CN102597116A - 可固化组合物、涂覆底片的方法、以及被涂覆的底片 - Google Patents
可固化组合物、涂覆底片的方法、以及被涂覆的底片 Download PDFInfo
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Abstract
一种可固化组合物,包含:由化学式X-Si(OR1)(OR2)(OR3)表示的环氧硅烷,其中,R1-R3表示C1至C4烷基,并且X表示具有至少一个环氧环的有机基;由化学式表示的氟化硅烷;其中:Rf表示具有3至5个碳原子的全氟烷基,R4表示H或C1至C4烷基,并且R5-R7表示C1至C4烷基;以及光酸。另外公开了所述可固化组合物用于涂覆底片,从而在所述底片上提供保护涂层的用途。
Description
技术领域
本公开广义地涉及用于底片的保护涂层。
背景技术
在印刷电路工业中,通常由以高分辨率的一系列点线表示的承载与电路相对应的图像的照相掩模被称作底片。通常使用计算机辅助设计(CAD)系统基于目标蓝图或数据来为暴露设备准备数据来制备底片。于是,这个数据被用来进行将设计图案(例如,电路图案)直接写入到乳状液照相干燥板上,所述乳状液照相干燥板已经通过在光学透明的基底(例如,玻璃基底、熔凝的二氧化硅或聚对苯二甲酸乙二醇酯(PET)、聚碳酸酯、或聚(甲基丙烯酸甲酯)基底)上形成光敏乳状液层的膜表面来制备。图像通常由多个细纹和密集间隔在一起的交叉点组成,并且通常被提供为设置在透明基底上的图像层,但在一些情况下其可以被设置在基底内部。在使用其制造印刷电路板期间,底片被正面向下设置在用来制造印刷电路板的光致抗蚀剂层上,并且通过透过底片使光致抗蚀剂暴露于高强度光来实现接触印刷。按照这种方式,单个底片能够被用来实现多个接触印刷。
底片设置在其上的光致抗蚀剂通常被层合在片铜上,并且当底片被从一个光致抗蚀剂传送到下一个光致抗蚀剂时小的毛刺或铜片的蓬乱边缘能够引起刮伤。底片还被频繁地使用软布来擦试以确保其无粉尘和棉绒。当在整个底片的表面擦试灰尘的微粒时,灰尘的微粒能够引起刮伤。由于在正常使用期间底片表面上的这种一般的磨损和撕裂,所以很多情况下必须通过显微镜法来检查底片以确保线条连续性。根据基底的尺寸和复杂情况,这种微观检测可花费2到3个小时。
由于典型的底片容易刮伤,并且由于在底片的正常使用期间模压是个严重的问题,所以通常采用保护膜和外涂层来保护该底片。例如,具有各种压敏粘合剂涂覆的聚酯膜已经被层合至底片的图像层以保护该图像。然而,由于它们的厚度,层合膜可引起光学失真并且因此能够引起分辨率的损耗。可通过使用液体组合物涂覆底片的表面来获得更簿的保护涂层。在应用之后,簿的液体涂层被硬化以产生所需的保护涂层。环氧硅烷和丙烯酸酯酯基(例如,聚氨酯丙烯酸酯)在这种涂层中是可用的,由于它们的对模压的抵抗力。许多保护外涂层具有有限的释放性质,然而,但是可能往往会粘到光致抗蚀剂的表面,特别是当例如高粘度阻焊层油墨的相对粘的材料存在时。结果,在从光致抗蚀剂移除期间能够损伤它们。
发明内容
在一个方面,本发明提供了一种可固化组合物,包括:
由下面的化学式表示的环氧硅烷:
X-Si(OR1)(OR2)(OR3)
其中,R1、R2以及R3独立地表示具有1至4个碳原子的烷基,并且X表示具有至少一个环氧环的有机基;
由下面的化学式表示的氟化硅烷:
其中:
Rf表示具有3至5个碳原子的全氟烷基;
R4表示H或具有1至4个碳原子的烷基;
R5、R6以及R7独立地表示具有1至4个碳原子的烷基;以及
Z表示二价有机连接基团;以及
光酸。
