CA1229610A - Colour-photographic recording material - Google Patents

Abstract

Colour-photographic recording material Abstract A colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, an interlayer and/or a protective layer, contains at least one novel polyalkylpiperidine compound of the formula I

(I) as a light stabiliser.
Colour images obtained by imagewise exposure and development of this colour-photographic recordlng material display good stability to the action of visible and ultra-violet light.
With respect to the definitions of the substituents and symbols in formula I, reference is made to claim 1.

Description

3-13711/5/+ By ~22~

Colour-photo~raphic recording material The present invention relates to a color-photographic recording material which, in at least one light-sensitive silver halide emulsion layer and/or ion at least one ox the conventional auxiliary layers, contains at least one novel polyalkylpiperidine light-stabiliser, and to the novel polyalkylpiperidine compounds.
In European Patent Application 11,051, a killer photographic recording material has already been described, which contains a polyalkylpiperidine light-stabiliser in order to improve the light fastness of the color images obtained with this material and to suppress undesired fogging.
It has now been found that, surprisingly an even better light-stabilising effect can be achieved when the compounds of the formula I, described below, are incorpor-axed unto the colour-photographic recording material.
The present application therefore relates to a colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, an inter-layer and/or a protective layer, contains at least one polyalkylpiperidine compound as a light stabilizer, wherein the polyalkylpiperidln~ compound is of the formula I
R5~
HO R o Al Shirley (I) (A) (CRY) n I I; R2 I

~2~9~

in which R1 and R3 independently of one another are hydra-gun or methyl, R2 is hydroxyl, C1-C12-alkyl, C3-C12-alkenyl, C3-C4 alkynyl, 2~hydroxyethyl, C2-C11-alkoxyalkyl, C7-C14-aralkyl or a group of the formula -(CH2)p-CH(R6)-X1 or -SHRIEKS, in which p is one of the numbers 1, 2 or 3, X1 is halogen, cyan, -OR, -OOZIER, -OC(O)N(R7)(R8), -cto)oR7 or -C(O)N(R7)(R8)9 X2 is halogen, cyan, 1,2-epoxy ethyl, -CORN or CONNER ) and R6 is hydrogen, methyl or phenol, being hydrogen, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, phenol, C7-C14-alXaryl or C7-C14-aralkyl and R8 being hydrogen or C1-C4-alkyl, or R7 and I, together with the nitrogen atom to which they are bonded, forming a 5-membered or 6-membered heterocyclic wrier, or R2 is a group of the formula II
L-CO- (II) in which L is hydrogen, C1-C12-alkyl, C2 C12-alkenylJ
C3-C4-alkynyl, C3-C12-cycloalkyl~C7-C14-~lkaryl, C7-C14-aralkyl, chloromethyl, unsubstituted phenol, phenol which is substituted by two C1-C~ Kyle and one hydroxyl, or a group -Ox , in which is C1-C12-alkyl, cyclohexyl, C2-C12-alkenyl, bouncily or phenol or L is a group of the formula III
R3~ R4 -(A) OH (III) ~R5 or R2 is a group of the formula IV
c 10 (IV) o Roll in which R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-alk~nyl, C3-C12-cycloalkyl, phenol, C7-C14-alkaryl or C7-C14-aralkyl and R11 additionally can also be hydrogen, or R2 is a group ox the formula V

~2~6 OH
If I R5 CH2~CH(R12)~(~-C) -(us,') if (V) in which A' is ethylene or a group -CHESHIRE and q is zero or 1, and R12 and R13 independently of one another are hydrogen, methyl, ethyl, phenoxymethyl or phenol, or R2 is a group of the formula VI
ox I\ SHEA R4 ! 'I' (VI) I C) - PA) 1, ./ n m I -in which B us a group Crower, in which r is a number from

2 to 12, or is C4-C8-alkenylene, C4-C8-alkynylene, phony-tone, xylylene, bitolylene, C5-C12-cycloalkylene or a group -COWAN -NHCO-, in which By is a groupCrH2r, phony-tone, naphthy~ne, tolylene or a group of the formulae R
CRY or -C -I -in which R' is hydrogen methyl or ethyl, R" is hydrogen or methyl and r is as defined above, or R2 is one of the groups Cicero or-OR15,in which z is the number 1 or 2, R14 it Cl-C12-alkyl, C7-C14-alkaryl or phenol and R15 is Cl-C12-alkyl, C~-C12-alkenyl, C7-C14-aralkyl or a group ox the formula L9-CO-, in which L' is as defined above for L, R4 and R5 independently of one another are Cl-C12-alkyl, C~-C12-cycloalkYl, C7-C14-aralkYl, C7-C14 alkaryl or phenol and R4 can additionally also be hydrogen or a group of the formula It Sue OH
\ / 5 ROY) - (C-Y) - R via) Kiwi I R
n which Al, , R3, R5, A, Y, m and n are as defined and Do O O
M is a direct bond, Cog -S-, -S-S-, -S-, -S-, -CH2-S-CH2-, Do -CH2-0-CH~-, -O- and -N(D3)-, and Do and Do independently of one another are hydrogen, Cl-C18-alkyl, alkyd inter-rutted by 1 to 3 -S- or phenol, or Do and Do together with the C atom linking them, form a 5-membered or 6-member Ed aliphatic ring and Do is hydrogen, Cl-C18-alkyl or phenol, Y is -N(R16)-~ in Welch R16 is hydrogen cl_cl8-alkyl~ c3-cl2-alkenYl, C3 C12-cyclo~lkyl, phenol, C7-C14-alkaryl~ C7-C14-aralkyl, C3-Cll at y y group of the formula VII

