CN116997831A - 抬头显示器用光学功能膜、光学层叠体、功能性玻璃、及抬头显示器系统 - Google Patents
抬头显示器用光学功能膜、光学层叠体、功能性玻璃、及抬头显示器系统 Download PDFInfo
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- CN116997831A CN116997831A CN202280021770.7A CN202280021770A CN116997831A CN 116997831 A CN116997831 A CN 116997831A CN 202280021770 A CN202280021770 A CN 202280021770A CN 116997831 A CN116997831 A CN 116997831A
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
- B32B17/1044—Invariable transmission
- B32B17/10458—Polarization selective transmission
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10165—Functional features of the laminated safety glass or glazing
- B32B17/10431—Specific parts for the modulation of light incorporated into the laminated safety glass or glazing
- B32B17/10467—Variable transmission
- B32B17/10495—Variable transmission optoelectronic, i.e. optical valve
- B32B17/10504—Liquid crystal layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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Abstract
本发明的抬头显示器用光学功能膜(10)具备(A)2层以上的位相差层(101)及(B)接着层(102)。接着层(102)与至少一层的位相差层(101)相邻,且接着层(102)的折射率和与接着层(102)相邻的位相差层(101)的快轴方向中的折射率的差的绝对值未达0.060。
Description
技术领域
本发明涉及例如应用于抬头显示器的较优选光学功能膜、光学层叠体、功能性玻璃、及使用这些的抬头显示器。
背景技术
作为在汽车、飞机等中对驾驶人员显示信息的方法为使用导航系统、抬头显示器(以下称为“HUD”)等。HUD为将从液晶显示器(以下也称为“LCD”)等图像投影装置投射的图像投影于例如汽车的挡风玻璃等的系统。
从图像显示装置射出的射出光会于反射镜反射,进一步在挡风玻璃反射后到达观察人员。观察人员会看到投影于挡风玻璃的图像,但图像看起来会像是位于比挡风玻璃更远的图像位置。该方法中,驾驶人员可在注视挡风玻璃前方的状态下在几乎不移动视线下获得各种信息,故比必须移动视线的以往汽车导航更为安全。
在HUD系统中,显示信息会与实际从挡风玻璃看到的景色重叠并投影,但显示光会在挡风玻璃的室内侧及室外侧的2个表面反射,故反射像会成为重影,存在不易看到显示信息的问题。
相对于该问题,已知在汽车用挡风玻璃使用可将偏光方向变更90°的位相差元件,据此可改善反射像成为重影的问题。例如专利文献1中揭示将S偏光的显示光以布鲁斯特角入射于内部具备膜状光旋转器的汽车用挡风玻璃时,部分S偏光在车内侧挡风玻璃表面反射,通过该表面的S偏光会通过光旋转器转换为P偏光,进一步在车外侧挡风玻璃表面使所有P偏光射出车外,从而预防重影。但是,在该汽车用挡风玻璃等中若无法非常有效地进行S偏光-P偏光间的转换,则会因未射出车外而折回的S偏光产生重影。
另外,作为抑制重影的其它方法,已知有将使用胆固醇液晶层制作的圆偏光反射膜夹于2片1/4波长板而形成光控制膜,并使用该光控制膜入射P偏光的技术(专利文献2)。该技术中,入射的线性偏光会通过1/4波长板而转换为圆偏光,在使用胆固醇液晶层制作的光反射膜转换的圆偏光会反射,据此可让观察人员视觉确认。但是,即使是该技术,仍希望入射于车内侧的1/4波长板的P偏光尽可能有效地转换为圆偏光,且希望通过胆固醇液晶层入射于车外侧1/4的波长板的圆偏光更有效地转换为P偏光。
[现有技术文献]
[专利文献]
专利文献1:日本特开平6-40271号公报
专利文献2:日本专利第5973109号公报。
发明内容
[发明所欲解决的课题]
本发明的目的在于提供在宽广波长区域具有优异的偏光转换能力的抬头显示器用光学功能膜、光学层叠体、功能性玻璃及使用这些的抬头显示器系统。
[用以解决课题的手段]
本发明的实施方式的抬头显示器用光学功能膜具备(A)2层以上的位相差层及(B)接着层,前述接着层与至少一层的位相差层相邻,且前述接着层的折射率和与前述接着层相邻的位相差层的快轴方向中的折射率的差的绝对值未达0.060。
本发明的一实施态样中,前述(B)接着层与2个位相差层相邻设置,且前述接着层的折射率与2层的位相差层的快轴方向中的各折射率的差的绝对值皆未达0.060。
根据本发明的一实施态样,前述(B)接着层在25℃的弹性模数与140℃的弹性模数的差为500MPa以下。
本发明的一实施态样中,前述(A)2层以上的位相差层中的至少一层为1/2波长板。
本发明的一实施态样中,前述(A)2层以上的位相差层皆为1/2波长板。
本发明的一实施态样中,前述(B)接着层为使硬化性化合物硬化而成的硬化膜。
本发明的一实施态样中,前述硬化性化合物为光硬化性化合物。
本发明的实施态样的抬头显示器用光学层叠体是在本实施方式的抬头显示器用光学功能膜上进一步层叠(C)中间膜。
本发明的实施态样的抬头显示器用功能性玻璃具备本实施方式的抬头显示器用光学功能膜或抬头显示器用光学层叠体、及(D)玻璃板。
本发明的实施态样的抬头显示器系统具备作为显示介质的本实施方式的抬头显示器用光学功能膜、抬头显示器用光学层叠体、或抬头显示器用功能性玻璃。
本发明的一实施态样中,从显示图像投影装置射出的光是从配置有前述(A)2层以上的位相差层中具有最高折射率的位相差层的一侧入射。
本发明的一实施态样中,从显示图像投影装置射出的光为S偏光。
[发明的功效]
根据本发明可实现在宽广波长区域具有优异的偏光转换能力的抬头显示器用光学功能膜、光学层叠体、功能性玻璃及使用这些的抬头显示器系统。
附图说明
图1表示本发明的抬头显示器用光学功能膜的一实施方式的侧面剖面图。
图2表示本发明的抬头显示器用光学层叠体的一实施方式的侧面剖面图。
图3表示本发明的抬头显示器用功能性玻璃的一实施方式的侧面剖面图。
图4表示本发明的抬头显示器系统的一实施方式的示意图。
图5表示本发明的抬头显示器系统的其它实施方式的示意图。
具体实施方式
以下参照附图说明本发明的实施方式。另外,下述实施方式仅为例示本发明的数个代表实施方式,可在本发明的范围内实施各种变更。另外,以下有时会省略“抬头显示器用”而仅记载为光学功能膜、光学层叠体、功能性玻璃。另外,“(甲基)丙烯酰基”、“(甲基)丙烯酸酯”等术语分别表示“丙烯酰基”或“甲基丙烯酰基”、“丙烯酸酯”或“甲基丙烯酸酯”。另外,“抬头显示器”有时会记载为HUD,用于位相差层的膜有时会记载为位相差膜。
[光学功能膜]
本发明的光学功能膜具备(A)2层以上的位相差层及(B)接着层,接着层与至少一层的位相差层相邻,且接着层的折射率和与该接着层相邻的位相差层的快轴方向中的折射率的差的绝对值未达0.060。据此可消除投影位置所造成的重影产生不均,可在不依赖投影位置而抑制重影的产生,故可提供在宽广波长区域具有优异的偏光转换能力的光学功能膜。
图1呈示本发明的光学功能膜的一实施方式,光学功能膜10中层叠有位相差层101及接着层102。图1中,接着层102分别与2个位相差层101相邻设置,也就是于接着层102的两面分别层叠2个位相差层101。层叠有接着层102及位相差层101时,在位相差层101中,后述支撑基板较优选为设置于光学功能膜10外侧,也就是设于不与接着层102接触的侧。
<(A)位相差层>
本发明的光学功能膜具有2层以上的位相差层,各位相差层所具有的位相差层为具有转换入射光的偏光轴的功能的层,可举例如(A-1)1/2波长板、(A-2)1/4波长板、(A-3)1/2波长板与圆偏光反射层的层叠体、(A-4)1/4波长板与圆偏光反射层的层叠体、及(A-5)其它具有任意位相差的层。2层以上的位相差层可任意组合上述(A-1)至(A-5)所记载地位相差层并使用,且分别可为相同或相异,但较优选为2层以上的位相差层中的至少一层为1/2波长板,更优选是皆为(A-1)1/2波长板,特优选为2层的1/2波长板。具体而言,较优选为(A)2层以上的位相差层整体发挥作为1/2波长板功能的态样,或是即使组合(A-1)至(A-5)的位相差层其整体也发挥作为1/2波长板功能的态样。圆偏光反射层例如较优选为使用胆固醇状液晶的胆固醇状液晶层。以液晶的配向性的观点来看,圆偏光反射层的厚度上限较优选为10μm以下,更优选为5μm以下。另一方面,以液晶的聚合性的观点来看,圆偏光反射层的厚度下限较优选为0.3μm以上,更优选为0.5μm以上。
<1/2波长板>
使用1/2波长板作为位相差层时,1/2波长板为具有将P偏光转换为S偏光或将S偏光转换为P偏光的功能,也就是具有转换偏光轴的功能的位相差元件。如此1/2波长板例如可通过将聚碳酸酯或环烯烃聚合物所构成的膜以位相差成为波长的1/2的方式单轴延伸,或是将水平配向的聚合性液晶以位相差成为波长的1/2的厚度配向而获得。一般而言,使用水平配向的聚合性液晶的1/2波长板是由聚合性液晶层及支撑基板所构成,该聚合性液晶层是作为具有转换偏光轴的作用的层,该支撑基板涂布有形成该聚合性液晶层的涂布液。但支撑基板并非本发明的光学功能膜的必要构成构件,也可将聚合性液晶层转印至其它基材(例如中间膜或玻璃板)而使用。通过使用1/2波长板可将不在表面反射而透射的S偏光或P偏光转换为P偏光或S偏光,故可降低配置于光学功能膜外侧的1/2波长板的支撑基板的反射,而可抑制重影的产生。
