DE2514314A1 - PHOTOGRAPHIC COUPLER AND ITS USE IN A LIGHT-SENSITIVE PHOTOGRAPHIC MATERIAL OR IN A PHOTOGRAPHIC COLOR DEVELOPER FOR THE GENERATION OF PHOTOGRAPHIC COLOR IMAGES - Google Patents

Description

Photographic coupler and its use in a photosensitive photographic material or in a photographic Color developer for the production of phctogiaphitch & 'i

Color images

The invention relates to a new yellow color forming photographic coupler and its use in a photosensitive photographic material or in a photographic Color developer for Εχ-generation of photographic color images.

In the production of photographic color images according to the subtractive color reproduction process, we use ent '-. Acklervcrbir.'. L-ir-; a?' orivvre aromatic alaine compound, iiisbesorxloro sir-e i?, N ~ disubstituted p-phenyl) diamiri compound; c, for d: 'e Rerh ϊ: ι tion

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of the silver halide grains in an exposed photographic emulsion layer is used and that which is formed at the same time Oxidation product of the developing agent couples with the color-forming coupler to form a blue-green, purple or yellow dye image.

The couplers used in the color development process are compounds with a phenolic one Hydroxyl group, an anilineamino group or a reactive group Methylene groups which form dyes by coupling with the oxidation product of the primary aromatic amine developer compound, which absorb light in the visible wavelength range.

The yellow dye images have a specific absorption to blue light in the wavelength range of about 400 up to about 500 m, u on. To the previously known ^ a yellow color forming couplers (hereinafter referred to as yellow color couplers belong to both ß-Ketoacetoacetic acid esters, ß-diketones, N, N-malonic acid diamides and oc-acylacetamides and the like. Among these compounds are those in in US Pat. No. 3,265,506, compounds of the pivaloylacetaniline type described on a large scale as yellow color couplers used in the field of color photography. While this class of couplers has many beneficial properties, they do have also have a number of disadvantages and are by no means entirely satisfactory. For example, these couplers generally exhibit poor coupling reactivity to the dyes that are involved in color development with certain useful color developing agents formed by these couplers, have poor lightfastness and those during color development formed leuco dyes are very stable and it is one

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further oxidation of the leuco dyes to produce the dye required by treatment in a strongly oxidizing bath.

Also those in the German Offenlegungsschrift 1 956 281 and in U.S. Patent 3,770,446, oc-phenoxyiso-butyrylacetanilide-type couplers are not satisfactory. These couplers have the disadvantage that those formed by these couplers Dyes have an absorption maximum in a proportionate way short-wave wavelength range and a broad absorption in a longer-wave wavelength range, which leads to Poor color rendering results in the production of the corresponding ß-ketoesters, which are the starting materials for the coupler is carried out by difficult procedures and that the yields are poor and the like.

It is therefore an object of the present invention to provide a new yellow color coupler indicate that can be used in color photography in a subtractive color process; Object of the invention it is particularly to provide a new yellow color coupler which has high coupling reactivity, see above that the dye formation completes in a color developing solution can be. Another object of the present invention is to provide a novel yellow color coupler which can provide a dye with excellent spectral absorption properties and excellent lightfastness provides and the after a simple Process and can be produced in a high yield. The aim of the invention is also to provide a method for producing of a dye image by developing a silver halide emulsion to be indicated in the presence of the new yellow color coupler. A

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Another object of the invention is to provide a photosensitive color photographic material with a silver halide emulsion containing the new yellow color coupler, and one Specify color developer solution that contains the new yellow color coupler contains. Finally, the aim of the invention is to provide a yellow dye image that is suitable for color reproduction after a Subtractive color method suitable spectral absorption properties and has excellent lightfastness.

These and other objects, features, and advantages of the invention will become apparent from the more detailed description of FIG Invention.

The objects of the invention are achieved with a new yellow color forming coupler (hereinafter referred to as yellow color coupler referred to), which forms the subject of the invention and is characterized by the following general formula

^R l P

I ¹ / ^R 3

X-S-C-C-CH-C-N I

R ₂ 0 Y
where mean:
X is an aliphatic, aromatic or heterocyclic group,

Y is a hydrogen atom or a coupling-off group, d. H. one Group that occurs when coupling with the oxidation product of a primary aromatic amine developing agent released can,

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R 1 and R ₉ , which may be the same or different from one another, individually each represent an aliphatic group or together form a ring and

R 1 and R 1, which can be the same or different from one another, each represent a hydrogen atom, an aliphatic, tnatic or heterocyclic group.

Suitable groups which are represented by X in the general formula I given above include aliphatic groups Groups with 1 to 40 carbon atoms, aromatic groups with 6 to 40 carbon atoms and heterocyclic groups having 3 to 40 carbon atoms.

Suitable examples of Y include groups which can be attached to the coupling via a nitrogen, oxygen or sulfur atom Position of the coupler are bonded ^ and Y can also be a hydrogen mean atom or a halogen atom.

Suitable groups represented by R, and R "v / earth, belong to groups with 1 to 10 carbon atoms each.

For suitable groups, represented by IL and R, include aliphatic groups with 1 to 40 carbon atoms aromatic groups having 6 to 40 carbon atoms and heterocyclic groups having 3 to 40 carbon atoms.

In the case of the ρ represented by JI in the general formula I aliphatic group is in particular an «Ali.yigruppe. The alkyl group can be in the form of a straight (uncrzv-i '.- tcin)

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Chain or in the form of a branched chain or in the form of a Ringes are present and it may preferably contain 1 to 20 carbon atoms. The alkyl group can be represented by one or more Alkoxy groups, ζ. B. methoxy, ethoxy, methoxyethoxy, octoxy groups and like groups, aryl groups, e.g. B. phenyl, tolyl? Naphthyl groups and like groups, heterocyclic groups e.g. B. imidazolyl, furyl, pyridyl groups and similar groups, Aryloxy groups, ζ. B. Phenoxy, ToIyIoxygruppen and the like Groups, ac ^ l groups, e.g. B. acetyl, benzoyl groups and the like Groups, acylamino groupsjZ. B. acetamido, butyramido, Benzamido groups and like groups, hydroxyl groups, halogen atoms, e.g. B. chlorine, bromine atoms and the like., And the like. Substituted be. If X is an aromatic or a heterocyclic group, is it preferably a phenyl? Naphthyl, pyridyl, furyl group and the like., By a or several alkyl groups, e.g. B. methyl, ethyl, tert-butyl, octyl, Octadecyl groups and like groups, alkoxy groups e.g. B. methoxy, ethoxy, methoxyethoxy, octoxy and the like Groups, aryl groups, e.g. B. Phenyl, ToIyI, naphthyl and similar groups, aryloxy groups, ζ. B. phenoxy, tolyloxy groups and like groups, acyl groups, e.g. B. acetyl, benzoyl groups and similar groups, acylamino groups e.g. acetamido, butyramido, benzamido groups and similar groups, hydroxyl groups, Halogen atoms, e.g. B. chlorine, bromine atoms and the like., And the like. Can be substituted.

The coupling-off group represented by Y may, in addition to a hydrogen atom and a halogen atom, e.g. Legs Acyloxy group (especially one alkylacyloxy group with 2 to 20 carbon atoms, an arylacyloxy group with 7 to 30 carbon

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Atoms of matter) as described in US Pat. No. 3,447,928 is a phenoxy group (particularly, a phenoxy group substituted by an electron attractive group) as described in US Pat US Pat. No. 3,408,194, a sulfoxy group (particularly an alkylsulfoxy group having 1 to 20 carbon atoms, an arylsulfoxy group having 6 to 25 carbon atoms), as described in US Pat. No. 3,415,652, a Group with a suIfimide structure as described in US Pat 3,730,722, a thiocyano group as described in U.S. Patent 3,253,924 Group with an imide structure (especially a succinimido group, a phthalimido group, a hydantoin group, an oxazolidinedione group, a derivative thereof) as described in US patent applications Nos. 235 937, 319 806 and 395 873, a sulfur atom-containing group (particularly a mercaptotetrazole group and a derivative thereof, a thiophenol group and a derivative thereof) as described in U.S. Patent 3,227,554 and in British Patent 1,224,555, a group containing an azo group (in particular a phenylazo group and a derivative thereof) as described in U.S. Patent 3,148,062, a group having a triazole structure (particularly a benzotriazole group and a Derivative thereof) as described in U.S. Patent 3,617,291 and U.S. Patent Application No. 454,525 Group with a pyrazole structure, as described in the German Offenlegungsschrift 2 163 811 and the like.

The aliphatic groups represented by R and Ε _Λ are preferably an alkyl group. The alkyl group can be in the form of a straight (unbranched) chain or

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are in the form of a branched chain and can contain 1 to 6 carbon atoms. The alkyl group may be substituted with one or more alkoxy, aryl, aryloxy groups and the like. R ₁ and R ^ can also together form a ring.

The aliphatic groups represented by R1 and R2 it is preferably an alkyl group. The alkyl group can be in the form of a straight (unbranched) chain, in the form of branched chain or in the form of a ring and it may contain 1 to 20 carbon atoms. The alkyl group can by one or more alkoxy, aryl, aryloxy groups and Like. Be substituted.

If R “and R are an aromatic group, it can be for example a substituted or unsubstituted phenyl group. Suitable substituents are monovalent Substituent, such as a halogen atom, a nitro, cyano, thiocyano, hydroxy, alkoxy, aryloxy, alkyl, alkenyl, aryl, Amino, carboxy, acyl, alkoxycarbonyl, ary1oxycarbony1, Carbamoyl, acylamino, sulfo, alkylsulfonyl, arylsulfonyl, Alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, sulfonymido group and the like, and also a divalent substituent which can form a condensed ring together with the phenyl group. Examples for condensed rings formed by phenyl groups having such a divalent substituent are one Naphthyl, quinolyl, isoquinolyl, chromanyl, coumaranyl, tetrahydronaphthyl and the like. These monovalent and divalent Substituents for their part can have further substituents.

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The heterocyclic groups represented by R1 and R2 are linked to the coupler moiety via a carbon atom which forms the heterocyclic ring and is one of the members representing the conjugated electron system of the ring. These heterocyclic groups include those of the thiophene series (e.g. 2-thienyl, 3-thienyl, 2-benzothienyl, 3-benzothienyl, 2-naphthothienyl, 3-naphthothienyl and the like), of the furan series (e.g. 2- Furyl, 3-furyl, 2-benzofuranyl, 3-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl and the like), the pyran series (e.g. 3-pyranyl, 4-pyranyl, 5-pyranyl, 6-pyranyl and the like.) .), the chromene series (e.g. 3-chromenyi, 4-chromenyl and the like), the pyrrole series (e.g. 2-pyrrole, 1-methyl-3-pyrrole and the like), the pyrazole series (e.g. B. 4-pyrazole, l-phenyl-3-p} ^ razole and the like), the pyridineae (e.g. 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-quinolyl, 3-quinolyl, 4- Quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl and the like), the pyrazine series (e.g. 2-pyrazinyl, 2-quinoxazinyl and the like), the pyrimidine series (e.g. 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-quinazoIinyl, 4-quinazolinyl and the like), the pyridazine series (e.g. 3-pyridazinyl, 4-pyridazinyl, 3-cinnolinyl, 4-cinnolinyl and the like), the indolizine series ( z. B. 1-indolizinyl, 2-indolizinyl, 3-indolizinyl, 5-indolizinyl, 6-indolizinyl, 7-indolizinyl and the like), the perimidine series (e.g. 2-perimidinyl and the like), the thiazole series ( e.g. 2-thiazoiyl, 2-benzothiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl and the like), the imidazole series (e.g. 2-benzoimidazolyl and the like), the oxazole series (e.g. Oxazoly.;., 4-0xazo ^: yl and the like), the 1,3,5-triazine series (e.g. 1,3,5-TrJ. ~ Azinyl and the like), the oxazine series and the like.