~'~ r2 VOW) I UREA
or a group -Z-D, in which Z is a -(CHIHUAHUAS group unsubsti-tuned or substituted by a methyl group, s being one of the numbers 2 to 4 and D being hydroxyl, -O'ER or -N(R18)(Rlg)~ in which R17 and R18 are hydrogen, Cluck-alkyd, C3-C12-cycloalkyl or a group of the formula VIII
OH

I \ / 5 (VIII) aye and R17 additionally can also be a group of the formula VII, Rig is hydrogen, Cl-C12-alkyl, C3-C12-cyclo y a group of the formula IX

, I 2 1 (IX) OH
R I! I
l OX

or R18 and Rig, together with the nitrogen atop to which they are bonded, form a 5-membered or embowered hotter-cyclic ring, or R16 is a group of the formula Ida l\ Ye, 2 1 C O I (Ida) OR i OR

Am it in which Q is as defined above for B, n is the number 1 and m is zero or 1, and A is ethylene or a group -CHESHIRE)- or -CHICAGO, in which R20 is hydrogen, methyl, ethyl, phenoxymethyl or phenol, E is cyan or a group -COREY, -CRY, -S02R22, -Pi-(O'ER, -C(O)NR24R25 or -COO, in which R21 is Cluck-Y 22 it Of Colloquial, C7-C14-alkaryl or phenol R
is Cl-Cla-alkyl, phenol or ally, and R24 and R25 indepen deftly of one another are hydrogen, Cl-C18-alkyl or phenol, and G is hydrogen, Cl-C18-alkyl, C3-C12-alkenyl, C3-C4-alkyllyl 7 C5-C12-cycloalkyl C6-C18-alkylcycloalkyl C6-C14-cycloalkylalkyl, C7-C14-aralkyl, C7-Clg-alkyl-aralkyl, phenol, or Cl-C18-alkyl which is substituted by phonics, C7-C10-alkylphenoxy, benzyloxy, cyclohexyloxy, ' 6' CRY or prig, R2Q being Cluck_ alkyd, C3-C12-cycloalkyl or a group of the formula VII, 27 g Of Cl~-alkyl~ C3-C12-cycloalkyl, phenol, C7-C 4-aralkyl or a group of the formula III and R28 being Cl-C18-alkyl, ally or phenol, or G is C2-C18-alkyl inter-rutted by -O-, -S-, -SO- or -S02-, a group of the formula VII or a group of the formula ~29 2 \ OH
OR

in which I and R30 independently of one another are Cl-C4-alkyl and R30 additionally can also be hydrogen, or, if E is a group -C(0)~ 2, G and R22 together are in-ethylene or tetramethylene.
Cl-C12-Alkyl substituents which may be present can be branched or unbranched alkyd, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, left.-bottle, n-pentyl, n-hexyl, n-octyl, 1,17 3,3-tetramethyl-bottle, n-nonyl, decal or dodecyl. Cl-C4-Alkyl is preferred. Cl-Cl~-Alkyl radicals R16 and R23 can add-tonally be 9 for example, tridecyl, tetradecyl, hexadecyl or octadecyl.
Cl-C4-Alkyl substituents which may be present are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl or tert,-butyl.
C3-C12-Alkenyl substituents which may be present are, for example, ally, methallyl, buttonhole, 2-hexenyl, 2-octenyl, 4-octenyl, disannul or 2-dodecenyl. Ally is preferred. C2-C12-Alkenyl substituents can add-tonally also be vinyl. In this case, vinyl and ally are preferred.

6.

