DE2634694A1 - PHOTOGRAPHIC COUPLER AND ITS USE TO CREATE PHOTOGRAPHIC IMAGES - Google Patents

Description

Photographic coupler and its use in the formation of photographic images

The invention relates to a new photographic coupler and its use for the production of photographic couplers Images; it relates in particular to a new photographic cyan coupler for use in photography, in which silver halides are used as photosensitive components.

In photography, it is widely used as a photosensitive component for recording light information a silver halide is used because it has excellent photographic properties such as excellent sensitivity and gradation. When a silver halide is used as a photosensitive component and when a When a color image is to be formed, the silver halide is generally made with a certain kind of a color Combined compound, and depending on the information recorded by the silver halide this is a color forming compound with

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of a certain type of reactive compound reacted to form a dye, i.e. a dye image. This color forming compound is called a coupler and is generally the reactive one Compound which is used in combination with the coupler for the formation of a dye to produce a Color developer such as an aromatic primary amine type developer.

It is known that when light information is recorded and developing a silver halide having a development nucleus in the presence of a coupler with a color developer the color developer reduces the silver halide to form silver, while the color developer itself oxidizes will. This creates an active oxidation product of the color developer and this reacts with the coupler to form a dye and a dye image corresponding to the information recorded on the silver halide.

Care is taken to keep the reaction between the coupler and the color developer at the active position of the coupler takes place and generally the active position is on an active methine or methylene group in the Kupp1ermo1ekül.

A coupler having a hydrogen atom at this active position is called a tetravalent coupler and a coupler with a leaving group in this active position which occurs during the reaction of the coupler with the color developer can be easily split off is referred to as a divalent coupler.

When the 4-valent coupler reacts with the color developer, four equivalents of silver halide with a developing

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germ per active position, the 2-valued coupler however, only requires two equivalents of silver halide per active position. Therefore delivers the same amount of the developed In silver, the divalent coupler produces a dye image of a higher concentration (density). If in the case of the 2-valued Coupler creates a group (bridging group) at the junction of the cleavable group that is linked to the active position is selected appropriately, it is possible to create a compound by cleavage of the To give the cleavable group a development inhibiting (inhibiting) activity. For example, a Divalent coupler having a leaving group containing a thio (-S -) group as a linking group as one Development inhibitor releasing couplers (DIR couplers) designated. Since in this coupler the development is inhibited depending on the amount of the developed silver this coupler can be used for various purposes. For example, the DIR coupler has so-called Intra-picture effects, e.g. those that change the tint of the picture control and make the image particles in the layer to which the coupler has been incorporated finer, as well as inter-image effects, e.g. those that improve the color tint in other layers. Also, the DIR coupler is below Exploitation of its effects on other layers for diffusion transmission systems used·

In addition, some divalent couplers, e.g. those which contain a dye residue in the leaving group, can be used for diffusion transfer systems, whereby the split off dye is used to generate a color image from the diffusible dye on an image receiving layer. A coupler of this type is called a diffusible dye-releasing couplers (DDR couplers). In addition, some have dyed 2-valued

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Coupler has a masking effect to complement a dye image. A coupler of this type is said to be more colored Called coupler.

As can be seen from the above, are 2-valued Coupler substantially superior to the 4-valent couplers and they are widely used because of their various uses.

Although the known divalent couplers with respect to different Properties are superior to the tetravalent couplers, they still lack some points. So is for example the rate of dye formation is slow and the divalent couplers tend to be a silver halide containing photosensitive layer to obscure or to discolor the photosensitive layer. aside from that they cannot be dispersed in sufficient concentrations in light-sensitive layers. One is therefore endeavored for a long time to eliminate this deficiency of the 2-valent couplers.

It is therefore the main object of the present invention to provide a novel divalent coupler which can be as mentioned above Does not have defects that conventional products have. The aim of the invention is also to provide a 2-valued Indicate cyan couplers excellent in photographic properties. Finally, the aim of the invention is a silver halide light-sensitive material containing such a divalent cyan coupler and a photographic one To specify the method in which such a 2-valent cyan coupler is used.

The invention now relates in particular to a bivalent photographic cyan coupler which has a removable group

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has, as the bridging group (connecting group) is a divalent group of the general group given below Formula I contains at the active position of the cyan coupler so that the oxy radical is on the side of the active position located:

E. 0
- 0 - C - C - (I)

wherein R ^ and R ₂ ^ ie have the meanings given below.

The novel 2-valent cyan coupler according to the invention has a high level because of the specific bridging group Speed of dye formation and does not result in fogging or discoloration of a photosensitive layer. It is also present in the layers of a photographically sensitive material, such as a photosensitive layer, well dispersible and it can therefore be dispersed in high concentrations in these layers. One from that cyan coupler produced dye has excellent resistance to light, heat and temperature, and he has the excellent absorption property that it does not have unnecessary absorptions but only sharp absorption owns. In addition, it is free from the development inhibiting effects of some conventional divalent couplers When, for example, the divalent cyan coupler of the present invention is incorporated into a silver halide photographically sensitive material is incorporated, the thickness of the photosensitive layer can be significantly reduced and high resolution and sharpness can be achieved in the dye image. Also, in the event a photosensitive multilayer material improves the penetration of light into the underlying layers and

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therefore, the photographic sensitivity can be increased.

The divalent cyan coupler of the present invention can generally can be represented by the following general formulas:

^R 1 A (OCCO - Y) _n ^Cll)

K where mean:

R ,, and Rp a hydrogen atom or an organic group, with the proviso that at least one of the radicals R ^ and Rp should be an organic group

A is an n-valent cyan coupler residue,

Y is a monovalent or divalent organic group; and R ^ or R ₂ can be bonded to the carbon atom of the carbonyl group via the group Y to form a ring, with the proviso that in this case R ^ or Rp and Y represent a divalent organic group,

(A ¹ - OCCO 9 - Y '(ill)

in the ^v '

R ₂ '

where mean:

R ^1,. and R ' _{2 is} a hydrogen atom or an organic group, with the proviso that at least one of the radicals R ¹ ^ and R ^f _{2 should be} an organic group,'

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A ^{1 is} a monovalent cyan coupler residue,

Y ^{1 is} an organic group with a valence of 2 or higher,

where R ¹ ^ i or R ¹ ρ can be bonded to the carbon atom of the carbonyl group via the group Y ¹ to form a ring, with the proviso that in this case R ¹ , or R ' _{2 is} a divalent organic group and Y ¹ represent an organic group with a valence of 3 or higher.

The types of the general formulas II and III given above are typical examples of the coupler of the present invention and the invention also encompasses a divalent coupler consisting of a mixture of couplers of formulas II and III. In the general formulas II and III given above, the cyan coupler radical is a radical which through Removal of the hydrogen atom or the cleavable group is formed at the active position of the cyan coupler, and when a plurality of active positions are present in a molecule, those introduced into these active positions can be Removable groups can be the same or different from one another or there can be a hydrogen atom in each of these active Positions are introduced. According to the invention, however, it is preferred that the cleavable groups in all active positions are introduced.

The term "organic group" as used herein is to be understood as meaning any monovalent or polyvalent group, the preferably aliphatic hydrocarbon radicals, aromatic hydrocarbon radicals, heterocyclic radicals, alkoxy groups, Phenoxy groups, naphthoxy groups, aliphatic hydrocarbons st off aminore st e, heterocyclic amino radicals and mercapto groups, all of which are saturated or singly or multiply unsaturated and optionally substituted, includes,

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The term "alkyl" used here is to be understood as meaning radicals or groups which contain 1 to 30, preferably 1 to 20, in particular contain 1 to 12, especially 1 to 6 carbon atoms. Those with 1 to 6, preferably 1 to 4-, in particular 1 or 2 carbon atoms are also referred to as “lower alkyl” or “IT-lower alkyl”.

The term "aryl" as used herein is preferably 5- or 6-membered monocyclic ^ or 9- or 10-membered To understand bicyclic best or groups that contain only carbon atoms or, in addition to carbon atoms, 1 to 4 heteroatoms from the group consisting of nitrogen, sulfur and oxygen. The phenyl group is particularly preferred. The aryl groups can be substituted and they preferably have 1 or 2 substituents.

The term "halogen" used here is to be understood as meaning fluorine, chlorine, bromine and iodine, preferably chlorine and bromine.

The term "heterocyclic Eest" used here means mono- or polycyclic, optionally condensed 3- to 20-membered, preferably 3- to 8-membered, in particular 4- to 6-membered rings to understand the one or contain several heteroatoms from the group consisting of nitrogen, oxygen and sulfur and optionally by one or several of the above-mentioned radicals can be substituted.

