US3738840A

US3738840A - Colour couplers

Info

Publication number: US3738840A
Application number: US00028422A
Authority: US
Inventors: B Anderson
Original assignee: Ilford Ltd
Current assignee: Ilford Imaging UK Ltd
Priority date: 1969-04-18
Filing date: 1970-04-14
Publication date: 1973-06-12
Anticipated expiration: 1990-06-12
Also published as: GB1254345A; CH532801A; DE2018562A1; BE749071A

Abstract

THIS APPLICATION DESCRIBES A COLOUR COUPLER SELECTED FROM THE CLASS CONSISTING OF COMPOUNDS OF THE GENERAL FORMULA:

(3-(R1-X-)PHENYL)-Q-B

AND OF THE GENERAL FORMULA:

(2-(R1-X-)PHENYL)-Q-B

WHEREIN IN THE ABOVE TWO FORMULAE B REPRESENTS A COLOUR COUPLER RESIDUE, Q IS A GROUP CONTAINING AN ALKALI SOLUBILISING RADICAL, R1 IS AN ALKYL GROUP CONTAINING AT LEAST 12 CARBON ATOMS AND X IS A DIRECT LINK OR -O-,

-CONH-

-SO2- OR SO2NH-, CORRESPONDING COMPOUNDS IN WHICH THERE IS A LINKING GROUP BETWEEN B AND Q AND CORRESPONDING COMPOUNDS IN WHICH THERE IS A LINKING GROUP BETWEEN Q AND THE PHENYL GROUP.

Description

June 12, 1973 a. ANDERSON @738,840

COLOUR COUILERS Filed April 14. 1970 2 Sheets-Sheet 1 Arr@ ulg ys United States Patent O1 hee U.S. Cl. 96-100 1 Claim ABSTRACT OF THE DISCLOSURE This application describes a colour coupler selected from the class consisting of compounds of the general formula:

XR1 and of the general formula:

X--R1 wherin in the above two formulae B represents a colour coupler residue, Q is a group containing an alkali solubilising radical, R1 is an alkyl group containing at least 12 carbon atoms and X is a direct link or -O,

-CONH- -SO2 or -SO2NH-, corresponding compounds in which there is a linking group between B and Q and corresponding compounds n which there is a linking group between Q and the phenyl group.

This invention relates to colour photography and in particular to photographic colour couplers.

Many modern processes of colour photography are based on the development of a developable silver salt photographic image by means of an aromatic primary amine compound, for example N:Ndiethyl p-phenylene diamine, or a derivative thereof in the presence of a socalled colour coupler, this being a compound which will couple With the oxidation products of the developer to yield a dye image, usually an azamethine or quinoneimine dye image, in situ with the developed silver.

In many of the processes the coupler contains alkali solubilising groups and is incorporated as an alkali solution into the emulsion layer or layers in which the corresponding dye image is ultimately to be formed. It is important that the coupler is fully compatible with the medium, usually gelatin, of the photographic emulsion since this allows thin layers to be obtained. A thin layer improves the sharpness of the image therein. It is also important that the colour coupler is substantive, i.e. it remains in the layer in Which it is incorporated.

Alkali-soluble substantive colour couplers can be said to have the general structure: B-Q-G where B is the colour coupler residue, by which is meant a group such that the compound B-H (and therefore also the compound B-NH2) is a compound which will react with the oxidation products of N-N-diethyl-p-phenylene diamine, formed during the development of a silver salt image with that compound to yield a dyestutf, Q is a group which includes an alkali solubilising radical, i.e. a radical which renders the colour coupler soluble in alkali solution so that it may be incorporated into an emulsion and G is a photographically inert organic radical of such molecular size and configuration as to render the coupler non-diffusing in the material during processing, i.e. it renders the 3,738,840 Patented June l2, 1973 colour coupler substantive to the gelatin once it has been incorporated therein. There may also be linking groups between the B and the Q group and between the Q and the G group.

