New LED UV booster for 剂
1
Kevin Poelmans, JoAnn Arceneaux, Steven Cappelle, Ellie Chen2
• Medium Pressure Hg Lamp vs UV LED Footprint
2 • 普通汞灯于UV LED的比较
• Major Market Trends and Technology advantages/disadvantages
• UV LED市场动向以及技术优化劣势对比
3
• Surmounting the Obstacles
• 解决方案
4
• Formulation & Discussion
• 配方与讨论3
Major market trends in UV LED – DRIVERS 市场趋势
Compact & scalable design of product line 高信赖设计理念，
保证了设备的稳定性、可靠性及固化的一致性
Instantaneous turning on and off 瞬间开关
Constant output 恒定输出的光照强度
Ease of handling heat-sensitive substrates 对热敏基材有利
Reduced electricity consumption 减少用电量
Increased lifetime – LED chips last ~ 30 000 operating hours
增长寿命
Reduced maintenance 降低了维护成本
No hazardous UVC & UVB wavelengths 没有UVC&UCB波长危害
Low operating temperatures 工作温度低
No O3 and no Hg 无臭氧和汞污染UV LED Technology, Perceived
Advantages/Disadvantages UV LED技术的优势与劣势
• Narrow emission band – energy efficient 发射波长窄 – 能量利用率高
• No or limited heat generation towards substrate 不产生热量，有利于热敏感基材
• Environment friendly 环保的
• Switch on / Switch off 随时开关
• User safety and flexbility in use 用户安全与便利
4
• Surface cure issues 表面固化问题
• Limited choice of PI 光引发剂的选择问题
•No beneficial effect of higher temperature in reaction speed 常温固化
反应速度问题5
Content-目录
1
• Medium Pressure Hg Lamp vs UV LED Footprint
2 • 普通汞灯于UV LED的比较
• Major Market Trends and Technology advantages/disadvantages
• UV LED市场动向以及技术优化劣势对比
3
• Surmounting the Obstacles
• 解决方案
4
• Formulation & Discussion
• 配方与讨论Medium Pressure Hg Lamp vs UV LED Footprint
普通汞灯于UV LED的比较
• Hg lamp: UVC, UVB, UVA, Visible light (可见光), IR红外线
• UV LED UVA, Visible light (可见光) → very narrow范围很窄
• Actual emission of LED is near the visible light wavelength range
• LED实际发光的波长范围与可见光很接近
6= T↑
UV Wavelength Penetration and Absorption
UV波长穿透与吸收
• Hg UV: All zones in the coating receive a certain amount of energy 汞灯UV可以覆盖所有区域
• LED wavelengths only reach the deeper layers of the coating LED波长只能在深层起作用
• No IR wavelengths, so no heat build up 没有红外线波长则没有热量产生
7
UV-C UV-B UV-A UV-V
Coating
涂层
Substrate
100 – 280
nm
280 – 315
nm
315 – 400
nm
400 – 700
nm
Hg UV
Bulk中间
Through 深层
IR
700 – 1800
nm
UV LED UV Wavelength Absorption UV吸收波长
8
LED 395 nm
• UV LED Cure: not only does the light not reach all layers of the coating, also the choice of
commercial PI that absorbs in this narrow band is very limited. UV LED固化：不仅不能覆盖所有
层面，与之配合的光引发剂的选择也非常有限。
• The ones that do absorb light in the region of 395 nm are intended for through cure optimization15 September 2018 9
UV LED
UV-A UV-V
Coating
Substrate
315 – 400
nm
400 – …
nm
Bulk
Through
O2
O2 O2
O2
O2
O2 O2 O2
O2 O2 O2
O2
O2 O2 O2 O2
O2
O2
O2 O2
O2
O2
O2
O2
O2
O2 O2
O2
O2
O2
O2 O2
O2 O2 O2
O2
O2
O2 O2 O2
O2
O2
O2
O2 O2
O2 O2 O2
O2 O2
O2
O2
O2
O2
O2 O2
O2
O2
O2
O2
O2 O2 O2
O2 O2 O2 O2 O2 O2
O2
O2 O O2
2 O O2
2
O2
O2
O2 O2
Oxygen Inhibition 氧阻聚
= SURFACE CURE ISSUES
表面固化问题15 September 2018 10
CONTENT-目录
1
• Medium Pressure Hg Lamp vs UV LED Footprint
2 • 普通汞灯于UV LED的比较
• Major Market Trends and Technology advantages/disadvantages
• UV LED市场动向以及技术优化劣势对比
3
• Surmounting the Obstacles
• 解决方案
4
• Formulation & Discussion
• 配方与讨论How to overcome oxygen inhibition?
