U.S. patent application number 17/049750 was filed with the patent office on 2021-08-12 for polyarylene sulfide-based resin composition and insert-molded product.
This patent application is currently assigned to Polyplastics Co., Ltd.. The applicant listed for this patent is Polyplastics Co., Ltd.. Invention is credited to Tatsuya Kanezuka, Katsuhei Ohnishi.
Application Number | 20210246311 17/049750 |
Document ID | / |
Family ID | 1000005596099 |
Filed Date | 2021-08-12 |
United States Patent
Application |
20210246311 |
Kind Code |
A1 |
Ohnishi; Katsuhei ; et
al. |
August 12, 2021 |
POLYARYLENE SULFIDE-BASED RESIN COMPOSITION AND INSERT-MOLDED
PRODUCT
Abstract
A polyarylene sulfide-based resin composition is disclosed
containing a polyarylene sulfide-based resin A, an inorganic filler
B, and olefinic copolymers C and D each having predetermined
structural units, wherein: the inorganic filler B contains a
fibrous inorganic filler B1 having a different diameter ratio of
1.5 or less and a fibrous inorganic filler B2 having a different
diameter ratio of 3.0 or more; a mass ratio B1/B2 of the fibrous
inorganic filler B1 and the fibrous inorganic filler B2 is 0.2 or
more and 5.0 or less; and the contents of the olefinic copolymers C
and D are respectively 3 parts by mass or more and less than 19
parts by mass and 3 parts by mass or more and 30 parts by mass or
less with respect to 100 parts by mass of the polyarylene
sulfide-based resin A.
Inventors: |
Ohnishi; Katsuhei;
(Fuji-shi, JP) ; Kanezuka; Tatsuya; (Fuji-shi,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Polyplastics Co., Ltd. |
Tokyo |
|
JP |
|
|
Assignee: |
Polyplastics Co., Ltd.
Tokyo
JP
|
Family ID: |
1000005596099 |
Appl. No.: |
17/049750 |
Filed: |
April 25, 2019 |
PCT Filed: |
April 25, 2019 |
PCT NO: |
PCT/JP2019/017676 |
371 Date: |
October 22, 2020 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29K 2081/00 20130101;
C08L 81/02 20130101; B29C 45/14336 20130101; C08L 2205/03 20130101;
B29K 2705/00 20130101; B29C 45/2708 20130101; B32B 15/08
20130101 |
International
Class: |
C08L 81/02 20060101
C08L081/02; B32B 15/08 20060101 B32B015/08; B29C 45/14 20060101
B29C045/14; B29C 45/27 20060101 B29C045/27 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 27, 2018 |
JP |
2018-086942 |
Claims
1. A polyarylene sulfide-based resin composition containing a
polyarylene sulfide-based resin A, an inorganic filler B, an
olefinic copolymer C, and an olefinic copolymer D, wherein: the
inorganic filler B contains a fibrous inorganic filler B1 having a
different diameter ratio of 1.5 or less and a fibrous inorganic
filler B2 having a different diameter ratio of 3.0 or more, the
different diameter ratio being a ratio of the long diameter and the
short diameter of a cross section perpendicular to the longitudinal
direction; a mass ratio B1/B2 of the fibrous inorganic filler B1
and the fibrous inorganic filler B2 is 0.2 or more and 5.0 or less;
the olefinic copolymer C contains an .alpha.-olefin-derived
structural unit and an .alpha.,.beta.-unsaturated acid glycidyl
ester-derived structural unit; the olefinic copolymer D contains at
least one olefinic copolymer selected from the group consisting of
an ethylene-.alpha.-olefinic copolymer D1 and an olefinic copolymer
D2 comprising an .alpha.-olefin-derived structural unit and an
.alpha.,.beta.-unsaturated carboxylic acid alkyl ester-derived
structural unit; the content of the olefinic copolymer C is 3 parts
by mass or more and less than 19 parts by mass with respect to 100
parts by mass of the polyarylene sulfide-based resin A; and the
content of the olefinic copolymer D is 3 parts by mass or more and
30 parts by mass or less in total with respect to 100 parts by mass
of the polyarylene sulfide-based resin A.
2. The polyarylene sulfide-based resin composition according to
claim 1, wherein the inorganic filler B further contains a
non-fibrous inorganic filler B3.
3. The polyarylene sulfide-based resin composition according to
claim 1, wherein the total content of the inorganic filler B is 90
parts by mass or more and 220 parts by mass or less with respect to
100 parts by mass of the polyarylene sulfide-based resin A.
4. The polyarylene sulfide-based resin composition according to
claim 2, wherein the content of the fibrous inorganic filler B2 is
20 parts by mass or more with respect to 100 parts by mass of the
polyarylene sulfide-based resin A and the content of the
non-fibrous inorganic filler B3 is 20 parts by mass or more with
respect to 100 parts by mass of the polyarylene sulfide-based resin
A.
5. The polyarylene sulfide-based resin composition according to
claim 2, wherein the non-fibrous inorganic filler B3 has an average
particle diameter of 10 .mu.m or more.
6. An insert-molded product having an insert member formed using a
metal, an alloy, or an inorganic solid and a resin member covering
at least a portion of a surface of the insert member, wherein the
resin member is formed using the polyarylene sulfide-based resin
composition according to claim 1.
7. The insert-molded article according to claim 6, wherein the
resin member has: at least one brittle portion which extends in a
predetermined direction and which comprises one or both of a welded
portion in which flow terminals of the resin composition have been
joined and a stress-concentrating portion in which stress generated
by expansion and contraction concentrates; and a trace of a gate on
a surface that extends in a direction approximately perpendicular
to a direction in which the at least one brittle portion extends.
Description
TECHNICAL FIELD
[0001] The present invention pertains to a polyarylene
sulfide-based resin composition and insert-molded product.
BACKGROUND ART
[0002] Insert-molded products are molded products in which an
insert member comprising metal, an inorganic solid, etc. and a
resin member comprising a thermoplastic resin composition are
integrally molded and are applied to wide fields such as automobile
components, electrical and electronic components, OA equipment
components, etc. However, the thermal expansion coefficients and
contraction coefficients due to temperature changes of the metal,
etc. and thermoplastic resin compositions that constitute
insert-molded products differ greatly, so there are cases of
insert-molded products breaking due to temperature changes during
use. Therefore, insert-molded products require high and low
temperature impact properties (thermal shock resistance).
[0003] Among thermoplastic resins, polyarylene sulfide-based resins
are known as resins with comparatively superior thermal shock
resistance. However, polyarylene sulfide-based resins have poor
toughness and are brittle, so there are cases of thermal shock
resistance falling when the structure of an insert member is
complex and a resin member has portions with large changes in
thickness as in components of, for example, power modules,
reactors, and the like used in hybrid electric vehicles (HEVs) and
when there are large high/low temperature changes in the
environment in which an insert member is used, such as components
around automobile engines. As a method to solve these problems,
there is the technique of blending a fibrous filler having a flat
cross-sectional shape with a polyarylene sulfide-based resin
(Patent Document 1).
