CN107428892B - 用于三维打印的光固化性组合物 - Google Patents
用于三维打印的光固化性组合物 Download PDFInfo
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- CN107428892B CN107428892B CN201680016615.0A CN201680016615A CN107428892B CN 107428892 B CN107428892 B CN 107428892B CN 201680016615 A CN201680016615 A CN 201680016615A CN 107428892 B CN107428892 B CN 107428892B
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Abstract
一种三维打印光固化性组合物包括按所述组合物的总重量计,20重量%至70重量%的丙烯酸氨基甲酸酯组分、20重量%至60重量%的多官能性环氧组分、1重量%至15重量%的单体组分和1重量%至8重量%的光引发剂组分。所述丙烯酸氨基甲酸酯组分包括丙烯酸酯与异氰酸酯封端的预聚物的封端反应产物且所述异氰酸酯封端的预聚物为聚异氰酸酯与至少一种具有至少3000g/mol的分子量的多元醇的反应产物。所述多官能性环氧组分包括一种或多种多官能性环氧化物。所述单体组分包括多官能性丙烯酸酯单体和多官能性乙烯基醚单体中的至少一个。
Description
技术领域
实施例涉及用于三维打印应用(也称为增材制造(additive manufacturing))的基于丙烯酸氨基甲酸酯/环氧树脂的光固化性组合物、使用其组合物的三维打印应用和使用其组合物的三维打印方法。
背景技术
三维(3-D)打印允许通过使用调配用于3-D打印的材料直接从计算机辅助设计产生物体,其已经设计以产生满足特定最终使用要求的物体。举例来说,在寻求柔性部件的情况下,可寻求提供指定范围内的肖氏A硬度(Shore A hardness)、拉伸强度和伸长率%的材料。如美国专利第6,569,373号中所论述,3-D打印允许使用二维层构建物体。举例来说,一种称为立体光刻的方法通过首先将构建平台降低至称为光敏树脂的成膜材料的桶中。接着,所需打印部分的薄截面通过用光化辐射源追踪形状的区域而聚合。此后,后续截面层在先前层的顶部上固化以获得3-D打印物体。
发明内容
实施例可通过提供用于基于柔性材料的物体的三维打印光固化性组合物而实现,其中以组合物的总重量计,组合物包括20重量%至70重量%的丙烯酸氨基甲酸酯组分、20重量%至60重量%的多官能性环氧组分、1重量%至15重量%的单体组分和1重量%至8重量%的光引发剂组分。丙烯酸氨基甲酸酯组分包括丙烯酸酯与异氰酸酯封端的预聚物的封端反应产物且异氰酸酯封端的预聚物为聚异氰酸酯与至少一种具有至少3000g/mol的分子量的多元醇的反应产物。多官能性环氧组分包括一种或多种多官能性环氧化物。单体组分包括多官能性丙烯酸酯单体和多官能性乙烯基醚单体中的至少一个。
附图说明
图1说明与根据实施例的组合物一起使用的例示性三维打印设备。确切地说,图1说明基于立体光刻的三维打印设备的例示性类型。
具体实施方式
实施例涉及用于使用三维打印设备打印三维柔性物体的光固化性组合物。柔性物体意指通过具有等于或小于95且任选地等于或大于40(例如根据ASTM D2240)的可测量肖氏A硬度的材料形成的具有柔性的物体。根据实施例,呈膜形式的柔性材料具有相对高断裂伸长率%(例如至少50%和/或50%至300%)和相对高拉伸强度(例如至少900psi和/或900psi至3500psi)。
存在多种三维打印装置,所述装置可通过处理馈入材料以获得最终打印物体的方法而不同。举例来说,三维打印设备可利用基于立体光刻的打印方法,所述方法包括用三维可打印调配物构建物体和固化所述物体。例示性基于立体光刻的打印方法可利用以下方法中的一个:(i)通过经由喷墨头分配树脂调配物和使用UV光源而构建物体,(ii)在浴槽中且使用激光***构建物体(例如倒置),和(iii)使用浴槽和UV光源构建物体(例如沿相反的方向)。举例来说,一种此类基于立体光刻的打印装置通过用激光追踪每一截面而将感光聚合物树脂的连续层固化到衬底平台上。在另一实例中,光敏树脂可使用喷墨头处理,其中截面图案沉积到表面上且在曝光于喷墨头之后的UV灯时固化。
参看图1,例示性基于立体光刻的三维打印设备包括激光1和扫描仪***2,激光1向扫描仪***2提供第一激光束3。扫描仪***2向立体光刻桶5提供第二激光束4。立体光刻桶5包括构建平台6和液体光敏树脂材料7,构建平台6浸没于所述材料中。使用第二激光束4和液体光敏树脂材料7,在构建平台6上形成膜层8(用于形成三维打印物体)。膜层8可分别形成固化树脂层。
根据实施例,用于基于柔性材料的物体的光固化性组合物(例如三维打印光固化性组合物)包括按光固化性组合物的总重量计的20重量%至70重量%(例如25重量%至65重量%、35重量%至60重量%、35重量%至55重量%、35重量%至50重量%、45重量%至50重量%等)的丙烯酸氨基甲酸酯组分。丙烯酸氨基甲酸酯组分包括丙烯酸酯与异氰酸酯封端的预聚物的封端反应产物,其中异氰酸酯封端的预聚物为聚异氰酸酯与至少一种具有至少3000g/mol(例如在3000g/mol与12,000g/mol之间、3500g/mol至10,000g/mol、3800g/mol至8,200g/mol等)的分子量的衍生多元醇的反应产物。丙烯酸氨基甲酸酯组分可包括一种或多种丙烯酸氨基甲酸酯,其为丙烯酸酯与异氰酸酯封端的预聚物的封端反应产物,其中异氰酸酯封端的预聚物为聚异氰酸酯与至少一种具有至少3000g/mol的分子量的衍生多元醇的反应产物。
按组合物的总重量计,组合物进一步包括20重量%至60重量%(例如30重量%至60重量%、30重量%至55重量%、35重量%至50重量%、35重量%至45重量%等)的多官能性环氧组分(就环氧官能性而言的多官能性)。多官能性环氧组分可包括一种或多种多官能性环氧化物,例如一种或多种双官能性环脂族环氧化物和/或一种或多种双官能性芳族环氧化物。举例来说,按多官能性环氧组分的总重量计,多官能性环氧组分可以5重量%至100重量%(例如5重量%至60重量%、5重量%至40重量%、5重量%至30重量%、5重量%至20重量%、5重量%至15重量%、5重量%至10重量%等)的量包括一种或多种双官能性芳族环氧化物(如包括一个芳族基的二环氧化物,例如二氧化二乙烯基苯)。
丙烯酸氨基甲酸酯组分与多官能性环氧组分的比率可为0.5:1.5至1.5:0.5和/或0.8:1.2至1:2.0.8。举例来说,当丙烯酸氨基甲酸酯组分的量显著高于(例如大至少三倍)多官能性环氧组分的量时,可能无法实现用于使用三维打印形成柔性物体的足够断裂伸长率%以及足够拉伸强度。当多官能性环氧组分的量显著高于(例如大至少三倍)丙烯酸氨基甲酸酯组分的量时,可能无法实现用于使用三维打印形成柔性物体的足够断裂伸长率%以及足够拉伸强度。
按组合物的总重量计,组合物也包括1重量%至15重量%的单体组分,所述单体组分包括多官能性丙烯酸酯单体(具有超过一个丙烯酸酯官能团)和多官能性乙烯基醚单体(具有超过一个乙烯基官能团)中的至少一个。以另一种方式说明,单体组分可包括一种或多种多官能性丙烯酸酯单体和/或一种或多种多官能性乙烯基醚单体。举例来说,单体组分可包括一种或多种二丙烯酸酯单体和/或一种或多种二乙烯基醚单体。单体组分可至少部分用作反应性稀释剂。
另外,按组合物的总重量计,组合物包括1重量%至8重量%的光引发剂组分。光引发剂组分可包括自由基光引发剂和/或阳离子型光引发剂。在例示性实施例中,包括自由基光引发剂和阳离子型光引发剂两者。
丙烯酸氨基甲酸酯组分
