Note: Descriptions are shown in the official language in which they were submitted.
TITLE
VIBRATION DAMPERS
FIELD OF THE I NVENTION
This invention relates to epoxy resin based
vibration dampers and more particularly to vibration
dampers excellent in vibration damping capacity as well as
in mechanical strength.
BACKGROUND OF THE INV~NTION
In order that vibration from a source of vibration
will not be transfe~red to other portions, it has been
widely practiced to allow an antivibration rubber or air
spring to stand at the contacting surface between the
source of vibration and other portions. In these
procedures, however, no attenuation of the vibration
~; itself of the source of vibration can be expected, even
though the transfer of the vibration can be inhlbited.
: ~ ~
On that account, there has been adopted a
procedure wherein a vibration damper is allowed to adhere
to a vibrating body so as to attenuate the vibration
itself of the vibrating body. In the case of using such a
vibration damper, attenuation o$ the vibration is aimed at
by converting vibrational energy into heat.
~ In inhibiting vibration of a vibrating body using
': ~: ~ :
:
1296f.~. 4
-- 2 --
a vibration damper, when amplitudes of adjacent vibrations
in an attenuation sine wave are taken as X1 and X2,
respectively, there is obtained an excellent vibration
inhibitory effect if a logarithmic decrement represented
by the following equation (1) becomes larger.
~S = ln(Xl/X2) ...(1)
The logarithmic decrement ~ itself is represented
by the following equation (2), using dissipation factor 7.
~ = ni~ --(2)
Accordingly, it can be said that a vibration
damper having a larger dissipation factor ~ has excellent
characteristics.
In using such a vibration da~per in practice,
there are a case wherein the vibration damper is used by
simply pasting it on a source of vibration (non-constraint
type) and a case wherein the vibration da~per is used by
inserting it between a~source of vibration and a
constraint plate (constraint type).
In the constraint type vibration damper wh.ich is
used by inserting it between the vibrating body and the
constraint plate, a dissipation factor~is represented
~364~4
approximately by the following equation (3).
E3 h3 ~ h31
E1 h3 ~ h1 /
~2 (3)
1 + 2g + ( 1+ 2 )g2
wherein El is Young's modulus of the vibrating body and E3
is Young's modulus of the constraint plate, hl is a
thickness of the vibrating body and h3 is a thickness of
the constraint plate, h3l is equal to h2 ~ (hl ~ h3)/2, h2
is a thickness of the vibration damper, 2 is dissipation
factor of the vibration damper itself, g is a share
parameter represented by the followiny equations (4) and
(5).
f ... (4)
G2 h1 / El
fs 1 ... (5)
47jE3h3h2 ~ 3p 1
wherein G2 is a modulus of rigidity of the vibration
damper and p1 is a density of t.he vibrating body.
It is understood from the above-mentioned
iZ96~s74 ` `
equations that preferable as the vibration dampers are
those having a large dissipation factor ~2 and a small
modulus of rigidity.
The vibration dampers are required to have
excellent moldability, mechanical strength, water
resistance and chemical resistance in addition to the
above-mentioned vibration damping capacity and, moreover,
to be usable even under the circumstances of high
temperature and high vacuum.
As vibration damping compositions used for forming
such vibration dampers as mentioned above, there have
heretofore been used polyamide type resins, polyvinyl
chloride type resins or resins consisting essentially of
epoxy resins.
However, vibration dampers formed from the
vibration damping compositions comprising polyamide type
resins as their principal components had such problems
that the conditions under which the vibration dampers are
used are limited since they are poor in water resistance
as well as in chemical resistance and, moreover, they are
low in mechanical strength. The vibration dampin~
compositions consisting essentially of polyvinyl chloride
type resins had such problems that they are difficult to
be formed into vibration dampers having complicated shapes
and further that the production of vibration dampers of
~29~
-- 5 --
many species but in small quantity requires a high cost of
production. Vibration dampers formed from the vibration
damping compositions consisting essentially of epoxy type
resins had such problems that when the vibration dampers
high in mechanical strength and excellent in service
durability as well as in moldability are intended to
obtain, the vibration dampers obtained are found poor in
vibration damping capacity and, on one hand, when the
vibration dampers excellent in vibration damping capacity
are intended to obtain, the vibration dampers obtained are
found low in mechanical strength and poor in service
durability as well as moldability.