[0004] Further, polyarylene sulfide-based resins are crystalline
resins and thus have so-called contraction coefficient anisotropy
in which the contraction coefficient of the resin in a cooling
process differs between the flow direction of the resin and a
direction perpendicular thereto. Due to such contraction
coefficient anisotropy, there are cases of warping and sinking
occurring in obtained insert-molded products and dimensional
accuracy falling. As a method to suppress the occurrence of
sinking, there is the technique of blending a fibrous reinforcing
agent having a flat cross-sectional shape with a substantially
linear polyarylene sulfide resin having a specific Na content and a
resin pH in a specific range (Patent Document 2). [0005] Patent
Document 1: JP 2005-161693 A [0006] Patent Document 2: JP
2006-328291 A
SUMMARY OF INVENTION
Technical Problem
[0007] The present invention addresses the problem of providing a
polyarylene sulfide-based resin composition with excellent thermal
shock resistance, low warpage property, and flowability and an
insert-molded product using the same.
Solution to Problem
[0008] In the research process, the present inventors discovered
that, by combining and blending an olefinic copolymer and, as an
inorganic filler to be blended alongside, fibrous fillers having
respectively predetermined and different diameter ratios that are
different from each other with a polyarylene sulfide-based resin,
superior thermal shock resistance can be maintained even when used
in a resin member of an insert-molded product having a structure in
which thermal shock resistance readily declines and furthermore,
low warpage property can simultaneously be achieved. Additionally,
there are cases in which moldability declines due to flowability of
the resin falling according to the type or combination of inorganic
fillers included in the composition, but the present inventors
found that superior thermal shock resistance can be achieved while
suppressing the decline of flowability of a resin composition by
combining and using a plurality of olefinic copolymers that have
predetermined compositions in the discovered blend of inorganic
fillers, completing the present invention.
[0009] That is, the polyarylene sulfide-based resin composition
according to the present invention contains a polyarylene
sulfide-based resin A, an inorganic filler B, an olefinic copolymer
C, and an olefinic copolymer D, wherein: the inorganic filler B
contains a fibrous inorganic filler B1 having a different diameter
ratio of 1.5 or less and a fibrous inorganic filler B2 having a
different diameter ratio of 3.0 or more, the different diameter
ratio being a ratio of the long diameter and the short diameter of
a cross section perpendicular to the longitudinal direction; a mass
ratio B1/B2 of the fibrous inorganic filler B1 and the fibrous
inorganic filler B2 is 0.2 or more and 5.0 or less; the olefinic
copolymer C contains an .alpha.-olefin-derived structural unit and
an .alpha.,.beta.-unsaturated acid glycidyl ester-derived
structural unit; the olefinic copolymer D contains at least one
olefinic copolymer selected from the group consisting of an
ethylene-.alpha.-olefinic copolymer D1 and an olefinic copolymer D2
containing an .alpha.-olefin-derived structural unit and an
.alpha.,.beta.-unsaturated carboxylic acid alkyl ester-derived
structural unit; the content of the olefinic copolymer C is 3 parts
by mass or more and less than 19 parts by mass with respect to 100
parts by mass of the polyarylene sulfide-based resin A; and the
content of the olefinic copolymer D is 3 parts by mass or more and
30 parts by mass or less in total with respect to 100 parts by mass
of the polyarylene sulfide-based resin A.
[0010] In the present invention, the inorganic filler B preferably
further contains non-fibrous inorganic filler B3. In the present
invention, the total content of the inorganic filler B is more
preferably 90 parts by mass or more and 220 parts by mass or less
with respect to 100 parts by mass of the polyarylene sulfide-based
resin A.
[0011] In the present invention, the content of the fibrous
inorganic filler B2 is preferably 20 parts by mass or more with
respect to 100 parts by mass of the polyarylene sulfide-based resin
A and the content of the non-fibrous inorganic filler B3 is
preferably 20 parts by mass or more with respect to 100 parts by
mass of the polyarylene sulfide-based resin A. The average particle
diameter of the non-fibrous inorganic filler B3 is preferably 10
.mu.m or more.
[0012] The insert-molded product according to the present invention
has an insert member formed using a metal, an alloy, or an
inorganic solid and a resin member covering at least a portion of a
surface of the insert member and the resin member is formed using
the abovementioned polyarylene sulfide-based resin composition.
[0013] In the present invention, the resin member can be configured
so as to have: at least one brittle portion which extends in a
predetermined direction and which comprises one or both of a welded
portion in which flow terminals of the resin composition have been
joined and a stress-concentrating portion in which stress generated
by expansion and contraction concentrates; and a trace of a gate on
a surface that extends in a direction approximately perpendicular
to the direction in which the at least one brittle portion
extends.
Effects of Invention
[0014] According to the present invention, a polyarylene
sulfide-based resin composition with excellent thermal shock
resistance, low warpage property, and flowability and an
insert-molded product using the same can be provided.
BRIEF DESCRIPTION OF DRAWINGS
[0015] FIGS. 1A and 1B schematically show one embodiment of the
insert-molded product, wherein A is a perspective view and B is a
plan view.
[0016] FIG. 2 schematically shows a state in which a welded portion
is formed.
[0017] FIG. 3 is an explanatory drawing of the measurement position
for low warpage property.
DESCRIPTION OF EMBODIMENTS
[0018] An embodiment of the present invention shall be explained in
detail below. The present invention is not limited by the following
embodiment and can be carried out with the addition of appropriate
modifications so long as the effects of the present invention are
not hindered.
[0019] [Polyarylene Sulfide-Based Resin Composition]
[0020] The polyarylene sulfide-based resin composition (hereafter
also simply referred to as "resin composition") is a resin
composition comprising a resin having a polyarylene sulfide-based
resin as a main component. "Having as a main component" means 80%
by mass or more, 85% by mass or more, or 90% by mass or more of the
resin components. The resin composition according to the present
embodiment contains a polyarylene sulfide-based resin A, an
inorganic filler B, an olefinic copolymer C, and an olefinic
copolymer D.
[0021] (Polyarylene Sulfide-Based Resin A)
[0022] The polyarylene sulfide-based resin A is a resin having a
repeating unit indicated by general formula (I) below.
--(Ar--S)-- (I)
(Ar indicates an arylene group.)
[0023] The arylene group is not particularly limited and can
include, for example, a p-phenylene group, an m-phenylene group, an
o-phenylene group, a substituted phenylene group, a
p,p'-diphenylenesulfone group, a p,p'-biphenylene group, a
p,p'-diphenyleneether group, a p-p'-diphenylenecarbonyl group, a
naphthalene group, etc. Among the repeating units indicated by
general formula (I) above, the polyarylene sulfide-based resin A
can, in addition to a homopolymer using identical repeating units,
be made a copolymer comprising heterogeneous repeating units
according to the use.
[0024] As the homopolymer, those having a p-phenylene group as the
arylene group and a p-phenylenesulfide group as the repeating units
are preferred. This is because homopolymers having a
p-phenylenesulfide group as a repeating unit possess extremely high
thermal resistance and display high strength, high toughness, and
furthermore, high dimensional stability in wide temperature ranges.
Molded products having extremely superior physical properties can
be obtained by using such homopolymers.
[0025] Copolymers that have a combination of two or more different
arylene sulfide groups from among arylene sulfide groups including
the abovementioned arylene groups can be used as the copolymer.
Thereamong, combinations comprising a p-phenylene sulfide group and
an m-phenylene sulfide group are preferred from the viewpoint of
obtaining molded products provided with high physical properties
such as thermal resistance, moldability, and mechanical properties.
Polymers comprising 70 mol % or more p-phenylene sulfide groups are
preferable and polymers comprising 80 mol % or more are yet more
preferable. The polyarylene sulfide-based resin A having a
phenylene sulfide group is a polyphenylene sulfide resin (PPS
resin).
