The present invention relates to a resin composition comprising a polylactic
acid resin and a thermoplastic resin other than a polylactic acid. More specifically, the
present invention relates to a resin composition which is improved in compatibility
between a polylactic acid resin and a thermoplastic resin other than a polylactic acid
10 resin.
[Background Art]
The present invention relates to a resin composition comprising a polylactic
acid resin and a thermoplastic resin other than a polylactic acid. More specifically, the
~ preseni-inveniionie~aies~io resin comp"siiion impove&-in c"mF*ii'Diliiy~
15 between a polylactic acid resin and a thermoplastic resin other than a polylactic acid
resin.
In recent years, a biodegradable polymer that is degraded in the natural
environment has attracted attention and has been studied all over the world from the
purpose of global environment protection. Examples of the biodegradable polymer
20 including an aliphatic polyester such as polylactic acid, polyhydroxybutyrate and
polycaprolactone are known.
Among others, a polylactic acid is a highly biologically-safe and
environmentally friendly polymer material because it is produced by using lactic acid
obtained from a plant-derived raw material or a derivative thereof as an ingredient.
1
Therefore, a polylactic acid is studied to be used as a general-purpose polymer and in
the form of a stretched film, a fiber, an injection molding product or the like.
However, since a polylactic acid is an aliphatic polyester, it is inferior in heat
resistance, a crystallization rate, moist heat resistance stability and mechanical
5 characteristics compared with a general-purpose polymer derived from petroleum and is
not yet widely used in the field requiring various physical properties. Thus, various
studies for improving each of the physical properties have been made.
For example, Patent literature 1 discloses a composition obtained by blending a
polybutylene terephthalate which is an aromatic polyester with a polylactic acid.
10 Although the purpose of the composition is to improve heat resistance and
crystallization properties by the presence of a polybutylene terephthalate, since the
composition is obtained by simply blending a polylactic acid and a polybutylene
terephthalate, the compatibility between them is not good, and since the dispersion state
or-ihe-polymer coiiiponenis 'oecoriies ifie compos~~ohna& a~~demer>Lor'oeing
15 inferior in mechanical characteristics.
Patent literature 2 discloses a composition obtained by blending a
polytrimethylene terephthalate which is an aromatic polyester with a polylactic acid.
Since the compatibility between a polytrimethylene terephthalate and a polylactic acid
is poor, the composition is improved in characteristics such as chemical resistance but
20 had a demerit of forming a coarse dispersion state of the polymer components.
Patent literature 3 discloses a technique characterized in that a polyfunctional
isocyanate compound is added, as a compatibilizer, to a blended product of a
polybutylene terephthalate which is an aromatic polyester and a polylactic acid.
Although it has been reported that the compatibility between a polybutylene
2
terephthalate and a polylactic acid is improved by adding a polyfunctional isocyanate
compound, the dispersion state of the polymer components was not sufficient.
Patent literature 4 discloses a resin composition containing at least one
polyester and a cyclic carbodiimide compound. However, the compatibility of the
5 polymer components is not studied.
[Patent literature 11 Japanese Unexamined Patent Application Publication No.
2006-36818
[Patent literature 21 Japanese Unexamined Patent Application Publication No.
2009-179783
10 [Patent literature 31 Japanese Unexamined Patent Application Publication No.
201 1-201997
[Patent literature 41 Pamphlet of International Publication No. WO 20101071213
[S
15 [Technical Problem]
It is an object of the present invention to provide a polymer alloy resin
composition which is improved in compatibility between a polylactic acid resin and a
thermoplastic resin other than a polylactic acid by solving problems in conventional art
in which there are issues caused by the insufficient compatibility between a polylactic
20 acid and a thermoplastic resin other than a polylactic acid, such as insufficient
improvement in each of the physical properties, deterioration in mechanical
characteristics and poor appearance.
[Solution to Problem]
The present inventors have made earnest studies for the polymer alloy resin
composition to improve the compatibility between a polylactic acid resin and a
thermoplastic resin other than a polylactic acid. As a result, the present inventors have
found that the compatibility between a polylactic acid resin and a thermoplastic resin
5 other than a polylactic acid is improved by adding a cyclic carbodiimide compound
having a specific structure to a polylactic acid resin and a thermoplastic resin other a
polylactic acid, and have completed the present invention.
That is, according to the present invention, provided is
1. A resin composition comprising 1 to 99 pasts by weight of a polylactic acid
10 resin (Component A), 1 to 99 pasts by weight of a thermoplastic resin (Component B)
other than a polylactic acid and 0.1 to 3 parts by weight of a cyclic carbodiimide
compound (Component C) represented by the following formula (i):
(wherein, X is a tetravalent group represented by the following formula (i-I); and AS' to
15 Ar" are each independently an optionally substituted ostho-phenylene group or
1,2-naphthalene-diyl group.)
Further, the following are also included in the present invention.
2. The resin composition according to preceding clause 1, wherein in the resin
composition, the polylactic acid resin (Component A) and the thermoplastic resin
5 (Component B) other than a polylactic acid form a continuous phase and dispersoids
dispersed and present in the continuous phase, the dispersoids have an average diameter
of 2 pm or less at an arbitrary cross-section of the composition, the difference in the
number of the dispersoids is less than 10% at optional 5 places having 15 pm length and
15 p n ~w idih in the coniinuous phase in ihe cross-section, a116 ihe polylactic acid resin
10 (Component A) has a carboxylic group concentration of lOxa equivalentslton or less
(wherein, a is parts by weight of Component A/(Parts by weight of Component A +
Parts by weight of Component B + Parts by weight of Component C)).
3. The resin composition according to preceding clause 1, wherein the polylactic
acid resin (Component A) includes a poly-L-lactic acid and a poly-D-lactic acid and
15 contains a stereocomplex polylactic acid crystal.
4. The resin composition according to preceding clause 1, wherein the
thermoplastic resin (Component B) other than a polylactic acid is a thermoplastic resin
capable of reacting with carbodiimide andfor isocyanate.
5. The resin composition according to preceding clause 1, wherein the
5
thermoplastic resin (Component B) other than a polylactic acid is at least one selected
from the group consisting of a polyester, a polyamide and an aromatic polycarbonate.
[Advantageous Effects of Invention]
5 The resin composition of the present invention is improved in compatibility
between a polylactic acid resin and a thermoplastic resin other than a polylactic acid.
Therefore, desired physical properties can be improved without impairing appearance or
mechanical characteristics. Accordingly, the resin composition can, needless to say,
be suitably used as a general resin molding product and in the field such as a fiber or a
10 film.
In addition, since a cyclic carbodiimide compound contained in the resin
composition of the present invention is efficiently reacted with the carboxyl group
terminals of the polylactic acid resin and the acidic components of the thermoplastic
- - resinother thana-polylactic acid wheniniproving~ilie corrpaiibiliiy, ihecarboxyl group
15 concentration of the polylactic acid resin in particular is lowered, thus enabling an
improvement of the moist heat stability of the resin composition.
Further, when the cyclic carbodiimide compound reacts with the carboxyl
group terminals of the polylactic acid resin and with a group and/or a bond in the
thermoplastic resin other than a polylactic acid capable of reacting with carbodiimide,
20 an isocyanate group is formed in a polymer compound structure, and the compatibility
may be further improved by the reaction of the polylactic acid resin with a group andlor
a bond in the thermoplastic resin other than a polylactic acid capable of reacting with
isocyanate. In addition, since the formation of a by-product of a free isocyanate
compound can be suppressed, the generation of malodor due to the isocyanate
6
compound can be suppressed and the working environment is not deteriorated.
[Description of Embodiments]
Hereinafter, the present invention will be described in detail.
5 The resin composition of the present invention is characterized by comprising 1
to 99 parts by weight of a polylactic acid resin (Component A), 1 to 99 parts by weight
of a thermoplastic resin (Component B) other than a polylactic acid and 0.1 to 3 parts by
weight of a cyclic carbodiimide compound (C compound) represented by the following
formula (i).
10
In the present invention, the polylactic acid resin (Component A) is a resin
whose main chain is primarily composed of a lactic acid unit represented by the
following formula (I). The term "primarily" in the present description is a proportion
- of preferably 90 to 100 mol%, more preferably 95 to 100 mol% and further more
1.5 preferably 98 to 100 mol%.
The lactic acid unit represented by the formula (I) has an L-lactic acid unit and
a D-lactic acid unit which are mutually optical isomers. The main chain of the
polylactic acid resin (Component A) preferably is primarily an L-lactic acid unit, a
7
D-lactic acid unit or a combination thereof. The proportion of the other units
constituting the main chain is preferably 0 to 10 mol %, more preferably 0 to 5 mol%
and further more preferably 0 to 2 mol%.
Examples of the other units constituting the main chain include units derived
5 from a dicarboxylic acid, a polyhydric alcohol, a hydroxycarboxylic acid and a lactone.
Examples of the dicarboxylic acid include succinic acid, adipic acid, azelaic
acid, sebacic acid, terephthalic acid, isophthalic acid and the like. Examples of
polyhydric alcohol include: aliphatic polyhydric alcohols such as ethylene glycol,
1,3-propane diol, polypropylene glycol, butauediol, pentanediol, hexanediol, octanediol,
10 glycerin, sorbitan, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene
glycol, polypropylene glycol and the like; or aromatic polyhydric alcohols such as a
compound formed by the addition reaction of ethylene oxide to bisphenol. Examples
of the hydroxycarboxylic acid include glycolic acid, hydroxybutyric acid and the like.
-Examples- of the^--lacione~include glycolitie; E-caprolacione; p-propiolaciorie,~
15 6-butyrolactone, p- or y-butyrolactone, pivalolactone, 6-valerolactone and the like.
In order to satisfy both the mechanical properties and moldability of a molding
product, the polylactic acid resin (Component A) has a weight average molecular
weight of preferably 100,000 to 500,000, more preferably 110,000 to 350,000 and
fusther more preferably 120,000 to 250,000. The weight average molecular weight is a
20 value measured in terms of standard polystyrene by gel permeation chromatography
(GPC).
When the polylactic acid resin (Component A) is a poly-L-lactic acid or a
poly-D-lactic acid and a homo-phase polylactic acid, the polylactic acid resin
(Component A) preferably has a crystal melting peak (Tmh) between 150 and 190°C
8
and a crystal melting heat (AHmsc) of 10 J/g or more as measured by a differential
scanning calorimeter (DSC). By satisfing the above range of the crystal melting point
and the crystal melting heat of the polylactic acid resin (Component A), the heat
resistance can be improved.
5 In addition, the main chain of a polylactic acid preferably is a stereocomplex
polylactic acid containing a stereocomplex phase formed by a poly-L-lactic acid unit
and a poly-D-lactic acid unit. The stereocomplex polylactic acid preferably shows a
crystal melting peak at 190°C or more as measured by a differential scanning
calorimeter (DSC).
10 The stereocomplex polylactic acid preferably has a stereocomplex
crystallization degree (S) defined by the following expression (a) of 90 to 100%.
S = [AHms/(AHmh + AHms)] x 100 (a)
(Note that AHms represents the crystal melting enthalpy of a stereocomplex polylactic
acid phase and AHmh represents the meiiing enihalpy of a polylactic acid homo-phase
15 crystal).
The stereocomplex polylactic acid has a crystal melting point of preferably 190
to 250°C and more preferably 200 to 230°C. The crystal melting enthalpy of the
stereocomplex polylactic acid measured by DSC is preferably 20 J/g or more, more
preferably 20 to 80 Jlg and further more preferably 30 to 80 Jlg.
20 If the stereocomplex polylactic acid has a crystal melting point of less than
19OoC, the heat resistance is deteriorated. In addition, if the stereocomplex polylactic
acid has a crystal melting point exceeding 250°C, molding is required to be performed
at a high temperature exceeding 250°C and it may become difficult to suppress thermal
decomposition of the resin. Therefore, the resin composition of the present invention
9
preferably shows a crystal melting peak at 190°C or more as measured by a differential
scanning calorimeter (DSC).
In the stereocomplex polylactic acid, the weight ratio of the poly-D-lactic acid
to the poly-L-lactic acid is preferably 90110 to 10190, more preferably 80120 to 20180,
5 further more preferably 30170 to 70130 and especially preferably 40160 to 60140, and
theoretically preferably as close as possible to 111.
The stereocomplex polylactic acid has a weight average molecular weight of
preferably 100,000 to 500,000, more preferably 110,000 to 350,000 and further more
preferably 120,000 to 250,000. The weight average molecular weight is a value
10 measured in terms of standard polystyrene by gel pelmeation chromatography (GPC).
Further, the polylactic acid resin (Component A) may be amorphous.
The poly-L-lactic acid and the poly-D-lactic acid can be produced by a
conventionally known method. For example, the poly-L-lactic acid and the
poly-D-lactic acid can be produced by ring-opening polymerizaiion of L-lactide and
15 D-lactide in the presence of a metal-containing catalyst. In addition, the poly-L-lactic
acid and the poly-D-lactic acid can be produced by solid-phase polymerization of a
low-molecular weight polylactic acid containing a metal-containing catalyst in the
presence or absence of an inert gas stream under reduced pressure or under atmospheric
pressure to an elevated pressure after optional crystallization or without clystallization,
20 as requested. Further, the poly-L-lactic acid and the poly-D-lactic acid can be
produced by a direct polymerization method of performing dehydration condensation of
lactic acid in the presence or absence of an organic solvent.
The polymerization reaction may be carried out in a conventionally known
reaction vessel, for example, in the ring-opening polymerization or direct
10
polymerization method, a vertical reactor or a horizontal reactor equipped with a stirring
blade for high viscosity such as a helical ribbon blade and the like can be used alone or
in parallel. In addition, a batch, continuous or semibatch system may be used and a
combination of thereof may be used.
