DE1075431B - Photographic, in particular color photographic recording and copying material - Google Patents

Description

GERMAN

It is known that a colored image can be produced by using certain developer solutions or adding a compound to the silver halide gelatin emulsion layer which, in the course of the development process, interacts with the oxidation products of the development The substance couples with the formation of a dye which is directly attached to the silver grains of the under development evoked silver image is reflected. Compounds of this type are hereinafter referred to as coupling components or coupler.

To be of practical use in color photography, a coupler must produce a dye image of suitable stability and spectral properties. In addition, the coupler must be capable of being incorporated into a photographic emulsion and be resistant to diffusion therein. Thus couplers can be incorporated in a photographic emulsion by u in the same a solution of the coupler in a water-immiscible solvent, such as tricresyl phosphate, dibutyl phthalate. The like., That is dispersed in an oil type _r. On the other hand, alkali-soluble couplers can also be used which, thanks to this property, can be dissolved directly in the photographic emulsion. A long alkyl chain. Although many inventions in the art of such color formers or couplers have been made in the art, only a few couplers have the above properties which ensure their practical use in color photography.

The invention relates to photographic silver halide gelatin layers for color photography with couplers, which are characterized by increased diffusion resistance, extremely high solubility in with water immiscible organic solvents and relatively low melting points. Even compared to known color couplers of the German Auslegeschrift 1 000 233 and the USA Patent 2 474 293 show the new couplers according to the invention a considerably better solubility in organic, with water immiscible solvents.

According to the invention, couplers are incorporated into photographic emulsions in a known manner represent a ketomethylene compound, a pyrazolone or a phenol, but an m-alkylphenoxyacyl radical as a substituent in which the alkyl group has at least 10 carbon atoms. This substituent can be easily inserted into color-forming molecules, which are a primary or secondary amino group, a reactive hydroxyl group, or other suitable attachment means own. The coupling components obtained in this way are extremely strong in water Photography, especially

color photographic.es recording

and copy material

Applicant;

General Aniline & Film Corporation,
New York,. NY (V. St. A.)

Representative: Dr.-Ing. Dr. jur, H. Mediger, patent attorney, Munich 9, Aggensteinstr. 13th

Claimed priority:
V. St. τ. America September 4th 1957

Robert Fleming Coles, North St. Paul, Minn. (V. St. A.), has been named as the inventor

Immiscible organic solvents, such as tricresyl phosphate, dibutyl phosphate and the like, are soluble and have low melting points, generally 100 ^° C. and below. This property is particularly desirable in a system in which aggregates or droplets of dye former and dye are dispersed, since such a system, once it contains the new couplers, exhibits little tendency to crystallize. The high solubility in organic solutions and the low melting point make these couplers suitable even for emulsions of the mixed grain type.

The coupling components in question correspond to the general formulas

R ₁ OH

A - N - c -: c - o

909 729/384

A-Y-N-C-C-O

■ '"■"" - ^ ■ 3 ■" ■ 4

In it, R _{1 is} hydrogen or an alkyliest (methyl, a primary aromatic amino developer to react

Ethyl, n-propyl, η-butyl, sec-butyl, amyl, isoamyl, ren is capable;

Hexyl, heptyl, etc.); R ₂ = long-chain alkyl radical with _

ία up to 20 carbon atoms (Capryl, Undecylyl, -LauryV · ■ · =?

