ITR-2012

Amorphous PLA for coating applications

TOYOBO CO.,LTD. Vylon Department Takashi Miyamoto

CONTENTS

1. About TOYOBO 2. About VYLOECOL

Key features Molecular design Grades and each specification Applications
(1)Packaging material

(2)Ship bottom paint

3.Conclusion

About TOYOBO
Date of establishment: May 3, 1882 Date of incorporation: June 26, 1914 Paid-in capital: \51,730,003,166 Number of employees on a nonconsolidated basis: 3,238 (as of March 31,2011) Number 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).

Molecular design PLLA

Co-polymerization of D-lactic acid molecurar weight down

Amorphous PLA
D-lactic acid

Pigment dispersible ionic group Tg adjustment aliphatic momomer

Grades and each specification

Grade weight (103) Tg ( group Biobased content (wt%) Typical application

BE-400 BE-430

43 25 25 25

50 50 30

Pigment dispersion

1 00 99 90 60

Heat seal adhesive Gravure ink binder Primer coating Dry lamination adhesive

BE-600 BE-910

Crosslinking

-10

Crosslinking

Solution viscosity of VYLOECOL (Solvent: Ethyl-acetate )

1000

BE-400 BE-910
B[dPas]
100

10

1 25 30 35 40 NV[wt%] 45 50 55

Solid content

Packaging material
Dry laminate adhesive application Substrate: Cellulose nonwoven 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

Substrate:25m PLA film Coated layer thickness: 3m 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
Dry lamination adhesion strength (N/cm) PLA resin/Cross linking agent (wt ratio) 100/0 1.2 100/5 4.1 100/10 3.2 100/15 3.0

Resin grade BE-910

Coated side Coating to one side

The Biodegradability of Cross-linked BE-910 - ISO14855, by OWS 100 90 80

Biodegradation (%)

70 60 50 40 30 20 10 0 -10 0 5 10 15 20 25 30 35 40 45

Time (Days)
Cellulose BE91OHX5 BE91OHX10

Heat-sealing property; Print side Cellophane 20m Heat-sealing property Water vapor barrier property Anti-blocking property PLA derived resin coat m each)

Cellophane and coat resin both are biomass products that are derived from renewable resources, and also holds the Biodegradability.

GFML Comparative Table

Test Item Coat resin Thickness Weight Tensile strength
Elongation at break

Unit

GFML#300
(coating Cellophane)
PLA derivative

PL#300 (Cellophane) 0.020 30.0 38 25 28 59 5.6 4000 2.5

mm g/m2

0.022 33.0 30 19 31 68 4.4 180 2.8

MD TD MD TD

N/15mm width N/15mm width cc/24hatm g/24hr

Oxygen permeability1
Moisture permeability

Haze

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

Paint Layer Self-polishing Layer (hydrolysis of resins) Sea Water (-CH2-CH-) C=O OTypical Resin M2+ (oil-based) OC=O R (-CH2-CH-) C=O ONa+

Antifouling Agents

Typical requirements for Resins 1. Resistance to cold flows 2. Suitable hydrolysis rates 3. Suitable solution viscosity

Cold flow test

Sample resins were coated on a disk. The disk spins round at 30 knots speed. Sailing model test

Good sample NG sample

Results of cold flow tests

Good

Cold Flow 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

Acrilic resins(Cu2+ ) 2.5 PLA ( Mg2+) 2 PLA 1.5 1 0.5 0 5 10 15 20 25 Time (day) 30 Hydrolysis rate(%)

Solution viscosity and ionic species

( 1460dPa.s) 200 Solution viscosity (dPa.s) Mg Ca 150 Cu

100

50

0.3

0.35

0.4

0.45

0.5 0.55 Reduced viscosity(dl/g)

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.

Thank you for your attentions

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