In the general formulas II and III given above, Rx., Rp, R ¹ ^ J and R'p can mean, for example: a hydrogen atom, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, an amino group, a substituted amino group, a sulfo group , a substituted or unsubstituted alkyl, alkenyl, aryl, heterocyclic group, alkoxy, aryloxy, arylthio, arylazo, acylamino, carbamoyl,

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Ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, morpholino, piperazyl and imidazolyl groups. They can also stand for divalent aliphatic hydrocarbon radicals, aromatic hydrocarbon radicals or heterocyclic radicals and composite divalent groups which contain or consist of 2 or more linked groups selected from the groups given above. In addition, all of these groups can be substituted. E ^ and ILj (or E ¹ ^ and E'p) can also be connected to one another to form an entrance. In this case, E ^ and Eo or E ¹ ^ and E ¹ ^ represent a divalent organic group.

Preferred examples of the group Y in the general formula II are aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, alkoxy groups, phenoxy groups, naphthoxy groups, aliphatic hydrocarbyl amino groups, heterocyclic amino groups and mercapto groups, and these groups may be substituted. Preferred examples of group Y ¹ in general formula III are m-valent aliphatic hydrocarbon radicals, aromatic hydrocarbon radicals, heterocyclic radicals, alkylenedioxy groups, arylenedioxy groups, alkylenediamine radicals, arylenediamino radicals and heterocyclic diamino radicals, and these groups can be substituted. In addition, the group Y 'may be an m-valent composite group containing two or more linked groups selected from the above groups, for example a divalent group containing a divalent aliphatic hydrocarbon radical and an arylene group linked thereto. In this case, k (a positive number) divalent aliphatic groups and 1 (a positive number) arylene groups may be connected to each other in the form of a block or in an arbitrary arrangement. In addition, these m-valent groups may have an oxygen atom, an imino group or the like at their end. Further

7 O 9 8 O 7/1 O 5 S.

can have two adjacent carbon atoms in the m-valent group by an oxygen atom, a sulfur atom, an imino group, a sulfonyl group, a carbonyloxy group, an aminocarbonyl group, a sulfonamido group or the like. Be interrupted. In the general formulas given above, II and III are η and m are preferably the number 1 or 2. However, if the coupler base is a polymer coupler known cyan coupler is used, η and m can also mean a number of 3 or more.

Examples of the cyan coupler residue of a preferred typical Couplers used according to the invention are, for example, those of the following general formulas:

(IV)

(V)

COF

- •

(VI)

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In the above general formulas "mean:

R-, a hydrogen atom, a halogen atom, an aliphatic atom Hydrocarbon radical, an acylamino group or a group -O-Rg or -S-Rg (where Rg is an aliphatic hydrocarbon remainder), if two or more groups R ^ are present in a molecule, these are equal to or from one another can be different. The aliphatic hydrocarbon radical can be substituted.

R ^ and Rr represent groups selected from aliphatic hydrocarbon radicals, aryl radicals and heterocyclic radicals. One of them may be a hydrogen atom, and these groups may be substituted. In addition, R ₂ and R ₁ - can be linked to one another to form a nitrogen-containing hetero ring.

ρ is an integer from 1 to 4 (in the general formula V stands for an integer from 1 to 3) and q is an integer from 1 to 5

The aliphatic hydrocarbon radical can be saturated or unsaturated, be linear, branched or cyclic. Preferred examples of aliphatic hydrocarbon radicals are alkyl groups, such as methyl, ethyl, isobutyl, dodecyl, octadecyl, cyclobutyl and cyclohexyl groups, and alkenyl groups, e.g. an allyl group. Typical examples of aryl radicals (aryl groups) are phenyl and naphthyl groups. Typical examples for heterocyclic radicals are pyridyl, quinolyl, thienyl, piperazyl and imidazoIyl groups. In the case of the substituent, the into the aliphatic hydrocarbon radical, the aryl radical or the heterocyclic radical can be incorporated, it can be, for example, a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, a sulfo group and substituted and

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unsubstituted alkyl, alkenyl, aryl, heterocyclic groups, alkoxy, aryloxy, arylthio, arylazo, acylamino, Carbamoyl, ester, acyl, acyloxy, sulfonamido, sulfamoyl, Sulfonyl, morpholino, piperazyl and imidazolyl groups Act.

The hetero ring formed by R ₂ and R ₁ - is preferably a nitrogen-containing hetero ring selected from the above-mentioned heterocyclic radicals.

In the general formulas II and III given above, the aliphatic hydrocarbon radical can be saturated or unsaturated, linear, branched or cyclic. Typical examples of a monovalent aliphatic hydrocarbon radical are alkyl and alkenyl groups, preferably methyl, ethyl, isobutyl, octyl, t-octyl, octadecyl, glyclobutyl, cyclohexyl and 2-horbornyl groups. Typical examples of the divalent aliphatic hydrocarbon radical are alkylene groups, preferably methylene, ethylene, butylene and hexylene groups. Typical examples of the aromatic hydrocarbon radical are aryl and arylene groups, preferably phenyl, naphthyl, phenylene and haphthylene groups. Preferred examples of the heterocyclic group include 3- and 6-membered heterocyclic groups containing a hetero atom such as nitrogen, oxygen and sulfur. Examples of monovalent groups are thienyl, pyridyl, quinolyl and oxadiazolyl groups, and examples of divalent groups are pyridinylene and quinolylene groups. Preferred acyl groups are acetyl, benzoyl and naphthoyl groups and preferred thioacyl groups are thioacetyl, thiobenzoyl and thionaphthoyl groups. Examples of sulfonyl groups are phenylsulfonyl, chlorosulfonyl and methanesulfonyl groups.

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In the general formulas II and III given above, the groups Y and Y ¹ can be substituted as stated above and the substituent can be one as stated above with regard to the general formulas IV ", V and VI has been.

Typical examples of the group that can be split off, the bridging (connecting) group being a divalent group contains, as represented by the general formula I, are the following:

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-OCHCOC ₀ Hc I ² '

CH,

-OCHCO I
CH,

-OCHCOMHCpHc

CH ₅

HH.

-OCHCONH

CH _x 0

-OCHCOOC ₂ H ₅

-OCHCOOCIL

C ₂ H ₅

/ Λ

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-OCHCOOCoHr

I ^{2 5}

CN

I ³

-OCCONH-

CH,

CH

-OCHCOOC ₀ H _n

-OCHCOOC ₁₂ H

Λ2 ^ι

-OCHCOOC ₂ H ₅

COO

-Cl

CONH

iIHH (/ \)

/ Λ

-OCHCONHC ₂ H ₁ -

0 9 8 g. ^ 1 / ^

2634684

-OCHCOOC ₄ H ₉ Cn)

CH _x
3

-OCHCOO- / \ -GIl

CH ₂ COO- / V-CH
CHv

-OCHCONHC ₂ H ₅ CH ₂ CONHC ₂ H ₅

-OCHCONHC ₁₂ H ₂₅ CH ₂ CONHC ₁₂ H ₂₅

-OCHCONH

CH ₂ CONHC ₂ H ₅

SO _x Na 3

SO _x Na 3

CH ₂ COOC ₄ H ₉ Cn)

-OCCOOC ₄ H ₉ C ^)

CH ₂ COOC ₄ HqCn)

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f \

-OCHCONH - // V-NHCOCHO-

CH ₂ COOC ₂ H ₅ CH ₂ COOC ₂ Hc

-0- / H 0

-0-CH

, CO

'CO

-0- / H

NC ₂ H ₅

-O-CH-CO

-0- / H

O / - \ O

"O O

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, COCH.

-0CH <

/ CHO-

CH ₂ CO

Couplers which have a leaving group, e.g., such as mentioned above, in the active position of the cyan coupler, as represented by the general formula Γ \ Γ, V or VI, are according to the invention preferably used. The reason why the coupler of the present invention has the above-mentioned excellent photographic Has properties, is presumably that it has a specific bridging (linking) group, such as mentioned above.

Below are some typical examples of the invention Couplers shown, but the couplers usable in the present invention are by no means limited to those shown below Coupler limited.

.CONH (GH ₂ ) ^ O.

OCHCOOC ₂ H ₅

(2)

C0KH (CH ₂ ) ₄ 0-

OCHCOIiHC ₂ H ₅

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CONH (CH ₂ ) ^ O-

~ ^tC 5 ^H 11

tC

CH ₂ COOC ₂ H ₅ OCHCONH

/ Γ \

OCHCONH \

CONH (CH ₂ )

^tC 5 ^K 11

OH

OCHCOOC ₂ H ₅ CH ₂ COOC ₂ H ₅

OH SO ^ Well
0

CH ₂ CONHC ₂ H ₅

SO ^ Well 5

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CH,

CON _x

OCHCOOC ₂ H ₅

OCHCOOC ₂ H ₅ COOC ₂ H ₅

COOH COOH

-OCHCOKH

NHCOCF ₂ CP ₂ H

CCHCOOCH ₂ - ^ / Vv C ₂ H ₅ ^{X === /}

OH

. CON

NH.

