Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~2~36~
HOE 82/F 100
The invention relates to the technical field of
fiber-reactive ago distaffs.
Specification No.
German Potent describes, in the
Table on columns 15/16, a muons distaff which con-
tarns a fiber reactive monochlorotr;azinyl radical and as
further f;ber-reactive radicals a ~-~sulfatoethylsulfonyl
group and a vinylsulfonyl group.
Jo have now found new, valuable, water-soluble ago
compounds of the general formula to)
I
A _ D - N - No NH ~s42 --X
X -- S02 3 S03M (1)
on which
M represents a hydrogen atom or the equivalent of a metal,
such as, in particular, of an alkali or alkaline earth
metal, such as, for example, of sodium potassium, lithium
or calcium,
is a Bunsen nucleus or a naphthalene nucleus,
R1 denotes a hydrogen atom or an a~kyl group of 1 to I
carbon atoms, such as, for example, an ethyl group or in
particular a methyl group, or a sulfa group owe the
I
-- 3
general formula -Sly where M has the a~ovementioned
meaning),
I is a hydrogen atom or an alkyd group of 1 to 4 carbon
atoms, such as, for example an ethyl group or in part-
cuter, a methyl group
R3 represents a hydrogen atom, an alkyd group of 1 to 4
carbon atoms, such as, for example, an ethyl group or, in
particular, a methyl group, or an alkoxy group of 1 to 4
carbon atoms, such as, for example, an ethics group or, in
particular a methoxy group, and
R4 denotes a hydrogen atom or an alkyd group of 1 to 4
carbon atoms, such as, for example, an ethyl group or, in
particular, a methyl group, or an alkoxy group of 1 to 4
carbon atoms, such as, for example, an ethics group or,
in particular, a methoxy group, where
R1, R2~ R3 and R4 ran be identical to or different from
one Arthur,
Y is a fluorine atom or a brom;ne atom or preferably a
chlorine atom and
on X denotes in each case a B-sulfatoethyl group of the
general formula -CH2-CH2-OS03M where M has the above-
mentioned meaning) or a B-thiosulfatoethyl group (of the
general formula -CHz~CH2-S-SO3~ where M has the above
mentioned mooning or a B-chloroethyl group or a vinyl
US group, where the two Us can be dental to or different
from one another, and
the group(s) of the formula -S02-X are in the Bunsen
nucleus in mote- or para-position relative to the ago
group or to the assaulted amino group or can be bonded in
Lo
the naphthalene nucleus on any positron, and
the second group of the formula -S03M us bonded on the
radical of the am;nonaphtholdisu'.fsn;c acid on mote- or
para-pos;t;on relative to the assaulted amino group.
The new ago compounds can be in the form of an
acid or in the form of their salts. whey are preferably
in the form of their salts, on particular the salts of
alkali or alkaline earth metals and they are also prefer-
ably used on the form of these salts for coloring (under-
dyeing and
stood here and below in the general sense and as including
printing) hydroxy- and/or carboxamide-containing mater-
pals, in particular fiber materials.
The present invention also relates to processes
for preparing the ago compounds of the general formula to)
mentioned and defined above. They can be prepared in the
manner of the invention by for example, reacting a come
pound of the general formula I
R1 HO NH NO to)
` R2 - - D-- N = No
X S2 ~503S S03M
.
on which D, R1~ R2, M, X and Y have the above mentioned
meanings and the second group of the formula -S03M in the
radical of the aminonaphtholdisulfonic acid us in the
mote- or para-position relative to the assaulted amino
group, with an aromatic amine of the general formula (3)
~L2~L3~0
Ho R4
S2~
in which R3, R4 and X have the above mentioned meanings
and the group of the formula SIX us bonded on the Bunsen
nucleus in mote- or para-posi~ion relative to the amino
group, or by reacting an ago compound of the general
formula to)
HO NH2
R2 _ D - N = N
X - SO MOWS SIAM
in Shea D, R1, R2, X and M have the above mentioned
meanings and the second group of the formula -S03M in the
radical of the am;nonaphtholdisulfonic acid is bonded in
mote- or para-posit;on relative to the amino group, with
a dlhalogenotriazinyl compound of the general formula (5)
R3
N R
2
in which Y, R3~ R4 and X have the abovementloned meanings
and the group of the formula -S02-X is bonded in the
Bunsen nucleus in mote- or para-position relative to the
assaulted amino group.
