Note: Descriptions are shown in the official language in which they were submitted.
1036756
lrhe present invention relates to a process for printing
hydrophobic fibre materials in accordance with the transfer
printing principle, which is characterised in that sublimable
azo dyestu~fs which are free from sulpho groups, of the
formula
(C~
~ ~=N ~ N~
are used,
wherein
Xl and X2 represent hydrogen or alkyl or cycloalkyl
radicals which are optionally substituted by non-
polar substituents and
n represents 1-3,
and the benzene ring A can contain non-ionic substituents which
are customary in dyestuff chemistry, and the benzene ring B
can contain customary non-polar substituents, which do not
significantly influence the sublimability of the base molecule.
In addition to hydrogen, suitable radicals Xl and X2 are
Cl-C4-alkyl or C5-C7-cycloalkyl radicals which are optionally
substituted by Cl-C2-alkoxy, halogen or phenyl.
Suitable non-ionic substituents, customary in dyestuff
chemistry, in A are N02, CN, halogen, S02CH3, S02C2H5,
Cl-C4-alkYl or Cl-c4-alkoxy~
Suitable non-polar substituents in B are Cl-C4-alkyl,
Cl-C4-alkoxy, halogen, benzyloxy, phenoxy, optionally halogen-
substituted Cl-C4-alkylcarbonylamino or formylamino.
"Halogen" preferably represents F, Cl and Br. Dyestuffs to
be used preferentially correspond to the formula ;
Le A 15 466 - 2 -
103~i756
ÇF~ p~
N=N ~ N ~ II
r~ ~
wherein
Yl = H, N02, CN, CF3 or CH3,
Y2 = Yl, Cl or Br,
y3 = H or Cl,
Rl and R2 = H, Cl-C4-alkyl, phenyl-Cl-C3-alkyl,
cyclopentyl, cyclohexyl, methylcyclohexyl, Cl-C4-
chloroalkyl or Cl-C2-alkoxy-Cl-C4-alkyl,
R3 = H, Cl-C4-alkyl, Cl-C4-alkoxy, phenoxy or
benzyloxy,
R4 = H, CH3, CF3, C2H5, Cl, Br or NHCOR5 and
R5 = H, Cl-C4-alkyl, Cl-C4-chloroalkyl, Cl-C4-bromo-
alkyl or methoxy-C2-C4-alkyl.
Preferred types are those, within the scope of the
formula II, wherein
a) Yl = N02 and Y2 and y3 = H,
b) Yl and Y2 = N02 and y3 = H,
c) Yl = CN, Y2 = N02 and y3 = H,
d) Yl and y3 = H and Y2 = CF3, as well as
e) Yl = N02; Y2 = CF3 and y3 = H
wherein
Rl-R4 have the indicated meaning.
Amongst these, in turn, preferred dyestuffs are those in which
R3 = H, CH3, OCH3 or OC2H5 and
R4 = H, CH3, C2Hs or Cl-
The dyestuffs of the formula (I) are prepared according
Le A 15 466 - 3 -
10367S6
to processes which are in themselves known, by diazotising an
aniline of the formula (III)
~CF~)n III
~ N~
and combining the diazonium compound with a collpling component
of the formula (IV).
