DESCRIPTION
RESIN COMPOSITION
5 TECHNICAL FIELD
The present invention relates to a resin composition
which comprises anaromatic polyester, is excellent in
hydrolysis resistance and flowability and suppresses the
generation of an isocyanate gas during molding.
10
BACKGROUND ART
Since aromatic polyester resins typified by
polyethylene terephthalate and polybutylene terephthalate
have excellentmechanicalproperties, electricalproperties,
15 heat resistance, weatherability, water resistance, chemical
resistance, solvent resistance andprocessability, they are
used as engineering plastics in a wide variety of fields such
as automobile parts and electric and electronic parts.
Meanwhile, in the automobile field, for the purpose
20 of improving fuelefficiencyas,oneofenvironmentalmeasures,
it is desired to reduce the weights of parts to be mounted
on vehicles, and resinparts arebecoming thinner andlighter.
Importance j:; now attached to the flowability of ;I material
so that a thin part can be manufactured therefrom. With
25 respect to the quality of each part, the further improvement
of mechanical strength such as tensile strength and moist
heat stability such as hydrolysis resistance is strongly
desired.
In recently years, the aromatic polyester resins have
30 often been used in sheets and films. Especially for
photovoltaic power generation (solar cells) application,
when an aromatic polyester resin is used as a back sealing
film (back sheet film), weatherability and hydrolysis
resistance, especiallylong-termhydrolysis resi~~ancea,re
2
required.
Since the aromatic polyester resins are inferior in
durability to fluorine-based resins and polyethylene-based
resins, various methods for improving durability are
5 proposed.
For example, Patent Documents 1 and 2 disclose that
hydrolysis resistance is improved by adding a
polycarbodiimide to an aromatic polyester resin.
However, it is known that when a polycarbodiimide
10 compoundisusedas anendcappingagentforapolymercompound,
the viscosity of the aromatic polyester resin is greatly
increased by a crosslinking reaction with the polyester
(Patent Document 3)
To mold this polyester whose viscosity has been
15 increased, it is necessaryto raise themolding temperature.
However, when the molding temperature is simply raised, the
obtainedmolded article becomes yellowish, or molding itself
become difficult because of the too high temperature should
be set.
2 0 When a carbodiimide compound is used as an end capping
agent for apolymercompound, a compoundhavinganisocyanate
group is liberated along with a reaction that the
polycarbodj i.rnide compound is bonded to the term.it~al of the
polyester, thereby generating a characteristic to the
25 isocyanate compound odor worsen the work environment.
To solve this problem, there is proposed a resin
composition comprising a novel compoundhaving carbodiimide
rings, each having only one carbodiimide group (may be
referred to as "cyclic carbodiimide compound" hereinafter)
30 as a carbodiimide having a structure that an isocyanate
compound is not liberated (Patent Document 4). In this
proposal, a resin composition which does not liberate an
isocyanate and has a high level of hydrol~ysis resistance is
obtained.
3
However, when a cyclic carbodiimide compound having
at least two carbodiimide rings, each having only one
carbodiimidegroup, is selectedfromamongtheaboveproposed
compounds as a thermoplastic aromatic polyester, there
5 arises a new problem that melt viscosity increases as
compared with a case where a conventionally known
polycarbodiimide compound is used though the degree of
improving hydrolysis resistance is high.
(Patent Document 1) JP-A 8-73719
10 (Patent Document 2) W02010/018662
(Patent Document 3 ) Japanese Patent No. 3618940
(Patent Document 4) W02010/071213
DISCLOSURE OF THE INVENTION
15 It is an object of the present invention to provide
a resin composition which solves the potential problems of
the above prior art, comprises an aromatic polyester resin
andhashighlevels of hydrolysis resistanceandmoldability.
In view of the above prior art, the inventors of the
20 present invention studied the use of a cyclic carbodiimide
compound having at least two carbodiimide rings, each having
only one carbodiimide group, and found that'a resin
composition which can attainthe above object canbe obtained
by containing an aromatic polyester resin, a cyclic
25 carbodiimide compound and a specific polyvalent hydroxyl
group-containing compound. The inventors made further
intensive studies and arrived at the present invention.
That is, an object of the present invention i.s attained
by the following invention.
30 1. A resin composition comprising an aromatic polyester
resin having a terminal carboxyl group content of not more
than 30 eq/ton (component A), a cyclic carbodiimide compound
having at least two carbodiimide ri.ngs, each having on1.y one
carbodiimide group (component B), and a polyvalent hydroxyl
4
group-conta~ningcompoundhavingahydroxylvalueofnotless
than 200 (component C).
2. The resincompositionintheaboveparagraphl, wherein
the component A contains polybutylene terephthalate in an
5 amount of not less than 50 mass%.
3. The r e s i n c o m p o s i t i o n i n t h e a b o v e p a r a g r a p h l , wherein
the component B is a cyclic carbodiimide compound havlng a
plurality of carbodiimide rings bonded thereto through a
spiro bond or a bond group.
10 4. The resin compositioninthe aboveparagraphl, wherein
the component B i s a cycliccarbodiimide compoundrepresented
by the following formula.
15 (In the above formula, X is a tetravalent group represented
by the followi-ng formula (i-1). ~ r lto ~r~ are each
independently an orthophenylene group or
1,2-naphthalene-diyl group which may be substituted by a
substituent. )
(i-1)
5. The resincomposition in the aboveparagraphl, wherein
the content of the component B is 0.1 to 3 parts by mass based
on 100 parts by mass of the component A.
6. The resincomposition in the aboveparagraphl, wherein
the component C is a polyhydric alcohol or a partla1 ester
thereof.
7. The resin composition inthe above paragraph 1, wherein
5 the component C has a hydroxyl value of not more than 1,000.
8. The reslncompositionintheaboveparagraph 6, wherein
the component C is a partial ester of a polyhydric alcohol
and a fatty acid having 12 or more carbon atoms.
9. The r e s i n c o m p o s i t i o n i n t h e a b o v e p a r a g r a p h l , wherein
10 the content of the component C is 0.05 to 5 parts by mass
based on 100 paits by mass of the component A.
10. The resln composition in the above paragraph 1 which
has a terminal carboxyl group content of not more than 5
eq/ton.
15 11. The resin composition in the above paragraph 1 which
has a melt viscosity at 280°C of not more than 300 Pa-s and
a reduced viscosity retention of not less than 50 % after
it is kept for 96 hours in a 12loC, 100 %RH (0.2 MPa) pressure
cooker test.
20 12. The resin composition in the above paragraph 2 which
has a melt viscosity at 260°C of not more than 300 Pa.s and
a reduced viscosity retention of not less than 80 % after
it is kept for 100 hours in a 121°C, 100 %RH (0.2 MPd) pressure
cooker test.
25 13. A method of producing a resin composition which
comprises an aromatic polyester resin having a terminal
carboxyl group content of not more than 30 eq/ton (component
A), a cyclic carbodiimide compoundhavingatleasttwo rings,
each having only one carbodiimide group (component B), and
30 a polyvalent hydroxyl group-containing compound having a
hydroxylvalue of not less than200 (componentc), comprising
the step of:
(i) melt kneading together the aromatic polyester
resin (component A) and the polyvalent hydroxyl
group-containing compound (component C ) and then adding and
melt kneading the cyclic carbodiimide compound (component
B) with the obtained rnixture;.or
(ii) adding the cyclic carbodiimide compound
5 (component B) and the polyvalent hydroxyl group-containing
compound (component C) to the aromatic polyester resin
(component A) at the same time and melt kneading them
together.
14. A molded article formed form the resin composition of
10 any one of the above paragraphs 1 to 12.
Effect of the Invention
The resincompositionofthepresent inventionhashigh
levels of hydrolysis resistance and moldability and rarely
1.5 generates an isocyanate gas during molding. The resin
composition of the present invention can be advantageously
used as amaterial for parts which are exposedto an external
environment for a long time, such as back sheets for solar
cells and solar cellmodules. It can also be advantageously
20 used as a material for thin parts which require flowability
at the time of injection molding, such as housings,
mechanical parts including wheels and gears, electric and
electronic pacts including connectors, constr~ctr~onmembers,
civil engineering members, agricultural materials,
25 automobile parts (interior and exteriorparts) and parts for
daily use.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is described in detail
30 hereinunder.

The aromatic polyester resin (component A) i.s a
thermoplastic polyester resin obtained through a reaction
between a dicarboxylic acid component comprising a
dicarboxylic acid compound and/or an ester forming
derivative thereof asthemaincomponentandadiolcomponent
c o m p r i s i n g a d i o l c o m p o u n d a n d / o r a n e s t e r f o r m i n g d e r i v a t i v e
5 thereof as the main component and comprises an aromatic
compound in at least one of the dicarboxylic acid component
and the diol component.
Examples of the dicarboxylic acid component are
aliphatic dicarboxylic acids, alicyclic dicarboxylic acids
10 and aromatic dicarboxylic acids.
The aliphatic dicarboxylic acids are aliphatic
dicarboxylic acids having 4 to 40 carbon atoms, preferably
aliphatic dicarboxylic acids having 4 to 14 carbon atoms,
such as succinic acid, glutaric acid, adipic acid, pimelic
15 acid, suberic acid, azelaic acid, sebacic acid,
undecanedicarboxylic acid, dodecanedicarboxylic acid,
hexadecanedicarboxylic acid and dimeric acid.
The alicyclic dicarboxylic acids are alicyclic
dicarboxylic acids having 4 to 40 carbon atoms, preferably
20 alicyclic dicarboxylic acids having 8 to 12 carbon atoms,
such as hexahydrophthalic acid, hexahydroisophthalic acid,
hexahydroterephthalic acid and himic acid.