以液晶的配向性的观点来看,如此1/2波长板的厚度上限较优选为10μm以下,更优选为5μm以下。另一方面,以液晶的聚合性的观点来看,1/2波长板的厚度下限较优选为0.3μm以上,更优选为0.5μm以上。光从相对于1/2波长板的主表面倾斜的位置入射时,有因光的入射角而使位相差变化的情形。此时为了更严密地配合位相差,故例如可使用调整位相差元件的折射率的位相差元件,据此可抑制伴随入射角的位相差变化。例如在以位相差元件的面内的慢轴方向的折射率为nx,在位相差元件的面内与慢轴方向正交的方向的折射率为ny,位相差元件的厚度方向的折射率为nz时,下述式(1)所示的系数Nz较优选为0.3以上1.0以下,更优选为0.5以上0.8以下的方式进行控制。
Nz=(nx-nz)/(nx-ny)...(1)
1/2波长板含有聚合性液晶层时,构成聚合性液晶层的液晶组合物涂布于支撑基板上。在1/2波长板用于HUD时,为了保持显示图像的视觉确认性,该支撑基板较优选为在可见光区域中为透明,具体而言为波长380nm以上780nm以下的可见光线透射率为50%以上即可,较优选为70%以上,更优选为85%以上。另外,支撑基板可着色或不着色,但较优选为着色较少。另外,支撑基板的折射率较优选为1.2以上2.0以下,更优选为1.4以上1.8以下。可因应用途适当地选择支撑基板的厚度,较优选为5μm以上1000μm以下,更优选为10μm以上250μm以下,特优选为15μm以上150μm以下。
支撑基板可为单层,也可为2层以上的层叠体。支撑基板的例子可举例如三乙酸纤维素(TAC)、压克力、聚碳酸酯、聚氯乙烯、聚烯烃及聚对苯二甲酸乙二酯(PET)等。这些中较优选为双折射性较少的三乙酸纤维素(TAC)、聚烯烃及压克力等。
接着说明使用上述具有聚合性基的向列型液晶单体而制作1/2波长板的方法。该方法是例如将具有聚合性基的向列型液晶单体溶解于溶剂中,接着添加光聚合引发剂。如此溶剂只要可溶解所使用的液晶单体即可,并无特别限定,可举例如环戊酮、甲苯、甲基乙酮、甲基异丁酮等,较优选为环戊酮及甲苯等。其后将该溶液以厚度尽可能均一的方式涂布于使用作为支撑基板的PET膜或TAC膜等塑胶基板上,一边通过加热去除溶剂,一边以可在支撑基板上形成液晶并配向的温度条件放置固定时间。此时,可在涂布塑胶膜表面之前,预先进行于所求配向方向的摩擦处理、或将可通过照射偏光发挥光配向性的光配向材料(配向膜涂布液)成膜于塑胶膜基板表面并照射偏光等的配向处理,据此可使液晶的配向更均一。因此可将1/2波长板的慢轴控制在所求角度,且可降低1/2波长板的雾度值。接着在保持该配向状态下以高压汞灯等于向列型液晶单体照射紫外线,使液晶的配向固定化,据此可得具有所求慢轴的1/2波长板。
<1/4波长板>
位相差层也可使用1/4波长板。1/4波长板为具有将圆偏光转换为线性偏光的功能的位相差元件。如此1/4波长板例如可将聚碳酸酯或环烯烃聚合物所构成的膜以位相差成为波长的1/4的方式单轴延伸,或是将水平配向的聚合性液晶以位相差成为波长的1/4的厚度配向,据此而获得。另外,与1/2波长板相同,1/4波长板较优选也为含有聚合性液晶层。此时,1/4波长板是由聚合性液晶层及支撑基板所构成,该聚合性液晶层是作为具有转换偏光轴的作用的层,该支撑基板涂布有形成该聚合性液晶层的涂布液。聚合性液晶层及支撑基板可使用与上述1/2波长板所使用的向列型液晶单体、支撑基板相同的材料。另外,与1/2波长板相同,支撑基板并非光学功能膜的必要构成构件,也可将聚合性液晶层转印至其它基材(例如中间膜或玻璃板)而使用。
在波长色散所造成的位相差偏差较大时,1/4波长板也可使用称为宽波带1/4波长板的位相差元件。宽波带1/4波长板是指可降低位相差的波长依赖性的位相差元件,可举例如将具有相同波长色散的1/2波长板及1/4波长板以各自的慢轴的夹角角度成为60°的方式层叠的位相差元件、降低位相差的波长依赖性的聚碳酸酯系位相差元件(帝人公司制:PUREACE WR-S)等。另外,如HUD,光的入射角为相对于1/4波长板倾斜入射时,因位相差元件而异有因光的入射角度使位相差变化的情形。此时,作为更严密地配合位相差的方法,例如可使用调整位相差元件的折射率的位相差元件,据此可抑制伴随入射角的位相差变化。作为如此例,在以位相差元件的面内的慢轴方向的折射率为nx,在位相差元件的面内与慢轴方向正交的方向的折射率为ny,位相差元件的厚度方向的折射率为nz时,以上述式(1)所示系数Nz较优选为0.3以上1.0以下,更优选为0.5以上0.8以下的方式进行控制。
以液晶的配向性的观点来看,1/4波长板的厚度上限较优选为10μm以下,更优选为5μm以下。另一方面,1/4波长板的厚度下限较优选为0.3μm以上,更优选为0.5μm以上。
使用作为位相差层的1/2波长板或1/4波长板较优选为包含具有聚合性液晶的聚合性液晶层。聚合性液晶是指分子内具有聚合性基且在某温度范围或浓度范围显示液晶性的向列型液晶单体。聚合性基可举例如(甲基)丙烯酰基、乙烯基、查耳酮基、桂皮酰基及环氧基等。另外,为了使聚合性液晶显示液晶性,较优选为分子内具有介晶基。介晶基是指例如联苯基、联三苯基、(聚)安息香酸苯酯基、(聚)醚基、亚苄基苯胺基、或苊并喹噁啉基等棒状、板状的取代基、或联三撑苯基、酞青基、或氮杂冠基等圆盘状的取代基,也就是具有诱导液晶相行为的能力的基。具有棒状或板状的取代基的液晶化合物是该技术领域所公开已知的杆状液晶。具有如此聚合性基的向列型液晶单体可举例如日本特开2003-315556号公报及日本特开2004-29824号公报等所记载的聚合性液晶、PALIOCOLOR系列(BASF公司制)及RMM系列(Merck公司制)等聚合性液晶。这些具有聚合性基的向列型液晶单体可单独使用或将多种混合使用。
另外,也可添加可与具有聚合性基的向列型液晶单体反应的不具液晶性的聚合性化合物。如此化合物可举例如紫外线硬化型树脂等。紫外线硬化型树脂可举例如二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯与1,6-六亚甲基二异氰酸酯的反应生成物、具有异三聚氰环的三异氰酸酯与季戊四醇三(甲基)丙烯酸酯的反应生成物、季戊四醇三(甲基)丙烯酸酯与异佛尔酮二异氰酸酯的反应生成物、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、双三羟甲基丙烷四(甲基)丙烯酸酯、三(丙烯酰氧基乙基)异三聚氰酸酯、三(甲基丙烯酰氧基乙基)异三聚氰酸酯、甘油三环氧丙基醚与(甲基)丙烯酸的反应生成物、己内酯改质三(丙烯酰氧基乙基)异三聚氰酸酯、三羟甲基丙烷三环氧丙基醚与(甲基)丙烯酸的反应生成物、三酸甘油酯二(甲基)丙烯酸酯、丙二醇二环氧丙基醚与(甲基)丙烯酸的反应生成物、聚丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、1,6-己二醇二环氧丙基醚与(甲基)丙烯酸的反应生成物、1,6-己二醇二(甲基)丙烯酸酯、甘油二(甲基)丙烯酸酯、乙二醇二环氧丙基醚与(甲基)丙烯酸的反应生成物、二乙二醇二环氧丙基醚与(甲基)丙烯酸的反应生成物、双(丙烯酰氧基乙基)羟基乙基异三聚氰酸酯、双(甲基丙烯酰氧基乙基)羟基乙基异三聚氰酸酯、双酚A二环氧丙基醚与(甲基)丙烯酸的反应生成物、(甲基)丙烯酸四氢糠酯、己内酯改质(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、聚丙二醇(甲基)丙烯酸酯、聚乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基羟基丙酯、丙烯酰基吗啉、甲氧基聚乙二醇(甲基)丙烯酸酯、甲氧基四乙二醇(甲基)丙烯酸酯、甲氧基三乙二醇(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸环氧丙酯、(甲基)丙烯酸甘油酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸N,N-二甲胺基乙酯、(甲基)丙烯酸2-氰基乙酯、丁基环氧丙基醚与(甲基)丙烯酸的反应生成物、丁氧基三乙二醇(甲基)丙烯酸酯及丁二醇单(甲基)丙烯酸酯等,这些可单独使用或多种混合使用。需以含有向列型液晶单体的组合物不会失去液晶性的程度添加这些不具液晶性的紫外线硬化型树脂,较优选为相对于具有聚合性基的向列型液晶单体100质量份为0.1质量份以上20质量份以下,更优选为1.0质量份以上10质量份以下。
上述具有聚合性基的向列型液晶单体及不具液晶性的聚合性化合物为紫外线硬化型时,为了使包含这些的组合物通过紫外线硬化而添加光聚合引发剂。光聚合引发剂可举例如2-甲基-1-[4-(甲基硫基)苯基]-2-N-吗啉基丙烷-1(IGM Resins B.V.公司制Omnirad(注册商标)907)、1-羟基环己基苯基酮(IGM Resins B.V.公司制Omnirad(注册商标)184)、4-(2-羟基乙氧基)-苯基(2-羟基-2-丙基)酮(IGM Resins B.V.公司制Omnirad(注册商标)2959)、1-(4-十二烷基苯基)-2-羟基-2-甲基丙烷-1-酮(Merck公司制Darocur(注册商标)953)、1-(4-异丙基苯基)-2-羟基-2-甲基丙烷-1-酮(Merck公司制Darocur(注册商标)1116)、2-羟基-2-甲基-1-苯基丙烷-1-酮(IGM Resins B.V.公司制Omnirad(注册商标)1173)及二乙氧基苯乙酮等苯乙酮系化合物;安息香、安息香甲基醚、安息香乙基醚、安息香异丙基醚、安息香异丁基醚及2,2-二甲氧基-2-苯基苯乙酮(BASF公司制Irgacure651)等安息香系化合物;苯甲酰基安息香酸、苯甲酰基安息香酸甲酯、4-苯基二苯基酮、羟基二苯基酮、4-苯甲酰基-4’-甲基二苯基硫醚、3,3’-二甲基-4-甲氧基二苯基酮(日本化药公司制KAYACURE(注册商标)MBP)等二苯基酮系化合物;以及噻吨酮、2-氯噻吨酮(日本化药公司制KAYACURE(注册商标)CTX)、2-甲基噻吨酮、2,4-二甲基噻吨酮(日本化药公司制KAYACURE(注册商标)RTX)、异丙基噻吨酮、2,4-二氯噻吨酮(日本化药公司制KAYACURE(注册商标)CTX)、2,4-二乙基噻吨酮(日本化药公司制KAYACURE(注册商标)DETX)及2,4-二异丙基噻吨酮(日本化药公司制KAYACURE(注册商标)DITX)等噻吨酮系化合物等。较优选的光聚合引发剂可举例如Irgacure(注册商标)OXE01、Irgacure(注册商标)OXE02、Irgacure(注册商标)OXE03、Irgacure(注册商标)OXE04(皆为BASF公司制)、Omnirad(注册商标)TPOH、Omnirad(注册商标)1300、Omnirad(注册商标)184、Omnirad(注册商标)369、Omnirad(注册商标)379、Omnirad(注册商标)819、Omnirad(注册商标)127、Omnirad(注册商标)907及Omnirad(注册商标)1173(皆为IGM Resins B.V.公司制),特优选为Omnirad(注册商标)TPOH、Irgacure(注册商标)OXE01、Irgacure(注册商标)OXE02、Omnirad(注册商标)1300及Omnirad(注册商标)907。这些光聚合引发剂可以使用1种或将多种以任意比率混合使用。