IV
~ N \
Examples of possible diazo components of the formula
(III) are: l-amino-2-trifluoromethylbenzene, 1-amino-4-tri-
fluoromethylbenzene, l-amino-2-chloro-4-trifluoromethylbenz-
ene, 1-amino-2-bromo-4-trifluoromethylbenzene, 1-amino-2-
methyl-4-trifluoromethylbenzene, 1-amino-2-trifluoromethyl-4-
chlorobenzene, l-amino-2-trifluoromethyl-4-methylbenzene, 1-
amino-2,4-bis-trifluoromethylbenzene, 1-amino-2,6-bis-tri-
fluoromethylbenzene, l-amino-2-chloro-5-trifluoromethylbenzene,
1-amino-2,5-bis-trifluoromethylbenzene, 1-amino-2,4,6-tris-
trifluoromethylbenzene, l-amino-2-trifluoromethyl-4-nitro-
benzene, l-amino-2-nitro-4-trifluoromethylbenzene, 1-amino-2-
trifluoromethyl-4,6-dinitrobenzene, 1-amino-2,4-bis-trifluoro-
methyl-6-nitrobenzene, 1-amino-2,6-bis-trifluoromethyl-4-nitro-
benzene, 1-amino-4-trifluoromethyl-2,6-dinitrobenzene, l-amino-
2-cyano-4-trifluoromethylbenzene, 1-amino-2-trifluoromethyl-4-
cyanobenzene, l-amino-4-trifluoromethyl-2,6-dicyanobenzene,
l-amino-2-trifluoromethyl-4,6-dicyanobenzene, 1-amino-2,6-
trifluoromethyl-4-cyanobenzene, 1-amino-4-trifluoromethyl-2-
nitro-6-cyanobenzene, 1-amino-2-trifluoromethyl-4-cyano-6-
Le A 15 466 - 4 _
1036756
nitrobenzelle~ l-amino-2-cllloro-4~(~-bis-tr.ifllloromethylbenzene,
:I.-amino-2-fluoro-4-trifluoromethylbenzene, 1-amino-2-fluoro-
4,~-bis-trifluoromethylbenzene, 1-alllino-2~(,-dichloro-4-tri-
fl~oromethyl.aniline, :l-amino-2-trifluoromct~ly`l-5-.nitrobenzene,
l-(N~N-diethylamino)-~-trifluoromethylbenzene, I.-(N-ethyl-N-
benzy:Lamino)-~-trifluoromethy:lben2ene~ :1-am.ino-2-trifluoro-
methyl-4-methylsulphonylbenzene, 1-amino-2-trifluoromethyl-4-
ethylsulphonylbenzene~ l-amino-2,G-bis-trifluoromethyl-4-
nitrobenzene and l-amino-2-methoxy-4-nitro-6-trifluoromethyl-
benzene.
Examples of possible coupling components of the formula(IV) are: N,N-dimethylaniline, N,N-diethylaniline, N,N-di-
n-propylaniline, N,N-diisopropylaniline, N,N-di-n-butyl-
aniline, N-methyl-N-benzylaniline, N-ethyl-N-benzylaniline,
N-n-propy`l-N-benzylaniline, N-methyl-N-~-phenylethylaniline,
N-ethyl-N-~-phenylethylaniline, N-n-butyl-N-~-phenylethyl-
aniline, N-methyl-N-cyclopentylaniline, N-ethyl-N-cyclopentyl-
aniline, N-methyl-N-cyclohexylaniline, N-ethyl-N-cyclohexyl-
aniline, N-n-butyl-N-cyclohexylaniline, N,N-di-benzylaniline,
N-benzyl-N-cyclohexylaniline, N-~-phenethyl-N-cyclohexyl-
aniline, N-m~thyl-N-~-chloroethylaniline, N-ethyl-N-~-chloro-
ethylaniline, N-methyl-N-~-chloropropylaniline, N-ethyl-N-~-
chloropropylaniline, N-ethyl-N-~-chloropropylaniline, N-ethyl-
N-~-bromoethylaniline, N-n-propyl-N-~-chloroethylaniline, N-
propyl-N-~-chloroethylaniline, N-benzyl-N-~-chloroethylaniline,
N-cyclohexyl-N-~-chloroethylaniline, N,N-bis-~-chloroethyl-
aniline, N-~-phenylethyl-N-~-chloroethylaniline, l-(N,N-
dimethylamino)-3-methylbenzene, 1-(N,N-diethylamino)-3-
methylbenzene, l-(N,N-di-n-propylamino)-3-methylbenzene, 1-
