Clay-containing dispersing composition for carriers used in the disperse dyeing of hydrophobic textiles

Improvements in the disperse dyeing process for hydrophobic textiles by the use of novel dye carrier formulations are disclosed. The carrier composition for use in disperse dyeing of hydrophobic textile material preferably comprises an alkylphthalimide carrier component and a clay dispersing agent. Dye baths and methods of disperse dyeing of a hydrophobic textile material are also disclosed. The use of clay as a dispersing agent allows for the use of carrier compositions with reduced health and environmental hazards without adversely affecting dyeing characteristics.

BACKGROUND OF THE INVENTION 
The invention relates to the use of smectite clays as dispersing agents for 
dye carriers in the dyeing of hydrophobic textiles. 
Certain hydrophobic textiles such as polyester (polyethylene terephthalate, 
sometimes known as PET), triacetate and aramid textiles are difficult to 
dye with disperse dyes at temperatures below their glass transition 
temperatures (T.sub.g). Adequate dyeing rates are achieved when the dyeing 
temperature exceeds T.sub.g, and economic dyeing rates are achieved with 
high temperature dyeing (ca. 130.degree. C.). Adequate rates of disperse 
dyeing of hydrophobic textiles at lower temperatures can be achieved by 
the use of dye carrier compounds, sometimes referred to as dye assistants 
or accelerants (referred to herein by the term "dye carrier" or "carrier 
component"). Dye carriers have an affinity for and an ability to swell or 
plasticize the textile fibers and may be visualized as "carrying" the dye 
into the fibers. Dye carriers are typically low molecular weight, 
aromatic, hydrophobic organic oils that facilitate the dyeing process by 
plasticizing the surfaces of the fibers so that dye molecules can 
penetrate more rapidly and at lower temperatures. Examples of popular 
compounds for use as dye carriers in dyeing polyester textile material 
include aromatic and halogenated aliphatic hydrocarbons and phenols, such 
as o-phenylphenol, diphenyl or chlorinated benzenes, alkylphthalimide 
compounds, biphenyl, and o-chlorotoluene. 
Effective carrier compounds are insoluble in the aqueous dye bath and are 
added to the dye bath as emulsions with the aid of a dispersing agent. 
Effective dispersing systems for carrier compounds must perform two 
functions: (1) the function of maintaining the organic carrier dispersed 
in an aqueous solution; and (2) the function of allowing the organic 
carrier to come into contact with the surface of the fiber. For some 
dispersing agents, these functions may be at odds with each other in that 
a strong dispersing agent may partition the carrier oil into the aqueous 
phase, allowing reduced contact with the hydrophobic textile. 
The use of carrier agents in disperse dyeing of textiles is well known, 
including the use of alkylphthalimides and derivatives thereof. See for 
example U.S. Pat. Nos. 3,574,513, 4,780,105 and 4,994,089, and British 
patent 2,247,470, granted Mar. 4, 1992. 
Many of the commonly used dye carrier formulations present health and 
environmental risks. While the use of dye carriers such as 
alkylphthalimides would minimize these risks, as well as objectionable 
odor of some previous carriers, performance versus cost concerns with 
previous alkylphthalimide carrier formulations have resulted in their 
being underutilized in the industry. Therefore, there is a long felt need 
for dye carrier formulations which are more acceptable as concerns safety 
and which deliver effective, efficient performance in the dyeing process. 
BRIEF SUMMARY OF THE INVENTION 
The present invention allows for improvements in the disperse dyeing 
process for hydrophobic textiles, especially PET, by the use of novel dye 
carrier formulations. 
One aspect of the invention relates to a carrier composition for use in 
disperse dyeing of an hydrophobic textile, the carrier composition 
comprising an alkylphthalimide carrier component and a clay dispersing 
agent. 
Another aspect of the invention relates to a method of disperse dyeing a 
hydrophobic textile to a predetermined extent, the method comprising: (a) 
providing a hydrophobic textile, (b) providing an aqueous dye bath 
comprising a disperse dye and a dye carrier composition, the dye carrier 
composition comprising a dye carrier and a clay dispersing agent capable 
of dispersing the dye carrier in the dye bath, and (c) contacting the 
textile with the dye bath until the hydrophobic textile is dyed to the 
predetermined extent. 
DETAILED DESCRIPTION OF THE INVENTION 
It has been discovered, according to the present invention that smectite 
clays, especially bentonites, may be used as dispersing agents for carrier 
compounds in the disperse dyeing of hydrophobic textiles. The compositions 
and methods of the present invention have many advantages in the dyeing 
process. The odorless, nonvolatile carrier compositions of the present 
invention have environmental safety advantages, due to the inherently 
lower biochemical oxygen demand (BOD) and chemical oxygen demand (COD) 
associated with clays compared to organic chemical dispersants 
(emulsifiers). The carrier compositions of the present invention give 
enhanced dyeing yield and quality, such as more uniform dyeing. It is 
unexpected that there is substantially no spotting of this carrier, since 
such spotting can occur when using organic dispersants, due to separation 
of the carrier agent in the dye bath. In addition, the present invention 
allows the disperse dyeing to be conducted under atmospheric conditions 
and results in good yield. There is also no or minimal cross-staining of 
other, more hydrophilic fibers typically used in blends of different 
fibers. 
