US3770447A

US3770447A - Light-sensitive silver halide color photographic material containing indazolone couplers

Info

Publication number: US3770447A
Application number: US00213814A
Authority: US
Inventors: I Boie; W Schulte; D Freitag; F Nittel; W Pelz; H Krimm
Original assignee: Agfa Gevaert AG
Current assignee: Agfa Gevaert AG
Priority date: 1970-12-29
Filing date: 1971-12-29
Publication date: 1973-11-06
Anticipated expiration: 1990-11-06
Also published as: BE777352A; GB1350229A; IT945653B; DE2064304A1; FR2121036A5; CH569309A5; CA982395A

Abstract

A light-sensitive photographic material with at least one silver halide emulsion layer which contains indazolone derivatives as couplers for the production of the magenta partial image, which indazolone couplers are represented by the following formula:

WHEREIN THE RADICALS R1, R2, X, Y and Z are denoted in the description.

Description

United States Patent [1 1 Boie et a1.

[ Nov. 6, 1973 LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING INDAZOLONE COUPLERS [75] lnventors: lmmo Boie, Cologne; Walter Schulte,

Opladen; Willibald Pelz, Cologne; Heinrich Krimm, Krefeld-Bockum; Dleter Freitag, Krefeld; Fritz Nittel, Cologne, all of Germany [73] Assignee: Agfa-Gevaert Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Dec. 29, 1971 [21] Appl. No.: 213,814

[30] Foreign Application Priority Data Dec. 29, 1970 Germany P 20 64 304.3

[52] US. Cl 96/100, 96/56.5, 260/310 [51] Int. Cl G03c 1/40 [58] Field of Search 96/100, 56.5

[56] References Cited UNITED STATES PATENTS 2,673,801 3/1954 Jennen 96/100 $043,694 7/1962 Barr et al 96/56.5 3,199,983 8/l965 Kocpkc et a1 96/100 Primary Examiner-J. Travis Brown AttorneyArthur G. Connolly et al.

[57] ABSTRACT A light-sensitive photographic material with at least one silver halide emulsion layer which contains indazolone derivatives as couplers for the production of the magenta partial image, which indazolone couplers are represented by the following formula:

8 Claims, No Drawings LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL CONTAINING INDAZOLONE COUPLERS This invention relates to a light-sensitive color photographic material with at least one silver halide emulsion layer which contains indazolone derivatives as color couplers for the production of the magenta partial image.

It is known to produce color photographic images by chromogenic development, i.e., by developing exposed silver halide emulsion layers by means of suitable color forming developer substances, so-called color developers, in the presence of suitable color forming couplers, the oxidation product of the developer substances produced in areas corresponding to the silver image reacting with the color coupler to form an image which consists of dye. The color developers commonly used are aromatic compounds which contain primary amino groups, especially those of the p-phenylene diamine type.

The color couplers and the dyes obtained from them by chromogenic development must satisfy numerous requirements in practice. The color couplers should have a high rate of coupling with the oxidation product of the color developer. The color couplers and the dyes obtained from them must be sufficiently stable to light, elevated temperature and moisture. This applies both to fresh material and to the processed material. For example, residual coupler still present in the image whites of the processed material must not undergo yellowing. Furthermore, the dyes should be sufficiently resistant to gaseous reducing or oxidizing agents and they must be fixed in a diffusion-fast form in the image layer and in the process of chromogenic development they should be deposited as a very fine grain. Furthermore, the mechanical properties of the layers should not be impaired by the color couplers and lastly the dyes produced from the color couplers in the course of chromogenic development should have a suitable absorption curve with a maximum corresponding to the color of the partial image which is required to be produced and at the same time they should have as little side absorption as possible. In the ideal case, a magenta dye should be almost completely absorbent to green light and high transmittent to blue and red light.