OBJECT OF THX INVENTION
The present invention is intended to solve such
problems associated with the prior art as mentioned above,
and an object oP the invention is to provide vibration
dampers having excellent vibration damping capacity and
being excellent in mechanical strength, service durabil.ity
and moldability.
SUMMARY OF TH~ INVENTION
The Pirst vibration damper of the present
invention is obtained by reacting (a) an epoxy resin
comprising polyglycidyl ether of polyol or its polymer
i296~74
Witll (b) a curing agent followed by curing, and
characterized in that said vibration damper has a maximum
value of a dissipation factor ~ being at least 1.3, a
tensile strength at rupture, elongation and elastic
modulu~ in tensile according to JIS K~113 being 0.05-3.0
kgf/mm2, 20-300% and 0.1-6.0 kgf/mm2, respectively, a
compression ~trength according to JIS R6911 being 0.5
kgf/mm , and Izod impact strength according to JIS K6911
being at least 5 kgf cm/cm or being not ruptured.
The second vibration damper of the invention is
characterized in that said vibration damper is obtained by
reacting (a) an epoxy resin comprising polyglycidyl ether
of polyol or it~ polymer with (b) a curing agent in the
presence of (c) a compound having a softening point of
less than 25C followed by curing, said compound being a
polymer containing as a principal component aromatic
hydrocarbons, phenols or polymers comprising at least one
member selected from among them.
The vibration dampers of the invention have
excellent vibration damping capacity and are excellent in
mechanical strength, service durability and moldability.
In particular, the first vibration dampers of the
invention have excellent vibration damping capacity and,
moreover, they are excellent in mechanical strength,
service durability and moldability and, in addition
~Z964 4
thereto, they are free of v~latile components and stable
even when used under the circumstances of high temperature
or high vacuum.
DETAILED DESCRIPTION OF THE INVENTION
The vibration dampers of the present invention are
illustrated below in detail.
Fig. 1 is a diagram to show the relation between
phase difference ~ , dynamic storage elastic modulus E',
dynamic loss elastic Modulus E" and complex elastic
modulus E of vibration damper.
The first vibration damper of the present
invention is obtained by reacting (a) an epoxy resin
comprising polyglycidyl ether of polyol or its polymer
with (b) a curing agent, and has specific physical
properties as will be mentioned later.
The epoxy resin (a), as mentioned above, is a
polyglycidyl ether of polyol or its polymer, and typical
examples of usable polyglycidyl ethers are such compounds
as enumerated below.
(a) Diglycidyl ethers of polyols having 2 to 15 carbon
atoms such as ethylene glycol, diethylene glycol,
triethylene glycol, polyethylene glycol, propylene glycol,
dipropylene glycol, dipropylene glycol, tripropylene
glycol, polypropylene glycol, 1,2-butylene glycol, 1,3-
lZ9~4
- a -
butylene glycol, 1,4-butylene glycol, di(1,4-butylene
glycol), poly(1,4-butylene glycol), neopentyl glycol, 1,6-
hexanediol, di~6-hydroxyhexyl)ether, 1,8-octanediol, di(8-
hydroxyoctyl)ether, 1,10-decanediol, di(10-
hydroxydecyl)ether, phenylethylene glycol,
di~phenylethylene glycol), etc.
~ b) Glycerol triglycidyl ether, polyglycerol
polyglycidyl ether, trimethylolpropane diglycidyl ether,
etc.
(c) Triglycidyl ether of propylene oxide adduct of
trimethylolpropane, triglycidyl ether of propylene oxide
adduct of pentaeryt~ritol, etc.
Usable as the curing agent (b) are amines, acid
anhydrides, polyamides, dicyandiamide, etc. Examples of
useful amine~ are N-aminoethyl piperazine,
diethylenetriamine, triethylenetetraamine,
trimethylhexamethylenediamine, isophoronediamine,
metaxylylenediamine, metaphenylenediamine,
diaminodiphenylmethane, etc. Examples of useful acid
anhydrides are phthalic anhydride, trimellitic anhydride,
methyl tetrahydrophthalic anhydride, dodecenyl succinic
anhydride, ethylene glycol bis(anhydrotrimmelitate),
maleic anhydride, etc.
