Note: Descriptions are shown in the official language in which they were submitted.
The present inven-tion relates to a resin composition
having an electromagnetic wave shielding ef~ect, and more partic-
ularly to a resin composition for shielding the transmission of
electromagne-tic waves thereby to prevent disorders or troubles
caused by electromagne-tic waves.
This application is a divisional application of copend-
ing application No. 462-546 filed September 6, 198~.
In the conventional systems, electronic instruments,
such as business machines, electronic computers and television
receivers, generate elec-tromagnetic waves by themselves to cause
malfunctions and/or noises in the neighbouring electronic instru-
ments.
On the other hand, the electronic instruments are
affected by the electromagnetic waves emitted from the adjacent
electronic instruments, leadin~ to malfunction thereof or genera-
tion of noises tharefrom.
~ roubles by the electromagnetic waves have been obvi-
~ ated at some extent when the housing of such electronic instru-
: ments are made of metal plates or aluminum die castings which can
shield the transmission
~: 35
~ .
- 1 -
~:
, ~?'~,
, . ~
'
of electromagnetic waves.
However, plastics materials have been
predominantly used for the housings of elec-tronic
instruments in recent years, because of the merits
that they are easily molded to have various designs
and that they are light in weight.
However, the plastics materials are generally
poor in conductivity and have substantially no
electromagnetic wave shielding effect. It is, -thus,
necessitated to process the plastics materials to
provide them with electromagnetic wave shielding
~ effect when they are used for the housing of electronic
; instruments.
Particularly, in recent years, xadiation of
electromagnetic waves has been severely prohibi~ed by
the domestic and foreign regulations. Under these
circumstances, there is an increasing demand for the
plastics materials provided with electromagnetic wave
shielding effects.
Various methods for providing the plastic
materials with the electromagnetic wave shielding
effect have hitherto been investigated, the known methods
including application of an aluminum foil or a
conductive tapej flame spraying with molten zinc,~
coating with a conductive paint, metal plating on the
.:~
~ ~ ~ plastics materials, vacuum evaporation coating, spattering
::
~ 2 -
^,: ,
'' `
.
:~
ion plating and molding a conductive plastic material
added with a conductive filler.
However, the method of application of an
aluminum foil or a conductive tape for the provision
of electromagnetic wave shielding effect is not used
practically, since it has the disadvantages that
extreme skillfullness i5 required and that it is not
suited for the housings having complicated shapes.
The method of flame spraying with molten zinc
and the method of coating with a conductive paint have
been predominantly used at the present time. However,
these methods have the disadvantages that the thickness
of the lining or coating becomes uneven when the housing
has a complicated shape and that the adhesiveness of
the llning or coating to the substrate is insufficient to
result in exfoliation of the conductive layer, leading
to the loss of the electromagnetic wave shielding effect
or even causing a risk of firing.
Although -the durability and adhesiveness of
the metal plated on the plastics materials are satisfactory,
only few kinds of plastics materials can be plated with
metals and the articles to be plated are limited to those
; of small dimensions.
,:
Satisfactory electromagnetic wave shielding
effect can be provided by the metal evaporation techniques
including the vacuum evaporation coating, spattering and
- 3
: ~,
,
_ .. .
- , ~
; ~ '` ~` '' '
.. .
' :
ion plating. ~30wever, these techniques have not been
applied ~or commexcial scale productions, since they
require expensive apparatuses and skillful operations.
Contrary to the aforementioned methods wherein
conductive layers are formed on the surfaces of molded
plastics materials to provide the electromagnetic wave
shielding effect, the molded products made of a
composite conductive plastics material containing a
conductive filler mixed and dispersed in a matrix
plastics material is averted from the impairment of
electromagnetic wave shielding effect or from the risk
of firing caused by exfoliation of conductive layer.
However, the known conductive plastics molded
articles have the disadvantages that satisfactory
electromagnetic wave shielding effect cannot be obta;ned
unless a large amount of conductive filler is added to
the matrix plastics material, and that the physical
proper-ties of the resultant plastics material are
deteriorated or the appearance of the molded article
is impaired with serious increase in cost as the
quantity of the filler added to the matrix plastic
material is increased.
Particularly, as the amount of added
conductive ~iller is increased, the dispersibility of
the filler is lowered to result in uneven dispersion
thereof. Especially when carbon fibers are used for
- 4 ~
.
the conductive filler, the fibers are broken during the kneading
step to lower the electromagnetlc wave shlelding effect. If some
parts of the expensive carbon fibers are replaced by another
inexpensive conductive filler in order to decrease the ccntent of
the carbon fibers, the fibrous and pulverized fillers present in
the mixed condition become hardly dispersed in the matrix resin,
leading to deterioration of moldability of the plastics material
and deterioration of the properties of the molded articles. If
the resultant plastics material is molded at a higher temperature
in order to improve the moldability thereof, the matrlx resin is
decomposed or otherwise damaged so that the physical prcperties
and the appearance of the molded articles are deteriorated and
the coloring property of the resin becomes poor.
The present invention provides a resin composition
having improved electromagnetic wave shielding effect, comprising
a resin ingredient and carbon fibers which are uniformly disper-
sed in the resin ingredient and are not suhstantially broken or
cut at the step of mixing and dispersing them.
The present invention also provides a resin composition
having improved electromagnetic wav shielding effect and having
improved fluidity and excellent moldability.
The present invention again provides a resin composi-
tion having improved electromagnetic wave shieldlng effect, which
can be molded at a reasonably low melting temperature to avoid
deterioration of physical properties, appearance and colouring
property of the matrix resin.
The present invention also provides a resin composition
having improved electromagnetic wave shielding effect, which has
a ~lame-retarding property and is improved in thermal and mecha-
; nical properties.
The present invention again provides a resin composi-
-- 5 --
`~ :
~ 3~ ~
t.i.on, which has an extremely high electromagnetic wave shieldingeffect and may be coloured freely.
The resin compos~tion having an electromagnetic wave
shielding effect, according to -the present lnvention, comprises
35 to 9o wt.~ of a copolymer of an ethylenic unsaturat~d nit-
rile, a diene rubber and an aromatic vinyl compound or a mixture
of said copolymer with another copolymer of ethylenic unsaturated
nitrile and an aromatic vinyl compound; 1 to 25 wt.% of a plasti-
cizer; and 5 to 40 wt.% of carbon fibers with metallized sur-
faces.
The single Figure of the accompanying drawings is a
schematic illustration showing the tester for the determlnation
of the electromagnetic wave shielding effect of the plastics
molded ar~icle made of the resin composition according to the
invention.
:
'~.`
~ 25
:~:
.
:,
~, ~
_ ~; _
, ~
,
, ... .. .
.
The ma-trix resin for the resin composition having an
electromagnetic wave shielding effect~ according to the present
invention, is a copolymer of an ethylenic unsaturated nitrile, a
diene rubber and an aromatic vinyl compound or a mixture thereof
with another ~opolymer of an ethylenic unsaturated nitrile and an
aromatic vinyl compound.
The ethylenic unsaturated nitrile used in the invention
includes, for example, acrylonltrile, methacrylonitrile, ethy-
acrylonitrile and methyl methacrylonitrile. The particularlypreferred are acrylonitrile and methacrylonitrile.