OCHCONH- / ^) CH,

(12)

COCH

OH

CON

COOH

(13)

OH _Γχ OH

CONH - </ \> - HNOC

OCHCOOC ₂ Hn OCHCOOC ₂ H ₅

CH CH,

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The compounds according to the invention specified above can can be produced according to the following processes:

For example, a naphthol type coupler according to in "Journal of the American Chemical Society", 64, 798 (194-2) ,, methods described are synthesized. In particular becomes 1,4 ~ dihydroxy-2-naphthoic acid with a carbonyl compound, which is a halogen atom or another substituent in a corresponding a-chloro-oc-alkyl acetate, a-bromo-ot-alkylacetylamide or contains a-bromo-a-alkoxycarbonylmethyl acetate, in a solvent such as acetone, dimethylformamide or the like. In the presence of pyridine, sodium carbonate, sodium hydroxide or Like. Reacted at room temperature or elevated temperature and the naphthoic acid obtained, such as 1-hydroxy-4 ~ (1-ethoxycarbonylethoxy) -2-naphthoic acid, i-Hydroxy-4- (1-ethylaminocarbonylethoxy) -2-naphthoic acid, 1-Hydroxy-4- (diethylsuccinyloxy) -2-naphthoic acid or the like, is converted into the corresponding phenyl ester using a conventional method odet converted into the corresponding acid chloride. Then it will be the phenyl ester or the acid chloride with heating or in a solvent such as benzene in the presence of pyridine, Sodium carbonate or the like, reacted directly with a suitable amine at room temperature or elevated temperature. on thus the desired coupler can be obtained. In addition, the desired coupler can be prepared by reaction a free acid with a corresponding amine at room temperature in the presence of dicyclohexylcarbodiimide.

A phenol type coupler can be synthesized from a 1,4-dihydroxybenzoic derivative in the manner described above * If desired, the desired coupler or its derivative can be prepared by blocking one of the hydroxyl groups of the 1,4-dihydroxybenzene derivative used as a starting material with, for example, an acetyl group, a

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Benzoyl group or the like by acylation to form a corresponding carbonyl methoxy derivative and hydrolyzing the same with an acid such as hydrochloric acid, Sulfuric acid or the like, or an alkali such as sodium hydroxide, potassium hydroxide or the like. When the acylation is not is suitable, one of the hydroxyl groups becomes a benzyloxy group benzylated, the above reaction is carried out, and then hydrogen gas is introduced to effect the reduction and remove the benzyl group.

In the following synthesis examples, some typical examples for the synthesis of the coupler according to the invention are given described in more detail.

Synthesis example 1 .

0.05 mol of i-hydroxy-2-naphthoic acid was dissolved in 70 ml of DMF and 10 ml of a 40% aqueous sodium hydroxide solution was added to the resultant solution while introducing nitrogen gas added dropwise. Then 0.05 moles of ethyl a-bromopropionate were added was added dropwise and the mixture was stirred at 40 ° C. for 3 to 4 hours to effect the reaction. After completion After the reaction, the reaction mixture was poured into ice / hydrochloric acid and the crystals formed were passed through Separated by filtration and recrystallized from acetonitrile, a compound having a melting point of 178 ° C received. Then 0.01 mol of the i-hydroxy-4— [1- (ethoxycarbonyl) ethoxy] -2-naphthoic acid and 0.01 mol of N- (S 2,4-di-tert-amylphenoxy) butylamine dissolved in 60 ml of dry dioxane, and 0.01 mol of dicyclohexylcarbodiimide was added to the solution added »The reaction was carried out at room temperature for 2 hours with stirring. After the Reaction, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure and subjected to column chromatography separated, whereby one connects with

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a melting point of 75 ° C (yield 52%) was obtained. the Elemental analysis confirmed that "this compound was the above-mentioned compound (1)."

Synthesis example 2

0.05 mol of 1,4-I) i-hydroxy-2-naphthoic acid was dissolved in 70 ml of DMF and 10 ml of a 4-0% strength aqueous sodium hydroxide solution were added dropwise to the solution obtained in this way, while introducing nitrogen gas. Then 0.05 mol of a-bromo-propionylethylamide, dissolved in 15 ml of DMI ¹ , was added dropwise and the reaction was carried out at 50 ° C. for 3 to 4 hours with stirring. After the completion of the reaction, the reaction mixture was poured into ice / hydrochloric acid, and the precipitated crystals were separated by filtration and recrystallized from acetonitrile to give a compound having a melting point of 192 ^° G. Then 0.01 mol of the 1-hydroxy-4- [1- (ethylaminocarbonyl) ethoxy] -2-naphthoic acid thus obtained was dissolved in 60 ml of dry dioxane and 0.01 mol of dicyclohexylcarbodiimide was added to the solution. The reaction was carried out at 50 to 60 ^{0 O for 30 minutes with stirring.} After the completion of the reaction, the reaction mixture was filtered and the by-produced dicyclohexylurea was removed. The filtrate was concentrated under reduced pressure and η-hexane was added. The precipitated crystals were separated by filtration and recrystallized from η-hexane to obtain a compound having a melting point of 95 ° C. (yield 65 ° / o) . The element analysis confirmed that the compound was the above-mentioned compound (2).

Synthesis example 5

0.05 mol of 1,4-dihydroxy-2-naphthoic acid was added to 70 ml of DMF dissolved and 10 ml of a 40% aqueous Na-

η η η a ο. τ / ι η C

trium hydroxide solution was added dropwise. Then, 0.05 mol of diethyla bromosuccinate dissolved in 15 ml of DMF was added dropwise and the reaction was carried out at 50 ° C. for 3 to 4 hours with stirring. After completion of the reaction, the reaction mixture was poured into ice / hydrochloric acid, and the precipitated crystals were separated by filtration and recrystallized from acetonitrile, whereby a compound having a melting point of 176 ^° C. was obtained. Then, 0.01 mol of the compound thus obtained and 0.01 mol of n-dodecylbutylamine were dissolved in 60 ml of dry dioxane, and 0.01 mol of dicyclohexylcarbodiimide was added to the solution and the reaction was carried out at 50 ° C for about 30 minutes. After the completion of the reaction, the reaction mixture was filtered and the by-produced dicyclohexylurea was removed. The filtrate was concentrated under reduced pressure and separated by column chromatography to obtain a compound having a melting point of 68 ^° C. (yield 35%). Elemental analysis and the like confirmed that the compound obtained was the above-mentioned compound (4) acted.

Synthesis example 4-

1-Hydroxy-4 ~ Ci- (4-nitro-anilinocarbonyl) -2-äthylaminocarbonyl- äthoxyü-N- [ 5 - (3-n-dodecyloxyphenoxy) butyl] -2-naphthamide, prepared by the same process as in in the above Synthesis Examples was reduced by an ordinary method with zinc and hydrochloric acid. The amino compound obtained in this way was diazotized and coupled in the alkaline state with disodium 2-hydroxy-3,6-disulfonate, a compound with a melting point of above 300 ° C. being obtained (yield 60%). Elemental analysis and the like confirmed that this compound was the above-mentioned compound (5).

Various couplers can be prepared by the above synthetic method. The results of the Element ar analysis of the couplers described above, along with those of couplers produced according to the above procedures described were prepared, in the following Table summarized.

Values of the Elem entaranalyse (%)

Coupler 1 calculated H values found C. H values ITr. 2 C. 8.35 IT 72.93. 8.67 Ή 3 73-06 8.53 2.37 73.24 8.45 2.22 4th 73.18 7.65 4.74 71.81 7.51 4.72 VJl 71-51 8.34 4.17 68.36 8.49 4.49 6th 68.48 5.63 2.58 58.29 5.76 2.67 7th 58.55 7.86 6.21 74.09 7.43 6.29 8th 74.19 7.45 6.18 68.92 7.75 6.42 9 69.02 4.89 3.83 49.18 4.72 3.96 10 49.33 6.75 2.62 64.53 6.48 2.15 11 64.33 8.26 3.75 75.65 8.41 3.92 12th 75-36 5-79 2.44 66.08 5.53 2.71 13th 66.19 8.10 9.65 68.76 8.49 9.69 69.12 5.33 1.68 67.24 5.62 1.37 67 _? 05 4.12 4.30

Those prepared by the method described above Couplers of the present invention have a much higher rate of dye formation in the color development stage than the conventional 4-valent couplers and 2-valent couplers Couplers which have an aryloxy group as a peelable group, such as e.g. a phenoxy or nitrophenoxy group, or one via a Ester-linked group, such as an acetoxy or benzoyloxy group. Also, compared to the conventional Couplers with a similar structure, the couplers according to the invention in photographic protective colloids, like gelatin, more easily dispersible. The oil-soluble couplers of the present invention have excellent solubility in coupler solvents. The couplers of the present invention having a hydrophilic group are excellent Can be used in fishery dispersions. The so-called "outside type" couplers of the present invention, the outside used by light-sensitive materials can be very easily added to a color developer or the like. Because of these advantageous properties, when couplers according to the invention are in photosensitive layers of Incorporated into photographic sensitive materials as so-called "inside-type" couplers, the thickness of the light-sensitive Layer are significantly reduced and the image sharpness and the other properties of the resulting Color images can be greatly improved. Furthermore, the couplers of the present invention have no adverse effect on the Color development and they are particularly characterized in that they have no discoloration or no other defects as a result of their good responsiveness. A dye obtained using the coupler of the present invention has been formed has excellent absorption properties, as indicated above.

