DE2658573A1 - PROCESS FOR DEVELOPING IMAGERATIVE EXPOSED LIGHT SENSITIVE COLOR PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL - Google Patents

Description

50 709 - Dr.O? .

Applicant ν Konishiroku Photo Industry Go.,. Ltd.

■■; ^{: v} 4-40, 3-Chome, Mtionbashi-Muro-machi, Chuo-ku ■ Tokyo / Japan

Process for developing an image-wise exposure fair photosensitive color photographic silver halide

nidmaterials

The invention relates to a new coupler for use in photography; it concerns in particular a new magenta coupler for use in photography in which a silver halide is used as a photosensitive component.

In photography, a silver halide is widely used as a photosensitive component for photo recording purposes used because it has excellent photographic properties such as excellent sensitivity and gradation. When a silver halide is used as a photosensitive component to form a color image is used, the silver halide is generally mixed with a certain type of color-forming compound and according to the information recorded in the silver halide, it becomes color-forming Compound reacted with a certain type of reactive compound to form a dye, which

7Ü982S708S9

creates a dye image.

This color-forming compound is referred to as the coupler and, in the case of the reactive compound, the combination is used with the coupler to form a dye, it is generally a color developing agent, e.g., an aromatic amine primary developing agent.

It is well known that when exposed (light-recorded) Silver halide grains with development nuclei in the presence a coupler and a color developing agent, the color developing agent the silver halide to developed silver and at the same time the color developing agent itself is oxidized to form an active one Oxidation product of the color developing agent, this oxidation product reacting with the coupler to form of a dye, and as a result, one of the in a dye image corresponding to the information recorded on the silver halide. ”In this case, the reaction takes place between the coupler and the oxidation product of the color developing agent at the active site (position) of the Coupler instead of and generally this active center is on an active methylene or methine group in the coupler molecule. Couplers like those in photography are used, form yellow, magenta and cyan dyes and these couplers are known under the name yellow coupler, magenta coupler (Magenta coupler) and cyan coupler (cyan coupler).

Among the couplers used in the above dye image forming process are the 5-pyrazolone compounds and the pyrazolone [1,5-a] benzimidazo! compounds are known

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as a magenta coupler with an active methylene group, the upon coupling with an oxidation product of a color developing agent can form a dye. Among these compounds, the 5-pyrazo ion compounds become main ones used in color photography to produce a magenta dye image.

There are already various magenta couplers "made from 5-pyrazolone compounds known. However, these known magenta couplers do not always have the desired properties. To from practical. Being usable from a standpoint it is generally desired that a magenta coupler is sufficiently soluble in solvents, an excellent one Shelf life (shelf life) in a hot and humid atmosphere (environment) has no decomposition and no discoloration entails and has a favorable color forming activity. In addition, a dye image produced therewith must have good absorption spectral properties, a good color density and a good gradation and against light, Be resistant to heat and moisture. In addition, magenta couplers are believed to be advantageous in which neither one Discoloration nor coloration of unreacted couplers remaining in a non-color-developed portion occurs. Needless to say, it is also desirable that such magenta couplers be easily manufactured can and are also not expensive. So, for example those in U.S. Patents 2,600,788 and 2,933,391 and in British patents 9% 261 and 1 173 described i-phenyl-5-pyrazdlone compounds with two or three halogen substituents on the 1-phenyl group known magenta couplers with relatively favorable absorption spectral properties However, if magenta couplers from the above-mentioned i-phenyl-5-pyrazolone compounds for Manufacture of a photosensitive color photographic

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Materials used, they have several disadvantages. For example, the stability of what is produced from it photographic material insufficient if the material is stored in a hot and humid atmosphere (environment); under the influence of poisonous gases such as formalin gas, in the atmosphere there is a yellow discoloration (formation of yellow Color spots); or the color density decreases with the point in time the formation of a dye image by the reaction of the Coupler with a color developing agent. Furthermore, these magenta couplers have the serious disadvantage that the remaining in a non-color developed portion after the color developing treatment of the photographic material Magenta coupler, which did not react during the development of the color, leads to a yellow discoloration which on exposure to it of light, heat, moisture and the like. Occurs. These disadvantages, namely, the decrease in color density and that Occurrence of yellow discoloration (formation of yellow colored spots), are related to the color rendering of multilayered color photographic light-sensitive materials regarded as very disadvantageous.

It is therefore an object of the present invention to provide a novel magenta coupler which is those described above Does not have any disadvantages. The first object of the invention is in particular to provide a new magenta coupler which is disclosed in a multilayered color photographic light-sensitive material is stable without it being exposed to Heat and moisture will cause it to turn yellow. Another object of the invention is to provide a new magenta coupler in which the non-color-developed coupler remaining after the color development treatment does not turn yellow caused as a result of exposure to light, poor and moisture. The aim of the invention is also to provide a new

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• Ms -

Indicate magenta coupler in which the color density does not decrease under the influence of a formalin gas. in the atmosphere _{β A} further object of the invention is to provide a new magenta coupler which exhibits a favorable color-forming effect at the time of color development, gives a dye having a high density, advantageous absorption spectral properties and excellent resistance (stability) to light, heat and moisture having. The aim of the invention is also to indicate a new magenta coupler which is sufficiently soluble in solvents and has an advantageous color-forming effect on color development. .

Another object of the invention is to provide a multilayered color photographic light-sensitive material which contains the novel magenta coupler according to the invention and a has excellent color rendering properties.

The magenta couplers used in the present invention are excellent Purpurroijkupp ler among the 1-phenyl-5-pyxaz ο ion compounds represent with which the above objects of the invention can be achieved.

In the new purple-red couplers used according to the invention they are 1-pentahalophenyl-5-pyrazolone compounds. Particularly preferred examples of these compounds are those having a structure as shown below general formula I or II.

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-As

- σ

II

In the general formulas given above, R ^, R2 and Rj- each denote groups as used in customary 5-pyrazolone magenta couplers, in particular R ^, R ^ and R ₁ denote - individually in each case straight-chain (unbranched) or branched Alkyl having 1 to 30, preferably 1 to 22 carbon atoms, alkenyl (such as methyl, ethyl, isopropyl, tert-butyl, n-hexyl, tert-octyl, n-dodecyl, n-docosyl, allyl, 2-butenyl and the like), cycloalkyl (such as cyclohexyl, norbornyl and the like), substituted alkyl and cycloalkyl (v / where the substituents are selected from the group consisting of halogen, nitro, cyano, aryl, alkoxy, aryloxycarbonyl, alkoxycarbonyl, aryloxycarbonyl, suIfο, sulfamoyl , Carbamoyl, acylamino, ureido, the heterocycles, arylsulfonyloxy and

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Oxo, such as β-gyanoethyl, β-chloroethyl, benzyl, nitrobenzyl, dichlorobenzyl, p-ethoxycarbonylethyl,,) f- (2,4- di-tert-amylphenoxy) propyl, β-phenoxyethyl and the like), aryl , which can have one or more substituents (the substituents being selected from the group alkyl, alkoxy, aryloxy, halogen, carboxy, alkoxycarbonyl, aryloxycarbonyl, acylamino, carbamoyl, IT-alkylcarbamoyl., sulfonamido, sulfamoyl, N-alkylsulfamoyl, N, N-pialkylsulfamoyl, N-arylsulfamoyl, hydroxy, cyano, acyl ^ -alkylsuccinmido, N-alkylamino, Ν, ΪΓ-Malkylamino, ureido and nitro, such as, for example, phenyl, 2-chlorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2,4 --Dichlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-tert-butylphenyl, 4-tert-octylphenyl, 4-methoxyphenyl, 4-octadecyloxyphenyl, 4-phenoxyphenyl, 3-carboxyphenyl, 3-A ^ hOXj / -carbonylphenyl , 3-acetamidophenyl, 3- (2, ^L V ~ di-1ert. -Amylphenoxyacetamido) phenyl, 4 {α- (2,4-di-tert-amylphenoxy) butylamido} -phenyl, ^ -N-dodecylcarbamoylphenyl, 4 - N-dodecylsulfamoylphenyl, 3-Ph enylsulfonamidophenyl, 4- cyanophenyl, 3-nitrophenyl, 4- nitrophenyl and 3- (dodecylsuccinmido) phenyl and the like), alkoxycarbonyl, aryloxycarbonyl (such as methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl and the like), substituted oxyoxy, ethoxy, Phenoxy, tolyloxy and the like), substituted thio (such as ethylthio, propylthio, phenylthio, tolylthio and the like), substituted amino (such as N-ethylamino, N-propylamino, ΪΓ-octadecylamino, N., N-diethylamino, N-benzylamino , N-methyl-N-phenylamino and the like), cycloalkylamino (such as piperidino, morpholino, pyrrolidinyl and the like), amide (such as acetamide, benzamide, palmitoylainide, myristoylamide, (2,4-di-tert-amylphenoxy) acetamide , oc- (4-butylphenoxy) propionamide, cc- (3-pentadecylphenoxy) butylamide, 3- (2,4 ~ di-tert-amylphenoxyacetamido) -benzamide, 3-a- (2,4-di-tert.- amylphenoxy) butylaraidobenzamide, 3-dodecylsuccinimido-benzamide, 3-phenylsulfonamido-benzamide, 3- (3-dodecyloxyphenoxyacetamido) benzamide and the like), anilino, which has one or more substituents similar ch those of

