Note: Descriptions are shown in the official language in which they were submitted.
2 G1 2 ~
., ~
A-17710/+
Stabilizers for colour photo~raphic recordin~ materials
: . .
The present invention relates to the stabilization of photographic dyes and dye couplers by
the addition of a stabilizer in at least one layer of photographic recording materials. The
addition can be made, for example, in the yellow layer, the magenta layer or the cyan
layer.
Most silver dye image processes customary nowadays are based on a chemical reaction
between a dye coupler - a compound having a reactive methylene or pseudo-methylene
group - and an oxidized developer. The developer - usually a p-phenylene diaminederivative - is oxidized by the photosensitized silver halide with the formation of metallic
silver. The oxidized developer is the real reagent for the formation of the dye.
Depending on their chemical structures, the dye couplers require either 2 or 4 mol of silver
per mol of coupler. One speaks, therefore, of di-equivalent or tetra-equivalent couplers.
Colour photographic materials based on a process of this type have at least three
colour-sensitive layers which contain three different kinds of couplers:
(a) The yellow layer, containing a yellow coupler. These are in most cases B-keto-
carboxyamides.
(b) The cyan layer, containing a cyan coupler. These are in most cases phenols;
naphthols or pyrazolazoles.
(c) The purple or magenta layer, containing a magenta coupler. These are in most cases
pyrazolones, pyrazoloazoles, cyanoacetylcoumarones or open-chain
acylacetonitriles.
In order to prevent diffusion of the couplers into the adjacent layer, the compounds are
provided with hydrophobic ballast groups or are bound into polymeric structures.
The yellow dyes formed after development have an inadequate fastness to light. The
fastness to light can be improved to a certain extent by introducing above the yellow layer
2~239~
a layer containing a UV absorber, as suggested, for example, in US-A 3,253,921.
Another and a better course is to add special stabilizers to the yellow layer. These must
not react with the coupler or the developer. Various phenolic compounds have been
suggested as stabilizers of this type, but particularly p-hydroxybenzoic acid ester
derivatives, such as have been suggested, for example, in US-A 4,228,235, and
combinations of stearically hindered amines with phenols, such as have been suggested,
for example, in EP-A 114,029. Molelcular combinations of hindered amines and phenolic
groups have also been suggested, for example in EP-A 82,817 and EP-A 103,540.
Stabilizers of this type have led to a considerable increase in fastness to light, but there is
still an interest in improvements in the fastness to light of the yellow dyes.
The magenta dyes and couplers are also not adequately fast to light. In addition, many
magenta couplers are unstable to heat when stored in the dark. As in the case of the yellow
dyes, filter layers containing UV absorbers, in particular hydroxyphenylbenzotriazoles,
have also been suggested for the magenta dyes and couplers, for example in US-A
3,533,794, but this is not adequate for present-day requirements in respect of fastness to
light.
. .,
The addition of stabilizers to the magenta layer is effective. Suitable additives are, in : -
particular, hydroquinone derivatives, such as are described, for example, in US-A
3,935,016.
The cyan dyes must also be stabilized. This can also be effected by means of UV absorber
filter layers or by the addition of special stabilizers to the cyan layer. Stabilizers of this
type can, for example, be phenols or hindered amines, as described in EP-A I 13,124.
Photographic colour films are also known from JP-A 49/134,326 containing stabilizèrs of
the formula
R
HO ~ Z--Rl or [ HO ~ z - co
R R
'.
,
' .
~: 20239~
- 3-
in which R is tert-C4alkyl or tert-C5alkyl, Z is 1-3 C-alkylene or imino, Rl is
C-alkylthiodisubstituted s-triazine and Zl is a polyvalent, aliphatic or cycloaliphatic
group.
Colour photographic products are known from 3P-A 59/005-246 which have a layer of a
- yellow dye on a base and have, in the yellow dye, a compound of the formula
[ R~ y--C--O--X--t C
... .
in which Rg is H, alkyl or aryl, Rlo and Rll are alkyl, X is alkylene or arylene and Y is - -
alkylene.
`,t
Compounds similar to those mentioned above have also been disclosed in JP-A
:: 50-023,822 and 54-154,325 and in EPA 310,551, 310,552 and 309,917.
,, :
The compounds mentioned did not, however, give satisfaction in all activities, for example
in light stabilization. It was therefore the object of the present invention to provide novel ~ -
' stabilizers for stabilizing colour photographic materials. Some of the compounds
mentioned as stabilizers are novel.
The present invention relates to a colour photographic recording material containing, in at
least one of the chromogenic colour photographic layers, as a stabilizer, at least one
compound of the formula I
:~ R
L R H~CH--,C,~A
in which Rl is alkyl having 1 to 18 C atoms, cycloalkyl having S to 12 C atoms, cycloalkyl
which has S to 12 ring C atoms and is substituted by 1 to 3 C1-C4alkyl groups, phenyl or
aralkyl having 7 to 9 C atoms, R2 is H, alkyl having 1 to 18 C atoms, cycloalkyl having S
2023~
4 -
to 12 C atoms, cycloalkyl which has S to 12 ring C atoms and is substituted by 1 to 3
Cl-C4alkyl groups, phenyl or aralkyl having 7 to 9 C atoms, and R3 iS H or CH3 and n is
the number 1 or 2, in which, if n is 1, A is -oR4 or--N/ and R4 iS alkyl having 1 to 24
\R6
C atoms, C3-C20alkyl which is interrupted by at least one -O-, -S- or -NR7-~ or C3-C20alkyl
which is interrupted by at least one -O-, -S- or -NR7- and is substituted by at least one
hydroxyl group, or is a group of the formula
.: ~
: / H3C CH3
)(~S or ~<N--R24
CH3CH2 ~< \--7<
H3C CH3
.,
. l in which R7 iS hydrogen, Cl-CI2alkyl or phenyl and R24 is alkyl having 1 to 4 carbon
atoms, allyl, benzyl, a radical of the formula
j .
,,1, ,.
t ~
~ ~ 4ng :
--CH2CH20--CO--C~ HCH2~ OH or CoR25
. CH3 C4Hg
.. , :
in which R25 is alkyl having 1 to 24 carbon atoms or allyl, or R4 iS Cl-C24alkyl which is
substituted by -OH, -OCOR8 or -P(O)(OR9)2 in which R8 is Cl-Cl8alkyl,
Cs-CI2cycloalkyl, cycloalkyl which has ~ to 12 ring C atoms and is substituted by 1 to 3 ~: -
Cl-C4alkyl groups, C2-CI8alkenyl, C7-CI5aralkyl, phenyl or C7-CIsalkaryl and R9 is ~ ~ :
: hydrogen, Cl-Cl8alkyl, Cs-CI2cycloalkyl, cycloalkyl which has 5 to 12 ring C atoms and ~:
is substituted by 1 to 3 Cl-C4alkyl groups, C2-Cl8alkenyl, C7-Clsaralkyl, phenyl, naphthyl
or C7-CIsalkaryl, or R4 is C5-CI2cycloalkyl, cycloalkyl which has 5 to 12 ring C atoms
and is substituted by 1 to 3 Cl-C4alkyl groups, C2-CI8alkenyl, C7-Clsaralkyl,
C7-Cl8alkaryl, phenyl or a group -CH2CH(OH)Rl in which R10 is C7-Cl2aralkyl or .
-CH20Rlland Rll is cyclohexyl, phenyl, tolyl or benzyl, or R4 is a group of the forrnula
--Ic~lc~Y--Rl4 in which R12 and Rl3 independently of one another are hydrogen or
.` ' .
~-
~, 2~2~9~ `
.
s
C1-Cl8alkyl, Y is -O- or -S- and R14 is a group of the formula
H~C1~COORI7
in which Rls and Rl6 independently of one another are hydrogen or methyl, m is 0 or 1
and R17 is hydrogen, Cl-C24alkyl, Cs-CI2cycloalkyl, cycloalkyl which has 5 to 12 ring C
atoms and is substituted by 1 to 3 Cl-C4alkyl groups, C2-CI8alkenyl, C7-CIsaralkyl,
phenyl or C7-CI6alkalyl, or Rl4 is a group of the formula ~CH--cooRl7 in which R18 is
hydrogen, C~-CIgalkyl or a group CoORI7 in which Rl7 is as defined, or Rl4 is hydrogen,
phenyl, Cs-CI2cycloalkyl, cycloalkyl which has 5 to 12 ring C atoms and is substituted by
1 to 3 Cl-C4alkyl groups, C2-CI8alkenyl, benzyl or a group of the formula -
r' j Rl9
--CH2
R20
in which Rl9 and R20 independently of one another are H, methyl or -C(CH3)3, subject to
the proviso that Rl9 and R20 are not at the same time H, and Rs and R6 independently of
one another are H, C~-CI2alkyl, C3-C20alkyl interrupted by 1 or more -O-, ~
Cs-CI2cycloalkyl, cycloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3 . ~:
C1-C4alkyl groups, phenyl, phenyl which is substituted by Cl-CI2alkyl, Cl-C4alkoxy or
halogen, C3-Cgalkenyl, C7-CIsaralkyl or C2-C4hydroxyalkyl, or R5 and R6 together are
tetramethylene or pentamethylene or tetramethylene or pentamethylene interrupted by -O-, :
-NR21- or -S(O)q- in which R21 is hydrogen, Cl-Cl2alkyl or phenyl and q is 0, 1 or 2, or, if
n is 2, A is a group of the formula O-X'-O- in which X' is C2-CI0alkylene,
C4-Cgalkenylene, C4-Cgalkynylene, cyclohexylene, or C4-C40alkylene which is interrupted
by one or more members of the series --CH--, -O-, -S(O)q- and -NR22- in which R22 is
hydrogen or Cl-CI2alkyl or phenyl and q i~ 0, 1 or 2, or A is a group of the fortnula
. . . :
. .: ~
`: `
202~9~
- 6-
.' . (~X)b
' _0~o_
.,
in which Rx is an alkyl group having 1 to 8 C atoms and b is 0, 1 or 2, or A is a group of
:~ - theformula
_0~l~o-
or A is a group of the formula
CH3
or A is a group of the formula
-O-CH2-CH(OH)-CH2-O-X2-O-CH2CH(OH)-CH2-O- in which x2 is the same as X' or is
. ~ .