"Hydrophobic textile", as used herein, means any textile material 
containing at least some yarns, filaments or fibers with a low affinity 
for water, including but not limited to, polyester, nylon, polypropylene, 
acrylic, polyurethane, triacetate, aramid (such as Kevlar.RTM. and 
Nomex.RTM.) and blends of such materials with each other or blends of such 
materials individually or together with other fibers such as cotton and 
wool. Hydrophobic textiles may be woven, nonwoven or knitted fabric, as 
well as yarns, fibers, or filaments, or other products made therefrom, 
such as carpeting, clothing, or any number of other finished goods. 
The present invention may be used with any disperse dyes suitable for use 
in disperse dyeing hydrophobic textiles. A great many such dyes are known 
and they include virtually any color in the spectrum. See, for example, 
The American Association of Textile Chemists and Colorists, 1997, Buyers 
Guide, pp. 91-98. They are readily available from a number of commercial 
sources. 
The dye carrier may be any compound which functions to enhance dye 
penetration of the hydrophobic textile. Dye carriers which may be used in 
accordance with this invention include, but are not limited to, 
orthophenylphenol, butyl cellosolve benzoate, butyl benzoate, biphenyl, 
orthochlorotoluene, trichlorobenzene and alkylphthalimides of both higher 
and lower molecular weight. Preferred as dye carriers in the present 
invention are phthalimide compounds and particularly alkylphthalimides. 
One aspect of the invention relates to a carrier composition for use in 
disperse dyeing of hydrophobic textile, the composition comprising a dye 
carrier component and a clay dispersing agent. 
The carrier composition of the present invention preferably contains as the 
carrier agent an alkylphthalimide carrier component. The use of a clay 
dispersing agent in conjunction with an alkylphthalimide carrier component 
has significantly and unexpectedly enhanced the performance of the 
alkylphthalimide carrier. 
"Alkylphthalimide carrier component", as used herein, includes any 
alkylphthalimide compound or its functionally equivalent derivatives, or 
mixtures of such compounds, such as those disclosed, for example, in U.S. 
Pat. Nos. 3,574,513, 4,780,105 and 4,994,089, and British Patent 
2,247,470, granted Mar. 4, 1992, the disclosures of which are hereby 
incorporated herein by reference. Other preferred phthalimide compounds 
are those having the following structural formula: 
##STR1## 
where R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are independently H 
or alkyl groups of 1 to 3 carbon atoms, m is 0 or 1, n is 1 to 6 and x is 
0 or 1. 
Alkylpthalimide compounds may include N-substituted phthalimides which are 
substituted on the nitrogen by straight chain or branched chain alkyl 
radicals. Examples of alkylphthalimide components that may be used in the 
carrier composition of the present invention include, but are not limited 
to, methyl phthalimide, ethyl phthalimide, n-propyl phthalimide, isopropyl 
phthalimide, n-butyl phthalimide, sec-butyl phthalimide, N-ethyl 
phthalimide, N-isopropyl phthalimide, N-butyl phthalimide, N-isobutyl 
phthalimide, N-2-ethyl hexyl phthalimide, N-ethoxymethyl phthalimide, 
N-propoxymethyl phthalimide, and N-methyl carbonyl-N-methoxyl phthalimide. 
Preferred alkylphthalimide carrier compounds are those having alkyl groups 
of twelve or less carbon atoms. Strongly preferred are alkylphthalimides 
which are liquid at the temperature of use. The presently most preferred 
compounds are n-butyl phthalimide and isopropyl phthalimide, and preferred 
mixtures of alkylphthalimide carrier components include a mixture 
comprising a 3:1 weight ratio of n-butyl phthalimide to isopropyl 
phthalimide (a euthetic mixture). 
"Clay dispersing agent" as used herein refers to any type of smectite clay, 
such as montmorillonite or Japan clay, including bentonite (sodium 
montmorillonite) or Fuller's earth (calcium montmorillonite) which is 
capable of performing a dispersing function for an insoluble, hydrophobic 
dye carrier in an aqueous medium. Suitable clays are those disclosed in 
U.S. Pat. Nos. 3,989,631, 4,178,254 and 4,844,821, or an organoclay as 
disclosed in U.S. Pat. No. 5,130,028. The disclosures of all of these 
patents are hereby incorporated herein by reference. 
The clay component is smectite clay having the general characteristics as 
described in Kirk-Othmer Encyclopedia of Chemistry, Third Edition, 
6:391-394 (1989) and Ullmann's Chemical Encyclopedia, A7:116-119, 124-125, 
and 131-133 (1994), the disclosures of both being incorporated herein by 
reference. The preferred clay is a bentonite clay, and more particularly, 
a sodium bentonite clay in the form of a free-flowing powder or 
agglomerate. The presently preferred bentonite has the following 
characteristics: the powder has a brightness on the Hunter Color Scale of 
L greater than 87; a cation exchange capacity of about 75 milliequivalents 
per 100 g; a particle size of about 0.2.mu. to about 1.1 mm, preferably 
about 2.mu. to about 10.mu. (averaging about 4.mu.) as a powder and about 
0.4 mm to about 1.1 mm as an agglomerate; a moisture content of 10.+-.2% 
in powder form or 12.+-.2% in agglomerate form; a swelling volume of at 
least about 18 ml, based on 2 g in 100 ml water; a pH (at a 2% suspension) 
of about 9 to about 11; a loose bulk density of 550.+-.50 g/l in powder 
form and about 830.+-.50 g/l in agglomerate form; with a powder residue on 
a 45.mu. screen of a maximum of about 5%. The presently preferred 
bentonite has the following chemical analysis: SiO.sub.2, about 70.0%; 
Al.sub.2 O.sub.3, about 16.0%; MgO, about 2.7%; Na.sub.2 O, about 2.8%; 
Fe.sub.2 O.sub.3, about 1.3%; K.sub.2 O, about 1.0%; CaO, about 1.1%; and 
about 5% loss on ignition. A preferred white sodium bentonite clay may be 
obtained from American Colloid Company, Arlington Heights, Ill., for 
example. 