The diene rubber used in the invention includes one or
more of conjugated 1,3-dienes, such as butadiene, isoprene~ 2-
chloro-1,3-butadiene, 1-chloro-1,3-butadiene and piperylene,
which forms rubbery polymers, the particularly preferred being
butadiene.
;:
;~
~ 30
.
:
~; 35
'
.
.
The aromatic vinyl compound used in the
invention includes, for example, styrene, a-methylstyrëhe,
vinyltoluene, divinylbenzene and chlorostyrene, which
may be used singly or in combination. A favourable
result can be obtained, in the present invention, when
styrene is used singly as the aromatic vinyl compound.
A more favourable result may be obtained
when the copolymer of the ethylenic unsaturated nitrile,
the diene rubber and the aromatic vinyl compound is a
graft copolymer prepared by graft~copolymerizing 20
to 75 parts, preferably 20 to 60 parts, by weight of a
diene rubber or a diene-containing polymer containing
not less than 50 wt% of diene rubber with 80 to 25 parts,
~ preferably 80 to 40 parts, by weight of a mixture of an
.~ : lS ethylenic unsaturated nitrile and an aromatic vinyl
compound.
~; If a mixture of a copolymer of ethylenic
unsaturated nitrile, a diene rubber and an aromatic
:
vinyl compound with another copolymer of an ethyleneic
unsaturated nitrile and an aromatic vinyl compound
is used, the mixing ratio of the former to the latter
; may range within 25 to 99 parts by weight of the
~; former to l~ to 75 parts by weight o~ the latterj
preferably within 35 to 65 parts by weight of the former
to 65 to 35 parts by weight of the latter. I~ the
mixing ratio is out of the aforementioned range, the
`:
j,
. - 8 -
;- ~ ~ ~ .. ...
,
. ~ .
moldability and the properties of the resultant
composition are deteriorated. The process for the
preparation of the copolymers and the mixture thereof
are well-known in the art, and disclosed, for example,
in the speci~ication of Japanese Patent Publication
No. 37675/1976.
Specific examples of the plasticizers used
in the composi.tion of the invention include phthalic
acid esters r such as dibutyl phthalate and di-2-
ethylhexyl phthala-te; fatty acid esters~ such as di-2-
ethylhexyl adipate, dibutyl sebacate, di-2 ethylhexyl
sebacate and di-2--ethylhexyl azelate; epoxides, such as
epo`xidized fatty acid monoesters, epoxidized soybean oil
and epoxidized linseed oil; phosphoric acid esters,
: such as tricresyl phosphate, tri-2-ethylhexyl
phosphate and tributoxyethyl phosphate;
.
~ ~ ethers, such as triethyleneglycol di-2-ethyl butylate,
;~ 20 dibutylcarbitol adipate and dihutylcarbitol formal;
polyesters, such as adipic acid polyesters, sebacic acid
: polyesters and azelaic acid polyesters; and chlorinatad
plasticizers, such as chlorinated aliphatic esters and
chlorinated paraffins. Particularly preferred
plasticizers are phthalic acid esters, phosphoric acid
esters and fatty acid esters~
_ g _
-
~ ' ~
.
.
'
6~
When it is desired to provide the resin
composition of the present invention with -the flame-
retarding property, a plasticizer selected fxom phosphoric
acid derivatives and ethylene/propylene terpolymers is
used.
Specific examples of the flame-retarding
plasticizers of phosphoric acid derivatives are tri(2-
ethylhexyl) phosphate, 2-ethylhexyl diphenyl phosphate,
tributoxyethyl phosphate, triphenyl phosphate, cresyl
diphenyl phosphate, isodecyl diphenyl phosphate,
tricresyl phosphate, trixylenyl phosphate, mixed aryl
phosphates, phenyl/isopropyl phenyl phosphate, mixed
~ triaryl phosphates and tris~chloroethyl) phosphate.
;~ Particularly preferred results can be obtained by
~;~ 15 ~ using 2-ethylhexyl diphenyl phosphate and tricresyl
phosphate sin~ly or in combination.
~ avorite flame-retarding property may be
obtained by using the ethylene/propylene terpolymer as
the plasticizer in the resin composition of the invention.
The ethylene/propylene terpolymer used as the plasticizer
:~ .
include copolymers of ethylene and propylene polymerized
with a small amount of unsaturated compound as the third
component. The terpolymer may be composed to 50 to 80 mol~
of ethylene, 20 to 50 mol% of propylene and 0.5 to 10 mol%
of an unsaturated third compound, and the most preferable
:
-~ composition contains 60 to 70 mol~ of ethylene, 30 to
~ ~ - 10 -
. .
. .
126O~J8~
40 mol~ of propylene and 0.5 to 5 mol% of an unsaturated
third compound.
Dienes and/or trienes may be generally used as
the third unsaturated compound, inter alia l,4~hexadiene,
dicyclopentadiene and ethylidene norbornene are
particularly preferred because of their excellent
copolymerizability and low cost~
The contenk of the plasticizer in the resin
composition of the invention may range within l to 25 wt%,
preferably within 2 to 15 wt%. If the content of the
plasticizer is less than 1 wt~, the viscosity of the
~- molten resin composition at the kneading step becomes
too high to cause breakdown of the carbon fibers and to
result in insufficient dispersion of the fibers, thereby
to lower the electromagnetic wave shielding effect and
~ to deteriorate the moldability of the resultant resin
; composition. On the contrary, if the content of the
plasticizer is more than 25 wt%, the physical properties
including the resistance to heat of the resin
composition are lowered and the molded products become
sticky due to bleeding of the plasticizerO When the
flame-retarding plasticizer is used, satisfactory fl~me-
retarding effect cannot be expected if the content
thereof is less than 1 wt~. When a phosphoric acid
derivative is used as the flame-retarding plasticizer,
particularly preferablè content thereof ranges within
:
,.. , .. ,. .. " ~,.. .
.
-: ~ ., ' .
2 to 8 wt~. On the other hand, when -the
ethylerle/propylene terpolymer is used as the plasticizer,
particularly preferable content thereoE ranges within 5 to
10 wt%.