The compounds used as magenta-forming couplers, i.e. color couplers which are suitable for producing the magenta color image, are generally derivatives of 2- pyrazolone-S. lndazolone derivatives are also occasionally used as magenta-forming couplers (see US Pat.

specification No. 2,673,801, 2,964,402, 3,199,983 and 3,486,892. The disadvantages of indazolone couplers, apart from their comparatively low coupling intensity compared with that of pyrazolone couplers, is their tendency to undergo brown discoloration in the course of prolonged storage inthe presence of light. It is particularly this last mentioned property which considerably restricts the use of indazolone couplers for the production of color photographic images on paper or other supporting materials which images are to be exposed to light. Another disadvantage of these couplers is that the strongly polar structure of the original indazolone nucleus leads to the formation of compounds with high melting points even if the substituents of the derivatives are non-polar. Indazolone couplers which are readily soluble in ethyl acetate, methylene chloride and similar organic solvents have not previously been known. This property, combined with the usually high melting points, has hitherto made it difficult to use indazolone couplers in photographic layers.

It has now been found that indazolone couplers which may be preparedby a new process involving alkylation of the nucleus of anthranilic acid esters with suitably substituted styrene derivatives or the corresponding a-carbinols followed by indazolone ring closure are characterised by exceptionally advantageous properties both as regards their higher sensitivity and as regards their reduced tendency to undergo brown discoloration in the presence of light.

The subject of the invention, therefore, is a lightsensitive color photographic material having at least one silver halide emulsion layer, containing a magenta coupler represented by the following formula NH Ill X and Y may be the same or different and represent hydrogen, halogen, e.g., chlorine, alkyl with l to 18 carbon atoms, thioalkyllwith 1 to 18 carbon atoms,

phenyl, aroxy, for example phenoxy, or acylamino in which the acyl group maybe derived from aliphatic or aromatic carboxylic acids or sulfonic acids, the said groups may carry additional substituents, e.g., halogen, hydroxyl, carboxyl, acylamino or carbonyl groups;

X or Y may form together with R or R a cycloalkane ring, for example a cyclohexane ring.

Z hydrogen or a group which renders the compound soluble in alkalis, for example carboxyl or sulfo, optionally in the anionic form, or sulfamyl, optionally substituted with monoalkyl or dialkyl or aryl groups.

Preferred are color couplers of the following formula:

Y I ia NH i H wherein R hydrogen or alkyl, preferably with l to 3 carbon atoms;

In order to obtain couplers which are sufi'iciently fast to diffusion, it is preferred to use indazolone derivatives in which at least one of the radicals R,, R X, Y and Z contains a large hydrocarbon radical with at least 12 carbon atoms. Preferably, at least one of the radicals X and Y is halogen, alkyl, alkoxy, aroxy or acylamino.

The following couplers have proved to be especially suitable:

Moltin Number Coupler point C.

CH3 NH S 03H 2 CH; 0 240244 I Melting point C.)

Coupler Number invention, a suitably Substituted styrene, optionally in the dimeric form, or the corresponding a-carbinol is reacted with anthranilic acid esters with the aid of acid catalysts to aklylate the anthranilic acid esters in the -positio'n. indazolone ring closure in then carried out in a known manner. If desired, a sulfo group may finally be introduced. The method of preparation will now be explained with the aid of a few examples. 5-[a-(4-l-lexadecyloxy-3"-sulfophenyl)-isopropyl]- indazolone (Coupler 2) 1 mol of dimeric isopropenyl phenol is dissolved in 1 litre of propanol at elevated temperature and 2.4 mol of KOH are added. 2.6 mol of cetyl bromide are run into the reaction mixture which is then heated under reflux for 3 hours and filtered while hot through a suction filter. The diether (l) separates from the filtrate.

Yield: 65%, m.p.: 64C.

. CmHa30--+ COOCH3 CH NH2 210 g of dimeric p-cetoxy-isopropenyl benzene (I), 600 g of methyl anthranilate and 25 g of the catalyst K 20 (montmo rillonite catalyst of Sudchemie, Munich) are heated to 225C under nitrogen for 30 minutes. The reaction mixture isfiltered through a suction filter while still hot and the excess ester is distilled off under vacuum. The residue is triturated with petroleum ether,

cooled and filtered through a suction filter.

Yield: 160 g, m.p.: 70C.