709828/0 86 9

-As -

Have aryl group (such as aniline, 2-chloroaniline, 2,4-dichloroanilino, 2-fluoroanilino, 2-methoxyanilino, 2— Chloro-4-nitroanilino, 2-chloro-4-palmitoylamidoanilino, 2-chloro-5- (2,4 ~ di-tert-amylphenoxyacetamido) anilino, 2-methoxy-5-myristoylamidoanilino, 2-methoxy-5-dodecyloxycarbonylanilino, 2-chloro-5-N-dodecylcarbamoylanilino, 2-metho: xy-5-N, ir-dibutylcarbainoylanilino , 2-methoxy- 5-pb-enylsulfonamidoanilino, 2-chloro-5-octadecylaminoanilino, 2-trifluoromethylanilino, 2-chloro-5-K '> N-dodecylsulfanioylanilino, 2-chloro-5- (4-tert-octylphenylsulfarnoyl) anilino, 2,4-dichloro-5-palmitoylamidoanilino, 2-Ch.lor-5-dodecylsuccinimidoanilino, 2-chloro-5-octadecenylsuccinimidoanilino, 2-chloro-5-perfluoropropionamidoanilino and the like), N-alkylacylamino, B-arylacylamino, If-alkylureido, K-arylureido, IT-alkylthioureido, Carbamoyl (v / ie N-Octadecylcarbamoyl, N-Methjrl-N -phenylcarbamoyljund like) or G-uanidino (such as guanidino, H-alkylguanidino, IT arylguanidino and the like).

IL) stands for hydrogen or a so-called removable group that can be released during the reaction with a color developer compound (v / ie alkyl, substituted alkyl, arylazo, substituted arylazo (e.g. p-hydroxyphenylazo, p-methoxyphenylazo, m-ctilorphenjrlazo, maphthylazo and like), heterocyclic azo, alkoxy, aralkoxy, aryloxy, substituted aryloxy (such as m-chlorophenyloxy, p-ethoxycarbonylphenoxy, p-phen; / ls \ :. lfonylphenoxy and the like), heterocyclic oxy, arylthio, substituted arylthio ( v / ie e.g. m-Dodec.ylcarbanioylphenylthio, p-chlorophenylthio, m-cyanophenylthio, p-methylphenylthio and the like), heterocyclic thio, acyloxy, alkoxycarbonyloxy, alkoxyoxalyloxy, aryloxyoxalyloxy, aryloxyoxalyloxy, aryloxyoxalyloxy, substituted aryloxyoxalyloxy, e.g. m-Methoxj ^r phenoxyoxalylox5 ^r and the like), carbonylmethoxy (such as,

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PropylajninacarbönylmethO: x ^, .lthoxycarbQnylme.tb.oxy, Dodeeylcarbonylmethoxy: and the like), acylamino, 1 -Pip eridyl, F, Hr-Dialkj'-lamino, _H, li-: diacylamino, succinimido, Diphe.nylmetb.yl, - ■ substituted biphenylmethyl. . (like ζ..Β .. · bis- (p-chlorophenyl) -methyl, p-chlorophenylphenyl methyl, bis (p-cyanophenyl) iaethyl and the like; *);,.; Triphenylmethyl, substituted triphenylmethyl (like-ζ.Β. Tris ~ (p-chlorophenyl) methyl, metachlorophenyldiphenylmethyl and the like), acyl, halogen, -Sulfο, thiocyanate), 2-BenztriazOl, Cinnamoyloxy, substituted cinnamoyloxy (e.g. ο, - p-Dichlor.cinnamoyloxy, p-Methylcinnamoyloxy, ß-Methi ^ l- " C5.nnainoyloxy; tmd: like i). Particularly preferred as a substitute

tes-alkyl _: for "Ep are diphenylmethyl and triphenylmethyl, in which phenyl can have one or more substituents, such as.halogen, alkyl., .alkoxy, aryl, aryloxy, alkenyl, ■ alkenyl oxy, acyl, amino -, '"Cyano, acylamino, carbamoyl, sulfamic acid and the rest of a heterocyclic song.

E ^ stands for a so-called split-off group that occurs during the implementation can be released with a parbo developer compound. The group that can be split off is divalent and suitable Nete examples are alkylene, arylene, -arylenedioxy, arylenedithio, a heterocyclic nucleus (ring), sulfur, alkylenes dicarbonyloxy and dglo -As alkylene for R ^, methylene is preferred, which can be substituted by alkyl, alkoxy, aryl, aryloxy, aralkyl and / or aralkyloxy. ...

In the general poriaeln given above I and II mean X ^ to X ^ i- individually each halogen, in particular chlorine, bromine and fluorine. ... ·

In the above, stated; general formula I, X ^ ,, Xp, X ^ _V rX ^ and ^ Xc all mean the same halogen atom or they can each mean different halogen atoms which are selected

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are from the group of chlorine, bromine and fluorine atoms "

In the general formula II, X ^, X ₁ - ,, Xg, Xq, Xj ₀ , Xj ^, Xy, ρ, Xy, ^, Xy \ u and X ^ ₁ - can all mean the same halogen atom or they can each be different Halogen atoms are selected from the group consisting of chlorine, bromine and fluorine atoms, and phenyl groups which these halogen atoms have can be the same pentahalogen-substituted group or different pentahalogen-substituted groups.

Typical examples of the 1-pentahalogenophenyl group in the general formulas I and IΓ are as follows: 1-pentachlorophenyl, 1-ifeitabromophenyl, 1-pentafluorophenyl, 1- (2,4-, 6-trichloro-3,5-difluorophenyl), 1 - (4 ~ chloro-2,3,5,6-tetrafluorophenyl), 1- (2,4-D.ichlor-3,5,6-trifluorophenyl), 1- (4 ~ bromo-2,3,5, 6-tetrachlorophenyl), 1- (4 ~ bromo-2,3,5,6-tetrafluorophenyl), 1- (2-bromo-3, 4 ·, 5,6-tetrofluorophen ^ ¹ !), Λ - (2,3,4-, 5-tetrachloro-6-fluorophenyl), 1- (2,3,4 ·, 6-tetrachlor-5-fluorophenyl), 1- (2,3,5,6-tetrachlor -4-fluorophenyl) and 1- (2,3,5,6-tetrachloro-4-iodophenyl).

Among the conventional i-phenyl-5-pyrazolone magenta couplers with zv / ei or three halogen substituents on the 1-phenyl group those with three halogen substituents on the 1-phenyl group are useful, and especially those with one 1- (2,4-, 6-trihalophenyl) group with halogen substituents in the 2, 4 and 6 pitches are used extensively. Nevertheless, with these conventional "1- (2,4-, 6-trihalophenyl) -5-pyrazolone couplers insufficient colored dye density and insufficient color sensitivity be achieved. In addition, the colored dye does not have satisfactory absorption spectral properties and is resistant to light, heat and moisture

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unstable. There is also the occurrence of yellow discoloration (Formation of yellow spots of color) and the decrease in color density under the action of a formalin gas to observe",

In contrast, the magenta couplers of the present invention, namely the i-pentahalogenophenyl-5-pyrazolone compounds, have the property that a high color density can be obtained in color development Occurrence of yellowing (formation of yellow color stains) in the non-color-developed portion is less, and that the formed magenta dye image is very resistant to light, heat and moisture. The magenta couplers according to the invention also have the characteristic property that the absorption of the second absorption band of the magenta dye obtained therewith is low in the region of blue light and that they have advantageous absorption spectral properties from the standpoint of color reproduction. In particular, in the case of a coupler with a structure in which an anilino group is in the 3-position of the pyrazoion core (ring), the absorption maximum is shifted to the side of the longer-wave range by introducing a pentahalogenophenyl group in the 1-position, see above that the desired absorption is achieved while the secondary absorption becomes small, so that favorable results can be obtained from the standpoint of color reproduction. Since the inventive 1-Pentahalog;. Enphen> ^r l-5-pyrazolone magenta couplers provide a high color density, the film thickness of the magenta layer can be lowered in a light-sensitive photographic material v / ground, and the consequence is that the sharpness and transparency of the resulting resulting magenta dye image advantageously

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can be improved. Because of the high color density and the high color sensitivity, they are suitable according to the invention used magenta couplers for use in high temperature and high speed development. Because of the narrow The magenta couplers according to the invention have secondary absorption bands of the magenta dye obtained therewith furthermore the property that the concentration of the colored magenta coupler used can be kept to a minimum and that, as a result, the film thickness of the magenta layer in the color photographic light-sensitive material can be reduced. Furthermore, those used according to the invention have Purple coupler the excellent property that they are free from a denaturation reaction with a poisonous gas (such as formalin gas or the like) in the emulsion and that the occurrence of yellowing (formation of yellow stain) with the lapse of time is little.

