CN1078981A - 汽车工业中用作外涂层粉末涂料的粘结剂组合物 - Google Patents
汽车工业中用作外涂层粉末涂料的粘结剂组合物 Download PDFInfo
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- CN1078981A CN1078981A CN 93106047 CN93106047A CN1078981A CN 1078981 A CN1078981 A CN 1078981A CN 93106047 CN93106047 CN 93106047 CN 93106047 A CN93106047 A CN 93106047A CN 1078981 A CN1078981 A CN 1078981A
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- adhesive composition
- coating
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- powder coating
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
- C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
在汽车制造业中用作外涂层的粉末涂料的粘结
剂组合物。粘结剂组合物包括含羟基的聚酯和含羟
基的聚丙烯酸酯和保护的六亚甲基二异氰酸酯三聚
物。聚酯的羟值为20-100mgKOH/g树脂，酸值
小于10mgKOH/g树脂，聚丙烯酸酯的羟值为40
-150mgKOH/g树脂，酸值小于20mgKOH/g树
脂。三聚物是用1，2，4-三唑保护的。
Description
本发明涉及汽车制造工业中用作外涂层粉末涂料的粘结剂组合物。
外涂层或装饰涂层是涂覆系统的最后一层，它通常施于底漆、底涂层或表面上。
按汽车制造业现有技术的介绍，作为两组分体系使用的光亮外层涂料是用异氰酸酯固化的基于丙烯酸酯树脂的含溶剂的涂料体系。为了满足减少溶剂排放的要求，高固体含量的体系已经被使用。减少溶剂排放的唯一途径仍然是使用粉末涂料作为汽车的光亮涂料（Lattke E."Pulverlack am Aceto aus der Sicht der Autoindustrie"，刊登在″Der Pulvertreff 92，23.01.92，München″）。
对所述用途的粉末涂料体系来说，与含溶剂的体系有着同样的要求。这些要求与例如流动性、抗化学品性、光泽和户外耐久性有关（Kinza，W.″Pulverklarlack fur die Karosseriebes-chichtung，″刊登在″Die EPS-Praxis 1991，25.11.91，91，Bad Neuheim"）。目标是在低于150℃的固化温度下获得这些特性。在现有粉末树脂体系中，还没有发现能满足所有这些要求特性的体系。基于酸-环氧固化反应的体系能部分满足一些特性，但是，这些粉末涂料至今还远远不能获得好的流动性、好的抗化学品性、高光泽、高抗划伤、好的机械性能和好的户外耐久性等综合的优良特性。基于含羟基的聚合物和含保护的异氰酸酯基的固化剂的体系也能获得若干上述特性。这些体系的固化温度通常都高于170℃，该固化温度对于汽车（光亮）外涂层来说是太高了。
本发明的目的是提供一种粘结剂组合物，它能在较低的温度下固化，并且能给出全部的所需特性。能在汽车外表面形成光亮外涂层的粉末涂料。
本发明的粘结剂组合物包括羟值为20-100（mg KOH/g树脂）、酸值小于10（mg KOH/g树脂）的含羟基的聚酯或羟值为40-150（mg KOH/g树脂）、酸值小于20（mg KOH/g树脂）有含羟基的聚丙烯酸酯和保护的六亚甲基二异氰酸酯三聚物。
本发明粘结剂组合物在130℃-160℃固化得到的粉末涂料具有最佳流动性、抗汽油性、柔韧性和透明度。
按照本发明优选实施例，异氰酸酯三聚物用1，2，4-三唑保护。
含羟基的聚合物与含保护的异氰酸酯基团的粘结剂的重量比通常在90∶10到50∶50的范围内。
粘结剂组合物还可包括羟基官能的聚酯和羟基官能的聚丙烯酸酯的混合物。
在约100℃的温度下，通过例如挤塑的方法将羟基官能的聚合物与保护的交联剂共混，静电喷涂后，它们可以在130℃-170℃之间的温度下固化。
必要时可以添加常用添加到例如填料、流动助剂和/或稳定剂以及颜料，优选的是在挤塑过程中添加。
影响粉末涂料性能的参数和粉末涂料的生产技术见174-300页，Powder Coatings，Chemistry and Technology by Tosko Misev（John Wiley and sons;1991）。