CH3 NH .3 #JLID 100 g of compound (II) are dissolved in 200 ml of glacial'acetic acid-and after the addition of 50 ml of concentrated hydrochloric acid the compound is diazotised with amyl nitrite at to C. After one hour, the nitrite excess is destroyed with urea and the diazonium salt solution is run into a solution, which has been cooled to 5 to 10C, of 87 g of SnCl 2 H O in 200 ml of concentrated hydrochloric acid. The reaction mixture is then diluted with water and decanted. It is washed twice with water and the residue is then boiled for 8 minutes in 2N sodium hydroxide solution and the re- To prepare the indazolone couplers according to the Melting Number Coupler point C.)

a0 5 s a 200 "HMO NH sulting solution is then stirred into a mixture of ice and HCl filtered through a suction filter and dried. The crude product is recrystallized from ethyl acetate or methanol.

Yield: 60 g, m.p.: 92C.

S 03H CH3 0 g 50 g of compound (III) are introduced into 400 ml of concentrated sulfuric acid at 0C and the mixture is then stirred at room temperature for half an hour, poured on to ice and decanted. It is then boiled with acetonitrile and recrystallized from propanol.

Yield: 35 g, m.p.: 244C. 5-[a-(2'-Hexadecyloxyphenyl)-ethyl]-indazolone (Coupler 4) COOH: CH3 Q-MD- OCMH33 o-l-lydroxy-acetophenone is etherified with cetyl bromide under alkaline conditions by a known process and the keto group is then reduced to alcohol with sodium borohydride. (o-Cetoxyphenylmethyl carbinol, m.p. 43C.)

g of this carbinol I 500 g of methyl anthranilate, and

25 g of catalyst K 20 are heated to C with introduction of nitrogen and the nitrogen carries with it the water of reaction. The reaction mixture is filtered hot and the excess of anthranilic acid ester is distilled off. The residue is precipitated with ligroin and recrystallized from ethanol.

Yield: 130g, m.p.: 65C.

lndazolone ring closure is carried out in the usual manner and Coupler 4 is obtained.

The new magenta-forming couplers are superior to the known indazolone couplers in three respects. Firstly, their stability is greatly improved, especially their stability to light, and, secondly, the new couplers have a greatly reduced tendency to undergo brown discoloration in the presence of light and, thirdly, the products are much more readily emulsifiable provided the molecule does not contain any group which renders it soluble in alkalis. A particularly remarkable characteristic is the increase in the coupling sensitivity by 3 to 5 DIN, which enables the new components to be used also for highly sensitive photographic material.

The magenta dyes obtained from the new color coupiers by means of N,N-diethyl-p-phenylene diamine or- N-butyl-n-w-sulfobutyl-p-phenylene diamine as developer have exceptionally good spectral properties. The side densities in the blue region and especially in the red region are very low.

The compounds according to the invention are, therefore, valuable color couplers which, on chromogenic development, yield magenta dyes which have excellent stability characteristics. They are eminently suitable for use in light-sensitive silver halide emulsion layers of single layered or multilayered photographic material. However, the magenta-forming couplers need not necessarily be incorporated in light-sensitive layers, but could be introduced into a layer of binder adjacent to a light-sensitive silver halide emulsion layer.

The magenta-forming couplers according to the invention may be incorporated with the silver halide emulsion by one of the known methods or they may be incorporated with another binder mixture. In those cases where the couplers according to the invention are so-called emulsifying couplers, i.e., hydrophobic compounds, incorporation of these couplers is carried out in a known manner by dissolving them in suitable organic solvents, e.g., in esters of aliphatic carboxylic acids, especially in ethyl acetate, or in methylene chloride, and emulsifying this solution in the silver halide emulsion which is ready for casting. Occasionally this method may advantageously be modified by using oily coupler solvents at the same time. This method has been disclosed in [1.8. Pat. Nos. 2,304,940 and 2,322,027.

If the couplers are alkaline, they are added to the -casting solutions for the photographic layers in the form of an aqueous alkaline solution.

Suitable light-sensitive emulsions are emulsions of silver halides such as silver chloride, silver bromide or mixtures thereof, optionally with a small silver iodide content of up to mols percent, in one of the commonly used hydrophilic binders such as protein binders, especially gelatine, or polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives such as carboxyalkyl cellulose, and especially carboxymethyl cellulose, or derivatives of alginic acid.

