Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
This invention relates to organofunctional silicone
agents for the treatment o fibers. More precisely this
invention relates to a mixture comprising two
organofunctional silicones which can impart durable
pliability, smoothness, crease resistance, compression
recovery and elongation recovery to fiber materials.
Various agents consisting of oryanopolysiloxanes and
their compositions have been proposed in attempts to impart
pliability, smoothness~ crease resistance and recovery
characteristics to fl,iber materials.
For example, dimethylpolysiloxane and its emulsion
have been used to impart pliability. Treatment agents
consisting of a methylhydrogenpolysiloxane~ a
dimethylpolysiloxane capped with terminal hydroxyl groups and
a catalyst or their condensation reaction; or treatmen~
agents consisting of a methylhydrogenpolysiloxane, a
vinyl-group-containing diorganopolysiloxane and a catalyst
for their addition reaction, are known to be used for
imparting durable pliability, crease resistance and recovery
characteristics.
Examples of organofunctional silicone agents include
an agent consisting o~ an organopolysiloxane having at least
two epoxy groups per molecule and an organopolysiloxane
having an amino group, to be used for smoothing organic
synthetic fibers, as disclosed in Canadian Patent No.
916,544; a treatment agent consisting of a
diorganopolysiloxane capped at both ends with hydroxyl
groups, an organosilane having both an amino group and an
alkoxy group per molecule and/or its hydrolyzed and condensed
products, as disclosed in U.S. Patent No. 3,962,500; a
5 ~ 8 '1
treatment agent consistiny of an aminoalkyl trial~oxysilane
and an epoxy-group-eontaining organopolysiloxane, as
disclosed in U.S. Patent Nos. 3r980~599 and 4,062,999; a
treatment agent comprising a carboxylfunctional silicone, as
diselosed in U.S. Patent No. 3,812,201 and
diorganopolysiloxanes capped at both ends with
triorganosiloxy groups, having two or more aminoalkyl groups
per molecule, as diselosed in U.S. Patent No. 3,766,115.
However, these conventional agents have their
L0 respeeti~e drawbaeks. For example, the agents primarily
eonsisting of dimethylpolysiloxane oil do not impart durable
pliability and smoothness although erease resistance and
reeovery characteristies are satisfactory. In the ease of
the agents containing alkoxysilanes as an indispensable
component, the alkoxysilanes are easily hydrolyzed when used
in emulsions and ~he life of the treatment bath is
undesirably reduced. There is also the drawback that the
feel is too stiff. There is another drawback in that the
agent is not suitable for the treatment of synthetic fiber
produets beeause the curing reaetion does not proeeed
satisfactorily unless the heating eonditions are strietly
eontrolled. In the ease of the agents eontaining
methylhydrogenpolysiloxane as an indispensable component,
there are the drawbacks tha~ thle curing r~aetion does not
proceed satisfaetorily unless a eatalyst is used, and that
the life of the treatment bath is too short if a eatalyst is
used. In the case of the agents primarily consisting of an
epoxy-group-eontaining organopolysiloxane and an
amino-group-containing organopolysiloxane, satisfaetory
1155~
durability cannot be obtained unless the treatment is
liberally applied.
Copolymers of aminofunctional silicones and
carboxylfunctional silicones have been disclosed in U.S.
Patent Nos. 2,754,284 and 3,338,943 as being useful fiber-
and film-forming compositions and coating and pulp treating
compositions, respectively. However, these compositions are
not suitable for the treatment of fibers to provide a good
feel for fiber materials produced therefrom.
1 1~ It is an object of this invention to overcome the
above-mentioned drawbacks of the conventional treatment
agents for the treatment of fibers. It is thus an object of
this invention to provide agents for the treatment of fibers
which inpart durable pliability, smoothness, crease
resistance, compression recovery and elongation recovery to
fiber materials simply by applying the composition to a fiber
material and drying at room temperature or by slight heat
treatment. An extension of life of the treatment bath is
also obtained.
These and other objects are achieved by the
fiber-treating compositions of this invention comprising a
mixture of an aminofunctional diorganopolysiloxane which is
expressed by the formula
R R R
A ~-t~io)m (liO3n Si-A
R Q R
; (NHCH2CH2taNHR'
and a carboxylfunctional diorganopolysiloxane which is
expressed by the formula
1155~
R" R" R"
B (SiO)~ tSiO)j - - Si-B
- Rl' Q' R"
COOR'''
The application of either component ta) or component
(b) alone imparts only non-durable pliability and smoothness
to fiber materials. ~ith a combination of both components,
the amino groups in component (a) react with the carboxyl
- groups in component (b) when a mixture of components (a) and
;~ 10 (b) is simply dried at room, or at slightly elevated,
temperature and very strong bonds are formed as a result of
crosslinking. Therefore, not only are durable pliability and
smoothness imparted, but also crease resistance, compression
recovery and elongation recovery can be imparted. The term
"durable" implies that the material is durable for a long
period with good resistance to washing in water and to dry
cleaning.
