Title of Invention

AN ALIPHATIC POLYESTER RESIN COMPOSITION

Abstract An aliphatic polyester resin composition is provided which is excellent, in heat resistance, mold ability and hydrolysis resistance. The aliphatic polyester resin composition comprises a biodegradable polyester resin (A) essentially including an a- and/or β-hydroxycarboxylic acid unit and cross linked by at least one cross linking agent (B) selected from the group consisting of (meth) acrylate compounds and polyvalent isocyanate compounds, wherein some or all of carboxyl groups of the resin (A) are blocked by 0.01 to 20 parts by mass of a terminal blocking agent (C) based on 100 parts by mass of the resin (A).
Full Text TECHNICAL FIELD
The present invention relates to an aliphatic
polyester resin composition, a preparation method
therefor, and a molded article and a foamed article
produced from the resin composition. Particularly, the
invention relates to an aliphatic polyester resin
composition which comprises a crosslinked biodegradable
polyester resin with its terminal carboxyl groups at
least partly blocked and is excellent in heat resistance,
moldability and hydrolysis resistance, and to a
preparation method for the resin composition and a molded
article and a foamed article produced from the resin
composition.
BACKGROUND ART
Polylactic acids are more excellent'in heat
resistance with higher glass transition temperatures
(Tg) than other biodegradable resins, but the heat
resistance of the polylactic acids in a temperature range
higher than Tg is no: necessarily high. Since the
polylactic acids have lower crystallization rates, the
molding cycle for injection molding should be increased.
Further, the polylac.ic acids have lower melt
viscosities, so that molding conditions are
significantly limited. Therefore, the molding
productivity is relatively low.
For improvement of the heat resistance and the
productivity, the inventors of the present invention
previously proposed , and JP-2003-128901 and
JP-A-2003-238789 tha;; a biodegradable polyester is

crosslinked by addition of a (meth)acrylate compound or
a polyvalent isocyanate compound. Further, the
inventors proposed in JP-A-2003-147182 that a layered
silicate is additionally used.
On the other hard, JP-A-2001-261797 discloses a
technique for improving the heat resistance and the
hydrolysis resistance by blocking terminal carboxyl
groups of a polylactic acid by a specific carbodiimide
compound.
The heat resistance and moldability of the
polylactic acids are improved by the crosslinking and
the addition of the layered silicate. However, the
polylactic acids fail to maintain their physical
properties due to hydrolysis during prolonged storage
or during use under severely humid and hot conditions.
Therefore, the practicality of the polylactic acids is
not sufficient under such conditions.
Further, the polylactic acid with its terminal
groups blocked by the carbodiimide compound as disclosed
in JP-A-2001-261797 is not suitable for production of
injection molded articles, foamed articles and
blow-molded articles.
DISCLOSURE OF THE INVENTION
To solve the aforesaid problems, it is an object
of the present invention to provide an aliphatic
polyester resin composition excellent in heat resistance,
moldability and hydrolysis resistance, a preparation
method therefor, and a molded article produced from the
resin composition.
The inventors of the present invention have found
that the aforesaid problems are solved only by utilizing
the crosslinking and the terminal group blocking of a
biodegradable aliphatic: polyester resin in combination,
and attained the present invention.
The present invention is summarized as follows:


(1) An aliphatic polyester resin composition
comprising a biodegradable polyester resin (A) which
essentially comprises an a- and/or p-hydroxycarboxylic
acid unit and crosslinked by at least one crosslinking
agent (B) selected from the group consisting of
(meth)acrylate compounds and polyvalent isocyanate
compounds, wherein seme or all of carboxyl groups of the
resin (A) are blocked by 0.01 to 20 parts by mass of a
terminal blocking agent (CI based on 100 parts by mass
of the resin (A).
(2) In the aliphatic: polyester resin composition (1),
the terminal blocking agent (C) comprises at least one
compound selected from the group consisting of
carbodiimide compounds, epoxy compounds, oxazoline
compounds, oxazine compounds and aziridine compounds.
(3) In the aliphatic: polyester resin composition (1),
the crosslinking agent (B) is present in a proportion
of 0.01 to 10 parts by mass based on 100 parts by mass
of the biodegradable polyester resin (A).
(4) In the aliphatic polyester resin composition (1),
the biodegradable polyester resin (A) essentially
comprises one of poly(L-laotic acid), poly(D-lactic
acid), a copolymer of L-lactic acid and D-lactic acid
and a blend of poly(L-lactic acid) and poly(D-lactic
acid) .
(5) The aliphatic polyester resin composition (1)
further comprises 0.05 to 30 parts by mass of a layered
silicate based on 100 parts by mass of the biodegradable
polyester resin (A).
(6) A method for preparing the aliphatic polyester
resin composition (1) comprises: mixing a biodegradable
polyester resin (A) and a terminal blocking agent (C);
and then mixing a crosslinking agent (B) with the
resulting mixture.
(7) A molded article or a foamed article is produced
from any of the aliphatic polyester resin compositions
3

BRIEF DESCRIPTION OF THE ACCOMPANING DRAWING
Fig. 1 is a graph illustrating a relationship
between crystallinity (θ) and time (minute) for
determining a crystallization rate index according to
the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will hereinafter be
described in detail.
The biodegradable polyester resin (A) to be used
in the present invention essentially comprises an a-
and/or p-hydroxycarboxylic acid unit. Examples of the
a- and/or p-hydroxycarboxylic acid unit include L-lactic
acid, D-lactic acid, glycolic acid, 3-hydroxybutyric
acid, 3-hydroxyvaler ic; acid, and 3-hydroxycaproic acid,
among which L-lacticacid, D-lactic acid or a mixture
of L-lactic acid and D-lactic acid is preferred for
industrial mass production.
Therefore, the biodegradable polyester resin (A)
to be used in the present invention is po1y (L- and/or
D-lactic acid), poly ( glycolie acid),
poly(3-hydroxybutyric acid), poly(3-hydroxyvaleric
acid) or poly (3-hydroxycaproic acid) , or a copolymer or
a blend of any of these polymers.
In consideration of the mechanical strength and
heat resistance of an article molded from the inventive
aliphatic polyester resin composition, the a- and/or
P-hydroxycarboxylic acid unit is preferably present in
a proportion of not smaller than 50 mol%, more preferably
not smaller than 60 mol%, most preferably not smaller
than 7 5 moll, in the biodegradable polyester resin (A) .
The biodegradable polyester resin (A) preferably has a
melting point of not lower than 120°C, more preferably
not lower than 150°C. The melting point can be
4

controlled by properly selecting the type and amount of
the hydroxycarboxylic acid unit.
The biodegradable polyester resin (A) is prepared
by a known melt polymerization method, as required, in
combination with a solid state polymerization method.
Poly(3-hydroxybutyric acid) and poly(3-hydroxyvaleric
acid) may be microbiologically prepared.
As required, another biodegradable resin component
may be copolymerized or blended with the poly(a- and/or
P-hydroxycarboxylic acid) as the major component of the
biodegradable polyester resin (A), as long as the heat
resistance of the poly(a- and/or p-hydroxycarboxylic
acid) is not deteriorated. Examples of the
biodegradable resin component include aliphatic
polyesters such as polyethylene succinate and
polybutylene succinate which are prepared from a diol
and a dicarboxylic acid, poly (ω-hydroxyalkanoates) such
as poly(e-caprolactone), poly(butylene
succinate-co-butylene terephthalate) and poly(butylene
adipate-co-butylene terephthalate) which are
biodegradable even with aromatic components, polyester
amides, polyester carbonates, and polysaccharides such
as starch. A non-biodegradable resin component may be
copolymerized or blended with the poly(α- and/or
P-hydroxycarboxylic acid) without departing from the
scope of the present invention.
The molecular weight of the biodegradable
polyester resin is not particularly limited, but the
biodegradable polyester resin preferably has a weight
average molecular weight of not smaller than 50,000 and
not greater than 1,00C,000, more preferably not smaller
than 80,000 and not greater than 1,000,000. If the
weight average molecular weight is smaller than 50,000,
the melt viscosity of the resin composition is too low.
On the other hand, if the weight average molecular weight
is greater than 1,000,000, the moldability of the resin


