CN1330679A - 可用x射线造影检测的塑料模塑组合物 - Google Patents
可用x射线造影检测的塑料模塑组合物 Download PDFInfo
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- CN1330679A CN1330679A CN99814348A CN99814348A CN1330679A CN 1330679 A CN1330679 A CN 1330679A CN 99814348 A CN99814348 A CN 99814348A CN 99814348 A CN99814348 A CN 99814348A CN 1330679 A CN1330679 A CN 1330679A
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- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- NTHXOOBQLCIOLC-UHFFFAOYSA-N iohexol Chemical compound OCC(O)CN(C(=O)C)C1=C(I)C(C(=O)NCC(O)CO)=C(I)C(C(=O)NCC(O)CO)=C1I NTHXOOBQLCIOLC-UHFFFAOYSA-N 0.000 description 1
- 229960001025 iohexol Drugs 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- VYAGDYWTCWDKIS-UHFFFAOYSA-N phenobutiodil Chemical compound CCC(C(O)=O)OC1=C(I)C=C(I)C=C1I VYAGDYWTCWDKIS-UHFFFAOYSA-N 0.000 description 1
- 229950009173 phenobutiodil Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
本发明涉及可由X射线造影检测的塑料材料。所述塑料材料包括低分子量碘化合物。本发明还涉及生产所述塑料材料的方法并涉及低分子量碘化合物在塑料材料中改进透明X射线反差方面的应用以及含有低分子量碘化合物并且具有改进的X射线反差的玩具。
Description
本发明提供了含有低分子量碘化合物的可用X射线造影的塑料材料，制备含有低分子量碘化合物的可用X射线造影的模塑组合物的方法，低分子量碘化合物在透明塑料材料中改进X射线反差方面的应用以及含有低分子量碘化合物的具有改进的X射线反差的玩具。
医学领域及儿童玩具领域在寻求可通过X射线在人体中检测到的具有尽可能高透明度和良好机械性能的材料。与金属物品相反，一般在X射线影像上检测不到塑料制成的玩具。这些类型的模塑组合物可通过适当添加剂做成可用X射线造影的。
这些类型的模塑组合物描述于例如DE-A 195 45 289中。在该专利中，描述了由含有BaSO4添加剂的ABS制成的可用X射线造影的热塑性模塑组合物。
X射线可检测的模塑组合物还描述于Silberman-Hazony的《聚合物科学工程百科全书》(1988)，14，1-8中。描述了含有作为X射线造影剂的各种重金属的热塑性材料。此外，提到了含卤三聚物。
最后，FR 2223403描述了类似于US 3,361,700和3,645,955中所述的含有含碘水杨酸、苯甲酸及其酯的PVC及其它乙烯基聚合物。但是，PVC不适于用于要求高透明度和良好机械性能的应用。
DE-A 197 26 191和专利US 3,469,704及其中引用的DE-A 17 20812描述了由含有含碘端基基团的聚碳酸酯制成的透明塑料模塑组合物。但是，在某些环境中，它们会涉及相当高的额外合成成本，因为聚合物链本身必须改性。
最后，US 3,382,207公开了作为聚碳酸酯添加剂的含碘二苯基碳酸酯。
因此，现有技术目前尚不能提供适当的可用X射线造影的用于透明塑料器件的塑料材料。由于其卓越的机械性能，迄今为止聚碳酸酯已特别用于要经受高机械应力的透明玩具器件。现在，欲意开发一类在常规X射线照片范围内可被检测到同时具有不变的高透明性并且对其机械性能造成尽可能最小损害的塑料材料。塑料材料仍可被检测得到的层厚应尽可能小，且最多为1.2mm。
目的是通过在标准热塑性材料中使用易于获得的添加剂以开发出在X射线影像中显示出适当反差同时还具有良好机械特性和透明性的模塑组合物。因为探索的是用于儿童玩具的材料，基于毒物学原因要避免添加重金属。