The present invention relates to a fiber-treating
composition comprising (a) a polydiorganosiloxane having the
formula
R R R
A (SiO)m (SiO)n Si-A
R Q R
(NHCH2CH2~aNH~ '
wherein each R represents a monovalent hydrocarbon residue
having from 1 to 20 carbon atoms, R' represents a hydrogen
atom or a monovalent hydrocarbon residue, ~ represents R or
-Q~NHCH2CH2~aNHR', Q represents a divalent hydrocarbon
residue, m is a positive integer, n is an integer, m + n has
a value of at least 10, m/tn + 2) has a value of from 5/1 to
500/1, and a is an integer from 0 to 10 and which contains at
least two -QtNHCH2CH2taNHR' groups per ~olecule; and (b) a
polydiorganosiloxane having the formula
R" R" R"
B ~Sio)k ~SiO) j --Si-B
R" f ~ R"
COOR" '
wherein each R" represents a monovalent: hydrocarbon residue
having from 1 to 20 carbon atoms, R"' represents a hydrogen
atom or a monovalent hydrocarbon residue, B represents R" or
-Q'-COOR" ', Q' represents a divalent hydrocarbon residue, k
is a positive integer, 1 is an integer, k + i has a value of
at least 107 k/(~ + 2) has a value of from 5/1 to 500/1 and
which has at least two Q'-COOR"' groups per molecule.
Component (a) contains an average of at least two
silicon bonded aminofunctional radicals per molecule, said
radicals having the formula -Q(NHCH2CH2)aNHR'. These
radicals may be bonded to terminal silicon atoms (A denoting
-Q(NHCH2CH2)aNHRI) and/or backbone silicon atoms of the
polydiorganosiloxane (a).
Examples of R' radicals in the aminofunctional
radic~l include the hydrogen radical and monovalent
hydrocarbon residues such as methyl, ethyl, propyl and
phenyl.
Examples of divalent hydrocarbon residues denoted by
Q in the aminofunctional radical include alkylene radicals,
such as -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH~CH(CH3)CH2-,
-(CH2)4-, and alkylenearylene radicals, such as -(CH2)2C6H4-.
Q is preferably the propylene radical.
S
5 8 ~
The value of a in the aminofunctional radicals can
be 0, thereby defining monoamino radicals of the formula
-QNHR', or an integer from 1 to 10, thereby defining
polyamino radicals, such as -QNHCH2CH2NHR',
-QNHCH2CH2MHCH2CH2NHR' etc. A preferred aminofunctional
radical in the compositions of this invention has the formula
-CH2CH2CH2NHCH2CH2NH2-
Examples of monovalent hydrocarbon residues denoted
by R in component (a) include alkyl radicals, such as methyl,
ethyl, propyl, butyl~ pentyl; alkenyl radicals, such as
vinyl; halogenated radicals, such as 3,3,3-trifluoropropyl
and aryl radicals, such as phenyl. The R radicals in
component (a) can be identical or not, as desired~
Preferably all R radicals are methyl radicals although a
mixture of methyl radicals and other monovalent hydrocarbon
residues, such as phenyl or vinyl, is very often used.
In the formula for component (a) m is an integer
greater than zero and n is an integer equal to or greater
than zero. Of course, it is to be understood that
polydiorganosiloxanes do not constitute a single molecular
species and that the values of m and n in the component (a)
will be average values.
The average values of m and n are such that the
value of the sum of m ~ n is at least 10 and the value of the
quotient m/(n ~ 2) is from 5/1 to 500/1. For example, when n
is zero, _ must be at least 10, but not more than 1000. Of
course, in this case, all radicals denoted by A are ~',
-Q(NHCH2CH2)aNHR' radicals. Similarly, when n has a value of
3, _ must have a value of from 25 to 2500. In this case
1 ~ ~5~84
radicals denoted by A can be R radicals and/or
-Q(NHCH2CH2)aNHR' radicals.
If the value of m + n is less than 10, the imparting
of pliability and smoothness to a textile are poor due to
adsorption of the component into the interior of the fibers.