composition is reduced.
The crosslinking agent (B) to be used for
crosslinking the biodegradable polyester resin (A)
comprises at least one crosslinking agent selected from
the group consisting of (meth)acrylate compounds and
polyvalent isocyanate compounds. The (meth)acrylate
compounds and the polyvalent isocyanate compounds may
be used in combination.
Preferred examples of the (meth)acrylate compounds
include a compound which conta.ins two or more (meth) acryl
groups in its molecule and a compound which contains one
or more (meth)acryl groups and one or more glycidyl
groups or vinyl groups in its molecule. These compounds
are highly reactive with the; biodegradable polyester
resin (A), and provide a resin composition less liable
to contain residual monomers and less liable to be
colored. Specific examples of the (meth)acrylate
compounds include glycidyl methacrylate, glycidyl
acrylate, glycerol dimsthacrylate, trimethylolpropane
trimethacrylate, trimethylolpropane triacrylate,
allyloxypolyethylene glycol monoacrylate,
allyloxypolyethylene glycol rr.onomethacrylate, ethylene
glycol dimethacrylate, diethylene glycol
dimethacrylate, polyethylene glycol dimethacrylate,
polyethylene glycol diacrylate, polypropylene glycol
dimethacrylate, polypropylene glycol diacrylate and
polytetramethylene glycol dimethacrylate (whose
alkylene glycol moiety may contain copolymerized
alkylenes having various molecular lengths), butandiol
methacrylate and butandiol acrylate, among which
ethylene glycol dimethacrylate, diethylene glycol
dimethacrylate, polyethylene glycol dimethacrylate and
polypropylene glycol dimethacrylate are preferred for
the safety and the reactivity.
Preferred examples of the polyvalent isocyanate
compounds include compounds which are highly reactive


with the biodegradable polyester resin (A) and provide
a resin composition less liable to contain residual
monomers. Specific examples of the polyvalent
isocyanate compounds include hexamethylene
diisocyanate, tolylene diisocyanate, diphenylmethane
diisocyanate, xylylene diisocyanate, naphthylene
diisocyanate, isophorone diisocyanate, polyesters
modified with polyvalent isocyanates,
poly (meth) acrylic acici compounds modified with
polyvalent isocyanates and compounds obtained by
modifying polyvalent alcohols with polyvalent
isocyanates, and mixtures of any of these compounds,
among which hexamethylene diisocyanate and tolylene
diisocyanate are preferred for the safety and the
reactivity.
The aforesaid crosslinking agent (B) is preferably
blended in the biodegradable polyester resin (A) in a
total amount of 0. 01 to L0 parts by mass, more preferably
O.01 to 5 parts by mass, further more preferably 0.01
to 1 part by mass, based on 100 parts by mass of the
biodegradable polyester resin (A) . If the amount of the
crosslinking agent is smaller than 0.01 part by mass,
the heat resistance and the moldability intended by the
present invention cannot be provided. If the amount of
the crosslinking agent is greater than 10 parts by mass,
the crosslinking degree is too high, so that the
operability is reduced.
Where the polyvalent isocyanate compound is used
as the crosslinking ager.t (B) , a blend amount of greater
than 5 parts by mass ma^ result in deterioration of the
operability and the safety because an unreacted portion
of the isocyanate compound is liable to evaporate.
Further, reheating reduces the molecular weight of the
resulting resin composition. Therefore, the blend
amount is preferably not greater than 5 parts by mass
based on 100 parts by mass of the biodegradable polyester


resin (A).
A method for the crosslinking by the crosslinking
agent (B) is not particularly limited, but the simplest
method is such that the biodegradable polyester resin
(A) is melt-mixed with the crosslinking agent (B).
Where the biodegradable polyester resin (A) is
melt-mixed with the crosslinking agent (B), a peroxide
is preferably added as a crosslinking assist agent for
increasing the crosslinking degree. Preferred
examples of the peroxide include organic peroxides which
are excellent in d i s p e r s i b i1i t y in the resin. Specific
examples of the organic peroxides include benzoyl
peroxide, bis (butylperoxy)trimethylcyclohexane,
bis(butylperoxy)methylcyclododecane, butyl
bis(butylperoxy)valerate, dicumyl peroxide, butyl
peroxybenzoa t e , dibutyl peroxide,
bis(butylperoxy)diisopropylbenzene,
dimethyldi(butylperoyy)hexane,
dimethyldi(butylperoxy)hexyne and butylperoxycumene.
The peroxide is preferably blended in the biodegradable
polyester resin (A) i:i an amount of 0.1 to 10 parts by
mass, more preferably 0.1 to 5 parts by mass, based on
100 parts by mass of the biodegradable polyester resin
(A). If the blend amount is smaller than 0.1 part by
mass, the effect of increasing the crosslinking degree
is reduced. A blend amount of greater than 10 parts by
mass is not preferred in terms of costs.
In the inventive aliphatic polyester resin, some
or all of carboxyl groups of the biodegradable polyester
resin (A) should be blocked by the terminal blocking
agent (C). A terminal blocking degree is not
particularly limited, but may be properly adjusted
depending on the application of the resin. However, the
ratio of the blocked terminal carboxyl groups of the
resin (A) is preferably not lower than 20%, more
preferably not lower than 50%, most preferably not lower


than 90%, with respect to the terminal carboxyl groups
of the resin (A) before the terminal blocking.
A method for blocking the terminal carboxyl groups
of the biodegradable polyester resin (A) is to add a
proper amount of a terminal blocking agent of a
condensation type such as a.n aliphatic alcohol or an
amide compound into a polymerization system in the
polymerization of the resir. and cause a
dehydration-condensation reaction at a reduced pressure
For easy control of the polymerization degree of the
resin, however, it is preferred to add a terminal
blocking agent of an addition type upon completion of
the polymerization or when the polymerized resin is
melted again.
The terminal blocking agent of the addition type
preferably comprises at least one compound selected from
the group consisting of carbodiimide compounds, epoxy
compounds, oxazoline compounds, oxazine compounds and
aziridine compounds.
Specific examples of the carbodiimide compounds
include N,N'-di-2,6-diisopropylphenylcarbodiimide,
N,N'-di-o-tolylcarbodiimide,
N, N' -diphenylcarbodiinide,
N,N'-dioctyldecylcarbodiimide,
N,N' -di-2,6-dimethylpnenylcarbodiimide,
N-tolyl-N'-cyclohexylcarbodiimide,
N,N' -di-2, 6-di-tert-butylphenylcarbodiimide,
N-tolyl-N'-phenylcarbodiimide,
N,N'-di-p-nitrophenylcarbodiimide,
N,N'-di-p-aminophenylcarbodiimide,
N,N' -di-p-hydroxyphen/lcarbodiimide,
N,N'-di-cyclohexylcarJ3odiimide,
N,N' -di-p-tolylcarbodiimide,
p-phenylenebis-di-o-tolylcarbodiimide,
p-phenylenebis-dicyclohexylcarbodiimide,
hexamethylenebis-dicyclohexylcarbodiimide,