Myristyl, pentadecyl palmityl, stearyl, etc.); R ^ = R ₂ - & ^: _

or an aryl group (phenyl, halophenyl, such as

Chlorine, dichlorophenyl or trichlorophenyl, α-naphthyl, β-naphthyl, etc.) ; A = containing the coupling function

Molecular parts, e.g. B. "reactive methylene or phenolic Hydroxyl group associated with the oxidation products io II. {,. I. -'C - N - alkylene -;

OH

and

OH

- C - N - arylene -

. Typical representatives of the couplers according to the invention are:

1. 4,6-dichloro-2-a- (3'-pentadecylphenoxy) -n-butyramidophenol

HIGH

ill,

Cl- / "\ - N - C - C - 0 - 1 / \ C ₂ H ₅ \ J Cl CH

2. ^ (l-Oxy ^ -naphthonyl-N'-ta-iS-pentadecylphenoxyJ-n-butyryy-l.ö-hexanediamine

^0H OH HOH

Il I I Il I

_{C - N - (CH 2} ) ₆ - N - C - C - O

3 .. N - (^ - CMOR-l-oxy-2-naphthoyl) -N '-] | a- (3-pentadecylphenoxy) -n-butyryl] -l, 6-hexanediamine ^0H OH HOH

| N - arylene.

y \ A "'ι Ii ι

^ YyC-N- (CHs) ₆ -NCCO

Cl

C ₁₅ H ₃₁

4. N- (1-Oxy-2-naphthoyl -) - N '- [α- (3-pentadecylphenoxy) -n-butyryl] -m-phenylenediamine

HIGH

C ₁₅ H

₁₅ H ₃₁

5. 3-a- (3'-Pentadecylphenoxy) -n-butyramido -1- (2 ', 4', 6'-trichlorophenyl) -5-pyrazolone

HIGH

CH ₅ ,

C =

- O - C - C - N - C

I U / O ft D 1

6. 3-a- (3'-Pentadecylplienoxy) -n'-butyrairiido-1-phenyl-5-pyrazolone

HIGH

. \ —0 — C — C — — C

7. 1- (2'-Chlorophenyl) -3-a- (3'-pentadecylphenoxy) -n-butyramido-S-pyrazolone

HIGH

1. ■ J. I "■ vQ — c — e — N — c —CH ₂

CoH,

C.0

, - Cl

α-Benzoyl-3-α - [- (3'-pentadecylphenoxy) -n7butyramido] acetanilide

0 OH HOH

YC CH ₂ - CN

Ν — C — C — 0

C ₂ H ₅

C ₁ = He

'9. N- {p- [N'-Benzyl-N '- (p-tolyl) -sulfamyl] -phenyl} -a- {p - [- (3-pentadecylphenoxy) -butyramido] -tenzoylj-acetamide

HOH O OH

C-CH ₉ -C -N

10. α-Benzoyl-δ-chloro-S-fa-IS'-pentadecylplienoxyJ-rL-butyramidoJ-acetanilide

O OH HOH

C-CH ₂ -CN-

Cl-

, _N— C— C— O

C ₂ H ₅

1,057,431

" 8th

11. 6-chloro-a- (2'-metlioxybenzoyl) -3- [o- (3'-peiitadecylphenoxy) -n-butyramido] -acetaiilide

O O H H O H

λ. Ii II! / κ I Il I / \ ^

Xp-C-CH ₂ -C-Ν -, / Χ, -Ν-CC-O-γ Χ

^{0CH3 ClJ} / C ₂ H ₅

12. N- {2-CMor-4- [a- (3-pentadecylphenoxy) -ii-butyrainido] -pheiiyl} -l-oxy-2-naplithartiide

OH ο _H Cl

I II-! I "" -

Ύ H 0 H

C ₂ H ₅

C15H;

13. N- {6-Chloro-3- [α- (3-pentadecylphenoxy) -n -butyramido] -plienyl} -l-oxynapitliamide ^0H OH HOH

I J. ./. J Il I : - ν— f -X- ν - c - c - ο

he I

^C XT 'C ₂ H ₅

14. 4-chloro-2- [a- (3'-pentadecylphenoxy) -n-butyramido] phenol ^0H H 0 H

N - C - C - O -, i ^ X

i Ί

Cl

C15H31

15. 4 ₎ 6-dichloro-2- [α- (3'-pentadecylphenoxy) acetamido] -plienol OH _{H o}

I Il

N - C - CH ₂ - 0 -ι

Cl

16. 4-chloro-3-methyl-2- [a- (3'-pentadecylphenoxy) -ii-propionainido] -phenol ^0H H 0 H

