DE1810464C - Color photographic developing process - Google Patents

Description

i 810

The Krlliuluiin beliiffl a I'liibplKilogniphifie.s Development process in which a silver-like loguiiid-crowned Pholographic recording material with a printed line in the presence of a color coupling, (lur fin Pyrii / .okleriviil is, is being developed.

The known color couplers have a reactive group ιιιιΓ, normally a reactive methylene group, which reacts with the oxidation products of primary animal amines consisting of primary animal amines with the formation of a / o-, imlainin-, imlainin- oiler indophenol dyes according to the Koiisi hirbkupplers und tier used developer connection. If the reactive group of the color coupler consists of an unsubstituted reactive methylene group, then the oxidation products of wrapping compounds, which are formed when 4 equivalents of silver are wrapped around, are required for the preparation of one equivalent substance. Reference is made, for example, to the hitch by CE M ees and T. 11. J a tu es, au "The Theory of the! 'Holographic Process", MacMillan Company, New York I% C>, p. 3 ¹ JO to J ¹ yy. Such color couplers are normally referred to as so-called 4-equivalent couplers.

However, it is also known, for example from British patent specification 736 922, so-called 2-equivalent couplers to use. These couplers are color couplers with a reactive one Methylene group, of which I is hydrogen atom through an Ilalogenatom, z. D. a chlorine atom, has been replaced. Trot / replacement of one hydrogen atom Coupling takes place through a halogen atom to form the same dye, which is then produced when the reactive methylene group is unsubstituted. The Halogcnaloin is used during the coupling reaction displaces. The effect of this displacement, however, is that it leads to the generation of a Equivalent dye only the oxidation products of developer compounds are required, which are in the F.r / euguiig form only 2 equivalents of silver.

Two-equivalent uncouplers have several significant advantages compared to -I equivalent uncouplers. Hey yours Only half the amount of silver halide is required to produce the dye, which in the case of the use of 4-equivalent couplers is required. This can reduce the cost of producing the enamel and, moreover, an improvement in the quality of the produced skin is achieved. Using It is therefore possible to use 2-equival tips with lower Silberhalogeiiidinengen get along what again the production of thinner skin snakes enables. Lead thin layers of miilsion again, as is well known, to a more favorable Hildauf-Ii) SUiIg. The reduction of the emulsion visual strength has the further advantage that the opacity of the emulsion layer is decreased, d. H. so that more light enters an emulsion layer below the emulsion layer, can get. The use of 2-equivalency coupling is therefore particularly advantageous (> <> at tier Er / eugiing of 'Mehrfaibigen farbphotogiaphischeu Materials with several emulsion layers out. Thin, DiId-forming layers are also particularly desirable because they form a lead to less light scattering and because at fif, let their use produce sharper dildos.

From British patent specification 918 128 pyrazolinoben / .imida / olfarbkuppler are known, of which a Toil 2-Äi | uiviilenlkuppler are, and which at the Coupling with oxidation products of color winding compounds Form purple dyes. Rs hui, however, be tempted to just watch these couplers unsatisfactory color image if they are in Silver halide emulsionon in the form of a dispersion which has been obtained by dissolving the color coupler in an organic Solvent and dispersing the solution in an aqueous solution of a hydrophilic colloid, for example Gelatin. The couplers have the disadvantage that their coupling activity occurs in the usual color solutions is relatively low,

The invention is based on the object of providing 2 and 1-equivalency couplers which react quickly with the oxidation product primary amines, which are used as color developers, couple and a good color photographic Lic-hlabsorplion have.

It has been found that 11-pyrazo! O [3,2-cj-s-iriazole Color couplers producing purple-red dyes are valuable, which are due to their absorption properties excellent as a purple color coupler for the production of color photographic recording materials suitable. The color couplers have the advantage that they react quickly with the oxidation products Commonly known color developing agents react in common color developing solutions. The dyes produced using the color couplers have at most a very low absorption in the red and blue areas of the spectrum and have excellent light stability.

