CN101010290A - 二亚铵化合物及其用途 - Google Patents
二亚铵化合物及其用途 Download PDFInfo
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- CN101010290A CN101010290A CNA2005800297642A CN200580029764A CN101010290A CN 101010290 A CN101010290 A CN 101010290A CN A2005800297642 A CNA2005800297642 A CN A2005800297642A CN 200580029764 A CN200580029764 A CN 200580029764A CN 101010290 A CN101010290 A CN 101010290A
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- Prior art keywords
- compound
- diimmonium compound
- near infrared
- infrared light
- diimmonium
- Prior art date
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Classifications
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Abstract
公开一种不含锑和砷的近红外光吸收化合物,这种化合物具有优良的稳定性,特别是耐热性、耐光性和耐湿热性。还公开一种近红外光吸收滤光片,该滤光片可以用上述近红外光吸收化合物制备,其诸如耐光性和耐热性的性能优良,还公开滤光器和光记录介质。具体公开了具有下式(1)表示的二亚铵化合物和用该二亚铵化合物制得的红外光吸收滤光片。具体揭示了近红外光吸收滤光片在其透明支承体上具有含该二亚铵化合物的粘合剂层,以及使用这种近红外光吸收滤光片的滤光器。下式(1)中,R1至R8独立地表示氢原子或任选取代的脂族烃残基;R9至R11独立地表示可具有卤原子的脂族烃残基;环A和环B还可以具有取代基。
Description
技术领域
本发明涉及一种在近红外区有吸收的化合物及其用途。本发明特别涉及无毒并且耐热性、耐光性和溶解性优良的二亚铵化合物,使用该二亚铵化合物的近红外光吸收滤光片,以及使用该二亚铵化合物的滤光器和光信息记录介质。
背景技术
二亚铵化合物作为近红外(近-IR)射线吸收材料一直广为人知(如参见专利文献1至3)并被广泛应用于近红外光吸收滤光片,隔热膜,太阳镜等。然而,这些化合物中,包含六氟锑酸根离子和六氟砷酸根离子等作为抗衡离子的那些化合物因为相对优良的耐热性而一直被使用,这些化合物中主要使用包含六氟锑酸根离子作为抗衡离子的那些化合物。但是,在重金属的使用受到管制的工业领域,尤其是电气材料领域,希望研制不含这类金属的化合物,因为含锑化合物被分类为是毒性物质。作为解决上述问题的方法,有使用高氯酸根离子、六氟磷酸根离子和硼氟酸根离子作为抗衡离子的方法,但是从耐热性以及耐湿热性方面,这些抗衡离子都不充分。此外,还提出含有机抗衡离子如萘二磺酸的化合物(如参见专利文献2),但是这种化合物的摩尔吸收系数低且化合物本身呈淡绿色,因此,其实际使用的领域很有限。此外,已知有包含三氟甲磺酸根离子、二(三氟甲烷)磺酸亚胺等的化合物(如参见专利文献1、4和5),但是据说这些化合物不具有足够的耐热性和耐湿热性,因此需要开发更优良的化合物。
此外,近红外光是用于远程操作电器和设备用的光束,因此发射近红外光的机器和设备可能引起在周边安装的电器和设备操作不当。因此,需要安装具有在这些机器和设备的前表面屏蔽近红外光的功能的滤光器。
这些电器和设备中,近年来,PDP(等离子体显示板)频繁用于大型电视。PDP按照以下原理产生图像所需的可见光:在密封于夹在两个扁平玻璃之间的单元内的稀有气体(如氖和氙)上施加电压,产生紫外光;使产生的紫外光辐照在所述单元壁表面上涂敷的发光体上。然而,PDP在发射可见光的同时还发射有害的电磁波如近红外光、对人体有害的电磁波以及橙色光束(下面称作氖光),橙色光束源自氖气并且能减少红光。因此,需要在PDP上装备滤光器,使有用的可见光通过该滤光片,但遮蔽包括近红外光的有害的电磁波。
用于滤光器中的近红外光吸收滤光片可以通过以下方法制造,使用聚合物树脂作为粘合剂,在透明支承体的表面或者功能薄膜的表面上涂布吸收近红外光的化合物(近红外光吸收化合物),所述功能薄膜例如是用来遮蔽对人体有害的电磁波的薄膜(下面称作遮蔽电磁波的薄膜)。有许多吸收近红外光的化合物可应用于该领域,但经常使用二亚铵化合物或二亚铵化合物与另一种吸收近红外光的化合物的组合,因为二亚铵化合物对近红外光具有宽的吸收波长范围。
然而,当使用树脂作为粘结剂将二亚铵化合物涂布在树脂膜上来制备近红外吸收滤光片时,普通的二亚铵化合物不仅具有上述有害性的缺点,而且还存在如已指出的耐热和耐湿热稳定性不足的问题。
专利文献6公开了稳定二亚铵化合物的技术,即制造含二亚铵化合物的聚合物树脂层,同时控制树脂层中残留的溶剂量至特定比例或更小。但是,这种技术需要一定的操作来控制残留溶剂量,因此需要研制在采用更常规的涂敷方法和干燥方法进行涂敷时具有高的耐热性和耐湿热性的二亚铵化合物。专利文献7公开一种具有近红外光吸收性的滤光片,该滤光片具有包含在透明聚合物树脂涂层中的二亚铵化合物,该化合物具有二(氟烷基磺酰基)酰亚胺阴离子或三(氟烷基磺酰基)负碳离子,该专利文献指出这类二亚铵化合物,特别是具有二(氟烷基磺酰基)酰亚胺阴离子的二亚铵化合物,特定例子的这类化合物具有良好的耐热性和耐湿热性。但是,该专利文献并没有描述具体化合物的名称、具体的制备方法、具有三(氟烷基磺酰基)负碳离子的二亚铵化合物的物理性质或应用实例。此外,作为制备包含在树脂膜中的近红外光吸收化合物的方法,有制备包含在粘性层中近红外光吸收化合物的方法,该粘性层用于将聚合物树脂膜与支承体粘性结合。这种方法可以制备包含在功能膜(如组成滤光片的抗反射膜和电磁波屏蔽膜)的粘性层中的近红外光吸收化合物,因此与需要另外形成含近红外光吸收化合物层的方法相比,由于取消了一个涂敷步骤而具有降低成本的优势。但是,这种方法因为比制备包含在聚合物树脂膜或涂层中的近红外光吸收化合物方法在耐热性和耐湿热性方面的问题更加严重而被认为在技术方面存在较大的障碍。
专利文献1:日本专利公报(KOKOKU)No.07-51555(第2页)
专利文献2:日本专利公开公报(KOKAI)No.10-316633(第5页)
专利文献3:日本专利公报(KOKOKU)No.43-25335(第7-14页)
专利文献4:国际公开小册子WO2004/068199
专利文献5:国际公开小册子WO2004/048480
专利文献6:日本专利公开公报(KOKAI)No.2000-227515
专利文献7:日本专利公开公报(KOKAI)No.2005-49848(第2-12页)
发明内容
本发明解决的问题
在上述情况下,完成了本发明,本发明的一个目的是提供一种不含如锑的重金属的近红外光吸收化合物,这种化合物具有优良的稳定性,尤其是耐热性、耐光性和耐湿-耐热性;提供近红外光吸收滤光片(特别用于等离子体显示板);和耐大气腐蚀性优良的光记录介质和树脂组合物。本发明的另一个目的是提供使用本发明的二亚铵化合物的近红外光吸收滤光片的特别优选的实施方式。
解决上述问题的手段
本发明人为解决上述问题进行了深入的研究,结果发现,一种具有特定结构的二亚铵化合物能解决上述各种问题,因而完成了本发明。具体地,本发明涉及:
(1)一种由下式(1)表示的二亚铵化合物:
式中,R1至R8各自独立地表示氢原子或脂族烃残基,所述脂族烃残基可以具有取代基,R9至R11各自独立地表示可以有一个卤原子的脂族烃残基,环(A)和(B)还可以独立地具有取代基;
(2)按照(1)所述的二亚铵化合物,式(1)所示的二亚铵化合物是由下式(2)表示的化合物:
式中,R1至R8和R9至R11具有与对式(1)所述的相同的含义;
(3)按照(1)或(2)所述的二亚铵化合物,式(1)中的R9至R11都是含有氟原子的脂族烃残基;
(4)按照(3)所述的二亚铵化合物,所述含有氟原子的脂族烃残基是三氟甲基;
(5)按照(1)至(4)中任一项所述的二亚铵化合物,式(1)中R1至R8都是直链或支链烷基;
(6)按照(5)所述的二亚铵化合物,所述直链或支链烷基是C1-C6直链或支链烷基;
(7)按照(6)所述的二亚铵化合物,所述直链或支链烷基是C2-C5直链或支链烷基;
