Note: Descriptions are shown in the official language in which they were submitted.
~ lB57~(~
D.N. ~111
NOVET. COMrOSITIO~S AN~ PROCESSES
NNNNN~RNNN~N~NN~NNNR~NN~NNNN~NNNNNNNNNNNNNNNN~NNR~
BACKGROUND OF THE_INVENTION
(a) Field of the Invention
This invention relates to the field of chemistxy and
more particularly to novel acid addition salts of poly(N-substi-
tuted sulfonamido) phthalocyanines useful as direct dyes, par-
ticularly in the dyeing of cellulose, to storage-stable concen-
trated aqueous dye compositions prepared therefrom; and to pro:
cesses for preparing said phthalocyanines, said acid addition
salts and said storage-stable concentrated aqueous dye solutions.
(b) Description of the Prior Art
A class of organic compounds known as direct dyes are
known to be useful as dyeing agents for paper and fabrics. Among
this group of organic compounds there are named phthalocyanine~
and their acid addition ~alts. However, heretofore Xnown phthalo-
cyanines and their known acid addition salts have suffered from
a number of deficiencie3 when employed as dyes for coloring cel-
lulose in the form of bleached pulp of the type ysed for the man-
u~acture of household paper goods such as paper napkins~ paper
toweling, facial ti~sueC and so forth. Thus~ they have been found
to undesirably bleed out of paper products colored with them when
the article is brought into contact with common household solu-
tions~ for example~ water~ milk~ soapy solutions, detergent solu-
tions~ alcoholic beverages, vinegar, rubbing alcohol and so forth~
They have also been found to have relatively poor substantivity to
--1--
~ 16S7~)
bleached pulp and have suffered from a low rate and degree of
exhaust from dyeing solutions containing them. They have also
been found to have a relatively poor degree of color discharge
when bleached with hypochlorite or "chlorine" bleach. There is
thus a need for water-soluble phthalocyanine dyestuffs for
coloring bleached pulp which have a high bleed resistance, good
substantivity, a high rate and a high degree of exhaust from
aqueous dyeing solutions in which they are utilized, and a high
degree of color discharge when bleached with hypochlorite or
"chlorine" bleach.
The following items to date appear to constitute the
most relevant prior art with regard to the instant invention.
United StatesPatent 4,069,064, issued January 17, 1978
to Nett et al., discloses a phthalocyanine formulation which is
stabilized against recrystallization and change of modification
ant which contains as the stabilizer a salt or the corresponding
homogeneous mixture, of (a) one or more phthalocyanine deriva-
tives o~ the formula Pc~-X-NRlR2]n, where Pc is an n-valent
radical of the metal-free phthalocyanine, of a copper phthalo-
cyanine or of a mixture of these, X is -CH2-, SO2-NR-alk-,
-CH2-COO-C2H4- or -CH2-CH2-COO-C3H6-, R is hydrogen, alkyl
of 1 to 20 carbon atoms, phenyl, phenyl which is substituted
by methyl, methoxy, ethoxy or chlorine, -(C2H4-NH)zH or
-(C3H6-NH)zH, R2 ls hydrogen, alkyl of 1 to 6 carbon atoms
or cycloalkyl o~ 6 to 8 carbon atoms, alk is linear or
branched saturated alkylene of 2 to 6 carbon atoms, R is
hydrogen or alkyl of 1 to 4 carbon atoms, and R and R2 may
be linked to one another, n is a number from 2 to 5, z is
an integer from 1 to 3 and the group -NRlR2 may also be
576~)
a heterocyclic ring selected from the group consisting of
morpholinyl, thiomorpholi~l, piperazinyl, N-methylpiperazinyl,
N-ethylpiperazinyl, piperidinyl, pyrrolidinyl and
(CH ~ N- and
~) a saturated or unsaturated aliphatic sulfonic acid of
8 to 20 carbon atoms, a benzenesulfonic or naphthalenesulfonic
acid, substituted by one or two alkyl groups each of 6 to 20
carbon atoms, and in which the benzene or naphthalene nucleus
can be substituted by a hydroxyl group, or mixtures thereof,
the molar ratio of ~a) : (~) being from 1:1 to 1:5, and the
said salt or corresponding mixture acting as a stabilizer in
the formulation.
United States Patent No. 2,863,875, issued December 9,
1958 to Bienert et al., discloses a phthalocyanine dyestuff
containing the group [-S02N(Rl)R2(NR3R4)]n wherein Rl is a
hydrogen or a lower alkyl, R2 is a lower alkylene, R3 and R4
are lower alkyl or hydroxy lower alkyl and n is one to eight.
United States Patent 4,036,585, issued July 17, 1977
to James et al., discloses a copper phthalocyanine dyestuff
bearing the groups [-S02NHCH2CH2NHCH2CH2CN]n wherein n is 3 to 4.
United States Patent 3,053,849, issued September 11,
1962 to Clark et al., discloses phthalocyanine dyestuffs of the
formula
~ (S03H)a
PC--~S02-L)b
~S02-M) C
wherein Pc is a phthalocyanine; L is [-NH(CHR3CH2Y)m-CHR4CHR5X];
R3, R4 and R5 are hydrogen or alkyl; Y is -NH-, -N-lower alkylene,
I ~B576~
-O- or -S-; m is O or l; X is Cl, Br, sulfo or sulfonyloxy;
M is amino or substitu~ed amino; a is 0-2; b is 1-3; and C is
1-3 provided that the sum of a+b+c does not exceed four.
United States Patent 3,057,873, issued October 9,
1962 to Pugin et al., discloses phthalocyanine dyestuffs of
[(XlS2)m~PC~~S03 ~3)n3[X2 ~]n wherein Pc is a
phthalocyanine radical; Xl is a polyalkylene polyamine con-
taining at least one lipophilic radical and at least three
basic nitrogen atoms; X2 is the ammonium cation of such a
polyalkylene polyamine; and m+n is 2 to 4.
German Offenlegungschrift 2,629,675, published
3anuary 20, 1977 in the name of CIBA GEIGY AG, discloses a
stable concentrated liquid preparation of a paper dye of the
copper phthalocyanine class which preparation contains 15 to
50 percent by weight of the dye of the formula CuPc[S02NH~CH2)3-
~CH2)3]2 to 3 [S03H]1 to 2 wherein CuPc represents copper
phthalocyanine, or the alkali salt thereof, dissolved in 30 to
65 percent by weight of water, 5 to 15 percent by weight of N-
methylpyrrolidone, 1 to 7 percent by weight of benzyl alcohol,
and 1 to 5 percent by weight of a lower aliphatic carboxylic acid.
SUMMARY OF THE INV~NTION
In one of its composition of matter aspects, the in-
vention relates to storage-stable dye compositions comprising
aqueous solutions of acid addition salts of poly(N-substituted
sulfonamido) copper phthalocyanines.
In a second composition of matter aspect, the inven-
tion relates to acid addition salts of poly(N-substituted
sulfonamido) copper phthalocyanines.
In a third composition of matter aspect, the invention
relates to poly{N-[2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido}
copper phthalocyanines.
-- 4 --
~ ~657sn D.N. 8111
In a ~ourth composition of matter aspect, the invention
relates to poly[N-[N-~2-aminoethyl3-2-aminoethyl]sulfonamido~
copper phthalocyanine~.
In a fifth composition of matter aspect, the invention
relates to poly[N-(3-aminopropyl)sulfonamido] copper phthalocya-
nines.
In one of its process aspects, the invention relates ~o
a process for preparing a storage-stable aqueous dye solution which
comprises interacting a single acid or a mixture of acids with poly-
(N-substituted sulfonamido) copper phthalocyanines in a mixture of
a glycol or urea and water.
In a second process aspect, the invention relates to a
process for preparing acid addition salts of poly(N-substituted
sulfonamido) copper phthalocyanines which comprises interactin~
lS a single acid or a mixture of acids with poly(N-substituted sulfon-
amido) copper phthalocyanines.
I~ a third process aspect, the invention relates to a
process for preparing poly~N-t2-~2-oxo-imidazolidin-l-yl)ethyl]
sulfonamido} copper phthalocyanines which comprises interacting
poly(chloro~ulfonyl) copper phthalocyanines with an excess of 1-
(2-aminoethyl)-2-imidazolidinone.
In a fourth process aspect, the invention relates to a
process for preparing poly ~ -[N-(2-aminoethyl)-2-aminoethyl]sulfon-
amido~ copper phthalocyanines which comprises hydrolyzing poly~N-
t2-(2-oxo-imidazolidin-1-yl)ethyl]sulfonamido~ copper phthalocya-
nines in a strong acidic medium and then rendering the resulting
mixture alkaline to obtain poly N-tN'-(2-aminoethyl)-2-aminoethyl]-
sulfonamido copper phthalocyanines.
In a fifth process aspect, the invention relates to a
process for preparing poly[N-(3-aminopropyl)sulfonamido] copper
-5-
` - ~16~76n
D.N. 8111
phthalocyanine~ which compri~es interacting poly~chlorosulfonyl)
ccpp~r phthalocyanines with an exces~ of N-acetylpropylenediamine~
hydrolyzing the re~ulting polytN-(3-acetylaminopropyl)sulfonamido]
copper phthalocyanines in an acid medium and rendering the result-
S ing mixture alXaline to obtain poly[N-(3-aminopropyl)sulfonamido
copper phthalocyanines.
DETAILED DESCRIPTION I~CLUSIVE OF THE
pREFERRED EMBODIMENTS
More specifically, thi~ invention in the first of its
composition of matter aspects resides in novel storage-stable dye
compositions comprising concentrated, free-flowing aqueous solutions
containing by weight of the entire composition: (a) as the dye
constituent approximately 9 to approximately 40 percent of acid
addition salt~ of a phthalocyanine of the formula
- ~ ~ 2-~
lg CuPc m
_ ~ 3
Formula I
with a single acid or mixed acids wherein: Pc is phthalocyanine,
Q i8 selected from the group consisting of -NH(CH2)yNtR)2, and
-NH(C~2)y~H(CH2)yNH2 in which R is selected from the group con-
sisting of hydrog-n, Cl to C4 alXyl and Cl to C4 hydroxyalkyl and
y is a number ~rom two to four, m i9 a number from one to flve,
and n $s a number from zero to one (b) from zero to approximately
10 percent of a Cl to C3 alkanesulfonic acld; tc) approximately 5
to approximately 30 percent of an aliphatic or hydroxyaliphatic
carboxylic acid, or in an inorganic acid; td) approximately 5 to
approximately 25 percent of urea or a glycol selected from the
group consistlng of ethyIene glycol, propylene glycol, diethylene
glycol and diethylene glycol monoethyl ether; and (e) the remainer
! being water.
-6-
Pl
.~
1 18S76~ D.N. 8111
In a first particular embodiment in accordance with
the ~ir~t of its composition of matter aspects, the invention
sought to be patented resides in the novel ~torage-stable dye
compositions conta1ning as the dye constituent acid addition
salts of a phthalocyanine according to Formula I wherein Q is
-NH(CH2)yN(R)2 having the formula
rcuP~O 2N~ ( Cl~ 2 ) yN ~
L ~J- L3~
Formula II
with a single acid or mixed acids wherein: Pc, R, m, n, and y
each have the same respective meanings given in Farmula I.
