Perstorp's Paul Kelly gave a presentation at Chinacoat 2013 on Intermediates for the design and control of Hard and Soft UV curing coatings.

1. Intermediates for the design
and control of Hard and Soft
UV curing coatings
用于设计和控制硬质和柔感紫外光固化涂料的中间体
Paul Kelly
Perstorp Group

2. UV curable coatings with customized physical
characteristics
 Tg
 modulus
 impact strength
 hardness
 resistance
can be achieved !
by design and control of polyol intermediate
定制紫外光固化涂料的物理特性如:
 Tg
 模量
 抗冲击强度
 硬度
 耐受性
均可实现！
利用对多元醇中间体的设计和控制

3. Content
目录
 Introduction to Perstorp
 柏斯托简介
 Hard Coat overview
 硬质涂料概览
 Soft feel / Soft Touch Introduction
 柔感/柔软触感简介
 Glass Transition
 玻璃态转变
 Parameters affecting Tg
 影响 Tg 的参数
 Preliminary results
 初步结果
 Conclusions
 结论

4. Introduction to Perstorp
Sustainable solutions through
innovative chemicals
柏斯托简介
通过创新化学品实现的
可持续解决方案

5. Perstorp Today
今日柏斯托
The Perstorp Group
柏斯托集团
 1881 – Perstorp was formed
 柏斯托成立于 1881 年
 Family owned for more than 100 years
 拥有超过 100 年历史的家族产业
 Since 2005 controlled by PAI partners,
a French private equity company
 自 2005 年由法国私募股权公司 PAI 合
作伙伴控制
 Approximately 1,500 employees in
22 countries
 约 1,500 名员工分布 22 个国家和地区
 Annual turnover of around
1.3 billion EUR
 World leader of several products for
resins and paints
 年营业额约 13 亿欧元
 世界领先的几款产品于树酯与涂料应用

6. From raw materials
to end product
从原材料
到最终产品
 The foundation of the Group’s
activities is considerable expertise
in organic chemistry, particularly
aldehydes
 我集团业务的基础主要涉及有机化学
领域，尤其是醛类
 We are among the largest global
producers of Penta and TMP
polyols, specialty polyols, and
organic acids with a highly
integrated production tree
 我们是全球最大的 Penta（季戊四
醇）、TMP（三羟甲基丙烷）多元醇、
特种多元醇和有机酸生产商之一，拥
有非常完整的产品系列

7. Sales office & agents
销售办事处和代理商
Sales offices
1. Germany
2. France
3. Italy
4. Netherlands
5. Poland
6. Russia
Regional hub
East Europe - Moscow
7. Spain
8. Sweden
16. China
Regional hub
North Asia - Shanghai
Regional hub
West Europe - Perstorp
9.
10.
11.
12.
Turkey
United Kingdom
Argentina
Brazil
Regional hub
Latin America – São Paulo
13. Chile
14. Mexico
15. USA
Regional hub
North America - Toledo
17. India
Regional hub
South Asia/ME/Africa - Mumbai
18.
19.
20.
21.
22.
Japan
Korea
Singapore
Taiwan
United Arab Emirates

8. Hard coats and Soft Feel
硬质涂料和柔感

9. Hard
硬质

10. Hard applications
硬质应用
“Opto-electrical”
applications
光电应用
Other “rigid” plastic
applications
其他“刚性”塑料应用
Automotive
applications
Industrial
metal
applications
Graphics
Glass
applications
油墨应用
汽车应用
玻璃涂料应用
工业金属应用
Screens
Cosmetic packaging
(lipsticks, compacts etc.)
Pipes
保险杠
屏幕
Bumpers
管道
化妆品包装
Scratch resistant
inks and coatings
Bottles
瓶子
耐划伤油墨和涂料
Films and panels
Helmets
Wheel trims
Housings
Signage
薄膜和面板
头盔
轮框
外壳
标牌
Optical fibres
Skis
Headlights
光纤
滑雪板
灯头
Cosmetic
packaging
化妆品包装
Mobile telephones
Household appliances
(Vacuum cleaners etc.)
Motorcycle
Fairings
家用电器
摩托车整流罩
Building products (Frames,
door handles etc.)
Interior
plastics
建筑产品
内饰塑料
移动电话
Computers
电脑
Solar panels
Medical
太阳能电池板
医疗设备
And many others!!!!!
还有更多其他选择！！！
Mirrors
镜子
Lens
镜片

