Note: Descriptions are shown in the official language in which they were submitted.
1177997
The present invention relates to silicone
compositions for the treatment of fibers. More precisely, it
concerns polysiloxane compositions which can impart water
repellency an~ oil repellency to fiber materials.
Conventionally, water repellency is imparted to ,iber
materials using methylhydrogenpolysiloxane or
dimethylpolysiloxane directly, or as an emulsion or solution
in an organic solvent, a catalyst for curing and with
subsequent heat treatment. In this case, the treated fiber
materials actually demonstrate an effective water repellency,
but their oil repellency is poor.
Therefore, a specific fiber treatment agent priMarily
consisting of fluorinated hydrocarbons i5 generally used in
order to impart oil repellency to the fiber materials. In
this case, this treatment agent is very expensive and the
treatment process is very difficult because of a limitation of
solvents for dilution. In addition, the drawbac~ cannot be
avoided tnat an undesirable feel is given to the treated fiber
materials and in particular to fabrics for clothing.
In Kokai Japanese Patent No. Sho 50(1975)-140388, i.
was proposed that a partially hydrolyzed condensation product
of diorganopolysiloxanes having perfluoroalkyl-alkoxysiloxane
and alkyl-alkoxysiloxane units and having OH groups at both
ends can be used for dirt protection on inorganic materials
such as slate slabs and tiles. However, it is actually very
difficult for such a resin-like coating agent to penetrate
into the interior of fiber materials. In terms of chemical
composition, such an agent is completely different from the
compositions of this invention.
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In Japanese Patent No. Sho 47~1972)-38$05, it was
proposed that a filter cloth having excellent durability with
respert to twistiny and excellent lubrication properties can
be obtained by treating an inorganic fiber cloth with an
organopolysiloxane containins trifluoromethyl-substltuted
aromatic groups. In this case, the obtained cloth lacks
washing resistance and hot water washing resistance because of
the noncuring nat~re of the treatment agent.
In Japanese Patent No. Sho 42(1967)-2637, a method
lD for imparting water repellency to the fibrous organic
materials was proposed by the treatment of the fibrous
materials with vapor of silanes containing perfluoroalkyl
groups. According to this method, the control of the
treatment process is very difficult and there is the drawback
that retention and durability of the treatment effects are
poor.
It is an object of this invention to provide
compositions which durably impart both oil repellency and
water repellency to fiber materials. This object, and others
which will be obvious upon considering the following
disclosure and appended claims, are obtained by the present
invention wherein a curable organopolysiloxane composition
comprising a linear organopolysiloxane comprising
silicon-atom-bound fluorinated hydrocarbon radicals,
silicon-atom-bound un~ubstituted hydrocarbon radicals and
silicon-atom-bound hydrogen atoms is mixed with a
dehydrogenation condensation catalyst and the resulting
composition of this invention is applied to a fiber material.
1177997
The present invention relates to a composition for
the treatment of Eibers, said composition being obtained bv
mixing components comprisiny (A) a siloxane component
comprising (a) a substantially linear
organohydrogenpolysiloxane which has at least 5 mol percent of
RQsio2/2 units and at least three silicon-atom-bound hydrogen
atan per molecule, wherein R denotes an unsubstituted
monovalent hydrocarbon radical haviny from 1 to 6 carbon atoms
and Q denotes a fluorinated monovalent hydrocarbon radical or
1~ (b) a mixture comprising (b)(l) a substantially linear
organopolysiloxane which consists of from 5 to 1~0 mol percent
of RUsio2/2 units and from 0 to 35 mol percent of R'R"SiO2/2
units and which has a silicon-atom-bound hydroxyl radical at
each terminus, wherein R and Q are as denoted above and R' and
R" denote unsubstituted monovalent hydrocarbon radicals and
(b)(2) an organohydrogenpolysiloxane which has at least three
silicon-atom-bound hydrogen atoms per molecule wherein the
organic radicals are unsubstituted monovalent hydrocarbon
radicals and (B) a curing catalyst component for
dehydrogenation condensation between silicon-atom-bound
hydro~en atoms or between silicon-atom-bound hydro~en atoms
and silicon-atom-bound hydroxyl radicals.
