U.S. patent application number 12/181461 was filed with the patent office on 2009-03-26 for long fiber filler reinforced resin pellet.
This patent application is currently assigned to ASAHI KASEI CHEMICALS CORPORATION. Invention is credited to Yoshikuni Akiyama, Hiroaki Furukawa, Hiroshi Kamo, Takaaki Miyoshi, Koji Sarukawa, Kazunori Terada, Kazuo Yoshida.
Application Number | 20090081462 12/181461 |
Document ID | / |
Family ID | 38437223 |
Filed Date | 2009-03-26 |
United States Patent
Application |
20090081462 |
Kind Code |
A1 |
Miyoshi; Takaaki ; et
al. |
March 26, 2009 |
LONG FIBER FILLER REINFORCED RESIN PELLET
Abstract
The invention provides a long fiber filler reinforced resin
pellet composed of a long fiber filler and a thermoplastic resin
blend. In the pellet, the long fiber filler is aligned to form a
spiral with a central axis along the longitudinal direction of the
pellet, and the pellet has a skin layer part with a lower content
of the long fiber filler, and a core part with a higher content of
the long fiber filler, thereby the cross-section of the core part
is in a range of 30% to 70% of the cross-section of the pellet. The
thermoplastic resin blend in the pellet is composed of
polyphenylene ether and a thermoplastic resin other than
polyphenylene ether.
Inventors: |
Miyoshi; Takaaki; (Tokyo,
JP) ; Kamo; Hiroshi; (Tokyo, JP) ; Sarukawa;
Koji; (Tokyo, JP) ; Yoshida; Kazuo; (Tokyo,
JP) ; Akiyama; Yoshikuni; (Tokyo, JP) ;
Furukawa; Hiroaki; (Tokyo, JP) ; Terada;
Kazunori; (Tokyo, JP) |
Correspondence
Address: |
GREENBLUM & BERNSTEIN, P.L.C.
1950 ROLAND CLARKE PLACE
RESTON
VA
20191
US
|
Assignee: |
ASAHI KASEI CHEMICALS
CORPORATION
Tokyo
JP
|
Family ID: |
38437223 |
Appl. No.: |
12/181461 |
Filed: |
July 29, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2007/052001 |
Feb 6, 2007 |
|
|
|
12181461 |
|
|
|
|
Current U.S.
Class: |
428/407 ;
264/5 |
Current CPC
Class: |
Y10T 428/2998 20150115;
C08J 5/043 20130101; C08L 77/00 20130101; C08J 2377/00 20130101;
C08L 23/12 20130101; C08J 2367/02 20130101; C08J 2323/12
20130101 |
Class at
Publication: |
428/407 ;
264/5 |
International
Class: |
B32B 5/16 20060101
B32B005/16 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 27, 2006 |
JP |
2006-049469 |
Claims
1. A long fiber filler reinforced resin pellet, comprising a long
fiber filler and a thermoplastic resin blend, wherein: the long
fiber filler is aligned, in said pellet, to form a spiral with a
central axis along a longitudinal direction of said pellet; and
said pellet has a skin layer part with a lower content of the long
fiber filler, and a core part with a higher content of the long
fiber filler, a cross-section of said core part being in a range
from 30% to 70% of the cross-section of said pellet; and said
thermoplastic resin blend comprises polyphenylene ether and a
thermoplastic resin other than polyphenylene ether.
2. The long fiber filler reinforced resin pellet according to claim
1, wherein a ratio of an average fiber length of said long fiber
filler to the length of said long fiber filler reinforced resin
pellet exceeds 1.0.
3. The long fiber filler reinforced resin pellet according to claim
1, wherein a rate of said long fiber filler in said long fiber
filler reinforced resin pellet is from 30 to 70% by mass.
4. The long fiber filler reinforced resin pellet according to claim
1, wherein said long fiber filler is a glass fiber.
5. The long fiber filler reinforced resin pellet according to claim
1, wherein a reduced viscosity (a chloroform solution of 0.5 g/dL
concentration, measured at 30.degree. C.) of said polyphenylene
ether is in a range from 0.30 to 0.55 dL/g.
6. The long fiber filler reinforced resin pellet according to claim
1, wherein said polyphenylene ether is a copolymer comprising
2,3,6-trimethylphenol, and a rate of a unit of said
2,3,6-trimethylphenol in the polyphenylene ether is from 10 to 30%
by mass.
7. The long fiber filler reinforced resin pellet according to claim
1, wherein said thermoplastic resin other than the polyphenylene
ether is one or more selected from the group consisting of a
styrenic resin, an olefinic resin, polyester, polyamide,
polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone,
polysulfone and polyaryl ketone.
8. The long fiber filler reinforced resin pellet according to claim
1, wherein said thermoplastic resin other than the polyphenylene
ether is one or more selected from the group consisting of
homo-polystyrene, rubber-modified polystyrene,
acrylonitrile-styrene copolymer and N-phenylmaleimide-styrene
copolymer.
9. The long fiber filler reinforced resin pellet according to claim
8, wherein a rate of said polyphenylene ether in said thermoplastic
resin blend is from 10 to 90% by mass.
10. The long fiber filler reinforced resin pellet according to
claim 1, wherein said thermoplastic resin other than the
polyphenylene ether is one or more selected from the group
consisting of polypropylene, liquid crystal polyester, polyamide,
polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone,
polysulfone and polyaryl ketone.
11. The long fiber filler reinforced resin pellet according to
claim 10, wherein the rate of said polyphenylene ether in said
thermoplastic resin blend is from 1 to 50% by mass.
12. The long fiber filler reinforced resin pellet according to
claim 1, further comprising a compatibilizer.
13. The long fiber filler reinforced resin pellet according to
claim 12, wherein said compatibilizer is a compound having one or
more functional groups selected from the group consisting of an
epoxy group, an oxazolyl group, an imide group, a carboxylic group
and an acid anhydride group.
14. The long fiber filler reinforced resin pellet according to
claim 1, further comprising a sterically-hindered phenol-based
antioxidant in an amount from 0.1 to 5 parts by mass based on 100
parts by mass of said thermoplastic resin blend.
15. The long fiber filler reinforced resin pellet according to
claim 1, further comprising a flame retardant without halogen in an
amount from 5 to 50 parts by mass based on 100 parts by mass of
said thermoplastic resin blend.
16. The long fiber filler reinforced resin pellet according to
claim 1, further comprising a filler other than the long fiber
filler.
17. A resin pellet blend comprising: 100 parts by mass of the long
fiber filler reinforced resin pellet according to claim 1; and 0.5
to 150 parts by mass of a resin pellet without the long fiber
filler.
18. The resin pellet blend according to claim 17, wherein a rate of
said long fiber filler in said resin pellet blend is from 10 to 60%
by mass.
19. The resin pellet blend according to claim 17, wherein said
resin pellet without the long fiber filler further comprises a
filler other than the long fiber filler.
20. The resin pellet blend according to claim 19, wherein said
filler other than the long fiber filler is one or more fillers
selected from the group consisting of a hydroxide of an element
selected from magnesium and calcium; an oxide of an element
selected from the group consisting of magnesium, titanium, iron,
copper, zinc and aluminum; zinc sulfide, zinc borate, calcium
carbonate, talc, wollastonite, glass, carbon black, carbon nanotube
and silica; and an average particle size of said filler other than
the long fiber filler is not more than 1 mm.
21. A molded article produced by melt-molding of the long fiber
filler reinforced resin pellet according to claim 1.
22. A process for producing a long fiber filler reinforced resin
pellet, wherein the pellet comprises a long fiber filler and a
thermoplastic resin blend; said long fiber filler is aligned, in
said pellet, to form a spiral with a central axis along a
longitudinal direction of said pellet; and said pellet comprises a
skin layer part with a lower content of the long fiber filler, and
a core part with a higher content of the long fiber filler, the
cross-section of said core part being in a range from 30% to 70% of
the cross-section of said pellet, said thermoplastic resin blend
comprises polyphenylene ether and a thermoplastic resin other than
polyphenylene ether; and the process for producing the long fiber
filler reinforced resin pellet comprises the steps of: (1)
producing said thermoplastic resin blend in a molten state by an
extruder, (2) impregnating said long fiber filler with said
thermoplastic resin blend in the molten state, (3) forming a resin
strand by drawing and twisting, and (4) cutting said resin strand
to a pellet form.
23. The process for producing the long fiber filler reinforced
resin pellet according to claim 22, wherein the process for
producing the long fiber filler reinforced resin pellet comprises
the steps (1) to (4) in said successive order.
24. The process for producing the long fiber filler reinforced
resin pellet according to claim 22, wherein the step (1) further
comprising producing said thermoplastic resin blend in the molten
state by blending said polyphenylene ether and said thermoplastic
resin other than the polyphenylene ether.
25. The process for producing the long fiber filler reinforced
resin pellet according to claim 22, wherein a set temperature of a
dipping bath in the step (2), in which said long fiber filler is
impregnated in said thermoplastic resin blend in the molten state,
is higher by 20.degree. C. or more than a set temperature of the
extruder in said step (1).
26. The process for producing the long fiber filler reinforced
resin pellet according to claim 22, wherein a drawing speed in said
step (3) is in a range from 10 to 150 m/min.
27. A molded article produced by melt-molding of the resin pellet
blend according to claim 17.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation-in-part of International
Application No. PCT/JP2007/052001 filed on Feb. 6, 2007 claiming
benefit of priority of Japanese Patent Application No. 2006-049469
applied on Feb. 27, 2006 in Japan, and the entire disclosure of
International Application No. PCT/JP2007/052001 is incorporated
herein by reference.
TECHNICAL FIELD
[0002] The present invention relates to a long fiber filler
reinforced resin pellet. The present invention also relates to a
resin pellet blend including the long fiber filler reinforced resin
pellet, a molded article produced by melt-molding of the long fiber
filler reinforced resin pellet, etc., a process for producing the
long fiber filler reinforced resin pellet, and the like.
BACKGROUND ART
[0003] Since a thermoplastic resin has superior formability, it is
used broadly for an automobile and machine related use, building
materials, housing equipment parts and the like. Among others a
thermoplastic resin composition reinforced by compounding glass
fibers is very valuable for reduction of a part weight and the
number of parts, by replacing metal materials owing to its superior
mechanical strength and moldability. Further, since the reinforced
thermoplastic resin compositions have excellent impact strength
(especially, surface impact strength) and rigidity, they are used
broadly for components receiving a high load, or components
receiving repeated loads.
[0004] Patent Literature 1 discloses a pultrusion method, by which
a glass fiber roving is impregnated while a resin strand being
drawn to obtain pellets, in which the length of the reinforcing
fiber and the length of the pellet are identical, as a realizing
means for a long fiber filler reinforced composition. The method is
still now most popularly utilized.
[0005] However a long fiber reinforced resin composition has
difficulty in wettability of fibers with the resin, because the
contact time between the resin and the fibers is limited, as
compared with a usual short fiber reinforced resin composition,
which is prepared by melt-blending in an extruder with short fibers
such as chopped strand, so that studies have been made to improve
the wettability.
[0006] For instance, Patent Literature 2 discloses a method to
select a thermoplastic resin having a considerably low melt
viscosity, so that continuous aligned filaments can be well wetted
by the thermoplastic resin.
[0007] Further, Patent Literature 3 discloses a technique to
improve flexibility or buckling strength of a long fiber strand by
twisting the same, and Patent Literature 4 discloses a production
process with high productivity by means of such twisting.
[0008] [Patent Literature 1] Japanese Patent Publication No.
52-3985
[0009] [Patent Literature 2] Japanese Patent Publication No.
63-37694
[0010] [Patent Literature 3] Japanese Patent Application Laid-Open
No. 05-169445
[0011] [Patent Literature 4] Japanese Patent Application Laid-Open
No. 2003-175512
[0012] However according to the technique disclosed by Patent
Literature 2, the interface strength between a resin and fibers is
insufficient that the produced pellets may cause longitudinal
fractures during transportation, or a long fiber filler may detach
from a pellet to cause such phenomenon that the detached long fiber
filler sticks on a product bag or a hopper of a molding machine
and, as a consequence, the market has been requesting improvement
thereof. Further, since the interface strength between a resin and
fibers is insufficient and the pellet surface is not glossy, the
friction resistance between pellets becomes higher, which causes
another problem of defective feeding into a molding machine.
[0013] In case, for example, polypropylene or polyamide is used as
a resin, and subjected to strong twisting based on the technologies
disclosed by Patent Literatures 3 and 4, the twisted long fibers
are not well fibrillated due to the melt viscosity of the resin
during fabrication in a molding machine, which results in
insufficient exhibition of potential properties of high heat
resistance or impact strength.
[0014] An object of the present invention is to provide a long
fiber filler reinforced resin pellet, having good wettability
between the long fiber filler and a thermoplastic resin blend,
extremely suppressing longitudinal fracture of a pellet during
pellet transportation and detachment of a long fiber filler from a
pellet, showing good pellet appearance, and further having superior
fibrillation property of a long fiber filler during molding,
enabling to mold a molded article with extremely high heat
resistance and impact strength.
DISCLOSURE OF THE INVENTION
[0015] The present inventors have intensively studied to find a
solution for the above object and have discovered that, by aligning
in a pellet the long fiber filler in a long fiber filler reinforced
resin pellet forming a spiral with a central axis along the
longitudinal direction of the pellet, the above object can be
attained, thereby completing the invention.
[0016] The present invention provides a long fiber filler
reinforced resin pellet, a resin pellet blend including the long
fiber filler reinforced resin pellet, a molded article produced by
melt-molding of the long fiber filler reinforced resin pellet,
etc., a process for producing the long fiber filler reinforced
resin pellet, and the like, as described below.
1.
[0017] A long fiber filler reinforced resin pellet, comprising a
long fiber filler and a thermoplastic resin blend, wherein:
[0018] the long fiber filler is, in said pellet, to form a spiral
with a central axis along a longitudinal direction of said pellet;
and
[0019] said pellet has a skin layer part with a lower content of
the long fiber filler, and a core part with a higher content of the
long fiber filler, a cross-section of said core part being in a
range from 30% to 70% of the cross-section of said pellet; and
[0020] said thermoplastic resin blend comprises polyphenylene ether
and a thermoplastic resin other than polyphenylene ether.
2.
[0021] The long fiber filler reinforced resin pellet according to
1., wherein a ratio of an average fiber length of said long fiber
filler to the length of said long fiber filler reinforced resin
pellet exceeds 1.0.
3.
[0022] The long fiber filler reinforced resin pellet according to
1. or 2., wherein a rate of said long fiber filler in said long
fiber filler reinforced resin pellet is 30 to 70% by mass.
4.
[0023] The long fiber filler reinforced resin pellet according to
any one of 1.-3., wherein said long fiber filler is a glass
fiber.
5.
[0024] The long fiber filler reinforced resin pellet according to
any one of 1.-4., wherein a reduced viscosity (a chloroform
solution of 0.5 g/dL concentration, measured at 30.degree. C.) of
said polyphenylene ether is in a range from 0.30 to 0.55 dL/g.
6.
[0025] The long fiber filler reinforced resin pellet according to
any one of 1.-5., wherein said polyphenylene ether is a copolymer
comprising 2,3,6-trimethylphenol, and a rate of a unit of said
2,3,6-trimethylphenol in the polyphenylene ether is from 10 to 30%
by mass.
7.
[0026] The long fiber filler reinforced resin pellet according to
any one of 1.-6., wherein said thermoplastic resin other than the
polyphenylene ether is one or more selected from the group
consisting of a styrenic resin, an olefinic resin, polyester,
polyamide, polyarylene sulfide, polyarylate, polyetherimide,
polyethersulfone, polysulfone and polyaryl ketone.
8.
[0027] The long fiber filler reinforced resin pellet according to
any one of 1.-7., wherein said thermoplastic resin other than the
polyphenylene ether is one or more selected from the group
consisting of homo-polystyrene, rubber-modified polystyrene,
acrylonitrile-styrene copolymer and N-phenylmaleimide-styrene
copolymer.
9.
[0028] The long fiber filler reinforced resin pellet according to
8., wherein a rate of said polyphenylene ether in said
thermoplastic resin blend is from 10 to 90% by mass.
10.
[0029] The long fiber filler reinforced resin pellet according to
any one of 1.-7., wherein said thermoplastic resin other than the
polyphenylene ether is one or more selected from the group
consisting of polypropylene, liquid crystal polyester, polyamide,
polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone,
polysulfone and polyaryl ketone.
11.
[0030] The long fiber filler reinforced resin pellet according to
10., wherein the rate of said polyphenylene ether in said
thermoplastic resin blend is from 1 to 50% by mass.
12.
[0031] The long fiber filler reinforced resin pellet according to
any one of 1.-11., further comprising a compatibilizer.
13.
[0032] The long fiber filler reinforced resin pellet according to
12., wherein said compatibilizer is a compound having one or more
functional groups selected from the group consisting of an epoxy
group, an oxazolyl group, an imide group, a carboxylic group and an
acid anhydride group.
14.
[0033] The long fiber filler reinforced resin pellet according to
any one of 1.-13., further comprising a sterically-hindered
phenol-based antioxidant in an amount from 0.1 to 5 parts by mass
based on 100 parts by mass of said thermoplastic resin blend.
15.
[0034] The long fiber filler reinforced resin pellet according to
any one of 1.-14., further comprising a flame retardant without
halogen in an amount from 5 to 50 parts by mass based on 100 parts
by mass of said thermoplastic resin blend.
16.
[0035] The long fiber filler reinforced resin pellet according to
any one of 1.-15., further comprising a filler other than the long
fiber filler.
17.
[0036] A resin pellet blend comprising:
[0037] 100 parts by mass of the long fiber filler reinforced resin
pellet according to any one of 1.-16.; and
[0038] 0.5 to 150 parts by mass of a resin pellet without the long
fiber filler.
18.
[0039] The resin pellet blend according to 17., wherein a rate of
said long fiber filler in said resin pellet blend is from 10 to 60%
by mass.
19.
[0040] The resin pellet blend according to 17. or 18., wherein said
resin pellet without the long fiber filler further comprises a
filler other than the long fiber filler.
20.
[0041] The resin pellet blend according to 19., wherein said filler
other than the long fiber filler is one or more fillers selected
from the group consisting of a hydroxide of an element selected
from magnesium and calcium, an oxide of an element selected from
the group consisting of magnesium, titanium, iron, copper, zinc and
aluminum; zinc sulfide, zinc borate, calcium carbonate, talc,
wollastonite, glass, carbon black, carbon nanotube and silica; and
an average particle size of said filler other than the long fiber
filler is not more than 1 mm.
21.
[0042] A molded article produced by melt-molding of the long fiber
filler reinforced resin pellet according to any one of 1.-16.
22.
[0043] A process for producing a long fiber filler reinforced resin
pellet, wherein the pellet comprises a long fiber filler and a
thermoplastic resin blend;
[0044] said long fiber filler is aligned, in said pellet, to form a
spiral with a central axis along a longitudinal direction of said
pellet; and
[0045] said pellet comprises a skin layer part with a lower content
of the long fiber filler, and a core part with a higher content of
the long fiber filler, the cross-section of said core part being in
a range from 30% to 70% of the cross-section of said pellet;
[0046] said thermoplastic resin blend comprises polyphenylene ether
and a thermoplastic resin other than polyphenylene ether; and
[0047] the process for producing the long fiber filler reinforced
resin pellet comprises the steps of:
(1) producing said thermoplastic resin blend in a molten state by
an extruder, (2) impregnating said long fiber filler with said
thermoplastic resin blend in the molten state, (3) forming a resin
strand by drawing and twisting, and (4) cutting said resin strand
to a pellet form. 23.
[0048] The process for producing the long fiber filler reinforced
resin pellet according to 22., wherein the process for producing
the long fiber filler reinforced resin pellet comprises the steps
(1) to (4) in said successive order.
24.
[0049] The process for producing the long fiber filler reinforced
resin pellet according to 22. or 23., wherein the step (1) further
comprising producing said thermoplastic resin blend in the molten
state by blending said polyphenylene ether and said thermoplastic
resin other than the polyphenylene ether.
25.
[0050] The process for producing the long fiber filler reinforced
resin pellet according to any one of 22.-24., wherein a set
temperature of a dipping bath in the step (2), in which said long
fiber filler is impregnated in said thermoplastic resin blend in
the molten state, is higher by 20.degree. C. or more than a set
temperature of the extruder in said step (1).
26.
[0051] The process for producing the long fiber filler reinforced
resin pellet according to any one of 22.-25., wherein a drawing
speed in said step (3) is in a range from 10 to 150 m/min.
[0052] According to the present invention, a long fiber filler and
a thermoplastic resin blend have good wettability, which suppresses
extremely longitudinal fracture of a pellet during transportation
and detachment of a long fiber filler from a pellet, offers good
pellet appearance and superior fibrillation property of a long
fiber filler during molding, and can provide a long fiber filler
reinforced resin pellet able to mold a molded article with
extremely high heat resistance and impact strength.
BEST MODE FOR CARRYING OUT THE INVENTION
[0053] The best mode for carrying out the present invention
(hereinafter referred to as "the Embodiment") will be explained in
more detail below. The present invention should not be limited to
the following Embodiment, and various changes may be made therein
within the spirit of the invention.
[0054] A long fiber filler reinforced resin pellet according to the
Embodiment (hereinafter occasionally abbreviated simply as "the
pellet") is a pellet composed of a long fiber filler and a
thermoplastic resin blend.
[0055] The long fiber filler is aligned in the pellet forming a
spiral with the central axis along the longitudinal direction of
the pellet, the lead of the spiral is 20 mm to 80 mm, the pellet
has a skin layer part with a lower content of the long fiber filler
and a core part with a higher content of the long fiber filler, and
the cross-section of the core part is in a range of 30% to 70% of
the cross-section of the pellet.
[0056] The thermoplastic resin blend (hereinafter occasionally
abbreviated simply as "the resin") contains polyphenylene ether and
a thermoplastic resin other than polyphenylene ether.
(Long Fiber Filler)
[0057] The long fiber filler to be used in the long fiber filler
reinforced resin pellet according to the Embodiment is aligned in
the pellet forming a spiral with the central axis along the
longitudinal direction of the pellet, the lead of the spiral is 20
mm to 80 mm, the pellet has a skin layer part with a lower content
of the long fiber filler and a core part with a higher content of
the long fiber filler, and the cross-section of the core part is in
a range of 30% to 70% of the cross-section of the pellet.
[0058] In the Embodiment, the long fiber filler is aligned in the
pellet forming a spiral with the central axis along the
longitudinal direction of the pellet, thereby the longitudinal
direction of the pellet means the extending direction of the long
fiber filler, and, in case the pellet form is a cylindrical pellet,
the direction of its height.
[0059] In the Embodiment, "aligned forming a spiral" means that the
long fiber filler exists in the pellet in a twisted state.
[0060] In the Embodiment, since the long fiber filler is aligned in
the pellet forming a spiral with the central axis along the
longitudinal direction of the pellet, longitudinal fracture of the
pellet during transportation and detachment of the long fiber
filler from the pellet can be suppressed.
[0061] In the Embodiment, the long fiber filler may exist as a
fiber bundle forming a spiral in the pellet, so that detachment of
the long fiber filler from the pellet can be suppressed, forming
the pellet of excellent appearance. More preferably, the fiber
bundle of the long fiber filler forms a single bundle in the
pellet.
[0062] In the Embodiment, a long fiber filler is "not aligned in a
spiral form" means that the long fiber filler exists in the pellet
in a not twisted state, and examples of a pellet without alignment
in a spiral form include pellets disclosed by Patent Literature 1
and Patent Literature 2.
[0063] In the Embodiment, the lead of a spiral has the same meaning
as the lead of a screw, and specifically, it means a distance along
the longitudinal direction over the strand surface, which a long
fiber filler aligned in spiral advances in rotating once
(360.degree.) around the outer surface of a strand.
[0064] In the Embodiment, with the lead of the spiral of 20 mm or
longer, deterioration of the pellet appearance due to detachment at
the interface between the resin and the long fiber filler, or
deterioration of the fibrillation property during molding may be
suppressed. Further, with the lead of the spiral of 80 mm or
shorter, longitudinal fracture of the pellet during transportation,
detachment of the long fiber filler from the pellet and defective
feeding into a molding machine during molding may be
suppressed.
[0065] In the Embodiment, the lead of the spiral is preferably 25
mm or longer, more preferably 27 mm or longer, and further
preferably 30 mm or longer. Further, the lead of the spiral is
preferably 75 mm or shorter, more preferably 60 mm or shorter, and
further preferably 55 mm or shorter.
[0066] In the Embodiment, the pellet has a skin layer part with a
lower content of the long fiber filler, and a core part with a
higher content of the long fiber filler, and the cross-section of
the core part is in a range of 30% to 70% of the cross-section of
the pellet.
[0067] The skin layer part with a lower content of the long fiber
filler means a region continued from the pellet surface composed of
the resin, in which the fill content of the filled long fiber
filler is less than half of the fill content of the filled long
fiber filler in the pellet as a whole, and for example, if the fill
content of the long fiber filler in the pellet is 40% by mass, the
region with the fill content of the long fiber filler less than 20%
by mass is meant as the skin layer part. In the Embodiment,
however, a region with half or less of the fill content of the long
fiber filler in the pellet is also deemed as the core part and
excluded from the skin layer part, if categorized in the following
case: as the long fiber filler exists in a twisted state, an
envelope of the long fiber filler may be defined in the pellet, and
the region inside the envelope surrounded by the region containing
the long fiber filler, namely the region not continuing from the
surface is excluded from the skin layer part.