使用二苯基酮系化合物或噻吨酮系化合物作为光聚合引发剂时,为了促进光聚合反应而可并用助剂。如此助剂可举例如三乙醇胺、甲基二乙醇胺、三异丙醇胺、正丁胺、N-甲基二乙醇胺、甲基丙烯酸二乙胺基乙酯、米其勒酮、4,4’-二乙胺基苯酮、4-二甲胺基安息香酸乙酯、4-二甲胺基安息香酸(正丁氧基)乙酯、及4-二甲胺基安息香酸异戊酯等胺系化合物。
上述光聚合引发剂及助剂的添加量较优选为在不会影响液晶组合物的液晶性的范围内使用,其量相对于该液晶组合物中以紫外线硬化的化合物100质量份较优选为0.5质量份以上10质量份以下,更优选为2质量份以上8质量份以下。另外,助剂相对于光聚合引发剂较优选为含有0.5倍量以上2倍量以下的范围。
[(B)接着层]
本发明的光学功能膜具备与(A)2层以上的位相差层的至少一层位相差层相邻的接着层,且该相邻的位相差层的快轴方向中的折射率与(B)接着层的折射率的差的绝对值未达0.060。接着层与2个位相差层相邻设置时,较优选为接着层的折射率与2层的位相差层的快轴方向中的各折射率的差的绝对值皆未达0.060。
<折射率>
接着层与位相差层相邻。接着层的折射率需要与相邻的位相差层的快轴方向中的折射率为相同程度,具体而言,折射率的差的绝对值未达0.060,较优选为未达0.055,更优选为未达0.045,特优选为未达0.040。接着层的折射率及位相差层的快轴方向中的折射率可使用市面贩卖数码折射计等测定。
接着层的折射率较优选为1.400以上1.800以下。接着层的折射率上限依照较优选顺序为1.750、1.700、1.650,特优选为1.600。接着层的折射率下限依照较优选顺序为1.450、1.500,特优选为1.550。因此,(接着层的折射率最优选为1.550以上1.600以下。另外,接着层的折射率可将形成接着层所使用的后述接着剂组合物的硬化膜使用分光光度计(例如岛津制作所制UV-3600)而测定。另外,实现上述折射率的方法可举出选择未硬化状态中的折射率为1.400以上1.700以下的接着剂组合物。接着剂组合物的未硬化状态中的折射率上限依照较优选顺序为1.700、1.650、1.600、1.550,特优选为1.545。接着剂组合物的未硬化状态中的折射率下限依照较优选顺序为1.400、1.450、1.500,特优选为1.520。因此,接着剂组合物的未硬化状态中的折射率最优选为1.520以上1.545以下。
另外,与接着层相邻的位相差层的快轴方向中的折射率较优选为1.500以上1.850以下。位相差层的快轴方向中的折射率上限依照较优选顺序为1.800、1.750、1.700、1.650,特优选为1.620。位相差层的快轴方向中的折射率下限依照较优选顺序为1.550、1.560、1.570、1.580、1.590,特优选为1.595。因此,位相差层的快轴方向中的折射率最优选为1.595以上1.620以下。另外,2层位相差层与接着层相邻时,也就是2层位相差层通过接着层而接着时,位相差层的快轴方向中的折射率与接着层的折射率的上述关系需要在与两位相差层之间成立。
<平均反射率>
接着剂层的平均反射率较优选为5.000%以上7.000%以下。于基材上制作使后述接着剂组合物硬化而成的硬化膜后,使用分光光度计(例如岛津制作所制UV-3600)测定多次400nm以上700nm以下的波长范围的偏光入射时的接着层(硬化膜)的正交反射率,并计算其平均,据此可求平均反射率。接着剂层的平均反射率上限依照较优选顺序为6.950%、6.850%、6.750%、6.650%,特优选为6.600%。另外,接着剂层的平均反射率下限依照较优选顺序为5.500%、5.580%、5.590%、5.600%,特优选为5.700%。因此,接着剂层的平均反射率最优选为5.700%以上6.600%以下。
另外,位相差层的平均反射率较优选为5.000%以上8.000%以下。位相差层的平均反射率上限依照较优选顺序为7.500%、7.000%、6.500%,特优选为6.000%。另外,位相差层的平均反射率下限依照较优选顺序为5.100%、5.200%,特优选为5.300%。因此,位相差层的平均反射率最优选为5.300%以上6.000%以下。
<弹性模数>
接着层中,室温中的弹性模数与高温中的弹性模数的差较优选为500MPa以下。室温较优选为5℃以上40℃以下,更优选为25℃。高温较优选为70℃以上200℃以下,更优选为140℃。也就是,最优选为25℃的弹性模数与140℃的弹性模数的差为500MPa以下。通过使用显示如此弹性模数的接着剂而可降低橘皮(orange peel)的问题。在此,橘皮也被称为柚皮状(日文:ゆず肌),为膜的凹凸所造成的缺点。专利文献1及2等所揭示以往的光学膜容易产生成型性不良或层间剥离等问题,另外,若通过接着剂使膜彼此贴合并通过聚乙烯丁醛等中间膜以玻璃板夹持并压接,则会有产生一些被称为橘皮的缺点,而损及作为挡风玻璃的美观的情形。通过使25℃的弹性模数与140℃的弹性模数的差为500MPa以下,即使通过中间膜将本发明的光学功能膜以玻璃板夹持并压接,也可抑制橘皮的产生,可实现优异美观的挡风玻璃。
于基材上制作使后述接着剂组合物硬化而成的硬化膜后,使用万能试验机(例如A&D公司制TENSILON万能试验机RTG-1210)测定接着层(硬化膜)的弹性模数,据此可求接着层的弹性模数。室温及高温中的接着层的弹性模数较优选为500MPa以下,更优选为350MPa以下,又更优选为300MPa以下。弹性模数为根据JIS K 7127:1999(ISO527-3:2012)的测定方法使用拉伸试验机以速度100mm/min拉伸试料,而求试料断裂时的强度及伸长率,并由试料变形前的最大弹性(SS曲线的最大斜率的切线的一次方程式)测定。
<硬化性化合物>
接着层较优选为使硬化性化合物硬化而成的硬化膜。硬化性化合物可举例如热硬化性化合物或光硬化性化合物等,较优选为光硬化性化合物。
<热硬化性化合物>
热硬化性化合物可举例如具有环氧基、氧杂环丁烷基等环状醚结构的硬化性化合物。具有环状醚结构的热硬化性化合物并无特别限定,可举例如环氧树脂(含有脂环式环氧树脂的脂肪族环氧树脂或芳香族环氧树脂)、氧环丁烷树脂、呋喃树脂等。以反应速度或通用性的观点来看,这些中较优选为环氧树脂(可含有脂肪族环,例如碳数3至12的脂肪族环)、氧环丁烷树脂。环氧树脂并无特别限定,可举例如酚酚醛清漆型、甲酚酚醛清漆型、联苯基酚醛清漆型、三酚酚醛清漆型、二环戊二烯酚醛清漆型等酚醛清漆型;双酚A型、双酚F型、2,2’-二烯丙基双酚A型、氢化双酚型、聚氧丙烯双酚A型等双酚型等。另外,其它也可举出环氧丙胺等。
作为环氧树脂的市面贩卖品,酚酚醛清漆型环氧树脂可举例如EPICLON(注册商标)系列的N-740、N-770、N-775(皆为DIC公司制)、Epikote(注册商标)152、Epikote(注册商标)154(皆为JAPAN EPOXY RESIN公司制)等。甲酚酚醛清漆型可举例如EPICLON(注册商标)系列的N-660、N-665、N-670、N-673、N-680、N-695、N-665-EXP、N-672-EXP(皆为DIC公司制);联苯基酚醛清漆型可举例如NC-3000P(日本化药公司制);三酚酚醛清漆型可举例如EP1032S50、EP1032H60(皆为JAPAN EPOXY RESIN公司制);二环戊二烯酚醛清漆型可举例如XD-1000-L(日本化药公司制)、HP-7200(DIC公司制);双酚A型环氧化合物可举例如Epikote(注册商标)828、Epikote(注册商标)834、Epikote(注册商标)1001、Epikote(注册商标)1004(皆为JAPAN EPOXY RESIN公司制)、EPICLON(注册商标)850、EPICLON(注册商标)860、EPICLON(注册商标)4055(皆为DIC公司制);双酚F型环氧化合物的市面贩卖品可举例如Epikote(注册商标)807(JAPAN EPOXY RESIN公司制)、EPICLON(注册商标)830(DIC公司制);2,2’-二烯丙基双酚A型可举例如RE-810NM(日本化药公司制);氢化双酚型可举例如ST-5080(东都化成公司制);聚氧丙烯双酚A型可举例如EP-4000、EP-4005(皆为旭电化工业公司制)等。另外,脂环式环氧树脂并无特别限定,可举例如Celloxide(注册商标)2021、Celloxide(注册商标)2080、Celloxide(注册商标)3000(以上皆为Daicel-UCB公司制)等。
氧环丁烷树脂的市面贩卖品可举例如ETERNACOLL(注册商标)EHO、ETERNACOLL(注册商标)OXBP、ETERNACOLL(注册商标)OXTP、ETERNACOLL(注册商标)OXMA(皆为宇部兴产公司制)等。具有这些环状醚基的硬化性化合物可单独使用或并用2种以上。
<光硬化性化合物>
光硬化性化合物可举例如具有乙烯基、乙烯基醚基、烯丙基、马来酰亚胺基、(甲基)丙烯酰基等的树脂。以反应性或通用性的观点来看,这些中较优选为具有(甲基)丙烯酰基的树脂,例如(甲基)丙烯酸酯化合物。
具有(甲基)丙烯酰基的树脂可举例如(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基丙酯、1,4-丁二醇单(甲基)丙烯酸酯、卡必醇(甲基)丙烯酸酯、丙烯酰基吗啉、属于含有羟基的(甲基)丙烯酸酯与多元羧酸化合物的酸酐的反应物的半酯、聚乙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、三羟甲基丙烷聚乙氧基三(甲基)丙烯酸酯、甘油聚丙氧基三(甲基)丙烯酸酯、羟基三甲基乙酸新戊二醇的ε-己内酯加成物的二(甲基)丙烯酸酯(例如日本化药公司制KAYARAD(注册商标)系列的HX-220、HX-620等)、季戊四醇四(甲基)丙烯酸酯、二季戊四醇与ε-己内酯的反应物的聚(甲基)丙烯酸酯、二季戊四醇聚(甲基)丙烯酸酯(例如日本化药公司制KAYARAD(注册商标)DPHA等)、单或聚环氧丙基化合物与(甲基)丙烯酸的反应物的环氧基(甲基)丙烯酸酯等(甲基)丙烯酸酯化合物。
