Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
5 ~1 35
The present invention relates to noncurable sealing
materials.
Sealing materials can be roughly divided into
noncurable sealing materials and curable sealing materials.
Both types of materials are used for filling joints for the
purpose of water-tigh~ness and air-tightness, and are widely
utilized in construction and engineering work, vehicles,
automobiles and airpl-anes. Especially in the case of
construction work, these sealing materials are widely usPd at
joints between various parts, to seal windows to window
frames and to fill joints and gaps produced by the occurrence
of cracks.
Noncurable glazier's putty and oily caulking
materials are known as noncurable sealing materials. The
former consists primarily of oils and fats and the latter
also consists primarily of oils and fats, polybutene and
alkyd resins. Thus, they have poor weather resistance.
There is the drawback that the life of these noncurable
sealing materials is short when they are used outdoors.
There is also the drawback that they cannot be used at
locations having high temperatures because of their poor heat
resistance. In addition, such materials which comprise
silicone oil sealing materials and sealing ~aterials
consisting primarily of nonreactive silicone oil and a filler
have the drawback that separation of oil phase occurs easily.
If a highly viscous silicone oil is used for decreasing the
oil phase separation, the viscosity of the sealing material
is increased and there is the drawback that workability
during the sealing process decreases.
~1*~
The present invention provides a new material
without the drawbacks of the above-mentioned known common
noncurable sealing materials.
This invention relates to a noncurable sealing
material comprising a composition which increases in
viscosity on contact with moisture, does not cure and
substantially maintains its initial viscosity when stored in
a container which does not subs~antially allow moisture to
penetrate, consisting essentially of a product obtained by
mi~ing the following ingredients under substantially
anhydrous conditions:
ta) 100 parts by weight of a polydiorganosiloxane having
silicon-atom-bonded hydroxyl groups a~ the terminus of
the molecule chains, the organic groups of the poly-
diorganosiloxane being substituted or unsubstituted
monovalent hydrocarbon radicals and said polydiorgano-
siloxane having a viscosity of 0.5 m2/s or less at
25C,
~b) from 1 to 500 parts by weight of a filler, and
(c) an amount of an organosilicon compound sufficient to
supply silicon-bonded nitrogen groups or groups having
silicon-oxygen nitrogen bonds in at least the same
molar amount as the total molar amount of silicon-atom-
bonded hydroxyl groups in (a), said organosilicon
compound having two moisture hydrolyzable groups per
molecule and said groups being selected from the group
consisting of silicon-bonded nitrogen groups and groups
having silicon-oxygen-nitrogen bonds.
The components of this invention will be explained
t~ .
individually below. Component (a) is a polydiorganosiloxane
of the following general formula having silicon atom-bound
hydroxyl groups at the terminus of the molecular chain:
R
H0- _ Si - 0 - H
R m
where R represents substituted or unsubstituted monovalent
hydrocarbon radicals selected from among methyl, ethyl,
propyl, octyl, phenyl, vinyl and 3,3,3 trifluoropropyl
groups, and m is a number such that ~he viscosity at 25C is
0.5 m2/s or less. If the viscosity at 25C exceeds 0 5 m~/s,
the workability when the composition is prepared by adding a
filler, component (b) and a chain extension agent, component
(c), and the workability and process when the composition is
discharged from containers such as cartridges, tubes and
plastic film containers, becomes very poor. In addition, if
the viscosity is too low, the composition leaks out of the
sealed container and the increase in viscosity is inadequate
after filling a gap or cavity. The viscosity preferably
ranges from 0.00005 to 0.05 m2/s.
The silicon-atom-bonded hydroxyl group at the
terminus of the molecular chain is a functional group which
is required for the cond~nsation of component (a) with
component (c) in the presence of moisture for obtaining
higher molecular weight and higher viscosity.
Component (a) can be a polymer of a single viscosity
or a mixture of two or more viscosities.
Component (b) of this invention is a filler which is
used to modify the viscosity of component (a). For example,
the following fillers can be used: dry-process silica (fumed
silica), wet-process silica (precipitated silica),
diatomaceous earth, fine quartz powder, talc, mica powder,
calcium carbonate, magnesium carbonate, carbon black,
asbestos powder and glass powder.
The amount of component (b) ranges from 1 to 500
parts by weight per 100 parts by weight of component (a).
However, it is arbitrarily selected within the
above-mentioned range according to the types of fillers used
and in particular, the specific gravity and thickening
ability, and according to the viscosity of organopoly-
siloxane. In the case of the fillers having a highthickening ability, i.e., dry-process silica, wet-process
silica, carbon black, asbestos powder, nonsurface-treated
light and fine calcium carbonate, the amount used is
relatively small, while in the case of the fillers having a
relatively low thickening ability, i.e., diatomaceous earth,
fine quartz powder, mica powder, surface-treated precipitated
calcium carbonate and heavy calcium carbonate, the amount
used is perferably higher.
