CN1040224C - 聚氯乙烯部件用的涂料及用途和用其涂覆的聚氯乙烯部件 - Google Patents
聚氯乙烯部件用的涂料及用途和用其涂覆的聚氯乙烯部件 Download PDFInfo
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Abstract
本发明涉及用于聚氯乙烯部件的涂料组合物,基于介质、交联剂和热塑性粉末。它特别适用于涂敷窗户、百叶窗和门用的聚氯乙烯部件。这样涂敷的聚氯乙烯精加工件具有特殊的冲击强度和抵抗磨损、摩擦和恶劣气候的能力。
Description
本发明涉及一种涂层,具有彩色或透明膜的形式,有光滑或结构外观;并涉及它的制备方法、用它涂敷聚氯乙烯底材的应用、特别涉及用作聚氯乙烯精加工件及其配件的制品(窗架、卷帘、卷帘箱等)。本发明还涉及这种涂敷过的由聚氯乙烯制成的部件和精加工件及其配件。
聚酰胺基的涂料具有特别广泛的用途,包括用于木材(家具、办公家具)、铝(预上漆工业,作为卷帘涂料)、塑料底材(数据处理、音响和视频设备)上的涂料和地面涂料(停车场、运动场)。
已经申请了一些特别针对这些应用的专利,涉及预上漆类型的应用我们将提到欧洲专利EP-0047508。这篇专利描述了一种利用皮带上漆(卷材涂漆法)工艺来涂敷金属物体的涂料组合物。该涂料组合物的特征在于它含有一种包含羟基官能团的介质、一种嵌段多异氰酸酯和一种聚酰胺粉末。然后将该涂层在200~260℃温度下交联25~50秒,这个温度太高以致于不能用在变形极限在60℃~80℃范围内的硬质聚氯乙烯部件上。
日本申请54.64945,在18个月时以JP 55157661号公开于1980年12月9日,描述了一种基于聚酰胺6或6.6或6.10、硅油和一种特殊氨基甲酸乙酯预聚物的涂料,设计用于汽车工业涂敷聚氯乙烯滑轨。采用这种涂料是为了获得与摩擦系数相关的专门特性。
法国专利FR 1469096要求了一种用作地面涂料的用空气干燥的聚氨酯/聚酰胺体系的权利,预期目的是防滑作用。
这些部件和配件可以通过挤出或模塑得到。
聚氯乙烯窗户的缺点之一是它的白色。
生产彩色聚氯乙烯精加工件,要求解决复杂技术问题,特别涉及在很宽的色彩范围内和可接受的经济条件下的冲击性能、美学上的均匀性和耐久性的问题。
目前已知的四种可能赋予部件色彩的技术是:
-整体着色(Colouring in bulk)
-共挤出
-饰面(Veneering)
-上漆
整体着色很难,因为聚合物和颜料的某些成分之间的不相容性导致材料对紫外光表现出不良性能。
共挤出要点是将白色聚氯乙烯构件和在部件外层部分的彩色聚甲基丙烯酸甲酯(PMMA)一起挤出。尽管该技术已被充分掌握并且是可靠的,但也产生了许多障碍,主要是经济情况。制造和储存费用非常高。
饰面是目前采用最广泛的技术。它的要点是当部件离开挤出机时将聚合物膜热粘合到部件上。这样就得到了性能优良的彩色部件,该方法已被采用多年,没有明显的不足。
然而,这种技术有两个缺点:由于工作现场条件经常比较差,冲击性能经常是靠不住的,并且最重要的是高储存费。实际上,保存和制定一个标明多种颜色的商品清单是必要的。而且,色彩范围通常是受约束的,主要是由于储存的限制。
本发明的一个目的是提供一种用于聚氯乙烯部件的涂料。
本发明的另一个目的是上述涂料涂覆在聚氯乙烯部件上或由聚氯乙烯制成的精加工件及其配件上的应用。
本发明又一个目的是提供涂覆了本发明涂料组合物的聚氯乙烯制成的部件或精加工件及其配件。
已经发现了一种涂层,由单层或多层涂料组成,该涂料用整体着色或无色的热塑性树脂在加颜料或未加颜料的液态漆中的分散体组成,该液态漆包括一种(或多种)介质和一种可溶于有机溶剂的交联剂。随后将该涂料沉积在聚氯乙烯精加工件上,然后在多数情况下在大约50℃的红外烘箱中使之交联。
这些聚酰胺基的涂料使克服大量相关的限制成为可能,特别是涉及美学方面、对紫外线的性能和冲击强度。在应用中的高度柔性使消除储存的缺陷成为可能。
本发明是一种用于聚氯乙烯部件的涂料组合物,包含:
a)介质,b)交联剂,c)悬浮体状的细分散的热塑性树脂,可加可不加颜料、染料和填料,d)溶剂,
该介质可使聚氯乙烯的添加剂和增塑剂慢慢从漆膜中渗出,该漆膜是在形成粘附于聚氯乙烯上的膜时通过交联上述组合物得到的。