C3-C4-Alkynyl radicals R2~ G and L are, for example, propargyl, n-but-l-ynyl or n-but-2-ynyl.
Propargyl is preferred.
C3-Cll-Alkoxyalkyl radicals R2 and Rl3 are for example, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-butoxyethyl, 2-n-butoxypropyl 9 2-n-octoxyethyl, 3-n-octoxypropyl or 6-n-butoxyhexyl. Additionally, a C2-alkoxyalkyl radical can also be methoxymethyl.
Halogens Al and X2 are, for example, bromide iodine and in particular chlorine.
C3-C12-Cycloalkyl su~stituents which may be pro-sent are, for example, cyclopropyl, cyclopentyl, cycle-Huxley, cycloheptyl, a-methylcyclohexyl, cyclooctyl, cycle-nonyl, cyclodecyl or cyclododecyl. Cyclohexyl is preferred.
C7-C14-Alkaryl substituents which may be present are, for example, phenol substituted by Cl-C4-alkyl, such as p-tolyl, 2,4-dimethylphenyl, 2,6-dimethylphanyl, 2 9 4-diethylphenyl, 2,6-diethylphenyl, 4-tert.-butylphenyl, 2,4-di-tert.-butylphenyl or 2,6-di-tert.-butylphenyl.
2,4-Di-tert.-butylphenyl and 2~4-dimethylphenyl are preferred.
5-Membered or 6-membered heterocycl~c rings, formed by and R8 or R18 and R19 together with the nitrogen atom to which they are bonded, are, for example, pyrrolidine~
oxazolidine, piperidine or morpholine radicals.
C7-C14-Aralkyl substituents which may be present are, for example, bouncily 9 p-methylbenzyl, p-tert.-butyl~
bouncily, l-phenylethyl, ,-dimethylbenzyl or 2-phenylethyl.
In -Crower- groups B, By or Q, in which r is a number between 1 and lo, r preferably is a number between 2 and 8. Examples are ethylene, ethylene, trim ethylene, tetramethylene, hexamethylene, octamethylene, none-ethylene, 2,2,4-trimethylhexamethylene, decamethylene and dodecamethylene.
C4-C8-Alkenylene radicals B or Q are, for example, Lo but-2-en-1,4-ylene~
C4-C8-Alkynylene radicals B or Q are, for example, but-2-yn-1,4-ylene.
C5-C12-Cycloalkylene radicals B and Q are, for example, cyclopentylene, cyclohexylene, cyclooctylene 9 cyclodecylene or cyclododecylene. Cyclohexylene is preferred.
Cl-C12-Alkyl radicals G, substituted by phonics, benzyloxy, cyclohexyloxy or cyan, can, for example, be one of the following radicals: 2-phenoxyethyl, bouncily-oxyethyl, cyclohexyloxymethyl, 2-cyanoethyl, cyanomethyl or 3-cyanopropyl.
C6-Cl~-Alkylcycloalkyl radicals G are, for example;
methylcyclohexyl, ethylcyclohexyl, butylcyclohexyl, left.-butylcyclohexyl, dodecylcyclohexyl, ethylcyclopentyl or butylcyclopentyl and C6-C14-cycloalkylalkyl radicals G
are, for example, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, cyclohexylhexyl, cyclohexyloctyl, cycle-pentylpropyl or cyclopentylhexyl.
Cl-C18-Alkyl radicals G, substituted by C7-C10-alkylphenoxy, can be for example, p-methylphenoxymethyl, p-methylphenoxyethyl, p-methylphenoxypropyl, pert butylphenoxymethyl, p-tert,-butylphenoxyethyl, 2,4-dimethylphenoxymethyl, 2,4-dimethylphenoxyethyl1 Dow-tert.-butylphenoxyethyl, 2,6-di-tert.-butylphenoxymethyl or 2,4,6-trimethylphenoxyethyl.
Colloquial radicals G interrupted by I So -SO- or -S02- are, for example 9 one of the following radix eels: methoxymethyl, 2-butoxyethyl, 2-octyloxyethyl~
isopropoxymethyl, 3-butylthiopropyl, 2-decylthioethyl, 2-(isohexylsulfinyl)-ethyl, 2-(butylsulfonyl)-ethyl or 2-(ethylsulfonyl)-propyl, If R2 is a group of the formula V or of the for-mute VI, and if R16 is or contains a group of the formula VII or of the formula IX, not more than two groups of the formula VII may be present in total in the compound of 9 96~
the formula I.
Those colour-photographic recording materials are preferred which contain, as the light stabilizer, at least one compound of the formula X

HOWE Amen ` 2 I
R5 C^~3 Churl in which R1 is hydrogen or methyl, R4 and R5 independently of one another are C1-C4-alkyl and additionally R4 can also be hydrogen or a group of the formula Pa OH
, R

(Pa) iamb- I '-R2 CH;~CH3 in which M is a direct bond, -CK(D2)- or -S- and Do is hydrogen or C1-C~-alkyl, A is ethylene, ethylene or a group -SCHICK-, in which E is cyan, -COUCH or -COUCH
and G is hydrogen, Cl-C18-alkyl, ally, cyclohexyl, bouncily or one of the two groups of the formulae C~3~c3 /C(C~3)3 ./ \; and -SUE / YO-YO
._. . = .
; c.3 Jo in which Rho is methyl or tert.-butyl, or E and G together form a group -COUCH-, n and m are as defined above, R2 it hydroxyl, C1-C4-alkyl, ally, methallyl, propargyl, bouncily, 2-hydroxyethyl, C2-C7-alkoxyalkyl or a group of ~%~

the formula -(CH2)p-CH(R6)-Xl or -SHRIEKS in w p is one of the numbers I 2 or 3, Al is halogen, cyan, I , -OOZE , -OZONE )(R8), COY or CON )(R83, X2 is halogen, Cowan, 1,2-epoxyethyl, -COY or -Cowan )(R83 and is hydrogen, methyl or phenol being hydrogen, Cl-C8-alkyl, vinyl, ally, methallyl, C5-c8-cycloalkyl 9 phenol or C7-C10-aralkyl and R8 being hydrogen or methyl, or R2 is a group of the formula II, in which L is hydrogen, Cl-C4-alkyl, vinyl, allele cycle-Huxley, phenol, bouncily 7 chloromethyl or a group -O , in which is Cl-C8-alkyl 7 cyclohexyl 9 vinyl, ally or methallyl, or L is a group of the formula III~ in which m, A, R4 and R5 are as defined for these preferred come pounds, and R3 is hydrogen, or R2 is a group of the for-mute IV, in which Rio and Roll independently of one another are Cl-C12-alkyl, cyclohexyl or phenol and Roll additionally can also be hydrogen, or Rz is a group of the formula XI

