03 amorphous pla for coating applications miyamoto pdf
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Amorphous PLA for coating applications
TOYOBO CO.,LTD.
Vylon Department
Takashi Miyamoto
ITR-2012
CONTENTS
1. About TOYOBO 2. About VYLOECOL ①Key features ②Molecular design ③Grades and each specification ④Applications (1)Packaging material (2)Ship bottom paint 3.Conclusion
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About TOYOBO
①Date of establishment: May 3, 1882 ②Date of incorporation: June 26, 1914 ③Paid-in capital: \51,730,003,166 ④Number of employees on a nonconsolidated basis: 3,238 (as of March 31,2011) ⑤Number of employees on a consolidated basis 10,178 (as of March 31,2011)
Key features
●VYLOECOL is amorphous polylactic acid.
●VYLOECOL dissolves in most of the general organic solvents due to its amorphous state. ●VYLOECOL shows the good adhesion property to regular polylactic acid film. ●Every grade provides high functionality of either pigment-dispersible binder or cross-linking property. ●VYLOECOL shows high-grade biodegradability and some grades are listed as the approved materials by JBPA (Japan Bio-plastic Association).
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Molecular design
●●●●●●●●●●●●●●●● PLLA Co-polymerization of D-lactic acid molecurar weight down
●●●●●●●●●●● Amorphous PLA
●●●●●●△●●●●● Pigment dispersible △:ionic group
●●●●●●□□□□□● Tg adjustment □:aliphatic momomer
●:D-lactic acid
Grades and each specification Grade
Molecular weight (×103)
Tg ( ℃)
Functional group
Biobased content (wt%)
Typical application
BE-400 43 50 - 1 00 Heat seal adhesive
BE-430 25 50 Pigment dispersion
99 Gravure ink binder
BE-600 25 30 Cross- linking
90 Primer coating
BE-910 25 -10 Cross- linking
60 Dry lamination adhesive
1
10
100
1000
25 30 35 40 45 50 55
NV[wt%]
ηB[dPa
・s]
BE-400
BE-910
Solution viscosity of VYLOECOL (Solvent: Ethyl-acetate )
Solid content
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Packaging material - Dry laminate adhesive application -
Substrate: Cellulose non-woven sheet and PLA film of other company Application: BE-910 is used for the adhesive to bond film with sheet.
Adhesion strength of dry lamination adhesive
Resin grade
Coated side
Dry lamination adhesion strength (N/cm) PLA resin/Cross linking agent (wt ratio)
100/0 100/5 100/10 100/15
BE-910 Coating to one side 1.2 4.1 3.2 3.0
Substrate:25μm PLA film Coated layer thickness: 3μm Drying condition: 60℃ for 15min Laminate condition: 0.9m/min ×29N/cm2 for 15min Cross linking agent: Colonate HX(made by Nippon Polyurethane, Aliphatic Isocyanate) Aging condition: 40℃ for 3days
The Biodegradability of Cross-linked BE-910 - ISO14855, by OWS -
-10
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30 35 40 45
Time (Days)
Biod
egra
datio
n (%
)
Cellulose BE91OHX5 BE91OHX10
Cellophane and coat resin both are biomass products that are derived from renewable resources, and also holds the Biodegradability.
Heat-sealing property; Print side
Heat-sealing property Water vapor barrier property Anti-blocking property
PLA derived resin coat (1μm each)
Cellophane (20μm)
GFML Comparative Table Test Item Unit GFML#300
(coating Cellophane) PL#300
(Cellophane) Coat resin PLA derivative -
Thickness mm 0.022 0.020
Weight g/m2 33.0 30.0
Tensile strength
MD N/15mm width 30 38
TD N/15mm width 19 25
Elongation at break
MD % 31 28
TD % 68 59
Oxygen permeability※1 cc/㎡・24h・atm 4.4 5.6
Moisture permeability※2 g/㎡・24hr 180 4000
Haze※3 % 2.8 2.5
※1 JIS K 7126 ※2 JIS Z 0208 ※3 JASCO Corporation turbidimeter These figures are test values and is not guaranteed values or standared values.
Ship Bottom Paint Applications
This area was coated by PLA based ship bottom paints on the 16th of Dec 1999.
Mechanism of Antifouling
Ship Bottom
Sea Water
Paint Layer
Antifouling Agents
Self-polishing Layer (hydrolysis of resins)
(-CH2-CH-) C=O O-
M2+
O-
C=O R
(-CH2-CH-) C=O O-
Na+
Typical Resin (oil-based)
Typical requirements for Resins
1. Resistance to cold flows 2. Suitable hydrolysis rates 3. Suitable solution viscosity
Cold flow test
NG sample
Sample resins were coated on a disk. The disk spins round at 30 knots speed.
Good sample
Sailing model test
Results of cold flow tests
Cold Flow
Good
NG 0 0.2 0.3 0.4 0.5 0.6 0.7
● ● ●
Reduced viscosity (dl/g)
●
Molecular design for Ship Bottom Paint
●●●●●●●●●●●●● Amorphous PLA The Hydrolysis rate is not enough
●●●●●-COO- M2+ -OOC-●●●●● M: Metal Key structure
Hydrolysis rates of PLA resins
Hydrolysis rate(%
)
0 5 10 15 20 25 30 Time (day)
0.5
1
1.5
2
2.5
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● ●
●
● ●
●
●
●
● ●
● ●
● ● ● ● ●
Acrilic resins(Cu2+ )
PLA ( Mg2+)
PLA
Solution viscosity and ionic species
Solution viscosity (dPa.s)
0.3 0.35 0.4 0.45 0.5 0.55 Reduced viscosity(dl/g)
50
100
150
200 ●
●
● ( 1460dPa.s)
●
●
● ●
● ●
Mg
Ca
Cu
Ship Bottom Paint Applications
This area was coated by PLA based ship bottom paints on the 16th of Dec 1999.
Performance tests of a ship on site
The Ship bottom was cheked on the 13th of Dec 2002.
Conclusion
1.Amorphous PLA resin is promising for coating applications. 2.Developments of biodegradable adhesives
and inks have been completed. 3.There are several possibilities to
commercialize PLA based Ship bottom paint and others.
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