(8)按照(7)所述的二亚铵化合物,所述直链或支链烷基是乙基、正丙基、正丁基、异丁基或正戊基;
(9)按照(1)至(4)中任一项所述的二亚铵化合物,式(1)或式(2)中R1至R8所表示的可以具有一取代基的脂族烃残基中的取代基各自独立地是卤原子、氰基、硝基、羟基、羧基、碳酰胺基、烷氧基羰基、酰基、芳基或烷氧基;
(10)按照(9)所述的二亚铵化合物,R1至R8都是被氰基取代的烷基;
(11)按照(10)所述的二亚铵化合物,被氰基取代的烷基是氰基丙基;
(12)一种树脂组合物,其特征是包含(1)至(11)中任一项所述的二亚铵化合物和树脂;
(13)近红外光吸收滤光片,其特征是具有一层包含(1)至(11)中任一项所述的二亚铵化合物的层;
(14)按照(13)所述的近红外光吸收滤光片,所述包含二亚铵化合物的层是粘性层;
(15)按照(14)所述的近红外光吸收滤光片,所述粘性层包含防锈剂;
(16)按照(15)所述的近红外光吸收滤光片,所述防锈剂是1H-苯并三唑;
(17)按照(14)至(16)中任一项所述的近红外光吸收滤光片,所述粘性层中有机酸的含量相对于粘性层质量为小于或等于0.5质量%;
(18)按照(14)至(17)中任一项所述的近红外光吸收滤光片,所述粘性层包含在550-620nm波长有最大吸收的化合物以及式(1)的二亚铵化合物;
(19)一种用于等离子体显示板的滤光片,其特征是包含(13)至(18)中任一项所述的近红外光吸收滤光片和电磁波遮蔽层;
(20)等离子体显示板,具有按照(19)所述的等离子体显示板的滤光片;
(21)光信息记录介质,其特征是包含一层含按照(1)至(11)中任一项所述的二亚铵化合物的记录层。
发明效果
本发明具有近红外光吸收性质的二亚铵化合物是一种不包含锑和砷的化合物,该化合物是无毒物质并具有大于或等于100,000的摩尔吸收度,且耐热性、耐光性优良,具有高溶解性。与含六氟磷酸根离子、高氯酸根离子或氟硼酸根离子的常规二亚铵化合物相比,本发明的二亚铵化合物具有特别优良的耐热性和耐湿热性。本发明的二亚铵化合物因为具有这些特性而被优选用作在如近红外光吸收滤光片、隔热膜和太阳镜中的吸收近红外光的材料,并且特别优选用于等离子体显示器的近红外光吸收的滤光片。
本发明的使用二亚铵化合物的近红外光吸收滤光片能充分吸收在700-1,100nm波长范围内的近红外光。特别是,当二亚铵化合物包含于负载在透明支承体上的粘性层中时,近红外光吸收滤光片显示优良的耐热性和耐湿热性,并且不会引起近红外光吸收度下降,该层不会变色并且表面质量不会变差。因此,将这种近红外光吸收滤光片与另一种功能膜结合的滤光器用于PDP时,显示优良的性能,并充分解决了上述问题。
此外,本发明的光信息记录介质与含普通二亚铵化合物的光信息记录介质相比,明显提高了耐光性。此外,本发明的二亚铵化合物在制备光信息记录介质时具有足够的溶解性,并且具有优良的可加工性。此外,若将本发明的二亚铵化合物制成为包含在例如有机着色物的薄膜中,所述有机着色物的薄膜是光信息记录介质的记录层,形成的光信息记录介质在再记录操作中显示明显提高的耐久性和耐光稳定性。
具体实施方式
本发明的二亚铵化合物是由一个特定二亚铵阳离子和两个作为抗衡离子的特定阴离子组成的盐,可以由以下式(1)表示:
式(1)中,R9至R11各自独立地表示可以具有卤原子的脂族烃残基。所述脂族烃残基包括优选有1-36个碳原子的饱和和不饱和的、直链、支链和环烷基,更优选是含1-20个碳原子的可具有取代基的饱和直链烷基,最优选是具有1-4个碳原子的上述烷基。卤原子优选是氟、氯、溴或碘原子,更优选是氟、氯或溴原子,最优选是氟原子。所述基团的具体例子包括:饱和直链烷基,如甲基、三氟甲基、二氟甲基、单氟甲基、二氯甲基、单氯甲基、二溴甲基、二氟氯甲基、乙基、五氟乙基、四氟乙基、三氟乙基、三氟氯乙基、二氟乙基、单氟乙基、三氟碘乙基、丙基、七氟丙基、六氟丙基、五氟丙基、四氟丙基、三氟丙基、二氟丙基、单氟丙基、全氟丁基、全氟己基、全氟辛基和全氟辛基乙基;不饱和烷基,如烯丙基、四氟烯丙基、三氟乙烯基和全氟丁基乙烯基;支链烷基,如异丙基、五氟异丙基、七氟异丙基、全氟-3-甲基丁基和全氟-3-甲基己基;环烷基,如环己基。在式(1)中,R9至R11优选都是相同的。此外,R9和R10、R9和R11或者R10和R11都可以连接形成环烷基。
特别优选的是R9至R11都是具有氟原子的脂族烃残基。该残基的具体例子包括:三氟甲基、二氟甲基、单氟甲基、五氟乙基、四氟乙基、三氟乙基、二氟乙基、七氟丙基、六氟丙基、五氟丙基、四氟丙基、三氟丙基和全氟丁基,优选是三氟甲基、二氟甲基、五氟乙基、三氟乙基、七氟丙基、四氟丙基和全氟丁基;更优选三氟甲基。在上述各基团中,除非另外指出,烷基部分是直链的。
式(1)中,环(A)和(B)可以在除了1-位和4-位外的位置分别具有1-4个取代基。可以连接的取代基包括,例如卤原子、羟基、低级烷氧基、氰基和低级烷基。卤原子包括,例如,氟原子、氯原子、溴原子和碘原子。低级烷氧基包括,例如,C1-C5烷氧基,如甲氧基和乙氧基,低级烷基包括,例如,C1-C5烷基,如甲基和乙基。优选是在式(1)中,任何一个环(A)和环(B)在除了1-位和4-位外的位置没有取代基,或者环(A)和环(B)两者均被卤原子(具体是氯原子、溴原子和氟原子)、甲基或氰基取代。
当环(B)具有取代基时,四个环(B)优选都具有相同的取代基,此外,取代基优选连接在相对于和环(A)相连的氮原子的间位。
R1至R8各自独立地表示氢原子或者可有取代基的脂族烃残基。脂族烃残基指从饱和或不饱和的直链、支链或环状脂族烃基去除一个氢原子形成的基团。碳原子数为1-36,优选1-20。
不含取代基的饱和脂族烃残基或不饱和脂族烃残基的具体例子包括:甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、辛基、癸基、十二烷基、十八烷基、异丙基、环戊基、环己基、乙烯基、烯丙基、丙烯基、戊炔基、丁烯基、己烯基、己二烯基、异丙烯基、异己烯基、环己烯基、环戊二烯基、乙炔基、丙炔基、己炔基、异己炔基和环己炔基。这些残基中,优选的残基包括:C1-C5饱和脂族直链或支链烃残基或者不饱和脂族烃残基,如甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、叔戊基、乙烯基、烯丙基、丙烯基和戊炔基。
本发明中,R1至R8都优选是直链或者支链烷基,更优选(C2-C5)直链或支链烷基。特别优选的直链或支链烷基的具体例子包括:乙基、正丙基、正丁基、异丁基和正戊基。
含有取代基的脂族烃残基中的取代基的例子包括,例如卤原子(如F、Cl和Br)、羟基、烷氧基(如甲氧基、乙氧基和异丁氧基)、烷氧基烷氧基(如甲氧基乙氧基)、芳基(如苯基和萘基;芳基还具有取代基)、芳氧基(如苯氧基)、酰氧基(如乙酰氧基、丁酰氧基、己酰氧基和苯甲酰氧基;芳氧基还可含有取代基)、氨基、烷基取代的氨基(如甲基氨基和二甲基氨基)、氰基、硝基、羧基、碳酰胺基、烷氧基羰基(如甲氧基羰基和乙氧基羰基)、酰基、酰胺基(如乙酰胺基)、磺酰胺基(如甲烷磺酰胺基)和磺基。这些取代基中,优选的取代基是卤原子、氰基、硝基、羟基、羧基、碳酰胺基、烷氧基羰基、酰基、芳基或烷氧基。
具有取代基的脂族烃残基的具体例子包括:氰基取代的(C1-C6)烷基,如氰基甲基、2-氰基乙基、3-氰基丙基、2-氰基丙基、4-氰基丁基、3-氰基丁基、2-氰基丁基、5-氰基戊基、4-氰基戊基、3-氰基戊基、2-氰基戊基和3,4-二氰基丁基;烷氧基取代的(C1-C6)烷基,如甲氧基乙基、乙氧基乙基、3-甲氧基丙基、3-乙氧基丙基、4-甲氧基丁基、4-乙氧基丁基、5-乙氧基戊基和5-甲氧基戊基;氟化(C1-C8)烷基,如三氟甲基、单氟甲基、五氟乙基、四氟乙基、三氟乙基、七氟丙基、全氟丁基、全氟丁基乙基、全氟己基、全氟己基乙基、全氟辛基和全氟辛基乙基。
具有取代基的脂族烃残基的优选例子包括被氰基取代的烷基。优选的二亚铵化合物的例子包括:其中的R1至R8都是被氰基取代的烷基的二亚铵化合物,其中的R1至R8中至少一个是被氰基取代的烷基的二亚铵化合物。在此,被氰基取代的烷基的具体例子包括氰基丙基。
在式(1)的二亚铵化合物中,R1至R8可以相互独立。例如,一个氨基可以被未取代的直链烷基和氰基取代的烷基所取代;可以被未取代的支链烷基和氰基取代的烷基所取代;或者可以被未取代的直链烷基和未取代的支链烷基所取代。
本发明的式(1)中所示的二亚铵化合物中,优选的化合物的例子包括下式(2)所示的化合物。
式(2)中,R1至R8和R9至R11具有与对上述式(1)所述内容相同的定义。
按照本发明式(1)所示的二亚铵化合物可以与例如专利文献3中所述方法一致的方法来制得。具体地,将对苯二胺与1-氯-4-硝基苯之间的Ullmann反应的产物还原,获得下式(3)表示的化合物:
式(3)中,环(A)和环(B)具有与对上述式(1)所述内容相同的定义。
然后,式(3)表示的化合物与对应于所需R1至R8的卤化化合物(例如,当R1至R8都是正C4H9时的正C4H9Br)在有机溶剂中,优选在水溶性极性溶剂如二甲基甲酰胺(DMF)、二甲基咪唑啉酮(DMI)和N-甲基吡咯烷酮(NMP)在30-160℃,优选在50-140℃反应,获得下式(4)表示的化合物,式(4)中,取代基R1至R8都相同。或者,在制备下式(4)表示的化合物(例如,下面将描述的化合物与化合物19的前体)但不包括式(4)表示的所有取代基R1至R8都相同的化合物时,首先通过使式(3)表示的化合物与预定摩尔数(例如对每1摩尔由式(3)表示的化合物用4摩尔)的一种试剂(n-C4H9Br)反应,在R1至R8中的四个基团中引入正丁基,然后使制得的化合物与所需摩尔量(例如,对每1摩尔式(4)化合物中的胺用4摩尔试剂)的引入其余取代基(异丁基)所需的试剂(异C4H9Br)反应,制备式(4)表示的化合物。或者,在制备除上述化合物外的其它任意化合物时可以采用类似于制备化合物19的方法。
然后,如上所述获得的式(4)所示的化合物进行氧化反应,方法是加入2当量的对应于下式(5)的氧化剂(如银盐),在有机溶剂,优选在水溶性极性溶剂如DMF、DMI和NMP中,于0-100℃,优选5-70℃进行氧化反应,获得式(1)表示的二亚铵化合物。或者,如上所述获得的式(4)所示的化合物用氧化剂如硝酸银、高氯酸银和氯化铜进行氧化,然后在该反应溶液中加入具有式(5)所示的阴离子的酸或盐进行盐交换,获得式(1)表示的二亚铵化合物。或者,在如上所述获得的式(4)所示的化合物中加入具有式(5)所示的阴离子的酸或碱金属盐,然后,在上述的产物中加入无机酸如上述硝酸银和高氯酸银的氧化剂,进行氧化反应,获得式(1)表示的二亚铵化合物。
本发明由式(1)表示的二亚铵化合物的具体例子示于下面表1。表1中关于R1至R8的列中,n-是“正”的缩写,指直链,i-是“异”的缩写,指支链,cy指“环”。关于环(A)和环(B)的列中,在除了1-位和4-位外的位置未被取代的情况用“4H”表示,被取代的位置是相对于连接在环(A)上的氮原子的位置。此外,在关于R1至R8列中,当R1至R8都是正丁基时,该式缩写为“4(n-C4H9,n-C4H9)”,例如当一个是异戊基时其余是正丁基,换句话说,当取代基的四种组合中之一是异戊基,其余三个组合是正丁基时,该式缩写为“3(n-C4H9,n-C4H9),(n-C4H9,i-C5H11)”。此外,在关于R9至R11的列中,有3个或更多个碳原子的烷基部分都是由直链形成。
表1 二亚铵化合物的具体例子
本发明的树脂组合物包含树脂和本发明由式(1)所示的二亚铵化合物。
本发明树脂组合物中所用的树脂的具体例子包括:乙烯基化合物的加成聚合物,如聚乙烯、聚苯乙烯、聚丙烯酸类、聚丙烯酸酯、聚乙酸乙烯酯、聚丙烯腈、聚氯乙烯和聚氟乙烯;聚甲基丙烯酸类,聚甲基丙烯酸酯,聚偏二氯乙烯,聚偏二氟乙烯,聚偏氰乙烯(polyvinylidene cyanide,乙烯基化合物或氟基化合物的共聚物,如偏二氟乙烯/三氟乙烯共聚物,偏二氟乙烯/四氟乙烯共聚物和亚乙烯基二氰/乙酸乙烯酯共聚物;含氟树脂,如聚三氟乙烯、聚四氟乙烯和聚六氟丙烯;聚酰胺如尼龙6和尼龙66,聚酰亚胺,聚氨酯,多肽,聚酯如聚对苯二甲酸乙二醇酯;聚碳酸酯,聚醚如聚甲醛;环氧树脂,聚乙烯醇和聚乙烯醇缩丁醛。
对制备本发明树脂组合物的方法及树脂组合物的使用方法没有特别的限制,但是可以采用如下的公知方法:
(1)将树脂与本发明的二亚铵化合物进行捏合、加热和模塑,制得树脂片或膜的方法;
(2)使本发明的二亚铵化合物与树脂单体或树脂单体的预聚物在聚合催化剂存在下进行浇铸聚合,制得树脂片或膜的方法;
(3)制备含本发明树脂组合物的漆,并将该漆涂布在透明树脂片、透明膜或透明玻璃片上的方法;
(4)使用含本发明的二亚铵化合物和树脂(胶粘材料)的树脂组合物(胶粘剂)制备层压树脂片、层压树脂膜或层压玻璃片的方法;
(5)在涂布胶粘剂的步骤中将含本发明的二亚铵化合物的胶粘剂在透明支承体的表面上(当透明支承体具有上述功能时,在不阻碍该功能侧的表面上)形成粘性层并使该粘性层保留二亚铵化合物的方法。
尽管处理温度和形成膜(形成树脂片)的条件依据使用的树脂(基体树脂(base resin))可以不同,但上述制备方法(1)通常包括:在基体树脂的粉末或颗粒中加入本发明的二亚铵化合物,并在150-350℃进行加热和熔化,然后进行模塑制备树脂片;或者采用挤出设备形成薄膜(形成树脂片)的方法。虽然本发明的二亚铵化合物在基体树脂中的加入量可依据制造的树脂片或膜的厚度、吸收强度和对可见光的透射比而不同,但以基体树脂的总质量为基准,该加入量通常为0.01-30质量%,优选0.03-15质量%。
上述方法(2)可采用在聚合催化剂存在下将本发明的二亚铵化合物、树脂单体或树脂单体的预聚物注入一个模具(模头)并通过反应固化该树脂单体或树脂单体的预聚物,或将上述物质倒入一模头并在模头中固化,形成硬的产物来对它们进行模塑的方法。许多树脂通过这种方法可以成形,但可以应用于这种模塑方法的树脂的具体例子包括:丙烯酸类树脂、二甘醇二(碳酸烯丙酯)树脂、环氧树脂、酚-醛树脂、聚苯乙烯树脂和有机硅树脂。其中,优选基于甲基丙烯酸甲酯的本体聚合的浇铸方法,因为这种方法制成的丙烯酸片的硬度、耐热性和耐化学性优良。本发明的二亚铵化合物在树脂中的浓度可依据制造的树脂片或膜的厚度、吸收强度和对可见光的透射比而不同,但以基体树脂的总质量为基准,该浓度通常为0.01-30质量%,优选0.03-15质量%。
在上述方法中,可使用已知的热自由基聚合引发剂作为聚合反应催化剂。可使用的聚合催化剂的具体例子包括过氧化物,如过氧化苯甲酰、过氧化对氯苯甲酰,以及过碳酸二异丙酯和偶氮化合物如偶氮二异丁腈。催化剂的含量一般为二亚铵化合物和树脂单体或树脂单体预聚物的混合物总质量的0.01-5质量%。热聚合步骤的加热温度一般为40-200℃,聚合反应时间一般约为30分钟至8小时。除热聚合法外,可以采用在树脂中加入光聚合引发剂和光敏剂并对树脂进行光聚合的方法。
上述方法(3)包括以下方法:将本发明的二亚铵化合物溶于树脂(粘合剂)和有机溶剂来制备漆的方法;在树脂存在下将本发明的二亚铵化合物细粉碎并将细颗粒分散在水中获得水基漆的方法。前一种方法中,可以使用例如脂族酯树脂、丙烯酸类树脂、密胺树脂、聚氨酯树脂、芳族酯树脂、聚碳酸酯树脂、聚乙烯基型树脂、脂族聚烯烃树脂、芳族聚烯烃树脂、聚乙烯醇树脂、聚乙烯-改性树脂,或它们的共聚物树脂作为粘合剂。本发明的二亚铵化合物用于这种方法并溶解在用作粘合剂的树脂中时,所述粘合剂的玻璃化转变温度(Tg)相对较低,如Tg为70℃时,二亚铵化合物不会引起变性,因此能形成耐热性和耐湿热性优良的涂层。
前一种方法还可以使用卤素类有机溶剂、醇类有机溶剂、酮类有机溶剂、酯类有机溶剂、脂族烃类有机溶剂、芳族烃类有机溶剂或醚有机溶剂,或者它们的混合物作为有机溶剂。本发明的二亚铵化合物在树脂中的浓度可依据形成的涂层的厚度、吸收强度和对可见光的透射比而不同,但以树脂(粘合剂)的总质量为基准,该浓度通常为0.1-30质量%。
可以通过旋涂机、绕线棒刮涂器、辊涂机或喷枪将按照上述方式制备的漆施涂到透明树脂薄膜、透明树脂片或透明玻璃片上,得到近红外光吸收滤光片等。
上述方法(4)中,可以使用用于如有机硅树脂、聚氨酯树脂和丙烯酸型树脂的树脂的粘合剂,或者用于层压玻璃的已知透明粘合剂如聚乙烯醇缩丁醛粘合剂和乙烯-乙酸乙烯酯型粘合剂作为用于粘性材料的粘合剂。按照下面方式使用含0.1-30质量%的本发明二亚铵化合物的胶粘剂来制造滤光器等,即用这种胶粘剂将透明树脂片相互粘合在一起,将一个树脂片和一个树脂薄膜粘合在一起,一个树脂片和一个玻璃片粘合在一起,两个树脂薄膜相互粘合在一起、将一个树脂薄膜与一个玻璃片粘合在一起、以及将两个玻璃片粘合在一起。
此外,在上述(1)至(4)的方法中,在捏合或混合步骤,可以加入在模塑树脂时使用的常规添加剂,如紫外光吸收剂和增塑剂。
下面描述上述的方法(5)。
如上得到的本发明的树脂模塑的制品可以应用于下述场合:例如吸收近红外光用的片或薄膜(近红外光吸收滤光片),削减红外光所需的滤光片或薄膜,如隔热膜、光学制品和太阳镜。
下面,将描述使用本发明的二亚铵化合物的近红外光吸收滤光片,这种滤光片是本发明的二亚铵化合物最具特性的应用。