4,4' -dicyclohexylmetnaneca rbodiimide,
ethylenebis-diphenylcarbodiimide,
N,N'-benzylcarbodiimide,
N-octadecyl-N'-pheny.l carbodiimide,
N-benzyl-N'-phenylcarbodiimide,
N-octadecyl-N'-tolylcarbodiimide,
N-cyclohexyl-N'-tolylcarbodiimide,
N-phenyl-N'-tolylcarbodiimide,
N-benzyl-N'-tolylcarbodiimide,
N,N'-di-o-ethylphenylcarbodiimide,
N,N'-di-p-ethylphenylcarbodiimide,
N,N'-di-o-isopropylphenylcarbodiimide,
N,N'-di-p-isopropylphenylcarbodiimide,
N,N'-di-o-is obutylphenylcarbodiimide,
N,N'-di-p-isobutylphenylcarbodiimide,
N,N' -di-2, 6-diethylphenylcarbodiimide,
N, N' -di-2-ethyl-6-isopropylphenylcarbodiimide,
N,N'-di-2-isobutyl-6-isopropylphenylcarbodiimide,
N, N'-di-2,4,6-trimetrylphenylcarbodiimide,
N,N'-di-2,4,6-triisopropylphenylcarbodiimide,
N,N'-di-2,4,6-triisokutylphenylcarbodiimide,
diisopropylcarbodiimi de, dimethylcarbodiimide,
diisobutylcarbodiimicle, dioctylcarbodiimide,
t-butylisopropylcarbcdiimide,
di-p-naphthylcarbodiimide, di-t-butylcarbodiimide and
aromatic polycarbodiimides. Other examples of the
carbodiimide compounds include polymers of any of these
compounds. These carbodiimide compounds may be used
either alone or in combination. In the present
invention, any of the aromatic carbodiimides, in
particular N,N'-di-2, b-diisopropylphenylcarbodiimide,
or a polymer of any of these compounds (having a
polymerization degree of about 2 to about 20) is
desirably used. It is particularly preferred to use any
of the carbodiimide compounds having a saturated cyclic
structure such as a cyclohexane ring, particularly


4,4 ' -dicyclohexylmethane carbodiimide, or a polymer of
any of these compounds (having a polymerization degree
of about 2 to about 20).
Examples of the =poxy compounds include
N-glycidylphthalimide, N-glycidyl-4-methylphthalimide,
N-glycidyl-4,5-dimeth/lphthalimide,
N-glycidyl-3-methylphthalimide,
N-glycidyl-3,6,-dimethylphthalimide,
N-glycidyl-4-ethoxyphthalimide,
N-glycidyl-4-chlorophthalimide,
N-glycidyl-4,5-dichlorophthalimide,
N-glycidyl-3,4,5,6-tetrabromophthalimide,
N-glycidyl-4-n-butyl-5-bromophthalimide,
N-glycidylsuccinimide, N-glycidylhexahydrophthalimide,
N-glycidyl-1,2,3,6-tetrahydrophthalimide,
N-glycidylmaleinimide,
N-glycidyl-a,p-dimethylsuccinimide,
N-glycidyl-a-ethylsuccinimide,
N-glycidyl-a-propylsv. ccinimide, N-glycidylbenzamide,
N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide,
N-glycidylstearamide,
N-methy1-4,5-epoxycyelohexane-1,2-dicarboxylimide,
N-ethyl-4, 5-epoxycyci. ohexane-1, 2-dicarboxylimide,
N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylimide,
N-naphthyl-4,5-epoxycyclohexane-l,2-dicarboxylimide,
N-tolyl-3-methyl-4,5-epoxycyclohexane-l,2-dicarboxyl
imide, o-phenylphenyl glycidyl ether, 2-methyloctyl
glycidyl ether, phenyl glycidyl ether,
3 -(2-xenyloxy)-1,2-epoxypropane, allyl glycidyl ether,
butyl glycidyl ether,, lauryl glycidyl ether, benzyl
glycidyl ether, cyclohexyl glycidyl ether, a-cresyl
glycidyl ether, p-t-butylphenyl glycidyl ether,
glycidyl methacrylate, ethylene oxide, propylene oxide,
styrene oxide, octylene oxide, 2-ethylhexyl glycidyl
ether, hydroquinone diglycidyl ether, resorcin
diglycidyl ether, 1,6-hexandiol diglycidyl ether and


hydrogenated bisphenol-A diglycidyl ether. Other
examples of the epoxy compounds include diglycidyl
terephthalate, diglycidyl tetrahydrophthalate,
diglycidyl hexahydrophthalate, dimethyl diglycidyl
phthalate, phenylene diglycidyl ether, ethylene
diglycidyl ether, tramethylene diglycidyl ether,
tetramethylene diglycidyl ether, hexamethylene
diglycidyl ether, sorbitol diglycidyl ether,
polyglycerol polyglycidyl ether, pentaerythritol
polyglycidyl ether, diglycerol polyglycidyl ether,
glycerol polyglycidyl ether, trimethylolpropane
polyglycidyl ether, resorcinol diglycidyl ether,
neopentylglycol diglycidyl ether, ethylene glycol
diglycidyl ether, diethylene glycol diglycidyl ether,
polyethylene glycol diglycidyl ether, propylene glycol
diglycidyl ether, dipropylene glycol diglycidyl ether,
polypropylene glycol diglycidyl ether and polybutadiene
glycol diglycidyl ether.
One or two or more compounds may be arbitrarily
selected from these epoxy compounds for blocking the
terminal carboxyl groups of the aliphatic polyester
resin. In terms of the reactivity, ethylene oxide,
propylene oxide, phenyl glycidyl ether, o-phenylphenyl
glycidyl ether, p-t-butylphenyl glycidyl ether,
N-glycidylphthalimide, hydroquinone diglycidyl ether,
resorcin diglycidyl ether, 1,6-hexandiol diglycidyl
ether, hydrogenated bisphenol-A diglycidyl ether,
ethylene glycol diglycidyl ether, polyethylene glycol
diglycidyl ether, 1,6-hexandiol diglycidyl ether and
trimethylolpropane polyglycidyl ether are preferred.
Specific examples of the oxazoline compounds
include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline,
2-propoxy-2-oxazoline, 2-butoxy-2-oxazoline,
2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline,
2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline,
2-nonyloxy-2-oxazoline, 2-decyloxy-2-oxazoline,
12

2-cyclopentyloxy-2-oxazoline,
2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline,
2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline,
2-phenoxy-2-oxazoline, 2-cresyl-2-oxazoline,
2-o-ethylphenoxy-2-oxazoline,
2-o-propylphenoxy-2-oxazoline,
2-o-phenylphenoxy-2-oxazoline,
2-m-ethylphenoxy-2-oxazoline,
2-m-propylphenoxy-2-o:cazol:L:ne,
2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline,
2-ethyl-2-oxazoline, 2-propyl-2-oxazoline,
2-butyl-2-oxazoline, 2-pentyl-2-oxazoline,
2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline,
2-octyl-2-oxazoline, 2-nonyI-2-oxazoline,
2-decyl-2-oxazoline, 2-cyclopentyl-2-oxazoline,
2-cyclohexyl-2-oxazol:..ne/ 2--allyl-2-oxazoline,
2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline,
2-phenyl-2-oxazoline, 2-o-ethylphenyl-2-oxazoline,
2-o-propylphenyl-2-ox£zoline,
2-o-phenylphenyl-2-oxezoline,
2-m-ethylphenyl-2-oxa2:oline,
2-m-propylphenyl-2-oxazoline and
2-p-phenylphenyl-2-oxazoline. Other examples of the
oxazoline compounds include 2,2'-bis ( 2-oxazoline) ,
2,2'-bis ( 4-methyl-2-oxazoline) ,
2,2'-bis (4,4' -dimethyl-2-oxa.zoline) ,
2,2'-bis (4-ethyl-2-oxazoline) ,
2,2'-bis (4,4'-diethyl-2-oxazoline) ,
2,2'-bis (4-propyl-2-oxazoline) ,
2,2'-bis (4-butyl-2-oxazoline) ,
2,2'-bis (4-hexyl-2-oxazoline) ,
2,2'-bis (4-phenyl-2-oxazoline) ,
2,2'-bis (4-cyclohexyl-2-oxazoline) ,
2 , 2'-bis (4-benzyl-2-oxazoline) ,
2 ,2'-p-phenylenebis (2-oxazoline) ,
2,2'-m-phenylenebis(2-oxazoline) ,
13

