Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
7~3
FIELD OF THE INVENTION AND RELATES ART ST~TEMENT
This invention relates to a polyamide resin
co~position with an excellent impact resistarlce,
particularly that at low temperature, and thermal
5 resistance as well as a low level of anisotropy of
mechanical properties. More particularly, it relates to a
polyamide resin composition which comprises (a) a polyamide
resin, (b) a polyphenylene ether type resin and (c) a
hydrogenated block copolymer type elastomer which is a
copolymer comprising a vinyl aromatic compound polymer
block A and an olefinic compound polymer block B, the
degree of unsaturation of the block B not exceeding 20~.
The composition can be used in a wide field including the
field of materials for automative, electric, electronic,
and mechanical industry.
Although polyamide resins have excellent
mechanical properties, chemical resistance, abrasion
resistance etc., they are poor in impact resistance,
particularly that at low temperature. Accordingly, they
are restricted as to their field of applications.
Various compositions have been proposed to
obviate the above-mentioned drawback. Compositions
incorporated with elastomers have been disclosed (Japanese
Patent Application Kokoku (Post-Exam. Publn.) No.
11,941/85, published March 29, 1985, Japanese Patent
Application Kokai (Laid-Open) Nos. 7,443/83 and 56,451/84,
published January 17, 1983 and March 31, 1~8~,
respectively), but they have a drawback of being poor in
impact strength at low temperatures. Further, they have
another drawback of decreased thermal resistance owiny to
the-incorporation of elastomars.
Japanese Patent Application KGkai (Laid-Open)
No. 49~753/81, published May 6, 1981 discloses a
composition which comprises 100 parts by weight of a resin
(I) consisting of 5 to 95~ by weight of polyphenylene
oxide and 95 to 5% by weight of polyamide, 5 to 100 parts
by weight of a rubber-like substance (II), and 0.01 to 50
parts by weight of a compound having in the molecule
simultaneously (a) a carbon-carbon double bond or a carbon-
carbon triple bond, and (b) a carboxylic acid group, acid
anhydride group, acid amide group, imido group, carboxylic
ester group, epoxy group, amino group or hydroxyl group
and which undergoes no phase separation in molding and is
excellent in solvent resistance and impact strength and is
hence of high practical value. However, the composition
is unsatisfactory in low temperature impact resistance.
U.S. Patent No. 4,315,086 discloses a
composition excellent in solvent resistance and impact
resistance which comprises 100 parts by weight of a resin
(I) consisting of 5 to 95% by weight of polyphenylene oxide
and 95 to 5% by weight of polyamide, and 0.01 to 30 parts
by weight of at least one substance selected from (A)
liquid diene polymers, (B) epoxy compounds, and (C)
compounds having simultaneously (a) an ethylenic carbon-
-- 2
~ ~9~
1 carbon double bond or a carbon-carbon tripple hond and (b)
a carboxylic acid ~roup, acid anhydride group, acid arnide
group, imido grollp, carbo~ylic ester group, amino gro-lp or
hydroxyl group, but it has an unsatisfactory low
S temperature impact strength.
U.S. Patent No. 4,421,892 discloses a composi~
tion excellent in thermal resistance and impact strength
which comprises 5 to 95~ by weight of an aromatic
polyether type resin, 0.5 to 90% by weight of a copolymer
containing as its components a styrene type compound and
an ~ unsaturated dicarboxylic acid anhydride, 1 to 90%
by weight of polyamide, and 0 to 80% by weight of an
impact strength reinforcing material. However, this
composition is not excellent in low temperature impact
strength and is also unsatisfactory in thermal resistance.
U.S. Patent No. 4,600,741 discloses a composi-
tion excellent in chemical resistance and impact resist-
ance which comprises a polyphenylene ether resin, a
polyamide resin, and a polyphenylene ether resin modified
with an acyl compound comprising (i) a structure oE the
o
general formulas (X-C-t, wherein X denotes F, Cl, Br, I,
or OH, and/or O-C-R, wherein R denotes a hydrogen atom,
alkyl radical, or aryl radical, and (ii) one member
selected from a carboxylic acid, acid anhydride, acid
amide, carboxylic ester, amine, and hydroxyl group, said
(i) and (ii) being covalent-bonded through a divalent
.. ..
~, .
~ ~i9~7~
1 hydrocarbon radical. However, even when the co~position
is further incorporatecl with lmpact resistance improving
agents such as natural rubber, polybutadiene, butadiene/
styrene copolymer, and hydrogenated butadiene/styrene
copolymer, the resulting composition is still unsatis-
factory in low temperature impact resistance
Among compositions comprising polyphenylene
ether resin and polyamide resin, Noryl GTX ~a trade name,
mfd. by General Electric Co.) is commercially availabe as
a material for automobile outer panels. The features of
this PPE/PA type polymer alloy is described in Plastic
Age, No. 2, 160 - 163 ~1986). Noryl GTX 910 has an impact
strength at -30C of about 13 kg-cm/cm and a thermal
resistance, as expressed in terms of heat distortion tem-
perature (4.6 kg/cm2 load), of 190C. The alloy assumesa form wherein PPE is micro-dispersed in the continuous
phase of PA, and comprises an utterly incompatible
microdispersions when judged from the determination of its
dynamic viscoelasticity. As to the details of its phase
structure, it is described in the Proceedings, p 53 - 58
(Jan. 1987), of Tokai Symposium on "Material Characteri-
zation and Material Design~ sponsored by the Tokai Branch
of The Soc. of Polymer Science, Japan that it assumes a
state featured by, so to call it, a sea-island-lake-like
structure wherein PPE is dispersed in the continuous phase
of PA and further rubber is dispersed in said PPE, and the
dispersed particles of PPE have mostly a particle diameter
of 2 to 4 ~m.
r~2~j97~
1 ~he present inventors have previously found, as
a composition of polyamide resin excellent in irnpact
stren~th and rigidity, a composition characterized by
comprising (A) not less than 10~, by weight and not more
than 35~ by weight of at least one copolymer selected from
the group consisting of styrene type hydrocarbon polymer
block - conjugated diene type elastomer block copolymers
and styrene type hydrocarbon polymer block - olein type
elastomer block copolymers, ~B) not less than 2% by weight
and not more than the percentage by weight of (A) of a
maleic anhydride-modified polyphenylene ether type resin,
and (C) not less than 30~ by weight and not more than 88
by weight of a polyamide resin [Japanese Patent Appli-
cation Kokai (Laid-Open) No. 204,262/86]. ~owever, when
the above-mentioned composition is processed by conven-
tional forming methods such as injection molding, the
resulting formed articles show so called anisotropy of
mechanical properties, a phenomenon wherein mechanical
properties differ markedly between the direction or resin
flow and the direction perpendicular to the former.