One or a mixture oE two or more of carbon fibers
wi-th metollized surEaces such as carbonized
polyacrylonitrile fibers, carbonized pitch fibers and
carbonized phenolic compound fibers is used in the resin
composition of the invention. Surperior electromagnetic
wave shielding effect can be attained by using the
carbonized polyacrylonitrile fibers singlyO
It is desirous that the length of individual
carbon fiber be preferably in the range of from 0.5 to 20
; mm, most preferably in the range of from 2 to 10 mm. If
the length of individual fiber is less than 0.5 mm, the
conductivity of the resin composition is lowered to an
unsatisfactory level due to excessively small aspect ratio
of the fibers. On the contrary, if the length of
individual fiber is longer than 20 mm, the fluidity of the
; 20 resin composition is extremely lowered to deteriorate the
moldabillty thereof signiflcantly with attendant
deterioration of the appearance and mechanical properties
of the molded products. In~addition, the conductivity of
the resin composition is rather lowered, since the fibers
, ,::
~ 25 are not evenly dispersed throughout the composition. The
.
carbon fibers may preferably have the diameters ranging
- 12 -
"~ :
:~ :
:
-
:: ~
.: ~
- .,
''~ ' ,
within 3 to 25~1, more preferably within 5 to 12~. The
fibers are ap-t to be broken under the shearing ac-tion
at the kneading step to lessen -the aspect ratio of the
fibers or to be entangled with each other to form
fiber balls to lessen the dispersibility thereof,
resulting in unsatisfactory conductivity of the resin
composition, if the diameter of individual fibers is
less than 3~l. On the contrary, if the diameter of
individual fibers is more than 25~, the conductivity
of the resin composition becomes unsatisfactory since
the aspect ratio of the fibers is too small. The
bundle count of -the carbon fibers may range preferably
within 1,000 to 20,000, more preferably within 3,000
to 15,000. If the bundle count is less than 1,000,
the bundled fibers are apt to be entangled with each
other to form fiber balls to lessen the dispersibility
thereof and to result in unsatisfactory conductivity
of the resultant resin composition. On the contrary,
,
if the bundle count is more than 20,000, the fiber
bundles cannot be cloven efEectively even by the
; shearing action at the kneading step, leading to
uneven dispersion of the flbers to result in inferior
conductivity of the resin composition. Carbon fibers
with metallized. s~es may be produced by coating
- 13 -
.,
~lz~
the surfaces of -the carbon Eibers with a metal, such
as Ni, Cu or Al, by the plating, vacuum evaporation
coating or spa-t-tering processes.
The content of the carbon fibers in the
resin composition should range within 5 to 40 wt%,
- preferably l0 to 25 w-t%. If the content thereof is
less than 5 wt~, substantial electromagnetic wave
shielding effact cannot be provided. On the contrary,
if the con-tent thereof exceeds 40 wt%, the resultant
resin composition is hardly molded through extrusion
or injection molding and the physical propeties of the
; molded products are deteriorated.
In the present invention, a conductive
carbon black may be added to the composition in
addltion to the aforementioned carbon fibers.
Specific examples of the conductive carbon black
~ include furnace black, channel black and the like such
;~ as S.C.F. ~Super Conductive Furnace) black, E.C.F.
(Electric Conductive Furnace) black, a by-product
black such as "Ketchen Black" ~vailable from Nippon
E.C. Co., Ltd. and acetylene black. It is preferred
that the carbon black satisfies at least one of the
following features of:
; .
" :~
r ~ ~ 14
''
~ . ` '
(1) Having highly developed structure;
(2) Having small particle size;
(3) Having large specific sur~ace area;
(4) Containing only a small amount of impurities
which capture electrons; and
(5) Having high degree of graphitization.
The preferable ~uantity of the carbon black
added to the composition varies depending on the kind
of the used carbon black, particularly on the specific
10 surface area thereof, and may range within 2 to 30
wt~, more pr:eferably 3 to 15 wt%. If the added amount
of the carbon black is less than 2 wt~, the volume
resistivity of the molded product becomes uneven to
~ result in inferior electromagnetic wave shielding
; 15 effect. On the contrary, if the added amount of the
carbon black exceeds 30 wt%~ the resin composition is
hardly molded by extrusion or injection molding and the
~;;: physical properties of the molded product become inferior.
~: ~ An alkylamine antistatic agent may also be
20 added to the resin composition. Pxeferable antistatic
agents are amine compounds having hydroxyethyl groups
and represented by the following formula of:
~ (CH CH O) H
-~ : R -N 2 2 m
(CH2CH20) nH
wherein Rl is an alkyl or alkenyl group
having 8 to 22 carbon atoms, and m and n are
- jS_
~'
... :
8~1L
integers of 1 to 10.
The compounds set forth above are well-known
in the art, and it is preferred to use those
represen-ted by the aforementioned formula wherein
2 < m + n ~ 10.
Representative amine compounds having
hydroxyethyl groups are N,N-bis(hydroxyethyl) tallow
amine, polyoxyethylene lauryl amine and fatty acid
esters of polyoxyethylene lauryl amine. Amongst
them, M,N-bis(hydroxyethyl) tallow amine is the most
preferred.
The amount of the added alkyl amine antistatic
agent may range within 0.5 to 10 wt%, preferably i
to 5 wt~. The effect of lowering the volume resistivity
of the molded product cannot be expected when the added
::
amount of alkyl amine antistatic agent is less than 0.5 wt~
so that the electromagnetic wave shielding effect is
not improved. On the contrary, if the amount of the added
alkyl amine~antistatic agent is more than 10 wt~,
the resin~composition is excessively lubricated to affect
adversely the dispersibility of the carbon fihers at the
compounding step so that the resin composition becomes
hardly molded through~extrusion or injection~molding
with attendant undesirable results that the physical
propertiee~and the electromagnetic wave shielding effect
of the molded product become inferior.
~ ~ - 16 -
:': ~ . - ' : :
,
:: ' , -
A halogen-containing organic flame retarder and
an auxiliary Elame-retardirlg agent may also be added to
provide the resin composition with potent resistance to
Eiring. Specific examples of halogen-containing organic
flame retarder include chlorinated paraffins,
tetrabromobisphenol-A and oligomers thereof,
decabromobiphenyl ethers, hexabromobiphenyl ethers,
pentabromobiphenyl ethers, pentabromotoluene,
pentabromoethylbenzene, hexabromobenzene, pentabromophenol,
tribromophenol derivatives, perchloropentanecyclodecane,
hexabromocyclododecane,tris(2,3~dibromopropyl-1)-
isocyanurate, tetrabromobisphenol-S and derivatives
thereof, 1,2-bis(2,3,4,5,6-pentabromophenoxy)ethane,
1,2-bis(2,4~6-tribromophenoxy)ethane, brominated
styrene oligomers, 2,2-bis-(4(2,3-dibromopropyl)-3,5-
dibromophenoxy3propane, tetrachlorophthalic anhydride
and tetrabromophthalic anhydride.
The auxiliary flame-retarding agents which
may be used in the resin composition of the invention
include antimony trioxide, sodium antimonate, zinc
borate, and oxides and sulfides of zirconium and
.
molybdenum, the most favourable result being obtained
; by the use of antimony trioxide.
The amount of the halogen-containing organic
flame retarder added to the resin composition varies
depending on the required degree of 1ame resistant
, ~ .
- 17 -
~2~
property and also on the content of the flame-retarding
plasticizer, and ranges generally from 2 to 35 wt~,
preferably from 5 to 25 wt~.
~he flame-retarding effect hecomes insufficient
if the amount of the added halogen-containing organic
falme retarder is less than 2 wt~, whereas the thermal
and mechanical properties of the molded product become
inferior if the amount of added halogen-containing
organic flame retarder exceeds 35 wt%.
The added amount of the auxiliary flame-
retarding agent may be within 0.4 to 21 wt% and the
ratio thereof-to the halogen-containing organic flame
- retarder should be within the range of from 6/10 to
2/10, preferably from 5/10 to 3/10. Satisfactory
synergistic effect of retarding the propagation of flame
cannot be obtained if the added amount of the auxiliary ..
flame-retarding agent is less than 0.4 wt~, whereas the
mechanical properties of the molded product are
,
~ ~ deteriorated if the added amount of the auxiliary
,.
flame-retarding agent exceeds 21 wt%.
