CA1062409A - Basic dye composition - Google Patents

Abstract

ABSTRACT
Basic dye compositions comprising one or more finely dispersed difficultly soluble dye complex salts composed of one or more water-soluble basic dyes and one or more dispersants capable of being ionically bonded to said basic dye. The dye compositions can be used to obtain level dyeing of acid modified polyester and polyacrylonitrile fibrous articles without causing significant coloration of machinery and process workers.

Description

~ ~ .

- ~06Z4C~9 This invention relates to basic dye compositions comprising one or more finely dispersed difficultly water-soluble dye complex salts com-posed of one or more water-soluble basic dyes and one or more dispersants capable of being ionically bonded to said basic dye, which are suitable for dyeing acid modified polyester and polyacrylonitrile fibrous articles.
According to one aspec~ of the invention there is provided a basic dye composition in finely divided form which comprises a complex salt of low water solubility formed by ionic bonding between one or more water-soluble basic dyes and at least one anionic dispersant capable of being ionically bonded to the basic dye or dyes, wherein the anionic dispersant is selected from the group consisting of alkali metal9 alkaline earth metal.
a~monium and aluminium salts of (a) a candensate of formaldehyde with 1-or 2- naphthalenesulfonic acid, (b) a condensate of formaldehyde with methyl naphthalenesulfonic acid, (c) lignin sulfonic acid and (d) alkyl sulfate and the amount of anionic dispersant present is greater than the stoichiometric amount re.quired to react with the water-soluble basic dye but less than 15 parts by weight per part by weight of the water-soluble dye~
According to a further aspect of the invention there is provided a process for the preparation of a basic dye composition which comprises a 2Q finely dlvided complex salt of low water solubility, which process comprises reac~ing a water-soluble basic dye and an anionic dispersant capable of being ionically bonded to said basic dye to form tbe complex salt of low water-solubility, wherein the anionic dispersant is selected from the group consisting of alkali metal, alkaline earth metal, ammonium and aluminium salts of (a~ a condensate of formaldehyde with 1- or 2-naphthalenesulfonic acid, (b) a condensate of formaldehyde with methyl naphthalenesulfonic acid, tc) lignin sulfonic acid and (d) alkyl sulfate and the amount of anionic dispersant present is greater than the stoichiometric amount required to react with the water-soluble basic dye but is less than 15 parts by weight 3Q per part of the water-soluble basic dye.
Il .

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~624~g In general, dyes are classified by method of application ~dyeing properties) rather than by their chemical nature although this is not in-variably true. Classification by structure would lead to confusion since many dyes which are closely related chemically behave quite differently in dyeing. For instance, C.I. Basic Violet 14 and C.I. Acid Violet 19 differ Qnly in the solubilizing sulfonic acid group on the latter, but their dyeing behaviour is entirely different. (See Encyclopedia of Chemical Technology, vol.7, p. 507). Persons skilled in the art understand that basic dyestuffs are water soluble and they are quaternary ammonium salts or amines which form 1~ easily stable quaternary ammonium salts with acid. Moreover "basic dyestufs"
are suitable for dyeing wool, silk, leather, polyocrylonitrile the acid-modified polyester and the like. Therefore even i~ a dyestuff is basic by virtue of an amino group, wlthout the said chemical properties and without being suitable for the above uses it i8 not considered a "basis dyestuff" and it is not suitable for use in this inventian.
Basic dyes have heretofore been marketed and used in the form of powders and crystals, in some cases mixed with appropriate solid diluents or assistants. -It has however been appreciated that these dye powders have several 2Q undesirable defects. For instance, water-soluble powdery dyes having a high tinting strength tend to get scattered during packing, weighing, pouring or shaking, and cause contamination, irritation and discoloration. Further, i they are not stored under good conditions, they tend to coagulate into very difficultly soluble agglomerates due to the action of moisture and heat.
As a means for overcoming these problems, a process is known for dyeing anionic polymeric fibers using a finely dispersed complex compound of a basic dye with a composite poly-acid selected from the group consisting of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolyb-dic acid and silicotungstomolybdic acid (see Japanese Patent Publication No.
19369/67).

~ - la -~L06240~
. .
In this process~ it is necessary to employ molybdenum and ~ungs~
ten which are more expensive than the starting materials used in the forma-tion of the dye complex salts of this invention. Furthermore, the waste :
water recovered from the dyeing step of this known process contains salts of these composite poly-acids and hence, problems are encountered in the treatment of such waste water. In contrast, in this invention, a cheap commercial dispersant may be employed, and since salts of such heavy metals as molybdenum and - lh.
~
','''.

~LOG%409 tungsten are not con~ained in the resulting waste water, the water is e~sier to treat. Also, in this invention, a very good manufacturing efficiency can be attained because preparation of the dye complex salt can be conducted simultaneously with dispersion of the dye.
German Patent Application Laid-Open Specification No. 1,921,277 dis-closes a p~ocess for preparing a dye composition by finely dispersing a com-plex composed of a specific aromatic sulfonic acid and a basic dye. If an aromatic sulfonic acid is employed as an anion, a large amount of water must be used in the complex-forming reaction and a filtration step is required beore the dispersing step~ In short, an additional step must be conducted.
Furthermore, this process is defective in that the yield of the dye complex is low. Moreover, when the aromatic sulfonic acid is left in waste water ~` ;
from the step of dyeing anionic polymeric fibers, the COD (Chemical Oxygen Demand~ and BOD (Biochemical Oxygen Demand) values are decreased. In contrast, the anionic dispersant used in the present invention has none of these defects and exhibits good properties, and therefore the invention has indus-trial advantages.
As pointsd above, the basic dye composition of this invention com-prises a difficultly soluble complex salt of a water-soluble basic dyc and an anionic dispersant in which cations of the dye are relatively tightly bonded to anions of the anionic dispersant, and therefore, dissociation of the ions does not occur at ordinary temperatures, though this undesirable phenomenon ;
is inevitably observed in conventional basic dyes~ Accordingly, unlike con-ventional powdery or liquid basic dyes, the basic dye composition of this invention does not cause conta~ination or coloration of human bodies, various vessels and the like Furthermore, the properties of the basic dye composi-tion of this invention hardly change with the passage of time, because the dye is composed of a relatively stable complex salt~
Any dyes h~ving a basicity sufficient to form the difficultly soluble complex salt t~gether with the anionic dispersant can be used as the starting material for the dye composition of this invention~ Accordingly, the basic dyes which may be used in this invention lnclude a variety of dyes differing