The carrier composition of the present invention is in the form of a stable 
substantially anhydrous composition of the carrier component and the clay 
dispersing agent. Minor or trace amounts of water may be included, 
particularly if other optional ingredients as noted below are present. 
Carrier compositions containing some water are acceptable, but those 
containing no or only trace amounts of water are more stable. The carrier 
composition comprises the carrier component, and preferably the 
alkylphthalimide carrier component, at a concentration of about 30 weight 
% (based on the total weight of the carrier composition) to about 90 
weight % and the clay dispersing agent at a concentration of about 10 
weight % to about 42 weight %, the balance including any optional 
components. Preferably, the carrier composition comprises the lower 
alkylphthalimide carrier component at a concentration of about 45 weight % 
to about 75 weight % and the clay dispersing agent at a concentration of 
about 25 weight % to about 35 weight %. More preferably, the carrier 
composition comprises the lower alkylphthalimide carrier component at a 
concentration of about 58 weight % to about 68 weight % and the clay 
dispersing agent at a concentration of about 31 weight % to about 34 
weight %. 
The carrier composition may also comprise other optional auxiliary 
components. Such optional auxiliaries include but are not limited to 
viscosity control agents and leveling agents. The viscosity control agent 
is preferred so that the composition is readily pourable or pumpable. The 
leveling agent is preferred to provide better, more uniform distribution 
of the dyes. 
A preferred viscosity of the carrier composition is about 12,000 centipoise 
("cp") to about 16,000 cp, and preferably about 14,000 cp, as measured by 
a Brookfield LVT viscometer at 12 rpm using a size 3 spindle. 
Non-limiting examples of preferred viscosity control agents include 
ethoxylated linear or branched alcohols, such as tridecyl alcohol, with 
three moles of ethoxylation ("TDA 3"), tridecyl alcohol, with six moles of 
ethoxylation ("TDA 6"), and Nedol.TM. 9-3, available from Shell Chemicals, 
Inc., Houston, Tex., for example. When a viscosity control agent is used, 
it may be present in an amount of up to about 5 weight %, preferably about 
1.5 weight % to about 4 weight %, and more preferably about 3.2 weight % 
to about 3.8 weight %. All of these weight percentages are based on the 
weight of the carrier composition. 
Non-limiting examples of preferred leveling agents include ethoxylated 
oleic acid with 14 moles of ethoxylation ("mono oleate 14EO"), ethoxylated 
oleic acid with 12 moles of ethoxylation ("mono oleate 12EO") and 
ethoxylated oleic acid with 16 moles of ethoxylation ("mono oleate 16EO"). 
When a leveling agent is used, it may be present in an amount of up to 
about 5 weight %, preferably about 1 weight % to about 3 weight %, and 
more preferably about 1 weight % to about 1.2 weight %. All of these 
weight percentages are based on the weight of the carrier composition. 
Other optional ingredients may also be included in the carrier composition 
of the present invention including, without limitation, wetting agents, 
biocides, antifoaming agents, and acids or bases to adjust the pH to an 
appropriate level, depending on the intended use with a particular 
disperse dye, for example. 
The carrier composition of the present invention may be made readily using 
standard commercial equipment. A suitable general procedure is as follows, 
but many variations may be made, as long as the desired substantially 
uniform and smooth composition is achieved. The phthalimide or other dye 
carrier component is charged to a vessel, such as a Cowles mixer fitted 
with a shear blade. While mixing at low speed of about 100 to about 200 
rpm, the clay is added to the phthalimide or other dye carrier component 
in the mixing vessel. The mixture is mixed at this low speed until the 
clay is wetted, which may take on the order of about 3 hours. When the 
clay is wetted, the mixer is switched to high speed shear mixing at about 
3500 to about 4000 rpm. The mixture is mixed at high speed until a smooth, 
uniformly blended mixture is obtained. During high speed mixing, the 
mixture is preferably cooled to keep the temperature at about 55.degree. 
to about 60.degree. C. After a suitable period of time, such as about 2 to 
about 2.5 hours, and after achieving the desired smoothly blended mixture, 
the optional ingredients, such as the viscosity control agent and leveling 
agent are mixed, preferably at the high speed for another period of time 
until all ingredients are thoroughly blended, for example, for about 30 
minutes. Following the uniform blending of all optional ingredients, the 
mixer preferably is run at low speed mixing to make it easier to cool the 
mixture to about 30.degree. to about 35.degree. C. The mixture is then 
discharged through a bag filter and placed in appropriate containers for 
storage or shipping. 
The carrier composition of this invention is used in an aqueous dye bath 
for disperse dyeing of a hydrophobic textile also comprising a disperse 
dye and water. The carrier agent component of the carrier composition will 
not effectively be able to be separately mixed directly in the dye bath or 
water used for the dye bath, even if the clay dispersing agent is added 
later, without first making a premix of the carrrier composition in which 
the carrier is dispersed with a dispersing agent, in the case of the 
present invention, a clay dispersing agent as discussed above. It is also 
not possible to make a dye bath according to the present invention by 
first separately mixing in a dye bath or in the water used for the dye 
bath the clay dispersing agent of this invention, followed by the separate 
addition of the carrier material, because the carrier oil splits out as a 
separate oil phase. Nor is it possible to simultaneously, but separately 
add the carrier and the clay dispersing agent to the dye bath or water 
used for the dye bath, for the same reason. The carrier oil will adversely 
spot the textiles. 
