Note: Descriptions are shown in the official language in which they were submitted.
9~06
WATER R~PELLENT COMPOSITION
The present invention relates to a water repellent
composition, and more particularly to a composition which
is capable of imparting water repellency mainly to
organic or inorganic fibers, coating compositions or
shaped products of inorganic hydraulic materials such as
gypsum, gypsum slagr calcium silicate, concrete and
autoclaved lightweight concrete.
Compounds such as paraffins, metal salts of fatty
acids, asphalts and silicones, have been used as agents
for imparting water repellency to such materials.
However, parafEins do not provide ade~uate water
repellency for applications whexe high temperature
treatment is involved. On the other hand, metal salts of
fatty acids and asphalts have difficulties that they tend
to decrease the strength of the shaped products and the
shaped products are likely to be thereby colored.
SiIicone compounds are satisfactory in such respects, but
they have a problem that they are expensive.
The present inventors have conducted extensive
researches to obtain an inexpensive water repellent agent
while maintaining the desirable features of the silicone
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compounds, and have surprisingly found that by using a
silicone oil in combination with a compound having a
certain specific separation index relative to the
silicone oil, the above-mentioned problems can be solved
without reducing the water repellency even when the
amount of the silicone oil is reduced to a level of 70%
or less of the conventional silicone oil-type water
repellents (silicone oil: 100%). The present invention
has been accomplished on the basis of this discovery.
The present invention provides a water repellent
composition being liquid at room temperature, which
comprises a silicone oil and a substantially non-volatile
paraffinic oil or low molecular weight hydrocarbon resin,
wherein the separation index of the paraffinic oil or low
molecular weight hydrocarbon resin to the silicone oil is
at most 0.4.
Now, the present invention will be described in
detail with reference to the preferred embodiments.
As the silicone oil constituting the water repellent
composition of the present invention, various
conventional materials may be employed. However, linear
polymers which usually have a viscosity of from 0.5 to
10l centistokes, preferably from 102 to 108 centistokes,
at 25C and which is liquid at a temperature of from 0 to
40C, such as polydimethylsiloxane and its modified
product, may suitably be employed. As specific examples,
there may be mentioned SH-200 (tradename, dimethylpoly-
siloxane, manufactured by Toray Silicone Co., Ltdo)~
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36
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KF-54 (tradename, methylphenylpolysiloxane manufactured
by Shinetsu Chemical Industries Co., Ltd.), KF-9g
(tradename, methylhydrodienepolysiloxane, manufactured by
Shinetsu Chemical Industries Co., Ltd.), SF-8418
(tradename, methylcarboxypolysiloxane, manufactured by
Toray Silicone Co., Ltd.), a modified
dimethylpolysiloxane having OH groups at both terminals,
and aminomethyl polysiloxane.
As the substantially non-volatile paraffinic oil to
be used in the present invention, a fraction separated
from a petroleum and refined, and composed essentially of
paraffinic compounds, a lubricant oil such as a turbine
oil or a machine oil containing such a fraction or a
liquid paraffin, which is liquid at a temperature of from
0 to 40C, may be mentioned. As the substantially
non--volatile low molecular weight hydrocarbon resin, a
polybutene, a polybutadiene, an epoxidized polybutadiene,
a low molecular weight polymer of an ~-olefin having from
16 to 18 carbon atoms, a petroleum resin,or a
coumarone-indene resin, which usually has a molecular
weight of up to 5000 and which is liquid at a temperature
of from 0 to 40C, may be mentioned. Here,
"substantially non-volatile" means that when the water
repellent composition of the present invention is applied
to an object, the paraffinic oil or low molecular weight
hydrocarbon resin in the composition will remain without
evaporation for a long period of time.