; If the ratio of Lhe auxiliary flame-retarding
agent to the halogen-containing organic flame retarder
is less than 2/10, synergistic flame-retarding effect
cannot be xealized to result in unsatisfactory flame-
~retarding function, whereas the mechanical properties
:: ~
~ of the molded product becomes inferior if the ratio of
~ ,
~ - ~8 -
'
,
:: ' ' ' '
,~ ,.. `,,.,.,, ,....... ~ :
~, ,
' :
83~
the former to the latter exceeds 6/10.
In order to further improve the properties of
the resin composition of the invention, antioxidants,
internal or external lubrican-ts and stabilizers may be
added thereto. Antioxidan-ts which may be added to the
resin composition of the invention include phenolic
antioxidants, sulfur base antioxidants and phosphor base
antioxidants. Specific examples of the phenolic
antioxidants are 2,6-di-tert-butyl-p-cresol,
2,2'-methylenebis(4-methyl-6-tert-butylphenol),
4,4'-butylidenebis(3-methyl-6-tert-butylphenol?, 4,4'-
thiobis(3-methyl-6-tert-butylphenol), butylhydroxyanisole
and tetraki~[methylene-3(3,5-di-tert-butyl-4~hydroxyphenyl)-
propionatelmethane; the specific examples of the sulfur
` LS base antioxidants are dilauryl thiodiproplonate, distearyl
thiodipropionate, lauryl stearyl thiodipropionate,
dimyristyl thiodipropionate and distearyl
'-thiodibutylate; and the specific examples of the
phosphor base antioxidants are tridecyl phosphite, diphenyl
phenyl phosphite~triphenyl phosphite and trinonylphenyl
. . .
phosphite. These antioxidants may be used singly or in
combination. Decomposition or deterioration due to
oxidation of the resin composition can be prevented by
~ .
adding one ox more of the aEorementioned antioxidants,
preferably r in an amount of 0.01 to 4 parts by weight
to 100 parts by weight of the resin composition.
1 9
.. ' ``' '' - ` '"" '
. :
'.
~L2~181
The internal or external lubricants which may
be added to the resin composition of the invention include
paraffins and hydrocarbon resins, such as paraffin waxes,
liquid paraffins, paraffin base synthetic waxes and
polyethylene waxes; fatty acids, such as stearic acid
and hydroxystearic acid; fatty acid amide.s, such
as stearoamide, oxystearoamide, oleyl amide,
methylenebisstearoamide and methylenebisbehenamide;
fa-tty acid esters, such as n-butyl stearate, methyl
hydroxystearate and esters o~ saturated fatty acids;
~atty acid alcohols, such as higher alcohols, and
esters of higher alcohols and partial esters of fatty
acids and polyhydric alcohols, such as esters of
. ; glycerine and fatty acids! triglyceride of hydroxystearic
; 15 acid and esters of sorbitan and fatty acids. One or
a mixture of two or more of the internal or external
lubricants set forth above may be used.
; The stabilizers which may be added to the
resin composition of the invention include metallic
~: 20 soaps, sal~s of inorgnic acids, organic tin compounds
: ~ : and composite stabilizers, Specific examples of
:
the metallic soaps are zinc stearate, calcium stearate,
~ zinc laurate and cadmium 2-~thylhexoate; examples of
;.;; ; ~ the salts of inorganic acids being tribasic lead sulfate,
~ 25 basic lead sulfite and lead-barium compounds; axamples
of the organic .tin compounds being dibutyl tin laurate,
~ ,
- 20 -
~ ' ~ ` ,,
.
dibutyl tin dimaleate, and di-n-octyl tin maleate polymers;
and examples of the composite stabilizers are calcium-
zinc base stabilizers, barium-lead base stabilizers
and cadmium-barium-zinc base stabilizers. These
; 5 stabilizers may be used singly or in combination.
~ny one or more of the aforementioned internal
and/or external lubricants and/or stabilizers may be
added to the resin composition, preferably, in a xatio
of 0.01 to 4 parts by weight to 100 parts by weight
; 10 of the resin composition to improve the fluidity of the
resin cGmpOSitiOn at the moldin~ step and to prevent
decomposition or deterioration of ~he resinous lngredient.
The process for the preparation of the resin
composition of the invention will now be described.
The copolymer of an ethylenic unsaturated nitrile, a
diene rubber and an aromatic vinyl compound may be
in the form of powder, bead or pellet. The copolymer
or mixture thereof with another copolymer of an
. .
ethylenic unsaturated nitrile and an aromatic vinyl
compound is mixed with the plasticizer and the
carbon fibers and optionally with other ingredients.
In order to lmprove the moldability of the resin
composition and to improve the properties of the
molded products, it is preferred that the ethylenic
unsaturated nitrile/diene rubber/aromatic vinyl
compound copolymer be in the form of powder and the
- 21 -
'
..
,,,~ '.
. :
,
ethylenic unsatur~ted nitrile/axomatic vinyl compound
copolymer be in the form of bead. In order to
uniformalize or homogenize the resin composition, the
mixture is mixed and kneaded usiny a kneader or
extruder, such as Bumbury's mixer, cokneader, single
spindle extruder or double spindle extruder. The
mixture may be subjected to pre-mixi~g process using
a tumbler or high speed mixer prior to the mixing
and kneading step.
The mixed and kneaded resin composition is
then charged in a hopper of an injection molding machine
to be melted in a plasticizing cylinder of the injection
molding machine, and the molten resin composition is
injected into a mold and then cooled to be solidi.fied.
Solidified molded mass is removed from the mold to
o~tain an injection molded article made o~ the resin
composition of the invention. Likewise~ the mixed and
kneaded resin composition is charged in a hopper of an
extuder to be melted in a plasticizing c~linder of the
extrude~, and the molten resin composition is extruded
through a die attached to th~ end of the extruding
cylinder to form an extruded product made of the resin
composition of the in~ention.
~ ~ .
The present invention will now be described
more specificall~ by rèferring to Examples thereof.
-- 22 -
'~
:
~ , ~
Examples 1 to 8
A powder-form ABS resin (acrylonitrile/butadiene/
styrene copolymer resin) having a composition composed
of 10 wt~ of acrylonitriler 50 wt% of butadiene and
40 wt~ of styrene and a bead-form AS resin (acrylonitrile/
styrene copolymer resin) having a composition composed
of 30 wt~ of acrylonitrile and 70 wt% of styrene were
used. A plasticizer available from Kao Soap Co., Ltd.
e~n~,~
under the ~R~b-~a~e "VYNYCIZER #80" was used as khe
plasticizer in the resin composition. Carbonized
polyacrylonitrile (referred to as "PAN" in the following
Tables) chopped strands (Length 6 mm, Daimeter. 7~
Bundle Count: 12,000) available from Toho Rayon Co.,
~rf-~e~e~
Ltd. under the T~a~r-Wa~e "BESFIGHT HTAC6S" were used
as the carbon fibers. One part, by weight, for each
of an antioxidant and zinc stearate were added to
100 parts, by weight, of the resin. The compositions are
shown in Table 1. Each of the compositions was put
-~ ~ inko a Bumbury's mixer heated to 140C to be mixed
and kneaded until the temperature of the mixture reached
~ 190C. Immediately after the mixture was discharged from
-" the mixer, it was rolled through mixing rollers to form
~ a sheet which was cooled and then crushed into pellets.
