DE2437405A1 - MULTI-LAYER COLOR PHOTOGRAPHIC MATERIAL - Google Patents

Description

No. 210, Nakanuma, Minami Ashigara-Shi, Kanagawa, Japan

Multi-layer coloring photographic material

The invention relates to a multilayer color photosensitive Material, especially a multi-layer color photosensitive Material, its color reproducibility, color image sharpness and granularity are improved by using a compound having a particular chemical structure and properties - which selectively use an intermediate layer of color rectification effect guaranteed. The color photosensitive material hereinafter referred to as -color-sensitive.es material.

In general, color photographic material consists of two or more light-sensitive emulsion layer units, each light-sensitive emulsion layer unit having an independent function, i.e. conventional multilayer color photographic materials contain a support and thereon a light-sensitive emulsion layer _{(RL) containing a cyan coupler 8 mainly} is sensitive to red light (visible light of essentially greater wavelength than about 58O mn), a light-sensitive nucleus containing a purple coupler (GL) ₅ which is mainly sensitive to green light (visible light with essentially 500 to 600 nm wavelength) and a photosensitive emulsion layer (BL) containing a yellow coupler which is mainly sensitive to blue light

Bank accounts: H. Aufhäuser, Munich 173533

BLZ 700 306 00 BLZ 700 70010

Postal check account Munich 46212-801 BLZ 70010080

(Light of essentially shorter wavelength than about 500 nra).

In addition, an intermediate layer (ML), a filter (FL) for filtering out the UT range or a special wavelength range, an atrium protective layer (AHL), an intermediate layer with a masking function (ML), a protective layer (PL) and the like are provided so that each of the aforementioned light-sensitive emulsion seal units can develop its own independent function ο

It is known to use colored couplers such as so-called BIR couplers (development inhibitor releasing couplers), DIH hydroquinone derivatives or DIH uncolored couplers in order to improve color reproducibility. These couplers are described in ÜS-PS 2,449,966, 2,455,170, 2,600,733, 2,423,054, 3,148,062, 2,933,603, British Patent No. 1,044,773 and related patents in view of improvements in GE Barr , J _c Ro I'hirtle ά P _c . W _s Vittum "Photographic-Science and Eng.", Vol. ₀ 13. pp. 74-80 (1969h ibid-, S _e 2H - 21? (1969), and also US Pat. No. 3,277,554, 3,620,746, 3 379 529 _f 3,632,345 and 3,622,323

Colored couplers have the serious disadvantage that the couplers themselves are colored. Since the DJ-H couplers themselves form dyes during color development, they are seriously limited in their chemical structure. so that the properties of the dye capable requirem-un- gen for color imaging materials meet su themselves different, and the coupler are subject to terms ilirsr "Using ainer Beschränkujrig (including üsthoils sur removal of dyes from the lichteupfiniiichen Llaterial). In addition, have been dia The 3I.R couplers obtained have the disadvantage that they are always unstable.

The previously known; 8og9nann-: s: i D1R ~ -hydroehinone derivatives

503808/1018 BAO ORIGINAL

have too low a DIR activity in conventional color developers, although they have the advantage of being coated in any kind of photosensitive emulsion and colloidal Layers can be used. In addition, they couple with aromatic primary amines as developers (for example from the p-phenylenediamine series or the, p-aminophenol series) below By-product formation of cyan dye (this is referred to as "abnormal coloration"). We must continue to do so DIR hydroquinone derivatives in a given photosensitive Layer or colloidal layer can be set and protected from light-sensitive halogen silver grains, what generally difficult. On the other hand, DIR hydroquinone couplers were known as DIR (inhibitor releasing Developer) act, and a stable, strong interlayer / interimage effect and the effect to improve the Color image sharpness could not be achieved. It was found, that where hydroquinone derivatives in a multilayered light-sensitive material, insufficiently defined in a special colloidal layer and not protected from light-sensitive silver halide grains, the interlayer / interimage effect, which is essentially take place between the photosensitive emulsion layers can, in general, is seriously degraded.

An object of the invention is to overcome the aforementioned disadvantages and, in particular, to provide a multilayer light-sensitive color photographic material for Available to provide the one-hydroquinone derivative for the intermediate Contains layer color correction (ICG) with high DIR activity and has improved color reproducibility.

Another object of the invention is to provide a new To provide hydroquinone derivative for interlayer color correction that can eliminate the "abnormal coloring" able.

Another object of the invention is to provide a

S0980S / 1019

multilayered light-sensitive color photographic material to make available, which contains a new hydroquinone derivative, which in a special light-sensitive emulsion layer or colloidal layer fixed or set "and protected from light-sensitive silver halide grains can be.

Another object of the invention is to improve the method of using couplers so that the new hydroquinone derivative for interlayer color correction can develop high DIR activity.

Another object of the invention is to provide an improved A method of forming color images in a multilayer color photographic light-sensitive material to provide the the new interlayer / color correction hydroquinone derivative contains.

The aforementioned tasks and other tasks are apparent from the description below.

The foregoing objects are achieved by a multilayer pes light-sensitive color photographic material containing ensure a support and thereon at least two light-sensitive emulsion layers, the images with sufficiently different colors, wherein the light-sensitive material preferably in each of the photosensitive emulsion layers a 2 equiv ent coupler or contains a 4-equivalent anilino magenta coupler, "and at least one of the light-sensitive emulsion layers and colloidal layers contains a hydroquinone derivative or a hydroquinone precursor thereof substituted by a heterocyclomonothio group and an aliphatic monothio group, an aryl monothio group or an aryl oxy group, an aliphatic oxy group contains a ballast group with 3 or more G atoms.

The subject of the invention is thus a multi-layer »

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photosensitive color photographic material that featured is through a support and on top of it at least two photosensitive halide silver emulsion layers, the images ensure with essentially different color tones, the photosensitive material 2-equivalent coupler and / or 4-equivalent anilinopyrazolone couplers and at least one of the photosensitive halide silver emulsion layers or a colloidal layer of the light-sensitive material is a hydroquinone derivative or a. Hydroquinone precursor, substituted by a HeterocycOommoiMorest and an Aliphatomonothioiest ^ an aryl monothio radical, an aliphatooxy radical,. suitable aryloxy radical or a heterocyelooxy radical, and with one Ballast group of .. 3 or more carbon atoms.

In the case of the intermediate layer / color correction (ICC) hydroquinone derivatives used according to the invention are compounds that are a diffusible development retarder in the Release color development according to image development, selectively the color development of an adjacent photosensitive Delay emulsion layer and, as a result, an interlayer / color correction effect guarantee. The hydroquinone derivatives or precursors thereof are preferably involved to those compounds which carry a heterocyclic monothio radical which can be a development retarder, and those with an aliphatic thio radical or an aliphatic Oxy radical with 8 or more carbon atoms is substituted, which at the same time serves as ballast groups' »Preferably acts they are compounds. "of the general formula I A · ·

'S-Z'

(D

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in which A and A ¹ each represent a hydrogen atom or a radical which can be eliminated by a base (for example an alkoxycarbonyl radical, an acyl radical or an Alko3 & lyl radical ) _t - and & t _m ±% r or Q to form a ring (for example an oxathiol ring) can combine P, Q or R each a hydrogen atom, an alkyl radical (for example with 1 to 32 carbon atoms, for example a methyl, ethyl, 1 >> 3i3-tetramethylbutyl or n-pentadecyl group), an aryl radical (for example a phenyl or p-tolyl group), a -SY radical / where Y is an alkyl radical (for example with 1 to 18 carbon atoms, for example a 2-ethylhexyl, n-dodecyl, hexadecyl- , n-octadecyl, hydroxycarbonylmethyl, ethoxycarbonylmethyl or 2-hydroxyethyl group), or an aryl radical (for example a phenyl group) 7, a hydroxyl group, a halogen atom, the radical -SZ, an alkoxy radical or an aryloxy radical (for example the radical - 0-Y, in which Y has the aforementioned meaning), or a heter mean ocyclic ring; Z represents a heterocyclic radical which, photographically, is essentially TrrerlYvorlregT7 \ m * d, in particular a tetrazolyl radical (for example a 1-phenyltetrazolyl group), a triazolyl radical (for example a 4-phenyl-1,2,4-triazol-5-yl - or 3-n-pentyl-4-phenyl-1,2,4-triazol-5-yl group), a thiadiazolyl radical (for example a 2-methylthio-1,3,4-thiadiazol-5-yl or 2- Amino-1,3> 4-thiadiazol-5-yl group), an oxadiazolyl group (for example a 2-phenyl-1,3 »4-oxadiazol-5-yl group), a tetrazaindenyl group (for example a 6-methyl-1, 3,3a-7-tetrazainden-4-yl or 6-n-nonyl-1,3,3a, 7-tetrazainden-4-yl group), an oxazolyl radical (for example a benzoxazol-2-yl group) or a thiazolyl radical ( for example a benzothiazol-2-yl group). In particular, of P, Q and R ^, R can mean the radical -SZ. A ballast group is contained in the chemical structure of the molecule, preferably in the chemical structure of P, Q or R, and ■ at least one of the radicals P, Q and R represents the radical YS-.