Rather than separately adding the carrier composition ingredients to the 
dye bath or the dye bath water, to make a dye bath according to the 
present invention, the carrier and clay dispersing agent must first be 
formed into the carrier composition of the invention. Then the carrier 
composition, per se, is added to the dye bath or water used to make the 
dye bath. 
Clay/phthalimide carrier compositions of the present invention may be added 
to the aqueous dye bath in number of different ways, all of which result 
in satisfactory dispersibility of the carrier in the dye bath. For 
example, the carrier composition may be added directly to the water with 
strong mixing. However, optimal dispersibility of the carrier composition 
is achieved by predispersion of the carrier formulation in water as a 
concentrate. Predispersion may be done, for example, by placing the 
carrier formulation in a container and slowing adding water to the carrier 
formulation with vigorous mixing. The water is at a temperature of about 
90.degree. F. to about 120.degree. F. and the mixing should be sufficient 
to keep the entire mixture turning. At a ratio of about 2 to about 3 parts 
water to 1 part of the clay/phthalimide carrier composition, the mixture 
will become an "inverse emulsion," with water as the internal phase. At 
this point, the mix will be very thick and have an almost paste-like 
consistency. At this stage, water addition is stopped and the mixing 
continues until the paste is smooth and completely free of lumps. When the 
mixture is smooth, the water addition is restarted and the water is slowly 
added with mixing until the concentrated dispersion of the carrier 
composition is pourable or pumpable. A preferred pourable or pumpable 
concentrate results when the ratio of water to carrier composition is 
about 10 to 1 or until the mixture is pourable. This concentrated 
predispersion mixture is then added to the dye bath in an amount to 
achieve the desired quantity of the carrier composition, calculated on a 
non-diluted basis, in the dye bath. 
Use of this preferred method results in a dispersion that is very stable in 
the dye bath. If the dye bath is allowed to stand without agitation for a 
length of time that the clay/phthalimide carrier component settles as a 
fine powder, it is easily redispersed by mixing. Settling of 
clay/phthalimide carrier component does not result in irregular dyeing. 
Even in the extreme situation of the clay/phthalimide carrier component 
being deposited on the fabric in an undispersed or poorly dispersed form, 
there is no resulting irregularity in the uniformity of the dyeing and 
satisfactory dyeing results are achieved without spotting. 
With traditional carrier formulations, satisfactory dyeing results are 
typically not achieved with poorly dispersed carrier formulations. 
Although traditional carrier formulations typically "bloom" into water 
well and easily form very uniform milky dispersions, they tend to cream to 
the top of a dye bath that is allowed to stand without agitation. This 
cream will deposit onto the fabric and cause dye-spots. Dye-spots will 
also form if the traditional carrier formulation is allowed to splatter 
onto the fabric in the undispersed form. 
The invention also relates to a method of disperse dyeing to a 
predetermined extent a hydrophobic textile. The method comprises the steps 
of (a) providing a hydrophobic textile, (b) providing an aqueous dye bath 
comprising a disperse dye and dye carrier composition, the dye carrier 
composition comprising a dye carrier and a clay dispersing agent capable 
of dispersing the dye carrier in the dye bath and (c) contacting the 
textile with the dye bath until the hydrophobic textile is dyed to the 
predetermined extent. 
The aqueous dye bath includes water and the desired disperse dye, the 
carrier composition according to the present invention and other desired 
additives, such as chelating agents, acids or bases to adjust the pH of 
the dye bath to the appropriate level based on the characteristics of the 
dye being used and the textile being dyed, as well as various other 
optional ingredients such as other wetting agents, antifoaming agents, and 
the like, well known to those skilled in the dyeing art. 
Dyers typically refer to the amounts of ingredients in a dye bath based on 
the weight of the textile or fabric being dyed, rather than as amounts 
based on the total amount of ingredients in the dye bath, per se, without 
the fabric. The amount of dye and dye carrier will depend upon the shade 
and depth of color desired for a particular fabric, and therefore, when 
references are made to the amounts of dye and the carrier composition of 
the invention used in the dyeing method of the invention, the amount will 
be based on a percentage by weight of the textile or fabric being dyed, 
referred to as the "percentage on weight of the fabric" ("% owf"). 
The dye may be present in the dye bath in a concentration owf of about 
0.001% to about 0.25% for pastels, about 0.25% to about 0.75% for light 
shades, about 0.75% to about 1.5% for medium shades and about 1.5% to at 
least about 3% for dark shades. The carrier composition will be present in 
the dye bath in a concentration owf of about 0.5% to about 20%, preferably 
about 1.5% to about 15%, and more preferably about 2% to about 10%. 
Although the method of the present invention may be varied by the various 
dye houses to suit the particular needs of their customers, the method of 
the present invention generally comprises weighing the textile to be dyed 
and loading it into any of the several types of dyeing apparatus used 
throughout the industry, such as Theis Jet and atmospheric beck equipment. 
The vessel or bin containing the textile is then filled to an appropriate 
level with water and the textile is circulated in the water while the 
water is heated to the indicated dyeing temperature associated with the 
particular dispersed dye. While the textile is being circulated, chelate 
is added if desired to sequester any unwanted metal ions in the system and 
the appropriate pH adjustment is made, if necessary, often by adding the 
appropriate amount of acid, such as acetic acid, to obtain the desired pH. 