_O~o--or
O {} c ~a --
3 ` ~ ~
or A is a group of the formula ~ ::
~x3
23 ~2
in which X3 is C2-CIOalkylene and R23 is hydrogen, C~-C12alkyl or phenyl.
A colour photographic recording material as described above containing at least one
compound of the formula I in which Rl is alkyl having 1 to 8 C atoms, cyclohexyl, phenyl
:--. 2l~2~3
,; ,
~ -7-
-:
. or C7-Cgphenylalkyl, R2 is hydrogen, alkyl having 1 to 8 C atoms, cyclohexyl, phenyl or
, . C7-Cgphenylalkyl and R3 is hydrogen is suitable.
.--. .
Another suitable colour photographic recording material contains at least one compound
of the formula I in which, if n is 1, A is -oR4 or -NRsR6 in which R4 is alkyl having 1 to
:, - 18 C atoms, C3-C20alkyl which is interrupted by 1 to 3 -O- or -S-, or C3-C20alkyl which is
substituted by 1 to 2 -OH and interrupted by 1 to 3 -O- or -S-, or R4 is Cl-Cgalkyl .
- substituted by -P(O)(OR9)2 in which R9 is hydrogen, C1-CI2alkyl, Cs-CI2cycloalkyl,
C3-C18alkenyl, benzyl, phenyl or tolyl, or R4 is Cs-CI2cycloalkyl, C2-CI8alkenyl,
; C7-CI0aralkyl, C7-CI8aralkyl, phenyl or a group -CH2CH(OH)RI in which Rl is ::
~ C7-CI0aralkyl or -CH20RIl in which Rll is cyclohexyl, phenyl, tolyl or benzyl, or R4 is a
: group of the formula ~ :
:: :
--C~CI~Y--R14 ~ : :
'~ R12 R13 -
" :~
in which Rl2 and Rl3 independently of one another are hydrogen or Cl-C~2alkyl, Y is -O~
. or-S-, and Rl4 is a group of the formula
--,CH--,CH--CoOR17
R15 R16
in which Rl5 and Rl6 independently of one another are hydrogen or methyl and Rl7 is
Cl-CI2alkyl, cyclohexyl, C2-CI8alkenyl, C7-C9aralkyl, phenyl or C7-CI6alkaryl, or Rl4 is a
group of the formula
--CH--CH--CoOR17
R18
:
in which Rl8 is hydrogen, Cl-CI2alkyl or a group CoORI7 and in which Rl7 is as defined
above, or Rl4 is phenyl, cyclohexyl, C2-Cgalkenyl, benzyl or a group of the formula
. . ~
~` Rl9 ~ ~:
--CH2~ OH
R20 :
:: 2~2~
8 -
~, . in which Rl9 and R20 independently of one another are H, methyl or -C(CH3)3, subject to
~3 the proviso that Rl9 and R20 are not at the same time H, and Rs and R6 independently of
- ~, one another are hydrogen, Cl-C12alkyl, C3-C20alkyl which is interrupted by 1 to 3 -O-,
cyclohexyl, phenyl, C3-C6alkenyl or benzyl, or Rs and Rfi together are tetramethylene or
,' pentamethylene or tetramethylene which is interrupted by one -O-, or, if n is 2, A is a
- ~ - group of the forrnula -O-X'-O- in which X' is C2-C8alkylene, C4-C8alkenylene,
. ~ C4-CI2alkylene which is interrupted by 1 to 3 members of the series --CH--, -O-, ~S(O)q~
`' and-NRZ2-inwhichR22ishydrogen,Cl-Clzalkylorphenyl,phenylene,-CH2C C-CH2-
or -(CH2CH20)aCH2CH2- in which a is 1, 2 or 3 and q is 0, 1 or 2, or A is a group of the
. ' formula ~--x3--N--in which X3 is alkylene having 4 to 8 C atoms.
:` h
..,
A preferred colour photographic recording material contains at least one compound of the ::
formula I in which Rl is alkyl having 1 to 4 C atoms, R2 is hydrogen or alkyl having 1 to 4
~' C atoms and R3 is hydrogen. : :
. It is very particularly preferable for Rl and R2 to be tert-butyl and for R3 to be hydrogen in
~ compounds of the formula I.
~ Another preferred colour photographic recording material contains at least one compound
~ of the formula I in which, if n is 1, A is -oR4 in which R4 is alkyl having 1 to 18 C atoms,
`:'l alkenyl having 2 to 18 C atoms or alkyl which has 3 to 12 C atoms and is interrupted by
one or two -O-, or R4 is a group of the formula -CH2-CH2-S-(CH2)m-CH2-CooRI7 in :
.~. which m is O or 1 and Rl7 is Cl-Cl2alkyl, or R4 is -CH2-P(o)(oR3)2 or
-CH2-CH2-P(O)(OR9)2 in which R9 is C2-Csalkyl, or A is--N/ in which Rs is
R6
: hydrogen and R6 is C2-C4alkenyl or C3-C8alkyl which is interrupted by -O-, or, if n is 2, A
is a group of the formula -O-X'-O- in which X' is an alkylene group having 2 to 4 C
atoms, -CH2-CH=CH-CH2-, an alkenylene group having 4 to 8 C atoms or an alkylenegroup which has 2 to 6 C atoms and is interrupted by one -S-, -O- or--s--CH- S -, or A is
~3 '
; ~'
2 ~ 2 ~
.f g
i
lf a group of the formula ~--X3--N--in which X3 is alkylene having 4 to 8 C atoms.
fi
A colour photographic recording material containing at least one compound of the formula
I in which Rl and R2 are a tert--butyl group and R3 is hydrogen is particularly preferred.
f A colour photographic recording material which is also particularly preferred is one
ff containing at least one compound of the formu]a I in which, if n is 1, A is -oR4 in which
` ' R4 is alkyl having 1 to 18 C atoms, alkenyl having 12 to 18 C atoms,
~-j -CH2-CH2-S-C(CH3)3 or -CH2-CH2-O-CH2-CH2-O-C2Hs, or, if n is 2, A is -O-X'-O- in
which X' is alkylene having 2 to 4 C atoms or alkylene which has 4 to 6 C atoms and is
interrupted by one -O- or -S-. ;
~ .
Further particularly preferred colour photographic recording materiaïs contain at least one
compound of the formula I in which Rl and R2 are each tert--butyl and R3 is hydrogen
and, if n is 1, A is -oR4 in which R4 is -CH3,--CH2--CH2--CH--CH2--C(CH3)~f or Cl8H37,
CH3
; or, if n is 2, A is -O-X'-O- in which X' is -CH2-CH2-S-CH2-CH2- or
, -CH2-CH2-O-CH2-CH2--
~i .
Another particularly preferred colour photographic recording material contains at least one
~;' compound of the formula I in which Rl is tert-butyl, R2 and R3 are hydrogen and, if n is 1,
,i A is a group -oR4 in which R4 is methyl, -C8Hl7 or -(CH2)8CH=CH(CH2)7CH3, or, if n is
j 2, A is a group of the formula -O-X'-O- in which X' is -Cl:I2-CH2-S-CH2-CH2- or
-CH2-CH2-O-CH2-CH2--
If Rl, R2, R8, R9, Rl2, Rl3 or Rl8 are, for example, alkyl having 1 to 18 C atoms, these
groups embrace, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobuiyl, t-butyl,
pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, -
tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, 2-ethylbutyl, 1-methylpentyl,
1,3-dimethylbutyl, 1,1,3,3-tetramethylbutyl, 1-methylhexyl, isoheptyl, 1-methylheptyl,
1,1,3-trimethylhexyl, 1,1,3,3-tetramethylhexyl, I-methylundecyl or 3,5,5-trimethylhexyl.
R4 or R17 can be alkyl having 1 to 24 C atoms. Examples can be taken from the above
enumeration, to supplement which reference may be made, for example9 to eicosyl,heneicosyl and docosyl. -
- l O -
:i
R5, R6, R7, R9, R21, R22 or R23 can be C1-C~2alkyl. Appropriate examples can be taken
analogously from the above enumeration. -
... .
; i
: R' can be C1-Cgalkyl, and here too appropriate examples can be taken from the statement.
,
Rl,R2,R4,R5,R6, R9, Rl4, Rl5, R16 or Rl7 can be Cs-C~2cycloalkyl. Examples of such
groups are cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl, cyclohexyl beingparticularly preferred.
Examples of cycloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3 :
C1-C4alkyl groups are 2-methylcyclohexyl, 4-methylcyclohexyl, dimethylcyclohexyl,
trimethylcyclohexyl or t-butylcyclohexyl.
If Rl, R2, R4,R5,R6,R8,R9,RI0, Rl4 or Rl7 are aralkyl having 7 to 9 C atoms or having 7
to 15 C atoms, phenylalkyl groups are preferred. Examples of these are benzyl, phenethyl,
~-methylbenzyl or a,-dimethylbenzyl. Benzyl is preferred.
.~ :
` If, for example, R4is C3-C20alkyl which is interrupted by at least one -O-, -S- or -NR7-,
these groups are, for example, radicals such as -CH2-CH2-S-C(CH3)3 or
-CH2-CH2-O-CH2-CH2-O-C2Hs. -CH2-CH2-O-CH2-CH2-O-CH2-CH2-OH may be
mentioned as an example ofR4 as a C3-C20alkyl radical which is substituted by at least
one -OH group and is interrupted by at least one -O-, -S- or -NR7-. Examples of a radical
R4 when it is Cl-C24alkyl substituted by -P(O)(OR9)2 are -CH2-P(O)(OC4Hg)2 and
-CH2-CH2-P(O)(OC4H9)2-
:
~i R4,R5,R6,R8,R9,RI4,Rl5 or Rl6 can be C2-CI8alkenyl or C3-C8alkenyl.