Preferred storage-stable dye compositions within the ambit of
this particular embodiment are: (a) a composition containing
by weight of the entire composition approximately 7 to approxi-
mately 12 percent of a dye constituent of Formula II wherein R is
hydrogen, y is three, and m is two to three, approximately i to
approximately 3 percent of methanesulfonic acid, approximately 7
to approximately 12 percent of acetic acid, approximately 3 to
approximately 8 percent of ethylene glycol and approximately 82
to approximately 65 percent of water (b) a composition containing
by weight of the entire composition approximately 20 to approxi-
mately 25 percent of a dye constituent of Formula II wherein R is
methyl, y is three and m i8 two to three, approximately 2 to ap-
proximately E3 percent methanesulfonic acid, approximately 20 to
approximately 25 percent acetic acid, approximately 8 to approxl-
mately 14 percent ethylene glycol and approxlmately 50 to approxi-
mately 2B percent percent water (c) a composition containing by
weight of the entire composition approximately 26 to approximately
32 percent of a dye con~tituent of Formula II wherein R is methyl,
y is three, and m i9 two to three, approximately 17 to approximate-
ly 25 percent of acetic acid, approximately 8 to approximately 14
percent of ethylene glycol, and approximately 49 to approximately 29 m~
-7-
, --~. . .
76n
D.N. 8111
percent of water; and ~d) a composition containing by weight
of the entire composition approximately 26 to approximately ~2
percent of a dye constituent of Formula II wherein R is methyl,
y is three, and m ~s two to three, approximately S to approxi-
mately lO percent of glycolic acid, approximately 20 to approxi-
mately 26 percent of urea, and approximately 49 to approximately
68 percent of water.
In a second particular embodiment in accordance with
the first of its composition of matter aspect, the invention
sought to be patented resides in the novel storage-stable dye
compositions containing as the dye constituent acid addition salts
of a phthalocyanine according to Formula I wherein Q is -NH(CH2)y~
NH(CH2)yNH2 having the formula
rCuP ~ 02~H~CH2)yNH( 2 y
L ~ 3~ n
Formula III
with a single acid or mixed acids wherein: Pc, m, n, and y each
have the same respective meanings given in Formula I. Preferred
storage-stable dye composition~ within the ambit of this particular
embodiment are: (a) a composition containing by weight of the
entire composition approximately l9 to approximately 24 percent of
a dye constituent of Formula III wherein y iq two and m is two to
three, approximately 21 to approximately 26 percent of acetic acid,
approximately 2 to approximately 7 percent of methanesulfonic acid,
approximately 9 to approximately 15 percent of ethylene glycol~ and
approximately 49 to approximately 28 percent of water (b~ a compo-
sition containing by weight of the entire composition approximately
15 to approximately 21 percent of a dye constituent of Formula III
wherein y is two and m is two to three, approximately 23 to approxi-
mately 29 percent of glycolic acid, approximately l to approximately
-8-
~ lB57~f) D.N. 8111
6 percent of methanesulfonic acid, approximately 6 to approxi-
mately 12 percent of ethylene glycol, and approximately SS to
approximately 32 percent of water (c) a composition containing
by weight of the entire composition approximately lS to approxi-
mately 21 percent of a dye constituen~ of Formula III wherein yis two, and m is two to three, approximately 23 to approximately
29 percent of glycol~c acid9 approximately 1 to approximately 6
percent of methanesulfonic acid, approximately 6 to approximately
12 percent of propylene glycol, and approximately 55 to approxi-
mately 32 percent of water; and (d) a composition containing byweight of the entire composition approximately 15 to approximately
21 percent of a dye constituent of Formula III wherein y is two,
and m is two to three, approximately 23 to approximately 29 per-
cent of glycolic acid, approximately 1 to approximately 6 percent
of methanesulfonic acid, approximately 6 to approximately 12 per-
cent of diethylene glycol monoethyl ether, and approximately 55 to
approximately 32 percent of water.
In a second composition of matter aspect, the invention
sought to be patented resides in the novel acid addition salts of
a phthalocyanine of the formula
LCuP ~ m
0
Formula I
with a single acid or mixed acids wherein: Pc is phthalocyanine;
Q is selected from the group consisting of -NH(CH2)yN(R)2 and
-NH(CH2)yNH(CH2)yNH2 in which R is selected from the group consist-
ing of hydrogen, Cl to C4 alkyl and Cl to C4 hydroxyalkyl and y is a
number from two to four m is a number from one to five; and n is a
number from zero to one having a total of at least (0.5 m) but not
more than ~2 m) complexed molecules of one or more acids selected
_g_
1 16~7S~ D.N. 8111
from the group consisting of hydrochloric acid, hydrobromic acid,
acetic acid, propion~c acid, glycolic acid, 3-hydroxypropionic
acid~ lactic acid, methanesulfonic acid, and ethanesulfonic acid.
In a first particular embodiment in accordance with the
second of its composition of matter aspect, the invention sought
to ~e patented resides in the novel acid addition salts of a
phthalocyanine according to Formula I wherein Q is -~H(CH2) N(R)2
having the formula
rcUPc ~ o2NH(CH2)yN(R)~
L ~ 3~ ~
Formula II
with a single acid or mixed acids wherein: Pc, R, m, n, and y
each have the same respective meanings given in Formula I. Pre-
ferred acid additlon salts of phthalocyanines of Formula II fal-
ling within the ambit of this particular embodiment are: (a)
wherein R i~ hydrogen, y is three and m is two to three having
one to two complexed glycolic acid molecules and 0.5 to one sulfonic
acid substituent and having 0.5 to 1.5 complexed methanesulfonic
acid molecules, one to two complexed acetic acid molecules and 0.5
to one sulfonic acid substituent.; (b) wherein R is methyl, y is
three and m is one to three having 0.5 to two complexed methane
sulfonic acid molecules and 0.5 to one sulfonic acid substituent
and having two to three complexed glycolic acid molecules and 0.3
to 0.8 sulfonic acid substituent and ~c) wherein R is hydroxyethyl,
y is three and m is one to three having one to two complexed methane-
sulfonic acid molecules and 0.5 to one sul$onic acid substituent.
--10--
P~
~ ~57~(~
D.N. 8111
In a second particular embodiment in accordance withthe second of its composition of matter aspects, the invention
~ought to be patented resldes in the novel acid addition salts
of a phthalocyanine according to Formula I wherein Q is -NH(CH2)y~
S NH(CH2)y~H2 having the formula
---E 2NH ~ CH 2 ) y~H ( CH 2 ) yNH ~l ,
. C~Pc ~ 3~ n
Formula III
with a single acid or mixed acids wherein Pc, m, n, and y each
have the same respective meanings given in Formula I. Particularly
preferred acid addition sales of phthalocyanine of Formula III
falling within the ambit of this particular embodiment are those
wherein y is two and m is one to three having one to three com-
plexed hydrochloric acid molecules and 0.5 to one sulfonic acid
substituent having three to five complexed hydrochloric acid
molecules and 0.5 to one 3ulfonic acid substituent; having 0.5
to two complexed acetic acid molecules and 0.5 to one sulfonic
acid substituent; having one to three complexed glycolic acld
moleculeq and 0.5 to one sulfonic acid substituent; having one
to four complexed methanesulfonic acid molecules and 0.5 to one
sulfonic acid substituent and having one to three complexed meth-
anesulfonic acid molecules~ 0.5 to three complexed acetic acid mole-
cules and 0.5 to one sulfonic acid substituents.
In a third composition of matter aspect, the invention
sought to be patented resides in the novel phthalocyanine~ having
the formula
1 16~76~)
D.N. 8111
i r 1~2 ~
. _-- SO 2~HC 2H4 ~ ~
L ~ . ~ 8 ~ ",
Formula IV
wherein Pc is phthalocyanine, m is a number from one to five and
n is a number from zero to one.
In a fourth composition of matter aspect, the invention
sought to be patented resides in the novel phthalocyanines having
the formula
r p~0 2NHc2H4NHc2H4 ~ m
3~ n
Formula V
wherein m i8 a number from one ~o five and n is a number from zero
to one.
In a fifth compo~ition of matter aspect~ the invention
sought to be patented resides in the novel phthalocyanines having
the formula
r p~o2~C3H6~
~ ~ 3~ n
Formula VI
wherein m is a number from one to five and n is a number from zero
to one.
In one of its process aspect~, the invention sought to
be patented resides in a process for preparing storage-stable aque-
ous dye compositions containing acid addition salts of poly(N-sub-
-12-
P~
1 ~576~) D N. 8111
stituted .sulfonamido) copper phthalocyanines of Formula I which
comprise.s interacting approximately 0.5 to approximately 10
molecular equivalents of a sin~le acid or a mixture of acids
with approximately one molecular equivalent of copper phthalo-
cyanine having at least one and not more than five -SO2Q ~ubsti-
tuents and zero to one sulfonic acid substituent in a mixture of
water, urea or a glycol chosen from the group consisting of
ethylene glycol, propylene glycol, diethylene glycol and diethylene
glycol monoethyl ether, a Cl to C3 alkanesulfonic acid, and an
aliphatic or hydroxyaliphatic carboxylic acid or an inorganic
acid, said components being used ln appropriate quantities to
produce by weight of the entire composition approximately 9 to
approximately 40 percent of a dye constituent, approximately 5
to approximately 25 percent of urea or a glycol, ~ero to approxi-
mately 10 percent of an alkanesulfonic acid, approximately 5 to
approximately 30 percent of an aliphatic or hydroxyaliphatic
carboxylic acid or inorganic acid and the remainder being water.
In a second process aspect, the invention sought to be
patented resides in a process for preparing ~cid addition salts
of a poly(~-substituted sulfonamido) copper phthalocyanine of
Formula I which comprises interacting approximately 0.5 to approxi-
mately 10 molecular equivalents of a single acid or a mixture of
acids with approximately one molecular equivalent of copper phthalo-
cyanine having at least one and not more than five -SO2Q substi-
tuents and zero to one sulfonic acid substituent.
In a third process aspect, the invention sought to be
patented resides in the process for preparing a copper phthalocya-
nine having one to five N-t2-~2-oxo-imidazolidin-1-yl)ethyl]sulfon_
amido substituents and zero to one sulfonic acid substituent accord-
ing to Formula IV which comprises interacting a copper phthalocya-
nine having one to six chlorosulfonyl su~stituents with an excess
-13-
.- ~
"` ` ~ 1~S76()
D.N. 8111
of 1-(2-aminoethyl)-2-imidazolidinone in the pre~ence of an alkall
metal oarbonace.and.pyridine. . .