Typical examples of the magenta couplers of the present invention are from an i-pentahalophenyl-5-pyrazolone compound given below, it should be noted, however, that the invention is in no way limited to the according to the invention usable magenta coupler is limited.

Exemplary couplers according to the invention: 1. ^H 2? S- ^CH 3

2.

70982870869

H ₉ CO - C ₁

² I Il ^] O = C. Ii

Nk

fcs

-Vr-

H ₂ OO = C _n
Br

Br

- ^C 14 ^H 29

SO ₃ H

HO, S - C

³ I O = C

ci

C - NHCOC

Il

N Cl

ci γ ci

Cl

H ₂ C -C - NHCOCE ₂ O

o = c r

Cl

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QS - C r

O = C

C * OC ₀ H, -

Ii

P. T ^F
Cl C -
Il MCO- / It
β Cl Si
V ¹ Λ
Cl TCl
Cl ■ tr η NHC ₁₈ H ₃₇ ² I.
O = C _n Γ »'
λ. -C -
Il P.

Br

Cl

10, H ₀ CC - NH

mcocH,

ei 1, ci

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Ci

H ₀ CC - JIH

² J Ii

O = C N -

^ Jf /

• is

COCH,

OCH,

H ₂ = -

C - NH

Il

N Cl

HHCOC,

3 ^H 27

Cl

H ₀ CC - HH

² I Il

O = C N

N ₁ /

Cl

MCOC ₁₅ H ₂₇

Cl

Cl

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Cl

² I.
O = C _n C -. NH
. Il ■
N Br J ^ Br Br ⁵ ^ f Br
Br-

Cl

H ₀ CC - NH

² I Il

O = C. N

Cl

- C = Cl

Cl

c - mco Il

N Cl

NHCOCE ₂ O

Cl

CH ₃ O

H I

= N-C I O = C,

Cl

C-NHCO

Il

N Cl

ci y ci

Cl ^tC 5 ^H H

^tC 5 ^H ll

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N = N-C- ^ C-HH

O = CL-. YY'- X _n /

° \ Λ / ^σι

ci

Cl

HO-f VN = N - C—— C-NH-

f.

OH,

Cl. ± , Cl

ci γ ci

Br

N -'Hs

N -; N

^ C

- S - C C -

15th

Br 1

Br

H ₂ C-C-NHCONH

O = ^

c:

NHCOCHO. C.

Cl

709 8 2870 8B9

I CH - C C -

I if

he

Cl

H
I.
Λ ρ ΛΤΤΤ- Cl
\ = C _n Il
, N 1ΜΠ Λ = Cl ί ⁰¹ >
Cl Cl Λ \ $ / NHCOC ₁₃ H ₂₇ Cl

> CH-

Cl

25. H.

H ₂₇ C ₁₃ CONH ^ VCH = CH-COO-C = C -

OCH ^

til

ci 1, ci

ei T ei

Cl

I C

O = C

C - NHCOCH

^tC 5 ^H ll

b / VS

Br T Br Br

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Cl

H ₂ C- C -
I] O = C _n H
N F. ^ JN—
J: Cl F. Cl

Cl

H ₀ CC - NH

CO-CH-C _1Q H 18

N <I

CO-CH

Cl

O = C. C.

C-NH-

IN

Cl

cAAcI

Cl

NHCOCHO I

> Ν ·

N, Cl 1 Γ ^ C = O V πι Cl ^ Cl Cl

H I - C

O = C.C.

C-CH.

I ν

Cl

Cl

70.9828 / 08B9

Cl

Cl

-NE-C

Il

N. Cl

Cl

C = O Cl

it ο ο = α Cl

σ-ΝΗ- ^ \

ci

Cl

Br Cl

C ₁₅ H ₂₇ CONH

C - CH - C-

Il I I J

N C = O CH ,, C.

\ _Ν /

ci J ei

F.

CH ₃ O- /

C-NH

Br

MCOC ₁₅ H ₂₇

ρ γ "ρ ρ T

Cl P

- ψ - ^C 12 ^H 25

CO - CH,

Cl

C-NH-

NHCO (CH ₀ ), 0

), 0f VtC ^ ₁ t ί \. / 5 11

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Cl

O = C. "
C.

C -

Il · ^:

^C 2 ^H 5

Cl

Cl

H ₉ C
O = C

0 - M-

Il

ci

fflC0CH _o CH _o CH_0C _o H _c -. ■ .c, 2 i £ ^

Cl

H
ι r
Cl C -
π Cl "Λ I.
σ
ι Il
Λ M- / I.
O = C _n . NHC0 (CH _{2) 3} 0 Cl K he

^tC 5 ^E ll

> CH-

H Cl

C -C - ΜΙ I! ο = α ν

CO - CH -

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39.

H
J
η -C -
Il I ii
O = C N I. Vy ^c1 cA

Cl

> CH

X = /

The i-pentahalophenyl-5-pyrazolone compounds according to the invention can be prepared by the general procedure for the synthesis of 1-phenyl-5-pyrazolone compounds are, for example, by a method as described in US Patents 23 69 489, 23 76 380, 24 72 581, 26 00 788, 29 33 391 and 36 15 506, in British Patent ' . 956 261 and Japanese Patent Publication ITr. 20 636/1970 is described. In addition, this can be used as a starting material for the production of the inventive 1-pentahalophenyl-5-pyrazolone compounds Pentahalogenphenylhydrazine used can be prepared by the general procedure as described in the "Journal of the Chemical Society ", Volume 1960, pp. 1771, and Volume 1971, Page 172, "Yuki Kagabutsu Gosei-Ho (Process for the Synthesis of Organic Compounds ", Volume 19, page 26," lTippon Kagaku Zasshi "Volume 89, page 321, and the French patent 1 408 502 is described.

The following is a few examples of production the i-pentahalophenyl-5-pyrazolone purple-red coupler according to the invention explained in more detail.

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Synthesis example 1

1- (2,3,4,5,6-pentachlorophenyl) -3-heptadecyl-5-pyrazolone [Synthesis of Kugpier According to the Invention (2) J

50 g of pentachloroaniline in 250 ml of acetic acid were heated to 60.degree and stirred. The mixture obtained was added to A solution of 14.5 g of sodium nitrite in 120 ml of concentrated sulfuric acid was added dropwise over a period of 30 minutes. After completion After the addition, the mixture was heated to 60 ° C. for a further 30 minutes and then cooled to 5 ° C. with ice water. In the Mixture was at a temperature below 15 C, a solution of 175 g of tin (II) chloride dihydrate in 150 ml of concentrated Hydrochloric acid was added dropwise. After the addition is complete the mixture was stirred at 25 ° C. for 1 hour, and the reaction liquid was filtered off with suction and filtered the separated crystals were washed with 20 ml of water. After making them alkaline with ammonia water (d = 0.88) the crystals obtained in this way are filtered off with suction and then dried at 80 ° C., crude pentachlorophenylhydrazine was obtained. The crude pentachlorophenyl hydrazine was under Using a Soxhlet extractor with chloroform extracted. After removal of the chloroform, 45 g of pentachlorophenyl hydrazine, mp 177 to 180 ° C., were obtained. Elementary analysis:

calc .: C 25.70 H 1.07 N 9.99 Cl 63.22 found: 25.68 1.19 9.82 64.20%

Then 5.6 g of the resulting pentachloropheny1-hydrazine, 6.9 g of methyl stearoyl acetate and 1.4 g of acetic acid in 120 ml of ethanol were refluxed for 2 hours. After completion after the reaction, the reaction liquid was 1.5 g

