Specification
^
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Description
Title of Invention: THERMOPLASTIC RESIN COMPOSITION
HAVING HIGH DURABILITY
Technical Field
[0001]
The present invention relates to a thermoplastic
resin composition, particularly to a thermoplastic resin
composition having durability, particularly, high bending
fatigue resistance, and a molded article formed from the
thermoplastic resin composition.
Background Art
[0002]
Thermoplastic polyurethanes (TPU) as urethanic
thermoplastic elastomers (TPE), since having good
elasticity and being excellent in abrasion resistance,
mechanical strength, chemical resistance and the like,
are used as materials of belt products, tubes, hoses and
other various types of molded articles,
[0003]
However, molded articles formed from thermoplastic
polyurethanes, if used for a long time in the state of
being continuously or intermittently subjected to a large
load, come to be damaged and broken in some cases. For
example, if belt products formed from thermoplastic
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polyurethanes are used for a long time, belt members and
the like abrade and crack in some cases.
[0004]
Japanese Patent Laid-Open No. 11-34 9804 discloses a
blend containing a thermoplastic polyurethane and an
ethylene-propylene rubber (EPM) and/or a modified
ethylene-propylene rubber (modified EPM) in a proportion
of the former / the latter (in weight ratio) = 3/1 to
999/1. However, molded articles using the blend, if used
for a long time under a heavy load state, cannot always
be said to have sufficient durability, particularly,
sufficient bending fatigue resistance.
Citation List
Patent Literature
[0005]
Patent Literature 1: Japanese Patent Laid-Open No. 11-
349804
Summary of Invention
Technical Problem
[0006]
Therefore, it is an object of the present invention
to provide a thermoplastic resin composition capable of
providing a thermoplastic resin molded article not
causing abrasion, damage, cracks, breaks and the like and
being remarkably excellent in durability even if the
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molded article is used for a long time in the state of
being subjected to a large load or even if the time of
being subjected to a load is short, and a molded article
formed from the thermoplastic resin composition.
It is another object of the present invention
particularly to provide a thermoplastic resin composition
useful as a material for a belt product and the like
having remarkably high durability usable without damage
for a long time, and a molded article formed from the
thermoplastic resin composition.
Solution to Problem
[0007]
As a result of detailed studies on the relationship
between the bending fatigue resistance and the shape and
diameter of a dispersed particle into a thermoplastic
resin composition comprising a thermoplastic resin and a
modified ethylene copolymer, and obtained by dispersing
the modified ethylene copolymer (B) into the
thermoplastic resin (A) in order to achieve the above
objects, the present inventors have found that the
regulation of the average dispersed particle aspect ratio
and the average dispersed particle diameter in specific
ranges remarkably improves the durability (particularly,
bending fatigue resistance) of a molded article formed
from the thermoplastic resin composition. It also has
been found that the blending of a polyurethane-based
M
4 -
thermoplastic elastomer (thermoplastic polyurethane) with
a modified ethylene-propylene-diene copolymerized rubber
(modified EPDM), which has often been utilized as
industrial crosslinked rubber products, and has not been
used as a modifier for other resins so far, can provide a
molded article remarkably improved in not only the
abrasion resistance but also the bending fatigue
resistance, and thus remarkably excellent in durability.
These findings have led to the completion of the present
invention by carrying out further studies.
[0008]
That is, the present invention provides a
thermoplastic resin composition comprising a
thermoplastic resin (A) and a modified ethylene copolymer
(B) dispersed in the thermoplastic resin (A), and
obtained by dispersing the modified ethylene copolymer
(B) into the thermoplastic resin (A), wherein the
modified ethylene copolymer (B) in the thermoplastic
resin composition has an average dispersed particle
aspect ratio of 1 to 3.5, and an average dispersed
particle diameter of not more than 3 \xm.
[0009]
The modified ethylene copolymer (B) is preferably a
copolymer, modified with an unsaturated carboxylic acid
or a derivative thereof, of ethylene with at least one
monomer component selected from the group consisting of
(i) olefin components except for ethylene, (ii) diene
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5 -
components and (iii) ester components having an
ethylenically unsaturated group.
[0010]
The thermoplastic resin (A) is preferably at least
one selected from the group consisting of polyamide
resins, polyester resins, polycarbonate-based resins and
polyacetal resins.
[0011]
The thermoplastic resin (A) is preferably a
thermoplastic elastomer (TPE) (Al) as well. The
thermoplastic elastomer (Al) is preferably at least one
selected from the group consisting of polyurethane-based
thermoplastic elastomers (All), polyester-based
thermoplastic elastomers (A12) and polyamide-based
thermoplastic elastomers (A13).
[0012]
The weight proportion [(B)/(A)] of the modified
ethylene copolymer (B) to the thermoplastic resin (A) is,
for example, in the range of 0.1/99.9 to 60/40.
[0013]
The present invention also provide a thermoplastic
resin composition being a thermoplastic elastomer alloy
comprising a polyurethane-based thermoplastic elastomer
(All) and a modified ethylene-propylene-diene
copolymerized rvibber (Bl), and obtained by dispersing the
modified ethylene-propylene-diene copolymerized rubber
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6 -
{Bl) into the polyurethane-based thermoplastic elastomer
(All).
[0014]
The weight proportion [{Bl)/(A11)] of the modified
ethylene-propylene-diene copolymerized rubber (Bl) to the
polyurethane-based thermoplastic elastomer (All) is, for
example, in the range of 0.1/99.9 to 60/40. The modified
ethylene-propylene-diene copolymerized rubber (Bl) is
preferably an ethylene-propylene-diene copolymerized
rubber modified with an unsaturated carboxylic acid or a
derivative thereof. The modified ethylene-propylenediene
copolymerized rubber (Bl) in the thermoplastic
elastomer alloy preferably has an average dispersed
particle aspect ratio of 1 to 3.5 and an average
dispersed particle diameter of not more than 3 pm.
[0015]
The each thermoplastic resin composition preferably
has a hardness (JIS K6253, durometer type A) of not less
than 60.
[0016]
The present invention further provides a molded
article (excluding belts) formed from the each
thermoplastic resin composition.
[0017]
The molded article includes tubes, hoses, adsorption
pads, vibration-proof dampers, vibration-proof joints,
shock absorbers, casters, rollers and packings.
^ ^
[0018]
In the present description, the hardness is a value
measured according to JIS K6253 (durometer type A).
However, in Examples, there were cases where measurement
was carried out using durometer type D (which will be
described to the effect).
Advantageous Effects of Invention
[0019]
The thermoplastic resin composition according to the
present invention can provide a thermoplastic resin
molded article which is not only excellent in the
abrasion resistance but also remarkably excellent in the
durability (particularly, bending fatigue resistance),
hardly causes abrasion, damage, cracks, breaks and the
like even if the molded article is used for a long time
in the state of being impressed with a large load or even
if the time of being subjected to a load is short, and is
remarkably excellent in the durability and has a long
life in the case where the thermoplastic resin
composition is deformed and even in the case where the
thermoplastic resin composition is used in the vicinity
of another deforming material and is directly or
indirectly subjected to an impact and an influence
thereof.
Brief Description of Drawings
!^u
[0020]
[Figure 1] Figure 1 is a SEM photograph of a pellet
cross-section of a thermoplastic elastomer alloy (an
alloy of an EPDM and an etheric TPU) obtained in
Comparative Example 4.
[Figure 2] Figure 2 is a SEM photograph of a pellet
cross-section of a thermoplastic elastomer alloy (an
alloy of a maleic anhydride-modified EPDM and an etheric
TPU) obtained in Example 4.
[Figure 3] Figure 3 is a SEM photograph of a pellet
cross-section of a thermoplastic elastomer alloy (an
alloy of an EPDM and an esteric TPU) obtained in
Comparative Example 6.
[Figure 4] Figure 4 is a SEM photograph of a pellet
cross-section of a thermoplastic elastomer alloy (an
alloy of a maleic anhydride-modified EPDM and an esteric
TPU) obtained in Example 7.
[Figure 5] Figure 5 is a graph indicating a relationship
between the blend ratio of a modified ethylene copolymer
in a thermoplastic resin composition and the bending
fatigue resistance.
[Figure 6] Figure 6 is a graph indicating results of
tensile tests of resin compositions obtained in Examples
14 to 18 and Comparative Examples 11 to 15.
[Figure 7] Figure 7 is a TEM photograph of a sheet crosssection
of a resin composition obtained in Comparative
Example 11.
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does not include a substance corresponding to a modified
ethylene copolymer (B).
[0022]
Examples of the thermoplastic resin (A) include
polyurethane-based resins, polyester-based resins,
polyamide-based resins, polyimide-based resins,
polystyrenic resins, polycarbonate-based resins,
polyolefinic resins, acrylic resins, methacrylic resins,
fluororesins, silicone-based resins, polyacetal resins
(polyoxymethylene), polyarylate resins, polyphenylene
ethers, polyphenylene sulfides, polysulfones,
polyethersulfones, polyetheretherketones, vinyl chloride
resins and polyvinylic resins, but are not limited
thereto as long as they are capable of dispersing a
modified ethylene copolymer (B). The thermoplastic resin
(A) may be used singly or plurally, or may use a
multicomponent singly or plurally such as copolymers,
additions, blends and alloys. The thermoplastic resin
(A) has a weight-average molecular weight of, for example,
5,000 to 1,000,000, and preferably 10,000 to 500,000.
[0023]
More specific examples of the thermoplastic resin
(A) include, for example, polyamide-based resins such as
polyamide 11, polyamide 12, polyamide 6, polyamide 66,
polyamide 610, polyamide 612, polyamide 666, polyamide 46,
polyamide lOT, polyamide 6T and aramid resins (whole
aromatic polyamide); polyester-based resins such as
B
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polyethylene terephthalate, polybutylene terephthalate
and polyethylene naphthalate; polyimide; polystyrene;
polycarbonate; polyolefinic resins such as polyethylenes
and polypropylenes; fluororesxns such as polyvinylidene
fluorides, polytetrafluoroethylenes, polyvinyl fluorides,
polychlorotrifluoroethylenes, perfluoroalkoxyfluororesins,
ethylene tetrafluoride-propylene hexafluoride copolymers,
ethylene-ethylene tetrafluoride copolymers and ethylenechlorotrifluoroethylene
copolymers; polyacetal resins;
polyethersulfones; polyetheretherketones; and polyvinylic
resins such as polyvinyl alcohols and ethylene vinyl
alcohols. Additives such as reinforcing fillers such as
glass fibers may be incorporated in these thermoplastic
resins (A). Also amorphous materials {thermoplastic
resins) having no distinct melting point, in the case of
being molded by a thermoplastic resin molding machine,
can be incorporated. The thermoplastic resin (A) may be
resins obtained from fossil raw materials and natural
resins as well.
[0024]
Among the above, the thermoplastic resin (A) is
preferably at least one selected from the group
consisting of polyamide-based resins, polyester-based
resins, polycarbonate-based resins and polyacetal resins.
[0025]
[Thermoplastic elastomer (Al)]
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12
As the thermoplastic resin (A), a thermoplastic
elastomer (TPE) (Al) may be preferably used. The
thermoplastic elastomer (Al) comprises a hard phase (hard
segment) and a soft phase (soft segment), and though
exhibiting properties as a rubber at normal temperature,
is a polymer exhibiting thermoplasticity at high
temperatures. Use of the thermoplastic elastomer (Al)
can improve the abrasion resistance, mechanical strength
and molding processability of a thermoplastic resin
composition.
[0026]
The thermoplastic elastomer (Al) may be used singly
or as a mixture of two or more. As the thermoplastic
resin (A), a thermoplastic elastomer (Al) and a resin
other than a thermoplastic elastomer may be concurrently
used.
[0027]
Examples of the thermoplastic elastomer (Al) include
polyurethane-based thermoplastic elastomers (All),
polyester-based thermoplastic elastomers (A12),
polyamide-based thermoplastic elastomers (A13),
polystyrenic thermoplastic elastomers (A14),
fluoropolymer-based thermoplastic elastomers (A15),
polyvinyl chloride-based thermoplastic elastomers (A16),
polyolefinic thermoplastic elastomers (A17) and
polyimide-based elastomers (A18), but are not limited
thereto. The thermoplastic elastomer (Al) may also be a
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thermoplastic elastomer in which a resin, an elastomer
and/or an oligomer component are blended (mixed). The
thermoplastic elastomer (Al) may be used singly or in
combinations of two or more. Among the above
thermoplastic elastomers (Al), preferable are
polyurethane-based thermoplastic elastomer (All),
polyester-based thermoplastic elastomers (A12) and
polyamide-based thermoplastic elastomers (A13), and
especially preferable are polyurethane-based
thermoplastic elastomers (All).