The examples of these can be selected analogously from allyl, 2-methallyl, 2-butenyl,
trans-2-butenyl, 2-hexenyl, trans-2,4-hexadienyl, or hexenyl, decenyl, undecenyl,
heptadecenyl, oleyl, cis-9-octadecenyl, trans-9-octadecenyl, cis,cis-9,12-octadecadienyl or
cis,cis,cis-9,12,15-octadecatrienyl.
cis-9-Octadecenylandtrans-9-octadecenyl areprefe}red.
R8 and R9 can be C7-CI5alkaryl9 Rl7 can be C7-CI6alkaryl and R4 can be C7-CI8alkaryl.
Examples are methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl,
~ 2~
.
,. . .
j isopropylphenyl, t-butylphenyl, methyl-t-butylphenyl, di-t-butylphenyl or
-, 2,6-di-t-butyl-4-methylphenyl.
Examples of R4 as a group of the formula
--CH--CH--Y--R14,
;
in which Rl4 is
.,
= CH----CH--CooR17,
R1S Rl 6
are -CH2-CH2-S-CH2-CH2-COOCI-C8alkyl and -CH2-CH2-S-CH2-COOCI-C8alkyl.
Cl-C8alkyl can be methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl,
heptyl or octyl.
.i
Z
, Rs and R6 can also be C3-C20alkyl which is intelTupted by at least one -O-. Examples of
' these are -CH2-CH2-O-CH3 or -CH2-CH2-O-CH2-CH2-O-CI-C8alkyl in which Cl-C8alkyl
can be taken analogously from the above statement.
,
If, for example, Rs and/or R6 are phenyl which is substituted by Cl-C12alkyl, Cl-C4alkoxy
or halogen, examples of these groups are o-, m- or, preferably, p-toluidine, 2-chloroaniline
or, preferably, 4-chloroaniline or o-, m- or, preferably p-anisidine (methoxyaniline).
Rs and R6 can also be C2-C4hydroxyalkyl. Examples are -CH2-CH2-OH, -
-CH2-CH~-CH2-OH or-CH2-CH2-CH2-CH2-OH.
Rs and R6 together can be C4alkylene or Csalkylene, accordingly tetramethylene or
pentamethylene, or tetramethylene or pentamethylene which is interrupted by -O-, -S(O)q-
or -NR2l- in which R21 and q can be as defined above. Examples of these are
-CH2-CH2-O-CH2-CH2-. -cH2-cH2-NH-cH2-cH2- or-CH2-CH2-S(0)2-CH2-CH2-.
If X', x2 or X3 iS C2-CIOalkylene, examples of these are ethylene, trimethylene,tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene,
.
: . , .
2~2~
.,
- 1 2 -
., .
decamethylene, 1-methyl-1,2-ethanediyl, 1-ethyl-1,2-ethanediyl,
2,2-dimethyl-1,3-propanediyl or 2-ethyl-2-n-butyl-1,3-propanediyl. Examples of alkylene
which has 4 to 40 C atoms and is interrupted by --CH--, -O-, ~S(O)q and/or-NR22-, in
which R22 can be as defined above and q is 0, 1 or 2, are
-- H--CH--s--c--s--CH~cH~ -cH2-cH2-o-cH2-cH2-~-cH2-cH2-s-cH2-cH2 or
-CH2-CH2-S(0)2-CH2-CH2--
X' can also be C4-C8alkenylene, for example 2-butene- 1 ,4-diyl.
If X' is C4-C8alkynylene, an example of this is 2-butyn- 1,4-diyl.
It is preferable to employ compounds of the formula I in which A is -oR4 or -O-X'-O-.
A preferred colour photographic recording material contains, in the chromogenic colour
photographic layers, at least one compound of the formula I as described above. Typical
examples of such compounds of the formula I are listed in the table below. Rl, R2, R3, n
and A in the forrnula I are as defined in ~he table below.
.
,:
,. . :
~':
. . ~
~; .. . - ........ . ,, . . . :., ~ .
2~23~5
-13-
~' Table:
.~ . Rl R2 R3 n A . .
:~ C(CH3)3 C(CH3)3 H _ -OCH3
_
C(CH3)3 C(CH3)3 H 1; -OC~ H37
C(CH3)3 C(cH3)3 H _ .OÇH2CH(C2HS)C4H9
C(CH3)3 C(CH3)3 H _ ~3CH2CH2SC(CH3)3
C(CH3)3 C(CH3)3 H 2 -ocH2cH2scH2cH2o-
C(CH3)3 C(CH3)3 H _ -ocH2cH2scH2cH2coocH3
::. C(CH3)3 C(CH3)3 H _ -ocH2cH2scH2cooc2Hs
~,
C(CH3)3 C(CH3)3 H 2 - OcH2cH2s-c-scH2cH2
,,,.,,' . ~ ' ::
,~ C(CH3)3 C(CH3)3 H I -NHCH2CH=cH2
~, _ . _
,~, C(CH3)3 C(CH3)3 H _ -NHCH2CH20CH3
C(CH3)3 C(CH3)3 H I -OCH2CH20cH2cH20c2Hs
_
~ii C(CH3)3 C(CH3)3 H _ -OCH2P(O)(Oc4H9)2
.j C(CH3)3 C(CH3)3 H 2 -ocH2cH2ocH2cH2
~ . _
t, C(CH3)3 C(CH3)3 H 2 -OCH2CH=CHCH20-
!: 1 C(CH3)3 C(CH3)3 H 2 -OCH2C--CCH20-
;~ . C(CH3)3 C(CH3)3 H 2 -NH(CH2)6NH- ~:
C(CH3)3 C(CH3)3 H 2 -OCH2CH20-
.j . C(CH3)3 H H _ -OCH3
C(CH3)3 H H _ -OC3H17
. C(CH3)3 H H _ -O(CH2)8CH=CH(CH2)7cH3
!: C(CH3)3 H H 2 -OCH2CH2SCH2cH20
Some of the compounds described as stabilizers in the chromogenic colour photographic
layers according to the present invention are novel.
,
~ The novel compounds according to the present invention have the general formula la
;
., .
.
.
2~23~5
. . ,
- 14-
. ~3 . C(CH3)3
J ~ ~CH r CH- r, ~ /~ la
' ~i O
in which n is a number 1 or 2, and, if n is 1, A is -oR4 or--N/ , and R4 is H, alkyl
."~ R6
having 1 to 24 C atoms, C3-C20alkyl which is interrupted by at least one -O-, -S- or -NR7-,
~. or C3-C20alkyl which is interrupted by at least one -O-, -S- or -NR7- and is substituted by
-' at least one hydroxyl group, or is a group of the formula
~,:
''' /= \
`, 2)C~or
... ~ CH3CH2 0 --< '
~ H3C CH3
in which R7 is hydrogen, Cl-CI2alkyl or phenyl and R24 is alkyl having 1 to 4 carbon
:~:, atoms, allyl, benzyl, a radical of the formula
..,
` :, t C4Hg
--eH2eH20- C--,cHcH2~ OH or COR2s
!:~ CH3 C4H9
,~
in whieh R2s is alkyl having 1 to 24 carbon atoms or allyl, or R4 is Cl-C24alkyl which is ~:
!~.' substituted by -OH, -OCOR8 or -P(O)(OR9)2 in which R8 is Cl-Cl8alkyl, Cs-CI2eyclo- :~-
.. alkyl, eyeloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3 Cl-C4alkyl
groups, C2-Cl8alkenyl, C7-Clsaralkyl, phenyl, naphthyl or C7-CIsalkaryl and R9 is
hydrogen, Cl-Cl8alkyl, Cs-Cl2cycloalkyl, cycloalkyl which has 5 to 12 ring C atoms and
is substituted by 1 to 3 Cl-C4alkyl groups, C2-Cl8alkenyl, C7-Clsaralkyl, phenyl, naphthyl
or C7-Clsalkaryl, or R4 is Cs-Cl2cycloalkyl, cycloalkyl which has 5 to 12 ring C atoms
and is substituted by 1 to 3 Cl-C4alkyl groups, C2-Cl8alkenyl, C7-Clsaralkyl, C7-Cl8-
: - ' . ',~,`"~
: - ' ~ : :
.
: .
