JPH0354554A - Use of pyrazolone triazole photographic color coupler class - Google Patents

Abstract

PURPOSE: To improve the shelf stability of a raw film by incorporating a specified coupler into it. CONSTITUTION: The coupler (A) obtd. by bonding a tert. carbon group to the nucleus of a 1H-pyrazolo[1,5-b]-1,2,4-tirazole coupler is incorporated into a photosensitive material contg. silver halide whose silver chloride content is >80%. A compd. represented by formula I may be used as the coupler A. In the formula I, each of R<1> and R<3> is a (substd). alkyl, at least one of R<1> and R<3> is a group represented by formula II (where each of R<4> -R<6> is a halogen, alkyl, etc.) and R<2> is H or a group releasable by coupling. A concrete example of the compd. represented by the formula I is a compd. represented by formula III (where R is t-butyl).

Description

Detailed Description of the Invention [Industrial Application Field] This invention relates to IH-virazolo (1,5
-bl-1.2.Relating to the use of 4-triazole couplers. [Prior art] IH-Birazoro C1. 5-b)-1.2.4-triazole couplers are described, for example, in U.S. Pat. No. 4,621,0
It is described in specification No. 46. European Patent Specification No. 0. No. 177,765, a coupler of the formula is incorporated into a silver chlorobromide (50% bromine) emulsion. This coupler is said to have good fixing properties and provide dye images that release yellowing.

PROBLEM TO BE SOLVED BY THE INVENTION Nowadays, color photographic paper processable in the PA4 process comprises a silver halide emulsion having at least 80% silver chloride, preferably substantially pure silver chloride. ．． Most If{-virazolo(1,5-b)-1,2,4-triazole couplers provide photographic materials with low raw film storage stability when incorporated into silver chloride emulsions, i.e. When the material is stored after manufacture and before exposure and processing, it exhibits a significant increase in Dmin compared to freshly coated material.Structures of the Invention The present invention improves the raw film storage properties of couplers. The present invention is directed to the use of certain LH-virazolo[1,5-b)-1.2.4-triazole couplers in silver chloride photographic materials for use in silver chloride photographic materials. Therefore, this problem is solved by IH-pyrazolo(1.5-b)- in a silver halide photographic light-sensitive material containing more than 80% chloride.
1. 2. The solution is to use 4-triazole couplers containing a tertiary carbon on the core for the purpose of improving raw film stability. The present invention also provides that 1H-
Virazoro (1.5-b)-1. 2. The present invention also provides a photographic light-sensitive material comprising a support carrying at least one of the above emulsion layers having the couplers containing a tertiary carbon group on a lyazole coupler nucleus.

The silver halide emulsion preferably comprises at least 90% silver chloride, and in particular substantially pure chloride radicals.

Preferred couplers have the formula: where R1 and R3 are each an alkyl group or a substituted alkyl group, R2 is hydrogen or a coupling-off group, and at least one of R1 and R'' is The following formula (wherein R4, R5 and R- are independently a halogen atom, or alkyl, cycloalkyl, amino, aryl, cyano, nitro, heterocyclic or the formula -L-T?'
represents a group, in the formula 1 L-R' group, L is a linking group, R7 is an alkyl, aryl, heterocyclic group, and Ra in the above formula
．． Any two of Rs and R6 can represent a heterocyclic group or an alicyclic group, and R4. Any of R% and R6 may be optionally substituted), all of which groups and substituents do not adversely affect the intended properties of the coupler.
When R1 or R3 in the above general formula is a tertiary alkyl group, they preferably contain 4 to 8 carbon atoms and t
-butyl, t-pentyl or t-octyl. R1 and R3 can also contain 1 to 25 carbon atoms and provide ballast groups that render the coupler non-diffusive in the photographic layer. Ra. Examples of Rs and R& are chlorine, bromine and fluorine; alkyl groups containing 1 to 20 carbon atoms;
For example, methyl, ethyl, proyl, butyl, pentyl, ethylhexyl and eicosyl; cyclohexyl and cyclopentyl; dioctylamino, dimethylamino and dodecylamino; aryls containing 6 to 20 carbon atoms, such as phenyl, naphthyl and mesityl; cyano Nitro: A heterocyclic group consisting of atoms selected from carbon, oxygen, nitrogen and sulfur atoms necessary to complete a 5- or 6-membered ring, such as pyrrolyl, oxazolyl and pyridyl.

Examples of L include O, S, Co, C01SOx.
SO, Rl' and R9 in these formulas are
independently hydrogen, alkyl such as alkyl containing 1 to 30 carbon atoms, e.g. methyl, ethyl, proyl, butyl or eicosyl or aryl such as aryl containing 6 to 20 carbon atoms, e.g. , phenyl or naphthyl; or heterocyclic groups consisting of atoms selected from carbon, nitrogen, oxygen and sulfur atoms necessary to complete the 5- or 6-membered heterocycle, such as virolyl, oxazolyl and pyridyl.

