Note: Descriptions are shown in the official language in which they were submitted.
1- 2048890
SIT.ICONF. TExTIT~F FINISHFS
FIELD O~ T~E INVENTION
The present invention is directed to
silicone copolymers which can produce durable
hydrophilic finishes on cotton te~tiles. More
particularly, the invention is directed to a method
of treating cotton textiles to impart softness and
durable hydrophilic properties to the te~tiles.
BACKGROUND OF THE INV~TION
Te~tiles, and particularly cotton and cotton
blend textiles, are often treated with silicone
finishing agents to provide softness, improve tear
strength, flex abrasion, processibility and wrinkle
recovery. These finishing agents are generally
applied to the te~tile from aqueous systems in
pad-dry-cure operations.
- Commonly employed types of si1icone
finishing agents are the polysilo~anes containing
pendant organic groups. The silicone finishing
agents which have been typically used heretofore have
hydrophobic properties and result in the fabrics
having little or no water absorbency. When
hydrophilic silicone copolymers are used, the
te~tiles have improved hydrophilic properties, but
these finishes generally have poor dura~ility. To
improve the durability of the hydrophilic silicone
finishes, reactive or curable organomodified
silicones are generally used.
One example of the efforts to produce
durable silicone finishes on te~tiles is disclosed in
D-16388-1
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U.S. Patent No. 4,459,383. The fiber-treating
composition includes at-least two reactive
organosilicones which are able to react with each
other and form durable finishes. The organomodified
silicones include (1) an epo~y-substitutes silo~a-ne
and (2) an amino or carbo~y-substituted and
polyether-containing siloxane copolymer. The epoxy
silicone is reacted with the amino-containing
silo~ane or alternatively the carbo~yl-containing
siloxane during curing to crosslink the siloxanes
onto the fibers.
Other silicone finishing agents include
silicone copolymers having polyo~yalkylene
substituents and hydrolyzable di- or trialkoxysilyl
groups. The silicones are applied to the fabric in
the presence of moisture where the alkoxysilyl groups
are hydrolyzed and cured at elevated temperatures.
One example of this form of silicone finishing agent
is disclosed in U.S. Patent No. 4,283,519. A
hydrophilic organosilicone includes a trialko~ysilyl
pendant group and a polyoxyethylene/polyoxypropylene
chain terminated with a hydrogen or an acyl group.
The silicone is applied to the fabric and cured by
heating in the presence of a catalyst.
U.S. Patent No. 4,758,646 discloses a bis
(alko~ysilyl) polyether copolymer as a fabric sizing
agent. The sizing agent is applied to the-fabric and
cured by heating to produce a hydrophilic finish
having antistatic and soil release properties.
Glyo~al has been known to react with cotton
and produce durable press finishes for cotton related
fabrics such as that disclosed in U.S. Patent No.
4,472,167. In this patent, an aqueous solution of
D-16388-1
~ 3 ~ 20~890
glyo~al, glycol and an acid catalyst is applied to a
cellulosic textile and cured by heating. The glyoxal
is reported to form acetal crosslinks with
cellulose. The glycol is added as a coreactant
additive to modify the length of the crosslinks in
the network. An optional silanol-terminated silicone
is reported to produce a treated fabric having
considerable water repellency.
U.S. Patent No. 4,269,603 discloses a
durable press treatment for te~tile fabrics using an
aqueous solution of glyoxal, a reactive hydrophobic
silicone and a catalyst. The treating composition is
cured at about 177C to 204C. This curing
temperature has the disadvantage of producing a
significant loss of tear strength of the fabric. The
treating composition is reported to impart wrinkle
resistance and smooth drying performance.
The present invention is directed to a
method of producing hydrophilic silicone finishes for
cellulose-containing te~tiles, using glyoxal to bind
silicone copolymers to the te2tile. The resulting
silicone finishes are durable to washing and impart
soft hydrophilic properties and durable press
properties to the treated fabric.
SUMMARY OF THE INV~NTION
The present invention is directed to
finished te~ile materials and to a method of
imparting durable hydrophilic softness to
cellulose-containing te~tile materials. The
hydrophilic finishes produced are sufficiently
dura~le to withstand repeated washings in water
D-16388-1
~889~
and/or home laundering. The textile finish can be
used with or without other te~tile finishes.