The coupler of the present invention can be used in a variety of ways

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can be used by suitable selection of the combination of the basic structure and the cleavable group. if for example the cyan coupler residue is a water-soluble group such as. e.g. a sulfonic acid or carboxylic acid group, contains, the coupler is diffusible and if the leaving group itself is diffusible, the coupler can can be used as a diffusible coupler for the so-called external type photographic process in which it is used in a liquid color developer can be incorporated. An example of such a coupler is the one mentioned above Coupler

In addition, the coupler of the present invention having a diffusible Cyan coupler residue and a nondiffusible cleavable group such as a long chain aliphatic Hydrocarbon radical, e.g. an octadecyl group, can also be used for the outdoor-type photographic process when the non-diffusivity of the detachable group is mediocre and the overall structure, in which the cyan coupler radical is bound to the cleavable group in the active position, is diffusible. In addition to the above-mentioned coupler (8), the above-mentioned couplers (11) can also preferably be used as the external type couplers. and (13) can be used.

In the outdoor type photographic process, it is known that a coupler is incorporated in a liquid color developer and when a coupler-free photosensitive material, particularly a black-Y / white-silver halide photosensitive material (sometimes referred to as outside-type photosensitive material), with one When the color developer is developed, the color developer and the diffusible coupler penetrate into the light-sensitive one Material and the color developer reacts with the diffuse

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Sionable 'coupler in the presence of a silver halide ^ with a development nucleus, whereby a dye, i.e. ultimately a dye image, is formed. If a multicolored Image is produced, the color is developed one after the other with different color developers that use different couplers (e.g. cyan, magenta and yellow couplers) included, carried out.

Such a liquid color developer can be used in addition to the color developing agent and the coupler contain various photographic additives conventionally used for one liquid color developer preparation can be used, e.g. alkali metal sulfites, carbonates, bisulfites, bromides and -iodide. A typical composition of such a liquid developer is as follows:

Color developing agent 1 to 5 S.

anhydrous sodium sulfite 1 to 3 g

anhydrous sodium carbonate 10 to 60 g

Potassium bromide 0.5 to 1.5 g

Coupler 1 to 3 g

Water ad 1 1

The coupler according to the invention, especially those mentioned above Outside-type couplers containing liquid color developers has better solubility than conventional couplers and it has the excellent properties mentioned above.

A coupler · which has a diffusible cyan coupler residue and a diffusible split-off group, as Whole, however, is non-diffusible, a coupler containing a non-diffusible cyan coupler residue and a has diffusible detachable group and as a whole is non-diffusible, as well as a coupler which has a non-

7098Ö7 / 10B5

Has diffusible blue-green coupler residue and a diffusible cleavable group and diffusible as a whole are suitably used for the diffusion transfer photographic process. To these groups To make diffusible, methods of the selection of ' Groups with a low molecular weight and / or the introduction of water-soluble groups as mentioned above, e.g., a sulfonic acid group. In order to make these groups non-diffusible, methods for Introduction of a long-chain aliphatic hydrocarbon residue and / or the selection of a group with a relatively high molecular weight can be used.

Also a coupler with a diffusible cyan coupler residue and a diffusible cleavable group for the diffusion transfer process when used for the formation of an image in the color development step Chemical residue that is not required is non-diffusible. In particular, if a hydroquinone residue, a resorcinol residue or the like in the diffusible cyan coupler residue or the group which can be split off is introduced directly or via a suitable bridging group, the can couplers obtained thereby can be successfully used for the diffusion transfer process. This procedure can be based on Couplers are used in which the diffusivity properties of the cyan coupler radical and the cleavable Group are different from the above. When the diffusion transfer process is applied, an image is generated either by a method in which a through the Reaction between the cyan coupler residue and the color developer, cyan dye formed for image formation is used, or a method in which the cleavable group isolated during color development is used for image formation is used. In the first-mentioned procedure

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the blue-green dye obtained should be diffusible and in the last-mentioned process a compound formed by isolating the cleavable group from the active position should be diffusible. If this isolated compound is used, the compound should also be colored. For example, the compound should contain a coloring radical, for example an azo dye. Cleavable groups of this type can be represented, for example, by the general formulas VII and VIII given according to the following: _Ώ

-OCOO-D ( _VII)

E ₂
and

-OCCO- (viii)

D ¹
where D and D ¹ each represent a dye residue

In the general formulas VII and VIII given above, the dye radicals are preferably water-soluble and preferred Examples are monovalent residues of azo dyes, azomethine dyes, indoaniline dyes, indopheno! Dyes and Anthraquinone dyes

Examples of couplers used in the diffusion transfer process are suitable are, for example, the couplers (5) and (12) given above.

In the diffusion transfer method, it is known that a photosensitive material is used in combination with an image receiving material used. In this photographic process, the light-sensitive material is exposed to

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on the image receiving material at the latest in the development stage is laid, thereby forming an image on the image receiving material. For example, one containing a coupler is used SiTber halide light-sensitive material in combination with an image-receiving layer on a support with one therebetween arranged adhesive layer (subbing layer), an intermediate layer and the like., Is used and after-the photosensitive Silver halide material has been exposed, the photosensitive layer is placed on the photosensitive Silver halide material on the image receiving layer of the image receiving material, optionally arranging a protective layer therebetween. A liquid color developer spreads between the two layers and causes development, with one formed in the photosensitive layer Dye diffuses onto the image receiving layer and is transferred to this. Finally, the image receiving layer becomes peeled from the photosensitive material and a color image is formed on the peeled image-receiving material. Various methods are known for practicing this diffusion transfer photographic process. So For example, a photosensitive material forms one integral unit with an image receiving material, whereby the Steps of placing the photosensitive material on the image receiving material and peeling off the image receiving material can be omitted from the photosensitive material. In this case, however, if there is a boundary layer between the image receiving material and the photosensitive Material or an adjoining (adjacent) layer is an opaque layer, the support of the photosensitive Material be transparent and the photosensitive material is exposed through this transparent support. If the boundary layer or the adjoining (neighboring) layer is essentially transparent, this can be ultimately obtained image will be adversely affected by the image in the light-sensitive material, at least

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one of these layers in the stages after exposure should be made opaque. This is done, for example, in the color development stage. With the integrated A combination of this type containing a photosensitive material and an image receiving material must be at least one of the The support of the image receiving material and the photosensitive material must be transparent and the exposure is through the transparent carrier carried out. After exposure, a liquid color developer penetrates the interface area between the photosensitive material and the image receiving material or in the vicinity of this interface, whereby an image is formed in the image receiving layer.

According to another type of diffusion transfer process, a liquid color developer is in an image receiving material included, and development and image transfer can be effected by only an exposed places photosensitive material on the image receiving material.

The couplers of the present invention can be used with success for anyone Type of diffusion transfer process to be used. In general, the coupler according to the invention is used in a photosensitive layer is incorporated, and in this case, a photosensitive layer is preferably used silver halide light-sensitive material is used. The coupler is generally used in an amount of from about 0.07 "to about 0.7 »preferably from 0.1 to 0.4 moles per mole of silver halide incorporated.

Usually a so-called internal type coupler is used in used a state in which it is in a photosensitive material, particularly a silver halide photosensitive material, is incorporated. Preferably a non-dif-

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fusible coupler used to prevent other layers are adversely affected by the coupler. Among the above couplers that are used for the diffusion transfer process those that are nondiffusible can be used with success as such an indoor type coupler can be used. Couplers with a nondiffusible coupler moiety are special preferred. In this case, the group that can be split off can either be diffusible or non-diffusible.

As the coupler of this type, couplers (1), (2), (3), 00, (5), (6), (7), (9) and (10) are preferably used.