These heterocyclic groups can be replaced by one or more

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the following substituents: a halogen atom, a nitro, cyano, thiocyano, hydroxy, Alkoxy, aryloxy, alkyl, alkenyl, aryl, amino, carboxy, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, acylamino, Siifo, alkyl sulfonyl, arylsulfonyl, alkoxysulfonyl, aryloxysulfonyl, sulfamoyl, sulfonamido and the like.

Among the yellow color couplers of the general formula I given above, those compounds are preferred in which either R or R, denotes a phenyl group in which one of the Ortho positions is substituted by a halogen atom, e.g. B. a fluorine, chlorine, bromine atom and the like., an alkoxy group, e.g. B. methoxy, ethoxy, propoxy, octoxy and the like., A Aryloxy group, e.g. B. a phenoxy, tolyloxy group and the like., an alkyl group, e.g. B. a methyl, ethyl, butyl group and the like., Or an amino group, e.g. B. an N, N-dimethylamino, N-n-butyl-N-n-octylamino group and the like. In addition, by Substituting the meta position, the para position, or both the meta and the para positions of the phenyl group, the duKhR "or R, is represented with one of the above monovalent substituents affect the properties of the couplers themselves and the dye produced therefrom can be varied and adapted to the particular application.

Among the yellow color couplers used in the present invention are, in particular, the compounds of the ones given below general formula preferred

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- ii -

X-S-C- COCHCOI] K - // \\ -

II

where mean:

X, Y, R ₁ and R _{9 are} the same as those referred to above

the general formula I have been given,

a halogen atom (e.g. fluorine, chlorine, bromine and the like) an alkyl group (e.g. methyl, ethyl, tert-butyl and the like), an alkoxy group (e.g. methoxy, ethoxy, propoxy, octoxy and the like), a Aryloxy group (e.g. phenoxy, methy! Phenoxy and The like.) or an N-substituted amino group (e.g. N, N-dimethylamino, N-butyl-N-octylamino and like),

Q ₉ , Q_ and Q ", which are the same or different from one another

can, each a hydrogen atom, a halogen atom (e.g. fluorine, chlorine, bromine and the like), an alkyl group (e.g. methyl, ethyl, amyl, octadecyl and the like), an alkoxy group (e.g. methoxy, ethoxy, dodecyloxy and the like), an aryl group (e.g. phenyl, methylphenyl, and the like), an aryloxy group. (e.g. phenoxy, methylphenoxy and

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like.), an alkoxycarbonyl group (ζ, B. Äthoxycarbonyl, Hexadecyloxycarbonyl and the like) 5 a Carbamoyl group (e.g. methylcarbamoyl, dodecylcarbamoyl, N-iJ- (2,4-di-tert-amylphenoxy) butylcarbamoyl and the like)> a sulfamoyl group (e.g. Methylsulfamoyl, diethylsulfamoyl, N-y- (2,4-di-tert-amy! Phenoxy) propylsulfamoyl and the like), an alkylamino group (e.g. ethylamino, N, N-dimethylamino and the like)) an arylamino group (e.g. anilino and the like), a sulfonamino group (e.g. methylsulfonamino, a- (3-pentadecylphenoxy) propylsulfonamino and the like), an acylamino group (ζ. B. Acetamido, a- (3-Pentadec3'lphenoxy) butyramido and the like.) a carboxy, sulfo, cyano or hydroxyl group.

Methods for forming yellow color images using the photographic couplers of the present invention include an embodiment in which the yellow color couplers in a photographic emulsion layer are present, and an embodiment in which the yellow color couplers are in a color developing solution available. The former is referred to as the "coupler-in-the-emulsion type", the couplers usually being used during the manufacture of the photographic light-sensitive materials be incorporated into an emulsion layer. The latter is referred to as the "coupler-in-the-developer type", the Couplers in the Hegel are dissolved in a color developing solution and diffuse into an emulsion layer during color development.

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Couplers which can be used in the ^M coupling-in-the emulsion type are preferably fixed in a specific emulsion layer. That is, these couplers must be resistant to diffusion. If this is not the case, they migrate Couplers enter the photographic light-sensitive material and form dyes in other emulsion layers with a different spectral sensitivity, which leads to a marked reduction in the color reproducibility of the photographic materials.

In order to make the couplers resistant to diffusion, a group is preferably introduced into the coupler molecule, the one contains hydrophobic group with at least 8, preferably up to 32 carbon atoms. Such groups are usually referred to as bailast groups. The ballast group can either directly or via an amino, ether, thioether, carbonamide. Sulfonamido, ureido, ester, imido, carbonyl, carbamoyl, Sulfamoyl, sulfonyl bond or the like. Bonded to the copper structure be.

In the yellow color couplers of the present invention, any of the known ballast groups are used. Many ballast groups are known and for example in U.S. Patents 2,600,783, 2,865,751, 3,337,344 and 3,418,129 in the Japanese Patent Publications Nos. 27 563/1964 and 19 035/1970 and in Japanese Patent Applications Nos. 35 379/1973 and 69 383/1973 and the like. Described and these can be used with advantage in the photographic couplers according to the invention.

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Typical hydrophobic couplers include an alkyl group, an alkenyl group, an alkoxyalkyl group, an alkyl-substituted one Ary! Group, an Alko>; y- substituted aryl group, a terphenyl group and the like. And these groups can be replaced by a halogen atom, e.g. B. fluorine, chlorine and the like., A nitro, Cyano, alkoxycarbonyl, amido, carbaraoyl, sulfonamido groups and the like. Be substituted.

Specific examples of ballast groups that can be used in accordance with the invention can be used are the following:

I. Alkyl groups and Alkeny! Groups, such as. B.

/ H ₀ ^ \ r ρ- '

4 9 ^ ^c 8 ^H i7

II. Alkoxyalkyl groups, e.g. B.

- (CK ₂ ) JO- (CHg) ₇ CH ₃₁ - (CH ₂ ) ₃ OCH ₂ -CH - (. CH ₂ ) ₈ -CH ₃

C ₂ H ₅

v, ^T IE in Japanese Patent Publication No. 27 536/64 be sehrieben s ind.

III. Alkylary groups, e.g. B.

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IV.Alkylaryloxyalkyl groups, e.g. B.

CK ₂ O-

-CHO-T

- (CH _p ), 0-

-CH ₂ O-

CH _x -C-CH ₇

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V. Acylaminoalkyl groups, e.g. B. CH C ^ T YC

Tj
12 ^L 25

p ²

-CH ₂ CH ₂ NHCOCH ₂ CH ₂ Kv ^ ^

as described in U.S. Patents 3,333,344 and 3,418,129;

VI. Alkoxyary groups and aryloxyary groups, e.g. B.

QH ₇₁ T, (n)

V /

VII. Residues with a long-chain aliphatic alkyl or alkenyl group and a water-solubilizing carboxy or sulfo group, e.g. B.

GH ₂ COOH SO ₃ H

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VIII, alkyl groups substituted by esters, ζ. Β. -CH-C ₁₆ H -, -, (η), -CK ₂ -CH ₂ -COOC ₁₂ H ₂ , - (η)

IX. alkyl groups substituted by aryl or a heterocyclic ring, e.g. B.

'V> -IiECCCH ₂ CH-C ₁₈ H ^ ₇ (η),

COOCH

-CE ₂ CH ₂ -

X. Aryloxyalkylcarbonyl-substituted ary groups, ζ. Β.

A coupler having a diffusion-resistant group in the molecule can be dissolved in an organic solvent and in the form of fine particles can be incorporated into a photographic emulsion in the usual manner. An example for

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a method of dispersing the couplers which is particularly well suited for practicing the invention, is described in more detail in U.S. Patent 3,676-137. Organic solvents that can be used to dissolve the coupler are described in U.S. Patents 2,322,027, 3,253,291, 3,574,627 and the like. These solvents include those that are hardly soluble in water and have a high boiling point (above about 170 C) and in a color photographic light-sensitive material together with the couplers remain, e.g. B. substituted hydrocarbon ^ carboxylic acid esters, Carboxamides, phosphoric acid esters, ethers and the like. Specific examples of these solvents are di-n-butyl phthalate, Di-isooctyl azelate, di-n-butyl sebacate, tricresyl phosphate, Tri-n-hexyl phosphate, Ν, Ν-diethylcapryiamide, butyl-m-pentadecylphenyl ether, chlorinated paraffin and the like. In combination with the high-boiling solvent, an auxiliary solvent can be used with advantage which are removed during the manufacture of the photographic light-sensitive material can to make it easier to undo the coupler. Examples of such solvents are propylene carbonate, ethyl acetate, Butyl acetate, cyclohexanol, tetrahydrofuran, cyclohexanone and the like.

In order to form a fine dispersion of öilöslichen coupler in a hydrophilic substance having a high molecular _weight} used in a photographic emulsion> is to facilitate, a surfactant is suitably used. Particularly suitable are an anionic surface-active agent, such as sodium cetyl sulfate, sodium p-dodecylt-nonzoisulfonate, sodium nonylnaphthalene sulfonate, sodium di- (2-ethyl-

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hexyl) α-sulfosuccinate and the like, and a nonionic surfactant such as sorbitan sesquioleate, sorbitan monolaurate and the like. To prepare a dispersion of an oil-soluble coupler, an emulsifying device is preferably used, z. B. a homogenizer, a colloid mill, an ultrasonic wave emulsifying device and the like.

A diffusion resistant coupler that has both a ballast group and a carboxylic acid group or a sulphuric acid group is soluble in a neutral or weakly alkaline aqueous solution. By adding an aqueous In solution of the coupler to form a photographic emulsion, the coupler can be incorporated into the photographic emulsion will. It is believed that the coupler is in a micelle form in the hydrophilic high molecular weight substance is made resistant to diffusion.

A diffusible coupler that is not resistant to diffusion making group can be used by adding it to a color developing solution having a primary aromatic Contains amine color developing agent.

Representative examples of yellow color couplers according to the invention of the general formula I given above are the following:

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(1)

(2) ^ '- ■ Clilor ^^^ - rA-C ^. ^ - di-to ^ -aiaylphsiio- (2-ät'iiyli.i2io-2-Küthyl propionyl} acetanilide

(3) 2'-chlorine - (2 ~ ri-nonylthic ~ 2- £ othyJ.propicnyl} scet
GV) 2'-h'ei; ho-y- (2-B-octariGC _l , .- lt} :: io-2-ii; ethylprcpionyi

acetajnilid

(6) i \ ^! --Giilor- (2 - ethylthio-2 - n; 2thjlpropio
(?) 2'-I.ot -: "·: · ■.} ■« ν ^l --nitro- (£. "- ethylthio - 2-r '-. 3tiiylpropJoriyI) - acetani.?.it" :.

(8) 2'-chloro-5'-n-dodecanesulfonamido- (2-cyclohexythio-; 2-methylpropionyl) acGtanilide!

