DE2140309A1 - Photographic recording material - Google Patents

Description

PATENT LAWYERS DR.-ING. WOLFF, H. BARTELS, DR. BRANDES, DR.-ING. HERO

July 27, 1971

MUNICH 22

THIERSCHSTRASSE 8

TELEPHONE: (0611) 293297 25/2

Registration number. 123 107

EASTMAN KODAK COMPANY, 343 State Street, Rochester, New York State, United States of America

Photographic recording material

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■ The invention relates to a photographic recording material, consisting of a support and at least one light-sensitive silver halide emulsion layer applied thereon and optionally intermediate and / or top layers, at least one layer being one dissolved in one or more solvents Contains coupler compound.

It is known that indophenol, Color images produced by indoaniline, azo and azomethine dyes to some extent before exposure to actinic radiation by adding certain phenolic compounds with a condensed Let protect heterocyclic ring system as stabilizers. Such / additives are generally used incorporated into the layers in which the color images are produced, either in the form of dispersions in a solvent or together with a color coupler and a solvent.

The procedure can be that the stabilizers are first dissolved in a solvent, e.g. in di-n-butyl phthalate, whereupon the resulting solution is incorporated into a gelatin solution. The mixture obtained can then by a Colloid mill to be given.

Examples of the manufacture and use of such image stabilizers can be found in U.S. Patent 3,432,300.

It is also known that to stabilize photographic Images usually require a not inconsiderable amount of stabilizer. For example, it has been shown that concentrations of up to about 2 moles of stabilizer per mole of coupler are often not uncommon. Disadvantageous in use such high stabilizer concentrations and the

/ "Color images stabilizing or protective

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_ ¹ Z _

The amount of solvent required for such stabilizer concentrations is that the photographic images obtained often swell up and have inadequate physical properties in various respects, i.e. they are as a rule considerably softer and more hard than their counterparts unstabilized recording materials.

Furthermore, such layers produced using gelatin have a tendency to become porous and to curl during the photographic development process. A disadvantage of many of the known image stabilizers _p is also that they have a relatively high melting point and easy to crystallize-prior to or during the coating, especially when used then _s using geringerLÖsurfsmittelmengen xverden. This can lead to blockages of the coating devices, which in turn lead to "streaky or otherwise incompletely coated materials"

The object of the invention is to provide a photographic recording material from which color photographic images of improved stability can be produced without having to accept the disadvantages of the previously known processes. A very special aim was to create a new recording material which can not only be used for the production of color photographic images with increased stability ₈ but also has an improved service life and a reduced mass volume and an improved profile with reduced weight.

The invention was based on the knowledge that a certain Class of so-called sterically hindered phenols outstanding as

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Use stabilizers and at the same time as coupler solvents leaves.

The invention relates to a photographic recording material, consisting of a support and at least one light-sensitive silver halide emulsion layer applied thereon and optionally intermediate and / or top layers, at least one layer being one in one or more solvents contains dissolved coupler compounds, which is characterized in that it contains the coupler compound in a solvent or contains dissolved solvent mixture which consists of a sterically hindered phenol of the following formula:

A-OH

in which A represents, consists or contains a substituted phenyl radical.

The sterically hindered phenols used in the manufacture of a photographic recording material according to the invention are hydrophobic in nature. They can be used alone or in a mixture with other conventionally known coupler solvents and / or so-called easily removable auxiliary solvents. The use of sterically hindered phenols which have a melting point of not higher than 10O ⁰ C or at least when used with other solvents, ie other customary known coupler solvents and / or auxiliary solvents, to a so-called combined melting point of not higher than 100 ⁰ C lead. Such solvent systems preferably remain liquid at room temperature or at temperatures slightly above room temperature.

- 4a -

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The sterically hindered phenols used according to the invention act in terms of their dissolving capacity like the usual known high-boiling hydrophobic photographic coupler solvents, e.g., of the type known from U.S. Patent 2,304,939, but unlike the known coupler solvents image stabilizing properties,

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-r- ⁶

atd »-e · .

In the given formula A-OH, A can be any substituted phenyl radical, i.e. A can inter alia. also a phenyl radical with one be fused-on heterocyclic radical in the 4-5 position with respect to the OH group.