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In the present invention, the paraffinic oil and low
molecular hydrocarbon resin are required to have a
separation index of at most 0.4 to the silicone oil. If
the separation index of the paraffinic oil and low
molecular hydrocarbon resin exceeds 0.4, the water
repellency will be inadequate. In such a case, a
compatibilizing agent, which improves compatibility of
oils to the silicone oil, is added to bring the
separation index to a level of at most 0.4. Specific
examples of such a compatibilizing agent include a
surfactant having a HLB of from 0 to 6 such as a sorbitan
dialkylester, a sorbitan trialkylester, an
alkylphenol-polyethylene glycol condensation product, a
fatty acid-polyethylene glycol condensation product, an
aliphatic alcohol-polyethylene glycol condensation
product, an aliphatic amide-polyethylene glycol
condensation product or a polypropylene
glycol-polyethylene glycol condensation product; a
perfluoroalcohol-polypropylene glycol-isocyanate
condensation product; a monohydric alcohol ester of a
fatty acid; a polyhydric alcohol monoester of a fatty
acid; a polyhydric alcohol diester of a fatty acid; a
copolymer of an ~-olefin having from 6 to 52 carbon atoms
with a maleic acid monoester or maleic acid diester; or a
modified ethylene-vinyl acetate copolymer, which improves
the compatibility of the silicone oil with the paraffinic
oil or low molecular weight hydrocarbon resin~ Among
these, the copolymer of an ~-olefin having from 6 to 52
~ ~ ~9 ~ 3
carbon atoms with a maleic acid monoester or maleic acid
diester is preferred. The control of the separation
index of the paraffinic oil and low molecular weight
hydrocarbon resin can conveniently be conducted by adding
the above-mentioned compatibilizing agent to the mixture
comprising a silicone oil and the paraffinic oil and/or
low molecular weight hydrocarbon resin. In such a case,
the amount of the compatibilizing agent is suitably
selected within a range of from 0.1 to 50% by weight
relative to the above-mentioned mixture.
In the present invention, the separation index is a
value obtained by introducing 25 g of a liquid obtained
by mixing the silicone oil and the above-mentioned
variable liquid compound in the weight ratio of 3 : 2 or
such a liquid with an addition of a compatibilizing agent
in the above-mentioned range, into a 50 ml beaker, and
stirring it with a Teflon stirring element (length:
20 mm, diameter: 6 - 8 mm) by a magnetic stirrer at 1200
rpm for 5 minutes, then transferring the liquid mixture
to a test tube having a diameter of about 17 mm, and
leaving it to stand still at a temperature of from 15 to
30C for 60 minutes, whereupon the height of the
transparent layer formed is divided by the total height
of the liquid to obtain a value as the separation index.
Accordingly, in the case where a water repellent
composition contains a compatibilizing agent, its
separation index is obtained by conducting the above-
mentioned measurement by using as a test sample a
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composition obtained by adding to a composition
comprising the silicone oil and the paraffinic oil or low
molecular weight hydrocarbon resin in the weight ratio of
3 : 2, a compatibilizing agent in an amount to bring its
ratio relative to the paraffinic oil or low molecular
weight hydrocarbon resin to the above-mentioned ratio of
the compatibilizing agent to the paraffinic oil or low
molecular weight hydrocarbon resin in the water repellent
composition.
In the water repellent composition of the present
invention, the mixing ratio of the silicone oil and the
paraffinic oil or low molecular weight hydrocarbon resin
is preferably within a range of from 70 : 30 to 10 : 90
by weight ratio. Particularly preferred is a range of
from 60 : 40 to 20 : 80. If the silicone oil is less
than the above ratio, the water repellency will be
inadequate, and if it exceeds the above ratio, the cost
of the water repellent composition tends to be expensive,
such being undesirable.
In the present invention, the above-mentioned
silicone oil and the paraffinic oil or low molecuar
weight hydrocarbon resin, if necessary, together with a
compatibilizing agent, are dispersed and mixed in
accordance with a conventional method by e.g. a turbine
vane stirrer or a homomixer, or dissolved in an organic
solvent such as toluene or benzene, to obtain a water
repellent composition.