丙烯酸氨基甲酸酯组分包括至少一种衍生自多元醇组分的丙烯酸氨基甲酸酯,所述多元醇组分包括至少一种多元醇,例如使用双金属氰化物(DMC)催化剂或基于碱金属氢氧化物和/或碱金属甲氧化物的催化剂。丙烯酸氨基甲酸酯组分包括丙烯酸酯(一种或多种丙烯酸酯)与异氰酸酯封端的预聚物组分的封端反应产物,而异氰酸酯封端的预聚物组分为聚异氰酸酯(一种或多种聚异氰酸酯)与包括至少一种具有至少3000g/mol的分子量的多元醇的多元醇组分的反应产物。多元醇可为聚醚多元醇。举例来说,多元醇组分可包括任何聚醚多元醇,且排除其它多元醇,如聚酯多元醇。
举例来说,丙烯酸氨基甲酸酯为基于聚氨基甲酸酯的预聚物(例如衍生自聚异氰酸酯)与至少一种仅使用基于DMC的催化剂合成以形成已经历丙烯酸酯封端的异氰酸酯封端的预聚物的多元醇的反应产物。除DMC衍生的多元醇以外,用于形成基于聚氨基甲酸酯的预聚物的反应混合物可包括至少一种其它多元醇(例如DMC衍生的多元醇可占与任选的其余部分一起使用的多元醇的总量的大于75重量%的大部分,所述其余部分为另一聚醚多元醇、聚酯多元醇和/或多胺)。基于聚氨基甲酸酯的预聚物为用于形成丙烯酸氨基甲酸酯的多元醇与聚异氰酸酯(如聚氨基甲酸酯领域中已知的二异氰酸酯,其包括二异氰酸甲苯酯-TDI和二苯亚甲基二异氰酸酯-MDI的纯、聚合和改性形式)的反应产物。根据一个例示性实施例,聚异氰酸酯为具有至少2的标称异氰酸酯官能度的单体TDI或MDI(例如TDI的2,2和2,6异构体或MDI的2,2和2,4异构体的掺合物)。
基于聚氨基甲酸酯的预聚物可在催化剂,如所属领域中已知的基于锡的催化剂和/或基于胺的催化剂存在下形成。基于聚氨基甲酸酯的预聚物可形成为按所得基于聚氨基甲酸酯的预聚物的总重量计,具有1重量%至7重量%(例如1重量%至5重量%)的游离NCO(即游离异氰酸酯部分)含量。
用于形成丙烯酸氨基甲酸酯(以形成基于聚氨基甲酸酯的预聚物的方式)的多元醇组分包括至少一种具有大于3000g/mol的高分子量的多元醇(例如衍生自DMC催化剂)。举例来说,按多元醇组分的总重量计,多元醇组分包括至少75重量%具有大于3000g/mol的分子量的多元醇。举例来说,多元醇(如衍生自DMC催化剂或非DMC催化剂)可具有大于3000g/mol且小于12000g/mol的分子量。
多元醇,如至少一种具有大于3000g/mol的分子量的多元醇可具有低不饱和度水准,使得多元醇具有小于0.100meq/g聚合物的不饱和度。多元醇的不饱和水准可小于0.050meq/g聚合物、小于0.020meq/g聚合物和/或小于0.015meq/g聚合物。多元醇可具有低单醇含量,例如按用于形成丙烯酸氨基甲酸酯的多元醇组分的总重量计小于3.0重量%至不可测量的低量。另外,多元醇可具有高分子量以及低多分散性(Mw/Mn)。举例来说,多分散性可为1.0至1.2。
在例示性实施例中,至少一种用于形成丙烯酸氨基甲酸酯的多元醇不衍生自基于碱金属氢氧化物和/或碱金属甲氧化物的催化剂。确切地说,至少一种多元醇可仅衍生自基于DMC的催化剂(且可能不衍生自基于KOH的催化剂或其它基于碱金属氢氧化物和/或碱金属甲氧化物的催化剂)。包括用基于KOH的催化剂产生的多元醇的聚氧丙烯可导致羟基端基转化为对常规偶合反应无反应的乙烯基。举例来说,在常规碱催化的氧丙烯化期间,环氧丙烷竞争重排为烯丙醇在反应过程期间不断地产生可烷氧基化不饱和单醇。此单体物质的聚烷氧基化可产生宽分子量范围的单醇,其增加多分散性且减少所得产物的总官能性。另外,用基于KOH的催化剂产生的高分子量多元醇可具有高不饱和水准,例如大于0.15meq/g聚合物。相比之下,用基于DMC的催化剂产生的高分子量多元醇可具有较低不饱和水准,例如小于0.01meq/g聚合物。这可等于分别地,基于KOH的催化剂相对于基于DMC的催化剂衍生的多元醇上的无反应端基的28%相对于2%。
基于聚氨基甲酸酯的预聚物以丙烯酸酯封端以根据实施例形成丙烯酸氨基甲酸酯。丙烯酸酯封端反应可在催化剂,如所属领域中已知的基于锡的催化剂和/或基于胺的催化剂存在下进行。丙烯酸酯封端可通过单丙烯酸酯进行。举例来说,丙烯酸酯封端可使用不同于单体组分中包括的多官能性丙烯酸酯中的任一种的丙烯酸酯进行。丙烯酸氨基甲酸酯可含有衍生自基于聚氨基甲酸酯的预聚物(具有异氰酸酯封端的基团)的氨基甲酸酯基(和任选地脲基,其中包括此类基团为所属领域中已知的),所述预聚物的至少90%以丙烯酸酯化合物封端。丙烯酸酯化合物可理解为包括具有以下分子式的丙烯酸酯离子:
CH2=CHCOO- 式1
基于聚氨基甲酸酯的预聚物的丙烯酸酯封端可在形成基于聚氨基甲酸酯的预聚物之后进行。例示性丙烯酸酯包括丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯和甲基丙烯酸羟丙酯。
举例来说,基于聚氨基甲酸酯的预聚物为聚异氰酸酯和衍生自基于DMC的催化剂的多元醇的反应产物。丙烯酸氨基甲酸酯可为基于聚氨基甲酸酯的预聚物与至少一种丙烯酸酯的反应产物。举例来说,丙烯酸氨基甲酸酯可制备为含有聚氨基甲酸酯寡聚物的末端不饱和异氰酸酯与烷氧基化多元醇的反应产物,例如如美国专利第5,578,693号中所论述。含有聚氨基甲酸酯寡聚物的末端不饱和异氰酸酯可如下制备:通过使至少一种聚异氰酸酯与至少一种多元醇反应以形成异氰酸酯封端的预聚物、使未反应的末端异氰酸酯基的一部分与至少一种羟基官能性丙烯酸酯或羟基官能性乙烯基醚反应以形成末端不饱和含异氰酸酯的氨基甲酸酯寡聚物,和使其余的末端异氰酸酯基与至少一种烷氧基化多元醇反应,如美国专利第5,578,693号中所论述。
三维打印组合物可排除其它丙烯酸氨基甲酸酯,且仅包括作为丙烯酸酯与异氰酸酯封端的预聚物的封端反应产物的丙烯酸氨基甲酸酯,异氰酸酯封端的预聚物为聚异氰酸酯与至少一种具有至少3000g/mol的分子量的衍生多元醇的反应产物。举例来说,组合物可排除聚乙二醇与(甲基)丙烯酸化多元醇寡聚物的直接官能化(甲基)丙烯酸化氨基甲酸酯寡聚物衍生物。
丙烯酸氨基甲酸酯组分可为在形成具有多官能性环氧组分、单体组分和光引发剂组分的组合物之前(例如在混合之前)形成的预先形成的组分。以另一种方式说明,丙烯酸氨基甲酸酯组分可在形成光固化性组合物之前形成。
多官能性环氧组分
实施例包括多官能性环氧组分,例如包括一种或多种双官能性(即包括两个环氧官能团)环脂族环氧化物和/或一种或多种双官能芳族环氧化物。环脂族环氧化物包括环氧官能团(例如C2H2O)融合至环脂族环的分子中的一个或多个环脂族环。在例示性实施例中,双官能性环脂族环氧化物可包括两个环脂族环,其上各自具有一个连接的环氧官能团,因此环氧官能团仅连接至环脂族环。两个不同环脂族环可通过羧酸酯基连接。两个环脂族环可各自包括5至6个碳原子。例示性双官能性环脂族环氧化物为3,4-环氧环己基甲基-3,4-环氧基环己烷甲酸酯。
在例示性实施例中,光固化性组合物可排除其它环氧化物,除了双官能性环脂族环氧化物和/或双官能性芳族环氧化物。举例来说,组合物可排除并非双官能性环脂族环氧化物和/或双官能性芳族环氧化物的任何缩水甘油基型脂族环氧树脂、基于双酚A的环氧树脂、基于双酚F的环氧树脂、酚醛清漆环氧树脂和缩水甘油基胺环氧树脂。
单体组分
单体组分包括多官能性丙烯酸酯单体(即包括两个或更多个丙烯酸酯官能团的单体)和多官能性乙烯基醚单体(即包括两个或更多个乙烯基的单体)中的至少一个。举例来说,单体组分可包括二丙烯酸酯单体和/或二乙烯基醚单体。单体组分可至少部分用作反应性稀释剂。
单体组分可包括按单体组分的总重量计的90重量%至100重量%的一种或多种二丙烯酸酯单体、按单体组分的总重量计的90重量%至100重量%的一种或多种二乙烯基醚单体或按单体组分的总重量计的90重量%至100重量%的一种或多种二丙烯酸酯单体和一种或多种二乙烯基醚单体。
例示性多官能性丙烯酸酯单体包括二甲基丙烯酸氨基甲酸酯、二甲基丙烯酸1,3-甘油酯、二丙烯酸1,6-己二醇酯、二甲基丙烯酸1,6-己二醇酯、二丙烯酸1,4-丁二醇酯、二甲基丙烯酸1,4-丁二醇酯和二甲基丙烯酸三乙二醇酯。例示性多官能性乙烯基醚单体包括二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、1,4-环己烷二羟甲基二乙烯基醚、二丙二醇二乙烯基醚、三丙二醇二乙烯基醚、1,6-己二醇二乙烯基醚和1,4-丁二醇二乙烯基醚。