In the case of the ICC hydroquinone derivatives according to the invention ballast groups used is an aliphatic one

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Remainder with about 8 "to 32 C-atoms for the ballast generation.

A first feature of the hydroquinone derivatives of the invention and in particular the compounds of general formula I is in

. or the Y-S residue. In general, the reduction characteristic is DIR activity of the hydroquinone derivatives by introducing of a Z-S residue. On the other hand, the introduction of a Y-S radical (Y is preferably an aliphatic Rest) to an increase in the reducing property ir the ■ DIR activity of the hydroquinone derivatives.

A second feature of the invention is that if the ballast group, preferably Y-Re.st, is an aliphatic radical with about 8 or more carbon atoms, the so-called "abnormal coloration" is prevented and ballast properties are guaranteed can be. On the other hand, the "abnormal coloring" due to the hydroquinone derivative can be prevented by using a substituent in 3 or 4 positions. _jf

A third characteristic is that the affinity of the hydroquinone derivative to organic solvents, couplers, hydroquinone derivatives, UV absorbers and the like, which are the same - used early, can be increased by introducing a Y-S residue.

A fourth feature is that the hydroquinone derivatives of the invention is comparatively easily synthesized and manufactured can be.

Further features of the invention emerge from the following Description. .

Some examples of compounds of the invention are given below specified. ,.

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Connection no.

(1) 2-n-dodecylthio-5- (1'-phenyltetrazole-5 ¹ -

ylthio) hydroquinone; P. 131 to 132 ⁰ C

(2) 2-n-octadecylthio-5- (i'-phenyltetrazole-5-

ylthio) hydroquinone; F. 132 to 133 ⁰ O

(3) 2-n-hexadecylthio-5- (1'-phenyltetrazole-5-

yithio) hydroquinone; P. 129 to 131 ⁰ C

(4) 2- ^ 2 », 5'-dihydroxy-6 '- (1" -phenyltetrazole-5 "-

ylthio) -4 ^f - (1 '! ^f , 1 "*, 3"', 3 " ^f -tetramethylbutyl) 7-phenylthiopzoic acid dec. 196 ⁰ C

(5) 2- / 2 », 5 ^f -dihydroxy-6 '- (i" -phenyltetrazole-5 "-

ylthio) -3 '- (1 "', 1"', 3 ^Ift , 3 "' -tetramethylbutylji / -phenylthiobenzoic acid; dec. 182 to 183 ° C

(6) 2- (1'-phenyltetrazol-5'-ylthio) -3-phenylthio-6-

(1 ", 1", 3 ", 3" -tetramethylbutyl) hydroquinone;

P. 147 ⁰ C

(7) 2- (1-phenyltetrazol-5'-yithio) -3-phenylthi0-5-

(1 ", 1", 3 ", 3" -tetraniethylbutyl) -hydroquinone;

P. 148 to 149 ⁰ C

(8) 2,5-dihydroxy-5- (1'-phenyltetrazol-5 * -yithio) -

4- (1 ", 1", 3 ", 3 ^'r -tetranethylbutyl) -phenylthioessigsäurej P. 133 ⁰ C.

(9) 2- / 2 , 5'-dihydroxy-3 ^f -n-hexadecylthio-6 »- (1» -

phenyltetrazol-5 "-yithio) / - phenylthiobenzoic acid; dec. 143 to 145 ⁰ C

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(10), 2-n-hexadecylthio-5- (1'-phenyltetrazole-S ¹ -

ylthio) ~ 6-phenylthiohydroquinone F. 94 "to 96 ⁰ C

(11) 4- (1 * -Phenyltetrazol-5 '-ylthio) -5-hydroxy-7-

(1 ", 1", 3 ", 3" -tetremethylbutyl) -benzoxathiol-2-one; F. Ί76 ^{0 C;}

(12) 2- / 2 ^l , 5'-Diiiydroxy-6 ^t - (1 ^tl -piienyltetrazol-5 ^tl -

ylthio) -3 '- (1 "', 1". ·, 3 "', 3'" -tetramethylbutyl_) 7-phenylthiobenzoate; F. 106 to 107 ⁰ G

(13) 2- / 2 ^f , 5 '-dihydroxy-6 · - (1 ^u -ph.enyltetrazol-5 "-

ylthio) -4 '- (1 "'., 1"', 3 "', 3 ^1M -tetramethylbutyl) / - phenylthiobenzoic acid methyl ester; dec. 197 ⁰ C

(14) 2- / 2 », 5'-dihydroxy-3 '-rn-pentadecylthio-ö · - (1" -

phenyl 1 e1; razol-5 "-ylthio_) 7-phenylthiobenzoesäureriethylester dec 93 to 95 ⁰ C.

(15) 2-n-Octyloxycarbonylmethylthio-6-phenyl ~ 3- (1'-

phenyltefrazol-5'-ylthio) hydroquinone; Decomp. 113 to 115 ⁰ C

(16) 2-p-nitrophenylthio-3- (1 '-pheiiyltetrazol-5' -

ylthio) -6- (1 ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone ^ F. 173 "to 174 ^° C

(17) 2- (2'-methylthio-1 », 3 ¹ , 4'-thiadia2; ol-5 ^f -

ylthio) -6- (1 ", 1", 3'S 3 "-tetraraethylbutyl) -hj'-drochinonj F. 163 ⁰ C.

(13.) '■ 3- (2'-l. ^F ίethylthio-1', 3 ^t , 4 ^s -ΐhiadiazole-5 ^l -

io) -6- (1 ^i!, 1 ", 3", 3 "-tetramethylbutyl) -

hydroquinone; F. 220 ⁰ G '

'B 0980-8 / 10 1.9

(19) 2,3-bis (2'-methylthio-1 ', 3 *, 4 ^? -Thiadiazole-5-

ylthio) -6- (1 ", 1", 3 ", 3 ⁿ tetramethylbutyl) -hyarochinon; F. 202 ⁰ C.

(20) 2- (3'-n-pentyl-4'-phenyl-1, 2, 4 ^f -triazole-5'-

ylthio) -5- (1 ", 1", 3 ", 3" -tetramethylbutyl) hydroquinone; F. 193 ⁰ C

(21) 2- (6 ^l -I.Iethyl-1 ^I , 3 ', 3a · _f 7'-tetrazainden-4 ^l -

ylthio) -6- (1st ", 1", 3 ", 3 ^t! -tetra: aethylbutyl) -hydrochmone; m.p. 223 ⁰ G

(22). 2,3-bis- (6'-methyl-1 ', 3 », 3a ·, 7 · -tetrazaindeIl-

iΌ) -6- (1 ", 1", 3 ", 3 ^tf -tetramethylbutyl) -

-hyo.ro chinone; F. 215 ⁰ G

(23) 2-n-hexadecylthio-5- (2'-iaethvithio-1 ', 3' _y 4 ^f -

thiadiazol-5 '' - ylthio) hydroquinone; F. 120 ⁰ C.

(24) 2- / 2 ', 5' -dihydrox./-6· - (2 "-raethylthio-1", 3 ", 4" -

thiadiazol-5 "-ylthio) -3 '- (1 ^irt , V", 3 "', 3"'-

te traniethylbutyl27 ~ phenylthiobenzoic acid; F. 193 to 194 ⁰ C

(25) 2- (2 '~ Ainino-1', 3 ^f , 4 '™ thiadiazol-5'-ylthio) -5-

(1 ", 1", 3 ", 3" -tetramethylbutyl) hydroquinone; F. 243 ⁰ G

(26) ' 2- / 2 ', 5 '~ dihydrox: / - 6 «- (2" -anino-1 ", 3", 4 "-

thiadiaaol »5" -ylthio) -5- (1 ^ltl , 1 "', 3"', 3 ^sc -

tetr ame t hy lbiit y 1) / - phenyl t hi ob en ζ ο e acid e; P. 203 ⁰ G

(27) 2- (2 »-amino-1 ', 3 ^f , 4 ^? - tMadiazol-5 ^f -ylthio) -3-

n-aoecylthio-6-C 1 ", 1 ^i!, 3", 3 "~ tetramethylbutyl) hydroquinone; P. 127 ⁰ G

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(28) 2- (6'-tert-butyl-1, ^^ ajT