[0026] According to general manufacturing methods therefor,
polyarylene sulfide-based resins A having a molecular structure
that is substantially linear and does not have a branched or
cross-linked structure and those with a structure having branches
or cross-linking are known, but a resin of any of these types is
effective in the present embodiment.
[0027] The melt viscosity of the polyarylene sulfide-based resin A
is preferably 5 Pas or more and 50 Pas or less and more preferably
7 Pas or more and 40 Pas or less measured at 310.degree. C. and at
a shear rate of 1,216 sec.sup.-1. When the melt viscosity is 5 Pas
or more and 50 Pas or less, superior thermal shock resistance and
favorable flowability can be maintained.
[0028] The manufacturing method for the polyarylene sulfide-based
resin A is not particularly limited and the resin can be
manufactured with conventionally known manufacturing methods. For
example, the polyarylene sulfide-based resin A can be manufactured
by, after synthesizing a low molecular weight polyarylene
sulfide-based resin A, polymerizing at a high temperature in the
presence of a publicly known polymerization promoter to increase
the molecular weight.
[0029] (Inorganic Filler B)
[0030] The inorganic filler B contains a fibrous inorganic filler
B1 and a fibrous inorganic filler B2 (hereafter also referred to as
"inorganic fillers B1 and B2") having respective predetermined
different diameter ratios that differ from one another.
[0031] "Different diameter ratio" means "the long diameter of a
cross section perpendicular to the longitudinal direction (longest
linear distance of the cross section)/the short diameter of the
cross section (longest linear distance in a direction perpendicular
to the long diameter)". "Fibrous" means a shape with a different
diameter ratio of 1 or more and 10 or less and an average fiber
length (cut length) of 0.01-3 mm. In the present embodiment, the
term "fibrous" is distinguished from "tabular" (a shape with a
different diameter ratio greater than 10 and an aspect ratio of 1
or more and 500 or less) and "particulate" (a shape with a
different diameter ratio of 1 or more and 10 or less and an aspect
ratio of 1 or more and 2 or less), which will be discussed below.
These shapes are all initial shapes (shapes before melt-kneading).
"Aspect ratio" means "longest linear distance in the longitudinal
direction/the short diameter of a cross section perpendicular to
the longitudinal direction (the longest linear distance in a
direction perpendicular to the line with the longest distance in
the cross section)". The different diameter ratio and the aspect
ratio can both be calculated using a scanning electron microscope
and image processing software. Further, manufacturers' values
(numerical values that the manufacturer has published in catalogs,
etc.) can be employed as the average fiber length (cut length).
[0032] The present embodiment contains a combination of a fibrous
inorganic filler B1 having a different diameter ratio of 1.5 or
less and a fibrous inorganic filler B2 having a different diameter
ratio of 3.0 or more. Thereby, even when an insert-molded product
has a structure in which thermal shock resistance readily declines,
an insert-molded product with excellent thermal shock resistance,
excellent low warpage property, and high dimensional precision can
be manufactured.
[0033] (Fibrous Inorganic Filler B1)
[0034] The fibrous inorganic filler B1 is preferably a fibrous
inorganic filler having a different diameter ratio of 1.5 or less,
preferably 1.0 or more and 1.3 or less. By containing an inorganic
filler B1 having such a different diameter ratio, the molding
contraction coefficient and the linear expansion coefficient of an
insert-molded product can be lowered and the mechanical and
physical properties and thermal shock resistance can be improved.
For example, general fibrous inorganic fillers in which the
cross-sectional shape in a direction perpendicular to the
longitudinal direction is round or approximately round can be
raised as the inorganic filler B1.
[0035] The cross-sectional area of the fibrous inorganic filler B1
is preferably 1.times.10.sup.-5 to 1.times.10.sup.-3 mm.sup.2 and
more preferably 2.times.10.sup.-5 to 8.times.10.sup.-3 mm.sup.2 in
terms of further enhancing the ease of manufacturing and
reinforcing effects. The "cross-sectional area" can be considered
to be a value in which, when the longest linear distance of the
cross-section of the fibrous inorganic filler B1 measured using a
scanning electron microscope and image processing software is set
as the long diameter and the shortest linear distance of the
cross-section of the fibrous inorganic filler B1 measured in the
same manner is set as the short diameter, the value of the long
diameter and the short diameter multiplied is further multiplied by
.pi..
[0036] Further, with the objective of lightening the specific
weight of the resin composition, etc., hollow fibers can be used as
the fibrous inorganic filler B1.
[0037] As the fibrous inorganic filler B1, there are mineral fibers
such as glass fibers, carbon fibers, zinc oxide fibers, titanium
oxide fibers, wollastonite, silica fibers, silica-alumina fibers,
zirconia fibers, boron nitride fibers, silicon nitride fibers,
boron fibers, and potassium titanate fibers, metal fibrous
substances such as stainless steel fibers, aluminum fibers,
titanium fibers, copper fibers, and brass fibers, etc. and one or
two or more of these can be used. Among these, glass fibers and
carbon fibers are preferable.
[0038] The fibrous inorganic filler B1 may be surface-treated with
various generally known surface treatment agents such as
epoxy-based compounds, isocyanate-based compounds, silane-based
compounds, titanate-based compounds, and fatty acids. Due to the
surface treatment, adhesion with the polyarylene sulfide-based
resin A can be improved. A surface treatment agent may be applied
to the fibrous inorganic filler B1 in advance before material
preparation to perform a surface treatment or a convergence
treatment or may be added simultaneously during material
preparation.
[0039] The content of the fibrous inorganic filler B1 is preferably
10 parts by mass or more and more preferably 20 parts by mass or
more and 110 parts by mass or less with respect to 100 parts by
mass of the polyarylene sulfide-based resin A in terms of improving
mechanical and physical properties and thermal shock
resistance.
[0040] (Fibrous Inorganic Filler B2)
[0041] The fibrous inorganic filler B2 is a fibrous inorganic
filler in which the different diameter ratio is 3.0 or more,
preferably 3.5 or more, and more preferably 3.8 or more. The upper
limit of the different diameter ratio is 10.0 or less, preferably
8.0 or less, and more preferably 6.0 or less. By comprising an
inorganic filler B2 having such a different diameter ratio, the
anisotropy of the molding contraction coefficient and the linear
expansion coefficient of an insert-molded product can be lowered
and low warpage property, mechanical and physical properties, and
thermal shock resistance can be improved. By combining the fibrous
inorganic filler B2 with the fibrous inorganic filler B1, effects
in which both thermal shock resistance and low warpage property are
established that are superior to those using the fibrous inorganic
filler B1 alone or using the fibrous inorganic filler B1 in
combination with a non-fibrous inorganic filler (for example,
non-fibrous inorganic filler B3 discussed below) and/or another
fibrous inorganic filler (for example, fibrous inorganic filler B4
discussed below) can be obtained.
[0042] Fibrous inorganic fillers having a cross-sectional shape
perpendicular to the longitudinal direction such as an elliptical
shape, an oval shape, a semicircular shape, a cocoon shape, a
rectangular shape, or a shape similar thereto can be raised as the
fibrous inorganic filler B2. A "cocoon shape" is a shape in which
the central vicinity of an oval in the longitudinal direction is
inwardly recessed.