光引发剂组分
光引发剂组分包括一种或多种光引发剂。举例来说,光引发剂组分可包括一种或多种自由基光引发剂和/或一种或多种阳离子光引发剂。举例来说,可使用所属领域中已知用于三维打印的组合物的光引发剂,例如可使用所属领域中已知用于基于立体光刻的方法的光引发剂。
例示性自由基光引发剂以足以引发聚合反应的量包括在曝光于辐射,如紫外线和/或可见光辐射时产生自由基的化合物。自由基光引发剂可为单一化合物、两种或更多种活性化合物的混合物或两种或更多种不同化合物(如共引发剂)的组合。例示性阳离子光引发剂以足以引发聚合的量包括在曝光于辐射,如紫外线和/或可见光辐射时形成非质子酸或布朗斯特酸(Bronsted acid)的化合物。使用的阳离子型光引发剂可为单一化合物、两种或更多种活性化合物的混合物或两种或更多种不同化合物(如共引发剂)的组合。阳离子型光引发剂可与光敏剂,例如9,10-二乙氧基蒽共同使用以使得阳离子型光引发剂能够经较宽波长范围被激活。
光固化性组合物
组合物可用于制备用于三维打印技术,例如用于基于立体光刻的三维打印方法的材料,其具有所需肖氏A硬度(例如40至95)、良好伸长率%值(例如至少50%)和良好拉伸强度(例如至少900psi)。良好伸长率%和良好拉伸强度的组合在使用三维打印方法形成的柔性物体中是高度所需的。举例来说,由于拉伸强度和伸长率%通常被认为成反比,所述特性中的一个的升高通常导致另一特性的减小。因此,寻求在所需肖氏A硬度下提供伸长率%和拉伸强度的良好平衡的材料。
在例示性实施例中,组合物可在光引发剂和光化辐射存在下组合丙烯酸氨基甲酸酯、双官能性环氧化物(如3,4-环氧环己基甲基3,4-环氧基环己烷甲酸酯)和单体/稀释剂(如二丙烯酸酯或二乙烯基醚)以制备用于形成柔性三维打印物体的材料,如在下文示意图1中所示。举例来说,示意图1中的方法可利用基于立体光刻的三维打印方法。
在例示性实施例中,组合物可在光引发剂和光化辐射存在下组合丙烯酸氨基甲酸酯、双官能性环氧化物3,4-环氧环己基甲基3,4-环氧基环己烷甲酸酯和二氧化二乙烯基苯,以及二丙烯酸酯或二乙烯基醚的单体以制备用于形成柔性三维打印物体的材料,如在下文示意图2中所示。举例来说,示意图2中的方法可利用基于立体光刻的三维打印方法。
组合物的所得反应产物可包括至少两种不同相:(1)相对软多元醇相,和(2)相对较硬环氧树脂/丙烯酸酯/氨基甲酸酯相。当参看DMA(动态机械分析)数据时,此类材料可展现至少两个不同玻璃转化温度峰,例如可展现经一定温度范围实现组合的玻璃-橡胶状态的相分离形态。在存在相异的玻璃转化温度的情况下,在两个玻璃转化温度峰之间的任何温度处,已从脆性玻璃相过渡为橡胶状态的橡胶相和尚未转化为橡胶状态的脆性玻璃相共存。这可允许对应相的两个玻璃转化温度之间的更均一机械特性,且可在用作用于三维打印柔性物体的光固化性组合物时提供增强的特性。举例来说,存在橡胶相允许可变形的材料且存在刚性玻璃相提供一种增强机制,所述增强机制提供材料的足够肖氏A硬度、增加的拉伸强度和/或增加的机械完整性(如储能模量)。相比之下,仅展现一个玻璃转化温度的材料完全为低于玻璃转化温度的玻璃且因此为脆性的且可能不能够为用于三维打印柔性物体的光固化性组合物提供足够断裂伸长率%和拉伸强度。此类单一玻璃转化材料可完全为高于玻璃转化温度的橡胶,其中材料可能不具有用于三维打印的柔性物体的足够机械强度。
除非另外指明,否则所有份数和百分比都是以重量计。除非另外规定,否则所有分子量值是按数目平均分子量计。除非另外规定,否则所有提及的官能度是基于标称官能度(如所属领域的技术人员将理解)。
实例
所述实例如下文所论述地制备。确切地说,首先合成丙烯酸氨基甲酸酯。接着,制备且分析例示性和比较组合物。以下描述为近似的,例如就材料特性和工艺规范而言。
丙烯酸氨基甲酸酯合成
丙烯酸氨基甲酸酯经由下文所述的方法用多元醇制备,其中首先合成预聚物,且其次,对所得预聚物进行丙烯酸酯封端程序。
在丙烯酸氨基甲酸酯合成中,主要使用的材料为如下:
异氰酸酯单体二异氰酸甲苯酯,即TDI掺合物,具有大致80重量%的TDI的2,4异构体和大致20重量%的TDI的2,6异构体(可以VORANATETM T-80形式从陶氏化学公司(The DowChemical Company)购得)。
多元醇1 基于DMC催化的聚丙烯的二醇(即2的标称羟基官能度),具有大致4000g/mol的分子量和大致0.007meq/g的不饱和度(可以VORANOLTM LM 4000形式从陶氏化学公司购得)。
多元醇2 基于DMC催化的聚丙烯的二醇,具有大致8000g/mol的分子量(可以VORANOLTM LM 8000形式从陶氏化学公司购得)。
丙烯酸酯 基于丙烯酸羟乙酯(HEA)羟烷基酯单体的溶液,包括至少约95重量%的HEA(可以ROCRYLTM 420形式从陶氏化学公司购得)。
步骤1包括使用多元醇的预聚物合成。确切地说,在步骤1中,将异氰酸酯(大致75克)和多元醇1(大致827克)馈入至装备有顶部搅拌装置、温度控制探头、加料漏斗和氮气入口的干燥2升4颈圆底烧瓶。将反应器加热至80℃且添加一滴二月桂酸二丁基锡。搅拌反应物大致2小时。如通过滴定所测定,预聚物的最终NCO含量(即异氰酸酯部分含量)为大致2%。
步骤2包括来自步骤1的所得预聚物的丙烯酸酯封端。确切地说,在步骤2中,将丙烯酸酯(大致54.3克)添加至来自上文的所得预聚物(大致881克),且在45C下搅拌反应物2小时。通过FT-IR(约2250cm-1)观测残余异氰酸酯。再添加一滴二月桂酸二丁基锡且再继续搅拌2小时,其后如通过FT-IR分析所观测,不存在NCO拉伸(即在FT-IR分析中,所述异氰酸酯官能团不存在可观测的激励模式,使得NCO拉伸等于使用FT-IR分析时的吸收率)。所得材料提及为丙烯酸氨基甲酸酯1,其用于3D打印调配物,且论述于下文。
丙烯酸氨基甲酸酯合成的例示性示意图说明如下:
基于上文,显示丙烯酸氨基甲酸酯1包括异氰酸酯封端的预聚物衍生的丙烯酸酯封端的芳族氨基甲酸酯。
使用如关于丙烯酸氨基甲酸酯1在上文所述的相同方法制备丙烯酸氨基甲酸酯2,除了使用较高分子量多元醇(即具有8000g/mol的分子量的多元醇2)。
三维可打印调配物
在3D打印组合物的制备中,主要使用的材料为如下:
丙烯酸氨基甲酸酯1 二丙烯酸酯官能性氨基甲酸酯-丙烯酸酯预聚物,如上文所论述地合成。
丙烯酸氨基甲酸酯2 二丙烯酸酯官能性氨基甲酸酯-丙烯酸酯预聚物,如上文所论述地合成。
环氧化物2 二氧化二乙烯基苯,一种双官能环氧化物,其可通过使二乙烯基苯与过氧化氢反应而制备。
丙烯酸酯 二丙烯酸1,6-己二醇酯,即二丙烯酸酯单体(可以SR238形式购自ARKEMA)。
乙烯基醚 三乙二醇二乙烯基醚,即二乙烯基醚单体,也称为3,6,9,12-四氧杂十四-1,13-二烯,具有202g/mol的分子量(购自BASF)。
工作实例1至7是根据下表1中示出的大致调配物制备。
表1
断裂伸长率%和拉伸强度是根据ASTM D1708计算。肖氏A硬度是根据ASTM D2240的修改版本,使用折叠膜样品测量。50℃下的储能模量是从动态机械分析(DMA)数据提取。使用压模从膜切割尺寸47.5mm×7mm的DMA样品条且随后使用TA Instruments Ares II流变仪以扭转模式分析。以振荡模式(1Hz),在-90℃至200℃的3℃/min温度匀变下测量线性粘弹性反应(具有自动应力调节的4%应力)。
根据下表2中示出的大致调配物制备比较实例A至D。比较实例A和B并不含环氧组分。按三维可打印调配物的总重量计,比较实例C包括大于70重量%的丙烯酸氨基甲酸酯1。比较实例D包括大于60重量%的环氧化物1。
表2
N/A=不可用
参看比较实例A至D,可见未实现相对高断裂伸长率%和拉伸强度的组合。
另外,商业材料的特性获自从和Systems在线可用的技术数据表。就下表3而言,此类商业材料展现低断裂伸长率%或低拉伸强度。相比之下,参考上表1,工作实例1-7展现相对高断裂伸长率%和相对高拉伸强度的组合。
表3