,, ~ ~ : :
The thus formed pellets were charged in a
hopper o~ an 8-ounce injection~molding machine to be
melted in a plasticizing cylinder of the machine, and
: `::
~ ~ - 23 -
.. .
: : .,
.. .. . .
: . ;~.
:: . ~' -': ;
::
, . .
~e~ injected in-to a mold.
The mold was the one provided with a 2 mm~
direct gate for molding a housing of 15 cm square and
having an wall thickness of 3 mm.
The thus molded products had excellent physical
properties, improved resistance to heat and improved
electromagnetic wave shielding effect, as shown in
Table 1.
Examples 9 to 11
Each of the compositions set forth in Table 1
was pelletized similarly to Example 1, and charged in
a hopper of an extruder having a cylinder of 40 mm in
diameter (L/D = 24) to be melted therein at 200C.
The molten mass was allowed to pass through a die for
molding a single layer sheet.
: `
The die had a width of 600 mm and the lip
gap was adjusted to 3.5 mm. As the result, a single
; layer sheet havlng a thickness of 3 mm was formed.
~` ~ The thus formed single layer sheets had
~s 20 excellent physical properties, improved resistance to
heat and improved~electromagnetic wave shielding effect,
as shown in Table 1.
:
Examples 1~ and 13
A powder-form MBS resin (methacrylonitrile/
butadiene/styrene copolymer resin) composed of
50 wt~ of~methacrylonltrile, 10 wt~ of butadiene and
.~:
~; - 24 ~
; :: . : ~
:.
~2~0~
40 wt~ of styrene was used in placa of the powder~form
acrylonitrile/butadiene/styrene copolymer resin~ Other
ingredients used in the compositions were the same as
used in Example l. The compositions were pelletized
similarly to Example l and then subjected to injection
molding to form molded products. The properties of the
molded products were tested to reveal that they were
improved in physical properties, resistance to heat
and electromagnetic wave shielding effect, as shown
in Table l.
Example l4
A pellet-form ABS resin (acrylonitrile/butaidene/
; styrene copolymer resin) composed of 20 wt% of ~.
acrylonitrile, 20 wt~ of butadiene and 60 wt%
; 15 :of styrene was used in place of the ~BS resin as used
in Example l to prepare the resin composition shown in
~:~ Table l. The resin composition was pelletized similarly
to Example l and subjected to injection molding to form a
. : . :
~ : molded:product. The properties of the molded product
,
were tested to reveal~that it had excellent physical
properties,~improvéd resistance to heat and improved
: : . : ~
electromagnetic wave shielding~effe~t.
: Comparative E~ d_Z
: Injection molded products were produced from
the compositions set forth in Table 2 in accordance
: with the procedures similar to Example l, except in
~: :
~ : : :
~ - 25 -
. .
:
~ `
~L2~
that one composition contained a plastici~er in an amount
of less than the range defined in the claims whereas the
other composition contained the plasticizer in an amount
more than the defined range.
The properties of the injection molded products
were tested. The results are shown in Table 2.
Comparative Examples 3 and 4
Injection molded products were produced from
the compositions set forth in Table 2 in accordance
with the procedures similar to Example l, except in that
~ one composition contained carbon fibers in an amount of
; less than the range defined in the claims whereas the
~; other composition contained carbon fibers in an amount
more than the defined range.~
The properties of~the injection molded products
were tested. The results are shown in Table 2.
~ ~ -
26 -
:
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~ '~ " ' .
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27 --
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:
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-- 28 --
,, . . ~ .
,
Table 2
_ _ _ I
Comparat .ve Exzmple
1 2 3 4
..
Resin
Powder-form ABS Resin (wt%) 33.8 2235.2 16
Powder-form MBS ~esin (wt%) _ _ _ _
Bead-form AS Resin (wt%)50~7 33 52.824
Carrç~o-
sition Pellet-form ~BS Resin (wt%) _ _ _
_
Plasticizer
Di-2-ethylhexyl Phthalate (wt~) 0.5 30 10 10
.
Adipic Acid Polyester (wt%) . _ _ _
~, . _ __
~ Carbon Fibers
: PAN Chopped Strand (wt~) 15 15 2 50
_ _.- - .
:: Electromagnetic Wave
Shielding Effect ~dB) 12 40 5~ 55
: _ 2
Tensile Strength (kg~mm ) 4.5 2.74.4 1.6
;~ : _ . _. _ . _.
: ~ Bending Strength (kgjmm ) 6.5 4.56.5 2.3
: Pro- ~ . . _
Bending Modulus of : 2
perty Elasticity (kg/mm 3 300 220 230 280
~ ._
Izod Impact Strength (kg-cm/cm) 12 22 24 10
~ ', _
Vicat Softening:Point (C)95 50 75 75
_ _ . . ___
. . .
~ - 29 -
The properties of the molded products set
for-th in Tables 1 and 2 and throughout the other
Examples and Comparative Examples were determined by
the following test methods.
(1) Electromagneti~ Wave Shielding E~fect:
Using the tester for the determination of
electromagnetic wave shielding effect as shown
in the appended drawing, the effects of respective
molded articles were determined through the
DENKA method. In detail, a plastics molded article
2 was mounted in a shield box 1 so that the tested
article 2 traversed the box 1 to separate the
latter into two sections, a high frequency wave
:
~ emitter antenna 3 being contained in one section
:~ 15 and a receiver antenna 4 being contained in the
other section~ The hlgh frequency wave emitter
-; antenna 3 was connected to a tracking generator
6 which was energized to generate high frequency
. ~: wave of a predetermined voltage. The wave passing
: 20 through the:traversing article 2 was received by
. the receiver antenna 4. The voltage of the wave
passing through the article 2 and received by.the
:; receiver antenna 4 ~as compared with the voltage
of the wave emitted from the emitter antenna 3
to determine the electromagnetic wave shielding
efect of the article 2.
~:
; ~ - 30 -
::
.
~;26~
(2) Tensile S-trength:
Tensile strengths of respective molded articles
were determined generally in accordance with the
JIS K 6871 Method.
(3) Bending Strength & Bending Modulus of Elasticity:
These values were determined generally in
accordance wi-th the ASTM D-790 Method.
(4) Izod Impact Streng-th(with Notch):
Izod impact strengths of respective molded
articles were determined generally in accordance
with the JIS K-6871 Method.
(5) Vicat Softening Point:
Vicat softening points of respective molded
articles were determined generally in accordance
with the JIS K-7206 Method.
Examples 15 to 29
The powder-form ABS resin(acrylonitrile/
butadiene/styrene copolymer resin) as used in Example
1 and the bead-form AS resin (acrylonitrile/styrene
copolymer resin) as used ln Example 1 were used. The
same plasticizer and the same carbon fibers as used in
:
~xample 1 were used.
At the carbon black used as the one available
r/~e,~
from Cabot Corp. under the "VULCAN XC-72"
which had a Dsp oil absorption of about 180 cm /100 g,
an N2 specific surface area of about 180 m2/g and a
:
:::: :
~, - 31 -
. .
