CN100390234C - 用于电子设备的外壳 - Google Patents

用于电子设备的外壳 Download PDF

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CN100390234C
CN100390234C CNB2004800194552A CN200480019455A CN100390234C CN 100390234 C CN100390234 C CN 100390234C CN B2004800194552 A CNB2004800194552 A CN B2004800194552A CN 200480019455 A CN200480019455 A CN 200480019455A CN 100390234 C CN100390234 C CN 100390234C
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plastics
polyamide
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G·埃斯
R·诺伊豪斯
K-M·赖因弗兰克
R·克罗伊斯
G·朔贝尔
W·古廷
K·乌斯克
M·森德勒
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34928Salts
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/34Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477Six-membered rings
    • C08K5/3492Triazines
    • C08K5/34924Triazines containing cyanurate groups; Tautomers thereof
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    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06Polyamides derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1372Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1397Single layer [continuous layer]

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  • Injection Moulding Of Plastics Or The Like (AREA)
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Abstract

本发明涉及一种用于电子设备的外壳。所述外壳由耐热、阻燃的热塑性塑料通过注射成型制备而得。所述热塑性塑料是具有无卤阻燃性的聚酰胺基塑料。

Description

用于电子设备的外壳
本发明涉及一种用于电子设备的外壳,其由一种具有无卤阻燃性的耐热性热塑性塑料组成,本发明还涉及该塑料用于通过注射成型制备所述外壳的用途。
如今,用于电子设备的大表面积外壳通常由热塑性塑料生产。在这些电子设备具有显示屏的情况下,如电视机、视频监视器或计算机监视器,一个需要考虑的特殊因素是电子元件会释放出大量热量,电子设备的外壳因此而变得非常热。
鉴于产品安全性的考虑,如果设备发生故障,或者暴露于外部热量,如燃烧的蜡烛,则为了防止起火或阻止火势蔓延,在某些情况下需要在热塑性塑料中加入阻燃剂。但是,许多这些阻燃剂是卤化的,其本身会引发额外的危险,因为这些化学药品的使用会产生毒物。因而,一度使用具有无卤阻燃性的热塑性塑料,例如由聚亚苯基醚和抗冲击聚苯乙烯组成的高分子共混物(PPE/HIPS)或聚碳酸酯/丙烯腈-丁二烯-苯乙烯共聚物的共混物(PC/ABS)。
但是,这些材料在外壳的生产过程以及成品设备的使用过程中存在许多缺点。比如,第一,通过注射成型制备外壳的过程要求相对长的周期,这导致了相应的低产率。第二,当前现有技术使用的材料产生令人不满意的表面质量以及模具表面的再生产精度。因此,许多外壳需要另外上漆。其它可能提及的缺点是对应力开裂有高敏感性,这使得外壳在机械应力下很容易破裂,并且在连续暴露于UV辐照的条件下具有强烈的变黄倾向,在浅色外壳的情况下尤其明显。
因此,本发明的一个目的是提供一种用于电子设备、尤其是具有显示屏的电子设备的外壳,如电视机、视频监视器或计算机显示器,所述外壳可由具有无卤阻燃性的热塑性塑料通过注射成型的加工方法制得。选择的这种具有无卤阻燃性的热塑性塑料例如能够缩短生产周期,同时提高表面质量和模具表面的再生产精度。本发明的另一目的是降低对应力开裂的敏感性,提高塑料的抗泛黄能力。
我们发现,这一目的可以通过由聚酰胺基热塑性塑料制备所述外壳来实现。与现有技术使用的PPE/HIPS共混物和PC/ABS共混物相比,聚酰胺基热塑性塑料具有改善的表面质量和更短的注模周期。
为了实现本发明的目的,所述聚酰胺基熟塑性塑料是包含至少一种聚酰胺的塑料。其可以是脂族或部分芳族聚酰胺,可以含有部分晶体结构或无定型结构。根据本发明制造的用于电子设备的外壳优选由脂族聚酰胺制备。特别适用于本发明的材料包括尼龙-6、尼龙-6,6、尼龙-6/6,6共聚酰胺或它们的混合物。本发明使用的混合物也可以是由具有相同单体单元和不同溶液粘度的聚酰胺组成的混合物。为制备所述外壳,优选使用溶液粘度低于140ml/g的自由流动的聚酰胺,该粘度根据ISO 307在包含0.005g/ml样品的硫酸溶液中测定。
为了满足消防的要求,用于制备电子设备外壳的热塑性塑料应该具有阻燃性。已经发现,聚酰胺即使在不添加阻燃剂的情况下也具有阻燃性。加入阻燃剂可提高其阻燃性。DE-A-2827867先前已经公开了具有无卤阻燃性的热塑性塑料。其中将含磷的碳化合物与含氮碱、即三聚氰胺和/或双氰胺和/或胍结合用作阻燃剂。另外,DE-A-19607635公开了次膦酸或二次膦酸的钙和铝盐可以用作聚酰胺塑料中的阻燃添加剂。
已经发现,即使不同时使用次膦酸盐,三聚氰胺氰脲酸酯的使用也可以使阻燃性显著提高。因此,使用三聚氰胺氰脲酸酯作为阻燃添加剂的优点是也可以省略使用含磷化合物。
用于电视机、视频监视器或计算机显示器的外壳特别属于大表面积元件。若要获得短的周期和清洁的表面,就需要聚合物熔体在模具内迅速分配。这可以通过使用低粘度聚合物熔体来实现。而且,在高粘度聚合物熔体的情况下填充模腔所需要的注射压力明显高于低熔体粘度的塑料的情况。在高粘度熔体和过低的注射压力的情况下,聚合物熔体在到达加工件边缘之前就会在模具内出现早期硬化现象,从而使制得的元件具有不适当的形状。
下述实施例用于进一步解释本发明。
为了研究热塑性塑料的性质,每种情况的测试板是使用一个测试模具注射成型。这些测试板用于测试以下各性质:UL 94阻燃性等级,与乙醇接触的抗应力开裂性,UV泛黄,表面质量,以及注射成型的周期。研究了当前用于制备电子设备外壳的PPE/HIPS和ABS/PC的性质。将根据本发明用于制备外壳的聚酰胺基热塑性塑料的测试结果与这些后面的结果进行对比。
对比例C1
研究了例如由Noryl V 180 HF得到的PPE/HIPS的性质。阻燃性研究根据Underwriters Laboratories Inc.的UL 94进行。为此,将一个垂直悬挂的测试板与火焰接触,然后考察火势蔓延的速率和塑料的滴落行为。根据样片厚度,阻燃等级分为V-0、V-1和V-2级,其中V0级为最好的等级。
UV泛黄现象是根据ISO 4892测试。为此,将样片以0.55W/m2的剂量在波长340nm的光束下曝光1000小时。然后使用Optronic Colour Flash 45对色度进行测定。
为了研究抗应力开裂性,将样品于室温下在乙醇中贮藏7天。之后,将样品干燥,根据ISO 527-2测试断裂接伸应力的下降值。该值在此定义为断裂时占原始拉伸应力的百分比。
为确定注射成型加工过程的周期,在测试模具内将测试件注射成型。为确定周期,将时间缩短直到测试件的质量下降。
通过对测试板表面质量的目测分析确定表面质量,将测试板分为1-5五个等级,1级为很好,5级为很差。
每个测试结果参见表1。
对比例C2
研究了用于制备电子设备外壳的商品名为Bayblend FR 2000的商用ABS/PC共聚物的性质。考察了如对比例C1中所述的性质。结果同样参见表1。
实施例1
研究了具有下述混合规格的聚酰胺混合物的性质:
59.00%的溶液粘度约为150ml/g的尼龙-6
33.00%的溶液粘度约为125ml/g的尼龙-6,6
8.00%的三聚氰胺氰脲酸酯
所述添加剂由双螺杆挤出机挤出形成聚酰胺混合物,然后通过注射成型机进行进一步加工。考察了如对比例C1中所述的性质。结果同样参见表1。
实施例2
按照实施例1的混合规格,用溶液粘度约为125ml/g的尼龙-6代替溶液粘度约为125ml/g的尼龙-6,6。聚酰胺混合物同样通过双螺杆挤出机制备,然后由注射成型机进行进一步加工。同样考察了如对比例C1中所述的性质。结果参见表1。
实施例3
研究了按照下述混合规格由双螺杆挤出机制备的聚酰胺:
100%的溶液粘度约为150ml/g的尼龙-6
制得的聚酰按通过注射成型机进行进一步加工,并做了应用于其他塑料的研究。同样,结果参见表1。
实施例4
由双螺杆挤出机制备了具有下述混合规格的聚酰胺:
100%的溶液粘度约为150ml/g的尼龙-6,6
该聚酰胺也由注射成型机进行进一步的加工,并做了应用于其他塑料的研究。同样,这些研究的结果参见表1。
表1
Figure C20048001945500061