实例E为TangoBlackPlus FLX980(购自),其为用于三维打印的基于丙烯酸的调配物。实例F为TangoBlack FLX973(购自),其为用于三维打印的基于丙烯酸的调配物。实例G为TangoGray FLX950(购自),其为用于三维打印的基于丙烯酸的调配物。实例H为SL Flex(购自Systems),其为基于环氧树脂的三维打印材料。实例I为Flex w/Flexseal(购自Systems),其为用于选择性激光烧结(SLS)的热塑性弹性材料,SLS不同于基于立体光刻的方法(SLA)。如所显示,就工作实例1至7而言,根据实施例的组合物提供良好伸长率和断裂、良好拉伸强度和良好肖氏A硬度。
Claims (9)
1.一种用于基于柔性材料的物体的三维打印光固化性组合物,所述组合物包含:
按所述组合物的总重量计,45重量%至50重量%的丙烯酸氨基甲酸酯组分,所述丙烯酸氨基甲酸酯组分包括丙烯酸酯与异氰酸酯封端的预聚物的封端反应产物,所述异氰酸酯封端的预聚物为聚异氰酸酯与至少一种具有至少3000g/mol的分子量的多元醇的反应产物;
按所述组合物的总重量计,35重量%至45重量%的包括一种或多种双官能性环脂族环氧化物和一种或多种双官能性芳族环氧化物的多官能性环氧组分,其中所述双官能性环脂族环氧化物和所述双官能性芳族环氧化物包括两个环氧官能团;
按所述组合物的总重量计,5重量%至15重量%的包括多官能性丙烯酸酯单体和多官能性乙烯基醚单体中的至少一个的单体组分,所述多官能性丙烯酸酯单体包括两个或更多个丙烯酸酯官能团,所述多官能性乙烯基醚单体包括两个或更多个乙烯基;和
按所述组合物的总重量计,1重量%至8重量%的光引发剂组分,所述光引发剂组分包括一种或多种自由基光引发剂和一种或多种阳离子光引发剂。
2.根据权利要求1所述的组合物,其中所述一种或多种双官能性芳族环氧化物的量为5重量%至60重量%,按所述多官能性环氧组分的总重量计。
3.根据权利要求1所述的组合物,其中所述多官能性环氧组分包括按所述多官能性环氧组分的总重量计,5重量%至60重量%的量的二氧化二乙烯基苯。
4.根据权利要求2所述的组合物,其中所述多官能性环氧组分包括按所述多官能性环氧组分的总重量计,5重量%至60重量%的量的二氧化二乙烯基苯。
5.根据权利要求1到4中任一项所述的组合物,其中所述单体组分包括以下中的一个:
(a)按所述单体组分的总重量计,90重量%至100重量%的一种或多种二丙烯酸酯单体,
(b)按所述单体组分的总重量计,90重量%至100重量%的一种或多种二乙烯基醚单体,或
(c)按所述单体组分的总重量计,90重量%至100重量%的一种或多种二丙烯酸酯单体和一种或多种二乙烯基醚单体。
6.根据权利要求1到4中任一项所述的组合物,其中所述丙烯酸氨基甲酸酯组分为在形成具有所述多官能性环氧组分、所述单体组分和光引发剂组分的所述组合物之前形成的预先形成的组分。
7.一种包括根据权利要求1到6中任一项所述的组合物的打印的三维柔性物品,所述组合物经光固化。
8.一种使用根据权利要求1到6中任一项所述的组合物和三维打印装置形成的打印的三维柔性物品,所述装置包括用于分配所述组合物的分配机构和用于对所述组合物进行光固化的光固化机构。
9.一种基于立体光刻的三维打印方法,其包含分配根据权利要求1到6中任一项所述的组合物以形成柔性物品的阶段。
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PCT/US2016/019499 WO2016153711A1 (en) | 2015-03-23 | 2016-02-25 | Photocurable compositions for three-dimensional printing |
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Families Citing this family (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11602412B2 (en) | 2016-12-23 | 2023-03-14 | 3M Innovative Properties Company | Printable compositions including polymeric and polymerizable components, articles, and methods of making articles therefrom |
EP3658990B1 (en) | 2017-07-28 | 2023-11-08 | Stratasys Ltd. | Formulations usable in additive manufacturing of a three-dimensional object made of a soft material |
WO2019021292A1 (en) | 2017-07-28 | 2019-01-31 | Stratasys Ltd. | METHOD AND SYSTEM FOR MANUFACTURING AN OBJECT HAVING PROPERTIES OF A BLOOD VESSEL |
ES2967291T3 (es) | 2017-07-28 | 2024-04-29 | Stratasys Ltd | Procesos de fabricación aditiva que emplean un material que presenta propiedades de un tejido corporal blando |
JP7197561B2 (ja) | 2017-07-28 | 2022-12-27 | ストラタシス リミテッド | 硬組織の特性を具備する物体を製作するための方法及びシステム |
US10434704B2 (en) * | 2017-08-18 | 2019-10-08 | Ppg Industries Ohio, Inc. | Additive manufacturing using polyurea materials |
US11616302B2 (en) | 2018-01-15 | 2023-03-28 | Rogers Corporation | Dielectric resonator antenna having first and second dielectric portions |
CN108455966B (zh) * | 2018-01-17 | 2020-09-01 | 龙泉市金宏瓷业有限公司 | 一种基于光固化的3d打印陶瓷材料及其制备方法 |
WO2019169211A1 (en) * | 2018-03-02 | 2019-09-06 | Formlabs, Inc. | Latent cure resins and related methods |
KR20210005628A (ko) * | 2018-04-20 | 2021-01-14 | 디에스엠 아이피 어셋츠 비.브이. | 적층 제조용 복사선 경화성 조성물 |
US11552390B2 (en) | 2018-09-11 | 2023-01-10 | Rogers Corporation | Dielectric resonator antenna system |
US20220033678A1 (en) * | 2018-09-24 | 2022-02-03 | Basf Se | Photocurable composition for use in 3d printing |
TWI820237B (zh) | 2018-10-18 | 2023-11-01 | 美商羅傑斯公司 | 聚合物結構、其立體光刻製造方法以及包含該聚合物結構之電子裝置 |
CN113169455A (zh) | 2018-12-04 | 2021-07-23 | 罗杰斯公司 | 电介质电磁结构及其制造方法 |
