Polyazo compound and method for dyeing or textileprinting fiber material using the same

FIELD OF THE INVENTION
The present invention relates to a novel polyazo compound and a salt thereof.
BACKGROUND OF THE INVENTION
As a dye for dyeing or textile printing a fiber material, for example, azo compounds having a vinyl sulfone reactive group have hitherto been known (e.g. JP-A-50-178, JP-A-63-77947, JP-A-6-287463).
However, even when these azo compounds are used for dyeing or textile printing fiber materials such as natural or regenerated cellulose fiber, they do not satisfy the reproducibility, levelness, color value, build-up properties, chlorine atom treated water fastness, tap water chlorine atom fastness, light fastness, perspiration light fastness, etc. Therefore, it has been desired to develop a dye which satisfies these performances. Also, it has strongly been desired to develop a dye which causes little discoloration at the time of various processing treatments; affords a dyed or textile-printed product having excellent storage stability; and exhibits high effective dyeing ratio capable of reducing a coloration of dyeing waste water with the recent increase of interest about environmental problems.
Under these circumstances, the present inventors have studied intensively for the purpose of obtaining a dye which is excellent in reproducibility and levelness, and exhibits high build up properties, high color value and high effective dyeing ratio in a dyeing and textile-printing treatment of fiber materials; and affords a dyed or textile-printed product which is excellent in fastnesses, particularly chlorine atom treated water fastness, tap water chlorine atom fastness, light fastness and perspiration light fastness, causes little discoloration at the time of various processing treatments, and exhibits excellent storage stability. As a result, it has been found that a specific polyazo compound or a salt thereof has desired performances. Thus, the present invention has been accomplished.
SUMMARY OF THE INVENTION
The present invention provides a polyazo compound represented by the following formula (I): ##STR2## wherein A represents unsubstituted phenylene, phenylene substituted with at least one non-reactive substituent, unsubstituted naphthylene or naphthylene substituted with at least one non-reactive substituent;
E represents unsubstituted hydroxynaphthylene, or hydroxynaphthylene substituted with at least one non-reactive substituent;
m, m.sup.1 and m.sup.3 independently represent an integer of 0 or 1;
B represents hydrogen atom, --SO.sub.2 -Z in which Z represents --CH.dbd.CH.sub.2 or --CH.sub.2 CH.sub.2 Y in which Y represents a group eliminatable by the action of an alkali, or a group represented by the following formula (1), (2) or (3): ##STR3## wherein
G represents a group represented by the following formula (4) or (5): ##STR4## wherein
"a" represents to bond with A or E; and R represents hydrogen atom or optionally substituted lower alkyl;
R.sup.1 represents a group represented by the following general formula (7), (8), (9) or (10): ##STR5## wherein
R.sup.7 represents hydrogen atom or optionally substituted lower alkyl;
D represents optionally substituted phenylene or optionally substituted naphthylene;
Z represents the same definition as above;
W.sup.1 represents optionally substituted straight-chain or branched lower alkylene;
R.sup.8 represents hydrogen atom, optionally substituted lower alkyl or --W.sup.1 --CH.sub.2 SO.sub.2 Z in which W.sup.1 and Z represent the same definition as above;
W.sup.2 and W.sup.3 independently represent straight-chain or branched alkylene having 2 to 6 carbon atoms;
Q represents --O-- or --NR.sup.9 -- in which R.sup.9 represents hydrogen atom or lower alkyl; and
p represents an integer of 1 to 6;
R.sup.2, which is same as or different from R.sup.1, represents fluorine atom; chlorine atom; optionally substituted amino; --OR.sup.10 or --SR.sup.10, in which R.sup.10 represents hydrogen atom, optionally substituted lower alkyl or optionally substituted phenyl;
a group represented by the following formula (6): ##STR6## wherein R.sup.6 represents hydrogen atom, lower alkyl, carbamoyl or carboxyl;
or a group represented by the formula (7), (8), (9) or (10);
R.sup.3 and R.sup.4 independently represent fluorine atom, chlorine atom or hydrogen atom; and
R.sup.5 represents hydrogen atom, fluorine atom, chlorine atom, cyano or lower alkyl;
and
B.sup.1, which is same as or different from B, represents hydrogen atom or a group represented by the formula (1), (2) or (3); provided that when B represents hydrogen atom, B.sup.1 represents a group represented by the formula (1), (2) or (3); and when B.sup.1 represents hydrogen atom, B represents --SO.sub.2 -Z in which Z represents the same definition as above or a group represented by the formula (1), (2) or (3);
or a salt of the polyazo compound represented by the formula (I).
The present invention also provides a method for dyeing or textile-printing a fiber material, using the polyazo compound represented by the formula (I).
The present invention will be explained in detail hereinafter.
DETAILED DESCRIPTION OF THE INVENTION
The group represented by B in the formula (I) is hydrogen atom, --SO.sub.2 -Z in which Z represents same meaning as above or group represented by the formula (1), (2) or (3). Among them, hydrogen atom, --SO.sub.2 -Z in which Z represents same meaning as above and a group represented by the formula (1) are preferred as B. Particularly, hydrogen atom and a group represented by the formula (1) are preferred as B. When B.sup.1 is hydrogen atom, B represents --SO.sub.2 -Z in which Z represents same meaning as above or a group represented by the formula (1), (2) or (3).
The group represented by B.sup.1 in the formula (I) is hydrogen atom or group represented by the formula (1), (2) or (3). Among them, hydrogen atom and a group represented by the formula (1) are preferred. When B represents hydrogen atom, B.sup.1 represents a group represented by the formula (1), (2) or (3).
As a group represented by G in the formula (1), (2) or (3), a group of the formula (4) is preferred.
As the substituent R.sup.1 of the formula (1), groups of the general formulas (7) and (8) are preferred.
As the substituent R.sup.2 of the formula (1), fluorine atom, chlorine atom, groups of the general formulas (7) and (8) and amino groups represented by the following formulas (16) and (17): ##STR7## wherein
R.sup.15 represents hydrogen atom, cyano or optionally substituted lower alkyl;
R.sup.16 represents hydrogen atom, optionally substituted lower alkyl, optionally substituted phenyl, optionally substituted naphthyl or optionally substituted cycloalkyl having 5 to 7 carbon atoms in the cycloalkyl moiety;
n represents 1 or 2; and
Q.sup.2 represents --O--, --S--, --CH.sub.2 --, --SO.sub.2 -- or --NR.sup.17 in which R.sup.17 represents hydrogen atom or lower alkyl are preferred. Among them, a group represented by the formula (7), (8), (16) or (17) is preferred.
In the formula (I) representing the polyazo compound of the present invention, A represents optionally substituted phenylene or optionally substituted naphthylene. Examples of the optionally substituted phenylene include unsubstituted phenylene, phenylene substituted with 1, 2 or 3 substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo, carboxy, nitro, acylamino preferably having 1 to 4 carbon atoms, sulfo and a group represented by the following general formula (18) or (19):
--NHCOR.sup.18 (18)
--NHSO.sub.2 R.sup.18 (19)
wherein R.sup.18 represents optionally substituted lower alkyl, optionally substituted phenyl or optionally substituted naphthyl.
Examples of the phenyl group represented by "-A-B" in the formula (I) include the following groups: ##STR8## wherein B has the same definition as above. Among them, groups having a substituent at the ortho-position relative to the bonding position of the azo group are preferred. Examples of the particularly preferred group include groups represented by the following formulas: ##STR9## wherein B has the same definition as above.
Examples of the optionally substituted naphthylene represented by A in the formula (I) include unsubstituted naphthylene or naphthylene substituted with 1, 2 or 3 sulfo groups.
Specific examples of the naphthyl group represented by -A-B in the formula (I) include groups represented by the following formulas: ##STR10## wherein B has the same definition as above. Among them, groups having a substituent at the ortho-position relative to the bonding position of an azo group are preferred. Particularly preferred are groups represented by the following formulas: ##STR11## wherein B has the same definition as above.
Examples of the optionally substituted hydroxynaphthylene represented by E in the formula (I) include unsubstituted hydroxynaphthylene and hydroxynaphthylene substituted with substituents selected from 1, 2 or 3 sulfo groups, a group represented by the formula (18) or a group represented by the formula (19). As the substituent of hydroxynaphthylene represented by E, 1, 2 or 3 sulfo groups and a group represented by the formula (18) are preferred.
Preferred examples of the group represented by "-E-B.sup.1 " in the formula (I) include groups represented by the following formulas: ##STR12## wherein B.sup.1 has the same definition as above.
Among them, groups represented by the following formulas: ##STR13## wherein B.sup.1 has the same definition as above are particularly preferred.
The group represented by R in the formula (4) representing G is hydrogen atom or optionally substituted lower alkyl. The optionally substituted lower alkyl represented by R is, for example, alkyl having 1 to 4 carbon atoms in the alkyl moiety. Examples of the substituent on the alkyl represented by R include hydroxy, cyano, alkoxy preferably having 1 to 4 carbon atoms, halogeno, carbamoyl, carboxy, alkoxycarbonyl preferably having 1 to 4 carbon atoms in the alkoxy moiety, alkylcarbonyloxy preferably having 1 to 4 carbon atoms in the alkyl moiety, sulfo and sulfamoyl.
Specific examples of the alkyl represented by R include methyl, ethyl, n-propyl, iso-propyl, 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-carbamoylbutyl, 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-sulfamoylpropyl and 4-sulfamoylbutyl.
As R, hydrogen atom, methyl or ethyl is preferred. Among them, hydrogen atom is particularly preferred.
D in the formula (7) represents optionally substituted phenylene or optionally substituted naphthylene Examples of the phenylene represented by D include unsubstituted phenylene or phenylene substituted with 1 or 2 substituents selected from the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo. Specific examples thereof include: ##STR14## wherein a bond represented by "d" indicates a bond attached to nitrogen atom. Among them, groups represented by the following formulas: ##STR15## wherein d has the same definition as above are preferred. Particularly preferred groups are groups represented by the following formulas: ##STR16## wherein d has the same definition as above.
Examples of the optionally substituted naphthylene represented by D include unsubstituted naphthylene and naphthylene substituted with 1 or 2 sulfo groups. Specific examples thereof include those represented by the following formulas: ##STR17## wherein d has the same definition as above. Among them, groups represented by the following formulas: ##STR18## wherein d has the same definition as above are preferred.