[0068] In the Embodiment, the core part with a higher content of
the long fiber filler means a part of the cross-section of the
pellet excluding the skin layer part with a lower content of the
long fiber filler. In the Embodiment, since the long fiber filler
is added in the pellet in a twisted state, it exists in an
aggregated form in the pellet, and the skin layer part and the core
part can be easily discriminated by observing the cross-section of
the pellet under a microscope.
[0069] In the Embodiment, by limiting the cross-section of the core
part within 30 to 70% of the cross-section of the pellet, the
appearance of the pellet can be substantially improved and an
effect of improvement of the feed property into a molding machine
is obtainable. As for the pellet appearance, glossy appearance can
be obtained providing a pellet with high quality appearance.
[0070] In the Embodiment, the cross-section of the core part is
preferably 35% or more of the cross-section of the pellet, more
preferably 40% or more, and further preferably 45% or more.
Further, the cross-section of the core part is preferably 65% or
less of the cross-section of the pellet, and more preferably 60% or
less.
[0071] In the Embodiment, the cross-section of the core part may be
determined by observing at least 10 cross-sections of a pellet and
averaging the cross-sections of the core part, as described in more
detail in an Example below.
[0072] In the Embodiment, the length of the long fiber filler ("the
fiber length") is preferably 3 mm or longer, more preferably 4 mm
or longer and further preferably 5-mm or longer, in order to make
high enough the heat resistance and impact strength of a molded
article produced by melt-molding of the long fiber filler
reinforced resin pellet, etc. (hereinafter occasionally abbreviated
simply as "molded article"). Further, the length of the long fiber
filler is preferably 50 mm or shorter, from the viewpoint of the
handling property at molding, more preferably 30 mm or shorter, and
further preferably 20 mm or shorter.
[0073] In the Embodiment, concerning the fiber length of the long
fiber filler, in order to obtain a pellet with excellent appearance
and fewer longitudinal fracture, the fiber length of the contained
long fiber filler is preferably longer than the length of the
pellet containing the long fiber filler, and more preferably the
ratio of the average fiber length of the long fiber filler to the
length of the pellet exceeds 1.0.
[0074] Further preferably, the ratio of the average fiber length of
the long fiber filler to the length of the pellet is in a range of
1.01 to 1.2, further preferably 1.02 or higher, and especially
preferably 1.03 or higher. Meanwhile, the ratio of the average
fiber length of the long fiber filler to the length of the pellet
is more preferably 1.15 or lower, further preferably 1.1 or lower,
and especially preferably 1.08 or lower.
[0075] In the Embodiment, the length of a pellet means the length
of the longitudinal direction of the pellet, and for example in
case of a cylindrical pellet it means the height.
[0076] In the Embodiment, the content of the long fiber filler in
the pellet is preferably 30 to 70% by mass.
[0077] By keeping the content of the long fiber filler in the
pellet at 30% by mass or higher, drawing property during pellet
production can be improved and the viscosity of the strand during
pellet production can be kept at an appropriate viscosity level.
Further, by keeping the content of the long fiber filler in the
pellet at 70% by mass or lower, penetration of the resin into the
long fiber filler can be improved to enhance the wettability, by
which the drawing speed of the strand during pellet production can
be controlled comfortably.
[0078] More preferably, the content of the long fiber filler in the
pellet is 40% by mass or higher, and further preferably 45% by mass
or higher. And the content of the long fiber filler in the pellet
is more preferably 60% by mass or lower, and further preferably is
55% by mass or lower.
[0079] In the Embodiment, examples of a long fiber filler to be
used for the long fiber filler reinforced resin pellet include one
or more long fiber filler selected from the group consisting of a
carbon fiber, a glass fiber, a metal fiber and an aramid fiber may
be exemplified.
[0080] In the Embodiment, the long fiber filler is preferably one
or more selected from a carbon fiber and a glass fiber, and is more
preferably a glass fiber from the viewpoint of enhancement of
strength and rigidity of an molded article of the long fiber filler
reinforced resin pellet according to the embodiment.
[0081] In the Embodiment, although there is no particular
restriction on the diameter of the long fiber filler, it is
preferably 5 .mu.m or larger, more preferably 8 .mu.m or larger,
and further preferably 10 .mu.m or larger. And preferably the
diameter of the long fiber filler is 25 .mu.m or shorter, more
preferably 20 .mu.m or shorter, and further preferably 17 .mu.m or
shorter.
[0082] In the Embodiment, the long fiber filler, which surface is
coated appropriately with a coupling agent, a binder, etc. in order
to improve the wettability or handling property of the resin, may
be used.
[0083] Examples of a coupling agent include an amino, epoxy, chlor,
mercapto and cationic silane coupling agents, and an amino silane
coupling agent can be favorably used.
[0084] As a binder, a binder containing one or more selected from:
a maleic anhydride compound, a urethane compound, an acryl
compound, an epoxy compound and a copolymer of such compounds; may
be exemplified, and a binder containing a urethane compound can be
favorably used.
[0085] A favorable content of a binder in the long fiber filler is
0.1 to 0.5% by mass. By coating a binder on the surface of the long
fiber filler at the content of 0.1% by mass or higher, the
longitudinal fracture of the pellet can be prevented, and by
coating a binder on the surface of the long fiber filler at the
content of 0.5% by mass or lower, the fibrillation property of the
long fiber filler at the step of impregnating the long fiber filler
with the resin is not deteriorated and deterioration of the
productivity can be suppressed.
[0086] The content of a binder is more preferably 0.15% by mass or
higher, further preferably 0.2% by mass, and still further
preferably 0.25% by mass or higher. And the content of a binder is
more preferably 0.45% by mass or lower, further preferably 0.4% by
mass or lower, and still further preferably 0.35% by mass or
lower.
(Thermoplastic Resin Blend)
[0087] In the Embodiment, a thermoplastic resin blend used for the
long fiber filler reinforced resin pellet is composed of
polyphenylene ether and a thermoplastic resin other than
polyphenylene ether.
(Polyphenylene Ether)
[0088] In the Embodiment, by use of polyphenylene ether in the
thermoplastic resin blend the melt viscosity of the resin is
increased appropriately and the twisted long fiber filler can be
extremely easily fibrillated during molding.
[0089] By the improved fibrillation property during molding, the
effect of the use of the long fiber filler, namely high strength
and rigidity of a molded article can be achieved to a maximum
extent.
[0090] In the Embodiment, polyphenylene ether is a homo- or
copolymer having a recurring structural unit represented by the
following formula (1).
##STR00001##
[0091] wherein O represents an oxygen atom, and R.sub.1 to R.sub.4
independently represent a group selected from the group consisting
of hydrogen, halogen, a linear or branched C1 to C7 alkyl group, a
phenyl group, a C1 to C7 haloalkyl group, a C1 to C7 aminoalkyl
group, a C1 to C7 hydrocarbyloxy group and a halohydrocarbyloxy
group, provided that a halogen atom and an oxygen atom are
separated by at least 2 carbon atoms.
[0092] In the Embodiment, there is no particular restriction on the
production process of polyphenylene ether, so far as it is a
publicly known process. Examples of a production process include
those disclosed by U.S. Pat. No. 3,306,874, U.S. Pat. No.
3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358,
Japanese Patent Application Laid-Open No. 50-51197, Japanese Patent
Publication No. 52-17880 and Japanese Patent Publication No.
63-152628.
[0093] Examples of polyphenylene ether include
poly(2,6-dimethyl-1,4-phenylene ether),
poly(2-methyl-6-ethyl-1,4-phenylene ether),
poly(2-methyl-6-phenyl-1,4-phenylene ether),
poly(2,6-dichloro-1,4-phenylene ether).
[0094] As a copolymer of polyphenylene ether, a copolymer of
2,6-dimethylphenol with other phenols may be exemplified, for
example, a copolymer with 2,3,6-trimethylphenol or a copolymer with
2-methyl-6-butylphenol.
[0095] From the standpoint of commercial availability,
poly(2,6-dimethyl-1,4-phenylene ether), a copolymer of
2,6-dimethylphenol and 2,3,6-trimethylphenol, or the blend thereof
is preferable as polyphenylene ether. In case a copolymer of
2,6-dimethylphenol and 2,3,6-trimethylphenol is used, concerning
the contents of the respective monomer units, a copolymer
containing 10 to 30% by mass of the structural unit of
2,3,6-trimethylphenol in the polyphenylene ether copolymer is
preferable, more preferable 15 to 25% by mass, and further
preferable 20 to 25% by mass.
[0096] In the Embodiment, the reduced viscosity (.eta..sub.sp/c:
dL/g, a chloroform solution of 0.5 g/dL concentration, measured at
30.degree. C.) of polyphenylene ether is preferably in a range of
0.30 to 0.55 dL/g. The reduced viscosity of the polyphenylene ether
is more preferably 0.53 dL/g or lower, further preferably 0.45 dL/g
or lower, and still further preferably 0.36 dL/g or lower.
[0097] By making the reduced viscosity of the polyphenylene ether
at 0.30 dL/g or higher, a pellet with superior fibrillation
property of the long fiber filler during molding can be obtained,
and at 0.55 dL/g or lower, the wettability can be improved.
[0098] In the Embodiment, a blend of 2 or more types of
polyphenylene ether having different reduced viscosities can be
used without particular restrictions. Examples include a blend of a
polyphenylene ether with the reduced viscosity of approximately
0.40 dL/g and a polyphenylene ether with the reduced viscosity of
approximately 0.50 dL/g, and a blend of a low molecular weight
polyphenylene ether with the reduced viscosity of approximately
0.08 to 0.12 dL/g and a polyphenylene ether with the reduced
viscosity of approximately 0.50 dL/g.
[0099] In case a blend of 2 or more types of polyphenylene ether
having different reduced viscosities is used, the reduced viscosity
of the blended polyphenylene ether is preferably in a range of 0.30
to 0.55 dL/g.
[0100] In the Embodiment, the polyphenylene ether may be modified
using a modifier, and examples of a modifier include saturated or
unsaturated dicarboxylic acids and derivatives thereof, such as
maleic anhydride, N-phenylmaleimide, malic acid, citric acid and
fumaric acid; and vinyl compounds, such as styrene, acrylic ester
and methacrylic ester.
[0101] In case a modified polyphenylene ether is used as the
polyphenylene ether, the same may be modified in advance, or may be
modified by adding a modifier during melt-extrusion to produce the
resin.
(Thermoplastic Resin Other than Polyphenylene Ether)
[0102] Although there is no particular restriction on the
thermoplastic resin other than polyphenylene ether, an example
thereof is one or more selected from the group consisting of a
styrenic resin, an olefinic resin, polyester, polyamide,
polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone,
polysulfone and polyaryl ketone. The thermoplastic resin other than
polyphenylene ether may be used alone or as a blend of the above
thermoplastic resins.
[0103] A preferable thermoplastic resin other than the
polyphenylene ether is one or more selected from the group
consisting of polypropylene, liquid crystal polyester, polyamide,
polyarylene sulfide, polyarylate, polyetherimide, polyethersulfone,
polysulfone, polyaryl ketone, homo-polystyrene, rubber-modified
polystyrene, acrylonitrile-styrene copolymer and
N-phenylmaleimide-styrene copolymer.
[0104] In case, as a thermoplastic resin other than the
polyphenylene ether, one or more thermoplastic resins having
relatively low affinity to the polyphenylene ether selected from
the group consisting of an olefinic resin such as polypropylene,
polyester such as liquid crystal polyester, polyamide, polyarylene
sulfide, polyarylate, polyetherimide, polyethersulfone, polysulfone
and polyaryl ketone are used, the content of the polyphenylene
ether in the resin is preferably in a range of 1 to 50% by mass.
The content of the polyphenylene ether in the resin is more
preferably 5% by mass or higher, further preferably 10% by mass or
higher, and still further preferably 15% by mass or higher. And the
content of the polyphenylene ether in the resin is more preferably
45% by mass or lower, further preferably 40% by mass or lower, and
still further preferably 35% by mass or lower.
[0105] By making the content of the polyphenylene ether 1% by mass
or higher, the heat resistance of the polymer can be favorably
enhanced. From the standpoint of inhibition of deterioration of the
wettability with the long fiber filler, the content of the
polyphenylene ether is preferably 50% by mass or lower.
[0106] In case, as a thermoplastic resin other than the
polyphenylene ether, one or more polystyrenic resins, which are
thermoplastic resins having relatively high affinity to the
polyphenylene ether, selected from the group consisting of
homo-polystyrene, rubber-modified polystyrene,
acrylonitrile-styrene copolymer and N-phenylmaleimide-styrene
copolymer, the content of the polyphenylene ether in the resin is
preferably in a range of 10 to 90% by mass. The content of the
polyphenylene ether is more preferably 20% by mass or higher, and
further preferably 30% by mass or higher. And the content of the
polyphenylene ether is more preferably 80% by mass or lower,
further preferably 70% by mass or lower, and still further
preferably 60% by mass or lower.
(Styrenic Resin)
[0107] In the Embodiment, examples of a styrenic resin include
homo-polystyrene, rubber-modified polystyrene (generally called as
high-impact polystyrene), styrene-butadiene block-copolymer and/or
a hydrogenated product thereof, styrene-isoprene block-copolymer
and/or a hydrogenated product thereof, and a copolymer of styrene
and radically copolymerizable vinyl monomer.
[0108] Specific examples of a vinyl monomer radically
copolymerizable with styrene include vinyl cyanide compounds, such
as acrylonitrile and methacrylonitrile; vinyl carboxylic acids and
esters thereof, such as acrylic acid, butyl acrylate, methacrylic
acid, methyl methacrylate and ethylhexyl methacrylate; unsaturated
dicarboxylic anhydrides and derivatives thereof, such as maleic
anhydride and N-phenylmaleimide; and diene compounds, such as
butadiene and isoprene, and two or more of them may be combined and
copolymerized.
[0109] From the viewpoint of commercial availability, examples of a
preferable styrenic resin include homo-polystyrene, rubber-modified
polystyrene, acrylonitrile-styrene copolymer,
N-phenylmaleimide-styrene copolymer and a blend thereof.
[0110] Concerning homo-polystyrene and rubber-modified polystyrene,
from the viewpoint of maintenance of balance between flowability
and mechanical strength of the obtained thermoplastic resin blend,
homo-polystyrene and rubber-modified polystyrene having the reduced
viscosity (measured at 30.degree. C. in a toluene solution of 0.5
g/100 mL concentration) in a range 0.5 to 2.0 dL/g are preferable.
The reduced viscosity of homo-polystyrene and rubber-modified
polystyrene is more preferably 0.7 dL/g or higher and further
preferably 0.8 dL/g or higher. And the reduced viscosity of
homo-polystyrene and rubber-modified polystyrene is preferably 1.5
dL/g or lower and more preferably 1.2 dL/g or lower.
[0111] Concerning an acrylonitrile-styrene copolymer, from the
viewpoint of chemical resistance and heat resistance of the
obtained thermoplastic resin blend, an acrylonitrile-styrene
copolymer containing 3 to 30% by mass of acrylonitrile in the
copolymer as a structural unit is preferable.
[0112] The content of acrylonitrile in the copolymer is more
preferably 5% by mass or higher, and further preferably 7% by mass
or higher. And the content of acrylonitrile in the copolymer is
more preferably 20% by mass or lower, further preferably 15% by
mass or lower, and further preferably 10% by mass or lower.
[0113] The acrylonitrile-styrene copolymer may be a copolymer
further copolymerized with butadiene in an amount of 30 parts by
mass or less based on 100 parts by mass of the
acrylonitrile-styrene copolymer.
[0114] As an N-phenylmaleimide-styrene copolymer, from the
viewpoint of heat resistance of the obtained thermoplastic resin
blend and affinity to polyphenylene ether, an
N-phenylmaleimide-styrene copolymer having 15 to 70% by mass of
N-phenylmaleimide in the copolymer as a structural unit is
preferable.
[0115] The content of N-phenylmaleimide in the copolymer is more
preferably 20% by mass or higher, and further preferably 25% by
mass or higher. And the content of N-phenylmaleimide in the
copolymer is more preferably 65% by mass or lower, and further
preferably 60% by mass or lower.
[0116] The N-phenylmaleimide-styrene copolymer may be a copolymer
further copolymerized with acrylonitrile in an amount of 30 parts
by mass or less based on 100 parts by mass of the
N-phenylmaleimide-styrene copolymer.
[0117] From the viewpoint of maintaining the heat resistance of the
obtained thermoplastic resin blend, the glass transition
temperature of an N-phenylmaleimide-styrene copolymer is preferably
in a range of 140.degree. C. to 220.degree. C.
[0118] In the Embodiment, the glass transition temperature is, for
example, the glass transition temperature observed by a DSC
apparatus measured at the temperature elevation speed of 20.degree.
C./min.
(Olefinic Resin)
[0119] In the Embodiment, examples of an olefinic resin include
polyethylene, polypropylene, an ethylene-.alpha.-olefin copolymer
and an ethylene-acrylate copolymer, and polypropylene (hereinafter
occasionally abbreviated simply as "PP") is preferable.
[0120] In the Embodiment, examples of polypropylene include a
crystalline propylene homopolymer and a crystalline
propylene-ethylene block copolymer composed of a crystalline
propylene homopolymer portion produced in the first polymerization
step and a propylene-ethylene random copolymer portion produced in
the second or later polymerization step by copolymerizing
propylene, ethylene and/or at least one other .alpha.-olefin, such
as 1-butene and 1-hexene. Polypropylene may be a blend of a
crystalline propylene homopolymer and a crystalline
propylene-ethylene block copolymer.
[0121] In general, polypropylene is produced by polymerization
using a titanium trichloride catalyst or a titanium halide catalyst
supported on a magnesium chloride support or the like in the
presence of an alkyl aluminum compound, in a polymerization
temperature range of 0 to 100.degree. C., and a polymerization
pressure range of 3 to 100 atm. Thereby a chain transfer agent such
as hydrogen may be added to regulate the molecular weight of a
polymer. As a polymerization process, both a batch process and a
continuous process are possible, and a solution polymerization or a
slurry polymerization using a solvent, such as butane, pentane,
hexane, heptane and octane may be selected, and further, a bulk
polymerization in a monomer without a solvent, or a gas phase
polymerization in a monomer gas may be applied.
[0122] In order to enhance the isotacticity of polypropylene and
polymerization activity, as an third component an electron donating
compound may be used as an internal donor component or an external
donor component. As an electron donating compound, such publicly
known compounds as exemplified may be used: ester compounds, such
as .di-elect cons.-caprolactone, methyl methacrylate, ethyl
benzoate and methyl toluate; phosphites, such as triphenyl
phosphite and tributyl phosphite; phosphoric acid derivatives, such
as hexamethylphosphoric triamide; alkoxyester compounds; aromatic
monocarboxylic acid esters and/or aromatic alkylalkoxysilanes;
aliphatic hydrocarbon alkoxysilanes; various ether compounds; and
various alcohols and/or various phenols.
[0123] In the Embodiment, the density of a propylene polymer
portion in polypropylene is generally 0.90 g/cm.sup.3 or higher,
preferably 0.90 to 0.93 g/cm.sup.3, and more preferably 0.90 to
0.92 g/cm.sup.3.
[0124] The density of a propylene polymer portion can be easily
measured by an underwater replacement method according to JIS
K-7112. In case polypropylene is a copolymer containing propylene
as a main component and .alpha.-olefin, a copolymer portion is
extracted from the polypropylene by a solvent such as hexane, and
the density of the residual propylene polymer portion can be easily
measured by the above underwater replacement method according to
JIS K-7112.
[0125] In the Embodiment, it is effective to increase the density
of the polypropylene by adding a publicly known nucleating agent.
Although there is no restriction on the type of a nucleating agent
insofar as crystallization of polypropylene can be promoted,
examples may include organic nucleating agents, such as a metal
salt of an aromatic carboxylic acid, a sorbitol derivative, an
organic phosphate and an aromatic amide compound; and inorganic
nucleating agents such as talc.
[0126] In the Embodiment, from the viewpoint of improving the
wettability of the long fiber filler with the thermoplastic resin
blend, the MFR (according to JIS K-6758: 230.degree. C., load 21.2
N) of polypropylene is preferably 10 g/10 min or higher, more
preferably 20 to 50 g/10 min, further preferably 25 to 40 g/10 min,
and still further preferably 30 to 40 g/10 min.
(Polyester)
[0127] In the Embodiment, examples of polyester include
polybutylene terephthalate, polypropylene terephthalate,
polyethylene terephthalate, polyethylene naphthalate, polybutylene
naphthalate, polypropylene naphthalate and liquid crystal
polyesters; and among them liquid crystal polyesters are
preferable.
[0128] In the Embodiment, the liquid crystal polyester means such
polyester as is called as a thermotropic liquid crystal polymer.
Examples of a thermotropic liquid crystal polymer include, but not
limited thereto, a thermotropic liquid crystal polyester containing
p-hydroxybenzoic acid, alkylene glycol or terephthalic acid as a
main structural unit, a thermotropic liquid crystal polyester
containing p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as
main structural units, and a thermotropic liquid crystal polyester
containing p-hydroxybenzoic acid and 4,4'-dihydroxybiphenyl as well
as terephthalic acid as main structural units.
[0129] As the liquid crystal polyester to be used in the
Embodiment, the following structural units (A) and (B) and, as
necessary, (C) and/or (D) may be favorably used.
##STR00002##
[0130] The structural units (A) and (B) are respectively a
structural unit of polyester derived from p-hydroxybenzoic acid and
a structural unit derived from 2-hydroxy-6-naphthoic acid.
[0131] By incorporating the structural units (A) and (B), a resin
having a good balance of heat resistance, flowability and
mechanical properties such as rigidity can be obtained.
[0132] The X in the structural units (C) and (D) is one or two or
more groups independently selected from the following group:
##STR00003##
[0133] The structural unit (C) is preferably a structural unit
derived from ethylene glycol, hydroquinone, 4,4'-dihydroxybiphenyl,
2,6-dihyroxynaphthalene, bisphenol A, etc., more preferably a
structural unit derived from ethylene glycol,
4,4'-dihydroxybiphenyl and hydroquinone, and further preferably a
structural unit derived from ethylene glycol and
4,4'-dihydroxybiphenyl.
[0134] The structural unit (D) is preferably a structural unit
derived respectively from terephthalic acid, isophthalic acid,
2,6-naphthalenedicarboxylic acid, etc., and more preferably a
structural unit derived from 2,6-naphthalenedicarboxylic acid and
terephthalic acid.
[0135] The structural unit (C) or (D) may use one or more of the
above-described structural units simultaneously. In case more than
one are used simultaneously, concerning the structural unit (C),
for example, a structural unit derived from ethylene glycol and a
structural unit derived from hydroquinone, a structural unit
derived from ethylene glycol and a structural unit derived from
4,4'-dihydroxybiphenyl, as well as a structural unit derived from
hydroquinone and a structural unit derived from
4,4'-dihydroxybiphenyl may be exemplified. Concerning the
structural unit (D), a structural unit derived from terephthalic
acid and a structural unit derived from isophthalic acid as well as
a structural unit derived from terephthalic acid and a structural
unit derived from 2,6-naphthalenedicarboxylic acid may be
exemplified.
[0136] Although there are no particular restrictions on the usage
ratio among the structural units (A), (B), (C) and (D) in a liquid
crystal polyester, it is basically preferable that the structural
units (C) and (D) are used in substantially same molar
quantities.
[0137] The following structural unit (E) constituted of the
structural units (C) and (D) may be used as a structural unit in a
liquid crystal polyester.
O--X--OCO--X--CO [Formula]7
(E)
[0138] The X in the structural unit (E) is same as described
above.
[0139] Specific examples of the structural unit (E) include a
structural unit derived from ethylene glycol and a structural unit
derived from terephthalic acid, a structural unit derived from
hydroquinone and a structural unit derived from terephthalic acid,
a structural unit derived from 4,4'-dihydroxybiphenyl and a
structural unit derived from terephthalic acid, a structural unit
derived from 4,4'-dihydroxybiphenyl and a structural unit derived
from isophthalic acid, a structural unit derived from bisphenol A
and a structural unit derived from terephthalic acid, as well as a
structural unit derived from hydroquinone and a structural unit
derived from 2,6-naphthalenedicarboxylic acid.
[0140] In the Embodiment, the liquid crystal polyester may,
according to need and in a small amount to the extent that the
characteristics and effects of the Embodiment are not impaired,
employ a structural unit derived from other aromatic dicarboxylic
acids, aromatic diols and aromatic hydroxycarboxylic acids.
[0141] In the Embodiment, by melting a liquid crystal polyester,
the temperature at which a liquid crystal phase starts to appear
(hereinafter referred to as "LC transition temperature") is
preferably in the range from 150 to 350.degree. C., and more
preferably in the range from 180 to 320.degree. C. By setting the
LC transition temperature in said range, the obtained resin can
have a favorable color tone and a good balance of heat resistance
and moldability.
[0142] As a specific measuring method of the LC transition
temperature in the Embodiment, the liquid crystal polyester is
observed under a polarizing microscope with a heated stage by
heating the same at a temperature elevating rate of 1.degree.
C./min, to find a temperature at which an anisotropic molten phase
is observed.
[0143] In the Embodiment, the dielectric tangent (tan .delta.) of a
liquid crystal polyester at 25.degree. C., 1 MHz is preferably 0.03
or less, and more preferably 0.025 or less.
