DESCRIPTION
STEREOCOMPLEX POLYLACTIC ACID FILM AND RESIN COMPOSITION
[Field of the Invention]
The present invention relates to a stereocomplex polylactic acid film
5 especially excellent in transparency and a resin composition, more particularly to a
stereocomplex polylactic acid film for which low retardation is required.
[Background Art]
As a transparent polymeric substrate for optical use, for example, for liquid
display, touch panel, etc., a cellulosic film such as triacetyl cellulose, a polyester film
10 such as polyethyleneterephthalate film, a polycarbonate film, etc. are known.
However, since these resins originate fi-om petroleum which is a fmite
resource as the starting material, a problem of depletion of the petroleum resource is
concerned.
In recent years, a polylactic acid polymer is drawing attention as a material
15 with which the above-mentioned problem may be solved. As a fact, there have been
a lot of studies and developments on this material. The problem of depletion of
resource may be solved by using a polylactic acid polymer, since its starting material is
a plant material, such as corn. However, since polylactic acid has a lower glass
transition temperature compared to the conventional petroleum-derived material, such
20 as polycarbonate, crystallization is needed to provide heat resistance for practical use
of polylactic acid polymer. Crystallization lowers the transparency and causes a
problem that polylactic acid polymer cannot be used for optical use.
On the other hand, it is known that stereocomplex polylactic acid is formed by
mixing poly-L-lactic acid which consists of L-lactic acid unit and poly-D-lactic acid
1
which consists of D-lactic acid unit in a solution or molten state (for example, Patent
Document 1 and Non-patent Document 1) and that this stereocomplex polylactic acid
exhibits higher transparency and heat resistance compared to poly-L-lactic acid and
poly-D-lactic acid.
5 Furthermore, although there is a method to further improve the transparency
by controlling fluidity at extrusion process or using a nucleating agent for the
stereocomplex polylactic acid (for example, Patent Document 2, 3 and 4), a film
stretching operation and the like are required to obtain the transparency sufficient for
optical use even using these techniques. Such operation is not applicable to a
10 polarizer protection film for polarizing plate, a substrate for a transparent conductive
laminate, etc. for which low retardation is required. In addition, there has been a
problem that the crystalline structure such as spherocrystal causes depolarization, even
if the haze is low. The depolarization is evaluated by an increase of brightness when
a film is inserted between a pair of polarizing plates in a crossed Nicol arrangement.
15 [Citation List]
[Patent Document 1] Japanese Patent Laid-Open Publication No.S63-241024
Patent Document 2] Japanese Patent Laid-Open Publication No.2008-248162
[Patent Document 3] Japanese Patent Laid-Open Publication No.2004-359828
[Patent Document 4] Japanese Patent Laid-Open Publication No.2009-263561
20 [Non-patent Document 1] Macro molecules, 24, 5651 (1991)
[Disclosure of the Invention]
The present invention aims at solving the problems of the conventional art
mentioned above to provide a stereocomplex polylactic acid film excellent in
2
transparency and a resin composition.
[Means for Solving the Problem]
The present inventors studied the technique to modify the stereocomplex
polylactic acid by adding various additives in view of the above-mentioned
5 conventional techniques and found that, surprisingly, the stereocomplex polylactic acid
exhibits a different behavior when a specific amide compound which has been known
as a nucleating agent for polyolefin resin is added, compared to other compounds
known as the nucleating agent for polyolefin resin.
The present inventors have completed the present invention by an extensive
10 investigation based on this fmding.
Thus, the present invention includes the following items.
1. A stereocomplex polylactic acid film containing an amide compound
represented by the following general formula (1):
^ / (1)
(wherein Ri represents a residue obtainable by removing all carboxyl groups from
1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid; three or four R2
20 may be the same as or different from each other and each represents a hydrogen atom
or a linear or branched chain alkyl group having 1-10 carbon atoms; and k represents
an integer of 3 or 4).
2. The stereocomplex polylactic acid film according to the above-mentioned
item 1, wherein the amide compound is a compound represented by the following
3
formula (2):
^ - ^ (2)
3. The stereocomplex polylactic acid film according to the above-mentioned
item 1, wherein its crystallinity (C) is 90% or more.
10 4. The stereocomplex polylactic acid film according to the above-mentioned
item 1, wherein its crystallinity (C) is 70% or less.
5. The stereocomplex polylactic acid film according to the above-mentioned
item 1, wherein its stereocomplex crystallinity (S) is 90% or more.
6. The stereocomplex polylactic acid film according to the above-mentioned
15 item 1, wherein its haze is 1% or less.
7. The stereocomplex polylactic acid film according to the above-mentioned
item 1, wherein the absolute value of its out-of-plane retardation (Rth) is 20 nm or
less.
8. The stereocomplex polylactic acid film according to the above-mentioned
20 item 1, wherein its out-of-plane retardation (Rth) is -20 nm or less.
9. A stereocomplex polylactic acid resin composition containing an amide
compound represented by the following general formula (1):
^ / (1)
4
(wherein Ri represents a residue obtainable by removing all carboxyl groups from
1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid; three or four R2
5 may be the same as or different from each other and each represents a hydrogen atom
or a linear or branched chain alkyl group having 1 to 10 carbon atoms; and k
represents an integer of 3 or 4).
10. The stereocomplex polylactic acid resin composition according to the
above-mentioned item 9, wherein the amide compound is a compound represented by
10 the following formula (2):
W, CH,
[Advantage of the Invention]
According to the present invention, a stereocomplex polylactic acid film
especially excellent in transparency and a resin composition are provided by using
plant-derived materials, considering for the environment.
20 [Best Mode for Carrying Out the Invention]
Hereinafter, the present invention will be illustrated in detail.

The stereocomplex polylactic acid film of the present invention contains an
amide compound represented by the following general formula (1):
5
(wherein Ri represents a residue obtainable by removing all carboxyl groups from
5 1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid; three or four R2
may be the same as or different from each other and each represents a hydrogen atom
or a linear or branched chain alkyl group having 1 to 10 carbon atoms; and k
represents an integer of 3 or 4).
Content of the amide compound is preferably 0.05 to 2.0 parts in weight,
10 more preferably 0.1 to 1.5 parts in weight, even more preferably 0.12 to 1.0 parts in
weight, especially preferably 0.15 to 0.8 parts in weight relative to 100 parts in weight
of the stereocomplex polylactic acid resin.
If the content is less than 0.05 parts in weight, the effect of addition of the
amide compound cannot be obtained. If the content is more than 2.0 parts in weight,
15 the amide compound cannot be dispersed well and the haze increases.
In addition, known organic or inorganic materials may be added to the
stereocomplex polylactic acid film in the range where the heat resistance, optical
properties and mechanical properties needed are not affected. For example, calcium
silicate, talc, kaolinite, montmorillonite and other organic compounds may be used in
20 combination with the amide compound.
In the present invention, the mechanism of development of transparency by
the addition of the above-mentioned amide compound is not necessarily clear. In
addition, the present invention is not bound to any specific mechanism or theory.
The crystallinity (C) of the stereocomplex polylactic acid used in the present
6
invention is the value obtained by the following equation from the heat of crystal
fusion (AHm) of polylactic acid moiety at the first temperature rising and the heat of
crystallization (AHc) of polylactic acid moiety generated by crystallization during
temperature rising in the differential scanning colorimetry (DSC).
5 (C)={(AHn,-AHc)/ AH„} X 100(%)
The crystallinity (C) represents the crystalline state of the stereocomplex
polylactic acid film and is preferably in the range of 90% or more, more preferably in
the range of 95% to 100%, especially preferably in the range of 98% to 100%, most
preferably 100%, depending on its application. When the crystallinity is in this range,
10 the heat resistance (shape stability) of the stereocomplex polylactic acid film is good
even if it is used alone.
On the other hand, the stereocomplex polylactic acid film of the present
invention may be used as a non-crystalline state without crystallization treatment,
because the stereocomplex polylactic acid film of the present invention without
15 crystallization treatment is excellent in transparency even if the crystallization
proceeds spontaneously under the using environment, storage environment, or the like.
It is noted that the non-crystalline state means that the crystallinity (C) is 70% or less,
preferably 60%) or less, more preferably 50%) or less, especially preferably 40%) or less,
most preferably 30% or less.
20 However, the stereocomplex polylactic acid film in the non-crystalline state
with the crystallinity (C) of 70% or less significantly softens above the glass transition
temperature of polylactic acid, so that it is preferable that the film be used in a
laminated state with other substrate such as film or glass. Its suitable application
includes, for example, protection of polarizer in a polarizing plate.
7
The polarizing plate is generally used in a laminated state composed of a PVA
(polyvinyl alcohol) polarizer film interleaved between two polarizer protection films
and adhered to a glass substrate. Therefore, the heat resistance (shape stability) is not
required for the stereocomplex polylactic acid film used alone as the polarizer
5 protection film.