[0028]
[Polyurethane-based thermoplastic elastomer (All)]
As the polyurethane-based thermoplastic elastomer
(All), known thermoplastic polyurethanes (TPU) can be
used. The thermoplastic polyurethane can be used singly
or in combinations of two or more. The thermoplastic
polyurethane is usually obtained by reacting a
polyisocyanate, a long-chain polyol and a chain extender,
and as required, other isocyanate-reactive compounds.
[0029]
The polyisocyanate is not especially limited as long
as it is a compound having at least two isocyanate groups
in the molecule. The polyisocyanate includes, for
example, aliphatic polyisocyanates, alicyclic
polyisocyanates, aromatic polyisocyanates and araliphatic
(aromatic-aliphatic) polyisocyanates. The polyisocyanate
can be used singly or in combinations of two or more.
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[0030]
Examples of the aliphatic polyisocyanate include
aliphatic diisocyanates such as 1,3-trimethylene
diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-
pentamethylene diisocyanate, 1,6-hexamethylene
diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene
diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene
diisocyanate, 2'-methyl-l, 5-pentamethylene diisocyanate,
3-methyl-l,5-pentamethylene diisocyanate, 2,4,4-
trimethyl-1,6-hexamethylene diisocyanate and 2,2,4-
trimethyl-1,6-hexamethylene diisocyanate.
[0031]
Examples of the alicyclic polyisocyanate include
alicyclic diisocyanates such as 1,3-cyclopentane
diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-
cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-
trimethylcyclohexyl isocyanate (isophorone diisocyanate),
4,4'-methylenebis(cyclohexyl isocyanate), methyl-2,4-
cyclohexane diisocyanate, methyl-2,6-cyclohexane
diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-
bls(isocyanatomethyl)cyclohexane and norbornane
diisocyanate.
[0032]
Examples of the aromatic polyisocyanate include
aromatic diisocyanates such as m-phenylene diisocyanate,
p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-
tolylene diisocyanate, naphthylene 1,4-diisocyanate,
- 15 -
naphthylene 1,5-diisocyanate, 4,4'-diphenyl diisocyanate
(4,4'-biphenyl diisocyanate), 4,4'-diphenylmethane
diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-
diphenylmethane diisocyanate, 4,4'-diphenyl ether
diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and 4,4'-
diphenylpropane diisocyanate.
[0033]
Examples of the araliphatic polyisocyanate include
araliphatic diisocyanates such as 1,3-xylylene
diisocyanate, 1,4-xylylene diisocyanate, co,©'-
diisocyanato-1,4-diethylbenzene, 1,3-bis(1-isocyanato-lmethylethyl)
benzene, 1,4-bis(1-isocyanato-l-methylethyl)
benzene and 1,3-bis(a,a-dimethylisocyanatomethyl)benzene.
[0034]
As the polyisocyanate, suitably usable are 1,6-
hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl
isocyanate), 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-
bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
4,4'-diphenylmethane diisocyanate, 1,3-xylylene
diisocyanate, 1,4-xylylene diisocyanate, norbornane
diisocyanate and 1,3-bis(a,adimethylisocyanatomethyl)
benzene.
[0035]
As the polyisocyanate, also usable are dimers,
trimers, reaction products or polymers of the above
16
exemplified aliphatic polyisocyanates, alicyclic
polyisocyanates, aromatic polyisocyanates and araliphatic
polyisocyanates (for example, a dimmer or a trimer of
diphenylmethane diisocyanate, reaction products of
trimethylolpropane and tolylene diisocyanate, reaction
products of trimethylolpropane and hexamethylene
diisocyanate, polymethylene polyphenyl isocyanates,
polyether polyisocyanates, polyester polyisocyanates and
the like) and the like.
[0036]
Examples of the long-chain polyol include polyether
polyols, polyester polyols, polycarbonate polyols,
polyolefin polyols and polyacryl polyols. The long-chain
polyol has a number-average molecular weight of usually
not less than 500, preferably 500 to 10,000, still more
preferably 600 to 6,000, and further still more
preferably 800 to 4,000. The long-chain polyol can be
used singly or in combinations of two or more.
[0037]
Examples of the polyether polyol include
polyalkylene ether glycols such as polyethylene ether
glycols, polypropylene ether glycols and
polytetramethylene ether glycols (PTMG), and additionally
copolymers containing a plurality of alkylene oxides
(alkylene oxide-another alkylene oxide) as monomer
components, such as ethylene oxide-propylene oxide
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- 17 -
copolymers. Among the polyether polyols, especially
preferable are polytetramethylene ether glycols (PTMG).
[0038]
As the polyester polyol, usable are, for example,
polycondensates of a polyhydric alcohol and a polyvalent
carboxylic acid, ring-opened polymers of cyclic esters
(lactones), and reaction products of three components of
a polyhydric alcohol, a polyvalent carboxylic acid and a
cyclic ester (lactone). In the polycondensates of a
polyhydric alcohol and a polyvalent carboxylic acid, as
the polyhydric alcohol, usable are, for example, ethylene
glycol, diethylene glycol, propylene glycol, dipropylene
glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol,
2-methyl-l,3-propanediol, 1,5-pentanediol, neopentyl
glycol, 1,6-hexanediol, S-methyl-l, 5-pentanediol, 2,4-
diethyl-1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol,
glycerol, trimethylolpropane, trimethylolethane,
cyclohexanediols (1,4-cyclohexanediol and the like),
cyclohexanedimethanols (1,4-cyclohexanedimethanol and the
like), bisphenols (bisphenol A and the like), and sugar
alcohols (xylitol, sorbitol and the like). On the other
hand, examples of the polyvalent carboxylic acid include
aliphatic dicarboxylic acids such as malonic acid, maleic
acid, succinic acid, glutaric acid, adipic acid, suberic
acid, azelaic acid, sebacic acid and dodecanedioic acid;
alicyclic dicarboxylic acids such as 1,4-
cyclohexanedicarboxylic acid; and aromatic dicarboxylic
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18
acids such as terephthalic acid, isophthalic acid, orthophthalic
acid, 2,6-naphthalenedicarboxylic acid, paraphenylenedicarboxylic
acid and trimellitic acid. In the
ring-opened polymers of cyclic esters, examples of the
cyclic ester include propiolactone, p-methyl-6-
valerolactone and e-caprolactone. In the reaction
products of three components, the above exemplified
polyhydric alcohols, polyvalent carboxylic acids and
cyclic esters and the like can be used. Among the
polyester polyols, preferable are adipate-based polyester
polyols [for example, C2-6 alkylene adipates such as
poly(ethylene adipate), poly(diethylene adipate),
poly(propylene adipate), poly(tetramethylene adipate),
poly(hexamethylene adipate) and poly(neopentylene
adipate)] which are polycondensates of adipic acid and a
polyhydric alcohol (for example, one or two or more of
alkane diols having 2 to 6 carbon atoms such as ethylene
glycol, 1,4-butanediol, neopentyl glycol and 1,6-
hexanediol), caprolactone polyols obtained by ringopening
polymerization of 8-caprolactone, polyester
polyols obtained by ring-opening polymerization of pmethyl-
8-valerolactone using a polyhydric alcohol such as
ethylene glycol, and the like.
[0039]
Examples of the polycarbonate polyol include
reaction products of a polyhydric alcohol and phosgene, a
chloroformate ester, a dialkyl carbonate or a diaryl
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19
carbonate (a polyhydric alcohol and a compound selected
from the group consisting of phosgene, a chloroformate
ester, a dialkyl carbonate and a diaryl carbonate); and
ring-opened polymers of cyclic carbonate esters (alkylene
carbonates and the like). In the reaction products of a
polyhydric alcohol and phosgene, as the polyhydric
alcohol, specifically usable are the above exemplified
polyhydric alcohols {for example, ethylene glycol,
propylene glycol, 1,3-butanediol, 1,4-butanediol,
neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol and
1,9-nonanediol). In the ring-opened polymers of cyclic
carbonate esters, examples of the alkylene carbonate
include ethylene carbonate, trimethylene carbonate,
tetramethylene carbonate and hexamethylene carbonate.
Here, the polycarbonate polyol suffices if being a
compound having carbonate bonds in the molecule and
having hydroxyl groups at the terminals, and may have
ester bonds together with the carbonate bonds. Typical
examples of the polycarbonate polyol include
poly(hexamethylene carbonate) diols, diols obtained by
ring-opening addition polymerization of a lactone to a
poly(hexamethylene carbonate) diol, and cocondensates of
a poly(hexamethylene carbonate) diol and a polyester diol
or a polyether diol.
[0040]
The polyolefin polyol is a polyol having an olefin
as a component of a skeleton (or a main chain) of a
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20 -
polymer or a copolymer, and having at least two hydroxyl
groups in the molecule (particularly at the terminals).
The above olefin may be an olefin (for example, an aolefin
such as ethylene or propylene) having a carboncarbon
double bond at the terminal, may be an olefin (for
example, isobutene) having a carbon-carbon double bond at
a site other than the terminals, or further may be a
diene (for example, butadiene or isoprene). Typical
examples of the polyolefin polyol include substances
(compounds) obtained by modifying, with hydroxyl groups,
the terminals of butadiene- or isoprene-based polymers
such as butadiene homopolymers, isoprene homopolymers,
butadiene-styrene copolymers, butadiene-isoprene
copolymers, butadiene-acrylonitrile copolymers,
butadiene-2-ethylhexyl acrylate copolymers, butadiene-noctadecyl
acrylate copolymers.
[0041]
The polyacryl polyol is a polyol having a
(meth)acrylate as a component of a skeleton (or a main
chain) of a polymer or a copolymer, and having at least
two hydroxyl groups in the molecule (particularly at the
terminals). As the (meth)acrylate, suitably used are
alkyl (meth)acrylate esters [for example, Cl-20 alkyl
(meth)acrylate esters]. As the polyol, every material
other than materials cited here can be used.
[0042]
U |
21 -
As the chain extender, usable are chain extenders
usually used in production of thermoplastic polyurethanes,
and the type thereof is not especially limited, and lowmolecular
weight polyols and polyamines and the like can
be used. The chain extender has a molecular weight of
usually less than 500, and preferably not more than 300.
The chain extender can be used singly or in combinations
of two or more.
[0043]
Typical examples of the chain extender include
polyols (particularly, diols) such as ethylene glycol,
diethylene glycol, propylene glycol, 1,3-propanediol,
1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,2-
pentanediol, 2,3-pentanediol, neopentyl glycol, 1,6-
hexanediol, 3-methyl-l,5-pentanediol, 1,4-cyclohexanediol
and 1,4-cyclohexanedimethanol, and polyamines
(particularly, diamines) such as hexamethylenediamine,
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 4,4'-
raethylenebis-2-chloroaniline. Among these, diols are
especially preferable.
[0044]
As the thermoplastic polyurethane, preferable are
thermoplastic polyurethanes obtained by reacting a
polyisocyanate, a long-chain polyol and a chain extender
in the range of the ratio (NCO/isocyanate-reactive
groups), of the molar number of isocyanate groups of the
polyisocyanate and the molar number of isocyanate^^
22
reactive groups (hydroxy1 group, amino group and the
like) of the long-chain polyol and the chain extender, of
0.9 to 1.3, especially 0.95 to 1.1. The proportion of
the long-chain polyol to the chain extender, [the former
/ the latter (molar ratio)], can suitably be selected in
the range of, for example, 0.1 to 1.0, and preferably 0.2
to 2, according to physical properties and the like of
the thermoplastic polyurethane. In the above reaction,
in order to promote the reaction, as required, a catalyst
such as a tertiary amine, an organometal compound or a
tin compound may be used.
[0045]
The thermoplastic polyurethane usually has a weightaverage
molecular weight Mw of 5,000 to 1,000,000. The
thermoplastic polyurethane has thermoplasticity, though
some exhibit no distinct melting point. The
thermoplastic polyurethane can be molded by a common
thermoplastic resin molding machine such as extrusion,
injection molding, heat press or the like.
[0046]
The hardness of the thermoplastic polyurethane is,
but not limited to, from the viewpoint of raising
mechanical properties of the thermoplastic resin
composition (thermoplastic elastomer alloy and the like)
according to the present invention, preferably not less
than 60 (for example, 60 to 96), more preferably not less
than 78 (for example, 78 to 96), still more preferably
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- 23
not less than 89 (for example, 89 to 95), and especially
preferably not less than 91 (for example, 91 to 94), in
hardness of JIS K6253 (durometer type A). From the
viewpoint of letting the thermoplastic resin composition
(thermoplastic elastomer alloy and the like) have
reasonable flexibility and raising the bending fatigue
resistance, the thermoplastic polyurethane has a hardness
in the range of, for example, 60 to 93, and especially
preferably 78 to 91 (particularly 78 to 88).