The hydrophilic finish of the invention is
produced by forming a chemical bond between the
cellulose portion of a textile substrate and a
hydrophilic silicone via acetal formation with
glyo~al. The hydrophilic finish-forming composition
is a mi~ture of glyoxal, glycol, a reactive
hydrophilic silicone and an acid catalyst. The
cellulose-containing textile is impregnated with the
composition and subjected to reactive conditions,
such as heating. The hydrophilic silicone then
becomes fixed to the textile to impart durable
hydrophilic properties.
The preferred reactive silicones are the
hydrophilic silicone random copolymers having a
hydro2yl terminated organic polyether substituent.
Preferably the silicone copolymers have primary or`
secondary hydroxyl terminated polyoxyalkylene
chains. Preferably the polyoxyalkylene is a
polyo~yethylene or a polyo~yethylene/polyo~ypropylene
copolymer where the ethyleneo~ide content is such
that the silicone is hydrophilic. The silicone
copolymer may also be a terpolymer of polysiloxane,
polyo~yethylene or polyo~yethylene/polyoxypropylene
terminated with a hydroxy-, alko~y-, acetoxy-end
group and pendant groups which bear hydro~yl, amine,
amide or thiol groups or groups capable of forming
hydro~yl gro~ps under reactive conditions. The
preferred functional groups which are able to form
hydro~yl groups are epo~y-pendant groups.-
The reactive hydrophilic silicone whencombined with the glyoxal and glycol provides durable
D-16388-1
2048890
hydrophilic softness to the textile and enhanced
durable press performance compared to the glyoxal-
glycol system alone. A hydrophilic silicone copolymer,
which becomes chemically linked to the textile,
provides improved durable wrinkle recovery angles,
smooth drying performance and increased tear strength
to the treated fabrics.
In accordance with one aspect of the present
invention, there is provided a process of forming
durable hydrophilic silicone finishes on textiles
formed at least partially of cellulosic fibers such
finishes withstanding repeated washing in water which
process comprises:
a) impregnating the textile with a finishing agent
in the form of an aqueous solution comprising by weight
about 1% to 5~ glyoxal, about 1% to 15~ glycol, about
1% to 15% hydrophilic silicone copolymer, about 0.1 to
2% acid catalyst and 0~ to 2~ catalyst activator based
on the weight of the solution, the hydrophilic silicone
copolymer being at least one organomodified silicone
copolymer selected from the group consisting of (i)
R R
R3SiO...(S:O)n(S )m...SiR3
q ~2
wherein R at each occurrence is a monovalent
hydrocarbon radi~al; n is an integer and m is an
integer equal to or greater than l; and R2 has the
formula -(CH2)~(oR3)y(0R4)zR5 wherein oR3 and oR4 are
repeating units; R3 and R4 are the same or different
and sele~ted from the group consisting of C2H4 and
C3H6; ~, y and z are integers with the proviso that
and at least y or z are not zero; R5 is hydro~yl, n,
m, ~, y and z are selected such that the silicone is
soluble or dispersible in water at room temperature;
and (ii)
2d48890
5a
~ R R
R3siO...(s-o)n(s:o)m(s-o)o---siR3
~- ~2 ~6
wherein R, n and m are as above, and o is an integer
of at least l; R2 at each occurrence has the formula
-(CH2-)1~(oR3)y(0R4)zR~
wherein ~, y, z, R3 and R4 are as above, R5 is
hydroxy-, alkoxy- or acetoxy-, and R6 is a monovalent
organic radicàl having a reactive group selected from
the group consisting of epo~ide, hydrosyl, diol,
amine, amide and thiol groups and n, m, o, x, y and z
are such that the silicone is solu~le or dispersible
in water at room temperature; and
(b) heating the textile to a temperature of 120 -
180C to cure the finishing agent.
