CN1813220B - 特别是用于立体平版印刷制备耳机的低粘度、可辐照固化的配制剂 - Google Patents
特别是用于立体平版印刷制备耳机的低粘度、可辐照固化的配制剂 Download PDFInfo
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- CN1813220B CN1813220B CN2004800177082A CN200480017708A CN1813220B CN 1813220 B CN1813220 B CN 1813220B CN 2004800177082 A CN2004800177082 A CN 2004800177082A CN 200480017708 A CN200480017708 A CN 200480017708A CN 1813220 B CN1813220 B CN 1813220B
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- dimethylacrylate
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Abstract
本发明涉及一种用于立体平版印刷的生物相容性的低粘度可辐照固化的配制剂，特别是用于在医用技术领域用于生产耳机，该配制剂包括：a)55-95重量％基于双酚A或者双酚F的单体二甲基丙烯酸酯或低聚二甲基丙烯酸酯，b)0-20重量％的官能度n小于4和粘度小于15Pas的聚氨酯甲基丙烯酸酯，c)2-15重量％的粘度小于5Pas的单体脂族或者环脂族二甲基丙烯酸酯，d)0-15重量％的粘度小于3Pas的单官能甲基丙烯酸酯，e)0.5-6重量％的一种光引发剂或者多种光引发剂的组合，其吸收处于所用激光辐照波长范围内，f)0.0001-2重量％的抑制剂2，2，6，6-四甲基-1-哌啶基氧(自由基)，也可以和已知抑制剂组合，g)0-40重量％填料，h)0-5重量％色料，i)0-5重量％的常规添加剂如紫外稳定剂或者流动添加剂，其中组分a)-h)的含量总和为100重量％。
Description
本发明涉及一种用于立体平版印刷制备医用技术产品、特别是用于制备耳机的低粘度、可辐照固化的配制剂，其基于至少两种具有可自由基聚合的甲基丙烯酸官能团的化合物，和至少一种用于合适的化合物的聚合的合适光引发剂，和至少一种用于稳定化该立体平版印刷树脂的特定抑制剂2，2，6，6-四甲基-1-哌啶基氧(自由基)，该抑制剂与其他在立体平版印刷树脂技术中已知的抑制剂相比适于用作这种组合物的非常有益的配制剂组分.
由美国专利申请4575330已知利用立体平版印刷可将低粘度可辐照固化的树脂或者树脂混合物用于制备三维物品.
此外由美国专利5487012和WO 01/87001已知立体平版印刷可以有利地用于制备耳机.在立体平版印刷工艺中三维物品由低粘度、可辐照固化的配制剂以下面方式构成，该配制剂的每一薄层(约0.0025-0.01mm)借助光化学辐照以特定方式进行预固化以使得所得到层在这一位置具有制品的所需横截面形状.同时得到的层聚合到在前一步骤中固化的层上.整个物体的构成借助计算机调节的激光器系统例如Nd:YVO4固体激光器(Viper si2SLA系统，3D Systems公司，美国)实现。产生的模塑体视需要例如通过辐照固化进行后固化.
在立体平版印刷工艺中对可采用的树脂配制剂提出了特别的要求。对此特别提及辐照敏感性、树脂配制剂的粘度以及借助激光固化预固化的模塑体的强度.这种不完全固化的模塑体在立体平版印刷技术中称为生坯，而这种通过E模量和抗弯强度来表征的生坯的强度称为生坯强度。生坯强度是对于立体平版印刷实践中的一个重要参数，因为具有低生坯强度的模塑体在立体平版印刷工艺中可能在其自身重量下变形或者其可能在例如用氙弧灯或者卤素灯后固化期间下陷或者弯曲。因此，应当理解的是，考虑到上述要求使用难于调整和配制的组合物。
例如由H.Kodama在Rev.Sci.Instrum.52(11)，1170-1173(1981)公开了一种低粘度的可辐照固化的树脂配制剂，其由不饱和聚酯、丙烯酸酯、苯乙烯和聚合引发剂构成。但是考虑到立体平版印刷技术中的用途，该树脂配制剂的生坯强度低和光敏性不足.