本发明的近红外光吸收滤光片只需具有一层含本发明的二亚铵化合物的层,因此可以是在一基片上具有一层含本发明的二亚铵化合物的树脂层的滤光片,或者是基片本身是由含本发明的二亚铵化合物的树脂组合物(或其固化物质)形成的片、薄膜、板或层。对用于基片的材料没有特别的限制,只要是通常用于近红外光吸收滤光片,但是通常使用上述树脂或玻璃的基片。含本发明的二亚铵化合物的片、薄膜、板或层的厚度通常约为0.1μm至10mm,可依据目标近红外光的削减比例选择适当的厚度。如上所述,本发明的二亚铵化合物的含量也可以依据目标近红外光的削减比例适当选择。所用的基片在形成并加工成板、薄膜等之后的透明度应尽可能高为宜。
本发明的近红外光吸收滤光片可以只含有本发明的式(1)所示的二亚铵化合物中一种作为近红外光吸收化合物,然而,本发明的近红外光吸收滤光片也可以通过组合使用两种或更多种本发明的二亚铵化合物,或者一起使用本发明的二亚铵化合物与除本发明的二亚铵化合物之外的近红外光吸收化合物来制备。除了本发明的二亚铵化合物之外的近红外光吸收化合物包括,例如,有机化合物,如酞菁类化合物、花青类化合物和二硫醇镍络合物;铜化合物,如金属铜、硫化铜和氧化铜;含氧化锌为主要组分的金属混合物;金属化合物或它们的混合物,如钨化合物、氧化铟锡(ITO)和锑掺杂的氧化锡(ATO)。
为了改变近红外光吸收滤光片的色调,该滤光片还可以含有着色用物质(用来调色的着色物质),这些物质在可见光区在不抑制本发明效果的范围内具有吸收作用。或者,还可以制造只含一种用来调色的着色物质的滤光片,然后将其粘合到本发明的近红外光吸收滤光片。
在等离子体显示器的前面板上使用这种近红外光吸收滤光片时,滤光片对可见光必须具有尽可能高的透射比,至少为40%,优选至少为50%。近红外光吸收滤光片削减在700-1,100nm区域的近红外光,并对在该区域的近红外光的平均透射比通常为小于或等于50%,优选小于或等于30%,更优选小于或等于20%,最优选小于或等于10%。
本发明的近红外光吸收滤光片是在可见光区显示很高透射比的优良近红外光吸收滤光片,因为不含锑和砷而对环境无害,并能吸收宽范围的近红外光。与不含锑但含高氯酸根离子、六氟磷酸根离子或硼氟酸根离子的常规近红外光吸收滤光片相比,本发明的滤光片的稳定性优良。此外,本发明的二亚铵化合物在制备近红外光吸收滤光片所用的溶剂中具有足够高的溶解性,因此滤光片具有优良的可加工性。本发明的近红外光吸收滤光片尤其具有杰出的耐热性、耐湿热性和耐光性,几乎不会发生因受热分解的反应,因此近红外光吸收滤光片几乎不会在可见光区着色。
使用本发明式(1)所示的二亚铵化合物的近红外光吸收滤光片可以采用上述的方法(1)至(5)中任一种方法制造,但优选方法(3)、(4)和(5);特别优选方法(5),该方法是在涂布胶粘剂的步骤中,由含本发明的二亚铵化合物的胶粘剂在透明支承体的表面上(当透明支承体具有上述功能时,在不会阻碍该功能一侧的表面上)形成粘性层,并使该粘性层保留二亚铵化合物,优选方法(5)的原因是该方法因减少了涂布步骤的次数从而降低了成本的优点。
下面,详细描述通过在粘性层中加入式(1)表示的本发明的二亚铵化合物制成的近红外光吸收滤光片。
在粘性层中可以只含有用于本发明的由式(1)表示的二亚铵化合物,但是也可以与一种或多种除了式(1)表示的二亚铵化合物外的近红外光吸收化合物一起使用。可一起使用的其它类型的近红外光吸收化合物例子包括:上述化合物;除本发明的式(1)表示的二亚铵化合物之外的二亚铵化合物;亚硝基化合物或其金属盐;有机化合物如花青类化合物、squalirium基化合物、硫醇镍络合物盐、酞菁类化合物、萘酚菁类化合物(naphthalocyanine-based compound)、三芳基甲烷基化合物、萘醌基化合物和蒽醌基化合物;无机化合物如氧化锑锡、氧化铟锡和稀土金属的六硼化物如六硼化镧。自然,式(1)的二亚铵化合物可以单独使用,或者以与另一种或多种式(1)的二亚铵化合物的混合物形式使用。当式(1)的二亚铵化合物与另一种近红外光吸收化合物一起使用时,在使用的混合物中优选包含40-100质量%本发明的式(1)的二亚铵化合物。
下面,详细描述制备在粘性层中包含式(1)的二亚铵化合物的近红外光吸收滤光片的方法。
对用于本发明的近红外光吸收滤光片的支承体的种类和厚度没有特别的限制,只要支承体是高度透明的,没有瑕疵,并能持久用作光学薄膜。支承体的具体例子包括:聚合物树脂的薄膜,所述树脂例如是聚酯基(下面称作PET)树脂、聚碳酸酯基树脂、三乙酸酯基树脂、降冰片烯基树脂、丙烯酸类树脂、纤维素树脂、聚烯烃基树脂和聚氨酯基树脂。还可以使用含有吸收来自外部紫外光的紫外线吸收材料的透明支承体,以稳定如薄膜的内部部件的功能。支承体的表面可以进行电晕放电处理、等离子体处理、辉光放电处理、粗糙化处理或化学处理,或者在支承体上可以有一层打底胶浆(anchor coat agent)或底涂剂的涂层,以提高与涂布剂的粘合性。支承体更优选是如具有以下的一种或多种功能的薄膜或片材,例如,减反射性、防炫光/抗反射性、防静电性、防污性、氖光吸收性、电磁波屏蔽性、调色性等,因为在支承体上形成具有近红外光吸收能力的粘性层时,制成的滤光片可同时具有透明支承体所具有的功能以及近红外光吸收能力,还因为这种形式在制造工艺方面的优点并能提供优良的滤光器。
下面,描述使用具有上述功能的支承体(膜)的例子。
第一个例子是减反射薄膜,通过在如PET的透明支承体的表面涂敷低折射率剂(low refractivity agent)与聚合物树脂(粘结剂)和其它添加剂,这种薄膜能抑制来自外部光的反射,或者是通过在透明支承体和低折射率层之间提供硬涂层和高折射率层以控制从各层反射的光使它们相互抵消从而获得改进可见度(visibility)的薄膜。第二个例子的是防炫光/抗反射薄膜,通过在上述减反射薄膜的高折射率层或其它层中加入细小粒子,使来自外部的光不规则地反射,来达到进一步提高可见度。防炫光/抗反射薄膜可以Arctop系列(Asahi Glass)、Kayacoat ARS系列(Nippon Kayaku Co.,Ltd)、Kayacoat AGRS系列(NipponKayaku Co.,Ltd)和ReaLook系列(Nippon Oil&Fats)的商标方便购得。
第三个例子是电磁波屏蔽薄膜,这种薄膜包括网格型和薄膜型,所述网格型中,在透明支承体上保留一定几何形状如网格的超细金属丝如铜丝,所述薄膜型中,在透明支承体上保留有保持在光透明性范围的超薄薄膜。但是,优选使用网格型的透明电磁波屏蔽薄膜作为本发明的近红外光吸收滤光片的支承体。
具有本发明所需的其它功能的透明支承体包括具有以下一种单一功能或同时具有多种功能的薄膜:氖光吸收性、紫外光吸收性、防静电性、防污性和调色性。这种薄膜可以采用本领域公知的方法如对包含具有特定功能的化合物的组合物进行模塑的方法来制备。
对作为粘性层的主要组分的粘结剂树脂(下面称作粘性材料)没有特别的限制,只要能将本发明的二亚铵化合物均匀地分散在其中,在保持透明度的同时与透明支承体的表面粘合,并且不会降低滤光器的功能。可使用的粘性材料的例子包括以下树脂的粘性材料:丙烯酸基树脂、聚酯基树脂、聚酰胺基树脂、聚氨酯基树脂、聚烯烃基树脂、聚碳酸酯基树脂、橡胶基树脂和有机硅基树脂;优选丙烯酸基树脂的粘性材料,因为丙烯酸基树脂在透明度、粘合性和耐热性方面性能优良。丙烯酸基树脂的粘性材料可以通过共聚作为主组分的不含官能团的丙烯酸烷基酯与除该丙烯酸烷基酯外的具有官能团的丙烯酸烷基酯或具有官能团的单体组分来形成。用于共聚的除不含官能团的丙烯酸烷基酯外的具有官能团的丙烯酸烷基酯或具有官能团的单体组分的用量为0.1-20质量份,优选为1-10质量份,相对于100质量份不含官能团的丙烯酸烷基酯组分计。
不含官能团的丙烯酸烷基酯的例子包括其中烷基具有1-12个碳原子的丙烯酸烷基酯和甲基丙烯酸烷基酯,如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯、(甲基)丙烯酸癸酯、(甲基)丙烯酸十一烷基酯和(甲基)丙烯酸十二烷基酯。需要时可以一起使用两种或多种上述丙烯酸烷基酯。
一种起到与下面所述的交联剂的交联点功能的化合物可用于除丙烯酸烷基酯外的具有官能团的丙烯酸烷基酯或具有官能团的单体。对这种化合物没有特别的限制,但包括含羟基的(甲基)丙烯酸酯单体,如(甲基)丙烯酸2-羟基乙酯和(甲基)丙烯酸羟基丙酯;含氨基的(甲基)丙烯酸酯单体,如N,N-二甲基氨基乙基丙烯酸酯和N-叔丁基氨基乙基丙烯酸酯;丙烯酸和马来酸。需要时,可以一起使用两种或多种上述化合物。
胶粘剂优选用作包含交联剂的组合物,该组合物能交联如上述丙烯酸类树脂的粘性材料。根据上述单体的类型适当使用交联剂。可使用的交联剂的例子包括:脂族二异氰酸酯,如1,6-己二异氰酸酯和1,6-己二异氰酸酯的三羟甲基丙烷加成物;多异氰酸酯化合物,如芳族二异氰酸酯,如甲苯二异氰酸酯和甲苯二异氰酸酯的三羟甲基丙烷加成物;三聚氰胺化合物,如丁基-醚化的苯乙烯三聚氰胺和三羟甲基三聚氰胺;二胺化合物,如六亚甲基二胺和三乙二胺;环氧树脂基化合物,如双酚-A/表氯醇;脲树脂基化合物;以及金属盐,如氯化铝、氯化铁和硫酸铝。交联剂的混合量,相对于100质量份粘性材料,通常为0.005-5质量份,优选0.01-3质量份。
