用于包装涂料和油墨的LED固化助推剂

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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