同样从生产技术的观点来看由美国专利4100141公开的树脂配制剂的光敏性不足.在此低光敏性意味着对于模塑体生产需要的时间长。因此，必须调节该立体平版印刷配制剂的光敏性以使得由低粘度可辐照固化的树脂配制剂的激光辐照的目标射入深度和所耗费的辐照能量的比率以低的辐照能量实现尽可能大的固化深度同时高的聚合程度、良好的生坯强度和足够的树脂配制剂防止自发聚合的稳定性。部分满足上述要求的液态、可辐照固化的树脂配制剂例如记载于美国专利5476748或者在WO 99/50711中.但是这种称为“杂混体系”的配制剂含有自由基和阳离子可聚合组分的组合.其由下列组分构成：第一组分，由液态的双或多官能环氧化合物或者由双官能或者更多官能的环氧化合物的混合物组成；第二组分，由阳离子光引发剂或者由多种阳离子光引发剂的混合物组成；第三组分，由用于自由基聚合反应的光引发剂或者多种光引发剂的混合物和由至少一种(甲基)丙烯酸酯官能度n大于2的低粘度聚(甲基)丙烯酸酯、至少一种二丙烯酸酯和至少一种选自羟基封端的聚醚、聚酯和聚氨酯的聚醇组分组成。本领域技术人员已知的是，这种配制剂在毒理学方面被评价为不利的，因而不能或者仅能受限制地用于生产医用产品.例如已知阳离子光引发剂可能导致皮肤刺激和过敏反应。在这种配制剂中使用的具有环氧官能团的化合物也起到类似的作用.此外本领域技术人员还已知丙烯酸酯化合物同样具有增加的过敏性潜力，因而树脂组合物(例如在EP 0425441、EP 0914242和EP 0579503中记载的)由于生物相容性问题而不能用于生产例如耳机。对于在医用技术方面的用途经证实基于双酚A或者双酚F和具有官能度n≥2的聚氨酯甲基丙烯酸酯的单体或低聚二甲基丙烯酸酯是有利的.但与丙烯酸酯化合物的基团相比，对于立体平版印刷技术甲基丙烯酸酯化合物的基团具有较低的反应性.由此产生了上述涉及激光辐照进入深度和预固化制品的生坯强度的缺点。由于这种化合物类型较低的反应性，还需要加入用于自由基聚合反应的一种或多种较高浓度的光引发剂.这导致对于树脂组合物的自发聚合稳定性差.此外本领域技术人员还已知在立体平版印刷工艺中在生产具有大量低质量小零件制品时存在立体平版印刷树脂配制剂的高机械应力和热应力，这可能导致立体平版印刷树脂的自发聚合或者树脂组合物的性能改变和由此生产的模塑体性能改变。这一方面是归因于在低树脂消耗量时在平板上固定和预固化的模塑体相对频繁地从立体平版印刷装置的构造室中移出。由此导致在构造室中立体平版印刷树脂的温度收缩。另一方面在耳机生产时产生模塑体的较大表面积对体积比。本领域技术人员已知在自由基聚合由于进入的氧气而使抑制层残留在模塑体的表面上。这样，仅为不完全聚合的或未聚合的树脂在构造过程中由试件表面溶解到立体平版印刷树脂中。.