If it exceeds 1000, emulsification of the component is
difficulto Therefore, the value of m + n is preferably from
100 to 1000. If the value of m/~n + 2) is less than 5/1, the
imparting of pliability and smoothness to the textile are
poor, while i it exceeds 500/1, the imparting of cr'~ase
resistance, compression recovery and elongation recovery are
poor.
A preferred aminofunctional-radical-containing poly-
diorganosiloxane has the formula
Me3sio(Me2sio)m(Me7io)nsiMe3
( CH2 ) 3N~CH2CH2NH2
Polydiorganosiloxanes bearing aminofunctional
radicals are well known in the silicones art; some are
commercially available. Their preparation needs no further
elaboration here. A suitable preparative method can be found
in U.S. Patent No. 3,512,915
Componènt (b) contains an average of at least two
silicon-bonded carboxylfunctional radicals per moleclle, said
radicals haviny the formula -Q'COOR' " . These radicals may
be bonded to terminal silicon atoms (B denoting -Q'COOR" ')
and/or backbone silicon atoms of the polydiorganosiloxane
(b).
Examples of divalent hydrocarbon residues denoted by
Q' in the carboxylfunctional radical are the same as those
~,~.b. 7
1~5r3~
noted for Q above. The Q' radicals in component (b) may be
the same as, or different from, the Q radicals in component
(a).
Rl" in the carboxylfunctional radical can be
hydrogen, thereby defining carboxylic-acid-functional
radicals of the formula -QICOOH, such as CH2CH2COOH; or a
monovalent hydrocarbon residue, such as methyl, ethyl and
hexyl, thereby defining carboxylic-ester-functional radicals,
such as -CH2CH2COOCH3 and -C~2CH(CH3)COOCH2CH3.
Examples of monovalent hydrocarbon~ residues denoted
by R" in component (b) include methyl, ethyl, propyl, benzyl,
dodecyl, stearyl, 3,3,3-trifluoropropyl, beta-phenylethyl,
alpha-methyl-beta-phenylethyl, vinyl and phenyl. The R"
radicals in component (b) can be identical or not, as
desired. Preferably all R" radicals are methyl although a
mixture oE methyl radicals and other monovalent hydrocarbon
residues, such as phenyl or vinyl, is very often used.
In the formula for component (b) k is an integer
greater than zero and i is an integer equal to or greater
than zero. Of course, it is to be understood that
polydiorganosiloxanes do not constitute a single molecular
species and that the values of k and 1 in component (b) will
be average values.
The average values of k and i are such that the
value of the sum k + i is at least 10 and the value of the
quotient ~/(i + 2) is from 5/1 to 500/1. Of course, when i
is ~ero all radicals denoted by B in component (b) must be
-Q'COQR" ' radicals.
If the value of k + 1 is less than 10, the imparting
of pliability and smoothness to a textile are poor due to
1 ~ S~8~
adsorption of the component into the interior of the fibers.
If it exceeds 1000, emulsification of the component is
difficult. Therefore, the value of k ~ i is preerably from
100 to 1000. If the value of k/(i ~ 2) is less than 5/1, the
imparting of pliability and smoothness to a textile are poor,
while if it exceeds S00/1 the imparting of crease resistance,
compression recovery and elongation recovery are poor.
A preferred carboxylfunctional-radical-containing
polydiorganosiloxane has the formula
Me3SiO(Me2SiO)ktMefiO);SiMe3
CH2CH2COOH
Polydiorganosiloxanes bearing carboxylfunctional
radicals are well known in the silicone art; their
preparation needs no elaboration here. A suitable method for
their preparation is disclosed in U.S. Patent No. ~L,076,695
A treatment bath is prepared by dissolving
components (a) and (b), for example, in an organic solvent
such as toluene, xylene, benzene, n-hexane, heptane, mineral
terpene, perchloroethylene or chlorothene. The treatment
solution can be applied to fiber materials by any method such
as spraying, applying with a roller or immersion. The
solution can be emulsified with an appropriate emulsifier,
such as sulfates of higher alcohols, alkylbenzenesulfonates,
higher alcohol polyoxyalkylene adducts, higher fatty acid
polyoxyalkylene adducts, alky~phenol polyoxyalkylene adducts
and higher fatty acid sorbitan esters, before use and then
the emulsion can be applied to fiber materials by spraying,
applying with a roller or immersion.
l .1~5~
Both components can be dissolved or emulsi~ied
individually and a mixture of both solutions or emulsions can
be applied to the fiber materials. Alternatively, one of
these solutions or emulsions is appli~d first to the fiber
materials and subsequently the other solution or emulsion is
applied. The important point is that the treatment can be
carried out by any arbitrary methods as long as both
components coexist on the fiber materials. However, for
homogeneous treatment of the fibers, the fiber materials are
lQ preferably treated with a treatment agent prepared by
combining both components in advance.