11. Hard Coat requirements
for Scratch resistance
硬质涂料
对耐刮擦性能
As a general “rule of thumb”,
high cross-link density leads to improved
scratch resistance.
按一般“经验法则”，高交联密度可增强耐刮擦性。
高Tg 则不一定能产生良好的耐刮擦性。
Generally high Tg – Tg does not lead to
scratch resistance.
 High functional aliphatic urethane acrylate
and high functional monomers such as DPHA,
Di-PEPA, Di-TMPTA, PETIA are typically used
to give scratch resistance.
 High functional materials are often brittle
and can lose adhesion, due to shrinkage.
 Dendritic acrylate gives high scratch
resistance, toughness, low shrinkage
and adhesion.
 使用高官能度的脂肪族聚氨酯丙烯酸酯和高官能
度的单体(如 DPHA、Di-PEPA、Di-TMPTA 和
PETIA)都可获得较好的耐刮擦性。
 高官能度的产品通常较为脆，并且会缩边而导致
附着性不好。
 超支化丙烯酸酯具有良好的耐刮擦性、韧性、低
缩边和良好的附着性。

12. Scratch resistance comparison (scotchbrite)
耐刮擦性对比 (scotchbrite)
Gloss loss, %
14
Tg Comparison
BADGE DA = 60°C
DPHA
= 94°C
Hard UA
= Up to 85°C*
2F UA
= -25°C to 40°C*
Dendritic PA = 40°C to 75°C*
12
10
8
6
4
* = Typical value
2
0
DPHA
Dendritic
acrylate
BADGE DA
Flexible 2-func
epoxy acrylate
UA
Crosslink Density decreasing
 DPHA and Dendritic acrylates show lowest gloss loss
and highest scratch resistance
 The performance of BADGE DA indicates that hardness
is not the only requirement for scratch resistance.
(BADGE DA has quite low scratch resistance)
 DPHA和超支化丙烯酸酯的光泽度损失最小，耐刮擦性最好
 BADGE DA的结果显示硬度不是实现耐刮擦性的唯一必要
条件 。（BADGE DA 的耐刮擦性极低）

13. Dendritic Polymers
超支化聚合物
Characterised by
 Large number of primary hydroxyl
groups
 Densely branched polymer backbone
 Extensive formulation possibilities
特性
 大量伯羟基基团
 密集分支的聚合物骨架
 可制定丰富配方
General schematic view

14. Comparison of polyol for hardcoat
对比应用于硬质涂料的多元醇
Di-Penta
acrylate (DPHA)
Acrylate of
Boltorn P501
Acrylate of
Boltorn P500
13,000
600
500
30 mins
5H-6H
3H-4H
H-2H
72 hours
5H-6H
5H-6H
3H-4H
8H-9H
8H-9H
8H-9H
Δ % gloss
0.4
1.6
3.6
Final gloss
90.3
88.1
80.5
0.4
1.7
2.2
No
Yes
Yes
Acrylated Polyol type
Viscosity, mPas @ 23C
粘度
Pencil hardness
铅笔硬度
PC sheet
(250µ)
Glass
Scratch
(scotch brite, 50 rubs)
抗划伤性
Erichsen-flex
(Aluminium, mm)
柔韧性
Adhesion
(cross-cut, PC Sheet)
附着性

15. Soft Feel / Soft Touch / Haptic
柔感 / 柔软触感 / 触感

16. Soft touch applications
柔软触感应用
“Opto-electrical”
applications
Other “rigid” plastic
applications
Automotive
applications
Graphics
Glass
applications
Wood
Coatings
光电应用
其他“刚性”塑料应用
汽车应用
玻璃涂料应用
木器漆
Films and panels
薄膜和面板
Cosmetic packaging
(lipsticks, compacts etc.)
化妆品包装
Interior plastics
内饰塑料
Reports etc.
报告
Bottles
瓶子
Furniture
家具
Mobile telephones
移动电话
Helmets
头盔
Fake leather
effect
伪造皮效果
Signage
标牌
Decoration and
display
装饰和陈列
Flooring
地板
Computer
Housings and Mice
电脑外壳和鼠标
Skis
滑雪板
Cosmetic
packaging
化妆品包装
Household appliances
(Vacuum cleaners etc.)
家用电器
Pharmaceuticals
制药
油墨应用
Building products
(Frames, door handles
etc.)
建筑产品
Medical
医疗设备
And many others!!!!!
还有更多其他选择！！！

17. UV ”Soft-feel”
Requirements
UV“柔感”
必要条件
1. Soft-feel / soft touch effect
 Gives sense of luxury, high-quality
and comfort
 Described as haptic, soft-touch,
silky-peachy etc…
 Very subjective (a tactile perception)
 Problem to qualify and quantify
the effect.
1.