从这此可以看出，在借助立体平版印刷技术生产耳机时，低粘度可辐照固化的树脂组合物的稳定化是一个重要的参数。因此在生产技术观点来看，在尽可能恒定的激光辐照射入深度时可以将所述立体平版印刷树脂配制剂的临界能量按相应的用途进行调节是理想的。
本发明的任务在于提供一种用于制造医用产品特别是耳机的立体平版印刷树脂配制剂，其既满足机械的、毒理学的要求，又满足借助立体平板印刷快速制造的要求。现已发现，由一种或多种彼此不同的基于双酚A或者双酚F的单体或者低聚二甲基丙烯酸酯组成的低粘度的树脂混合物，其此外还含有官能度n小于4和粘度小于10Pas的聚氨酯甲基丙烯酸酯，额外的粘度小于3Pas的单体脂族或环脂族二甲基丙烯酸酯和2，2，6，6-四甲基-1-哌啶基氧(自由基)，可用于立体平版印刷技术，且其在借助激光进行固化时产生预固化的模塑体，该模塑体特征在于高生坯强度。令人吃惊的是还发现，借助抑制剂2，2，6，6-四甲基-1-哌啶基氧(自由基)可生产可辐照固化的低粘度立体平版印刷树脂配制剂，其临界能量与激光辐照的进入深度的比率可以在宽范围内调节。通过固化获得的模塑体除了良好的机械性能外还具有优异的生物相容性，其为硬弹性的(hartelastisch)并可进行例如研磨或上漆。
因此本发明的主题在于一种低粘度的可辐照固化的立体平版印刷树脂，其包含：
a)55-95重量％基于双酚A或者双酚F的单体或者低聚二甲基丙烯酸酯，
b)0-20重量％官能度n小于4和粘度小于15Pas、优选小于10Pas的聚氨酯甲基丙烯酸酯，
c)2-15重量％粘度小于5Pa s、优选小于3Pa s的单体脂族或者环脂族二甲基丙烯酸酯，
d)0-15重量％粘度小于3Pa s的单官能甲基丙烯酸酯，
e)0.5-6重量％的一种光引发剂或者多种光引发剂的组合，其吸收在所用激光辐照波长范围内，
f)0.0001-2重量％的抑制剂2，2，6，6-四甲基-1-哌啶基氧(自由基)，也可以和立体平版印刷领域技术人员已知的抑制剂组合，
g)0-40重量％填料，
h)0-5重量％色料，
i)0-5重量％的常规添加剂如紫外稳定剂或者流动添加剂，其中组分a)-h)的含量总和为100重量％。
优选本发明的混合物含有：
a)60-90重量％的乙氧基化度n小于10的n重乙氧基化双酚A二甲基丙烯酸酯或者乙氧基化度n小于10的多种n重乙氧基化双酚A二甲基丙烯酸酯的混合物，
b)5-17重量％的官能度n小于4且粘度小于10Pa s的脂族或者环脂族聚氨酯甲基丙烯酸酯，
c)3-10重量％的粘度小于3Pa s的单体脂族或者环脂族二甲基丙烯酸酯，
d)2-10重量％的粘度小于3Pa s的单官能甲基丙烯酸酯，
e)1-4重量％的一种光引发剂或者多种光引发剂的组合，其吸收处于所用激光辐照波长范围内，
f)0.005-0.05重量％的抑制剂2，2，6，6-四甲基-1-哌啶基氧(自由基)，其也可以和立体平版印刷领域技术人员已知的抑制剂相组合，
g)0-20重量％的填料，
h)0-5重量％的色料，
i)0.01-3重量％的常规添加剂例如紫外稳定剂或者流动添加剂，其中组分a)-h)的含量总和为100重量％。
适合作为组分(a)的化合物的是例如(n)-烷氧基化双酚A的二甲基丙烯酸酯如双酚A乙氧基化物(2)二甲基丙烯酸酯、双酚A乙氧基化物(4)二甲基丙烯酸酯、双酚A丙氧基化物(2)二甲基丙烯酸酯、双酚A丙氧基化物(4)二甲基丙烯酸酯以及(n)-烷氧基化双酚F的二甲基丙烯酸酯例如双酚F乙氧基化物(2)二甲基丙烯酸酯和双酚F乙氧基化物(4)二甲基丙烯酸酯，双酚F丙氧基化物(2)二甲基丙烯酸酯、双酚F丙氧基化物(4)二甲基丙烯酸酯和它们的混合物.优选使用基于双酚A的单体或者低聚二甲基丙烯酸酯，尤其是双酚A乙氧基化物(2)二甲基丙烯酸酯和双酚A乙氧基化物(4)二甲基丙烯酸酯.尤其优选的是这两种基于双酚A的二甲基丙烯酸酯的混合物，其中双酚A乙氧基化物(4)二甲基丙烯酸酯的含量大于双酚A乙氧基化物(2)二甲基丙烯酸酯的含量.
在本发明的配制剂中作为组分(b)使用的官能度小于4的聚氨酯甲基丙烯酸酯是本领域技术人员已知的，并可以已知的方式制备，其中例如将羟基端基的聚氨酯和甲基丙烯酸反应得到相应的聚氨酯丙烯酸甲酯，或者将异氰酸酯端基的预聚物和羟基甲基丙烯酸酯反应.对应的方法从例如EP 0579503中已知.聚氨酯甲基丙烯酸酯也可以商购获得，例如以商标名从Piccadilly Chemicals公司获得，以商品名CN 1963从Sartomer公司获得和以商标名从Rahn公司获得.
