Note: Descriptions are shown in the official language in which they were submitted.
-- 1 --
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 CHAR 1
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
-- 3 --
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 -
R1CH2 SHEA 3
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
WRECK 2 1
~'~ 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.
-- 7 -
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
-- 8 --
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
~%~
-- 10 --
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
R5
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
I / 3
\.~.~ 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
- 13 -
I R311 1\.~.3/ 2
HOWE I+ HEY NO
R5/ CH2TG OH SHEA R
WHO E Rl\CH\3/CH2Rl
R5 SHUCKS WORRY
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
16 3 2 1
4\, Jo R3 Rl\CH\3/CH2Rl
R / Amen ON 2
16 3 2 1
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~
-- 19 --
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
- 22 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
- 24 -
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
3 3
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
0
0 26
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
5 - I
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 --¦