A can advantageously be the radical of a hydroxyphenyl ether, for example a p-alkoxy-m-alkylphenyl radical or a p-oxyisobornyl-substituted Phenyl radical or a 6-hydroxychroman radical, a 5-hydroxycoumaran radical or a hexahydrodibenzofuran-5-ol radical.

It has proven to be particularly advantageous if for production a recording material according to the invention, a coupler solvent is used, which is composed of at least one sterically hindered phenol of one of the following formulas or at least one sterically hindered phenol of one of the following formulas Contains formulas;

II.

R ₁

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R ₂ and IV

where mean:

R, Rj,
Around

, R.

an alkyl or p-isobornyl radical,

R ₂ , each a hydrogen atom or an alkyl or R, alkoxy radical, where it applies that (a) R- can additionally be an alkene radical and (b) only one of the radicals R and R- in formula I can be a hydrogen atom ;

a hydrogen atom or an alkyl, alkoxy or aryl radical;

and in each case a hydrogen atom © or an alkyl radical;

a hydrogen atom or a short-chain alkyl radical or a remainder of the formula:

N-Rq, in which R _{0 is} an aryl grate 1 ^yy

^R 10 and

a radical of the formula NR _n wherein R _n and R

is an alkyl radical.

have the meanings given,

1O

a nitrogen-containing 5- or 6-membered heterocyclic Ring, or a residue of the formula

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2U0309 ϊ

-O-Rq or -OR- _Q in which R _g and R. _{Q have} the meanings given.

If Rq has the meaning of an alkyl radical, this can be linear or branched-chain. The alkyl radical preferably has 1 to 22 carbon atoms. The alkyl radical can also consist of a cycloalkyl radical. Such a cycloalkyl radical preferably has 3 to 8 ring carbon atoms. R ₀ can thus be, for example, a methyl, propyl, isopropyl, t-butyl, octyl, dodecyl, octadecyl, n-docosanyl, cyclooctyl or cyclopropyl radical or an isobornyl radical.

If R, R ₁ , R ₂ , R and R ₄ are alkyl radicals, these can also consist of cycloalkyl radicals. Otherwise, the alkyl radicals represented by R, R ₁ , R 2, R j and R ₄ can be linear or branched-chain. They preferably have 1 to 20 carbon atoms. Of particular importance are compounds in which R, R ₁ , R ₂ , R ₃ and R. represent short-chain alkyl radicals or corresponding cycloalkyl radicals. If R, R 1, R ₂ , R, and R are alkoxy radicals, these preferably also have 1 to 20 carbon atoms.

Specifically, R, R, R ₂ , R and R can be, for example, methyl, butyl, 2,2-dimethylbutyl, octyl, dodecyl, octadecyl, eicosonyl, cyclooctyl and cyclopropyl radicals. One or more of these alkyl, cycloalkyl and Axkjci alkoxy radicals can be further substituted, ζ, B. by hydroxyl, carboxyl, carbalkoxy, acyloxy, sulfo, sulfonyloxyamido, alkoxy, aryl and / or aryloxy radicals and / or ilalogen atoms. Typical such substituents by which the alkyl, cycloalkyl and alkoxy radicals can be substituted are, for example, chlorine atoms, methoxy, octyloxy, carbomethoxy, CH ₃ -CO-O-, phenyl-, naphthyl-, phenoxy-

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and naphthoxy residues.

R ₃ can additionally be an alkylene, in particular a short-chain alkylene radical, for example a pentene-3 radical substituted in the 4-position by a short-chain alkyl radical, e.g. a 4-methyl-3-pentenyl radical,

If R ₆ , R ₇ and R _{g have} the meaning of alkyl radicals, then these likewise preferably have from T to 22 carbon atoms. This means that R ₆ , R and R _g can be, for example, methyl, ethyl, octyl, w & i or dodecyl radicals.