",, ~, ,
'
particle size of about 30 ~m. An alkyl amine antistatic
agent avallable from Kao Soap Co., Ltd. under the Trade-
~d~r~
"ELECTRO STRIPPER-EA" was used as the antistatic
agent.
Each of the compositions set forth in Table 3
was further added with an antioxidant and zinc stearate,
and put into a Bumbury's mixer heated to 140C to be
melted and kneaded. Immediately after the temperature
o~ the kneaded mixture reached 190C, the mixture
was discharged from the mixer and rolled between mixing
rollers into a sheet, which was cooled and then crushed
; into pellets~
; The pellets were charged in a hopper of an
8-once injection machine to be melted in -the
plasticiæing cylinder of the machine, and the molten
ma~s was injected into a mold.
The mold was provided with a 2 mm~ direct gate
for molding a housing of 15 cm square and having a
wall thickness of 3 mmO
~ The thus molded products had excellent physical
; properties, improved resistance to heat and improved
electromagnetic wave shielding effect, as shown in Table
3.
, ~ ~ Examples 30 to 34
Each of the compositions as set forth in
Table 4 was pelletizsd in accordance with the procedures
3~ -
' , -
:: :
:
.
~:~6(~ 3..~
similar to Example 1, and charged in a hopper of an
extruder having a cylinder of 40 mm in diameter (L/D - 24)
to be melted in the cylinder. The molten composition
in the cylinder was then extruded through a die for moldiny
a single layer sheet, the die being maintained at 200C.
The die had a width of 600 mm and a lip gap of
3.5 mm. As the result of extrusion, a single layer
sheet having a thickness of 3 mm was formed.
The thus formed single layer she0t had excellent
physical properties, improved resistance to heat and
improved electromagnetic wave shielding efect, as shown
in Table 4.
Examples 35 and 36
A powder-form MBS resin (methacrylonitrile/
butadiene/styrene copolymer resin) composed of 50 wt%
of methacrylonitri~e, 10 wt~ of butadiene and 40 wt%
of styrene was used in place of the powder-form
acrylonitrile/butadiene/styrene copolymer resin used in
Example 1. The compositions as set forth in Table 4
~were pelletized generally following to the procedures
as described in Example 1. Injection molded products
were produced from the thus prepared`pelletsO The
properties of the molded products wexe tested to reveal
~ that they had improved~physical properties, improved
~ ~ 25 resistance to heat and improved electromagnetic wave
shielding effect.
- 33 -::
' ' ' ' .
:
~IL26~
Example 37
A pellet-Eorm ABS resin (acrylonitrile/butadiene/
styrene copolymer resin) composed oE 20 wt% of
acrylonitrile, 20 wt% of butadiene and 60 wt~ of styrene
was used. The composition as set forth in Table 4 was
pelletized generally following to the procedures as
described in Example 1. An injection molded product
was formed from the pellets and subjected to tests.
The tesults of the tests revealed that the molded
product had improved physical properties, improved
resistance to heat and improved electromagnetic wave
shielding effect.
.
~ Comparative Examples 5 and 6
::
Generally following to the procedures as
descrlbed in Example 1, injection molded products were
produced from the compositions as set forth in Table 4,
one composition containing the plasticizer in an amount
less than the range defined in the appended claim~ whereas
the other composition containing the plasticizer in an
amount more than the defined range. The properties of
the injection molded products are shown in Table 4~
: : .
~ As shown, the product of Comparative Example 5 is inferior
:
in electromagnetic wave shielding effect due to inadequate
dispersion of carbon fibers, and the product of Comparative
Example 6 is inferior in resistance to heat due to
excessively high content of plasticizer.
- 34 -
.~ '
., , . " . . . ~ ,, ~. .
~.
.
::
.
Compa.rative Examples 7 and 8
Generally following to the procedures as
described in Example 1, injection molded products were
produced from the compositions as set forth in Table 4,
one composition containing carbon fibers in an amount
- less khan the range defined in the appended claims
whereas the other composition containing carbon fibers
in an amount more than the defined range. The properties
of the injection molded products are shown in Table 4.
As shown, the product of Comparative Example 7 has an
inferior electromagnetic wave shielding effect, whereas
the product of Comparative Example 8 has a low impact
strength.
::
/
:
~. /
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:~ /
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, - 35 -
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~ - 37 -
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-- 38 -
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Example 38
Molded products were produced similarly to
Example 15 while using the same resins, the same carbon
black and the same antistatic agent. However, the length,
diameter and bundle count of the used carbon fibers w~re
varied as shown in Table 5. The properties of the molded
products were tested similarly to the preceding Examples.
The results are shown in Table 5~
.
/
~ /
/-- _
:
~ ~ - 40 -
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., '`.
;
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_ _ _ __ _ _
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~ -- 4 2
`; ~ . :,
~
Example 39 ~Run Nos. 1 to 8)
The same resins and the same carbon fibers as
used in Example 1 were used with a tetrabromobisphenol-A
~ en
available from Teijin Kasei Limited under the ~de
Plamc "FIREGUARD 2000", as a halogen-containing flame
retarderl and antimony trioxide produced by Nippon
Mining Company Limited, as an auxiliary flame-retarding
agent.
Further added as a flame-retarding plasticizer
of phosphoric acid derivative was tricresyl phosphate
produced by Daihachi Kagaku K.K.~
The compositions set forth in the following
Table 6 were further added with an antioxidant, a
stabilizer made of tribasic lead and ~inc stearate, and
put into a Bumbury's mixer heated to 140C to be melted
and kneaded. Each of the kneaded mixture was discharged
from the mixer after the temperature thereof reached
190C, and xolled immediately between mixing rollers
to form a sheet, which was cooled and then crushed into
~ pellets.
; ~ The pelléts~were charged in a h ~ er of an 8-ounce
injection molding machine to be injected into a mold for
molding a housing of 15 cm square and having a wall
thickness of 3 mm, the~ mold being provided with a direct
gate having a diameter of 2 mm~
` As shown in Tàble 6, the thus molded products
~ .
~ 3 -
:: :
. .
.
" ' : ` '
.8~
were improved in physical properties, resistance to heat
and electromagnetic wave shielding eEfect, as well.
Example 39 (Run No. 9)
The composit.ion as set forth in T.able 6 was
pelletized similarly to Run No. 1 of Example 39, and
the pellets were charged in a hopper of an extruder
having a cylinder of 40 ~n in diameter (L/D = 24) to
be melted and extruded through a die for forming a
single layer sheet, the die being maintained at 200C.
The die had a width of 600 mm and the lip gap
was adjusted to 3 5 mm. As the result, a single layer
sheet having a thickness of 3 mm was formed.
As shown in Table 6, the thus produced single
layer sheet had excellent physical properties, improved
lS resistance to heat and .improved electromagnetic wave
shielding effect.
Exam le 39 (Run Nos. 10 and 11
P
A powder-form MBS resin ~methacrylonitrile/
butadiene/styrene copolymer resin) composed of 50 wt%
of methacrylonitrile, 10 wt% of butadiene and 40 wt% of
styrene was used in place of the powder-form ABS copolymer
resin used in Run Nos. 7 and B. The compositions as set
:forth in Table 6 were pelletized similarly to Run No. 1
~; ~ of Example 39, and injection molded products were
;: : 25 produced using the thus prepared pellets..... The results of
: ~ tests showed that the molded products. had excellent
:
~ 4~ -
.