(9) 2 ^l chlorine 5 '' n-dodeGyloxycarbonyl- (2-ethylthio-2-! Riethylj. "-. Ropionyl) acetanilide i

(10) 2 «-n-octadecyloxy- (2-aefehylthio-2-methylpropionyl)
acetanilide

(11) 2 · -Methoxy-5 '- (V (2, Z _f -di-tert-araylphenoxy) butyramido) - (2-ethylthio-2-rr: ethylpropionyl) acetanilide

(12) 2'-chloro-ii '- (3- (2, / _f -di-tert-a :: iylphenoxy) propylsulfair _: ü yl] - (2-iEo-propylthio-2-iiietljylproploiiyl) acetanilide

(13) 2'-Hetho: -: y-5'-C ² ~ (2, /; - di-tert-anylphenoxy) butyramiUcl -i (2-ethylthio-2-methylr.ropionyl) & c-ei-.r .nilid

(lif) 2 ', / f' -Dichlor - {2- Q- (? _ , l _t - di-t ert.-at,: ylphenoxy) - j

propylLhio) -Z-mothylproiiionyljacctaiiilii; ;

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(.15) 2 ¹ -Methcxy-i} '- (^ - On-pentadccylphenoxy) butyraaidq} (2-ethylthio-2 -;:; othyipropioiijl) acota; _; ilid

(16) 2'-chlorine - 5 ¹ - (k - (2, / j -di-t er vamylphenoxy) butyramido} - (2-pher.ylthio ~ 2 ~ methylpropionyl) acetaliilide ■

(17) 2-chlorine-5 ~ (z- (2,4-di-1erVa.-. Ylphenoxy) butyraaidcTj (2-pher.ylthio-2 -: nothylpropunyl) acetauilide

(18) 2'-i-iethoxy- (2- (3-tolylthio) -2-kethylpropionylI-acetaliilide

(19) α- (5,5-tamethyl-3-hydantoinyl) -α- (2-Sthylthio-2-ise-thylpropionyl) -2'-chloro-5 "- (Ji- (2, Z ₁ - di" t ert "-a · yi phenoxy) butyrasiif'o ^ acetanilide

- - (20) a- (5,5 ~ Diiaetuyl-2, ij-dioxc-3-oxazolidinyl) -a- (2-ethylthio-2-xaotliylpropionyl) -2 »-chlor -— 5 '- ^ - ( 2, it-di-tert-aKylphenox.y) butyraraido) acetanilide

(21) a- (p- (oÖBce ~) bromo'b enzotriaaol-l-yl) -a- (2-ethylthio ~ 2-raeth3'lpropior) yl) ~ 2 ^l -n-octadücyloxy acetanilide

(22) a- (5,5-Diraethyi-2 ₅ l | -dio>: o-3-oxazolidinyl) -a- (2-ethylthio-2-ir: ethylpropiouyl) -2 '-msthoxy- ^ ¹ - Qi - (Z , 4-di-tert, -amylphenoxy) butyramido] acetanilide

(23) a- (4-Carboxypheno2: y) -a- (2-n-octylthlo-2-ißethylpropiojsyl) -2'-aietlioxy acetanilide

( Zk ) α- (2, if-Bio: -: ol, 3-benzoxaain-3-yD -a- (2- äfchylthio-2-methylpropionyl) -2 '-ch3 or -5' - ^ - (2, -f-öi-tertv-aaylphenoxy) -acttanilide

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a- (l-Phenyl-5-tetra /, olylthio) -a- (2-ethylthio-2-methylpropionyl) -2 '-chlor ~~ 5' -Qy- (2, i (~ di-tert.- amylphenoxy) butyraii.ido) acetanilide 'I

(26) a- (5-Ket hyl-2-benzotriazolyl) -α- (2-ethylthio-2-ethyl-propicnyl) -2 '-chlor-5' - (k- ( 2, L · - di-tert .-c'imylpiienoxy) -

butyramido) acetanilide ^:

(2?) A- (2, if-] C; ioxo-l, 3-ber: zcxazin-3-yl) -a- (2-ethylthio-,

2-mobhylpropionyl) -2'-methoxy-3 '~ Γί · ι- (2, /j-di-tert.-aicylphenoxy )-!

butyrai :: idoj acetanilide j

(2.8) a "(3 - ^ - Octad-3cylcarbar: .oylj;: henoxy) -a- (2-ethyltliio-

2-methylpropionyl) -3 ', 5' -ciicsrboxyacetanilid.

(29) et- ( 3 - Ti-Octauccylc = ?. rba. .Oyl nueny 1 thio) -α- (2-ethyithio-

2-L1O thyD.propiony 1) ~ 3 ', 5' - the arbox.y; cc g t aiiilid

(30) N- (2-Bsi-iZDtLiszolyl) -? - ethyltbio-2-kethylproplonyl-

(31) a- (l-Müthyl - ^ - ni3tho: -: y-3-hydantoynyl) ~ a- (2-ä.thylthao ~

acotanlj.id
(32) a-Cj.-EGnayl-J ^ -ia

butyra.'iiidcy accta:.: ': "J id

5098A2 / 0912 _BAD OBSGiNAL

Among the yellow color couplers of the general formula I according to the invention, the couplers in which Y is a hydrogen atom can easily be prepared in an overall yield of about 50 to about 70% by a synthesis process which can be shown schematically as follows:

X-SM

ZCC-CH ₂ -CO

^ XS-? - C - CH ₂ -

R ₂ 0

III

IV

^ ³ 4

R,

- ^ - XSCC- CH- - C - IV

R ₂ O

wherein Z is a halogen atom, e.g. B. chlorine or bromine, R ^ an alkyl group with 1 to 5 carbon atoms, ζ. Β. Ethyl, methyl, butyl and the like., Or an ary! Group, ζ. B. Phen}? -] and the like, M an alkali metal, ζ. B. sodium, potassium and the like _? and R ₁ , R 1, Ro ₅ R 1 and X have the meanings given above for the general formula T.

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The compound of general formula III used as the starting material can be used can be easily prepared by a method disclosed in U.S. Patent Application No. 369 650 is described.

The compound of the general formula IV can be prepared easily and in high yield by reacting the compound of the general formula III with the compound of the formula X-SM in a suitable organic solvent such as benzene, an ether, e.g. B. diethyl ether, a halogenated hydrocarbon, Dimethylformamide, formamide, and the like, at about 0 to about 40 ° C.

The compound of general formula V can be readily prepared by condensing the compound of the general formula IV with the compound of formula IIN _N _3 using a

known method, for example the method described in US Pat. No. 3,265,506 and the like.

Among the yellow color couplers according to the invention the general Formula I, the couplers in which Y represents a halogen atom can be easily prepared by a conventional method be, in which the compound of general formula V with a molecular halogen in a solvent such as chloroform, Carbon tetrachloride, acetic acid and the like., Is reacted.

In addition, the yellow color couplers according to the invention can use the general Formula I in which Y represents a group other than a V7asscrstoffatom and a halogen atom, easily by a method be made by using a coupler of the general

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mean formula I, in which Y is a halogen atom, with an alkali metal salt of a corresponding coupling-off group, such as in U.S. Patent Application Nos. 235,937, 319,806 and 395,873 and Japanese Patent Application No. 33 238/1973 and the like.

Some specific synthesis examples are given below. Unless otherwise stated, all parts, percentages, ratios and the like given therein relate to. on weight.

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Synthesis example 1

Preparation of 2'-chloro-5 ¹ - [2- (2,4- di-tert-amylphenoxy) butyramido] - (2-ethylthio-2-methylpropionyl) acetanilide (Coupler 1) ;

Stage 1: Manufacture5_von_Äthjl- (2-äthjlthio-2-meth2l-

To a solution of 31 g of ethyl mercaptan and 300 ml of anhydrous benzene, 12 g of sodium hydride were added while cooling with an ice bath. The sodium salt of ethyl mercaptan was formed with evolution of hydrogen gas. A solution containing 119 g of iithyl (2-bromo ~ 2-methylpropionyl) acetate, prepared according to the process described in US Pat. No. 369,650, dissolved in the mixture was added dropwise to the mixture, while stirring and cooling with an ice bath 200 ml of anhydrous benzene. After completion of the addition, the Reafctionsmischung was 2 hours (α. E. At 20 to 30 ⁰ g) at room temperature. After 2 hours, the reaction mixture was poured into about 1 liter of ice water and the mixture was extracted twice with 300 ml of diethyl ether each time. The extract was washed with water and dried. After the solvent had been removed, the residue was distilled under reduced pressure and 75 g of the desired compound, boiling point 80 to 85 ° C./0.5 mmHg, were obtained in a yield of 68 %.

Stage 2: Production_of_2 ^ _z Ghlor-5 ^ ₌ f2 ₌ (2 _x ^ -di-tert ^ -amylphenoxy) butyramidoJ _- (2-ethylthio-2-methylpropionyl) -acetanilide

A mixture of 21.8 g / ithyl- (2-ethylthio-2-methylpropionyl) acetate, obtained in the above step 1, et al

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5 g of 2-Ghlor-5- [2- (2,4-di-tert-amylphenoxy) butyramido] aniline was stirred for 3 hours under a reduced pressure of 50 to 100 mmHg in an oil bath at 15O ⁰ G. The reaction mixture was recrystallized from ligroin to obtain 51 .g (83% yield) of Coupler (1), mp 65 to 68 ⁰ C.

Elemental analysis for C, ^ H ^^ N ₂ 0 ^ SCl:

Calcd .: C66.50, H 8.10, N 4.53 Found: C 66.23, H 7.95, N 4.55

Synthesis example 2

Preparation of 2 ^l -chloro-5'- | A- (2,4-di-tert-amylphenoxy) -butyramidoj- (2-ethylthio-2-methylpropionyl) acetanilide (coupler 2)

A mixture of 21.8 g of ethyl (2-ethylthio-2-methylpropionyl) acetate, which had been obtained in step 1 of Synthesis Example 1, 44.5 g of 2-chloro-5-f4- (2,4-di- tert-amylphenoxy) butyramido] aniline and 500 ml of xylene were refluxed for 10 hours. The xylene was distilled off from the reaction mixture and the residue was recrystallized from acetonitrile, 53 g (yield 87 %) of the coupler (2) being obtained, mp 121 to 122 ° G.

Elemental analysis for Cv ^ H ^ NoC- ^ SC ^

Calc .: G 66.46, H 8.09, N 4.63 found: G 66.23, H 7.95, N 4.55

Synthesis example 3

Preparation of 2'-methoxy-5'-nitro- (2-äthylthio-2-methyl propionyl ^ ac etaniid (coupler 7)

A mixture of 21.8 g of ethyl- (2-ethylthio-2-methylpropionyl-

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acetate obtained in Step 1 of Synthesis Example 1 and 16.8 g of 2-methoxy-5-nitroaniline were stirred for 4 hours under a reduced pressure of 50 to 100 mmHg at 150 ° C. in an oil bath. The reaction mixture was recrystallized from .Acetonitrile and 29 g (yield 85%) of the coupler (7), mp 138 to 140 ^° C., were obtained.

Elemental analysis for C ^ _{1 -Hp 0} NoOcS:

Calcd .: C 52.89, H 5.94-, N 8.36 Found: C 52.88, H 5.88, N 8.23

Synthesis example 4

Preparation of 2'-methoxy-5 '- [4- (2,4-di-tert-amylphenoxy) -butyramido3- (2-ethylthio-2-methylpropionyl) acetanilide (Coupler 11);

Stage 1: Production_of_2 ^ -Methox ^ -5 ^ -amino- (2-ätJiyltlito-2 _:: S®thyl ^ ro ^ ion ^ l) acetanilide

A mixture of 20 g of the 2 ^I methoxy-5'-nitro (2-ethylthio-2-methylpropionyl) acetanilide obtained in the synthesis example 3, 20 g of reduced iron, 150 ml of glacial acetic acid, 20 ml of methanol and 20 ml of water was refluxed with stirring for 15 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The extract was washed with water and dried. The solvent was distilled off under reduced pressure. The residue was the essentially pure desired compound.

Stage 2: Production_von_2 ^ -Methoxj ^^ lf ^ - ^^ - di ^ tert. -amyl _z

acetanilide
A mixture of 18 g of that obtained in step 1 above

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The residue, 20 g of 4- (2,4-di-tert-gmylphenoxy) butyryl chloride, 5 ml of triethylamine and 300 ml of acetonitrile were refluxed for 40 minutes with stirring. The reaction mixture was cooled and the precipitated triethylamine hydrochloride was separated off by filtration. The acetonitrile was distilled off from the filtrate under reduced pressure. The residue was recrystallized from ethanol and 25 g (yield? 0%) of the coupler (11), mp 57 to 60 ^° C., were obtained.

Elemental analysis for C ^ t-HcoN? ^ ^0:

Calcd .: 0 68.57, H 8.71, N 4.59 Found: C 68.68, H 8.50, N 4.58

Synthesis example 5

Preparation of 2'-methoxy-5 '- [2- (2,4-di-tert.-amylphenoxy) -butyramido] - (2-ethylthio-2-methylpropionyl ") acetanilide (coupler 13)

A mixture of 82 g of the obtained in Synthesis Example 3 2'-Methoxy-5'-nitro (2-ethylthio-2-methylpropionyl) acetanilide and 800 ml of glacial acetic acid was heated to 90 ⁰ C. To the mixture was slowly added 80 g of reduced iron over a period of 4 minutes under a nitrogen atmosphere and with stirring. The reaction mixture was cooled to room temperature and then 24.1 g of sodium acetate was added followed by 97 g of 2- (2,4-di-tert-amylphenoxy) butyryl chloride and the mixture was stirred vigorously for 1 hour. The reaction mixture was filtered to remove the insoluble substances. The filtrate was poured into 1 l of ethyl acetate, washed four times with 1 l of a saturated aqueous sodium chloride solution each time and then dried with sodium sulfate. After the ethyl acetate had been distilled off, the residue was recrystallized from ethanol and 110 g (yield Γ W) of the coupler 13), m.p. 65 to 67 ° C.