The aromatic dicarboxylic acids are aromatic
dicarboxylic acids having 8 to 16 carbon atoms such as
25 phthalic acid, isophthalic acid, terephthalic acid,
methyiisophthalic acid, methylterephthalic acid,
naphthalenedicarboxylic acids including
2,6-naphthaienedicarboxylic
acid,4,4'-biphenyldicarboxylic acid, 4,4'-diphenoxyether
30 dicarboxylic acid, 4,4'-dioxybenzoic acid,
4,'-diphenylmethanedicabroxylic acid and
4,4'-diphenylketone dicarboxylic acid, and derivatives
thereof. The derivatives are ester formable derivatives
such as lower alkylesters, arylesters and acid anhydrides.
8
These dicarboxylic acid components may be used alone
or in combination of two or more. Preferred dicarboxylic
acid components are aromatic dicarboxylic acids such as
terephthalic acid, isophthalic acid and
5 naphthalenedicarboxylic acids. Terephthalic acid and
2,6-naphthalenedicarboxylic acid are particularly
preferred. Preferably, the dicarboxylic acid component
contains an aromatic dicarboxylic acid in an amount of not
less than 50 mol%, preferably not less than 80 mol% and more
10 preferablynot less than 90molR. Further, apolycarboxylic
acid such as trimellitic acid or pyromellitic acid, or an
ester forming derivative thereof (such as an alcohol ester)
may be used as required. When this polyfunctional compound
is used, a branched thermoplastic polyester resin can be
15 obtained.
Examples ofthe diolcomponentinclude aliphatic diols,
polyoxyalkylene glycols and alicyclic diols.
The aliphatic diols are aliphatic diols having 2 to
12 carbon atoms, preferably aliphatic diols having 2 to 10
20 carbon atoms, such as ethylene .glycol, trimethylene glycol,
propylene glycol, 1,4-butanediol, 1,3-butanediol,
neopentyl glycol, hexanediol, octanediol and decanediol.
The pnlyoxyalkylene glycols are glycols hclving a
plurality of oxyalkylene units whose alkylene group has 2
25 to 4 carbon atoms. Examples thereof include diethylene
glycol, dipropylene glycol, ditetramethylene glycol,
triethylene glycol, tripropylene glycol and
polytetramethylene glycol.
The alicyclic diols include 1,4-cyclohexanediol,
30 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Aromatic diols such as hydroquinone, resorcinol,
bisphenol, 2,2-bis(4-hydroxyphenyl)propane,
2,2-bis-(4-(2-hydroxyethoxy)phenyl)propane and xylylene
glycol.. may be used in combination with the above diol
component.
These diols components may be used alone or in
combination of two or more. Preferred diol components are
alkylene glycols having 2to 10 carbon atoms suchas ethylene
5 glycol, trimethylene glycol, propylene glycol and
1,4-butanediol.
Preferably, an alkylene glycol having 2 to 10 carbon
atoms is contained in the diol component in an amount of not
less than 50 mol%, preferably not less than 80 mol% and more
10 preferably not less than 90 mol%. Further, a polyol or an
ester forming derivative thereof such as glycerin,
trimethylol propane, trimethylol ethane or pentaerythritol
maybe usedas required. When suchapolyfunctionalcompound
is used, a branched thermoplastic polyester resin can be
15 obtained.
As the aromatic polyester resin (component A) may be
used a copolyester obtained from two or more of the above
dicarboxylic acid components and the diol components, or a
copolyester obtained from an oxycarboxylic acid component
20 or a lactone component as another copolymerizable monomer
(may be referred to as "copolymerizable monomer"
hereinafter) .
Examples of the oxycarboxylic acid includ(.:
oxycarboxylic acids such as oxybenzoic acid, oxynaphthoeic
25 acid, hydroxyphenylaceticacid, glycolicacidandoxycaproic
acid, and derivatives thereof. Examples of the lactone
include lactones having 3 to 12 carbon atoms such as
propiolactone, butyrolactone, valerolactone and
caprolactone (such as E-caprolactone).
3 0 In the copolyester, the content ofthe copolymerizable
monomer can be selected from a range of 0.01 to 30 mo18,
generally 1 to 30 mol8, preferably 3 to 25 mol8 and more
preferably 5 to 20 mol%. When a homopolyester and a
copolyester are used in combination, the content of the
10
copolymerizable monomer is 0.1 to 30 mol% (preferably 1 to
25 mol%, more preferably 5 to 25 mol%) based on the total
of allthemonomers, andthehomopolyester/copolyester ratio
can be selected from a range of 99/1 to 1/99 (weight ratio),
5 preferably 95/5 to 5/95 (weight ratio) and more preferably
90/10 to 10/90 (weight ratio).
The preferred aromatic polyester resin (component A)
is a homopolyester or a copolyester comprising an alkylene
arylate unit such as alkylene terephthalate or alkylene
10 naphthalate as the main component (for example, 50 to 100
mol%, preferably 75 to 100 mol%).
Examples ofthe polyalkylene terephthalate include
polyalkylene terephthalates whose alkylene moiety has 2 to
4 carbon atom, such as polyethylene terephthalate (PET),
15 polytrimethylene terephthalate (PTT) and polybutylene
terephthalate (PBT), and 1,4-cyclohexanedimethylene
terephthalate (PCT) .
Examples of the polyalkylene naphthalate include
polyalkylene naphthalates whose alkylene moiety has 2 to 4
20 carbon atoms, such as polyethylene naphthalate,
polypropylene naphthalate and polybutylene naphthalate.
They may be used alone or in combination of two or more.
The particularly preferred aromatic polyester resin
(component A) is a homopolyester resinor a copolyesterresin
25 comprising not less than 80 mol% (specifically not less than
90 mol"; of an alkylene arylate unit whose alkylene moiety
has 2 to 4 carbon atoms, such as ethylene terephthalate,
trimethylene terephthalate, tetramethylene terephthalate
or tetramethylene-2,6-naphthalate. Polyethylene
30 terephthalate resin, polytrimethylene terephthalate resin,
polybutylene terephthalate resin and
polytetramethylene-2,6-naphthalene dicarboxylate resin are
such examples. Out of these, polyethylene terephthalate
resin and polybutylene terephthalate resin are preferred,
and polybutylene terephthalate resin is particularly
preferred.
The aromatic polyester resin (component A) preferably
comprises not less than 50 mass% of polybutylene
5 terephthalate.
The terminal carboxyl group content of the aromatic
polyester resin (component A) is not more than 30 eq/ton.
The terminal carboxyl group content is preferably not more
than 25 eq/ton.
10 According to the present invention, although the
hydrolysis resistance of the resin composition can be
improved by using the cyclic carbodiimide compound
(component B), when the terminal carboxyl group content of
the aromatic polyester resin (component A) is too high, the
15 hydrolysis resistance ofthe resin composition is not fully
enhanced. Therefore, the terminal carboxyl group content
of the aromatic polyester resin (component A) must be not
more than 30 eq/ton.
The intrinsic viscosity (IV) of the aromatic polyester
20 resin (component A) is preferably not less than 0.6 dL/g,
more preferablynot less than 0.7 dL/g. The above intrinsic
viscosity is preferably not more than 1.3 dZ/g, more
preferably rrot more than 1.2 dL/g. An intrinsic viscosity
of 0.6 to 1.3 dL/g may be achieved by blending together
25 aromatic polyester resins (component A) having different
intrinsic viscosities, for example, an aromatic polyester
resin having an intrinsic viscosity of 1.5 dL/g and an
aromatic polyester resin having an intrinsic viscosity of
0.5 dL/g. The intrinsic viscosity (IV) can be measured at
30 35°C in o-chlorophenol or a mixed solvent of phenol and
tetrachloroethane (mass ratio of 60/40). When an aromatic
polyester resin having an intrinsic viscosity within this
range is used, satisfactory hydrolysis resistance can be
obtained and the melt viscosity can be reduced efficiently.
12
When the intrinsic viscosity is too low, the effect of
improving hydrolysis resistancemay not be obtained andwhen
the intrinsic viscosity is too high, melt viscosity at the
time of molding becomes high and a flowing failure or a
5 charging failure of the resin may occur in a metal mold.
A commercially available product or what is produced
by copolymerizing (polycondensing) a dicarboxylic acid
component or a reactive derivative thereof, a diolcomponent
or a reactive derivative thereof and optionally a
10 copolymerizable monomer by a commonly used method, for
example, transesterification reaction or direct
esterification may be used as 'the aromatic polyester resin
(component A) .
Preferably, the resin composition of the present
15 invention has a terminal carboxyl group content of not more
than5 eq/ton. Withinthis range, especiallyhighhydrolysis
resistance is obtained. Theterminalcarboxylgroup content
is more preferably not more than 3 eq/ton.
Desirably, the resin composition of the present
20 invention has a reduced viscosity retention of not less than
50 % after 100 hours in a 121°c, 100 %RH (0.2 MPa) pressure
cooker test. When the reduced viscosity retention is not
less than 50 %, the finally obtained film, i.e., a molded
article has sufficientlyhigh hydrolysis resistance without
25 greatly reducing its mechanical strength.
The present invention includes a polybutylene
terephthalate resin composition which comprises not less
than 50 mass% of polybutylene terephthalate based on the
total mass of the aromatic polyester resin (component A) and
30 has a melt viscosity at 260°C of not more than 300 Pa.s and
a reduced viscosity retention of not less than 80 % after
100 hours in a 121°C, 100 %RH (0.2 MPa) pressure cooker test.
In the polybutylene terephthalate resin composition
oi the present invention, the content of polybutylene
13
terephthalate is not less than 50 mass% based on the total
mass of the component A. To obtain the characteristic
properties of polybutylene terephthalate, the content of
polybutylene terephthalate is preferably not less than 90
5 mass%, particularly preferably not less than 95 mass% and
most preferably not less than 97.5 mass%.
