CN1090212C - 丙烯酸酯基颜料制剂的连续制备方法 - Google Patents
丙烯酸酯基颜料制剂的连续制备方法 Download PDFInfo
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- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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Abstract
本发明提供颜料制剂的制备方法和用颜料制剂着色的高分子量有机材料。所述制备方法包括将着色组合物与单体混合、同时在挤压机中于高温下使单体聚合,由此进行以下步骤:(A)将以下组分连续引入挤压机中(a)40-90%(重量)的颜料,(b)60-10%(重量)的至少一种选自丙烯酸酯和甲基丙烯酸酯的单体,由此颜料和单体量的总和为100%,如果需要时,(c)组分(b)量的0-10%(重量)的引发剂,(B)同时混合组分(a)、(b)以及需要时和(c),(C)从挤压机中连续取出获得的反应混合物。
Description
本发明涉及通过将着色组合物与单体混合、同时在挤压机中于高温下使单体聚合来制备颜料制剂的方法。
由于改进工业卫生的强烈倾向,消费者越来越多从粉状颜料转向使用颜料制剂。然而,颜料制剂一方面确实包含颜料,而另一方面也含有载体材料。因此,通过使用颜料制剂,将载体材料与颜料一起引入应用体系中。为了最大限度地减小载体材料在最终应用中的可能影响,载体材料的浓度应该尽可能地低,换句话说,颜料浓度应该尽可能地高,同时保持最佳分散性能。
一般来说,颜料制剂的生产方法使用现成的聚合物和现成的颜料作为原料,然后将颜料分散到聚合材料中。生产方法基本上由两个步骤组成:先生产聚合材料然后进行颜料的分散。EP-A 456 610和EP-A 542 669描述了颜料制剂的生产方法,该制剂包含至多10%(重量)的着色组合物,但都用于缩聚树脂,诸如热固性交联树脂(磺酰胺和乙醛的本体缩合)和聚酰胺、聚酯、聚碳酸酯或聚氨酯树脂之类,由此将生成所述缩聚树脂的反应物(单体)与着色组合物一起,连续引入挤压机中,并在其中于高温下进行聚合。这些方法的主要缺点是只可以将至多10%的着色组合物混入缩聚树脂中。
因此,本发明的目的是提供含有高于l0%颜料的颜料制剂的生产方法。
因此,发现通过将着色组合物与单体混合、同时在挤压机中于高温下使单体聚合的颜料制剂制备方法,其特征在于
(A)将以下组分连续送入挤压机中
(a)40-90%(重量)的颜料,
(b)60-10%(重量)的至少一种选自丙烯酸酯和甲基丙烯酸酯的
单体,从而颜料和单体量的总和为100%,如果需要时,
(c)组分(b)量的0-10%(重量)的引发剂,
(B)同时将组分(a)、(b)以及需要时和(c)在挤压机中混合,
(C)从挤压机中连续取出获得的反应混合物。
此外,也发现了用本发明颜料制剂着色的高分子量有机材料及其制备方法。
可以按照本发明使用的颜料是通常用于高分子量有机材料着色剂工业的任何固态着色剂。这些固态着色剂包括有机颜料和无机颜料以及炭黑。典型的有机颜料是喹吖啶酮、二酮吡咯并吡咯、蒽醌、苝、靛蓝、喹啉酮、异吲哚啉酮、异二氢吲哚、二噁嗪、酞青或偶氮系列的颜料或它们的混合物。
无机颜料适宜的实例是金属氧化物颜料,诸如氧化铁、氧化钛和氧化铬之类;镉颜料,诸如硫化镉之类;铋颜料,诸如钒酸铋之类;铬酸盐颜料,诸如铬酸铅之类;钼酸盐颜料,诸如钼酸铅之类等;或它们的混合物。也可以使用所有种类颜料的混合物。
待引入挤压机的颜料的量选择为引入的颜料和单体总量的40-90%,优选40-80%,更优选45-80%,最优选45-75%(重量)。
因此,本发明颜料制剂中颜料的量尤其取决于聚合度,通常为总组合物的40-90%(重量),最好为50-75%(重量),在某些情况下可以高达60-75%(重量)。
本发明特别感兴趣的丙烯酸酯单体是式(I)单体
CH2=CR1-COOR2 (I)
其中R1是氢或甲基,
R2是氢、C1-C12烷基、CH2-CH2-N(R3)(R4)、CH2-CH=CH2、
CH2CF3、CH2-CH2OR3或CH2-CHOH-R3,
R3和R4相互独立,为氢或C1-C4烷基,以及丙烯腈、丙烯酰胺、苯乙烯、乙酸乙烯酯、乙烯醇,或它们的混合物。
C1-C12烷基一般为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、2-乙基己基、壬基、癸基或月桂基;优选C1-C4烷基,诸如甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基或叔丁基;更优选甲基、乙基和正丁基。
也可以使用由上述单体获得的预聚物。
