US3891445A - Color photographic light-sensitive materials - Google Patents

Abstract

A color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing a coupler represented by the following general formula (I)

wherein Q represents a coupler residue which can form a dye on reaction with an oxidation product of an aromatic primary amino developing agent; R1 represents an alkyl group, an aralkyl group, an alkoxy group, an alkoxyalkyl group, an acylamido group or an alkoxycarbonyl group, each having from 4 to 20 carbon atoms; R2 represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; m represents an integer of 1 to 4; n represents an integer of 1 to 4; and the sum of m + n is 2 to 5; and R1 and R2 can combine to form a non-metallic atom-containing five membered or six membered ring. These couplers have excellent solubility in coupler solvents and good stability to heat.

Description

United States Patent 11 1 Arai et al.

[ COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS [75] Inventors: Atsuaki Arai; Yasushi Oishi, both of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Kanagawa, Japan [22] Filed: June 18, 1974 [2]] Appl. No.: 480,456

[30] Foreign Application Priority Data June 20, 1973 Japan 48-69383 [52] US. Cl 96/100; 260/310 R; 260/562 R; 260/571 [5 l] Int. Cl G03c 1/40 [58] Field of Search 96/100, 74

[56] References Cited UNITED STATES PATENTS 3,285,747 ll/1966 Coles 96/100 3,737,3l8 6/1973 lnoue et al 96/100 Primary E.\'aminer.l. Travis Brown Anorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A color photographic light-sensitive material which June 24, 1975 comprises a support having thereon at least one silver halide emulsion layer containing a coupler repre sented by the following general formula (l) 3 (R Q NHCOC o (1) wherein 0 represents a coupler residue which can form a dye on reaction with an oxidation product of an aromatic primary amino developing agent; R, represents an alkyl group, an aralkyl group, an alkoxy group, an alkoxyalkyl group, an acylamido group or an alkoxycarbonyl group, each having from 4 to 20 carbon atoms; R represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having I to 5 carbon atoms or an alkoxy group having I to 5 carbon atoms; m represents an integer of l to 4; n represents an integer of l to 4; and the sum of m n is 2 to 5; and R and R can combine to form a non-metallic atom-containing five membered or six rnembered ring. These couplers have excellent solubility in coupler solvents and good stability to heat.

12 Claims, No Drawings 1 COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic light-sensitive material. More particularly, it relates to a color photographic light-sensitive material which contains a novel coupler having an aryloxyisobutyramido group, as an oleophilic group.

2. Description of the Prior Art In general, couplers having an oleophilic diffusionresistant group suitable for use in the production of color photographic light-sensitive materials having good photographic characteristics need to fulfill the following properties.

1. Both the coupler and the dye formed therefrom by color development should have a good solubility in a high boiling organic solvent (for example tricresyl phosphate) which is employed to disperse the coupler.

2. The coupler should have good stability when incorporated into a silver halide photographic emulsion and provide a stable coating on a support without deposition of the coupler.

3. The coupler should have good diffusion-resistance and should not diffuse into other layers.

4. The coupler should have a high coupling reactivity and should produce a dye image having good spectral absorption characteristics as well as good stability to heat, humidity and light.

5. The coupler should be capable of being produced in high purity from low cost raw materials in a simple manner with good reproducibility.

For the purpose of improving the sharpness of color images, it is desired to reduce the thickness of emulsion layers, and thus use of the least amount as possible of a high boiling solvent for dispersing the couplers is desired. It is also necessary to properly maintain the coupler dispersion particles in a stable condition in order to improve the coupling reactivity of coupler and the stability of the dye images.

Many investigations have hitherto been made on oleophilic diffusion-resistant groups which are quite important in the development of an oil-soluble incorporated type coupler which fulfills the above-described conditions.

ln conventional oil-soluble couplers represented by the following general formula (ll) 5 (II) Q NH C W wherein Q has the same meaning as defined above, W represents a diffusion-resistant group, a group having from 9 to 28 carbon atoms has been selected as a diffusion resistant group. When couplers having a group of less than 9 carbon atoms are used, because of their insufficient oil solubility and diffusion-resistance, they partially dissolve into a developer solution or diffuse from an emulsion layer in which they have been incorporated to other layers to reduce the color reproducibility of the color photographic light-sensitive material. On the other hand, when couplers having a group of more than 28 carbon atoms are used, due to their increased molecular weight, the extinction coefficient per unit weight or volume of the dyes formed is small. In addition, the solubility of the couplers per se decreases due to van der Waal attractive forces based on such a group, resulting in a large amount of organic solvent being required and, disadvantageously, an increase in the thickness of the emulsion layers is required to obtain sufficient color density in the emulsion layers.

As the substituent in the general formula (ll), a substituted or unsubstituted aliphatic acyl group, for example, l an n-tridecanoyl group as described in the specification of Japanese patent Application No. 21,454/73 and (2) a B-(N-n-pentadecyl-n-butyramido)propionyl group as described in the specification of Japanese Patent Publication No. 2837/64, is known. As a diffusion-resistant group containing an aromatic ring, for example, (3) a 2,4-di-tert.-amylphenoxyacetyl group as described in the specification of U.S. Pat. Nos. 2,589,004 and 2,600,788, (4) a 2,4-di-sec.-amylphenoxyacetyl group as described in the specification of Japanese Patent Publication No. 3660/69, (5) an 0r-(2,4-di-tert.- amylphenoxy)butyryl group as described in the specification of U.S. Pat. No. 2,801 ,l7l, (6) an a (2- tetradecyl-4-chloro-S-methylphenoxy)butyryl group as described in specification of German Offenlegungsschrift No. l,9l5,948, (7) a 2,4-di-tert.-amyl-6-chlorophenoxyacetyl group as described in the specification of German Offenlegungsschrift No. 2,028,601, and (8) a 3-n-pentadecylphenoxyacetyl group as described in the specification of U.S. Pat. No. 2,908,573 and British Pat. No. 852,922, and the like are known.

Among them, a coupler containing diffusion-resistant group l due to its high aliphatic character, has insufficient solubility in a high boiling organic solvent which is used as a solvent for dispersing an oil-soluble cou pler. In particular, a benzoylacetoanilide type yellow coupler and a phenol type cyan couper containing such a group has poor coupler dispersion stability and often the deposition of coupler results. In the case of a coupler containing diffusion resistant group (2 the purification and crystallization of the coupler during preparation of the coupler are generally difficult. Many procedures are needed to obtain a coupler of high purity, and hence, this is not advantageous from the standpoint of cost. Further a coupler which contains as the diffusion-resistant group such a long alkyl group generally has a low melting point and is quite soluble in organic solvents at relatively high temperatures, but has the disadvantages that the solubility depends greatly on the temperature and coupler is difiicult to dissolve in organic solvents.

On the other hand, it is recognized that a coupler having an aryloxyalkylacylamido group is advantageous in that the solubility of such a coupler in organic solvents tends to be less temperature dependent. In addition, an emulsion layer containing such a coupler has a high film strength and there is less movement of the coupler in an emulsion layer.

Diffusion-resistant groups (3), (4), (7) and (8) exhibit substantially similar properties, and particularly cyan, magenta and yellow couplers containing diffusion-resistant group (3) are described in many references as typical oil-soluble incorporated type couplers. For example. in the specification of US. Pat. No. 2,618,64l the following coupler examples (A, B and C) are described.

CouplerA (cyan) Cl I\HCOCH O-. )-C H (t) Coupler B (magenta) (t)H C -QOCH CO H- c a (t) colts-i3 N :8

\N/ Cl l Cl i CouplerC (yellow) However, these couplers have high melting points, a tendency toward crystallization and insufticicient solubility in conventional high boiling coupler solvents. Thus, due to coupler deposition, a stable dispersion of the coupler in high concentration is difficult to obtain.

Of these couplers, those having diffusion-resistant group (4) generally have low melting points. This is because the raw material. 2,4-di-sec.-amylphenol, includes isomers which are introduced into the coupler, and consequently isolation and purification of the coupler in high purity are difficult, resulting in decreasing the yield of the coupler. On the contrary, in couplers having an oleophilic group in which an alkyl substituent is introduced into the (Jr-position of the alkylacyl group such as the diffusion-resistant groups (5) and (6) (in each of (5) and (6) an ethyl group is introduced), solubility in organic solvents is greatly improved, however,

the reaction between the a-halobutyric acid and phenol used in preparing the coupler is not very sufficient in view of the yield obtained and thus this is not advantageous from an economical standpoint. 5 Further. the most disadvantageous characteristic which couplers containing diffusion resistant groups (3) to (8) have is the dye images formed from these couplers by color development in multilayer color light-sensitive materials in which these couplers are incorporated tend to have reduced heat stability. This is particularly marked in indophenol type dye images prepared from cyan couplers. These facts have been recognized from detailed investigations on the heat stability of dyes formed from various kinds of couplers and the influence of the couplers which exists on the dyes, and, in addition, from comparison tests using photographic films which are prepared by dispersing couplers, coating the coupler dispersion on a support and drying. SUMMARY OF THE INVENTION An object of the present invention is to produce color light-sensitive materials which have excellent photographic properties and color image stability using couplers which have sufficient diffusion-resistance and high solubility in high boiling organic solvents and for which a stable dispersion can be obtained and the thickness of layers can be decreased due to use ofa decreased amount of solvent, and which can be easily prepared using readily available raw materials.