2,2'-o-phenylenebis (2-oxazoline) ,
2,2'-p-phenylenebis{4-methyl-2-oxazoline),
2,2'-p-phenylenebis(4,4'-dimethyl-2-oxazoline),
2,2'-m-phenylenebis(4-methyl-2-oxazoline),
2,2' -m-phenylenebis(4,4'-dimethyl-2-oxazoline) ,
2,2'-ethylenebis(2-oxazoline),
2,2' -tetraraethylenebis(2-oxazoline) ,
2,2'-hexamethylenebis (2-oxazoline) ,
2,2'-octamethylenebis (2-oxazoline) ,
2,2'-decamethylenebi s(2-oxazoline) ,
2,2' -ethylenebis(4-methyl-2-oxazoline) ,
2, 2' -tetramethylenebi,:; (4, 4' -dimethyl-2-oxa zol i ne ) ,
2,2' - 9, 9'-diphenoxyethanebis (2-oxazoline) ,
2,2'-cyclohexylenebis |2-oxazoline) and
2,2'-diphenylenebis(2-oxazoline).
Further other examples of the oxazoline compounds
include polyoxazoline compounds containing any of the
aforesaid compounds as a monomer unit, e.g., copolymers
of styrene and 2-isopropenyl-2-oxazoline. One or two
or more compounds may oe arbitrarily selected from the
aforesaid oxazoline compounds for blocking the terminal
carboxyl groups of the biodegradable polyester resin (A) .
In terms of the heat resistance, the reactivity and the
affinity for the biodegradable polyester resin (A),
2,2'-m-phenylenebis (2-oxazoline) and
2,2'-p-phenylenebis (2-oxazoline) are preferred.
Specific examples of the oxazine compounds include
2-methoxy-5,6-dihydro-4H-l,3-oxazine,
2-ethoxy-5,6-dihydro-4H-l,3-oxazine,
2-propoxy-5,6-dihydro-4H-l,3-oxazine,
2-butoxy-5,6-dihydro-4H-l,3-oxazine,
2-pentyloxy-5,6-dihydro-4H-l,3-oxazine,
2-hexyloxy-5,6-dihydrc-4H-l,3-oxazine,
2-heptyloxy-5,6-dihydro-4H-l,3-oxazine,
2-octyloxy-5,6-dihydrc-4H-l,3-oxazine,
2-nonyloxy-5,6-dihydrc-4H-l,3-oxazine,


2-decyloxy-5,6-dihydro-4H-l,3-oxazine,
2-cyclopentyloxy-5,6-dihydro-4H-1,3-oxazine,
2-cyclohexyloxy-5,6 - d i h y d r o - 4 H - 1,3-oxazine,
2-allyloxy-5,6-dihydro-4H-1,3-oxazine,
2-methallyloxy-5, 6-dihydro-4H-l, 3-oxazine and
2-crotyloxy-5, 6-dihydro-4H--l, 3-oxazine. Other
examples of the oxazine compounds include
2,2'-bis (5,6-dihydro-4H-l,3-oxazine) ,
2,2'-methylenebis(5,6-dihydro-4H-l,3-oxazine) ,
2,2'-ethylenebis(5,6-dihydro-4H-l,3-oxazine),
2, 2' -propylenebis (5, 6-dihyd.ro-4H-l, 3-oxazine) ,
2,2'-butylenebis(5,6-dihydro-4H-l,3-oxazine),
2,2'-hexamethylenebis(5,6-dihydro-4H-l,3-oxazine),
2,2'-p-phenylenebis(5,6-dihydro-4H-l, 3-oxazine) ,
2,2'-m-phenylenebis (5,6-dihydro-4H-l,3-oxazine) ,
2,2'-naphthylenebis (5,6-dihydro-4H-l,3-oxazine) and
2,2'-P,P'-diphenyleneois(5,6-dihydro-4H-l,3-oxazine).
Further other examples of the oxazine compounds include
polyoxazine compounds containing any of the aforesaid
compounds as a monomer unit. One or two or more
compounds may be arbitrarily selected from the aforesaid
oxazine compounds for blocking the terminal carboxyl
groups of the biodegradable polyester resin (A) such as
polylactic acid.
Specific examples of the aziridine compounds
include compounds obtained by addition reaction of a
mono-, bis- or poly-iiocyanate compound and
ethyleneimine.
The terminal blocking agent (C) should be blended
in the biodegradable polyester resin (A) in an amount
of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts
by mass, more preferably 0.5 to 8 parts by mass, based
on 100 parts by mass of the biodegradable polyester resin
(A). If the blend amount is smaller than 0.01 part by
mass, the hydrolysis resistance intended by the present
invention cannot be provided. On the other hand, a blend


amount of greater than 20 parts by mass is neither
effective nor preferable in terms of costs.
The inventive aliphatic polyester resin
composition is prepared by melt-mixing the biodegradable
polyester resin (A) , the crosslinking agent (B) and the
terminal blocking agent: (C) by means of a common extruder
such as a uniaxial extruder or a biaxial extruder, a roll
kneader, a Brabender kreader or the like. At this time,
it is also effective to use a static mixer or a dynamic
mixer in combination vith the extruder. In order to
facilitate the kneadirg, it is preferred to use the
biaxial extruder.
In the present invention, it is preferred to add
the terminal blocking agent (C) to the biodegradable
polyester resin (A), knead the resulting mixture, then
add the crosslinking acent (E) to the mixture and knead
the mixture. By blending the terminal blocking agent
(C) and the crosslinking agent (B) in this order, the
resin composition is effectively imparted with the
hydrolysis resistance. Therefore, it is preferred to
employ, for example, a mathod such that the biodegradable
polyester resin (A) and the terminal blocking agent (C)
are supplied into a main supply port of the extruder and
then the crosslinking agent (B) is added from a middle
portion of the extruder or a method such that the
biodegradable polyester resin (A) is supplied into a main
supply port of the extruder, then the terminal blocking
agent (C) is added fron a first feed port provided at
the middle of the extruder (a feed port closest to the
main supply port) and the crosslinking agent (B) is added
from a second or subsequent feed port. Alternatively,
the biodegradable polyester resin (A) preliminarily
terminal-blocked and the crosslinking agent (B) may be
supplied together into the extruder, and kneaded.
When the ingredients are supplied into the extruder,
the ingredients may be dry-blended, and a known transport


means such as a powder feeder or a pressure pump may be
used .
The layered silicate (D) may be blended in the
inventive aliphatic polyester resin composition for
further improvement of the moldability of the resin.
The layered silicate may be a natural silicate or a
synthetic silicate. Exemplary preparation methods for
the synthetic silicate; are a melt method, an
intercalation method and a hydrothermal method, and the
silicate may be synthesized by any of these methods.
Preferred examples of the layered silicate include
smectites, vermiculites and swelled fluorinated mica.
Examples of the smectites include montmorillonite,
beidellite, hectorite and saponite. Examples of the
swelled fluorinated mica include Na-type silicon
tetrafluoride mica, Na-type taeniolite and Li-type
taeniolite. Among these layered silicates,
montmorillonite and Na-type silicon tetrafluoride mica
are preferred. A cation exchange capacity is preferably
25 to 200meq/100g.
The layered silicate (D) is preferably blended in
the biodegradable polyester resin (A) in an amount of
O.05 to 30 parts by mass , more preferably 0.1 to 15 parts
bymass, further more preferably 0.5 to 10 parts by mass,
based on 100 parts by mass of the biodegradable polyester
resin (A). If the blend amount is smaller than 0.05
parts by mass, improvement of the heat resistance and
the moldability cannot be expected. On the other hand,
if the blend amount is greater than 30 parts by mass,
it is difficult to finely disperse the layered silicate
in the resin, and the resulting resin is liable to have
a reduced toughness.
It is preferred to preliminarily treat the layered
silicate (D) with organic cations. Examples of the
organic cations include protonized primary to tertiary
amines, quaternary ammoniums and organic phosphoniums.