5 An alcohol may be used as a polymerization initiator. Such an alcohol
preferably does not inhibit the polymerization of a polylactic acid and is nonvolatile and
examples of such an alcohol which can be suitably used include decanol, dodecanol,
tetradecanol, hexadecanol, octadecanol, ethylene glycol, trimethylol propane,
pentaerythritol and the like. It can be said a preferred embodiment from a viewpoint of
10 prevention of fusion of a resin that a polylactic acid prepolymer used in the solid-phase
polymerization method is crystallized in advance. The prepolymer is polymerized in a
solid state in the temperature range from the glass transition temperature to less than the
melting point of the prepolymer in a fixed vertical or horizontal reaction vessel or a
reaction vessel (such as a rotary kiln and the like) which roiates by itself such as a
15 tumbler or a kiln.
Examples of the metal-containing catalyst include a fatty acid salt, a carbonate,
a sulfate, a phosphate, an oxide, a hydroxide, a halide, an alcoholate and the like of an
alkali metal, an alkaline earth metal, rare earths, transition metals, aluminum,
germanium, tin, antimony, titanium and the like. Among these, preferred are a fatty
20 acid salt, a carbonate, a sulfate, a phosphate, an oxide, a hydroxide, a halide and an
alcoholate which contain at least one metal selected from tin, aluminum, zinc, calcium,
titanium, germanium, manganese, magnesium and a rare earth element.
From the viewpoint of catalytic activity and reduced side reactions, preferred
examples of the catalysts include tin compounds, specifically tin-containing compounds
1 1
such as stannous chloride, stannous bromide, stannous iodide, stannous sulfate, stannic
oxide, tin myristate, tin octylate, tin stearate, tetraphenyl tin and the like. Among these,
suitably exemplified are tin (11) compounds, specifically diethoxy tin, dinonyloxy tin,
tin (11) myristate, tin (11) octylate, tin (11) stearate and tin (11) chloride.
5 The amount used of the catalyst is 0.42~10" to 100xl0-~(m ol), and preferably
1.68~10t-o~ 4 2.1 XIO-" (mol), and pal-ticularly preferably 2.53~10-301 6.8~10"( mol)
per 1 kg of lactide from the viewpoint of reactivity and the color and stability of the
resulting polylactide.
The metal-containing catalyst used for the polymerization of the polylactic acid
10 is preferably deactivated by a conventionally known deactivator prior to use of the
polylactic acid. Examples of such a deactivator include organic ligands consisting of a
group of chelate ligands which have an imino group and can coordinate with a
15 phosphoric acids having an acid value of 5 or less such as dihydride oxophosphoric (I)
acid, dihydride tetraoxodiphosphoric (11, 11) acid, hydride trioxophosphoric (111) acid,
dihydride pentaoxodiphosphoric (111) acid, hydride pentaoxodiphosphoric (11, IV) acid,
dodecaoxohexaphosphoric (111) acid, hydride octaoxotriphosphoric (111, IV, IV) acid,
octaoxotriphosphoric (IV, 111, IV) acid, hydride hexaoxodiphosphoric (111, V) acid,
20 hexaoxodiphosphoric (IV) acid, decaoxotetraphosphoric (IV) acid,
hendecaoxotetraphosphoric (IV) acid,eneaoxotriphosphoric (V, IV, IV) acid and the
like.
Further, examples of such a deactivator include orthophosphoric acid
represented by the formula xHzO yP205 in which x/y=3, a polyphosphoric acid in
12
which 2>x/y>l and which is referred to as diphosphoric acid, triphosphoric acid,
tetraphosphoric acid, pentaphosphoric acid, and the like depending on the degree of
condensation and a mixture thereof, metaphosphoric acid in which x/y=l, especially
trimetaphosphoric acid and tetrametaphosphoric acid, an ultraphosphoric acid in ~vhich
5 l>x/y>O and which has a network structure with a residual part of phospholus pentoxide
structure (which may be collectively referred to as a metaphosphoric acid compound)
and an acidic salt of these acids, a partial or whole ester of monovalent or multivalent
alcohols or polyalkylene glycols and a phosphono-substituted lower aliphatic carboxylic
acid derivative.
10 From the viewpoint of catalyst deactivation ability, orthophosphoric acids
represented by the formula xH20 yPzO5 and in which x/y=3 are prefesred. Also
prefeued are polyphosphoric acids and a mixture thereof in which 2>x/y>l and which
are referred to as diphosphoric acid, triphosphoric acid, tetraphosphoric acid,
pentaphospiioric- acid;or the~like depending oii ilie deggreec of coiideiisaiion;
15 metaphosphoric acid in which x/y=l, especially trimetaphosphoric acid and
tetrametaphosphoric acid; an ultraphosphoric acid in which l>x/y>O and which has a
network structure with a residual part of phosphorus pentoxide structure (which may be
collectively referred to as a metaphosphoric acid compound); an acidic salt of these
acids; and a partial or whole ester of monovalent or multivalent alcohols of these acids
20 or polyalkylene glycols.
The metaphosphoric acid-based compounds used in the present invention
include cyclic metaphosphoric acids in which approximately 3 to 200 phosphate units
are condensed, ultra-region metaphosphoric acids having a three-dimensional network
structure, and salts thereof such as alkali metal salts, alkali earth metal salts and onium
13
salts. Among these, preferably used are a cyclic sodium metaphosphate, ultra-region
sodium metaphosphate, dihexylphosphonoethyl acetate (may be abbreviated as DHPA
hereinafter) of a phosphono-substituted lower aliphatic carboxylic acid derivative, and
the like.
5 The polylactic acid resin (Component A) preferably has a lactide content of 1
to 5,000 ppm by weight is preferred. If lactide is present in a large amount in the
polylactic acid resin (Component A), the resin is deteriorated during melt processing,
the color tone of the resin is degraded and the resin may not be used as a product.
Although a poly-L-lactic acid and/or poly-D-lactic acid usually contain 1 to 5%
10 by weight of lactide immediately after melting ring-opening polymerization, the content
of lactide may be reduced to a suitable range by a conventionally known lactide
reduction method, that is, by performing following methods such as vacuum
devolatizing in a uniaxial or multiaxial extruder, high vacuum treatment in a
15 from the time point of completion of polymerization of the poly-L-lactic acid and/or
poly-D-lactic acid to the formation of polylactic acid.
As the lactide content becomes lower, the melt stability and moist heat
resistance stability of the resin are improved. However, since lactide present in the
resin has an advantage of reducing the melt viscosity of the resin, it is rational and
20 economical to adjust the lactide content corresponding to a desired purpose. That is, it
is rational to set the lactide content to 1 to 1,000 ppm by weight where the practical melt
stability is achieved. In addition, more preferably the range of 1 to 700 ppm by weight,
further more preferably 2 to 500 ppm by weight, and especially preferably 5 to 100 ppm
by weight is selected. When the polylactic acid resin (Component A) has a lactide
14
content of such a range, the stability of a resin during melt-forming of a molding
product of the present invention is improved, an advantage of efficiently performing
production of the molding product is improved and moist heat resistance stability and
low gas volatility of the molding product are enhanced.
5 The stereocomplex polylactic acid can be obtained by bringing the
poly-L-lactic acid and poly-D-lactic acid into contact with each other in a weight ratio
of 10190 to 90110, preferably by melting and bringing them into contact with each other
and more preferably by melt kneading them. The contact temperature is preferably
220 to 290 OC, more preferably 220 to 280°C and further more preferably 225 to 27S°C,
10 from the viewpoint of the improvement in stability and the degree of stereocomplex
crystallization during melting of the polylactic acid.
Although the melt kneading method is not particularly limited, a
conventionally known melt mixing device of a batch or continuous system is suitably
used. For example, although there may be used a melt stirring tank, a uniaxial or
15 biaxial extruder, a kneader, an shaft-less cage-type stissing tank, "Viborac" (trade name)
manufactured by Sumitomo Heavy Industries, Inc., N-SCR manufactured by Mitsubishi
Heavy Industries, Ltd., or a tubular polymerizer equipped with a spectacle-shaped blade
or lattice blade stirrer manufactured by Mitachi, Ltd., Kenics type stirrer or a Sulzer
SMLX type static mixer, there are suitably used an shaft-less cage-type stirring tank
20 which is a self-cleaning type polymerizer, N-SCR and a double-screw extruder, from
the viewpoint of productivity and quality, especially color tone of the polylactic acid.
qhermoplastic Resin (Component B) other than Polylactic Acid>
In the present invention, the thermoplastic resin (Component B) other than a
polylactic acid is a polymer which reacts with carbodiimide andlor isocyanate. The
15
polymer, for example, has a group and/or a bond capable of reacting with carbodiimide
and/or isocyanate. Examples of the group and/or bond capable of reacting with
carbodiimide include a carboxyl group, a sulfonic acid group, a sulfinic acid group, a
phenolic hydroxyl group, a hydroxyl group, an epoxy group, a phosfonic acid group, a
5 phosphinic acid group and the like. Examples of the group and/or bond capable of
reacting with isocyanate include a hydroxy group, an amino group, a thiol group, a
carboxyl group, a urethane bond, a urea bond and the like.
The polymer is not particularly limited, and examples of the polymer include at
least one selected from the group consisting of a polyester other than a polylactic acid, a
10 polyamide, a polycarbonate, a polyamide-imide, a polyimide, a polyolefin, a
polyurethane, a graft copolymer, a styrene-based resin, an epoxy resin, a phenol resin, a
vinyl ester resin and a terminal-modified product thereof.
Preferred examples of the polymer include at least one selected from the group
~ c~ onsi~ stlilg~ofa~polyeste~~otthhaenr a-~polylactica cid, apolyamide and~atraromatic
15 polycarbonate.
Since an object of the present invention is to improve compatibility between a
polylactic acid resin and a thermoplastic resin other than a polylactic acid, the present
invention provides a remarkable effect especially when using, as the thermoplastic resin
(Component B) other than a polylactic acid, a resin having low compatibility with a
20 polylactic acid, for example, an aromatic polyester such as a polybutyleneterephthalate,
a polyethyleneterephthalate and the like, a polyether ester elastomer, and an aromatic
polycarbonate.
In addition, the theimoplastic resin (Component B) other than a polylactic acid
may be used in combination with two or more.
16
(Polyester other than Polylactic Acid)
Examples of a polyester other than a polylactic acid include a polymer or a
copolymer obtained by polycondensation of at least one selected from a dicarboxylic
acid or an ester-forming derivative thereof, a diol or an ester-forming derivative thereof,
5 a hydroxycarboxylic acid or an ester-forming derivative thereof and lactone. A
preferred example is a thermoplastic polyester.
Such a thermoplastic polyester may contain a crosslinking structure obtained
by treating with a radical generation source, for example, an energy activating ray, an
oxidant and the like for the purpose of the moldability or the like.
10 Examples of the dicarboxylic acid or the ester-forming derivatives include an
aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid,
2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid,
bis(p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether
dicarboxylic acid, 5-tetrabutyl phosphonium isophthalic acid, 5-sodium sulfoisophthalic
15 acid and the like; an aliphatic dicarboxylic acid such as oxalic acid, succinic acid, adipic
acid, sebacic adic, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, dimer
acid and the like; an alicyclic dicarboxylic acid such as 1,3-cyclohexane dicarboxylic
acid, 1,4-cyclohexane dicarboxylic acid and the like; and an ester-forming derivative
thereof.
20 In addition, examples of the diol or the ester-forming derivative thereof
include: an aliphatic glycol having 2 to 20 carbon atoms, that is, ethylene glycol,
1,3-propanediol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol,
1,6-hexanediol, decamethylene glycol, cyclohexane dimethanol, cyclohexane diol,
dimer diol and the like; a long chain glycol having a molecular weight of 200 to
17
100,000, that is, polyethylene glycol, polytrimethylene glycol, polyl,2-propylene glycol
and polytetramethylene glycol and the like; and an aromatic dioxy compound, that is,
4,4'-dihydroxybiphenyl, hydroquinone, test-butyl hydroquinone, bisphenol A, bisphenol
S, bisphenol F and the like; and an ester-forming derivative thereof.
Further, examples of the hydroxycarboxylic acid include glycolic acid,
hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid,
hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and an
ester-forming derivative thereof. Examples of the lactone include caprolactone,
valerolactone, propiolactone, undecalactone, 1,s-oxepan-2-one and the like.
10 The polyester other than a polylactic acid is exemplified by an aromatic
polyester obtained by polycondensation of an aromatic dicarboxylic acid or an
ester-forming derivative thereof and an aliphatic diol or an ester-forming derivative
thereof as main components. Examples of the aromatic dicarboxylic acid or the
-ester-forming derivative thereof - - include either ierephihalic acid- -or
15 napl~thalene-2,6-dicarboxyliacc id or an ester-forming derivative thereof. Examples of
the aliphatic diol or the ester-forming derivative thereof include ethylene glycol,
1,3-propanediol, propylene glycol and butanediol.
Specific examples of the polyester include polyethylene terephthalate,
polyethylene naphthalate, polytrimethylene terephthalate, polypropylene naphthalate,
20 polybutylene terephthalate, polybutylene naphthalate, polyethylene
(terephthalatelisophthalate), polytrimethylene (terephthalate/isophthalate), polybutylene
(terephthalate/isophthalate), polyethylene terephthalate-polyethylene glycol,
polytrimethylene terephthalate-polyethylene glycol, polybutylene
terephthalate-polyethylene glycol, polybutylene naphthalate-polyethylene glycol,
18
polyethylene terephthalate-poly(tetramethy1ene oxide) glycol, polytrimethylene
terephthalate-poly(tetramethy1ene oxide) glycol, polybutylene terephthalate-poly
(tetramethylene oxide) glycol, polybutylene naphthalate-poly(tetramethy1ene oxide)
glycol, polyethylene (terephthalate1isophthalate)-poly(tetsamethy1ene oxide) glycol,
5 polytrimethylene (terephthalate1isophthalate)-poly(tetsamethy1ene oxide) glycol,
polybutylene (terephthalate1isophthalate)-poly(tetramethy1ene oxide) glycol,
polybutylene (terephthalatelsuccinate), polyethylene (terephthalate/succinate),
polybutylene (terephthalateladipate), polyethylene (terephthalateladipate) and the like.