柔感 / 柔软触感效果
具有豪华、高品质的舒适感受
可称为触感、柔软手感、柔滑等形容词
非常主观的感觉（触觉）
难以对效果进行定性和定量。

18. UV ”Soft-feel”
Requirements
UV“柔感”
必要条件
2. Matt/ Gloss
 Usually matt coatings – few hundred
µm thickness
2. 哑光/高光泽度
 一般为哑光涂料, 厚度为几百 µm
3. Resistance
 Especially chemical & scratch
resistance – often more difficult to
achieve in matt
4. Adhesion
 Multiple substrates, so normal
requirements exist.
5. Etc, etc, etc.
 All of the normal requirements apply
3. 耐受性
 尤其是耐化学性和耐刮擦性 – 于哑光
涂料中较难实现
4. 附着性
 适合多种基材，要求简单。
5. 其他
 一般要求均能满足

19. Objective
目标
Design novel Urethane Acrylate based
on new speciality Polyols
基于新的特种多元醇设计新型聚氨酯丙烯酸酯
UV curing Haptic formulation
matting agents, powders and waxes
(Highly influential)
 Used to affect microstructure + topography
of the coating surface
 Controlled particle size
 Hardness influences
Coatings Resin properties –
(what we can design)
 Tg
 Crosslink density
 Flexibility
 Chemical & scratch resistance
 Viscosity
 Colour
 Cure speed
紫外光固化触感配方
消光剂、粉末和蜡（极具影响力）
 用于改善涂料表面的微观结构和形态
 可控粒径
 硬度影响
涂料树脂特性 – （我们能怎样设计）
 Tg
 交联密度
 柔韧性
 耐化学性和耐刮擦性
 粘度
 色度
 固化速度

20. Existing
Technology
现有
技术
 Solvent-borne 2K – Most widely used
 Waterborne polyurethane systems
 Focus on 100% UV curable
formulations
 双组分溶剂型 – 广泛使用
 水性聚氨酯体系
 专注于 100% 紫外光固化配方

21. Tg – Glass Transition
Temperature
Reversible transition from hard to “rubbery” state
 Measured by DSC (Differential scanning calorimetry)
or DMA (Dynamic Mechanical Analysis)
 Primary Tg is most commonly applied to thermoplastic
amorphous or semi-crystalline materials
 Primary Tg is just one transition that can be measured
in polymers
 Sometimes called “a” transition, “b” transition etc.
or “primary”, “secondary” etc.
 The “a” transition is generally the true Tg for
a thermoplastic material.
 In highly cross-linked systems, the “b” or secondary
transition measures rotations around and between
cross-links.
Tg – 玻璃化温度
由硬质到“弹性”状态的可逆转变
 通过 DSC(示差扫描量热法)或DMA(动态力学分
析)测得
 初级 Tg 最常用于无定形或半结晶热塑性材料
 初级 Tg 仅仅是聚合物中可测的一次转换
 有时被称作“a”转换、“b”转换等或“初级”、“次级”等
 “a ”转换通常是热塑性材料的实际 Tg。
 在高度交联的体系中，“b”或次级转换测量的是交联
体周围或交联体之间的旋转。
Mw between 2 crosslinking knots (Mc)
Thermoplastic behaves like noodles
热塑性像面条：
 Dry = solid
干=固体; 熟=移动
 Cooked = mobile
Thermoset is locked by cross-links
 a little like knitted wool
热固性的交叉链接有点像针织的毛绒。

22. Tg – For UV
Cured System
Tg – 适用于紫外光
固化体系
Reversible transition from hard to
“rubbery” state
 UV cured systems are typically “thermoset”
and cross-linked
 High functionality to ensure good resistance
properties
 Functionality must not be too high
or it will restrict transition
 Low secondary transition Tg is desired
to give soft feel
 Too low Tg will reduce resistance
properties
 Linear molecular chains allows
greatest control of Tg.
由硬质到“弹性”状态的可逆转变
 紫外光固化体系通常为“热固性”和交联型
 高官能度以确保良好的耐受性能
 官能度不能过高而影响转换受到限制
 低次级Tg可带来柔感
 过低的 Tg 会降低耐受性
 线性分子链可最大程度地控制Tg。