Some of the internal type couplers are practically colorless, and they form a dye by reacting with an oxidation product of the color developer which is formed during color development. Other couplers of this type are so-called! " ¹ colored couplers, and they can be used for color correction by the masking process. Coupler (5) is preferably used as the coupler of this type The colored coupler is removed from the light-sensitive material system and, at the same time, a cyan dye is formed by reacting with the color developer practically colorless coupler used.

The inside-type couplers are classified into two groups: one that contains a hydrophilic group in the molecule, and another that contains an oleophilic group in the molecule. When these couplers are used, for example, in coating compositions incorporated for the production of photosensitive layers becomes the first-mentioned coupler group, viz

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the so-called Fischer dispersion type couplers, in the form of a solution or dispersion in an alkaline solution incorporated and the last-mentioned group of couplers, namely the so-called couplers of the protected type (protection type) ^ are in the form of a solution in a coupler solvent incorporated. A typical example of a coupler according to the invention, which belongs to the first-mentioned group, is the above-mentioned coupler (7), and when the above-described dispersing method is used, they exhibit couplers of the invention have much better dissolution properties than the conventional couplers and they offer several advantages. For example, a dye image with a higher concentration (density) can be obtained, the transparency of the layer can be greatly improved and the resolving power can be improved considerably.

In general, the coupler of the present invention is used in an amount from about 0.07 "to about 0.7, preferably from 0.1 to 0.4 moles incorporated into the light-sensitive material per mole of silver halide. When the coupler is used to adjust (correct) the Color or to improve the properties of other couplers is used, the coupler of the invention is used in one Amount of from about 0.01 to about 0.1, preferably from about 0.03 to about 0.07 moles per mole of silver halide is used.

As stated above, the coupler of the present invention can be used for the accomplishment of various objects and it has excellent properties for any use . on.

The light-sensitive material to which the coupler of the present invention is applied is preferably a light-sensitive material Silver halide material and the coupler of the present invention can for various light-sensitive silver halide materials,

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e.g. for a light-sensitive silver halide material, to be used in the diffusion transfer method described above, an ordinary photosensitive one Negative material, an ordinary photosensitive material Reversal material, an ordinary photosensitive Positive material, a light-sensitive direct positive material and for special light-sensitive silver halide materials (e.g. for X-ray photography, for photography with high resolution, for infrared photography and for ultraviolet photography).

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As the silver halide for the silver halide light-sensitive material for example, silver chloride, silver iodide, silver iodobromide, silver chlorobromide and silver chloride iodobromide be used. These silver halides are produced by various processes, for example by the neutral process, the ammonia process, the mixing process in which one simultaneous mixing is carried out, the conversion process and the like. And each suitable production process is selected depending on the kind of the light-sensitive material. When using a mixed silver halide the mixing ratio of two or more of the silver halides is appropriately selected. For example using a silver halide having a relatively low sensitivity and a finer one Particle size silver chloride used as the main component, but when a coupler with a relatively high sensitivity is used, the content of silver chloride is reduced. As a silver halide can be used for a direct-positive photosensitive Material of the reverse type, for example and solarization type can be used. in the generally, this silver halide is optically or chemically sensitized to give an appropriate one to the silver halide grains To give veil. The silver halide is especially chemically sensitized with active gelatin, a sulfur sensitizer, such as allylthiocarbamide, thiourea, cystine or the like, a selenium sensitizer, a reduction sensitizer such as a stannous salt, a polyamine or the like, a noble metal sensitizer, in particular a gold sensitizer, such as potassium gold (III) thiocyanate, potassium chloroaurate, 2-gold (I) sulfobenzothiazole methochloride, a water-soluble salt of ruthenium, rhodium or iridium, ammonium chlorpalladate,

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2634634

Potassium chloroplatinate, sodium chloropalladite or the like (some these act as a sensitizer or as an antifoggant, depending on the amount used) or a combination of the two or more of the above-mentioned sensitizers, e.g. B. a combination of a gold sensitizer and a sulfur sensitizer or a combination of a gold sensitizer and a selenium sensitizer.

The silver halide can be optically sensitized for the desired wavelength range. For example, it can be with a Cyanine dye, e.g. B. a zeromethine dye, a monomethine dye, a dimethine dye or a trimethine dye, a merocyanine dye, or a combination of two or more of these dyes are optically sensitized (supersensitized).

A photosensitive layer is prepared by dispersing of the silver halide in a suitable protective colloid. In general, for the production of a photosensitive layer and from other layers, such as B. an intermediate layer, a protective layer, a filter layer, an image receiving layer, a pH adjustment layer (which is used, for example, as a layer disposed below the image-receiving layer is) and the like. Used. In addition, colloidal albumin, cellulose derivatives and synthetic resins such as polyvinyl compounds (e.g. B. Polyvinyl alcohol) ^ can be used individually or in combination. Furthermore, in combination with the protective colloids mentioned above, acetyl cellulose with an acetyl content of 19 to 26% and a water-soluble ethanolamine cellulose acetate can be used.

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Films and sheets of substrates such as paper, coated paper can be used as supports for the photosensitive material (e.g. a laminate of polyethylene and paper), glass, cellulose acetate, cellulose nitrate, polyester, polycarbonate, polyamide, Polystyrene and polyolefin can be used. These substrates can be subjected to various surface treatments , for example, a hydrophilization treatment to improve the layer adhesion. To this end you can for example, a saponification, a corona discharge, a subbing treatment (application of an adhesive layer) and a Hardening (setting) can be applied.,

The photosensitive material consists of at least one Carrier and at least one light-sensitive applied thereon Material. In general, the photosensitive material has a multilayer structure, as do other suitable ones Comprises layers arranged in suitable positions depending on the desired uses. For example, a color photosensitive material can be at least comprise two photosensitive layers sensitized to different wavelength ranges, and these light-sensitive layers can contain couplers which form different colored dyes.

The coupler of the invention forms a cyan dye, when its cyan coupler residue is used. In this case the cyan coupler becomes general for a photosensitive material in combination with divalent or tetravalent ones Couplers, e.g. A magenta coupler such as 5-pyrazolone and a yellow coupler which is one between two carbonyl groups

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contains arranged active methylene group, used. In the case of an indoor type photosensitive material these couplers are incorporated into light-sensitive layers, each of which is sensitized for suitable wavelength ranges are. In the case of a light-sensitive pseudocolor material, the coupler according to the invention can be used individually or in Combination can be used with the same type of coupler and in this case the relationship between the sensitized wavelength range and the coupler not in accordance with its relationship in an ordinary color photosensitive material.

The sensitized to a certain wavelength range photosensitive layer may consist of two or more layers. These layers can be used in terms of sensitivity be different from each other and in each of these layers different types of couplers, e.g. B. a 2-valued Couplers and a tetravalent coupler which form the same color may be incorporated. This procedure becomes general used to improve resolution and sensitivity.

As stated above, the coupler of the present invention can be used in combination can be used with another bivalent or tetravalent coupler. For example, the coupler according to the invention in combination with a 2-valent coupler, e.g. B. a so-called colored coupler (e.g. a coupler, in which a removable group containing an azo group as a bridging group is bonded to the active position of the coupler is) or a so-called DIR coupler (a coupler that releases a development inhibitor during color development,

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ζ. B. a coupler in which a thio group-containing removable group is bonded to the active position of the coupler is) can be used.

There can be various photographic additives in a photosensitive Layer and / or in other layers (e.g. an intermediate layer, an adhesive layer (subbing layer), a filter layer, a protective layer or an image-receiving layer). Examples of such photographic Additives include stabilizers, such as mercury compounds, triazoles, azaindenes, zinc salts and cadmium lazes, sensitizers, such as quaternary ammonium salts and polyethylene glycols, agents to improve the film properties, such as glycerine, hydroxyalkanes, ethylene bisglycol esters and polymer emulsions, hardeners, such as formaldehyde, halogen-substituted fatty acids, disulfonic acid chloride, bisaziridine and ethy1enimines, distributing agents, such as saponin, polyethylene glycol lauryl monoether, polyethylene glycol oleyl monoether and sulfated and alkylated polyethylene glycol salts, organic solvents such as coupler solvents (high-boiling solvents and low-boiling solvents, e.g. dibutyl phthalate, tricresyl phosphate, acetone, methanol, ethanol and ÄthylcellosoIve), so-called DIR compounds, which occur in the Color development release a development inhibitor and a can form practically colorless compounds, antistatic agents, antifoam agents, ultraviolet absorbers, fluorescent brighteners, Anti-slip agents, matting agents, antihalation agents and anti-irradiation agents. These additions can be used individually or in Form of combinations can be used.