作为聚氨酯甲基丙烯酸酯优选使用官能度n小于4和从脂族原料制备的那些，尤其是从HEMA和TMDI所得的异构体混合物7，7，9-(或者7，9，9-)三甲基-4，13-二氧代-3，14-二氧杂-5，12-二氮杂十六烷-1，16-二醇-二甲基丙烯酸酯.作为组分(c)的化合物可以例如使用1，3-丁二醇二甲基丙烯酸酯、1，6-己二醇二甲基丙烯酸酯、1，3-丁二醇二甲基丙烯酸酯、二甘醇二甲基丙烯酸酯、乙二醇二甲基丙烯酸酯、二甲基丙烯酸新戊酯、聚乙二醇二甲基丙烯酸酯、三甘醇二甲基丙烯酸酯和四甘醇二甲基丙烯酸酯并优选1，4-丁二醇二甲基丙烯酸酯。这些产物可以商购获得，例如从Sartomer公司获得.
在本发明的配制剂中可以示例性含有作为组分(d)的下列化合物：甲基丙烯酸烯丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸正丁酯、甲基丙烯酸异丁酯、甲基丙烯酸正己酯、甲基丙烯酸-2-乙基己酯、甲基丙烯酸正辛酯、甲基丙烯酸正癸酯、甲基丙烯酸正十二烷基酯、甲基丙烯酸异冰片酯、甲基丙烯酸异癸酯、甲基丙烯酸月桂酯、甲基丙烯酸硬脂酯、甲基丙烯酸-2-羟乙酯、甲基丙烯酸-2-羟丙酯和甲基丙烯酸-3-羟丙酯、甲基丙烯酸四氢糠酯和甲基丙烯酸环己酯.尤其优选甲基丙烯酸乙酯.
作为组分(e)可以使用在相应辐照下形成自由基的所有类型的光引发剂。对此已知的光引发剂是苯偶姻类的化合物，苯偶姻醚类，例如苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚和苯偶姻异丙基醚、苯偶姻苯基醚和苯偶姻乙酸酯，苯乙酮类，例如苯乙酮、2，2-二甲氧基苯乙酮和1，1-二氯苯乙酮、偶苯酰、偶苯酰缩酮类，例如苯偶酰二甲基缩酮和苯偶酰二乙基缩酮，蒽醌类例如2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌和2-戊基蒽醌，三苯膦、苯甲酰基氧化膦类如2，4，6-三甲基苯甲酰基二苯基氧化膦(Luzirin TPO)和双(2，4，6-三甲基苯甲酰苯基)氧化膦、二苯酮类如二苯酮和4，4’-双-(N，N’-二甲基氨基)二苯酮、噻吨酮类或者呫吨酮类，吖啶衍生物、吩嗪衍生物、喹喔啉衍生物或者1-苯基-1，2-丙二醇-2-O-苯甲酰肟、1-氨基苯酮类或1-羟基苯酮类如1-羟基环己基苯基酮、苯基-(1-羟基异丙基)酮和4-异丙基苯基-(1-羟基异丙基)酮.尤其优选的与Nd:YVO4固体激光器结合使用的化合物是双(2，4，6-三甲基苯甲酰基)苯基氧化膦、2，4，6-三甲基苯甲酰基二苯基氧化膦、2-羟基-2-甲基苯丙酮、羟基环己基苯基酮和这些光引发剂的混合物.