The resin composition of the present invention has a
melt viscosity at 260°C of preferably not more than 1,000
Pa.s, more preferably not more than 300 Pa-s. When the melt
10 viscosity at 260°C is not more than 1,000 Pa.s, specifically
not more than 300 Pa-s, injection molding becomes easy and
yellowing does not occur during melt film formation and melt
molding.
15
The resin composition of the present invention
comprises a cyclic carbodiimide compound (component 8)
having at least two carbodiimide rings, each having only one
carbodiimide group, for the aromatic polyester resin
20 (component A).
In the present invention, theterm"carbodiimide ring"
means a ring having only one carbodiimide group in a compound
whose atoms are bonded together to form a cyclic ::tructure,
so-called "cyclic compound". The cyclic carbodiimide
25 compound (component B) as a whole is a compound having at
least two carbodiimide rings, each having only one
carbodiimide group (-N=C=N-), in one molecule. A compound
having this structure has the great effect of improving the
moist heat durability of the aroma-tic polyester resin
30 (component A) and does not generate an isocyanate compound
through an end capping reaction.
The number of atoms in the cyclic structure
constituting the carbodiimide ring is preferably 8 to 50,
more preferably 10 to 30, much more preferably 10 to 20 and
14
particularly preferably 10 to 15.
The number of atoms in the cyclic structure means the
number of atoms constituting the cyclic structure directly.
For example, the number of atoms of an 8-membered ring is
5 8, and the number of atoms of a 50-membered ring is 50. When
the number of atoms in the cyclic structure is 8 or more,
the stabilityofthe cyclic carbodiimide compound (component
8) is high, whereby it is easy to store and use it. From
the viewpoint of reactivity, the upper limit of the number
10 of ring members is not particularly limited but a cyclic
carbodiimide corr.pound having 50 or less atoms (component B)
iseasilysynthesized, therebymakingitpossibletosuppress
a rise in cost.
The molecular weight of the cyclic carbodiimide
15 compound (component B) is preferably 100 to 1,000. Above
100, the structural stability and volatility of the cyclic
carbodiimide compound (component B) become advantageous.
Below 1,000, synthesi-s in a dilution system is not required
in the production of a cyclic carbodiimide and the yield
20 hardly lowers, all which are advantageous in terms of cost.
From the above points of view, the molecular weight is more
preferably 100 to 750, much more preferably 250 to 750. The
molecular weight of the cyclic carbodiimide compound
(component B) means weight averagemolecular weight when the
25 cyclic carbodiimide compound (component B) has a molecular
weight distribution.
The component B is preferably a cyclic carbodiimide
compound whose carbodiimide rings are bonded together
through a spiro bond or a bond group. When the cyclic
30 carbodiimide compound takes this structure, the effect of
improvingthemoistheatdurabilityofthe aromaticpolyester
resin (component A) can be further enhanced.
The component B is particularly preferably a compound
represented by the following formula.
(In the above formula, X is a tetravalent group represented
by the following formula - 1 ) Arl to Ar4 are each
5 independently an orthophenylene group or
1,2-naphthalene-diyl group which may be substituted by a
substituent.)
The following compounds.are examples of the cyclic
10 carbodiimide compound (component B) having at least two
carbodiimide rings, eachhaving onlyone carbodiimide group,
which can be used in the present invention.
... ...
"mu and "n" are each an integer of 1 to 6
5 (When a cyclic carbodiimide compound is added to the main
chain of a polymer, "n" is the number of recurring units of
the polymer. )
("p", "m" and "n" are each an integer of 1 to 6.)

("n" is an integer of 1 to 6.)
-- MeOOC N C - COOMe
5 ("m" is an integer of 0 to 3, and "n" is an integer of 0 to 3.)
("m" is an integer of 0 to 5, and "n" is an integer
of 0 to 5.)
10
("n" is an integer of 1 to 6.)
These compounds can be produced based on the
5 disclosures of W02010/071211 and JP-A 2011-256139.
The content of the cyclic carbodiimide compound
(component B) in the resin composition is preferably 0.1 to
3 parts by mass, more preferably 0.3 to 2 parts by mass and
much more preferably 0.5 to 1.5 parts by mass based on 100
10 parts by mass of the aromatic polyester resin (component A).
When the content of the component B falls within the above
range, the effect ofthe carbodiimide canbeobtainedwithout
denaturing the properties of the substrate.
15
The polyvalent hydroxyl group-containing compound
(component C) is a compound having at least two hydroxyl
groups in one molecule. The polyvalent hydroxyl
20 group-containing compound (component C) has a hydroxyl value
of not less than 200 as will be described hereinafter. The
polyvalent hydroxyl group-containing compounds (component
C) having a hydroxyl. value of not Less than 200 may be used
alone or in combination of two or more.
This polyvalent hydroxyl group-containing compound
(component C) enhances the flowability of the resin
composition. In general, although flowability can be
improvedwhena componentwhichenhances flowabilityis added
5 to an aromatic polyester resin, it is i.mpossible to avoid
the deterioration of the characteristic properties such as
mechanical strength and toughness of the aromatic polyester
resin. However, by using the polyvalent hydroxyl
group-containing compound (component C) having a hydroxyl
10 value of not less than 200, the flowability of the resin
composition at the time of melting can be improved
efficiently while the characteristic properties of the
aromatic polyester resin are maintained at high levels.
The polyvalent hydroxyl group-containing compound
15 (component C) having a hydroxyl value of not less than 200
also serves as ahydrolysisresistanceacceleratingaidwhich
promotesthe componentBfs effectofimprovingthehydrolysis
resistance ofthe resin composition in the resin composition
comprising the cyclic carbodiimide compound (component B).
20 Although the cause of this is not identified, it is assumed
that the polyvalent hydroxyl group-containing compound
(component C) having a hydroxyl value of not less than 200
suppresses ;.i rise in the viscosity of the resin composition
to improve melt kneadability, whereby a reactionbetween the
25 aromatic polyester resin (component A) and the cyclic
carbodiimide compound (component B) is carried out
efficiently.
Therefore, when the polyvalent hydroxyl
group-containing compound (component C) having a hydroxyl
30 value of not less than 200 is contained in the resin
composition, use is made of the characteristic properties
of the aromatic polyester resin (component A), and the
hydrolysis resistance of the resin composition can be
improved while the flowability of the resin composition is
enhanced.
What is produced by a conventionally known method may
be used or a commercially available product may bepurchased
and used as the polyvalent hydroxyl group-containing
5 compound (component C) having a hydroxyl value of not less
than 200.
The hydroxyl value of the polyvalent hydroxyl
group-containing compound (componentc) is notlessthan200.
The preferred hydroxyl value is not less than 250. When the
10 above hydroxyl value is not less than 200, the above
flowability improving effect tends to be enhanced.
Meanwhile, the hydroxyl value of the polyvalent
hydroxyl group-containing compound (component C) is
p r e f e r a b l y n o t m o r e t h a n 1 , 0 0 0 , morepreferablynotmorethan
15 800, much more preferably not more than 600 and particularly
preferably not more than 500. When the above hydroxyl val.ue
is not more than 1,000, a further effect that the occurrence
of a mold deposit can be effectively suppressed at the time
of molding the obtained resin composition can be obtained.
2 0 In addition, since a reaction between the polyvalent
hydroxyl group-containing compound (component C) and the
aromatic polyester resin (component A) is prevented from
proceeding excessively, themolecularweightoftl-I[? aromatic
polyester resin (component A) hardly drops and the
25 characteristic properties such as mechanical properties,
hydrolysis resistance, heat resistance and chemical
resistanceofthearomaticpolyester resin (componentA) tend
to be retained.
In the present application, the hydroxyl value is
30 measured by JOCS method 2.3.6.2-1996 (pyridine/acetic
anhydridemethod) (The JOCS StandardMethods forthe Analysis
of Fats, Oils and Related Materials).
Examples of the polyvalent hydroxyl grou~l-containing
compound (component C) include polyhydric alcohols and
2 2
partial esters thereof. The component C is preferably a
partial ester of a polyhydric alcohol and a fatty acidhaving
12 or more carbon atoms.
The polyhydric alcohol is, for example, a compound
5 havingat leasttwohydroxymethylgroups in the samemolecule
Examples thereof include ethylene glycol, propylene glycol,'
1,3-propanediol, 1,4-butanediol, 1,6-hexanediol,
diethylene glycol, polyethylene glycol, polypropylene
glycol, polytetramethylene glycol, trimethylol methane,
10 pentaerythritol, dipentaerythritol, tripentaeryhtritoland
sorbitols. At least one selected from these is preferably
used, and they may be used alone or in combination of two
or more.
Preferably, the fatty acid of a partial ester of a
15 polyhydric alcohol has 12 or more carbon atoms from the
viewpoint of flowability. Examples ofthe fatty acid havi.ng
12 or more carbon atoms include lauric acid, oleic acid,
palmiticacid, stearicacid, 12-hydroxystearic acid, behenic
acid andmontanic acid. The fattyacidis preferably a fatty
20 acid having 12 to 32 carbon atoms, particularly preferably
a f a t t y a c i d h a v i n g 1 2 t o 2 2 c a r b o n a t o m s . More specifically,
lauric acid, stearic acid, 12-hydroxystearic acid and
behenic acid are particularly preferred. By using a fatty
acid having 12 or more carbon atoms, the heat resistance of
25 the resin tends to be fully retained advantageously. When
thenumberofcarbonatomsis 32 or less, theabove flowability
improving effect becomes high advantageously.
To provide flowability at the time of melting to the
resin composition and ensure the obtained molded body to
30 retain almost all the physical properti-es of the aromatic
polyester resin (component A) without deteriorating them,
an ether obtained by addition polymerizing alkylene oxide
with a glycerin fatty acid ester or dig1yceri.n is preferred
as the polyvalent hydroxyl. group-containing compound
2 3
(component C) .
