CN1065633C - 热稳定偏振器 - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
当其表面用硅酸盐层密封时就可制得具有含聚乙炔聚合物极化层的热稳定性、柔性偏振器。
Description
本发明涉及含有具有硅酸盐封闭表面的含聚乙炔(PAC)聚合物(POLPAC)极化层的热稳定柔性偏振器。本发明还涉及进一步粘结到外层上的这类偏振器。
美国专利4818624叙述了用有机硅烷进行表面甲硅烷基化使光偏振器稳定化的方法。由于仅在49-74℃(120-165°F)经24小时后就观察到脱色和颜色改变现象，所以其稳定效果是不够的。
由各基质层生产各层之间有粘合剂层的层压品的方法已经公开。美国专利5，049，427叙述了含有一种含PAC聚合物极化芯层和透明外层的层压偏振器，各层之间通过特殊的聚氨酯-聚脲粘结。
尽管POLPAC偏振器已经具备了优良的性能，但是在极端条件下的稳定性仍不能令人满意。在90℃贮存500小时后，其非偏振光的透过率发生变化，该透过率的变化值△T非偏大于5％。
然面，偏振器在经受特别高度加热的光显示器(例如小汽车中的仪表盘)中的应用仅当在这种条件下偏振器的光学性能△T非偏和△P的恶化程度至多为5％时才成为可能，这里△P是指偏振度的变化值。在玻璃板之间粘结后其光学性能可在100℃在1000小时内保持恒定的POLPAC偏振器已有报导。然而就加工性能和生产柔性塑料显示器这两方面而言这种层状体系不太适用于生产要求最好使用柔性偏振器的显示器。
因此，本发明的目的是生产能满足上述条件的、基于含PAC聚合物的层压偏振器。
令人惊奇的是，现已发现，如果用硅酸盐层将POLPAC偏振器的表面密封就可达到这个目的。
此外，本发明还涉及一种包含含PAC聚合物极化芯层和涂布在其两侧的透明、柔软外层的层压、柔性偏振器，其特征在于所述芯层和两个外层是通过硅酸盐层粘结的，而且按此方法层压成的偏振器是柔性的。
硅酸盐层是指该偏振器也可用来层压到玻璃片上、光学透镜上或棱镜上。如果使用一种有机粘合剂将偏振器的一个侧面粘结到一个玻璃显示器上或者其它玻璃元件上，则使用硅酸盐层就足以保护其自由表面。
硅酸盐层较好是以水溶液的形式涂布到芯层上和／或两个外层上。
适用的硅酸盐水溶液是已知的钠水玻璃和钾水玻璃的水溶液。
普通类型的钠水玻璃的固体含量为25-60％(重量)，SiO2含量为20-40％(重量)，其余的固体含量为Na2O，而普通类型的钾水玻璃的固体含量为25-40％(重量)，SiO2含量为20-30％(重量)，其余的固体含量为K2O。为了获得较薄的硅酸盐层，可以用水稀释这些溶液。
SiO2含量较好应尽可能高些，即SiO2／Na2O的重量比较好是≥3，或SiO2／K2O的重量比≥2．2。
使用硅酸盐层表示不必象美国专利5，049，427所述的那样，使用大量的有机溶剂。
硅酸盐层，即使层厚≤2μm也可以使PAC偏振器的性能稳定。为了得到热稳定粘结的层压品，较好是要求每平方米粘结表面含有100mg-2g的水玻璃(固体)。
在优选的实例中，在用硅酸盐溶液涂布之前，要用硅烷或硼酸盐处理芯层和／或外层。这一措施尤其可以提高粘结强度。
适用的硅烷应符合下面通式：Si(R1)n(R2)4-n其中R1基团，彼此独立地可为卤素或烷氧基，R2基团，彼此独立地可为烷基或链烯基，n为2、3或4。
烷基和烷氧基基团R1和R2可以是取代的。
适用的硅烷的例子有：四甲氧基硅烷、四乙氧基硅烷、甲基三甲氧基硅烷、二甲基二甲氧基硅烷、乙基三乙氧基硅烷、二甲基二氯硅烷、乙烯基甲基二氯硅烷和乙烯基三乙氧基硅烷。硅烷也可以直接混合，例如通过乳化，进入到硅酸盐溶液中。
适用的硼酸盐的例子是硼酸和硼砂。硼酸和硼酸盐也可以直接混合到或溶解在水玻璃溶液中。
涂布硅烷和硼酸盐时，尤其可以把芯层和／或外层浸渍在这些化合物的溶液中，或者，当这些化合物是液体时，可直接浸渍在这种纯化合物中，然后再将其取出。浸渍吸收量是如此之少以致无法用重量法来准确测定，不过一般小于1g·m2。
外层的厚度例如可为5μm-1mm，较好为20-200μm。极化芯层的厚度例如可为1-200μm，较好为5-50μm。
外层的例子有芳族聚酯、聚丙烯腈、聚(甲基)丙烯酸酯、聚砜、芳族聚碳酸酯、醋酸纤维素酯、乙酰丁酸纤维素酯、聚酰胺、聚乙内酰脲、聚酰亚胺、聚酰胺酰亚胺、聚对亚苯基苯并二咪唑类和-噁唑类以及聚醚酮，优选的是聚酯、聚(甲基)丙烯酸酯、聚碳酸酯和纤维素醚。这些材料的透明性是它们最重要的特点。这些材料通常以薄膜形式使用。
极化芯层是由含有PAC的聚合物产品制成的偏振器，其基体是一种含有极性基团的聚合物，其最大偏振度至少为90％，较好至少为95％，更好至少为98％，最大二色性比QE=5，或更大，较好为10或更大，两种情况均基于可见光的范围。这类偏振器以薄膜形式使用，其中优选方向由拉伸产生。拉伸度ε大于200％，较好至少为400％，更好为500-1000％。
直线偏振光的偏振度P和拉伸度ε的定义如下：
(L=拉伸后的长度，LO=拉伸前的长度)
