U.S. patent application number 12/461446 was filed with the patent office on 2009-12-10 for polyamide resin and hinged molded product.
This patent application is currently assigned to Mitsubishi Chemical Corporation. Invention is credited to Tatsuya Hitomi, Masaaki Miyamoto, Yuuichi Nishida.
Application Number | 20090306330 12/461446 |
Document ID | / |
Family ID | 35428385 |
Filed Date | 2009-12-10 |
United States Patent
Application |
20090306330 |
Kind Code |
A1 |
Miyamoto; Masaaki ; et
al. |
December 10, 2009 |
Polyamide resin and hinged molded product
Abstract
A polyamide resin comprising a dicarboxylic acid constitutional
unit comprising an adipic acid unit and a diamine constitutional
unit comprising a pentamethylenediamine unit and a
hexamethylenediamine unit wherein a weight ratio of the
pentamethylenediamine unit to the hexamethylenediamine unit being
in the range of 95:5 to 60:40; a vibration-welded molded product
having an excellent vibration welding strength, a hinged molded
product and a binding band having an excellent low-temperature
toughness, and a filament having an excellent transparency which
are obtained from the polyamide resin; and a hinged molded product
comprising a polyamide resin constituted of an adipic acid unit and
a pentamethylenediamine unit.
Inventors: |
Miyamoto; Masaaki;
(Kitakyushu-shi, JP) ; Hitomi; Tatsuya;
(Kitakyushu-shi, JP) ; Nishida; Yuuichi;
(Kitakyushu-shi, JP) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Assignee: |
Mitsubishi Chemical
Corporation
Tokyo
JP
|
Family ID: |
35428385 |
Appl. No.: |
12/461446 |
Filed: |
August 12, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11596619 |
Mar 9, 2007 |
|
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PCT/JP2005/009144 |
May 19, 2005 |
|
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12461446 |
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Current U.S.
Class: |
528/310 |
Current CPC
Class: |
C12P 13/02 20130101;
D01F 6/80 20130101; C08L 77/06 20130101; C08K 7/04 20130101; C08G
69/265 20130101; C12P 13/001 20130101; C08K 7/04 20130101 |
Class at
Publication: |
528/310 |
International
Class: |
C08G 69/08 20060101
C08G069/08 |
Foreign Application Data
Date |
Code |
Application Number |
May 21, 2004 |
JP |
2004-152059 |
Claims
1. A polyamide resin comprising a dicarboxylic acid constitutional
unit comprising an adipic acid unit and a diamine constitutional
unit comprising a pentamethylenediamine unit and a
hexamethylenediamine unit, a weight ratio of the
pentamethylenediamine unit to the hexamethylenediamine unit being
in the range of 95:5 to 60:40.
2. A polyamide resin according to claim 1, wherein the
pentamethylenediamine unit is formed from pentamethylenediamine
which is produced from lysine using a lysine decarboxylase, cells
capable of producing the lysine decarboxylase or a treated product
of the cells.
3. A polyamide resin according to claim 1, wherein the content of
the adipic acid unit in the dicarboxylic acid constitutional unit
is not less than 90% by weight, and a total content of the
pentamethylenediamine unit and the hexamethylenediamine unit in the
diamine constitutional unit is not less than 90% by weight.
4. A polyamide resin according to claim 1, wherein when the
polyamide resin is subjected to DSC measurement, a ratio of an
endothermic peak area of the polyamide resin as measured at a
temperature of not lower than 240.degree. C. to a whole endothermic
peak area thereof is not more than 60%.
5. A polyamide resin according to claim 1, wherein the polyamide
resin is a copolymer obtained by polycondensing an aliphatic
diamine component comprising pentamethylenediamine and
hexamethylenediamine with a dicarboxylic acid component comprising
adipic acid.
6. A polyamide resin according to claim 5, wherein the
polycondensation is a heat-polycondensation.
7. A polyamide resin according to claim 5, wherein the copolymer is
obtained by polycondensing a salt of the aliphatic diamine and the
dicarboxylic acid.
8. (canceled)
9. A polyamide resin composition comprising the polyamide resin as
defined in claim 1, and an inorganic filler, a content of the
inorganic filler being 0.01 to 150 parts by weight on the basis of
100 parts by weight of the polyamide resin.
10. A polyamide resin composition according to claim 9, wherein the
inorganic filler is a glass fiber.
11. A vibration-welded molded product comprising the polyamide
resin as defined in claim 1.
12. A hinged molded product comprising the polyamide resin as
defined in claim 1.
13. A binding band comprising the polyamide resin as defined in
claim 1.
14. A filament comprising the polyamide resin as defined claim
1.
15. A hinged molded product comprising a polyamide resin
constituted of an adipic acid unit and a pentamethylenediamine
unit.
16. A hinged molded product according to claim 15, wherein a
content of the adipic acid unit in a dicarboxylic acid
constitutional unit of the polyamide is not less than 90% by
weight, and a content of the pentamethylenediamine unit in a
diamine constitutional unit of the polyamide resin is not less than
90% by weight.
17. A hinged molded product according to claim 15, wherein the
polyamide resin is obtained by heat-polycondensing an aliphatic
diamine component comprising pentamethylenediamine with a
dicarboxylic acid component comprising adipic acid.
18. A hinged molded product according to claim 15, wherein the
polyamide resin is obtained by subjecting a salt of
pentamethylenediamine and adipic acid to heat polycondensation.
19. A hinged molded product according to claim 17, wherein the
pentamethylenediamine is produced from lysine using a lysine
decarboxylase, cells capable of producing the lysine decarboxylase
or a treated product of the cells.
20. A vibration-welded molded product comprising the polyamide
resin composition as defined in claim 9.
21. A hinged molded product comprising the polyamide resin
composition as defined in claim 9.
22. A binding band comprising the polyamide resin composition as
defined in claim 9.
23. A filament comprising the polyamide resin composition as
defined in claim 9.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polyamide resin, and more
particularly to a polyamide resin comprising an adipic acid unit, a
pentamethylenediamine unit and a hexamethylenediamine unit as
constitutional components thereof which can be produced by using
raw materials that are free from generation of carbon dioxide
(CO.sub.2) causing global warming problems; and a vibration-welded
molded product having an excellent vibration welding strength, a
hinged molded product and a binding band having an excellent
low-temperature toughness, and a filament having an excellent
transparency which are produced from the polyamide resin. Further,
the present invention relates to a hinged molded product, and more
particularly to a hinged molded product obtained from a polyamide
resin that is more excellent in hinge property and heat resistance
(melting point) than those of 6-nylon, and simultaneously has a
good rigidity (bending modulus) equal to or higher than that of
6-nylon.
BACKGROUND ARTS
[0002] 6-nylon and 66-nylon are resins having excellent
moldability, heat resistance, chemical resistance and mechanical
properties and, therefore, have been extensively used in various
applications such as automobile and vehicle-related parts, electric
and electronic parts, household or business electric
equipment-related parts, computer-related parts, facsimile or
copier-related parts, mechanical parts, packaging materials and
fishing materials. In particular, in the application field of
automobile and vehicle-related parts, intensive studies have been
made to apply these nylons to under-hood parts for automobiles such
as intake manifold, hinged clip (hinged molded product), binding
band, resonator, air cleaner, engine cover, rocker cover, cylinder
head cover, timing belt cover, gasoline tank, gasoline sub-tank,
radiator tank, inter-cooler tank, oil reservoir tank, oil pan,
electric power steering gear, oil strainer, canister, engine mount,
junction block, relay block, connector, corrugated tube and
protector.
[0003] These under-hood parts for automobiles have been required to
have a higher strength in order to meet various requirements owing
to a complicated-structure of the parts and a reduced thickness
thereof for the purpose of weight reduction. Among these under-hood
parts for automobiles, the intake manifold having a larger size is
more susceptible to a weight-reduction effect than the other
automobile parts by decreasing a thickness thereof. However, the
intake manifold must be kept safe without damage thereto even when
an internal pressure thereof is increased owing to backfire of an
engine, etc. Therefore, at the present time, reduction in thickness
of these parts such as the intake manifold is possible only to a
limited extent.
[0004] In recent years, as the material for resin intake manifolds,
there has been mainly used glass fiber-reinforced 6-nylon, and the
intake manifolds have been mainly produced therefrom by a
vibration-welding method. Also, there has been proposed the resin
intake manifold produced by using 56-nylon instead of the 6-nylon
(for example, refer to Patent document 1). However, the 56-nylon
tends to be insufficient in vibration-welding strength, and further
deteriorated in retention heat stability, and, therefore, is
unsuitable for large-size molded products requiring a long molding
cycle time such as intake manifolds. For this reason, it has been
demanded to provide polyamide resins having more excellent
vibration-welding strength and retention heat stability than those
of 56-nylon.
[0005] There is also known a 56/66 nylon containing a smaller
amount of 56-nylon and a larger amount of 66-nylon (ratio
56/66=0.5/99.5 to 40/60 mol % and preferably 0.5/99.5 to 10/90 mol
%) (for example, refer to Patent document 2). Since the polyamide
resin of this type aims at suppressing gelation of 66-nylon while
maintaining functions of 66-nylon, the amount of 56-nylon added
thereto is small. Therefore, it is considered that the polyamide
resin exhibits only a vibration-welding strength substantially
identical to that of 66-nylon, though it is not clearly known.
Thus, in order to apply the polyamide resin to production of
large-size thin-walled molded products, further improvement in
properties thereof are required.