Accordingly, in practical applications, the composition is
restricted as to forming methods and uses.
In recent years, requirements for improving the
impact resistance of polyamide resin have increased
further as the resin has come to be more widely used.
Impact resistance is usually expressed in terms of Izod
impact strength. When polyamide resin is use singly, its
Izod impact strength is several to about 10 kg-cm~cm (with
- 5 -
. .
. '' ~ .
~,, , ~ .
:,
- . ' ;
:. . ..... -- - ...
~LX~ t~
1 notcn; determined under an absolute dry condi~ion) at 23C
and decreases down to 2 to 3 kg~cm/cm or less ~It lower
temperatures. ~ccordingly, the field oE appl~cation of
the resin alone is subject to limitation.
5 OBJECT AND SUMMARY OF THE INVENTION
The object of this invention is to improve the
impact resistance of polyamide resin. More particularly,
it is to provide a polyamide resin composition which has
an improved low temperature impact resistance while
retaining a high level of thermal resistance and which
shows a low-level of anisotropy oE mechanical properties
when formed or molded.
After extensive studies conducted to obtain such
an improved resin composition, the present inventors have
found a novel polyamide resin composition which can answer
the object of this invention.
Thus, this invention relates, in one aspect, to
an impact-resistant polyamide resin composition which
comprises
(a) a polyamide resin (hereinafter abbreviated as PA),
(b) â polyphenylene ether type resin (hereinafter
abbreviated âS PPE), and
(c) a hydrogenated block copolymer type elastomer
(hereinafter abbreviated as TPE) which is a copolymer
containing a vinyl aromatic compound polymer block A and
an olefinic compound polymer block B, the degree of
unsaturation of the block B not exceeding 20~,
.
,
., , .. ~
',
~97~7~
l the diame~er of the dispersed phase of PPE dispersed in
the said composition being 0.6 ~m or less, and the
insoluble portion of the composition remaining ~fter
extraction thereof with formic acid ollowed by chloroform
being 20~ by welght or more relative to the total amount
of PPE and TPE present in the composition.
In another aspect, this invention relates to a
process for producing an impact-resistant polyamide resin
composition comprising
(a) a polyamide resin,
(b) a polyphenylene ether type resin, and
(c) a hydrogenated block copolymer type elastomer which is
a copolymer containing a vinyl aromatic compound polymer
block A ar,d an olefinic compound polymer block B, the
degree of unsaturation of the block B not exceeding 20%,
the diameter of the dispersed phase of PPE dispersed in
the said composition being 0.6 ~m or less, and
the insoluble portion of the composition remaining after
extraction thereof with formic acid followed by chloroform
being 20~ by weight or more relative to the total amount
of PPE.and TPE present in the composition
which process comprises melt kneading a polyphenylene
ether type resin obtained by reacting, in the presence of
: a radical producing agent, a 1,2-substituted olefinic
compound having an acid anhydride structure with a polymer
obtained by oxidative polymerization of at least one
phenolic compound represented by the general formula
~ : .
7~3
R~ ~R5
R2 Rl
R1, R2, R3, R4 and R5 are, independently, a
hydrogen atom, nalogen atom, or substituted or unsubsti~
tuted hydrocarbon group, provided that at least one of
them must be hydrogen,
a hydrogenated block copolymer type elastomer obtained by
reacting, in the presence of a radical producing agent, a
1,2-substituted olefinic compound having an acid anhydride
structure with a hydrogenated block copolymer which is a
copolymer containing a vinyl aromatic compound polymer
block A and an olefinic compound polymer block B, the
degree of unsaturation of the said block B not exceeding
20%, and
a polyamide resin.
BRIEF DESCRIPTION OF THE DRAWINGS
Figs. l to 3 and 5 to 13 are electron
photomicrographs oE the compositions of Examples of this
invention and Comparative Examples which have been stained
with osmium tetroxide. Deeply stained portions are
dispersed phases of PPEt whereas white, not stained
portions are the dispersed pnase of TPE. Portions with
scattered micro dots are PA phases.
Fig.4 is an electron photomicrograph of the
- 8 -
~ .
.. , ~
~ 7~
1 composi`tion of Comparative Example 4 which has been
stained with osmium tetroxide lightly and then Wittl
ruthenium tetroxide. Deeply stained portions are
dispersed phase o 'rPE; white, not stained portions are
S the dispersed phases of PPE; and lightly stained portions
are PA phases.
- DESCRIPTION OF THE PREFERRED EM~ODIMENT
The polyamide resins which can be used in this
invention include polycondensation products o a
dicarboxylic acid with a diamine, polycondensation
products of an ~-aminocarboxylic acid, and ring opening
polymerization products of a cyclic lactam. As specific
examples thereof, there may be mentioned aliphatic
polyamides such as nylon 6, nylon 4,6, nylon 6,6, nylon
6,10, nylon 11, and nylon 12; aliphatic-aromatic poly-
amides such as poly(hexamethylene terephthalamide),
poly(hexamethylene isophthalamide), and poly(tetramethyl-
ene isophthalamide); and the copolymers and mixture
thereof.
The polyphenylene ether type resin used in this
invention is a polymer obtained by the oxidative polymeri-
zation of at least one phenolic compound represented by
the general formula
.. ,., -
:. :
~.. :.- :.. :........... ..
, .., ", ......
37~
R ~ l~5
2 Rl
n Rl, R2, R3, R4 and R5 are, independently, a
hydrogen atom, halogen atom, or substituted or unsubsti-
tuted hydrocarbon group, provided that at least one of
them must be hydrogen. That is, said polymer may include
any of the products obtainable by oxidative polymeri ation
of phenolic compounds.
SpecifiC examples of Rl, R2, R3, R4 and R5 in
the above general formula include hydrogen, chlorine,
fluorine, bromine, iodine, methyl, ethyl, propyl, butyl,
chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxy-
methyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl,
; phenyl, chlorophenyl, methylphenyl, dimethylphenyl, and
ethylphenyl.
Specific examples of the compound represented by
the above general formula include phenol, o-, m- or
p-cresol, 2,6-, 2,5-, 2,4- and 3,5-dimethylphenol,
2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethyl-
phenol, 2-methyl-6-ethylphenol, and 2,3,5-, 2,3,6- and
2,4,6~trimethylphenol. These phenolic compounds may also
be used in combinations of two or more kinds thereof.
The phenolic compounds of the above general
formula may also be copolymerized with phenolic compounds
other than those of the said formula, such as bisphenol A,
-- 10 --
~, ,
- ~ :
~ '7~
l tetrabromobisphenol A, resorcinol, and hydroquinone.
