JPH02120738A - Photographic recording material containing magenta coupler and chalcogen azolium salt - Google Patents

Abstract

PURPOSE: To suppress the blocking of the development of a photographic material contg. a prescribed coupler and to enhance sensitivity and contrast by adding a specified chalcogen azolium salt. CONSTITUTION: A hydrolyzable chalcogen azolium salt contg. a quat. substituent having a carbon chain broken by a group represented by formula I, e.g. a compd. represented by formula II is added to a photographic material contg. a silver halide emulsion and a pyrazolotriazole magenta coupler blocking the development of silver halide. In the formula I, L is a combining group, each of T and T<1> is carbonyl or sulfonyl, R<1> is hydrocarbon or amino and m is 1-3. In the formula II, each of R<2> and R<3> is H, halogen, etc., R<4> is H, 1-8C alkyl, etc., Q is the group represented by the formula I, X is an intermediate chalcogen atom, Y is a counter ion and n is 0 or 1. A compd. represented by formula III may be used as the salt represented by the formula II. The coupler may be a compd. represented by formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to photography, and more particularly to photographic recording materials containing magenta dye-forming couplers.

[Conventional technology]

Various types of magenta dye-forming couplers are known. - type is U.S. Pat. No. 3.725.
067 and 4.443.536 and British Patent Nos. 1.247.493 and 1.252.4
For example, pyrazolotriazoles which may contain various substituents including ballast groups are mentioned in No. 18 and No. 1.253.933.

Although such couplers generally provide very favorable photographic results, it has been observed that certain pyrazolotriazole couplers have an inhibiting effect on the development of silver halide in photographic emulsions. This reduces the sensitivity and contrast of the resulting dye image.

[Problem to be solved by the invention]

Therefore, it has been awaited to provide a photographic recording material that solves the problem of inhibition of silver halide development without adversely affecting photographic properties.

The inventors have discovered that special hydrolyzable chalcogen azolium salts containing special quaternary substituents can overcome the development inhibition of silver 10genide caused by pyrazolotriazole couplers.

[Means to solve the problem]

The present invention comprises a photographic lambda silver halide emulsion layer and a pyrazolo IJ azole magenta coupler which inhibits the development of silver halide, and further comprises a compound having the following formula (wherein L is a divalent bonding group and , T is a carbonyl group or a sulfonyl group, T1 is each independently present carbonyl group or sulfonyl group, R1 is a hydrocarbon residue or an amino group, and m represents an integer of 1 to 3) A photographic recording material is provided which also comprises a hydrolysable chalcogen azolium salt of an intermediate chalcogen containing a quaternary substituent having a carbon chain interrupted by a divalent group of the formula:

Pyrazolotriazole couplers that have been found to inhibit silver halide development include compounds of the following formula: 〇H Quaternary chalcogen azolium salts that have been found to be effective in reducing silver halide development inhibition caused by special pyrazolotriazole coupler compounds are described in U.S. Pat. No. 4,578,348. Are listed.

These salts contain hydration which cleaves the chalcogen azolium ring between the 2- and 3-positions (i.e., between the ring chalcogen atom and the carbon atom located between the ring chalcogen atom and the nitrogen atom). You will receive a resolution. When hydrolyzed, these salts have the effect of suppressing silver halide development inhibition caused by the couplers.

As a specific example, a compound represented by the following formula (II) can be used as a reagent that releases the development inhibition of silver halide caused by a special pyrazolotriazole coupler when hydrolyzed: In, R2 and R3 are independently a hydrogen atom; a halogen atom:
Aliphatic hydrocarbon moiety or aromatic hydrocarbon moiety which may optionally be linked via a divalent oxygen atom or sulfur carbon; cyano group; amino group; amidino group; sulfonamide group; sulfamoyl group; ureido group; Thiourido group; Hydroxyl group: Formula -COM or -30
2M, in which M is an aldehyde, a ketone, an acid,
is a group selected to complete an ester, thioester, amide or salt; or R2 and R3 may together represent atoms completing a fused ring: R4 is a hydrogen atom, 1 to 1 carbon atom; an alkyl group of about 8 or an aryl group of 6 to about 10 carbon atoms; Q represents a quaternary substituent; X represents an intermediate chalcogen atom; Y represents a charge harmonizing and n is 0 or 1.

The preparation of the quaternary chalcogen azolium salt is described in US Pat. No. 4,578,348, which is incorporated herein by reference.

