Property of ADEKA Corporation, Proprietary – To be maintained in confidence

Newly developed high performance

light stabilizer for greenhouse films

20th International Conference Indian Petrochem-2018

Shinichi Ishikawa Head of Technical Services, General Manager

Additives Solution Department, Polymer Additives R&D

ADEKA Corporation

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 2

Newly developed light stabilizer

Introduction

Conclusion

• Characteristics of newly developed light stabilizer

• Identification of light stabilizer

• Agricultural PolyOlefin (PO) film market information

Advanced light stabilizer technology in Greenhouse film

application

• Weatherability under medium sulfur fumigation condition

• Weatherability under severe sulfur fumigation condition

Agenda

• Trend of the Greenhouse film

• Optimization of sulfur fumigation condition

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 3

Introduction

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 4

Applications Usage Requirement Period

[year]

Percentage

[%]*

Greenhouse

• External covering

• Long term

weatherability

• Transparency

• Heat retention, etc

3 < 38

Mulch

• Ground covering

• Keeping ground

temp.

• Weed suppression

• Mid term

weatherability

• Color is Black,

Silver, Green, etc

1~3 37

Silage

• Wrapping

preservation of grass

• Disposable

• Adhesion during

storage

< 1 25

Long term weatherability has been required for greenhouse

application, so the suitable light stabilizer system has to be used.

*Agricultural Films Market by Applications & Polymers –Global Trends & Forecasts to 2017

Types of Agricultural film

©PIXTA

©PIXTA

©PIXTA

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 5

0

200

400

600

800

1000

1200

1400

1600

1800

2000

2017 2018 2019 2020

Am

ou

nt

of

PO

Demand of PO compounds for greenhouse has been continuously increasing.

Global demand of PO for greenhouse

1.44 million ton

*Agricultural Films Market by Applications & Polymers –Global Trends & Forecasts to 2017

(KMT/Year)

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 6

S

H2SO3 H2SO3

S S

Hot Plate Sulfur

Agrichemical spray

Cl

S

P

N

H

X

Inactivation Sulfur fumigation

Trend of Greenhouse Film

Low basicity HALS should

be necessary for long-term

use of greenhouse.

The greenhouse films used for long term are exposed to sunlight, so high

weatherability is most important.

HALS is essential to give long-term weatherability for agricultural film.

However

Pesticide, Sulfur etc… are used for preventing damage to crops from disease

and harmful insects. Especially sulfur fumigation is increasing, 2,000 =>

3~4,000ppm in agricultural film

On the other hand, HALS is

inactivated by sulfur and pesticide

due to acid-base reaction.

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 7

Newly developed light stabilizer

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 8

Identification of light stabilizer

LS-2: 50% Active Component LDPE MB

Main component : LS-1 (ADK STAB LA-81)

Pellet Form

LS-1 (ADK STAB LA-81)

High M.W. (>2000)

Conventional LS (ADK STAB LA-94G)

N N

N N

HN

(CH2)6 N

HN

NH CH2

n

NC11H23O O N OC11H23O

O

NO-Alkyl type HALS

LS-3 NO-Alkyl type HALS (commercially available)

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 9

Characteristics of LS-1

NC11H23O O N OC11H23O

O Features Low basicity

Low polarity (good compatibility with polyolefins)

Basicity of LS-1 and other HALS

LS-1

Solubility of HALS

4.3

11.4

11.6

0 5 10 15

ConventionalLS

LS-3

LS-1

pKb *using pH meter in MeOH

HALS Heptane Methanol

LS-1 >50 0.1

LS-3 1.4 0.3

conventional

LS 4.2 0.1

(g/100g-solvent)

LS-1 is expected to have an excellent

compatibility with polyolefin

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 10

Advanced light stabilizer technology

in Greenhouse film application

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 11

Formulation • LLDPE (MFR=2.0) : 100

• Phenolic AO-1 (0.05%) / Phosphite P-1 (0.10%) / Ca-St (0.05%)

Light stabilizer (1.0 or 2.0%(LS-2))

Evaluation Condition

Processing condition of blown film

• Single screw extrusion

φ20mm L/D=25

• Ring die

diameter : 25mm, slit width : 0.8 mm

• Film thickness : 40~50 μm

• Fold width : 80~90 mm

• Temperature : 190℃

• Winding speed : 4.5~5.0 m/min

Sulfur fumigation condition

• Condition A (Severe)

• Condition B (Medium)

Accelerated weathering test ISO 4892-2 (Xenon-Weather-O-Meter)

• Radiation : 60 W/m²

• WL region : 300-400 nm

• BPT : BST65 ºC with water spray

Evaluation condition

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 12

Initial color after processing Photograph of film after processing

w/o LS LS-2 LS-1 LS-3 Conventional LS

LS-2 has no negative influence on the initial color of film

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 13

0

0.05

0.1

0.15

0.2

0.25

w/o LS LS-1 LS-2 LS-3 ConventionalLS

Δ C

.I.