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~06Z409 in chemical form. Some of them are ordinarily called cationic dyes, and also included are basic dyes which act as a cationic chromatic group in an acidic aqueous medium. As basic dyes suitable for the formation of the difficultly soluble dye complex salts, there may be mentioned, for example, di- and tri-aryl methane dyes, pyronine dyes, Rhodamine ~trademark) dyes, acridine dyes, Safranine (trademark) dyes, oxazine dyes, quinoline dyes, thiazole dyes, basic azo dyes, basic azomethine dyes, basic polymethine dyes, basic asopoly-methine dyes, basic anthraquinone dyes, basic quinophthaline dyes, basic phthalocyanine dyes, and the like.
These basic dyes can be used both alone and as mi~tures of two or more of them in appropriate proportions.
The lignin sulfonic acid has the following basic structure C ~ S03H
J
C

OCH

and it has one sulfonic acid group per two benzene nuclei. It is usually recovered from the waste water obtained at the pulp-preparing step and is not a single compound but a mixture having a molecular weight of from several :
hundreds to several millions. It is a macromolecular electrolyte that is dissociated in water. It also has properties as a surface active agent.
As the alkyl sulfate there may be mentioned, for example, sodium lauryl sulfate and ammonium lauryl sulfate.
The anionic dispersant is employed in an amount of from 1 to 15 ;
parts per part of the water-soluble basic dye. These dispersants can be used singly, or two or more of them can be used in combination.

, . , ~L06Z409 The basic dye composition of this invention is prepared by bonding the water-soluble basic dye ionically to the anionic dispersant to form a difficultly soluble dye complex salt and then dispersing the complex salt with the anionic dispersant. In practice, it is preferred to prepare the `~
basic dye composition according to the following methods:
(1~ The water-soluble basic dye is dissolved or suspended in water and the anionic dispersant is mixed with the solution to form the difficultly ~;; ;
soluble dye complex sal~, which is then dispersed with the excess of the anionic dispersant not participating in the reaction or a fresh supply of the 10 dispersant by mixing and agitation. i ~2) The water-soluhle basic dye is dissolved or suspended in water and -the anionic dispersant is then mixed with this solution to form the diffi-cultly soluble dye complex salt, which is then dispersed in the state dis-solved in water or in the form of an aqueous slurry with the excess of the dispersant not participating in the reaction or a fresh supply of the disper- , sant by employing known mechanical dispersing means such as a colloid mill or i' ball mill or known dispersing techniques such as grinding or agitation to-gether with sand. --~3) The water-solu~le basic dye is dissolved or suspended in water and the anionic dispersant is mixed with the solution to form the difficultly soluble dye complex salt~ The complex salt is dispersed with the excess of the dispersant not participating in the reaction or a fresh supply of the dispersant by mixing and agitation, and in order to disperse it more sufficiently, known conventional dispersing techniques such as those men-tioned in t2) above are employed.
The composition thus obtained is dried to powder or ~ade pasty, and it is marketed in the powdery or pasty form. At this step, it is possible to add to the composition dextrin as an extender or dyeing assistant.

As disclosed in the Color Index, 2nd edition~ Vol. 1, page 1617, it 30 is ~nown th~t basic dyes are precipitated as water-insoluble pigments upon con- ; ~-tact with a composite poly-acid such as phosphomolybdic acid. Further, as taught by German Patent Application Laid-Open Specificatlon No 1,921,277 basic `:

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.

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dyes react with a specific aromatic sul~onic acid to form a dif~icultly soluble dye salt. If these dye-acid complex compounds and difficultly soluble aromatic sulfonic acid-dye salts are dispersed with an anionic dis-persant and are used for dyeing anionic acid-modified polymeric fibers such as acid-modified polyacrylonitrile fibers and acid-modified polyester fibers, the linkages between the basic dye and the poly-acid or aromatic sulfonic acid are severed and the basic dyes are quantitatively formed on the anionic poly-meric fibers. The released composite poly-acid moiety or aromatic sulfonic acid moiety is re~oved in the state contained in the used dye bath or in a 10 washing liquor used in the finishing treatmen~
In the basic dye composition of this invention, a basîc dye is ionically bonded to the anionic dispersant to form a substantially difficultly soluble complex salt. This co~plex salt is finely dispersed and with increase in temperature, it is gradually decomposed and only the basic dye is select-ively absorbed on fibers to give excellent, level dyeing. Therefore, the use of a levelling agent, as is customarily employed in this field, is not essential.
Since the basic dye composition of this invention consists substant-ially of the already-formed complex~ it is possible to conduct single bath dyeing by employing the dye composition in combination with a dye of another type, such as an acid dye, a disperse dye or a direct dye, that cannot normally be used in combination with an ordinary basic dye because of a tendency to form a complex therewith. Furthermore, the dye composition of this invention is very s~able against change in pH and hence dyeing can be performed under neutral conditions. These are substantial advantages of the basic dye composi-tion of this invention. 0 In the use of ordinary cationic dyes for printing, it is necessary, in order to dissolve them, to add a dye-solubilizing agent and to conduct heating at a high temperatu~e~ Furthermore, even when they are dissolved, crystals are readily precipitated by cooling or upon contact with a paste, and therefore there is a danger that specks will be formed, In the case of the dye composition of this invention there is no danger of the formation of ' . ' ' , ` ~'' '. ' '` : .' ' ' ' .
: . ~