The invention relates to a color photographic Development process in which a silver halide hally photographic material containing a primary amine in the presence of a Color coupler which is a pyrazole derivative is developed, which is characterized in that one carries out the development in the presence of a color coupler of the following formulas:

2N

II.

or "\ ⁷ , - ·

N
i
H

where mean:

R _{1 is} a hydrogen or halogen atom, a carboxyl group optionally esterified by an aliphatic alcohol having I to 22 carbon atoms or a phenol, or a group of the formulas - SO _a I 1; - O - ■ R ₁ oiler - S - R ₁ , in which R _{1 is} an optionally substituted aryl group, an optionally substituted amino group or a group of the formula R ₅ - N - · N -, in which R - is the radical of a diazotizable aromatic or heterocyclic amine, or an acyloxy, sulfonyloxy, thiocyano, henzotnazolyl or imido group and

R _{2 is} a radical of the formula which is split off ^{during c ″ arbentwicklung}

= --- ■ = CIl R ₃

where R _{; 1 is} an alkyl group with L to 22 carbon atoms, an aralkyl group with a moiiocyelic aroma

tables reads and an alkyl ring with I to 22 C-Aloniüii oiler is an aryl group of the phenyl group, wohei iliu J- uiicl 6-Siollumjüu the rings through possibly substituted alkyl groups or Arnlkylocler Aryl groups or hclerocycli ^ he groups or prinillre, secondary or tortillru amino groups or Acylaiiiido, hydroxy, alkoxy, carboxyl or esterified Carboxyl groups can be substituted,

Typical Siibslitiients which can be in the J and / or 6 Sldlung are straight or branched wedge-shaped, optionally substituted alkyl groups with I to 22 carbon atoms, z, II. Methyl, ethyl, n-propyl, isopropyl -, sec-bulyl, 1-butyl, tert-ainyl, lert-pentyl, n-llexyl, n-dodecyl, n-doeosyl, 2-chloro-n-butyl, 2-Llydroxyilthyl-, 2-I ¹ IIeHyIaIlIyI-, 2 '(2,4, G-trichloropheiiyl) -üIhyl- or 2-Ainini) IUIiylgruppen. If the 1- and / or 6-positions are substituted by aryl groups, these preferably consist of groups of the phenyl or naphthyl groups, that is to say, for example, of phenyl, ν- or / i-naph- 2, lliyl-, 4- Muthylphenyl, 2,4,6 - trichlorophenyl, 2 - (. 'Liloro-.v-naplithyl, 3-ethyl- \ - naphlhyl, 2-metlioxyphenyl or 3-acylaniidophenyl groups. Are the 3- and / or 6-positions substituted by heterocyclic groups, these can for example consist of pyridyl or thienyl groups. Amino groups that can be in the 3- and / or 6-positions are ζ. Π. Docosylamino, phenylamino, tolylaniino, 4 (3-sulphu) benzamido) amino, 4-cyanophynylamino, 2-trilluoromethylphenylamino or benzothiazoloamino types. Acylamido groups which can be in the J-uiul / or fj positions are, for example, ethylcarbonamido, n-decylcarbonainido, phenylethylcarbonamido, phenylcarbonamido; 2,4,6-trichlorophenylcarbonamido-; 4-methylplienylcurbonainido-; 2-ethoxyphenylcarbonamido-; 2 - [(2,4-di-tert-amylphenoxy) acetamido] benzamido or x- or / f-methylcarbonamido groups. Examples of alkoxy groups are: methoxy, ethoxy, n-ethityloxy, n-hexoxy, n-dodecyloxy and n-docosoxy groups. Carboxyl groups or esterified carboxyl groups which can be in the 3- and / or 6-positions are, for example, methoxycarbonyl, ethoxycarbonyl, n-docosoxycarbonyl or phenoxycarbonyl lips.

If the meaning of a halogenamine in the given formula is IR ₁ , this can consist, for example, of a chlorine, bromine or iodine atom. If R ₁ consists of a group of the formula R ₁ - O - or R ₁ --- S -, then R _{1 can,} for example, be an alkyl group from the phenyl or napitol group, for example a phenyl or tolyl group. BeSItZtR ₁ denotes an optionally substituted amino group, this can have the meaning of an amino group such as have been described in connection with the substitution of the J and 6 positions.

R _{; 1} can be, for example, a methyl, ethyl, butyl, phenylethyl, phenyl or tertiary aminoplieiiyl group.

To carry out the Farhphotographic Ent Color couplers suitable for the winding process according to the invention are, for example:

Table I.