(N,N-diisopropylamino)-3-methylbenzene, 1-(N,N-di-n-butyl-
amino)-3-methylbenzene, 1-(N-methyl-N-benzylamino)-3-methyl-
Le A 5 466 - 5 -
~036756
benzene, l-(N-ethyl-N-benzylamino)-3-methylbenzene, l-(N-n-
propyl-N-benzylamino)-3-methylbenzene, l-(N-methyl-N-~-phenyl-
ethylamino)-3-methylbenzene, l-(N-ethyl-N-~-phenylethylamino)-
3-methylbenzene, 1-(N,n-butyl-N-~-phenylethylamino)-3-methyl-
benzene, 1-(N-methyl-N-cyclopentylamino)-3-methylbenzene, 1-
(N-ethyl-N-cyclopentylamino)-3-methylbenzene, l-(N-methyl-N-
cyclohexylamino)-3-methylbenzene, ].-(N-ethyl-N-cyclohexyl-
amino)-3-methylbenzene, 1-~N,N-dibenzylamino)-3-methylbenzene,
l-(N-benzyl-N-cyclohexylamino)-3-methylbenzene, l-(N-~-phenyl-
ethyl-N-cyclohexylamino)-3-methylbenzene, l-(N-methyl-N-~-
chloroethylamino)-3-methylbenzene, l-(N-ethyl-N-~-chloroethyl-
amino)-3-methylbenzene, 1-(N-methyl-N-~-chloropropylamino)-3-
methylbenzene, l-(N-ethyl-N-~-chloropropylamino)-3-methylbenz-
ene, l-(N-ethyl-N-~-chloropropylamino)-3-methylbenzene, l-(N-
ethyl-N-~-bromoethylamino)-3-methylbenzene, l-(N-benzyl-N-~-
chloroethylamino)-3-methylbenzene, l-(N-cyclohexyl-N-~-chloro-
ethylamino)-3-methylbenzene, l-(N-~-phenylethyl-N-~-chloro-
ethylamino)-3-methylbenzene, 1-(N,N-bis-~-chloroethylamino)-3-
methylbenzene, l-(N,N-dimethylamino)-3-chlorobenzene, l-(N,N-
diethylamino)-3-chlorobenzene, 1-(N-ethyl-N-benzylamino)-3-
chlorobenzene, l-(N-ethyl-N-~-phenylethylamino)-3-chlorobenz-
ene, l-(N-ethyl-N-cyclohexylamino)-3-chlorobenzene, l-(N-
ethyl-N-~-chloroethylamino)-3-chlorobenzene, l-(N,N-diethyl-
amino)-3-bromobenzene, 1-(N-ethyl-N-benzylamino)-3-bromobenz-
ene, 1-(N-ethyl-N-~-chloroethylamino)-3-bromobenzene, l-(N,N-
dimethylamino)-3-acetylaminobenzene, 1-(N,N-dimethylamino)-3-
propionylaminobenzene, 1-(N,N-dimethylamino)-3-formylamino-
benzene, l-(N,N-dimethylamino)-3-chloroacetylaminobenzene,
l-(N,N-dimethylamino)-3-~-chloropropionylaminobenzene, 1-
(N,N-diethylamino)-3-formylaminobenzene, l-(N,N-diethylamino)-
3-acetylaminobenzene, 1-(N,N-diethylamino)-3-butyrylamino-
Le A 15 466 - 6 -
10;~67S6
benzene, l-(N,N-diethylamino)-3-chloroacetylaminobenzene, 1-
(N,N-ethylbenzylamino)-3-acetylaminobenzene, l-(N-ethyl-N-
benzylamino)-3-chloroacetylaminobenzene, l-(N-ethyl-N-benzyl-
amino)-3-formylaminobenzene, 1-(N,N-dibutylamino)-3-formyl-
aminobenzene, l-(N,N-dibutylamino)-~-chloroacetylaminobenzene,
l-(N,N-dimethylamino)-2-methoxy-5-formylaminobenzene, l-(N,N-
dimethylamino)-2-methoxy-5-acetylaminobenzene, l-(N,N-diethyl-
amino)-2-methoxy-5-acetylaminobenzene, 1-(N,N-diethylamino)-2-
ethoxy-5-acetylaminobenzene, 1-(N,N-diethylamino)-2-phenoxy-
5-acetylaminobenzene, 1-(N,N-diethylamino)-2-benzyloxy-5-
acetylaminobenzene, l-(N,N-diethylamino)-2-methyl-5-acetyl-
aminobenzene, l-(N,N-diethylamino)-2-methyl-5-chlorobenzene,
l-(N,N-diethylamino)-2,5-dimethylbenzene, l-(N,N-diethylamino)-
