Fiber-treatment agent composition

A composition and method for treating fibers is based on a mixture of an organopolysiloxane having at least one amino-substituted hydrocarbon radical directly bonded to a silicon atom and a carboxylic acid containing at least one ethylene oxide unit. The carboxylic acid reacts with the amino radicals to reduce yellowing and oxidation of the fiber treatment. The composition and method provide non-yellowing fibers and a treatment agent that does not gel during use, such as when exposed to carbon dioxide and/or used to treat carbon fibers.

BACKGROUND OF THE INVENTION 
The present invention relates to a fiber-treatment agent composition. 
Fiber-treatment agents based on organopolysiloxane containing the group 
represented by the formula --CH.sub.2 CH.sub.2 CH.sub.2 NHCH.sub.2 
CH.sub.2 NH.sub.2 have been used to impart lubricity to fibrous materials 
composed of natural fibers such as cotton, flax, silk, wool, angora, and 
mohair; regenerated fibers such as rayon and Bemberg; semisynthetic fibers 
such as acetate; and synthetic fibers such as polyesters, polyamides, 
polyacrylonitriles, polyvinyl chlorides, Vinylon, polyethylenes, 
polypropylenes, and Spandex. Refer to Japanese Patent Publication Number 
57-43673 (43,673/82). However, fibers treated with such an 
organopolysiloxane containing the group represented by the formula 
--CH.sub.2 CH.sub.2 CH.sub.2 NHCH.sub.2 cH.sub.2 NH.sub.2 are subject to 
yellowing due to a spontaneous oxidation occurring with time. Moreover, 
when continuous lubrication using rollers is carried out from a bath 
containing such an organopolysiloxane lubricant, moisture and carbon 
dioxide are absorbed from the atmosphere, and a white turbidity appears in 
the bath and the precipitation of a gel occurs. Furthermore, when such an 
organopolysiloxane is used for high-temperature oiling or lubrication as 
in the treatment of carbon fiber, for example, polyacrylonitrile-based 
carbon fiber, the organopolysiloxane is degraded to a gum, which sticks on 
the rollers, etc. This has the unfortunate effect of causing the fiber to 
snap. 
BRIEF SUMMARY OF THE INVENTION 
The present invention, having as its object a solution to the 
aforementioned problems, introduces a fiber-treatment agent which not only 
imparts excellent lubrication and softness, but which also does not yellow 
the fibrous material and is not subject to gelation or gum formation or 
the development of a white turbidity during storage, treatment, or 
heating. 
The aforesaid object is achieved by means of a fiber-treatment agent 
composition comprising (A) an organopolysiloxane represented by the 
formula 
##STR1## 
wherein R is a monovalent hydrocarbon group; A is an R group or a group 
with the formula --R.sup.1 (NHCH.sub.2,CH.sub.2,).sub.a NH.sub.2,; R.sup.1 
is a divalent hydrocarbon group; a=zero to 10; p and q are zero or more; 
with the proviso that p+q=10 to 2,000, and there is at least one --R.sup.1 
(NHCH.sub.2,CH.sub.2,).sub.a NH.sub.2 group in each molecule; and (B) 0.2 
to 5.0 moles, per 1 mole of primary and secondary amino groups in 
component (A), of a compound represented by the formula R.sup.2,O(C.sub.2 
H.sub.4 O).sub.b R.sup.3 COOH wherein R.sup.2 is a monovalent hydrocarbon 
group having 10 to 20 carbon atoms, b is at least one, and R.sup.3 is a 
divalent hydrocarbon group.

DETAILED DESCRIPTION OF THE INVENTION 
To explain the preceding in greater detail, component (A) is an 
organopolysiloxane as represented by the following general formula and 
which has at least one --R.sup.1 (NHCH.sub.2 CH.sub.2).sub.a NH.sub.2 
group in each molecule. 
##STR2## 
In the above organopolysiloxane formula R is a monovalent hydrocarbon 
group; A is an R group or a group with the formula --R.sup.1 (NHCH.sub.2 
CH.sub.2).sub.a NH.sub.2 ; R.sup.1 is a divalent hydrocarbon group; a=zero 
to 10; p and q are zero or more; with the proviso that p+q=10 to 2,000. 
R in the above formula is a monovalent hydrocarbon group, as exemplified by 
alkyl groups such as methyl, ethyl, propyl, and butyl; aralkyl groups such 
as 2-phenylethyl and 2-phenylpropyl; halogen-substituted alkyl groups such 
as 3,3,3-trifluoropropyl; alkenyl groups such as vinyl, propenyl, and 
butadienyl; cycloalkyl groups such as cyclohexyl; aryl groups such as 
phenyl and naphthyl; and alkayl groups such as tolyl and xenyl. Alkyl, 
alkenyl, and aryl groups are preferred. Furthermore, within a single 
molecule, R may be only a single species or may comprise different 
species. 