It is well known that the interaction of such couplers with gelatin may increase the viscosity of the formulation. In some cases the viscosity increase occurs immediately on mixing, in others it takes place slowly over several hours. and the increase may also depend on the pH of the formulation. Ideally the coupler should give little or no viscosity increase with gelatin solutions at pH 6-8, and the formulation should have a constant viscosity for the time necessary to complete its coating as a layer.

One particular G group which has been widely used to achieve substantivity is the para-n-dodecylphenyl group. It has now been found that surprising advantages may be obtained if instead of the para-n-dodecylphenyl group an ortho-n-dodecylphenyl group or a meta-n-dodecylphenyl group, or the phenyl groups having a long chain alkyl group linked directly or indirectly to the ortho or meta position is used.

According to the present invention, therefore, there is provided a colour coupler selected from the class consisting of compounds of the general Formula I:

and of the general Formula Il:

wherein the above two formulae B represents a colour coupler residue, Q is a group containing an alkali solubilising radical, R1 is an alkyl group containing at least 12 carbon atoms and X is a direct link or O -SO2- or -SO2NH-, corresponding compounds in which there is a linking group between B and Q and corresponding compounds in which there is a linking between Q and the phenyl group.

The colour couplers containing such ortho or metasubstituted groups in general show a greater solubility and lower increase in viscosity when added to gelatin solutions, and tend to give dye images with better spectral absorption characteristics than the corresponding parasubstituted isomers.

Exemplary of the general structure of the colour couplers of the present invention are colour couplers of the general Formulae II to XIII.

wherein the above formulae X, R1 and B have the meanings assigned to them above, R2 is a hydrogen atom or an acyl group and A is a linking group. The linking groups A which may be present are, for example:

(1) in general Formulae III and IX, phthalimide linkages as described in British patent specification No. 1,039,- 452. Couplers of this type are exemplied herein in colour couplers 1-36 and 61468 as set forth later,

(2) in general Formulae IV and X, phthalimide linkages described in British patent specification No. 944,838. Colour couplers of this type are exemplied herein in colour couplers 37-41 as set forth later,

(3) in general Formulae V and XI, imide and in particular succinimide or phthalimide linkages as described in British patent specification No. 949,944. An example of such a colour coupler is l-hydroxy-2-N(3-n-dodecy1- phenyl) 3 :4-phthalimide naphthamide,

(4) in general Formulae VI and XII, n-propionylamino linkages as described in British patent specication No. 830,797. An example of such a colour coupler is 1- phenyl 3-[3-[N-(mn-dodecylphenyl)-acetylamino] carboxy-n-propionylamino -S-pyrazolone,

(5) in general Formulae VII and XIII, phthalimide linkages as described in British patent specification No. 997,550. An example of such a colour coupler is 2- carboxy N (l-phenyl-S-pyrazolonyl-3)benzamide-4- N(3dodecy1phenyl) sulphonamide,

(6) in general Formulae VIII and XIV, pyromellitic diamide linkages, as described in British patent specica- CFI The colour couplers of this invention contain a solubilising group, for example a carboxyl group, or a group which is converted to a carboxyl group by aqueous alkali. For example colour couplers of general Formulae III, IV, V, VII, IX, X, XI and XIII contain ve membered cyclic imide rings, colour couplers of general Formulae VIII and XIV contain two such rings, which imide rings may be converted to the amic acid having a free carboxylic acid group by treatment with aqueous alkali in the presence of a solvent such as a lower alcohol, for example n-propanol, followed by acidification. The couplers of this invention are generally incorporated in a gelatino silver halide emulsion by means 0f their alkali solubilising groups, i.e. as the salts of the amic acid. The behaviour of the imide rings may be Written When mixed with the emulsion the exact state of the free carboxylic group will be determined by the particular colour forming structure and the pH of the mixture.

Suitable B groups which may be used in the color couplers of the invention are for example:

(l) Those which contain a -COCHZCO- group, for example benzoyl-4-amino-2-methoxyacetanilide, 4 methoxybenzoylacet-4amino2methoxyanilide, the 2-alkoxybenzoylacet-amino-anilides described in British patent specification No. 595,314, or the aminobenzoylacetmethoxy-anilides of British patent specification No. 800,408, and which give yellow dyestufs on colour development with substituted p-phenylene diamines.