Next, the dye carrier composition of the present invention is added, 
preferably but not necessarily in a predispersed form as set forth above, 
while the circulation continues to achieve uniform distribution of the 
foregoing components throughout the textile. Disperse dyes, typically 
predispersed with and mixed with water, are then added to the dye bath 
containing the circulating textile. The temperature of the circulating dye 
bath and textile is then raised to the desired level and maintained until 
the dyes are exhausted or diffused into the fibers of the textile to the 
predetermined extent, depending upon the shade desired. The dye bath 
containing the dyed textile is then cooled to ambient temperature, at 
which point the dye bath is drained. The dyed textile is then rinsed, and 
if needed, scoured to remove any loose dyes. After the appropriate 
rinsing, the dyed textile is dried. 
The present invention will now be described in more detail with reference 
to the following specific, non-limiting examples. 
As used in Example 1, Table 1, the term "percent", "%" or the like, refers 
to the percent by weight of the particular ingredient or component to 
which the term refers, based on the weight of the composition, bath or 
other overall product of which the component forms a part, as should be 
clear from the context in which it is used, unless otherwise noted. In the 
other Tables of Example I and in the other following examples, the amounts 
of ingredients are stated as weight percents based on the weight of the 
textile or fabric being dyed (owf). 
Most of the examples include an "ACS Yield" reading. This number is 
determined using an "Applied Color System" Spectro Sensor.RTM. II 
instrument, Model 1400 PC, from Applied Color Systems, Inc., Princeton, 
N.J., which measures depth of shade only, which is related to the amount 
of dye affixed to the fiber. The higher the ACS yield, the more dye is 
bonded to the fabric. This number does not reflect other factors which are 
also critical to color perception, such as cast (is it too red or too 
blue, etc.) and brightness (is it eye-catching or dull). Where the ACS 
Yield does not apply, alternate descriptions of the results are provided.

EXAMPLE 1 
Example 1 is a demonstration that dispersing systems based on sodium 
bentonite clays are equally as effective as traditional organic dispersing 
systems, both non-ionic or anionic, in creating effective polyester dye 
carrier formulations. 
Example 1, Table 1 provides the composition of all of the carrier 
formulations discussed in Example 1 and in the following examples. The dye 
carrier compositions identified in Example 1, Table 1 as F1915H, F1933P 
and F1960C are compositions according to the present invention. They were 
prepared using the ingredients of Table 1 and following the method set 
forth above concerning making and predispersing the carrier composition of 
the invention. The other CAROLID.RTM. and ECOLID.RTM. carriers (Sybron 
Chemicals Inc., Birmingham, N.J.) are commercially available dye carriers 
used for comparison purposes. Two of the carrier formulations, 
CAROLID.RTM. TOP and CAROLID.RTM. SFC employ the commonly used carrier 
compounds o-chloro toluene and biphenyl. The other five carrier 
formulations, CAROLID.RTM. NOL, ECOLID.RTM. STU, F1915H, F1933P, and 
F1960C, employ n-butyl and isopropyl phthalimide mixtures as the carrier 
compounds. 
The experiment outlined in Example 1, Table 2 compares the clay dispersing 
system with a nonionic organic dispersing system, with phthalimide 
mixtures as the carrier compounds. Whether the carriers are present in the 
dye bath at either 6% or 8% owf, the yield is improved when the clay 
dispersant is used. Comparison of the two types of carrier dispersing 
systems indicated that the carrier tended to separate slowly to the 
surface when the organic dispersant was used and that the carrier remained 
in suspension or settled slightly, but was easily redispersed, when clay 
was used as the dispersant. 
The F1915H and F1933P carrier compositions of the present invention 
included small amounts of water by virtue of their formulations using 
polyethylene glycol 14 monooleate (PEG 14 monooleate) in the form of a 30 
weight % aqueous solution. F1960C used anhydrous PEG 14 monooleate. While 
all three compositions were acceptable with respect to stability and 
dyeing results, F1960C was the most stable and is preferred. 
The experiments outlined in Example 1, Tables 3-5 compare the clay 
dispersing system with anionic organic dispersing systems, with 
phthalimide mixtures as the carrier compounds. A variety of dyeing 
temperatures, from 207.degree. F. to 260.degree. F., are indicated in 
these tables. In all of the experiments detailed in Tables 3-5, higher 
yields were obtained with a carrier formulation containing a clay 
dispersing system than with a carrier formulation containing an anionic 
organic dispersing system. 
TABLE 1 
__________________________________________________________________________ 
Example 1 
CARRIER FORMULATIONS 
PERCENT IN COMPOSITION 
Carolid .RTM. 
Ecolid .RTM. 
Carolid .RTM. 
Carolid .RTM. 
F1915H 
F1933P 
F1960C 
NOL STU TOP SFC 
__________________________________________________________________________ 
Phthalimides.sup.1 
58.8 
63.0 
63.0 
68.4 81.6 
Clay.sup.2 
29.4 
30.9 
32.4 
Water 8.5 
PEG 14 
Monooleate 
(30 wt % 
11.8 
3.6 
aqueous 
solution) 
PEG 14 
Monooleate 1.1 
(anhydrous) 
3 Mole EO 
Tridecanol 2.5 
3.5 
Nonionic/ 
Anionic 23.1 29.4 
Emulsifiers 
Nonionic 
Emulsifiers 18.4 
Anionic 
Emulsifiers 5.6 
O-chloro- 
Toluene 69.3 48.3 
Biphenyl 25.1 22.3 
__________________________________________________________________________ 
.sup.1 Phthalimides: eutectic mixture of nbutyl and isopropyl phthalimide 
(3:1 weight ratio) 
.sup.2 clay: sodium bentonite (bleaching clay) of approximately 2-10 
microns particle size. 