1. 7-m - [. Airamidophenylthio-6-methyl-3-propyl H -pyrazolo [3,2-c | -s-triazole;

2, .UVV-Diirboxyplienyl-ri-hoptndecyl-11 l-pyrazolo [3,2-c] -s- | riazole;

3,3-llexyl-6-methyl-lll-pynrzolo [3,2-e] -s-lriii / .olyl-

7-sulfonic acid;

4,6-Metliyl-3-peiiladecyl-7-plienoxy-l I l-pyrazolo-

[3,2-c | -s-triazole;

5, 7-Ainino-n-liexyl - () - ynethyl-IH-pyrazololJ, 2-c | -

s-triiizole;

6, 6-methyl-3-phcn, vl-7, J'- |) yridylazo-III-pyrii / olo

I H -pyrazc) lo [3,2-c | -s-triazole;

7, 7-Acc! Oxy-6-methyl-3-pciiladeoyl-IH-pyra / .olo [3,2-c) -s-triazole;

8, 3- [4- [v- (3-t.-Butyl-4 "hydroxy |) henoxy) letradcaiianiido | -2-chloro) phenyl-ii-nielhyl-l I l-pyriizolo [J, 2-c | -s-triazole;

9,7-Butylmelhylen-6-ynethyl-3-plicnyl-111-pyi azolo [3,2-c] -s-iriazole; ,

K). 7-Men / .ylidene-6-methyl-3-phenyl-

I1 l -pyrazolo [3,2-cj-s-triazole;

11. 6-Methyl-3-pentadccyl-7-thiocyaiiato-I H-pyrazolo [3,2-c] -s-triazole;

12. 7-Benzotriaz () | -2-yl-6-iuethyl-3-peiitadecyl-I H -pyrazolo [J, 2-c | -s-triazole;

13. o-Methyl-T-methylsulphonoxyO-pcntadecyl-I H-pyrazolo [3,2-c] -s-triazole;

14. 3-l-Iepta (lecyl-6-methy | -7-phthalimido-1 H-pyrazolo [3,2-c] -s-triazole;

15. 7-Butylaminomethyl-6-methyl-3-undeeyl-1 H -pyrazolo [3,2-c] -s-triazole;

1.6. 3-p-acetamidophenyl-IF-pyrazolo [3,2-c | -s-triazole;

17. 3-p-Tj-illuoroi-diethylphenyl-1 H -pyrazolo [J, 2-c) -s-triazole;

18. 3 - «- naphthyl-1 H -pyrazolo [3,2-cj-s-triazole;

19. 3,2'-thienyl-1 H -pyrazolo [3,2-c | -s-triazole;

20. 6-Benzamido-3-phenyl-1 H -pyrazolo [3,2-c] -s-triazole;

21. 3-F ^ dTOXy-O-InCtIIyI-1H -pyrazolo [3,2-c] -s-triazole;

22. 3-Ethoxy-6-methyl-1H-pyrazolo [3,2-c | -s-triazole;

23. 6-methyl-1H-pyrazolo [3,2-c | -s-triazolyl-3,7-dicarboxylic acid;

24. Octyl-o-methyl-1H-pyrazoloP ^ -cj-s-triazolyl-3-carboxylate.

The color couplers used according to the invention can be prepared by ring closure of compounds of the formula:

III.

N NH

R "-

'--NH -NH- CO - R ₇

COOR ₈

wherein R ₀ , R ₇ and R _{8 are} optionally substituted alkyl, aryl, aralkyl or amino groups, in the presence of POC1 _; , in an inert solvent, e.g. B. benzene, or by ring closure of compounds of the formula:

N NlI

J-NH-N-CH-R ₇

COOR ₁₁

ι Q 1 η / ß / Γ

ι υ ι υ τ υ τ \

5 J 6

wherein R ₀ , R ₇ and R _{8 transfer} the meaning already given to image receiving layers, which preferably

have, in the presence of bromine and sodium acetate, a mordant layer for pickling or fixing

Acetic acid. of the transferred dyes.

