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

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

Content

Introduction to Perstorp

Hard Coat overview

Soft feel / Soft Touch Introduction

Glass Transition

Parameters affecting Tg

Preliminary results

Conclusions

柏斯托简介

硬质涂料概览

柔感/柔软触感简介

玻璃态转变

影响 Tg 的参数

初步结果

结论

目录

Sustainable solutions through innovative chemicals

Introduction to Perstorp

通过创新化学品实现的 可持续解决方案

柏斯托简介

Perstorp Today 今日柏斯托

The Perstorp Group

1881 – Perstorp was formed

Family owned for more than 100 years

Since 2005 controlled by PAI partners, a French private equity company

Approximately 1,500 employees in 22 countries

Annual turnover of around 1.3 billion EUR

World leader of several products for resins and paints

柏斯托集团

柏斯托成立于 1881 年

拥有超过 100 年历史的家族产业

自 2005 年由法国私募股权公司 PAI 合作伙伴控制

约 1,500 名员工分布 22 个国家和地区

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

From raw materials to end product

The foundation of the Group’s activities is considerable expertise in organic chemistry, particularly aldehydes

We are among the largest global producers of Penta and TMP polyols, specialty polyols, and organic acids with a highly integrated production tree

从原材料 到最终产品

我集团业务的基础主要涉及有机化学领域，尤其是醛类

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

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

Regional hub West Europe - Perstorp

9. Turkey 10. United Kingdom 11. Argentina 12. Brazil

Regional hub Latin America – São Paulo

13. Chile 14. Mexico 15. USA

Regional hub North America - Toledo

16. China

Regional hub North Asia - Shanghai

17. India Regional hub South Asia/ME/Africa - Mumbai

18. Japan 19. Korea 20. Singapore 21. Taiwan 22. United Arab Emirates

Hard coats and Soft Feel

硬质涂料和柔感

Hard

硬质

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 汽车应用

Industrial metal applications 工业金属应用

Graphics 油墨应用

Glass applications 玻璃涂料应用

Screens 屏幕

Cosmetic packaging (lipsticks, compacts etc.) 化妆品包装

Bumpers 保险杠

Pipes 管道

Scratch resistant inks and coatings 耐划伤油墨和涂料

Bottles 瓶子

Films and panels 薄膜和面板

Helmets 头盔

Wheel trims 轮框

Housings 外壳

Signage 标牌

Mirrors 镜子

Optical fibres 光纤

Skis 滑雪板

Headlights 灯头

Cosmetic packaging 化妆品包装

Lens 镜片

Mobile telephones 移动电话

Household appliances (Vacuum cleaners etc.) 家用电器

Motorcycle Fairings 摩托车整流罩

Computers 电脑

Building products (Frames, door handles etc.) 建筑产品

Interior plastics 内饰塑料

Solar panels 太阳能电池板

Medical 医疗设备

And many others!!!!! 还有更多其他选择！！！

Hard Coat requirements for Scratch resistance

As a general “rule of thumb”, high cross-link density leads to improved scratch resistance.

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.

硬质涂料 对耐刮擦性能 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。 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。

Scratch resistance comparison (scotchbrite) 耐刮擦性对比 (scotchbrite)

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)

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* * = Typical value

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）

0

2

4

6

8

10

12

14

DPHA Dendriticacrylate

BADGE DAepoxy acrylate

Flexible 2-funcUA

Gloss loss, %

Crosslink Density decreasing

Dendritic Polymers

Characterised by Large number of primary hydroxyl

groups Densely branched polymer backbone Extensive formulation possibilities

General schematic view

超支化聚合物

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

Acrylated Polyol type Di-Penta acrylate (DPHA)

Acrylate of Boltorn P501

Acrylate of Boltorn P500

Viscosity, mPas @ 23C 粘度

13,000 600 500

Pencil hardness 铅笔硬度

PC sheet (250µ)

30 mins 5H-6H 3H-4H H-2H

72 hours 5H-6H 5H-6H 3H-4H

Glass 8H-9H 8H-9H 8H-9H

Scratch (scotch brite, 50 rubs) 抗划伤性

Δ % gloss 0.4 1.6 3.6

Final gloss 90.3 88.1 80.5

Erichsen-flex (Aluminium, mm) 柔韧性

0.4 1.7 2.2

Adhesion (cross-cut, PC Sheet) 附着性

No Yes Yes

Comparison of polyol for hardcoat 对比应用于硬质涂料的多元醇

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

Soft touch applications 柔软触感应用

“Opto-electrical” applications 光电应用

Other “rigid” plastic applications 其他“刚性”塑料应用

Automotive applications 汽车应用

Graphics 油墨应用

Glass applications 玻璃涂料应用

Wood Coatings 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

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！！！

UV ”Soft-feel” Requirements

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.