Sacroiliac -(A') --I I (XI) . _ . , in which n, R4, R5 and Y are as defined for these pro-furred compounds, A' it ethylene or a group -CHESHIRE)-, q is zero or 1, and R12 and R13 independently of one another are hydrogen or methyl, or R2 is a group ox the formula XII
SHEA / 3 o ~._.~ n m OH (XII) SHEA SHEA \R5 in which A, R4, R5, Y, n and m are as defined for these preferred compound sand B is a group -Shari or -CONH-~CHz~-rNHCO-~ in which r is one of the numbers 2 to 8, or C4-C8-alkenylene, xylylene or bitolylene, or Rz is ~2~36~L~

one of the groups -S02Rl4 of -Oriole, in which Rl4 is Cl-C4-alkyl, p-tolyl or phenol and R15 is Cl-C4-alkyl9 bouncily or a group of the formula LO in which L t it as already defined for L in these preferred compounds, and Y is N(Rl6)-, in which R16 is hydrogen, Cl-C12-alkyl, cyclohexyl, C3-C7-alkoxyalkyl or a group of the formula XIII
Jo 3 - (SHEA Jo -R
C~3 OH
I
- / 4 (XIII) -OH

in which r, m, At , R4 and R5 are as already defined for these preferred compounds.
Those colour-photographic recording materials are particularly preferred which contain, as the light stab-loser, at least one compound of the formula ZOO

\.~.~ m R2 (XIV) R5~ I SHEA
in which m is zero or l, A is ethylene or ethylene, I
and R5 independently of one another. are methyl or left.-( 16) in which Rl6 is hydrogen or Cl-C8-alkyl, and is hydroxyl, methyl, ally, bouncily, 2-hydroxyethyl, acutely, acryloyl, methoxy, Aztecs or a group of the formula MY 11 ._ I
I OH (XV) - 12 . ~22~
in which m, A, R4 and R5 are as defined for these pro-furred compounds, or is a group of the formula IV, in which Rio is Cl-C8-alkyl, cyclohexyl or phenol and Roll is hydrogen, Cl-C8-alkyl or cyclohexyl.
Those colour-photographic recording materials are also particularly preferred which contain, as the light stabilizer, at least one compound of the formula XIV7 in which is a group of the formula o ~C(cH3) 3 Ho 2 \ / OH
C(CH3)3 and m, A, R4, R5 and Y are as defined in the last define-lion of preferred compounds, as well as those color-photographic recording materials which contain, as the light stabilizer, at least one compound of the formula XIV, in which A is a group -CHICAGO)-, in which E is cyan, -COUCH or -COUCH and G is hydrogen or one of the two groups of the formulae C(~3)3 Jo 2 and -Shea -OH
C6 I I (OH ) or E and G together form a group -COUCH-, is -CHOW
acutely or acryloyl and m, R4, R5 and Y are as defined in the last definition of preferred compound.
Also of interest are colour-photographic recording materials which contain, as the light stabilizer, at least one compound of thy formula I, in which A is a group -CHICAGO)-, m and n are the number 1 and R2 is -OH
-S02R14, -O'ER or a group of the formulae V or VI.
They can likewise be prepared by methods known per so and according to the equation I R311 1\.~.3/ 2 HOWE I+ HEY NO

WHO E Rl\CH\3/CH2Rl G OH SHEA R
T being a group -N(R?2, -SKIN or -OR, in which R is methyl or ethyl, R2 being -OH, -S02R14, -O'ER or a group of the formulae V or VI and Al, R3, R4, R5, E, G and Y
being as defined above.

Of particular interest are the compounds of the formula I.
These compounds are novel and, as such, are also a subject of the present invention They can be prepared, according to methods known per so, by amidation of known 4-aminopiperidine compounds, approximately in accordance with the equation o'er RlXC~3/CH2Rl R / (A) -C-X + I JO_./ 2 4\, Jo R3 Rl\CH\3/CH2Rl R / Amen ON 2 X being chlorine or -OR, in which is methyl or ethyl, 1 I I R4, R5, R16, A and m being as defined above - 14 - ~Z~6~

In a variant, it is possible in both cases to pro-pare the compounds mentioned by known reactions on -the ring nitrogen of the compound of the formula R, R3 R~cH,3~c {I
R5 (em (Cowan Ho SHARI
for example by alkylation, acylation or addition Typical representatives of the compounds of the formula I are listed in Tables I to V which follow.

I Lo -- 15 _ I okay o o

3: I ) Jo I

I, ., z _ ' I .

no - 16- Lo . _ I
_ - 17 isle , I; ''AYE Jo , o owe ,.

C I o o - 18 - Lo 2g~

~L22~

The compounds of the formula I are scarcely soluble in water and, for this reason, they are dissolved in a low-boiling organic solvent, such as methyl acetate ethyl acetate, carbon tetrachloride, chloroform, methanol eta-not, n-butanol, Dixon, acetone or Bunsen, in a high-boiling organic solvent, such as tricresyl phosphate, dimethylformamide, dim ethyl sulfoxide, di-n-butyl phthalate or ethyl N-diphenylcarbamate, or in a solvent mixture con-sitting ox the above mentioned low-boiling and high-boiling organic solvents, the solution obtained is added to a pro-tective killed solution, such as especially an aqueous gelatin solution, and the mixture is dispersed by means of a killed mill, a homogenizer or by applying ultra-sonic.
The dispersions thus obtained are then used for the preparation of the layers of colour-photographic recording materials. Theselayerscan, for example be inter-layersorprotectivelayers,but especially light-sensitive (forexamp~ blue-sensitive, green-sensitive and red-sensitive) silver halide emulsion layers in which, when the exposed recording material is developed, cyan dyes magenta dyes and yellow dyes are formed from the cores-pounding color couplers.
If desired, the light stabilizer can also be asp-lied in the treatment baths which are used after color development, for example in fixing baths and/or washing baths, but a certain volubility of the compounds of the formula I in alcohols (methanol/ethanol), aqueous alkali ardor water is necessary in that case. If the diffusion transfer method is used, the light stabilizer can be incur-prorated not only into the customary photographic emulsion layers, but also into a receiving layer.