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Elemental analysis for G ^^^^ o ^ tß '·

Calcd .: C 68.63, H 8.69, N 4.62 found: C 68.68, H 8.50, N 4.58

Synthesis example 6

Preparation of 2'-n-octadecyloxy- (2-ethylthio-2-methyl propionyl) acetanilide (coupler 10)

A mixture of 21.8 g of the ethyl (2-ethylthio-2-methylpropionyl) acetate obtained in Step 1 of Synthesis Example 1 and 36.1 g of 2-octadecyloxyaniline was added for 4 hours under a reduced pressure of 50 to 100 mmHg stirred in an oil bath at 15O ⁰ G. The reaction mixture was recrystallized from ethanol to obtain 45.3 g (yield 85 .of the coupler (10), IT. 60 to 62 ⁰ C.

Elemental analysis for C _XO H _C! -KO _Z S:

Calcd .: C 70.55, H 10.40, N 2.59 found: C 70.20, H 10.31, N 2.62

Synthesis example 7

Production of 2'-methoxy- (2-n-octadecylthio-2-methyl- ■ propionyl) acetanilide (coupler 4)

Stage 1: Production of _{Ethyl- (2 ::} n-octadec _t vlthio-2 - meth2l ₌

A mixture of 14.3 g of stearyl mercaptan and 200 ml of anhydrous benzene was heated with stirring, added slowly 1.2 g sodium hydride was added. To the reaction slurry a solution containing 13.2 g / ithyl- (2-bromo ~

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2-methylpropi.onyl) acetate and 20 ml of anhydrous benzene, added slowly with stirring. After the addition was complete, the reaction mixture was taken out from the ice bath and stirred for 3 hours. The reaction mixture was then poured into ice water and neutralized by adding glacial acetic acid. The mixture was extracted with 300 ml of ethyl acetate, the extract was washed twice with a saturated sodium chloride aqueous solution. The ethyl acetate phase was dried with anhydrous sodium carbonate. After the ethyl acetate was distilled off, the residue was purified using silica gel chromatography (eluting solvent: chloroform) to obtain 16.2 g (yield 62 %) of the desired compound, T ?. 34 to 57 ° C.

Step 2: Production of Y22_2 ^ -Methoxy- £ 2-n-octadecylthio-2-

A mixture of 8.0 g of the ethyl (2-n-octadecylthio-2-methylpropionyl) acetate obtained in the above Step 1 and 3.2 g of o-anisidine was placed in an oil bath under a reduced pressure of 60 mmHg for 3 hours from 140 ^° C. and then the excess o-anisidine was removed under a reduced pressure of 1 mmHg. The reaction mixture was recrystallized from ethanol and 7.9 g (yield 83%) of the coupler (4-), mp 59 to 61 ^° C., were obtained.

Elemental analysis for 71 1 ^H 53 ^] H 10 , 27, N 2, 76 ber. : C 71 .83, H 10 , 28, N 2, 70 found : C .63,

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S ynthesebeis pie! 8th

Preparation of 2'-chloro-5 '- [4— (2,4-di-tert-amylphenoxy) -butyramido] - (2-phenylth ■ io-2-methylpropionyl) acetanil · id (Coupler 16)

Stage 1: Production_von_Äth2l -_ (2- £ henylthio-2-methylDropionyl) acetate

To a solution of 11.5 g of metallic sodium dissolved in 250 ml of ethanol, 55 g of thiophenol was added and then was the ethanol is distilled off. After adding 400 ml of formamide to the residue to make a uniform solution the solution was immersed in an ice bath and 119 g of ethyl (2-ethylthio-2-methylpropionyl) acetate were added to the solution slowly admitted. After the addition was completed, the reaction mixture was taken out of the ice bath and kept for 3 hours touched. The reaction mixture was poured into 1 l of water and extracted twice with 800 ml of diethyl ether each time. Of the Extract was made with a saturated aqueous sodium chloride solution washed and dried over anhydrous sodium carbonate. After distilling off the diethyl ether was the The residue was recrystallized from η-hexane and 112 g (yield 84%) of the desired compound were obtained.

Stage 2: Production_of_2 ^ _:: Chlor-5 _> | _- ^ _z £ 2 _A 4 _:: di ₌ tert ^ - £ henoxy) butyramiao] _{> =} (2-phenylthio-2-methylpropion, 7l) -acetanilide

A mixture of 5.2 g of ethyl (2-phenylthio-2-methylpropionyl) acetate and 8.8 g of 2-chloro-5-f4- (2,4-di-tert-amylphenoxy) butyramidojaniline in 30 ml of xylene was refluxed for 5 hours. The reaction mixture became the xylene distilled off and the residue was recrystallized from acetonitrile, giving 11.5 g (yield 85 ^) of the coupler (16)

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obtained, m.p. 144 to 145 ° C.
Elemental analysis for C ^ q

Calculated: C 68.55, H 7.52, N 4.11 Found: G 68.62, H 7.37, N 4.21

Synthesis example 9

Preparation of 2 ¹ -Chlor-5 ¹ - [2- (2,4-di-tert-amylphenoxjO-butyramidoJ - ^ - phenylthio - ^ - methyrpropiony ^ acetanilide (coupler 17)

A mixture of 5.2 g of the ethyl (2-phenylthio-2-methylpropionyl ^> ) acetate obtained in stage 1 of the synthesis example 8 and 8.8 g of 2-chloro-5-i2- (2,4-di -tert-amylphenoxy) -butyramido] aniline was stirred for 3 hours under a reduced pressure of 15 to 20 mmllg in an oil bath at 150.degree. The reaction mixture was recrystallized from η-hexane and 9.8 g were obtained (yield 75% of the coupler (1/1), P. 73 to 75 ° C.

Elemental analysis for C ^ oH ^ NpOnSCl:

Calc .: G 68.36, H 7.4 /, Ij 4.21 Found: C 68.62, H 7.37, M 4.21

Synthesis example 10

Preparation of α - (5,5-Dimethyl-2,4-dioxo-3-oxazolidinyl.) -Ot- (2-ethylthio-2-methylpropionyl) -2'-methoxy-5 ^l - [4- (2,4 -di tert-amylphenoxy ) butyr amide o] acetanilide (coupler 22)

To a solution of 9 g of the 2 ¹ -methoxy-5 ¹ - [4- (2,4-di-tert.-Amylphenoxy) butyra! Tiiao] - (2-äthylthJ.o-2-meta , / propionyl ^< ) acetanilicr, dissolved in 150 ml of carbon tetrachloride, gives 2.25 g of bromine at room temperature

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slowly added dropwise with stirring. After the addition was complete, the mixture was stirred for 2 hours. The reaction mixture was sufficiently washed with a saturated aqueous sodium chloride solution to form a carbon tetrachloride solution of α -Bromo- oL- (2-ethylthio-2-methylpropionyl) -2'-methoxy-5 '- / 4- (2,4-di-tert .-amylphenoxy) butyramidojacetanilide. The solution was slowly added dropwise to a solution of 3.5 S 5,5-dimethyl-2,4-dioxooxazolidine, 1.6 g of potassium hydroxide, 20 ml of methanol and 300 ml of dimethylformamide at room temperature with stirring. After the addition was complete, the reaction mixture was stirred for 2 hours. The reaction mixture was poured into 500 ml of ethyl acetate, sufficiently washed with a saturated sodium chloride aqueous solution, and dried with anhydrous sodium sulfate. After distilling off the solvent, the residue was recrystallized from ethanol to give 7.5 g (.Ausbeute 67 * / °) of the coupler (22), mp 155-156 ⁰ C.

Slemental analysis for C ^ ₀ H ₁ -., N ^ OgS:

calc .: G 64.0, H 7.82, N 5.4-9 Found: C 64.95, H? 1, N 5.69

Synthesis Example 11

Production of oil (5,5-dimethyl-2,4-dioxo-3-oxazoliαinyl) - <i- (2-ethylthio-2-methylpropionyl) -2 ^l -chlor-5 ^l - / 4- (2,4 -di tert-amylphe ti oxy) buty r- amidoj apetanilid (coupler 20)

The same processes were carried out as described in synthesis example 10, but this time the 2'-chloro-5 ' - [** ■ - (2,4-di-tert. Amylphenoxy) butyramidoJ- ( 2-ethylthio-2-methylpropionyl) acetanilide and 5,5-dimethyl-2,4-dioxooxazoliain were used, with formation of the coupler (20) in a yield of 83 / έ, 'F. 145 to 150 ⁰ O.

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Elemental analysis for C ZqHi- ^ N- * C

Calcd .: C 62.88, H 7.35, N 5.57. Found: C 63.00, H 7.32, N 5.65

Sy nthesesbeis pieI 1 2

Preparation of d - ["5- (or 6-) bromobenzotriazol-1-ylJ-Oi- (2-ethylthio-2-methylpropionyl) -2'-n-octadecyloxyacetanilide (Coupler 21)

The same procedures as described in Synthesis Example 10 were carried out, this time using the 2'-n-octadecyloxy- (2-; ethylthio-2-methylpropionyl) acetanilide and 5-bromobenzotriazole obtained in Synthesis Example 6, to form the coupler (21 ) in a yield of 69%, Έ. 64 to 66 ⁰ C.

Elemental analysis for C ₂₀ H ₁ -, BrN ,, 0-, S:

Calc .: C 62.54, H 7.88, B 7.83 found: C 62.53, H 7.87, K 7.68

Synthesis Example 13

Preparation of oL- (2,4-Dioxo-1,3-benzoxazin-3-yl) -GL- (2-ethylthio-2-methylpropionyl) -2'-chloro-5'-f4- (2,4-di -tert.- amylphenoxy) butyramido] acetanilide (coupler 2 4)

The same procedures as described in Synthesis Example 10 were carried out, this time the 2'-chloro-5 '- [4- (2,4-di-tert-amylphenoxy) -butyramidoJ- (2-ethylthio- 2-methylpropionyl) acetanilide and 1,3-benzoxazine-2,4-dione were used, with formation of the coupler (24) in a yield of 73%, m.p. 1 ^ 4 to 196 ^° C.