In a fourth process aspect, the invention sought to be
patented resides in the process fox preparing a copper phthalo-
cyanine having one to five N-[N'-(2-aminoethyl)-2-aminoethyl]sul-
fonamido substituents and zero to one sulfonic acid substituent
according to Formula V which comprises in a first step hydrolyzing
a copper phthalocyanine having one to five N-~2-(2-oxo-imidazolidin-
l-yl)ethyl]sulfonamido substituents and zero to one sulfonic acid
substituent in a strong acidic medium and in a second step render-
ing the resulting mixture from the first step alkaline to obtain
the copper phthalocyanine having one to five N-~N'-(2-aminoethyl)-2-
aminoethyl~sulfonamido substituents and zero to one sulfonic acid
substituent. ~ .
In a fifth process aspect, the invention sought to be
patented reside~ in the process for preparing a copper phthalocya-
nine having one to five N-(3-aminopropyl)sulfonamido substituent~
and zero to one ~ulfonic acid substituent according to Formula VI
which comprise~ in the first step interacting a copper phthalocya-
nine having one to six chlorosulfonyl substituents with an exce~s
of N-acetylpropylenediamine in the presence of an alkali metal car-
bonate and pyridine, and in a second step the resulting copper
phthalocyanine having one to five N-(3-acetylaminopropyl)sulfon-
amido substituents and zero to one sulfonic acid substituent i~
hydrolized in an acid medium and in a third step the resulting mix-
ture i~ rendered alkaline to obtain the copper phthalocyanine hav-
ing one to five N-(3-aminopropyl)sulfonamido substituents and zero
to one sulfonic acid substituent.
The term "phthalocyanine" is used herein in the generic
sense to mean the cla~s of tetraazoporphins in which each of four
I -14_
t~
7~n
D.N. 8111
pyrrole nuclei is fu~ed to an aromatic nucleus, e.g. that of
benzene. Phthalocyanine itself (tetrabenæotetraazoporphin) i~ a
well-known example of the class, and the prefixed term ~copperu
means that the phthalocyanine contains a copper ion in complex
combination.
The terms ~complexed acid molecules", "complexed hydro-
chloric acid molecules", ~complexed methanesulfonic acid moleculec"~
"complexed acetic acid molecules" and ~complexed glyc~lic acid
molecules" are used herein to mean that the respective acid mole-
cules are present in the dyestuff molecule in the form of acidaddition adducts. It will, of course, be understood that the pre-
cise type of bonding will depend on the condition in which the dye-
stuff molecule exists, that is, as a discrete solid or dissolved
in solution. Thus, ii the former, it would be expected that the
acidic materials would be bound by quaternization of primary, secon-
dary and tertiary amino substituents of the aminoalXylenesulfonam-
ido tail chain~ while in the latter, it would be expected although
the aminoalkylenesulfonamido substituents would also by predomi-
nantly in the quaternized form, some dissociation is possible in
such an "acid-base" system.
It i5 well known by those ~killed in the art of phthalo-
cyanine chemi~try that synthetic processe~ for the chlorosulfonation
of phthalocyanine molecules almost invariably produce mixtures of
3ubstituted products rather than~a single product having a specific
number of substituent~. This is, of cour~e, the case with the in-
~tant compounds. The methods of chlorosulfonation of the phthalo-
cyanines are known and usually give mixture of chlorosulfonated
product~ comprising~ for example, bis-, tris- and tetrachlorosul-
fonates. The fact that mixtures are obtained and not a single com-
pound i~ not in any way deleterious to the use of the products as
..:
--15--
7 6 ()
D.N. 8111
dyestuffs~ The procedures taught in U.S. Patent No. 2,86~,875
which have been followed to produce the requisite metal phthalo-
cyanine sulfonic acid chloride dye~tuff intermediates herein, as
would be expected have been found to produce mixture-~ of substi-
tuted phthalocyanine molecules. Accordingly, the terms liXe zeroto one, one to three, one to five, and the like adopted in the
claims and in the disclosure to describe the number of N-substituted
sulfonamido and sulfonic acid substituents on the subject phthalo-
cyanines as well as the number of complexed acid molecules mean~
the average number of said substituents per molecule of phthalo-
cyanine. The ~eaning of these terms may be illustrated with refer-
ence to the amount or number of sulfonic acid substituents which are
introduced into the phthalocyan1ne compounds as a result of hydroly-
sis of the sulfonic acid c~loride portion of the molecule both dur-
ing isolation from its reaction mass and during the interaction ofthe sulfonic acid chloride with an appropriate amine in an aqueous
medium to obtain the desired phthalocyanine sulfonamido derivative.
It i8 obvious that there cannot be 0.5 of a sulfonic acid substitu-
ent on the phthalocyanine molecule. This figure is, of course, an
average value which results from the presence in the mixture of
phthalocyanine molecules having either zero or one sulfonic acid
substituent.
The instant novel acid addition salt forms of the poly-
(N-sub~tituted sulfonamido) copper phthalocyanine dyestuffs provide
shades of turquoise. They have valuable properties as water-soluble
direct dyes useful in the dyeing art for coloring natural fibers,
synthetic fiber-forming materials and cellulose materials such a~
threads, sheets, filament~, textile fabrics and the liXe as well
as in the manufacture of paper, varnishes, ink~, coatings and pla~-
tics. Further the free base forms of the polv(N-substituted sulfon-
amido) copper phthalocyanines including the poly N-[2-(2-oxo-imida-
zolidin-l-yl)ethyl] sulfonamido derivative are useful as pigments
and as pigment additlves.
-16-
I lB~7S()
D.N. 8111
The mixtures of poly~N-substituted sulfonamido1 copper
phthalocyanines and the water-soluble acid addition salts thereof
of this invention are characterized by good lightfastness. The
mixtures of the phthalocyanines in the form of their water-~olu-
ble acid addition salts are useful as dyes for dyeing operations,and in the water-insoluble free-base form as well as their acid
addition salt forms as pigments for printing operations on woven
and non-woven substrates made from natural fibers, such as wool,
cellulose or linen, those made from semi-synthetic fibers, such
as regenerated cellulose as represented by rayon or viscose, or
those made from synthetic fibers, such as polyaddition, polycon-
densation or polymeri~ation compounds. Such dyeings or printings
can be carried out in accordance with the usual dyeing and print-
ing processes.
The mixtures of the poly(~-substituted sulfonamido) copper
phthalocyanines and their acid addition salt forms of this invention
are al~o suitable for surface coloring or printing paper products
and cardboard as well as for coloring paper pulps. Moreover, they
are useful for incorporation into lacquers and films of various
constitution~ for example, those made from cellulose acetate, cel-
lulose propionate~ polyvinyl chloride, polyethylene, polypropylene,
polyamides, polyesters of alkyd resins. In addition, the subject
compounds are suitable for coloring natural or synthetic resins,
for example~ acryllc resins, epoxy resins, polyester resins, vinyl
resins~ polystyrene resins, or alkyd resins.
The mixtures of poly(N-substituted sulfonamido) copper
phthalocyanines are readily converted to the corresponding water-
soluble dyes by treatment in an aqueous solution containing from
0.5 to 10 equivalents of one or more of an inorganic acid, ali-
phatic or hydroxyaliphatic carboxylic acid and alkanesulfonic acid
'
-17-
1 ~6~7~)
D.N. 8111
selected from the group consiqting of hydrochlor~c, hydrobromic,
acctic, propionic, glycolic, 3-hydroxypropionic, lactic, methane-
sulfonic and ethanesulfonic aclds.
The mixtures of the acid addition salt forms can be iso-
lated from the aqueous solution in which they are formed by tech-
niques well known in the art, for example, by salting out, preci-
pitation or concentration by evaporation. However, the mixtures
of water-soluble dyes thus formed are readily utilized in the form
of aqueous solutions for many of their applications, especially
for dyeing cellulose. Accordingly, it is particularly preferred
to retain the mixtures of dyes in a concentrated aqueous solution
of the type regularly employed in the paper industry for dyeing
paper products.
The acid addition salt forms are especially valuable dye~
for imparting stable turquoise blue shades to paper both sized and
unsi~ed. For use in the paper trade, the mixtures of the acid addi-
tion ~alt forms of this invention have several outstanding advan-
tages. Their high degree of water-~olubility makes them particu-
larly suitable for the preparation of liquid dye concentrates which
are preferred in the paper industry. The use of concentrated a~ue-
ous solutions is particularly advantageous in view of the increasing
trend toward automation, since these solutions are conveniently
handled and added to the pulp slurry in accurately measured amounts
by mean~ of pump and meters. The subject aqueous dye concentrates
are particula~ly suited to metered dyeing operations because they
have low visco~ity which remains essentially unchanged over long
periods under ordinary storage conditions. Their low viscosity pro-
vides another advantage in that they dissolve readily in the pulp
slurry and prevent specking or blotching seen when more viscous
dye concentrates are used. A further advantage of the concentrated
a~ueou-q solutions is that of convenience in shipping and handling.
-18-
"
6576()
D.N. 8111
In shipping and in u~e, the high degree of solubility of the
acid addition salt orms permit handling of solution~ containing
a higher dye content and results in a desirable decrease in the
weight and volume of solution per amount of dye. Furthermore,
the concentrated aqueous dye solutions are more convenient for
the paper mills in that the handling of dry dye, with the con-
comitant dusting and caking problems a~sociated with dissolving
the dye prior to its addition to the pulp slurry are eliminated.
The subject dye~ constitu~ing the mixtures of my inven-
tion are also less prone to ~bleed" when paper impregnated there-
with is wet and placed in contact with moist white paper. Thi~
is a particularly desirable property for dyes designed for color-
ing paper to be used in facial tissues, napkins, paper towels and
the like wherein it càn be foreseen that the colored paper, wetted
with common household liquids such as water, soap and detergent
solutions, milk, carbonated and alcoholic beverages, vinegar, rub-
bing alcohol, and so forth, may come in contact with other surface~,
such as textiles, paper and the liXe which should be protected from
8tain. Another advantageous property of the~e new mixtures of
~0 water-soluble dyes for use in the paper trade is found in their
high degree of color discharge when bleached with hypochlorite or
"chlorine" bleach. This property of the mixtures of the acid addi-
tion salt forms is particularly desired by papermakers in order that
dyed paper may be completely bleached prior to reproces~ing.
Still another advantageous property of the mixtures of water
soluble dyestuffs of thls invention is found in their hi~h re-
sistance to a change of shade when used to color cellulosic ma-
terials, which have either previously been treated with or are
treated sub~equent to dyeing , with wet-strength resin.
lg
.~,
~ 7Sn D.N. 8111
I have also Eound that the dye~ of this invention have
a high de~ree of substantivity for bleached fiber such as is used
in most colored disposable paper products. Moreover, they are ab-
sorb~d by cellulosic fibers from aqueous solution at a very rapid
rate. These properties are advantageous to the paper industry,
because it allows the dye to be added to the pulp just prior to
formation of the sheet.