In the formula (6), R.sup.6 represents hydrogen atom, lower alkyl, carbamoyl or carboxyl. Specific examples of the lower alkyl represented R.sup.6 include an alkyl group having 1-4 carbon atom, such as methyl, ethyl, n-propyl, isopropyl, n-butyl iso-butyl and sec-butyl.
As R.sup.6, hydrogen atom, carbamoyl and carboxyl are preferred. Among them, carboxyl is particularly preferred.
In the formula (7), R.sup.7 represents hydrogen atom or optionally substituted lower alkyl. Specific examples of the lower alkyl represented R.sup.7 include those exemplified above as examples of lower alkyl represented by R in the formula (4). As R.sup.7, hydrogen atom, methyl and ethyl are preferred. Among them, hydrogen atom is particularly preferred.
W.sup.1 in the formula (8) represents optionally substituted lower alkylene. Examples of the lower alkylene represented by W.sup.1 include straight-chain or branched alkylene having 1 to 5 carbon atoms in the alkylene moiety. Specific examples thereof include methylene, ethylene, methylmethylene, trimethylene and tetramethylene. Examples of the substituent of the lower alkylene include halogeno, hydroxy, sulfate, carboxy, cyano, lower alkylcarbonyloxy, lower alkoxycarbonyl, carbamoyl, and --SO.sub.2 Z (wherein Z has the same definition as above).
Examples of the alkyl in the lower alkylcarbonyloxy a substituent on the alkylene represented by W.sup.1, include alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl. Examples of the alkoxy in the lower alkoxycarbonyl, a substituent on the alkylene represented by W.sup.1, include alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy and sec-butoxy.
Examples of the preferred group for W.sup.1 include methylene, ethylene, methylmethylene, trimethylene and tetramethylene. Among them, methylene and ethylene are particularly preferred.
R.sup.8 in the general formula (8) represents hydrogen atom, optionally substituted lower alkyl and a group represented by --W.sup.1 --CH.sub.2 SO.sub.2 Z (wherein W.sup.1 and Z have the same definitions as above). Specific examples of the optionally substituted lower alkyl represented by R.sup.8 include those exemplified above as examples of lower alkyl represented by R in the formula (4).
As R.sup.8, hydrogen atom, methyl and ethyl are preferred. Among them, hydrogen atom is particularly preferred.
W.sup.2 and W.sup.3 in the formula (9) represent straight chain or branched alkylene having 2 to 6 carbon atoms. Specific examples of the lower alkylene represented by W.sup.2 or W.sup.3 in the formula (9) include ethylene, methylmethylene, trimethylene and tetramethylene.
Among them, ethylene is preferred.
In the general formula (9), Q represents --O-- or --NR.sup.9 in which R.sup.9 represents hydrogen atom or lower alkyl. Specific examples of the lower alkyl represented by R.sup.9 include alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl.
Among them, --O-- and --NH-- are preferred, and --O-- is particularly preferred.
In the formula (10), p represents an integer of 1 to 6. As "p", the integer, 2, 3 or 4 is preferred.
Z in the general formulas (7), (8), (9) and (10) represents --CH.dbd.CH.sub.2 or --CH.sub.2 CH.sub.2 Y in which Y represents a group which is eliminatable by an action of an alkali. Examples of the group represented by Y include sulfate, thiosulfate, phosphate, acetate and halogeno. Among them, chloro or sulfate is particularly preferred. Preferred examples of Z include groups such as --CH.dbd.CH.sub.2, --CH.sub.2 CH.sub.2 Cl and --CH.sub.2 CH.sub.2 OSO.sub.3 H.
R.sup.2 in the formula (1) may be amino. Examples of the amino represented by R.sup.2 include those represented by the formulas (16) and (17).
R.sup.15 in the general formula (16) represents hydrogen atom, cyano or optionally substituted lower alkyl. Specific examples of the lower alkyl represented by R.sup.15 include those exemplified above as examples for lower alkyl represented by R in the formula (4). Preferred examples of the group represented by R.sup.15 include alkyl having 1 to 4 carbon atoms which is unsubstituted or substituted with alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, hydroxy or sulfate. Among them, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, .beta.-hydroxyethyl, .beta.-sulfate ethyl, .beta.-sulfo ethyl, .beta.-methoxyethyl and .beta.-carboxyethyl are particularly preferred.
R.sup.16 in the general formula (16) represents hydrogen atom, optionally substituted lower alkyl, optionally substituted phenyl, optionally substituted naphthyl or optionally substituted cycloalkyl having 5 to 7 carbon atoms in the cycloalkyl moiety. Specific examples of the lower alkyl include those exemplified above as examples of lower alkyl represented by R in the formula (4).
Examples of the optionally substituted phenyl represented by R.sup.16 in the formula (16) include unsubstituted phenyl and phenyl substituted with 1, 2 or 3 substituents selected from the group consisting of sulfo, halogeno, lower alkyl, lower alkoxy, carboxy and nitro.
Specific examples of the lower alkyl, the substituent on the phenyl represented by R.sup.16, include alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and sec-butyl. Specific examples of the lower alkoxy, the substituent on the phenyl represented by R.sup.16, include alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy and sec-butoxy.
Preferred examples of the optionally substituted phenyl represented by R.sup.16 include phenyl, 2-, 3- or 4-sulfophenyl, 2,4- or 2,5-disulfophenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methoxyphenyl, 2-carboxy-4- or 5-sulfophenyl, 2-sulfo-4- or 5-methylphenyl, 2-sulfo-4- or 5-methoxyphenyl, 2-methyl-4- or 5-sulfophenyl and 2-methoxy-4- or 5-sulfophenyl.
The optionally substituted naphthyl represented by R.sup.16 is, for example, naphthyl which is unsubstituted or substituted with 1, 2 or 3 sulfo groups.
The optionally substituted cycloalkyl having 5 to 7 carbon atoms represented by R.sup.16 is, for example, cycloalkyl which is unsubstituted or substituted with methyl, ethyl, fluorine atom, chlorine atom or hydroxy.
In the general formula (16), when R.sup.16 is optionally substituted phenyl, R.sup.15 is preferably hydrogen, methyl or ethyl. When R.sup.16 is optionally substituted naphthyl, R.sup.16 is preferably hydrogen.
Q.sup.2 in the general formula (17) represents --O--, --S--, --CH.sub.2 --, --SO.sub.2 -- or --NR.sup.17 -- in which R.sup.17 represents hydrogen atom or lower alkyl. Specific examples of the lower alkyl represented by R.sup.17 include lower alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and sec-butyl.
In the general formula (17), n is preferably 2 and Q.sup.2 is preferably --CH.sub.2 -- or --O--.
Examples of the group, B or B.sup.1, represented by the general formula (2) include groups represented by the following formulas: ##STR19## wherein G has the same definition as above. The lower alkyl group represented by R.sup.5 in formula (2) preferably has 1 to 4 carbon atoms.
R.sup.2 in the formula (1) may be a group represented by --OR.sup.10 or --SR.sup.10 in which R.sup.10 represents hydrogen atom, optionally substituted lower alkyl or optionally substituted phenyl. Specific examples of the lower alkyl group represented by R.sup.10 include same optionally substituted lower alkyl groups to those exemplified above as examples of lower alkyl represented by R in the formula (4).
Examples of the optionally substituted phenyl represented by R.sup.10 is phenyl which is unsubstituted or substituted with 1, 2 or 3 substituents selected from the group consisting of sulfo, halogeno, lower alkyl, lower alkoxy, carboxy and nitro.
Specific examples of the lower alkyl, the substituent on the phenyl represented by R.sup.10, include alkyl having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and sec-butyl. Specific examples of the lower alkoxy, the substituent on the phenyl represented by R.sup.10, include alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy and sec-butoxy.
R.sup.18 in the formula (18) and (19) represents optionally substituted lower alkyl, optionally substituted phenyl or optionally substituted naphthyl. Specific examples of the lower alkyl include optionally substituted lower alkyl having 1 to 4 carbon atoms which is the same as those described above as examples for R in the general formula (4).
As the lower alkyl represented by R.sup.19, methyl, ethyl or 2-carboxyethyl are preferred.
Examples of the optionally substituted phenyl represented by R.sup.18 include phenyl which is unsubstituted or substituted with 1, 2 or 3 substituents selected from the group consisting of sulfo, halogeno, lower alkyl preferably having 1 to 4 carbon atoms, lower alkoxy preferably having 1 to 4 carbon atoms, carboxy and nitro.
Examples of the optionally substituted naphthyl represented by R.sup.18 include naphthyl which is unsubstituted or substituted with 1, 2 or 3 sulfo groups.
In the general formula (I), m.sup.3 is preferably 0.
The polyazo compound represented by the formula (I) of the present invention can be produced in the following manner.
When m.sup.3 is 1, the manner is as follows:
A compound represented by the following formula (II):
B-A-NH.sub.2 (II)
wherein A and B have the same definitions as above, or a salt thereof is diazotized; and then
the diazotized compound is diazo-coupled with a compound represented by the following formula (III): ##STR20## wherein m has the same definition as above, or a salt thereof to obtain a compound represented by the following formula (III-1): ##STR21## wherein A, B and m have the same definitions as above, or a salt thereof.
The compound thus obtained, i.e. Compound (III-1) or its salt, is diazotized; and, then, the diazotized compound is diazo-coupled with a compound represented by the following formula (III-2): ##STR22## wherein m.sup.1 has the same definition as above, or a salt thereof to obtain a compound represented by the following formula (IV): ##STR23## wherein A, B, m and m.sup.1 have the same definitions as above, or a salt thereof.
Thereafter, the compound thus obtained, i.e. Compound (IV) or its salt, is diazotized; and, then, the diazotized compound is diazo-coupled with a compound represented by the following general formula (V);
H-E-B.sup.1 (V)
wherein E and B.sup.1 have the same definitions as above, or a salt thereof to obtain a polyazo compound represented by the formula (I) or a salt thereof of the present invention.
When m.sup.3 is 0, the polyazo compound of the present invention can be produced by diazotizing a compound represented by the formula (III-1) or a salt thereof, followed by diazo-coupling the diazotized compound with a compound represented by the formula (V).
When B is a group represented by the formula (1), the amino compound of the formula (II) can be obtained by condensing a compound represented by the following general formula (VI):
R.sup.1 --H (VI)
wherein R.sup.1 has the same definition as above, a compound represented by the following formula (VII):
R.sup.2' --H (VII)
wherein R.sup.2' has the same definition as R.sup.2 mentioned above except for excluding fluorine atom and chlorine atom, and a compound represented by the following general formula (VIII):
H.sub.2 N-A-G-H (VIII)
wherein A and G have the same definitions as above with a 2,4,6-trihalogeno-s-triazine in any order.