[0043] The cross-sectional area of the fibrous inorganic filler B2
is preferably 1.times.10.sup.-5 to 1.times.10.sup.-3 mm.sup.2 and
more preferably 1.times.10.sup.-4 to 5.times.10.sup.-4 mm.sup.2 in
terms of further enhancing ease of manufacturing and the effects of
the combination with the fibrous inorganic filler B1. The
"cross-sectional area" can be considered a value in which, when the
longest linear distance of the cross-section of the fibrous
inorganic filler B2 measured using a scanning electron microscope
and image processing software is set as the long diameter and the
shortest linear distance of the fibrous inorganic filler B2
measured in the same manner is set as the short diameter, the value
of the long diameter and the short diameter multiplied is further
multiplied by .pi.. The average length of the fibrous inorganic
filler B2 is not particularly limited, but considering the
mechanical and physical properties, the molding processability,
etc. of the molded product, the average fiber length in a molded
product is preferably 50-1000 .mu.m. The "average fiber length" is
as described above. Similar to the fibrous inorganic filler B1,
hollow fibers can also be used as the inorganic filler B2. The
material of and surface treatment performed as necessary on the
fibrous inorganic filler B2 are also the same as for the fibrous
inorganic filler B1 described above and the descriptions are
therefore omitted here.
[0044] The content of the fibrous inorganic filler B2 is preferably
20 parts by mass or more and more preferably 25 parts by mass or
more and 100 parts by mass or less with respect to 100 parts by
mass of the polyarylene sulfide-based resin A in terms of further
improving the thermal shock resistance by further enhancing the
effects of combination with the inorganic filler B1.
[0045] The content ratio of the inorganic fillers B1 and B2 is, as
a mass ratio B1/B2 of the inorganic fillers B1 and B2, 0.2 or more
and 5.0 or less, preferably 0.3 or more and 4.0 or less, more
preferably 0.4 or more and 4.0 or less, and still more preferably
0.4 or more and 3.8 or less. By setting B1/B2 to 0.2 or more and
5.0 or less, a resin composition with both superior thermal shock
resistance and low warping can be obtained.
[0046] (Other Fillers)
[0047] The inorganic filler B can contain other inorganic fillers,
as necessary, in addition to inorganic fillers B1 and B2 described
above in order to improve dimensional stability, suppress the
generation of metal-corroding gas, etc. The other fillers can
include a non-fibrous inorganic filler B3, another fibrous
inorganic filler B4 with a different diameter ratio that is
different from those of inorganic fillers B1 and B2 described
above, etc. These other fillers can also be surface treated as
described above.
[0048] The non-fibrous inorganic filler B3 can include particulate
inorganic fillers, tabular inorganic fillers, etc. As described
above, "particulate" means a shape with a different diameter ratio
of 1 or more and 10 or less and an aspect ratio of 1 or more and 2
or less and "tabular" means a shape with a different diameter ratio
greater than 10 and an aspect ratio of 1 or more and 500 or
less.
[0049] Among non-fibrous inorganic fillers B3, particulate
inorganic fillers can include carbon black, silica, quartz powder,
glass beads, glass powder, talc (particulate), silicates such as
calcium silicate, aluminum silicate, and diatomaceous earth, metal
oxides such as iron oxide, titanium oxide, zinc oxide, and alumina,
metal carbonates such as calcium carbonate and magnesium carbonate,
metal sulfates such as calcium sulfate and barium sulfate, and,
additionally, silicon carbide, silicon nitride, boron nitride,
various metal powders, etc. Among these, calcium carbonate and
glass beads can preferably be used.
[0050] Among non-fibrous inorganic fillers B3, for example, glass
flakes, talc (tabular), mica, kaolin, clay, alumina, various metal
foils, etc. can be raised as tabular inorganic fillers. Among
these, glass flakes and talc can preferably be used. With
objectives such as improving dimensional accuracy and improving
mechanical and physical properties, two or more of the
abovementioned inorganic fillers can be mixed and used in the
non-fibrous inorganic filler B3.
[0051] When the non-fibrous inorganic filler B3 is a particulate
filler, the average particle diameter (50% d) thereof in its
initial shape (the shape before melt-kneading) is preferably 10
.mu.m or more, more preferably 12 .mu.m or more, and yet more
preferably 15 .mu.m or more in terms of further improving
mechanical strength and thermal shock resistance. Further, the
upper limit is preferably 50 .mu.m or less, more preferably 45
.mu.m or less, and yet more preferably 40 .mu.m or less. When the
non-fibrous inorganic filler B3 is a tabular filler, the average
particle diameter thereof in its initial shape (the shape before
melt-kneading) is preferably 10 .mu.m or more and 100 .mu.m or
less, more preferably 15 .mu.m or more and 900 .mu.m or less, and
particularly preferably 20 .mu.m and 800 .mu.m or less. The average
particle diameter (50% d) means the median diameter of the 50%
integral value in a particle size distribution measured with a
laser diffraction/scattering method.
[0052] The amount of the non-fibrous inorganic filler B3 blended is
preferably 20 parts by mass or more and more preferably 25 parts by
mass or more with respect to 100 parts by mass of the polyarylene
sulfide-based resin A in terms of improving mechanical strength and
thermal shock resistance. In particular, the contents of the
abovementioned fibrous inorganic filler B2 and the non-fibrous
inorganic filler B3 both are preferably 20 parts by mass or more,
more preferably 22 parts by mass or more, and particularly
preferably 25 parts by mass or more with respect to 100 parts by
mass of the polyarylene sulfide-based resin A. When the contents of
the fibrous inorganic filler B2 and the non-fibrous inorganic
filler B3 are both 20 parts by mass or more with respect to 100
parts by mass of the polyarylene sulfide-based resin A, more
superior thermal shock resistance can be attained even when an
insert-molded product has a structure in which thermal shock
resistance readily declines. The upper limit of the amount of the
non-fibrous inorganic filler B3 blended is preferably a mass ratio
of 80 or less and more preferably 65 or less with the polyarylene
sulfide-based resin A in terms of suppressing the lowering of
mechanical and physical properties.
[0053] The other fibrous inorganic filler B4 can include fibrous
inorganic fillers in which the different diameter ratio exceeds 1.5
or is 1.6 or more and less than 3.0. The material of the fibrous
inorganic filler B4 is the same as that of the fibrous inorganic
fillers B1 and B2 described above and the descriptions are
therefore omitted here.
[0054] The total content of the inorganic filler B is preferably 90
parts by mass or more and 220 parts by mass or less, more
preferably 100 parts by mass or more and 200 parts by mass or less,
and particularly preferably 110 parts by mass or more and 180 parts
by mass or less with respect to 100 parts by mass of the
polyarylene sulfide resin A in terms of causing the effects due to
the combination of the abovementioned inorganic fillers B1 and B2
to be exhibited while maintaining the properties of the polyarylene
sulfide-based resin A.
[0055] (Olefinic Copolymer C)
[0056] The olefinic copolymer C contains an .alpha.-olefin-derived
structural unit and an .alpha.,.beta.-unsaturated acid glycidyl
ester-derived structural unit as copolymer components. Because the
composition contains such an olefinic copolymer C, the thermal
shock resistance of insert-molded products can be enhanced
remarkably. Among these, the olefinic copolymer C is preferably an
olefinic copolymer that further contains a (meth)acrylic acid
ester-derived structural unit. The olefinic copolymer may be used
alone or in a combination of two or more. Below, (meth)acrylic acid
ester is also referred to as (meth)acrylate. For example,
(meth)acrylic acid glycidyl ester is also referred to as glycidyl
(meth)acrylate. Further, in the present specification
"(meth)acrylic acid" means both acrylic acid and methacrylic acid
and "(meth)acrylate" means both acrylate and methacrylate.