11
Method Advantages Disadvantages
Inert Gas 通入惰性气体 Does not adversely affect coating
properties不改变漆膜特性
Expensive; difficult to implement
成本高,实施性差
Waxes 蜡 Inexpensive/成本低 Affects final coating properties;
time needed for migration
Films 覆膜 Good solution when film becomes
part of product
Cost/disposal of film when not part
of product
Increase PI Concentration
增加引发剂 Easy to implement
Increased residuals/by-products;
reduced coating properties; cost
Increase Light Intensity光强 May not affect coating properties Part of existing equipment; cost
REACTIVE CHEMICALS:化学反应
Thiols 硫醇
Improved thermal resistance;
reduced moisture absorption;
improved adhesion
Odor; stability of formulations; cost
Amines 胺 Inexpensive; possible improved
adhesion
Yellowing upon or after cure;
residual odor; moisture sensitivity
Ethers 醚 Can be used in large quantities
Affects coating properties; reduced
temperature resistance; possible
reduced water resistanceHow to keep Oxygen
Method 方法
Inert Gas blanket
Waxes
Protective Films
Increase PI Concentration
Increase LED power
Chemical modification:
(Abstractable) Hydrogen donors
活泼的氢供体
Mon-O-O Mon-O-O-H + R
R-H
Mon
R-Mon
Mon
Mon
● ●
●
Thiols > Amines > Ethers
硫醇类 > 氨类 > 醚类13
BINDERS 树脂
• Cost-effective 低成本
• High Reactivity 高反应活性
• Coating Properties 涂料性能
DILUTING ACRYLATES 单体
• Reactivity 反应活性
• Diluting power 稀释能力
LED BOOSTERS LED助推器
• Thiol UV LED booster 硫醇类
• Amino UV LED booster 氨类
ram
14
BINDERS 树脂
• EB 3700 (Epoxy Acrylate; good reactivity, high chemical resistance 环氧丙烯酸酯，高反应活性，
高耐化学性)
• EB 3639 (Modified Epoxy Acrylate; high reactivity, high flexibility, good chemical resistance 改性
环氧丙烯酸酯，高反应活性，高柔韧性，良好耐化学性)
• EB 8465 (Aliphatic Urethane Acrylate; good reactivity, good chemical resistance, low color;
benchmark used in this studies 脂肪族聚氨酯丙烯酸脂；良好的反应性，良好的耐化学性，
低黄变；LED UV固化研究的标杆树脂)
DILUTING ACRYLATES 稀释型
• EB 81 (Modified Polyether Acrylate 改性聚酯丙烯酸酯)
• EB 892 (tetrafunctional Polyester Acrylate; moderate reactivity, good chemical resistance 四官能
聚酯丙烯酸酯，快速反应和良好耐化学性)
LED BOOSTERS LED 助推剂
• EB P115 (tertiary amine coinitiator; excellent reactivity 氨类助引发剂，优异的反应
速度)
• Additol LED01 (Mercapto LED booster, NPAL stabilized, 硫醇类LED固化助推剂)15 tion 试配方
EBECRYL® 8465(3‐functional UA)
DPGDA
ADDITOL®ADDITOL LED 01
IRGACURE®2100
65
10
20
5
Viscosity (mPa.s) 4000
Application : Barcoater , thickness as mentioned
Curing : LED 8W/cm2
395 nm, geometry LED and distance LED to substrate as
mentioned16
Reactivity – Coating thickness
反应性-漆膜厚度
10µm 30µm
Distance LED to substrate (cm)
5x 3
5x 3
5x 4
15x 1
15x 1
15x 2
0.5
1
2
SPF, on Leneta, thickness as mentioned
Reactivity (m/min) ‐ tacky with Carbon
Significant lower reactivity for thin coatings (<20µ) 1517
Reactivity ‐ Viscosity & Dilution
反应性-稀释黏度
EBECRYL®8465
DPGDA
ADDITOL® LED 01
IRGACURE®IRGACURE2100
49
26
20
5
57
18
20
5
65
10
20
5