If R ^f ^ has the meaning of a radical of the formula

^R 1O

thus R _g preferably has the meaning of a phenyl, naphthyl or benzyl radical. R ₁₀ is preferably a short-chain alkyl radical. R ₁₀ can be, for example, a methyl, octyl or octadecyl radical. Accordingly, the can be given by the formula

^R 1O

for R ¹ , the radical represented may be, for example, an N-methyl-N-naphthylamino radical or an N-octyl-N-naphthylamino radical or an N-octyl-N-phenylamino radical «

If R _{5 is} an alkyl or alkoxy radical, these radicals preferably have from T to 8 carbon atoms. If Rr has the meaning of an aryl radical, this preferably consists of an aryl radical of the phenyl or naphthyl series. R ^ can thus be, for example, a methyl, methoxy, butoxy,

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Decyloxy, octyl, octadecyl, phenyl or naphthyl radical. Owns Z is the meaning of a radical of the formula

^R 1O

so here R _g and R ^ _{0 have} the meaning already given, ie Rg can be, for example, a phenyl, naphthyl or benzyl radical, it being understood that these aryl radicals can optionally be further ring-substituted, for example by alkyl and / or alkoxycarbonyl radicals and / or halogen atoms. R ₁₀ is preferably a short-chain alkyl radical.

Z stands for a nitrogen-containing 5- or 6-membered heterocyclic Ring, this can for example consist of a piperidyl, pyridyl, pyrrolidyl, quinolino, or tetrahydropyranyl ring.

The number and size of the alkyl radicals that make up the phenolic Rings that can be substituted can be very different, depending on the diffusion and solubility properties desired. The ring substituents preferably consist of methyl, isopro-

en pyl, t-butyl, t-octyl and n-octadecyl radicals and the corresponding further substituted alkyl radicals in which the alkyl radical is substituted, for example, by hydroxyl, carboxyl, carbalkoxy, Acetoxy-, SuIfo-, Acetamido-, Benzamidfio-, Methoxy-, Butoxy-, Dodecyloxy-, Phenoxy and / or naphthoxy groups and / or halogen atoms.

The invention enables the production of photographic recording materials for the production of color photographic images with improved image stability, in particular improved stability of the purple dye image. The improved image stability is achieved without coating defects in the

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Production of the recording materials must be accepted and without impairing the quality of the recording materials produced through the use of those used according to the invention Solvent suffers. The sterically hindered phenols used according to the invention as coupler solvents also make it possible a slight dissolution of the couplers, so that there is no premature crystallization in the preparation of the coupler solutions, which could hinder the manufacturing process of the recording materials.

The solvent stabilizers used for the production of a photographic recording material according to the invention leave can be easily produced, e.g. by reacting an appropriately substituted phenol with a diene, terpene or enol ether in Presence of a Lewis acid, for example zinc chloride or by Implementation of an enamine with a quinone.

Further details and other production methods for producing the solvents used according to the invention can be found, for example in U.S. Patents 3,184,457 and 3,432,300.

Typical, advantageous solvent stabilizers for manufacture of a photographic recording material according to the invention are, for example:

1. Z ^ -dimethyl ^ -methyl-o-hydroxy ^ -octyl-chroman,

2.2 ^ -Dimethyl ^ -isopropyl-ö-hydroxy-y-octyl-chroman,

3. 2-methyl-2- (4,8-dimethyl) nonyl-6-hydroxy-7- (or - & -) - octylchromane,

4. 2- (N-methyl-N-phenyl) amino-3,3-dimethyl-5-hydroxycoumaran,

5. 2-methyl-2-hexadecyl-6-hydroxy-7-t.-butyl-chΓoman,

6. 2,2-dimethyl-4-isopropyl-5-methyl-6-hydroxy-7-methyloxychroman,

7. 2,2,4,5-tetramethyl 1-6-hydroxy-7,8-dimethoxychroman,

8. 2-methyl-2-hexadecyl ~ 6-hydroxy-8-t.-butylchroman,

9. 2-methyl-2 (4,8-dimethyl) nonyl-5-methyl-6-hydroxy-7,8-dimethoxychroman,

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10. 2-methyl-2 (4,8-dimethyl) nonyl-6-hydroxy-7-t.-butylchroman,

11. 2- (N-Methyl-N-phenyl) amino-3,3-dimethyl-5-hydroxy-6-t-butylben ζofuran,

12. 2-Hydroxy-3-octyl-5a-methyl-8-isopropyl-5a, 6,7,8,9,9a-hexahydrodibenzofuran,

