Fiber-reactive phthalocyanine compound having both vinylsulfone type and dihalogenotriazinyl groups

A phthalocyanine compound represented by the following formula, ##STR1## wherein Pc is a metal-containing or metal-free phthalocyanine residue, R.sup.1 is a hydrogen atom or substituted or unsubstituted lower alkyl group, A is a substituted or unsubstituted phenylene or naphthylene group, Y is --SO.sub.2 CH.dbd.CH.sub.2 or --SO.sub.2 CH.sub.2 CH.sub.2 Z, in which Z is a splittable group by the action of an alkali, W is a bridging group of the following formula, ##STR2## in which R.sup.2 and R.sup.3 are independently a hydrogen atom or a methyl or ethyl group, and n is an integer of from 2 through 6, X is a halogen atom, a is 0 or a number of not more than 2 (0.ltoreq.a.ltoreq.2), and b and c are independently a number of 1 through 3 (1.ltoreq.b.ltoreq.3, 1.ltoreq.c.ltoreq.3), provided that the total of a, b and c is not more than 4 (a+b+c.ltoreq.4), which is useful for dyeing or printing materials, particularly cellulose fiber materials, in a brilliant turquoise blue color excellent in various fastness properties.

The present invention relates to a fiber-reactive phthalocyanine compound, 
a method for producing the same and a method for dyeing or printing 
materials using the same. 
More specifically, the present invention relates to a phthalocyanine 
compound having both fiber-reactive groups, i.e. a so-called vinylsulfone 
type group and a dihalogenotriazinyl group, a method for producing the 
same and a method for dyeing or printing materials, particularly hydroxyl 
group- or amide group-containing fiber materials in a turquoise blue color 
using the phthalocyanine compound. 
As known, there are many kinds of fiber-reactive dyes, and among them, 
reactive dyes having both a so-called vinylsulfone type reactive group 
such as .beta.-sulfatoethylsulfonyl group, and a halogenotriazinyl group 
are particularly prominent because of their characteristic dye 
performances. As phthalocyanine dyes of this kind, Published Examined 
Japanese Patent Application No. 26488/1963 discloses a phthalocyanine 
compound represented by the following formula in a free acid form, 
##STR3## 
wherein CuPc is a copper phthalocyanine residue. Generally speaking, in 
order to be commercialized, fiber-reactive dyes are required to be 
superior in various dye performances such as fastness properties, 
solubility, exhaustion and fixing abilities, build-up, level-dyeing and 
wash-off properties, and insusceptibility to changes in dyeing 
temperatures and bath ratios. In order to be commercially accepted, the 
above known phthalocyanine compound waits for an improvement in such 
various dye performances. 
The present inventors have undertaken extensive studies to find a 
fiber-reactive phthalocyanine compound meeting with such requirements, and 
found a novel phthalocyanine compound. 
The present invention provides a phthalocyanine compound represented by the 
following formula (I) in a free acid form, 
##STR4## 
wherein Pc is a metal-containing or metal-free phthalocyanine residue, 
R.sup.1 is a hydrogen atom or a substituted or unsubstituted lower alkyl 
group, A is a substituted or unsubstituted phenylene or naphthylene group, 
Y is --SO.sub.2 CH.dbd.CH.sub.2 or --SO.sub.2 CH.sub.2 CH.sub.2 Z, in 
which Z is a splittable group by the action of an alkali, W is a bridging 
group of the following formula 
##STR5## 
in which R.sup.2 and R.sup.3 are independently a hydrogen atom or a methyl 
or ethyl group, and n is an integer of from 2 through 6, X is a halogen 
atom, a is 0 or a number of not more than 2 (0.ltoreq.a.ltoreq.2), and b 
and c are independently a number of from 1 through 3 (1.ltoreq.b.ltoreq.3, 
1.ltoreq.c.ltoreq.3), provided that the total of a, b and c is not more 
than 4 (a+b+c.ltoreq.4), and a method for producing the phthalocyanine 
compound of the formula (I), which comprises (1) reacting a phthalocyanine 
sulfochloride with an arylamine compound represented by the following 
formula (II), 
##STR6## 
wherein R.sup.1, A and Y are as defined above, and a diamine compound 
selected from piperazine and compounds represented by the following 
formula (III), 
##STR7## 
ps wherein R.sup.2, R.sup.3 and n are as defined above, to obtain an 
intermediate compound represented by the following formula in a free acid 
form (IV), wherein Pc, W, R.sup.1, A, Y, a, b and c are as defined above, 
and then reacting the intermediate compound of the formula (IV) with a 
trihalogenotriazine represented by the following formula (V), 
##STR8## 
wherein X is as defined above, or (2) reacting the diamine compound with 
the trihalogenotriazine of the formula (V) to obtain a dihalogenotriazine 
compound represented by the following formula (VI), 
##STR9## 
wherein W and X are as defined above, and then reacting the phthalocyanine 
sulfochloride with the dihalogenotriazine compound of the formula (VI) and 
the arylamine compound of the formula (II). 