To improve stability of dye images is one of the most important problems in the production of color lightsensitive materials and it is necessary not only to improve the stability of the dyes per se which are formed by color development, but also to remove factors which promote the fading of the dyes. Investigations in great detail have been made on the effects due to the presence of other substances on the heat stability of color developed dyes in a solution system and it has been found that the effect of variations in the structure of couplers present is very great and surprisingly that in a coupler which contains a substituted phenoxyalkylacyl group as difi'usion resistant group. the structure of the NHCOCH CO- alkylacyl moiety of the group greatly influences the heat fading of the developed dyes.

As the results of various investigations, it has been discovered that the objects of the present invention can be accomplished by the use of a coupler having a new type of diffusion resistant group represented by the general formula (I) described hereinafter, in an incorporated-coupler system in which a diffusion resistant coupler which is insoluble or slightly soluble in water is dissolved in a high boiling point organic solvent which is immiscible with water and dispersed in a photographic emulsion.

Accordingly this invention provides a color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing a coupler represented by the general formula (I) Cll wherein 0 represents a coupler residue forming a dye on reaction with the oxidation product of an aromatic primary amino developing agent; R, represents an alkyl group, an aralkyl group, an alkoxy group, an alkoxyalkyl group, an acylamino group or an alkoxy carbonyl group, each having from 4 to 20 carbon atoms; R; represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having l to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms; m is an integer of l to 4; n is an integer of 1 to 4; and the sum of m n is 2 to 5; and R and R may combine together to form a five-membered or a six membered nonmetallic atom containing ring.

DETAILED DESCRIPTION OF THE INVENTION Q in the general formula (I) can be a phenol or a naphthol coupler residue containing a phenolic hydroxy group, a pyrazolone, a cyanoacetophenone or an acylacetonilide coupler residue containing an active methylene group, or a derivative thereof in which the active position is substituted (the so called twoequivalent type coupler). When Q is a phenol or naphthol compound, the coupler is a cyan dye forming cou- A pler; when Q is a pyrazolone or a cyanoacetophenone compound, the coupler is a magenta dye forming coupler, and when Q is an acylacetoanilide compound the coupler is a yellow dye forming coupler. Examples of m i ty are as follows:

- O CH R 0 CH R G-CH R, C \Q o 0 R O O etc 3 f C\ C C 2 R such coupler residues are residues of the couplers disclosed in the following U.S. Patents.

Yellow: U.S. Pat. Nos. 3,277,155; 3,415,652; 3,447,928; 3,408,194; 2,875,057; 3,265,506; 3,409,439; 3,551,155; 3,551,156; 3,582,322, etc.

Magenta: U.S. Pat. Nos. 2,600,788; 2,983,608; 3,006,759; 3,062,653; 3,214,437; 3,253,924; 3,311,476; 3,419,391; 3,419,808; 3,476,560; 3,582,322, etc.

Cyan: U.S. Pat. Nos. 2,474,293; 2,698,794; 3,034,892; 3,214,437; 3,253,924; 3,311,476;

3,458,315; 3,582,322; 3,591,383; etc,

It is preferred from a synthetic standpoint that R, and R: be positioned at the 3- and 5-positions on the phenoxy ring. When R, and R are connected together to form a ring, they are preferrably positioned at the 3- and 4-positions of the phenoxy ring as shown in the following formula:

wherein A, i.e., the combinations of R, and R represents a divalent group necessary to form a S-membered or 6-membered ring, and which can contain one or more oxygen atoms together with carbon atoms.

For A, a divalent group having from 2 to about 35 carbon atoms, for example, those represented by the following formula are preferred:

wherein B represents CH- or O; R R,, R and R., each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and p represents 0 or 1.

Specific examples of the For diffusion resistance, the total number of carbon atoms contained in the moiety 9 5 (R macoo 0 CH5 2 m is suitably from about 14 to 42, and preferably from 18 to 32.

In the present invention, as the coupling residue for Q the following residues are particularly preferred.

13 @wocacozm F c- COCHCONH R12 CH3 X Y w ca e-cosmonaca x CIII-CH-X wherein R represents a mono-valent atom or group, such as a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amino group, an acylamino group; R. represents a hydrogen atom or a monovalent group attached to the 3-, 4- or 5-position of the anilide ring, such as a halogen atom, a cyano group, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, an acylamino group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an imido group, an alkylsulfonyl group, an arylsulfonyl group, etc.; R represents an aryl group, particularly a phenyl group substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group, an acylamino group, etc.; R represents one or more mono-valent atoms or groups, such as a hydrogen atom, a halogen atom, an alkyl group. an alkoxy group, an aryloxy group, etc.; R represents a mono-valent group, such as an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, an acylamino group, an ureido group, an anilino group, or an alicyclicamino group, etc.; R represents one or more mono-valent atoms or groups, such as a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or an acylamino group, etc.; R represents a mono-valent atom or group, such as a hydrogen atom, an alkyl group, an aryl group, etc.; R represents a di-valent group, such as an alkylene group. an arylene group, etc.; X represents a hydrogen atom or a coupling-off group which splits off on coupling with the oxidation products of an aromatic primary amino developing agent, for example. such as a halogen atom, an alkoxy group. an aryloxy group, an acyloxy group, a sulfonyl group, an arylthio group, a heterocyclicthio group, a cyclic imido group, an arylazo group. a cyclic sulfonylacylamino group. etc.; Y represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a N,N-dialkylamino group, etc.

The couplers represented by the general formula (I), which can be used in the present invention, can be prepared easily and in high yield by the reaction of an amino compound represented by the general formula (III):

NH- Q wherein O has the same meaning as defined above, with an appropriate acid chloride derived in conventional manner from an a-(substituted phenoxy)isobutyric acid represented by the general formula (IV):

(R ca (IV) 2 m -o-%-cooa wherein R R. m and n have the same meaning as defined above.

Further, the yellow two-equivalent couplers and the magenta two-equivalent couplers illustrated as examples can be prepared from the coresponding fundamental couplers according to the methods such as those described in the specifications of US. Pat. Nos 3,447,928; 3,408,l94; and 3,265,506, German Offen- Iegungsshrift Nos. 2,213,461; and 2,263,875.

The substituted phenoxy isobutyric acids represented by the general formula (IV), such as, for example, w(4-nonylphenoxy )isobutyric acid, a-( 3-n-dodecyoxyphenoxy )isobutyric acid, a-( 4-ethoxyoctylphenoxy )isobutyric acid, a-( 3-n-pentadecylphenoxy )isobutyric acid, and 01-( 3 -pentadecyl-4- chlorophenoxy )isobutyric acid, a-( 3 pentadecyl-4- methoxyphenoxy)isobutyric acid, a-(2-methyl-2-nhexyadecylchromanyl-fi-oxy)isobutyric acid, a-(2-noctadecyl-Z,3-dihydrobenzofuranyl-5-oxy)isobutyric acid, etc. are novel compounds. They can be prepared in high yield in a one step reaction according to the method described in M. Julia Bull. Soc. Chim. France, 1956, 776, in which the corresponding substituted phenol is heated with acetone and chloroform in the presence of an alkali metal hydroxide to form the alkali metal salt of the carboxylic acid represented by the general formula (IV), followed by neutralization with a mineral acid such as hydrochloric acid.

Specific examples of couplers which can be used in the present invention are illustrated below, but these are only examples of couplers represented by the general formula (I) described above and are not to be considered as limiting the invention.