It is well known that polymers oE phenolic
compound can be obtained by oxi~atively polymerizing the
compound by means of oxygen or an oxygen-containing gas
using an oxidative coupling catalyst. For example,
polymers can be obtained by reacting phenolic compounds
with oxygen in the presence of a copper or manganese
complex.
Further~ there can also be used a graft
copolymer obtained by grafting a styrene type compound to
the above-mentioned phenolic compound polymer. Examples
of the styrene type compound include styrene, ~-methyl-
styrene, methylstyrene, vinyltoluene, and chlorostyrene.
Further, to improve processability, styrene type
polymers may be added within a range not detrimental to
the mechanical properties of the product. As specific
examples of such styrene type polymers, there may be
mentioned styrene homopolymer; rubber-modified polystyrene
resins using various kinds of rubbers, for example,
polystyrene modified with butadiene type rubber (of
various content of microstructures), polystyrene modified
with acrylic rubber, polystyrene modified with ethylene-
propylene copolymer, polystyrene modified with ethylene-
propylene-diene copolymer rubber, and polystyrene modified
with butadiene-styrene rubber; styrene-acrylonitrile
copolymer, butadiene-styrene-acrylonitrile copolymer
(so-called ABS resin), butadiene-styrene-methyl methacry-
late copolymer, and styrene-ethylene copolymer.
..~' .
,~
7~
1 The hydrogenated block copolymer type e:lastolner
used in this invention is a hydroyenated block A copol~mer
containing a vinyl aromatic compound polymer block A and
an olefinic compound polymer block B, the degree of
unsaturation of the block B not exceeding 20%.
The hydrogenated block copolymer containing a
vinyl aromatic compound polymer block A and an olefinic
compound polymer block B, used in this invention, is
obtained by selective hydrogenation of t'ne conjugated
diene portions of a block copolymer containing a vinyl
aromatic compound polymer block and a conjugated diene
type compound polymer block.
Among the above-mentioned block copolymer
; containing a vinyl aromatic compound polymer block and a
conjugated diene type compound polymer block, there may be
mentioned a linear ~lock copolymer represented by the
formulas (X~Y)n, (X-Y-X')n, X-~ Y-X-Y-t-nX, or X-t-Y-x tnY
(n is an integer from 1 to 10) which is a copolymer
consisting of a vinyl aromatic compound polymer blocks (X)
and (X') and a conjugated diene type compound polymer
block (Y) (X and X' may be the same or di~ferent), and a
radial block copolymer represented by the general formulas
[(Y-~) ] ~2Z' [(X~Y)n ~ 2Z' [(Y~X)n~Y ]m+2Z
[(X-Y)n-X ~ z (wherein X, Y and n are as defined above;
m is an integer from 1 to 4 and Z is the residue of a
coupling agent such as silicon tetrachloride and tin
tetrachloride or that of an initiator such as a polyfunc-
tional organolithium compound).
~ ' . ' ' , .
.. ~
., . ~'............... .....
7~
1Typical examples of vinyl aromatic compounds
used herein include styrene, ~-methylstyrene, vinylxylene,
ethylvinylxylene, vinylnaphthalene, and the mixtures
thereof. These of conjugated d.iene type compounds include
butadiene, isoprene, 1,3-pentadiene, 2,3-diethylbutadiene,
and the mixtures thereof.
The terminal blocks of these block copolymers
may be the same or different from each other.
The number average molecular weight of these
block copolymers is 10,000 to 800,000, preferably 20,000
to 500,000.
The content of the vinyl aromatic compound in
these block copolymers is preferably 10 to 70% by weight,
more preferably 10 to 55% by weight.
15The hydrogenated block copolymer used in this
invention is obtained by selective hydrogenation of the
conjugated diene portion of the above-mentioned block
; copolymer. For example, a hydrogenated block copolymer
wherein not more than 20~ of the aromatic double bonds in
the vinyl aromatic compound polymer block and at least 80%
of the aliphatic double bonds in the conjugated diene
compound polymer block have been hydrogenated can be
obtained by hydrogenating the above-mentioned block
ccpolymer according to the method described in Japanese
Patent Application Rokoku (Post-Exam. Publn.) No; 8704/67,
published September 10, 1986.
The ~degree of unsaturation of block B~ referred
to in this invention means the proportion of carbon-carbon
double bonds contained in the block B, and is usually in a
- 13 -
. ~ ~
: . , . ' ' ' ,:
, :: .. ,: . : .. :
, .: , ...
': .' ' .
1 range not e~ceeding 20Q~. It can be deter~ined by instru-
mental analysis such as nuclear magnetic resonance method
and infrared absorption spectroscopy, and chemcial
analysis such as idodometric titration.
These hydrogenated block copolymers can be used
each alone or as a mixture of two or more thereof.
In the resin composition of this invention, the
compounding ratio is not specifically limited so long as
it is a composition comprising polyamide, PPE anD TPE, the
diameter of dispersed phase of PPE dispersed in the said
composition being 0.6 ~m or less and the insoluble portion
of the composition after extraction thereof with formic
acid followed by chloroform being 20~ by weight or more.
More preferably, the content of polyamide resin
is in the range of 45 to 75% by weight. A content of less
than 40% by weight is unfavorable because sometimes it
leads to a low thermal resistance. A content exceeding
75% by weight is unfavorable because sometimes it results
in the decrease of low temperature impact strength.
The content of PPE is more preferably in the
range of 5 to 40~ by weight. A content of less than 5~ by
weight is unfavorable because it results in the decrease
of low temperature impact strength. A content exceeding
40% by weight is unfaovrable because it leads to the
decrease of thermal stability in molding.
The content of TPE is more preferably in the
range of 10 to 30~ by weight. A content of less than 10%
by weight is unfavorable because it results in the
- 14 -
: : .
, . ::. ,
: .
. . .~ ~ - :.,
.. ..
~ ~ 9~
1 decrease of low temperature impact strength. A content
e~ceeding 30~ by weight is unfavorable becau.se lt results
in a low thermal resistance.
The morphology of the composition of this
invention can be examined by observing with a transmission
electron microscope an ultrathin slice of the composition
stained and fixed by means of osmium tetroxide and/or
ruthenium tetroxide. In the morphology of the composition
of this invention, PA forms a continuous pnase, whereas
PPE and TPE form dispersed phases. More particularly, for
example in case of nylon 6,6, the main structure of
dispersed phases involve such phase structures as a TPE
dispersed phase enveloping PPE, a TPE dispersed phase
enveloping PPE and PA, and a TPE dispersed phase envelop-
lS ing PA; and in case of nylon 6 they invo~ve a TPE
dispersed phase enveloping PPE and PA, and a dispersed
phase of PPE alone. The PPE dispersed phases range in
their size from a very finely dispersed phase to a
dispersed phase reaching several ~m in diameter.