13. 2-t.-Octyl-4-dodeGyloxyphenol _#

14. 2-t-octyl-4-isobornyloxyphenol,

15. 2- (γ-carboxyethyl) -α-piperidino-3,3-dimethyl-5-hydroxy-6-t, -butylcoumaran,

16. 2- ^ ~ N-methyl-N- (p-carboxymethyl) benzyl_7amino-3,3-dimethyl-5-hydroxy-6-t, -butylcoumaran ,

17. 2-Hydroxy-3-octyl-5a-methyl-8-isopropyl-5a, 6,7,8,9,9ahexahydrodibenzofuran,

18. 2 - ^ 'N-methyl-N- (p-carboxymethyl) benzyl_7amino-3,3-dimethyl-5-hydroxy-6-t, -octylcoumaran,

19. 2-Hydroxy-5a- (N-methyl-N-phenyl) -amino-5a, 6,7,8,9,9ahexahydrodibenzofuran,

20. 2-methyl-2- (4-methyl) -3-penteny1-6-hydroxy-7-t.-octyIchroman, 21. 2,2,5,7,8-Pentaπlethyl-4-isopropyl-6-chroman,

22, a-tocopherol,

23, ß-tocopherol,

24, γ-tocopherol and

25, δ-tocopherol,

Compounds of the formula A-OH are effective stabilizers for protecting a wide variety of dyes, including photographic ones Masking dyes and especially effective stabilizers for protecting dye images caused by chromogenic Development of 5-pyrazolone color couplers were obtained, normally used in color photography, in particular for the production of crimson colorants,

Typical masking dyes that stabilize according to the invention let are known, for example, from "Encyclopedia

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2U0309 - «r-

Chemical Technology ", Volume 5, pages 812 to 845 (1964) and from" The Journal of Photographic Science ", Volume 14 (1966) pp. 260-277.

For example, the photographic recording materials according to the invention can be used for the production of magenta dyes suitable color couplers of the US patents

2 600 788, 2 725 292, 2 908 573, 3 006 759, 3 062 653, 3 152 896,

3,311,476 and 3,419,391 of the known type included.

Cyan dye-forming color couplers used in the manufacture of a photographic recording material are, for example, from US patents 2,474,293,

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2 725 292, 2 895 826 and 2 908 5 73 are known. Such chromogenic development converts them into blue-green dyes Couplers are typically phenolic or napoleic Links. The dyes and dye images obtained from these color couplers can be advantageously obtained with the aid protect the stabilizers used according to the invention from the adverse effects of light.

Yellow dye-forming couplers used in the manufacture of a photographic material according to the invention are known from US Pat. No. 2,908,573, for example. The for the production of inventively stabilizable Color couplers used in yellow dye images typically consist of so-called ketomethylene compounds.

If the stabilizers used according to the invention are sterically hindered phenols are used together with other solvents, for example the known high-boiling organic coupler solvents known, for example, from U.S. Patents 2,304,939 and 2,322,027, be used.

\ A typical, easily removable, low-boiling and / or water-soluble co-solvents that can be used with the sterically hindered phenols, for example ethyl acetate, is. Such a cosolvent can facilitate the dissolution of the coupler compounds in the hindered phenol. Such solvents, which together with the

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Sterically hindered phenols can be used to dissolve the couplers are, for example, from the USA patents 2 801 170, 2 801 171 and 2 949 360 are known.

It has proven to be useful to use the sterically hindered phenols of the formula A-OH in concentrations of about 1/10 to about 5 times the weight of the organic color coupler to be dissolved to use. It has proven to be particularly advantageous to use a concentration corresponding to the coupler solvent half to 2 times the weight of the coupler.

The support of the photographic recording material according to of the invention can consist of one of the conventionally known supports which are customarily used for the production of photographic Recording materials can be used, for example made of cellulose acetate and polyterephthalate and other materials such as those described in Duffin's book "Emulsion Chemistry", Chapter 3, pages 47 to 56, 1966. Suitable supports also include those made of paper or others fibrous materials that are coated with a hydrophobic layer that repels water and not water absorbed or adsorbed.