TW202043298A (zh) | 2019-05-30 | 2020-12-01 | 美商羅傑斯公司 | 用於立體微影的光可固化組合物、形成該組合物的方法、使用該組合物的立體微影方法、藉由該立體微影方法形成的聚合物組件、及包含該聚合物組件的裝置 |
WO2020249673A1 (en) * | 2019-06-14 | 2020-12-17 | Huntsman International Llc | A curable polyurethane based resin for use in additive manufacturing |
EP3990254A1 (en) * | 2019-06-26 | 2022-05-04 | Henkel IP & Holding GmbH | Curable compositions |
WO2021004383A1 (en) * | 2019-07-09 | 2021-01-14 | Luxcreo (Beijing) Inc. | Prepolymer with multiple functional groups for printing three-dimensional objects and method of using the same |
US20210069860A1 (en) * | 2019-09-11 | 2021-03-11 | Applied Materials, Inc. | Compositions and Methods of Additive Manufacturing of Polishing Pads |
US12006442B2 (en) | 2019-09-11 | 2024-06-11 | Applied Materials, Inc. | Additive manufacturing of polishing pads |
CN112538135B (zh) * | 2019-09-23 | 2021-09-28 | 中国科学院兰州化学物理研究所 | 一种异氰酸酯墨水及其制备方法和应用 |
EP3838592A1 (en) * | 2019-12-17 | 2021-06-23 | Evonik Operations GmbH | Composition comprising polyesters for additive manufacturing |
EP4117918A1 (en) | 2020-03-13 | 2023-01-18 | Basf Se | Photo-curable composition for 3d printing, its preparation and use, and method of forming 3d-printed objects by using the same |
US11482790B2 (en) | 2020-04-08 | 2022-10-25 | Rogers Corporation | Dielectric lens and electromagnetic device with same |
US20230322998A1 (en) * | 2020-06-02 | 2023-10-12 | Blue Cube Ip Llc | Photo-curable resin composition for use in stereolithography |
CN112062896B (zh) * | 2020-08-25 | 2022-05-31 | 南方科技大学 | 吸能3d打印材料及其制备方法和吸能装置 |
JP2023540738A (ja) * | 2020-09-03 | 2023-09-26 | ビーエーエスエフ ソシエタス・ヨーロピア | 反応性ポリウレタンエラストマー |
CN112250804A (zh) * | 2020-10-23 | 2021-01-22 | 浙江大学 | 一种二次固化3d打印树脂 |
CN115043987B (zh) * | 2022-07-26 | 2024-02-02 | 珠海赛纳三维科技有限公司 | 一种3d打印用组合物、打印方法和装置 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101898423A (zh) * | 2003-12-03 | 2010-12-01 | 奥布吉特几何有限公司 | 用于三维模型印刷的组合物和方法 |
WO2014100238A2 (en) * | 2012-12-21 | 2014-06-26 | Dow Global Technologies Llc | Phase-segmented non-isocyanate elastomers |
Family Cites Families (83)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3660145A (en) * | 1970-12-21 | 1972-05-02 | Ford Motor Co | Epoxy resin and acrylic rubber-urethane-acrylate paint and painting process |
US3859382A (en) * | 1972-01-19 | 1975-01-07 | Firestone Tire & Rubber Co | Method of making nylon constituent block copolymers of predetermined pliability at low temperatures |
US4003751A (en) * | 1974-09-05 | 1977-01-18 | Union Carbide Corporation | Coating and ink compositions |
USRE30212E (en) * | 1974-09-05 | 1980-02-12 | Union Carbide Corporation | Coating and ink compositions |
US4144156A (en) * | 1976-04-14 | 1979-03-13 | Basf Aktiengesellschaft | Manufacture of unsymmetric monoacetals of aromatic 1,2-diketones employable as photoiniatiators |
US4145515A (en) * | 1976-12-01 | 1979-03-20 | Congoleum Corporation | Method of forming storage-stable polyurethane prepolymers |
US4508916A (en) * | 1979-04-11 | 1985-04-02 | Minnesota Mining And Manufacturing Company | Curable substituted urethane acrylates |
DE2936039A1 (de) * | 1979-09-06 | 1981-04-02 | Bayer Ag, 5090 Leverkusen | Wasserdispergierbare, durch strahlen vernetzbare bindemittel aus urethanacrylaten, ein verfahren zu ihrer herstellung sowie die verwendung dieser bindemittel in waessriger dispersion auf dem anstrich-, druckfarben- und textilsektor |