在另一方面,本发明提供了涂覆底片的方法,该方法包括将可固化组合物涂覆到底片的至少一部分上并且使该可固化组合物固化,其中该可固化组合物包含:
由下面的化学式表示的环氧硅烷:
X-Si(OR1)(OR2)(OR3)
其中,R1、R2以及R3独立地表示具有1至4个碳原子的烷基,并且X表示具有至少一个环氧环的有机基;
由下面的化学式表示的氟化硅烷:
其中:
Rf表示具有3至5个碳原子的全氟烷基;
R4表示H或具有1至4个碳原子的烷基;
R5、R6以及R7独立地表示具有1至4个碳原子的烷基;以及
Z表示二价有机连接基团;以及
光酸。
在又一方面,本发明提供了包括底片的被涂覆的底片,所述底片具有设置在其主表面的至少一部分上的保护涂层;其中,该保护涂层包括可固化组合物的反应产物,所述可固化组合物包含:
由下面的化学式表示的环氧硅烷:
X-Si(OR1)(OR2)(OR3)
其中,R1、R2以及R3独立地表示具有1至4个碳原子的烷基,并且X表示具有至少一个环氧环的有机基;
由下面的化学式表示的氟化硅烷:
其中:
Rf表示具有3至5个碳原子的全氟烷基;
R4表示H或具有1至4个碳原子的烷基;
R5、R6以及R7独立地表示具有1至4个碳原子的烷基;以及
Z表示二价有机连接基团;以及
光酸。
在一些实施例中,环氧硅烷由选自如下的式表示:
和
其中R1、R2以及R3独立地表示具有1至4个碳原子的烷基,并且Q表示无干扰基的二价有机连接基团。在一些实施例中,环氧硅烷选自包括β-(3,4-环氧环己基)乙基三甲氧基硅烷和γ-环氧丙氧基丙基三甲氧基硅烷的组。
在一些实施例中,Rf为全氟丁基。在一些实施例中,R4为甲基。
在一些实施例中,可固化组合物包含基于可固化组合物的总重量计的少于5重量%的挥发性有机溶剂。
有利地,根据本发明的可固化组合物能够被用来在底片表面上提供保护涂层(特别是在图像层上),所述保护涂层提供模压和污垢抵抗力并且通过粘附到发粘材料例如某些光致抗蚀剂来抵抗移除。
如本文使用的:
术语“光酸”指的是如果暴露于光(通常紫外和/或可见光)就生成强效路易斯酸(如,强效的足以使环氧树脂固化)的化合物;并且
术语“环氧环”是常规的并且指的是具有两个四配位碳原子和一个氧原子的三元环。
具体实施方式
根据本发明的可固化组合物总体上包括一个或多个环氧硅烷化合物、一个或多个氟化硅烷、以及一个或多个光酸。组合物另外可以包含溶剂;然而,通常在基本上不存在溶剂时最有利地实现本发明。
可用的环氧硅烷由下面的化学式表示:
X-Si(OR1)(OR2)(OR3)。
R1、R2以及R3独立地表示具有1至4个碳原子的烷基。例如,R1、R2以及R3可以独立地表示甲基、乙基、丙基、或丁基基团。
X表示有机基,其是单价的并且具有至少一个环氧环。
在一些实施例中,环氧硅烷由选自如下的式表示:
和
其中R1、R2以及R3如此前所定义的并且Q表示无干扰基的二价有机连接基团。在通过N、S或O原子、磺酰基、硝基基团、卤素、羰基、或它们的组合取代或不取代至少一个碳原子的情况下,Q的实例包括直链的、环状的、和/或支链的亚烷基、亚芳基、以及它们的组合。环氧硅烷化合物可以是单体、低聚的,或在一些情况下甚至是聚合物的,前提条件是它们具有可聚合的环氧基以及可聚合的三烷氧基甲硅烷基。
通常,可固化环氧硅烷化合物是具有端部的可聚合的环氧基和端部的可聚合的硅烷基的环氧-封端的硅烷化合物,这些基的跨接为如上文所描述的。
可用的环氧硅烷的实例包括:环氧丙氧基甲基三甲氧基硅烷、环氧丙氧基甲基三乙氧基硅烷、环氧丙氧基甲基三丙氧基硅烷、环氧丙氧基甲基三丁氧基硅烷、β-环氧丙氧基乙基三甲氧基硅烷、
β-环氧丙氧基乙基三乙氧基硅烷、β-环氧丙氧基乙基三丙氧基硅烷、