_ 20 _ I

It is possible to employ any desired cyan couplers, magenta couplers and yellow couplers, which are used for the formation of the said dyes and hence the color images They can be dissolved, for example, in an alkaline soul-lion or in a high-boiling organic solvent, these solutions then being dispersed in an aqueous gelatin solution and being incorporated in-to a photographic silver halide Emil-soon. They can also be added to colour-photographic developers.
In the photographic recording material according to the present invention, the light stabilizer according to formula I can be combined in the same layer not only with the color couplers, but additionally also with ultra-violet absorbers.
The silver halide emulsions preferably contain gelatin as the binder, if appropriate as a mixture with other high-molecular natural or synthetic compounds.
The silver halide emulsions can, for example, be silver bromide emulsions, silver chloride emulsions or silver iodide emulsions, ortheycanalsobe those emulsion it which contain a mixture of silver halides, for example silver bromide/iodide emulsions or silver chloride/bromids emulsions.
The emulsions can be sensitized chemically and they can also contain customary organic stabilizers and anti-fogging agents as well as customary plasticizers, or example glycerol. The emulsions can also be hardened with the hardeners customary for gelatin. Moreover, the Emil-sons can contain customary coating assistants. The emulsions can be applied to customary bases for photo-graphic recording material.
To develop the colour-photographic recording mat-trial, the customary developer baths can be used. As a rule, these contain a developer substance of the p-pheny-London type, a development retarder, such as poles-slum bromide, an antioxidant, such as sodium sulfite, and a base, for example an alkali metal hydroxide or alkali metal carbonate. The developing baths can also contain a customary anti-fogging agent and completing agents.
The light stabilizers to be used according to the invention are in certain cases also suitable for protect-in colour-photographic layers, in which the dyes are incorporated directly into the emulsion and the image it produced by selective bleaching.
The quantity of light stabilizer, if appropriate in combination with a customary ultraviolet absorber, can vary within wide limits and is approximately within the range from 1 to 2,000 my, preferably 1 to 800 and in part-cuter 400 my, per m of the layer into which it is (or they are) incorporated.
If the photographic material contains an agent which absorbs W light, this agent can be present in the same layer or in the adjacent layer.
The ultraviolet absorber can be present in one layer, together with the light stabilizer, or in an adjac-en layer. The weight ratio between a customary ultra-violet absorber and the light stabilizer of the formula I

is about (5-10):1, and the molar ratio is about (10-20):1.
Examples of ultraviolet absorbers are compounds ox the benzophenone, acrylonitrile, thia20lidone, benzotriazole, oxazole, thiazole and imidazole type.
The color images obtained with the recording mat-trial according to the invention by exposure and development display very good light fastness to visible and ultraviolet light. The compounds of the formula I are virtually colorless, so that there is no discoloration of the images; additionally, they are well compatible with the customary photographic additives present in the individual layers; due to their high effectiveness, the quantity in which they are used can be reduced, and they are thus pro-vented from precipitating or crystallizing out 7 when they are incorporated as an organic solution into the aqueous binder emulsions which are used for the preparation of photographic layers. The individual processing steps, necessary after the exposure of the photographic recording material, for the production of the color images are not adversely affected by the light stabilizers. Moreover, theformatlonofso-called abrasion fog, which frequently occurs in the case ox blue-sensitive emulsions 7 can be largely suppressed. This abrasion fog can, for example, occur if mechanical stresses, for example turning, bending or rubbing, are exerted on photographic materials (silver halide emulsion layers present on a base of natural or synthetic materials) during manufacture or during treatment before development TO James 7 The Theory of the Photo-graphic Process, Thea edition, Macmillan, New York, NAY.
1977, pages 23 et seq. and pages 166 et seq.).
The examples which follow explain the present invent lion, without restricting it.
Preparation Examples Example l: 4.1 g of 2,2,6,6-tetramethylpiperidinyl-4-~-(3,5-di-ter-t.-butyl-4-hydroxyphenyl)-propionamidee, 2.8 g of methyl iodide and 6 5 g of an hydrous potassium carbonate are heated under reflwc in 100 ml of acetone for four hours.

I
_ 23 _ The acetone is evaporated off and the residue is dissolved in 150 ml of ether, washed with water and dried After evaporation of the solvent, a yellow oil which crystal-loses from acetonitrile is obtained. This gives 2.6 g (60 %) of 1,2,2~6,6-pentamethylpiperidinyl-4-~-(3,5-di-tert.-butyl-4~hydroxyphenyl) propionamide as colorless crystals having a melting point of 132 - 134C ( stabilizer l).
Example 2: 4.1 g of 2,2,6,6-tetramethylpiperidinyl-4-~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionamide are stirred at 90C in 80 ml of acetic android for twelve hours. The solvent is evaporated off in vacua, and the residue is dissolved in 50 ml of methanol and the solution is slowly ~eddropwi~e t~l50 ml oflD~ium ode solution The solid is filtered off with suction, dried at 50C and disk solved in 50 ml of acetone. The acetone solution is clarified by filtration, diluted with 150 ml of ether and cooled to 0C, and the precipitate obtained is filtered off with suction This gives 3.1 g (69 Jo of acutely-2,2,6,6-tetramethylpiperidinyl-4~ (3~5-di-tert.-butyl-4-hydroxyphenyl~-propionamide as colorless crystals having a melting point of 130 - 132C (light stabilizer 2).
Example I: 4.7 g of 2,2,6,6-tetramethylpiperldinyl-4-~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-N-butyl-propiionamide are stirred at 90C in 80 ml of acetic android for twelve hours. The solvent is evaporated off in vacua, and the orange-coloured oil is heated in 60 ml of petroleum ether at 50C forte minutes The precipitate is filtered off with suction, washed with petroleum ether and dried at 50C. This gives 3.5 g (68 %) of 1-acetyl-2,2,6,6-tetra-methylpiperidinyl-4~ 3,5-di-tert.-butyl-4-hydroxyphenyl)-N-butyl--propionam~de as a colorless powder having a melt-in point of 133 - 135C (light stabilizer Example 4: 4.1 g of 2,2,6,6-tetramethylpiperidinyl-4-~-(395-di-tert.-butyl-4-hydroxyphenyl)-propion~mide are disk solved in 150 ml of acetonitrile. 1.5 g of triethylamine are added and the solution is warmed to 60C. 1.0 g of -I