R.sup.1 in the above formula is a divalent hydrocarbon group, and examples 
in this regard are alkylene groups such as methylene, n-propylene, 
n-butylene, isobutylene, and isopropylene; arylene groups such as 
phenylene; and alkylenearylene groups such as ethylenephenylene. Alkylene 
is typically selected from among these. The value of a is zero to 10, and 
p and q are numbers with values of zero or more. 
A is --R.sup.1 (NHCH.sub.2 CH.sub.2).sub.a NH.sub.2 or an R group. When 
both of the two A groups are --R.sup.1 (NHCH.sub.2 CH.sub.2).sub.a 
NH.sub.2, q may be zero. 
Furthermore, the value of p+q is to be 10 to 2,000. The basis for this is 
as follows. Only a meager softness and smoothness are imparted to the 
fibrous material at values below 10, while emulsification becomes 
difficult at values in excess of 2,000. 
Considering the structure of component (A), it is the diorganopolysiloxane 
moiety which functions to develop softness and smoothness, while the amino 
group moiety functions to form a salt with component (B). 
Component (B) comprises a compound as represented by the general formula 
R.sup.2 O(C.sub.2 H.sub.4 O).sub.b R.sup.3 COOH. It forms a salt with the 
amino groups in component (A), or forms an amide bond with the amino 
groups in component (A) according to the heating conditions, and functions 
to improve both the stability of the composition and the resistance to 
yellowing. In addition, this component functions to improve the emulsion 
stability when the composition under consideration is emulsified. 
The group R.sup.2 in the above formula is a monovalent hydrocarbon group 
having 10 to 20 carbon atoms, and examples in this regard are branched 
alkyl groups and linear alkyl groups such as the undecyl group, lauryl 
group, myristyl group, and cetyl group; alkenyl groups such as the oleyl 
group; alkaryl groups such the octylphenyl group and nonylphenyl group; 
and aralkyl groups such as the phenyloctyl group. While b should have a 
value of at least one, values of 3 to 15 are preferred. R.sup.3 is a 
divalent hydrocarbon group, and examples here are alkylene groups such as 
methylene, ethylene, propylene, and isobutylene, as well as 
alkylenearylene groups such as the --C.sub.2 H.sub.4 C.sub.6 H.sub.4 -- 
group. Alkylene groups are preferred, and the methylene group is 
particularly preferred. 
Component (B) can be obtained, for example, by an addition reaction between 
ethylene oxide and stearyl alcohol or octylphenol, followed by 
carboxylation by a dehydrochlorination reaction with monochloroacetic acid 
or similar compounds. 
The component (B) under consideration is employed in a quantity giving 0.2 
to 5.0 moles per 1 mole primary and secondary amino groups in component 
(A). Yellowing prevention and the prevention of the development of gel and 
white turbidity do not appear at less than 0.2 moles. Furthermore, the 
hand becomes poor in excess of 5 moles. 
The composition of the present invention may be prepared by simply mixing 
components (A) and (B) to uniformity; however, mixing while heating at 40 
to 180 degrees Centigrade is preferred. 
The composition of the present invention can be directly adhered as such on 
fibrous materials, but treatment may also be conducted with it dissolved 
in an organic solvent, for example, toluene, xylene, benzene, n-hexane, 
heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl 
acetate, butyl acetate, mineral turpentine, perchloroethylene, 
trichloroethylene, etc. Treatment may also be conducted with it emulsified 
using a cationic or nonionic surfactant. 
Examples of cationic surfactants in this regard are quaternary ammonium 
hydroxides (and salts thereof) such as octyltrimethylammonium hydroxide, 
dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, 
octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammonium 
hydroxide, didodecyldimethylammonium hydroxide, 
dioctadecyldimethylammonium hydroxide, beef tallow trimethylammonium 
hydroxide, and cocotrimethylammonium hydroxide. 
Examples of nonionic surfactants in this regard are polyoxyalkylene alkyl 
ethers, polyoxyalkylene alkylphenol ethers, polyoxyalkylene alkyl esters, 
polyoxyalkylene sorbitan alkyl esters, polyethylene glycols, polypropylene 
glycols, and diethylene glycol. 
The surfactant is preferably used at 5 to 50 weight parts and more 
preferably at 10 to 30 weight parts per 100 weight parts 
organopolysiloxane comprising component (A). 
While water may be used in arbitrary quantities and its use quantity is not 
crucial, in general it will be used in a quantity affording an 
organopolysiloxane concentration of 5 to 60 weight%. It is particularly 
preferred that water be used in a quantity giving an organopolysiloxane 
concentration of 10 to 40 weight%. 