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Sodium ethylate is added and the mixture is refluxed for 30 minutes. The liquid thereby obtained was then poured into 300 ml of water containing 10 ml of concentrated hydrochloric acid, and the precipitated white crystals were separated by filtration and then dried. After recrystallization from ethanol, 6 g of the desired compound were obtained in the form of white crystals, mp 105-107 ° C.
Elemental analysis:

calc .: C 54.70 H 6.53 N 4.90 Cl 31.05 found: 54.91 6.40 4.77 31.21 %

Synthesis Example · 2

1- (2,3,4,5,6-pentachlorophenyl) -3- (2,4-di-tert-amyiphenoxyacetarnido) -5-pyrazolone J [Synthesis of the coupler according to the invention (6) J

10 g pentachloropheny! Hydrazine, 8.3 g ethyl-ß-ethoxy-ß-iminopropionate hydrochloride, 3.5 g of sodium acetate and 2 g of acetic acid in 150 ml of methanol were refluxed for 1 hour, 5.5 g of sodium methylate were added to the reaction liquid and refluxed for 30 min., then it was poured into 300 ml of water containing 15 ml of acetic acid, and the precipitated crystals were separated off by filtration and then dried. After recrystallization from acetonitrile, 7 g of 1- (2,3,4,5,6-pentachlorophenyl) -3-amino-5-pyrazolone were obtained in the form of a pale brown powder, F. 245 to 247 C. Elemental analysis:

calc .: C 31.11 H 1.16 N 12.09 Cl 51.02 found: 30.99 1.10 11.89 51.13%

Then 3.5 g of the 1,3,4,5,6-pentachlorophenyl) -3-amino-5-pyrazolone obtained were added and 4 g of 2,4-di-tert-amylphene

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- rs- -

_x 2858573

oxyacetic acid chloride in 50 ml of acetonitrile for 5 hours Refluxed. Thereafter, the reaction mixture was treated with 1 ml of methanol and refluxed for 30 minutes and the solvent was removed under reduced pressure. After recrystallization of the residue from a methanol / η-hexane (4/1) mixture, 3 g of the desired compound were obtained in the form of a white powder, F. 175 to 178 C. Elemental analysis:

calc .: G 52.15 H 4.86 N 6.75 Cl 28.50 found ■ 52.04 4.92 6.68 28.33 %

Synthesis example 3

1- (2,3,4,5,6-pentachlorophenyl) -3- (2-chloro-5-acetamidoaniline ^ -5-pyrazolone Synthesis of the coupler according to the invention (H) J

27 g perfluorobenzene and 76.3 g hydrazine hydrate in a mixture from 54 ml of water and 160 ml of ethanol x -rden for 12.5 hours refluxed. Thereafter became the reaction liquid cooled, with 400 ml of water / ver sets, extracted with methylene chloride and dehydrated over anhydrous magnesium sulfate, then the methylene chloride was removed, after recrystallization the residue from n-hexane gave 16 g of pentafluoropheny / hydrazine, F 76 to 78 C. Elemental analysis;

calc .: C 36.38 H 1.53. W 14.14 F 47.95 found ! .... 36.43 1.68 14.04 48 ₉ OO %

Then 3.6 g of 2-chloro-5-acetamidoaniline and 4.8 g Ethyl-ß-ätlioxy-ß-imino-propionate hydrochloride in 30 ml of methanol Stirred for 24 hours at room temperature, then the mixture became Boiled under reflux for 1 hour. The methanol was removed under reduced pressure, the oily which remained

709828/0889

The product was heated together with 20 ml of benzene and the ammonium chloride formed was removed by filtration. After removal of the benzene from the benzene filtrate, ethyl β-ethoxy-β- (2-chloro-5-acetaminophenyl imino) propionate was obtained quantitatively. To the compound thus obtained, 4 g of pentafluorophenyl hydrazine prepared as above and 50 ml of ethanol were added, and the mixture was refluxed for 20 hours and then cooled. 1.1 g of ilatriuramethylate were added to the mixture and the mixture was refluxed for 30 minutes. The reaction liquid was poured into 200 ml of water containing 20 ml of acetic acid, and the precipitated crystals were separated by filtration and then dried. After recrystallization from acetonitrile, 3.5 g of the desired compound were obtained in the form of small white platelets with a temperature of 223 to 225 ^° C.
Elemental analysis:

calc .: G 47.18 H 2.32 N 12.94 F 21.95 Cl 8.19 found: 47.18 2.25 12.86 21.74 S.00%

Synthesis example 4

1- (2,3,4,5,6-Pentachlorophenyl) -3- (2-chloro-5-myristoylamidoaniline) ■ 5-gyrazolone synthesis of the ball according to the invention (13) 1

The same reaction as in Synthesis Example 3 was carried out except that 7 g of 2-chloro-5-myristoyiamidoaniline were used this time and 5.6 g of pentachlorophenyhydrazine in place of that in that Synthesis Example 3 used 2-chloro-5ecetoamidoaniline and pentafluorophenyl hydrazine, respectively. After recrystallization 5 g of the desired compound were obtained from ethyl acetate in the form of small white needles, mp 142 ° to 144 ° C.

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-X-

Elemental analysis:

her: C 50.97 H 5.01 N 8.19 Cl 31.13 found: 51.10 5.07 8.09 31.13%

Synthesis Example · 5

l- (2,3,4 ', 5,6-pentachlorophenyl) -3- (2-chloro-5-myristoylainidoaniline) 4-oc-naphthylazo-5-pyrazo lon '[synthesis of the invention according to en

To a mixture of 0.8 g of α-naphthylamine and 10 ml of a 10% aqueous hydrochloric acid solution became a solution of 0.4 g of sodium nitrite in 3 ml of water was added dropwise, the mixture being cooled to a temperature below 5 ° C. Put an end to it After the addition, the mixture was kept below 5 ° C. and stirred for a further 30 minutes, a diazotized liquid being obtained became. Then a solution of 3.4 g of l- (2,3,4,5 ^ 6-pentachlorophenyl) -3 - ^ - chloro-S-myristoylaminoaniline) -5-pyrazolone, prepared as indicated in Synthesis Example 4, in 60 ml of pyridine while kept at a temperature below 10 ° C was added dropwise to the diazotized liquid obtained above and stirred. After the addition was complete, stirring was stopped continued for an additional 30 min, and the mixture was then poured into 200 ml of 10% hydrochloric acid aqueous solution and the precipitated crystals were separated by filtration and then dried. After recrystallization the desired compound was obtained from ethyl acetate in the form of rust-brown crystals, F. 241 to 245 C. Elemental analysis:

calc .: C 55.92 H 4.81 N 10ß3 Cl 25.40 Found: 55.89 4.71 10.25 25.38%

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Synthesis example 6

4,4 ¹ -p-chlorobenzylidene-bis-1- (2,3,4,5,6-pentachlorophenyl) -3- (2-chloro-5-myristoylamidoanilino) -5-pyrazolone synthesis of the coupler according to the invention (24) J

6.8 g of 1- (2,3,4,5,6-pentachlorophenyl) -3- (2-chloro-5-myristoylamidoanilino) -5-pyrazolone as obtained in Synthesis Example 4, and 0.7 g ρ-chlorobenzaldehyde in a mixture of 50 ml of ethanol and 1 ml of triethylamine were refluxed for 5 hours. At the end of this time, the ethanol was removed and the residue was dissolved in ethyl acetate and the solution was washed with dilute hydrochloric acid. The ethyl acetate layer was then evaporated to dryness and the residue was recrystallized from ethyl acetate to give 3.5 g of the desired compound in the form of white crystals, mp 185-188 ° C.
Elemental analysis:

calc .: C 52.42 H 4.80 U 7.52 Cl 30.95 found: 52.40 4.77 7.60 30.72%

Other exemplary couplers of the present invention can also be used can be easily synthesized in a manner similar to that explained above. The exemplary synthesized in this way Couplers individually underwent a coupling reaction with an oxidation product of 4-amino-3-methyl-17-ethyl-N-ß-methanesulfonamidoethyl aniline sulfate to obtain magenta dyes.

Any of the resulting purple-red dyes (magenta dyes) was dissolved in methanol to measure the absorption spectrum in the visible region. The wavelength of absorption

709828/0889

maximums of any purple dye (l-long taupe it) is given in the following Table I, In addition, in the Table I below for the couplers (18) according to the invention, (19) and {20) the wavelength of the absorption maximum of each colored magenta couplers are given in brackets.

