Dye compositions

This invention discloses compositions and methods for dyeing natural proteinaceous and synthetic polyamide fibers, particularly wool, silk and nylons, utilizing dye assistants effective with both acid and disperse dyes, such assistants being synergistic combinations of (a) dicyclopentenyl alcohol with (b) certain other materials, none of the components in either (a) or (b) being, in themselves, effective dye assistants for both acid and disperse dyes.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to the dyeing of natural proteinaceous and synthetic 
polyamide fibers, particularly the normal and specialty nylons. 
2. Description of the Prior Art 
The dyeing of nylons--manufactured fibers in which the fiber-forming 
substance is any long chain synthetic polyamide having recurring amide 
groups as part of the chain--may, depending on the specific type of nylon 
involved--be accomplished with many different classes of dyes, e.g.: 
basic, acid, disperse, direct, etc. The acid and disperse dyes are in wide 
commercial use and the dye compositions of this invention utilize these 
classes of dyes. For reasons of speeding of dyeing, maximum utilization of 
dye and improving evenness of color throughout the dyed fiber, these dyes 
are generally used in conjunction with "assistants" (sometimes designated 
as "carriers")--materials which promote the attainment of speedy dyeing, 
maximum dye utilization, etc. There are a number of assistants 
commercially available but the experiments carried out in the work leading 
to this invention indicated that, generally, an assistant effective with 
acid dyes is not optimum for disperse dyes and vice versa. Use of only one 
assistant for both acid and disperse dyeing would be advantageous to a 
dyer in that inventories of different assistants could be reduced and 
there would be less possibility of erroneous selection of assistant. 
It has now been found that combining certain materials which in themselves 
are not effective assistants both for acid and disperse dyeing of nylon 
and other fibers, results in combinations which are synergistically 
effective with both types of dyes. 
SUMMARY OF THE INVENTION 
In accordance with this invention there have been found dye assistants 
effective with both acid and disperse dyes, such assistants comprising a 
combination of (a) dicyclopentenyl alcohol with (b) one or more other 
materials which themselves are not effective dye assistants with both acid 
and disperse dyes. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
Dicyclopentenyl alcohol has the structure 
##STR1## 
can be prepared in the manner described by Bruson and Reiner, JACS 67, pp. 
723 (1945) and has the properties described in U.S. Pat. No. 3,634,016. 
Hydrogenated dicyclopentenyl alcohol is also effective and can be prepared 
as described in U.S. Pat. No. 3,062,782. In U.S. Pat. No. 3,634,016, 
dicyclopentenyl alcohol--therein designated "dicyclopentyl alcohol"--and 
hydrogenated dicyclopentenyl alcohol--therein designated "hydrogenated 
dicyclopentyl alcohol"--are disclosed as dye assistants for acid dyes with 
nylon. In U.S. Pat. No. 3,923,453, dicyclopentenyl alcohol--therein 
designated "dicyclopentyl alcohol"--is disclosed as being useful, in 
admixture with benzyl alcohol, as a dye assistant for acid dyes with 
nylon. It has now been found that combinations of dicyclopentenyl alcohol 
with lower alkyl benzoates (by lower alkyl is meant alkyl radicals 
containing from one to six carbon atoms) or with dibenzyl ether are 
effective dye assistants not only for acid dyes, but also for disperse 
dyes. 
When used, in the dyeing system described in Example I, to dye certain 
specialty nylons comprised of 40% or greater of the condensation product 
of 4,4'-diamino-dicyclohexyl methane and decanodicarboxylic acid having 
the basic repeating unit: 
##STR2## 
all of the three aforedescribed materials were found to be unsatisfactory 
as assistants for all the acid and disperse dyes tested herein. 
However, certain combinations of dicyclopentenyl alcohol with lower alkyl 
benzoates or with dibenzyl ether were found to exceed the performance, as 
dye assistants, that would be predicted by assuming a mere arithmetic 
averaging of the properties of the members of the combinations. In fact, 
the combinations were found generally to be effective with both acid and 
disperse dyes. It was further observed that, when dyeing the 
aforedescribed specialty nylon, dye compositions comprising the disperse 
dye Eastman Polyester Navy Blue 2R-LSW (Eastman Chemical Products, Inc.; 
C.I. Disperse Blue 79) with the combinations as assistants gave 
commercially acceptable dyeing results. This contrasts with the outcome 
found when the individual members of the combinations were used with this 
dye: all gave unacceptable results due to the dyed fiber being a blue-gray 
hue rather than a navy blue, or due to uneven dyeing, or due to incomplete 
utilization of the dye. 