Further, the above-mentioned water repellent
composition may be used in the form of an emulsion by
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emulsifying it with an addition of water and, if
necessary, together with a surfactant. To obtain an
emulsion, the silicone oil, the paraffinic oil or low
molecular weight hydrocarbon resin and water may
simultanesouly be mixed without preliminarily preparing
the above-mentioned water repellent composition. If a
compatibilizing agent is employed in such a case, it is
advantageous from the viewpont of the formation of an
emulsion that the compatibilizing agent is preliminarily
incorporated to the silicone oil or to the paraffinic oil
or low molecular weight hydrocarbon resin.
As the surfactant to be employed for the preparation
of the emulsion, there may be mentioned, in addition to
the nonionic surfactants mentioned above, those which are
commonly employed as emulsifying agents. The nonionic
surfactants to be used for the emulsion may have a HLB of
at least 6. However, those having a high emulsifying
action are preferred.
Specifically, there may be mentioned nonionic
surfactants such as an ethylene glycol condensation
product of a sorbitan alkyl ester, a fatty
acid-polyethylene glycol condensation product, an
aliphatic amide-polyethylene glycol condensation product,
an aliphatic amine-polyethylene glycol condensation
product, an aliphatic alcohol-polyethylene glycol
condensation product, an alkylphenol-polyethylene glycol
condensation product, and a polypropylene glycol-
polyethylene glycol condensation product; anionic
surfactants such as a sodium alkylsulfonate and sodium
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dialkylsulfosuccinate; and cationic surfactants such as
an alkyl amine salt and a polyoxyethylene alkyl amine
salt. Further, paraffin oxide, ester wax or a salt
thereof may also be employed. These surfactants may be
used preferably in the minimum amount required for
emulsifying the mixture comprising the silicone oil and
the paraffinic oil or low molecular weight hydrocarbon
resin to water~ Usually, it is added in an amount of
from 2 to 30% by weight, preferably from 2 to 20% by
weight, relative to the water repellent composition. For
the emulsification of the above composition, conventional
methods such as a homomixer, a colloid mill, a valve
homogenizer and the ultrasonic waves, may be employed.
Further, for the purpose of increasing the viscosity
of this emulsion or improving the stability, water-
soluble polymer compounds, for example, synthetic
polymers such as a polyvinyl alcohol, a polyethylene
imine, a polyacrylic acid, a styrene-maleic anhydride
copolymer or their salts; cellulose derivatives such as
methyl cellulose, carboxymethyl cellulose or
hydroxymethyl cellulose, may be added. Such a water-
soluble polymer compound is used usually in an amount of
from 0.01 to 10~ by weight, preferably from 0.01 to 6% by
weight. If the amount of the addition is less than 0.01
weight %, no adequate improvement in the stability can be
expected. On the other hand, if the amount exceeds 10~
by weight, an adverse effect to the water repellency may
be brought about, such being undesirable.
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Conventional methods may be employed for the
application of the water repellent composition of the
present invention to organic or inorganic fibers, coating
compositions or inorganic hydraulic materials. For
instance, there may be mentioned a method for
incorporation wherein the water repellent composition is
added and dispersed in a slurry of inorganic hydraulic
materials, a method wherein the water repellent
composition is coated or sprayed on to the surface of
fibers or shaped articles, or a method in which fibers or
shaped articles are dipped in the water repellent
composition. Further, various additives may also be
incorporated during the above-mentioned processing or
treatment without any particular restriction.
As discussed .in detail in the foregoing, the water
repellent composition of the present invention comprises
a silicone oil and a paraffinic oil or low molecular
weight hydrocarbon resin having a certain specific
separation index to the silicone oil, whereby the amount
of the silicone oil can be substantially reduced as
compared with conventional silicone oil-type water
repellents, and yet the composition has high water
repellency substantially equal to the conventional
products and yet is inexpensive as compared with the
conventional products. Further, while the conventional
silicone oil-type water repellents may not impart
ade~uate water repellency in the case where the substrate
is cotton or paper, the water repellent composition of
the present invention is capable of imparting water
06
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repellency without being restricted to the type of the
substrate.