Examples of the primary amines include octylamine,
dodecylamine and octadecylamine. Examples of the
secondary amines inc.ude dioctylamine,
methyloctadecylamine and dioctadecylamine. Examples
of the tertiary amines include dimethyloctylamine,
dimethyldecylamine, oimetbyllaurylamine,
dime thy lmyri st ylamine: , dimethylpalmitylamine,
dimethylstearylamine, dilaurylmonomethylamine,
tributylamine, N,N-dimethylaniline, trioctylamine,
dimethyldodecylamine and didodecylmonomethylamine.
Examples of the quaternary ammoniums include
tetraethylammonium, trimethyloctadecylammonium,
dimethyldioctadecylammonium,
dihydroxyethylmethyloctadecylammonium,
methyldodecylbis(polyethylene glycol)ammonium and
methyldiethy1(polypropylene glycol)ammonium.
Examples of the organic phosphoniums include
tetraethylphosphonium, tetrabutylphosphonium,
tetrakis(hydroxymethyi)phosphonium and
2-hydroxyethyltriphenylphosphonium. These cations
may be used either alcne or in combination.
A method for treating the layered silicate with the
organic cations is to disperse the layered silicate in
water or an alcohol and add a salt of the organic cations
to the resulting dispersion with stirring to exchange
inorganic ions of the layered silicate with the organic
cations, followed by filtering, washing and drying of
the resulting product.
Where the layered silicate (D) is used in the
present invention, an alkylene oxide or a compound having
a hydroxycarboxylic ac:.d unit may be added as a
dispersion improving agent to the biodegradable
polyester resin (A) for improvement of the
dispersibility of the layered silicate (D) in the
biodegradable polyester resin (A) . Such a compound has
affinity for both the biodegradable polyester resin and


the layered silicate, and is easily intercalated between
layers of the layerec. silicate to improve the
dispersibility of the layered silicate in the resin.
Examples of the alkylene oxide include polyethylene
glycol and polypropylene glycol. Examples of the
compound having a hydroxycarboxylic acid unit include
polylactic acid, polyhydroxybutyric acid and
poly(s-caprolactone). The compound having a
hydroxycarboxylic acid unit may be a compound with its
terminal carboxyl groups replaced with hydroxyl groups
(e.g., polycaprolactoadiol). The compound to be used
as the dispersion improving agent preferably has a number
average molecular weight of 200 to 50,000, more
preferably 500 to 20,000. If the molecular weight is
smaller than 200, a gas will emanate during the molding
or bleed-out from the resulting molded article will occur
If the molecular weight is higher than 50,000, the
intercalation of the compound between the layers of the
layered silicate will be insufficient.
The dispersion improving agent is preferably
blended in the biodegradable polyester resin (A) in an
amount of 0.01 to 20 parts by mass, more preferably 0.02
to 10 parts by mass, based on 100 parts by mass of the
biodegradable polyester resin (A) . If the blend amount
is smaller than 0.01 part by mass, the effect of the
addition of the dispersion improving agent will be small.
If the blend amount is greater than 20 parts by mass,
the mechanical strengti and the heat resistance of the
resin will be reduced. Exemplary methods for blending
the dispersion improving agent include a method such that
the layered silicate (D) is preliminarily impregnated
with the dispersion improving agent, a method such that
the dispersion improving agent is mixed with the layered
silicate (D) in the presence of water or an organic
solvent and then the water or the organic solvent is
removed by filtering or the like, a method such that the


dispersion improving agent is added when the
biodegradable polyester resin and the layered silicate
are melt - kneaded, and a method such that the dispersion
improving agent is added together with the layered
silicate when the biodegradable polyester resin is
synthesized. Among these methods, the method of
preliminarily mixing the dispersion improving agent with
the layered silicate is preferred.
A pigment, a heat, stabilizer, an antioxidant, a
weather resistant agent , a flame retarder, a plasticizer,
a lubricant, a mold release agent, an antistatic agent,
a filler or the like nay be added to the inventive
aliphatic polyester resin ccmposition, as long as the
properties of the aliphatic polyester resin composition
are not significantly deteriorated. Examples of the
heat stabilizer and the antioxidant include hindered
phenols, phosphorus conpounds, hindered amines, sulfur
compounds, copper compounds and halides of alkali metals,
and mixtures of any of these compounds. The heat
stabilizer, the antioxidant, the weather resistant agent
or a like additive is generally added during the melt
kneading or the polymerization. Exemplary inorganic
fillers include talc, cailcium carbonate, zinc carbonate,
wollastonite, silica, alumina, magnesium oxide, calcium
silicate, sodium alumiiate, calcium aluminate, sodium
aluminosilicate, magnesium silicate, glass balloon,
carbon black, zinc oxide, antimony trioxide, zeolites,
hydrotalcite, metal fibers, metal whiskers, ceramic
whiskers, potassium titanate, boron nitride, graphite,
glass fibers and carbon fibers. Exemplary organic
fillers include naturally existing polymers such as
starch, cellulose particles, wood powder, bean curd
refuse, chaff, wheat bran and kenaf, and products
obtained by modifying :hese polymers.
A method for mixing another thermoplastic resin
and/or the filler with the inventive aliphatic polyester


resin composition is not particularly limited. For
example, the aliphatic polyester resin, the
thermoplastic resin and/or the filler are kneaded by
means of a uniaxial extruder, a biaxial extruder, a roll
kneader, a Brabender kneader or the like after heating
and melting. It is also effective to use a static mixer
or a dynamic mixer in combination with the aforesaid
extruder.
Various articles can be molded from the inventive
aliphatic polyester resin composition by a known molding
method. At least one molding method selected from an
injection molding method, a blow molding method, an
extrusion molding method and a foam molding method is
preferably used.
An ordinary injection molding method as well as a
gas injection molding method, an injection press molding
method and an expansior injection molding method may be
employed as the injection molding method. A cylinder
temperature for the injection molding should be not lower
than the melting point I'm or the fluidizing temperature
of the resin, preferably 18 0 to 230°C, more preferably
190 to 220°C. If the molding temperature is too low,
short molding will occur to result in unstable molding,
and overload is liable to occur. On the other hand, if
the molding temperature is too high, the aliphatic
polyester resin will be decomposed and, therefore, the
resulting molded articLe will have a reduced strength
or be colored. The temperature of a mold should be not
higher than Tm-20°C. Where the crystallization of the
biodegradable polyester resin in the mold is to be
promoted for increasing the heat resistance of the
biodegradable polyester resin, the mold temperature is
preferably kept at a temperature of Tg+20°C to Tm-20°C
for a predetermined period and then cooled to not higher
than Tg. Where the crystallization of the resin in the
mold is not reguired, the mold temperature may be


immediately cooled to not higher than Tg. Where
post-crystallization is required, heat treatment is
preferably performed at a temperature of Tg to Tm-20°C.
Exemplary blow molding methods to be employed for
producing a blow-molded article from the inventive
aliphatic polyester resin composition include a direct
blow molding method in which the article is molded
directly from material chips, an injection blow molding
method in which a preform (bottomed parison) prepared
by injection molding is blow-molded, and a draw blow
molding method. Further, a hot parison method in which
a preform is blow-molded immediately after preparation
of the preform, or a cold parison method in which a
preform is once cooled and taken out and then reheated
to be blow-molded may be employed. A temperature for
the blow molding shou...d be Tg+20°C to Tm-20°C. If the
blow molding temperature is lower than Tg+20°C, the
molding will be difficult, and the resulting blow-molded
container will have an insufficient heat resistance. On
the other hand, if the blow molding temperature is higher
than Tm-20°C, the resulting blow-molded container is
liable to have an uneven wall thickness, and draw-down
will occur due to reduction of viscosity.
The extrusion molding method to be employed for
producing an extrusion-molded article from the inventive
aliphatic polyester resin composition will be described.
A T-die method or a round die method may be employed as
the extrusion molding method. A temperature for the
extrusion molding should be not lower than the melting
point Tm or the fluidizing temperature of the aliphatic
polyester resin composition, preferably 180 to 230°C,
more preferably 190 to 220°C. If the molding
temperature is too low, unstable molding will result,
and overload is liable to occur. On the other hand, if
the molding temperature is too high, the biodegradable
polyester resin (A) will be decomposed and, therefore,