The lower alkyl benzoate of the preferred embodiment is butyl benzoate 
which is, like dicyclopentenyl alcohol and dibenzyl ether, a known 
compound and an article of commerce. While butyl benzoate is recommended 
as a dye assistant for both acid and disperse dyeing of the aforedescribed 
specialty nylons, the experimental work leading to this invention showed 
that butyl benzoate, alone, was not an effective assistant for all the 
disperse dyes herein tested. The dicyclopentenyl alcohol/butyl benzoate 
combinations of this invention were, however, effective with all these 
disperse dyes. 
The percentage of dicyclopentenyl alcohol in the preferred combinations, 
with either butyl benzoate or dibenzyl ether, may be from about 10 to 90 
weight percent, but preferably from about 30 to 70 weight percent of the 
combination, the other component comprising the remainder. The assistants 
of the present invention are essentially insoluble in water and to be 
effective in the normally-used aqueous dye baths must be emulsified or 
otherwise dispersed in water. A convenient method of supplying these 
assistants for industrial use in as emulsifiable concentrates--a mixture 
of emulsifying agents and assistants which, when stirred with a minimum of 
energy into water, will give a usable emulsion. While the amount and type 
of emulsifying agent for specific dyes and fibers is determined by 
experience and experiment, a generally useful emulsifier system is one 
containing both anionic and non-ionic emulsifiers. Typical of anionic 
emulsifiers is the isopropylamine salt of dodecylbenzene sulfonic acid, of 
non-ionic emulsifiers is a polyoxyethylene derivative of castor oil. 
Various amounts of the aforedescribed assistants can be used in order to 
accomplish the results of the present invention. The use of excess 
assistant while possible, is wasteful since after an efficient amount has 
been added, no additional beneficial results are achieved by an excess. 
The amount of assistant to be used, expressed as a weight ratio of 
assistant-to-dye should be between about 1:1 and 20:1, the precise amount 
depending on the fiber-dye-process conditions. (By "assistant" is meant 
the active components of a formulation, e.g. in Example I, the 80 weight 
percent emulsifiable concentrate contains 80% "assistant"). The amount of 
dye in the dye bath is commonly expressed as a weight percentage 
on-weight-of-fiber (OWF) and may be from about 0.1 to 10 with OWF 
percentages of from 1 to 5 being typical of commercial practice. 
"Acid dyes" are in general salts of organic acids wherein the colorant 
portion of the dye is the anionic (negatively charged) moiety. The 
assistants of this invention are useful with fibers which can be dyed 
effectively with acid dyes, such fibers include the natural proteinaceous 
fibers such as wool and silk and the synthetic polyamide fibers such as 
the different types of nylons (e.g. nylon 66 or the aforedescribed 
specialty nylons). 
"Disperse" dyes are called so because they are almost insoluble in 
water--which is the most commonly used dyeing medium--and are applied in 
the form of finely-divided particles which are dispersed in water. The dye 
assistants of this invention are useful also in the dyeing of fibers for 
which disperse dyes are used. Such fibers include modified regenerated 
natural products such as secondary cellulose acetate and cellulose 
triacetate, and totally synthetic fibers such as the polyesters (e.g.--the 
long chain condensation product of terephthalic acid and ethylene glycol) 
and the synthetic polyamides (e.g.--nylon 66 or the aforedescribed 
specialty nylon). 
The actual procedures described below in Example I for the applying of dyes 
to fibers using the dye assistants of the present invention, are typical 
of those suggested for superatmospheric pressure dyeing of the 
aforedescribed specialty nylons which require relatively rigorous dyeing 
conditions. (See, for example, pp. 321-327, "Book of Papers, 1974 National 
Technical Conference" published in 1974 by the American Association of 
Textile Chemists and Colorists). Less rigorous conditions would be usable 
with nylons such as nylon 66 into which dyes diffuse more rapidly. With 
the appropriate modifications in processing, other methods of applying the 
dye--such as printing, padding, spraying onto the fiber, etc. are usable. 
In addition to dyes and dye assistants, dyeing formulations usually contain 
various auxiliary agents. These agents can include emulsifiers, anionic, 
cationic or non-ionic, for emulsifying or dispersing the dye and dye 
assistant in water. pH control may be accomplished by the addition of 
formic acid, acetic acid and the like. Sodium phosphate may be used for 
water softening, natural or artificial gums may be used to control the 
thickness of the formulation, surfactants may be used to improve wetting 
of the fabric, etc. The decision as to what and how much auxiliary to use 
and the sequence of addition usually rests with the dyemaster, his 
decisions being made on the basis of his experience of dyeing in general 
and of the fibers and dyes used in a particular dyeing operation. In 
Example I, a blend of the isopropylamine salt of dodecylbenzene sulfonic 
acid and a polyoxyethyated castor oil is used to emulsify the dye 
assistants, sodium hexametaphosphate is used for wetting purposes, 
mono-sodium phosphate is used as a buffer for pH control and sodium 
N-methyl-N-oleoyl taurate is a surfactant/emulsifier. This invention, 
however, is not limited to these particular auxiliaries nor the 
proportions used. 