The treatment agent of this invention is typically
applied to fiber materials in an amount of 0.1 to 4 wt% as a
total of both components, based on the weight of the fiber
material.
When the organic solvent and/or the water is
subsequently removed by allowing the material to stand at
room temperature, or by blowing hot air on the materials, or
by heating, a cross-linking reaction occurs rapidly between
the amino groups in component (a) and the carboxyl groups
(acid and/or ester) in component ~b). As a result, durable
pliabilityr smoothness, crease resistance, compression
recovery and elongation recovery can be imparted to the
treated fiber material. Thus, in a preferred embodiment the
compositions of this invention contain an equal, or
approximately equal, number of -QtNHCH2CH2)aNHR' radicals and
-Q-COOR "' radicals. In terms of work efficiency and
improvement in durability, the treated fiber materials are
preferably dried by blowing hot air on them or by heating
1 1 5 ~
instead of by allowlng them to stand at room temperature. If
desirable, an appropriate catalyst for curing can be added~
The fiber materials to be treated with this
; treatment agent may include natural fibers such as wool,
silk, linen, cotton and asbestos, regenerated fibers such as
rayon and acetate, synthetic Eibers such as polyester,
polyamide, vinyl, polyacrylonitrile, polyethylene,
polypropylene and spandex, glass fibers, carbon fibers and
silicon carbide fibers. With respect to the shapes of the
materials, the following can be treated: staples, filaments,
tows, yarns, woven fabrics, knitted fabrics, nonwoven fabrics
and resin-coated cloths. However, the materials can be
treated effectively if they are treated continuously in a
sheet form as in woven fabrics, knitted fabrics, nonwoven
fabrics and mattress filler flocking.
The following examples are disclosed to illustrate,
but not limit, the present invention. All parts, ratios and
percentages are by weight unless otherwise specified. All
viscosities were measured at 25C. Me denotes the methyl
radical.
Crease resistance of textile samples was measured by
the Monsanto method as described in JIS L 1079, "Test Method
for Synthetic Fiber Woven Fabrics, for Untreated Fabric and
Various Treated Fabrics With or Without Dry Cleaning".
~riefly this method is conducted as follows:
A test specimen with a size of 1 cm x 4 cm is cut.
This test specimen is folded in two so that each side of the
fold has a size of 1 cm x 2 cm. The folded test specimen is
inserted between glass plates and left undisturbed ~ith a
load of 500 g for 5 minutes. After releasing the load, the
'
1 .15558~
test specimen is carefully picked up with a pair of tweezers
and the folded section is hung over a taut wire with a
diameter of 0.51 mm. After 5 minutes, the angle of opening
of the fabric is measured as the angle (a) subtended by two
straight lines drawn from the axis of the taut wire tO the
center of each olded section of the sample.
The crease resistance (A), expressed in %, is
calculated from the following formula as an average value of
10 sets of data determined respectively along the vertical
and horizontal directions of the textile and rounded to the
nearest lnteger
A (%) = ~ x 100
180
Example 1
~n amino-group-containing organopolysiloxane having
the formula
Me3SiO(Me2SiO)24g(MeSiO)sSiMe3
( CH2 ) 3NHCH2CH2NH2
(viscosity 1100 cSt, 1 part) and a carboxyl-group~containing
organopolysiloxane of the formula
Me3SiO(Me2SiO)24gtMeSiO)sSiMe3
CH2CH2COOH
(viscosity 1400 cSt, 1 part) were dissolved in toluene (98
parts) and the solution obtained served as a treatment
solution. Changes in viscosity and gelation did not occur
when this treatment solution was left standiny at room
temperature for 5 days.
A 100% wool sharkskin weave man's suit fabric was
immersed in this treatment solution and subsequently removed
from the solution. The fabric was squeezed using a mangle
roll to such a degree that the amount of the
12
1 155~8~
organopolysiloxanes which adhered was 1.5~, and dried in air.
Subsequently, the fabric was heat-treated at 150C for 3
minutes.
For comparison, treatment solutions were prepared
under the same conditions as described above except that
either the amino-group-containing organopolysiloxane alone or
the carboxyl-group-containiny organopolysiloxane alone was
used. The fabric was treated under the same conditions.