[0144] In the Embodiment, the dielectric tangent is a value
determined by a measuring method according to JIS-K6911. The
smaller the dielectric tangent is, the smaller the dielectric loss
is, which is preferable for suppressing generation of electric
noises, when the resin is used as a raw material for
electrical/electronic parts. The dielectric tangent (tan .delta.),
especially at 25.degree. C. in a high frequency region, namely in a
region of 1 to 10 GHz, is preferably 0.03 or less, and more
preferably 0.025 or less.
[0145] In the Embodiment, the apparent melt viscosity of a liquid
crystal polyester (at LC transition temperature+30.degree. C.,
under a shear rate of 100 sec.sup.-1) is preferably 10 to 3,000
Pas, more preferably 10 to 2,000 Pas, and further preferably 10 to
1,000 Pas. By making the apparent melt viscosity in the
above-described region, the flowability of the resin becomes
favorable.
[0146] In the Embodiment, as a specific measuring method of the
apparent melt viscosity, a method to measure a viscosity at the
aforementioned shear rate with a capillary rheometer may be
exemplified.
(Polyamide)
[0147] In the Embodiment, there is no restriction on the type of
polyamide, insofar as an amide bond {--NH--C(.dbd.O)--} is included
in a recurring structure of a polymer.
[0148] Examples of a manufacturing process of a polyamide include,
but not limited thereto, ring-opening polymerization of lactams,
polycondensation of a diamine and a dicarboxylic acid, and
polycondensation of an aminocarboxylic acid.
[0149] In the Embodiment, examples of a diamine include aliphatic
diamine, alicyclic diamine and aromatic diamine.
[0150] Specific examples of a diamine include
tetramethylenediamine, hexamethylenediamine,
undecamethylenediamine, dodecamethylenediamine,
tridecamethylenediamine, 1,9-nonanediamine,
2-methyl-1,8-octanediamine, 2,2,4-trimethylhexamethylenediamine,
2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine,
1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane,
m-phenylenediamine, p-phenylenediamine, m-xylylenediamine and
p-xylylenediamine.
[0151] In the Embodiment, examples of a dicarboxylic acid include
aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and
aromatic dicarboxylic acid.
[0152] Specific examples of a dicarboxylic acid include adipic
acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid,
1,1,3-tridecanedioic acid, 1,3-cyclohexanedicarboxylic acid,
terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid
and dimer acid.
[0153] In the Embodiment, examples of lactams include .di-elect
cons.-caprolactam, enantholactam and .omega.-laurolactam.
[0154] In the Embodiment, examples of an aminocarboxylic acid
include .di-elect cons.-aminocaproic acid, 7-aminoheptanoic acid,
8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic
acid, 12-aminododecanoic acid and 13-aminotridodecanoic acid.
[0155] In the Embodiment, examples of polyamide copolymers obtained
by polycondensation of one or a mixture of two or more of lactams,
diamine, dicarboxylic acid and/or .omega.-aminocarboxylic acid may
be used as a polyamide. Further, polyamide copolymers obtained by
polymerizing lactams, diamine, dicarboxylic acid and/or
.omega.-aminocarboxylic acid in a polymerization reactor to a low
molecular weight oligomer stage, and then in an extruder or the
like reacting it to a high molecular weight, may be also favorably
used.
[0156] Examples of a polyamide resin to be used favorably as a
polyamide of the Embodiment include polyamide 6, polyamide 66,
polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide
612, polyamide 6/66, polyamide 6/612, polyamide MXD
(m-xylylenediamine) 6, polyamide 6T, polyamide 6I, polyamide 6/6T,
polyamide 6/6I, polyamide 66/6T, polyamide 66/6I, polyamide 6T/6I,
polyamide 6/6T/6I, polyamide 66/6T/6I, polyamide 6/12/6T, polyamide
66/12/6T, polyamide 6/12/6I, polyamide 66/12/6I and polyamide 9T;
wherein polyamide 6I means a polyamide resin polymerized between
hexamethylenediamine and isophthalic acid, and polyamide 6/6T means
a polyamide copolymer resin among .di-elect cons.-aminocarboxylic
acid, hexamethylenediamine and terephthalic acid. Further, two or
more of the above polyamide resins may be additionally
copolymerized in an extruder or the like and used as a
polyamide.
[0157] As the polyamide of the Embodiment, from the viewpoint of
the improvement of the heat resistance of a molded article of the
obtained long fiber filler reinforced pellet, a polyamide having an
aromatic ring in a recurring structural unit is preferable.
Specific examples include polyamide MXD (m-xylylenediamine) 6,
polyamide 6T, polyamide 6I, polyamide 6/6T, polyamide 6/6I,
polyamide 66/6T, polyamide 66/6I, polyamide 6T/6I, polyamide
6/6T/6I, polyamide 66/6T/6I, polyamide 6/12/6T, polyamide 66/12/6T,
polyamide 6/12/6I, polyamide 66/12/6I and polyamide 9T; wherein
polyamide 6T/6I, polyamide 66/6T/6I and polyamide 9T are more
preferable, and polyamide 9T is further preferable. A mixture of
the preferable polyamides may be also used.
[0158] In the Embodiment, the viscosity of a polyamide measured in
96% sulfuric acid according to ISO 307 is preferably in a range of
70 to 160 mL/g, and more preferably in a range of 80 to 150
mL/g.
[0159] If the viscosity of a polyamide is 70 mL/g or higher, the
drawing property of a strand during pellet production can be well
regulated, and if it is 160 mL/g or lower, the wettability between
the long fiber filler and the resin can be well regulated.
[0160] As the polyamide of the Embodiment, a mixture of two or more
polyamides of the same polyamide type but with different viscosity
numbers may be used. Examples of a mixture of polyamides include a
mixture of a polyamide with the viscosity number of 170 mL/g and a
polyamide with the viscosity number of 80 mL/g, and a mixture of a
polyamide with the viscosity number of 120 mL/g and a polyamide
with the viscosity number of 115 mL/g.
[0161] The viscosity of a mixture of polyamides, which can be
measured after dissolving the mixture of polyamides in 96% sulfuric
acid according to ISO 307, is preferably in the above-described
range.
[0162] In the Embodiment, the terminal amino group concentration of
a polyamide is preferably 5 .mu.mol/g or higher, more preferably 10
.mu.mol/g or higher, further preferably 12 .mu.mol/g or higher, and
still further preferably 15 .mu.mol/g or higher in order to improve
the compatibility between a polyamide and a polyphenylene ether. In
order to regulate well the wettability between the long fiber
filler and the resin, the terminal amino group concentration of a
polyamide is preferably 45 .mu.mol/g or lower, more preferably 40
.mu.mol/g or lower, further preferably 35 .mu.mol/g or lower, and
still further preferably 30 .mu.mol/g or lower.
[0163] In the Embodiment, the terminal carboxyl group concentration
of a polyamide is preferably 20 .mu.mol/g or higher from the
viewpoint of flowability or mechanical properties such as rigidity
of the resin, and more preferably 30 .mu.mol/g or higher; and
preferably 150 .mu.mol/g or lower, more preferably 100 .mu.mol/g or
lower, and further preferably 80 .mu.mol/g or lower.
[0164] In the Embodiment, although there is no particular
restriction on the ratio of the terminal amino group concentration
to the terminal carboxyl group concentration of a polyamide
(terminal amino group concentration/terminal carboxyl group
concentration), it is preferably 1.0 or less from the viewpoint of
mechanical properties, more preferably 0.9 or less, further
preferably 0.8 or less, and still further preferably 0.7 or less.
And by making the ratio of the terminal amino group concentration
to the terminal carboxyl group concentration of a polyamide 0.1 or
higher, the pellet can be stably produced.
[0165] In the Embodiment, a publicly known method can be used as a
regulating method of the terminal amino group concentration and the
terminal carboxyl group concentration of a polyamide. For example,
a method of adding a terminal regulating agent, such as a diamine
compound, a monoamine compound, a dicarboxylic compound, a
monocarboxylic compound, an acid anhydride, monoisocyanate, a
monoacid halide, monoesters and monoalcohols, to reach the
predetermined terminal concentrations in a polymerization stage of
the polyamide resin, may be exemplified.
[0166] Examples of a terminal regulating agent reacting with a
terminal amino group include aliphatic monocarboxylic acids, such
as acetic acid, propionic acid, lactic acid, valeric acid, caproic
acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid,
palmitic acid, stearic acid, pivalic acid and isobutyric acid;
alicyclic monocarboxylic acids, such as cyclohexane carboxylic
acid; aromatic monocarboxylic acids, such as benzoic acid, toluic
acid, .alpha.-naphthalenecarboxylic acid,
.beta.-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid
and phenylacetic acid; and a mixture of a plurality of compounds
arbitrarily selected therefrom. Preferable monocarboxylic acid
compounds are, in view of reactivity, stability of capped termini,
price, etc., acetic acid, propionic acid, lactic acid, valeric
acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid,
myristic acid, palmitic acid, stearic acid and benzoic acid, and
more preferable is benzoic acid.
[0167] Examples of a terminal regulating agent reacting with a
terminal carboxyl group include aliphatic monoamines, such as
methylamine, ethylamine, propylamine, butylamine, hexylamine,
octylamine, decylamine, stearylamine, dimethylamine, diethylamine,
dipropylamine and dibutylamine; alicyclic monoamines, such as
cyclohexylamine and dicyclohexylamine; aromatic monoamines, such as
aniline, toluidine, diphenylamine and naphthylamine; and a mixture
of a plurality of compounds arbitrarily selected therefrom.
Preferable monoamine compounds are, in view of reactivity, a
boiling point, stability of capped termini, price, etc.,
butylamine, hexylamine, octylamine, decylamine, stearylamine,
cyclohexylamine and aniline.
[0168] In the Embodiment, in view of its accuracy and easiness, the
concentrations of a terminal amino group and a terminal carboxyl
group of a polyamide are preferably determined from integral values
of the characteristic signals corresponding to the respective
terminal groups by .sup.1H-NMR, for example, according to the
method disclosed by Japanese Patent Application Laid-Open No.
07-228775. A favorable solvent for the measurement is deuterated
trifluoroacetic acid. Even measuring by an apparatus with
sufficient resolving power, the number of scanning for summation by
.sup.1H-NMR is preferably at least 300 cycles.
[0169] The measurement of the concentration of a terminal amino
group or terminal carboxyl group of a polyamide can be made also by
a measurement method using titration as disclosed by Japanese
Patent Application Laid-Open No. 2003-55549.
[0170] To avoid influences of coexisting additives or lubricants,
quantitative measurement by .sup.1H-NMR is more preferable.
[0171] In the Embodiment, by regulating terminal amino groups
and/or terminal carboxyl groups using a terminal capping agent,
active termini are capped therewith. If, for example, benzoic acid
belonging to a monocarboxylic acid is used as a terminal capping
agent, a terminal group capped with a terminal phenyl group is
generated.
[0172] In the Embodiment, the concentration of the capped terminal
groups in a polyamide is preferably 20% or higher, more preferably
40% or higher, further preferably 45% or higher, and still further
preferably 50% or higher. While, the concentration of the capped
terminal groups in a polyamide is preferably 85% or lower, more
preferably 80% or lower, and further preferably 75% or lower.
[0173] In the Embodiment, the capped terminus rate of a polyamide
can be calculated according to the following mathematical formula
using the measured numbers of terminal carboxylic groups, terminal
amino groups and terminal groups capped by a terminal capping agent
existing in the polyamide:
Capped terminus rate (%)=[(.alpha.-.beta.)/.alpha.].times.100
wherein .alpha. represents the total number of terminal groups of
molecular chains (generally equal to 2 times the polyamide molecule
number), .beta. represents the summed number of uncapped residual
terminal carboxylic groups and terminal amino groups.
[0174] In the Embodiment, the water content of a polyamide is
preferably in a range of 500 to 3,000 ppm, and more preferably in a
range of 500 to 2,000 ppm.
[0175] By making the water content of a polyamide 500 ppm or
higher, a pellet with a favorable color tone can be obtained, and
making it 3,000 ppm or lower, sharp viscosity decrease of the resin
can be inhibited.
[0176] In the Embodiment, the measurement method of the water
content is based on a water vaporization method specifically
according to ISO 15512 Method B.
(Polyarylene Sulfide)
[0177] In the Embodiment, polyarylene sulfide is a polymer
containing a recurring unit of arylene sulfide represented by the
following formula generally in the amount of 50 mol % or more,
preferably 70 mol % or more, and more preferably 90 mol % or
more:
[--Ar--S--]
wherein Ar represents an arylene group.
[0178] In the Embodiment, examples of an arylene group include a
p-phenylene group, a m-phenylene group, a substituted-phenylene
group, a p,p'-diphenylene sulfone group, a p,p'-biphenylene group,
a p,p'-diphenylenecarbonyl group and a naphthylene group; wherein
examples of a substitution group include C1 to C10 alkyl groups and
phenyl groups.
[0179] In the Embodiment, a polyarylene sulfide may be a
homopolymer having one kind of an arylene group as a structural
unit, or a copolymer obtained by using a mixture of two or more
different arylene groups from the viewpoint of processability or
heat resistance. A favorable polyarylene sulfide is a polyphenylene
sulfide, in which an arylene group is a phenylene group, and a
polyphenylene sulfide having a recurring unit of p-phenylene
sulfide as a main constituting element (hereinafter occasionally
abbreviated simply as "PPS") is preferable in view of its superior
processability, heat resistance, and industrially easy
availability.
[0180] In the Embodiment, examples of a production process of a
polyarylene sulfide include a method for polymerizing a halogenated
aromatic compound, such as p-dichlorobenzene, in the presence of
sulfur and sodium carbonate; a method for polymerizing it in a
polar solvent in the presence of sodium sulfide or sodium
hydrogensulfide and sodium hydroxide, or hydrogen sulfide and
sodium hydroxide or sodium aminoalkanoate; and a method for
self-condensating p-chlorothiophenol; but a method for reacting
sodium sulfide and p-dichlorobenzene in an amide solvent, such as
N-methylpyrrolidone and dimethylacetamide, or a sulfone solvent,
such as sulfolane, is applied favorably.
[0181] In the Embodiment, trichlorobenzene may be used as a
branching agent according to need, in order to introduce a branch
structure in a molecular chain of polyarylene sulfide.
[0182] In the Embodiment, there is no restriction on the production
process of polyarylene sulfide, insofar as it should be a publicly
known process. Processes disclosed in U.S. Pat. No. 2,513,188,
Japanese Patent Publication No. 44-27671, Japanese Patent
Publication No. 45-3368, Japanese Patent Publication No. 52-12240,
Japanese Patent Application Laid-Open No. 61-225217, U.S. Pat. No.
3,274,165, Japanese Patent Publication No. 46-27255, Belgium Patent
No. 29437 and Japanese Patent Application Laid-Open No. 05-222196,
and the prior arts described in said patents may be
exemplified.
[0183] In the Embodiment, a PPS produced by the above publicly
known polymerization methods is usually a linear type PPS.
[0184] In the Embodiment, after polymerized to a linear type PPS,
the same may be subjected to a heat treatment at a temperature
below the melting point of the PPS (e.g. 200 to 250.degree. C.) in
the presence of oxygen to promote oxidative cross-linking, so that
the polymer molecular weight and the viscosity are appropriately
increased to obtain a cross-linked PPS. The cross-linked PPS
includes a half cross-linked PPS, in which cross-linking is
minimal.
[0185] Either or a mixture of both of a linear type PPS and a
cross-linked PPS may be used as PPS. Mixed use of a linear type PPS
and a cross-linked PPS is preferable in view of the effect of
making small the particle size of a dispersed phase of
polyphenylene ether.
[0186] In the Embodiment, to reduce pellet whitening or mold
depositing on the occasion of molding attributable to PPS, it is
preferable that the content of oligomers contained in PPS is 0.7%
by mass or less with respect to PPS.
[0187] In the Embodiment, the oligomer contained in PPS means a
substance extracted into a methylene chloride solution, when PPS is
extracted by methylene chloride. Generally oligomers contained in
PPS are a substance known as impurities of PPS, and the content of
oligomers can be measured specifically according to the following
method.
[0188] Into 80 mL of methylene chloride 5 g of PPS powder is added,
and a Soxhlet extraction is conducted for 6 hours, then after
cooling down to room temperature, a methylene chloride extract
solution is transferred to a weighing bottle. Then the vessel used
for the extraction is washed 3 times using total 60 mL of methylene
chloride, and the washing liquid is recovered into the weighing
bottle. Then, by heating to about 80.degree. C. the methylene
chloride in the weighing bottle is removed by evaporation, and the
amount of the residue is weighed. From the residue amount an
extracted amount by methylene chloride, namely the oligomer amount
in PPS can be determined.
[0189] In the Embodiment, the melt viscosity of polyarylene sulfide
at 300.degree. C. under a shear rate of 100 sec.sup.-1 is
preferably 10 to 150 Pas, more preferably 10 to 100 Pas, and
further preferably 10 to 80 Pas.
[0190] If the melt viscosity of polyarylene sulfide at 300.degree.
C. under a shear rate of 100 sec.sup.-1 is 10 Pas or higher, the
resin can have superior mechanical properties, and if it is 150 Pas
or lower, impregnation of the resin into the long fiber filler is
improved.
[0191] In the Embodiment, the melt viscosity of polyarylene sulfide
at 300.degree. C. under a shear rate of 100 sec.sup.-1 can be
measured by a capillary rheometer. For example it can be measured
at 300.degree. C. under a shear rate of 100 sec.sup.-1 by
Capirograph (Toyo Seiki Seisaku-sho, Ltd.) using a capillary of
capillary length=10 mm and capillary diameter=1 mm.
(Polyarylate)
[0192] In the Embodiment, polyarylate is a polymer having an
aromatic ring and an ester bond in the structural unit, and called
also as poly(aryl ester). As a polyarylate, a polyarylate having a
recurring unit represented by the following formula (2), for
example composed of bisphenol A and terephthalic acid and/or
isophthalic acid, is preferably used.
[0193] In the Embodiment, a polyarylate containing terephthalic
acid and isophthalic acid at a molar ratio of about 1:1 is
preferable from the viewpoint of heat resistance of a molded
article and toughness of the resin.
##STR00004##
[0194] In the Embodiment, as a polyarylate a commercial product may
be utilized, for example "U polymer" (Trade name of Unitika Ltd.)
may be utilized.
[0195] As for molecular weight of a polyarylate, the number average
molecular weight measured by gel permeation chromatography (GPC)
and reduced to polystyrene is preferably 5,000 to 300,000, more
preferably 10,000 to 300,000, and further preferably 10,000 to
100,000. If the number average molecular weight of a polyarylate is
5,000 or higher, heat resistance of a molded article is improved
and mechanical strength of the resin tends to increase, and if it
is 300,000 or lower, flowability of the resin is improved and the
dispersion phase of polyether phenol tends to disperse in smaller
size.
[0196] In the Embodiment, a specific measurement method of a number
average molecular weight reduced to polystyrene is: a measured
value by GPC using chloroform as a solvent, under a condition of a
column temperature of 40.degree. C., is fit to a detection
time-molecular weight curve measured in advance for a standard
polystyrene under the same conditions to obtain the reduced
molecular weight. Thereby, the concentration of a polyarylate in
the chloroform solution is 1 g/L. A detector is preferably a UV
absorption detector measuring around 280 nm.
(Polyethersulfone, Polyetherimide and Polysulfone)
[0197] Polyethersulfone, polyetherimide and polysulfone to be used
in the Embodiment may be selected appropriately from a group of
publicly known amorphous super-engineering plastics.
[0198] Specific examples of a polyethersulfone product include
Radel A, Radel R (Registered trade names of Solvay Advanced
Polymers), Mitsui PES (Mitsui Chemicals), and Ultrason E
(Registered trade name of BASF Japan Ltd.).
[0199] Specific examples of a polyetherimide product include Ultem
(Registered trade name of SABIC Innovative Plastics).
[0200] Specific examples of a polysulfone product include Udel and
Mindel (Registered trade names of Solvay Advanced Polymers) and
Ultrason S (Registered trade name of BASF Japan Ltd.).
(Polyaryl Ketone)
[0201] In the Embodiment, polyaryl ketone is a thermoplastic resin
having aromatic rings, an ether bond and a ketone bond in the
structural unit, and polyether ketone, polyetherether ketone and
polyether ketone ketone can be exemplified.
[0202] In the Embodiment, a polyetherether ketone having a
recurring unit represented by the following formula (3) is
favorably used.
##STR00005##
[0203] In the Embodiment, as a polyetherether ketone a commercial
product may be utilized, examples thereof include PEEK 151G, PEEK
90G, PEEK 381G, PEEK 450G and PEK (Registered trade names of
Victrex) and Ultrapek (PEKEKK) (Registered trade name of BASF); and
PEEK (Registered trade names of Victrex) can be favorably
utilized.
[0204] One type of polyaryl ketone, or two or more types in
combination may be used.
[0205] In the Embodiment, as for the molecular weight of a polyaryl
ketone, the melt viscosity may be used as an index, and the melt
viscosity is preferably in a range of 50 to 5,000 Pas (500 to
50,000 Poise), more preferably 70 to 3,000 Pas, further preferably
100 to 2,500 Pas, and still further preferably 200 to 1,000
Pas.
[0206] If the melt viscosity of a polyaryl ketone is 50 Pas or
higher, the mechanical strength of the resin tends to be improved,
and if it is 5,000 Pas or lower, the moldability of the resin tends
to be improved.
[0207] In the Embodiment, the melt viscosity of a polyaryl ketone
is an apparent melt viscosity measured by extruding the polyaryl
ketone heated to 400.degree. C. through a nozzle with inner
diameter of 1 mm and length of 10 mm under a load of 100 kg.
(Compatibilizer)
[0208] In the Embodiment, if as a thermoplastic resin other than
polyphenylene ether a resin with considerably low affinity with
polyphenylene ether, such as one or more selected from the group
consisting of an olefinic resin, polyester, polyamide, polyarylene
sulfide, polyetherimide, polyethersulfone, polysulfone and polyaryl
ketone, is used, a compatibilizer between a polyphenylene ether and
a thermoplastic resin other than polyphenylene ether should be
preferably used.
[0209] In case a thermoplastic resin other than polyphenylene ether
is an olefinic resin, a compatibilizer is preferably used, because
polyphenylene ether and an olefinic resin are in principle
incompatible. A thermoplastic resin blend of an olefinic resin and
polyphenylene ether is so structured that in a continuous phase of
an olefinic resin polyphenylene ether is dispersed playing an
important role in fortifying the heat resistance of the amorphous
part of the olefinic resin beyond the glass transition
temperature.
[0210] In order to improve the compatibility between them, a
copolymer having a chain segment with high compatibility with an
olefinic resin and a chain segment with high compatibility with
polyphenylene ether can be used as a compatibilizer. As a copolymer
with such compatibilities a copolymer with polystyrene
chain-polyolefin chain may be exemplified.
[0211] In the Embodiment, examples of a compatibilizer between an
olefinic resin and polyphenylene ether include a copolymer having a
polyphenylene ether chain-polyolefin chain, and a hydrogenated
block copolymer prepared by hydrogenating a block copolymer having
at least 2 polymer blocks A composed mainly of an aromatic vinyl
compound and at least 1 polymer block B composed mainly of a
conjugated diene compound, but a hydrogenated block copolymer is
preferable.
[0212] Examples of a hydrogenated block copolymer as a
compatibilizer between an olefinic resin and polyphenylene ether
include hydrogenated block copolymers produced by hydrogenating
block copolymers having structures of A-B-A, A-B-A-B,
(A-B--).sub.4--Si and A-B-A-B-A. Thereby A means a polymer block
composed mainly of an aromatic vinyl compound, and B means a
polymer block composed mainly of a conjugated diene compound.
[0213] The content of an aromatic vinyl compound in a polymer block
A and the content of a conjugated diene compound in a polymer block
B are preferably at least 70% by mass respectively.
[0214] A preferable hydrogenated block copolymer is a block
copolymer produced by hydrogenating the olefinic unsaturated bonds
originated from a conjugated diene compound in a block copolymer
composed of an aromatic vinyl compound and a conjugated diene
compound, to be decreased to 50% or lower, preferably to 30% or
lower, and more preferably to 10% or lower.
[0215] In the Embodiment, a block copolymer useful as a
compatibilizer between an olefinic resin and polyphenylene ether is
same as a block copolymer for an impact modifier as is described
hereinbelow, and in case an olefinic resin is used as a
thermoplastic resin other than polyphenylene ether, the block
copolymer has both functions of a function for a compatibilizer and
a function for an impact modifier. Among the block copolymers for
an impact modifier described below, a so-called high vinyl type
block copolymer, in which 1,2-vinyl bond rate of a polybutadiene
segment, namely a conjugate diene compound segment, is 50% to 90%,
can be used also favorably as a compatibilizer between
polyphenylene ether and an olefinic resin.
[0216] If polyester is a thermoplastic resin other than
polyphenylene ether, examples of a preferable compatibilizer
include compounds having an epoxy group, an oxazolyl group, an
imide group, a carboxylic acid group and an acid anhydride group;
and a compound having an epoxy group is more preferable.
[0217] Specific examples include glycidyl methacrylate/styrene
copolymer, glycidyl methacrylate/styrene/methyl methacrylate
copolymer, glycidyl methacrylate/styrene/methyl
methacrylate/methacrylate copolymer, glycidyl
methacrylate/styrene/acrylonitrile copolymer,
vinyloxazoline/styrene copolymer, N-phenylmaleimide/styrene
copolymer, N-phenylmaleimide/styrene/maleic anhydride copolymer and
styrene/maleic anhydride copolymer. Further, a graft copolymer such
as a graft copolymer of ethylene/glycidyl methacrylate copolymer
and polystyrene may be also used.
