CA1069369A - Color photographic silver halide materials with new 2-equivalent yellow couplers - Google Patents
Color photographic silver halide materials with new 2-equivalent yellow couplersInfo
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- CA1069369A CA1069369A CA216,483A CA216483A CA1069369A CA 1069369 A CA1069369 A CA 1069369A CA 216483 A CA216483 A CA 216483A CA 1069369 A CA1069369 A CA 1069369A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
- C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D237/14—Oxygen atoms
- C07D237/16—Two oxygen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
- C07D237/26—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings condensed with carbocyclic rings or ring systems
- C07D237/30—Phthalazines
- C07D237/32—Phthalazines with oxygen atoms directly attached to carbon atoms of the nitrogen-containing ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/32—One oxygen, sulfur or nitrogen atom
- C07D239/34—One oxygen atom
- C07D239/36—One oxygen atom as doubly bound oxygen atom or as unsubstituted hydroxy radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/86—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in position 4
- C07D239/88—Oxygen atoms
- C07D239/90—Oxygen atoms with acyclic radicals attached in position 2 or 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
- C07D239/96—Two oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D241/20—Nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/44—Benzopyrazines with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/08—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 condensed with carbocyclic rings or ring systems
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
- G03C7/30517—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution
- G03C7/30535—2-equivalent couplers, i.e. with a substitution on the coupling site being compulsory with the exception of halogen-substitution having the coupling site not in rings of cyclic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
COLOR PHOTOGRAPHIC SILVER HALIDE MATERIALS WITH
Abstract of the Disclosure New 2-equivalent yellow couplers for the production of yellow dye images in color photographic silver halide materials having as splittable group a nitrogen containing 6-membered heteroaromatic ring which is linked by the said nitrogen atom to the coupling position of the coupler molecule and capable of splitting off during coupling at the coupling position. The heteroaromatic ring contains a carbonyl group or a corresponding tautomeric hydroxy substituted carbon atom at the 2-position and is either hydroxy substituted at the 4-position or contains at least one other ring nitrogen atom at the 3-, 4-, 5- or 6-position; and in the case where the ring contains two adjoining ring nitrogen atoms the ring is substituted at the 5-position.
Abstract of the Disclosure New 2-equivalent yellow couplers for the production of yellow dye images in color photographic silver halide materials having as splittable group a nitrogen containing 6-membered heteroaromatic ring which is linked by the said nitrogen atom to the coupling position of the coupler molecule and capable of splitting off during coupling at the coupling position. The heteroaromatic ring contains a carbonyl group or a corresponding tautomeric hydroxy substituted carbon atom at the 2-position and is either hydroxy substituted at the 4-position or contains at least one other ring nitrogen atom at the 3-, 4-, 5- or 6-position; and in the case where the ring contains two adjoining ring nitrogen atoms the ring is substituted at the 5-position.
Description
mis invention relates to new 2-equivalent yellow couplers and their use for the production of yellow dye images in color photographic silver halide materials~
In the production of color photographic images, it is usual to develop the exposed silver halide in a light-sensi-tive silver halide emulsion layer with an aromatic developer containing primary amine groups. The color couplers react with the oxidized color developer to form an image dye corresponding to the silver image.
In subtractive three-color photography a light-sensitive multi-layer material is generally used containing red-sensi-tized, a green-sensitized and a blue-sensitized silver halide emulsion layer. When these are developed, using suitable couplers, they give a blue-green, a purple and ~ellow image respectively.
The couplers used to ~orm blue dyes are generally phenols or naphthols, those producing magenta are usually pyrazolones and those producing yellow are generally compounds containing a methylene group with two carbonyl groups attached theretoO m e dyes formed by coupling are azomethines, indamines or indophenols, according to the coupler and the developer usedO
! The conventional yellow couplers contain an active methylene group which reacts during development with the oxidized color developer four equi~alents of developable silver halide being required for the reaction. mese co~plers are therefore called ~-equivalent coupl~rs. Other known couplers contain a methylene group in which ~ne hydrogen A-G 1206 - 2 - ~
~)69369 `:
atom is replaced by a group which splits off during the coupling reaction. In the latter case only two equivalents of developable silver halide are required to form the dye.
., ~.
For this reason these couplers are called 2-equivalent couplers. For yellow couplers the following splittable groups ;' have already been suggested:
~`~ 10 Halogen, as described, for example, in French Patent ,~ ~
5pecification Nos. 991 453 and 869 169; US Patent Specification Nos. 2 728 658 and 3 277 155 and British ; 10 Patent Specification NoO 1 351 395;
,.,,t 20 the group OR, where R = alkyl, aryl or a heterocyclic or an acyl radical, as described, for example, in British Patent Specification NoO 1 092 506, in French Patent Specifications Nos. 1 411 385 and 1 385 696 and in US Patent Specification Nos. 3 447 928 and 3 408 194;
3. a group SR, as described, for example, in British Patent Specification NoO 953 454 and US Patent Specification No. 3 265 506;
4~ a group: R1 ~ ~ R2 -N
\ ~ ~ \ R
as described in US Patent Specification No. 3 617 291;
the radicals S03H and SCN, as described in British Patent Specification NoO 638 039 and US Patent Specification No. 3 253 924;
~L0693~9 6. a group:
/co-~ /so2-.~
-N Z or -N Z
\CO-' \CO_ ~
as described in German Offenlegungsschriften NosO
In the production of color photographic images, it is usual to develop the exposed silver halide in a light-sensi-tive silver halide emulsion layer with an aromatic developer containing primary amine groups. The color couplers react with the oxidized color developer to form an image dye corresponding to the silver image.
In subtractive three-color photography a light-sensitive multi-layer material is generally used containing red-sensi-tized, a green-sensitized and a blue-sensitized silver halide emulsion layer. When these are developed, using suitable couplers, they give a blue-green, a purple and ~ellow image respectively.
The couplers used to ~orm blue dyes are generally phenols or naphthols, those producing magenta are usually pyrazolones and those producing yellow are generally compounds containing a methylene group with two carbonyl groups attached theretoO m e dyes formed by coupling are azomethines, indamines or indophenols, according to the coupler and the developer usedO
! The conventional yellow couplers contain an active methylene group which reacts during development with the oxidized color developer four equi~alents of developable silver halide being required for the reaction. mese co~plers are therefore called ~-equivalent coupl~rs. Other known couplers contain a methylene group in which ~ne hydrogen A-G 1206 - 2 - ~
~)69369 `:
atom is replaced by a group which splits off during the coupling reaction. In the latter case only two equivalents of developable silver halide are required to form the dye.
., ~.
For this reason these couplers are called 2-equivalent couplers. For yellow couplers the following splittable groups ;' have already been suggested:
~`~ 10 Halogen, as described, for example, in French Patent ,~ ~
5pecification Nos. 991 453 and 869 169; US Patent Specification Nos. 2 728 658 and 3 277 155 and British ; 10 Patent Specification NoO 1 351 395;
,.,,t 20 the group OR, where R = alkyl, aryl or a heterocyclic or an acyl radical, as described, for example, in British Patent Specification NoO 1 092 506, in French Patent Specifications Nos. 1 411 385 and 1 385 696 and in US Patent Specification Nos. 3 447 928 and 3 408 194;
3. a group SR, as described, for example, in British Patent Specification NoO 953 454 and US Patent Specification No. 3 265 506;
4~ a group: R1 ~ ~ R2 -N
\ ~ ~ \ R
as described in US Patent Specification No. 3 617 291;
the radicals S03H and SCN, as described in British Patent Specification NoO 638 039 and US Patent Specification No. 3 253 924;
~L0693~9 6. a group:
/co-~ /so2-.~
-N Z or -N Z
\CO-' \CO_ ~
as described in German Offenlegungsschriften NosO
2 213 461 and 2 057 541 and British Patent Specification ; 5 No. 1 3~1 179;
7. certain pyridones and pyridazones, as described in German Offenlegungsschrift No. 2 318 8070 The advantage of 2-equivalent couplers compared with 4-equivalent couplers is well known in principle:
The amount of silver halide required to form a specific amount of dye is about half as much as is required using 4-equivalent couplers, so that less silver halide is requir~d to produce the light-sensitive photographic material. As a result~ the layer of emulsion can be thinner, which in turn has an advantageous e~fect on the resolution and sharpness of the photographic materialO
Among the ~-equivalent yellow couplers known in the art which have the above mentioned splittable groups, those having a halogen as splittable group have proved to be particularly suitable in practice, because when color development is carried out9 a sufficiently large reactivity of the 2-equivalent yellow couplers is necessary to guarantee sufficient color densities even with short developing processes.
In practice, however, 2-equi~alent yellow couplers with flourine as the splittable radical have, for preparative reasons, not been successful. 2-equivalent yellow couplers A-G 1206 ! ¦ - 4 -.
~0693~9 i,~
with chlorine as the splittable radical, on the other hand, frequently have an adverse effect on the photographic proper-ties of the silver halide emulsionO As described in British Patent Specification NoO 1 351 395, only certain yellow couplers of the benzoyl acetanilide type with chlorine as the separable radical are relatively inert and influence the formation of colored fog during development only slightlyO
Nevertheless, even the said couplers do not satisfy photo-graphic requirements in every respect, since an increase in fog formation during development cannot be completely excluded where unprocessed photographic material containing these couplers is stored in moist and warm conditions.
- There has been no lack of practical attempts to find new 2-equiY.alent yellow couplers which should be easily accessible for preparative purpose and whose reactivity in the develop-ment of color photographs should be sufficient or at least comparable with that of the 2-equivalent couplers known at present which have fluorine or chlorine as the splittable group. In this respect, however, the 2-equivalent yellow couplers known in the art with splittable groups, described in the above paragraphs 2 to 5 and 7~ are inferior to the 2-equivalent yellow couplers having fluorine or chlorine as splittable groupO
One further problem, not yet sati~factorily solved in practice, is the fact, that the 2-equivalent couælers must be permanently absorbed into the hydrophilic colloidal layers of the photographic mater~al in finely distributed form, A-G 1206 - 5 ~ ~
~L0693~9 `:
without either recryqtallizing out in the layer or otherwise influencing the photographic or mechanical properties of the layers in any adverse wayO
Furthermore, if photographic material is stored for some length of time, particularly in moist and warm conditions, the 2-equivalent couplers should be sufficiently stable to avoid separation of the splittable group before color development takes place. On the other hand, the splittable group should be easily and completely separated during the process, in order to attain a high concentration of color in the images as well as adequate sensitivity. m ese properties must, of course, be independent of the method of the addition of the couplers to the hydrophilous colloidal layersO Non-diffusing hydrophobic couplers are usually firstly solved either by the use of solubilizing groups in alkaline solution or by the use of an organic solvent, and are th~ emulsified with the gelatin - solution in the usual manner, possibly with the addition of an oily coupler solvent. m e reactivity of the couplers depends in a known way on how the emulsion is produced. To obtain a su~ficient reactivity of 2-equivalent couplers, which is independent of how they are added to the layer, the hydro-philic colloidal layer and/or the hydrophobic drop of oil must be able to influence favourably the separation of the splittable group during color development by means of solvationO
The splittable group, of course, should be photographi-cally inert and should not have any influence on the colors formed or on the stability of the remaining color coupler in the layerO
iO1~93~9 The compounds described in British Pstent Specification No.