含有PAC的聚合物产品的生产方法可参见例如美国专利5，049，427，其中乙炔是在适当催化制存在下，在一种聚合物溶液中进行聚合的。
适用的聚合物的例子有：聚氯乙烯、聚乙烯醇缩丁醛、聚乙烯醇(PVA)、部分水解的聚醋酸乙烯酯(PVAC)和其它含乙烯基醇的(共)聚合物、聚丙烯腈、含丙烯腈的共聚物、聚乙烯基吡咯烷酮、甲基纤维素和其它纤维素衍生物，以及聚碳酸酯。优选PVA和部分水解PVAC的溶液。
聚合物溶剂的例子有N-甲基吡咯烷酮(NMP)、二甲基甲酰胺(DMF)、二甲基亚砜(DMSO)等。聚合物在溶剂中的浓度为1-20％(重量)，较好为2-10％(重量)。
本发明的新型层压偏振器的特点是具有众多优异性能：
1．透光率高，
2．耐光度高，
3．极化芯层的热稳定性好，
4．优异的机械性能。
本新型偏振器适用于所有需要使用偏振膜或偏振箔的应用领域，尤其用在光学器件中(例如偏光显微镜、照相术、太阳镜和滑雪护目镜的抗反射涂层)，以及用于例如手表、计算器、袖珍计算机、计算机、指示器、投影显示器、游戏机、摄录机以及平面屏幕电视机等中的各种显示器。
在80℃，甚至没有添加稳定剂的非层压POLPAC薄膜也具有良好的稳定性，在80℃的空气中经500小时后，透光率的变化率(△T)为2-3％，偏振度的变化率(△P)小于1％。
本新型偏振器除含有聚乙炔外，还可包含其它二色性物质，例如碘或二色性染料。但是聚乙炔组分至少应占二色性物质总重量的50％，较好至少占80％。
实例1
层厚为11μm、拉伸700％的POLPAC薄膜的透光率T=38．7％(波长600nm)，偏振度P=99．99％。在80℃经过500小时后，透光率增加到41．7％，而偏振度只降至99．89％。
实例2
与实例1相同的薄膜在90℃保存仅270小时后其透光率(波长600nm)增加5．1个百分点，而偏振度则降低1．84个百分点。
实例3
将POLPAC薄膜浸没在硅酸钠水溶液中，然后干燥。600nm波长的透光率为36．3％，偏振度P=99．95％。在90℃经1446小时后这些数值实际上没有变化：T=36．6％，P=99．96％。
实例4
将聚乙炔含量为1．5％(重量)的聚乙烯醇／聚乙炔薄膜(A)拉伸约600％。拉伸后膜厚为12μm。
按如下方法层压该薄膜：
用钠水玻璃涂布厚度约100μm的三醋酸纤维素酯(CTA)的一个侧面。将上述聚乙烯醇／聚乙炔薄膜贴到用钠水玻璃涂布过的CTA薄膜的经涂布的一面上。将第二张三醋酸纤维素酯薄膜涂布有钠水玻璃的一侧贴到上述的聚乙烯醇／聚乙炔薄膜的自由表面上。令该薄膜层制品通过橡胶压延机，随后在80℃固化10分钟。
然后用波长为600nm的光测量其光学数据：T=35．2％， P=99．9％。
在90℃贮存500小时后这些数值没有变化。在160℃贮存16小时后测得如下数据：T=35．1％， P=99．9％。
实例5
将POLPAC薄膜在含有10％(重量)硅烷的四乙氧基硅烷／THF溶液中浸渍5分钟，干燥后粘合在二张100μm厚的CTA薄膜之间。为此，可将POLPAC膜铺在CTA膜上涂布有硅酸钠溶液的一侧上。然后将第二张同样涂布了硅酸钠溶液的CTA膜通过湿硅酸盐层铺在POLPAC膜还未被保护的一侧，该薄膜层制品通过压延机的橡胶壁压在一起，然后在95℃干燥5分钟。该层压品强度高，强行剥离将导致芯层破裂或者CTA膜被撕废。该层压品柔软得可以反复弯曲许多次而不会破裂或失去其优良的热稳定性。
在120℃测试该层压膜的稳定性。加热试验之前，对600nm波长光的透光率T为36．6％，偏振度为99．9％。在120℃经过1000小时后，T只降到36．1％，偏振度仍为99．9％。
Claims (10)
1．具有含聚乙炔聚合物极化层的热稳定、柔性偏振器，其特征在于该偏振器具有硅酸盐密封的表面。
2．按照权利要求1的偏振器，其特征在于所述表面的密封是通过硅酸盐溶液实现的。
3．按照权利要求1的偏振器，其特征在于所述表面的密封是通过钠水玻璃或钾水玻璃实现的。
4．按照权利要求2的偏振器，其特征在于表面的密封是通过100mg-2g水玻璃固体／平方米被封面积实现的。
5．按照权利要求1的偏振器，其特征在于它还具有贴在两侧上、并通过硅酸盐层粘合到极化层上的透明、柔性外层。
6．按照权利要求4的偏振器，其特征在于所述极化层和／或外层在用硅酸盐溶液涂布之前用一种硅烷进行处理。
7．按照权利要求2的偏振器，其特征在于所述硅酸盐溶液与硅烷和／或硼酸盐混合。
8．按照权利要求5的偏振器，其特征在于所述硅烷符合下面通式：Si(R1)n(R2)4-n
其中R1基团彼此独立地可为卤素或烷氧基，R2基团彼此独立地可为烷基或链烯基，n是2、3或4。
9．按照权利要求1的偏振器，其特征在于所述聚合物至少有一部分是聚乙烯醇。
10．按照权利要求1的偏振器，其特征在于它还含有其它二色性物质。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19944430096 DE4430096A1 (de) | 1994-08-25 | 1994-08-25 | Thermostabile Polarisatoren |