The best mode contemplated by the inventor of carrying
out this invention will now be described as to enable any person
skilled in the art to which it pertains to make and use the same~
In accordance with one of the process aspects of thi~
invention, acid addition salt forms of the poly(N-substituted
sulfonamido) copper phthalocyanines of Formula I are obtained by
interacting approximately 0.5 to approximately 10 molecular equlva-
lents of an organic or inorganic acid or a combination of organicand inorganic acid~ for example, methanesulfonic acid, acetic
acid~ glycolic acid~ and hydrochloric acid with approximately one
molecular equivalent of copper phthalocyanine bearing at least one
but not more than five -SO2Q substituents and from zero to one
sulfonic acid substituent wherein Q has the meaning given in For-
mula I. The reaction is conveniently carried out in an aqueous
medium at a temperature in the range of 15C to 80C. The acid
addition salt forms are readily isolated by various conventional
mean~, for example~ by evaporation of the solvent, by salting-out
or more preferably by the addition of a miscible non-solvent~ for
example, a short chain aliphatic alcohol or a low molecular weight
ketone.
-20-
~ ~S7~(~ D.N. 8111
~lternatively, the acid addition salt orms of poly-
(N-sub~tituted sulfonamido) copper phthalocyanines can be obtained
from storage-stable compositions containing them by salting-out
techniques or by the addition of a miscible non-solvent, for exam-
S ple, a short chain aliphatic alcohol or a low molecular weight
Xetone.
In accordance with a further process aspect of the pre-
sent invention, the storage-stable dye compositions containing
acid addition salt forms of poly(~-substituted sulfonamido) copper
phthalocyanines of Formula I are obtained by interacting an or- ~
ganic or inorganic acid or a combination of organic and inorganic
acids with a copper phthalocyanine bearing at least one but not
more than five -SO2Q subst-ituents wherein Q has the same meaning
given in Formula I and zero to one sulfonic acid substituent in a
mixture of water and urea or a glycol~ for example, ethylene glycol
or propylene glycol. The reaction is conveniently carried out at
a temperature in the range of 15C to 50C with the preferred
temperature being ambient temperature. The said components aro
used in appropriate quantities to produce by weight of the entire
composition approximately nine to approximately forty percent of
a dye constituent, approximately five to approximately twenty-
five percent of urea or a glycol, zero to approximately ten percent
of an alkanesulfonic acid, approximately five to approximately
thirty percent of an allphatic or hydroxyaliphatic carboxylic acid
or an inorganic acid and the remainder being wa~er.
The requisite poly~N-substituted sulfonamido) copper
phthalocyanine~ for the preparation of the acid addition salts
of Formula I are prepared by first chlorosulfonating a copper
phthalocyanlne. The chlorosulfonated copper phthalocyanine~ are
readily obtained by the procedure similar to that taught in
-21-
.
~ ~657~n D.N. ~lll
U.S~ Patent No. 2,B63,875. Thus, copper phthalocyanine is
interacted with chlorosulfonic acid and thionyl chloride in the
proper ratios depending on the amount of chlorosulfonic acid
substitution desired. The reaction is conveniently carried ou~
S in excess chlorosulfonic acid. The reaction mixture is then
poured onto ice to obtain the desired polytchlorosulfonated)
copper phthalocyanine.
In accordance with a third procçss aspect of the inven-
tion, the compounds represented by Formula II wherein R is hydro-
gen and y is three, are conveniently prepared by interacting a
poly(chlorosulfonated) copper phthalocyanine with an excess o~ ~-
acetyl-~,3-propylene diamine in the presence of an alkaline carbo-
nate, for example, potassium carbonate and an organic base, for
example, pyridine. The reaction is advantageously carried out in
an aqueous medium at a temperature in the range of 15C to 75C.
The intermediate poly N-(N'-acetylaminopropylsulfonamido) copper
phthalocyanine is isolated by filtration. The poly N-(N'-acetyl-
aminopropylsulfonamido) copper phthalocyanine i8 then hydrolyzed
in aqueous dilute mineral acid at the reflux temperature, that is,
a temperature in the range of 95 to 105C. The desired products
of Pormula VI are i~olated by rendering the solution from the hydrol-
y8i5 slightly alkaline with concentrated aqueous ammonia.
The compounds represented by Formula II wherein R i~ Cl
to C~ alkyl are conveniently prepared by interacting a poly(chloro-
sulfonated) copper phthaiocyanine with an excess of N,N-dialkyl-
alkylenediamine, for example, dimethylaminopropylamine in the pres-
ence of an alkaline carbonate, for example, sodium carbonate and an
organic base, for example, pyridine. The reaction is conveniently
carried out in an aqueous medium at a temperature in the range of
I l~S7Sn D.N. 8111
15 to 85C. The desired products of Formula II wherein R is
Cl to C4 alkyl are conveniently isolated by filtration.
The compounds represented by Formula II wherein R i~
Cl to C4 hydroxyalkyl are conveniently prepared by interacting
S a poly(chlorosulfonate~) copper phthalocyanine with an excess
of N,N-dialkanolalkylenediamine, for example, diethanolaminopro-
pylamine in the presence of an alXaline carbonate, for example,
sodium carbonate and an organic base, for example, pyridine. The
reaction is conveniently carried out in an aqueous medium at a
temperature in the range of 15 to 90C. The product is isolated
by filtration.
In accordance with a still further process aspect of
the invention, the compounds represented by Formula V are prepared
by interacting a poly(chlorosulfonated) copper phthalocyanine with
lS an excess of 1-(2-aminoethyl)imidazolidinone. The reaction is con-
veniently carried out in an aqueous medium in the presence of an
alkaline carbonate, for example, potassium carbonate and an organic
base, for example, pyridine at a temperature in the range of 20
to 75Ç. After isolation, the resulting poly{N-~2-(2-oxoimidazoli-
din-l-yl)ethyl~ sulfonamido}copper phthalocyanine of Formula IV is
hydrolyzed in a dilute aqueous acid. The hydrolysis solution is
then made slightly alkaline by the addition of aqueous ammonia and
; the poly{N-[~'-(2-aminoethyl)-2-aminoethyl] sulfonamido~copper
phthalocyanines of Formula V are isolated.
Thé requisite 1-(2-aminoethyl?imidazolidinone intermedi-
ate i8 a known compound readily obtained by procedures taught in
U.S. Patent Nos. 2,613,212 and 2,868,727. Thus, one molscular equiv-
alent of urea is interacted with one molecular equivalent of di-
ethylene triamine liberating ammonia. The reaction can be carried
out neat or in 'the preqence of water which is distilled off during
J ~ 57~)
D.N. ~111
the course of the reaction. The reaction is conveniently carried
out at a temperature over the ran~e of 100 to 250C. The 1-(2-
aminoethyl)imidazolidinone can be used directly from the reaction
or it can be distilled at reduced pressure before using.
S The requisite N-acetyl-1~3-propylenediamine intermediate
is a known compound readily obtained by procedures known in the
art. In a first step, 2-methyl-1~4~5~6-tetrahyaropyrimidine was
prepared in a manner similar to that described in Japanese Patent
No. 15,925 (1967)(Chemical Abstracts 68 39331n) by heating 1,3-
propylenediamine and acetonitrile in the presence of sulfur.
After cooling slightly, a small portion of elemental zinc ~as added
to the reaction mixture and the 2-methyl-1,4,5,6-tetrahydropyrimi-
dine was distilled at reduced pressure from the reaction mass.
Finally, the 2-methyl-1,4,5,6-tetrahydropyrimidine was refluxed
lS with water for two hours and cooled to obtain a solution of ~-
acetyl-1,3-propylenediamine.
The reactive amine intermediates required for inter-
action wlth poly~chlorosulfonyl) copper phthalocyanines to ob-
tain the compounds of Formula II wherein R is Cl to C4 alkyl are
known compounds whose preparation is well-known in the prior art.
The following compounds are exemplary of these reactive amine
compounds useful in the practice of this invention.
3-Dimethylaminopropylamine
3-Diethylaminopropylamine
3-Dibutylaminopropylamine
2-Dimethylaminoethylamine
2-Diethylaminoethylamine
2-Diisopropylaminoethylamine
4-Diethylaminobutylamine
-24- _
ll6576n D.N. 8111
The reactive N-acetyl amine intermediates required for
interaction with poly(chlorosulfonyl) copper phthalocyanine~ to
obtain the compounds of Formula II wherein R is hydro~en after
hydrolysis are prepared from diamines well known in the prior art
by the proces~ described above or by other procedures. The follow-
ing compounds are exemplary of these reactive amine compounds use-
ful in the practice of this invention.
Ethylenediamine
Propanediamine
- Butanediamine
The following examples set forth the methods of prepara-
tion of the storage-~table dye compositions containing the acid
addition salt forms of poly(N-substituted sulfonamido) copper
phthalocyanines, acid addition salts of poly(N-substituted sulfon-
lS amido) copper phthalocyanine~, and poly(~-substituted sulfonamido)
copper phthalocyanines. All percentage of the constituent~ of
the dye compositions given in the following examples are by weight.
Included in the following examples are the results of the "bleed"
tests a3 described in Example 1 of samples of pàper prepared from
pulp dyed with the products of the following examples. In theQe
"bleed" tests the dyed sample of paper is wetted with the appro-
priaté household liquid and placed as a filter between clean, dry,
white filter paper. After a period of time the so-called "sand-
wich" i8 disasQembled and the component piece mounted and dried.
The filter paper~ are then examined under daylight and evaluated
wlth respect to the amount of dye which bled from the dyed paper
sample to the f~lter paper~ The evaluations are graded on the
basis of the following scale:
. .
:
_25-
1 16576~ D.N. 8111
B ed Grade Definition
none no observable bleed
trace first noticeable bleed
slight approximately twice the ~race amount
S of dye bleed
moderate approxima~ely four times the trace
amount of dye bleed
appreciable approximately eight times the trace
amount of dye bleed
much approximately sixteen times the trace
amount of dye bleed
very much approximately thirty-two times the
trace amount of dye bleed
-26-
P~
.. .
~ ~576(~
D.N. ~111
Example 1
A. Over approximately forty-five minute3, ~0.0 ~ of copper
phthalocyanine wa~ gradually added to 336~0 ml of chlorosulfonic
acid with stirring while maintaining 45 to 50C by mean~ of an
external cold water bath. While maintaining 45 to 50C, 76.8 ml
of thionyl chloride was slowly added to the mixture. After the
addition, the reaction mixture was gradually heated to a gentle
reflux at 88C.and the reflux temperature slowly ro~e to 115C.
The reaction mixture was maintained at 115 to 1201C for four
hours and then cooled to ambient temperature to obtain a solution
containing predominantly copper phthalocyanines trisulfonic acid
chloride.