acrylic acid chloride is added drops and the mixture is stirred for one further hour after the addition. The reaction mixture is filtered and -the filtrate is evapo-rated. After purification by column chromatography, 2.0 g of l-acryloyl-2,2,6,6-tetramethylpiperidinyl-4~ Dow-tert.-butyl-4-hydroxyphenyl)-propionamide having a melting point of 149 to 151C are obtained (light stabilizer 4).
Example 5: The procedure described in Example 4 is no-peeled, using the corresponding amount of twitter-methylpiperidinyl-4-~-(3~5-di-tert.-butyl-4-hydroxmy-pAenyl)-N-butylpropionamide. l-Acryloyl-2,2,6~6-tetra-methylpiperidinyl-4-~-(3,5-di-tert.-butyl-4-hydroxxyphenyl) N-butylpropionamide having a melting point of 148 to 149C
it obtained (light stabilizer I
Allocation examples Example pa and b 0.087 g of the yellow coupler of the formula SHEA Clue CH3-C-COC`:iCO~
SHEA l \~--iCO(C:i ) 0-- ~--C5H (~) `\; . _ .
it` issue SHEA
(c~3)2~

and 0.026 g of one of the light stabilizers indicated in the tables which follow are dissolved in 2.0 ml of a mix-lure of tricresyl phosphate and ethyl acetate (1 5 g in 100 ml). To this solution, 7.0 ml of a 6 % gelatin solution, 0.5 ml of an 8 % solution of the wetting agent of the formula SHEA OH
Cry O- (OH OH 0) 350 No in ~3:4) isopropanol/water and 0.5 ml of water are added, and the whole is emulsified ultrasonically for 5 minutes at a power of 100 watt.
2.0 ml ox a silver bromide emulsion having a sit-Yen content of 6.0 g per lithe, 0.7 ml of a 1 % aqueous solution of the hardener of the formula I ~--50 ala and 3.8 ml ox water are added to 2.5 ml of the emulsion thus obtained, and the mixture is adjusted to a pi value of 6~5 and coated onto subbed, plastic-coated, white paper mounted on a glass plate.
After solidification, the paper is dried at room temperature in a circulating-air oven.
After 3 days 7 samples cut to 35 x 180 mm are exposed behind a step wedge at 3,000 lug x seconds and then processed by the Kodak Ektaprint 2 process a One part of the yellow wedges thus obtained is irradiated in an Atlas Weather-O meter with a 2,500 to xenon lamp behind a US filter (Kodak 2C) with I Joule/
cm and a second part is irradiated with 168 KJoule/cm2 (one further comparative sample of each does not contain any light stabilizer The table shows the percentage decrease in den-sty, the original density being 1.0:
With W filter Light stabilizer Density loss at 440 no inter cent No. ED = 1.0), quantity of light 63 KJ/cm~ 168 KJ/cm2 . _ ___ 2 b) A part of the yellow wedges obtained is irradiated as described under a) but without a W filter, with 21 KJoule/cm2 and a further part is irradiated, likewise without a W filter, with 63 KJoule/cm2 (one further comparative sample ox each does not contain any light stabilizer).
The table shows the percentage decrease in den-sty, the original density being 1.0:

I
_ 27 _ Without W filter ._ _.
Light stabilizer Density loss at 440 no inter cent No. (D = 1.0), quantity of light 21 KJ/cm2 I KJ/cm 14 1 37 --¦

Claims (15)

WHAT IS CLAIMED IS:

1. A colour-photographic recording material which, in at least one light-sensitive silver halide emulsion layer, an interlayer and/or a protective layer, contains at least one polyalkylpiperidine compound as a light stabiliser, wherein the polyalkylpiperidine compound is of the formula I

(I) in which R1 and R3 independently of one another are hydro-gen or methyl, R2 is hydroxyl, C1-C12-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, 2-hydroxyethyl, C2-C11-alkoxyalkyl, C7-C14-aralkyl or a group of the formula -(CH2)p-CH(R6)-X1 or -CH(R6)-X2, in which p is one of the numbers 1, 2 or 3 X1 is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)OR7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R7)(R8) and R6 is hydrogen, methyl or phenyl, R7 being hydrogen, C1-C12-alkyl, C2-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-C14-aralkyl and R8 being hydrogen or C1-C4-alkyl, or R7 and R8, together with the nitrogen atom to which they are bonded, forming a 5-membered or 6-membered heterocyclic ring, or R2 is a group of the formula II
L-CO- (II) in which L is hydrogen, C1-C12-alkyl, C2-C12-alkenyl, C3-C4-alkynyl, C3-C12-cycloalkyl, C7-C14-alkaryl, C7-C14-aralkyl, chloromethyl, unsubstituted phenyl, phenyl which is substituted by two C1-C4-alkyls and one hydroxyl, or a group -OR9, in which R9 is C1-C12-alkyl, cyclohexyl, C2-C12-alkenyl, benzyl or phenyl, or L is a group of the formula III