Component (b) can be a single filler or a mixture of
two or more fillers.
Component (c) i5 a component which helps increase
molecular weight and viscosity by lengthening the polydi-
organosiloxane chain, component (a), when the sealing
material of this invention is discharged into air from a
sealed container. That is, component (c) is a bifunctional
diorganosilane or bifunctional diorganosiloxane which is
hydrolyzable with water. These compounds are generally
expressed by the general formula:
RlR2S iX2
where Rl and R2 are each an unsubstituted or substituted
monovalent hydrocarbon radical and X is a hydrolyzable group
selected from the group consisting of silicon-bonded nitrogen
groups and groups having silicon-oxygen-nitrogen bonds, or
the general formula:
,Rl R Rl
R2 --S iO ---S i--X
where R, Rl, R2 and X are defined above, and n has a value in
the range of from ~ to 30 inclusive. In addition, the
above-mentioned diorganosiloxane can contain a cyclic group.
In these formulas, R, R1 and R2 represent alkyl groups such
as methyl, ethyl, and propyl, alkenyl groups such as vinyl,
allyl and butadienyl, aryl groups such as phenyl, xylenyl and
naphthyl, cycloalkyl groups such as cyclohexyl, cycloalkenyl
groups such as cyclohexenyl, aralkyl groups such as benzyl,
alkaryl groups such as tolyl and xylyl, and their substituted
groups. R, Rl and R2 can be selected from the same or
different groups.
X is a group which is hydrolyzable with water and
~0 which is bonded to a 5il icon atom. Examples of the hydro-
R3
lyzable groups are amino groups (-N~ 4), amido groups
/ R9 0 Rll
~- N - C - Rl~, imido groups ~ N = CORl ~ , lactam groups
( lR13~ ), aminoxy groups ( O - N ~ ), oxime groups
~- o - N = C ~ or - O - N = C R14~ .
~ ~R8 L I ~
~ ~s~35
In these formulas, R3 through R12 each represent a
hydrogen atom or unsubstituted or substituted monovalent
hydrocarbon radical. Examples are the same as those
described as examples of R, Rl and R2. In terms of ease of
preparation of silanes and siloxanes having these functional
groups, R3 through R12 are preferably selected from among
unsubstituted or substituted monovalent hydrocarbon radicals.
R13 and R14 represent alkylene groups.
Examples of component (c) are as follows:
aminosilanes and aminosiloxanes such as:
(CH3)2Si[NH(C4H9~)]
(CH3)2Si[NH(C6H5)]
(CH3)2si[N(CH3)2]2~ (CH3)(c6Hs)si[N(cH3)2]
(CH3)(CH2=CH)Si[N(cH3)2]2'
(CH3)2Si[N(C2H5)2]2
(CH3)(C6Hs)Si[N(cH3)(c2H5)]2~
fH3 fH3
(CH3)2N 7io Isi N(CH3)2~
CH3 CH3
20fH3 -fH3- fH3
(CH3)2N - fiO sio si - N(CH3)2
CH3 _CH3 15 CH3
aminoxysilanes and aminoxysiloxanes such as:
(CH3)2Si[ON(CH3)2]2, (CH3)(c6Hs)si[ON(c 3)2 2
(CH3)(CH2-CH)si~ON(cH3)2]2 r
(CH3)2Si[ON(CH3)(c2H5)]2
(CH3)(CH2=CH)si[ON(c2H5)2]2
s
fH3 CIH3 ¦~ CH3 ~ ~ fH3 ~ ¦
( CH3 ) 2No - i iO Isi - oN ( CH3 ) 2 , ~ l io ~ l io~
CH3 CH3 C3H7 2 / 1 2
c2H5 C2HS
fH3 ~f~3' fH3
(C83)2NO - SiO .- SiO - Si - ON (CH3)2
CH3 _CH3 4 CH3
or oximesilanes and oximesiloxanes such as:
(CH3)2$i[ON=C(CH3)2~2, tcH3)(cH2=cH)si[oN=c(cH3~2]2
(CH3)2Si[ON=C(CH3)(c2H5)]2
(cH3)(c6Hs)si~oN=c(cH3)(c~H5)]2
(CH3)2Si~oN=C(C~2)3CH2]2~ -
fH3 ~f~3' fH3
(CH3)2C=NO - SiO - SiO - Si - ON=C(CH3)
CH3 _CH3 4 CH3
CIH3 CH3 fH3
(C2H5)2C=NO - li - SiO ~ ON=C(C2H5)2 ;
c~3 CH3 20CH3
or amidosilanes and amidosiloxanes such as:
ICH3 11
(CH3)2Si[ - N - C -CH3~2, (CH3)(CH2=CH)-
fH3 R fH3 11
Si[ - N - C - CH3~2, (CH3)(C6~s)Si[ - N - C - CH3]2,
` - f2H5 1l
(CH3)~CH2=CH)Si[ - N - C - CH3]2,
C6H5 I f6H5 8
(CH3)2Si[ - N - C CH3]2, (CH3)(C6H5)Si[ N 3 2
fH3 1l
(CH3)2Si[ - N - C - C4H9]2'
8 CIH3 fH3fH3 fH3 8 R fH3 fH3
CH3 - C - N - SiOfi - N - C - CH3, CH3 - C - N - SiO -
C~3CH3 CH3
rfH~ fH3 CH3 1l
SiO - Si - N - C - CH3 ;
CH3 1oCH3
or imidosilanes and imidosiloxanes such as:
fH3
(CH3)2Si[ - N=COCH3]2, (CH3)(CH2=~CH)Si-
fH3 f2H5
[ - N=COCH3]2, (CH3)2Si[ - N = COCH3]2,
f6H5 fH3
(CH3)2Si[ - N=COCH3]2, (CH3)(C6H5)Si[ - N=COCH3]2,
f2H5
(CH3)(CH2=CH)Si~ - N=COCH3]2,
fH3 ICH3 IH3 fH3 fH3
CH30C=N - liO - liO - Si - N=COCH3 ;
CH3 CH3 10CH3
. ~
or lactamsilanes and lactamsiloxanes such as
(cH3)2si ~ ~ fo 1 ( cH3) (cH2=cH~si-
H2 ~ (CH2)~ 2
1 , (CH3)(C6Hs)S~ 1 '
~ H2 ~ (CH2)~ 2 ~H2 ~(CH2)~ 2
(CH3)(CH2 CH)Si r l 1
~H2 ~ (C~2)~ 2
( CH3 ) 2S i - ~ CO 1 ~
2 ~ (CH2)~ 2
fH3 CH3 f~3
7 lio lio - fi - ~ fo.
(CH2)4 - CH2 CH3 CH3 6 CH3 CH2 - ~CH2)4
Component ~c) can be a single compound of two or more compounds.
However, when two or more types are used in a mixture, an X group
which is hydrolyzable is preferably selected from the same type of
group. The amount of organosilicon compound used is an amount
sufficient to supply silicon-bonded nitrogen groups or groups
having silicon-oxygen-nitrogen bonds in at least the same molar
amount as the total molar amount (mol%) of silicon atom-bonded
hydroxyl groups at the terminus of the molecular chain in
component (a).
By so doing, the composition o-f this invention can be
preserved for a long period when prepared under substantially
anhydrous conditions and when stored under substantially anhydrous
conditions. When it is discharged into air, a highly viscous
product is obtained and an extremely viscous form of putty can be
produced.
In addition to components (a), (b) and (c), a catalyst
which accelerates the reaction between componen~ (a) and component
(c), e.g., diorganotin dicarboxylate, can be added. In addition,
various additives which are generally compounded in the
conventional silicone oil sealing materials, e.g., inorganic
pigments, organic pigments, heat resistance agents,
tackiness-improving agents, anti-sagging agents, and flame
retardants, can be added.
The composition of this invention can be produced as
follows. For example, component (b) is added to component (a) and
the mixture is blended in any of various types of blenders until a
homogeneous mix~ure is obtained. After degassing, component (c)
is added and the mixture is again blended until a homogeneous
mixture is obtained. In this case, the moisture must b~
eliminated as much as possible from the mixture of component (a)
and component (b), and component (c) must be added and blended
under substantially anhydrous conditions. The obtained sealing
material can be sucked up by a caulking gun and subsequently used
in sealing work. Alternatively, the sealing material can be
packed in a container which does not allow substantial amounts of
moisture to permeate, e.g. cartridges, aluminum foil tubes and
plastic film containers, and sealed for preservation. Thereafter,
the stored sealing material can be used when needed.
The sealing material of this invention has the following
characteristics and effects: (1) If it is stored in a container
which does not allow substantial amounts of moisture to permeate 7
the viscosity is unchanged after long-term storage; ~2) because a
polydiorganosiloxane having a low viscosity is used, it can be
easily discharged from the container; (3) a gap or cavity can be
easily filled; (4) the finishing work for the position filled is
very easy; (5) the viscosity increases greatly in a time period of
from one day to a few days after filling and an extremely viscous
putty-like substance can be obtained; and (6) the obtained
putty-like substance has excellent air tightness and
water-tightness, and no oil phase separation occurs after it is
stored for a long period. This noncurable sealing material is
especially useful as a sealing material for construction and civil
engineering work.