向本发明的混合物中添加作为引发剂或稳定剂的2，2，6，6-四甲基-1-哌啶基氧(自由基).在实施例1中2，2，6，6-四甲基-1-哌啶基氧(自由基)的浓度对激光辐照的进入深度和临界能量的影响在附图1和2中给出。激光进入深度和临界能量借助窗玻璃(Windowpane)方法确定，该方法记载于P.F.Jacobs和D.T.Reid，Rapid Prototyping &Manufacturing，Society of Manufacturing Engineers，Dearborn，MI，1992，第一版，263-280页.从附图可以得知，添加少量的2，2，6，6-四甲基-1-哌啶基氧(自由基)在仅少量改变了激光辐照的进入深度时已经导致临界能量的强烈增加.抑制剂2，2，6，6-四甲基-1-哌啶基氧(自由基)对立体平版印刷树脂相关参数Ec(临界能量，mJ cm-2)和Dp(激光进入深度，mils)的影响不同于在现有技术中添加到对应的立体平版印刷树脂中的抑制剂例如氢醌单甲基醚的影响。在实施例2中氢醌单甲基醚对参数Ec和Dp的影响在附图3和4中给出.与抑制剂2，2，6，6-四甲基-1-哌啶基氧(自由基)的影响相比，立体平版印刷树脂的临界能量仅能通过显著更高的氢醌单甲基醚浓度在显著较小的范围内调节.此外，该抑制剂氢醌单甲基醚对激光进入深度的影响大于使用2，2，6，6-四甲基-1-哌啶基氧(自由基)的情况.当必须调节有色或者不透明的立体平版印刷树脂的参数时，这尤其不利，因为通过添加颜料或者染料激光进入深度同样降低.按上述实施方式可能造成在生产技术的观点来看不希望的模塑体构造时间延长.在医用技术领域的立体平版印刷树脂的情况下和尤其是用于制备耳机的立体平版印刷树脂的情况下，有色或不透明的立体平版印刷树脂配制剂尤其重要.
实施例1：
70.3-x重量％ 双酚A乙氧基化物(4)二甲基丙烯酸酯
14.4重量％ 双酚A乙氧基化物(2)二甲基丙烯酸酯
9.2重量％ 7，7，9-(或7，9，9-)三甲基-4，13-二氧代-3，14-
二氧杂-5，12-二氮杂-十六烷-1，16-二醇二
甲基丙烯酸酯
4.6重量％ 1，4-丁二醇二甲基丙烯酸酯
1.5重量％ 双(2，4，6-三甲基苯甲酰基)苯基氧化膦
x重量％ 2，2，6，6-四甲基-1-哌啶基氧(自由基)
2，2，6，6-四甲基-1-哌啶基氧(自由基)以x＝0；0.005；0.01；0.02和0.05重量％的浓度使用.
实施例2
70.3-x重量％ 双酚A乙氧基化物(4)二甲基丙烯酸酯
14.4重量％ 双酚A乙氧基化物(2)二甲基丙烯酸酯
9.2重量％ 7，7，9-(或7，9，9-)三甲基-4，13-二氧代-3，14-
二氧杂-5，12-二氮杂-十六烷-1，16-二醇二
甲基丙烯酸酯
4.6重量％ 1，4-丁二醇二甲基丙烯酸酯
1.5重量％ 双(2，4，6-三甲基苯甲酰基)苯基氧化膦
x重量％ 氢醌单甲基醚
抑制剂氢醌单甲基醚以x＝0；0.1；0.2；0.4；0.6；1和2重量％的浓度使用。
附图1：2，2，6，6-四甲基-1-哌啶基氧的浓度对根据实施例1的树脂配制剂的激光进入深度Dp的影响。
附图2：2，2，6，6-四甲基-1-哌啶基氧的浓度对根据实施例1的树脂配制剂的临界能量的影响.
附图3：氢醌单甲基醚的浓度对来自实施例2的树脂配制剂的激光进入深度Dp的影响.
附图4：氢醌单甲基醚的浓度对来自实施例2的树脂配制剂的临界能量的影响.
本发明的混合物中视需要可以添加本领域技术人员已知的添加剂，例如流动助剂、紫外稳定剂、润湿剂、填料、染料和颜料.在本发明意义上合适的染料是蒽醌染料制剂，例如从Bayer公司以商品名Macrolex购得.