-6- (1 ", 1", 3 ", 3" -tetraraethylbutyl) -

hydroquinone; P, 144 ^° C

(29) 2- (6'-n-Nonyl-1 ', 3 ⁿ , 3a ^f , 7 ^t -tetrazainden-4 ^l -

ylthio) -6- (1 ", 1", 3 ", 3" -tetramethylbutyl) -hydroquinone; F. 16.2 to 163 ⁰ C

(30) 2- (4 ^l -phenyl-1 ^t , 2 », 4'-tria25ol-5 ^l -ylthio) -2-

(1 " i 1" j J "j 3" -tetrainethylbutyl) hydroquinone; F. 230 ⁰ O '"

(31) 2- (2 »-Phenyl-1», i ^f , 4'-oxadiazol-5 ~ ylthio) -5-

(1 ", 1", 3 ", 3" -tetraiaethylbutyl) -hydroquinone; F. 190. ⁰ C

(32) 2- (1V-phenyltetrazol-5'-ylthio) -5-n-octyloxy-

carbonylmethylthiohydroquinone

(33) 2-tert, -dodecylthio-5- (1'-phenyltetrazole-5 ¹ -

ylthiο) hydroquinone

(34) 2- (Benzoxazol-2'-ylthio) -5-n-octadecylhydro-

chinone

(35) 2- (2'Methylphenylthio) -6-n-octadecylthio-3- (1 '

phenyltetrazol-5 "-ylthio) hydroquinone

(36) ■ 2-n-Octyloxyce, rbonylmethylthip-3- (1'-phenyl-

tetrazol-S'-yithioJ-ö-p-tolylhydroquinone *

(37). 2-ethoxycarbonylmethylthio-6-n-hexadecylthio-

3- (1 ^L -phenyltetrazol-5 -ylthio ^t) hydroquinone 'and

(38) - 2-Phenylthio-3- (1'-phenyltetrazol-5'-ylthio) -

S-n-dodecylthiohydroquinone.

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The compounds of general formula I can according to the in

i.e., the methods described in U.S. Patent 3,379,529, by addition. reaction of a mercapto compound with a benzoquinone will.

The general manufacturing process is specific in the following Examples described. Unless otherwise stated, all parts, percentages, proportions and others refer to Information on weight.

Production example 1

316 g of 2-n-hexadecylthio-p-benzoquinone are dissolved in 1 liter of methanol dissolved while stirring and cooling with ice. The mixture is then gradually added dropwise with a solution, obtained by dissolving 155 g of i-phenyl-5-mercaptotetrazole in 800 ml of methanol has been produced. After the dropwise addition, the mixture is stirred for 3 hours while cooling with ice. After 8 hours at room temperature has stirred, crystals separate out.

The crystals thus formed are separated by filtration and recrystallized from benzene. One obtains 350 g of 2-n-hexadecylthio-5 ~ (1'-phenyl-tetrazol-5-yl-thio) hydroquinone, melting at 129 to 131 ⁰ C.

Production Example 2 (Compound No. 6)

15 g of 2- (ί'-phenyltetrazol-5-yl-thio) -6- (1 ", 1", 3 ", 3" -tetrame- 'thylbutyl) -p-benzoquinone are added to 150 ml of methanol with stirring and cooling added with ice. A solution prepared by dissolving 4.5 g of thiophenol in 25 ml of methanol is then added dropwise to the mixture. After the dropwise addition, the mixture is stirred for 3 hours while cooling with ice. After the crystals thus formed have been separated off by filtration, it is recrystallized from a hexane / ethyl acetate mixture. 7.5 g are obtained in this way

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2- (1 x -Phenyltetrazol-5'-yl-thio) -3-phenylthio-6- (1 ", 1", 3 ", 3" tetramethylbutyl) hydroquinone, mp 147 ⁰ C.

Production Example 3 (Compound No. 20)

13 g of 3-mercapto-5-n-pentyl-4-phenyl-1,2,4-triazole are "stirred in 200 ml of!.! Ethanol while cooling with ice. To this, 12 g of 2- (1 ×, 1 ', 3', 3'-Tetramethylbutyl) ~ p-benzochino ■;: L. After the addition, the mixture is stirred for 2 hours while cooling with ice and then left to stand overnight at room temperature (about 20 to 30 ^° C.) After the methanol has been removed under reduced pressure, diethyl ether is added to the residue, and the crystals which have separated out are separated off by filtration and crystallized from ethyl acetate.

!, lan receives 5 g of 2- (3 ^t -n-peiityl-4'-phenyl-1, 2,4-triazol-5'-ylthio) -5- (i ", 1", 3 ", 3" - tetramethylbutyl) hydroquinone from F.

198 ⁰ C. '*

The couplers which can be used according to the invention are 4- or 2-equivalent couplers, in particular ballast groups bearing couplers used as a photographic element. It has been found that the combined use the ICC hydroquinone derivative of the invention and a coupler with a specific chemical structure leads to a particularly strong "DIR effect". The invention is based on this Discovery.

Couplers preferred according to the invention have the general formulas II, III, Iv, V and VI, e.g.

(II)

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in which R _{1 is} an alkyl radical from the group consisting of primary, secondary and tertiary alkyl radicals (for example an!.! ethyl, propyl, n-butyl, tert-butyl, hexyl, 2-hydroxyethyl or 2-phenylethyl group ), an alkoxy group (for example a methoxy, ethoxy or benzyloxy group), an aryloxy group (for example a phenoxy group), an aryl group, a heterocyclic ring (for example a quinolinyl, pyridyl, benzofuranyl or oxazolyl group), an amino group (for example a methylamino, diethylamino, dibutylamino, phenylamino, tolylamino, 4 - ('3-sulfobenzaniino) anilino, 2-chloro-4-acylaminoanilino, 2-chloro-5-alkoxycarbonylc / niliro- , 2-trifluoromethylphenylamino or cycloalkylamino group), a carboniamido group (for example an alkylcarbonamido group such as an ethyl carbonamido group, an aryl carbonamido group, a heterocyclic carbonamido group, for example a benzothiasolylcarbonainido group, a sulfonamido group, or a heterocyclic suIamido group), a uronocyclic sulfonamido group m is, for example, an alkylureido radical, an arylureido radical or a heterocyclic ureido radical); R _? an aryl radical (for example a naphthol, phenyl, 2,4,6-trichlorophenyl, 2-chloro-4,6-dimethylphenyl, 2,6-dichloro-4-methoxyphenyl, 4-methylphenyl, 4- Acylaminophenyl, 4-alkylaminophenyl, 4-trichloromethylphenyl or 3, 5 ~ di "bromophenyl group), a heterocyclic radical (for example a benzofuranyl, naphthoxazolyl or quinolinyl group) * an alkyl radical from the group of primary, secondary and tertiary alkyl radicals ( for example a methyl, ethyl, tert-butyl or benzyl group); Z ^ is a radical which can be eliminated during color development, for example an acyloxy radical, an aryloxy radical, a halogen atom, a thiocyanate group, a disubstituted one. Amino group, an amido group (for example an alkylsulfonamido, arylsulfonaraido-j, heterocyclic sulfonamido, alkylcarbonamido or arylcarbonamido group), an arylosycarbonyloxy group, an alkoxycarbonyloxy group, a ben-sotriazolyl group, a heterocyclic group, an indazolyl group le are described in ÜS-PS 3 227 550, 3 252 924, 3 311 476, and 3 419 391, DT-OS 2 015 367, as well as US-PA 471 639), or otherwise Z- is a residue, at the

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To release a development retarder (attenuator) capable, for example, of an aryl monothio radical (for example a 2-aminophenylthio or 2-hydroxycarbonylphenylthio group), a heterocyclic monothio radical (for example a tetrazolyl, Triazinyl, iriazolyl, gxazolyl, oxadiazolyl, di.azolyl, thiazyl or thiadiazolyl group), a heterocyclic group Imido radical (for example a 1-benzotriazolyl, 1-indazolyl or 2-benzotriazolyl group) (for example can those radicals or groups are used that are described in US Pat 3 148 062, 3 227 554, 3 615 506 and 3 701 783 are described) is.