β-环氧丙氧基乙基三丁氧基硅烷、β-环氧丙氧基乙基三甲氧基硅烷、
α-环氧丙氧基乙基三乙氧基硅烷、α-环氧丙氧基乙基三丙氧基硅烷、
α-环氧丙氧基乙基三丁氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、
γ-环氧丙氧基丙基三乙氧基硅烷、γ-环氧丙氧基丙基三丙氧基硅烷、γ-环氧丙氧基丙基三丁氧基硅烷、β-环氧丙氧基丙基三甲氧基硅烷、
β-环氧丙氧基丙基三乙氧基硅烷、β-环氧丙氧基丙基三丙氧基硅烷、
β-环氧丙氧基丙基三丁氧基硅烷、α-环氧丙氧基丙基三甲氧基硅烷、
α-环氧丙氧基丙基三乙氧基硅烷、α-环氧丙氧基丙基三丙氧基硅烷、
α-环氧丙氧基丙基三丁氧基硅烷、γ-环氧丙氧基丁基三甲氧基硅烷、
δ-环氧丙氧基丁基三乙氧基硅烷、δ-环氧丙氧基丁基三丙氧基硅烷、
δ-环氧丙氧基丁基三丁氧基硅烷、δ-环氧丙氧基丁基三甲氧基硅烷、
γ-环氧丙氧基丁基三乙氧基硅烷、γ-环氧丙氧基丁基三丙氧基硅烷、
γ-环氧丙氧基丁基三丁氧基硅烷、δ-环氧丙氧基丁基三甲氧基硅烷、
δ-环氧丙氧基丁基三乙氧基硅烷、δ-环氧丙氧基丁基三丙氧基硅烷、
α-环氧丙氧基丁基三甲氧基硅烷、α-环氧丙氧基丁基三乙氧基硅烷、
α-环氧丙氧基丁基三丙氧基硅烷、α-环氧丙氧基丁基三丁氧基硅烷、
(3,4-环氧环己基)甲基三甲氧基硅烷、(3,4-环氧环己基)甲基-三乙氧基硅烷、(3,4-环氧环己基)甲基三丙氧基硅烷、(3,4-环氧环己基)-甲基三丁氧基硅烷、(3,4-环氧环己基)乙基三甲氧基硅烷、
(3,4-环氧环己基)乙基三乙氧基硅烷、(3,4-环氧环己基)乙基三丙氧基硅烷、(3,4-环氧环己基)乙基三丁氧基硅烷、(3,4-环氧环己基)丙基三甲氧基硅烷、(3,4-环氧环己基)丙基三乙氧基硅烷、
(3,4-环氧环己基)丙基三丙氧基硅烷、
(3,4-环氧环己基)丙基三丁氧基硅烷、(3,4-环氧环己基)丁基-三甲氧基硅烷、(3,4-环氧环己基)丁基三乙氧基硅烷、(3,4-环氧环己基)-丁基三丙氧基硅烷、以及(3,4-环氧环己基)丁基三丁氧基硅烷。
例如,在本发明的实施过程中可用的额外的环氧硅烷的实例在美国专利No.4,049,861(Nozari);No.4,100,134(Robins等人);以及No.4,293,606(Zollinger等人)中有所描述。
环氧硅烷通常包含基于可固化组合物的总重量计的至少50、60、70、80、或90重量%的可固化组合物,然而也可以另外使用其他的量。更典型地,他们包含基于可固化组合物的总重量计的约80重量%至约98重量%的可固化组合物。
通常,环氧硅烷基本上不含干扰阳离子环氧聚合化反应的基团(即,干扰基团),然而这不是必要条件。如将由本领域的普通技术人员所了解的,干扰基团的实例可以包括碱性基团,例如包含1°、2°、和/或3°胺和/或膦、以及羟基(除结合到硅的之外)的基团;
可用的氟化硅烷由下面的化学式表示:
Rf表示具有3至5个碳原子的全氟烷基基团。实例包括全氟丙基、全氟丁基以及全氟戊基。
R4表示H或具有1至4个碳原子的烷基。实例包括H、甲基、乙基、丙基以及丁基。
R5、R6以及R7独立地表示具有1至4个碳原子的烷基。实例包括甲基、乙基、丙基以及丁基。
Z表示二价有机连接基团。在通过N、S、或O原子、磺酰基、硝基、卤素、羰基、或它们的组合取代或不取代至少一个碳原子的情况下,Z的实例包括直链的、环状的、和/或支链亚烷基、亚芳基、以及它们的组合。
氟化硅烷可以包含基于可固化组合物的总重量计少于50、40、30、20、10、5、2、或甚至1重量%可固化组合物,然而也可以另外使用其他的量。通常,它们包含基于可固化组合物的总重量计少于15重量%可固化组合物。