TABLE 2 
______________________________________ 
Example 1 
COMISON OF CLAY TO NONIONIC EMULSIFIER KAGE 
UNDER ATMOSPHERIC CONDITIONS 
______________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 20/1 
Equipment: Ahiba AG, Model WBRG-7 Laboratory Dye Apparatus 
Procedure: 
1) Set temperature of dye bath at 120.degree. F., with water and fabric 
only. 
2) Add acetic acid to obtain a pH 5.5-6.0, Plexene .TM. Extra Conc. 
and carrier. 
3) Run 10 minutes. 
4) Add dye. 
5) Raise temperature 3.degree. F./min. to 207-209.degree. F. and run 
for 
1 hour, then drain. 
6) Rinse with hot water, drain and dry. 
______________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 24 25 26 27 
______________________________________ 
Disperse Red 60 
4.0 4.0 4.0 4.0 
Acetic Acid 56% 
0.5 0.5 0.5 0.5 
Plexene .TM. Extra 
0.5 0.5 0.5 0.5 
Conc..sup.1 
F1915H 6.0 8.0 
Ecolid STU 6.0 8.0 
ACS Yield Reading 
100* 103 107 106 
______________________________________ 
.sup.1 40% aqueous solution of EDTA tetrasodium salt available from Sybro 
Chemicals Inc. 
*Standard 
TABLE 3 
______________________________________ 
Example 1 
COMISON OF CLAY TO ANIONIC EMULSIFIER KAGE 
UNDER ATMOSPHERIC CONDITIONS 
______________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 20/1 
Equipment: Ahiba AG, Model WBRG-7 Laboratory Dye Apparatus 
Procedure: See Example 1; Table 2 
______________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 
43 46 44 47 45 48 
______________________________________ 
Resolin Blue 
0.35 0.35 0.35 0.35 0.35 0.35 
FBL 
Resolin Red 
0.25 0.25 0.25 0.25 0.25 0.25 
FB 200% 
Terasil 1.0 1.0 1.0 1.0 1.0 1.0 
Yellow 2GW 
Acetic Acid 
0.5 0.5 0.5 0.5 0.5 0.5 
56% 
Plexene .TM. 
0.25 0.25 0.25 0.25 0.25 0.25 
Extra Conc 
F1933P 4.0 5.0 6.0 
Carolid .RTM. 4.0 5.0 6.0 
NOL 
ACS Yield 
100* 90 104 93 106 91 
Reading 
______________________________________ 
*Standard 
TABLE 4 
__________________________________________________________________________ 
Example 1 
COMISON OF CLAY TO ANIONIC EMULSIFIER KAGE 
AT INTERMEDIATE TEMPERATURE AND MODERATE PRESSURE 
__________________________________________________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 10/1 
Equipment: Laboratory Launderometer 
Procedure: 
1)-4) 
See Procedure, Example 1, Table 2, Steps 1-4. 
5) Seal the vessel and raise temperature 3.degree. F./min. to 217.degree. 
F. 
6) Run 45 minutes, then drain. 
7) Rinse with hot water, drain and dry. 
__________________________________________________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 
3 6 12 15 1 4 10 13 
__________________________________________________________________________ 
Intrasil 
1.0 1.0 1.0 1.0 0.17 
0.17 
0.17 
0.17 
Yellow 2GW 
Intrasil 
0.1 0.1 0.1 0.1 
Scarlet 2RV 
Intrasperse 2.50 
2.50 
2.50 
2.55 
Red GFL 
Terasil 1.1 1.1 1.1 1.1 0.33 
0.33 
0.33 
0.33 
Blue R 200% 
Acetic acid 
0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 
56% 
Plexene .TM. 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
Extra Conc. 
F1933P 4 6 4 6 
Carolid .RTM. NOL 
4 6 4 6 
ACS Yield 
98 95 100* 
100 101 101 100 96 
Reading 
__________________________________________________________________________ 
*Standard 
TABLE 5 
__________________________________________________________________________ 
Example 1 
COMISON OF CLAY TO ANIONIC EMULSIFIER KAGE 
UNDER ATMOSPHERIC CONDITIONS 
__________________________________________________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 20/1 
Equipment: Ahiba AG, Model WBRG-7 Laboratory Dye Apparatus 
Procedure: See Example 1, Table 2 
__________________________________________________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 19 21 20 22 25 27 26 28 
__________________________________________________________________________ 
Resolin Red FB 200% 2.0 2.0 
2.0 2.0 
Terasil Yellow 2GW 
3.0 
3.0 
3.0 3.0 
56% Acetic Acid 
0.5 
0.5 
0.5 0.5 
0.5 0.5 
0.5 0.5 
Plexene .TM. Extra Conc. 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
F1933P 6.0 8.0 6.0 8.0 
Carolid .RTM. NOL 
6.0 8.0 6.0 8.0 
ACS Yield Reading 
93 89 100* 
91 89 84 100 88 
__________________________________________________________________________ 
*Standard 
EXAMPLE 2 
Example 2 is a demonstration that the use of clay as a dispersant in 
carrier formulations allows for the use of non-hazardous carrier 
formulations in lieu of commonly used hazardous carrier formulations, with 
comparable results in dye yield. 