[0006] Hinged molded products have been frequently used for
under-hood parts for automobiles. At the present time, the hinged
molded products requiring a high heat resistance have been produced
from 66-nylon, whereas the hinged molded products requiring a high
toughness have been produced from 6-nylon. The 66-nylon has a
melting point as high as 264.degree. C. and a high crystallinity
and, therefore, is slightly low in toughness. Therefore, the hinged
molded products produced from the 66-nylon tend to suffer from
breakage upon bending. On the other hand, the 6-nylon has a lower
crystallinity than that of the 66-nylon and, therefore, exhibits a
good toughness. However, the melting point of the 6-nylon is
224.degree. C., i.e., much lower by 40.degree. than that of the
66-nylon.
[0007] With the recent increasing tendency that hinged parts have a
complicated shape, it has been demanded to provide polyamide resins
having a more excellent hinge property than that of 6-nylon.
Further, with the reduction or compactness in size of an engine
room of automobiles, it has been demanded to provide polyamide
resins having a higher heat resistance (melting point). In
addition, these polyamide resins are required to have a rigidity
(bending modulus) identical to or higher than that of 6-nylon.
[0008] As the method of improving a hinge property of hinged molded
products, there is known the method of blending the polyamide resin
with a boron nitride powder and an aliphatic carboxylic acid
derivative (for example, refer to Patent document 3). However, it
is considered that the resin composition of this type fails to
exhibit an improved heat resistance (melting point).
[0009] Also, there is known the method of blending the polyamide
resin with a polyolefin such as polypropylene and polyethylene (for
example, refer to Patent document 4 However, the polyamide resin
composition of this type tends to be deteriorated in heat
resistance (melting point) or mechanical properties such as bending
modulus as compared to those of the polyamide resin.
[0010] As the polyamide resin satisfying both the above hinge
property and the heat resistance (heat-deforming temperature),
there is known the polyamide resin composition composing an
aromatic polyamide resin, a modified polyolefin, and an
epoxy-containing polymer or an epoxidated diene-based block
copolymer (for example, refer to Patent documents 5 and 6).
However, the bending modulus of the polyamide resin composition of
this type is as low as about 1500 to 1900 MPa which is considerably
deteriorated as compared to a bending modulus of ordinary 6-nylon
(about 2550 MPa) and that of ordinary 66-nylon (about 2940 MPa).
Therefore, the polyamide resin composition tends to be deficient in
rigidity as an important mechanical property. For this reason, it
has been demanded to provide polyamide resins capable of exhibiting
more excellent hinge property and heat resistance (melting point)
than those of 6-nylon and simultaneously having a rigidity (bending
modulus) identical to or higher than that of 6-nylon.
[0011] Also, as the raw material of the polyamide resin, there are
used so-called fossil materials such as naphtha. However, with the
recent requirements for prevention of global warming by suppressing
discharge of carbon dioxide as well as establishment of recycling
type society, it has been demanded to replace the material for
production of the polyamide resins with a biomass-derived raw
material. More specifically, it has been required that the
polyamide is produced from such a raw material having a high
biomass ratio (ratio of the biomass-derived material to the whole
raw materials used for production of the polyamide resin).
[0012] The use of the biomass-derived material has been extensively
demanded in various application fields including not only
automobiles, but also electric and electronic parts, films and
filaments. Specific examples of these parts include
vibration-welded molded products such as the above intake manifold
having an excellent vibration welding strength, hinged molded
products and binding bands having an excellent low-temperature
toughness, and filaments having an excellent transparency.
[0013] Known polyamide resins produced by polymerizing the
biomass-derived material include, for example, 56 nylon. The 56
nylon has substantially the same heat resistance and mechanical
properties as those of 6 nylon or 66 nylon. As the method for
production of the 56 nylon, there are known the method of
heat-polycondensing diaminopentane with adipic acid (for example,
refer to Patent document 7), and the method of preparing a salt of
diaminopentane and adipic acid and then heat-polycondensing the
salt (for example, refer to Patent document 8). However, as
described above, the 56 nylon tends to be deteriorated in
vibration-welding strength and retention heat stability. For this
reason, it has been demanded to develop polyamide resins which can
be produced by polymerizing a biomass-derived raw material, and are
capable of providing binding bands having an excellent
low-temperature toughness and filaments having an excellent
transparency. However, there are conventionally unknown hinged
molded products produced from the 56 nylon.
Patent Document 1: Japanese Patent Application Laid-open (KOKAI)
No. 2004-269634
Patent Document 2: PCT Pamphlet No. 93/00385
Patent Document 3: Japanese Patent Application Laid-open (KOKAI)
No. 7-82474.
Patent Document 4: Japanese Patent Application Laid-open (KOKAI)
No. 9-249808.
Patent Document 5: Japanese Patent Application Laid-open (KOKAI)
No. 9-124934
Patent Document 6: Japanese Patent Application Laid-open (KOKAI)
No. 2000-204243.
Patent Document 7: Japanese Patent Application Laid-open (KOKAI)
No. 2003-292612
[0014] Patent Document 8: U.S. Pat. No. 2,130,948
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
[0015] Thus, the present invention has been made in view of the
above conventional problems, and an object of the present invention
is to provide a polyamide resin which is excellent in
vibration-welding strength, retention heat stability,
low-temperature toughness and transparency, and can be produced
from a biomass-derived material.
[0016] Another object of the present invention is to provide a
polyamide resin composition containing the above polyamide
resin.
[0017] A further object of the present invention is to provide a
vibration-welded molded product, a hinged molded product, a binding
band and a filament which comprise the above polyamide resin or
polyamide resin composition.
[0018] The other object of the present invention is to provide a
hinged molded product produced from a polyamide resin which is more
excellent in hinge property and heat resistance (melting point)
than those of 6-nylon and simultaneously exhibit a good rigidity
(bending modulus) identical to or higher than that of 6-nylon.
Means for Solving the Problem
[0019] As a result of the present inventors' earnest study for
solving the above problems, it has been found that the above
objects can be attained by such a polyamide resin constituted of an
adipic acid unit, a pentamethylenediamine unit and a
hexamethylenediamine unit in which a ratio between contents of the
pentamethylenediamine unit and the hexamethylenediamine unit lies
within a specific range, and that a hinged molded product
containing a polyamide resin constituted of an adipic acid unit and
a pentamethylenediamine unit can simultaneously satisfy a good
hinge property, a high heat resistance (melting point) and a good
rigidity (bending modulus). The present invention has been attained
on the basis of the above findings.
[0020] That is, in a first aspect of the present invention, there
is provided a polyamide resin comprising a dicarboxylic acid
constitutional unit comprising an adipic acid unit and a diamine
constitutional unit comprising a pentamethylenediamine unit and a
hexamethylenediamine unit, a weight ratio of the
pentamethylenediamine unit to the hexamethylenediamine unit being
in the range of 95:5 to 5:95, and the pentamethylenediamine unit
being formed from pentamethylenediamine which is produced from
lysine using a lysine decarboxylase, cells capable of producing the
lysine decarboxylase or a treated product of the cells.
[0021] In a second aspect of the present invention, there is
provided a polyamide resin comprising a dicarboxylic acid
constitutional unit comprising an adipic acid unit and a diamine
constitutional unit comprising a pentamethylenediamine unit and a
hexamethylenediamine unit, a weight ratio of the
pentamethylenediamine unit to the hexamethylenediamine unit being
in the range of 95:5 to 60:40.
[0022] In a third aspect of the present invention, there is
provided a polyamide resin composition comprising the above
polyamide resin and an inorganic filler, a content of the inorganic
filler being 0.01 to 150 parts by weight on the basis of 100 parts
by weight of the polyamide resin.
[0023] In a fourth aspect of the present invention, there is
provided a vibration-welded molded product comprising the above
polyamide resin or the above polyamide resin composition.
[0024] In a fifth aspect of the present invention, there is
provided a hinged molded product comprising the above polyamide
resin or the above polyamide resin composition.
[0025] In a sixth aspect of the present invention, there is
provided a binding band comprising the above polyamide resin or the
above polyamide resin composition.
[0026] In a seventh aspect of the present invention, there is
provided a filament comprising the above polyamide resin or the
above polyamide resin composition.
[0027] In a eighth aspect of the present invention, there is
provided a hinged molded product comprising a polyamide resin
constituted of an adipic acid unit and a pentamethylenediamine
unit.
EFFECT OF THE INVENTION
[0028] The polyamide resin or polyamide resin composition of the
present invention is excellent in vibration-welding strength,
retention heat stability, low-temperature toughness and
transparency. Also, the polyamide resin or polyamide resin
composition of the present invention can provide a vibration welded
molded product, a hinged molded product, a binding band and a
filament. In particular, the hinged molded product produced from
the polyamide resin of the present invention can exhibit an
extremely high hinge property. Further, the polyamide resin of the
present invention can be produced from a biomass-derived material,
and is thus expected to exhibit a remarkably high effect of
reducing a burden to environments in various industrial fields.
Therefore, the present invention has a high industrial value in
this regard. In addition, the hinged molded product of the present
invention can exhibit an extremely high hinge property, and have a
higher heat resistance (melting point) than that of a hinged molded
product produced from 6 nylon as well as mechanical properties
identical to or higher than those of the hinged molded product
produced from 6 nylon. For this reason, the hinged molded product
is suitable, in particular, as, hinged parts used in an engine room
of automobiles, and may also be useful as various hinged parts.