; 1,331,179 and United States Patent Specification No. 3,671,291 are not satisfactory in practice, since their stability in unprocessed photographic materials is inadequate when exposed to moist warm air. On this point men-tion should also be made of the Canadian Patent Application Serial No.
201,911.
The Canadian Patent Application ~uoted above suggests the use of 2 equivalent yellow couplers, which are easily prepared and which have as splittable group a 5-membered unsaturated heterocyclic group containing nitrogen which heterocyclic group has a C=C double bond (which is part of the unsaturated or aromatic heterocyclic ring) adjoining the nitrogen atom, across which linking with the active methylene group of the yellow coupler takes place. lmidazoles are the preferred splittable group, preferably containing electro-negative substituents.
The yellow couplers named above are, admi~tedly, superior as regards both production and stability during storage to those described in the United States Patent Specification No. 3,671,291, however, the preparation o~ the heterocyclic group containing elect-ronegative substituents required -for substituting the chlorine atom of the corresponding 2-equivalent couplers with chlorine as splittable group, is not without problems. For instance, four reaction steps are required for the production of an imidazole carboxylic ester.
Moreover, nitro-imidazole compounds for instance are easily ac-`~ cessible and extremely suitable as a separable group, : ~0~9369 but ~hey are yellow in color and can therefore give rise to color distor-tions.
It was, therefore, necessary in practice to produce new 2-equivalent ycllow couplers, which can easily be prepared and which are excellently suitable for use in light-sensitive color photographic materials to produce the yellow partical images and whose photographic properties are superior to those couplers known at present.
It now has been found that certain nitrogen containing 6-membered heteroaromatic compounds are particularly suitable for the produc-tion of splittable groups for 2-equivalent yellow coupler compounds. The heteroaromatic compound contains a carbonyl carbon atom or its tautomeric hydroxyl-substituted carbon atom at the 2-position adjacent to the nitrogen atom and is either hydroxy-substituted at the 4-position or contains at least one other ring-nitrogen atom at the 3-, 4-, 5- or 6-position of the heterocyclic ~ing and in the case where two nitrogen atoms are contained which are adjoining to each other the heterocyclic ring is hydroxy-substi-tuted at the 5-position.
The heterocyclic compound can easily link to the coupling posi-tion of a 2-equivalent yellow coupler by known means by the said nitrogen atom, whereby the corresponding 2-equivalent yellow coupler with chlorine as splittable group are reacted with the salts of the said heterocyclic compound. The protuction of the salt of the said heterocyclic compound is as easy as with compounds of the above mentioned Canadian Patent Application Serial No. 201,911.
~ ~0693~;9 :
Thus, according to the present invention the splittable groups are derived especially from 3-hydroxy-pyridazinons-6, pyrimidinone-2 or pyrimidinone-6, pyrazinone-2, 4-hydroxy-pyridinone-2, 1,2,4- or 1,2,3-triazinones, which may be substi-tuted. Suitable benzo-condensed derivatives of the above heterocyclic compounds are, for example, ~uinazolinones, benzotriazinones or quinoxalinones.
In the heterocyclic splittable groups of this invention ; the nitrogen atom adjoining the carbonyl group is therefore sufficiently electron-deficient to form the corresponding B salts with thoir bases, and sufficiently nucleophilic to ef~ect a smooth substitution with the halogen atom of the ~ active methylene group of the yellow coupler usedO Of course, the polarity of the splittable group also has a marked e~fect on the reaction speed of the corresponding couplers with the oxidized color developerO Polar substituents, such as hydroxyl or acid groups or groups such as carbonyl or nitrogen in the splittable group promote the reaction speed of the coupler with the oxidized color developer but can, conversely, cause instability of the coupler during storageO The yellow couplers of this invention with new heterocyclic splittable groups are not only very easy to produce, but are also particularly stable during storage, even in extreme storage conditions; in addition they ar~ extremely reactive so that during chromogenouæ development the heterocyclic radical is easily split offO Their sensitivity and color yteld are out-standing. Moreover, the splittable groups of the yellow couplers in this! invention in comparison with the correspon-ding 4-equlvalent yellow couplers bring about no adverse A-~ 1206 - 9 -10693~;9 changes in the absorptive power of the colors produced from them nor that of the remaining coupler radical when they are used for color photography and are chromogeneously developed.
According to one embodiment o~ the present invention 5 there is provided a light-sensitive color photographic material with at least one silver halide emulsion layer and 2-equivalent yellow coupler of the ~ollowing formula:
~ N ~
where 0 K - represents a yellow coupler radical substituted in the methylene group, e~g. an open-chain keto-methylene coupler radical, such as ~or example an acyl acetonitrile coupler radical or an acyl acetyl coupler radical;
A and B together represent:
X Y X OH
1) -C-C- 2) -C=N-or 3) -N=C-and D and E together represent:
~' X' X
1) -C=C- 2) -C=N-or 3) -N=C-or A and B together, or D and E together represent:
4) -N=N-~0~;93f~9 in which ormulae X and Y can be either the same or preferably different and represent hydrogen, alkoxy such as methoxy, halogen, acyl, acyloxy, acylamino, carbamyl, sulfamyl, alkyl, preferably with 1 - 4 C atoms, especially methyl, aryl, such as phenyl or X and Y together represent the atoms required for a condensed aromatic or heteroaromatic ring; X' and Y' represent the same as X
and Y or hydroxy; provided that D and E together represent OH H
- C = C -unless at least one of the groups A and B together as well as D and E
together represents one of ~2) and (3) above or D and E together complete a condensed aromatic or heteroaromatic ring and provided that D and E together do not complete a condensed benzene ring unless A and B together represent one of (2) and (3) above.
If X and Y or X' and Y' represent phenyl or together form the ring members necessary for an aromatic or heteroaromatic ring, preferably a benzene ring, then the phenyl radical or condensed ring may be further substituted, e.g. with alkyl in particular trifluoralkyl, alkoxy, alkylthio, ~' ; aryl, acyl, acyloxy, acylamino, carbamyl, sulfamyl, carboxy~ nitro, cyano, halogen.
The 2-equivalent coupler radical K which forms a yellow color in accordance with this invention is derived from the usual known 4-equivalent couplers. Preferred couplers for this invention are those of the general formula above, where K represents an open-chain ketomethylene yellow coupler radical, e.g. acylacetonitrile or acylacetyl coupler in particular of the following formula (I):
Bl (I) B - C - CH - B' where B represents an alkyl radical with 1 - 32 C-atoms, : preferably 1 - 18 C-atoms, branched or unbranched;
in the case of a secondary or tertiary alkyl radical the secondary or tertiary carbon atom should preferably be linked directly with the carbonyl radical;
/oa, 1 1<~ 1 or an alkoxyalkyl radical, a ~b~ }~cef} radical, a heterocyclic radical or an aryl radical, especially : 10 a phenyl radical which may, i~ necessary, be substi-tuted on e or several time~ by alkyl with 1 - 18 C-atoms, aryl, aralkyl9 alkoxy with 1 - 18 C-atoms, aroxy, halogen (eOg. fluorine or bromine), acyl, acyloxy, acylamino, amino-, carbamyl- or sulfamyl groups which m~y be substituted by identical or dif~erent arylaralkyl? alkyl or heterocyclic radicals, sulfo or carboxy; ~
B' represents cyano or the group ., -C-N
~ represents hydrogen or a short-chain alkyl radical with 1 ~ 5 C-atoms, for example a methyl or ethyl radical and ~0693f~9 R2 represents an alkyl radical with 1 - 18 C-atoms or preferably an aryl radical, for example a phenyl radical which may be substituted by identical or different groups such as alkyl with 1 - 18 C-atoms, alkoxy with 1 - 18 C-atoms, aryl, aralkyl, aroxy, halogen (eOgO fluorine or bromine), acyl, acyloxy, acylamino, amino, carbamyl or sulfamyl groups which may be substituted by identical or different aryl, aralkyl, alkyl or heterocyclic radicals, sul~o or carboxy.
Preferred coupler radicals are naturally those which are derived from 4-equivalent yellow couplers having extremely suited properties with respect to absorption of the dyes and of the stability of the azomethine dyes produced on chromogenic development. Benzoylacetanilides in particular o-alkoxybenzoyl-acetanilides and pivaloylacetanilides which may be substituted in the anilid group of the coupler molecule by one or several _ ,~
optionally one to three substituents preferably in the ~ , 4-and 5-position o~ the anilid group are found to be of pre-ferred practical importance.
The new yellow couplers of this invention are easily produced unexpectealy stable during storage when they ar~ used C c>~ llng in light-sensitive materials and they possess a high bonding capacity, iOeO they give color images with a high color de~sJ7~y o~tr-~tion and high sensitivity and they are extremely suitable ~or use in light-sensitive sllver halide emulsion layers of single or multi-layered color photographic materialgO
However, it is not absoIutely necessary for the yellow couplers to be incorporated into the light-sensitive layers;
lC~69369 it is also possible to accomodate them in a layer of binder adjacent to the light-sensitive silver halide emulsion layer.
The yellow couplers of this invention can be used as diffusionfast or non-diffusionfast couplers for the formation of yellow dye images in color photography according to a further embodiment of the invention by a suitable choice of substituents R1, R2, B or B' as defined abo~eO To o~tain a sufficient degree of diffusionfastness, the substituents R1, R2, B or B', preferably B or B', are provided with radicals which prevent diffusion, eOgO straight-chain or branched alkyl radicals with 10 - 18 C-atoms, or they can be substituted by ; alkyl-substituted phenoxy radicals which are bonded either directly or indirectly via -0-, -S- 9 -CONH- ~ -NHCO- ~ -S02NH--NHS02 or other intermediate members to the radicals B, B' 9 . 15 R1 or R2 (which may be aromatic)0 If solubility in alkalis is desired, at least one of the radicals B, B', R1 or R2 may carry groups which favour this property, especially sulfo groupsO
P~ P/~Us/~k e~pler5 DiffuEion-promotin~ g~Y~ff~ are particularly suitable for use in developer solutions, in order to develop the yellow color in exposed color films which contains no yellow coupler.