[0047]
The thermoplastic polyurethane preferably uses a
polyester polyol or a polyether polyol as the long-chain
polyol. Among these, the thermoplastic polyurethane is
especially preferably adipate-based TPUs using an
adipate-based polyester polyol as the long-chain polyol,
caprolactone-based TPUs using a caprolactone polyol as
the long-chain polyol, and PTMG-based TPUs using a
polytetramethylene ether glycol (PTMG) as the long-chain
polyol.
[0048]
As the thermoplastic polyurethane, commercially
available products can be used. Examples of the
commercially available products include an adipate-based
TPU of 80 in hardness (an adipate-based TPU with a
hardness of 80, a hardness of 80), an adipate-based TPU
of 90 in hardness, a caprolactone-based TPU of 90 in
*
- 24 -
hardness, a PTMG-based TPU of 92 in hardness, and an
adipate-based TPU of 92 in hardness.
[0049]
[Polyester-based thermoplastic elastomer (A12)]
As the polyester-based thermoplastic elastomer (A12),
known polyester-based thermoplastic elastomers can be
used. The polyester-based thermoplastic elastomer {A12)
can be used singly or in combinations of two or more.
The polyester-based thermoplastic elastomer {A12) can be
produced by a known method such as the esterification
reaction or the transesterification reaction.
[0050]
The polyester-based thermoplastic elastomer (A12) is
preferably, for example, polyester-based thermoplastic
elastomers having as main constituting units a hard
segment composed of an aromatic polyester unit and a soft
segment composed of an aliphatic polyether unit and/or an
aliphatic polyester unit,
[0051]
The aromatic polyester unit is mainly a unit formed
of an aromatic dicarboxylic acid or an ester-forming
derivative thereof (a Cl-4 alkyl ester, an acid halide or
the like) and a diol or an ester-forming derivative
thereof (an acetylated derivative, an alkaline metal salt
or the like). Specific examples of the aromatic
dicarboxylic acid include terephthalic acid, isophthalic
acid, phthalic acid, naphthalene-2,6-dicarboxylic acid.
- 25 -
naphthalene-2,7-dicarboxylic acid, anthracenedicarboxylic
acid, diphenyl-4,4'-dicarboxylic acid (biphenyl-4,4'-
dicarboxylic acid), diphenoxyethanedicarboxylic acid,
4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic
acid and sodium 3-sulfoisophthalate. Specific examples
of the diol include diols having a molecular weight of
not more than 400, and include, for example, aliphatic
diols such as 1,4-butanediol, ethylene glycol,
trimethylene glycol, pentamethylene glycol, hexamethylene
glycol and neopentyl glycol, decamethylene glycol;
alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-
dicyclohexanedimethanol and tricyclodecanedimethanol; and
aromatic diols such as xylylene glycol, bis{phydroxy)
diphenyl (bis{p-hydroxy)biphenyl), bis(phydroxy)
diphenylpropane, 2,2'-bis [ {4- (2-
hydroxyethoxy)phenyl)]propane, bis[4-(2-
hydroxyethoxy)phenyl] sulfone, 1,1-bis[4-(2-
hydroxyethoxy)phenyl]cyclohexane and 4,4'-dihydroxy-pterphenyl.
These aromatic dicarboxylic acids or esterforming
derivatives thereof, and diols and ester-forming
derivatives thereof may be concurrently used in two or
more, respectively- Preferable aromatic polyester units
include a polybutylene terephthalate unit derived from
terephthalic acid and/or dimethyl terephthalate and 1,4-
butanediol, and a unit composed of a polybutylene
terephthalate unit derived from terephthalic acid and/or
dimethyl terephthalate and a polybutylene isophthalate
4
- 26 -
unit derived from isophthalic acid and/or dimethyl
isophthalate and 1,4-butanediol.
[0052]
Examples of an aliphatic polyether constituting the
aliphatic polyether unit include poly(ethylene oxide)
glycols, poly(propylene oxide) glycols,
poly(tetramethylene oxide) glycols, poly(hexamethylene
oxide) glycols, copolymers of ethylene oxide and
propylene oxide, ethylene oxide addition polymers of
poly(propylene oxide) glycols and copolymer glycols of
ethylene oxide and tetrahydrofuran. Among these,
preferable are poly(tetramethylene oxide) glycols,
ethylene oxide addition products of poly(propylene oxide)
glycols and copolymer glycols of ethylene oxide and
tetrahydrofuran. Examples of an aliphatic polyester
constituting the aliphatic polyester unit include poly(scaprolactone)
s, polyenantholactones, polycaprolactones,
polybutylene adipates and polyethylene adipates. Among
these, preferable are poly (s-caprolactone)s, polybutylene
adipates, polyethylene adipates, and the like.
[0053]
The soft segment composed of an aliphatic polyether
unit and/or an aliphatic polyester unit has a numberaverage
molecular weight of preferably 300 to 6,000, and
especially preferably 500 to 4,000, in the copolymerized
state.
[0054]
^
- 27 -
The ratio of the hard segment composed of an
aromatic polyester unit and the soft segment composed of
an aliphatic polyether unit and/or an aliphatic polyester
unit in the polyester-based thermoplastic elastomer is
not especially limited, but is, for example, the former /
the latter (weight ratio) = 1/99 to 99.5/0.5, and
preferably 50/50 to 99/1.
[0055]
[Polyamide-based thermoplastic elastomer (A13)]
As the polyamide-based thermoplastic elastomer (A13),
known polyamide-based thermoplastic elastomers can be
used. The polyamide-based thermoplastic elastomer (A13)
can be used singly or in combinations of two or more.
[0056]
As the polyamide-based thermoplastic elastomer (A13),
preferable are, for example, polyamide-based
thermoplastic elastomers having as main constituting
units a hard segment composed of a polyamide unit and a
soft segment composed of an aliphatic polyether unit
and/or an aliphatic polyester unit.
[0057]
Examples of a polyamide constituting the polyamide
unit include nylon 6, nylon 66, nylon 11 and nylon 12.
Examples of an aliphatic polyether constituting the
aliphatic polyether unit include the same aliphatic
polyethers as exemplified in the term of the polyesterbased
thermoplastic elastomer. Among these, preferable
IP
- 28
are poly(tetramethylene oxide) glycols, ethylene oxide
additions of poly(propylene oxide) glycols, and copolymer
glycols of ethylene oxide and tetrahydrofuran. Examples
of an aliphatic polyester constituting the aliphatic
polyester unit include the same aliphatic polyesters as
exemplified in the term of the polyester-based
thermoplastic elastomer. Among these, preferable are
poly (e-caprolactone)s, polybutylene adipates,
polyethylene adipates, and the like.
[0058]
[Other thermoplastic elastomers]
As the polystyrenic thermoplastic elastomer (A14),
the fluoropolymer-based thermoplastic elastomer (A15),
the polyvinyl chloride-based thermoplastic elastomer
(A16), the polyolefinic thermoplastic elastomer (A17) and
the polyimide-based elastomer {Al8), usable are
respective known elastomers.
[0059]
As the thermoplastic resin (A), from the viewpoint
of the adhesion with a modified ethylene copolymer (B),
preferable are resins having, in the molecule (for
example, on the main chain, terminals and side chains of
a polymer), functional groups (or functional groups
having affinity) reactive, in heating and mixing, with
modifying groups (for example, a carboxyl group or its
salt, a carboxylate ester group, an acid anhydride group,
a carboxylic acid halide group, an amido group, an imido
¥ 29
group, a glycidyl group (epoxy group), a halogen atom, an
amino group, an imido group, a phosphino group, a thioxy
group and a silicon-containing group, which will be
described later) of the modified ethylene copolymer (B).
Examples of such a resin include thermoplastic resins
having, on the terminals of a polymer main chain,
functional groups such as a hydroxyl group, a carboxyl
group, an amino group and a thiol group, for example,
polyamide-based resins, polyester-based resins,
polycarbonate-based resins, polyacetal resins,
polyphenylene ethers, polyphenylene sulfides,
polyurethane-based thermoplastic elastomers (All),
polyester-based thermoplastic elastomers (A12) and
polyamide-based thermoplastic elastomers (A13).
[0060]
[Modified ethylene copolymer (B)]
In the present invention, as the modified ethylene
copolymer (B), usable are known modified ethylene
copolymers. The modified ethylene copolymer (B) can be
used singly or in combinations of two or more. The
modified ethylene copolymer (B) has a weight-average
molecular weight of, for example, 5,000 to 1,000,000, and
preferably 10,000 to 500,000.
[0061]
The modified ethylene copolymer (B) is an ethylene
copolymer modified with an unsaturated carboxylic acid or
a derivative thereof or another functional group.
¥
- 30 -
Examples of the ethylene copolymer include copolymers of
ethylene with at least one monomer component selected
from the group consisting of (i) olefin components except
for ethylene, (ii) diene components and (iii) ester
components having an ethylenically unsaturated group.
Examples of the olefin component except for ethylene
include a-olefins having 3 to 12 carbon atoms such as
propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-
octene and 1-decene. Examples of the diene component
include non-conjugated dienes such as ethylidene
norbornene, dicyclopentadiene and 1,4-hexadiene.
Examples of the ester component having an ethylenically
unsaturated group include alkyl (meth)aerylate esters
such as methyl (meth)acrylate and ethyl (meth)acrylate,
and vinyl carboxylate esters such as vinyl acetate and
vinyl propionate.
[0062]
Typical examples of the ethylene copolymer include
ethylene-propylene-diene copolymers (ethylene-propylenediene
rubbers; EPDM), ethylene-propylene copolymers
(ethylene-propylene rubbers; EPM), ethylene-methyl
(meth)acrylate copolymers, ethylene-ethyl (meth)acrylate
copolymers and ethylene-vinyl acetate copolymers. Among
these, especially preferable are ethylene-propylene-diene
copolymers (ethylene-propylene-diene rubbers; EPDM) and
ethylene-propylene copolymers (ethylene-propylene
rubbers; EPM).
$
- 31 -
[0063]
Examples of an unsaturated carboxylic acid used for
modification of the ethylene copolymer include acrylic
acid, methacrylic acid, maleic acid, fumaric acid,
tetrahydrophthalic acid, itaconic acid, citraconic acid,
crotonic acid, isocrotonic acid and
norbornenedicarboxylic acid. Examples of a derivative of
an unsaturated carboxylic acid include esters of
unsaturated carboxylic acids [for example, glycidyl
(meth)acrylate and maleate esters], acid anhydrides
(maleic anhydride and the like), salts, acid halides,
amides and imides. An ethylene copolymer modified with
an unsaturated carboxylic acid or a derivative thereof
has, in the molecule, a carboxyl group or a salt thereof,
a carboxylate ester, an acid anhydride group, a carboxyl
acid halide group, an amido group, an imido group or the
like.
[0064]
Other functional groups used for modification of the
ethylene copolymer are not especially limited as long as
they are capable of chemically modifying the ethylene
copolymer. The other functional groups include, for
example, a glycidyl group {epoxy group), a halogen atom,
an amino group, an iraido group, a phosphino group, a
thioxy group, a silicon atom-containing group. These
functional groups may be incorporated singly or in two or
more.
32
[0065]
Modification of an ethylene copolymer can be carried
out, for example, by heating and kneading the ethylene
copolymer and an unsaturated carboxylic acid or a
derivative thereof in the presence of a graft
polymerization initiator [for example, a peroxide
initiator such as 1,3-bis(t-butylperoxyisopropyl)benzene
or dicumyl peroxide]. Modification of an ethylene
copolymer can be carried out also by further using an
unsaturated carboxylic acid (acrylic acid, methacrylic
acid or the like) as another comonomer when ethylene and
a comonomer such as an ester having an ethylenically
unsaturated bond [methyl (meth)acrylate, ethyl
(meth)acrylate, vinyl acetate or the like] are
copolymerized. Further, modification of an ethylene
copolymer with the above another functional group can
also be carried out by a known method. Modification may
use a chemical reaction such as random copolymerization,
alternating copolymerization, block copolymerization or
graft copolymerization, may use a state of a reaction
intermediate, or may use a physical modification such as
addition, coexistence or generation.