If appropriate, the hydrophobic surfaces of layer supports can be used with a hydrophobic surface made of a hydrophobic resin with ^ electrons are irradiated, as for example is known from British patents 971 058 and 1 060 526 and US patents 2 864 755 and 2 864 756, to improve the adhesion of hydrophilic colloid layers on the hydrophobic surfaces. If necessary, however, can also be made from

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"6

- rs—

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hydrophobic polymers can be used, i.e. the hydrophobic polymers can either be applied to other substrate materials can be applied or used directly for the production of substrates. Typical substrate with hydrophobic surfaces which can be used for the production of recording materials according to the invention, are, for example, polyethylene terephthalate film substrates irradiated with electrons, i.e., substrates that are irradiated with electrons in such a way that they have a contact angle of \> reni-P have less than 45 °. Such layer supports can, for example, according to the method known from US Pat. No. 3,220,842 getting produced. The layer support surface can furthermore, for example, consist of an irradiated with electrons Consist of a chromium halide complex, e.g. a stearatochrome dichloride complex, which has been irradiated with electrons according to the method known from US Pat. No. 3,117,865. In the end can be used to produce the recording materials according to the In accordance with the invention, supports with gelatin layers can also be used, e.g. Electron radiation is hardened, as is the case, for example from Belgian patent 671 661 is known.

Other suitable hydrophobic layer support surfaces , which can be irradiated with SixkK electrons in order to increase their adhesion to hydrophilic emulsion layers, consist, for example, of poly-α-olefins, preferably poly-α-olefins made from olefins with 2 to 10 carbon atoms, e.g. polyethylene, Polypropylene, poly (3-methylbutene-1), poly (octene-I), poly (decene-I) and the like, also made from polyamides, polyacetals, polycarbonates and cellulose esters and also cellulose ethers, for example cellulose triacetate, cellulose acetate butyrate and ethyl cellulose.

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V (T-

The hydrophobic material, e.g. a poly-olefin, can be applied to the Paper backing can be applied by conventionally known methods, for example by extruding a melt of a Poly-α-olefin or by applying a solution of the polyolefin. The substrate can optionally contain a wide variety of customary functional additives, e.g. pigments, for example titanium dioxide and antistatic compounds such as those described in US Pat. No. 3,253 to be discribed.

The following first describes the production of some according to the invention described as a solvent usable sterically hindered phenols.

A) To a mixture of 40 ml acetic acid, 22.2 g of n-octylhydroquinone and 0.2 g of zinc chloride, 8.6 g of 2,5 dimethyl-2,4-hexadiene was added, itforauf the resulting mixture for 2 hours at 60 ⁰ C was heated. Two drops of concentrated sulfuric acid were then added, followed by heating for an additional TO minutes. Finally, the mixture was slowly poured into 500 ml of cold water, an oily yellow reaction product separating out. This was subjected to molecular distillation. 17 g of 2,2-dimethyl-4-isopropyl-6-hydroxy-7-octylchroman with a melting point of -16 ° C. were obtained.

B) Became a slurry of 5.4 g of quinone in 50 ml of benzene slowly a solution of 8.35 g of N-methyl-N-phenylisobutenylamine added to 25 ml of benzene, while cooling to 40 to 50 ° C. The reaction mixture was then left to stand for 12 hours at room temperature, whereupon the solid precipitate formed was filtered off and purified by recrystallization. A total of 6 g of 2- (N-methyl-N-phenyl) amino-3,3-dimethyl-5-hydroxychoumaran were obtained obtain.

C) The process described under A) xuurden 2,3-dimethoxyhydroquinone and 2,7,11 ~ trimethyl-1-dodecen-3 - ol reacted with one another, In this way 2-methyl-2 (4,8-dimethyl) nonyl-5-methyl-6-hydroxy-7,8-dimethoxychroman became with a boiling point of

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2H03-09

128 ⁰ C / T μ obtained ..

D) The process described under B) gave 2-hydroxy-S-octyl-Sa-methyl-e-isopropyl-Sa, 6,7,8,9,9a-hexahydrobenzofuran with a boiling point of 170 ° C / 2u. It was Proceed in such a way that a slurry of 0.05 Moles of t-butylquinone in 50 ml of benzene slowly added a 0.05 molar solution of N-methyl-N-phenylisobutenylamine in 25 ml of benzene became.