In the condensation reaction between the above compounds and 2,4,6-trihalogeno-s-triazine, the order is not specifically limited and the reaction conditions are not specifically limited either, although the first condensation, i.e. the condensation reaction with unsubstituted 2,4,6-trihalogeno-s-triazine is preferably carried out at the temperature of -10 to 40.degree. C. and pH 2-9, the second condensation, i.e. the condensation reaction with the dihalogeno-s-triazine obtained in the first condensation, is preferably carried out at the temperature of 0 to 70.degree. C. and pH 2-9, and the third condensation, i.e. the condensation reaction with the halogeno-s-triazine obtained in the second condensation, is preferably carried out the temperature of 10 to 100.degree. C. and pH 2-7.
When B represent a group of formula (1) in which R.sup.2 represent halogen, the compound represented by the general formula (II) can be obtained by omitting the third condensation according to the above synthesis method.
When B is a group represented by the general formula (2), the compound represented by the general formula (II) can be obtained by condensing a compound represented by the formula (VIII) with a compound represented by the following general formula (IX): ##STR24## wherein R.sup.3, R.sup.4 and R.sup.5 have the same definitions as above, and X represents halogen atom.
When B is a group represented by the general formula (3), the compound represented by the general formula (II) can be obtained by condensing a compound represented by the formula (VIII) with a compound represented by the following formula (X): ##STR25##
In the naphthol compound (V), when E is substituted with a group represented by the formula (18), a naphthol compound (V) can be produced by condensing a compound represented by the general formula (XI), (XVIII) or (XIX): ##STR26## wherein R.sup.18 has the same definition as above; X.sup.1 represents halogen atom; and R.sup.18' represents alkylene such as ethylene, trimethylene or tetramethylene, and a divalent bonding group such as 1,2-phenylene with a compound represented by the following formula (XII): ##STR27## wherein m.sup.2 represents an integer of 0 to 3.
In the naphthol compound (V), when E is substituted with a group of the formula (19), a naphthol compound (V) can be obtained by condensing a compound represented by the following formula (XIII):
X.sup.1 --SO.sub.2 R.sup.18 (XIII)
wherein X.sup.1 and R.sup.18 have the same definitions as above, with a compound represented by the formula (XII).
Furthermore, in the naphthol compound (V), when B.sup.1 is represented by the general formula (1), a naphthol compound (V) can be obtained by condensing compounds represented by the formulas (VI) and (VII) and a compound represented by the following formula (XVI): ##STR28## wherein m.sup.2 and R have the same definitions as above, with a 2,4,6-trihalogeno-s-triazine in any order.
In the condensation reaction between the above compounds and 2,4,6-trihalogeno-s-triazine to obtain the compound of formula (V), the order is not specifically limited and the reaction conditions are not specifically limited either, although the first condensation is preferably carried out at the temperature of -10 to 40.degree. C. and pH 2-9, the second condensation is preferably carried out at the temperature of 0 to 70.degree. C. and pH 2-9, and the third condensation is preferably carried out the temperature of 10 to 100.degree. C. and pH 2-7.
When B.sup.1 represents a group of formula (1) in which R.sup.2 represents halogen, the compound represented by the general formula (V) can be obtained by omitting the third condensation according to the above synthesis method.
In the naphthol compound (V), when B.sup.1 is a group represented by the formula (2), a naphthol compound (V) can be obtained by condensing a compound represented by the general formula (XVI) with a compound represented by the general formula (IX).
In the naphthol compound (V), when B.sup.1 is represented by the general formula (3), the naphthol compound (V) can be obtained by condensing a compound represented by the general formula (XVI) with a compound represented by the formula (X).
Other intermediates and starting materials for the preparation of the polyazo compounds of formula (I) may be obtained by the application or adaptation of known method.
As the 2,4,6-trihalogeno-s-triazine used for producing the polyazo compound of the formula (I) wherein B or B.sup.1 is a group represented by the general formula (1), 2,4,6-trifluoro-s-triazine and 2,4,6-trichloro-s-triazine are preferred.
Specific examples of the compounds represented by the formulas (III) and (III-2) include 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid, 6-amino-4-hydroxynaphthalene-2-sulfonic acid, and 6-amino-4-hydroxynaphthalene-2,7-disulfonic acid.
Among them, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid is preferred.
Specific examples of the compounds represented by the general formulas (VI) and (VII) include 3-(2-sulfate ethylsulfonyl)aniline, 3-vinylsulfonylaniline, 3-(2-chloroethylsulfonyl)aniline, 3-(2-acetoxyethylsulfonyl)aniline, 4-(2-sulfate ethylsulfonyl)aniline, 4-vinylsulfonylaniline, 3-(2-sulfate ethylsulfonyl)-4-methoxyaniline, 3-vinylsulfonyl-4-methoxyaniline, 5-(2-sulfate ethylsulfonyl)-2-methoxyaniline, 5-vinylsulfonyl-2-methoxyaniline, 4-(2-sulfate ethylsulfonyl)-5-methyl-2-methoxyaniline, 4-vinylsulfonyl-5-methyl-2-methoxyaniline, 4-(2-sulfate ethylsulfonyl)-2-sulfoaniline, 4-vinylsulfonyl-2-sulfoaniline, 6-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene, 5-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene, 4-(2-sulfate ethylsulfonyl)-1-aminonaphthalene, 5-(2-sulfate ethylsulfonyl)-1,7-disulfo-2-aminonaphthalene, N-ethyl-3-(2-sulfate ethylsulfonyl)aniline, N-ethyl-4-(2-sulfate ethylsulfonyl)aniline
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H,
H.sub.2 N(CH.sub.2).sub.3 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 N(CH.sub.2).sub.3 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
H.sub.2 N(CH.sub.2).sub.3 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H,
H.sub.2 N(CH.sub.2).sub.4 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 N(CH.sub.2).sub.4 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
H.sub.2 N(CH.sub.2 ).sub.4 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H,
HN (CH.sub.2 CH.sub.2 SO.sub.2 CH.dbd.CH.sub.2).sub.2,
HN (CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 Cl).sub.2,
HN (CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H).sub.2, ##STR29##
H.sub.2 NCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 NCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
H.sub.2 NCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H, ##STR30##
H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H,
H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
H.sub.2 N (CH.sub.2).sub.3 O (CH.sub.2).sub.3 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 N (CH.sub.2).sub.3 OCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
and
H.sub.2 NCH.sub.2 CH.sub.2 O (CH.sub.2 ).sub.3 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H.
Among them, 3-(2-sulfate ethylsulfonyl)aniline, 3-vinylsulfonylaniline, 3-(2-chloroethylsulfonyl)aniline, 4-(2-sulfate ethylsulfonyl)aniline, 4-vinylsulfonylaniline, N-ethyl-3-(2-sulfate ethylsulfonyl)aniline, N-ethyl-4-(2-sulfate ethylsulfonyl)aniline,
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H,
H.sub.2 N (CH.sub.2).sub.3 SO.sub.2 CH.dbd.CH.sub.2,
H.sub.2 N (CH.sub.2).sub.3 SO.sub.2 CH.sub.2 CH.sub.2 Cl,
and
H.sub.2 N (CH.sub.2).sub.3 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H
are preferred.
Specific examples of the compound represented by the formula (VII) include
nicotinic acid; nicotinic acid amide; pyridine; amine such as ammonia, 1-aminobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-amino-3,4- or -3,5-dimethylbenzene, 1 -amino-2-, -3- or -4-ethylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or -4-ethoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 3- or 4-amino-phenymelthanesulfonic acid, 2-, 3- or 4-aminobenzenesulfonic acid, 3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, 5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid, 4-amino-5-methylbenzene-1,2-disulfonic acid, 2-, 3-or 4-aminobenzoic acid, 5-aminobenzene-1,3-dicarboxylic acid, 5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic acid, 5-amino-2-ethoxybenzenesulfonic acid; N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3- or -4-methylbenzene, 1-ethylamino-4-chlorobenzene, 1-ethylamino-3- or -4-methylbenzene, 1-(2-hydroxyethyl)-amino-3-methylbenzene, 3- or -4-methylaminobenzoic acid, 3- or 4-methylaminobenzenesulfonic acid, 4-amino-3-carboxybenzenesulfonic acid, 3-amino-4-carboxybenzenesulfonic acid, 2-amino-4-methylbenzenesulfonic acid, 2-amino-5-methylbenzenesulfonic acid, 2-amino-4-methoxybenzenesulfonic acid, 2-amino-5-methoxybenzenesulfonic acid, 3-amino-4-methoxybenzenesulfonic acid, 4-amino-3-methoxybenzenesulfonic acid, 3-amino-4-methylbenzenesulfonic acid, 4-amino-3-methylbenzenesulfonic acid, morpholine, piperidine, pyrrolidine, cyclohexylamine, cyclopentylamine, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, dimethylamine, diethylamine, methylethylamine, allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol, 2-methylaminoethanol, bis-(2-hydroxyethyl)amine, 2-acetylaminoethylamine, 1-amino-2-propanol, 3-methoxypropylamine, 1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid, aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, .epsilon.-aminocaproic acid, benzylamine, 2-, 3- or 4-chlorobenzylamine, bis-(2-sulfatoethyl)amine, 4-methylbenzylamine, N-methylbenzylamine, 2-, 3- or 4-sulfobenzylamine, 2-phenylethylamine, 1-phenylethylamine and 1-phenyl-2-propylamine;
aromatic compound such as phenol, 1-hydroxy-2-, -3- or -4-methylbenzene, 1-hydroxy-3,4- or -3,5-dimethylbenzene, 1-hydroxy-2-, -3-or -4-ethylbenzene, 1-hydroxy-2-, -3- or -4-methoxybenzene, 1-hydroxy-2-, -3- or -4-ethoxybenzene, 1-hydroxy-2-, -3- or -4-chlorobenzene, 3- or -4-hydroxy-phenylmethanesulfonic acid, 3-hydroxybenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 5-hydroxybenzene-1,3-disulfonic acid, 6-hydroxybenzene-1,4-disulfonic acid, 4-hydroxybenzene-1,2-disulfonic acid, 4-hydroxy-5-methylbenzene-1,2-disulfonic acid, 3- or 4-hydroxybenzoic acid, 5-hydroxybenzene-1,3-dicarboxylic acid, 5-hydroxy-2-ethoxybenzenesulfonic acid, 2-hydroxynaphthalene-1-sulfonic acid, 4-hydroxynaphthalene-1-sulfonic acid, 5-hydroxynaphthalene-1-sulfonic acid, 6-hydroxynaphthalene-1-sulfonic acid, 7-hydroxynaphthalene-1-sulfonic acid, 6-hydroxynaphthalene-1-sulfonic acid, 1-hydroxynaphthalene-2-sulfonic acid, 4-hydroxynaphthalene-2-sulfonic acid, 5-hydroxynaphthalene-2-sulfonic acid, 6-hydroxynaphthalene-2-sulfonic acid, 7-hydroxynaphthalene-2-sulfonic acid, 8-hydroxynaphthalene-2-sulfonic acid, 4-hydroxynaphthalene-1,3-disulfonic acid, 5-hydroxynaphthalene-1,3-disulfonic acid, 6-hydroxynaphthalene-1,3-disulfonic acid, 7-hydroxynaphthalene-1,3-disulfonic acid, 8-hydroxynaphthalene-1,3-disulfonic acid, 2-hydroxynaphthalene-1,5-disulfonic acid, 3-hydroxynaphthalene-1,5-disulfonic acid, 4-hydroxynaphthalene-1,5-disulfonic acid, 4-hydroxynaphthalene-1,6-disulfonic acid, 8-hydroxynaphthalene-1,6-disulfonic acid, 4-hydroxynaphthalene-1,7-disulfonic acid, 3-hydroxynaphthalene-2,6-disulfonic acid, 4-hydroxynaphthalene-2,6-disulfonic acid, 3-hydroxynaphthalene-2,7-disulfonic acid, 4-hydroxynaphthalene-2,7-disulfonic acid, 6-hydroxynaphthalene-1,3,5-trisulfonic acid, 7-hydroxynaphthalene-1,3,5-trisulfonic acid and 4-hydroxynaphthalene-1,3,6-trisulfonic acid;
aliphatic compound such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 2-chloroethanol, 2-methoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, 2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-cyanoethanol, 2-sulfate ethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2- or 3-or 4-chlorobenzyl alcohol, 4-methylbenzyl alcohol, 2-, 3- or 4-sulfobenzyl alcohol, 2-phenyl ethanol and 1-phenyl-2-propanol;
H.sub.2 O;
and compounds wherein hydroxy of the above compounds is substituted with mercapto.