As to the diameter of the PPE dispersed phase of
the composition according to this invention, it is
preferable that most of the PPE dispersed phases have a
diameter of 0.6 ~m or less. A diameter of less than 0.01
~m, namely so fine a dispersion is to make observation
with an electron microscope virtually impossible even at amagnification of 10,000, is unfavorable because it leads
to the decrease of low temperature impact strength. On
the other hand, when the number of particles larger than
- 15 -
'. ' ~ ' ." . ' .
~. . .
.~ , .. . .. .
l 0.6 ~m is large, it leads to the decrease o~ low
temperature impact strength and is hence unfavorable.
The diameter of the PPE dispersed phase is
measured with an electron photomicrograph taken at a
magnification of lO,000. ~hen the phase is elliptic, the
length of its major axis (~) and that of the minor axis
(~) (defined herein as the distance between the points at
which a perpendicular line drawn through the center of the
major axis intersects the ellipsoid) were determined, and
a value D calculated from the equation D ~ (~ + ~)/2 is
taken as the diameter of the dispersed phase.
The insoluble portion of the composition of this
invention remaining after extraction thereof with formic
acid followed by chloroform is preferably 20% by weight or
more relative to the total amount of PPE and TPE in the
composition. Further, from the viewpoint of practical
molding processability, it is not more than 150% by
weight. An insoluble proportion of less than 20% by
weight is unfavorable ~ecause it leads to the decrease of
low temperature impact strength and/or to anisotropy of
mechanical properties of formed articles.
The insoluble portion is determined in the
following manner. A formed article is pulverized mechani-
cally to give powders having a particle diameter of about
0.5 mm or less. After l g of the powdery composition is
weighed accurately, and mixed with 50 ml of 39~ formic
acid. The mixture is stirred at room temperature (20 to
25C) for 5 hours, filtered through a glass filter to
- 16 -
;, '. ~ . .
.. - . .. ~ - .
~ 7~7~
1 separate insoluble matter, which is then washed with
formic acid, water and acetone, and then dried. The
insoluble matter is then mixed with 50 ml o~ chloroform,
and the mixture is stirred at room temperature (20 to
25C) for 17 hours, and then filtered throu~h a glass
filter to separate insoluble matter, which is washed with
chloroform and methylene chloride, dried and then
weighed The amount of PPE and TPE in the composition can
be determined by first calculating the amount of polyamide
from the amount of nitrogen in the composition obtained by
elemental analysis and then by substraction. If addi-
tives are contained in the composition they are removed
before the calculation of the polyamide amount.
The characteristics of the present composition
lS lies in the state of the dispersion of each said component
(a), (b) and (c) and the insoluble portion of the composi-
tion remaining after the extraction while a polyamide
resin, a polyphenylene ether resin and an elastomer of a
hydrogenated block copolymer are employed. The above-
mentioned characteristics are attained firstly byemploying the present process mentioned hereinafter which
is entirely different from that of the conventional one.
Although the detailed physico-chemical mechanism
showing the excellent effect in the present invention is
not clear, it is believed that it can be attained by the
process of the present invention that the dispersed state
of the present composition is not a mere mixture of PA,
- 17 -
,~
. .-- ~ -.
.... .
~ - ',. ~; '.
~9t7,~,~
1 PPE alld rrpE~ but the :Eormation of a stable dispersioll of
PPE and TPE in the PA phase which may have been clerived
rom a strong interactlon between them which has never been
known, whereby a smaller particle size of PPE ~pecified as
in this invention can be formed therein; and that a higher
content of said insoluble portion can be attained as a
result of employing the present process.
The resin composition of this invention may be
incorporated, at optional steps of its production and
molding, with other ingredients including pigments, dyes,
reinforcing materials, fillers, thermal stabilizers,
antioxidants, weather proofing agents, nucleating agents,
lubricant, plasticizers, antistatic agents, and other
polymers within a range not detrimental to its moldability
and mechanical properties.
A preferred process for producing the resin
composition of this invention comprises melt-kneading a
polyphenylene ether type resin obtained by reacting, in
the presence of a radical producing agent, a 1,2-substi-
tuted olefinic compound having an acid anhydride structurewith a polyrner obtained by oxidative polymerization of at
least one phenolic cornpound represented by the general
formula
.
- 18 -
"
'
7~7~
R~ R 5
R2 Rl
1 wherein Rl, R2, R3, R4 and R5 arer independentlyr a
hydrogen atom, halogen atom, or substituted or unsubsti-
tuted hydrocarbon group, provided that at least one of
them must be hydrogen; a hydrogenated block copolymer type
elastomer obtained by reacting, in the presence o a radi-
cal producing agent, a 1,2-substituted olefinic compound
having an acid anhydride structure with a hydrogenated
block copolymer which is a copolymer containing a vinyl
aromatic compound polymer block A and an olefinic compound
polymer block B, the degree of unsaturation of the said
block B not exceeding 20%; and a polyamide resin. Another
process may also be used which comprises melt-kneading
optional two components preliminarily and then
melt-kneading the remaining component therewith.
As specific examples o 1,2-substituted olefinic
compounds having a carboxylic acid group, acid anhydride
group, or epoxy group, there may be mentioned maleic
anhydride, maleic acid, itaconic anhydride, fumaric acid,
methylnadic anhydride, dichloromaleic anhydride, acrylic
acid, methacrylic acid, and glycidyl methacrylate.
The radical producing agents usuable in this
invention include organic peroxides and diazo compounds
known to the art. As speciic examples thereof, mention
: -- 19 --
'
: -.; ~ , .-:
: , ~;
.. ,. ,
1 may be made o~ ben~oyl peroxide, dicumyl peroxide, t-buty:L
hydropero~ide, cumene hydroperoxide, and aæobisisobutyro-
nitrile. These radical producing agents may also be used
in a combination of two or more kinds thereof.
In executing the present invention, the poly-
phenylene ether type resin to be used is not specifically
limited as to the method of its production. For example,
the following methods can be used.
(1) a method which comprises adding a 1,2-substituted
olefinic compound having a carboxylic acid group, acid
anhydride group, or epoxy group to a solution containing
the polymer of a phenolic compound in the presence of a
radical producing agent and stirring the resulting mixture
at 50 to 200C for several ten minutes to several hours.
(2) a method which comprises making the reaction compo-
nents contact with one another by melt-kneading them in a
system containing substantially no solvent or a small
amount of solvent.