In addition, even in a state that the stereocomplex polylactic acid film of the
present invention is not adhered to a glass substrate, it crystallizes at lower
temperature than the temperature at which PVA starts heat shrinkage. Therefore, it is
possible to prevent the decrease of the polarization degree, because the stereocomplex
10 polylactic acid film prevents the heat shrinkage of PVA before PVA starts shrinking by
heat.
By using the stereocomplex polylactic acid film in such non-crystalline state,
for example, reduction of production cost by eliminating the heat treatment process of
the film and improvement of adhesiveness with an epoxy adhesive used for adhesion
15 with the PVA polarizer may be expected.
In regard to the transparency of the stereocomplex polylactic acid film, for
example, the total light transmittance is 80% or more, preferably 85% or more, more
preferably 90%) or more, especially preferably 91% or more, most preferably 92%) or
more. The haze is !%> or less, preferably 0.8%) or less, more preferably 0.5%) or less,
20 especially preferably 0.4%) or less, most preferably 0.3% or less.
Although the thickness of the stereocomplex polylactic acid film may be
determined as needed, it is about 10 to 500 \xm from a viewpoint of strength and
workability such as handling properties, more preferably 15 to 300 |j,m, especially
preferably 20 to 200 |xm.
8
Although the stereo complex polylactic acid film must contain the
stereocomplex polylactic acid resin described later, other resins may be blended with
the stereocomplex polylactic acid resin from a viewpoint of the heat resistance, optical
properties and mechanical properties required.
5 Resins which may be blended include, for example, polyamide resin,
polyacetal resin, polyolefm resin such as polyethylene resin and polypropylene resin,
polystyrene resin, acrylic resin, polyurethane resin, chlorinated polyethylene resin,
chlorinated polypropylene resin, aromatic polyketone resin, aliphatic polyketone resin,
fluorine resin, polyphenylene sulfide resin, polyether ketone resin, polyimide resin,
10 thermoplastic starch resin, AS resin, ABS resin, AES resin, ACS resin, polyvinyl
chloride resin, polyvinylidene chloride resin, vinylester resin, MS resin, polycarbonate
resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin,
polyphenylene oxide resin, poly-4-methyl-pentene-l, polyetherimide resin, polyvinyl
alcohol resin, etc. Among them, acrylic resin, especially polymethyl methacrylate, is
15 preferred from a viewpoint of good compatibility and close refractive index.
Content of the stereocomplex polylactic acid resin in the stereocomplex
polylactic acid film is preferably 80 wt% or more, more preferably 85 wt% or more,
even more preferably 90 wt% or more, particularly preferably 95 wt% or more, most
preferably 98 wt% or more. If the content of the stereocomplex polylactic acid resin
20 is less than 80 wt%, the stereocomplex polylactic acid resin hardly crystallizes,
sometimes causing a problem with the heat resistance and transparency.
In regard to the heat resistance of the stereocomplex polylactic acid film, the
absolute value of the dimension change rate when heat-treated, for example, at I20°C
for 60 minutes is 3% or less, preferably 2% or less, more preferably 1.5% or less,
9
especially preferably 1% or less, most preferably 0.5% or less.
In addition, since the stereocomplex polylactic acid film of the present
invention is excellent in transparency after crystallization even without stretching
treatment, it is possible to realize the low retardation property. For example, the
5 in-plane retardation (R) defmed by the following equation is 10 nm or less, preferably
5 nm or less, more preferably 3 rmi or less, especially preferably 2 nm or less, most
preferably 1 nm or less. The absolute value of the out-of-plane retardation (Rth) is
20 nm or less, preferably 15 nm or less, more preferably 10 nm or less, especially
preferably 5 rmi or less, most preferably 3 nm or less.
10 The retardation in the present invention is herein defmed as follows:
In-plane retardation (R)=|nx-ny| X d
Out-of-plane retardation (Rth)={(nx+ny)/2-nz} Xd
wherein Ux, Uy and n^ are each three dimensional refractive index of the film,
corresponding to the refractive index in the x-axis direction which is the maximum
15 refractive index in the film plane (nx), the refractive index in the y-axis direction which
is perpendicular to the x-axis in the film plane (Uy), and the refi"active index in the
normal direction of the film (Uz), respectively, d is the thickness (nm) of the
retardation film.
Furthermore, the stereocomplex polylactic acid film containing the amide
20 compound of the present invention surprisingly provides the out-of-plane retardation
(Rth) of-20nm or less easily depending on the heat treatment conditions.
In addition, when the retardation property is needed depending on the
application, the required retardation property may be developed by stretching
treatment.
10

The stereocomplex crystallinity (S) of the stereocomplex polylactic acid used
in the present invention is a value obtainable by the following equation from the heat
of fusion of polylactic acid homocrystal observed below 190°C (AHnih) and the heat
5 of fusion of polylactic acid stereocomplex crystal observed at 190°C or higher
(AHnisc) by differential scanning calorimetry (DSC).
(S)=[AHm,e/(AHmh+AHmsc)] X 100
The stereocomplex crystallinity (S) is preferably 90% to 100%, more
preferably 95% to 100%, especially preferably 98% to 100%, especially preferably
10 100%.
The stereocomplex crystallinity (S) of 90% or more makes it possible to keep
high transparency and high heat resistance.
In order to suitably satisfy the above-mentioned stereocomplex crystallinity
(S), it is preferable that the weight ratio of poly-D-lactic acid component and
15 poly-L-lactic acid component in polylactic acid be 90/10 to 10/90.
More preferably the ratio is 80/20 to 20/80, more preferably 30/70 to 70/30,
especially preferably 40/60 to 60/40, the ratio being selected theoretically as close as
possible to 1/1.
Poly-L-lactic acid component and poly-D-lactic acid component may be
20 produced by conventionally known method.
For example, those components may be produced by ring opening
polymerization of L-lactide or D-lactide in the presence of a metal-containing catalyst.
Those components may also be produced by solid-phase polymerization of low
molecular weight polylactic acid containing a metal-containing catalyst under reduced
11
pressure or normal to increased pressure and in the presence or absence of inert gas
flow after crystallization or without crystallization as needed. Those components
may also be produced by direct polymerization of lactic acid through dehydration
condensation in the presence or absence of organic solvent.
5 The polymerization reaction may be carried out using a conventionally known
reaction vessel. For example, a vertical or horizontal reactor equipped with a stirring
blade for high viscosity, such as a helical ribbon blade, may be used alone or in
parallel for ring opening polymerization or direct polymerization. Any of batch type,
continuous type or semi-batch type reactors or a combination thereof may be used.
10 Alcohol may be used as a polymerization initiator. Alcohol which does not
inhibit polymerization of polylactic acid and is not volatile is preferred. For example,
decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, ethylene glycol,
trimethylol propane, pentaerythritol, etc. may be suitably used.
Polylactic acid prepolymer to be used for the solid-phase polymerization is
15 crystallized in advance as a preferred embodiment from a viewpoint of prevention of
fiision of the resin pellet. The prepolymer is polymerized in a solid state in a fixed
vertical or horizontal reaction vessel or in a reaction vessel which rotates by itself (a
tumbler or kiln such as a rotary kiln) in a temperature range from the glass transition
temperature to below the melting temperature of the prepolymer.
20 As a metal-containing catalyst, alkaline metal, alkaline earth metal, rare
earthes, transition metals, aliphatic acid salt, carbonate, sulfate, phosphate, oxide,
hydroxide, halide, alcoholate of aluminum, germanium, tin, antimony, titanium, etc.
are exemplified.
Among them, aliphatic acid salt, carbonate, sulfate, phosphate, oxide,
12
hydroxide, halide, and alcoholate containing at least one metal selected from tin,
aluminum, zinc, calcium, titanium, germanium, manganese, magnesium and rare earth
elements are preferred.
As a preferred catalyst, a tin compound, specifically a tin-containing
5 compound such as staimous chloride, staimous bromide, stannous iodide, stannous
sulfate, stannic oxide, tin myristate, tin octylate, tin stearate, or tetraphenyl tin is
exemplified due to their high catalyst activity and low degree of side reaction.
Among them, tin (II) compounds, specifically diethoxytin, dinonyloxytin, tin
(II) myristate, tin (II) octylate, tin (II) stearate, tin (II) chloride, etc. are suitably
10 exemplified.
Amount of the catalyst to be used is 0.42 X 10"* to 100 X 10^ mol, especially
1.68 X 10^ to 42.1 X lO""* mol, considering the reactivity as well as the color hue and
stability of polylactides to be obtained, especially preferably 2.53 X 10^ to 16.8 X 10""*
mol, relative to 1kg of lactide.
15 It is preferable that the metal-containing catalyst which was used for
polylactic acid polymerization be inactivated by a conventionally known inactivator
prior to use of polylactic acid.