In addition, the aliphatic polyester other than a polylactic acid is exemplified
10 by a polymer primarily composed of an aliphatic hydroxycarboxylic acid or a polymer
or a copolymer obtained by polycondensation of an aliphatic polyvalent carboxylic acid
or an ester-forming derivative thereof and an aliphatic polyhydric alcohol as main
components.
he polymer primarily composed of an aliphatic hydroxycarboxylic acid caKbe
15 exemplified by a polycondensate or a copolymer of glycolic acid, hydroxypropionic
acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid and the like.
Among others, examples of the polymer primarily composed of an aliphatic
hydroxycarboxylic acid include polyglycolic acid, poly3-hydroxybutyric acid,
poly4-polyhydroxybutyric acid, poly3-hydroxyhexanoic acid or a polycaprolactone and
20 a copolymer thereof.
In addition, an example of the polymer primarily composed of an aliphatic
hydroxycarboxylic acid includes a polymer primarily composed of an aliphatic
polyvalent carboxylic acid and an aliphatic polyhydric alcohol. Examples of the
polyvalent carboxylic acid include: an aliphatic dicarboxylic acid such as oxalic acid,
19
succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid,
glutaric acid, dimer acid and the like; an alicyclic dicarboxylic acid unit such as
1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like; and
an ester-forming derivative thereof. In addition, examples of the diol component
5 includes: an aliphatic glycol having 2 to 20 carbon atoms, that is, ethylene glycol,
1,3-propanediol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol,
1,6-hexanediol, decamethylene glycol, cyclohexane dimethanol, cyclohexane diol,
dimer dial and the like; a long chain glycol having a molecular weight of 200 to
100,000, that is, polyethylene glycol, polyl,3-propylene glycol, polyl,2-propylene
10 glycol and polytetramethylene glycol. Specific examples thereof include polyethylene
adipate, polyethylene succinate, polybutylene adipate or polybutylene succinate, a
copolymer thereof and the like.
Further, an example of a wholly aromatic polyester includes a polymer
~~~~ ~~--p obtaiiied-~~by- poly-coii~eiisaiioiio f aii~~ai~oiiiaciaiPc' irox;ylic acid~or esier.foiining
15 derivative thereof, preferably terephthalic acid or naphthalene-2,6-dicarboxylic acid, or
an ester-forming derivative thereof and an aromatic polyvalent hydroxy compound or an
ester-forming derivative thereof as main components.
Specifically, for example,
poly(4-oxyphenylene-2,2-propylidene-4-oxyphenylene-terephthaloyl-co-isophtha1oyl)
20 and the like is exemplified.
The polyester other than a polylactic acid can be produced a well-known
method (for example, described in "Saturated Polyester Resin Handbook "(written by
Kazuo Yugi, Nikkan Kogyo Shimbun (published on December 22, 1989), etc.).
Further, examples of the polyester other than a polylactic acid include: an
20
unsaturated polyester resin obtained by copolymerization of an unsaturated polyvalent
carboxylic acid or an ester-forming derivative thereof; and a polyester elastomer
containing a low-melting-point polymer segment, in addition to the above polyesters.
Examples of the unsaturated polyvalent carboxylic acid include maleic
5 anhydride, tetrahydromaleic anhydride, fumaric acid, endomethylene tetrahydromaleic
anhydride and the like.
The polyesters other than a polylactic acid in the present invention may be a
polyester elastomer obtained by copolymerizing a flexible component. The polyester
elastomer is a block copolymer consisting of a high melting point polyester segment and
10 a low melting point polymer segment having a molecular weight of 400 to 6,000, as
described in a known document, for example, Japanese Unexamined Patent Application
Publication No. 11-92636. A polymer formed only by a high melting point polymer
segment has a melting point of 150°C or more. A low melting point polymer segment
consisting of an aliphatic polyester produced from a polyaikylene glycols or an aliphatic
15 dicarboxylic acid having 2 to 12 carbon atoms and an aliphatic glycol having 2 to 10
carbon atoms has a melting point or a softening point of 80°C or less.
The polyester other than a polylactic acid preferably contains, as a main
repeating unit, at least one selected from the group consisting of butylene naphthalene,
ethylene teraphthalate, trimethylene terephthalate, ethylene naphthalene dicarboxylate
20 and butylene naphthalene dicarboxylate.
(Polyamide)
The polyamide is a thermoplastic polymer having an amide bond which is
obtained fsom an amino acid, a lactam, or a diamine and a dicarboxylic acid or an
amide-forming derivative thereof as main constitutional raw materials.
2 1
As the polyamide in the present invention, there may be used a polycondensate
obtained by condensation of a diamine and a dicarboxylic acid or an acyl activator
thereof, a polymer obtained by polycondensation of an aminocarboxylic acid, a lactam
or an amino acid, or a copolymer thereof. Examples of the diamine include an
5 aliphatic diamine and an aromatic diamine.
Examples of the aliphatic diamine include tetramethylenediamine,
hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine,
2,2,4-trimethylhexamethylenediamine,2 ,4,4-trimetl~ylhexamethylenediamine,
5-methylnonamethylenediamine, 2,4-dimethyloctamethylenedianline,
10 metaxylylenediamine, para-xylylenediamine, 1,3-bis(aminomethyl)cyclohexane,
bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane,
bis(aminopropyl)piperazine, aminoethylpiperazine, and the like.
15 Examples of the aromatic diamine include p-phenylenediamine,
m-phenylenediamine, 2,6-naphthalenediamine, 4,4'-diphenyldiamine,
3,4'-diphenyldiamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenylsulfone,3 ,4'-diaminodiphenylsnlfone,4 ,4'-diaminodiphenyl ketone,
3,4'-diaminodiphenyl ketone, 2,2-bis(4-aminophenyI)propane, and the like.
20 Examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic
acid, sebacic acid, dodecanoic acid, terephthalic acid, isophthalic acid,
naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid,
5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid,
hexahydroisophthalic acid, diglycolic acid, and the like.
22
Examples of the polyamide include an aliphatic polyamide such as
polycaproamide (Nylon 6), polytetramethylene adipamide (Nylon 46),
polyhexamethylene adipamide (Nylon 66), polyhexamethylene sebacamide (Nylon 610),
polyhexamethylene dodecamide (Nylon 612), polyundecamethylene adipamide (Nylon
5 116), polyundecanamide (Nylon 1 I), polydodecanamide (Nylon 12), and the like.
In addition, examples of the polyamide include: an aliphatic-aromatic
polyamide such as polytrimethylhexamethylene terephthalamide, polyhexamethylene
isophthalamide (Nylon 61), polyhexamethylene terephthal/isophthalamide (Nylon
6T/61), polybis(4-aminocyclohexyl)methane dodecamide (Nylon PACM12),
10 polybis(3-methyl-4-aminocyclohexyl)methane dodecamide (Nylon Dimethyl PACM12),
polymetaxylylene adipamide (Nylon MXD6), polyundecamethylene terephthalamide
(Nylon 11 T), polyundecamethylene hexahydroterephthalamide (Nylon 1 lT(H)) and a
copolymerization polyamide thereof, or a copolymer or a mixture thereof.
- - Furiher, exaiilples of ihe polyanlide include poly(p-phenyleiie ierephihalamide),
15 poly(p-phenylene terephthalamide-co-isophthalamide), and the like.
Examples of the amino acid include w-aminocaproic acid, w-aminoenanthic
acid, w-aminocaprylic acid, w-aminopergonic acid, w-aminocapric acid,
1 1-aminoundecanoic acid, 12-aminododecanoic acid, para-aminomethylbenzoic acid
and the like. Examples of the lactam include w-caproiactam, w-enantholactam,
20 w-capryllactam, w-laurolactam and the like.
The molecular weight of these polyamides is not particularly limited.
However, such polyamides preferably have a relative viscosity of 2.0 to 4.0, as
measured in a 98% concentrated sulfuric acid solution having a polyamide
concentration of 1% by weight at 25OC.
23
These amides can be produced according to a well-known method, for example,
"Polyamide Resin Handbook" (written by Osamu Fukumoto, Nikkan Kogyo Shimbun,
Ltd. (published on Janualy 30, 1988)).
The polyamides include a polyamide known as a polyamide elastomer.
5 Examples of such polyamides include a graft or block copolymer obtained by a reaction
of a polyamide-forming component having 6 or more carbon atoms with a
poly(a1kylene oxide) glycol. The linkage between the polyamide-forming component
having 6 or more carbon atoms and the poly(alky1ene oxide) glycol component is
usually an ester bond or an amide bond. However, the linkage is not particularly
10 limited by these bonds, and a third component, such as a dicarboxylic acid or a diamine
may be used as a reaction component of both components.
Examples of the poly(alky1ene oxide) glycols include: a block or random
copolymer of polyethylene oxide glycol, poly(l,2-propylene oxide) glycol,
poly(l,3-propylene oxide) glycol, poly(teiramethy1ene oxide) glycol,
15 poly(hexamethy1ene oxide) glycol and ethylene oxide with propylene oxide; and a block
and random copolymer of ethylene oxide with tetrahydrofuran. The poly(alky1ene
oxide) glycol has a number average molecular weight of 200 to 6,000, more preferably
300 to 4,000 in terms of polymerizability and rigidity.
As the polyamide elastomer for use in the present invention, preferred is a
20 polyamide elastomer obtained by polymerization of caprolactam, polyethylene glycol,
and terephthalic acid.
(Aromatic Polycarbonate)
The aromatic polycarbonate is obtained by reacting a dihydric phenol and a
carbonate precursor.
Representative examples of the dihydric phenol used here include
liydroquinone, resorcinol, 4,4'-biphenol, 1,l-bis(4-hydroxyphenyl)ethane,
2,2-bis(4-hydroxypheny1)propane (generally called bisphenol A),
2,2-bis(4-hydroxy-3-methylpheny1)propane 2,2-bis(4-hydroxyphenyl)butane,
5 1,l-bis(4-hydroxypheny1)-1-phenylethane, 1,l-bis(4-hydroxyphenyl)cyclohexane,
1,l -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl) ketone, bis(4-hydroxyphenyl) ester;
bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene,
9,9-bis(4-hydroxy-3-methylpheny1)fluorene and the like. The dihydric phenol
~~ ~~~~ ~ preferably i s a bis(4-hydroxypheny1)alkane;and-am on got hers,^
15 especially preferred and generally used from the viewpoint of excellent toughness and
deformation characteristics.
There may be used a special polycarbonate produced using dihydric phenols
other than a bisphenol-A based polycarbonate which is a general purpose polycarbonate.
For example, a polycarbonate (a single polymer or a copolymer), which is produced
20 using 4,4'-(m-phenylenediisopropylidene) diphenol,
1,l-bis(4-hydroxyphenyl)cyclohexane,
1,l -bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene as a
part or whole of the dihydric phenol component, is suitable for applications requiring
25
especially severe dimensional change or shape stability due to water absorption.
The aromatic polycarbonate can be produced by a method well known by
various literatures and patent gazette, for example, an interfacial polymerization method,
a melt transesterification method, a solid phase transesterification method of a carbonate
5 prepolymer, a ring-opening polymerization method of a cyclic carbonate compound,
and the like.
The viscosity average molecular weight of the aromatic polycarbonate is not
particularly limited and is preferably 1 x 1 o4 to 5x 1 04, mmo preferably 1 . 41~o 4 to 3x 1o 4
and further more preferably 1 . 4 ~ 1 0to~ 2 .4~10~I.f the polycarbonate has a viscosity
10 average molecular weight of less than 1 x lo4, sufficient toughness or crack resistance for
practical use may not be obtained. On the other hand, a resin composition obtained
from a polycarbonate having a viscosity average molecular weight exceeding 5x104, is
inferior in versatility because a generally high molding temperature is required or a
~ -~ ~ - - ~ ~ ~ ~~ ~~~ ~~~~ special~molciingmethodi s-required. 'The~high-mlding~temperatuirse iikely to cause^^
15 deterioration in deformation characteristics or rheological characteristics of the resin
composition.

In the present invention, the cyclic carbodiimide compound (Component C) is
represented by the following formula (i):
Wherein, X is a tetravalent group represented by the following formula (i-1),
and AI' to Ar4 are each independently an optionally substituted ortho phenyl group or
1,2-naphthalene-diyl group. Examples of the substituent include an alkyl group having
5 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a
nitro group, an amide group, a hydroxyl group, an ester group, an ether group, aldehyde
group and the like. In addition, these aromatic groups may have a heterocyclic ring
structure containing a hetero atom. Examples of the hetero atom include 0, N, S and
The cyclic carbodiimide compound (Component C) has a cyclic structure.
The cyclic structure bas one carbodiimide group (-N=C=N-) in which the first nitrogen
and the second nitrogen of the group are bonded by a bonding group. There is only
one carbodiimide group in a cyclic structure.
27
The cyclic carbodiimide compound preferably has a molecular weight of 100 to
1,000, If the molecular weight is less than 100, the cyclic carbodiimide compound
may have problems with the stability of the structure and volatility. In addition, if the
molecular weight is more than 1,000, the cyclic carbodiimide compound may have a
5 problem in terms of cost because the synthesis in a dilute system is required and the
yield is reduced in producing the cyclic carbodiimide. From such a viewpoint, the
cyclic carbodiimide compound has a molecular weight of preferably 100 to 750 and
more preferably 250 to 750.