In accordance with another aspect of the present
invention, there is provided a heat curable textile
finishing agent for forming durable hydrophilic
finishes on textiles formed at least partially of
cellulosic fibers, such finishes withstanding repeated
washing in water, which finishing agent in the form of
an aqueous solution comprising by weight about 1% to 5%
glyoxal, about 1% to 15% glycol, about 1% to 15%
hydrophilic silicone copolymer, about 0.1 to 2% acid
catalyst and 0% to 2% catalyst activator based on the
weight of the solution, the hydrophilic silicone
copolymer being at least one organomodified silicone
copolymer selected from the group consisting of (i)
R R
R3sio~(s-o)n(s-o)m~siR3
~ ~2
wherein R at each occurrence is a monovalent
hydrocarbon radical; n is an integer, m is an integer
- 2048890
5b
equal to or greater than 1; and R2 has the formula
-(CH2)~-(oR3)y(0R~)~R5 wherein, oR3 and OR~ are repeating
units; R3 and R~ are the same or different and selected
from the group consisting of C2H~ and C3H6; x, y, z are
integers with the proviso that x and at least y or z are
not zero; Rs is hydroxyl, n, m, x, y and z are selected
such that the silicone is soluble or dispersible in water
at room temperature; and
(ii) ~. R R
R3SiO...(S-O)n(s O)m(s o)o~SiR3
~ h2 -6
wherein R, m and n are as above and o is an integer of at
least 1; R2 at each occurrence has the formula -(CH2)~-
(oR3)y(0R~)~Rs wherein x, y, z, R3 and R~ are as above, Rs
is hydroxy-, alkoxy- or acetoxy, and R6 is a monovalent
organic radical having a reactive group selected from the
group consisting of epoxide, hydroxyl, diol, amine, amide
and thiol groups and n, m, o, x, y and z are ~uch that
the silicone is soluble or dispersible in water at room
temperature.
In accordance with yet a further aspect of the
present invention, there is provided a textile formed at
least partially of cellulosic fibers having a durable
hydrophilic finish that withstands repeated w~;ng in
water produced by the steps of:
a) impregnating the textile with a finishing agent
in the form of an aqueous solution comprising by weight
about 1% to 5% glyoxal, about 1% to 15% glycol, about 1%
to 15% hydrophilic silicone copolymer, about 0.1 to 2%
acid catalyst and 0% to 2% catalyst activator based on
the weight of the solution, the hydrophilic silicone
copolymer being at least one organomodified silicone
copolymer selected from the group consisting of (i)
~'
5c 2048890
R3sio~(s-o)n(s-o)m~siR3
". R2
wherein R at each occurrence is a monovalent
hydrocarbon radical; n is an integer and m is an
integer equal to or greater than l; and R2 has the
formula -(CH2)s-(oR3)y(OR4)zR5 wherein oR3 and oR4
are repeating units; R3 and R4 are the same or
different and selected from the group consisting of
C2H4 and C3H6; s, y, z are integers with the proviso
that s and at least y or z are not zero; R5 i5
hydrosyl, n, m, s, y and z are selected such that the
silicone is soluble or dispersible in water at room
temperature; and
(ii)
R - _
R3SiO...(S-O)n(S O)m(S-O)o...SiR3
~ ~2 q6
wherein R, m and n are as above a~d o is an integer
of at least l; R2 at each occurrence has the formula
-(CH2)~(0R3)y(0R4)2R5 wherein s, Yr Z, R3 and R4 are
as above, R5 is hydroxy-, alkoxy- or aceto~y, and R6
is a monovalent organic radical having a reactive
group selected from the group consisting of eposide,
hydrosyl, diol, amine, amide and thiol groups and n,
m, o, s, y and 2 are such that the silicone is
soluble or dispersible in water at room temperature;
and
b) heating the textile to a temperature of 120 -
180C to cure the finishing agent.
. ~,
'L~
~048890
5d
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a
method of applying hydrophilic finishes to the
surface of cellulose-containing te~tiles to impart
durable hydrophilic properties. The resulting
te~tiles have improved softness, wettability, and
durable press properties. The hydrophilic finish can
be applied to woven and nonwoven testiles containing
cellulose fibers, such as for esample cotton, flas,
hemp and jute. The testile may be a blend of
cellulose fibers and synthetic fibers such as, for
esample, a cotton/polyester blend.
The process of the invention applies a
finishing agent solution to a testile and cures the
finishing agent on the testile. The finishing agent
solution includes glyosal, glycol, an acid catalyst
and a reactive hydrophilic silicone copolymer having
a hydrosyl terminated polyether chain.
Alternatively, the hydrophilic silicone copolymer may
~be a terpolymer with a polyether having hydrosy-,
alkosy- or acetosy-end groups and functional pendant
groups bearing hydrosyl, amine, amide or thiol group
or groups capable of forming reactive hydrosyl
groups. The functional pendant group may be, for
P~
~3~
_ 6 - ~0~8890
e~ample, an epo~y-pendant group. The hydrophilic
silicone having the hydro~yl group or functional
group capable of forming hydroxyl groups under
reaction conditions is linked to the cellulose
substrate to impart durable hydrophilic properties to
the te~tile. The chemical linkage between the
cellulose and the silicone is formed by the use of
the acid catalyzed reaction of glyoxal, silicone and
cellulose. The finish is generally produced by
applying an aqueous solution of the silicone
copolymer, glyo~al, glycol and acid catalyst to the
cellulose textile, which is then dried and cured by
heating at about 120 to about 180C.