A description is subsequently given of the ether
obtained by addition polymerizing alkylene oxide with a
glycerin fatty acid ester or dig1ycerj.n. The glycerin fatty
5 acid ester is an ester comprising g1yceri.n and/or a
dehydration condensate thereof and a fatty acid.
Glycerin fatty acid esters obtained by using a fatty
acidhaving12 ormore carbon atoms are preferred. The fatty
acids having 12 or more carbon atoms include lauric acid,
10 oleic acid, palmitic acid, stearic acid, 12-hydroxystearic
acid, behenic acid and montanic acid. Fatty acids having
12 to 32 carbon atoms are preferred, and fatty acids having
12 to 22 carbon atoms are particularly preferred.
Preferred examples of the glycerin fatty acid ester
15 include glycerin monostearate, glycerin monobehenate,
diglycerin monostearate, triglycerin monostearate,
triglycerin stearic acid partial ester, tetraglycerin
stearic acidpartial ester, decaglycerinlauric acidpartial
ester and glycerin mono12-hydroxy stearate.
2 0 The ether obtained by addition polymerizing alkylene
oxide with diglycerin is, for example, polyoxypropylene
diglyceryletherobtainedbyadditionpolymerizingpropylene
oxide with diglycerin, or polyoxyethylene diglyccryl ether
obtained by addition polymerizing ethylene oxide with
25 diglycerin. In the present invention, out of these ethers,
polyoxyethylene diglyceryletheris particularlypreferably
used.
The content of the polyvalent hydroxyl
group-containing compound (component C ) in the resin
30 composition is preferably 0.05 to 5 parts by mass, more
preferably 0.1 to 3 parts by mass and more preferably 0.5
to 2 parts by mass based on 100 parts by mass of the aromatic
polyester resi.n (component A). When the content of the
polyvalent hydroxyl group-containing compound is not less
than 0.05 part by mass, the flowability improving effect
tends to be fully obtained advantageously and when the
content is not more than 5 parts by mass, the poor appearance
of a molded article and the contamination of a mold by gas
5 production during molding rarely occur advantageously.

The resin composition of the present invention may be
produced by melt kneading together the aromatic polyester
10 resin (component A), the cyclic carbodiimide compound
(component B) and the polyvalent hydroxyl group-containing
compound (component C).
The timing of adding the polyvalent hydroxyl
group-containing compound (component C) to the system is
15 important. When the polyvalent hydroxyl group-containing
compound having a hydroxyl value of not less than 200
(component C) is not added before the carbodiimide compound
(component B) is added to the aromatic polyester resin
(component A), thickening occurs by the carbodiimide
20 compound (component B) before a , t h i c k e n i n g p r e v e n t i o n e f f e c t
is obtained by adding the component C, thereby making it
difficult to obtain the resin composition oE the present
invention if the component C is added after the a~.iditiono f
the component B.
2 5 Therefore, (I) the carbodiimide compound (component
B) should be added and melt kneaded in the coexistence of
thearomaticpolyester resin (component A) andthepolyvalent
hydroxyl group-containing compound (component C), or (11)
the polyvalent hydroxyl group-containing compound
30 (component C) and the carbodiimide compound (component B)
should be added to and melt kneaded with the aromatic
polyester resin (component A) at the same time.
In the case of the above (I), when the aromatic
polyester resin (component A) and the polyvalent hydroxyl
group-containingcompound (component C) aremadecoexistent,
before the addition of the carbodiimide compound (component
B), they a r e preferably melt !
10 The resin composition of the present invention may
comprise a stabilizer. Stabilizers which are used for
ordinarythermoplastic resins maybe used as the stabilizer.
Examplesthereof include antioxidants andlightstabilizers.
By blending these, molded articles which are excellent in
15 mechanical properties, moldability, heat resistance and
durability can.be obtained.
The antioxidants include hindered phenol-based
compounds, hindered amine-based compounds,
phosphorus-based compounds such as phosphite-based
20 compounds and thioether-based.compounds.
The hindered phenol-based compounds include
n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-
propionate,
n-octadecyl-3- (3' -methyl-5' -.tert-butyl-4' -hydroxyphenyl)
25 -propionate,
n-tetradecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)-
propionate,
1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)
-propionatel,
30 1,4-butanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)
-propionate],
2,2'-methylene-bis(4-methyl-tert-butylphenol),
triethylene glycol-bis[3-(3-tert-butyl-5-methyl4-
tetrakis [methylene-3- (3', 5' -di-tert-butyl-4-
hydroxyphenyl)propionate]me-thane and
3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-
methylphenyl)propionyloxy)-l,l-dimethyethyl)2,4,8,10-
5 tetraoxaspiro (5,5) undecane.
The hindered amine-based compounds include
N,N' -bis-3- (3' ,5' -di-tert-butyl-4' -hydroxyphenyi)
propionyl hexamethylenediamine,
N,N' -tetramethylene-bis [3- (3' -methyl-5' -tert-butyl-4' -
10 hydroxyphenyl) propionyl] diamine,
N,Nf -bis [3- (3,5-di-tert-butyi-4-hydroxyphenyl) -
propionyllhydrazine, N-saiicyloyl-N'-salicylidene
hydrazine, 3-(N-salicyloy1)amino-1,2,4-triazole and
N,N'-bis[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)
15 propionyloxy]ethyl]oxyarnide. Out of these, triethyiene
glycol-bis[3-(3-tert-butyl-5-methyl-4-l~ydroxyphenyl)-
propionate] and
tetrakis [methylene-3- ( 3 ' , 5' -di-tert-butyl-4-
hydroxyphenyl)propionate]methane are preferred.
20 The phosphite-based compounds are preferably
compounds having at least one P-O bond bonded to an aromatic
group, such as tris(2,6-di-tert-butylphenyl')phosphite,
tetrakis (2,G--di-tert-butylphenyl4), 4' -biphenyleile
phosphite,
25 bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite,
2,2-methylenebis(4,6-di-tert-butylpheny1)octyl
phosphite,
4,4'-butylidene-bis(3-methyl-6-tert-butylphenyl-ditri.
decyl)phosphite,
30 1,1,3-tris(2-methyl-4-ditridecylphosphite-5-tertbutylphenyl)
butane, tris(mixed mono- and
di-nonylphenyl)p hosphites, tris (nonyl.)p hosphite and
4,4'-isopropylidenebis(phenylphosphite).
Out of these, tris(2,6-di-tert-butylphenyl)phosphite,
2,2-methylenebis( 4,6-di-tert-butylphenyl)o ctyl phosphi.te,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite
and
tetral
The resin composition of the present invention may
3 1
compriseanorganicorinorganiccrystallizationaccelerator.
When the resin composition comprises a crystallization
accelerator, a molded article.which is excellent in
mechanical properties, heat resistance and moldability can
5 be obtained.
That is, moldability and crystallinity areimproved
by using a crystallization accelerator, thereby making it
possible to obtain a molded article having excellent heat
resistance and moist heat-resistant stability through
10 sufficient crystallization during normal injectionmolding.
In addition, the production time of the molded article can
be greatly shortened, with the result that an economical
effect can be great.
Crystallization nucleating agents which are generally
15 used for crystalline resins may be used as the
crystallization accelerator used in the present invention,
and both inorganic and organic crystallization nucleating
agents may be used.
The inorganic crystallization nucleating agents
20 include talc, kaolin, silica, syntheticmica, clay, zeolite,
graphite, carbon black, zinc oxide, magnesium oxide,
titanium oxide, calcium carbonate, calcium sulfate, barium
sulfate, caLcium sulfide, boron nitride, m~ntmor~llonite,
neodymium oxide, aluminum oxide and phenyl phosphate metal
25 salts. Preferably, these inorganic crystallization
nucleating agents are treated with a dispersion aid to
enhance their dispersibilities in the composition and their
effects so as to be well dispersed to a primary particle
diameter of 0.01 to 0.5 pm.
30 The organic crystal nucl-eating agents include organic
carboxylic acidmetal salts such as calciumbenzoate, sodium
benzoate, lithium benzoate, potassium benzoate, magnesium
benzoate, barium benzoate, calcium oxalate, disodium
terephthalate, dilithium terephthalate, dipotassiurn
terephthalate, sodium laurate, potassium laurate, sodium
myristate, potassium myristate, calcium myristate, barium
myristate, sodium octanoate, calcium octanoate, sodium
stearate, potassium stearate, lithium stearate, calcium
5 stearate, magnesium stearate, barium stearate, sodium
montanate, calcium montanate, sodium toluate, sodium
salicylate, potassiumsalicylate, zinc salicylate, aluminum
dibenzoate, sodium P-naphthoate, potassium P-naphthoate and
sodium cyclohexane carboxylate, and organic sulfonic acid
10 metal salts such as sodium p-toluene sulfonate and sodium
sulfoisophthalate.
Organic carboxylic acid amides such as stearic acid
amide, ethylene bislauric acid amide, palmitic acid amide,
hydroxystearic acid amide, erucic acid amide and trimesic
15 acid tris(tert-butylamide), low-density polyethylene,
high-density polyethylene, polyisopropylene, polybutene,
poly-4-methylpentene, poly-3-methylbutene-1, polyvinyl
cycloalkane, polyvinyl trialkylsilane, high-melting point
polylactic acid, sodium salts of an ethylene-acrylic acid
20 copolymer, sodium salts of a styrene-maleic anhydride
copolymer (so-called "ionomers"), benzylidene sorbitol and
derivatives thereof such as dibenzylidene sorbitolare also
included.
Out of these, at least one selected from talc and
25 organic carboxylic acidmetal salts ispreferablyused. The
crystallization accelerators may be used alone or in
combination of two or more in the present invention.