[0218] In the Embodiment, as a compatibilizer between polyester and
polyphenylene ether, glycidyl methacrylate/styrene copolymer,
vinyloxazoline/styrene copolymer, N-phenylmaleimide/styrene
copolymer and N-phenylmaleimide/styrene/maleic anhydride copolymer
are preferable, and glycidyl methacrylate/styrene copolymer is more
preferable.
[0219] Although there is no particular restriction on the ratio of
a compound, which is a monomer in the copolymers, having one or
more functional groups selected among an epoxy group, an oxazolyl
group, an imide group, a carboxylic acid group and an acid
anhydride group to a styrenic compound, but from the viewpoint of
silver streaking at injection molding or die deposit at extruding,
a compound having one or more functional groups selected among an
epoxy group, an oxazolyl group, an imide group, a carboxylic acid
group and an acid anhydride group is preferably 50% by mass or
less.
[0220] In the Embodiment, the addition amount of a compatibilizer
between polyester and polyphenylene ether, based on 100 parts by
mass of polyphenylene ether plus liquid crystal polyester, is
preferably 0.1 parts by mass or more from the viewpoint of the
tensile strength of the pellet, and preferably 10 parts by mass or
less from the viewpoint of the flame retardancy of the pellet, more
preferably from 1 to 7 parts by mass, and further preferably from
3.5 to 6 parts by mass.
[0221] Although there is no particular restriction on the addition
method of a compatibilizer, preferably it should be added together
with polyphenylene ether, or its masterbatch, which is produced in
advance by melt-blending with polyester, should be added with
polyphenylene ether.
[0222] Thereby it is required that polyphenylene ether constitutes
a dispersed phase, and polyester constitutes a continuous phase. By
the continuous phase constituted by polyester, chemical resistance
of the pellet and rigidity of the resin become superior. The
dispersion morphology can be judged easily by observation under,
for example, a transmission microscope. A preferable particle size
of the dispersed polyphenylene ether is 40 .mu.m or less, and more
preferably 20 .mu.m or less.
[0223] In the Embodiment, in case an impact improver described
below is added, the impact improver should preferably exist in the
polyphenylene ether dispersed phase. It is also useful for the
thermoplastic resin blend of the Embodiment to form a
sea/island/lake structure, in which polyester exists also in the
dispersed phase of the polyphenylene ether phase, by selecting a
production process. An example of a specific production process for
forming a sea/island/lake structure is that, using an extruder with
more than one feeding ports at different extruder zones,
polyphenylene ether, a part of liquid crystal polyester and
according to need a compatibilizer therefor are fed to the initial
extruder feeding port, and the rest of the liquid crystal polyester
is fed to a downstream feeding port of the extruder.
[0224] In case a thermoplastic resin other than polyphenylene ether
is polyamide, examples of a compatibilizer include the
compatibilizers disclosed precisely in Japanese Patent Application
Laid-Open No. 08-48869 and Japanese Patent Application Laid-Open
No. 09-124926. All of those disclosed compatibilizers can be used,
and a combined use is also possible.
[0225] In the Embodiment, among said compatibilizers, maleic acid
or derivatives thereof, citric acid or derivatives thereof, and
fumaric acid or derivatives thereof are preferable.
[0226] In the Embodiment, the content of the compatibilizer is,
based on 100 parts by mass of a mixture of polyamide and
polyphenylene ether, preferably from 0.01 to 25 parts by mass, more
preferably from 0.05 to 10 parts by mass, and further preferably
from 0.1 to 5 parts by mass.
[0227] In the Embodiment, polyphenylene ether particles exist
dispersed in the continuous phase of polyamide preferably with the
average particle size from 0.1 to 5 .mu.m, more preferably with the
average particle size from 0.3 to 3 .mu.m, and further preferably
from 0.5 to 2 .mu.m.
[0228] In the Embodiment, an impact improver described below
preferably exists in the dispersed phase of polyphenylene
ether.
[0229] In case a thermoplastic resin other than polyphenylene ether
is polyarylene sulfide, a thermoplastic resin blend composed of
polyarylene sulfide and polyphenylene ether is preferably so
constituted that polyphenylene ether is dispersed in a matrix of
polyarylene sulfide, and polyphenylene ether takes advantage of its
high glass transition temperature and plays an important role in
supporting the heat resistance beyond the glass transition
temperature of the amorphous part of polyarylene sulfide.
[0230] Polyarylene sulfide and polyphenylene ether are
incompatible, and to improve the compatibility, a copolymer of
compounds containing an epoxy group and/or an oxazolyl group is
useful.
[0231] In the Embodiment, by adding a compatibilizer, generation of
a flash on a molded article molded with the pellet can be
remarkably reduced.
[0232] In case such effect is not required, a compatibilizer may be
unnecessary.
[0233] In the Embodiment, as a compatibilizer between polyarylene
sulfide and polyphenylene ether, a copolymer of an unsaturated
monomer having an epoxy group and/or an oxazolyl group and a
monomer with main constituent of styrene can be favorably used.
[0234] A monomer with main constituent of styrene means a monomer
component containing 65% by mass or more, more preferably from 75
to 95% by mass, of styrene and a monomer copolymerizable with
styrene. Examples include a copolymer of an unsaturated monomer
having an epoxy group and/or an unsaturated monomer having an
oxazolyl group and styrene, and a copolymer of an unsaturated
monomer having an epoxy group and/or an unsaturated monomer having
an oxazolyl group and styrene/acrylonitrile (=90 to 75% by mass/10
to 25% by mass).
[0235] Examples of the unsaturated monomer having an epoxy group
include glycidyl methacrylate, glycidyl acrylate, vinylglycidyl
ether, glycidyl ether of hydroxyalkyl (meth)acrylate, glycidyl
ether of polyalkylene glycol(meth)acrylate and glycidyl itaconate;
and glycidyl methacrylate is preferable.
[0236] As the unsaturated monomer having an oxazolyl group, a
vinyloxazoline compound may be exemplified, and, for example,
2-isopropenyl-2-oxazoline can be industrially available and
favorably utilized.
[0237] Examples of other monomers to be copolymerized with the
unsaturated monomer having an epoxy group and/or an oxazolyl group
include styrene and additionally as a copolymer component a vinyl
cyanide monomer such as acrylonitrile, vinyl acetate, and
(meth)acrylic acid ester.
[0238] It is preferable to contain in the copolymer from 0.3 to 20%
by mass of a structural unit of an unsaturated monomer having an
epoxy group and/or an unsaturated monomer having an oxazolyl group,
more preferable to contain from 1 to 15% by mass, and further
preferable to contain from 3 to 10% by mass.
[0239] By using the compatibilizer containing from 0.3 to 20% by
mass of an unsaturated monomer having an epoxy group and/or an
unsaturated monomer having an oxazolyl group, the compatibility
between polyarylene sulfide and polyphenylene ether can be
maintained high, and generation of a flash on a molded article
molded with the obtained pellet can be remarkably reduced. Further,
the balance between heat resistance as well as toughness (impact
strength) and mechanical strength is positively influenced.
[0240] Examples of the copolymer include styrene/glycidyl
methacrylate copolymer, styrene/glycidyl methacrylate/methyl
methacrylate copolymer, styrene/glycidyl methacrylate/acrylonitrile
copolymer, styrene/vinyloxazoline copolymer and
styrene/vinyloxazoline/acrylonitrile copolymer.
[0241] In the Embodiment, the content of a compatibilizer is, based
on 100 parts by mass of the total amount of polyphenylene ether
plus polyarylene sulfide, preferably from 0.5 to 5 parts by mass,
more preferably from 1 to 5 parts by mass, and further preferably
from 1 to 3 parts by mass.
[0242] If the content of a compatibilizer is 0.5 parts by mass or
higher, the compatibility between polyarylene sulfide and
polyphenylene ether becomes well, and if it is 5 parts by mass or
lower, the average particle size of polyphenylene ether forming a
dispersed phase becomes 10 .mu.m or less, which can reduce
remarkably generation of a flash on a molded article molded with
the obtained pellet, and influence positively the balance between
heat resistance (impact strength) as well as toughness and
mechanical strength. In case the compatibilizer is not used, a
molded article with high heat resistance and impact resistance is
obtained.
[0243] Thereby polyphenylene ether particles preferably exist
dispersed in the continuous phase of polyarylene sulfide with the
average particle size of 10 .mu.m or less, more preferably 8 .mu.m
or less, and further preferably 5 .mu.m or less. It is effective to
keep the average size of the dispersed particles at 10 .mu.m or
less for preventing deterioration of appearance and detachment
phenomenon of the obtained pellet. Further, it is preferable that
an impact improver described below should exist in the dispersed
phase of polyphenylene ether.
[0244] In case a thermoplastic resin other than polyphenylene ether
is a thermosetting resin of polyarylate, polyetherimide,
polyethersulfone, polysulfone and polyaryl ketone, as a
compatibilizer all of the compatibilizers described above with
respect to polypropylene, polyamide, polyarylene sulfide and
polyester with polyphenylene ether can be used. Since said resins
have in general high processing temperatures and therefore most of
the terminal functional groups are inactivated to a reaction, it is
preferable to use an appropriately selected compatibilizer after
causing some kind of chemical reaction (e.g. a scission reaction of
a molecular chain by heat or a peroxide).
[0245] Without such a reaction, compatibilization is also possible.
More particularly, addition of a small amount of polyarylate as
compatibilizer between polyphenylene ether and polyaryl ketone is
very useful to enhance the compatibility between them.
[0246] In the Embodiment, as a compatibilizer between polyphenylene
ether and a thermoplastic resin other than polyphenylene ether an
inorganic metal oxide can be also used. Examples thereof include
oxides of one or more metals selected from the group consisting of
zinc, titanium, calcium, magnesium and silicon; and among them zinc
oxide is preferable.
(Stabilizer)
[0247] In the Embodiment, for stabilization of polyphenylene ether
and/or a thermoplastic resin other than polyphenylene ether,
various publicly known stabilizers can be favorably used.
[0248] Examples of a stabilizer include metallic stabilizers, such
as zinc oxide and zinc sulfide; antioxidants such as a
sterically-hindered phenol based antioxidant, a phosphorus based
thermal stabilizer and a sulfur based thermal stabilizer; and
organic stabilizers, such as a sterically-hindered amine based
photo stabilizer and a benzotriazole based UV absorber.
[0249] A preferable content of the stabilizer is from 0.1 to 5
parts by mass based on 100 parts by mass of the thermoplastic resin
blend.
[0250] In the Embodiment, a sterically-hindered phenol based
antioxidant is preferable as a stabilizer.
[0251] Specific examples include Irganox 1098 (Registered trade
name) and Irganox 1076 (Registered trade name) available from Ciba
Specialty Chemicals Ltd.
[0252] In the Embodiment, although the step of impregnating the
long fiber filler with the thermoplastic resin blend is vulnerable
to an atmospheric oxygen, by addition of a sterically-hindered
phenol based antioxidant the discoloration of the obtained pellet
can be prevented.
[0253] In the Embodiment, the content of the sterically-hindered
phenol based antioxidant is preferably 0.1 parts by mass or higher
based on 100 parts by mass of the thermoplastic resin blend, more
preferably 0.2 parts by mass or higher, and further preferably 0.3
parts by mass or higher. Further, the content of the
sterically-hindered phenol based antioxidant is preferably 5 parts
by mass or lower, more preferably 3 parts by mass or lower, and
further preferably 2 parts by mass or lower.
(Flame Retardant)
[0254] In the Embodiment, an organic and inorganic flame retardant
may be added in order to give a flame retarding property. Examples
of a flame retardant include a halogen-containing compound, an
antimony compound, a phosphorus based flame retardant, a cyclic
nitrogen-containing compound, a silicon compound and a metal
hydroxide. Among them, a phosphorus based flame retardant, a cyclic
nitrogen-containing compound and a silicon compound are preferable
in view of flame retardancy as well as density lowering
property.
[0255] Examples of a phosphorus based flame retardant include red
phosphorus, an organophosphate compound, a phosphazene compound,
phosphinic acid salts, phosphonic acid salts and a phosphoramide
compound.
[0256] Examples of an organophosphate compound include triphenyl
phosphate, phenyl bis(dodecyl)phosphate, phenyl bis(neopentyl)
phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl
diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate,
bis(2-ethylhexyl).sub.p-tolyl phosphate, tritolyl phosphate,
bis(2-ethylhexyl) phenyl phosphate, tris(nonylphenyl)phosphate,
didodecyl p-tolyl phosphate, tricresyl phosphate, dibutyl phenyl
phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl
bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl
phosphate, bisphenol A bis(diphenyl phosphate),
diphenyl(3-hydroxyphenyl) phosphate, bisphenol A bis(dicresyl
phosphate), resorcinol bis(diphenyl phosphate), resorcinol
bis(dixylenyl phosphate), 2-naphthyl diphenyl phosphate, 1-naphthyl
diphenyl phosphate and di(2-naphthyl)phenyl phosphate.
[0257] Examples of an organophosphate compound further include
aromatic condensation phosphate compounds represented by the
following formula (4) or (5).
##STR00006##
[0258] wherein Q1, Q2, Q3 and Q4 independently represent a C1 to C6
alkyl group, R1 and R2 represent a methyl group, and R3 and R4
independently represent a hydrogen atom or a methyl group. The n
represents an integer of 1 or larger, n1 and n2 independently
represent integers from 0 to 2, and the m1, m2, m3 and m4
independently represent an integer from 1 to 3.
[0259] An aromatic condensation phosphate compound is in general a
mixture, in which the compounds with n representing integers 1 to 3
occupy 90% or more, and available as a mixture further containing
multimers with n higher than 3 and other byproducts.
[0260] Examples include a bisphenol A based aromatic condensation
phosphate, such as a phosphate compound containing bisphenol A
bis(diphenyl phosphate) as a main component (CR741, Daihachi
Chemical Ind.) and a phosphate compound containing bisphenol A
bis(dixylenyl phosphate) as a main component; and a resorcin based
aromatic condensation phosphate, such as a phosphate compound
containing resorcinol bis(dixylenyl phosphate) as a main component
(PX200, Daihachi Chemical Ind.) and a phosphate compound containing
resorcinol bis(diphenyl phosphate) as a main component (CR?733S,
Daihachi Chemical Ind.). A resorcin based and a bisphenol A based
aromatic phosphate compound are preferable in terms of volatility
and heat resistance, and a resorcin based and a bisphenol A based
aromatic condensation phosphate compound with the acid value of 0.5
or lower, preferably 0.1 or lower, are more preferable in terms of
water resistance and electrical properties, and a bisphenol A based
aromatic condensation phosphate compound is further preferable.
[0261] As a phosphazene compound, compounds having a cyclic or
linear structure represented by the following formula (6) are
exemplified, but a compound with a cyclic structure is preferable.
A phenoxy phosphazene compound with a 6-membered or 8-membered
ring, where n=3 or 4, is more preferable.
##STR00007##
[0262] wherein R represent independently a C1 to C20 aliphatic or
aromatic group, the n represents 3 or a larger integer.
[0263] The compound may be cross-linked by a cross-linking group
selected from the group consisting of a phenylene group, a
biphenylene group and a group represented by the following formula
(7).
##STR00008##
[0264] wherein X represents --C(CH.sub.3).sub.2--, --SO.sub.2--,
--S-- or --O--.
[0265] The phosphazene compound represented by the formula (6) is a
publicly known compound, and described, for example, in "Inorganic
Polymers" (Pretice-Hall International, Inc.), by James E. Mark,
Harry R. Allcock, Robert West, 1992, p 61-p 140. Synthesis example
to prepare such phosphazene compounds are disclosed in Japanese
Patent Publication No. 03-73590, Japanese Patent Application
Laid-Open No. 09-71708, Japanese Patent Application Laid-Open No.
09-183864, Japanese Patent Application Laid-Open No. 11-181429,
etc. For example, in case of synthesis of an uncrosslinked cyclic
phenoxy phosphazene compound, according to the method described in
"Phosphorus Nitrogen Compounds", (Academic Press), by H. R. Allcock
(1972), a toluene solution of sodium phenolate is added dropwise
with stirring into 580 g of a 20% chlorobenzene solution containing
1.0 unit mol (115.9 g) of dichlorophosphazene oligomer (a mixture
of trimer 62% and tetramer 38%), and the mixture is left reacting
at 110.degree. C. for 4 hours to obtain, after purification, the
uncrosslinked cyclic phenoxy phosphazene compound.
[0266] Since a phosphazene compound contains a higher content of
phosphorus in the compound than in an ordinary phosphate compound,
addition of a small amount can assure sufficient flame retardancy.
Further, owing to its superior hydrolysis resistance and
thermolysis resistance, the deterioration of physical properties of
a thermosetting resin composition can be decreased. Consequently, a
phosphazene compound is a preferable compound as a phosphorus based
flame retardant, and a phosphazene compound with the acid value of
0.5 or lower is more preferable in view of flame retardancy as well
as water resistance and electrical properties.
[0267] Phosphinic acid salts include a phosphinate by the formula
(8) or (9), and/or a diphosphinate and/or a condensation product
thereof (hereinafter occasionally abbreviated simply as "phosphinic
acid salt").
##STR00009##
[0268] wherein R.sup.1 and R.sup.2, the same or different,
represent linear or branched C1 to C6 alkyl and/or aryl or phenyl,
R.sup.3 represents linear or branched C1 to C10 alkylene, C6 to C10
arylene, C6 to C10 alkylarylene or C6 to C10 arylalkylene, M
represents one or more selected among calcium (ion), magnesium
(ion), aluminum (ion), zinc (ion), bismuth (ion), manganese (ion),
sodium (ion), potassium (ion) and a protonated nitrogen base, m is
2 or 3, n represents an integer of 1 to 3 and x is 1 or 2.
[0269] The phosphinic acid salts in the Embodiment can be produced
by a publicly known process as disclosed in European Patent
Application Laid-Open No. 699708, Japanese Patent Application
Laid-Open No. 08-73720. For example, a phosphinate can be produced
by reacting phosphinic acid in an aqueous solution with a metal
carbonate, a metal hydroxide or a metal oxide, but not limited
thereto. It can be produce also by a sol-gel process, etc. The
phosphinic acid salts are generally monomeric compounds, but under
certain circumstances depending on reaction conditions, it may
contain polymeric phosphinic acid salts, which are condensation
products with the degree of condensation of 1 to 3.
[0270] In the Embodiment, examples of a phosphinic acid include
dimethylphosphinic acid, ethylmethylphosphinic acid,
diethylphosphinic acid, methyl-n-propylphosphinic acid,
methane-di(methylphosphinic acid), benzene-1,4-(dimethylphosphinic
acid), methylphenylphosphinic acid, diphenylphosphinic acid and a
mixture thereof.
[0271] As a metal component one or more selected among calcium ion,
magnesium ion, aluminum ion, zinc ion, bismuth ion, manganese ion,
sodium ion, potassium ion and/or a protonated nitrogen base can be
exemplified, and one or more selected among calcium ion, magnesium
ion, aluminum ion and zinc ion are preferable.
[0272] Examples of the phosphinic acid salts include calcium
dimethylphosphinate, magnesium dimethylphosphinate, aluminum
dimethylphosphinate, zinc dimethylphosphinate, calcium
ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum
ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium
diethylphosphinate, magnesium diethylphosphinate, aluminum
diethylphosphinate, zinc diethylphosphinate, calcium
methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate,
aluminum methyl-n-propylphosphinate, zinc
methyl-n-propylphosphinate, calcium methane-di(methylphosphinate),
magnesium methane-di(methylphosphinate), aluminum
methane-di(methylphosphinate), zinc methane-di(methylphosphinate),
calcium benzene-1,4-(dimethylphosphinate), magnesium
benzene-1,4-(dimethylphosphinate), aluminum
benzene-1,4-(dimethylphosphinate), zinc
benzene-1,4-(dimethylphosphinate), calcium methylphenylphosphinate,
magnesium methylphenylphosphinate, aluminum
methylphenylphosphinate, zinc methylphenylphosphinate, calcium
diphenylphosphinate, magnesium diphenylphosphinate, aluminum
diphenylphosphinate and zinc diphenylphosphinate.
[0273] In the Embodiment, as phosphinic acid salts are preferable
from the viewpoint of flame retardancy and suppression of mold
deposit, calcium dimethylphosphinate, aluminum dimethylphosphinate,
zinc dimethylphosphinate, calcium ethylmethylphosphinate, aluminum
ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium
diethylphosphinate, aluminum diethylphosphinate and zinc
diethylphosphinate, and among them aluminum diethylphosphinate is
more preferable.
[0274] In the Embodiment, from the view point of mechanical
strength and article appearance of a molded article to be obtained
by molding the pellet, the average particle size (d50%) of a
phosphinic acid salt is preferably 0.5 .mu.m or larger, more
preferably 1.0 .mu.m or larger, and further preferably 2 .mu.m or
larger. Further, the average particle size of the phosphinic acid
salts is preferably 40 .mu.m or less, more preferably 20 .mu.m,
further preferably 15 .mu.m or less, and still further preferably
10 .mu.m or less.
[0275] In the Embodiment, if the number average particle size of a
phosphinic acid salt is 0.5 .mu.m or larger, at fabrication such as
melt blending, handling property and feeding property into an
extruder are improved and favorable quality resin can be obtained.
Further, if the average particle size of the phosphinic acid salt
is 40 .mu.m or less, it exerts such effects that high mechanical
strength of a molded article becomes easily attainable and the
surface appearance of the molded article becomes improved.
[0276] Concerning the particle size distribution of a phosphinic
acid salt, the ratio (d75%/d25%) of the particle size at 75% of the
order counted from the small side (d75%) to the particle size at
25% (d25%) is preferably larger than 1.0 and equal to or less than
5.0, more preferably from 1.2 to 4.0, and further preferably from
1.5 to 3.0. By using a phosphinic acid salt with the d75%/d25%
value beyond 1.0 but not more than 5.0, the surface impact strength
of a molded article can be remarkably improved.
[0277] In the Embodiment, the average particle size (d50%) and the
particle size distribution are based on the particle sizes related
to volume measured by a laser diffraction/scattering particle size
distribution analyzer. The measurement is conducted using a 3%
aqueous solution of isopropanol as a dispersing medium for the
phosphinic acid salts. More specifically, a measurement can be
conducted using a laser diffraction/scattering particle size
distribution analyzer LA-910 (Horiba, Ltd.) by: first carrying out
a blank test with only a dispersing medium of a 3% aqueous solution
of isopropanol, and then conducting a measurement after adding a
test sample to satisfy the specified transmission rate (from 95% to
70%). Thereby dispersion of a test sample in the dispersing medium
is carried out by sonication for 1 min.
[0278] Unreacted materials or byproducts may remain in the
phosphinic acid salts of the Embodiment to the extent that the
effect of the Embodiment should not be impaired.
[0279] In the Embodiment, two or more types of the phosphorus based
flame retardants may be used in combination.
[0280] In the Embodiment, the content of the phosphorus based flame
retardant is preferably from 1 to 50 parts by mass based on 100
parts by mass of the thermoplastic resin blend, more preferably
from 1 to 40 parts by mass, further preferably from 2 to 30 parts
by mass, and still further preferably 3 to 25 parts by mass.
[0281] If the content of the phosphorus based flame retardant is 3
parts by mass or higher based on 100 parts by mass of the
thermoplastic resin blend, the flame retardancy of the pellet
becomes good. Further, if it is 40 parts by mass or lower,
mechanical strength and thermal form stability of a molded article
are good.
[0282] Examples of the silicon compound include silicone, a
silsesquioxane cage or a partially cleaved structure thereof and
silica.
[0283] Silicone means an organosiloxane polymer, which may have a
linear structure, a cross-linked structure or a structure mixed of
them in certain ratio. It may be used singly or as a mixture among
them, however from the viewpoint of flame retardancy and
flowability, that having a linear structure is preferable. From the
viewpoint of flame retardancy and impact strength, a silicone
having a functional group in a molecule as a terminal group or a
side chain group is preferable. As a functional group, an epoxy
group and an amino group are preferable.
[0284] Specifically, silicone fluid, modified silicone fluid and
silicone powder produced by Dow Corning Toray Silicone Co., Ltd.
and straight silicone fluid, reactive silicone fluid, non-reactive
silicone fluid and KMP series silicone powder produced by Shin-Etsu
Chemical Co., Ltd., etc. can be used. Either of a fluid type and a
solid type may be used.
[0285] The viscosity at 25.degree. C. of a fluid type is preferably
10 to 10,000 mm.sup.2/s, more preferably 100 to 8,000 mm.sup.2/s,
and further preferably 500 to 3,000 mm.sup.2/s.
[0286] The average particle size of a solid type is preferably 0.1
to 100 .mu.m, more preferably 0.5 to 30 .mu.m, and further
preferably 0.5 to 5 .mu.m.
[0287] In the Embodiment, the added content of a silicone is in
view of a flame retardant effect preferably 0.1 parts by mass or
more based on 100 parts by mass of the thermoplastic resin blend,
and in view of suppression of rigidity decrease preferably 10 parts
by mass or less. More favorably the lower limit is 0.3 parts by
mass, and further preferably 0.5 parts by mass. More favorably the
upper limit is 5 parts by mass, and further preferably 2 parts by
mass.