~O~iZ4~)9 ~ ~
such specks. Moreover, in the case of ordinary ca~ionic dyes, an undercloth ;;~
is readily contaminated at the printing step and this contamina~îon cannot readily be removed and results in various operational troubles~ However, the dye composition of this invention causes little, if any, such contamination.
This invention will now be described in more detail by re~erence to the following Examples, in which all "parts" and "%" are on a weight basis unless otheTwise indicated. It should be noted that ~he scope of this inven- ~;
tion is by no means limited by these Examples~ j Example 1 33 par~s of a basic yellow dye, C.I. Basic Yellow 11 (C.I. No.
48055) was added ~o 400 parts of water, and the mixture was agitated suffic-iently. Then, 66 parts of a dispersant ~a sodium salt of a condensate of formaldehyde~with 2-naphthalenesulfonic acid) was gradually added to the dye solution, whereby a difficultly soluble dye complex was formed. This complex was mixed and agitated and thereby was gradually finely dispersed. The result-ing fine dispersion was spray-dried according to customary procedures to obtain l00 parts of a composition of the above yellow dye. ;
In this Example, the dye complex could be dispersed advantageously ~
by the combined use of the above means and known mechanical dispersing means. ~`;
~ e~c_~
26 parts of a basîc orange dye, C.I. Basic Orange 21 (C.I. No. ~
48035) was added to 350 parts of water, and the mixture was agitated suffic- `
lently~ Then, 2 parts of anhydrous sodium carbonate was added to the solu~
tion to make it neutral. When 74 parts of the same dispersant as used in Example 1 was added to the solution, a difficultly soluble dye complex salt was precipitated. This complex salt was finely dispersed by grinding it sufficiently in a ball mill and drying it to obtain 100 parts of a composition ;~
of the above orange dye.
Example 3 27 parts of a yellow dye represented by the following formula ~ -''~: '' ~L06Z409 ;' :' ' ' C\3 ~CH3 -N ~C - -CH = N - N a OCH3 Cl c~l3 C~3 ., .
was added and dissolved in 300 par~s of water. ~nhen 67 5 parts of the same dispersant as used in Example 1 was added to the solution, a difficultly soluble dye salt was precipitated and a part of the salt was finely dispersed.
In order to disperse the complex salt sufficientlr, it was ground in the pre-sence of sand at 45 to 50C. Then, 5.5 parts o dextrin was added and the mixture was dried to obtain 100 parts of a composition of the above yellow dye, which exhibited a tinting strength comparable to that of 100 parts of a commercially available product of the above yellow dye.
Example 4 30 parts of a red dye represented by the following formula ~ ~ C CH c ~H ~ ~ / 3 ¦~ 3 was added to 400 parts of waterl and the mixture was agitated sufficiently.
When 20 parts of a dispersant ( a sodium salt of lignin sulonic acid ) was added to the solution, a dye complex salt was precipitated. Then, 45 parts of ~he sam~ dispersant as used in Example 1 was added and the mixture was suficiently ground in a ball mill, dried and pulverized to obtain a dye `
,. ~
composition~

Formation o dye complex salts and compositions thereof were con-ducted in the same manner as described above with the use of the basic dyes and anionic dispersants indicated in Table 1.

_7-~ 106Z409 ~

Table 1 r`~
Basic Dye Dispersant sodium salt of i.
CH CH 2-naphthalenesulfonic

3 \ ~ 3 C H acid-formaldehyde Cl ~ / 2 5 condensate '~. - :
1. U /~ CH = C ~ N Cl~

2. ~ ~ ~ Cll = CH - ~ N C1~3 C~H~CN C~3 2 4 2 5 .'.~' .~
~``', ,' . .

3~ ~<>r al =N--N--C} Cl Cl~) r C2H4CH3 .
~:~ 20

4~ (~</r CH --N--N ~(}N =N ~ Cl~
I G) ,. . .
C~3 sodium salt of lignin CH3 C~13 C2H sulfonic acid

5. ~ ~ ~ CH - CH - ~ N Cl ~ ;

30 C~

,j. '; ' .

'': . ''''' lOt~Z409 Crable 1 contId.) Basic Dye Dispersant i~
sodiu~ salt of CH 2-naphthalenesulfonic ~-C 3 \ / 3 CH3 acid-formaldehyde `~
~ / condensate

6~ /~ CH = CH ~ N Cl~

2 4 2 .
.,, ' ,". ;- ,.