The present invention also provides a method for dyeing or printing 
materials, which comprises using the phthalocyanine compound of the 
formula (I). 
In the formula (I), a preferred phthalocyanine residue Pc is a 
metal-containing one. The metals include cobalt, nickel and copper, 
preferably nickel and copper. 
A preferred bridging group W is that of the formula, 
##STR10## 
wherein R.sup.2, R.sup.3 and n are as defined above. Particularly 
preferred are those having hydrogen atoms as R.sup.2 and R.sup.3, and 2 or 
3 as n. 
With respect to the unsubstituted or substituted alkyl group represented by 
R.sup.1, the alkyl is preferably the one having 1 to 4 carbon atoms, and 
the substituent includes, for example, a halogen atom and a hydroxyl, 
cyano, alkoxy, carboxy, carbamoyl, alkoxycarbonyl, alkylcarbonyloxy, sulfo 
or sulfamoyl group. Examples of preferred R.sup.1 are hydrogen, methyl, 
ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, 2-hydroxyethyl, 
2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 
4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 
2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 
2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl, 
chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 
3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl, 
3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 
2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbuyl, 
methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 
2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 
4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, 
ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 
3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 
4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 
2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 
2-sulfamoylethyl, 3-sulfoamoylpropyl, 4-sulfamoylbutyl, and the like. Of 
these, particularly preferred is hydrogen. 
The phenylene group A includes those unsubstituted or substituted with one 
or two members selected from, for example, methyl, ethyl, methoxy, ethoxy, 
chlorine, bromine and sulfo, and the naphthylene group A includes those 
unsubstituted or substituted with one sulfo. Preferred examples thereof 
are as follows: 
##STR11## 
(In the above formula, the asterisked linkage is bonded to 
##STR12## 
The splittable group Z includes sulfuric acid ester group, thiosulfuric 
acid ester group, phosphoric acid ester group, acetic acid ester group and 
halogen atom. Of these, preferred is sulfuric acid ester group, and thus 
preferred Y is --SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H. 
The halogen atom X includes chlorine, bromine and fluroine. Of these, 
preferred are chlorine and fluorine, particularly chlorine. 
The phthalocyanine compound of the formula (I) provided by the present 
invention is usually in a mixture of two or more. In other words, a, b and 
c are each average number. Exceptionally, however, the phthalocyanine 
compound (I) may be a single compound. That is, a b and c may be an 
integer. 
The phthalocyanine compound (I) may be in a free acid or preferably in a 
salt of alkali metal or alkaline earth metal. Of these, preferred are 
sodium, potassium and calcium salts. 
Among the phthalocyanine compounds of the formula (I), preferred are those 
having the following formula in a free acid form, 
##STR13## 
wherein CuPc is a copper phthalocyanine residue, R.sup.4 is a hydrogen 
atom or a sulfo or methoxy group, and a', b' and c' are independently a 
number of 1 to 2, provided that the total of a', b' and c' is not more 
than 4. 
The phthalocyanine compound of the formula (I) can be produced, for 
example, in the following manner. 
A mixture of phthalocyanine sulfochloride, the diamine compound selected 
from piperazine and compounds of the formula (III), and the arylamine 
compound (II) can be subjected to condensation reaction, obtaining the 
intermediate compound of the formula (IV). The condensation can be carried 
out in an aqueous medium at a temperature ranging from 0.degree. to 
50.degree. C., while controlling the pH within a range of 5 to 9. 
Successively, the intermediate compound-containing reaction mixture can be 
subjected to condensation with the trihalogenotriazine of the formula (V). 
The condensation can be carried out in an aqueous medium at a temperature 
ranging from 0.degree. to 50.degree. C., while controlling the pH within a 
range of 2 to 8, thus obtaining the desired phthalocyanine compound (I). 
