innovative approach by advanced additives in expansion of ... · +ao-20 for long term heat...

Ryo Yokoyama, Naoko Dai, Naoshi Kawamoto

Polymer Additives R&D Laboratory, ADEKA Corporation

Innovative Approach by Advanced Additives in Expansion of Applications of Polyolefins

1

PP

PE

PVC

ABS

Engineering plastic

Super engineering plastic

HV cabel

[パーセンテージ]

Other cable and

the others

11%

Demand of Plastic Compounds in 2017

2

PP and PE

Automotive

37%

Appliances

25%

Consumer/House

wares

21%

Other

11%

Packaging

6%

PP: 5,400 kton

PE: 740kton

Property of ADEKA Corporation Proprietary – To be maintained in confidence

Consumer/House

25%

wares

Total: 66,000 kton

Quoted: Market Analysis Report from FUJI KEIZAI 2018

ADEKA’s Additives can contribute to expand the market of polyolefin compound 2

Contents

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

1. Flame Retarded(FR) with Extreme Performance

2. Light Stabilizer for Agricultural Film in Severe Sulfur Condition

3

4 Property of ADEKA Corporation

Proprietary – To be maintained in confidence

1. Flame Retardant for Polyolefin Compounds

Applications:

Stadium Chair, Electronics Enclosure

5

Demand of Flame Retarded Plastics

1975

940

1623

1054

892

709

1327

862

237 kT

Epoxy

Polyesters

Polyolefins

PVC

ABS

PA

PS

PU

PET/PBT

Applications of FR Polyolefins

Property of ADEKA Corporation


Quoted: Townsend Solutions Plastic Additives 2017

Demand of FR plastics in global: > 9,600 kton

etc..

E&E

Automotive W&C

Stadium chair Building

Demand: 290kton

By Polymer type

FR used for Polyolefin and ADEKA’s Solution

68.06

139.8

28.4

27.6

kT

Aluminium Trihydrate

Brominated type

Chlorinated

Phosphorous

The largest quantity of Flame retarded polyolefins is by Br type even now. However, PP with Br type FR can not achieved the requirement on weatherabiltiy, long term heat resistance…



Demand for E&E application : 290 kton

6

ADEKA’s solution is ADKSTAB FP-2500S +GF for High Flame retardancy +AO-20 for Long term heat resistance +LA-402AF for Weatherability

Quoted: Townsend Solutions Plastic Additives 2017

Br-FR / Sb2O3 ADK STAB FP-2500S

Strong Fire Dark smoke

Weak Fire Intumescent Layer

These combustion behaviors are notably different with respect to the fire intensity and smoke.

Both samples are classified UL-94 V-0, but burning behavior differs :

7

Combustion Behavior of Flame Retarded PP

Intumescent system is a shield formation on the polymer surface

Intumescent system blocks radiation and depresses pyrolysis gas diffusion.

Fire Source Polymer Surface

Intumescent shield

Shield it from • Heat radiation • Pyrolysis gas diffusion

Radiation

Pyrolysis gas

O2

8

ADK STAB FP-2000 series

Intumescent System

UL Verified Mark

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

FP-2500S has obtained the UL Verified Mark for the first time in functional materials

9

UL94 5V Achievement by FP-2500S in GFPP

Formulation 1 2 3 4

PP-b[MFR=30] 70 68 47 40

FP-2500S 30 32 23 30

GF(SGF) 30 30

Flame retardancy @ 1.6mm

UL-94V V-2 V-0 V-0 -

UL-94 5V NR NR NR 5VA

Some internal parts of copy machine and EV are required to pass UL94 5VA (High class of UL standard).

Property of ADEKA Corporation Proprietary – To be maintained in confidence

Combination of FP-2500S and GF can achieve 5VA.

10

PP impact copolymer [MFR=30]

11

Properties Method Unit

FP-2500S

(30%)

30% GF

Density g/cm3 1.365

F. M ASTM D790 MPa 8,200

Tensile Elongation ASTM D648 % 4.1

Tensile Strength ASTM D648 MPa 73.2

HDT/A at 1.82MPa ASTM D648 ºC 145

Charpy Impact

notched at 23ºC ASTM D6110 kJ/m2 5.8

Flame

Retardancy/1.6mm UL-94V V-0

Flame

Retardancy/1.6mm UL-94 5VA 5VA

*PBT/FR

with

10% GF

1.49

4,700

3.5

90

205

5.1

V-0

-

If TS and HDT meet requirements, 30% GF/PP containing FR-1 would be an alternative for engineering plastics.