500h 1000h 3000h

w/o sulfur fumigation

Weatherability –ΔCarbonyl Index-

LS-2 showed same weatherability as other LS in case of no

sulfur fumigation

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 14

0

1000

2000

3000

4000

5000

0 1000 2000 3000

pp

m

Exposure Time (h)

Optimization of sulfur fumigation condition

PO film was exposed to sulfur fumed by

heating of sulfur on the hot plate in a box.

PO film was put under weathering test.

• Amount of sulfur: 5.0 g

• Heat condition: 160 ⁰C, 4 h

• Sulfur fumigation cycle:

Once every 120h exposure

Sulfur fumigation condition

Sulfur fumigation treatment model Sulfur fumigation treatment

4,000ppm Sulfur at 3,000h

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 15

Machine for tensile test

SHIMADZU AG-Xplus

Speed:500mm/min

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 16

Weatherability ~Tensile strength~

0

10

20

30

40

50

60

LS-1 LS-2 LS-3 Conventional LS

Ten

sile

str

engt

h (

MPa

)

0h 840h 1200h 2040h

Degradation

Standard

With severe sulfur fumigation

LS-2 showed the best weatherability among other LS from tensile

strength point of view under severe sulfur fumigation condition

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 17

Weatherability ~Elongation retention~

With severe sulfur fumigation

0

20

40

60

80

100

120

140

LS-1 LS-2 LS-3 Conventional LS

Elo

nga

tio

n r

eten

tio

n (

%)

840h 1200h 2040h

LS-2 showed the best weatherability among other LS from tensile

elongation point of view under severe sulfur fumigation condition

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 18

Summary-1

Better initial color stability

No issue on weatherability with no sulfur condition

The best weatherability under severe sulfur condition

Advanced Light Stabilizer, LS-2, could provide…

Sulfur fumigation condition…

• Amount of sulfur: 5.0 g

• Heat condition: 160 degree C, 4 hours

• Sulfur fumigation cycle: Every 120 hours exposure

Following sulfur fumigation condition can achieve 4,000ppm

sulfur content at 3,000 hours exposure… severe condition

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 19

0

1000

2000

3000

4000

5000

0 1000 2000 3000

Medium sulfur fumigation condition

• Amount of sulfur: 5.0 g

• Heat condition: 160 ⁰C, 4 h

• Sulfur fumigation cycle:

Once per 120h exposure

Severe

Sulfur fumigation conditions

• Amount of sulfur: 5.0 g

• Heat condition: 160 ⁰C, 4 h

• Sulfur fumigation cycle:

Once per 360h exposure

Medium

Sulfur fumigation conditions

0

1000

2000

3000

4000

5000

0 1000 2000 3000

pp

m

Exposure Time (h)

4,000ppm Sulfur at 3,000h

2,000ppm Sulfur at 3,000h

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 20

0

10

20

30

40

50

60

LS-1 LS-2 LS-3 Conventional LS

Ten

sile

str

en

gth

(M

Pa)

0h 2040h

Weatherability ~Tensile strength~

Degradation

Standard

With medium sulfur fumigation

LS-2 showed the best weatherability among other LS from tensile

strength point of view under medium sulfur fumigation condition as well

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 21

0

20

40

60

80

100

120

LS-1 LS-2 LS-3 ConventionalLS

Elo

nga

tio

n r

eten

tio

n (

%)

Weatherability ~Elongation retention~

With medium sulfur fumigation Exposure Time: 2,040h

LS-2 showed same weatherability as LS-1 and LS-3 from tensile

elongation point of view under medium sulfur fumigation condition

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 22

Summary-2

The best weatherability under medium sulfur

condition as well. However, the performance of LS-1

and LS-3 should also be acceptable.

Advanced Light Stabilizer, LS-2, could provide…

Sulfur fumigation condition…

• Amount of sulfur: 5.0 g

• Heat condition: 160 degree C, 4 hours

• Sulfur fumigation cycle: Every 360 hours exposure

Following sulfur fumigation condition can achieve 2,000ppm

sulfur content at 3,000 hours exposure… medium condition

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 23

Conclusion

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 24

Conventional LS

>3000 ppm

1500~3000 ppm

< 1500 ppm

LS-2

LS-1, LS-2

and LS-3

Conclusion

Positioning of Light Stabilizer p

erf

orm

an

ce

Sulfur fumigation level

High

Low

LS-2 is the most suitable light stabilizer under high sulfur fumigation condition.

Property of ADEKA Corporation, Proprietary – To be maintained in confidence 25

Thank you for your attention !

Local Contact:

ADEKA India Pvt. Ltd.

B-206 & 207, Dynasty Business Park, Andheri Kurla Road,

J.B. Nagar, Andheri East, Mumbai-400 059

Tel:+91-22-4026-3301/2