E) A mixture of acetic acid, t-butyl hydroquinone and zinc chloride and dodecene was reacted according to the method described under A). This time, however, a temperature of from 20 to 25 ^° C. was used. Furthermore, the reaction mixture was allowed to stand for 12 hours. The 2-t-octyl-4-dodecyloxyphenol obtained had a boiling point of 182 to 183 ° C./0.5 min.

F) A slurry of t-octylquinone in BEnzol was after the process described under B) for N-methyl-N-phenylethenylamine admitted. Thus became 2-hydroxy-5-a- (N-methyl-N-phenylamino) -5a, 6,7,8,9,9a-hexahydrodibenzofuran obtained with a boiling point of 24O ° C / 1 μ.

The following examples are intended to illustrate the invention in more detail.

example 1

50 mg of the coupler 1-C2,4-dimethyl-6-chlorophenyl) -3- / ~ 3- [a- (m ~ pentadecylphenoxy) -butyramido) which gives a purple-red dye image Benaamido / -5-pyrazolone were in iix di-n-butyl phthalate hereinafter referred to as capping solvent Y, g

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2H0309

solves. The solution was then added to an 8% gelatin solution, whereupon the coupler solution was dispersed in the gelatin solution in a colloid mill. The dispersion was then in a green light sensitized silver chloro-. registered bromide emulsion, whereupon the emulsion on a cellulose acetate ^ has been applied. The coupler compound and dispersion method used are known from Example 1 of US Pat. No. 3,432,300.

The green-sensitive recording material obtained contained 50 mg of silver, 250 mg of gelatin and 50 mg of coupler and solvent Y per 0.0929 m ^{2 of} support surface.

A further recording material was produced according to the method described under A., but this time the Coupler compound in 25 mg of solvent Y and 25 mg of the im

following specified compound no. 1 carrier surface was dissolved.

per 0.0929 m shift

Melting point = 46-48 ⁰ C

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-vs-

C.

Another recording material was produced by the method described under A., but this time using 50 mg of the indicated sterically hindered phenol as the coupler solvent
became.

Phenol (Compound No. 1) was used per 0.0929 m ^{2 of} support area

The recording materials A to C have been developed and ψ in a conventional manner, as is the United States Patent 3,189,452 is described, for example, in column 8, process D, then exposed through a continuous wedge with green light coal stages.

The recording materials developed had practically the same photographic and physical properties Sensitivity, Fog, Contrast and D

The recording materials A to C were then subjected to a fading test subjected »by exposing them to simulated northern daylight for 27.1 χ JO Lux hours, by the method described, for example, in column 6, lines 34 through 43 of U.S. Patent 3,432,300. The fading " grad was then determined at a peak wavelength at a density of 1.0.

The degree of fading of the recording materials A to C was 86 I, 371 and 251, respectively.

Example 2

Following the procedure described in Example 1, three further

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tere recording materials, corresponding to the recording materials A through C, except that the coupler solvent # 1 was substituted for the coupler solvent No. 2 for the production of the recording materials D and C used became.

OH

Melting point - -16 ⁰ C

The photographic and physical properties of the three Recording materials were practically the same.

The balance of the three recording materials produced was included;

Recording material A: 861; Recording material B: 31%; Recording material C: 19%.

Example 3

Following the procedure described in Example 1, additional recording materials were prepared using the coupler solvents 4,9,12,13,19,22 and 25. The

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Coupler solvent once together with the coupler solvent Y is used and on the other hand as the sole coupler solvent. The results obtained are summarized in Table A below. In this table, X denotes one of the compounds 4,9,12,13,19,22 or 25.

Table A.

Connect
application no. Comparative mate
rial with 50 mg Y
Fading in i. Solvent Y
(25 mg)
Compound X (25 mg)
Fading in I. Compound X (50mg)
Fading in I. 4th 67 % 53 I. 30 % 9 54 p 27 % 18 % 12th 97 * 42 % 27 % 13th 83 p 17 % 10 I. 19th 61% 28 % 18 \ 22nd 77 I. 67 I. 30 % 25th 77 I. 40 I. 20 %

Some compounds, especially δ-tocopherol (compound no.25) provide a relatively modest dye stabilizing effect when they are used as solvents together with a prior art coupler solvent (coupler solvent Y) in the specified ones Concentrations are used. However, they are extremely effective when used as the sole coupler solvent will.