*Reference) Polyplastics HP

Properties of GF-PP with FP-2500S

12

Heat

Rele

ase R

ate

(kW

/ m

2)

ADK STAB FP-2500S retained its flame retardancy after oven aging.

bad

good 0

200

400

600

0 5 10 15 20

APP Before oven aging

After 1500 h

Total HRR at 4 min. 0 h : 12 MJ/m²

1500 h : 61 MJ/m²

bad

good 0

200

400

600

0 5 10 15 20

Before oven aging

After 1500 h

Total HRR at 4 min. 0 h : 10 MJ/m²

1500 h : 16 MJ/m²

ADK STAB FP-2500S

Heat Resistance of FP-2500S after Oven Ageing at 150oC

Time / min

Combination of FP-2500S and AO-20 can maintain the performance.

13

Heat Resistance of FP-2500S after Oven Ageing at 150oC

Weatherability and Flame Retardancy

Formulation ICP [96.4- X] / FR [X] / Beige pigment [3] / AO-60 [0.1] / 2112 [0.1] / Ca-St [0.1] / LA[0.3]

The combination of FP-2000 series with LA-402AF shows the excellent weatherability without reducing flame retardancy.

0

20

40

60

80

100

0 1000 2000 3000

Glo

ss r

etai

ne

d ［

%］

With ADK STAB LA-402AF

Br-FR/Sb2O3(18%/6%)

FP-2500S (32%)

Exposure time / h

FP-2500S / LA-402AF Flame retardancy maintained after 3000h

Application example： Outdoor building materials, Stadium chair, Automotive etc.

Xenon- W-O-Meter (65oC, with spray)


Proprietary – To be maintained in confidence 14

With ADK STAB LA-402AF

15

Summary

ADEKA’s Solution is ADKSTAB FP-2500S, +GF for High Flame Retardancy +AO-20 for Long Term Heat Resistance +LA-402AF for Weatherability

You can enhance the performance as you need for each application

16

2. Light Stabilizer for Agricultural Film

in Severe Sulfur Condition

Application: Greenhouse Film



Types of Agricultural Film

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 Global Trends & Forecasts to 2017 MarketsandMarkets

©PIXTA

©PIXTA

©PIXTA

17

Global Demand of PO for Greenhouse

0

500

1000

1500

2000

2017 2018 2019 2020

Am

ou

nt

of

PO

Demand of PO compounds for greenhouse has been continuously increasing.

1.44 million ton

(KMT/Year)

18

*Agricultural Films Market Global Trends & Forecasts to 2017 MarketsandMarkets

Trend of Greenhouse Film

S

H2SO3 H2SO3

S S

Hot Plate Sulfur

Agrichemical spray

Cl

S

P

N

H

X

Inactivation

Sulfur fumigation

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.

19

Light Stabilizers in Evaluation

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)

20

Characteristics of LS-1 (ADK STAB LA-81)

NC11H23O O N OC11H23O

O

Features Low basicity

Low polarity

(good compatibility with polyolefins) LS-1 (ADEKA STAB LA-81)

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

21

Evaluation Condition

Formulation ・LLDPE (MFR=2.0) : 100

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

Light stabilizer (1.0-2.0)

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 • Each 120h (Severe Condition)

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

22

Sulfur Fumigation Methodology

0

1000

2000

3000

4000

5000

0 1000 2000 3000

pp

m

Exposure Time (h)

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

3,000ppm Sulfur at 2,000h

23

Tensile s

trength

(M

Pa)

0

10

20

30

40

50

60

LS-1 LS-2 LS-2 LS-3

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

1%

LS-2

1% 1%

LS-2

2%

Weatherability -Tensile Strength-

Elo

ngati

on r

ete

nti

on (

%)

0

20

40

60

80

100

120

LS-1 LS-2 LS-2 LS-3

840h

1200h

2040h

LS-2 showed the best weatherability among other LS from tensile elongation point of view under severe sulfur fumigation condition

With Severe Sulfur Fumigation

1%

LS-2

1% 1%

LS-2

2%

Weatherability -Elongation Retention-

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 26

Conclusion

Conventional LS

>3000 ppm

1500~3000 ppm

< 1500 ppm

LS-2

LS-1, LS-2 and LS-3

Positioning of Light Stabilizer p

erf

orm

ance

Sulfur fumigation level High

Low

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

27

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Thank you for your Attention !!

innovative approach by advanced additives in expansion of ... · +ao-20 for long term heat...

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