~L~22~36~
-- 6 --
The dihalogenotriazinylamino compounds of the
general formula to) can be prepared in analogy to known
Moe by coupling the diazonium salt of an amino compound
of the general formula ~63
R1
2 \
R --D--NH2 (63
X So
on which D, R1, R2 and X have the above mentioned meanings
and the group of the formula -S02X is bonded in the Bunyan
nucleus on mote- or para-pos;tion relative to the amino
group, with 1-(2',4'-dihalo~eno-1',3',5'-triazin-6'-yl)-
amino-8-hydroxynaphthalene-3,6- or -4r6-disulfonic acid.
The reaction of dihalogenotri3z;nyL compounds of the
general formulae (2) and (5) with the corresponding amino
compounds can also be carried out on analogy to a known
method. These reactions are described for example, in
WIFE Beech Fibre-reactive Dyes, London 1970~ pages 148 et
seq. The abovement;oned coupling reaction is preferably
carried out within a pi range between 4 and 7 at a tempera-
lure between 0C and 30C. The condensation reactions
of the dihalogenotriazinyl compounds with the amino come
pounds are generally carried out in an aqueous medium, of
appropriate in the presence of an organic solvent, at a
temperature between 0C and 70C~ preferably between
20C and 70C, and preferably at a pH-value of from 4 to 7.
The process according to the invention can thus be
carried out by reacting the diazonium salt of the amino
36g~
-- 7
compound of the general formula I and the aniline come
pound of the general formula to) in any order with 1-
(2',4'-dihalogeno-1l,3',5'-triazin-6'-yl)-amino-8--naphthol-
3,6- or -4,~-disulfonic acid.
The hydraulic acid liberated in the course of the
condensation reactions us bound by means of ac;d-b;nd;ng
agents such as, for example, sodium hydroxide, potassium
hydro~;de, sodium carbonate, potassium carbonate, sodium
bicarbonate, potassium bicarbonate sodium acetate or a
basic sodium phosphate.
Examples of amino compounds of the general formula
(3) which can be used as starting compounds for preparing
the muons compounds of the invention are I sulfite-
ethylsulfonyl)-ani!ine, 2-methoxy-5-~-sulfatoethylsulfon-
yl)-aniline, 2,5-dimethoxy-4-~-sulfatoethylsulfonyL)-
aniline, 2-methoxy-4-t~-sulfatoethylsulfonyl)-aniline, 4-
methoxy-5-(~-sulfatoethylsulfonyl)-aniline, 2,4-d;methoxy-
I sulfatoethylsulfonyl~-an;l;ne, 2-methoxy-5-methyl-4-
(~-sulfatoethylsulfonyl)-aniline, 2-methyl-5-(~-sulfato-
ethylsulfonyl)-an;l;ne, 2,5-dimethyl-4-(~-sulfatoethyl-
sulfonyl)-an;l;ne, 2~6-d;methyl-4-t~-sulfatoethylsulfonyl)-
aniline, 4-methyl-3-t~-sulfatoethylsulfonyl)-aniline and
on particular 4-~-sulfatoethylsulfonyl)-an;l;ne and those
derivatives of these aniline compounds in which the -
sulfatoethylsulfonyl group has been replaced by a vinyl-
sulfonyl, a ~-th;osulfatoethylsulfonyl or a chloroethyl-
suifonyl group.
Examples of amino compounds of the general formula
16) which can be used as starting compounds in the proper
I
-- 8 --
lion of the ago compounds of the invention are I
suLfatoethylsulfonyl)-an;l;ne, methyl sulfatoethyl-
sulfonyl)-aniline, 4-methyl-3-(~-sulfatoethylsulfonyl)-
aniline, 2,5-d;methyl-4-(~-sulfatoethylsulfonyl)-aniline,
2~6-dimethyl-4-(~-sulfatoethylsulfonyl~-aniline, I
sulfatoethylsulfonyl)-aniline-2-sulfonic acid, 6 (I-
sulfatoethylsulfonyl)-2-aminonaphthalene-1-sulfonito acid,
8-(~-sulfatoethylsulfonyl)-2-aminonaphthalenY, So
sulfatoethylsulfonyl)-2-am;nonaphthaleneO sulfite-
ethylsulfonyl)-2-aminonaphthalene-6-sulfon;c acid and in
particular 4-(~-sulfatoethylsulfonyl)-an;line and those
derivatives of these aniline and naphthylamine compounds
in which the ~-sulfatoethylsulfonyl group has been no-
placed by a vinylsulfonyl, ~-thiosulfatoethylsulfonyl or
~-chloroethylsulfonyl group.