当暴露于光化辐射(例如,UV或可见光)时,光酸形成阳离子引发剂。在本发明中使用的可固化组合物包含光酸以使可固化组合物阳离子聚合。可用的光酸的实例包括二芳基碘盐、三芳基硫盐、苯甲基硫盐、苯甲酰甲基硫盐、N-苯甲基吡啶盐、N-苯甲基吡嗪盐、N-苯甲基铵盐、鏻盐、肼盐以及硼酸铵盐。三芳基锍盐和二芳基碘盐是特别地可用的。当然盐的负抗衡离子(即,阴离子)的选择将影响其性能。通常,阴离子应该是基本上不干扰环氧基或烷氧基硅烷的阳离子聚合反应的阴离子。实例包括四氟硼酸盐、六氟磷酸盐、三(氟化芳磺酰基)甲基化物、以及六氟锑酸根。
因此,示例性可用的光酸包括:Va簇元素的盐,例如为三苯基苯甲酰甲基磷六氟磷酸盐;VIa簇元素的盐,例如为三苯基锍四氟硼酸盐、三苯基锍六氟磷酸盐以及三苯基锍六氟锑酸根;以及VIIa簇元素的盐,例如诸如二苯基碘氯化物和二芳基碘六氟锑酸根的碘盐。芳族盐及作为环氧化合物的聚合反应中的光酸的它们的使用在美国专利No.4,058,401(Crivello);No.4,069,055(Crivello);No.4,101,513(Fox等人)以及No.4,161,478(Crivello)中有详细的描述。
例如,市售的光酸包括例如以商品名CYRACURE UVI-6976(碳酸丙二酯中的三芳基锍六氟锑酸根盐的混合物)以及UVI-6992得自Dow Chemical Co(Midland,MI)的那些。
光酸通常以有效量在本发明的组合物中提供(即,当暴露于光化辐射时能有效地使可固化组合物固化的量)。光酸的量通常在基于可固化组合物的总重量计的1重量%至5重量%的范围内,然而也可以使用其他的量。
可固化组合物还可以包含一种或多种聚环氧化合物。聚环氧化合物可例如加速组合物的聚合。其也可用于调节固化组合物的柔软性或降低其脆性。可用的聚环氧化合物的实例包括二环氧化物,例如在美国专利No.4,293,606(Zollinger等人)中所公开的那些二环氧化物。如果存在,聚环氧化合物通常是脂环族二环氧化物化合物,例如3,4-环氧环己基甲基-3,4-环氧环己烷羧化物。
根据本发明的可固化组合物可以另外包括其他任选组分,例如为一个或多个可固化一-硅烷和/或二-硅烷(例如,以调整硬度)、钛酸盐、和/或锆酸盐;表面活性剂;消光剂;以及无机粒子。实例包括四甲氧基硅烷、四乙氧基硅烷、甲基三乙氧硅烷、二甲基二乙氧基硅烷、十八烷基三乙氧基硅烷、甲基三氯硅烷、四甲基原钛酸盐、四乙基原钛酸盐、四异丙基原钛酸盐、四乙基铅酸盐、四异丙基铅酸盐、以及四丙基铅酸盐。
在一些实施例中,然而,可固化组合物可以包含一种或多种溶剂,例如酮(例如,丙酮或甲基异丁基酮)、酯(例如,乙酸乙酯)或醚(例如,甲基叔-丁基醚或四氢呋喃)。通常,本发明的可固化组合物包含基于组合物的总重量计少于10%的溶剂,并且更通常少于5%。有利地,本发明的可固化组合物包含基于组合物的总重量计少于1%的溶剂,或是无溶剂的。
可以使用本领域内已知的涂层技术可轻易地将根据本发明的可固化组合物涂敷到底片,所述涂层技术例如为喷涂、浸涂、凹版印刷涂布、辊涂、刮涂、以及帘式淋涂。通常,施加可固化组合物以形成介于约0.5微米与约40微米之间的固化厚度,更通常约2微米与10微米之间的固化厚度,但是也可以使用其他的厚度。
根据本发明的可固化组合物可以通过暴露于光化辐射来进行固化,所述光化辐射例如为可见和/或紫外光,可任选地与热相结合。暴露条件的选择完全在本领域普通技术人员的能力范围之内。