The textiles treated in accordance with the
invention possess durable hydrophilic softness. In
the presence of an acid catalyst, glyo~al forms
acetal links between the cellulose and hydroxyl group
of the silicone copolymer.
The silicone copolymers of the invention are
preferably random hydrophilic silicone copolymers
having a polyoxyalkylene chain, hydroxyl groups or
functional groups capable of forming hydro~yl groups
under reactive conditions, and are reactive with
glyoxal to form linkages between the silicone and the
cellulose te~tile via the acetal formation. In a
preferred embodiment of the invention, the reactive
silicone is a copolymer having a polyether chain with
hydro~yl end groups or alternatively a terpolymer
with polyether and reactive pendant groups.
The preferred silicone copolymer is
represented by the formula:
D-16388-1
- 7 - 20~8890
R3 Si(S O)n(S:O)m...SiR3
~ -2
wherein R at each occurrence is a monovalent
hydrocarbon radical. R may be, for e~ample, an alkyl
preferably having from 1 to 4 carbon atoms, aryl or
arylalkyl. Most preferably R is methyl. In the
above formula, n is an integer and m is an integer
equal to or greater than 1. For egample, n may be
about 10 to about 150. R2 at each occurrence is
represented by the formula
-(CH2)x(oR3)y(0R9)zR5
with recurring units oR3 and oR4, where R3 and R4 are
the same or different and are C2H4 or C3H6. R5 is
hydro~yl. In the formula, x, y and z are integers
with the proviso that g and at least y or z are not
zero. In the formula, n, m, g, y and z are selected
such that the silicone is soluble or at least
slightly soluble or dispersible in water at room
temperature. The amount of ethyleneo~ide in the
copolymer is sufficient to impart hydrophilic
properties to the silicone copolymer. R2 consisting
of oxyethylene and oxypropylene moieties linked in a
random chain or in a block chain preferably has a
molecular weight of about 150 to about 6,000 most
preferably of about 3S0 to about 4,000.
In an alternative preferred embodiment the
hydrophilic silicone copolymer has the general
formula:
R R R
R3SiO...(SiO)n(SiO)m(SiO)o...SiR3
R R2 R6
D-16388-1
2048890
wherein R, n and m are as above and o is an integer
of at least 1. R2 at each occurrence is represented
by the formula
-(CH2)s(oR3)y(0R4)zRS
wherein s, y, z, R3 and R4 are as above and RS is
hydro~y-, alkosy- or acetosy-. The-alkosy preferably
has 1 to 4 carbon atoms. In the preferred
embodiment, R2 has a molecular weight of about lS0 to
6,000 and most preferably about 3S0 to 4,000. The
amount of ethyleneoside in the copolymer is
sufficient to impart hydrophilic properties to the
silicone copolymer. R6 is a monovalent organic
radical having one or more hydrosyl, diol, amine,
amide, thiol or eposide groups. Preferably R6 has a
pendant group selected from the group consisting of
hydro~yl, diol and eposide group. In the preferred
embodiment R6 is
selected from the group consisting of -R7-CH-CH2,
R7 ~ , R7CH20H, R7CH(oH)CH20H and
R7 O =, wherein R7 is a divalent organic radical
OH
such es methylene, ethylene, propylene, phenylene,
-C3H60CH2- and (CH2)3-O-. Most preferably R6 is
-(cH2)3ocH2cH-cH2~ -(CH2)2 ~' -C3H60H,
~ _OH
-C3H6-0CH2CIH_CIH2 or C2H4
OH OH
i ~
~S
9- 204~890
In the preferred embodiments, the silicone
copolymer is soluble or dispersible in water. The
silicone copolymer may be a liquid at room
temperature or a wa~y solid. Generally, the water
solubility is enhanced by increasing the weight
ratio of the polyo~yethylene group to the
polyo~ypropylene and to the silicone backbone in the
molecule. For moderately water soluble silicone
copolymers, a suitable surfactant may be used to
disperse the silicone in water.
