CN1082065C - 抗静电着色热塑性模塑材料 - Google Patents
抗静电着色热塑性模塑材料 Download PDFInfo
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
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- 229920005601 base polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical compound C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
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- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 1
- 229940093500 ethoxyquin Drugs 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- NDBYXKQCPYUOMI-UHFFFAOYSA-N platinum(4+) Chemical compound [Pt+4] NDBYXKQCPYUOMI-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical group C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
热塑性模塑化合物,包括A)一种可溶于其内的染料,和B)一种N,N-双(2-羟乙基)-C6-C22-烷基胺或N,N-双(2-羟乙基)-C6-C22链烯基胺,该化合物具有按德国标准DIN53409规定低于300的Hazen色数。
Description
本发明涉及热塑性模塑材料,包括:
A)一种可溶于其内的染料,如
B)一种N,N-双(2-羟乙基)-C6-C22-烷基胺或N,N-双(2-羟乙基)
-C6-C22链烯基胺,该化合物具有按德国标准DIN53409规定的
低于300的Hazen色数。
本发明还涉及生产模塑制品的方法和由这些模塑材料模塑的制品。
塑料材料通常含有各种类型的添加剂,以便使模塑材料适应某些应用,包括,如所公知的抵抗在塑料上聚集的不希望的静电荷的抗静电性能。
为此常用的添加剂为N,N-双(2-羟乙基)-C6-C22-烷基胺类或链烯基胺类,它们中的一些可以在市场上买到。
对于以可溶性染料着色的塑料,这些双(羟乙基)胺类有缺陷:它们减弱了着色度,减弱的程度随着在模塑材料和模塑制品生产中的加工温度增高以及抗静电剂的初始杂质的增加而变大。
本发明的一个目的是补救这一缺陷。
我们发现这个目的通过上述定义的热塑性模塑材料而达到的。
可适用的模塑材料的透明着色剂为各种结构的可溶性染料,例如偶氮染料类,蒽醌染料类一甲碱类染料类以及二氢吲哚和尼格色基类。对于配合物类,优选用铬的。详情见Einfarben vonKunststoffen的专论[Coloring of plastics],由GermanEngineers′Association编辑,VDI-Verlag Dusseldorf 1975,P.225ff。
在模塑材料中可溶性染料的浓度取决于所需颜色强度,一般的范围为0.00005至5,优选为0.0001至2.5%,按重量计。
本发明的热塑性模塑材料的组分(B)是一种N,N-双(2-羟乙基)-C6-C22-烷基胺或N,N-双(2-羟乙基)-C6-C22-链烯基胺,相应具有如下结构:
这里R分别是C6-C22-烷基或C6-C22-链烯基。这些化合物,是最熟知不过的,是通过使环氧乙烷与一种胺R-NH2反应的惯用方法获得的。
优选使化合物B)中的R为C12-C18-正-烷基。不同的乙氧化胺类B的混合物也适用,例如,由德国Akzo,Duren,生产的市售商品ArmostatR400,是乙氧基化的C12-和C14-烷基胺类的混合物。
作为本发明的一个基本特征,化合物B)的Hazen色数小于300。Hazen色数按德国标准DIN53409测定,并且也称为APHA值(American Public Health Association)。它表示铂(当六氯铂(IV)酸钾(K2PtCl6)和钴(II)的氯化物(CoCl2·6H2O)按1.246∶1的比例在1000ml的盐酸水溶液中)的毫克数,具有在相同光程时与试样相同或基本相同的颜色。色数300相当于浅淡黄色。
当化合物B)的Hazen色数低于300时,以可溶性染料着色的塑料的颜色将保持不变。当色数大于300时,上述不希望的变色会在加工条件下和其后的时间进程中发生,估计这是由于杂质趋于发生不希望的反应,而反应生成物增加了着色。
因此,需要提纯色数超过300的化合物B),例如通过蒸馏或通过诸如活性碳之类的吸附剂的处理。优选使化合物的色数低于260。
按静电化合物B)在模塑材料中的比例通常为0.01至10%,优选0.05至8%,特别优选0.1至5%。
优选以均匀母料的形式不仅使用染料A),也使用抗静电剂B),这些母料含有上述的塑料和较大量的一种或多种添加剂。它们比纯化合物A)或B)单独使用更容易均匀地混入大量的塑料中去。