JPS59104725A (ja) * | 1982-12-06 | 1984-06-16 | Fuji Photo Film Co Ltd | 磁気記録媒体 |
GB8827847D0 (en) * | 1988-11-29 | 1988-12-29 | Ciba Geigy Ag | Method |
GB8913090D0 (en) * | 1989-06-07 | 1989-07-26 | Ciba Geigy Ag | Method |
US5869592A (en) * | 1991-08-19 | 1999-02-09 | Maxdem Incorporated | Macromonomers having reactive side groups |
US5264061A (en) * | 1992-10-22 | 1993-11-23 | Motorola, Inc. | Method of forming a three-dimensional printed circuit assembly |
JP3117394B2 (ja) * | 1994-11-29 | 2000-12-11 | 帝人製機株式会社 | 光学的立体造形用樹脂組成物 |
WO1996035756A1 (fr) * | 1995-05-12 | 1996-11-14 | Asahi Denka Kogyo Kabushiki Kaisha | Composition a base de resines stereolithographiques et procede de stereolithographie |
US5578693A (en) | 1995-09-05 | 1996-11-26 | Bomar Specialties Company | Multifunctional terminally unsaturated urethane oligomers |
JPH1087963A (ja) * | 1996-09-20 | 1998-04-07 | Japan Synthetic Rubber Co Ltd | 樹脂組成物および繊維質材料成形型 |
US20020045126A1 (en) * | 1996-09-20 | 2002-04-18 | Tsuyoshi Watanabe | Photo-curable resin compositions and process for preparing a resin-based mold |
JP3724893B2 (ja) * | 1996-09-25 | 2005-12-07 | ナブテスコ株式会社 | 光学的立体造形用樹脂組成物 |
US5744514A (en) * | 1996-10-31 | 1998-04-28 | Borden Chemical, Inc. | Coated optical fibers having a reduced content of extractable and volatile material |
JP3626302B2 (ja) * | 1996-12-10 | 2005-03-09 | Jsr株式会社 | 光硬化性樹脂組成物 |
JP3765896B2 (ja) * | 1996-12-13 | 2006-04-12 | Jsr株式会社 | 光学的立体造形用光硬化性樹脂組成物 |
US5931803A (en) * | 1997-04-04 | 1999-08-03 | Playtex Products, Inc. | Epoxy coated tampon applicator having a pierce-through fingergrip |
JP4204113B2 (ja) * | 1997-12-04 | 2009-01-07 | 株式会社Adeka | 新規な芳香族スルホニウム化合物、これからなる光酸発生剤およびこれを含む光重合性組成物、光造形用樹脂組成物ならびに光学的立体造形法 |
US6136497A (en) * | 1998-03-30 | 2000-10-24 | Vantico, Inc. | Liquid, radiation-curable composition, especially for producing flexible cured articles by stereolithography |
US6117326A (en) * | 1998-06-26 | 2000-09-12 | Rohm And Haas Company | Capillary electrochromatography separation media |
SG98433A1 (en) * | 1999-12-21 | 2003-09-19 | Ciba Sc Holding Ag | Iodonium salts as latent acid donors |
US6569373B2 (en) * | 2000-03-13 | 2003-05-27 | Object Geometries Ltd. | Compositions and methods for use in three dimensional model printing |
CN1180001C (zh) * | 2000-05-24 | 2004-12-15 | 旭化成株式会社 | 具有高的伯端羟基比率的聚碳酸酯二醇 |
US20040071980A1 (en) * | 2000-07-12 | 2004-04-15 | Mcbain Douglas S. | Method for in-mold coating a polyolefin article |
US6617033B1 (en) * | 2000-07-12 | 2003-09-09 | Omnova Solutions Inc. | Method for in-mold coating a polyolefin article |
US20020155309A1 (en) * | 2001-02-21 | 2002-10-24 | Zhixin Li | Mold release and anti-blocking coating for powder-free natural or synthetic rubber articles |
US20030092801A1 (en) * | 2001-11-15 | 2003-05-15 | Giorgio Agostini | Rubber composition comprised of functionalized elastomer and starch composite with coupling agent and tire having at least one component thereof |
US20030192643A1 (en) * | 2002-03-15 | 2003-10-16 | Rainer Schoenfeld | Epoxy adhesive having improved impact resistance |
WO2003082945A1 (fr) * | 2002-04-03 | 2003-10-09 | Kyowa Hakko Cmemical Co., Ltd. | Resine de polyalcenyle ether |
GB0212062D0 (en) * | 2002-05-24 | 2002-07-03 | Vantico Ag | Jetable compositions |
GB0212977D0 (en) * | 2002-06-06 | 2002-07-17 | Vantico Ag | Actinic radiation curable compositions and their use |