2 ~ 2 ~
:
' .
alkaryl, phenyl, naphthyl or a group -CH2CH(OH)R1 in which Rl is C7-Cl2aralkyl or
-CH20R11and R11 is cyclohexyl, phenyl, tolyl or benzyl, or R4 is a group of the forrnula
CH--~CH--Y--R14 in which Rl2 and Rl3 independently of one another are hydrogen or
C1-Cl8alkyl, Y is -O- or -S- and Rl4 is a group of the forrnula
~H~CL~6
.~ .
in which Rls and R16 independently of one another are hydrogen or methyl, m is O or 1
and R17 is hydrogen, Cl-C24alkyl, Cs-CI2cycloalkyl, cycloalkyl which has 5 to 12 ring C
atoms and is substituted by 1 to 3 Cl-C4alkyl groups, C2-CI8alkenyl, C7-CIsaralkyl,
phenyl or C7-CI6alkaryl, or Rl4 is a group of the formula ~ cooRI7 in which Rl8 is
hydrogen, Cl-CI8alkyl or a group CoORI7 in which R17 is as defined, or R14 is hydrogen,
l phenyl, Cs-C12cycloalkyl, Cs-C12cycloalkyl substituted by 1 to 3 C1-C4alkyl groups,
.~l C2-CI8alkenyl, benzyl or a group of the formula
,.1 Rl9 ::
--CH2~ OH
~`,
in which Rl9 and R20 independently of one another are H, methyl or -C(CH3)3, subject to
the proviso that R19 and R20 are not at the same time H, and Rs and R6 independently of
one another are hydrogen, Cl-Cl2alkyl, C3-C20alkyl interrupted by at least one -O-,
Cs-CI2cycloalkyl, cycloalkyl which has 5 to 12 ring C atoms and is substituted by 1 to 3
Cl-C4alkyl groups, phenyl, phenyl which is substituted by C1-CI2alkyl, Cl-C4alkoxy or
halogen, C3-C8alkenyl, C7-CIsaralkyl or C2-C4hydroxyalkyl, or Rs and R6 together are
tetramethylene or pentamethylene or tetramethylene or pentamethylene interrupted by -O-,
-NR21- or -S(O)q- in which R21 is hydrogen, Cl-Cl2alkyl or phenyl and q is 0, 1 or 2, or, if
n is 2, A is a group of the formula O-X'-O- in which X' is C2-C~Oalkylene,
C4-C8aLkenylene, C4-C8alkynylene, cyclohexylene, or C4-C40alkylene which is interrupted
by one or more --CH--, -O-, ~S(O)q~ or -NR22- in which R22 is hydrogen or Cl-CI2alkyl
' '.
or phenyl and q is 0, 1 or 2, or A is a group of the formula
,
., . ~; :: : . . . . :
,~ ..... . . . .. .
' 2 (~ 2 3 g ~ ~
3 1 6 -
,,,
o~o-
- - in which Rx is an alkyl group having 1 tO 8 C atoms and b is 0, 1 or 2, or A is a group of
, ~ the formula
or A is a group of the forrnula
~CU3~a ~
or A is a group of the formula
-O-CH2-CH(OH)-CH2-O-X2-O-CH2-CH(OH)-CH2-O- in which x2 is the sarne as X' or is
. . I
~, --0~30--or
--{~C~o_ ' ~ ~
or A is a group of the formula
N--x3~
R23 ~23 ~::
in which X3 is C2-CIOalkylene and R23 is hydrogen, Cl-Cl2allcyl or phenyl. ~ ~:
The meanings mentioned as suitable and preferred for A and n in compounds of the
2~2~
- 1 7 -
:',
formula I also result in suitable and preferred compounds in novel compounds of the
forrnula la.
~.1
Novel compounds of the formula Ia which are particularly preferred are those in which n
3 iS 1 and A is -oR4 and R4 is an alkyl group having 1 to 18 C atoms or an alkenyl group
- having 2 to 18 C atoms, or n is 2 and A is -O-X'-O- in which X' is C2-C8alkylene or
C4-Cl2alkylene which is interrupted by 1 to 3 -O-, -S- or -NR22-, or X' is phenylene, R22
being hydrogen, C1-CI2alkyl or phenyl.
. ~ .
In other particularly preferred novel compounds of the formula Ia n is 1 and R4 is
~, Cl-CI8alkyl or Cl2-CI8alkenyl, or n is 2 and A is -O-CH2-CH2-S-CH2-CH2-O- or
-O-CH2-CH2-O-CH2-CH2-O-
.,
Accordingly, exarnples of novel compounds are those of the formula Ia in which n is 1 and
CH3
A is -OCH3, -OC8H~7,--O--CH2--CH2--CH--CH2--C(CH3)3 or
-O-(CH2)8-CH=CH-(CH2)7-CH3, or in which n is 2 and A is -O-CH2-CH2-S-CH2-CH2-O-
or-o-cH2-cH2-o-cH2-cH2-
The compounds of the formula I and of formula Ia according to the present invention can
be obtained, for example, by a Michael addition reaction in which the reaction follows the
equation below: .
Rl R3 Rl R3
tlO~ + --CN2:C--C--OR4 _ 110~C112--CR-- -OR~
Rl, R2, R3 and R4 can be as defined above.
The process is carried out, for example, by reacting the substituted phenol with the
olefinic ester in a stoichiometric excess in the presence of a catalytic amount of a base, for
example a quaternary ammonium base, an alkali metal amide or an alkali metal alkoxide,
at a temperature between 150 and 220C.
~ 2023
:'
- l o -
j A detailed description of the process can be seen in US Patent Specification 4,529,809
I mentioned initially.
~ ,
- ~ In particular, the lower alkyl esters (R4 = Cl-C4alkyl, especially methyl) are prepared in
., this manner. The other esters can be obtained, for example, by transesterification in
` accordance with the general equation:
,, .
n HO ~CH2--CH--C-oR4 + n-A' H
R
.~
!: - Rl R3
, Cat. ¦ HO ~ t
Rl, R2 and R3 are as defined above, whereas A' is -oR4 (R4 not Cl-C4alkyl) or-O-X'-O-
~3 and R40 is Cl-C4alkyl.
~'.3' Examples of suitable catalysts are dibutyltin oxide, ti-(O-i-C3H7)4, LiNH2, LiH, LiOH,
' j KOR, NaOR or LiOR, R being H or Cl-CIOalkyl, or
~: I R~
~ ~ R" ' in which R', R" and R"' independently of one another are H or alkyl
:' R " ~ .:
having 1 to 10 C atoms.
'~ :
The process is suitably carriedout in a solvent, such as benzene, toluene, xylene,
dime~hylformamide and the like.
. ~ ~
Another process for the preparation of the compounds according to the invention follows
the general equation below for the esterification~
- 2 ~ 2
'
19 -
l R3 Rl R3
CH3 . ~ CH3 O
HO ~ CH2- CH- CO2H+ A ~Hn id HO ~ CH2-CH- C- -A'+ nH20
R2 catalyst R ~ n
,3 Rl,R2,R3 and A' can be as defined above. The reaction is carried out in the presence of
an acid as catalyst. Thus the catalyst used can, for example, be a bleaching earth, such as
Tosil L80S, or p-toluenesulfonic acid. The acids of the formula III can be obtained, for
example, by saponifying esters of the formula II.
p A process which is also suitable for preparing compounds according to the present
invention is the reaction of a corresponding acid chloride with a compound of the formula
; A-OH. The process can be described in greater detail by means of the equation below:
1~ ~
~¦ Rl R3 Rl R3
CH3 O ~ CH3 O .
n HO ~ /~ CH2- CH- CCI+ A~Hn > HO ~\ /~ CH2-CH- C- - A + nHCI
acccptor R ~ _ n
IV
, ~
Rl,R2,R3, and A are as defined above. The examples of acid acceptors which can be
employed are pyridine, triethylamine or an alkali metal hydroxide, such as NaOH or KOH.
The compounds of the fornnula IV can be obtained by customary acid chlorination of
compounds of the formula III.
:
Another process for the preparation of compounds of the formulae I and Ia according to
the present invention follows the equation:
: R
HO~ ~ ~R3 Rl
R ~ CH2- CH- C - OR * ~ HO ~ R3 lCH3 RS
O R CH2-CH- C - N + ROR
'
20239~a
- 20 -
Rl, R2, R3, RS and Rfi are as defined above. R and R* independently of one another are,
-1 for example, hydrogen or Cl-C4alkyl. The reaction is carried out by the application of heat
!:i at, for example, 80-190C.
-' The present invention also relates to the use of compounds of the formula I, as described
, above, as stabilizers andlor coupler solvents for colour photographic recording material.
- If compounds of the formula (I) are liquid, they can be employed as solvents for the
photographic couplers.
The present invention also relates to the use of compounds of the formula Ia, according to
the above description, as stabilizers and/or coupler solvents for colour photographic
recording material.
,
If desired, further stabilizers known per se, for example antioxidants and light stabilizers
and especially phenolic antioxidants and sterically hindered amines, can be used in
addition to the compounds of the formula I used as stabilizers and/or coupler solvents. --
An antioxidative stabilization and an enhancement of the light stabilization is effected by
this means.
Examples of phenolic antioxidants are other compounds containing a sterically hindered
phenol group. Most of these compounds contain at least one group of the formula
`' R29
HO
R30
in which R29 and R30 independently of one another are Cl-CI2alkyl, cyclohexyl, phenyl or
C7-Cgphenylalkyl and R30 can also be hydrogen.
Antioxidants containing at least one group of the formula
~.
, ,, ., , . . . . , . . ~ . - . . , -
,1
:~ 3 --
~ .
.
`~- 2 ~ 2 ~
; I .
(CH3)3C H3C
. HO ~ or
~i j (CH3)3C(CH3)3C
,. i A j
are preferred.
~i, The following compounds are examples of antioxidants of this type:
Alkvlated monophenols, for example 2,6-di-tert-butyl-4-methylphenol,
~, 2-tert--butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,
i~ . 2,6-di-tert--butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol,
~;. 2,6-di-cyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol,
2,6-di-octadeycl-4-methylphenol, 2,4,6-tri-cyclohexylphenol,
; ~ 2,6-di-tert-butyl-4-methoxymethylphenol, and 2,6-dinonyl-4-methylphenol.
1 Alkylated hydroguinones, for example 2,6-di-tert-butyl-4-methoxyphenol,
1 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, and
;~ 2,6-diphenyl-4-octadecyloxyphenol.
Hvdroxvlated thiodiPhenyl ethers, for example, 2,2'-thio-bis-(6-tert-butyl4-methylphenol),
2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert--butyl-3-methylphenol), and4,4'-thio-bis-(6-tert-butyl-2-methylphenol).