推荐的丙烯酸酯单体是那些R1是氢或甲基而R2是C1-C4烷基的式(I)单体或其混合物。
特别推荐的是甲基丙烯酸甲酯(“MMA”)和丙烯酸丁酯(“BA”)的混合物,优选40-80%(重量)的MMA和60-20%(重量)的BA,更优选50-75%(重量)的MMA和50-25%(重量)的BA,最优选60-75%(重量)的MMA和40-25%(重量)的BA,总量为100%。
用于本发明的引发剂一般为通常用于聚合的引发剂,例如过氧化物、过酸酯、氢过氧化物和某些偶氮化合物以及它们的混合物。推荐的引发剂选自过新癸酸叔丁酯(TBPND)、碳酸叔丁基过氧乙基己酯(TBPEHC)、过新癸酸叔戊酯(TAPND)、过新戊酸叔戊酯(TAPPI)、过新戊酸叔丁酯(TBPPI)、2,5-二甲基-2,5,-二(2-乙基己酰过氧)己烷(DHPEH)、过氧-2-乙基己酸叔戊酯(TAPEH)、过氧-2-乙基己酸叔丁酯(TBPEH)、过氧-3,5,5-三甲基己酸叔丁酯(TBPIN)和它们的混合物。
特别推荐的是新癸酸叔丁酯和碳酸叔丁基过氧乙基己酯的混合物,优选范围为50-85%(重量)的TBPND和50-15%(重量)的TPEHC,总和为100%,特别优选的重量比范围为(70-80)/(30-20)(TBPND/TBPEHC)。
引发剂的量优选为丙烯酸单体的2-8%(重量),更优选3-5%(重量)。
反应温度最好选择为90-200℃。
通常任何种类的挤压机都可以用来进行本发明的方法,例如双螺杆挤压机或捏合型挤压机,最好是同向旋转双螺杆挤压机,特别是同向旋转、紧密啮合式挤压机。挤压机的长度与直径之比一般不是关键,L/D范围优选20-80,更优选35-60。
挤压机中的聚合反应以与已知方法类似的方法进行,例如在TheCanadian Journal of Chemical Engineering,71,June 1993中描述的方法。
在推荐实施方案中,组分(a)、(b)以及需要时和(c)以某种方式混合,使得颜料分散、最好是均匀分散在单体材料(a)中。
在推荐实施方案中,反应混合物在反应结束时,在取出前通过已知方法进行脱气和过滤。
回收的颜料制剂通常为粒状或粉状。一般来说,它们是自由流动的、干燥的、低尘颜料浓缩物,可理想地适用于加入大量相同材料中或加入大量不同的高分子量有机材料(例如塑料材料)中,产生均一的着色塑料,可以挤塑或模塑为纤维、单丝、薄膜或油漆、印刷墨水或需要高度颜料分散体的其它应用。可以用按照本发明获得的颜料制剂着色的典型的高分子量有机材料包括纤维素醚和纤维素酯,典型的是乙基纤维素、硝基纤维素、乙酸纤维素酯、丁酸纤维素酯;中性树脂或合成树脂,典型的是聚合树脂或缩合树脂,诸如氨基塑料等,最好为脲/甲醛树脂和三聚氰胺/甲醛树脂、醇醛树脂、酚醛塑料、聚碳酸酯、聚烯烃、聚苯乙烯、聚氯乙烯、聚酰胺、聚氨酯、聚酯、ABS、对聚苯氧、橡胶、酪蛋白、硅氧烷和有机硅树脂,可以单独使用或以混合物使用。
因此,本发明的另一实施方案涉及用所需量的本发明颜料制剂着色的高分子量有机材料。另一实施方案涉及着色高分子量有机材料的制备方法,即将本发明颜料制剂与高分子量有机材料用已知方法混合。
用本发明方法获得的本发明颜料制剂的用量可以为待着色高分子量有机材料的0.01-50%(重量),最好为0.2-20%(重量)。
一般描述本发明后,给出以下实施例说明本发明的具体实施方案。所有份数和百分比都按重量计,除非另外说明。实施例1:将30kg黄色铬酸铅颜料(Homachrome Yellow GMXAH-25)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为60∶40(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为70∶30(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=40)中,通过量分别为5.85kg/h(颜料)、3.15kg/h(单体混合物)和0.095kg/h(引发剂混合物)。挤压机分为13个等长的区,每个区单独加热。应用以下温度曲线图(1=输入区,13=输出区):区 1 2 3 4 5 6 7 8 9 10 11 12 13T[℃] 30 30 30 60 90 120 150 150 120 120 150 150 160
