Title of Invention

POLYAMIDE, POLYAMIDE COMPOSITION, AND METHOD FOR PRODUCING POLYAMIDE

Abstract The present invention relates to a polyamide obatainable by polymerizing an (a) dicarboxylic acid comprising at least 50 mol% of an alicyclic dicarboxylic acid and a (b) diamine comprising at least 50 mol% of a diamine having a substituent branched from a main chain.
Full Text

DESCRIPTION
POLYAMIDE, POLYAMIDE COMPOSITION, AND METHOD FOR
PRODUCING POLYAMIDE
Technical Field
[0001]
The present invention relates to a polyamide, a
polyamide composition, and a method for producing
polyamide.
Background Art
[0002]
Polyamides represented by polyamide 6 and polyamide
66 (hereinafter, sometimes referred to as "PA6" and
"PA66", respectively) and the like have excellent molding
processability, mechanical properties, or chemical
resistance. Therefore, polyamides are widely used as a
material for various parts, such as for automobiles,
electric and electronic parts, industrial materials, and
daily and household articles.
[0003]
In the automotive industry, as an environmental
measure, there is a need to lighten the weight of the
automobile body by using a metal substitute in order to
reduce exhaust gases. To respond to this need,
polyamides are being increasingly used for exterior


materials, interior materials and the like. Further, the
level of the properties required for polyamide materials,
such as heat resistance, strength, and appearance, is
dramatically increasing. However, the temperature in the
engine room is also tending to increase, so that the need
to increase the heat resistance of polyamide materials is
growing stronger.
Further, in the electric and electronics industry,
such as household appliances, there is a need for
increased heat resistance for polyamide materials which
are capable of withstanding the increased melting point
of the solder required for lead-free solder for using
surface mounting technology (SMT) .
PA6 and PA66 polyamides are unable to satisfy these
requirements in terms of heat resistance, since their
melting point is low.
[0004]
To resolve the above-described problems with
conventional polyamides such as PA6 and PA66, a high-
melting-point polyamide has been proposed. Specifically,
a polyamide formed from terephthalic acid and
hexamethylenediamine (hereinafter, sometimes referred to
as "PA6T") has been proposed.
However, PA6T is a high-melting-point polyamide
having a melting point of about 370°C. Therefore, even
if a molded product is obtained by melt kneading,
pyrolysis of the polyamide is severe, which makes it


difficult to obtain a molded product having sufficient
properties.
[0005]
To resolve the above-described problem with PA6T, a
high-melting-point semi-aromatic polyamide (hereinafter,
sometimes referred to as "6T-based copolyamide") and the
like comprising terephthalic acid and a
hexamethylenediamine as main components has been proposed.
This high-melting-point semi-aromatic polyamide has a
melting point lowered to about 220 to 340°C by
copolymerizing an aliphatic polyamide, such as PA6 and
PA66, and the amorphous aromatic polyamide formed from
hexamethylendiamine and isophthalic acid (hereinafter,
sometimes referred to as "PA6I) and the like with PA6T.
[0006]
As a 6T-based copolyamide, Patent Document 1
describes an aromatic polyamide (hereinafter, sometimes
referred to as "PA6T/2MPDT) which is formed from an
aromatic dicarboxylic acid and an aliphatic diamine, in
which the aliphatic diamine is a mixture of
hexamethylenediamine and 2-methylpentamethylenediamine.
[0007]
Further, in contrast to an semi-aromatic polyamide
formed from an aromatic dicarboxylic acid and an
aliphatic diamine, a high-melting-point aliphatic
polyamide (hereinafter, sometimes referred to as "PA4 6")
formed from adipic acid and tetramethylenediamine, and an


alicyclic polyamide formed from an alicyclic dicarboxylic
acid and an aliphatic diamine, and the like have been
proposed.
[0008]
Patent Documents 2 and 3 describe a semi-alicyclic
polyamide (hereinafter, sometimes referred to as "PA6C
copolyamide") which is formed from an alicyclic polyamide
(hereinafter, sometimes referred to as "PA6C") formed
from 1,4-cyclohexanedicarboxylic acid and
hexamethylenediamine, and another polyamide.
Patent Document 2 describes that electric and
electronic parts formed from a semi-alicyclic polyamide
blended with 1 to 40% of 1,4-cyclohexanedicarboxylic acid
as a dicarboxylic acid unit have improved solder heat
resistance. Patent Document 3 describes that for
automobile components, fluidity, toughness and the like
are excellent.
[0009]
In addition, Patent Document 4 describes that a
polyamide formed from a dicarboxylic acid unit comprising
1,4-cyclohexanedicarboxylic acid and a diamine unit
comprising 2-methyl-1,8-octanediamine has excellent light
fastness, toughness, moldability, low weight, heat
resistance and the like. Moreover, as a production
method for such a polyamide, Patent Document 4 describes
that a polyamide having a melting point of 311°C is
produced by reacting 1,4-cyclohexanedicarboxylic acid and


1, 9-nonanediamine at 230°C or less to produce a
prepolymer, which is then subjected to solid phase
polymerization at 230°C.
Further, Patent Document 5 describes that a
polyamide using 1,4-cyclohexanedicarboxylic acid having a
trans/cis ratio of from 50/50 to 97/3 as a raw material
has excellent heat resistance, low water absorbance, and
light fastness.
[0010]
Patent Document 1: National Publication of International
Patent Application No. 1994(Hei 6)-503590
Patent Document 2: National Publication of International
Patent Application No. 1999 (Hei 11)-512476
Patent Document 3: National Publication of International
Patent Application No. 2001-514695
Patent Document 4: Japanese Patent Laid-Open No. 9-128 68
Patent Document 5: WO 2002/048239 pamphlet
Disclosure of the Invention
Problems to be Solved by the Invention
[0011]
Although 6T-based copolyamides certainly have
properties such as low water absorbance, high heat
resistance, and high chemical resistance, their fluidity
is low, and their moldability and the surface appearance
of the molded product is insufficient. In addition,
their toughness and light fastness is poor. Consequently,


there is a need for improvement for applications which
require a good molded product appearance, such as an
exterior component, or which are exposed to sunlight and
the like. Moreover, 6T-based copolyamides have a large
specific weight, so that there is a need for improvement
in terms of reducing weight as well.
[0012]
Although the PA6/2MPDt described in Patent Document
1 can partially improve on the problems of conventional
PA6T copolymers, the level of improvement in terms of
fluidity, moldability, toughness molded product surface
appearance, and light fastness is insufficient.
[0013]
Although PA4 6 has good heat resistance and
moldability, PA4 6 suffers from the problems of high water
absorbance. Further, the dimensional change and
deterioration in mechanical properties due to water
absorbance is very large. Thus, in some cases PA46
cannot satisfy the dimensional change requirement
required for automobile applications.
[0014]
The PA6C copolyamide described in Patent Documents 2
and 3 also suffers from problems such as having a high
water absorbance and insufficient fluidity.
For the polyamides described in Patent Documents 4
and 5 too, the improvement in terms of toughness,
rigidity, and fluidity is insufficient.


[0015]
It is an object of the present invention to provide
a polyamide having a high melting point, which has
excellent heat resistance, fluidity, toughness, low water
absorbance, and rigidity.
Means for Solving the Problems
[0016]
As a result of continued intensive investigations
into resolving the above-described problems, the present
inventors discovered that a polyamide obtained by
polymerizing, as the main constituent components, an
alicyclic dicarboxylic acid and a diamine having a
substituent branched from a main chain can resolve the
above-described problems, thereby arriving at the present
invention.
[0017]
More specifically, the present invention is as
follows.
(1) A polyamide obtainable by polymerizing (a)
dicarboxylic acid comprising at least 50 mol% of an
alicyclic dicarboxylic acid and (b) diamine comprising at
least 50 mol% of a diamine having a substituent branched
from a main chain.
(2) The polyamide according to (1), wherein the diamine
having the substituent branched from the main chain is 2-
methylpentamethylenediamine.


(3) The polyamide according to (1) or (2), wherein the
alicyclic dicarboxylic acid is 1,4-
cyclohexanedicarboxylic acid.
(4) The polyamide according to any one of (1) to (3),
wherein the dicarboxylic acid further comprises an
aliphatic dicarboxylic acid having 10 or more carbon
atoms.

(5) The polyamide according to any one of (1) to (4),
which is obtainable by further copolymerizing with a (c)
lactam and/or aminocarboxylic acid.
(6) The polyamide according to any one of (1) to (5),
which has a melting point of from 270 to 350°C.
(7) The polyamide according to any one of (1) to (6),
which has a trans isomer ratio of from 50 to 85%.
(8) The polyamide according to any one of (1) to (7),
which has a b value of 0 or less.
(9) A polyamide composition comprising:
(A) a polyamide according to any one of (1) to (8);
and
(B) an inorganic filler.
(10) A polyamide composition comprising:
(A) a polyamide according to any one of (1) to (8);
and
(C) a copper compound and a metal halide.
(11) A polyamide composition comprising:
(A) a polyamide according to any one of (1) to (8);
and


(D) a halogen-based flame retardant.
(12) A polyamide composition comprising:
(A) a polyamide according to any one of (1) to (8);
and
(E) a phosphinate and/or diphosphinate.
(13) A polyamide composition comprising:
(A) a polyamide according to any one of (1) to (8);
and
(F) a stabilizer.
(14) An automobile component, comprising a polyamide
composition according to any one of (9) to (13).
(15) The automobile component according to (14), which is
an automobile air intake system component or an
automobile cooling system component.
(16) A method for producing a polyamide, comprising a
step of polymerizing an (a) dicarboxylic acid comprising
at least 50 mol% of an alicyclic dicarboxylic acid and a
(b) diamine comprising at least 50 mol% of an aliphatic
diamine having a substituent branched from a main chain.
(17) The method for producing the polyamide according to
(16), wherein the polymerization is carried out while
maintaining a trans isomer ratio at from 50 to 80%.
(18)A polyamide obtainable by the method of (16) or (17).
Advantages of the Invention
[0018]


According to the present invention, a high-melting-
point polyamide can be provided, which has excellent heat
resistance, fluidity, toughness, low water absorbance,
and rigidity.
Best Mode for Carrying Out the Invention
[0019]
A best mode for carrying out the present invention
(hereinafter referred to as "the present embodiment") is
described below in more detail. However, the present
invention is not limited to the following embodiment, and
can be variously modified within the scope of the intent
of the invention.
[0020]
Polyamide
The polyamide according to the present embodiment is
a polyamide obtained by polymerizing the following (a)
and (b):
an (a) dicarboxylic acid comprising at least 50 mol%
of an alicyclic dicarboxylic acid, and
a (b) diamine comprising at least 50 mol% of a
diamine having a substituent branched from a main chain.
In the present embodiment, "polyamide" means a
polymer which has an amide (-NHC0-) bond in a main chain.
[0021]
(a) Dicarboxylic acid


The (a) dicarboxylic acid used in the present
embodiment comprises at least 50 mol% of an alicyclic
dicarboxylic acid.
By comprising at least 50 mol% of the alicyclic
dicarboxylic acid as the (a) dicarboxylic acid, the
polyamide can be obtained which simultaneously satisfies
heat resistance, fluidity, toughness, low water
absorbance, rigidity and the like.
[0022]
Examples of the (a-1) alicyclic dicarboxylic acid
(also referred to as cycloaliphatic dicarboxylic acid)
include alicyclic dicarboxylic acids having an alicyclic
structure with 3 to 10 carbon atoms, and preferably 5 to
10 carbon atoms, such as 1,4-cyclohexanedicarboxylic acid,
1,3-cyclohexanedicarboxylic acid, and 1,3-
cyclopentanedicarboxylic acid. The alicyclic
dicarboxylic acid may optionally have a substituent.
[0023]
In the present embodiment, examples of the
substituent include an alkyl group having 1 to 4 carbon
atoms, such as a methyl group, an ethyl group, a n-propyl
group, an isopropyl group, a n-butyl group, an isobutyl
group, and a tert-butyl group.
[0024]
From perspectives such as heat resistance, fluidity,
and rigidity, 1,4-cyclohexanedicarboxylic acid is
preferred as the alicyclic dicarboxylic acid.


As the alicyclic dicarboxylic acid, one kind may be
used, or two or more kinds may be used in combination.
[0025]
Alicyclic dicarboxylic acids have trans and cis
geometric isomers.
The alicyclic dicarboxylic acid used as a raw
material monomer may be either a trans or a cis isomer.
The alicyclic dicarboxylic acid may also be used as a
mixture of trans and cis isomers in various ratios.
Since alicyclic dicarboxylic acids isomerize in a
fixed ratio at high temperatures, and the cis isomer has
a higher water solubility than the trans isomer in an
equivalent amount of salt with a diamine, as the raw
material monomer, a trans isomer / cis isomer ratio is,
based on molar ratio, preferably 50/50 to 0/100, more
preferably 40/60 to 10/90, and still more preferably
35/65 to 15/85.
The alicyclic dicarboxylic acid trans isomer / cis
isomer ratio (molar ratio) can be determined by liquid
chromatography (HPLC) or NMR.
[0026]
Examples of an (a-2) dicarboxylic acid other than
the alicyclic dicarboxylic acid in the (a) dicarboxylic
acid used in the present embodiment include aliphatic
dicarboxylic acids and aromatic dicarboxylic acids.
[0027]


Examples of the aliphatic dicarboxylic acid include
straight-chain or branched saturated aliphatic
dicarboxylic acids having 3 to 20 carbon atoms, such as
malonic acid, dimethylmalonic acid, succinic acid, 2,2-
dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-
diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric
acid, 2,2-dimethylglutaric acid, adipic acid, 2-
methyladipic acid, trimethyl adipic acid, pimelic acid,
suberic acid, azelaic acid, sebacic acid, dodecanedioic
acid, tetradecanedioic acid, hexadecanedioic acid,
octadecanedioic acid, eicosane diacid, and diglycolic
acid.
[0028]
Examples of the aromatic dicarboxylic acid include
aromatic dicarboxylic acids, which are unsubstituted or
substituted with various substituents, having 8 to 20
carbon atoms, such as terephthalic acid, isophthalic acid,
naphthalene dicarboxylic acid, 2-chloroterephthalic acid,
2-methylterephthalic acid, 5-methylisophthalic acid, and
5-sodium sulfoisophthalic acid.
Examples of the various substituents include an
alkyl group having 1 to 6 carbon atoms, an aryl group
having 6 to 12 carbon atoms, an arylalkyl group having 7
to 2 0 carbon atoms, a halogen group such as a chloro
group or a bromo group, an alkylsilyl group having 3 to
10 carbon atoms, and a sulfonic acid group or salt
thereof, such as a sodium salt.


[0029]
As the dicarboxylic acid other than the alicyclic
dicarboxylic acid, from perspectives such as heat
resistance, fluidity, toughness, low water absorbance,
and rigidity, an aliphatic dicarboxylic acid is preferred,
and more preferred is an aliphatic dicarboxylic acid
having 6 or more carbon atoms.
Of these, from perspectives such as heat resistance
and low water absorbance, an aliphatic dicarboxylic acid
having 10 or more carbon atoms is preferred.
Examples of the aliphatic dicarboxylic acids having
10 or more carbon atoms include sebacic acid,
dodecanedioic acid, tetradecanedioic acid,
hexadecanedioic acid, octadecanedioic acid, and
eicosanedioic acid.
Of these, from perspectives such as heat resistance,
sebacic acid and dodecanedioic acid are preferred.
As the dicarboxylic acid other than the alicyclic
dicarboxylic acid, one kind may be used, or two or more
kinds may be used in combination.
[0030]
To the extent that the object of the present
embodiment is not harmed, the (a) dicarboxylic acid may
further include a trivalent or higher polyvalent
carboxylic acid, such as trimellitic acid, trimesic acid,
and pyromellitic acid.


As the polyvalent carboxylic acid, one kind may be
used, or two or more kinds may be used in combination.
[0031]
A ratio of the (a-1) alicyclic dicarboxylic acid in
the (a) dicarboxylic acid is at least 50 mol%. The ratio
of the alicyclic dicarboxylic acid is 50 to 100 mol%, and
preferably 60 to 100%. By setting the ratio of the
alicyclic dicarboxylic acid to be at least 50 mol%, the
polyamide can be obtained which simultaneously satisfies
heat resistance, fluidity, toughness, low water
absorbance, rigidity and the like.
A ratio of the (a-2) dicarboxylic acid other than
the alicyclic dicarboxylic acid in the (a) dicarboxylic
acid is 0 to 50 mol%, and preferably 0 to 40%.
[0032]
It is preferred that the (a-1) alicyclic
dicarboxylic acid is 50.0 to 99.9 mol% and the (a-2)
aliphatic dicarboxylic acid having 10 or more carbon
atoms is 0.1 to 50.0 mol%. It is more preferred that the
(a-1) alicyclic dicarboxylic acid is 60.0 to 90.0 mol%
and the (a-2) aliphatic dicarboxylic acid having 10 or
more carbon atoms is 10.0 to 40.0 mol%. It is still more
preferred that the (a-1) alicyclic dicarboxylic acid is
70.0 to 85.0 mol% and the (a-2) aliphatic dicarboxylic
acid having 10 or more carbon atoms is 15.0 to 30.0 mol%.
[0033]


In the present embodiment, the (a) dicarboxylic acid
is not limited to the compounds described above as
dicarboxylic acids. The dicarboxylic acid may be a
compound equivalent to those described above.
Examples of compounds equivalent to those described
above are not especially limited, as long as such
compound can have the same dicarboxylic acid structure as
a dicarboxylic acid structure derived from the above-
described dicarboxylic acids. Examples thereof include
anhydrides and halides of the dicarboxylic acid.
[0034]
(b) Diamine
The (b) diamine used in the present embodiment
comprises at least 50 mol% of a diamine having a
substituent branched from a main chain.
By comprising at least 50 mol% of the diamine having
the substituent branched from the main chain in the (b)
diamine, the polyamide can be obtained which
simultaneously satisfies fluidity, toughness, rigidity
and the like.
[0035]
Examples of the substituent branched from the main
chain include an alkyl group having 1 to 4 carbon atoms,
such as a methyl group, an ethyl group, a n-propyl group,
an isopropyl group, a n-butyl group, an isobutyl group,
and a tert-butyl group.
[0036]


Examples of the (b-1) diamine having the substituent
branched from the main chain include branched saturated
aliphatic diamines having 3 to 20 carbon atoms, such as
2-methylpentamethylenediamine (also referred to as 2-
methyl-1,5-diaminopentane) , 2,2,4-
trimethylhexamethylenediamine, 2,4,4-
trimethylhexamethylenediamine, 2-
methyloctamethylenediamine, and 2,4-
dimethyloctamethylenediamine.
From perspectives such as rigidity, the diamine
having the substituent branched from the main chain is
preferably 2-methylpentamethylenediamine.
As the diamine having the substituent branched from
the main chain, one kind may be used, or two or more
kinds may be used in combination.
[0037]
Examples of a (b-2) diamine other than the diamine
having the substituent branched from the main chain in
the (b) diamine used in the present embodiment include
aliphatic diamines, alicyclic diamines, and aromatic
diamines.
[0038]
Examples of the aliphatic diamines include straight-
chain saturated aliphatic diamines having 2 to 20 carbon
atoms, such as ethylenediamine, propylenediamine,
tetramethylenediamine, pentamethylenediamine,
hexamethylenediamine, heptamethylenediamine,


octamethylenediamine, nonamethylenediamine,
decamethylenediamine, undecamethylenediamine,
dodecamethylenediamine, and tridecamethylenediamine.
[0039]
Examples of the alicyclic diamines (also referred to
as cycloaliphatic diamines) include 1,4-
cyclohexanediamine, 1,3-cyclohexanediamine, and 1,3-
cyclopentanediamine.
[0040]
Examples of aromatic diamines include meta-
xylylenediamine.
[0041]
From perspectives such as heat resistance, fluidity,
toughness, low water absorbance, and rigidity, an
aliphatic diamine and an alicyclic diamine are preferred
as the diamine other than the diamine having the
substituent branched from the main chain. More preferred
is a straight-chain saturated aliphatic diamine having 4
to 13 carbon atoms, still more preferred is a straight-
chain saturated aliphatic diamine having 6 to 10 carbon
atoms, and even still more preferred is
hexamethylenediamine.
As the diamine other than the diamine having the
substituent branched from the main chain, one kind may be
used, or two or more kinds may be used in combination.
[0042]


To the extent that the object of the present
embodiment is not harmed, the (b) diamine may further
include a trivalent or higher polyvalent aliphatic amine,
such as bishexamethylenetriamine.
As the polyvalent aliphatic amine, one kind may be
used, or two or more kinds may be used in combination.
[0043]
A ratio of the (b-1) diamine having the substituent
branched from the main chain in the (b) diamine is at
least 50 mol%. The ratio of the diamine having the
substituent branched from the main chain is 50 to 100
mol%, and preferably 60 to 100%. By setting the ratio of
the diamine having the substituent branched from the main
chain to be at least 50 mol%, the polyamide can be
obtained which has excellent fluidity, toughness,
rigidity and the like.
[0044]
A ratio of the (b-2) diamine other than the diamine
having the substituent branched from the main chain in
the (b) diamine is 0 to 50 mol%, and preferably 0 to 40%.
[0045]
An added amount of the (a) dicarboxylic acid is
preferably about the same molar amount as an added amount
of the (b) diamine. Considering escape out of the (b)
diamine reaction system during the polymerization
reaction, based on an (a) dicarboxylic acid molar amount
of 1.00, the total (b) diamine molar amount is preferably


0.90 to 1.20, more preferably 0.95 to 1.10, and still
more preferably 0.98 to 1.05.
[0046]
(c) Lactam and/or aminocarboxylic acid
From the perspective of toughness, it is preferred
to obtain the polyamide according to the present
embodiment by further copolymerizing with a (c) lactam
and/or aminocarboxylic acid.
The term "(c) lactam and/or aminocarboxylic acid"
used in the present embodiment means a lactam and/or
aminocarboxylic acid capable of polycondensation.
The lactam and/or aminocarboxylic acid is preferably
a lactam and/or aminocarboxylic acid having 4 to 14
carbon atoms, and more preferably a lactam and/or
aminocarboxylic acid having 6 to 12 carbon atoms.
[0047]
Examples of the lactam include butyrolactam,
pivalolactam, s-caprolactam, caprylolactam, enantholactam,
undecanonelactam, and laurolactam (dodecanolactam).
Of these, from the perspective of toughness, s-
caprolactam, laurolactam and the like are preferred, and
s-caprolactam is more preferred.
[0048]
Examples of the aminocarboxylic acid include co-
aminocarboxylic acid and a, co-aminocarboxylic acid, which
are compounds obtained by opening the ring of the above-
described lactams.