Alkvlidene bisphenols, for example 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol),
2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol), 2,2'-methylene-
bis-[4-methyl-6-(-methylcyclohexyl)-phenol], 2,2-methylene-
bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol),
2,2'-methylene-bis-(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol),
2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol), 2,2'-methylene-
bis-E6-(a-methylbenzyl)-4-nonylphenol], 2,2'-methylene-
bis-[6-(a,-dimethylbenzyl)-4-nonylphenol], 4,4'-methylene-bis-(2,6-di-tert--butylphenol),
4,4'-methylene-bis-(6-tert-butyl-2-methylphenol),
I ,1 -bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane,
2,6-bis-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
: . :
. , . ' ' :
2 ~ 2 3 .~
22 --
1,1,3-tris-(S-tert-butyl-4-hydroxy-2-methylphenyl)-butane,
1, 1 -bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane,
ethylene glycol-bis-[3,3-bis-(3'-tert--butyl-4'-hydroxyphenyl)-butyrate],
bis-(3-tert-butyl-4-hydroxy-S-methylphenyl)-dicyclopentadiene, and
bis-[2-(3'-tert-butyl-2'-hydroxy-S'-methylbenzyl)-6-tert-buty 1-4-methylphenyl]
terephthalate.
Benzyl compounds, for example
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
bis-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl
3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,
bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol terephthalate,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate,
1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, dioctad~cyl
3,5:di-tert-butyl-4-hydroxybenzylphosphonate, calcium salt of monoethyl
3,5-di-tert-butyl-4-hydroxybenzylphosphonate and
1,3,5-tris-(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
Esters of B-(3.5-di-tert-butyl-4-hvdroxyphenyl)-propionic acid with monohydric or
polyhydric alcohols, for example methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris-(hydroxyethyl) isocyanurate and N,N'-bis-(hydroxyethyl)-oxamide.
Esters of ~-(S-tert-butYI-4-hYdroxy-3-methvlphenvl)-propionic acid with monohydric or
polyhydric alcohols, for example methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris-(hydroxyethyl) isocyanurate and N,N'-bis-(hydroxyethyl)-oxamide.
Esters of ~-(3,~cvclohexvl-4-hydroxyphenol)-propionic acid with monohydric or
polyhydric alcohols, for example methanol, octadecanol, 1,6-hexanediol, neopentyl glycol,
~hiodiethylene glycol, diethylenè glycol, triethylene glycol, pentaerythritol,
tris-(hydroxyethyl) isocyanurate and N,N'-bis-(hydroxyethyl)-oxamide.
Esters of 3,5-di-tert-butYI-4-hydroxYbenzoic acid with monohydric or polyhydric alcohols
or phenols, for example 2,4-di-tert-butylphenol or 2,4-di-tert-pentylphenol.
.
,,, ?
"' ''
2 0 2 3 9
~ - 23 -
"
.~., Amides of ~-(3~5-di-tert-butYl-4-hvdroxvphenvl)-propionic acid, for example
',, ? N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamet hylenediamine,
N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimeth ylenediamine and
N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazi ne.
~?
- . Further examples are the compounds of the following formulae:
C(CH3)3
CH-C3H7 ~CH-CHz- ~H-R R = ~ OH
'? R/ R/
t CH3
C(CH3)
` CH3 ~ -cH2-coocH2cH2ooc-cH2-l-CH3R~ = ~ OH
:.` CH3
[ Ç~(CH2)3C CH~ c R~ = CH3 ~ OH
:, H3 4 ~
., .
HO CH3
., CH3 ~ C - (CH2)3 - COOC6H13
C6H1300C--(CH2)3 C--~J I
I l CH3
CH3 OCH3
HO~CH~Ct C~N--CO CH=CH
(CH3 3C 2 H3C C~13
' . ' '-'
3 ~
2~23~
24 -
,: ~
J (CH3)3C CH3
HO ~ CU2CU2COOC2u5 ~CU3
.'~
(CH3)3C~
HO ~ 2 21~ 2 5)2
CH;~)~C
. ~
. ~ H3
~ y H3 ~3ocH~cooclzH~5
,, H3C CH3 . ~.
Instead of the free phenols it is also possible to use masked phenols. Examples of these are
esterified, sulfonylated, carbamoylated or silylated phenols. The free phenols aIe formed
from these during development.
t ~ ~
The photographic layers can also contain phenolic compounds which act as light
stabilizers for the colour image and also as agents against colour cast They can be present,
on the~r own or together with other additives, in a light-sensi~Live layer (colour layer) or in
an intermediate layer. C~ompounds of this type are described in greater detail in the
following patent Speci~lcations: US-A 3,700,455, 3,591,281, 3,573,052, 4,030,931,
4,174,220, 4,178,184,4,228,235, 4,279,990, 4,346,165, 4,366,226, 4,447,523, 4,528,264,
4,581,326, 4,562,146 and 4,559,297, GB-A 1,309,277, 1,547,302, 2,023,862, 2,135,788,
2,139,370 and 2,156,091; DE A~2,301,060, 2,347,708, 2,526,468, 2,621,203, 3,323,448- -
DD-A200,691 and214,468 EP-A 106,799, 113,124, 125,522, 159,912, 161,577, 164,030,
167,762 and 176,845; JP-A 74/134,326,76/127,730, 76/30462, 77/3822, 77/154,632,
78/10842, 79/48535,79no830, 79n3032, 79/147,038, 79/154,325, 79/155,836,
8V142,638, 83/224,353, 84/5246, 84n2443, 84/87456, 84/192,246, 84/lg2,247,
84/204,039, 84/204,040, 84/212,837, 84/220,733, 841222,836, 84/228,249, 86/2540, ;~;
~";
~' ` .
~ ~!
2~2~
., i.
- 25 -
~i.~
86,8843, 86/18835, 86/18836, 87/11456, 87/42245, 87/62157, 86/6652 and also in
Research Disclosure 79/17,804.
Examples of sterically hindered amines as light stabilizers are the polyalkylpiperidine
light stabilizers which can be employed and which can be low-molecular (MW < 700) or
- higher-molecular (oligomers and polymers). They contain the characteristic group A
RH2C~ ~CH3 R
' --N/ \~
' \ /\ (A)
RH2C CH3
. ~ .
in which R is hydrogen or methyl. This group can be present in the molecule once or
several times. Piperidine derivatives containing the group A in which R is hydrogen are
prçferred. These are derivatives of 2,2,6,6-tetramethylpiperidine. These
polyalkylpiperidines preferably carry one or two polar substituents in the 4-position or a
polar Spiro ring system is attached to the 4-position.
A detailed description of light stabilizers of this type and of their preferred forms is
available, for example, in EP-A 0,290,391.
The weight ratio of compounds of the formula I to other antioxidants and light stabilizers
can vary within a wide range. The weight ratio of compounds of the formula I to the other
antioxidants and light stabilizers is preferably 1:10 to 10:1, in particular, 1:5 to 3:1.
Provided that the compounds of the formula I and, if present, further stabilizers are water
soluble, they can be added in the form of an aqueous solution to the photsgrahic gelatin
emulsion when the latter is prepared. However, many of these compounds are only very
slightly soluble in water, and they are then dissolved in an organic solvent or solvent
mixture, and the solution is emulsified in a gelatin solution which is then added to the
photographic gelatin emulsion when the latter is prepared. It is preferable to use as the
solvent a mixture of a low-boiling and a high-boiling solvent and to remove the
low-boiling solvent during the emulsification. Examples of low-boiling solvents which
can be used are methyl acetate, ethyl acetate, carbontetrachloride, methylenechloride, -~
:: '
~- 2 1~ 2 ~
~.
- 26 -
., .
chloroform, methanol, ethanol, dioxane, acetone or benæne. Examples of high-boiling
solvents are dimethylformamide, dimethyl sulfoxide, dialkyl phthalates or triaryl
phosphates.
-, The stabilizer solution can be dispersed in the gelatin solution, for example, in a colloid
mill or in a homogenizer or by using ultrasonic sound. Surface-active agents (emulsifiers)
: can also be added in this process. Fine dispersion is essential for the homogeneous
~ distribution of the stabilizers in the photograhic layer.
I~:
The amount of the compound of the formula I added is generally up to 1 g/m2, preferably
10-300 mg/m2, per layer. If a combination of compounds of the forrnula I with other
stabilizers is used, the amount added in total is suitably also up to 1 g/m2, preferably
10-300 mg/m2.
~:
The addition can be made, for example, to one or two or all three of the dye-silver layers.
Addition to the yellow layer is particularly important. The sensitized silver halide and the
particular dye coupler are present in the layers. In addition, the layers can contain further
stabilizers and/or other additives.
:
~ The yellow couplers are preferably compounds of the formula IX
,
Rl--CO--CH--CO--NHR2
,.; in which Rl is alkyl or aryl, R2 is aryl and Q is hydrogen or a group which can be split off
~` by reaction with the oxidized developer.
.
One group of yellow couplers is constituted by compounds of the formula IX in which R
` is tert-butyl and R2 is a group of the formula
. . .:
R3 R4 - ~:
s \~
R5
\~
R6
.', 2~2~L~a
- 27 -
in which R3iS hydrogen, halogen, alkyl or alkoxy and R4, Rs and R6 are hydrogen,halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, a carbamoyl group, a
sulfonyl or sulfamoyl ~roup, an alkysulfonamido group, an acylamino group, a ureido
group or an amino group.
Preferably, R3iS chlorine, R4 and Rs are hydrogen and R6 is an acylamino group. Also
included are the compounds of the formula
. ' R8
NHco(cHR7) ~ Rg
. (CH3)3C- CO- CH- CO- NH ~ R5
.. Cl
~`
: in which x is 1-4, Rs is hydrogen or alkyl and R8 and R9 are alkyl.
Another group of yellow couplers has the formula X
:, Rlo
R~COCH(Q~CONH ~ NHCOCH(Q)CORI
RI~J~Rl3 X
12 ;, . ~:
in which Rlo is hydrogen, halogen or alkoxy, Rll, Rl2 and Rl3 are hydrogen, halogen,~:
alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, a carbamoyl group, a sulfonyl -
group, a sulfarnoyl group, a sulfonamido group, an acylamino group, a ureido group or an
amino group and Rl and Q are as defined above.
