Highly Functional Bioplastics (PLA compounds) Used for Electronic Products

Kazuhiko Inoue, Shin Serizawa, Midori Yamashiro, and Masatoshi Iji

Eco-Material, Fundamental and Environmental Research Laboratories, NEC
34 Miyukigaoka, Tsukuba, Ibaraki 305-8501, Japan
E-mail: K-inoue@dv.jp.nec.com, Tel: 81 29 850 1520
Abstract
We have developed highly functional bioplastics
(biomass-based plastics), polylactic acid composites, which
improve the environmental friendliness of electronic products.
A kenaf-fiber-reinforced polylactic acid has high heat
resistance, high impact strength, and good moldability, and its
use in PC parts and mobile phone housing has started from
September 2004 and May 2006 respectively. A
thermoreversibly cross-linked polylactic acid has excellent
shape memory and recyclability (i.e., rewritable shape
memory), and will be used to create freestyle (wearable)
mobile products, shape of which users can easily adjust to their
own preferences.
Keywords
Bioplastic, kenaf fiber, heat resistance, shape memory,
recycling
1. Introduction
In recent years, interest in developing bioplastics to reduce
greenhouse gas (CO2) emissions and conserve petroleum
resources has been increasing. In particular, polylactic acid
(PLA) has the potential for use in electronic applications.
However, the physical properties of PLA are insufficient to be
widely used in electronic products. Specifically, its heat
resistance and impact strength are inferior to conventional
plastics such as ABS and polycarbonate. Moreover, the
crystallization rate of PLA is very low.
Concerning these issues, little is known about how to
improve these PLA properties by using biomass-based
materials. In particular, no remarkable improvements in the
housing of electronic products have been reported yet. Given
these circumstances, kenaf has recently been gaining a lot of
attention as a biomass-based additive.
Kenaf has a
significantly high ability to fixate CO2, and its photosynthesis
speed is more than three times higher than that of typical plants.
The kenaf fiber/PLA composite [1] or the composites of kenaf
fiber/petroleum-based plastics [2] have been studied recently.
However, these studies focused on a sheet application using
compression molding for automobile and building materials,
while housing applications using injection molding for
electronic products have not been examined.
We have improved the properties of PLA, such as heat
resistance, mechanical properties, and moldability enabled by
adding kenaf fiber. We also show the increase of in the impact
strength of PLA/kenaf fiber composites achieved by

1-4244-1186-6/07/$25.00 2007 IEEE

eliminating the short particles (crushed particles) from kenaf

fiber and adding flexibilizer.
To expand the use of biomass-based materials, we focused
on an intelligent bioplastic with a rewritable shape memory,
which has advantages over conventional petroleum-based
plastics. Petroleum-based shape memory plastics are already
on the market and have proved useful, but a rewritable shape
memory has not yet been used in such plastics because of the
dilemma posed by conventional shape memory mechanisms.
Generally, a shape memory plastic consists of a thermoplastic
phase and a frozen phase [3, 4]. The initial shape is memorized
in the frozen phase and can be recovered through the shape
memory effect. Therefore, the creation of the frozen phase
strongly affects the shape memory. Conventional rewritable
shape memory plastics cannot hold a stable shape memory
without creep [4, 5] because they use intermolecular bonds,
like crystal domain or hydrogen bonds, for the frozen phase, as
in the case of polyurethane plastics [3]. To create a stable shape
memory, the frozen phase must be rigidly formed using a
cross-linked structure with a stable covalent bond, as in the
case of a cross-linked polypropylene [3]. Unfortunately,
cross-linked plastics cannot be melted and recycled.
We have developed thermoreversible cross-linked
polylactic acid (TCP) using thermoreversible covalent bonding
based on the Diels-Alder reaction [6]. The rewritable shape
memory behavior of TCP was verified. The mechanism of TCP
was also investigated by dynamic mechanical analysis (DMA),
UV spectrometry, and differential scanning calorimetry (DSC).
2. Experiment
2-1. PLA/kenaf composite
Two kinds of kenaf fibers were prepared as follows. The
bast fiber was crushed to a length of less than 5 mm (average
length 3 mm). Another kenaf fiber was used with the bast fiber
cut to prevent the generation of crushed particles (average
length 5 mm).
The PLA/kenaf fiber composites (kenaf fiber: 5 30 wt%)
were prepared by kneading these components with a
twin-screw extruder at 184C. The PLA/kenaf fiber (5 mm)
composites and PLA/kenaf fiber (5 mm)/flexibilizer (a
copolymer of lactic acid and aliphatic polyester) composites
were also prepared with a single-screw extruder at 184C. Test
pieces 125 mm 13 mm 3.2 mm in size were obtained by
using an injection molding machine. All test pieces were
annealed at 100C for 4 h.
The characteristics of the PLA/kenaf composites were
measured by JIS K7191-2, JIS K7171 and JIS K7110 methods.
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IEEE Polytronic 2007 Conference