Examples of such a cyclic carbodiimide compound (Component C) include the
10 following compounds.
In addition, these cyclic carbodiimide compound (Component C) can be
produced by a method well known by various literatures and patent gazette, for example,
a method described in Pamphlet of International Publication No. WO 2010/071213).
5 The cyclic carbodiimide compound (Component C) is bifunctional (two
carbodiimide groups) as shown in formula (i) and the cyclic carbodiimide compounds
- - illustrated below can be used in combination.
m, n = integer of 1 to 6
5 (If the cyclic carbodiimide compound is added to the main chain of the
polymer, n is the number of repeating units of the polymer).
(p, m, n = integer of 1 to 6)
5
n = integer of 1 to 6
(n = integer of 1 to 6)
0
(n = integer of 1 to 6)
(n = integer of 1 to 6)
(n = integer of 1 to 6)
Me0 OMe
(n = integer of 1 to 6)
(m, p = integer of 1 to 5, n = integer of 1 to 6)
(nl, n = integer of 0 to 3)
MeOOC -- /
N-C- N COOMe
( n=~ integer of 0 to 3, n = integer of 0 to 3)
(m = integer of 0 to 5, n = integer of 0 to 5)
The resin composition of the present invention comprises 1 to 99 parts by
weight of the polylactic acid resin (Component A), 1 to 99 parts by weight of the
thermoplastic resin (Component B) other than a polylactic acid and 0.1 to 3 pasts by
5 weight of the cyclic carbodiimide compound (Component C).
The amount of polylactic resins (Component A) is 1 to 99 parts by weight
based on 100 parts by weight of the resin composition. If the amount of the polylactic
acid resin (Component A) is more than 99 parts by weight, the effect of improving each
of the physical properties by the thermoplastic resin (Component B) other than a
10 - polylactic may-not be sufficient. From the viewpoint of the environmental load
reduction effect of the resin composition, the amount of the polylactic acid resin
(Component A) preferably is 50 to 99 parts by weight.
The amount of thestnoplastic resin (Component B) other than a polylactic acid
is 1 to 99 pasts by weight based on 100 pasts by weight of the resin composition. If the
15 amount of the thermoplastic resin (Component B) other than a polylactic acid is 1 parts
by weight or less, the effect of improving each of the physical properties by the
thermoplastic resin (Component B) other than a polylactic may not be sufficient.
From the viewpoint of the environmental load reduction effect of the resin composition,
the amount of the thermoplastic resin (Component B) other than a polylactic acid
20 preferably is 1 to 49.99 parts by weight.
34
The amount of the cyclic casbodiimide compound (Component C) is 0.1 to 3
pasts by weight based on 100 parts by weight of the resin composition. If the amount
of the cyclic carbodiimide compound (Component C) is less than 0.1 pasts by weight,
there may be no significance for applying the cyclic carbodiimide compound
5 (Component C). In addition, if the amount of the cyclic carbodiimide compound
(Component C) exceeds 3 pasts by weight, the effect of improving the compatibility
may not be sufficient. From the viewpoint of the compatibility between the polylactic
acid resin (Component A) and the thermoplastic resin (Component B) other than a
polylactic acid, the amount of the cyclic carbodiimide compound (Component C) is in
10 the range of 0.1 to 3 parts by weight, preferably an amount in which the amount of the
cyclic carbodiimide group of the carbodiimide compound (Component C)
corresponding to 1 equivalent of a group and/or a bond capable of reacting with the
carbodiimide in the resin composition is 0.1 to 5 equivalents, and more preferably an
~~~ ~ ~ amo~ u~ nt-~in~~~which~~theoamf tohuen-cta rbodiimide -group of the cyclic-carbodiimide
15 compound (Component C) corresponding to 1 equivalent of a group and/or a bond
capable of reacting with the carbodiimide in the resin composition is 0.7 to 1.5
equivalents.

The resin composition of the present invention can be produced by
20 melt-kneading the polylactic acid resin (Component A), the thermoplastic resin
(Component B) other than a polylactic acid and the cyclic carbodiimide compound
(Component C). In addition, the resin composition of the present invention can be
produced by melt-kneading the polylactic acid resin (Component A) and the cyclic
carbodiimide compound (Component C) and then adding the thermoplastic resin
35
(Component B) other than a polylactic acid, followed by melt-kneading the resulting
mixture. On the other hand, the resin composition of the present invention can be
produced by melt-kneading the thermoplastic resin (Component B) other than a
polylactic acid and the cyclic carbodiimide compound (Component C) and then adding
5 the polylactic acid resin (Component A), followed by melt-kneading the resulting
mixture.
In addition, when the polylactic acid resin (Component A) is a stereocomplex
polylactic acid, a stereocomplex polylactic acid is formed and the resin composition of
the present invention can be produced by mixing a poly-L-lactic acid and a
10 poly-D-lactic acid of the polylactic acid resin (Component A), the thermoplastic resin
(Component B) other than a polylactic acid and the cyclic carbodiimide compound
(Component C).
A method for mixing by adding the cyclic carbodiimide compound
- - (Component-C) to the polylactic acid resin (Component A) and/or the ihermopiasiic
15 resin (Component B) other than a polylactic acid is not particularly limited, and there
may be employed a method in which the cyclic carbodiimide compound (Component C)
is added as a solution, a melt or a master batch of the polylactic acid resin (Component
A) and/or the thermoplastic resin (Component B) other than a polylactic acid to be
applied, or a method in which a solid of the polylactic acid resin (Component A) andlor
20 the thermoplastic resin (Component B) other than a polylactic acid is brought into
contact with a liquid in which the cyclic carbodiimide compound (Component C) is
dissolved, dispersed or melted to impregnate the cyclic carbodiimide compound
(Component C), as used in conventionally well-known methods.
In the case of employing a method in which the cyclic carbodiimide compound
36
is added as a solution, a melt or a master batch of the polylactic acid resin (Component
A) andfor the thermoplastic resin (Component B) other than a polylactic acid to be
applied, a conventionally known kneading device may be used to add the cyclic
carbodiimide compound (Component C). In kneading, the cyclic carbodiimide
5 compound (Component C) is preferably kneaded in a solution state or a molten state
from the viewpoint of unifolm kneading. The kneading device is not particularly
limited, and examples of the kneading device include a conventionally known vertical
reaction vessel, a mixing tank, a kneading tank or a uniaxial or multiaxial horizonal
kneading device such as a uniaxial or multiaxial extruder or kneader. The mixing time
10 is not particularly specified and is 0.1 minutes to 2 hours, preferably 0.2 minutes to 60
minutes and more preferably 0.2 minutes to 30 minutes, depending on the mixing
device and mixing temperature.
As a solvent, there may be used a solvent which is inert to the polylactic acid
~ ~ ~~ ~ - ~ p ~esi1l(~oi1-ipolie~ii~t /x>a iidlor tlilic t:iciiiioplastic fesiil (~oii-ip~l~ecll)t other~tliaai~
15 polylactic acid and the cyclic carbodiimide compound (Component C). Especially, a
solvent which has an affinity to both the compounds and at least partially dissolves the
both compounds is preferred.
As the solvent, for example, there may be used a hydrocarbon-based solvent, a
ketone-based solvent, an ester-based solvent, an ether-based solvent, a halogen-based
20 solvent and an amide-based solvent.
Examples of the hydrocarbon-based solvent include hexane, cyclohexane,
benzene, toluene, xylene, heptane, decaneand the like. Examples of the ketone-based
solvent include acetone, methyl ethyl ketone, diethyl ketone, cyclohexanone,
isophorone and the like.
Examples of the ester-based solvent include ethyl acetate, methyl acetate, ethyl
succinate, methyl carbonate, ethyl benzoate, diethylene glycol diacetate and the like.
Examples of the ether-based solvent include diethyl ether, dibutyl ether, tetrahydrofuran,
dioxane, diethylene glycol dimethyl ether, triethylene glycol diethyl ether, diphenyl
5 ether and the like. Examples of the halogen-based solvent include dichloromethane,
chloroform, tetrachloromethane, dichloroethane, 1,11,2,2'-tetrachloroethane,
chlorobenzene, dichlorobenzene and the like. Examples of the amide-based solvent
include formamide, N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone and the like. These solvents may be used alone or as a mixed
10 solvent, as desired.
In the present invention, the solvent is used in an amount of 1 to 1,000 parts by
weight based on 100 parts by weight of the resin composition. If the amount of the
solvent is less than 1 part by weight, there is no significance of using the solvent. In
addition, the upper limii of ihe amouni used of ihe solveni is, ihough not particularly
15 limited, approximately 1,000 parts by weight from the viewpoints of handleability and
reaction efficiency.
In the case of employing a method in which a solid of the polylactic acid resin
(Component A) and/or the thermoplastic resin (Component B) other than a polylactic
acid is brought into contact with a liquid in which the cyclic carbodiimide compound
20 (Component C) is dissolved, dispersed or melted thereby impregnating the latter, a
method of bringing the solid of the polylactic acid resin (Component A) and/or
thermoplastic resin (Component B) other than a polylactic acid into contact with the
cyclic carbodiimide compound (Component C) dissolved in a solvent as described
above, a method of bringing a solid polylactic acid resin (Component A) and/or
38
thermoplastic resin (Component B) other than a polylactic acid into contact with an
emulsion liquid containing the cyclic carbodiimide compound (Component C) or the
like are used. As the contacting method, there may be suitably employed a method of
immersing the polylactic acid resin (Component A) and/or the thermoplastic resin
5 (Component B) other than a polylactic acid, a method of applying or spraying to the
polylactic acid resin (Component A) and/or the thermoplastic resin (Component B)
other than a polylactic acid or the like.
A compatibilization reaction by the cyclic carbodiimide compound
(Component C) can be carried out at room temperature (25OC) to 30OoC. However, the
10 reaction is further accelerated at preferably 50 to 280°C, more preferably 100 to 280°C
from the viewpoint of reaction efficiency. Although the reaction readily proceeds at a
temperature at which the polylactic acid resin (Component A) andlor the thermoplastic
resin (Component B) other than a polylactic acid are melted, the reaction is preferably
carried out at a temperature lower than 300°C in order to suppress the evaporation and
15 decomposition of the cyclic carbodiimide compound (Component C). The use of the
solvent is effective for reducing the melting point and increasing the stirring efficiency
of the polylactic acid resin (Component A) and/or the thermoplastic resin (Component
B) other than a polylactic acid.
The resin composition of the present invention is such that in the resin
20 composition, the polylactic acid resin (Component A) and the thermoplastic resin
(Component B) other than a polylactic acid form a continuous phase and dispersoids
dispersed and present in the continuous phase, the dispersoids have an average diameter
of 2 pm or less at an arbitrary cross-section of the composition, the difference in the
number of the dispersoids is less than 10% at optional 5 places having 15 pm length and
39
15 pm width in the continuous phase in the cross-section, and the polylactic acid resin
(Component A) has a carboxylic group concentration of lOxa equivalentslton or less
(wherein, a is parts by weight of Component A/(Parts by weight of Component A +
Parts by weight of Component B + Parts by weight of Component C)) .
5 Which of the polylactic acid resin (Component A) and the thermoplastic resin
(Component B) other than a polylactic acid forms a continuous phase depends on their
ratio or the types of the thermoplastic resin (Component B) other than the polylactic
acid. For example, the above form, in which the polylactic acid resin (Component A)
forms a continuous phase and one selected fsom the group consisting of a polyester, a
10 polyamide and an aromatic polycasbonate forms the dispersoids, can be realized by
setting the polylactic acid resin (Component A) at 50 to 99 parts by weight, the
thermoplastic resin (Component B) other than a polylactic acid selected from the group
consisting of a polyester, a polyamide and an aromatic polycarbonate at 1 to 49.99 pasts,
~~~~~ an& the-carbodiiiriidecoiripound (Coiriporient C) iii such a way that a carbodiirnide~
15 group of the cyclic carbodiimide compound (Component C) is set at 0.5 to 2 equivalents
to 1 equivalent of a group andlor a bond capable of reacting with carbodiimide in the
resin composition.
Here, the average diameter of dispersoids is a value obtained in the following
manner: by selecting 10 dispersoids starting from the one having the largest diameter in
20 the order of decreasing diameters in an electron microscopic photographs taken by
scanning electron microscopy observation using the method described in Examples,
from which the average value of the diameter is calculated. If the shape of the
dispersoids is substantially circular, a half of the sum of the long diameter and the short
diameter is defined as a diameter of the dispersoids, and if the shape of the dispersoids
40
is polygonal, a diameter of the circumscribed circle is defined as a diameter of each of
the dispersoids, and then the average value was calculated.
In the resin composition of the present invention, the average diameter of the
dispersoids is 2 pm or less and preferably 1.5 pm or less from the viewpoint of
5 compatibility.
In addition, the difference in the number of the dispersoids is defined as a
numerical value given by the following expression (c), wherein the average value and
the standard deviation are calculated in the following manner: a frame having a length
of 15 pm and a width of 15 pm is selected at 5 arbitrary places in an electron
10 microscopic photograph taken by scanning electron microscopy observation, the
number of dispersoids in each frame is counted, from which the average value and the
standard deviation of the number of the dispersoids are calculated for the 5 places.
In addition, if a dispersoid is present on the line defining the frame, this
dispersoid was counie
15 Difference in the number of the dispersoids = [Standard deviation1Average
value] x 100 (c)
In the resin composition of the present invention, the difference in the number
of the dispersoids is less than 10% and preferably less than 5% from the viewpoint of
compatibility.
20 In the resin composition of the present invention, the polylactic acid resin
(Component A) has a carboxyl group concentration of lOxa equivalentslton or less in
the resin composition and preferably 5xa equivalentslton or less, from the viewpoint of
moist heat stability (wherein, a represents parts by weight of A/(parts by weight of
Component A + parts by weight of Component B +parts by weight of Component C)).