Of the ago compounds of the invention those are
particularly noteworthy which have the general formula (1)
on which D denotes a Bunsen nucleus and R1, R2, R3 and
R4 each represent a hydrogen atom or in which D denotes
a naphthalene nucleus, R1 us a hydrogen atom or a sulfa
group, and R2, R3 and R4 each represent a hydrogen atom.
Of the ago compounds of the invention, those are
also preferred in which the X groups represent a vinyl
group or, on particular, a ~-sulfatoethyl group.
Other noteworthy ago compounds of the invention
are those described in Examples 1, I 7, 16, 30, 42 and 49.
The formula I compounds prepared in the manner
of the invention can be separated from the synthesis soul-
lion by generally known methods, for example either by
3122~L36~
precipitating them from the reaction medium by means of
electrolytes such as, for example, sodium chloride or
potassium chloride, or by evaporating the reaction soul-
lion, for example by spray drying where a buffer substance
can be added to thus reaction solution.
The ago compounds of the invention have valuable
distaff properties. because of the two fiber-react;ve
groups of the vinylsulfonyl series and because of the
halogenotriaz;nyl radical, they have fiber-react;ve pro-
purities The new compounds are preferably used for coloring in the general sense defined earlier) hydroxy- and/or
~arboxam;de-contain;ng materials, for example on the form
of sheet-Like structures, such as paper or leather or
films, such as, for example, those made of polyamide, or
in the unshaped state, sushi as, for example, polyamide or
polyurethane, but on particular these materials in fiber
form The solutions of these ago compounds obtained in
the synthesis of compounds of the invention can also be
used directly in dyeing as Cody compositions/ of approp-
rate after a buffer substance has been added or the soul-
ton has been concentrated or diluted. The present invent
lion therefore also relates to the use of compounds of the
general formula (1) coloring yin the above sense) these
materials or rather to processes for coloring such materials
on a completely conventional manner in which a compound
of the general formula I is used as colorant.
The materials are preferably used in the fornl of
fiber materials, on particular on the form of textile
fibers, such as yarns, packages or fabrics.
~L2~2~L3~C~
- 10 -
Hydroxy - containing materials are those of natural
or synthetic organ, such as, for example, cellulosic
fiber materials or their regenerated products and polyvinyl
alcohols. Cellulosic fiber materials are preferably
S cotton, but also other vegetable fibers, such as linen,
hemp, jute or Rome fibers; examples of regenerated cell-
logic fibers are viscose staple and filament viscose.
Examples of carboxam;de-conta;n;ng materials are synthetic
and natural polyamides and polyurethane, in particular
in the form of fibers, for example wool and other animal
hairs, silk, leather, nylon-6,6, Nolan nylon-11 and
Nolan
The novel compounds of the general formula (1) can
be applied and fixed to said substrates, in particular
said fiber materials, by the application techniques known
for water-soluble distaffs, in particular those known for
~ater-solubler f;ber-reactive distaffs.
For instance, applied to cellulose fibers by
exhaust methods from a long liquor using various acid-
2Q binding agents and, if appropriate, neutral salts, swishes sodium chloride or sodium sulfate, they give very good
color yields and excellent color buildup Dyeing is
preferably carried out in an aqueous bath at temperatures
between 60 and 105C, if appropriate at temperatures of
up to SKYE under pressure, and, if appropriate, in the
presence of customary dyeing auxiliaries. The dyeing can
be carried out by introducing the material into a warm
bath and gradually raising the temperature of this bath
to the desired dyeing temperature and completing the
36~
dyeing process at thus temperature Neutral salts which
accelerate the exhaustion of the distaff can be added to
the bath, of desired only after the actual dyeing topper-
lure has been reached.