丙烯酸类粘性材料因为在聚合物中不含不饱和键而具有优良的粘合强度、内聚能力和对光和氧的高稳定性,并在选择单体类型和分子量方面有较高的自由度,因此胶粘剂优选包括丙烯酸类粘性材料。粘性材料优选为高分子量(高聚合度)的,以保持与透明支承体的粘合性。具体地,主要聚合物的平均分子量(Mw)优选为约600,000-2,000,000,更优选约800,000-1,800,000。
在等离子体显示板(PDP)中,由上面保留有氖光吸收化合物的透明支承体制成的氖光吸收滤光片通常用于削减波长在550-620nm范围的橙色氖光,这种氖光来自于在显示板上施加电压时产生的Ne气,这种氖光不可避免地降低红光的色纯度,因此必须在显示器的前面削减到一定程度。当使用含本发明的二亚铵化合物的粘性层时,在该粘性层中可以包含具有氖光吸收能力的化合物。由此制成的粘性层能同时吸收近红外光和氖光。在此,氖光吸收化合物包括,例如,吖卟啉化合物(azaporphyrin compound),如四吖卟啉化合物、花青化合物、squalirium化合物、偶氮甲碱化合物、呫吨化合物、氧杂菁化合物(oxonolcompound)和偶氮化合物。将所述化合物加入到粘性层时,化合物优选是四吖卟啉化合物,因为四吖卟啉化合物的耐热性和耐湿热性优良。
还必须将电磁波屏蔽滤光器放置在PDP的前侧,因为电磁波是从显示器的表面发射的,从健康角度,认为电磁波对人体会造成伤害。因此,可以使用各种类型的电磁波屏蔽滤光器,但是因为网格型电磁波屏蔽滤光器具有优良的电磁波屏蔽能力的原因而主要使用这类滤光器。如上所述,所述滤光器由其上具有一定几何形状(如网格)的超细金属丝如铜丝的透明支承体制成,将这种滤光器放置在PDP的前面,通过捕获有害电磁波并将其耗散到地面,能防止有害的电磁波泄漏到观察者一侧。但是,这种滤光器有时在耐久性方面存在问题,原因是金属如铜的网格表面通过透明支承体保持与空气接触的状态,尽管取决于制造方法和形状,但因此在将粘性层施涂在表面或者施涂到另一个功能薄膜并通过该粘性层将薄膜固定在表面上时,粘性层主要因为如铜的金属的氧化引起变色。解决这种问题的有效方法如下:
(1)预先在粘性层中加入防锈剂,以防止变色;和
(2)减少粘性层中有机酸量至最小。
此外,网格型电磁波屏蔽膜有时降低表面的透明度,因为这种网格型电磁波屏蔽膜是采用以下步骤制造的,即对如铜的金属箔表面进行粗糙化以使铜箔与透明薄膜以足够的粘合性粘合,用粘合剂将铜箔固定在透明支承体,采用蚀刻技术通过溶解除去格栅线外的部分,同时只留下格栅线,并由此将铜箔的粗糙表面的形状转印到涂敷在透明支承体的固化粘合剂层的表面上,并留在该表面上。为此原因,对聚合物树脂表面进行进一步的处理,以使表面光滑,膜透明,但是这种透明化处理会增加成本,因此希望能省略该处理。将含防锈剂的粘性层施涂到网格型电磁波屏蔽膜上,该膜具有暴露于外部的如铜的金属格栅表面(下面称作网格表面),换句话说,将含防锈剂的粘性层施涂在仍没有进行透明化处理的电磁波屏蔽膜上。据发现,通过在网格表面上形成粘性层或者将其上已形成粘性层的功能膜通过该粘性层施压固定到电磁波屏蔽膜的网格表面,粘合剂层上的粗糙表面可以被消除,且薄膜会变透明。这种方法是一种更合理的方法。此外,随粘性层的折射率接近表面粗糙化的粘合剂层的折射率,该粘合剂层的透明度提高,因此当制备胶粘剂时,必须考虑折射率能满足上述条件。
对上述方法(1)中所使用的防锈剂没有特别的限制,只要具有防止金属生锈的能力。可使用的防锈剂的具体例子包括:2-氨基吡啶、2-氨基嘧啶、2-氨基喹啉、氨基三嗪或氨基三唑和它们的取代的衍生物,苯并三唑基化合物、苯基四唑和2-氨基三噻唑。这些防锈剂中,优选苯并三唑基化合物,还优选1H-苯并三唑,因为这种化合物容易处理。防锈剂的用量相对于粘合和涂敷后的粘性层的为0.01-10质量%,优选0.05-5质量%。
对上述方法(2),优选通过将有机酸用量降至最小或者需要时增加纯化步骤,将用作粘性层中的粘性物质的含羧基单体如丙烯酸和马来酸的有机酸物质的含量控制到小于或等于0.5质量%。
液体胶粘剂可采用以下方法制备,将本发明的式(1)的二亚铵化合物与作为胶粘剂主要组分的粘性材料、聚合反应引发剂、交联剂、紫外线吸收剂、调色用着色物质以及其它必需的组分一起充分溶解或分散在如甲基乙基酮的(MEK)的溶剂中;将该液体胶粘剂涂敷在透明支承体的表面,干燥后的层厚度为5-100μm,优选10-50μm。对涂敷方法没有特别的限制,包括以下方法:用刮条涂布机、反向涂布机、comma涂布机或凹槽辊涂布机将该液体胶粘剂施涂到透明支承体上,对其进行干燥使粘性层粘合到透明支承体上;用刮条涂布机、反向涂布机、comma涂布机或凹槽辊涂布机将液体胶粘剂施涂到支承体的脱模薄膜上,对该胶粘剂进行干燥,并将粘性层转移到透明支承体上。优选设计的本发明的近红外光吸收滤光片能对波长为700-1,100nm的近红外光的透射比小于或等于20%,更优选小于或等于10%。本发明的二亚铵化合物在胶粘剂中的含量只要能与上面条件相配,通常为相对粘性层的1-20质量%。
下面,本发明的滤光器可通过下面方法制得:将本发明的近红外光吸收滤光片,特别是具有位于本发明的透明支承体上的含本发明二亚铵化合物的粘性层的近红外光吸收薄膜作为主要部件的近红外光吸收滤光片,叠加在具有下面所述功能的透明支承体(薄膜)上。可以将本发明的滤光器预先粘合到透明玻璃板或塑料片上后,放置在PDP的前面,或者可以将本发明的滤光器直接固定到PDP的前面。上述粘性层只要通过施压粘合到玻璃或薄膜上就具有足够的强度,但是也可以按照需要在加热时将粘性层施压粘合到玻璃或薄膜上来提高粘合强度。
下面说明具有功能的透明支承体的例子。在实例中,参考字符NIR表示近红外光,参考字符Ne表示氖光,括号部分表示本发明的近红外光吸收滤光片。由这些结构例子可以清楚地理解,使具有一定功能的透明支承体如减反射透明支承体上的粘性层含有本发明的式(1)二亚铵化合物以及氖光吸收化合物是有利的。
(1)(减反射透明支承体/NIR-Ne吸收-调色粘性层)/电磁波屏蔽膜;
(2)(减反射透明支承体/NIR-调色吸收粘性层)/电磁波屏蔽膜/粘性层/Ne吸收膜;
(3)减反射薄膜/(NIR-Ne吸收粘性层/电磁波屏蔽透明支承体);
(4)(防炫光-减反射透明支承体/NIR-Ne吸收聚合物树脂层)/电磁波屏蔽膜;
(5)减反射薄膜/(NIR-Ne吸收-调色粘性层/PET透明支承体)/粘性层/电磁波屏蔽膜;
(6)减反射薄膜/(NIR-吸收粘性层/Ne-吸收透明支承体)/粘性层/电磁波屏蔽膜;
(7)减反射薄膜/粘性层/电磁波屏蔽膜/(NIR-吸收-调色粘性层/Ne-吸收透明支承体);
(8)减反射薄膜/粘性层/电磁波屏蔽膜/(NIR-Ne-吸收粘性层/PET透明支承体)。
因此,本发明设计的近红外光吸收滤光片,其粘性层含有本发明的二亚铵化合物,是在可见光区显示很高透射比的优良近红外光吸收滤光片,因为不含锑和砷而对环境无害,并能吸收宽范围的近红外光。与不含锑但含高氯酸根离子、六氟磷酸根离子或硼氟酸根离子的常规近红外光吸收滤光片相比,本发明的滤光片的稳定性优良。此外,本发明的二亚铵化合物在制造近红外光吸收滤光片时使用的溶剂中具有足够高的溶解性,因此该滤光片具有优良的可加工性。本发明的近红外光吸收滤光片尤其有杰出的耐热性、耐湿热性和耐光性,几乎不会因受热发生分解反应,因此近红外光吸收滤光片几乎不会在可见光区着色。由于本发明的近红外光吸收滤光片具有这些特性,这种滤光片可以单独使用,但特别适合于等离子体显示器用的滤光器。
下面,描述本发明的光信息记录介质。
本发明的光信息记录介质包含在基片上的记录层,其特性是记录层中含有本发明的二亚铵化合物。所述记录层可以只包含二亚铵化合物或二亚铵化合物与不同的添加剂如粘合剂一起的混合物。这种情况下,由本发明的二亚铵化合物记录信息。
也可以在光信息记录介质的记录层中加入本发明二亚铵化合物和二亚铵化合物以外的有机着色物质的混合物,将信息记录在有机着色物质中,因此提高了光信息记录介质的耐光性。这种光信息记录介质中,供记录信息用的有机着色物质包括:花青基染料、squarylium基染料、靛苯胺基染料(indoaniline-based pigment)、酞菁基染料、偶氮基染料、部花青基染料、聚甲炔基染料、萘醌基染料和吡喃鎓基染料。这种方法中,记录层中本发明的二亚铵化合物的用量,相对于1摩尔有机着色物质通常为0.01-10摩尔,优选0.03-3摩尔。