The compositions of this invention form a cured film
having both oil repellency and water repellency on fibers by
the formation of cross-links by dehydrogenation due to the
catalytic action of component (B) with component (A).
Component (A) can be component (a) alone or a mixture of
component (b)(l) and component (b)(2).
Component (a) is a component which imparts both oil
repellency and water repellency. This component ~a) contains
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at least three silicon-atom-bound hydrogen atoms per mol~cule.
The cross-l.nks are formed by dehydrogenation condensation due
to the catalytic ac~ion o~ component (~) and a cured film is
for.ned on the fiber surface. The silicon-atom-bound hydr3gen
atoms are present generally in the form of RHSiO2/2 units,
such as (CH3)(H)Sio2/2 units, in the molecular chain and/or in
the form Qf ER2SiO1~2 units, such as (~)(C~3)2Sil/2 units~ ~t
the molecular chain terminals.
In the molecular chain, diorganosiloxane units having
the formula R~R~Sio2/2r such as (CH3)2SiO2/2, can be present
in addition to RQSiO2/2 units and RHSiO2/2 units; however, a
satiq~actory oil repellency cannot be obtained unless at least
of 5 mol percent of RQSio2/2 units is present in the molecule.
Examples of R radicals in component (a) include alkyl
radicals, such as methyl, ethyl, and propyl; alkenyl radicals,
such as vinyl and allyl; and phenyl radicals.
Examples of Q radicals in component (a) include
CF3C~2C~2 - CF3CF2CH2C~2 ~ CF3CH2CH2CEI2 ~ CF3CF2CH2CH2CH
(CF3)2CHCH2- CF3(c6H4)cH2cH2/ CF3(C6H4) and
CF3CF2CF2(~H4)CH2cH2-
Examples of R' and R" radicals in component (a)
include alkyl radicals, such as methyl, ethyl and octyl;
alkenyl radicals such as vinyl and allyl; aryl radicals, such
as phenyl and tolyl; and arylalkyl radicals, such as benzyl
and beta-phenylethyl. R' and R" can denote the same or
different radicals.
In addition to HR2Siol/2 units component ~a) can De
endblocked with other units such as R3SiOl/2 units, such as
(CH3)3SiOl/2 units, (CH2=CH)(CH3)(C6Hs)SiOl/2 units and
(CH3)2(c6H5)siOl/2 units; and R2~Siol/2 units, such as
~7799~
(C~3C~2C~2!(CH3),Si~l/2 units and
(cF3c~2c~2)~CH3)(~2-cH)siol /2 units.
~ xamples of RQSiO2/2 units in the molecular chain of
Cm?~ent (~) include (CF3CH2CH2)~CH3)sio2/2 units,
(CF3c~2c~2)(c6H5~siO2/2 units, (~F3cH2cH2)(cH2=cH)sio2/2
units, (CF3~F2CH2CH2)(C~3)SiO2/2 units and
(~3C~H~CH3)Sio2/2 units.
Examples of R'R"SiO2/2 units in component (a) include
(C~3)2S102/2 units~ (CH3)~C6Hs)Sio2/2 units,
(CH3)(CH2=CH)SiO2~2 units, (C6Hs)2SiO2/2 units,
(C6H5)(C~2=C~)SiO2/2 units and (cH3)(~6H5cH2)sio2/2 units-
Component (a) can be prepared by any of the
well-known methcds for prepariny endblocked
polydiorganosiloxanes. For example, a suitable mixture of
hydrolyzable silanes, such as (CF3CH2CH2)(CH3)SiC12,
(C~3)(~)SiC12 and (CH3)3SiC1 can be cohydrolyzed and
equilibrated under the influence of silanol-condensing and
siloxane-equilibrating catalyst. Alternatively, a suitable
mixture of cyclosiloxanes and endblocked siloxanes, su~h as
~(CF3cH2c~2)(cH3)siO}3~ {(CH3)(H)SiO}4 and (CH3)3SiOSi(CH3)3
can be equilibrated under the influence of a
siloxane-e~uilibrating catalyst.
