Amine pyrazole nickel phthalocyanine dyes for coloration

Details Amine pyrazole nickel phthalocyanine dyes for coloration Amine pyrazole nickel phthalocyanine dyes for coloration

1993-08-17

2001-08-07

Higel, Floyd D. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Azo

C534S619000, C534S638000, C534S603000, C534S613000, C534S626000

Reexamination Certificate

active

06271355

ABSTRACT:

This invention relates to a dye suitable for use in the coloration of materials having a hydroxy or —NH— group, to a process for its manufacture, to a process for the coloration of materials with the dye and to materials so colored.
According to the present invention there is provided a dye which, in the free acid form, is of Formula (1):
wherein:
NiPc is a nickel phthalocyanine radical;
r has a value from 1 to 3 inclusive;
m has a value from 1 to 3 inclusive;
p has a value from 0 to 1 inclusive;
R
1
is H, alkyl, substituted alkyl, aryl or substituted aryl;
R
2
, R
3
and R
4
are each independently H, C
1-6
-alkyl or substituted C
1-6
-alkyl;
A is phenylene, substituted phenylene, C
1-6
-alkylene or substituted C
1-6
-alkylene;
Q is a labile substituent;
B is phenylene, phenylene substituted by 1 or 2 sulpho groups, or phenylene substituted by an alkyl or alkoxy group;
Z is H or alkyl; and
X and Y are each independently H, alkyl, alkoxy, halogen, carboxy or sulpho;
provided that r+m+p does not exceed 4.
It is preferred that the substituents shown in brackets in Formula (1) are bonded to the 3-positions of the phenyl rings in the phthalocyanine nucleus.
When any of A, R
1
, R
2
, R
3
and R
4
are substituted it is preferred that the substituents are independently selected from CH
3
, OCH
3
, halo, NO
2
CN, NHCOCH
3
, NH
2
and especially hydroxy, sulpho and carboxy.
R
1
, R
2
, R
3
and R
4
are preferably independently H or C
1-4
-alkyl, especially H.
When the group represented by A is C
1-6
-alkylene it is preferably C
1-3
-alkylene such as —CH
2
CH
2
13
or —CH
2
CH
2
CH
2
—. However, it is preferred that A is phenylene or substituted phenylene, more preferably phenylene, especially 1,3-phenylene.
A labile substituent is one capable of being displaced by nucleophilic substitution during exhaust dyeing to form a covalent bond between the triazinyl ring in Formula (1) and the nucleophile. The labile substituent Q is preferably halo such as F or Br, and more especially Cl. However, Q can also be a quaternary ammonium group such as tri-(C
1-4
) alkyl ammonium, e.g. (CH
3
)
3
N
+
— or a pyridinium group such as one derived from a pyridine carboxylic acid e.g. from nicotinic acid or isonicotinic acid.
B is preferably phenylene or phenylene substituted by 1 or 2 sulpho groups or by a group selected from C
1-4
-alkyl, especially methyl and C
1-4
-alkoxy, especially methoxy. It is more preferable that B is phenylene or phenylene substituted by 1 or 2 sulpho groups, especially by 2 —SO
3
H groups. As examples of groups represented by B there may be mentioned 4-sulpho-1,3-phenylene and 4,6-disulpho-1,3-phenylene.
Z is preferably H or C
1-4
-alkyl, especially methyl.
It is preferred that X and Y are each independently selected from the group H, C
1-4
-alkyl, carboxy, C
1-4
-alkoxy, halogen and sulpho, more preferably H, methyl, methoxy, Cl, Br and sulpho.
For convenience of manufacture it is preferred that the sum of r+m+p is 4. p preferably has a value of 0. In a particularly preferred class of dyes p has a value of 0, and r+m is 4 and the ratio of r:m is in the range 1:3 to 3:1, especially approximately 1:2 to 2:1.
In a preferred aspect of the present invention the dye comprises a composition containing two or more of the structures of Formula (1) as hereinbefore defined, especially structures which differ only in the respective values of r, m and p; such compositions are of value in the coloration of cellulosic materials and leathers.
The present invention also provides a process (wherein R
1
, R
2
, R
3
, R
4