US7713604B2 (en) * | 2002-06-17 | 2010-05-11 | 3M Innovative Properties Company | Curable adhesive articles having topographical features therein |
EP1539451A2 (en) * | 2002-08-20 | 2005-06-15 | The Regents of the University of Colorado | Polymer derived ceramic materials |
US20050181214A1 (en) * | 2002-11-22 | 2005-08-18 | John Robert Campbell | Curable epoxy compositions, methods and articles made therefrom |
US20050170188A1 (en) * | 2003-09-03 | 2005-08-04 | General Electric Company | Resin compositions and methods of use thereof |
TW583226B (en) * | 2002-12-17 | 2004-04-11 | Ind Technology Res Inst Materi | Formulation in preparing solid electrolytic capacitor and process thereof |
TWI230832B (en) * | 2003-01-24 | 2005-04-11 | Sipix Imaging Inc | Novel adhesive and sealing layers for electrophoretic displays |
US7112616B2 (en) * | 2003-03-25 | 2006-09-26 | Fuji Photo Film Co., Ltd. | Two-photon absorbing polymerizable composition and polymerization process thereof |
US20060293404A1 (en) * | 2003-04-24 | 2006-12-28 | Santobianco John G | New class of amine coinitiators in photoinitiated polymerizations |
US20060231982A1 (en) * | 2003-07-23 | 2006-10-19 | Xiaorong You | Viscosity reducible radiation curable resin composition |
US7018463B2 (en) * | 2003-07-24 | 2006-03-28 | Lens Technology I, Llc | Abrasion resistant coating composition |
WO2005095513A1 (en) * | 2004-03-25 | 2005-10-13 | Kraton Polymers Research B.V. | Thermoplastic gel compositions that can be converted into thermoset gel compositions by exposure to radiation |
US20050238815A1 (en) * | 2004-04-27 | 2005-10-27 | Dvorchak Michael J | UV curable coating composition |
US7166649B2 (en) * | 2004-04-27 | 2007-01-23 | Ashland Chemical, Inc. | Polyester-polyether hybrid urethane acrylate oligomer for UV curing pressure sensitive adhesives |
US7268172B2 (en) * | 2004-10-15 | 2007-09-11 | Bayer Materialscience Llc | Radiation curable compositions |
DE102004057292A1 (de) * | 2004-11-26 | 2006-06-01 | Klebchemie, M.G. Becker Gmbh & Co Kg | Verfahren zur Herstellung von reaktiven Polyurethanzusammensetzungen |
JP4872247B2 (ja) * | 2005-06-16 | 2012-02-08 | Basfコーティングスジャパン株式会社 | 熱硬化性塗料組成物 |
US7691557B2 (en) * | 2005-06-29 | 2010-04-06 | Dymax Corporation | Polymerizable composition exhibiting permanent color change as cure indicator |
US20100152314A1 (en) * | 2005-09-29 | 2010-06-17 | Cmet Inc. | Resin composition for stereolithography |
US7915319B2 (en) * | 2005-12-19 | 2011-03-29 | Henkel Corporation | Visible light curing systems, methods for reducing health risks to individuals exposed to systems designed to cure curable compositions by exposure to radiation, methods for bonding substrates and visible light curing compositions |
CA2649516C (en) * | 2006-04-17 | 2014-11-04 | Kuraray Co., Ltd. | Molded article and method for production thereof |
WO2007136003A1 (ja) * | 2006-05-24 | 2007-11-29 | Dic Corporation | 光ディスク及び光ディスク用紫外線硬化型組成物 |
JP5280615B2 (ja) * | 2006-06-16 | 2013-09-04 | シーメット株式会社 | 光学的立体造形用樹脂組成物 |
US7655278B2 (en) * | 2007-01-30 | 2010-02-02 | Sabic Innovative Plastics Ip B.V. | Composite-forming method, composites formed thereby, and printed circuit boards incorporating them |
JP5135564B2 (ja) * | 2007-06-12 | 2013-02-06 | デクセリアルズ株式会社 | 接着剤組成物 |
US20090004579A1 (en) * | 2007-06-27 | 2009-01-01 | Dsm Ip Assets B.V. | Clear and colorless three-dimensional articles made via stereolithography and method of making said articles |
