DE2634694C2 - Color photographic recording material and color developer for developing an exposed color photographic recording material - Google Patents

Description

3. Color developer for developing an exposed color photographic recording material which contains p-phenylenediamine and a photographic two-equivalent cyan coupler which has an amld group in the o-position and a cleavable group in the p-position which has an O atom with the coupling agent Group connected IsU characterized in that the two-equivalent blue green coupler corresponds to the formulas I or II and the explanations of claim 1 or 2.

The invention relates to a color photographic recording material having at least one light-sensitive material Silver halide emulsification containing at least one two-equivalent cyan coupler found in o-position has an Amldgruppe and in p-position has a removable group, which via an O atom with the _ coupling group is connected, as well as a color developer for developing an exposed color photographic

Iphl's recording material, the p-phenylenediamine and a photographic two-equivalent cyan coupler of the aforementioned type contains.

From US-PS 34 76 563 and DE-OS 22 14 489 two-equivalent blue-green couplers are already known, in the p-position of an aryloxy group have a removable radical which has an oxygen atom with 2> of the coupling group, which in color photographic recording materials has at least a light-sensitive outer halide layer and in color developers for developing a exposed such color photographic recording material can be used. These known two-equivalent blue-green couplers however, provide color images with today's requirements in color development no longer sufficient color density and stability. 3fl

The object of the invention is to provide a color photographic recording material and a color developer to provide, which contain a two-equivalent cyan coupler, the color images with high color density and high stability ^ "" generated.

This object is achieved with a color photographic recording material according to claim 1 or one Color developer according to claim 3 gelfi ..

The characteristic feature of the Zwci-Äqulvalent blue-green coupler used in the invention is In addition to an amld group arranged in the o-position, the cleavable group arranged in the p-position of the following given general formula (Hl), which is connected to the coupling group via an O atom:

R ₁ O -40

I Il

- O —C —C— (Π1)

wherein Ri and R _{1 have} the meanings given in claim 1.

The Zwcl-Äqulvalcnt blue-green coupler used according to the invention enables a high dye formation rate, without the photosensitive silver halide demulsions of a color photographic To obscure or discolor recording material that contains it or is treated with it. He leaves like that In any layers of the color photographic recording material, for example in the light-sensitive Silver halide emulsion layer of the same, disperses well and can also be used in high concentrations Be settled in these layers. One using this two equivalent cyan coupler The color image produced has excellent resistance to heat and light as well as excellent Absorption properties. It does not inhibit the development of the color image, as it does with conventional s? Two equivalent cyan couplers are often the case. When incorporating that used according to the invention Zwel-Äqulvalent Blue-Green Coupler In a color photographic recording material the thickness of the light-sensitive Silver halide demulsions can be reduced significantly, so that after developing a color image with a high resolution and a high sharpness is obtained. In addition, in the In the case of a multi-layered drawing, the penetration of light into the underlying layers can be avoided can be improved, thereby increasing the photographic sensitivity.

The color photographic material and the color developer of the invention may be photographic Zwel-Äqulvalent cyan uncoupler of the general formula (1) given in claim 1 or contain one of the general formula (II) given in claim 1 or a mixture thereof.

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

The term "aryl" used here is preferably 5- or 6-member monocyclic or 9- or lOglledige b! cyclic groups to understand which only carbon atoms or in addition to carbon atoms still contain 1 to 4 heteroatoms from the group nitrogen, sulfur and oxygen. Particularly preferred '.st the phenyl group. The aryl groups can be substituted and they preferably have 1 or 2 substituents.

The term "halogen" used here includes fluorine, chlorine, bromine and iodine, preferably chlorine and Bromine, understand.

The term “heterocyclic group” used here includes mono- or polycyclic, optionally condensed 3 to 20-membered, preferably 3 to 8-membered, in particular 4 to ogledged rings understand that contain one or more heteroatoms from the group nitrogen, oxygen and sulfur and may optionally have one or more of the sub-substituents mentioned below.

Particularly favorable results have been obtained using a two-valence Rlava green photographic coupler of the formula (I) or (H) given in claim 1, wherein A is an In o-position by a Amide radical substituted phenol or naphthol group of the general formula means:

or

where mean:

^J5 R) a hydrogen atom, a halogen atom, a substituted or unsubstituted, saturated or unsaturated alkyl radical, an acylamino group or a group -OR ₆ or -SR ₆ , where R _{6 is} an alphatic hydrocarbon! Is, and in which, when two or more groups R _{3 are present} in a molecule, these may be the same or different from one another,

R ₄ and R ₅ each represent a substituted or unsubstituted alkyl radical, aryl radical or heterocyclic radical *> ojcr in which R ₄ and Rj are linked to one another to form a nitrogen-containing heterogeneous length

can,

P is an integer from 1 to 3 and q is an integer from I to S.

The Allphall hydrocarbon radical can be saturated or unsaturated, linear, branched or cyclic.

Preferred examples of suitable Allphall hydrocarbon radicals are alkyl groups, such as methyl, ethyl, Isobutyl, dodecyl, octadecyl, cyclobutyl and cyclohexyl groups, and alkenyl groups such as the allyl group.

Typical examples of suitable aryl radicals? are phenyl and naphthyl groups.

Preferred examples of suitable heterocyclic radicals are pyridyl, chlnolyl, thlenyl, plperazyl and Ό Imldazolyl groups.