When R4 is a hydrogen atom, ring opening occurs automatically after the chalcogenazolium salt of the above formula is incorporated into the silver halide emulsion. If the p)I of the silver halide emulsion is too low for ring opening, treatment with a base, such as an aqueous alkaline solution of an alkali metal or alkaline earth metal or ammonium hydroxide, is carried out before incorporation into the silver halide emulsion. It's okay.

Whether pre-hydrolyzed or automatically hydrolyzed in situ, the salt removes the silver halide development inhibition caused by the special pyrazolotriazole coupler and removes the silver halide development inhibition of formula (II). Those which can be derived by hydrolysis of the compound are represented by the following formula (III): In the above formula, R', R', R', Q, X, Y and n have the meanings as defined above. has.

In a particularly preferred embodiment of the quaternary substituent Q, the following formula (I'V
), -T-fNH-T1iR1 (IV) where L represents a divalent bonding group such as an optionally substituted divalent hydrocarbon group. T is a carbonyl group or a sulfonyl group; T1 is an independently present carbonyl group or a sulfonyl group; R' is an optionally substituted hydrocarbon residue, or represents an amino group: and m is 1 to 3
is an integer.

In a preferred embodiment of the invention, T is a carbonyl group,
And T1 is a sulfonyl group. However, either or both of T and T1 may be either a carbonyl group or a sulfonyl group. Furthermore, m is 1
In larger cases, T1 may be carbonyl or sulfonyl groups occurring independently of each other in those present.

L is preferably an alkylene group of 1 to about 8 carbon atoms (
That is, it is an alkanediyl group).

In particularly preferred embodiments of the invention, L is either a methylene group or an ethylene group.

R1 is preferably a primary or secondary amino group, an alkyl group of 1 to about 8 carbon atoms (e.g. methyl, ethyl, propyl, i-propyl, n-butyl, l-butyl, t-butyl,
-butyl, neopentyl or n-octyl) or an aryl (eg phenyl or naphthyl) group of 6 to about 10 carbon atoms. When R1 completes a secondary amine, it is an optionally substituted hydrocarbon residue, preferably an alkyl group of from 1 to about 8 carbon atoms or from 6 to about 8 carbon atoms, as described above. Can be substituted with about 10 aryl groups. It is also recognized that R1 can be chosen to complete a bis compound if desired. For example, R1 can be a hydrolyzed chalcogenazolium ring bonded to L with a shape similar to L, thereby incorporating a second hydrolyzed chalcogenazolium ring into the compound that can release development inhibition.

In the formula (I'V), m is preferably 1.

Preferred groups for R4 are described above in connection with formula (II) and formula (I), but R4 can be any other substituent that is compatible with the hydrolytic ring opening of the chalcogenazolium salt in the embodiments shown. It is also recognized that it can take a form. Generally, the simpler the form of R4, the easier hydrolysis will be achieved. Specifically, it is recognized that R4 may include a substituent that does not permit automatic hydrolysis of the quaternary chalcogen azolium salt in the silver halide emulsion coating.

X, R2 and R3 can be taken together to complete any convenient chalcogenazolium nucleus or hydrolyzed chalcogenazolium nucleus, with the chalcogen atom provided being an intermediate chalcogen atom. Intermediate chalcogen atoms are sulfur, selenium, and tellurium, and are called "intermediate chalcogen atoms" because they are Group III atoms of the periodic table of elements, excluding those with the highest and lowest atomic numbers. It is called chalcogen.

When X is a sulfur atom or a selenium atom, R2
and R3 can take any form found in known nuclear-containing thiazolium and selenazolium rings. R2 and R3 are independently a hydrogen atom or a halogen atom; a hydrocarbon moiety (for example, an alkyl group,
aryl group, alkaryl group or aralkyl group)
, may optionally be linked via a divalent oxygen atom or sulfur atom (for example, an alkoxyl group, an aryloxyl group, an alkoxyl group, an alkylthio group,
arylthio group, alkarylthio group or aralkylthio group); cyano group; amino group (primary amino group,
(including secondary amine groups and tertiary amine groups); amidino groups (e.g., acetamide groups and butyramide groups);
Sulfonamide groups (e.g., alkyl or arylsulfonamide groups); sulfamoyl groups (e.g., alkylmot, < is an arylsulfamoyl group); ureido groups (e.g., 1-ureido, 3-phenyl-1-ureido, or 3 -methyl-1-ureido group); a thioureido group (e.g., a thioureido group corresponding to the exemplified ureido group above); a hydroxyl group; or a group of the formula -COM or -SO□M (wherein M has the meaning given above); ).

The alkyl moieties of the foregoing and other groups preferably contain from 1 to about 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, amyl, hexyl or octyl). most preferably containing from 1 to about 4 carbon atoms and further substituted with other groups such as halogen atoms, cyanogen groups, aryl groups, carboxyl groups, alkylcarbonyl groups, arylcarbonyl groups and aminocarbonyl groups. may have been done.