US7994238B2 (en) * | 2007-09-04 | 2011-08-09 | General Electric Company | Article and associated method |
US20090104364A1 (en) * | 2007-10-17 | 2009-04-23 | Ppg Industries Ohio, Inc. | Non-weldable coating compositions exhibiting corrosion resistance properties |
US20090186306A1 (en) * | 2007-11-09 | 2009-07-23 | Klas Tommy Haraldsson | Polymeric microfluidic devices from liquid thermoset precursors |
EP2223299B1 (en) * | 2007-11-27 | 2015-03-11 | Southbourne Investments Ltd. | Holographic recording medium |
US20090176907A1 (en) * | 2008-01-08 | 2009-07-09 | Ramesh Subramanian | Direct-to-metal radiation curable compositions |
US20090214790A1 (en) * | 2008-02-25 | 2009-08-27 | Stephen Simpson | Method of making an ink-printed fibrous web |
US9624171B2 (en) * | 2008-06-06 | 2017-04-18 | Basf Se | Photoinitiator mixtures |
IL200995A0 (en) * | 2008-10-01 | 2010-06-30 | Bayer Materialscience Ag | Polyether-based polyurethane formulations for the production of holographic media |
EP2385971A4 (en) * | 2009-01-08 | 2013-06-26 | Univ Western Ontario | SELF-CLEANING COATINGS |
BR112012014900B1 (pt) * | 2009-12-17 | 2019-09-10 | Dsm Ip Assets Bv | processo para fabricação de aditivo com base em substrato |
US8385703B2 (en) * | 2010-03-02 | 2013-02-26 | Corning Incorporated | High numerical aperture multimode optical fiber |
JP5757749B2 (ja) * | 2010-05-19 | 2015-07-29 | 富士フイルム株式会社 | 重合性組成物 |
RU2013103824A (ru) * | 2010-09-24 | 2014-08-10 | Коутингс Форейн АйПи Ко., ЛЛК | Композиция покрытия для металлических проводников |
CN103429631B (zh) * | 2010-12-20 | 2018-07-24 | 粘合化学M.G.贝克尔有限及两合公司 | 具有耐磨填料的反应性聚氨酯组合物 |
JP5966500B2 (ja) * | 2011-05-02 | 2016-08-10 | 株式会社リコー | シリコーン化合物、該シリコーン化合物を用いた光硬化型液体インク及びその製造方法 |
CN103649160B (zh) * | 2011-05-13 | 2016-01-13 | 陶氏环球技术有限责任公司 | 绝缘制剂 |
EP2574647A1 (en) * | 2011-09-30 | 2013-04-03 | Cytec Austria GmbH | Aqueous coating compositions |
JP2014139293A (ja) * | 2012-12-20 | 2014-07-31 | Dow Global Technologies Llc | エポキシ樹脂組成物、それを製造する方法、およびその物品 |
US20140275320A1 (en) * | 2013-03-14 | 2014-09-18 | Allnex IP S.à.r.I. | Methods for making elastomers, elastomer compositions and related elastomers |
US9383511B2 (en) * | 2013-05-02 | 2016-07-05 | Corning Incorporated | Optical fiber with large mode field diameter and low microbending losses |
US20190270844A1 (en) * | 2016-09-26 | 2019-09-05 | Sabic Global Technologies B.V. | Homogeneous amorphous high heat epoxy blend composite compositions, articles, and uses thereof |
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2016
- 2016-02-25 EP EP16714079.7A patent/EP3274155B1/en active Active
- 2016-02-25 CN CN201680016615.0A patent/CN107428892B/zh active Active
- 2016-02-25 ES ES16714079T patent/ES2879637T3/es active Active
- 2016-02-25 WO PCT/US2016/019499 patent/WO2016153711A1/en active Application Filing
- 2016-02-25 US US15/559,564 patent/US20180046076A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101898423A (zh) * | 2003-12-03 | 2010-12-01 | 奥布吉特几何有限公司 | 用于三维模型印刷的组合物和方法 |
WO2014100238A2 (en) * | 2012-12-21 | 2014-06-26 | Dow Global Technologies Llc | Phase-segmented non-isocyanate elastomers |
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ES2879637T3 (es) | 2021-11-22 |
EP3274155A1 (en) | 2018-01-31 |
EP3274155B1 (en) | 2021-06-02 |
WO2016153711A1 (en) | 2016-09-29 |
CN107428892A (zh) | 2017-12-01 |
US20180046076A1 (en) | 2018-02-15 |
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