By the expression that component (a) is substantially
linear it is meant that it is completely linear, i.e.
consisting only of molecular chain silicon atoms linked by
only 2 oxygen atoms and terminating silicon atoms linked by
only one oxygen atom; or only slightly branched, i.e. further
comprisin~ only trace amounts of silicon atoms linked by three
or four oxygen atoms.
1177997
Component (a) is generally a liquid at room
temperature and preferably has a viscosity of from 20 to
100,000 centistokes at 25C.
Component ~a) is generally used alone; however, it
can be used as a mixture with a diorganopolysiloxane havlng
silicon-atom-bound hydroxyl radicals at each terminus, i.e. a
hydroxyl-endblocked pol~diorsanosiloxane. Examples of
hydroxyl-endbloc!~ed polydiorganosiloxane include component
(b)(l) delineated below and siloxar.es having the formula
HO(~'R~siO)XH w~erein x is a positive integer and R' and R"
are as delineated above.
Component (b), which can be used alternatively to
component (a), is a mixture comprisiny components (b)(l) and
(b)(2). Lik~ component (a) component (b)'l) confers both oll
repellency and water repellency to treated fibers. Component
~b)(2) is the crosslinking agent for component (b)(l), said
crosslinks being formed between silicon-atom-bound hydrogen
atoms and silicon-atom-bound hydroxyl radicals under the
influence of component (B) to form a cured film on the fiber
surface.
Component (b)(l) is a substantially linear
organpolysiloxane, where the expression substantially linear
is as defined above for component (a), and can range from a
freely flowing liquid to a slowly flowing gum at room
temperature.
As with component (a), component (b)(l) must have at
least 5 l~ol percent of RQSio2/2 units in its molecular chain
in order to provide a satisfactory oil repellency for a
treated fi~er. All siloxane units in component (b)~l) can be
RQSi2/2 units. Any siloxane units in component (b)(l) which
are not R~SiO2/2 units are R~R~'sio2/2 units. Examples of
1177997
R'R"SiO~/2 units and RUsio2/2 in component ~b)(l) are as noted
above for component (a).
Component ~b)(l~ can be prepared by any of the
weil-~nown methods for preparing hydroxyl-endblocked
polydiorganosiloxanes. Typically a hydrolyzable silane; such
as RQSiCl27 such as (CF3C~2CP~2)(C~3)~iC12, or a mixture of
hydrolyzable silanes; such as RQSiC12 and R'R"SiC12, such as
(CF3c~2cP-2)(~H3~sicl2 and ~CH3)2SiC12, is hydrolyzed in a
solvent ~nd the hvdrolyzate condensed in the presence of a
silanol-condensing catalyst.
Component ~b)(2) i9 a cross-linking agent for
component (b)(1). Examples of this component are
organohydrogenpolysiloxanes in which both terminals are capped
with organic groups, such as (CH3)3s~O{(cH3)(~)sio}xsi(cH3)3
diorganosiloxane/organohydrogensiloxane copolymers in which
both terminals are capped with organic groups, such as
(C~3)3SiO~(CH3)2SiO}X{(C~3)(H)SiO}ySi(CH3)3,
organohydrogenpolysiloxanes having silicon-atom-bound hydrogen
atoms at both terminals, such as (H)(C~3)2Sio-
{(CH3)(H)Si~}X{(CH3)2SiO}ySi(C~3)2H and organohydrogencyclic-
polysiloxanes, such as {(CH3)(H)SiO}X. Examples of the
organic groups in (b)(2) are generally methyl groups, phenyl
groups and vinyl yroups. This component is generally in a
liquid form at room temperature wherein x and ~ are positive
integers. Organohydrogenpolysiloxanes are well known in the
siiicone polymer art and need no furtner elaboration here as
to composition and/or to methods of preparation.