本发明的光信息记录介质包含在基片上的含本发明二亚铵化合物和该二亚铵化合物外的颜料的记录层,以及需要时的反射层和保护层。可以使用任何已知的基片作为基片。基片包括例如玻璃片、金属片或塑料片或薄膜。制造基片的塑料树脂是例如丙烯酸类树脂、聚碳酸酯树脂、甲基丙烯酸类树脂、聚砜树脂、聚酰亚胺树脂、非晶形聚烯烃树脂、聚酯树脂和聚丙烯树脂。对基片的形状,可以是各种形状,如盘、卡、片和成卷薄膜的形式。
为能在记录时容易跟踪,在玻璃或塑料基片上形成导槽。还在玻璃和塑料基片上形成塑料粘合剂或者无机氧化物和无机硫化物制成的底涂层,所述底涂层的热导率系数宜小于基片的热导率系数。
本发明的光信息记录介质的记录层可以通过以下步骤形成,将例如本发明的二亚铵化合物,较好是本发明的二亚铵化合物与另一种有机着色物质溶解在已知的有机溶剂中,如四氟丙醇(TFP)、八氟戊醇(OFP)、双丙酮醇、甲醇、乙醇、丁醇、甲基溶纤素、乙基溶纤素、二氯乙烷、异佛尔酮和环己酮中;如果需要可加入粘合剂;并用旋涂机、刮条涂布机或辊涂机等将制成的溶液施涂在基片上。记录层还可以通过其它方法制造,如真空沉积法、溅射法、刮刀刮涂法、浇铸法和将基片浸在溶液中的浸涂法。在上述描述中,可使用的粘合剂包括丙烯酸类树脂、聚氨酯树脂或环氧树脂等。
考虑到记录灵敏度和反射比,记录层厚度宜为0.01-5μm,更好为0.02-3μm。
如果需要,本发明的光信息记录介质可以具有在记录层下面的底涂层以及在记录层上的保护层,还可以在记录层和保护层之间形成反射层。形成反射层时,该反射层可以由金、银、铜和铝,优选金、银或铝的金属形成。这些金属可以单独使用或以这些金属的两种或多种的合金使用。反射层可采用真空沉积法、溅射法或离子镀敷法等方法形成。反射层厚度为0.02-2μm。某些情况,在反射层上形成的保护层一般可采用下面步骤形成:通过旋涂法施涂可紫外线固化的树脂,然后用紫外光辐照使涂膜固化。除了上述树脂外,可以使用环氧树脂、丙烯酸类树脂、有机硅树脂、聚氨酯树脂等作为形成保护膜的材料。这样的保护膜厚度一般为0.01-100μm。
在本发明的光信息记录介质上通过下面方式进行信息记录和图像生成,用如半导体激光、氦氖激光、He-Cd激光、YAG激光和Ar激光的光点型激光的集中的高能光束通过基片或从与基片相反面辐照记录层。通过用低能激光束辐照记录层,并检测从形成凹陷的部分和未形成凹陷的部分反射的光量或透射通过这些部分的光量之间的差异,来读出信息或图像。
与含常规二亚铵化合物的光信息记录介质相比,本发明的光信息记录介质显示显著提高了的耐光稳定性。此外,本发明式(1)所示的二亚铵化合物具有用于制备光信息记录介质的足够的溶解性以及优良的可加工性。将这种二亚铵化合物作为光稳定剂加入到例如对应于光信息记录介质的记录层的有机着色物质薄膜中时,在光信息记录介质重复使用时,该化合物也能显著提高光信息记录介质的耐久性以及耐光稳定性。
实施例
下面,参照实施例更详细地说明本发明,但是本发明不限于这些实施例。此外,除非另外指出,实施例中的“份”和“%”均以质量为基准。此外,以下对λmax的测定值中,认为±4nm的差额是测量条件所造成的并且是允许的。
实施例1
将4份N,N,N′,N′-四(p-二(正丁基)氨基苯基)-对苯二胺加入到20份DMF中,加热至60℃时溶解于DMF。然后,在上述液体中加入8份含58.4%三(三氟甲基磺酰基)甲烷(由3M公司制备)的水溶液。随后,在该液体中加入溶解在23.5份DMF中的1.6份硝酸银,对形成的液体加热和搅拌30分钟。通过以下步骤获得7份为表1中1号的二亚铵化合物:从上面的液体中滤出不溶物,在该反应液体中加入水和甲醇以沉淀晶体,滤出沉淀的晶体,用甲醇,然后用水洗涤,并对晶体进行干燥。
λmax:1,101nm(二氯甲烷),摩尔吸收系数(ε):107,000
实施例2
将6份N,N,N′,N′-四(p-二(异丁基)氨基苯基)-对苯二胺加入到36份DMF中,加热至60℃时溶解于DMF。然后,在上述液体中加入10.1份含58.4%三(三氟甲基磺酰基)甲烷的水溶液。随后,在该液体中加入溶解在35份DMF中的2.32份硝酸银,对形成的液体加热和搅拌30分钟。通过下述步骤获得8.4份为表1中2号的二亚铵化合物:从上面的液体中滤出不溶物,在该反应液体中加入水以沉淀晶体,滤出沉淀的晶体,用甲醇,然后用水洗涤,并对晶体进行干燥。
λmax:1,109nm(二氯甲烷),摩尔吸收系数(ε):107,000
实施例3
将3份N,N,N′,N′-四(p-二(正丙基)氨基苯基)-对苯二胺加入到20份DMF中,加热至60℃时溶解于DMF。然后,在上述液体中加入6.7份含52%三(三氟甲基磺酰基)甲烷的水溶液。随后,在该液体中加入溶解在25份DMF中的1.4份硝酸银,对形成的液体加热和搅拌30分钟。通过以下步骤获得2份为表1中26号的二亚铵化合物:从上面的液体中滤出不溶物,在该反应液体中加入水和甲醇以沉淀晶体,滤出沉淀的晶体,用甲醇,然后用水洗涤,并对晶体进行干燥。
λmax:1,098nm(二氯甲烷),摩尔吸收系数(ε):107,000
实施例4
将5份N,N,N′,N′-四(p-二(正氰基丙基)氨基苯基)-对苯二胺加入到30份DMF中,加热至60℃时溶解于DMF。然后,在上述液体中加入7.8份含58.4%三(三氟甲基磺酰基)甲烷的水溶液。随后,在该液体中加入溶解在30份DMF中的2.1份硝酸银,对形成的液体加热和搅拌30分钟。通过以下步骤获得5.4份为表1中3号的二亚铵化合物:从上面的液体中滤出不溶物,在该反应液体中加入水和甲醇以沉淀晶体,滤出沉淀的晶体,用甲醇,然后用水洗涤,并对晶体进行干燥。
λmax:1,066nm(二氯甲烷),摩尔吸收系数(ε):110,000
实施例5
将2份N,N,N′,N′-四(p-二乙基氨基苯基)-对苯二胺加入到20份DMF中,加热至60℃时溶解于DMF。然后,在上述液体中加入4.5份含58.4%三(三氟甲基磺酰基)甲烷的水溶液。随后,在该液体中加入溶解在20份DMF中的1.1份硝酸银,对形成的液体加热和搅拌30分钟。通过以下步骤获得0.8份为表1中21号的二亚铵化合物:从上面的液体中滤出不溶物,在该反应液体中加入水和甲醇以沉淀晶体,滤出沉淀的晶体,用甲醇,然后用水洗涤,并对晶体进行干燥。
λmax:1,087nm(二氯甲烷),摩尔吸收系数(ε):101,000
实施例5A
将3份N,N,N′,N′-四(p-二(正戊基)氨基苯基)-对苯二胺加入到40份DMF中,加热至60℃时溶解于DMF。然后,在上述液体中加入5.3份含52%三(三氟甲基磺酰基)甲烷的水溶液。随后,在该液体中加入溶解在30份DMF中的1.1份硝酸银,对形成的液体加热和搅拌60分钟。通过以下步骤获得1.9份为表1中5号的二亚铵化合物:从上面的液体中滤出不溶物,在该反应液体中加入水和甲醇以沉淀晶体,滤出沉淀的晶体,用甲醇,然后用水洗涤,并对晶体进行干燥。
λmax:1,106nm(二氯甲烷),摩尔吸收系数(ε):108,000
其它化合物的例子可以按照上述实施例的情况,通过在相应阴离子存在下用氧化剂对相应的苯二胺衍生物进行氧化来制备。
实施例6
将0.06份在上述实施例1中制备的表1的编号1的二亚铵化合物溶解于0.94份MEK(甲基乙基酮)。在该溶液中加入3.4份Folet GS-1000(SokenChemical&Engineering Corporation生产的丙烯酸树脂的商品名,Tg:100-110℃),混合后形成涂敷溶液。将该溶液涂敷在Cosmoshine A4300(ToyoboCorporation制备的聚酯薄膜的商品名),厚度为2-4μm,涂膜于80℃进行干燥。因此,制得本发明的近红外光吸收滤光片。
分别用上述实施例中获得的2号和3号的二亚铵化合物进行类似的处理,可获得本发明的近红外光吸收滤光片。
实施例7
采用与实施例6中相同的方法制得本发明的近红外光吸收滤光片,除了将粘合剂树脂Folet GS-1000(Soken Chemical&Engineering Corporation生产的丙烯酸树脂的商品名,Tg:100-110℃)改变为Acrydica LAL-115(Dainippon Ink&Chemicals,Inc.生产的丙烯酸树脂的商品名,Tg:70℃),将1号二亚铵化合物改变为2号二亚铵化合物。
评价试验(1)
(耐热性稳定性试验)
将实施例6和实施例7中制得的各近红外光吸收滤光片在100℃的烘箱内停留480小时,测试滤光片的耐热性稳定性。通过用UV-3150(ShimadzuCorporation制造的光谱光度计的商品名),测定在该稳定性试验之前和之后该滤光片的最大吸收波长下的吸光率变化,来评价保留的颜料量。