The content of the crystallization accelerator is
preferably 0.01 to 30 parts by mass, more preferably 0.05
30 to 20parts bymass basedon 100partsbymass ofthe aromatic
polyester resin (component A).

The resln composltlon of the present invention may
comprise an organic or inorganic f i l l e r . When t h e r e s i n
composition comprises a f i l l e r component, a molded a r t i c l e
having excellentmechanicalproperties, heat r e s i s t a n c e and
rnoldability can be obtained.
5 Examples of the organic f i l l e r include chip f i l l e r s
such as r i c e husk chips, wooden chips, bean curd refuse, old
paper crushed chips and apparel crushed chips, fibrous
f i l l e r s such as plant f i b e r s i n c l u d i n g c o t t o n f i b e r s , hemp
f i b e r s , bamboo f i b e r s , wooden f i b e r s , kenaf f i b e r s , j u t e
10 f i b e r s , banana f i b e r s and coconut f i b e r s , pulp a n d c e l l u l o s e
f i b e r s obtained from these plant f i b e r s , animal f i b e r s
including s i l k , wool, Angora, cashmere and camel f i b e r s , and
s y n t h e t i c f i b e r s including polyester f i b e r s , nylon f i b e r s
a n d a c r y l i c f i b e r s , andpowdery f i l l e r s suchaspaperpowders,
15 wooden powders, c e l l u l o s e powders, r i c e husk powders, f r u i t
s h e l l powders, c h i t i n powders, chitosan powders, protein
powders and s t a r c h powders. From t h e viewpoint of
moldability, paper powders, wooden powders, bamboo powders,
c e l l u l o s e powders, kenaf powders, r i c e husk powders, f r u i t
20 s h e l l powders, c h i t i n powders, chitosan powders, protein
powders and s t a r c h powders are p r e f c r r e d , andpaperpowders,
wooden powders, bamboo powders, c e l l u l o s e powders and kenaf
powders a r e more p r e f e r r e d . Paper powders and wootlcn powders
are much more p r e f e r r e d . Paper powders are p a r t i c u l a r l y
25 preferred.
Organic f i l l e r s d i r e c t l y obtained from n a t u r a l
productsmaybe usedbut organic f i l l e r s recycled fromwaste
materials such as used paper, waste timber and used clothing
may also be used.
30 Conifers such as yellow p i n e , c e d a r , cypress and f i r ,
andbroadleaf t r e e s such as beech, chinquapin and eucalyptus
are preferred as timber.
Paper powders p r e f e r a b l y c o n t a i n an adhesive,
e s p e c i a l l y an emulsion-based adhesive such as vinyl a c e t a t e
3 4
resin-based emulsion or acrylic resin-based emulsion which
is generally used to process paper, or a hot melt adhesive
such as polyvinyl alcohol-based adhesive or polyamide-based
adhesive from the viewpoint of moldability.
5 In the present invention, the content of the organic
filler is not particularly limited but preferably 1 to 300
parts by mass, more preferably 5 to 200 parts by mass, much
more preferably 10 to 150 parts by mass and particularly
preferably 15 to 100 parts by mass based on 100 parts by mass
10 of the aromatic polyester resin (component A) from the
viewpoints of moldability and heat resistance. When the
content of the organic filler is lower than 1 part by mass,
the effect of improving the moldability of the composition
becomes small and when the content is higher than 300 parts
15 by mass, i-t is difficult to disperse the filler uniformly,
or the strength and appearance as well as moldability and
heat resistance of the composition as a material may
deteriorate disadvantageously.
The composition of the present invention may comprise
20 an inorganic filler. By mixing an inorganic filler, a
composition having excellent mechanical properties, heat
resistance and moldability can be obtained. 'The inorganic
filler used in the present invention is a fibrous, lamellar
or powdery filler which is generally used to reinforce an
25 ordinary thermoplastic resin.
Examples of the inorganic fiLler include fibrous
inorganic fillers such as carbon nanotubes, glass fibers,
asbestos fibers, carbon fibers, graphite fibers, metal
fibers, potassium titanate whiskers, aluminum borate
30 whiskers, magnesium-based whiskers, silicon-based whiskers,
wollastonite, imogolite, sepiolite, asbestos, slag fibers,
xonotlite, gypsum fibers, silica fibers, silica-alumina
fibers, zirconia fibers, boron nitride fibers, silicon
nitride fibers and boron fibers, and lamellar and particul-ate
3 5
inorganic fillers such as lamellar silicates, lamellar
silicates exchangedwith an organic oniumion, glass flakes,
non-swellable mica, graphite,.metal foils, ceramic beads,
talc, clay, mica, sericite, zeolite, bentonite, dolomite,
5 kaolin, powdery silicic acid, feldspar powder, potassium
titanate, shirasu balloon, calcium carbonate, magnesium
carbonate, barium sulfate, calcium oxide, aluminum oxide,
titanium oxide, aluminum silicate, silicon oxide, gypsum,
novaculite, dawsonite and carbon nanoparticles including
10 white clay fullerene.
The lamellar silicates include smectite-based clay
minerals such as montmorillonite, beidellite, nontronite,
saponite, hectorite and sauconite, clay minerals such as
vermiculite, halloysite, kanemite and kenyaite, and
15 swellable micas such as Li-fluor-taeniolite,
Na-fluor-taeniolite, Li-fluor-te%ra-silicic mica and
Na-fluor-tetra-silicic mica. They may be natural or
synthetic. Out of these, smectite-based clay minerals such
as montmorillonite and hectorite, and swellable synthetic
20 micas such as Li-fluor-taeniolite and
Na-fluor-tetra-silicic mica are preferred.
Out of these inorganic fillers, fibrous or lamellar
inorganic fi I lers are preferred, and glass fibers,
wollastonite, aluminum borate whiskers, potassium titanate
25 whiskers, mica, kaolin and cation exchanged lamellar
silicates are p~rticularly preferred. The aspect ratio of
the fibrous filler is preferably 5 or more, more preferably
10 or more, much more preferably 20 or more.
The fillermaybecoatedorbundledwithathermoplastic
30 resin such as an ethylene-vinyl acetate copolymer or a
thermosetting resin such as epoxy resin, or treated with a
coupling agent such as aminosilane or epoxysilane.
The content of the inorganic filler is preferably 0.1
to 200 parts by mass, more preferably 0.5 to 100 parts by
3 6
mass, muchmorepreferablylto 50partsbymass, particularly
preferably 1 to 30 parts by mass and most preferably 1 to
20 parts by mass based on 100 parts by mass of the aromatic
polyester resin (component A) .
5

The resin composition of the present invention may
comprise a release agent. As the release agent used in the
present invention may be used a release agent which is used
10 for ordinary thermoplastic resins.
Examples cf the release agent include fatty acids,
fatty acid metal salts, oxyfatty acids, paraffins,
low-molecular weight polyolefins, fatty acid amides,
alkylenebis fatty acid amides, aliphatic ketones and
15 modified silicones. When the resin composition comprises
one of these release agents, a molded article having
excellent mechanical properties, moldability and heat
resistance can be obtained.
Thesereleaseagentsmaybeusedaloneorincombination
20 of two or more. The content of the release agent is
preferably 0.01 to 3 parts by mass, more preferably 0.03 to
2 parts by mass based on 100 parts by mass of the aromatic
polyester rrsin (component A).
25
The resin'composition of the present invention may
comprise an antistatic agent. Exampl-es of the antistatic
agent include quaternary ammonium salt-based and
sulfonate-based compounds such as
30 (P-1auramidepropionyl)trimethylarnrnoniums ulfate and sodium
dodecylbenzene sulfonate, and alkyl phosphate-based
compounds. In the present invention, these antistatic
agents may be used a1.one or in combination of two or more.
The content of the antistatic agent is preferab1.y 0.05
to 5 parts by mass, more preferably 0.1 to 5 parts by mass
based on 100 parts by mass of the aromatic polyester resin
(component A) .
5
The resin composition of the present invention may
comprise a plasticizer. Generally known plasticizers may
beusedastheplaticizer. Theplasticizersmaybeusedalone
or in combination of two or more. The content of the
10 platicizer is preferably 0.01 to 30 parts by mass, more
preferably 0.05 to 20 parts by mass, much more preferably
0.1 to 10 parts by mass based on 100 parts by mass of the
aromatic polyester resin (component A). In the present
invention, a crystallization accelerator and a plasticizer
15 may be used independently but preferably in combination.

The resin composition of the present invention may
comprise an impact resistance improver. The impact
20 resistance improver is not particularly limited as long as
it can be used to improve the impact resistance of a
thermoplasticresin. Forexample, at least one selectedfrom
the followinq impact resistance improver may bc used.
Specific examples of the impact resistance improver
25 include ethylene-propylene copolymer,
ethylene-propylene-nonconjugated diene copolymer,
ethylene-butene-1 copolymer, acrylic rubbers,
ethylene-acrylic acid copolymer and alkali metal salts
thereof (so-called "ionomers"), ethylene-glycidyl
30 (meth)acrylate copolymer, ethylene-acrylate copolymers
(such as ethylene-ethyl acrylate copolymer and
ethylene-butyl acrylate copolymer), modified
ethylene-propylene copolymer, diene rubbers (such as
polyhutadiene, polyisoprene and polychloroprene),
38
diene-vinyl copolymers (such as styrene-butadlene random
copolymer, styrene-butadlene block copolymer,
styrene-butadiene-styrene block copolymer,
styrene-isoprene random copolymer, styrene-isoprene block
5 copolymer, styrene-isoprene-styrene block copolymer,
polybutadierle-styrene graft copolymer and
butadiene-acrylonitrile copolymer), polyisobutylene,
copolymer of isobutylene and butadiene or isoprene, natural
rubber, Thiokol rubber, polysulfide rubber, polyurethane
10 rubber, polyether rubber and epichlorohydrin rubber.