If Z- in the above formula is a hydrogen atom, R _{1 represents} an amino group. Such compounds are so-called 4-equivalent couplers which show a particularly strong “BIR effect”. This is an effect that is so far completely unknown. Preferred examples of these compounds have the general formula III

(III)

509 808/1019

in the R, an aryl radical (for example a phenyl, 2-chlorophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2-bromophenyl , 2-cyanoplienyl-, 4-cyanophenyl-, 3-nitrophenyl-, 4-nitrophenyl-, 4-methylphenyl-, 2,6-dimethylphenyl-, 4-butylphenyl-, 2-trifluoromethylphenyl-, 2-ethoxyphenyl-, 4- Phenylphenyl-, 4-Phenoxyphenyl-, N-Methy 1- benzamidophenyl-, N, N-Dipheirylc arbamylphenyl-, N, N-Diphenylsulfanylphenyl-, N, IT-Di "butylsu.lfamylphenyl-, Phenyl-N-Methylsulfonaiiidophenyl- , 2-i-diethyl-5-nitrophen.yl-, 2-chloro-5-cyanophenyl-, 5-chloro-2-methylphenyl-, 2,6-dichloro-4-methylphenyl-, 2,4-chloro -6-methylene-1-phenyl-, 2-chloro-4,6-dimethylphenyl-, 2,6-dichloro-4-methoxyphenyl-, 2,6-dichloro-4-nitrophenyl-, 2,4,6-trimethyl-3 -nitrophenyl or 2,4,6-trinethyl-3 ~ substituted aminoplienyl group) or a heterocyclic ring (for example a 2-thiazolyl, 2-benzothiazolyl, 2-benzoxazolyl, 2-oxazolyl, 2-iniidazolyl or 2-benziraidazolyl group, or a similar group cher 5- or 6- £ lieäri; ^; ; it is heterocyclic radical); Zp represents a V / ass only off atom or the same eliminable residue as defined _{for Z 1;} B represents a ballast group (a residue having from about 3 to about 32 carbon atoms-i to make the coupler diffusible, specific examples are given below); and X is an alkoxy radical with 1 to 13 carbon atoms or a halogen atom (for example a fluorine, chlorine or bromine atom),

Rh-CO-CH-CO-NH-R ₅

((IV)

in the R. an alkyl radical from the group primary, secondary and tertiary alkyl radicals (for example a tert-biityl, 1,1-diraethylpropyl or 1,1-dimethyl-1-methoxyphenoxymethyl group), an aryl group (for example a phenyl group, an alkylphenyl group, like 'a 3-i'Iethylphenyl- or ^ -Cttsdecylphenylgruppe, an alkoxyphenyl group such as a 2-iethoxyphenyl or 4-methoxyphenyl group, a halophenyl group, 2-halo-5-alkamidophenyl group, a 2-chloro-5- / oC - (2, 4-di-tert.-a.Myl-

509808/1019 ß ^AD original

phenoxy) -butyramido7-phenyl, 2-methoxy-S-alkaliidophenyl or 2-chloro-5 ^ -sulfonamidophenyl group); R ₁ - an aryl radical (for example a 2-chlorophenyl-, Z-halo-s-alkamidophenyl-, 2-chloro-5- / ~ oC - (2,4-di-tert-amylphenoxy) -acetamido7-pkenyl -, 2-chloro-5- (4-methylphenylsulfonamidο) -phenyl- 'or 2-methoxy-5- (2,4-di-tert-amylphenoxy) -acetammophenyl group) represents; and Z-> is a radical that can be eliminated during the color development, for example a halogen atom (especially a fluorine atom), an acyloxy radical, aryloxy radical, heteroaromatic carbonyl radical, a hydroxyl group, sulfimido group, alkylsulfoxy radical, arylsulfioxoxy radical, phthaiimido group, .yl group, dioxocazolidinyl group, indazolyl group or dioxothiazolidinyl group. These examples are described in US-PS 3227550, 3253924 _S 3277155, 3265506, 3403194, 3415652, French Patent No. 1,411,384, British Patents 944,490, 1,040,710 and 1 11S 028, as well as DT-OS 2 057 941, 2 163 312, 2 213 46 and 2 219. Z-. can also mean a radical that is capable of releasing a development retarder (reducer), for example an aryl monothio radical (for example a phenylthio or 2-carboxyphenylthio group), a heterocyclic thio radicalj a 1-benzotriazole or i-beiizodiazole group, and in particular those in the US -PA 454 525 described radicals "or groups ^

OH ■

(V)

(VI)

509808/1019

in which Eg is a substituent generally used for cyan couplers, for example a carbamyl group (e.g. an alkylcarbamyl group, an arylcarbamyl group such as a phenylcarbamyl group, a heterocyclic carbamyl group such as a beiizothiazolylcarbamyl group, a sulfamyl group (e.g. an alkylsulfamyl group) Arylsulfamyl group, such as a phenylsulfamyl group or a heterocyclic sulfamyl group), an alkoxycarbonyl or aryloxycarbonyl group; R _{7 is} an alkyl group, aryl group, heterocyclic group, an amino group (for example an amino, alkylamino or arylamino group), a carbonamido group (for example an alkylcarbonamido or arylcarbonamido group), a sulfamido group, a sulfamyl group (for example an alkylsulfamyl or arylsulfamyl group ), or a carbamyl group; R ^, R _q and R. ,,. each have a meaning as _{defined under R 7} , or represent a halogen atom or an alkoxy radical; and Z, is a group which can be eliminated upon color development, i.e. a group as defined by Z ₁ , or a halogenato: .i (for example a chlorine, bromine or iodine atom), an indazolyl, cyclic Imido-j Acyloxy ™, aryloxy, alkoxy, sulfo, arylazo or heterocyclic azo groups (examples of these are in US-PS 2,423,730, 3,227,550 and 3,311,476, as well as GB-PS 1 Ο84 and 1 165 563).

The couplers of the invention can also be colored couplers. Such couplers are described, for example, in U.S. Patents 2 983 608, 3 005 712 and 3 034-392, GB-PS 936 621, 1,269,073 ;; 536 211 and 627 814, as well as PR-PS 930 372, 1 091 903s 1 257 837, 1 333 303 and 2 015 649.

The couplers used according to the invention are preferably provided with ballast groups. The purpose of the couplers is _{: a} hydrophobic radical with about 3 to 32 carbon atoms that is built into the coupler molecule. Such a remainder is called a ballast group (reads more diffusion-proof). The ballast group can be directly or with the skeletal structure of the coupler

509808/1019

2437A05

via a bond, for example an imino, ether, carbonaniido, sulfonamido, ureido, ester, iinido, carbamoyl or sulfamoyl group. ^/ . '

Several specific examples of ballast groups are given in the specific Examples of the couplers according to the invention are described.

Specific examples of suitable ballast groups are: ■

(I) alkyl and alkenyl radicals, such as

-CHj-CH (C ₂ Hs) ₂ , -C ₁₂ H ₂₅ . -C ₁₆ H ₃₃ , -C ₁₇ H ₃₃ .

(II) Alkox: ralkj, ^r lrecte ,, v / ie

- (CH ₂ ) 3-O- (CH ₂ ) ₇ CH ₃ , - (CH ₂ ) 3 OCH ₂ -CH- (CH ₂ ) 8-CH ₃ j

C ₂ H ₅

(described in the published JA-PA 27 536/64?

(III) alkaryl radicals, such as

C ₉ H ₁₉ , -U V

(IV) alkylaryloxyalkyl radicals, v / ie

-CH ₂ O

CsHii (t),

CsHn (t)

-CH ₂ O

C ₁₅ H ₃₁ (n),

509808/1019

IAD OFUQiNAL

-CH ₂ O

C ₅ HuCt),

CH ₃ -C-CH ₃

CH ₂ -Ci ₁ H ₉ (t)

C ₅ HnCt)

(V) Acylamido alkyls, such as

/ COC ₁₅ H ₃ I.

-CH ₂ CH ₂ N

-CH ₂ CH ₂ N

COC13Η2 7 C3H7

-CH ₂ Ch ₂ NHCOCH ₂ CH ₂ N

COC ₁₃ H ₂₇ C ₃ H ₇

(described in UvS-PS 3 333 344 md 3 418 129), (VI) alkoxyaryl radicals and aryloxyaryl radicals, such as

(VLi) fcubstituenten with a long-chain aliphatic, alkyl or alkenyl radical vciä. a water-solubilizing carboxyl or ijulfogrivope, such as

-CH-CH = CH-C ₁₆ H ₃₃ , -CH-C ₁₆ H ₃₃ CH ₂ COOH SO ₃ H

509808/1019

(VIII) Ester-substituted alkyl radicals, such as

-CH-Ci ₆ H ₃₃ Cn) ₃ -CH ₂ -CH ₂ -COOCi ₂ H ₂₅ Cn)

COOC ₂ Hs j

(IX) aryl or heterocyclo-substituted alkyl radicals, such as

-CH ₂ -CH ₂ -C 'V) -NHCOCH ₂ CH-Ci ₈ H 3 7 (η),

COOCH ₃

-CH ₂ CH ₂

(X) arylox / all-ioxycarbonylsubstituted aryl radicals, such as

C ₈ H ₁₁ Ct) CH ₃ X

/ ^) - COOCH ₂ CO
CH ₃

Especially when used in combination with an ICC hydroquinone derivative of the general formula I show couplers of the general Formulas II, IV, V and VI have a particularly strong "DIR effect", compared to 4-equivalent couplers with corresponding chemical structures. However, the mechanism is so far not yet fully clarified. Without intending to imply any limitation, it is assumed that the oxidized color developers, since it does not oxidize a reducing dye of a leuco form in the coupling between the 2-equivalent coupler and an aromatic primary amine derivative to form a dye require the exchange oxydate with the ICC hydroquinones accelerate. Also the mechanism, like that by the

509808/1019

BATH ORIGINAL

general formula III reproduced coupler a particularly ■ show a pronounced "DIR effect" is not known at present.