Alternatively, a mixture of the diamine compound and the 
trihalogenotriazine (V) can be subjected to condensation reaction, 
obtaining the dihalogenotriazine compound of the formula (VI). The 
condensation can be carried out in an aqueous medium at a temperature 
ranging from 0.degree. to 30.degree. C., while controlling the pH within a 
range of 5 to 9. Then, the phthalocyanine sulfochloride can be subjected 
to first condensation with any one of the arylamine compound (II) and the 
above dihalogenotriazine compound-containing reaction mixture, followed by 
second condensation with the remaining one, thus obtaining the desired 
phthalocyanine compound (I). The first and second condensation reactions 
can be carried out in an aqueous medium at a temperature of 0.degree. to 
30.degree. C., while controlling the pH within a range of 5 to 9, and at a 
temperature of 10.degree. to 50.degree. C., while controlling the pH 
within a range of 5 to 9, respectively. 
The phthalocyanine compound (I) produced in accordance with the present 
invention may be in a liquid form obtainable by removing inorganic salts 
and/or adding a dyeing improver, if necessary, after completion of the 
reaction, or may be formed into a powdery product by subjecting the above 
liquid or the reaction mixture as such to evaporation such as spray-drying 
and the like, or into either liquid or powdery product through salting out 
of the desired compound in a conventional manner using an electrolyte. 
The compound (I) of the present invention has fiber-reactive groups, and 
can be used for dyeing or printing hydroxyl group- or amide 
group-containing materials, which are preferably in a fibrous form. The 
fiber materials may be blended products. 
The hydroxyl group-containing materials include natural or synthetic 
hydroxyl group-containing fiber materials such as cellulose fiber 
materials, cellulose-containing fiber materials, regenerated products 
thereof and polyvinyl alcohol. Examples of the cellulose fiber materials 
are cotton and other vegetable fibers such as linen, hemp, jute and ramie 
fibers. Examples of the regenerated cellulose fibers are viscose staple 
and filament viscose. 
The amide group-containing materials include synthetic or natural polyamide 
and polyurethane. Examples of the materials, particularly in the fibrous 
forms, are wool and other animal furs, silk, leather, polymide-6,6, 
polyamide-6, polyamide-11 and polyamide-4. 
The dyeing may be carried out in a suitable manner, which can be selected 
from conventional manners depending on the physical and chemical 
properties of said fiber materials. 
For example, cellulose fiber materials can be dyed using the compound (I) 
by an exhaustion dyeing, padding or printing method. 
The exhaustion dyeing can be carried out at a relatively low temperature in 
the presence of an acid binding agent such as sodium carbonate, trisodium 
phosphate, sodium hydroxide and the like, if desired using a neutral salt 
such as sodium sulfate, sodium chloride and the like, optionally together 
with dissolving assistants, penetrants or level dyeing agents. The neutral 
salt which can be used for promoting exhaustion of the dye may be added to 
a dye bath at the time when a temperature reaches a level desired for the 
dyeing, or prior thereto. Alternatively, the neutral salt may be added 
thereto dividedly. 
The padding can be carried out by padding the fiber materials at ambient 
temperature or an elevated temperature, and after drying, steaming or 
dry-heating the materials to perform the dye-fixation. 
The printing can be carried out in a one-phase or two-phase manner. The 
one-phase printing may be conducted by printing the fiber materials with a 
printing paste containing an acid binding agent such as sodium hydrogen 
carbonate and the like, followed by steaming at a temperature of 
100.degree. to 160.degree. C. The two-phase printing may be conducted by 
printing the fiber materials with a neutral or weakly acidic printing 
paste, and passing the materials through a hot alkaline bath containing an 
electrolyte or overpadding the materials with an alkaline padding liquor 
containing an electrolyte, followed by a steaming or dry-heating 
treatment. 
For the preparation of the printing paste, a paste or emulsifier such as 
sodium alginate, starch ether and the like may be used, if desired, 
together with a conventional auxiliary agent such as urea and/or a 
dispersing agent. 
The acid binding agent useful for fixing the compound of the present 
invention on the cellulose fiber materials includes water-soluble basic 
salts consisting of alkali or alkaline earth metals and inorganic or 
organic acids or compounds capable of liberating alkalis under heating 
conditions. Preferred are alkali metal hydroxides and alkali metal salts 
of inorganic or organic acids having a weak or medium strength. 