70 9-8 2 β / 0-8 8 9

Table I. according to
Coupler
No. - Np * ν ν \ j ι \ j required according to 1
Coupler
No. wavelength
his absorption
ion maximum 21 wavelength
of the absorption
t ion smaximunis 1 548 22nd 558 2 549 23 550 3 548 24 540 4th
1 562 25th 540 5 559 26th 541 6th 556 27 556 7th 539 28 540 8th 554 23 540 9 528 30th 541 10 540 31
I. 549 11 540 :
i 32 540 12th 538 33
j 540 13th 540 !
I 34
I. 540 14th 540 \
I 35 540 15th 543 540 - 16 542 I 31
ι - 540 y - 17th 554 1
j 38 540 I. 18th 554 (431) j 39 540 19th 540 (434) t 539 j 20th 533 {432}

709328/0889

To form a magenta dye image using a magenta coupler according to the invention, any of the so-called photographic processes, of the indoor type, can be used, wherein the magenta coupler is incorporated into a silver halide photographic light-sensitive material, and it can any so-called external type photographic process in which the magenta coupler is incorporated into a color developer can be employed is incorporated. For example, when a magenta coupler according to the invention is applied to the photographic Internal type processes of couplers usually in a high boiling point organic solvent having a boiling point of 175 G or higher, for example in butyl phthalate, dioctyl phtha lat, triphenyl phosphate, tricresyl phosphate, phenoxyethanol, diethyl Glycol monophertyl ether, diethoxyethyl phthalate, diethyl laurylamide and dibutyllaurylamide, or in a low-boiling organic solvent, such as. B. ethyl acetate, butyl acetate, Methanol, ethanol, butanol, acetone, ß ~ ethoxyethyl acetate, methoxytriglycol acetate, Dioxane or fluorinated alcohol either alone or in the form of a mixture, dissolved. The resulting solution is mixed with an aqueous gelatin solution that is a surface-active Contains agent, and the mixture is made in a high speed rotary mixer or in a colloid mill treated to produce an emulsified dispersion which is then incorporated directly into a silver halide emulsion. Alternatively the emulsified dispersion obtained in this way is finely divided after solidification (gelling) and then applied a process, for example by washing with water, treated to remove the low-boiling organic solvent therefrom to remove, and then the emulsified dispersion thus treated can be incorporated into a silver halide emulsion. the

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Magenta couplers according to the invention which are soluble in alkali can also be incorporated into a silver halide emulsion by the so-called Fischer dispersion process. In this case, the amount of magenta coupler to be incorporated is generally preferably 10 to 300 g per mol of silver _v this amount but can of course also be varied depending on the type of the magenta coupler used, depending on the intended use and the like.

In a silver halide color photographic light-sensitive material, into which the magenta coupler according to the invention has been incorporated, not only a combination of Couplers for the generation of other dye images such as e.g. Yellow couplers and blue-green couplers, but also various ones Kinds of photographic additives can be used. Examples of yellow couplers, which are preferably used in combination with the invention Magenta couplers which can be used are such as those described in, for example, the French patent 1,291,110, U.S. Patents 2,875,051, 3,408,194 and 3,447,828, in Japanese Patent Publication No. 19 031/1971, in Japanese Patent Laid-Open No. 29 432/1973, 66 834/1973 and 10 736/1974, and Japanese Patent Application Nos. 119 053/1970 and 79 309/1973 are.

Typical examples of cyan couplers, preferably in combination used with the magenta coupler of the present invention are z. Such as those disclosed in U.S. Patents 2,423,730, 2,801,171, 2,895,826 and 2,474,293 in Belgian Patent specification 779 512, in British patent specification 1,084,480,

709828/0869

in the Japanese Offenlegungssehrift Kr. 37 425/1972 and in Japanese Patent Application Nos. 57 829/1973, 69 866/1973, 10 787/1974, 25 .388 / 1974, 37 160/1974, 19 621/1975, 94 294/1975 and 16 056/1974 are examples of colored cyan couplers which can also be used are e.g. B. the one ^ as shown in U.S. Patents 3,034,892 and

2,521,908 ₅ in British Patents 1,255,111 and 1,084,480 and Japanese Patent Application Nos.

55 665/1971, 57 829/1973, 69 866/1973, 16 057/1974, 25 388/1974 and 37 160/1974. By veneering the invention Magenta couplers in combination with the above yellow couplers, cyan couplers and colored cyan couplers a light-sensitive color photographic product is obtained Silver halide material with excellent photographic Properties, especially excellent color rendering. In a photosensitive color photographic Silver halide material in which a Couplers can also be used, if necessary other purple couplers by colored purple couplers in grain ' can be used with “Typical examples of such Matchmakers are those as described in the U.S. laws

3 127 269, 2 600 788, 3 519 429, 3 419 39I ₅ 3 062 653, 3 061 432, 3 005 712, 2 983 608 and 2 801 171, in British Patents 1,342,553 and 937,621, in US Pat German patents sindoSelbst described 2162778 and 1810 464 ₃ in Japanese Patent application Kr ₀ 8433/1969, Japanese Patent publication No. ₀ 60 479/1971 and Japanese Offenlegungssehriften Kr, 29 639/1974 625/1974 123 .and then _s when the magenta coupler according to the invention is used in combination with another magenta coupler or with another colored magenta coupler

709828/0 * 69

is used or when a colored magenta coupler of the present invention is used in combination with other magenta couplers or with other colored magenta couplers or if two or more magenta couplers of the present invention in combination are used with each other, an excellent silver halide color photographic light-sensitive material is obtained

In the silver halide color photographic light-sensitive material, to which the present invention is applicable becomes useful for preparing a photosensitive emulsion a hydrophilic colloid is used, such as e.g. B. gelatin, a gelatin derivative, colloidal albumin, agar, gum arabic, cellulose, Acrylamide, imidized polyacrylamide, casein, a vinyl alcohol polymer, z. B. a vinyl alcohol / vinyl cyanoacetate copolymer, containing a urethane carboxylic acid group or a cyanoacetyl group, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate and polymers produced by polymerization of protein or saturated acylated protein with a vinyl group containing monomer have been. Silver halides usable in the light-sensitive emulsion include e.g. B. silver bromide, silver chloride, Silver iodobromide, silver chloride bromide and silver chloride iodide bromide, optionally in a conventional photographic Silver halide emulsion can be used.

One in the silver halide color photographic light-sensitive material, to which the present invention is applicable, silver halide emulsion used may be any of commonly used various processes

709828/0869

will. Suitable are ζ. B. the procedure as it is in Japanese Patent Publication Kr. 7772/1971, or a method as described in U.S. Patent 2,592,250 is a method of making the so-called reverse emulsion by forming an emulsion, the silver salt particle contains, of which at least one silver salt has a higher solubility than silver bromide, in which case at least a part of these particles is converted into a silver bromide salt or a silver iodobromide salt, or a process for the production of a Lippmann emulsion, the fine-grained Contains silver halide with an average particle diameter of less than 0.1 λι. The silver halide emulsion can also be sensitized using chemical sensitizers, e.g. B. sulfur sensitizers, such as allyl thiocarbamide, thiourea, allyl isocyanate, cystine; active or inalüven selenium sensitizers; Precious metal sensitizers, like gold compounds, e.g. B. potassium chloroaurate, Gold (lll) trichloride, potassium gold (lll) thiocyanate, 2-gold (I) thiabenzothiazole methyl chloride and the like, palladium compounds, such as Ammonium chlorpalladate, sodium chlorpalladite and the like, platinum compounds, such as potassium chloroplatinate, ruthenium compounds, rhodium compounds and iridium compounds or combinations of these sensitizers. In addition to chemical sensitization, the emulsion can also be reduction-sensitized with reducing agents and it can be stabilized by using triazoles, imidazoles, azaindenes, benzothiazolium compounds, Zinc compounds, cadmium compounds, mercaptans or mixtures thereof. Sensitizing agents can be added to the emulsion Compounds of a thioether, quaternary ammonium salt or polyalkylene oxide type are incorporated. In addition, the

709828/0869

Emulsion wetting agent, such as ζ. B. glycerol, dihydroxyalkanes, such as 1,5-pentanediol, esters of an ethylene bisglycolic acid, bis-ethoxydiethylene glycol succinate, fine-grained ones dispersible in water High molecular weight compounds obtained by emulsion polymerization contain plasticizers, agents for improving film properties and the like. Various types of additives such as those used in photography can also be used in the emulsion, e.g. B. film hardener, such as compounds of the ethyleneimine type, dioxane derivatives, oxypolysaccharides, Dicarboxylic acid chlorides and diesters of a methanesulfonic acid, coating auxiliaries such as saponin and sulfosuccinates, Fluorescent brighteners, anti-static agents, anti-discoloration agents and the like can be incorporated.

A blue-sensitive, green-sensitive and red-sensitive emulsion as used in a light-sensitive color photographic silver halide material to which the present invention is applicable can be optically sensitized using suitable sensitizing dyes in order to make these emulsions ^{sensitive to the respectively desired 1} light-sensitivity wavelength ranges do. Various dyes can be used as the sensitizing dye e, and they can be used alone or as a combination of two or more thereof. Examples of sensitizing dyes which can be advantageously used are those shown below.