按照与实施例6中相同的方法,制备用于比较的近红外光吸收滤光片,除了表1中1号二亚铵化合物被N,N,N′,N′-四(p-二(正丁基)氨基苯基)苯二亚铵的六氟锑酸盐(化合物(A))、N,N,N′,N′-四(p-二(正丁基)氨基苯基)苯二亚铵的二(三氟甲烷磺酰基)酰亚胺化物(imidate)(化合物(B))、N,N,N′,N′-四(p-二(氰基丙基)氨基苯基)苯二亚铵的二(三氟甲烷磺酰基)酰亚胺化物(化合物(C))和N,N,N′,N′-四(p-二(异丁基)氨基苯基)苯二亚铵的二(三氟甲烷磺酰基)酰亚胺化物(化合物(D))替代。对这些滤光片进行同样的测定。结果列于表2。
此外,使用N,N,N′,N′-四(p-二(氰基丙基)氨基苯基)苯二亚铵的六氟锑酸盐和N,N,N′,N′-四(p-二(i-丁基)氨基苯基)苯二亚铵的六氟锑酸盐进行类似的试验,但无法按照上述情况制备近红外光吸收滤光片,因为这些化合物对于溶剂没有足够的溶解性。
表2耐热性稳定性试验
实施例6(比较)(比较)实施例6(比较)实施例7实施例6(比较) | 化合物 | 颜料残留率(%) | |
试验前 | 试验后 | ||
1号(A)(B)2号(D)2号3号(C) | 100100100100100100100100 | 80.149.432.387.282.887.181.453.5 |
由表2的结果可以清楚知道, 与使用已知的二亚铵化合物获得的近红外光吸收滤光片相比,本发明的近红外光吸收滤光片具有更高的颜料残留率,对热条件显示更好的耐热性。由表2的结果还可以知道,即使是使用Tg相对较低的粘性材料制成的近红外光吸收滤光片也具有类似于使用Tg相对较高的粘性材料制成的近红外光吸收滤光片的优良的热稳定性。
评价试验(2)
(耐湿热性稳定性试验)
按照下面方式,使用与评价试验(1)中所用的相同的近红外光吸收滤光片,测试对耐湿热性的稳定性。
将实施例6和实施例7中制得的本发明的近红外光吸收滤光片以及制备的比较用的近红外光吸收滤光片在60℃和90%RH(相对湿度)环境停留480小时,用上述的光谱光度计,测定在该稳定性试验之前和之后滤光片的最大吸收波长下的吸光率变化,来评价保留的颜料量。
表3耐湿热性稳定性试验
实施例6(比较)(比较)实施例6(比较)实施例7实施例6(比较) | 化合物 | 颜料残留率(%) | |
试验前 | 试验后 | ||
No.1(A)(B)2号(D)2号3号(C) | 100100100100100100100100 | 79.650.656.588.083.188.079.652.4 |
由表3的结果可以清楚知道,与在阳离子位置具有同样取代基的比较例相比,本发明的近红外光吸收滤光片具有更高的颜料残留率,对高温和高湿度环境显示更好的耐湿热性。由表3的结果还可以知道,使用Tg相对较低的粘性材料制成的近红外光吸收滤光片具有类似于使用Tg相对较高的粘性材料制成的近红外光吸收滤光片的优良的耐湿热稳定性。
实施例8
按照下面步骤制造吸收近红外光和氖光的薄膜:制备均匀的涂敷液体,即,对下面表4所示的用于胶粘剂的各物质进行混合和溶解;用comma涂布机,以0.8米/分钟速率,将该涂敷液体施涂到MRF-75(Mitsubishi Polyester FilmCorporation生产的脱模PET薄膜的商品名,厚度为75μm),形成18μm厚度的粘性层;涂膜于110℃进行干燥。将该薄膜粘贴在透明支承体上的KayacoatARS-D250-125(Nippon Kayaku Co.,Ltd.生产的减反射薄膜的商品名)的减反射涂层的背面,该层叠物于35℃老化2天,形成本发明的近红外光吸收滤光片,该滤光片具有减反射性、近红外光吸收性、氖光吸收性和调色性。此外,将该滤光片上的脱模薄膜剥离,将其余的薄膜通过粘性层粘贴到以下电磁波屏蔽膜1上,形成用于PDP的滤光器,结构为(减反射透明支承体/NIR-Ne-吸收和调色粘性层)/电磁波屏蔽膜1,这种滤光器能简便制造并具有优良的光学性能。
表4
材料 | 用量 |
2号化合物的二亚铵化合物TAP-2(Yamada Chemical Co.,Ltd.生产的氖光吸收剂的商品名)Tinuvin 109(商品名,UV吸收剂,由Ciba-Geigy生产)KAKASET Yellow GN(黄色着色物的商品)KAYASET Blue N(蓝色着色物的商品)PTR-2500T(Nippon Kayaku Co.,Ltd.生产的丙烯酸类树脂的商品名)M12ATY(Nippon Kayaku Co.,Ltd.生产的固化剂的商品名)L45EY(Nippon Kayaku Co.,Ltd.生产的固化剂的商品名)C-50(Soken Chemical&Engineering生产的固化剂的商品名)甲基乙基酮 | 1.0份0.096份1.2份0.006份0.0072份120.0份0.324份0.444份0.142份84.0份 |
(注)TAP-2:四吖卟啉化合物;Tinuvin 109:苯并三唑基化合物;KAKASETYellow GN:(色指数)溶剂黄93,Nippon Kayaku Co.,Ltd.生产;KAYASETBlue N:(色指数)溶剂蓝35,Nippon Kayaku Co.,Ltd.生产;M12ATY:金属螯合物化合物;L45EY:异氰酸酯化合物:C-50:硅烷偶联剂;
(制备电磁波屏蔽膜1)
按照下面步骤制造具有一定透明度的电磁波屏蔽膜1:通过Nikaflex SAF(环氧树脂粘合剂片的商品名,Nikkan Industries Co.,Ltd.生产,厚20μm)的粘合剂层,将具有粗糙表面的厚18μm的导电材料的电解铜箔层叠在CosmoshineA-4100(Toyobo Corporation生产的PET薄膜的商品名,厚度为50μm)上,使该粗糙面与环氧树脂粘合剂片接触,在180℃和30kgf/cm2条件下加热,将它们粘合,通过光刻步骤(光刻胶膜粘贴-曝光-显影-化学蚀刻-光刻胶膜剥离),在制成的有铜箔的PET薄膜的PET薄膜上形成铜格栅图案,格栅线宽度为25μm,线间距为500μm;在铜格栅图案的表面上施涂均匀混合下表5中所示的粘合剂组分制成的粘合剂,干燥后的涂层厚度约为40μm,作为透明化处理。
表5
材料 | 用量 |
TBA-HME(Hitachi Chemical Corporation生产的聚合物环氧树脂的商品名)YD-8125(Tohto Kasei Corporation生产的双酚A型环氧树脂的商品名)IPDI(掩蔽的异氰酸酯,Hitachi Chemical Corporation生产)2-乙基-4-甲基咪唑甲基乙基酮环己烷 | 100份25份12.5份0.3份300份15份 |
实施例9
采用与实施例8相同的方法,制造具有减反射性、近红外光吸收性和氖光吸收性并含有防锈剂的本发明的近红外光吸收滤光片,除了使用以下方式制备的涂敷液体,即,将0.067份防锈剂1H-苯并三唑加入表4所示的胶粘剂的原料中,充分混合,将它们溶解在一溶剂中。将滤光片的脱模薄膜剥离,通过粘性层将剩余的薄膜粘贴到以下电磁波屏蔽膜2的网格表面,形成用于PDP的滤光器,其结构为(减反射透明支承体/NIR-Ne-吸收和调色粘性层)/电磁波屏蔽膜2,该滤光器能简便地制造并具有优良的光学性能。
(制备电磁波屏蔽膜2)
按照下面步骤制造透明度略差的电磁波屏蔽膜2:通过上述的Nikaflex SAF的粘合剂层,将具有粗糙表面的厚18μm的导电材料的电解铜箔层叠在Cosmoshine A-4100(Toyobo Corporation生产的PET薄膜的商品名,厚度为100μm)上,使该粗糙面与环氧树脂粘合剂片接触,在180℃和30kgf/cm2条件下加热,将它们粘合,通过光刻步骤,在制成的有铜箔的PET薄膜上形成铜格栅图案,格栅线宽度为25μm,线间距为500μm。
实施例10
采用与实施例8相同的方法,制造具有减反射性、近红外光吸收性和氖光吸收性但在粘性层中不含有机酸的本发明的近红外光吸收滤光片,除了将上述表4所示的胶粘剂的原料中的丙烯酸类树脂(商品名为PTR-2500T)改变为PTR-5500(商品名,没有加入有机酸的丙烯酸类树脂,Nippon Kayaku Co.,Ltd生产)。将滤光片的脱模薄膜剥离,通过粘性层将剩余的薄膜粘贴到上述电磁波屏蔽膜2的网格表面,形成用于PDP的滤光器,其结构为(减反射透明支承体/NIR-Ne-吸收和调色粘性层)/电磁波屏蔽膜2,该滤光器能简便地制造并具有优良的光学性能。
实施例11
采用与实施例8相同的方法,制造本发明的近红外光吸收滤光片,该滤光片使用PET薄膜作为透明支承体,并在粘性层中含有2号的二亚铵化合物,不同之处是,使用除上述表4所示的用于胶粘剂的氖光吸收剂、黄色着色物和蓝色着色物之外的原料,且使用Cosmoshine A4300(商品名,PET薄膜,由ToyoboCorporation生产,厚度为100μm)替代Kayacoat ARS-D250-125。