The commercially available Carolid.RTM. TOP product (as described in 
Example 1; Table 1) contains both monochlorotoluene and biphenyl as 
carrier agents and provides in Example 2, Table 1, the following health 
information on the Material Safety Data Sheet: 
TABLE 1 
______________________________________ 
Example 2 
CAS NO. compound OSHA PEL.sup.1 
ACGIH CEILING.sup.2 
______________________________________ 
25168-05-2 
monochlorotoluene, 
50 ppm 50 ppm 
mixed isomers 
92-52-4 biphenyl 0.2 ppm 0.2 ppm 
______________________________________ 
.sup.1 PEL = Permissable Exposure Levels 
.sup.2 ACG/H = American Conference of Government Industrial Hygiensts. 
A material data sheet written for the commercial carrier formulations 
Carolid.RTM. NOL or Ecolid.RTM. STU, or for the carrier formulations of 
the present invention designated F1933P, F1915H, or F1960C, all of which 
employ a phthalimide mixture as the carrier agent, would not be required 
to report warnings because of the nontoxic nature of the phthalimides. In 
addition to presenting potential health concerns, compositions containing 
a mixture of chlorotoluenes and biphenyls have a strong objectionable odor 
that can permeate throughout a manufacturing facility and linger for long 
periods. Use of carrier compositions containing phthalimide carrier 
compounds does not result in the production of objectionable odors. 
From an environmental standpoint, use of carrier formulations containing 
phthalimide compounds would also be preferable. Note the BOD/COD 
information and the volatile organic contents information shown in Example 
2, Table 2, below. 
TABLE 2 
______________________________________ 
Example 2 
BOD.sup.1 
COD.sup.2 VOC.sup.3 
______________________________________ 
Carolid .RTM. TOP 
-- 2,300,000 ppm 
95% 
(chlorotoluene; 
biphenyl) 
Ecolid .RTM. STU 
137,000 ppm 
1,754,000 ppm 
38% 
(phthalimides/ 
organic emulsifiers) 
F1933P 
(phthalimides/ 
82,000 ppm 
1,555,000 ppm 
20% 
clay emulsifiers) 
______________________________________ 
.sup.1 BOD = biological oxygen demand 
.sup.2 COD = chemical oxygen demand 
.sup.3 VOC = volatile organic contents 
Example 2, Tables 3-6 show comparisons in dyeing performance between 
F1933P, which contains phthalimide carrier compounds formulated with a 
clay dispersant according to the present invention, and Carolid.RTM. TOP, 
which contains chlorotoluene and biphenyl compounds formulated with 
organic emulsifiers. Comparisons were made at a variety of dyeing 
temperatures, ranging from 207.degree. F. to 260.degree. F., and with a 
variety of dye combinations. In each case, the dye yield obtained using 
the non-hazardous F1933P carrier formulation was equal to or superior to 
the dye yield obtained with the more hazardous Carolid.RTM. TOP carrier 
formulation. Additionally, and importantly, the dispersibility of the 
F1933P carrier formulation was equal to that of the chlorotoluene organic 
carrier formulation. 
TABLE 3 
__________________________________________________________________________ 
Example 2 
PHTHALIMIDE/CLAY CARRIER FORMULATIONS 
MATCH THE PERFORMANCE OF A HAZARDOUS CARRIER 
FORMULATION AT INTERMEDIATE TEMPERATURES 
AND MODERATE PRESSURES 
__________________________________________________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 10/1 
Equipment: Laboratory Launderometer 
Procedure: See Example 1, Table 4 
__________________________________________________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 3 9 12 18 1 7 10 16 
__________________________________________________________________________ 
Intrasil Yellow 
2GW 1.0 
1.0 
1.0 1.0 0.17 
0.17 
0.17 
0.17 
Intrasil 
Scarlet 2RV 
0.1 
0.1 
0.1 0.1 
Intrasperse Red GFL 2.50 
2.50 
2.50 
2.50 
Terasil 1.1 
1.1 
1.1 1.1 0.33 
0.33 
0.33 
0.33 
Blue R 200% 
Acetic acid 56% 
0.5 
0.5 
0.5 0.5 0.5 0.5 0.5 0.5 
Plexene .TM. Extra 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
Conc. 
F1933P 4 6 4 6 
Carolid .RTM. TOP 
4 6 4 6 
ACS Yield Reading 
98 91 100* 
101 101 103 100* 
100 
__________________________________________________________________________ 
*Standards 
TABLE 4 
______________________________________ 
Example 2 
UTILITY OF CLAY IN MAKING INNOCUOUS CARRIER 
FORMULATION MATCHES THE PERFORMANCE OF HAZARDOUS 
FORMULATIONS AT HIGH TEMPERATURE 
______________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 10/1 
Equipment: Laboratory Launderometer 
Procedure: 
1)-4) See Example 1, Table 2, Steps 1-4. 
5) Seal vessel and raise temperature 3.degree. F./min. to 260.degree. 
F. 
6) Run 30 minutes, then drain. 
7) Rinse with hot water, drain and dry. 
______________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 7 5 8 6 
______________________________________ 
Foron Navy 3.0 3.0 3.0 3.0 
2GL 100% 
Acetic Acid 56% 
0.5 0.5 0.5 0.5 
Plexene .TM. 0.25 0.25 0.25 0.25 
Extra Conc. 