509842/0912

for ^C 42 H ₅₂ I. J ₃ O, ? ^c IS: N 5 , 60 25th 1 431 4th Slement analysis . : C 64, 70 H 6th , 73, N 5 , 41 ber . : C 64, 78 H 6th , 68, found

Synthesis example 14

Preparation of CL - (2,4-Dioxo-1,3-benzoxazin-3-yl) - <ÖC- (2-ethylthio-2-methylpropionyl) -2'-methoxy-5 '- [4- (2,4 -di-tert- amylphenoxy) butyramido] acetanilide (coupler 27)

The same procedures as described in Synthesis Example 10 were carried out except that this time the 2 ¹ -methoxy-5 '- [4- (2,4-di-tert-amylphenoxy) butyramidoj- (2 _T ethylthio-2-methylpropionyl) acetanilide, and 1,3-benzoxazine-2,4-dione were used, to give the coupler (27) in a yield of 76%, mp 118

up to 120 ⁰ O. for ^C 43 74, H 7th .29, N 5 , 36 Elemental analysis : C 66 67, H 7th , 11, N 5 , 4-3 ber. : C 66 found

The yellow color coupler according to the invention of the general formula (I) can be used singly or in combination of two or more compounds. The yellow color coupler according to the invention can also be used together with one or more couplers other than those of the general formula (I). Examples of such couplers that can be used are tetravalent or divalent yellow color couplers of the diketomethylene type, for example those as they are z. B. in U.S. Patents 3,277,155, 3,415,652, 3,447,928, 3,408,194,

2 875 057, 3 265 506, 3 409 439, 3 551 155, 3 551 156 and

3,582,322 and Japanese Patent Application OPI No. 26133/1972, 66834/1973, 66835/1973 and 66836/1973 are described, tetravalent or divalent magenta color couplers from

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Pyrazolone or imidazolone type, for example those such as ζ. See U.S. Patents 2,600 7 & 8, 2,983,608, 3,006,752, 3,062,653, 3,214,437, 3,253,924, 3,311,476, 3,419,391, 3,419,808, 3,476,560, and 3,582,322 , in Japanese Patent Publication No. 20636/1970 and in Japanese Patent Application OPI No. 26133/1972, ql -naphthol or phenol type tetravalent or divalent cyan color couplers, e.g. Such as those disclosed, for example, in U.S. Patents 2,474,293, 2,698,794, 3,034,892, 3,214,437, 3,253,924, 3,311,476, 3,458,315, 3,582,322 and 3,591,383, and in U.S. Pat Japanese Patent Publication Nos. 11340/1967 and 32461/1969 are described. In addition, DIR couplers, for example those as they are, for. Example, in U.S. Patents 3,227,554, 3,297,445, 3,253,924, 3,311,476, 3,379,529, 3,516,831, 3,617,291 and 3,705,801 and described in German Offenlegungsschrift 2,163,811, are used v / earth. The couplers can be incorporated into a photographic material using methods such as those described in U.S. Patents 2,322,027 and 2,801,171 and the like. The couplers of the present invention and other couplers can be incorporated into the same or different silver halide emulsion layers or into layers adjacent thereto or other layers.

The amount of coupler used in the present invention can vary depending on the type of photographic light-sensitive material used and the treatment applied or development. In the case of the coupler-in-the-erculsion type a range of from about 0.02 to about 1 mole per mole of silver halide in the emulsion layer is particularly preferred. if the amount incorporated much less than about 0.02 IiIoI per mole of silver halide is a large amount of silver halide required to achieve the desired color density and in doing so, the light scattering in the emulsion layer decreases too, which leads to a reduction in the sharpness of the image leads. The increase in the syllable t-Beschicntungsmen ^ e leads

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also to an increase in the thickness of the emulsion layer, which in turn leads to an increase in the time required for treatment or development. On the other hand, if the incorporated If the amount is much greater than about 1 mole per mole of silver halide, there remain couplers which are involved in color development are not converted into dyes in the .Emulsion layer and reduce the efficiency of the coupler utilization. This is disadvantageous from an economical point of view and leads to an increase in the thickness of the emulsion layer, which is accompanied by the disadvantages described above. When the coupler of the present invention is used in an amount is incorporated outside the range given above, the advantages obtainable by the present invention cannot be sufficiently preserved.

In the case of a coupler-in-developer type, an amount within the range of about 0.2 to about 50 grams of coupler per 1000 ml of color developing solution is suitable. When the amount added is much less than about 0.2 g of coupler per 1000 ml of color developing solution, the disadvantages described above occur. On the other hand, when the amount added is much larger than about 50 g of capper per 1000 ml of color developing solution, there arises the disadvantage that a large amount of a water-miscible organic solvent must be used to dissolve the coupling xj of a color developing solution and the disadvantage suggests that a large amount of alkali is required to prepare the color developing solution, in addition to the disadvantages described above. A particularly preferred addition amount is within the range of 1 to 10 g per 1000 ml of color developing solution.

The silver halide photographic emulsion used in the present invention can be used, contains a photosensitive silver halide, z. B. silver chloride, silver bromide, silver chloride bromide, Silver chloride iodide, silver iodiabrornid, oilberchloriajodidbrornid and the like contained in a hydrophilic material

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Rait dispersed high molecular weight is _h and it can be prepared by various processes.

For suitable hydrophilic materials with a high molecular weight, contained in the photographic emulsion include proteins such as gelatin and the like, high-density electrolytes having a high molecular weight, e.g. B. polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and the like, high molecular weight amphoteric materials, e.g. B. polyacrylamide treated after the Hoffman reaction is, an acrylic acid / N-vinylimidazole copolymer and the like.

The silver halide photographic emulsion can also be various Contain additives such as are added to conventional color photographic silver halide emulsions, e.g. B. a chemical sensitizer, a stabilizer, an antifoggant, a hardener, a spectral sensitizing dye, a surface active agent, or the like.

Examples of suitable chemical sensitizers include gold compounds such as chloro aurates and gold trichloride, as described in U.S. Patents 2,399,085, 2,50,085, 2,597,856 and 2,597,915, salts of a noble metal such as platinum, palladium, iridium, Rhodium and ruthenium, as described in US Pat. For example, in US Pat. Nos. 1,574,944, 2,410,689, 3,189 and 3,501,313, tin (II) salts, amines and other reducing compounds such as are described e.g. As described in US Patents Z 487 850, 2 698 5I8, 2,521,925, 2,521,926, 2,694,637, • 2,983,610 and 3,201,254 and the like.

Examples of suitable stabilizers or antifoggants include the most diverse known compounds,

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ζ. B. heterocyclic compounds, mercury-containing compounds, mercapto compounds or metal salts, e.g. B. 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, 3-methylbenzothiazole and i-phenyl-5-mercaptotetrazole. Other examples of such compounds are for example in U.S. Patents 1,758,576, 2,110,178, 2,131,038, 2,173,628, 2,697,040, 2,304,962, 2,324,123, 2,39,198, 2,444,605-2 444 608, 2 566 245, 2 694 716, 2 697 099, 2 708 162, 2 728 663- % 728 665,

2,476,536, 2,824,001, 2,843,491, 2,886,437, 3,052 5 ^ 4,

3 137 577, 3 220 839, 3 226 231, 3 236 652, 3 251 691,

3,252,799, 3,287,135, 3,326,681, 3,420,668 and 3,622,339 and in British Patents 893,428, 403,789, 1,173,609 and 1200 188 as well as in "The Theory of the Photographic Process" by C. E. K. Mees and T. H. James, 3rd edition, MacMillan, New York (1966), and in the literature cited therein.

Examples of suitable hardeners include an aldehyde-type compound such as formaldehyde and glutaraldehyde, a ketone compound such as diacetyl and cyclopentadione, a reactive halogen-containing compound such as bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro -1,3,5-triazine _t and such compounds as described in US Patents 3,288,775 and 2,732,303 and in British Patents 974,723 and 1,167,207, a reactive olefin containing compound, e.g. B. divinyl sulfone, 5 - acetyl-1,3-diacryloylhexahydro-1,3,5-triazine and. those described in U.S. Patents 3,635,718 and 3,232-63 and British Patent 994-869, an N-methylol compound such as. N-hydroxymethylphthalimide and those described in U.S. Patents 2,732,316 and 2,586,168, an isocyanate compound, e.g. Such as those described in US Pat. No. 3,103,437, an aziridine compound, e.g. Such as those described in U.S. Patents 3,017,280 and 2,983,611, an acid derivative, e.g. B. Such as described in US patents

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2,725,294 and 2,725,295 are a carbodiimide compound, z. B. those as described in U.S. Patent

3 100 704, an epoxy compound, e.g. B. those as described in U.S. Patent 3,091,537 are an isooxazole-type compound, e.g. B. such as her in U.S. Patents 3,321,313 and 3,543,292 are a halocarboxyaldehyde, e.g. B. mucochloric acid, a dioxane derivative, e.g. B. dihydroxydioxane and dichlorodioxane, and a inorganic hardeners such as chrome alum and zirconium sulfate. Instead of the above compounds can also be precursors of hardeners, such as. B. the alkali metal bisulfite-aldehyde adducts, Methylol derivatives of hydantoin, primary fatty nitro alcohols and the like can be used.

Suitable spectral sensitizing dyes according to the invention may be used include a cyanine dye, e.g. B. a merocyanine, cyanine and carbocyanine. These Cyanine dyes can be used singly or in combination. You can also use spectral sensitization methods using a combination of a gyanine dye and a styryl dye. Examples for suitable spectral sensitizing dyes are for example in US Patents 2,493,748, 2,519,001, 2 977 229, 3 480 434, 3 672 897, 3 703 377, 2 688 545,

2,912,329, 3,397,060, 3,615,635 and 3,628,964, in British Patents 1,195,302, 1,242,588 and 1,293,862, in German Offenlegungsschrift 2 030 326 and 2 121 780, in Japanese Patent Publications 4936/1968, 14030/1969 and 10773/1968, in U.S. Patents 3,511,664, 3,522,052,

3 527 641, 3 615 613, 3 615 632, 3 617 295, 3 635 721 and

3,694,217 and British Patents 1,137,580 and 1 216 203 and the like. The sensitizers can be used as desired depending on the spectral range, the sensitivity and the like, based on the purpose and the use of the photographic materials to be sensitized, to be selected.

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The surface active agents can be used singly or in the form of a mixture. These are usually called Coating aids used. In some cases, however, they are used for emulsifying, dispersing, sensitizing, for Improving photographic properties, antistatic properties, preventing adhesion, and the like used. The surface active agents can be classified into natural surface active agents such as Saponin; non-ionic surfactants such as alkylene oxides, Glycerins and glycidols; cationic surfactants such as higher alkyl amines, quaternary ammonium salts, heterocyclic compounds such as pyridine and the like, phosphonium or sulfonium compounds; anionic surfactants Means that have an acid group, ζ. Β. a carboxylic acid, sulfonic acid, phosphoric acid, sulfuric acid ester or Contain phosphoric ester group; amphoteric surfactants Agents such as amino acids, aminosulfonic acids, amino alcoholsulfuric acid esters or amino alcohol / phosphoric acid esters. Some Examples of such surfactants that can be used in accordance with the invention can be used are, for example, in US patents 2 271 623, 2 24-0 472, 2 288 226, 2 739 891, 3 068 101, 3 158 484, 3 201 253, 3 210 191, 3 294 540, 3,415,649, 3,441,413, 3,442,654, 3,475,174 and 3,545,974, in the German Offenlegungsschrift 1 942 665 and in the British Patents 1,077,317 and 1,198,450 and in "Kaimenkasseizai no Gosei to sono Oyo (Synthesis and Application of Surface Active .Agents)" by Ryohei Oda et al, Maki Shoten (1964), A. W. Perry, "Surface Active Agents", Interscience Publication Inc. (1958) ^ and J. P. Sisley, "Encyclopedia of Surface Active Agents "Volume II, Chemical Publishing Co. (1964).

The photographic emulsion can be applied to a substantially planar material that will remain in place during treatments or developments are not subject to major dimensional changes, e.g. B. on a rigid support, e.g. B. made of glass, metal

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or ceramic, or on a flexible carrier, as desired. Representative examples of flexible carriers are such as they are generally used for photographic materials, e.g. B. a cellulose nitrate, a cellulose acetate, Cellulose acetate butyrate, cellulose acetate propionate, polystyrene, Polyethylene terephthalate, polycarbonate film, a laminate made of these polymers, a thin glass film and paper. The carrier can also, with advantage, be a paper coated with baryta, a paper that is coated or laminated with an oL olefin polymer, especially one made from an olefin monomer having 2 to 10 carbon atoms has been, such as polyethylene, polypropylene and ethylene / butene copolymers, or a synthetic resin film can be used in which the adhesion to other polymers and the Printing properties improved by roughening its surface as described, for example, in Japanese Patent Publication No. 19068/1972.

These supports can be transparent or opaque (opaque) depending on the intended use of the photographic materials. Colored transparent supports can also be used containing a dye or pigment. Such colored supports are already used in X-ray films and are for example in "J. ÜMPTE", 'Volume 67, page 296 (1958), described. Suitable examples of opaque supports include opaque films that can be incorporated by incorporation a dye or pigment, such as. B. titanium oxide and zinc oxide, have been made into a transparent film or synthetic resin films whose surface has been treated as in Japanese Patent Publication, for example No. 19068/1972 are described, as well as opaque materials such as. B. paper. There can also be papers that are light shield strongly, and use synthetic resin films containing, for example, carbon black or dyes. When liability is insufficient between a support and a photographic layer, an adhesive layer (subbing

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layer) which adheres to both the support and the photographic layer. The surfaces of the carriers can also be achieved by a corona discharge, a UV radiation treatment, pretreated a flame treatment or the like to further improve adhesion.