An image-receiving layer that is separated from a light-sensitive

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2634594

Union material as described above and prepared for the diffusion transfer process in combination with used in the light-sensitive material consists of at least one support mentioned above and one thereon applied image receiving layer and, if necessary, can also have other layers, such as. B. a protective layer, an adhesive layer (subbing layer) and a pH regulating layer. In addition, photographic additives such as those indicated above can be added to these layers as required are to be incorporated. For example, to prevent back diffusion or ipadiation of the diffusible Dye produced during color development from the light-sensitive material diffuses into the image-receiving layer is preferably incorporated into the image-receiving layer a compound capable of holding the dye or to make it non-diffusible. Such Compound can be incorporated into a layer adjacent to the image receiving layer. Suitable examples are pickling agents, such as B. Polymers of aminoguanidine derivatives of vinyl methyl ketone, as described in US Pat. No. 2,882,156, and mordants as in U.S. Patent Nos. 3,271,147 and 3,271,148. Typical examples of such a compound incorporated into the image receiving layer or one thereon Adjacent (adjacent) layer can be incorporated, are also pH regulators, such as inorganic and organic Acids.

A liquid color developer used for color development of the exposed light-sensitive material contains a color developing agent as the main ingredient. Typical examples of color developing agents are primary aromatic ones

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Arain compounds, such as ρ-phenylenediamines. For example are used: diethyl-p-phenylenediarnine hydrochloride, Monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-amino-5- (N-ethyl-N-dodecylamino) toluene, N-ethyl-N-ß-methanesulfoamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-ß-methanesulfonamidoethyl-4-aminoaniline and 4-N-ethyl-N-ß-hydroxyethylaminoaniline, N-ethyl-N-ß-methoxyethyl-3-methyl-4-aminoaniline-ptoluenesulfonate, N-ethyl-N- [2- (2-methoxyethoxy) ethyl] -3-methyl-4-aminoaniline-p-toluenesulfonate, N-Ethyl-N- £ 2- [2- (2-methoxyethoxy) ethoxy] ethyl) -3-methyl-4-aminoaniline-p-toluenesulfonate and N-Ethyl-N- [2- {2- (2- [2- (2-methoxyethoxy) ethoxy] ethoxy) ethoxyethyl] -3-methyl-4-aminoaniline-p-toluenesulfonate.

These color developing agents can be used singly or in combination, or they can be used if desired can be used in combination with a black and white developing agent such as hydroquinone. The liquid color developer generally contains an alkaline agent such as sodium hydroxide, ammonium hydroxide, sodium carbonate, sodium sulfate, sodium sulfite or the like. It can also contain various additives, such as. B. an alkali metal halide such as potassium bromide, and a Development control agents such as citrazinic acid. With a certain one Diffusion transfer process becomes the liquid color developer previously incorporated into an image receiving layer. In this case, it is possible to use a method in which the color developing agent from the alkaline agent and in which only the alkaline agent or only the color developing agent is incorporated into the image-receiving layer, which is then treated with the other component during development will.

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The coupler according to the invention forms a blue-green dye by reaction with the oxidation product of the color developing agent, which is formed when the silver halide with the liquid Color developer is developed, and some couplers according to the invention also form other dyes (including a cyan dye).

When the silver halide or the developed silver in the photosensitive If material is to be removed after color development, a fixing solution, a bleaching solution, a combination of a fixing solution and a bleaching solution or a bleach-fixing solution is used. This treatment will in combination with other different treatments, for example washing with water, stopping and stabilizing, carried out. Solvents for silver halide are used for fixing, such as. B. sodium thiosulphate and ammonium thiosulphate, and potassium ferricyanide, iron (III) ammonium ethylenediamine tetraacetate are used for bleaching and sodium ethylenediamine tetraacetate is used.

The coupler of the present invention having the above structure is, as noted above, far over the conventional divalent couplers in terms of photographic properties think.

The invention is illustrated in more detail by the following examples, without, however, being restricted thereto.

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example 1

A coupler was used as shown in the table below I is indicated, and 10 g of the coupler were added to a liquid mixture of 20 ml of dibutyl phthalate and 60 ml of ethyl acetate and the temperature was raised to 60 ° C to completely dissolve the coupler. The solution obtained was with 5 ml of a 10% aqueous solution of alkanol B (alky! naphthalene sulfonate, prepared from Du Pont) and 200 ml of a 5% gelatin solution and the mixture was mixed using eluted with a colloid mill to obtain a coupler dispersion.

The dispersion thus prepared then became 500 g of a high sensitivity Silver iodobromide negative gelatin emulsion (containing 6.0 mol% silver iodide) was added and the mixture was shaped coated in a layer on a cellulose triacetate film support and dried.

The sample produced in this way was exposed through an optical step wedge (gray wedge) and exposed for 10 minutes at 20 ° C. with a liquid Color developer having the following composition developed:

N-ethyl-N-ß-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.0 g

anhydrous sodium sulfite 2.0 g

Sodium carbonate monohydrate 50.0 g

Potassium bromide 1.0 g

Sodium hydroxide. 0.55 g

Benzyl alcohol 4.0 ml

Water ad 1 1

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The sample was then subjected to a stop and fix treatment using a conventional method for 10 minutes washed with water and bleached for 5 minutes at 20 C with a bleaching solution of the following composition:

Potassium ferricyanide 100 g

Potassium bromide 50 g

Water ad 1 1

The sample was then washed with water for 5 minutes and at 20 ° C. for 5 minutes with a fi: g2nd specified composition fixed:

and for 5 minutes at 20 C with a fixing solution of the following

Sodium thiosulfate heptahydrate 250 g

Water ad 1 1

Then the sample was washed again with water for 25 minutes and dried.

The photographic properties of the sample thus treated were measured, with the results shown in Table I below were obtained.

709807/105 5

sample
No. used
Coupler relative gamma
(γ) maximum Table I. image Resistance to
humidity 1 Coupler (l) Sensation
opportunity 1.17 density
(D)
Max wavelength light
authenticity 74% 2
3 Coupler (4)
Comparison
coupler (1) 131 1.20
1.00 2.22 of absorption
maximums Q)
Max 91% 76%
68% 140
100 2.33
1.95 700 nm 92 %
90 % 7098 700 nm
700 nm ο
-J 1055

In the above table, the relative sensitivity is based on the sensitivity of the sample 3 prepared using the comparative coupler (1), which was set at 100. The comparative coupler (1) had the structure shown below. The light fastness is expressed by the ratio (%) between the residual density after 16 ~ hours of exposure in a Xenon Fade-O-Meter and the density before exposure. The resistance to moisture is expressed by the ratio (%) between the residual density after storage for 2 weeks at a relative humidity of 80%
Storage.

of 80% and a temperature of 50 C and the density before

The comparative coupler (1) disclosed in U.S. Patent 2,474,293 has the following structure:

COKH-f-CH ₂ -) _7j O- ^ \> -tC ₅ H ₁ ^

Cl

As can be seen from the results in Table I above, the coupler of the present invention has excellent photographic properties Properties (high sensitivity, calculated Lightfastness and excellent resistance to moisture) ajfund those using the invention Coupler prepared sample gives a color image with a high definition.

When coupler (2) was used in place of couplers (1) and (4), it was found that coupler (2) was a coupler of Indoor type was that of excellent photographic properties

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similar to Couplers (1) and (4).
Example 2

A liquid mixture of 20 ml of dibutyl phthalate and 60 ml Ethyl acetate was added to 10 g of the coupler (10) and the temperature was raised to 60 ° C. to completely dissolve the coupler. The resulting solution was mixed with 5 ml of a 10% strength aqueous solution of alkanol B and 200 ml of a 5% strength aqueous solution Gelatin solution was mixed, and the mixture was emulsified using a colloid mill to obtain a coupler dispersion became.

The dispersion thus prepared became 500 g of a red-sensitive one Silver iodobromide emulsion (with 4.0 mol% silver iodide) with a high sensitivity was added and the mixture was coated on a cellulose acetate film support and dried to obtain a photographic sensitive material having a permanent coating.

The light-sensitive material was exposed to light in the same manner as in Example 1 and with a for 12 minutes at 21 ° C liquid developer with the following composition:

Methyl 3.0 g

anhydrous sodium sulfite 50.0 g

Hydroquinone 6.0 g

anhydrous sodium carbonate 40.0 g

Potassium bromide 3.5 g

Potassium thiocyanate 2.0 g

Water ad 1 1

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The sample was then stopped using standard procedures, cured and washed with water, and thereafter it was subjected to secondary exposure to white light. then the sample was treated with a liquid color developer of the composition given below at 21 G for 13 minutes COLOR DEVELOPMENT:

N, N-diphenyl-2-methyl-p-phenylenediamine 3.0 g

anhydrous sodium sulfite 4.0 g

Sodium carbonate monohydrate 20.0 g

Potassium bromide 2.0 g

Water ad 1 1

The sample was then stopped, washed with water, bleached and fixed using conventional methods Washed for 20 minutes in running water and dried, whereby a positive blue-green dye image with excellent transparency and an absorption maximum at 700 nm received.