As such inactivator, for example, an organic ligand composed of a group of
chelate ligand which has an imino group and is capable of coordinating with a
20 polymerization metal catalyst, phosphoric acid having a low oxidation number of 5 or
less, such as dihydride oxophosphoric (I) acid, dihydride tetraoxodiphosphoric (II, II)
acid, hydride trioxophosphoric (III) acid, dihydride pentaoxodiphophoric (III, III) acid,
hydride pentaoxodiphosphoric (II, IV) acid, dodecaoxohexaphosphoric (III) acid,
hydride octaoxotriphosphoric (III, IV, IV) acid, octaoxotriphosphoric (IV, III, IV) acid,
13
hydride hexaoxodiphosphoric (III, V) acid, hexaoxodiphosphoric (IV) acid,
decaoxotetraphosphoric (IV) acid, hendecaoxotetraphosphoric (IV) acid,
eneaoxotriphosphoric (V, IV, IV) acid, and the like, phosphoric acids represented by
the formula xH20-yP205, including orthophosphoric acid wherein x/y=3,
5 polyphosphoric acid wherein 2>x/y>l and referred to as diphosphoric acid,
triphosphoric acid, tetraphosphoric acid, pentaphosphoric acid, and the like, depending
on the degree of condensation and a mixture thereof, metaphospheric acid wherein
x/y=l, inter alia trimetaphosphoric acid and tetrametaphosphoric acid, ultraphosphoric
acid wherein l>x/y>0 and having a network structure with a residual part of
10 phosphorus pentaoxide structure (They are sometimes collectively denoted by
metaphosphoric acid compounds.) and acidic salt of these acids, partial or whole ester
of monovalent or multivalent alcohols or polyalkyleneglycols, phosphono-substituted
lower aliphatic carboxylic acid derivatives, and the like are exemplified.
From a viewpoint of catalyst deactivation potential, phosphoric acids
15 represented by the formula xH20-yP205, including orthophosphoric acid wherein
x/y=3, polyphosphoric acid wherein 2>x/y>l and 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 wherein
x/y=l, inter alia trimetaphosphoric acid and tetrametaphosphoric acid, ultraphosphoric
20 acid wherein l>x/y>0 and having a network structure with a residual part of
phosphorus pentaoxide structure (They are sometimes collectively denoted by
metaphosphoric acid compounds.) and acidic salt of these acids, oxophosphoric acid
partial ester of monovalent or polyvalent alcohols or polyalkyleneglycols or acidic
esters of thereof, phosphono-substituted lower aliphatic carboxylic acid derivatives,
14
and the above-mentioned metaphosphoric acid compounds are preferably used.
The above-mentioned metaphosphoric acid compounds include a cyclic
metaphosphoric acid composed of about 3 to 200 phosphoric acid units condensed,
ultra region metaphosphoric acid having a three-dimensional network structure and
5 alkaline metal salts, alkaline earth metal salts, and onium salts thereof Among these,
a sodium salt of cyclic metaphosphoric acid, a sodium salt of uhra region
metaphosphoric acid, dihexylphosphono ethyl acetate (hereinafter sometimes
abbreviated as DHPA), which is a phosphono-substituted lower aliphatic carboxylic
acid derivative, and the like are preferably used.
10 Lactide content of polylactic acid used in the present invention is preferably I
to 5000 ppm. Lactide contained in polylactic acid may degrade the resin during the
melting process, worsen the color hue, sometimes causing the product unusable.
Although poly-L-lactic acid and or poly-D-lactic acid usually contains 1 to 5
wt% of lactide immediately after melting ring opening polymerization, the content of
15 lactide may be reduced to suitable range by performing a conventionally known lactide
reducing technique, such as vacuum evaporation in a single- or multi-screw extruder
or a high vacuum treatment in the polymerization apparatus alone or in combination at
any stage from the time point of termination of polymerization of poly-L-lactic acid
and/or poly-D-lactic acid to molding of polylactic acid.
20 Although lower lactide content improves the melt stability and hygrothermal
stability of the resin, it is rational and economical to make the content suitable to the
desired purpose, considering the advantage of lowering the melt viscosity of the resin.
Thus, it is rational to set the lactide content to 1 to 1000 ppm where the practical melt
stability is achieved. More preferably the range of 1 to 700 ppm, more preferably 2
15
to 500 ppm, especially preferably 5 to 100 ppm is selected.
Since the polylactic acid component contains lactide in such range, the
stability of polylactic acid at melt-film forming of stereocomplex polylactic acid to be
used in the present invention is improved, leading to the advantage of efficient
5 production, and hygrothermal stability and low gas generation may be enhanced.
The weight average molecular weight of polylactic acid to be used in the
present invention is selected considering the relationship between the moldability and
the mechanical and thermal properties of the molded articles obtained. Thus, the
weight average molecular weight is preferably 80,000 or more, more preferably
10 100,000 or more, more preferably 130,000 or more, in order to exert the mechanical
and thermal properties such as the strength, elongation, heat resistance, etc. of the
molded articles.
However, since the melt viscosity of polylactic acid increases in an
exponential manner as the weight average molecular weight increases, molding
15 temperature should be set higher than the heat resistance temperature of polylactic acid
in some cases in order to have the viscosity of polylactic acid within the moldable
range when melt molding such as injection molding is carried out.
Specifically, polylactic acid film discolors due to the thermal degradation of
polylactic acid when molded above 300°C and possibly looses a commercial value.
20 Therefore, the weight average molecular weight of polylactic acid is
preferably 500,000 or less, more preferably 400,000 or less, more preferably 300,000
or less. Thus, the weight average molecular weight of polylactic acid is preferably
80,000 to 500,000, more preferably 100,000 to 400,000, more preferably 130,000 to
300,000. When the weight average molecular weight exceeds 300,000, melt
16
viscosity becomes too high, possibly making the melt film-forming difficult.
A ratio of weight average molecular weight (Mw) and number average
molecular weight (Mn) is called molecular weight distribution (Mw/Mn). Larger
molecular weight distribution means that the proportion of larger or smaller molecules
5 than the average molecular weight is high.
Thus, for example, polylactic acid of weight average molecular weight of
about 250,000 and molecular weight distribution of 3 or more possibly contains a high
proportion of molecules with molecular weight above 250,000, causing high melt
viscosity, which is not preferable for molding for the above-mentioned meaning.
10 Also, polylactic acid of relatively small weight average molecular weight of about
80,000 and large molecular weight distribution possibly contains a high proportion of
molecules with molecular weight below 80,000, causing poor durability of mechanical
properties of the molded article, which is not preferable for usage. From this
viewpoint, the range of molecular weight distribution is preferably 1.5 to 2.4, more
15 preferably 1.6 to 2.4, more preferably 1.6 to 2.3.
Polylactic acid in the present invention may be used to form a film by
contacting, preferably in a molten state, more preferably by melting and kneading, the
poly-L-lactic acid component and poly-D-lactic acid component in a weight ratio of
10/90 to 90/10 as mentioned above. The obtained film may be subjected to the
20 process such as stretching as needed to be used as a stereocomplex polylactic acid film
mentioned above. The contact temperature of poly-L-lactic acid component and
poly-D-lactic acid component is selected in the range of 210°C to 290°C, preferably
220 °C to 280°C, more preferably 225°C to 275°C, from a viewpoint of improvement
of melt stability and stereocomplex crystallinity of polylactic acid.
17
Although the meh kneading method is not particularly limited, conventionally
known batch type or continuous type melt kneading apparatus is suitably used. For
example, a melting/stirring vessel, a single screw extruder, a twin screw extruder, a
kneader, an anaxial basket-type stirring vessel, "Viborac (registered trade name)"
5 manufactured by Sumitomo Heavy Industries, Ltd., N-SCR manufactured by
Mitsubishi Heavy Industries, Ltd., a spectacle-shaped blade or lattice blade or a
Kenix-type stirrer manufactured by Hitachi Ltd., or a tubular polymerizer equipped
with a Sulzer-type SMLX static mixer, and the like may be used. Among them, a
spectacle-shaped blade, an anaxial basket-type stirring vessel, N-SCR, a twin screw
10 ruder, and the like, which are self-cleaning type polymerizers, are suitably used from a
viewpoint of productivity and quality, especially color hue, of polylactic acid.
Preferably, a specific additive may be added to polylactic acid of the present
invention so long as it does not compromise the purpose of the present invention, in
order to facilitate the formation of stereocomplex polylactic acid crystal in a stable and
15 efficient manner.
For example, a phosphoric acid ester metal salt may be added as a
stereocomplex crystallization promoter. As these phosphoric acid ester metal salts,
"Adekastab (registered trade name)" NA-11 and "Adekastab (registered trade name)"
NA-71 made by ADEKA Corporation, and the like are suitably exemplified.