B. To a mixture of 200.0 ml of water, 70.0 g of sodium chlo-
ride, 1000 g of ice and 0.3 ml of a nonionic wetting agent ~nonyl-
phenyl polyethylene glycol ether) there was added slowly 85.0 ml of
the copper phthalocyanine trisulfonic acid chloride solution from
part A above while maintaining 20C by the addition of 345.0 g of
ice with vigorous stirring. After stirring for approximately fif-
teen minutes, 50.0 ml of xylene was 810wly added and the agitation
continued for f~fteen additional minutes before stopping the stir-
ring. The water layer wa~ separated from the bottom and the organic
layer containing the dye~tuff was washed twice with 1300.0 ml of
water, separating after each wash. There was added to the result-
ing organic layer 75.0 ml of water, 31.6 g of 1-(2-aminoethyl)-2-
imidazolidinone, 20.7 g of potassium carbonate and 1.0 ml of pyri-
dine producing a slurry having a pH of 10.3 which wa~ ~tirred over-
night at amb~ent temperature. In the morning the pH was 9.95.
The slurry was sequent~ally heated at 45 to 50C for one hour and
at 60 to 65C for one and three quarters hours before cooling to
-27_
P~
3 ~6576~ D.N. 8111
room temperature. The solids were collected by filtration,
washed with 500.0 ml of one percent aqueou~ sodiwn chloride and
dried in vacuo at 90C to obtain 35.6 g of solids containing as
the major component bis-N-~[2-~2-oxo-imidazolidin-1-yl)ethyl]-
sulfonamido~ copper phthalocyanine (Formula IV: m-l to 3; and
n=0 to 1).
C. With stirring, 10.0 g of the product from part B above
was added to a mixture of 60.0 ml of water and 35.0 g of concen-
trated sulfuric acid. The mixture was heated at reflux for appro-
ximately sixteen hours, cooled and with stirring poured into 200.0
ml of water. The resulting slurry was made alkaline to Brilliant~
Yellow te~t paper by the addition of approximately 45.0 ml of con-
centrated ammonium hydroxide. After stirring for thirty minutes, an
additional 10.0 ml of conc~ntrated ammonium hydroxide was added.
m e solid was collected by filtration, washed with 200.0 ml of one
percent aqueous sodium chloride solution and dried in vacuo at 50C
to obtain 8.5 g of a blue colored solid being predominantly bis-N-~
~N~-(2-aminoethyl)-2-aminoethYl~sulonamido~ copPer phthalocYanine
(Formula III: y~2 m=l to 3, and n=0 to 1). The visible absorption
spectrum of a dilute acetic acid solution of the dye~tuff containing
0.02 g of dye per liter of solution showed a maximum at 625 millimi-
crons~ AØ7886.
D. A mixture of 20.7 g of predominantly bis-N-{~N'-(2-amino-
ethyl)-2-aminoethyl]sulfonamido} copper phthalocyanine prepared in
a manner similar to that described in part C above, 35.0 ml of water,
22.5 g of glacial acetic acid, 10.8 g of ethylene glycol and 4.7 g
of 95 percent methanesulfonic acid was stirred until a deep blue so-
lution resulted. m e visible ab~orption spectrum of a diluted aque-
ous solution of this dye~tuff solution containing 0.12 g of dye per
liter of solution showed a maximum at 623 millimicrons, A=1.03.
~ ~s~
D.N. 8111
This concentrate, containing approximately 11.5 percent ethylene
glycol, approximately 22 percent dye component, approximately
24 percent acetlc acid, approximately 4.8 percent methanesulfonic
acid and approximately 37.7 percent water each by weight of the
entire composition, had a viscosity of 50 cen~ipoise~.
The storage-stability of the concentrated dye solution
obtained directly above was evaluated by comparing its initial
visco~ity with that obtained after subjecting the solution to
heating in a closed container in a hot-air oven at 120F for a
period of time After 472 hours at 120F, the aged concentrated
solution had a viscosity of 75 centipoise~.
Sized and unsized paper dyed with aqueous dilutions of
this concentrate, according to ~he procedure described hereinbelow
had a turquoise shade and was found to be highly bleachable ap-
proximately 90 percent of the dyestuff was destroyed, in the bleachte~t described hereinbelow. The dye was also found to produce no
bleed in the water-bleed test, the soap-bleed test and the milk-
bleed test when tested in accord with the procedure described here-
inbelow.
E. Sub~tituting propylene glycol for ethylene glycol in
part D above, a solution was produced which further diluted to a
concentration containing 0.12 g of dye per liter, showed a maximum
in the visible absorption spectrum at 624 millimicron~, A=0.996.
F. When diethylene glycol monoethyl ether was sub3tituted
for ethylene glycol in part D above, a solution was produced which
further diluted to a concentration containing 0.12 g of dye per
liter, the visible absorption ~pectrum showed a maximum at 624
millimicrons, A=0.996.
G. A mixture of 22.0 g of predominantly bis-N-{~N'-(2-amino-
ethyl)-2-aminoethyl]sulfonamido} copper phthalocyanine prepared in
a manner similar to that described in part C above, 54.0 ml-of water,
10.8 g of ethylene glycol, 31.4 g of 70 percent glycolic acid and
4.5 g of 9~ percent methanesulfonic acid was stirred for appro-
-29-
7 ~ ~
D.N. 8111
ximately ei~hteen hours at ambient temperature. The visible
absorption ~pectrum of an a~ueous solution of this dyestuff con-
taining 0.12 g of dye per liter of solution showed a maximum at
622 millimicrons, A_0.7812. This concentrate containing appro-
ximately 18 percent phthalocyanine dyestuff~ approximately 25.6percent glycolic acid, approximately 3.7 percent methanesulfonic
acid, approximately 8.7 percent ethylene glycol and approximately
44 percent water, each by weight of the entire composition, had a
viscosity of 200 centipoises. The storage stability of the concen-
trated dye solution obtained above was demonstrated by comparing~the initial viscosity, 200 centipoises, with the viscosity, 150
centipoises, of the solution aged for 223 hours in a hot-air
oven at 125F. m e concentrate had bleach and bleed properties
identical to the concentrate of part D hereinabove.
DYEING PROCEDURE
A, A O.l percent ~tock dye solution was prepared by dilut-
~ng 2.95 g of the concentrated dye solution containing mixed
methanesulonic acid-acetic acid addition salts of predominantly
bi~-N-{tN'-~2-aminoethyl)-2-aminoethyl]sulfonamido} copper phthalo-
cyanine prepared in Example 1, part D above to one liter volumewith distilled water. With stirring, 30.0 ml of the 0.1 percent
dye solution was added to 100.0 g of an aqueous slurry containing
approximately 3 percent of bleached kraft pulp (600 Canadian Stan-
dard Freenessj. Agitation wa~ continued for approximately fifteen
minutes prior to dilution with water to a volume of four liters
wlth agitation. The dyed pulp was then formed into an 8 by 8 inch
square of paper by means of a filter-box. The paper sheet wa~
pressed between two blotters and then dried at 180F for four min-
utes between two fresh dry blotters to yield a uniformly dyed tur-
quoise paper sheet.
-30-
116$76n D.N. 8111
B. Sized Paper Grade~:
With stirring 30 ml of the 0.1 percent stock dye ~olu-
tion was added to 100 g of an aqueous slurry containing 3 percent of
bleached kraft pulp (600 Canadian Standard Freeness). After
approximately three minutes of stirring, 5.0 g of a 1.5 percent
water solution of papermaXer~s alum was added. Stirring wa~ con-
tinued for approximately fifteen minutes before it was diluted to
four liters with water and the pH adjusted to 5.0 with dilute
sulfuric acid. The dyed fiber slurry was drawn into an 8 by 8
inch square of paper and dried as described in part A above.
TESTING PROCEDU~ES
The following test procedures were employed to determine
the resistance of the dyestuffs to bleed in moist paper, to bleed
from paper in the presence of soap or milk, and to bleaching witb
hypochlorite bleach.
Water "Bleed" Test
This procedure is a modification of the AATCC Standard
Test Method 15-1962, "Colorfastness to Perspiration~.
Test pieces consisting of four plies, each one inch
square, are cut from the dyed paper to be tested. One or more
dyed papers of known dye migration quality are included in the test
series as standards.
The absorbent material consists of filter paper having
a relatively smooth finish (Whatman ~1, 4.25 cm. dia. equivalent).
Z5 ln addition, smooth, flat, glass or clear plastic plates of ade-
quate stiffness, measuring two inches wide and three inches long,
are required as separating plates. A 1000 gram weight serves as
a dead weight loading.
-31- -
:
~LBS7B~
D.N. 8111
Four filter paper absorbent pieces are u~ed for each
dyed paper test square, two for each s~de.
The migration test "sandwich" i9 constructed as fol-
1OWA. A separating plate is placed on a horizontal support and
two pieces of the filter paper placed centrally on this plate
with the smoother side up. The square dyed paper test piece~,
held by tweezers, are immersed in tap water at room temperature
for five ~econds, drained for five seconds, and immediately cen-
tered on the filter paper. Immediately, two pieces of filter
paper are centered on the test square and followed at once by
another ~eparating plate. Thi5 "sandwich" is pressed for a mo-
ment with the fingers, after which, without delay, a piece of
filter paper is positioned on the top separating plate as before
to receive a second test square of wetted dyed paper. The above
lS procedure is then repeated as rapidly as possible and without
lnterruption, stacklng one "sandwich" on the othér, until all
dyed paper test piece~ have been put under te~t.
As soon as a stack is completed, a 1000 gram weight i8
centered on the top separating plate. The stack is allowed to
stand at room temperature (75F) for flfteen minutes.
At the end of the migration period, the stacX is di~-
assembled, and each dyed paper test square and its filter paper
absorbonts clipped to a supporting card. A separate card is used
fôr each te~t square. The dyed paper test squares and filter
papers are air dried at room temperature for at leaqt two hours
(in the dark) before ranking. Relative degrees of dye migration,
as compared to that from standard samples, are determined by visual
rating~, in daylight, of the intensity of dye stain on the filter
paper surface~ which had been in contact with the test square.
,
-3~_
, ~
l1~$7~n D.N. 8111
Soap_~leed Test
This procedure utilizes the ~ame method employed in
the Water-~leed Test described above~ except that the dyed paper
test squares are immersed in a 0.5 percent tap water solution of
white soap flakes (a mixture of 80 percent sodium soap and 20
percent potas~ium soap produced from 70 percent tallow and 30
A percent coconut oil glyceride blend; ~Ivory~ brand, Proctor and
Gamble Co.) at 120F, instead of water alone.
Milk-Bleed Test
This procedure utilizes the same method employed in
the water-bleed test described above, except that the dyed paper
squares are immersed in room temperature homogenized milk instead
of water.
Bleach Te~t
This procedure compares the degree to which the color
of dyed pape~rs would be discharged in a waste paper recovery
operation employing hypochlorite bleach.
A preliminary estimate of bleachability is obtained by
placing a dxop of hypochlorite bleach, containing 2.5 percent
available chlorine on the dyed paper and allowing it to dry at
room temperature. From this test, both rate and degree of bleach-
ing are estimated.