Specific examples of couplers suitable for the invention are given below. However, the invention is of course not limited to these couplers.

Yellow coupler

/ Y-17 <? C - (2,4-Dioxo-5, 5-dimethylo3cazolidine2 / l) - 4L -pivaloyl-2-chloro-5 -, /% £ _ - (2,4-di-tert. -aniylphenoxy) -butyraniido7-acetanilide

/ Y-2 /. oC- (4-Carboxy'phenoxy) - oL -pivaloyl ~ 2-chloro-5- / ~ V- - (2,4-di-tert-amylphenoxy) -butyramido7-acetanilide

/ Y-37 oL- / 3- ( 1-Benzyl-2,4-dioxo) -hydantoin / - oC -pivaloyl-2-methoxy-5- / ~ o <- (2,4-di-tert.-A : nylphenoxy) -butyraniido7- acetanilide

A-47 ^ -Benzoyl- o ^ - (2-benzothiazolylthio) -4 - // H- ( / ~ -phenyl propyl) -N- (4-tolyl) -sulfamyl7-acetanilide

/ 7-57 i ^ - /! - (1-Benzyl-2,4-dioxo) -hydantoin7- oL -pivaloyl-2-chloro-5- / ~ oC - (2,4-di-tert-anylphenoxy) -butyramido7-acetanilide

/ Y-67 oL-Benzoyl- oC - (5- or 6-bromo-1-benzotriazolyl) -5- / ^r "o <(2,4-di-tert-amylphenoxy) -propionamido7-2-chloroacetanilide

/Ί.-Ί7 oC- (4-Iethoxybenzoyl) - ÖC- / 3- (2,4-dioxohydantoin7-2-chloro-5 - / "" p4 - (2,4-di-tert-aniylpheiioxyj- butyramido / acetanilide

/ 7-37 ö ^ -Octadecanoyl- oC- (5- or b-broin-i-benzotriazolyl) -2,5-dimethox.yacetanilide

509808/1019

BAD ORiQlNAL

/ 7-97 ei - (4-Methoxybenzoyl ) -p ^ - (3, 5-dioxoraorpholino ) -5-f

(2,4-di-tert-amylphenox _< y -) - TDutyramido7-2-cliloraGetanilid

Purple coupler

/ UY / 1 - (2,4,6-trichlorophenyl) -3- _< / 3 - ^ - (2,4-cLi-tert-amylphenoxy) -acetarnido j-benzamido7-4-aetoxy-5-pyrazolone

/ 1-2 / 1 - (2,4,6-trichloropienyl) -3-hexadecanainido-4- (4-hydroxyphenyl) azo-5-pyrazolone

/ M-37 1- (2,4,6-Trichloropienyl) -3- (2-chloro-5-tridecanoylamino) -aniliiio-5-pyrazolone

/ 13-47 "'- (2, 4,6-Triclilorplienyl) -3- (2-clilor-5-tetradecylox2 / -car- ■ bonyl) -a: iiliiio-4- ( 1-naphtliylazo) -5-p.yrazoloii

/ il-57 1 - (2,4-dichloro-6-methoxyplienyL) ~ 3- / r2-chloro-5-tridecaiioyl amino) -anil ir_ ο 7- 4-b en ζ; / l ο xy car b onyl ο x; f- 5 — ρ yr a ζ ο 1 on

/ Π-6 / 1- / 4- {oC- (2,4-Di-tert.-aniylplieiiox3 _i i ") - acetaaiido j -phenyl7-3- (4-Hiethoxyanilino) -4- (5- or 6- bromo ~ 1-benzotriazolyl) ~ 5-pyrazolone

/ EI-77 1- (2,4,6-triclorophenyl) -3 - / _ ^/ 3- - ^ (2,4-di-tert-amylp] ienoxy) -acetamido? -benzal "Jlido7-4-piperidino-5-p.yrazolone

/ M-37 1- (2, 4, 6-trichlorophenyl) -3- / 3- (2, <-di-tert.-amylplien.oxyacetanido) -benzaniido7-4-ethoxycarbonyloxy-5-pyrazolone

. / Π-9/1 -Benzyl-3- / 2-chloro-5- (tetradecananido) -8 ^ 11111107-4- (5- or 6-meth; 7l-1-beiizotriazolyl) -5-pyrazoloii

Fi-107 1- / 4- {c6- (2,4-di-tert-ai: i.jlpiienoxy) -acetaraido

3-ethox; y-4- (5- or 6-bro.n-1 -benzotriazolyl) -5-pyrazolone

509808/1019

~ 24 -

/JS.- 11 / 1- (2, 4,6- _{Trichi or P} hen: / l) -3- / 3- {oL- (2,4-di-tert-amyl-phenoxy) -aceta : nido j -'benzaraido7-4-phenyls'alf onamido-5-pyrazolone

Bl aiig r ünkup to1 e r

/ p-} 7 1 -H7droxy-4-chloro-III / ~ o6 - (2,4-di-tert-amylphenoxy) -but; yl7-2-naph thani d

/ -2 / 5-i-diethyl-4,6-dichloro-2- / ~ oi. - (3-: i-pentadecylphenoxy) -butyramdo7-ph.enol

~ y / "'-Hydroxy-4-iodo-N-dodecyl-2-naphtha-: ₁ iid

/ Ö-47 5-methoxy-2- / ~ * 5 <_{> /} - (3-n-pentadec.ylphenoxy) -butyramido7-4- (1-phenyl-5-tetrazolylthio) -phenol

/ CJ-57 Ί-Hydroxy-4- / 2- (2-hexyldecylcxycarbonyl) -phenylazo7-2- / H- (1-

/ 5-67 5-Methoxy-2 ~ / "c <_ - (3-n -pentadecylphenoxy) -butyramido7-4- (1-phenyl-5-tetrazolylthio) -phenol.

The couplers of the present invention are roughly classified into two groups : Fisher-type couplers, the water-solubilizing agents Have groups such as carboxyl, hydroxyl or sulfo groups, and hydrophobic couplers.

As a method of adding or dispersing couplers to or in an emulsion or a method of adding to a halosilver— emulsion in gelatin or a hydrophilic colloid, the known methods can be used. examples for this are Mixing the coupler with a high-boiling organic solvent (boiling point, for example above 170 C), such as dibutyl phthalate, Tricresyl phosphate, waxes, higher fatty acids or esters thereof (especially glycerol esters with lower Fatty acids or aliphatic citric acid esters) for the purpose of

509808/1019 ..._, ....

BAD ORiüiMAL

Dispersion (described in U.S. Patents 2,304,939 "and 2,322,027, as well as the JA-PA 75 126/73)> the mixing

of the coupler with a low-boiling organic solvent (boiling point for example below 170 ^° C.) or a water-soluble organic solvent for the purpose of dispersion, the dispersing of the coupler using a high-boiling solvent in connection with this (described in US Pat. No. 2,801,170, 2nd 301 171 and 2 949 360), and, if the coupler itself has a sufficiently low melting point (for example below 75 ^° C.), dispersing the coupler alone (for example described in DT-PS 1 143 707) or in combination with other couplers to be used together, such as colored couplers and uncolored couplers.

The ICC hydroquinone derivatives of the invention can be used in dispersed in the same way as the hydrophobic couplers. Preferably they are with the hydrophobic coupler or with conventionally used hydroquinone derivatives mixed and dispersed for use. The proportion of the IGC hydroquinone derivative is preferably not more than 20 percent by weight based on the total amount of the couplers used.

Conventional anion-active surfactants, that is to say surface-active substances (such as sodium alkylbenzenesulfonates, sodium dioctyl stilfosuccinates, sodium dodecyl sulfates, sodium alkylnaphthalene sulfonates or couplers of the fishery type), amphoteric surfactants (for example N-tetradecyl-n-betaine-di- polyol surfactants), or non-tetradecyl-nebetaine-di- (for example sorbitan monolaurate) can be used.

The Eirrulsion used according to the invention is un a silver halide photographic gelatin emulsion, the grains of silver chloride, silver bromide, silver iodide or mixtures contains of this, silver halide grains can alter the crystal habit the (1 0 0) area, the (1 1 1) area or a mixture thereof. It can be regular grains or around Trade grains with twin planes. The grain size is to

509808/1019

Example about 0.04 to 2 u.

