JPH03215856A - Photographic element containing yellow pigment image forming coupler of benzoyl acetanilide - Google Patents

Abstract

PURPOSE: To increase solubility in a coupler solvent by using a benzoylacetanilide coupler having an aryloxy group releasable by coupling, represented by a specified formula and contg. a ballast substituent made of an alkyl group with a chain broken by an ester group in at least one of rings. CONSTITUTION: A benzoylacetanilide coupler having an aryloxy group releasable by coupling and represented by formula I has improved solubility in a coupler solvent. In the formula I, at least one of rings A, B has a ballast group R1 made of an alkyl group with a chain broken by an ester group and the ballast group is represented by the formula -(CH2 )p -L<1> -(CH2 )q -CH3 . The coupler is dissolved in a coupler soln. and the resultant soln. is dispersed in an aq. gelatin soln. The solvent is, e.g. dibutyl phthalate, tricresyl phosphate, diethyl-lauramide or 2,4-di-tert.-amylphenol.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to photographic yellow dye image-forming couplers of penzoylace 1 anilide and photographic elements containing them.

[Conventional technology]

Pertaining to penzoylacel anilides containing heterocyclic coupling-off groups, e.g. U.S. Pat. No. 4,230,851
No. 4,327,175 and No. 4,529,69
Couplers such as those described in No. 1 are known.

[Problem to be solved by the invention]

In recent years, henzoylacetanilide couplers with aryloxy force-pulling leaving groups have attracted attention as providing image dyes with excellent hue and high extinction coefficient.

However, do these couplers reach the desired solubility in the coupler solvent (2)? There is a tendency to

This class of couplers is described in U.S. Patent No. 4,511,649.
It is generally described in the specification of No. 1 (Coupler 10),
The valance l group is attached to the anilide ring of the coupler through an ester group, and the moiety has the formula -CO
-0-C+zll■5. Such a balas 1・
Grouped couplers do not reach the desired solubility in the coupler solvent.

[Means to solve the problem]

The present invention solves the above problems by providing a photographic element containing a benzoylacetanili type F coupler having an aryloxy force-pulling leaving group that exhibits improved solubility in the coupler solvent, and The couplers are represented by the following formula (I).

(3) In the above formula, Rl is a cyclic or acyclic group containing less than 20 carbon atoms, which may be substituted or unsubstituted, and may be branched or unbranched. is a hydrocarbon or ballast group, R2 is an aryl group of 6 to 20 carbon atoms, which may be substituted or unsubstituted, and at least one of the rings A and B is such that the chain is formed by an ester group. Halast substituents consisting of interrupted alkyl groups (
R'). This ballast substituent is R
1 may be included.

The couplers of this invention have one or more ballast substituents of sufficient size and configuration to ensure non-diffusivity so that they do not diffuse into the photographic element. As will be appreciated, the required bulk can be shared by more than one substituent, if desired.

These halastic groups may form part of R1,
and/or can be bonded (4) directly or indirectly to one or both of rings (A) and (B).

The aryl group R2 is an alkyl group, an amide group, an ester group, a carpamoyl group, a sulfonamide group,
It may be substituted with one or more substituents selected from a sulfamoyl group, a sulfone group, an ether group, a thioether group, a nitrile group, a nitro group, and a halogen atom.

These ballast groups can be represented by the following formula.

(CH2)p-L'-(CH2). -CH3 In the above formula, l, I are -O-CO or -co-o-te, and p and q are each from 1 to 25.

Examples of valance l groups that can be used in couplers of the invention include (C}Iz) z-CO-0-C+ zLs-n+ -
(CL) Z-0-CO-C7}11 sn, (C
H2) Io-0-Co-CzH5-n and -(Cl
lz)z-0-CO-Cll(Et)Bu.

A preferred group of couplers in the present invention is represented by the following formula (II):
It is indicated by.

(5) In the above formula, R3 and R'&J are each a substituted or unsubstituted alkyl group, L is -COO-, OCO, -NI1
7GO- , -CONR7, -NIl7SO2 , -
S (JNR'., -O-, oSOz or a single bond, R6 is aru 1: tr, amine 1'' group, carbamoyl group, snorefopumido group, snolesonmo inoleco.1
R? is H or anoleni-1-nole, and the balas 1-group in the formula is l? 1 and/or &J: to R'(
6) If R4 is not a halaste group, -Ll? ' is trifluoromethyl, chloro, -N
HPO (OR) 2 or -PO (OR) 2 (
In these formulas, R is alkyl or aryl. Specific examples of groups that R1 and R3 can represent include cyclic aliphatic groups with 5 or 6 carbon atoms, which may be substituted or unsubstituted, saturated or unsaturated; group groups and acyclic groups of 1 to 20 carbon atoms, such as methyl, ethyl, n-butyl, n-dodecyl, n-hexadecyl, n
-undecyl and benzyl groups.