~ C 3 '~

7. ~ ~ ~1 - CH ~ O Cl~

C2H40C4Hg C~3 . ' ,

8. ~ CH - CH ~ H2 Cl~
1 ~3 CH3 ~ ~.
:-~o Example 5 35 parts of a yellow dye represented by the following formula HC - ~ N ~ Ct~
N /C N = N 11 ~ C1~3 was added to 400 parts of water, and the mixture was agitated sufficiently.
When 65 parts of the same dispersant as used in Example 1 was gradually added to the solution, a dye complex salt was precipitated. Then, the reac-tion mixture was sufficiently ground in a ball mill, dried and pulverized toobtain 100 parts of a dye composition.
-~, _g_ , .~ :
j.

- `' 3L~62409 ,', .: '' Example 6 30 parts of a red dye represented by the following formula .~ , . :,, 1~ G~N P
CH2CH2CNH2 I Cl~

was added to 350 parts of water, and the mixture was sufficiently agitated.
l~hen 70 parts of the same dispersant as used in Example 1 was added to the liD solution, a dye complex salt was prec;pitated. The reaction mixture was sufficiently ground, dried and pulverized to obtain 100 parts of a dye com-position.
:.!:. ` ' . ' .
Example 7 40 parts of a red dye represented by the followinj~ formula ~ , .
HC _ N - CH3 C2H5 N / N N O N \ Cl / 2 was added to 400 parts of waterJ and the mixture was sufficiently agitated.
Then, 2.5 parts of anhydrous sodium carbonate was added to the soluti~n to adjust the pH to a neutral value. ThenJ 60 parts of the same dispersant as ':~
used in Example 1 was added to the solution and the precipitated dye complex ;~
salt was sufficiently ground. The fine aqueous dispersion of the dye complex salt was spray dried to obtain 100 parts of a dye composition~

Example 8 17 parts of a blue dye represented by the following formula P~ C~O ~[X ~C N = N ON/

-10- ,, ., .
, .

~ ,.i ... .

- \ `
'` 113 62~(~9 was added to 300 parts of water and dissolved therein. ~hen 44.2 parts of the same dispersant as used in Example 1 was gradually added to the solution, a difficultly soluble dye complex salt thus formed was precipitated. After I
completion of the addition of the dispersant, ~he reaction mixture was ~-sufficiently ground in a ball mill. Then, 38.8 parts of d~xtrin was added ~,~
and the fine aqueous dispersion of the dye complex salt was spray dried to obtain 100 parts of a dye composition.
ExamE~le 9 18 parts of a blue dye represented by the following formula CH30 ~ 5 / C4H9 ~ ~3 C H CN

was added and dissolved into 300 parts of water~ When 40 parts of the same dispersant as used in Example 4 (a sodium salt of lignin sulfonic acid) was added to the solution, a dye complex salt was precipitated and gradually dis- `
persed finely. A ball mill was employed to disperse the complex salt suffic-iently~ The resulting liquid dispersion of the dye complex was incorporated with 42 parts of sodium sulfate, and the mixture was dried and pulverized to obtain 100 parts of a dye composition. ~`
Example 10 25 parts of a blue dye represented by the following formula o NHCH3 o N~l - (C~2)3N ~ C~13 al350 C~1 was added to 400 parts of water and agîtated sufficiently. Then, 65 parts of the same dispersant as employed in Example 1 was gradually added to the solution, and a dye complex salt thus formed was finely dispersed by means of a ball mill~ Then, 10 parts of dextrin was added to the dispersed complex ~.....

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1062409 ~
salt, and the mixt~re was dried to obtain 100 parts of a dye composition.
With use of the basic dyes and anionic dîspersants indicated in Table 2, the formatîon dye complex salts and the grinding thereof was con-ducted în the same manner as described above. .
Table 2 ~ .
Basic Dye Dispersant . ~
" .
sodium salt of 2-naphthalenesulfonic acid-formaldehyde ., 1.C - ~3 - CH3 / CH3 condensate N C - N = ~ ~ N Cl CH - O sodium salt of methyl- .:
naphthalenesulfonic .
acid-formaldehyde /s \ condensate ;~
2.~ /~ N N ~ O

C~ - CII Cll OCII` C~13 OH .
.'',~,.' '.:';

CH3~ / CH3 ~.
N '' 2 ~:~
; C2114CNH2 sodium salt of ;, 2-naphthalensulfonic CH O acid-formaldehyde ~`
3 ~ ~ /S \ c~ndensate :;
4~ ~ ~ -N =N - ~ ~ C1~3 ~`~1 .'.
~113 C2~5 ,~
' , . .

: .....

1~6Z~09 tTable 2 cont'd.~
Basic Dye Dispersant .
sodium sal~ of 2-naphthalenesulfonic acid-formaldehyde ~:
condensate N - N ~ N -.

C2~4C~ Cl~ C2 4 C2 5 sodium salt of lignin - .~.
C H sulfonic acid and CH30 ~ / S r~x / 2 5 sodium salt of ~ ~ ~ N c N -( ~ N 2-naphthalenesulfonic 6~ -J \ ~ acid^for~aldehyde 3 Cl~ C2ll4~3~ condensate ''. ', sodium salt of 2-naphthalenesulfonic acid-formaldehyde ~.;
CH30~v~ fS \ /__~ ~ Cl~ condensate N /~ ~ N ~ ..
I ~ C~
~':

Example 11 .
25 parts of a red dye represented by the follo~ing formula .~:

..~

02N ~ N ._ N - a N /
C2~14N ~CH3 C 1(3 , ~ , C~3 ;
was added to 400 parts of water and the mixture was agitated sufficiently. .`~
Then, 60 parts of the same dispersant as used in Example 1 was gradually added to the solution, and a dye complex salt thus formed was finely ground~il.. . -by a ball mill, incorporated with 15 parts of dextrin and dried to obtain 100 '; :
parts of a co.mposi*i.on of the above dye, ~hich exhibited a tinting strength : : .3 comparable to that of 100 parts of a commercially available product of the above dye. . ::~
-13- . :