—C — C — 0

^CHs CH ₃

Cl

i U / ö 401

The following example illustrates the application of the novel coupling component of the invention.

example

1.5 g of 3-a- (3'-pentadecylphenoxy) -n-butyramido-1- (2 ', 4', 6'-trichlorophenyl) -5-p5n: azolone are dissolved in 6.0 g of a mixture of phenethyl alcohol, tricresyl phosphate, n-butyl phthalate 5: 4: 1 and disperses the solution in 20 ecm of a 6% aqueous gelatin solution containing 0.05 ecm of lauryl sulfate. The emulsification will carried out by rapid stirring in a small Wering mixer. The coupler dispersion obtained is with 50 g of a molten silver halide gelatin emulsion, which is appropriately sensitized and stabilized, mixed and then poured onto a suitable support, solidified and dried in the usual manner. This emulsion layer becomes after exposure to 2-amino-5-diethylaminotoluene as a developing substance develops and after the usual removal of the silver gives a crimson image.

The emulsion layer described can be combined in a multipack with other emulsion layers which also contain coupling components according to the invention, but also with such Layers that contain coupling components that have been customary up to now.

Various photographic developing substances can be used with the coupling components of the invention to be used. The primary aromatic amino developers are generally useful, including of phenylenediamines and aminophenols. The alkylphenylenediarnines can be substituted in the amino group as well as in the ring. Suitable compounds are for example 4-aminoaniline, 4-ethylammoaniline, 2-diethylaminoaniline, 4-dialkylaminoaniline, e.g. B. 4-dimethylaminoaniline, 4-diethylaminoaniline, 4- [N - (/ S-oxyethyl) -N-ethyl] aminoaniline, 4-Amino-N-ethyl-N - (/ 5-methanesulfonamidoethyl) -2-methylanilmsulfate etc. The developing substances are preferably used in the form of their chlorides or acid sulfates, which are more soluble and are more stable than the free bases. All of the compounds mentioned have a primary amino group, so that the oxidation product of the developer with the dye coupling components after development Able to couple formation of dye images. After the usual removal of the silver image by fading and fixing only leaves the dye image in the emulsion layer.

A suitable developing solution can, for example, have the following composition:

2-amino-5-diethylaminotoluene 2 g

Sodium carbonate (anhydrous) 20 g

Sodium sulfite (anhydrous) ...... 2 g

Potassium bromide 0.2 g

Water to prepare 1000 ecm

The halogen silver emulsion layers containing the dye formers and exposed are developed in the usual way.

The dye formers according to the invention are usually added to the emulsion layers during their production incorporated. However, it is also possible to add them to the shift later, especially at the time of development incorporated by adding a silver halide emulsion layer which does not yet contain any such dye-forming agents with a solution of a primary aromatic amino developer and a dye former The coupling component is present in the halogen silver emulsion layer at the time of development, be it that it was already contained in this layer since its production or only at the time of development in it is incorporated.

The preparation of the new dye formers is illustrated by the examples given below.

A. Manufacture of intermediate products

A solution of 608 g (2.0 mol) of m-pentadecylphenol and 160 g (4.0 mol) of sodium hydroxide is added 1300 ecm of 95% ethanol in a three-necked three-liter bottle equipped with a reflux condenser, stirrer and dropping funnel, cools slightly in water and adds 334 g (2.0 mol) of a-bromobutyric acid at such a rate that that a moderate reflux occurs, then heated to reflux temperature for 3 hours, sets another 20 g Sodium hydroxide and 42 g of a-bromobutyric acid after, heated for a further 3 hours, repeated the replenishment second and third time, then pour the solution into 41 Ice water, strongly acidifies with hydrochloric acid, collects the precipitated product, washes with water, then with it cold methanol and recrystallized from 21 methanol. 600 g of the intermediate product are obtained with a melting point of 81 to 84 ° C.