[0066]
The modification ratio with an unsaturated
carboxylic acid or a derivative thereof or the another
functional group in the modified ethylene copolymer (B)
is, as a content rate of a structural unit containing
- 33 -
groups originated (derived) from the unsaturated
carboxylic acid or the derivative thereof, or a
structural unit containing the another functional group,
for example, about 0.1 to 20 wt%, preferably about 0.5 to
10 wt%, and still more preferably about 1 to 8 wt%, with
respect to the whole modified ethylene copolymer (a whole
amount of the modified ethylene copolymer). If the
content rate is too low, the improving effect of the
abrasion resistance and the bending fatigue resistance in
blending with a thermoplastic resin (A) is liable to
become small. By contrast, if the content rate is too
high, properties as a copolymer intrinsic to an ethylene
copolymer become liable to decrease, making difficult the
maintenance of the copolymer and also making difficult
the regulation of the properties.
[0067]
The modification of an ethylene copolymer may be
carried out independently for the ethylene copolymer
before being blended with a thermoplastic resin, or may
be carried out simultaneously in a stage of blending a
before-modification ethylene copolymer with a
thermoplastic resin. An unreacted carboxylic acid or
derivative thereof may be removed, or may be used as it
remains.
[0068]
The modified ethylene copolymer (B) is preferably a
copolymer, modified with an unsaturated carboxylic acid
»
34
or a derivative thereof, of ethylene with at least one
monomer component selected from the group consisting of
(i) olefin components except for ethylene (particularly,
a-olefins containing at least propylene), (ii) diene
components and (iii) ester components having an
ethylenically unsaturated group. Among these, especially
preferable are polymers obtained by modifying a copolymer
of ethylene, an olefin except for ethylene (particularly,
a-olefin containing at least propylene) and/or a diene
with an unsaturated carboxylic acid or a derivative
thereof (particularly maleic anhydride).
[0069]
A preferable modified ethylene copolymer (B)
includes modified ethylene-propylene-diene copolymerized
rubbers (modified EPDM) (Bl), modified ethylene-propylene
rubbers (modified EPM) (B2) and carboxylic acid-modified
ethylene acryl rubbers (acid-modified ethylene acryl
elastomers) (B3). Among these, preferable are modified
ethylene-propylene-diene copolymerized rubbers (modified
EPDM) (Bl).
[0070]
[Modified ethylene-propylene-diene copolymerized
rubber (Bl)]
In the present invention, as the modified ethylenepropylene-
diene copolymerized rubber (Bl) (modified EPDM),
usable are known modified ethylene-propylene-diene
copolymerized rubbers. The modified ethylene-propylene%
- 35 -
diene copolymerized rubber (Bl) can be used singly or in
combinations of two or more.
[0071]
An ethylene-propylene-diene copolymer (EPDM) is a
copolymer of ethylene, propylene and a non-conjugated
diene. Examples of the diene include 5-ethylidene-2-
norbornene, dicyclopentadiene and 1,4-hexadiene. A
modified ethylene-propylene-diene copolymerized rubber
(modified EPDM) (Bl) used in the present invention is
obtained by modifying an EPDM with, for example, an
unsaturated carboxylic acid or a derivative thereof (an
ester, an acid anhydride, a salt, an acid halide, an
amide, an imide, or the like) or another functional group.
Examples of the unsaturated carboxylic acid or the
derivative thereof include, as in the above, acrylic acid,
methacrylic acid, maleic acid, fumaric acid,
tetrahydrophthalic acid, itaconic acid, citraconic acid,
crotonic acid, isocrotonic acid, norbornenedicarboxylic
acid, glycidyl (meth)acrylate, maleate esters and maleic
anhydride, and the unsaturated carboxylic acid or the
derivative thereof may have a structure of an ester salt,
a metal salt thereof and the like. J\mong these,
preferable are acrylic acid, methacrylic acid and maleic
anhydride, and especially preferable is maleic anhydride.
The another functional group includes, for example, a
glycidyl group, a halogen atom, an amino group, an imido
group, a phosphino group and a thioxy group.
4
- 36 -
[0072]
Modification of an EPDM can be carried out, for
example, by heating and kneading the EPDM and an
unsaturated carboxylic acid or a derivative thereof in
the presence of a graft polymerization initiator [for
example, a peroxide initiator such as l,3-bis(tbutylperoxyisopropyl)
benzene or dicumyl peroxide]. The
ratio of ethylene and propylene in an EPDM used as a raw
material is, from the viewpoint of properties thereof as
an elastomer, and the like, for example, the former / the
latter (weight ratio) = 10/90 to 95/5, and preferably
about 50/50 to 85/15. The content rate of a structural
unit originated from a diene component in an EPDM is, for
example, about 0.1 to 25 wt%, preferably about 1 to 20
wt%, and more preferably about 2 to 10 wt%, to the whole
EPDM.
[0073]
The modification ratio with an unsaturated
carboxylic acid or a derivative thereof in the modified
ethylene-propylene-diene copolymerized rubber (Bl) is, as
a content rate of a structural unit originated from the
unsaturated carboxylic acid or the derivative thereof,
for example, about 0.1 to 20 wt%, preferably about 0.5 to
10 wt%, and more preferably about 1 to 8 wt%, with
respect to the whole modified EPDM (a whole amount of the
modified EPDM) . If the content rate is too low, the
improving effect of the abrasion resistance and the
^
37
bending fatigue resistance in blending with a
thermoplastic resin (A) [for example, the polyurethanebased
thermoplastic elastomer (Al)] is liable to become
small. By contrast, if the content rate is too high, the
function as an elastomer becomes liable to decrease.
[0074]
The modification of an EPDM may be carried out
independently for the EPDM before being blended with a
TPD, or may be carried out simultaneously in a stage of
blending a before-modification EPDM with a TPU. An
unreacted carboxylic acid or a derivative thereof may be
removed, or may be used as it remains.
[0075]
The modified ethylene-propylene-diene copolymerized
rubber (Bl) has a melt flow rate (ASTM D1238, 280°C/2.16
kg) of, for example, 5 to 80 g/lO-min, and preferably 10
to 40 g/lO-min.
[0076]
As the modified ethylene-propylene-diene
copolymerized rubber (Bl), commercially available
products may be used. Examples of the commercially
available product include "Fusabond N416" by trade name
(maleic anhydride-modified EPDM, Du Pont K.K.).
[0077]
A modified ethylene-propylene-diene copolymerized
rubber (Bl) to become a dispersoid in a resin composition
may be crosslinked, or uncrosslinked. For example.
- 38 -
dynamic crosslinking means,^ in which crosslinking is
carried out with thermoplasticity being maintained, may
be used,
[0078]
Although a modified ethylene-propylene-diene
copolymerized rubber (Bl) is often crosslinked and then
utilized as industrial rubber products so far, and has
not been so much used as a modifier for other resins, it
has been found according to the present invention that
making the copolymerized rubber dispersed and contained
in a thermoplastic resin can remarkably improve
properties of the thermoplastic resin.
[0079]
As the modified ethylene-propylene copolymerized
rubber (modified EPM) (B2) as well, known modified
ethylene-propylene copolymerized rubbers can be used.
The modified ethylene-propylene copolymerized rubber can
be used singly or in combinations of two or more. An
ethylene-propylene copolymer (EPM) is a copolymer of
ethylene and propylene, and the modification of the EPM
can be carried out similarly to the modification of the
EPDM. As the acid-modified ethylene acryl elastomer (B3)
as well, known acid-modified ethylene acryl elastomers
can be used. The acid-modified ethylene acryl elastomer
(B3) can be used singly or in combinations of two or more,
[0080]
[Thermoplastic resin composition]
- ^
39 -
The thermoplastic resin composition according to the
present invention is a resin composition comprising the
thermoplastic resin (A) and the modified ethylene
copolymer (B), and obtained by dispersing the modified
ethylen copolymer (B) into the thermoplastic resin (A),
as described above,
[0081]
In the present invention, the weight proportion
[(B)/(A)] of the (B) to (A) is, though depending on the
kinds of the components (A) and (B), usually in the range
of 0,1/99.9 to 60/40. The lower limit of the proportion
(ratio) is preferably 1/99, more preferably 3/97, and
especially preferably 7.5/92.5; and the upper limit
thereof is preferably 55/45, more preferably 50/50, still
more preferably 30/70, and especially preferably 25/75
(particularly, 22/78) . More specifically, the weight
proportion [ (B)/(A)] of the (B) to (A) is preferably
0.1/99.9 to 30/70, more preferably 1/99 to 25/75, and
still more preferably 3/97 to 22/78 (particularly,
7.5/92.5 to 22/78), If the proportion is too low, the
improving effect of the durability of the abrasion
resistance, and the bending fatigue resistance becomes
small. By contrast, if the proportion is too high,
properties (mechanical strength and the like) intrinsic
to the thermoplastic resin become liable to decrease.
[0082]
-^^P'
- 40 -
The present inventors have found that in a resin
composition which is obtained by dispersing the modified
ethylene copolymer (B) into the thermoplastic resin (A)
and comprises the thermoplastic resin (A) and the
modified ethylene copolymer (B), the durability such as
the bending fatigue resistance of molded articles of the
resin composition exhibits a more improved value than a
value anticipated for the each material as a single
material. That is, it has been found that an actually
acquired value of the bending fatigue resistance of a
blend of a thermoplastic resin (A) and a modified
ethylene copolymer (B) is higher than a value thereof
calculated on the assumption of the additivity being held
in the blend, thus providing a synergistic effect. For
example, in Figure 5 [which is a graph indicating a
relationship between the blend ratio (wt%) of a modified
ethylene copolymer (MAH-EPDM) and the bending fatigue
resistance, based on data of Examples and Comparative
Examples described later], a line (dotted line in Figure
5) connecting values of the bending numbers of times by a
straight line in the cases of the blend ratio of MAH-EPDM
being 0 wt% and 100 wt% indicates values of the bending
numbers of times in respective blend ratios on the
assumption of the additivity being held. By contrast,
the result of a resin composition (solid line in Figure
5) is a result of the bending numbers of times, which are
by far more than the dotted line, thus being conceivably
c
- 41
a synergistic effect. The synergistic effect is large in
the case of using a thermoplastic elastomer (Al) as the
thermoplastic resin (A) (for example, a polyurethanebased
thermoplastic elastomer), and is remarkable
particularly in the case of using a modified ethylenepropylene-
diene copolymerized rubber as the modified
ethylene copolymer (B).
[0083]
In the thermoplastic resin composition according to
the present invention, in addition to the above (A) and
(B), as required, additives can be blended. Examples of
the additives include antioxidants, ultraviolet absorbers,
plasticizers, stabilizers, mold lubricants, surfactants,
antistatic agents, electroconductive materials, colorants
(pigments, dyes), flame retardants, foaming agents, slip
agents, lubricants, bulking agents, crosslinking agents,
solvents, developing solutions, extenders, waxes, oils,
greases, processing aids, processing agents, reinforcing
materials, fillers, antiblocking agents and antiaging
agents.
[0084]
In the thermoplastic resin composition according to
the present invention, in addition to the above (A) and
(B), as required, reinforcing materials can be
incorporated. Examples of the reinforcing materials
include fibers, powders, clothes, substrate materials,
long fibers, short fibers, glass clothes, fabrics, carbon
42 -
nanotubes, fullerenes, graphites, carbon blacks, silicas,
foams, beads, inorganic fillers, heat dissipation fillers,
electroconductive fillers, ceramics, fine ceramics and
carbon fibers.
[0085]
In the thermoplastic resin composition according to
the present invention, the total content of the
thermoplastic resin (A) and the modified ethylene
copolymer (B) is, for example, not less than 60 wt%,
preferably not less than 80 wt%, and more preferably not
less than 90 wt%,
[0086]
The modified ethylene copolymer (B) in the
thermoplastic resin composition according to the present
invention has an average dispersed particle aspect ratio
(= major diameter / minor diameter) of 1 to 3.5,
preferably 1 to 3, and more preferably 1 to 2. An
average dispersed particle aspect ratio near 1 means that
in an actual thermoplastic resin composition, the
disperse shape of the (B) dispersed is near a true sphere.
Here, the average dispersed particle aspect ratio is
calculated from a major diameter / a minor diameter of
island phases (disperse phase) in a planarized visual
field when a disperse state of a material at an arbitrary
place of a thermoplastic resin composition is observed by
known means (SEM, TEM, AFM or the like) . The modified
ethylene copolymer (B) in the thermoplastic resin
#
- 43 -
composition according to the present invention has an
average dispersed particle diameter of not more than 3 |um,
and preferably not more than 1 |nm. An average dispersed
particle aspect ratio nearer 1, that is, nearer a true
sphere, is better. A smaller average dispersed particle
diameter is better. If the average dispersed particle
aspect ratio is in the above range, since the degree of
anisotropicity is very low and there is no directivity, a
high rigidity is exhibited on stresses from every
direction. Consequently, the dispersed particle exhibits
the effect as a reinforcing filler in every direction.