,, ' ,,.: . .
'.',~' ~

0624~9`
;, .. ....
Example 12 35 parts of a yellow dye represented by the following formula ;
;,., :.'~ " ' H3C ~ N - ~2C - C - ~ N = N - ~ NH~2H4 , . . .
was added to 400 parts of water and the mdxture was sufficiently agitated.
Then, 65 parts of the same dispersant as used in Example 1 was gradually added to the solution, and the resulting dye complex salt was ground in a ?, ~
ball mill and dried to obtain 100 parts of a dye composition. ~ ;
Example 13 4' ` '' ' ' .
22 parts of a blue dye represented by the following formula ~

.. . .
C~3--N = C ~ IH3 OC2H5 Cl ~ '~' ~ ;

was added to 350 parts of water, and the mixture was sufficiently agitated. ,~
Then, 55 parts of the same dispersant as used in Example 1 was gradually added to the solution, and the resulting dye complex salt was sufficîently ground, incorporated with 23 parts of dextrin and dried to obtain 100 parts of a composition of the above dye~ `
Example 14 ~
.;~. :.
28 parts of a blue dye represented by the following formula ~

C2~15 ~ ~ /~ / ~3 :~' ' C~H5 C2~5 ~
~ ;
, : .
was added to 300 parts of water, and the mixture ~as sufficiently agitated.
Then, 72 parts of the same dispersan~ as used in Example 1 was gradually ..

106Z409 :~

added to the solution, and the resulting dye complex salt was ground by a ball mill. The resulting substantially liquid dispersion was dried and pulverized to obtain a composition of the above dye.
The above procedures were repeated by employing instead of the above blue dye a dye represented by ~he following formula i ~ N/ ~ O / ~ N- ~ Cl~

1~ C2H5 ~.`. , , and a similar composition was obtained~
Example lS
33 parts of a green dye represented by the following formula `.

~ ~ C =~
CNH4C2 ~ C2H4CN ",~ ~, was added to 350 parts of water, and the mixture was sufficiently agitated.
20 Then, 67 parts of the same dispersant as used in Example 1 was gradually . ~ :
added to the solution, and the resulting dye complex salt was sufficiently ~ :
ground in a ball mill, dried and pulverized to obtain 100 parts of a dye com~
position. ' Example 16 .
10 parts each of dyes represented by the following formula .

~ CH = CH - HN - ~ OCH3 Cl~

3~ C~13 ."'~':' 15~
, ~

- ~06;~4C39 . ~ .

2 ~ N - N - O - N ~3 C2H4N ~ CH3 -CH3 ;~
and N = N{}N / ~) ~, ' ¦ ~) C2H~I,CN ,.

'~' were added to 300 parts of water and the mixture was sufficiently agitated. ^~
Then, 70 parts of the same dispersant as employed in Example 1 was gradually added to the solution, and the resulting dye complex salt was sufficiently ground in a ball mill and dried to obtain lO0 parts of a composition of a mixture of the dyes indicated above. This mixture was quite homogeneous. `;
In the same manner as described above, basic dyes were reacted with "
dispersants and resulting dye complex salts were ground and finely pulverized to obtain compos~tions of the dispersants and dyes indicated in Table 3. d Table 3 ;
Basic Dye Dispersant .;
sodium salt of ,;~
2-naphthalenesulfonic ~ acid-formaldehyde 1. (CH ~ NCH C0 O - N - N - ~ - p condensate H

J
''"" '" ~

2~(CH3)2N O I ~ N~C~l3)2 Cl O "'' ' ' -16_ ,'' ,' ' . .

`` 10~2409 (Table 3 cont'd.) Basic Dye Dispersant sodium salt of 2-naphthalenesulfonic :
acid-formaldehyde CH3 condensate ~c~c C\ O Cl ,, tC2H5)2N /C = 0 1 3 .

(C2 sl2 ~ ~ ~ C1 o C00C2H

,~ ~'',...

\ O -CH3 C1~3 ~C2H5)2N N N = N ~ N
: ~ C2H4CN ~ ;

6, (CH3)2N \ S N~CH3)2 C1~3 "
~ N ~

'' .'': .
, , , ,''~
~0 -17~

, . ~, .

~L062409 ~

~Table 3 cont'd.) Basic Dye Dispersant sodium salt of 2-naphthalenesulfonic `
acid-formaldehyde condensate ;~
~ 2 7` ~ ~ CH NtCH ) ,.
Cl~
:

~ .
25 parts of a yellow dye represented by the following formula ,', ', ' ~...
C~13 C~13 ~13 CH - N - N - ~ Cl Cl~
! ~ .

,.: .
was added to 250 parts of water, and the mixture was sufficiently agitated. ` ;

Then, 75 parts of a dispersant (highly pure product of sodium lauryl sulfate) ~, . . . ~
was gradually added to the solution~ The resulting difficultly soluble dye complex salt was gradually dispersed finely, which was sufficiently ground by ;
a ball mill, dried and pulverized to obtain lO0 parts of a dye composition.
,,: . , In the same manner as described above, dye complex salt compositions ~
were prepared from the basic dyes and anionic dispersants indicated in Table `-4.
Table 4 Basic Dye Dispersant CH3 sodium lauryl sulfate -~
~highly pure product) 1. N~ ~ N = N ~ O N / C1~ 112 ZnC12 ~ ;

...