熔体在第9区于5mbar压力下脱气,在第12区挤出并过滤。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为98%。实施例2:将30kg黄色铬酸铅颜料(Homachrome Yellow GMXAH-25)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为75∶25(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为70∶30(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=40)中,通过量分别为5.85kg/h(颜料)、3.15kg/h(单体混合物)和0.095kg/h(引发剂混合物)。以实施例1描述的相同方式(相同参数)进行挤塑。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为95%。共聚物的重均分子量(Mw)大约为25000g/mol。数均分子量(Mn)大约为8800g/mol,产生的多分散性为2.8。实施例3:将25kg绿色酞青颜料(BASF的Acnalin Supra Green FG;C.I.颜料绿7)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为60∶40(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为70∶30(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=40)中,通过量分别为2.5kg/h(颜料)、2.5kg/h(单体混合物)和0.10kg/h(引发剂混合物)。以实施例I描述的相同方式(相同参数)进行挤塑。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为98%。共聚物的重均分子量(Mw)大约为32,4000g/mo1。数均分子量(Mn)大约为14,200g/mol,产生的多分散性为2.3。实施例4:将25kg红色DPP颜料(Ciba;CHROMOPHTHALDPP RedBP,C.I.颜料红254)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为60∶40(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为70∶30(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=40)中,通过量分别为2.50kg/h(颜料)、2.50kg/h(单体混合物)和0.100kg/h(引发剂混合物)。以实施例1描述的相同方式(相同参数)进行挤塑。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为99%。共聚物的重均分子量(Mw)大约为31,2000g/mol。数均分子量(Mn)大约为10,100g/mol,产生的多分散性为3.1。实施例5:将25kg蓝色酞青颜料(C.I.颜料蓝15;BASF的AcnalinSurpa Blue G)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为70∶30(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为70∶30(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=52)中,通过量分别为4.40kg/h(颜料)、3.60kg/h(单体混合物)和0.216kg/h(引发剂混合物)。挤压机分为16个等长的区,每个区单独加热。应用以下温度曲线图(1=输入区,16=输出区):区 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16T[℃] 30 30 30 60 90 120 150 150 150 150 150 120 120 150 150 160
熔体在第12区于5mbar压力下脱气,在第15区挤出并过滤。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为98%。共聚物的重均分子量(Mw)大约为139000g/mol。数均分子量(Mn)大约为7000g/mol,产生的多分散性为2.0。实施例6:将25kg红色Cinquasia颜料(C.I.颜料紫19;Acramin PinkBN)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为70∶30(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为70∶30(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=52)中,通过量分别为4.40kg/h(颜料)、3.60kg/h(单体混合物)和0.216kg/h(引发剂混合物)。