Perstorp Capa™ for Radiation Curing Chinacoat 2013

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Information about Perstorp Capa™ for Radiation Curing Chinacoat 2013

Published on February 14, 2014

Author: PerstorpGroup



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

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 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

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

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

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

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

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 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

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。

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)

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

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

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 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!!!

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。

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

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

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

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。

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。

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

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

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”

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。

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

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.

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

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。

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

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

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

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。

谢谢 Contact – Paul Kelly

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