应用实施例
实施例3一种浅黄色不透明立体平版印刷树脂：
66.69重量％ 双酚A乙氧基化物(4)二甲基丙烯酸酯
15.6重量％ 双酚A乙氧基化物(2)二甲基丙烯酸酯
10重量％ 7，7，9-(或7，9，9-)三甲基-4，13-二氧代-3，14-
二氧杂-5，12-二氮杂-十六烷-1，16-二醇二
甲基丙烯酸酯
5重量％ 1，4-丁二醇二甲基丙烯酸酯
1.5重量％ 双(2，4，6-三甲基苯甲酰基)苯基氧化膦
0.8重量％ 热解硅酸
0.4重量％ 氧化铁颜料
0.01重量％ 2，2，6，6-四甲基-1-哌啶基氧(自由基)
实施例4蓝色透明立体平版印刷树脂：
69.035重量％ 双酚A乙氧基化物(4)二甲基丙烯酸酯
15.6重量％ 双酚A乙氧基化物(2)二甲基丙烯酸酯
10重量％ 7，7，9-(或7，9，9-)三甲基-4，13-二氧代-3，14-
二氧杂-5，12-二氮杂-十六烷-1，16-二醇二
甲基丙烯酸酯
3.8重量％ 1，4-丁二醇二甲基丙烯酸酯
1.5重量％ 双(2，4，6-三甲基苯甲酰基)苯基氧化膦
0.03重量％ 蒽醌染料制剂(含有C.I溶剂蓝97)
0.025重量％ 紫外稳定剂
0.01重量％ 2，2，6，6-四甲基-1-哌啶基氧(自由基)
实施例5红色透明立体平版印刷树脂：
69.055重量％ 双酚A乙氧基化物(4)二甲基丙烯酸酯
15.6重量％ 双酚A乙氧基化物(2)二甲基丙烯酸酯
10重量％ 7，7，9-(或7，9，9-)三甲基-4，13-二氧代-3，14-
二氧杂-5，12-二氮杂·十六烷-1，16-二醇-二
甲基丙烯酸酯
3.8重量％ 1，4-丁二醇二甲基丙烯酸酯
1.5重量％ 双(2，4，6-三甲基苯甲酰基)苯基氧化膦
0.025重量％ 紫外稳定剂
0.01重量％ 偶氮染料红H
0.01重量％ 2，2，6，6-四甲基-1-哌啶基氧(自由基)
上述树脂与立体平版印刷技术相关的参数在表1中给出。所有粘度测量在23℃时用来自Bohlin Instruments公司的CVO 120流变仪进行。抗弯强度、E模量和伸长率的测定按照EN ISO 178(1996)用来自Zwick公司的Zwick1-测试机进行.为借助上述窗玻璃方法测量Ec值和Dp值，测量了10个窗玻璃试件的平均值。所述试件借助装备有Nd:YVO4固体激光器的Viper si2 SLA设备制备。生坯用Innovation Meditech公司的频闪发光单元(Stroboskop-Belichtungseinheit)Sonolux PR借助4000次闪光进行后固化。
此外，对来自实施例3-5的经固化的立体平版印刷树脂配制剂试件进行该配制剂的细胞毒性、刺激性和过敏性或者过敏性潜力研究。
为了测定刺激效果，按照ISO 10993-10(2002)、ISO 10993-12(2002)和ISO 17025(1999)在新西兰兔上进行测试.对这些动物皮内注射对比溶液和来自试件的测试提取液.从该试验得知，上述立体平版印刷树脂配制剂的刺激性可忽略。
在其他用于测定哺乳动物细胞培养(L929)在试件上的生物反应性的测试系列中按照ISO 10993-5(1999)、ISO 10993-12(2002)和ISO 17025(1999)进行了洗提试验.没有发现L929哺乳动物细胞的生物反应性(0级).因此上述材料不具有细胞毒性，因而满足ISO10993-5的规定.
此外对该试件的过敏性潜力和敏化性质借助基于ISO 10993-10(2002)、ISO 10993-12(2002)的系列测试依据F.N.Marzulli和H.I.Maibach(编辑)第五版，1996，403页、440-441页，HemispherePublishing Corporation，New York，B.Magnusson和A.M.Kilgman，J.Invest.Dermatol.52：268-276(1969)，B.Magnusson和A.M.Kligman，1970，Allergic contact dermatitis in the guinea pig.Identification of contact allergens，Sprin gfield，IL.：Thomas evaluiert进行了评定.上述立体平版印刷配制剂不会诱发生物反应(0％敏化).根据Kligman的标度这是1级反应性，因此该立体平版印刷配制剂的过敏潜力分级为弱.按照Magnusson和Kligman的1级敏化程度被视为不明显。
从该结果明确可知，根据本发明的立体平版印刷树脂配制剂可用于医用技术领域中、尤其是用于制造耳机.