Examples of suitable yellow couplers which are to be used according to the invention are as follows:
.. . ~ , . . ~ .. . - . .
Table 1 --- 0~ N
B-C0-CH-C0-NH~/~ 9 x = ~--x ~. ~ "
R"
. . . . . . . .
No. B R' R" mOp C
.
1 ~ ll H ~ 1 2 t-butylC1 6H33 -S02NEICH3 130-131 _~ 6H33 S02N ( CH3 ) 4 t-butylCl -NH-C 0~ ( CH2 ) 3 180 ~ o _ .
L~ ~'1 -NHCOC~5H31 7 t-butyl ~ lla -S02NHCH3 . .
110~93~9 No. B . R" mOp. C
8 t-butyl Cl C14H29 47-50 _ .
9 t-butyl C1 C14H29 60-63 .
~ 10 t-butyl Cl CH3 '1 _ . _ :~ 11 t-butyl C16H33 H 98-99 12 C16 33 -O,H3 -S0z-Yu )C1BH37 -S2-NH ~ ~ 8 H3 ~ -N(cH3)c18H37 -S02NHCH3 110-111 .- ,..... - - ..
~3 , .. . . . .
., 10~93~;9 No. B R' R" m-p- C ¦
=~ ¦ ( ~ C1 aH37 -502NHC4H9 LL~:~ w 110693fà9 ~ ., ~ ~
j _ ~ -
7. certain pyridones and pyridazones, as described in German Offenlegungsschrift No. 2 318 8070 The advantage of 2-equivalent couplers compared with 4-equivalent couplers is well known in principle:
The amount of silver halide required to form a specific amount of dye is about half as much as is required using 4-equivalent couplers, so that less silver halide is requir~d to produce the light-sensitive photographic material. As a result~ the layer of emulsion can be thinner, which in turn has an advantageous e~fect on the resolution and sharpness of the photographic materialO
Among the ~-equivalent yellow couplers known in the art which have the above mentioned splittable groups, those having a halogen as splittable group have proved to be particularly suitable in practice, because when color development is carried out9 a sufficiently large reactivity of the 2-equivalent yellow couplers is necessary to guarantee sufficient color densities even with short developing processes.
In practice, however, 2-equi~alent yellow couplers with flourine as the splittable radical have, for preparative reasons, not been successful. 2-equivalent yellow couplers A-G 1206 ! ¦ - 4 -.
~0693~9 i,~
with chlorine as the splittable radical, on the other hand, frequently have an adverse effect on the photographic proper-ties of the silver halide emulsionO As described in British Patent Specification NoO 1 351 395, only certain yellow couplers of the benzoyl acetanilide type with chlorine as the separable radical are relatively inert and influence the formation of colored fog during development only slightlyO
Nevertheless, even the said couplers do not satisfy photo-graphic requirements in every respect, since an increase in fog formation during development cannot be completely excluded where unprocessed photographic material containing these couplers is stored in moist and warm conditions.
- There has been no lack of practical attempts to find new 2-equiY.alent yellow couplers which should be easily accessible for preparative purpose and whose reactivity in the develop-ment of color photographs should be sufficient or at least comparable with that of the 2-equivalent couplers known at present which have fluorine or chlorine as the splittable group. In this respect, however, the 2-equivalent yellow couplers known in the art with splittable groups, described in the above paragraphs 2 to 5 and 7~ are inferior to the 2-equivalent yellow couplers having fluorine or chlorine as splittable groupO
One further problem, not yet sati~factorily solved in practice, is the fact, that the 2-equivalent couælers must be permanently absorbed into the hydrophilic colloidal layers of the photographic mater~al in finely distributed form, A-G 1206 - 5 ~ ~
~L0693~9 `:
without either recryqtallizing out in the layer or otherwise influencing the photographic or mechanical properties of the layers in any adverse wayO
Furthermore, if photographic material is stored for some length of time, particularly in moist and warm conditions, the 2-equivalent couplers should be sufficiently stable to avoid separation of the splittable group before color development takes place. On the other hand, the splittable group should be easily and completely separated during the process, in order to attain a high concentration of color in the images as well as adequate sensitivity. m ese properties must, of course, be independent of the method of the addition of the couplers to the hydrophilous colloidal layersO Non-diffusing hydrophobic couplers are usually firstly solved either by the use of solubilizing groups in alkaline solution or by the use of an organic solvent, and are th~ emulsified with the gelatin - solution in the usual manner, possibly with the addition of an oily coupler solvent. m e reactivity of the couplers depends in a known way on how the emulsion is produced. To obtain a su~ficient reactivity of 2-equivalent couplers, which is independent of how they are added to the layer, the hydro-philic colloidal layer and/or the hydrophobic drop of oil must be able to influence favourably the separation of the splittable group during color development by means of solvationO
The splittable group, of course, should be photographi-cally inert and should not have any influence on the colors formed or on the stability of the remaining color coupler in the layerO
iO1~93~9 The compounds described in British Pstent Specification No.
; 1,331,179 and United States Patent Specification No. 3,671,291 are not satisfactory in practice, since their stability in unprocessed photographic materials is inadequate when exposed to moist warm air. On this point men-tion should also be made of the Canadian Patent Application Serial No.
201,911.
The Canadian Patent Application ~uoted above suggests the use of 2 equivalent yellow couplers, which are easily prepared and which have as splittable group a 5-membered unsaturated heterocyclic group containing nitrogen which heterocyclic group has a C=C double bond (which is part of the unsaturated or aromatic heterocyclic ring) adjoining the nitrogen atom, across which linking with the active methylene group of the yellow coupler takes place. lmidazoles are the preferred splittable group, preferably containing electro-negative substituents.
The yellow couplers named above are, admi~tedly, superior as regards both production and stability during storage to those described in the United States Patent Specification No. 3,671,291, however, the preparation o~ the heterocyclic group containing elect-ronegative substituents required -for substituting the chlorine atom of the corresponding 2-equivalent couplers with chlorine as splittable group, is not without problems. For instance, four reaction steps are required for the production of an imidazole carboxylic ester.
Moreover, nitro-imidazole compounds for instance are easily ac-`~ cessible and extremely suitable as a separable group, : ~0~9369 but ~hey are yellow in color and can therefore give rise to color distor-tions.
It was, therefore, necessary in practice to produce new 2-equivalent ycllow couplers, which can easily be prepared and which are excellently suitable for use in light-sensitive color photographic materials to produce the yellow partical images and whose photographic properties are superior to those couplers known at present.
It now has been found that certain nitrogen containing 6-membered heteroaromatic compounds are particularly suitable for the produc-tion of splittable groups for 2-equivalent yellow coupler compounds. The heteroaromatic compound contains a carbonyl carbon atom or its tautomeric hydroxyl-substituted carbon atom at the 2-position adjacent to the nitrogen atom and is either hydroxy-substituted at the 4-position or contains at least one other ring-nitrogen atom at the 3-, 4-, 5- or 6-position of the heterocyclic ~ing and in the case where two nitrogen atoms are contained which are adjoining to each other the heterocyclic ring is hydroxy-substi-tuted at the 5-position.
The heterocyclic compound can easily link to the coupling posi-tion of a 2-equivalent yellow coupler by known means by the said nitrogen atom, whereby the corresponding 2-equivalent yellow coupler with chlorine as splittable group are reacted with the salts of the said heterocyclic compound. The protuction of the salt of the said heterocyclic compound is as easy as with compounds of the above mentioned Canadian Patent Application Serial No. 201,911.
~ ~0693~;9 :
Thus, according to the present invention the splittable groups are derived especially from 3-hydroxy-pyridazinons-6, pyrimidinone-2 or pyrimidinone-6, pyrazinone-2, 4-hydroxy-pyridinone-2, 1,2,4- or 1,2,3-triazinones, which may be substi-tuted. Suitable benzo-condensed derivatives of the above heterocyclic compounds are, for example, ~uinazolinones, benzotriazinones or quinoxalinones.
In the heterocyclic splittable groups of this invention ; the nitrogen atom adjoining the carbonyl group is therefore sufficiently electron-deficient to form the corresponding B salts with thoir bases, and sufficiently nucleophilic to ef~ect a smooth substitution with the halogen atom of the ~ active methylene group of the yellow coupler usedO Of course, the polarity of the splittable group also has a marked e~fect on the reaction speed of the corresponding couplers with the oxidized color developerO Polar substituents, such as hydroxyl or acid groups or groups such as carbonyl or nitrogen in the splittable group promote the reaction speed of the coupler with the oxidized color developer but can, conversely, cause instability of the coupler during storageO The yellow couplers of this invention with new heterocyclic splittable groups are not only very easy to produce, but are also particularly stable during storage, even in extreme storage conditions; in addition they ar~ extremely reactive so that during chromogenouæ development the heterocyclic radical is easily split offO Their sensitivity and color yteld are out-standing. Moreover, the splittable groups of the yellow couplers in this! invention in comparison with the correspon-ding 4-equlvalent yellow couplers bring about no adverse A-~ 1206 - 9 -10693~;9 changes in the absorptive power of the colors produced from them nor that of the remaining coupler radical when they are used for color photography and are chromogeneously developed.
According to one embodiment o~ the present invention 5 there is provided a light-sensitive color photographic material with at least one silver halide emulsion layer and 2-equivalent yellow coupler of the ~ollowing formula:
~ N ~
where 0 K - represents a yellow coupler radical substituted in the methylene group, e~g. an open-chain keto-methylene coupler radical, such as ~or example an acyl acetonitrile coupler radical or an acyl acetyl coupler radical;
A and B together represent:
X Y X OH
1) -C-C- 2) -C=N-or 3) -N=C-and D and E together represent:
~' X' X
1) -C=C- 2) -C=N-or 3) -N=C-or A and B together, or D and E together represent:
4) -N=N-~0~;93f~9 in which ormulae X and Y can be either the same or preferably different and represent hydrogen, alkoxy such as methoxy, halogen, acyl, acyloxy, acylamino, carbamyl, sulfamyl, alkyl, preferably with 1 - 4 C atoms, especially methyl, aryl, such as phenyl or X and Y together represent the atoms required for a condensed aromatic or heteroaromatic ring; X' and Y' represent the same as X
and Y or hydroxy; provided that D and E together represent OH H
- C = C -unless at least one of the groups A and B together as well as D and E
together represents one of ~2) and (3) above or D and E together complete a condensed aromatic or heteroaromatic ring and provided that D and E together do not complete a condensed benzene ring unless A and B together represent one of (2) and (3) above.