Coupler I a-( 4-Methoxybenzoyl)-2-chloro-5-{ a-( 4-tert.-amylphenoxy)-isobutyramidol acetanilide Coupler II a-Benzoyl-2-methoxy-5- {a-( 4-nonylphenoxy )isobutyramido} -acetanilide Coupler III a-( 4-Methoxybenzoyl )-2-chloro-5-{rx-( 3 -n-pentadecylphenoxy)isobutyramido}acetanilide Coupler IV a-( Z-Methoxybenzoyl )-a-acetoxy-2-chloro-5- a-( 3- n-pentadecylphenoxy )isobutyramido}acetanilide Coupler V a-( 4-Methoxybenzoyl )-a-(4-carboxyphenoxy )-2- chloro-5-{a-( 3-n-pentadecylphenoxy )isobutyramido}acetanilide Coupler VI a-(4-Methoxybenzoyl)-oz-N-phthalimido)-2-chloro- 5-{a-( 3-n-octyloxyphenoxy )isobutyramido} acetanilide Coupler VII oz-Pivaloyl-Z-chloro-S- {a-(4-tertamylphenoxy )isobutyramidol acetanilide Coupler VIII a-PivaloyI-a-- {-4-(4-benzyloxyphenylsulfonyl)phenoxy} -2-chloro-5- {a-( tert.-amylphenoxy)isobutyramidol acetanilide Coupler IX a-Iivaloyl-2-chloro-5- a( 3-pentadecylphenoxy)isobutyramidolacetanilide Coupler X a-Pivaloyl-a-( lethylcarbamoylphenylthio )-2- chloro-5-{-a-(3-n-pentadecylphenoxy)isobutyramido}acetanilide Coupler XI a-Pivaloyl-a-( 5 ,5-dimethyl-3-hydantoin y] )-2- methoxy-S- {a-( 3-n-pentadecylphenoxy )isobutyramido) acetanilide Coupler XII a-Pivaloyl-oz-( 2-benzotriazolyl)-2-chloro-5- {a-( 4- ethoxybutylphenoxy )isobutyramido} acetanilide Coupler XIII a-PivaIoyl-a-( 2,4-dioxo-5 ,5-dimethyl-3- oxyazolydinyl )-2-chIoro-5- {oz-( 3-n-pentadecylphenoxy )isobutyramido} acetanilide Coupler XIV a-PivaloyI-a-( l-phenethyl-3-hydantoinyl )-2- methoxy-5-a-(4-nonylphenoxy)isobutyramido acetanilide Coupler XV a- {a-( 4-Tolyloxy )isobutyryl -2-chlor0-5- (a-( 3 -npentadecylphenoxy( isobu tyramido Iacetanilide Coupler XLIV 1 -Hydroxy-4-iodo-2-l N-[4-{a-( 3-n-pentadecylphenoxy)isobutyramidolbenzyl] lnaphthamide Coupler XLV 2- {a-( 3-n-Pentadecyl-4- chlorophenoxy )isobutyramido }-4,6-dichloro-5- methylphenol Coupler XLVI 1-( 2,4.6-Trichlorophenyl )-3- {01-( 3 n-pentadecyl-4- methoxyphenoxy )isobutyramido }-5-pyrazolone Coupler XLVll 2-{ a-( 2-Methyl-2-n-hexadecylchromanyl-6- oxy )isobutyramido) -4.6-dichloro-5-methylphenol Coupler XLVIII 1-(2,6-Dich1oro-4-methoxyphenyl)-3-[3-{oz-(3-npentadecyl-4-hydroxyphenoxy)isobutyramidolbenzamidol-S-pyrazolone Coupler XLIX SYNTHESIS EXAMPLE 1 Synthesis of a-(4-Methoxybenzoyl)-2-chloro-5-{a- (3-n-pentadecy1phenoxy )isobutyramido lacetanilide (Coupler III) A crude product, a-(B-n-pentadecylphenoxy)isobutyric acid chloride obtained by the reaction of 19.5 g of a-(B-n-pentadecylphenoxy)isobutyric acid and 18 g of thionyl chloride in the presence of a catalytic amount of dimethylformamide (0.5 g of DMF in 55 of benzene) in benzene, and 15.9 g of 01-(4- methoxybenzoyl)-2-chloro-5aminoacetanilide were reacted by heating in a solvent mixture of 40 ml of acetonitrile and 40 ml of ethyl acetate for 6 hours. After some solid material was removed by filtration, the liltrate was concentrated under reduced pressure, and the residue was recrystallized from a solvent mixture of acetonitrile and ethyl acetate (3:1 by volume) to give 27.0 g of Coupler Ill as colorless crystals with a melting point of 92C.

Found: C: 71.25 percent, H: 7.79 percent, N: 4.06 percent Calculated for C H,-, -,O -,N Cl: C: 71.13 percent, H: 8.03 percent. N: 3.73 percent SYNTHESIS EXAMPLE 2 Synthesis of a-Pivaloyl-Z-chloro-S- {a-( 3-npentadecylphenoxy)-isobutyramido} acetanilide (Coupler IX) 53.7 g of a-pivaloyl-Z-chloro-5-aminoacetanilide and an acid chloride prepared in a manner similar to that described in Synthesis Example 1 from 80 g of a-( 3-npentadecylphenoxy)isobutyric acid were reacted by heating in a solvent mixture of 100 ml of acetonitrile and 60 ml of ethylene chloride for 5.5 hours. After treating in a manner similar to that described in synthesis Example 1, the crude product was recrystallized from petroleum ether to give 105 g of Coupler IX as colorless crystals with a melting point of 7375C.

Found C: 71.19 percent, H: 390 percent, N: 4.37 percent Calculated for C;,,,H,-,;O,N- -Cl: C: 71.06 percent. H: 9.08 percent, N: 4.61 percent SYNTHESIS EXAMPLE 3 Synthesis of a-Pivaloyl-cx-( l-phenethyl-3- hydantoinyl)-2-methoxy-5- {a(4- nonylphenoxy)isobutyramido acetoanilide (Coupler XIV) Into a solution containing 1 1.0 g of a-pivaloyl-2- methoxy-5-{a-(4- nonylphenoxy)isobutyramido acetanilide dissolved in 100 ml of chloroform; was added with stirring at 15C a solution containing 3.3 g of bromine dissolved in 20 ml of chloroform, and reacted for 30 minutes. The reaction mixture was washed twice with 30 ml of cold water, and then to the reaction mixture were added 6.0 g of N-phenethylhydantoin and 3.2 g of triethylamine and the reaction mixture was refluxed on a water bath for 6 hours. The reaction mixture was washed with water and concentrated under reduced pressure. The residue was recrystallized from a solvent mixture of petroleum ether and acetonitrile to give 5.7 g of Coupler XIV as white crystals with a melting point of 8285C.

Found: C: 70.12 percent. H: 7.73 percent, N: 7.39 percent Calculated for C,,H,-,,,O;N,: C: 70.03 percent H: 7.69 percent, N: 7.43 percent SYNTHESIS EXAMPLE 4 Synthesis of l-(2.4,6-Trichlorophenyl)-3-l3-{(Jr-(4 tert-amylphenoxy )isobutyramido} benzamidol-S- pyrazolone (Coupler XXIV) 40.0 g of l-(2,4,6-trichlorophenyl)-3-(3-aminobenzamido)-5-pyrazolone and an acid chloride prepared in a manner similar to that described in Synthesis Example 1 from 25.0 g of a-(4terL-amylphenoxy )isobutyric acid were refluxed in a solvent mixture of ml of acetonitrile and 40 ml of ethylene chloride for 6 hours. After removing some solid material by filtration. the filtrate was concentrated under reduced pressure. Into the residue. 20 g of sodium acetate and 40 ml of acetic acid were dissolved, the solution was poured into ice water with stiring and the crystals are collected by filtration. The crude crystals were recrystallized by a solvent mixture (3:1 by volume) of acetonitrile and ethyl acetate to give 37.7 g of Coupler XXIV as colorless crystals with a melting point of 142143C.

Found: C: 58.77 percent, H: 5.37 percent, N: 8.36 percent Calculated for C;,,H:;1O,N CL;,: C: 59.09 percent, H: 4.92 percent, N: 8.90 percent SYNTHESIS EXAMPLE 5 Synthesis of 1-( 2,4,6-Trichlorophenyl )-3-[ 3- {a-( 3-npentadecylphenoxy-isobutryamidolbenzamido]-5- pyrazolone (Coupler XXV) 20.0 g of 1(2.4,6-trichlorophenyl)-3-(3-aminobenzamido)-5-pyrazolone and an acid chloride prepared in a manner similar to that described in Synthesis Example 1 from 12.5 g of u-(Ln-pentadecylphenoxy)isobutyric acid were refluxed in a solvent mixture of 40 ml of acetonitrile and 40 ml of ethylene chloride for 5.5 hours. The reaction mixture was treated in a manner similar to that described in Synthesis Example 4. The crude product was recrystallized from ethanol to 15 give 17.2 g of Coupler XXV as colorless crystals with a melting point of l37l38C.

Found: C: 63.87 percent. H: 6.65 percent. N: 7.25 percent Calculated for c.,H.,.o.N.c|.,; C: 63.94 percent. H: 6.63 percent. N: 7.28 percent SYNTHESIS EXAMPLE 6 Synthesis of l-(2,4.6-Trichlorophenyl)-3-[2-chloro- -{a-(3-n-pentadecyl-phenoxy)isobutyramido} anilino]-5-pyrazolone (Coupler XXVlll) 23.0 g of l-(2.4,6-trichlorophenyl)-3-{(2-chloro-5- amino)anilino}-5-pyrazolone and an acid chloride prepared in a manner similar to that described in Synthesis Example I from 19.8 g of a-(3-n-pentadecylphenoxy)isobutyric acid were refluxed in l ml of acetonitrile for 3 hours. The reaction mixture was treated in a manner similar to that described in Synthesis Example 4. The crude product was recrystallized from a solvent mixture of acetonitrile and hexane (l:2 by volume) to give 28.5 g of Coupler XXXVI" as colorless crystals with a melting point of l03105C. Found: C: 6l .98 percent. H: 6.39 percent, N: 7.l8 percent Calculated for C..,H.-,..O;.N Cl C: 6l .86 percent. H: 6.44 percent. N: 7.22 percent SYNTHESIS EXAMPLE 7 Synthesis of 2-{a-(4-tert.- Amylphenoxy )isobutyramido }-4.6-dichloro-5- methylphenol (Coupler XXXIX) 22.8 of 2-amino-4.6-dichloro-S-methylphenol hydrochloride and an acid chloride prepared in a manner similar to that described in Synthesis Example I from 25.0 g of a-(4-tert-amylphenoxy)isobutyric acid were refluxed in a solvent mixture of 70 ml of acetonitrile and 40 ml of ethylene chloride for 4 hours. After removing some solid material by filtration, the filtrate was concentrated to half volume and crystals were collected. The crude crystals were recrystallized from acetonitrile to give 37.0 g of Coupler XXXIX as colorless crystals with a melting point of l53l 64C.