Particularly preferred are sodium salts and potassium salts. Examples 
thereof are sodium hydroxide, potassium hydroxide, sodium hydrogen 
carbonate, sodium carbonate, sodium formate, potassium carbonate, sodium 
hydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, 
sodium silicate, sodium trichloraacetate and the like. 
The dyeing of natural or synthetic polyamide and polyurethane fiber 
materials can be carried out by performing exhaustion in an acid or weak 
acid bath, while controlling the pH to a desired value, and then making 
the bath neutral, or in some cases alkaline to perform the fixation. The 
dyeing temperautre ranges usually from 60.degree. to 120.degree. C. In 
order to achieve a level dyeing, there may be used a conventional level 
dyeing agent such as a condensation product between cyanuric chloride and 
3 times by mole of aminobenzensulfonic aicd or aminonaphthalenesulfonic 
acid, or an addition product between stearylamine and ethylene oxide, and 
the like. 
The present compound can be characterized by excellent dye performances in 
the dyeing or printing of fiber materials, particularly cellulose fiber 
materials. For example, the compound can give a dyed product excellent in 
light fastness, wet fastness such as washing resistance, peroxide-washing 
resistance, acid-hydrolysis resistance and alkali resistance, and abrasion 
fastness and iron fastness. The compound can also exhibit excellent 
build-up, level-dyring and wash-off properties, favorable solubility and 
high exhaustion and fixation percentages. Moreover, the compound can 
hardly be affected by changes in a dyeing temperature and a dyeing bath 
ratio, so that a dyed product with a constant quality can be given with 
superior reproducibility.

The present invention is illustrated in more detail with reference to the 
following Examples, which are only illustrative and are not intended to 
limit the scope of the present invention. In Examples, parts and % are by 
weight, and CuPc and NiPc are copper phthalochyanine residue and nickel 
phthalocyanine residue, respectively. 
EXAMPLE 1 
Copper phthalocyanine tetrasulfochloride (97 parts on a dry basis) in a wet 
cake was suspended thoroughly in ice water (500 parts), and 
ethylenediamine (6 parts) and aniline-4-.beta.-sulfatoethylsulfone (28 
parts) were added thereto. The mixture was gradually heated to 30.degree. 
C., and stirred at that temperature at that temperature for 15 hours, 
during which the pH was kept within a range of 6 to 8 using a 15% aqueous 
sodium carbonate solution. Thereafter, the reaction mixture was cooled to 
5.degree. C., and mixed with cyanuric chloride (18 parts). The mixture was 
stirred at a temperature of between 5.degree. and 20.degree. C., while 
keeping the pH within a range of 6 to 8, until the condensation was 
completed to obtain a phthalocyanine compound of the following formula in 
a free acid form. 
##STR14## 
The phthalocyanine compound obtained was readily dissolved in water to show 
a blue color. When used as a fiber-reactive dye, the compound can give a 
dyed or printed product of a brilliant turquoise blue color having 
excellent fastness properties such as light fastness and wet fastness 
including washing resistance, acid-hydrolysis resistance and alkali 
resistance. 
EXAMPLE 2 
Copper sulfophthalocyanine trisulfochloride (95 parts on a dry basis) in a 
wet cake was suspended thoroughly in ice water (400 parts), and 
ethylenediamine (9 parts) and aniline-4-.beta.-sulfatoethylsulfone (30 
parts) were added thereto. The mixture was gradually heated to 25.degree. 
C., and stirred at that temperature for 20 hours, during which the pH was 
controlled within a range of 6 to 8 using a 15% aqueous sodium carbonate 
solution. Thereafter, the reaction mixture was cooled to 5.degree. C., and 
then mixed with cyanuric chloride (28 parts). The mixture was stirred at a 
temperature of between 10.degree. and 20.degree. C., while controlling the 
pH within a range of 6 to 8, until the condensation reaction was completed 
to obtain a phthalocyanine compound of the following formula, 
##STR15## 
The compound obtained was readily dissolved in water to show a blue color. 
When used as a fiber-reactive dye, the compound can give a dyed or printed 
product of a brilliant turquoise blue color having excellent fastness 
properties like in Example 1. 