the resulting extrusion-molded article will have a
reduced strength or be colored. Sheets, pipes and the
like are produced by the extrusion molding. For
improvement of the heat resistance of these articles,
a heat treatment may be performed at a temperature not
lower than the glass transition temperature (Tg) of the
aliphatic polyester resin composition and not higher
than Tm-20°C.
The sheets thus produced may be deep-drawn, for
example, by vacuum forming, air pressure forming or
vacuum air pressure forming. Temperatures for the deep
drawing and the heat treatment are preferably from
Tg + 20°C to Tm-20°C. If the deep drawing temperature is
lower than Tg+20°C, the deep drawing will be difficult,
and the resulting container is liable to have an
insufficient heat resistance. On the other hand, if the
deep drawing temperature is higher than Tm-20°C, the
resulting container is liable to have an uneven wall
thickness and a poorer impact resistance with its
orientation lost.
Any common foaming methods may be employed for
producing a foamed article from the inventive aliphatic
polyester resin composition. By means of an extruder,
for example, a foaming agent decomposable at the melting
point of the resin is preliminarily blended with the
resin and the resulting mixture is extruded from a
slit-like nozzle into a sheet or from a round nozzle into
a strand. Examples of the decomposable foaming agent
include azo compounds such as azodicarbonamides and
barium azodicarboxylates, ni~roso compounds such as
N,N'-dinitrosopentamethylenetetramine, hydrazine
compounds such as 4 , 4 ' -oxybis (benzene sulfonyl
hydrazide) and hydrazicarbonamide, and inorganic
foaming agents such as sodium hydrogencarbonate.
Alternatively, a volatile foaming agent may be injected
from a middle portion cf the extruder for foaming the


resin. Examples of such a foaming agent include
inorganic substances such as nitrogen, carbon dioxide
and water, and organic solvents typified by hydrocarbons
such as methane, ethane, butane and pentane, fluorinated
compounds and alcohols such as ethanol and methanol.
Further, foamed particles may be produced by preparing
particles of the resin composition, preliminarily
impregnating the resin particles with the organic
solvent, water or a like foaming agent, and changing the
temperature and/or the pressure to foam the resin
particles.
By employing any of the aforesaid molding methods,
various molded articles can be produced from the
inventive aliphatic polyester resin composition.
Specific examples of the molded articles include
tableware such as dishes, bowls, pots, chopsticks,
spoons, forks and knives, containers for fluids,
container caps, rulers,, stationery such as writing
utensils, clear cases and CD cases, daily commodities
such as sink corner strainers, trash boxes, washbowls,
tooth brushes, combs end hangers, agricultural and
horticultural materials such as flower pots and seeding
pots, toys such as plastic models, electrical appliance
resin components such as air conditioner panels,
refrigerator trays and housings, and automotive resin
components such as bunpers, interior panels and door
trims.
Specific examples of the containers for fluids
include drinking cups and beverage bottles for milk
beverages, cold beverages and alcoholic beverages,
temporary storage containers for seasonings such as soy
sauce, sauce, mayonnaise, ketchup and cooking oil,
containers for shampoo and rinse, cosmetic containers,
and agricultural containers. The shapes of the
containers for fluids are not particularly limited, but
the containers preferably have a depth of not smaller


than 5mm for containing the fluids. The wall
thicknesses of the containers are not particularly-
limited, but are preferably not smaller than 0.1mm, more
preferably 0.1 to 5mm, for strength.
Sheets and pipes can be produced from the inventive
aliphatic polyester resin composition. Specific
applications of the sheets and the pipes include material
sheets for deep drawing, material sheets for batch
foaming, cards such as credit cards, desk pads, clear
files, straws, and agricultural and horticultural rigid
pipes. Further, the sheets may be deep-drawn for
production of deep-drawn articles such as food
containers, agricultural and horticultural containers,
blister packages and press-through packages. The
shapes of the deep-drawn articles are not particularly
limited, but the deep-drawn articles preferably have
depths of not smaller than 2mm for containing food, goods
and drugs. Further, the deep-drawn articles preferably
have wall thicknesses of not smaller than 50µm, more
preferably 150 to 50µm. Specific examples of the food
containers include fresh food trays, instant food
containers, fast food containers and lunch boxes.
Specific examples of the agricultural and horticultural
containers include seeding pots. Specific examples of
the blister packages include food containers as well as
packages for various commodities including stationery,
toys and dry batteries..
Examples of the foamed articles produced from the
inventive resin composition include: bulk containers,
pads for iron containers and cushioning materials in a
packaging field; binders, cut files and cut boxes in a
stationery field; core materials for partitions, sign
boards, buffer wall materials and camping floor boards
in an architectural field; cases for video cameras and
cassettes and core materials for OA cases in an
electrical appliance field; fresh food packages,


confectionery packages and food trays in a food field;
door mats, toilet mats, kitchen mats, bath mats, garden
mats, mats for hospitals, screen materials and animal
rejection fences in a daily commodity material field;
seed beds and cases for hydroponic seed bases in an
agricultural material field; and fish net buoys, fishing
floats, oil fence buoys and cooler boxes in a fishery
material field.
According to the present invention, the aliphatic
polyester resin composition excellent in heat resistance,
moldability and hydrolysis resistance can be provided
by an industrially feasible technique. The resin
composition can be used for injection molding and blow
molding. Articles molded from the resin composition
maintain their physical properties even during use under
severely humid and hot conditions and during prolonged
storage .
Example s
The present invention will hereinafter be
described further specifically by way of examples.
However, it should be understood that the invention be
not limited to the following examples.
The following measurement methods were employed
for evaluation of Examples; and Comparative Examples
described blow.
(1) Molecular weight
The weight average molecular weight of polylactic
acid was determined at 40°C with the use of
tetrahydrofuran as an eluent by means of a gel permeation
chromatography (GPC) device ( available from Shimadzu Co . ,
Ltd. ) having a differential refractometer, and expressed
on the basis of polystyrene calibration standards. A
sample was dissolved in chloroform and diluted by THF.
(2) Flexural breakdown strength
In conformity with ASTM-790, a test strip having


a size of 150mmxl0mmx3 . 2 mm was prepared, and the flexural
breakdown strength was measured with a load being applied
to the test strip at a deformation rate of lmm/min.
(3) Melt flow rate (MFR)
In conformity with JIS K7210, the melt flow rate
was measured under conditions D specified in Table 1 of
Appendix A of JIS K7210 (with a load of 21.2N at a test
temperature of 190°C).
(4) Crystallization rate index (see Fig. 1)
With the use of a DSC machine (Pyrisl DSC available
form Perkin Elmer Corporation), a sample was heated at
a temperature increasing rate of +500°C/min from 20°C to
200°C, and kept at 200°C for 5 minutes. Then, the sample
was cooled at a temperature decreasing rate of -500°C/min
from 200°C to 130°C, and kept at 130°C for crystallization
With the final crystal1inity (0) defined as 1, as shown
in a graph of Fig. 1, time required for the crystallinity
to reach 0.5 was determined as the crystallization rate
index (min).
(5) Amount of terminal carboxyl groups
First, 0.15g of a resin was dissolved in 20ml of
methylene chloride, and an indicator (Phenol Red) was
added to the resulting solution. Then, the solution was
titrated with a 0.IN KOH solution.
(6) Evaluation of injection moldability
With the use of ai injection molding machine
(IS-100E available from Toshiba Machine Co., Ltd.), a
resin was injection-mo ded in a releasable cup mold
(having a diameter of 3 8mm and a height of 300mm and kept
at a temperature of 110°C) at a molding temperature of
200°C, and a minimum cycle time required for proper
release of a cup was determined.
(7) Evaluation of hydrolysis resistance
A test strip having a size of 15Ommx10mmx3.2mm in
conformity with ASTM-790 and pellets were stored in a
constant temperature/constant humidity chamber (Model