通过常用的制备方法，由主要为芳香族的多元羧酸可以制得适宜的聚酯。适宜的酸包括邻苯二甲酸、间苯二甲酸、对苯二甲酸、1，2，4，5-苯四酸、1，2，4-苯三酸、3，6-二氯邻苯二甲酸、四氯邻苯二甲酸，及其酸酐、酰氯或低级烷基酯（如果可得到的话）。羧酸组分通常至少含50%（重量）、优选的至少含70%（摩尔）的间苯二甲酸和/或对苯二甲酸。
此外，尤其是脂肪族二醇例如乙二醇、丙-1，2-二醇、丙-1，3-二醇、丁-1，2-二醇、丁-1，4-二醇、丁-1，3-二醇、2，2-二甲基丙二醇-1，3（二新戊二醇）、己-2，5-二醇、己-1，6-二醇、2，2-[二（2-羟基乙氧基）]苯基丙烷和少量的多元醇例如甘油、己三醇、季戊四醇、山梨醇、三羟甲基乙烷、三羟甲基丙烷和三（2-羟基）异脲酸酯可以被采用。也可以用环氧化合物来代替二醇或多元醇。优选的醇组分至少含50%（摩尔）新戊二醇。
新戊二醇和/或三羟甲基丙烷是优选的多元醇，因为这些多元醇能够给出很好的户外耐久性。
适宜的多元酸包括环脂族和/或无环多元羧酸，例如环己烷二羧酸、四氢邻苯二甲酸、六氢桥亚甲基四氢邻苯二甲酸、壬二酸、癸二酸、癸烷二羧酸、脂肪酸二聚物、己二酸、丁二酸和马来酸。通常它们的用量至多为羧酸总量的30%（摩尔），优选的至多为20%（摩尔）。羟基羧酸和/或内酯也可以使用，例如12-羟基硬脂酸、ε-己内酯和羟基新戊酸与新戊二醇形成的酯。在制备过程中还可以加入少量的一元羧酸如苯甲酸、叔丁基苯甲酸、六氢苯甲酸和饱和的脂族一元羧酸。
聚酯可以通过本身已知的方法通过酯化作用或酯交换作用制备，制备过程中可以存在常用的催化剂如氧化二丁基锡或肽酸叔丁酯。选择适宜的制备条件和适宜的COOH/OH比，使得树脂的羟值为20-100（mg KOH/g树脂）、酸值小于10（mg KOH/树脂）。
按照本发明更优选的实施例，聚酯基于40-100%（摩尔）间苯二甲酸和0-60%对苯二甲酸为二元羧酸（间苯二甲酸和对苯二甲酸合起来为100%（摩尔））。更优选的为间苯二甲酸的量高于60%（摩尔）。
聚酯也可以基于两种以上的二元羧酸。
官能度大于或等于3的单体的用量优选低于其它单体的12%。数均分子量（Mn）优选的为1500-5000。分子量和支链组分的量合起来要保证聚酯的官能度为2.0-4.0较好。
羟基官能的丙烯酸酯树脂通常基于（甲基）丙烯酸羟乙酯、（甲基）丙烯酸羟丙酯和（甲基）丙烯酸甲酯。树脂也可以基于（甲基）丙烯酸和（甲基）丙烯酸烷基酯例如（甲基）丙烯酸乙酯、（甲基）丙烯酸异丙酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸正丙酯、（甲基）丙烯酸异丁酯、乙基己基丙烯酸酯和/或（甲基）丙烯酸环己酯和乙烯基化合物如苯乙烯。
按照本发明优选实施例，羟基官能的丙烯酸酯树脂基于：
a）10-35%（重量）甲基丙烯酸羟乙酯
b）2-25%（重量）丙烯酸正丁酯，和
c）50-70%（重量）甲基丙烯酸甲酯。
其中a+b+c＝100%（重量）。
羟基官能的丙烯酸酯树脂可以通过聚合来制备：第一步，将溶剂如甲苯、二甲苯或乙酸丁酯加入反应器中。然后加热至溶剂沸腾，随后用例如2-4小时的时间加入单体、引发剂和硫醇（可加可不加）然后在回流温度下保持例如2小时。用升高温度随后真空蒸馏例如1-2小时的方法蒸去溶剂。然后将产物沥干、冷却。
欧洲专利申请EP-A-4571介绍了基于羟基官能聚合物的粉末、溶剂型漆中使用1，2，4-三唑保护的异氰酸酯。但是，EP-A-4571并没有指出用本发明特点的粘结剂组合物能够解决汽车制造业中的所述问题。
美国专利申请US-A-4748242公开了含异氰脲酸酯基的多异氰酸酯的制备方法：将含与脂族伯碳原子相连的空间未受阻异氰酸酯基和与叔碳原子（该碳原子成为脂族环体系的一部分）相连的空间受阻异氰酸酯基的脂族-环脂族二异氰酸酯和1，6-二异氰酸根合己烷的混合物进行三聚作用。该专利还给出了按该方法生产的含异氰脲酸酯基的多异氰酸酯及其用途，用于聚氨酯漆较好，它可以取保护的形式，因为异氰酸酯成分在多异氰酸酯生产过程中形成加聚产物。适宜的保护剂包括1，2，4-三唑。为了生产漆粘结剂，可以将保护的异氰酸酯（不是必须的）、多官能反应组分、催化剂和其它常用添加剂如颜料（不是必须的）相互混合，用常用混合装置均化，可以添加溶剂和稀释剂，也可以不加，然后用常用方法，以溶液或熔融、或固态形式将其施于待涂物体上。US-A-4748242并没有指出用该方法制备可用作汽车外壳光亮涂层的粉末涂料。
本发明粉末涂料也可以用于木制品或用作一般用途的工业外涂层，机器设备的外涂层，特别是金属如罐、家用物品和其它小件设备的外层涂料。
实验1-3
聚酯树脂的制备