In the case of the substituent, the In the aliphatic hydrocarbon radical, the aryl radical or the heterocyclic Rest can be incorporated, it can be, for example, a halogen atom, an Nltrogruppe, a hydroxyl group, a carboxyl group, an amino group, a substituted amino group, a sulfo group or a substituted or unsubstituted alkyl, alkenyl, aryl, heterocyclic. Alkoxy, aryloxy, Arylthlo-, arylazo-, acylamino-, carbamoyl-, ester-, acyl-, acyloxy-, sulfonamldo-, sulfamcyl-, sulfonyl-, Morphollno, plperazyl or imldazolyl group.

The hetero ring formed by R ₄ and R «is preferably a nitrogen-containing hetero ring which can be selected from the above-mentioned heterocyclic groups.

The aliphatic hydrocarbon radicals in the formulas

R ₁ O

A — O — C — C —Y and

R ₁ O

A-O-C

(D

can be saturated or unsaturated, linear, branched or cyclic.

Typical examples of suitable monovalent illphallic hydrocarbon radicals are alkyl and alkynyl groups, preferably methyl, ethyl, isobulyl, oclyl, tert-octyl, ocladecyl, cyclobutyl, cyclohexyl and 2-norbornyl groups.

Typical examples of suitable divalent alphutl.schc hydrocarbon radicals are alkylene groups. preferably Methylene, ethylene, butylene and oxylene groups.

Typical examples of suitable aromatic hydrocarbon radicals are aryl and aryl groups, preferably Phenyl, naphthyl, phenylene and naphthyl groups.

Preferred examples of heterocyclic groups include S and 6-membered heterocyclic groups containing a Heteroatom, e.g. B. nitrogen, oxygen or sulfur contain. Examples of suitable monovalent heterocycle see radicals are thlenyl, pyridyl, chlnolyl and oxadlazoly groups, and examples of suitable divalent groups heterocyclic radicals are pyrldinylene and chlorolylene groups.

Preferred acyl groups are acetyl, benzoyl and naphthoyl groups and preferred thloacyl groups are Thioacetyl, thlobenzoyl and thonaphthoyl groups.

Preferred examples of suitable sulfonyl groups are phenylsulfonyl, chlorosulfonyl and methanesulfonyl groups.

The groups represented by Y and Y 'in the above formulas (I) and (II) may be substituted and the substituents can be as described above with regard to the Formulas (IV) and (V) are given.

Typical examples of the separable group, which as a bridging group is an essential group contains, as indicated by the general formula

R ₁ O
- O —C —C— (HD

are the following:

-OCHCOC ₂ H ₅
CH,

-OCHCONHC ₂ H ₅
CH ₃

—OCHCONH

CH ₃

-OChCOOC ₂ H ₅
CH ₃

60 65

CH ₃
--OCCONH

CH ₃
-OCHCOOC ₂ H ₅

COOC ₂ H ₅

-OCHCOOC ₁₂ H ₂₅ COOC ₁₂ H ₂₅

-OCHCOOC ₂ H,

COO
—OCHCONH

CONH
-OCHCONHC ₂ H ₅

CONH-

- OCHCOOC ₄ H ^ n) J
CH ₂ COOC ₄ H ^ n)

CH ₃ -OCHCOO

CH ₂ COO

CH ₃

-OCHCONHCjH ₅ CHjCONHC ₂ Hj

-OCHCONHC ₁₂ H ₂ J CHjCONHCuHj ₅

—OCHCONH

CH ₂ CONHCjH ₅

-CH ₁

SO ₃ Na

SSE

SO ₃ Na

CH ₂ COOC ₄ H ^ n) -OCCOOC ₄ IUn) CHjCOOC ₄ H, (n)

- OClCONH - <Γ \ - NHCOCHO-

CHjCOOC ₂ Hs CHjCOOCjH ₅

0;

- Ο —CH

-O- ^ H

CO

X)

Vn-C ₂ H ₅

-O- <St.

^ o

- 0 —CH-CO

CH ₂ -SO ₂

/ COCH _2x -OCH <> CHO-

111

30 35 40

50

55

60

65

Couplers who have a removable group, e.g. B. a », such as mentioned above, In the active position of the cyan coupler, as represented by the general formula IV or V, are according to the invention preferably used. The reason why the coupler of the present invention does the above possesses excellent photographic properties. Probably the fact that it is a specific bridging one (Linking) group, as mentioned above, has. Some examples of the founding type couplers are given below.

CONH (CH ₂ ) ₄ O

OCHCOOC ₂ H ₅ CH ₃

IC ₅ H ₁₁

OH

CONH (CHj) ₄ O ^ f V-IC ₅ H ₁₁

IC ₅ H ₁₁

OCHCONHC ₂ H ₅ CH ₃

OH

CONH (CH ₂ J ₄ O- <f> -tC ₅ H "

CH ₂ COOC ₂ H ₅

IC ₅ H ₁ ,

OCHCONH

OCHCONH
CH ₂ COOC ₂ H ₅

CONH (CH ₂ J ₄ O

CONHC ₁₂ H ₂ ,

IC ₅ H ₁ ,

IC ₅ H ₁₁

(5)

(6)

(7)

(8th)

(9)

OH

CONH (CH ₂ ) ₄ O

OCHCONH

CH ₂ CONHC ₂ H

SO ₃ Na

OH

CONH (CH ₂ J ₁ - / ~~ S-NHCOCHain)

CH ₃ Ο - C - CH ₃

OH

CON

OCHCOOC ₂ H ₅

CN

C ₂ H ₅

/ COOH

COOH

OH

CON (CH ₂ ) 2SO ₃ K

OCHCOOC ₂ H ₅ COOC ₂ H ₅

IC ₅ H ₁₁

IC ₁ H ₁₁ -Z ^ S-OCHCONH C ₂ H ₅

NHCOCFjCF ₂ H

OCHCOOCH ₂ -C ₂ H ₅

(10)