As the aminocarboxylic acid, a straight-chain or
branched saturated aliphatic carboxylic acid having 4 to
14 carbon atoms substituted at the co position with an
amino group is preferred. Examples thereof include 6-
aminocaproic acid, 11-aminoundecanoic acid, and 12-
aminododecanoic acid. Further examples of the
aminocarboxylic acid include para-aminomethylbenzoic acid.
[0049]
As the lactam and/or aminocarboxylic acid, one kind
may be used, or two or more kinds may be used in
combination.
[0050]
An added amount of the (c) lactam and/or
aminocarboxylic acid is preferably 0 to 20 mol% based on
a total molar amount of the respective monomers of (a),
(b), and (c).
[0051]
When polymerizing the polyamide from the (a)
dicarboxylic acid and the (b) diamine, a known end-
capping agent can be added for molecular weight
regulation.
Examples of the end-capping agent include
monocarboxylic acids, monoamines, acid anhydrides such as
phthalic anhydride, monoisocyanates, monoacid halides,
monoesters, and monoalcohols. From the perspective of
thermal stability of the polyamide, monocarboxylic acids
and monoamines are preferred.


As the end-capping agent, one kind may be used, or
two or more kinds may be used in combination.
[0052]
Examples of monocarboxylic acids which can be used
as the end-capping agent are not especially limited, as
long as the monocarboxylic acid is reactive with an amino
group. Examples thereof include: aliphatic
monocarboxylic acids such as formic acid, acetic acid,
propionic acid, butyric acid, valeric acid, caproic acid,
caprylic acid, lauric acid, tridecyl acid, myristic acid,
pulmitic acid, stearic acid, pivalic acid, and isobutyric
acid; alicyclic monocarboxylic acids such as cyclohexane
carboxylic acid; and aromatic monocarboxylic acids such
as benzoic acid, toluic acid, a-naphthalene carboxylic
acid, p-naphthalene carboxylic acid, methylnaphthalene
carboxylic acid, and phenylacetic acid.
As the monocarboxylic acid, one kind may be used, or
two or more kinds may be used in combination.
[0053]
Examples of monoamines which can be used as the end-
capping agent are not especially limited, as long as the
monoamine is reactive with a carboxyl group. Examples
thereof 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;


and aromatic monoamines such as aniline, toluidine,
diphenylamine, and naphthylamine.
As the monoamine, one kind may be used, or two or
more kinds may be used in combination.
[0054]
Preferred combinations of the (a) dicarboxylic acid
and (b) diamine include, but are not limited to, (a-1) at
least 50 mol% or more of alicyclic dicarboxylic acid and
(b-1) at least 50 mol% or more of 2-
methylpentamethylenediamine. More preferred is (a-1) at
least 50 mol% or more of 1,4-cyclohexanedicarboxylic acid
and (b-1) at least 50 mol% or more of 2-
methylpentamethylenediamine.
By polymerizing these combinations as the polyamide
components, a high-melting-point polyamide can be
obtained which simultaneously satisfies heat resistance,
fluidity, toughness, low water absorbance, and rigidity.
[0055]
In the polyamide according to the present embodiment,
the alicyclic dicarboxylic acid structure exists as cis
and trans geometric isomers.
The trans isomer ratio of the alicyclic dicarboxylic
acid structure in the polyamide represents the ratio of
trans isomers based on the whole alicyclic dicarboxylic
acid in the polyamide. The trans isomer ratio is
preferably 50 to 85 mol%, more preferably 50 to 80 mol%,
and still more preferably 60 to 80 mol%.


As the (a-1) alicyclic dicarboxylic acid, it is
preferred to use an alicyclic dicarboxylic acid having a
trans/cis ratio (molar ratio) of 50/50 to 0/100. However,
as the polyamide obtained by polymerization of the (a)
dicarboxylic acid and (b) diamine, the trans isomer ratio
is preferably 50 to 85 mol%.
By setting the trans isomer ratio in the above-
described range, in addition the characteristics of a
high melting point and excellent toughness and rigidity,
the polyamide has qualities which simultaneously satisfy
rigidity during heating due to a high glass transition
temperature, fluidity, which is generally a quality that
conflicts with heat resistance, a high crystallinity, and
low water absorbance.
These characteristics of the polyamide are
especially pronounced for a polyamide formed from the
combination of (a) at least 50 mol% or more of 1,4-
cyclohexanedicarboxylic acid and (b) at least 50 mol% or
more of 2-methylpentamethylenediamine, and which has a
trans isomer ratio of from 50 to 85 mol%.
In the present embodiment, the trans isomer ratio
can be measured by the method described in the below
examples.
[0056]
A method for producing the polyamide according to
the present embodiment is not especially limited, as long
as it is a polyamide production method which comprises a


step of polymerizing an (a) dicarboxylic acid comprising
at least 50 mol% of an alicyclic dicarboxylic acid and a
(b) diamine comprising at least 50 mol% of a diamine
having a substituent branched from a main chain.
It is preferred that a method for producing the
polyamide further comprises a step of increasing the
degree of polymerization of the polyamide.
[0057]
As illustrated by the following production method
examples, there are various methods for producing the
polyamide.
1) Heating an aqueous solution or an aqueous suspension
of the dicarboxylic acid and the diamine, or an aqueous
solution or an aqueous suspension of a mixture of the
dicarboxylic acid, the diamine salt, and another
component (hereinafter, abbreviated as "that mixture" in
the following paragraphs), and polymerizing while
maintaining the melt state (hereinafter, sometimes
abbreviated as "hot melt polymerization").
2) Increasing the degree of polymerization while
maintaining a solid state at a temperature at or below
the melting point of the polyamide obtained by hot melt
polymerization (hereinafter, sometimes abbreviated as
"hot melt polymerization / solid phase polymerization")
3) Heating an aqueous solution or an aqueous suspension
of the dicarboxylic acid and the diamine or a mixture
thereof, and increasing the degree of polymerization by


further re-melting the precipitated prepolymer with an
extruder such as a kneader (hereinafter, sometimes
abbreviated as "prepolymer / extrusion polymerization").
4) Heating an aqueous solution or an aqueous suspension
of the dicarboxylic acid and the diamine or a mixture
thereof, and increasing the degree of polymerization
while maintaining the precipitated prepolymer in a solid
state at a temperature at or below the melting point of
the polyamide (hereinafter, sometimes abbreviated as
"prepolymer / solid phase polymerization").
5) Polymerizing the dicarboxylic acid and the diamine,
or a mixture thereof, while maintaining a solid state
(hereinafter, sometimes abbreviated as "solid phase
polymerization").
6) A "solution method" in which polymerization is
carried out using a dicarboxylic acid halide equivalent
to the dicarboxylic acid and the diamine.
[0058]
In the polyamide production method, it is preferred
to carry out polymerization while maintaining the trans
isomer ratio of the alicyclic dicarboxylic acid at from
50 to 85%. From the perspective of fluidity of the
polyamide, it is more preferred to carry out
polymerization while maintaining at from 50 to 80%
By maintaining the trans isomer ratio in the above-
described range, especially at 80% or less, a high-


melting-point polyamide having excellent color tone and
tensile elongation can be obtained.
In the polyamide production method, to increase the
melting point of the polyamide by increasing the degree
of polymerization, it is necessary to increase the
heating temperature and/or lengthen the heating time.
However, in such a case, the polyamide may color due to
the heating and the tensile elongation may deteriorate
due to thermal degradation. Further, a rate of increase
of the molecular weight may also dramatically deteriorate.
To prevent deterioration in the coloration of the
polyamide and deterioration in tensile elongation due to
thermal degradation, the polymerization is preferably
carried out while maintaining the trans isomer ratio of
the alicyclic dicarboxylic acid at 80% or less.
[0059]
Since it is easy to maintain the trans isomer ratio
at 80% or less, and since the obtained polyamide has
excellent color tone, it is preferred to produce the
polyamide by 1) hot melt polymerization and 2) hot melt
polymerization / solid phase polymerization.
[0060]
In the polyamide production method, the
polymerization mode may be either a batch method or a
continuous method.
The polymerization apparatus is not especially
limited. Examples of the polymerization apparatus


include known apparatuses, such as an autoclave type
reactor, a tumbler type reactor, and an extruder type
reactor such as a kneader.
[0061]
The polyamide production method is not especially
limited. For example, the polyamide can be produced by
the batch hot melt polymerization method described below.
Batch hot melt polymerization may be carried out by,
for example, with water as a solvent, concentrating an
approximately 40 to 60 mass% solution containing the
polyamide components ((a) dicarboxylic acid, (b) diamine,
and optionally (c) lactam and/or aminocarboxylic acid) in
a concentration tank operated at a temperature of 110 to
180°C and a pressure of about 0.035 to 0.6 MPa (gauge
pressure) to about 65 to 90 mass% to obtain a
concentrated solution. Then, this concentrated solution
is transferred to an autoclave, and heating is continued
until the pressure in the vessel reaches 1.5 to 5.0 MPa
(gauge pressure). Subsequently, the pressure is kept at
1.5 to 5.0 MPa (gauge pressure) while extracting water
and/or the gas component. When the temperature reaches
about 250 to 350°C, the pressure is reduced to
atmospheric pressure (gauge pressure of 0 MPa) . After
reducing the pressure to atmospheric pressure, the water
produced as a byproduct can be effectively removed by
reducing the pressure as necessary. Then, the pressure
is increased with an inert gas such as nitrogen, and a


polyamide melt product is extruded as a strand. This
strand is cooled and cut to obtain a pellet.
[0062]
The polyamide production method is not especially
limited. For example, the polyamide can be produced by
the continuous hot melt polymerization method described
below.
Continuous hot melt polymerization can be carried
out by, for example, with water as a solvent, pre-heating
an approximately 40 to 60 mass% solution containing the
polyamide components in the vessel of a preliminary
apparatus to a temperature of 40 to 100°C. Then, the
pre-heated solution is transferred to a concentration
tank /reactor, and concentrated to about 70 to 90% at a
pressure of about 0.1 to 0.5 MPa (gauge pressure) and a
temperature of about 200 to 270°C to obtain a
concentrated solution. This concentrated solution is
discharged into a flusher having a temperature maintained
at about 200 to 350°C. Subsequently, the pressure is
reduced to atmospheric pressure (gauge pressure of 0 MPa).
After reducing the pressure to atmospheric pressure, the
pressure is reduced as necessary. Then, a polyamide melt
product is extruded as a strand. This strand is cooled
and cut to obtain a pellet.
[0063]


A molecular weight of the polyamide in the present
embodiment is determined by using relative viscosity ηr
at 25°C as an index.
From the perspectives of mechanical properties such
as toughness and rigidity, and of moldability, the
polyamide according to the present embodiment preferably
has a molecular weight at a relative viscosity r|r at 25°C
at a 1% concentration in 98% sulfuric acid as measured
based on JIS-K6810 of 1.5 to 7.0, more preferably 1.7 to
6.0, and still more preferably 1.9 to 5.5.
Measurement of the relative viscosity at 25°C can be
carried out based on JIS-K6810 as described in the below
examples.
[0064]
From the perspective of heat resistance, the
polyamide according to the present embodiment preferably
has a melting point, referred to as Tm2, of from 270 to
350°C. The melting point Tm2 is preferably 270°C or more,
more preferably 275°C or more, and still more preferably
280°C or more. Further, the melting point Tm2 is
preferably 350°C or less, more preferably 340°C or less,
and still more preferably 330°C or less.
By setting the polyamide melting point Tm2 to be
270°C or more, a polyamide having excellent heat
resistance can be obtained. By setting the polyamide
melting point Tm2 to be 350°C or less, pyrolysis of the


polyamide during melt processing such as extrusion and
molding can be suppressed.
[0065]
From the perspective of heat resistance, a heat of
fusion AH of the polyamide according to the present
embodiment is preferably 10 or more J/g, more preferably
14 or more J/g, still more preferably 18 or more J/g, and
even still more preferably 20 or more J/g.
[0066]
Measurement of the melting point (Tm1 or Tm2) and
the heat of fusion AH of the polyamide according to the
present embodiment can be carried out based on JIS-K7121
as described in the below examples.
Examples of the melting point and heat of fusion
measurement apparatus include the Diamond-DSC,
manufactured by PERKIN-ELMER Inc..
[0067]
The polyamide according to the present embodiment
preferably has a glass transition temperature Tg of from
90 to 170°C. The glass transition temperature is
preferably 90°C or more, more preferably 100°C or more,
and still more preferably 110°C or more. Further, the
glass transition temperature is preferably 170°C or less,
more preferably 165°C or less, and still more preferably
160°C or less.
By setting the polyamide glass transition
temperature to be 90°C or more, a polyamide having


excellent heat resistance and chemical resistance can be
obtained. By setting the polyamide glass transition
temperature to be 170°C or less, a molded product having
a good appearance can be obtained.
Measurement of the glass transition temperature can
be carried out based on JIS-K7121 as described in the
below examples.
Examples of the glass transition temperature
measurement apparatus include the Diamond-DSC,
manufactured by PERKIN-ELMER Inc..
[0068]
The polyamide according to the present embodiment
preferably has a melt shear viscosity r|s of 20 to 140
Pa-s, more preferably 25 to 115 Pa-s, and still more
preferably 30 to 90 Pa-s.
The melt shear viscosity can be measured based on
the method described in the below examples.
By setting the melt shear viscosity to be in the
above-described range, a polyamide having excellent
fluidity can be obtained.
[0069]
The polyamide according to the present embodiment
preferably has a tensile strength of 70 MPa or more, more
preferably 80 MPa or more, and still more preferably 85
MPa or more.
Measurement of the tensile strength can be carried
out based on ASTM D638 as described in the below examples.


By setting the tensile strength to be 70 MPa or more,
a polyamide having excellent rigidity can be obtained.
[0070]
The polyamide according to the present embodiment
preferably has a tensile elongation of 3.0% or more, more
preferably 5.0% or more, and still more preferably 7.0%
or more.
Measurement of the tensile elongation can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile elongation to be 3.0% or more,
a polyamide having excellent toughness can be obtained.
[0071]
The polyamide according to the present embodiment
preferably has a water absorbance of 5.0% or less, more
preferably 4.0% or less, and still more preferably 3.0%
or less.
Measurement of the water absorbance can be carried
out based on the method described in the below examples.
By setting the water absorbance to be 5.0% or less,
a polyamide composition having excellent low water
absorbance can be obtained.
[0072]
The polyamide according to the present embodiment
preferably has a color tone b value of 0 or less, and
more preferably -2 or less.
The color tone b value can be measured by the method
described in the below examples.


By setting the color tone b value to be 0 or less, a
polyamide composition having excellent resistance to heat
discoloration can be obtained.
[0073]
(B) Inorganic filler
The polyamide composition according to the present
embodiment is a polyamide composition comprising the
above-described (A) polyamide and a (B) inorganic filler.
As a polyamide composition, by comprising the (B)
inorganic filler, a polyamide composition can be obtained
having especially excellent rigidity while satisfying
heat resistance, fluidity, toughness, and low water
absorbance, without harming the polyamide qualities of
having excellent heat resistance, fluidity, toughness,
low water absorbance, rigidity and the like.
Polyamides such as PA6 and PA66 cannot satisfy these
requirements in terms of heat resistance, since their
melting point is low.
The polyamide composition also has excellent light
fastness and color tone as a polyamide composition,
despite comprising the inorganic filler. [0074]
The (B) inorganic filler used in the present
embodiment is not especially limited. Examples thereof
include a glass fiber, a carbon fiber, a calcium silicate
fiber, a potassium titanate fiber, an aluminum borate
fiber, glass flakes, talc, kaolin, mica, hydrotalcite,
calcium carbonate, zinc carbonate, zinc oxide, calcium


monohydrogen phosphate, wollastonite, silica, zeolite,
alumina, boehmite, aluminum hydroxide, titanium oxide,
silicon oxide, magnesium oxide, calcium silicate, sodium
aluminosilicate, magnesium silicate, Ketchen black,
acetylene black, furnace black, carbon nanotubes,
graphite, brass, copper, silver, aluminum, nickel, iron,
calcium fluoride, isinglass, montmorillonite, expandable
fluorine mica, and an apatite.
As the inorganic filler, one kind may be used, or
two or more kinds may be used in combination.
[0075]
From perspectives such as rigidity and strength, a
glass fiber, a carbon fiber, glass flakes, talc, kaolin,
mica, calcium carbonate, calcium monohydrogen phosphate,
wollastonite, silica, carbon nanotubes, graphite, calcium
fluoride, montmorillonite, expandable fluorine mica, and
an apatite are preferred as the (B) inorganic filler.
[0076]
More preferably, the (B) inorganic filler is a glass
fiber or a carbon fiber. Among glass fibers and carbon
fibers, those having a number average fiber diameter of 3
to 30 urn, a weight average fiber length of 100 to 750 µm,
and an aspect ratio (L/D) of number average fiber length
to number average fiber diameter of from 10 to 100 may be
preferably used from the perspective of exhibiting high
properties.


Further, wollastonite is more preferred as the (B)
inorganic filler. Among wollastonites, a wollastonite
having a number average fiber diameter of 3 to 30 µm, a
weight average fiber length of 10 to 500 |xm, and an
aspect ratio (L/D) of from 3 to 100 may be more
preferably used.
In addition, as the (B) inorganic filler, talc, mica,
kaolin, silicon nitride and the like are more preferred.
Even among talc, mica, kaolin, silicon nitride and the
like, those having a number average fiber diameter of 0.1
to 3 µm may be more preferably used.
[0077]
Measurement of the number average fiber diameter and
the weight average fiber length of the inorganic filler
may be determined by dissolving a molded product of the
polyamide composition in a solvent in which the polyamide
dissolves, such as formic acid, arbitrarily selecting 100
or more, for example, of the inorganic filler particles
from the obtained insoluble component, and observing
these selected particles with an optical microscope, a
scanning electron microscope or the like.
[0078]
A method for producing the polyamide composition
according to the present embodiment is not especially
limited, as long as it is a method which mixes the above-
described (A) polyamide and (B) inorganic filler.