[0288] The cyclic nitrogen-containing compound is a cyclic organic
compound containing a nitrogen element. Specifically, melamine
derivatives, such as melamine, melem and melon, can be used
favorably, and from the viewpoint of volatility melem and melon are
preferable.
[0289] The added content of a cyclic nitrogen-containing compound
is in view of a flame retardant effect preferably 0.1 parts by mass
or more based on 100 parts by mass of the thermoplastic resin
blend, and in view of suppression of rigidity decrease preferably
10 parts by mass or less. More favorably the lower limit is 0.3
parts by mass, and further preferably 0.5 parts by mass. More
favorably the upper limit is 5 parts by mass, and further
preferably 2 parts by mass.
(Filler Other than Long Fiber Filler)
[0290] In the Embodiment, the pellet may further contain according
to need a filler other than the long fiber filler, such as a
fibrous filler with the fiber length of 3 mm or less, and a
granular filler with the particle size of 1 mm or less. As a
fibrous filler with the fiber length of 3 mm or less, one or more
selected from carbon fiber, glass fiber, metal fiber and aramid
fiber can be exemplified, and one or more selected from carbon
fiber and glass fiber are preferable. More preferable is glass
fiber.
[0291] In this connection, the fiber length of the fibrous filler
with the fiber length less than 3 mm is not counted in the
calculation of the average fiber length of the long fiber filler of
the Embodiment.
[0292] Examples of a granular filler with the particle size of 1 mm
or less include a hydroxide of an element selected from magnesium
and calcium; an oxide of an element selected from the group
consisting of magnesium, titanium, iron, copper, zinc and aluminum;
and one or more fillers selected from the group consisting of zinc
sulfide, zinc borate, calcium carbonate, talc, wollastonite, glass,
carbon black, carbon nanotube and silica. Among them a hydroxide of
an element selected from magnesium and calcium; an oxide of an
element selected from the group consisting of magnesium, titanium
and zinc; zinc sulfide, zinc borate, calcium carbonate, talc,
wollastonite, glass, carbon black and carbon nanotube are
preferable; and a hydroxide of calcium, an oxide of an element
selected from titanium and zinc; zinc sulfide, calcium carbonate,
talc, wollastonite and carbon black are more preferable.
[0293] Concerning the added content of a filler other than the long
fiber filler, it should be added in the long fiber filler
reinforced resin pellet preferably at 20% by mass or less,
preferably at 15% by mass or less, and preferably at 10% by mass or
less. There is no particular restriction on the lower limit of the
added content of a filler other than the long fiber filler, and the
minimum quantity required to express the intended effect by
addition should be added. If nucleating effect is expected, the
added content of a filler other than the long fiber filler is
preferably 0.01% by mass or higher, more preferably 0.05% by mass
or higher, and further preferably 0.1% by mass or higher. If an
effect on the dimensional stability is expected, an indicative
minimum content is preferably 0.5% by mass or higher, more
preferably 1% by mass or higher, and further preferably 5% by mass
or higher.
[0294] In the Embodiment, wollastonite is obtained by purifying,
crushing and classifying a natural mineral with a component of
calcium silicate. An artificially synthesized product can be also
used. As for the size of wollastonite, that with the average
particle size from 2 to 9 .mu.m and the aspect ratio of 5 or higher
is preferable, more preferable is that with the average particle
size from 3 to 7 .mu.m and the aspect ratio of 5 or higher, and
further preferable is that with the average particle size from 3 to
7 .mu.m and the aspect ratio of 8 or higher and 30 or lower.
[0295] In the Embodiment, talc obtained by purifying, crushing and
classifying a natural mineral with a component of magnesium
silicate can be favorably used, and the crystallite diameter on the
(002) diffraction plane of talc by wide-angle X-ray diffraction is
preferably 570 .ANG. or more.
[0296] The (002) diffraction plane of talc can be confirmed by
identifying the existence of talc
[Mg.sub.3Si.sub.4O.sub.10(OH).sub.2] using a wide-angle X-ray
diffraction apparatus, and verifying that an interlayer distance
thereof is identical with the lattice spacing of the (002)
diffraction plane of talc of about 9.39 .ANG.. The crystallite
diameter on the (002) diffraction plane of talc is calculated from
the half-width of the peak thereof.
[0297] As for morphology of talc, the average particle size is
preferably in a range from 1 to 20 .mu.m, and the particle size
distribution, in which the ratio (d75%/d25%) of the particle size
at 75% of the order counted from the small side (d75%) to the
particle size at 25% (d25%) is in a range from 1.0 to 2.5, is
preferable. The ratio (d75%/d25%) is more preferably in a range
from 1.5 to 2.2, and the average particle size is more preferably
from 1 to 16 .mu.m, and further preferably from 3 to 9 .mu.m.
[0298] In the Embodiment, the average particle size and the
particle size distribution of talc are based on the particle sizes
related to volume measured by a laser diffraction/scattering
particle size distribution analyzer. Further, they are the values
measured using ethanol as a dispersing medium for talc.
[0299] In the Embodiment, as an oxide of an element selected from
titanium and zinc are exemplified titanium dioxide and zinc oxide,
and titanium dioxide is preferable.
[0300] Titanium dioxide may be a treated titanium dioxide, which
surface is treated with alumina, a silicon compound and/or
polysiloxane, and the content of titanium dioxide is preferably in
a range from 90 to 99% by mass, and more preferably in a range from
93 to 98% by mass. In this case the surface treatment agent is not
counted in the amount of the titanium dioxide.
[0301] The average particle size of the titanium dioxide is
preferably in a range from 0.05 to 1 .mu.m, more preferably in a
range from 0.1 to 0.5 .mu.m, and further preferably in a range from
0.2 to 0.4 .mu.m.
[0302] In the Embodiment, the average particle size is a value
measured by a centrifugal sedimentation method and means a weight
median diameter. Thereby a solvent to disperse the granular filler
should be appropriately selected depending upon a type of the
granular filler, and for example in case of titanium dioxide a
solution of sodium hexametaphosphate is preferably used.
[0303] In the Embodiment, various additives other than those
described above may be added according to need. Additives generally
added to compositions of plastics and rubber-like polymers maybe
used without particular restrictions. Examples of additives include
the additives described in "Additive Chemicals for Rubbers and
Plastics (Gomu-Purasuchikku Haigou Yakuhin)" (Polymer Digest Co.,
Ltd.). Specific examples include a naphthenic, paraffinic, aromatic
process oil to be used as a rubber softener, a plasticizer, such as
fatty acid esters, aliphatic dibasic acid esters, phthalates and an
epoxidized soybean oil, pigments such as iron oxides, a lubricant,
such as stearic acid, behenic acid, zinc stearate, calcium
stearate, magnesium stearate and ethylene bis-stearyl amide, a mold
release agent, an organic polysiloxane, a flame retardant
assistant, an antistatic agent and a colorant. The mixture of two
or more of the additives may be used.
(Long Fiber Filler Reinforced Resin Pellet)
[0304] The long fiber filler reinforced resin pellet of the
Embodiment is a pellet composed of the long fiber filler and the
thermoplastic resin blend.
[0305] In the Embodiment, the average length of the long fiber
filler reinforced resin pellet is preferably 3 mm or longer, more
preferably 5 mm or longer, and further preferably 8 mm or longer.
Further, the average length of the long fiber filler reinforced
resin pellet is preferably 50 mm or shorter, more preferably 40 mm
or shorter, and further preferably 15 mm or shorter.
[0306] In order not to deteriorate the impact strength of a molded
article molded from the long fiber filler reinforced resin pellet
of the Embodiment, the average length is preferably 3 mm or longer,
and in order not to deteriorate the feeding property to an
extruder, the average length is preferably 50 mm or shorter.
[0307] In the Embodiment, the average length of the pellet is the
value determined by averaging all the pellet lengths measured by
calipers for 50 pellets sampled arbitrarily.
[0308] In the Embodiment, the average diameter of the long fiber
filler reinforced resin pellet is preferably 0.5 mm or larger, more
preferably 1 mm or larger, and further preferably 2 mm or larger.
Further, the average diameter of the long fiber filler reinforced
resin pellet is preferably 8 mm or less, more preferably 5 mm or
less, and further preferably 4 mm or less.
[0309] The average diameter of the pellet is the value determined
by averaging the maximum diameter (in case of an ellipse the major
diameter) and the minimum diameter (in case of an ellipse the minor
diameter) measured by calipers for each of 50 pellets sampled
arbitrarily to obtain a mean value, and averaging the diameter mean
values of all the pellets.
(Resin Pellet Blend)
[0310] In the Embodiment, the long fiber filler reinforced resin
pellet may be used also as a resin pellet blend, in which from 0.1
to 150 parts by mass of a resin pellet without a long fiber filler
are added based on 100 parts by mass of the long fiber filler
reinforced resin pellet.
[0311] The content of the resin pellet without a long fiber filler
is 0.5 parts by mass or more based on 100 parts by mass of the long
fiber filler reinforced resin pellet, preferably 1 part by mass or
more, and more preferably 2 parts by mass or more. Further, the
content of the resin pellet without a long fiber filler is 120
parts by mass or less, preferably 100 parts by mass or less, and
more preferably 80 parts by mass or less.
[0312] In order not to decrease the impact resistance of a molded
article made of a resin pellet blend, the content should preferably
not exceed the upper limit, and in case a color master batch is
used as a resin pellet without a long fiber filler the content
should be preferably not less than the lower limit in order to
maintain the easiness of coloring.
[0313] In the Embodiment, the content of the long fiber filler in
the resin pellet blend is preferably 10% by mass or more of the
total amount of the resin pellet blend, more preferably 15% by mass
or more, further preferably 20% by mass or more, and still further
preferably 25% by mass or more. Further, the content of the long
fiber filler in the resin pellet blend is preferably 60% by mass or
less, more preferably 55% by mass or less, and further preferably
50% by mass or less.
[0314] In order not to decrease the impact strength of a molded
article molded from the resin pellet blend, the content is
preferably 10% by mass or more, and from the viewpoint of limiting
the molding temperature, it is preferably 60% by mass or less.
[0315] In the Embodiment, a resin pellet without a long fiber
filler may further contain a filler other than the long fiber
filler, and as a filler other than the long fiber filler, a
granular filler may be exemplified.
[0316] Examples of a granular filler include a hydroxide of an
element selected from magnesium and calcium, an oxide of an element
selected from the group consisting of magnesium, titanium, iron,
copper, zinc and aluminum, and one or more fillers selected from
the group consisting of zinc sulfide, zinc borate, calcium
carbonate, talc, wollastonite, glass, carbon black, carbon nanotube
and silica.
[0317] The average particle size of a granular filler is preferably
1 mm or less, and specifically those granular fillers exemplified
as usable for the long fiber filler reinforced resin pellet may be
exemplified.
[0318] The content of a granular filler to be added to a resin
pellet without a long fiber filler is preferably 50% by mass or
less in the resin pellet without a long fiber filler, more
preferably 40% by mass or less, and further preferably 30% by mass
or less. There is no particular restriction on the lower limit of
the granular filler to be added, and the minimum quantity required
to express the intended effect by addition should be added. An
indicative addition amount of the granular filler is preferably 5%
by mass or more, more preferably 10% by mass or more, and further
preferably 15% by mass or more.
[0319] In the Embodiment, as a resin component constituting the
resin pellet without a long fiber filler one or more selected from
the group consisting of a styrenic resin, an olefinic resin,
polyester, polyamide, polyarylene sulfide, polyetherimide,
polyethersulfone, polysulfone and polyaryl ketone are exemplified,
and a more preferable composition further contains polyphenylene
ether.
[0320] In the Embodiment, as a resin component constituting the
resin pellet without a long fiber filler, the thermoplastic resin
blend described hereinabove in connection with the long fiber
filler reinforced resin pellet can be favorably used.
[0321] In the Embodiment, a long fiber filler reinforced resin
pellet and a resin pellet without a long fiber filler may contain
an impact improver according to need. Although there is no
particular restriction on the usable impact improver, a preferably
applicable improver is at least one selected depending on the
requirement out of a block copolymer composed of a polymer block A
mainly constituted of at least one aromatic vinyl compound and a
polymer block B mainly constituted of at least one conjugated diene
compound (such block copolymer hereinafter occasionally simply
abbreviated as "the block copolymer"), and an
ethylene/.alpha.-olefin copolymer.
[0322] In the polymer block mainly constituted of an aromatic vinyl
compound, "mainly constituted of" means that the block is
constituted of at least 50% by mass of an aromatic vinyl compound.
More preferably is the content 70% by mass or more, further
preferably 80% by mass or more, and still further preferably 90% by
mass or more.
[0323] In the polymer block mainly constituted of a conjugated
diene compound, "mainly constituted of" means similarly that the
block is constituted of at least 50% by mass of a conjugated diene
compound. More preferably is the content 70% by mass or more,
further preferably 80% by mass or more, and still further
preferably 90% by mass or more.
[0324] In the Embodiment, a polymer block in the block copolymer
may be a copolymer block, and an aromatic vinyl compound content in
a random copolymer part may be distributed uniformly or changing
monotonously.
[0325] In a copolymer block there may exist respectively a
plurality of uniform distribution parts and/or monotonously
changing distribution parts of an aromatic vinyl compound content,
and further in a copolymer block a plurality of parts of different
aromatic vinyl compound contents may exist. In these cases, even if
a smaller amount of a conjugated diene compound or other compound
is bonded randomly in a block of an aromatic vinyl compound, so
long as the block is constituted 50% by mass or more of an aromatic
vinyl compound, such block is deemed as the block copolymer mainly
constituted of an aromatic vinyl compound. The same is true with a
conjugated diene compound.
[0326] As the block copolymer composed of a polymer block A mainly
constituted of an aromatic vinyl compound and a polymer block B
mainly constituted of a conjugated diene compound, generally block
copolymers having the following structures can be exemplified.
[0327] (A-B).sub.n, A-(B-A).sub.n-B, B-(A-B).sub.n+1,
[(A-B).sub.k].sub.m+1-Z, [(A-B).sub.k-A].sub.m+1-Z,
[(B-A).sub.k].sub.m+1-Z, [(B-A).sub.k-B].sub.m+1-Z
wherein Z represents a residue of a coupling agent or a residue of
an initiator of a multi-functional organolithium compound. The n, k
and m are respectively an integer of 1 or higher, generally from 1
to 5.
[0328] Among the above, the block copolymer is preferably a block
copolymer having a bonding structure selected from A-B type, A-B-A
type and A-B-A-B type, more preferably having A-B-A type or A-B-A-B
type, and further preferably having A-B-A type. A mixture of them
is naturally acceptable.
[0329] In the Embodiment, as an aromatic vinyl compound to be used
for a block copolymer of an aromatic vinyl compound/a conjugated
diene compound, one or more may be selected from, for example,
styrene, .alpha.-methyl styrene, vinyl toluene, p-tert-butyl
styrene and diphenylethylene, and styrene is preferable. The
content of an aromatic vinyl compound in a block copolymer of an
aromatic vinyl compound/a conjugated diene compound can be selected
favorably in general from 1 to 70% by mass, preferably from 5 to
55% by mass, and more preferably from 10 to 55% by mass.
[0330] As a conjugated diene compound to be used for a block
copolymer of an aromatic vinyl compound/a conjugated diene
compound, one or more may be selected from, for example, butadiene,
isoprene, 1,3-pentadiene and 2,3-dimethyl-1,3-butadiene, and
butadiene, isoprene and a combination thereof are preferable.
[0331] In the Embodiment, the block copolymer may be a hydrogenated
block copolymer. A hydrogenated block copolymer means the block
copolymer of an aromatic vinyl compound/a conjugated diene compound
that is hydrogenated to regulate the rate of an aliphatic double
bond (i.e. the hydrogenation rate) in the polymer block mainly
constituted of a conjugated diene compound in a range beyond 0 and
100%. The hydrogenation rate of the hydrogenated block copolymer is
preferably 50% or higher, more preferably 80% or higher, and
further preferably 98% or higher.
[0332] As a specific example of a hydrogenation method, in a
hydrocarbon solvent a hydrogenation catalyst and hydrogen gas are
added for causing a hydrogenation reaction to decrease olefinic
unsaturated bonds derived from a conjugated diene compound existing
in the block copolymer so that a hydrogenated block copolymer can
be obtained. There is no particular restriction on the method for
hydrogenation reaction, insofar as olefinic unsaturated bonds
derived from a conjugated diene compound existing in the block
copolymer can be decreased.
[0333] In the Embodiment, the block copolymer of an aromatic vinyl
compound/a conjugated diene compound having a functional group,
which is prepared by further reacting the block copolymer with an
unsaturated compound having a functional group (e.g. a carboxylic
group, an acid anhydride group, an ester group and a hydroxy
group), and a hydrogenated block copolymer having a functional
group, which is prepared by hydrogenation of said block copolymer,
can be also used.
[0334] In the Embodiment, the mixture of the non-hydrogenated block
copolymer and the hydrogenated block copolymer can be used as the
block copolymer without any problem.
[0335] In the Embodiment, as disclosed in the pamphlet of WO
02/094936, a block copolymer that is totally or partially modified
or a block copolymer blended in advance with an oil may be also
favorably utilized.
[0336] In the Embodiment, an ethylene/.alpha.-olefin copolymer is a
copolymer of ethylene and at least one type of C3 to C20
.alpha.-olefin. Specific examples of said C3 to C20 .alpha.-olefin
include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene,
1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene,
1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene,
3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene,
4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene,
4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene,
11-methyl-1-dodecene, 12-ethyl-1-tetradecene and a combination
thereof. A copolymer using a C3 to C12 .alpha.-olefin out of said
.alpha.-olefins is preferable.
[0337] The content of an .alpha.-olefin in the
ethylene/.alpha.-olefin copolymer is preferably from 1 to 30 mol %,
more preferably from 2 to 25 mol %, and further preferably 3 to 20
mol %.
[0338] In the Embodiment, at least one type of a non-conjugated
diene, such as 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene,
5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene and
5-(1'-propenyl)-2-norbornene, may be further copolymerized.
[0339] In general, an ethylene/.alpha.-olefin copolymer may be also
used as an ethylene/.alpha.-olefin copolymer having a functional
group that is prepared by reacting an ethylene/.alpha.-olefin
copolymer with an unsaturated compound having a functional group
(e.g. a carboxylic group, an acid anhydride group, an ester group
and a hydroxy group), a copolymer of ethylene and a monomer having
a functional group (e.g. an epoxy group, a carboxylic group, an
acid anhydride group, an ester group and a hydroxy group) and a
copolymer of ethylene/.alpha.-olefin/a monomer having a functional
group.
[0340] In the Embodiment, the content of an impact improver to be
added is preferably from 1 to 15 parts by mass based on total 100
parts by mass of polyphenylene ether and a thermoplastic resin
other than polyphenylene ether, and more preferably from 3 to 12
parts by mass.
[0341] If the content is 1 part by mass or higher, the toughness of
a molded article molded from a long fiber filler reinforced pellet
is improved, and if the content is 15 parts by mass or lower,
mechanical strength and heat resistance become superior.
[0342] In the Embodiment, a long fiber filler reinforced resin
pellet, a resin pellet without a long fiber or a resin pellet blend
may further contain an electroconductive carbon filler.
[0343] Examples of an electroconductive carbon filler include
electroconductive carbon black, carbon nanotube and carbon
fiber.
[0344] An example of electroconductive carbon black is Ketjen Black
(EC, EC-600JD) available from Ketjen Black International Co.
Ltd.
[0345] An example of carbon nanotube is a carbon fibril (BN FIBRIL)
available from Hyperion Catalysis International Inc. Among carbon
fibrils, a carbon fibril as disclosed in the pamphlet for WO
94/23433 is preferable.
[0346] In the Embodiment, although there is no particular
restriction on the method for adding the electroconductive carbon
filler, examples thereof include:
(1) By production of the long fiber filler reinforced resin pellet,
an electroconductive carbon filler and the thermoplastic resin
blend are premixed; (2) By production of a resin pellet without a
long fiber filler, an electroconductive carbon filler and the resin
component are premixed; and (3) By production of the resin pellet
blend, the long fiber filler reinforced resin pellet, according to
need a resin pellet without a long fiber and a master batch, in
which an electroconductive carbon filler is premixed with a
thermoplastic resin other than polyphenylene ether, are
admixed.
[0347] Also in the methods (1) and (2), an electroconductive carbon
filler should preferably be added in the form of a master batch
premixed with a thermoplastic resin other than polyphenylene ether.
In case an electroconductive carbon filler in a master batch is
electroconductive carbon black, the content thereof should be
preferably from 5 to 15% by mass, and in case of other
electroconductive carbon fillers, the content thereof should be
preferably from 10 to 30% by mass. More preferably, in case an
electroconductive carbon filler is electroconductive carbon black,
the content is from 7 to 12% by mass, and in case of other
electroconductive carbon fillers, the content is from 15 to 25% by
mass.
[0348] Examples of a master batch, in which an electroconductive
carbon filler is already admixed in a thermoplastic resin other
than polyphenylene ether, more particularly technical examples in
case polyamide is used as the thermoplastic resin, include a master
batch in which electroconductive carbon black is dispersed
homogeneously in polyamide in advance as disclosed in Japanese
Patent Application Laid-Open No. 02-201811, a masterbatch in which
electroconductive carbon black is dispersed in polyamide with
appropriate nonuniformity as disclosed by the present inventor in
U.S. Pat. No. 6,942,823, and a carbon fibril master batch, such as
a master batch of polyamide 66/carbon fibril (trade name: Polyamide
66 with FIBRIL.TM. Nanotubes RMB4620-00; carbon fibril content 20%)
available from Hyperion Catalysis International Inc. Similar
examples can be presented for thermoplastic resins other than
polyamide.
[0349] As a master batch in the Embodiment, a master batch in which
electroconductive carbon black is dispersed in a thermoplastic
resin with appropriate nonuniformity is preferable.
[0350] A preferable master batch with appropriate nonuniformity in
dispersion means more specifically, if under an optical microscope
a continuous area of 3 mm.sup.2 is observed, at least a part of
electroconductive carbon black exists forming aggregates with the
major diameter from 20 to 100 .mu.m in number of 1 to 100. In more
preferable master batch, if under an optical microscope a
continuous area of 3 mm.sup.2 is observed, the aggregates of
electroconductive carbon black with the major diameter from 20 to
100 .mu.m exist in number of 2 to 30.
[0351] The observation of the aggregates of electroconductive
carbon black in a master batch may follow the method disclosed in
U.S. Pat. No. 6,942,823.
(Production Process for Long Fiber Filler Reinforced Resin
Pellet)
[0352] A production process for the long fiber filler reinforced
resin pellet of the Embodiment includes the steps of: (1) producing
a thermoplastic resin blend in a molten state by an extruder, (2)
impregnating a long fiber filler into the thermoplastic resin blend
in a molten state, (3) forming a resin strand by drawing and
twisting, and (4) cutting the resin strand to a pellet form.
[0353] In the Embodiment, the steps (1) to (4) are preferably
included continuously in said successive order.
[0354] In the Embodiment, a facility including, as disclosed in
Japanese Patent Application Laid-Open No. 2003-175512, an extruder
for melting and blending the resin, a dipping bath vessel installed
downstream thereof for impregnating the resin into reinforcing long
fibers, and twisting rolls for twisting a resin impregnated resin
strand, should preferably be used.
[0355] In the Embodiment, twisting the long fiber filler may have
an effect on accelerating impregnation of a resin into the long
fiber filler. The step has another effect of discharging air
trapped among fibers of the long fiber filler outside the
cross-section of the strand.
[0356] Examples of a method for twisting include a method of
rotating the outlet of a die around the axis of the strand by a
motor, and a method using a twister which rotates the strand during
drawing around the axis along the drawing direction of the
strand.
[0357] In the Embodiment, for example, a twister has facing rolls
with differently oriented rotating axes, and by passing the resin
impregnated long fiber filler through the rolls of the twister the
same can be twisted. The twister is installed preferably between a
water bath and a pelletizer.
[0358] As an extruder to be used for melting and kneading the resin
in the step (1), any of a single screw extruder, a twin screw
extruder and a kneader may be used, and a twin screw extruder is
preferable.
[0359] Examples of a specific process for producing a thermoplastic
resin blend in a molten state include (1A) a method by which a
thermoplastic resin blend prepared in advance by melting and
kneading polyphenylene ether and a thermoplastic resin other than
polyphenylene ether is fed into an extruder to be molten again,
(1B) a method by which polyphenylene ether and a thermoplastic
resin other than polyphenylene ether are respectively fed
simultaneously to the same feeding port of the extruder for melting
and kneading, and (1C) a method by which polyphenylene ether and a
thermoplastic resin other than polyphenylene ether are respectively
fed to different feeding ports of the extruder for melting and
kneading, and any of them may be applied.
[0360] Among them, the method (1B) or (1C) is more preferable.
[0361] Which of the method (1B) or (1C) is more preferable, depends
on a type of the thermoplastic resin other than polyphenylene ether
to be used. For example, if a resin highly compatible with
polyphenylene ether is used as the thermoplastic resin other than
polyphenylene ether, the method (1B) may be selected generally. On
the other hand with a resin poorly compatible with polyphenylene
ether, the method (1C) is preferable generally. More specific
examples thereof include, a method by which polyphenylene ether and
a compatibilizer are charged through a feeding port of the
extruder, and after a functionalization step of polyphenylene ether
a thermoplastic resin other than polyphenylene ether is added for
kneading through a different feeding port located at a downstream
stage, and a method by which a mixture of a part of the
thermoplastic resin other than polyphenylene ether and
polyphenylene ether is charged through a feeding port of the
extruder, and the rest of the thermoplastic resin other than
polyphenylene ether is charged to a downstream feeding port. In any
case by use of a thermoplastic resin poorly compatible with
polyphenylene ether, a publicly known production process effective
for compatibilization may be applied.