(11)

CONH (CH ₂ ) «O- <f S-IC ₅ H ₁₁

IC ₅ H ₁₁

CH ₃

(12)

C ₁ H

(13)

CON

OCHCOOC ₁₂ H ₂₅ Oi) COOC ₁₂ H ₂ JOi)

OH

CONH-

COOH

COOH

-HNOC

OCHCOOCiH ₅

CH,

OCHCOOC ₂ H ₅ CH ₃

The compounds according to the invention given above can be prepared by the following processes will:

For example, a naphthol-type coupler can be found in the Journal of the American Chemical Society ", 64, 798 (1942), can be synthesized. In particular, 1,4-dihydroxy-2-naphthoic acid is used with a carbonyl compound which has a Halcrene atom or another substituent in one corresponding a-chloro-ar-alkyl acetate, ar-bromo-ar-alkylacetylamine or ar-bromo-a-alkoxycarbonylmethyl acetate contains. In a solvent such as acetone, dimethylformamide or the like, In the presence of Pyrldln, sodium carbonate, Sodium hydroxide od. The like. Reacted at room temperature or elevated temperature and the thereby obtained naphthoic acid, e.g. B. l-hydroxy-4- (l-ethoxycarbonylethoxy) -2-naphthoic acid, l-hydroxy-4- (läthy! Amlnocarbonylathoxy) -2-naphthoäure, l-Hydroxy-4- (diethylsucclnyloxy) -2-naphthoic acid or the like Using a conventional procedure, In the corresponding phenyl ester or In the corresponding Converted to acid chloride. Then the phenyl ester or the acid chloride is heated or in one Solvent, such as benzene, in the presence of Pyrldln, sodium carbonate or the like. At room temperature or elevated temperature reacted directly with a suitable amine. Aui these catfish can be the desired one Coupler can be obtained. In addition, the desired coupler can be prepared by reacting any one of them free acid with a corresponding amine at room temperature in the presence of Dlcyclohexylcarbodllmld.

A phenol type coupler is as described above from a 1,4-dihydroxybenzene derivative can be synthesized. If desired, the desired coupler or its derivative can be prepared by blocking one of the hydroxyl groups of the, 4-hydroxybenzene derivative used as the starting material with, for example, an Acctylgruppe, a Benzoylgruppc od. The like. By acylation to form a corresponding carbonyl methoxy derivatives and hydrolyzing them with an acid such as hydrochloric acid, Sulfuric acid or the like, or an alkali such as sodium hydroxide, potassium hydroxide or the like If acylation is not suitable, one of the hydroxyl groups becomes an oxyloxy group, it becomes the

IO

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 invention

Coupler described in more detail.

5 Synthesis example 1

0.05 mol of 1-hydroxy-2-naphthoic acid was dissolved in 70 ml of DMF and added to the resulting solution 10 ml of a 40 μl aqueous sodium hydroxide solution were added dropwise while introducing nitrogen gas. Then 0.05 mol of ethyl cr-bromopropionate was added dropwise and the mixture was for 3 to 4 hours at Stirred 40 ° C to cause the reaction. After the completion of the reaction, the reaction mixture was in Poured ice / hydrochloric acid, and the crystals formed were separated by filtration and taken out Recrystallized acetonitrile to give a compound having a melting point of 178 ° C. then 0.01 mol of the l-hydroxy-4-U- (ethoxycarinnyl) ethoxy] -2-naphthoic acid thus obtained and 0.01 mol of N- ( <5-2,4-Dl-tert-amylphenoxy) butylamine dissolved in 60 ml of dry Dloxan and 0.01 mol Dicyclohexylcarbodiamld added. The reaction was carried out at room temperature for 2 hours with stirring carried out. After the completion of the reaction, the reaction mixture was filtered and the filtrate was taken under concentrated under reduced pressure and separated by column chromatography, whereby one compound with a melting point of 75 "C (yield 52 *). Elemental analysis confirmed that it was Compound was the compound (1) given above.

Synthesis example 2

0.05 mol of 1,4-Dlhydroxy-2-naphthoic acid were dissolved in 70 ml of DMF and 10 ml of a 40% aqueous sodium hydroxide solution were added dropwise to the solution thus obtained while introducing nitrogen gas. 0.05 mol of c-bromoproplonylethylamine, dissolved in 15 ml of DMF, were then 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 ° C. Then 0.01 mol of the l-hydroxy-4- [l- (äthylamlnocarbonyl) ethoxy] -2-naphthoic acid thus obtained were dissolved in 60 ml of dry Dloxane and 0.0! Moles of dicyclohexylcarbodiment added. The reaction was carried out at 50 to 60 ° C. for 30 minutes without 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 give a connects a dung with a melting point of 95 ° C (yield 65 *). Elemental analysis confirmed that the compound was compound (2) given above.

Synthesis example 3

0.05 mol! ^ - Dihydroxy ^ -naphthoic acid was dissolved in 70 ml of DMF and added to the resulting solution 10 ml of a 40 'algae aqueous sodium hydroxide solution were added dropwise while introducing nitrogen gas. Then 0.05 mol of diethyl a-bromosuccinate, dissolved in 15 ml of DMF, was added dropwise and the reaction was 3 to Carried out for 4 hours with stirring at 50 ° C. After the completion of the reaction, the reaction mixture became poured into EL / hydrochloric acid, and the precipitated crystals were separated by filtration and recrystallized from acetonitrile to give a compound with a melting point of 176 ° C received. Then, 0.01 mol of the compound thus obtained and 0.01 mol of n-dodecylbutylamine were added to 60 ml of dry Dloxan was dissolved and 0.01 mol of Dlcydohexylcarbodllmid 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 flow rate was concentrated under reduced pressure and separated by column chromatography to give a compound with a melting point of 68 ° C was obtained (yield 35%). Elemental analysis and the like confirmed that the compound thus obtained was compound (4) given above.