Further, the polyamide resin and the hinged molded product of the
present invention can be produced from a biomass-derived material,
and is thus expected to exhibit a remarkably high effect of
reducing a burden to environments in various industrial fields.
Therefore, the present invention also has a high industrial value
in this regard.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 is an explanatory view for determining an endothermic
peak area.
[0030] FIG. 2 is an explanatory view for determining an endothermic
peak area.
[0031] FIG. 3 is a side view showing a welded side of respective
hollow parts as primary molded products used in a vibration welding
test in Examples according to the present invention in which FIG.
3(a) is a view showing the hollow part having a convex portion as a
welding margin in its portion to be welded; and FIG. 3(b) is a view
showing the hollow part having a flat portion to be welded.
[0032] FIG. 4 is a perspective view showing the hollow part used in
a vibration welding test in Examples according to the present
invention.
[0033] FIGS. 5(a) and 5(b) are a side view and a top view,
respectively, showing a hinged molded product used in a
low-temperature hinge property test in Examples according to the
present invention.
[0034] FIGS. 6(a) and 6(b) are a side view and a top view,
respectively, showing a binding band used in a low-temperature band
breaking test in Examples according to the present invention.
[0035] FIG. 7 is an explanatory view for a low-temperature hinge
property test conducted in Examples according to the present
invention.
[0036] FIG. 8 is an explanatory view for a low-temperature band
breaking test conducted in Examples according to the present
invention.
EXPLANATION OF REFERENCE NUMERALS
[0037] 1: Upper opening portion [0038] 1': Upper opening portion
[0039] 2: Lower opening portion
Preferred Embodiments of the Invention
[0040] The present invention is described in detail below. Although
typical examples of preferred embodiments of the present invention
are explained hereinafter, these examples are only illustrative and
not intended to limit the scope of the present invention. First,
the polyamide resins according to the first and second aspects of
the present invention are described. The polyamide resins according
to the first and second aspects of the present invention are
respectively constituted of a dicarboxylic acid constitutional unit
comprising an adipic acid unit and a diamine constitutional unit
comprising a pentamethylenediamine unit and a hexamethylenediamine
unit.
[0041] The content of the adipic acid unit in the dicarboxylic acid
constitutional unit of the polyamide resin is usually not less than
90% by weight and preferably not less than 95% by weight. The
dicarboxylic acid constitutional unit may be composed of the adipic
acid unit only. The total content of the pentamethylenediamine unit
and the hexamethylenediamine unit in the diamine constitutional
unit of the polyamide resin is usually not less than 90% by weight
and preferably not less than 95% by weight. The diamine
constitutional unit may be composed of the pentamethylenediamine
unit and the hexamethylenediamine unit only.
[0042] In the polyamide resin according to the first aspect of the
present invention, the weight ratio of the pentamethylenediamine
unit to the hexamethylenediamine unit in the diamine constitutional
unit is 95:5 to 5:95, preferably 95:5 to 60:40 and more preferably
90:10 to 70:30. In the polyamide resin according to the second
aspect of the present invention, the weight ratio of the
pentamethylenediamine unit to the hexamethylenediamine unit in the
diamine constitutional unit is 95:5 to 60:40, preferably 92.5:7.5
to 65:35 and more preferably 90:10 to 70:30. When the weight ratio
of the pentamethylenediamine unit to the hexamethylenediamine unit
is more than 95%, the resultant polyamide resin tends to be
deteriorated in vibration-welding strength, retention heat
stability and transparency of the filament produced therefrom. On
the other hand, When the weight ratio of the pentamethylenediamine
unit to the hexamethylenediamine unit is less than the
above-specified range, the resultant polyamide resin tends to be
deteriorated in vibration-welding strength, retention heat
stability, low-temperature toughness, transparency of the filament
produced therefrom and biomass ratio. Meanwhile, the weight ratio
of the pentamethylenediamine unit to the hexamethylenediamine unit
in the diamine constitutional unit of the polyamide resin may be
determined, for example, by the following method. That is, the
polyamide resin is hydrolyzed with an acid or an alkali to
decompose the resin into pentamethylenediamine,
hexamethylenediamine and adipic acid as constitutional units
thereof, and contents of the respective components are determined
by a liquid chromatography, etc., using a calibration curve
previously prepared.
[0043] The polyamide resin of the present invention may be in the
form of either a blended mixture of homopolyamides or a copolymer
as long as these polymers contain the above constitutional units.
More specifically, the polyamide may be in the form of a blended
mixture of a polyamide 56 homopolymer and a polyamide 66
homopolymer or a copolyamide comprising pentamethylenediamine,
hexamethylenediamine and adipic acid as constitutional units
thereof. Among them, the copolyamide is especially preferred in
order to achieve the aimed effects of the present invention.
[0044] The polyamide resin of the present invention may also
contain comonomer components other than pentamethylenediamine,
hexamethylenediamine and adipic acid as essential constitutional
units thereof in an amount of usually less than 10% by weight and
preferably less than 5% by weight unless the addition thereof
adversely affects the aimed effects of the present invention.
Examples of the comonomer components may include amino acids such
as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic
acid and p-aminomethylbenzoic acid, and lactams such as
.epsilon.-caprolactam and .omega.-laurolactam.
[0045] Examples of the dicarboxylic acid as the comonomer component
may include aliphatic dicarboxylic acids such as oxalic acid,
malonic acid, succinic acid, glutaric acid, adipic acid, pimelic
acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid,
dodecanedioic acid, brassilic acid, tetradecanedioic acid,
pentadecanedioic acid and octadecanedioic acid, alicyclic
dicarboxylic acids such as cyclohexanedicarboxylic acid, and
aromatic dicarboxylic acids such as phthalic acid, isophthalic
acid, terephthalic acid and naphthalenedicarboxylic acid.
[0046] Examples of the diamine as the comonomer component may
include aliphatic diamines such as ethylenediamine,
1,3-diaminopropane, 1,4-diaminobutane, 1,7-diaminoheptane,
1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane,
1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane,
1,14-diaminotetradecane, 1,15-diaminopentadecane,
1,16-diaminohexadecane, 1,17-diaminoheptadecane,
1,18-diaminooctadecane, 1,19-diaminononadecane,
1,20-diaminoeicosane and 2-methyl-1,5-diaminopentane; alicyclic
diamines such as cyclohexane diamine and bis-(4-aminohexyl)methane;
and aromatic diamines such as xylenediamine.
[0047] The polymerization degree of the polyamide resin of the
present invention is not particularly limited. A 98 wt % sulfuric
acid solution of the polyamide resin (concentration of the
polyamide resin: 0.01 g/mL) has a relative viscosity of usually 1.5
to 8.0 and preferably 1.8 to 5.0 as measured at 25.degree. C. When
the relative viscosity of the solution is less than 1.5, the
polyamide resin tends to be insufficient in strength upon actual
use. When the relative viscosity of the solution is more than 8.0,
the polyamide resin tends to be deteriorated in fluidity and
exhibit a poor moldability.
[0048] When the polyamide resin of the present invention is
subjected to DSC measurement, the ratio of an endothermic peak area
of the polyamide resin as measured at a temperature of not lower
than 240.degree. C. to a whole endothermic peak area thereof is
usually not more than 60% and preferably not more than 50%. When
the ratio of the endothermic peak area of the polyamide resin as
measured at a temperature of not lower than 240.degree. C. to a
whole endothermic peak area thereof is more than 60%, the polyamide
resin tends to be deteriorated in a vibration-welding strength,
retention heat stability and low-temperature toughness. The DSC
measurement may be conducted using "Robot DSC" manufactured by
Seiko Denshi Kogyo Co., Ltd. In the specific procedure for the DSC
measurement, about 5 mg of the obtained polyamide resin is placed
in a sample pan, heated to 290.degree. C. under a nitrogen
atmosphere, and then held at 290.degree. C. for 3 min. Thereafter,
the polyamide resin is cooled to 30.degree. C. at a temperature
drop rate of 20.degree. C./min and successively held at 30.degree.
C. for 3 min. and then heated again from 30.degree. C. to
290.degree. C. at a temperature rise rate of 20.degree. C./min to
observe and measure an endothermic peak thereof. An endothermic
peak area of the polyamide resin is determined from the thus
prepared endothermic peak curve.
[0049] The method of determining the endothermic peak area of the
polyamide resin is explained by referring to FIGS. 1 and 2. In
endothermic peaks observed in the range between 200.degree. C. and
290.degree. C., when the temperature of an endothermic peak
observed as a minimum temperature is expressed by a (.degree. C.)
and the temperature of an endothermic peak observed as a maximum
temperature is expressed by b (.degree. C.), and endothermic points
observed at temperatures (a-50(.degree. C.)) and (b+10(.degree.
C.)) are expressed by X1 and X2, respectively, the endothermic peak
area is defined by such an area surrounded by a line (L) connecting
the endothermic points X1 and X2 and the endothermic peak curve
(refer to the hatched portion in FIG. 1). Meanwhile, as shown in
FIG. 2, if the line (L) connecting the endothermic points X1 and X2
(indicated by a dashed line in FIG. 2) is intersected with the
endothermic peak curve between the endothermic points X1 and X2,
the endothermic peak area is defined by an area surrounded by the
endothermic peak curve and a bending line (X1-C--X2) wherein C is a
point at which the endotherm becomes minimum between the
endothermic peaks (i.e., the hatched portion shown in FIG. 2).