Examples of the method for mixing the polyamide and
the inorganic filler include mixing the polyamide and the
inorganic filler using a Henschel mixer or the like, then
feeding the resultant mixture to a melt kneader and
kneading, and blending the inorganic filler in the
polyamide turned into a melt state by a single-screw or
twin-screw extruder from a side feeder.
[0079]
The method for feeding the components constituting
the polyamide composition may be carried out by feeding
all of the constituent components all at once to the same
feed opening, or by feeding from different feed openings
for each constituent component.
The melt kneading temperature is preferably about
250 to 375°C at a resin temperature.
The melt kneading time is preferably about 0.5 to 5
minutes.
The apparatus for performing the melt kneading is
not especially limited. Known apparatuses, for example,
a melt kneader such as a single-screw or twin-screw
extruder, a Banbury mixer, and a mixing roll, may be used.
[0080]
A blend amount of the (B) inorganic filler is
preferably 0.1 to 200 parts by mass, more preferably 1 to
180 parts by mass, and still more preferably 5 to 150
parts by mass, based on 100 parts by mass of the (A)
polyamide.


By setting the blend amount to 0.1 parts by mass or
more, mechanical properties such as toughness and
rigidity of the polyamide composition improve in a good
manner. Further, by setting the blend amount to 200
parts by mass or less, a polyamide composition having
excellent moldability can be obtained.
[0081]
To the extent that the object of the present
embodiment is not harmed, the polyamide composition
comprising the (B) inorganic filler may comprise
additives which are customarily used in polyamides, such
as a pigment, a dye, a fire retardant, a lubricant, a
fluorescent bleaching agent, a plasticizing agent, an
organic antioxidant, a stabilizer, an ultraviolet
absorber, a nucleating agent, rubber, and a reinforcement.
[0082]
A relative viscosity ηr at 25°C, A melting point Tm2,
and A glass transition temperature Tg of the polyamide
composition comprising the (B) inorganic filler according
to the present embodiment can be measured by the same
methods as the measurement methods for the above-
described polyamide. Further, by setting the measurement
values for the polyamide composition comprising the (B)
inorganic filler in the same ranges as the ranges
preferred for the measurement values of the above-
described polyamide, a polyamide composition having


excellent heat resistance, moldability, and chemical
resistance can be obtained.
[0083]
The polyamide composition comprising the (B)
inorganic filler preferably has a melt shear viscosity r\s
of 30 to 200 Pa-s, more preferably 40 to 180 Pa-s, and
still more preferably 50 to 150 Pa-s.
The melt shear viscosity can be measured based on
the method described in the below examples.
By setting the melt shear viscosity to be in the
above-described range, a polyamide composition having
excellent fluidity can be obtained.
[0084]
The polyamide composition comprising the (B)
inorganic filler preferably has a tensile strength of 140
MPa or more, more preferably 150 MPa or more, and still
more preferably 160 MPa or more.
Measurement of the tensile strength can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile strength to be 140 MPa or
more, a polyamide composition having excellent rigidity
can be obtained.
[0085]
The polyamide composition comprising the (B)
inorganic filler preferably has a tensile elongation of
1.0% or more, more preferably 1.5% or more, and still
more preferably 2.0% or more.


Measurement of the tensile elongation can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile elongation to be 1.0% or more,
a polyamide composition having excellent toughness can be
obtained.
[0086]
The polyamide composition comprising the (B)
inorganic filler preferably has a water absorbance of
5.0% or less, more preferably 4.0% or less, and still
more preferably 3.0% or less.
Measurement of the water absorbance can be carried
out based on the method described in the below examples.
By setting the water absorbance to be 5.0% or less,
a polyamide composition having excellent low water
absorbance can be obtained.
[0087]
(C) Copper compound and metal halide
The polyamide composition according to the present
embodiment is a polyamide composition which comprises the
above-described (A) polyamide and a (C) copper compound
and metal halide.
As a polyamide composition, by comprising a (C)
copper compound and metal halide, a polyamide composition
can be obtained having excellent heat resistance,
fluidity, toughness, low water absorbance, and rigidity,
as well as excellent heat aging resistance, without
harming the polyamide qualities of having excellent heat


resistance, fluidity, toughness, low water absorbance,
rigidity and the like.
[0088]
Examples of the copper compound used in the present
embodiment include copper halide, copper acetate, copper
propionate, copper benzoate, copper adipate, copper
terephthalate, copper isophthalate, copper salicylate,
copper nicotinate, copper stearate, and copper complex
salts coordinated to a chelating agent such as
ethylenediamine, and ethylenediaminetetraacetic acid.
[0089]
As the copper compound, preferred are copper iodide,
copper(I) bromide, copper(II) bromide, copper(I) chloride,
and copper acetate, and more preferred are copper iodide
and/or copper acetate, due to their excellent heat aging
resistance and ability to suppress metal corrosion of the
screw and cylinder parts (hereinafter, sometimes referred
to as "metal corrosion") during extrusion.
As the copper compound, one kind may be used, or two
or more kinds may be used in combination.
[0090]
A blend amount of the copper compound in the
polyamide composition is preferably 0.01 to 0.6 parts by
mass, and more preferably 0.02 to 0.4 parts by mass,
based on 100 parts by mass of the (A) polyamide.
By setting the blend amount of the copper compound
in the above-described range, sufficient heat aging


resistance improves and copper precipitation and metal
corrosion can be suppressed.
[0091]
It is preferred to comprise the copper compound so
that, based on 106 parts by mass of the polyamide, the
copper content is preferably 50 to 2,000 parts by mass,
more preferably 100 to 1,500 parts by mass, and still
more preferably 150 to 1,000 parts by mass.
By comprising 50 to 2,000 parts by mass of copper in
the polyamide composition, a polyamide composition having
excellent heat aging resistance can be obtained.
[0092]
Examples of the metal halide used in the present
embodiment exclude copper halides.
The metal halide is a salt of a Group 1 or 2 metal
element in the periodic table with a halogen. Examples
thereof include potassium iodide, potassium bromide,
potassium chloride, sodium iodide, and sodium chloride.
Potassium iodide and potassium bromide are preferred.
As the metal halide, one kind may be used, or two or
more kinds may be used in combination.
Potassium iodide is preferred as the metal halide,
due to its excellent heat aging resistance and ability to
suppress metal corrosion.
[0093]
A blend amount of the metal halide in the polyamide
composition is preferably 0.05 to 20 parts by mass, and


more preferably 0.2 to 10 parts by mass, based on 100
parts by mass of the (A) polyamide.
By setting the blend amount of the metal halide in
the above-described range, sufficient heat aging
resistance improves and copper precipitation and metal
corrosion can be suppressed.
[0094]
It is preferred to comprise the copper compound and
the metal halide in the polyamide composition so that the
ratio between the copper compound and the metal halide
has a halogen and copper molar ratio (halogen/copper) of
from 2/1 to 50/1. The halogen and copper molar ratio
(halogen/copper) is more preferably 2/1 to 40/1, and
still more preferably 5/1 to 30/1.
It is preferred that the halogen and copper molar
ratio is 2/1 or more, because copper precipitation and
metal corrosion can be suppressed. Further, if the
halogen and copper molar ratio is 50/1 or less, the
problem of corrosion of the molding machine screw and the
like can be suppressed, without harming mechanical
properties such as toughness and rigidity.
[0095]
Although advantageous effects can be obtained even
if the copper compound and the metal halide are
respectively used by themselves, in the present
embodiment it is preferred to blend both of these


components in order to improve the performance of the
obtained polyamide composition.
[0096]
Examples of the method for producing the polyamide
composition according to the present embodiment include,
for example, adding the (C) copper compound and metal
halide individually or as a mixture during the
polymerization step of the (A) polyamide (hereinafter,
sometimes abbreviated as "production method 1"), and
adding the (C) copper compound and metal halide
individually or as a mixture to the (A) polyamide using
melt kneading (hereinafter, sometimes abbreviated as
"production method 2").
[0097]
In the method for producing the polyamide
composition, when adding the (C) copper compound and
metal halide, these may be added as is as a solid or in
an aqueous solution state.
The "polymerization step of the polyamide" in
production method 1 refers to any of the steps until
completion of polymerization of the polyamide from the
raw material monomers. The addition may be carried out
at any stage.
The apparatus for performing the melt kneading in
production method 2 is not especially limited. Known
apparatuses, for example, a melt kneader such as single-


screw or twin-screw extruder, a Banbury mixer, and a
mixing roll, may be used.
Of these, it is preferred to use a twin-screw
extruder.
The melt kneading temperature is preferably a
temperature about 1 to 100°C higher than the melting
point of the (A) polyamide, and more preferably about 10
to 50°C higher.
A shear rate in the kneader is preferably about 100
sec-1 or more. An average dwell time during the kneading
is preferably about 0.5 to 5 minutes.
[0098]
To the extent that the object of the present
embodiment is not harmed, other additives may be added
for dispersing the copper compound and the metal halide
in the polyamide.
Examples of these other additives include, as a
lubricant, higher fatty acids such as lauryl acid, higher
fatty acid metal salts of a higher fatty acid and a metal
such as aluminum, higher fatty acid amides such as N,N-
ethylenebis(stearamide), and waxes such as polyethylene
wax.
Further examples thereof include organic compounds
having at least one amide group.
[0099]
By further comprising the (B) inorganic filler in
the polyamide composition comprising the (C) copper


compound and metal halide, a polyamide composition having
even better mechanical properties, such as toughness and
rigidity, can be obtained.
A blend amount of the inorganic filler is preferably
0.1 to 200 parts by mass, more preferably 1 to 180 parts
by mass, and still more preferably 5 to 150 parts by mass,
based on 100 parts by mass of the polyamide.
By setting the blend amount of the inorganic filler
to 0.1 parts by mass or more, mechanical properties such
as toughness and rigidity of the polyamide composition
improve in a good manner. Further, by setting the blend
amount of the inorganic filler to 200 parts by mass or
less, a polyamide composition having excellent
moldability can be obtained.
[0100]
To the extent that the object of the present
embodiment is not harmed, the polyamide composition
comprising the (C) copper compound and metal halide may
comprise additives which are customarily used in
polyamides, such as a pigment, a dye, a fire retardant, a
lubricant, a fluorescent bleaching agent, a plasticizing
agent, an organic antioxidant, a stabilizer, an
ultraviolet absorber, a nucleating agent, rubber, and a
reinforcement.
[0101]
A relative viscosity r|r at 25°C, a melting point Tm2,
and a glass transition temperature Tg of the polyamide


composition comprising the (C) copper compound and metal
halide according to the present embodiment can be
measured by the same methods as the measurement methods
for the above-described polyamide. Further, by setting
the measurement values for the polyamide composition
comprising the (C) copper compound and metal halide in
the same ranges as the ranges preferred for the
measurement values of the above-described polyamide, a
polyamide composition having excellent heat resistance,
moldability, and chemical resistance can be obtained.
[0102]
The polyamide composition comprising the (C) copper
compound and metal halide preferably has a melt shear
viscosity T|s of 30 to 200 Pa-s, more preferably 40 to 180
Pa-s, and still more preferably 50 to 150 Pa-s.
The melt shear viscosity can be measured based on
the method described in the below examples.
By setting the melt shear viscosity to be in the
above-described range, a polyamide composition having
excellent fluidity can be obtained.
[0103]
The polyamide composition comprising the (C) copper
compound and metal halide preferably has a tensile
strength of 140 MPa or more, more preferably 150 MPa or
more, and still more preferably 160 MPa or more.
Measurement of the tensile strength can be carried
out based on ASTM D638 as described in the below examples.


By setting the tensile strength to be 140 MPa or
more, a polyamide composition having excellent rigidity
can be obtained.
[0104]
The polyamide composition comprising the (C) copper
compound and metal halide preferably has a tensile
elongation of 1.0% or more, more preferably 1.5% or more,
and still more preferably 2.0% or more.
Measurement of the tensile elongation can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile elongation to be 1.0% or more,
a polyamide composition having excellent toughness can be
obtained.
[0105]
The polyamide composition comprising the (C) copper
compound and metal halide preferably has a water
absorbance of 5.0% or less, more preferably 4.0% or less,
and still more preferably 3.0% or less.
Measurement of the water absorbance can be carried
out based on the method described in the below examples.
By setting the water absorbance to be 5.0% or less,
a polyamide composition having excellent low water
absorbance can be obtained.
[0106]
The polyamide composition comprising the (C) copper
compound and metal halide preferably has, as a molded
product, a strength half-life of 40 days or more, more


preferably 45 days or more, and still more preferably 50
days or more.
Measurement of the strength half-life can be carried
out based on the method described in the below examples.
By setting the strength half-life to be 40 days or
more, a polyamide composition having excellent heat
resistance, and especially excellent heat aging
resistance, can be obtained.
[0107]
The polyamide composition comprising the (C) copper
compound and metal halide preferably has a breaking
stress of 45 MPa or more, more preferably 50 MPa or more,
and still more preferably 55 MPa or more.
Measurement of the breaking stress can be carried
out based on the method described in the below examples.
By molding a polyamide composition having a breaking
stress of 45 MPa or more, a polyamide composition having
excellent vibration fatigue resistance can be obtained.
[0108]
The polyamide composition comprising the (C) copper
compound and metal halide preferably has a tensile
strength retention rate after dipping of 60% or more,
more preferably 75% or more, and still more preferably
80% or more.
Measurement of the tensile strength retention rate
after dipping can be carried out based on the method
described in the below examples.


By molding a polyamide composition having a tensile
strength retention rate after dipping of 60% or more, a
polyamide composition having excellent LLC resistance can
be obtained.
[0109]
(D) Halogen-based flame retardant
The polyamide composition according to the present
embodiment is a polyamide composition which comprises the
above-described (A) polyamide and a (D) halogen-based
flame retardant.
As the polyamide composition according to the
present embodiment, by comprising the (D) halogen-based
flame retardant, a polyamide composition can be obtained
having excellent heat resistance, fluidity, toughness,
rigidity, and low water absorbance, as well as excellent
flame resistance, without harming the polyamide qualities
of having excellent heat resistance, fluidity, toughness,
rigidity, and low water absorbance.
Further, even though the polyamide composition
according to the present embodiment comprises a halogen-
based flame retardant, it has excellent light fastness,
and even has excellent color tone as a polyamide
composition.
[0110]
The (D) halogen-based flame retardant used in the
present embodiment is not especially limited, as long as
it is a flame retardant which comprises a halogen element.


Examples thereof include chlorine-based flame retardants
and bromine-based flame retardants, for example.
As such a flame retardant, one kind may be used, or
two or more kinds may be used in combination.
[0111]
Examples of chlorine-based flame retardants include
chlorinated paraffin, chlorinated polyethylene,
dodecachloropentacyclooctadeca-7,15-diene (Dechlorane
Plus 25®, manufactured by Occidental Corporation), and
HET anhydride.
[0112]
Examples of bromine-based flame retardants include
hexabromocyclododecane (HBCD) , decabromodiphenyl oxide
(DBDPO), octabromodiphenyl oxide, tetrabromobisphenol A
(TBBA), bis(tribromophenoxy)ethane,
bis(pentabromophenoxy)ethane (BPBPE), a
tetrabromobisphenol A epoxy resin (TBBA epoxy), a
tetrabromobisphenol A carbonate (TBBA-PC),
ethylene(bistetrabromophthal)imide (EBTBPI) ,
ethylenebispentabromodiphenyl,
tris(tribromophenoxy)triazine (TTBPTA),
bis(dibromopropyl)tetrabromobisphenol A (DBP-TBBA),
bis(dibromopropyl)tetrabromobisphenol S (DBP-TBBS),
brominated polyphenylene ether (including
poly(di)bromophenylene ether etc.) (BrPPE), brominated
polystyrene (including polydibromostyrene,
polytribromostyrene, crosslinked brominated polystyrene


etc.) (BrPS), brominated crosslinked aromatic polymers,
brominated epoxy resins, brominated phenoxy resins,
brominated styrene-maleic anhydride polymers,
tetrabromobisphenol S (TBBS),
tris(tribromoneopentyl)phosphate (TTBNPP),
polybromotrimethylphenylindan (PBPI), and
tris(dibromopropyl)-isocyanurate (TDBPIC).
[0113]
From the perspective that an amount of corrosive
gases produced during melt processing such as extrusion
and molding is low, exhibition of flame resistance, and
mechanical properties such as toughness and rigidity, the
(D) halogen-based flame retardant is preferably a
brominated polyphenylene ether (including
poly(di)bromophenylene ether etc.) and a brominated
polystyrene (including polydibromostyrene,
polytribromostyrene, crosslinked brominated polystyrene
etc.). A brominated polystyrene is more preferred.
[0114]
The brominated polystyrene is not especially limited,
and may be produced, for example, by polymerizing a
styrene monomer to produce a polystyrene, and then
brominating a benzene ring on the polystyrene.
Alternatively, the brominated polystyrene may be produced
by polymerizing a brominated styrene monomer
(bromostyrene, dibromostyrene, tribromostyrene etc.).


A bromine content in the brominated polystyrene is
preferably 55 to 75 mass%. By setting the bromine
content to 55 mass% or more, the bromine amount required
for achieving flame resistance can be satisfied with a
small brominated polystyrene blend amount, and a
polyamide composition having excellent heat resistance,
fluidity, toughness, low water absorbance, and rigidity,
as well as excellent flame resistance, can be obtained
without harming the qualities possessed by a polyamide.
Further, by setting the bromine content to 75 mass% or
less, a polyamide composition can be obtained which is
not easily pyrolyzed during melt processing such as
extrusion and molding, can suppress gas occurrence and
the like, and has excellent resistance to heat
discoloration.
[0115]
The polyamide composition comprising the (D)
halogen-based flame retardant may also further comprise
any of a (G) flame retardant auxiliary, a (H) polymer
comprising an α,β-unsaturated dicarboxylic acid anhydride,
and the (B) inorganic filler.
[0116]
By further comprising the (G) flame retardant
auxiliary in the polyamide composition comprising the (D)
halogen-based flame retardant, a polyamide composition
having even better flame resistance can be obtained.