Synthesis example 4

l-Hydroxy-4- [l- (4-nltro-anlllnocarbonyl) -2-äthylamlnocarbonyläthoxy] -N- [o- (3-n-dodecyloxynhenoxy) butyl] -2-naphihamld, prepared by the same process as in the synthesis mist plates above was reduced by a conventional method with zinc and hydrochloric acid. The amniotic compound obtained was dlazotized and in the alkaline state with disodium-2-hydroxy- & ö 3,6-disulfonate coupled, whereby a compound with a melting point of above 300 ° C was obtained (Yield 60%). Elemental analysis and the like confirmed that this compound is the one given above Compound (5) acted.

Various couplers can be prepared by the above synthesis method. the Elemental analysis results of the above-described couplers are along with those of <> 5 Couplers made by the procedure described above are shown in the table below summarized.

Elemental analysis (%) H 26 34 694 values N Values of calculated values 8.35 H 2.22 Coupler C. 8.53 found 8.67 4.72 No. 73.06 7.65 N C. 8.45 4.49 1 73.18 8.34 2.37 72.93 7.51 2.67 2 71.51 5.63 4.74 73.24 8.49 6.29 3 68.48 7.86 4.17 71.81 5.76 6.42 4th 58.55 7.45 2.58 68.36 7.43 3.96 5 74.19 4.89 6.21 58.29 7.75 2.15 6th 69.02 6.75 6.18 74.09 4.72 3.92 7th 49.33 8.26 3.83 68.92 6.48 2.71 8th 64.33 5.79 2.62 49.18 8.41 9.6i ' 9 75.36 8, .Ό 3.75 64.53 5.53 1.37 10 66.19 5.35 2.44 75.65 8.49 4.30 H 69.12 9.65 66.08 5.62 12th 67.05 1.68 68.76 ! 3 4.12 67.24

Ή The couplers according to the invention produced by the process described above have a much higher dye formation rate in the color development stage than the conventional 4-value couplers and 2-value couplers which contain an aryloxy group as a removable group, e.g. B. a phenoxy or Nltrophenoxygruppe, or a group attached via an ester, such as. B. an acetoxy or benzoyloxy group contain. In addition, are compared with the conventional couplers with a similar structure

M the couplers according to the invention in photographic protective cones, such as gelatin, more easily dispersible. The oil-soluble couplers of the present invention have excellent solubility in coupler solvents. The couplers of the present invention which have a hydrophilic group are excellent in utility in fishermen's dispersions. The couplers of the present invention which are not incorporated into the photosensitive recording material can very easily be added to a color developer or the like. Because of these advantageous properties, when the couplers of the present invention are incorporated into the photosensitive layers of photographically sensitive painters, the thickness of the photosensitive layer can be substantially reduced and the sharpness and other properties of the resulting color image can be greatly improved. Furthermore, the coupler erflndungsgemäßen exert no adverse effect on dc color development and are particularly characterized by the fact that they do not cause discoloration or no other defects as a result of your good responsiveness. A dye formed using the coupler of the present invention has excellent absorption properties, as mentioned above.

The coupler of the present invention can be used in various ways by appropriately selecting the combination of the basic structure and the removable group. For example, if a blue-green coupler remains a water-soluble group, such as B. a sulfonic acid or carboxylic acid group, the coupler is dlffuslonsfählg and when the leaving group itself is diffusible, the coupler can be used as a diffusible coupler for photographic processes in which it is contained in a liquid color developer. An example of such a coupler is the above-mentioned coupler (8).
In addition, the coupler of the present invention comprising a diffusible cyan coupler residue and a

5Ii non-dlffuslonsable removable group, e.g. B. a long-chain aliphatic hydrocarbon radical, e.g. B. an ocladecyl group. contains, can also be contained in color rollers if the non-Dlffuslonsfählgkelt The detachable group is mediocre and the overall structure in which the cyan coupler remainder is active Position bound to the detachable group. Is, is diffusible. Except for the above coupler (8) As such couplers, couplers (11) and (13) given above can also preferably be used.

A typical composition of a color developer is as follows:

Color developer blend 1 to 5 g

anhydrous sodium sulfite I to 2 g

anhydrous sodium carbonate 10 to 60 g

«Ι Potassium bromide 0.5 to 1.5 g

Coupler 1 to 3 g

Water ad I I

The couplers according to the invention, in particular the above-mentioned couplers, have better solubility <> s than conventional couplers and have the excellent properties mentioned above.

A coupler, or a diffusible cyan coupler residue and a diffusible cleavable group has, but as a whole is non-diffuslonsRthlg, a coupler that has a non-diffuslonsföhigen cyan coupler residue and line has diffusible, cleavable groups and, as a whole, is non-diffusible,

as well as a coupler, which creates a non-dull blue-green coupler and a dlffuslonsense can be split off Has group and is illusion-filled as a whole, are useful for the photographic diffusion transfer process used. In order to make these groups diffusible, methods of Selection of groups with a low molecular weight and / or the formation of water-soluble ones Groups as mentioned above e.g. B. a Sulfonsüurcgruppe can be used. In order to avoid these groups To make it possible to use methods for guiding a long-term aliphatic hydrocarbon slcs and / or the selection of a group with a relatively high molecular weight will.