These include compounds of the formula X in which Rl is tert-butyl, Rlo is chlorine, Rl I : ~
and Rl3 are hydrogen and Rl2 is alkoxycarbonyl. ~ ~ -
The detachable group Q in the compounds of the formula IX and X can be hydrogen or
halogen or it is a heterocyclic group
; ~
:1 2~2~a
i
28-
. . .
~'1 ' . .
:., ,, . ~:
in which Rl4 is an organic divalent group which completes the ring to form a 4-membered
~,~A to 7-membered ring, or Q is a group -ORI5 in which Rls is alkyl, aryl, acyl or a
` -, heterocyclic radical.
The compounds of the following formulae are typical examples of customary yellowcouplers:
,~ ~
Cl
` ~ (CH3)3C--CO--CH~Q)--CONH~ C5H~ I-tcrt.
CO(CH2)30~ CsHl l-tert~ :
a) Q = --o ~ } so
' o
b) Q= --N
~ N--CH2C6H5 ~ ~
`I o
~CH(CH3)2 .~
c) Q = --N S
N--so2{}CH3
O :~
d) Q = --N N
-:: -~:
COOCH3 ~ ~:
~.:
:
- 29 -
.
fi 13
e) Q = --N N
; ') Cl
~` (CH3)3C - CO-CH(Q~-CONH ~ C12H5 CsHll-tcrt.
NHCO - CH - O ~ CsH~ crt.
. , .
0~
., f) Q= --N
O
; ~ . :
:~ O . -:
CH- OC2H5 ~.
g) Q = --N
:1 ~ N - Bc~yl ~.:
O '',,':
:~ Cl
i (cH3)3c-co-cH(Q~-coNH ~ NHco-cH(Q}-co-c(cH3)3 ~;
,:`j COOC12H25
. N _l CH(CH3)2 . : :
,~ /
h) Q= --N ::~
- r S ~CH3
Further examples of yellow couplers can be found in US-A 2,407,210, 2,778,658, ~ -
, 2,875,057, 2,908,513, 2,908,573, 3,227,155, 3,227,550, 2,253,924, 3,265,~06, 3,277,155,
3,408,194, 3,341,331, 3,369,895, 3,384,657, 3,415,652,3,447,928, 3,551,155, 3,582,322,
; ' : '
. .
~: :' :
r -
2~2
- 30-
3,725,072, 3,891,445, 3,933,501, 4,115,121, 4,401,752 and 4,022,620, in DE-A 1,547,868,
2,057,941, 2,162,899, 2,163,813, 2,213,461, 2,219,917, 2,261,361, 2,261,362, 2,263,875,
2,329,587, 2,414,006 and 2,422,812 and in GB-A 1,425,020 and 1,077,874.
The yellow couplers are eustomarily used in an amount of 0.05-2 mole, preferably 0.1-1
- mole, per mole of silver halide.
Magenta couplers can be, for example, simple 1-aryl-5-pyrazolones or pyrazole
' derivatives which are condensed with 5-membered hetero-rings, for example
imidazopyrazoles, pyrazolopyrazoles, pyrazolotriazoles or pyrazolotetrazoles.
. .
One group of magenta eouplers is constituted by 5-pyrazolones of the formula XI,
, Q ~R~7
D
o N~N XI
'. R16 :
sueh as are described in British Patent Specification 2,003,473. In these, Rl6 is hydrogen, ~;
alkyl, aryl, alkenyl or a heteroeyclic group and Rl7 is hydrogen, alkyl, aryl, a heteroeyclie
group, an ester group, an alkoxy group, an alkylthio group, a earboxyl group, an arylamino -
group, an aeylamino group, a (thio)urea group, a (thio)earbamoyl group, a guanidino
group or a sulfonamido group.
R20
R17ispreferablyagroup--Rl8
Rlg
in whieh Rl8 is imino, aeylamino or ureido, Rl9 is hydrogen, halogen, alkyl or alkoxy and
R20 is hydrogen, alkyl, aeylamino, earbamoyl, sulfamoyl, sulfonarnido, alkoxycarbonyl,
acyloxy or a urethane group.
If Q' is hydrogen, the magenta eoupler is tetra-equivalent in relation to the silver halide.
Compounds of the formula
: ` 2 ~ 2 ~
` ` - 31 -
....
~', cl
'.' HN~
''~ o~
- ¦ . R20
~i Cl~//~rCI
,.,
~i. 1
;'` Cl
in which R20 is as defined above are typical examples of this type of magenta couplers.
Further examples of tetra-equivalent magenta couplers of this type can be found in US-A
3 2,983,608, 3,061,432, 3,062,653, 3,127,269, 3,152,896, 3,311,476, 3,419,391, 3,519,429, -
3,558,319, 3,582,322, 3,615,506, 3,684,514, 3,834,908,3,888,680, 3,891,445, 3,907,571,
~ I 3,928,044, 3,930,861,3,930,866 and 3,933,500. ~ ~
.`.1 . .~. .: .
If Q' in formula XI is no~ hydrogen, but a group which is eliminated in the course of the
reaction with the oxidized developer, the magenta coupler is di-equivalent. Q' can in this
, case be, for example, halogen or a group attached to the pyrazole ring via O, S or N.
Di-equivalent couplers of this type give a higher colour density and are more reactive
towards the oxidized developer than are the corresponding tetra-equivalent magenta
, couplers. Q' is preferably an O-alkoxyarylthio group.
:~ :
` Examples of di-equivalent magenta couplers are described in US-A 3,006,579, 3,419,391,
~ 3,111,476, 3,432,521, 3,214,437, 4,032,346,3,701,783, 4,351,897 and 3,227,554, in EP-A
;~ 133,503, in DE-A 2,944,601, and in JP-A 78/34,044, 74/53,435, 74/53,436, 75/53,372 and
75/122,935.
: ,.
2 pyrazolone rings can be attachèd via a divalent Q', and so-called bis-couplers are then
, obtained. Examples of these are described in US-A 2,632,702, US-A 2,618,864, GB-A
968,461, GB-A 786,859, JP-A 76/37,646, 59/4,086, 69/16,110, 69/26,589, 74/37,854 and
74l29,638.
As mentioned above, it is also possible to use as magenta couplers pyrazoles which have
'~
:
20233 4~
- 32 -
. ~
' been condensed with S-membered heterocyclic structures - so-called pyrazoloazoles. The
. advantages of these compared with simple pyrazoles are that they exhibit colours of
' ' greater stability to forrnaldehyde solution and clearer absorption spectra.
. .,
They can be represented by the general forrnula XII
RI~Q'
Za XII
, I 1 .
,, . ZC.... Zb
; . ~,-
in which Za~ Zb and Zc are the groups needed to complete a 5-membered ring which can
contain up to four nitrogen atoms. Accordingly, the compounds can be
';, pyrazoloimidazoles, pyrazolopyrazoles, pyrazolotriazoles or pyrazolotetrazoles. Rl7 and
, Q' are as defined in formula XI. .
i Pyrazolotetrazoles are described in JP-A 85/33,522; pyrazolopyrazoles in JP-A 85/43,695;
pyrazoloimidazoles in JP-A 85/35,732, JP-A 86/18,949 and US-A 4,500,630; and
pyrazolotriazoles in JP-A 85/186,567, JP-A 86/47,957, JP-A 85/215,687, JP-A
85/197,688, JP-A 85/172,982, EP-A 119,860, EP-A 173,256, EP-A 178,789, EP-A
178,788 and in Research Disclosure 84/24,624.
Other pyrazoloazole magenta couplers are described in: JP-A 86/28,947, JP-A 85/140,241,
JP-A 85/262,160, JP-A 85n13,937, EP-A 177,765, EP-A 176,804, EP-A 170,164, EP-A
164,130, EP-A 178,794, DE- 3,516,996 and DE-A 3,508,766 and Research Disclosures81/20,919, 84/24,531 and 85/25,758. -~
Cyan couplers can be, for example, derivatives of phenol, 1-naphthol or
pyrazoloquinazolone. Preferred structures are those of the formula XIII
.. :
2 ~ 2 ~
,,
- 33 -
~, IOH
'iR21~ R23
~ J~ XIII
. R22 ~ R24
Q
, in which R2l, R22, R23 and R24 are hydrogen, halogen, alkyl, carbamoyl, amido,
sulfonamido, phosphoramido or ureido. R21 is preferably H or Cl; R22 is preferably an
alkyl or arnido group. R23 is preferably an amido group and R24 is preferably hydrogen. Q"
, is hydrogen or a leaving group which is removed in the course of the reaction with the
cxidized developer. A detailed enumeration of cyan couplers is to be found in US-A
4,456,681.
..,
The following are examples of customary cyan couplers:
. ! t-C5H,I
OH
H3C~NHCO--CH--O~C5HIl-t
I cl . .
, t-C5HI I
¦ OH
C ~NHCO--CHr O ~ 3 C5H ~ ~ -t
H3C
Cl
~:
.
s: ~
`` - 2~2~5
34
i ,' ~ t-C5HlI
Cl~"NHCO--CH--O~C5H~I-t
Cl
t,';
~, t-C4Hg
c~ b NHCO--CH--O~C4Ug-t
ii`'` Cl ~ ~-
F F
~O--CH-CONH~ F
CH(CH3)2 Cl
:. Cl
~C5H~ ~ O--CH--CONH~
,.,~ C6H13 Cl
"~! Further examples of cyan couplers are to be found in the following US Patent
Specifications: 2,369,929, 2,423,730, 2,434,272, 2,474,293, 2,521,908, 2,698,794,
2,706,684, 2,772,162, 2,801,171, 2,895,826, 2,908,573, 3,034,892, 3,046,129, 3,227,550,
3,253,294, 3,311,476, 3,386,301, 3,419,390, 3,458,315,3,476,560, 3,476,563, 3,516,831,
3,560,212, 3,582,322, 3,583,971, 3,591,383, 3,619,196, 3,632,347, 3,652,286, 3,737,326,
.,, , . ~
~i, . . .