The padding method also gives excellent color
yields and a very good color build-up on cellulosic fibers,
with toe aid of an acid-bînding agent
on which the dyes can be foxed on a customary mannerly
material padded with the dye liquor,
leaving the to stand at room temperature or Elena-
ted temperatures, for example up to about 60C~ by steaming
or by means of dry heat
Strong prints having well-del;neated contours and
a clear white ground are also obtained in customary print-
no methods for cellulose fibers, which can be carried
out in one step - for example by printing with a print
paste containing sodium bicarbonate or a different acid-
binding agent and then steaming at Tao 103C - or in two
steps, for example by printing with a neutral or weekly
acid print paste and then fixing either by passing the
printed goods through a hot electrolyte-containing alga-
line bath or by over padding with an alkaline electrolyte-
containing paid jug liquor and then leaving the over padded
material to stand or steaming it or treating it with
dry heat. The outcome of the prints varies only little
Thea changing fixing cond;t;ons.
In dry heat fixing by customary thermof;x;ng
methods, hot air at 120 to 200C us used. In addition to
customary steam at 101 to 103C, it is also possible to
use superheated steam or saturated steam at temperatures
of us to 160C.
36~
- 12 -
Examples of agents which bond acid and effect the
fixation of the compound of the formula I on cellulosic
fibers are ~ater-soluble basic salts of alkali metals and
also alkaline earth metals Thea inorganic or organic acids,
or compounds which liberate alkali when heated. The
alkali metal hydroxides and alkali metal salts of weak to
medium inorganic or organic acids are particularly note-
worthy, the sodium and putts compounds in particular
being intended among the alkali metal compounds. Examples
1Q of such acid-binding agents are sodium hydroxide, poles-
slum hydroxide, sodium carbonate, sodium bicarbonate,
potassium carbonate, sodium format, sodium dihydrogen-
phosphate, sodium hydroge~phosphate, sodium trichloro-
acetate, sodium silicate and trisodium phosphate.
The treatment of compounds of the invention with an
acid-b;nding agent, if appropriate under heat, chemically
bonds the compounds of the invention (distaffs) to the
cellulose fiber; applied on dyeing and printing methods,
they are distinguished on these fiber materials by a high
degree of fixation. The cellulose dyeings have excellent
wet fastness properties after the customary after treatment
whereby unfixed distaff is removed by rinsing, in portico-
far since the unfixed distaff can be readily washed out
thanks to the fact that it is readily soluble on cold water.
Dyeings and prints prepared with the novel come
pounds of the general formula (1) are distinguished by
very bright shades. The dyeings and prints on cellulosic
fiber materials, in particular, have a good light fastness
and very good wet fastness properties, such as washing,
:
I
milling, water, seawater, crusading and acid as well
as alkaline perspiration fastness properties, and also a
Good pleating vastness, hot pressing fastness and rubbing
fastness.
Moreover, the novel compounds of the general for-
mute (1) can also be used for the fiber-reactive dyeing
of wool. It us possible to dye, with very good fastness
properties even wool finished to be non-felting or low-
felting of for example H. Rat, Lehrbuch don Textile
chemise textbook of Textile Chemistry, published by
Springer, 3rd edition (1972), pages 295 - 299, in portico-
far the finish by the Hercosett process (page 2~8); and
J.Soc. Dyers and Colorists 1972, 93 - 99, and 1975, 33 -
44)~
The wool is dyed in a customary known manner from
an acidic medium. Thus, acetic acid andlor ammon;um sulk
fate or acetic acid and ammonium acetate or sodium acetate,
for example, are added to the dye bath to obtain the
desired phi To ensure acceptable levelness it is
advisable to add customary leveling auxiliaries such as,
for example, those based on a reaction product of cyan uric
chloride with 3-times the molar amount of an aminobenzene-
sulfon;c acid and/or of an aminonaphthalenesulfonic acid
or those based on a reaction product of for example,
stearylamine with ethylene oxide Thus for example, the
compound of the general formula (1) us subjected to phi
controlled exhaustion, preferably first from an acid dye-
bath with a pi of about 3.5 to 5.5, and toward the end
of the dyeing tome the pi us then shifted into the neutral
2~3~)
or possibly weakly alkaline range as far as a pi value of
8.5 to bring about the full reactive bond between the come
pound of the formula to) and the fiber, in particular for
obtaining deep shades The unfixed distaff is dissolved
away at the same tome.