[0050] The melting point (Tm) of the polyamide resin of the present
invention as observed on a high-temperature side is usually 225 to
255.degree. C. and preferably 230 to 253.degree. C. Meanwhile, the
melting point is determined as the endothermic peak temperature
observed in the DSC measurement. When two or more endothermic peaks
are detected, the polyamide resin has a plurality of melting points
corresponding to the endothermic peaks.
[0051] The polyamide resin of the present invention may be blended
with other components at an optional stage from production
(polycondensation) of the polyamide resin to molding thereof unless
the addition thereof adversely affects the aimed effects of the
present invention. Examples of the other components blended in the
polyamide resin may include antioxidants and/or heat stabilizers,
weather-resisting agents, nucleating agents, mold release agents
and/or lubricants, pigments, dyes, plasticizers, antistatic agents,
flame retardants and other polymers.
[0052] Specific examples of the antioxidants and/or heat
stabilizers may include hindered phenol-based compounds,
hydroquinone-based compounds, phosphite-based compounds and
substituted compounds thereof, copper halides and iodine compounds.
Specific examples of the weather-resisting agents may include
resorcinol-based compounds, salicylate-based compounds,
benzotriazole-based compounds, benzophenone-based compounds and
hindered amine-based compounds. Specific examples of the nucleating
agents may include inorganic fine particles such as talc, kaolin,
silica and boron nitride, metal oxides and high-melting nylons.
Specific examples of the mold release agents and/or lubricants may
include aliphatic alcohols, aliphatic amides, aliphatic bisamides,
bisureas and polyethylene waxes. Specific examples of the pigments
may include cadmium sulfide, phthalocyanine and carbon black.
Specific examples of the dyes may include nigrosine and aniline
black. Specific examples of the plasticizers may include octyl
p-oxybenzoate and N-butyl benzenesulfonamide.
[0053] Specific examples of the antistatic agents may include alkyl
sulfate-type anionic antistatic agents, quaternary ammonium
salt-type cationic antistatic agents, nonionic antistatic agents
such as polyoxyethylene sorbitan monostearate, and betaine-based
amphoteric antistatic agents. Specific examples of the flame
retardants may include melamine cyanurate, hydroxides such as
magnesium hydroxide and aluminum hydroxide, ammonium
polyphosphates, brominated polystyrenes, brominated polyphenylene
oxides, brominated polycarbonates, brominated epoxy resins, and
combination of these bromine-based compounds with antimony
trioxide. Specific examples of the other polymers may include other
polyamides, polyethylene, polypropylene, polyesters,
polycarbonates, polyphenylene ethers, polyphenylene sulfides,
liquid crystal polymers, polysulfones, polyether sulfones, ABS
resins, SAN resins and polystyrenes.
[0054] Among these components, when the polyamide resin is used for
injection molding and non-reinforcing purposes for hinged molded
products, binding bands, etc., the nucleating agents or mold
release agents are preferably dry-blended in the polyamide resin in
order to enhance a moldability thereof unless the addition thereof
adversely affects the aimed effects of the present invention.
[0055] The polyamide resin of the present invention (including
homopolyamide and polyamide copolymer) may be produced by known
methods. Specific methods for producing the polyamide resin are
described in "Handbook for Polyamide Resins" edited by FUKUMOTO,
Osamu (published by Nikkan Kogyo Newspaper Co., Ltd.), etc. The
polyamide 56 copolymer is preferably produced by the method of
polycondensing an aliphatic diamine component comprising
pentamethylenediamine and hexamethylenediamine in a total amount of
usually not less than 90% and preferably not less than 95% with a
dicarboxylic acid component comprising adipic acid in an amount of
usually not less than 90% and preferably not less than 95%. More
specifically, in the preferred production method, a salt of
pentamethylenediamine and adipic acid and a salt of
hexamethylenediamine and adipic acid are prepared, and mixed with
each other under the coexistence of water, and then the resultant
mixture is heated to allow a dehydration reaction
(heat-polycondensation) thereof to proceed. In this case, by
varying a mixing ratio between the salt of pentamethylenediamine
and adipic acid and the salt of hexamethylenediamine and adipic
acid, it is possible to obtain polyamide resins having different
copolymerization compositions from each other. The mixing ratio
between the salt of pentamethylenediamine and adipic acid and the
salt of hexamethylenediamine and adipic acid is preferably
controlled such that the molar ratio of the aliphatic diamine to
the dicarboxylic acid is usually in the range of 1.00:1 to
1.05:1.
[0056] Meanwhile, in the present invention, the heat
polycondensation means a process for production of polyamide resins
in which a maximum temperature of the polymerization reaction
mixture reaches 200.degree. C. or higher. The upper limit of the
maximum temperature is usually not more than 300.degree. C. in the
consideration of a heat stability of the polyamide resin upon the
polymerization reaction. The polymerization reaction may be
conducted by either a batch method or a continuous method.
[0057] The polyamide resin produced by the above method may be
further subjected to solid phase polymerization after the heat
polycondensation, thereby enhancing a molecular weight of the
obtained polyamide resin. The solid phase polymerization may be
conducted, for example, by heating the polyamide resin at a
temperature of not lower than 100.degree. C. and not higher than a
melting point thereof in vacuum or under an inert gas
atmosphere.
[0058] In the polyamide resin described in the first aspect of the
present invention, pentamethylenediamine as the raw component may
be produced from lysine using a lysine decarboxylase, cells capable
of producing the lysine decarboxylase or a treated product of the
cells. In the polyamide resin described in the second aspect of the
present invention, pentamethylenediamine as the raw component is
also preferably produced from lysine using a lysine decarboxylase,
cells capable of producing the lysine decarboxylase or a treated
product of the cells. The use of such a pentamethylenediamine
produced from lysine enables the resultant polyamide resin to
exhibit a high biomass ratio (ratio of a biomass-derived raw
material to whole raw materials used for production of the
polyamide resin). The biomass ratio (ratio of a biomass-derived raw
material to whole raw materials used for production of the
polyamide resin) in the polyamide resin of the present invention is
preferably not less than 5%. When the biomass ratio in the
polyamide resin is less than 5%, it is not possible to attain the
effect of suppressing generation of carbon dioxide causing the
global warming problem.
[0059] More specifically, the above pentamethylenediamine may be
produced, for example, by the following method. That is, a
lysine-containing solution is subjected to enzymatic
decarboxylation reaction while adding an acid to the
lysine-containing solution so as to keep a pH value of the solution
suitable for the enzymatic decarboxylation reaction. Examples of
the acid used in the enzymatic decarboxylation reaction may include
inorganic acids such as hydrochloric acid, sulfuric acid and
phosphoric acid, and organic acids such as acetic acid. The
obtained reaction product solution may be subjected to ordinary
separation and purification methods to recover liberated
pentamethylenediamine therefrom. When a dicarboxylic acid such as
adipic acid is used as the acid added upon the enzymatic
decarboxylation reaction, it is also possible to recover a
pentamethylenediamine dicarboxylate which may be directly used as
the raw material for production of the polyamide. The method of
producing pentamethylenediamine adipate by enzymatic
decarboxylation reaction of lysine using adipic acid as the above
acid is described in Japanese Patent Application Laid-open (KOKAI)
No. 2005-6650.
[0060] Next, the polyamide resin composition according to the third
aspect of the present invention is explained. The polyamide resin
composition of the present invention comprises the polyamide resin
according to the first or second aspect of the present invention,
and an inorganic filler.
[0061] Examples of the inorganic filler may include graphite,
barium sulfate, magnesium sulfate, calcium carbonate, magnesium
carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc
oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum,
copper, iron, stainless steel, glass fiber, glass flakes, glass
beads, carbon fiber, talc, silica, kaolin, clay, wollastonite,
mica, boron nitride, potassium titanate, aluminum borate,
bentonite, montmorillonite, synthetic mica, etc. Among these
inorganic fillers, glass fiber is preferred because of a high
reinforcing effect and relatively low costs thereof.
[0062] As the glass fiber, there may be used those glass fibers
ordinarily used for thermoplastic resins. Among these glass fibers,
preferred are chopped strands produced from E-glass (alkali-free
glass). The fiber diameter of the glass fiber is usually 1 to 20
.mu.m and preferably 5 to 15 .mu.m. The glass fiber is preferably
surface-treated with a silane coupling agent, etc., in order to
enhance adhesion to the polyamide resin.
[0063] The inorganic filler may be blended in the polyamide resin
at an optional stage from production (polycondensation) of the
polyamide resin to molding thereof. The inorganic filler is
preferably charged into an extruder which is in the course of
molding the polyamide resin, and melt-kneaded with the polyamide
resin therein.
[0064] The amount of the inorganic filler blended is 0.01 to 150
parts by weight and preferably 0.01 to 100 parts by weight based on
100 parts by weight of the polyamide resin. When the amount of the
inorganic filler blended is more than 150 parts by weight, the
resultant composition tends to be deteriorated in fluidity.
[0065] The polyamide resin composition of the present invention may
also be blended with other components at an optional stage from
production (polycondensation) of the polyamide resin to molding
thereof unless the addition thereof adversely affects the effects
of the present invention. Examples of the other components may
include those described in the first and second aspects of the
present invention, namely, antioxidants and/or heat stabilizers,
weather-resisting agents, nucleating agents, mold release agents
and/or lubricants, pigments, dyes, plasticizers, antistatic agents,
flame retardants and other polymers.