本发明的涂层包含以粉末形式存在的固体热塑性树脂,颗粒尺寸最大为200微米,优选在0.5~60微米之间。相对于干燥涂层,热塑性树脂的重量百分数可占0.5~80%,优选0.5~40%。介质优选为一种可溶于溶剂的聚合物。
交联剂也最好可溶于溶剂中。
一旦被交联,该漆料必然是耐恶劣气候、耐久和耐清洗剂的。而且它必须粘结在聚氯乙烯上。
优选情况是应该形成具有足够大网眼的网状结构,以使聚氯乙烯的添加剂和增塑剂可以慢慢渗出。
这种可包含也可不包含羟基和/或羧基的介质可以是例如聚丙烯酸酯、环氧树脂、聚醚、聚酯、己内酯或乙烯基类型。
按照本发明的一种优选形式,该漆料是两种树脂A1和A2的混合物。
A1是一种包含羟基和/或羧基的树脂,例如,是聚丙烯酸酯、环氧树酯、聚醚、聚酯或己内酯类型的树脂。
A2是一种包含羟基和/或羧基的氯化乙烯基树脂。
树脂A1和A2优选具有350~35000的数均分子量,并具有羟基和/或羧基官能度,以重量百分数表示,为0.5~6,优选0.8~4。
介质可占干燥涂层重量的20~99.5%。
按照本发明的优选形式,树脂A1是羟基化的聚酯树脂,树脂A2是羟基化的乙烯基乙酰氯化物的共聚物。
轻度支化的羟基化聚酯树脂对膜的性能(耐候性、耐化学性、时间上的耐久性)起了主要贡献;事实上,在用硬化剂交联以后,正是轻度支化使获得带相对大的网眼的三维聚合物网状结构成为可能,这种网状结构可以使增塑剂存在于聚氯乙烯当中,随时间慢慢渗出材料,穿过涂料膜而不剥离它。更窄网眼的聚合物晶格将不能使增塑剂迁移透过漆膜,并且随时间将造成涂层剥离。
被相对极化和氯化(如聚氯乙烯)的羟基化乙烯基乙酰氯化物共聚物树脂促进了对聚氯乙烯底材的粘结性;被羟基化的事实使得它还有可能与异氰酸酯硬化剂发生交联,且不降低漆膜的耐冲击性。
采用的交联剂优选芳香族的、脂肪族的或环脂族的异氰酸酯化合物,并且最好是二异氰酸酯和三异氰酸酯。在这种情况下,包含羟基(和/或)羧基官能团/异氰酸酯的聚合物对被称作聚氨酯。
还采用了一种未封闭的多异氰酸酯化合物作为交联剂。采用封闭的多异氰酸酯并不脱离本发明的范围,前提是在与聚氯乙烯相容的温度下它可被解封。
作为二异氰酸酯的实例可以提到1,6-六亚甲基二异氰酸酯(HTD),4,4′-二苯基甲烷二异氰酸酯(HMDI)和3-异氰酸根合甲基-3,5,5-三甲基环己基异氰酸酯(IPDI),这些实例是本申请人的公司特别优选的。
就羧基化的丙烯酸聚合物而论,还可以采用环氧化物丙烯酸酯作为交联剂。
交联剂的加入量优选使交联剂中活性基与包含羟基(和/或)羧基的聚合物中活性基的摩尔比在0.6~1.5范围内,最好为0.7~1.3。
热塑性树脂是指软化点在100℃~230℃之间的热塑性聚合物,并优选聚酰胺。作为适宜的聚酰胺,可以提到的有由一种或多种每分子包含6~12个碳原子的ω-氨基一元羧酸或相应的内酰胺组成的聚合物,例如:聚己内酰胺(PA-6),ω-氨基十一烷酸的聚合物(PA-11)和聚ω-十二碳内酰胺(PA-12)或共聚物,例如,己内酰胺和ω-氨基十一烷酸的共聚物(PA-6/11),己内酰胺和ω-十二碳内酰胺的共聚物(PA-6/12),以及己内酰胺、ω-氨基十一烷酸和ω-十二碳内酰胺的共聚物(PA-6/11/12)。
适宜的聚酰胺还可以是二胺例如1,6-己二胺的缩聚产物和二元羧酸的缩聚物,该二元羧酸有例如:己二酸、癸二酸、十二二酸和对苯二酸。这些聚酰胺的代表例子包括:聚(亚己基己二酰胺)(PA-6-6),聚(亚己基癸二酰胺)(PA-6,10)和聚(亚己基十二二酰胺)(PA-6.12)。可以用也可不用聚酰胺的混合物,前提是它们的软化点在110~230℃范围内。优选采用PA-11、PA-12、PA-6/12和/或PA-12.12,单独使用或混合使用。
热塑性树脂还指聚醚酰胺,其中包括聚醚酯酰胺,尤其是指专利FR 2273021和FR 2401947中描述的聚醚酯酰胺。
可以通过研磨聚合物或直接聚合成所需粒子尺寸来获得粉末,正如在专利EP 192515中特别描述的那样。
按照本发明,热塑性树脂的软化点在110℃~230℃范围内,优选120℃~210℃。软化点通常借助于Koefler台来测定。