2~2~
:
... ..
3,758,308, 3,839,044, 3,880,661, 4,004,929, 4,124,396, 4,333,999, 4,463,086 and
3 4,456,681.
. !
The colour developers customarily used for colour photographic materials are
p-dialkylaminoanilines. Examples of these are 4-amino-N,N-diethylaniline,
3-methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-a-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-~-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N--methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-a-methoxyethylaniline,
3--methanesulfonamidoethyl-4-amino-N,N-diethylaniline,
3-methoxy-4-amino-N-ethyl-N--hydroxyethylaniline,
3-methoxy-4-amino-N-ethyl-N--methoxyethylaniline,
3-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,N-dimethylaniline,
N-ethyl-N--[-t-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline,
N-ethyl-N--(-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and the salts of suchcompounds, for example sulfates, hydrochlorides or toluene sulfonates.
The compounds of the formula I which can be used in accordance with the invention can
be incorpoMted into the colour photographic material together with the dye coupler and, if
appropriate, other additives, by dissolving them beforehand in high-boiling organic
solvents. It is preferable to use solvents which boil above 160C. Typical examples of
such solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or
fatty acids, and also alkyamides and phenols.
.i .
In most cases a low-boiling solvent is also used, in addition, in order to facilitate the
incorporation of the addititives into the colour photographic material. Examples of
solvents of this type are esters, for example ethyl acetate, alcohols, for example butanol,
ketones, for example, methyl isobutyl ketone, chlorinated hydrocarbons, for examplè
methylene chloride, or amides, for example dimethylformamide. If the additives are
themselves liquid they can also be incorporated into the photographic material without the
aid of solvents.
Further details concerning high-boiling solvents which can be used are to be found in the
following patent specifications.
Phosphates: GB-A 791,219, BE-A 755,248 and JP-A 76n6,739, 78127,449, 78/218,252,
1 ~"` 2~3~
36
78/97,573, 79/148,113, 82/216,177, 82/93,323 and 83/216,177.
Phthalates: GB-A 791,219 and JP-A 77/98,050, 82/93,322, 82/216,176, 82/218,251,
83/24,321, 83/45,699 and 84n9,888.
` ) Amides: GB-A 791,219 and JP-A 76/105,043,77/13,600, 77/61,089, 84/189,556 and
US-A 928,741.
'. J, Phenols: GB-A 820,329, FR-A 1,200,657 and JP-A 69/69,946, 70/3,818, 75/123,026,
, 75/82,078, 78/17,914,78/21,166, 82/212,114 and 83/45,699.
. ~
Other oxygen-containing compounds: US-A 3,748,141 and 3,779,765, JP-A 73/75,126,
74/101,114, 74/10,115,75/101,625, 76/76,740, 77/61,089 and BE-A 826,039.
.~;
Other compounds: JP-A 72/115,369, 72/130,258,73/127,521, 73n6,sg2, 77/13,193,
77/36,294 and 79/95,233 and Research Disclosure 82/21,918.
The amount of high-boiling solvent is suitably within the range from 0.1 to 300 %,
preferably 10 to 100 %, relative to the dye coupler.
The photographic layers can also contain colour cast inhibitors. These prevent the
formation of colour casts such as are formed, for example, by reaction of the coupler with
unintentionally oxidized developer or with by-products of the colour formation process.
Colour cast inhibitors of this type are in most cases hydroquinone derivatives, but can also
be derivatives of aminophenols, gallic acid or ascorbic acid. Typical examples of these are
to be found in the following patent specifications: US-A 2,360,290, 2,336,327, 2,403,721,
2,418,613, 2,675,314, 2,701,197, 2,704,713,2,728,659, 2,732,300 and 2,735,365; EP-A
124,877; JP-A 75/92,988, 75/92,989, 75/93,928, 75/110,337 and 77/146,235.
The photograhpic layers can also contain so-called DIR couplers, which produce
colourless compounds with the oxidized developer. They are added in order to improve
the sharpness and grain of the colour images.
The photographic layers can also contain UV absorbers. These filter out the UV light and
thus protect the dyes, the couplers or other components from degradation by light.
Examples of UV absorbers of this type are 2-(2-hydroxyphenyl)-benzotriazoles,
2-hydroxybenzophenones, salicylic acid esters, acrylonitrile derivatives or thiazolines. UV
absorbers of this type are listed in greater detail in, for example, the following patent
specifications: US-A 3,314,794, 3,352,681, 3,705,805, 3,707,375, 4,045,229,3,700,455,
.
~ , .
" ~ ~ r
-37
3,533,794,3,698,907,3,705,805 and 3,738,837 and JP-A 71/2784. The
2-(2-hydroxyphenol)-benzotriazoles are preferred UV absorbers.
,".~
The photographic layers can also contain certain phosphorus-III compounds, in particular
i phosphites and phosphonites. These act as a light stabilizer for the colour images and as a
- -~ dark storage stabilizer for magenta couplers. They are preferably added to the high-boiling
1 solvents, together with the coupler. Phosphorus-lII compounds of this type are described
-, in greater detail in the following patent specifications: US-A 4,407,935, US-A 4,436,811,
-, EP-A 181,289, JP-A 73/32,728, JP-A 76/1420 and JP-A 55/67,741.
~ ~ :
J The photographic layers can also contain organometallic complexes which are light
rl stabilizers for the colour images, particularly for the magenta dyes. Compounds of this
~, type and their combination with other additives are described in greater detail in the
:i following patent specifications: US-A 4,050,938,4,239,843,4,241,154,4,242,429,
4,241,155,4,242,430,4,273,854,4,246,329,4,271,253,4,242,431,4,248,949,4,245,195,~ 4,268,605,4,246,330,4,269,926,4,245,018,4,301,223,4,343,886,4,346,165 and
- 4,590,153; JP-A 81/167,138,81/168,652,82/30,834 and 82/161,744; EP-A 137j271, -
161,577 and 185,506; DE-A 2,853,865.
., .
The photographic layers can also contain hydroquinone compounds. These act as light
stabilizers for the dye couplers and for the colour images and also as interceptors of
oxidized developer in the interrnediate layers. They are used particularly in the magenta
layer. Hydroquinone compounds of this type and their combinations with other additives
are described in greater detail in the following patent specifications: US-A 2,360,290,
2,336,327,2,403,721,2,418,613,2,675,314,2,701,197,2,710,801,2,732,300,2,728,659,2,735,765,2,704,713,2,937,086,2,816,028,3,582,333,3,637,393,3,700,453,3,960,570,3,935,016,3,930,866,4,065,435,3,982,944,4,232,114,4,121,939,4,175,968,4,179,293,3,591,381,3,573,052,4,279,990,4,429,031,4,346,165,4,360,589,4,346,167,4,385;111,4,416,978,4,430,425,4,277,558,4,489,155,4,504,572 and 4,559,297, FR-A 885,982;
GB-A 891,158,1,156,167,1,363,921,2,022,274,2,066,975,2,071,348,2,081,463,
2,117,526 and 2,156,091; DE-A 2,408,168,2,726,283,2,639,930,2,901,520,3,308,766,3,320,483 and 3,323,699; DD-A 216,476,214,468 and 214,469, EP-A 84,290,110,214,
115,305,124,915,124,877,144,288,147,747,178,165 and 161,577; JP-A 75/33,733,
75/21,249,77/128,130,77/146,234,79no,036,79/133,131,81/83,742,81/87,040,
81/109,345,83/134,628,82/22,237,82/112,749,83/17,431,83/21,249,84ns,249,
84/149,348,84/~82,785,84/180,557,84/189,342,84/228,~49,84/101,650,79/24,019,
~:
.
~:.
.~ ~ ~
2~23~ ~
-38-
79/25,8~3, 86/48,856,86/4~,857, 86l27,539, 86/6652, 86f72,040, 87/11,455, 87/62,157
and also in Research Disclosures 79/17,901, 79/17,905,79/18,813, 83/22,827 and
84/24,014.
The photographic layers can also contain derivatives of hydroquinone e~hers. These
compounds act as light stabilizers and are particularly suitable for stabilizing magenta
dyes. Compounds of this type and their combination with other additives are described in
greater detail in the following patent speci~lcations: US-A 3,285,937, 3,432,300,
3,519,429, 3,476,772,3,591,381,3,573,052, 3,574,627, 3,573,050, 3,698,909, 3,764,337,
3,930,866, 4,113,488, 4,015,990, 4,113,495, 4,120,723,4,155,765, 4,159,910, 4,178,184,
4,138,259, 4,174,220,4,148,656, 4,207,111, 4,254,216, 4,314,011, 4,273,864, 4,264,720,
4,279,990, 4,332,886, 4,436,165, 4,360,589, 4,416,978, 4,385,111, 4,459,015 and
4,559,297; GB-A 1,347,556, 1,366,441, 1,547,392, 1,557,237 and 2,135,788; DE-A
3,214,567; DD 214,469; EP-A 161,577, 167,762, 164,130 and 176,845; JP-A 76/123,642,
77/35,633, 77/147,433, 78/126, 78/10,430,78/53,321,79/24,019, 79/25,823,79/48,537,
79/44,521,79/56,833,79no,036,79/70,830, 79/73,032, 79/95,233, 79/145,530, 80/21,004,
80/50,244, 80/52,057,80170,840, 80/139,383, 81/30,125, 81/151,936, 82/34,552,
82/68,833, 82/204,0~6, 82/204,037, 83/134,634, 83/207,039, 84/60,434, 84/101,650,
84/87,450, 84/149,348, 84/182,785, 86n2,040, 87/11,455, 87/62,157, 87/63,149, 86/2151,
86/6652 and 86/48,855 and in Research Disclosure 78/17,051.