[0057] The .alpha.-olefin is not particularly limited and can
include, for example, ethylene, propylene, butylene, 1-pentene,
1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene,
4-methyl-1-hexene, etc. Among these, ethylene is preferable. One or
two or more selected from the substances described above can be
used as the .alpha.-olefin. The content of copolymer components
derived from the .alpha.-olefin is not particularly limited and,
for example, can be 1% by mass or more and 8% by mass or less in
the entire resin composition.
[0058] For example, the .alpha.,.beta.-unsaturated acid glycidyl
ester can include substances having the structure indicated by
general formula (II) below.
##STR00001##
[0059] (R.sub.1 is hydrogen, or an alkyl group with a carbon number
of one or more and 10 or less.)
[0060] For example, compounds indicated by general formula (II)
above can include acrylic acid glycidyl esters, methacrylic acid
glycidyl esters, ethacrylic acid glycidyl esters, etc. Among these,
methacrylic acid glycidyl esters are preferred. An
.alpha.,.beta.-unsaturated acid glycidyl ester can be used alone
and two or more can also be used in combination. The content of the
copolymer components derived from .alpha.,.beta.-unsaturated acid
glycidyl esters is preferably 0.05% by mass or more and 0.6% by
mass or less in the entire resin composition. When the content of
the copolymer components derived from .alpha.,.beta.-unsaturated
acid glycidyl esters is in this range, deposition of mold deposits
can be suppressed while maintaining thermal shock resistance.
[0061] The (meth)acrylic acid ester is not particularly limited and
can include, for example, acrylic acid esters such as methyl
acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate,
n-butyl acrylate, n-hexyl acrylate, isobutyl acrylate, n-amyl
acrylate, and n-octyl acrylate; and methacrylic acid esters such as
methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,
isopropyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate,
isobutyl methacrylate, n-amyl methacrylate, and n-octyl
methacrylate. Among these, methyl acrylate is preferred. A
(meth)acrylic acid ester can be used alone two or more can also be
used in combination. The content of the copolymer components
derived from (meth)acrylic acid esters is not particularly limited,
but can be, for example, 0.5% by mass or more and 3% by mass or
less in the entire resin composition.
[0062] Olefinic copolymers comprising an .alpha.-olefin-derived
structural unit and an .alpha.,.beta.-unsaturated glycidyl
ester-derived structural unit and olefinic copolymers further
comprising a (meth)acrylic acid ester-derived structural unit can
be manufactured by copolymerizing with conventionally known
methods. For example, the abovementioned olefinic copolymers can be
obtained by performing commonly known copolymerization with a
radical polymerization reaction. The type of the olefinic copolymer
is not particularly questioned, but for example, may be a random
copolymer or may be a block copolymer. Further, the above olefinic
copolymer may be an olefinic grafted copolymer in which, for
example, polymethyl methacrylate, polyethyl methacrylate,
polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, poly
2-ethylhexyl acrylate, polystyrene, polyacrylonitrile, an
acrylonitrile-styrene copolymer, a butyl acrylate-styrene
copolymer, etc. are chemically bonded to the olefinic copolymer
with a branched or cross-linked structure.
[0063] The olefinic copolymer C used in the present embodiment can
contain other copolymer component-derived structural units so long
as the effects of the present invention are not hindered.
[0064] More specifically, as the olefinic copolymer C, there are,
for example, glycidyl methacrylate-modified ethylenic copolymers,
glycidyl ether-modified ethylenic copolymers, etc. and among these,
glycidyl methacrylate-modified ethylenic copolymers are
preferred.
[0065] As glycidyl methacrylate-modified ethylenic copolymers,
there are glycidyl methacrylate graft-modified ethylenic
copolymers, ethylene-glycidyl methacrylate copolymers,
ethylene-glycidyl methacrylate-methyl acrylate copolymers, ethylene
glycidyl methacrylate-ethyl acrylate copolymers, ethylene-glycidyl
methacrylate-propyl acrylate copolymers, ethylene-glycidyl
methacrylate-butyl acrylate copolymers, etc. Among these, because
particularly superior metal-resin composite molded bodies are
obtained, ethylene-glycidyl methacrylate copolymers and
ethylene-glycidyl methacrylate-methyl acrylate copolymers are
preferred and ethylene-glycidyl methacrylate-methyl acrylate
copolymers are particularly preferred. "BONDFAST" (manufactured by
Sumitomo Chemical, Co., Ltd.), etc. can be included as specific
examples of ethylene-glycidyl methacrylate copolymers and
ethylene-glycidyl methacrylate-methyl acrylate copolymers.
[0066] For example, glycidyl ether graft-modified ethylene
copolymers, glycidyl ether-ethylene copolymers, etc. can be
included as glycidyl ether-modified ethylene copolymers.
[0067] The content of the olefinic copolymer C is 3 parts by mass
or more and less than 19 parts by mass with respect to 100 parts by
mass of the polyarylene sulfide-based resin A and from the
viewpoint of thermal shock resistance, the content is preferably 5
parts by mass or more, more preferably 7 parts by mass or more, and
yet more preferably 9 parts by mass or more with respect to 100
parts by mass of the polyarylene sulfide-based resin. Meanwhile,
from the viewpoint of flowability, the content of the olefinic
copolymer C is preferably less than 19 parts by mass, more
preferably 18 parts by mass or less, and yet more preferably 17
parts by mass or less with respect to 100 parts by mass of the
polyarylene sulfide-based resin A.
[0068] (Olefinic Copolymer D)
[0069] The olefinic copolymer D comprises one or more olefinic
copolymers selected from the group consisting of olefinic copolymer
D1 and olefinic copolymer D2 described below. By containing not
only the olefinic copolymer C, but the olefinic copolymer D, the
polyarylene sulfide-based resin composition of the present
embodiment can have a certain flowability as a resin composition
while the thermal shock resistance of insert-molded products is
enhanced.
[0070] The content of the olefinic copolymer D is 3 parts by mass
or more and 30 parts by mass or less, more preferably 5 parts by
mass or more and 25 parts by mass or less, and yet more preferably
6 parts by mass or more and 20 parts by mass or less in total with
respect to 100 parts by mass of the polyarylene sulfide-based resin
A.
[0071] (Olefinic Copolymer D1)
[0072] The olefinic copolymer D1 contains ethylene and an
.alpha.-olefin as copolymer components. In the olefinic copolymer
D1, the carbon number of the .alpha.-olefin is preferably 3-20,
more preferably 5-20, and yet more preferably 5-15. The olefinic
copolymer D1 may be a random copolymer or a block copolymer. The
olefinic copolymer D1 may be a copolymer comprising 5-95% by mass
ethylene and 5-95% by mass of the .alpha.-olefin. As specific
examples of the olefinic copolymer D1, there are ethylene-octene
(EO) copolymers, ethylene-propylene copolymers, ethylene-butylene
copolymers, ethylene-pentene copolymers, ethylene-hexene
copolymers, ethylene-heptene copolymers, etc. and furthermore,
these copolymers can be mixed and used.
[0073] (Olefinic Copolymer D2)
[0074] The olefinic copolymer D2 contains an .alpha.-olefin-derived
structural unit and an .alpha.,.beta.-unsaturated carboxylic acid
alkylene ester-derived structural unit as copolymer components and
may be a random, block, or graft copolymer and the copolymer may be
modified by at least one selected from the group consisting of
unsaturated carboxylic acids, acid anhydrides thereof, and
derivatives thereof. The .alpha.-olefin in the olefinic copolymer
D2 is not particularly limited, but as examples thereof, there are,
for example, ethylene, propylene, butylene, 1-pentene, 1-hexene,
1-heptene, 1-octene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc.