可以采用沸点在40℃~310℃之间,优选在77℃~193℃之间的有机溶剂,作为增溶由羟基化的和/或羧基化的聚合物和交联剂组成的介质的溶剂。这些溶剂必须不使聚氯乙烯变脆。
溶剂的代表例子包括:二甲苯和甲苯类型的芳烃,乙酸乙酯、乙酸丁酯或乙酸乙二醇酯-乙氧基丙酸乙酯类型的脂肪族酯,酮如甲基·乙基酮、甲基异丁基酮和双丙酮醇,脂肪醇如丁醇、异丙醇、甲醇、乙醇和2-甲氧基丙醇(市场上以Dow Chemical公司的DowanolPM名称销售),沸点在30~160℃之间的脂肪烃(市场上例如以Total或Shell Chimie公司的商标Hydrosol Essence A、B、C、D、E、F、G或H销售)。溶剂占组合物总重量百分数的10~70%,优选占30~50%。
涂料组合物可含可不含一种或多种常用助剂或添加剂,例如:分散剂、改善流变性能的防流挂剂、消泡剂、抗紫外线稳定剂、流平剂、增塑剂、光亮调节剂和固化促进剂如对-甲苯磺酸、重金属盐和胺。
给涂料和热塑性树脂着色的适宜颜料属于常用类型,即性质上可以是有机或无机的酸性、中性或碱性颜料。如果需要,可将颜料进行预处理以改善它们的性能。作为适宜颜料的一个实例,可以提到的有二氧化钛、氧化铁红、钼铬橙、铬酸铅、炭黑和酞菁颜料。这里颜料还指金属颜料如铝和不锈钢。颜料与整个干燥涂层的比可达60%。
涂料组合物基本不含硅油类型的产物。后者的产物使涂层很滑而不能修整;修整材料粘不上。
按照本发明,不同的涂层可以用各种液体涂敷技术来涂敷,但优选采用用混合空气或无空气的气枪来喷涂,或者采用气枪、小碗式的或高速盘式的静电喷涂工艺。
在涂敷之前,底材可进行一次或多次表面处理以改善涂层的粘结性。举例来说,可进行底材表面的除油,氧化型处理如燃烧、电晕放电和等离子体处理。
在用涂料涂敷完底材之后,通常在一个加热到20℃~80℃,优选40℃~60℃之间的烘箱中将该涂层固化2~24小时,或者在表面温度为50~100℃之间的红外炉下固化5~30分钟。
按照本发明,借助于涂敷得到的组合物材料由下列部分组成:
-厚度可在10~100微米,优选在10~40微米之间的单涂层或多涂层,
-底材,优选各种厚度的聚氯乙烯部件。
按照本发明涂敷的聚氯乙烯部件和精加工件的优点是:
-高耐候性(耐紫外光、潮湿等),
-高冲击强度,即使在低温下(不剥落),
-高抗划伤性,
-在Erichsen model 435试验中的耐力:高于15牛顿,
-被涂部件可以弯曲或承受其它形变,涂敷件保持不变。
此外,还观察到下列三种性能:
-在窗户密封处的耐磨性(在开窗和关窗过程中的磨损),
-未涂敷聚氯乙烯拉伸弹性的保留(而且甚至在老化后可以改善这种拉伸弹性,因为涂层保护了聚氯乙烯并防止了表面微裂),
-能够保留聚氯乙烯的可焊接性(部件和焊缝周围可被涂敷,且焊缝的机械强度与未被涂敷的聚氯乙烯一样好)。
部件可被涂敷、切割和装配以得到精加工件。焊接并未改变涂敷件。
本申请人发现这样涂敷的聚氯乙烯精加工制品对于喷砂引起的磨损和防风毡的磨损都有高的抵抗力,这种防风毡可能存在于,例如,窗户移动部分或门的移动部分所靠的框架上。
喷砂试验如下:
在80磅/平方英寸的气压和40~60立方英尺/分的流速下,用玻璃珠(尺寸:在53~105微米之间)以6厘米的恒定距离喷15秒。
普通聚氨酯:6~8秒后涂层剥落。
15秒后全部聚氨酯都消失了。
用聚酰胺填充的聚氨酯:
观察到有一些光泽损失和颜色变化。
防风刷的耐磨试验:
滑孔的20000次冲击:10000次冲击后产品开始微微泛光但保持完好。
还发现聚氯乙烯精加工件的这种涂层对冲击的承受能力以及对洗涤剂和玻璃清洗产品的承受能力都很好。
这种涂层适应由加热或精加工件的变形引起的膨胀而不产生任何损坏或微裂。
下列实施例是对本发明的举例说明,但不局限于此。
除非另外声明,所示的量都是以重量表示。
实施例1
A)涂料的制备
通过将涂料的各组分按一定比例混合分散在一种或多种溶剂中来制备研磨料。
操作在一个球磨机中进行。
一旦分散已完成,就将剩余的涂料加入并使各组分充分混合,然后调节涂料粘度。
B)涂料的构成
重量(g)
研磨
轻度支化的羟基化的聚酯树脂
-羟基含量: 4.3%
-当量: 395
-20℃下的相对密度: 1.17
-23℃下的粘度: 2200毫帕·秒