Examples of R7 include alkyl containing 1 to 30 carbon atoms, such as methyl, ethyl, proyl, butyl,
Mention may be made of pentyl and eicosyl; aryls such as those containing 6 to 20 carbon atoms, e.g.
Examples include phenyl and naphthyl; or atoms selected from carbon, nitrogen, oxygen and sulfur atoms.
or a 6-membered heterocyclic group, such as an oxazole, pyridine, virol or thiophene ring.
When any two of R4, RS and R6 form a heterocyclic group (ring), this may be oxazole, pyridine, virol and thiophene, or
If they form a cycloaliphatic ring system, this may be cyclohexyl, norbornyl or adamantyl.

The coupling-off group Rz may be a halogen atom or an aryloxy or arylthio group.

The couplers used in the present invention can be made by methods known in the art. Typically, the couplers of this invention are combined with a silver halide emulsion layer coated on a support to form a photographic element. As used herein, the term "in combination" means that the coupler is incorporated into a silver halide emulsion layer or an adjacent layer so that it is capable of reacting with silver halide development chemicals during processing. means.

These photographic elements can be single color elements or multicolor elements. In multicolor elements, the magenta dye couplers of this invention are generally combined with green-sensitive emulsions, but they can be sensitized to emulsions or panchromatic hooks sensitized in another region of the spectrum, or orthochromatically It can be sensitized or combined with unsensitized emulsions. Multicolor elements contain dye image forms or units sensitive to each of three primary regions of the spectrum. Each unit can be composed of a single emulsion layer or multiple emulsion layers sensitive to a given region of the spectrum.
Each layer of elements, including these layers of image-forming units, can be arranged in various orders as known in the art.

A typical multicolor photographic element includes at least one yellow,
a support carrying yellow, magenta and cyan dye image-forming units comprising at least one blue-sensitive, green-sensitive or red-sensitive silver halide, respectively, in combination with a magenta or cyan dye organic coupler, and a magenta dye; At least one of the organic couplers is a coupler of this invention. The element may include additional layers such as filter layers and barrier layers.

The following discussion of materials suitable for use in the emulsions and elements of this invention is published in Research Disclosure.
ch Disclosure) + December 1978, Item 17643 (Industrial Op.
ports Ltd. Published by the Ol
dHarbourmaster's. 8North
Street+ Emsworth, Hants PO
IO 7DD, U. K. ) would be done by quoting.

This publication is referred to below as 'Research Disclo.
It is abbreviated as "sure".

The silver halide emulsions used in the elements of this invention may be either negative-working or positive-working. Suitable emulsions and methods for their preparation are described in Rese
arch Disclosure, Sections 1 and 2 and the literature cited therein. Suitable vehicles for the emulsion layer and other layers of the elements of this invention are described in Research Disclosure, Part I
Described in Section X and the documents cited therein. In addition to the couplers of this invention, elements of the invention include Resea
rchDisclosure. Section ■, paragraph D
, E, F and G and the references cited therein.

The couplers of this invention and any additional couplers,
Research Disclosure, Section 1, Paragraph C and the references cited therein. The photographic elements of this invention, or their individual layers, may contain optical brighteners (Research Disclosure. Section V).
), antifoggants and stabilizers (Resea
rchDisclosure (see Section ■)
, antistain agents and image dye stabilizers (Research
Disclosure, Section ■, Baragraph ■ and J.), light absorbers and scattering materials (Rese.
Arch Disclosure, Section ■), hardening agents (Research Disclosure
, Section XI), plasticizers and lubricants (Res.
Search Disclosure, section xn), antistatic agents (Research Disclosure, Section xn)
sure, section xm) Matting agents (Rese)
arch Disclosure, Section X), as well as developer modifiers (Research Disclosure, Section
closures, Section XXI). These photographic elements are Research Disclos
ure, Section X and the literature cited therein.

These photographic elements can be exposed to actinic radiation, typically in the visible region of the spectrum, and are
osure, Section X■ is formed and then processed to create a Research Disclo
A visible dye image, such as that described in Section XII, can be observed. The step of forming a visible dye image includes the steps of contacting the element with a color developing agent to reduce the developable silver halide and oxidize the color developing agent. The oxidized color developing agent reacts with the coupler in turn to form a dye.

Preferred color developing agents include p-phenylenediamines. Particularly preferred are 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamido)ethylaniline sulfate hydrate, and 4-amino-3-methyl-N,N-diethylaniline sulfate hydrate.
Methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-ano-3-β-(methanesulfonamito)ethyl-N,N-diethylaniline hydrochloride and 4
-Agono N-ethyl-N-(2-methoxyethyl)-
m-}luidine p-toluenesulfonate.