The glycol employed in the process may be a
suitable diol which is able to react with the
glyoxal. Glycols suitable for the process of the
invention include, for example, straight chain
alkanediols having the formula, HOR8OH, wherein R8
is an alkylene group having 2 to 12 carbon atoms or
polyoxyalkylenes (polyethylene glycol or
polypropylene glycol). The glycols preferably have
a molecular weight of less than about 200. The most
preferred glycols are diethylene glycol and
triethylene glycols. Other glycols which may be
used include, for e~ample, ethylene glycol,
propylene glycol and dipropylene glycol.
The glyoxal used is suitably a commercial grade
material commonly supplied as a 40% aqueous
solution. Although less preferred, the glyoxal may
be obtained as a solid which is subsequently
dissolved in water to form a solution of a desired
concentration.
The preferred acidic catalysts are Bronsted or
Lewis acids capable of catalyzing the reaction of
the glyo~al with the cellulose. Suitable acid
catalyst include, for example, p-toluenesulfonic
D-16388-1
2048890
acid, zinc chloride, zinc tetrafluoroborate,
aluminum chloride, magnesium chloride, aluminum
chlorohydroxide and mi~tures thereof. In the
preferred embodiment, the catalyst is a mi~ture of
aluminum sulfate and tartaric acid as a catalyst -
activator. Other acid catalyst activators which are
effective include citric acid, glycolic acid, lactic
acid, malic acid and mixtures thereof. The mole
ratio of the acid to aluminum sulfate may range from
0.5:1 to 15:1. The preferred range of tartaric acid
to aluminum sulfate is about 0.5:1 to 5:1.
In the process of the invention the finishing
agent is prepared as an aqueous solution containing
about 1% to about 5% glyoxal on a solids basis,
about 1% to about 15% by weight of a glycol, about
1% to 15% by weight hydrophilic silicone polymer,
about 0.1% to 2% by weight acidic catalyst and 0% to
2% of catalyst activator. Preferably the molar
ratio of glyoxal to glycol is about 1:1 to 1:2 in
the finishing agent. Suitably the aqueous solution
contains from about 3% to 15~ by weight of a 40%
glyoxal solution, 3% to 15% by weight glycol, 1% to
5% by weight hydrophilic silicone copolymer, 0.1% to
1% catalyst and 0% to 0.5% by weight of an optional
acid catalyst activator with the balance to 100%
with water.
The cellulose-containing textile is preferably
impregnated in a bath with the treating solution and
wet pick-up adjusted to 100% of the weight of the
dry textile. Alternatively, the treating solution
may be applied by spraying or by other suitable
applicators. The moisture content of the
impregnated textile maybe initially reduced by
D-16388-1
2048890
11
heating at an elevated temperature for about 2 to
about 8 minutes and preferably about 3 minutes prior
to substantial curing. The treated textile may then
be cured by heating to a sufficient temperature for
a sufficient period of time. The drying temperature
may vary depending on the te~tile composition but
will generally range from about 50C to 110C and is
preferably about 85C. The te~tile is then heated
to cure the finishing agent on the textile at a
temperature of about 110C to 180C. The treated
te~tile can be dried and cured in a one step heating
process by heating the textile at a temperature of
about 110 to about 180C. The heating time to dry
and cure the finishing agent is dependent on the
amount of water remaining from the treating solution
to be evaporated and the curing temperature.
Suitably the curing time is about 0.5 to 5 minutes.
Alternatively the heating step may be initiated, for
example, at about 50C and gradually heated to about
180C over a sufficient period of time to dry and
cure the finishing agent on the te~tile.
The following e~amples illustrate the preferred
embodiments of the invention and are not intended to
be limiting. The treated te~tiles were evaluated
and compared for properties and characteristics.
The testing methods employed were the standard
methods as understood by those skilled in the art
and include Wrinkle Recovery Angle by AATCC Method
66-1984, Durable Press Appearance by AATCC Method
124-1984, Wettability Test by AATCC Method 39-1980,
Fabric Conditioning by ASTM Method D-1776-74, and
Elmendorf Tearing Strength by ASTM D-1682-64.
D-16388-1
- - 12 - 2048890
The fabric used in the following examples
was a bleached, desized mercerized cotton print
cloth, Style 400M by Testfabric, Inc., Middlesex,
N.J. The softness of the treated fabric was
evaluated by a hand panel and the tested fabrics were
rated using a scale of 1 to 10, where 1 is the
softest and 10 is the harshest. In the following
- examples, durability is intended to refer to the
resistance of the hydrophilic silicone to repeated
washing or laundering. The durability of the
hydrophilic silicone on the te~tile was assessed by
determining the amount of the silicone on the treated
fabrics before and after five machine washing cycles
as conducted by AATCC standard machine wash
conditions with AATCC Detergent 124 and standard
drying procedure. Durable press properties are
intended to refer to the overall properties of the
textile including shrinkage control, wrinkle recovery
angle, and smooth drying performance.