2-ethyl-5-formylaminobenzene, 1-(N,N-diethylamino)-2-propoxy-
5-acetylaminobenzene~ 1-(N,N-diethylamino)-2-methoxy-5-
chloroacetylaminobenzene, l-(N-ethyl-N-benzylamino)-2-methoxy-
5-acetylamin~obenzene, 1-(N-ethyl-N-cyclohexylamino)-2-methoxy-
5-acetylaminobenzene, 1-(N-ethyl-N-~-chloroethylamino)-2-
methoxy-5-acetylaminobenzene, 1-(N,N-ethylamino)-2-methoxy-5-
methylbenzene, 1-(N,N-diethylamino)-2-methoxy-5-chlorobenzene,
l-(N-benzyl-N-n-butylamino)-2-methoxy-5-acetylaminobenzene and
l-(N,N-dibenzylamino)-2-phenoxy-5-chloroacetylaminobenzene.
The transfer printing process is generally known and
has been described, for example, in French Patent Specifica-
tions 1,223,330 and 1,334,829. The dyestuffs, for example
in the form of so-called printing inks, such as are described,
for example, in French Patent Specification 1,573,698, or in
the form of pastes, are applied to temporary supports
(paper, other cellulosic materials, such as cotton or
cellophane, metal foils and the like, such as are known, for
example, from French Patent Specification 1,575,069). These
Le A 15 466 - 7 _
10367S6
printing inks are dyestuff solutions, also containing syn-
thetic resin, in suitable organic solvents, such as benzene,
toluene, xylene, chlorobenzene, chloroform, dichloroethane,
trichloroethylene, perchloroethylene, ethanol, iso-propanol,
benzyl alcohol, cyclohexanone, ethyl acetate or their mixtures.
However, the printing inks and printing pastes can also be
formulated on an aqueous basis and are thus dispersions of the
dyestuffs in water, which in addition con~k customary dis-
persing agents and thickeners (compare French Patent Specifi-
cation 1,223,330) and US Patent Specification 3,647,503).
The printing inks can be printed by the customary printing
processes (relief printing, gravure printing, offset printing,
film printing or screen printing).
Suitable substrates for transfer printing with dye-
stuffs of the formula I are textile materials which consistwholly or predominantly of polyesters, such as polyethylene
glycol tereph~halate, poly-1,4-bis-hydroxymethylcyclohexane
terephthalate or cellulose triacetate and cellulose 2~-acetate
or of polyamides or polyacrylonitrile, but also non-textile
plastics articles, such as films, tapes or blocks of
commercially available polymerisation or polycondensation
plastics.
Particularly suitable dyestuffs I sublime in the range
from 140-250C, preferably from 160-220C.
Example 1
A) 75 g of the dyestuff of the formula
~F~
0~ N~N=N~N~C~ C~ ~:1
C~
50 g of an anionic dispersing agent, for example a lignin-
Le A 15 466 - 8 -
1036756
sulphonate or a condensation product of naphthalenesulphonic
acid and formaldehyde, and 100 ml of water are mixed and
converted to a finely divided form by grinding for 10 hours
in a ball mill.
The dispersion thus obtained, which contains approx.
30% of crude colourant, is stable on storage.