向装有温度计、搅拌器和蒸馏装置的3升反应器中，加入表1的单体（按摩尔计）。加入额外的1%（重量）新戊二醇以补充损失的二醇。搅拌，同时将氮气流从反应混合物上方缓慢通过，然后将温度升至170℃，在此温度下水形成。将温度再逐步升至最高温度240℃，蒸去水。继续反应直至聚酯的酸值小于12mg KOH/g。该过程的最后部分在减压下进行。表2列出了羟值（mg KOH/g树脂）、用埃米拉（Emila）流变仪测出的粘度（单位：dPa.s，165℃）和玻璃化转变温度（Tg，Mettler TA-3000系统5℃/分钟）。
表1 单体（摩尔）
第一步 实验.1 实验.2 实验.3
IPA 1) 4.70 6.56 2.87
NPG 2) 8.17 8.24 8.09
TPA 3) 2.68 0.90 4.43
第二步
IPA 1.57 1.57 1.57
第三步
TMP 4) 0.79 0.20 1.37
NPG 0.78 1.34 0.20
其中：
1）IPA＝间苯二甲酸
2）NPG＝新戊二醇
3）TPA＝对苯二甲酸
4）TMP＝三羟甲基丙烷
表2
实验.1 实验.2 实验.3
Mn 1) 2805 2805 2805
F 2) 3.00 2.25 3.75
OH 3) 56 43 66
Visc. 4) 105 60 180
Tg 5) 51 50 53
其中：
1）Mn＝理论分子量
2）F＝官能度
3）OH＝羟值，单位：mg KOH/g树脂
4）Visc＝埃米拉粘度，165℃，dPa.s
5）Tg＝玻璃化转变温度℃（Mettler TA 3000系统5℃/分钟）。
实验4和5
丙烯酸酯树脂的制备
向装有温度计、搅拌器和回流冷凝器的6升反应器中，加入1500g甲苯。搅拌，同时将氮气流从反应混合物上方缓慢通过，然后升温至回流温度。单体混合物包括总量为3000g的单体（比例见表3），其中溶解有给定量的引发剂（Luperox 575TM;Atochem）。然后用3小时的时间将该混合物加入反应器中。将反应器的温度保持在回流温度。加入单体混合物2小时后，装上分离罐，升温并抽真空以除去溶剂。
表3给出了单体重量百分比、用埃米拉流变仪测出的粘度（dPa.s。165℃）和玻璃化转变温度（Tg，Mettler TA-3000，系统5℃/分钟）。
表3
实验4 实验5
HEMA 1) 22.7 17.6
MMA 2) 57.7 60.8
BA 3) 14.2 13.8
Lup 575 4) 5.4 7.8
Visc. 450 95
Tg 57 46
其中
1）HEMA＝甲基丙烯酸羟乙酯
2）MMA＝甲基丙烯酸甲酯
3）BA＝甲基丙烯酸丁酯
4）Lup 575＝Luperox 575TM
实验6
交联剂的制备
向装有温度计、搅拌器和回流冷凝器的2升反应器中加入750g六亚甲基二异氰酸酯三聚物（Tolonate HDTTM，由Rhone Poulenc提供）和271.2g 1，2，4-三唑（由Chemie Linz提供）。搅拌，同时将氮气流通过反应混合物上方，逐步升温。当反应混合物已被加热至90℃时，关掉加热器，必要时将反应器冷却以保证反应混合物的温度不超过100℃，因为这是一个放热反应。从反应温度稳定之时起，用滴定的方法每半小时测定游离NCO的百分比一次。必要时，可以加入数滴二丁基锡月桂酸酯，使反应加快。当游离NCO的最几乎降为零时，反应停止，然后从反应器中倒出清洁的产品。
实施例Ⅰ
粘结剂组合物和粉末涂料的制备
在100℃下，用挤塑机将471g实验1的聚酯树脂、4g流动助剂（BYK 361TM;BYK）和2g安息香混合。挤出物冷却、研磨、过筛，小于90微米筛分用作粉末涂料。将粉末涂料静电喷涂于铝板上。喷有粉末涂料的板在炉中烘30分钟，温度为150℃。
实施例Ⅱ
采用495g实验2的聚酯、105g实验6的交联剂、4g BYKTM361和2g安息香，重复实施例Ⅰ。
实施例Ⅲ
采用453g实验3的聚酯、147g实验6的交联剂、4g BYKTM361和2g安息香，重复实施例Ⅰ。
实施例Ⅳ
采用432g实验4的丙烯酸酯、168g实验6的交联剂、4g BYKTM361和2g安息香，重复实施例Ⅰ。
实施例Ⅴ
采用458g实验5的丙烯酸酯、142g实验6的交联剂、4g BYKTM361和2g安息香，重复实施例Ⅰ。
目测实施例Ⅰ-Ⅴ获得的粉末涂料的外观、透明度和流动性。抗汽油性的测量方法为：将浸有汽油的棉毛块置于涂料上2小时，用一薄片物体将其盖住，然后目检涂料侵蚀情况。机械性能用“埃氏缓慢渗透试验”（按ISO-1520/DIN53156）和“反向冲击试验”（按ASTM-2794/69）进行。
表4
实施例的粉末
I II III IV V
流动性 g1)vg1)g g vg
透明度 vg vg vg vg vg
外观 g g g g g
抗汽油性 vg g vg vg vg
ESP2)>8mm >8mm >8mm >8mm >8mm
抗冲击强度3)60ip4)40ip 60ip <20ip <20ip
其中：
1）g＝好，Vg＝很好
2）ESP＝埃氏缓慢渗透
3）抗冲击强度
4）ip＝英寸磅