The (G) flame retardant auxiliary used in the
present embodiment is not especially limited. Examples
thereof may include antimony oxides such as diantimony
trioxide, diantimony tetroxide, diantimony pentoxide, and
sodium antimonate; tin oxides such as tin monoxide and
tin dioxide; iron oxides such as iron (II) oxide and γ-
iron oxide; other metal oxides such as zinc oxide, zinc
borate, calcium oxide, aluminum oxide (alumina), aluminum
oxide (boehmite), silicon oxide (silica), titanium oxide,
zirconium oxide, manganese oxide, molybdenum oxide,
cobalt oxide, bismuth oxide, chromium oxide, tin oxide,
nickel oxide, copper oxide, and tungsten oxide; metal
hydroxides such as magnesium hydroxide and aluminum
hydroxide; metal powders of aluminum, iron, titanium,
manganese, zinc, molybdenum, cobalt, bismuth, chromium,
tin, antimony, nickel, copper, tungsten and the like;
metal carbonates such as zinc carbonate, calcium
carbonate, magnesium carbonate, and barium carbonate;
metal borates such as magnesium borate, calcium borate,
aluminum borate; and silicone.
As the (G) flame retardant auxiliary, one kind may
be used, or two or more kinds may be used in combination.
[0117]
From the perspective of the flame resistance effect,
the (G) flame retardant auxiliary used along with the (D)
halogen-based flame retardant is preferably an antimony
oxide such as diantimony trioxide, diantimony tetroxide,


diantimony pentoxide, and sodium antimonate, a tin oxide
such as tin monoxide and tin dioxide, an iron oxide such
as iron (II) oxide and γ-iron oxide, zinc oxide, and zinc
borate. More preferred are an antimony oxide such as
diantimony trioxide, diantimony tetroxide, and diantimony
pentoxide, and zinc borate, and still more preferred is
diantimony trioxide.
[0118]
To increase the flame retardance effect, it is
preferred to use a (G) flame retardant auxiliary having
an average particle size of 0.01 to 10 µm.
The average particle size may be measured using a
laser diffraction/scattering type particle size
distribution analyzer or a precise particle size
distribution analyzer.
[0119]
By further comprising the (H) polymer comprising the
α,β-unsaturated dicarboxylic acid anhydride in the
polyamide composition comprising the (D) halogen-based
flame retardant, a polyamide composition having excellent
flame resistance and also mechanical properties such as
toughness and rigidity can be obtained.
Examples of the (H) polymer comprising the α, β-
unsaturated dicarboxylic acid anhydride used in the
present embodiment include a polymer comprising the α, β-
unsaturated dicarboxylic acid anhydride as a copolymer


component, and a polymer modified with the α, β-
unsaturated dicarboxylic acid anhydride.
[0120]
Examples of the α,β-unsaturated dicarboxylic acid
anhydride include the compounds represented by the
following general formula (1).
General formula (1)

In general formula (1), R1 and R2 are each
independently a hydrogen or an alkyl group having 1 to 3
carbon atoms.
[0121]
Examples of the α,β-unsaturated dicarboxylic acid
anhydride include maleic anhydride and methyl maleic
anhydride. Maleic anhydride is preferred.
Examples of the polymer comprising the α,β-
unsaturated dicarboxylic acid anhydride as a copolymer
component include a copolymer of an aromatic vinyl
compound and an α,β-unsaturated dicarboxylic acid
anhydride.
Examples of the polymer modified with the α,β-
unsaturated dicarboxylic acid anhydride include a
polyphenylene ether resin and a polypropylene resin

modified with an α,β-unsaturated dicarboxylic acid
anhydride.
[0122]
From the perspective of efficiency in improving
flame retardance (exhibiting flame retardance with a
small added amount), a copolymer of an aromatic vinyl
compound and an α,β-unsaturated dicarboxylic acid
anhydride is preferred as the (H) polymer comprising an
α,β-unsaturated dicarboxylic acid anhydride.
[0123]
Examples of the aromatic vinyl compound used in the
present embodiment include the compounds represented by
the following general formula (2).
General formula (2)

In general formula (2), R3 and R4 are each
independently a hydrogen or an alkyl group having 1 to 3
carbon atoms, and k denotes an integer of 1 to 5.
[0124]
Examples of the aromatic vinyl compound include
styrene, α-methylstyrene, and p-methylstyrene. Styrene
is preferred.
In the present embodiment, when the polymer
comprising the α,β-unsaturated dicarboxylic acid
anhydride comprises the aromatic vinyl compound component,

it is thought that the aromatic vinyl compound component
has an affinity with the halogen-based flame retardant
(brominated polystyrene etc.), and assists in the
dispersion of the halogen-based flame retardant in the
polyamide matrix, thereby allowing finer dispersion of
the halogen-based flame retardant, due to the α,β-
unsaturated dicarboxylic acid anhydride component having
an affinity with or reacting with the polyamide.
[0125]
From perspectives such as flame resistance, fluidity,
and resistance to pyrolysis, the ratio of the aromatic
vinyl compound component and the α,β-unsaturated
dicarboxylic acid anhydride component in the copolymer of
the aromatic vinyl compound and the α,β-unsaturated
dicarboxylic acid anhydride is preferably set so that the
aromatic vinyl compound component is 50 to 99 mass%, and
the α,β-unsaturated dicarboxylic acid anhydride component
is 1 to 50 mass%. The ratio of the α,β-unsaturated
dicarboxylic acid anhydride component is more preferably
5 to 20 mass%, and still more preferably 8 to 15 mass%.
By setting the ratio of the α,β-unsaturated
dicarboxylic acid anhydride component to 1 mass% or more,
a polyamide composition having excellent mechanical
properties such as toughness and rigidity as well as
excellent flame resistance can be obtained. Further, by
setting the ratio of the α,β-unsaturated dicarboxylic
acid anhydride component to 50 mass% or less,


deterioration of the polyamide composition due to the
α,β-unsaturated dicarboxylic acid anhydride can be
prevented.
[0126]
By comprising the above-described (B) inorganic
filler in the polyamide composition comprising the (D)
halogen-based flame retardant, a polyamide composition
having excellent mechanical properties such as toughness
and rigidity can be obtained.
[0127]
A method for producing the polyamide composition
according to the present embodiment is not especially
limited, as long as the method mixes the above-described
(A) polyamide and the (D) halogen-based flame retardant.
Further, examples of the method for producing the
polyamide composition comprising the (D) halogen-based
flame retardant include a method in which the (G) flame
retardant auxiliary and the (H) polymer comprising the
α,β-unsaturated dicarboxylic acid anhydride and/or the
(B) inorganic filler are further mixed.
Examples of the method for mixing the polyamide and
the halogen-based flame retardant include mixing the
polyamide and the halogen-based flame retardant, and
optionally the flame retardant auxiliary, the polymer
comprising the α,β-unsaturated dicarboxylic acid
anhydride, and/or the inorganic filler, using a Henschel
mixer and the like, feeding the resultant mixture to a


melt kneader, and kneading. Another example thereof
includes forming in advance using a Henschel mixer and
the like a mixture of the polyamide and the halogen-based
flame retardant, and optionally the flame retardant
auxiliary and/or the polymer comprising the α,β-
unsaturated dicarboxylic acid anhydride with a single-
screw or a twin-screw extruder, feeding the resultant
mixture to a melt kneader, kneading, and then, optionally,
adding the inorganic filler from a side feeder.
[0128]
The method for feeding the components constituting
the polyamide can be carried out by feeding all of the
constituent components all at once to the same feed
opening, or by feeding from different feed openings for
each constituent component.
[0129]
The melt kneading temperature is preferably about
250 to 375°C at a resin temperature.
The melt kneading time is preferably about 0.5 to 5
minutes.
As the apparatus for performing the melt kneading,
it is preferred to use a known apparatus, for example a
melt kneader such as a single-screw or twin-screw
extruder, a Banbury mixer, and a mixing roll.
[0130]
A blend amount of the (D) halogen-based flame
retardant, and a blend amounts of the optional (G) flame


retardant auxiliary, (H) polymer comprising an α,β-
unsaturated dicarboxylic acid anhydride and/or (B)
inorganic filler, are not especially limited.
The blend amount of the halogen-based flame
retardant in the polyamide composition is preferably 30
to 60 parts by mass, more preferably 35 to 55 parts by
mass, and still more preferably 40 to 50 parts by mass,
based on 100 parts by mass of the polyamide.
By setting the blend amount of the halogen-based
flame retardant to be 30 parts by mass or more, a
polyamide composition having excellent heat resistance
can be obtained. Further, by setting the blend amount of
the halogen-based flame retardant to be 60 parts by mass
or less, the occurrence of decomposition gases during
melt kneading, deterioration in fluidity during molding
processing, and adherence of a contaminating substance to
the mold die can be suppressed. In addition,
deterioration in mechanical properties such as toughness
and rigidity and deterioration in the molded product
appearance can be suppressed.
[0131]
A blend amount of the flame retardant auxiliary in
the polyamide composition is preferably 0 to 30 parts by
mass, more preferably 1 to 30 parts by mass, still more
preferably 2 to 20 parts by mass, and even still more
preferably 4 to 15 parts by mass, based on 100 parts by
mass of the polyamide.


By blending the flame retardant auxiliary, a
polyamide composition having even better flame resistance
can be obtained. Further, by setting the blend amount of
the flame retardant auxiliary to be 30 parts by mass or
less, the viscosity during melt processing can be
controlled in a suitable range, an increase in torque
during extrusion can be suppressed, and deterioration in
moldability during molding processing and deterioration
in the molded product appearance can be suppressed.
Moreover, a polyamide composition having excellent
toughness and the like can be obtained without harming
the polyamide qualities of having excellent mechanical
properties such as toughness and rigidity.
[0132]
A blend amount of the polymer comprising an α,β-
unsaturated dicarboxylic acid anhydride in the polyamide
composition is preferably 0 to 20 parts by mass, more
preferably 0.5 to 20 parts by mass, still more preferably
1 to 15 parts by mass, and even still more preferably 2
to 10 parts by mass, based on 100 parts by mass of the
polyamide.
By blending the polymer comprising the α,β-
unsaturated dicarboxylic acid anhydride, the fine
dispersion effects of the halogen-based flame retardant
in the polyamide due to compatibilizing effect can be
increased, so that a polyamide composition having an
excellent effect in improving flame resistance and


strength can be obtained. Further, by setting the blend
amount of the polymer comprising the α,β-unsaturated
dicarboxylic acid anhydride to be 20 parts by mass or
less, a polyamide composition having excellent strength
and the like can be obtained without harming the
polyamide qualities of having excellent mechanical
properties such as toughness and rigidity.
[0133]
A blend amount of the inorganic filler in the
polyamide composition is preferably 0 to 200 parts by
mass, more preferably 0.1 to 200 parts by mass, still
more preferably 1 to 180 parts by mass, and even still
more preferably 5 to 150 parts by mass based on 100 parts
by mass of the polyamide.
By blending the inorganic filler, mechanical
properties such as toughness and rigidity of the
polyamide composition improve in a good manner. Further,
by setting the blend amount of the inorganic filler to
200 parts by mass or less, a polyamide composition having
excellent moldability can be obtained.
[0134]
To the extent that the object of the present
embodiment is not harmed, the polyamide composition
comprising the (D) halogen-based flame retardant may
comprise additives which are customarily used in
polyamides, such as a pigment, a dye, a fire retardant, a
lubricant, a fluorescent bleaching agent, a plasticizing


agent, an organic antioxidant, a stabilizer, an
ultraviolet absorber, a nucleating agent, rubber, and a
reinforcement.
[0135]
A relative viscosity ηr at 25°C, a melting point Tm2,
and a glass transition temperature Tg of the polyamide
composition comprising the (D) halogen-based flame
retardant according to the present embodiment can be
measured by the same methods as the measurement methods
for the above-described polyamide. Further, by setting
the measurement values for the polyamide composition
comprising the (D) halogen-based flame retardant in the
same ranges as the ranges preferred for the measurement
values of the above-described polyamide, a polyamide
composition having excellent heat resistance, moldability,
mechanical properties such as toughness and rigidity, and
chemical resistance can be obtained.
[0136]
The polyamide composition comprising the (D)
halogen-based flame retardant preferably has a tensile
strength of 140 MPa or more, more preferably 150 MPa or
more, and still more preferably 160 MPa or more.
Measurement of the tensile strength can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile strength to be 140 MPa or
more, a polyamide composition having excellent rigidity
can be obtained.


[0137]
The polyamide composition comprising the (D)
halogen-based flame retardant preferably has a tensile
elongation of 1.0% or more, more preferably 1.5% or more,
and still more preferably 2.0% or more.
Measurement of the tensile elongation can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile elongation to be 1.0% or more,
a polyamide composition having excellent toughness can be
obtained.
[0138]
The polyamide composition comprising the (D)
halogen-based flame retardant preferably has a water
absorbance of 5.0% or less, more preferably 4.0% or less,
and still more preferably 3.0% or less.
Measurement of the water absorbance can be carried
out based on the method described in the below examples.
By setting the water absorbance to be 5.0% or less,
a polyamide composition having excellent low water
absorbance can be obtained.
[0139]
The flame resistance of the polyamide composition
comprising the (D) halogen-based flame retardant is
measured based on UL-94VB.
The polyamide composition preferably has a flame
resistance of V-2 or more, more preferably V-l or more,
and more preferably V-0.


[0140]
The polyamide composition comprising the (D)
halogen-based flame retardant preferably has a flow
length of 15 cm or more, more preferably 17 cm or more,
and still more preferably 20 cm or more.
The flow length can be measured by the method
described in the below examples.
By setting the flow length to 15 cm or more, a
polyamide composition having excellent fluidity can be
obtained.
[0141]
(E) Phosphinate and/or diphosphinic acid
The polyamide composition according to the present
embodiment is a polyamide composition comprising the
above-described (A) polyamide and an (E) phosphinate
and/or diphosphinate (hereinafter, sometimes collectively
referred to as "phosphinate").
Examples of phosphinic acid include the compounds
represented by the following general formula (I).
General formula (I)

Examples of diphosphinic acid include the compounds
represented by the following general formula (II).
General formula (II)


In general formulae (I) and (II), R5 and R6, and R7
and R8, are each independently selected from the group
consisting of an alkyl group having 1 to 6 carbon atoms,
an aryl group having 6 to 12 carbon atoms, and an
arylalkyl group having 7 to 20 carbon atoms. R9 is
selected from the group consisting of an alkylene group
having 1 to 10 carbon atoms, an arylene group having 6 to
10 carbon atoms, an alkylarylene group having 7 to 20
carbon atoms, and an arylalkylene group having 7 to 20
carbon atoms. M is selected from the group consisting of
calcium (ion), magnesium (ion), aluminum (ion), and zinc
(ion), m is 2 or 3, n is 1 or 3, and x is 1 or 2.
[0142]
In the present embodiment, examples of the alkyl
group include straight-chain or branched saturated
aliphatic groups.
In the present embodiment, examples of the aryl
group include aromatic groups, which are unsubstituted or
substituted with various substituents, having 6 to 20
carbon atoms, such as a phenyl group, a benzyl group, an
o-toluyl group, and a 2,3-xylyl group.
[0143]

As the polyamide composition according to the
present embodiment, by comprising the (E) phosphinate, a
polyamide composition can be obtained having excellent
heat resistance, fluidity, toughness, low water
absorbance, and rigidity, as well as having excellent
flame resistance, without harming the polyamide qualities
of having excellent heat resistance, fluidity, toughness,
low water absorbance, and rigidity.
Further, the polyamide composition according to the
present embodiment also has excellent light fastness and
color tone as a polyamide composition, despite inclusion
of the phosphinate.
[0144]
The (E) phosphinate used in the present embodiment
can be produced in an aqueous solution using phosphinic
acid and a metal component, such as a metal carbonate, a
metal hydroxide, or a metal oxide, as described in
European Patent Application Publication No. 699708 and
Japanese Patent Laid-Open No. 8-73720.
Although such compounds are essentially monomeric
compounds, depending on the reaction conditions,
polymeric phosphinates having a degree of condensation of
1 to 3 based on the environment are also included.
[0145]
Examples of the phosphinic acid and diphosphinic
acid for the (E) phosphinate include dimethylphosphinic
acid, ethylmethylphosphinic acid, diethylphosphinic acid,


methyl-n-propylphosphinic acid,
methanedi(methylphosphinic acid), benzene-1,4-di
(methylphosphinic acid), methylphenylphosphinic acid, and
diphenylphosphinic acid.
[0146]
Examples of the metal component for the (E)
phosphinate include a calcium ion, a magnesium ion, an
aluminum ion, and a zinc ion.
[0147]
Examples of the (E) phosphinate 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
methylenebis(methylphosphinate), magnesium
methylenebis(methylphosphinate), aluminum
methylenebis(methylphosphinate) , zinc
methylenebis(methylphosphinate), calcium phenylene-1,4-
bis(methylphosphinate), magnesium phenylene-1,4-
bis(methylphosphinate), aluminum phenylene-1,4-


bis(methylphosphinate), zinc phenylene-1,4-
bis(methylphosphinate),
calcium methylphenylphosphinate, magnesium
methylphenylphosphinate, aluminum methylphenylphosphinate,
zinc methylphenylphosphinate,
calcium diphenylphosphinate, magnesium
diphenylphosphinate, aluminum diphenylphosphinate, and
zinc diphenylphosphinate.
As the (E) phosphinate, one kind may be used, or two
or more kinds may be used in combination.
[0148]
From the perspectives of the flame resistance and
the electric properties of the polyamide composition, and
also from the perspective of phosphinate synthesis, the
(E) phosphinate is preferably calcium dimethylphosphinate,
aluminum dimethylphosphinate, zinc dimethylphosphinate,
calcium ethylmethylphosphinate, aluminum
ethylmethylphosphinate, zinc ethylmethylphosphinate,
calcium diethylphosphinate, aluminum diethylphosphinate,
and zinc diethylphosphinate.
[0149]
From the perspectives of mechanical properties such
as toughness and rigidity and of the appearance of the
molded product obtained by molding the polyamide
composition, it is preferred to use the (E) phosphinate
as a powder ground to a particle size of 100 µm or less,


and more preferably as a powder ground to a particle size
of from 50 µm or less.
It is preferred to use the (E) phosphinate as a
powder having a particle size of 0.5 to 20 µm, because
not only does this allow a polyamide composition which
exhibits high flame resistance to be obtained, but the
strength of the molded product is also substantially
increased.
The average particle size may be measured using a
laser diffraction/scattering type particle size
distribution analyzer or a precise particle size
distribution analyzer.
[0150]
The (E) phosphinate does not have to be a completely
pure. It is acceptable for certain amounts of unreacted
products or byproducts to remain.
[0151]
The polyamide composition comprising the (E)
phosphinate may also further comprise any of the (G)
flame retardant auxiliary and the (B) inorganic filler.
By further comprising the (G) flame retardant
auxiliary in the polyamide composition comprising the (E)
phosphinate, a polyamide composition having even better
flame resistance can be obtained.
The (G) flame retardant auxiliary is not especially
limited, as long as it a flame retardant auxiliary
described above. Of those, preferred are metal oxides


such as zinc oxide, iron oxide, calcium oxide, aluminum
oxide (alumina), aluminum oxide (boehmite), silicon oxide
(silica), titanium oxide, zirconium oxide, manganese
oxide, molybdenum oxide, cobalt oxide, bismuth oxide,
chromium oxide, tin oxide, antimony oxide, nickel oxide,
copper oxide, and tungsten oxide, metal hydroxides such
as magnesium hydroxide and aluminum hydroxide, metal
powders of aluminum, iron, titanium, manganese, zinc,
molybdenum, cobalt, bismuth, chromium, tin, antimony,
nickel, copper, tungsten and the like, metal carbonates
such as zinc carbonate, calcium carbonate, magnesium
carbonate, and barium carbonate, metal borates such as
zinc borate, magnesium borate, calcium borate, aluminum
borate, and silicone.
As the (G) flame retardant auxiliary, one kind may
be used, or two or more kinds may be used in combination.
[0152]
From the perspective of flame resistance, as the (G)
flame retardant auxiliary used with the (E) phosphinate,
preferred are calcium oxide, aluminum oxide (alumina),
aluminum hydroxide (boehmite), magnesium hydroxide, and
zinc borate.
As the zinc borate, more preferred is a zinc borate
represented by xZnO.yB2O3-zH2O (wherein x > 0, y > 0, and z
> 0). Still more preferred are 2ZnO-3B2O3.3. 5H2O,
4ZnOB2O3-H2O, and 2ZnO3B2O3.


These zinc borate compounds may be treated with a
surface treatment agent such as a silane coupling agent
and a titanate coupling agent.
The flame retardant auxiliary preferably has a
particle size of 30 µm or less, more preferably 15 µm or
less, and still more preferably 7 µm or less.
[0153]
A blend amount of the (E) phosphinate and a blend
amounts of the optional (G) flame retardant auxiliary
and/or (B) inorganic filler, in the polyamide composition
according to the present embodiment are not especially
limited.
The blend amount of the phosphinate in the polyamide
composition is preferably 20 to 90 parts by mass, more
preferably 25 to 80 parts by mass, and still more
preferably 30 to 60 parts by mass, based on 100 parts by
mass of the polyamide.
By setting the blend amount of the phosphinate to be
20 parts by mass or more, a polyamide composition having
excellent flame resistance can be obtained. Further, by
setting the blend amount of the phosphinate to be 90
parts by mass or less, deterioration in fluidity during
molding processing can be suppressed. In addition,
deterioration in mechanical properties such as toughness
and rigidity and deterioration in the molded product
appearance can be suppressed.
[0154]


A blend amount of the flame retardant auxiliary in
the polyamide composition is preferably 0 to 30 parts by
mass, more preferably 1 to 30 parts by mass, still more
preferably 1 to 20 parts by mass, and even still more
preferably 2 to 15 parts by mass, based on 100 parts by
mass of the polyamide.
By blending the flame retardant auxiliary, a
polyamide composition having even better flame resistance
can be obtained. Further, by setting the blend amount of
the flame retardant auxiliary to be 30 parts by mass or
less, the viscosity during melt processing can be
controlled in a suitable range, an increase in torque
during extrusion can be suppressed, and deterioration in
moldability during molding processing and deterioration
in the molded product appearance can be suppressed.
Moreover, a polyamide composition having excellent
toughness can be obtained without harming the polyamide
qualities of having excellent mechanical properties such
as toughness and rigidity.
[0155]
A blend amount of the inorganic filler in the
polyamide composition is preferably 0 to 200 parts by
mass, more preferably 0.1 to 200 parts by mass, still
more preferably 1 to 180 parts by mass, and even still
more preferably 5 to 150 parts by mass, based on 100
parts by mass of the polyamide.