4 1
If the carboxyl group concentration of the resin composition of the present
invention is in the above range, the resin composition has a further improved
compatibility. Therefore, it is a matter of course that impact absorbing properties are
improved when the resin composition is formed into a resin molding, yarn breakage
5 does not occur in the fiber formation (melt spinning) and yarn unevenness can be further
reduced even if the fiber diameter is reduced, and also film breakage or the like does not
occur in the film forming process and the film thickness unevenness can be further
reduced even if the thickness is reduced, thus the resin composition can be suitably used
in a fiber, a film and the like as its application.
10 The resin composition of the present invention can be used by using all
well-known additives and fillers within the limit which does not deteriorate the effect of
invention, including, for example, a stabilizer, a crystallization accelerator, a filler, a
release agent, an antistatic agent, a plasticizer, an impact resistance improver, a terminal
~ blockiiig ageiii aiidiiie lik
15
The resin composition of the present invention may contain a stabilizer. As
the stabilizer, a stabilizer used for a general thermoplastic resin can be used. Examples
of the stabilizer include an antioxidant and a light stabilizer. A molding product
having excellent mechanical characteristics, moldability, heat resistance and durability
20 can be obtained by blending these agents.
Examples of the antioxidant include a hindered phenol-based compound, a
hindered amine-based compound, a phosphite-based compound and a thioether-based
compound.
Examples of the hindered phenol-based compound include
42
2,2'-methylene-bis(4-methyl-t-butylphenol),
triethylene g l y c o l - b i s ( [ 3 - ( 3 - t - b u t y l - 5 - m e t h y l - 4 - h y d ~ e ] ,
tetrakis[methylene-3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate]methane,
3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-l,l-dimethylethyl]-
10 2,4,8,1O-tetraoxaspiro[5.5]undecane, and the like.
Examples of the hindered amine-based compound include
N,N'-bis-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine,
N,N'-tetramethylene-bis[3-(3'-methyl-5'-t-butyl-4'-hydroxyphenyl)propionyl]diamine,
~ ~;~~~bis[~;(3;~;di-~bu~Y~i~-hy~pr~oopXioYnPyh~]ehnyyd)ra zine,~ ~~~~ ~ ~ ~ ~ ~~~~~ ~-~ ~
15 N-salicyloyl-N'-salicylidenehydrazine, 3-(N-salicyloy1)amino-1,2,4-triazole,
N,N'-bis[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}ethyl]oxyamide and the
like. Preferably,
triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate],
tetrakis[methylene-3-(3',5'-di-t-butyl-4-hydroxyphenyl)propionate]methane and the like
20 are cited.
The phosphite-based compound is preferably a compound having at least one
P-0 bond attached to an aromatic group and specifically is exemplified by
tris(2,6-di-t-butylphenyl)phosphite,
tetrakis(2,6-di-t-butylphenyl)-4,4'-biphenylenephosphite,
43
5 tris(mixed mono- and di-uonylphenyl)phosphite, tris(nonylphenyl)phosphite,
4,4'-isopropylidenebis(pheny1-dialkylphosphite),
2,4,8,1O-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo
[d,f][l,3,2]dioxaphophepin (Sumilizer (trade mark) GP), and the like.
Among these, there may be preferably used tris(2,6-di-t-butylphenyl)phosphite,
10 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite,
bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite,
tetrakis(2,6-di-t-butylphenyl)-4,4'-biphenylenephosphite,
2,4,8,1O-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo
-[d,~[l,3;2]dioxaphophepinand ihe li
15 Specific examples of the thioether-based compound include
dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate,
distearyl thiodipropionate, pentaerythritol-tetrakis(3-laurylthiopsaphate),
pentaerythritol-tetrakis(3-dodecylthiopropionate),
pentaerythritol-tetrakis(3-octadecylthiopropionate),
20 pentaerphritol-tetrakis(3-myristylthiopropionate),
pentaerythitol-tetrakis(3-stearylthiopropionate) and the like.
Specific examples of the light stabilizer include a benzophenone-based
compound, a benzotriazole-based compound, an aromatic benzoate-based compound, an
oxalic acid anilide-based compound, a cyanoacrylate-based compound, a hindered
44
amine-based compound and the like.
Examples of the benzophenone-based compound include benzophenone,
2-hydroxy-4-(2-hydroxy-3-methyl-acryloxyisopropoxy)benzophenonaen,d the like.
Examples of the benzotriazole-based compound include
2-(3,5-di-t-amyl-2-hydroxyphenyl)-5-chlorobenzotriazole,
2-(5-t-butyl-2-l~ydroxyphenyl)benzotriazole,
2-[2'-hydroxy-3',5'-bis(a,a-dimetl~ylbenzyl)phenyl]benzotriazole,
20 2-[2'-hydroxy-3',5'-bis(a,a-dimethylbenzyl)phenyl]-2H-be~azole,
2-(4'-octoxy-2'-hydroxyphenyl)benzotriazole, and the like.
Examples of the aromatic benzoate-based compound include alkylphenyl
salicylates such as p-t-butylphenyl salicylate, p-octylphenyl salicylate and the like.
Examples of the oxalic anilide-based compound include
45
2-ethoxy-2'-ethyloxalic acid bisanilide, 2-ethoxy-5-t-butyl-2'-ethyloxalic acid bisanilide,
2-ethoxy-3'-dodecyloxalic acid bisanilide, and the like.
Examples of the cyanoacrylate-based compound include
ethyl-2-cyano-3,3'-diphenyla crylate, 2-ethylhexyl-cyano-3,3'-diphenyla clylate, and the
5 like.
Examples of the hindered amine-based compound include
bis(2,2,6,6-tetramethyl-4-piperidyl)oxalate,
bis(2,2,6,6-tetramethyl-4-piperidyl)malonate,
20 bis(2,2,6,6-tetramethyl-4-piperidy1)sebacate bis(2,2,6,6-tetramethyl-4-piperidyl)adipate,
bis(2,2,6,6-tetramethyl-4-piperidyl)teqhthalate,
1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxye) thane,
a,a'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene,
bis(2,2,6,6-tetramethyl-4-piperidyl) tolylene-2,4-dicarbamate,
46
bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-l,6-dicarbamate,
tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate,
tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-l,3,4-tricarboxylate,
1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}-2,2,6,6-tetramethylpiperidinae ,
5 condensate of 1,2,3,4-butane tetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol
and ~,~,~',~'-tetramethy1-3,9-[2,4,8,1O-tetraoxaspiro[5.5]undecane]dimethaannold, t he
like. In the present invention, the stabilizer components may be used alone or in
combination of two or tnore. As the stabilizer components, prefel~eda re the hindered
phenol-based compound andlor the benzotriazole-based compound.
10 The amount of the stabilizer is preferably 0.01 to 3 parts by weight, more
preferably 0.03 to 2 parts by weight based on 100 parts by weight of the resin
composition.

~~ ----- ~~ ~~p~~~~ ~ Tlie-resiii~~~iiiij~o~fi trhie~- piif eseiii-iiiveiitioii- iiiaj. coiitaiii aii organic of
15 inorganic crystallization accelerator. By including a crystallization accelerator in the
resin composition, a molding product having excellent mechanical characteristics, heat
resistance and moldability can be obtained.
That is, there may be obtained a molding product, which is improved in
moldability and crystallinity by application of the crystallization accelerator, is fully
20 crystallized even in ordinary injection molding and has excellent heat resistance and
moist heat stability. In addition, the time for producing the molding product can be
significantly shortened and the economical effect is large.
As the clystallization accelerator used in the present invention, there may be
used a crystallization nucleating agent which is generally used for a crystalline resin.
47
Both an inorganic crystallization nucleating agent and an organic crystallization
nucleating agent may be used.
Examples of the inorganic crystallization nucleating agent include talc, kaolin,
silica, synthetic mica, clay, zeolite, graphite, carbon black, zinc oxide, magnesium oxide,
5 titanium oxide, calcium carbonate, calcium sulfate, barium sulfate, calcium sulfide,
boron nitride, montmorillonite, neodymium oxide, aluminum oxide, metal salt of
phenylphosphonate, and the like. These inorganic crystallization nucleating agents are
preferably treated with various dispersion aids and are in a highly dispersed state such
that the primary particle diameter is approximately 0.01 to 0.5 pm in order to improve
10 the dispersibility in the resin composition and effects thereof.
Examples of the organic crystallization nucleating agent include: an organic
carboxylic acid metal salt such as calcium benzoate, sodium benzoate, lithium benzoate,
potassium benzoate, magnesium benzoate, barium benzoate, calcium oxalate, disodium
terephthalate, diiithium terephthalate, dipotassium terephthalate, sodium lauraie,
15 potassium laurate, sodium myristate, potassium myristate, calcium myristate, barium
myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium
stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium
montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate,
zinc salicylate, aluminum dibenzoate, sodium P-naphthoate, potassium P-naphthoate,
20 sodium cyclohexanecarboxylate and the like; and an organic sulfonic acid metal salt
such as sodium p-toluenesulfonate, sodium sulfoisophthalate, and the like.
In addition, examples of the organic crystallization nucleating agent include: an
organic carboxylic acid amide such as stearic acid amide, ethylenebis lauric acid amide,
palmitic acid amide, hydroxystearic acid amide, erucic acid amide,
48
tris(t-buty1amide)trimesate and the like; and low-density polyethylene, high-density
polyethylene, polyisopropylene, polybutene, poly(4-methylpentene),
poly(3-methylbutene-I), polyvinyl cycloalkane, polyvinyl trialkylsilane, branched-type
polylactic acid, sodium salt of an ethylene-acrylate copolymer, a sodium salt of a
5 styrene-maleic anhydride copolymer (so-called "ionomer"), benzylidene sorbitol and a
derivative thereof, for example, dibenzylidene sorbitol and the like.
Among these, talc and at least one selected from the organic carboxylic acid
metal salts are preferably used. These crystallization accelerators used in the present
invention may be used alone or in combination of two or more.
10 The amount of the crystallization accelerator is preferably 0.01 to 30 parts by
weight, and more preferably 0.05 to 20 parts by weight based on 100 parts by weight of
the resin composition.

-- T h e resin-composition of the preseni invention may coniain an organic or
15 inorganic filler. By including a filler component in the resin composition contains, a
molding product having excellent mechanical characteristics, heat resistance and
moldability can be obtained.
Examples of the organic filler include: a chip-like filler such as rice husk,
wooden chips, bean curd refuse, crushed waste paper material, clothing crushed material
20 and the like; a fibrous filler such as plant fiber including cotton fiber, hemp fiber,
bamboo fiber, wooden fiber, kenaf fiber, jute fiber, banana fiber, coconut fiber and the
like or pulp and cellulose fiber obtained from these plant fibers, an animal fiber
including silk, wool, Angora, cashmere, camel fiber and the like; synthetic fibers such
as polyester fiber, nylon fiber, acrylic fiber and the like; and a powdely filler such as
49
paper powder, wooden powder, cellulose powder, rice husk powder, fruit shell powder,
chitin powder, chitosan powder, protein powder, starch powder and the like. From the
viewpoint of moldability, preferred are paper powder, wooden powder, bamboo powder,
cellulose powder, kenaf powder, rice husk powder, fmit shell powder, chitin powder,
5 chitosan powder, protein powder and starch powder, preferred are paper powder,
wooden powder, bamboo powder, cellulose powder and kenaf powdel; more preferred
are paper powder and wooden powder, and especially preferred is paper powder.
These organic fillers directly obtained from natural products may be used but
organic fillers recycled from waste materials such as used paper, waste timber and used
10 clothing may also be used.
In addition, prefemed examples of wooden materials include: conifers such as
yellow pine, cedar, cypress, fir and the like; and broadleaf trees such as beech,
chinquapin, eucalyptus and the like.
~~~-~ Fromthe-viewpoint of rnoldabiliiy; paperpowder--preferably -contains
15 especially an adhesive which contains an emulsion-based adhesive which is usually
used in processing paper such as a vinyl acetate resin-based emulsion or an acrylic
resin-based emulsion and a hot melt adhesive such as a vinyl alcohol-based adhesive, a
polyamide-based adhesive and the like.
The blending amount of the organic filler is not pa~ticularly limited in the
20 present invention, but is preferably 1 to 300 pasts by weight, more preferably 5 to 200
parts by weight, further more preferably 10 to 150 parts by weight and particularly
preferably 15 to 100 pasts by weight, based on 100 pasts by weight of the resin
composition from the viewpoint of moldability and heat resistance. If the blending
amount of the organic filler is less than 1 past by weight, the effect of improving the
50
moldability of the composition is small, and if the blending amount exceeds 300 parts
by weight, the filler is difficult to be uniformly dispersed, and may unfavorably
deteriorate the strength as a material and appearance in addition to moldability and heat
resistance.
5 The composition of the present invention preferably contains an inorganic filler.
When composition contains an inorganic filler, a composition having excellent
mechanical characteristics, heat resistance and moldability may be obtained. As the
inorganic filler used in the present invention, there may be used a fibrous, plate-like or
powdery inorganic filler which is used to reinforce a general thermoplastic resin.
10 Specific examples of the inorganic filler include: a fibrous inorganic filler such
as carbon nanotube, glass fibel; asbestos fiber, carbon fiber, graphite fiber, metal fiber,
potassium titanate whisker, aluminum borate whisker, magnesium-based whisker,
silicon-based whisker, wollastonite, imogolite, sepiolite, asbestos, slug fiber, zonolite,
- gypsum fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon
15 nitride fiber, boron fiber and the like; and a plate-like or particulate inorganic filler
including layered silicates, lamellar silicates exchanged with an organic onium ion,
glass flakes, non-swelling mica, graphite, metal foils, ceramic beads, talc, clay, mica,
sericite, zeolite, bentonite, dolomite, kaolin, powdery silicic acid, feldspar powder,
potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium
20 sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide,
gypsum, novaculite, dosonite, white clay, carbon nanoparticles such as fullerene, and
the like.