, NiPc, p, r, m, A, B, X, Y, Z are as defined above and Q is halo) for the manufacture of dyes of Formula (1) which comprises coupling a compound of formula NiPc(SO
2
Cl)
p+r+m
with a diamine of formula HN(R
2
)—A—N(R
3
)(R
5
) (wherein R
5
is either H or a protecting group, especially a protecting group which is removable by hydrolysis, for example CH
3
CO—) to give compound of Formula (2):
NiPc(SO
2
Cl)
p+r
[(SO
2
N(R
2
)—A—N(R
3
)(R
5
)]
m
  (2)
which is treated with aqueous base to convert (SO
2
Cl) to (SO
3
H) and remove the protecting group R
5
when present to give a compound of Formula (3):
NiPc(SO
3
H)
p+r
[(SO
2
N(R
2
)—A—N(R
3
)H]
m
  (3)
A compound of formula HN(R
4
)—B—NH
2
is reacted with a cyanuric halide, preferably below 10° C., to give a mono-adduct which is subsequently diazotised using a diazotising agent, e.g. NaNO
2
, at below 5° C. to give a diazo suspension of Formula (4) which is coupled, preferably in the presence of phosphate buffer, with a compound of Formula (5) to give a dichlorotriazinyl azo yellow component of Formula (6).
The dyes of Formula (1) wherein p has a value of 0 are prepared by condensing compounds of Formulae (3) and (6), preferably at a pH of between 6.5 and 7.
Dyes of Formula (1) wherein Q is quaternary ammonium can be prepared by making the corresponding compound in which Q is Cl, which is preferably prepared by the above process, then reacting with the appropriate amine to make the corresponding quaternary ammonium salt.
Dyes of Formula (1) wherein p is greater than 0 can be prepared by using the above process except that the compound of Formula (2) is reacted with an amine of formula R
1
NH
2
before said treatment with aqueous base.
It is to be understood that the present invention relates not only to dyes of Formula (1) but also to salts thereof, particularly the salt with an alkali metal, ammonia or a water-soluble amine especially the sodium, lithium, potassium or mixed sodium/lithium salt.
The term “dye” when used in this specification as a noun does not limit the invention to compounds which are intended for use as a dye, although in a preferred embodiment the compounds of the invention are in fact intended for use as dyes.
The dye of the invention is characterised by its good dyeing properties, and in particular its good build up on cotton, its attractive green shade and excellent fastness to wet treatments and to light. The surprisingly high solubility of a dye according to the invention in salt solutions is of great value in exhaust dyeing where such solutions are used. The dye is also valuable for colouring leather on which it is found to have good build up properties, good penetration and excellent fastness to wet treatments and to light.
According to a further aspect of the present invention there is provided a process for the coloration of a material, particularly a material having a hydroxy or —NH— group, such as a cellulosic material (e.g. cotton, jute, hemp or flax), animal hairs, an animal skin or a leather, comprising applying thereto a dye of Formula (1). It is preferred that the coloration of cellulosic materials is performed under alkaline conditions, for example in the presence of an acid binding agent. For the coloration of animal hairs, skins and leather coloration is preferably performed under weakly acid conditions. A still further aspect of the invention provides materials, such as those described above, when colored by the coloration process or with a dye of Formula (1).


REFERENCES:
patent: 3082201 (1963-03-01), Koller
patent: 3123594 (1964-03-01), Koller et al.
patent: 3362949 (1968-01-01), Benz et al.
patent: 3697500 (1972-10-01), Ackermann et al.
patent: 3988310 (1976-10-01), Gerlach et al.
patent: 4515598 (1985-05-01), Meininger et al.
patent: 659820 (1984-02-01), None
patent: 0947779 (1964-01-01), None
patent: 1003786 (1965-09-01), None
patent: 1035006 (1966-07-01), None

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