Aryl groups and the aryl portion of other groups preferably contain from 6 to about 10 carbon atoms (eg, phenyl or naphthyl groups) and include substituted or unsubstituted groups. Useful substituents include halogen atoms, cyano groups, alkyl groups, carboxyl groups, alkylcarbonyl groups, arylcarbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups and aminocarbonyl groups.

In a preferred embodiment, R' and R2 are taken together;
It forms one or more fused carbocyclic aromatic rings, any of which rings may be optionally substituted, such as a benzo ring or a naphtho ring. When X is a sulfur atom or selenium, the salt is a benzothiazolium salt, a benzoselenazolium salt, an α- or β-naphthothiazolium salt or an α- or β-naphthoselenazolium salt, e.g. , a quaternary unsubstituted salt, or conversely a quaternary salt in which the condensed carbon ring is substituted. Substituents of fused carbocycles (
(if present) can be selected from among the individual substituents defined above for R2 and R3. Generally, the fused carbocyclic substituents (if present) are selected from among those present on the corresponding nucleus in cyanine, merocyanine and hemicyanine dyes.

When the intermediate chalcogen is represented by tellurium, R2 and R3 are together a carbocyclic aromatic ring, such as a fused benzo ring or a fused α- or β-naphtho ring. The carbocyclic aromatic ring is an unsubstituted or aliphatic or aromatic group in which the hydrocarbon portion is optionally a divalent oxygen or sulfur atom, an amino group, an amide group, a sulfone group, Amide group, sulfamyl group, ureido group, thioureido group, hydroxyl group, formula -
COM and -SO□M (wherein M is an atom selected from acids, esters, thioesters or salts) It's okay. Particularly preferred benzo or naphtho ring substituents are alkyl, alkoxyl, alkylthio and hydroxyl substituents, wherein the alkyl substituents have from 1 to 8 carbon atoms, most preferably from 1 to 4 carbon atoms. be.

Y in formula (n) and formula (III) provides an electronically neutral compound. Y can be selected from a wide range of ions known to be compatible with silver halide emulsions. If the chalcogenazolium salt or hydrolyzed chalcogenazolium salt is betaine, n can be 0 since there should be no counter ion to match the charge. In the absence of ionizable substituents, the quaternary chalcogenazolium salt of formula (II) has a single positive charge, so R4 is an acid anion, such as a halide or p-toluenesulfonate. Formula (III) in the absence of ionizable substituents
Since the hydrolyzed quaternary chalcogen azolium salt of ) has a single negative charge, Y is a cation, e.g. or an alkaline earth metal or ammonium cation.

A preferred chalcogenazolium salt that can be used in the present invention is represented by the following formula (V):

Special quaternary chalcogen azolium salts falling within the scope of formula (V) include those represented by the following formula: where R', Y and n have the meanings as defined above.
li2) Desired 1iblJ2 and M3PTS = p-)
Luenesulfonate PTS = p-1-Luenesulfonate PTS = p-Toluenesulfonate The above chalcogen azolium salt is described in U.S. Pat.
No. 8.348 describes the photographic halogenation caused by a specific pyrazolotriazole magenta coupler, although it is used for the purpose of improving the sensitivity/fog relationship in photographic recording materials, including color photographic light-sensitive materials. It is not recognized to have any utility in removing silver development inhibition.

The chalcogen azolium salt can be added to the silver halide emulsion at any time after precipitation of the silver halide grains up to just before coating. It has been found to be effective to prevent inhibition of silver halide development by pyrazolotriazole coupler compounds, and the amount of chalcogen azolium salts incorporated into the silver halide layer is approximately 0.00% of these per mole of silver. old to about 10 mmol. Preferred salt concentrations are from about 0.1 to about 2.0 mmol thereof per mole of silver.

The present invention also provides a method for reducing silver halide development inhibition in a photographic recording material comprising a pyrazolotriazole magenta coupler, comprising: a silver halide emulsion containing the following formula (in the above formula, L is a divalent bonding group, T is a carbonyl group or sulfonyl group, TI is each independently present carbonyl group or sulfonyl group, R1 is a hydrocarbon residue or an amino group, and m is The present invention relates to the above method of adding a hydrolyzable chalcogen azolium salt of an intermediate chalcogen containing a quaternary substituent having a carbon steel interrupted by divalent groups (representing an integer from 1 to 3).

The silver halide emulsions can contain silver halide grains of all conventional shapes or sizes.

