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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
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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
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Introduction
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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
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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)
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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.
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Newly developed light stabilizer
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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)
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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
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Advanced light stabilizer technology
in Greenhouse film application
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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
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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
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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
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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
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Machine for tensile test
SHIMADZU AG-Xplus
Speed:500mm/min
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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
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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
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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
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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
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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
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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
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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
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Conclusion
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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.
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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