20 It is preferable that the phosphoric acid ester metal salt be used in an amount
of 0.001 to 2 wt%, preferably 0.005 to 1 wt%, more preferably 0.01 to 0.5 wt%, more
preferably 0.02 to 0.3 wt% relative to the weight of polylactic acid. If the amount is
too small, the effect to increase the stereocomplex crystallinity (S) is small. If the
amount is too large, the melting point of the stereocomplex crystal unfavorably
18
decreases.
Known nucleating agent for crystallization may be used in combination in
order to enhance the effect of the phosphoric acid ester metal salt as needed. Among
them, calcium silicate, talc, kaolitiite, montmorillonite, and an organic amide
5 compound may be suitably selected.
The amount of the above-mentioned nucleating agent for crystallization to be
used is selected in the range of 0.03 to 5 wt%, preferably 0.04 to 2 wt%, more
preferably 0.05 to 1 wt%, relative to polylactic acid.
The content of carboxylic acid group, which may be contained in polylactic
10 acid through its production, should be as small as possible. For this reason, it is
preferable to use the polymer obtained by ring opening polymerization of lactide using
an initiator other than water or the polymer with carboxylic acid group minimized by a
chemical treatment after polymerization.
Polylactic acid in the present invention may be copolymerized polylactic acid
15 obtained by copolymerizing L-lactic acid or D-lactic acid with other components
having an ester formation ability. As a copolymerizable component,
hydroxycarboxylic acids such as glycolic acid, 3-hydroxybutyric acid,
4-hydroxybutyric acid, 4-hydroxyvaleric acid, 6-hydroxycaproic acid, as well as
compounds having a plurality of hydroxylic groups in the molecule such as ethylene
20 glycol, propyrene glycol, butanediol, neopentyl glycol, polyethylene glycol, glycerine,
pentaerythritol, etc. or derivatives thereof, and compounds having a plurality of
carboxylic acid groups in the molecule such as adipic acid, sebacic acid, fumaric acid,
etc. and derivatives thereof are exemplified.
Various additives which are added in order to improve the properties of
19
polylactic acid may deteriorate the optical properties in many cases. If these
additives are used in combination with the amide compound of the present invention,
the optical properties are not likely to be deteriorated.
For example, it is known that carbodiimide compounds are added in order to
5 improve the hydrolysis resistance of polylactic acid. Although the optical properties
are generally deteriorated when a carbodiimide compound is added, it is possible to
satisfy both of the optical properties and hydrolysis resistance at a high level if the
carbodiimide compound is used in combination with the amide compound of the
present invention.
10
The most characteristic of the present invention is that the stereocomplex
polylactic acid film contains the amide compound represented by the following
general formula (1).
^ / (1)
(wherein Ri represents a residue obtainable by removing all carboxyl groups from
1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid; three or four R2
may be the same as or different from each other and each represents a hydrogen atom
20 or a linear or branched chain alkyl group having 1 to 10 carbon atoms; and k
represents an integer of 3 or 4.)
Specific examples of the amide compound represented by the above general
formula (1) include 1,2,3-propanetricarboxylic acid tricyclohexylamide,
1,2,3-propanetricarboxylic acid tri(2-methylcyclohexylamide),
20
1,2,3-propanetricarboxylic acid tri(3-methylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-methylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-ethylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-ethylcyclohexylamide),
5 1,2,3-propanetricarboxylic acid tri(4-ethylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-n-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-n-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-isopropylcyclohexylamide),
10 1,2,3-propanetricarboxylic acid tri(3-isopropylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-isopropylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-n-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-n-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-butylcyclohexylamide),
15 1,2,3-propanetricarboxylic acid tri(2-isobutylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-isobutylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-isobutylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-sec-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-sec-butylcyclohexylamide),
20 1,2,3-propanetricarboxylic acid tri(4-sec-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-tert-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-tert-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-tert-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-pentylcyclohexylamide).
1,2,3-propanetricarboxylic acid tri(4-n-hexylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-heptylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-octylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri[4-(2-ethylhexyl)cyclohexylamide],
5 1,2,3-propanetricarboxylic acid tri(4-n-nonylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-decylcyclohexylamide),
1,2,3-propanetricarboxylic acid [(cyclohexylamide)di(2-methylcyclohexylamide)],
1,2,3-propanetricarboxylic acid [di(cyclohexylamide)(2-methylcyclohexylamide)],
1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic
10 acid tetra(2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-niethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
15 tetra(4-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
20 tetra(3-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
0 0
tetra(2-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
5 tetra(3-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
10 tetra(4-n-pentylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-hexylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-heptylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-octylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra[4-(2-ethylhexyl)cyclohexylamide], 1,2,3,4-butanetetracarboxylic acid
15 tetra(4-n-nonylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-decylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
[di(cyclohexylamide)di(2-methylcyclohexylamide)], etc.
Among the above-mentioned amide compounds, the amide compound
wherein R2 in the above general formula (1) is a hydrogen atom or a linear or branched
20 chain alkyl group with 1 to 4 carbon atoms is preferred.
Specifically, 1,2,3-propanetricarboxylic acid tricyclohexylamide,
1,2,3-propanetricarboxylic acid tri(2-methylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-methylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-methylcyclohexylamide),
23
1,2,3-propanetricarboxylic acid tri(2-ethylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-ethylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-ethylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-n-propylcyclohexylamide),
5 1,2,3-propanetricarboxylic acid tri(3-n-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-propylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-isopropylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-isopropylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-isopropylcyclohexylamide),
10 1,2,3-propanetricarboxylic acid tri(2-n-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-n-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-n-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-isobutylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-isobutylcyclohexylamide),
15 1,2,3-propanetricarboxylic acid tri(4-isobutylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-sec-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-sec-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-sec-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(2-tert-butylcyclohexylamide),
20 1,2,3-propanetricarboxylic acid tri(3-tert-butylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(4-tert-butylcyclohexylamide),
1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic
acid tetra(2-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-niethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
24
tetra(4-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
5 tetra(2-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
10 tetra(4-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
15 tetra(3-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(2-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
20 tetra(2-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(4-tert-butylcyclohexylamide), etc. are exemplified.
Among these preferred amide compounds, the amide compound wherein R2 in
the above general formula (1) is a hydrogen atom or a methyl group is especially
25
preferred from a viewpoint of the balance of transparency and stiffiiess of the film
obtained and availability of the raw material of the amide compound. Specifically,
1,2,3-propanetricarboxylic acid tricyclehexylamide, 1,2,3-propanetricarboxylic acid
tri(2-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid
5 tri(3-methylcyclo hexylamide), 1,2,3-propanetricarboxylic acid
tri(4-methylcyclo hexylamide), 1,2,3,4-butanetetracarboxylic acid
tetracyclo hexylamide, 1,2,3,4-butanetetracarboxylic acid
tetra(2-methylcyclo hexylamide), 1,2,3,4-butanetetracarboxylic acid
tetra(3-methylcyclo hexylamide), 1,2,3,4-butanetetracarboxylic acid
10 tetra(4-methylcyclohexylamide), etc. are exemplified.
In addition, when improvement effect of transparency is especially required,
the amide compound wherein Ri in the above general formula (1) is a residue
obtainable by removing all carboxyl groups from 1,2,3-propane tricarboxylic acid is
especially preferred. Specifically, 1,2,3-propanetricarboxylic acid
15 tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri(2-methylcyclohexylamide),
1,2,3-propanetricarboxylic acid tri(3-methylcyclo hexylamide),
1,2,3-propanetricarboxylic acid tri(4-methylcyclohexylamide), etc. are exemplified.
Among them, 1,2,3-propanetricarboxylic acid tri(2-methylcyclohexylamide)
represented by the following formula (2) is preferred from a viewpoint of the effect
20 and availability of the raw material.
26
CHa CHj
H H
5 I
^ ^ (2)
The above-mentioned amide compounds may be used alone or in combination
of two or more kinds as needed.
The crystal form of the amide compound of the present invention is not
10 particularly limited so long as the effect of the present invention is achieved and any
crystal forms such as hexagonal crystal, monoclinic crystal, cubical crystal, etc. may
be used. These crystals are known or may be produced according to known methods.
Although it is preferable that the purity of the amide compound of the present
invention be substantially 100%, it may contain some impurities. Even if the amide
15 compound contains some impurities, recommended purity of the amide compound is
preferably 90wt% or more, more preferably 95wt% or more, especially preferably
97wt% or more. As the impurities, monoamide of dicarboxylic acid or its ester
compound or diamide of monocarboxylic acid or its ester compound, both derived
from reaction intermediate or unreacted substance, and imide compound derived from
20 side reaction, and the like are exemplified.