Found: C: 62.23 percent. H: 6.60 percent, N: 3.24 percent Calculated for C H O NCl- C:62.26 percent. H: 6.37 percent. N: 3.30 percent SYNTHESIS EXAMPLE 8 Synthesis of 2-{a-(3-n- Pentadecylphenoxy)isobutyramido}-4.6-dichloro-5- methylphenol (Coupler XL) Found: C: 68.05 percent. H: 8.24 percent. N: 2.43 percent Calculated for IlZ J2 IK 'J: I 68-09 percent. 8.33 percent. N: 2.48 percent 5 As can be seen from the above Synthesis Examples.

the couplers which can be used in the present invention are especially advantageous from an economical standpoint in that they can be prepared in a simple manner and a good reproducibility by reacting a novel a-(subl0 stituted)isobutyric acid hydrochloride. which can be prepared in highly purity and high yield by reacting an easily available substituted phenol with acetone and chloroform in the presence of an alkali metal hydroxide. with a yellow. magenta or cyan color coupler residue containing an amino group.

The couplers which can be used in the present invention are a novel class ofcompounds. and in comparison with a similar series of couplers having diffusion resistant groups l to (8) including the known acylamide 0 group described hereinbefore. they have a low melting point and excellent solubility in a high boiling (e.g.. above l75C) organic solvent and thus stable emulsion layer can be obtained without the deposition of coupler crystals in the emulsion layer when they are dispersed 5 in a silver halide photographic emulsion and coated on a support and dried. Due to such characteristics, it is possible to greatly reduce an amount of the high boiling solvent needed for dispersion, which is extremely advantageous for improving the image sharpness of images. Further. while a coupler having a straight chain alkylacyl group (for example Comparative Coupler J described hereinafter) has a very low melting point but shows a low solubility at low temperature due to the high temperature dependency of the solubility and hence tends to be deposited at low temperature, the couplers according to the present invention do not have such disadvantages and furthermore they are characterized by less temperature dependence of solubility as compared with a similar series of couplers.

Using a series of phenolic cyan couplers represented by the general formula (v). the melting points and the soiubilities in ethyl acetate at 20C of the couplers of the present invention and comparison couplers are illustrated below. The comparison couplers have the same structure as the couplers of the present invention except for the diffusion resistant groups. and were pre- -pared according to the method described in US Pat.

Nos. 2,801.17] and 2,908,573.

22.8 g of 2-amino-4,6-dichloro-S-methylphenol hy- OH drochloride and an acid chloride prepared in a manner I similar to that described in Synthesis Example I from C 39.0 g of a-(3-n-pentadecylphenoxy)isobutyric acid Nhco w were refluxed in l20 ml of acetonitrile for 7 hours. The General Formula (2') reaction mixture was treated in a manner similar to that CH described in Synthesis Example 7. The crude product 3 I was recrystallized from acetonitrile to give 41.0 g of C1 Coupler XL as colorless crystals with a melting point of Coupler Diffusion Resistant Melting Solubility in Group W Point Ethyl Acetate at 20C (Cl (WW/F) A CH -O C -.H,,(t) 15s 1.3

Continued Coupler Difl'usion Resistant Melting Solubility in Group W Point Ethyl Acetate at 20C ("Cl (wt%) E 3 D -CHO C,-.H, (l) lSl-l52 20.0

5 "n m E -CH- CH -O Q C,-,Hi (l) 119-120 175 F CHgCH- -CH1-O C,-,H||(t) l24-l25 29.5

G CH O 129-[30 2.1

31 IE H c|-| 0 Q 70 32.5

1 5 3I J (CH 2CH;; 76 24.3

C IS Coupler XL of the C0 73 44,0

Present i invention C :1

Furthermore it has been recognized that the dye images formed by color development in a conventional manner of color light-sensitive materials prepared using the couplers of the present invention have markedly superior heat stability as compared with those formed from known couplers having the above described diffusion resistant groups. This fact is a discovery would not be predicted from the known art, and is to be noted (as shown in Example 4).

Also the melting points of typical yellow and magenta couplers represented by the general formula (I) which Structures and Melting Point ("C) of Typical Yellow and Magenta Couplers Difl-usion Resistant Group W Known Group Invention Group QNHCO CH -O C Hn(t) CHO C.-.Hu(t) H (r) 5 ll C H ('l C H 3 i n) Coupler K Coupler L Coupler lll (H O Q -COCH. .CONH I33 110 92 HCO- CH" Cl Coupler M Coupler N Coupler IX CH;.-(I--COCH' 'CONH [37-438 88 90 73-75 Continued Structures and Melting Point (C) of Typical Yellow and Magenta Couplers Diffusion Resistant Group W Known Group Invention Group CO O-NHCO -CH O C,H ,(tl CH() Q C,-,H,,tt)

H it) S 2 C H (n CH;-C-NHCO O Coupler B Coupler O Coupler XXV HCO- N l77-l78 l4l-l42 l37-l38 Cl Cl Coupler P Coupler Q Coupler XXVlll CH- NH NHCO- Cl ,Cl Cl As can be seen from the results in the above table,

the couplers of the present invention have in common lower melting points as compared with the comparison couplers 0f the homologous series, and stable and very fine dispersions can be obtained even when the dispersion is prepared under the conditions of a reduced amount of the high boiling organic solvent. The coatings prepared under such conditions can also provide dye images of transparency and clear color hue by color development as will be seen in the Examples set out below.

The couplers of the present invention can be incorporated into a hydrophilic colloid of photographic materials using any known technique. For example, the coupler can be dissolved in a high boiling (e.g., above 175C) solvent such as dibutyl phthalate, tricresyl phosphate or trihexylphosphate as described in, e.g., U.S. Pat. No. 2,322,027 together with, ifdesired, a subsidiary solvent such as ethyl acetate, tetrahydrofuran acetophenone, isopropyl acetate, ethyl propionate, B-ethoxyethyl acetate, n-butyl carbitol acetate, etc., and then the solution is dispersed in a hydrophilic colloid binder.

Also. a coupler solution can be prepared using only the subsidiary solvent without using the high boiling solvent and the solution can be dispersed in a hydrophilic colloid binder.

The coupler dispersion prepared in the manner illustrated above is mixed with a silver halide emulsion such as a silver bromide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide or silver iodide emulsion or a so-called conversion halide type silver halide emulsion as described in British Pat. No. 635,841 and U.S. Pat. Nos. 2,592,250 and 3,622,3 l8, and together with, if desired, an additional hydrophilic colloid binder and then the mixture is applied to a support.

The dispersion of at least one coupler of the present invention and, if desired. in combination with at least one known coupler which is not within the scope of the couplers of the present invention, in a hydrophilic colloid binder which is prepared by the above described method can be used as a component of at least one emulsion layer of a multi-layer silver halide photographic material which is based on the three color subtractive system and which has at least one bluesensitive silver halide emulsion layer containing a yellow dye forming coupler, at least one green-sensitive silver halide emulsion layer containing a magenta dye forming coupler and at least one red-sensitive silver halide emulsion layer containing a cyan dye forming coupler. As the emulsions for the multi-layer photographic material, any known silver halide emulsion can be advantageously used, for example, such as those disclosed in U.S. Pat. Nos. 3,582,322; 3,622,3 l 8; 3,547,640; 3,672,898; 3,516,83l; 3,7l5,208; 3,737,3 l2, 3,705,803; 3,705,799; 3,703,375; 3,379,529; 3,402,046; 3,620,747; 3,450,536; 3,726,681; U.S. patent applications Ser. No. 206,060, filed Dec. 8, I97]; and Ser. No. 259,l09, filed June 2, 1972.

As a support to which the emulsion layer containing the dye forming coupler of the present invention is applied, any known support which can be used for conventional photographic materials can be appropriately used. These include a cellulose ester film such as cellulose nitrate, cellulsoe acetate, etc., a polyester film such as polyethylene terephthalate, etc., a polyvinyl chloride film, a polystyrene film, a polycarbonate film, a paper, a so-called baryta coated paper which is prepared by coating a barium sulfate layer on a paper support, a film which is prepared by laminating a cellulose ester, polyester, polyvinyl chloride, polystyrene or polycarbonate on a paper or a baryta coated paper, a synthetic paper, etc. A suitable coating amount of the coupler is about X to about l X 10 mol/m", preferably 2 X 10 to 3 X 10 mol/m and for the silver halide a suitable coating amount ranges from about 5 X 10 to about 1 X 10 mol/m preferably 2 X 10 to 3 X 10 mol/m'-.

As the hydrophilic colloid which can be used in the coupler dispersion of the present invention and the above described emulsion layer of photographic materials, for example, gelatin. a gelatin derivative (acylated gelatin. graft gelatin, etc.). albumin, gum arabic, agar agar, cellulose derivative (acetyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose. etc.), a synthetic resin (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamido, etc.), and any other known hydrophilic colloid can be employed.