Method (1) is favorably adopted if the necessary
reaction apparatus and purification apparatus are already
in hand. Method (2) has advantages in that the rnodifi-
cation of the polymer can be performed with inexpensive
equipment such as a general purpose twin screw extruder
and in a short time without the need of steps of solvent
removal and polymer purification.
More preferably, a method is adapted which
comprises reacting 0.05 to 15 parts by weight, preferably
0.1 to 7 parts by weight, of a 1,2-substituted olefinic
- 20 -
,' :
. ,
}~
1 compound having an acid anhydri.de steucture with 100 parts
by weight of the polymer of a phenolic compound in ~he
presence of 0.05 to 5 parts by weight, preferably 0.1 to 3
parts by weight, o a eadical producing a~ent in the tem-
perature range o 200 to 350C, preferably 220 to 330C.
As specific examples of a 1~2-substituted
olefinic compound having a carboxylic acid group or acid
anhydride geoup used in the reaction with the hydrogenated
block copolymer, there may be mentioned maleic anhydride,
maleic acid, itaconic anhydride, fumaric acid, methylnadic
anhydride, dichloromaleic anhydride, acrylic acid, and
methacrylic acid.
As to the radical producing agent employed for
the reaction o~ the above-mentioned block copolymer with
the above-mentioned 1,2-substituted olefinic compound,
there may be used benzoyl peroxide, dicumyl peroxide,
t-butyl hydroperoxide, cumene hydroperoxide, azobisiso-
butyronitrile, and the like. These radical producing
agents may also be used in a combination of two or more
thereof.
Although no particular limitation is placed as
to the method of preparing the hydrogenated block
copolymer type elastomer used in this invention, those
methods are not preferable in which the resulting
elastomer has a markedly increased melt viscosity and
hence a poor processability. A preferred method comprises
reacting a hydrogenated block copolymer with an unsatu-
rated carboxylic acid anhydride or with an unsaturated
- 21 -
. .:
' ' .
~2 ~
1 carboxylic acid in the presence oE a radical lnitiator in
an e~truder.
The amount of the 1,2-substituted olefinic
compound having a carboxylic acid group or an acid
anhydride group added to the hydrogenated block copolymer
is preferably 0.05 to 10 parts by weight, more preferably
0.1 to 5 parts by weight, relative to 100 parts by weight
of the hydrogenated block copolymer. When the added
amount is less than 0.05~ by weight, the resulting polymer
is poor in the effect expected for modified hydrogenated
block copolymer, and cannot give a satisfactory impact
resistance when compounded into a final composition. At
an added amount exceeding 10% by weight, further increase
in the effect of modification is scarecely observed as
compared with products of smaller added amount.
As typical examples of melt-kneading apparatus
which can be used in this invention, mention may be made
of extruders, mixing rolls, Banbury mixture, and
kneaders. Particularly preferable in this invention is
the method of kneading using a twin screw extruder. The
kneading temperature, though depending also on the melting
temperature of component resins, is preferably 220 to
350C for kneading a mixture wherein no polyamide resin is
contained, and is a temperature ranging from the melting
point of polyamide resin to a temperature of 100C higher
than its melting point for kneading a mixture wherein
polyamide resin is contained.
The composition of this invention can be
- 22 -
.-.~
... ... ..
:: :
~ 7~
1 processed by known methods of Eorming yenerally used eor
thermoplastic resins, for example injection molding,
extrusion, flo~ molding and vacuum forming.
EFFECT OF THE INVENTION
Products obtained by simply mixing by mechanical
means such polymers incompatible with one another as PA
resin, a phenolic compound polymer, and a block copolymer
which is a copolymer containing a vinyl aromatic compound
polymer block A and an olefinic compound polymer block 3,
; lO the degree of unsaturation of the block B not exceeding
20%, do not form a dispersed phase, or even when they form
a dispersed phase, they give rise to macroscopic phase
separation in moldins; or even when such phenomena do not
occur, they are very brittle.
Since the polyphenylene ether type resin used in
this invention is a product obtained by reacting a 1,2-
substituted olefinic compound having a carboxylic acid
group, acid anhydride group, or epoxy group with a
phenolic compound polymer, it can form, in the final resin
composition, dispersed phases wherein amount all of the
particles are present as fine particles of 0.6 ~m or less.
Also, since the block copolymer type elastomer
: used in this invention is a product obtained by reacting a
1,2-substituted olefinic compound having a carboxylic acid
group or acid anhydride group with the above-mentioned
block copolymer, it can form dispersed phases in the
composition.
:~2S;~7~
1 Further, in the polyphenylene ether ~ype resin
and the block copolymer type el~stomer, which are polymecs
to which a 1,2-substituted olefinic compound having a
carboxylic acid group, acid anhydride group, or epoxy
group has been reacted, it is considered that the double
bond moiety of the olefinic compound has undergone
grafting to leave a polar group, namely carboxylic acid
group, acid anhydride group or epoxy group, bonded to the
main chain of PPE and TPE. It is estimated that the
above-mentioned polar group reacts with the terminal amino
group or carboxylic acid group of PA and the amido group
present in its main chain, whereby the PP2 dispersed phase
and TPE dispersed phase are stabilized. Further, it is
estimated that said reaction results in the increase of
insoluble portion remaining after extraction with formic
acid, a solvent for PA, and with chloroform, a solvent for
PPE and TPE, thereby to give a composition which has an
insoluble portion of 20~ by weight or more and is of
excellent mechanical properties and low anisotropy thereof.
Example
This invention will be further described below
with reference to Examples in order to be more clearly
understood. However, the scope of this invention is not
limited to these Examples. In the Examples, all ~parts~
are part by weight.
- 24 -
~ 7
l Example l
(l) Preparation of maleic anhydride mocli~ied polyphen~-
l~ne ether type resin
Poly(2,6-dimethylphenylene-1,4-ether) with a
number average polymeeization degree of 140, di-t-butyl
peroxide, and maleic anhydride were dry-blended in a
weight ratio of 100/l/5 at room temperature. ~y means of
a twin screw extruder with vent of reverse rotation type,
a screw diameter of 30 mm and L/D of 30, the blend was
melted under conditions of a cylinder temperature of 300C
and a screw rotating speed of 75 rpm, then extruded at a
residence time of l minute, passed through a cooling bath,
and then pelletized. A 0.05 g portion of the pellet was
formed into film of about 15 ~m thickness by the use of
chloroform. The film was then heated with ethanol under
reflux in a Soxhlet's extractor for 10 hours. It was then
dried and used as the sample for infrared spectrophoto-
metry. The presence of the -CO2- structure in the
sample originating from the reaction with maleic anhydride
was confirmed from the analysis of the absorption peak of
1700 ~ l~00 cm l in the infrared absorption spectrum.