After the ring closure, the group R _{8 can be}

Separate treatment with sulfuric acid. 5th, within the framework of color pholographic development

Compounds of the formula III can be mixed with developer compounds used by different processes.

scl7.ung of compounds of the formula are used, d. H. for example:

■ Kr ^ ij RN-diethyl-p-phenylenediamine hydroclilond; N-Me-

I thyl-p-phenylcndiamine hydrochloride; Ν, Ν-dimethyl

"_! _Is] iJKiu ¹⁰ P-plienylenediamine hydrochloride; 2-amino-5-diethyl

^{K | i} ^ / - inn inH ₂ aminotoluene hydrochloride; 2-amino-5- (N-ethyl-N-lau-

! ryl) toluene; N-Ethyl-N-zS-Metliansulphonamidoathyl-

COOR ₈ 3-methyl-4-aminoaniIine sulphate; N-ethyl-N - /? - melhan-

sulphonamidoalliyl-4-aminoaniline; 4-N-ethyl-N- / J-hy-

wherein R “and R _{8 have} the meaning given, 15-hydroxyethylaminoaniline; 3-methyl-4-N-ethyl-N- / i-hy-

with an acid chloride, e.g. B. of the formula ClCOR ₇ , in droxyälhylaminoaniline; N- (2-amino-5-diethylamino-

Presence of a base, e.g. B. pyridine. phenyläthyOinelhansulphonamidohydrochlorid or

Compounds of the formula IV can be classified according to the p-aminophenol and their substitution product in

by H. Beyer and Mit. in Ber. 89 (1956) p. 2552 where the amino group is not substituted.

process described. 20th

To carry out the color pholographic ent Example 1
Winding method of the invention can be used to record 0.194g of 6-methyl-3-n-pentadecyl-1H-pyrazolo [3,2-c] -nimgsnialcrialicn which have been in at least s-triazolyl-7-carboxylic acid at 8O ⁰ C in 0 , 39 ml of a photosensitive silver salt layer, in particular dissolved N, N-Diälhyllauramid. To the Kupplcrlösung iTaste a photosensitive Silberhalogenidemul- 25 was then 8O ⁰ C. solution of 12.8 ml of a sionsi-.hich; or in a pass to this emulsion layer 10 "/ ₀ igcn inert Knocliengelatine and 1.2 ml of an adjacent layer a color coupler of the eye- 5 ° / _o by weight Triisopropylnaplithalinsulplionatlösung added formulas I or. 11. The mixture was measured using a

The new color couplers are homogenized in the photographic ultrasonic mixer. Then were

Recording material as in Entwicklcrlösungen 30 8.8 ml water and 0.9 ml of a 7.5 ° / _o solution of

saponin was added to develop a color photographic on-screen, and the mixture was filtered

drawing material is used.

in the latter case, the color couplers were in the dye to the lillrat was thereupon 6.77 g of a

developing baths are dissolved or dispersed. Bromoiodide emulsion with 0.69 g of silver to cecbci.

The to carry out the color pholographic 35 whereupon the mixture obtained on a usual

Film base used in the development process of the invention was applied in such a manner that on

purple dye-forming couplers are largest- a carrier area of 0.0929 m ^2, 150 mg of silver, 40 m;

partly colorless, but germinate also be colored. Coupler and 425 mg gelatin (dry weight) cnf-

namely if R _{1 is} an Azores! or R _{2 is} the remainder of a fell. The light-sensitive recording material obtained

aromatic aldehyde. It is assumed that the material was then image-crechl exposed and an-

that the coupling takes place in position 7, the closing for 10 minutes at 20 ⁰ C in a color

Ktippler act as so-called 2-equivalent couplers, developers of the following composition c: it-

arsj-, 1 if R _{1 is} a hydrogen atom, in wraps:

which! "they all represent 4-equivalent uncouplers. Wmsst _{8 (n}

The 7i.r implementation of the method of the invention «5 waVscWcies'Nalriümsulfi. '.'. '.'. "2 Or

Used couplers can diffundicrharc couplers ^ mino-S-diälhylaminololuol-

be non-diffusible couplers or couplers from hvdrochl irid

] ischer-Tj ρ The non-diffusing couplers koji-sodium carbonate-mono-drate "'20 0 i

new in Sill-erhalogcnidemulMonen with help \ 0.1 high-sodium bromide 171

boiling coupling components are introduced. 50 aufaefülit-iiif irvrT, «i ⁸

The silver salt layer of the to carry out the iiwirtteiAlt to 10? _f2 vo

Method of the I turn used photograph! - ^{p11 whom} «-» »Sesieiu aul 10.8 1 (22 C)

see drawing markings or the silver salt- After the development the Aufreiclimn ^ s-

Layers of such a recording material are placed in a Sa'urcslop fixer and then h eh

are preferably brought from the usual known silver 55 Fcryanidblcichbad. Subsequently was