Further, the water repellent composition of the
present invention has excellent alkali resistance. For
instance, when applied to a substrate like concrete which
becomes alkaline in the presence of water, the water
repellent composition of the present invention does not
undergo a deterioration in the water repellency which
used to be the case where a conventional water repellent
of silicone alone was used, and it is also possible to
maintain the water repellency for a long period of time.
When a conventional water repellent of silicone alone
is applied to a substrate coated with an oil-type coating
compositlon, the water repellent tends to be repelled,
while the water repellent composition of the present
invention has a lipophilic nature, and can be applied to
such a substrate without being repelled.
Furthermore, the water repellent composition of the
present ivnention has autoclave resistance and is capable
of imparting excellent water repellency to a substrate to
be subjected to autoclave treatment such as a calcium
silicate shaped product or an autoclaved lightweight
concrete, while it is capable of imparting excellent
water repellency to a substrate even when it is dried at
room temperature in contrast with the conventional
paraffin-type water repellents.
Now, the present invention will be described in
further detail with reference to Examples, Comparative
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Examples and Test Bxamples. However, it should be
understood that the present invention is by no means
restricted by these specific Examples.
In the following description, "parts" and "%" mean
"parts by weight" and "% by weight", respectively.
Further, the silicone oil used in the Examples and
Comparative Examples, was SH-200 (manufactured by Toray
Silicone Co., Ltd., viscosity: 500 cst/25 C).
EXAMPLE 1
To a mixture comprising 60 parts of a turbine oil
having a separation index of 0.44 (Diamond Turbine Oil
#68, manufactured by Mitsubishi Petroleum Co., Ltd.) and
40 parts of the silicone oil, 2 parts of sorbitan
dioleate having a HLB of 2.1 was added, and the mixture
was thoroughly mixed and dispersed by a homomixer to
obtain an oily composition ~a).
The separation index of the turbine oil was adjusted
to 0.31 by the addition of the sorbitan dioleate.
COMPARATIVE EXAMPLE 1
In Example 1, the turbine oil and the silicone oil,
without an addition of the sorbitan dioleate, were mixed
and dispersed by the homomixer to obtain an oily
composition (b). The separation index of the turbine oil
was 0.44.
EXAMPLE 2
102 parts of the composition (a) obtained in Example
1 and 100 parts of deionized water were emulsified by a
~2~j9~
homomixer to obtain an emulsion (c) having a solid
content of 50.3%.
E~A~PLE 3
231 parts (1 mol) of ~-olefins having from 16 to 18
( ~ 7Lra Je 1" Q ~
carbon atoms (Dialen 168,/ manufactured by Mitsubishi
Chemical Industries Limited) and 189 parts (1.1 mol) of
diethyl maleate were charged into a 1 liter four necked
flask, and heated to 160C under a nitrogen atmosphere.
Then, to this mixture, 9.66 parts (0.066 mol) of
di-tert-butylperoxide was added in portions of 1/8 in an
interval of 20 minutes under stirring. After the
addition, the reaction was conducted for further 1 hour
at the same temperature.
After the completion of the reaction, light boiling
components and unreacted monomers contained in the
reaction mixture were distilled off under a reduced
pressure of from 1 to 3 mmH~ to obtain an ~-olefin
(C16-C18)-diethyl maleate copolymer ~hereinafter referred
to as PAR 168 Et).
4 parts of PAR 168 Et thus obtained and 40 parts of a
turbine oil (Diamond Turbine Oil #68) and 60 parts of the
silicone oil were mixed and dispersed by a homomixer to
obtain an oily composition.
The separation index of the turbine oil was adjusted
to 0.11 by the addition of PAR 168 ~t. To this mixture,
2 parts of a propylene oxide-ethylene oxide copolymer
(HLB: 11.6) as an emulsifier and 109 parts of deionized
water were added, and the mixture was emulsified by a
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homomixer to obtain an emulsion (d) having a solid
content of 49.3~.
EXAMPLE 4
40 parts of a polybutene having a separation index of
0.00 and 60 parts of the silicone oil were mixed and
dispersed by a homomixer to obtain an oily composition.