23. Required Properties
必要性能
Before Cure
 Viscosity – Liquid at room temperature
(∼40Pa⋅s)
 Mw (target 1,000 per acrylate funtionality)
 Formulation freedom
‒ control with reactive diluent or
”passive resin”
 Solvent free
 Low colour
 Compatible with powder additives
固化前
 粘度 – 在室温下呈液态 (~40Pa⋅s)
 Mw （每个丙烯酸酯官能度的目标为 1,000）
 配方设计自由
‒ 通过活性稀释剂或“钝化树脂”进行控制
 无溶剂型
 低色度
 与粉末添加剂相容
hv
After Cure
 Relatively low Tg (-20°C to -50 °C)
 MW between cross-links – target 1,000-2,000
 Relatively low crosslinking density
 Adhesion to plastics
 Flexibility
hv
固化后
 相对较低的 Tg（-20°C 至 -50°C ）
 交联体之间的分子量 – 目标为 1,000-2,000
 相对较低的交联密度
 可附着于塑料
 柔韧性

24. Urethane acrylate design
聚氨酯丙烯酸酯设计
Acrylate
“end cap”
丙烯酸酯封端
Aromatic or
aliphatic
Isocyanate
芳香族/脂肪
异氰酸酯
Aromatic or
aliphatic
Isocyanate
Acrylate
”end cap”
basic design
Functionality dictated by
 Polyol “backbone”
 NCO
 End cap
官能度取决于：
 多元醇主结构
 异氰酸酯
 封端
Much more than
innovative chemical
solutions

25. Why choose Capa™
”Backbone”?
为何选择 Capa™
“骨架”？
Characteristics associated with
Oligomers based on Capa™
 Flexibility
‒ Oligomers are flexible and tough.
 Low Viscosity
‒ Oligomers typically show lower
viscosity for equivalent Mwt.
 Durability
‒ Exterior durability.
‒ High abrasion resistance.
 Control of Tg.
‒ Possibility for “soft feel”
与基于 Capa™ 的低聚物相关的特性
 柔韧性
‒ 低聚物具有高弹性和高强度。
 低粘度
‒ 对比当量分子量，低聚物的粘度都低。
 耐久性
‒ 室外耐久性。
‒ 高耐磨性。
 Tg 的控制。
‒ 可形成“柔感”

26. Capa™
Capa™ Monomer
OHROH
Catalyst
Capa™ Polyol
The reaction is “ring opening”
“开环”反应
 low temperatures, less catalyst
and no water
 低温，催化剂少且不生成水
 clean polyester polyol, narrow Mw
distribution and clearly defined
functionality.
 高纯度聚酯多元醇、较窄的分子量分
布和清晰界定的官能度。

27. Capa™ Polyols
Capa™ 多元醇
 Grades can be tailored depending on type
of “initiator”.
 “Initiator” has significant effect
on properties.
 可根据“起始剂”的类型进行分级。
 “起始剂”对性能有显著影响。
 Functionality of the “initiator” repeated in
the polymer polyol, so di-, tri- and multi
functional polyols can be produced.
 “起始剂”的官能度能在聚合物多元醇中重
复出现，因此可生成二元、三元以及多官
能度的多元醇。
Capa 2 series – 200 – 8,000 Mw
Diols
Capa 3 series – 300 – 3,000 Mw
Triols
Putting the care
into chemicals

28. Capa™ polyol design
Capa™ 多元醇设计
Routes of investigation
 Adduct
 Direct acrylation
研究路线
 加合物
 直接丙烯酸酯化
1.
2.
O
 Capa extension
1,000 Mw per OH
 react with adduct
isocyanate/2-HEA
 异氰酸酯加合物/2-HEA
反映
O
O
O
 partial acrylation 部分丙烯酸酯化
 graft Capa 接枝
 react with di-isocyanate or adduct
NB. These materials are shown as tri-functional, but can be made as di-, tri, or multi-functional and
combined to achieve best balance of properties.