The emulsion used in accordance with the invention can be jet method, a double jet method, a triple jet method, a back mix method or a conversion method get v / earth. Examples of hydrophilic colloids which are used to produce the emulsions according to the invention are gelatin, "cellulose derivatives, alginates, hydrophilic synthetic polymers (for example polyvinyl alcohol, Polyvinylpyrrolidone, polystyrene sulfonic acid, polyhydroxyethyl ~ acrvlat or polydiethylafninoethyl acrylate). Furthermore you can Plasticizers to improve the dimensional accuracy of the films and polymer latices, for example of polymethyl methacrylate, Polyethyl acrylate, or polybutyl acrylate, can be used.

The halogen silver emulsions used according to the invention can use the chemical sensitization process conventionally used. be subjected. Examples of these are gold sensitization, as described in US Pat. No. 2,399,0 & 3, 2,597,856 and 2,597,915, reduction sensitization, as described in US Pat. No. 3,437,850 and 2,521,925, and sulfur sensitization, as described in U3 -PS 1,623,499 and 2,410,689, as well as sensitization methods that work using metal ions other than silver, as in US Pat

2,448,060, 2,566,245 and 2,566,263 or combinations the aforementioned awareness-raising process.

In addition, spectral sensitizing methods conventionally used for color-sensitive materials can also be used find to be applied.

Suitable examples of spectral sensitizers and the methods for their use are disclosed in U.S. Patents 3,397,060 and

3,522,052, GB-PS 1,216,203 and DT-OS 2,030,326.

Furthermore, conventionally used stabilizers can be used (for example 4-hydroxy-1,3,3a, 7-tetrazaindene derivatives),

509808/1019

Antifoggants (e.g. mercapto compounds or benzotriazoles), coating auxiliaries, hardeners, wetting agents, . Sensitizers (e.g., onium derivatives such as those described in U.S. Patents 2,271,623, 2,283,226 and 2,334,864 quaternary ammonium salts), as well as those in US-PS 2,703,162, 2,531,332, 2,533,990, 3,210,191 and 3,158,484 Polyalkylene oxide derivatives. Finally, dyes can be used for anti-irradiation and, as an ingredient for Layer of the color-sensitive material of the invention, a filter layer, a mordant layer (layer for fixing the dye) qdef a colored one containing hydrophobic dyes Shift, be present.

The photosensitive emulsion used in the present invention is applied to various supports. Suitable supports are, for example, foils or plates made of cellulose acetate, polyethylene terephthalate, polyethylene, polypropylene, glass, chalk paper, resin-coated paper or synthetic paper. Suitable coating amounts, based on silver, are in the range from about 0.01 to 50 g / m 2, with respect to the compounds of the general formula I from about 0.001 to 10 g / m 2 and with respect to the couplers of the general formulas II to 71 from about 0.001 up to 50 g / m ² .

The photographic light-sensitive materials of the invention are developed using a color developing solution processed, which as a color developer, for example, a conventional p-phenylenediamine derivative or p-aminophenol derivative contains. Preferred p-phenylenediamine derivatives are, for example, p-amino-N-ethyl-N-ß- (methanesulfoamidoethyl) -m- toluidine sesquisulfate monohydrate, diethylamino-p-phenylenediamine sesquisulfite, p-Amino-NjN-diethyl-m-toluidine hydrochloride or. p-Amino-N-ethyl-N-S-hyo-roxyäthjrlan.ilin-sesquisulfat-monohydrate. Known developers for color negative material, color negative or color positive material for cinema purposes, color papers can be used and instant color-sensitive materials. Examples of color development are disclosed in the publication

509808/1019

JA-PA 35 749/70, the JA-PA 67 79-3 / 69, 13 313/70 and 19 516/71, the DT-OS 2 233 OpI, and in H. Gordon "The British Journal of Photograph- / Nov. 15, 1954, C. 'j <j3 ff: ibid. Sept. 9, 1955, 5.440 ff; ibid. Jan. 6, 1956, T-. 2 ff; 5. Horwitz, ibid. 22. April 1960, p. 212 ff; E. Gehret, ibid. 4. IJ & rz 1960, Ö. 122 ff; ibid. May 7, 1965, · -. "96 ff; and J. Lieech, ibid. April 3, 1959, pp. 182 ff.

herden so-called "D ± R coupler" or 'Qi;iH;. ^r drochinoiideriva, te ^:! is used, it becomes difficult to bleach the reduced silver with a bleaching solution or to remove the silver halide and reduced silver with a bleach-fixing solution.

Multi-layer color sensitive material of the invention can be prepared using a bleach solution having a redox potential (^ "- ..) (as defined below ) of. - 150 bio + 1000 mV, which contains a halide ion and a metal as or an organic oxidizing agent, be silver-bleached. Examples of metal salts are the salts of transition metals, in particular the salts or complement salts of Ti ^H ", Y ^{J +} , Cr, Cu ⁺ , i.In ' ⁺ , i.in ^J " ^r , Cn.- ⁴ ", Pe ⁰⁺ or Co · ³ " ¹ ". Examples of organic oxidations: agents are p-olfophenylquinone, oulfonaphthoquinone, "Bruster-blue radical" or "Weitz radical ¹ '. These are for example in U.S. Patents 2,507,133, 2,529,9o1, 2,625,477, 2,743,000, 2,310,643 and 2,705,201, the G3-PS 1,111,313, 777,635, 1,032,024, 1,014 396 and 9 32 934, as well as the known JA-PA 14 035/70 and 13 ^ 944 / 6o.

The aforementioned Ξ _ο _ _Ί value is determined v / ie fol- ^ t:

The measurement of E "^" takes place at 2 ^ 5 - 0.2 ⁰ C using a 7erbv.na-Plati: ele! Ctrode, the standard electrode is a silver / silver chloride electrode (Model EA-216, Manufacturer i.letrolra Ltd.) and a potentiometer (Hodell D-436, manufacturer Hetroha Ltd.).

509808/1019

BATH

Examples of the solution are described below. Bleach-fixing solution Aj.

Fe- (IIi) -sdz of ethylenediarninxetraacetic acid 40 g

Ammonium thiosulphate (70 ^) 150 ml

Sodium sulfate (anhydrous) 120 g

Water supplemented to 1000 ml

^H = ⁶ > ³ ' ^E redox = - 30 mV

redox
Bleach solution B:

Potassium bromide 20 g

Iron (IH) chloride (6H ₂ O) 41.5

Water, added to 11

PH = 1.5 5 E _redox = 720 mV
Bleach solution G;

Ammonium bromide 160 g

Aqueous ammonia (30 ^r fi) 23 ml of iron (III) salt of ethylenediaminetetraacetic acid 130 g

Glacial acetic acid 13.5 ml

Water, added to 1 1 "

pH = 5.75; E _redox =

mV

The multilayer photosensitive material obtained in the present invention is preferably treated with a bleaching solution or a bleach-fixing solution having an E _n value of 100 to 1000 mV

reaox

processed, vsn to remove the silver salt.

An experimental example illustrating this feature of the invention is given below.

509 808/1019

BATH ORIGINAL

Experimental example

The oxidation potential (E) is measured with regard to the hydroquinone derivative to be used according to the invention and for comparative compounds. The deepening of E takes place voltametrically, where Ξ means the potential "at which an electron is withdrawn from the connection at the anode. The oxidation potential is determined at 25 ^° C. in acetonitrile solution which contains sodium perchlorate (0.1 N) as the carrier electrolyte A hotation platinum electrode serves as the Ano.de and a saturated calomel electrode (SGS) as a comparison electrode.

- ΰ -5

Solution takes place at a concentration of 1 χ 10 ^r to 1 χ 10 LIol / liter according to the method described in DT-OS 2 010 762 tuid 2 219 437.

Attempt ITr. Connection E (volts)

_ O2C

(1) Compound 2 0.870

(2) 2- (1 ', 1 ·, 3', 3'-tetranethylbutyl) -

hy dr ο c hin on 0.310

(3) 2, 5-di- (1 ·, 1 «, 3 ', 3'-tetramethyl-

butyl) hydroquinone 0.320

(4) 2- ( 1 ', 1', 3 ^f , 3'-tetramethylbutyl) -

5- (1-phenyl-tetrazol-5-yl-thio) -hydroquinone 0.956

From the above results it can be seen that the reducing properties of hydroquinone derivatives can be achieved by replacing the tetramethylbutyl group improved by an n-octadecylthio group in this pail the n-octadecylthio group serves at the same time as a ballast group.

The examples explain the Srfinduiis.