Among these, ethylene is preferable. One or more selected from the
substances described above can be used as the .alpha.-olefin.
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl
acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate,
2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate,
ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate,
2-ethylhexyl methacrylate, hydroxyethyl methacrylate, etc. can be
used as the .alpha.,.beta.-unsaturated carboxylic alkyl ester in
the olefinic copolymer D2.
[0075] Acrylic acid, methacrylic acid, maleic acid, fumaric acid,
itaconic acid, crotonic acid, methyl maleic acid, methyl fumaric
acid, mesaconic acid, citraconic acid, glutaconic acid, monomethyl
maleate, monoethyl maleate, monoethyl fumarate, methyl itaconate,
methyl maleic anhydride, maleic anhydride, methyl maleic anhydride,
citraconic anhydride, etc. are examples of the unsaturated
carboxylic acid or anhydride thereof used as a modifier and one or
two or more of these is used.
[0076] As specific examples of the olefinic copolymer D2, there are
copolymers of ethylene and a (meth)acrylic acid ester such as
ethylene ethyl acrylate (EEA) copolymers, ethylene methyl
methacrylate copolymers, etc.
[0077] The content of the olefinic copolymer C and the content of
the olefinic copolymer D are not particularly limited so long as
they are within specified ranges, but from the viewpoint of thermal
shock resistance, the content of the olefinic copolymer C is
preferably the same as or greater than the content of the olefinic
copolymer D.
[0078] Further, of the olefinic copolymer D1 and the olefinic
copolymer D2, it is more preferable that the olefinic copolymer D2
be used as the olefinic copolymer D.
[0079] (Other Additives, etc.)
[0080] Publicly known additives generally added to thermoplastic
resins and thermosetting resins, that is, burr suppressing agents,
mold release agents, lubricants, plasticizers, flame retardants,
colorants such as dyes and pigments, crystallization accelerators,
nucleating agents, various antioxidants, thermal stabilizers,
weatherproofing stabilizers, anti-corrosion agents, etc. can be
blended with the resin composition in accordance with the desired
performance so long as the effects of the invention are not
hindered in order to impart desired properties in accordance with
the objective thereof. Burr suppressing agents can include, for
example, branched type polyphenylene sulfide-based resins, silane
compounds, etc. with extremely high melt viscosities as described
in WO 2006/068161 A, WO 2006/068159 A, etc. Silane compounds
include various types such as vinylsilane, methacryloxysilane,
epoxysilane, aminosilane, and mercaptosilane and while, for
example, vinlytrichlorosilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
.gamma.-mercaptotrimethoxysilane, etc. are listed, silane compounds
are not limited thereto. The content of the additives can be set
to, for example, 5% by mass or less in the entire resin
composition.
[0081] Further, in addition to the abovementioned components, a
small amount of another thermoplastic resin component can also be
supplementally used in combination in the resin composition in
accordance with the objective thereof. The other thermoplastic
resin used here may be any resin that is stable at high
temperatures. For example, this can include aromatic polyesters
that comprise an aromatic dicarboxylic acid and a diol or an
oxycarboxylic acid, etc., such as polyethylene terephthalate and
polybutylene terephthalate, polyamides, polycarbonates, ABS,
polyphenylene oxides, polyalkyl acrylates, polysulfones,
polyethersulfones, polyetherimides, polyetherketones, fluororesins,
etc. Further, two or more of these thermoplastic resins can be
mixed and used. The content of the other thermoplastic resin
component can be set to, for example, 20% by mass or less, 15% by
mass or less, or 10% by mass or less in the entire resin
composition.
[0082] Preparation of the resin composition can easily be carried
out using equipment and methods that are commonly used as
conventional methods for resin composition preparation. For
example, any of 1) methods for, after components are mixed,
preparing pellets by kneading and extruding with a single- or
twin-screw extruder and then molding, 2) methods for, first
preparing pellets of a different composition, mixing a
predetermined amount of the pellets and molding, and then obtaining
a molded product of the objective composition, 3) methods for
directly introducing one or more components in a molding machine,
etc. can be used. Further, methods for setting part of the resin
components as a fine powder and adding this part to the other
components and mixing are preferred methods to achieve a uniform
blend of these components.
[0083] The polyarylene sulfide-based resin composition of the
present embodiment is a resin composition with excellent thermal
shock resistance, low warpage property, and flowability and by
making use of these properties, the composition is useful in
various applications. Among these, the composition is especially
preferably used for automobile/vehicle-related insert members that
have structures that are complicated and have portions with large
changes in thickness or are used in environments with large
high/low temperature changes. As automobile/vehicle-related
components, there are components around engines, drive system
components, cooling system components, etc. As components around
engines, there are inverter cases, current sensors, capacitor
cases, reactors, bus bar components, etc. in hybrid electric
vehicles (HEVs). As drive system components, there are motor
insulators, rotation sensors, etc. As cooling system components,
there are water pumps, oil pumps, flow control units, etc. Among
these, application to inverter cases, current sensors, reactors,
and bus bar components is preferred.
[0084] [Insert-Molded Product]
[0085] FIGS. 1A and 1B show an example of an insert-molded product
according to the present embodiment schematically. A is a
perspective view and B is a plan view of A. As shown in FIG. 1A, an
insert-molded product 1 has an insert member 11 and a resin member
12 that covers at least a portion of a surface of the insert
member. The insert member 11 is formed from a metal, an alloy, or
an inorganic solid, is a rectangular column having four corner
portions 120a-d, and is partially embedded in the resin member 12.
The resin member 12 is formed from the abovementioned polyarylene
sulfide-based resin composition and has four brittle portions
130a-d comprising welded portions and stress-concentrating
portions. The brittle portions 130a-d are formed in an
approximately rectangular shape so as to extend in a predetermined
direction. The brittle portions 130a-d may be configured consisting
only of either the welded portions or the stress-concentrating
portions.
[0086] The "stress-concentrating portions" are portions that
concentrate stress generated by expansion and contraction of the
resin composition. The stress-concentrating portions can include,
for example, corner portions, cutout portions, damaged portions,
through holes, punched portions, thin portions, locations with
large changes in thickness, flow mark portions, etc. One or more
stress-concentration portions may be formed. The corner portions
120a-d of the rectangular columnar insert member 11 in the
insert-molded product 1 shown in FIG. 1A are disposed so as to
point toward side surfaces of the resin member 12. In addition, a
distanced between the tips of the corner portions (sharp corners)
of the insert member 11 and the side surfaces of the resin member
12 is roughly 1 mm and the vicinities thereof are thin
stress-concentrating portions 130a-d. As shown by the regions drawn
with hatched lines, the brittle portions 130a-d are configured in
an approximately rectangular shape from the ridge lines of the
regions of the corner portions 120a-d of the insert member 1
embedded in the resin member 12 to the side surfaces of the resin
member 12.