Claims (7)

1.一种用于包含阴极射线管或平面显示屏的电子设备的外壳,该外壳由耐热、阻燃的热塑性塑料通过注射成型制备而得,其中所述塑料具有聚酰胺基结构,特征在于所述塑料包含至少两种具有不同溶液粘度的聚酰胺的混合物。
2.根据权利要求1所述的外壳,其中所述塑料包含尼龙-6。
3.根据权利要求1所述的外壳,其中所述塑料包含尼龙-6,6。
4.根据权利要求1所述的外壳,其中所述聚酰胺基塑料包含未卤化的阻燃剂。
5.根据权利要求4所述的外壳,其中所述阻燃剂是三聚氰胺氰脲酸酯。
6.根据权利要求1所述的外壳,其中所述电子设备是电视机或监视器。
7.耐热、阻燃的并包含至少两种具有不同溶液粘度的聚酰胺的混合物的聚酰胺基热塑性塑料在通过注射成型制备用于包含阴极射线管或平面显示屏的电子设备的外壳中的用途。
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EP1646690B1 (de) 2010-12-29
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BRPI0412378A (pt) 2006-09-19
US20070043149A1 (en) 2007-02-22
CA2531771A1 (en) 2005-01-20
EP1646690A1 (de) 2006-04-19
KR101011311B1 (ko) 2011-01-28
DE502004012066D1 (de) 2011-02-10
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