A more accurate test, approximating paper mill proce-
dure, is performed by defibering three grams of dyed paper in
150 ml of distilled water using a kitchen blender. The defibered
pulp slurry is placed in a jar and hypochlorite is adde* to the
extent desired, usually 2.5 percent available chlorine based on
the weight of the dry fiber. The slurry consisting of pulp and
hypochlorite is adjusted to pH 9 with dilute sulfuric acid or
dilute aqueou~ solution of sodium hydroxide and placed in a water
bath to maintain the interval in the temperature range of 115F
~ Tr~e ~ a~k~ _33_
-
1 16$7fi~ D.N. 8111
to 125F. After the te~t i~ started, the jar is loo~ely capped.
~t five minute intervals, the cap is tightened and the jar in-
verted twice to circulate the liquor. The cap is loosened between
inversions. After twenty minutes, the p~ is checked, and if higher
S than 7.5, is adjusted thereto. The test is then continued for an
additional twenty minutes (with five minutes between inversions).
The terminal pH is generally found to ~e 6.0-6.5. An excess of
sodium thiosulfate is added as an antichlor, mixed for five min-
uteY and the slurry is diluted to a concentration of approximately
0.3 percent of fiber. Sheets are then prepared at pH 7 without
a washing step. Finally, this sheet is pressed and dried in a ~
paper dryer. Control dyeings at specific levels can then be made
to accurately determine the loss of strength of color on bleach-
ing.
.. .. ..
Example 2
A. To 20.0 ml of solution from Example 1 part D above, 20.0
ml of isopropyl alcohol was added with stirring, and the solid
which separated from solution was collected by filtration and
washed with isopropyl alcohol. The filter cake was redissolved
in approximately 25 ml of water and isopropyl alcohol was added
to precipitate the acid addition salt. The resulting dark blue
solid was collected by filtration, washed with isopropyl alcohol
and dried in vacuo at 90C to obtain 5.7 g of the mixed methane-
sulfonic acid-acetic acid addition salts of predominantly bis-N-
{~N!(2-aminoethyl)-2-aminoeth~l~sulfonamido~ CopPer phthalocyanine.
Elemental analysis established that this product has an average per
molecule of approximately 1.9 [N'-(2-aminoethyl1-2-aminoethyl]-
sulfonamido substituents, approximately 0.8 sulfonic acid substi-
tuent, approximately 1.9 complexed methanesulfonic acid molecules
and approximately 1.9 complexed acetic acid molecules. The visi-
ble absorption spectrum of the mixed methanesulfonic acid-acetic
acid addition salts of the dyestuff in water containing 0.02 g of
dye per liter of sol~tion showed a maximum at 620 millimicron~
A=0.625.
-34-
~ . .
1 ~6576(~
D.N. 8111
Unsized paper dyed with an aqueous dilution of
mixed meth~nesulfonic acid-acetic acid addition salts of thi~
dyestuff containing 0.1 g of dye pex 100.0 ml o solution,
according to the procedure described above, had a turquoise shade
S and was found to be highly bleachable; approximately 9~.5 per-
cênt of the dyestuff wa~ destroyed, in the bleach test described
above. The dye was also found to produce no bleed in the water-
bleed test, only a slight bleed in the soap-bleed test and a
trace of bleed in the milk_bleed test.
B. With stirring, 5.0 g of the solid product prepared in a
manner similar to Example 1, part C above was slowly added to
100.0 ml of distilled water and 30.0 ml of 95 percent methanesul-
fonic acid was added in 10.0 ml incruments over three hours at
70-75C. After cooling, ~he solution was slowly added to 400.0 ml
of isopropyl alcohol to obtain the dark blue solid which was col-
lected by filtration. The filtered solid was dissolved in approxi-
mately 60 ml of distilled water and heated in the range of 70-75C
for ten minutes. After cooling to ambient temperature, the result-
ing ~olution was slowly added to approximately 400 ml of acetone
to precipitate the acid addition salts. The resulting dark blue
solid was collected by filtration and dried at 50C to obtain the
methanesulfonic acid addition salts of predominantly bis-N-~N'-
(2-aminoeth 1)-2-aminoeth l]sulfonamido~ co er hthaloc anine.
Y Y J PP P Y
Elemental analysis established that this product has an average
of approximately two ~N'-(2-aminoethyl)-2-aminoethyl] sulfonamido
substituents, approximately 0.8 sulfonic acid substituent and
approximately two complexed methanesulfonic acid molecules. The
visible absorption spectrum of dilute methanesulfonic acid addi-
tion salt solution containing 0.02 g of dye per liter of solution
showed a maximum at 622 millimicrons, A=0.648.
,
i
~; -35-
. . I .
.,
~ 16576(~
D.N. 8111
Unsized paper dyed with an aqueous dilution containing
0.1 g per 100 ml of ~olution of the methanesulfonic acid addition
salts of the dyestuff according to the procedure described above
had a turquoise shade and was found to be highly bleachable appro-
ximately 97 percent of the dyestuff was destroyed, in the bleach
test described above. The dye was also found to produce no bleed
in the water-bleed test, only a slight bleed in the soap-bleed
test and a trace bleed in the milk-bleed test.
C. With stirring, 12.0 ml of ~lacial acetic acid was slowly
added to 5.0 g of a product prepared in a manner similar to Exam-
ple 1, part C suspended in 100.0 ml of distilled water. After
stirring approximate7y two hours at 70-75C~the resulting solution
was cooled and poured into 500.0 ml of isopropyl alcohol. The
resultant mixture was heated on a steam bath for approximately
ninety minutes, cooled and the dark blue solid was collected by
filtration. The resulting wet solid was dissolved in approximately
60 ml of water by heating at 70-75C for one hour. After cooling
to ambient temperature~ the dark blue solution wa~ added to
400.0 ml of acetone and digested on a steam bath for one hour. An
additional 200~0 ml of acetone was added to the mixture and the
dark blue ~olid was collected by filtration and dried in vacuo at
50C to obtain the acetic acid addition salts of predominantly
bis-N-~[N'-2-aminoéthyli-2-aminoethyl]sulfonamido~ copper phthaio-
L - J
cyanine. Elemental analysis established that this product has an
average per molecule of approximately 1.8 [N'-~2-aminoethyl)-2-amino-
ethyl] sulfonamido substituents, approximately 0.8 sulfonic acid
substituent and approximately oné complexed acetic acid molecule.
The visible absorption spectrum of the acetic acid addition salts
in water containing 0.02 g of dye per liter of solution showed a
maximum at 629 millimicrons, A=0.6~0.
.
__
-
1 16576n
D.N. 8111
Unsized paper dyed with an aqueous dilution containing
0.1 g per 100.0 ml of the acetic acid addition saits of ~he dye-
stuff according to the procedure described above had a turquoise
shade and was found to be highly bleachable approximately 95
S percent of the dyestuff was destroyed in the bleach t~At des-
cribed above. The dye was also found to produce no bleed in the
water-bleed test, only a slight bleed in the soap-bleed te~t and
a trace of bleed in the milk-bleed 'test.
D. Proceeding in a manner similar to that described in
part C above, 5.0 g of a product prepared in a manner similar to
Example 1, part C, was interacted with 10.0 ml of 70 percent
glycolic acid and poured into 400.0 ml of acetone and the solid
collected by filtration. After redissolving the solid in water
and adding the solution to acetone, the dar~ blue solid was iso-
lated by filtration and dried in vacuo at 50C to obtain the glY-
colic acid addition salts of predominantly bis-N-{[N'-(2-amino-
ethYl)-2-aminoethyl]sulfonamido~-copper phthalocyanine. Elemental
analysi~ established that this product has an average per molecule
of approximately two ~ (2-aminoethyl)-2-aminoethyl] sulfonamido
substituents~ approximately 0.9 ~ulfonic acid substituent, and
approximately two complexe'd glycolic acid molecules. The visible
absorption spectrum of the glycolic acid addition salts in water
containing 0.02 g of dye per liter of solution showed a maximum
at 620 millimicron8~ A~0.544.
Unsized'paper dyed with an aqueous dilution containing
0.1 g per 100.0 ml of the glycolic acid addition salts of this dye-
~tuff according to the procedure'described above had a turquoise
~hade and was found to be highly bleachable; approximately 98 per-
cent of the dyestuff was destroyed in the bleach test described
above. The dye was also found to produce no bleed in the water-
bleed test; a very slight bleed in the soap-bleed test, and only
~ ~657S~ D.N. 8111
a trace of bleed in ~.e milk-bleed test.
E. Wi~. stirring, 25.0 ml of 37 percent a~ueous hydrochloric
acid was slowly added to a mixture of 5.0 g of a product prepared
in a manner similar to that described in Example 1, part C above
S and 50.0 ml of water. After stirring for approximately two hour
the resulting mixture was allowed to sit at ambient temperature
overnight. In the morning the dark blue solid was collected by
filtration. The water wet solid was mixed with 110.0 ml of dic-
tilled water and 15.0 ml of 37 percent hydrochloric acid. After
stirring for approximately ten minutes, 250.0 ml of isopropyl alco-
hol was added and the resulting mixture was stirred for five addi~
tional minutes. The resulting dark blue solid was collected by
filtration, washed three times each with 50.0 ml of isopropyl alco-
hol and dried in vacuo at 60C to obtain the hydrochloric acid addi-
tion salts of predominantlY bis-N-{[N'-(2-aminoethyl)-2-aminoethyl~-
w~ __do3 coPper phthalocvanine. Elemental analysis established
that this product has an average per molecule of approximately 2.1
~N'-(2-aminoethyl)-2-aminoethyl] sulfonamido substituents, approxi-
mately 0.9 sulfonic acid substituent and approximately 4.2 complexed
hydrochloric acid molecules. The visible absorption spectrum of the
hydrochloric acid addition salts in water containing 0.02 q of dye
per liter of solution showed a maximum at 622 millimicrons, A=0.7544.
Unsized paper dyed with aqueous dilution containing 0.1 g
per 100.0 ml of the hydrochloric acid addition salts of this dyestuff
2S according to the procedure described above had a turquoise shade and
was found to be highly bleachable, approximately 95 percent of the
dyestuff Was de~troyed in the bleach test described above. The dye
was also found to produce no bleed in the water-bleed test, a slight
bleed in the soap-bleed test and a trace of bleed in the milk-bleed
test.
-38-
16~76n
D.N. 8111
F. To 5.0 g of a product prepared in a manner similar to
that described in Example 1~ part C above suspended in 100.0 ml
of distilled water~ there was added dropwise 12.0 ml of 37 per-
cent hydrochloric acid. The mixture was heated at 60-70C for
approximately one hour and then cooled to ambient temperature.
The resulting dark blue solid was collected by filtration and
washed four time each with 25.0 ml portions of acetone. With
stirring~ the wet filter cake was dissolved in 50.0 ml of water
at 50-55C. The solution was cooled to ambient temperature and
60.0 ml of acetone was added. The resulting mixture was added to
500.0 ml of isopropyl alcohol. ~he dark blue solid which resulted
was filtered and dried to obtain the hydrochloric acid addition
salts of predominantly bis-N-{~N'-(2-aminoethyl)-2-aminoethyl]-
sulfonamido} copPer phthalocyanine. Elemental analysis established
that this product has an average per molecule of approximately 2.1
[N'-(2-aminoethyl)-2-aminoethyl]sulfonamido substituents~ approxi-
mately 0.7 sulfonic acid substituent and approximately 2.1 com-
plexed hydrochloric acid molecules. The visible absorption spec-
trum of the hydrochloric acid addition salts in water containing
0.02 g of dye per liter of solution showed a maximum at 620 milli-
m~crons, A=0.702.