[0066] Next, the vibration-welded molded product according to the
fourth aspect of the present invention, the hinged molded product
according to the fifth aspect of the present invention, the binding
band according to the sixth aspect of the present invention and the
filament according to the seventh aspect of the present invention
are explained below. The vibration-welded molded product, hinged
molded product, binding band and filament of the present invention
respectively comprise the polyamide resin according to the first or
second aspect of the present invention or the polyamide resin
composition according to the third aspect of the present
invention.
[0067] The vibration-welded molded product of the present invention
may be produced by the following method. First, a plurality of
parts are respectively molded from the polyamide resin or the
polyamide resin composition to form primary molded products. The
method of forming the primary molded products is not particularly
limited, and there may be used any optional molding methods such as
an injection-molding method, a film-forming method, a melt-sinning
method, a blow-molding method and a vacuum forming method. Among
these molding methods, preferred is the injection-molding method.
The shape of the primary molded product is not particularly
limited, and the primary molded product may be of any desired
shape. Also, the shapes of a plurality of the primary molded
products may be identical to or different from each other.
[0068] Next, a plurality of the thus molded parts as primary molded
products are bonded together by vibration welding to obtain a
vibration-welded molded product. In the vibration welding method, a
frequency of vibration used therefor is usually 100 to 300 Hz, and
an amplitude thereof is usually 0.5 to 2.0 mm and preferably 0.8 to
1.6 mm. The welding pressure used in the vibration welding is
usually 0.5 to 10 MPa and preferably 0.8 to 6 MPa. When the welding
pressure is too high or too low, the resultant vibration-welded
molded product tends to be deteriorated in welding strength. In
particular, when the welding pressure is too low, welded portions
of the obtained vibration-welded molded product tend to be
insufficient in welding strength, resulting in poor air tightness
in the case where the molded product is a hollow product. The
welding time used under a given pressure may be controlled so as to
obtain the aimed welding margin, and a retention time of the molded
product after stopping application of the vibration may be
controlled so as to allow the welded portions to be fully
solidified.
[0069] The hinged molded product and binding band of the present
invention may be obtained by molding the polyamide resin or the
polyamide resin composition of the present invention into a desired
shape by any optional methods similarly to those used for
production of the primary molded product of the vibration-welded
molded product. Among the molding methods, especially preferred is
an injection-molding method.
[0070] Specific examples of the hinged molded product and the
binding band may include hinged clips, hinged connectors, hinged
binding bands, etc. The thickness of the hinged portion of these
products is usually 0.2 to 0.8 mm and preferably 0.3 to 0.6 mm.
When the thickness of the hinged portion is less than 0.2 mm, the
polyamide resin used in the hinged portion tends to be deteriorated
in fluidity. On the other hand, when the thickness of the hinged
portion is more than 0.8 mm, the crystallinity of the polyamide
used in the hinged portion tends to be increased, so that the
hinged portion tends to suffer from breakage or cracks upon
bending.
[0071] The filament of the present invention may be produced by
forming the polyamide resin or the polyamide resin composition of
the present invention into a filament shape by a melt-spinning
method. The filament of the present invention is preferably applied
to a pile-containing portion of respective constituting layers
(including a base fabric, a pile layer and a packing layer) of a
mat. In particular, when applying the filament to such a mat
requiring a good anti-fouling property, the filament of the present
invention is preferably blended with a nucleating agent such as
talc, silica, kaolin and clay. The filament of the present
invention may also be applied to not only the constituting layers
of the mat, but also carpets for domestic use, carpets for offices,
carpets for automobiles, raw threads for clothing, etc.
[0072] As described above, the polyamide resin and the polyamide
resin composition of the present invention may be formed into a
desired shape by an optional molding method such as an
injection-molding method, a film-forming method, a melt-spinning
method, a blow-molding method and a vacuum forming method. For
example, the polyamide resin and the polyamide resin composition of
the present invention may be used in injection-molded products,
films, sheets, filaments, tapered filaments, fibers, etc., as well
as adhesives and paints.
[0073] Specific examples of the applications of the polyamide resin
and the polyamide resin composition of the present invention may
include automobile and vehicle-related parts, e.g., automobile
under-hood parts such as intake manifold, hinged clips (hinged
molded products), binding bands, resonators, air cleaners, engine
covers, rocker covers, cylinder head covers, timing belt covers,
gasoline tanks, gasoline sub-tanks, radiator tanks, intercooler
tanks, oil reservoir tanks, oil pans, electric gears, oil
strainers, canisters, engine mounts, junction blocks, relay blocks,
connectors, corrugated tubes and protectors, automobile exterior
parts such as door handles, fenders, hood bulges, roof rail legs,
door mirror stays, bumpers, spoilers and wheel covers, automobile
interior parts such as cup holders, console boxes, accelerator
pedals, clutch pedals, shift lever pedestals and shift lever
knobs.
[0074] Further, the polyamide resin and the polyamide resin
composition of the present invention may also be used in various
applications, e.g., fishing-related materials such as fishing lines
and fishing nets; and electric and electronic related parts,
domestic and office electric equipment parts, computer-related
parts, facsimile and copier-related parts and mechanical parts such
as typically switches, micro slide switches, DIP switches, switch
housings, lamp sockets, binding bands, connectors, connector
housings, connector shells, IC sockets, coil bobbins, bobbin
covers, relays, relay boxes, capacitor cases, motor interior parts,
small size motor cases, gears and cams, dancing pulleys, spacers,
insulators, casters, terminal boards, electric tool housings,
starter insulating portions, fuse boxes, terminal housings, bearing
retainers, speaker diaphragms, heat-resisting containers,
electronic oven parts, rice boiler parts and printer ribbon
guides.
[0075] Next, the hinged molded product according to the eighth
aspect of the present invention is explained. The hinged molded
product according to the eighth aspect of the present invention
contains the polyamide resin constituted of an adipic acid unit and
a pentamethylenediamine unit, and may comprise the polyamide resin
solely.
[0076] The content of the adipic acid unit in the dicarboxylic acid
constitutional unit forming the polyamide resin is usually not less
than 90% by weight, preferably not less than 95% by weight, and the
dicarboxylic acid constitutional unit may comprise the adipic acid
unit solely. The content of the pentamethylenediamine unit in the
diamine constitutional unit forming the polyamide resin is usually
not less than 90% by weight, preferably not less than 95% by
weight, and the diamine constitutional unit may comprise the
pentamethylenediamine unit solely.
[0077] The polyamide resin used in the eighth aspect of the present
invention may contain comonomer components other than the essential
pentamethylenediamine and adipic acid constitutional units in an
amount of usually less than 10% by weight and preferably less than
5% by weight based on the weight of the whole constitutional units,
unless the addition thereof adversely affects the aimed effects of
the present invention. As the comonomer components, there may be
used such comonomer components as explained with respect to the
polyamide resins according to the first and second aspect of the
present invention, dicarboxylic acids as a comonomer, and diamines
as a comonomer (1,6-diaminohexane is also usable).
[0078] The polymerization degree of the polyamide resin used in the
eighth aspect of the present invention is not particularly limited,
and may be substantially identical to those of the polyamide resins
according to the first and second aspects of the present
invention.
[0079] The polyamide resin used in the eighth aspect of the present
invention usually has two melting points (Tm), i.e., about
255.degree. C. and about 232.degree. C. Meanwhile, the method of
measuring the melting points is substantially identical to the
method used for measuring the melting point of the polyamide resins
according to the first and second aspects of the present
invention.
[0080] The production method, heat-polycondensation, solid phase
polycondensation and polymerization method of the polyamide resin
used in the eighth aspect of the present invention are
substantially identical to those described with respect to the
polyamide resins according to the first and second aspects of the
present invention.
[0081] In the polyamide resin used in the eighth aspect of the
present invention which is produced by the above method,
pentamethylenediamine as a raw component thereof is preferably
produced from lysine using a lysine decarboxylase, cells capable of
producing the lysine decarboxylase or a treated product of the
cells. By using such a pentamethylenediamine as produced from
lysine, the biomass ratio of the polyamide resin (ratio of a
biomass-derived raw material to whole raw materials used in the
polyamide resin) can be enhanced. The biomass ratio of the
polyamide resin (ratio of a biomass-derived raw material to whole
raw materials used in the polyamide resin) is preferably not less
than 25%. When the biomass ratio is less than 25%, it may be
difficult to attain the effect of suppressing generation of carbon
dioxide causing the global warming problem.
[0082] The method of producing the above pentamethylenediamine is
substantially identical to the production method described with
respect to the polyamide resins according to the first and second
aspects of the present invention.
[0083] The polyamide resin used in the eighth aspect of the present
invention may be blended with other components at any optional
stage from production (polycondensation) of the polyamide resin to
molding thereof, unless the addition thereof adversely affects the
aimed effects of the present invention. Examples of the other
components blended in the polyamide resin may include those
described with respect to the polyamide resins according to the
first and second aspects of the present invention, namely,
nucleating agents, antioxidants and/or heat stabilizers,
weather-resisting agents, mold release agents and/or lubricants,
pigments, dyes, plasticizers, antistatic agents, flame retardants
and other polymers. Among these components, when the polyamide
resin is used for injection-molding and non-reinforcing purposes
for hinged molded products, binding bands, etc., the nucleating
agent or mold release agent is preferably dry-blended in the
polyamide resin in order to enhance a moldability thereof, unless
the addition thereof adversely affects the aimed effects of the
present invention.
[0084] The hinged molded product according to the eighth aspect of
the present invention may be obtained by forming the polyamide
resin of the present invention into a desired shape by an optional
molding method. Examples of the molding method may include an
injection-molding method, a film-forming method, a melt-sinning
method, a blow-molding method and a vacuum forming method. Among
these molding methods, especially preferred is the
injection-molding method.