Specific examples of the layered silicates include: smectite-based clay minerals
such as montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite and the
51
like; clay minerals such as vermiculite, halocite, kanemite, kenyaite and the like; and
swelling micas such as Li-type fluorine taeniolite, Na-type fluorine taeniolite, Li-type
tetrasilicic fluorine mica, Na-type tetrasilicic fluorine mica and the like. They may be
natural or synthetic. Among these, preferred are smectite-based clay minerals such as
5 montmorillonite, hectorite and the like and swelling synthetic micas such as Li-type
fluorine taeniolite and Na-type tetrasilicic fluorine mica.
Among these, preferred is a fibrous or plate-like inorganic filler and
particularly preferred are glass fiber, wollastonite, aluminum borate whisker, potassium
titanate whisker, mica, kaolin and cation exchanged layered silicate. The fibrous filler
10 has an aspect ratio of preferably 5 or more, more preferably 10 or more, and hrther
more preferably 20 or more.
Such fillers may be covered or bundled with a thermoplastic resin such as an
ethylene-vinyl acetate copolymer and the like or a thermosetting resin such as epoxy
resin snd the like, or is trested 7ii:h a coupling agent such as an ~ ~ n o s i l a nzefi,
15 epoxysilane and the like.
The amount of the inorganic filler is preferably 0.1 to 200 parts by weight,
more preferably 0.5 to 100 parts, further preferably 1 to 50 parts, preferably in particular
1 to 30 parts, and the most preferably 1 to 20 parts by weight based on 100 parts by
weight of the resin composition.
20
The resin composition of the present invention may contain a release agent.
As the release agent used in the present invention, a release agent used for a general
thermoplastic resin may be used.
Specific examples of the release agent include fatty acids, fatty acid metal salts,
52
oxy fatty acids, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene
bis fatty acid amides, aliphatic ketones, fatty acid partially saponified esters, fatty acid
lower alcohol esters, fatty acid polyhydric alcohol esters, fatty acid polyglycol esters,
modified silicones and the like. A shaped polylactic acid product having excellent
5 mechanical characteristics, moldability and heat resistance can be obtained by blending
these agents.
The fatty acids preferably have 6 to 40 carbon atoms, and specific examples of
the fatty acid include oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic
acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid,
10 montanic acid and a mixture thereof. The fatty acid metal salt is preferably an alkali
metal salt or an alkali earth metal salt of a fatty acid having 6 to 40 carbon atoms, and is
exemplified by calcium stearate, sodium montanate, calcium montanate and the like.
Examples of the oxyfatty acid include 1,2-oxystearic acid, and the like. The
paraffin is preferabiy a parafin having 18 or more carbon atoms and is exemplified by
15 liquid paraffin, natural paraffin, microcrystalline wax, petrolactam and the like.
The low molecular weight polyolefins preferably have a molecular weight of
5,000 or less and are exemplified by polyethylene wax, maleic acid modified
polyethylene wax, oxide type polyethylene wax, chlorinated polyethylene wax,
polypropylene wax and the like. The fatty acid amides preferably have 6 or more
20 carbon atoms and are exemplified by an oleic acid amide, an esucic acid amide, a
behenic acid amide and the like.
The alkylenebis fatty acid amides preferably have 6 or more carbon atoms and
are exemplified by methylenebis stearic acid amide, ethylenebis stearic acid amide,
N,N-bis(2-hydroxyethyl)stearic acid amide and the like. The aliphatic ketones
53
preferably have 6 or more carbon atoms and are exemplified by higher aliphatic
ketones.
Examples of the fatty acid partially saponified ester include montanic acid
partially saponified esters and the like. Examples of the fatty acid lower alcohol ester
5 include stearic acid esters, oleic acid esters, linoleic acid esters, linolenic acid esters,
adipic acid esters, behenic acid esters, arachidonic acid esters, montanic acid esters,
isostearic acid esters and the like.
Examples of the fatty acid polyhydric alcohol ester include glycerol tristearate,
glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythsitol
10 tristearate, pentaerythsitol distearate, pentaerythsitol monostearate, pentaerythritol
adipate stearate, sorbitan monobehenate and the like. Examples of the fatty acid
polyglycol ester include polyethylene glycol fatty acid esters, polypropylene glycol fatty
acid esters and the like.
he modified silicone include polyether-modified silicone, higher
15 fatty acid alkoxy modified silicone, higher fatty acid-containing silicone, higher fatty
acid ester modified silicone, methacryl modified silicone, fluorine modified silicone and
the like.
Among these, preferred are fatty acids, fatty acid metal salts, oxyfatty acids,
fatty acid esters, fatty acid partially saponified esters, paraffins, low-molecular weight
20 polyolefins, fatty acid amides and alkylenebis fatty acid amides, and more preferred are
fatty acid partially saponified esters and alkylenebis fatty acid amides. Among others,
preferred are montanic acid esters, montanic acid partially saponified esters,
polyethylene wax, oxidized polyethylene wax, sorbitan fatty acid esters, erucic acid
amide and ethylenebis stearic acid amide, and particularly preferred are montanic acid
54
partially saponified esters and ethylenebis stearic acid amide.
These release agents may be used alone or in combination of two or more.
The amount of the release agent is preferably 0.01 to 3 parts by weight, and more
preferably 0.03 to 2 parts by weight based on 100 parts by weight of the resin
5 composition.

The resin composition of the present invention may contain an antistatic agent.
Examples of the antistatic agent include quaternary ammonium salt-based compounds,
sulfonate-based compounds and alkyl phosphate-based con~poundsu ch as
10 (p-lauramidepropionyI)trimethylammonium sulfate, sodium dodecylbenzenesulfonate,
and the like.
These antistatic agents used in the present invention may be used alone or in
combination of two or more. The amount of the antistatic agent is preferably 0.05 to 5
- pasts by weighi and more preferably 0.1 to 5 paris by weighi based-on 100 parts by
15 weight of the resin composition.

The resin composition of the present invention may contain a plasticizer.
Generally known plasticizers may be used as the plasticizer. Examples of the
plasticizer include a polyester-based plasticizer, a glycerin-based plasticizer, a
20 polyvalent carboxylic acid ester-based plasticizer, a phosphate-based plasticizer, a
polyalkylene glycol-based plasticizer, an epoxy-based plasticizer, and the like.
Examples of the polyester-based plasticizer include: a polyester comprising an
acid component such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid,
naphthalenedicarboxylic acid, diphenyldicarboxylic acid and the like and a diol
55
component such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol, diethylene glycol and the like; and a polyester
comprising a hydroxycarboxylic acid such as polycaprolactone and the like. These
polyesters may be terminally blocked with a monofunctional carboxylic acid or a
5 monofunctional alcohol.
Examples of the glycerin-based plasticizer include glycerin monostearate,
glycerin distearate, glycerin monoacetomonolaurate, glycerin monoacetomonostearate,
glycerin diacetomonooleate, glycerin monoacetomonomontanate, and the like.
Examples of the polyvalent carboxylic acid ester-based plasticizer include: a
10 phthalic acid ester such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate,
diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate and the like; a trimellitic
acid ester such as tributyl trimellitate, trioctyl trimellitate, trihexyl trimellitate and the
like; an adipic acid ester such as isodecyl adipate, n-decyl-n-octyl adipate and the like; a
citric acid cztcr zuch az tributyl acctylcitratc and-thc likc; an azclaic acid cztcr zuch az
15 bis(2-ethylhexy1)azelate and the like; and a sebacic acid ester such as dibutyl sebacate,
bis(2-ethylhexy1)sebacate and the like.
Examples of the phosphate-based plasticizer include tributyl phosphate,
tris(2-ethylhexyl)phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate
and diphenyl-2-ethylhexyl phosphate.
20 Examples of the polyalkylene glycol-based plasticizer include a polyalkylene
glycol such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol,
poly(ethylene oxide-propylene oxide) block and/or random copolymers, an ethylene
oxide addition polymer of bisphenols, a tetrahydrofuran addition polymer of bisphenols
and the like; or a terminal blocking agent compound such as a terminal epoxy modified
56
compound, a terminal ester modified compound, a terminal ether modified compound
and the like.
Examples of the epoxy-based plasticizer include: epoxy triglyceride
comprising an alkyl epoxystearate and soybean oil; and an epoxy resin produced by
5 using bisphenol A and epichlorohydrin as raw materials.
Specific examples of other plasticizers include: a benzoic acid ester of an
aliphatic polyol such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate,
triethylene glycol-bis(2-ethylbutyrate) and the like; a fatty acid amide such as stearic
acid amide and the like; a fatty acid ester such as butyl oleate and the like; an oxyacid
10 ester such as methyl acetylricinoleate, butyl acetylricinoleate and the like;
pentaerythritols; a fatty acid ester of pentaerythritols; various sorbitols; a polyacrylic
acid ester; a silicone oil; paraffins; and the like.
As the plasticizer, especially preferably used are at least one selected from a
-- polyester-based plasticizer, a polyalkylene-based plasiicizer, a glycerin-based plasiicizer,
15 pentaerythritols and a fatty acid ester of pentaerythritols, which may be used alone or in
combination of two or more.
The amount of the plasticizer is preferably 0.01 to 30 parts by weight, more
preferably 0.05 to 20 parts by weight, and further preferably 0.1 to 10 parts by weight
based on 100 parts by weight of the resin composition. In the present invention, a
20 crystallization nucleating agent and a plasticizer may be used individually alone and are
more preferably used in combination.

The resin composition of the present invention may contain an impact
resistance improver. The impact resistance improver can be used to improve the
57
impact resistance of a thermoplastic resin and is not pa~ticularlyli mited. For example,
at least one selected from the following impact resistance improvers may be used.
Specific examples of the impact resistance improver include an
ethylene-propylene copolymer, an ethylene-propylene-nonconjugated diene copolymer,
5 an ethylene-butene-1 copolymer, various acrylic rubbers, an ethylene-acrylic acid
copolymer and an alkali metal salt thereof (so-called an ionomers), an
ethylene-glycidyl(metli)acrylate copolymer, an ethylene-acrylic acid ester copolymer
(for example, an ethylene-ethyl acrylate copolymer and an ethylene-butyl acrylate
copolymer), a modified ethylene-propylene copolymer, a diene lubber (for example, a
10 polybutadiene, a polyisoprene and a polychloroprene), a diene-vinyl copolymer (such as
a styrene-butadiene random copolymer, a styrene-butadiene block copolymer,
styrene-butadiene-styrene block copolymer, a styrene-isoprene random copolymer, a
styrene-isoprene block copolymer, a styrene-isoprene-styrene block copolymer, a
polybuiadietle-siyreiie graft copoiyn~era nd a buiadiene-acryioniiriie copolymer), a
15 polyisobutylene, a copolymer of isobutylene and butadiene or isoprene, a natural rubber,
a thiokol rubber, a polysulfide rubber, a polyurethane rubber, a polyether rubber, an
epichlorohydrin rubber and the like.
Further, there may be also used an impact resistance improver having different
degrees of crosslinking, an impact resistance improver having various micro-structures,
20 for example, a cis structure and a trans structure, a so-called core-shell type multilayer
structure polymer which is composed of a core layer and one or more shell layers
covering the core layer and in which adjacent layers are composed of different polyn~ers,
or the like.
Furthermore, the various (co)polymers described in the above specific
58
examples may be any of a random copolymer, a block copolymer, a block copolymer or
the like, and may be used as an impact resistance improver of the present invention.
The amount of the impact resistance improver is preferably 1 to 30 parts by
weight, more preferably 5 to 20 parts by weight, and further preferably 10 to 20 parts by
5 weight based on 100 parts by weight of the resin composition.

The resin composition of the present invention may contain a terminal blocking
agent. The terminal blocking agent reacts with a past or whole of a carboxyl group
terminal to block the carboxyl group terminal, and examples of the terminal blocking
10 agent include addition reaction type compounds such as a carbodiimide compound, an
epoxy compound, an oxazoline compound, an oxazine compound and the like. As the
carbodiimide compound, a cyclic carbodiimide compound described in Pamphlet of
International Publication No. WO 2010/071213 may be suitably used.
- -The amount of the tesminal blocking ageni is preferably 0.01 to 10 paris by
15 weight, more preferably 0.1 to 5 parts by weight, and further preferably 0.2 to 2 parts by
weight based on 100 parts by weight of the resin composition.

Further, the resin composition of the present invention may contain a
thermosetting resin such as a phenol resin, a melamine resin, a thermocurable polyester
20 resin, a silicone resin, an epoxy resin and the like within a range without departing from
the object of the present invention. In addition, the resin composition of the present
invention may contain a flame retardant such as a bromine-based, a phosphorus-based, a
silicone-based, antimony compound-based flame retardant and the like in a range
without departing from the object of the present invention. Further, the resin
59
composition may contain a colorant including an organic or inorganic dye or a pigment,
for example, an oxide such as titanium dioxide, a hydroxide such as alumina white, a
sulfide such as zinc sulfide, a fessocyanide compound such as iron blue, a chromate
such as zinc chromate, a sulfate such as barium sulfate, a carbonate such as calcium
5 carbonate, a silicate such as ultramarine blue, a phosphate such as manganese violet,
carbon such as carbon black, and a metal colorant such as a bronze powder, an
aluminum powder and the like. In addition, the resin composition may contain
additives including: a nitroso-based colownt such as Naphthol Green B and the like, a
nitro-based colorant such as Naphthol Yellow S and the like, an azo-based colorant such
10 as Naphthol Red, Chromophthal Yellow and the like, a phthalocyanine-based colorant
such as Phthalocyanine Blue, Fast Sky Blue and the like, a condensation polycyclic
colorant such as Indanthrene Blue and the like; and a slidability improver such as
graphite, a fluororesin and the like. These additives may be used alone or in
c o m b i n a t i o n o f t-i~o~or-more
15
[Examples]
Hereinafter, the present invention will be described in more detail by examples,
but the present invention is not limited by these examples. In addition, each of the
values in the present examples was determined according to the following methods.