The dyeing method described here us also applique-
able to preparing dyeings on fiber materials made of other
natural polyamides or of synthetic polyamides and polyp
urethanes. The maternal to be dyed is generally introduced
unto the dye bath at a temperature of about 43C and agitated
thereon for some tome, the dye bath is then adjusted to the
desired weakly acid preferably weakly acetic acid, phi
and the actual dyeing is carried out at a temperature bet-
wren I and 98C~ However, the dyeings can also be
carried out at the boil or on sealed dyeing machines at
temperatures of up to 106C. Since compounds of the
general formula (1) are very readily soluble in water,
they can with advantage also be used on customary continue-
out dyeing methods The t;nctor;al strength of the novel
pa compounds of the general formula to) is very high.
The ago compounds of the invention produce very
bright yellowish to bluish red dyeings on the materials
mentioned, preferably fiber materials.
The examples, which follow, serve to illustrate
the invention. The parts are parts by weight and the per-
cent ages are percentages by weight, unless otherwise
stated Parts by weight relate to parts by volume as the
kilogram relates to the liter.
The compounds described on the examples by formula
~j2~3~)
are given in the form of the free acid; they are generally
prepared and isolated on the form of their salts, prefer-
ably sodium or potassium salts, and are used for dyeing on
the form of their salts. Similarly, the starting come
S pounds mentioned on the following examples, in particular tabled examples, in the form of the free acid can be used
in the synthesis in the form of the acid or in the form
of their salts, preferably alkali metal salts, such as
sodium or potassium salts
Example 1
a) A suspension of 225.2 parts of 1-amino-8-naphthol-
4,6-disuLfonic acid in 1,440 parts of water and 720 parts
of ice us admixed by efficient stirring with 155.Z parts
of cyan uric chloride; the reaction batch is stirred at a
temperature battalion 3 and 5C and pi 1.7 Tao, maintained
by means of sodium bicarbonate, for 4 hours.
b) The diazonium salt of the dyes component is pro-
pared in a separate operation: a solution at pi 6.7t~ 6.8
of 224.8 parts of 4-B-sulfatoethylsulfonylaniline in 640
parts of water is admixed with 105 parts by volume of a 40%
strength aqueous sodium nitrite solution. This mixture is
alloyed to slow with efficient stirring into a mixture of
800 parts of crushed ice and 70 parts by volume of 95%
strength aqueous sulfuric acid. The resulting mixture is
stirred at 0C t~5C for one hour, and, as customary,
excess nitrous acid is then destroyed with a little amino-
sulfonic acid
c) The primary condensation product prepared in this
example under a), from cyanur;c chloride and an amino-
naphtholdisulfon;c acid us combined with the d;azon;umsalt solution described in this example under b). To
start the coupling reaction the strongly acid reaction
mixture is adjusted at a temperature of about 5C to pi
4.0 - 4.5 by means of calcium carbonate and the tempera-
lure is raised to 15 - 20C. Stirring us continued at
this pi and this temperature for some hours, until the
coupling has ended.
d) The solution of the muons compound of c) us come
brined with a solution, having a pi 5.5 Jo 6.0, of 247.3 parts of~-~-sulfatoethylsulfonylanil;ne in 640 parts of water.
The pi us maintained at about 5, and the reaction mixture
is heated to a temperature of 60 to 65C on the course
of two hours. The mixture is then wrought to a pi of 6.0 to
6.5 by means of calcium carbonate, and the precipitated
calcium sulfate us filtered off loath suction after 15
minutes and washed with water. The combined filtrate and
wash-water is freed from calcium ions by adding sodium
oxalate, the calcium oxalate is filtered off with suction,
2Q and the filtrate is spray-dried.
The product comprises about 1~120 parts of a pow
don which contains electrolyte salts predominantly sodium
chloride and sodium sulfate) and 7û% of the sodium salt of
the compound of the formula
~22~L~6~
- 17 -
Of
N N
Ho NH N - NH Sly
S2 ~03S OOZE
fH2 S03H
CHIHUAHUAS
Thus compound has very good distaff properties and on
application by the application and fixing methods custom-
cry on industry for fiber-reactive distaffs produces, on
the materials mentioned in the descriptive section, such
as cellulosic fiber materials, in particular cotton,
strong red dyeings and prints having very good fastness
properties, of which the most noteworthy are the very good
washing, light, alkali acid, water, seawater, perspire-
lion and rubbing fastness properties. The dyeings Aurelius distinguished by their high degree of fixation on the
cellulose materials.