[0362] In order to add a filler other than the long fiber filler
into the long fiber filler reinforced resin pellet of the
Embodiment, there is no particular restriction on the feeding
location for said filler, and it may be fed similarly as a resin to
a feeding port at the most upstream location or to a feeding port
located at the stage where the resin has reached a molten state. An
extruder with a plurality of feeding ports in downstream stages can
be favorably used.
[0363] In the Embodiment, the set temperature of the dipping bath
in the step (2) should preferably be set at a temperature, at which
the melt viscosity at a shear rate of 1,000 sec.sup.-1 becomes in a
range from 10 to 200 Pas. The melt viscosity of a thermoplastic
resin blend is more preferably 20 Pas or higher, further preferably
30 Pas or higher, and still further preferably 40 Pas or higher.
The melt viscosity of a thermoplastic resin blend is more
preferably 180 Pas or lower, further preferably 150 Pas or lower,
and still further preferably 100 Pas.
[0364] Although the melt viscosity of a thermoplastic resin blend
may vary depending upon a type of a thermoplastic resin other than
polyphenylene ether, the viscosities of respective resin
components, and existence or non-existence and a quantity of a
compatibilizer, it is very effective to regulate appropriately the
set temperature of the dipping bath, so that the melt viscosity of
the resin can be adjusted to a desired value.
[0365] The set temperature of the dipping bath in the step of
impregnating the long fiber filler with the thermoplastic resin
blend in a molten state, should be preferably set at a temperature
higher by 20.degree. C. or more than a set temperature of the
extruder in the step for producing the thermoplastic resin blend in
a molten state. This temperature setting is also valuable for
adjusting the viscosity of the molten resin in the aforementioned
viscosity range. More preferably, the set temperature of the
dipping bath is higher by 30.degree. C. or more than a set
temperature of the extruder in the step for producing the
thermoplastic resin blend in a molten state. Although there is no
particular upper limit of the set temperature of the dipping bath,
to avoid degradation of the resin, 50.degree. C. may be a practical
limit.
[0366] The temperature, at which the melt viscosity of a
thermoplastic resin blend at a shear rate of 1,000 sec.sup.-1 falls
within 10 to 200 Pas, is in a range from 280 to 350.degree. C. in
case a thermoplastic resin other than polyphenylene ether is, for
example, PPS, and therefore, as a rough rule, the thermoplastic
resin blend is required to be so prepared that the melt viscosity
at 310.degree. C. and a shear rate of 1,000 sec.sup.-1 falls within
10 to 200 Pas.
[0367] In the Embodiment, it is preferable to install several rolls
in the dipping bath in order to fibrillate the long fiber filler
and accelerate the impregnation.
[0368] The drawing speed of a resin strand in the step (3) of the
production process of the pellet of the Embodiment is preferably
from 10 to 150 m/min, more preferably 20 m/min or higher, and
further preferably 35 m/min. The drawing speed of a resin strand is
more preferably 100 m/min or lower, and further preferably 80
m/min.
[0369] The drawing speed of a resin strand in the step (3) is from
10 to 150 m/min, which is higher than a usual speed enabling
utilization of the non-Newtonian property of viscosity, so that
improvement of impregnation of the resin into the long fiber filler
can be effectuated effectively.
[0370] There is no particular restriction on the production process
for a resin pellet without a long fiber filler that is able to
constitute the resin pallet blend of the Embodiment, insofar as it
is publicly known, and any apparatus among a single screw extruder,
a twin screw extruder, Brabender and a kneader may be used.
[0371] There is no particular restriction on the production process
for a resin pellet blend containing a long fiber filler reinforced
resin pellet of the Embodiment, but a production process to mix a
desired amounts of the long fiber filler reinforced resin pellet
and the resin pellet without a long fiber filler using a
blending/agitating apparatus, such as a tumbler, a screw blender
and a Henschel mixer, is preferable.
(Molded Article)
[0372] A molded article of the Embodiment is a molded article to be
obtained by melt-molding the long fiber filler reinforced resin
pellet, and a molded article to be obtained by melt-molding the
resin pellet blend.
[0373] In the Embodiment, a molded article includes a bulk-form
molded article by injection molding, a film/sheet-form molded
article by extrusion or inflation molding and a molded article by
profile extrusion molding.
[0374] Molded articles obtained by melt-molding the pellet and/or
the resin pellet blend may be used industrially as various parts.
They can be used favorably, for example, for electrical or
electronic parts, such as an IC tray materials and a chassis and a
cabinet for various disk players, OA parts and machine parts for
various computers and their peripheral devices, etc., further for a
cowl of a motorbike, automobile exterior parts, such as a fender, a
door panel, a front panel, a rear panel, a locker panel, a rear
bumper panel, a back door garnish, an emblem garnish, a panel for a
feeding port of fuel, an over fender, an outer door handle, a door
mirror housing, a bonnet air intake, a bumper, a bumper guard, a
roof rail, a roof rail leg, a pillar, a pillar cover, a wheel
cover, various aerodynamic parts as represented by a spoiler,
various decorations and emblems, and interior parts, as represented
by an instrument panel, a console box and a trim.
[0375] In the Embodiment, an electroconductive molded article
containing an electroconductive carbon filler can be favorably
utilized for mechanical parts requiring preventive measures against
malfunctioning caused by static electricity and interior or
exterior parts requiring electroconductivity.
[0376] In the Embodiment, it is preferable to use an injection
molding machine equipped with a screw for a long fiber filler for
injection-molding the long fiber filler reinforced resin pellet
from the viewpoint of maintaining the length of the long fiber
filler long in a molded article. The weight average fiber length of
the long fiber filler in a molded article is preferably in a range
from 1 mm to 7 mm. The more preferable lower limit is 1.2 mm or
longer, and the more preferable upper limit is 5 mm. From the
viewpoint of suppression of the anisotropy and improvement of the
surface impact strength of a molded article to be obtained, the
lower limit is preferably 1 mm or longer, and from the viewpoint of
prevention of deterioration of the appearance of a molded article,
the upper limit is preferable set at 7 mm or shorter.
EXAMPLES
[0377] The Embodiment will now be described in more detail by way
of Examples thereof and Comparative Examples, provided that the
Embodiment should not be limited to the Examples. The evaluation
methods and the measurement methods in the Embodiment are described
below.
(Resins Used)
Polyphenylene Ether
[0378] polyphenylene ether (PPE-1): reduced viscosity
.eta..sub.sp/c: 0.51 dL/g [0379] a polymer composed of
2,6-dimethylphenol
[0380] polyphenylene ether (PPE-2): reduced viscosity
.eta..sub.sp/c: 0.42 dL/g [0381] a polymer composed of
2,6-dimethylphenol
[0382] polyphenylene ether (PPE-3): polyphenylene ether polymerized
according to Japanese Patent Publication No. 60-34571 [0383]
reduced viscosity .eta..sub.sp/c: 0.32 dL/g [0384] a polymer
composed of 2,6-dimethylphenol
[0385] polyphenylene ether copolymer (PPE-4): polyphenylene ether
copolymer polymerized according to Japanese Patent Application
Laid-Open No. 64-33131 [0386] reduced viscosity .eta..sub.sp/c:
0.53 dL/g [0387] a polymer composed of 2,6-dimethylphenol (75%) and
2,3,6-trimethylphenol (25%) Resin Other than Polyphenylene
Ether
[0388] Styrenic Resin
[0389] homo-polystyrene (PS-1): Polystyrene 680 procured from PS
Japan Corp.
[0390] homo-polystyrene (PS-2): Styron 685 (Registered trade name)
procured from Dow Chemical Co. (USA)
[0391] high impact-polystyrene (PS-3): high impact-polystyrene
procured from PS Japan Corp. [0392] rubber content: 8%
Olefinic Resin
[0393] polypropylene (PP-1): homo-polypropylene [0394] density=0.90
g/cm.sup.3, MFR=35 g/10 min (230.degree. C., load 21.2 N)
[0395] polypropylene (PP-2): homo-polypropylene [0396] density=0.91
g/cm.sup.3, MFR=40 g/10 min (230.degree. C., load 21.2 N)
[0397] polypropylene (PP-3): homo-polypropylene [0398] density=0.90
g/cm.sup.3, MFR=1.2 g/10 min (230.degree. C., load 21.2 N)
Polyester
[0399] liquid crystal polyester (LCP): liquid crystal polyester
prepared according to Preparation Example 1
[0400] melting point (DSC method): 319.degree. C.
[0401] melt viscosity (330.degree. C., shear rate 100 sec.sup.-1):
18 Pas
Polyamide
[0402] polyamide 6,6 (PA66): Vydyne 48BX (Registered trade name)
procured from Solutia Inc. (USA)
[0403] polyamide 9,T (PA9T): polyamide 9T prepared according to
Preparation Example 2 [0404] terminal amino group concentration: 20
.mu.mol/g [0405] terminal carboxyl group concentration: 65
.mu.mol/g
Polyarylene Sulfide
[0406] polyphenylene sulfide (PPS-1): cross-linked type
poly(p-phenylene sulfide) [0407] melt viscosity (shear rate 100
sec.sup.-1, 300.degree. C.): 130 Pas [0408] oligomer content: 0.6%
by mass
[0409] polyphenylene sulfide (PPS-2): semi-cross-linked type
poly(p-phenylene sulfide) [0410] melt viscosity (shear rate 100
sec.sup.-1, 300.degree. C.): 140 Pas [0411] oligomer content: 0.5%
by mass
[0412] polyphenylene sulfide (PPS-3): linear type poly(p-phenylene
sulfide) [0413] melt viscosity (shear rate 100 sec.sup.-1,
300.degree. C.): 110 Pas [0414] oligomer content: 0.3% by mass
[0415] polyphenylene sulfide (PPS-4): linear type poly(p-phenylene
sulfide) [0416] melt viscosity (shear rate 100 sec.sup.-1,
300.degree. C.): 75 Pas [0417] oligomer content: 0.3% by mass
[0418] polyphenylene sulfide (PPS-5): linear type poly(p-phenylene
sulfide) [0419] melt viscosity (shear rate 100 sec.sup.-1,
300.degree. C.): 38 Pas [0420] oligomer content: 0.5% by mass
[0421] polyphenylene sulfide (PPS-6): linear type poly(p-phenylene
sulfide) [0422] melt viscosity (shear rate 100 sec.sup.-1,
300.degree. C.): 14 Pas [0423] oligomer content: 0.5% by mass
[0424] polyphenylene sulfide (PPS-7): semi-cross-linked type
poly(p-phenylene sulfide) [0425] melt viscosity (shear rate 100
sec.sup.-1, 300.degree. C.): 180 Pas [0426] oligomer content: 0.5%
by mass
[0427] polyphenylene sulfide (PPS-8): cross-linked type
poly(p-phenylene sulfide) [0428] melt viscosity (shear rate 100
sec.sup.-1, 300.degree. C.): 240 Pas [0429] oligomer content: 0.5%
by mass
[0430] polyphenylene sulfide (PPS-9): semi-cross-linked type
poly(p-phenylene sulfide) [0431] melt viscosity (shear rate 100
sec.sup.-1, 300.degree. C.): 310 Pas [0432] oligomer content: 0.4%
by mass
Polyarylate
[0433] polyarylate (PAR): U-Polymer U-100 (Registered trade name)
procured from Unitika Ltd.
Polyaryl Ketone
[0434] polyetherether ketone (PEEK): VICTREX PEEK 151G (Registered
trade name) procured from Victrex plc.
Impact improver (By use in PP, it functions also as a
compatibilizer.)
[0435] polystyrene block-hydrogenated polybutadiene-polystyrene
block-(SEBS-1) [0436] bound styrene content: 43%, 1,2-vinyl bond
content of polybutadiene segment: 75%, number average molecular
weight of polystyrene chain: 15,000, hydrogenation rate of
polybutadiene segment: 99.8%
[0437] polystyrene block-hydrogenated polybutadiene-polystyrene
block (SEBS-2) [0438] bound styrene content: 60%, 1,2-vinyl bond
content of polybutadiene segment: 80%, number average molecular
weight of polystyrene chain: 24,000, hydrogenation rate of
polybutadiene segment: 99.2%
[0439] polystyrene block-hydrogenated polybutadiene-polystyrene
block (SEBS-3) [0440] bound styrene content: 33%, 1,2-vinyl bond
content of polybutadiene segment: 47%, number average molecular
weight of polystyrene chain: 29,000, hydrogenation rate of
polybutadiene segment: 99.8%
[0441] polystyrene block-hydrogenated polybutadiene-polystyrene
block (SEBS-4) [0442] bound styrene content: 60%, 1,2-vinyl bond
content of polybutadiene segment: 55%, number average molecular
weight of polystyrene chain: 24,000, hydrogenation rate of
polybutadiene segment: 99.2%
Flame Retardant
[0443] phosphate based flame retardant (FR-1): CR-741 procured from
Daihachi Chemical Ind.
[0444] aluminum phosphinate (FR-2): Exolit OP930 (Registered trade
name) procured from Clariant.
Long Fiber Filler
[0445] glass fiber filler (LGF): ER2400T-448N procured from Nippon
Electric Glass Co., Ltd. [0446] long glass fiber filament roving of
2,400 tex with fiber diameter of 17 .mu.m
Compatibilizer
[0447] maleic anhydride (MAH): CRYSTAL MAN-AB procured from NOF
Corporation
[0448] styrene/glycidyl methacrylate copolymer (SG-C) [0449]
containing 5% by mass of glycidyl methacrylate [0450] weight
average molecular weight: 110,000
[0451] styrene/2-isopropenyl-2-oxazoline copolymer (SO--C) [0452]
containing 5% by mass of 2-isopropenyl-2-oxazoline [0453] weight
average molecular weight: 146,000
Stabilizer
[0454] sterically-hindered phenolic antioxidant (Irg1098) [0455]
Irganox 1098 (Registered trade name) procured from Ciba Specialty
Chemicals Ltd.
Preparation Example 1
Production of LCP
[0456] In a 2-L polymerization reactor with a stirrer and a
evaporation line p-hydroxybenzoic acid, 2-hydroxy-6-naphthoic acid,
hydroquinone, 2,6-naphthalenedicarboxylic acid and acetic anhydride
were charged and subjected to a polycondensation eliminating acetic
acid according to the following procedures. The reactor charged
with raw materials was heated from 40.degree. C. to 190.degree. C.
over 3 hours under a nitrogen gas atmosphere, kept at 190.degree.
C. for 1 hour, further heated up to 325.degree. C. over 2 hours,
and left for reaction for 10 min. Next the reactor was vacuumed to
20 mmHg at 325.degree. C. for 20 min, and left for reaction
additionally for 5 min to complete polycondensation. As the result
of polymerization, substantially theoretical amount of acetic acid
was distilled off to obtain the liquid crystal polyester having the
theoretical structural formula as represented by the following
formula.
[0457] The melting point by DSC was 319.degree. C. The melt
viscosity measured using a capillary rheometer at 330.degree. C.
and shear rate of 1,000 sec.sup.-1 was 18 Pas. Concerning a
composition, the ratio of components represents mol ratio.
##STR00010##
Preparation Example 2
Production of Aromatic Polyamide
Polyamide 9T
[0458] According to the method described in an example of Japanese
Patent Laid-Open No. 2000-103847, terephthalic acid as a
dicarboxylic acid component, 1,9-nonamethylenediamine and
2-methyl-1,8-octamethylenediamine as diamine components, octylamine
or benzoic acid as a terminal capping agent, sodium hypophosphite
monohydrate as a polymerization catalyst, and distilled water were
charged into an autoclave, which was closed hermetically (water
content in the reaction system: 25% by mass). After replaced
thoroughly with nitrogen, the autoclave was heated up over 2 hours
to the internal temperature of 260.degree. C. with stirring, and
left reacting under the same condition. The internal pressure was
46 atm.
[0459] Next, keeping the internal temperature of the reactor at
260.degree. C. and the water content at 25% by mass, the reaction
product was discharged through a nozzle (6 mm diameter) at the
bottom of the reactor over 3 min under a nitrogen atmosphere into a
container at normal temperature and pressure, and dried at
120.degree. C. to obtain foamless powder-form primary
polycondensate.
[0460] Then, the powder-form primary polycondensate was heated up
to 250.degree. C. over 2 hours under a nitrogen atmosphere and with
stirring, and kept under the same condition for a predefined time
period to conduct a solid state polymerization.
[0461] Measurements of the capped terminus rate and the terminal
group concentration of the obtained aromatic polyamide were
conducted according to the measurement of the capped terminus rate
described in an example of Japanese Patent Application Laid-Open
No. 07-228689, and quantitative analysis of a phosphorus element
was conducted by inductively coupled plasma (ICP) spectrometry
using IRIS/IP manufactured by Thermo Jarrell Ash Corp. using the
wave length of 213.618 (nm). The terminal amino group concentration
was 20 .mu.mol/g, the terminal carboxyl group concentration was 65
.mu.mol/g, and the capped terminus rate was 55%.
[0462] Using the resin pellets and strands obtained in Examples 1
to 70, the evaluations of the following items were conducted.
[Evaluation Items]
(Melt Viscosity of Resin)
[0463] By Capirograph (Toyo Seiki Seisaku-sho, Ltd.) using a
capillary of capillary length=10 mm and capillary diameter=1 mm,
apparent melt viscosities were measured at 2 shear rates containing
the shear rate of 1,000 sec.sup.-1 at an individually described
temperature, and the value was determined by extrapolating them to
1,000 sec.sup.11.
(Lead of Spiral of Long Fiber Filler)
[0464] During extrusion of a long fiber filler reinforced resin
pellet, about 30 cm of a strand was sampled, and the length
required for 1 round on the outer surface of the strand by a
pattern of a twist of the contained long fiber filler (glass fiber)
standing out on the outer surface of the strand was directly
measured.
(Ratio of Average Fiber Length of Long Fiber Filler to Length of
Pellet)
[0465] After measuring the average length of pellets, the resin
component of the pellets was burnt at 650.degree. C. in an
electrical oven. Then out of the obtained long fiber fillers (glass
fibers), only the lengths of the fiber fillers which were 3 mm or
longer were measured by an image analyzer and the weight average
fiber length was calculated according to the following formula and
the ratio of the average fiber length of the long fiber filler to
the length of the pellet was determined. Thereby at least 500
fibers were measured.
Lw=.SIGMA.(Li.sup.2.times.Ni)/(Li.times.Ni)
wherein Lw represents the weight average fiber length, Li
represents representative fiber lengths of respective groups and Ni
represents numbers of the long fiber fillers of the respective
groups. Thereby the long fiber fillers were classified to groups at
0.1 mm intervals and the median fiber length of the fiber length
range was designated as the representative fiber length of the
group. As a specific example, long fiber fillers (glass fibers)
having the fiber length beyond 3 mm and equal to or less than 3.1
mm are classified into a group whose representative fiber length is
designated as 3.05 mm.
(Rate of Long Fiber Filler)
[0466] The resin component of a resin pellet was burnt in an
electrical oven set at 650.degree. C., and based on the weighed
residue weight the rate of the contained long fiber filler (glass
fiber) was determined.
(Impregnation Property of Resin into Long Fiber Filler)
[0467] A propyl alcohol solution of methyl red as a color indicator
was prepared by adding 1 cm.sup.3 of hydrochloric acid to adjust
the pH and improve coloring property of methyl red into a 50
cm.sup.3 of a saturated solution of methyl red in propyl alcohol.
Arbitrarily selected 10 strands were dipped in the solution up to 1
cm from the fracture cross-section for about 30 min. Thereafter the
strands were taken out and a longitudinal penetration situation of
the color indicator was examined. Then the impregnation property of
a resin into a long fiber filler was evaluated according to the
penetration situation of the color indicator from the fracture
cross-section of the strand. By averaging the penetration distances
of the 10 strands, rating was given according to: in case the
average penetration length is 5 mm or less: "good"; in case 5 mm to
10 mm: "fair"; and in case 10 mm or longer: "poor".
(Ratio of Cross-Section of Core Part to Core-Section of Pellet)
[0468] A pellet was cut to the width direction by a microtome to a
flat cross-section, which was observed under an optical microscope
with reflection light and photographed. By image analysis the ratio
of the cross-section of the core part to the core-section of the
pellet was calculated.
(Appearance of Pellet Surface)
[0469] The pellet surface was visually observed. A pellet with
sufficient glossy surface was rated as A, a pellet with partly not
glossy surface was rated as B, and a pellet with mostly not glossy
surface was rated as C.
(Longitudinal Fracture of Pellet)
[0470] Randomly selected 100 pellets were enclosed hermetically in
a 50 cm.sup.3 metal container and shaken at an amplitude of 50 mm
and a frequency of 60 cycles/min, and then the pellets inside were
taken out and the number of pellets that have caused a longitudinal
fracture was counted.
(Detachment of Long Fiber Filler)
[0471] The amount of the long fiber fillers (glass fibers) attached
to the wall surface of the metal container at the evaluation of the
longitudinal fracture of pellets was visually rated.
(Fibrillation Property of Long Fiber Filler)
[0472] The obtained long fiber filler reinforced resin pellet was
molded to a multi-purpose test specimen with the thickness of 4 mm
according to ISO 294-1 using IS100GN (Toshiba Machine Co., Ltd.)
equipped with a screw having a low compression ratio suitable for
molding a long fiber filler reinforced resin pellet. The resin
component of the obtained multi-purpose test specimen was burnt at
650.degree. C. in an electrical oven, after slow cooling the
specimen was taken out gently, and the form retainability of the
ash (whether the form of a multi-purpose test specimen is
maintained by the network of a long fiber filler) was rated.
Thereby with good fibrillation property of a long fiber filler, a
network of a long fiber filler is easier to be formed during
molding, which increases the form retainability. On the contrary
with poor fibrillation property during molding, the network is
formed insufficiently and the form retainability becomes very poor.
Consequently, the fibrillation property of a long fiber filler was
rated by the form retainability.
[0473] The criteria of the form retainability are shown below:
[0474] AA: The form of a multi-purpose test specimen is
substantially maintained.
[0475] A: The form except a part around a gate is maintained.
[0476] B: The form of a flow front is only maintained.
[0477] C: The form is not maintained.
(Surface Impact Strength of Molded Article)
[0478] The obtained long fiber filler reinforced resin pellet was
molded to a flat test specimen with the size of
50.times.90.times.2.5 mm using IS100GN (Toshiba Machine Co., Ltd.)
equipped with a screw having a low compression ratio suitable for
molding a long fiber filler reinforced resin pellet. Using the
obtained test specimen, the total absorbed energy at an impact test
at 23.degree. C. was measured by Graphic Impact Tester (Toyo
Seiki-Seisakusho, Ltd.) using a holder of diameter 40 mm and a
striker of diameter 12.7 mm and mass of 6.5 kg impacting from the
height of 128 cm.
(DTUL of Molded Article)
[0479] A multi-purpose test specimen with the thickness of 4 mm
according to ISO 294-1 was molded by the same extruder used for
molding a test specimen for measuring surface impact strength.
[0480] Using the obtained multi-purpose test specimen, a flatwise
deflection temperature under load was measured according to ISO 75
with loads of 0.45 MPa and/or 1.8 MPa.
(Charpy Impact Strength of Molded Article)
[0481] A multi-purpose test specimen with the thickness of 4 mm
according to ISO 294-1 was molded by the same extruder used for
molding a test specimen for measuring surface impact strength.
Using the obtained multi-purpose test specimen, a notched Charpy
impact strength was measured at 23.degree. C. according to ISO
179.
(Flexural Strength of Molded Article)
[0482] Using the multi-purpose test specimen obtained similarly as
the test specimen for Charpy impact strength, a flexural strength
was measured according to ISO 178.
<Production of PS/PPE1>
[0483] The maximum cylinder temperature of a co-rotating twin screw
extruder (ZSK25: Coperion) with L/D=42, having an upstream feeding
port and a downstream feeding port, was set at 320.degree. C.
PS/PPE1 was obtained by feeding 20 parts by mass of PPE-1 and 20
parts by mass of PS-1 respectively through the upstream feeding
port to the extruder, and feeding 60 parts by mass of PS-1 through
the downstream feeding port; to be melt-blended, while evaporating
a volatile matter under a reduced pressure through a venting port
provided downstream of the downstream feeding port; and cooling by
water, drawing and cutting the strand. Thereby the screw rotation
speed was set at 300 rpm. The melt viscosity of the obtained
PS/PPE1 was measured by a capillary rheometer to find that the
temperature was about 300.degree. C. at which the melt viscosity at
a shear rate of 1,000 sec.sup.-1 became 20 to 100 Pas.
<Production of PS/PPE2>
[0484] Except that 50 parts by mass of PPE-1 and 20 parts by mass
of PS-1 were respectively fed through the upstream feeding port to
the extruder, and that 30 parts by mass of PS-2 was fed through the
downstream feeding port, all other conditions were performed
identically with the production of PS/PPE1 to obtain PS/PPE2. The
melt viscosity of the obtained PS/PPE2 was measured by a capillary
rheometer to find that the temperature was beyond 320.degree. C. at
which the viscosity at a shear rate of 1,000 sec.sup.-1 became 200
Pas.