F~x~MpT~
A mercerized, 100% cotton print cloth was
treated with the aqueous treating composition as set
forth in Table I below. Wet pick-up was adjusted to
100% by weight of the dry fabric. The treated
fabrics were dried in a forced draft oven for about 3
minutes at B5C. Subsequently, the dried treated
fabrics were cured by heating in a forced draft oven
at 125C for 2 minutes. The durability of the
hydrophilic silicone copolymers was determined by a
comparison of the silicone level on treated fabrics
before washing and after five washing cycles.
D-16388-1
- 13 - 2 048 8~0
Standard AATCC machine wash conditions using AATCC
Detergent 124 and drying were applied. The
durability to washing is calculated as the percentage
of initial level of the silicone determined on the
unwashed fabrics. The accuracy of the analytical
method was 10%.
TA8LE 1
SAMPLE N0. 1 2
Comparative Samples A
Percent by ~e;ght
Glyoxal, 40% solution 6.0 12.0 6.0
Diethylene glycol 8.8 8.8
(I) Me3SiO(Me2S;0)13(MeSj0)5SiMe3 2.0 2.0 2.0 2.0
C3H6(C2H4)7H
Aluminum sulfate octadecahydrate 0.770.77 0.77
Tartaric acid hydrate 0.370.37 0-37
~ater 8Z.0676.06 90.8698.0
Durability of the silicone 65% 72% 33% 12%
The above data show a significant increase
in the durability of the hydrophilic silicone
copolymer on the cotton fabric from the treating
solution containing glyo~al, diethylene glycol, and
an acid catalyst compared to a similar treating
solution without diethylene glycol or the silicone
used alone.
D-16388-1
- 14 - 2048890
EXAMPLE 2
A similar textile treatment was conducted on
a mercerized cotton fabric using the process as in
Example 1 for different treating solutions containing
silicone copolymers having different silicone to -
polyethyleneo~ide ratios. The durability of the
silicone on the fabric was determined as in E~ample
1. The treating solution and resulting durability
are shown in Table 2.
TABLE Z
SAMPLE N0. 1 3 4 S
Percent by ~eight
Glyoxal, 40% solution 6.0 6.0 6.0 6.0
Diethylene glycol 8.8 8.8 8.8 8.8
(I) Me3SiO(Me25iO)13(MeSi0)5SiMe3 2.0 - - ~
C3H6(0C2H4)70H
(II) Me35iO(Me25iO)3û(MeSiO)5SiMe3 - 2.0
C3H6(0CzH4)70H
(III) Me3SiO(Me2SiO)45(MeSiO)5SiMe3 - - 2.0
C3H6(0C2H4)70H
(IV) Me3SiO(Me2SiO)75(MelSiO)lOSiMe3 2.0
C3H6(0C2H4)70H
Aluminum sulfate octadecahydrate 0.77 0.77 0.77 0.77
Tartaric acid h~drate 0.37 0.37 0.37 0-37
~ater 82.06 82.06 82.06 82.06
% ethylene oxide 50 37 28 33
Durabilit~ of the Silicone (%) 65 41 -(spots) 33
D-16388-1
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The above data demonstrate that as the
hydro~yl functionality and hydrophilicity increases
as represented by the percent of the ethylene o~ide
in the copolymer, the durability of the hydrophilic
silicone finish increases.
EXAMPT,F. 8
A textile treatment as in E~ample 1 was
conducted on 100% cotton fabric using different
treating solutions to compare the durability of
silicones having a terminal primary or secondary
hydroxyl groups on the organic group. The fabric was
treated, dried and cured as in Example 1.
~ARLF. 3
SAMPLE N0. 6 7
Glyoxal, 40% solution 6.0 6.0
Diethylene glycol 8.8 8.8
(V) Me3SiO(Me2SiO)40(MefiO)lOSiMe3 2.0
C3H6 (0C2H4 ) 12H
(VI) Me3SiO(Me2siO)4o(Melsio)losiMe3 2.0
(random copolymer) C3H6(0c2H4)s(0c3H6~6oH
Aluminum R-~lfate octadecahydrate . 0.77 0.77
Tartaric acid hydrate 0.37 0.37
Water 82.06 82.06
Durability ~ 50% 2~%
D-16388-1
- 16 - 20~8~90
The durability of the hydrophilic silicone
on the textile as shown in Table 3 is significantly
greater for the silicone of Sample 6 having a primary
hydroxyl group on the polyethyleneoxide pendant
group. The primary hydro~yl group on the
polyo~yethylene is more reactive than the secondary
hydroxyl end group on the
polyo~yethylene/polyoxypropylene pendant group, and
produces a finish that is more durable to repeated
washing.