以实施例5描述的相同方式(相同参数)进行挤塑。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为94%。共聚物的重均分子量(Mw)大约为176000g/mol。数均分子量(Mn)大约为7100g/mol,产生的多分散性为2.5。实施例7:将25kg玉红色DPP颜料(Ciba;IRGAZINDPP RUBINETR,C.I.颜料红264)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为61∶39(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为80∶20(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=52)中,通过量分别为2.40kg/h(颜料)、3.60kg/h(单体混合物)和0.144kg/h(引发剂混合物)。以实施例5描述的相同方式(相同参数)进行挤塑。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为98%。实施例8:将30kg TiO2(C.I.颜料白6,Aquatone White Plus)装入失重给料器中。用氮气吹扫计量容器,然后装入甲基丙烯酸甲酯(MMA)和丙烯酸丁酯(BA)单体,重量比为61∶39(MMA∶BA),总共30kg。将3kg的TBPND和TBPEHC的过氧化物混合物装入第二个计量容器中,重量比为80∶20(TBPND∶TBPEHC)。将颜料、单体混合物和引发剂混合物计量加入同向旋转双螺杆挤压机(L/D=52)中,通过量分别为6.00kg/h(颜料)、2.00kg/h(单体混合物)和0.080kg/h(引发剂混合物)。以实施例5描述的相同方式(相同参数)进行挤塑。挤出物收集在一个容器中,打碎并研磨。聚合反应的收率为95%。实施例9:2.91kg聚甲基丙烯酸甲酯(DIAKONLG 156,ICI;维卡软化点(完全软化)(装载5kg)(DIN 53460 B):95℃,按照ASTMD1238-73的熔体流动指数(10kg):16g/10min)于70℃干燥2小时,然后与0.09kg实施例2中获得的产物混合。混合物通过滚筒混合,于200℃在双螺杆挤压机上加工、造粒,再于70℃干燥。粒状产物于240℃注塑。以PMMA的相同方式,用以下试验化合物试验实施例2中获得的颜料制剂:聚乙烯(PE,Stamylex,DSM)聚苯乙烯(PS,SHELL的N3000;熔体流动指数MFI 200/5(DIN 53735):9g/10min)聚丙烯(PP,MoplenZ30S,DSM)丙烯腈-苯乙烯-丙烯酸酯(ASA,Luran776 S/SE,BASF;维卡软化点(VST/A/50):104℃)丙烯腈-丁二烯-苯乙烯(ABS,RonfalinFX50,DSM)聚酰胺(PA,UltramidB35K,BASF)聚对苯二甲酸丁二醇酯(PBT,CrastinS600,Ciba)聚碳酸酯(MAKROLON2800,BAYER,Vicat(VST/B/120):148℃)
模塑板都没有显示出在实施例2获得的颜料制剂和试验化合物之间的不相容作用。
此外,按照实施例4-6生产的制剂也在上述应用实施例中进行试验。在这些扩展的试验系列中,用以下聚合物取代聚甲基丙烯酸甲酯:聚苯乙烯(SHELL的N3000;熔体流动指数MFI 200/5(DIN 53735):9g/10min)丙烯腈-苯乙烯-丙烯酸酯(ASA,Luran776 S/SE,BASF;维卡软化点(VST/A/50):104℃)聚酰胺(PA,UltramidB35K,BASF)聚对苯二甲酸丁二醇酯(PBT,CrastinS600,Ciba)聚碳酸酯(MAKROLON2800,BAYER,Vicat(VST/B/120):148℃)
模塑板都没有显示出在实施例4-6中获得的颜料制剂和试验化合物之间的不相容作用。实施例10:在100ml烧瓶中装入40ml玻璃珠、23.07g实施例1中获得的颜料制剂和30.0g粘合剂聚酰胺墨水(含有25.37份聚酰胺树脂EURELON 931(WHITCO)、7.46份脲醛树脂LAROPALK80(BASF;软化点(DIN 53180):75-85℃,酸值(ISO 3682,DIN 53402):最大值1mgKOH/g)、2.24份Wax AL3(BASF)和64.93份溶剂混合物(正丙醇∶异丙醇∶石油溶剂油140F(SHELL;CAS-No.64742-88-7,熔点为180-210℃的脂肪烃,密度(15℃,ASTM D 1298)∶0.788 g/cm3)(=1∶1∶1))。混合物在Skandex油漆振荡器上分散60分钟,然后用于黑白应用形式。没有观察到不相容作用。