The production method of the amide compound of the present invention is not
particularly limited so long as the intended amide compound is obtainable. For
example, the amide compound may be produced from a specific aliphatic
polycarboxylic acid component and a specific alicyclic monoamine component
T 7
according to a conventionally known method (For example, a specific aliphatic
polycarboxylic acid and a specific alicyclic monoamine in the amount of 3 to 20
equivalents relative to the acid are reacted in an inert solvent at 60°C to 200°C for 2 to
10 hours, as described in Japanese Patent Laid-open publication H07-242610.).
5 As the above-mentioned aliphatic polycarboxylic acid component,
1,2,3-propanetricarboxylic acid, 1,2,3,4-butanetricarboxylic acid and derivatives
thereof, such as acid chloride or anhydride or ester with a lower alcohol having 1 to 4
carbon atoms are exemplified. These aliphatic polycarboxylic acid components may
be subjected to the amide production alone or in the mixture of two kinds.
10 The above-mentioned alicyclic monoamine component is at least one kind
selected from a group consisting of cyclohexylamine and cyclohexylamine substituted
with a linear or branched chain alkyl group having 1 to 10 (preferably 1 to 4) carbon
atoms. They may be subjected to the amide production alone or in the mixture of two
or more kinds.
15 Specifically, cyclohexylamine, methylcyclohexylamines such as
2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine,
2-ethylcyclohexylamine, 2-n-propylcyclohexylamine, 2-isopropylcyclohexylamine,
2-n-butylcyclohexylamine, 2-isobutylcyclohexylamine, 2-sec-butylcyclohexylamine,
2-tert-butylcyclohexylamine, etc. are exemplified.
20 The above-mentioned alkyl-substituted cyclohexylamine may be any of
cis-isomer, trans-isomer, and the mixture of these stereoisomers. Preferred ratio of
the cis-isomer: trans-isomer is in the range of 50:50 to 0:100, the range of 35:65 to
0:100 being especially preferable.
Although particle diameter of the amide compound of the present invention is
not particularly limited so long as the effect of the present invention is achieved, it is
preferable that the particle diameter be as small as possible from a viewpoint of the
rate of dissolution (or time of dissolution) to the molten resin. When the particle
diameter is measured by laser diffraction light scattering method, recommended
5 maximum particle diameter of the amide compound is 200 |am or less, preferably 100
\im or less, more preferably 50 ^m or less, especially 10 ^im or less.
As the method to adjust the maximum particle diameter to the above range, a
pulverizing apparatus known in the art may be generally used and a known
classification apparatus may be used as needed. Specifically, a fluidized bed counter
10 jet mill lOOAFG (trade name, manufactured by Hosokawa Micron Group), a
supersonic jet mill PJM-200 (trade name, manufactured by Nippon Pneumatic MFG.
Co., Ltd.), a pin mill, etc. are exemplified as the pulverizing apparatus and a vibration
sifter, a dry-type classifier (such as Cyclone and Micron Separator), etc. are
exemplified as the classification apparatus.
15
The method to add the amide compound to stereocomplex polylactic acid in
the present invention is not particularly limited and conventionally known various
methods may be used as needed. For example, the compounds may be mixed using a
tumbler, a V-type blender, Supermixer, Nauta mixer, Banbury mixer, a kneading roll, a
20 single screw or twin screw extruder, or the like.
In addition, it is also possible to prepare in advance a masterbatch containing
the amide compound of the present invention in high concentration and knead it with
stereocomplex polylactic acid prepared separately to adjust to the intended additive
concentration.
29

The production method of the stereocomplex polylactic film is not
particularly limited and it may be produced according to a known method. For
example, the film is formed by extrusion molding using an extruder and the like
5 equipped with I-dye, T-dye, circular dye, etc.
In the case of extrusion molding, the shaped article may be produced by
extruding the molten resin onto a cooling drum to adhere and cool the molten resin
onto the rotating cooling drum. In order to tightly adhere the molten resin onto the
cooling drum, techniques such as increasing the temperature of the casting drum,
10 nipping the resin with the rolls, or electrostatic adhesion may be used. When an
electrostatic adhesion method is used, an unstretched film with few surface defects
may be obtained by admixing an electrostatic adhesive agent such as a quartemary
phosphonium salt of sulfonic acid and applying a charge from the electrode to the
molten surface of the film without contact, thereby tightly adhering the film to the
15 rotating cooling drum.
In addition, the unstretched film may be cast molded by using a solvent which
dissolves the resin composition, for example, such as chloroform and methylene
dichloride, to make a solution followed by cast-drying and solidifying.
The unstretched film may be subjected to the uniaxial stretching in the
20 direction of the mechanical flow or to the uniaxial stretching in the transverse direction,
perpendicular to the the direction of the mechanical flow. In addition, a biaxially
stretched film may be produced by stretching according to a sequential biaxial
stretching using a roll and tenter, a simultaneous biaxial stretching using a tenter, a
biaxial stretching by tubular stretching, etc.
Although the stretching ratio is not particularly limited, the stereocomplex
polylactic acid film of the present invention is excellent in transparency after
crystallization even without a stretching treatment or with a low stretching ratio.
The film is crystallized by heat treatment. The technique and time of the
5 heat treatment are not particularly limited so long as the temperature is the
crystallization temperature (Tc) - 20°C or above and the melting temperature (Tm) -
20°C or below.
In addition, the film of the present invention may be provided with other
functional layer using the conventionally known method as needed. For example,
10 easily adhesive layer, transparent conductive layer, easily lubricant layer, hard coat
layer, adhesive layer, etc. may be exemplified. In addition, surface activation
treatments such as UV ozone treatment, plasma treatment, amine treatment, corona
treatment, acid treatment and alkaline treatment are possible.
[Examples]
15 Hereinafter, the present invention will be illustrated in more detail referring to
the examples. The present invention is in no way limited by these examples. It
should be noted that each value in the present invention was determined by the
following methods.

20 (1) Weight average molecular weight (Mw) and number average molecular weight
(Mn) of polymer:
Weight average molecular weight and number average molecular weight of
polymer were measured by gel permeation chromatography (GPC) and converted to
the standard polystyrene. The GPC measuring apparatus comprising a detector,
RID-6A differential refractometer manufactured by Shimadzu Corporation., and a
column, TSK gel G3000HXL, TSK gel G4000HXL, TSK gel G5000HXL and TSK
guard column HXL-L manufactured by Tosoh Corporation connected in series or a
column, TSK gel G2000HXL, TSK gel G3000HXL and TSK guard column HXL-L
5 manufactured by Tosoh Corporation connected in series was used.
The measurement was performed using chloroform as an eluting solvent and
injecting 10 (jl of the sample with a concentration of 1 mg/ml (chloroform containing
1% hexafluoroisopropanol) at a temperature of 40°C and a flow rate of LO ml/min.
(2) Glass transition temperature (Tg), crystallization temperature (Tc), melting
10 temperature (Tm), heat of crystallization (AHc), heat of crystal fusion (AHm),
crystallinity (C), stereocomplex crystallinity (S):
These items were measured using DSC2920 Modulated DSC manufactured
by TA Instruments, at the first temperature elevation with a temperature elevation rate
of20°C/min.
15 (3) Haze:
Haze was measured using a hazemeter (MDH2000) manufactured by Nippon
Denshoku Industries Co., Ltd.
(4) Thickness:
Thickness was measured using an electron micrometer manufactured by
20 Anritsu.
(5) In-plane retardation (R) and out-of-plane retardation (Rth):
Measurement was done using a spectroscopic ellipso meter (Ml 50)
manufactured by JASCO Corporation.
(6) Dimension change rate:
The distance between two points marked in advance on the film was
measured using a real-time scanning laser microscope (trade name "1LM21D")
manufactured by Lasertec Corporation. The dimension change rate was obtained as
an absolute value from the change of distance between the two points before and after
5 heat treatment divided by the value before heat treatment.
(7) Brightness with crossed Nicol arrangement:
This was evaluated from the brightness when a sample film was inserted
between a pair of polarizing plates disposed in a crossed Nicol arrangement on the
backlight at an angle to give the minimum brightness of the transmitted light. The
10 brightness of the transmitted light when the film was not inserted was 0.05 cd/m^ and
the polarization degree of the polarizing plate used was 99.8%.
(8) Adhesive strength of the polarizing plate
The adhesive strength was rated "good" when the adhered interface between
the polarizing plates prepared was not peeled off by inserting a cutter blade. The
15 adhesive strength was rated "poor" when the interface was peeled off.
(9) Comprehensive evaluation
The sample with the haze of 1% or less and the brightness in the crossed
Nicol arrangement of 1 cd/m^ or less was rated "good". Other samples were rated
"poor".