29. Control of crystallinity
结晶度控制
1. Careful selection of
“initiator”
2. Co-polymer
modification of polyol
1. 精心挑选“起始剂”
2. 共聚物改性的多元醇
Reduction of
crystallinity
in oligomers
based on Capa™
低结晶的Capa™低聚物

30. Experimental
实验
Viscosity comparison (20% TPGDA)
粘度对比
Sample 1. = 1.1 Pas
Sample 2. = 1.2 Pas
Two samples were prepared for comparison;
Both use 2,000 Mw caprolactone
制备两种样品用于对比；
均使用分子量为 2,000 的 Caprolactone（己内酯）
1. based on 2,000 Mw (Capa™ 2200A)
2. based on modified Caprolactone co-polymer
(Capa™ 612065).
1. 基于 2,000 的分子量 (Capa™ 2200A)
2. 基于改性 Caprolactone (己内酯) 共聚物 (Capa™
612065)。
In each case the polyol was made into a
polyurethane acrylate, using IPDI and HEA.
均使用 IPDI（异佛尔酮二异氰酸酯）和 HEA（丙烯
酸羟乙酯）将多元醇制成聚氨酯丙烯酸酯。
Both samples appeared similar immediately
after preparation.
经过制备后，两种样品的表现相似。

31. Experimental (cont.)
实验（续）
2h
2 小时 “未改性”样品开始变得“不
透明”
2,5 小时 开始变白
3 小时
完全变白，具有相当高的粘，
但仍不是固态
> 3 小时 已变为固态
“unmodified” sample starts
To look “opaque”
2,5 h It begins to look white
3h
It is completely white, really
high viscous but still not solid
> 3h It has become solid
NB. After 2 hours stored at 60°C, both
samples are liquid once more.
注意：在 60°C 下保存 2 小时后，两种
样品都再次变成了液体。
The “modified” sample remains clear throughout
“改性”样品仍保持完全透明

32. Preliminary study of Tg
(by DSC)
Tg 的初步研究
(示差扫描量热法)
The effect of chain length:
Functionality
 Using existing directly acrylated
polyols (Not UA)
 Tested as UV formulation
‒ acrylate resin (∼ 100% solid
content) + 4 wt% Irg 500
链度的影响：官能度
 直接使用现有丙烯酸酯化多元醇 (非
UA 聚氨酯丙烯酸酯)
 光固化配方测试
‒ 丙烯酸酯树脂（~ 100% 固含量）
+ 4%（重量百分比）Irg 500
Backbone type
Mn (g/mol)
Mn
per acrylate
Viscosity (Pa⋅s)
at 25/70°C
Tg (°C)
after UV curing
Capa™ (TMP core)
1,300
~430
0.48 / 0.07
-22
Capa™ (Penta core)
1,400
~350
0.65 / 0.08
-13
Capa™ (Di-penta core)
2,100
~350
1.2 / 0.136
-12
Rising Tg

33. Preliminary study of Tg
(by DSC)
Tg 的初步研究
(示差扫描量热法)
The effect of structure on Tg
and viscosity
 Type of NCO
 UA V/s Direct acrylation
 Ethoxylation
结构对 Tg 和粘度的影响
 异氰酸酯类型
 UA (聚氨酯丙烯酸酯) 对比 直接
丙烯酸酯化反应
 乙氧基化
Backbone type
Mn
(g/mol)
Mn
per acrylate
Viscosity (Pa⋅s)
at 25/70°C
Tg (°C)
after UV curing
(EO)TMP
+ IPDI/HEA
1,800
~600
390 / 3.9
-13
Capa™ (TMP core)
1,300
~430
0.48 / 0.07
-22
Capa™ (TMP core)
+ IPDI/HEA
2,500
~800
750 / 14
13
800
~130
21 / 0.33
77
1,100
~180
16 / 0.4
75
Penta + HDI
Penta + Tolonate™
(ex Vencorex)
As shown on previous slide

34. Conclusions
结论
 Tg can be controlled to allow formulation
of hard or soft coat formulations.
 Hard coats are greatly influenced by cross-link
density
 Dendrimer acrylate (BoltornTM) gives
balance of hardness resistance, Tg and
toughness.
 Soft feel formulation is more dependent
on the secondary Tg.
 A balance of cross-link density,
molecular weight and linear structure
gives best combination of resistance and
low Tg.
 High molecular weight Caprolactone based
Urethane acrylate gives resistance and
relatively low Tg, but crystallinity must be
controlled by use of copolymerisation with
Lactide.
 通过对Tg 的控制可获得硬质或软质涂料配方。
 硬质涂料主要受交联密度影响。
 超支化丙烯酸酯 (BoltornTM) 可实现硬度、
Tg 和韧性的完美平衡。
 柔触觉配方更多取决于 其次级Tg 。
 平衡交联密度、分子量和线性结构实现了
耐受性和低 Tg 的完美组合。
 基于高分子量 己内酯的聚氨酯丙烯酸酯具有耐
受性和相对较低的 Tg，但其结晶度必须通过与
丙交酯的共聚作用进行控制。

35. 谢谢
Contact – Paul Kelly
paul.kelly@perstorp.com