实施例11:对于饱和色应用,将40ml玻璃珠、26.9g实施例2产物、5.0g溶剂混合物(由41.2份乙酸丁二醇酯、29.4份乙酸丁酯和29.4份二甲苯组成)和12.5g研磨漆料(由70份含羟基丙烯酸树脂MACRYNALSM 510n(HOECHST;格氏色标准(ASTM D 1544):<2,羟基值(DIN 53783):大约150mg KOH/g固体树脂)、24份所述溶剂混合物、3份PERENOLEI(HENKEL;油滑添加剂,密度(20℃):0.815-0.835g/cm3,固体含量:24-28%)和3份聚硅氧烷嵌段共聚物VP-PERENOLS4(HENKEL;密度(20℃):0.950-0.970g/cm3,固体含量:47-50%)组成)装入100ml玻璃罐中。混合物在Skandex油漆振荡器上分散大约20分钟。然后加入22.5g丙烯酸树脂MACRYNALSM510n,然后再分散5分钟。
对于1∶10钛白还原,按照饱和色应用的相同步骤。然而,使用17.5g TiO2(RCR-2)和2.69g实施例2产物(而不是26.9g)。
对于饱和色应用以及1∶10钛白还原,在应用前直接加入15.5g脂族聚异氰酸酯DESMODURN75(BAYER;在乙酸1-甲氧基-2-丙酯/二甲苯(1∶1)中大约75%,按六亚甲基-1,6-二异氰酸酯计,密度(DIN53217,20℃):107g/cm3,粘度(DIN 53211):59s)。混合物在黑白涂敷板上配漆。让应用物蒸发30分钟,然后让其再固化30分钟。
应用物没有显示出与颜料制剂载体体系之间的不相容作用。实施例12:将339g饱和的羧化聚酯树脂URALACP5401(DSM;粘度(TM 2005):200-400dPa·s)、25.5g异氰酸三缩水甘油酯(赋予良好的耐候性,ARALDITEPT 810(CIBA)、7g吸附于SiO2上的丙烯酸酯共聚物(作为防缩孔和流平添加剂)BYK365P(Byk-Chemie;丙烯酸酯含量:63%,煅烧后的残渣:33%,表观密度(DIN 53468):650g/l)、3.5g苯偶姻、38g实施例1中获得的颜料制剂、75g TiO2和12g BaSO4(Sachtleben的Blanc Fixe F)在小容器(kitchenette)中混合3次15秒,制备预混合物。预混合物在Prism 16mm双螺杆挤压机上挤塑。用于挤压机不同区的温度描绘范围为65-110℃。冷却后,挤出物进行研磨并通过100μm筛网筛选。粉末用Wagner ESB EPG 2020CG静电喷枪喷到铝Q板上。铝板在空气循环烘箱中于180℃固化20分钟。应用物没有显示出不相容的作用。
按照实施例4-8生产的颜料制剂以完全相同方式进行试验。这些制剂也没有显示出不相容的作用。实施例13:制备300ml研磨料,该研磨料含有48.32%的基于合成脂肪酸的非干燥的短油醇酸树脂SETAL 84 XX-70(Akzo-Nobel;脂肪酸含量:28%,邻苯二甲酸酐含量:45%,密度(DIN 53217):1.08g/cm3)、18.76%的非增塑三聚氰胺树脂SETAMINE US132-BB-70(Akzo-Nobel;密度(DIN 53217):1.02g/cm3,闪点(DIN 53213):35℃,不挥发物(ISO3251):69-73%)、21.86%芳烃混合物(平均值为120g/mol,沸点:162-176℃)SOLVESSO100(ESSO)、4.50%丁醇、2.25%Depanol J(Hoechst)、2.25%Isophoron 563(Huls)、0.04%Baysilone-LackadditiveMA(Bayer)和2.02%二甲苯。
用分散搅拌器分散混合物(含有24%TiO2和76%研磨料),直至颗粒大小<10μm,制备200g白漆。
100ml烧瓶中装入40ml玻璃珠、11ml研磨料和4.0g酞青绿粉状颜料。混合物在Skandex油漆振荡器上分散60分钟,然后用26ml研磨料配漆。
然后将烧瓶中的一半内容物(没有玻璃珠)加入100g白漆中,混合物搅拌大约5分钟(1∶12还原)。
用线束在黑白硬纸板上拉制薄膜,制备应用物。然后进行捏合试验。最后,应用物在周围温度下干燥5分钟,然后于160℃干燥6分钟。
然后将4.0g实施例3的制剂加入100g白漆中,混合物搅拌20分钟。在5分钟、10分钟、15分钟和20分钟后,按上述方法制备应用物。
该应用物与基于粉状颜料的应用物进行比较。表明与基于粉状颜料的应用物相比,使用实施例3的制剂时,颜色强度完全显现出。此外,基于实施例3的应用物表现出较好的光泽。
以完全相同的方式试验按照实施例4-6生产的颜料制剂。这些制剂显示出完全的颜色强度显现,也显示出较好的光泽。没有观察到不相容作用。
Claims (6)