总之，用本发明粘结剂组合物获得的粉末涂料可以用于汽车，它在较低的温度下固化，具有好的流动性、透明度、抗汽油性和柔韧性等综合优势。
Claims (10)
1、在汽车制造业中用作外涂层的粉末涂料的粘结剂组合物，其特征在于粘结剂组合物包括羟值为20-100(mgKOH/g树脂)、酸值小于10(mgKOH/g树脂)的含羟基的聚酯或羟值为40-150(mgKOH/g树脂)、酸值小于20(mgKOH/g树脂)的含羟基的聚丙烯酸酯和保护的六亚甲基二异氰酸酯三聚物。
2、权利要求1的粘结剂组合物，其特征在于三聚物是用1，2，4-三唑保护的。
3、权利要求1-2的任一粘结剂组合物，其特征在于：聚酯基于40-100%（摩尔）间苯二甲酸和0-60%（摩尔）对苯二甲酸。
4、权利要求1-3的任一粘结剂组合物，其特征在于：聚酯基于新戊二醇和/或三羟甲基丙烷。
5、权利要求1-4的任一粘结剂组合物，其特征在于：聚丙烯酸酯基于
a）10-35%（重量）甲基丙烯酸羟乙酯，
b）5-25%（重量）丙烯酸正丁酯，和
c）50-70%（重量）甲基丙烯酸甲酯，
其中a+b+c＝100%。
6、权利要求1-5的任一粘结剂组合物的制备方法：在约100℃的温度下，用挤塑的方法将羟基官能的聚合物和保护的六亚甲二异氰酸酯三聚混合。
7、权利要求1-5的任一粘结剂组合物用于制备粉末涂料的用途，在汽车制造业中，所述粉末涂料可以用作外壳的光亮外涂层。
8、粉末涂料，包括权利要求1-5的任一粘结剂组合物和汽车制造业中外层涂层常用的添加剂。
9、部分或全部的涂覆底物，其特征在于涂覆材料是用权利要求1-5的任一粘结剂组合物制得的涂料。
10、实施例介绍和说明的粘结剂组合物、方法、粘结剂组合物的用途、粉末涂料和底物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE9200451A BE1005819A3 (nl) | 1992-05-15 | 1992-05-15 | Bindmiddelsamenstelling voor poedercoatings toepasbaar in de automobielindustrie. |
| BE9200451 | 1992-05-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1078981A true CN1078981A (zh) | 1993-12-01 |
Family
ID=3886268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93106047 Pending CN1078981A (zh) | 1992-05-15 | 1993-05-14 | 汽车工业中用作外涂层粉末涂料的粘结剂组合物 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5580660A (zh) |
| EP (1) | EP0640106B1 (zh) |
| CN (1) | CN1078981A (zh) |
| AU (1) | AU4358893A (zh) |
| BE (1) | BE1005819A3 (zh) |
| DE (1) | DE69309459T2 (zh) |
| TW (1) | TW270937B (zh) |
| WO (1) | WO1993023447A1 (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374478C (zh) * | 2003-08-02 | 2008-03-12 | 巴斯福涂料股份公司 | 热固化性透明涂覆材料及其制备和用途 |
| CN101191029B (zh) * | 2006-12-01 | 2011-05-18 | 比亚迪股份有限公司 | 用于金属基材的底层涂料组合物及其制备方法和多层涂层 |
| CN102408823A (zh) * | 2010-09-21 | 2012-04-11 | 荒川化学工业株式会社 | 具有活性能量线固化薄膜的塑料薄膜用非水基底漆以及具有活性能量线固化薄膜的塑料薄膜 |
| CN108977039A (zh) * | 2018-08-07 | 2018-12-11 | 太仓佩琦涂料有限公司 | 双重固化uv清漆 |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1008721A3 (nl) | 1994-09-21 | 1996-07-02 | Dsm Nv | Bindmiddelsamenstelling voor poederverfformuleringen. |