Example 2
__
19.4 parts of cyanur;c chloride and 31.9 parts of
1-amino-~-naphthol-3,6-disulfon;c acid are rapidly added
with efficient stirring to a mixture of 330 parts of water
and 40 parts of ice. The mixture is stirred eta pi of 1.5 to
2.0 and a temperature between 10 and 15C for about 3~5
hours. The solution of this primary condensation product
us then clarified by means of kieselguhr and it ltration.
This solution is combined with a conventionally
sodium nitrite and sulfuric acid d;azotized aqueous sup-
~2~6~
- 18 -
pension of the diazon;um salt of 41.1 parts of I
sulfatoethylsulfonyl)-2-aminonaphthalene-1-sulfonito acid
and the strongly acid coupling mixture is then brought to
pi 4.0 - US by means of calcium carbonate at a tempera
lure of about 10C and is stirred at 10 to 14C and
within this pi range for a few hours.
A solution (at pi 5) of 29.5 parts of 4 -I-
sulfatoethylsuLfonylaniline in 100 parts of water is then
added, and the batch is stirred at 18 to 22C for two to
three hours, us then heated to 50 to 55C and us held at
thus temperature for 30 minutes while the pi is kept at a
constant value of 4.0 to 4.5 by means of calcium carbonate.
The batch us then stirred at 18 to 20C for a few hours,
the calcium sulfate is filtered off with suction and
US washed with water, and on thus combined filtrate and wash
water the calcium ions are precipitated by means of sodium
oxalate at pi 4.5 - 5.0 and 30C. The mixture us
filtered after one hour of stirring, and the muons come
pound of the invention is isolated from the filtrate by
Z0 spray-drying.
The product comprises 155.6 parts of a dark red
powder Shea, in addition to electrolyte salts, contains
about 73% of the sodium salt of the compound of the formula
Sue HO . NH ~N~NH kiwi
Do N _ No 1 2
S2 H 3 S03H SHEA
CH2-CH2-0S03~ .
2;~36~
- 19 -
This muons compound of the invention has very good
fiber reactive distaff properties and on application by
the printing and dyeing methods customary in industry for
f;ber-reactive distaffs produces, for example, on cell-
logic fiber materials strong red dyeings and prints of very good manufacturing and end-use fastness properties,
of which the most noteworthy are the light fastness, the
Nash, persp;rat;on, water and seawater fastness properties
and the resistance to chlorinated tap water. The degree
of fixation of this muons compound of the invention on
cellulosic fiber materials is very high
Examples to 72
The tabled examples which follow describe
further muons compounds of the invention, with the aid
5 of their components, by the general formula aye
or
N N
Ho NH N
Do ON - N aye)
~03S S03~
They can be prepared in a manner of the invention, for
example in analogy to one of the above illustrative
examples, from their components (cyan uric chloride, cyan-
arc bromide or cyanur;c fluoride, the amino compound D1-NH2,
corresponding to formula to) as dyes component, I
amino naphthol-3,6- or -4,6-disulfonic acid as coupling
component (which us characterized in the particular tabled
:~22~3~
- 20 -
examples by the position of one of the sulfa groups relative
Jo the amino group) and the amiss compound ANN correspond-
in to formula (3)). They have very good f;ber-reactive
distaff properties and on application by the application
methods customary in the dyeing and printing industry,
preferably by the application and fixing methods customary
in industry for fiber-reactive distaffs, produce, on the
materials mentioned on the descriptive section, such as,
on particular, cellulose fiber materials, strong dyeings
and prints having good fastness properties and the shade
indicated in the particular tabled example.
- 21 -
s ,
, .. .. .. ... .. .. ..