B) The aqueous dispersion obtained according to A) can
be converted to a printing paste as follows: 50 to 200 g are
worked into a paste with 400 g of a 10% strength carob bean
flour ether thickener and 550 to 400 ml of water.
C) A paper is printed with this printing paste by the
gravure printing process. If this paper is pressed against
a textile of polyester fibres for 15 to 60 seconds at 200C,
a clear, deep red print with good fastness properties is
obtained.
Example 2
A) 40 to 50 g of the dyestuff used in Example 1 are worked
into a paste with 5 to 10 g of an emulsifier mixture of
ethoxylated nonylphenol (4 to 12 mols of ethylene oxide) in
water. 10 g of ethylcellulose N4 (Hercules Powder) and
30 to 40 parts of a maleate resin which has been prepared by
condensation of colophony with maleic acid are added. The
mixture is kneaded at 80 to 100C for approx. 2 hours and is
then ground on one of the customary mills. A finely
granular dyestuff powder is obtained.
B) 200 g of the dyestuff powder obtained according to A)
are introduced into a mixture of 730 g of ethanol, 50 g of
ethylene glycol and 20 g of ethylcellulose N22 (Hercules
Powder), whilst stirring.
C) Papers can be printed with the printing ink thus
obtained by the gravure printing process. Textiles of
Le A 15 466 - 9 -
~0367S6
cellulose triacetate or polyamide, for example knitted
fabrics, can be printed with these printed papers by the
transfer process, and deep red prints are obtained.
The dyestuff of Example 1 was prepared as follows:
~0 parts of finely powdered 1-amino-2-trifluoromethyl-4-
~itrobenzene were dissolved in 300 parts of concentrated
sulphuric acid whilst stirring; during this time the tempera-
ture should not exceed 20C. The solution is then cooled
to 0C and nitrosylsulphuric acid prepared by dissolving 20
parts of sodium nitrite in 80 parts of concentrated sulphuric
acid is gradually added dropwise at the same temperature.
The mixture is stirred for approx. 2 hours longer at 0C.
The diazonium salt solution thus prepared is now added
gradually at 0-5C, whilst stirring well, to a solution of
58 parts of 1-(N-ethyl-N-~-chloroethylamino)-3-methylbenzene
in 2,000 parts of water and 50 parts of concentrated hydro-
chloric acid, to which 10 parts of amidosulphonic acid have
been added. The coupling reaction starts immediately.
It can be accelerated by buffering with a solution to pH 4-5
by means of sodium acetate. After completion of coupling,
the azo dyestuff formed is filtered off, washed with water
until free of salt and dried. 116 parts of a red dyestuff
powder are obtained.
The table which follows lists further dyestuffs which
are obtained when the diazo component of column 2 is diazo-
tised and combined with the coupling component of column 3 to
give the azo dyestuff, and also lists the shades obtainable
therewith in accordance with the process indicated in Example 1.
Le A 15 466 - 10 -
~036~S6
g ~
~,~ ~ = = = =
~ & ,_ ,, ,
~ ~ ~ ~ b ~ ~
o :Z = = = = =
t,
<~ o
,~
,
~Z;
~036756
~o ~ $~ = = =
, 3~
~ ~ ~ X
o~ _ \ / \/ \Z/ \/ ~ /
~3 b b b ~3
C~
o Z~ = = = = =
-
~ z; a- o
10367S6
_~
O~ ~ ~d ~ = = = =
~ 1~ v) h
_
C~ ~
"~ :~
~ V ~ ~ o ~ ~ o~ O
3 b
"~¢1
,~ o
.
~ ~; ,, ~ ~ ~ o
~036756
o
_ ~u~ o~, ~ ~ r ~ " =
~ o ~ ~ o ~ _ ~ \ /
o~ o=~ ~o~
o ~
'~ o
-
æ ~ c~ ~ ~ u,
--14--
~0367S6
d ~ ~3o
o~
~ ,~
=~ \~/ \ / \ /
_
~ ~ ~ .
8 ~ = =
Zc~,
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~.