Among them, ammonia, 1-aminobenzene, 1-amino-2-, 3- or -4-methylbenzene, 1-amino-3,4- or -3,5-dimethylbenzene, 1-amino-2-, -3- or -4-ethylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 2-, 3- or 4-aminobenzenesulfonic acid, 6-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,4-disulfonic acid, 2-, 3- or 4-aminobenzoic acid, N-methylaminobenzene, N-ethylaminobenzene, morpholine and 2-aminoethanesulfonic acid are preferred.
Specific examples of the compound represented by the formula (VIII) include 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 2-methyl-1,4-diaminobenzene, 4-methyl-1,3-diaminobenzene, 2-ethyl-1,4-diaminobenzene, 4-ethyl-1,3-diaminobenzene, 2-methoxy-1,4-diaminobenzene, 4-methoxy-1,3-diaminobenzene, 2-ethoxy-1,4-diaminobenzene, 4-ethoxy-1,3-diaminobenzene, 2,5-di-methyl-1,4-diaminobenzene, 4,6-dimethyl-1,3-diaminobenzene, 2-methyl-5-methoxy-1,4-diaminobenzene, 2,5-dimethoxy-1,4-diaminobenzene, 2-chloro-1,4-diaminobenzene, 2-bromo-1,4-diaminobenzene, 2-sulfo-1,4-diaminobenzene, 4-sulfo-1,3-diaminobenzene, 2-sulfo-5-methyl-1,4-diaminobenzene, 2-sulfo-5-methoxy-1,4-diaminobenzene, 2-sulfo-5-chloro-1,4-diaminobenzene, 2-sulfo-5-bromo-1,4-diaminobenzene, 4-sulfo-6-methyl-1,3-diaminobenzene, 4-sulfo-6-methoxy-1,3-diaminobenzene, 4-sulfo-6-ethoxy-1,3-diaminobenzene, 4-sulfo-6-chloro-1,3-diaminobenzene, 4-sulfo-6-bromo-1,3-diaminobenzene, 2,5-disulfo-1,4-diaminobenzene, 4,6-disulfo-1,3-diaminobenzene, 3-methylamino-6-sulfoaniline, 3-ethylamino-6-sulfoaniline, 3-aminomethyl-6-sulfoaniline, 4-aminomethyl-2-sulfoaniline, and 5-aminomethyl-2-aminonaphthalene-1-sulfonic acid.
Among them, 4-sulfo-1,3-diaminobenzene is preferred.
Specific examples of the compound represented by the formula (XVI) include 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid, 7-methylamino-4-hydroxynaphthalene-2-sulfonic acid, 6-amino-4-hydroxynaphthalene-2-sulfonic acid, 6-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 8-amino-4-hydroxynaphthalene-2-sulfonic acid, 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid and 5-amino-4-hydroxynaphthalene-2,8-disulfonic acid.
Among them, 7-amino-4-hydroxynaphthalene-2-sulfonic acid and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid are preferred.
Specific examples of the compound represented by the formula (IX) include 2,4,6-trifluoro-5-chloropyrimidine, 4,6-difluoro-5-chloropyrimidine, 2,4,6-trifluoropyrimidine, 2,4,5,6-tetrachloropyrimidine and 2,4,6-trifluoro-5-cyanopyrimidine.
Specific examples of the compound represented by the formula (XI) include acetyl-chloride, propionyl chloride, butyryl chloride, benzoyl chloride, p-nitrobenzoyl chloride and p-methoxybenzoyl chloride.
Specific examples of the compound represented by the formula (XVIII) include acetic anhydride, propionic anhydride and butanoic anhydride.
Specific examples of the compound represented by the formula (XIX) include succinic anhydride, glutaric anhydride and phthalic anhydride.
Specific examples of the compound represented by the formula (XII) include 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid, 6-amino-4-hydroxynaphthalene-2-sulfonic acid, 6-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 8-amino-4-hydroxynaphthalene-2-sulfonic acid, 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid and 5-amino-4-hydroxynaphthalene-2,8-disulfonic acid.
Among them, 7-amino-4-hydroxynaphthalene-2-sulfonic acid and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid are preferred.
Specific examples of the compound represented by the formula (XIII) include methanesulfonyl chloride, phenylsulfonyl chloride and p-toluenesulfonyl chloride.
Specific examples of the compound represented by the formula (II) include
compound having a reactive substituent, such as 3-(2-sulfate ethylsulfonyl)aniline, 3-vinylsulfonylaniline, 3-(2-chloroethylsulfonyl)aniline, 3-(2-acetoxyethylsulfonyl)aniline, 4-(2-sulfate ethylsulfonyl)aniline, 4-vinylsulfonylaniline, 3-(2-sulfate ethylsulfonyl)-4-methoxyaniline, 3-vinylsulfonyl-4-methoxyaniline, 5-(2-sulfate ethylsulfonyl)-2-methoxyaniline, 5-vinylsulfonyl-2-methoxyaniline, 4-(2-sulfate ethylsulfonyl)-5-methyl-2-methoxyaniline, 4-vinylsulfonyl-5-methyl-2-methoxyaniline, 4-(2-sulfate ethylsulfonyl)-2-sulfoaniline, 4-vinylsulfonyl-2-sulfoaniline, 6-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene, 5-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene, 4-(2-sulfate ethylsulfonyl)-1-aminonaphthalene and 5-(2-sulfate ethylsulfonyl)-1,7-disulfo-2-aminonaphthalene; and
compound having no reactive substituent, such as 2-, 3- or 4-sulfoaniline, 2,4- or 2,5-disulfoaniline, 2-carboxy-4- or 5-sulfoaniline, 2-sulfo-4-methoxyaniline, 2-sulfo-4-methylaniline, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 2-aminonaphthalene-4,8-disulfonic acid, 2-aminonaphthalene-3,6-disulfonic acid, 2-aminonaphthalene-6,8-disulfonic acid, 2-aminonaphthalene-3,7-disulfonic acid, 2-aminonaphthalene-4,7-disulfonic acid, 2-aminonaphthalene-5,7-disulfonic acid, 2-aminonaphthalene-1,5,7-trisulfonic acid, 2-aminonaphthalene-4,6,8-trisulfonic acid, 2-aminonaphthalene-3,6,8-trisulfonic acid and 1-aminonaphthalene-3,6,8-trisulfonic acid, in addition to compound which can be obtained from the compounds represented by the general formulas (VI), (VII) and (VIII) and 2,4,6-trihalogeno-s-triazine.
Among them, 5-(2-sulfate ethylsulfonyl)-2-methoxyaniline, 5-vinylsulfonyl-2-methoxyaniline, 4-(2-sulfate ethylsulfonyl)-5-methyl-2-methoxyaniline, 4-vinylsulfonyl-5-methyl-2-methoxyaniline, 4-(2-sulfate ethylsulfonyl)-2-sulfoaniline, 4-vinylsulfonyl-2-sulfoaniline, 6-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene, 5-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene, S-(2-sulfate ethylsulfonyl)-1,7-disulfo-2-aminonaphthalene, 2-, 3-or 4-sulfoaniline, 2,4-or 2,5-disulfoaniline, 2-sulfo-4-methoxyaniline, 2-sulfo-4-methylaniline, 2-aminonaphthalene-1-sulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 2-aminonaphthalene-1,5,7-trisulfonic acid and 2-aminonaphthalene-3,6,8-trisulfonic acid are preferred.
Examples of the compound represented by the general formula (V) include 3-, 4- or 5-sulfo-1-naphthol, 3,6-disulfo-1-naphthol, 3,8-disulfo-1-naphthol, ,6,8-trisulfo-1-naphthol, 6-, 7- or 8-sulfo-2-naphthol, 3,6-disulfo-2-naphthol and 6,8-disulfo-2-naphthol, in addition to
compound which can be obtained from the compound represented by the formulas (XI), (XVIII) or (XIX) and the compound represented by the formula (XII);
compound which can be obtained from the compounds represented by the general formulas (XIII) and (XII); compound which can be obtained by the compounds represented by the general formulas (VI), (VII) and (XVI) and 2,4,6-trihalogeno-s-triazine;
compound which can be obtained from the above compounds represented by the general formulas (XVI) and (IX); and compound which can be obtained from the above compound represented by the general formula (XVI) And the above compound represented by the general formula (X).