IW221 available from yamato Science Co., Ltd.) at a
temperature of 60°C and a humidity of 95% for 15 to 30
days. Then, the flexural breakdown strength of the test
strip was measured, and the MFR of the pellets was
measured after the pellets were dried at 50°C for 50 hours
in a vacuum condition. The flexural breakdown strength
was evaluated as a retention ratio (%) which was
determined on the basis of an initial flexural breakdown
strength.
Ingredients and .auxiliary materials used for
Examples and Comparative Examples are as follows.
A. Biodegradable polyester resins
- Resin A: Polylactic acid (having a weight average
molecular weight of 203,000, an L-lactic acid ratio of
99%, a D-lactic acid ratio of 1%, a melting point of 168°C
and an MFR of 3g/10 man)
• Resin B: A blend containing the resin A (polylactic
acid) and a copolymer of terephthalic acid, adipic acid
and 1,4-butandiol (having a melting point of 108°C and
an MFR of 5g/10 min) in a mass ratio of 90/10
B. Crosslinking agents
(1) (Meth)acrylate compounds
• PEGDM: Polyethylene glycol dimethacrylate (available
from Nippon Yushi Co., Ltd., and having an ethylene
glycol polymerization degree of 4)
• EGDM: Ethylene glycol dimethacrylate (available from
Nippon Yushi Co., Ltd.)
• DEGDM: Diethylene glycol dimethacrylate (available
from Nippon Yushi Co., Ltd.)
(2) Polyvalent isocyanate compound
■ HMDI: Hexamethylene ciisocyanate (available from
Nakarai chemical Ltd.)
- Di-t-butylperoxide (available from Nippon Yushi Co.,
Ltd.) was used as a crosslinking assist agent.
C. Terminal blocking agents
• CDI: N,N'-di-2,6-diisopropylphenylcarbodiimide


(STABAKSOL I available from Bayer Corporation)
• CDP: Aromatic polycarbodiimide (STABAKSOL P available
from Bayer Corporation)
• CDC: Polycyclohexylcarbodiimide (LA-1 available from
Nisshinbo Industries, Inc.)
■ EPX: p-t-butylphenyl glycidyl ether (DENACOL EX-146
available from Nagase Chemical Co., Ltd.)
• EX: Ethylene glycol diglyc;_dyl ether (DENACOL EX-810
available from Nagase Chemical Co., Ltd.)
• OXZ : 2,2'-m-phenyleneois(2-oxazoline) (available from
Tokyo Chemical Industry Co., Ltd.)
D. Layered silicate
• SBN-E: Montmorilloni:e with its interlayer ions
replaced by t rimethyloc.t adecylammonium ions (available
from Hojun Co., Ltd. and having an average particle
diameter of 2 . 5(im)
• MEE: Synthesized fluorinated mica with its interlayer
ions replaced by dihydroxyethylmethyldodecylammonium
ions (available from Corp Chemical Co., Ltd. and having
an average particle diameter of 6.3(j.m)
Example 1
First, 100 parts by mass of the resin A and 0.8 parts
by mass of the terminal blocking agent CDI were
dry-blended and supplied into a hopper of a biaxial
extruder (PCM-30 available from Ikegai Co., Ltd., and
having a die having three 4-mm diameter holes, an
extrusion head temperature of 210°C and a die outlet
temperature of 190°C). Then, a solution containing 0.2
parts by mass of PEGDM and 0 ,. 4 parts by mass of the
crosslinking assist agent dissolved in 1 part by mass
of an acetyltributyl citrate plasticizer was injected
into a middle portion of a kneader by means of a pump.
The resulting mixture was extruded, pelletized and dried.
Thus, an aliphatic polyester resin composition was
prepared. The results cf the evaluation of the physical


properties and the hydrolysis resistance of the
composition thus prepared are shown in Table 1.
Examples 2 to 18 and Comparative Examples 1 to 6
Resin compositions were prepared in substantially
the same manner as in Example 1, except that different
types and amounts of biodegradable polyester resins,
crosslinking agents, lamellar silicates and terminal
blocking agents were ised as shown in Table 1. Then,
the resin compositions were evaluated. The results of
the evaluation are shown in Table 1. In Examples 5, 6,
8, 9, 11, 12 and 13 ard Comparative Example 4, the
addition of the layered silicate was achieved by
dry-blending the biodegradable polyester resin and the
layered silicate and supplying the resulting mixture
into the hopper.
Example 19
First, 100 parts b/ mass of the resin A was supplied
into the hopper of the same biaxial extruder as employed
in Examples 1 to 18. Then, a solution containing 0.2
parts by mass of PEGDM and 0.4 parts by mass of the
crosslinking assist agent dissolved in 1 part by mass
of an acetyltributyl citrate plasticizer was injected
into a first feed port provided at the middle of the
kneader (a feed port closest to the hopper) by means of
a pump, and 1.5 parts by mass of the terminal blocking
agent CDI was supplied into a second feed port by a feeder,
The resulting mixture was extruded, pelletized and dried,
Thus, an aliphatic polyester resin composition was
prepared. The results of the evaluation of the resin
composition are shown ;.n Table 1.




Table 1 (to be continued)

32

Table 1

* Symbol - in evaluation means that measurement was impossible. (For flexural breakdown strength, test strips had strength insufficient for
the measurement. For MFR, samples had an extremely reduced molecular weight such that polymer's nature was lost.)
* Crosslinking agent and terminal blocking agent were added in this order in Example 19, and in reverse order in other examples.
33

As apparent fron Table 1, the resin compositions
of Examples 1 to 19 were excellent in injection
moldability with higher crystallization rate indices.
These resin compositions maintained their physical
properties (e.g., strength) even after having been
stored under the severely humid and hot conditions for
the evaluation of the hydrolysis resistance.
On the contrary, the resin composition of
Comparative Example 1 had a lower crystallization rate,
a longer injection molding cycle and a poorer moldability,
because no crosslinking agent was added. Further, the
hydrolysis resistance was poorer.
The resin compositions of Comparative Examples 2
to 6 had virtually no hydrolysis resistance, because no
terminal blocking age it was added.
Further, the following facts are revealed.
A comparison between Example 2 and Comparative
Example 1 shows that the resin composition of Example
2 with the polylactic acid crosslinked by the PEGDM had
a significantly higher crystallization rate and a
significantly shorter injection molding cycle than the
resin composition of Comparative Example 1. Although
the same type and amount of terminal blocking agent was
used, the resin composition of Example 2 was more
excellent in hydrolysis resistance. Therefore, the
resin composition prepared by utilizing the terminal
blocking and the crosslinking in combination was more
excellent in physical property retention under the high
temperature and high humidity conditions than the
terminal-blocked resin.
A comparison between Examples 1 to 4 and Comparative
Example 2 shows that the resin compositions of Examples
1 to 4 maintained their physical properties even after
having been stored under the high temperature and high
humidity conditions for the evaluation of the hydrolysis
resistance, because proper amounts of the terminal