1.颜料制剂的制备方法,包括将着色组合物与单体混合、同时在挤压机中于90-200℃的温度下使单体聚合;其特征在于
(A)将以下组分连续引入挤压机中
(a)40-90%(重量)的颜料,
(b)60-10%(重量)的至少一种选自丙烯酸酯和甲基丙烯酸酯
的单体,由此颜料和单体量的总和为100%,如果需要
时,
(c)组分(b)量的0-10%(重量)的引发剂,
(B)同时将组分(a)、(b)以及需要时和(c)在挤压机中混合,
(C)从挤压机中连续取出获得的反应混合物。
2.按照权利要求1的方法,其特征在于,将各种组分混合,使得颜料分散在单体材料中。
3.权利要求2的方法,其中的颜料是均匀分散的。
4.按照权利要求1的方法,其特征在于,在反应结束时、在取出反应混合物之前,将反应混合物进行脱气和过滤。
5.按照权利要求1-4之一的方法,其中所用的丙烯酸酯单体选自丙烯酸酯、丙烯腈、丙烯酰胺、苯乙烯、乙酸乙烯酯、乙烯醇或它们的混合物,其中丙烯酸酯的结构式为:
CH2=CR1-COOR2 (I)
其中R1是氢或甲基,
R2是氢、C1-C12烷基、CH2-CH2-N(R3)(R4)、CH2-CH=CH2、CH2CF3、
CH2-CH2OR3或CH2-CHOH-R3,
R3和R4相互独立,为氢或C1-C4烷基。
6.用按照权利要求1-5之一方法制备的颜料制剂着色的高分子量有机材料。
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WO2006009161A1 (ja) * | 2004-07-21 | 2006-01-26 | Matsushita Electric Industrial Co., Ltd. | 多層情報記録媒体及びその製造方法 |
DE102004036542B4 (de) * | 2004-07-28 | 2007-07-12 | Dilo Trading Ag | Elektrodenmasse zur Verwendung in einer Lithium-Polymer-Zelle und Verwendung der Elektrodenmasse |
WO2007026765A1 (ja) * | 2005-08-30 | 2007-03-08 | Matsushita Electric Industrial Co., Ltd. | 多層情報記録媒体およびその製造方法、並びに多層情報記録媒体の製造装置とこの製造装置を構成する多層情報記録媒体製造用スクリーン |
EP1881031A1 (en) * | 2006-07-21 | 2008-01-23 | Arkema France | Non PVC thermoplastic compositions |
US8461229B2 (en) * | 2006-10-25 | 2013-06-11 | Basf Se | Heat-stable encapsulated pigments |
US11427658B2 (en) | 2018-01-11 | 2022-08-30 | Lg Chem, Ltd. | Method for manufacturing low molecular weight acrylic resin |
CN109632572B (zh) * | 2018-12-25 | 2021-03-30 | 山西霍家长化合成橡胶有限公司 | Pdva油漆聚合终点判定方法 |
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US3637545A (en) * | 1968-01-17 | 1972-01-25 | Plastugil Plastiques Et Elasto | Process of preparing methyl methacrylate polymers |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
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BE592554A (zh) * | 1959-07-03 | 1900-01-01 | ||
US3370470A (en) * | 1965-08-26 | 1968-02-27 | Neugebauer Gerhard | Sealing arrangement for liquid-filled manometer casing |
US3770470A (en) * | 1972-12-13 | 1973-11-06 | Cabot Corp | Pigmented resin compositions |