Specific examples of the compound which can be obtained from the compound represented by the general formula (XI), (XVIII) or (XIX) and the compound represented by the general formula (XII) include:
6- or 7-acetylamino-3-sulfo-1-naphthol,
6- or 7-propionylamino-3-sulfo-1-naphthol,
6- or 7-(2-carboxyethylcarbonylamino)-3-sulfo-1-naphthol,
6- or 7-benzoylamino-3-sulfo-1-naphthol,
6- or 7-methanesulfonylamino-3-sulfo-1-naphthol,
6- or 7-phenylsulfonylamino-3-sulfo-1-naphthol,
6- or 7-(p-toluenesulfonylamino)-3-sulfo-1-naphthol,
8-acetylamino-3, 5-disulfo-1-naphthol,
8-propionylamino-3,5-disulfo-1-naphthol,
8-(2-carboxyethylcarbonylamino)-3,5-disulfo-1-naphthol,
8-benzoylamino-3,5-disulfo-1-naphthol,
8-methanesulfonylamino-3,5-disulfo-1-naphthol,
8-phenylsulfonylamino-3,5-disulfo-1-naphthol,
8-(p-toluenesulfonylamino)-3,5-disulfo-1-naphthol,
8-acetylamino-3, 6-disulfo-1-naphthol,
8-propionylamino-3,6-disulfo-1-naphthol,
8-(2-carboxyethylcarbonylamino)-3,6-disulfo-1-naphthol,
8-benzoylamino-3,6-disulfo-1-naphthol,
8-methanesulfonylamino-3,6-disulfo-1-naphthol,
8-phenylsulfonylamino-3, 6-disulfo-1-naphthol,
and
8-(p-toluenesulfonylamino)-3,6-disulfo-1-naphthol.
The polyazo compound (I) of the present invention and a raw material thereof may take the form of a free acid, a salt thereof or a mixture thereof. An alkali metal salt, an alkaline earth metal salt and a mixture containing them are preferred. Among them, a sodium salt, a potassium salt, a lithium salt and a mixture containing them are particularly preferred.
The polyazo compound (I) of the present invention can be used as a dye for dyeing and textile-printing a fiber material. The fiber material dyed or textile-printed by the polyazo compound (I) may be any one which has a hydroxy group and/or an amide group, and is not specifically limited. Examples thereof include natural or regenerated cellulose fiber, natural or synthetic polyamide fiber, polyurethane fiber, hide and a mixed fabric material containing them.
Examples of the natural cellulose fiber include cotton, linen, hemp, jute and ramie fiber. Preferred is cotton.
Specific examples of the regenerated cellulose include rayon, polynosic, cupra fiber and those having trade names such as "Tencel", "Tafcel". "Modal" and "Celtima".
Specific examples of the natural or synthetic polyamide fiber include wool, silk, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.
Examples of the mixed fabric material include mixed fabric material of the above fiber materials and synthetic fibers such as polyester, nylon, acrylic, etc., in addition to mixed fabric material of the above fiber materials.
Using the compound of the present invention, the above fiber materials can be dyed or textile-printed by a method according to physical/chemical properties.
Specific examples of the method include exhaustion dyeing method, cold batch-up method, continuous dyeing method, textile-printing method.
Examples of the exhaustion dyeing method include a method of carrying out the dyeing at the temperature of about 30 to 100.degree. C. in the presence of an acid binder such as sodium carbonate, sodium hydrogencarbonate, sodium tertiary phosphate and sodium hydroxide by optionally adding a neutral salt such as sodium sulfate and sodium chloride, and optionally using in combination with a solubilizing agent, an osmotic agent, leveling agent or the like. The acid binder and neutral salt may be added in one portion or in several portion according to a normal method.
When the cellulose fiber is dyed by the cold batch-up method, the method may be carried out by padding with a neutral salt such as sodium sulfate and sodium chloride, and an acid binder such as sodium hydroxide and sodium silicate, followed by standing the resultant dyed product in a seal-packing material at a constant temperature.
When the cellulose fiber is dyed by the continuous dyeing method, there may be used a one-phase padding method or a two-phase padding method. The one-phase padding method may be carried out by padding at room temperature or elevated temperature in the presence of an acid binder such as sodium carbonate and sodium hydrogencarbonate according to a known method, followed by steaming or dry heating. The two-phase padding method may be carried out by dipping a fiber in a padding solution wherein the compound of the present invention is dissolved, padding a neutral salt such as sodium sulfate and sodium chloride and an acid binder such as sodium hydroxide and sodium silicate, followed by steaming or dry heating.
Examples of the textile-printing method include a method of textile-printing a cellulose fiber with a textile-printing paste containing an acid binder such as sodium hydrogencarbonate in one phase, followed by steaming at high temperature of not less than 80.degree. C.; and a method of textile-printing a cellulose fiber with a neutral or weak-acid textile-printing paste, passing it through an alkaline bath containing an electrolyte or overpadding with an alkaline padding solution containing an electrolyte, followed by steaming or dry heating. The textile-printing paste may contains a sizing agent such as sodium alginate and starch ether and/or an emulsifier and may optionally contains a textile-printing aid such as urea and/or a dispersant.
When the cellulose fiber is dyed or textile-printed using the compound of the present invention, the acid binder is not specifically limited and there can be used, for example, sodium carbonate, sodium hydrogencarbonate, sodium tertiary phosphate, sodium hydroxide, sodium silicate, potassium hydroxide, sodium formate, potassium carbonate, sodium primary or secondary phosphate and sodium trichloroacetate.
When the synthetic or natural polyamide fiber or polyurethane fiber is exhaustion-dyed, there may be adopted a method in which the compound of the present invention is exhausted in an acid or weak-acid dye bath under the control of pH and, then, the pH is changed into neutral or alkali at the temperature of about 60 to 120.degree. C. There may be optionally used a leveling agent such as condensate of cyanuric chloride and aminobenzenesulfonic acid, condensate of cyanuric chloride and aminonaphthalenesulfonic acid and adduct of stearylamine and ethylene oxide.
The polyazo compound of the present invention can be optionally used in combination with other dyes as far as the feature of the present invention is not adversely affected in order to obtain a desired hue. The dye used in combination with the polyazo compound of the present invention may be any reactive dye other than the polyazo compound of the present invention, and is not specifically limited. Examples thereof include
dyes having at least one group selected from the group consisting of sulfatoethyl sulfone group, vinyl sulfone group, monochlorotriazine group, monofluorotriazine group, mononicotinic acid triazine group, dichlorotriazine group, difluoromonochloropyrimidine group and trichloropyrimidine group;
dyes which are commercially available under the trade name of Sumifix, Sumifix Supra, Remazol, Levafix, Procion, Cibacron, Basilen, Drimarene, Kayacion, Kayacelon React, etc.;
dyes described in respective gazettes such as JP-A-50-178, JP-A-56-9483, JP-A-56-15481, JP-A-56-118976, JP-A-56-128380, JP-A-57-2365, JP-A-57-89679, JP-A-57-143360, JP-A-58-191755, JP-A-59-15451, JP-A-59-96174, JP-A-59-161463, JP-A-60-6754, JP-A-60-123559, JP-A-60-229957, JP-A-60-26054, JP-A-61-126175, JP-A-61-155469, JP-A-61-225256, JP-A-63-77974, JP-A-63-225664, JP-A-1-185370,
JP-A-3-770, JP-A-5-117538, JP-A-5-247366 and JP-A-6-287463; and
dyes represented by C.I. Reactive Blue 19 and C.I. Reactive Black 5.
According to the present invention, there can be obtained a dye exhibiting excellent reproducibility, that is, affording dyed or textile-printed product having good quality regardless of changes of dyeing temperature, amount of neutral salt and acid binder and dye bath ratio, excellent levelness, high build-up properties, high color value and high effective dyeing ratio in a dyeing and textile-printing treatment of fiber materials; and capable of affording a dyed or textile-printed product having various excellent fastnesses, particularly chlorine atom treated water fastness, tap water chlorine atom fastness, light fastness and perspiration light fastness. The resultant dyed product or textile-printed product causes little discoloration at the time of various processing treatments such as fixing treatment and resin treatment and is also superior in storage stability. Therefore, there is little influence due to contact with a basic substance derived from a plastic bag, which is considered to be caused during storage in the plastic bag.
The following Examples further illustrate the present invention in detail but are not to be construed to limit the scope thereof. In the Examples, "parts" and "%'s" are by weight unless otherwise stated.

EXAMPLE 1
In an aqueous solvent, 18.8 parts of 4-sulfo-1,3-diaminobenzene was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method. The resultant condensate was condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method. The product was diazotized by using sodium nitrite, and then diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid according to a normal method to obtain a monoazo compound. This monoazo compound was further diazotized by using sodium nitrite and then diazo-coupled with 30.4 parts of 3,6-disulfo-1-naphthol to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR31##
EXAMPLE 2
In an aqueous solvent, 26.8 parts of 4,6-disulfo-1,3-diaminobenzene was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method. The resultant condensate was condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method. The product was diazotized by using sodium nitrite, and then diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid, followed by condensing the resultant compound with 9.3 parts of aniline according to a normal method to obtain a monoazo compound. This monoazo compound was further diazotized by using sodium nitrite and then diazo-coupled with 30.4 parts of 3,6-disulfo-1-naphthol to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR32##
EXAMPLE 3
In an aqueous solvent, 23.9 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was condensed with 10.0 parts of succinic anhydride according to a normal method to obtain a naphthol derivative.