The dispersion containing the coupler of the present invention in the above described hydrophilic colloid or a mixture of the dispersion and a silver halide emulsion can be subjected to treatment under reduced pressure or washed with water as described in U.S. Pat. Nos. 2,949,360 and 3,396,027 prior to coating of the emulsion layer of the above described photographic material for removing the subsidiary solvent.

Furthermore, in a step of dissolving the couplers of the present invention, which preceeds the step of dispersing the solution into a hydrophilic colloid binder, the dissolution of the coupler can be facilitated, if desired, using heat or ultrasonic waves as is known in the art.

The above described multi-layer photographic material which includes the couplers of the present inven tion can have, in addition to the above described silver halide emulsion layers, other layers conventionally employed in light-sensitive materials, for example, a protective layer, a filter layer, an intermediate layer, an anti-halation layer, a subbing layer, a backing layer, a layer containing an ultraviolet absorber, etc. Also, as the binders for these layers, the hydrophilic colloid used for the above described emulsion layers can be used.

Each layer of the above described material containing the coupler of the present invention can further contain a known compound as a hardening agent for the hydrophilic colloid, for example, as described in C. E. K. Mees & T. H. James, The Theory oft/1e P11010- grap/zic Process, 3rd Ed., pp. 5560, Macmillan, New York (1966), US. Pat. Nos. 3,316,095; 3,232,764;

3,091,537; 3,321,313 and 3,543,292; British Pat. Nos. 974,723; 994,869 and 1,167,027; etc. Typical examples examples are aldehyde type compounds such as formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, 2,3-dihydroxy-l,4-dioxane, mucochloric acid, dimethylolurea, etcs, active vinyl type compound such as divinyLsulfone, methylene bismaleimide, 5-acetyl- 1,3-diacryloyl- 1 ,3,5-hexahydrotriazine, N,N,N triacryloyl-l,3,5-hexahydrotriazine, etc.; active halogen type compounds such as 2,4-dichloro--oxytriazine sodium salt, 2,4-dichloro-6-methoxytriazine, sebacic acid bischloromethyl ether, N,N -bis( achloroethylcarbamoyl)piperazine, etc.; epoxy type compounds such as bis( 2,3-epoxypropyl)methyl propyl ammonium para-toluene sulfonate, 1,4-bis(2,3'-

22 epoxypropuloxy)butane, 1,3-diglycidyl-5-(y-acetoxy- B-oxypropyl)-isocyanurate, etc.; ethyleneimine type compounds such as 2,4,6-triethyleneimino-l ,3,5- triazine, bis-B-ethyleneiminoethyl thioether, etc.; methane sulfonic acid ester type compounds such as l,2-di(methanesulfonyloxy )ethane, 1,4-di(methanesulfonyloxy)butane, l,5-di(methanesulfonyloxy)pentane, etc.

The emulsion which can be used in the light-sensitive material containing the coupler of the present invention can be chemically sensitized using the natural sensitizers in gelatin or using a sulfur compound as described in U.S. Pat. Nos. 1,574,944; 1,623,499 and 2,410,689, Also, the emulsion can be sensitized with a salt of a noble metal such as palladium, gold, ruthenium, rhodium, platinum, etc., as described in US. Pat. Nos. 2,448,060; 2,399,083 and 2,642,361. Further the emulsion can be sensitized with a reducing agent such as a stannous salt as described in U.S. Pat. No.

2,487,850. The emulsion can also be sensitized with a polyalkylene oxide derivative as described in U.S. Pat. Nos. 2,886,437; 3,046,134; 2,944,900 and 3,294,540. Moreover, the emulsion can be spectrally sensitized with a sensitizing dye, such as a cyanine dye or a merocyanine dye, as disclosed in U.S. Pat. Nos. 2,526,632; 2,503,776; 2,493,748; 3,384,486; 2,933,390; and 2,937,089.

The emulsion can contain a stabilizer such as a mercury compound, an azaindene, etc., as described in U.S. Pat. Nos. 2,131,038; 2,694,716; 2,886,437; 2,444,605; 2,728,663; 3,287,135; 3,236,652; 2,403,927; 3,266,897; 3,397,987; 2,839,405;

3,220,839; 2,566,263; and 2,597,915; a plasticizer such as glycerine, etc., as described in U.S. Pat. Nos. 2,960,404; 2,588,765 and 3,121,060; and British Pat No. 955,061 and a coating aid such as saponin, polyethylene glycol monolauryl ether, etc., as described in U.S. Pat Nos. 2,600,831; 3,133,816 and 3,666,478. Further the emulsion can contain an antistatic agent as described in U.S. Pat. Nos. 2,861,056; 3,206,312; and 3,428,451, an ultraviolet absorber as described in U.S. Pat. Nos. 3,253,921; 2,739,971; 2,739,888; and 3,250,617, a fluorescent whitening agent as described in U.S. Pat. Nos. 2,933,390; and 3,406,070, an antiirradiation dye as described in U.S. Pat. Nos. 3,253,921; 2,274,782; 2,527,583; and 2,956,879, etc.

In the light-sensitive material containing the coupler of the present invention any known couplers in addition to the couplers of the present invention can also be used. For example, as a yellow dye forming coupler there are the open chained ketomethylene type couplers and typical examples of such couplers are acylacetamide type couplers such as the benzoylacetanilides and the pivaloylacetanilides, etc., as desclosed in U.S. Pat. Nos. 3,277,155; 3,415,652; 3,447,928; 3,408,194; 2,875,057; 3,265,506; 3,409,439; 3,551,155; 3,551,156; 3,582,322, etc. As a magenta dye forming coupler, there are pyrazolone type couplers, indazolone type couplers, pyrazolobenzimidazole type couplers, cyanoacetyl type couplers, etc., as disclosed in U.S. Pat. Nos. 2,600,788; 2,983,608; 3,006,759; 3,062,653; 3,214,437; 3,253,924; 3,311,476; 3,419,391; 3,419,808; 3,476,560; 3,582,322, etc. Also as a cyan dye forming coupler there are phenol type couplers, naphthol type couplers, etc., as disclosed in U.S. Pat. Nos. 2,474,293; 2,698,794; 3,034,892;

23 3,214,437: 3,253,924; 3.31 L476; 3,582,322; 3,591,383; etc.

Each of these couplers can have at the active carbon atom of the coupling position. replacing hydrogen atoms of the active carbon atom, an atom or group capable of being split off on oxidative coupling with an aromatic primary amine developing agent such as a halogen atom or an ether, a thioether, an acyloxy. a phthalimido, a hydantoinyl, a thiocyano, a sulfo, a sulfino, a saccharinyl, a benzotriazolyl, etc., group. Also, the coupler can be a so-called colored coupler having a chromophore such as a diazo group, a styryl group, etc., as a splitting-off group. Further the coupler can have a so-called diffusion resistant group so as to prevent diffusion of the coupler in the emulsion layers. Also the coupler can have a group such as a sulfo group, a carboxy group, etc., for dispersing the coupler in a micellar state as an alkali metal salt or an alkaline earth metal salt thereof.

As a dispersing agent for preparing the coupler dispersion and as a coating aid for applying each coating composition in the production of the light-sensitive material of the present invention, any known surface active agent can be advantageously uses. For example, an anionic surface active agent having a sulfonic acid, a sulfuric acid. a phosphoric acid, a carboxylic acid or a salt thereof; a nonionic surface active agent having a hydroxy group; a cationic surface active agent having an ammonium, a phosphonium, an aniliniurn, a pyridinium, etc. group; and an amphoteric surface active agent having an anionic group and a cationic group in the same molecule; can be used.

The light-sensitive material of the present invention can be treated. after exposure, using known processing methods. For example, when the light-sensitive material of the present invention is intended to use for a negative or a positive material of a nega-posi type system, the material can be treated using the following main steps:

I. Color development 2. Stop or fixing 3. Bleaching followed by fixing, or blixing Of these steps step 2 can be omitted. Also, if desired, a hardening step for hardening the photographic layer or a pretreatment step in an alkaline bath for removing a resin backing layer can be used prior to step 1. Further. if desired, a hardening step can be employed between step 1 and step 2 or step 2 and step 3, or after step 3. Still further, if desired, a stabilizing step for improving the stability of the images can be used. Moreover, washing steps can be used between each of the steps or after the last step. After all of the processing steps are finished, the photographic material is dried. Suitable drying methods which can be used are natural dyring by allowing the material to stand in the air, heat drying, hot-air drying, drying with an infrared radiation, a drying with an electron beam, or any other known methods.

When the light-sensitive material of the present invention is intended to be used for a material of a reversal type system, the material can be treated using the following main steps:

I. Black and white development 2. Reversal exposure 3. Color development 4. Stop or fixing 5. Bleaching followed by fixing, or blixing Of these steps step 2 can be omitted when the color developer solution for step 3 contains a fogging agent. In reversal processing, a hardening step, an alkaline pre-bath step, a stabilizing step, a washing step can be, if desired, employed before or after each step described above, as in the above described nega-posi type processing step. Also after finishing all of the processing steps, the photographic material is dried in the same manner as described in the nega-posi type processing step.