属于单或聚环氧丙基化合物与(甲基)丙烯酸的反应物的环氧基(甲基)丙烯酸酯所使用的环氧丙基化合物并无特别限制,可举例如双酚A、双酚F、双酚S、4,4’-联苯基酚、四甲基双酚A、二甲基双酚A、四甲基双酚F、二甲基双酚F、四甲基双酚S、二甲基双酚S、四甲基-4,4’-联苯酚、二甲基-4,4’-联苯基酚、1-(4-羟基苯基)-2-[4-(1,1-双-(4-羟基苯基)乙基)苯基]丙烷、2,2’-亚甲基-双(4-甲基-6-叔丁基酚)、4,4’-亚丁基-双(3-甲基-6-叔丁基酚)、三羟基苯基甲烷、间苯二酚、对苯二酚、邻苯三酚、具有二亚异丙基骨架的酚类、1,1-二-4-羟基苯基芴等具有芴骨架的酚类、酚化聚丁二烯、溴化双酚A、溴化双酚F、溴化双酚S、溴化酚酚醛清漆、溴化甲酚酚醛清漆、氯化双酚S、氯化双酚A等多酚类的环氧丙基醚化物。
这些属于单或聚环氧丙基化合物与(甲基)丙烯酸的反应物的环氧基(甲基)丙烯酸酯可通过使该环氧基与同当量的(甲基)丙烯酸进行酯化反应而获得。该合成反应可通过一般已知方法进行。例如将间苯二酚二环氧丙基醚、与其同当量的(甲基)丙烯酸、催化剂(例如苄基二甲胺、三乙胺、苄基三甲基铵氯化物、三苯基膦、三苯基锑化氢等)、及聚合抑制剂(例如对苯二酚单甲醚、对苯二酚、甲对苯二酚、啡噻嗪、二丁基羟基甲苯等)一起添加,例如于80至110℃进行酯化反应。如此所得的(甲基)丙烯酸化间苯二酚二环氧丙基醚为具有自由基聚合性的(甲基)丙烯酰基的树脂。
硬化性化合物较优选为热硬化性树脂或光硬化性树脂,更优选为光硬化性树脂,特优选为分子内兼具有3个以上的(甲基)丙烯酰基的光硬化性树脂。分子内兼具有3个以上的(甲基)丙烯酰基及极性官能团的光硬化性树脂可举例如季戊四醇三丙烯酸酯(例如KAYARAD(注册商标)PET-30,日本化药公司制)、二季戊四醇五丙烯酸酯与二季戊四醇六丙烯酸酯的混合物(例如KAYARAD(注册商标)DPHA,日本化药公司制)、2-羟基-3-丙烯酰氧基甲基丙烯酸丙酯(例如701A,新中村化学工业公司制)、乙氧基化异三聚氰酸三丙烯酸酯(例如A-9300,新中村化学工业公司制)、ε-己内酯改质三-(2-丙烯酰氧基乙基)异三聚氰酸酯(例如A-9300-1CL,新中村化学工业公司制)等(甲基)丙烯酸酯单体化合物、双酚A型环氧基丙烯酸酯(例如R-115F、R-130、R-381等,日本化药公司制)、双酚F型环氧基丙烯酸酯(例如ZFA-266H,日本化药公司制)、酸改质环氧基丙烯酸酯(例如ZAR系列、ZCR系列,日本化药公司制)等环氧基丙烯酸酯树脂,聚酯系氨甲酸乙酯丙烯酸酯(例如UX3204、UX-4101、UXT-6100,日本化药公司制)、混合系氨甲酸乙酯丙烯酸酯(例如UX-6101、UX-8101,日本化药公司制)、聚醚系氨甲酸乙酯丙烯酸酯(UX-937、UXF-4001-M35,日本化药公司制)、酯系氨甲酸乙酯丙烯酸酯(例如DPHA-40H、UX-5000、UX-5102D-M20、UX-5103D、UX-5005,日本化药公司制)等氨甲酸乙酯丙烯酸酯树脂。分子内具有3个以上的(甲基)丙烯酰基的光硬化性树脂更优选为具有3个以上10个以下的(甲基)丙烯酰基,又更优选为具有4个以上8个以下的(甲基)丙烯酰基。
硬化性化合物的含量相对于接着层的总质量较优选为0.5质量%以上90质量%以下,更优选为5质量%以上70质量%以下。
<硬化剂>
接着层所使用的硬化性化合物较优选为使用硬化剂而硬化。另外,有时硬化剂与硬化引发剂有所区别,但在此将两者合称为硬化剂。
使用热硬化性化合物作为硬化性化合物时,较优选为并用热硬化剂。但热硬化性化合物为具有环状醚的热硬化性化合物时,也可适合使用通过光而产生阳离子或阴离子的光阳离子引发剂或光阴离子引发剂。
热硬化剂使用通过非共用电子对或分子内的阴离子而进行亲核反应的化合物。如此热硬化剂可举例如胺系硬化剂(以下也称为胺类)、酰肼系硬化剂(以下也称为酰肼类)、咪唑系硬化剂(以下也称为咪唑类)、聚酰胺树脂、二氰二胺、异氰酸酯、硫醇系硬化剂(硫醇类)、酚系硬化剂(酚类)等,但并不限定于这些。
胺类可举出脂肪族链状胺、脂肪族环状胺、芳香族胺、改质胺(胺加成物、酮亚胺等)等。另外,可为伯胺、仲胺、叔胺、季胺的任一者,以反应性的观点来看较优选为伯胺或仲胺。具体的胺类可举例如二胺基二苯基甲烷、二胺基二苯基砜、4,4’-二胺基-3,3’-二甲基二苯基甲烷、二胺基二苯基醚、二乙基甲基苯二胺、2-甲基-4,6-双(甲基硫基)-1,3-苯二胺、双苯胺、二乙基甲苯二胺、二乙基硫甲苯二胺、N,N’-双(仲丁胺基)二苯基甲烷等芳香族胺、甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、乙二胺、四甲基乙二胺、六亚甲基二胺、降莰烷二胺、聚醚胺、三撑乙四胺、四撑乙五胺等脂肪族胺、改质胺等。这些中较优选为二乙基甲基苯二胺、4,4’-二胺基-3,3’-二甲基二苯基甲烷、二乙基甲苯二胺。
酰肼类尤其适合使用有机酰肼化合物。有机酸酰肼化合物可举例如水杨酰肼、对苯二甲酰肼、间苯二甲酰肼、2,6-萘甲二酰肼、2,6-吡啶二酰肼、1,2,4-苯三酰肼、1,4,5,8-萘甲酸四酰肼、焦蜜石酸四酰肼等芳香族酰肼。另外,脂肪族酰肼可举例如甲酰肼、乙酰肼、丙酰肼、乙二酰肼、丙二酰肼、丁二酰肼、戊二酰肼、己二酰肼、庚二酰肼、癸二酰肼、1,4-环己烷二碳酰肼、二羟基丁二酰肼、羟基丁二酰肼、亚胺基二乙二酰肼、N,N’-六亚甲基双半卡肼、羟基丙三酰肼、氮基乙三酰肼、环己烷三碳酰肼、1,3-双(肼基碳基乙基)-5-异丙基乙内酰脲等具有乙内酰脲骨架,较优选为具有缬胺乙内酰脲骨架(乙内酰脲环的碳原子经异丙基取代的骨架)的二酰肼化合物、三(1-肼基羰基甲基)异三聚氰酸酯、三(2-肼基羰基乙基)异三聚氰酸酯、三(1-肼基羰基乙基)异三聚氰酸酯、三(3-肼基羰基丙基)异三聚氰酸酯、双(2-肼基羰基乙基)异三聚氰酸酯等。以硬化反应性与潜伏性的平衡的观点来看,这些中较优选为间苯二甲酰肼、丙二酰肼、己二酰肼、三(肼基羰基甲基)异三聚氰酸酯、三(1-肼基羰基乙基)异三聚氰酸酯、三(2-肼基羰基乙基)异三聚氰酸酯,三(3-肼基羰基丙基)异三聚氰酸酯,特优选为三(2-肼基羰基乙基)异三聚氰酸酯。
咪唑类可举例如2-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑、2,4-二胺基-6(2’-甲基咪唑(1’))乙基-均三嗪、2,4-二胺基-6(2’-十一烷基咪唑(1’))乙基-均三嗪、2,4-二胺基-6(2’-乙基,4-甲基咪唑(1’))乙基-均三嗪、2,4-二胺基-6(2’-甲基咪唑(1’))乙基-均三嗪异三聚氰酸加成物、2-甲基咪唑异三聚氰酸的2:3加成物、2-苯基咪唑异三聚氰酸加成物、2-苯基-3,5-二羟基甲基咪唑、2-苯基-4-羟基甲基-5-甲基咪唑、1-氰基乙基-2-苯基-3,5-二氰基乙氧基甲基咪唑的各种咪唑类、及这些咪唑类与邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三酸、焦蜜石酸、萘二羧酸、马来酸、草酸等多元羧酸的盐类。
硫醇类可举例如Karenz MT(注册商标)系列的PE1、BD1、NR1(皆为昭和电工公司制)、三羟甲基丙烷三(3-巯基丁酸酯)、三羟甲基乙烷三(3-巯基丁酸酯)等。另外,硫醇系硬化剂是指分子内具有至少一个硫醇基(SH)的硬化剂。
酚类可举例如将酚(可具有各种取代基)与福马林在酸催化剂下进行缩合反应而得的酚酚醛清漆类或双酚A、双酚S等。
使用热硬化剂时可并用硬化促进剂。硬化促进剂可举出酚类、有机酸、膦类、咪唑等。另外,硬化促进剂也包括具有作为热硬化剂的功能的化合物。
酚类可举例如将酚(可具有各种取代基)与福马林在酸催化剂下进行缩合反应而得的酚酚醛清漆类或双酚A、双酚S等。
有机酸可举出有机羧酸或有机磷酸等,较优选为有机羧酸。有机羧酸的具体例可举例如邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三酸、二苯基酮四羧酸、呋喃二羧酸等芳香族羧酸、琥珀酸、己二酸、十二烷二酸、癸二酸、硫二丙酸、环己烷二羧酸、三(2-羧甲基)异三聚氰酸酯、三(2-羧基乙基)异三聚氰酸酯、三(2-羧基丙基)异三聚氰酸酯、双(2-羧基乙基)异三聚氰酸酯等。
膦类可举例如三苯基膦、四苯基鏻四苯基硼酸盐等。
咪唑类可举例如2-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-甲基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-十一烷基咪唑、2,4-二胺基-6(2’-甲基咪唑(1’))乙基-均三嗪、2,4-二胺基-6(2’-十一烷基咪唑(1’))乙基-均三嗪、2,4-二胺基-6(2’-乙基-4-甲基咪唑(1’))乙基-均三嗪、2,4-二胺基-6(2’-甲基咪唑(1’))乙基-均三嗪异三聚氰酸加成物、2-甲基咪唑异三聚氰酸的2:3加成物、2-苯基咪唑异三聚氰酸加成物、2-苯基-3,5-二羟基甲基咪唑、2-苯基-4-羟基甲基-5-甲基咪唑、1-氰基乙基-2-苯基-3,5-二氰基乙氧基甲基咪唑等。
<光引发剂>
使用光硬化性化合物作为硬化性化合物时,较优选为并用光引发剂。但光硬化性化合物具有通过双键等自由基进行链聚合反应的官能团,故并非排除使用例如通过热产生自由基的热自由基引发剂。
光引发剂较优选为光自由基聚合引发剂。光自由基聚合引发剂只要为通过照射紫外线或可见光而产生自由基并开始链聚合反应的化合物,则无特别限定,可举例如二苯乙二酮二甲基缩酮、1-羟基环己基苯基酮、二乙基噻吨酮、二苯基酮、2-乙基蒽醌、2-羟基-2-甲基苯丙酮、2-甲基-〔4-(甲基硫基)苯基〕-2-N-吗啉基-1-丙烷、2,4,6-三甲基苯甲酰基二苯基膦氧化物、樟脑醌、9-芴酮、二苯基二硫化物等。市面贩卖品可举例如IRGACURE(注册商标)系列的651、184、2959、127、907、369、379EG、819、784、754、500、OXE01、OXE02、DAROCURE(注册商标)1173、LUCIRIN(注册商标)TPO(皆为BASF公司制)、SEIKUOL(注册商标)系列的Z、BZ、BEE、BIP、BBI(皆为精工化学公司制)等。
