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Positively Innovative

Durable fluoropolymer coating base

ZEFFLE for PV 25 08

2015

法律声明：本讲义只作交流学习之用，内容仅供参考，转载需经原作者同意并注明出处，本组委会保留一切法律追诉的权利，此活动的最终解释权归亚洲光伏创新论坛所有。

・Daikin Industries ・Fluorochemicals ・Fluorocoating ZEFFLE GK ・ZEFFLE GK application example ・ZEFFLE GK for PV backsheet


3

Daikin Industries

Corporate Data

Company Name Daikin Industries, Ltd.

(Head Office: Osaka , Japan)

Incorporated 1934（founded in 1924）

Capital 85 billion yen

Sales 1,783 billion yen (fiscal 2013:consolidated)

Number of

Employees 56,240 (March, 2014:consolidated)

Number of Group

Companies

209 consolidated subsidiaries (28 in Japan; 181 overseas) (March, 2014)


4

Daikin Industries

Daikin Group Companies : 209 companies （March,2014）

Ratio of Overseas Sales 71%

（fiscal 2013:consolidated）

Japan 5,128 (29%)

Overseas 12,703

(71%)

Japan 29%

China 18% Asia &

Oceania 13%

Europe 14%

Americas 20%

Other

(hundred million yen)

Sales Breakdown by Global Region


5

Properties of Fluorine Compounds

Unique properties of Fluorine Compounds

Chemical

resistance

Low gas

permeability

Heat

resistance

Water and Oil proof

Non- stick Anti-fouling

Lubricity

Weather

resistance

Insulation

performance

Flame

resistance

Low

refractive

index

We are driven to give innovative solutions for our partners based on these properties and our core technologies.


6

Fluorochemical Manufacturing Process

A wide variety of Fluorochemical products

Offering a wide variety of Fluorochemicals deriving from fluorspar.

Monomer

Sulfuric

acid

H2SO4

Anhydrous fluoric acid

HF

fluorspar

Fluorocarbon gas

Fluoropolymers

Fluoropolymer Films

Fluoroelastomers

Fluoro Coatings

Water and oil repellents

Fluorinated anti-

fingerprint Coatings

Mold release agents

Additives

Fluorinated intermediates

Fluorinated oils, etc.

Chloro-

form etc. Etching agents


7

base monomer weather ability

bake or

cure

onsite paint

chemical resistance

soil remove ability

chlorine

2F base excellent high temp.

bake unable bad fair free

3FCl base fair rt～ cure

able fair fair chlorine

4F base ZEFFLE GK excellent

rt～ cure

able excellent excellent free

Fluoropolymer transition for various exterior coating

year

1970 1980 1990

Coating material developing history


8

Chemical structure of ZEFFLE GK (４F type)

Tetra fluoro ethylene

Polyflon Teflon

ＰＴＦＥ

C C

F F

F F

Feature: Weatherability Chemical resistance Heat resistance

Fault: Poor solvent solubility High temp bake No compatibility

Resolving fault as it leaves the feature

Modifying

C C

H H

Y H

OH

C C

H H

Z H

C C

F F

F F F F

C C

F F

TFE

Cross-linkage

Coatability Compatibility with additives

TFE

Weatherability Chemical stability Heat resistance


9

ZEFFLE GK Conventional Acrylic urethane

3 Y 6 Y

Coating surface after exposure (By SEM)

Gloss retention White panel (TiO2), exposure slope: 30°facing south

0

20

40

60

80

100

120

0 1 2 3 4 5 6

%

Glo

ss

R

ete

nti

on

ZEFFLE GK

Acrylic urethane

0

20

40

60

80

100

120

0 1 2 3 4 5 6 7 8 9 10

Years of Exposure

% G

loss

Rete

nti

on

ZEFFLE GK (Clear)

Acrylic

in Okinawa

in Florida

ZEFFLE GK

Acrylic

urethane

Weather Resistance test for ZEFFLE coating


10

Machine Supplier Light Source Test Condition

QUV QUV/se Q-Panel Lab

Products

UVB-313 ASTM D4587

4hours UV/60℃

4hours condensation/50℃

The Accelerated Weathering Test Condition

Accelerated durability Test for ZEFFLE coating

ZEFFLE GK

Acrylic


11

ZEFFLE GK（±0ｕ）

initial 45μm

QUV-2000h 45μm

Polyurethane （－14ｕ）

initial 45μm

QUV-2000h 31μm

ＱＵＶ-test (2000ｈ)

45μ 45μ 31μ

45μ

Accelerated durability Test for ZEFFLE coating


12

・Bond energy C-F: 485kJ/mol (strong) C-Cl: 326kJ/mol (weak) ・MAX UV energy -------- 411kJ/mol

⇒C-Cl: bond cleavage

weak

CTFE

Cl

ZEFFLE 4F:TFE

TFE

very strong

CTFE

Cl

UV

Cl -

3FCL：CTFE

C C

F F

F F

C C

F F

Cl F

Advantage of ZEFFLE 4F


13

Advantage of ZEFFLE 4F ～Dispersibility～

0

1

2

3

4

5

370 390 410 430 450

%T

nm

Light transmittance ZEFFLE

4F B

Light transmitta

nce

25μ

2.67% (450nm)