The compositions of the present invention contemplate dye preparations 
containing the aforedescribed combinations as essential dye assistants and 
either an acid or a disperse dye. The pH of these compositions may be any 
value commonly used for acid or disperse dyeing--typically from about 3 to 
slightly below 7; the dyebath of Example I has a pH of about 6.5. These 
compositions can have as optional additional components the aforementioned 
general type of auxiliary agents to control the physical and chemical 
conditions of the dyeing. The specific additives to be used and their 
amounts depend upon the particular fiber to be dyed and on the operating 
conditions chosen.

The following Example I illustrates methods of preparing and applying the 
dye compositions of the present invention, which is not limited thereto. 
The dyes used in the present invention and identified in Example I are 
representative of the classes of acid and disperse dyes and were chosen to 
give the three primary colors of red, blue and yellow since by suitable 
combination of these colors it is possible to obtain a wide variety of 
hues. Unless otherwise specified all temperature are in degrees Celsius, 
weights in grams and volumes in milliliters. Where "dye assistant" is 
specified, the reference is to the emulsifiable concentrate or aqueous 
dispersion; with the assistants of this invention, this concentrate 
contains 80 weight percent active components, 20 weight percent 
emulsifiers. 
EXAMPLE I 
PREATION OF DISPERSE OR ACID DYEBATH COMPOSITION AND DYEING PROCEDURE 
Experimental dye assistants were first formulated into emulsifiable 
concentrates by admixture at 30.degree.-40.degree. C. with emulsifiers to 
make a homogeneous: 
______________________________________ 
Emulsifiable Concentrate 
______________________________________ 
Dye Assistant 80 parts weight 
Trydet 3300 15 
Trylox CO-40 5 
100 
______________________________________ 
(Trydet 3300 is the isopropylamine salt of dodecylbenzene sulfonic acid, 
Trylox CO-40 is a polyoxyethylene derivative of castor oil. 
To an Atlas Electric Devices Company's Launder-Ometer, Model LHTP stainless 
steel test container were charged: 
Approximately 300 ml tap water at about 50.degree. C. 
5 ml of 3% (wt) solution of sodium hexametaphosphate 
5 ml of 3% (wt) solution of monosodium phosphate 
5 ml of 3% (wt) solution of sodium N-methyl-N-oleoyl taurate* 
1 ml of an aforedescribed emulsifiable concentrate of dye assistant 
FNT *(Igepon T-51) 
(The tap water used in this example had a hardness of about 40 parts per 
million, but the invention is not limited to water of this hardness. The 
degree of hardness permissible depends upon the conditions peculiar to a 
particular dye formulation/fiber combination and a dyemaster will use 
water softeners to adjust hardness if he deems this necessary). 
The above mixture was stirred until it became homogeneous. Then 0.2 gram (2 
percent on-weight-of-fiber) of the dye to be used in the experiment was 
dissolved in about 84 ml of lukewarm tap water and this solution added to 
the above mixture. This final mixture was the completed dyebath and was, 
if necessary, adjusted to a volume of 400 ml by addition of tap water so 
as to give, with a 10 gram fiber sample, a bath-to-fiber ratio of 40:1. A 
10 gram sample of the aforedescribed specialty nylon (type 470 or type 
472, either giving substantially the same dyeing results, and in the form 
of swatch of Qiana.RTM. (Dupont's T.M.) was next added to the dyebath and 
the preparation stirred. The stainless steel container was then sealed 
pressure-tight and placed in the Launder-Ometer which was then switched 
"on" (at all times during the "on" condition, the dyebath was stirred by 
reason of its container being continually rotated in a manner which 
regularly inverted and righted it thus imparting a sloshing motion to the 
contained dyebath). The Launder-Ometer bath temperature was then rapidly 
(about 15 minutes) raised from room temperature (20.degree.-25.degree. C.) 
to 70.degree. C. at which temperature the programmed heating mode of the 
Launder-Ometer was used to bring the bath temperature from 70.degree. C. 
to 100.degree. C. over a period of 45 minutes and from 100.degree. C. to 
130.degree. C. over a period of 30 minutes. The bath was then held for one 
hour at 130.degree. C. with the container contents under autogeneous 
pressure. 
At the conclusion of this period, the programmed cooling mode of the 
Launder-Ometer was used to cool the bath to approximately 50.degree. C. 
over a period of 50 to 60 minutes and the Launder-Ometer switched to 
"off". 
After cooling, the container was removed from the Launder-Ometer, and 
emptied of its liquid contents. The degree of exhaustion of the dye was 
visually noted and observations made of loss of dyebath or of presence of 
glycerin in the container-- both of which conditions were caused by faulty 
sealing of the container. No data were taken from runs showing such signs 
of leakage; the experiment was repeated until a satisfactory run was 
obtained. 