另外,光自由基聚合引发剂中,365nm中的摩尔吸光系数(ε)较优选为50mL/g·cm以上10000mL/g·cm以下,更优选为100mL/g·cm以上8000mL/g·cm以下,又更优选为1000mL/g·cm以上7500mL/g·cm以下。另外,摩尔吸光系数是以甲醇或乙腈为溶剂而测定。这些中,365nm中的摩尔吸光系数(ε)为100mL/g·cm以上10000mL/g·cm以下的光自由基聚合引发剂可举例如Omnirad(注册商标)651(甲醇中ε=360mL/g·cm)、Omnirad(注册商标)907(甲醇中ε=4700mL/g·cm)、Omnirad(注册商标)369(甲醇中ε=7900mL/g·cm)、Omnirad(注册商标)379(甲醇中ε=7900mL/g·cm)、Omnirad(注册商标)819(甲醇中ε=2300mL/g·cm)、Omnirad(注册商标)TPO(乙腈中ε=4700mL/g·cm)、IRGACURE(注册商标)OXE-01(乙腈中ε=7000mL/g·cm)、IRGACURE(注册商标)OXE-02(乙腈中ε=7700mL/g·cm)等,但并不限定于这些。
使用光自由基聚合引发剂时,其含量相对于粘合剂树脂的总量100质量份较优选为0.01质量份以上10质量份以下。该含量上限更优选为7质量份,又更优选为5质量份,特优选为4质量份,最优选为3质量份。另外,该含量下限更优选为0.05质量份,又更优选为0.1质量份,特优选为1质量份,最优选为1.5质量份。
<热自由基聚合引发剂>
对光硬化性化合物使用热自由基聚合引发剂时,该热自由基聚合引发剂只要为通过加热而产生自由基并开始链聚合反应的化合物,则无特别限定,可举例如有机过氧化物、偶氮化合物、安息香化合物、安息香醚化合物、苯乙酮化合物、苯并频哪醇等,较优选为使用苯并频哪醇。有机过氧化物可由市面贩卖品获得,例如Kayamec(注册商标)系列的A、M、R、L、LH、SP-30C、Perkadox(注册商标)系列的CH-50L、BC-FF、L-40ES(Kadox B-40ES)、14、16、Trigonox(注册商标)系列的22-70E、23-C70、121、121-50E、121-LS50E、21-LS50E、42、42LS、Kayaester(注册商标)系列的P-70、TMPO-70、CND-C70、OO-50E、AN、Kayabutyl(注册商标)系列的B、Kayacarbon(注册商标)系列的BIC-75、AIC-75(Kayaku Akzo公司制)、PERMEK(注册商标)系列的N、H、S、F、D、G、PERHEXA(注册商标)系列的H、HC、TMH、C、V、22、MC、PERCURE(注册商标)系列的AH、AL、HB、PERBUTYL(注册商标)系列的H、C、ND、L、PERCUMYL(注册商标)系列的H、D、PEROYL(注册商标)系列的IB、IPP、PEROCTA(注册商标)ND(日油公司制)等。另外,偶氮化合物可由市面贩卖品获得,例如VA-044、V-070、VPE-0201、VSP-1001(FUJIFILM和光纯药工业公司制)等。
使用热自由基聚合引发剂时,其含量相对于粘合剂树脂的总量100质量份较优选为0.01质量份以上10质量份以下。该含量上限更优选为7质量份,又更优选为5质量份,特优选为4质量份,最优选为3质量份。另外,该含量下限更优选为0.05质量份,又更优选为0.1质量份,特优选为1质量份,最优选为1.5质量份。因此,接着层中的含量的最优选范围为1.5质量份以上3质量份以下。
[光学层叠体]
本发明的光学层叠体是在上述光学功能膜进一步层叠中间膜。中间膜较优选为热塑性树脂的树脂膜,特优选为聚乙烯丁醛的膜。中间膜可为1片或多片,但较优选为具有光学功能膜经2片中间膜所夹持的结构的光学层叠体。
图2呈示本发明的光学层叠体的一实施方式,光学层叠体20具有光学功能膜10经2片中间膜201所夹持的结构,光学功能膜10例如相当于图1的光学功能膜。如此光学层叠体20为通过层合中间膜201及光学功能膜10而制作。
<(C)中间膜>
中间膜可使用热塑性树脂,较优选可使用一般使用的车用中间膜。如此的车用中间膜可举例如聚乙烯丁醛系树脂(PVB)、聚乙烯醇树脂(PVA)、乙烯/乙酸乙烯酯共聚系树脂(EVA)、或环烯烃聚合物(COP)。以这些树脂制作的中间膜作为夹层玻璃用中间膜的用途广泛,因而为优选。另外,中间膜的厚度只要为在将光学层叠体应用于后述HUD系统时不会影响显示光的反射的范围,则无特别限定,可因应用途适当地设计。
本发明所使用的中间膜中可适当地添加掺配紫外线吸收剂、抗氧化剂、抗静电剂、热稳定剂、着色剂、接着调整剂等,特别是分散有吸收红外线的微粒子的中间膜在制作高性能遮热夹层玻璃时较为重要。吸收红外线的微粒子使用选自由Sn、Ti、Zn、Fe、Al、Co、Ce、Cs、In、Ni、Ag、Cu、Pt、Mn、Ta、W、V、Mo所成组的金属、该金属的氧化物、该金属的氮化物、或含有这些中的至少2种以上的复合物等具有导电性的材料的微粒子。另外,这些材料中可掺配Sn、Sb、F等。尤其,在可见光线区域中为透明的锡掺杂氧化铟(ITO)、锑掺杂氧化锡(ATO)、氟掺杂氧化锡在使用作为要求遮热夹层玻璃的透明性的建筑用、汽车用窗时为较优选。分散于中间膜的吸收红外线的微粒子的粒径较优选为0.2μm以下。若微粒子的粒径为0.2μm以下,则可抑制可见光线区域的光散射并吸收红外线,可在不产生雾度下确保电波通过性及透明性,且可维持与未添加的中间膜同等的接着性、透明性、耐久性等物性,进一步可在一般夹层玻璃生产线作业中进行夹层玻璃化处理。另外,中间膜使用PVB时,为了使中间膜的含水率保持为最优选,故在恒温恒湿房间进行层合化处理。另外,中间膜可使用其一部分经着色的中间膜、具有隔音功能的夹芯层的中间膜、为了减轻HUD中的鬼影现象(重影)而于厚度倾斜的中间膜(楔形)等。
中间膜与光学功能膜的层合方法并无特别限制,可举例如使用夹辊同时压接中间膜与光学功能膜并层合的方法。层合时,夹辊可加热时可一边加热一边压接。另外,中间膜与光学功能膜的密接性较差时,可预先进行通过电晕处理、等离子体处理等表面处理后再进行层合。
中间膜可在溶解于溶剂的状态下直接层叠于光学功能膜的单面或两面。使用聚乙烯丁醛系树脂(PVB)时,丁醛化度的下限值较优选为40摩尔%,更优选为55摩尔%,特优选为60摩尔%。另一方面,丁醛化度的上限值较优选为85摩尔%,更优选为80摩尔%,特优选为75摩尔%。另外,丁醛化度可通过红外线吸收光谱(IR)法测定,例如可使用FT-IR测定。
聚乙烯丁醛系树脂的羟基量的下限值较优选为15摩尔%,上限值较优选为35摩尔%。若羟基量未达15摩尔%,则会降低夹层玻璃用中间膜与玻璃板的接着性、或降低夹层玻璃的抗穿透性。另一方面,羟基量若超过35摩尔%,则中间膜会变硬。
聚乙烯丁醛系树脂可通过将聚乙烯醇以醛进行缩醛化而调制。聚乙烯醇通常通过使聚乙酸乙烯酯皂化而获得,一般使用皂化度80摩尔%以上99.8摩尔%以下的聚乙烯醇。另外,聚乙烯醇的聚合度上限值较优选为4000,更优选为3000,特优选为2500。聚合度若超过4000,则难以形成中间膜。
<功能性玻璃>
本发明的功能性玻璃具有上述光学功能膜或光学层叠体及(D)玻璃板。玻璃板可为1片或多片,但较优选为具有上述光学功能膜或光学层叠体以2片玻璃板夹持而成的结构的功能性玻璃。如此功能性玻璃适合使用作为HUD系统中的显示介质。
使用本发明的光学功能膜或光学层叠体制作功能性玻璃时,于2片玻璃板之间配置光学功能膜或光学层叠体,并以高温、高压压接,据此可获得于夹层玻璃内配置有光学层叠体的功能性玻璃。图3呈示本发明的功能性玻璃的一实施方式。图3所示功能性玻璃30具有光学层叠体20以2片玻璃板301夹持而成的结构,光学层叠体20为光学膜10以2片中间膜102所夹持。如图3所示,在光学层叠体20上层叠玻璃板301时,中间膜201也具有作为用以维持2片玻璃板301与光学层叠体20的密接性的粘着剂或接着剂的功能。
<(D)玻璃板>
功能性玻璃例如可通过将上述光学功能膜或光学层叠体贴合于玻璃板而制作。作为将光学功能膜或光学层叠体贴合于玻璃板的方法一例,可将粘着剂或接着剂涂布于该光学功能膜或光学层叠体的单侧或两侧,接着贴合玻璃板,据此而获得。粘着剂或接着剂并无特别限制,但较优选为在之后要剥离时重工性优异的粘着性优选的材料,例如聚硅氧粘着剂、丙烯酸系粘着剂等。
玻璃板例如只要具有即使将本发明的功能性玻璃利用作为挡风玻璃也可充分视觉确认前方景色的透明性,则无特别限定。另外,玻璃板的折射率较优选为1.2以上2.0以下,更优选为1.4以上1.8以下。另外,玻璃板的厚度、形状等也只要在不影响显示光反射的范围内,则无特别限定,可因应用途适当地设计。另外,这些玻璃板中可于反射面设置多层膜所构成的增强反射膜、兼具遮热功能的金属薄膜层。这些膜可提高入射偏光的反射率,但例如使用本发明的功能性玻璃作为汽车用挡风玻璃时,较优选为以功能性玻璃的可见光线透射率成为70%以上的方式调整反射率。
具体说明使用本发明的光学功能膜或光学层叠体制作功能性玻璃的方法的一例。首先准备2片玻璃板。将功能性玻璃使用作为汽车的挡风玻璃用夹层玻璃时,使用以浮法制作的钠钙玻璃。玻璃可为透明或着色为绿色的玻璃,并无特别限制。这些玻璃板所使用的厚度通常约为2mmt,但因应近年来玻璃的轻量化的要求,也可使用厚度比2mmt稍为更薄的玻璃板。将玻璃板裁切为特定形状并对玻璃边缘实施倒角后,进行洗涤。需要黑色框状或点状印刷时,则将其印刷于玻璃板。需要形成为如挡风玻璃般的曲面形状时,则将玻璃板加热至650℃以上,其后通过铸模压制或通过自重弯曲等以使2片成为相同面形状的方式整形,之后冷却玻璃。此时若冷却速度过快则会于玻璃板产生应力分布,而形成强化玻璃,故慢慢地冷却。将如上述方式制作的玻璃板中的1片水平放置,于其上重叠本发明的光学功能膜或光学层叠体,进一步放置另1片玻璃板。接着,以切割机裁切去除从玻璃边缘突出的光学功能膜、中间膜。其后,一边将层叠为三明治状的玻璃板、光学功能膜或光学层叠体之间存在的空气脱气,一边加热至80℃至100℃,而进行预备接着。使空气脱气的方法有将玻璃板/光学功能膜或光学层叠体/玻璃板的层叠体以耐热橡胶等所制成的橡胶袋包裹所进行的袋法、仅将玻璃板端部以橡胶环覆盖并密封的环法等2种,可使用任一种方法。预备接着结束后,将从橡胶袋取出的玻璃板/光学功能膜或光学层叠体/玻璃板的层叠体、或取下橡胶环的层叠体放入高压釜中,在10至15kg/cm2的高压下加热至120℃至150℃,在该条件加热、加压处理20分钟至40分钟。处理后冷却至50℃以下后,进行除压,从高压釜中取出玻璃板/光学功能膜或光学层叠体/玻璃板所构成的本发明的功能性玻璃。