The amount of component (b)(2) is preferably an
arnount which is sufficient to give silicon-atom-bound hydrogen
atoms in a molar proportion greater than the molar proportion
of the silicon-atom-bound hydroxyl grou~s in component (b)(l).
il7~;g~7
~ oloponent (B) is an indispensable component for
cross-link formaticn among components (a) or among component
(b)(l) and component (b)~2). Examples of this component
include acid salts of heavy metals, such as tin, lead,
zirconium, zinc, iron and man~anese. In particular,
carboxylic acid salts, titanic acid esters and platinic acid
salts are preferred.
Examples of these acid salts include dibutyltin
diacetate, d-butyltin dilaurate, dioctyltin dilaurate,
dibutyltin dioctylate, tin octylate, tin dioctylate,
diisooctylic acid mercaptoacetate, zinc octylate, zirconium
naphthenate, manganese naphthenate, iron naphthenate,
tetrabutyl orthotitanate and chloroplatinates.
Component (~) is generally used in an amount of 0.1
to 20 parts by weight to 100 parts by weight of component (A).
An appropriate proportion can be selected according to the
types and amounts of functional groups in component ~A) and
he curing conditions. In particular, it can be appropriately
selected according to the temperature that is used to cure
~0 component (A).
The c~mpositions of this invention for the treatment
of fibers are easily produced simply by mixing component (a)
and com~onent (B), or by mixing component ~b) consisting of
components (b)(l) and (b)(2), and component ~B).
When fiber materials are treated with the
compositions of this invention, the treatment is preferably
carried out in a solution using an appropriate diluent such as
acetone, methyl ethyl ketone, methyl isopropyl ketone, diethyl
ketone, cyclohexanone, acetylacetone, tetrahydro~uran,
dioxane, ethyl acetate, propyl acetate, butyl acetate, amyl
acetate, methyl propionate, ethyl propionate,
~I77997
dimethylformamide, dimethylacetamide and methyl cellosolve
acetate. In some cases, other solvents whlch are commonly
used for or~anopolysiloxanes, such as toluene, xylene,
isopropyl alcohol and hexane, can be mixed with the
above-mentioned solvents in an appropriate amount.
In addition, water and an appropriate surfactant, for
example, selected from among higher alcohol sulfates,
alkylbenzenesulfonates, higher alcohol polyoxyalkylene
adducts, Aigher fatty acid polyoxyalkylene adducts,
alkylphenol polyoxyalkylene adducts and fatty acid ester
polyoxyalkylene adducts, can be added to the compositions of
this invention as a diluent and the obtained eMulsions applied
to the fi~er materials.
The compositions of this invention, or their dilute
solutions in an organic solvent or their emulsions are used
for the treatment of fiber materials following common methods
which are generally used as fiber treatment processes. For
example, processes such as immersion, roller-coating or
spraying are applicable. If desirable, the treatment is
carried out with heating. As a result, durable water
repellency and oil repellency can be imparted to the surface
of fiber materials or within the interior layer of fi~er
materials.
As additional effects, a mold-release property and
pliability can be imparted to the fiber materials. The fiber
materials specified in this invention may be natural fibers
such as wool, silk, cotton, flax, asbestos, regenerated fibers
such as rayon and acetate, synthetic fibers such as
polyesters, polyamides, polyvinyl alcohols, polyacrylics and
~779~
polyolefins, and other fibers, such as glass fibers. The
compositions of this invention are applicable to these fiber
materials in various forms such as fibers, ~ilaments, knitted
materi=ls, woven abrics, and nonwoven fabrics. Preferably,
it is most effective to carry out the treatment continuously
on sheet fo~ls such as knitted fabrics and nonwoven fabri~s.