(2) Preparation of maleic anhydride-modified hydrogenated
block copolymer
A uniform mixture of 100 parts by weight of a
hydrogenated block copolymer (Kraton G1652, mfd. by Shell
Chemical Co.; styrene content; 29~; SEBS-typer S denoting
styrene and EB denoting ethylene butylene), 1.2 parts by
weight of maleic anhydride, and 0.3 part by weight of
- 25 -
'' ' .
,' . :
: -,
-
1 ~ ~9~7~
1 Perhexa (a trade name oE a peroxide, mfd. b~ Nippo~l Oil &Fat Co., Ltd.) was fed to a twin screw extruder (screw
diameter 45 mm; L/D: 33; with vent) and subjected to
maleic acid addition reaction at a cylinder temperature oE
260C while unreacted rnaleic anhydride was being removed
by suction through the vent hole. The resulting modified
hydrogenated block copolymer was dried by heating it under
reduced pressure and analyzed to show an addition amount
of maleic anhydride of 0.6% by weight. The addition
amount of maleic anhydride was determined by titration
with sodium methylate.
(3) Preparation of composition
A mixture of 50 parts of nylon 6,~ ILeona 1300S,
mfd. by Asahi Chemical Industry Co., Ltd.), 25 parts of
the maleic anhydride-modified polyphenylene ether type
resin obtained in (1) above, and 25 parts of the maleic
anhydride-modified hydrogenated block copolymer obtained
in (2) above was extruded through a twin screw extruder
(screw diameter: ~5 mm, L/D: 33) set at 300C, then passed
through a cooling bath, and pelletized. The pellets were
dried at 80C for 8 hours under reduced pressure an~ then
injection-molded under the following conditions to obtain
molded pieces for determination of their properties.
- 26 -
,
.. . . ~ . . .. . . . . . . . . . . .. .. .. . .. .... , . .. . . . . . ~ . . . . . .
~'
" .
: . ,:
~ '7~
1 Injection moldin~ machine 1 oz.
Cylinder temperature 290C
Injection pressure 700 kg/cm2
Injection time lS seconds
Cooling time 20 seconds
~old temperature 80C
(4) Determination of properties
Thermal resistance: A 1/8" thick test piece was
used to determine its heat distortion temperature at 4.6
kg/cm2 load under an absolte dry condition according to
ASTM D 648.
Impact resistance: Izod impact strength was
determined by using a 1/8" thick test piece with notch at
room temperature (23C) and under an absolute dry
condition according to AST~ D 256.
Low temperature impact resistance: Izod impact
strength at -30C was determined by using a 1/8" thick
test piece with notch.
Rigidity: Flexural modulus was determined by
using a 1/8" thick test piece under absolute dry condition
according to AS~M D790-80.
Anisotropy of mechanical properties: A test
piece having a notch in the direction of resin flow cut
from the gate part and a test piece having a notch in the
direction perpendicular to resin flow cut from the central
part were prepared from flat plates of 12 x 8 cm and 1/8"
: thickness. I~od impact strength was determined according
- 27 -
'..'
.. . .. . . . . ..... ... . . . . .. .... . .. ..... .. .. .. .. . . .. . .... . . . .
.. . .. :, ~ . . .
~ ~i9 7
1 to ASTM D 256 with the test pieces under an absolute dr,~
condition. The anisotropy of mechanical propertles was
defined in terms of the ratio of the impact strength at
the gate part to that at the central part and calculated
by the following equation.
Aniso~ropy of mechanical properties
Impact strength at gate part _ x 100 (~)
Impact strength at central part
The results of these determinations are shown in
Table 1. It can be seen that the composition has remark-
ably excellent impact strength not only at room
temperature but also at -30C, and has also excellent
thermal resistance; further it has ve-ry well balanced
mechanical properties, the anisotropy of mechanical
properties being 91%.
Figs. 1 and 2 are transmission electron
photomicrographs of molded articles. The photograph of
Fig. 2 shows the morphology of a molded article formed
after residence in an injection machine at 310C for 10
minutes. Though the dispersed phases of elastomer are in
an agglomerated states, the PPE dispersed phase do not
form agglomeration and most of the dispersed phases are
about 0.5 ~m or less in size; the number of dispersed
phases larger than 0.6 ~m was found to be only one. The
impact strength at 23C of the said molded article
subjected to 10 minutes of residence is 55 kg-cm/cm, a
- 28 -
.
..
...
: ,
l property oE a considerably high level, reveali.ng that the
composition shows remarkably excellent residence stability
in molding machines.
comparative ~xample l
s The properties of the nylon 6,6 resin used in
Example l are shown in Table l.
Comparative Example 2
The procedures of Example 1 were repeated by
using a hydrogenated block copolymer (Kraton Gl652, mfd.
by Shell Chemical Co.) in place of the maleic anhydride-
modified hydrogenated block copolymer used in Example l.
The results, shown in Table l, reveals that the resulting
composition is very poor in anisotropy of mechanical
properties. Fig. 3 shows the electron photomicrograph of
the composition.
Comparative Example, 3
The procedures of Example l were repeated except
that unmodified polyphenylene ether was used in place of
the maleic anhydride-modified polyphenylene ether used in
Example l, and the results obtained are shown in Table l.
The resulting composition shows low values both in low
temperature impact strength and thermal resistance. The
electron photomicrograph of the composition is shown in
Fig. 4.
- 29 -
' ~ ;
.... .
. . .~ . ~
~ 97
1 Comparatlve Example 4
Under the same conditions as in Example 1, a
mixture of 50 parts of nylon 6,6 (Leona 1300 S, mfd. by
~sahi Chemical Industry Co., Ltd.), 25 parts oE poly-
(2,6-dimethylphenylene-1,4-ether) having a number average
polymerization degree of 140, 25 parts of a hydrogenated
block copolymer (Kraton G1652, mfd. by Shell Chemical Co.)
and 1 part of maleic anhydride was melt-kneaded and injec-
tion-molded to determine their properties. The results
are shown in Table 1. The electron photomicrograh of the
resulting composition is shown in Fig. 5.
Comparative Example 5
The procedures of Comparative Example 4 were
repeated except that 0.3 part of di-t-butyl peroxide was
further added to the formulation of Comparative Example
4. The results obtained are shown in Table 1. The
electron photomicrograph of the resulting composition is
shown in Fig. 6.
- 30 -
-
.. ..
' '. ' ~
. . . . . ...
-. -"
.
37~7~3
~ o _ _ __ _ _ _ _,
'~a~ ~o
~ C~
o X
C~ ~
__ _
*
~ o Ln U~ ~ ~ o
,~n1
~o
,_1 C s s ~ ~ ~ e 1 dP
Q :~
E~ . . _ _
~ 00 .