Further, impact resistance improvers having different
degrees of crosslinking, impact resistance improvers having
various micro-structures such as cis-structure and
trans-structure, and core-shell type multi-layer polymers,
15 each consisting of a core layer and at least one shell layer
covering the core layer, and having adjacent layers made of
different types of polymers, may also be used.
Even when the (co)polymers listed above are random
copolymers orblock copolymers, theymaybeusedas the impact
20 resistance improver of the present invention.
The content of the impact resistance improver is
preferably 1 to 30 parts by mass, more preferably 5 to 20
parts by mass, much more preferably 10 to 20 part.s by mass
based on 100 parts by mass of the aromatic polyester resin
25 (component A).

The resin composition of the present invention may
comprise a thermosetting resin such as phenolic resin,
30 melamine resin, silicone resin or epoxy resin in limits not
prejudicial to the spirit of the present invention. The
resin composition ofthe present inventionmay also comprise
a flame retardant such as bromine-based, phosphorus-based,
silicone-based or antimony compound in limits not
3 9
p r e j u d i c i a l t o t h e i n t e n t of t h e p r e s e n t i n v e n t i o n . The
r e s i n composition may f u r t h e r comprise a c o l o r a n t i n c l u d i n g
an o r g a n i c o r i n o r g a n i c dye o r pigment, f o r example, a n p x i d e
such a s t i t a n i u m d i o x i d e , a hydroxide such a s alumina white,
5 a s u l f i d e such a s z i n c s u l f i d e , a f e r r o c y a n i d e compound such
a s i r o n blue, a chromate such a s z i n c chromate, a s u l f a t e
such a s b a r i u m s u l f a t e , a carbonate such a s c a l c i u m c a r b o n a t e
a s i l i c a t e such a s u l t r a m a r i n e b l u e , a phosphate such a s
manganese v i o l e t , carbon such a s carbon b l a c k , o r a metal
10 c o l o r a n t s u c h a s b r o n z e p o w d e r o r aluminurnpowder. The r e s i n
composition may s t i l l f u r t h e r comprise a n i t r o s o - b a s e d
condensation p o l y c y c l i c c o l o r a n t such a s Naphthol Green B,
a n i t r o - b a s e d c o n d e n s a t i o n p o l y c y c l i c c o l o r a n t such a s
Naphthol Yellow B, an azo-based condensation p o l y c y c l i c
15 c o l o r a n t such as Naphthol Red o r Chromophthal Yellow, a
phthalocyanine-based condensation p o l y c y c l i c c o l o r a n t such
a s Phthalocyanine Blue o r Fast Sky Blue, o r IndanthreneBlue,
andaslidabilityacceleratorsuchasgraphiteor f l u o r o r e s l n .
These a d d i t i v e s may be used alone o r i n combination of two
20 o r more.

A molded a r t i c l e o b t a i n e d from t h e r e s i n composition
of t h e p r e s e n t i n v e n t i o n can be formed by i n j e c t i o n molding,
25 e x t r u s i o n m o l d i n g , v a c u u m o r p r e s s u r e m o l d i n g orblowmolding.
Examples ofthemoldedarticleincludepellets, f i b e r s , c l o t h ,
f i b e r s t r u c t u r e s , f i l m s , s h e e t s and s h e e t nonwoven f a b r i c s .
The m e l t molding method o f a p e l l e t of t h e r e s i n
composition of t h e p r e s e n t i n v e n t i o n is not l i m i t e d a t a l l ,
30 and p e l l e t s produced by known p e l l e t p r o d u c t i o n methods can
b e advantageously used. That is, a c o n v e n t i o n a l l y known
method i n which a r e s i n composition extruded i n t o a s t r a n d
o r p l a t e is c u t i n a i r o r water a f t e r t h e r e s i n j.s completely
s o l i d i f i e d o r while it is s t i l l molten and not completely
solidified can be advantageously employed in the present
invention.
Injection molding is carried out at a cyl-inder
temperature of 230 to 290°C and a mold temperature of
5 preferably 30 to 120°C, more preferably 40 to 110°C from the
viewpoint of crystallizing a molded article and increasing
the molding cycle at the time of injection molding.
These molded articles include housings, mechanical
parts such aswheels and gears, electricandelectronicparts
10 such as connectors, constructionmembers, civil engineering
members, agriculturalmaterials, automobile parts (interior
and exterior parts) and parts for daily use.
The film and sheet of the present invention are formed
by conventionally known methods. For example, the film and
15 sheet are formed by molding techniques such as extrusion
molding and cast molding. That is, an unstretched film is
extruded by using an extruder having a T die or circular die
and further stretched and heated to be formed. The
unstretched film may be directly used as a sheet. To form
20 a film, a material obtained by melt kneading together the
resin composition and the above-described components in
advance may be used, or these components may be melt kneaded
together at I-he time of extrusion mol~ding to be formed. An
unstretched film having few surface defects can be obtained
25 by mixing an electrostatic adhesive such as a su1foni.c acid
quaternaryphosphoniumsaltwiththemolten resin at the time
of extruding the unstretched film.
Further, an unstretched film can also be cast molded
by dissolving the resin composition and additive components
30 in a common solvent such as chloroform or methylene
dichloride, casting the resultiing solution and drying and
solidifying it.
The unstretched film may be stretched monoaxially in
the mechanical flow direction or in a direction orthogonal
4 1
tothemechanical flow d i r e c t i o n . A b i a x i a l l y oriented film
canbeproducedbycarryingoutseyuentialbiaxial s t r e t c h i n g
with r o l l e r s and a t e n t e r , simllltaneous b i a x i a l s t r e t c h i n g
with a t e n t e r , or tubular b i a x i a i s t r e t c h i n g . Further, the
5 film is generally heat s e t a f t e r s t r e t c h i n g s o as t o suppress
i t s h e a t shrinkage. Thestretchedfilmobtainedasdescribed
above may be o p t i o n a l l y subjected t o a s u r f a c e a c t i v a t i o n
treatment suchas plasma treatment, aminetreatmentorcorona
treatment i n accordance with a conventionally known method.
10 The film or sheet of the present invention may be used
alone or i n combinationwithanother type of a f i l m o r sheet.
When it is used i n combination with another type of a f i l m
or sheet, it is assembledwith a f i l m o r sheet made of another
material t o obtain, for example, a laminate, or with another
15 f o r m s u c h a s a n i n j e c t i o n m o l d e d a r t i c l e o r a f i b e r s t r u c t u r e .
EXAMPLES
The following examples are provided f o r the purpose
of f u r t h e r i l l u s t r a t i n g the present invention but are in no
20 way t o be taken as l i m i t i n g .
Examples 1 t o 3 and Comparative Examples 1 t o 5
1. Measurement values i n the examples were obtajned by the
following methods.
25 (1) I d e n t i f i c a t i o n o f cycliccarbodiimidestructurebyNMR
The synthesized c y c l i c carbodiimide compound
(component B) was confirmed by 'H-NMR and 1 3 ~ - ~Th~e ~ .
JNR-EX270 of JEOL Ltd. was used for NMR. Heavy chl.oroform
was used as a solvent.
30 ( 2 ) I d e n t i f i c a t i o n of carbodiimide skeleton of cyclic
carbodiimide (component B) by IR
The existence of the carbodiimide skeleton of the
synthesized c y c l i c carbodiimide compound (component B) was
confirmed by E'T-IR a t 2,100 t o 2,200 cm-I which is the
characteristic of a carbodiimide. The Magna-750 of
Thermonicoley Co., Ltd. was used for FT-IR.
(3) Melt viscosity
The melt viscosity of the resin composition was
5 confirmed with a rheometer. The Rheometer ARES of TA
Instruments was used. The melt viscosity was measured at
a temperature of 260°C and a shear rate of 1 s-l in a nitrogen
atmosphere for 6 secondsasrneasurementconditions. Themelt
viscosity at this point was confirmed.
10 The melt viscosity characteristics (MV) of a pellet
sample of the resin composition were measured by using
Capilograph 1B (of Toyo Seiki Seisaku-sho, Ltd.) and a 41
mm x 20 mmL capillary at a furnace body temperature of 260°C
and a shear rate of 1,000 sec-' based on IS011443:2005 after
15 it was dried at 140°C for 3 hours.
(4) Carboxyl group content
The resin composition was dissolved in purified
o-cresol in a nitrogen stream and titrated with a 0.05 N
potassium hydroxide ethanol solution by using Brornocresol
20 Blue as an indicator.
(5) Reducedviscosity retention (stabilityto hydrolysis)
The reduced viscosity retention of the resin
composition when it was treated at 121°C and 100 %RH (0.2
MPa) for100 hours in apressure cooker tester was evaluated.
2 5 The reduced viscosity (qsplc)w as measured at 35°C with
an Ubbellohde viscometer by dissolving 40 mg of the sample
in 10 ml of a mixed solvent of tetrachloroethane and phenol
( I / ) and the reduced viscosity retention ( % ) was obtained
fromthe reducedviscosityafterthe treatment ofthe sample
30 as a numerator and the reducedviscositybeforethetreatment
of the sample as a denominator.
(6) Existence of generation of isocyanate odor
When the resin composition was melt kneaded at 250°C
for 5 minutes, sensory evaluation was made according to
4 3
whetherameasurerdetectedanisocyanate smell or not. "Not
detected" means that an Isocyanate smell is not detected and
"detected" means that the isocyanate smell is detected.
5 Components A to C
(1) Aromatic polyester resin (component A)
Polybutylene terephthalate manufactured by WinTech
Polymer Ltd. was used (may be referred to as "(Al)
hereinafter) .