UV“柔感” 必要条件

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。

UV ”Soft-feel” Requirements

2. Matt/ Gloss Usually matt coatings – few hundred

µm thickness

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

UV“柔感” 必要条件

2. 哑光/高光泽度 一般为哑光涂料, 厚度为几百 µm

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

Design novel Urethane Acrylate based on new speciality Polyols

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

Objective 目标

基于新的特种多元醇设计新型聚氨酯丙烯酸酯

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

Existing Technology

Solvent-borne 2K – Most widely used Waterborne polyurethane systems Focus on 100% UV curable

formulations

现有 技术

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

Mw between 2 crosslinking knots (Mc)

Thermoplastic behaves like noodles Dry = solid Cooked = mobile

Thermoset is locked by cross-links a little like knitted wool

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。

热塑性像面条： 干=固体; 熟=移动

热固性的交叉链接有点像针织的毛绒。

Tg – For UV Cured System

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.

Tg – 适用于紫外光 固化体系

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。

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

hv

Required Properties

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

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

必要性能

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

Urethane acrylate design 聚氨酯丙烯酸酯设计

Much more than innovative chemical solutions

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

Why choose Capa™ ”Backbone”?

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”

为何选择 Capa™ “骨架”？

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”

OHROH Catalyst

Capa™ Monomer

Capa™ Polyol

The reaction is “ring opening”

low temperatures, less catalyst and no water

clean polyester polyol, narrow Mw distribution and clearly defined functionality.

Capa™

“开环”反应

低温，催化剂少且不生成水

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。

Grades can be tailored depending on type of “initiator”.

“Initiator” has significant effect on properties.

Functionality of the “initiator” repeated in the polymer polyol, so di-, tri- and multi functional polyols can be produced.

Capa 2 series – 200 – 8,000 Mw

Diols

Capa 3 series – 300 – 3,000 Mw

Triols

Putting the care into chemicals

Capa™ Polyols Capa™ 多元醇

可根据“起始剂”的类型进行分级。 “起始剂”对性能有显著影响。

“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。

OO O O

1. 2.

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.

Capa™ polyol design

Routes of investigation Adduct Direct acrylation

Capa™ 多元醇设计

研究路线 加合物 直接丙烯酸酯化

Capa extension 1,000 Mw per OH

react with adduct isocyanate/2-HEA

异氰酸酯加合物/2-HEA反映

partial acrylation 部分丙烯酸酯化 graft Capa 接枝 react with di-isocyanate or adduct

1. Careful selection of “initiator”

1. 精心挑选“起始剂”

2. Co-polymer modification of polyol

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

Control of crystallinity 结晶度控制

Two samples were prepared for comparison; Both use 2,000 Mw caprolactone

1. based on 2,000 Mw (Capa™ 2200A) 2. based on modified Caprolactone co-polymer

(Capa™ 612065).

In each case the polyol was made into a polyurethane acrylate, using IPDI and HEA.

Both samples appeared similar immediately after preparation.

Viscosity comparison (20% TPGDA) 粘度对比

Sample 1. = 1.1 Pas Sample 2. = 1.2 Pas

Experimental 实验

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. 基于 2,000 的分子量 (Capa™ 2200A) 2. 基于改性 Caprolactone (己内酯) 共聚物 (Capa™

612065)。

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。

经过制备后，两种样品的表现相似。

The “modified” sample remains clear throughout

“改性”样品仍保持完全透明

Experimental (cont.)

2 h “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。

实验（续）

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

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

Preliminary study of Tg (by DSC)

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

Tg 的初步研究 (示差扫描量热法)

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

(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

Penta + HDI 800 ~130 21 / 0.33 77

Penta + Tolonate™ (ex Vencorex) 1,100 ~180 16 / 0.4 75

As shown on previous slide

Preliminary study of Tg (by DSC)

The effect of structure on Tg and viscosity Type of NCO UA V/s Direct acrylation Ethoxylation

Tg 的初步研究 (示差扫描量热法)

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

Conclusions

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.

结论

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。

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