(2) Those which contain a cyanacetyl group or a pyrazolone ring for example 4 w cyanacetylaniline, 1 methyl 3 amino 5 pyrazolone, 1( -hydroxyethyl) 3- amino 5 pyrazolone, 1phenyl3amino5 pyrazolone and substituted l-aryl-3-amino-S-pyrazolone as described in British patent specification Nos. 547,- 064; 680,474; 680,488; the 1 heterocycle-S-amino-S- pyrazolones as described in British patent specification No. 599,919, the 1-(aminoaryl)-3-coumarilyamine 5- pyrazolones of British Patent specification No. 865,720 or the l-phenyl-3-aminoarylamin 5 pyrazolones described in British patent specification No. 968,461 and British patent specification No. 956,261 or the l-halogen-phenyl-3-amino pyrazolones described in British patent specification No. 1,173,943 or the 1cyanohalo genphenyl-3-amino pyrazolones of British patent speciiication No. 1,170,859 and which give magenta dyestuts on colour development with substituted p-phenylene diamines,

(3) phenols and 1-naphthols, which contain an amine group, for example, 4-chloro-5-methyl-Z-aminophenyl or the aminophenols described in British patent specication Nos. 797,131; 754,306; 1amino5naphthol N(aminoethyl)-l-hydroxy 2 naphthamide or similar N-substituted naphthamides containing an amino group, as described in British patent specification No. 902,266 which may also be substituted in the 4-position, as described in British patent specication No. 757,368 and which give cyan dyestulfs on colour development with substituted p-phenylene diamines.

The following examples will serve to illustrate the invention.

EXAMPLE 1 Examples of couplers of General Formula III Colour couplers of general Formula III were produced @8346 w 6 is a straight chain dodecyl group as shown in the followwherein B has the value indicated in the following Table 1, A is a phenyl group and X is a direct linkage and R1 ing general formula:

\ -o ONE- C H TABLE 1 u C011- pler M.P., hmz. ot No. B C. derived dye *Il 11H00-Q 0 CH:

2....-- C1 1oz-194 m-@-w f x5.

CN-E

C1 N--III C1 /-NHOC@ CH, l

s. CN 1an-184 55s @Ii-N Il C" o G,

212-213 54a CN- N--ll c O CI s-.-.-.'.. 2oz-204 54s i -NHoC-Q o/ C,

9..--.. CN m4-205 549 o1-`N--N I ll /o\ o (1)/ Ca omo-@ cocnmoNH-Q 11...... 0B 175176 ess CONHKCHBCHzl This particular coupler was prepared in the amic acid form.

The colour couplers of Table l are obtained by condensing an anhydride of formula with a colour coupler amine B.NH2, where B is as defined in the table. The condensations are generally carried out in acetic acid at the boil and where the couplers precipitate they are collected from the hot reaction mixture, l

Coupler No. 1

A mixture of 2.95 parts of 1-phenyl-3-(3-aminobenzonylamino)--pyrazolone, 4.35 parts of 4-(3-dodecylphenylaminocarbonyl)phthalic anhydride and 50 parts of acetic acid is stirred under reux for 2 hours. The yellow precipitate formed is collected by ltration from the hot reaction mixture, washed first with acetic acid and finally with ethyl acetate. The 5.6 parts of 4-(4 dodecylphenylaminocarbonyl)N (3-[1-phenyl-5-pyrazolyl-3]aminocarbonyl phenyl)phthalimide are obtained as a yellow solid melting at Z55-256 C. On analysis the compound was found to contain 72.4% carbon, 6.2% hydrogen and 9.9% nitrogen (C43N45N5O5 requires 72.5% of carbon, 6.3% hydrogen and 9.8% nitrogen).

'I'he 4-(3-dodecylphenylaminocarbonyl)phthalic anhydride used in the above may itself be prepared as follows:

A solution of 10.4 parts of m-dodecylaniline in 40 parts of monochlorobenzene is added dropwise over 2 hours to a stirred solution of 8.4 parts of trimellitic anhydride acid chloride in parts of monochlorobenzene at 95- C. The mitxure is stirred for a further 30 minutes at 95-100 C. and then allowed to cool overnight to crystallise. The pale yellow solid is collected by filtration and washed well with ethyl acetate. The 13.4 parts of 4-(3 dodecylphenylaminocarbonyl)phthalic anhydride are obtained as a yellow solid melting at 122-l24 C.