[0087] The "welded portions" are portions where flow terminals of
the resin composition are bonded (welded). The mechanical strength
of welded portions tends to deteriorate more than that at other
locations. How the welds are formed shall be explained, referring
to FIGS. 1A, 1B, and 2. The insert-molded product 1 is manufactured
in a mold having a gate in a bottom surface X side and therefore
has a trace of a gate on the bottom surface X, which is not
illustrated. When injection molding the insert-molded product 1,
the resin composition is injected into the cavity of the mold from
the mold gate (not illustrated) in the bottom surface X side of the
insert-molded product 1, as shown in FIGS. 1A, 1B, and 2. Injected
resin stream Q branches into multiple resin streams Q.sub.1,
Q.sub.2 with the bottom surface of the insert member 11 as the
origin. The resin streams Q.sub.1, Q.sub.2 respectively flow along
the side surfaces of the insert member 11 and, at the ridge line
portions of the corner portions 120a-d of the insert member 11,
rejoin at an angle in which respective angles of attack
.theta..sub.1, .theta..sub.2 are less than 90.degree. with respect
to the ridge lines (for example, 0.degree. or more and 45.degree.
or less) and are bonded at this interface. These bond portions
become welded portions and constitute the brittle portions 130a-d.
In FIG. 2, for convenience of explanation, only the brittle portion
130c is illustrated, but each of the brittle portions 130a-d is
formed in a rectangular shape from each ridge line of the corner
portions 120a-d of the insert member 1 to the side surfaces of the
resin member 12. In the insert-molded product 1, the positions at
which the welded portions and the stress-concentrating portions
match and the brittle portions 130a-d are formed so as to comprise
both the welded portions and the stress-concentrating portions.
[0088] The insert-molded product 1 formed as described above has at
least one of the brittle portions 130a-d extending in a
predetermined direction and has a trace of a gate on a surface X
extending in a direction approximately perpendicular to the
direction in which the at least one of the brittle portions 130a-d
extends. "Approximately perpendicular" means an angle of
approximately 75.degree. to 105.degree., including a right angle.
Due to the insert-molded product 1 having a resin member comprising
the resin composition as in the present embodiment, declines in
thermal shock resistance are prevented even in an insert-molded
product having such a structure and an insert-molded product having
excellent thermal shock resistance can be configured. Further,
dimensional accuracy can also be enhanced by simultaneously
achieving low warpage property.
[0089] The metal, alloy, or inorganic solid constituting the insert
member 11 is not particularly limited, but is preferably a
substance that will not deform or melt when contacting the resin
during molding. For example, these can include metals such as
aluminum, magnesium, copper, and iron, alloys of said metals such
as brass, and inorganic solids such as glass, ceramics, etc.
[0090] The manufacturing method for the insert-molded product is
not particularly limited and, for example, the abovementioned resin
composition and an insert member formed in a desired shape
beforehand can be insert molded. Insert molding can be, for
example, composite molding by fitting an insert member in a mold
ahead of time and filling the outside thereof with the
abovementioned resin composition by injection molding,
extrusion-compression molding, etc. The shape and size of the
insert-molded product are not particularly limited.
EXAMPLES
[0091] The present invention will be explained more specifically by
showing the following examples, but the interpretation of the
present invention is not limited thereby.
Examples 1-9 and Comparative Examples 1-10
[0092] Using the materials indicated below, polyarylene
sulfide-based resins, inorganic fillers, and olefinic copolymers
were dry blended with the compositions and at the content ratios
shown in Table 1. Resin composition pellets of the examples and
comparative examples were obtained by feeding these to a twin-screw
extruder with a cylinder temperature of 320.degree. C. and
melt-kneading.
[0093] (Polyarylene Sulfide-Based Resin)
[0094] Polyarylene Sulfide-based Resin A: Polyphenylene sulfide
(PPS) resin, "Fortron KPS" manufactured by KUREHA CORPORATION (melt
viscosity: 20 Pas (shear rate: 1,216 sec.sup.-1, 310.degree.
C.))
[0095] (Measurement of Melt Viscosity of the Polyarylene
Sulfide-Based Resin)
[0096] The melt viscosity of the abovementioned polyarylene
sulfide-based resin A was measured as follows.
[0097] Using a capillograph manufactured by Toyo Seiki Seisaku-sho,
Ltd., the melt viscosity was measured at a barrel temperature of
310.degree. C. and a shear rate of 1,216 sec.sup.-1 using a 1
mmo.times.20 mmL/flat die as the capillary.
[0098] (Inorganic Fillers)
[0099] Fibrous Inorganic Filler B1: Glass fibers, approximately
round cross section, long diameter: 10.5 .mu.m, short diameter:
10.5 .mu.m, long diameter/short diameter ratio: 1.0, "Chopped
Strands ECS03T-747H" manufactured by Nippon Electric Glass Co.,
Ltd.
[0100] Fibrous Inorganic Filler B2: Glass fibers, elliptical cross
section, long diameter: 28 .mu.m, short diameter: 7 .mu.m, long
diameter/short diameter ratio: 4.0, "Chopped Strand with Modified
Cross Section CSG 3PA-830" manufactured by Nitto Boseki Co,
Ltd.
[0101] Fibrous Inorganic Filler: Glass fibers, elliptical cross
section, long diameter: 20 .mu.m, short diameter: 10 .mu.m, long
diameter/short diameter ratio: 2.0, "Chopped Strand with Modified
Cross Section CSG 3PL-962" manufactured by Nitto Boseki Co,
Ltd.
[0102] Fibrous Inorganic Filler: Glass fibers, cocoon-shaped cross
section, long diameter: 24 .mu.m, short diameter: 12 .mu.m, long
diameter/short diameter ratio: 2.0, "Chopped Strand with Modified
Cross Section CSH 3PA-860" manufactured by Nitto Boseki Co,
Ltd.
[0103] Non-fibrous Inorganic Filler B3: Calcium carbonate, average
particle diameter (50% d): 25 .mu.m, "MC-35W" manufactured by ASAHI
KOHMATSU CO., LTD.
[0104] (Olefinic Copolymers)
[0105] Olefinic Copolymer C: "BONDFAST 7M" manufactured by Sumitomo
Chemical, Co., Ltd., comprising 67% by mass ethylene, 6% by mass
methacrylic acid glycidyl ester, and 27% by mass methyl acrylate as
copolymer components.
[0106] Olefinic Copolymer D1: Ethylene-octene copolymer, "Engage
8440" manufactured by Dow Chemical Japan Limited
[0107] Olefinic Copolymer D2: Ethylene-ethyl acrylate copolymer,
"NUC-6570" manufactured by NUC CO., LTD.
[0108] [Evaluation]
[0109] (Flowability)
[0110] Using a capillograph manufactured by Toyo Seiki Seisaku-sho,
Ltd., the melt viscosity (Pas) was measured at a barrel temperature
of 310.degree. C. and a shear rate of 1,000 sec.sup.-1 using a 1
mmo.times.20 mmL/flat die as the capillary. The results are shown
in Table 1. The flowability is excellent when the melt viscosity is
250 Pas or less.
[0111] (Thermal Shock Resistance)
[0112] Using the resin compositions obtained in the examples and
comparative examples and insert members (1.41 cm.times.1.41
cm.times.height 2.4 cm rectangular columnar shape) made of S35C as
defined by JIS G4051:2005 Carbon Steels for Machine Structural Use
and insert injection molding such that the smallest thickness of
the resin portion became 1 mm by flowing the resin compositions
into a mold from the gate in the surface X side in FIGS. 1A and 1B
under conditions of a 320.degree. C. cylinder temperature and a
150.degree. C. mold temperature, insert-molded products 1 as shown
in FIGS. 1A and 1B were manufactured and made into test pieces.
[0113] Repeating a cycle of cooling the test pieces at -40.degree.
C. for 1.5 hours and heating the test piece at 180.degree. C. for
1.5 hours using a hot-cold shock tester (manufactured by ESPEC
CORP.), the brittle portions were observed every 20 cycles. The
number of cycles when cracks arose in the brittle portions was
evaluated as an index of the thermal shock resistance. The results
are shown in Table 1. The thermal shock resistance is excellent
when the number of cycles was 150 or more and the thermal shock
resistance is particularly excellent when the number of cycles was
170 or more.