[0087]
Molded articles in the disperse state as described
above are resultantly concluded to be improved in
durability, for example, to an instantaneous stress or a
stress repeated for a long time. The phenomenon of
abrasion, stress crack or solvent crack is a phenomenon
in which in thermoplastic resin molded articles causing
the phenomenon, originally present countless invisible
flaws and incisions are subjected to stimuli, stresses or
stress concentrations from outside, or notches and the
like directly made from the outside make starting points,
so that crazes are generated and grow further to cracks,
and finally lead to strength decrease and fracture of the
resin molded articles. Although there are cases where
crazes on the way stage are a few, a large number of
crazes are already present on sites having been subjected
#
44 -
to stresses in molded articles in many cases, and the
crazes are sometimes united to thereby grow as cracks.
That is, incisions to become micro-starting points,
through phenomena such as growth, linking, branching and
deepening, grow into crazes and cracks. Since the crack
growth is a result of that an elastic energy of a molded
article withstanding a stress exceeds a surface energy of
the molded article, the crack is a physical phenomenon
developed as a result that the surface energy cannot
support the molded article. Here, in the case of molded
articles constituted of usual single materials, it is
remarkably difficult to suppress growth of incisions and
generated crazes, which allows easy growth according to
the stress, and finally leads to breakage. The breakage
means not only a large fracture of the whole but also
includes fractures in microscopical areas. The surface
energy as a crack resistance is highest in a spherical
shape; and that a dispersoid is spherical provides a
large resistance to cracks in the dispersoid, resultantly
providing a large resistance of a resin layer as a
disperse medium to cracks. Impartation of such an
inhomogeneous structure can provide a thermoplastic resin
composition better in durability than the case of being
of a homogeneous structure, in deformations, movements,
works and loads {which mean usage in various types of
dynamic fatigues such as abrasion tests, bending fatigue
tests, impact resistance tests, fracture tests, and
45 -
actual usage and specifications) whereby incisions,
crazes, cracks and notches cause fracture, breakage,
chipping and checking.
[0088J
Use of the thermoplastic resin composition according
to the present invention retard the growth of incisions,
crazes, cracks, notches and the like in microscopical
regions, and can thus retard cracking and fracture of
molded articles and can resultantly prevent serious
damage, because resisting effects including relaxation,
dispersion and adsorption of the initial-stage stress
concentration when the incisions and the like in the
microscopical regions start to grow are attained because
of being a micro phase separation structure having a
nearly spherical disperse phase. From the above, it is
conceivable that since the disperse state is a micro
inhomogeneous state of a sea-island structure in which a
nearly spherical island component is micro-dispersed, and
is a micro-dispersion of a viscoelastic material having a
relatively flexible property, the disperse phase can
absorb the energy and becomes an energy buffering
material to the growth and linking and the like of cracks,
and effectively suppresses the growth of cracks and the
like particularly in the initial period. In the present
invention, if the average dispersed particle diameter and
the average dispersed particle aspect ratio are in the
above ranges, the energy adsorption efficiency is
#
- 46 -
remarkably high. Therefore, molded articles obtained
from the thermoplastic resin composition according to the
present invention are excellent not only in the abrasion
resistance but remarkably excellent in the durability
such as the bending fatigue resistance, and are
remarkably suppressed in damage such as abrasion and
cracks even if the molded articles are used in the state
of being imparted with a large load for a long time or
repeatedly imparted with a load, thus remarkably
elongating the life. Besides, even if the island
component is of a micro spherical particle shape, if the
component amount is increased, the restraint of the
island component progresses; so heat becomes liable to be
generated due to stresses and movements to which the
molded articles are subjected; thus, separation is caused
between the sea component and the island component in
repeated deformation for a long time, which leads to the
generation of cracks. From the above, the most
preferable blend according to the present invention is
such that the (B) in an elastomer form is dispersed in an
average dispersed particle aspect ratio of 1 to 1.6 and
an average dispersed particle diameter of not more than 3
]m, and [(B)/(A)] is 3/97 to 60/40. With these factors
in these ranges, particularly the growth of incisions,
crazes, cracks, notches and the like in the resin
composition is suppressed also in the case where the
resin composition is subjected to a stress concentration
- 47 -
and a repeated stress, whereby molded articles excellent
in the durability in dynamic applications can be provided.
[0089]
The average dispersed particle aspect ratio and the
average dispersed particle diameter can be measured by a
scanning electron microscope (SEM), a transmission
electron microscope (TEM), further an atomic force
microscope (AiFM), and the like.
[0090]
The hardness of the thermoplastic resin composition
according to the present invention is not especially
limited, but the hardness in JIS K6253 (durometer type A)
is preferably not less than 60 (for example, 60 to 95),
more preferably not less than 78 (for example, 78 to 95),
still more preferably not less than 89 (for example, 89
to 95), and especially preferably not less than 91 (for
example, 91 to 95) . From the viewpoint of having a
reasonable flexibility and enhancing the bending fatigue
resistance, the hardness of the thermoplastic resin
composition is, for example, in the range of 60 to 93,
and especially preferably in the range of 77 to 91
(particularly 77 to 88). The hardness of the
thermoplastic resin composition can be regulated by the
hardness of a thermoplastic resin (A), the weight
proportion of the modified ethylene copolymer (B) to the
thermoplastic resin (A), the kinds and amounts of
additives, and the like.
#
- 48 -
[0091]
The breaking strength (JIS K7311) of the
thermoplastic resin composition according to the present
invention depends largely on a resin to become a
continuous phase (sea phase), but is, for example, 25 to
100 MPa, preferably 30 to 80 MPa, and more preferably 35
to 75 MPa; and the breaking elongation (JIS K7311) is,
for example, 300 to 1,000%), preferably 350 to 800%, and
more preferably 400 to 700%.
[0092]
The thermoplastic resin composition according to the
present invention can be produced by mixing the
thermoplastic resin (A), the modified ethylene copolymer
(B), and the additives used according to needs by the
same method as the case of preparing usual polymer alloys
or polymer blends. For example, the thermoplastic resin
composition can be produced by pre-mixing the
thermoplastic resin (A), the modified ethylene copolymer
(B), and the additives used according to needs in
predetermined proportions, and thereafter, kneading the
mixture under heating, under pressure, in the presence of
a solvent or the like by using a single-screw extruder, a
twin-screw extruder, a mixing roll, a Banbury mixer, a
batch-type kneader, a reactor, a reactive molding machine,
an injection molding machine or the like. In the case of
carrying out heating and kneading using an extruder, the
composition is extruded in a strand form, and may be cut
- 49 -
into a suitable length to thereby make a granule such as
a pellet. Besides the above method, the thermoplastic
resin composition can be produced also by charging and
mixing the modified ethylene copolymer (B) and/or the
additives during the production of the thermoplastic
resin (A) . In the case of using a thermoplastic
elastomer (Al) such as a thermoplastic polyurethane
(polyurethane-based thermoplastic elastomer) as the
thermoplastic resin (A), a thermoplastic elastomer alloy
can be obtained.
[0093]
The average dispersed particle aspect ratio and the
average dispersed particle diameter of the modified
ethylene copolymer (B) in the thermoplastic resin
composition according to the present invention can be
regulated by the kinds and the degrees of crosslinking of
the thermoplastic resin (A) and the modified ethylene
copolymer (B), the viscosity ratio and the volume ratio
of the thermoplastic resin (A) and the modified ethylene
copolymer (B), the magnitude of a shearing force
impressed in kneading a mixture containing the
thermoplastic resin (A) and the modified ethylene
copolymer (B) , and the like. In more detail, the
disperse state of the composition can be controlled by
regulating respective amounts (vol%) and shearing
viscosities of the thermoplastic resin (A) and the
modified ethylene copolymer (B) and regulating a molding
1^
- 50
method and the like, for example, at a temperature and a
shearing rate at which both the thermoplastic resin (A)
and the modified ethylene copolymer (B) become flowable.
In a completely incompatible blend system, the case where
one component has a higher vol% than the other or the
case where one component has a lower shearing viscosity
than the other basically takes a sea-island structure;
and the higher-vol% and/or lower-shearing viscosity
component forms a sea side {continuous phase). The case
where respective vol% and shearing viscosities approach
closely provides a structure in which both components
form micro-continuous phases. On the other hand, the
case where the shearing viscosity of a sea component
becomes higher than that of an island component due to a
reaction of the components during kneading includes a
case where the sea-island structure reverses during the
kneading; and a dual-continuous phase develops, though
being a very complicate structure, during the phase
transformation. The reaction used here may be a
crosslinking (curing) of one component, or may involve a
viscosity decrease due to a molecular weight decreasing
phenomenon by transesterification, hydrolysis and the
like of the other component. In the case of a dualcontinuous
phase, although the average dispersed particle
aspect ratio becomes large, since a shearing force can be
most highly transmitted to both components, a microdispersion
can be provided if kneading is carried out
- 51 -
through this process. Further in a sea-island structure,
with respect to the shape of the island side, a shape
near a spherical one is resultantly obtained in the case
where an island-side resin is strongly and quickly
kneaded in a sea-side resin having a relatively low
shearing viscosity as compared with the island side
rather than in the case where both the components have
shearing viscosities close to each other. That is, in
order to obtain micro-dispersing and spherical dispersing
shape, the viscosity condition, the volume ratio
condition and the like of both the components are usually
different. For example, in a reaction-type polymer blend,
by reasonably determining the kneading condition and the
addition condition, the spherical dispersion and the
micro-dispersion can be both satisfied simultaneously.
For example, by using the above-mentioned resin kneading
machine for a suitable time (for example, 30 sec to 15
min) and at a suitable shearing force according to the
materials and the like, the average dispersed particle
aspect ratio and the average dispersed particle diameter
of the modified ethylene copolymer (B) can be made in the
above-mentioned range. At this time, the charging amount
and charging timing are determined according to the
shearing viscosity of each component. The composition is
returned to normal temperature at a rate as near
quenching as possible so that these disperse states are
not destroyed. Thereby, a thermoplastic resin
«
- 52 -
composition having a desired fixed disperse state can be
obtained. As described above, the simultaneous
satisfaction of both the spherical dispersion and the
micro-dispersion is difficult. However, by designing the
viscosities, the amounts and the kinds of components of a
resin composition, the kneading method and the molding
condition, the present invention can achieve the
simultaneous satisfaction of both, and can obtain a
thermoplastic resin composition excellent in the
durability.
[0094]
The thermoplastic resin composition according to the
present invention can be subjected to melt molding,
thermal processing, press molding and the like, and can
provide various types of molded articles by an optional
method such as extrusion, injection molding, blow molding,
calendar molding, casting, coating, sheeting and
lamination.
[0095]
A production method of molded articles of the
thermoplastic resin composition according to the present
invention is not especially limited; molding may be
carried out after the thermoplastic resin composition is
fabricated in advance, or the thermoplastic resin
composition according to the present invention can also
be produced simultaneously when molding is carried out
(for example, a side feed system and a dry blend system).
- 53
The side feed system is a method in which for example,
two components are charged from different feeders to an
extruder in order to regulate mutual melt states to be
blended in a polymer blend. The dry blend system
involves mixing resin materials to be blended in a pellet
form in advance and charging the mixture in the state in
a molding machine (a resin molding machine such as an
extruder or an injection molding machine). The
thermoplastic resin composition according to the present
invention suffices if holding thermoplasticity in the
fabrication time of the composition, and after the
fabrication, may or may not have the thermoplasticity.
There are cases where a final product is a resin
composition having no thermoplasticity, for example, by
addition of a crosslinking agent.
[0096]
[Thermoplastic elastomer alloy]
The thermoplastic resin composition being a
thermoplastic elastomer alloy according to the present
invention (hereinafter, simply referred to as the
"thermoplastic elastomer alloy according to the present
invention" in some cases} is, for example, a composition
comprising the polyurethane-based thermoplastic elastomer
(All) and the modified ethylene-propylene-diene
copolymerized rubber (Bl), and obtained by dispersing the
modified ethylene-propylene-diene copolymerized rubber
(Bl) into the polyurethane-based thermoplastic elastomer
t
- 55 -
(particularly 7.5/92.5 to 22/78). If the proportion is
too low, the improving effect of the durability of the
abrasion resistance and bending fatigue resistance
becomes small. By contrast, if the proportion is too
high, properties (mechanical strength and the like)
intrinsic to the thermoplastic resin are liable to
decrease.