The acid chloride of the product is prepared by adding a mixture of 200 g of the acid just obtained and 300 ecm thionyl chloride for 24 hours. Most of the excess thionyl chloride is degassed by means of an aspirator and the rest under the pressure of a vacuum pump below 40 ° C. The remaining oily acid chloride can be used without further purification.

B. Preparation of the dye formers

amido] phenol

A solution of 26.7 g (0.15 mol) of 2-amino-4,6-dichlorophenol in 350 ml of dry benzene is mixed with 15 g (0.15 mol) of potassium acetate. The mixture is cooled to 10 ° C., 61.5 g (0.15 mol) of the acid chloride obtained according to A are added dropwise with stirring and the mixture is stirred in the cold for 3 hours and then on the steam bath for 1 hour. After adding decolorizing charcoal, the mixture is filtered, the benzene is removed on the steam bath under reduced pressure, the residue is treated with ice and water, the resulting mass is stirred with dilute sodium bicarbonate solution in a Waring mixer, nitrated and dried. The dyestuff can be applied in this form or further purified by recrystallization from low boiling petroleum ether (melting point 57 to 59.5 ^east C).

b) N-tl-Oxy ^ -naphthoylJ-N'-Ca-ß-pentadecyrphenoxy) -n-butyryl] -l, 6-hexanediamine

OH ο Η

_C - N - (CHJ _{6 - NH 2}

One brings phenyl-1-oxy-2-naphthenate with 4 mol excess

developed according to the invention. So it is enough that the 70 shot of hexamethylenediamine in cold benzene

909 729/384

Reaction. A solution of 14.3 g (0.05 mol) is cooled of the amine obtained in this way in 100 ecm of dry benzene on ice and 20.5 g (0.05 mol) of the acid chloride obtained according to A. are added dropwise with stirring Add dropwise 29 ecm (0.25Mol) of triethylamine and stir the reaction mixture 2 hours in the cold and 2 hours with heating, nitrated, removes the solvents at reduced pressure and dilute the residue with 100 ecm petroleum ether with a boiling point of 30 up to 60 ° C. The solution is cooled on ice, the solid substance is collected and uncrystallized from ethanol. 22 g of the dye binder with a melting point of 92 to 94 ° C. are obtained.

c) N- (4-chloro-1-oxy-2-naphthoyl) -N '- [α- (3-pentadecylphenoxy) -n-butyryl] -1,6-hexanediamine

This dye binder is hergesteüt analogously to b) and recrystallized from ethanol. Melting point at 78 up to 79 ° C.

d) N-1-Oxy-2-naphthoyl) -N '- [α- (3-pentadecylphenOxy) -n-butyryl] -m-phenylenediamine

NH,

The Arnine formula is made by adding the free acid obtained according to A with m-nitroanuine in a phosphazo reaction in the presence of phosphorus trichloride brings to reaction and then reduced catalytically over platinum oxide.

A mixture of 9.6 g (0.02 mol) of the amine thus obtained and 5.3 g (0.02 mol) of phenyl 1-oxy-2-naphthenate are placed on a metal bath at 160 to 170 ° C under Heated vacuum until no more phenol distills off. It is recrystallized from about 300 ecm of methanol and 8.5 g of the dye former has a melting point 82 to 84 ° C.

e) 1- (2 ', 4', 6'-trichlorophenyl) -3- [a- (3'-pentadecylphenoxy) -n-butyramido] -5-pyrazolone

A suspension of 8.3 g (0.03 mol) of 3-amino-1- (2 ', 4', 6'-trichlorophenyl) -5-pyrazolone in 100ccm is treated N-methyl-2-pyrrolidone dropwise with stirring at 10 ° C with 12.2 g (0.03 mol) of the acid chloride prepared according to A, then added dropwise with 2.5 ecm (0.03 mol) pyridine, stir 1 hour, leave overnight

stand and pour the solution into ice water. The excreted, Slowly solidifying oil is mixed with ethanol triturated, deposited by filtration and recrystallized from glacial acetic acid. The dye former obtained in this way melts at 133 to 134 ° C.