:
physical properties, improved resistance to heat and
improved electromagnetic wave shieldiny effect.
Example 39 (Run No. 12)
A pellet-form ABS resin (acrylonitrile/
butadiene/styrene copolymer resin) composed of 20 wt~
of acrylonitrile, 20 wt% of butadiene and 60 wt%
of styrene was used. The composi-tion set forth in
Table 6 was pelletized similarly to Run No. 1 of
Example 39, and an injection molded product was produced
using the thus prepared pellets. The results of tests
showed that the molded product had excellent physical
properties, improved resistance to heat and improved
electromagnetic wave shielding effect.
Example 39 (Run No. 13)
A composition similar ~o that of Run No. 2
of Example 39 except in that 2-ethylhexyldiphenyl~
phosphate was used in place of tricresyl phosphate~
was pelletized generally following to the procedures as
described in Example 17 An injection molded product
was produced using the thus prepared pellets, ~nd
sub~ected to tests. The results of the tests showed
that the molded product had excellent physical properties,
improved resistance to heat and improved electromagnetic
wave shielding effect.
: .
:: :
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o I ~1 ~ I ~ In n ~ t )
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-- 46 --
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_ _ . _ _.
a~ u ) In CO Ltl 0~ CO
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_ __............ _ _
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~D ~ U~ ~D ~ ~ t~
_ _ _ _ _ _ __
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_ _
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_ __ _ __ _
o o o o o n T
~ ~ u~ n ~ co ~
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O . . O CO O O~1
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_ _ __ ~ ~ _~ ..
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~ ~ ~ ~ ~ ~
~ ~ IJ l0 ,1 ~ ~
0 U~ V~ 3 U Id C:l t~
O ~ ~ ~ ~-~ ~ ~1
h ~ r l ~~ U~ H !~
~ ~ - 1 ~1~ d 1
0 ~1 Ul ~ . ~ 1 ~ ~1 11
~ ~ ~ ~ ~ ~ O ~` .
-1 ~)~J N ~: 0 ~1
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~ ~ o
:. ~ ~L h
_ _ _ _
-- 47 --
~:
.
... , `
.. ;. : .
. .
The properties of the molded product shown
in Table 6 and other Tables were determined by the
following test methods.
(1) Thermal Deformation Temperature:
The temperature was determined generally
in accordance with the JIS K-7207 Method (Load-
Flexture Temperature Determination Test for Rigid
Plastics).
(2) UL~94 Combustion Test:
The test was conducted generally in accordance
with the UL-94 Vertical Combustion Test Method.
(3) Oxygen Index:
The oxygen index was determined generally
in accordance with the JIS K-7201 Method.
Example 40 (Run Nos. 1 to 83
Used as the resinous components were a powder-
form ABS resin (acrylonitrile/butadiene/styrene copolymer
resin) composed of l0 wt% of acrylonitrile, 50 wt~ of
butadiene and 40 wt% of styrene, and a head-form AS
resin (acrylonitrile/st~rene copolymer resin) composed
of 30 wt~ of acrylonitrile and 70 wt% of styrene. Further
added as an ethylene/propylene terpolymer was an
ethylene/propylene/dicyclopentadiene resin produced
and sold by Mitsui Petrochemical Industries, L d. under
-~e~
the ~A~-N~ "EPT-#lQ45".
Used as the carbon fibers were carbonized
~': : :
; - 48 -
~,;
,, ,
.
: : ~ ' '
: ,
~ , , ,, ~ - ,
pOlyacrylonitrile chopped strands having a fiber length of
6 mm, a fiber diameter of 7~ and a boundle count of 12,000
and available from Toho Rayon Co., Ltd. under the Trade~
*~ "BESFIGHT HTAC6S". A tetrabromobisphenol-~ available
~o c~e ~r~
from Teijin Kasei Limited under the ~ e~e "FIREGUARD
2000" was used as a halogen-containing organic flame
retarder, and antimony trioxide available from Nippon
Mining Company, Limited was used as an auxiliary flame-
retarding agent.
The compositions as set forth in Table 7 were
further added with an antioxidant, a stabilizer made
of tribasic lead and zinc stearate, and the mixtures
were put in a Bumbury's mixer heated to 140C. Each
of the compositions was discharged from the mixer after
the temperature thereof reached 190C, and processed
immediately through mixing rollers to form a sheett
which was cooled and then crushed inko pellets.
The pellets were charged in a hopper of an
8-ounce injection molding machine to be injected into
a mold for molding a housing of 15 cm square and having
:: ,
: a wall thickness of 3 mm~ the mold being provided with
a direct gate having a port diameter of 2 mm~.
The thus molded products were excellent in
:
mechanical properties, and improved in resistance
2S to heat and electromagnetic wave shielding effectt as
, ~:
: welI.
49 -
- .
:~ :
'' . .
Example 40 (Run Nos. 9 to 11)
The compositions as set forth in Table 7 were
pelletized similarly to ~un No. l of Example 40, and the
thus prepared pellets were charged in a hopper of an
extruder having a 40 mm diameter cylinder (L/D = 24~ to
be melted and then extruded through a die for forming
a single layer sheet, the die being maintained at 200C.
The die had a width of 600 mm and the lip gap
was adjusted to 3.5 mm. By pasing the molten mass through
the die,, a single layer sheet having a thickness of 3 mm
was formed.
As shown in Table 7, the formed single layer
sheets were excellent in mechanical properties and
resistance to heat and improved in flame-retarding
property and electromagnetic wave shielding effect.
Example 40 (Run Nos. l2 and 13~
~ A powder-form MBS resin (methacrylonitrile/
butadienejstyrene copolymer resin) composed of 50 wt%
of methacrylonitrile, 10 wt% of butadiene and 40 wt% of
.
styrene was used in place of the powder-form acrylonitrile/
butadiene/styrene copolymer resin used in Run No. l of
' Example 40. The compositions as set forth 'in Table 7
were pelletized similarly to Run NoO'l of Example 40,
:
and injection molded products were produced from the
thus prepared pellets. The test results of the molded
~products showed that they were exceIlent in physical
50 -
~ " ~
:. .
properties, resistance to heat, flame-retarding property
and electromagnetic wave shielding efEect.
Exam le 40 (Run No 14)
P
A pellet-form ABS resin (acrylonitrile/
butadiene/styrene copolymer resin~ composed of 20 wt~
of acrylonitrile, 20 wt~ of butadiene and 60 wt%
of styrene was used to prepare the compos~tion shown
in Table 7. The composition was pelletized similarly
to Run NoO 1 of Example 40 and then molded to form
an injection molded product. The properties of the
molded product were tested to find that it had high me~ical
strengths~ excellent resistance to heat, improved flame-
ratarding property and improved electromagnetic wave
shielding effect.
