03 Amorphous PLA for Coating Applications Miyamoto PDF

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

®

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).

®

®

®

®

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

®

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

●

● ●

●

● ●

●

●

●

● ●

● ●

● ● ● ● ●

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.

All Rights Reserved

ﾌﾟﾚｾﾞﾝﾃｰｼｮﾝ用

Thank you for your attentions