[0114] (Low Warpage Property)
[0115] Using the resin compositions obtained in the examples and
comparative examples, five 80 mm.times.80 mm.times.1.5 mm thick
tabular resin molded products 2 were manufactured by injection
molding under conditions of a cylinder temperature of 320.degree.
C., a mold temperature of 150.degree. C., and a holding pressure of
70 MPa. Placing the first sheet of the tabular resin molded product
2 on a horizontal surface, the height from the horizontal surface
was measured at 9 locations on the tabular resin molded product 2
using a CNC image measurement device manufactured by Mitutoyo
Corporation (model: QVBHU404-PRO1F) and the average height was
calculated from the obtained measurement values. The filled circles
in FIG. 3 show the measured locations (d.sub.1=3 mm and d.sub.2=37
mm). A plane parallel to the horizontal surface of which the height
from the horizontal surface is identical to the average height was
set as a reference plane. The maximum height and minimum height
from the reference plane were selected from the heights measured at
the nine locations and the difference between the two was
calculated. Similarly, the difference was also calculated for the
other four tabular resin molded products and the five values were
averaged and set as the amount of warping. The results are shown in
Table 1. The lower the amount of warping, the better the low
warpage property.
TABLE-US-00001 TABLE 1 EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE
EXAMPLE MATERIAL 1 2 3 4 5 6 PPS A 100 100 100 100 100 100 FIBROUS
INORGANIC 95 54 54 56 56 59 FILLER B1 (DIFFERENT DIAMETER RATIO:
1.0) FIBROUS INORGANIC 54 41 41 42 42 45 FILLER B2 (DIFFERENT
DIAMETER RATIO: 1.0) FIBROUS INORGANIC -- -- -- -- -- -- FILLER
(DIFFERENT DIAMETER RATIO: 2.0, CROSS SECTION: OVAL) FIBROUS
INORGANIC -- -- -- -- -- -- FILLER (DIFFERENT DIAMETER RATIO: 2.0.
CROSS SECTION: COCOON-SHAPED) NON-FIBROUS -- 54 54 56 56 59
INORGANIC FILLER B3 OLEFINIC 14 14 11 14 11 15 COPOLYMER C OLEFINIC
-- -- -- -- -- -- COPOLYMER D1 OLEFINIC 5 5 8 8 11 15 COPOLYMER D2
B1/B2 1.8 1.3 1.3 1.3 1.3 1.3 TOTAL FILLER 150 150 150 154 154 163
AMOUNT THERMAL SHOCK 150 180 170 200 190 250 RESISTANCE (CYCLES)
LOW WARPAGE 0.04 0.05 0.05 0.05 0.05 0.05 PROPERTY (mm) MELT
VISCOSITY 240 230 220 235 230 240 (Pa s) EXAMPLE EXAMPLE EXAMPLE
COMPARATIVE COMPARATIVE MATERIAL 7 8 9 EXAMPLE 1 EXAMPLE 2 PPS A
100 100 100 100 100 FIBROUS INORGANIC 56 37 107 59 56 FILLER B1
(DIFFERENT DIAMETER RATIO: 1.0) FIBROUS INORGANIC 42 61 31 45 42
FILLER B2 (DIFFERENT DIAMETER RATIO: 1.0) FIBROUS INORGANIC -- --
-- -- -- FILLER (DIFFERENT DIAMETER RATIO: 2.0, CROSS SECTION:
OVAL) FIBROUS INORGANIC -- -- -- -- -- FILLER (DIFFERENT DIAMETER
RATIO: 2.0. CROSS SECTION: COCOON-SHAPED) NON-FIBROUS 56 25 40 59
56 INORGANIC FILLER B3 OLEFINIC 14 12 15 30 22 COPOLYMER C OLEFINIC
8 7 9 -- -- COPOLYMER D1 OLEFINIC -- -- -- -- -- COPOLYMER D2 B1/B2
1.3 0.6 3.5 1.3 1.3 TOTAL FILLER 154 123 177 163 154 AMOUNT THERMAL
SHOCK 180 230 170 280 230 RESISTANCE (CYCLES) LOW WARPAGE 0.05 0.05
0.05 0.05 0.05 PROPERTY (mm) MELT VISCOSITY 220 190 240 380 320 (Pa
s) COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE MATERIAL EXAMPLE
3 EXAMPLE 4 EXAMPLE 5 EXAMPLE 3 PPS A 100 100 100 100 FIBROUS
INORGANIC 54 53 54 54 FILLER B1 (DIFFERENT DIAMETER RATIO: 1.0)
FIBROUS INORGANIC 41 40 -- -- FILLER B2 (DIFFERENT DIAMETER RATIO:
1.0) FIBROUS INORGANIC -- -- 41 -- FILLER (DIFFERENT DIAMETER
RATIO: 2.0, CROSS SECTION: OVAL) FIBROUS INORGANIC -- -- -- 41
FILLER (DIFFERENT DIAMETER RATIO: 2.0. CROSS SECTION:
COCOON-SHAPED) NON-FIBROUS 54 53 54 54 INORGANIC FILLER B3 OLEFINIC
19 16 14 14 COPOLYMER C OLEFINIC -- -- -- -- COPOLYMER D1 OLEFINIC
-- -- 5 5 COPOLYMER D2 B1/B2 1.3 1.3 -- -- TOTAL FILLER 150 146 150
150 AMOUNT THERMAL SHOCK 170 120 80 70 RESISTANCE (CYCLES) LOW
WARPAGE 0.05 0.05 0.6 0.6 PROPERTY (mm) MELT VISCOSITY 280 240 230
235 (Pa s) COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE MATERIAL
EXAMPLE 7 EXAMPLE 8 EXAMPLE 9 EXAMPLE 10 PPS A 100 100 100 100
FIBROUS INORGANIC -- 158 -- 100 FILLER B1 (DIFFERENT DIAMETER
RATIO: 1.0) FIBROUS INORGANIC 158 -- -- 14 FILLER B2 (DIFFERENT
DIAMETER RATIO: 1.0) FIBROUS INORGANIC -- -- -- -- FILLER
(DIFFERENT DIAMETER RATIO: 2.0, CROSS SECTION: OVAL) FIBROUS
INORGANIC -- -- 100 -- FILLER (DIFFERENT DIAMETER RATIO: 2.0. CROSS
SECTION: COCOON-SHAPED) NON-FIBROUS -- -- 100 43 INORGANIC FILLER
B3 OLEFINIC 17 17 5 17 COPOLYMER C OLEFINIC 9 9 10 9 COPOLYMER D1
OLEFINIC -- -- -- -- COPOLYMER D2 B1/B2 -- -- -- 7.0 TOTAL FILLER
158 158 200 158 AMOUNT THERMAL SHOCK 60 200 50 190 RESISTANCE
(CYCLES) LOW WARPAGE 0.01 0.8 0.06 0.7 PROPERTY (mm) MELT VISCOSITY
250 260 350 240 (Pa s) THE CONTENT UNITS ARE PARTS BY MASS.
REFERENCE SIGNS LIST
[0116] 1 Insert-molded product [0117] 2 Tabular resin molded
product [0118] 11 Insert member [0119] 12 Resin member [0120]
120a-d Corner portions [0121] 130a-d Brittle portions [0122] Q
Resin flow
* * * * *