如此所得的功能性玻璃可使用作为普通汽车、小型汽车、轻型汽车等的挡风玻璃,也可使用作为大型特殊汽车、小型特殊汽车的挡风玻璃、侧边玻璃、后挡玻璃、天窗玻璃。另外,也可使用作为铁路车辆、船舶、飞机的窗户,另外,也可使用作为建材用及产业用窗材。因应使用形态可将功能性玻璃与具有UV阻隔或调光功能的构件层叠或贴合而使用。
[抬头显示器系统]
图4为以示意图呈示本发明的HUD系统的一实施方式。图1所示HUD系统具备将呈示显示图像的显示光形成为S偏光或P偏光并射出的显示图像投影装置(显示器)2、将从显示图像投影装置2射出的显示光反射的反射镜3、及从显示图像投影装置2射出的S偏光或P偏光所入射的本发明的功能性玻璃4。从显示图像投影装置2射出的S偏光或P偏光于反射镜3反射,该反射的显示光照射于作为挡风玻璃发挥功能的功能性玻璃4,据此S偏光或P偏光会通过光径5到达观察人员1,并可视觉确认显示图像的虚像6。另外,图4所示HUD系统中,从显示图像投影装置2射出的显示光会通过反射镜3入射于功能性玻璃4,但也可从显示图像投影装置2直接入射于功能性玻璃4。另外,也可从显示图像投影装置2将呈示显示图像的显示光以随机光射出并于反射镜3反射,该反射光在到达功能性玻璃4前会通过偏光板,据此调整从显示图像投影装置2射出的偏光,并使所求偏光照射于功能性玻璃4。另外,图4所示HUD系统是作为显示介质而具备功能性玻璃,但也可作为显示介质而具备本发明的光学功能膜、光学层叠体。
使用1/2波长板作为位相差层且入射光为S偏光时,以布鲁斯特角入射于功能性玻璃4的光的一部分会于功能性玻璃4表面直接反射,并被观察人员1视觉确认。另一方面,通过功能性玻璃4的入射光于内部通过1/2波长板而转换为P偏光。其后光从功能性玻璃4射出至空气中时会成为布鲁斯特角,故抑制P偏光的反射,而不易产生鬼影现象。另外,入射光为P偏光时,以布鲁斯特角入射于功能性玻璃4,据此抑制在玻璃表面的反射,而不易产生鬼影现象。另一方面,通过功能性玻璃4的入射光于内部通过1/2波长板转换为S偏光。其后光从功能性玻璃4射出至空气中时会直接反射,并被观察人员1视觉确认。如上述,无关于偏光的种类,以本发明的方式使用抬头显示器系统,据此可提供可抑制鬼影现象的产生且视觉确认性优异的抬头显示器。
<显示图像投影装置>
显示图像投影装置2只要可射出所求P偏光或S偏光且最终到达功能性玻璃4,则无特别限定,可举例如液晶显示装置(LCD)、有机EL显示器(OELD)等。显示图像投影装置2为液晶显示装置时,射出光通常为线性偏光,故可直接使用。另一方面,显示图像投影装置2为有机EL显示器时,例如图5所示,显示图像投影装置2可由光源2A、及可射出P偏光或S偏光的偏光板2B所构成。另外,将HUD系统用于汽车时,液晶显示装置、有机EL显示器例如可于如仪表板的光射出口配置偏光板、1/2波长板等光学构件,并以可从显示图像投影装置2射出P偏光或S偏光的方式调整。另外,显示图像投影装置2所使用的光源并无特别限定,可使用激光光源或LED光源等。另外,可以使构成位相差层的位相差元件的中心反射波长对应上述光源的发光光谱的方式设定,据此可更有效地使显示图像更鲜明。
<反射镜>
本发明的HUD系统可任选具备反射镜3。反射镜3只要可使来自显示图像投影装置2的显示光朝功能性玻璃4反射,则无特别限定,例如可由平面镜、凹面镜等所构成。使用凹面镜作为反射镜3时,凹面镜可将来自显示器的显示光以特定放大率放大。
本发明的HUD系统中,以相对于功能性玻璃4的S偏光或P偏光的布鲁斯特角为α时,从显示图像投影装置2射出的光入射于作为显示介质的功能性玻璃4的入射角较优选为α-10°至α+10°的范围,更优选为α-5°至α+5°的范围。另外,入射角是指与显示介质(功能性玻璃4)表面垂直的轴和入射于显示介质表面的光的夹角角度(以下将该入射角称为“入射角X”)。
本发明的HUD系统的一实施态样中,使用1/2波长板作为光学功能膜,显示介质为功能性玻璃4,且从显示图像投影装置2射出的显示光为S偏光时,使从显示图像投影装置2射出的S偏光通过反射镜3以α-10°至α+10°的范围入射,也就是相对于与功能性玻璃4表面垂直的轴以布鲁斯特角附近的角度入射,较优选为以布鲁斯特角α的入射角入射,据此可抑制通过功能性玻璃4转换的P偏光于车外侧玻璃板的反射,可抑制重影的产生。也就是,若S偏光的入射角为未达α-10°或超过α+10°时,S偏光的入射角会从布鲁斯特角附近的角度偏移,故通过1/2波长板转换的P偏光的反射会增加,而有产生重影的情形。
本发明的HUD系统中,从显示图像投影装置射出的光较优选为从(A)2层以上的位相差层中具有最高折射率的位相差层的配置侧入射。从显示图像投影装置射出的光为S偏光时,因视角提高,故在广泛视角区域中视觉确认人员可无压力地利用HUD系统。
另外,本发明的HUD系统的其它实施态样中,较优选为使用将1片或2片以上的圆偏光反射层(胆固醇状液晶层)作为位相差层以2片1/4波长板夹持而成的层叠体,显示介质为功能性玻璃,且从显示图像投影装置2射出的显示光为P偏光。一般来自路面的反射光为S偏光,故偏光太阳眼镜以可吸收S偏光的方式设计。因此,在利用S偏光的以往HUD系统中,通过偏光太阳眼镜的HUD的显示图像的视觉确认性会极端降低。另一方面,若为P偏光到达观察人员的利用P偏光的HUD系统,则可抑制重影的产生,且在配戴偏光太阳眼镜时也可提高显示图像的视觉确认性。另外,圆偏光反射层为胆固醇液晶层时,通过圆偏光反射层的圆偏光会通过第二1/4波长板而转换为原来的P偏光,该第二1/4波长板以与第一1/4波长板的慢轴正交的位置关系设置慢轴。经转换的P偏光也同样地以布鲁斯特角附近到第二1/4波长板外侧的车外侧玻璃面入射。因此也可大幅降低第二1/4波长板外侧的车外侧玻璃面的P偏光的反射,其结果可大幅改善重影的产生。
本发明的HUD系统中,例如设置含有具备1/2波长板的光学功能膜的功能性玻璃时,为了有效地进行偏光转换(例如将P偏光转换为S偏光,或将S偏光转换为P偏光),较优选为将从与功能性玻璃表面垂直的轴倾斜45°以上65°以下的位置入射的S偏光的偏光轴或P偏光的偏光轴与光学功能膜的慢轴的夹角角度θ控制为35°以上47°以下。通过使入射于功能性玻璃的S偏光或P偏光的入射角为45°以上65°以下的范围,在P偏光入射于功能性玻璃时,理论上可将功能性玻璃表面的反射率抑制在2%以下。通过的P偏光通过1/2波长板转换为S偏光,且经转换的S偏光于入射侧相反侧的功能性玻璃与空气的界面反射。反射的S偏光通过1/2波长板再次转换为P偏光,该P偏光会到达观察人员。另外,S偏光入射于功能性玻璃时,S偏光会在功能性玻璃表面反射,该S偏光会到达观察人员。通过的部分S偏光会通过1/2波长板转换为P偏光,经转换的P偏光会在不于入射侧相反侧的功能性玻璃或功能性玻璃与空气的界面反射下通过。如上述,控制入射于功能性玻璃的S偏光或P偏光的入射角X,据此可抑制重影的产生。另外,角度θ未达35°或超过47°时,将入射于功能性玻璃的P偏光转换为S偏光或将S偏光转换为P偏光的偏光轴转换性能较低,其结果有产生重影之忧。通过适当控制该角度θ,1/2波长板可显示良好偏光轴转换性能,其结果可更鲜明地视觉确认显示图像。
光学功能膜具备1/2波长板时,为了适当控制偏光轴转换性能,故角度θ较优选为由下述式(2)及(3)计算的值。在此说明下述式(2)及(3)的技术意义。入射于含有如此光学功能膜的功能性玻璃的S偏光或P偏光在通过具有与空气相异的折射率的介质的1/2波长板时,入射于1/2波长板的入射角X会变化。在此,以S偏光或P偏光相对于功能性玻璃的入射角X为α,以实际入射于1/2波长板的入射角X,也就是1/2波长板的折射角为β,以空气的折射率为nα,以1/2波长板的折射率为nβ,根据司乃耳定律,sinα/sinβ=nβ/nα成立,若将该式简化为求β的方程式,则可推导出式(3)。另一方面,以入射于功能性玻璃的S偏光的偏光轴为x轴,以P偏光的偏光轴为y轴,以y轴与1/2波长板的慢轴的夹角为θ时的位相差值为Re时,通过向量解析,y轴表示为Re·cosθ,x轴表示为Re·sinθ。在此,已知1/2波长板的偏光轴转换性能在相对于1/2波长板的慢轴以45°入射光时会成为最大,故理论上S偏光的偏光轴或P偏光的偏光轴与光学功能膜的慢轴的夹角角度θ较优选为45°。但是,如上述,即使以入射于功能性玻璃的S偏光的偏光轴或P偏光的偏光轴与光学功能膜的慢轴的夹角角度为θ,但实际上入射于1/2偏光板的角度为β。因此,有关于Re·cosθ的y轴(理论上的y轴),若求x轴往中心倾斜角度β时的y轴(事实上的y轴),则Re·cosθ/事实上的y轴=sin(90°-β)成立,事实上的y轴表示为Re·cosθcosβ。如上述,1/2波长板的慢轴与S偏光的偏光轴或P偏光的偏光轴的夹角角度较优选为45°。为了使入射于功能性玻璃的S偏光或P偏光的偏光轴与1/2波长板的慢轴的夹角角度成为45°,x轴(Re·sinθ)需要等于事实上的y轴(Re·cosθcosβ),故求得Re·sinθ=Re·cosθcosβ。将该式简化,据此推导出式(2)。如上述,根据由下述式(2)及(3)计算的值,以与实际入射于1/2偏光板的角度β的关系严密地控制角度θ,据此可最大限度地利用1/2波长板所显示的偏光轴转换性能。
tanθ=cosθ...(2)
θ:1/2波长板的慢轴与对功能性玻璃以任意入射角α入射的S偏光或P偏光的偏光轴的夹角角度。
α:S偏光或P偏光对功能性玻璃的入射角。
nα:空气的折射率。
nβ:1/2波长板的折射率。
角度θ的范围较优选为控制于该角度θ值的±5°的范围,更优选为控制于±3°的范围。角度θ若为满足由上述式(2)及(3)计算的值的角度的±5°的范围外,则1/2波长板所表示的偏光转换效率会变低。根据由上述式(2)及(3)计算的值控制角度θ的范围,据此可抑制1/2波长板的偏光转换效率的降低。
代入式(3)的1/2波长板的折射率,以1/2波长板的慢轴方向的折射率为nx,在1/2波长板的面内与慢轴方向正交的方向的折射率为ny,1/2波长板的厚度方向的折射率为nz,将这些的和的平均值使用作为平均折射率。另外,使用市面贩卖品的1/2波长板时,平均折射率可使用目录等的记载值。另外,使用后述聚合性液晶作为1/2波长板的材料时,若使用液晶本来的寻常光折射率no及非寻常光折射率ne,则平均折射率表示为(nx+ny+nz)/3=(no+no+ne)/3。若表示由式(2)及(3)计算的θ的具体例,例如空气的折射率为1.00,使用折射率1.55的1/2波长板,且S偏光或P偏光的入射角X为45°时,根据式(2)及(3),θ值为42°,故θ的范围较优选为37°以上47°以下,更优选为39°以上45°以下。S偏光或P偏光的入射角X为50°时,根据式(2)及(3),θ值为41°,故θ的范围较优选为36°以上46°以下,更优选为38°以上44°以下。另外,S偏光或P偏光的入射角X为56°或60°时,根据式(2)及(3),θ值为40°,故θ的范围较优选为35°以上45°以下,更优选为37°以上43°以下。另外,S偏光或P偏光的入射角X为65°时,根据式(2)及(3),θ值为39°,故θ的范围较优选为34°以上44°以下,更优选为36°以上42°以下。