因此，本申请提供了含有至少一种低分子量碘化合物的可用X射线造影的塑料材料，其特征在于，碘化合物以0.1-25wt.％的量存在并且选自D-甲状腺素、L-甲状腺素、碘葡酰胺、N，N’-二(2，3-二羟丙基)-5-[N-(2，3-二羟丙基)-乙酰氨基]-3，4，6-三碘间苯二甲酰胺、α-(2，4，6-三碘苯氧基)-丁酸、β-溴-2，4，6-三碘苯乙醚、乙二醇-4-(碘苯基)-甲基醚-甲基醚以及下列通式(I)、(II)、(III)的芳族化合物：
其中R、R’、R”、R”’＝COOH、OH、NHCOR””、CONHR””、OR””、Cl、Br、F、R””，其中R””可以是H或含有1-18个碳原子的线性或支化烷基基团。而且，l＝0至5，m＝0至5-1，n＝0至3，o＝0至3-n，p＝0至4，q＝0至4-p，r＝0至4，s＝0至4-r，t＝0至5，u＝0至5-t。
为了制备碘葡酰胺见J.Cell.Biol.1991，113，45，为了制备Iohexol(N，N’-二(2，3-二羟丙基)-5-[N-(2，3-二羟丙基)-乙酰氨基]-3，4，6-三碘间苯二甲酰胺)见Sigma-Aldrich Chemie GmbH，Steinheim，德国，为了制备Baygnostil(α-(2，4，6-三碘苯氧基)-丁酸)见Bayer AG，Leverkusen，德国。
所有上述含碘化合物的混合物也是适宜的。
下列化合物是特别适宜的：4，4’-二碘联苯、2，3，5-三碘苯甲酸、2，4，6-三碘苯酚、4-碘苯酚、3-碘苯酚、2-碘苯酚、3，5-二碘水杨酸、3，5-二碘-2-羟基苯甲酸、4-碘苯甲酸、3-碘苯甲酸、2-碘苯甲酸、2，6-二甲基-4-碘苯酚、2-碘-4-苯基苯酚、3，3’-二碘-2，2’，6，6’-四甲基-4，4’-双酚、2，6-二碘-4-甲基苯酚、3，5-二碘-2-羟基苯甲酸、2，4-二氯-6-碘苯酚、1，4-二甲氧基-2，3-二甲基-5-碘苯、1，2-二甲氧基-4-碘苯、2，2’-二碘-4，4’，5，5’-四甲氧基联苯、4-碘-3-苯基苯甲醚、1，2-二甲氧基-3，4-二甲基-5-碘苯、2，2’-二碘-3，3’-二甲基-4，4’，5，5’-四甲氧基联苯、1，4-二甲氧基-2-碘-5-甲基苯、1，2-二甲氧基-4-碘-5-甲基苯、1，2-二碘-4，5-二甲氧基苯、2，2’-二碘-3，3’，4，4’，5，5’-六甲氧基联苯、2，2’-二碘-4，4’-二甲氧基-3，3’，5，5’-四甲基联苯，非常特别优选4，4’-二碘联苯。
可用X射线造影的塑料材料包含用量为0.5-20wt.％，优选为0.8-10wt.％且特别优选为1-5wt.％的低分子量碘化合物。
透明的热塑性材料优选用作塑料，特别优选烯属不饱和单体的聚合物和/或双官能团反应性化合物的缩聚物。
特别适宜的塑料为基于二酚的聚碳酸酯或共聚碳酸酯、聚丙烯酸酯或共聚丙烯酸酯及聚甲基丙烯酸酯或共聚甲基丙烯酸酯如聚甲基丙烯酸甲酯或共聚甲基丙烯酸甲酯，或者与苯乙烯的共聚物如透明的聚苯乙烯/丙烯腈(SAN)，以及透明的环烯烃、对苯二甲酸的缩聚物或共缩聚物如聚对苯二甲酸乙二酯或共聚对苯二甲酸乙二酯(PET或CoPET)或二醇改性的PET。
本领域技术人员用聚碳酸酯和/或共聚碳酸酯获得了优异的结果。
在本发明的上下文中热塑性芳族聚碳酸酯为均聚碳酸酯或共聚碳酸酯；聚碳酸酯可以是直链的或用已知方式支化的。
这些聚碳酸酯以已知方式由二酚、碳酸衍生物、任选地链终止剂及任选地支化剂制备。
在近40年内的许多专利文件中均提到了关于制备聚碳酸酯的细节。在此仅例举参考Schnell的“聚碳酸酯的物理与化学”，聚合物评论，9卷，Interscience Publishers，纽约，伦敦，悉尼1964；D.Freitag，U.Grigo，P.R.Muller，H.Nouvertne，BAYER AG，“聚碳酸酯”，见聚合物科学与工程百科全书，11卷，第2版，1988，648-718页并最后参考Drs.U.Grigo，K.Kirchner和P.R.Müller的“聚碳酸酯”，Becker/Braun，Kunststoff-Handbuch，3/1卷，聚碳酸酯、聚缩醛、聚酯、纤维素酯，Carl Hanser Verlag Münich，维也那1992，117-299页。
用于制备聚碳酸酯的适宜二酚为例如氢醌、间苯二酚、二羟基联苯、二(羟基苯基)-链烷烃、二(羟基苯基)-环烷烃、二(羟基苯基)-硫醚、二(羟基苯基)-醚、二(羟基苯基)-酮、二(羟基苯基)砜、二(羟基苯基)亚砜、α，α’-二(羟基苯基)-二异丙基苯、及其核被烷基化和核被卤化的化合物。