通过以下非限制性实例进一步说明本发明的目的和优点,但这些实例中所述的具体材料及其用量,以及其他条件和细节不应视为对本发明进行不当限定。
实例
除非另外指明,否则在实例及本说明书的其余部分中的所有份数、百分数、比率等均为以重量计。
材料
除非另外指出,否则所有的溶剂均为获自商业来源的标准试剂等级,且无进一步纯化而进行使用。
A-186为β-(3,4-环氧环己基)乙基三甲氧基硅烷,可购自MomentiveAdvanced Materials(Albany,NY)。
A-187为γ-环氧丙氧基丙基三甲氧基硅烷,可购自MomentiveAdvanced Materials。
PAG-1为光酸,是在以商品名CYRACURE UVI-6974来自DowChemical Company(Midland,MI)的碳酸丙二酯中的50%三芳基锍六氟锑酸根溶液。
PAG-2为光酸,(C12H25Ph)2I(+)SbF6 (-),基本上使用在美国专利No.4,279,717(Eckberg等人)的实例4中描述的方法来制备。
TEOS为四乙基原硅酸酯,可得自Sigma-Aldrich Corporation(St.Louis,MO)。
EP-1为双-(3,4-环氧环己基甲基)己二酸,以ERL-4299得自DowChemical Company。
EP-2为3,4-环氧环己基甲基-3,4-环氧环己基羧化物,以ERL-4221得自Dow Chemical Company。
ES-1是A-187和PAG-1的以按重量计92∶8的比率的共混物。
ES-2是A-186和PAG-1的以按重量计92∶8的比率的共混物。
ES-3是A-187和PAG-2以按重量计97∶3的比率的共混物。
FA-1为CF3CF2CF2CF2S(=O)2N(CH3)CH2CH2CH2Si(OCH3)3。基本上通过美国专利No.5,274,159(Pellerite等人)的实例6的工序来制备,不同的是使用CF3CF2CF2CF2S(=O)2N(CH3)CH2CH=CH2而不是使用C8F17S(=O)2N(CH3)CH2CH=CH2)。
测试方法
接触角测试
将待评价的固化涂层在异丙醇(IPA)中用手振摇进行清洗1分钟,接着让IPA蒸发掉后测量水(H2O)和十六烷(HD)接触角(。在购自ASTProducts(Billerica,MA)视频接触角分析仪上(VCA-2500XE),直接使用试剂级十六烷(得自Aldrich Chemical Co.)和经过滤系统(可购自Millipore Corp.(Billerica,MA))过滤的去离子水执行测试。记录的值为至少三滴液滴测量值的平均值,在液滴的右侧和左侧进行测量。液滴体积对于静态接触角测量为5微升,对于前进和后退接触角测量为1-3微升。
标记排斥性测试
使用来自Sanford(Bellwood,IL)的黑Sharpie标记在待评价的整个固化涂层的表面画线条。对样品进行了针对其外观和排斥Sharpie标记黑油墨的能力的评定。“是”等级意指至少存在对标记的一些排斥性,如通过标记油墨的珠缘确定的,而“否”等级意指没有观察到排斥性。
耐溶剂性测试
选择的有机溶剂的一滴滴剂(~1.25cm直径)被放置在待评价的固化涂层上。允许溶剂在室温下蒸发并且在视觉上评定和记录在样品的外观方面的改变。等级“C”意指透光的表面(即,涂层没有改变)。
钢丝棉耐久性测试