| DEP4430096.4 | 1994-08-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1140842A CN1140842A (zh) | 1997-01-22 |
| CN1065633C true CN1065633C (zh) | 2001-05-09 |
Family
ID=6526500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95116628A Expired - Fee Related CN1065633C (zh) | 1994-08-25 | 1995-08-25 | 热稳定偏振器 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5676885A (zh) |
| EP (1) | EP0703470B1 (zh) |
| JP (1) | JPH0868908A (zh) |
| CN (1) | CN1065633C (zh) |
| CA (1) | CA2156671A1 (zh) |
| DE (2) | DE4430096A1 (zh) |
| FI (1) | FI953952A (zh) |
| TW (1) | TW327675B (zh) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5867316A (en) * | 1996-02-29 | 1999-02-02 | Minnesota Mining And Manufacturing Company | Multilayer film having a continuous and disperse phase |
| GB9806313D0 (en) * | 1997-06-28 | 1998-05-20 | Sharp Kk | Method of making a spatial light modulator method of making a cell wall for a spatial light modulator spatial light modulator and cell wall for such aspatial |
| US6005713A (en) * | 1998-08-21 | 1999-12-21 | 3M Innovative Properties Company | Multilayer polarizer having a continuous and disperse phase |
| US7329434B2 (en) * | 2005-02-23 | 2008-02-12 | Eastman Kodak Company | Polarizing layer with adherent protective layer |
| DE102010043200A1 (de) * | 2010-02-10 | 2011-08-11 | Johnson Controls Automotive Electronics GmbH, 75196 | Anzeigeelement für eine Anzeigeeinheit in einem Fahrzeug |
| US9366900B2 (en) | 2010-03-05 | 2016-06-14 | Nitto Denko Corporation | Adhesive for polarizing plate, polarizing plate, method for producing same, optical film, and image display device |
| US9977264B2 (en) | 2012-08-21 | 2018-05-22 | Mitsubishi Gas Chemical Company, Inc. | Polarizing lens for sunglasses |
| CN112789528B (zh) * | 2018-09-25 | 2023-08-29 | 日东电工株式会社 | 偏光板及其制造方法、以及包含该偏光板的图像显示装置 |
| CN110609643B (zh) * | 2019-08-29 | 2021-02-23 | 武汉华星光电半导体显示技术有限公司 | 触控结构及显示面板 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4812520A (en) * | 1985-07-30 | 1989-03-14 | The Unites States Of America As Represented By The United States Department Of Energy | Method for the preparation of novel polyacetylene-type polymers |