~ ,a~ O x
~ 4~ ~ /
,1 '~ ~ 4~ ~ ~
0 4 h O O O
~; o a~ E~ `~ ~ u~ ~1 0
I S S ~ C~ ~ ~ ~ 'O ~
a~ v .L) a) o oa) ~ s 4-1 0
~ ~ a~ ~ ~ ~ ~ .L~ ~ ~--
.,, .,, ~ ~ .,, a~ c o
a~ ~ ~ ~ ~ ~ ,, ,~
~:1 C C ~'C5 ~ ~ (~ O S E~
~, ~ o ~ a) a~~ .-, u~ u~ t~
S ~ ~ S V V ~: ~ ~ ~ +
s:: ~ ~ c ~~ ~ c a~ ,~ ~a
c c ~ c ~ a~ ~a) ~ P~
a~ al a) ~ ~a ,~ o~ :~ (3 ~
V .C C V ~~ :~ C~_~ ~ 1 r~ 4
1 ~r1 Ql Ql~r-l O O r-l .~1 X ~1 rc O ro _
o al ~1 ~ al ~ ~ ~ o ~1) o _LJ U~
,~ ,~ ~ ~ ,~ ~a ~a Ql ,~ ~ ~ ~ c c
~1 a~ o o (~~ o (a ~) la P I H 11~
æ ~ ~ ~ s ~ O _ P~ ~ _
~ 31 --
.. ~ . -
: . -' .:
- : .
:
:;:
~ti97~7
_ __
L~ ~ o o
o
a~
_ _ ._
~ CO C~ o
In O a~ ~'
s~
o e e c, N~ v~
V V o ~ dP
~ :~: ~ U~
_ _ .
~O ra
o ta ~ u,
~1) 4 ~ aJ
Q~ X U~
~ ~ ~_ ~i
11:~ (1~ ~_1
US ~
O
S <IJ V h
~ C J.~ C) Ll V
O a~ u~ a~ JJ ~ Q
~1 h ~ ~ ~ a E~
J- V o_ ~1 ::1
U~ 07 ~ ~ 4~ ~ r
.LJ ~; ~:1 O O.U
~) .LJ h V O ~ ~JI
C.) O O~ E~ ::~ H ~::
1~1 a~ ~L) ~ ~--a~ ~-1
~ ~4 U U~ ~ ~ O h *
E~ ~ ~ ,~ ~ h Ul
~1 o ~_1 o ~ U~ h J~
,., . ~ O .,, a
I ~~r X u~ .~ ~ ~
o o ~ ~ a) ~ O O
N J~) N ~J C) .--1 ~ a) N Z
H IIS H ~J ~! E4 A Q~
_ .
! 3 ~
.~
~.. ~- . "`
:- ~ :. ::: , : .
, . ` ` ~ .
': - `::
:-`: . ::
" ~ . ` :
37~8
,~, , -~ _ . __ _ _~
I~,E u~ N ~I ~r C)
1~ o 1~ ~ ~1 .
~ LO ~ ~ O O
0 t)li~ . .
~ . _ _ . E _
E~ ~ ~ o L~ u~ . r-
~ :. ~ ~
o ~ U~ . L~
E ~- m
tjJ~
_ Ul - __
'~C ~ ~ '
_ ___ ._ O 0
E-~ ~1 ~7 ~
,_, ~-1 ~ ~` ~a, ',
_ . c ~Ei
n ~o ~ o ~ ~
. 1~ ~7 ~ ~ rl ~
`~
-
3 4 --
.. .. ..
, : . :: ~.
~ 7~7
1 Examples 2 to 10
Compositlons were prepared from mixtures
comprising the three components, used in Ex~mple 1, in
proportions shown in Table 2, and their properties are
shown in Table 2.
Compositions were obtained which were remarkably
excellent in impact strength, particularly that at -30C,
and also excellent in thermal resistance and of low level
of anisotropy of mechanical properties.
The test pieces obtained by molding the composi-
tions of Examples 4, 6 and 9 after residence of 10 minutes
at 310C in an injection machine showed considerably high
values of Izod impact strength at 23C of 77, 73 and 65
kg-cm/cm, respectively, revealing also their resistance
stability in molding machines.
Flgs 7 to 11 show the electron photcmicro-
graphs of the compositions of Examples 2, 3, 4, 7 and 9,
respectively.
Comparative Examples 6 and 7
Compositions were obtained by melt-kneading, by
extrusion, mixtures comprising the three components, used
in Example 1, in proportions shown in Table 2. Their
properties are shown in Table 2.
The compositions of Comparative Examples 6 and 7
are both excellent in thermal resistance but show low Izod
impact stren~th at -30C. Further, when they are retained
in an injection molding machine at 310C, increase of
. ,, ; , ~
'''~. '' "
.. "" ~ '' , .
~X~ 7~7~
1 their viscosity is observed after 5 minutes and injection
molding becomes impossihle after 10 minutes oE residence.
Fig. 12 shows the electron photomicrograph oE
the composition of Comparative Example 6.
- 36 -
.. .
.. .: .~ : -~
. ~ -
.- -
- - ~-- - - - -~ - -
I
a u~ o L~ ~ ~ ~ 9 o o
~ ~ ~ ~ ~ ~ ~ ~ ~o o
~ ~1 ,~ ~ ~
-- . -- - ~ -- -
o u~ u~ ~ r~ o~ r- o o
~r ~ ~ v~l ~ ~ ~ ~ o
~0 In
~ D ~ 1: 1~ dP ~
E~ _ _. _
_
~ o
a
~C
4~ ,aJ~ ~ ~ \ ~ ~
~1 . o ~1 C) E~ 5: !
~ ~ U O O O _ C~ C ~
v a) o ~I)~Ll Ll ~:1 a~ ~ u~
~ O ~,_1 L~ ~J O 11~ L~ ~ ~' 3
.,, ,, ~ a) tl~c ~ 1 E~ L) .L) O ^ ,_
~ aJ 4 E3 ~a ,~ ~ u~ u~ ,-~ ~ :~
~c ~ ~ ~ a) + v v v E~ ~0
~o '~ ~ .~ v ~a ~c P~ a v ~
c ~ c a~ q :~ ~ ~ ~ ~oo u~ ~ a
t~ O ~ O ~ O ~ .~ ~1 0 '~ ~ L~
C ~ ,1 o~1 ~v u~ ~l ~ . 5
o a) ~ aJ ~ v Q, ~ c~ ":1 ~ I V ~r x
~1 ~ r-l ~--1 ~Ll U~ H t~S O O ilS ~
~ ~15 0 (T5 ~ 1~ ~,1 C~ N V ~ ~1
Z C~ ,C _ H J~ 5 _ _
-- 37 -
7~7
_ ~ ~
o
Cr~
C
_ s
V
V dP ,~ _
_
Q (:~ ~I
x a)
~ ~ aJ
V V V ~
._~ ~ C O
a)
~ V
.c v a
C) ~ V
~ SV S Z
~U ~ L~
O
u~ ~ a) ~ *
Q~ a) v ~
O-,~ U~ V
~ v ~n
V ~ ..