F1933P 2 4 
Carolid .RTM. TOP 2 4 
ACS Yield Reading 
100 100* 102 97 
______________________________________ 
*Standard 
TABLE 5 
______________________________________ 
Example 2 
UTILITY OF CLAY IN MAKING INNOCUOUS CARRIER MATCH 
THE PERFORMANCE OF HAZARDOUS CARRIER 
______________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 20/1 
Equipment: Ahiba AG, Model WBRG-7 Laboratory Dye Apparatus 
Procedure: See Example 1, Table 2. 
______________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 43 49 44 50 45 51 
______________________________________ 
Resolin Blue FBL 
0.35 0.35 0.35 0.35 
0.35 0.35 
Resolin Red FB 200% 
0.25 0.25 0.25 0.25 
0.25 0.25 
Terasil Yellow 2GW 
1.0 1.0 1.0 1.0 1.0 1.0 
Acetic Acid 56% 
0.5 0.5 0.5 0.5 0.5 0.5 
Plexene .TM. Extra 
0.25 0.25 0.25 0.25 
0.25 0.25 
Conc. 
F1933P 4.0 5.0 6.0 
Carolid .RTM. TOP 4.0 5.0 6.0 
ACS Yield Reading 
100* 96 104 98 106 95 
______________________________________ 
*Standard 
TABLE 6 
__________________________________________________________________________ 
Example 2 
UTILITY OF CLAY IN MAKING INNOCUOUS CARRIER FORMULATIONS 
MATCHES THE PERFORMANCE OF HAZARDOUS FORMULATIONS 
UNDER ATMOSPHERIC CONDITIONS 
__________________________________________________________________________ 
Fabric: 100% Textured Woven Polyester 
Liquor/Fabric Ratio: 20/1 
Equipment: Ahiba AG, Model WBRG-7 Laboratory Dye Apparatus 
Procedure: See Example 1, Table 2. 
__________________________________________________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 19 23 20 24 25 29 26 30 
__________________________________________________________________________ 
Resolin Red FB 200% 2.0 2.0 
2.0 2.0 
Terasil Yellow 2GW 
3.0 
3.0 
3.0 3.0 
56% Acetic Acid 
0.5 
0.5 
0.5 0.5 
0.5 0.5 
0.5 0.5 
Plexene .TM. Extra Conc. 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
0.25 
F1933P 6.0 8.0 6.0 8.0 
Carolid .RTM. TOP 
6.0 8.0 6.0 8.0 
ACS Yield Reading 
93 91 100* 
96 89 77 100* 
89 
__________________________________________________________________________ 
*Standards 
EXAMPLE 3 
Example 3 demonstrates that the use of a carrier formulation containing 
clay as the dispersing agent and a phthalimide mixture as the carrier 
equals the performance of current standard carrier formulations with 
regard to "cross-staining". 
Cross-staining is a phenomenon that occurs when cellulosic yarns and 
polyester yarns are woven into a fabric at right angles to each other. For 
example, polyester yarn may be used in the warp direction and cellulosic 
yarn may be used in the filling direction. This construction is used when 
particular types of stripes are desired the final fabric. Traditionally, 
the fabric is dyed in two stages, wherein the fabric is first treated to 
dye one type of fiber and is then treated to dye the second type of fiber. 
Recently, cross-staining has become much more of an issue in the industry. 
It is becoming popular to dye the polyester and the cotton fibers of the 
fabric in a single-bath, two-step process. The single-bath, two step 
process saves time and energy costs, but precludes the elimination of 
cross-stains. Therefore, cross-staining will interfere with the dyeing of 
the cotton portion and will make achieving the correct shade on the cotton 
fibers very difficult. Therefore, it is critical that a dye carrier 
formulation for polyester dyeing not contribute more to the cross-staining 
phenomenon. 
The experiment outlined in Example 3, Table 1 demonstrates that 
cross-staining occurred with all of the carrier formulations. The 
experiment also demonstrated that the cross-staining that occurred with 
the clay/phthalimide carrier formulation was equivalent to the 
cross-staining that occurred with standard carrier formulations, which is 
an acceptable level of cross-staining according to industry standards. 
TABLE 1 
______________________________________ 
Example 3 
______________________________________ 
Fabric: 50% Polyester/50% Cotton 
Liquor/Fabric Ratio: 20/1 
Equipment: Ahiba AG, Model WBRG-7 Laboratory Dye Apparatus 
Procedure: (Dye only the polyester portion, 
then observe the staining on the cotton) 
See Example 1, Table 2. 
______________________________________ 
Amounts, in % on the weight of the fabric 
Dye or (Run no.) 
auxiliary 1 2 3 4 5 
______________________________________ 
Terasil Yellow 
0.75 0.75 0.75 0.75 
0.75 
2GW 
Resolin 0.19 0.19 0.19 0.19 
0.19 
Red FB 200% 
Resolin 0.26 0.26 0.26 0.26 
0.26 
Blue FBL 
56% Acetic Acid 
0.5 0.5 0.5 0.5 0.5 
Plexene .TM. 
0.25 0.25 0.25 0.25 
0.25 
Extra Conc. 
F1933P 3 
Carolid .RTM. NOL 3 
Carolid .RTM. TOP 3 
Carolid .RTM. SFC 3 4 
Ratings* 2-3 2-3 2-3 2 2 
______________________________________ 
*AATCC GreyScale Ratings for Evaluating Staining 
Rating 1 Heavy Staining 
Rating 5 Very light or no stain 
It will be appreciated by those skilled in the art that changes could be 
made to the embodiments described above without departing from the broad 
inventive concept thereof. It is understood, therefore, that this 
invention is not limited to the particular embodiments disclosed, but it 
is intended to cover modifications within the spirit and scope of the 
present invention as defined by the appended claims.