20
(1) Stereocomplex polylactic acid resin (Al):
To 100 parts in weight of L-lactide (manufactured by Musashino Chemical
Laboratory, Ltd., optical purity 100%) was added 0.005 parts in weight of tin octylate
and allowed to react for 2 hours at 180°C under a nitrogen atmosphere in a reactor
11
equipped with a stirring blade. Phosphoric acid of 1.2 equivalents relative to tin
octylate was added. Remaining lactide was then removed under a reduced pressure
of 13.3 Pa, followed by cutting into chips to obtain poly-L-lactic acid (LI). The
weight average molecular weight of poly-L-lactic acid (LI) obtained was 152,000,
5 glass transition temperature (Tg) was 55°C and melting temperature was 175°C.
Poly-D-lactic acid (Dl) was obtained by performing the polymerization under
the same conditions as the preparation of poly-L-lactic acid mentioned above, except
that L-lactide was replaced by D-lactide (manufactured by Musashino Chemical
Laboratory, Ltd., optical purity 100%). The weight average molecular weight of
10 poly-D-lactic acid (Dl) obtained was 151,000, glass transition temperature (Tg) was
55°C and melting temperature was 175°C.
Each of 50 parts in weight of poly-L-lactic acid (LI) and poly-D-lactic acid
(Dl) obtained by the above two operations and a phosphoric acid ester metal salt
("Adekastab (registered trade name)" NA-71 manufactured by ADEKA Corporation,
15 0.1 parts in weight) were supplied through the first supply inlet of a twin screw
kneader and melt kneaded at a cylinder temperature of 250°C, extruded as a strand into
a water vessel, cut into chips using a chip cutter to obtain the stereocomplex polylactic
acid resin (Al). The stereocomplex crystallinity (S) was 100%, glass transition
temperature (Tg) was 55°C and the melting temperature (Tm) was 216°C.
20 (2) Stereocomplex polylactic acid resin (A2):
Ninety-five parts in weight of the stereocomplex polylactic acid resin (Al)
and 5 parts in weight of "Acrypet (registered trade name)" VHOOl, or polymethyl
methacrylate manufactured by Mitsubishi Rayon Co., Ltd., were dried at 100°C for 5
hours under vacuum and supplied through the first supply inlet of a kneader
Through the second supply inlet was supplied 0.3 parts in weight of the amide
compound represented by the following formula (2), or "Rikaclear (registered trade
name)" PCI manufactured by New Japan Chemical Co., Ltd., melt kneaded at a
cylinder temperature of 230°C and a vent pressure of 13.3 Pa under vacuum
5 evacuation, extruded as a strand into a water vessel, cut into chips using a chip cutter
to obtain the stereocomplex polylactic acid resin (A2).
^ (2)
[Example 1]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
15 5 hours. Then, 0.3 parts in weight of the amide compound represented by the
following formula (2), or "Rikaclear (registered trade name)" PCI manufactured by
New Japan Chemical Co., Ltd., was added to 100 parts in weight of the stereocomplex
polylactic acid resin (Al) and the mixture was dry blended.
The blend was melt kneaded in an extruder at 230°C, melt extruded as a film
20 through a T-die at a die temperature of 230°C, adhered to and solidified on the surface
of a cooling drum at 40°C, and peeled off to obtain a film. This film was fiirther heat
set at a temperature of 125°C to obtain the stereocomplex polylactic acid film. When
the film obtained was heat treated at 120°C for 60 minutes, the absolute value of the
dimension change rate was 3% or less.
\ ^ ° <^ ° \^
^ (2)
[Example 2]
The stereocomplex polylactic acid resin (A2) was vacuum dried at 110°C for
5 hours. Then, the resin was melt kneaded in an extruder at 230°C, melt extruded as
10 a film through a T-die at a die temperature of 230°C, adhered to and solidified on the
surface of a cooling drum at 40°C, and peeled off to obtain a film. The film obtained
was further heat set at a temperature of 125°C to obtain the stereocomplex polylactic
acid film. When the film obtained was heat treated at 120°C for 60 minutes, the
absolute value of the dimension change rate was 3% or less.
15 [Example 3]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
5 hours. Then, 0.4 parts in weight of the amide compound represented by the
following formula (2) ("Rikaclear (registered trade name)" PCI manufactured by New
Japan Chemical Co., Ltd.) and 0.8 parts in weight of a cyclic carbodiimide compound
20 having a structure represented by the following formula (3) were added to 100 parts in
weight of the stereocomplex polylactic acid resin (Al) and the mixture was dry
blended. The blend was melt kneaded in an extruder at 230°C, melt extruded as a film
through a T-die at a die temperature of 230°C, adhered to and solidified on the surface
of a cooling drum at 40°C, and peeled off to obtain a film. The film obtained was
36
further heat set at a temperature of 125°C to obtain the stereocomplex polylactic acid
film. When the film obtained was heat treated at 120°C for 60 minutes, the absolute
value of the dimension change rate was 3% or less.
5
CHj CHj
" a b
(3)
The cyclic carbodiimide compound of the above formula (3) was obtained by
the following operation according to the description in Example 2 of International
20 Publication 2010/071211.
A reaction apparatus equipped with a stirrer and a heater was charged with
o-nitrophenol (0.11 mol), pentaerythrityl tetrabromide (0.025 mol), potassium
carbonate (0.33 mol) and N,N-dimethylformamide (200 ml) under a nitrogen
atmosphere. The mixture was allowed to react at 130°C for 12 hours. DMF was
removed by reduced pressure. The solid obtained was dissolved into 200 ml of
dichloromethane and separated three times with 100 ml of water. The organic layer
was dehydrated with 5 g of sodium sulfate and dichloromethane was removed by
reduced pressure to obtain the intermediate product (nitro body).
5 Then, the intermediate product (nitro body) (0.1 mol), 5% palladium carbon
(Pd/C) (2 g), and 400 ml of ethanol/dichloromethane (70/30) were charged into a
reaction apparatus equipped with a stirrer. The apparatus was replaced with
hydrogen five times. The mixture was allowed to react with hydrogen continuously
supplied at 25°C. The reaction was terminated when reduction of hydrogen stopped.
10 Pd/C was recovered and the mixed solvent was removed to obtain the intermediate
product (amine body).
Then, a reaction apparatus equipped with a sturer, a heater and a dripping
funnel was charged with triphenylphosphine dibromide (0.11 mol) and 150 ml of
1,2-dichloroethane under a nitrogen atmosphere. To this mixture a solution of the
15 intermediate product (amine body) (0.025 mol) and triethylamine (0.25 mol) in 50 ml
of 1,2-dichloroethane was added dropwise slowly at 25°C under stirring. After
completion of the addition, the mixture was allowed to react at 70°C for 5 hours.
Then, the reaction solution was filtered and the filtrate was separated five
times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium
20 sulfate and 1,2-dichloroethane was removed by reduced pressure to obtain the
intermediate product (triphenylphosphine body).
Then, a reaction apparatus equipped with a stirrer and a dripping fimnel was
charged with di-tert-butyl dicarbonate (0.11 mol), N,N-dimethyl-4-aminopyridine
(0.055 mol) and 150 ml of dichloromethane under a nitrogen atmosphere and the
resultant mixture was stirred. To this mixture a solution of the intermediate product
(triphenylphosphine body) (0.025 mol) dissolved in 100 ml of dichloromethane was
added dropwise slowly at 25°C. After completion of the addition, the mixture was
allowed to react for 12 hours. Then, dichloromethane was removed and the solid
5 obtained was purified to obtain the cyclic carbodiimide compound.
[Example 4]
The fdm obtained in Example 3 was fixed on a metal frame and heat treated at
90°C for 50 hours to obtain the stereocomplex polylactic acid fdm. When the film
obtained was heat treated at 120°C for 60 minutes, the absolute value of the dimension
10 change rate was 3% or less.
[Comparative Example 1]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
5 hours. Then, the resin was melt kneaded in an extruder at 230°C, melt extruded as
a film through a T-die at a die temperature of 230°C, adhered to and solidified on the
15 surface of a cooling drum at 40°C, and peeled off to obtain a film. The film obtained
was heat set at a temperature of 125°C to obtain the stereocomplex polylactic acid film.
When the film obtained was heat treated at 120°C for 60 minutes, the absolute value of
the dimension change rate was 3% or less.
[Comparative Example 2]
20 The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
5 hours. Then, 0.3 parts in weight of the amide compound represented by the
following formula (4) and commercially available as a nucleating agent for polyolefm
resin, "NJSTAR (registered trade name)" NUlOO manufactured by New Japan
Chemical Co., Ltd., was added to 100 parts in weight of the stereocomplex polylactic
39
acid resin (Al) and the mixture was dry blended. The blend was melt kneaded in
an extruder at 230°C, melt extruded as a film through a T-die at a die temperature of
230°C, adhered to and solidified on the surface of a cooling drum at 40°C, and peeled
off to obtain a film. The film obtained was heat set at a temperature of 125°C to
5 obtain the stereocomplex polylactic acid film. When the film obtained was heat
treated at 120°C for 60 minutes, the absolute value of the dimension change rate was
3% or less.