`:

106Z409 j`

(Table fl cont'd.) .. :.
Basic Dye ~ispersant '-.; . . .:
sodium lauryl sulfate (highly pure product) .
CH

~ I ~ N = N- ~ ~ ~ cl~? ~`.'~ ;
2, CH30 S \ . :
C2~1~?0H ;~

, .` ': ;:
~ ~ CH3 / CH3 3 ~ S~ ~ N Cl~ " :. ~ .
CH30 C112 ~ ~

sodium lauryl sulate ~ .
~N C ~1 (highly pure product) .:
~ \ / 2 5 and naphthalenesulfonic i:
0 N ~ ~ N = N ~ ~ N acid-formaldehyde .::
4 2 ~ \--~/ \ ~3 CH condensate i.
~ CH3 Cl~ ?,'~,' ;
,'~" ' ' .:, :.
~ / CH3 5. ~N~

Example 18 (ordinary dy~ing method) :, 2 parts of the basic red dye composition prepared in Example 6 was ;
sufficiently mixed ~n 5000 parts of warm water containing 1 part of glacial '. :: :
acetic acid to form a dye bath~ Then, 10~ parts of a yarn of polyacryloni- :
trile fibers:was immersed in said dye bath at 60qC~ and the temperature of the dye bath was elevated to 98 to 100C~ over a period of 30 minutes~ ~`
Dyeing was conducted at this temperature for 60 minutes, and the dyed~yarn ?? _ ~
"~ `' " ' ' 1062409 ~
" . :. , was washed with water~ ~-A clear red dyeing was ob~ained. Contamination of the worker's body or the dyeing vessel was insignificant.

Example 19 tshor~ time dyeing method) , . .
4 parts of a basic yellow dye composition prepared in Example 5 was sufficiently mixsd into 5000 parts of warm water containing 1 part of glacial acetic acid to form a dye bath. Then, 100 parts of a cloth of polyacryloni-trile fibers was immersed in the dye bath at ~0C~ and the temperature of the dye bath was elevated to 100C. over a period of 10 minutes. Dyeing was con~
ducted at this temperature for 30 minutes~ and the dyed cloth was then washed with water. A level yellow dyeing was ob~ained in a short time without .; .
employing a ratarding agent. Accordingly, this method was very advantageous -from an economical viewpoint.
Example 20 ~one bath dyeing of acrylic and wool mixed fibers) 1 part of a basic blue dye composition prepared in Example 14 was dispersed in 10 parts of water. Separately, 2 parts of Kayanol Milling Blue BW ~acid dye manufactured by Nippon Kayaku K.K.) was dissolved in 20 parts of hot water. Both the solutions were added 6000 parts of water containing 1 part of glacial acetic acid to form a dye bath. Then, 100 parts of a yarn of `
mix spun fibers of acrylonitrile: wool ~S0:50) was immersed in the dye bath at 60C. The temperature of the dye bath was elevated to 100C. at a rate of lqC. per minute, ant dyeing was conducted a~ this temperature for 60 minutes.
Then, the dye bath was gradually cooled. In the case of ordinary cationic '!;',.
dyes, if an expensive precipitation-preventing agent is not used, tarring occurs and no level dyeing is obtained. However, in the case of the dye composition of this invention, a level dyeing was obtained without using such ,~ . .
an additive, and the dyeing operation could be performed very easily. `

Bxample 21 (dyeing of 65:35 mixed acrylic and rayon fibers) 1 part of a basic yellow dye composition obtained in Example 5 was dissolyed in slightly warm water maintained at about 40C~ Separately, 1 part of Kayarus Supra Ye~low RL (direct dye of high grade manufactured by Nippon Kayaku K.R.) was dissolved in hot water. Both the solutions were '-.

,~, : ` ~0624~9 `~:

added to 4500 parts of pure water incorporated with 0.2 part of glacial acetic acid, and the resulting dye bath was heated to 70C. Then, 12 parts of anhydrous sodium sulfa~e was added to the bath, and 120 parts of a yarn of -acrylonitrile-rayon mixed spun fibers was thrown in~o the bath. The tempera-ture of the dye bath was elevated to 100C. over a period of about 30 minutes and at this temperature dyeing was conducted for 60 minutes. The dye bath was cooled to 60C. and a fixing treatment was conducted according to cus-tomary procedures. A fast dyeing of a concentrated yellow color could easily be obtain~d.
In the case of ordinary cationic dyes, a good reproducibility can-not be obtalned when the pH of a dye bath is 5 to 6 as in this Example. In contrast, the co~iposition of this invention was very stable even at such a bath pH, and a variety of direce dyes could be used in combination.
Example 22 ~dyeing of 50:50 acrylonitrile-polyester mixed fibers) 1 part of a basic yellow dye composition prepared in Example 5 and 2 parts of Kayalon Polyester Yellow YL-SE (C.I. Disperse Yellow 60 manufac- `;
tured by Nippon Kayaku K.K.; disperse dye) were dispersed in slightly warm water, and the dispersion was diluted with 6000 parts of water. Then, 0.5 part of glacial acetic acid, 10 parts of dichlorobenzene and 1 part of sor-bitan monolaurate were added to the bath and sufficiently mixed therein.
Then, 100 parts of a yarn of acrylonitrile-polyes~er mix spun fibers was immersed in the bath, and the temperature of the dye bath was elevated to 100C. from 60C. at a rate of 1C. per minute~ Dyeing was conducted at this temperature for 60 minutes to obtain a fast dyeing of a clear lemon yellow color.
The dyes could easily be dissolved and no problems occurred with -the basic dye composition, disperse dye and carriers. Dyeing could be carried out without substan~ial contamination of the dyeing vessel.
Example 23 ~Dyeing of 50:50 acrylonîtrile-cotton mixed fiber yarn) . . .
0,4 part of a basic blue dye composition prepared in Example 14, 1 part of Procion Brilliant Blue H-5G (C.I. Reactive Blue 25), 0.7 part of glacial acetic acid and 0,5 part of sodium acetate were dissolved and dis- ;~

.