10 The reduced viscosity of the aromatic polyester resin
(Al) was 0.84 dl/g (intrinsic viscosity was 0.69 dL/g) . The
carboxylgroupcontent, meltviscosityand reducedviscosity
retention ofthe aromatic polyester resin are shownin Table
1.
15 (2) Cyclic carbodiimide compound (component B)
The cyclic carbodiimide compound (component B) was
manufactured by the following method.
o-nitrophenol (0.11 rnol), pentaerythritol
tetrabromide (0.025 rnol), potassiumcarbonate (0.33mol) and
20 200 ml of N,N-dimethylformamide were fed to a reactor
equipped with a stirrer and a heater in an N2 atmosphere and
reacted at 130°C for 12 hours, DMF was removed under reduced
pressure, the obtained solid was dissolved in 200 ml of
dicloromethane, and the resulting solution was separated
25 with100mlofwater 3times. Anorganic layerwas dehydrated
with 5 g of sodium sulfate, and dichloromethane was removed
under reduced pressure to obtain an intermediate product
(nitro compound) .
Then, the intermediate product (nitro compound) (0.1
30 mol), 5 % palladium carbon (Pd/C) (2 g) and 400 ml of an
ethanol/dichloromethane mixed solvent (70/30) were fed to
a reactor equippedwith a stirrer, hydrogen substitutionwas
carried out 5 times, and a reaction was carried out while
hydrogen was always suppl.ied at 25OC and terminated when the
4 4
amount of hydrogen did not decrease any more. Pd/C was
collected, and the mixed solvent was removed to obtain an
intermediate product (amine compound).
Then, triphenylphosphine dibromide (0.11 mol) and 150
5 ml of 1,2-dichloroethane were fed to a reactor equipped with
a stirrer, a heater and a dropping funnel in an N2 atmosphere
and stirred. A solution obtained by dissolving the
intermediate product (amine compound) (0.025 mol) and
triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was
10 gradually added dropwise tothe resulting solution at 25OC.
After the end of zddition, a reaction was carried out at 70°C
for5hours. Thereafter, t h e r e a c t i o n s o l u t i o n w a s : t i l t e r e d ,
and the filtrate was separated with 100 ml of water 5 times.
An organic layer was dehydrated with 5 g of sodium sulfate,
15 and 1,Z-dichloroethane was removed under reduced pressure
to obtain an intermediate product (triphenylphosphine
compound) .
Thereafter, di-tert-butyl dicarbonate (0.11 mol),
N,N-dimethyl-4-aminopyridine (0.055 mol) and 150 ml of
20 dichloromethane were fed to a reactor equipped with a stirrer
and a dropping funnel in an NZ atmosphere and stirred. 100
ml of dichloromethane containing the intermediate product
(triphenylphosphine compound) (0.025mol) dissolvcdtherein
was gradually added dropwise to the resulting solution at
25 25'C. After the end of addition, a reaction was carried out
for 12 hours. Thereafter, a solid obtained by removing
dichloromethane was purified to obtain the following cyclic
carbodiimide compound having two carbodiimide rings, each
having only one carbodiimide group (B1: molecular weight of
30 516) as the component C. The structure of this cyclic
carbodiirnide compound (Bl) was checked by NMR and IR.
(3) Polyvalent hydroxyl group-containing compound
(component C)
5 The following compounds were used as the component C.
Polyvalent hydroxyl group-containing compound (Cl):
p e n t a e r y t h r i t o l m a n u f a c t u r e d b y T o k y o C h e m i c a l I n d u s t r y C o . ,
Ltd., hydroxyl value of 1,648
Polyvalent hydroxyl group-containing compound (C2) :
10 trimethylolethane manufactured by Tokyo Chemical Industry
Co., Ltd., hydroxyl value of 1,401
Example 1
After I00 parts bymass ofthe aromaticpolyester resin
15 (Al) was vacuum dried at 110°C for 5 hours, 1 part by mass
of the cyclic carbodiimide compound ( D l ) and 1 part by mass
of the polyvalent hydroxyl group-containing compound (C1)
having a hydroxyl value of 200 or more were added to and melt
kneaded with the above aromatic polyester resin at a resin
20 temperature of 250°C for 5 minutes by using Labo Plastomill
(of Toyo Seiki Seisaku-sho, Ltd.) to obtain a resin
composition (Ml). An isocyanate smell was n o detected
duringtheproductionofthe resincomposition. Thecarboxyl
group content, melt viscosity and reduced viscosity
25 retenti.on of this composition are shown in Table I..
Example 2
A r e s i n c o m p o s i t i o n (M2) was o b t a i n e d i n t h e samemanner
a s i n Example 1 except t h a t t h e amount of t h e p o l y v a l e n t
5 hydroxyl group-containing compound ( C l ) was changed from 1
p a r t by mass t o 1 . 5 p a r t s by mass. An i s o c y a n a t e smell was
notdetectedduringtheproduction o f t h e r e s i n composition.
The carboxyl group c o n t e n t , m e l t v i s c o s i t y and reduced
v i s c o s i t y r e t e n t i o n of t h i s composition a r e shown i n Table
10 1.
Comparative Example 1
A r e s i n composition (M3) w a s o b t a i n e d i n t h e samemanner
as i n Example 1 except t h a t t h e p o l y v a l e n t hydroxyl
15 group-containing compound ( C l ) was n o t a d d e d . An i s o c y a n a t e
s m e l l was not d e t e c t e d d u r i n g t h e p r o d u c t i o n o f t h e r e s i n
composition. The c a r b o x y l g r o u p c o n t e n t , m e l t v i s c o s i t y a n d
reduced v i s c o s i t y r e t e n t i o n of t h i s compositi.on a r e shown
i n Table 1.
2 0
Example 3
A r e s i n c o m p o s i t i o n ( M 4 ) was o b t a i n e d i n t h e samemanner
as i n Example 1 except t h a t t h e p o l y v a l e n t hydr-oxyl
group-containing compound was changed from ( C l ) t o (C2) . An
25 i s o c y a n a t e s m e l l was not d e t e c t e d d u r i n g t h e production of
t h e r e s i n composition. The carboxyl group c o n t e n t , melt
v i s c o s i t y and reduced v i s c o s i t y r e t e n t i o n of t h i s
composition a r e shown i n Table 1.
30 Comparative Example 2
A r e s i n c o m p o s i t i o n (M5) was o b t a i n e d i n t h e s a m e m a n n e r
a s i n Comparative Example 1 except t h a t the c y c l i c
carbodiimide compound ( B l ) a s t h e component B w a s changed
t o p o l y c a r b o d i i m i d e Sb-Phaving a l i n e a r s t r u c t u r e (STABAXOL
(registered trademark) L' of Rhein Chemie Japan Ltd.). An
isocyanate smell was detected during the production of the
resin composition. The carboxyl group content, melt
viscosity and reduced viscosity retention of this
5 composition are shown in Table 1.
Comparative Example 3
Aresincomposition (M6) wasobtainedinthesamemanner
as in Comparative Example 1 except that the cyclic
10 polycarbodiimidecompound (Bl) as the component Bwas changed
to polycarbodiimide LA-1 having a linear structure
(Carbodilite (registered trademark) LA-1 of Nisshinbo
Chemical Inc.). An isocyanate smell was detectedduringthe
production of the resin composition. The carboxyl group
15 content, melt viscosity and reduced viscosity retention of
this composition are shown in Table 1.
Comparative Example 4
Aresincomposition (M7) wasobtainedinthesamemanner
20 as in Comparative Example 1 except that the cyclic
carbodiimide compound (Bl) as the component B was changed
tomonocarbodiimide Sb-I havingalinear structure (STABAXOL
(registered trademark) I of Rhein Chemie Japan, 1,td.I. An
isocyanate smell was detected during the production oE the
25 resin composition. The carboxyl group content, melt
viscosity and reduced viscosity retention of this
composition are shown in Table 1.
Comparative Example 5
3 0 A resin compos:i.tion (M8) was obtained in the same manner
as in Example 1 except that stearyl alcohol manufactured by
Wako Pure Chemical Industries, Ltd. which is a primary
alcohol was used in place of the polyhydric alcohol (Cl) as
the polyvalent hydroxyl group-containing compound having a
4 8
hydroxyl v a l u e of not l e s s t h a n 200. An i s o c y a n a t e smell
was not d e t e c t e d d u r i n g t h e p r o d u c t i o n of t h e r e s i n
composition. The c a r b o x y l g r o u p c o n t e n t , m e l t v i s c o s i t y a n d
reduced v i s c o s i t y r e t e n t i o n of t h i s composition a r e shown
5 i n Table 1.
IP
CD
Table 1
Reference
Example
A1
100
-
.
.
-
26.3
Example
Abbreviation
pbw
Type
pbw
type
pbw
eq/ton
Composition
properties
Resin composition
Thermoplastic
aromatic
polyester resin
(component A)
Carbodiimide
compound
(component B)
Polyvalent
hydroxyl
group-containing
compound
(component C)
Carboxyl group
content
3
M 4
10 0
B1
1
C 2
1
0.1
1
M 1
100
B 1
1
C 1
1
0.0
2
M2
100
B1
1
C1
1.5
0.2
Melt viscosity
Melt viscosity
characteristics
(MV)
Shear rate of 1000
s -1
i
Pa.s
Pa.s
Reduced viscosity
retention
Isocyanate smell
80.5
109
pbw: parts by weight
%
95.7
122
37.8
not
detected
56.7
8 7
92.8
not
detected
113.4
138
91.1 ----
not
detected
88.8
not
detected
Composition
Resin
aromatic
polyester resin
compound
Polyvalent
hydroxyi groupcontaining
compound
content
Melt viscosity
Melt viscosity
characteristics
Character-
Shear rate of
istic
properties
1000 s-I
1 1 Reduced
viscosity
retention
Isocyanate smell
Table 1 (Continued)
Comparative Example
1 2 3 4 5
Abbreviation M3 M5 M 6 M7 M8
pbw 1 100 1 100 1 100 1 100 1 100 1
Type B 1 Sb-P LA- 1 Sb-I B 1
I I
--
stearyi
type . - .
alcohol
pbw . - 1
5 1
Examples 4 to 13 and Comparative Examples 6 to 15
The properties of molded products obtained from the
resincompositions of the present application were checked.