If X and Y or X' and Y' represent phenyl or together form the ring members necessary for an aromatic or heteroaromatic ring, preferably a benzene ring, then the phenyl radical or condensed ring may be further substituted, e.g. with alkyl in particular trifluoralkyl, alkoxy, alkylthio, ~' ; aryl, acyl, acyloxy, acylamino, carbamyl, sulfamyl, carboxy~ nitro, cyano, halogen.
The 2-equivalent coupler radical K which forms a yellow color in accordance with this invention is derived from the usual known 4-equivalent couplers. Preferred couplers for this invention are those of the general formula above, where K represents an open-chain ketomethylene yellow coupler radical, e.g. acylacetonitrile or acylacetyl coupler in particular of the following formula (I):
Bl (I) B - C - CH - B' where B represents an alkyl radical with 1 - 32 C-atoms, : preferably 1 - 18 C-atoms, branched or unbranched;
in the case of a secondary or tertiary alkyl radical the secondary or tertiary carbon atom should preferably be linked directly with the carbonyl radical;
/oa, 1 1<~ 1 or an alkoxyalkyl radical, a ~b~ }~cef} radical, a heterocyclic radical or an aryl radical, especially : 10 a phenyl radical which may, i~ necessary, be substi-tuted on e or several time~ by alkyl with 1 - 18 C-atoms, aryl, aralkyl9 alkoxy with 1 - 18 C-atoms, aroxy, halogen (eOg. fluorine or bromine), acyl, acyloxy, acylamino, amino-, carbamyl- or sulfamyl groups which m~y be substituted by identical or dif~erent arylaralkyl? alkyl or heterocyclic radicals, sulfo or carboxy; ~
B' represents cyano or the group ., -C-N
~ represents hydrogen or a short-chain alkyl radical with 1 ~ 5 C-atoms, for example a methyl or ethyl radical and ~0693f~9 R2 represents an alkyl radical with 1 - 18 C-atoms or preferably an aryl radical, for example a phenyl radical which may be substituted by identical or different groups such as alkyl with 1 - 18 C-atoms, alkoxy with 1 - 18 C-atoms, aryl, aralkyl, aroxy, halogen (eOgO fluorine or bromine), acyl, acyloxy, acylamino, amino, carbamyl or sulfamyl groups which may be substituted by identical or different aryl, aralkyl, alkyl or heterocyclic radicals, sul~o or carboxy.
Preferred coupler radicals are naturally those which are derived from 4-equivalent yellow couplers having extremely suited properties with respect to absorption of the dyes and of the stability of the azomethine dyes produced on chromogenic development. Benzoylacetanilides in particular o-alkoxybenzoyl-acetanilides and pivaloylacetanilides which may be substituted in the anilid group of the coupler molecule by one or several _ ,~
optionally one to three substituents preferably in the ~ , 4-and 5-position o~ the anilid group are found to be of pre-ferred practical importance.
The new yellow couplers of this invention are easily produced unexpectealy stable during storage when they ar~ used C c>~ llng in light-sensitive materials and they possess a high bonding capacity, iOeO they give color images with a high color de~sJ7~y o~tr-~tion and high sensitivity and they are extremely suitable ~or use in light-sensitive sllver halide emulsion layers of single or multi-layered color photographic materialgO
However, it is not absoIutely necessary for the yellow couplers to be incorporated into the light-sensitive layers;
lC~69369 it is also possible to accomodate them in a layer of binder adjacent to the light-sensitive silver halide emulsion layer.
The yellow couplers of this invention can be used as diffusionfast or non-diffusionfast couplers for the formation of yellow dye images in color photography according to a further embodiment of the invention by a suitable choice of substituents R1, R2, B or B' as defined abo~eO To o~tain a sufficient degree of diffusionfastness, the substituents R1, R2, B or B', preferably B or B', are provided with radicals which prevent diffusion, eOgO straight-chain or branched alkyl radicals with 10 - 18 C-atoms, or they can be substituted by ; alkyl-substituted phenoxy radicals which are bonded either directly or indirectly via -0-, -S- 9 -CONH- ~ -NHCO- ~ -S02NH--NHS02 or other intermediate members to the radicals B, B' 9 . 15 R1 or R2 (which may be aromatic)0 If solubility in alkalis is desired, at least one of the radicals B, B', R1 or R2 may carry groups which favour this property, especially sulfo groupsO
P~ P/~Us/~k e~pler5 DiffuEion-promotin~ g~Y~ff~ are particularly suitable for use in developer solutions, in order to develop the yellow color in exposed color films which contains no yellow coupler.
Examples of suitable yellow couplers which are to be used according to the invention are as follows:
.. . ~ , . . ~ .. . - . .
Table 1 --- 0~ N
B-C0-CH-C0-NH~/~ 9 x = ~--x ~. ~ "
R"
. . . . . . . .
No. B R' R" mOp C
.
1 ~ ll H ~ 1 2 t-butylC1 6H33 -S02NEICH3 130-131 _~ 6H33 S02N ( CH3 ) 4 t-butylCl -NH-C 0~ ( CH2 ) 3 180 ~ o _ .
L~ ~'1 -NHCOC~5H31 7 t-butyl ~ lla -S02NHCH3 . .
110~93~9 No. B . R" mOp. C
8 t-butyl Cl C14H29 47-50 _ .
9 t-butyl C1 C14H29 60-63 .
~ 10 t-butyl Cl CH3 '1 _ . _ :~ 11 t-butyl C16H33 H 98-99 12 C16 33 -O,H3 -S0z-Yu )C1BH37 -S2-NH ~ ~ 8 H3 ~ -N(cH3)c18H37 -S02NHCH3 110-111 .- ,..... - - ..
~3 , .. . . . .
., 10~93~;9 No. B R' R" m-p- C ¦
=~ ¦ ( ~ C1 aH37 -502NHC4H9 LL~:~ w 110693fà9 ~ ., ~ ~
j _ ~ -
3,-X ~ ~D a . ~ ~ ~
o a: ~ ~ ~
~1 z o ~=
.. . ~ , .. ~ ,. ... . .. .
~10693~9 Table 1 (cont.) q' ~
B-CO-CH_CONH ~ X = ~ N
R"
No. B R' . - m.p.C
.. .. .
22 t-butyl C16H33 -S02NHCH3 78 Z4 t-butyl Cl -NHCO(CH2/ 0 ~ 200 . 5 25 t-butyl C16H33 S02N(CH3)2 65-67 _ . ... _ ,C~C1 4H29 26 t ~utyl Cl -COO-CH 55 C1 4H29 . . ~. -27 ~ OCH3 H 84 28 t-b~tll 0~14HZ9 105 ~LO~9;~t;i9 Table 1 (cont. ) IR ' 0~ N l B-CO-CH-CONH~ X =¢~ N
R~ I
Cl , . . . .
NQ . B R' R" mp C
_ , ~t~ 3 -S02NHCH3 30 t-butyl C1 4H29-S02NHCH3 . 96-99 .
31 t_bUtYI C 16~ . 67 6B
. ' "' L ~I~ s L ~ ,, . ~ ICH2 ~t C4Hg .
l~t~
o, 1 ~t ~ ~ o~
' ~0~;93~9 . ..
~ tC - ~ ~tC C'~
. . ..... __ I 1~ PC C X ~ tC
i~ ~ ~ ~ ~
:, ~; ' m ~
:~ ,_~. ~ ' .~_ ;93~;9 ~ ~ +~
~c I ~ I
L~ . ,~
---r A-a 12()6 - 2~ ~
10693~9 ~ ~ ~ `
X z ~ o ~ ~ ~
1l~ I ~ Z-~
~ ~ ¢~ ~
.
I¢ 1~ 1 o I 50 1 ~o --~ .
a~ ~3 ~= I ~ I ~
A-G 1206 - 24 _ ~L0~9;~;9 o~ ~ ~ o ;~
~ ~`
~ i L ~
10693~9 . '_-~ ~
~069369 _ .
- ~Z; ~- ~;
:~ ~~ -~ ' ~m~ ~
.
_ oNm oN N
~~ U2 U~ U~ U~
i~ r I~1~
~ ~ ~. ~ ~
:
; A-G 1206 - 27 - -10~93f~9 L~
~ Q~
~, ~ ~ ~ ~o ~ ~
o ~, ~ ~ U~
.
~0693~;9 . oC~ :~ ~ o ~ ,~ o ~ ~ ~
.
L~L I ~
10693~9 ,~.~, o o ~r: ~: , ~ ~1 .
V~ ~ ~ V
~ ~' ~()693~9 r - . .
-: ` , ;,: . -10~;93~;9 ~:~
,=:z " ~ ~ ~ ~
h~ ~i ~ I ~
~1 ~
. . . .
L~L~ I OD ¦ GD ¦ D
10~93~:;9 lo~ I
~ ~ . ~
~C _ I I
: ~_- ~ ~ A ~ :~
D-~ ~ _ ~ o O ~ c ~
~)~ O ' ~' ~
1.0~93f~9 ~r ~ ~ .
- ~ 3 ... . .
V' ~ a~ ~c~ :r~
L~ ~ ~ z~, I N
~ V ~ O
iO693~9 As already mentioned, the yellow couplers in this in-vention may be produced in a conventional manner by reaction o~ the corresponding 2-equivalent couplers having chlorine as their splittable group with the corresponding heterocyclic compound in the presence of a base, as is described, for ;; example, in German Offenlegungsschrift 2 213 4610 m e reaction can take place in an aprotic solvent, pre-ferably a polar solvent, such as, for example, acetonitrile or dimethyl formamide, and with the use of suitable bases, such as aliphatic amines, e.gO triethylamine; basic hetero-cyclic compounds, e.gO pyridine; or alkali s~lt~ of alcoholates, e.g. sodium alcoh~late. me reaction is also particularly successful in the presence of hexamethyl phosphoric acid tri-A~ C~a~'~n ; ~ amide as solvent as described in ~ritih patent application 20~
Serial No. ~5 3~1J740 The heterocyclic compounds required ~or the said reaction ; can be prepared by known methods. For example, 3-hydroxy-pyridazinone-6 can be obtained from suitable substituted maleic acid derivatives by reaction with hydrazine. By re-action o~ suitably substituted B-dicarbonyl compounds with urea, good yields of p~rimidinones are possible. Pyrazinones are formed from suitable substituted ~-amino-aldehydes or oC-~mino ketones by oxidation in air. Quinoxalinones are - produced fr,om o-phenylene diamines with ~ -keto carboxylic acid, such as, ~or example, pyroracemic acid; a~d 1,2t4-tri-azinones are produced by reaction of semicarbazide with oC-di~eto qompounds (e.g. benzil)O 1,2,3-benzotriazinone is produced by dehydration of o-diazobenzo amides, The reaction of u~ea with ~-amino benzoyl compounds gives 2-quinazolinone.