通过使用能够在膜的表面上振荡(使用橡胶垫圈)固定在触笔上的钢丝棉的机械设备,在涂层方向的幅材横向上测定待评价的固化涂层的钢丝棉耐磨性。触笔以超过10cm宽的扫描宽度、3.5次擦拭/秒的速率振荡,其中“1次擦拭”定义为单程通过10cm。触笔具有直径为3.8mm、具有200g负载的平坦、圆柱形几何形状。设备装备有平台,其上放置重量以增加触笔垂直施加至膜表面的力。钢丝棉可以商品名“#0000-超细(#0000-SUPER-FINE)”购自Rhodes-American(HomaxProducts的一个部门)(Bellingham,WA),并可直接使用。对每个实例的单个样品进行测定,记录施加到触笔的重量(以克计)和测试过程中使用的擦拭次数50。在该测试之后,对样品进行针对刮伤的存在的检查,并且如上文所描述对水和十六烷接触角进行测量以确定涂层的耐久性。
清洁薄纸耐久性测试
待评价的固化涂层的耐久性以与钢丝棉耐久性测试类似的方式来进行测量,不同的是来自Bausch Lomb Inc.(Rochester,NY)的预润湿的视觉救助者(Sight Savers)透镜清洁薄纸&被用于耐久性测试,并且通过手而不是使用触笔来对涂层进行擦试。在通过手施加适度压力对固化膜的表面进行擦试20次之后,在视觉上检查表面的外观。等级“C”意指涂层保持透光的并且没有观察到损坏。
硬度测试
待评价的固化涂层的硬度使用来自Paul N.Gardner Co.,Inc.(Pompano Beach,FL)的Gardo/Wilff铅笔划痕硬度测定仪(Gardo/WilffWilborn Pencil Scratch Hardness Tester)来进行测量。针对该测试,使用不同硬度(例如,4H,5H,6H等)的铅笔将涂层刮伤。涂层能够继续存在而没有遭受损坏的最高硬度被指定为涂层的硬度。
实例1-9和比较例A-C
实例1-9通过以如表1中记录的预定的用量(以紧接组分的括号中指示的重量)来混合所需的环氧-硅烷和短尾含氟化合物添加剂来制备。比较例A-C根据如表1中指示的各种环氧-硅烷而没有任何含氟化合物添加剂来制备。用于实例1-9和比较例A-C的所有样品都是均匀的和澄清的溶液,指示出环氧-硅烷和含氟化合物添加剂是相容的。所得溶液然后被使用来自RD Specialties(Webster,NY)的No.6缠线棒涂覆在待发的聚对苯二甲酸乙二醇酯(PET)基底上,并且然后在空气中在可购自Atlanta Light Bulbs,Inc.(Tucker,GA)的两个Sylvania GermicidalG15T8(15W)灯泡下2分钟进行固化。对实例1-9和比较例A-C的涂层进行了针对其标记排斥性、水以及十六烷接触角的测试。结果记录在下表1中。
实例10-13
实例10-13以与实例1-9相同的方式来制备,不同的是涂层在如表2上所指示的玻璃或聚碳酸酯(PC)基底上制备。对涂层进行了针对其水和十六烷接触角的测试。结果记录在下表2中。
实例14-16
运行实例14-16来对具有不同固化条件和后续的老化时间的玻璃或聚对苯二甲酸乙二醇酯基底的由根据本发明包含95份数ES-1和5份数FA-1的组合物制备的涂层的硬度性质进行评价。实例14和16通过使样本暴露于可购自Atlanta Light Bulbs,Inc.(Tucker,GA)的Sylvania Germicidal G15T8(15W)灯泡下2分钟来进行固化。实例15通过使涂层暴露于配备有来自Gaithersburg,MD的H-灯泡的Light-Hammer 6UV处理器,在以3米/分钟的速度移动的传送带线路上的在100%灯功率的氮气环境下操作来进行固化。固化的样品被老化所需的时间段并且使用上文所描述的用于测量硬度的测试方法来进行测量所得涂层的硬度。基底、老化时间以及所得涂层的硬度记录在下面的表3中。
表3
实例17至22