The trimellitic anhydride acid chloride used here may be prepared by the action of thionyl chloride on trimellitic anhydride.

The wavelength of maximum light absorption quoted in the table relates to the dye obtained by reversal processing of a coated layer containing the colour coupler using 4-amino-Nethyl-N--hydroxyethylaniline sulphate as colour developing agent.

In some cases the colour couplers have been examined in negative or paper systems using the same colour developing agent. ln these instances the bmx value quoted is suflixed with the letter N or P.

A typical example of the preparation and processing of a photographic layer is as follows:

A mixture of 2.35 parts of coupler No. 1, 3.3 parts of 2 N potassium hydroxide solution and 5 parts of npropyl alcohol is warmed to dissolve. The solution so obtained is screened and diluted with 30 parts of distilled water, and added to parts of a green sensitised gelatino silver halide emulsion containing silver halide equivalent to 2.4 parts of silver and 7.5 parts of gelatin, The emulsion is made up to a total of 250 parts by the addition of distilled water and then coated onto film base and the coated layer dried. When the photographic layer is exposed to green light, developed in a black and white developer, reexposed to light and developed in a colour developer containing 4-amino-N-ethyl-N-- hydroxyethyl aniline sulphate, bleached and fixed, a magenta dye image with light absorption maximum at 544 millimicrons is obtained.

EXAMPLE 2 Further colour couplers of general Formula III were produced. In these couplers B has the value indicated in Table 2 which follows, A is a phenyl group, X is O and R1 is a dodecyl group as shown in the following formula:

co U \CO conn@ .CinHzs 1 1 TABLE Z-Continued M.P., km. of C. derived dye CON HCHz. CH2- CON HCHzCHr- CONHCH 33..-.- OCHs C O CHzC ONH- OCH;

C O CHzCONH CHI 36..... NOI

A typical preparation is as follows:

place of the anhydride of Formula XV there is used OG QlO This is prepared as follows:

an anhydride 0f the formula 10 A mixture of 5.9 parts of l-phenyl-3 (3-aminobenzoyl) Cono amino-S-pyrazolone, 9.4 parts of 4chlorocarbonyl-N(3 n-dodecycloxyphenyl)phthalimide and 75 parts of gla- *CO cial acetic acid is heated under reux for 2 hours and 15 allowed to cool. The yellow solid is collected by lltration and washed well with ethyl acetate. The 13.6 parts of ONE-Q 3 {3 [1,3-dioxo-2-(3-dodecycloxyphenyl) dihydroisoin- (s dol 5 ylcarbonylamino]benzamido}l-phenyl-S-pyrazo- -CHHN (XVI) 20 lone are obtained as a solid melting at ZIO-212 C. On EXAMPLE 3 analysis the compound is found to contain 70.5% carbon, Colour couplers of general FormulaIV 6'0 hydrogen and 9'4% nitrogen (C43H45N50- re' quires 71.0% carbon, 6.2% hydrogen and 9.6% nitro- Colour` couplers of general Formula IV were prepared wherein B has the value indicated in Table 3 which 25 gem follows. A is a phony1 group, x is -oand R1 is a The 4h10r0arbony1 N- (3 -nd0dey1oxypheny1 dodecyl group as shown in the following general formula: phthalimide may be prepared by the method described cour-Q B-NELOC-@lvo .CH

TABLE 3 Coupler MP., am, o1 No. B C, derived dye b\ G--NHO C-Q O/ Cs CH.O @COCH.GOHN COHN@ 39....- OCH. 153 443m @monomer-Q 4o.-.- OCB, 164-168 152(P) 39..---

41..... 117-120 esstN) on /coNHroHmom- The colour couplers of Table 3 are obtained by condensing an acid chloride of formula OCI XVII with a colour coupler amine BNH2 where B is as dened in the table.

for 4-chlorocarbonyl-N-n-octadecylphthalimde in Exam- 65 ple 1 of British patent specification No. 944,838.