[0085] Specific examples of the hinged molded product and the
thickness of the hinged portion thereof are substantially identical
to those described with respect to the hinged molded product
according to the fifth aspect of the present invention.
EXAMPLES
[0086] The present invention is described in more detail below by
the following examples, but these examples are only illustrative
and not intended to limit the scope of the present invention.
Meanwhile, among the following Examples and Reference Examples,
Examples 1 to 8 and Reference Examples 1 to 5 are concerned with
the first to seventh aspects of the present invention, and Example
9 and Reference Example 6 are concerned with the eighth aspect of
the present invention. Various properties described in the present
invention were measured by the following methods.
[0087] The present invention is described in more detail below by
the following examples, but these examples are only illustrative
and not intended to limit the scope of the present invention. The
methods for evaluating various properties of the polyamide resin,
the polyamide resin composition, the molded products produced
therefrom, and the hinged molded product are explained below.
(1) Relative Viscosity (.eta.r):
[0088] A 98% sulfuric acid solution of the polyamide resin
(concentration: 0.01 g/mL) was prepared, and a relative viscosity
thereof was measured at 25.degree. C. using an Ostwald type
viscometer.
(2) DSC (Differential Scanning Calorimetry):
[0089] The DSC measurement was conducted using "Robot DSC"
manufactured by Seiko Denshi Kogyo Co., Ltd. First, about 5 mg of
the polyamide resin was charged into a sampling pan, and heated to
290.degree. C. under a nitrogen atmosphere and held at 290.degree.
C. for 3 min to completely melt the resin. Thereafter, the molten
polyamide resin was cooled to 30.degree. C. at a temperature drop
rate of 20.degree. C./min to measure an exothermic peak temperature
observed during the temperature drop. The thus observed exothermic
peak temperature was determined as a temperature-drop
crystallization temperature (T(.degree. C.)). Successively, the
polyamide resin was held at 30.degree. C. for 3 min, and then
heated again from 30.degree. C. to 290.degree. C. at a temperature
rise rate of 20.degree. C./min to measure an endothermic peak
thereof and determine an endothermic peak area therefrom. The
temperature of the thus observed endothermic peak was determined as
a melting point (Tm) of the polyamide resin. When a plurality of
endothermic peaks were detected, the temperatures thereof were
determined as a plurality of melting points of the polyamide
resin.
(3) Retention Heat Stability:
[0090] 7 g of the polyamide resin as a sample was placed in a 18 cc
test tube, and the test tube filled with the sample was
hermetically sealed under a nitrogen atmosphere and immersed in an
oil bath maintained at a temperature higher by 30.degree. C. than
the melting point of the polyamide resin (melting point+30.degree.
C.). After the elapse of 9 hr, the sample was recovered to measure
a relative viscosity thereof. A viscosity retention rate of the
polyamide resin was calculated from the relative viscosity values
thereof measured before and after the retention test.
(4) Vibration-Welding Test:
(4-1) Pressure Test for Hollow Product:
<Primary Molding of Parts of Hollow Product>
[0091] A glass fiber-reinforced polyamide resin composition was
formed into a pair of parts of a hollow product each having a
thickness of 2 mm and a welding surface width of 4 mm as primary
molded products as shown in FIGS. 3(a) and 3(b). The primary
molding was performed at a resin temperature of 270.degree. C. and
a mold temperature of 80.degree. C. using an injection molding
machine "IS 350 Model" manufactured by Toshiba Kikai Co., Ltd.
<Vibration Welding of Parts of Hollow Product>
[0092] Using a vibration welding machine "VIBRATION WELDER Model
2800" manufactured by Emerson Japan, Ltd., the above pair of parts
of the hollow product were bonded together by vibration welding.
The vibration welding was conducted under the conditions including
a welding pressure as shown in Table 1, a vibration frequency of
240 Hz, a vibration amplitude of 1.5 mm, a welding margin of 1.5
mm, a retention pressure substantially identical to the welding
pressure immediately before stopping the vibration, and a retention
time of 5.0 sec, thereby obtaining a vibration-welded molded
product (hollow product) as shown in FIG. 4. Upon the above
vibration welding, the dimension of the welding margin of each part
of the hollow product was controlled using a non-contact welding
dimension controller (WDC) "CX132 Model" manufactured by Emerson
Japan, Ltd.
<Pressure Test for Hollow Product>
[0093] The thus obtained hollow product was subjected to a pressure
test. Using a pressure tester manufactured by Toyo Seiki Seisakusho
Co., Ltd., two upper openings (1) and (1') (opening diameter: 32
mm.phi.) of the hollow product were closed, and a hydraulic
pressure was applied to an inside of the hollow product through a
lower opening (2) (opening diameter: 32 mm.phi.) at a pressure
gradation rate of 980 kPa/min to measure the pressure upon breaking
of the vibration-welded molded product. The test was repeated 3
times every welding pressure, and an average of the measured values
was calculated to determine a pressure-resisting strength of the
hollow product.
(4-2) Vibration-Welding Strength Test for Rectangular Test
Piece:
<Primary Molding of Rectangular Test Piece>
[0094] A glass fiber-reinforced polyamide resin composition was
molded to form two primary molded products of a rectangular
parallelepiped shape each having a bottom surface of 25 mm.times.4
mm and a height of 60 mm. The primary molding was conducted at a
resin temperature of 270.degree. C. and a mold temperature of
80.degree. C. using an injection molding machine "J75-ED Model"
manufactured by Japan Steel Works, LTD.
<Vibration Welding of Rectangular Test Piece>
[0095] Using a vibration welding machine "VIBRATION WELDER Model
2800" manufactured by Emerson Japan, Ltd., the above two primary
molded products were bonded together at bottom surfaces thereof by
vibration welding. The vibration welding was conducted under the
conditions including a welding pressure as shown in Table 1, a
vibration frequency of 240 Hz, a vibration amplitude of 1.5 mm, a
welding margin of 1.5 mm, a retention pressure substantially
identical to the welding pressure immediately before stopping the
vibration, and a retention time of 5.0 sec, thereby obtaining a
vibration-welded molded product constituted from the above two
primary molded products welded together at the bottom surfaces
thereof. Upon the above vibration welding, the dimension of the
welding margin of the vibration-welded molded product was
controlled using a non-contact welding dimension controller (WDC)
"CX132 Model" manufactured by Emerson Japan, Ltd.
<Vibration Welding Strength Test for Rectangular Test
Piece>
[0096] The thus obtained vibration-welded molded product was
subjected to a vibration welding strength test. Using "TENSILON
UTM-III-2500" manufactured by A & D Corp., the vibration-welded
molded product was subjected to a tensile test at a distance
between chucks of 60 mm and a pulling velocity of 5 mm/min to
measure a strength thereof upon breaking. The six molded products
were tested every welding pressure, and an average of the measured
values was calculated to determine a vibration welding strength of
the molded product.
(5) Evaluation of Mechanical Properties (Tensile Test, Bending Test
and Notched Charpy Impact Test)
[0097] The glass fiber-reinforced polyamide resin composition and
the non-reinforced polyamide resin composition were respectively
molded into ISO test pieces according to ISO Standard. The molding
was conducted using an injection molding machine "J75EII Model"
manufactured by Japan Steel Works, LTD., at a resin temperature of
270.degree. C. and a mold temperature of 80.degree. C. for the
glass fiber-reinforced polyamide resin composition or at a resin
temperature of 265.degree. C. and a mold temperature of 80.degree.
C. for the non-reinforced polyamide resin composition. The thus
molded ISO test pieces were subjected to a tensile test, a bending
test and a notched Charpy impact test according to respective ISO
Standards.
(6) Low-Temperature Hinge Property:
[0098] The non-reinforced polyamide resin composition was molded
into a hinged molded product as shown in FIG. 5 and a binding band
as shown in FIG. 6. The molding of the hinged molded product was
conducted using an injection molding machine "PS40 Model"
manufactured by Nissei Plastic Industrial Co., Ltd., at a resin
temperature of 265.degree. C. and a mold temperature of 80.degree.
C. The molding of the binding band was conducted using an injection
molding machine "SE50D Model" manufactured by Sumitomo Heavy
Industries, Ltd., at a resin temperature of 265.degree. C. and a
mold temperature of 80.degree. C. The hinged portion of these
molded products had a length of 2 mm, a width of 40 mm and a
thickness of 0.4 mm.
[0099] The hinged molded product was cooled in a
constant-temperature oven maintained at a temperature shown in
Table 2 for 2 hr. Meanwhile, as the constant-temperature oven,
there was used a large-size chamber capable of allowing a measuring
person to enter therein for conducting the test. After cooling the
hinged molded product for 2 hr, the measuring person entered into
the constant-temperature oven and was standing-by for 10 min to
completely eliminate adverse influences of temperature change due
to the entrance of the measuring person. Thereafter, the test was
conducted by bending the hinged portion from 90.degree.
(perpendicularly bent state) to 180.degree. (flat state relative to
a floor) as shown in FIG. 7. More specifically, while holding the
molded product at its horizontal surface portion with one hand, the
vertical surface portion thereof was rapidly bent with the other
hand. The twenty hinged molded products were tested every measuring
temperature. The number of the hinged molded products whose hinged
products were free from breakage was counted as a measured value of
the test.