[0098]
As described above, in the thermoplastic elastomer
alloy comprising the polyurethane-based thermoplastic
elastomer (All) and the modified ethylene-propylene-diene
copolymerized rubber (Bl) and obtained by dispersing the
modified ethylene-propylene-diene copolymerized rubber
(Bl) into the polyurethane-based thermoplastic elastomer
(All), a synergistic effect of the bending fatigue
resistance by blending is especially remarkable.
[0099]
Observation by a scanning electron microscope (SEM)
of a molded article cross-section of the thermoplastic
elastomer alloy according to the present invention
reveals that the modified ethylene-propylene-diene
copolymerized rubber (Bl) is highly micro-dispersed in a
matrix composed of the thermoplastic polyurethane (All)
(see Figures 2 and 4). For example, according to a SEM
photograph at a magnification of 2,000 times, in a
thermoplastic elastomer alloy composed of a modified EPDM
and an etheric TPU, no particulate shape cannot be
56
observed though unevenness is slightly seen; and in a
thermoplastic elastomer alloy composed of a modified EPDM
and an esteric TPU, almost no unevenness is observed. By
contrast, in the case of using a non-modified EPDM in
place of the modified EPDM, the particle of EPDM can be
clearly observed; particularly in a thermoplastic
elastomer alloy composed of an EPDM and an esteric TPU,
it is clearly observed that spherical particles of the
EPDM are dispersed in a matrix of the esteric TPU. The
average particle diameter of the particle observed at
this time is a value exceeding 3 [am. That the
dispersibility is remarkably improved in a thermoplastic
elastomer alloy composed of a modified EPDM and a TPU
(especially, an esteric TPU) is presumably because the
polarity of modified sites in the modified EPDM has an
affinity for polar sites of the TPU.
[0100]
Further observation of a molded article crosssection
of the thermoplastic elastomer alloy according to
the present invention using an atomic force microscope
(AFM) reveals particles, which are not observed by SEM,
and which are highly micro-dispersed, of the modified
EPDM in a matrix (thermoplastic polyurethane) [see Figure
12 (Example 4) and Figure 13 (Example 7)]. According to
these AFM photographs, it is found that in either of the
thermoplastic elastomer alloy composed of the modified
EPDM and the etheric TPU, and the thermoplastic elastomer
«
- 57 -
alloy composed of the modified EPDM and the esteric TPU,
the particles are dispersed in an average dispersed
particle diameter of not more than 1 ^m. If these
results and the above-mentioned results of SEM
photographs are collectively considered, an effect of the
affinity of modified sites for the matrix is obvious.
[0101]
The modified ethylene-propylene-diene copolymerized
rubber (Bl) in the thermoplastic elastomer alloy
according to the present invention has an average
dispersed particle aspect ratio of, for example, 1 to 3.5,
preferably 1 to 3, and more preferably 1 to 2. The
modified ethylene-propylene-diene copolymerized rubber
(Bl) in the thermoplastic elastomer alloy according to
the present invention has an average dispersed particle
diameter of, for example, not more than 3 pm, and
preferably not more than 1 |am. The average dispersed
particle aspect ratio nearer 1, that is, the particle
nearer a true sphere, is better. The smaller average
dispersed particle diameter is better. The simultaneous
realization of both can be said to be better.
[0102]
In the thermoplastic elastomer alloy according to
the present invention, in addition to the above (All) and
(Bl), as required, additives can be blended. Examples of
the additives include antioxidants, ultraviolet absorbers,
plasticizers, stabilizers, mold lubricants, surfactants.
^m
- 58 -
antistatic agents, electroconductive materials, colorants
(pigments, dyes), flame retardants, foaming agents, slip
agents, lubricants, bulking agents, crosslinking agents,
solvents, developing solutions, extenders, waxes, oils,
greases, processing aids, processing agents, reinforcing
materials, fillers, antiblocking agents and antiaging
agents.
[0103]
In the thermoplastic elastomer alloy according to
the present invention, the total content of a
thermoplastic polyurethane (All) and a modified ethylenepropylene-
diene copolymerized rubber (Bl) is, for example,
not less than 85 wt%, preferably not less than 90 wt%,
and still more preferably not less than 95 wt%.
[0104]
The hardness of the thermoplastic elastomer alloy
according to the present invention is, but not limited to,
preferably not less than 60 (for example, 60 to 95), more
preferably not less than 78 (for example, 78 to 95),
still more preferably not less than 8 9 (for example, 89
to 95), and especially preferably not less than 91 (for
example, 91 to 95), in hardness of JIS K6253 (durometer
type A) . From the viewpoint of having a reasonable
flexibility and raising the bending fatigue resistance,
the hardness of the thermoplastic elastomer alloy is, for
example, in the range of 60 to 93, and especially
preferably in the range of 77 to 91 (particularly, 77 to
J^^
59 -
88) . The hardness of the thermoplastic elastomer alloy
can be regulated by the hardness of the thermoplastic
polyurethane (All), the weight proportion of the
thermoplastic polyurethane (All) to the modified
ethylene-propylene-diene copolymerized rubber (Bl), the
kinds and amounts of additives and the like.
[0105]
The breaking strength (JIS K7311) of the
thermoplastic elastomer alloy according to the present
invention depends on a thermoplastic elastomer to become
a continuous phase (sea component), but is, for example,
25 to 100 MPa, preferably 30 to 80 MPa, and more
preferably 35 to 75 MPa; and the breaking elongation (JIS
K7311) thereof is, for example, 300 to 1,000%, preferably
350 to 800%, and more preferably 400 to 700%.
[0106]
The thermoplastic elastomer alloy according to the
present invention can be produced by mixing the
thermoplastic polyurethane (All), the modified ethylenepropylene-
diene copolymerized rubber (Bl), and the
additives used according to needs by the same method as
the case of preparing usual polymer alloys or polymer
blends. For example, the thermoplastic elastomer alloy
can be produced by pre-mixing the thermoplastic
polyurethane (All), the modified ethylene-propylene-diene
copolymerized rubber (Bl), and the additives used
according to needs in predetermined proportions, and
- 60
thereafter, kneading the mixture under heating, under
pressure, in the presence of a solvent or the like by
using a single-screw extruder, a twin-screw extruder, a
mixing roll, a Banbury mixer, a batch-type kneader, a
reactor, a reactive molding machine, an injection molding
machine or the like. In the case of carrying out heating
and kneading using an extruder, the alloy is extruded in
a strand form, and may be cut into a suitable length to
thereby make a granule such as a pellet. Besides the
above method, the thermoplastic elastomer alloy according
to the present invention can be produced also by charging
the modified ethylene-propylene-diene copolymerized
rubber (Bl) and/or the additives during the production of
the thermoplastic polyurethane (A).
[0107]
The thermoplastic elastomer alloy according to the
present invention can be subjected to melt molding or
thermal processing, and can provide various types of
molded articles by an optional method such as extrusion,
injection molding, blow molding, calendar molding, press
molding or casting.
[0108]
A production method of molded articles of the
thermoplastic elastomer alloy according to the present
invention is not especially limited; molding may be
carried out after the thermoplastic elastomer alloy is
fabricated in advance, or the thermoplastic elastomer
- 61 ~
alloy according to the present invention can also be
produced simultaneously when molding is carried out (for
example, a side feed system and a dry blend system). The
thermoplastic elastomer composition according to the
present invention suffices if holding thermoplasticity in
the fabrication time of the composition, and after the
fabrication, may or may not have the thermoplasticity.
There are cases where a final product is an elastomer
composition having no thermoplasticity, for example, by
addition of a crosslinking agent, as in the case of the
thermoplastic resin composition. The explanation of the
blending, the composition, the mechanism and the like is
the same as that of the cases of the resin (A) and the
modified ethylene copolymer (B).
[0109]
[Molded article]
Molded articles obtained from the thermoplastic
resin composition according to the present invention and
the thermoplastic elastomer alloy according to the
present invention are excellent not only in the abrasion
resistance but remarkably excellent in the bending
fatigue resistance, and hardly cause abrasion, damage,
cracks, breaks and the like even if being used
continuously or intermittently in the state of being
impressed with a large load, thus providing remarkably
excellent durability and an elongated life. Therefore,
the molded articles are especially useful as belts such
$
- 62 -
as flat belts and V belts, tubes and hoses as well,
adsorption pads, vibration-proof dampers, vibration-proof
joints, shock absorbers, casters, packings, soles (shoe
sole), switches, valves, filters, rolls, rollers (paperdischarge
rollers, paper-feed rollers), clips, films,
sheets, tires, casters, mats, gloves, adhesive bandages,
robes, surface leathers, bags, instrument panels, snow
chains, skiing boots, spring covers, pumps, and physical
functional materials (artificial hearts and the like).
Among these as the molded articles according to the
present invention, preferable are belts such as flat
belts and V belts, tubes, hoses, adsorption pads,
vibration-proof dampers, vibration-proof joints, shock
absorbers, casters, rollers (paper-discharge rollers,
paper-feed rollers and the like), packings, and the like,
in which these durability is remarkably improved because
the bending fatigue resistance is very high.
[0110]
[Belt]
Conveyance belts and transmission belts require
bending fatigue resistance, abrasion resistance, heat
resistance, durability and the like as a flat belt, V
belt or the like. Belts are usually imparted with a
tensile force and used in an elongated state. Belts are
used in combination with resin-made or metal-made pulleys
rotating at a high speed, and are contacted with pulleys,
cause to be wound round pulleys and to fit thereon, and
#
- 63
are exposed to collision with and rubbing on conveyed
materials, and the like. The thermoplastic resin
composition according to the present invention, since
being excellent particularly in the bending fatigue
resistance, can effectively be used as belts used in
layouts in which the belts undergo severe bending fatigue,
such as layouts in which a plurality of pulleys are
combined and layouts having small-diameter pulleys. A
too soft belt causes creeping deformation and the like,
and reduces the life; and a too hard belt gives a large
abrasion amount and the like, and also reduces the life.
Having reasonable flexibility, abrasion resistance and
bending fatigue resistance gives a highest performance to
belts. Belts are produced in a long shape by laminating
a resin or an elastomer with a fiber, a woven fabric or
the like by a thermoplastic molding machine of extrusion
or the like. The belts are used as they are in some
cases, but usually, are subjected to endless processing
and used in the state of having a continuous belt back
surface.
[0111]
[Tube]
Tubes are resin or elastomer products in a single
tube form, and usually have joints on both ends. Since
tubes have flexibility, the tubes have a high degree of
freedom of piping and have a feature of being capable of
deforming to movements of fixing parts, and other
f
- 64 -
features. Tube materials require bending fatigue
resistance, abrasion resistance, flexibility, air
permeation resistance, flame retardancy, sealability at
engagement with joints, and the like. Contacting and
rubbing often occur to deformations and movements; and in
the case of using resin materials and elastomer materials
of the thermoplastic resin composition according.to the
present invention excellent in the abrasion resistance
and the bending fatigue resistance, the abrasion amount
and occurrence of cracks due to bending are suppressed,
thus contributing to elongation of the life of products.
The flexibility of tubes serves as a sealing effect
between the tubes and joints; and that tubes are not too
flexible suppresses deformation at caulking parts for a
long time. Tubes are produced by extrusion or the like.
[0112]
[Hose]
Hoses are used in applications of liquid transport,
and require properties including oil resistance, chemical
resistance, fatigue resistance, impact resistance,
abrasion resistance, pressure resistance and local
bending. Although using methods of hoses overlap with
those of the tubes, since the hoses have a laminate
structure combined with a reinforcing layer, the pressure
of an internal fluid often becomes high. In the case of
using resin materials of the thermoplastic resin
composition according to the present invention excellent
- 65 -
in the bending fatigue resistance, the hoses are
effective in applications requiring the bending fatigue
resistance, the repeated bending and the like. Hoses are
produced by using as a reinforcing layer a layer in which
fibers are woven, laminating the layer with a resin or an
elastomer, and integrating the laminate by extrusion or
the like.
[0113]
[Adsorption pad]
Adsorption pads are contacting jigs used for fixing,
conveying and moving materials to be adsorbed. For
example, materials to be adsorbed are lifted and moved by
depressurizing an adsorption pad interior by vacuum
adsorption or the like. Adsorption pads require the
adsorbability of a part thereof contacting with a
material to be adsorbed, the flexibility for not causing
excessive deformation of the material to be adsorbed and
the airtightness for efficiently adsorbing the material
to be adsorbed, and the durability for repeated usage
thereof. The thermoplastic resin composition according
to the present invention excellent in the bending fatigue
resistance can achieve improvements in the flexibility
and the durability. The products are produced by
injection molding, blow molding or the like.