~ ~ ~ O ~1
~0367S6
~q
~ ~ ~ ~ =
.
C`l
O D D ~ ~ D
D
_
~ ~)Z~
~ ~ = =
O Z
~1
~Z
-1~
1036756
,~ h
h
:p:, ~ \ / oz
o Z b~
o
'~
8 æ n ~ ~ ~
--17--
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z~ = = = =
~z;
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_ ~
~ ~ C`l u~ U)
~ ~ æ æ
Z;
'~ o~ = = = =
o
~:Z; ~ , o
--19--
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~ ~ ~l
;~ ~ ~ h o
O ~ ~ ~
C'~
N Z
.~ O
O
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u~
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o . ,~, ,
o a~
o) ~ s~ , ~
o
ta ~ a~
~3 :~ h h O h = :'
.. _ _ .
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~ ~ ~ nN ~ ~
~ \ / ~ \ y ~ \ / N~\ / ~-- --
~ [~ o`~ o`[~oo`~o~o [~
c~
a c~ : z
_ _. _ ..
~t .
X ~o ~ ~o
Le A 15 466 - 22 -
10:1S7S6
o ~ ~ a~
~I h
o
.
O
U~
. ,~
C~
O ~ n f ~ r n y
O ~ ~ 0~
0~ C~
~a ' Z s
O
~ ~ ~ ~ r~
Le A 15 466 - 23 -
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o ~ ~ o
~! ~ ~, : h ~ : .9
, a~ =, a~ a~
~ I ~ b ~a~ [~a~a~
~ Z N
~ ~ Z
O Z
1~ O
~ .
~0 ~
I~ I~ I` I~
- 24 -
1036756
O ~ ~ ~ h ~ ,D
a n 3 3~ ~3 A ~ A
J~ [~ ~ 3 ~3~3
~d Z
o o - -
~ z ,~ o oo
- 25 -
~036~S6
~ ~ o
O _ ~ ~ ~ _ _
~ 0~ o~, 0~ 0~
- ----
~ ~z ~ ~
o
Z o~ 00 00 00 `D
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103675~
o
U~
a~ ~
,,
o ,~
~o ~ o~
o~ C~
o . Z
N ~`1
O
a~
0
0 0 0
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Le A 15 466 - 27 -
, ~036756
a~
h o
O C~ N ;~ ~0
O ~
+~ . _
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-
C~
E ~ cr~
~ . cr~
~ Z
Le A 15 466 - 28 -
1036756
o ~ =
V
N ~N N
O N ~ j N
O ~ ~ z ~ o
O ~ ~, N ~ N ~
N ~
.. .. _
~Z
Le A 15 466 - 29 -
1036756
h
bO
.~ ~ ~
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' \A Z ~3
t~
+' __
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Le A 15 466 - 30 -
~036756
e
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1036756
8 ~
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Le A 15 466 - 33 -
1036756
~ ~o ~
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P c ~ N
a ~ ~ 0
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N O Q O
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Le A 15 466 - 34 -
~036756
E~! ~ h ,Q h
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O ~ ~ ~ ~ W
O w w ~N ,~
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Le A 15 466 - 35 -
1036756
bD ~
o ~ ' ~ ~
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cq ~i ,~ h o
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Le A 15 466 - 37 -
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a)
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Le A 15 466 - 38 -
1036756
ko
ko
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Le A 15 466 - 39 -
~036756
a~
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Le A 15 466 - 40 -
~0367S6
. ~ ~.
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U~ ~ ~ h h ~ :~
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Z
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- 41 -
11~36756
~ R
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10367S6
g h ~ v~ C~ ~ 3
h h ~ h
N ~ i N
O '-- T N N ~N _~
O N ~ N
L Z Z Z
N N N ~N
Z
L \~
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10367S6
,,
~d h ~ o ~ = =
~1 ~r~
tt O a~ ~>
U~ ~ S~
al N , ~ ~ ~ N
g ^
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Le A 15 466 - 45 -
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