Also a coupler with a dlffuslonsfählgcn blue-green coupler residue and a dlffuslonsfahlgen abspalibarcii Group can be used for the diffusion transfer method, if that for the creation of a Image In the color development stage, the color development is not necessary. In particular when a hydrochloride residue, a resorcinol residue or the like in the dlffuslonsfahlgen blue-green coupler residue or the group which can be eliminated can be introduced directly or via a suitable bridging group obtained couplers can be used with success for the diffusion transfer process. This procedure can can be applied to couplers in which the diffusion possibilities of the cyan coupler residue and of the leaving group are different from those mentioned above. When the Dlffuslons transmission method is applied, an image is generated either by a process in which a through the reaction cyan dye formed between the cyan coupler body and the color developer for image formation is used, or by a process in which the isolated during color development is cleavable Group is used for image generation. In the former method, the obtained blue-green dye should be diffusible and in the latter process one should be by isolation of the group which can be split off from the active position can be dlffuslonsfahlg. If those If the isolated compound is used, the compound should also be colored. For example, the Compound a coloring radical, e.g. B. an azo dye. Detachable groups of this type can can be represented, for example, by the general formulas VI and VII given below:

R ₁

- OCCO-D (VI)

R ₂
and

R,

- OCCO— (VD)

D '

where D and D 'each represent a dye residue.

In the general formulas VI and VII given above, the dye residues are preferably water-soluble and preferred examples are monovalent residues of azo dyes, azomethine dyes, indo-anil dyes, Indophenol dyes and anthraquinone dyes ^

Examples of couplers which are suitable for the oil transfer process are e.g. B. those given above Coupler (5) and (12).

The couplers of the present invention can be used with success in any type of fluid transfer process be applied. In general, the coupler of the present invention becomes a photosensitive one In this case, a photosensitive layer is preferably used as the photosensitive layer SllberhalogenldmatTlal 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 mol per mol of silver halide.

As a rule, a coupler is used which In a photosensitive material, particularly a photosensitive SiberhalogenldmaterlaJ, is incorporated. A non-dlffuslonsian coupler is preferred used to prevent other layers from being adversely affected by the coupler. Under the above-mentioned couplers which can be used for the oil transfer process those that are not capable of diffusion can be used with success. Coupler with a non-dlffuslon capable Coupler residues are particularly preferred. In this case, the group which can be split off can either be split off or be non-diffusible.

As the coupler of this type, couplers (1), (2), (3), (4), (5), (6), (7), (9) and (10) are preferably used.

Some of these couplers are practically colorless and they react with an oxidation product to form the Color developer formed during color development is a dye. Other couplers of this type are so called colored couplers and they can be used for color correction after the masking process be used. The coupler (5) is preferably used as a coupler of this type. In the masking process the color of the colored coupler disappears upon color development or the colored coupler disappears is removed from the system of the photosensitive material and at the same time is by reaction with a cyan dye formed in the color developer. In this way the color of the colored coupler becomes used for color correction (color adjustment). In general, this colored coupler is used in combination

used with a practically colorless coupler.

The couplers contained in the recording material are divided into two groups: one, which contains a hyJrophilic group in the molecule, and another which contains an oleophilic group in the molecule contains. If these couplers are used, for example, in coating compositions for the production of photosensitive Layers are incorporated, the first-mentioned coupler group, nilmilch the so-called coupler vom Flscher-Dlsperslons-Typ, In the form of a solution or dispersion Incorporated and in an alkaline solution , * - € last mentioned group of couplers is worked in the form of a solution in a coupler solvent. A typical example of a coupler according to the invention belonging to the first-mentioned group is heard, is the coupler given above (7) and if the above-described dispersing process is

When applied, these inventive couplers have much better resolution properties than the conventional couplers and they offer various advantages. For example, a dye image having a higher concentration (density) can be obtained, the transparency of the layer can be greatly improved, and the resolving power can be considerably improved.
In general, the coupler of the present invention is incorporated into the light-sensitive material in an amount of from about 0.07 to about 0.7, preferably from 0.1 to 0.4 mol per mol of silver halide. When the coupler is used for adjusting (correcting) color or improving the properties of other couplers, the coupler of the present invention is used in an amount of from about 0.01 to about 0.1, preferably from about 0.03 to about 0.07 mol per mol Silver halide vcrA-end !.

The coupler of the present invention can be used in combination with any of their 2-valent or 4-valent couplers

be used. For example, the coupler according to the invention can be used in combination with a 2-value Couplers, e.g. B. a so-called colored coupler (e.g. a coupler in which one has an azo group bonded as a bridging group-containing removable group to the active position of the coupler Ist) or a so-called DIR coupler (a coupler that acts as a developer during color development releases, e.g. B. a coupler in which a leaving group containing a Thlogruppe to the active position of the coupler is bound), can be used.

example 1

A coupler as shown in Table 1 below was used, and 10 g of the coupler - ^w were added to a liquid mixture of 20 ml of di-butyl phthalate and 60 ml of ethyl acetate and the

The temperature was raised to 60 ° C to completely dissolve the coupler. The resulting solution was

with 5 ml of a 10% lgcn aqueous solution of alkylnaphthalene sulfonate and 200 ml of a 5% lgcn gelatin solution mixed and the mixture was eluted using a colloid mill with a coupling agent

was received,
The dispersion produced in this way was then converted into 500 g of a highly sensitive Sllberjodldbromld-Negatlv-Gelai! F! Eemu! S! Of! irnit 6.0 Mo! - * SUberjod'd) was added and the mixture was in the form of a layer on a