实例17-22被运行以说明在玻璃基底上添加交联剂对由根据本发明的组合物制备的涂层的硬度的影响。通过以预定的用量(按紧挨着组分的括号中指示的重量)混合所需的环氧硅烷、含氟化合物添加剂以及交联剂来制备若干组合物。然后,溶液被涂覆在玻璃基底上并且通过在空气中使所述溶液暴露于可购自Atlanta Light Bulbs,Inc.(Tucker,GA)的Sylvania Germicidal G15T8(15W)灯泡下2分钟来进行固化。固化的样品被老化所需的时间段(在室温RT下24小时,或在100℃下10分钟),并且使用上文描述的用于测量硬度的测试方法来测量所得的涂层的硬度。表4记录了涂层的组分,包括使用的交联剂以及涂层质量和固化后立刻测得的涂层的硬度、在室温下的24小时以后的硬度以及在100℃下10分钟以后的硬度的定性估计。
使用上文描述的方法分别确定如上文中在实例中所述制备的若干涂层的清洁薄纸耐久性和耐溶剂性。涂层对多种有机溶剂的耐溶剂性被确定,所述多种有机溶剂包括乙酸乙酯(EtOAc,可购自J.T.Baker(Philipsburg,NJ))、异丙基醇(IPA,可购自VWR International(WestChester,PA))、N,N-二甲基甲酰胺(DMF,可购自Aldrich ChemicalCompany(Milwaukee,WI)),丙酮、甲苯、甲乙酮(MEK),全部可购自EMD Chemicals,Inc.(Gibbstown,NJ)。表5(在下面)记录了根据上文所描述的实例而制备的若干涂层的清洁薄纸耐久性和耐溶剂性。
使用上文描述的方法来确定如在上文中的实例中描述的制备的若干涂层的钢丝棉耐久性。表6(在下面)记录测试结果。
本文所提到的所有专利和公开在此全文以引用方式并入本文。除非另外指明,否则本文给出的所有实例均被认为是非限制性的。在不脱离本发明的范围和精神实质的条件下,本领域技术人员可对本发明进行各种修改和变更,并且应当理解,本发明不应当不当地受限于本文中所述的示例性实施例。
Claims (21)
3.根据权利要求1所述的可固化组合物,其中,所述可固化组合物包含基于所述可固化组合物的总重量计的少于5重量%的挥发性有机溶剂。
4.根据权利要求1所述的可固化组合物,其中,所述Rf为全氟丁基。
5.根据权利要求4所述的可固化组合物,其中,所述R4为甲基。
6.根据权利要求1所述的可固化组合物,其中,所述环氧硅烷选自β-(3,4-环氧环己基)乙基三甲氧基硅烷和γ-环氧丙氧基丙基三甲氧基硅烷。
10.根据权利要求8所述的方法,其中,所述可固化组合物包含基于所述可固化组合物的总重量计的少于5重量%的挥发性有机溶剂。
11.根据权利要求8所述的可固化组合物,其中,所述Rf为全氟丁基。
12.根据权利要求11所述的可固化组合物,其中,所述R4为甲基。
13.根据权利要求8所述的方法,其中,所述环氧硅烷选自β-(3,4-环氧环己基)乙基三甲氧基硅烷和γ-环氧丙氧基丙基三甲氧基硅烷。
17.根据权利要求16所述的被涂覆的底片,其中,所述可固化组合物包含基于所述可固化组合物的总重量计的少于5重量%的挥发性有机溶剂。
18.根据权利要求16所述的可固化组合物,其中,所述Rf为全氟丁基。
19.根据权利要求18所述的可固化组合物,其中,所述R4为甲基。
20.根据权利要求15所述的被涂覆的底片,其中,所述环氧硅烷选自β-(3,4-环氧环己基)乙基三甲氧基硅烷和γ-环氧丙氧基丙基三甲氧基硅烷。
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US61/227,228 | 2009-07-21 | ||