Such curing agent (b) as illustrated above is used
in such an amount that the functional group reacting with
1296~74
the epoxy group in the curing agent becomes 0.6-1.4
equivalents, preferably 0.8-1.2 equivalents based on one
equivalent of the epoxy group contained in the afQre-
mentioned epoxy resin.
The first vibration damper of the invention
obtained in the manner now described has a maximum value
of dissipation factor ~ being at least 1.3, a tensile
strength at rupture, elongation and elastic modulus in
tensile according to JIS K7113 being 0.05-3.0 kgf/mm2, 20-
300% and 0.1-5.0 kgf/mm2, respectively, a compression
strength according to JIS K6911 being at least 0.5
kgf/mm , and Izod impact strength according to JIS K6911
being at least 5 kgf cm/cm.
The second vibration damper of the invention is
obtained by reacting (a) the aforesaid epoxy resin with
(b) the aforesaid curing agent in the presence of (c) a
compound having a softening point of less than 25C
followed by curing, said compound (c) being a polymer
containing as a principal component aromatic hydrocarbons,
phenols or polymers comprising at least one member
selected from among them.
The compound (c) used in the process for obtaining
the second vibration damper of the invention includes such
compounds as enumerated below.
(i) Aromatic hydrocarbons having a softening point of
12g~
-- 10 --
less than 25 C, such as toluene, xylene, styrene, ~-
methylstyrene, divinylbenzene, ethylbenzene, etc. or
mixtures thereof.
(ii) Phenols having a softening point of less than
25C, such as cresols, vinylphenols, propylphenols,
butylphenols, octylphenols, nonylphenols, dinonylphenols,
dimethoxy-4-methylphenol, etc. or mixtures thereaf.
(iii) Condensates of the above-mentioned aromatic
hydrocarbons, phenols of mixtures containing as a
principal component at least one compound selected from
among them with formaldehyde, said condensates having a
softening point of less than 25C.
(iv) Polymers of the above-mentioned aromatic
hydrocarbons, phenols of mixtures containing as a
principal component at least compound selected from among
them, said polymers having a softening point of less than
25C
The compounds ~c) as illustrated above are used in
an amount of 30 - 700 parts by weight, preferably 50
500 parts by weight based on 100 parts by weight of
the sum total of the epoxy resin (a) and the curing agent
~b)-
In order to improve their mechanical strength, thevibration dampers of the present invention may be
incorporated, if necessary, with inorganic or organic
i~g6~Y4
fillers. Examples of useful inorganic fillers include
mica, glass flake, scaly iron oxide, asbestos, etc., and
those of useful organic fillers include synthetic pulp,
polyamide flber, carbon fiber r polyester fiber, etc.
The vibration dampers of the present invention are
produced by an ordinary molding process wherein a
vibration damping composition is first prepared according
to the usual method by thoroughly mixing the aforesaid
epoxy resin (a) with the aforesaid curing agent ~b) and,
according to circumstances, together with the above-
mentioned compound tc) and further, optionally, together
with plasticizers or fillers, and after defoaming, this
vibration damping composition is cured at a temperature up
to 200C to a desired form.
EFFECT OF THE INVENTION
The vibration dampers of the present invention
have excellent vibration damping capacity and, moreover,
they are excellent in mechanical strength, service
durability and moldability. In particular, the first
vibration dampers of the invention have excellent
vibration damping capacity and, moreover, the~ are
excellent in mechanical ~trength, service durability and
moldability and, in addition thereto, they are free from
volatile components and excellent in stability even when
~;~g~4
- 12 -
used under the circumstances of high temperature or high
vacuum.
The present invention is illustrated below with
reference to examples, but it should be construed that the
invention is in no way limited to those examples.
~xample 1
-
To lO0 g of 1,6-hexanediol diglycidyl ether having
epoxy equivalent 150 g/equivalent was added 100 g of a
curing agent obtained by adding 1 part by weight of 2,4,6-
tris(dimethylaminomethyl)phenol to 100 parts by weight of
4-methyl-1,2,3,6-tetrahydrophthalic anhydride, followed by
thorough mixing at room temperature. There was prepared a
vibration damping composition.