R2(I-') in the coupling-off group [2N) is shown below along with an abbreviation that may be specified herein.

(7) The dye-forming couplers 1n of this invention can be used in the manner and for the purposes for which color-forming couplers have been traditionally used in the photographic art.

Typically, a silver genide emulsion layer coated on a support and the coupler neck of the present invention are assembled to form a photographic element. As used herein, the term "in conjunction with" refers to processing in which the cuffler reacts with the halogenated steel development composition or the I:I silver-genide emulsion layer or its means incorporating them into adjacent layers.

(}{) A typical coupler is dissolved in a coupler solvent and this solution is dispersed in an aqueous gelatin solution. Examples of coupler solvents that can be used include dibutyl phthalate,
Tricresyl phosphate, diethyl lauramide and 2,4-di-tert-amylphenol are mentioned. Additionally, auxiliary coupler solvents, such as ethyl acetate, cyclohexanone, and 2-(2-butoxyethoxy)ethyl acetate, which are removed from the dispersion prior to incorporation into the photographic element, can also be used.

Photographic elements of the present invention can be single color or multicolor elements. In multicolor elements, it is common for the yellow dye-forming couplers of this invention to be combined with blue-sensitive emulsions, but they may be combined with emulsions sensitive to different regions of the spectrum, or they may be combined with emulsions that are panchromatically scattering, It is also possible to combine with orthoromically sensitive emulsions or non-sensitized emulsions. Multicolor elements contain dye image-forming units that cast light in each of three primary areas of color. 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 the element, including these layers of image-forming units, can be arranged in various orders known in the art.

A typical multicolor photographic element comprises a yellow dye image-forming unit comprising at least one blue-sensitive silver halide emulsion layer in combination with at least one yellow dye-forming coupler, which is a coupler of this invention, and a magenta dye-forming coupler. at least one coupler or cyan dye-forming coupler
The support comprises a support carrying magenta dye image-forming units and cyan dye image-forming units comprising at least one green-sensitive silver halide emulsion layer or red-sensitive silver halide emulsion layer, respectively, in combination with seeds.

The element may include additional layers such as filter layers.

In the following discussion of materials suitable for use in the emulsions and elements of this invention, Research Disclosure+ (R
search disclosure). ．． 19
December 1978, Item 17643. (Indus
trial Opportunities Ltd. (
I0) The Old Harbor-master's+
8 North Street, Emsworth
, ! {ants POIO 7DD+ U. K. +Published). This publication is referred to as rRes
It will be identified as EARCHDisclosure J.

The silver halide emulsions used in 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 I and II and the references cited therein. Suitable vehicles for the emulsion layer and other layers of the elements of this invention are described in Research Disclosure+ Section 1 and the references cited therein.

In addition to the coupler 4 of this invention, elements of the invention include Rese
Additional couplers may be included as described in Arch Disclosure, Section 1, Paragraphs D, EF and G and the references cited therein.

The coupler of this invention and any additional coupler (I1
) can be incorporated into eel elements and emulsions.

The photographic elements of this invention or their individual layers may contain bleaching agents (see Research Disclosure Section V), antifoggants and stabilizers (Research Disclosure Section V).
chDisclosure Section 2], stain inhibitors and image dye stabilizers (Research
sclosure, Section ■, paragraphs I and J), light absorbers and scattering materials (Research
h Disclosure, Section ■), hardening agents (Research Disclosure, Section
ff section), plasticizers and lubricants (Resea
rch Disclosure + Section X■), matting agents (Research Disclosure
e, Section XVI) as well as development modifiers (R
esearch Disclosure No. XXItl,
(see also).

Photographic elements of the present invention are manufactured by Research Disclo
It can be coated on a variety of supports, such as those described in Chap.

Photographic elements are typically exposed to actinic radiation in the visible region of the spectrum and
e, form a latent image as described in Section ■, and then process it in (I2) Research DISCFsl'l'
Visible dye complexes such as those described in Section XIX can be formed. 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 produce a dye.