By further blending the inorganic filler, mechanical
properties such as toughness and rigidity of the
polyamide composition improve in a good manner. Further,
by setting the blend amount of the inorganic filler to
200 parts by mass or less, a polyamide composition having
excellent moldability can be obtained.
[0156]
To the extent that the object of the present
embodiment is not harmed, the polyamide composition
comprising the (E) phosphinate may comprise additives
which are customarily used in polyamides, such as a
pigment, a dye, a fire retardant, a lubricant, a
fluorescent bleaching agent, a plasticizing agent, an
organic antioxidant, a stabilizer, an ultraviolet
absorber, a nucleating agent, rubber, and a reinforcement.
[0157]
A relative viscosity ηr at 25°C, a melting point Tm2,
and a glass transition temperature Tg of the polyamide
composition comprising the (E) phosphinate can be
measured by the same methods as the measurement methods
for the above-described polyamide. Further, by setting
the measurement values for the polyamide composition
comprising the (E) phosphinate in the same ranges as the
ranges preferred for the measurement values of the above-
described polyamide, a polyamide composition having
excellent heat resistance, moldability, mechanical


properties such as toughness and rigidity, and chemical
resistance can be obtained.
[0158]
The polyamide composition comprising the (E)
phosphinate preferably has a tensile strength of 140 MPa
or more, more preferably 150 MPa or more, and still more
preferably 160 MPa or more.
Measurement of the tensile strength can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile strength to be 140 MPa or
more, a polyamide composition having excellent rigidity
can be obtained.
[0159]
The polyamide composition comprising the (E)
phosphinate preferably has a tensile elongation of 1.0%
or more, more preferably 1.5% or more, and still more
preferably 2.0% or more.
Measurement of the tensile elongation can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile elongation to be 1.0% or more,
a polyamide composition having excellent toughness can be
obtained.
[0160]
The polyamide composition comprising the (E)
phosphinate preferably has a water absorbance of 5.0% or
less, more preferably 4.0% or less, and still more
preferably 3.0% or less.


Measurement of the water absorbance can be carried
out based on the method described in the below examples.
By setting the water absorbance to be 5.0% or less,
a polyamide composition having excellent low water
absorbance can be obtained.
[0161]
A flame resistance of the polyamide composition
comprising the (E) phosphinate is measured based on UL-
94VB. The polyamide composition preferably has a flame
resistance of V-2 or more, more preferably V-1 or more,
and more preferably V-0.
[0162]
The polyamide composition comprising the (E)
phosphinate preferably has a full filling pressure of 15
to 50%, more preferably 18 to 48%, and still more
preferably 20 to 45%.
The full filling pressure can be measured by the
method described in the below examples.
By setting the full filling pressure in the above-
described range, a polyamide composition having excellent
fluidity can be obtained.
[0163]
(F) Stabilizer
The polyamide composition according to the present
embodiment is a polyamide composition which comprises the
above-described (A) polyamide and an (F) stabilizer.


As the polyamide composition according to the
present embodiment, by comprising the (F) stabilizer, a
polyamide composition can be obtained having excellent
heat resistance, fluidity, toughness, low water
absorbance, and rigidity, as well as excellent resistance
to heat discoloration and weatherability, without harming
the polyamide qualities of having excellent heat
resistance, fluidity, toughness, low water absorbance,
and rigidity.
[0164]
The (F) stabilizer used in the present embodiment is
at least one kind selected from the group consisting of
phenolic-based stabilizers, phosphite-based stabilizers,
hindered amine-based stabilizers, triazine-based
stabilizers, sulfur-based stabilizers, and inorganic
phosphorus-based stabilizers.
As the stabilizer, one kind may be used, or two or
more kinds may be used in combination.
[0165]
Examples of phenolic-based stabilizers are not
especially limited, and may include hindered phenol
compounds.
Examples of hindered phenol compounds include N,N'-
hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-
hydroxyphenylpropionamide)], pentaerythrityl-tetrakis[3-
(3,5-di-t-butyl-4-hydroxyphenyl) propionate], N,N'-
hexamethylenebis(3,5-di-t-butyl-4-hydroxy-


hydrocinnamamide), triethyleneglycol-bis[3-(3-t-butyl-5-
methyl-4-hydroxyphenyl) propionate], 3,9-bis{2-[3-(3-t-
butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-
dimethylethyl}-2,4,8,10-tetraoxaspiro[5, 5]undecane, 3,5-
di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester,
l,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-
hydroxybenzyl)benzene, and 1,3,5-tris(4-t-butyl-3-
hydroxy-2,6-dimethylbenzyl) isocyanurate.
As the phenolic-based stabilizer, one kind may be
used, or two or more kinds may be used in combination.
[0166]
Examples of phosphite-based stabilizers are not
especially limited, and may include trioctyl phosphite,
trilauryl phosphite, tridecyl phosphite, octyldiphenyl
phosphite, trisisodecyl phosphite, phenyl diisodecyl
phosphite, phenyl di(tridecyl) phosphite, diphenyl
isooctyl phosphite, diphenyl isodecyl phosphite,
diphenyl(tridecyl) phosphite, triphenyl phosphite,
tris(nonylphenyl) phosphite, tris(2,4-di-t-butylphenyl)
phosphite, tris(2,4-di-t-butyl-5-methylphenyl) phosphite,
tris(butoxyethyl) phosphite, 4, 4'-butylidene-bis(3-
methyl-6-t-butylphenyl-tetra-tridecyl) diphosphite,
tetra(C12 to C15 mixed alkyl)-4,4'-isopropylidenediphenyl
diphosphite, 4,4'-isopropylidenebis(2-t-butylphenyl)-
di(nonylphenyl) phosphite, tris(biphenyl) phosphite,
tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-
hydroxyphenyl)butane diphosphite, tetra(tridecyl)-4,4'-


butylidenebis(3-methyl-6-t-butylphenyl) diphosphite,
tetra(Cl to C15 mixed alkyl)-4,4'-isopropylidenediphenyl
diphosphite, tris(mono-di mixed nonylphenyl) phosphite,
4,4'-isopropylidenebis(2-t-butylphenyl)-di(nonylphenyl)
phosphite, 9,10-di-hydro-9-oxa-10-phosphorphenanthrene-
10-oxide, tris(3,5-di-t-butyl-4-hydroxyphenyl) phosphite,
hydrogenated-4,4'-isopropylidenediphenyl polyphosphite,
bis(octylphenyl)-bis(4,4'-butylidenebis(3-methyl-6-t-
butylphenyl)-1,6-hexanol diphosphite, hexa(tridecyl)-
1, 1, 3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane
triphosphite, tris(4,4'-isopropylidenebis(2-t-
butylphenyl) phosphite, tris(1, 3-stearoyloxyisopropyl)
phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl
phosphite, 2,2-methylenebis(3-methyl-4,6-di-t-
butylphenyl) 2-ethylhexyl phosphite, tetrakis(2,4-di-t-
butyl-5-methylphenyl)-4,4'-biphenylene diphosphite, and
tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene
diphosphite.
As the phosphite-based stabilizer, one kind may be
used, or two or more kinds may be used in combination.
[0167]
Examples of phosphite-based stabilizers may also
include pentaerythritol-type phosphite compounds.
Examples of pentaerythritol-type phosphite compounds
include 2,6-di-t-butyl-4-methylphenyl-phenyl-
pentaerythritol diphosphite, 2,6-di-t-butyl-4-
methylphenyl-methyl-pentaerythritol diphosphite, 2,6-di-


t-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritol
diphosphite, 2,6-di-t-butyl-4-methylphenyl-isodecyl-
pentaerythritol diphosphite, 2,6-di-t-butyl-4-
methylphenyl-lauryl-pentaerythritol diphosphite, 2,6-di-
t-butyl-4-methylphenyl-isotridecyl-pentaerythritol
diphosphite, 2,6-di-t-butyl-4-methylphenyl-stearyl-
pentaerythritol diphosphite, 2,6-di-t-butyl-4-
methylphenyl-cyclohexyl-pentaerythritol diphosphite, 2,6-
di-t-butyl-4-methylphenyl-benzyl-pentaerythritol
diphosphite, 2,6-di-t-butyl-4-methylphenyl-
ethylcellosolve-pentaerythritol diphosphite, 2,6-di-t-
butyl -4 -me thy lphenyl-butyl carbitol-pentaerythritol
diphosphite, 2,6-di-t-butyl-4-methylphenyl-octylphenyl-
pentaerythritol diphosphite, 2,6-di-t-butyl-4-
methylphenyl-nonylphenyl-pentaerythritol diphosphite,
bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol
diphosphite, bis(2,6-di-t-butyl-4-
ethylphenyl)pentaerythritol diphosphite, 2, 6-di-t-butyl-
4-methylphenyl-2,6-di-t-butylphenyl-pentaerythritol
diphosphite, 2,6-di-t-butyl-4-methylphenyl-2,4-di-t-
butylphenyl-pentaerythritol diphosphite, 2, 6-di-t-butyl-
4-methylphenyl-2,4-di-t-octylphenyl-pentaerythritol
diphosphite, 2,6-di-t-butyl-4-methylphenyl-2-
cyclohexylphenyl-pentaerythritol diphosphite, 2,6-di-t-
amyl-4-methylphenyl-phenyl-pentaerythritol diphosphite,
bis(2,6-di-t-amyl-4-methylphenyl)pentaerythritol


diphosphite, and bis(2,6-di-t-octyl-4-
methylphenyl)pentaerythritol diphosphite.
As the pentaerythritol-type phosphate-based
stabilizer, one kind may be used, or two or more kinds
may be used in combination.
[0168]
As the pentaerythritol-type phosphite compound,
bis(2, 6-di-t-butyl-4-methylphenyl)pentaerythritol
diphosphite, bis (2,6-di-t-butyl-4-
ethylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-
amyl-4-methylphenyl)pentaerythritol diphosphite, and
bis(2, 6-di-t-octyl-4-methylphenyl)pentaerythritol
diphosphite are preferable. Bis(2, 6-di-t-butyl-4-
methylphenyl)pentaerythritol diphosphite is more
preferable.
[0169]
Examples of the hindered amine-based stabilizer are
not especially limited, and may include 4-acetoxy-
2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-
tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-
tetramethylpiperidine, 4- (phenylacetoxy)-2,2,6,6-
tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-
tetramethylpiperidine, 4-methoxy-2,2,6,6-
tetramethylpiperidine, 4-stearyloxy-2,2,6,6-
tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-
tetramethylpiperidine, 4-benzyloxy-2,2,6,6-
tetramethylpiperidine, 4-phenoxy-2,2,6,6-


tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-
tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-
2,2, 6,6-tetramethylpiperidine, 4-(phenylcarbamoyloxy)-
2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-
piperidyl)-carbonate, bis(2,2,6,6-tetramethyl-4-
piperidyl)-oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl)-
malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate,
bis(2, 2, 6, 6-tetramethyl-4-piperidyl)-adipate,
bis(2,2,6,6-tetramethyl-4-piperidyl)-terephthalate, 1,2-
bis(2,2,6,6-tetramethyl-4-piperidyloxy)-ethane, α,α'-
bis(2,2,6, 6-tetramethyl-4-piperidyloxy)-p-xylene,
bis(2,2,6,6-tetramethyl-4-piperidyl)-tolylene-2,4-
dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl)-
hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl-
4-piperidyl)-benzene-1,3,5-tricarboxylate, tris (2,2,6,6-
tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate, 1-
[2-{3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionyloxy}butyl] -4-[3-(3, 5-di-t-butyl-4-
hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine,
and a condensation product of 1,2,3,4-
butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-
piperidinol, and β,β,β', β'-tetramethyl-3,9-[2,4,8,10-
tetraoxaspiro(5,5)undecane]diethanol.
As the hindered amine-based stabilizer, one kind may
be used, or two or more kinds may be used in combination.
[0170]


Examples of the triazine-based stabilizers are not
especially limited, and may include hydroxyphenyl
triazines.
Examples of the hydroxyphenyl triazines include
2,4, 6-tris(2'-hydroxy-4'-octyloxy-phenyl)-1,3,5-triazine,
2-(2'-hydroxy-4'-hexyloxy-phenyl)-4,6-diphenyl-1,3,5-
triazine, 2-(2'-hydroxy-4'-octyloxyphenyl)-4,6-bis(2',4-
dimethylphenyl)-1,3,5-triazine, 2- (2',4'-
dihydroxyphenyl)-4,6-bis(2',4'-dimethylphenyl)-1,3,5-
triazine, 2, 4-bis(2'-hydroxy-4'-propyloxy-phenyl)-6-
(2',4'-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis(4'-methylphenyl)-1,3,5-triazine,
2-(2'-hydroxy-4'-dodecyloxyphenyl)-4,6-bis (2 ',4'-
dimethylphenyl)-1,3,5-triazine, 2,4,6-tris(2'-hydroxy-4'-
isopropyloxyphenyl)-1,3,5-triazine, 2,4,6-tris(2'-
hydroxy-4'-n-hexyloxyphenyl)-1,3,5-triazine, and 2,4,6-
tris(2'-hydroxy-4'-ethoxycarbonylmethoxyphenyl)-1,3,5-
triazine.
As the triazine-based stabilizer, one kind may be
used, or two or more kinds may be used in combination.
[0171]
Examples of sulfur-based stabilizers are not
especially limited, and may include
pentaerythrityltetrakis(3-laurylthiopropionate),
dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-
thiodipropionate, and distearyl-3,3'-thiodipropionate.


As the sulfur stabilizer, one kind may be used, or
two or more kinds may be used in combination.
[0172]
Examples of inorganic phosphoros-based stabilizers
are not especially limited, and may include phosphoric
acids, phosphorous acids, hypophosphorous acids,
phosphoric acid metal salts, phosphorous acid metal salts,
and hypophosphorous acid metal salts.
[0173]
Examples of phosphoric acids, phosphorous acids, and
hypophosphorous acids include phosphoric acid,
phosphorous acid, hypophosphorous acid, pyrophosphorous
acid, and diphosphorous acid.
[0174]
Examples of the phosphoric acid metal salts,
phosphorous acid metal salts, and hypophosphorous acid
metal salts include salts formed from compounds of the
above-described phosphoric acids and the like with Group
1 metals in the periodic table.
[0175]
It is preferred that the inorganic phosphorus-based
stabilizer is a soluble compound. Examples thereof
include sodium phosphate, sodium phosphite, and sodium
hypophosphite. More preferred is sodium phosphite and
sodium hypophosphite, and still more preferred is sodium
hypophosphite.


The inorganic phosphorus-based stabilizer may also
be a hydrate (preferably, a hydrate of sodium
hypophosphite (NaH2PO2-nH2O) ) .
As the inorganic phosphorus-based stabilizer, one
kind may be used, or two or more kinds may be used in
combination.
[0176]
A blend amount of the (F) stabilizer in the
polyamide composition according to the present embodiment
is preferably 0.01 to 5 parts by mass, more preferably
0.02 to 1 part by mass, and still more preferably 0.1 to
1 part by mass, based on 100 parts by mass of the
polyamide.
By blending 0.01 parts by mass or more of the (F)
stabilizer a polyamide composition which has excellent
resistance to heat discoloration and weatherability can
be obtained. In addition, by blending 5 parts by mass or
more of the (F) stabilizer, silver streaks on the surface
of the molded product during molding of the polyamide
composition can be suppressed, and a molded product
having excellent mechanical properties such as toughness
and rigidity can be obtained.
[0177]
A method for producing the polyamide composition
comprising the (F) stabilizer according to the present
embodiment is not especially limited, as long as it is a
method which mixes the above-described (A) polyamide and


the (F) stabilizer. Examples thereof include blending
the stabilizer in the polyamide, blending the stabilizer
during polymerization of the polyamide, blending the
stabilizer when mixing the polyamide with another resin,
adhering the stabilizer to the surface of a powder or
pellet of the polyamide, blending the stabilizer in the
polyamide by melt kneading, and blending a master batch
of the stabilizer in the polyamide. Alternatively, a
combination of these blending methods may be employed.
[0178]
Examples of the method for mixing the polyamide and
the stabilizer include mixing the polyamide and the
stabilizer using a Henschel mixer or the like, then
feeding the resultant mixture to a melt kneader and
kneading, and blending the stabilizer in a polyamide
turned into a melt state by a single-screw or twin-screw
extruder from a side feeder.
The method for feeding the components constituting
the polyamide composition can be carried out by feeding
all of the constituent components all at once to the same
feed opening, or by feeding from different feed openings
for each constituent component.
[0179]
The melt kneading temperature is preferably about
250 to 375°C at a resin temperature.
The melt kneading time is preferably about 0.5 to 5
minutes.


As the apparatus for performing the melt kneading,
it is preferred to use a known apparatus, for example a
melt kneader such as a single-screw or twin-screw
extruder, a Banbury mixer, and a mixing roll.
[0180]
To the extent that the object of the present
embodiment is not harmed, the polyamide composition
comprising the (F) stabilizer may comprise additives
which are customarily used in polyamides, such as an
inorganic filler, a pigment, a dye, a fire retardant, a
lubricant, a fluorescent bleaching agent, a plasticizing
agent, an organic antioxidant, an ultraviolet absorber, a
nucleating agent, rubber, and a reinforcement.
[0181]
A relative viscosity r|r at 25°C, a melting point Tm2,
and a glass transition temperature Tg of the polyamide
composition comprising the (F) stabilizer according to
the present embodiment can be measured by the same
methods as the measurement methods for the above-
described polyamide. Further, by setting the measurement
values for the polyamide composition comprising the (F)
stabilizer in the same ranges as the ranges preferred for
the measurement values of the above-described polyamide,
a polyamide composition having excellent heat resistance,
moldability, and chemical resistance can be obtained.
[0182]


The polyamide composition comprising the (F)
stabilizer according to the present embodiment preferably
has a melt shear viscosity ηs of 20 to 110 Pa-s, more
preferably 25 to 90 Pa-s, and still more preferably 30 to
80 Pa-s.
The melt shear viscosity can be measured based on
the method described in the below examples.
By setting the melt shear viscosity to be in the
above-described range, a polyamide composition having
excellent fluidity can be obtained.
[0183]
The polyamide composition preferably has a tensile
strength of 80 MPa or more, more preferably 85 MPa or
more, and still more preferably 90 MPa or more.
Measurement of the tensile strength can be carried
out based on ASTM D638 as described in the below examples.
By setting the tensile strength to be 80 MPa or more,
a polyamide composition having excellent rigidity can be
obtained.
[0184]
The polyamide composition preferably has a tensile
elongation of 1.0% or more, more preferably 2.0% or more,
and still more preferably 3.0% or more.
Measurement of the tensile elongation can be carried
out based on ASTM D638 as described in the below examples.


By setting the tensile elongation to be 3.0% or more,
a polyamide composition having excellent toughness can be
obtained.
[0185]
The polyamide composition preferably has a water
absorbance of 5.0% or less, more preferably 4.0% or less,
and still more preferably 3.0% or less.
Measurement of the water absorbance can be carried
out based on the method described in the below examples.
By setting the water absorbance to be 5.0% or less,
a polyamide composition having excellent low water
absorbance can be obtained.
[0186]
The polyamide composition comprising the (F)
stabilizer according to the present embodiment preferably
has a change in color tone Ab before and after reworking
of 9 or less, and more preferably 6 or less.
Measurement of the change in color tone Ab can be
carried out based on the method described in the below
examples.
By setting the change in color tone Ab to be 9 or
less, a polyamide composition having excellent resistance
to heat discoloration can be obtained.
[0187]
The polyamide composition comprising the (F)
stabilizer preferably has a color difference AE of 9 or
less, and more preferably 5 or less.