(III) or R2 is a group of the formula IV

(IV) in which R10 and R11 independently of one another are C1-C12-alkyl, C3-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl or C7-C14-aralkyl and R11 additionally can also be hydrogen, or R2 is a group of the formula V

(V) in which A' is methylene or a group -CH2-CH(R13)- and q is zero or 1, and R12 and R13 independently of one another are hydrogen, methyl, ethyl, phenoxymethyl or phenyl, or R2 is a group of the formula VI

(VI) in which B is a group CrH2r, in which r is a number from 2 to 12, or is C4-C8-alkenylene, C4-C8-alkynylene, pheny-lene, xylylene, bitolylene, C5-C12-cycloalkylene or a group -CONH-B1-NHCO-, in which B1 is a group CrH2r, pheny-lene, naphthylene, tolylene or a group of the formulae in which R' is hydrogen, methyl or ethyl, R" is hydrogen or methyl and r is as defined above, or R2 is one of the groups -S(O)zR14 or -OR15, in which z is the number 1 or 2, R14 is C1-C12-alkyl, C7-C14-alkaryl or phenyl and R15 is C1-C12-alkyl, C3-C12-alkenyl, C7-C14-aralkyl or a group of the formula L'-CO-, in which L' is as defined above for L, R4 and R5 independently of one another are C1-C12-alkyl, C3-C12-cycloalkyl, C7-C14-aralkyl, C7-C14 alkaryl or phenyl and R4 can additionally also be hydrogen or a group of the formula Ia (Ia) in which R1, R2, R3, R5, A, Y, m and n are as defined and M is a direct bond, , -S- -S-S-, , , -CH2-S-CH2-, -CH2-O-CH2-, -O- and -N(D3)-, and D1 and D2 independently of one another are hydrogen, C1-C18-alkyl, alkyl inter-rupted by 1 to 3 -S- or phenyl, or D1 and D2, together with the C atom linking them, form a 5-membered or 6-membered aliphatic ring and D3 is hydrogen, C1-C18-alkyl or phenyl, Y is -N(R16)-, in which R16 is hydrogen, C1-C18-alkyl, C3-C12-alkenyl, C3-C12-cycloalkyl, phenyl, C7-C14-alkaryl, C7-C14-aralkyl, C3-C11 alkoxyalkyl, a group of the formula VII

(VII) or a group -Z-D, in which Z is a -(CH2)s group unsubsti-tuted or substituted by a methyl group, s being one of the numbers 2 to 4 and D being hydroxyl, -OR17 or -N(R18)(R19), in which R17 and R18 are hydrogen, C1-C12-alkyl, C3-C12-cycloalkyl or a group of the formula VIII

(VIII) and R17 additionally can also be a group of the formula VII R19 is hydrogen, C1-C12-alkyl, C3-C12-cycloalkyl or a group of the formula IX

(IX) or R18 and R19, together with the nitrogen atom to which they are bonded, form a 5-membered or 6-membered hetero-cyclic ring, or R16 is a group of the formula IXa (IXa) in which Q is as defined above for B, n is the number 1 and m is zero or 1, and A is methylene or a group -CH2-CH(R20)- or -CH2-C(E)(G)-, in which R20 is hydrogen, methyl, ethyl, phenoxymethyl or phenyl, E is cyano or a group -C(O)OR21, -C(O)R22, -SO2R22, -P(O)--(OR23)2, -C(O)NR24R25 or -CHO, in which R21 is C1-C4-alkyl, R22 is C1-C12-alkyl, C7-C14-alkaryl or phenyl, R23 is C1-C18-alkyl, phenyl or allyl, and R24 and R25 indepen-dently of one another are hydrogen, C1-C18-alkyl or phenyl, and G is hydrogen, C1-C18-alkyl, C3-C12-alkenyl, C3-C4-alkynyl, C5-C12-cycloalkyl, C6-C18-alkylcycloalkyl, C6-C14-cycloalkylalkyl, C7-C14-aralkyl, C7-C19-alkyl-aralkyl, phenyl, or C1-C18-alkyl which is substituted by phenoxy, C7-C10-alkylphenoxy, Benzyloxy, cyclohexyloxy, cyano, -COOR26,-OCOR27 or -P(O)(OR28)2, R26 being C1-C18-alkyl, C3-C12-cycloalkyl or a group of the formula VII, R27 being C1-C18-alkyl, C3-C12-cycloalkyl, phenyl, C7-C14-aralkyl or a group of the formula III and R28 being C1-C18-alkyl, allyl or phenyl, or G is C2-C18-alkyl inter-rupted by -O-, -S-, -SO- or -SO2-, a group of the formula VII or a group of the formula in which R29 and R30 independently of one another are Cl-C4-alkyl and R30 additionally can also be hydrogen, or, if E is a group -C(O)R22, G and R22 together are tri-methylene or tetramethylene.

2. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkylpiperidine compound of the formula X

(X) in which R1 is hydrogen or methyl, R4 and R5 independently of one another are C1-C4-alkyl and additionally R4 can also be hydrogen or a group of the formula Xa (Xa) in which M is a direct bond, -CH(D2)- or -S- and D2 is hydrogen or C1-C8-alkyl, A is methylene, ethylene or a group -CH2-C(E)(G)-,in which E is cyano, -COCH3 or -COOCH3 and G is hydrogen, C1-C18-alkyl, allyl, cyclohexyl, benzyl or one of the two groups of the formulae and in which R30 is methyl or tert.-butyl, or E and G together form a group -CO-(CH2)4-, n and m are as defined in claim 1, R2 is hydroxyl, C1-C4-alkyl, allyl, methallyl, propargyl, benzyl, 2-hydroxyethyl, C2-C7-alkoxyalkyl or a group of the formula -(CH2)p-CH(R6)-X1 or -CH(R6)-X2, in which p is one of the numbers 1, 2 or 3, X1 is halogen, cyano, -OR7, -OC(O)R7, -OC(O)N(R7)(R8), -C(O)R7 or -C(O)N(R7)(R8), X2 is halogen, cyano, 1,2-epoxyethyl, -C(O)OR7 or -C(O)N(R7)(R8) and R6 is hydrogen, methyl or phenyl, R7 being hydrogen, C1-C8-alkyl, vinyl, allyl, methallyl, C5-C8-cycloalkyl, phenyl or C7-C10-aralkyl and R8 being hydrogen or methyl, or R2 is a group of the formula II, in which L is hydrogen, C1-C4-alkyl, vinyl, allyl, cyclohexyl, phenyl, benzyl, chloromethyl or a group -OR9, in which R9 is C1-C8-alkyl, cyclohexyl, vinyl, allyl or methallyl, or L is a group of the formula III, in which m, A, R4 and R5 are as defined in this claim, and R3 is hydrogen, or R2 is a group of the formula IV, in which R10 and R11 independently of one another are C1-C12-alkyl, cyclohexyl or phenyl and R11 additionally can also be hydrogen, or R2 is a group of the formula XI

(XI) in which n, R4, R5 and Y are as defined in this claim, A' is methylene or a group -CH2-CH(R13)-, q is zero or 1, and R12 and R13 independently of one another are hydrogen or methyl, or R2 is a group of the formula XII

(XII) in which A, R4, R5, Y, n and m are as defined in this claim and B is a group ?CH2?r or -CONH?CH?rNHCO-, in which r is one of the numbers 2 to 8, or C4-C8-alkenylene, xylylene or bitolylene, or R2 is one of the groups -SO2R14 or -OR15, in which R14 is C1-C4-alkyl, p-tolyl or phenyl and R15 is C1-C4-alkyl, benzyl or a group of the formula L'-CO-, in which L' is as already defined for L in this claim, and Y is -N(R16)-, in which R16 is hydrogen, C1-C12-alkyl, cyclohexyl, C3-C7-alkoxyalkyl or a group of the for-mula XIII

(XIII) in which r, m, A, R2, R4 and R5 are as already defined in this claim.

3. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkylpiperidine compound of the formula XIV

(XIV) in which m is zero or 1, A is methylene or ethylene, R4 and R5 independently of one another are methyl or tert.-butyl, Y
is -N(R16)-, in which R16 is hydrogen or C1-C8-alkyl, and R2 is hydroxyl, methyl, allyl, benzyl, 2-hydroxyethyl, acetyl, acryloyl, methoxy, acetoxy or a group of the formula XV

(XV) in which m, A, R4 and R5 are as defined in this claim, or is a group of the formula IV, in which R10 is C1-C8-alkyl, cyclo-hexyl or phenyl and R11 is hydrogen, C1-C8-alkyl or cyclo-hexyl.

4. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkylpiperidine compound of the formula XIV

(XIV) in which R2 is a group of the formula and m, A, R4 R5 and Y are as defined in claim 3.

5. A colour-photographic recording material according to claim 1, which contains, as the light stabiliser, at least one polyalkylpiperidine compound of the formula XIV

(XIV) in which A is a group -CH2-C(E)(G)-, in which E is cyano, -COCH3 or -COOCH3 and G is hydrogen or one of the two groups of the formulae and or E and G together form a group -CO?CH2)4-, R2 is -CHO, acetyl or acryloyl and m, R4, R5 and Y are as defined in claim 3.

6. A colour-photographic recording material according to claim 1, which contains the light stabiliser in combin-ation with a cyan coupler, magenta coupler and yellow coupler.

7. A colour-photographic recording material according to claim 1, which contains the light stabiliser in combin-ation with an ultraviolet absorber.

8. A colour-photographic recording material according to claim 7, wherein the ultraviolet absorber is a compound of the benzophenone, acrylonitrile,thiazolidone, benzo-triazole, oxazole, thiazole or imidazole type.

9. A colour-photographic recording material according to claim 1, which contains the light stabiliser in combin-ation with a cyan coupler, magenta coupler and yellow coupler and with a UV absorber in the same layer.

10. A colour-photographic recording material according to claim 1, which contains 1 to 2,000 mg of the light stabi-liser per m2 of the layer into which the latter is incor-porated.

11. A process for the production of photographic colour images by imagewise exposure and colour develop-ment of a colour-photographic recording material according to claim 1.

12. A photographic colour image obtained by the pro-cess according to claim 11.

13. A compound of the formula I, in which Y is -N(R16)-and n is the number 1, and R1, R2, R3, R4, R5, R16, A and m are as defined in claim 1.

14. A compound according to claim 13, of the formula X, wherein Y is -N(R16)- and n is the number 1, and R1, R2, R4, R5, R16, A and m are as defined in claim 2.

15. A compound according to claim 13, of the formula XIV, wherein Y is -N(R16)- and R2, R4, R5, R16' A and are as defined in claim 3.