In particular, the emulsion may be regular (e.g. cubic or octahedral) or irregular (e.g. polyhedral or tabular).
It is possible to include primary, medium or fine silver halide grains.

High aspect ratio tabular grain emulsions, such as Wilgus
U.S. Pat. No. 4,434,226 to Daubend et al.
414.310 of ick et al., 4 of 1lley.
．． No. 399.215, 4.433 of Solberg et al.
．． No. 048, Mignot No. 4.386.156,
4.504.570 of 3vans et al., Maska
Sky, No. 4, 400.463, Wey et al., No. 4.
No. 414.306, Maskasky No. 4.435.
501 and 4.643.966 and Dau
Particularly preferred are those described in Bendick et al. 4.672.027 and 4.693.964. In addition, silver bromoiodide having a higher molar ratio of iodine in the center than in the outer surface of the grain, for example, British Patent No. 1,027.146; Japanese Patent Publication No. 54-48521
Publication; U.S. Patent No. 4.379.837; U.S. Patent No. 4.4
No. 44.877; No. 4, No. 665.012: No. 4.68
No. 6.178: No. 4.565.778; No. 4.728
．． No. 602; No. 4.668.614; No. 4.636.
Particularly preferred are those described in EP 461; and EP 264.954. The silver halide emulsion may be either monodispersed or polydispersed as a precipitate. The grain size distribution of the emulsion can be adjusted by a silver halide grain separation method or by blending silver halide of various grain sizes.

U.S. Patent No. 1.195.432; U.S. Patent No. 1.951.93
No. 3; No. 2, 448.060; No. 2,628.167
Sensitizing compounds such as copper, thallium, lead, bismuth,
Cadmi and Group I noble metals may be present during precipitation of the silver halide emulsion.

This emulsion was published by Glafkides on Photogr.
aph icChemistry, 1.365-3
Pages 68 and 301-304 (Founta
in Press, London, 1953);
Photograp by G, F, Duf in
hic Emulsion Chemistry, 6
Pages 0-72 (Focal Press Ltd,.

Excess halogen ion ripened emulsion as described in London, 1966): U.S. Patent No. 3.320.069
Thiocyanate-ripened emulsions as described in No.
U.S. Patent No. 3.271.157; U.S. Patent No. 3.574.62
8 and 3,737.313 or U.S. Pat. No. 3.78.
4.381 Specification and Re5earch Disc
losure, No. 134. June 1975, I
Weak silver halide solvent-containing emulsions such as those described in US Pat.

The surface of the silver halide emulsion may be sensitized.

Noble metals (eg gold), intermediate chalcogens (eg sulfur, selenium or tellurium) and reduction sensitizers can be used alone or in combination, with combinations being particularly preferred.

A preferred sensitization method uses sulfur and gold.

A typical chemical sensitizer is Re5earch Discl.
osure.

Listed in December 1978, Item 17643, Section ■.

Silver halide emulsions can be spectrally sensitized with dyes belonging to various classes, including cyanines, merocyanines, complexes of cyanines and merocyanines (e.g. tri-, tetra- and polynuclear cyanines and merocyanines); oxonol, hemioxonol,
Included are vorimethine pigments including styryl, merostyryl and streptocyanin. Specific spectral sensitizing dyes are described in the above-mentioned Re5earch Disclosure.
, Item 17643, Section ■.

The silver halide emulsions as well as other layers of the photographic recording material of the invention may contain hydrophilic colloids as vehicles, used alone or in combination with other polymeric materials (eg latex).

Suitable hydrophilic materials include substances of natural origin, such as proteins, protein derivatives, cellulose derivatives (e.g. cellulose esters), gelatin (e.g. alkali-processed gelatin such as bovine bone or skin gelatin or pig skin gelatin). acid-treated gelatin), gelatin derivatives (such as acetylated gelatin and phthalated gelatin), or polysaccharides (such as
dextran and gum arabic), zein, casein, pectin, collagen derivatives, collodion, agar, kudzu and albumin. These vehicles can be cured by conventional methods. Details of vehicles and curing agents can be found in the above-mentioned Re5earch Disclos.
ure, Item 17643, Sections ■ and X.

〔Effect of the invention〕

The effects of the present invention are explained below: Silver bromoiodide tabular grains (4.5 mol % I) with a uniform diameter of 3.2 mm and a thickness of 0.147 mm are
No. 4,433,048 to G. et al.