Examples of sensitizing dyes used in the blue-sensitive Emulsion can be used are e.g. B. see how them

709828/0889

for example in German Patent 929 080, in U.S. Patent 3,149,105 and Japanese Patent Publication No. 14 83O / 1971. Examples of in the sensitizing agent that can be used for the green-sensitive emulsion Dyes are those disclosed, for example, in U.S. Patents 1,939,201, 2,072,908, 2,739,149, and 2,945,763 and in British Patent No. 505,979 which are cyanine dyes, herocyanine dyes or composite cyanine dyes. Typical examples of those that can be used in the red-sensitive emulsion Sensitizing dyes are those cyanine dyes, Merocyanine dyes or compound cyanine dyes as described, for example, in U.S. Patents 2,269,234, 270,3378, 2,442,710, 2,454,629 and 2,776,280. In the green-sensitive emulsion or in the red-sensitive emulsion Such cyanine dyes, merocyanine dyes or composite cyanine dyes can also advantageously be emulsified may be used as described, for example, in U.S. Patents 2,213,995, 2,493,748, and 2,519,001, and in US Pat the German patent specification 929 080 are described.

A silver halide color photographic light-sensitive material with an incorporated magenta coupler according to the invention, if required for special purposes, also a coupler other than that of the present invention Purple coupler included. In this case the coupler should be incorporated into the photographic material should, expediently have the same or as similar a coupling reaction rate as that according to the invention Purple coupler. For example, a colored magenta coupler for masking purposes in the red-sensitive emulsion

709828/0869

sion layer can be incorporated »Furthermore, in any light-sensitive Layer or in an adjacent layer, a suitable coupler can be incorporated, depending on the intended use is selected from couplers which, during development, correspond to the density of the image to be developed can release a development inhibitor; suitable examples of this are those in the British patent 953,454 described various development inhibitor releasing couplers. In a corresponding way you can also development inhibitor releasing compounds which do not contain couplers in place of the development inhibitor releasing couplers can be incorporated into such a layer or layers as indicated above. Typical examples of such compounds are e.g. B. those such as those in German patents 2,362,752 and 2,405,442, in Japanese Patent Publication No. 22 514/1971, in Japanese Patent Laid-Open 77 635/1974 and 36 125/1975 and in Japanese Patent Application Nos. 60411/1974 and 77 510/1974 sindo A development inhibitor that is released during development from such a development inhibitor Coupler or such a development inhibitor releasing compound according to the image density is prevented when in a photosensitive emulsion layer is included, the development corresponding to the image density to produce the so-called internal image effect (Intra-image defect), e.g. B. control of image tint, grain refinement of the image and enhancement the clarity and sharpness of the picture. On the other hand, the development inhibitor diffuses when it has been released, into another layer, the so-called interimage effect

709828/0863

(Interpicture effect), such as ζ. B. a masking effect, a prevention the development of another layer corresponding to the image density in the layer from which the development inhibitor is diffused, and an improvement in color by the inhibition of the development of the other layer in the case of exposure to monochromatic light is. Therefore, the coupler or the compound releasing such a development inhibitor is used for Obtaining two types of picture effects, i. H. the indoor picture effect (Intra-picture effect) and the inter-picture effect (inter-picture effect).

A silver halide color photographic light-sensitive material, which contains a magenta coupler according to the invention, is made by applying a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer and other make-up layers, in each of which, if necessary, various photographic additives, as indicated above, are incorporated, to one Applying carrier subjected to corona discharge treatment, flame treatment or ultraviolet irradiation treatment has been subjected, or by using an adhesive layer or using intermediate layers applies to a carrier. As a carrier can be used with advantage materials such. B. Baryta paper, with polyethylene coated paper, art paper made from polypropylene, a glass plate, a cellulose acetate, cellulose nitrate or polyester film, e.g. B. a film made of polyethylene terephthalate, a Po ^ amidfilm, a polycarbonate film and a Polystyrene film. These carriers are appropriate depending on the

709828/0869

intended use of the photosensitive color photographic Selected silver halide material. According to the invention the desired effect and the desired effect can also be achieved in an advantageous manner if the light-sensitive emulsion layers in any order in a light-sensitive color photographic Silver halide material are arranged that according to the invention should be produced.

A silver halide color photographic light-sensitive material, to which the present invention is applied, color development becomes appropriate after exposure subjected, preferably using a color development process, that on a photosensitive color photographic So-called internal type silver halide material (internal type) is employed, although a color development method of the so-called Outside type (outside type) can be applied. When a color development process of the outside type is employed, for example, a color developer in the present invention can be as follows specified composition can be used:

Color developer

A-amino-S-methyl-N-ethyl-N- (ß-methanesulfonamidoethyl) aniline sulfate 5.0 g

Sodium sulfite. 2.0 g

Benzyl alcohol 3.5 ml

Sodium carbonate 82 g

Potassium bromide 1.0 g

Coupler 0.005 molar equivalent of water to 1 liter

. 709828/0869

On the other hand, when the indoor type color development method is used a color developer for a so-called indoor type color photographic material with the composition specified below are used, however, which preferably contains the coupler as specified in the above-mentioned external type color developer. Depending on the application, the pH value control of the color developer in the developer or other various photographic additives may be used in addition will"

A typical example of color developers for a color photographic So-called indoor type material is a color developer with the following composition:

Color developer ■

A-Amino-3-methyl-N-ethyl-N- (ß-methanesulfonamidoethyl) -

aniline sulfate 5.0 g

Sodium sulfite (anhydrous) 2.0g

Benz3 * l alcohol 3.8 ml

Sodium carbonate (monohydrate) 50 g

Potassium bromide 1.0 g

Potassium hydroxide - 0.55 g

Water ad 1 liter

The color developing agents used in the present invention are preferably primary aromatic amine compounds _t, and · particularly preferred Entwicklerverbindun- 'gen are p-phenylenediamines such as!' !, N-diethyl-p-phenylenediamine, --N-Cj -sulfobutyl-p-phenylenediamine, 2-amino-5-diethyl-

■■ -. . 7098-28 / 0869

amino toluene, p-amino-ii-ethyl-N-ß-hydroxyethylaniline, 4-amino-3-meth3 ^ 1-N-ethyl-lH [3-methanesulfonamidoethyl) aniline, 4-amino-3-methyl- U- ethyl-N- (B-methoxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N-ethyl-N ^ - (β-methoxyethoxy) ethyl laniline and the like, and these compounds can form mineral acid salts or tosyl salts.

An inventive light-sensitive color photographic silver halide material which has been subjected using such a developer of a color development processing can use a suitably selected combination of conventional photograph! See treatment solutions treated \ Examples of such treatments are treatments that can be performed using various treatment solutions , z, 3 _O with a stop solution containing an organic acid, with a stop fixing solution containing fixing components such as organic acids and hypo- or ammonium thiosulfates, with a fixing solution containing a fixing component such as hypo- or ammonium thio contains sulfate _v , with a bleaching solution containing an iron (III) salt of an aminopolycarboxylic acid and a halogenated alkali as the main component, with a bleach-fixing solution containing a fixing component, such as. B. contains an iron (III) salt of an amino acid or ammonium thiosulfate, and with a stabilizing solution, and treatments such as. B. washing with water and drying,

A typical embodiment for a color development process for the light-sensitive color photographic used in the present invention Inside-type negative material is explained in more detail below. 70 9 8 28/0889

5V

Treatment stages

Treatment stage_ (at 38 ° C) color development bleaching

Wash with water fix

Wash with water to stabilize

Handling IuIIg _- S duration

3 min. 15 sec.

6 min. 30 sec,

3 Hin. 15 sec.

6 min. 30 sec,

3 min. 15 sec.

1 min. 30 sec.

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

Color developer

4-Amino-3-methyl ~ N-ethyl-N- (ß-hydroxyethyl) aniline sulfate

Sodium sulfite anhydrous, hydroxylamine hemisulfate Sulfuric acid Potassium carbonate anhydrous Potassium bicarbonate anhydrous Potassium sulfite anhydrous Potassium bromide sodium chloride

Trisodium salt of nitrilotriacetic acid (monohydrate)

Potassium hydroxide water

ad

4.8 g G 0.14 G 1.98 G 0.74 G 28.85 G 3.46 G 5.10 G 1.16 G 0.14 G 1.20 G 1.48 1 liter

Bleach solution

Iron ammonium salt of ethylenediaminetetraacetic acid Diammonium salt of ethylenediaminetetraacetic acid

Ammonium bromide -.