含有可溶性染料A)和乙氧基化合物B)的热塑性模塑材料可以以各种聚合物为基础。
特别适合的聚合物有:苯乙烯、α-甲基苯乙烯、丙烯腈或甲基丙烯腈的均聚物和共聚物,C1-C12烷基丙烯酸酯和甲基丙烯酸酯的均聚物和共聚物,以及丁二烯的均聚物和共聚物。
这类聚合物的例子为:—聚苯乙烯,—苯乙烯和丙烯腈的共聚物,共中苯乙烯可以全部或部分地被α-甲基苯乙烯替代,而丙烯腈全部或部分地被甲基丙烯腈替代,及—用聚甲基甲基丙烯酸酯替代。
也可以使用这些聚合物与弹性聚合物的混合物,例如聚丁二烯和/或聚烷基丙烯酸酯。
更适合的基础材料为下列物质的均-和共聚物:乙烯、丙烯、异丁烯和1-丁烯。适合的还有诸如聚酯、聚酰胺、聚氨酯、聚碳酸酯和聚亚苯醚之类的缩聚和加聚产物。
此外,染料A)和乙氧化胺B)也可以加入到基于上述聚合物的掺合物的热塑性模塑材料中。
当然,本发明的模塑材料还可以另外包含加工和应用助剂,例如润滑剂、脱模剂、阻燃剂、颜料、抗氧化剂、紫外线稳定剂,还可以按常规量加入纤维和粉状填料以及增强剂。
本发明的模塑材料按通常的方法生产,所以没有必要就这一点作更专门的描述。
可以用该模塑材料生产按通常的方式的各种模塑制品,例如用挤出法或注射成型法。
本发明的模塑材料以其高着色稳定性而引人注目。以挤出法获得的塑料颗粒的颜色在进一步的加工过程中不发生变化,而且制得的模塑制品的颜色稳定。
在使用溶剂黄93(《色料索引》编号48160)的场合,使用本发明的模塑材料具有特殊的优点,原因是用这种对塑料着色特别重要的染料进行着色,先前证实特别容易脱色。
实施例
67%(重量)的苯乙烯和33%(重量)的丙烯腈的市售共聚物按已知的方法,与下列的0.003%(重量)的染料混合物A)直接掺混:—结构(I)的溶剂黄93(《色料索引》编号(C.I.No.48160),含有70%(重量)的染料混合物,—具有下列结构的溶剂紫13(C.I.No.60725),含有该种染料混合物的24%(重量),—溶剂红139,具有如下结构,含有该种染料混合物的6%(重重),及下述两者中任何一个B/1)2%(重量)的双(乙氧基化的)C12-正-烷基胺和双(乙氧基化
的)C14-正-烷基胺的混合物,其Hazen色数为250,或用于对比B/1′)2%(重量)的相应于B/1)的混合物,其Hazen色数为320,在挤出机内挤出并造粒。
将此颗粒在230℃和280℃时做成圆片。
抗静电剂的Hazen色数按德国标准DIN53409的规定测定;浓度各以模塑材料的重量计。
通过目测在230℃和280℃时所制圆片颜色不同于采用相同方法但不用抗静电剂所制的圆片颜色的程度,来判断此混合物的着色稳定性。与这些比较例的圆片比较,含有B/1)物质的圆片显示没有 变色发生,不依赖于其注塑熔融温度看出对于使用B/1’)物质情况时的着色质量更差。
Claims (6)
1.热塑性模塑材料,含有
A)一种可溶于其内的染料,和
B)一种N,N-双(2-羟乙基)-C6-C22-烷基胺或N,N-双(2-羟乙基)-C6-C22链烯基胺,该化合物具有按德国标准DIN53409规定的低于300的Hazen色数。
3.如权利要求1或2所述的热塑性模塑材料,其中的热塑性聚合物是苯乙烯、α-甲基苯乙烯、丙烯腈、甲基丙烯腈、C1-C12-烷基丙烯酸酯或甲基丙烯酸酯的均聚物或共聚物或共轭脂族二烯烃。
4.如权利要求1或2所述的热塑性模塑材料,其中的热塑性聚合物是乙烯、丙烯、异丁烯和1-丁烯的均聚物或共聚物。
5.权利要求1至4中的任何一项的热塑性模塑材料的应用,其中将该热塑性模塑材料用于生产模塑制品。
6.一种模塑成形的制品,其特征在于该制品是由权利要求1至4的任一项权利要求的热塑性模塑材料模塑成形的。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19501907.5 | 1995-01-23 | ||
DE19501907A DE19501907A1 (de) | 1995-01-23 | 1995-01-23 | Antistatisch ausgerüstete, gefärbte thermoplastische Formmassen |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1138061A CN1138061A (zh) | 1996-12-18 |
CN1082065C true CN1082065C (zh) | 2002-04-03 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN96105581A Expired - Fee Related CN1082065C (zh) | 1995-01-23 | 1996-01-23 | 抗静电着色热塑性模塑材料 |
Country Status (6)
Country | Link |
---|---|
US (1) | US5736598A (zh) |
EP (1) | EP0722978B1 (zh) |
JP (1) | JPH08253622A (zh) |
KR (1) | KR100382670B1 (zh) |
CN (1) | CN1082065C (zh) |