Measurement of the color difference AE can be
carried out based on the method described in the below
examples.
By setting the color difference AE to be 9 or less,
a polyamide composition having excellent weatherability
can be obtained.
[0188]
Molding
The polyamide or polyamide composition according to
the present embodiment can be used to obtain various
kinds of molded products using known molding methods,
such as press molding, injection molding, gas-assisted
injection molding, welding molding, extrusion, blow
molding, film molding, hollow molding, multilayer molding,
and melt spinning.
[0189]
The polyamide or polyamide composition according to
the present embodiment can be preferably used as a raw
material for automobile components. Examples of
automobile components include an air intake system
component, a cooling system component, an interior
component, an exterior component, and an electronic
component.
Examples of the automobile air intake system
component are not especially limited, and may include an
air intake manifold, an intercooler inlet, an exhaust
pipe cover, an inner bushing, a bearing retainer, an


engine mount, an engine head cover, a resonator, and a
slot body.
Examples of the automobile cooling system component
are not especially limited, and may include a chain cover,
a thermostat housing, an outlet pipe, a radiator tank, an
alternator, and a delivery pipe.
Examples of an automobile fuel system component are
not especially limited, and may include a fuel delivery
pipe and a gasoline tank case. Examples of the interior
system component are not especially limited, and may
include an instrument panel, a console box, a glove box,
a steering wheel, and a trimming.
Examples of the external component are not
especially limited, and may include a molding, a lamp
housing, a front grill, a mud guard, a side bumper, a
door mirror stay, and a roof rail.
Examples of the electrical component are not
especially limited, and may include a connector, a wire
harness connector, a motor component, a lamp socket, an
on-board sensor switch, and a combination switch.
[0190]
A molded product obtained from the polyamide
composition according to the present embodiment,
especially from the polyamide composition comprising the
(C) copper compound and metal halide, has excellent heat
resistance, rigidity, toughness, moldability, low water
absorbance and the like. Further, such a molded product


also has even better vibration fatigue resistance,
fluidity, and heat aging resistance. Accordingly, this
molded product can be preferably used as an automobile
air intake system component.
The molded product has a strength half-life of
preferably 40 days or more, more preferably 45 days or
more, and still more preferably 50 days or more.
Measurement of the strength half-life can be carried out
based on the method described in the below examples.
By setting the strength half-life to be 40 days or
more, an automobile air intake system component having
excellent heat resistance, especially heat aging
resistance, can be obtained.
The molded product has a breaking stress of
preferably 45 MPa or more, more preferably 50 MPa or more,
and still more preferably 55 MPa or more. Measurement of
the breaking stress can be carried out based on the
method described in the below examples.
By setting the breaking stress to be 45 MPa or more,
an automobile air intake system component having
excellent vibration fatigue resistance can be obtained.
The molded product preferably has a water absorbance
of 5.0% or less, more preferably 4.0% or less, and still
more preferably 3.0% or less. Measurement of the water
absorbance can be carried out based on the method
described in the below examples.


By setting the water absorbance to be 5.0% or less,
an automobile air intake system component having
excellent low water absorbance can be obtained.
[0191]
A molded product obtained from the polyamide
composition according to the present embodiment,
especially from the polyamide composition comprising the
(C) copper compound and metal halide, has excellent heat
resistance, rigidity, toughness, moldability, and low
water absorbance. Further, such a molded product also
has even better LLC resistance. Accordingly, this molded
product can be preferably used as an automobile cooling
system component.
The molded product has a strength half-life of
preferably 40 days or more, more preferably 45 days or
more, and still more preferably 50 days or more.
Measurement of the strength half-life can be carried out
based on the method described in the below examples.
By setting the strength half-life to be 40 days or
more, an automobile cooling system component having
excellent heat resistance, especially heat aging
resistance, can be obtained.
The molded product has a tensile strength retention
rate after dipping of preferably 60% or more, more
preferably 75% or more, and still more preferably 80% or
more. Measurement of the tensile strength after dipping


can be carried out based on the method described in the
below examples.
By setting the tensile strength retention rate after
dipping to be 60% or more, an automobile cooling system
component having excellent LLC resistance can be obtained.
The molded product has a water absorbance of
preferably 5.0% or less, more preferably 4.0% or less,
and still more preferably 3.0% or less. Measurement of
the water absorbance can be carried out based on the
method described in the below examples.
By setting the water absorbance to be 5.0% or less,
an automobile cooling system component having excellent
low water absorbance can be obtained.
[0192]
The molded product of the polyamide or polyamide
composition according to the present embodiment can be
obtained using commonly known plastic molding methods,
such as press molding, injection molding, gas-assisted
injection molding, welding molding, extrusion, blow
molding, film molding, hollow molding, multilayer molding,
and melt spinning.
The molded product obtained from the polyamide or
polyamide composition according to the present embodiment
has excellent heat resistance, toughness, moldability,
and low water absorbance. Therefore, in addition to
automobile uses, the polyamide or polyamide composition
according to the present embodiment can be preferably


used, for example, as a material for various parts, such
as in electric and electronic parts, industrial materials,
and daily and household articles. Further, the polyamide
or polyamide composition according to the present
embodiment can be preferably used in extrusion
applications.
[0193]
Examples of the electric and electronic parts are
not especially limited, and may include a connector, a
switch, a relay, a printed wiring board, an electronic
component housing, a power point, a noise filter, a coil
bobbin, and a motor end cap.
Examples of the industrial machinery are not
especially limited, and may include a gear, a cam, an
insulation block, a valve, a power tool component, an
agricultural implement component, and an engine cover.
Examples of the daily and household articles are not
especially limited, and may include a button, a food
container, and office equipment.
Examples of the extrusion applications are not
especially limited, and may include a film, a sheet, a
filament, a tube, a rod, and a hollow molded product.
Examples
[0194]
The present embodiment will now be described in more
detail using the following examples and comparative


examples. However, the present embodiment is not limited
to only these examples.
The raw materials and measurement methods used in
the examples and comparative examples are shown below.
In the present embodiment, 1 kg/cm2 refers to 0.098 MPa.
[0195]
Raw materials
The following compounds were used in the examples,
(a) Dicarboxylic acid
(1) 1,4-Cyclohexanedicarboxylic acid (CHDA), trade name
1,4-CHDA HP Grade (trans/cis (molar ratio) = 25/75),
manufactured by Eastman Chemical Company
(2) Terephthalate acid (TPA), trade name Terephthalate
acid, manufactured by Wako Pure Chemical Industries, Ltd.

(3) Adipic acid (ADA), trade name Adipic acid,
manufactured by Wako Pure Chemical Industries, Ltd.
(4) Suberic acid (C8DA), trade name Suberic acid,
manufactured by Wako Pure Chemical Industries, Ltd.
(5) Azelaic acid (C9DA), trade name Azelaic acid,
manufactured by Wako Pure Chemical Industries, Ltd.
(6) Sebacic acid (C10DA), trade name Sebacic acid,
manufactured by Wako Pure Chemical Industries, Ltd.
(7) Dodecanedioic acid (C12DA), trade name Dodecanedioic
acid, manufactured by Wako Pure Chemical Industries, Ltd.
(8) Tetradecanedioic acid (C14DA), trade name
Tetradecanedioic acid, manufactured by Tokyo Chemical
Industry Co., Ltd.


(9) Hexadecanedioic acid (C16DA), trade name
Hexadecanedioic acid, manufactured by Tokyo Chemical
Industry Co., Ltd.
[0196]
(b) Diamine
(10) 2-Methylpentamethylenediamine (2MPD), trade name 2-
Methyl-1,5-diaminopentane, manufactured by Tokyo Chemical
Industry Co., Ltd.
(11) Hexamethylenediamine (HMD), trade name
Hexamethylenediamine, manufactured by Wako Pure Chemical
Industries, Ltd.

(12) 1,9-Nonamethylenediamine (NMD), trade name 1,9-
Nonanediamine, manufactured by Sigma-Aldrich
(13) 2-Methyloctamethylenediamine (2MOD), produced with
reference to the production method described in Japanese
Patent Laid-Open No. 05-17413.
(14) Mixture of 2,2,4-trimethyl-1,6-hexanediamine and
2,4,4-trimethyl-1,6-hexanediamine (TMHD) , trade name
C,C,C-1,6-hexanediamine, manufactured by Sigma-Aldrich
[0197]
(B) Inorganic filler
(15) Glass fiber (GF), trade name ECS03T275H, average
fiber diameter 10 µm , cut length 3 mm, manufactured by
Nippon Electric Glass Co., Ltd.
[0198]
(C) Copper compound and metal halide


(16) Copper iodide (CuI), trade name Copper iodide (I),
manufactured by Wako Pure Chemical Industries, Ltd.
(17) Potassium iodide (KI), trade name Potassium iodide,
manufactured by Wako Pure Chemical Industries, Ltd.
(18) Ethylene bis-stearylamide, trade name Armowax EBS,
manufactured by Lion Corporation
[0199]
(D) Halogen-based flame retardant
(19) Polystyrene bromide, trade name SAYTEX® HP-7010G
(bromine content based on elemental analysis: 63 mass%),
manufactured by Albemarle Corporation
[0200]
(E) Phosphinate
(20) Aluminum diethylphosphinate (DEPAl), produced with
reference to the production method described in Japanese
Patent Laid-Open No. 08-73720.
[0201]
(F) Stabilizer
(F-1) Phenolic-based stabilizer
(21) N,N'-hexane-l,6-diylbis[3-(3,5-di-t-butyl-4-
hydroxyphenyl propionamide)] , trade name IRGANOX® 1098,
manufactured by Ciba Japan
(F-2) Phosphite-based stabilizer
(22) Bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol
diphosphite, trade name ADEKA STAB® PEP-36, manufactured
by ADEKA Corporation
(F-3) Hindered amine-based stabilizer


(23) Bis-(2,2,6,6-tetramethyl 4-piperidyl)-sebacate,
trade name Sanol® 770, manufactured by Ciba Japan
(F-4) Triazine-based stabilizer
(24) 2-(2'-Hydroxy-4'-hexyloxyphenyl)-4,6-diphenyl-1,3,5-
triazine, trade name TINUVIN 167FF, manufactured by Ciba
Japan
(F-5) Inorganic phosphorus-based stabilizer
(25) Sodium hypophosphite, trade name Sodium
hypophosphite, manufactured by Wako Pure Chemical
Industries, Ltd.
[0202]
(G) Flame retardant auxiliary
(26) Diantimony trioxide, trade name Diantimony trioxide,
manufactured by Daiichi F.R.
(27) Zinc borate 2ZnO3B2O3.3. 5H2O, trade name Firebrake®
ZB, manufactured by U.S. Borax

(28) Magnesium hydroxide, trade name Kisuma® 5, average
particle size: 0.8 µm, manufactured by Kyowa Chemical
Industry Co., Ltd.
[0203]
(H) Polymer comprising an α,β-unsaturated dicarboxylic
acid anhydride
(29) Copolymer of styrene and maleic anhydride, trade
name DYLARK® 332 (copolymer of styrene 85 mass% and
maleic anhydride 15 mass%), manufactured by NOVA
Chemicals
[0204]


Amount of polyamide component calculation
The mol% of the (a-1) alicyclic dicarboxylic acid
was determined by calculating the (number of moles of the
(a-1) alicyclic dicarboxylic acid added as a raw material
monomer / number of moles of all the (a) dicarboxylic
acid added as a raw material monomer) x 100.
The mol% of the (b-1) diamine having the substituent
branched from the main chain was determined by
calculating the (excluding the additionally-added portion,
number of moles of the (b-1) diamine having the
substituent branched from the main chain added as a raw
material monomer / number of moles of all the (b) diamine
added as a raw material monomer) x 100.
Further, the mol% of the (c) lactam and/or
aminocarboxylic acid was determined by calculating the
(number of moles of the (c) lactam and/or aminocarboxylic
acid added as a raw material monomer / number of moles of
all the (a) dicarboxylic acid + number of moles of all
the (b) diamine + number of moles of the (c) lactam
and/or aminocarboxylic acid added as raw material
monomers) x 100.
[0205]
Measurement methods
(1) Melting points Tml, Tm2 (°C)
Melting points Tml, Tm2 were measured using the
Diamond-DSC, manufactured by PERKIN-ELMER Inc., based on
JIS-K7121. Measurement was carried out under conditions


of a nitrogen atmosphere, by taking Tm1 (°C) as the
temperature at the endothermic peak (melting peak) which
appeared when the temperature of a specimen of about 10
mg was increased to 300 to 350°C depending on the melting
point of the sample at a rate of temperature increase of
20°C/min. Tm2 was taken as the temperature of the
maximum peak temperature of the endothermic peaks
(melting peaks) which appeared when, after maintaining
the temperature in a melt state at the maximum
temperature for 2 minutes, lowering the temperature to
30°C at a rate of temperature decrease of 20°C/min and
then after maintaining at 30°C for 2 minutes, similarly
increasing the temperature at a rate of temperature
increase of 20°C/min. The total peak surface area was
taken as the heat of fusion AH (J/g)• In cases where
there was a plurality of peaks, areas having a AH of 1
J/g or more were determined to be peaks. If there are
two peaks, for example, one at a melting point of 295°C,
AH = 20 J/g, and another one at a melting point of 325°C,
AH = 5 J/g, the melting point was taken to be 325°C.
[0206]
(2) Glass transition temperature Tg (°C)
The glass transition temperature was measured using
the Diamond-DSC, manufactured by PERKIN-ELMER Inc., based
on JIS-K7121. Measurement was carried out under
conditions of using liquid nitrogen to rapidly cool a
molten sample obtained by melting a specimen with a hot


stage (EP80, manufactured by Mettler) to solidify the
sample for use as a measurement sample. Using 10 mg of
this sample, the temperature was increased to a range of
from 30 to 350°C at a rate of temperature increase of
20°C/min, and the glass transition temperature was
measured.
[0207]
(3) Relative viscosity ηr at 25°C
Measurement of the relative viscosity at 25°C was
carried out based on JIS-K6810. More specifically, using
98% sulfuric acid, a 1% concentration solution (ratio of
(polyamide 1 g) / (98% sulfuric acid 100 mL)) was
prepared, and the relative viscosity was measured under
temperature conditions of 25°C.
[0208]
(4) Melt shear viscosity r|s (Pa.s)
Fluidity was evaluated in terms of the melt shear
viscosity r|s at a shear rate of 1,000 sec-1 under
temperature conditions of +20°C the melting point
determined in the above item (1). More specifically, the
measurement method was carried out using the twin
capillary rheometer RH7-2 model manufactured by ROSAND
(UK) . Two orifices were used, which had a die diameter
of 1.0 mm, a die inlet angle of 180°, and L/D of 16 and
0.25.
[0209]
(5) Tensile strength (MPa) and tensile elongation (%)


Tensile strength (MPa) and tensile elongation (%)
were measured based on ASTM D638 using a dumbbell
injection molding test piece (3 mm thick) for ASTM
tensile testing. The molding test piece was molded by
mounting a dumbbell test piece (3 mm thick) die (die
temperature = Tg + 20°C) for ASTM tensile testing (ASTM
D638) on an injection molding machine (PS40E,
manufactured by Nissei Plastic Industrial Co., Ltd.), and
molding at a cylinder temperature of (Tm2 + 10)°C to (Tm2
+ 30)°C.
[0210]
(6) Water absorbance (%)
The pre-testing mass (mass before water absorbance)
of a dumbbell injection molding test piece (3 mm thick)
for ASTM tensile testing was measured in a post-molding
dry state (dry as mold). The test piece was dipped in
80°C pure water for 24 hours. The test piece was then
removed from the water, and moisture adhering to the
surface was wiped off. The test piece was then left for
30 minutes under a constant-temperature constant-humidity
(23°C, 50 RH%) atmosphere, and the post-molding mass
(mass after water absorbance) was measured. The increase
in the mass after water absorbance as compared with the
mass before water absorbance was taken as the water
absorbance amount. The average ratio of the water
absorbance amount with respect to the mass before water


absorbance for the number of test runs n = 3 was taken as
the water absorbance (%) .
[0211]
(7) Copper concentration, halogen concentration, and
molar ratio of halogen and copper (halogen/Cu)
The copper concentration was quantified by charging
sulfuric acid into a specimen, adding nitric acid to the
resultant mixture while heating to dissolve the organic
component, maintaining the volume of the solution
constant with pure water, and quantifying the
concentration by ICP emission analysis (high-frequency
plasma emission analysis). A Vista-Pro manufactured by
Seiko Instruments & Electronics Ltd. was used for the ICP
emission analysis apparatus.
The halogen concentration was quantified by, using
iodine as an example, combusting a specimen in a flask
purged with high-purity oxygen, trapping the produced gas
in an absorbing solution, and quantifying the iodine in
the trapped solution using potentiometric titration with
a 1/100 N silver nitrate solution.
The molar ratio of halogen and copper (halogen/Cu)
was calculated using the above respective quantified
values from the molecular weights converted into moles.
[0212]
(8) Strength half-life (days)
The dumbbell injection molding test piece (3 mm
thick) for ASTM tensile testing described in the above


item (5) was heat treated for a predetermined period in a
hot-air oven at 200°C, and the tensile strength was
measured based on ASTM-D638. Then, the tensile strength
after the heat treatment as compared with the tensile
strength before the heat treatment was calculated as the
tensile strength retention rate. The length of heat
treated time at which the tensile strength retention rate
was 50% was taken as the strength half-life.
[0213]
(9) Breaking stress (MPa)
The dumbbell injection molding test piece (3 mm
thick) for ASTM tensile testing described in the above
item (5) was loaded with a tension load by a sinusoidal
wave of frequency 20Hz under a 120°C atmosphere using the
hydraulic servo fatigue testing machine EHF-50-10-3
manufactured by Saginomiya Seisakusho Co., Ltd., to
determine the breaking stress (MPa) at 1,000,000 times.
[0214]
(10) Color tone b value
Dumbbell injection molding test pieces (ASTM
dumbbell,3 mm thick) for ASTM tensile testing were
obtained by injection molding a polymer pellet with an
injection molding machine under injection molding
conditions of a cylinder temperature of Tm2 + 30°C, a die
temperature of Tg + 20°C, and a molding cycle of 60
seconds. Using the Colorimeter ND-300A manufactured by
Nippon Denshoku Industries Co., Ltd., the initial molded


product color tone b value was determined. Measurement
was carried out using 3 dumbbell injection molding test
pieces, measuring each piece 3 times at a middle section
of the widened portion on the opposite gate side, and
taking the average value thereof.
[0215]
(11) Color tone difference Ab
Dumbbell injection molding test pieces (ASTM
dumbbell,3 mm thick) for ASTM tensile testing were
obtained by injection molding a polymer pellet with an
injection molding machine under injection molding
conditions of a cylinder temperature of Tm2 + 30°C, a die
temperature of Tg + 20°C, and a molding cycle of 60
seconds. Using the Colorimeter ND-300A manufactured by
Nippon Denshoku Industries Co., Ltd., the color tone b
values of the initial molded product and the molded
product after 1,000 hours were determined. The
difference between these values was taken as Ab.
Measurement was carried out using 3 dumbbell injection
molding test pieces, measuring each piece 3 times at a
middle section of the widened portion on the opposite
gate side, and taking the average value thereof.
[0216]
(12) Color difference AE
The color difference AE after 1,000 hours was
evaluated for a natural color molded product based on ISO
4892-2 using a dumbbell injection molding test pieces (3


mm thick) for ASTM tensile testing. The Ci4000 (xenon
lamp) manufactured by ATLAS was used as the testing
machine. Using the Colorimeter ND-300A manufactured by
Nippon Denshoku Industries Co., Ltd., the color
difference (AE) between the initial molded product and
the molded product after 1,000 hours was determined.
Measurement was carried out using 3 dumbbell injection
molding test pieces, measuring each piece 3 times at a
middle section of the widened portion on the opposite
gate side, and taking the average value thereof.
[0217]
(13) Trans isomer ratio
30 to 40 mg of polyamide was dissolved in 1.2 g of
hexafluoroisopropanol deuteride, and the trans isomer
ratio was measured by 1H-NMR. For 1,4-
cyclohexanedicarboxylic acid, the trans isomer ratio was
determined from the ratio of the peak surface area at
1.98 ppm derived from trans isomers and the peak surface
areas at 1.77 ppm and 1.8 6 ppm derived from cis isomers.
[0218]
(14) Flame resistance
Flame resistance was measured using the UL94 method
(standard specified by Underwriters Laboratories Inc.,
U.S.A.). Molding of the test piece (127 mm long, 12.7 mm
wide, and 1/32 inch thick) was carried out by mounting a
die (die temperature = Tg + 20°C) of the UL test piece on
an injection molding machine (PS40E, manufactured by