f) 3- [α- (3'-Pentadecylphenoxy) butyramido] -1-phenyl-5-pyrazolone

ίο You work as according to e), but replace the pyrazolone there by 3-amino-1-phenyl-5 ^ pyrazolone. The received Dye bond melts at 63 to 64 ° C.

g) 1 - (2'-Chlorophenyl) -3- [α- (3 '-pentadecylphenoxy) ^X 5 n -butyramido] -5-pyrazolone

The procedure is as in e), but the pyrazolone there is replaced by 3-amino-1- (2'-chlorophenyl) -5-pyrazolone. The dye mixture thus obtained melts after recrystallization from acetonitrile at 84 to 85 ° C.

h) α-Benzoyl-3- [α- (3'-pentadecylphenoxy) -n-butyramido] acetanolide

By reacting ethyl benzoylacetate and m-nitroanüin in boiling xylene and then catalyzed Reaction of the formed nitro compound over platinum oxide the amine of the formula is obtained

.NH,

A solution 45 Man startled by 4.4 g (0.015 mole) of the chloride of this amine in 25 cc of dry pyridine at ice from, treated dropwise with 6.1 g (0.015 mol) of the produced according to A acid chloride, can be several hours at room temperature and then the mixture is poured into ice water mixed with an excess of hydrochloric acid, the solid substance which separates out is collected, water and cold methanol are added and the mixture is crystallized from about 300 ecm of methanol. 5.2 g of the colorless dye binder with a melting point of 55 to 56 ° C. are obtained.

i) N- {p- [N'-Benzyl-N'- (p-tolyl) -sulfamyl] -phenyl} - [a- {p- [a- (3-pentadecylphenoxy) -butyramido] -benzoyl} -acetamide

By reaction of ethyl p-nitrobenzoylacetate and N'-benzyl-N '- (p-tolyl) -sulfanilamide and subsequent catalytic reduction of the nitro group is obtained Amide of the formula

O H

HoN- / \ - C - CH "- C - N

SO ₂ N

CH,

Starting from this amine, the amine is obtained after the nitro group with Raney nickel Method according to h) the specified dye binder. the formula

65 k) a-Benzyl-6-chloro-3- [a- (3'-pentadecylphenoxy) -

n-butyramido] acetanilide CH

By reaction of the acid chloride obtained according to A » with 4-CHor-3-rdtroanüin and subsequent reduction HIGH

I 11 I. o-c-c-ν

NH ₂

I 0/5 431

Heating 10 g (0.02 mol) of this amine with 0.4 g (0.02 mol) ethyl benzoyiacetate in xylene gives the dye former specified above.

Claims (2)

Claim: 1. Photographic, in particular color photographic recording and copying material, characterized by at least one halogen silver emulsion layer which contains a dye former of the general formula I R ₁ OH or II A-Y-N-C-C-O Contains, where R _{1 is} hydrogen or an alkyl radical, R _{2 is} an alkyl radical with 10 to 20 carbon atoms, R _{3 is} hydrogen, an alkyl or an aryl radical, A is a dye-forming coupling radical, namely a reactive methylene or phenolic hydroxyl group, and Y is one of the groups O H O H - C - N - alkylene, - C - N - arylene, --N - arylene means. 2. Photographic material according to claim 1, characterized in that the dye former of Formula I corresponds and A is represented by a naphthol or a pyrazolone. Considered publications:
German Auslegeschrift No. 1000 233;
U.S. Patents Nos. 2,706,683, 2,706,685,
511,231, 2,474,293, 2,322,027, 2,304,940, 2,369,489;
"Zeitschrift für Angewandte Chemie", 1944, p. 113 ff. © 90 ^ 729/384 2.60