3 3 3 3 I, 3 3 3
ill O O O O O O O O
I- _ _ _ _ _ _ _ _
I, t It, Jo c I, c
_
Jo Jo v Jo I 'I
O
O Q I W I
O
,, _ O no
m Q Q Q O E Q Q Q Q Q Q
O o u)
Q
1 1 1 1 1 1 I,
O J
J J J J J 'I
I C
C C C C C I I
Z O O O O o O Jo I Jo I
C C I CO I
C _ _ _ _ _ c C C`'
O r Jo I I I Ill I
Q Jo KIWI ^ I ^ a
E a c E on
O O O O O O O I I I Jo I --
Y Y Us C CO I CUT Jo
I (U ID a _ I o I ox: o IT o I r
O I ~>~
c no --x --I -- -- -- x
., Jo I tlJ~ alp QJ J O JO YE Jo O O
E ~.~ C TV c TV C TV I n r I,
I _ J J Jo J
'`' I-- `' --`-- -- -- s r s I _
I C I C I I C I C I I I
no I Jo 111 11:1 N ~13 a N N a N Us
l l l l l l l l l
J _ J J J
Jo ' Jo Jo
C C C C C C C C
Z O I a O O O O O O O
O C O
I- _ ., _ _ _ _ _ _ _
Jo
-- -- c_ a _ _ _ _ _ _ _
C O Jo C Jo
arc TV r
C I
oat I -- Q' q'
Q O Jo C O O O O O O O
E I C I
O us o I 13 I
___ __ _ _ _ _ _ _ _
N Us C (t) '- C COO Cut C (O C V) C lo C TV C
Jo _ O I '' I ''I ''I ' I
., ~_JQJ Jo Jo Jo C~LJ do Jo I J
I SUE I I C I C I C I C I I C I C
~11)
X I Us OWE 00 O` O
ELI E ,_ I_
3Ç;~3
- 22 -
a .,
I O
Jo L Jo t L C L. C I_
_ JO J J J J _ J J J J
V
C
O I
"_ t- C Q Jo (I! to fly fly I I I I
O Jo t_ L I_
I c _ O Q '= E E F E E E Q Q Q Q
O O it) Us I)
Q
a
I C
I I I J I I I I I C
O -- Jo J J O --` O
Jo _ J S '' J--'
I t- I C Jo
c C to n I C C C
Z -- O O a 0 1) 0 0 0 5
O O
I _ (0 to I I J I
---- Jo owe c-- -- _ a,
I >~~ C Al C C I (It O
Ox I - to J I I
OX >" O O-- C I `- I --x Jo O o o J
C I (I I C
I- O (~111:~r I I Ivy I I I o
Ox I Jo O
C J J JO J X J J JO Jo J' J J J 'I
., E O Jo O Of I '- I
E n Cut c' C -C C -- c c TV TV) c I-- C
Of I Jo o o o a
J JUDGE a. QJ awl I c~cJ I .. J
Us J S J I: Jo JUT I`-- 'I 'I '-- 'I 'I
I I C I I I C I C I C
N Jo Jo ) N u) N us
I I I I I I I I
_ _ _ _ _ _ _ _ _
N
-r CCC~CCC~ I
Z O O O O O O O O I O
_ _ l O
u) u) on u) v) us on Lo c In
Jo _ J J J J _ J J a at .~/) J
C O,
at c c
C rut C r .
o a I,
Q O O O O O O O O O
E
O C Ill
O ^ O
_ _ _ _ _ _ _ _ , _ a-- -- --
O Jo Al a aye I) E
N I) C C It C I C TV C m C I C Us C I-- C C C TV C
J I J Jo Jo Jo Jo C~_J C~J ~_~ I Jo Jo
I C I C I I C I C I C I C I C I I C I C
I _
so Q us Jo l_ ox O` O SO
ELI E N . I N Jo N N
(U .
I
-- 23 -
a)
I
L L L I L L. I_
J J J J J J J J J J J
o a
C O Q
O I_ L. r I_ Y
_ O MU a
U) Il.) ::~ L Q Q Q Q Q Q Q E E E E
O O U) 1~1 I)
C I '.
I II , I I J
I J -- O -- O
^ r I,
-- '' I C (U
Jo Jo c I a
C aye-- IT O'' I_ Jo Owe 0 a.)
2 O OX C l O O
C _ Noah _ I I _ Jo no
inn -- C I
In_ a,-- ~--~ --I ox c ----
C _ Jo I CUT C
O I 'I-- E us
E C)`-- C`-- OX Jo O l --X Owe I c I C
O o i O C I Lo
Us C O I-- O Us II I I
OX I ^ Jo I Jo
O _------_~-- _ x ala -- -- ---- x-- x--
C ' YE Jo I) O Of O O
., I I C O C -- Us C I, C I:
I I Ox Ox Y (I O O Y O
Jo us YE -- Jo --s _ us , _ s _ so _
0 lo J I N urn us I'M on
(I Jo
I C
Z O
..