在乙酸丁酯中稀释到60%重量。
此溶液称为树脂A 21.00
羟基化的乙烯基乙酰氯化物的共聚
物型的树脂
-羟基含量: 2.3%
-相对密度: 1.39
-数均分子量: 27000
-玻璃化转变温度: 79℃
-特性粘度: 0.53
在下列溶剂中形成的重量浓度为20%的溶液中:
-羟基化的乙烯基乙酰氯化物的共聚物: 20 26.70
-乙酸丁酯: 31
-乙酸甲氧基丙酯: 16
-甲基·乙基酮: 33
100
此溶液称为树脂B
研磨添加剂:
-湿润剂: 0.15
-触变剂: 0.30
研磨颜料:
-酞菁蓝 0.55
-金红石二氧化钛 0.80
-炭黑 0.40
-铬黄 10.30
补体:
-树脂A: 10.45
-树脂B: 13.35
-表面活性剂: 0.35
-在乙酸甲酯中重量浓度为10%的锌盐: 1.70
-在二甲苯中重量浓度为5%的月桂酸二丁酯:0.40
-粒子尺寸在20~60微米之间的聚酰胺11热
塑性树脂 4.65
粘度调节:
-二甲苯 2.00
-乙酸丁酯 6.90
100.00
在使用时将15份重量的多异氰酸酯硬化剂加入到100份重量的这种组合物中(多异氰酸酯的特性:基于六亚甲基二异氰酸酯(HMDI)的“缩二脲”型脂肪族多异氰酸酯,固体含量:75%,NCO含量:16.4%,23℃下的粘度:250毫帕·秒)。
C)涂敷
在用适当溶剂的混合物对聚氯乙烯底材去油之后,用气枪喷涂该涂层,然后在50℃下交联12小时;这样涂敷后,在敞开空气中冷却底材。得到的组合物材料由下列部分组成:-聚氯乙烯部件,-厚度约25~40微米的表面涂层。试验1:-泰伯尔法耐磨仪(NFT 30015):CS17碾轮循环1000次载荷:500克;重量损失110毫克-粘结性:NFT 30038-得分0-QUV(NFT 30036):经过1600小时QUV之后,我们有相对于灰度为4~5的降解。粘结性良好:得分0-冲击(NFP 24500)冷(-10℃)在1米高落下的1千克冲击下无断裂(即在-10℃下能量为2焦耳)。
Claims (13)
1、用于聚氯乙烯部件的涂料组合物,包含:
a)相对干燥涂层,20-99.5%的介质,该介质为轻度支化的可包含也可不包含羟基和/或羧基的聚丙烯酸酯、环氧树脂、聚醚、聚酯、己内酯或乙烯基类型的树脂;
b)异氰酸酯化合物或环氧化物丙烯酸酯交联剂,所述交联剂加入量使交联剂中活性基与包含羟基和/或羧基的聚合物中活性基的摩尔比在0.6~1.5范围内;
c)悬浮体状的细分散的聚酰胺或聚醚酰胺热塑性树脂,可加可不加颜料、染料和填料;
d)溶剂。
2、根据权利要求1的组合物,其特征在于所述的介质是两种树脂A1和A2的混合物:
A1是一种包含羟基和/或羧基的轻度支化的树脂,
A2是一种包含羟基和/或羧基的氯化乙烯基树脂。
3、根据权利要求2的组合物,其特征在于树脂A1是羟基化的聚酯树脂,树脂A2是羟基化的乙烯基乙酰氯化物的共聚物。
4.根据权利要求1的组合物,其特征在于交联剂中活性基与包含羟基和/或羧基的聚合物中活性基的摩尔比在0.7~1.3范围内;
5.根据权利要求1的组合物,其特征在于所述的热塑性树脂为干燥涂层重量的0.5-80%。
6.根据权利要求5的组合物,其特征在于所述的热塑性树脂为干燥涂层重量的0.5-40%。
7.根据权利要求1的组合的,其特征在于所述的溶剂为整个组合物重量的10-70%。
8.根据权利要求7的组合的,其特征在于所述的溶剂为整个组合物重量的30-50%。
9、根据权利要求1-8之一的组合物,其特征在于交联剂是未封闭的多异氰酸酯化合物。
10、根据权利要求1-8之一的组合物,其特征在于细分散的热塑性树脂是聚酰胺粉末。
11、根据权利要求9的组合物,其特征在于细分散的热塑性树脂是聚酰胺粉末。
12、权利要求1-11之一的组合物涂敷在聚氯乙烯部件上或由聚氯乙烯制成的精加工件及其配件上的应用。
13、涂敷了权利要求1-11之一的组合物的由聚氯乙烯制成的部件或精加工件及其配件。
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FR9301316A FR2701268B1 (fr) | 1993-02-05 | 1993-02-05 | Peintures à base de poudres de polyamide destinées au revêtement de profilés PVC. |