[0114]
[Vibration-proof damper]
«
- 66 -
In apparatuses generating vibration such as
precision devices, acoustic devices, machine tools and
automobiles, apparatuses disliking vibration from others,
and the like, vibration-proof dampers absorb the
vibration so as to stop outgo of the vibration from the
apparatuses or to make the vibration to be hardly
transmitted to the apparatuses. In such applications,
the vibration-proof dampers, though being always exposed
to vibration, require a high damping property to convert
the kinetic energy, a vibration controllability to alter
the resonance of a vibration frequency, the durability to
repeated motions thereof, a high strength, and the like.
The thermoplastic resin composition according to the
present invention is adaptable to such requirements.
Since the vibration-proof dampers are often used at
fulcrums to support loads and thereby always subjected to
a weight, the vibration-proof dampers are liable to cause
compression set and tension set. In order to solve this,
the vibration-proof dampers are made to have a
crosslinked structure, and a laminate structure with a
metal plate in some cases. The vibration-proof dampers
can be used also as adhesive sheets used as springs. The
vibration-proof dampers are produced by molding methods
such as injection molding, compression molding, blow
molding and press molding.
[0115]
[Vibration-proof joint]
67 -
Vibration-proof joints are used for power
transmission apparatuses and the like which suppress the
transmission of vibration from vibration sources.
Interposing a vibration-proof joint resultantly damps
vibration generated at tubes, hoses, piping and the like,
and apparatus vibration. Such applications require a low
compression set, a high damping property, the durability,
a high strength, and the like. The thermoplastic resin
composition according to the present invention is
adaptable to these required performances. The vibrationproof
joints are produced by molding methods such as
extrusion, injection molding, compression molding and
blow molding.
[0116]
[Shock absorber]
Shock absorbers are apparatuses to damp vibration of
mechanical structures and vibration generated in
buildings. The shock absorber is a leading concept of
the vibration-proof damper and the vibration-proof joint.
On requirements using elastomer components, the shock
absorbers have effects of converting a received vibration
energy to vibration having a different period, and
converting it to heat. Since the shock absorbers are
subjected to continuous bending fatigue in the course of
deforming motions at this time, having the bending
fatigue resistance thereto leads to provide products
excellent in durability.
- 68
[0117]
[Caster]
Casters refer to rollers and wheels installed on
grounding surfaces of mechanical apparatuses, conveyance
vehicles, wagons and the like. The casters require a
high mechanical strength in order to withstand the
apparatus weights, and properties such as gripping
resistance, durability, impact resistance and heat
resistance. The gripping resistance sometimes requires
flexibility in order to raise the friction resistance
with floor surfaces and ground surfaces, and therefore
repeats a small deformation and a deformation recovery
partially centered on the grounding point of the casters
in some cases. The casters require the bending fatigue
resistance in order to withstand this. The thermoplastic
resin composition according to the present invention,
since being excellent in the abrasion resistance and the
bending fatigue resistance, satisfy the performance
required for the casters. The casters are produced by
injection molding, compression molding, blow molding,
press molding or the like.
[0118]
[Roller]
Rollers such as paper-feed rollers and paperdischarge
rollers require the abrasion resistance, the
friction coefficient stability, a small compression set
and the like. The thermoplastic resin composition
- 69 -
according to the present invention being excellent in the
bending fatigue resistance and the abrasion resistance is
effective to improve the abrasion resistance and the
bending fatigue resistance, and can provide the rollers
excellent in the durability. This property is suitable
for applications other than paper transport, for example,
rollers imparted with a gripping power. The roller
products are produced by extrusion, injection molding,
compression molding, blow molding, lamination or the like.
[0119]
[Packing]
Packings are used for the purposes of the
airtightness of moving portions and movable portions of
devices, shafts, members and the like, sealing and
encapsulation of chemical substances such as lubricants
and greases, liquids and solids, and buffering and
smoothening their motions; in the case where devices and
the like are subjected to rotation motions and
reciprocating motions, and are repeatedly attached and
detached, packings are exposed to the motions, and the
use of the thermoplastic resin composition according to
the present invention excellent in the bending fatigue
resistance can secure packing properties over a long
period. The packing products are produced by injection
molding, extrusion, press molding or the like.
Examples
n
- 70 -
[0120]
Hereinafter, the present invention will be described
more specifically by way of Examples and Comparative
Examples. The present invention is not any more limited
thereto. The average dispersed particle aspect ratio and
the average dispersed particle diameter of dispersed
particles in a thermoplastic resin composition
(thermoplastic elastomer alloy or the like) were measured
by a scanning electron microscope (SEM), a transmission
electron microscope (TEM) and an atomic force microscope
(AFM).
[0121]
Materials used in Examples and the like are shown
below,
[0122]
(1) TPU-1: an adipate-based TPU (thermoplastic
polyurethane) of 90 in hardness
(2) TPU-2: a caprolactone-based TPU (thermoplastic
polyurethane) of 90 in hardness
(3) TPU-3: a PTMG-based TPU (thermoplastic polyurethane)
of 92 in hardness
(4) TPU-4: an adipate-based TPU (thermoplastic
polyurethane) of 92 in hardness
(5) TPU-5: an adipate-based TPU (thermoplastic
polyurethane) of 80 in hardness
#
- 71 -
(6) TPEE: trade name "Hytrel 4777" (a thermoplastic
polyester elastomer, made by Du Pont-Toray Co., Ltd.)
(7) TPAE: trade name "UBESTA XPA 9040X1" (a thermoplastic
polyamide elastomer, made by Ube Industries, Ltd.)
(8) POM: trade name "Duracon M90-44" {a polyacetal resin,
made by Polyplastics Co., Ltd.)
(9) PEN: trade name "Teonex TN8065S" (a polyethylene
naphthalate resin, made by Teijin Chemicals Ltd.)
[0123]
(1) MAH-EPDM: trade name "Fusabond N416" (a maleic
anhydride-modified ethylene-propylene-diene copolymerized
rubber, made by Du Pont K.K.)
{2) X-EA: trade name "Baymac" (an acid-modified ethylene
acryl elastomer, made by Du Pont K.K.)
(3) MAH-EPM: trade name "Tafmer MP0610" (a maleic
anhydride-modified ethylene-propylene copolymerized
rubber, made by Mitsui Chemicals Inc.)
[0124]
EPDM: trade name "EP21" (an ethylene-propylene-diene
copolymerized rubber, made by JSR Corp.)
[0125]
Example 1
100 parts by weight of TPU-1 and 10 parts by weight
of MAH-EPDM were kneaded using a twin-screw extruder
(made by Technovel Corp., trade name "KZW20TW-30"). The
#
- 72
extruder was set at a barrel temperature of 200°C (here,
a feeder portion temperature of 160°C) and a screw
rotation frequency of 300 rpm; and the resins were melt
kneaded, and passed through a pelletizer to thereby
fabricate a pellet. The obtained pellet was injection
molded using an injection molding machine (made by Nissei
Plastic Industrial Co., Ltd., trade name "NEX110-18E") to
thereby fabricate test pieces [100 mm x 100 mm x 2 mm
thick (for abrasion test), 120 mm x 10 mm x 4 mm thick
(for Demattia flex test)].
[0126]
Comparative Example 1
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-1 alone as a raw material resin.
[0127]
Example 2
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-2 and 10 parts by weight of MAH-EPDM as raw
material resins.
[0128]
Comparative Example 2
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-2 alone as a raw material resin.
[0129]
#
- 73
Example 3
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-3 and 5 parts by weight of MAH-EPDM as raw
material resins. An MAH-EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1.23 and an average dispersed
particle diameter of 0.35 jam.
[0130]
Example 4
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-3 and 10 parts by weight of MAH-EPDM as raw
material resins. An MAH-EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1.11 and an average dispersed
particle diameter of 0.42 [m..
[0131]
Example 5
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-3 and 20 parts by weight of MAH-EPDM as raw
material resins. An MAH-EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1.08 and an average dispersed
particle diameter of 0.52 |jm.
[0132]
74 -
Comparative Example 3
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-3 alone as a raw material resin.
[0133]
Comparative Example 4
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-3 and 10 parts by weight of EPDM as raw
material resins. An EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1.1 and an average dispersed
particle diameter of 5.8 |am.
[0134]
Example 6
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-4 and 5 parts by weight of MAH-EPDM as raw
material resins. An MAH-EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1 and an average dispersed
particle diameter of 0.62 |jm.
[0135]
Example 7
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-4 and 10 parts by weight of MAH-EPDM as raw
1^
- 75 -
material resins. An MAH-EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1.08 and an average dispersed
particle diameter of 0.52 \xm.
[0136]
Example 8
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-4 and 20 parts by weight of MAH-EPDM as raw
material resins. An MAH-EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1.85 and an average dispersed
particle diameter of 0.77 [xm.
[0137]
Example 9
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-5 and 10 parts by weight of MAH-EPDM as raw
material resins.
[0138]
Comparative Example 5
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-4 alone as a raw material resin.
[0139]
Comparative Example 6
#
- 76
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-4 and 10 parts by weight of EPDM as raw
material resins. An EPDM particle in an obtained
thermoplastic elastomer alloy had an average dispersed
particle aspect ratio of 1.1 and an average dispersed
particle diameter of 3.2 |jm.
[0140]
Evaluation tests
An abrasion loss (mg) after the rotation number of
1,000 times using a Taber abrasion tester using an
abrasion wheel H-22 at a load of 9.8 N was measured for
the test piece of 100 mm x 100 mm x 2 mm thick, according
to JIS K7311. The results are shown in Table 1.
[0141]
A Demattia flex test was carried out according to
JIS K62 60. A notch of 0.5 ram in depth was cut across the
nearly entire length in the width direction of a middle
portion of the long side (a position of 60 mm from the
end in the longitudinal direction) on the strip test
piece of 120 mm x 10 mm x 4 mm thick, and the notched
test piece was provided for the test. The test was
carried out under the condition of a maximum distance
between chucks of 80 mm, a motion distance between the
chucks of 7 0 mm and a bending speed of 97 times/min, and
77 -
a bending number of times (bending fatigue number of
times) until the depth of a crack from the notch of the
test piece reached 3.5 mm was measured. The results are
shown in Table 1.
[0142]
A hardness was measured according to JIS K6253
(durometer type A), The pellet was injection molded by
an injection molding machine (made by Nissei Plastic
Industrial Co., Ltd., trade name "NEX110-18E") to thereby
fabricate test pieces of 100 ram x 100 ram x 2 mm thick;
three sheets thereof were stacked to thereby prepare a
test piece of 6 mm in thickness; and a measurement of a
hardness was carried out using the stacked test piece.
The results are shown in Table 1.
[0143]
A tensile test was carried out according to JIS
K7311, and a breaking strength (MPa) and a breaking
elongation (%) were determined. The results are shown in
Table 1. Test pieces for the tensile test were
fabricated by stamping out the test pieces for the
abrasion test.
[0144]
«
- 78 -
Cross-sections of the pellets obtained by a twinscrew
extruder were cut out by a freezing microtome, and
observed using a scanning electron microscope (made by
Hitachi High-Technologies Corp., trade name "S-4300") at
a magnification of 2,000 times. A SEM photograph of a
cross-section of the pellet obtained in Comparative
Example 4 is shown in Figure 1; a SEM photograph of a
cross-section of the pellet obtained in Example 4, in
Figure 2; a SEM photograph of a cross-section of the
pellet obtained in Comparative Example 6, in Figure 3;
and a SEM photograph of a cross-section of the pellet
obtained in Example 7, in Figure 4. Cross-sections of
the pellets were further observed using an atomic force
microscope (AFM). An AFM photograph of a cross-section
of the pellet obtained in Example 4 is shown in Figure
12; and an AFM photograph of a cross-section of the
pellet obtained in Example 7 is shown in Figure 13.
[0145]
From the evaluation results shown in Table 1, it is
clear that the molded articles formed using a
thermoplastic elastomer alloy according to the present
invention are remarkably better not only in the Taber
abrasion loss but also in the bending fatigue resistance
than the molded articles formed from a thermoplastic
polyurethane alone, and the molded articles formed from a
thermoplastic elastomer alloy composed of a thermoplastic
polyurethane and a non-modified ethylene-propylene-diene
79
copolymerized rubber. The case where a modified
ethylene-propylene-diene copolymerized rubber is added
can improve the abrasion resistance and the bending
fatigue resistance without spoiling the material property
of a thermoplastic polyurethane. Although even the case
where a non-modified ethylene-propylene-diene
copolymerized rubber is added exhibits an improving
affect in some degree of the bending fatigue resistance
in some cases, the cases of largely improving the
abrasion resistance and the bending fatigue resistance
are cases of a thermoplastic polyurethane alloyed with a
modified ethylene-propylene-diene copolymerized rubber.