Cellulose acetate film base applied and dried.
The sample produced in this way was exposed through an optical step cell (gray cell) and for 10 minutes

developed at 20 "C with a liquid color developer of the following composition:

N-Ethyl-N-Zf-rnethansulfonamldoathyl ^ -rnethyM-arnlnoanllinsulfat 5.0 g

anhydrous sodium sulfite 2.0 g

Sodium carbonate monohydrate 50.0 g Potassium bromide 1.0 g

• 15 sodium hydroxide 0.55 g

Benzyl alcohol 4.0 ml Water ad I I

The sample was then subjected to a stop and fix treatment using a conventional procedure, Washed for 10 minutes with water and for 5 minutes at 20 ° C with a Blelch solution of the following specified composition bleached:

Kallumferricyanld 100 g Potassium bromide 50 g

Water ad 1 I.

The sample was then washed with water for 5 minutes and with a for 5 minutes at 20 ° C Fixing solution of the composition given below fixes:

w> Sodium thlosulfate heptahydral 250 g

Water ad 11

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

The photographic properties of the sample thus treated were measured, whereby the In the following Results given in Table 1 were obtained.

Table I. used
Coupler relative
Sensation
opportunity 26th 34 694 wavelength
of the absorption
tiunmaxi-
mums (To,; ,,) image
Lichi-
echiness resistance
against
humidity Sample no. Coupler (1)
Coupler (4)
Comparison
coupler (1) 131
140
100 Gamma (y) maximum
Density (D _n ,,,) 700 nm
700 nm
700 nm 91%
92%
90% 74%
76%
68% 1
2
3 1.17
1.20
1.00 2.22
2.33
1.95

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 (!) Had the structure given below. The light fastness is expressed by the ratio (%) between the residual density after exposure to light exposure in a Xenon-Fade-O-Meier and the density before exposure. UIe resistance to moisture is expressed as the ratio (%) between the residual density after storage for 2 weeks at a relative humidity of 80% and a temperature of 50 "C and the density before storage.

The comparative coupler (1) described in US Pat. No. 2,474,293 has the following structure:

IC ₅ H ₁ ,

CONH-

CH

As can be seen from the results in Table 1 above, the coupler of the present invention is excellent photographic properties (high sensitivity, excellent lightfastness and excellent resistance to moisture) on and using the invention Coupler produced sample gives a color image with a high degree of focus.

When coupler (2) was used in place of couplers (1) and (4), it was found to be excellent exhibited photographic properties similar to those of the couplers (Π and (4)).

Example 2

10 g of the coupler (10) were added to a liquid mixture of 20 ml of di-butyl phthalate and 60 ml of ethyl acetate was added and the temperature was raised to 60 ° C to completely dissolve the coupler. The one with it The solution obtained was with 5 ml of a 10% lgen aqueous solution of alkylnaphthalenesulfonate and 200 ml of a 5% gelatin aqueous solution was mixed and the mixture was made using a colloid mill emulsified, whereby a coupling agent was obtained.

The dispersion thus prepared was added to 500 g of a red-peeled silver iodine bromide demulslon (with 4.0 mol % silver iodine) having a high sensitivity, and the mixture was applied in the form of a layer on a celuose acetate film support and dried, whereby a photographic repellant-sensitive material with a permanent coating was obtained.

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

Methol

anhydrous sodium sulfite

Hydroquinone

anhydrous sodium carbonate

Potassium bromide Kalumthlocyanat

water

2.0 g ad 1 I.

30 J5 40 45

50

55

The sample was then stopped, cured, and washed with water using standard procedures and then it was subjected to secondary exposure to white light. Then sample became 13 For minutes at 2 ° C with a liquid color developer of the composition given below color developed:

15th

N.N-Diphenyl-2-methyl-p-phenylenedlamine 3.0 g

anhydrous sodium sulphide 4.0 g

Sodium carbonate monohydral 20.0 g Potassium bromide 2.0 g

Water ad 1 1

The sample was then stopped using conventional methods, washed with water, bleached and fixed and 20 min. long washed in running water and dried, using a posl tlves blue-green dye image with excellent transparency and an absorption maximum ίο received 700 nm.

From the foregoing it can be seen that the coupler of the present invention when used for a reversal photosensitive material exhibited excellent photographic properties.

Example 3

In a liquid mixture of 20 ml Trlcresylphosphai and 60 ml ethyl acetate were 20 g of a coupler, as indicated in Table II below, dissolved and processed in the same way as in Example 1 A coupler dispersion is produced from the solution. The coupler spersloii was 100 ml of a highly sensitive Sl! Bc? Iodldbromldemulslon was added and the mixture was in the form of a layer on a film support μ applied and dried to obtain a photosensitive material.

The light-sensitive material was exposed to light using conventional procedures and for 3 minutes and 15 minutes Seconds at 38 ° C with a liquid color developer of the composition given below developed:

N-Ethyl-N ^ / f-hydroxyäthyDO-methyM-amlnoanlllnhydrochlorld 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 I.