TV
OWE
C IJ
O QJ I
I o v n
E I.
O
.
v
N Us C
I-_
I
I*
X I JO OWE` O JO
36~3
Q,
,
no mu) us
Q ' D I.
J J J J J I_ J _ J J J
I m '' ''
c
O a,
I Jo C o
O I> ~~_ Jo L
E E E E E E E Q E YE E
o o Us
.
O -- -- O Jo ^
Jo Jo J
MU I
I C C
O _ I) O O
Z I O
--' I O J a, --' CJ
I a c or) c I O O O O O O
E X I -- --' C i C X Jo O O 'Of I
O O Cut 0 C
U C OX ' it I I I O
O axe -- -- x
C If JO O Jo OWE Jo E Jo a) a
Jo I ~,~~ C C US C TV
E I --I Y O I' O I --I -- I '
-- S _ s _
I C I C
^ ^ _
Jo
T C C C C
Z O O O O
I I
J J J Jo
Q
a a on
-- -- C -- C -- C
c o o o o o ooze o Jo a o Jo
C Jo Y
O I I I I a, , c
Q O V 'O I 0 O O O ~-~
E
Tao Q (I Q
o o o o-,
N us c TV C TV Con C C
I _ E CAL En E
lo I I I I 1
I
X Q I_ 00 O` O it Ill JO I 00 O`
Jo E it) it it
- 2 5 Lo
, s s , s s s
S 'I r Jo Jo .~. .~_ Jo
n L n n n
J J J J J J J _ J J J J
C
O
I S C O Q 0
O t_ L I_
_ o a a a
Q E Q E Q E Q E Q E E E E
O O TV
Q
I C
I I _ I Jo I _ I
O J _
J J r- I J t-
I
I a. I. C
O O O -- ' I O O QJ
Z C I ^ O
_ _ Us --
I:
Us U J en_ --
J J Ox O `-- Owe O O J O 11~ J (IT
c no c I Jo us C C
t_
E O O I C: x I J O I C --I C
O Jo O
(U t I O I
o _ _ x-- a, _ x a) -- x J J J
c a o o o o Jo
Jo Us TV) I I V) S S
E I --I -- O Of -- (11 I I O O
I, ., S-- I
I C I C I
N Jo
C C
2 O O
l l
,_ J JO
I
us on Al
C
C O O O O O O O Ox QJ O O O
S J +- I J- US
C
Q O -I 'U 'D -O O -I
y
O Jo Q Q to
(Of
J C I.) J
O Owe Owe
N in C C C C
I - O I I O
., I E YE
no J
I I
I
X Q O - IT Us JO I 00 O` O N
I
~;~2~3~
-- 26 --
a
r- , s
_ .. .. .
TV Jo c5~ 3 'O
-- a,,_ aye at a Baja QJ J J I
Q I_ Q n n
r~r_~r~,~r~,~r~
o
I -- C O Q(IJa~ no no n
Y O Jo I_ L. L.
., I J O
E E Q Q Q Q CAL Q E E
o o U) TV
a a,
C
'' I J I I_ ., I
-- O -- O--`
Jo _ _>., r .,
I Jo c I
Al C C CC,
`-- I-- CJ O O a O`-- I -- O
2 ^ C O Y C C
to Jo 'I J J Y ~~' J Us 'I J 'I
CC I I -- Jo I I, J J
J Cry U) J J C ~,~
I_ C J JO Jo Jo O --I C
C ~.~ C m c
Jo ICKY: MU) 'I 'I I J I 1 C- J
O I I Y Jo I J 'C J
E I --x Jo O O `-- c I I -- x O O
O us o c Y I Irk o c Y
O em I I I Jo o a--
o X I-- _ -- _-- X OX I> I-- --
C O O E aye ~>~ Jo O Jo O O En a, --
., to C TV I C '- C'- Y C
Hi Jo O Ox (I I-- I '' C
S Us _ S _ S _
I I I C I I I C
ION 1 Us ON 10 (O I)
I
:1: C
2 O
_ ,`
I I
Us
-- C
C O O O O O O O O O
Jo (- _ Y
C Y
o q, I, , , , , . .... ..
Q O
E C v
O no Q
O O--
N us C C
I I O
., E
I, _
I
JO V)
x Q 0 I O` O-- N
Us E OWE JO JO JO JO OWE 1'1~