From the above, it can be seen that the inventive Coupler exhibited excellent photographic properties when used for a reversal photosensitive material.

Example 3

In a liquid mixture of 20 ml of tricresyl phosphate and 60 ml of ethyl acetate, 20 g of a coupler as shown in Table II below was dissolved and added to the same As in Example 1, a coupler dispersion was prepared from the solution. The coupler dispersion became 100 ml added highly sensitive silver iodobromide emulsion and the

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The mixture was applied in the form of a layer on a film support and dried to form a photosensitive material received.

The light-sensitive material was made using conventional ones Method exposed and 3 minutes and 15 seconds at 38 C with a liquid color developer of the following Composition developed:

N-ethyl-N- (ß-hydroxyethyl) -3-methyl-4-aminoaniline hydrochloride 5.0 g

Anhydrous sodium sulfite 2.0 g

Sodium carbonate 50.0 g

Potassium bromide 1.0 g

Sodium hydroxide 0.55 g

Water ad 1 1

Then the sample was bleached with a bleach solution for 6 minutes at 38 ° C bleached with the following composition:

Disodium ethylenediamine tetraacetate 40.0 g

Ferric chloride 30.0 g

Sodium carbonate monohydrate 20.0 g

Potassium bromide 30.0 g

Water ad 1 1

The sample was then washed in the usual way with water, fixed and stabilized, whereby a positive image was obtained an absorption maximum at 520 to 535 nm and a blue-green dye image with an absorption maximum at 700 nm received. The photographic properties of the sample were measured and the results given in Table II below were obtained.

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In the following table the relative sensitivity is related on the sensitivity of the sample prepared using the comparative coupler (2) given below the value of which was set at 100.

The Vei ^ Leichkuppler (2) used, which in the US patent 3 034 892 had the following structure:

-tC.H

COCH-

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CD CD CO O

CD cn Cn

used
Coupler relative
Sensitive
speed Table II Wavelength of the
Absorption
maximums (A)
Max sample
No. Coupler (5)
Comparison
coupler (2) 138
100 maximum
density
(D)
Max 700
700 4th
5 1.8
1.6

Wavelength of the absorption maximum the mask

520 500

In the table above, the wavelength of the absorption maximum of the mask is the wavelength of the absorption maximum the color of the coupler itself.

As can be seen from this example, the inventive Couplers on-the-so-called masking processes are used. From the results shown in the above table, it can be seen that the coupler is excellent in this case as well Had photographic properties and that the invention Coupler was significantly better than the conventional coupler in terms of sensitivity and density, and was excellent Gave a dye image with improved sharpness.

Example 4

The coupler (7) was incorporated into a highly sensitive silver iodobromide negative emulsion by the Fischer dispersing method (the amount of the coupler used was 0.2 mol per mol of silver halide) and the emulsion became in the form of a layer applied to a cellulose triacetate film support in a conventional manner and dried. The sample obtained in this way was exposed to light and for 3 minutes at 24 ° C. with an alkaline liquid developer the following composition treated:

Sodium sulfite 2.0 g

4-N-ethyl-N-ß-hydroxyethylaminoaniline 11.0 g

Water ad 1 1

During the above development, the photosensitive layer became the sample is placed on an image-receiving layer of an image-receiving material which contains dimethyl-β-hydroxyethyl-γ-stearoamidopropylammonium hydrogen phosphate in the image-receiving layer contained, and after the

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Development became the image receiving material from the photosensitive one Material removed. A sharp blue-green negative image with excellent results was found on the image receiving material photographic properties formed. This confirmed that the coupler of the present invention was also excellent Represents couplers for use in diffusion transfer color photography.

Example 5

The coupler (8) was dissolved in methanol and, using this solution, became an outside-type liquid color developer produced with the following composition:

N, N-diethyl-2-methyl-p-phenylenediamine 2.0 g

anhydrous sodium sulfite 2.0 g

Sodium carbonate monohydrate 20.0 g

Potassium bromide 1.0 g

Coupler (8) 2.0 g

Water ad 1 1

One by applying a highly sensitive silver iodobromide emulsion produced in the form of a layer on a polyethylene terephthalate film provided with an adhesive layer (subbing layer) Sample was exposed to light and for 3 minutes at 24 C with the above-mentioned external-type liquid color developer developed. The developed sample was washed with water using standard procedures for 4 minutes, for 5 minutes bleached, washed with water for 5 minutes, fixed for 5 minutes, washed with water for 30 minutes, and dried. This gave a blue-green dye image with an absorption

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tion maximum at 700 ran and a high spectral characteristic, which also had excellent other photographic properties.

If the above procedures are repeated in the same manner using the coupler (11) in place of the The above-mentioned coupler (8) correspondingly gave an excellent dye image with an absorption maximum obtained at 700 nm. As a result, it was confirmed that the coupler of the present invention is an excellent external type coupler.

Example 6
Dispersion A

In a solvent mixture of 22 ml of tricresyl phosphate and 6.0 0.15 g of the coupler (5) and 2.0 g of the known coupler 1-hydroxy-N- [£ - (2,4-di-t-amylphenoxy) butyl] -2-naphthamide were added ml of ethyl acetate dissolved and a coupler dispersion was prepared from this solution in the manner indicated in Example 1.

Dispersion B

In addition, 0.20 g of the known DIR compound were added to dispersion A 2- (1-Phenyl-5-tetrazolylthio) -4- [2- (2,4-di-t-amylphenoxy) acetamido] indanone admitted.

Dispersion C

In the same manner as indicated above with reference to dispersion B, this dispersion was prepared under Use of 0.1 g of the known DIR coupler 1-hydroxy-4- (1-phenyl-5-tetrazolylthio) -2- (2-tetradecyloxyphenyl) -naththamide instead of the DIR connection given above.

709807/1055

Dispersion D

In the same manner as indicated above with reference to dispersion B, this dispersion was prepared using Use of the known comparative coupler (2) instead of the coupler (5) according to the invention.

Each dispersion became 100 ml of a red sensitive silver iodobromide emulsion (with 7.0 Mo1% silver iodide) with a high Sensitivity was added and the mixture was coated on a film support and dried. on thus 4 photosensitive materials were obtained.

These light-sensitive materials were exposed to light in the usual manner and then in the same manner as in Example 3 treated. The photosensitive material B was the materials A, C and D in terms of gradation in that obtained Superior dye image. In addition, the dye image formed using Photosensitive Material B exhibited excellent graininess and sharpness. The results obtained are given in Table III below.

709807/1055

photosensitive veil Table III gamma Graininess Sharpness Ui
00 material relative (RMS) (U 0.5) ι sensitivity O 0.22 1.00 CO A. 0.11 0.72 53 50 CO
CD B. 0.13 100 0.71 40 40 -J C. 0.14 97 0.72 43 42 O D. 92 45 43 cn
CJl 95

N) CO Ca) J> CD CO

The RMS value is a value that is preserved was obtained by multiplying the standard deviation of the change in density value obtained by scanning of a round microdensitometer with an abbot as do gs diameter of 25 / U, with a factor of 1000. The U 0.5 value is it is a spatial frequency value at which the MT factor is reduced to 50%.