Example 3
A A water wet filter cake containing approximately 30.5 g
of copper phthalocyanine trisulfonic acid chloride, prepared simi-
lar to Example 1~ part B'above wherein the trisulfonic acid chlo-
ride was filtered from the ice water after drowning, was added to
200.0 ml of cold water and the temperature adjusted to 5C by the
addition of ice. Slowly qodium carbonate was added to the slurry
until it wa~ slightly alkaline to ~rilliant Yellow test paper and-
25.0 g of 3-dimethylaminopropylamine and 1.0 ml of pyridine was
added. After ~tirring overnight at ambient temperature, the ~lurry
57~
D.N. 8111
was heated at 70-~0c for one and one-half hours. The slurry wa~
cooled to room temperature, the solid collected by filtration and
washed with 500.0 ml of one percent aqueou~ sodium chloride ~olu-
tion. After drying in vacuo at 85C, there was obtained 34.5 g of
predominantly bis~N-[(3-dlmethylaminopropyl)sulfonamido] copper
phthalocyanine (Formula II ya3 R=CH3; m=l to 3; n=0 to 1), a
blue solid. The visible absorption spectrum of a dilute acetic
acid solution of the dyestuff containing 0.02 q of dye per liter
of solution showed a maximum at 618 millimicrons, A=0.7646~
Sized and unsized paper dyed with dilutions of this dye~-
stuff in 0.05 percent aqueous acetic acid, according to the proce-
dure described above, had a turquoise shade and was found to be
highly bleachable, in the bleach test described above. The dye
was also found to produce no bleed in the water-bleed test and to
bleed slightly in the soap-bleed test when tested in accord with
the procedures described above.
9. A mixture of 4.0 g of a product prepared similar to that
described in part A abové and 50.0 ml of ethyl cellosolve was
heated at reflux temperature for approximately one hour, cooled to
ambient temperature and the blue solid wa~ collected by filtra-
tion, washed with 50.0 ml of distilled wat,er and dried in vacuo
at 50C to obtain 0.8 g of a deep blue solid.
This 0.8 g of deep blue solid was suspended in 35.0 ml
of distilled water and with stirrlng 2.0 ml of 95 percent aqueous
methanesulfonic acid was slowly added. The resultant mixture wa~
stirred at 50C for approximately one hour, cooled to ambient tem-
perature and poured rapidly into 300.0 ml of acetone. The dar~
blue solid which precipitated was collected by filtration. The
wet filter cake wa~ dissolved in 50.0 ml of distilled water with
stirring at 70C. After stirring one hour at 70C, the resulting
solution was cooled to ambient temperature a~d rapidly poured into
-40-
D.N. 8111
1 1~576(~
400.0 ml of acetone. The re~ulting mixture wa~ stirred at 50C
for approximately one hour, cooled and allowed to stand at ambient
tempera~ure overnight. The dark blue solid which formed was col-
lected by filtration and dried at 50C in vacuo to obtain the meth-
anesulfonic acid addition salts of predominantly bis-N-~(3-di-
methylaminopropyl)sulfonamido] copper phthalocyanine. Elemental
analysis established that this product has an average per molecule of
approximately 1.85 (3-dimethylaminopropyl) sulfonamido substituents,
0.85 sulfonic acid substituents and one complexed methanesulfonic
acid molecule. The visible absorption spectrum of an aqueous solu-
tion containing 0.02 g of the methanesulfonic acid addition salt~
per liter of solution showed a maximum at 618 millimicrons, A=0.628.
C. A mixture of 30.0 g of predominantly bis-~-[(3-dimethyl-
aminopropyl)sulfonamido~ copper phthalocyanine prepared in a man-
ner similar to that described above in part A, 40.0 ml of water,
24.0 g of urea and 12.0 ml of 70 percent aqueous glycolic acid wa~
stirred until all the solid~ were in solution. The resulting solu-
tion contained approximately 28.4 percent dye constituent, approxi-
mately 7.8 percent glycolic acid, approximately 22.6 percent urea
and approxlmately 41.2 percent water and had a viscosity of 140
centipoise8.
Sized and unsized paper dyed with aqueous dilutions of
thi~ concentrate, according to the procedure de~cribed above, had
a turquoi~e shade and was found to be highly bleachable, in the
bleach test described above. The dye was al~o found to produce
no bleed in the water-bleed test and to bleed slightly in the
~oap-bleed teqt when te~ted in accord with the procedure described
above.
1 ~ ~5 ~ ~ n D.N. 8111
D. A mixture of 21.0 g of predominantly bis-N-[(3-dimethyl-
aminopropyl)sulfonamido3 copper phthalocyanine prepared in a man-
ner similar to that described in Example 3, part A above, 28.0 ml
of water, 15.4 g of glacial acetic acid and ~.0 g of ethylene gly-
col was stirred until a deep blue solution resulted containing the
acetic acid addition salts of predominantlY bis-N-[(3-dimethyl-
aminopropyl)sulfonamido] copper phthalocvanine. The resulting
concentrate contained approximately 24 percent dye constituent,
approximately 21.3 percent acetic acid, approximately 11.3 percent
ethylene glycol and approximately 38.7 percent water. The visible
absorption spectrum of a diluted aqueous solution of the acetic
acid addition salts solution containing 0.12 g of dye per liter
of solution showed a maximum at 618 millimicrons, A=1.308
E. Proceeding in a manner similar to that described in
lS Example 2, part A above, 25.0 ml of the solution from Example 3,
part C was slowly added to 500.0 ml of isopropyl alcohol. The
resulting solid was collected by filtration and redissolved in
25.0 ml of distilled water. The solution was added to 500.0 ml
of i~opropyl alcohol. The resulting solid was collected by fil-
tration, washed with isopropyl alcohol and dried to obtain 7.5 g
of the ~lycolic acid addltion salt of predominantly bis-N-[(3-
dimethylaminopropyl)sulfonamido] copper phthalocYanine, a dark
blue solid. The visible absorption spectrum of a dilute aqueous
solution of the acetic acid addition salt containing 0.02 g of
dye per liter of solution ~howed a maximum at 620 millimicrons,
A=0.70.
Unsi~ed paper dyed with aqueous dilutions of the acid
addition salts containing 0.10 percent dye, according to the pro-
cedure described above had a turquoise shade and was found to be
-~2-
~ . . .
~ 16576~
D.N. 8111
highly bleachable; approximately 95 percent of ~he dyes~uff wa~
destroyed. The dye was also found to produce only a trace of
bleed in the water-bleed test.
.
F. A mixture of 21.0 g of predominantly bis-N-t(3-dimethyl-
aminopropylamino)sulfonamido] copper phthalocyanine prepared in
a manner similar to that described in Example 3, part A above,
38.0 ml of water, 10.8 g of ethylene glycol, 21.0 g of glacial
acetic acid and 4.5 g of 98 percent methanesulfonic acid was mixed
until a deep blue solution resulted. This concentrate contained
approximately 22 percent dye constituent, approximately 22 percent
acetic acid, approximately 4.7 percent methanesulfonic acid, ap-
proximately 11.3 percent ethylene glycol and approximately 40 per-
cent water. The visible absorption spectrum of a diluted aqueous
solution of the mixed acetic acid-methanesulfonic acid addition
salts solution containing 0.12 g of dye per liter of solution
showed a maximum at 619 millimicrons, A=1.116.
Unsized paper dyed with an aqueous dilution containing
0.1 g per 100.0 ml of the mixed acetic acid-methanesulfonic acid
addition salt~ of the dyestuff according to the procedure above,
had a turquoise shade and was found to be highly bleachable; appro-
ximately 95 percent of the dyestuff was destroyed, in the bleach
test described above. The dye was also found to produce a trace
of bleed in the water-bleed test.
G. A mixture of 4.0 q of predominantly tris-N-[(3-dimethyl-
2S aminopropyl)sulfonamido] copper phthalocyanine prepared similar to
in part A above, utilizing 25.7 equivalents of chlorosulfonic acid
and 5.24 equivalents of thionyl chloride per equivalent of copper
phthalocyanine in the preparation of the chlorosulfonated copper
phthalocyanine, 100.0 ml of distilled water and 5.0 ml of 70 per-
cent aqueous glycol$c acid wa~ heated and stirred until all the
-43-
57~()
D.N. 8111
solid was dissolved. The resulting solution was slowly poured
into 600.0 ml of isopropyi alcohol with stirring. The dark blue
solid which separated was collected by filtration, and washed
with isopropyl alcohol. The alcohol-wet solid was dissolved in
100.0 ml of distilled water and the resulting solution was slowly
added with stirring into 700.0 ml of isopropyl alcohol. The ~ly-
colic acid salts of predominantlv tris-N-[(3-dimethYlaminoProPYl)
sulfonamido] copper phthalocyanine that had precipitated was
collected by filtration, washed with isopropyl alcohol and dried.
Elemental analysis established that this product has an average
per molecule of approximately 2.85 (3-dimethylaminopropyl)sulfona-
mido substituents, approximately 0.45 sulfonic acid substituent
and approximately 2.4 complexed glycolic acid molecules. The visi-
ble absorption spectrùm of a dilute aqueous solution containing
0.02 g of the glycolic acid addition salts per liter of solution
~howed a maximum at 619 millimicrons, A~0.731.
Unsized paper dyed with an aqueous dilution containing
0.1 g of the glycolic acid addition salts of the dyestuff per 100.0
ml of solution according to procedure described above had a tur-
' quoise shad,e and wac found to be highly bleachable; approximately95 percent of the dyestuff was de~troyed in the bleach test des-
cribed above. The dyed paper was also found to have a trace of
bleed in the water-bleed test.
A. Proceeding in a manner similar to that described in
Example 1, part A above, 17 g of copper phthalocyanine was inter-
acted with thionyl chloride in chlorosulfonic acid. The resulting
filter ca~e was suspended in 85.0 ml of cold water and the tempera-
ture ad~uYted to 15C by the addition of ice. Slowly the resulting
slurry was neutralized by the additlon of potassium carbonate until
Brilliant Yellow test paper showed a light pink color.
-44-
~ .
~` 1 16~76(~
D.N. 8111
B. With stirring, 2-methyl-1,4,5,6-tetrahydropyrimidin0
was prepared in a mann~r similar to that described in Japanese
Patent No. 15,925 (1967) (Chemical Abstracts 68:39331n) by
interacting one equivalent of l,3-propylenediamine with one
equivalent of acetonitrile in the presence of sulfur. A small
portion of el~mental zinc was added to the reaction mass and
there was obtained by distillation at reduced pressure, 14.5 g
of 2-methyl-1,4,5,6-tetrahydropyrimidine. The 2-methyl-1,4,5,6-
tetrahydropyrimidine was refluxed in water for two hours and
cooled to obtain a solution of N-acetyl-1,3-propylenediamine.