1~624(19 persed into 5000 parts of pure water. Then, 200 parts of a yarn of acrylic and cotton mixed fibers was immersed in the so obtained dye bath, and the temperature of the dye bath was elevated to 100C. from 70C. over a period of 20 minutes. Dyeing was conducted at this temperature for 40 minutes. Then, the bath was gradually cooled to 90C. and 250 parts of anhydrous sodium sul-fate was added to the bath. Then, the temperature was further lowered and at 80C. 700 parts of soda ash was added. The yarn was thus treated for 40 minutes and water soaping was carried out to obtain a fast dyeing of a turquoise blue color. -~

Example 24 (continuous pad-steam dyeing of acryl fiber-tufted carpet) Material to be dyed:
Vonnel-tufted carpet (substrate being cotton) lO parts -Pad bath composition:
Dye ~composition prepared in Example 3) 10 parts Starch paste 2 parts 50% tartaric acid lO parts ,~ ~ `
Water 978 parts Dyeing method:
Fibers immersed in the above pad bath for 1 to 2 seconds were squeezed by a special rubber mangle so that the weight of the fibers was l.9 .~
times the dry weight. Then, the fibers were treated for lO minutes in a steamer at 180C., and then, they were treated at 60C. for lO minutes in a washing tank containing 1000 parts of water incorporated with 2 parts of non-ionic activating agent, thereby to obtain a dyeing of a clear orange-like yellow color.
In this dyeing method, the substrate cloth was hardly contaminated with the cationic dye and in view of the dye-absorbed state, it was found that the resulting dyeing was excellent in levelness.
Example 25 (printing) A color paste liquid mixture was prepared from 4 parts of a dye compositlon prepared in Example 4, 56 parts of carboxy methyl cellulose type thickener (diluted to 20% concentration and taking the form of a highly vis-* Trademark for a polyacrylonitrile fiber ;

` 106;~4~9 cous liquid), 3 parts of tartaric acid, 4 parts of urea and 33 parts of water, and this color paste was printed on a polyacrylonitrile cloth and the printed ' -cloth was dried at room temperature. Then, the cloth was subjected to the steaming treatment at 100C. for 30 minutes. The dyed cloth was washed with w æ er to obtain a printed cloth of a clear red color. `
Example 26 1 part of a raw powder of C.I~ Basic Red 46 was insolubilized with C, It~,S ~5~3 a, 3 parts of sodium lauryl sulfate ~ , and the mixture was blended ~`
and dispersed in a colloid mill and dried. Then, 4 parts of the so obtained dye powder was dispersed and dissolved in 1500 par~s of warm water maintained at 40C. and the pH was adjusted by addition of 1 part of glacial acetic acid.
.
Then, 100 parts of a plain weave fabric of Dacron (trademark) T-64 (basic dye-dyeable polyester) was immersed in the so obtained dye bath9 and the tempera- 'il-ture of the dye bath was gradually elevated to 120C~ over a period of 30 minutes, Dyeing was conducted at this temperature for 60 minutes and the `~
temperature of the dye bath was lowered to obtain a dyeing of a concentrated ;`
red color. In this Example, a level dyeing could be obtained without use of an assistant, and although the dyeing exhibited a concentrated color, no dye -was left after the dyeing operation and the waste water was colorless and transparent. When the above dyeing procedures were repeated with the use of ;
.,: ., .
ordinary water-soluble basic dyes, the dye absorption rate was extremely high ;
at temperatures approximating 110C. and it was difficult to obtain a level :
dyeing.
~xample 27 A mixture of 80 parts of C.I. Basic Orange 21, 170 parts of C.I.
Basic Green 4 and 350 parts of C~I~ Basic Red 18 was insolubilized with 1500 parts of sodium lauryl sulfa~e, and the insolubilized dye mixture was dis- :
persed and dried. Then, 8 parts of the so obtained black dye was dispersed and dissolved in 4000 parts of water, and 1 part of Kayakalan Black TLB (acid dye manufactured by ~ippon Kayaku K,K.) was added thereto, following which the - `
pH was adjusted to 4 to S by addition of 1 part of glacial acetic acid. Then, 100 parts of a yarn of 70.30 acrylic and wool mixed fibers was immersed in the ,; .
-23- ~
~ .', ~:)6Z409 so obtained dye bath~ The tempera~ure of the bath was elevated from room temperature to lOO~C. over a period of 30 to 40 minutes and dyeing was con-ducted for 90 minutes at this temperature. Both the acrylic and wool fibers were readily dyed simultaneously to obtain a level dyeing of a black color.
When 1 part of sodium polyoxyethylene lauryl sulfate ~C12 ~ O(CH2 CH20)nS0 ~ a] was added prior to the dissolution of said black dye and dyeing was conducted in the same manner, a level dyeing similar to the above was obtained.
When commercially available products of the foregoing water-soluble basic dyes were employed without the insolubilizing treatment, the resulting ~ `~
dyeing had a much reduced concentration and an intended hue could not be obtained. ~urther, specks of the insoluble material were stuck to the dyed product and the fas~ness to abrasion was extremely poor.
~nhen the above composition was employed, however, formation of specks was not observed and the fastness to abrasion was very good.
(In this Example, all the parts correspond to percent values based on the weight of commercially available water-soluble basic dyes used in the comparative run.) Ex~mple 28 0.9 part of a composition of C~I. Basic Red 29 and a naphthalene-sulfonic acid-formaldehyde condensate, 0.5 part of glacial acetic acid, 0.1 part of crystalline sodium acetate and 0.9 part of polyoxyethylene nonyl-phenyl ether ~CgH~t ~ O(CH2CH20)nH, n = 8 - 16] were dissolved in 1000 parts of water, and 20 parts of a highly bulky yarn of polyacrylic fibers having anionic groups was immersed in the so obtained dye bath, and the temperature of the dye bath was elevated to 98 to 100C. over a period of 30 minutes. Dyeing was conducted at this temperature for 60 minutes. The dye bath was cooled and the dyed yarn was taken out of the bath~ The optical density of the remaining liquid was measured by an automatic-recording ~
3Q phQtoelectric s~ectFometer~ Model EPR~2 manufactured by Hitachi Seisakusho i;
and it was found that the dye absorption was 96~7%~
When the above procedures were repeated without the addition of ;