To this composition, 2 parts of an emulsifier (Pluronic
tr ~L ~ G rn C~, r 1~
L-64, ~r~ ~, an ethylene oxide-propylene oxide
copolymer, HLB: 10.1, manufactured by Asahi Denka Kogyo
K.K.) and 100 parts of deionized water were added, and
emulsified by a homomixer to obtain an emulsion (e)
having a solid content of 50.2~.
EXAMPLE 5
To a mixture of 51 parts of a coumarone-indene resin
having a separation index of 0.40 and 34 parts of
silicone oil, 0.5 part of a polyalkylene glycol-
isocyanate condensation product containing perfluoroalkyl
t~C 1P~
groups (Megafac F 184, t~e~, manfuactured by
Dainippon Ink & Chemicals Inc.) was added to obtain a
mixture (so that the separation index was adjusted to
0.10). To this mixture, 16 parts of a
dimethylethanolamine salt of oxidiæed paraffin (mp: 70 C,
acid value: 43) and 2 parts of an alipha-tic
f f c. lt . ~ ~, r ~
amide-ethylene oxide adduct (Esomide HT 50, tr~cn~c,
Lion Aczo Co., Ltd.) were dissolved at 80C~ and then 200
parts of deionized water of 80C was added, and the
mixture was emulsified by a homomixer to obtain an
emulsion (f) having a solid content of 30.2%~
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COMPARATIVE EXAMPLE 2
40 parts of a turbine oil having a separation index
of 0.44 (Diamond Turbine Oil #68) and 60 parts of the
silicone oil were mixed and dispersed by a homomixer, and
t~ . ~ ~ r k~
then 2 parts of an emulsifier (Pluronic L 44, ~*~f~K~,
an ethylene oxide-propylene oxide copolymer, manufactured
by Asahi Denka Kogyo K.K.) and 100 parts of deionized
water were added to obtain an emulsion (g) having a solid
content of 50.4%.
COMPARATIVE EXAMPLE 3
100 parts of the silicone oil, 2 parts of a propylene
oxide-ethylene oxide copolymer (HLB: 6.3) as an
emulsifier, and 100 parts of deionized water were
emulsiied by a homomixer to obtain an emulsion (h)
having a solid content of 50.2%.
Test Examples 1 to 5
A glass mat ~p= 0.025) was dipped in a liquid
obtained by diluting the emulsion (d), (e), (g) or (h)
with water to bring the solid content to 1~. After water
drainage for 1 hour, the mat was dried at 150C for 2
hours. To this, water was sprayed in accordance with JIS
L 1092 spray testl whereby the water absorption was
measured. The results are shown in Table 1. For the
purpose of comparison, the results obtained in a system
where no water repellent was added, are also shown.
From Table 1, it is evident that the water repellent
compositions having a separation index of less than 0.4
show water repellency substantially equal to the silicone
oil.
Test Examples 6 to 10
6.7 g of cotton broadcloth was dipped in a bath
containing 5% as the solid content of the emulsion (d),
(e), (g) or (h), and treated by 1 dip, 1 nip with a
squeezing rate of 76%. Then, the cloth was pre-dried at
aoc for 3 minutes, and then cured at 130C for 5 minutes
by using a pin tenter. Further, the cloth was heated in
a dryer of 150C for 2 hours. The water repellency of
this cloth was measured in accordance with JIS L-1004,
and the water absorption after the evaluation of the
water repellency was measured. The results are shown in
Table 2. For the purpose of comparison, the results in
the case where no water repellent was added, are also
given.
Test Examples 11 to 13
A non-sized paper having a weight of 123 g/m2 was
dipped for 1 minute in a bath containing 1% as a solid
content of the emulsion (d), (g) or (h), and squeezed by
rollers, and after measuring the pick-up amount, pressed
at 120C for from 2 to 3 minutes, and further heated in a
dryer of 170C for 2 hours. Then, it was pretreated in
accordance with 3IS P-8111, and then the water resistance
(stockigt sizing degree) was measured in accordance with
JIS P-8122. Ihe results are shown in Table 3.