From the results of the disperse state checking test (SEM
observation), it is clear that the disperse states are
better in order of an esteric TPU-EPDM < an etheric TPUEPDM
< an etheric TPU-maleic anhydride-modified EPDM < an
esteric TPU-maleic anhydride-modified EPDM. It is
further clear from the AFM photograph that any of the
thermoplastic elastomer alloys composed of a modified
EPDM and an etheric TPU and the thermoplastic elastomer
alloys composed of a modified EPDM and an esteric TPU are
dispersed in an average dispersed particle diameter of
not more than 1 ^im.
[0146]
The reason why the Taber abrasion and the bending
number of times are remarkably improved is conceivably
that a retardation effect of crack extension of the
#
- 80 -
microdispersion of the modified ethylene copolymer
component having an energy absorbing effect changes
states from the severe abrasion progress called adhesion
wearing of TPU to the mild abrasion progress. This is
because the thermoplastic elastomer alloy is obtained as
a combination in which a modified ethylene copolymer
component (elastomer component) is near a spherical shape
like a micro phase separation structure, and
microdispersed in a TPU. In a simply blended state in no
consideration of compatibility and shearing viscosity,
the shape of the island (dispersoid) is usually irregular
and in a mechanically crushed-like shape in many cases,
and then, the adhesive force between the island layer
(disperse phase) and the sea layer (continuous phase) is
weak; exfoliation is liable to be caused at the interface
when a stress is impressed on molded articles; and the
resistance to crack generation also from the island shape
becomes poor. These cause inferior durability in some
cases. However, the thermoplastic resin composition and
the thermoplastic elastomer alloy according to the
present invention, by increasing the adhesive surface of
the island layer (disperse phase) and the sea layer
(continuous phase) and raising the adhesive force, can
provide a disperse form in which the island layer
(disperse phase) is micro-dispersed and in a nearly true
spherical shape, and can be remarkably improved in the
durability under the motion condition impressed with
f
- 81 -
repeated loads, stresses and deformations. Nobody has
developed such properties and confirmed the effects, and
the properties and effects have been found by exhaustive
devices by the present inventors.
[0147]
- 82 -
[ T a b l e 1
Table 1
TPU-1
TPU-2
TPU-3
TPU-4
TPU-5
MAH-EPDM
(Phr)
MAH-EPM
(phr)
EPDM (phr)
Taber
Abrasion
Amount (mg)
Bending
Number Of
Times (times)
JISA
Hardness
Breaking
Strength
(MPa)
Breaking
Elongation
{%)
Aspect Ratio
Average
Dispersed
Particle
Diameter
Example
1
100
10
9.3
400,000
90
-
Comp.
Ex.1
100
12.9
5,000
92
-
Example
2
100
10
6.3
18,000
87
-
Comp.
Ex.2
100
11.5
3,000
88
-
Example
3
100
5
8.1
8,000
92
1.23
0.35
Example
4
100
10
8.5
250,000
92
1.11
0.42
Example
5
100
20
8.5
170,000
90
1.08
0.52
Comp.
Ex.3
100
12.5
3,000
92
-
Comp.
Ex.4
100
10
12.4
40,000
91
1.1
5.8
Example
6
100
5
11
15,000
93
57
560
1
0.62
Example
7
100
10
6.8
330,000
93
47
510
1.08
0.52
Example
8
100
20
10.8
270,000
91
38
490
1.85
0.77
Comp.
Ex.5
100
16.4
5,000
95
52
520
-
Comp.
Ex.6
100
10
16.6
17,000
91
1.1
3.2
Example
9
100
10
7.4
1,800,000
79
-
^
83 -
[0148]
Example 10
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPU-4 and 150 parts by weight of MAH-EPDM as
raw material resins.
[0149]
Comparative Example A
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of MAH-EPDM alone as a raw material resin.
[0150]
Example 11 (an example using a polyester-based
thermoplastic elastomer)
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPEE and 10 parts by weight of MAH-EPM as raw
material resins.
[0151]
Comparative Example 7
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPEE alone as a raw material resin.
[0152]
Example 12 {an example using a polyamide-based
thermoplastic elastomer)
$•
14 -
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPAE and 10 parts by weight of MAH-EPDM as raw
material resins.
[0153]
Comparative Example 8
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of TPAE alone as a raw material resin.
[0154]
Example 13 (an example using a polyacetal resin)
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of POM and 10 parts by weight of MAH-EPDM as raw
material resins.
[0155]
Comparative Example 9
A pellet and test pieces were fabricated by the same
operation as in Example 1, except for using 100 parts by
weight of POM alone as a raw material resin.
[0156]
The above-mentioned evaluation tests were carried
out using the tfest pieces obtained in Examples 10 to 13,
Comparative Example A and Comparative Examples 7 to 9.
In Example 11 and Comparative Example 7, the hardnesses
were values measured according to JIS K6253 (durometer
type D) . The results are shown in Table 2.
#
- 85 -
[0157]
i^iSaiS{^^aiiia^a^8fei^^ii^featt«fewi;.|iiijiu!i.jagP"g!W'!
- 87 -
[0158]
By using the each evaluation result (bending number
of times) of Comparative Example 5 (MAH-EPDM: 0 wt%).
Example 7 (MAH-EPDM: 9 wt%), Example 8 (MAH-EPDM: 17 wt%),
Example 10 (MAH-EPDM: 60 wt%), and Comparative Example A
(MAH-EPDM: 100 wt%) obtained in the above, a relationship
between the blend ratio (wt%) of a modified ethylene
copolymer (MAH-EPDM) in a thermoplastic resin composition
(a thermoplastic elastomer alloy) and the bending fatigue
resistance is expressed as a graph (single logarithmic
graph) (see Figure 5). In Figure 5, the abscissa is the
blend ratio (wt%) of MAH-EPDM, and the ordinate is the
bending number of times. (a) of Figure 5 is a graph
obtained by plotting data of Comparative Example 5 and
Comparative Example A and connecting these two points by
a straight line (broken line). (b) of Figure 5 is a
graph obtained by plotting data of Comparative Example 5,
Example 1, Example 8, Example 10 and Comparative Example
A and connecting the each point by a straight line (solid
line). (c) of Figure 5 is a graph obtained by
superposing (a) and (b) of Figure 5.
[0159]
As shown in Figure 5, the bending fatigue
resistances of the molded articles of the resin
compositions in which the modified ethylene copolymer (B)
is dispersed into the thermoplastic resin (A) has more
p
improved values than expected in each single material,
and exhibits a synergistic effect.
[0160]
Examples 14 to 20 and Comparative Examples 10 to 16
(examples using other modified ethylene copolymers)
100 parts by weight of the total of a polyethylene
naphthalate resin (PEN) as a thermoplastic resin and X-EA
as a modified ethylene copolymer (the ratio of both the
components are shown in Table 3), variable amounts shown
in Table 3 of a fatty acid metal salt (magnesium
stearate), a phenol resin and a metal oxide (magnesium
oxide) as curing agents, and one part by weight of an
antiaging agent (2,2,4-trimethyl-l,2-dihydroquinoline
polymer) were added to and kneaded in a Laboplasto Mill
(made by Toyo Seki Seisaku-sho, Ltd., trade name "4C150")•
First, the resins were sufficiently fused and kneaded,
and thereafter the curing agents were added, and after
the curing (crosslinking) reaction, the antiaging agent
was added. The reaction was checked by changing behavior
of the kneading torque value. The kneading temperature
was set at 260°C, and the kneading was carried out for a
total of 10 min. Thereafter, test pieces [100 mm x 100
mm X 2 mm thick (for abrasion test)] were fabricated by
press molding. Respective evaluation test pieces such as
tensile test pieces were stamped out from the abrasion
test pieces. Bending fatigue test pieces were fabricated
by injection molding. Comparative Example 10 was a PEN
*
- 89
resin itself in which no additives except for an
antiaging agent was added, and a sheet thereof was
obtained by injection molding. Comparative Example 16
was prepared by kneading PEN resin and non-modified EPDM
at a temperature near the melting point of the PEN by a
Laboplasto Mill. Examples 19 and 20 were prepared by
varying the blend proportion of PEN to X-EA and kneading
by a twin-screw extruder in place of the Laboplasto Mill.
The others were the same as Example 15. Properties of
the obtained thermoplastic resin compositions and the
average dispersed particle aspect ratios of the dispersed
particles (X-EA particle and the like) were measured and
evaluated by the above-mentioned methods. The results
are shown in Table 3. The tensile elastic modulus, the
modulus strength at 20% elongation, the tensile strength,
the tensile elongation rate (tensile elongation) and the
tension set were measured by a tensile test according to
JIS K7311. The hardnesses (Shore A) in Table 3 are
values measured according to JIS K6253 (durometer type A) ,
and the hardnesses (Shore D) therein are values measured
according to JIS K6253 (durometer type D).
[0161]
The results (tensile elongation rates, tensile
strengths) of the tensile tests of the resin compositions
obtained in Examples 14 to 18 and Comparative Examples 11
to 15 are shown in Figure 6. In the graph of Figure 6,
the abscissa is the tensile elongation rate (%), and the
#
- 90
ordinate is the tensile strength (MPa), Symbol a in the
graph is data of Comparative Example 11; b. Comparative
Example 12; c, Comparative Example 13; d. Comparative
Example 14; e. Comparative Example 15; f, Example 14; g.
Example 15; h. Example 15; i, Example 17; and j , Example
18.
[0162]
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Documents
Application Documents
| # |
Name |
Date |
| 1 |
8391-delnp-2013-Abstract.pdf |
2014-03-12 |
| 1 |
8391-DELNP-2013.pdf |
2013-10-07 |
| 2 |
8391-delnp-2013-Correspondence-Others-(25-10-2013).pdf |
2013-10-25 |
| 2 |
8391-delnp-2013-Claims.pdf |
2014-03-12 |
| 3 |
8391-delnp-2013-Form-3-(05-12-2013).pdf |
2013-12-05 |
| 3 |
8391-delnp-2013-Correspondence-others.pdf |
2014-03-12 |
| 4 |
8391-delnp-2013-Description (Complete).pdf |
2014-03-12 |
| 4 |
8391-delnp-2013-Correspondence Others-(05-12-2013).pdf |
2013-12-05 |
| 5 |
8391-delnp-2013-Drawings.pdf |
2014-03-12 |
| 5 |
8391-delnp-2013-Correspondence-Others-(24-02-2014).pdf |
2014-02-24 |
| 6 |
8391-delnp-2013-GPA.pdf |
2014-03-12 |
| 6 |
8391-delnp-2013-Form-1.pdf |
2014-03-12 |
| 7 |
8391-delnp-2013-Form-5.pdf |
2014-03-12 |
| 7 |
8391-delnp-2013-Form-2.pdf |
2014-03-12 |
| 8 |
8391-delnp-2013-Form-3.pdf |
2014-03-12 |
| 9 |
8391-delnp-2013-Form-5.pdf |
2014-03-12 |
| 9 |
8391-delnp-2013-Form-2.pdf |
2014-03-12 |
| 10 |
8391-delnp-2013-Form-1.pdf |
2014-03-12 |
| 10 |
8391-delnp-2013-GPA.pdf |
2014-03-12 |
| 11 |
8391-delnp-2013-Drawings.pdf |
2014-03-12 |
| 11 |
8391-delnp-2013-Correspondence-Others-(24-02-2014).pdf |
2014-02-24 |
| 12 |
8391-delnp-2013-Description (Complete).pdf |
2014-03-12 |
| 12 |
8391-delnp-2013-Correspondence Others-(05-12-2013).pdf |
2013-12-05 |
| 13 |
8391-delnp-2013-Form-3-(05-12-2013).pdf |
2013-12-05 |
| 13 |
8391-delnp-2013-Correspondence-others.pdf |
2014-03-12 |
| 14 |
8391-delnp-2013-Correspondence-Others-(25-10-2013).pdf |
2013-10-25 |
| 14 |
8391-delnp-2013-Claims.pdf |
2014-03-12 |
| 15 |
8391-DELNP-2013.pdf |
2013-10-07 |
| 15 |
8391-delnp-2013-Abstract.pdf |
2014-03-12 |