Next, several parts of this emulsion were added to sodium thiosulfate (2.5 m
g/Ag mol), tetrachlorite (III) potassium (1,25 mg/Ag mol), sodium thiocyanate (80 mg/Ag mol) and the green-sensitive dye anhydro-5-chloro-9-ethyl-5'-phenyl-3. '
-(3-sulfobutyl') -3-(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt and anhydro-11-ethyl-1,1'-bis(3
-Sulfopropyl) Natsuta (1,2-d) Oxazolocarbocyanine hydroxide sodium salt (0,7 mmol/Ag mol) mixture was used to chemically and spectrally sensitize to the fringes of the visible spectrum. . A magenta dye-forming coupler dispersion, identified as C-1 above, was added to several parts of the chemically and spectrally sensitized emulsion.

1 for 1 copy. 36 mg/Ag mole of the chalcogen azolium salt identified as S-1 above was added. Next, a coating film containing the above components was prepared as follows.

The coating composition described above was applied to separate sections of a gelatin-subbed cellulose triacetate film support. The coating weights were: silver bromoiodide (1,08 g Ag/m'), gelatin (2,15 g/m'), magenta dye-forming coupler (0,57 g/m'). Then gelatin (2,15 g/m'). , 15 g/m') and a hardener bisvinylsulfonyl methyl ether 1.75% (based on total gelatin) was applied.

The resulting photographic element was tested with graded density test specimens from 0 to 4.0 and Wratten No. 974 Luther (
Wratten is an Eastman Kodak Co.
, U, S, A product name) 600W, 55
Imagewise exposure was performed to a tungsten light source at 1/100 seconds. Processing is done by Br1tish Journal ofP
photography Annual, 1979.20
37 types of coloring methods described on pages 4 to 206
．． The development was carried out at 7° C. for 2 minutes and 15 seconds. Result is,
The coatings containing chalcogenazolium salt S-1 were shown to have improved relative sensitivity and contrast values.

Furthermore, embodiments of the invention include: a photographic recording material in which the pyrazolo IJ azole coupler has one of the following formulas: A photographic recording material represented by the following formula: In the above formula, R2 and R3 are independently a hydrogen atom; a halogen atom; an aliphatic group optionally connected via a divalent oxygen atom or a sulfur atom; or aromatic hydrocarbon moiety diano group; amino group; amide group; sulfonamide group; sulfamoyl group; ureido group; thioureido group:
Hydroxyl group: or formula -COM or -SO□M
(wherein M is a group selected to complete an aldehyde, ketone, acid, ester, thioester, amide or salt), or R2 and R3
can represent atoms that together complete a fused ring; R4 is a hydrogen atom; an alkyl group of 1 to about 8 carbon atoms;
or an aryl group of 6 to 10 carbon atoms; Q represents a quaternary substituent; X is an intermediate chalcogen atom; Y represents a charge-adjusting counterion; and n is ,0
or 1.

A photographic recording material in which R4 is a hydrogen atom.

Photographic record where the quaternary substituent Q is represented by the following formula, where L represents an optionally substituted alkylene group having 1 to 8 carbon atoms; T represents a carbonyl group or is a sulfonyl group: T1 is each independently present carbonyl group or sulfonyl group;
and R1 represents a primary or secondary amine group or an alkyl group having a hydrocarbon residue or amino group of 1 to about 8 carbon atoms; and m is an integer from 1 to 3.

A photographic recording material, wherein T is a carbonyl group and T1 is a sulfonyl group.

A photographic recording material, wherein the group is a methylene group or an ethylene group.

A photographic recording material in which m is 1.

A photographic recording material, wherein the X is a sulfur atom.

A photographic recording material in which the chalcogen azolium salts are present in an amount of about 0.01 to about 10 mmol thereof per mole of silver.

from about 0.1 to about 2 of them per mole of silver,
A photographic recording material present in OmiIJ molar amounts.

The chalcogen azolium salt has the following formula: Photographic recording material shown in .

A photographic recording material in which the salt is a compound represented by the following formula: A photographic recording material in which the silver halide emulsion is chemically sensitized.

A photographic recording material in which the emulsion is sensitized with sulfur and gold.

Claims (1)

[Scope of Claims] 1. A photographic recording material containing a photographic silver halide emulsion layer and a pyrazolotriazole magenta coupler that inhibits the development of silver halide, further comprising the following formula ▲ mathematical formula, chemical formula, table, etc. ▼ (In the above formula, L is a divalent bonding group, T is a carbonyl group or a sulfonyl group, T^1 is a carbonyl group or a sulfonyl group that exists independently, and R^1 is a hydrocarbon residue. hydrolyzable chalcogen azolium of intermediate chalcogens containing a quaternary substituent having a carbon chain interrupted by a divalent radical of The above-mentioned photographic recording material, characterized in that it also contains salt.