Test Examples 14 to 16
To a commercially available vinyl acetate-type
emulsion coating composition tmanufactured by Kansai
Paint Co., Ltd., solid content 57%), the emulsion (d),
(g) or (h) was added in an amount of 5% as a non-volatile
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component. The coating composition was coated on the
surface of a gypsum board in an amount of about 300 g/m2.
The coated board was dried at 60C for 1 hour. Then, 1
ml of deionized water was dropped thereon, and a watch
glass was placed thereon, whereupon the time until the
water drop disappeared completely was measured to
determine the water resistance. The results are shown in
Table 4.
Test Examples 17 to 24
To a slurry comprising 160 parts of Porland cement,
143 parts of silica powder, 0.2 part of metal aluminum
and 200 parts of water, the water repellent composition
as identified in Table 5 was mixed to bring the non-
volatile content to 2 parts, and the mixture was poured
into a mold frame. The mixture was foamed and cured.
The molded product was taken out rom the mold frame and
cured with steam in an autoclave at 180C under 10
kg/cm G for 5.5 hours, and dried at 105C for further 10
hours to obtain an autoclaved lightweight concrete. The
concrete was placed in water of 20C at a position 30 mm
below the water surface, and left to stand for 2~ hours,
whereupon the water absorbance was determined based on
the weight change. The results are shown in Table 5.
Test Examples 25 to 28
The emulsion (c), (g) or (h) was coated on the
surface of a commercially available concrete block in an
amount of 100 g/m2, and dried for 3 days at room
temperatureO After drying, 1 ml of water was droped, and
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a watch dish was put thereover to prevent the
evaporation, whereby the time until the water drop
disappeared completely was measured to determine the
water resistance. With respect to the case where no
water repellent was applied, the water resistance was
measured in the same manner, and the results are also
shown in Table 6.
Table 1
Test Water Separation ~mount Water
Example repellent index added Absorbance
composition __ (%) (%)
1 d (60~) 0.11 2.2 22.2
2 e (60%) 0.00 2.4 24.7
3 g (60%) 0.44 2.2 40.0
4 h (100%) _ 2.1 21.2
Nil _ _ 49.5
Note 1. The (%) in the column for the water repellent
composition indicates the silicon content in the
active ingredient.
Note 2. The amount added means 100 times the value obtained
by dividing the weight of the non-volatile content
in the water repellent composition remaining on the
substrate by the weight of the substrate.
The same applies to the following Tables.
18 -
Table 2
Test Water Separa- Amount Water Water
Example repellent tion added repellency absorb-
composition index t~.) _ ance (%)
6 d (60%)0.11 3.8 70 20.2
7 e t60%)0.00 3.8 70 23.3
8 g (60~.) 0.443.8 50 31.3
9 h (100%) _3.8 50 49.0
Nil _ _ 69.4
Table 3
Test WaterSeparation Amount Water
F.xample repellent index added (%) repellency
composition (Stoc~gt/sec.)
11 d t60%)0.11 16.0 161
12 g t60%)0.44 17.4 8
13 h (100%) 15.2 0
Table 4
-
Test WaterSeparation Amount Water
Example repellent index added (%) resistance
com~osition (min)
14 d (60~)0.11 5.0 40
g (60%)0.44 5.0 11
16 h (100~) 5.0 17
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Table 5
Test Water Separation Amount Water
Example repellent index added (%) absorbance
composition (%)
17 a (40%) 0.31 2.0 26.1
18 c (40%) 0.31 2.0 17.0
19 d (60%) 0.11 2.0 17.2
e (60%) 0.00 2.0 18.0
21 f (34%) 0.10 2.0 19.2
22 b (40%) 0.44 2.0 38.2
23 g (60%) 0.44 2.0 54.3
24 h (100%) 2.0 18.5
Table 6
Test Water Separation Water
Example repellentindex resistance
composition . (min)
c (40%) 0.31 1440 ore more
26 g ~60%) 0.44 32
27 h (100%) _ 30
28 Nil