~
An ethylene/propylene/ethylidenenorbornene
terpolymer resin available from Mitsui Petrochemical
r/~deiJ~
Industries, Ltd. under the ~h-~e-~fme "EPT~#3045" was
used in place of the ethylene/propylene/dicyclopentadiene~
20~ terpolymer resin used in Run No. 1 of Example 40. The
compositions as se~forth in Table 7 were pelletized
similarly to Run No. l of Example 40 and then molded
to form injection molded products. The properties of the
molded products were tested to find that they had high
mechanical strengths, excellent resistance to heat,
: : .: :
improved flame-retarding property ~nd improved electro-
- 51 -
.~,
.
, ~
: . , . :.
, ~: :
`
... . :.
~26~
magnetic wave shielding effect.
Comparative Examples 9_and 10
Injection molded products were produced from
the compositions as set forth in Table 8 generally
following to the procedures as dPscribed in Run No. 1
of Example 40, one composition containing an ethylene/
propylene/dicyclopentadiene terpolymer resin in an amount
less than the range defined in the claims whereas the
other composition containing the same terpolymer resin
in an amount of more than the defined range.
The resul-ts of tests for determining the
properties of the molded products are shown in Table 8.
; Comparative Examples 11 and 12
Injection molded products were produced from
the compositions as set forth in Table 8 generally
following ~o the procedures as described in Run No. 1
of Example 40, one composition containing carbon fibers
in an amount of less than the range defined in the
claims whereas the other composition containing the
carbon fibers in an amount of more than the defined
range.
The results of tests for determining the
properties o~ the molded products are shown in Table 8.
:
The ethylene/propylene/DCPD resin appearing
in Tables 7 and 8 means a terpolymer of ethylene,
`
~ propylene and dicyclopentadiene, and the ethylene/
: ~ : :
- 52 -
: ~ :
; ~ .
,
:..... ~ :
~6~ .a
propylene/ENB resin appeaxing in the same Tables mean a
terpolymer of ethylene, propylene and ethylidenenorbornene.
/
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Example 41 (Run Nos. 1 to 6~
-
Used as the res.in components were a powder-
form ABS resin (acrylonitrile/butadiene/styrene copolymer
resinl composed of 10 wt% of acrylonitrile, 50 wt~ of
butadiene and 40 wt~ of styrene, and a bead-form AS resin
(acrylonitrile/styrene copolymer resin) composed of
30 w-t~ of acrylonitrile and 70 wt~ of styrene. The used
plasticizer was a tricresyl phosphate available from
Daihachi Xagaku K.X., and the used conductive filler
was the nic~el-plated carbonized polyacrylonitrile
chopped strands having a fiber length of 6 mm~ a fiber
diameter of 7~ and a bundle count of 12,000, available
from Toho Rayon Co., Ltd. under the ~radc Ma~c "BESFIGHT
M.C.".
l part by weight of an antioxidant and 1 part
by weight of zinc stearate were added to lO0 parts by
weight of the resinous components of each composition
to prepare each of the compositions set forth in Table 9.
Each of the compositions was put in a Bumbury's mix~r
heated to 140C to be mixed and kneaded. After the
temperature of the mixture reached 190C, the mixture
was discharged from the mlxer and then immedîately rolled
through mixing rollers to form a sheet, which was cooled
and then crushed into peLlets.
~ The pellets were charged in a hopper of an
~ 8-ounce injection molding machine to be melted and
: `- :
~ - 58 -
,, .
.
-then injected into a mold for molding a housing of 15 cm
square and having a wall thickness of 3 mm, the mold being
provided with a direct gate having a port diameter of
2 mm~.
The thus molded products had excellent physical
properties, improved electromagnetic wave shielding
effect, excellent resistance to heat and good appearance.
Example 41 (Run Nos. 7 and 8)
The compositions as set forth in Table 9 were
pelletized similarly to Run No. 1 of Example 41, and
the pellets were charged in a hopper of an extruder
having a cylinder o 65 mm in diameter (L/D = 25) to
be melted and then extruded through a die for forming
a single layer sheet.
The die had a width of 600 mm and the lip gap
was adjusted to 3.5 mm. By passing the molten mass
through the die, a single layer sheet having a thickness
of 3 mm was produced. ~
The thus formed single layer sheets had
excellent physical properties, improved electromagnetic
wave shielding effect, excellent resistance to heat and
good appearance~ as shown in Table 9.
Example 41 (Run Nos. 9 and lO)
A powder-form MBS resin (methacrylonitrile/
butadiene/styrene copolymer resin~ composed of 40 wt~
of methacrylonitrile, 20 wt% of butadiene and 40 wt% of
~- - 5g ~
'
~- v,~
- '
,
styrene was used in place of the powder-form acrylonitrile/
butadiene/styrene copolymer resin used in Example 41
Run Nos. 1 and 2 to prepare the compositions as set forth
in Table 9. The compositions were pelletized similarly
to Run No. 1 of Example 41, and injection molded products
were produced from the pellets. Test results rsvealed
that the molded products had excellent physical properties,
excellent resistance to heat, improved electromagnetic
wave shielding effect and good appearance.
Example 41_(Run No. 11)
A pellet-form ABS resin (acrylonitrile/butadiene~
styrene copolymer resin) composed of 20 wt% of acrylonitrile,
20 wt% of butadie~e and 60 wt~ of styrene was used
to prepare the composition as set forth in Table 9.
The composition was pelletized similarly to Run No. 1
of Example 41, and an injection molded prodoct was
produced from the pellets. The test results revealed
that the molded product had excellent physical properties,
excellent resistance to heat, improved electromagnetic
wave shielding efect and good appearance.
Example 41 (Run No. 12~
;~ As shown in Table 9/ copper-plated carbon fibers
were used in place of the conductive filler as used in
Run No. 1 of Example 41. An injection molded product
was produced from the composition generally following
to the procedures as described in Run No. 1 of Example 41.
- 60 -
: ,
~ ` . .: ' ' `: `
The test results revealed that the molded product
had excellent physical properties, excellent resistance
to heat, improved electromagnetic wave shielding effect
and good appearance.
S Exam le 41 (Run Nos. 13 and 14)
P _ .
In~ection mo~ded products were produced
similarly to Run No. 1 of Example 41, except in that
dioctylphthalate (DOP) produced by Daihachi Kagaku
K.K. was used in place oE the plasticizer used in Run No. 1
of Example 41. The compositions are shown in Table 9.
The test results revealed that the molded products had
excellent physical properties, excellent resistance to
heat, improved electromagnetic wave shielding effect
and good appearance.
Comparative Examples 13 and 14
Injection molded products were produced
similarly to Run No. 1 of Example 41, except in that
one composition contained Ni-plated carbon fibers in an
amount of less than the defined range whereas the other
composition contained the Ni-plated carbon fiber~ in an
: amount of more than the defined range, as shown in
Table 10.
The properties o the injection molded products
are shown in Table 10.
~; 25 Compa~ative Example 15
: An injection molded product was produced
: ~
~ - 61 -
s.imilarly to Run No. 1 of Example 41, except in that
brass fibers available from Aisin Seiki Co., Ltd. under
the -~r~a~-~ame "AISIN METAL FIBER' were used in place
of the conductive filler used in Run No. 1 of Example 41.
The properties of the injec~ion molded product
are shown in Table 10.
/
/
: /
: :
- 62 -
: .
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