A photographic layer containing one of these colour couplers is prepared by the method described in Example 1.

wherein B had the value indicated in Table 4 which follows, A was a phenyl group, X was a direct link and R1 was a dodecyl group as shown in the following general formula:

16 The above coupler is obtained by condensing an anhydride of formula /CO /CO\ CO C B N/ \N O\ /N-Q CO \CO 12H25 (XVIII) C0 C0 H with 1-phenyl-3-amino-S-pyrazolone using the conditions TABLE 4 given for the couplers of Table 5 which follows in MP f 10 Example 5.

. msx.0 Coupler No. B Ci derived dye EXAMPLE 5 42 210.212 533 Further Colour couplers of general FormulaVIH were IT--IIII prepared wherein B has the value indicated 1n Table 5 C Q which follows, A is a phenyl group, X is -O- and R1 0% \C is a dodecyl group as shown in the following general formula:

/CO /Co B-N\ N-Q CO \CO CizHzs TABLE 5 Coupler M.P., km. of No. nC. derived dye 43..--- CN 23a-241 548 @N-N I Il C C- o CH2 H l a /C" 2N-@Vr CN- N--I C- o CH2 QN-af C- O CH2 N- N H C- O CH:

N-r o o-NHoC-Q 1I-11 Cl o\ /c-NHoc-Q o/ CH,

17 18 TABLE 5-Continued Coupler MP., hun. of No. B 0. derived dye 1f t a( me@ 52.-.-- No, 23o-232 542 N-N Il C O/ Cz 53..--- 232-234 555 N NOI-@ret i /C\ O Cz 5a..-- 00H5 20o 43s (1 cH.o-coCH,CoNH- 55...-- 00H. 21o 44o (P) 55...-- 00H5 215 44o (P) @cocmooNH-Q l I CH3 57W. 00H5 21g-22a 452 (P) l CH 58-...- ci 212-213 f1-@5a 01 /C\ /C- O/ CH2 The colour couplers of Table 5 are obtained by condensing an anhydride of formula C O /CO\ 0 CMH (XIX) with a colour coupler amine, BNHZ, where B is as defined in the table. 70

A typical preparation is as follows:

A mixture of 2.8 parts of 1-(3:4:5-trich1orophenyl) 3-amino-5-pyrazolone, 4.76 parts of N-(3-dodecyloxyphenyl)pyromellitic mono-imide mono-anhydride and 50 parts of glacial acetic acid is stirred under redux for 2 75 hours. The yellow precipitate formed is filtered from the A photographic layer containing one of the above colour couplers may be prepared by the method given for the couplers of Example 1, except that an additional equivalent of 2 N potassium hydroxide solution is required to dissolve the coupler, i.e. 5.0 parts in place of 3.3 parts.

EMMPLE 6 Colour couplers of general Formula IX Colour couplers of general Formula 1X wherein B has the value indicated in Table 6 which follows, A is a phenyl group, X is -O- and R1 is a dodecyl group as shown in the following general formula:

\CO -CONHQ CizHzs TABLE 6 Coupler M.P., mx o! No. B C. derived dye N-If /-NHOC O CH2 62...: CN 13D-136 :7.7.:;7.'.^.'.

@1g-ff O CH2 O \CH2 QN-t /C- O CH:

@IGN-4 Q O CH2 67...-r 0H 1 154-155 658 (P) 68-..: OH l 112-115 686 (P) CONH(CH2)5CH3 1 These particular couplers were prepared in the "am1c acid form.

2l The colour couplers of Table 6 are obtained by condensing an anhydride of formula with a colour coupler amine EBNHZ, where B is as defined in Table 6. The condensations are generally carried out in acetic acid at the boil and where the couplers precipitate they are collected from the reaction mixture, otherwise they crystallise on cooling and are filtered off. The product is then recrystallised from an organic solvent where possible.

`In some cases it is advantageous to prepare the couplers in the amic acid form. In these instances the condensation is generally carried out in ethyl acetate at the boil, often in the presence of a little acetic acid.