| US4866147A (en) * | 1985-07-30 | 1989-09-12 | The United States Of America As Represented By The United States Department Of Energy | Soluble silylated polyacetylene derivatives and their use as percursors to novel polyacetylene-type polymers |
| DE3615765A1 (de) * | 1986-05-10 | 1987-11-12 | Bayer Ag | Polarisatoren auf polyacetylenbasis und ihre herstellung |
| US4818624A (en) | 1986-12-19 | 1989-04-04 | Polaroid Corporation, Patent Department | Stabilized light-polarizing material |
| DE3905027A1 (de) * | 1988-12-21 | 1990-06-28 | Bayer Ag | Hochwirksame polarisatoren |
| DE3842968A1 (de) | 1988-12-21 | 1990-06-28 | Bayer Ag | Laminierte polarisatoren |
| DE3905519A1 (de) * | 1989-02-23 | 1990-08-30 | Bayer Ag | Hochwirksame polarisatoren |
| EP0511590B1 (en) * | 1991-04-30 | 1997-10-15 | Matsushita Electric Industrial Co., Ltd. | Functional laminated chemically adsorbed films and methods of manufacturing the same |
-
1994
- 1994-08-25 DE DE19944430096 patent/DE4430096A1/de not_active Withdrawn
-
1995
- 1995-07-25 TW TW084107663A patent/TW327675B/zh active
- 1995-08-14 DE DE59509835T patent/DE59509835D1/de not_active Expired - Fee Related
- 1995-08-14 EP EP19950112762 patent/EP0703470B1/de not_active Expired - Lifetime
- 1995-08-17 JP JP23068795A patent/JPH0868908A/ja not_active Ceased
- 1995-08-18 US US08/516,888 patent/US5676885A/en not_active Expired - Fee Related
- 1995-08-22 CA CA 2156671 patent/CA2156671A1/en not_active Abandoned
- 1995-08-23 FI FI953952A patent/FI953952A/fi unknown
- 1995-08-25 CN CN95116628A patent/CN1065633C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2156671A1 (en) | 1996-02-26 |
| FI953952A (fi) | 1996-02-26 |
| CN1140842A (zh) | 1997-01-22 |
| FI953952A0 (fi) | 1995-08-23 |
| US5676885A (en) | 1997-10-14 |
| TW327675B (en) | 1998-03-01 |
| DE4430096A1 (de) | 1996-02-29 |
| EP0703470B1 (de) | 2001-11-14 |
| JPH0868908A (ja) | 1996-03-12 |
| EP0703470A1 (de) | 1996-03-27 |
| DE59509835D1 (de) | 2001-12-20 |
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