Preferred color developing agents are phnylene diamines. Particularly preferred are 4-amino-3-methyl-N,N-jethylaniline hydrochloride, 4-amino-3-methyl-N,N-jethylaniline hydrochloride;
-Methyl-N-ethyl N-β-(methanesulfonamido)ethylaniline sulfate hydrate, 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β-(methane sulfonamide) edyl-N,N-diethylaniline hydrochloride and 4-amino-N-ethyl-N=(2-methoxyethyl)-m-}
Examples include luidine-p-}luenesulfonate.

Negative working silver halide emulsions yield negative images through this processing step (I3). Positive (or inverted)
To obtain an image, this step develops the exposed silver halide by processing it with a colorless developing agent (no dye is produced).
The element is then uniformly fogged to leave developable 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.

Specific examples of couplers according to the invention are listed in Table 1 below.

(I4) 1st top - crushed left gupni L sail r 1 -CI+3 -COO(C
I+2) 20-COCI Jlzs-n2 -
(Ctlz) + ocOOczlls -CI
3 - (Cllz) I OCOOC2115
-CI': +4 n-Buo -
CO2Cll2CI+20CO(CI+2>6CI+
35 n-Boo -COzCI
IzCIIzOCOCII(I!t)Bun The coupler cheek of the invention can be manufactured in a manner known per se. The specific manufacturing process is shown below.

〔Example〕

The following examples are included to provide a further understanding of the invention.

(I5) ■± Each test coupler (0.24g) along with di-n-butyl phthalate (0.12g) and ethyl acetate (0.72g) for Cab 11
) was accurately weighed into a standard test tube fitted with a cotton wool stopper. These samples were placed in a water bath preheated to 75-80°C, stirred occasionally for 15 minutes, and then left to stand at room temperature. After removing these samples from the water bath,
5, 10, 15, 20, 25, 30, 4560.
Tested for crystallization (or signs of opacification) at 90 and 120 minute intervals.

These results are shown in Table 2 along with the results for comparative couplers of the prior art (the structural formulas of all of which are shown in Table 1). It can be seen that the couplers of the present invention exhibit solubility that significantly surpasses their linear counterparts.

This test is considered a good indicator of how the coupler is likely to behave in photographic applications.

(I6) First A table ■ COO (CH2) zO-COC+ 21125-n>
120 C1 COOC+ 411zq-n 20-25 3 (CI12)I. -COOC2}+5 60-90 5 COO- (CHz) 2-OCOCH (E t)
-CJq-n>120 (glassy) C5 COOC+ zHzs-n <5 (I7) 1-1 Table CO. ? Shifu 1 Fu: 2 1 (trans 1 -1.-r
? ' -OR2Cl -CI
13 -COOC+ 41129-II
S01'C2-Cllj-COOC+ 6l1
3:+-n SDr'C3 -C+ zl
lzs-n-C I
SDPC4 -C+zllzs-n -
CF3 SDPC5-Bu
-n -COzC+ ■llzs-n
11-promoundecanoic acid (53 g, 0.2 mol) and concentrated sulfuric acid (Imf) in SDP ethanol (250 zn)
The solution of fi) was heated under reflux for 24 hours. After cooling to room temperature, the mixture was concentrated to half its initial volume by evaporation under reduced pressure. The residue was poured into water (400d) and extracted with diethyl ether (3 x 300mE). Next, (I8) the combined extracts were dissolved in saturated sodium bicarbonate solution (3×2
00m) and then with water (3 x 200mg!.). After drying over MgSO4, the solvent was removed in vacuo to give a yellow oil (55.5 g, 95%).

? Bromoester from (a) (55.3 g, 0.19 mol), 4-hydroxyacetophenone (25.7 g, 0.19 mol) and potassium carbonate (26.1 g, 0.19 mol) in setone (2'50d). 19 mol) was heated under reflux for 2 days with stirring. After cooling to room temperature,
Water (500 mR) was added and the whole mixture was dissolved in ethyl acetate (3
Extracted with X 300m). Next, add 3
N sodium hydroxide solution (300d), water (2x30
0 m), 3N HCffi solution (200 Id), then water (2X300 Id). MgSO. After drying above, the solvent was removed under reduced pressure and the residue was recrystallized from methanol to give a white solid (42.9 g, 65%).

Experimental value F C , 72.33. H, 9.41i
(I9) as CZI}13■04 Theoretical value: C, 72.36; H, 9.2
Potassium t-butoxide (21.3 g, 0.19 mol) in 6% diethyl carbonate (56.6 g, 0.48 mol)
The product from (b) (42 g, 0.12 mol) was added portionwise to the suspension at 75° C. over 10 minutes. Heating was continued at 95°C for 1 hour. After cooling to 50 °C, the suspension was poured into cold water (I2) and diluted with ethyl acetate (3X
400 mR). The organic solution was dried and evaporated under reduced pressure to yield the product as a yellow waxy solid (47 g, 93
%) was obtained. This material was used in the next reaction without further purification.