EXAMPLE 3 
Copper phthalocyanine trisulfochloride (87 parts on a dry basis) in a wet 
cake was suspended thoroughly in ice water (550 parts), and then 
ethylenediamine (6 parts and aniline-3-.beta.-sulfatoethylsulfone (42 
parts) were added thereto. The mixture was heated to 30.degree. C., and 
stirred at that temperature for 15 hours, during which the pH was 
controlled within a range of 6 to 8 using a 20% aqueous sodium carbonate 
solution. Thereafter, the reaction mixture was cooled to 5.degree. C., and 
then mixed with cyanuric chloride (18 parts), and the mixture was stirred 
at a temperature of between 5.degree. and 15.degree. C., while controlling 
the pH within a range of 6 to 8, until the condensation reaction was 
completed to obtain a phthalocyanine compound of the following formula. 
##STR16## 
The compound obtained was readily dissolved in water to show a blue color. 
When used as a fiber-reactive dye, the compound can give a dyed or printed 
product of a brilliant blue color excellent in fastness properties like in 
Example 1. 
EXAMPLE 4 
Cyanuric chloride (18 parts) was suspended thoroughly in water (200 parts) 
cooled to 5.degree. C., and then ethylenediamine (6 parts) was added 
thereto. The mixture was stirred at that temperature to complete the 
condensation, while controlling the pH within a range of 5 to 7. 
On the other hand, copper phthalocyanine tetrasulfochloride (97 parts on a 
dry basis) in a wet cake was suspended thoroughly in ince water (400 
parts), and then aniline-3-.beta.-sulfatoethylsulfone (28 parts) was added 
thereto. The mixture was stirred at 10.degree. to 20.degree. C. for 5 
hours, during which the pH was controlled within a range of 6 to 7 using a 
15% aqueous sodium carbonate solution. To this reaction mixture was added 
the above cyanuric chloride-ethylenediamine reaction mixture, and the 
resulting mixture was gradually heated to 30.degree. C. and stirred at 
that temperature for 15 hours, during which the pH was controlled within a 
range of 6 to 8, thus obtaining a phthalocyanine compound the following 
formula. 
##STR17## 
The compound obtained was readily dissolved in water to show a blue color. 
When used as a fiber-reactive dye, the compound can give a dyed or printed 
product of a brilliant tarquoise blue color excellent in fastness 
properties like in Example 1. 
EXAMPLES 5 TO 58 
In a manner similar to any one of Examples 1 to 4, each phthalocyanine 
compound corresponding to the following formula (VII) can be obtained. In 
this manner, the kinds and amounts of the phthalocyanine sulfochloride, 
diamine compounds, arylamine compound and cyanuric chloride can be 
determined so as to correspond to each phthalocyanine compound shown in 
the following Table. 
##STR18## 
__________________________________________________________________________ 
Example 
Compound corresponding to the formula (VII) 
No. W R.sup.1 AY a b c Color 
__________________________________________________________________________ 
5 
H 
##STR19## 2 1 1 Turquoise blue 
6 " " 
##STR20## " " " " 
7 " " 
##STR21## " " " " 
8 " " 
##STR22## " " " " 
9 " CH.sub.3 
##STR23## " " " " 
10 " CH.sub.2 CH.sub.3 
" " " " " 
11 " CH.sub.2 CN 
" " " " " 
12 " CH.sub.2 CONH.sub.2 
" " " " " 
13 " CH.sub.2 CO.sub.2 H 
" " " " " 
14 " CH.sub.2 CH.sub.2 OH 
" " " " " 
15 " CH.sub.2 CH.sub.2 OCH.sub.3 
" " " " " 
16 " CH.sub.2 CH.sub.2 CN 
" " " " " 
17 " CH.sub.2 CH.sub.2 CONH.sub.2 
" " " " " 
18 " CH.sub.2 CH.sub.2 CH.sub.3 
" " " " " 
19 " CH.sub.2 CH.sub.2 SO.sub.2 NH.sub.2 
" " " " " 
20 " 
##STR24## 
" " " " " 
21 " 
##STR25## 
" " " " " 
22 " CH.sub.2 CH.sub.2 SO.sub.3 H 
" " " " " 
23 
##STR26## H 
##STR27## " " " " 
24 " CH.sub.2 CH.sub.3 
" " " " " 
25 
##STR28## H " " " " " 
26 " CH.sub.2 CH.sub.3 
" " " " " 
27 
##STR29## H " " " " " 
28 " CH.sub.2 CH.sub.3 
" " " " " 
29 
##STR30## H " " " " " 
30 " CH.sub.2 CH.sub.3 
" " " " " 
31 
##STR31## H " " " " " 
32 
##STR32## CH.sub.2 CH.sub.3 
" " " " " 
33 