2-2. Rewritable shape memory PLA

Thermoreversible cross-linked PLA (TCP) was
synthesized. First, polyfurfurylpolylactic acid (PFP) [7] and
tris-(2-maleimidoethyl) amine (TMI) [8] were synthesized, and
then, plate-shaped test pieces (10 mm 40 mm 1 mm) were
molded with them. The plates were melted and used to mold a
new shape of the letter N (20 mm 25 mm 5 mm). The glass
transition temperature (Tg) of TCP was 49oC.
O
O

OH

4-s-t

O
O

r O
O

O
O

s
+

OH

160oC, 10 min
100oC, 1 h

PFP

N
O

TMI

160oC, 10 min
Rapid cool (r.t.)

TCP

Scheme 1. Thermoreversible cross-linking by Diels-Alder

reaction.
3. Results and Discussion

PLA/kenaf fiber composites compared with that of crushed

kenaf fiber.
The kenaf fiber was pulled out of the PLA matrix without
being fractured during the impact test. The long kenaf fiber
increases the amount of energy required for pulling it out, so
the impact strength of the PLA composite with kenaf, but
without crushed particles, was higher than that of the PLA
composite with kenaf containing crushed particles. Moreover,
instead of using the twin-screw extruder, as in the previous test,
the impact strength was further improved by preparing the
composite with a single-screw extruder, which prevents the
kenaf fiber from being ground (generation of crushed fiber
particles) during the kneading process.
Adding a flexibilizer, mainly made with biomass (a
copolymer of lactic acid and aliphatic polyester), to the
composite further improved the impact strength, which
exceeded those of the ABS/GF composites (Table 1).

3-1. PLA/kenaf composite

3-1-1. Effect of kenaf fiber on PLA
The crystallization rate of PLA was improved by adding
kenaf fiber. In the differential scanning calorimetric test, the
exothermic peak of the PLA/kenaf fiber composite was 5.6
minutes, and that of PLA was greater than 30 minutes. In
general, crystalline PLA has good mechanical properties
compared with those of amorphous PLA, but the crystallization
of PLA requires an annealing process after the molding. We
have discovered that the kenaf fiber could make the annealing
process unnecessary by adjusting molding conditions.
Normally, cellulose in natural plant fibers acts as a nucleating
agent for crystallization of polymers [9]. The kenaf fiber,
which also contains cellulose, probably acted as a nucleating
agent for PLA crystallization.
The heat resistance and modulus of PLA were greatly
improved by adding kenaf fiber. The distortion temperature of
the PLA/kenaf fiber composite exceeded that of the
petroleum-based plastic (ABS) when the composite contained
15% or more kenaf fiber. In addition, the modulus of the PLA
also increased according to the kenaf fiber content. However,
the impact strength of the PLA/kenaf fiber composite was still
insufficient.
Generally, inorganic fillers, such as glass fiber, improve
heat resistance, which is demonstrated by measurements of
distortion temperature and stiffness of crystalline polymers
including PLA, because the inorganic fillers promote the
crystallization and prevent deformation of molded pieces [10].
The kenaf fiber probably has the same synergistic effect as
inorganic fillers to improve heat resistance and stiffness.
3-1-2. Improvement in impact strength of PLA/kenaf
composite
We found that eliminating the crushed particles from kenaf
fiber improves the impact strength of PLA/kenaf fiber
composite. As shown in Table 1, long kenaf fiber without
crushed particles has a higher effect on the impact strength of

Table 1. Characteristics of PLA/kenaf composites*

No.
1
Resin
PLA
Fiber (wt%)
Kenaf (<5 mm)
0
0
Kenaf (5 mm)
0
Glass
0
Flexibilizer (wt%)
DTUL
(C)
66
Impact
(kJ/m2) 4.4
Strength
Flexural
(GPa)
4.5
Modulus
Flexural
(MPa)
132
Strength

2
PLA

3
PLA

4
PLA

5
ABS

20
0
0
0
120

0
20
0
0
109

0
20
0
20
104

0
0
20
0
100

3.1

5.5

7.8

4.8

7.6

7.1

6.8

7.3

93

115

72

110

*PLA composites containing kenaf fiber (5mm) and/or

flexibilizer were kneaded by single-screw extruder. The other
composites were kneaded by twin-screw extruder.