A-G 1206 _ 35 _ .. . .
10693~9 Pyrazinones-4 can be produced by reaction of ~-keto carboxylic esters with thiourea followed by reduction with nickel; similarly, the corresponding ,` benzo-condensed compound of quinazolinone can be produced by reaction of o-amino benzoic acid with formamide. In each case the reaction conditions of these reactions are well known in principle and need not therefore be des-cribed here.
The preparation of several couplers used in this invention is described in detail below:
Preparation of coupler No. 5
o a: ~ ~ ~
~1 z o ~=
.. . ~ , .. ~ ,. ... . .. .
~10693~9 Table 1 (cont.) q' ~
B-CO-CH_CONH ~ X = ~ N
R"
No. B R' . - m.p.C
.. .. .
22 t-butyl C16H33 -S02NHCH3 78 Z4 t-butyl Cl -NHCO(CH2/ 0 ~ 200 . 5 25 t-butyl C16H33 S02N(CH3)2 65-67 _ . ... _ ,C~C1 4H29 26 t ~utyl Cl -COO-CH 55 C1 4H29 . . ~. -27 ~ OCH3 H 84 28 t-b~tll 0~14HZ9 105 ~LO~9;~t;i9 Table 1 (cont. ) IR ' 0~ N l B-CO-CH-CONH~ X =¢~ N
R~ I
Cl , . . . .
NQ . B R' R" mp C
_ , ~t~ 3 -S02NHCH3 30 t-butyl C1 4H29-S02NHCH3 . 96-99 .
31 t_bUtYI C 16~ . 67 6B
. ' "' L ~I~ s L ~ ,, . ~ ICH2 ~t C4Hg .
l~t~
o, 1 ~t ~ ~ o~
' ~0~;93~9 . ..
~ tC - ~ ~tC C'~
. . ..... __ I 1~ PC C X ~ tC
i~ ~ ~ ~ ~
:, ~; ' m ~
:~ ,_~. ~ ' .~_ ;93~;9 ~ ~ +~
~c I ~ I
L~ . ,~
---r A-a 12()6 - 2~ ~
10693~9 ~ ~ ~ `
X z ~ o ~ ~ ~
1l~ I ~ Z-~
~ ~ ¢~ ~
.
I¢ 1~ 1 o I 50 1 ~o --~ .
a~ ~3 ~= I ~ I ~
A-G 1206 - 24 _ ~L0~9;~;9 o~ ~ ~ o ;~
~ ~`
~ i L ~
10693~9 . '_-~ ~
~069369 _ .
- ~Z; ~- ~;
:~ ~~ -~ ' ~m~ ~
.
_ oNm oN N
~~ U2 U~ U~ U~
i~ r I~1~
~ ~ ~. ~ ~
:
; A-G 1206 - 27 - -10~93f~9 L~
~ Q~
~, ~ ~ ~ ~o ~ ~
o ~, ~ ~ U~
.
~0693~;9 . oC~ :~ ~ o ~ ,~ o ~ ~ ~
.
L~L I ~
10693~9 ,~.~, o o ~r: ~: , ~ ~1 .
V~ ~ ~ V
~ ~' ~()693~9 r - . .
-: ` , ;,: . -10~;93~;9 ~:~
,=:z " ~ ~ ~ ~
h~ ~i ~ I ~
~1 ~
. . . .
L~L~ I OD ¦ GD ¦ D
10~93~:;9 lo~ I
~ ~ . ~
~C _ I I
: ~_- ~ ~ A ~ :~
D-~ ~ _ ~ o O ~ c ~
~)~ O ' ~' ~
1.0~93f~9 ~r ~ ~ .
- ~ 3 ... . .
V' ~ a~ ~c~ :r~
L~ ~ ~ z~, I N
~ V ~ O
iO693~9 As already mentioned, the yellow couplers in this in-vention may be produced in a conventional manner by reaction o~ the corresponding 2-equivalent couplers having chlorine as their splittable group with the corresponding heterocyclic compound in the presence of a base, as is described, for ;; example, in German Offenlegungsschrift 2 213 4610 m e reaction can take place in an aprotic solvent, pre-ferably a polar solvent, such as, for example, acetonitrile or dimethyl formamide, and with the use of suitable bases, such as aliphatic amines, e.gO triethylamine; basic hetero-cyclic compounds, e.gO pyridine; or alkali s~lt~ of alcoholates, e.g. sodium alcoh~late. me reaction is also particularly successful in the presence of hexamethyl phosphoric acid tri-A~ C~a~'~n ; ~ amide as solvent as described in ~ritih patent application 20~
Serial No. ~5 3~1J740 The heterocyclic compounds required ~or the said reaction ; can be prepared by known methods. For example, 3-hydroxy-pyridazinone-6 can be obtained from suitable substituted maleic acid derivatives by reaction with hydrazine. By re-action o~ suitably substituted B-dicarbonyl compounds with urea, good yields of p~rimidinones are possible. Pyrazinones are formed from suitable substituted ~-amino-aldehydes or oC-~mino ketones by oxidation in air. Quinoxalinones are - produced fr,om o-phenylene diamines with ~ -keto carboxylic acid, such as, ~or example, pyroracemic acid; a~d 1,2t4-tri-azinones are produced by reaction of semicarbazide with oC-di~eto qompounds (e.g. benzil)O 1,2,3-benzotriazinone is produced by dehydration of o-diazobenzo amides, The reaction of u~ea with ~-amino benzoyl compounds gives 2-quinazolinone.
A-G 1206 _ 35 _ .. . .
10693~9 Pyrazinones-4 can be produced by reaction of ~-keto carboxylic esters with thiourea followed by reduction with nickel; similarly, the corresponding ,` benzo-condensed compound of quinazolinone can be produced by reaction of o-amino benzoic acid with formamide. In each case the reaction conditions of these reactions are well known in principle and need not therefore be des-cribed here.
The preparation of several couplers used in this invention is described in detail below:
Preparation of coupler No. 5
4.4 g benzo triazinone are dissolved in 200 ml acetonitrile whilst stirring, ant then 20 g 2,4-dimethoxybenzoyl- ~-chloro-(2'-cetyloxy-
5~-N-methylsulfamoyl-acetanilide and 5.25 ml of a 30 % sodium methylate solution are adted. The reaction mixture is boiled for one hour using a reflux condenser. &bsequently it is filtered and the solution is stirred into iced water. After the precipitate has been sucked off, the reaction product is dissolved in hot isopropanol, clarified with ac~ive charcoal, cooled and the supernatant solution decanted off. The residue is then puri-fied with petroleum ether.
Yield: 14 g of coupler No. 5.
Preparation of coupler No. 29 3.6 g 7-chloro-4-quinazolinone, 12 g ~-pivaloyl- ~ chloro-(2-cetyloxy-5-N-methylsulfamoyl~acetanilide and 3.4 ml of a 30 % sodium methy-late solution are dissolved in 100 ml acetonitrile and 50 ml dimethyl forma-mide and boiled for 2 hours in a reflux condenser. After evaporating the solvents, the residue is stirred with methanol and the resulting product is recrystallized from methanol. Yield: 8 g of coupler No. 29~
10~;93~9 Preparation o coupler No. 6 4.6 g 3-phenylureidopyrazinone-2, 12 g ~piv810yl- C~-chloro-~2-cetyloxy-5-N-methylsulfamoyl)-acetanilide and 3.4 ml of a 30 % methylate solution are dissolved in 200 ml dimethylsulfoxide and warmed for 2 hours to 60 - 70C. After cooling, the reaction solution is added to 800 ml water and the precipitated reaction product is recrystallized from isopropanol.
Yield: 8 g of coupler No. 6.
Preparation of coupler No. 42 2.7 g 2-phenyl-4,5-dichloro-pyrimidinone-6 and 5.9 ~ ~-pivaloyl-c~-chloro-(2-cetyloxy-5-N-methylsulfamoyl acetanilide are mixed with 100 ml acetonitrile and 1.85 ml of a 30 % methylate solution and boiled for 2 hours in a reflux condenser. Subsequently, the reaction product is added to iced water and the precipitated reaction product is recrystallized from methanol.
Yield: 4.5 g of coupler No. 42 Preparation of coupler No. 60 To a solution of 15 g O~pivaloyl-ci-chloro-(2-cetyloxy-5-N-methylsulfamoyl~acetanilide in 150 ml hexamethyl phosphoric acid triamide are added 2.9 g maleic acid hydrazide at a temperature of 50C and then 3.5 g potassium-t-butylate, portion by portion. After a reaction time of 2 hours at 50C, the reaction mixture is added to ice/HCl, and the precipitated product is filtered off and washed with water, After the usual purification process, the product is recrystallized from ether.
Yield: 6 g of coupler No. 60.
10~;93~;9 Preparation of cou~ler No. 19 The preparation is as described for coupler NoO 60, except that 4 g uracil are used instead of maleic acid hydra-zide, and 4 g potassium-t-butylate instead of ~.5 gO
Yield: 2.7 g of cou~ler NoO 190 The preparation of the other couplers used in this in-vention can be carried out by analogous methods.
As regards those yellow couplers in this invention which are diffusionsfast, they are extremely emulsifiable, very resistant to digestion in the coating solution and in the photographic material and do not impair the photographic ; proparties of the emulsion, even under extreme conditions of storage.