4.06% (450nm)

P/B (TiO2/Resin) = 0.83, Solid cont.=58%

0

10

20

30

40

50

60

0 50 100

Dis

pe

rsib

ilit

y

20°

Gro

ss

Disper time（min）

Daikin ZEFFLE 4F Fluorocoating A Fluorocoating B


14

S-UV 1000h ※clear paint on white board

ZEFFLE 4F Fluorocoating 3F Acrylic type

Advantage of ZEFFLE 4F ～Weatherability～


15

ZEFFLE GK application example

Monorail in Okinawa

青岛海湾大桥

武汉天兴州大桥


16

南京

大胜关

长江大桥

苏通

长江大桥

嘉绍跨江

大桥

杭州湾

大桥

辽河

特大桥

泸州泰安

长江大桥



17

港珠澳大桥海中桥隧工程总长约35.6km，其中香港段长约6km，粤港澳三地共同建设的主体工程长约29.6km。主体工程分为桥梁工程和岛隧工程两部分，其中桥梁工程长约22.9km.

钢箱梁涂装面积为570万平方米，氟碳树脂用量在280T左右。



18

Coating

Coating

Film

Film EVA side

EVA side

PET

PET

Adhesive

C C

F F

Cl F

C C

F F

F F

C C

H F

H H

PVF type (1F) F: 41wt%

C C

H F

H F

PVDF type (2F) F: 59wt%

TFE type (4F ZEFFLE GK) F: 76wt%

CTFE type (3FCl) F: 49wt%

F-Film type backsheet

F-Coat type backsheet

PET polyethylene terephthalate

F-type Backsheets of various kinds


19

ZEFFLE GK

ZEFFLE GK

F-Film

F-Film

PET Film layer

F-Film layer

38～20μm

ZEFFLE Coating

ゼッフル塗膜層

PET Film layer

10～13μm

No adhesive between ZEFFLE and PET/EVA.

Reduction in fluoro-layer thickness by more than half

F-Film EVA side EVA side

Polyester Polyester

Adhesive

ZEFFLE coating layer

Advantage of ZEFFLE Backsheet


20

Backsheet Technical Data ～Weatherability～

Test with S-UV Tester (UV 100mW/cm2 :12hrs ⇔ 95%RH :12hrs)

100/100 (0hr) 100/100 (600hrs)

40

60

80

100

0 200 400 600

(%)

(hr)

F-film type （38μ）

F-coat type (10μ)

PET

Nylon type

PET multilayer (containing barrier layer）

ZEFFLE GK / PET / ZEFFLE GK (10μ）

Retention of Tensile Strength

Adhesion of ZEFFLE (cross-cut test)

tape

peel

substrate


21

Backsheet Technical Data ～Weatherability～試験機：サンシャインウェザーメーターサンプルサイズ：60×50mm

ﾌｨﾙﾀ条件：　#255放射照度：　78.5 W/㎡ (300-400nm)BPT ：　63℃槽内湿度：　50%rhスプレー：　120分中18分

倍率：100倍0h 1000h

B-1

KPT

B-2

TPE

B-3

ZPE

B-4

PPE

KPX

TPX

ZPX

PPX

0h 1000h

BS photo after

SWOM 1000h

78.5W/m2(300-400nm) 63℃、50%RH shower:18min/120min

Results of collaborative research with

Suga Weathering Technology Foundation スガウェザリング技術振興財団


22


Sunshine WOM 78.5W/m2(300-400nm) 63℃、50%RH shower:18min/120min

Super Xenon WOM 180W/m2(300-400nm) 63℃、50%RH shower:18min/120min

Results of collaborative research with Suga WeatheringTechnology Foundation

スガウェザリング技術振興財団


23


Results of collaborative research with Suga WeatheringTechnology Foundation

スガウェザリング技術振興財団

KPX TPX ZPX PPX

Outdoor-exposure test for 18months at Suga Test Instruments (東京新宿)

⊿E 5.64 8.00 2.29 8.60 ⊿YI 6.56 4.36 1.96 4.43


24

Module Technical Data ～Weatherability～

Results of collaborative research with AIST consortium 産総研コンソーシアム

Retention of generating efficiency after Damp heat 3500hrs

DH elapsed time [hrs]

Pow

er

gen

era

tion

eff

icie

ncy

keep

ing

rati

o

Film BS

(FFC-30)


25

Module Technical Data ～Weatherability～

Pmax: 96.4%

Pmax: 27.0%

Pmax: 45.8%

Pmax: 15.7%

ZPE Coating BS

DH4000 initial

uncorroded

corroded

corroded

corroded

Results of collaborative research with AIST consortium

Film BS


26

non-fluorinetype

Film type Coating type Film type

Disperse pigment ★ ★★★ ★

UV shielding ★ ★★★ ★

Weatherability ★★★ ★★★ ★

Thickness 20～40μm 10～30μm 30～50μm

Adhesive necessary unnecessary necessary

Cost ★ ★★ ★★★

Cost performance ★★ ★★★ ★★

fluorine type

ZEFFLE

Advantage of ZEFFLE Backsheet ～Conclusions～


27

南非lesedi 155MW 高沙窝50MW

And more・・・


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