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辐射固化介绍-沙多玛


Radiation Curing Technology
Kenji Mar.2012

What is Radiation Curing?

What is Radiation Curing?
? “Reacted in Place Technology”
?Polymerization of reacti

ve molecules by the action of “radiation” ?Fast curing time (Dry time < 1 Second) ?Potential for 100% reactive ingredients

? Two possible radiation sources
?EB (Electron Beam) ? Curing by accelerated electrons in the engery range of 90 to about 250 KeV (Kilo-elektron-volt) ?UV (Ultra-Violet ) ? Curing by UV-light in the specific wave length of 240 to about 420 nm

2

What Can UV/EB Curing do for you?

Printing Inks
Inkjet Screen Flexo Offest

labels, banners, posters, coding and marking, etc.

DVD/CDs, shirts, hats, glass, flyers, posters, wood, etc.

plastic, paper, or cardboard.

Cigarette package Wine package Labels Magazines,etc

4

Coatings
Wood And Vinyl Automotive Electronics Applicances

Flooring, Cabinets, Doors, Windows, Mouldings Furniture, etc.

Refinish, Lambs, Glass, Plastic parts,etc

Laptops, Cellphones, LCD, Touch panels, Optical films,etc

Fridge TV, Air-conditioner, etc

5

Adhesives

Labels

Medical

Industrial

Labels on glass, plastic bottles, along with adhesive labels used for other food, beverage, pharmaceutical and other packaging materials.

medical applications such as: syringes, Intravenous delivery systems, endoscopes, hearing aids, Dental fillings, etc.

Industrial grade bonding and fixing of glass, metal, electronics, and plastic devices. Ideal for industrial manufacturing processes.

6

What is the benefit of UV/EB Curing?

Comparison with conventional coatings
Solvent-Borned Systems
V.O.C.

Physical drying Solvent evaporation
Solvent
Polymer

Final Film

8

Comparison with conventional coatings
Water-borned Systems
V.O.C.

Water

Physical drying: evaporation and particles of coalescence
Water Coalescing agent

Final Film

Polymer
9

Comparison with conventional coatings
Radiation Curing

hn

Crosslinking
Oligomers Monomers

Final film

Photoinitiator

10

Environmental Advantages
? Environmentally friendly – “Green Technology” ? Reduce or eliminate solvent emissions
? Acrylate monomers are used as reactive diluents to lower viscosity for application ? Potential for 100% solids coating system ? Low or no Volatile Organic Compound’s (VOC)

? VOC solvents directive 1999/13/CE in the EU
? End of 2007 a maximum amount of VOC emissions is imposed. ? Depends on the volume of solvent used per year ? Pressure on VOC reduction will continue

11

Production Advantages
? Reduce or eliminate solvent recovery costs ? Reduce cleaning costs ? UV or EB energy consumption cost less than gas-fired ovens or driers
?90 k/year average for conventional solvent or waterborne ?15 k/year UV curing unit

? Smaller production space for energy curing systems
?Space needed using UV curing is 10 times less than air drying ?Typical space for thermal oven : 50-100 m? ?Typical space for a UV oven : 5 – 10m?

? Increased Productivity and Output
?Immediate curing (less than 1s) – Time is money! ?Moderate temperature increase during the curing process ?Immediate processing of the object after curing ?No need to cool down before stacking

? Technology easily adapt to existing production lines
12

Performance Advantages
? Ease of formulation changes
? ? ? ? Large raw material selection Hundreds of discreet backbone structures Functionality and backbone chemistry are easily varied New polymer is formed with each small formulation change

? Better performance from final cured product
? Systems can range from very hard to very flexible ? Improved resistance to abrasion, scratch

? Excellent chemical and stain resistance
? Acids, bases, water, solvents, household stains, etc…

? Improved heat resistance ? Allow to use of heat sensitive substrates

13

Disadvantages of UV curing
? Curing Thickness
?UV is absorbed by the formulation, does not penetrate very deep ?Limited thickness : 100?m usually considered as the max for high speed lines ?Higher thickness transparent coatings can be cured but at slower speeds

