( " ) ( ) : 2009-0078142

(N uclear Infra C onstruction)

EB (D e s ig n o f H ard C o a tin g R e s in s

a n d P ro c e s s O p tim iza tio n o f EB C u rin g )

.

EB (

) .

2010. 07.

:

:

:

"

- 1 -1

.

2009-0078142

2009.04.01

2010.03.31

(1)/

(1)

EB

: 2

: 2

:

: 30,000

:

: 30,000

: 2

: 2

:

: 30,000

:

: 30000

: :

( 500 ) 32

/EB

in-mold decoration(IMD) foil

EB .

IMD

Erichsen 12 mm /EB .

EB

3H , 0.31 .

EB

UV EB

.

( 5 )

IMD,

IMD, hard coating, resin, electron beam, curing, process optimization

2

.

l . : EB

n .

()

. IMD foil

. IMD foil

EB

.

EB

. /

. EB

. EB

. UV UV

gravure ink offset ink UV

prism sheet UV

. EB UV

EB

.

EB ( EB

) EB

.

m .

IMD /EB

EB

IMD .

.

EB

(FT- IR ) ( )(steel wool abrasion

)(Erichsen ) (SEM ) . EB

/UV /EB

.

- 3 -

.

IV.

IMD .

/EB Erichsen 12 mm

. 3H 0.31

. EB

. UV UV

EB .

V .

(EB)

.

. EB

(VOC) .

.

EB

. EB

. 1) /EB

2) EB EB 3)

UV EB IMD /EB

.

- 4 ~4

.

S U M M A R Y

Many companies have discovered the advantage and benefits of electron beam (EB)

curing over conventional coating systems. Some of these advantages include environmental

compliance, rapid cure, and improved physical properties and performance compared to

conventional systems. However, there are extensive difficulties in selection of resins

suitable for EB curing which will allow formation of good quality in a low-cost

commercially satisfactory manner. There are also remained a need for processing

optimization which would allow the commercial exploitation of EB curing.

It is an object of this study to develop a system of EB curing resins which will be used

as the hard coating layer of in-mold decoration (IMD ) foils. It is a further object of this

study to establish a relationship between processing conditions and coating properties. It is

an additional object of this study to provide a database for the selection of apparatus

which would allow the commercial exploitation of EB curing.

The EB curable resins and curing techniques, which will be developed for the hard

coating layer of IMD foils can be used in a variety of applications such as protective

coatings, printing inks, photoresists, adhesives, sealants and plastic parts for three

dimensional imaging because it allows many industries to exploit the EB curing cycle's

advantage to reduce the processing time and costs while meeting the demanding

requirements of high-performance products.

- 5

.

C O N T E N T S

Chapter 1. Outline of the research project................................................................................................................8

Chapter 2. Present status of technical development............................................................................................10

Chapter 3. Contents and results ....................................................................................................................................17

Chapter 4. Research achievement and contributions........................................................................................ 28

Chapter 5. Application plan of research results .....................................................................................................30

Chapter 6. International technology information in the process of development 3 1

Chapter 7. Reference..........................................................................................................................................................32

.

1. ...............................................................................................................................................8

2. ...........................................................................................................................................10

3. ................................................................................................................................17

4. .................................................................................................................28

5. .................................................................................................................................... 30

6. ................................................................................................31

7. ..................................................................................................................................................................... 32

- i -7

.

1.

In mold in mold decorationQMD) in mold labelingQML) .

IML

. die cutting

. IMD

. 3

. IMD

( 1).

1. IMD

IMD IMD foil IMD foil

. IMD foil

PET film Release layer (3) Hard coating

layer (4) Anchor layer I(5) Anchor layer II(6) Color layer (7) Anchor layer III(8)

Anchor layer IV(9) Al metalizing(10) Anchor layer V(11) Adhesive layer

. 5 ym IMD

.

in mold

. 3H

.

(dual cure) .

hydroxyl carboxyl

UV EB(electron beam)

- 8 -

.

. hydroxyl isocyanate

roll blocking

in mold 3

.

.

IMD foil . IMD foil

EB

. EB

.

/ . EB

. EB

.

leveling,

. UV UV gravure ink offset ink

UV prism sheet

UV .

EB UV

EB

. EB

( EB )

EB

.

- 9 -

.

2.

1. UV I960 80W

UV .

. 1 UV/EB 2003

. graphic art

.

kton

Segment NA Europe Japan ChinaCoatings 28 27 16 16

GA 39 23 10 4

Electronics 10 3 15Adhesives 3 2

total 80 53 43 20AGR% 4 6 7 25

1. UV/EB (2003)

ApplicationMarket (ty)

2000 2001 2002

Cotings 15,710 16,260 16,290Wood coalings 8,000 7,650 7,400PVC floor coating TOO TOO mFilm coalings 280 330 480Metal coatings 300 290 280Vac. Coatings 2.300 2,500 2,800Cpti1 disk coatings 390 0 560Cptlcal fiber coalings 2.300 2.7 2,300Ceramiccoaiings 1,200 1,300 1,500Release coatings 240 250 270

Inks 8,340 6.730 9,200Offset ink G.OOO 6,2M G,40Gravure ink 1.290 1.310 1,340Metal coatings ink 0 650 800Sikscregn ink 440 490 530Flexoinh SO 130

Photoresists 16,700 13,980 15.120Dry film resist 3,000 2.200 2,300Liquid resist 5,900 5.300 5,800Eldctro-deposition resist 320 300 320Resistfor LCD 1,800 1.600 1, 0Barrier rib lor PDF 90 160 400Ssmicorductor resist 3.600 2. 0 2,600Photo polymer plate 2,000 1,900 1,900

Others &50 960 1,460Rapid prototyping 50 60 60Adh iv 600 900 1,400

Total 41,400 , 930 42,070

2. UV/EB

10

.

2 UV/EB . UV/EB

.

( 3).

Monomers

RadicalAcrylatesVinylsOthers

Cationic

Cycloaliphatic epoxides Glydgyl ether Vinyl ether Oxetane

Oligomers

Radical

Epoxy acrylates Urethane acrylates Polyester acrylates Acrylic polymer acrylates Silicone acrylates Unsaturated polyesters

Cationic

Cycloaliphatic epoxides Glydgyl ether Vinyl ether Oxetane

Initiators

Radical

BenzophenoneAcetophenoneThioxanthoneAcyl phosphine oxideOthers

Cationiclodonium salt Sulfonium salt Others

Anionic Dithio carbamate salt

3. Photo curable

epoxy, urethane, polyester, acrylic polymer silicone

.

: isocynate

( polyester diol

)UV/EB

( 50 nm filler

)/ (/

)dual cure ( urethane

UV/EB .

) EB (EB

. EB PMMAPC 4 )

/ .

- _11

.

.

EB UV/EB 10%

. EB 100 UV (5-20

) 20-50 UV

photo initiator additives UV

.

2. EB

.

2 . 2

100 eV . 200 keV

1 2000 2 .

2 2

EB .

. (C)

12 6(Au) 197 79. 16.4

197 98.5 .

1:1.2 25% .

80% (1/1.25)

. . 2

2 2 . EB

EB .

EB .

LET(Linear Energy

Transfer) .

. EB EB EB

2 3 . PE PS EB

.

12

.

2.

3.

EB (1)

? ? (2) ?

.

.

100 Gy

. PMMA 10 kGy .

10 kGy

.

3.

UV EB

.

. EB

UV

.

.

.

(Differential Scanning Calorimery DSC)

J

en

erg

y

2e