blocking agent were used for the terminal blocking. In
Examples 1 to 4, different amounts of the terminal
blocking agent ranging from 0.5 to 8 parts by mass were
added and, as a result, it was found that the physical
property retention ratio was increased correspondingly
to the amounts of the added terminal blocking agent.
In Examples 5 and 6, the addition of the layered
silicate increased the crystallization rate thereby to
reduce the injection mo1ding cycle as compared with
Example 3 in which the resin composition was prepared
substantially in the same manner except that no layered
silicate was added. Although Example 5 and Comparative
Example 3 differ in whether or not the terminal blocking
agent was added, the resin composition of Example 5 with
the terminal-blocked resin maintained its physical
properties even after having been stored under the high
temperature and high humidity conditions for the
evaluation of the hydrolysis resistance.
Examples 7 to 9 in which the polylactic acid was
crosslinked by the isocyanate compound (HMDI) provided
the same effect as Examples 3, 5 and 6 in which the
polylactic acid was crosslinked by the PEGDM.
In Examples 10 and 11, the blend of the polylactic
acid and the copolymer of terephthalic acid, adipic acid
and 1, 4-butandiol was used as the biodegradable resin,
but the addition of the crosslinking agent or the
addition of the crossl Inking agent and the layered
silicate increased the crystallization rate and reduced
the injection molding cycle. Although Examples 10 and
11 differ from Comparative Examples 5 and 6 in whether
or not the terminal blocking agent was added, the resin
composition with the terminal-blocked resin maintained
its physical properties: even after having been stored
under the high temperature and high humidity conditions
for the evaluation of the hydrolysis resistance.
In Examples 12 and 13 in which the resin was


terminal-blocked by the epoxy compound and the oxazoline
compound, respectively, the physical properties were
maintained even after .storage under the high temperature
and high humidity conditions for the evaluation of the
hydrolysis resistance.
In Examples 14 and 15 in which CDP and CDC were
respectively employed as the terminal blocking agent
unlike in Example 1, the crystallization rate indices
and the injection molding cycles were equivalent to those
of Example 1, and the hydrolysis resistance was slightly
improved as compared with Example 1.
In Example 16 in which EX was employed as the
terminal blocking agent unl:.ke in Example 1, the
crystallization rate index, the injection molding cycle
and the hydrolysis resistance were slightly improved as
compared with Example 1.
In Examples 17 and 18, the (meth)acrylate compound
having shorter ethylene glycol chains was employed
instead of PEGDM for the crosslinking, but physical
properties equivalent to those of Example 3 were
provided.
In Example 19, the crosslinking agent and the
terminal blocking agent, were added in reverse order as
compared with Examples 1 to 18. As a result, the
crystallization rate and the injection molding cycle
were equivalent to those in Examples 1 to 3, but the
hydrolysis resistance was slightly poorer even with the
addition of a greater amount of the terminal blocking
agent as compared with Examples 1 to 3. However, the
hydrolysis resistance vas significantly improved as
compared with Comparative Example 1 in which the
crosslinking agent was not added. Therefore, the resin
composition of Example 19 hac. sufficiently practical
propert ies.


WE CLAIM;
1. An aliphatic polyester resin composition comprising a
biodegradable polyester resin (A) with essentially comprises an
a- and/or β-hydroxycarboxylic acid unit wherein some or all of
carboxyl groups of the resin (A) are blocked by 0.01 to 20 parts
by mass of a terminal blocking agent (C) consisting of
carbodiimide compounds based on 100 parts by mass of the
resin (A), and further is crosslinked by at least one crosslinking
agent (B) selected from the group consisting of (meth) acrylate
compounds and polyvalent isocyanate compounds, and a
peroxide.
2. An aliphatic polyester resin composition as set forth in claim 1,
wherein the crosslinking agent (B) is present in a proportion of
0.01 to 10 parts by mass based on 100 parts by mass of the
biodegradable polyester resin (A).
3. An aliphatic polyester resin composition as set forth in claim 1,
wherein the biodegradable polyester resin (A) essentially
comprises one of poly (L-lactic acid), poly (D-lactic acid), a
copolymer of L-lactic acid and D-lactic acid) and a bend of poly
(L-lactic acid) and poly (D-lactic acid).
4. An aliphatic polyester resin composition as set forth in claim 1,
comprising 0.05 to 30 parts by mass of a layered silicate
(D) based on 100 parts by mass of the biodegradable polyester
resin (A).


5. A method for preparing an aliphatic polyester resin composition
which comprises a biodegradable polyester resin (A) essentially
comprising an a- and 3-hydroxycarboxylic acid unit wherein
some or all of carboxyl groups of the resin (A) are blocked by
0.01 to 20 parts by mass of a terminal blocking agent (C)
consisting of carbodiimide compounds based on 100 parts by
mass of the resin (A), and further being crosslinked by at least
one crosslinking agent (B) selected from the group consisting of
(meth) acrylate compounds and polyvalent isocyanate
compounds, and a peroxide, the method comprising: mixing the
biodegradable polyester resin (A) and the terminal blocking
agent (C); and then mixing the crosslinking agent (B) and the
peroxide with the resulting mixture.
6. A molded article or a foamed article produced from an aliphatic
polyester resin composition as recited in any one of claims 1 to
4.
Dated this 26th DAY OF DECEMBER, 2005.
I. BANERJEE
OF L.S. DAVAR & CO.
APPLICANTS' AGENT

An aliphatic polyester resin composition is
provided which is excellent, in heat resistance,
mold ability and hydrolysis resistance. The aliphatic
polyester resin composition comprises a biodegradable
polyester resin (A) essentially including an a- and/or
β-hydroxycarboxylic acid unit and cross linked by at
least one cross linking agent (B) selected from the group
consisting of (meth) acrylate compounds and polyvalent
isocyanate compounds, wherein some or all of carboxyl
groups of the resin (A) are blocked by 0.01 to 20 parts
by mass of a terminal blocking agent (C) based on 100
parts by mass of the resin (A).

Documents:

2695-KOLNP-2005-FORM-27.pdf

2695-kolnp-2005-granted-abstract.pdf

2695-kolnp-2005-granted-claims.pdf

2695-kolnp-2005-granted-correspondence.pdf

2695-kolnp-2005-granted-description (complete).pdf

2695-kolnp-2005-granted-drawings.pdf

2695-kolnp-2005-granted-examination report.pdf

2695-kolnp-2005-granted-form 1.pdf

2695-kolnp-2005-granted-form 18.pdf

2695-kolnp-2005-granted-form 2.pdf

2695-kolnp-2005-granted-form 26.pdf

2695-kolnp-2005-granted-form 3.pdf

2695-kolnp-2005-granted-form 5.pdf

2695-kolnp-2005-granted-reply to examination report.pdf

2695-kolnp-2005-granted-specification.pdf

2695-kolnp-2005-granted-translated copy of priority document.pdf


Patent Number 230338
Indian Patent Application Number 2695/KOLNP/2005
PG Journal Number 09/2009
Publication Date 27-Feb-2009
Grant Date 25-Feb-2009
Date of Filing 26-Dec-2005
Name of Patentee UNITIKA LTD.
Applicant Address 50, HIGASHI-HOMMACHI 1-CHOME, AMAGASAKI-SHI, HYOGO
Inventors:
# Inventor's Name Inventor's Address
1 KAZUE UEDA C/O UNITIKA LTD., RESEARCH AND DEVELOPMENT CENTER 23, UJI KOJAKURA, UJI-SHI, KYOTO 611-0021
2 TATSUYA MATSUMOTO C/O UNITIKA LTD., RESEARCH AND DEVELOPMENT CENTER 23, UJI KOJAKURA, UJI-SHI, KYOTO 611-0021
3 TAKUMA YANO C/O UNITIKA LTD., RESEARCH AND DEVELOPMENT CENTER 23, UJI KOJAKURA, UJI-SHI, KYOTO 611-0021
4 FUMIO MATSUOKA C/O UNITIKA LTD., RESEARCH AND DEVELOPMENT CENTER 23, UJI KOJAKURA, UJI-SHI, KYOTO 611-0021
PCT International Classification Number C08J 3/24
PCT International Application Number PCT/JP2004/009300
PCT International Filing date 2004-06-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2003-184804 2003-06-27 Japan