By the preparation of the light-sensitive color materials according to the present invention diffusionfast yellow couplers of the above general ~ormula can be incorporated into the casting composition o~ a silver halide emulsion ~ other colloidal layers which are in water-permeable relation thereto by any known means. For example, the water-soluble color couplers, iOe. those containing one or several water-soluble groups such as a sul~o or carboxyl group (as an acid or salt) can be incorporated into the casting composition of the specific layer from an aqueous solutionO Similarly, color couplers which are not or which are insu~ficien~ly water-soluble are incorporated from a solution into, respectively,suitable water-miscible or non-water-miscible, h~gh-boiling or low-boiling~organic solvents or mixtures thereofO m ere-upon, the solution obtained is dispersed in a hydrophilic colloidal composition (using, if necessary, a wetting or a :
... .. .:. .- - .
dispersing agent) wnich forms either the whole or simply a part of the binding agent of the colloidal layer. Moreover, the hydrophilic colloidal composition may contain any other type of ingredient besides the colloidO The non-water-soluble color couplers which contain fluoro-~ul~onyl groups or carb-oxylic acid ester groups such as ethoxy carbonyl groups may also be converted by alkaline hydrolysis into the corresponding sulfonic acids or carboxylic acids respectively, which in turn can be incorporated into hydrophilic colloidal compositions in the form o~ their alkali metal salts from aqueous solutions.
me solution of the color couplers does not need to be directly dispersed or dissolved in the casting composition of silver halide emulsion or some other water-permeable layer.
The ~olution may advantageously first be dispersed or dissolved ~o~ , in an aqueous~,llight-sensitive solution of a hydrophilic colloid; subsequently, the mixture obtained is thoroughly mixed with .the ca~ting composition o~ the light-sensitive silver halide emulsion or other water-permeable layer just before casting (after removal of the organic solvent used).
E urther details about particularly suitable techniques for the incorporation of color couplers into the hydrophilic colloidal layers of photographic materials may be found in the Dutch Patent Application NosO 6 516 423, 6 516 424,
Yield: 14 g of coupler No. 5.
Preparation of coupler No. 29 3.6 g 7-chloro-4-quinazolinone, 12 g ~-pivaloyl- ~ chloro-(2-cetyloxy-5-N-methylsulfamoyl~acetanilide and 3.4 ml of a 30 % sodium methy-late solution are dissolved in 100 ml acetonitrile and 50 ml dimethyl forma-mide and boiled for 2 hours in a reflux condenser. After evaporating the solvents, the residue is stirred with methanol and the resulting product is recrystallized from methanol. Yield: 8 g of coupler No. 29~
10~;93~9 Preparation o coupler No. 6 4.6 g 3-phenylureidopyrazinone-2, 12 g ~piv810yl- C~-chloro-~2-cetyloxy-5-N-methylsulfamoyl)-acetanilide and 3.4 ml of a 30 % methylate solution are dissolved in 200 ml dimethylsulfoxide and warmed for 2 hours to 60 - 70C. After cooling, the reaction solution is added to 800 ml water and the precipitated reaction product is recrystallized from isopropanol.
Yield: 8 g of coupler No. 6.
Preparation of coupler No. 42 2.7 g 2-phenyl-4,5-dichloro-pyrimidinone-6 and 5.9 ~ ~-pivaloyl-c~-chloro-(2-cetyloxy-5-N-methylsulfamoyl acetanilide are mixed with 100 ml acetonitrile and 1.85 ml of a 30 % methylate solution and boiled for 2 hours in a reflux condenser. Subsequently, the reaction product is added to iced water and the precipitated reaction product is recrystallized from methanol.
Yield: 4.5 g of coupler No. 42 Preparation of coupler No. 60 To a solution of 15 g O~pivaloyl-ci-chloro-(2-cetyloxy-5-N-methylsulfamoyl~acetanilide in 150 ml hexamethyl phosphoric acid triamide are added 2.9 g maleic acid hydrazide at a temperature of 50C and then 3.5 g potassium-t-butylate, portion by portion. After a reaction time of 2 hours at 50C, the reaction mixture is added to ice/HCl, and the precipitated product is filtered off and washed with water, After the usual purification process, the product is recrystallized from ether.
Yield: 6 g of coupler No. 60.
10~;93~;9 Preparation of cou~ler No. 19 The preparation is as described for coupler NoO 60, except that 4 g uracil are used instead of maleic acid hydra-zide, and 4 g potassium-t-butylate instead of ~.5 gO
Yield: 2.7 g of cou~ler NoO 190 The preparation of the other couplers used in this in-vention can be carried out by analogous methods.
As regards those yellow couplers in this invention which are diffusionsfast, they are extremely emulsifiable, very resistant to digestion in the coating solution and in the photographic material and do not impair the photographic ; proparties of the emulsion, even under extreme conditions of storage.
By the preparation of the light-sensitive color materials according to the present invention diffusionfast yellow couplers of the above general ~ormula can be incorporated into the casting composition o~ a silver halide emulsion ~ other colloidal layers which are in water-permeable relation thereto by any known means. For example, the water-soluble color couplers, iOe. those containing one or several water-soluble groups such as a sul~o or carboxyl group (as an acid or salt) can be incorporated into the casting composition of the specific layer from an aqueous solutionO Similarly, color couplers which are not or which are insu~ficien~ly water-soluble are incorporated from a solution into, respectively,suitable water-miscible or non-water-miscible, h~gh-boiling or low-boiling~organic solvents or mixtures thereofO m ere-upon, the solution obtained is dispersed in a hydrophilic colloidal composition (using, if necessary, a wetting or a :
... .. .:. .- - .
dispersing agent) wnich forms either the whole or simply a part of the binding agent of the colloidal layer. Moreover, the hydrophilic colloidal composition may contain any other type of ingredient besides the colloidO The non-water-soluble color couplers which contain fluoro-~ul~onyl groups or carb-oxylic acid ester groups such as ethoxy carbonyl groups may also be converted by alkaline hydrolysis into the corresponding sulfonic acids or carboxylic acids respectively, which in turn can be incorporated into hydrophilic colloidal compositions in the form o~ their alkali metal salts from aqueous solutions.
me solution of the color couplers does not need to be directly dispersed or dissolved in the casting composition of silver halide emulsion or some other water-permeable layer.
The ~olution may advantageously first be dispersed or dissolved ~o~ , in an aqueous~,llight-sensitive solution of a hydrophilic colloid; subsequently, the mixture obtained is thoroughly mixed with .the ca~ting composition o~ the light-sensitive silver halide emulsion or other water-permeable layer just before casting (after removal of the organic solvent used).
E urther details about particularly suitable techniques for the incorporation of color couplers into the hydrophilic colloidal layers of photographic materials may be found in the Dutch Patent Application NosO 6 516 423, 6 516 424,
6 600 098, 6 600 099 and 6 600 628, in the Belgian Patent Specification NoO 750 889, in the UOSo Patent Specification No. 2 304 940 and in the British Patent Specification No.
A-G 1206 _ 39 _ 106i93~9 To produce photographic color images, an exposed layer of silver halide emulsion is developed with an aromatic primary amino-developer in the presence of a color coupler according to the invention. me developer substances used may be any color developer which are able to yield azomethine dyes by chromogenic development. Suitable substances are aromatic compounds, such as ~-phenylene diamine and i*s derivatives, for example N,N-dialkyl-~-phenylenediamine, N,N-die~hyl-~-phenylenediamine, N,N-dialkyl-N'-sulfomethyl-~-phenylenediamine and N,N-dialkyl-N'-carboxymethyl-~-phenylenediamineO
Suitable light-sensitive emulsions are emulsions of silver halides, such as silver chloride, silver bromide or mixtures thereof which may have a small content of silver iodide up to 10 Mols-%, in one of the hydrophilic binding agents normally used. Gelatin is the preferred binding agent for the photographic layers. m is can, howeverJ be replaced wholly or in part by other natural or synthetic binding agents. Suitable natural binding agents are eOgO alginic acid and its derivatives such as salts 9 esters or amides;
- cellulose derivatives such as carboxymethylcellulose;
alkylcellulose such as hydroxyethylcellulose; starch or its derivatives such as ethers or esters; or caragenates.
Among the synthetic binding agents, polyvinylalcohol, partially saponified polyvinylacetate, polyvinylpyrrolidone and ~ e like should be mentionedO
me emulsions may also be chemically sensitized, eOg.
by the addition of suliur-containing compounds during chemical ripening, ~cr example, allylisothiocyanate, allyl-A-G 1206 _ 40 _ 10693~9 thiourea and sodiumthio~ulfateO Furthermore, reducing agents such as, for example, the tin compounds described in Belgian Patent Specification Nos. 493 464 or 568 687, as well as polyamines such as diethyltriamine or aminomethane sulfinic acid derivatives (as in Belgian Patent Specification 547 323) may also be used as chemical sensitizers. In addition, the rare metals such as gold, platinum, palladium, iridium, ruthenium or rhodium are suitable as chemical sensitizersO
m is method of chemical sensitization has been described in the article by R. KOSLOWSKY, ZoWisS.Phot., Vol. 46, 65 - 72, (1951).
It is also possible to sensitize the emulsions with polyalkyleneoxide derivatives, e.g. with polyethylene oxide having a molecular weight o~ from 1.000 to 20.000, and further with the condensation products of alkylene oxides and aliphatic alcohols, glyccls, cyclic dehydration products of hexitoles; with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
The condensation products have a molecular weight of at least 700, preferably of more than 1000. To obtain special ef~ects, the sensitizers can, of course, be combined, in the manner described in Belgian Patent Specification No. 537 278 and in British Patent Speci~ication NoO 727 982.
me emulsions must exhibit suf~icient sensitivity in the blue region of the æpectrumO For this 9 unsensitized emulsions are generally used, their sensitivity depending on that of the specific silver halide used.
. . ~
.
10693~9 It is, however, also possible to sensitize the silver halide emulsions in the blue region of the spectrum, e.g. by sensi-tizers such as are described in the Briti~h P~tent Speci-fication No. 1 285 078.
m e emulsions can cont~in conventional stabilizers, e.gO
homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercuric salts, sulfonium mercuric double salts and other mercury compoundsO Other suitable stabilizers are azaindenes, pre-ferably tetra- and pentazaindenes, especially those which are substituted with hydroxyl or amino groupsO Such compounds have been described in the article by BIRR, Z.Wiss.PhotO, Vol. 47~ 2 ~ 58 ~1952)o Other æuitable stabilizers are hetero-cyclic mercapto compounds, e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
m e emulsions can be hardened in the U5Ual manner~ for example with formaldehyde or with haIo~en-substitut~d alde-hydes containing a carboxyl group such ac mucobromic acid~
d$ketones, methane sulfonic acid ester and dialdehydes~
me following examples illustrate the advantages of the couplers of this invention:
Exam~a~_~
2 m~ol of the couplers (~ormula given below) are each dissolved in ~ ml ethyl acetate and, after adding 0.5 g di-butylphthalate, emulsified with 20 ml of a 5 % gelatin ~olution at 60C in the usual way. The emulsion contains 0.16 g sodium dodecylbenzosulfonateO
Sub~equently the emulsion is mixed with 85 g of a 7.5 %
gelatin solution, containing 1.93 g dispersed silver bromide, A-G 1206 ` - 42 -10693~;9 and then diluted with water until the casting viscosity is reachedO
After casting the emulsion on to a transparent support of cellulose triacetate, the material thus produced is ex-posed behind a grey step wedge and cut into several test samplesO
One test sample is stored for 7 days at 57C and 34 %
relative humidity in a heating cupboard before being photo-graphically processed.