<Production of PS/PPE3>
[0485] Except that 40 parts by mass of PPE-2 and 10 parts by mass
of PS-1 were respectively fed through the upstream feeding port to
the extruder, and that 50 parts by mass of PS-1 were fed through
the downstream feeding port, all other conditions were performed
identically with the production of PS/PPE1 to obtain PS/PPE3. The
melt viscosity of the obtained PS/PPE3 was measured by a capillary
rheometer to find that the temperature was about 310.degree. C. at
which the melt viscosity at a shear rate of 1,000 sec.sup.-1 became
20 to 100 Pas.
<Production of PS/PPE4>
[0486] Except that the PPE to be fed through the upstream feeding
port was changed to PPE-3, all other conditions were performed
identically with the production of PS/PPE1 to obtain PS/PPE4. The
melt viscosity of the obtained PS/PPE4 was measured by a capillary
rheometer to find that the temperature was about 280.degree. C. at
which the melt viscosity at a shear rate of 1,000 sec.sup.-1 became
20 to 100 Pas.
<Production of PS/PPE5>
[0487] Except that the PPE to be fed through the upstream feeding
port was changed to PPE-4, all other conditions were performed
identically with the production of PS/PPE1 to obtain PS/PPE5. The
melt viscosity of the obtained PS/PPE5 was measured by a capillary
rheometer to find that the temperature was about 330.degree. C. at
which the melt viscosity at a shear rate of 1,000 sec.sup.-1 became
20 to 100 Pas.
<Production of PS/PPE6>
[0488] Except that the 55 parts by mass of PPE-1 and 45 parts by
mass of PS-2 were respectively fed through the upstream feeding
port to the extruder and that nothing was added through the
downstream feeding port, all other conditions were performed
identically with the production of PS/PPE1 to obtain PS/PPE6.
[0489] This PS/PPE6 was blended with a long fiber filler reinforced
resin pellet and used when the properties of a molded article were
measured.
<Production of PA/PPE1>
[0490] The maximum cylinder temperature of a co-rotating twin screw
extruder (ZSK40MC: Coperion) with L/D=48, having an upstream
feeding port and a downstream feeding port; 12 temperature
regulating blocks, each block constituting L/D=4; and an
auto-screen changer block; and thereby the upstream feeding port
being located at the first block, the downstream feeding port at
the sixth block and a venting ports for removing a volatile matter
by evaporation under a reduced pressure at the fifth and tenth
blocks; was set at 320.degree. C. Feeding 35 parts by mass of
PPE-1, 0.1 parts by mass of MAH, 10 parts by mass of SEBS and 5
parts by mass of PS-3 were respectively fed through an upstream
feeding port to the extruder to be melt-blended, and successively
50 parts by mass of PA66 was fed through a downstream feeding port
to be subjected to melt-blending, to obtain PA/PPE1. Thereby the
screw rotation speed was at 450 rpm. The melt viscosity of the
obtained PA/PPE1 was measured to find that the temperature was
about 300.degree. C. at which the melt viscosity at a shear rate of
1,000 sec.sup.-1 became 15 to 100 Pas. The melt viscosity at
280.degree. C. was confirmed to be 220 Pas.
<Production of PA/PPE2>
[0491] Using the same extruder as in the production of PA/PPE1, 40
parts by mass of PPE-2, 0.4 parts by mass of MAH were dry-blended
and fed through the upstream feeding port to the extruder to be
melt-blended, and successively 60 parts by mass of PA9T were fed
through a downstream feeding port to be melt-blended to obtain
PA/PPE2. All of other conditions were identical with the production
of PA/PPE1. The melt viscosity of the obtained PA/PPE2 was measured
to find that the temperature was 330.degree. C. at which the melt
viscosity at a shear rate of 1,000 sec.sup.-1 became 15 to 100
Pas.
<Production of PA/PPE3>
[0492] Except that the polyphenylene ether was changed to PPE-3,
all other conditions were performed identically with the production
of PA/PPE1 to obtain PA/PPE3.
<Production of PA/PPE4>
[0493] Except that the polyphenylene ether was changed to PPE4, all
other conditions were performed identically with the production of
PA/PPE1 to obtain PA/PPE4.
<Production of PP/PPE1 to PP/PPE5>
[0494] The cylinder temperature of the extruder used for production
of PA-PPE1 was set at 290 to 310.degree. C., and a resin blend with
a blend composition described in Table 1 was fed through the
upstream feeding port of the extruder, melt-blended and vented from
vacuum venting ports at 2 locations under the vacuum of the
absolute vacuum pressure of 95 kPa or less while melt-blending to
produce 5 types of resin blends of PP/PPE1 to PP/PPE5. Thereby SEBS
exerted two functions of a compatibilizer between PP and
polyphenylene ether and an impact improver. The melt viscosities of
the obtained resin blends were measured under the conditions of
280.degree. C. and 300.degree. C. and at a shear rate of 1,000
sec.sup.-1, and are included in Table 1.
TABLE-US-00001 TABLE 1 PP/PPE Unit 1 2 3 4 5 PP-1 part by mass 60
50 PP-2 part by mass 60 50 PP-3 part by mass 50 PPE-2 part by mass
40 50 50 PPE-3 part by mass 40 50 SEBS-1 part by mass 10 SEBS-2
part by mass 10 10 Melt viscosity Pa s 68 55 125 120 300 of resin
(280.degree. C., 1000 sec.sup.-1) Melt viscosity Pa s 45 29 87 80
210 of resin (300.degree. C., 1000 sec.sup.-1)
<Production of PPS/PPE1 to PPS/PPE16>
[0495] The cylinder temperature of the extruder used for production
of PA-PPE1 was set at 290 to 310.degree. C., and a resin blend with
a blend composition described in Table 2 was fed through the
upstream feeding port of the extruder, melt-blended, and vented
from vacuum venting ports at 2 locations under the vacuum of the
absolute vacuum pressure of 95 kPa or less while melt-blending to
produce 16 types of resin blends of PPS/PPE1 to PPS/PPE16. Further,
the melt viscosities of the obtained resin blends were measured at
300.degree. C. and a shear rate of 1,000 sec.sup.-1, and are
included in Table 2.
TABLE-US-00002 TABLE 2 PPS/PPE Unit 1 2 3 4 5 6 7 8 9 10 11 12 13
14 15 16 PPS-1 part by mass 70 63 PPS-2 part by mass 60 90 PPS-3
part by mass 65 60 50 60 PPS-4 part by mass 60 PPS-5 part by mass
95 60 70 PPS-6 part by mass 60 PPS-7 part by mass 60 PPS-8 part by
mass 60 PPS-9 part by mass 60 PPE-2 part by mass 30 37 10 35 5 30
PPE-3 part by mass 40 40 50 40 40 40 40 40 40 40 SEBS-3 part by
mass 5 5 5 SEBS-4 part by mass 5 SG-C part by mass 1 1.5 3 1 2 2 6
2 0.5 2 3 2 2 2 SO-C part by mass 2 Melt viscosity Pa s 130 130 140
140 110 110 110 110 75 38 38 38 14 180 240 310 of PPS (100
sec.sup.-1) Melt viscosity Pa s 90 110 160 30 150 160 500 330 190
18 140 95 130 320 350 410 of resin (1000 sec.sup.-1)
<Production of LCP/PPE1>
[0496] The maximum cylinder temperature of the extruder used for
production of PS/PPE1 was set at 330.degree. C., and 30 parts by
mass of PPE-2, 15 parts by mass of LCP and 5 parts by mass of SG-C
were respectively fed through the upstream feeding port to the
extruder and 55 parts by mass of LCP was fed through the downstream
feeding port, to be melt-blended, while evaporating a volatile
matter under a reduced pressure through a venting port provided
downstream of the downstream feeding port. The strand was cooled by
water, drawn and cut to obtain LCP/PPE1. Thereby the screw rotation
speed was 300 rpm. The melt viscosity of the obtained LCP/PPE1 was
measured by a capillary rheometer to find that the temperature was
about 330.degree. C. at which the melt viscosity at a shear rate of
1,000 sec.sup.- became 20 to 100 Pas.
<Production of LCP/PPE2>
[0497] Except that 55 parts by mass of PPE-1, 15 parts by mass of
LCP and 5 parts by mass of SG-C were respectively fed through the
upstream feeding port, and that 30 parts by mass of LCP was fed
through the downstream feeding port, all other conditions were
performed identically with LCP/PPE1 to obtain LCP/PPE2. The melt
viscosity of the obtained LCP/PPE2 was measured by a capillary
rheometer to find that the temperature was beyond 330.degree. C. at
which the viscosity at a shear rate of 1,000 sec.sup.-1 became 200
Pas.
<Production of LCP/PPE3>
[0498] Except that 40 parts by mass of PPE-2, 30 parts by mass of
LCP and 5 parts by mass of SG-C were respectively fed through the
upstream feeding port to the extruder to be melt-blended; that
successively 30 parts by mass of LCP were fed through the
downstream feeding port; and that 7 parts by mass of FR-1 were fed
through a liquid feeding nozzle located further downstream; all
other conditions were performed identically with the production of
LCP/PPE1 to obtain LCP/PPE3. The melt viscosity of the obtained
LCP/PPE3 was measured by a capillary rheometer to find that the
temperature was about 320.degree. C. at which the melt viscosity at
a shear rate of 1,000 sec.sup.-1 became 20 to 100 Pas.
<Production of LCP/PPE4>
[0499] Except that the polyphenylene ether to be fed through the
upstream feeding port was changed to PPE-3, all other conditions
were performed identically with the production of LCP/PPE2 to
obtain LCP/PPE4.
<Production of PEEK/PPE>
[0500] The maximum cylinder temperature of the extruder used for
production of PS/PPE1 was set at 355.degree. C., and 30 parts by
mass of PPE-2, 15 parts by mass of PEEK and 5 parts by mass of PAR
were respectively fed through the upstream feeding port to the
extruder and 55 parts by mass of PEEK were fed through the
downstream feeding port, to be melt-blended, while evaporating a
volatile matter under a reduced pressure through a venting port
provided downstream of the downstream feeding port. The strand was
cooled by water, drawn and cut to obtain PEEK/PPE. Thereby the
screw rotation speed was set at 300 rpm. The melt viscosity of the
obtained PEEK/PPE was measured by a capillary rheometer to find
that the temperature was about 380.degree. C. at which the melt
viscosity at a shear rate of 1,000 sec.sup.-1 became 20 to 100
Pas.
Example 1 to Example 5
Examples and Comparative Examples
[0501] The maximum cylinder temperature of an extruder in a
production facility of a long fiber reinforced resin, which was a
co-rotating twin screw extruder (ZSK25: Coperion) provided with an
feeding port at an upstream zone and a dipping bath with resin
impregnating rolls (Kobe Steel, Ltd.) installed at the front end of
the co-rotating twin screw extruder, was set at 320.degree. C., and
PS/PPE1 was fed through the extruder feeding port, and molten at a
screw rotation speed of 300 rpm and filled in the dipping bath with
resin impregnating rolls. Meanwhile, 2 long-fiber glass fiber
rovings with filament diameter of 17 .mu.m (ER2400T-448N by Nippon
Electric Glass Co., Ltd.) were introduced from a roving supply
stand to the dipping bath with resin impregnating rolls, where the
molten resin in the dipping bath was impregnated into the
long-fiber glass fiber rovings, which were then continuously drawn
out through a nozzle (diameter 2.8 mm) of the dipping bath at the
drawing speed of 15 m/min forming a single strand, cooled and
solidified in a water bath, passed through twisting rolls for
twisting varyingly the resin strand allowing to form twists of
various lead lengths, and then cut by a pelletizer to 10 mm pellet
length. Thereby the set temperature of the dipping bath was
300.degree. C. Further, the extrusion rate of the extruder was so
regulated that the glass fiber content became about 50% by
mass.
[0502] Example 1 to Example 5 were different only in strength of
twisting on the strand, and all other conditions were the same. The
strength of twisting was changed by changing the rotation speed of
the rolls of a twister placed between the water bath and the
pelletizer.
[0503] Using the obtained resin pellets and strands, various
evaluations were conducted. The results are shown in Table 3.
Thereby, the evaluations of Charpy impact strength, flexural
strength, high load DTUL were conducted by dry-blending 60 parts by
mass of the obtained long fiber filler reinforced resin pellet and
40 parts by mass of PS/PPE6 pellet, then molding them under the
conditions of cylinder temperature at 310.degree. C. and a mold
temperature at 90.degree. C., and conducting measurements thereof.
The results are shown in Table 3.
Example 6
Example
[0504] Except that PS/PPE1 was changed to PS/PPE2, all other
conditions were performed identically with the example 3 to obtain
a long fiber filler reinforced resin pellet, on which evaluations
were conducted. The results are shown in Table 3.
Example 7
Comparative Example
[0505] Using chopped strand glass fiber (the surface being treated
by a similar compound as for the long-fiber glass fiber) with
filament diameter of 17 .mu.m and fiber length of 3 mm, a composite
pellet composed of 28% by mass of PS/PPE1, 42% by mass of PS/PPE6
and 30% by mass of chopped strand glass fiber was prepared. Thereby
using the extruder used for preparing PS/PPE1 and setting the
maximum set temperature of the cylinder at 300.degree. C., the
resin components were fed through the upstream feeding port, and
the chopped strand glass fiber was fed through the downstream
feeding port, and melt-extruded. The stand was cut to obtain a
composite pellet with length of about 3 mm and diameter of about 3
mm. The measurement results of Charpy impact strength, flexural
strength, high load DTUL are shown in Table 3.
Example 8
Example
[0506] Setting at 330.degree. C. the cylinder temperature of the
extruder in the same production facility of a long fiber reinforced
resin as used in the example 1 to example 5, PS/PPE3 was fed
through the extruder feeding port, molten at a screw rotation speed
of 300 rpm and filled in the dipping bath with resin impregnating
rolls. As in the example 1 to example 5, the long-fiber glass fiber
rovings were introduced to the dipping bath with resin impregnating
rolls, where the molten resin in the dipping bath was impregnated
into the two long-fiber glass fiber rovings, which were then
continuously drawn out through a nozzle part of the dipping bath at
the drawing speed of 23 m/min forming a single strand, cooled and
solidified in a water bath, passed through twisting rolls for
twisting the resin strand to form a twist with a lead length of 30
mm, and then cut by a pelletizer to a pellet with a pellet length
of 10 mm. Thereby the set temperature of the dipping bath was
320.degree. C.
[0507] Further, the extrusion rate of the extruder was so regulated
that the glass fiber content became about 50% by mass. The glass
fiber content determined according to the later measurement of ash
was 52.5% by mass.
[0508] Using the obtained resin pellets and strands, evaluations as
in the example 1 to example 5 were conducted. Thereby, the
evaluation of impact strength and DTUL of a molded specimen was
conducted by pellet-blending 57 parts by mass of the long fiber
filler reinforced resin pellet obtained in this example and 43
parts by mass of PS/PPE6 pellet, so that the glass fiber content
became 30% by mass, and conducting similarly measurements of the
properties thereof. The results are shown in Table 3.
Example 9
Example
[0509] Except setting the cylinder temperature of the extruder at
280.degree. C., the screw rotation speed at 150 rpm and the
temperature of the dipping bath at 280.degree. C., all others
procedures were identical with the example 8 to obtain a long fiber
filler reinforced resin pellet. The evaluations were conducted
similarly as in the example 8, and the results thereof are shown in
Table 3.
Example 10 to Example 12
Examples and Comparative Example
[0510] Except that the resin blend of PS/PPE was changed to
PS/PPE4, PS/PPE5 or only PS-1 without polyphenylene ether as
described in Table 3, all other procedures and evaluations were
performed identically with the example 3. The results are shown in
Table 3. As for the example 12, in order to evaluate a composition
without polyphenylene ether, 60 parts by mass of the obtained
pellet were blended with 40 parts by mass of the pellet of PS-1,
and the blend was molded under the conditions of the cylinder
temperature at 210.degree. C. and the mold temperature at
80.degree. C., which was then evaluated. The results are shown in
Table 3.
TABLE-US-00003 TABLE 3 Ex. 1 Ex. 5 Ex. 7 Ex. 12 Com. Ex. 2 Ex. 3
Ex. 4 Com. Ex. 6 Com. Ex. 8 Ex. 9 Ex. 10 Ex. 11 Com. Item Unit Ex.
Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. (Composition/
conditions of long fiber filler reinforced resin pellet) PS/PPE1 %
by mass 48.5 48.5 48.5 48.5 48.5 28 PS/PPE2 % by mass 49 PS/PPE3 %
by mass 47.5 47.5 PS/PPE4 % by mass 49 PS/PPE5 % by mass 49 PS/PPE6
% by mass 42 PS-1 % by mass 49 Content of long % by mass 51.5 51.5
51.5 51.5 51.5 51 30*2) 52.5 52.5 51 51 51 fiber filler Temperature
of .degree. C. 320 320 320 320 320 320 300 330 280 320 320 210
extruder cylinder Set temperature of .degree. C. 300 300 300 300
300 300 -- 320 280 300 300 210 dipping bath Drawing speed of m/min
15 15 15 15 15 15 -- 23 23 15 15 15 strand (Properties of long
fiber filler reinforced resin pellet) Spiral lead of long mm 10 25
40 60 100 40 -- 30 30 40 40 40 fiber filler Ratio of average --
1.14 1.08 1.03 1.01 1.00 1.03 -- 1.05 1.05 1.03 1.03 1.03 fiber
length of long fiber filler to length of pellet Impregnation good,
fair good good good poor fair -- good fair good good good property
of resin fair, into long fiber filler poor Cross-section ratio % 56
68 65 60 46 45 -- 67 52 65 62 42 of core part to pellet Appearance
of A, B, C C B A B C C -- A B A A B pellet surface Longitudinal
pellet number none none none 6 15 10 -- none 5 none none none
fracture Detachment of long quantity none none none a few many a
few -- none a few none none none fiber filler Fibrillation property
AA-C B A A AA B A A A AA AA C of long fiber filler (Properties of
molded article of pellet blend*.sup.1)) Charpy impact kJ/m.sup.2 18
20 22 20 16 18 10 16 14 20 22 12 strength of molded article
Flexural strength of MPa 187 188 190 188 182 185 170 177 175 200
195 -- molded article DTUL of molded .degree. C. 140 141 141 140
138 139 135 138 137 143 145 92 article *.sup.1)pellet blend:
adjusted to the composition containing 30% by mass of glass fiber
*2)chopped strand glass fiber used
[0511] As obvious from the results in Table 3, all the pellets of
the long fiber filler reinforced resins of Examples had excellent
wettability, could extremely suppress longitudinal pellet fracture
during transportation and detachment of the long fiber filler from
the pellet, were superior in pellet appearance and were superior in
fibrillation property of the long fiber filler during molding,
enabling to mold a molded article with very high heat resistance
and impact resistance.
[0512] On the other hand, in the examples 1 and 5, in which the
spiral lead was outside the range of 20 mm to 80 mm, in comparison
of the fibrillation property of long fiber filler, only a form at
the flow front part was maintained indicating insufficient
fibrillation property.
[0513] In the example 5 with the spiral lead of 100 mm, many
detached long fiber fillers were recognized.
[0514] In the example 7, in which chopped strand glass fiber was
used instead of the long fiber filler, since the glass fiber length
in a molded article was not sufficient, the impact strength,
flexural strength and heat resistance were insufficient.
[0515] Further, in the example 12 without polyphenylene ether, the
fibrillation property was not sufficient and a molded article
thereof had insufficient strength in the flexural strength,
etc.
Example 13 to Example 23
Examples and Comparative Examples
[0516] Using the same extruder as in the example 1 and setting the
set temperature of the cylinder at 230.degree. C. to 300.degree. C.
and the set temperature of the dipping bath at 220.degree. C.,
280.degree. C. or 300.degree. C., PP/PPE1 to PP/PPE5 and PP-1 were
fed respectively through the feeding port of the twin-screw
extruder, and were impregnated in the dipping bath which
temperature was regulated at 220.degree. C., 280.degree. C. or
300.degree. C., into 2 long-fiber glass fiber rovings, which were
then continuously drawn out through an outlet nozzle (diameter
about 3.5 mm) of the dipping bath at the drawing speed of 20 m/min
forming a strand, which was after twisting cut by a pelletizer to a
pellet length of 10 mm. Thereby the extrusion rate of the extruder
was so regulated that the glass fiber content in the long fiber
reinforced resin composition became 39% by mass.
[0517] Using the obtained resin pellets and strands, evaluations
were conducted. The results are shown in Table 4. Thereby, blend of
a long fiber filler reinforced resin pellet and a pellet without a
long fiber filler was not conducted as in the example 1, the long
fiber filler reinforced resin pellet was injection-molded singly
and the properties were evaluated.
TABLE-US-00004 TABLE 4 Ex. 21 Ex. 22 Ex. 23 Ex. 13 Ex. 14 Ex. 15
Ex. 16 Ex. 17 Ex. 18 Ex. 19 Ex. 20 Com. Com. Com. Unit Ex. Ex. Ex.
Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. (Composition/ conditions of long
fiber filler reinforced resin pellet) PP/PPE1 % by mass 61 61
PP/PPE2 % by mass 61 61 PP/PPE3 % by mass 61 61 PP/PPE4 % by mass
61 61 PP/PPE5 % by mass 61 61 PP-1 % by mass 61 Content of long %
by mass 39 39 39 39 39 39 39 39 39 39 39 fiber filler Set
temperature of .degree. C. 280 300 280 300 280 300 280 300 280 300
220 dipping bath Drawing speed of m/min 20 20 20 20 20 20 20 20 20
20 20 strand (Properties of long fiber filler reinforced resin
pellet) Spiral lead of long mm 50 70 45 25 60 45 51 60 54 45 45
fiber filler Ratio of average -- 1.03 1.02 1.03 1.11 1.02 1.01 1.03
1.03 1.04 1.04 1.04 fiber length of long fiber filler to length of
pellet Impregnation good, good fair good good fair good fair fair
poor poor poor property of resin fair, into long fiber filler poor
Cross-section ratio % 47 55 44 37 36 45 53 41 79 77 39 of core part
to pellet Appearance of pellet A, B, C B A B A B B B B C C A
surface Longitudinal pellet number none none 2 none none none 3 4
48 37 37 fracture Detachment of long quantity none none a few none
a few a few a few a few many many none fiber filler Fibrillation
property AA-C A A AA AA A A AA A B C C of long fiber filler
(Properties of molded article) Charpy impact KJ/m.sup.2 32 33 34 31
18 17 17 18 12 14 8 strength of molded article Flexural strength of
MPa 173 170 171 173 190 187 186 188 171 170 145 molded article DTUL
of molded .degree. C. 153 152 154 155 154 155 156 157 152 150 113
article under low load
[0518] As obvious from the results in Table 4, all the pellets of
the long fiber filler reinforced resins of Examples had excellent
wettability, could extremely suppress longitudinal pellet fracture
during transportation and detachment of the long fiber filler from
the pellet, were superior in pellet appearance and were superior in
fibrillation property of the long fiber filler during molding,
enabling to mold a molded article with very high heat resistance
and impact resistance.
[0519] On the other hand, in the examples 21 and 22, in which the
cross-section of the core part exceeded 70% of the pellet
cross-section, longitudinal pellet fracture occurred in many
pellets, and many long fiber fillers were detached. Furthermore,
the fibrillation property was not sufficient and the surface
appearance of the pellets was not glossy.
[0520] Further, in the example 23, in which polyphenylene ether was
not contained, longitudinal pellet fracture occurred in many
pellets, the fibrillation property was not sufficient and in
appearance property the pellet surface was not glossy. Furthermore,
the molded article did not have sufficient strength in impact
resistance, etc.
Example 24 to Example 29
Examples and Comparative Examples
[0521] Setting at 280.degree. C. the cylinder temperature in the
same production facility of a long fiber reinforced resin as used
in the example 1, PA/PPE1 was fed through the extruder feeding
port, molten at a screw rotation speed of 300 rpm and filled in the
dipping bath with resin impregnating rolls. Meanwhile, 2 long-fiber
glass fiber rovings of 2,400 tex with fiber diameter of 17 .mu.m
(ER2400T-448N by Nippon Electric Glass Co., Ltd.) were introduced
from a roving supply stand into the dipping bath with resin
impregnating rolls, where the molten resin in the dipping bath was
impregnated into the long-fiber glass fiber rovings, which were
then continuously drawn out through a nozzle part (diameter 2.7 mm)
of the dipping bath at the drawing speed of 15 m/min forming a
single strand, cooled and solidified in a water bath, passed
through twisting rolls for twisting varyingly the resin strand
allowing to form twists of various lead lengths, and then cut by a
pelletizer to 10 mm pellet length. Thereby the set temperature of
the dipping bath was 300.degree. C.
[0522] Thereby, the extrusion rate of the extruder was so regulated
that the glass fiber content became about 50% by mass. The glass
fiber content determined according to the later measurement of ash
was 54% by mass.
[0523] Example 24 to Example 29 were different only in strength of
twisting, and all other conditions were the same. The strength of
twisting was changed by changing the rotation speed of the rolls of
a twister placed between the water bath and the pelletizer.
[0524] Using the obtained resin pellets and strands, evaluations
were conducted. The results are shown in Table 5. Thereby, blend of
a long fiber filler reinforced pellet and a pellet without a long
fiber filler was not conducted as in the example 1, the long fiber
filler reinforced pellet was injection-molded singly and the
properties were evaluated.
Example 30
Example
[0525] Except that the set temperature of the dipping bath was set
at 280.degree. C., all others were conducted identically as in the
example 26. The results are shown in Table 5.