优选的二酚为4，4’-二羟基联苯、2，2-二(4-羟基苯基)-丙烷、2，4-二(4-羟基苯基)-2-甲基丁烷、1，1-二(4-羟基苯基)-对二异丙基苯、2，2-二(3-甲基-4-羟基苯基)-丙烷、2，2-二(3-氯-4-羟基苯基)-丙烷、二(3，5-二甲基-4-羟基苯基)-甲烷、2，2-二(3，5-二甲基-4-羟基苯基)-丙烷、二(3，5-二甲基-4-羟基苯基)-砜、2，4-二(3，5-二甲基-4-羟基苯基)-2-甲基丁烷、1，1-二(3，5-二甲基-4-羟基苯基)-对二异丙基苯、2，2-二(3，5-二氯-4-羟基苯基)-丙烷、2，2-二(3，5-二溴-4-羟基苯基)-丙烷和1，1-二(4-羟基苯基)-3，3，5-三甲基环己烷。
特别优选的二酚为2，2-二(4-羟基苯基)-丙烷、2，2-二(3，5-二甲基-4-羟基苯基)-丙烷、2，2-二(3，5-二氯-4-羟基苯基)-丙烷、2，2-二(3，5-二溴-4-羟基苯基)-丙烷、1，1-二(4-羟基苯基)-环己烷和1，1-二(4-羟基苯基)-3，3，5-三甲基环己烷。
这些及其它适宜的二酚描述于例如US-PS 3 028 635，2 999 835，3 148 172，2 991 273，3 271 367，4 982 014和2 999 846，德国专利文件1 570 703，2 063 050，2 036 052，2 211 956和3 832396，法国专利文件1 561 518，专著“H.Schnell的聚碳酸酯的物理与化学，Interscience Publishers，纽约1964”及日本专利文件62039/1986，62040/1986和105550/1986中。
在均聚碳酸酯的情况中，只使用一种二酚；在共聚碳酸酯的情况中，使用多种二酚。
适宜的碳酸衍生物为例如光气或碳酸二苯基酯。
适宜的链终止剂为单酚或一元羧酸。适宜的单酚为苯酚本身，烷基酚如甲酚、对叔丁基苯酚、对正辛基苯酚、对异辛基苯酚、对正壬基苯酚和对异壬基苯酚，卤代酚如对氯苯酚、2，4-二氯苯酚、对溴苯酚和2，4，6-三溴苯酚及其混合物。
优选的链终止剂为对叔丁基苯酚。
适宜的一元羧酸为苯甲酸、烷基苯甲酸和卤代苯甲酸。
优选的链终止剂为式(I)的酚：
其中R为氢、叔丁基或支化或未支化C8和/或C9烷基基团。
相对所用的具体二酚的摩尔数，所用链终止剂的量为0.1-5mol.％。链终止剂可在进行光气化作用之前、期间或之后加入。
适宜的支化剂为聚碳酸酯化学中已知的三官能团或三官能团以上的化合物，特别为含有三个或三个以上酚OH基团的化合物。
适宜的支化剂为例如间苯三酚、4，6-二甲基-2，4，6-三(4-羟基苯基)-2-庚烯、4，6-二甲基-2，4，6-三(4-羟基苯基)-庚烷、1，3，5-三(4-羟基苯基)-苯、1，1，1-三(4-羟基苯基)-乙烷、三(4-羟基苯基)-苯基甲烷、2，2-二[4，4-二(4-羟基苯基)-环己基]-丙烷、2，4-二(4-羟基苯基-异丙基)-苯酚、2，6-二(2-羟基-5’-甲基-苄基)-4-甲基苯酚、2-(4-羟基苯基)-2-(2，4-二羟基苯基)-丙烷、六(4-(4-羟基苯基-异丙基)-苯基)邻苯二甲酸酯、四(4-羟基苯基)-甲烷、四(4-(4-羟基苯基-异丙基)-苯氧基)-甲烷和1，4-二(4’，4”-二羟基三苯基)-甲基)-苯以及2，4-二羟基苯甲酸、均苯三酸、氰尿酰氯和3，3-二(3-甲基-4-羟基苯基)-2-氧代-2，3-二氢吲哚。
相对所用的具体二酚的摩尔数，任选使用的支化剂的量为0.05-2mol.％。
支化剂可在初始时与二酚和链终止剂一起引入到碱水相中或可在光气化作用之前加入，溶解在有机溶剂中。在酯交换法的情况中，支化剂与二酚一起使用。
所有这些制备热塑性聚碳酸酯的步骤均是本领域技术人员所熟悉的。
塑料材料自然构成组合物的主要部分，因此其一般以相对整个混合物75.0-99.9wt.％，优选80-99.8wt.％，特别优选90-99.2wt.％且非常特别优选95-99wt.％的量存在。
为了获得改进的组合物，还可另外存在至少一种通常存在于热塑性塑料，优选聚碳酸酯和共聚碳酸酯中的其它添加剂，例如稳定剂，特别是热稳定剂，尤其是有机亚磷酸盐(或酯)或膦，脱模剂，例如甘油或四羟甲基甲烷的脂肪酸酯，其中不饱和脂肪酸还可全部或部分环氧化，尤其是一硬脂酸甘油酯或四硬脂酸季戊四醇酯(PETS)，阻燃剂，抗静电剂，紫外吸收剂，例如三唑，填料，发泡剂，着色剂，颜料，光学增亮剂，酯交换催化剂及成核剂等，相对整个混合物优选各自的量最多为5wt.％，优选为0.01-5wt.％，特别优选相对塑料材料的量为0.01-1wt.％，如例如EP 0 839 623 A1或EP 0 500 496A1中所述。
这些添加剂的混合物也是可以的。