如上述,本发明中,通过控制入射于光学功能膜的S偏光或P偏光的偏光轴与1/2波长板的慢轴的夹角θ,而可进一步提高1/2波长板所显示的偏光轴转换性能。此时,以1/2波长板的慢轴的控制性及生产成本的观点来看,特优选为使用含有聚合性液晶层作为具有转换偏光轴的作用的层的1/2波长板。另外,如上述1/2波长板的波长分散性只要适合于抬头显示器用途,则无特别限制,但为了在可见光区域的宽广波长范围内正确地进行偏光转换,故较优选为具有反向波长分散性。一般而言,高分子为双折射的绝对值在短波长侧变大的正常分散,但若为通过控制可见光的各波长的双折射Δn的值而在长波长侧双折射会变大的液晶化合物,则可获得反向波长分散性。另外,通过将具有因应化合物的波长分散特性的适当位相差值的多个位相差板以适当的慢轴的组合层叠,也可获得反向波长分散性。在使用层叠如此多个位相差板的1/2波长板时,对于各个位相差板的慢轴角,以上述方式适当控制入射于光学功能膜的S偏光或P偏光的偏光轴与1/2波长板的慢轴的夹角θ,据此可使1/2波长板显示良好偏光轴转换性能,其结果可进一步鲜明地视觉确认显示图像。
(实施例)
以下通过实施例详细说明本发明。实施例中“份”为质量份。另外,本发明在不超出其主旨范围内并不限定于以下实施例。另外,在未特别说明下,室温为20℃±5℃的范围内。
[实施例1]
<涂布液(接着剂)的调制>
混合A至I所示成分而调制具有表1所示组成比的涂布液(接着剂1至9)。对所调制的接着剂1至9,使用数码折射计(ATAGO公司制“RX-7000α”)测定各接着剂的硬化前的折射率。另外,使用粘度计(东机产业公司制“TVE-22L”)测定各接着剂的粘度。另外,表1中的成分量为质量份。
[表1]
A:丙烯酸4-羟基丁酯(4-HBA,大阪有机化学工业公司制)。
B:正苯基丙烯酸苯氧基乙酯(Miramer M1142,MIWON公司制)。
C:双酚A型环氧基丙烯酸酯(KAYARAD(注册商标)R-115F,日本化药公司制)。
D:双酚F型环氧基丙烯酸酯(KAYARAD(注册商标)R-381,日本化药公司制)。
E:2,4,6-三甲基苯甲酰基二苯基膦氧化物(Omnirad(注册商标)TPO-H,IGMResins B.V.公司制)。
F:氨甲酸乙酯丙烯酸酯(UX-0937,日本化药公司制)。
G:EO改质酚丙烯酸酯(PHE-2,第一工业制药公司制)。
H:双酚A型环氧基丙烯酸酯(VISCOAT700HV,大阪有机化学工业公司制)。
I:二环戊烯基氧乙基丙烯酸酯(FA512-AS,Showa Denko Materials公司制)。
<接着剂硬化膜的折射率测定>
于作为支撑基板的三乙酸纤维素(TAC)膜(TacBright公司制,P960:厚度60μm)涂布接着剂1至9,将高压汞灯(HARISON TOSHIBA LIGHTING公司制)以120W输出照射5至10秒UV而固定化,据此于支撑基板上制作接着剂硬化膜1至9。接着,对接着剂硬化膜1至9使用分光光度计(岛津制作所制“UV-3600”)测定400nm至700nm的偏光入射时的接着层的正交反射率,由其平均值R1通过下述式(4)计算接着层的折射率n。另外,支撑基板(基材)的折射率N为1.487。结果呈示于表2。
<接着剂硬化膜的弹性模数测定>
于铝基板涂布接着剂1至9,在其上迭压东洋纺公司制聚酯膜COSMOSHINE(注册商标)A4100,将高压汞灯(HARISON TOSHIBA LIGHTING公司制)以120W输出照射5至10秒UV而固定化,据此于铝基板上制作厚度140至160μm的接着剂硬化膜1至9。接着将接着剂硬化膜裁切为宽度1cm、长度4cm,使用TENSILON万能试验机(A&D公司制“RTG-1210”)以拉伸速度100mm/分钟的条件分别于25℃及140℃中进行拉伸试验,而测定弹性模数。结果呈示于表2。
[表2]
平均反射率[%] | 折射率n | 弹性模数[MPa] | |
接着剂硬化膜1 | 6.205 | 1.573 | 1649.1 |
接着剂硬化膜2 | 6.245 | 1.574 | 1834.7 |
接着剂硬化膜3 | 6.217 | 1.573 | 967.6 |
接着剂硬化膜4 | 6.534 | 1.584 | 185.6 |
接着剂硬化膜5 | 6.508 | 1.583 | 360.4 |
接着剂硬化膜6 | 6.436 | 1.580 | 496.5 |
接着剂硬化膜7 | 5.793 | 1.559 | 238.2 |
接着剂硬化膜8 | 5.830 | 1.560 | 20.9 |
接着剂硬化膜9 | 5.492 | 1.548 | 21.2 |
R1={(N-n2)÷(N+n2)}2...(4)
R1:平均反射率
N:支撑基板的折射率
n:接着层的折射率
<位相差层的制作>
[涂布液(液晶组合物)的调制]
首先调制具有表3所示组成的涂布液(R1)。另外,表3中的成分量为质量份。
[表3]
使用所调制的涂布液R1用下述顺序制造3个1/2波长板。支撑基板使用以日本特开2002-90743号公报的实施例1所记载方法进行摩擦处理的TAC膜(TacBright公司制P960:厚度60μm)。另外,摩擦角度如表4所示,以膜的长度方向与1/2波长板的慢轴的夹角角度(以下称为“慢轴角度”)分别成为71.5°、50°及26.5°的方式设定。首先,将涂布液R1使用线棒以干燥后所得1/2波长板的厚度成为约2μm的方式于室温涂布于TAC膜的摩擦处理面上。将所得涂布膜于50℃加热2分钟去除溶剂,而形成液晶相。接着对液晶层以高压汞灯(HARISONTOSHIBA LIGHTING公司制)以120W输出照射5至10秒UV而固定化,据此制作于支撑基板上具有位相差层的位相差层1至3。另外,将所得位相差层1至3的各区域的位相差值以自动双折射计(王子测量机器公司制“KOBRA-21ADH”)测定,结果586nm中的位相差值分别为293nm、230nm、275nm。接着对位相差层1至3使用分光光度计(岛津制作所制“UV-3600”)测定400nm至700nm的偏光入射时的位相差层1至3的正交反射率,并计算平均值R2。其后,根据下述式(5)、(6)、(7)及(8),以各层的界面中的反射率r1、r2、r3与层整体的平均反射率R的关系成立的方式,计算位相差层的快轴方向中的折射率n2。另外,θ1为从空气中至位相差层的入射角,为5°,另外,θ2为从空气中入射至位相差层时的折射角,也就是从位相差层入射至配向膜时的入射角,θ3为从位相差层入射至配向膜时的折射角,也就是从配向膜入射至支撑基板时的入射角,θ4为从配向膜入射至支撑基板时的折射角,通过下式(9)、(10)及(11)而计算。根据各层的界面中的反射率r1、r2、r3而计算,空气的折射率n1为1.000,配向膜的折射率n3为1.531,支撑基板的折射率n4为1.487。结果呈示于表4。
平均反射率R2=r1+r2+r3...(5)
r1:从空气中入射至位相差层时的反射率
r2:从位相差层入射至配向膜时的反射率
r3:从配向膜入射至支撑基板时的反射率
r1=tan2(θ1-θ2)÷tan2(θ1+θ2)...(6)
r2=tan2(θ2-θ3)÷tan2(θ2+θ3)...(7)
r3=tan2(θ3-θ4)÷tan2(θ3+θ4)...(8)
θ1:从空气中入射至位相差层时的入射角(5°)
θ2:从空气中入射至位相差层时的折射角=从位相差层入射至配向膜时的入射角
θ3:从位相差层入射至配向膜时的折射角=从配向膜入射至支撑基板时的入射角
θ4:从配向膜入射至支撑基板时的折射角
n1:空气的折射率
n2:位相差层的快轴方向中的折射率
n3:配向膜的折射率
n4:支撑基板的折射率
[表4]
慢轴角度 | 位相差值[nm] | 平均反射率[%] | 折射率n | |
位相差层1 | 71.5° | 293 | 5.521 | 1.612 |
位相差层2 | 26.5° | 230 | 5.514 | 1.611 |
位相差层3 | 50.0° | 275 | 5.417 | 1.605 |
<光学功能膜的制作>
使用自动涂布装置(TESTER SANGYO公司制“PI-1210”)将接着剂1涂布于位相差层1,于其涂布面进一步配置位相差层2,以各位相差层彼此接着的方式以层叠机贴合位相差层1与位相差层2。接着,对贴合的层叠体以高压汞灯(HARISON TOSHIBA LIGHTING公司制)以120W输出照射5至10秒UV,使接着剂1硬化并获得贴合膜1。其后,将贴合膜1在加热至40℃的2mol/L的氢氧化钾水溶液中浸渍5分钟,以水洗涤后,于70℃干燥5分钟,据此制造光学功能膜1。
<光学层叠体的制作>
将含有作为塑化剂的三乙二醇二-2-乙基己酸酯的厚度为0.38mm的透明聚乙烯丁醛中间膜裁切为与光学功能膜1相同的尺寸,将光学功能膜1配置于2片聚乙烯丁醛中间膜之间,接着以层叠机加压压接,据此获得光学层叠体1。
<功能性玻璃的制作>
于2片与光学层叠体1相同尺寸且厚度为2mm的玻璃板间配置光学层叠体1,接着,通过加压、加热而获得功能性玻璃A。具体而言,于透明玻璃板上依次重叠光学层叠体1、透明玻璃板。将其以橡胶袋包裹,并在加热至90℃的高压釜中脱气10分钟,进行预接着。将其冷却至室温后,从橡胶袋取出,再次在高压釜中于135℃、12kg/cm2的高压下加热、加压30分钟,制作外观良好的插入有夹层玻璃用层叠体的功能性玻璃A。
<橘皮的评价>
功能性玻璃的橘皮的评价是在室内进行,于桌上放置功能性玻璃,使荧光灯照于半反射镜部并以目视评价反射像。评价基准设定如下,A或B评价为外观优异。结果呈示于表5。
A:荧光灯的反射像无失真。
B:荧光灯的反射像几乎无失真。若横移视点则反射像稍有波动。
C:因细小皱折的影响使荧光灯的反射像模糊。
D:因较大皱折的影响使荧光灯的反射像失真。
<抬头显示器的制作及显示图像的评价>
以图4所示配置制作抬头显示器。另外,作为显示图像投影装置2、反射镜3而设置可对功能性玻璃4射出P偏光的液晶显示面板,并将上述制作的功能性玻璃A配置于功能性玻璃4。于暗室内,以从显示图像投影装置2的P偏光的入射角相对于功能性玻璃A成为布鲁斯特角(约56°)的方式,使功能性玻璃A的构成中的位相差层的宽度方向对齐水平方向,并以位相差层1侧的玻璃板成为入射面的方式设置功能性玻璃A。以该配置从显示图像投影装置2投影图像时,可明亮且鲜明地投影显示图像。此时,使观测显示图像的视点于上下方向移动,并将可鲜明投影显示图像的范围作为视角记录。结果呈示于表5。