The photographic layers can be made using various Conventional coating processes are applied to a carrier, e.g. B. using a dip coating process, an air knife coating process, a curtain coating method and an extrusion coating method using a funnel as described in U.S. Patent 2,681,294. If so desired two or more layers can be applied simultaneously using the methods described in U.S. Patents 2,761,791, 3,508,947, 2,941,898, and 3,526,528 methods described.

The photographic light-sensitive material containing the yellow color coupler of the present invention can be prepared using a primary aromatic amine compound, e.g. B. a p-phenylenediamine derivative, are subjected to color development. Representative examples of color developer compounds are Ν, Ν-diethyl-p-phenylenediamine, 2-amino-5-cLiethylaminotoluene, 2-amino-5- (N-ethyl-N-laurylamino) toluene, 4- £ N-ethyl- N- ( β- hydroxyethyl) aminqj -aniline and the inorganic salts thereof, 4-amino-3-methyl-E'-ethyl-N- (y3-methanesulfonamidoethyl) -aniline sesquisulfate monohydrate, as described in US Pat. No. 2,193,015, N - (2-Amino-5-diethylaminophenylethyl) methanesulfonamido sulfate, as described in US Pat. No. 2,592, Ν, Ν-dimethyl-p-phenylenedianiine hydrochloride, 3-methyl-4-amino-H-ethyl-N-methoxyethylaniline, such as in Japanese Patent Application OPI No. 64933/1973, and the like. Color developing agents are also described in more detail by LFA Mason in "Photographic Processing Chemistry", pages 226 to 229, Focal Press, London (1966). Along with these p-phenylenediamine type developing agents

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can also. 3-pyrazolidones are used.

The color developing solution may contain various additives, if necessary. Typical examples of such additives are alkaline agents (e.g. alkali metal or ammonium hydroxides, carbonates or phosphates); PH adjusting agents or buffers (e.g. weak acids such as acetic acid, boric acid and the like, weak alkalis or salts thereof); Development accelerators (e.g. various pyridinium compounds or cationic compounds, as described, for example, in US Pat 553,990, 2,577,127 and 2,950,970; non-ionic compounds, e.g. polythioethers, as described, for example, in British patents 1,020,033 and 1,020,032; polymeric compounds with sulfite ester groups, e.g. those described in U.S. Patent 3,068,097; organic amines such as pyridine and ethanolamine; benzyl alcohol; hydrazines and the like); Antifoggants (e.g., alkali metal bromides, alkali metal iodides, nitrobenzimidazoles, e.g., those described in U.S. Patents 2,496,940 and 2,656,271; mercaptobenzimidazole; 5-methylbenztriazole, 1-phenyl-5-mercaptotetrazole, compounds for use in tendon developing solutions such as those described in U.S. Patents 3,115,864, 5,342,596, 3,295,976, 3,615,522 and 5,597,199, thiosulfonyl compounds, e.g., 3 such as described in British Patent 972 211, phenazine N-oxides, e.g., those as described in Japanese Patent Publication No. 41675/1971 and in "Kagaku Shashin Binran (Manual of Scientific Photography)", Volume II , Pages 29-4 /, and the like); Fluid to prevent discoloration (flake formation) or foam formation, e.g. As those described in US Patents 3,161 5'Ί una 5,161,514 una in British Patents 1,050 ^ ^-2:

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1 144 481 and 1 251 558 are described, accelerators with an interfacial effect, for example as described in the US patent 3 536 487 are described, preservatives (e.g. sulfites, bisulfites, hydroxyl; ninhydrochloride, form sulfite, Alkanolamine sulfite adducts and the like) and the like.

The couplers of the present invention can be used by adding them to such color developing solutions.

In the case of color reversal photosensitive materials, before black-and-white development was carried out for color development. Appropriate developing agents to be used can, are z. B. 4-aminophenols, such as 4-N-Metb.ylam.inophenolhemisulfat, 4-N-benzylaminophenol hydrochloride, 4-N, N-diethylaminophenol hydrochloride, 4-aminophenol sulfate and the like; 3-pyrazolidones, e.g. B. i-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone and the like; Polyhydroxybenzenes, e.g. B. hydroquinone, 2-methylhydroquinone, 2-phenylhydroquinone, 2-chlorohydroquinone, pyrogallol, Benzcatechol and the like; p-phenylenediamines, such as p-phenylenediamine hydrochloride, Ν, Ν-diethyl-p-phenylenediamine sulfate and the same; Ascorbic acid; N- (p-hydroxyphenyl) glycine and such as described by C. B. K. Mees and T. H. James in "The Theory of the Photographic Process", 3rd edition, chapter 13, MacMillan Co. (1966), and by L. F. A. Mason in "Photographic Processing Chemistry", pp. 16-30, Oxford Press (1966). Mixtures of these developer compounds can also be used.

After color development, the color photographic materials become bleached. Bleaching can be carried out at the same time as fixing. A bleach bath can be used if desired can be converted into a "blix bath" by adding a fixing agent. Can be used as bleach many compounds are used. Examples of usable

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Bleaching agents are: ferricyanides; Bichromates; water soluble Cobalt (III) salts, water-soluble copper (II) salts; water soluble Quinones; Nitrosophenol; Connections of a polyvalent Metal, such as iron (III), cobalt (III), copper (II) and the like, especially complex salts of such a polyvalent Cation, with an organic acid, such as an aminopolycarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, Iminodiacetic acid, N-hydroxyethylethylenediamine triacetic acid and the like, malonic acid, tartaric acid, malic acid, diglycolic acid and dithioglycolic acid and 2,6-dipicolinic acid; Peracids such as alkyl peracids, persulfates, permanganates and peroxides; Hypochlorites; Chlorine; Bromine and the like; you can used individually or in combinations. The bleaching solution can contain bleach accelerators, e.g. B. such as see them in U.S. Patents 3,042,520 and 3,24-1,966 and in Japanese Patent Publications 8506/1970 and 8836/1970 and various other additives may be added.

The coupler of the present invention has a high coupling reactivity to an oxidation product of a primary aromatic amine developing agent and removed rapidly the oxidation product of the developing agent formed during color development, so that the development of the Silver halide emulsion is accelerated. The inventive Coupler provides upon coupling with an oxidation product an aromatic primary amine developing agent Dye which has superior spectral absorption properties in that it is a pure yellow color devoid of any reddish tint, which is due to a lower absorption in a longer wave range, and thus has a has excellent color rendering properties in the subtractive color process.

That in the implementation of the coupler of the invention with a Oxidation product of a primary aromatic amine developer

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Compound formed dye image is stable and against Less sensitive to light and moisture and therefore has more than one during storage under severe conditions an extremely low tendency to fade over a long period of time. Therefore, the color photographic niche Image can be kept for a long period of time.

The coupler of the present invention can be used in high yield are made from starting materials that are readily available on an industrial scale. It is also possible at of the compound of the general formula (i) the properties of the coupler depending on the intended use of the Modify photographic light-sensitive material by selecting an appropriate group for X. During the introduction a ballast group to a pivaloylacetanilide type coupler Resistant to diffusion, to which the anilide ring is limited, becomes the degree of freedom of introduction a ballast group in the coupler of the invention increased to twice and it is therefore easy to provide the coupler with the necessary sufficient properties,

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

example 1

A solution prepared by heating a mixture of 23.1 g of the coupler (1) according to the invention, 2'-chloro-5 '- / ~ 2- (2,4-di-tert-amylphenoxy) butyramidoj - (2-ethylthio2-methylpropionyl) acetanilide, 25 ml of di-n-butyl phthalate and 50 ml of ethyl acetate at a temperature of 4-5 ° C, became 250 ml added to an aqueous solution containing 25 g of gelatin and 2.5 g of sodium dodecylbenzenesulfonate. The mixture was stirred and then for 30 minutes with a high speed mixer strongly stirred. The couplers were made along with the

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Finely dispersed solvent.

The entire dispersion was added to 1.0 kg of a photographic emulsion containing 54 g of silver iodobromide (iodide content 5 mol%) and 65 g gelatin, and 30 ml of a $% acetone solution of triethylphosphoramide were added as a hardener added. The pH of the mixture was adjusted to 6.0 and then the mixture became a layer of one Cellulose triacetate film base in a dry film thickness of 7.0 microns applied. This material is referred to as Sample A hereinafter. The sample contained 2.0 10 moles of coupler per 1 qm carrier.

Using the same procedure as above, a film was produced, but this time instead of coupler (1), coupler (17) of the present invention, 2 ¹ -chloro-5 ' - [2- (2,4-di -tert-amylphenoxy) butyramidoj - (2-phenylthio-2-methylpropionyl) acetanilide was used. This FiIiT ₁ is referred to as sample B in the following. Sample B contained 2.0 x 10 -4 moles of coupler per square meter of carrier.

For comparison, another film was made using the same procedure as described above, but this time instead of the coupler (1) 21.5 g of the coupler (a) 2'-chloro-5'- £ 2- (2,4-di-tert-amylphenoxy) butyramidojpivaloylacetanilide, bsi which was a compound corresponding to coupler (1) and coupler (17) was used became. This film is referred to as Sample C hereinafter. This sample contained 2.1 10 moles of coupler per 1 square meter of carrier.

These films are stepped sensitometric exposure and then treated or developed in the following manner.

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Treatment tem perature ( ⁰ C) time (min ")

1. Color development 20 15

2. Washing 18 1

3. first fixing 20 4-

4. "Washing 18 3

5. Bleaching 20 5

6. Washing 18 3

7. second fixing 20 3

8. Washing 18 .15

The color developing solution used here had the following composition:

Color developing solution A

anhydrous sodium sulfite Sodium carbonate monohydrate

3.0 S. 4-7.0 G 2.5 S. 2.0 S. 1,000 ml

hydrochloride
Potassium bromide
Water ad

An aqueous acidic solution was used as the fixing solution, which contained sodium thiosulfate and sodium sulfite, and as Bleach solution, a neutral solution was used, the potassium ferricyanide and potassium bromide.

After the development, the optical transmission density became of this specimen against blue light, with those in the Photographic values given below in Table I were obtained. The color images obtained were in each case clear yellow and had an absorption maximum at 455 ni / U.

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Coupler Table I. 100
101
99 -) Gamma maximum Movie
sample (Ό
(17)
(a) veil 1.33
1.45
1.26 1.70
1.85
1.64 A.
B.
C. 0.07
0.08
0.09

~% relative value of the to achieve a density of 0.10 above the Fog required amount of exposure.

In the following table II the maximum densities are given, which be in the development of each sample for different development times were obtained.

Table II

Development time (min)

Film rehearsal Coupler 10 15th 20th A. (D 1.56 1.70 1.75 B. (17) 1.73 1.85 1.89 C. (a) 1.48 1.64 1.70

The above results show that the invention Couplers provided higher sensitivity, gradation and color density than the known coupler, a pivaloylacetanilide type coupler. These results also show that the couplers of the present invention exhibited higher coupling activity than the pivaloylacetanilide type couplers.