O ~ O ~
~ N O V
rl O H N O
~: ~ ~ H Z
-- 38 --
.
- . - ': '' . -: '' -
..
:
;
:~ , . .
~i9~
_--o _ ~ ~ _ _ ~ __ _
~ ~D ~ ~ u~.l ~ ~ ~ , o
~ _ _ :3 0 ~ ~ a
a~ o o o ~ o o ~ o c~
X~ ~D ~ ~ ~D. ~ ~ ~ D
:a ___ _ _
a) - _ _ __ _ _ _
~ ~ o o o ~ ~ U:) ~ o
~ Ln ~ ~ ~ ~ ~ ~ ~o o
o ~ __ __ _ ~Co
_ a) o o o ~ ~ r~ _~ o _
~ ~ ~ ~ ~ ~ I~r ~ ~D ~ O
8 o ~ ~
o ~ ~ ~ ~ ~ o
~D ~ ~ In O ~ ~t' O
8~ ~o
, __
~:4 u~ O L~l ~ co ~o ~r o
8 ~ ~ ~
-- 3g --
_ ~` ~ I
_ O
_ ~ J
a~
O
tn
E~
_ r
~n~
U~
.
_ æ
~ ~ _
. CO * ~
-- 4 0
: ,
`, ` .
~, ' '' `',.~ `' ~
... . .
. '`' ' . `
~' ` ~ . `
~'x~ u~ u~ ~ ,,,lv ~ ~ ~r o o u
O (D ~ . _ __
a~ o u~ L~ O ~ ~ ~ ~
o ~n u~ ~ ~ ~ ~ ~ o
a.o Li, ~ ~ ~u~l ~ ~ ~ co o
~; - 41 -
.~
:- ~'.;':. . '
:. ' ,, :~ "
,
,
.: .
3~
'_ ~'
~ U~
~, ~
CL
a~ u~
.~
o
~r
. E
~ .
g
.
4 2 --
-: ' . '" ~ , "~
.. .-.,~,., . . :: .
9~
1 Example 11
A mixture of 50 parts of nylon 6 (Amilan 1017,
md. by Toray Industrials, Inc.) 25 parts of the maleic
anhydride-modiEied polyphenylene ether used in Example 1,
and 25 parts of the maleic anhydride-modified hydrogenated
block copolymer used in Example 1 was extruded through a
twin screw extruder (screw diameter: 45 mm, L/D: 33) set
at 300C, then passed through a cooling bath and
pelletized. The pellets thus obtained were dried at 80C
under reduced pressure and then injection-molded under the
following conditions to obtain test pieces for
determination of their properties.
Injection molding machine 1 oz.
Cylinder temperature 290C
Injection pressure 700 kg/cm2
Injection time 15 seconds
Cooling time 20 seconds
Mold temperature 80C
The results thus obtained are shown in Table 3.
The electron photomicrograph of the composition is shown
in Fig. 13.
Comparative Example 8
The properties of the nylon 6 resin used in
Example 11 is shown in Table 3.
43 -
~, .
37~
o _ _--; o _
o ~, o U
~ ~ l
~x
_ . _
a)
o ~ ~ A I ~ ~ r~ L~ O
U~ ~ ~ U~ ct~ o~ ~ ~ O
~o Ci~
~: ~
_ . __
'c ~ , ~ ~ d~ ~ O C> ~
Q D ~ ~ 1:~)
~; ~
C~
_ . _ _ .
~ 4~ ~ ~ ~ -
.,, -~ o c~ a
O S_~ O O ~ h ~; U ~
a) ~ ~1 0 ~) ~) ~)
I .C I C~ L~ O ~ ~ ~ ~
a) u ~ o ~ u o ~ ~ u,
~ ~ ~ ~ u a) ~ _ ~ ~ _t
r~ ~1 R 2 u~ C O C~ v ~ O ^ ,_~
a~ ~ ~ (~ ,, r-l P~ U~ O~ ~1 ~ :
s:: ~ ~ ~ ~C ~ E~ u ~ ~
~ ~ ~ ~ -1 ~4 Ul C) ~ U 4 O O
,c ~ ~ ~ ~ a~ + c~ v o
~: ~ ~: ~ ~:5 ~ ~ 0 ~ U
,~ ~: ~ ~: a) a) ~ ~_ ~ ~ ~ o~ v
~9 a) a ~ tn ~ ~ ~ ~ C~ ~ o .~J
V ~ V ~ C~ 4 ~1 1:~ .-1 o ~ O ~:5 ~ 4
~::-1 Q. -~ O ~1 0 O ~ ~_ ~ ~ . ::s
Oa) ~ a~ 4 U Q, al -,l rr:) ~ ~ I V ~r X
~-1~1 -1 ~ ~ 4 U~ ~ V O O
~~ O ~a ~ f~ 1--1 ~ N V N U a
Z~' ~ ~ Pl ~ H ~r5 H ~ m
-- -
-- 44 --
', ' :': ~ ' ","
""'`' ' ~ ~' - ..
7~7
d~
_ o
X
~ a) a)
~, V V
. ,~ ~
~ t,
V
s ~5
V ~C
V
o t
u~ ~ a
o~ a) V ~
o-,l m v
~ V o~
o ~ o ~
U~ Ql N O
O ~ C~
C Ll 1-
~
_ ~ J
`~
i -- ~5 --
~ ,. . .
: ~ .
~ .:
I :. .
~ ............ .
7~
l INDUSTRIAL AepLIcABILITy
one feature Oe the composition of this inventionis its excellent impact resistance, particularly an
excellent impact strenyth at low temperature, combined
with excellent thermal resistance.
Another feature of the composition is its low
level of anisotropy of mechanical properties.
Resultantly, the composition can be used in a wide field
of application without being restricted as to forming
techniques and uses.
A further is that the composition is stable even
when retained in molding machines for a long time in
molding. Resultantly, it is suitable also for forming a
large-size articles which require a long residence time.
Further, since a large amount of polyphenylene
ether type resin and of block copolymer type resin, which
are both nonhydroscopic, can be added to polyamide resin
according to the process of this invention, it also
exhibits an effect of decreasing the moisture absorption
of polyamide resin simultaneously with improving the
dimensional stability.
6 -
, ,, ~
: .. '`., :