以这种方式获得的不能透过X射线的聚合物组合物可通过使用常规方法如热压、纺丝、挤塑或注塑法转化成成型物品如玩具零件，以及纤维、薄膜、条带、板材、多壁板、容器、管材和其它部件。聚合物组合物还可被加工得到流延薄膜。因此本发明还提供了根据本发明的聚合物组合物在生产成型物品方面的应用。多层体系的应用也是令人感兴趣的。在这种情况下，具有较高浓度的含溴或含碘的添加剂的本发明聚合物组合物被以薄层形式施涂在由可透过X射线的聚合物制成的成型物品上。它可被同时施涂或刚好在基件成型之后，例如通过共挤塑或多组分注塑模塑之后施涂。但是，也可将其施涂在最终成型基件上，例如通过与薄膜层压或通过溶液涂布。所述模塑化合物特别适用于透明的儿童玩具零件或医学应用领域。这种模塑元件特别适用于小件儿童玩具。
实施例
实施例1
使用双螺杆挤塑机在280℃将94.7份Makrolon 2808与0.3份PETS和5份4，4’-二碘联苯一起复配并随后挤塑得到各种厚度的试验棒。这些模塑物品的性能归纳在表1中：
表1：E-模量：2840Mpa断裂伸长率：100％根据Izod 180-1a的缺口冲击容量：8模塑物品的碘含量：2.9％1.2mm厚试验棒：可用剂量为0.1rad的X射线检测到1.6mm厚试验棒：可用剂量为0.1rad的X射线检测到2.4mm厚试验棒：可用剂量为0.1rad的X射线检测到3.2mm厚试验棒：可用剂量为0.1rad的X射线检测到每一个模塑物品的透明度均大于85％。因此这些模塑物品可使用常规医学X射线设备在人体中检测到，即使是在骨头的阴影下。
加入4，4’-二碘联苯引起材料的软化。这可在玻璃化转变温度降低和较低的溶液粘度中得到证明。而且，还研究了在300℃的加工温度下是否产生4，4’-二碘联苯的分解产物。但是，当使用GC-MS时未发现其它产物。
表2归纳了其它低分子量碘化合物在280℃的低聚碳酸酯熔体(分子量Mn＝1500)中的试验结果：
表2：
其它低分子量碘化合物试验结果
| 碘化合物 | 于280℃在低聚碳酸酯中的行为 |
| 2，3，5-三碘苯甲酸 | 不分解，稍变色 |
| 3，5-二碘水杨酸 | 随着碘消失而分解，变为红色 |
| 4-碘苯甲酸 | 不分解，形成气泡 |
当与4，4’-二碘联苯比较时，上述碘化合物对于相同的X射线造影能力显示出较差的热稳定性。
总之，可以说含有4，4’-二碘联苯的聚碳酸酯提供了具有优异机械和光学性能的良好X射线反差。
Claims (14)
1.含有至少一种低分子量碘化合物的可用X射线造影的塑料材料，其特征在于碘化合物以0.1-25wt.％的量存在并且选自D-甲状腺素、L-甲状腺素、碘葡酰胺、N，N’-二(2，3-二羟丙基)-5-[N-(2，3-二羟丙基)-乙酰氨基]-3，4，6-三碘间苯二甲酰胺、α-(2，4，6-三碘苯氧基)-丁酸、β-溴-2，4，6-三碘苯乙醚、乙二醇-4-(碘苯基)-甲基醚-甲基醚以及下列通式(I)、(II)、(III)的芳族化合物：
其中R、R’、R”、R”’分别代表COOH、OH、NHCOR””、CONHR””、OR””、Cl、Br、F、R””，
其中R””可以是H或含有1-18个碳原子的线性或支化烷基基团，
并且l＝0至5，m＝0至5-1，n＝0至3，o＝0至3-n，p＝0至4，q＝0至4-p，r＝0至4，s＝0至4-r，t＝0至5，u＝0至5-t。
2.根据权利要求1的可用X射线造影的塑料材料，其特征在于，低分子量碘化合物选自通式(I)、(II)、(III)的化合物。
3.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，低分子量碘化合物选自下列名单：4，4’-二碘联苯、2，3，5-三碘苯甲酸、2，4，6-三碘苯酚、4-碘苯酚、3-碘苯酚、2-碘苯酚、3，5-二碘水杨酸、3，5-二碘-2-羟基苯甲酸、4-碘苯甲酸、3-碘苯甲酸、2-碘苯甲酸、2，6-二甲基-4-碘苯酚、2-碘-4-苯基苯酚、3，3’-二碘-2，2’，6，6’-四甲基-4，4’-双酚、2，6-二碘-4-甲基苯酚、3，5-二碘-2-羟基苯甲酸、2，4-二氯-6-碘苯酚、1，4-二甲氧基-2，3-二甲基-5-碘苯、1，2-二甲氧基-4-碘苯、2，2’-二碘-4，4’，5，5’-四甲氧基联苯、4-碘-3-苯基苯甲醚、1，2-二甲氧基-3，4-二甲基-5-碘苯、2，2’-二碘-3，3’-二甲基-4，4’，5，5’-四甲氧基联苯、1，4-二甲氧基-2-碘-5-甲基苯、1，2-二甲氧基-4-碘-5-甲基苯、1，2-二碘-4，5-二甲氧基苯、2，2’-二碘-3，3’，4，4’，5，5’-六甲氧基联苯、2，2’-二碘-4，4’-二甲氧基-3，3’，5，5’-四甲基联苯。