DE3323951A1 (de) * | 1983-07-02 | 1985-01-03 | Röhm GmbH, 6100 Darmstadt | Acrylatharze als bindemittel fuer farbmittelkonzentrate |
GB8320487D0 (en) * | 1983-07-29 | 1983-09-01 | Silberline Ltd | Metal pigment compositions |
FR2661917B1 (fr) * | 1990-05-11 | 1994-10-21 | Chimie Indle Sa Ste Nle | Pigments, procede et dispositif pour les fabriquer. |
US5229472A (en) * | 1991-07-04 | 1993-07-20 | Shell Oil Company | Anionic extruder polymerization process |
ES2101826T3 (es) * | 1991-11-04 | 1997-07-16 | Chimie Ind Sa Soc Nouv | Procedimiento para la preparacion de pigmentos, especialmente, pigmentos fluorescentes. |
DE4337482A1 (de) * | 1993-11-03 | 1995-05-04 | Basf Ag | Verfahren zur Herstellung von radikalisch vernetzbaren Copolymerisaten |
US5534055A (en) * | 1994-08-24 | 1996-07-09 | Bayer Corporation | Process for alpha-phase metal phthalocyanine pigments |
US5496405A (en) * | 1994-12-06 | 1996-03-05 | Bayer Corporation | Process for the preparation of organic pigments |
-
1997
- 1997-09-04 ES ES97810631T patent/ES2152075T3/es not_active Expired - Lifetime
- 1997-09-04 DE DE69703331T patent/DE69703331T2/de not_active Expired - Fee Related
- 1997-09-11 KR KR1019970046682A patent/KR19980024532A/ko active IP Right Grant
- 1997-09-11 CN CN97118631A patent/CN1090212C/zh not_active Expired - Fee Related
- 1997-09-12 JP JP9247369A patent/JPH1087712A/ja active Pending
- 1997-09-12 US US08/928,969 patent/US5905111A/en not_active Expired - Fee Related
-
1999
- 1999-01-26 US US09/237,642 patent/US6103795A/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3637545A (en) * | 1968-01-17 | 1972-01-25 | Plastugil Plastiques Et Elasto | Process of preparing methyl methacrylate polymers |
Also Published As
Publication number | Publication date |
---|---|
ES2152075T3 (es) | 2001-01-16 |
DE69703331D1 (de) | 2000-11-23 |
US6103795A (en) | 2000-08-15 |
DE69703331T2 (de) | 2001-03-15 |
CN1176979A (zh) | 1998-03-25 |
JPH1087712A (ja) | 1998-04-07 |
KR19980024532A (ko) | 1998-07-06 |
US5905111A (en) | 1999-05-18 |
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