10 ^^"Y^^^^
^ - ^ (4)
[Comparative Example 3]
Poly-L-lactic acid (LI) was vacuum dried at 110°C for 5 hours. Then, 0.3
parts in weight of the amide compound represented by the following formula (2), or
15 "Rikaclear (registered trade name)" PCI manufactured by New Japan Chemical Co.,
Ltd., was added to 100 parts in weight of poly-L-lactic acid (LI) and the mixture was
dry blended. The blend was melt kneaded in an extruder at 230°C, melt extruded as a
film through a T-die at a die temperature of 230°C, adhered to and solidified on the
surface of a cooling drum at 40°C, and peeled off to obtain a film. The film obtained
20 was heat set at a temperature of 125°C to obtain the polylactic acid film. When the
film obtained was heat treated at 120°C for 60 minutes, the absolute value of the
dimension change rate was 3% or less.
40
CH, CHj
^ ^ (2)
[Comparative Example 4]
Poly-L-lactic acid (LI) was vacuum dried at 110°C for 5 hours. Then, 0.3
parts in weight of the amide compound represented by the following formula (4) and
10 commercially available as a nucleating agent for polyolefin resin, "NJSTAR
(registered trade name)" NUlOO manufactured by New Japan Chemical Co., Ltd., was
added to 100 parts in weight of poly-L-lactic acid resin (LI) and the mixture was dry
blended. The blend was melt kneaded in an extruder at 230°C, melt extruded as a
film through a T-die at a die temperature of 230°C, adhered to and solidified on the
15 surface of a cooling drum at 40°C, and peeled off to obtain a film. The film obtained
was heat set at a temperature of 125°C to obtain the polylactic acid film. When the
film obtained was heat treated at 120°C for 60 minutes, the absolute value of the
dimension change rate was 3% or less.
\ „ ^ (4)
[Comparative Example 5]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
41
5 hours. Then, 0.3 parts in weight of the amide compound represented by the
following formula (5) and commercially available as a heavy metal inactivating agent
for polyolefin, "Adekastab (registered trade name)" CDA-1 manufactured by ADEKA
Corporation, was added to 100 parts in weight of the stereocomplex polylactic acid
5 resin (Al) and the mixture was dry blended. The blend was melt kneaded in
an extruder at 230°C, melt extruded as a film through a T-die at a die temperature of
230°C, adhered to and solidified on the surface of a cooling drum at 40°C, and peeled
off to obtain a film. The film obtained was heat set at a temperature of 125°C to
obtain the stereocomplex polylactic acid film. When the film obtained was heat
10 treated at 120°C for 60 minutes, the absolute value of the dimension change rate was
3% or less.
OH O N=s:=^
I / H
15 \ ^
[Comparative Example 6]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
5 hours. Then, 0.3 parts in weight of the hydrazide compound represented by the
following formula (6) and commercially available as a heavy metal inactivating agent,
20 "Adekastab (registered trade name)" CDA-6 manufactured by ADEKA Corporation,
was added to 100 parts in weight of the stereocomplex polylactic acid resin (Al) and
the mixture was dry blended. The blend was melt kneaded in an extruder at
230°C, melt extruded as a film through a T-die at a die temperature of 230°C, adhered
to and solidified on the surface of a cooling drum at 40°C, and peeled off to obtain a
film. The film obtained was heat set at a temperature of 125°C to obtain the
stereocomplex polylactic acid fdm. When the film obtained was heat treated at
120°C for 60 minutes, the absolute value of the dimension change rate was 3% or less.
OH O 0 OH
I " I II " 1
N X 0 0 'xy (6,
[Comparative Example 7]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
5 hours. Then, 0.3 parts in weight of zinc phenylphosphonate represented by the
10 following formula (7) and commercially available as a crystal nucleating agent for
polylactic acid ("Ecopromote (registered trade name)" NP) manufactured by Nissan
Chemical Industries, Ltd., was added to 100 parts in weight of the stereocomplex
polylactic acid resin (Al) and the mixture was dry blended. The blend was meh
kneaded in an extruder at 230°C, meh extruded as a film through a T-die at a die
15 temperature of 230°C, adhered to and solidified on the surface of a cooling drum at
40°C, and peeled off to obtain a film. The film obtained was heat set at a
temperature of 125°C to obtain the stereocomplex polylactic acid film. When the
film obtained was heat treated at 120°C for 60 minutes, the absolute value of the
dimension change rate was 3% or less.
20
[Comparative Example 8]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
5 hours. Then, 0.3 parts in weight of talc FG-15 manufactured by Nippon Talc Co.,
Ltd. was added to 100 parts in weight of the stereocomplex polylactic acid resin (Al)
and the mixture was dry blended. The blend was melt kneaded in an extruder at
5 230°C, melt extruded as a film through a T-die at a die temperature of 230°C, adhered
to and solidified on the surface of a cooling drum at 40°C, and peeled off to obtain a
film. The film obtained was heat set at a temperature of 125°C to obtain the
stereocomplex polylactic acid film. When the film obtained was heat treated at
120°C for 60 minutes, the absolute value of the dimension change rate was 3% or less.
10 [Comparative Example 9]
The stereocomplex polylactic acid resin (Al) was vacuum dried at 110°C for
5 hours. Then, 0.8 parts in weight of the cyclic carbodiimide compound having a
structure represented by the following formula (3) was added to 100 parts in weight of
the stereocomplex polylactic acid resin (Al) and the mixture was dry blended. The
15 blend was melt kneaded in an extruder at 230°C, melt extruded as a film through a
T-die at a die temperature of 230°C, adhered to and solidified on the surface of a
cooling drum at 40°C, and peeled off to obtain a film. The film obtained was heat set
at a temperature of 125°C to obtain the stereocomplex polylactic acid film. When the
film obtained was heat treated at 120°C for 60 minutes, the absolute value of the
20 dimension change rate was 3% or less.
44
(3)
The evaluation results of the film obtained by operations in Example 1 to 4 and
Comparative Examples 1 to 9 are shown in Tables 1, 2 and 3.
10
Table 1
Example 1 Example 2 Example 3 Example 4
Amide Amide Amide Amide
. . compound compound compound compound
JNucleatmg agent "Rikaclear" "Rikaclear" "Rikaclear" "Rikaclear"
PCI PCI PCI PCI
Amount of nucleating agent added „- „- „, „.
(wt%)
Addition of carbodiimide (Y/N) -., ,, ,, ,,
^ ' No No Yes Yes
Film thickness (nm) ^^ ^^ ^^ ^^
Stereocomplex crystallinity (S) (%) ^^^ ^^^ ^^^ ^^^
Crystallinity(C) (%) ~ ~ ~ ~
^^^^ ^"^"^ 0.21 0.32 0.25 0.39
In-plane retardation (R) (nm) „ . _ „ ^ „ . .
Out-of-plane retardation (Rth) 29 8 4 _9 4 _80 5
(nm) [ [ ; '___
Crossed Nicol brightness (cd/m^) ^ ^g ^ ^^ ^ 2g 0 72
Comprehensive evaluation ^ , ^ j ^ < ^j
^ Good Good Good Good
Table 2
Comparative Comparative Comparative Comparative
Example 1 Example 2 Example 3 Example 4
Amide Amide Amide
. compound compound compound
Nucleatmg agent "NJSTAR" "Rikaclear" "NJSTAR"
NUlOO PCI NUlOO
Amount of nucleating „, „- „-
agent added (wt%)
Addition of ,, T. , ,,, T,,
u A- J /-v/Tvn No No No No
carbodnmide (Y/N)
Film thickness (^m) ^^ ^^ ^^ ^^
Stereocomplex ~ ~ ~ ^ ^
crystallmity (S) (%)
Crystallinity(C) (%) ^^^ ^^Q ^^^ ^^^
"^^^ ^"'^"^ 3.20 35.20 22.81 84.12
In-plane retardation (R) ^^;^ 2^;^ ^^;^ ^^^
(nm)
Out-of-plane retardation ^^^ ^2.1 129.7 119.9
(Rth) (nm)
CrossedNicol 5 32 4 98 ^9 70 34 43
brightness (cd/m )
Comprehensive _ r. T. I eval, u^a t^i.o n | Poor | Poor | Po or | T^P oor
lable 3
Comparative Comparative Comparative Comparative Comparative
Example 5 Example 6 Example 7 Example 8 Example 9
Amide Hydrazide Zinc Talc
,, , ,. , compound compound phenylphosphoric
Nucleating agent "Adekastab" "Adekastab" acid
CDAl CDA6 "Ecopromote" NP
Amount of nucleating ^3 ^3 03 0.3
agent added (wt%)
Addition of carbodiimMe ^^ ^^ ^^ ^^ Yes
Film thickness (nm) 4O 4O 4O 40 40
Stereocomplex -^00 100 100 100 100
crystallmity (S) (%)
Crystallinity(C) (%) joO 100 100 100 100
^^^ ^"'""^ 24.40 3.17 2.10 4.11 5.11
In-plane retardation (R) 29.I 20.8 9.8 18.3 26.0
(™^
Out-of-plane retardation ^^ ^ 5^ ^ 30 2 41.2 57.9
(Rth) (nm)
CrossedNicol ^ ^^ 449 2.88 7.20 6.20
brightness (cd/m )
eval,u at,i.o n | Poor | Poor | Poor | Poor | Poor
46
[Example 5]
The stereocomplex polylactic acid film in uncrystallized state with the
crystallinity (C) of 26% was obtained by similar operation to Example 1, except that
5 the film obtained by adhering to and solidifying on a cooling drum at a temperature of
40°C and peeling off was not heat set.