Glacial acetic acid

Water 7898 28/0869

100 g

10 g

150 g

10 ml
ad 1 liter

The pH is adjusted to 6.0 using ammonia water.

Fixing solution

Ammonium thio sulfate. 175, above

Sodium sulfite anhydrous 8.6 g

Sodium metasulfite 2.3 g

Water . ad 1 liter

The pH is adjusted to 6.0 with acetic acid.

Stabilization solution

Formalin (37% aqueous solution) 1.5 ml

Konidax (a product of Konishiroku Photo

Ind. Co., Ltd.) 7.5 ml

Water ad 1 liter

A typical embodiment for a color development process for an inside type positive color photographic light-sensitive material as used in the present invention, e.g. B. the following:

Treatment levels

Treatment level (at 30 C) Duration of treatment

Color development 3 min. 30 sec.

Bleach-fix 1 min. 30 sec.

Wash with water for 2 min.

Stabilize 1 min.

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

709820/0869

-SS '

Color developer

4-Araino-3-methyl-N-ethyl-iJ- (β-sulfonamidoethyi) aniline sulfate " 5.0 g

Benzyl alcohol. 5.0 ml

Sodium hexametaphosphate 2.5 g

Anhydrous liatric sulfite 1.85 g

Sodium bromide 1.4 g

Potassium bromide 0.5 g

Borax 39.1 g water ad 1 liter

The pH is adjusted to 10.30 with sodium hydroxide.

Bleaching fixer solution

Iron amino salt of the acetylene diamine tetraacetic acid 61.0 g

Biammonium salt of ethylenediaminetetraacetic acid 5.0 g

Ammonium thio sulfate 124.5 g

Sodium metabisulfite 13.3 g

Sodium sulfate anhydrous 2.7 g

Water ad 1 liter

Stabilization solution

Glacial acetic acid 20 ml

Water ad 1 liter

The pH is adjusted to 3.5 to 4.0 with sodium acetate.

In addition, color development stages are also applicable which a color development, a bleach-fix and a washing with Include water. A photosensitive color photographic . Silver halide material to which the present invention is applicable can also be used to advantage in an image intensification treatment process used as it is for example

709828/0 * 89

Japanese Patent Publication Mr. 4G 419/1974 and in Japanese patent applications Er. 70 907/1974, 80321/1974 and 102 213/1974.

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

example 1

There were inventive couplers (2), (6), (S), (13) and (17) used. The control couplers (1), (2), (3), (4) and (5) given below were also used for comparison, each having a structure similar to that of the present invention Couplers but had a 1- (2,4,6-trichlorophenyl) group instead of the 1-pentahalophenyl group in each of the formulas the coupler according to the invention had "

Control coupler (1)

I- (2,4,6-Trichlorphenyl) -3-heptadecyl-5-pyrazolon Kontrο1lkupp1er (2) 1- (2j 4,6-Trichlorphenyl) - 3- (2,4- di- ter t. - amylphenoxyacetoamido) 5-pyrazolone
Control coupler (3) 1- (2,4 ₃ 6-trichlorophenyl) r-3- {3- (2,4-di-tert.-amylphenoxy acetamido) - benzamideJ- - 5-pyr a ζ ο ion control coupler (4 ) 1- {2 ₃ 4,6-trichlorophenyl) -3- (2-chloro-5-myristoylamido-aniline) -5-pyrazolone
Control Coupler (5) 1- (2j 4,6-trichlorophenyl) -3- J3- (2 _} 4-di-tert-amylphenoxyacetamido) benzamido ^ -4-acetoxy-5-pyrazolone

TÖ9828 / G889

10 g of each coupler was added to a mixture of 10 ml of tricresyl phosphate and 30 ml of ethyl acetate were added and the Tempex-atur was increased to 60 G to completely disengage the coupler. The resulting solution was mixed with 5 ml of a 10% aqueous solution Manufactured and sold by Alkanol B (alkylnaphthalene sulfonate from Du Pont) and 200 ml of a 5% aqueous Gelatin solution mixed and the mixture was made using a colloid mill, emulsified, a Rupplerdispersioii obtained became.

Subsequently was. the coupler dispersion prepared in this way in 500 g a gelatin silver chlorobromide emulsion (with 20 mol% silver bromide) incorporated and the emulsion obtained was applied in the form of a layer on a baryta paper and then dried In this way, 10 kinds of photosensitive ones were obtained silver halide color photographic materials (samples 1 to 10, each having a stable coating).

Each of the 10 different photosensitive ones obtained in this way Silver halide color photographic materials were identified by an optical gray wedge using a conventional method (Step Wedge) and then exposed using the color development process for color developed a positive color material from the indoor IVp, wherein a sample having a magenta color image formed thereon was obtained. For each sample thus prepared, the yellow color density was determined as the reflection density of an undeveloped area (an unexposed area) using a sensitometer (Type PD-7R manufactured by Konishiroku Photo

709828/0869

• st-

Ind. Co. Ltd.), the .rait equipped with a blue filter V7ar, measured to examine the yellow discoloration (yellow staining) of the non-color developed area ztx. Afterward was after 48 minutes exposure in a Xenon Fade-O-Meter (Type 6 χ HC, manufactured and sold by Tojro Rika Kogyo K.K.) the yellow color reflection density again for each sample of the non-color developed area was measured in the manner described above to determine the increase the yellow discoloration (yellow color stain image xmg) of the non-color-developed Area to be examined as a result of exposure to light. There were also before and after exposure of each sample with the Xenon Fade-O-Heter the magenta dye density a color developed area (an exposed area) of the sample measured by the same sensitometer as above, but equipped with a green filter to prevent discoloration and fading of the colored To examine the dye image as a result of exposure to light. The results thereby obtained are as follows Table II given. In this table is the discoloration-fading of the colored dye image through the residual dye image indicated, expressed by the ratio (%) between the density after exposure and the density before'der Exposure.

09828/0 869

-εν

Table II

Sample used. Yellow discoloration in discoloration-out-

IJr. Coupler to the non-color bleaching in

wrapped area of the dyed {density) dye image before the after the (residual dye · exposure. exposure. image (%))

1 required according to coupler (2) ⁰ ^ ¹ " ⁵ ^ ^{7717 3} ^"

2 control coupler (1) 0.16 0.28 80

3 according to Coupler (6) 0.08 0.12 82

4 control couplers (2) 0.11 0-19 76

5- required according to coupler (S) 0.10. 0.15 80

6 'control coupler (3) 0.13 0.24 72

7 according to the invention coupler (13) 0.12 0.14. 91

8 control coupler (4) 0.15 0.20 86

9 required according to coupler (17) 0.10 0.15 78

10 control couplers (5) 0.1 * 4- 0.22? 1

As can be seen from the above Table II, the samples "), <3), (5), (7) and (9), in which the couplers according to the invention (2), (6), (B) ₃ ( 13) and (17) were used, less yellow discoloration in the non-color developed area and less increase in yellow discoloration as a result of irradiation with light

709828/0889

Coupler very lightfast dye images were obtained, being the magenta ones produced by color development 1 'dye images have less discoloration and fading experienced as a result of exposure to light.

Separately from this, samples were made with magenta colored ones produced thereon Lildern made by doing the above Samples (1) to (10) only one color development each underwent. The samples produced in this way were individually measured for relative sensitivity, the (γ) (expressed by the tan © of the characteristic curve), and the value of the maximum density (reflection density) is determined, where the results given in Table III below were obtained. The following table shows the relative Sensitivity expressed by a helative value which is expressed in Each case was measured under the annalime that sensitivity of the samples in each of which the control coupler were used was 100.

7Ö9828 / Ü8S9

Table III

Sample. j. ■ j.

relative, Em

-'- sensitive ~ ■ " no

..... , - >': .., value of the' ■ maximum γ density

Küppier according to the invention (2) Control coupler (l)

required according to coupler (G) control coupler (2)

required according to coupler (8) control coupler (3)

erf. ,, acc. to coupler (13) Control coupler (4)

Required according to coupling: (17) control coupler (5)

0.96

2.-4-1

2.20

131 ^ • .00 J- 1.91 100 0.92 1.69 134 1.10 2.03 100 0.92 1.69 140 1.12 2.53 100 1.05 2.38 137 1.18 2.50 100 1.07 2.29

As can be seen from Table III above, the using the inventive couplers (2), (6), (3), (13) and (17) produced respective samples (samples (1), (3), (5), (7) and (9)) high values for the relative sensitivity, the γ and the maximum density compared to the control samples (Sample (2), (4), (6), (8) and (10)). It also follows that silver halide color photographic light-sensitive materials, in which the magenta couplers of the invention be used, a high sensitivity of the color

709828/0889

ORIGINAL! INSPECTED

display and magenta dye images with a high density, so that the couplers of the invention have excellent effects as magenta couplers.