实施例12
采用与实施例11相同的方法,制造本发明的近红外光吸收滤光片,该滤光片使用PET薄膜作为透明支承体,并在粘性层中含有1号的二亚铵化合物,不同之处是,使用1号二亚铵化合物替代2号二亚铵化合物。
比较例1
采用与实施例11相同的方法,制造比较用的近红外光吸收滤光片,该滤光片使用PET薄膜作为透明支承体,并在粘性层中含有下式(E)所示的二亚铵化合物,不同之处是,使用式(E)所示的二亚铵化合物替代2号二亚铵化合物。
比较例2
采用与实施例11相同的方法,制造比较用的近红外光吸收滤光片,该滤光片使用PET薄膜作为透明支承体,并在粘性层中含有下式(F)所示的二亚铵化合物,不同之处是,使用式(F)所示的二亚铵化合物替代2号二亚铵化合物。
比较例3
采用与实施例11相同的方法,制造比较用的近红外光吸收滤光片,该滤光片使用PET薄膜作为透明支承体,并在粘性层中含有下式(G)所示的二亚铵化合物,不同之处是,使用式(G)所示的二亚铵化合物替代2号二亚铵化合物。
评价试验(3)
(耐热性试验)
对实施例11和实施例12中制得的使用PET薄膜作为透明支承体的本发明各近红外光吸收滤光片以及在比较例1-3中制得的使用PET薄膜作为透明支承体的比较用的各近红外光吸收滤光片进行耐热性和耐湿热性测试。
无论二亚铵化合物的耐热性和耐湿热性是否变差,对波长为400-480nm的可见光和近红外光(波长为700-1,100nm)的吸收率都发生了变化,因此在这些波长区域(选择的三个波长)测定吸收率的变化。具体地,采用以下步骤测试耐热性和耐湿热性:在实施例和比较例中制得的各测试样品通过粘性层粘贴到1mm厚的浮法玻璃上;在80℃停留94小时,以测试耐热性,在60℃和90%RH(相对湿度)的恒热和恒湿浴中保持94小时,以测试耐湿热性;测定在上述试验之前和之后对三种波长(430nm,880nm and 980nm)的光的透射比;并观察粘性层的外观。
表6和表7列出外观的观察结果以及在各波长下透射比变化(在各波长下,试验后的透射比(%)-试验前的透射比(%))。
表6耐热性试验
实施例11实施例12比较例1比较例2比较例3 | 透射比变化(%) | 外观评价结果 | ||
430nm | 880nm | 980nm | 淡棕色且没有变化淡棕色和略微发黄淡棕色,变化很小变为淡黄色且发生积聚和不平变为淡黄绿色,并发生不平和大量积聚 | |
-1-46-15-25 | 194258 | 084244 |
表7耐湿热性试验
实施例11实施例12比较例1比较例2比较例3 | 透射比变化(%) | 外观评价结果 | ||
430nm | 880nm | 980nm | 淡棕色且没有变化淡棕色和略微发黄淡棕色,变化很小变为淡黄色且发生积聚和不平变为淡黄绿色,并发生不平和大量积聚 | |
-1-44-15-25 | 094858 | 094744 |
由表6和7的结果可以清楚知道,在耐热性和耐湿热性试验中,实施例11和实施例12的试片的粘性层中发生的不平以及在430nm波长时的变化都小于比较例2和比较例3的试片,因此外观几乎没有发生变化。与此不同,比较例1制得的试片显示近红外光吸光率明显下降。此外,实施例11的近红外光吸收滤光片在每个波长下的透射比变化以及外观的变化都小于实施例12的近红外光吸收滤光片。
Claims (21)
2.如权利要求1所述的二亚铵化合物,其特征在于,式(1)所示的二亚铵化合物是下式(2)表示的化合物,
式(2)中,R1至R8以及R9至R11具有与对式(1)所述的相同的含义。
3.如权利要求1或2所述的二亚铵化合物,其特征在于,式(1)中的R9至R11都是具有氟原子的脂族烃残基。
4.如权利要求3所述的二亚铵化合物,其特征在于,具有氟原子的脂族烃残基是三氟甲基。
5.如权利要求1-4中任一项所述的二亚铵化合物,其特征在于,式(1)中的R1至R8都是直链烷基或支链烷基。
6.如权利要求5所述的二亚铵化合物,其特征在于,所述直链烷基或支链烷基是C1-C6的直链或支链烷基。
7.如权利要求6所述的二亚铵化合物,其特征在于,所述直链烷基或支链烷基是C2-C5的直链或支链烷基。
8.如权利要求7所述的二亚铵化合物,其特征在于,所述直链烷基或支链烷基是乙基、正丙基、正丁基、异丁基或正戊基。
9.如权利要求1-4中任一项所述的二亚铵化合物,其特征在于,式(1)或式(2)中R1至R8表示的可具有取代基的脂族烃残基中的取代基各自独立地是卤原子、氰基、硝基、羟基、羧基、碳酰胺基、烷氧基羰基、酰基、芳基或烷氧基。
10.如权利要求9所述的二亚铵化合物,其特征在于,R1至R8都是被氰基取代的烷基。
11.如权利要求10所述的二亚铵化合物,其特征在于,被氰基取代的烷基是氰基丙基。
12.一种树脂组合物,该组合物包含如权利要求1-11中任一项所述的二亚铵化合物和一种树脂。
13.一种近红外光吸收滤光片,该滤光片具有一层包含如权利要求1-11中任一项所述的二亚铵化合物的层。
14.如权利要求13所述的近红外光吸收滤光片,其特征在于,所述包含二亚铵化合物的层是粘性层。
15.如权利要求14所述的近红外光吸收滤光片,其特征在于,所述粘性层包含防锈剂。
16.如权利要求15所述的近红外光吸收滤光片,其特征在于,所述防锈剂是1H-苯并三唑。
17.如权利要求14-16中任一项所述的近红外光吸收滤光片,其特征在于,粘性层中有机酸的含量为相对于该粘性层质量的0.5质量%或更小。
18.如权利要求14-17中任一项所述的近红外光吸收滤光片,其特征在于,所述粘性层包含在550-620nm波长区域具有最大吸收的化合物以及式(1)的二亚铵化合物。
19.一种用于等离子体显示板的滤光器,该滤光器包含如权利要求13-18中任一项所述的近红外光吸收滤光片以及电磁波屏蔽层。
20.一种等离子体显示板,具有权利要求19所述的用于等离子体显示板的滤光器。
21.一种光信息记录介质,该光信息记录介质包含含如权利要求1-11中任一项所述的二亚铵化合物的记录层。
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- 2005-09-02 EP EP05776988A patent/EP1787978B1/en not_active Not-in-force
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- 2005-09-02 JP JP2006535715A patent/JP4825676B2/ja not_active Expired - Fee Related
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CN105339438B (zh) * | 2013-07-05 | 2018-03-16 | 富士胶片株式会社 | 色素多聚体、着色组合物、硬化膜、彩色滤光片及制造方法、固体摄像元件及图像显示装置 |
Also Published As
Publication number | Publication date |
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JP4825676B2 (ja) | 2011-11-30 |
EP1787978B1 (en) | 2011-06-22 |
JP5414127B2 (ja) | 2014-02-12 |
US7521006B2 (en) | 2009-04-21 |
WO2006028006A1 (ja) | 2006-03-16 |
KR20070053740A (ko) | 2007-05-25 |
US20080067478A1 (en) | 2008-03-20 |
CN101010290B (zh) | 2011-08-03 |
JP2012012399A (ja) | 2012-01-19 |
KR101219108B1 (ko) | 2013-01-11 |
EP1787978A1 (en) | 2007-05-23 |
JPWO2006028006A1 (ja) | 2008-05-08 |
TW200624412A (en) | 2006-07-16 |
CA2578107A1 (en) | 2006-03-16 |
TWI374872B (zh) | 2012-10-21 |
EP1787978A4 (en) | 2008-09-10 |
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