To demonstrate the improved coupling reactivity was carried out the following experiment:

The inventive couplers (1) and (17) and · the. Coupler (a)

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were each with a cyan color coupler (b), ie with 4,6-di-dichloro-5-methyl-2- £ 'oL- (2,4-di-tert-amylph.enox _< 7) acetamidoj phenol, in a molar ratio of Mixed 2: 1 and color development was carried out using 4-amino-3-methyl-N, N-diethylaniline. By analyzing the ratio of the formed yellow dye to the cyan dye, the relative value based on the cyan dye coupler (b) of the reaction rate constant in the coupling reaction of the yellow dye coupler was calculated. The relative value of the reaction rate constant was determined by measuring the amounts of the two couplers in the obtained color image, which was prepared by mixing the two couplers X and Y, which provided different colors clearly separated from each other, and adding the mixture to an emulsion and then performing the Color development. If the cupola X has a color with the maximum density (D _v )

** "-Λ. ΙΪ13Χ

and a determination D developed in an intermediate stage, and when the coupler Y develops colors with (D ₇ ) mQv and D _v , respectively, the ratio R - ^ / R ^ of the reaction _{activities of the two couplers}

-Λ. Χ

can be expressed by the following equation: log (1 -)

% _m ^v "X ^y max

^Y log (1 - :

The coupling reactivity ratio B - ^ / Rj can be determined from the inclination of the straight line obtained by considering different groups of ΰ _χ - and D ^ - results by applying different stages of exposure of an emulsion containing a mixed coupler and carrying out color development two axes that intersect at right angles are plotted as log (1 - j) -. The invention

Max
according to coupler (1) and the coupler (17) according to the invention have a relative rate constant of 0.41 and 0.56, respectively,

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while the pivaloylacetanilide type coupler (a) has a relative Had rate constant of 0.32. These results clearly show that the couplers according to the invention have a high coupling reactivity and a high sensitivity, Deliver gradation and color density.

Example 2

Each of Samples A, B and C prepared in Example 1 was used subjected to a step-shaped sensitometric exposure and then developed in the same manner as in Example 1. The samples thus obtained were under exposure to a xenon light arc lamp of 1.5 KW (150,000 lux) through a UV filter, which absorbed practically all light with a wavelength of less than 400 m, u, for a period of Stored for 70 hours and the lightfastness of the color images was determined. The results obtained are in the given in Table III below.

Coupler Tabel III 27 .000 lux):
1.5 Film rehearsal (D 35 25th A. (17) Xenon arc lamp (150
70 hours
Do = 0.5 1.0 4-5 32 B. (a) 41 C. 37 ⁺⁾ 42 50

⁺ fading rate in% of the initial density for blue light (Do).

In addition, samples A, B and C, which had been subjected to the same development, were kept under high temperature and humidity conditions, ie at 60 ^° C. and 75 ° 70 WI, for 3 weeks

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stored for a long time and the authenticity of the color images was determined. The results thereby obtained are as follows Table IV given.

Coupler Tabel rv 75 % RH: 3 weeks (D 60 ⁰ G , 5 1.0 1.5 Film rehearsal (17) Do = O ⁺ > 4th 3 A. (a) 5 4th 4th B. 6th 5 4th G 7th

"* 4) The fading rate in % of the initial density for blue light (Do).

From the above results it can be seen that the invention Couplers provided color images with excellent lightfastness.

Example 3

A solution prepared by heating and dissolving a mixture of 29 »6 g of the coupler (22) according to the invention, ^ - (5,5-dimethyl-2,4-dioxo-3-oxazolidinyl) -oL- (2-ethylthio-2 methyl-propionyl) -2'-methoxy-5 '- [4- (2,4-di-tert-amylphenoxy) butylamidojacetanilid, 30 ml iii-n-butyl phthalate and 50 ml of butyl acetate at a temperature of 5O ⁰ C, was added to 300 ml of an aqueous solution containing 3.0 g of sodium di- (2-ethylhexylV QL-sulfosuccinate and 30 g of gelatin. The mixture was stirred and then passed through a preheated colloid mill five times. The couplers were combined with the Finely dispersed solvent.

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The entire dispersion was made up of? 00 g of a photographic Mixed emulsion containing 22.6 g of silver iodide bromide (iodide content

2 mol%) and 50 g of gelatin, 20 ml of a

3% acetone solution of triethylphosphoramide was added as a hardener. The mixture was then adjusted to pH 6.5 and applied in a dry film thickness of 3 »5 microns on a photographic Paper carrier applied, both of its surfaces coated with a polyethylene resin. A gelatin solution was correspondingly applied to the coating obtained in this way 1.0 micron dry film thickness to form a second layer.

Then in a dry film thickness of 3 »5 microns a green-sensitive silver halide emulsion applied to form a third layer which is a magenta color coupler (c) the. the structure given below

^{(t) CcH} - ww

CCNH -C- CK

I I

K CO

Cl

A gelatin solution containing 2- (2'-benzotriazolyl) -4,6-dibutylphenol as an ultraviolet absorber, applied to make a fourth layer. In a dry layer thickness of 4.0 microns was a red-sensitive silver halide emulsion, the one cyan color coupler (d) of the following indicated structure, applied to form a

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fifth layer and finally a gelatin solution was applied to a dry layer thickness of 0.5 microns Preparation of the uppermost layer, whereby a color copying paper was obtained.

OH'

Cl-

Coupler (d)

This color copying paper became optical through a color negative printed (exposed) and developed in the following manner:

Treatment temperature ( ⁰ C) time. (Min.

1. Color development 24-8

2. Stop "2

3. Bleach-fix "6 4 ·. Washing" 5

Thereby, a color developing solution of the following was given. used composition:

Color developing solution B
Benzyl alcohol
Sodium hexametapho sphat anhydrous sodium sulfite sodium carbonate monohydrate hydroxylamine sulfate

4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sesquisulfate monohydrate / turate

V / ater

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12, 0 ml 2.0 G 2.0 G 27 5 g 2.5 6th 4-, O G ad 1000 ml

In addition, the treatment batches specified below were used Compositions used:

Stop solution

anhydrous sodium sulfite 5.0 g

Glacial acetic acid 15.0 ml

Water to 1000 ml

Bleach-fix solution

Ammonium thiosulfate 105.0 g

Sodium sulfate 8.0 g

Sodium hydroxide 18.0 g

EDTA disodium salt 35.0 g

Iron (II.T) chloride hexahydrate 25.0 g

Potassium thiocyanate 10.0 g

Water to 1000 ml

The color copy obtained had a clear color and four, excellent color rendering. The lack of any red tint to the yellow color was particularly pronounced. That Yellow dye image had an absorption maximum at

Hi

This color copy was exposed to direct sunlight for 10 days, but the density of the yellow dye image in the region of an initial reflection density of 1.0 decreased by only 0.08. When it was stored at high temperature and under high humidity conditions, ie at 60 ^° C. and 75 % RH, for 10 days, practically no decrease in density was observed.

Example 4

A solution prepared by heating a mixture of Ρ '.', Ο g of the inventive coupler (16), 2 ^l -chlorine-5 ^t ~ [4- (2,4-di-t; cr> -l, .- amylplenoxy) but7 / r amido] - (2-phenylthio-2-methylpropionyl) -

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acetanilide, 25 ml of tri-n-hexyl phosphate and 40 ml of ethyl acetate to 45 ° C, was added to 250 ml of an aqueous solution, which contained 25 g gelatin and 1.25 S sodium cetyl sulfate. The mixture was stirred and then vigorously stirred on a high speed stirrer for 30 minutes. The matchmakers were finely dispersed together with the solvent.

The entire dispersion was added to 1.0 kg of a photographic emulsion containing 0.30 moles of silver bromide and 75 g of gelatin and then 10 ml of a 4% aqueous solution of the sodium salt of 2-hydroxy-4,6-dichloro-s-triazine added as hardener. After adjusting the pH to 6.5, the mixture was coated onto a cellulose acetate film support Applied in a dry film thickness of 7? 0 microns. This material is hereinafter referred to as a sample

- 5 D designated. The sample contained 1.9 x 10 -4 moles of coupler per

.m carrier.

For comparison, a film was produced by the same process as above, but this time instead of coupler 06) 25.0 g of a coupler (e), 2 ^l -chloro-5 '- [4 ~ (2,4-di-tert .-amy! phenoxy) butyramido] - (2-phenoxy-2-methylpropionyl) acetanilide, which was the coupler described in German Offenlegungsschrift 2,162,899. This film is referred to as Sample E hereinafter.

-3 2

This sample contained 1.9 x 10 -4 moles of coupler per meter of carrier.

These specimens were a stepped sensitoaietric Subjected to exposure and developed in the same manner as in Example 1 except that this time the color development For 12 minutes at 24 ° C using the method described in Example 5 Color developing solution B described above was carried out. After the development, the optical transmission density became this Samples were determined against blue light and the photographic properties given in the following table V were determined.

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- 59 stocks received.

Coupler veil Table V gamma maximum density sample (16)
(e) 0.06
0.06 Sensitivity * 1.24
1.19 1.65
1.61 D.
E. 100
99

* Relative value of the amount of exposure required to achieve a density of +0.10 above the fog.

In addition, samples D and E, which had been subjected to the same treatment or development, were ^{stored under high-temperature conditions (at 100 °} C.) for 3 hours, and the fastness of the color images was determined. The results obtained are given in Table VI below.

Coupler Tabel Vl hours , 5 sample 100 ⁰ C , 3 1.0 1 1
2 (16)
(e) Do = 0 , 5 1
3 D.
E. 2
3

It is clear from the above results that the coupler of the present invention has superior photographic properties and gave color images with better fastness than the known similar coupler.

Example 5

A solution prepared by heating a mixture of 24.1 g of the coupler (20) according to the invention, cc- (5,5-dimethyl-2,4-dioxo-3-oxazolidinyl) -a- (2-ethylthio-2-methylpropionyl) ) -2 ' -chlor-5 '-C4- (2,4-di-tert-amylphenoxy) butyramido] acetanilide, 25 ml of di-n-butyl phthalate, 1.0 g of 2,5-dioctyl hydroquinone

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and 35 ml of cyclohexanone at 60 ⁰ C, was added to 250 ml of an aqueous solution is added containing 1.5 g liatrium p-dodecylbenzenesulfonate and contained 25 g of gelatin. The mixture was stirred and then passed through a preheated colloid mill five times to give a fine dispersion of the coupler and solvent.

The entire coupler dispersion became 500 g of a photographic one Emulsion added, the 27.2 g of silver iodobromide (Iodide content 4.5 mol%) and 35 g gelatin, and then were 12.5 ml of a 3% acetone solution of triethylphosphoramide added as hardener. After adjusting the pH to 6.5, a coating solution was used for production prepared a blue-sensitive emulsion layer.

A gelatin solution containing black colloidal silver was applied as a first layer to a polyethylene terephthalate film support, in a dry layer thickness of 2.5 microns as an antihalation layer, as _a second layer a red-sensitive silver halide emulsion containing a cyan color coupler (b), 4,6-dichloro-5 -methyl-2- [oc- (2,4-di-tert-amylphenoxy) acetamido3-phenol contained, in a dry layer thickness of 4.5 microns, as a third layer a gelatin solution which contained 2,5-di-tert-octylhydroquinone , in a dry layer thickness of 1.5 microns, as the fourth layer a green-sensitive silver halide emulsion layer which contains a magenta color coupler (d), 1- (2,6-dichloro-4-methoxyphenyl) -3-J3-Coc- (2,4-di -tert.-amylphenoxy) butyr amido] benzamido} -5-pyrazolone contained, in a dry layer thickness of 4.5 microns and as a fifth layer a gelatin layer containing yellow colodal silver, in a dry layer thickness of 2.0 microns. The above-described coating solution for producing a blue-sensitive emulsion layer was applied to the fifth layer in a dry layer thickness of 2.0 microns and a gelatinous layer was applied as the top layer.

509842/0912

21 3 18th 10 21 12th 21 2 21 8th 18th 10

25U3U

- 6i -

tineschuta layer in a dry layer thickness of 1.0 Microns, thereby obtaining a color photographic film. The film was exposed and subjected to the following treatment or development:

Treatment temperature ( ⁰ Cj time (min .)

first development
(Black and white development)

To wash

uniform exposure

ζWide deve lopment
(Color η twist)

To stop

Bleach-fix

To wash

In the second development (color development), the color developing solution B given in Example 3 was used and also in the case of the bleach-fixing, the bleach-fixing solution described in Example 3 was used. When it was first developed a black and white developer solution (developer solution C) with the following composition is used:

Developer solution C

p-N-methylaminophenol 0.3 g

anhydrous sodium sulfite 38.0 g

Sodium carbonate monohydrate * 22.5 g

Potassium bromide 0.9 g

Citric acid 0.7 g

Potassium thiocyanate 1.0 g

Water to 1000 ml

The reversal color photographic image thus obtained exhibited a clear color and excellent color rendering on. The sharpness of the color images was also improved by reducing the thickness of the blue-and-white emulsion layer.