Example-2

The inventive couplers (4), (8), (16), (19), (24) and (28) are used. In the same way as in Example 1, magenta couplers were used for control, in which they were l-phenyl-5-pyrazolone compounds which had a similar Structure like the couplers of the invention, the however, a 1- (2,4,6-trichlorophenyl) group instead of the 1-fentahalogenphenyl group in every molecule of the devices of the invention Had couplers. 10 g of each coupler was added to a mixture of 10 ml of tricresyl phosphate and 30 ml of ethyl acetate and the temperature was raised to 50 ° C to completely dissolve the coupler.

The resulting solution was with 10 ml of a 1070igcn aqueous Solution of Alkanol B and 200 ml of 5% gelatin aqueous solution were mixed, and the resulting mixture was emulsified for the production of a coupler dispersion. The coupler dispersion thus produced was then put into 500 g of a highly sensitive Gelatene silver iodide broil negative emulsion (with 5 Ho 1% Silver iodide) incorporated and the resulting emulsion was applied in the form of a layer on a polyester film support and then dried. There were thus obtained 12 kinds of photographic light-sensitive materials (Samples (11) to (22)).

709828/0869

The coupler (4) according to the invention and the control coupler (6) were incorporated into the above highly sensitive silver iodobromide negative emulsion using the procedure described below incorporated. I. E. 10g of the coupler (4) according to the invention and the control coupler (6) were each with 40 ml of 1 η KOH mixed and the temperature was increased to 60 C, to release the coupler. The solution obtained in this way is carried along with it Water made up to 500 ml, then it was the same Way like the above 'dispersion in 500 g of the emulsion incorporated and the emulsion obtained wui'de in the form of a Layer applied to a Polyest.erfilinträger and then dried. -

After exposure using a conventional method through an optical step wedge (gray wedge), the resulting 12 samples were individually color developed using the above-described color development treatment filing for an indoor type color negative to obtain samples with magenta colored images formed thereon. ^;

In the samples obtained in this way with those produced thereon purple colored images were each the absorption maximum, the maximum density (the transmission density) and the three-color density (B / G value), where the in the results given in Table IV below were obtained. The B / G value is expressed by the value of the blue density that was measured at a value for the green density of 1.0 «

70982 8/0869

Tabel

Sample of coupler used

Absorption

functional

niaximum maximum B / G density value

Control coupler (7) according to coupler (16) Control coupler (δ) required according to coupler 09) Control (9)

required according to coupler (24) control coupler (10) required according to coupler (28) Kontr ο1lkupρ1er (11)

inventive coupler (4) Control coupler (6)

inventive coupler (8)

. 2758

2.30

0733

0.39

1.92 0.20 1.57 0.24 2.40 0.16 2.24 0.19 2.88 0.17 2.62 0.19 2.67 0.15 2.40 0.18 2.45 0.16 2.31 0.18

As can be seen from Table IV above, samples (11), (13), (15), (17), (19) and (21) in which the couplers according to the invention have been used, have a high effectiveness compared to the samples in which the control couplers were used as magenta couplers. this

709828/0869

shows that in silver halide color photographic light-sensitive materials using the couplers of the present invention, which consist of 1-pentahalogenophenyl-5-pyrazolone compounds, the amount of the coupler used can be decreased or the amount of the silver halide used can be decreased "that the film thickness of the furpour-red layer in the light-sensitive photographic material obtained can be reduced and that the dye image obtained can also be improved in terms of its sharpness and transparency"

Claims (1)

Claims 1. - Process for developing an image-wise exposed one silver halide color photographic light-sensitive material having a support and at least one silver halide emulsion layer applied thereon, characterized that the development in the presence of a 1-pentanalphenyl-5-pyrazolone compound is carried out,, 2. The method according to claim 1, characterized in that the development in the presence of a primary aromatic Amine developing agent is carried out. 3. The method according to claim 2, characterized in that a p-phenylenediarain is used as the developer compound. 4-, method according to any one of claims 1 to 3, characterized in, that a 1-pentahalogenphenyl-5-pyrazoIon compound is used, which is selected from the compounds of the general formula (I) given below or (II) ^X 1 C.
Il H H -R ₂ X ₂ Il
N
N I. = O i V - C
I. • ^X 5 I. I.
C. -X ₄ ·. (D 709828/0869 IHSPECTEO RC-C- R, -C-C- ^{3 4} 6v ^ v10 1V * k / i5. _N or TO YJ (II) where mean: R ^, R ^ and R ₁ - individually each alkyl, alkenyl, cycloalkyl, substituted alkyl or cycloalkyl, aryl, substituted aryl, alkoxycarbonyl, aryloxycarbonyl, substituted oxy, substituted thio, substituted amino, cycloalkylamino, amido, anilino, substituted anilino, K -Alkylacylamino, N-arylacylamino, N-alkylureido, N-arylureido, N-alkylthioureido, carbonyl or guanidino; Ro is hydrogen or a removable group, R ₂ . a divalent removable group and 1 * 2 '3 »- * · / μ» 5 »6' 7 '8' 9 '" Ήθ' ^ "ΙΊ '12' 13 * Ί4- and X ^ J- individually each halogen. 5. The method according to claim 4, characterized in that the leaving group Rq is a substituted alkyl group, which is selected from diphenylmethyl and triphenylmethyl, the phenyl radical having one or more substituents can, and that the divalent removable group R ^ is methylene or substituted methylene. 6. The method according to claims 1 to 5, characterized in that that the development is carried out in the presence of p-phenylenediamines. 703828/086 « - ⁷ Y- _β Process according to claims 1 to 6, characterized in that a 1-pentahalo-rcenphenyl-5-pyrazole-ion compound is used, which is selected from: O = C Cl Cl Cl ^tc 5 ^H ii Cl HoC Cl IiHCOCH ₃ 709828/0819 Cl H ₂ C
O = C C-NH-
Il -
■ N q
"NE [COCH ₂ O- / N F. F. F. CH _x H
I.
COO-C -C-NHCC
N I.
O = C
\ y Cl ^ NHCOCH Cl I \ r
^ tC ₅ H _{11 2} ο-5- Cl 709828/0869 C-NHCO Cl Cl V // "-N = N-C ■ C-NH O = C N ■ N ^ Cl 1 .Cl NHCOC ₁₃ H ₂₇ Cl ^ / ^ Cl Cl CH 7, O = C N ₁ / Cl Cl he y xi Br N - Ν < Il N-N ' H- -SC C-NHCOC. CH ^ ₁ O = C N Br Br Br Br 709828/0889 Br C-NHCONH Cl NHCOCHO Cl NHCOC ₁₃ H ₂₇ NHCOC ₁₅ H ₂₇ > CH f \ - Cl H ₂ C
O = C, Cl Cl -C-HH- / VN ^X Cl Cl "^ f Cl Cl "CO-CH, 709828/0889 H
ι -C-NH
Μ H-C-
ι Il
N I.
O = C NHCO (CHo) Cl H C- ² I-- O = C Cl Cl C-NH. If Cl ■ ' Cl O = C Cl Cl Cl 1 Cl 'CO-CH ₂ Cl Cl H I -C O = C Cl -C-HE Cl Cl J2 709828/0869 B. Silver halide color photographic light sensitive material having a support and at least one silver halide emulsion coated thereon, thereby characterized in that it is an i-Pentahalonenphenyl-5-pyrazolon- • connection contains. 9. Material according to claim 8, characterized in that it contains an i-pentahalophenyl-5-p.yrazolone compound, which is selected from the group of compounds of the general formula (I) or (II): - C 709828/0869 where mean: E ^ j, R ^ uniRc individually each alkyl, alkenyl, cycloalkyl, substituted alkyl or cycloalkyl, aryl, substituted aryl, alkoxycarbonyl, aryloxyearbonyl, substituted oxy, substituted thio, substituted amino, CyeIoalkylamino, Amido, aniline, substituted aniline, U-alkylacylamino, U-Arylacylaminö, ΪΓ-Alkylureido, Jff-Arylureido, N-Alkylthioureido, Carbamoyl or guanidino; R-hydrogen or a leaving group; R ₁ ^ is a divalent removable group and ■ ^ 1 '^ 2' ^ 3 '^ 4' ^ "5 * ^ 6 * ^ 7 '^"8' ^ 9 * ^ 1O '"^ 11' ^ 12 '^ 13 *
and X ^ c individually each halogen. 709828 / 08B9