In an aqueous solvent, 18.8 parts of 4-sulfo-1,3-diaminobenzene was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate was condensed with 28.1 parts of 4-(2-sulfate ethylsulfonyl)aniline according to a normal method. The product thus obtained was diazotized by using sodium nitrite, the diazotized product was diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid to obtain a monoazo compound. This monoazo compound was further diazotized by using sodium nitrite and then diazo-coupled with the above naphthol derivative to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR33##
EXAMPLE 4
According to the same manner as that described in Example 3 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6 and a compound of the column 7 shown in Table 1 in place of 7-amino-4-hydroxynaphthalene-2-sulfonic acid, succinic anhydride, 4-sulfo-1,3-diaminobenzene, 2,4,6-trichloro-s-triazine, 4-(2-sulfate ethylsulfonyl)aniline and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid used in Example 3, respectively, each corresponding polyazo compound was obtained. Using the polyazo compound thus obtained, dyeing was carried out and a dyed product having a color shown in the column 8 of Table 1 was obtained
The symbols used in the following tables and Example 27 represent the following compound:
1a: 7-amino-4-hydroxynaphthalene-2-sulfonic acid
1b: 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid
1c: 7-methylamino-4-hydroxynaphthalene-2-sulfonic acid
1d: 6-amino-4-hydroxynaphthalene-2-sulfonic acid
1e: 6-amino-4-hydroxynaphthalene-2,7-disulfonic acid
1f: 8-amino-4-hydroxynaphthalene-2-sulfonic acid
1g: 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid
1h: 5-amino-4-hydroxynaphthalene-2,8-disulfonic acid ##STR34## 3a 2,5-disulfoaniline
3b 2,4-disulfoaniline
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H 3c
H.sub.2 N (CH.sub.2).sub.3 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H 3d
H.sub.2 NCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 Cl 3e
H.sub.2 N (CH.sub.2).sub.3 SO.sub.2 CH.sub.2 CH.sub.2 Cl 3f
H.sub.2 N CH.sub.2 CH.sub.2 SO.sub.2 CH.dbd.CH.sub.2 3g
H.sub.2 N (CH.sub.2).sub.3 SO.sub.2 CH.dbd.CH.sub.2 3h
H.sub.2 NCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 SO.sub.2 CH.dbd.CH.sub.2 3i
HN (CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H).sub.2 3j
HO.sub.3 SOCH.sub.2 CH.sub.2 NHCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H 3k ##STR35## 4a: 3-(2-sulfate ethylsulfonyl)aniline 4b: 3-vinylsulfonylaniline
4c: 3-(2-chloroethylsulfonyl)aniline
4d: 3-(2-acetoxyethylsulfonyl)aniline
4e: 4-(2-sulfate ethylsulfonyl)aniline
4f: 4-vinylsulfonylaniline
4g: 3-(2-sulfate ethylsulfonyl)-4-methoxyaniline
4h: 3-vinylsulfonyl-4-methoxyaniline
4i: 5-(2-sulfate ethylsulfonyl)-2-methoxyaniline
4j: 5-vinylsulfonyl-2-methoxyaniline
4k: 4-(2-sulfate ethylsulfonyl)-5-methyl-2-methoxyaniline
4l: 4-vinylsulfonyl-5-methyl-2-methoxyaniline
4m: 4-(2-sulfate ethylsulfonyl)-2-sulfoaniline
4n: 4-vinylsulfonyl-2-sulfoaniline
4o: 6-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene
4p: 5-(2-sulfate ethylsulfonyl)-1-sulfo-2-aminonaphthalene
4q: 4-(2-sulfate ethylsulfonyl)-1-aminonaphthalene
4r: 5-(2-sulfate ethylsulfonyl)-1,7-disulfo-2-aminonaphthalene
4s: nicotinic acid
4t: nicotinic acid amide
4u: pyridine
4v: N-ethyl-3-(2-sulfate ethylsulfonyl1)aniline
4w: N-(2-cyanoethyl)-3-(2-sulfate ethylsulfonyl)aniline
4x: 2,4,6-trichloro-s-triazine
4y: 2,4,6-trifluoro-s-triazine
5a: 2-sulfoaniline
5b: 3-sulfoaniline
5c: 4-sulfoaniline
5d: 2-ethylaniline
5e: N-ethylaniline
5f: 4-chloro-N-ethylaniline
5g: N-(2-cyanoethyl)aniline
5h: N-phenyl-.beta.-alanine
5i: N-phenyltaurine
5j: 2-sulfo-4-methoxyaniline
5k: 4-methoxyaniline
5l: anthranilic acid
5m: 4-(n-butyl)aniline
5o: 4-(n-butoxy)aniline
5p: 3,6,8-trisulfo-2-aminonaphthalene
5q: .beta.-alanine
5r: taurine
5s: 7-aminobutyric acid
5t: H.sub.2 NCN
5u: aniline
5v: morpholine
5w: methanol
5x: phenol
5y: 1,5-disulfo-2-aminonaphthalene
5z: 1-sulfo-2-aminonaphthalene
6a: 2,4,6-trichloro-5-chloropyrimidine
6b: 2,4,6-trifluoro-5-chloropyrimidine
6c: 4,6-difluoro-5-chloropyrimidine
6d: 2,4,6-trifluoropyrimidine
6e: 2,4,5,6-tetrachloropyrimidine
6f: 2,4,6-trifluoro-5-cyanopyrimidine ##STR36## 6h: acetic anhydride 6i: propionic anhydride
6j: succinic anhydride
6k: benzoyl chloride
6l: methanesulfonyl chloride
6m: phenylsulfonyl chloride
6n: p-toluenesulfonyl chloride
7a: 3-sulfo-1-naphthol
7b: 4-sulfo-1-naphthol
7c: 5-sulfo-1-naphthol
7d: 3,6-disulfo-1-naphthol
7e: 3,8-disulfo-1-naphthol
7f: 3,6,8-trisulfo-1-naphthol
7g: 6-sulfo-2-naphthol
7h: 7-sulfo-2-naphthol
7i: 8-sulfo-2-naphthol
7j: 3,6-disulfo-2-naphthol
7k: 6,8-disulfo-2-naphthol
8a: 4-ethyl-1,3-diaminobenzene
8b: 4-methoxy-1,3-diaminobenzene
8c: 2-sulfo-1,4-diaminobenzene
8d: 4-sulfo-1,3-diaminobenzene
8e: 2-sulfo-5-methyl-1,4-diaminobenzene
8f: 2-sulfo-5-chloro-1,4-diaminobenzene
8g: 2,5-disulfo-1,4-diaminobenzene
8h: 4,6-disulfo-1,3-diaminobenzene
8i: 3-methylamino-6-sulfoaniline
8j: 3-ethylamino-6-sulfoaniline
8k: 3-aminomethyl-6-sulfoaniline
8l: 4-aminomethyl-2-sulfoaniline
8m: 5-aminomethyl-2-aminonaphthalene-1-sulfonic acid
TABLE 1______________________________________Col-umn Column Column Column Column Column Column Column1 2 3 4 5 6 7 8______________________________________19 1a 6k 3d 4x 8d 1b red20 1a 6k 8d 4x 4c 1b red______________________________________
EXAMPLE 5
According to the same manner as that described in Example 3 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6 and a compound of the column 7 shown in Table 2 in pace of 7-amino-4-hydroxynaphthalene-2-sulfonic acid, succinic anhydride, 4-sulfo-1,3-diaminobenzene, 2,4,6-trichloro-s-triazine, 4-(2-sulfate ethylsulfonyl) aniline and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid used in Example 3, respectively, each corresponding polyazo compound is obtained.
TABLE 2______________________________________Column Column Column Column Column Column Column1 2 3 4 5 6 7______________________________________ 5 1a 6b 8d 4x 4a 1b 6 1a 6c 8d 4x 4a 1b 7 1a 6d 8d 4x 4a 1b 8 1a 6e 8d 4x 4a 1b 9 1a 6f 8d 4x 4a 1b10 1a 6g 8d 4x 4a 1b11 1a 6i 8d 4x 4a 1b12 1a 6i 3c 4x 8d 1b13 1g 6i 8d 4x 4a 1b14 1a 6j 8d 4x 4a 1b15 1a 6j 3c 4x 8d 1b16 1a 6j 3a 4y 8d 1b17 1a 6j 3a 4y 8d 1e18 1a 6k 3a 4y 8d 1b21 1g 6k 8d 4x 4a 1b22 1a 6l 8d 4x 4a 1b23 1b 6l 8d 4x 4a 1b24 1a 6m 3c 4x 8h 1b25 1d 6m 4m 4x 8d 1b26 1a 6n 8d 4x 4a 1b______________________________________
EXAMPLE 6
In an aqueous solvent, 23.9 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was condensed with 14.1 parts of benzoyl chloride according to a normal method to obtain a naphthol derivative.
In an aqueous solvent, 25.3 parts of 2,5-disulfoaniline was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate was condensed with 18.8 parts of 4-sulfo-1,3-diaminobenzene according to a normal method. The product was diazotized by using sodium nitrite, the diazotized product was diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid, and then condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method to obtain a monoazo compound. This monoazo compound was further diazotized by using sodium nitrite and then diazo-coupled with the above naphthol derivative to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR37##
EXAMPLE 7
According to the same manner as that described in Example 6 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6 and a compound of the column 7 shown in Table 3 in place of 7-amino-4-hydroxynaphthalene-2-sulfonic acid, benzoyl chloride, 2,5-disulfoaniline, 4-sulfo-1,3-diaminobenzene, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid and 3-(2-sulfate ethylsulfonyl)aniline used in Example 6, respectively, each corresponding polyazo compound was obtained. Using the polyazo compound thus obtained, dyeing was carried out and a dyed product having a color shown in the column 8 of Table 3 was obtained.
TABLE 3______________________________________Col-umn Column Column Column Column Column Column Column1 2 3 4 5 6 7 8______________________________________3 1a 6j 3a 8d 1b 4a red______________________________________
EXAMPLE 8
According to the same manner as that described in Example 6 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6 and a compound of the column 7 shown in Table 4 in place of 7-amino-4-hydroxynaphthalene-2-sulfonic acid, benzoyl chloride, 2,5-disulfoaniline, 4-sulfo-1,3-diaminobenzene, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid and 3-(2-sulfate ethylsulfonyl)aniline used in Example6, respectively, each corresponding polyazo compound is obtained.