In particular, in the case of nonwoven fabrics, other binders
such as styrene-butadiene rubber latex and nitrile rubber
latex can be also added.
The present invention will be further explained in
the following examples. "Parts" indicated in the examples
aenotes "parts by weight". Me in the structural formula of
organopolysiloxane indicates a methyl group.
Example 1
An organopolysiloxane expressed by the following
structural ~ormula
Me Me Me ~e
Me - SiOtSiO)s tsiot40 Si - ~le
Me H CX2 Me
fH2
CF3
having a viscosity of 3,500 cSt at 25C (2 parts) was
dissolved in methyl ethyl ketone (97.8 parts). Subsequently,
dibutyltin dilaurate (0.2 parts) was added and dissolved
uniformly in the solution to provide treatment solution A.
For a comparison, a dimethyl/methylhydro~enpolysiloxane having
the same degree of polymerization as that of ~he polysiloxane
of this invention shown in the above-mentioned structural
formula was dissolved in toluene and a catlayst was added to
provide a comparative treatment solution B.
1177997
Subsequently, a piece of Tetoron (polyethylene
terephthalate) taffeta (plain woven fabric; 50 denier; lO x 10
cm) which had been scoured for desizing was immersed in the
respectlve treat~er.t solutions. The immersed p~ece was dried
by squeeziny using a mangle roller to such a desree that the
amount of silicon adhered was 2 wt~.
Suosequently, cross-links were formed by the
cehydroyenatlon condensation reaction by heatiny at 150C for
6 minutes. m:~e ~reated cloth was stretched at an angle of 45
and A9TM No. 2 oil and water were dropped on the cloth.
The cloth treated with the composition of this
invention demonstrated excellent water repellency and oil
repellency as shown in Table I.
Table I
Cloth treated Cloth treated
with with
treatment treatment
solution A solution B
Fiuid (this invention~(compar~tive Example)
Drops of ASTMhigh water instantaneous
No. 2 oilrepellency absorption of oil
no stains many stains
~rops of water high water high water
repellency repellency
2xample 2
An organopolysiloxane having the following structural
formula:
CH3 l CH=CH2 CH3 i
HO - SiO- _ _ -SiO _ _ - SiO - - H
CH3 x CH3 Y CH2CH2CF3 j z
where x:y:z (molar ratio) was 10:3:87, and which had a
viscosity of 3,000,000 cSt (lO0 parts), and a
methylhydrogenpolysiloxane of which both terminals were capped
*Trademark ll
117~ 7
with trimethylsilyl groups and which had a viscosity of 30 cSt
~5 parts) were dissolved in methyl isobutyl ketone
~300 parts~ by stirring. Subsequently, dibutyltin diacetate
(3 parts) was added to provide treatment soiution C. Two
pieces of asbestos plate with a length of 100 mm, a width of
50 mm and a thickness of 3 mm were immersed in this treatment
solution C for one minute. The pieces were lifted out of the
treatmenr solution C and the solvent was evaporated.
Subsequently the pieces were placed in a hot air dryer at
150C for curing for 10 minutes. As a resu}t, a firm glossy
protective film was formed on the surface of the asbestos
plate. A commercial adhesive tape for wrapping was stretched
over the treated plate and a load of 20 g/cm2 was applied to
the tape. After leaving the sample at room temperature for 20
hours, the tape had not adhered on the surface of the plate at
~11 .
The othar piece of the treated plate was immersed in
ASTM No. 1 oil for 5 weeks. Thereafter, the piece was cut and
the cut surface was examined for blackeniny due to the
permeation of oil. No evidence of permeation of oil was
found.
Example 3
A piece of Tetoron taffeta as in Example 1 was
treated with treatment solution C under the same conditions as
in Example 1. The resulting oil repellency and water
repellency were as excellent as those shown in Table I.
Example 4
A glass fiber fabric was treated with trea~ment
solution A under the same conditions as in Example '. The
resulting oil repellency and water repellency were excellent.