For each step of the above described nega-posi type processing and the reversal type processing, processing baths of known compositions can be used.

A suitable color developer solution is an alkaline solution containing a color developing agent. As the color developing agent, any known aromatic primary amino developing agent can be used, for example, phenylene diamines such as N,N-diethyl-paraphenylene diamine, N-ethyl-N-hydroxyethyl-para-phenylene diamine, N- ethyl-N-hydroxyethyl-2-methyl-para-phenylene diamine, N-ethyl-N-B-methanesulfonamidoethyl3-methyl-4-aminoaniline, N,N-diethyl-2-methyl-paraphenylene diamine, N-ethyl-N-ethoxyethyI-Z-methylpara-phenylene diamine, and the sulfates, hydrochlorides, sulfites, oxalates, etc. of these compounds. The color developer solution can further contain conventional additives such as a sulfate, a carbonate, a bisulfite, a bromide or an iodide of an alkali metal, benzyl alcohol, a water softener (such as sodium hexametaphosphate, an alkali metal hydroxide, hydroxylamine, a sulfate or a hydrochloride of hydroxylamine, etc.), a competing coupler (such as mono sodium l-amino-S- naphthol-3.6-disulfonate, citrazinic acid, etc.), if desired. Also the color developer solution can contain a fogging agent (such as N-butylamine, an alkali metal salt of borohydride, ethylene-diamine, etc.), when it is used as color developer for reversal type processing.

As the stop solution, a solution containing any known pH-reducing agent (such as acetic acid, phthalic acid, etc.) can be used.

As the fixing solution, a solution containing any known fixing agent (such as sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, etc.) can be used.

As the bleaching solution, a solution containing any known belaching agent (such as a ferricyanide, a bichromate, a ferric salt of ethylene-diamine tetraacetic acid, etc.) can be used.

When the bleaching step and the fixing step are carried out in a mono bath, a solution containing any known silver halide solvent and any known silver oxidizing agent can be used. Examples of such silver halide solvents are a thiosulfate, a thiocyanate, an organic diol containing an oxygen atom or a sulfur atom (such as 3-thiol ,5-pentanediol, 3,6-dithial ,8-octanediol, 9- oxa-3,6, l 2, l S-tetrathia-l ,l7-heptadecanediol, etc. a sulfur-containing organic dibasic acid or a salt thereof (such as ethylenebisthioglycolic acid, a sodium salt thereof, etc.), imidazolidinethione, and the like. Also examples of silver oxidizing agents are a ferricyanide, a quinone, a ferric salt. a cupric salt, a cobaltic salt, a complex salt of an ammonium ion or an alkali metal ion, and a ferric ion, a cupric ion or a cobalt ion, and an organic acid (examples of the organic acids are malonic acid, tartaric acid, ethylmalonic acid. malic acid, fumaric acid, diglycolic acid, dithioglycolic acid, ethyliminopropionic acid, nitrilotriacetic acid, ethyl- 25 enediamine tetraacetic acid, aminotriacetic acid, ethylenedithioglycolic acid. dithioglycolic acid. etc. or a chelate compound of ferric ion. cupric ion or a cobalt ion (examples of ligands of the chelate compounds are ethylenediamine, diethylenetriamine. triethylenetetraamine, diaminopropane, diaminocyclohexane. polyethyleneimine, acetylacetone, diethyldithiocarbamate, oxyquinoline, dithiozone. dipyridyl, phenanthrenine, etc.), and the like.

The couplers of the present invention can be used, in addition to the above described multi-layer photographic materials based on substractive three color system, in any silver halide light-sensitive materials which can form dye images by color development using an aromatic primary amino developing agent, such as color radiographic photographic materials, infrared-sensitive photographic materials, photographic materials for recording radar images, color micro-photographic materials, and the like.

The invention will now be explained in greater detail by reference to the following examples.

EXAMPLE 1 A mixture of 3.0 g or Coupler lX (a yellow color forming coupler), 1.5 ml of di-n-butyl phthalate, 2.0 ml of ethyl acetate and 0.15 g of sodium di(2-ethylhexyl)- B-sulfosuccinate was dissolved by heating to 60C and mixed with 25 ml of an aqueous solution at 40C containing 2.0 g of gelatin, and the mixture was stirred using a high speed mixer at 50C for 10 minutes to prepare a fine dispersion of the coupler.

The coupler dispersion was mixed with l50 g of a photographic emulsion containing 47 millimoles of silver iodobromide and 10 g of gelatin, and then 2 ml of a 1 percent aqueous solution of 4-hydroxy-6-methyll.3,3a.7-tetraazaindene, 5 ml of a 2 percent aqueous solution of the sodium salt of Z-hydroxy-4,6-dichloro-striazine and 2 ml of a 5 percent aqueous solution of saponin were added in order. The mixture was coated on a cellulose acetate film base in a dry thickness of 5 microns. On the emulsion layer, a gelatin layer of a dry thickness of 1 micron was coated as a protective layer.

The film was subjected to stepwise exposure for sensitometry and processed in the following steps.

CH O- Q-COCH CONH- The composition of the processing solutions used were as follows.

Color Developing Solution l (pH 105) Water 1000 ml Z-Amino-S-diethylaminotoluene 2.5 g Hydrochloride Sodium Sulfite (anhydrous) 5 g Sodium Carbonate (monohydrate) 47 g Potassium Bromide 2 g Fixing Solution (2H 4.2) Water l000 ml Sodium Thiosulfate (pentahydrate) 80 g Sodium Sulfite (anhydrous) 5 g Borax 6 g Glacial Acetic Acid 15 g Chromium Alum 7 g Bleaching Solution (EH 7.2) Water 1000 ml Potassium Ferricyanide [7 g Borax 5 g Potassium Bromide 7 g After processing and drying, the film provided clear yellow dye images having an absorption maximum at 448 millimicrons.

EXAMPLE 2 A solution prepared by heating to 80C a mixture of 7 g of Coupler ill (a yellow color forming coupler), 3.5 ml of di-n-butyl phthalate. 7 ml of n-butyl acetate and 0.1 g of sorbitan monolaurate was added I20 g of an aqueous solution at 50C containing 10 g of gelatin and 0.5 g of sodium triisopropylnaphthalene sulfonate (Alkanol B made by E. l. du Pont de Nemous, U.S.A.) and the mixture was passed 5 times through a pre-heated colloid mill to prepare a fine dispersion of the coupler.

All of the coupler dispersion collected by washing the colloid mill with cc of a warm water was mixed with 320 g of a photographic emulsion containing 0. l 0 moles of silver iodobromide and 21.3 g of gelatin. and then 5 ml of a 3 percent acetone solution of triethylene phosphamide was added. The mixture was coated on a baryta coated paper laminated with polyethylene in a dry thickness of 4 microns and dried.

For comparison, a film was prepared by earring out the same procedures as described above except that 7 g of a coupler having the following structure was used.

Comparison Coupler (a) Melting Point 955C Comparison Coupler (a) had the same structure as that of Coupler Ill except for the oil-soluble diffusion resistant group, and was prepared according to the method described in US. Pat. No. 2,908,573.

These two film samples were subjected to stepwise exposure for sensitometry and processed in the following steps.

Processing Step Temperature Time 1 Color Development 6 minutes I -Continued 3. Blixing 4. Wash 5 5. Stabilizing Bath 30 seconds The compositions of the processing solutions used were as follows.

Color Developer Solution 11 (pH 10.7)

Water 1000 ml Benzyl Alcohol 120 ml Sodium Hexarnetaphosphate 2.0 g Sodium Sulfite (anhydrous) 2.0 g Sodium Carbonate (monohydrate) 27.5 g Hydroxylamine Sulfate 2.5 g 4-Amino-3-methyl-N-ethyl-N-(B- 4.() g

methanesulfonamidoethyl )aniline Sesquisulfate Monohydrate Stop Solution After processing and drying, the color paper containing Coupler 111 and the sample containing Comparison Coupler (21) provided yellow dye images having an absorption maximum at 449 and 451 microns, respectively.

These color papers having dye images were stored in the dark at 60C and 75 percent relative humidity for 20 days and the fading of the images was measured. The results obtained are shown in the following table.

Rate of Fading (Rate of density after storage against the initial density 1) Sample lnitial Density Coupler Ill of the Present lnvention 12 Comparison Coupler (a) 21 18 As can be seen from the results in the table, the dye images formed according to the present invention using Coupler 111 have improved stability to heat and humidity, than the dye images formed from the light-sensitive material containing known Composition Coupler (a).

EXAMPLE 3 A solution prepared by heating to 65C a mixture of 10 g of Coupler XXV (a magenta color forming coupler), 5 g of tricresyl phosphate, 0.6 g of di-(Z- ethylhexyl)-B-sulfosuccinate and 5 ml of ethyl acetate was mixed with g of a 7 percent gelatin solution. and the mixture was stirred vigrorously using a high speed mixer for 10 min. to prepare a fine dispersion of the coupler.