Viscosity (25°C, mPa.s)
Fingernail resistant(m/min)
Gloss at 60°(%)
1000
5x1
90
2000
10x1
90
4000
15x1
90
Application : 30 µm on Leneta paper
Cured with 8W /cm2 395nm LED at 1cm substrate lamp distance,
Cure speeds drops with increasing DPGDA dilution.18
剂含量
EBECRYL® 8465
DPGDA
ADDITOL® LED 01
EBECRYL®892
IRGACURE® 2100
65
10
0
40
5
65
10
20
20
5
65
10
40
0
5
Viscosity(25°C, mPa.s)
Cure speed (m/min)
2300
5 x 4
2400
5 x 1
2500
40 x 1
40m/min with 40 parts LED boosterPart of 响
19
Ø Key oligomer 主体树脂反应性
Ø Distance LED to substrate LED灯到基材的距离
Ø Coating thickness 漆膜厚度
Ø Viscosity & Dilution 稀释黏度
Ø Dosage of LED booster助推剂比例20
• Medium Pressure Hg Lamp vs UV LED Footprint
2 • 普通汞灯于UV LED的比较
• Major Market Trends and Technology advantages/disadvantages
• UV LED市场动向以及技术优化劣势对比
• Surmounting the Obstacles
• 解决方案
4
• Formulation & Discussion
• 配方与讨论Printing technologies
• Flexography 100 – 500 mPa.s
• Roller printing 300 – 600 mPa.s
• Screen printing >1000 mPa.s
• Digital printing 5 – 20 mPa.s
• Litho ink > 50,000 mPa.sUV led application for package
UV LED在印刷中的具体应用
22
(1) Label and package标签和包装
用于标签打印的UV LED固化系统能提高生产率、降低能耗、降低较薄基材的热负荷、减少
聚酯薄膜片用料、并且对环境造成的影响较低。
(2) Shrink sleeve for bottle 瓶子印刷
UV LED固化技术可充分用于瓶标签机上；系统经设计后可直接打印到圆柱形容器上。光源
体积较小，很适合安装到空间有限的印刷机上。而热负荷的降低也实现了在较薄、热敏性较
高的基材上进行打印。
(3) Code and marking printing 编码和标记
UV LED固化灯的结构紧凑、性能先进、能耗低，很适合编码和标记打印。UV LED 可瞬间开
/关，所以只有在油墨固化时打开即可；这就更一步节省了能源、并延长了装置的使用寿命。
Others…Goal of the booster development
助推剂开发方向
23
•Increase reactivity 增加反应性
- Principle: Increase surface cure by re-activating slow propagating peroxyl
radicals and generating fast propagating ones.通过重新激活缓慢传播的过
氧自由基并产生快速传播的自由基来增加表面固化。
- Amine chemistry chosen to be most suitable选择胺类化学物质是最合适
-硫醇：引发效率高，气味大，价格高，稳定性差
-胺类：气味低，成本低，稳定性好，引发效率稍低Goal of the booster development
助推剂开发方向
24
•Design of the new product 新产品设计
- High amine content dramatically without losing acrylic double bonds 在丙
烯酸双键基础上增加胺含量
- Make booster polymeric: REACH exempt (for EMEA market), positive effect
on migration (LM) 增强聚合
- Cost effective 成本效益Value Proposition – EBECRYL LED 03
25
ØImproves adhesion, gloss and color strength. 增强附着力，光泽，色强
Ø Gives formulators more latitude in the formulation due to low viscosity, great effect at low
proportion and good rheology.由于粘度低，在低比例下具有很好的效果和良好的流变性，
使配方设计师在配方中具有更大的自由度
Ø Is uniquely designed for low migration applications. 低迁移设计
ØEBECRYL LED 03 can be used to either increase UV LED cure speed at existing PI
concentrations, or maintain UV LED cure speed at reduced PI concentrations. EBECRYL LED 03
可用于在现有PI浓度下提高UV LED固化速度，或在降低PI浓度时保持UV LED固化速度
LED03:
Amine Value: 166
Viscosity: 450 mPa.s
Color: 0.5 G•Pilot UV LED Unit：UV LED装置
- 365 nm 8W/cm² air-cooled Firejet 365nm-空气冷却装置
- 395 nm 8W/cm² water-cooled RX Fireline 395nm-水冷却装置
- Mounted on 1 conveyor 安装在同一个传输带上
- Distance to substrate 1 cm 到基材的距离为1cm