This stereocomplex polylactic acid film did not exhibit significant haze
increase even after crystallization by heat treatment at 110°C for 5 minutes in a state
that the dimension was fixed.
10 A polarizing plate was prepared by laminating the film obtained as a
protection film with a polarizer according to the following method.

A polyvinylalcohol film of the average molecular weight of about 2,400, the
degree of saponification of 99.9 mol% or more, and the thickness of 75 \im was
15 immersed in purified water at 30°C, then immersed in an aqueous solution of
iodine/potassium iodide/water haing the weight ratio of 0.02/2/100 at 30°C. Then,
the film was immersed in an aqueous solution of potassium iodide/boric acid/water
having the weight ratio of 12/5/100 at 56.5°C. The film was then washed with
purified water at 8°C and dried at 65°C to obtain a polarizer of polyvinylalcohol
20 having adsorbed iodine with orientation. Stretching was performed mainly during
the process of iodine dying and boric acid treatment. Total stretching ratio was 5.3.

The above-mentioned stereocomplex polylactic acid film and a saponified
triacetylcellulose film were treated with corona discharge at the surfaces to be
47
laminated with the polarizer. These films were coated with a light curing resin
"Adeka Optomer" KR-508 manufactured by ADEKA Corporation as an adhesive with
a thickness of 2 |im.
Immediately after coating, the stereocomplex polylactic acid film and the
5 saponified triacetylcellulose film were laminated on one side and another side of the
above-mentioned polarizer, respectively, interposed by the adhesive-coated surfaces,
using a laminate roll. Then, the laminate was irradiated from the both sides with a
metal halide lamp so that the accumulated light intensity in the wavelength of 320 to
400 nm was 600 mJ/cm^. The adhesive was cured at 50°C for 24 hours to obtain the
10 polarizing plate.
The polarizing plate obtained was not peeled off by inserting a cutter blade
between the adhesive interfaces and exhibited the sufficient adhesive strength.
The polarizing plate obtained was laminated with a glass plate using an
acrylic adhesive and subjected to an endurance test at 90°C for 100 hours. Neither
15 significant increase of haze nor decrease of polarization degree was observed after the
test. Therefore, the sufficient durability as the polarizing plate was confirmed. In
addition, only the stereocomplex polylactic acid film was scraped off from the
polarizing plate after the endurance test and analyzed to fmd that the crystallinity (C)
was 100%.
20 The properties of the uncrystallized film and polarizing plate obtained are
shown in Table 4.
[Comparative Example 10]
The uncrystallized stereocomplex polylactic acid film with the crystallinity
(C) of 23% and the polarizing plate prepared by using this film were obtained by
similar operation to Comparative Example 1, except that the film obtained by adhering
to and solidifying on a surface of a cooling drum at 40°C and peeling off was not heat
set.
The stereocomplex polylactic acid film obtained exhibited significant haze
5 increase after crystallization by heat treatment at 110°C for 5 minutes in a state that the
dimension was fixed.
The polarizing plate obtained was not peeled off by inserting a cutter blade
between the adhesive interfaces and exhibited the sufficient adhesive strength. The
polarizing plate obtained was laminated with a glass plate using an acrylic adhesive
10 and subjected to an endurance test at 90°C for 100 hours. Significant increase of
haze was observed after the test showing that this sample did not have the sufficient
durability as the polarizing plate.
In addition, only the stereocomplex polylactic acid film was scraped off from
the polarizing plate after the endurance test and analyzed to fmd that the crystallinity
15 (C) was 100%.
The properties of the uncrystallized film and polarizing plate obtained are
shown in Table 4.
[Example 6]
The stereocomplex polylactic acid film with the crystallinity (C) of 78% and
20 the polarizing plate were obtained by similar operation to Example 5, except that the
film was heat set at 90°C for 2 minutes in a state that the dimension was fixed after
peeling off
This stereocomplex polylactic acid film did not exhibit significant haze
increase even after crystallization by heat treatment at 110°C for 5 minutes in a state
/in
that the dimension was fixed.
However, the polarizing plate obtained was peeled off by inserting a cutter
blade between the adhesive interfaces and adhesive strength was not sufficient.
The polarizing plate obtained was laminated with a glass plate using an
5 acrylic adhesive and subjected to an endurance test at 90°C for 100 hours. Neither
significant increase of haze nor decrease of polarization degree was observed after the
test. Therefore the sufficient durability as the polarizing plate was confirmed. In
addition, only the stereocomplex polylactic acid film was scraped off from the
polarizing plate after the endurance test and analyzed to fmd that the crystallinity (C)
10 was 100%.
The properties of the film and polarizing plate obtained are shown in Table 4.
[Table 4]
Example 5 Comparative Example 6
Example 10
Uncrystallized film
Amount of nucleating agent added (%) 03 - 03
Thickness (|xm) 60 60 60
Stereocomplex Crystallinity (S) (%) 100 100 100
Crystallinity (C) (%) 26 23 78
Haze (%) 0,08 0,07 0.17
In-plane retardation (R) (nm) 49 42 5.1
Out-of-plane retardation (Rth) (nm) 3.8 4,8 7.2
Crossed Nicol brightness | (cd/m^) | 0.06 | 0.06 | 0.15
After heat treatment at 110°C, 5 min
Thickness (|im) 60 60 60
Stereocomplex Crystallinity (S) (%) 100 100 100
Crystallinity (C) (%) 100 100 100
Haze (%) 0^29 4,80 0.27
In-plane retardation (R) (nm) 4A. 24.9 53
Out-of-plane retardation (Rth) (nm) 5J 49A 6.5
Crossed Nicol brightness (cd/m^) 0.22 6J0 0.23
Adhesive strength of polarizing plate Good Good Poor
The results show that the stereocomplex polylactic acid film containing the amide
15 compound represented by the following general formula (1) exhibits sufficient heat
50
resistance, low retardation and excellent transparency by crystallization. In addition,
the film in the uncrystallized state can be especially suitably used as a protection film
for the polarizer in the polarizing plate.
5 f^Mc—R_/ \ j
(wherein Ri represents a residue obtainable by removing all carboxyl groups from
1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid; three or four Ri
may be the same as or different from each other and each represents a hydrogen atom
10 or a linear or branched chain alkyl group having 1 to 10 carbon atoms; and k
represents an integer of 3 or 4).

CLAIMS
1. A stereocomplex polylactic acid film containing an amide compound
represented by the following general formula (1):
(wherein Ri represents a residue obtainable by removing all carboxyl groups from
1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid; three or four R2
may be the same as or different from each other and each represents a hydrogen atom
10 or a linear or branched chain alkyl group having 1 to 10 carbon atoms; and k
represents an integer of 3 or 4).
2. The stereocomplex polylactic acid film according to claim 1, wherein the
amide compound is a compound represented by the following formula (2):
3. The stereocomplex polylactic acid film according to claim 1, wherein the
20 crystallinity (C) is 90% or more.
4. The stereocomplex polylactic acid film according to claim 1, wherein the
crystallinity (C) is 70% or less.
5. The stereocomplex polylactic acid film according to claim 1, wherein the
stereocomplex crystallinity (S) is 90% or more.
; 6. The stereocomplex polylactic acid film according to claim 1, wherein the haze |
•"* is 1% or less.
7. The stereocomplex polylactic acid film according to claim 1, wherein the
absolute value of the out-of-plane retardation (Rth) is 20 nm or less.
5 8. The stereocomplex polylactic acid film according to claim 1, wherein the
out-of-plane retardation (Rth) is -20nm or less.
9. A stereocomplex polylactic acid resin composition containing "an amide
compound represented by the following general formula (1):
•(wherein Ri represents a residue obtainable by removing all carboxyl groups from
1,2,3-propane tricarboxylic acid or 1,2,3,4-butane tetracarboxylic acid; three or four Ri
may be the same as or different from each other and each represents a hydrogen atom
15 or a linear or branched chain alkyl group having 1 to 10 carbon atoms; and k
represents an integer of 3 or 4).
10. The stereocomplex polylactic acid resin composition according to claim 9,
wherein the amide compound is a compound represented by the following formula (2):