The sample was then treated for 6 minutes at 38 ° C. with a Blelch solution of the composition given below bleached:

■> 5 Dlnairlumäthylendlamlntetraacetat 40.0 g

ElsenUIDchlorld 30.0 g Sodium carbonate monohydrate 20.0 g Potassium bromide 30.0 g

Water ad 1 1

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

In the following table, the relative sensitivity is based on the sensitivity of the sample prepared using the comparative coupler (2) given below, the value of which was set at 100.
The comparative coupler used (2). which is described in US-PS 30 34 892, had the following structure:

■ "IC ₅ H ₁ ,

CONH (CH ₂ J ₄ - 0 - <f
/ Ν / Χ /

COCH ₃

Table II Sample No. used relative maximum wavelength wavelength Coupler Sensitive- Density (D _max ) des Abscrp- des Absorpti-

wedge maximum maximum

mums (Anui) of the brand

4 couplers (5) 138 1.8 700 520

5 comparative 100 1.6 700 500

coupler (2)

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

As can be seen from this example, the coupler of the present invention can be used for the so-called masking method be applied. From the results given in the table above, it can be seen that the Coupler in this case also exhibited excellent photographic properties and that of the present invention Coupler was much better than the conventional one in terms of sensitivity and density Coupler and an excellent dye image with an improved sharpness gave.

Example 4

According to the Flscher-Dlspergler process, the coupler (7) was converted into a highly sensitive silver iodine bromide negative emulsion incorporated (the amount of the coupler used was 0.2 mol per mol of silver halide) and the emulsion was coated on a cellulose triacetate film support in the usual manner and dried. The sample obtained in this way was exposed to light and for 3 minutes at 24 ° C. with an alkaline treated liquid developer of the following composition:

Sodium sulfite 2.0 g

4-N-ethyl-N- / 3-hydroxyäthylamlnoanllln 11.0 g

Water ad I I

During the above development, the photosensitive layer of the sample was applied to an image receiving layer an image-receiving material placed which, in the image-receiving layer, is methyl - ^ - hydroxyathyl-y-stearo-amdopropylammonium hydrogen phosphate and after the development, the image receiving material was peeled off from the light-sensitive material. A sharp blue-green appeared on the image receiving material Negative image formed with excellent photographic properties. This confirmed that the The coupler of the present invention is also an excellent coupler for use in diffusion transfer color photography represents.

Example 5

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

N.N-Dläthyl ^ -methyl-p-phenylenedlamine 2.0 g

anhydrous sodium sulfite 2.0 g

Sodium carbonate monohydrate 20.0 g Potassium bromide I ₁ Og 5ü

Coupler (8) 2.0 g

Water ad I I

One by applying a highly sensitive Silberjodldbromldemulslon in the form of a layer on a A sample made of polyethylene terephthalate film provided with an adhesive layer (substrate layer) was tested and developed for 3 minutes at 24 ° C with the above-mentioned external type liquid color developer. The developed sample was washed with water for 4 minutes using standard procedures, Bleached for S minutes, washed with water for S minutes, fixed for S minutes, with for 30 minutes Water washed and dried. A blue-green dye picture with an absorption maximum was obtained at 700 nm and a high spectral characteristic, which is also excellent for other photographlse « Features.

When the above-described procedures were repeated on the same catfish using the coupler (11) instead of the coupler (8) given above, an excellent dye image with an absorption maximum at 700 nm was obtained in a corresponding catfish. As a result, it was confirmed that the coupler of the present invention is excellent in color developers. *>

Example 6 Dispersion A

In a solvent mixture of 22 ml of Trlcresylphosphal and 6.0 ml of ethyl acetate, 0.1 IS g of des Coupler (5) and 2.0 g of the known coupler I-hydroxy-N-li- (2,4-dl-t-amylphenoxy) butyI] -2-naphthamId dissolved and a coupler dispersion was prepared from this solution on the catfish indicated in Example I.

Dispersion B

In addition, 0.20 g of the known DIR compound 2- {1-phenyl-5-tetrazolylthlo) -4- [2- (2 _: 4-dlt-amylphenoxy) aciamldo] indanone were added to dispersion A.

Dispersion C

In the same manner as indicated above with reference to dispersion B, this dispersion was made prepared using 0.1 g of the known DIR coupler l-hydroxy-4- (l-phenyl-5-tetrazolylthlo) -2- (2-tetradecyloxyphenyl) -naththalide instead of the DIR connection given above.

₂₀ dispersion D

In the same manner as mentioned above with reference to Dispersion B, it became Dispersion prepared using the known comparative coupler (2) instead of the one according to the invention Coupler (S).

Each dispersion was added to 100 ml of a red-sensitive silver iodine bromide emulsion (with 7.0 mol% silver iodide) was added at a high sensitivity and the mixture was in the form of a layer on a Film base applied and dried. In this way, 4 photosensitive materials were obtained.

These photosensitive materials were exposed to light in a conventional manner and then to that given in Example 3 Catfish treated. Photosensitive material B was materials A, C and D with respect to

yy superior gradation in the dye image obtained. In addition, the dye image obtained using Photosensitive Material B was excellent in graininess and sharpness. The results obtained are given in Table III below.

Table III

.15

light-haze relative gamma

sensitive sensation

Materiality

⁴⁰ A 0.22 100 1.00

B 0.11 97 0.72

C 0.13 92 0.71

D 0.14 95 0.72

Graininess Sharpness (RMS) (U 0.5) 53 50 40 40 43 42 45 43

The RMS value is a value obtained by multiplying the standard abj | j

softening of the change in the density value obtained when scanning a round millimeter |]

tometers with a scanning diameter of 25 μ, with a factor of 1000. The U 0.5 -. Vert is $

by a spatial frequency value at which the MT factor is reduced to 50'Λ. ■ Wi

Example 7 (comparative item) $

This example shows that the photographic cyan couplers used in accordance with the invention US-PS 33 76 563 and the German Offenlegungsschrlft 22 14 489 known blue-green couplers technically superior are. ι

Samples of light-sensitive, color, photographic, halogenated materials were taken after the In

Example 1 prepared procedure. In which the In the welter below table specified: .j Cyan couplers were used. The samples produced in this way were individually exposed and imagewise

then develop using the solutions given below [\

Treatment stage (38 ° C) Rehabilitation duucr i · ' ¹ Color developing 3 min. 15 sec. Bleaching 6 min. 30 sec. Washing with water 3 min. 15 sec.