• to '

For further explanation of the examples: .iea FIGS. 1 to 13, of which FIGS. 1, 7 and 13 are embodiments with regard to the structure of the multilayered color photographic material of the invention and? Ifruron 2 to 6 and 3 to 12 show the relationship e.g. ; vische: i lo ^r _: (Belichtim ^ sneivre) and density (D)

509808/1019

demonstrate.
example 1

According to FIG. 1, four layers are applied to a transparent one Cellulose triacetate film applied as a carrier and to a Sample dried. The composition and the procedure for Preparation of each coating solution are given below .

First> j chi ent: Roterrof indl-iche emulsion layer

1 kg brorajodsilbererriulsioii (3 excess content 0.6 mol; iodide content 6 percent) are removed and, using 4 x .ΊΟ "*" ⁵ lol / mol silver of the sensitizer dye I and 1 χ 10 ~ ^ hol / hol silver of the sensitizer dye II spectrally sensitized. Separately from this, 100 g of coupler A are dissolved in a mixture of 100 ml of iricresylphosphate and 200 ml of ethyl acetate and then dispersed in 1 kg of a 10 percent gelatin solution using 4 g of sodium anonylbenzenesulfonate. 550 g of the emulsion I obtained in this way are added to the aforementioned spectrally sensitized emulsion. Furthermore, 2 g of 2,4-dichloro-6-hydroxytriazine-sodium salt-in the form of an aqueous solution are added with stirring. The solution obtained is used in an amount of 1.5 g SiIb er / m.

Second layer: intermediate layer

There are 1 kg of a 10 percent aqueous gelatin solution manufactured. 50 g of 2, -5-di-tert-octylhydroquinone are in 100 ml of tricresyl phosphate and dissolved in 1 kg of a 10 percent aqueous gelatin solution emulsified to obtain a dispersion as in Emulsion I. After getting 250 g of the obtained Emulsion and an aqueous solution containing 2 g of 2,4-dichloro-6-hydroxytriazole sodium salt contains, has added, is stirred. The solution obtained is applied in a dry thickness of 1.5 U.

509808/1019 _ΒΑηΛ

• ORIGINAL BATHROOM

Third layer: blue sensitive emulsion layer

After 1 kg of silver bromide emulsion (amount of silver 0.6 hol; iodide content 6 percent hol) has been removed, an emulsion thereof is prepared in the same way as described for the first layer. A dispersion of a coupler and a hydroquinone derivative according to Table I is then added in the amount also given in Table I. Then 2 g of 2,4-di-chloro-6-hydroxytriazine sodium salt are added as an aqueous solution. This emulsion is used in an amount of 2.0 g silver / m ¹ ".

Fourth layer: protective layer

0.2 g of fiatrium nonylbenzenesulfonate become 1 kg of a 10 percent strength Gelatin solution added. This solution is then applied in a dry thickness of 1.0 ρ.

The sensibi— lizer dyes are given below.

Sensitizer dye I anhydro-5,5'-dichloro-3,3'-disulfo-

propyl-9-ethyl-thiacarbocyanine hydroxide, Pyridinium salt

Sensitizer dye II anhydro-9-ethyl-3,3 ^f -di- (3 ~ sulfo-

propyl) -4,5, 4 '>5' dibenzothiacar- .. bocyaniiihydroxid, Triäthylaminsalz

Coupler A 1 -hydroxy-N- ^ "'} / - (2,4-di-tert. -

anylphe.iox ^ -prbpyl7-2-naphthamide

Each of the samples is exposed in stages using a blue light source, followed by uniform exposure to a hot light source. Then the Enty / icklmag or /. Verarbeitvr ..;: at 33 ⁰ G according to the process steps given below.

509808/1019

BATH ORIGINAL

Processing stage time (gin)

1. Color development ■ 3.5

2. Bleach 6.5

3. Soaking 3.25

4. Fixing 6.5

5. Soaking 3.25

6. Stabilization 3.25

The recipes used in the processing stages Processing solutions are given below ..

P arb ent like IcI er

Sodium nitrilotriacetate Sodium sulfite In at r iii: .ic arb onat Potassium bromide hydroxylamine u.lfat

4- (n-ethyl-ii-u-hydroxyethylamino) ~ 2-ethylaniline sulfate

Water, added to bleach solution

Ammonium bromide. 160, above Aqueous ammonia (28 ^) 25.0 ml

Iron salt of sodium ethyleiidiamine tetraacetate 130 g Glacial acetic acid '· "14 ml

V / ater, added to 11

Fixing solution

Sodium tetrapolyphosphate N at ri umsulfi t Ammonium thiosulfate (70 fr) Hatriumlry-drogensulfit Water, added to

509808/1019

1.0 G 4.0 S. 30.0 S. 1.4 ■ S 2.4 S. 4.5 S. 1 1

2.0 G BATH ORIGINAL 4.0 S. 175.0 ml 4.6 G 1 1

Stabilization lb'sunjg;

Formalin (40 ^) water, added to

The results are shown in Table I.

8.0 ml 11

Tabel Ί and ICC-hydroquinone used in US Pat
Emulsion layer ICC Hydro
chinone Mole / mole
Coupler Result bnis Per
be
No. Coupler
third Mole / hol
silver Connect
manure 2 0.15 Fig. 1 Coupler 0.10 It Il Fig. 2 2 Λ-77 0.10 - Fig. 3 -> Coupler
B *) 0.10 Connect
manure 2 0.15 Fig. 4th 4th Λ-77 0.10 - Fig. 5 5 / J-17 0.10 6th / J-17

*) ^ - (4-Methoxy-benzoyl) -2-chloro-5- / ~ oC ~ (2,4-di-tert-amylphenoxy) -butyramido-7-acetanilide (4 equivalent coupler)

Figures 2 to 6 show the characteristic obtained Curves in which the solid line shows the relationship between the blue filter optical density and log (exposure amount) and the dashed line represents the relationship between the red filter optical density and log (exposure), the former being the characteristic curve of the third layer (containing the yellow coupler) and the latter that of the first layer (the contains the cyan coupler).

When comparing the sample Ur. 1 with sample no. 2 it can be seen that the use of coupler / 7-77 produces a markedly strong interlayer / interimage effect compared to the use of coupler B. From a comparison of sample no. 4 with sample no. 5, the strong DIR effect is that of the invention

509808/1019

- 3b -

Compound 2 easy to understand.
Example 2

According to FIG. 7, four layers are applied to a transparent cellulose triacetate film as a carrier and become one Sample dried. The composition and the procedure for Preparation of each coating solution are given below:

First layer: red sensitive emulsion layer The same as the first layer in Example 1 Second layer: intermediate layer

Same as the second layer in Example 1 Third layer: Green sensitive emulsion layer

1 kg of bromoiodosilver emulsion (the same as in the first layer) is ^{spectrally sensitized using 3 × ΙΟ "" 5} hol / mol of silver of the sensitizing dye III and 1 χ 10 mol / mol of silver of the sensitizing dye IV. Separately from this, 100 g of the coupler given in Table II and a certain amount of hydroquinone derivative are used to prepare an emulsion in the same manner as in Emulsion I which is made with 2 g of 2,4-dichloro-6-hydroxytriazine sodium salt as aqueous solution is added with stirring. The solution obtained is used according to Example 1.

Fourth layer: protective layer

The same as the fourth layer in Example 1

Sensitizer dye III Anh / dro-9-ethyl-5,5'-dichloro-3,3'-

cLisulfoiDropyloxacarbocyanine, ITodium as 509808/1019

BATH ORIGINAL

Sensitizer dye IV

Anhydro-5,6,5,6-tetrachloro-1,1-diethyl-3, 3-sulfopropoxyethoxyethylimidazolocarbocyanine hydroxide, Sodium salt

Each of these samples is graded using a source of green light exposed, followed by a uniform exposure using a red light source. The sensitonetric Llesoung gei.iU.i3 example 1 results in those compiled in table II Results.

Table II Coupler
in the and ICG
third -Hydroquinone derivative,
Emulsion layer Connect
manure 10 used Result bugs Per
be
Wr. Coupler Mol / mol Ag ICC-Hydro-
chinone Mole / hol
Ag Fig. 6th /? - 57 0.10 Connect
manure 10 0.015- Pig. S. 7th / 3-i / 0.10 —.— Pig. 9 8th / 13-37 0.10 Connect
manure 10 0.015 Pig. 10 9 /? - 37 0.10 Pig. 11 10 Coupler
C *) 0.10 0.015 12th

*) 1- (2,4,6-Trichlorophenyl) -3- / 5- (2,4-di-tert-amyiphenoxyacetamido ) -benzaraido7-5 ~ py ^ aaolon (4-equivalent coupler)

FIGS. 8 to 10 show the characteristic curves obtained, in which the solid line shows the relationship between the green filter _{optical density and log (exposure area) f,} and the broken line shows the relationship between the red filter optical density and log (exposure amount) . The features and effects of the invention are evident from a comparison of the results of samples 6 and 8 with the results of samples 7/9 and, in particular, sample 10.