The following examples are presented for illustrative
purposes and should not be construed as limiting the scope of the
invention which is delineated in the ~laims.
"Parts" indicated in the following examples means "parts
by weight". The viscosity was the value at 25C. The atmosphere
for the sealing work was as followso 23-25C at 60-65% relative
humidity.
Example 1
Polydimethylsiloxane having hydroxyl terminal groups with
a viscosity of 0.015 m2/s (100 parts) was well mixed with light,
fine calcium carbonate without surface treatment (average particle
size: 0.1~ and BET relative surface .area: 7.5 m2/g) (45 parts).
After degassing, dimethyldi(N-methylacetamido)silane (8 parts~ was
added and the mixture was blended in a closed system without
contact with moisture. The mixture obtained was packed in an
aluminum tube. The material was squeezed out from the aluminum
tube by hand and a vertical joint with a depth of 5 mm and a width
of 8 mm, along a precast concrete plate, was filled with the
contents of the aluminum tube. After 3 days, an extremely viscous
putty had formed to a depth of 5 mm. After 6 months, no dripping
had occurred nor was any separation of an oil phase observed.
When this sealing material was stored in the aluminum tube at room
temperature for 6 months, no changes occurred in its
viscosity and it could still be squeezed ou~ very easily by
hand.
Example 2
Polydimethylsiloxane having hydroxyl kerminal
groups with a viscosity of 0.002 m2/s (100 parts~ was well
mixed with dry-process silica whose surface had been treated
with trimethylchlorosilane as a hydrophobic treatment and
whose BET relative surface area was 130 m2/g (20 parts).
After degassing, methylvinyldi(N,N-diethylaminoxy)silane (10
parts) was added. The mixture was blended in a closed
system without contact with moisture and the obtained
mixture was packed in a paper cartridge whose interior
surface was lined with aluminum foil. This paper cartridge
was loaded in a hand gun. The content was squeezed out by
hand and used to fill a horizontal groove between a plate of
glass and an aluminum window sash (depth: ~ mm, width: 4
mm). After 5 days, an extremely viscous putty had formed to
a depth of 7 mm. After 6 months, no separation of an oil
phase was found. When this sealing material was stored in
the paper cartridge for 6 months, no changes occurred in
viscosity and the sealing material could still be easily
squeezed out using a hand gun.
Example 3
Dimethylsiloxane-methylphenylsiloxane copolymer
having hydroxyl groups at the molecular chain terminus with
a viscosity of 0.008 m2/s (phenyl group content: 5 mol~)
(100 parts) was well mixed with dry-process silica having a
BET relative surface area of 200 m2/g (10 parts). After
degassing, methylphenyldl(N-cyclohexylamino)silane
(11 parts) was added and the mixture was blended in a closed
system without contact with moisture. The mixture was
packed in a cylindrical container made of polyvinylidene
chloride film and the container was wrapped with an
evaporation-aluminized polyvinylidene chloride film. After
6 months, the external evaporation-aluminized polyvinylidene
chloride film wrapper was taken off and the cyclindrical
container made of polyvinylidene chloride film was loaded in
a hand gun. The material was squeezed out by hand and a
horizontal groove between ALC panels (depth: 10 mm, width.
12 mm) was filled with the content. After 7 days, an
extremely viscous put~y was formed to a depth of 10 mm.
After 6 months, no separation of an oil phase was found.
Example 4
Sealing materials were prepared using the following
compounds as component (c) as shown in Table I under the
same conditions as in Example 1. The characteristics were
evaluated and are shown in Table I.
Example 5
In the sealing material as in Example 1, colloidal
calcium carbonate (120 parts) (average particle size: 0.04 ~,
BET relative surface area: 31 m2/g) with a treated surface
was used instead of the light, fine calcium carbonate under
the same conditions as in Example 1. The prepared sealing
material was packed in an aluminum tube. The material was
squeezed out from the aluminum tube and a horizontal groove
between a plate of glass and an aluminum window sash (depth:
7 mm, width: 4 mm) was filled with this sealing material.
After 5 days, an extremely viscous putty had formed to a
depth of 7 mm. After 6 months, no separation of an oil
13
phase had occurred. No changes occurred in its viscosity
after leaving this sealing material in the aluminum tube at
room temperature and the contents could s~ill be squeezed
out easily by hand.
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`` ' 15