C. To the slurry of predominantly copper phthalocyanine ~
trisulfonic acid chloride from part A above was added the solu-
tion of N-acetyl-1,3-propylenediamine from part B above, 8.9 g
of potassium carbonate and 1.0 ml of pyridine. Initially the p~
wa~ 11.2 and after stirring at ambient temperature overnight the
pH was 9.4. There was added to the mixture, 10.0 g of potassium
carbonate and the mixture was maintained at 55-60 for approxi-
mately five and one-half hours. ~he resultant solid was collected
by filtration~ washed four times each with 50.0 ml of one percent
aqueous sodium chloride and dried at 60-65C in vacuo to obtain
28.6 g of predominantly bis-N-{~3-(acetYlamino)propyl]sulfonamldo}
coPper phthalocyanlne.
D . To 400.0 ml of water there was added 25.0 g of the pro-
duct from part C above and 25.0 ml of concentrated hydrochloric
acid. The mixture was heated at reflux for approximately twenty-
four hours and cooled. Slowly~25.0 ml of ammonium hydroxide was
added to the mixture to render it alkaline to Brilliant Yellow
- - test paper. The slurry was then heated at 50-55C for approxi-
mately two hours, the solid was collected by filtration,
washed with 500.0 ml of one percent a~ueous sodium chloride solu-
tion and dried in vacuo at 45-50C to obtain 23.5 g of predomi-
-45- "
~ 1~57~)
D.N. 8111
nantly bis-N-[(3-amino~rop~l)sulfonamido] copper phthalocyanine
as a blue solid. (Formula II: y=~; ~=H; m=l to 3; n 0 to 1).
The visible absorption spectrum of a dilute acetic acid solution
of the dyestuff containing 0.02 g of dye per liter of solution
showed a maximum at 624 millimicrons, A=0.754.
Sized and unsized paper dyed with dilutions of this
dyestuff in 0.05 percent aqueous acetic acid, according to the
procedure described above, had a turquoise shade and was found
to be 90 percent bleachable, in the bleach test described above.
The dye was also found to produce no bleed in the water-bleed
test and to bleed only very slightly in both the soap-bleed te~t
and milk-bleed test when tested in accord with the procedures des-
cribed above.
E. A mixture of 21.1 g of predominantly bis-N-~(3-amino-
propyl)sulfonamido] copper phthalocyanine prepared as described
in part D above and 100.0 ml ethylene glycol monoethyl ether waq
heated at reflux for approximately one hour, cooled to ambient
temperature. ~he dark blue solid was collected by filtration,
washed with 50.0 ml of distilled water and dried at 50C in vacuo.
F- With stirring, 4.0 g of the solid obtained in part E above
was suspended in 100.0 ml of distilled water and 5.0 ml of 70 per-
cent aqueous glycolic acid was slowly added. After stirring the
resulting mixture for approximately one hour at 50C, it wa~
cooled to ambient temperature and slowly poured into 600.0 ml of
acetone. m e solid which separated was collected by filtration.
The wet filter cake was suspended in 75.0 ml of water with stirring
and heated at 70C for approximately one hour. The resulting solu-
tion was poured into 500.0 ml of acetone and this solution was then
added to 1000.0 ml of isopropyl alcohol. The dark blue solid which
formed was collected by filtration and dried at 50C in vacuo to
obtain 3.0 of the qlycolic acid salts of PredominantlY bis-N-~(3-
-46-
I
~ - .
~ ~6576n
D.N. 8111
aminopropyl)sulfonamido~ copper phthalocyanine. Elemental analys~s
established that thi~ product has an average per molecule of approxi-
mately 2.2 (3-aminopropyl)sulfonamido substituents, approximately
0.8 sulfonic acid substituent and approxi~ately 1.4 complexed gly-
colic acid molecules. The visible absorption spectrum of a diluteaqueous solution of the glycolic acid addition salts containin~
0.02 g of the acid addition salts per liter of solution showed a
maximum at 617 millimicrons, A-0.6408.
Unsized paper dyed with an aqueous dilution containing
0.1 g per 100.0 ml of the glycolic acid addition salts of the dye-
stuff according to the procedure described above had a turquoise
shade. The dye was found to have no bleed in the water-bleed test;
a slight bleed in the soap-bleed test, and a trace bleed in the
milk-bleed test described above.
G. A mixture of 12.6 of predominantly bis-~-~(3-amino-
propyl)sulfonamido] copper phthalocyanine obtained in part E
above, 97.0 ml of water, 6.5 g of ethylene glycol, 12.6 g of gla-
cial acetic acid and 2.7 g of 98 percent methanesulfonic acid was
stirred until the solids were dissolved. This concentrate, which
contained approximately 9.6 percent dye constituent, approximately
9.6 percent acetic acid, approximately 2 percent methanesulfonic
acid, approximately 5 percent ethylene glycol and approximately
73.7 percent water, was added to 500.0 ml of isopropyl alcohol
with stirring. The dark blue solid which precipitated was col-
~5 lected by filtration and washed with isopropyl alcohol. The alco- j
hol-wet solid was dissolved in 150.0 ml of distilled water and
isopropyl alcohol was added a second time. The dark biue solid
was collec~ed by filtration, washed with isopropyl alcohol and
dried in vacuo at 90-95C to obtain the mixed acetic acid-methane-
sulfonic acid addition salts ~_Eredominantly bis-~-[(3-aminopro-
pyl)su7fonamido] copper phthalocyanine.
-47-
1 16576~ D.N. 8111
Elemental analysis established that this product has an average
per molecule of approximately 2.2 (3-aminopropyl) sulfonamido
substituent~, approximately 0.8 sulfonic acid su~tituent,`
approximately one complexed methanesulfonic acid molecule and
approximately 1.2 complexed acetic acid molecules. The vi~ible
absorption spectrum of a dilute aqueou~ solution containing 0.02 g
of the mixed acetic acid-methanesulfonic acid addition salts per
liter of solution showed a maximum at 621 millimicrons, A=0.646.
Unsized paper dyed with an aqueous dilution containing
0.1 g of the mixed acetic acid-methanesulfonic acid addition sal~s
of the dyestuff per 100.0 ml according to the procedure described
above had a turquoi~e shade. The dyed paper was found to have no
bleed in the water-bleed test, a slight bleed in the soap-bleed
teRt; and a trace of bleed in the milk-bleed test.
Example 5
A~ To 200.0 ml of cold water~ a water wet filter cake con-
taining approximately 30.5 g of copper phthalocyanine trisulfonic
acid chloride was added and the temperature adjusted to 0-5C by
the addition of ice. Slowly sodium carbonate was added until the
slurry was slightly alkaline to Brilliant Yellow test paper. With
stirring 39.7 g of N,N-diethanolpropylenediamine and 1.0 ml of pyri-
dine were added and the resulting mixture wa~ stirred approximately
eighteen hours at ambient temperature. The resulting slurry wa~
then heated at 75-85C for approximately one-half hour~ cooled to
room temperature, the solid collected by filtration and washed
with 1000.0 ml of one percent aqueous sodium chloride solution.
After drying at 90C in vacuo,there was obtained 25.0 g of predomi-
nantly bis-N {[3-(diethanolamino)propylamino]sulfonamido} copper
phthalocyanine (Formula II: y=3; R=C2H40H; m=l to 3; n=0 to 1~
a blue solid. The vi~ible absorption spectrum of a dilute acetic
I -48-
~ 16~ 7S(~
D.N. 8111
acid solu~ion o~ the dyestuff containing 0.02 g of the dye per
liter of solution showed a maximum at 614 millimicrons, A=0.6S6.
Sized and unsized paper dyed with dilutions of this
dyestuff in 0~05 percent aqueous acetic acid, according to the
procedure described above, had a turquoise shade and was found
to be highly bleachable~ in the bleach test above. The dye was
found to produce no bleed in the water bleed test and to bleed
slightly in both the soap and milk-bleed tests when tested in
accord with the procedure described above.
B. A mixture of 5.O g of predominantly bis-N-~3-(dieth
anolamino)propylamino~sulfonamido} copper phthalocyanine ob-
tained in part A above, 100.0 ml of distilled water and ~.0 ml
of 98 percent methanesulfonic acid was stirred with heating until
all of the solid was in solution. After cooling to room tempera-
ture,the solution was poured with stirring into 400.0 ml of iso-
propyl alcohol. The blue solid that precipitatod was collected
by filtration and washed with isopropyl alcohol. The alcohol-wet
filter cake was dissolved in 100.0 ml of distilled water with heat-
ing and stirring. After cooling to ambient temperature,the solu-
tion was poured with stirring into 500.0 ml of isopropyl alco~ol.The blue solid that precipitated wa~ collected by filtration,
washed with three 100.0 ml portions of isopropyl alcohol, and
dried in vacuo at 50-55C to obtain 4.7 g of the methanesulfonic
acid addition salt~ of Dredominantl~ bis-N-r~3-(diethanolamino)-
propylamino]sulfonamido} copper phthalocyanine as a dark bluesolid. Elemental analysis established that this product haq an
average per molecule of approximately 2.2 (3-diethanolaminopro-
pyl)sulfonamido substituent~, approximately 0.8 sulfonic acid
substituent and approximately 1.4 complexed methanesulfonic acid
molecules. The visible absorption spectrum of an aqueous solu-
tion of the methanesulfonic ac~d salts containing 0.02 g of dy~
per liter of solution showed a maximum at 615 millimicrons, A=0.627.
-49-
~ 1657~)
D.~. 8111
Unsized paper dyed with an aqueous dilution containing0.1 g per 100.0 ml of the methanesulfonic acid addition salts of
the dyestuff according to the procedure above had a turquoise
shade and was found to be highly bleachable; approximately 97 per-
cent of the dyestuff was destroyed, in the bleach test describedabove. The dye was found to produce no bleed in the water-bleed
test.
It is contemplated that by following procedures similar
to those described in Examples 3 and 4 but employin~ the appro-
priate reactive amine intermediates required for interaction withpoly(chlorosulfonyl) copper phthalocyanines and further employing
the appropriate alkanesulfonic acid, aliphatic or hydroxyaliphatic
acid or inorganic acid there will be obtained the poly(substituted
sulfonamido) copper phthalocyanine acid addition salts of Formula
II~ Examples 6 - 14 presented in Table A hereinbelow:
TABLE A
Poly(N-substituted sulfonamido) copper.
phthalocYanine acid addition salts
Example R y m `Acid
6 ~CH3 3 4 HBr
7 C2H5 3. C2H5S03H
8 n 4 9 2 3 7
9 CH3 2 5 HOC3H6CH
C2H5 2 4 CH3CHOHCOOH
11 i C3H7 C2H5S03H
12 C2H5 4 2 3 7
13 H 2 S HOC3H6CH
14 H 4 3 HBr
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