Thè thus obtained vibration damping composition
was cured under the curing conditions of 120C x 3 hr, and
a vibration damper obtained thereby was measured in the
following manner for dissipation factor r~, volatile
component, tensile strength at rupture, tensional
elongation at rupture, elastic modulus in tension ,
compression strength, Izod impact strength and resistance
to chipping on bending.
Methods of measurement employed are as follows:
Conditions under which dissipation factor ~ of vibration
damper itself is measured)
~29~
- 13 -
Instrument: High-frequency viscoelasticity
spectrometer,
manufactured and sold by Iwamoto
Seisakusho K.K.
Temperature: -50 to 200C; sample, 2 mm width x
1 mm thick x 5 mm length
Frequency: 400 Hz
Method of measurement and Principle: In the case
where one end of a sample is fixed and the other end is
intended to vibrate in the lengthwise direction o~ the
sample, no measurement can be conducted in the direction
toward which the sample shrinks because the sample sags.
Therefore, at the outset, the sample is stretched to a
given extent, and the measurement is conducted while
applying dynamic displacement centering around the
stretched point of the sample. This stretch given at the
outset is called an initial strain (Ls) and a tension
produced when the initial strain is given is called an
~nitial tension (Fs).
When an amplitude ~Eo p) f the dynamic
displacement becomes larger than the initial strain, the
sample sags and the measurement comes to become
inoperable, and hence thi~ should be brought to attention
at the time when the mea~urement i9 conducted.
Complex elastlc modulus (Young's modulus): E*
~2964~ ~
- 14
(dyne/cm2) is calculated ac:cordin(3 to the following
equation using dynamic displacement : d L _ (cm), dynamic
force produced by applying the dynamic displacement to the
sample: ~ Fo p (dyne), length of the sample natural length
L (cm) prior to fixing the initial strain to the sample,
cross-sectional area of the sample : A (cm2), phase differ-
ence (Deg) between the dynamic displacement and
dynamic force, and frequency of vibration ~Hz).
E* - Vibrating stress (~ Fo_p / A ) e i(~ t+~
Vibrating strain (~Lo_p / L ) e w
= (aFo_p /~ Lo_p ) (L/A) ( cos~+ isin~)
Assuming E = ( Fo_p / Lo p ) ( L/A) ( cos ~ + isin~),
~mic storage E = E cos ~ (dyne/cm2 )
elastic modulus
D~mic loss elastic E = E sin ~ (dyne/cm2 )
modulus
~mic viscosity ~ = E / ~ (poise)
coefficient
Dissipation factor tan~= E / E =
= 2/~f
f = frequency ( Hz ~
As can be seen from the foregoing, the initial
strain and initial tension do not participate in the
1296'~4
- 15 -
calculation as illustrated above. The relation between
E', E", E* and ~ becomes as shown in Fig. 1.
A maximum value of the dissipation factor is shown
as ~ , and a temperature at which ~ is obtained is
~ max max
shown by (T~)max
(Method of measuring volatile component)
In accordance with the procedure as stipulated in
ASTM E595-77, there were obtained TML (Total Mass Loss) at
125C x 10 torr x 24 hours and CVCM (Collected Volatile
Condensable Materials).
(Method of measuring tensile strength at rupture, tensile
elongation at rupture and elastic modulus in tension)
The measurement was conducted in accordance with
JIS K~113 at a temperature of 25 + 0.2 C and a rate of
pulling of 10 mm/min, using No. 2 specimen.
(Method of measuring compression strength)
The measurement was conducted in accordance with
JIS K69111-5.19.1 at a temperature of 25 + 0.2C and a
rate of compressing of 1 mm/min.
(Method of measuring Izod impact strength)
The measurement was conducted in accordance with
JIS K6911-5.21 at a temperature of 25 ~ 0.2 C.
(Method of measuring resistance to chipping on bending)
The resistance to chipping on bending was
determined by bending a square column of the sample, 1/2 x
12~k~
1/2 x 5 inches, until the angles of both ends of the
sample becomes 90 to examine occurrence of fracture.
When no fructure occurred, the tested sample was
determined to come up to standard.