18th

continuation

Treatment run (38 ° C) Duration of treatment

Fixation Wash with water Stabilize

6 min. 30 sec. 3 min. 15 sec. I min. 30 sec.

The treatment solutions used in each of the above treatment columns had the following specified compositions:

Color developer ad 4.75 g 4-Amino-3-methyl-N-ethyl-N - (/} - hydroxyatliyl) aniline sulfate 4.25 g anhydrous sodium sulfite 2.0 g Hydroxylamine sulfate 37.5 g anhydrous potassium carbonate 1.3 g Sodium bromide 2.5 g Trlnalrrjm salt of nitrilotriacetic acid (monohydrate) '-, og KaüüffihyuröXiu ad Γ Γ water adjusted to pH 10.0 with potassium hydroxide Bleach solution 100 g Elsenammonium ethylcndium inlraacclate 10.0 g Dlammonium Ethylenediamine Clraacetul ad ί 50.0 g Ammonium bromide 10.0 ml Glacial acetic acid 1 I. water pH adjusted to 6.0 with ammonia water Fixing solution 162 ml Ammonium sulfate (50% water solution) ad 12.4 u Nalrlumsulfli anhydrous I \ water pH adjusted to 6.5 with acetic acid Stabilization solution 5.0 ml Formalin (37% aqueous solution) Solution of 5 g of polyoxyethylene-dl-tcrt-butylphenolälhcr 7.5 ml and 10 g of Ethylcnglykol in I I water I I water

The exposed samples were developed individually under the conditions specified above, and those were developed
The resulting color images were individually examined sensitometrically using the method given in Example I, the photographic properties given in Table IV below
became. In the following Table IV, the sensitivity is expressed by a relative value based on
the value 100, at which the sensitivity of the coupling coupler (I) of Example 1 was set.

Table IV : used coupler relative
Sensation
lich wedge gamma
(Y) maximum
density waves
length of
Absorption
lionsmaxi- image
Lightfast
Ness Moisture
resistance sample
No. mums according to the invention used
Coupler (I) 125 1.12 2.50 700 94 77 I. according to the invention, used
Coupler (4) 132 1.17 2.66 700 93 75 2 Coupler (3) according to
U.S. Patent 3,476,563 66 0.82 1.74 700 79 68 3 Coupler (5) according to
U.S. Patent 3,476,563 70 0.85 1.81 700 82 71 4th Coupler (6) according to
DT-OS 22 14 480 103 1.07 2.40 700 90 73 5

continuation

Sample of coupler used relative gamma maximum waves image Moisture No. Sensation (y) density length of Lightfast resistance opportunity (Dm") Absorption Ness maximization mums (At")

Coupler (18) according to 107 1.08 2.46 700 91 72

DT-OS 22! 4 489

Comparison coupler (1) 100 0.90 2.23 700 82 74

(U.S. Patent 2,474,293) des
according to the invention Example (1)

The values in the table above show that the cyan couplers used according to the invention with regard to their sensitizing and stabilizing effect, the US Pat. No. 3,476,563 and 2,474,293 as well as blue-green couplings known from German Offenlegungsschrift 22 14 489 are clearly superior, this applies in particular to the relative sensitivity, the gammu value and the lightness and moisture resistance.

2 (1

Claims (2)

Patent claims: Y is an optionally substituted monovalent heterocyclic. Represents alkyl, aryl, alkylamine, anlllno, alkoxy, aryloxy or benzyloxy group or together with R ₁ forms a hydrogenated alicyclic or heterocyclic ring, where Ri is hydrogen LsI ₁ Y 'is an optionally substituted divalent heterocyclic, alkylene, arylene, alkylenedloxy, arylendloxy, Alkylenedlamino or arylenediamino lip or a group comprising two or more of the contains the aforementioned groups bonded to one another and which contains an oxygen atom or an imino group can have at their end or in which two adjacent carbon atoms through an oxygen atom, a sulfur atom, an imino group, a sulfonyl group, a carbonyloxy group, a Aminocarbonyl group or a sulfonamino group can be interrupted, Ri is hydrogen or a methyl group, R _{3 is} an optionally substituted nitro, hydroxy, cyano, carboxyl, amino, substituted amino, sulfo, substituted or unsubstituted alkyl, alkenyl, aryl, heterocyclic, alkoxy, aryloxy, arylthlo, Arylazo, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamldo, sulfamoyl, sulfonyl, morphollno, plperazyl or imldazoly group means, A is a phenol or naphthol group, the In o -solution is substituted by an aml radical and in p-position the cleavable group R ₁ O I Il
—O — c — c— mn having. 2. Recording material according to claim 1, characterized in that A is a phenol or naphthol group the formula or ^(l? is. in which mean: R is a hydrogen atom, a halogen atom, a substituted or unsaturated, saturated or unsaturated one Alkylresi. an acylamino group or a group -O-R ,, or -S-R *, where R »is an aliphall- is a shear hydrocarbon residue, and in which, when two or more groups Ri in one molecule are present, they can be the same or different from each other,
Ht and Rs each represent a substituted or unsubstituted alkyl radical, aryl radical or heterocyclic radical, or in which R <and Rs are linked to one another to form a nitrogen-containing hetero length could be, ' ρ is an integer from I to 3 and
q is an integer from 1 to S.