The product from (c) (47
g, 0. 112 mol) and 3-amino-4-chloropenzotrifluoride (21.9 g, 0.11
2 mol) was heated under reflux for 5 hours. After the last time has elapsed, the volume of the mixture is reduced to 200 mR by distillation.
It was decreased by (20). After cooling to about 80°C, petroleum ether (b.p. 60-80"C, I
ffi). A pale yellow solid was collected by filtration and then recrystallized from petroleum ether (b.p. 60-80°C) to yield a white solid (40.5 g, 63%).

To a solution of the 4-equivalent coupler (40 g, 70.2 mmol) from (d) in dichloromethane (250 d) was added sulfuryl chloride (9.5 g, 70 d) in dichloromethane (I5d).
．． 2 mmol) was added slowly. After stirring for 20 hours at room temperature, the volatiles were evaporated under reduced pressure. The crude product was purified by silica gel column chromatography (eluent: 10% ethyl acetate in petroleum ether (b.p. 60-80"C)) and then recrystallized from methanol to give a white solid (25"C). .2g, 60%) was obtained.

Experimental value F C , 57.67i H , 5.56; C
l, 11.60F, 9.47; N, 2
．． 33CzJ34C1. (21) Theoretical value as hNOs: C, 57.62. H, 5.67; C
l, 11.73; F, 9.43; N,
Chloro coupler (24.5 g, 40
．． 5 mmol) and 4,4'-sulfonyldiphenol (
Triethylamine (I2.12 g, 120 mmol) was added to a solution of 40.5 g (162 mmol).

After stirring for 1 hour at 45-50"C under a nitrogen atmosphere, vigorously stirring cold water (300 d) and concentrated hydrochloric acid (I0 m!) were added.
) was gradually poured into the mixture. The entire mixture was diluted with ethyl acetate (5
00ml. ) and the organic solution was washed with 3N sodium carbonate solution (2×400d), 3N hydrochloric acid (300Id), then dried over MgSO4 and then evaporated under reduced pressure. The crude product was purified by silica gel column chromatography [gradient eluent di-petroleum ether (b.p. 60~
20% ethyl acetate in 80″C) to petroleum ether (b
．． p. Purification in 60% ethyl acetate at 60-80°C) followed by recrystallization from methanol (22) gave a white solid (3.5 g of I, 41%).

Experimental value: C, 60.29i H, 5.25; C
l, 4.16; F. 6.98 iN, 1.6
9; S, 3.91C41H43CIF3NO9
Theoretical value for S: C, 60.18; H, 5
．． 30; Cl, 4.33; F, 6.97; N. 1.7
1; 5, 3.92% In a particularly preferred embodiment of the present invention, the aryl group of R2 is an alkyl group, amide group, ester group, carbamoyl group, sulfonamide group, sulfamoyl group, sulfone group, or ether group at any position. , thioether group, nitrile group, nitro group and a halogen atom; or the ballast group has the following formula: (CH2),, -L' -(C}12 ). ．． -Cll+
(In the above formula, Ll represents -O-CO or -CO-0-); or the coupler is represented by the following formula (■): (23) [''In the two formulas, R3 and R4 are each a substituted or unsubstituted argyl group, Y is chloro or l-lifluoromethyl, and L is -COO-
, -OCO- , -NR'CO- , -CONR
' , ~NR7SOt, -SONR' , -0- ,
-OSOz or a single bond, and R6 is an argyl group, an amide group, a carbamoyl group, a sulfonami U group, a sulfamoyl group, a sulfone group, an engineered group, 2. is one or more substituents selected from Te/l/fi, ether convex, thioether group, 2I-lyl group, 21-mouth group, and haClgen atom, and R7 is H or Aryl-1-r; , and in the formula, the balas 1 group is composed of 173 and/or R4, and also when R4 is not a balas 1 group, -LR' is tolufluoro II methyl, chloro, (24) NHPO (OR) z or -PO(OR)2, where R is alkyl or allul.

Claims (1)

[Claims] 1. Comprising a silver halide emulsion layer and combining it with the following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the above formula, R^1 is a substitution a cyclic or acyclic aliphatic hydrocarbon group which may be substituted or unsubstituted and branched or unbranched;
R^2 is an aryl group which may be substituted or unsubstituted, and at least one of the rings A and B is a ballast substituent (R ^1).