Figure 1. A mobile phone using PLA/kenaf composite.

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As shown in the comparison with the ABS/GF, the

PLA/kenaf fiber (5 mm) and PLA/kenaf fiber (5
mm)/flexibilizer composites have characteristics that are
practical for use in electronic housing products. The example
of application of PLA/kenaf composite is shown in Figure 1.
3-2. Rewritable shape memory PLA
TCP exhibited rewritable shape memory (Figure 2).
Plate-shaped test piece (a) was deformed easily into a U-shape
at 60oC (b). The U-shape was maintained by cooling the
sample. Then, the original plate shape was restored in 15 s by
heating the sample to 60oC. The memory of the plate shape of
TCP was erased by disconnecting the cross-links with 160oC
heating. The reheated compound was molded not only into
plate shape (a), but also into the shape of the letter N (c). In the
new shape, the material still behaved as a shape memory plastic
(c and d). Thus, as shown here, this new biomass-plastic has a
stable shape memory and is rewritable (recyclable).

Figure 2. Rewritable shape memory with TCP.

DMA measurement indicated that the crystallinity of PLA
disappeared because of cross-linking. A large drop in the
elastic modulus at temperatures above Tg was observed for
TCP, resulting in easier deformation.
The thermoreversible reaction of the TCP was verified
using UV spectroscopy. The changes in the absorption (294
cm-1) of the maleimide moiety were monitored during heating
and cooling processes. The changes indicated that the
thermoreversible cross-linking worked well in the biomass
plastic.
The rewritability of the TCP was investigated using DSC.
The exothermal and endothermal peaks were attributed to the
association (at 100oC) and dissociation (at 160oC) of the
thermoreversible Diels-Alder reaction. Both of these peaks
were observed in repetitive measurements during heating
(+10oC/min) following rapid cooling (-50oC/min). This result
demonstrates that the thermoreversible Diels-Alder reaction
works repeatedly and that material recycling is possible.
4. Conclusions
The heat-resistant PLA/kenaf composite and the intelligent
rewritable shape memory PLA have been developed for
electronic products.

Adding kenaf fiber significantly increases the heat

resistance and modulus of PLA. Moreover, the inclusion of the
fiber increases the crystallization rate of PLA. The impact
strength of the PLA composite was increased by removing the
crushed particles from the kenaf fiber and by adding a
flexibilizer to the composite. The main characteristics of the
composites (PLA/kenaf fiber, PLA/kenaf fiber/flexibilizer) are
comparable to or superior to those of GF-reinforced ABS, a
representative petroleum-based plastic used in housing. These
results demonstrate that the developed composites can be
applied to the housing of electronic products.
The intelligent PLA with the thermoreversible cross-linked
network based on the Diels-Alder reaction performs rewritable
shape memory. This bioplastic has potential uses in many fields
requiring durable or high-performance products. As thinner,
more compact equipment is developed for use as wearable
computers, the bioplastic could be used to shape equipment to
users' bodies.
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Succinic acid mono-furan-2-ylmethyl ester (SFE). A
chloroform solution of furfuryl alcohol (1.0 mol),
succinic anhydride (1.1 mol), and a catalytic amount of
pyridine was refluxed for 15 h and then washed with
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acidified with aqueous hydrochloric acid until the pH
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chloroform. The organic layer was concentrated in vacuo
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solution of SEF (0.34 mol), TP (0.045 mol), WSC (0.33
mol), and pyridine (0.32 mol) was refluxed for 55 h, and
then washed with water. The polymeric product was
recrystallized by adding methanol and purified by silica
gel in a mixture of chloroform and ethyl acetate. The
75

filtrate was evaporated in vacuo to give PFP. The

substitution number of furan (3.1 eq./mol) and molecular
weight (4,400) were calculated using NMR data. DSC: Tg
= 37oC.
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