Nissei Plastic Industrial Co., Ltd.), and performing
molding at a cylinder temperature of (Tm2 + 20)°C. The
injection pressure was +2% the full filling pressure
during the molding of the UL test piece.
Flame graduation was based on the UL 94 standard
(vertical burning test). Further, test pieces which
failed V-2 were denoted as V-2 out.
[0219]
(15) Flow length (cm)
The flow length was determined by molding a 2 mm
thick x 15 mm wide piece with a molding machine set to
the below conditions, and evaluating based on the flow
length thereof (filled length, cm).
Molding was carried out by mounting a fluidity
evaluation (2 mm thick x 15 mm wide spiral flow path) die
(die temperature = Tg + 20°C) on an injection molding
machine (FN3000, manufactured by Nissei Plastic
Industrial Co., Ltd.), and performing molding at a
cylinder temperature of Tm2 + 20°C, an injection rate at
a 20% setting, and an injection pressure at a 34% setting.
[0220]
(16) Full filling pressure (%)
The full filling pressure (%) during the UL test
piece molding described in the above item (14) was shown.
The full filling pressure was determined by
standardizing the injection rates (99%) and measuring the
minimum pressure capable of completely filling melted


resin into the filling end inside the die, and
calculating the full filling pressure as a percentage of
the maximum pressure that the molding machine can apply.
[0221]
(17) Tensile strength retention rate after dipping (%)
The dumbbell injection molding test piece (3 mm
thick) for ASTM tensile testing of the above item (5) was
dipped for 1,000 hours in a 130°C aqueous solution of 50%
ethylene glycol. After leaving at room temperature, the
tensile test of the above item (5) was carried out to
measure tensile strength. The tensile strength retention
rate after dipping was determined as a ratio with respect
to the tensile strength measured after the molding.
[0222]
Example 1
A polyamide polymerization reaction was carried out
by "hot melt polymerization".
896 g (5.20 mol) of (a) CHDA and 604 g (5.20 mol) of
(b) 2MPD were dissolved in 1,500 g of distilled water to
produce an equimolar 50 mass% uniform aqueous solution of
the raw material monomers. 15 g (0.13 mol) of 2MPD was
additionally added to this uniform solution.
The obtained aqueous solution was charged into an
autoclave having an internal volume of 5.4 L
(manufactured by Nitto Kouatsu Co., Ltd.). The autoclave
was kept warm until the solution temperature (internal
temperature) was 50°C, and then the contents of the


autoclave were purged with nitrogen. Heating was
continued from a solution temperature of about 50°C until
the pressure in the autoclave tank was, in terms of gauge
pressure (in the following, pressure in the tank is
always expressed as gauge pressure), about 2.5 kg/cm
(the solution temperature in this system was about 145°C) .
While removing water from the system to maintain the
pressure in the tank at about 2.5 kg/cm2, heating was
continued so that the concentration of the aqueous
solution was concentrated to about 75% (the solution
temperature in this system was about 160°C). Removal of
water was stopped, and then heating was continued until
the pressure in the tank was about 30 kg/cm2 (the
solution temperature in this system was about 245°C) .
While removing water from the system to maintain the
pressure in the tank at about 30 kg/cm2, heating was
continued until 50°C below the final temperature. After
the solution temperature increased to 50°C below the
final temperature (here, 300°C) , while continuing heating,
the pressure in the tank was lowered over about 120
minutes to atmospheric pressure (gauge pressure of 0
kg/cm2) .
Subsequently, the heater temperature was adjusted so
that the final temperature of the resin temperature
(solution temperature) would be about 350°C. With the
resin temperature in that state, the tank contents were
kept for 30 minutes under a reduced pressure of 400 Torr


by a vacuum apparatus. Then, the pressure was increased
with nitrogen, and the resin was formed into a strand
from a lower spinneret (nozzle). This strand was water
cooled and cut, then discharged in pellet form to obtain
a polyamide. Table 4 shows the measurement results of
measurements carried out on the obtained polyamide based
on the above-described measurement methods.
[0223]
Examples 2 to 21
Polyamide polymerization ("hot melt polymerization")
was carried out by the method described in Example 1,
except that the compounds and amounts shown in Table 1 or
2 were used for the (a) dicarboxylic acid, (b) diamine,
and (c) lactam and/or aminocarboxylic acid, and that the
resin final temperature was the temperature shown in
Table 4 or 5. Tables 4 and 5 show the measurement
results of measurements carried out on the obtained
polyamides based on the above-described measurement
methods.
[0224]
Comparative Example 1
Polyamide polymerization ("hot melt polymerization")
was carried out by the method described in Example 1,
except that the compounds and amounts shown in Table 3
were used for the (a) dicarboxylic acid, (b) diamine, and
(c) lactam and/or aminocarboxylic acid, and that the


resin final temperature was the temperature shown in
Table 6.
In Comparative Example 1, during the polymerization,
since the resin solidified in the autoclave, a strand
could not be extracted. Therefore, after cooling, the
solidified product was extracted as a lump. This lump
was ground with a grinder to form roughly pellet-sized
objects. Since foaming was severe during molding, a
molded product could not be obtained.
[0225]
Comparative Examples 2 to 7
Polyamide polymerization ("hot melt polymerization")
was carried out by the method described in Example 1,
except that the compounds and amounts shown in Table 3
were used for the (a) dicarboxylic acid, (b) diamine, and
(c) lactam and/or aminocarboxylic acid, and that the
resin final temperature was the temperature shown in
Table 6. Table 6 shows the measurement results of
measurements carried out on the obtained polyamides based
on the above-described measurement methods.














[0232]
As is clear from the results of Tables 4 to 6, the
polyamides of Examples 1 to 21, in which a specific (a)
and (b) were polymerized, had especially excellent
properties for all of heat resistance, fluidity,
toughness, low water absorbance, and rigidity.
In contrast, in Comparative Example 1, which is a
polyamide comprising less than 50 mol% of 2-
methylpentamethylenediamine, the resin solidified during
the copolymerization. Consequently, not only could the
polyamide not be extracted as a strand, but a molded
product could not be obtained.
Further, for the polyamide of Comparative Example 4,
which was produced by the method disclosed in Patent
Document 1, fluidity was too low, and the molding
properties were insufficient. In addition, toughness was
also insufficient.
[0233]
Example 22
A polyamide polymerization reaction was carried out
by "hot melt polymerization / solid phase polymerization".
The hot melt polymerization was carried out using
the same charged amounts and the same procedures as in
Example 1 to obtain a polyamide (polyamide (I)). Table 7
shows the measurement results of measurements carried out
on the obtained polyamide based on the above-described
measurement methods. 1,300 g of the obtained polyamide


was charged into a ribbon stirring type heating apparatus
for solid phase polymerization (Ribocone, manufactured by
Okawara Corporation), and the heating apparatus was
purged with nitrogen at room temperature. While still
flowing nitrogen, heating was carried out for 12 hours so
that the resin temperature was 200°C. Subsequently,
while still flowing nitrogen, the temperature was lowered.
At about 50°C, the resin was extracted from the apparatus
still as a pellet to obtain a polyamide (polyamide (II)).
Table 7 shows the measurement results of measurements
carried out on the obtained polyamide based on the above-
described measurement methods.
Compared with polyamide (I), polyamide (II), which
had been subjected to solid phase polymerization, had an
increased relative viscosity at 25°C and an increased
tensile elongation. There was no change in the trans
isomer ratio before and after the solid phase
polymerization. Further, the degree of coloration also
did not change.
[0234]
Table 7 also shows the measurement results of
measurements carried out on the polyamide of Example 1
obtained by hot melt polymerization based on the above-
described measurement methods.


[0235]
Example 23
A polyamide polymerization reaction was carried out
by "prepolymer / solid phase polymerization".
500 g of distilled water was charged into 896 g
(5.20 mol) of (a) CHDA and 604 g (5.20 mol) of (b) 2MPD
to produce an equimolar 33 mass% slurry of the raw
material monomers. 15 g (0.13 mol) of 2MPD was
additionally added to this slurry.
The obtained slurry was charged into an autoclave
having an internal volume of 5.4 L (manufactured by Nitto
Kouatsu Co., Ltd.). The contents of the autoclave were
purged with nitrogen. After stirring for 30 minutes at
the solution temperature of 100°C, the temperature was
increased over 2 hours to 200°C. At this stage, the
pressure in the autoclave tank was 22 kg/cm2. The
temperature was increased to 220°C. The slurry was kept
for 2 hours while removing water from the system to
maintain the pressure in the tank at 22 kg/cm2. The
pressure in the tank was then lowered over 60 minutes to
atmospheric pressure (gauge pressure of 0 kg/cm2) .
Subsequently, the resin temperature (solution
temperature) was lowered to room temperature, and a
flange at a lower portion of the autoclave was removed,
whereby a solid-state polyamide prepolymer was obtained
(polyamide (I)). Table 7 shows the measurement results
of measurements carried out on the obtained prepolymer


based on the above-described measurement methods. The
trans isomer ratio of 1,4-cyclohexanedicarboxylic acid of
the prepolymer was 85%. Further, coloration was seen for
the polyamide (I).
Solid phase polymerization was carried out in the
same manner as in Example 22 using 1,300 g of the
obtained prepolymer to obtain a polyamide (polyamide
(II)) . Table 7 shows the measurement results of
measurements carried out on the obtained polyamide based
on the above-described measurement methods. Compared
with the prepolymer, although the polyamide (II) had an
increased relative viscosity, coloration was observed.
[0236]
Example 2 4
A polyamide polymerization reaction was carried out
by "prepolymer / extrusion polymerization".
The prepolymer was produced using the same charged
amounts and the same procedures as in Example 23 to
obtain a polyamide prepolymer (polyamide (I)). Using
1,300 g of the obtained prepolymer, post-polymerization
was carried out using an extrusion polymerization
apparatus (KRC Kneader, manufactured by Kurimoto, Ltd.)
The prepolymer was introduced with a jacket temperature
of 350°C and a degree of vacuum of -0.5 MPa (gauge
pressure) so that the dwell time would be 30 minutes.
The strand was cooled and cut to obtain a polyamide as a
pellet (polyamide (II)). Table 7 shows the measurement


results of measurements carried out on the obtained
polyamide based on the above-described measurement
methods. Compared with the prepolymer, although the
polyamide (II) had an increased relative viscosity at
25°C, coloration was observed.




[0238]
Polyamide composition comprising (B) inorganic filler
Example 25
The polyamide of Example 1 was used by drying under
a nitrogen flow so that the moisture content was adjusted
to about 0.2 mass%. Using a twin-screw extruder (TEM 35,
L/D = 47.6, set temperature 340°C, screw revolution
speed 300 rpm, manufactured by Toshiba Machine Co., Ltd.),
this dried polyamide was fed from a top feed opening
provided at the uppermost upstream portion of the
extruder. Glass fiber (GF) was fed from a side feed
opening on a downstream side of the extruder (the resin
fed from the top feed opening was in a sufficiently
molten state) . A melt kneaded product extruded from a
die head was cooled in a strand form, which was
pelletized to form polyamide composition pellets. The
blend amount was 55 parts by mass of glass fiber (GF)
based on 100 parts by mass of polyamide. Table 8 shows
the measurement results of measurements carried out on
the obtained polyamide composition based on the above-
described measurement methods.
[0239]
Examples 2 6 to 45
Examples 2 6 to 45 were carried out in the same
manner as Example 25, except that the respective
polyamides of Examples 2 to 21 were used instead of the
polyamide of Example 1. Tables 8 and 9 show the


measurement results of measurements carried out on the
obtained polyamide compositions based on the above-
described measurement methods.
[0240]
Example 4 6
Example 4 6 was carried out in the same manner as
Example 29, except that 100 parts by mass of glass fiber
(GF) based on 100 parts by mass of polyamide was used.
Table 9 shows the measurement results of measurements
carried out on the obtained polyamide composition based
on the above-described measurement methods.
[0241]
Comparative Example 8
An attempt was made to carry out Comparative Example
8 in the same manner as Example 25, except the polyamide
of Comparative Example 1 was used instead of the
polyamide of Example 1. However, the extrusion state was
very unstable, and a polyamide composition could not be
obtained.
[0242]
Comparative Examples 9 and 10
Comparative Examples 9 and 10 were carried out in
the same manner as Example 25, except that the respective
polyamides of Comparative Examples 2 and 3 were used
instead of the polyamide of Example 1. Table 10 shows
the measurement results of measurements carried out on


the obtained polyamide compositions based on the above-
described measurement methods.
[0243]
Comparative Example 11
Comparative Example 11 was carried out in the same
manner as Example 25, except that the polyamide of
Comparative Example 4 was used instead of the polyamide
of Example 1, and 100 parts by mass of glass fiber (GF)
based on 100 parts by mass of polyamide was used. Table
10 shows the measurement results of measurements carried
out on the obtained polyamide composition based on the
above-described measurement methods.
[0244]
Comparative Examples 12 to 14
Comparative Examples 12 to 14 were carried out in
the same manner as Example 25, except that the respective
polyamides of Comparative Examples 5 to 7 were used
instead of the polyamide of Example 1. Table 10 shows
the measurement results of measurements carried out on
the obtained polyamide compositions based on the above-
described measurement methods.








[0248]
From the results of Tables 8 to 10, the polyamide
compositions of Examples 25 to 4 6, which comprise a
polyamide obtained by polymerization of a specific (a)
and (b) and an inorganic filler, had especially excellent
properties for all of heat resistance, fluidity,
toughness, low water absorbance, and rigidity.
In contrast, in Comparative Example 8, which
comprises a polyamide obtained by polymerization of less
than 50 mol% of 2-methylpentamethylenediamine, the
extrusion state was unstable, and a polyamide composition
could not be obtained.
Further, for the polyamide compositions of
Comparative Examples 9 and 10, which comprise a polyamide
obtained by polymerization of less than 50 mol% of an
alicyclic dicarboxylic acid, heat resistance and low
water absorbance were poor.
In addition, for the polyamide composition of
Comparative Example 11, which comprises a polyamide
produced by the method disclosed in Patent Document 1,
melt shear viscosity was large, fluidity was too low, and
the molding properties were insufficient. In addition,
tensile elongation was small and toughness was also
insufficient.
[0249]
Polyamide composition comprising (C) copper compound and
metal halide

Production Example 1
A mixture of KI and ethylene bis-stearylamide was
obtained by mixing 85.1 parts by mass of KI and 10 parts
by mass of ethylene bis-stearylamide. The mixture was
thoroughly mixed with 4.9 parts by mass of Cul, and the
resultant product was granulated with a disk pelleter
(F5-11-175, manufactured by Fuji Paudal Co., Ltd.) to
obtain granules (1).
[0250]
Production Example 2
A mixture of KI and ethylene bis-stearylamide was
obtained by mixing 80.7 parts by mass of KI and 10 parts
by mass of ethylene bis-stearylamide. The mixture was
thoroughly mixed with 9.3 parts by mass of CuI, and the
resultant product was granulated with a disk pelleter
(F5-11-175, manufactured by Fuji Paudal Co., Ltd.) to
obtain granules (2).
[0251]
Production Example 3
A mixture of KI and ethylene bis-stearylamide was
obtained by mixing 88.0 parts by mass of KI and 10 parts
by mass of ethylene bis-stearylamide. The mixture was
thoroughly mixed with 2.0 parts by mass of CuI, and the
resultant product was granulated with a disk pelleter
(F5-11-175, manufactured by Fuji Paudal Co., Ltd.) to
obtain granules (3).


[0252]
Example 47
A polyamide composition was obtained by blending 6.1
parts by mass of the granules (1) produced in Production
Example 1 and 55 parts by mass of inorganic filler (GF)
based on 100 parts by mass of the polyamide of Example 1,
and melt kneading the resultant mixture with a twin-screw
extruder (TEM 35, fL/D = 47.6, set temperature 340°C,
screw revolution speed 300 rpm, manufactured by Toshiba
Machine Co., Ltd.). Table 11 shows the measurement
results of measurements carried out on the obtained
polyamide composition based on the above-described
measurement methods.
[0253]
Examples 4 8 to 67
Examples 4 8 to 67 were carried out in the same
manner as Example 47, except that the respective
polyamides of Examples 2 to 21 were used instead of the
polyamide of Example 1. Tables 11 and 12 show the
measurement results of measurements carried out on the
obtained polyamide compositions based on the above-
described measurement methods.
[0254]
Comparative Example 15
An attempt was made to carry out Comparative Example
15 in the same manner as Example 47, except the polyamide
of Comparative Example 1 was used instead of the


polyamide of Example 1. However, the extrusion state was
very unstable, and a polyamide composition could not be
obtained.
[0255]
Comparative Examples 16 to 21
Comparative Examples 16 to 21 were carried out in
the same manner as Example 47, except that the respective
polyamides of Comparative Examples 2 to 7 were used
instead of the polyamide of Example 1. Table 13 shows
the measurement results of measurements carried out on
the obtained polyamide compositions based on the above-
described measurement methods.
[0256]
Table 14 shows the measurement results of
measurements carried out on the polyamide of Example 2 9
based on the above-described measurement methods.
[0257]
Example 68
Example 68 was carried out in the same manner as
Example 51, except that 3.1 parts by mass of the granules
(1) of Production Example 1 based on 100 parts by mass of
the polyamide of Example 5 were used. Table 14 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.


[0258]
Example 69
Example 69 was carried out in the same manner as
Example 51, except that 9.2 parts by mass of the granules
(1) of Production Example 1 based on 100 parts by mass of
the polyamide of Example 5 were used. Table 14 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.
[0259]
Example 70
Example 70 was carried out in the same manner as
Example 51, except that 12.2 parts by mass of the
granules (1) of Production Example 1 based on 100 parts
by mass of the polyamide of Example 5 were used. Table
14 shows the measurement results of measurements carried
out on the obtained polyamide composition based on the
above-described measurement methods.
[0260]
Example 71
Example 71 was carried out in the same manner as
Example 51, except that 3.2 parts by mass of the granules
(2) of Production Example 2 based on 100 parts by mass of
the polyamide of Example 5 were used. Table 14 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.


[0261]
Example 72
Example 72 was carried out in the same manner as
Example 51, except that 15.0 parts by mass of the
granules (3) of Production Example 3 based on 100 parts
by mass of the polyamide of Example 5 were used. Table
14 shows the measurement results of measurements carried
out on the obtained polyamide composition based on the
above-described measurement methods.










[0266]
From the results of Tables 11 to 14, the polyamide
compositions of Examples 51 to 72, which comprise a
polyamide obtained by polymerization of a specific (a)
and (b), and a copper compound and metal halide, had
especially excellent properties for heat resistance,
fluidity, toughness, low water absorbance, and rigidity,
as well as for heat aging resistance.
In contrast, in Comparative Example 15, which
comprises a polyamide comprising less than 50 mol% of 2-
methylpentamethylenediamine, the extrusion state was
unstable, and a polyamide composition could not be
obtained.
Further, for the polyamide compositions of
Comparative Examples 16 and 17, which comprise a
polyamide obtained by polymerization of less than 50 mol%
of an alicyclic dicarboxylic acid, heat resistance and
low water absorbance were poor.
In addition, for the polyamide composition of
Comparative Example 18, which comprises a polyamide
produced by the method disclosed in Patent Document 1,
melt shear viscosity was large, fluidity was too low, and
the molding properties were insufficient. In addition,
tensile elongation was small and toughness was also
insufficient.