The emulsions may also be chemically sensitized, e.g. by adding compounds which contain sulfur to the process of chemical ripening, for example allyl isothiocyanate, allyl thiourea, and sodium thiosulfate. The chemical sensitizers used may also be reducing agents, e.g., the tin compounds described in Belgian Pat. specificaq N 4 514. 5 331d. 5.6. .16 or o m d ha diethylene triamine or aminomethane sulfinic acid derivatives, e.g. according to British Pat. No. 789,823.

Other suitable chemical sensitisers are noble metals and noble metal compounds, such as gold, platinum, palladium, iridium, ruthenium or rhodium. This method of chemical sensitisation has been described in the article by R. Kos lowsky, Z. Wiss. Phot. 46, 65-72 The emulsions may also be sensitised with polyalkylene oxide derivatives, e.g., with polyethylene oxide having a molecular weight of between 1,000 and 20,000 or with condensation products of alkylene oxides and aliphatic alcohols, glycols or cyclic dehydration products of hexitols with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides. The condensation products have a molecular weight of at least 700, and preferably more than 1,000. These sensitisers may, of course, be combined for the purpose of achieving special effects, as described in Belgian Pat. specification No. 537,278 and in British Pat. specification No. 727,982.

The emulsions which contain color-forming couplers may also contain spectral sensitizers, e.g., the usual monomethine or polymethine dyes such as cyanines, hemicyanines, streptocyanines, merocyanines, oxonoles, hemioxonoles, and styryl dyes, including also methine dyes which have three or more nuclei, for example rhodacyanines or neocyanines. Sensitizers of this kind have been described, for example, in the work by RM. Hamer, The Cyanine Dyes and Related Compounds (1964), Interscience Publishers, John Wiley and Sons. The color couplers according to the invention are, however, preferably used in emulsions which have been sensitized to green light.

The emulsions may contain the usual stabilisers, e.g. homopolar or salt-type compounds'of mercury which have aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds. Suitable stabilisers are also azaindenes, especially tetraand pentaazaindenes, and especially those which are substituted with hydroxyl or amino groups. Compounds of this type have been described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (1952). Other suitable stabilisers include heterocyclic mercapto compounds, e.g., phenyl mercaptotetrazole, quaternary benzothiazole derivatives, and benzotriazole.

The emulsions may be hardened in the usual manner, for example with formaldehyde or halosubstituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters, dialdehydes.

The usual color developers are used for producing the magenta partial image, e.g., the usual aromatic compounds of the para-phenylene type which contain at least one primary amino group. Suitable color developers are, e.g., N,N-dimethyl-p-phenylen diamine, N,N-diethyl-p-phenylene diamine, monomethyl-pphenylene diamine, N-butyLN-w-shlfobutyl-pphenylene diamine. Other suitable color developers have been described, e.g., in J. Am. Chem. Soc. 73, pages 3,100 to 3,125 (1951). It is preferred to use developers in which the two positions adjacent to the primary amino group are unsubstituted.

The following examples illustrate the invention:

Example 1 tained. Another wedge (b) is prepared by the same method with coupler (l) of the U.S. l at. No.

3,199,983. When the wedges are examined, the sensitivity of wedge (a) is found to be greater by 4 DIN. When both wedges are exposed to daylight, only wedge (b) shows brown discoloration of the whites.

Example 2 is cast on a transparent layer support. After develop-' ment with N,N-diethyl-p-phenylene diamine, the film is bleached and fixed in the usual manner. The coupler is found to be more sensitive by 4 DIN than the coupler in the comparison wedge (Coupler l of the US. Pat. No. 3,199,983). The absorption maximum is in the region of 552 nm.

Example 3 g of Coupler(S) are dissolved in 50 ml of ethyl acetate and, after the addition of 10 g of dibutyl phthalate, the solution is worked up as in Example 2. A magenta wedge which has an absorption maximum at 544 my. is obtained. The sensitivity is higher by 4 DIN than that of wedge (b) from Example 1.