TABLE 4______________________________________Column Column Column Column Column Column Column1 2 3 4 5 6 7______________________________________ 1 1a 6h 3a 8d 1b 4a 2 1a 6i 3a 8d 1b 4a 4 1a 6k 3a 8d 1b 4e 5 1a 6m 3a 8d 1b 4a 6 1a 6n 3a 8d 1b 4a 7 1a 6j 3a 8d 1d 4a 8 1a 4x 3b 8d 1b 4a 9 1a 6b 3b 8d 1b 4e10 1a 6c 3b 8d 1b 4a11 1a 6d 3b 8d 1b 4a12 1a 6e 3b 8d 1b 4a13 1a 6f 3b 8d 1b 4a14 1a 6g 3b 8d 1b 4a15 1a 6b 3c 8d 1b 5a16 1g 6i 3c 8d 1b 5c17 1g 6i 3c 8d 1b 4t18 1a 6j 3c 8d 1b 4s19 1a 6j 3c 8d 1b 5a20 1a 6k 3c 8d 1b 5a21 1a 6k 3c 8d 1b 4s22 1a 6j 3c 8d 1b 4a23 1a 6j 3c 8d 1b 5l24 1a 6j 3c 8d 1e 5b25 1a 6j 3c 8d 1e 5b26 1a 6j 5q 8d 1b 4a27 1a 6j 8d 4a 1b 4s28 1a 6k 8d 4a 1b 4s29 1a 6l 8d 4a 1b 5b30 1a 6j 8d 5r 1b 4a31 1f 6j 8d 5r 1b 4a32 1a 6k 8d 5r 1b 4a33 1a 6b 8d 5s 1b 4a34 1a 6b 8d 5t 1b 4e35 1a 6j 8d 5t 1b 4a______________________________________
EXAMPLE 9
In an aqueous solvent, 31.9 parts of 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate was condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method to obtain a naphthol derivative.
In an aqueous solvent, 41.1 parts of 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene was diazotized by using sodium nitrite, the diazotized product was diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid to obtain a monoazo compound. This monoazo compound was diazotized by using sodium nitrite and then diazo-coupled with the above naphthol derivative to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR38##
EXAMPLE 10
According to the same manner as that described in Example 9 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5 and a compound of the column 6 shown in Table 5 in place of 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 2,4,6-trichloro-s-triazine, 3-(2-sulfate ethylsulfonyl)aniline, 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid used in Example 9, respectively, each corresponding polyazo compound was obtained. Using the polyazo compound thus obtained, dyeing was carried out and a dyed product having a color shown in the column 8 of Table 5 was obtained.
TABLE 5______________________________________Column Column Column Column Column Column Column1 2 3 4 5 6 7______________________________________19 1a 4x 4e 4p 1b bluish red______________________________________
EXAMPLE 11
According to the same manner as that described in Example 9 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column S and a compound of the column 6 shown in Table 6 in place of 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 2,4,6-trichloro-s-triazine, 3-(2-sulfate ethylsulfonyl)aniline, 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid used in Example 9, respectively, each corresponding polyazo compound is obtained.
TABLE 6______________________________________Column Column Column Column Column Column1 2 3 4 5 6______________________________________ 1 1a 4x 4a 4i 1b 7 3c 4x 1a 4i 1b 8 3c 4x 1a 4i 1e 9 4e 4x 1a 4i 1b10 3c 4x 1a 4k 1b11 1a 4x 4v 4m 1b12 3c 4x 1a 4m 1b13 1g 4x 4e 4o 1b17 3c 4x 1g 4o 1b28 1h 4x 4e 4p 1b30 3c 4x 1a 4p 1b33 3c 4x 1a 4r 1b______________________________________
EXAMPLE 12
In an aqueous solvent, 31.9 parts of 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate was condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method. The product thus obtained was condensed with 9.3 parts of aniline according to a normal method to obtain a naphthol derivative.
In an aqueous solvent, 41.1 parts of 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene was diazotized by using sodium nitrite, the diazotized product was diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid to obtain a monoazo compound. This monoazo compound was diazotized by using sodium nitrite and then diazo-coupled with the above naphthol derivative to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR39##
EXAMPLE 13
According to the same manner as that described in Example 12 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5 and a compound of the column 6 shown in Table 7 in place of 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 3-(2-sulfate ethylsulfonyl)aniline, aniline, 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid used in Example 12, respectively, each corresponding polyazo compound is obtained.
TABLE 7______________________________________Column Column Column Column Column Column1 2 3 4 5 6______________________________________1 3a 1a 4a 4i 1b4 3c 1a 4t 4i 1b5 3c 1a 5a 4i 1b7 1a 5r 4a 4j 1b8 3a 1a 4a 4j 1e9 3a 1a 4a 4j 1d10 3b 1a 4a 4j 1b11 3b 1a 4a 4j 1a12 3c 1a 5a 4j 1b15 1a 4d 5a 4p 1b16 1a 5r 4a 4p 1b19 1a 5t 4a 4p 1b21 3c 1a 5b 4p 1b22 3c 1a 5k 4p 1b23 3o 1a 4a 4p 1b24 3c 1g 4a 4p 1b25 3c 1g 5e 4p 1b______________________________________
EXAMPLE 14
In an aqueous solvent, 31.9 parts of 5-amino-4-hydroxynaphthalene-2, 7-disulfonic acid was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate was condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method to obtain a compound, the free acid form of which being represented by the following formula (21): ##STR40##
In an aqueous solvent, 58.3 parts of a compound, the free acid form of which being represented by the following formula (22): ##STR41## was diazotized by using sodium nitrite and the diazotized product was diazo-coupled with the above-obtained compound (21) to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR42##
EXAMPLE 15
According to the same manner as that described in Example 14 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4 and a compound of the column 5 shown in Table 8 in place of the compound of formula (22), 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 3-(2-sulfate ethylsulfonyl)aniline and 2,4,6-trichloro-s-triazine used in Example 14, respectively, each corresponding polyazo compound was obtained. Using the polyazo compound thus obtained, dyeing was carried out and a dyed product having a color shown in the column 6 of Table 8 was obtained.
TABLE 8______________________________________Column 1 Column 2 Column 3 Column 4 Column 5 Column 6______________________________________1 2a 1a 4a 4x yellowish red2 2a 1f 4c 4x purple4 2a 3c 1a 4x yellowish red15 2e 3d 1a 4x yellowish red42 2p 1a 4a 4x red______________________________________
EXAMPLE 16
According to the same manner as that described in Example 14 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4 and a compound of the column 5 shown in Table 9 in place of the compound of formula (22), 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 3-(2-sulfate ethylsulfonyl)aniline and 2,4,6-trichloro-s-triazine used in Example 14, respectively, each corresponding polyazo compound is obtained.
TABLE 9______________________________________Column 1 Column 2 Column 3 Column 4 Column 5______________________________________5 2a 1c 4e 4x8 2b 1b 4a 4x9 2b 3g 1a 4x10 2c 1h 4m 4x11 2c 1a 4d 4x12 2d 1b 4g 4x13 2d 1f 4i 4x14 2e 1a 4h 4x16 2f 1a 4n 4x17 2f 1g 4f 4x18 2g 1b 4j 4x19 2g 3e 1a 4x20 2h 3h 1a 4x21 2h 1e 4o 4x22 2i 1c 4q 4x23 2i 1b 4p 4x24 2j 1a 4a 4x25 2j 1b 4a 4x26 2j 1d 4e 4x27 2j 3c 1a 4x28 2j 1a 4a 4y29 2j 3c 1a 4y30 2j 1a 3i 4y32 2k 1e 4r 4x33 2k 1b 4n 4x34 2l 1d 4a 4x35 2l 1e 4b 4x36 2m 1a 4r 4x37 2m 1b 4c 4x38 2n 1a 4v 4x39 2n 1c 4a 4x40 2o 1d 4k 4x41 2o 1e 4o 4x43 2p 1b 4g 4x44 2p 1a 4w 4x45 2p 1c 4a 4x46 2p 3c 1a 4x47 2p 1a 3f 4y48 2p 1a 3h 4y49 2p 1c 4a 4y51 2q 1a 4l 4x52 2q 1d 1a 4x54 2r 1b 4v 4x55 2s 1a 4k 4x56 2s 1c 4a 4x57 2t 1a 4a 4x58 2t 3d 1a 4x______________________________________
EXAMPLE 17
In an aqueous solvent, 31.9 parts of 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine and the resultant condensate was condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline to obtain a compound, the free acid form of which being represented by the following formula (21): ##STR43##
In an aqueous solvent, 50.3 parts of a compound, the free acid form of which being represented by the following formula (23): ##STR44## was diazotized by using sodium nitrite and the diazotized product was diazo-coupled with the above-obtained compound (21) in an aqueous solvent to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR45##
Thereafter, the compound thus obtained was reacted with 17.3 parts of 3-sulfoaniline in an aqueous solvent to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR46##
EXAMPLE 18
According to the same manner as that described in Example 17 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4 and a compound of the column 5 shown in Table 10 in place of the compound of formula (23), 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 3-(2-sulfate ethylsulfonyl)aniline and 3-sulfoaniline used in Example 17, respectively, each corresponding polyazo compound was obtained. Using the polyazo compound thus obtained, dyeing was carried out and a dyed product having a color shown in the column 6 of Table 10 was obtained.
TABLE 10______________________________________Column 1 Column 2 Column 3 Column 4 Column 5 Column 6______________________________________1 2a 1a 4a 5a yellowish red2 2a 1a 4a 5u yellowish red5 2a 3a 1a 4a yellowish red6 2a 3a 1a 4e yellowish red7 2a 3c 1a 5a yellowish red8 2a 3c 1a 5j yellowish red13 2a 1f 4a 5u purple14 2a 1g 4a 5u purple______________________________________
EXAMPLE 19
According to the same manner as that described in Example 17 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4 and a compound of the column 5 shown in Table 11 in place of the compound of formula (23), 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 3-(2-sulfate ethylsulfonyl)aniline and 3-sulfoaniline used in Example 17, respectively, each corresponding polyazo compound is obtained.
TABLE 11______________________________________Column 1 Column 2 Column 3 Column 4 Column 5______________________________________3 2a 1a 4e 4a4 2a 1a 4v 4a9 2a 3o 1e 5u10 2a 3c 1a 5k11 2a 3c 1a 4a12 2a 3c 1a 4e15 2b 1a 4e 5d16 2b 1c 4a 5c17 2c 1b 5r 4a18 2c 1a 4a 5g19 2d 1a 5i 4a20 2d 3c 1a 5l21 2e 3l 1a 5b22 2e 2a 4a 5a23 2g 1a 4a 5e24 2g 1a 4e 4s25 2j 1a 4a 5a26 2j 1a 4a 4t27 2j 1a 4a 4s28 2j 1a 5h 4a29 2j 3a 1a 4a30 2j 3b 1a 4a31 2j 3c 1a 5e32 2j 3c 1a 5f33 2j 3c 1a 5k34 2j 3c 1a 5l35 2j 3c 1a 4s36 2j 3k 1a 4a37 2k 1d 4a 5k38 2k 1e 4a 4u39 2l 3c 1d 5b40 2l 1e 5p 4a41 2p 1a 4e 4a42 2p 1a 4v 4a43 2p 1a 4a 4s44 2p 1a 4a 6m45 2p 3c 1a 4a46 2p 3c 1a 5o47 2p 3c 1a 5t48 2p 3c 1a 5q49 2q 1a 4a 5s50 2q 3c 1a 5u51 2r 1a 4a 5p52 2r 3b 1a 4a53 2r 1a 4v 6u54 2r 1a 5e 4e55 2t 1b 4a 5a56 2t 3c 1a 5u______________________________________
EXAMPLE 20
In an aqueous solvent, 23.9 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid is condensed with 14.1 parts of benzoyl chloride according to a normal method to obtain a naphthol derivative.