The treated fabrics were divided into two pieces
with a scissors. One of -these pieces was dipped in a mineral
terpene with a bath ratio of 1:200 with stirring for 15
min~tes. This process was applied as a surrogate Eor dry
cleaning. The dry cleaning was repeated three times. The
crease resistance was measured by the above-described
;~ Monsanto method.
As shown in Table I, the fabric treated with the
treatment agent of this invention demonstrated excellent
crease resistance and the decrease in this characteristic due
to dry cleaning was almost negligible.
Exam~le 2
An amino-group-containing organopolysiloxane of the
formula
Me3SiO(Me2SiO)34g(MefiO)7SiMe3
( CH2 ) 3NHCH2C~2NH2
(viscosity 2200 cSt, 1 part) and a carboxyl-group-containing
organopolysiloxane of the formula
Me3SiO(Me2SiO)34g(~leSiO)7(MeSiO)SiMe3
C8H17 CH2CH2COOH
(viscosity 2550 cSt, 1 part) were dissolved in
perchloroethylene (98 parts) and the resulting solution
5 5 8 ~
served as a treatment solution. Changes in viscosity and
yelation did not occur when this treatment solution was left
standing at room temperature for 5 days.
A two-bar weft knitted wooly polyethylene
terephthalate (75 denier) fabric was immersed in this
treatment solution and su~sequently removed from the
solution. The fabric was squeezed using a mangle roll to
such a degree that the amount of the organopolysiloxane which
adhered was 1.0~, and dried at 110C for 5 minutes.
For comparison, treatment solutions were prepared
under the same conditions as described above except that
either the amino-group-containing organopolysiloxane alone or
the carboxyl-group-containirlg organopvlysiloxane alone was
used. The fabric was treated under the same conditions.
With respect to the untreated knitted fabric and the
various treated knitted fabrics, the elongation recovery was
measured after the elongation/recovery process was repeated
ten times at a percentage of elongation of 40~ and 80%
according to JIS L 1080 "Test Method for Stretchability of
Woven Fabrics." The feel o the fabrics was examined
manually. As shown in Table II, the knitted fabrics treated
with the treatment solution of this invention demonstrated
excellent elongation recovery. The fabric had an appropriate
silky feel and a luxuriant resiliency. The fabric also had
excellent feel.
Example 3
The amino group-containing organopolysiloxane used
in Example 2 (35 parts), water (5 parts) and a
polyoxyethylene nonylphenol ether (a mixture of three types:
2 mol, 5 mol and 25 mol ethylene oxide adducts, adjusted to
14
1:lS~5~
HLB 12.0, 5 parts) were placed in a container and the mixture
~as blended thoroughly using a stirrer. Subsequently, water
(45 parts) was added to the mixture and an emulsion was
obtained.
Separately, the carboxyl-group-containing
organopolysiloxane used in Example 2 (35 parts)~ water (5
parts), and the polyoxyethylene nonylphenol ether described
above (adjusted to HLB 11.5, 5 parts) were placed in a
container and the mixture was blended thoroughly using a
stirrer. Subsequently, water (45 parts) was added to the
mixture and an emulsion was obtained.
The above-mentioned two types of treatment agents
were mixed at a ratio of 1 1 and the mixture was diluted with
water to such a degree that the amount of the
organopolysiloxanes was 2~. The dilute mixture of the
treatment agents served as a treatment solution. Changes in
viscosity, gelation and phase separation did not occur when
the treatment solution was left standing at room temperature
for 5 days.
The knitted fabric used in Example 2 was treated
with this ~reatment solution under the same conditions as in
Example 2. Both the elongation recovery and feel of the
; treated fabric were examined.
As shown in Table III, the knitted fabric treated
with the treatment agent of this invention demonstrated
excellent elongation recovery. The fabric had an appropriate
silky feel and a luxuriant resiliency. The fabric also had
excellent feel.
11~55~
Example 4
A treatment solution was prepared using the
amino-gro~p-contalning organopolysiloxane used in Example 1
(1 part), a carboxyl-group-containing organopolysiloxane of
the formula
Me3Si.O(Me?SiO)2~g(MeSio)sSiMe3
CH2CH2COOCH3
(viscosity 1200 cSt, 1 part) and xylene (98 parts)O A 100~
wool sharkskin weave men's suit fabric was treated with thi.s
treatment solution under the same conditions as in Example 1.
The crease resistance was measured as in Example 1. The
crease resistance before dry cleaning was 86, and the crease
resistance after dry cleaning was also 86. The treated
fabric demonstrated excellent pliability.
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