20 (1) Weight Average Molecular Weight (Mw) and Number Average Molecular Weight
(Mn) of Polymer:
The weight average molecular weight and number average molecular weight of
a polymer are measured in terms of standard polystyrene by gel permeation
chromatography (GPC).
GPC measurement was carried out by using the following detector and
columns, and injecting 10 p1 of a sample having a concentration of 1 mglml (chloroform
containing 1% of hexafluoroisopropano1) at a temperature of 40°C and a flow rate of 1.0
mllmin using chloroform as an eluent.
5 Detector: RID-6A differential refractometer of Shimadzu Corporation
Column: TSKgelG3000HXL, TSKgelG4000HXL, TSKgelG5000HXL and
TSKguardcolumnHXL-L of Tosoh Corporation connected in series, or
TSKgelG2000HXL, TSKgelG3000HXL and TSKguardcolumnHXL-L connected in
series.
10 (2) Carboxyl Group Concentration:
A sample was dissolved in purified o-cresol in a nitrogen gas stream and
titrated with an ethanol solution of 0.05 N potassium hydroxide using Bromocresol Blue
as an indicator.
~~ ~~~~ ---in~ aclditio~thcaer boxylgroup-concentration derived~fsomthe-polylacticacid
15 resin (Component A) was confirmed by the above method or 'H-NMR. ECA600
manufactured by JEOL was used for NMR measurement. The measurement was
carried out by adding hexylamine and using heavy chloroform and
hexafluoroisopropanol as solvents.
(3) DSC Measurement of Stereocomplex Crystallization Degree [S (%)I, Crystal
20 Melting Temperature and others:
A sample was heated to 250°C at a temperature elevation rate of 10°C/min
using DSC (TA-2920, manufactured by TA Instrument Co., Ltd.) in a nitrogen gas
stream in the first cycle and the glass transition temperature (Tg), the melting
temperature (Tm*) of stereocomplex phase polylactic acid crystals, melting enthalpy
6 1
(AHms) of stereocomplex phase polylactic acid crystals and melting enthalpy (AHmh)
of homo-phase polylactic acid crystals were measured.
The crystallization onset temperature (Tc*) and clystallization temperature (Tc)
were measured by quickly cooling the sample and then carrying out the second cycle
5 measurement under the same conditions. The stereo-formation degree is a value
calculated from the values of melting enthalpy of stereocomplex phase and homo-phase
polylactic acid crystals obtained by the above measurement using the following
expression (a).
S = [AHms/(AHrnh + AHms)] x 100 (a)
10 (Note that AHms represents the melting enthalpy of the stereocomplex polylactic acid
phase crystals and AHmh represents the melting enthalpy of the polylactic acid
homo-phase crystals)
(4) Identification of Cyclic Carbodiimide (Component C) Structure by NMR
~ ~ m~ea-sur-em~ent~s:
15 The synthesized cyclic carbodiimide compound was confirmed by 'H-NMR
and ' 3 ~ - T~he ~JNR~-EX.27 0 of JEOL Ltd. was used for the NMR measurement.
Heavy chloroform was used as the solvent.
(5) Identification of Carbodiimide Skeleton of Cyclic Carbodiimide (Component C) by
IR:
20 The existence of the carbodiimide skeleton of the synthesized cyclic
carbodiimide compound was confirmed by FTIR in a range of 2,100 to 2,200 cm-'
characteristic to a carbodiimide. The Magna-750 manufactured by Thermo Nicolet
Corporation was used for the FTIR analysis.
(6) Average Diameter of Dispersoids:
62
The average diameter of dispersoids in a resin composition was determined in
the following way. Ultrathin sections having a thickness of 80 nm were prepared from
each sample at normal temperature (25°C) using a microtome. Electron microscopic
photographs of these sections were obtained using a scanning electron microscope
5 (Quanta 250FEG, manufactured by FEI Co.). Then, an average diameter of
dispersoids was dete~mined. Ten dispersoids were selected from the photographs in
the order of descending diameters starting from the dispersoid having the largest
diameter, from which the average value was calculated and determined to be the
average value. If the shape of the dispersoid is substantially circular, a half of the sum
10 of the long diameter and the short diameter is defined as the diameter of the dispersoid,
and if the shape of the dispersoid is polygonal, a diameter of the circumscribed circle is
defined as the diameter of the dispersoid, and then the average value of dispersoids was
calculated.
~ (
15 An ultrathin section having a thickness of 80 nm was prepared from each
sample at normal temperature (25OC) using a microtome in order to determine a
difference in the number of the dispersoids in the resin composition. Electron
microscopic photographs of the thin section were obtained using a scanning electron
microscope (Quanta 250FEG, manufactured by FEI Co.).
20 Then, a frame having 15 pm length and 15 pm width was selected arbitrarily at
5 places on the pliotograph and dispersoids is counted in each frame, and the average
value and the standard deviation were calculated based on the numbers of the
dispersoids at the 5 places. The difference in the number of dispersoids is determined
as a numerical value given by the following expression (c).
63
In addition, if a dispersoid is present on the frame line, the dispersoid was
counted.
Difference in the number of the dispersoids = [Standard deviation/Average value] x 100
(c)
5 Hereinafter, the compounds used in the present examples will be described.

As the polylactic acid resin (Component A), the following polylactic acids
were produced and used.
[Production Example 11
10 Poly-L-lactic Acid Resin (Al):
In a reactor equipped with a stirring blade, 0.005 parts by weight of tin oxalate
was added to 100 parts by weight of L-lactide (with an optical purity of loo%, produced
by Musashino Kagaku Keukyusho Co., Ltd.) and the mixture was subjected to reaction
~~ ai-k800C-for-2 hours-under x~niirogenak~losphere. Pnosphoricacidwasaddedin an
15 amount 1.2 times the equivalent of tin octylate. Thereafter, the residual lactide was
removed at 13.3 Pa, and the resulting product was formed into chips to obtain a
poly-L-lactic acid resin (Al). The resulting poly-L-lactic acid resin had a weight
average molecular weight of 152,000, a melting enthalpy (AHmh) of 49 Jlg, a melting
point (Tmh) of 175"C, a glass transition point (Tg) of 55°C and a carboxyl group
20 concentration of 13 equivalents/ton.
[Production Example 21
Poly-D-lactic Acid Resin (A2):
A poly-D-lactic acid resin (A2) was obtained by carrying out the same
64
operations as in Production Example 1 except for using D-lactide (with an optical purity
of loo%, produced by Musashino Kagaku Kenkyusho Co., Ltd.) instead of the L-lactide
in Production Example 1. The resulting poly-D-lactic acid resin (A2) had a weight
average molecular weight of 151,000, a melting enthalpy (AHmh) of 48 Jlg, a melting
5 point (Tmh) of 175"C, a glass transition point (Tg) of 55°C and a carboxyl group
concentration of 14 equivalentslton.
[Production Example 31
Stereocomplex polylactic acid (A3):
A total 100 parts by weight of a polylactic acid resin composed of 50 parts by
10 weight of the poly-L-lactic acid resin (At) and 50 parts by weight of the poly-D-lactic
acid resin (A2) was mixed with 0.04 parts by weight of sodium
2,2'-methylenebis(4,6-di-t-butylpheny1)phophate ("Adekastab (registered tradename)"
NA-11: produced by ADEKA Corporation) using a blender. Thereafter, the resulting
~~~ m~~~ i~x- ture-wasdried~atiO~~°Ci for 5 hours and supplied into a vent-type~~dollb1e~-screw
15 extruder having a diameter of 30 mm4 (TEX30XSST, manufactured by The Japan Steel
Works, Ltd.) and then melt extruded into pellets at a cylinder temperature of 250°C, a
screw revolution of 250 rpm, a discharge rate of 9 kg/h and a vent vacuum of 3 kPa to
obtain a stereocomplex polylactic acid (A3). The resulting stereocomplex polylactic
acid (A3) had a weight average molecular weight of 130,000, a melting enthalpy
20 (AHms) of 56 Jlg, a melting point (Tm) of 220°C, a glass transition point (Tg) of 58"C,
a carboxyl group concentration of 16 equivalentslton and a stereocomplex
crystallization degree (S) of 100%.
-=Thermoplastic Resin (Component B) Other Than a Polylactic Acid>
As the thermoplastic resin (Component B) other than a polylactic acid, the
65
following thermoplastic resins were used.
B1: Polybutylene Terephthalate:
Polybutylene terephthalate produced by Aldrich Chemical Company, Inc. was
used. The polybutylene terephthalate had a melting point of 227"C, a viscosity
5 average molecular weight of 38,000, a reduced viscosity of 1.21 dllg and a carboxyl
group concentration of 4 1 equivalents/ton.
B2: Polyethylene Terephthalate:
Polybutylene terephthalate ("FK-OM") produced by Teijin Co., Ltd, was used.
The polybutylene terephthalate had a melting point of 260°C, a reduced viscosity of
10 0.64 dllg and a carboxyl group concentration of 25 equivalentslton.
B3: Polyester Elastomer:
A polyester elastomer ("Hytrel" (registered tradename)) produced by Du
Pont-Toray Co., Ltd. was used.
--~-~~~-~~-~ ~ ~4:~&0lllart"i~l j.c~bcjilate ~ i l aroiilatic-polj.ca&oiiatc rcsiii ("Paiilite~(registere6
15 tradename)"L-1225) produced by Teijin Chemicals Ltd. was used. The aromatic
polycarbonate resin had a viscosity average molecular weight of 22,500 and a refractive
index (nd) of 1.585.
B5: Nylon 6:
Nylon 6 ("A-1030SD) produced by Unitika Ltd. was used.
20
As the cyclic carbodiimide compound (Component C), the following compounds were
produced and used.
[Production Example 41
Cyclic Carbodiimide Compound (Cl):
0-nitrophenol (0.11 mol), pentaerythrityl tetrabromide (0.025 mol), potassium
carbonate (0.33 mol) and 200 ml of N,N-dimethylformamide were fed to a reaction
device equipped with a stirring apparatus and a heating apparatus under a nitrogen
5 atmosphere and the mixture was subjected to reaction at 130°C for 12 hours and then
DMF was removed under reduced pressure. The resulting solid was dissolved in 200
ml of dichloromeihane, and the resuliing solution was separated ihree times with 100 ml
of water. An organic layer was dehydrated with 5 g of sodium sulfate, followed by
removing dichloromethane under reduced pressure to obtain an intermediate product D
10 (nitro product).
Thereafter, the intermediate product D (0.1 mol), 5% palladium carbon (PdIC)
(2 g) and 400 ml of ethanolldichloromethane (70130) were fed to a reaction device
equipped with a stirring apparatus, hydrogen substitution was carried out five times, and
a reaction was carried out under the conditions of continuous hydrogen supply at 25OC.
15 When the reduction in the amount of hydrogen became negligible, the reaction was
completed. Pd/C was collected and the mixed solvent was removed to obtain an
intermediate product E (amine product).
67
Subsequently, triphenylphosphine dibromide (0.1 1 mol) and 150 ml of
1,2-dichloroethane were fed to a reaction device equipped with a stirring apparatus, a
heating apparatus and a dropping funnel under a nitrogen atmosphere, followed by
stirring. A solution obtained by dissolving the intermediate product E (0.025 mol) and
5 triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was gradually added dropwise
to the resulting mixture at 25OC. After the completion of the dropwise addition, a
reaction was carried out at 70°C for 5 hours. Thereafter, the reaction solution was
filtered, and the filtrate was separated 5 times with 100 ml of water. An organic layer
was dehydrated with 5 g of sodium sulfate, followed by removing 1,2-dichloroethane
10 under reduced pressure to obtain an intermediate product F (triphenylphosphine
product).
Next, di-te1.t-butyl dicarbonate (0.1 1 mol), N,N-dimethyl-4-aminopyridine
(0.055 mol) and 150 ml of dichloromethane were fed to a reaction device equipped with
-Kstirring apparatus and a dropping funnel under a nitrogen atmosphere, followed by
15 stirring. To the resulting mixture, 100 ml of dichloromethane in which the
intermediate product F (0.025 mol) was dissolved was gradually added dropwise at
25'C. After the completion of the dropwise addition, a reaction was carried out for 12
hours. Thereafter, a solid obtained by removing dichloromethane was purified to
obtain the cyclic carbodiimide compound (Cl: MW=516). The structure of the cyclic
20 carbodiimide compound was confirmed by NMR and IR.

Dl: "Stabaxol (registered trade name)" I LF (a carbodiimide compound, produced by
Rhein Chemie Co., Ltd.)
D2: "Stabaxol (registered trade name)" P400 (a carbodiimide compound, produced by
68
Rhein Chemie Co., Ltd.)
D3: "Carbodilite (registered trade name)" LA-1 (a carbodiimide compound, produced
by Nisshinbo Chemical Co., Ltd.)
[Example 11
5 The polylactic acid resin (A3), the thermoplastic resin (Bl) other than a
polylactic acid and the cyclic carbodiimide compound (Cl) in the blending ratio
described in Table 1 were melt-kneaded at a resin temperature of 250°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (MI). During melt-kneading, no
10 isocyanate odor was generated. Table 1 shows the results of the average diameter of
the dispersoids and the difference in the number of dispersoids of the resin composition
and the carboxyl group concentration of the polylactic acid.