In an aqueous solvent, 18.8 parts of 4-sulfo-1,3-diaminobenzene is condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate is condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method. The product thus obtained is diazotized by using sodium nitrite, the diazotized product is diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(a) to obtain a monoazo compound. This monoazo compound is further diazotized by using sodium nitrite and then diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(b) to obtain a bisazo compound. This bisazo compound is further diazotized by using sodium nitrite and then diazo-coupled with the above naphthol derivative to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR47##
EXAMPLE 21
According to the same manner as that described in Example 20 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6, a compound of the column 7 and a compound of the column 8 shown in Table 12 in place of 7-amino-4-hydroxynaphthalene-2-sulfonic acid, benzoyl chloride, 4-sulfo-1,3-diaminobenzene, 2,4,6-trichloro-s-triazine, 3(2-sulfate ethylsulfonyl) aniline, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid (a) and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid (b) used in Example 20, respectively, each corresponding polyazo compound is obtained.
TABLE 12______________________________________Col-umn Column Column Column Column Column Column Column1 2 3 4 5 6 7 8______________________________________ 3 1a 6b 3a 4x 8d 1b 1b 4 1a 6c 3a 4x 8d 1b 1b 5 1a 8d 8d 4x 4a 1b 1b 6 1a 6e 8d 4x 4a 1b 1b 7 1a 6f 3a 4x 8d 1b 1b 8 1a 6g 3a 4x 8d 1b 1b 9 1a 6h 3a 4x 8d 1b 1b10 1g 8h 3c 4x 8d 1b 1b11 1g 5h 8d 4x 4b 1b 1b12 1g 6h 8d 4x 8d 1b 1e13 1a 6i 3c 4x 8d 1b 1b14 1g 6j 3c 4x 8d 1b 1b15 1g 8j 8d 4x 4a 1b 1b16 1g 6j 8d 4x 4e 1b 1b17 1h 6j 8d 4x 4e 1b 1b18 1g 6k 8d 4x 4e 1b 1b19 1a 6l 8d 4x 4a 1b 1b20 1a 6m 8d 4x 4e 1b 1b21 1a 6n 8d 4x 4e 1b 1b22 1g 6i 4e 4y 8d 1b 1b23 1a 6j 4e 4y 8d 1b 1b______________________________________
EXAMPLE 22
In an aqueous solvent, 23.9 parts of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was condensed with 18.4 parts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate was condensed with 28.1 parts of 4-(2-sulfate ethylsulfonyl)aniline according to a normal method to obtain a naphthol derivative.
In an aqueous solvent,41.1 parts of 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene was diazotized by using sodium nitrite, the diazotized product was diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(c) to obtain a monoazo compound. This monoazo compound was diazotized by using sodium nitrite and then diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(d) to obtain a bisazo compound. This bisazo compound was diazotized by using sodium nitrite and then diazo-coupled with the above naphthol derivative to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR48##
EXAMPLE 23
According to the same manner as that described in Example 22 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6 and a compound of the column 7 shown in Table 13 in place of 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 2,4,6-trichloro-s-triazine, 4-(2-sulfate ethylsulfonyl)aniline, 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(c) and 7-amino-4-hydroxynaphthalene-2 r8-disulfonic acid(d) used in Example 22, respectively, each corresponding polyazo compound was obtained. Using the polyazo compound thus obtained, dyeing was carried out and a dyed product having a color shown in the column 8 of Table 13 was obtained.
TABLE 13______________________________________Col-umn Column Column Column Column Column Column Column1 2 3 4 5 6 7 8______________________________________ 1 1a 4x 4a 4m 1b 1b purple 2 1a 4x 4a 5j 1b 1b purple 3 1a 4x 4a 5y 1b 1b purple11 1g 4x 4a 5j 1b 1b purple13 1g 4x 4a 5y 1b 1b purple______________________________________
EXAMPLE 24
According to the same manner as that described in Example 22 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6 and a compound of the column 7 shown in Table 14 in place of 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 2,4,6-trichloro-s-triazine, 4-(2-sulfate ethylsulfonyl)aniline, 6-(2-sulfate etylsulfonyl)-1-sulfo-2-aminonaphthalene, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(c) and 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(d) used in Example 22, respectively, each corresponding polyazo compound was obtained.
TABLE 14______________________________________Column Column Column Column Column Column Column1 2 3 4 5 6 7______________________________________ 4 1a 4x 4e 5a 1b 1b 5 1g 4x 4a 4e 1b 1b 6 1g 4x 4a 4g 1b 1b 7 1g 4x 4a 4i 1b 1b 8 1g 4x 4a 4k 1b 1b 9 1g 4x 4a 4n 1b 1b10 1g 4x 4a 5a 1b 1b12 1g 4x 4a 5p 1b 1b14 1g 4x 4v 5j 1b 1b15 1g 4x 4v 5y 1b 1b21 3c 4x 1g 4e 1b 1b22 3c 4x 1g 4g 1b 1b23 3c 4x 1g 4i 1b 1b24 3c 4x 1g 4k 1b 1b25 3c 4x 1g 4m 1b 1b26 3c 4x 1g 5a 1b 1b27 3c 4x 1g 5j 1b 1b28 3c 4x 1g 5p 1b 1b29 3c 4x 1g 5y 1b 1b______________________________________
EXAMPLE 25
In an aqueous solvent, 18.8 parts of 4-sulfo-1,3-diaminobenzene was condensed with 18.4 carts of 2,4,6-trichloro-s-triazine according to a normal method and the resultant condensate was condensed with 28.1 parts of 3-(2-sulfate ethylsulfonyl)aniline according to a normal method.
In an aqueous solvent, the compound thus obtained was diazotized by using sodium nitrite, the diazotized product was diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(e) to obtain a monoazo compound. This monoazo compound was diazotized by using sodium nitrite and then diazo-coupled with 31.9 parts of 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid (f) to obtain a bisazo compound. This bisazo compound was diazotized by using sodium nitrite and then diazo-coupled with 30.4 parts of 3,6-disulfo-1-naphthol to obtain a compound, the form of a free acid of which is represented by the following formula: ##STR49##
EXAMPLE 26
According to the same manner as that described in Example 25 except for using a compound of the column 2, a compound of the column 3, a compound of the column 4, a compound of the column 5, a compound of the column 6 and a compound of the column 7 shown in Table 15 in place of 4-sulfo-1,3-diaminobenzene, 2,4,6-trichloro-s-triazine, 3-(2-sulfate ethylsulfonyl)aniline, 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(e), 7-amino-4-hydroxynaphthalene-2,8-disulfonic acid(f) and 3,6-disulfo-1-naphthol used in Example 25, respectively, each corresponding polyazo compound was obtained.
TABLE 15______________________________________Column Column Column Column Column Column Column1 2 3 4 5 6 7______________________________________ 3 3c 4x 8d 1b 1b 7c 5 3c 4x 8d 1b 1b 7d 6 8c 4x 4a 1b 1b 7e 7 8d 4x 4a 1b 1b 7f13 8d 4x 4b 1b 1b 7d14 8d 4x 4c 1b 1b 7d15 8d 4x 4d 1b 1b 7d16 8d 4x 4f 1b 1b 7d17 8d 4x 4h 1b 1b 7d18 8d 4x 4p 1b 1b 7d______________________________________
EXAMPLE 27
According to the same manner as that described in Example 14 except for using above-mentioned compound 2a, 1a, 4a and 4x in place of the compound of formula (22), 5-amino-4-hydroxynaphthalene-2,7-disulfonic acid, 3-(2-sulfate ethylsulfonyl)aniline and 2,4,6-trichloro-s-triazine used in Example 14, respectively, each corresponding polyazo compound was obtained.
EXAMPLE 28
0.3 Part of bisazo compound obtained in Example 27 was dissolved separately in 200 parts of water. Then 20 parts of sodium sulfate and 10 parts of cotton were added to the solution and the solution was heated to 70.degree. C. After 30 minutes at this temperature, 4 parts of sodium carbonate was added and dyeing was effected for an hour. Upon completion of dyeing, the product was subjected to rinsing and soaping to give an yellowish-red dyed product excellent in various fastness and having a good build-up properties.
EXAMPLE 29
Using compound obtained in Example 27, a color paste having the following composition was prepared:
______________________________________Bisazo compound 5 partsUrea 5 partsSodium alginate 50 partsHot water 25 partsSodium hydrogen carbonate 2 partsBalance (water) 13 parts______________________________________
The color paste was printed onto a mercerized cotton broad cloth, which was subjected to intermediate drying, rinsing with warm water, soaping, rinsing with warm water and drying to give an yellowish-red printed product excellent in various fastness.

Number	Date	Country
8-181830	Jul 1996	JPX
8-270168	Oct 1996	JPX
8-348937	Dec 1996	JPX
9-008690	Jan 1997	JPX

Number	Name	Date	Kind
4939243	Meininger et al.	Jul 1990
5686584	Dietz et al.	Nov 1997

Number	Date	Country
3519551	Dec 1986	EPX
281898	Sep 1988	EPX
0395951	Apr 1990	EPX
0712905	Nov 1995	EPX
1490447	Jun 1967	FRX
2634497	Mar 1978	DEX
3202120	Jul 1983	DEX
8-209016	Aug 1996	JPX

Polyazo compound and method for dyeing or textileprinting fiber material using the same

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Chemical Abstracts, Chemical Substance Index, vol. 99, Part 3, p. 4277CS, 1983.
Chemical Abstracts, Chemical Substance Index, vol. 106, Part 3, p. 5213CS, 1987.
Chemical Abstracts, vol. 115, abstr No. 94411 (1991).