4.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，低分子量碘化合物为4，4’-二碘联苯。
5.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，低分子量碘化合物以0.5-20wt.％，优选0.8-10wt.％且特别优选1-5wt.％的量存在。
6.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，塑料材料选自透明的热塑性材料，优选烯属不饱和单体的聚合物和/或双官能团反应性化合物的缩聚物。
7.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，塑料材料选自基于二酚的聚碳酸酯或共聚碳酸酯、聚丙烯酸酯或共聚丙烯酸酯及聚甲基丙烯酸酯或共聚甲基丙烯酸酯如聚甲基丙烯酸甲酯或共聚甲基丙烯酸甲酯，或者与苯乙烯的共聚物如透明的聚苯乙烯/丙烯腈(SAN)，以及透明的环烯烃、对苯二甲酸的缩聚物或共缩聚物如聚对苯二甲酸乙二酯或共聚对苯二甲酸乙二酯(PET或CoPET)或二醇改性的PET。
8.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，塑料材料选自聚碳酸酯或共聚碳酸酯。
9.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，塑料材料以相对全部混合物75.0-99.9wt.％，优选80-99.8wt.％，特别优选90-99.2wt.％且非常特别优选95-99wt.％的量存在。
10.根据至少一项上述权利要求的可用X射线造影的塑料材料，其特征在于，还另外存在至少一种通常存在于热塑性塑料，优选聚碳酸酯和共聚碳酸酯中的其它添加剂，例如稳定剂，特别是热稳定剂，尤其是有机亚磷酸盐或酯或膦，脱模剂，例如甘油或四羟甲基甲烷的脂肪酸酯，其中不饱和脂肪酸还可全部或部分环氧化，尤其是一硬脂酸甘油酯或四硬脂酸季戊四醇酯(PETS)，阻燃剂，抗静电剂，紫外吸收剂，例如三唑，填料，发泡剂，着色剂，颜料，光学增亮剂，酯交换催化剂及成核剂等，相对整个混合物优选各自的量最多为5wt.％，优选为0.01-5wt.％，特别优选相对塑料材料的量为0.01-1wt.％。
11.制备根据至少一项上述权利要求的可用X射线造影的塑料材料的方法，其特征在于，在挤塑之前、期间或之后将有关的物质彼此共混并随后任选地在另一个挤塑机中于适于生产模塑元件的温度进行挤塑。
12.至少一项上述权利要求的低分子量碘化合物在改进透明塑料材料X射线反差方面的应用。
13.根据权利要求12的应用，其特征在于，塑料材料选自基于二酚的聚碳酸酯或共聚碳酸酯、聚丙烯酸酯或共聚丙烯酸酯及聚甲基丙烯酸酯或共聚甲基丙烯酸酯如聚甲基丙烯酸甲酯或共聚甲基丙烯酸甲酯，或者与苯乙烯的共聚物如透明的聚苯乙烯/丙烯腈(SAN)，以及透明的环烯烃、对苯二甲酸的缩聚物或共缩聚物如聚对苯二甲酸乙二酯或共聚对苯二甲酸乙二酯(PET或CoPET)或二醇改性的PET，优选聚碳酸酯或共聚碳酸酯。
14.具有改进的X射线反差的玩具，含有根据权利要求1-10至少一项的塑料材料。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19857149.6 | 1998-12-11 | ||
| DE19857149A DE19857149A1 (de) | 1998-12-11 | 1998-12-11 | Röntgenkontrastierbare Kunststoffmassen |
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| US (1) | US6509406B1 (zh) |
| EP (1) | EP1155073A1 (zh) |
| JP (1) | JP2002532598A (zh) |
| CN (1) | CN1330679A (zh) |
| AU (1) | AU1861300A (zh) |
| CA (1) | CA2353860A1 (zh) |
| DE (1) | DE19857149A1 (zh) |
| HK (1) | HK1042910A1 (zh) |
| WO (1) | WO2000036002A1 (zh) |
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| CN112088068A (zh) * | 2018-05-08 | 2020-12-15 | 株式会社弘辉 | 助焊剂和软钎料材料 |