To emulsify the composition of the present invention, the surfactant as 
described above and a small quantity of the water are added to and mixed 
to homogeneity into the mixture of components (A) and (B). This may then 
be emulsified using an emulsifying device such as an homogenizer, colloid 
mill, line mixer, propeller mixer, vacuum emulsifier, or similar devices. 
Furthermore, the composition of the present invention may also contain 
other additives as known to the art, such as antistatics, softeners, 
creaseproofing agents, heat stabilizers, flame retardants, etc. 
The fibrous material can be treated using methods such as spray adhesion, 
roll application, brushing, immersion, dipping, etc. The add-on or uptake 
quantity will vary with the fibrous material and thus cannot be rigorously 
specified; however, in general it will fall within the range of 0.01 to 
10.0 weight% as organopolysiloxane fraction based on fibrous material. The 
fibrous material is then allowed to stand at the ambient temperature, 
subjected to a hot air flow, or is heat treated. 
The fibrous material may be composed of, for example, natural fiber such as 
wool, silk, flax, cotton, angora, mohair, and asbestos; regenerated fiber 
such as rayon and Bemberg; semisynthetic fiber such as acetate; synthetic 
fiber such as polyesters, polyamides, polyacrylonitriles, polyvinyl 
chlorides, Vinylon, polyethylenes, polypropylenes, and Spandex; and 
inorganic fiber such as glass fibers, carbon fibers, and silicon carbide 
fibers. It may take the form of, for example, the staple, filament, tow, 
top, or yarn, and in its structure may be, for example, a weave, knit, or 
nonwoven fabric. 
EXAMPLES 
The present invention is explained in greater detail, but not limited, in 
the following by illustrative examples. In the examples, unless specified 
otherwise, parts = weight parts, % = weight%, and the viscosity is the 
value measured at 25 degrees Centigrade. 
EXAMPLE 1 
Treatment baths (a) through (f) were prepared by blending toluene siloxane 
A and compound B as reported in Table 1. 
(siloxane A)-- 
##STR3## 
(compound B)--C.sub.1 3 H.sub.2 7 O(C.sub.2 H.sub.4 O).sub.3 CH.sub.2 COOH 
TABLE 1 
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formulation (parts) 
Components 
(a) (b) (c) (d) (e) (f) 
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Siloxane A 
9.2 9.2 9.2 9.2 9.2 0 
Compound B 
6.3 2.1 1.0 0.2 0 0 
Toluene 985.5 988.7 989.8 990.6 990.8 1000 
molar ratio: 
3 1 0.5 0.1 0 -- 
compound B to 
amino groups 
in siloxane A 
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Fluorescent-whitened 100% cotton broadcloth (50 cm .times.50 cm) was 
immersed for 10 seconds in the particular treatment bath. After removal, a 
100% expression ratio was obtained using squeeze rollers. The fabric was 
subsequently spread out and dried at room temperature (siloxane A 
add-on=0.9%), and was then heat-treated for 5 minutes in a hot-air drier 
at 150 degrees Centigrade and removed. 
The broadcloth fabric was then cut in two through the middle, and the 
degree of yellowing (.DELTA.YI) due to the heat treatment was determined 
on one piece using an SM Color Computer from the Suga Kikai Company. Using 
the remaining treated fabric, the flexural rigidity, which is indicative 
of the softness, was determined by the Clark method, and the crease 
resistance was measured by the Monsanto method (only in the warp direction 
for each fabric). In addition, a global evaluation as men's shirting was 
carried out base on the following criteria, and these results are reported 
in Table 2. 
+=good hand (flexural rigidity), no yellowing, crease resistance also 
excellent: entirely suitable as a treatment agent for men's shirting 
-=globally evaluated as somewhat unsatisfactory 
.times.=globally evaluated as unsuitable as a treatment agent for men's 
shirting (strong yellowing, also excessively slick) 
The results are reported in Table 2. The treatment agent of the present 
invention produced no yellowing, gave an excellent softness and crease 
resistance, and was very suitable for men's shirting. 
TABLE 2 
______________________________________ 
crease 
global 
flexural resis- 
evaluation 
yellowing rigidity tance for men's 
Treatment Bath 
(.DELTA.YI) 
(mm) (%) shirting 
______________________________________ 
(a) 1.21 36 83 + 
present (b) 1.18 34 84 + 
invention (c) 1.20 35 85 + 
(d) 1.29 34 85 + 
comparison (e) 8.01 37 78 x 
examples (f) -- 47 70 x 
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EXAMPLE 2 
The following treatment liquids were prepared in order to investigate the 
high-temperature stability which is an essential property in lubricants 
for polyacrylonitrile-based carbon fiber. The components are given in 
Table 3, and the siloxane A was the same as used in Example 1 (carboxylic 
acid/amino groups in siloxane A molar ratio = 1). 