[0267]
Polyamide composition comprising (D) halogen-based flame
retardant
Example 73
The polyamide of Example 1 was used by drying under
a nitrogen flow so that the moisture content was adjusted
to about 0.2 mass%. Using a twin-screw extruder (TEM 35,
speed 300 rpm, and output rate 50 kg/hr, manufactured by
Toshiba Machine Co., Ltd.), a pre-blended mixture of the
(A) polyamide, a (D) halogen-based flame retardant, a (G)
flame retardant auxiliary, and an (H) polymer comprising
an a, (3-unsaturated dicarboxylic acid anhydride was fed
from a top feed opening provided at the uppermost
upstream portion of the extruder. A (B) inorganic filler
was fed from a side feed opening on a downstream side of
the extruder (the resin fed from the top feed opening was
in a sufficiently molten state). A melt kneaded product
extruded from a die head was cooled in a strand form,
which was pelletized to form polyamide composition
pellets. The blend amount was, based on 100 parts by
mass of the (A) polyamide, 45.0 parts by mass of the (D)
halogen-based flame retardant, 7.0 parts by mass of the
(G) flame retardant auxiliary, 4.0 parts by mass of the
(H) polymer comprising an a, (3-unsaturated dicarboxylic
acid anhydride, and 70.0 parts by mass of the (B)
inorganic filler. Table 15 shows the measurement results


of measurements carried out on the obtained polyamide
composition based on the above-described measurement
methods.
[0268]
Examples 74 to 93
Examples 74 to 93 were carried out in the same
manner as Example 73, except that the polyamides of
Examples 2 to 21 were used instead of the polyamide of
Example 1. Tables 15 and 16 show the measurement results
of measurements carried out on the obtained polyamide
compositions based on the above-described measurement
methods.
[0269]
Example 94
Example 94 was carried out in the same manner as
Example 77, except that the (H) polymer comprising an
a, (3-unsaturated dicarboxylic acid anhydride was not
blended, and that 15.0 parts by mass of the (G) flame
retardant auxiliary and 75.0 parts by mass of the (B)
inorganic filler were used. Table 16 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.
[0270]
Example 95
Example 95 was carried out in the same manner as
Example 77, except that 7.0 parts by mass of magnesium


hydroxide as the (G) flame retardant auxiliary was used.
Table 16 shows the measurement results of measurements
carried out on the obtained polyamide composition based
on the above-described measurement methods.
[0271]
Comparative Example 22
An attempt was made to carry out Comparative Example
22 in the same manner as Example 73, except the polyamide
of Comparative Example 1 was used instead of the
polyamide of Example 1. However, the extrusion state was
very unstable, and a polyamide composition could not be
obtained.
[0272]
Comparative Examples 23 to 2 8
Comparative Examples 23 to 28 were carried out in
the same manner as Example 73, except that the polyamides
of Comparative Examples 2 to 7 were used instead of the
polyamide of Example 1. Table 17 shows the measurement
results of measurements carried out on the obtained
polyamide compositions based on the above-described
measurement methods.










[0276]
From the results of Tables 15 to 17, the polyamide
compositions of Examples 73 to 94, which comprise a
polyamide obtained by polymerization of a specific (a)
and (b) and a halogen-based flame retardant, had
especially excellent properties for all of heat
resistance, fluidity, toughness, low water absorbance,
and rigidity, as well as excellent flame resistance.
In contrast, in Comparative Example 22, which
comprises a polyamide obtained by polymerization of less
than 50 mol% of 2-methylpentamethylenediamine, the
extrusion state was unstable, and a polyamide composition
could not be obtained.
Further, for the polyamide compositions of
Comparative Examples 23 and 24, which comprise a
polyamide obtained by polymerization of less than 50 mol%
of an alicyclic dicarboxylic acid, heat resistance and
low water absorbance were poor.
In addition, for the polyamide composition of
Comparative Example 25, which comprises a polyamide
produced by the method disclosed in Patent Document 1,
the flow length was short, fluidity was too low, and the
molding properties were insufficient. In addition,
tensile elongation was small and toughness was also
insufficient.
For Comparative Example 28, which comprises PA66,
heat resistance and low water absorbance were poor.


[0277]
Polyamide composition comprising (E) phosphinate and/or
diphosphinate
Example 96
The polyamide of Example 1 was used by drying under
a nitrogen flow so that the moisture content was adjusted
to about 0.2 mass%. Using a twin-screw extruder having
one feed opening (top feed) on the upstream side and
another two feed openings, at a middle section of the
extruder and at the downstream side near the die (TEM 35,
(|)L/D = 47.6, set temperature 340°C, screw revolution
speed 100 rpm, and output rate 30 kg/hr, manufactured by
Toshiba Machine Co., Ltd.), the (A) polyamide was fed
from the top feed opening provided at the uppermost
upstream portion of the extruder, an (E) phophinate and a
(G) flame retardant auxiliary were fed from the feed
opening at the middle section of the extruder, and a (B)
inorganic filler was fed from the feed opening on the
downstream side near the die. A melt kneaded product
extruded from a die head was cooled in a strand form,
which was pelletized to form polyamide composition
pellets. The blend amount was, based on 100 parts by
mass of the (A) polyamide, 42.0 parts by mass of the (E)
phophinate, 2.0 parts by mass of the (G) flame retardant
auxiliary, and 48.0 parts by mass of the (B) inorganic
filler. Table 18 shows the measurement results of
measurements carried out on the obtained polyamide


composition based on the above-described measurement
methods.
[0278]
Examples 97 to 116
Examples 97 to 116 were carried out in the same
manner as Example 96, except that the polyamides of
Examples 2 to 21 were used instead of the polyamide of
Example 1. Tables 18 and 19 show the measurement results
of measurements carried out on the obtained polyamide
compositions based on the above-described measurement
methods.
[0279]
Example 117
Example 117 was carried out in the same manner as
Example 100, except that the (G) flame retardant
auxiliary was not blended. Table 19 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.
[0280]
Example 118
Example 118 was carried out in the same manner as
Example 100, except that 2.0 parts by mass of magnesium
hydroxide as the (G) flame retardant auxiliary was used.
Table 19 shows the measurement results of measurements
carried out on the obtained polyamide composition based
on the above-described measurement methods.


[0281]
Comparative Example 2 9
An attempt was made to carry out Comparative Example
29 in the same manner as Example 96, except the polyamide
of Comparative Example 1 was used instead of the
polyamide of Example 1. However, the extrusion state was
very unstable, and a polyamide composition could not be
obtained.
[0282]
Comparative Examples 30 to 35
Comparative Examples 30 to 35 were carried out in
the same manner as Example 96, except that the polyamides
of Comparative Examples 2 to 7 were used instead of the
polyamide of Example 1. Table 20 shows the measurement
results of measurements carried out on the obtained
polyamide compositions based on the above-described
measurement methods.








[0286]
From the results of Tables 18 to 20, the polyamide
compositions of Examples 96 to 118, which comprise a
polyamide obtained by polymerization of a specific (a)
and (b) and a phosphinate, had especially excellent
properties for all of heat resistance, fluidity,
toughness, low water absorbance, and rigidity, as well as
excellent flame resistance.
In contrast, in Comparative Example 29, which
comprises a polyamide obtained by polymerization of less
than 50 mol% of 2-methylpentamethylenediamine, the
extrusion state was unstable, and a polyamide composition
could not be obtained.
Further, for the polyamide compositions of
Comparative Examples 30 and 31, which comprise a
polyamide obtained by polymerization of less than 50 mol%
of an alicyclic dicarboxylic acid, heat resistance and
low water absorbance were poor.
In addition, for the polyamide composition of
Comparative Example 32, which comprises a polyamide
produced by the method disclosed in Patent Document 1,
the full filling pressure was large, fluidity was too low,
and the molding properties were insufficient. In
addition, tensile elongation was small and toughness was
also insufficient.
For Comparative Example 35, which comprises PA66,
heat resistance and low water absorbance were poor.


[0287]
Polyamide composition comprising (F) stabilizer
Example 119
A polyamide composition was obtained by blending 0.3
parts by mass of a stabilizer (21) N,N'-hexane-1,6-
diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]
based on 100 parts by mass of the polyamide of Example 1,
and melt kneading the resultant mixture using a twin-
screw extruder (TEM 35, L/D = 47.6, set temperature
340°C, screw revolution speed 300 rpm, manufactured by
Toshiba Machine Co., Ltd.). Table 21 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.
[0288]
Examples 120 to 139
Examples 120 to 139 were carried out in the same
manner as Example 119, except that the respective
polyamides of Examples 2 to 21 were used instead of the
polyamide of Example 1. Tables 21 and 22 show the
measurement results of measurements carried out on the
obtained polyamide compositions based on the above-
described measurement methods.
[0289]
Comparative Example 36
An attempt was made to carry out Comparative Example
36 in the same manner as Example 119, except the


polyamide of Comparative Example 1 was used instead of
the polyamide of Example 1. However, the extrusion state
was very unstable, and a polyamide composition could not
be obtained.
[0290]
Comparative Examples 37 to 42
Comparative Examples 37 to 42 were carried out in
the same manner as Example 119, except that the
respective polyamides of Comparative Examples 2 to 7 were
used instead of the polyamide of Example 1. Table 23
shows the measurement results of measurements carried out
on the obtained polyamide compositions based on the
above-described measurement methods.
[0291]
Example 14 0
Example 140 was carried out in the same manner as
Example 123, except that a stabilizer (22) bis(2,6-di-t-
butyl-4-methylphenyl)pentaerythritol diphosphite was used
instead of the stabilizer (21) N,N'-hexane-1,6-diylbis[3-
(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]. Table 24
shows the measurement results of measurements carried out
on the obtained polyamide composition based on the above-
described measurement methods.
[0292]
Example 141
Example 141 was carried out in the same manner as
Example 123, except that a stabilizer (23) bis(2,2,6,6-


tetramethyl-4-piperidyl)-sebacate was used instead of the
stabilizer (21) N,N'-hexane-1,6-diylbis[3-(3,5-di-t-
butyl-4-hydroxyphenyl propionamide)]. Table 2 4 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.
[0293]
Example 142
Example 142 was carried out in the same manner as
Example 123, except that a stabilizer (24) 2-(2'-hydroxy-
4'-hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine was used
instead of the stabilizer (21) N,N'-hexane-1,6-diylbis[3-
(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]. Table 24
shows the measurement results of measurements carried out
on the obtained polyamide composition based on the above-
described measurement methods.
[0294]
Example 143
Example 140 was carried out in the same manner as
Example 123, except that 0.1 parts by mass of a
stabilizer (25) sodium hypophosphite was used instead of
the stabilizer (21) N,N'-hexane-1,6-diylbis[3-(3,5-di-t-
butyl-4-hydroxyphenyl propionamide)]. Table 24 shows the
measurement results of measurements carried out on the
obtained polyamide composition based on the above-
described measurement methods.


[0295]
Example 144
Example 144 was carried out in the same manner as
Example 123, except that 0.5 parts by mass of the
stabilizer (21) N,N'-hexane-1,6-diylbis[3-(3,5-di-t-
butyl-4-hydroxyphenyl propionamide)] was used based on
100 parts by mass of the polyamide of Example 5. Table
24 shows the measurement results of measurements carried
out on the obtained polyamide composition based on the
above-described measurement methods.
[0296]
Example 145
Example 145 was carried out in the same manner as
Example 123, except that 3.0 parts by mass of the
stabilizer (21) N,N'-hexane-1,6-diylbis[3-(3,5-di-t-
butyl-4-hydroxyphenyl propionamide)] was used based on
100 parts by mass of the polyamide of Example 5. Table
24 shows the measurement results of measurements carried
out on the obtained polyamide compositions based on the
above-described measurement methods.
Table 24 also shows the measurement results of
measurements carried out on the obtained polyamide of
Example 5 based on the above-described measurement
methods.


[0297]
Example 14 6
A polyamide composition was obtained by blending 0.3
parts by mass of the stabilizer (21) N,N'-hexane-1,6-
diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)]
and 0.3 parts by mass of the stabilizer (22) bis(2,6-di-
t-butyl-4-methylphenyl)pentaerythritol diphosphite based
on 100 parts by mass of the polyamide of Example 5, and
melt kneading the resultant mixture using a twin-screw
extruder (TEM 35, L/D = 47.6, set temperature 340°C,
screw revolution speed 300 rpm, manufactured by Toshiba
Machine Co., Ltd.). Table 24 shows the measurement
results of measurements carried out on the obtained
polyamide composition based on the above-described
measurement methods.
[0298]
Example 147
A polyamide composition was obtained by blending 0.3
parts by mass of the stabilizer (22) bis(2,6-di-t-butyl-
4-methylphenyl)pentaerythritol diphosphite and 0.3 parts
by mass of the stabilizer (24) 2-(2'-hydroxy-4'-
hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine based on 100
parts by mass of the polyamide of Example 5, and melt
kneading the resultant mixture using a twin-screw
extruder (TEM 35, L/D = 47.6, set temperature 340°C,
screw revolution speed 300 rpm, manufactured by Toshiba
Machine Co., Ltd.). Table 24 shows the measurement


results of measurements carried out on the obtained
polyamide composition based on the above-described
measurement methods.
[0299]
Example 14 8
A polyamide composition was obtained by blending 0.3
parts by mass of the stabilizer (21) N,N'-hexane-1,6-
diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)],
0.3 parts by mass of the stabilizer (22) bis(2,6-di-t-
butyl-4-methylphenyl)pentaerythritol diphosphite, and 0.3
parts by mass of the stabilizer (23) bis(2,2,6,6-
tetramethyl-4-piperidyl)-sebacate based on 100 parts by
mass of the polyamide of Example 5, and melt kneading the
resultant mixture using a twin-screw extruder (TEM 35,
(j)L/D = 47.6, set temperature 340°C, screw revolution
speed 300 rpm, manufactured by Toshiba Machine Co., Ltd.).
Table 24 shows the measurement results of measurements
carried out on the obtained polyamide composition based
on the above-described measurement method.
[0300]
Example 14 9
A polyamide composition was obtained by blending 0.3
parts by mass of the stabilizer (21) N,N'-hexane-1,6-
diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl propionamide)],
0.3 parts by mass of the stabilizer (22) bis(2,6-di-t-
butyl-4-methylphenyl)pentaerythritol diphosphite, and 0.3
parts by mass of the stabilizer (24) 2-(2'-hydroxy-4'-


hexyloxyphenyl)-4,6-diphenyl-1,3,5-triazine based on 100
parts by mass of the polyamide of Example 5, and melt
kneading the resultant mixture using a twin-screw
extruder (TEM 35, L/D = 47.6, set temperature 340°C,
screw revolution speed 300 rpm, manufactured by Toshiba
Machine Co., Ltd.). Table 24 shows the measurement
results of measurements carried out on the obtained
polyamide composition based on the above-described
measurement method.










[0305]
From the results of Tables 21 to 24, the polyamide
compositions of Examples 117 to 149, which comprise a
polyamide obtained by polymerization of a specific (a)
dicarboxylic acid and (b) diamine, and a stabilizer, had
especially excellent properties for all of heat
resistance, fluidity, toughness, low water absorbance,
and rigidity, as well as excellent resistance to heat
discoloration and weatherability.
In contrast, in Comparative Example 36, which
comprises a polyamide obtained by polymerization of less
than 50 mol% of 2-methylpentamethylenediamine, the
extrusion state was unstable, and a polyamide composition
could not be obtained.
Further, for Comparative Examples 37 and 38, which
comprise a polyamide obtained by polymerization of less
than 50 mol% of an alicyclic dicarboxylic acid, heat
resistance and low water absorbance were poor.
In addition, for Comparative Example 39, which
comprises a polyamide produced by the method disclosed in
Patent Document 1, the melt shear viscosity was large,
fluidity was too low, and the molding properties were
insufficient. In addition, tensile elongation was small
and toughness was also insufficient.
For Comparative Example 42, which comprises PA66,
heat resistance and low water absorbance were poor.


[0306]
The present application is based on a Japanese
patent application filed on March 12, 2008 (Japanese
Patent Application No. 2008-62811), a Japanese patent
application filed on March 24, 2008 (Japanese Patent
Application No. 2008-75926), and a Japanese patent
application filed on October 10, 2008 (Japanese Patent
Application No. 2008-264182), whose contents are hereby
incorporated by reference herein.
Industrial Applicability
[0307]
The present invention can provide a high-melting-
point polyamide which has excellent heat resistance,
fluidity, toughness, low water absorbance, and rigidity.
Further, the polyamide according to the present invention
has industrial applicability, and can for example be
preferably used as a molding material for various parts,
such as in automobiles, electric and electronics,
industrial materials, and daily and household articles.


We Claim:
1. A polyamide obtainable by polymerizing (a)
dicarboxylic acid comprising at least 50 mol% of an
alicyclic dicarboxylic acid and (b) diamine comprising
at least 50 mol% of a diamine having a substituent
branched from a main chain.
2. The polyamide according to claim 1, wherein the
diamine having the substituent branched from the main
chain is 2-methylpentamethylenediamine.
3. The polyamide according to claim 1 or 2, wherein the
alicyclic dicarboxylic acid is 1,4-
cyclohexanedicarboxylic acid.
4. The polyamide according to any one of claims 1 to 3,
wherein the dicarboxylic acid further comprises an
aliphatic dicarboxylic acid having 10 or more carbon
atoms.
5. The polyamide according to any one of claims 1 to 4,
which is obtainable by further copolymerizing with a (c)
lactam and/or aminocarboxylic acid.
6. The polyamide according to any one of claims 1 to 5,
which has a melting point of from 270 to 350°C.
7. The polyamide according to any one of claims 1 to 6,
which has a trans isomer ratio of from 50 to 85%.
8. The polyamide according to any one of claims 1 to 7,
which has a b value of 0 or less.
9. A polyamide composition comprising:

(A) a polyamide according to any one of claims 1 to
8; and
(B) an inorganic filler.
10. A polyamide composition comprising:
(A) a polyamide according to any one of claims 1 to
8; and
(C) a copper compound and a metal halide.
11. A polyamide composition comprising:
(A) a polyamide according to any one of claims 1 to
8; and
(D) a halogen-based flame retardant.
12. A polyamide composition comprising:
(A) a polyamide according to any one of claims 1 to
8; and
(E) a phosphinate and/or diphosphinate.
13. A polyamide composition comprising:
(A) a polyamide according to any one of claims 1 to
8; and
(F) a stabilizer.
14. An automobile component, comprising a polyamide
composition according to any one of claims 9 to 13.
15. The automobile component according to claim 14,
which is an automobile air intake system component or an
automobile cooling system component.
16. A method for producing a polyamide, comprising a
step of polymerizing an (a) dicarboxylic acid comprising
at least 50 mol% of an alicyclic dicarboxylic acid and a

(b) diamine comprising at least 50 mol% of an aliphatic
diamine having a substituent branched from a main chain.
17. The method for producing the polyamide according to
claim 16, wherein the polymerization is carried out while
maintaining a trans isomer ratio at from 50 to 80%.
18. A polyamide obtainable by the method of claim 16 or
17.


The present invention relates to a polyamide
obatainable by polymerizing an (a) dicarboxylic acid
comprising at least 50 mol% of an alicyclic dicarboxylic
acid and a (b) diamine comprising at least 50 mol% of a
diamine having a substituent branched from a main chain.

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=UBlU0/3ToxXhuzDgL2hsYA==&loc=wDBSZCsAt7zoiVrqcFJsRw==


Patent Number 270055
Indian Patent Application Number 3326/KOLNP/2010
PG Journal Number 48/2015
Publication Date 27-Nov-2015
Grant Date 26-Nov-2015
Date of Filing 09-Sep-2010
Name of Patentee ASAHI KASEI CHEMICALS CORPORATION
Applicant Address 1-105 KANDA JINBOCHO, CHIYODA-KU, TOKYO 101-8101, JAPAN
Inventors:
# Inventor's Name Inventor's Address
1 SHIKANO, YASUKAZU 1-105 KANDA JINBOCHO, CHIYODA-KU, TOKYO 101-8101, JAPAN
2 SAKUMA, TERUAKI 1-105 KANDA JINBOCHO, CHIYODA-KU, TOKYO 101-8101, JAPAN
3 ARAMAKI, MASAAKI 1-105 KANDA JINBOCHO, CHIYODA-KU, TOKYO 101-8101, JAPAN
4 NITTO, YU 1-105 KANDA JINBOCHO, CHIYODA-KU, TOKYO 101-8101, JAPAN
5 IEDA, SHINJI 1-105 KANDA JINBOCHO, CHIYODA-KU, TOKYO 101-8101, JAPAN
6 MATSUI, HIROKI 1-105 KANDA JINBOCHO, CHIYODA-KU, TOKYO 101-8101, JAPAN
PCT International Classification Number C08G 69/26
PCT International Application Number PCT/JP2009/054693
PCT International Filing date 2009-03-11
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2008-062811 2008-03-12 Japan
2 2008-075926 2008-03-24 Japan
3 2008-264182 2008-10-10 Japan