,.~

.

~C~62409 polyoxyethylene nonylphenyl ether, the dye absorption was 82.6~. A denser dyeing was obtained when polyoxyethylene nonylphenyl ether was added.
Example 29 ', ' "' 0.3 part of a composition of C.I. Basic Blue 65 and a naphthalene-sulfonic acid-formaldehyde condensate, 0.3 part of C.I. Acid Yellow 70, 0.5 part of glacial acetic acid and 0.3 part of polyoxyethylene sorbitan mono-oleate of the following structure ;;

/ 0\
~12~ T C 1200~-C18H35 Hn(CH2CH20)HC ~ C~H(C~2cH2)n ~: .
- H(CH2CH20)nH

were added to water to form 1000 parts of a dye bath, Then, 20 parts of a mixed fabric of Cashmilon F (polyacrylonitrile fibers manufactured by Asahi Kasei) and wool (mixing ratio being 55:45) was immersed in the bath, and the temperature of the dye bath was elevated to 100C. over a period of 30 ~ , minutes~ Dyèing was conducted at this temperature for 60 minutes. The Casmillon F was dyed in a clear blue color and the wool was dyed a yellow ~ ~
color. There was thus~ obtained an excellent multi-color dyeing effect. .. ~!, , '.
Example 30 ~ -; 0.1 part of a composition of C~I. Basic Red 50 and a naphthalene- ;
sulfonic acid-formaldehyde condensate, 0.5 part of glacial acetic acid and ;
0.3 part of crystalline sodium sulfate were dissolved in waterJ and 0.1 part of polyoxyethylene stearylamine of the following structure / (C~l2~H2o)nH
18 3~ \ ~
~cH2cH2o)nH ''' ' ~' was added to the solution to obtain a dye bath. Then, a fabric of non-modified polyes~er fibers interwoven with stripes o polyacrylic fibers (mixing ratio being 99:1) was immersed in the dye bath, and the temperature of the dye bath was elevated to 100C~ over a period of 40 mlnutes~ Dyeing was conducted at this temperature for 60 minutes~ The polyacrylic fibers ~o~

t~ere dyed in a concen~rated red color and the polyester fibers were left `-white. Thus there was obtained a fabric having a red stripe pattern on a -;
white backgrotmd. Since contamination of the polyester fibers was extremely low, it was unnecessary to conduct soaping.

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.

. ' . -26-.,

Claims (6)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A basic dye composition in finely divided form which comprises a complex salt of low water solubility formed by ionic bonding between one or more water-soluble basic dyes and at least one anionic dispersant capable of being ionically bonded to the basic dye or dyes, wherein the anionic dis-persant is selected from the group consisting of alkali metal, alkaline earth metal, ammonium and aluminium salts of (a) a condensate of formaldehyde with 1- or 2- naphthalenesulfonic acid, (b) a condensate of formaldehyde with methyl naphthalenesulfonic acid, (c) lignin sulfonic acid and (d) alkyl sulfate and the amount of anionic dispersant present is greater than the stoichiometric amount required to react with the water-soluble basic dye but less than 15 parts by weight per part by weight of the water-soluble dye.

2. A basic dye composition set forth in claim 1, wherein the dis-persant is a condensate of formaldehyde with 1- or 2- naphthalene-sulfonic acid.

3. A basic dye composition set forth in claim 1, wherein the dispersant is a salt of a condensate of formaldehyde with methylnaphthalene-sulfonic acid.

4. A basic dye composition set forth in claim 1, wherein the dispersant is a salt of lignin sulfonic acid.

5. A basic dye composition set forth in claim 1, where the dispersant is a salt of an alkyl sulfate.

6. A process for the preparation of a basic dye composition which comprises a finely divided complex salt of low water solubility, which process comprises reacting a water-soluble basic dye and an anionic dis-persant capable of being ionically bonded to said basic dye to form the complex salt of low water-solubility, wherein the anionic dispersant is selected from the group consisting of alkali metal, alkaline earth metal, ammonium and aluminium salts of (a) a condensate of formaldehyde with 1- or 2-naphthalenesulfonic acid, (b) a condensate of formaldehyde with methyl naphthalenesulfonic acid, (c) lignin sulfonic acid and (d) alkyl sulfate and the amount of anionic dispersant present is greater than the stoichiometric amount required to react with the water-soluble basic dye but is less than 15 parts by weight per part of the water-soluble basic dye.