PCT/US2010/040349 WO2011011167A2 (en) | 2009-07-21 | 2010-06-29 | Curable composition, method of coating a phototool, and coated phototool |
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- 2010-06-29 JP JP2012521657A patent/JP5583210B2/ja not_active Expired - Fee Related
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CN105026446A (zh) * | 2012-11-13 | 2015-11-04 | 3M创新有限公司 | 可固化的防污组合物、使用方法以及制品 |
US10947396B2 (en) | 2012-11-13 | 2021-03-16 | 3M Innovative Properties Company | Curable antifouling composition, method of use, and articles |
CN105324407A (zh) * | 2013-06-21 | 2016-02-10 | 株式会社钟化 | 活性能量线固化性组合物 |
CN105324407B (zh) * | 2013-06-21 | 2017-07-28 | 株式会社钟化 | 活性能量线固化性组合物 |
US10227505B2 (en) | 2013-06-21 | 2019-03-12 | Kaneka Corporation | Active energy ray-curable composition |
US10563088B2 (en) | 2014-12-16 | 2020-02-18 | Kaneka Corporation | Photocurable and thermosetting resin composition, cured product, and laminate |
CN108541142A (zh) * | 2018-06-01 | 2018-09-14 | 河源诚展科技有限公司 | 一种pcb内层线路图形转移工艺 |
CN108541142B (zh) * | 2018-06-01 | 2021-07-20 | 河源诚展科技有限公司 | 一种pcb内层线路图形转移工艺 |
Also Published As
Publication number | Publication date |
---|---|
WO2011011167A2 (en) | 2011-01-27 |
JP5583210B2 (ja) | 2014-09-03 |
JP2012533675A (ja) | 2012-12-27 |
WO2011011167A3 (en) | 2011-04-21 |
US9096712B2 (en) | 2015-08-04 |
US20120107732A1 (en) | 2012-05-03 |
EP2456823A2 (en) | 2012-05-30 |
CN102597116B (zh) | 2013-12-11 |
EP2456823A4 (en) | 2012-12-26 |
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