■ halonide emulsion layers. fixed. Fs became a purple image in the cxponicr-

The rnuilsiiMisschichlen one for the implementation of the th districts from a dye, whose ab-

Verfahrcnsder I found the recording inscription maximum used was 540 ηιμ.

tiiiiici ials can in the usual way according to known In the drawing , Km ve A represents the absorption of the

Processes are chemically and spectrally sensitized. 60 dye, and curve B is the absorption of the comparison under

(in an advantageous embodiment of the term 2-stcarylpyrazolobenzimid'izole crhal-

Veilahii ns the lindunn there is the Auf / cichniings- tenci l-'arbsloffes. The ratio of l ^; urhkuppicr

Miik'iial from chum Sihichttrilger and at least three to solvent (N.N-diethyllauramid) was I: 3.

different sensitized emulsion layers, which The development ei followed at a pH value of J1.75 .

are angular about each other, (15 l: correspondingly advantageous results have been

Those in the process of the Ι-ιΊ'ιικΙιιημ are omitted when other developers \ erbi! Iduni? En vcr «vcn-

wiiould l'arbbildcr can also be detached, for example N, N-diethyl- "p-phenyls; i ·

one of the usual color diffusion materials, diamine hydrochloride. In the latter case, a

Dye with an absorption maximum at 531 ηιμ receive.

When using S-MethyM-amino-N-ß-methylsulphonamidoethylaniline a dye image with a dye with an absorption maximum at 536 ιτιμ was obtained.

Example 2

A further recording material was produced according to the method described in Example 1 and developed. This time 6-methyl-3-phenyl-1H-pyrazolo [3,2-c] -s-triazole was used as the color coupler. The ratio of color coupler: solvent was 1: 3. The dye of the developed image possessed an absorption maximum at 564 ΐημ.

Example 3

A further recording material was produced according to the method described in Example 1 and developed. This time 6-methyl-3 (2,4,4-trimethyl) pentyl-1H-pyrazolo [3,2-c] -s-triazole was used as the color coupler used. The ratio of color coupler to solvent was 1: 3. The dye of the developed The image had an absorption maximum at 540 ΐημ.

Example 4

First, a magenta dye forming developing solution of the following composition was prepared manufactured:

Sodium sulfite 2 g

2-Amino-5-diethylaminotoluene HCl .. 2 g

Sodium carbonate 20 g

Potassium bromide 2 g

6-methyl-3 (2,4,4-trimethyl) pentyl H -pyrazolo [3,2-c] -s-triazole (in

Ethanol solution) 1.5 g

made up to 1 liter with water

The developer solution was then adjusted to a pH of 11.5 by adding NaOH solution.

The resulting color developing solution was used to color develop a magenta image in a strip of exposed film having a silver halide emulsion layer. The silver in the strip was converted to silver halide by treatment with a ferricyanide-bromide bleach bath , and the silver halide was removed by treating the strip with a sodium thiosulfate fixer. Thus a magenta dye image of excellent quality was obtained. The dye had an absorption maximum at 541 ιτιμ.

Claims (1)

Claim: Color photographic.es development process, in which a silver halide photographic material having a primary Amine in the presence of a color coupler which is a pyrazole derivative is developed thereby characterized by the development in the presence of a color coupler of the following Formula performs: 35 II. ^ k. or where mean: R _{1 is} a hydrogen or halogen atom, a carboxyl group optionally esterified by an aliphatic alcohol having 1 to 22 carbon atoms or a phenol, or a group of the formulas - SO ₃ H; - O - R, or - S - R ₄ , in which R _{4 is} an optionally substituted aryl group, an optionally substituted amino group or a group of the formula R ₅ - N = N -, in which R _{5 is} the radical of a diazotizable aromatic or heterocyclic amine is, or an acyloxy, sulfonyloxy, thiocyano, benzotriazolyl or imido group and R _{3 is} a radical of the formula which is split off during color development = CH - R ₃ wherein R _{3 is} an alkyl group with 1 to 22 carbon atoms, an aralkyl group with a monocyclic aromatic radical and an alkyl radical with I to 22 carbon atoms or an aryl group of the phenyl series, the 3- and 6-positions of the rings being optionally substituted by Alkyl groups or aralkyl or aryl groups or heterocyclic groups or primary, secondary or tertiary amino groups or acylamido, hydroxy, alkoxy, carboxyl or esterified carboxyl groups can be substituted. For this 1 sheet of drawings 109624/247