Example 31 to Example 33
Example and Comparative Examples
[0526] Setting at 320.degree. C. the extruder cylinder temperature
in the same production facility of a long fiber reinforced resin as
used in the example 1, PA/PPE2 was fed through the extruder feeding
port, molten at a screw rotation speed of 300 rpm and filled in the
dipping bath with resin impregnating rolls. As in the example 24 to
example 29, long-fiber glass fiber rovings were introduced into the
dipping bath with resin impregnating rolls, where the molten resin
in the dipping bath was impregnated into the long-fiber glass fiber
rovings, which were then continuously drawn out through a nozzle
part (diameter 2.9 mm) of the dipping bath at the drawing speed of
23 m/min forming a single strand, cooled and solidified in a water
bath, passed through twisting rolls for twisting varyingly the
resin strand allowing to form twists of various lead lengths, and
then cut by a pelletizer to 10 mm pellet length. Thereby the set
temperature of the dipping bath was 330.degree. C.
[0527] Thereby, the extrusion rate of the extruder was so regulated
that the glass fiber content became about 50% by mass. The glass
fiber content determined according to the later measurement of ash
was 47% by mass.
[0528] Example 31 to Example 33 were different only in strength of
twisting, and all other conditions were the same. The strength of
twisting was changed by changing the rotation speed of the rolls of
a twister placed between the water bath and the pelletizer.
[0529] Using the obtained resin pellets and strands, evaluations as
in the example 24 to example 29 were conducted. The results are
shown in Table 5.
Example 34 to Example 35
Examples and Comparative Example
[0530] Except that the resin to be fed through the feeding port of
the extruder was changed to those described in Table 5, all others
were performed and evaluated identically with the example 26. The
results are shown in Table 5.
TABLE-US-00005 TABLE 5 Ex. 24 Ex. 28 Ex. 29 Ex. 31 Ex. 33 Ex. 36
Com. Ex. 25 Ex. 26 Ex. 27 Com. Com. Ex. 30 Com. Ex. 32 Com. Ex. 34
Ex. 35 Com. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.
(Composition/ conditions of long fiber filler reinforced resin
pellet) PA/PPE1 % by 46 46 46 46 46 46 46 mass PA/PPE2 % by 53 53
53 mass PA/PPE3 % by 46 mass PA/PPE4 % by 46 mass PA-2 % by 46 mass
Content of long % by 54 54 54 54 54 54 54 47 47 47 54 54 54 fiber
filler mass Set .degree. C. 300 300 300 300 300 300 280 330 330 330
300 300 290 temperature of dipping bath Drawing speed m/min 15 15
15 15 15 15 15 23 23 23 15 15 15 of strand (Properties of long
fiber filler reinforced resin pellet) Spiral lead of mm 14 31 41 71
144 -- 40 15 39 148 38 40 40 long fiber filler Ratio of -- 1.22
1.05 1.03 1.01 1.00 1.00 1.03 1.21 1.04 1.00 1.03 1.03 1.03 average
fiber length of long fiber filler to length of pellet Impregnation
good, good good good good good poor fair good good poor good good
good property of poor resin into long fiber filler Cross-section %
29 40 51 65 72 no 55 69 65 46 48 51 42 ratio of core core part to
pellet Surface gloss A, B, C C B A A B C B B A C A A A of pellet
Longitudinal number none none none 5 10 26 14 6 none 16 none none
none pellet fracture Detachment of quantity none none none a few a
few many a few none none many none none none long fiber filler
Fibrillation AA-C C A A A A AA B C AA AA AA AA C property of long
fiber filler (Properties of molded article) Surface impact J 45 43
47 43 46 46 43 42 40 39 39 50 26 strength of molded article DTUL of
.degree. C. 262 261 262 263 263 259 260 313 315 313 263 260 251
molded article
[0531] As obvious from the results in Table 5, all the pellets of
the long fiber filler reinforced resins of Examples had excellent
wettability, could extremely suppress longitudinal pellet fracture
during transportation and detachment of the long fiber filler from
the pellet, were superior in pellet appearance and were superior in
fibrillation property of the long fiber filler during molding,
enabling to mold a molded article with very high heat resistance
and impact resistance.
[0532] On the other hand, in any of the examples 24, 28, 31 and 33,
in which the spiral leads were outside the range of 20 mm to 80 mm,
and the example 29 without twisting, the pellets were not
well-balanced in all of longitudinal fracture, detachment,
appearance and fibrillation property of the pellet.
[0533] In the example 36, in which polyphenylene ether was not
contained, the fibrillation property was not sufficient and the
molded article did not have sufficient strength in impact
resistance.
Example 37 to Example 53
Examples and Comparative Examples
[0534] Setting at -290.degree. C. to 310.degree. C. the cylinder
temperature in the same production facility of a long fiber
reinforced resin as used in the example 1, PPS/PPE1 to PPS/PPE16 as
described in Table 6 and Table 7 were fed through the extruder
feeding port, molten at a screw rotation speed of 300 rpm and
filled in the dipping bath with resin impregnating rolls.
Meanwhile, 2 long-fiber glass fiber rovings of 2,400 tex with fiber
diameter of 17 .mu.m (ER2400T-448N by Nippon Electric Glass Co.,
Ltd.) were introduced from a roving supply stand into the dipping
bath with resin impregnating rolls, where the molten resin in the
dipping bath was impregnated into the long-fiber glass fiber
rovings, which were then continuously drawn out through a nozzle
part (diameter 3.2 mm) of the dipping bath at the drawing speed of
20 m/min forming a single strand, cooled and solidified in a water
bath, passed through twisting rolls for twisting varyingly the
resin strand allowing to form twists of various lead lengths, and
then cut by a pelletizer to 10 mm pellet length. Thereby the set
temperature of the dipping bath was 310.degree. C.
[0535] Thereby, the extrusion rate of the extruder was so regulated
that the glass fiber content became about 40% by mass. The glass
fiber content determined according to the later measurement of ash
was 39% by mass.
[0536] Using the obtained resin pellets and strands, evaluations
itemized in Table 6 and Table 7 were conducted. The results are
shown in Table 6 and Table 7. Thereby, blend of a long fiber filler
reinforced pellet and a pellet without a long fiber filler was not
conducted as in the example 1, the long fiber filler reinforced
pellet was injection-molded singly and the properties were
evaluated.
TABLE-US-00006 TABLE 6 Ex. 37 Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42
Ex. 43 Ex. 44 Item Unit Ex. Ex. Ex. Ex. Ex. Ex. Com. Ex. Com. Ex.
(Composition/conditions of long fiber filler reinforced resin
pellet) PPS/PPE1 % by mass 61 PPS/PPE2 % by mass 61 PPS/PPE3 % by
mass 61 PPS/PPE4 % by mass 61 PPS/PPE5 % by mass 61 PPS/PPE6 % by
mass 61 PPS/PPE7 % by mass 61 PPS/PPE8 % by mass 61 Content of long
fiber filler weight-% 39 39 39 39 39 39 39 39 Set temperature of
dipping .degree. C. 310 310 310 310 310 310 310 310 bath Drawing
speed of strand m/min 20 20 20 20 20 20 20 20 (Properties of long
fiber filler reinforced resin pellet) Spiral lead of long fiber
filler mm 60 70 45 25 60 45 120 82 Ratio of average fiber -- 1.02
1.01 1.03 1.09 1.02 1.03 1.00 1.01 length of long fiber filler to
length of pellet Impregnation property of good, good fair fair good
good good poor fair resin into long fiber filler fair, poor
Cross-section ratio of core % 42 62 44 37 55 45 87 53 part to
pellet Appearance of pellet A, B, C A B B A A A C C surface
Longitudinal pellet fracture number none 4 6 none none none 24 31
Detachment of long fiber quantity none a few a few none none none
many many filler Fibrillation property of long AA-C AA AA AA A AA
AA AA AA fiber filler (Properties of molded article) Charpy impact
strength of KJ/m.sup.2 24 23 21 28 26 24 14 16 molded article
Flexural strength of molded MPa 216 210 200 224 190 210 170 177
article DTUL of molded article .degree. C. 271 277 274 269 260 276
241 236
TABLE-US-00007 TABLE 7 Ex. 50 Ex. 51 Ex. 52 Ex. 53 Ex. 45 Ex. 46
Ex. 47 Ex. 48 Ex. 49 Com. Com. Com. Com. Item Unit Ex. Ex. Ex. Ex.
Ex. Ex. Ex. Ex. Ex. (Composition/conditions of long fiber filler
reinforced resin pellet) PPS/PPE9 % by mass 61 PPS/PPE10 % by mass
61 PPS/PPE11 % by mass 61 PPS/PPE12 % by mass 61 PPS/PPE13 % by
mass 61 PPS/PPE14 % by mass 61 PPS/PPE15 % by mass 61 PPS/PPE16 %
by mass 61 PPS-1 % by mass 61 Content of long fiber filler weight-%
39 39 39 39 39 39 39 39 39 Set temperature of dipping .degree. C.
310 310 310 310 310 310 310 310 310 bath Drawing speed of strand
m/min 20 20 20 20 20 20 20 20 20 (Properties of long fiber filler
reinforced resin pellet) Spiral lead of long fiber filler mm 45 30
40 45 60 70 70 45 45 Ratio of average fiber length -- 1.03 1.07
1.04 1.03 1.02 1.01 1.01 1.03 1.03 of long fiber filler to length
of pellet Impregnation property of good, good good good good good
poor poor poor good resin into long fiber filler fair, poor
Cross-section ratio of core % 45 39 41 43 52 72 76 80 45 part to
pellet Appearance of pellet A, B, C A A A A A C C C A surface
Longitudinal pellet fracture number none none none none none 13 17
14 none Detachment of long fiber quantity none none none none none
a few many many none filler Fibrillation property of long AA-C AA A
A AA AA B A A C fiber filler (Properties of molded article) Charpy
impact strength of KJ/m.sup.2 22 31 23 22 14 19 18 14 8 molded
article Flexural strength of molded MPa 195 210 190 190 167 172 180
175 180 article DTUL of molded article .degree. C. 272 265 270 268
248 253 246 251 259
[0537] As obvious from the results in Table 6 and Table 7, all the
pellets of the long fiber filler reinforced resins of Examples had
excellent wettability, could extremely suppress longitudinal pellet
fracture during transportation and detachment of the long fiber
filler from the pellet, were superior in pellet appearance and were
superior in fibrillation property of the long fiber filler during
molding, enabling to mold a molded article with very high heat
resistance and impact resistance.
[0538] On the other hand, in any of the examples 43 and 44, in
which the spiral leads were outside the range of 20 mm to 80 mm,
and the examples 50 to 52, in which the cross-section of the core
part exceeded 70% of the pellet cross-section, detachment from
pellets occurred in a large amount, longitudinal pellet fracture
occurred in many pellets, and surface appearances of the pellets
were not glossy.
[0539] In the example 53, in which polyphenylene ether was not
contained, the fibrillation property was not sufficient and the
molded article did not have sufficient strength in impact
resistance, etc.
Example 54 to Example 58
Examples and Comparative Examples
[0540] Setting at 330.degree. C. the cylinder temperature in the
same production facility of a long fiber reinforced resin as used
in the example 1, LCP/PPE1 was fed through the extruder feeding
port, molten at a screw rotation speed of 300 rpm and filled in the
dipping bath with resin impregnating rolls. Meanwhile, 2 long-fiber
glass fiber rovings of 2,400 tex with fiber diameter of 17 .mu.m
(ER2400T-448N by Nippon Electric Glass Co., Ltd.) were introduced
from a roving supply stand into the dipping bath with resin
impregnating rolls, where the molten resin in the dipping bath was
impregnated into the long-fiber glass fiber rovings, which were
then continuously drawn out through a nozzle part (diameter 2.7 mm)
of the dipping bath at the drawing speed of 22 m/min forming a
single strand, cooled and solidified in a water bath, passed
through twisting rolls for twisting varyingly the resin strand
allowing to form twists of various lead lengths, and then cut by a
pelletizer to 10 mm pellet length. Thereby the set temperature of
the dipping bath was 330.degree. C. The strength of twisting was
changed by changing the rotation speed of the rolls of a twister
placed between the water bath and the pelletizer.
[0541] Thereby, the extrusion rate of the extruder was so regulated
that the glass fiber content became about 50% by mass.
[0542] Using the obtained resin pellets and strands, various
evaluations were conducted. The results are shown in Table 8.
Thereby, measurements of Charpy impact strength, flexural strength
and high load DTUL were conducted by dry-blending 60 parts by mass
of the obtained long fiber reinforced pellet and 40 parts by mass
of LCP/PPE1 pellet, then molding them under the conditions of
cylinder temperature at 330.degree. C. and a mold temperature at
110.degree. C., and conducting evaluations thereof. The results are
shown in Table 8.
Example 59
Example
[0543] Using LCP/PPE2 instead of LCP/PPE1, procedures identical
with the example 55 were performed to obtain a long fiber filler
reinforced resin pellet. Then, 60 parts by mass of the obtained
long fiber reinforced pellet and 40 parts by mass of the pellet of
LCP/PPE1 were dry-blended and molded under the conditions of the
cylinder temperature at 330.degree. C. and the mold temperature at
110.degree. C. The properties of the molded specimen were
evaluated. The results are shown in Table 8.
Example 60
Comparative Example
[0544] Using chopped strand glass fiber (the surface being treated
by a similar compound as for the long-fiber glass fiber) with
filament diameter of 17 .mu.m and fiber length of 3 mm, a composite
pellet composed of the same resin composition as LCP/PPE1 and 30%
by mass of chopped strand glass fiber was prepared. Thereby using
the extruder used for preparing LCP/PPE1 and setting the maximum
set temperature of the cylinder at 330.degree. C., the resin
components were fed through the upstream feeding port, and the
chopped strand glass fiber was fed through the downstream feeding
port, and melt-extruded. The stand was cut to obtain a composite
pellet with length of about 3 mm and diameter of about 3 mm. By
preparing a composite pellet having the same composition with the
test specimen used for measuring the properties of a molded article
of the example 54 to example 58, Charpy impact strength, flexural
strength and high load DTUL were measured. The results are shown in
Table 8.
Example 61
Example
[0545] Setting at 330.degree. C. the extruder cylinder temperature
in the same production facility of a long fiber reinforced resin as
used in the example 54 to example 58, LCP/PPE3 was fed through the
extruder feeding port, molten at a screw rotation speed of 300 rpm
and filled in the dipping bath with resin impregnating rolls. As in
the example 54 to example 58, long-fiber glass fiber rovings were
introduced into the dipping bath with resin impregnating rolls,
where the molten resin in the dipping bath was impregnated into the
long-fiber glass fiber rovings, which were then continuously drawn
out through a nozzle part (diameter 2.7 mm) of the dipping bath at
the drawing speed of 15 m/min forming a single strand, cooled and
solidified in a water bath, passed through twisting rolls for
twisting the resin strand to form a twist with a lead length of 30
mm, and then cut by a pelletizer to 10 mm pellet length. Thereby
the set temperature of the dipping bath was 320.degree. C.
[0546] Thereby, the extrusion rate of the extruder was so regulated
that the glass fiber content became about 50% by mass. The glass
fiber content determined according to the later measurement of ash
was 52.5% by mass.
[0547] Using the obtained resin pellets and strands, the
evaluations as in the example 54 to example 58 were conducted.
Thereby, the evaluations of impact strength and DTUL of a molded
specimen were conducted by: pellet-blending 57 parts by mass of the
long fiber filler reinforced resin pellet obtained in the present
example and 43 parts by mass of LCP/PPE3 pellet to make the glass
fiber content at 30% by mass; then molding the blend; and
conducting similarly measurements thereof. The results are shown in
Table 8.
Example 62
Example
[0548] Except setting the cylinder temperature of the extruder at
300.degree. C., the screw rotation speed at 150 rpm and the
temperature of the dipping bath at 290.degree. C., all others were
performed identically with the example 61 to obtain a long fiber
filler reinforced resin pellet. The results are shown in Table
8.
Example 63
Example
[0549] Except that LCP/PPE4 was used instead of LCP/PPE1 in the
example 56, all others were performed identically with the example
56. Using the obtained resin pellet and strand evaluations were
conducted. The results are shown in Table 8.
Example 64
Example
[0550] Except that PEEK/PPE was used instead of LCP/PPE1 in the
example 56, and that the set temperature of the dipping bath was
set at 380.degree. C., all others were performed identically with
the example 56. Using the obtained resin pellet and strand
evaluations were conducted. The results are shown in Table 8.
TABLE-US-00008 TABLE 8 Ex. 54 Com. Ex. 55 Ex. 56 Ex. 57 Ex. 58 Com.
Ex. 59 Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64 Item Unit Ex. Ex. Ex. Ex.
Ex. Ex. Com. Ex. Ex. Ex. Ex. Ex. (Composition/conditions of long
fiber filler reinforced resin pellet) LCP/PPE1 % by mass 48.5 48.5
48.5 48.5 48.5 LCP/PPE2 % by mass 49 LCP/PPE3 % by mass 47.5 47.5
LCP/PPE4 % by mass 48.5 PEEK/PPE % by mass 48.5 Content of long
fiber % by mass 51.5 51.5 51.5 51.5 51.5 51 30*2) 52.5 52.5 51.5
51.5 filler Set temperature of .degree. C. 330 330 330 330 330 330
330 320 290 330 380 dipping bath Drawing speed of m/min 22 22 22 22
22 22 -- 15 15 22 22 strand (Properties of long fiber filler
reinforced resin pellet) Spiral lead of long mm 10 25 40 60 100 40
-- 30 30 40 40 fiber filler Ratio of average fiber -- 1.38 1.07
1.03 1.01 1.00 1.03 -- 1.05 1.05 1.03 1.03 length of long fiber
filler to length of pellet Impregnation property good, good good
good good fair poor -- good fair good good of resin into long fiber
fair, filler poor Cross-section ratio of % 52 55 65 70 85 45 -- 54
67 63 61 core part to pellet Appearance of pellet A, B, C C B A B C
C -- A C A A surface Longitudinal pellet number none none none 5 16
22 -- none 13 none none fracture Detachment of long quantity none
none none a few a few many -- none a few none none fiber filler
(Properties of molded article of pellet blend*.sup.1)) Charpy
impact J 11 13 15 14 8 5 5 16 13 18 17 strength of molded article
Flexural strength of MPa 225 230 234 231 151 86 144 192 175 238 241
molded article DTUL of molded .degree. C. 269 270 271 270 267 202
205 178 168 271 318 article *.sup.1)pellet blend: adjusted to the
composition containing 30% by mass of glass fiber *2)adjusted to
the composition containing 30% by mass of chopped strand glass
fiber
[0551] As obvious from the results in Table 8, all the pellets of
the long fiber filler reinforced resins of Examples had excellent
wettability, could extremely suppress longitudinal pellet fracture
during transportation and detachment of the long fiber filler from
the pellet, were superior in pellet appearance and were superior in
fibrillation property of the long fiber filler during molding,
enabling to mold a molded article with very high heat resistance
and impact resistance.
[0552] On the other hand, in the examples 54 and 58, in which the
spiral leads were outside the range of 20 mm to 80 mm, the surface
appearance of the pellet was not glossy.
[0553] In the example 60, in which chopped strand glass fiber was
used instead of the long fiber filler, such properties of a molded
article as impact strength, flexural strength and heat resistance
were found to be extremely inferior and insufficient.
Example 65
Comparative Example
[0554] Except that only LCP-1 was used instead of LCP/PPE1 in the
example 56, all others were performed identically with the example
56. Using the obtained resin pellet, Charpy impact value was
measured to obtain a mean value of 16 J (N=10). The dispersion of
the values was about .+-.4 J with respect to the mean value (12 J
to 20 J). On the other hand the dispersion in the example 56 was
.+-.2 J with respect to the mean value.
[0555] Further, by observing the molded specimen after burning,
almost all the glass fibers were found existing in an unfibrillated
bundle form and no form retainability was recognized.
[0556] Comparison between the respective Examples and Comparative
Examples described in Table 3 to Table 8 above reveals that in the
Embodiment addition of polyphenylene ether to a thermoplastic resin
other than polyphenylene ether increases extremely the fibrillation
property of a long fiber filler and further improves substantially
the quality stability of physical properties.
[0557] The above can be attributable to alloying of polyphenylene
ether, which improves the fibrillation property of the long fiber
filler, resulting in the quality stability of the thermoplastic
resin blend.
Example 66
Example
[0558] The cylinder temperature of an extruder in a production
facility of a long fiber reinforced resin, which was a co-rotating
twin screw extruder (ZSK25: Coperion) provided with an upstream
feeding port, a downstream feeding port and a dipping bath with
resin impregnating rolls (Kobe Steel, Ltd.) at the front end of the
co-rotating twin screw extruder, was set at 320.degree. C., and
according to the composition described in Table 8 a mixture of 100
parts by mass of PS/PPE4, 1.0 part by mass of Irg1098 and 1 part by
mass of Zinc sulfide as a white colorant was fed through the
upstream extruder feeding port, and 13 parts by mass of FR-2 based
on 100 parts by mass of PS/PPE4 were fed through the downstream
feeding port, and molten and blended at a screw rotation speed of
300 rpm to fill the dipping bath with resin impregnating rolls with
the molten resin. Meanwhile, 2 long-fiber glass fiber rovings of
2,400 tex with filament diameter of 17 .mu.m (using a polyurethane
resin as a binder) were introduced from a roving supply stand to
the dipping bath with resin impregnating rolls, where the molten
resin in the dipping bath was impregnated into the long-fiber glass
fiber rovings, which were then continuously drawn out through a
nozzle (diameter 3.2 mm) part of the dipping bath at the drawing
speed of 40 m/min forming a single strand, cooled and solidified in
a water bath, passed through twisting rolls for twisting the resin
strand to form a twist with a lead length of 30 mm to obtain a
resin strand. Thereby, the extrusion rate of the extruder was so
regulated that the glass fiber content became about 40% by
mass.
[0559] The flame retardancy and the color tone of the obtained
strand of the long fiber filler reinforced resin were observed. For
a comparison, the flame retardancy and the color tone without use
of Irg1098 and FR-2 are also shown in Table 9. Thereby the flame
retardancy of a strand of a long fiber filler reinforced resin was
judged by: whether a resin strand cut to 10 cm length contacted for
5 sec with the flame defined for the vertical burn test of UL94
should self-extinguish after removing the flame. If
self-extinguished, the time required until the extinguishment was
recorded. The color tone was judged visually. The results are shown
in Table 9.
Example 67 to Example 70
Examples
[0560] Replacing all of PS/PPE4 in the example 66 with PP/PPE2,
PA/PPE3, PPS/PPE6 and LCP/PPE4 respectively, the example 67 to
example 70 were carried out. The then temperatures of the extruder
cylinder and the dipping bath are shown in Table 9 respectively.
The flame retardancy and the color tone of the obtained strand were
evaluated as in the example 66. The results are shown in Table
9.
TABLE-US-00009 TABLE 9 Ex. 66 Ex. 67 Ex. 68 Ex. 69 Ex. 70 Item Unit
Ex. Ex. Ex. Ex. Ex. (Composition/conditions of long fiber filler
reinforced resin pellet) PS/PPE4 part by mass 100 PP/PPE2 part by
mass 100 PA/PPE3 part by mass 100 PPS/PPE6 part by mass 100
LCP/PPE4 part by mass 100 Zinc sulfide part by mass 1 1 1 1 1
Irg1098 part by mass 1 1 1 1 1 FR-2 part by mass 13 13 13 13 13
Content of long fiber filler % by mass 40 40 40 40 51.5 Temperature
of extruder .degree. C. 320 310 320 310 330 cylinder Set
temperature of .degree. C. 330 330 340 330 340 dipping bath Drawing
speed of strand m/min 40 40 40 40 40 (Properties of long fiber
filler reinforced resin pellet) Spiral lead of long fiber mm 30 30
30 30 30 filler Cross-section ratio of % 51 48 52 46 42 core part
of pellet (Properties of strand) Flame retardancy (time sec 7 16 9
3 1 until extinguishment) Color tone white white white yellow to
white brown (Properties of strand without Irg1098 and FR-2) Flame
retardancy (time sec burning burning burning 18 8 until
extinguishment) Color tone brown to yellow brown to brown to yellow
black black black
[0561] In Table 9 are shown the properties of the pellet and the
strand of the long fiber filler reinforced resin obtained in the
example 66 to the example 70. To make clearer the effect by
comparing the properties of the strands, the properties of the
composition without an stabilizer and a flame retardant are shown
in the lower rows. They demonstrate that the inclusion of a flame
retardant and a stabilizer, although they are otherwise conducted
under identical conditions, improves the flame retardancy and
further the color tone.
[0562] This application is base on Japanese Patent Application No.
2007-87117 applied on 2007 Mar. 29, Japanese Patent Application No.
2007-218349 applied on 2007 Aug. 24, and Japanese Patent
Application No. 2007-223267 as well as Japanese Patent Application
No. 2007-223272 applied on 2007 Aug. 29, and the content thereof
are herein incorporated by reference.
INDUSTRIAL APPLICABILITY
[0563] The present invention can provide a long fiber filler
reinforced resin pellet, having good wettability between a long
fiber filler and a thermoplastic resin, extremely suppressing
longitudinal fracture of a pellet during transportation and
detachment of a long fiber filler from a pellet, showing good
appearance, and having superior fibrillation property of a long
fiber filler during molding, enabling to mold a molded article with
extremely high heat resistance and impact resistance.
[0564] The present invention can be favorably applicable to, for
example, electrical/electronic parts, OA parts, machine parts, and
automobile exterior/interior parts.
* * * * *