(7) Low-Temperature Band Breaking Property:
[0100] The binding band was cooled in the constant-temperature oven
at a temperature as shown in Table 2. Meanwhile, as the
constant-temperature oven, there was used a large-size chamber
capable of allowing a measuring person to enter therein for
conducting the test. After cooling the binding band for 2 hr, the
measuring person entered into the constant-temperature oven and was
standing-by for 10 min to completely eliminate adverse influences
of temperature change due to the entrance of the measuring person.
Thereafter, the test was conducted by inserting one end of the band
into an opening provided at the other end of the band as shown in
FIG. 8 and then strongly pulling the one end of the band while
holding the other end thereof with one hand. The twenty binding
bands were tested every measuring temperature. The number of the
binding bands which were free from breakage was counted as a
measured value of the test.
(8) Transparency of Monofilament:
[0101] A 40 mm.phi. single-screw extruder manufactured by UNIPLAS
CORPORATION, and equipped at its tip end with a gear pump and a
nozzle with 18 holes each having a diameter of 0.6 mm was used as
an extruder for spinning. The polyamide resin was melted at a
temperature higher by 20.degree. C. than the melting point of the
polyamide resin (melting point+20.degree. C.), and melt-spun using
the above extruder, passed through a cooling water vessel at
20.degree. C. to cool and solidify the spun resin, stretched at
98.degree. C. in a wet heat condition, subjected to second-stage
stretching in a hot-air stretching vessel at 172.degree. C. and
then thermally fixed in the hot-air stretching vessel at
168.degree. C., thereby obtaining a monofilament having a diameter
of 0.079 mm. The thus obtained monofilament was visually observed
to evaluate a transparency thereof.
[0102] In the following Examples and Reference Examples, "AH salt"
produced by Rhodia Ltd., was used as an equimolar salt of
hexamethylenediamine and adipic acid. Whereas, an equimolar salt of
pentamethylenediamine and adipic acid was produced by the method
described in Examples 1 to 3 of Japanese Patent Application
Laid-open (KOKAI) No. 2005-6650.
Example 1
Polyamide Resin Composition and Vibration Welded Molded Product
[0103] 25 kg of water was added to 25 kg of a mixture containing
the equimolar salt of pentamethylenediamine and adipic acid and the
equimolar salt of hexamethylenediamine and adipic acid (as to the
weight ratio therebetween, refer to Table 1), and then 1.25 g of
phosphorous acid was added thereto to completely dissolve the
mixture under a nitrogen atmosphere, thereby obtaining a raw
material aqueous solution. The thus obtained raw material aqueous
solution was transported into an autoclave previously purged with
nitrogen using a plunger pump. By adjusting a jacket temperature
and a pressure in the autoclave to 280.degree. C. and 1.47 MPa,
respectively, the contents of the autoclave were heated to
270.degree. C. Next, the inside pressure of the autoclave was
gradually released and further reduced to terminate the reaction at
the time at which the agitation power reached a predetermined
value. After completion of the reaction, the inside pressure of the
autoclave was restored by supplying nitrogen thereinto, and the
contents of the autoclave were introduced into a cooling water
vessel in the form of a strand, and then pelletized using a rotary
cutter. The resultant pellets were dried at 120.degree. C. and 1
torr (0.13 kPa) until the water content thereof reached 0.1% or
lower, thereby obtaining a polyamide resin. The thus obtained
polyamide resin was subjected to evaluation of various properties
thereof.
[0104] 100 parts by weight of the obtained polyamide resin was
blended with 43 parts by weight of a glass fiber "T249H" produced
by Nippon Electric Glass Co., Ltd., thereby obtaining a glass
fiber-reinforced polyamide resin composition. The blending was
conducted using a twin-screw kneader "TEM-35B Model" manufactured
by Toshiba Machine Co., Ltd. The glass fiber was side-fed in order
to avoid a breakage thereof, and the melt-kneading temperature was
adjusted to 270.degree. C. The thus obtained polyamide resin
composition was subjected to vibration-welding test and evaluation
of mechanical properties thereof. The results are shown in Table
1.
Reference Example 1
[0105] The same procedure as defined in Example 1 was conducted
except that the composition of monomers charged in the raw salts
was changed as shown in Table 1, thereby obtaining a polyamide
resin. The thus obtained polyamide resin was blended with a glass
fiber by the same method as defined in Example 1, thereby obtaining
a glass fiber-reinforced polyamide resin composition. The thus
obtained polyamide resin composition was subjected to
vibration-welding test and evaluation of mechanical properties
thereof. The results are shown in Table 1.
Example 2
Polyamide Resin Composition, Hinged Molded Product and Binding
Band
[0106] 100 parts by weight of the polyamide resin obtained in
Example 1 was blended with 0.02 part by weight of talc as a
nucleating agent having an average particle size of 3.0 .mu.m and
then dry-blended, thereby obtaining a non-reinforced polyamide
resin composition. The thus obtained polyamide resin composition
was subjected to evaluation of a low-temperature hinge property, a
low-temperature band breaking property and mechanical properties
thereof. The results are shown in Table 2.
Reference Example 2
[0107] The same procedure as defined in Example 1 was conducted
except that the composition of monomers charged in the raw material
aqueous solution was changed as shown in Table 1, thereby obtaining
a polyamide resin. The thus obtained polyamide resin was blended
with talc by the same method as defined in Example 2 and then
dry-blended with each other, thereby obtaining a non-reinforced
polyamide resin composition. The thus obtained polyamide resin
composition was subjected to evaluation of a low-temperature hinge
property, a low-temperature band breaking property and mechanical
properties thereof. The results are shown in Table 2.
Reference Example 3
[0108] 25 kg of caprolactam produced by Mitsubishi Chemical
Corporation, 0.75 kg of water and 1.74 g of disodium hydrogen
phosphite pentahydrate were charged into a container, and after the
container was purged with nitrogen, the contents of the container
were dissolved at 100.degree. C. The thus obtained raw material
aqueous solution was transported into an autoclave. The heating of
the solution was initiated by adjusting a jacket temperature to
280.degree. C. Next, after heating the contents of the autoclave to
270.degree. C., the inside pressure of the autoclave was gradually
released and further reduced to terminate the polycondensation
reaction at the time at which the agitation power reached a
predetermined value. After completion of the reaction, the inside
pressure of the autoclave was restored by supplying nitrogen
thereinto, and the contents of the autoclave were introduced into a
cooling water vessel in the form of a strand, and then pelletized
using a rotary cutter. The resultant pellets were treated with a
boiled water in an amount of 1.5 times the amount of the pellets to
extract and remove unreacted monomers and oligomers therefrom. The
pellets from which the unreacted compounds were removed, were dried
at 120.degree. C. and 1 torr (0.13 kPa) until the water content
thereof reached 0.1% or lower, thereby obtaining a polyamide resin.
The thus obtained polyamide resin was subjected to evaluation of
various properties thereof.
[0109] The obtained polyamide resin was blended with talc by the
same method as defined in Example 2 and then dry-blended with each
other, thereby obtaining a non-reinforced polyamide resin
composition. The thus obtained polyamide resin composition was
subjected to evaluation of a low-temperature hinge property, a
low-temperature band breaking property and mechanical properties
thereof. The results are shown in Table 2.
Examples 3 to 8
Polyamide Resin and Filament
[0110] The same procedure as defined in Example 1 was conducted
except that the composition of monomers charged in the raw material
aqueous solution was changed as shown in Tables 3 and 4, thereby
obtaining a polyamide resin. The thus obtained polyamide resin was
subjected to evaluation of various properties thereof. Further, the
obtained polyamide resin was formed into a monofilament by the
method described in the above item "evaluation of transparency", to
evaluate a transparency thereof. The results are shown in Tables 3
and 4.
Reference Example 4
[0111] The same procedure as defined in Example 1 was conducted
except that the composition of monomers charged in the raw material
aqueous solution was changed as shown in Table 5, thereby obtaining
a polyamide resin. The thus obtained polyamide resin was subjected
to evaluation of various properties thereof. Further, the obtained
polyamide resin was formed into a monofilament by the method
described in the above item "evaluation of transparency", to
evaluate a transparency thereof. The results are shown in Table
5.
Reference Example 5
[0112] The same procedure as defined in Example 1 was conducted
except that the composition of monomers charged in the raw material
aqueous solution was changed as shown in Table 5, thereby obtaining
a polyamide resin. The thus obtained polyamide resin was subjected
to evaluation of various properties thereof. Further, the obtained
polyamide resin was formed into a monofilament by the method
described in the above item "evaluation of transparency", to
evaluate a transparency thereof. The results are shown in Table
5.