The untreated test samples are developed ~or 2 minutes or 8 mi~utes in a conventional color developer, containing diethyl-~-phenylene-diamine as developer, and are then bleached and fixed as usual. me stored test samples are developed in the same way for 8 minutes.
The couplers used are of the ~ollowing formula, the following Table showing the meanings of X:
CH3 0 o C16H33 CH~ - C - C - CH - C - NH -CH X
The sensitometric evaluation o~ the individual test samples is shown in the following Table which gives a compari-son between test samples using 2- and 4-equivalent couplers in relative val~es. C~umn 1 showæ the fog values ~S) obtained with those test samples developed for 8 minutes; column 4 compares the increa~e in basic fog values (~ S) between the test samples stored in the heating cupboard before being de~eloped for 8 minutes and the unstored test samples in relative values.
A-G 1206 _ 43 _ 10693f~9 o. ' o. .. ~o o o o ~, .~ O O~ E` a~
~, ~ CU, X~3 0 o ~_ a~
o . ~ .
o ~a o u~ ~i _~
~o. ~o. ~ C~
tQ O O , O O
1~1 :' _ ~, bO O 00 0 ,~ ~ .~ U~ ~D
o ~ o ~ I O
~ ~ h 0 m o o~c~ h ~;0 ~ h : . ~ . o .~om ~omoo . oom . _ 1~ ~ ~ ~ ~a ~ N , _ _ A-G 1206 ~ - 44 -10693~9 1~ L+ I~
~ .~ c~ 0. a~ o~
~ 0 ~ C~l ~ C~l . . .
~ ~ ~ . . ~
.~ ~ ~ o ~
~1 L
A-G 1206 - 44 a -10~93~9 As can be seen from the Table, the rates of reaction of the couplers of this invention (Nos. 2, 22, 60 and 44) are comparable to that of the reference coupler D, taken from the British Patent Specification No. 1,331,179, since the density values obtained for the variou~ development times are approximately equal.
However, the reference coupler D is adversely affected in stability during warm and damp storage so that a considerable increase in the fog value ~ S can be ob~ervedO
Compared with coupler C (described in the German Offen-legungsschrift DT-OS 2,318,807) the yellow couplers of this invention are remarkable on account of their greater sensi-tivity as well as their higher rate of reaction.
ExamPles 2 A photographic material was prepared with coupler No~ 5, as described in Example 1 above. A test sample of this material was stored in a heating cupboard (as described in Example 1) and a second test sample was developed immediately for 8 minutesO
The sensitometric evaluation of the test samples was carried out as in Example 1, the following results being obtained:
Coupler X S Sensi- Dmax ~ S
- - ; ,, ~
o ~ N~ 0.07 + 6.3 2~9 + 0.05 ~ N
A-G 1206 _ 45 _ 10693f~9 A comparison o~ these values with the corre~ponding values o~ the yellow couplers of this invention in the above Table shows that benzoylacetanilide yellow couplers also exhibit extremely good properties as regards reactivity, sensitivity and stability during storageO
A-G 1206 . - 46 -
A-G 1206 _ 39 _ 106i93~9 To produce photographic color images, an exposed layer of silver halide emulsion is developed with an aromatic primary amino-developer in the presence of a color coupler according to the invention. me developer substances used may be any color developer which are able to yield azomethine dyes by chromogenic development. Suitable substances are aromatic compounds, such as ~-phenylene diamine and i*s derivatives, for example N,N-dialkyl-~-phenylenediamine, N,N-die~hyl-~-phenylenediamine, N,N-dialkyl-N'-sulfomethyl-~-phenylenediamine and N,N-dialkyl-N'-carboxymethyl-~-phenylenediamineO
Suitable light-sensitive emulsions are emulsions of silver halides, such as silver chloride, silver bromide or mixtures thereof which may have a small content of silver iodide up to 10 Mols-%, in one of the hydrophilic binding agents normally used. Gelatin is the preferred binding agent for the photographic layers. m is can, howeverJ be replaced wholly or in part by other natural or synthetic binding agents. Suitable natural binding agents are eOgO alginic acid and its derivatives such as salts 9 esters or amides;
- cellulose derivatives such as carboxymethylcellulose;
alkylcellulose such as hydroxyethylcellulose; starch or its derivatives such as ethers or esters; or caragenates.
Among the synthetic binding agents, polyvinylalcohol, partially saponified polyvinylacetate, polyvinylpyrrolidone and ~ e like should be mentionedO
me emulsions may also be chemically sensitized, eOg.
by the addition of suliur-containing compounds during chemical ripening, ~cr example, allylisothiocyanate, allyl-A-G 1206 _ 40 _ 10693~9 thiourea and sodiumthio~ulfateO Furthermore, reducing agents such as, for example, the tin compounds described in Belgian Patent Specification Nos. 493 464 or 568 687, as well as polyamines such as diethyltriamine or aminomethane sulfinic acid derivatives (as in Belgian Patent Specification 547 323) may also be used as chemical sensitizers. In addition, the rare metals such as gold, platinum, palladium, iridium, ruthenium or rhodium are suitable as chemical sensitizersO
m is method of chemical sensitization has been described in the article by R. KOSLOWSKY, ZoWisS.Phot., Vol. 46, 65 - 72, (1951).
It is also possible to sensitize the emulsions with polyalkyleneoxide derivatives, e.g. with polyethylene oxide having a molecular weight o~ from 1.000 to 20.000, and further with the condensation products of alkylene oxides and aliphatic alcohols, glyccls, cyclic dehydration products of hexitoles; with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
The condensation products have a molecular weight of at least 700, preferably of more than 1000. To obtain special ef~ects, the sensitizers can, of course, be combined, in the manner described in Belgian Patent Specification No. 537 278 and in British Patent Speci~ication NoO 727 982.
me emulsions must exhibit suf~icient sensitivity in the blue region of the æpectrumO For this 9 unsensitized emulsions are generally used, their sensitivity depending on that of the specific silver halide used.
. . ~
.
10693~9 It is, however, also possible to sensitize the silver halide emulsions in the blue region of the spectrum, e.g. by sensi-tizers such as are described in the Briti~h P~tent Speci-fication No. 1 285 078.
m e emulsions can cont~in conventional stabilizers, e.gO
homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercuric salts, sulfonium mercuric double salts and other mercury compoundsO Other suitable stabilizers are azaindenes, pre-ferably tetra- and pentazaindenes, especially those which are substituted with hydroxyl or amino groupsO Such compounds have been described in the article by BIRR, Z.Wiss.PhotO, Vol. 47~ 2 ~ 58 ~1952)o Other æuitable stabilizers are hetero-cyclic mercapto compounds, e.g. phenylmercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
m e emulsions can be hardened in the U5Ual manner~ for example with formaldehyde or with haIo~en-substitut~d alde-hydes containing a carboxyl group such ac mucobromic acid~
d$ketones, methane sulfonic acid ester and dialdehydes~
me following examples illustrate the advantages of the couplers of this invention:
Exam~a~_~
2 m~ol of the couplers (~ormula given below) are each dissolved in ~ ml ethyl acetate and, after adding 0.5 g di-butylphthalate, emulsified with 20 ml of a 5 % gelatin ~olution at 60C in the usual way. The emulsion contains 0.16 g sodium dodecylbenzosulfonateO
Sub~equently the emulsion is mixed with 85 g of a 7.5 %
gelatin solution, containing 1.93 g dispersed silver bromide, A-G 1206 ` - 42 -10693~;9 and then diluted with water until the casting viscosity is reachedO
After casting the emulsion on to a transparent support of cellulose triacetate, the material thus produced is ex-posed behind a grey step wedge and cut into several test samplesO
One test sample is stored for 7 days at 57C and 34 %
relative humidity in a heating cupboard before being photo-graphically processed.
The untreated test samples are developed ~or 2 minutes or 8 mi~utes in a conventional color developer, containing diethyl-~-phenylene-diamine as developer, and are then bleached and fixed as usual. me stored test samples are developed in the same way for 8 minutes.
The couplers used are of the ~ollowing formula, the following Table showing the meanings of X:
CH3 0 o C16H33 CH~ - C - C - CH - C - NH -CH X
The sensitometric evaluation o~ the individual test samples is shown in the following Table which gives a compari-son between test samples using 2- and 4-equivalent couplers in relative val~es. C~umn 1 showæ the fog values ~S) obtained with those test samples developed for 8 minutes; column 4 compares the increa~e in basic fog values (~ S) between the test samples stored in the heating cupboard before being de~eloped for 8 minutes and the unstored test samples in relative values.
A-G 1206 _ 43 _ 10693f~9 o. ' o. .. ~o o o o ~, .~ O O~ E` a~
~, ~ CU, X~3 0 o ~_ a~
o . ~ .
o ~a o u~ ~i _~
~o. ~o. ~ C~
tQ O O , O O
1~1 :' _ ~, bO O 00 0 ,~ ~ .~ U~ ~D
o ~ o ~ I O
~ ~ h 0 m o o~c~ h ~;0 ~ h : . ~ . o .~om ~omoo . oom . _ 1~ ~ ~ ~ ~a ~ N , _ _ A-G 1206 ~ - 44 -10693~9 1~ L+ I~
~ .~ c~ 0. a~ o~
~ 0 ~ C~l ~ C~l . . .
~ ~ ~ . . ~
.~ ~ ~ o ~
~1 L
A-G 1206 - 44 a -10~93~9 As can be seen from the Table, the rates of reaction of the couplers of this invention (Nos. 2, 22, 60 and 44) are comparable to that of the reference coupler D, taken from the British Patent Specification No. 1,331,179, since the density values obtained for the variou~ development times are approximately equal.
However, the reference coupler D is adversely affected in stability during warm and damp storage so that a considerable increase in the fog value ~ S can be ob~ervedO
Compared with coupler C (described in the German Offen-legungsschrift DT-OS 2,318,807) the yellow couplers of this invention are remarkable on account of their greater sensi-tivity as well as their higher rate of reaction.