Example 4

According to U.S. Patent 3,189,452 under section

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In the process described in "Process A", a multilayer color negative film of camera sensitivity was produced. Of In addition, two corresponding color negative films were produced, but this time with di-n-butyl phthalate as the coupler solvent Y partially or completely, as described in Example 1, was replaced. There were correspondingly favorable results as in example 1 described received.

Example 5

Using the coupler solvents given in Example 1 three more multilayer color reversal films of camera speed were prepared following the procedure described in Example 2 of FIG U.S. Patent 2,984,567. The color images obtained were practically identical Stabilities as described in Example 1.

Example 6

The procedure described in Example 2 was repeated, but this time using the following developer compounds instead of 4-amino-3-methyl-N-ethyl-N-ß- (methanesulfonamido) ethylaniline sesquisulfate hydrate were used:

a) 4-Amino-3-methyl-N-ethyl-N-ß-hydroxyethylaniline sulfate,

b) 4-amino-N-ethyl-N-ß-hydroxyethylaniline sulfate,

c) 4-Amino-3-methyl-N, N-diethylaniline hydrochloride and

d) p-Amino-NjN-diethylaniline hydrochloride.

The recording materials obtained were then as in Example 1 has been subjected to the fading test described. Corresponding degrees of fading as described in Example 1 were obtained.

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Example 7

The procedure described in Example 2 was repeated, but instead of the bleaching and fixing step after color development a bleach-fix stage as described in British Patent No. 991,412 has been switched on. There were corresponding Results as obtained when testing recording materials A to C of Example 2.

Example 8

Following the procedure described in Example 1, three more Recording materials produced, but this time a higher-melting 7-t.-octyl isomer as the sterically hindered phenol of compound No. 1 having the following structural formula OH

CH.

Melting point = 118 to 120 ° C

was used.

To produce the recording material A, 25 mg per 0.0929 m ^{2 of} the substrate area of the t.-octyl isomer and an equivalent amount of the solvent Y were used to dissolve the color coupler compound.

To produce the recording material B, 25 mg per

/ 0900 «/ 17/1

2
0.0929 m of the solvent Y and an equivalent amount of the yt-octyl isomer and 25 mg of ethyl acetate were used as auxiliary solvents, the melt being applied directly to the layer support.

To produce recording material C, 25 mg of the t.-octyl isomer of compound 1 and 25 mg of ethyl acetate were used as auxiliary solvents in each case per 0.0929 m 2 of layer support surface. The melt was quenched, noodled and left to stand in a refrigerator for a week, then melted again and let for an hour:
applied to the substrate.

melted and warmed to 45 ° C for one hour and then up

The recording material B had a moderate curl. Furthermore, streaks were seen and the photographic image was deformed. The recording material C had broad stripes without an emulsion _{coating f,} which were evidently caused by recrystallization of the coupler compound.

U 3 η 0 J / j 7 *> 1

Claims (10)