Vibration damping capacity of a vibration damper
when it was assembled as a constraint type vibration
damper to a vibrating body was measured by the following
procedure. That is, a sample of the constraint type
vibration damper of a sandwich structure was prepared by
fitting to an aluminum vibrating plate of 300 mm length,
30 mm width and 5 mm thick a vibration damper of 3 mm
thick having the same area as in the vibrating plate and
an aluminum constraint plate of 2 mm thick having the same
area as in the vibrating plate, and ~ of the constraint
type vibration damper thus prepared was measured at a
vibration frequency of 400 Hz. The maximum value of
obtained was taken as ~s
The results obtained are shown in Table 1.
Examples 2-7
Example 1 was repeated except that such epoxy
resins as shown in Table 1 were used, respectively, in
place of 1,6-hexanediol diglycidyl ether used in Example
~ The results obtained are shown in Ta~le 1.
129~ 4
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O A o Oo c O ~O o __ __
A N 1 h :~
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h 111 P A ~ t~l A ~ ~. t~
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~ ~ ~ 'a Eh~ ~ ~ ~1 ~ ~ n t~ I
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129~4 `
-- / 8 --
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:
12~7~
Example 8
Example 1 was repeated except that in place of the
curing agent used in Example 1, there was used 140 g of a
curing agent obtained by adding 1 part by weight of 2,4,6-
tris(dimethylaminomethyl)phenol to 100 parts by weight of
dodecenylsuccinic anhydride.
The results obtained are shown in Table 2.
Example 9
Example 8 was repeated except that in place of the
epoxy resin used in Example 1, there were used a mixture
of 50 g of dipropylene glycol diglycidyl ether and 50 g of
tripropylene glycol diglycidyl ether, and the curing agent
used in Rxample ~ but changing the amount thereof to 136
g~
The results obtained are shown in Table 2.
Example 10
Example 9 was repeated except that there was used
the curing agent used in Example 8 but changing the amount
thereof to 106 g.
The results obtained are shown in Table 2.
;;
129~4
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O O O
~._ r~ o~
K~a o i~ i
N¦ ~I S ii ~ ., ~
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S" ~ O O O
,0 ~ ~ _ .r u) ~
S ~ ~ O~ ~ ~
:~ ~ss 8 o o o
: ~ . ~ ~n ,o,
_ .
4~4
- 21 -
Examples 11-12
The present examples illustrate the use of curing
agent~ other than acid anhydrides. Example 1 was repeated
except that as shown in Table 3, the kind and amount of
curing agents used were changed from those of the curing
agent used in Example 1,
The results obtained are shown in Table 3.
- 22 ~Z96~'74
55 ~ _ `
_ u7 ~r
o U~
o, .
O~ 4 ~ ~ :~ ~
~; ' ~,) 4 0 ~ R
U ~ O ;~ 4
~ A N-~;~
N I N N
~o,~ ~1 o o
0~4~
~ ~ t~
~ :~ ~ N
3 ~ ^~ N
~ _ _
0 ~ ~V ~ 0 0
~ 1~ ,U ,o. ~ ," u~ ,
~ ~ '~ U ~ ~ rl U
¦ ~ X ~j d 0~ 4 5~ ~ ~
,~ I ~X u~ ~a~~ u~
~ ~ I=
.
- 23 -
Example 13
To 100 g of 1,6-hexanediol diglycidyl ether having
an epoxy equivalent 150 g/e~uivalent were added 100 g of
condensate of xylene and formaldehyde (an average
molecular weight 400, liquid at 25C, a viscosity 750
cps/50C) and 100 g of a curing agent obtained by adding 1
part by weight of 2,4,6-tris(dimethylaminomethyl)phenol to
100 parts by weight of 4-methyl-1,2,3,6-tetrahydrophthalic
anhydride, and the resulting mixture was thoroughly mixed
to prepare a vibration damping composition.
The vibration damping composition obtained was
cured under the curing conditions of 120C x 3 hr, and the
vibration damper obtained was measured in the same manner
as in Bxample 1 for dissipation factor ~, Izod impact
strength and resistance to chipping on bending.
The results obtained are shown in Table 4.