50 g of the coupler dispersion was mixed with 170 g of a photographic emulsion containing 60 millimoles of silver iodobromide and 12 g of gelatin, and 5 ml of a 3 percent methanol solution of triethylene phosphamide was added. The mixture was coated on a cellulose acetate film base in a dry thickness of 5 microns and on the emulsion layer a gelatin layer having a dry thickness of 1 micron was coated as a protective layer and dried.

For comparison, a film was prepared by carrying out the same procedures as described above except that 8.7 g of a coupler having the following structure was used.

NBC 00 H O Comparison Coupler (B) Melting Point l77-l 78C Comparison Coupler (B) has the same structure as that of Coupler XXV except for the oil-soluble diffusion resistant group.

These two film samples were subjected to stepwise exposure for sensitometry and processed as described in Example 1, except for using a color developer solution having the following composition.

Color Developer Solution lll (pH Water 1000 ml Benzyl Alcohol 3.8 ml Sodium Sulfite (anhydrous) 2.0 g Sodium Hydroxide 1N solution) 14 ml 4 Amino-3methyl-N-ethyl-N-B- 5.0 g metha nesulfonamidoethyl )aniline Sesquisulfate Monohydrate Potassium Bromide 1.0 g Sodium Carbonate (monohydrate) 50.0 g

After processing and drying, both films provided magenta dye images having the spectral absorption characteristics shown in the following table.

Spectral Absorption Characteristics Ratio of a density at a wavelength 60 mp longer than the absorption maximum wavelength in the absorption maximum density.

As is shown in the above table, the color lightsensitive material according to the present invention containing Coupler XXV can provide a spectral absorption curve of a sharply cut form in comparison with the light-sensitive material containing known Comparison Coupler (B). The magenta dye image having such spectral absorption characteristics provides colors of high purity. especially a red color. in color reproduction based on the subtractive photographic system.

EXAMPLE 4 Using six kinds of 5-methyl-4,o-dichlorophenol type 5 Coupler XL (at cyan color forming coupler), l g of 2- l benzotriazolyl-S-n-amylphenol, l 1 ml of di-n-butyl phthalate. 0.2 g or sorbitan monolaurate and l5 ml of ethyl acetate and 150 ml of a gelatin solution containing g of gelatin and 0.4 g sodium dodecylbenzenesulfonate were stirred vigorously in a high speed mixer at 50C for 10 minutes to prepare a dispersion of the couplers in which the average diameter of the oil drop let containing the coupler was 0.2 microns. All of the coupler dispersion collected by washing the mixer with 200 ml of a warm water was added to 250 g of a photodichloro-s-triazine was added. The mixture was coated on a paper laminated on both surfaces with polyethylene in a dry thickness of 2.5 microns, and on the emulsion layer a gelatin layer having a dry thickness of l micron was coated and dried. This film was designated Sample (4-1).

Using the same procedures as described above except for using each of the couplers shown in the following table. five additional kinds of films were prepared.

Film Sample No. Comparison Coupler Amount Used 4-2 Compound A 4.7 g

These six color printing papers were subjected to stepwise exposure for sensitometry and processed as described in Example 2 to provide cyan dye images.

These samples having cyan dye images were stored under the conditions set forth in the following table for enforced fading testing. The results obtained are shown in the following table.

From these results it can be understood that the cyan dye images formed according to the present invention are more stable to fading due to heat and humidity. particularly to heat fading under dry conditions. than the cyan dye images formed from known couplers having similar structures. This fact illustrates that the color photographic images formed from the lightsensitive material of the present invention are more stable than those formed from conventionally known couplers, and can be stored for a long period of time.

EXAMPLE 5 A color printing paper was prepared according to the following procedures. Coating Solution 1 and Coating Solution 2 were simultaneously coated on a surface of a paper laminated on both sides with polyethylene using a slit hopper as described in U.S. Pat. No. 2,761,419. Coating Solution 1 and Coating Solution 2 were coated in order on the support and the dry thickness of each layer was 2.5 and 1.0 micron, respectively. Then Coating Solutions 3,4,5 and 6 were coated, in order, on the coating described above using the same slit hopper. The dry thickness of each layer was 3.0, 2.0, 2.0 and 1.0 micron, respectively.

Coating Solution l A mixture of 24 g of Coupler XIII (a yellow color forming coupler), 18 g of di-n-butyl phthalate and ml of ethyl acetate was dissolved by heating to 50C, the solution thus obtained was added to 600 ml of an aqueous solution containing 40 g of gelatin and 1.5 g of sodium dodecylbenzene sulfonate and then the mixture was passed 3 times through a homogenizer to prepare a coupler dispersion.

All of the coupler dispersion was added to 500 g of a photographic emulsion containing 0.] mole of silver chlorobromide (bromide content: mole percent, average grain size: 0.8 p.) and 40 g of gelatin, and then 60 mg of 5-methyl-6-hydroxyl .3,4-triazaindene and 20 ml of a 3 percent methanol solution of triethylene phosphamide was added.

Coating Solution 2 A mixture of 5 g of n-pentadecylhydroquinone. l5 g of di-n-butylphthalate and I ml of ethyl acetate was dissolved by heating to 50C. the solution thus obtained was added to l.000 ml of an aqueous solution containing 70 g of gelatin. 0.8 g of sodium dodecylbenzene sulfonate and 0.l g of sodium bisulfite. and then the mixture was passed 3 times through a homogenizer to prepare a dispersion. To the dispersion l .500 ml of water, L000 ml of a 2 percent aqueous solution of the potassium salt of poly-p-sulfostyrene and 20 ml of a 3 percent methanol solution of triethylene phosphamide was added.

Coating Solution 3 A mixture of 23 g of Coupler XXVlll (a magenta color forming coupler), 1.5 g of 2.5-di-tertoctylhydroquinone, l.5 g of 4.4.4',4'-tetramethyl-6.6'- dihydroxy-7.7'-dimethoxy-2,2-spirochroman, 20 g of tri-o-cresyl phosphate and 50 ml of ethyl acetate was dissolved by heating to 50C and the solution thus obtained was added to 600 ml of an aqueous solution containing 40 g of gelatin and L5 g of sodium pdodecylbenzene sulfonate. and then the mixture was passed 3 times through a homogenizer to prepare a coupler dispersion.

All of the coupler dispersion was added to l .000 g of a green-sensitive photographic emulsion containing 0.2 moles of silver chlorobromide (bromide content: 40 mole percent, average grain size: 0.25 14) and 90 g of gelatin. and then 120 mg of 5methyl-6-hydroxy-l ,3.4- triazaindene and 40 ml of a 3 percent methanol solution of triethylene phosphamide was added.

Coating Solution 4 A mixture of 5 g of 2-benzotriazolyl-4-tertbutylphenol. g of 2-benzotriazolyl-4-tert-butyl-6- iso-butylphenol, 5 g of 2.5-di-tert-octylhydroquinone, 35 g of di-n-butyl phthalate and 50 ml of ethyl acetate was dissolved by heating to 50C and the solution thus obtained was added to 750 ml of an aqueous solution containing 50 g of gelatin, I.8 g of sodium pdodecylbenzene sulfonate and 0.1 g of sodium bisulfite. and then the mixture was passed 3 times through a homogenizer to prepare a dispersion.

All of the dispersion was mixed with 750 ml of an aqueous solution containing 50 g of gelatin and 30 ml of a 3 percent methanol solution of triethylene phosphamide.

Coating Solution 5 A mixture of 17 g Coupler XL (a cyan color forming coupler), g of di-n-butyl phthalate and 40 ml of ethyl acetate was dissolved by heating to 50C and the solution thus obtained was added to 600 ml of an aqueous solution containing 40 g of gelatin and L5 g of sodium p-dodecylbenzene sulfonate and then the mixture was passed 3 times through a homogenizer to prepare a coupler dispersion.

All of the coupler dispersion was added to 500 g of a red-sensitive photographic emulsion containing 0.1 mole of silver chlorobromide (bromide content: 40 mole percent, average grain size: 0.25 p) and 45 g of gelatin, and then 60 mg of 5-methyl-6-hydroxy-l .3,4- triazaindene and ml of a 3 percent methanol solution of triethylene phosphamide was added.

Coating Solution 6 To 1.000 ml of an aqueous solution containing 40 g of gelatin. there were added l50 ml of a 2 percent aqueous solution of the potassium salt of poly-psulfostyrene. 20 ml of a 2 percent aqueous solution of sodium p-dodecylbenzene sulfonate and 50 ml of a 3 percent methanol solution of triethylene phosphamide.

The color printing paper thus prepared was exposed through a color negative image and subjected to the color developing treatment as described in Example 2. A clear color print comprising a yellow dye image hav' ing an absorption maximum at 442 mp. a magenta dye image having an absorption maximum at 540 mp. and a cyan dye image having an absorption maximum at 665 my. and having a maximum blue light density of 2.45. a maximum green light density of 2.55 and a maximum red light density of 2.40 was obtained.

EXAMPLE 6 A mixture of IO millimoles of a coupler of the present invention (as shown in the following table). 5.0 g of a high boiling coupler solvent and 10 ml of ethyl acetate was dissolved at refluxing and the solution was added to ml of an aqueous solution containing 0.5 g of pdodecylbenzene sulfonate and I0 g of gelatin and then the mixture was stirred vigorously using a homoblender to prepare a fine dispersion of the coupler.