1. Values in the examples were obtained by the following
5 methods.
(1) Melt viscosity characteristics (MV)
A pellet sample of the resin composition was measured
by using Capilograph IB (of Toyo Seiki Seisaku-sho, Ltd.)
and a $1 mm x 20 mmL capillary at a furnace body temperature
10 of26O0canda shearrateof1,000 ~ec~~basedonIS011443:2005
after it was drjed at 140°C for 3 hours.
(2) Tensile strength (TS)
Apellet sample ofthe resin composition was injection
molded at a resin temperature of 260°C, a mold temperature
15 of 80°C, an injection time of 15 seconds and a cooling time
of 15 seconds to obtain a IS03167 : 2002 tensile test specimen
after it was dried at 140°C for 3 hours and measured for its
tensile strength based on IS0527-1:1993 and 150527-2:1993.
The results are shown in Table 2.
20 (3) Pressure cooker test (PCT)
The test specimen used in the tensile strength test
was treated at 121°C and 100 %RH for 48 hours in a pressure
cooker tester to measure its tensile strength after the
treatment so as to obtain its strength retention before and
25 after the treatment. The test results are shown in Table
2. In Table 2, "impossible" means that the test specimen
could not be measured because it greatly deteriorated after
PCT and was therefore broken when it was fastened to a
measuring instrument at the time of measuring tensile
30 strength.
(4) Intrinsic viscosity
Amixed solvent of phenol and tetrachloroethane (mass
ratio of 60/40) was used to measure the intrinsic viscosity
o f t h e t e s t s p e c i m e n a t 3 5 " C b y u s i n g a n U b b e l l o h d e v i s c o m e t e r
52
ln accordance with a commonly used method.
(5) Amount of generated isocyanate gas
30 mg of a pellet sample of the resin composition was
heatedat 28O0Cfor 10minutes inaheatinqfurnacein a fixed
5 air stream (LOO ml/min) and the generated isocyanate gas was
collected to measure the amount of the isocyanate gas by gas
chromatography.
The results are shown in Table 2. The amount of the
generated isocyanate gas shown in Table 2 is a value based
10 on 1 g of the pellet sample.
(6) Existence of occurrence of mold deposit (MD)
An ISO3167:2002 tensile test specimen was formed 100
times continuously by injection molding a pellet sample of
the resin composition at a resin temperature of 260°C, a mold
15 temperature of 80°C, an injection time of 15 seconds and a
cooling time of 15 seconds after it was dried at 140°C for
3 hours to observe the existence of the occurrence of MD on
the mold visually. The following criteria were used. The
results are shown in Table 2.
20 0: MD is not observed even after 100 times or more of
continuous molding
A: MD is observed after I1 to 99 times of continuous molding
X : MD is observed after 10 times or less of continuocls molding
25 2. Components A to C
(1) Aromatic polyester resin (component A)
The same aromatic polyester resin (component A) as in
Example 1 was used.
(2) Cyclic carbodiimide compound (component B)
3 0 The STABAXOL (registered trademark) P400 of Rhein
Chemie JapanLtd. which is an aromaticcarbodiimide compound
was used as the carbodiimide compound 82 (component B)
besides Bl.
(3) Polyvalent hydroxyl group-containing compound
5 3
(component C)
The following compounds were used as the polyvalent
hydroxyl group-containing comgound (component C).
C3: glycerin mono-12-hydroxystearic acid ester (hydroxyl
5 value of 420, Rikemal (registeredtrademark) HC-100 of Riken
Vitamin Co., Ltd. )
C4: triglycerin stearic acid partial ester (hydroxyl value
of280, Rikemal (registeredtrademark) AF-70 of RikenVitamin
Co., Ltd. )
10 C6: decaglycerin monolaurate (hydroxyl value of 600, Poem
(registered trademark) L-021 of Riken Vitamin Co., Ltd.)
C7: propylene glycol monobehenate (hydroxyl value of 145,
Rikemal (registered trademark) PB-100 of Riken Vitamin Co.,
Ltd. )
15 (4) Others
The following compound was used as an antioxidant.
El: phenol-based antioxidant, IRGANOX (registered
trademark) 1010 of BASF Japan Ltd.
20
The aromatic polyester resin (Al), the cyclic
carbodiimide compound (component B), thepolyvalenthydroxyl
group-containing compound (component C) and the alltioxidant
(El) were weighed, dry blended together in a ratio shown in
25 Table 2 and melt kneaded together by means of a twin-screw
extruder (TEX-30 of The Japan Steel Works, Ltd.) at a
cylinder temperature of 260°C, a screw rotation speed of 130
rpm and an extrusion rate of 12 kg/h, and the extruded molten
resin in the form of a strand was cooled and cut with a
30 pelletizer to obtain a resin composition pellet sample.
Various evaluations were made on the obtainedpellet sample.
The results are shown in Table 2.

Table 2 (Continued)
Examples 14 and 15 and Comparative Example 16
(1) Aromatic polyester resin (component A)
Polyethylene terephthalate (FK-OM) manufactured by
Teijin Limited (may be referred to as "A2" hereinafter) was
used as the aromatic polyester resin (component A).
The aromatic polyester resin (A2) had an intrinsic
viscosity of 0.63 dL/g (reduced viscosity of 0.05 dl/g) and
a carboxyl group content of 15 eq/ton. Its melt viscosity
and reduced viscosity retention are shown in Table 3. When
A2wasusedasthe componentA, itsmeltviscositywasmeasured
(2) Cyclic carbodiimide compound (component B)
The above B1 was used as the carbodiimide compound
(component B) .
5 (3) Polyvalent hydroxyl group-containing compound
(component C)
The followi~lg compounds were used as the polyvalent
hydroxyl group-containing compound (component C).
C1: pentaerythritol (hydroxyl value of 1,645, manufactured
10 by Kanto Chemical Co., Inc.)
C3: glycerin mono-12-hydroxystearic acid ester (hydroxyl
value of 420, Rikemal (registered tradeniark) HC-100 of Riken
Vitamin Co., Ltd.)

15 The aromatic polyester resin (A2), the cyclic
carbodiimide compound (Bl) and the polyvalent hydroxyl
group-containing compound (component C) were weighed in
ratios shown in Table 3 and melt kneaded together by means
of Labo Plastomill (of Toyo Seiki Seisaku-sho, Ltd.) at a
20 resin temperature of 280"~for5 minutes to obtain resin
compositions (Examples14 and15andComparativeExample16).
An isocyanate smell was not detected during the production
oftheresincompositions. The carboxylgroupcontrnts, melt
viscosities and reduced viscosity retentions of the
25 compositions are shown in Table 3.

5 8
CLAIMS
1. A resin composition comprising an aromatic polyester
resin having a terminal carboxyl group content of not more
5 than 30 eq/ton (component A), a cyclic carbodiimide compound
having at least two carbodiimide rings, each having only one
carbodiimide group (component B) , and a polyval.ent hydroxyl
group-containingcompoundhavingahydroxylvalueofnotless
than 200 (component C) .
10
2. The resin composition according to claim 1, wherein
the component A contains polybutylene terephthal-ate in an
amount of not less than 50 mass%.
15 3. The resin composition according to claim 1, wherein
the component B is a cyclic carbodiimide compound havinq a
plurality of carbodiimide rings bonded thereto through a
spiro bond or a bond group.
20 4. The resin composition according to clalm 1, wherein
thecomponent Bis acycliccarbodiimidecompoundrepresented
by the following formula.
(In the above formula, X is a tetravalent group represented
25 by the fol.lowing formula (i-1). ~ r ' to ~r~ are each
independently an orthophenylene group or
1,2-naphthalene-diyl group which may be substituted by a
substituent.)
5. The resin composition according to claim 1, wherein
5 the content ofthe component Bis 0.1to 3 parts bymass based
on 100 parts by mass of the component A.
6. The resin composition according to claim 1, wherein
the component C is a polyhydric alcohol or a partial ester
10 thereof.
7. The resin composition according to claim 1, wherein
the component C has a hydroxyl value of not more than 1,000.
15 8. The resin composition according to claim 6, wherein
the component C is a partial ester of a polyhydric alcohol
and a fatty acid having 12 or more carbon atoms.
9. The resin composition according to claim 1, wherein
20 the content of the component C is 0.05 to 5 parts by mass
based on 100 parts by mass of the component A.
10. The resin composition according to claim 1 which has
a terminal carboxyl group content of not more than 5 eq/ton.
2 5
11. The resin composition according to claim 1 which has
a melt viscosity at 280°C of not more than 300 Pa.s and a
reduced viscosity retention of not less than 50 % after it
is kept for 100 hours in a 121°C, 100 %RH (0.2 MPa) pressure
cooker t e s ~ ' .
12, The r e s i n composition according Lo claim 2 whi.ch has
a melt v l s c , o s i t y a t 2 6 0 " ~of not more than 300 Pa.s and a
j
5 reduced vi.s8cosity r e t e n t i o n of not l e s s than 80 % a f t e r it
!
is kept f o r j l 0 0 hours i n a 121."C, 100 %RE$ ( 0 . 3 MPa) p r e s s u r e
1
cooker tes?.
13. A method of producing a r e s i n composition which
10 comprises