DE (2) | DE19501907A1 (zh) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0211651A2 (en) * | 1985-08-06 | 1987-02-25 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Method of improving the clarity of propylene polymers |
EP0267695A2 (en) * | 1986-11-11 | 1988-05-18 | Imperial Chemical Industries Plc | Composition comprising a carboxylic acid and an amine |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1262593B (de) * | 1965-05-07 | 1968-03-07 | Siemens Ag | Antistatika fuer Styrolpolymerisate |
GB1134949A (en) * | 1965-05-14 | 1968-11-27 | Sumitomo Chemical Co | Method for treating crude bis--ß-hydroxyethyl terephthalate |
DE3416896A1 (de) * | 1984-05-08 | 1985-11-14 | Bayer Ag, 5090 Leverkusen | Praktisch farblose, organische polyisocyanate, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von polyurethankunststoffen |
US5157067A (en) * | 1990-06-27 | 1992-10-20 | Ferro Corporation | Liquid colorant/additive concentrate for incorporation into plastics |
-
1995
- 1995-01-23 DE DE19501907A patent/DE19501907A1/de not_active Withdrawn
-
1996
- 1996-01-13 DE DE59603815T patent/DE59603815D1/de not_active Expired - Lifetime
- 1996-01-13 EP EP96100462A patent/EP0722978B1/de not_active Expired - Lifetime
- 1996-01-23 JP JP8009425A patent/JPH08253622A/ja not_active Withdrawn
- 1996-01-23 US US08/590,457 patent/US5736598A/en not_active Expired - Fee Related
- 1996-01-23 CN CN96105581A patent/CN1082065C/zh not_active Expired - Fee Related
- 1996-01-23 KR KR1019960001350A patent/KR100382670B1/ko not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0211651A2 (en) * | 1985-08-06 | 1987-02-25 | REXENE PRODUCTS COMPANY (A Delaware Corporation) | Method of improving the clarity of propylene polymers |
EP0267695A2 (en) * | 1986-11-11 | 1988-05-18 | Imperial Chemical Industries Plc | Composition comprising a carboxylic acid and an amine |
Also Published As
Publication number | Publication date |
---|---|
DE19501907A1 (de) | 1996-07-25 |
US5736598A (en) | 1998-04-07 |
CN1138061A (zh) | 1996-12-18 |
EP0722978B1 (de) | 1999-12-08 |
DE59603815D1 (de) | 2000-01-13 |
EP0722978A1 (de) | 1996-07-24 |
KR100382670B1 (ko) | 2003-07-18 |
JPH08253622A (ja) | 1996-10-01 |
KR960029386A (ko) | 1996-08-17 |
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