All ofthe coupler dispersion was mixed with 400 g of a photographic emulsion containing 0.] mole of silver iodobromide (iodide content: 3 mole percent, average grain size: 0.4 microns) and 35 9 of gelatin and then 12.0 ml of a 3 percent methanol solution of triethylene phosphamide and 500 cc of water were added. The mixture of each dispersion thus prepared was coated on a transparent cellulose acetate film base in a dry thickness of 6.0 microns to prepare films.

These films were subjected to stepwise exposure for sensitometry and processed in the same manner as described in Example I using 2-amino-5- diethylaminotoluene as a color developing agent. Dye images having the absorption maximum shown in the following table were obtained.

-Cntinued Coupler Coupler Solvent Absorption Maximum Wavelength of Dye lmage XXVlll TCP 545 XXIX THP 544 XXX TCP 543 XXX! 550 XXX" 550 XXXlll 551 XXXlV 539 XXXVI 546 XXXVII DB? 710 XXXlX 676 XL 675 XLl 674 XL" 666 XLlll 71 l XLlV 712 DPB: Di-n-hutyl phthalatc TC P: Tri-o-cresyl phosphate THP: Trim-hcxyl phosphate EXAMPLE 7 3.00 mg ofa cyan dye (MP. 139C, A,,,,, 659 mp1. e=3 1,500) which was obtained by the coupling of Coupler A (a phenol type cyan coupler) with N,N- diethyl-para-phenylenediamine using silver chloride as an oxidizing agent in an alkaline condition. 3.00 mg a coexisting coupler and 100 mu of di-nbutyl phthalate (DBP) were placed into a brown colored glass ampoule of a volume of 0.8 ml (0.5 X 4.0 cm) to protect from light and humidity, and the contents were dissolved by vibrating. The ampoule was dipped into an oil bath at a controled temperature of 110 1' 0.2C and rocked for -30 hours. Then the ampoule was opened and the amount of remaining dye was spectrometrically determined in methanol.

The influence of various coexisting couplers to the ratio of remaining dye is shown in the following table. la the table, the ratio of the remaining dye was illustrated using the rate of decrease in the absorption coefficient against that of the fresh dye.

ln the above experiments the couplers and DB? of high purity which had been purified in a conventional manner were used. Also the glass ampoules were washed with a chromic acid mixture. then with water vapor and dried.

Variation of Coexisting Coupler Ratio of Remaining Dye Control (without coupler) 94.6 Coupler A 49.9 Coupler D 84.2 Coupler G 52.0 Coupler H 83.7 Coupler XXXIX 93. l Coupler XL 92.8 Coupler XLI 91.7

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

l. A color photographic light-sensitive material which comprises a support having thereon at least one silver halide emulsion layer containing a coupler represented by the general formula CE I 3 (R Q NHCOC 0- wherein 0 represents a coupler residue forming a dye upon reaction with an oxidation product of an aromatic primary amino developing agent; R represents an alkyl group, an aralkyl group. an alkoxy group, an alkoxyalkyl group, an acylamido group or an alkoxycarbonyl group, each having from 4 to 20 carbon atoms; R, represents a hydrogen atom, a chlorine atom, a hydroxy group, an alkyl group having from I to 5 carbon atoms or an alkoxy group having from I to 5 carbon atoms; In represents an integer of l to 4; n represents an integer of l to 4; and the sum of m n is 2 to 5; and R and R: can form a non-metallic atom-containing five membered ring or a six membered ring.

2. The color photographic light-sensitive material as claimed in claim 1, wherein said coupler has the general formula (I315 2 Q-NHCOC o wherein Q, R, and R are as defined in claim 1.

3. The color photographic light-sensitive material as claimed in claim 1, wherein m is 1 and n is l and 0, R and R are as defined in claim I.

4. The color photographic light-sensitive material as claimed in claim 1, wherein said coupler has the general formula 1 i Q NHCOC wherein Q, R, and R are as defined in claim 1.

5. The color photographic light-sensitive material as claimed in claim 2, wherein R represents a hydrogen atom. a chlorine atom, a methyl group or a methoxy group.

6. The color photographic light-sensitive material as claimed in claim 3, wherein R represents a hydrogen 35 36 atom. a chlorine atom. a methyl group or a methoxy group.

7. The color photographic light-sensitive material as claimed in claim 2, wherein a total number of carbon atoms included in the R /N C CH 2 R -n l 5 R 14 l -NHCOC-O 1 C-CH-X g l (3H moiety is from M to 42. Y

8. The color photographic light-sensitive material as 15 claimed in claim 4, wherein a total number of carbon N c NH atoms included in the n l (i3 CH X CH 1 5 R1 0' -NHCOCl O 2 CH /N c NHCONH moiety IS from 14 to 42. R1 N 9. The color photographic light-sensitive material as Ll I claimed in claim 1, wherein Q represents an C CH X acylacetanilide. a cyanoacetophenone, a S-pyrazolone, ll :1 phenol or a l-naphthol coupler residue. 0

10. The color photographic light-sensitive material as claimed in claim 1, wherein Q represents a coupler residue having the formula R N N=C-1\HCO@ 14 I Qcoclmcomi fi 0H X X 0 R y 40 N I a C C5 X g -COZHCONHQ 15 X 0H 12 Y 1? T QO-CII-COCHCORH-Q x R 011 x R 1 CH CON 8 CB -i-COCiI-ECONH- wherein R represents a monovalent atom or group selected from the group consisting of a hydrogen atom, a halogen atom. an alkyl group. an alkoxy group. an amino group or an acylamino group; R is bonded to the 3-position, 4-position or 5-position of the anilide ring and represents a hydrogen atom or a monovalent group selected from the group consisting of a halogen atom. a cyano group. a carbamoyl group. an alkoxycarbony] group. a sulfamoyl group. an acylamino group, a nitro group. an alkyl group, an aryl group. an alkoxy group. an aryloxy group, an imido group. an alkylsulfonyl group or an arylsulfonyl group; R represents an aryl group selected from the group consisting ofa phenyl group substituted with a halogen atom. an alkyl group. an alkoxy group. an aryloxy group. a nitro group. a cyano group or an acylamino group; R, represents one or more monovalent atoms or groups selected from the group consisting of a hydrogen atom. a halogen atom, an alkyl group, an alkoxy group or an aryloxy group; Ru; represents a monovalent group selected from the group consisting of an alkyl group, an aryl group. an alkoxy group, a carbamoyl group, an acylamino group, a ureido group. an anilino group or an alicyclic amino group; R represents one or more monovalent atoms or groups selected from the group consisting of a halogen atom, and alkyl group, an alkoxy group. an aryloxy group or an acylamino group; R represents a monovalent atom or group selected from the group consisting ofa hydrogen atom, an alkyl group or an aryl group; Rm represents a divalent group sea 38 lected from the group consisting of an alkylene group or an arylene group; X, represents a hydrogen atom or a coupling-off group which is split off on coupling with the oxidation product of an aromatic primary amino developing agent and is selected from the group consisting of a halogen atom, an alkoxy group, an aryloxy group. an acyloxy group, a sulfonyloxy group, a cyclic diacylamino group, a cyclic sulfonylacylamino group; and Y represents a hydrogen atom, a halogen atom. an alkyl group, an alkoxy group, an aryloxy group or a N.N-dialkylamino group.

11. The color photographic light-sensitive material as claimed in claim I, wherein said coupler has the general formula Q rmcoc 0 CH C 5H5 (n) a phenol or a l-naphthol coupler residue.

Claims (12)

1. A COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL WHICH COMPRISES SUPPORT HAVING THEREON AT LEAST ONE SILVER HALIDE EMULSION LAYER CONTAINING A COUPLER REPRESENTED BY THE GENERAL FORMULA

2. The color photographic light-sensitive material as claimed in claim 1, wheRein said coupler has the general formula

3. The color photographic light-sensitive material as claimed in claim 1, wherein m is 1 and n is 1 and Q, R1 and R2 are as defined in claim 1.

4. The color photographic light-sensitive material as claimed in claim 1, wherein said coupler has the general formula

5. The color photographic light-sensitive material as claimed in claim 2, wherein R2 represents a hydrogen atom, a chlorine atom, a methyl group or a methoxy group.

6. The color photographic light-sensitive material as claimed in claim 3, wherein R2 represents a hydrogen atom, a chlorine atom, a methyl group or a methoxy group.

7. The color photographic light-sensitive material as claimed in claim 2, wherein a total number of carbon atoms included in the

8. The color photographic light-sensitive material as claimed in claim 4, wherein a total number of carbon atoms included in the

9. The color photographic light-sensitive material as claimed in claim 1, wherein Q represents an acylacetanilide, a cyanoacetophenone, a 5-pyrazolone, a phenol or a 1-naphthol coupler residue.

10. The color photographic light-sensitive material as claimed in claim 1, wherein Q represents a coupler residue having the formula

11. The color photographic light-sensitive material as claimed in claim 1, wherein said coupler has the general formula

12. The color photographic light-sensitive material as claimed in claim 11, wherein Q represents an acylacetanilide, a cyanoacetophenone, a 5-pyrazolone, a phenol or a 1-naphthol coupler residue.