Example 4 10 g of Coupler (19) are cast as described in Exam ple 2. After exposure, the film strip is subjected to the usual reversal process using N,N'-diethylamino-pphenylene diamine as developer substance. A magenta positive image is obtained. The increase in sensitivity compared with that of a film material which contains Coupler (1) of the US. Pat. No. 3,199,983 and has been developed in the same manner is 3 DIN. Absorption maximum 557 nm.

What we claim is: I

l. A light-sensitive photographic material containing at least one silver halide emulsion layer, which contains a magenta coupler of the following formula:

" iQ-Ej wherein R hydrogen or alkyl with l to 3 carbon atoms;

R, hydrogen or alkyl with l to 3 carbon atoms;

R alkyl with up to 17 carbon atoms and R and R may form a cycloalkane ring;

X and Y may be the same or different and represent hydrogen, halogen, alkyl with 1 to 18 carbon atoms, cycloalkyl, alkoxy with l to 18 carbon atoms, thioalkyl with l to 18 carbon atoms, phenyl, aroxy or acylamino;

X or Y may form together with R, or R a cycloalkane ring;

Z hydrogen or a group-which. rendersthe compound soluble in alkalis or sulfamyl.

2. A light-sensitive photographic material containing at least one silver halide emulsion layer, which contains a magenta coupler of the following formula:

wherein R hydrogen or alkyl with l to 3 carbon atoms;

R alkyl with up to 17 carbon atoms;

R and R may together form a cycloalkane ring;

X and Y may be the same or different and represent hydrogen, halogen, alkyl with l to 18 carbon atoms, alkoxy with l to 18 carbon atoms, aroxy or acylamirfo;

Z hydrogen, a group which renders the compound soluble in alkalis or sulfamyl.

3. A material as claimed in claim 11 in which Z denotes a sulfo group.

4. A material as claimed in claim 1 in which at least one of the radicals R,, R X, Y and Z contains a large hydrocarbon radical which has at least 12 carbon atoms.

5. A material as claimed in claim 1 in which at least one of the radicals X and Y is halogen, alkyl, alkoxy, aroxy or acylamino.

6. A material as claimed in claim 2 in which Z denotes a sulfo group.

7. A material as claimed in claim 2 in which at least one of the radicals R R X, Y and Zcontains a large hydrocarbon radical which has at least 12 carbon atoms. 1

8. A material as claimed in claim 1 in which at least one of the radicals X and Y is halogen, alkyl, alkoxy,

aroxy or acylamino.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent: No. 3 7 14! Dated Nov. 6. 197? Inventor(s) Ixnmo B018 et 8-1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Front page, under the heading [57] ABSTRACT, the general formula should read as follows:

Front page, second line after the formula, after "radicals" insert R Column 7, the left side of formula 29 should read as follows:

FORM M050 uscoMM-oc 60376-P69 v i a .5. GOVERNMENT PRINTING OFFICE I 'QB 0-366-334,

Patent No. 3 ,77o,1m7 Dated Nov. 6, 1973 Inventors Immo Bole et al 2 Column l3,zthe formula of claim 1 should read as follows:

Column 1, the formula. of claim 2 should read as follows:

:1 fjt z n/ r H Signed and sealed this 16th day of J uly l974.

(SEAL) Attest:

MCCOY M. GIBSON, JR. c. MARSHALL DANN Attesting Officer Commissioner of Patents

Claims

2. A light-sensitive photographic material containing at least one silver halide emulsion layer, which contains a magenta coupler of the following formula:
3. A material as claimed in claim 1 in which Z denotes a sulfo group.
4. A material as claimed in claim 1 in which at least one of the radicals R1, R2, X, Y and Z contains a large hydrocarbon radical which has at least 12 carbon atoms.
5. A material as claimed in claim 1 in which at least one of the radicals X and Y is halogen, alkyl, alkoxy, aroxy or acylamino.
6. A material as claimed in claim 2 in which Z denotes a sulfo group.
7. A material as claimed in claim 2 in which at least one of the radicals R1, R2, X, Y and Z contains a large hydrocarbon radical which has at least 12 carbon atoms.
8. A material as claimed in claim 1 in which at least one of the radicals X and Y is halogen, alkyl, alkoxy, aroxy or acylamino.