F.~Z~MpT.~ 4
This example considers the differences in
durability between silicone copolymers having
reactive hydro~yl end groups on the organo group and
non-reactive silicone copolymers having methoxy end
groups on the polyether organo group. In this
e~ample, compound VII is a hydrophilic silicone
copolymer with a terminal hydro~yl group on the
polyoxyethylene/polyoxypropylene chain. The organic
block included about 75% by weight polyo~yethylene.
Compound VIII is a methoxy terminated
polyoxyethylene/polyo~ypropylene silicone copolymer.
The organic block of compound VIII included about 75%
by weight polyoxyethylene. The treating solution
having the composition as shown in Table 4 was
applied to samples of mercerized, 100% cotton
fabric. The treated fabric was dried and cured in
one step in a forced air oven at 171C for 90
seconds. The fabric samples were washed using
standard washing procedures. The durabiLity of the
finish is shown in Table 4. This data clearly
demonstrate the increased durability of the silicone
D-16388-1
- 17 - 204~890
finish using the hydroxyl terminated polyether
modified silicone compared to a non-reactive
silicone. The residual durability of the
non-reactive silicone (VIII) is believed to be due to
the incomplete capping (85%) of the polyether. The
remaining 15% contains hydroxyl functionality which
may produce the semi-durable properties of this
sample.
TABLE 4
SAMPLE N0. 8 9
(% by weight)
Glyoxal, 40% ~olution 6.0 6.0
Diethylene glycol 8.8 8.8
Aluminum 6ulfate octadecahydrate 0.125 0.125
Tartaric acid hydrate 0.075 0.075
(VII) Me3SiO(Me2SiO~74(MefiO)9SiMe3 2.0
C3H6(0C2H4)23(0C3H6)60H
(VIII) Me3SiO(Me2SiO)74(MefiO)gSiMe3 - 2.0
C3H6(0C2H4)23(0C3H6)60Me
Water 83.0 83.0
Durability 56% 31%
FX~qpt.F. 5
The durability of the epo~y functional
hydrophilic silicones was evaluated in this e~ample.
The aqueous treating solutions were prepared as
Samples 10-13 according to Table 5. Compound I~ is
D-163B8-1
- 18 - 2 0~ 8 890
silicone terpolymer with a metho~y-terminated
polyo~yethylene/polyo~ypropylene and
(3,4-eposycyclohe~yl)ethyl functional group. The
polyo~yethylene/polyo~ypropylene included about 40%
by weight polyo~yethylene. Compound X is a silicone
terpolymer with 3-glycidylo~ypropyl and icetyl-
terminated polyo~yethylene/polyo~ypropylene, with
higher epo~y content than Compound IX. The
polyo~yethylene content in the polyo~yalkylene is
about 40% by weight. Compound X~ was a silicone
terpolymer of 3-glycidylo~ypropyl and acetyl-
terminated polyo~yethylene/polyosypropylene with
higher epo~y content than Compound ~. The
polyo~yethylene content in the polyo~yalkylene was
about 40% by weight. The solutions were applied to
the cotton fabric and adjusted to 10~% of the weight
of the dry fabric. The fabrics were dried and cured
in one step for 90 seconds at 171C in an oven. The
durability of each silicone is recorded in Table 5.
The data demonstrate high durability of the silicone
bearing epo~ide, which increases with the epo~y
content in the molecule.