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DE10206225C1 (de) * | 2002-02-15 | 2003-09-18 | Basf Coatings Ag | Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen |
DE10248324A1 (de) * | 2002-10-17 | 2004-05-06 | Basf Coatings Ag | Thermisch und mit aktinischer Strahlung härtbarer Beschichtungsstoff und Verfahren zum Beschichten miktoporöser Oberflächen |
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JP5153991B2 (ja) * | 2004-02-26 | 2013-02-27 | 日本ゴア株式会社 | 防水透湿性複合フィルムおよび防水透湿性複合生地 |
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CA2569899A1 (en) * | 2005-11-30 | 2007-05-30 | Christian Guillemette | Prefabricated window structure including a cosmetic aluminium sheet |
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1993
- 1993-02-05 FR FR9301316A patent/FR2701268B1/fr not_active Expired - Fee Related
-
1994
- 1994-01-26 NO NO19940269A patent/NO311141B1/no unknown
- 1994-01-31 EP EP94400198A patent/EP0610122A1/fr not_active Withdrawn
- 1994-02-01 US US08/190,748 patent/US5626958A/en not_active Expired - Fee Related
- 1994-02-02 JP JP6030897A patent/JP3065473B2/ja not_active Expired - Fee Related
- 1994-02-04 FI FI940528A patent/FI107806B/fi not_active IP Right Cessation
- 1994-02-04 MX MX9400930A patent/MX9400930A/es unknown
- 1994-02-04 ZA ZA94780A patent/ZA94780B/xx unknown
- 1994-02-04 PL PL94325671A patent/PL176750B1/pl not_active IP Right Cessation
- 1994-02-04 CA CA002114993A patent/CA2114993C/fr not_active Expired - Fee Related
- 1994-02-04 BR BR9400433A patent/BR9400433A/pt not_active Application Discontinuation
- 1994-02-04 AU AU54933/94A patent/AU667251B2/en not_active Ceased
- 1994-02-04 HU HU9400322A patent/HU220342B/hu not_active IP Right Cessation