Negative working silver halide emulsions yield negative images through this processing step. To obtain a positive (or reversal) image, this step develops the exposed silver halide (no dye) by processing with a non-color developing chemical, and then uniformly fogs the element so that it can be developed. It is possible to leave unexposed silver halide. Alternatively, direct positive emulsions can be used to obtain positive images. Development is followed by conventional bleaching, fixing or bleach-fixing steps to remove silver and silver halide, washing and drying. EXAMPLES The following examples are included for the purpose of furthering the understanding of the invention. Member 1 The couplers were dispersed and applied as follows.

Test coupler (3.0 mmol) dissolved in half the amount of coupler di-n-butyl phthalate and ethyl acetate (2.0 g) was added to aqueous gelatin (36 g) using ultrasonic stirring.
, 12.5%). The gelatin solution contained a small amount (0.5%) of diisobutyrnaphthalene sulfonic acid (sodium salt) as a surfactant. The resulting coupler dispersion was diluted to 200 g with water, and a green sensitized silver chloride photographic emulsion (100 g, 1.49% Ag
+4-5% gel).

This mixture was spread on a resin-coated paper support to obtain a layer with the following composition: 0.267 g Ag/0.54 mmol rrf coupler/bogelatin.
A protective gel supercoat containing 1.61 g/bo hardener was applied to the coating.

Sample strips of these applications are graded
(1 degree range O ~ 3, increment 0.15),
Developed with standard rKODAK J RA-4 processing solution. A sample strip from each application was exposed within a few days of application and l? Treated with A4 chemicals.

Similar strips were placed in a light-proof box and stored under ambient conditions for 29 weeks before exposure and processing. Sensitometric parameters of two sets of applications were measured. Stored applications can exhibit significantly higher Dminl values than freshly treated applications! It was observed. However, the addition of Dmin is 6-
Examples 1b and ld with LI3u substitutions
Compared to the related couplers 1a and fc (see below); Couplers Ua and ■b were tested as described in Example 1, except that the storage period was shortened to 17 weeks. The sensitometric measurements shown below revealed the benefits of the 6-L-nu substitution.

Coupler ■a and m with stabilizing compound ■in the following proportions
Coupler 2 Stabilizer 1 Solvent 3 (Dibutyl phthalate) Me Me This dispersion was coated with a green-sensitive silver chloride emulsion in the following coating sequence: Coupler: 0.57 mmol/nri Ai: 2
．． A set of sample strinops from each 4 mm J/nl application was incubated for 7 days at 50°C and 50% (relative humidity) at +19 locations and compared to an identical set stored at ambient temperature. . Both sets were stepped wedge exposed and processed (RX4). The sensitometric data shown below shows a larger Dmin in the groove than that stored at room temperature, but the difference is that the 5-t-Bu sample (Il
lb) is significantly low. IIIa Me +1.39 mb t-Bu 10.28 Embodiments of the invention include: tertiary carbon'Jg on the coupler core in the silver halide emulsion layer or its adjacent layer.
I II-Biraduro [l. 5-b)-1.
2. A photographic light-sensitive material carrying at least one light-sensitive silver halide emulsion having a 4-triazole coupler and in which at least 80 mol % of the halide is chloride.

An invention in which the coupler is of the formula: wherein R1 and R3 are each an alkyl or substituted alkyl group, and R2 is hydrogen or a coupling-off group, and at least one of R1 and R3 is of the formula: (In the formula, R4 RS and R6 are independently a halogen atom or alkyl, cycloalkyl, amino,
Aryl, cyano, nitro, heterocyclic group or formula -L
-R' group, in which L represents a linking group,
and R7 represents an alkyl, aryl, or heterocyclic group, and
Any two of R4, RS and R6 can form a heterocycle or an alicyclic ring, and the groups Ra. Either Rs or R6 may be optionally substituted)
and all of the foregoing groups and substituents are such that they do not adversely affect the intended coupler properties.

An invention in which R1 or R2 is a tertiary alkyl group containing 4 to 8 carbon atoms.

An invention in which the coupler comprises a decoupling group which is a halogen atom or an aryloxy group or an arylthio group.

An invention in which the emulsion is substantially pure silver chloride.

A yellow dye image, a magenta dye image and a cyan dye image in which the multicolor material is composed of a blue-sensitive, green-sensitive or red-sensitive silver halide emulsion layer in combination with at least one yellow dye, magenta dye or cyan dye coupler, respectively. A photographic material comprising a support carrying dye image-forming units, wherein at least one of said magenta dye-forming couplers is a coupler of the invention.

Claims (1)

[Scope of Claims] 1. 1H-pyrazolo[1,5
-b]-Use of 1,2,4-triazole couplers containing tertiary carbon groups on their core for the purpose of improving raw film stability.