Patent claims:

709807/1055

Claims (13)

Claims 1. Process for producing a cyan dye image, characterized in that an image-wise exposed light-sensitive color photographic silver halide material is used comprising a support and at least one silver halide emulsion layer coated thereon containing a color developing agent containing color developer in the presence of a bivalent cyan coupler of the general formula: A - (- OCCO - Y) I ⁿ ■ (ID where mean: A is an n-valent cyan coupler radical, Y is a monovalent or divalent organic group, η is an integer, R ₁ and R "individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the radicals R and R" should be an organic group, and where R, or R ~ via the group Y with the carbon atom of the carbonyl group can be linked to form a ring, with the proviso that in this case R, or R ₂ and Y are a divalent organic group, (in) 709807/1055 where mean: A ^{1 is} a monovalent cyan coupler radical, Y ^{1 is} a divalent or higher organic group, R ¹ , and R ¹ 2 individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the radicals R 'and R'"is an organic Should be group, and where R 'or R' _{2 can be} linked via the group Y to the carbon atom of the carbonyl group to form a ring, with the proviso that in this case R 'or R'"and Y represent a divalent organic group stand. 2. The method according to claim 1, characterized in that the cyan coupler residue ^{represented by A or A 1} is one which is derived from any of the cyan couplers of the general formulas given below: OH OH .CON « 4 5 and where mean: R ~ a hydrogen atom, a halogen atom, a substituted one or unsubstituted, saturated or unsaturated aliphatic hydrocarbon radical, an acylamino group or a group -O-Rg or -S-Rg (where R ^ is an aliphatic 709807/10 5 5 shear hydrocarbon radical), if two or more R "radicals are present in a molecule, these may be the same or different from one another; R, and R ₅ individually each represent a substituted or unsubstituted aliphatic hydrocarbon radical, an aryl radical and a heterocyclic radical, or in which R, and R can be linked to one another to form a nitrogen-containing hetero ring, ο an integer from 1 to 4, ρ an integer from 1 to 3 and q is an integer from 1 to 5. 3. The method according to claim 1, characterized in that that in the general formulas II and III η and m each denote the number 1 or 2. 4. The method according to any one of claims 1 to 3, characterized in g e that the color developing agent is a primary aromatic amine compound. 5. The method according to any one of claims 1 to 4, characterized in that the cyan coupler in the SiI-berhalide emulsion layer of the color photographic light-sensitive material is contained. A method according to any one of claims 1 to 4, characterized in that the blue-green coupler is in the color developer is included. 7. Process for producing a cyan dye image, characterized in that an imagewise exposed light-sensitive color photographic silver halo 709807/1055 Genid material with a carrier and at least one applied thereon A silver halide emulsion layer comprising a color developer containing a p-phenylenediamine in the presence of a 2-valent blue-green coupler of the general formula: R ^R 1 'Υ1 A - OCCO - Y, (A - 0CC0 42-Y ' _or A - 4-0CC0 - Y) ₂ where mean: Y is a monovalent or divalent organic group, Y 'is a divalent or trivalent organic group, R ₁ and R ₉ individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the radicals R _{1 and R 2 should be} an organic group , or in which R- or R ₂ can be bonded to the carbon atom of the carbonyl group via the group Y to form a ring, with the proviso that in this case R, or R "and Y represent divalent organic groups, R 'and R' individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the radicals R 'and R' should be an organic group, or in which R 'or R' ₉ to the carbon atom via the group Y ' the carbonyl group can be bonded to form a ring, with the proviso that in this case R 'or R' _{9 represent} a divalent organic group and Y ^{1 represents} a trivalent organic group, A and A ¹ each represent a cyan coupler residue derived from a cyan coupler of the general formula 709807/1055 -r- OH C0R _c or where mean: R "is a hydrogen atom, a halogen atom, a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon radical, an acylamino group or a -0-R- group. or -SR ₁ - ^{1 (in which R 1 is} an aliphatic hydrocarbon radical), where if two or more groups R ~ are present in a molecule, these can be the same or different from one another, R, and R ₁ - individually in each case a substituted or unsubstituted aliphatic hydrocarbon radical, an aryl radical and a heterocyclic radical or in which R, and Rj- can be linked to one another to form a nitrogen-containing hetero ring, ο an integer from 1 to 4, ρ is an integer from 1 to 3 and q is an integer from 1 to 5. 8. Bivalent photographic cyan coupler, g e k e η η drawings by the general formula A - (- OCCO - Y) _n (A'-OCCO- ^ Y'I or I.
R ₂ R ₂ ¹ 709807/1055 - 651 where mean: Y is a monovalent or divalent organic group, η is an integer, Y ^{1 is} a divalent or higher organic group, m is an integer, R, and R "individually in each case a hydrogen atom or a organic group, with the proviso that at least one of the radicals R., and R "should be an organic group, or in which R ₁ or R ₉ can be bonded to the carbon atom of the carbonyl group via the group Y to form a ring with which Provided that in this case R, or R "and Y represent a divalent organic group, R 'and R' individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the radicals R 'and R' denotes an organic group, or in which R 'or R ¹ ^ via the group Y ¹ to the carbon atom of Carbonyl group can be bonded to form a ring, with the proviso that in this case R 'or R '~ represent a divalent organic group and Y ^{1 represent} a trivalent or higher organic group, A and A ¹ each represent a cyan coupler residue derived from a cyan coupler of the general formula: 709807/105 5 COR _r or where mean: R "is a hydrogen atom, a halogen atom, a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon radical, an acylamino group or a group -0- ^R ₆ or -S-Rg (where R ^ is an aliphatic hydrocarbon radical) and in which, if two or more groups R ~ are present in a molecule, these can be the same or different from one another, R, and R ₁ - individually in each case a substituted or unsubstituted aliphatic hydrocarbon radical, an aryl radical and a heterocyclic radical or in which R, and R ₁ - can be connected to one another to form a nitrogen-containing hetero ring, ο an integer from 1 to 4,
ρ is an integer from 1 to 3 and
q is an integer from 1 to 5. 9. cyan coupler according to claim 8, characterized in that in the general formula η and m, respectively the number 1 or 2 mean. 709807/1055 10, silver halide color photographic light-sensitive material, characterized by a support and a photosensitive silver halide emulsion layer applied thereon, those a divalent cyan photographic coupler the general formula contains: A4-0CC0 - Y) _{n or} (A '- 0CC04 or R ₂ R ₂ ' 'm where mean: Y is a monovalent or divalent organic group, η is an integer, Y ^{1 is} a divalent or higher organic group, m is an integer, R .. and R ~ individually each a hydrogen atom or an organic group, with the proviso that at least one of the radicals R, and R_ should be an organic group, or in which R, or R "via the group Y to the carbon atom of the carboxyl group can be bonded to form a ring, with the proviso that in this case R- and R ₂ and Y represent a divalent organic group, R 'and R' individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the re- 709807/1055 fr * ste R ¹ -. and R ^{1 represents} an organic group, and in which R 'or R' ^{can be bonded to the carbon atom of the carbonyl group via the group Y 1} to form a ring, with the proviso that in this case R 'or R' is a divalent organic group and Y ^{1 represent} a trivalent or higher organic group, A and A ¹ each represent a cyan coupler residue derived from a cyan coupler of the general formula: or where mean: R _? a hydrogen atom, a halogen atom, a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon radical, an acylamino group or a group -0- ^R g or -S-Rg (in which R is an aliphatic hydrocarbon radical) and in which if two or more groups R- are present in a molecule, they can be the same or different from each other, _{R 1} and R 1 - individually each represent a substituted or unsubstituted aliphatic hydrocarbon radical, an aryl radical and a heterocyclic radical, or in which R ₁ and R 1. can be linked to one another to form a nitrogen-containing hetero ring, ο an integer from 1 to 4 » 7 09807/1055 ρ is an integer from 1 to 3 and q is an integer from 1 to 5. 11. The silver halide material of claim 10, characterized in that it is a label Inet that in the general formula η and m each mean the number 1 or 2. 12. Color developer for developing exposed photosensitive Lichen color photographic silver halide materials, characterized ge ichnet that he ρ-phenylenediamine and a divalent blue green photographic couplers of the general Formula contains: - Y) or (A ' - OCCO-) Y' , η ι m R ₂ R ₂ ¹ where mean: Y is a monovalent or divalent organic group, η is an integer, Y ^{1 is} a divalent or higher organic group, m is an integer, R ₁ and R "individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the radicals R ₁ and R" should be an organic group, and in which R, or R "via the group Y to the carbon atom of the carbonyl - 709807/1055 group can be bonded to form a ring, with the proviso that in this case R .. or R "and Y a represent divalent organic group, R 'and R'"individually each represent a hydrogen atom or an organic group, with the proviso that at least one of the radicals R 'and R' denotes an organic group, and in which R ¹ or R 'via the group Y ¹ to the carbon atom the carbonyl group can be bonded to form a ring, with the proviso that in this case R 'or R' represent a divalent organic group and Y ^{1 represents} a trivalent or higher organic group, A and A ¹ each represent a cyan coupler residue derived from a cyan coupler of the general formula: .R _Z -COR ₁ - or / \ CON < ^R 5 where mean: R- is a hydrogen atom, a halogen atom, a substituted or unsubstituted, saturated or unsaturated aliphatic hydrocarbon radical, an acylamino group or a group -0-R _fi or -S-Rc (where R, an aliphatic carbon 709807/1055 is hydrogen radical) and in which if two or more groups R "are present in a molecule, they are the same or one of the other can be different R, and R, each individually substituted or unsubstituted aliphatic hydrocarbon radical, an aryl radical and a heterocyclic radical or in which R 1 and R 1 - are linked to one another can be with the formation of a nitrogen-containing hetero ring, ο an integer from 1 to 4, ρ an integer from 1 to 3 and q is an integer from 1 to 5. 13. Color developer according to claim 12, characterized in that g e k e η η, that in the general formula η and m are each the number 1 or 2. 709807/1055