509808/1019

Example 3

A multi-layer color-sensitive material according to FIG. 13f consisting of a cellulose triacetate carrier is obtained thereon layers of the compositions given below manufactured.

First layer of antihalation layer Gelatin layer with black, colloidal silver Second layer ; Intermediate layer (ML)

Gelatin layer containing an emulsified dispersion of 2,5-di-tert-octylhydroquinone contains

Third layer: First red-sensitive emulsion layer (RL ₁ )

Bromiodine silver emulsion (iodide content -8 percent)

... coated "with an amount of silver of 1.2 g / m

Sensitizer dye I

(as in Example 1) 6 1O ~ ⁵ mol / mol silver sensitizer dye II

(as in Example 1) 1.5 10 ⁵ mol / mol silver

Coupler A "0.09 mole / mole silver

Coupler / O-57 0.02 mol / mol silver

Fourth layer: Second red-sensitive emulsion layer (RL ₀ )

Bromiodine silver emulsion (iodide content 3 percent)

... coated with an amount of silver of 1.1 g / m

Sensitizer Dye Ί · 3 χ 10 "^ Hol / mole of silver Sensitizer Dye II 1.2 χ 10 ~ ⁵ moles / mole of silver

Compound 14 0.02 mole / mole silver

Coupler / S- 5 / 0.06 mol / mol silver

Coupler ~ / Έ / 0.03 mol / mol silver

509808/1019

Fifth layer: intermediate layer (HL)

The same as the second layer

Sixth layer: First green sensitive emulsion layer

Silver bromide emulsion (iodide content 8%)

..ο coated with an amount of silver of 1.4

Sensitizer dye III

(as in Example 2) 3 10 " ⁵ Uol / liol silver sensitizer dye IV

(as in Example 2) Ix 10 ^-5 jiol / silver mole coupler / 13-87 '0.05 mole / silver Uol

Compound 1 0.002 hol / hol silver

Coupler / β-β / 0.001 mol / r.iol silver

Seventh layer: second green-sensitive emulsion layer I.

Bromiodide silver emulsion (iodide content 6 i.Iol%) .. »coated with an amount of silver of 1.5

Sensitizing dye III 2.5 χ 10 "" ⁵ mol / mol of silver Sensitizing dye IV 0.8 χ 10 ^-5 mole / silver mole coupler / 1-2 / 0.01 mole / silver joi

Coupler / 1-8 / 0.02 mol / mol silver

Compound 1 0.0003 mole / mole silver

Eighth layer: Yellow filter layer (YPL)

Gelatin layer, the yellow colloidal silver and a 2,5-di-tert-octylhydroquinone emulsion dispersion contains

Ninth layer: First blue-sensitive emulsion layer

Silver bromide emulsion (iodide content 6 mole percent)

... coated with an amount of silver of 1

Coupler /J.-Y/ 0.25 mole / mole silver

509808/1019

Tenth layer: Second blue sensitive emulsion layer (BLp)

Silver bromide emulsion (iodide content 6 mole percent) ... coated with an amount of silver of 1.1 g / m

Coupler /Y-1.7 '0.06 mol / mol of silver. . Compound 1.0.002 moles / mole silver

Eleventh layer: APL

This layer is obtained by coating with 1 kg of a superfine silver bromide emulsion (silver content 0.6 mol; iodide content 1.4 mole percent; mean grain size 0.03 p) in an amount of 2.3 g silver / m.

Twelfth layer: protective layer (PL)

Gelatin layer containing polymethyl methacrylate particles (diameter O, 5 uj,

Each of the aforementioned layers is, in addition to the aforementioned Composition, with a gelatin hardener, 2,4-dichloro- 6-hydroxy-s-triazine as the sodium salt, a surfactant (saponin) and a thickener (polystyrene sulfonic acid as potassium salt) in suitable amounts.

Separately from this, another sample is prepared in a similar manner, but with compound 14 and compound 1 can be omitted.

The two samples obtained in this way are cut into strips 35 in width and, in addition, a white light wedge exposure is used using a blue light source, a green light source and a bot light source .exposed to to carry out the sensitometric according to Example 1.

With the use of compound 14 and compound 1 'produced sample, the color staining is less, the

509808/1019

Granularity is finer, and a stronger masking effect is observed compared to another sample that does not have it
Connections have been made.

The invention can be applied to color negative photosensitive material, color reversal photosensitive material, material for color slide, color positive reflection photosensitive material or color paper. The invention can also be applied to others
Recording materials for technical purposes are used in which the recording of defined color images plays a role
plays. Finally, the hydroquinone derivatives of the invention can be widely applied to black and white light-sensitive material.

509808/1019

Claims (6)

Patent claims 1. Multi-layer, photosensitive color photographic Material characterized by a carrier and on it at least two light-sensitive! Halogen silver emulsion layers, Ensure the images with substantially different hues, the photosensitive material 2-equivalent couplers iind / or 4-equivalent anilinopyrazolone couplers contains and at least one of the photosensitive halide silver emulsion layers or a colloidal one Layer of light-sensitive material a hydroquinone derivative or a hydroquinone precursor substituted by a Hsterocyclomonothiorest and an Aliphatomonothiorest, an arylmonothio residue ^ d-nenAT ^ fetcicBsaEst ^ imn aryloxy residue or a heterocyclooxy radical, and with a ballast group of 8 or more carbon atoms. 2. Parbenphotographisch.es material according to claim 1, characterized in that that the hydroquinone derivative is used as a substituent contains a heterocyclic monothio group and an aliphatic monothio group or aryl monothio group and in its Molecule having a ballast group; > has about 3 to 20 carbon atoms. 3. Dyeing photographic material according to at least one of Claims 1 and 2, characterized in that the hydroquinone derivative is a compound of the general formula I. (D 509808/1019 is, in which A and A ¹ each represent a hydrogen atom or a radical which can be eliminated by a base, and A · is able to combine with Q or R to form a ring; P, Q or R each represent a hydrogen atom, an alkyl radical, an aryl radical, the radical -3-Y, where Y is an alkyl radical, aryl radical, a hydroxyl group or a halogen atom, or the radical -SZ, where Z is a heterocyclic radical, which is photographically substantially inert in a bound state, is an alkoxy group, aryloxy group, or a heterocyclic group. 4. Color photographic material according to at least one of the Claims 1 to 3 »characterized in that the hydroquinone derivative has the general formula I a (Ia) in which Z is a tetrazole ring; P, Q or R each a hydrogen atom, an alkyl group, aryl group, a hydroxyl group, a halogen atom, an alkoxy radical or a heterocyclic radical, where at least one of the substituents P, Q and R represent the radical Y-S-, where Y is an aliphatic radical or an aryl radical, and P, Q or R contain a ballast group with about 3 to 20 carbon atoms. 5. Color photographic material according to at least one of the claims 1 to 4, characterized by a content of couplers of the general formula II CH-Z ₁ (H) 509808/1019 in which R. is an alkyl, alkoxy, aryloxy, aryl or heterocyclic radical, an amino, carboxemido, sulfonamido or ureido group; R "represents an alkyl or aryl radical; and Z _{1 is} a group which can be split off upon parabalysis; IU-CO-CH-CO-NH-R ₅ Z ₃ (IV) in which R. is an alkyl or aryl radical; R, - an aryl radical represents; and Z-, is a group that can be eliminated in color development; and or OH (VI) in which R ^ - is a carbamyl, sulfamyl, alkoxycarbonyl or aryloxycarbonyl group; R _{7 is} an alkyl, aryl, heterocyclo, amino, carbonamido, sulfonamido, sulfamyl or carbamyl group; R ^, R _q and R. _Q each represent a radical which has the same meaning as R ₇ and further represents a halogen atom or an alkoxy radical; and Z. is a residue that can be eliminated upon color development. 509808/1019 6. Color photographic material according to at least one of claims 1 to 5, characterized in that the anilinopyrazolone coupler is a coupler of the general formula III (III) is in which R ^ is an aryl or heterocyclic radical; Zp is hydrogen or a group that can be eliminated upon color development; B represents a ballast group; and X is an alkoxy group having 1 to 18 carbon atoms or a halogen atom, · Use of the color photographic material according to one of Claims 1 to 6 for the production of color images. 8 »Embodiment. according to claim 7 »characterized in that an exposed, multi-layer, light-sensitive color photographic material is exposed and the developed multi-layer light-sensitive color photographic material is subjected to bleaching or bleach-fixing by removing the reduced silver or silver salt with a solution which has an E _e ^ _ox ~ ^ ^er * ^{from 10} ® ^{to 100} ° ^mV and contains a halide ion and iron {III) ion.