TABLE 3 
______________________________________ 
formulation (parts) 
Components (g)* (h)* (i) (j) (k) (l) 
______________________________________ 
Siloxane A 75.0 81.3 96.0 98.0 98.7 100 
Compound B-1** 
25.0 -- -- -- -- -- 
Compound B-2** 
-- 18.7 -- -- -- -- 
Caproic Acid 
-- -- 4.0 -- -- -- 
Acetic Acid -- -- -- 2.0 -- -- 
Formic Acid -- -- -- -- 1.3 -- 
None -- -- -- -- -- 0 
______________________________________ 
*This invention. 
**Compound B1 = C.sub.13 H.sub.27 (C.sub.2 H.sub.4 O).sub.7 CH.sub.2 COOH 
Compound B2 = C.sub.8 H.sub.9 (C.sub.6 H.sub.4)O(C.sub.2 H.sub.4 O).sub.5 
CH.sub.2 COOH 
PREATION OF THE TREATMENT LIQUIDS 
Siloxane A was placed in a 300 cc four-neck flask, the carboxylic acid as 
specified in Table 3 was then added, and a nitrogen seal was set up. 
Mixing to homogeneity was subsequently carried out at 140 to 150 degrees 
Centigrade. The obtained treatment liquids (g) through (1) were emulsified 
as detailed below to prepare the respective emulsions. 
______________________________________ 
Emulsion components: 
______________________________________ 
treatment liquid (g) through (l) 
20.0 parts 
polyoxyethylene (6 mole) ether of 
4.0 parts 
trimethylnonanol 
polyoxyethylene (10 mole) ether of 
1.0 part 
trimethylnonanol 
water 75.0 parts 
______________________________________ 
EMULSIFICATION METHOD: 
The two emulsifying agents were added to the treatment liquid (g) through 
(1), and this was mixed with a stirrer for 10 minutes. Five parts water 
was then added, followed by stirring for an additional 10 minutes. The 
remaining 70 parts water was then added, and mixing for 30 minutes 
afforded the emulsion. 
4 g of the particular emulsion prepared as described above was placed in an 
aluminum cup (diameter = 5 cm, depth = 1.5 cm), and a gelation test was 
conducted by varying the time held at 150 degrees Centigrade. Evaluation 
was conducted as follows. 
+=remains as an oil, almost no change in viscosity, no gel development 
-=substantial increase in viscosity, partial gel development 
.times.=completely gelled, no longer fluid, converted to a strongly sticky 
gel 
These results are reported in Table 4. The treatment agent composition of 
the present invention gave unusually good results and did not undergo 
gelation. 
TABLE 4 
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Holding Time in Hours at 
150 degrees Centigrade 
Treatment Liquid 
1 5 8 
______________________________________ 
Present (g) + + + 
Invention (h) + + + 
(i) + - x 
Comparison (j) + x x 
Examples (k) + x x 
(l) + x x 
______________________________________ 
EXAMPLE 3 
Treatment baths were respectively prepared by the addition of 95 parts 
water to 5 parts of the emulsion of (g) or (1) as prepared in Example 2. A 
commercial fluorescent whitened 100% cotton broadcloth (30 cm.times.30 cm) 
was dipped into each treatment bath for 10 seconds. 
After expressing to a 100% expression ratio on a mangle roll, drying was 
carried out at room temperature (silicone uptake = 1%). This was followed 
by heat treatment by placing the fabric in an oven for 3 minutes at 130 
degrees Centigrade. The hand of this treated fabric was then examined 
sensorially. A 5 cm .times. 10 cm specimen was also cut from the treated 
fabric. While half was covered with black paper, the degree of yellowing 
was evaluated (ranked) using a discoloration/fading gray scale based on 
JIS L-0804 upon exposure to light for 3 hours in a Fade-0-Meter 
lightfastness measurement instrument. 
According to Table 5, the fabric treated with the treatment agent of the 
present invention gave excellent results, with an excellent hand and 
little yellowing due to light. 
TABLE 5 
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Yellowing 
(rank) by 
Treatment Fade-O-Meter 
Liquid Hand Exposure 
______________________________________ 
Present (g) soft, but not limp; 
4 
Invention very suitable as 
broadcloth; appropriate degree 
of slickness 
(l) soft, but not limp; 
2 
very suitable as 
Comparison broadcloth; appropriate degree 
Examples of slickness 
no hard, the hand is 
4 
treat- very poor, also 
ment lacking in resilience 
______________________________________ 
EFFECTS OF THE INVENTION 
The present invention introduces a fiber-treatment agent which can impart 
an excellent lubricity and softness without causing the fibrous material 
to yellow, and which does not undergo gelation or gum formation or the 
development of white turbidity during storage, heating, or treatment. In 
addition, the composition of the present invention is easily emulsified, 
and the emulsions so prepared are very stable.