在表3中是市售可得的Vantico公司的不透明立体平版印刷树脂LLS71410的机械和化学参数，该树脂对于医用技术用途是相容的.从表中可知，比较而言本发明的配制剂有利地具有显著较低的粘度和较高的Dp值.此外本公开的配制剂的机械特性即抗弯强度和E模量显著高于市售获得的产品的值.此外还发现，Vantico公司的材料尽管被分级为无细胞毒性，但是在测定细胞毒性的系列测试中对应于1级，即诱发轻微的生物反应。在考虑到医用技术领域的应用时其对于本发明的配制剂并非如此。
所有来自本发明的实施例3-5的立体平版印刷树脂配制剂具有在生产技术角度来看理想的小于2250mPa s的粘度和生坯强度。
用于生产耳机的常规技术是基于加入到耳模的阴模中的自发聚合或者光固化的材料.与常规技术所用的用于生产耳机的材料相比(例如Dreve Otoplastik GmbH公司的
(参见表3))，经固化的模塑体的机械值即抗弯强度和E模量显著更高.
Claims (4)
1.生物相容的低粘度可辐照固化的配制剂，用于立体平版印刷或用于医用技术，其包含：
a)55-95重量％基于双酚A或者双酚F的单体二甲基丙烯酸酯或低聚二甲基丙烯酸酯，
b)0-20重量％的官能度n小于4和粘度小于15Pa s的聚氨酯甲基丙烯酸酯，
c)2-15重量％的粘度小于5Pa s的单体脂族或者环脂族二甲基丙烯酸酯，
d)0-15重量％的粘度小于3Pa s的单官能甲基丙烯酸酯，
e)0.5-6重量％的一种光引发剂或者多种光引发剂的组合，所述光引发剂的吸收处于所用激光辐照波长范围内，
f)0.0001-2重量％的抑制剂2，2，6，6-四甲基-1-哌啶基氧，或其和其它抑制剂的组合，
g)0-40重量％填料，
h)0-5重量％色料，
i)0-5重量％的常规添加剂，其中组分a)-i)的含量总和为100重量％。
2.权利要求1的配制剂，用于制备耳机。
3.生物相容的低粘度可辐照固化的配制剂，用于立体平版印刷或用于医用技术，其包含：
a)60-90重量％的乙氧基化度n小于10的n重乙氧基化的双酚A二甲基丙烯酸酯，或者乙氧基化度n小于10的n重乙氧基化双酚A二甲基丙烯酸酯的混合物，
b)5-17重量％的官能度n小于4和粘度小于10Pa s的脂族或者环脂族聚氨酯甲基丙烯酸酯，
c)3-10重量％的粘度小于3Pa s的单体脂族或者环脂族二甲基丙烯酸酯，
d)2-10重量％的粘度小于3Pa s的单官能甲基丙烯酸酯，
e)1-4重量％的一种光引发剂或者多种光引发剂的组合，所述光引发剂的吸收处于所用激光辐照的波长范围内，
f)0.005-0.05重量％的抑制剂2，2，6，6-四甲基-1-哌啶基氧，或其和其它抑制剂的组合，
g)0-20重量％的填料，
h)0-5重量％的色料，
i)0.01-3重量％的常规添加剂，其中组分a)至i)的含量总和为100重量％。
4.权利要求3的配制剂，用于制备耳机。
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| DE102004050868A1 (de) * | 2004-10-18 | 2006-04-20 | Dreve Otoplastik Gmbh | Niedrigviskose, strahlungshärtbare Formulierung zur Herstellung von Ohrpassstücken |
| DE102005050186A1 (de) * | 2005-10-18 | 2007-04-19 | Dreve Otoplastik Gmbh | Niedrigviskose, strahlungshärtbare Formulierung zur Herstellung von Ohrpassstücken mit antimikrobiellen Eigenschaften |
| US7354870B2 (en) * | 2005-11-14 | 2008-04-08 | National Research Council Of Canada | Process for chemical etching of parts fabricated by stereolithography |
| DE102007017195A1 (de) * | 2007-04-12 | 2008-10-16 | Dreve Otoplastik Gmbh | Biokompatible, strahlungshärtende Formulierung zur generativen Herstellung von medizintechnischen Produkten, insbesondere Ohrpassstücken und dentalen Formteilen, mittels Bildprojektionssystemen |
| DE102007041489A1 (de) | 2007-08-31 | 2009-03-05 | Deltamed Gmbh | Flexibler medizintechnischer Formkörper sowie Verfahren zu dessen Herstellung |
| EP2445028A1 (en) * | 2010-10-25 | 2012-04-25 | Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO | Opto-electric device and method of manufacturing an opto-electric device |
| EP2445029A1 (en) * | 2010-10-25 | 2012-04-25 | Nederlandse Organisatie voor toegepast -natuurwetenschappelijk onderzoek TNO | Multilayered protective layer, organic opto-electric device and method of manufacturing the same |