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| DE19940862A1 (de) * | 1999-08-27 | 2001-03-01 | Bayer Ag | Röntgenkontrastierbare Kunststoffformteile |
| GB0725070D0 (en) * | 2007-12-21 | 2008-01-30 | Iopharma Technologies Ab | Product |
| US8617700B2 (en) * | 2008-09-30 | 2013-12-31 | Sabic Innovative Plastics Ip B.V. | Thermoplastic composition having improved X-ray contrast, method of making, and articles prepared therefrom |
| US8404338B2 (en) | 2008-09-30 | 2013-03-26 | Sabic Innovative Plastics Ip B.V. | X-ray and/or metal detectable articles and method of making the same |
| WO2012019145A1 (en) | 2010-08-06 | 2012-02-09 | Endoshape, Inc. | Radiopaque shape memory polymers for medical devices |
| US8691915B2 (en) | 2012-04-23 | 2014-04-08 | Sabic Innovative Plastics Ip B.V. | Copolymers and polymer blends having improved refractive indices |
| EP2953650B1 (en) | 2013-02-08 | 2020-09-30 | Endoshape, Inc. | Radiopaque polymers for medical devices |
| EP2968620B1 (en) | 2013-03-15 | 2019-02-13 | Endoshape, Inc. | Polymer compositions with enhanced radiopacity |
| US20220133944A1 (en) | 2019-02-28 | 2022-05-05 | Speed Care Mineral Gmbh | Paste for marking textile fabrics and/or other products incapable of x-ray contrast |
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| US3361700A (en) | 1965-04-26 | 1968-01-02 | Sterling Drug Inc | Iodinated esters and resin compositions containing same |
| US3382207A (en) | 1965-09-30 | 1968-05-07 | Gen Electric | Flame-retardant polycarbonates |
| US3645955A (en) * | 1970-03-18 | 1972-02-29 | Scient Tube Products Inc | Plasticized radiopaque vinyl resin compositions |
| US3715331A (en) * | 1970-05-01 | 1973-02-06 | Coe Labor | Monomer soluble x-ray opaque methacrylate particles |
| FR2223403A1 (en) | 1973-03-28 | 1974-10-25 | Plastimer | Vinyl chloride resin compsn. contg. 2-hydroxy-3,5-diiodobenzoic acid - transparent to light and opaque to U.V. rays |
| US4093589A (en) * | 1977-02-03 | 1978-06-06 | General Electric Company | Non-opaque flame retardant polycarbonate composition |