~xamples 14-19
Example 1 wa.q repeated except that in place of the
1,6-hexanediol diglycidyl ether used in Example 13, there
were used such epoxy resins as shown in Table 4 were used,
respectively.
~ The results obtained are ~hown in Table 4.
:: :
~Zg~4
- 2~ -
_~ ' (o al a~ ~ ~ a~
~ o o o o o o _
~ o 0 o o o U~ U~
~ O N N N ~ ~
__ , __
~t I ~i O .4 ~ N O ~ N
N N N N N N N
20~S - oO a~ ~ ~t Or v~ ~N
~_ 4 _
Xq
0 ~ O U) N O It) U) ~
~ ~ ~ ~ = r = ~ ~
.~ ~ ~8
e ~ O ~ ~ ~
~ t. o ~ O h ~ h P~ ~ ~ ~
O ~ >- A ~ A tJ) A ,~ _~ ~ ~0
\'11 0 4 ~1 4 ~14 4 ?~ O A 4
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,, ~ ,. q ,1 0 ,. ~ ,, 8 ,,
qq ~ q ~ ~ ~ ~ ~ o
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'O P~u o''o ~ O 4~ ~o
m p. A :~ O :~ ~ p. ~I ~ :'~ h 4
4~ lU--~ P. ~1 * ~ P A ~IA
~ ~ ~ rl ~ ~ ~I 4 ~rl 4 '~
_ _ -I U Q ~ Q 'a E 'a ~ 0 Q 0 Il~
_~
1~ = ~ ~ . ~ 0 ~_
~29~
- 25 -
Example 20
~ xample 15 was repeated except that in place of
the curing agent used in Example 15, there was used 140 g
of a curing agent obtained by adding 1 part by weight of
2,4,6-tris(dimethylaminomethyl)phenol to 100 parts by
weight of dodecenylsuccinic anhydride.
The results obtained are shown in Table 5
Example 21
~ xample 20 was repeated except that in place of
the eposy resin used in Example 20, there was used a
mixture of 50 g of dipropylene glycol diglycidyl ether and
50 g of tripropylene glycol diglycidyl ether, and the
amount of the curing agent used was changed to 136 g.
The results obtained are shown in Table 5.
Example 22
Example 21 was repeated except that the amount of
the curing agent u~ed was changed to 106 g.
The results obtained are shown in Table 5.
Examples 23-24
The present examples illustrate the use of curing
agents other than acid anhydrides. ~xamples 16 was
repeated except that the kind and amount of the curing
~296~4
- 26 -
agents used were changed as shown in Table 6.
The results obtained are shown in Table 6.
lZ~ t74
o o o
~'P ~ ~ ~
~ ~ P. ~ P~ ~ P. ~
U1 ~ ~ ~ ~ ~ ~ ~ .
,- U Q) ~ ~ ~ a
U) ~ ~ ~ ~ ~ ~
~ o ~ ~ ~ ~ ~ t.
P: ~ ~ t~ ~q
.. _ ____
~' h h h
'' a ~ :~ ~
O h ~ O O O
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_
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~ 1 ,~ C')
.
.
P~
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.
129~ L~4
- 28 --
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~ ~ ~ o ~
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~9~
- 29 -
Examples 25-29
Example 15 was repeated except that in place of
the condensate of xylene and formaldehyde used as the
compound (c) in Example 15, there were used other
compounds, respectively, as shown in Table 7.
The results obtained are shown in Table 7.
~2~ 4
- 30 -
Comparative Example 1
The present example shows an instance wherein the
use of the compound (c) was omitted. Example 15 was
repeated except that the condensate of xylene and
formaldehyde was not used.
The results obtained are shown in Table ~.
Comparative Example 2
The present example demonstrates that a vibration
damper obtained by the use as the compound (c) of a
compound other than those specifically defined in the
present invention is found poor in vibration damping.
capacity.
~ xample 13 was repeated except that in place of
the condensate of xylene and formaldehyde used in Example
13, there was used dioctyl phthalate.
The results obtained are shown in Table 8.
It is understood from this example that a
vibration damper obtained in the example is rather
inferior in vibration damping capacity to the vibration
damper obtained in Comparative Example 1 by using no
compound (c).
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¦ ~ ~I ~ 1 = /1 ~ b
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:` ~
e '
;:
.