| DE19611821A1 (de) * | 1996-03-26 | 1997-10-02 | Huels Chemische Werke Ag | Verfahren zur Herstellung von in der Hitze härtbaren wetterstabilen Polyurethan-Pulverlacken sowie die danach erhaltenen Beschichtungen |
| DE19626886A1 (de) * | 1996-07-04 | 1998-01-08 | Huels Chemische Werke Ag | Blockierte Polyisocyanate, ein Verfahren zu ihrer Herstellung sowie deren Verwendung |
| DE19631269A1 (de) * | 1996-08-02 | 1998-02-05 | Bayer Ag | Mit 3,5-Dimethyl-1,2,4-triazol blockierte Polyisocyanate |
| DE19725742C2 (de) * | 1997-06-18 | 1999-11-04 | Herberts & Co Gmbh | Verwendung von Harnstoffverbindungen und Formaldehyd liefernden Substanzen in Klarlacküberzugsmitteln |
| US6255523B1 (en) | 1998-09-18 | 2001-07-03 | Mcwhorter Technologies, Inc. | Power coatings based on branched oligoesters and non-emissive uretdione polyisocyanates |
| US6248843B1 (en) * | 1998-09-18 | 2001-06-19 | Mcwhorter Technologies, Inc. | Powder coatings based on branched oligoesters and triazole blocked polyisocyanates |
| EP1028135A1 (en) * | 1998-12-28 | 2000-08-16 | Bayer Corporation | Method for making 1,2,4-Triazole blocked polyisocyanate crosslinkers, coating compositions and coatings prepared therefrom |
| US7214432B2 (en) * | 2003-09-30 | 2007-05-08 | General Electric Company | Coating compositions, their preparation, and coated articles made therefrom |
| AU2004287801A1 (en) * | 2003-11-03 | 2005-05-19 | M I 6 Technologies, Inc. | Spray-on paint protection film and method of applying same |
| US9359524B2 (en) * | 2013-10-15 | 2016-06-07 | Ppg Industries Ohio, Inc. | Polyesters and coatings containing the same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3721645A (en) * | 1971-02-25 | 1973-03-20 | Liner Technology Inc | Polyurethanes stabilized with 1,2,3-,1,2,4-1,2,5-,and 1,3,4-triazoles |
| DE2812252A1 (de) * | 1978-03-21 | 1979-10-04 | Bayer Ag | 1,2,4-triazol-blockierte polyisocyanate als vernetzer fuer lackbindemittel |
| CA1112243A (en) * | 1978-09-08 | 1981-11-10 | Manfred Bock | Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof |
| DE3541859A1 (de) * | 1985-11-27 | 1987-06-04 | Bayer Ag | Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung als isocyanatkomponente in polyurethanlacken |
| US4659799A (en) * | 1985-12-03 | 1987-04-21 | E. I. Du Pont De Nemours And Company | Amine vapor curable coating composition of an acrylic polymer and a polyisocyanate |
| US4824909A (en) * | 1986-04-10 | 1989-04-25 | Nippon Paint Co., Ltd. | Powder coating composition |
| DE3711374A1 (de) * | 1987-04-04 | 1988-10-20 | Huels Chemische Werke Ag | Polyurethan-pulverlacke, die nach aushaertung eine matte oberflaeche ergeben |
-
1992
- 1992-05-15 BE BE9200451A patent/BE1005819A3/nl not_active IP Right Cessation
-
1993
- 1993-05-11 TW TW082103681A patent/TW270937B/zh active
- 1993-05-12 AU AU43588/93A patent/AU4358893A/en not_active Abandoned
- 1993-05-12 DE DE69309459T patent/DE69309459T2/de not_active Expired - Fee Related
- 1993-05-12 EP EP93913622A patent/EP0640106B1/en not_active Expired - Lifetime
- 1993-05-12 WO PCT/NL1993/000097 patent/WO1993023447A1/en active IP Right Grant
- 1993-05-12 US US08/335,884 patent/US5580660A/en not_active Expired - Fee Related
- 1993-05-14 CN CN 93106047 patent/CN1078981A/zh active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374478C (zh) * | 2003-08-02 | 2008-03-12 | 巴斯福涂料股份公司 | 热固化性透明涂覆材料及其制备和用途 |
| CN101191029B (zh) * | 2006-12-01 | 2011-05-18 | 比亚迪股份有限公司 | 用于金属基材的底层涂料组合物及其制备方法和多层涂层 |
| CN102408823A (zh) * | 2010-09-21 | 2012-04-11 | 荒川化学工业株式会社 | 具有活性能量线固化薄膜的塑料薄膜用非水基底漆以及具有活性能量线固化薄膜的塑料薄膜 |
| CN102408823B (zh) * | 2010-09-21 | 2016-10-05 | 荒川化学工业株式会社 | 具有活性能量线固化薄膜的塑料薄膜用非水基底漆以及具有活性能量线固化薄膜的塑料薄膜 |
| CN108977039A (zh) * | 2018-08-07 | 2018-12-11 | 太仓佩琦涂料有限公司 | 双重固化uv清漆 |
Also Published As
| Publication number | Publication date |
|---|---|
| BE1005819A3 (nl) | 1994-02-08 |
| DE69309459D1 (de) | 1997-05-07 |
| EP0640106A1 (en) | 1995-03-01 |
| EP0640106B1 (en) | 1997-04-02 |
| US5580660A (en) | 1996-12-03 |
| AU4358893A (en) | 1993-12-13 |
| WO1993023447A1 (en) | 1993-11-25 |
| TW270937B (zh) | 1996-02-21 |
| DE69309459T2 (de) | 1997-10-23 |
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