| US10357435B2 (en) * | 2012-12-18 | 2019-07-23 | Dentca, Inc. | Photo-curable resin compositions and method of using the same in three-dimensional printing for manufacturing artificial teeth and denture base |
| PL2986654T3 (pl) * | 2013-04-18 | 2020-09-07 | Dentca, Inc. | Kompozycje żywicy fotoutwardzalnej i sposób ich zastosowania w drukowaniu trójwymiarowym do wytwarzania sztucznych zębów i podstawy protezy zębowej |
| JP6853779B2 (ja) * | 2014-12-18 | 2021-03-31 | ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ | 親水性ナノ粒子を含む放射線硬化性組成物 |
| US11485818B2 (en) | 2018-04-20 | 2022-11-01 | Covestro (Netherlands) B.V. | Radiation curable compositions for additive fabrication |
| US20240301111A1 (en) | 2020-11-30 | 2024-09-12 | Evonik Operations Gmbh | Radiation curable resin |
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- 2004-06-17 EP EP04738713A patent/EP1636651B8/de not_active Expired - Lifetime
- 2004-06-17 AT AT04738713T patent/ATE447200T1/de not_active IP Right Cessation
- 2004-06-17 CN CN2004800177082A patent/CN1813220B/zh not_active Expired - Fee Related
- 2004-06-17 AU AU2004252589A patent/AU2004252589B2/en not_active Ceased
- 2004-06-17 DE DE502004010300T patent/DE502004010300D1/de not_active Expired - Lifetime
- 2004-06-17 WO PCT/DE2004/001262 patent/WO2005001570A1/de active IP Right Grant
- 2004-06-17 JP JP2006520655A patent/JP4251368B2/ja not_active Expired - Fee Related
- 2004-06-17 US US10/561,651 patent/US7232646B2/en not_active Expired - Lifetime
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| EP0425441B1 (de) * | 1989-10-27 | 1995-12-27 | Ciba-Geigy Ag | Photoempfindliches Gemisch |
| EP0822445B2 (de) * | 1996-07-29 | 2005-02-09 | Huntsman Advanced Materials (Switzerland) GmbH | Flüssige, strahlungshärtbare Zusammensetzung, insbesondere für die Stereolithographie |
| CN1322309A (zh) * | 1998-10-05 | 2001-11-14 | 纳幕尔杜邦公司 | 可电离辐射成象的感光聚合物组合物 |
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| EP1385055B1 (en) * | 2002-07-18 | 2007-03-14 | 3D Systems, Inc. | Stereolithographic resins with high temperature and high impact resistance |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1813220A (zh) | 2006-08-02 |
| JP2007500759A (ja) | 2007-01-18 |
| CA2530069A1 (en) | 2005-01-06 |
| AU2004252589B2 (en) | 2007-03-22 |
| JP4251368B2 (ja) | 2009-04-08 |
| US7232646B2 (en) | 2007-06-19 |
| DE10328302A1 (de) | 2005-01-27 |
| AU2004252589A1 (en) | 2005-01-06 |
| US20060264526A1 (en) | 2006-11-23 |
| EP1636651B1 (de) | 2009-10-28 |
| ATE447200T1 (de) | 2009-11-15 |
| EP1636651B8 (de) | 2010-02-17 |
| WO2005001570A1 (de) | 2005-01-06 |
| EP1636651A1 (de) | 2006-03-22 |
| CA2530069C (en) | 2009-12-22 |
| DE502004010300D1 (de) | 2009-12-10 |
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