509842/0912

25H314

Example 6

To produce a film, a silver iodobromide emulsion (iodide content 2 mol%) was applied in the form of a layer in a dry layer thickness of 5> 0 microns and a silver coating amount of 150 ng per cm. The film was subjected to a stepped sensitometry exposure and then Ί0 minutes developed at 24 ⁰ C "Using the developer solution given below, then it was fixed, washed, bleached, rinsed, fixed and washed as in Example 1 to give a yellow dye image .

Color developing solution D

Anhydrous sodium sulfite I ₁ Og

4 — Amino-3-methyl-ΪΓ, IT-diet hy laniline hydrochloride sodium carbonate natmo no hydrate "potassium bromide 4- ^l -chloro (2-ethylthio-2-methylpropionyl) acetanilide (inventive coupler (6)) acetone

Sodium hydroxide (8% aqueous solution)

water

The color image thus obtained had a spectral absorption

2, 0 g 22nd , 5 e 1, 0 g 2, 0 g 20th , 0 ml 25th , 0 ml 950 ml

with an absorption maximum. at 455 mu. Example 7

A solution prepared by heating a mixture of 4-8.2 g of the coupler (20) according to the invention, a- (5,5-dimethyl-2,4-dioxo-3-oxasolidinyl) -a- (2-ethylthio-2) -methylpropionyl) 2 '-ch.lor-5' - [4- (2,4-di-tert.-amy! Phenoxy) butyramido] acetaliilide, 50 ml of di-n-butyl phthalate and 75 ml of cyclohexanone

5098 42/0912

60 ° C, was added to 500 ml of an aqueous solution which 2.5 g sodium p-dodecylbenzenesulfonate and 50 g gelatin contained. The mixture was stirred and then passed through a preheated colloid mill five times, one fine Dispersion of the coupler and the solvent was obtained.

The total coupler dispersion was 1.0 kg of a photographic Mixed emulsion containing 123 g of silver iodobromide (Iodide content 7.0 mol%) and 60 g of gelatin, and then 20 ml of a 4% aqueous solution of 2-hydroxy-4-, 6-dichloro-s-triazine sodium salt added as hardener. After adjusting the pH to 6.5, the mixture became applied in the form of a layer on a cellulose triacetate film support in a dry layer thickness of 5 »0 microns. This film is referred to as Sample F hereinafter.

To produce a sample G, the same procedure was carried out v / ie for sample F, this time 4-5 »8 g of the coupler according to the invention (20) and 2.7% of the coupler according to the invention (25} a- (1-phenyl -5-tetrazolylthio) -a- (2-ethylthio-2-methylpropionyl) -2'-chloro-5 ¹ - [4- (2,4-di-tert-amylphenoxy) -butyramido] acetanilide> were used.

Samples F and G were subjected to a slim line exposure through a 500 / µ slit width with X-rays and then treated or developed using the following treatment levels at 38 0: -

1. Color development 3 min. And 15 sec.

2. Bleach 6 "" 30 "

3. Wash 3 "" 15 » 4 ·. Fix 6 "" 30

5. Washing 3 "" 15

6. Stabilize 3 "" I5

509842/0912

25U314

Treatment solutions of the The following composition is used:

Color developer lö sunp ;

Sodium nitrilotriacetate 1.0 g

Sodium sulfite 4.0g

Sodium carbonate - 30.0 g

Potassium bromide _y 1.4 g

Hydroxylamine sulfate 2.4 g

4- (N-ethyl-N-ß ~ hydroxyethylamino) -2-methylanilirisulfate .4.5 g

Water ad 1 1

B calibration solution

Ammonium bromide 160.0 g

aqueous ammonia (28%) 25.0 ml

Sodium ethylenediamine tetraacetate

iron salt 130 g

Glacial acetic acid 14 ml

Water ad 1 1

Fixing solution

Sodium tetrapolyphosphate 2.0 g

Sodium sulfite 4.0 g

. Ammonium thiosulphate (70%) 175.0 ml

Sodium bisulfite 4.6 g

Water ad 1 1

Stabilization solution

Formalin (40%) 8.0 ml

Water ad 1 1

After the treatment in the manner described above, the optical density of the samples against blue light became determined using a microdensitometer and the following results were obtained:

509842/0912

- 65 -
Table VII optical density sample measured area 1.51
1.54
1.25
1.52 E.
ti
F.
It center
edge
center
edge

In the sample E, practically no difference in density was observed between the central area and the peripheral area. Against it In Sample F, a large difference in density was found between the central area and the peripheral area. Dao that is, a large edge effect was observed. The bar effects have the function, resolving power and sharpness of a photographic light-sensitive material to improve significantly. If one of the hydrogen atoms on the reactive methylene group in the invention Coupler replaced by another suitable group, the property described in this example can be the Couplers are imparted in addition to the properties that coupling reactivity is high that rapid development can be used and that the dye formation and the silver removal in a weakly oxidizing Drain the bath completely.

Example 8

A solution prepared by heating and dissolving a mixture of 59 g of the coupler (28) according to the invention, cc- (3-n-0ctadecylcarbamoylphenoxy) -a- (2-ethylthio-2-methylpropionyl) -3 ', 5'-dicarboxyacetanilide, 90 ml of N, N-diethyldodecylamide and 90 ml of cyclohexanone at 70 ° C, became 600 ial added to an aqueous solution containing 3.0 g of sodium p-dodecylbenzenesulfonate and contained 60 g gelatin. The mixture was stirred and then passed through a preheated colloid mill five times happens to form a fine dispersion of the coupler

509842/0912

- 66 and the solvent.

All of the coupler dispersion was mixed with 1 kg of a photographic emulsion containing 76.0 g of silver iodobromide (iodide content 5 »0 mol%) and 65 g of gelatin, and then 25 ml of a 4% aqueous solution of. 2-Hydroxy-4,6-dichloro-s-triazine sodium salt was added as a hardener. The mixture was applied in the form of a layer on a Celluloseacetatträgerin a dry film thickness of 5 ₅ O microns, and the thus obtained layer, a gelatin solution in the form of a layer in a dry film thickness of 1.0 micron as a protective layer to form a photosensitive element.

The following were applied to a polyethylene terephthalate carrier specified layers in the order given below applied to produce an image receiving sheet:

1.) A neutralizing layer containing 300 mg / 100 cm obtained by treating a vinyl methyl ether / maleic anhydride (molar ratio 1: 1) copolymer with butyl alcohol

tenen half ester and 60 mg / 100 cm 1,4-bis (2 ^f , 3'-epoxypropo: xy) -butane;

2.) a layer that controls the rate of neutralization,

containing 4-5 mg / 100 cm) of an n- "butyl acrylate / ß_Hydroxyäthylmethacrylat (Monomer ratio about 1: 1 ^ copolymer;

J.) an image receiving layer containing 18 nig / 100 cm of cetyltri-n-butylammonium chloride, 40 mg / 100 cm of gelatin and 2 mg / 100 cm ^{2 of} tetramethylolurea;

4.) a topcoat about 0.5 microns thick made by treating the surface with a 1% acetone solution of polyethylene glycol monocetyl ether.

A developer solution of the ingredients listed below was

& Q9- & 42/0912

25U3U

Composition prepared and incorporated in a breakable container. The container was made by folding a laminate film made of polyethylene, aluminum, cellophane and polyethylene and heat sealing the same to form a cavity for receiving the developer solution. The preparation and filling of the developer solution into the Containers were carried out in a freon gas.

Water 100 ml

Ascorbic acid 20 mg

4 ^ Amino ~ 3-methyl-N-ethyl-N ~ (ß-hydroxyethyl) aniline sulfate monohydrate 2.8 g

6-nitrobenzimidazole nitrate 15mg

Sodium hydroxide x 4 g

Sodium carboxymethyl cellulose 3.5 S

(Titanium dioxide 45 g

The above-described photosensitive material and the above-described image receiving material were applied Cut to a size suitable for testing, the coated surfaces of each material became mutually exclusive arranged opposite one another and between these materials was at one of the edges the one containing the developing solution Container firmly arranged.

The film unit thus prepared was exposed to light and passed through a pair of pressure rollers to break the container, and the developer solution was spread evenly to a layer thickness of 120 microns.

After 3 minutes, a was formed on the image-receiving layer clear yellow negative image observed. The measurement of the reflection density using blue light showed a density maximum of 1.5 and a density minimum of 0.3

509842/0912

25U314

The invention has been described above with reference to "preferred embodiments explained in more detail, however it goes without saying for the person skilled in the art that it is by no means restricted to this, but that it is in many respects can be changed and modified without departing from the scope of the present invention.

Claims;

509842/0912

Claims (13)

25U3U - 69 claims \\ J Photographic coupler, characterized by the general formula XSGC-CH-CN ι ti ι ti Ro O Y 0 (D where mean: X is an aliphatic, aromatic or heterocyclic one Group, X is a hydrogen atom or a coupling-off group, R, - and Rp each individually an aliphatic group or together a ring and R ^ and Rn are each a hydrogen atom, an aliphatic, aromatic or heterocyclic group. 2. Coupler according to claim 1, characterized in that in the general formula I X has an aliphatic group 1 to 40 carbon atoms, an aromatic group having 6 to 40 carbon atoms, or a heterocyclic group having 3 to 4-0 carbon atoms, R ^ and Rp each an aliphatic Group with 1 to 10 carbon atoms and R, and R ^ each has an aliphatic group with 1 to 40 carbon atoms, an aromatic group having 6 to 40 carbon atoms or a heterocyclic group having 3 to 40 carbon atoms mean. 509842/0 9 12 25H3U . - 70.J-. 3. Coupler according to claim 1 and / or 2, characterized in that X is an alkyl group having 1 to 20 carbon atoms. 4. Coupler according to claim 3, characterized in that the alkyl group is an unsubstituted alkyl group or an alkyl group which is substituted by one or more of the following substituents: an alkoxy group, an aryl group, a heterocyclic group, an aryloxy group, an acyl group, an acylamino group, a hydroxy group and / or a halogen atom. 5 · Coupler according to claim 1 and / or 2, characterized in that that in the general formula I X is a phenyl haphthyl, Means pyridyl or furyl group. 6. Coupler according to claim 5 »characterized in that it The phenyl group is an unsubstituted phenyl group or a phenyl group which is replaced by one or more of the following substituents is substituted: an AlleyI group, an alkoxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, a hydroxyl group and / or a halogen atom. 7. Coupler according to at least one of claims 1 to 6, characterized in that in the general formula I B ^ is an alkyl group having 1 to 6 carbon atoms. 8. Coupler according to at least one of claims 1 to 7 * characterized in that in the general formula I Eo represents an alkyl group having 1 to 6 carbon atoms. 9. Coupler according to claim 1, characterized in that he has the general formula 509842/0912 25H3H ^E l X-S-C-CCC where mean :. X, Y, IL and Rp each have the radicals specified in claim 1, Q ^] a halogen atom, an alkyl, alkoxy, aryloxy or IT-subsidized amino group, Q ₂ , Q * and Q ^ ,, which can be the same or different, each a hydrogen atom, a halogen atom, an alkyl, alkoxy, aryl, aryloxy, alkoxycarbonyl, orarbamoyl, sulfamoyl, alkylamino, Arylamino, suIfoamino, acylamino, carboxy, suIfo, cyano or hydroxyl group. 10 .. Phot ο graph is before silver halide emulsion, characterized in that that it contains a photographic coupler according to at least one of Claims 1 to 9. 11. Photographic light-sensitive material, thereby characterized in that it consists of a support and at least one layer of a silver halide emulsion applied thereon according to claim 10 exists. 12. Parbphotographic developer, characterized in that that it contains a photographic coupler according to at least one of Claims 1 to 9. 13. A method for generating color photographic images, characterized in that an imagewise exposed, silver halide photographic emulsion having a primary 509842/0912 25U3H aromatic amine -]? arb ent v »d ekle rverb inching in the presence of a photographic coupler, at least one egg Claims 1 to 9 developed. 5Q9842 / Q912