<重影亮度比评价:1/2波长板的偏光转换性能的评价>
将来自图像投影装置(显示图像投影装置2)的水平方向的线图像以相对于功能性玻璃A射出S偏光的条件投影,以色彩亮度计(KONICA MINOLTA公司制“Prometric IC-PMI”)拍摄反射像,并评价显示图像。对于在宽60cm中从左边起5cm的位置I、从左边起30cm的位置II、及从左边起43cm的位置III的3点,位置I的评价图像是从以位置I为起点从玻璃面垂直分开142cm的点X拍摄。位置II的评价图像是从点X往位置I的垂线往右倾斜10°亮度计的位置拍摄。位置III的评价图像是从点X往位置I的垂线往右倾斜15°亮度计的位置拍摄。通过各位置的拍摄图像解析,将功能性玻璃A的构成中图像投影装置侧的玻璃板与空气界面的线图像的反射亮度(主图像)除以相对于图像投影装置为内侧的玻璃与空气界面的线图像的反射亮度(重影),据此计算重影亮度比。结果呈示于表5。另外,表5所示重影亮度越低,则投影于功能性玻璃的图像越不易成为重影并难以视觉确认,可判断图像的视觉确认性良好。
<波带的评价>
使用分光光度计(岛津制作所制“UV-3600”)对所得功能性玻璃A测定380nm至780nm的偏光入射时的正交透射率。正交透射率表示绝对偏光片的吸收轴与功能性玻璃的慢轴正交时的透射率。将所测定的透射率转换为吸光度,并计算功能性玻璃A中的吸光度的半值宽度。结果呈示于表5。此时,若600nm至500nm中的透射率皆未达1%,则评价为宽波带,若有1%以上的范围,则评价为窄波带。
[实施例2]
除了使用接着剂2以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体2及功能性玻璃B。另外,使用所制作的功能性玻璃B并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[实施例3]
除了使用接着剂3以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体3及功能性玻璃C。另外,使用所制作的功能性玻璃C并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[实施例4]
除了使用接着剂4以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体4及功能性玻璃D。另外,使用所制作的功能性玻璃D并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[实施例5]
除了使用接着剂5以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体5及功能性玻璃E。另外,使用所制作的功能性玻璃E并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[实施例6]
除了使用接着剂6以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体6及功能性玻璃F。另外,使用所制作的功能性玻璃F并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[实施例7]
除了使用接着剂7以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体7及功能性玻璃G。另外,使用所制作的功能性玻璃G并以与实施例1相同方式评价波带、视角、重影亮度比、橘皮的程度。结果呈示于表5。
[实施例8]
除了使用接着剂8以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体8及功能性玻璃H。另外,使用所制作的功能性玻璃H并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[实施例9]
除了将入射面从位相差层1变更为位相差层2之外,以与实施例1相同方式而制作光学层叠体9及功能性玻璃I。另外,使用使用所制作的功能性玻璃I并以相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[比较例1]
除了使用接着剂9以取代接着剂1之外,以与实施例1相同方式而制作光学层叠体10及功能性玻璃J。另外,使用所制作的功能性玻璃J并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[比较例2]
除了使用位相差层3以取代位相差层1,并使用无位相差层的TAC膜以取代位相差层2之外,以与实施例1相同方式而制作光学层叠体11及功能性玻璃K。另外,使用所制作的功能性玻璃K并以与实施例1相同方式评价波带、视角、重影亮度比及橘皮的程度。结果呈示于表5。
[表5]
由表5的结果来看,实施例1至9的亮度比低,重影的产生受到抑制,且波带较宽广,故可获得在宽广波长区域具有优异的偏光转换能力的HUD用光学功能膜。另外,在实施例1至8中,入射光的入射面为具有高折射率的位相差层侧,故视角会提高,在广泛视角区域中视觉确认人员可无压力地利用HUD系统。另外,在实施例4至8中,接着层中室温的弹性模数与高温的弹性模数的差为500MPa以下,故可抑制橘皮的产生,可实现优异美观的挡风玻璃。
另一方面,在比较例1中,接着层的折射率与位相差层的快轴方向中的折射率的差较大,故亮度比较高且观察到重影的产生。另外,在比较例2中,由于位相差层仅为1层,故波带较窄,无法获得在宽广波长区域具有优异的偏光转换能力的HUD用光学功能膜。
(产业利用性)
本发明的光学功能膜在宽广波长区域具有优异的偏光转换能力。因此,具备如此光学功能膜的抬头显示器系统可消除因投影位置所造成的重影产生不均,故可在不依赖于拍摄位置而抑制重影的产生。因此,视觉确认人员可无压力地利用抬头显示器系统。
附图标记说明
1观察人员
2显示图像投影装置
2A光源
2B偏光板
3反射镜
4功能性玻璃
5光径
6显示图像
10光学功能膜
101 接着层
102 位相差层
20光学层叠体
201中间膜
30功能性玻璃
301玻璃板。
Claims (12)
1.一种抬头显示器用光学功能膜,具备(A)2层以上的位相差层及(B)接着层,
前述接着层与至少一层的位相差层相邻,
且前述接着层的折射率和与前述接着层相邻的位相差层的快轴方向中的折射率的差的绝对值未达0.060。
2.根据权利要求1所述的抬头显示器用光学功能膜,其中前述(B)接着层与2个位相差层相邻设置,
且前述接着层的折射率与2层的位相差层的快轴方向中的各折射率的差的绝对值皆未达0.060。
3.根据权利要求1或2所述的抬头显示器用光学功能膜,其中前述(B)接着层在25℃的弹性模数与140℃的弹性模数的差为500MPa以下。
4.根据权利要求1至3中任一项所述的抬头显示器用光学功能膜,其中前述(A)2层以上的位相差层中的至少一层为1/2波长板。
5.根据权利要求1至4中任一项所述的抬头显示器用光学功能膜,其中前述(A)2层以上的位相差层皆为1/2波长板。
6.根据权利要求1至5中任一项所述的抬头显示器用光学功能膜,其中前述(B)接着层为使硬化性化合物硬化而成的硬化膜。
7.根据权利要求6所述的抬头显示器用光学功能膜,其中前述硬化性化合物为光硬化性化合物。
8.一种抬头显示器用光学层叠体,为权利要求1至7中任一项所述的抬头显示器用光学功能膜上进一步层叠(C)中间膜。
9.一种抬头显示器用功能性玻璃,具备权利要求1至7中任一项所述的抬头显示器用光学功能膜或权利要求8所述的抬头显示器用光学层叠体、及(D)玻璃板。
10.一种抬头显示器系统,具备作为显示介质的权利要求1至7中任一项所述的抬头显示器用光学功能膜、权利要求8所述的抬头显示器用光学层叠体、或权利要求9所述的抬头显示器用功能性玻璃。
11.根据权利要求10所述的抬头显示器系统,其中从显示图像投影装置射出的光为从配置有前述(A)2层以上的位相差层中具有最高折射率的位相差层的一侧入射。
12.根据权利要求10或11所述的抬头显示器系统,其中从显示图像投影装置射出的光为S偏光。
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TWI649589B (zh) | 2014-10-10 | 2019-02-01 | 日商日本化藥股份有限公司 | 光反射薄膜,並使用其之光控制薄膜,光學薄膜,功能性玻璃及抬頭顯示器 |
JP2018017996A (ja) * | 2016-07-29 | 2018-02-01 | 日東電工株式会社 | 位相差層付偏光板および有機el表示装置 |
WO2018084076A1 (ja) * | 2016-11-04 | 2018-05-11 | 富士フイルム株式会社 | ウインドシールドガラス、ヘッドアップディスプレイシステム、およびハーフミラーフィルム |
JP2019152795A (ja) * | 2018-03-05 | 2019-09-12 | 日本精機株式会社 | ヘッドアップディスプレイ装置 |
JP7382392B2 (ja) * | 2019-03-13 | 2023-11-16 | 富士フイルム株式会社 | 投映像表示用部材、ウインドシールドガラスおよびヘッドアップディスプレイシステム |
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2022
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- 2022-03-16 KR KR1020237033206A patent/KR20230155489A/ko unknown
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US20240004194A1 (en) | 2024-01-04 |
KR20230155489A (ko) | 2023-11-10 |
JPWO2022196732A1 (zh) | 2022-09-22 |
EP4310558A1 (en) | 2024-01-24 |
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