-
The photographic layers can also contain phenolic thiane derivatives according to EP-A
0,310,551 and/or tetrahydrothiopyrane compounds according to EP-A 0,310,552 as
stabilizers.
The following examples illustrate the invention in greater detail. Parts and percentages are
by weight. The temperatures are quoted in C.
Examples:
1. Preparation of methvl 3-r3.5-di-tert-butvl-4-hydroxvphenvll-2-methvlpropanoate
Analogous to the state of the art, for example in accordance with Example 1 in US
4,529,089 from 2,6-di-tert-butylphenol and methyl methacrylate.
~i -
~2~
- 39 -
2. Octadecyl 3-(3'.5'-di-tert-butvl-4'-hvdroxyphenvl)-2-methylpropanoate
.-, OH OH :
(H3C)3C ~ c(CH3)3 (H3C)3C ~ C(CH3)3
+ HO--n C18H37 _ > ~ + CH30H
CH2--CH--C\ CH2--CH--C\
.' 3. ' CH3 OCH3 CH3 n C18H37
~, , :
30.6 g (0.1 mole) of methyl-2-methyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-propionate
and 27 g (0.1 mole) of 1-n-octadecanol are initially taken in a 4-necked glass flask and are
heated to 100C. 0.25 g (1 mole %) of dibutyltin oxide is then added and the mixture is
heated to 180C. In the course of this methanol is split off. The temperature is kept at
1 80C for 6 hours.
The reaction mixture is chromatographed over silica gel.
This gives 52.4 g _ 96.2 % of theory of an oil which slowly crystallizes.
Analysis: calculated 79.35 %C 11.84%H
found 79.57 % C 11.68 % H
3. The procedure described in Example 2 is repeated, except that the compound of the
formula
'I
H3C-H2C~CO~
is used instead of 1-n-octadecanol, affording the compound of the formula
, ~
2;~ 5
, - 40 -
:' ~
(H3C3C~C(CH3)
~, CH2~ CH--C--O~ O~
~, CH3 /\~ S
CH3
..1 '
' in the forrn of a yellow oil.
,1 4. 2-Ethylhexyl 3-(3',5'-di-t-butvl-4'-hydroxvphenyl)-2-methvlpropanoate
OH
(H3C)3C ~ C3(CH3)3 CH2 ,CH2 ~CH2
+ HO CH ~CH ~CH
H 1I H2C--CH3
H2C - C - C - O - CH3
~j CH3
~, OH
~1,(H3C)3C~C(CH3)3
H It ~CH~ ,CH2 ~CH2
H2C - C C - O CH2 CH2 CH3
H2C--CH3
61.3 g (0.2 mole) of methyl 2-methyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)-propionate
and 26 g (0.2 mole) of 2-ethyl-1-hexanol are initially taken in a 4-necked glass flask and
are heated to 100C. 1 g (2 mole %) of dibutyltin oxide is then added and the temperature
is raised to 1 80C. Methanol is split off. The reaction mixture is kept at 1 80C for 9 hours.
The product is obtained in the form of a resin in a yield of 79.4 g _ 98.2 % of theory. It is
purified by chromatographing the product over silica gel.
Analysis: calculated 77.18 % C 10.96 % H 11.86 %
found 77.05 %C 11.03 %H
.:~
2~2~g~
:
~; - 41 -
'~, '
J 5. Thiodiethvlene ~IYCOI biS-~2-methYI-3-(3~5~-di-t-bUtVI-4~-hVdrOXVPhenYI)-PrOPiOnate1
~; OH
~ . 1 (H3C)3C ~ CH2 CH2
, 2 ~ ¦¦ + HO \ ,S \; ,OH _3,
1 ~ H '' CH2 CH2
H2C--C - C - O - CH3
~ CH3
.: ,
~'
OH OH
(H3C)3C~ C3(CH3)3 (H3C)3C~C(CH3)3
O CH2 ,CH2 11 H~ + 2 CH3OH
` ' ~ H2C--C - C _ o \ ~s \ ~o--C - C--CH2
:1 CH3 CH2 CH2 CH3
.:', - '
, 91.9 g (0.3 mole) of methyl-2-methyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)-propion ate
- and 18.3 g (0.15 mole) of thiodiethylene glycol are initially taken in a 4-necked glass flask
and are heated to 100C. 0.4 g ( ^ 0.5 mole %) of dibutyltin oxide is added and the mixture
is heated to 180C, in the course of which methanol is split off. The temperature is kept at
1 B0C for 6 hours.
,
The resulting brown oil is subsequently purified by column chromatography, and 72.4 %
of the amount employed are obtained in the form of a viscous oil.
,
~Analysis: calculated 71.60 % C 9.31 % H 4.78 % 5ifound 71.66% C 9.08 %H 4.90% S ~ ~
- ~- .
~; 6. Preparation of methYI 3-r3-tert-butYI-4-hvdroxvphenvll-2-methYlpropanoate190 g of methyl 3-[3,5-di-tert-butyl-4-hydroxyphenyl]-2-methylpropanoate (0.62 mole)
`~ are stirred with 11.40 g of sarnphor-(10)-sulfonic acid (0.05 mole) for 24 hours at 120C.
The reaction is monitored by means of gas chromatography. The reaction mixture was ~ -
taken up in ethyl acetate, washed until neutral with sodium bicarbonate and water, and
- dried and the solvent was evaporated. The crude product is distilled under high vacuum.
Boiling point 115C/152mm[Hg].
1,~, ~ j
:
2 a 2 ~
::
` ~t - 42 -
- 1 93 g of methyl 3-[3-tert-butyl-4-hydroxyphenyl]-2-methylpropanoate are obtained in the
3 `:.~, form of a white solid. Melting point: 49C.
. I C(CH3)3
Formula: HO ~ CH2- C, H CO OCH3
'
s~ 7. Preparation of 2-methylpentvl 3-r3-tert-butvl-4-hYdroxyphenY1l-2-methYlpropanoate
2.5û g of methyl 3-[3-tert-butyl-4-hydroxyphenyl]-2-methylpropanoate (0.01 mole) are
stirred with 7.80 g of 2-methyl-1-pentanol (0.076 mole) and 0.10 g of dibutyltin oxide
(0.00040 mole) at 120C for 24 hours. The methanol formed in the reaction is distilled off
~, ~, continuously during the reaction. The reaction is monitored by means of thin-layer
chromatography. The excess 2-methyl-1-pentanol is distilled off at 100C and 15 mm Hg,
~, and the crude product is chromatographed over silica gel. 1.60 g of 2-methylpentyl
3-[3-tert-butyl-4-hydroxyphenyl]-2-methylpropanoate are obtained in the form of a
colourless viscous oil.
8. Preparation of 9-octadecenvl 3-r3-tert-butvl-4-hvdroxyDhenYIl-2-methYlpropanoate
73 g of 9-octadecenyl 3-[3-tert-butyl-4-hydroxyphenyl]-2-methylpropanoate are obtained
in the form of a colourless oil from 47.3 g of methyl
3-[3-tert-butyl-4-hydroxyphenyl]^2-methylpropanoate (0.20 mole), 112 g of
9-octadecen-1-ol (0.40 mole) and 0.50 g of dibutyltin oxide (0.0020 mole) in a mode of
preparation analagous to that of Example 6.
,
9.-11. Testing the stabilizers
0.087 g of the yellow coupler of the formula
. ~ .
,.s
~.~
"
r~i
., ~ .
: '1
2~23
.,.
, 43
. ......................................................................... .
- :~ Cl
(CH33--C--C0--CH--CONH~ fH2
` N~ >= N - S2 C(CH3)2
;: S 1 NH--CO--(CH2)30 ~
CH(C~13)2 ~ C(~H3 2
.. CH3 1CH2
~ CH3
~''. ~.
;~ and 0.029 g of one of the light stabilizers indicated in the following table are dissolved in
2 ml of a mixture of dibutyl phthalate and ethyl acetate (1.5 g/100 ml). To 1.0 ml of this
,'', solution are added 9.0 ml of a 2.3 % aqueous gelatin solution, the pH of which has been
adjusted to 6.5 and which contains 1.744 g/litre of the wetting agent ~)Nekal BX (sodium
diisobutylnaphthalene sulfonate).
.. -, .
~2, 3 :~
, ~ 3 CH
.: IX~503N.
~`~~CH ~CH3
~' CH3 CH2
The mixture is then emulsified for 3 minutes by means of ultrasonic sound.
To 5.0 ml of the coupler emulsion thus obtained are added 2 ml of a silver bromide
emulsion containing 6 g of silver per litre, and 1.0 ml of a 0.7 % aqueous solution of the
curing agent of the formula~
'. - ::
3 2
:
- 44 -
~ 1 Cl
,:, \
i k /~--OH
N
Cl
and the mixture is then cast onto plastic-coated paper measuring 13 x 18 cm. After a
curing time of 7 days the samples are exposed to light of 125 lux. second through a silver
step wedge and are then developed by the Kodak (~F,xtaprint 2 process.
`, The colour step wedges thus obtained are irradiated with a total of ~0 kilojoules per cm2
: by means of a 2500-watt xenon lamp in an Atlas Weather-Ometer behind a UV filter
j (Kodak 2C).
;
The percentage decreases in colour density at an original colour density of 1.0 are shown
in the following table.
P !
Table:
.'i
`. ~ Compound 60 kJlcm2 (UV filter)
. Example Slabilizer according Percentagc decrease ir
o exam colour dcnsity
Comparison None 33
. HO ~ CH2- C, H CO OCl8H37 2 16
~, C(CH3)3
. C(CH3)3
HO ~ CH2--CH.CO.OCH2- CH~C4Hg 3 25
C(CH3)3 CH3 C2Hs ~ -
.. C(CH3)3 - .. _
HO ~ CH2- C, H.CO.OCH2 CH2--- S 4 12
C(CH3)3 CH3 2
` ' '
'
,
. ,,~, . ~ ~ : , . ,