##STR33## H " " " " " 
34 " CH.sub.2 CH.sub.3 
" " " " " 
35 
##STR34## H " 1.5 
1 1.5 
" 
36 " " " 1.5 
1.5 
1 " 
37 " " " 1 1.5 
1.5 
" 
38 " " " 1 1 1 " 
39 " " " 0.5 
1 1.5 
" 
40 " " " 0.5 
1.5 
1 " 
41 
##STR35## " " 1.5 
1.5 
1 " 
42 " " " 1.5 
1 1.5 
" 
43 
##STR36## " 
##STR37## 2 1 1 " 
44 " " 
##STR38## " " " " 
45 " " 
##STR39## " " " " 
46 " " 
##STR40## " " " " 
47 " " 
##STR41## " " " " 
48 " " 
##STR42## " " " " 
49 " " 
##STR43## " " " " 
50 
##STR44## " 
##STR45## " " " " 
51 " CH.sub.2 CH.sub.3 
" " " " " 
52 
##STR46## " 
##STR47## " " " " 
53 " " 
##STR48## " " " " 
54 " " 
##STR49## " " " " 
55 " " 
##STR50## " " " " 
56 " " 
##STR51## " " " " 
57 " " 
##STR52## " " " " 
58 " " 
##STR53## " " " " 
__________________________________________________________________________ 
EXAMPLE 59 
Example 1 was repeated, provided that nikel phthalocyanine 
tetrasulfochloride was used in an equimolar amount to that of the copper 
phthalocyanine tetrasulfochloride used in Example 1, thereby obtaining a 
phthalocyanine compound of the following formula, 
##STR54## 
The compound obtained was readily dissolved in water to show a deep green 
color. When used as a fiber-reactive dye, the compound can give a dyed or 
printed product of a brilliant green color excellent in fastness 
properties such as light fastness and wet fastness including washing 
resistance, acid-hydrolysis resistance and alkali resistance. 
EXAMPLE 60 
Copper phthalocyanine tetrasulfochloride, ethylenediamine and 
aniline-4-.beta.-sulfatoethylsulfone were subjected to condensation in the 
same manner as in Example 1. To this reaction mixture cooled to 0.degree. 
C. was dropwise added 2,4,6-trifluoro-1,3,5-triazine (14 parts) along with 
a 15% aqueous sodium carbonate solution to control the pH within a range 
of 6 to 8, and the mixture was stirred at 50.degree. to 10.degree. C. and 
at that pH to complete the condensation, thus obtaining a phthalocyanine 
compound of the following formula. 
##STR55## 
EXAMPLE 61 
The phthalocyanine compound (0.1, 0.3 and 0.6 part) obtained in Example 1 
was respectively dissolved in water (200 parts). To each solution were 
added sodium sulfate (10 parts) and cotton (10 parts). The dyeing bath was 
heated to 60.degree. C. and then sodium carbonate (4 parts) was added 
thereto. Dyeing was continued at that temperature for 1 hour. The cotton 
was washed with water, soaped, again washed with water and then dried to 
obtain a dyed product of a brilliant turquoise blue color excellent in 
fastness properties such as light fastness and wet fastness. 
From the results of the above three dyeings, the compound was found to be 
excellent in solubility, build-up and level-dyeing properties and 
reproducibility. 
EXAMPLE 62 
The phthalocyanine compound (3 parts) obtained in Example 2 was dissolved 
in water (2000 parts), and sodium sulfate (200 parts) and cotton (100 
parts) were added thereto. The bath was heated to 50.degree. C. 30 Minutes 
thereafter, sodium hydroxide (30 parts) were added thereto, and dyeing was 
continued for 1 hour at that temperature. The cotton was washed with 
water, soaped, again washed with water and then dried to obtain a dyed 
product of a brilliant turquoise blue color having excellent fastness 
properties like in Example 61. 
EXAMPLE 63 
______________________________________ 
Composition of color paste 
______________________________________ 
Compound obtained in Example 1 
5 parts 
Urea 5 parts 
Sodium alginate (5%), thickener 
50 parts 
Hot water 25 parts 
Sodium hydrogencarbonate 
2 parts 
Balance (water) 13 parts 
______________________________________ 
Mercerized cotton broad cloth was printed with the color paste of the above 
composition, then pre-dried, steamed for 5 minutes at 100.degree. C., 
rinsed with hot water, soaped, again rinsed with hot water, and dried to 
obtain a printed product of a brilliant turquoise blue color excellent in 
fastness properties, particularly light fastness and wet fastness.