- 1994-02-04 KR KR1019940002127A patent/KR0129803B1/ko not_active IP Right Cessation
- 1994-02-04 SK SK127-94A patent/SK284002B6/sk unknown
- 1994-02-04 PL PL94302145A patent/PL176071B1/pl not_active IP Right Cessation
- 1994-02-05 CN CN94102401A patent/CN1040224C/zh not_active Expired - Fee Related
- 1994-02-05 TW TW083100965A patent/TW320649B/zh active
-
1996
- 1996-10-11 US US08/730,537 patent/US5972514A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55157661A (en) * | 1979-05-28 | 1980-12-08 | Toyoda Gosei Co Ltd | Automobile glass run |
CN1050035A (zh) * | 1989-08-11 | 1991-03-20 | 阿托化学公司 | 以聚酰胺和/或聚醚酯酰胺为基础的粉状热塑性组合物,其制备方法以及用于涂布金属基的应用 |
CN1075734A (zh) * | 1993-04-12 | 1993-09-01 | 哈尔滨玻璃钢制品厂 | 无毒环氧增韧涂料 |
Also Published As
Publication number | Publication date |
---|---|
CA2114993A1 (fr) | 1994-08-06 |
EP0610122A1 (fr) | 1994-08-10 |
FI940528A (fi) | 1994-08-06 |
KR0129803B1 (ko) | 1998-04-03 |
JP3065473B2 (ja) | 2000-07-17 |
SK284002B6 (sk) | 2004-07-07 |
SK12794A3 (en) | 1994-08-10 |
AU5493394A (en) | 1994-08-11 |
FI940528A0 (fi) | 1994-02-04 |
HUT68137A (en) | 1995-05-29 |
NO311141B1 (no) | 2001-10-15 |
CA2114993C (fr) | 2000-01-18 |
CN1092446A (zh) | 1994-09-21 |
US5972514A (en) | 1999-10-26 |
BR9400433A (pt) | 1994-08-23 |
PL302145A1 (en) | 1994-08-08 |
PL176071B1 (pl) | 1999-03-31 |
NO940269L (no) | 1994-08-08 |
TW320649B (zh) | 1997-11-21 |
FR2701268B1 (fr) | 1995-04-14 |
MX9400930A (es) | 1994-08-31 |
NO940269D0 (no) | 1994-01-26 |
AU667251B2 (en) | 1996-03-14 |
HU9400322D0 (en) | 1994-05-30 |
FR2701268A1 (fr) | 1994-08-12 |
PL176750B1 (pl) | 1999-07-30 |
JPH06287518A (ja) | 1994-10-11 |
HU220342B (hu) | 2001-12-28 |
US5626958A (en) | 1997-05-06 |
ZA94780B (en) | 1994-09-08 |
FI107806B (fi) | 2001-10-15 |
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