TABLE 5
S~mple No 10 11 12 13
~X by ~eight)
Gl~ox~l 40% 6 6 6
Dieth~lene glycol 8 8 8 8 8 5
Alurinum sulf~t~ oct~dec~hydr~te 0 2 0 2 0 2
T~rt~ric ~cid hydr~te 0 05 S 0 05
(IX) ~k3SiO(~e2SiO)85(~kSiO)~(MeSiO)nSiHe3 1 0 1 0
C2H4~0
C3H6(0~2H4)2s(0c3H6)27o~e3
n~n=7 5
epoxide content 0 25X
D-16388-1
2048890
lg --
(X) Me3sio(Me2sio)85(Mes;o)o(Mes;o)pMesio)qs;Me3 1.0
C3H60CH2-cH-cH2
o
C3H6(0C2H4~36(oC3H6)410COCH3
C3H6(0C2H4~13(0C3H6)15Coc 3
o+p~q=7.5
o/p-3:1
epox;de content 0.4%
(XI) Me3SiO(Me2S;0)85(MeSiO)s(MeSiO)sMeSiO)tSiMe3 1.0
C3H60CH2-CH-CH2
o
C3H6(0c2H4)36(0c3H6)4loco 3
C3H6(0CzH4)13(0C3H6)15ococ 3
2s+t=7.5
epox;de content 0.7%
Water 83.95 83.95 83.95 99.0
Durab;lit~ ~fter 5 washing cycles 61% 67% 79% 23%
F.XPIMPT.~ 6
The durability of the hydrophilic silicones
having diol pendant groups produced from the epo~y-
functional silicones is demonstrated in this e~ample
as Samples 14 and 15. Compounds IX and ~I from
~ample 5 were reflu~ed in a water/isopropanol
solution in the presence of 0.2% trifluoroacetic acid
for 2 hours to hydrolyze the epo~y group and form
Compounds XII and ~III respectively. The hydrolysis
efficiency was determined by titration of the
residual epo~ide to be 8~% to gO~. The treating
D-16388-1
- 20 - 20~8~ 90
solution was prepared as shown in Table 6 accordin~
to the method of Example 1. The treated fabric was
dried and cured at 171C for 90 seconds. The
durability of the silicone was determined as shown in
Table 6. This data shows that the silicones having
pendant diol groups have similar durability as the
epo~y-pendant silicones.
TABLE 6
Sample No. 14 15
(% by we;ght)
Glyoxal, 40% 6 6
Diethylene glycol 8.B 8.8
Aluminum sulfate octadecahydrate 0.2 O.Z
Tartaric acid hydrate 0.05 0.05
(XII) Me3SiO(Me25io)8s(Mesio)m(Mesio)nsiMe3 1.0
CzH4~1_
OH
C3H6 ( C2H4 ) 25 ( C3H6 ) 270Me
~n=7.5
(XIII) Me3sio~Me2sio)85(Mesio)s(Mesio)s(Mesio)tsiMe3 1.0
C3H60CH2--CH- ICH2
OH OH
C3H6(0C2H4)36(0C3H6)410COcH3
C3H6(0C2H4)13(0C3H6)15CCH3
2s~t=7.5
Hater 83.85 83.95
Durab;l;ty after 5 washing cycles 61% 6~%
D - 163 88 - 1
- 21 - 204~890
EXAMPLE 7
This e~ample evaluates the durable press
properties of the glyo~al-glycol-hydrophilic silicone
systems. The treating solutions were prepared in
accordance with Table 7. The solutions were applied
to the cotton fabric samples and adjusted to 100% of
the weight of the fabric. The fabrics were dried and
cured at 171C for 90 seconds. The properties of the
fabrics were determined as shown in Table 7.
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TABLE 7
Sample No. 16 17
Comparative Sample C
(% by weight)
Glyoxal, 40% 6.0 6.0 6.0
Diethylene glycol 8.8 B.8 8.8
Aluminum 6ulfate octadecahydrate 0.125 0.125 0.125
Tartaric acid hydrate 0.075 0.075 0.075
Copolymer IX 2.0
Copolymer VII 2.0
Water 83.0 83.0 85.0
Cond. WRA (f+w degrees)
initial 301 300 272
after 3 wa6he~ 295 285 230
tear 6trength 49% 44~ 31%
retention (w)
Wetting time (6econd6)
initial 9 6 6
after 3 wa6heR 30 10 3
Durable pre66 3.3 3.4 3.1
rating (average)
Softne6c 2.5 2.5 6
Copolymer6 VII and IX are a6 in Example 4 and Example 5
respectively.
The data demonstrate that the glyo~al,
glycol, hydrophilic silicone, catalyst process
results in improved tear strength, wrinkle recovery,
durable press rating and softness compared to the
glyoxal-glycol system without the silicone.
D-16388-1
- 23 - 2048890
The above examples are intended to be
exemplary of the preferred embodiments of.the
invention. It will be readily recognized by those
skilled in the art that other modifications and
embodiments can be made without departing from the
spirit and scope of the invention as set forth in the
following claims.
D-16388-1