2U0309 PATENT CLAIMS Photographic recording material consisting of a Layer support and at least one light-sensitive silver halide emulsion layer applied thereon and optionally Intermediate and / or top layers, at least one layer being one in one or more solvents contains dissolved coupler compound, characterized in that it contains the coupler compound in a solvent or Contains solvent mixture dissolved, which consists of a sterically hindered phenol of the following formula . A-OH in which A represents a substituted phenyl radical or contains one. 2. Photographic recording material according to claim 1, characterized characterized in that it is a sterically hindered phenol of the formula as the coupler solvent A-OH contains, in which A is the remainder of a hydroxyphenyl ether, one 6-hydroxychroman, a 5-hydroxycoumaran or a hexahydrodibenzofuran-5-ol is. 3. Photographic recording material according to claim 1, characterized characterized in that it contains a sterically hindered phenol of one of the following formulas as the coupler solvent 203308 / i / 41 2H0309 OH II. III. and IV «. R. Rr where mean: R and an alkyl or p-isobornyl radical; in each case a hydrogen atom or an alkyl or alkoxy radical, where it applies that (a) R ^ can additionally be an alkene radical and (b) only one of the radicals R
Can be hydrogen atom; and R .. in formula I. a hydrogen atom or an alkyl, alkoxy or aryl radical; 209808/1 -Vh- " Rr, Rj and Rg each represent a hydrogen atom or an alkyl radical; R ^f , a hydrogen atom or a short chain Alkyl radical or a radical of the formula: NR ₉ , ^R 1O
in which R _{9 is} an aryl radical and R _{10 is} an alkyl radical is and
Z is a radical of the formula NO ₉ ^R 1O
wherein R ₉ and R _{10 have} the meanings given have a nitrogen-containing 5- or 6-membered heterocyclic ring, or a radical of the formula -0-R ₉ or -0-R ₁₀ in which R ₉ and R _{10 have} the meanings given. 4. Photographic recording material according to claim 3, characterized characterized in that there is a sterically hindered phenol of one of the formulas I, II, or III as the coupling solvent contains, in which mean: Rq is an isobornyl radical, R is a hydrogen atom or an alkyl radical, R ₁ and R2 each represent a hydrogen atom or an alkyl radical, it being the case that in formula I at most one of the radicals R and R _{1 can be} a hydrogen atom, 209808/1741 2H0309 Rj is an alkyl or short-chain alkene radical; R., R ₅ and Rg each represent a short-chain alkyl radical and Z is a residue of the formula ' NO ₉ ^R 10 where R _{g is} a benzyl radical and R ^ _{0 is} a short-chain alkyl radical or a nitrogen-containing 5- or 6-membered heterocyclic radical. 5. Photographic recording material according to claim 3, characterized characterized in that it contains a sterically hindered phenol of the formula I as coupler solvent, in which: R, RJ and R ₅ each have a hydrogen atom or an alkyl or alkoxy radical, with the proviso that only one of the radicals R and R * is a hydrogen atom can and Rq is an alkyl or p-isobornyl radical. 6 .. Photographic recording material according to claim 3, characterized in that characterized in that it contains a sterically hindered phenol of the formula II as a coupler solvent in which mean: each a hydrogen atom or an alkyl or alkoxy radical, each is a hydrogen atom or an Aikaxjcx Alkyl radical, with the proviso that R is also a short-chain alkene radical, and a hydrogen atom or an alkyl, alkoxy or aryl radical. 208808/1141 R. and ^R 1 ^R 2 • ^R 3 and ^R 4 ^R 5 2U0309 7. Photographic recording material according to claim 3, characterized characterized in that it contains a sterically hindered phenol of the formula III as a coupler solvent, in which mean: R, R ₁ , R ₂ , R ₅ and each represents a hydrogen atom or an alkyl radical and a remainder of the formula NR ₉ ^R 1 in the r _g and 10 have the meaning given or a nitrogen-containing 5- or 6-membered heterocyclic radical. 8. Photographic recording material according to claim 3, characterized characterized in that it contains a sterically hindered phenol of the formula IV as the coupler solvent, in which mean: R, R-j, and Rg R ¹ , each represents a hydrogen atom or an alkyl or alkoxy radical and a short-chain alkyl radical or a radical of the formula NO ₉ wherein R ₉ and R have meaning. ^R 10 'the specified Be 203808/1741 2H0309 9. Photographic recording material according to claim 6, characterized in that it is used as a coupler solvent Contains sterically hindered phenol of the formula II, in which: (a) R is an n-octyl radical, R _{1 is} a hydrogen atom, R _{2 is} a methyl or isopropyl radical, R ₃ and R _{4 are} each a methyl radical and Rr is a hydrogen atom, or (b) R is an n-octyl radical, RJ is a hydrogen atom, R- is an isopropyl radical, R ₃ and R _{4 are} each a methyl radical and R _{5 is} a hydrogen atom, or (c) R, R ^ and R ₂ each represent a hydrogen atom, R _{3 is} an alkyl radical with 1 to 16 carbon atoms and R ₄ and R _{5 are} each a methyl radical « 10. Photographic recording material according to claims 1 to 9, characterized in that it contains the coupler solution in at least one silver halide emulsion layer. 209808/1741