| US4283447A (en) | 1979-05-18 | 1981-08-11 | Flynn Vincent J | Radiopaque polyurethane resin compositions |
| IL63876A0 (en) * | 1980-10-20 | 1981-12-31 | Population Res Inc | Radiopaque cyanoacrylates |
| US5330740A (en) * | 1993-03-01 | 1994-07-19 | Sterling Winthrop Inc. | Compositions of iodoaniline derivatives in film-forming materials for visualization of the gastrointestinal tract |
| GB9410578D0 (en) * | 1994-05-26 | 1994-07-13 | London Hospital Med Coll | Novel (meth)acrylate monomers and denture base compositions prepared therefrom |
| DE19545289A1 (de) | 1995-12-05 | 1997-06-12 | Bayer Ag | Thermoplastische Massen mit verbessertem Röntgenkontrast |
| DE19726191A1 (de) | 1997-06-20 | 1998-12-24 | Bayer Ag | Verwendung von Jod-phenyl-carbonat-haltigen Polycarbonaten zur Herstellung von speziellen Formteilen |
| WO1999012577A1 (en) * | 1997-09-05 | 1999-03-18 | Nycomed Imaging As | Polymer particles made of polyvinyl alcohol and comprising a contrast agent for chemoembolization |
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1999
- 1999-12-01 US US09/857,389 patent/US6509406B1/en not_active Expired - Fee Related
- 1999-12-01 EP EP99962191A patent/EP1155073A1/de not_active Withdrawn
- 1999-12-01 AU AU18613/00A patent/AU1861300A/en not_active Abandoned
- 1999-12-01 WO PCT/EP1999/009336 patent/WO2000036002A1/de not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112088068A (zh) * | 2018-05-08 | 2020-12-15 | 株式会社弘辉 | 助焊剂和软钎料材料 |
| US11833621B2 (en) | 2018-05-08 | 2023-12-05 | Koki Company Limited | Flux and solder material |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1861300A (en) | 2000-07-03 |
| JP2002532598A (ja) | 2002-10-02 |
| DE19857149A1 (de) | 2000-06-15 |
| EP1155073A1 (de) | 2001-11-21 |
| WO2000036002A1 (de) | 2000-06-22 |
| CA2353860A1 (en) | 2000-06-22 |
| US6509406B1 (en) | 2003-01-21 |
| HK1042910A1 (zh) | 2002-08-30 |
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