? Pigmented Systems
?UV is very prevalent in press inks ?Inks have much higher optical density ?Pigments compete with UV Photoinitiators – thin inks are best ?Formulations can be complicated

? Somewhat limited flexibility
?Curing mechanism induces shrinkage, stress generation hence adhesion is sometimes difficult ?Optimal performances needs crosslinking, crosslinking makes flexibility difficult ?But we always have products in our portfolio to solve this issue

? Complex, 3D Shapes are difficult to cure
?Requires special lamp systems and processes to distribute UV equally ?Dual curing technology can be a solution (peroxides or isocyanates) ?New plasma curing systems are being developed

14

EB versus UV

UV UV
Photo-initiator required (higher cost) N2 not always required Thickness and transparency limitation

EB EB
No Photo-initiator required Required N2 for free radical composition Can cure even opaque materials

No special licence requirements Oxygen inhibition
Able to cure 3-D objects Lower cost for UV unit

May required for state license No Oxygen inhibition
Limited to 2-D objects Much higher cost for EB unit

15

Formulation Comparisons

Formulation Comparisons
? UV Systems
? Monomers
? Reduce viscosity for application ? Reactive “solvents” ? Provide polymer’s properties

? Conventional Systems
? Solvents
? ? ? ? Volatile Contribute to VOC Subject to Regulation violation Reduce Viscosity for Application

Solvent!

17

Formulation Comparisons
? UV Systems
? Oligomers
? Backbone of the formulation ? Provides most of the mechanical properties

? Conventional Systems
? Resins
? Physical properties are preset from the resin manufacturer ? Less formulating latitude

18

Formulation Comparisons
? UV Systems ? Conventional

Monomer 25-100% Oligomer 0-75%

Resin 10-60%

Solvent 40-90%

Photoinitiator 0.5-10%

Additives 0-2% Pigments/Fillers 0-50%

Catalyst 0-6%

19

Mechanisms of photo-polymerization

Free Radical Propagation

PI

hv [PI]?

[PI]? R1 ? + R2? R1-M?

?Energy Absorption ?Radical Generation ?Initiation ?Propagation

R1? + M R1-M? + n M R1-MnM? + XH R1-MnM?

R1-MnMH + X?

X?

+M

XM?

?Chain transfer ?Termination
21

R1-MnM? + R1-M? R1-MnM? + R2
?

R1-MnM-M -R1

R1-MnM-R2

Cationic UV Curing
O

O

X:R

, ...

Photoinitiator : Ar3+SbF6-, Ar2I+SbF6-, …
Ar2I XArI *X+ +

UV

ArI *X-

+

+
ArI

Ar*

(Example : x = SbF6)

+

RH

+ R* + HX
H O X+

O HX

+
H O X+

R R O H R n XO
+

O

R

+
R

n

R

22

Free radical Vs Cationic initiation

Feature Cure Speed Post Cure Oxygen Inhibition Moisture Sensitivity Base Sensitivity Shrinkage Adhesion Durability Raw material

Cationic

Free-Radical Fast

Moderate?Fast Yes No
Yes Yes Small Good?Excellent Fair Limited

No
Yes

No No
Moderate Moderate?Excellent High Extensive
23

Electromagnetic Spectra

Light (visible radiant energy) has color names, but UV does not. UV is generally divided into three or four ranges. These ranges are general and not precisely defined, but are useful in distinguishing long, medium, short and vaccum wavelength UV. Electron Beam wave length is much shorter and hence generates a hudge amount of energy (? No need to use photoinititors) 24

Through and Surface Cure
short UV wavelength

More competition against PI at short wavelength

Long UV wavelength

Pigments Fillers Stabilizers Fillers

Pigments Stabilizers

Additives

Additives

Monomer
Oligomer

Monomer
Oligomer

SUBSTRATE

SUBSTRATE
25

Photo-initiator Selection
Long UV wavelength short UV wavelength PI with Absorption between 350-440 nm

PI with Absorption between 200-350 nm

Applications: clear/unpigmented coatings thin pigmented coatings

Applications: Pigmented coatings, Inks Thick coatings (>100 ? m)
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