
It shows good stability, the processing gives excellent results and it is easy to use the 'llini-jab J
It also achieves the purpose of high quality rapid-access processing, which is particularly useful in facilities.

An important feature of the present invention is the minimal development constraints that enable rapid access processing in the processing of photographic recording materials described above. Furthermore, this rapid access process does not require high development temperatures.

Claims (1)

[Claims] 1. A photographic recording material for development in a rapid, access developer composition substantially free of benzyl alcohol, comprising a support and a high chloride silver halide emulsion and a stock solution-deposit emulsion carried thereon. Photographic recording material as defined above, characterized in that it comprises at least one layer comprising an image-stabilizing reducing agent compound.