ExamPles 2 A photographic material was prepared with coupler No~ 5, as described in Example 1 above. A test sample of this material was stored in a heating cupboard (as described in Example 1) and a second test sample was developed immediately for 8 minutesO
The sensitometric evaluation of the test samples was carried out as in Example 1, the following results being obtained:
Coupler X S Sensi- Dmax ~ S
- - ; ,, ~
o ~ N~ 0.07 + 6.3 2~9 + 0.05 ~ N
A-G 1206 _ 45 _ 10693f~9 A comparison o~ these values with the corre~ponding values o~ the yellow couplers of this invention in the above Table shows that benzoylacetanilide yellow couplers also exhibit extremely good properties as regards reactivity, sensitivity and stability during storageO
A-G 1206 . - 46 -
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A light-sensitive material comprising at least one silver halide emulsion layer and in effective contact with it a 2-equivalent yellow coupler having a nitrogen-containing 6-membered hetero-aromatic ring capable of splitting off during coupling at the coupling position connected by said nitrogen atom to the coupling position of the yellow coupler, wherein the 2-equivalent coupler has the following formula:
in which K represents a yellow coupler radical substituted in the methylene group; A and B together represent (1) (2) or (3) D and E together represent:
(1) (2) or (3) or A and B together or D and E together represent:
(4) -N=N-;
X and Y represent hydrogen, alkyl, aryl, alkoxy, halogen, acyl, acyloxy, acylamino, carbamyl, sulfamyl or together represent the ring atoms necessary to complete a condensed aromatic or heteroaromatic ring;
X' and Y' represent the same as X and Y or may be hydroxy;
provided that D and E together represent unless at least one of the groups A and B together as well as D and E
together represents one of (2) and (3) above or D and E together complete a condensed aromatic or heteroaromatic ring and provided that D and E together do not complete a condensed benzene ring unless A and B together represent one of (2) and (3) above.
in which K represents a yellow coupler radical substituted in the methylene group; A and B together represent (1) (2) or (3) D and E together represent:
(1) (2) or (3) or A and B together or D and E together represent:
(4) -N=N-;
X and Y represent hydrogen, alkyl, aryl, alkoxy, halogen, acyl, acyloxy, acylamino, carbamyl, sulfamyl or together represent the ring atoms necessary to complete a condensed aromatic or heteroaromatic ring;
X' and Y' represent the same as X and Y or may be hydroxy;
provided that D and E together represent unless at least one of the groups A and B together as well as D and E
together represents one of (2) and (3) above or D and E together complete a condensed aromatic or heteroaromatic ring and provided that D and E together do not complete a condensed benzene ring unless A and B together represent one of (2) and (3) above.
2. A light-sensitive material according to claim 1, wherein K repre-sents an open-chain ketomethylene yellow coupler radical.
3. A light-sensitive material according to claim 2, wherein the open-chain ketomethylene coupler radical is an acylacetonitrile coupler radical or an acylacetyl coupler radical.
4. A light-sensitive material according to claim 2, wherein the open-chain ketomethylene coupler radical corresponds to the following formula:
in which B = represents an alkyl radical with 1 - 32 carbon atoms, an alkoxy-alkyl radical, a bicycloalkyl radical, a heterocyclic radical or an aryl radical.
B'= represents cyano or the group in which R1 = hydrogen or an alkyl radical with 1 - 5 carbon atoms;
R2 = an alkyl radical with 1 - 18 carbon atoms or a phenyl radical which may be substituted by alkyl with 1 - 18 carbon atoms, alkoxy with 1 - 18 carbon atoms, aralkyl, aryl, aroxy, acyl, acyloxy, halogen, acylamino, amino, carbamyl, sulfamyl, sulfo or carboxy.
in which B = represents an alkyl radical with 1 - 32 carbon atoms, an alkoxy-alkyl radical, a bicycloalkyl radical, a heterocyclic radical or an aryl radical.
B'= represents cyano or the group in which R1 = hydrogen or an alkyl radical with 1 - 5 carbon atoms;
R2 = an alkyl radical with 1 - 18 carbon atoms or a phenyl radical which may be substituted by alkyl with 1 - 18 carbon atoms, alkoxy with 1 - 18 carbon atoms, aralkyl, aryl, aroxy, acyl, acyloxy, halogen, acylamino, amino, carbamyl, sulfamyl, sulfo or carboxy.
5. A light-sensitive material according to claim 1, wherein the heteroaromatic ring is 3-hydroxy-pyridazinone-6, pyrimidinone-2, pyrimidinone-6, pyrazinone-2, 4-hydroxy-pyridinone-2 or a 1,2,4- or 1,2,3-triazinone derivative.
6. A light-sensitive material according to claim 5, wherein a quinazolinone, quinoxalinone or benzotriazinone is contained as a benzo-condensed derivative of the heterocyclic compound.
7. A light-sensitive material according to claim 6, wherein the quinazolinone heterocyclic group is substituted with at least one chloro or methyl substituent.
8. A process for the production of yellow color images which com-prises exposure and chromogenous development of a light-sensitive photo-graphic material comprising at least one silver halide emulsion layer in the presence of a p-phenylenediamine color developer and a 2-equivalent yellow coupler, the coupler having at the coupling position a nitrogen-containing 6-membered heteroaromatic ring which is linked to the coupling position by said nitrogen atom and splits off during development, wherein the 2-equivalent yellow coupler is of the following formula:
in which K represents a yellow coupler radical substituted in the methylene group;
A and B together represent:
(1) (2) or (3) D and E together represent:
(1) (2) or (3) or A and B together or D and E together represent:
(4) -N=N-;
X and Y represent hydrogen, alkyl, aryl, alkoxy, halogen, acyl, acyloxy, acylamino, carbamyl, sulfamyl or together represent the ring atoms necessary to complete a condensed aromatic or heteroaromatic ring;
X' and Y' represent the same as X and Y or may be hydroxy;
provided that D and E together represent unless at least one of the groups A and B together as well as D and E together represents one of (2) and (3) above or D and E together complete a condensed aromatic or heteroaromatic ring and provided that D and E together do not complete a condensed benzene ring unless A and B together represent one of (2) and (3) above.
in which K represents a yellow coupler radical substituted in the methylene group;
A and B together represent:
(1) (2) or (3) D and E together represent:
(1) (2) or (3) or A and B together or D and E together represent:
(4) -N=N-;
X and Y represent hydrogen, alkyl, aryl, alkoxy, halogen, acyl, acyloxy, acylamino, carbamyl, sulfamyl or together represent the ring atoms necessary to complete a condensed aromatic or heteroaromatic ring;
X' and Y' represent the same as X and Y or may be hydroxy;
provided that D and E together represent unless at least one of the groups A and B together as well as D and E together represents one of (2) and (3) above or D and E together complete a condensed aromatic or heteroaromatic ring and provided that D and E together do not complete a condensed benzene ring unless A and B together represent one of (2) and (3) above.
9. A process according to claim 8 wherein the heterocyclic ring which splits off during development is a 3-hydroxypyridazinone-6, pyrimidin-one-2, pyrimidinone-6, pyrazinone-2, 4-hydroxy-pyridinone-2 or 1,2, 4-triazinone or a benzo-condensed 1,2,3-triazinone.
10. A process according to claim 9, wherein a quinazolinone, quinoxa-linone or benzotriazinone is split off.
11. A process according to claim 10, wherein the quinazolinone hetero-cyclic group is substituted with at least one chloro or methyl substituent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732363675 DE2363675A1 (en) | 1973-12-21 | 1973-12-21 | COLOR PHOTOGRAPHIC MATERIAL WITH NEW 2-AEQUIVALENT YELLOW COUPLERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1069369A true CA1069369A (en) | 1980-01-08 |
Family
ID=5901459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA216,483A Expired CA1069369A (en) | 1973-12-21 | 1974-12-19 | Color photographic silver halide materials with new 2-equivalent yellow couplers |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS50117423A (en) |
| BE (1) | BE823093A (en) |
| CA (1) | CA1069369A (en) |
| CH (1) | CH597628A5 (en) |
| DE (1) | DE2363675A1 (en) |
| FR (1) | FR2255634B1 (en) |
| GB (1) | GB1489076A (en) |
| IT (1) | IT1026082B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1018702B (en) * | 1974-06-26 | 1977-10-20 | Minnesota Mining & Mfg | PHOTOGRAPHIC COPULANTS PIVALILACETA NILIDIC PHOTOGRAPHIC ELEMENTS THAT INCLUDE SUCH COPULANTS E.O THE COLORS FORMED FOR THE CHROME GENO DEVELOPMENT OF SAID COPULANTS AND METHOD FOR FORMING A PHOTOGRAPHIC IMAGE CA WITH DYES IN THE PRESENCE OF DETECT COOLANTS |
| GB1528462A (en) * | 1975-01-03 | 1978-10-11 | Agfa Gevaert | Preparation of 2-equivalent colour couplers for yellow |
| DE2545756A1 (en) * | 1975-10-11 | 1977-04-21 | Agfa Gevaert Ag | METHOD OF MANUFACTURING 2-AEQUIVAL YELLOW COUPLERS |
| DE3885068D1 (en) * | 1987-12-11 | 1993-11-25 | Ciba Geigy | Heat sensitive recording material. |
| WO1997049400A1 (en) * | 1996-06-27 | 1997-12-31 | Smithkline Beecham Corporation | Il-8 receptor antagonists |
-
1973
- 1973-12-21 DE DE19732363675 patent/DE2363675A1/en active Pending
-
1974
- 1974-12-09 BE BE1006314A patent/BE823093A/en unknown
- 1974-12-16 GB GB5419574A patent/GB1489076A/en not_active Expired
- 1974-12-19 IT IT5465274A patent/IT1026082B/en active
- 1974-12-19 CA CA216,483A patent/CA1069369A/en not_active Expired
- 1974-12-20 FR FR7442330A patent/FR2255634B1/fr not_active Expired
- 1974-12-20 CH CH1715174A patent/CH597628A5/xx not_active IP Right Cessation
- 1974-12-21 JP JP14633074A patent/JPS50117423A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2255634A1 (en) | 1975-07-18 |
| IT1026082B (en) | 1978-09-20 |
| CH597628A5 (en) | 1978-04-14 |
| DE2363675A1 (en) | 1975-06-26 |
| GB1489076A (en) | 1977-10-19 |
| FR2255634B1 (en) | 1979-02-23 |
| BE823093A (en) | 1975-06-09 |
| JPS50117423A (en) | 1975-09-13 |
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