The swatch was rinsed in lukewarm tap water and then washed by adding to 
its container 200 ml of solution, at 70.degree. C., containing 1% of an 
alkyl aryl polyether surfactant (Triton X-100) and 1% sodium pyrophosphate 
(Na.sub.4 P.sub.2 O.sub.7.10H.sub.2 O) and soaking for 10 minutes. The 
swatch was then washed with lukewarm tap water until free of the 
surfactant/phosphate wash solution. After drying at room temperature from 
16 to 24 hours, the swatch was heated in a forced draft oven for about 3 
minutes at 193.degree. C. in order to free it of the last trace of dye 
assistant and to stabilize the dye. It was then ironed to help eliminate 
wrinkles and the effectiveness of the dye assistant evaluated. This 
effectiveness is a combination of a number of performance factors which a 
dyemaster would not normally measure quantitatively, but would 
subjectively evaluate and integrate to get an overall estimate of the 
merit of the assistant. These factors include: completeness of exhaustion 
of dye from the dyebath (the more complete, the better the assistant) 
trueness of hue and intensity or saturation of the color of the dyed fiber 
and evenness of dyeing--i.e. there are no darker or lighter areas on the 
dyed fiber. The above factors were evaluated for each dye and dye 
assistant combination tested in this experimental work. With acid dyes, 
the evaluation of color trueness and intensity was made using only the 
experimentally dyed fabric itself, with disperse dyes the colors of the 
dyed fabrics were judged against an array of samples of polyester fabric 
dyed with the same dyes and various assistants and covering the range of 
assistant effectiveness from highly effective to low effectiveness. While 
a dyemaster usually would classify an assistant as highly effective or 
moderately effective or of low effectiveness with no attempt to further 
quantitate his judgement, a numerical scale is adopted here to better 
differentiate differences between assistants. This scale is shown in Table 
I. A rating of 4 or higher is considered to indicate an assistant with 
commercial utility--with the proviso however, that an off-hue color is not 
commercially acceptable even though consideration of other factors might 
lead to a rating of 4 or above. 
The procedure detailed in Example I was used to prepare numerous dye 
compositions utilizing the following three acid and three disperse dyes: 
______________________________________ 
Experimental 
Designation 
DYE DESCRIPTION 
______________________________________ 
1. Capracyl Red B (C.I. Acid Red 182) 
2. Supralan Yellow NR (C.I. Acid Yellow 121, 
C.I. No. 18690) 
3. Alizarine Supra Blue A (C.I. Acid Blue 25, 
C.I. No. 62055) 
4. Genacron Red B (C.I. disperse Red 88) 
5. Eastman Polyester Yellow GLW (C.I. disperse 
Yellow 42, C.I. No. 10338) 
6. Eastman Polyester Navy Blue 2R-LSW (C.I. 
disperse Blue 79) 
______________________________________ 
The following individual materials, and combinations were employed as dye 
assistants. Comparison of the results for the individual materials with 
those for the combinations illustrates the synergistic effects found and 
the particular effectiveness of the combinations with Eastman Polyester 
Navy Blue 2R-LSW (C.I. disperse Blue 79): 
______________________________________ 
Experimental 
Active Component of Assistant 
Designations 
(Ratios by Weight) 
______________________________________ 
A Dicyclopentenyl Alcohol 
B Butyl Benzoate 
C 7/3 Dicyclopentenyl Alcohol/Butyl Benzoate 
D Dibenzyl Ether 
E 7/3 Dicyclopentenyl Alcohol/Dibenzyl Ether 
F 3/7 Dicyclopentenyl Alcohol/Dibenzyl Ether 
______________________________________ 
TABLE I 
______________________________________ 
EFFECTIVENESS RATINGS OF DYE ASSISTANTS 
______________________________________ 
DYE ASSISTANTS, 
DYES, EXPERIMENTAL DESIGNATIONS 
EXPERIMENTAL ACID DISPERSE 
DESIGNATIONS 1 2 3 4 5 6 
______________________________________ 
A &lt;4 4 5 7 6 2- 3(1) 
B 8 8 8 7 8 2-3 
C 6 8 8 8 7 8 
A &lt;4 4 5 7 6 2-3(1) 
D 7 7 7 6 6 2-3(1) 
E 6 8 7 8 9(1) 7 
F (2) (2) (2) 8 9 5 
______________________________________ 
Note: 
(1)BlueGray Hue 
(2)This combination not tested with acid dyes 
Legend: Numerical Rating 
Effectiveness 
______________________________________ 
1 
2 Low 
3 
4 
5 Medium 
6 
7 
8 High 
9 
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