•Coatings & inks application:
- Leneta paper & plastic substrates
卡纸和塑料基材
- Layer thickness depending on application:
膜厚根据应用来调整
- Clear coating: 15µ
- Ink: 4 µ
Application & TEST conditions in lab trials
应用和实验室测试条件UV LED OPV formulation
OPV光油测试
27
Formulation Reference Less PI
EBECRYL LED
03 with less PI
EBECRYL 7100
with less PI
EBECRYL P115
with less PI
EBECRYL 3700 34 37 37 38 54
TMPEOTA 53 42 42 41 25
EBECRYL 145 (NPG(PO)2DA) 15
EBECRYL LED 03 15
EBECRYL 7100 15
EBECRYL P115 15
PI blending 13 5 5 5 5
Total 100 100 100 100 100
Viscosity @ 25˚C (cP, 100 s
-1
) 381 600 694 670 654
Cure speed(m/min) 70 10 70 40 50
Shrink(4 is the best) 2 4 3 1 1
Yellowing(Δb 72hr QUV) 3.5 1.2 2.7 3.8 4.528
IMPACT ON UV LED inkjet application
喷墨应用测试 Example Pigment paste
Ebecryl 151® 68,4
Stabilizer 1
Pigment wetting additive
package
5,6
PIGMENT 25
Example REFERENCE
IJ SPF
MODIFIE
D IJ SPF3
Pigment paste 20 20
Ebecryl 152® 72,5 62,5
TPO-L 6 6
DETX 1,5 1,5
EBECRYL® LED 03 10
0
5
10
15
20
SPF UV inkjet
ink
+ 10%
EBECRYL® LED
03
0.8
17.5
0.8
20
0.8
20
0.8
20
Yellow Cyan Black Magenta
(m/min)Impact on inkjet ink properties
喷墨应用
29
40
30
70
60
50
90
80
REF SPF EBECRYL LED 03
Viscosity (500 Hz), cP
CYAN
MAGENTA
YELLOW
BLACK
0.7
0.6
1
0.9
0.8
1.2
1.1
REF SPF EBECRYL LED 03
Optical Density
CYAN
MAGENTA
YELLOW
BLACK
80
70
60
REF SPF EBECRYL LED 03
20° Gloss
100
90
CYAN
MAGENTA
YELLOW
BLACK
50
40
Addition of EBECRYL LED 03 increases viscosity, optical density, and gloss + Optical Density & Gloss improvedREF LED03 LED03
EB 452 (PEA; 4f) 26,7 25 23,4
EB 145 (PO-2f) 26,7 25 23,3
PETIA (3,5f) 26,6 25 23,3
LED Booster - 5 10
PIGMENT (C: PAC
15:4)
20 20 20
TPO-L/DETX (50/50) 6 6 6
Wetting & dispersing
additive
3,8 3,8 3,8
Defoamer additive 0,48 0,48 0,48
FLEXO TEST formulation
柔印测试
Viscosities LED03 LED03
Shear rate 1.1 (mPa.s) 803 1410 1370
Shear rate 2500
(mPa.s)
439 573 712
30
Yellow
Cyan
Magenta
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
REF
LED03 5% LED03
10%
1.0
2.8
8.3
1.0
2.5
10.0
1.0
2.8
8.3Out look for Litho
胶印展望
Ø higher amine content up to the level where it doesn’t destroy
ink-water balance
提高胺含量并保证不影响水墨平衡
Ø Viscosity adjustment for tack
调整黏度使得与粘性匹配
Challenge for Litho ink:
ink-water balance 水墨平衡
Pigment wetting 颜料润湿性
High viscosity & Low tack 高黏度&低粘性www.allnex.com
结论与展望
Conclusions and outlook
• Challenges by changing from UV to LED
- Surface cure 表面固化
- Photo initiator 光引发剂
- Lamp power LED灯
- Color system 有色体系
• State of the art technical routes
- Physical and chemical 物理方法&化学方法
- Drawbacks for each of the possibilities 每一种可能性的劣势
• Development of a new LED Booster
- Higher amine content 高胺含量
- Higher reactivity 高反应性
- Examples from OPV, flexo and ink jet 在OPV, 柔印以及喷墨中的应用
- Litho ink 胶印油墨应用15 September 2018
Thank you
Ellie Chen
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