[Example 21
- - - -The polylacric acid resin (A3), the thermoplastic resin (B2) other than a
15 polylactic acid and the cyclic carbodiimide compound (Cl) in the blending ratio
described in Table 1 were melt-kneaded at a resin temperature of 275°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M2). During melt-kneading, no
isocyanate odor was generated. Table 1 shows the results of the average diameter of
20 the dispersoids and the difference in the number of dispersoids of the resin composition
and the carboxyl group concentration of the polylactic acid.
[Example 31
The polylactic acid resin (Al), the polylactic acid resin (A2), the thermoplastic
resin (Bl) other than a polylactic acid and the cyclic carbodiimide compouud (Cl) were
69
blended in the blending ratio described in Table 1 and to a total of 100 parts by weight
of the resulting mixture was added 0.04 parts by weight of a lithium
2,2'-methylenebis(4,6-di-t-butylphenyl)phosphate-basedn ucleating agent ("Adekastab
(registered tradename)" NA-11; produced by ADEKA Corporation). The resulting
5 mixture was melt-kneaded at a resin temperature of 275OC and a rotation speed of 30
rpm for 5 minutes using a Labo Plastmill (manufactured by Toyo Seiki Seisakusho Ltd.)
to obtain a resin composition M3.
During melt-kneading, no isocyanate odor was generated. Further, the resin
composition of (M3) had a stereocomplex crystallization degree of 100%. Table 1
10 shows the results of the average diameter of the dispersoids and the difference in the
number of dispersoids of the resin composition and the carboxyl group concentration of
the polylactic acid.
[Example 41
--~p~p~--~~--~~~-~~ --I -h- e- poiylaCtiC acid sin(iri), the the~fmopiastic (Bl)-oth~er~~thaa~n
15 polylactic acid and the cyclic carbodiimide compound (Cl) in the blending ratio
described in Table 1 were melt-kneaded at a resin temperature of 250°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M4). During melt-kneading, no
isocyanate odor was generated. Table 1 shows the results of the average diameter of
20 the dispersoidsand the difference in the number of dispersoids of the resin composition
and the carboxyl group concentration of the polylactic acid.
[Example 51
The polylactic acid resin (A3), the thermoplastic resin (Bl) other than a
polylactic acid and the cyclic carbodiimide compound (Cl) in the blending ratio
70
described in Table 1 were melt-kneaded at a resin temperature of 265°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M5). During melt-kneading, no
isocyanate odor was generated. Table 1 shows the results of the average diameter of
5 the dispersoids and the difference in the number of dispersoids of the resin composition
and the carboxyl group concentration of the polylactic acid.
[Example 61
The polylactic acid resin (Al) and the cyclic carbodiimide compound (Cl) in
the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
10 265'C and a rotation speed of 30 rpm for one minute using a Labo Plastmill
(manufactured by Toyo Seiki Seisakusho Ltd.). The thermoplastic resin (B3) other
than a polylactic acid was added to the resulting mixture, followed by melt-kneading at
a resin temperature of 240°C and a rotation speed of 30 ipm for two minutes to obtain a
~ ~~ p~ ~ - ~ ~ ~ . ~ ~ ~ resin composition ( ~ 6 ) . During melt:headirig,no isocyanate odor was-yenera~ed;
15 Table 1 shows the results of the average diameter of the dispersoids and the difference
in the number of dispersoids of the resin composition and the carboxyl group
concentration of the polylactic acid.
[Example 71
The polylactic acid resin (A3), the thermoplastic resin (B4) other than a
20 polylactic acid and the cyclic carbodiimide compound (CI) in the blending ratio
described in Table 1 were melt-kneaded at a resin temperature of 250°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M7). During nielt-kneading, no
isocyanate odor was generated. Table 1 shows the results of the average diameter of
7 1
the dispersoids and the difference in the number of dispersoids of the resin composition
and the carboxyl group concentration of the polylactic acid.
[Example 81
The polylactic acid resin (A3) and the cyclic carbodiimide compound (C1) in
5 the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
240°C and a rotation speed of 30 rpm for one minute using a Labo Plastmill
(manufactured by Toyo Seiki Seisakusho Ltd.). The thermoplastic resin (B5) other
than a polylactic acid was added to the resulting mixture, followed by melt-kneading at
a resin temperature of 240°C and a rotation speed of 30 ipm for two minutes to obtain a
10 resin composition (M8).
During melt-kneading, no isocyanate odor was generated. Table 1 shows the
results of the average diameter of the dispersoids and the difference in the number of
dispersoids of the resin composition and the carboxyl group concentration of the
15 [Example 91
The polylactic acid resin (A3) and the cyclic carbodiimide compound (Cl) in
the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
250°C and a rotation speed of 30 rpm for one minute using a Labo Plastmill
(manufactured by Toyo Seiki Seisakusho Ltd.). The thermoplastic resin (BI) other
20 than a polylactic acid was added to the resulting mixture, followed by melt-kneading at
a resin temperature of 250°C and a rotation speed of 30 rpm for two minutes to obtain a
resin composition (M9).
During melt-kneading, no isocyanate odor was generated. Table 1 shows the
results of the average diameter of the dispersoids and the difference in the number of
72
dispersoids of the resin composition and the carboxyl group concentration of the
polylactic acid.
[Example 101
A test specimen having a thickness of 4 mm according to IS0 specifications
5 was formed by using the composition (M7) obtained in Example 7 and an injection
molding machine (IS-ISOEN: manufactured by Toshiba Machine Co., Ltd.) at a
cylinder temperature of 250°C, a mold temperature of 120°C and a molding cycle of
100 seconds.
After the resulting test specimen was allowed to stand under an environment of
10 a temperature of 23°C and a relative humidity of 50% for 24 hours, an unnotched
impact value was measured according to IS0 specifications. The unnotched impact
value was 65 k ~ / m ~ .
[Comparative Example 11
~~~~~ ~ ~~~~ Without adding ihe cycIiccarbodiimide-~compouncithpe oiylaciicacid-resiu~
15 (A3) and the thermoplastic resin (Bl) other than a polylactic acid in the blending ratio
described in Table 1 were melt-kneaded at a resin temperature of 250°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M10). Table 1 shows the results of the
average diameter of the dispersoids and the difference in the number of dispersoids of
20 the resin composition and the carboxyl group concentration of the polylactic acid.
[Comparative Example 21
Without adding the cyclic carbodiimide compound, the polylactic acid resin
(A3) and the thermoplastic resin (B2) other than a polylactic acid in the blending ratio
described in Table 1 were melt-kneaded at a resin temperature of 275°C and a rotation
73
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (MI I). Table 1 shows the results of the
average diameter of the dispersoids and the difference in the number of dispersoids of
the resin composition and the carboxyl group concentration of the polylactic acid.
5 [Comparative Example 31
Without adding the cyclic carbodiimide compound (Component C), the
polylactic acid resin (Al) and the thermoplastic resin (Bl) other than a polylactic acid in
the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
250°C and a rotation speed of 30 rpm for 3 minutes using a Labo Plastmill
10 (manufactured by Toyo Seiki Seisakusho Ltd.) to obtain a resin composition (M12).
Table 1 shows the results of the average diameter of the dispersoids and the difference
in the number of dispersoids of the resin composition and the carboxyl group
concentration of the polylactic acid.
--p~[~~opi~iip~a ia~lyEex aiiiPl
15 Without adding the cyclic carbodiimide compound (Component C), the
polylactic acid resin (A3) and the thermoplastic resin (Bl) other than a polylactic acid in
the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
26S°C and a rotation speed of 30 ipm for 3 minutes using a Labo Plastmill
(manufactured by Toyo Seiki Seisakusho Ltd.) to obtain a resin composition (M13).
20 Table 1 shows the results of the average diameter of the dispersoids and the difference
in the number of dispersoids of the resin composition and the carboxyl group
concentration of the polylactic acid.
[Comparative Example 51
Without adding the cyclic carbodiimide compound (Component C), the
74
polylactic acid resin (Al) and the thermoplastic resin (B3) other than a polylactic acid in
the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
265OC and a rotation speed of 30 rpm for 3 minutes using a Labo Plastmill
(manufactured by Toyo Seiki Seisakusho Ltd.) to obtain a resin composition (M14).
5 Table 1 shows the results of the average diameter of the dispersoids and the difference
in the number of dispersoids of the resin composition and the carboxyl group
concentration of the polylactic acid.
[Comparative Example 61
Without adding the cyclic carbodiimide compound (Component C), the
10 polylactic acid resin (A3) and the thermoplastic resin (B4) other than a polylactic acid in
the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
250°C and a rotation speed of 30 rpm for 3 minutes using a Labo Plastmill
(manufactured by Toyo Seiki Seisakusho Ltd.) to obtain a resin composition (M15).
Tahle~~l-showths eresultsof thea-.rerage~diameteroft he dispers~idsandthedifference
15 in the number of dispersoids of the resin composition and the carboxyl group
concentration of the polylactic acid.
[Comparative Example 71
Without adding the cyclic carbodiimide compound (Component C), the
polylactic acid resin (A3) and the thermoplastic resin (B5) other than a polylactic acid in
20 the blending ratio described in Table 1 were melt-kneaded at a resin temperature of
240°C and a rotation speed of 30 rpm for 3 minutes using a Labo Plastmill
(manufactured by Toyo Seiki Seisakusho Ltd.) to obtain a resin composition (M16).
Table 1 shows the results of the average diameter of the dispersoids and the difference
in the number of dispersoids of the resin composition and the carboxyl group
75
concentration of the polylactic acid.
[Comparative Example 81
The polylactic acid resin (A3), the thermoplastic resin (Bl) other than a
polylactic acid and the other carbodiimide compound (Dl) in the blending ratio
5 described in Table 1 were melt-kneaded at a resin temperature of 250°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M17). During melt-kneading,
isocyanate odor was generated. Table 1 shows the results of the average diameter of
the dispersoids and the difference in the number of dispersoids of the resin composition
10 and the carboxyl group concentration of the polylactic acid.
[Comparative Example 91
The polylactic acid resin (A3), the thermoplastic resin (Bl) other than a
polylactic acid and the other carbodiimide compound (D2) in the blending ratio
~-p~-~~~ described-in~Table 1 ..?rere melt-k-qeaded~ata~resitne mperatureof 750°C and arotatian
15 speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M18). During melt-kneading,
isocyanate odor was generated. Table 1 shows the results of the average diameter of
the dispersoids and the difference in the number of dispersoids of the resin composition
and the carboxyl group concentration of the polylactic acid.
20 [Comparative Example 101
The polylactic acid resin (A3), the thermoplastic resin (Bl) other than a
polylactic acid and the other carbodiimide compound (D3) in the blending ratio
described in Table 1 were melt-kneaded at a resin temperature of 250°C and a rotation
speed of 30 rpm for 3 minutes using a Labo Plastmill (manufactured by Toyo Seiki
Seisakusho Ltd.) to obtain a resin composition (M19). During melt-kneading,
isocyanate odor was generated. Table 1 shows the results of the average diameter of
the dispersoids and the difference in the number of dispersoids of the resin composition
and the carboxyl group concentration of the polylactic acid.
5 [Comparative Example 111
A test specimen having a thickness of 4 mm according to IS0 specifications
was formed by using the composition obtained in Comparative Example 6 and an
injection molding machine (IS-150EN: manufactured by Toshiba Machine Co., Ltd.) at
a cylinder temperature of 250°C, a mold temperature of 120°C and a molding cycle of
10 100 seconds.
After the resulting test specimen is allowed to stand under an environment of a
temperature of 23°C and a relative humidity of 50% for 24 hours, an unnotched impact
value was measured according to IS0 specifications. The unnotched impact value was
26k/m2
[Table 1]

[Industrial Applicability]
The resin composition of the present invention is improved in compatibility
between a polylactic acid resin and a thermoplastic resin other than a polylactic acid
resin and may be suitably used as a resin molding or a molded product such as a film
and a fiber.

[CLAIMS]
[Claim I]
A resin composition comprising 1 to 99 parts by weight of a polylactic acid
resin (Component A), 1 to 99 parts by weight of a thermoplastic resin (Component B)
5 other than a polylactic acid and 0.1 to 3 parts by weight of a cyclic carbodiimide
compound (Component C) represented by the following formula(i):
(wherein, X is a tetravalent group represented by the following formula (i-1); and AS' to
As4 are each independently an optionally substituted ortho-phenylene group- or
10 l,2-naphthalene-diyl group.)
[Claim 2]
The resin composition according to claim 1, wherein in the resin composition,
the polylactic acid resin (Component A) and the thermoplastic resin (Component B)
other than a polylactic acid form a continuous phase and dispersoids dispersed and
present in the continuous phase, the dispersoids have an aveiage diameter of 2 pm or
less at an arbitrary cross-section of the composition, the difference in the number of the
dispersoids is less than 10% at optional 5 places having 15 pm length and 15 pm width
5 in the continuous phase in the cross-section, and the polylactic acid resin (Component
A) has a carboxylic group concentration of 10x0, equivalents/ton or less (wherein, u is
parts by weight of Component A/(Parts by weight of Component A + Parts by weight of
Component B + Parts by weight of Component C)).
[Claim 3]
The resin composition according to claim 1, wherein the polylactic acid resin
(Coniponent A) includes a poly-L-lactic acid and a poly-D-lactic acid and contains a
stereocomnplex polylactic acid crystal.
[Claim 4]
The resin composition according to claim 1, wherein the thermoplastic resin
(Component B) other than a polylactic acid is a thermoplastic resin capable of reacting
with carbodiimide andlor isocyanate.
[Claim 5]
The resin contposition according to claim 1, wherein the thermoplastic resin
(Component B) other than a polylactic acid is at least one selected from the group
consisting of a polyester, a polyamide and an aromatic polycarbonate.