A typical preparation is as follows:

tion contains silver halide equivalent to 8.1 parts per litre of silver, 3.26% of gelatin, 1.72% of polyvinyl alcohol and 0.7% of sodium dioctyl succinate. The pH is adjusted in the preparation of the formulation by the addition of the required amount o dilute hydrochloric acid to the emulsion before the addition of the coupler solution.

The formulation viscosities were measured in an Ostwald viscometer relative to water. In the comparison of FIG. 1, the viscosities were measured initially only since on holding the emulsion containing Example l2 of British patent speciiication No. 1,170,859 became too viscous to measure. In the comparison of FIG. 2 the viscosities were measured initially and again after holding the formulations at 40 C. for 31/2 hours.

I claim as my invention:

`1. Colour photographic material which comprises a silver halide emulsion layer comprising a colour coupler selected from the class consisting of a colour coupler of the general formula:

A mixture of 2.195' parts of l-phenyl-3-(3-aminobenzoylamino)5pyrazolone, 4.51 parts of 4-(2-dodecyloxyphenylaminocarbonyl)phthalic anhydride and 5 0 parts of acetic acid is stirred under reflux for 2 hours. After cooling the yellow precipitate is collected by filtration, washed with ethanol and dried at 60 C. The 6.3 parts of 4-(2-dodecyloxyphenylamino carbonyl) -N- (3[ l-phenyl-S-pyrazolony1-3]aminocarbonylphenyl)phthalimide are obtained as a solid melting at l52-l54 C. On analysis the compound is found to contain 70.6% carbon, 6.2% hydrogen and 9.8% nitrogen (C43H45N5O6 requires 70.6% carbon, 6.2% hydrogen and 9.6% nitrogen).

The 4-(2-dodecyloxyphenylaminocarbonyl)phthalic anhydride used above may itself be prepared by the method given for 4-(3-dodecylphenylamino carbonyl)phthalic an hydride using o-dodecyloxyaniline in place of m-dodecylaniline.

A photographic layer containing a coupler from Table 6 may be prepared by the method described for the couplers of Example 1.

EXAMPLE 7 'I'he improvement in viscosity of an emulsion containing a colour coupler of the invention is shown in FIG. 1 which compare Coupler No.6 (this invention) with Example l2 of British patent specification No. 1,170,859 which is the p-dodecyl isomer of Coupler No. 6.

lFIG. 2 compares Coupler No. 13 with its p-dodecyloxy isomer Coupler A which has the following formula lAgain the improvement in viscosity is illustrated.

The formulation used for the viscosity determination is obtained by adding a solution of coupler, prepared by dissolving l part of coupler in 2 parts of distilled n-propanol and 2 equivalents of 2 N potassium hydroxide solution at the boil, screening and diluting with Water, to green sensitised silver halide emulsion so that the nal formula- C12H25 and of the general formula:

X-Rl wherein, in the above two formulae B represents (i) a pyrazolene grouping of the structure A-N-N where A is a phenyl group, optionally carrying substituents selected -from chlorine, cyano and nitro groups, and n is zero or 1, or

(ii) a grouping of the structure optionally containing substituent groups selected from alkyl groups and halogen atoms, or (IV) a naphthol grouping of the structure 24 where W represents a radical of up to six methylene R1 is an alkyl group containing at least 12 carbon groups or a grouping atoms and X is a direct linkage, or an oxygen atom.

I 5 References Cited and Y is hydrogen or chlorine, UNITED STATES PATENTS Q represents a group selected from: 3,383,214 5/ 1968 Anderson 96-100 C0 3,328,419 6/1967 Anderson 96-10() 3,312,715 4/1967 Anderson 96-100 N 10 3,278,306 10/1966 Greenhalgh 96-100 CONH 3,161,512 12/1964 Greenhalgh 96-100 C0 3,127,269 3/ 1964 Greenhalgh 96-100 C O N NORMAN G. TORCHIN, Primary Examiner Nuo o* Co 15 E. C. KIMLIN, Assistant Examiner oo oo U.S. Cl. X.R.

CO CO