TABLE-US-00001 TABLE 1 Example Reference Unit 1 Example 1
Composition of monomers charged Salt of pentamethylenediamine wt %
80 100 and adipic acid Salt of hexamethylenediamine wt % 20 0 and
adipic acid .epsilon.-Caprolactum wt % 0 0 Properties of polyamide
resin Polyamide resin -- 56/66 56 nylon nylon Relative viscosity
[.eta.r] -- 3.00 3.00 Melting point (Tm) .degree. C. 245; 233 255;
232 Ratio of endothermic peak area % 28 62 as measured at
240.degree. C. or higher Relative viscosity after -- 2.65 2.18
retention test Relative viscosity retention % 88.3 72.7 rate after
retention test Blending ratio of resin composition Glass fiber wt
part 43 43 Pressure-resisting strength Welding pressure 0.98 MPa
kPa 1270 1210 1.47 MPa kPa 1170 1140 2.45 MPa kPa 1130 1060
Vibration-welding strength Welding pressure 1.52 MPa MPa 66.7 65.3
2.55 MPa MPa 68.5 59.7 3.82 MPa MPa 60.0 57.1 Mechanical properties
Tensile strength MPa 190 189 Tensile elongation % 4.1 3.8 Bending
strength MPa 251 253 Bending modulus MPa 8490 8610 Notched Charpy
impact strength kJ/m.sup.2 7.7 7.3 Biomass ratio of polyamide
resin.sup.1) % 33 41 Note .sup.1)Ratio of biomass-derived raw
material to whole raw materials used in the polyamide resin
TABLE-US-00002 TABLE 2 Reference Example Examples Unit 2 2 3
Composition of monomers charged Salt of pentamethylenedi- wt % 80
100 0 amine and adipic acid Salt of hexamethylenediamine wt % 20 0
0 and adipic acid .epsilon.-Caprolactum wt % 0 0 100 Properties of
polyamide resin Polyamide resin -- 56/66 56 nylon 6 nylon nylon
Relative viscosity [.eta.r] -- 3.00 3.00 3.00 Melting point (Tm)
.degree. C. 245; 233 255; 232 224 Ratio of endothermic peak % 28 62
0 area as measured at 240.degree. C. or higher Relative viscosity
after -- 2.65 2.18 -- retention test Relative viscosity retention %
88.3 72.7 -- rate after retention test Blending ratio of resin
composition Talc wt part 0.02 0.02 0.02 Low-temperature hinge
property (number of specimens free from breakage after testing
total 20 specimens) Temperature of constant- temperature oven
-20.degree. C. -- 19 20 6 -30.degree. C. -- 18 20 1 -40.degree. C.
-- 17 17 0 Low-temperature band breaking property (number of
specimens free from breakage after testing total 20 specimens)
Temperature of constant- temperature oven -10.degree. C. -- 17 9 19
-15.degree. C. -- 13 1 19 -20.degree. C. -- 5 0 13 Mechanical
properties Tensile strength MPa 86 88 82 Tensile elongation % 26 25
32 Bending strength MPa 107 111 98 Bending modulus MPa 2860 2850
2710 Notched Charpy impact kJ/m.sup.2 7.9 6.9 8.7 strength Biomass
ratio of polyamide % 33 41 0 resin Note 1): Ratio of
biomass-derived raw material to whole raw materials used in the
polyamide resin
TABLE-US-00003 TABLE 3 Examples Unit 3 4 5 Composition of monomers
charged Salt of pentamethylenedi- wt % 90 80 60 amine and adipic
acid Salt of hexamethylenedi- wt % 10 20 40 amine and adipic acid
.epsilon.-Caprolactum wt % 0 0 0 Properties of polyamide resin
Polyamide resin -- 56/66 56/66 56/66 nylon nylon nylon Relative
viscosity [.eta.r] -- 3.43 3.50 3.42 Melting point (Tm) .degree. C.
250; 231 247; 231 225; 184 Temperature-drop .degree. C. 190 183 175
crystallization temperature Moldability Molding temperature
.degree. C. 270 267 245 Transparency of filament -- Trans- Trans-
Trans- parent parent parent
TABLE-US-00004 TABLE 4 Examples Unit 6 7 8 Composition of monomers
charged Salt of pentamethylenedi- wt % 40 20 15 amine and adipic
acid Salt of hexamethylenediamine wt % 60 80 85 and adipic acid
.epsilon.-Caprolactum wt % 0 0 0 Properties of polyamide resin
Polyamide resin -- 56/66 56/66 56/66 nylon nylon nylon Relative
viscosity [.eta.r] -- 3.48 3.52 3.60 Melting point (Tm) .degree. C.
229; 207 245 250 Temperature-drop .degree. C. 181 195 197
crystallization temperature Moldability Molding temperature
.degree. C. 249 265 270 Transparency of filament -- Trans- Trans-
Trans- parent parent parent
TABLE-US-00005 TABLE 5 Reference Examples Unit 4 5 Composition of
monomers charged Salt of pentamethylenedi- wt % 100 0 amine and
adipic acid Salt of hexamethylenediamine wt % 0 100 and adipic acid
.epsilon.-Caprolactum wt % 0 0 Properties of polyamide resin
Polyamide resin -- 56 nylon 66 nylon Relative viscosity [.eta.r] --
3.72 4.06 Melting point (Tm) .degree. C. 256; 233 266
Temperature-drop .degree. C. 200 211 crystallization temperature
Moldability Molding temperature .degree. C. 276 286 Transparency of
filament -- Opaque Opaque
Example 9
[0113] 25 kg of water was added to 25 kg of an equimolar salt of
pentamethylenediamine and adipic acid, and then 1.25 g of
phosphorous acid was added thereto to completely dissolve the
mixture under a nitrogen atmosphere, thereby obtaining a raw
material aqueous solution. The thus obtained raw material aqueous
solution was transported into an autoclave previously purged with
nitrogen using a plunger pump. By adjusting a jacket temperature
and a pressure in the autoclave to 280.degree. C. and 1.47 MPa,
respectively, the contents of the autoclave were heated to
270.degree. C. Next, the inside pressure of the autoclave was
gradually released and further reduced to terminate the reaction at
the time at which the agitation power reached a predetermined
value. After completion of the reaction, the inside pressure of the
autoclave was restored by supplying nitrogen thereinto, and the
contents of the autoclave were introduced into a cooling water
vessel in the form of a strand, and then pelletized using a rotary
cutter. The resultant pellets were dried at 120.degree. C. and 1
torr (0.13 kPa) until the water content thereof reached 0.1% or
lower, thereby obtaining a polyamide resin. The thus obtained
polyamide resin was subjected to evaluation of various properties
thereof. The results are shown in Table 6.
[0114] 100 parts by weight of the obtained polyamide resin was
blended with 0.02 part by weight of talc as a nucleating agent
having an average particle size of 3.0 .mu.m and then dry-blended
with each other, thereby obtaining a non-reinforced polyamide resin
composition. The thus obtained polyamide resin composition was
subjected to evaluation of a low-temperature hinge property and
mechanical properties thereof. The results are shown in Table
6.
Reference Example 6
[0115] 25 kg of caprolactam produced by Mitsubishi Chemical
Corporation, 0.75 kg of water and 1.74 g of disodium hydrogen
phosphite pentahydrate were charged into a container, and after the
container was purged with nitrogen, the contents of the container
were dissolved at 100.degree. C. The thus obtained raw material
aqueous solution was transported into an autoclave. The heating of
the solution was initiated by adjusting a jacket temperature to
280.degree. C. After heating the contents of the autoclave to
270.degree. C., the inside pressure of the autoclave was gradually
released and further reduced to terminate the polycondensation
reaction at the time at which the agitation power reached a
predetermined value. After completion of the reaction, the inside
pressure of the autoclave was restored by supplying nitrogen
thereinto, and the contents of the autoclave were introduced into a
cooling water vessel in the form of a strand, and then pelletized
using a rotary cutter. The resultant pellets were treated with a
boiled water in an amount of 1.5 times the amount of the pellets to
extract and remove unreacted monomers and oligomers therefrom. The
pellets from which the unreacted compounds were removed, were dried
at 120.degree. C. and 1 torr (0.13 kPa) until the water content
thereof reached 0.1% or lower, thereby obtaining a polyamide resin.
The thus obtained polyamide resin was subjected to evaluation of
various properties thereof.
[0116] The obtained polyamide resin was blended with talc by the
same method as defined in Example 9 and then dry-blended together,
thereby obtaining a non-reinforced polyamide resin composition. The
thus obtained polyamide resin composition was subjected to
evaluation of a low-temperature hinge property and mechanical
properties thereof. The results are shown in Table 6.
TABLE-US-00006 TABLE 6 Example Reference Unit 9 Example 6
Composition of monomers charged Salt of pentamethylenedi- wt % 100
0 amine and adipic acid .epsilon.-Caprolactum wt % 0 100 Properties
of polyamide resin Polyamide resin -- 56 nylon 6 nylon Relative
viscosity -- 3.00 3.00 Melting point (Tm) .degree. C. 255; 232 224
Blending ratio of resin composition Talc wt part 0.02 0.02
Low-temperature hinge property (number of specimens free from
breakage after testing total 20 specimens) Temperature of constant-
temperature oven -20.degree. C. -- 20 6 -30.degree. C. -- 20 1
-40.degree. C. -- 17 0 Mechanical properties Tensile yield stress
MPa 88 82 Tensile break strain % 25 32 Bending strength MPa 111 98
Bending modulus MPa 2850 2710 Notched Charpy impact strength
kJ/m.sup.2 6.9 8.7 Biomass ratio of polyamide resin.sup.1) % 41 0
Note .sup.1)Ratio of biomass-derived raw material to whole raw
materials used in the polyamide resin
[0117] Although the present invention is described above with
respect to embodiments which are considered to be most practical
and preferable at the present time, the present invention is not
limited to these embodiments, and various changes and modifications
will be appropriately made within the scope of claims and a whole
of a specification of this application unless departing from the
subject matter and concept of the present invention, and it should
be construed that the changes and modifications are involved in
technical range of the present invention. Meanwhile, the present
patent application is based on Japanese Patent Application No.
2004-152059 filed on May 21, 2004, Japanese Patent Application No.
2005-144478 filed on May 17, 2005 and Japanese Patent Application
No. 2005-145847 filed on May 18, whole contents of which are
incorporated herein by reference.
* * * * *