TWI597531B - A polarizing film, a polarizing film with an adhesive layer, and an image display device - Google Patents
A polarizing film, a polarizing film with an adhesive layer, and an image display device Download PDFInfo
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Description
本發明關於一種偏光薄膜。此外,本發明關於一種使用前述偏光薄膜之附黏著劑層之偏光薄膜。前述偏光薄膜或附黏著劑層之偏光薄膜可單獨或作為將其積層而成之光學薄膜來形成液晶顯示裝置(LCD)、有機EL顯示裝置等影像顯示裝置。 The present invention relates to a polarizing film. Further, the present invention relates to a polarizing film using an adhesive layer of the aforementioned polarizing film. The polarizing film or the polarizing film with an adhesive layer can form an image display device such as a liquid crystal display (LCD) or an organic EL display device either alone or as an optical film formed by laminating the film.
液晶顯示裝置基於其影像形成方式,必須在形成液晶面板表面之玻璃基板的兩側配置偏光薄膜。一般而言,偏光薄膜係使用在偏光件之單面或兩面上以聚乙烯醇系接著劑等貼合有保護薄膜而成之物,該偏光件則由聚乙烯醇系薄膜與碘等之二色性材料所構成。 In the liquid crystal display device, it is necessary to arrange a polarizing film on both sides of the glass substrate on which the surface of the liquid crystal panel is formed, based on the image forming method. In general, a polarizing film is obtained by bonding a protective film to a single surface or both surfaces of a polarizing material with a polyvinyl alcohol-based adhesive or the like, and the polarizing member is made of a polyvinyl alcohol-based film and iodine. Made up of color materials.
此外,偏光薄膜在熱衝撃(例如95℃、250小時之高溫下試驗)之嚴苛環境下,會因偏光件之收縮應力變化,而有容易在偏光件之吸收軸方向上整體發生裂紋的問題。亦即,偏光薄膜對於前述嚴苛環境之熱衝撃的耐裂紋性不足。尤其,從薄型化之觀點出發,僅在偏光件單面上設置保護薄膜之單側保護偏光薄膜因其設有保護薄膜側之偏光件收縮應力與保護薄膜相反側之偏光件收縮應力之落差, 會在偏光件內部發生過剰應力,而有容易在偏光件之吸收軸方向上發生數百μm之微小裂紋至猶如貫通整面般之貫通裂紋等各種裂紋的問題。 In addition, in a severe environment where the polarizing film is tested by hot stamping (for example, at 95 ° C for 250 hours), the polarizing film changes due to the contraction stress of the polarizing member, and there is a problem that cracks easily occur in the absorption axis direction of the polarizing member. . That is, the polarizing film is insufficient in crack resistance against thermal shock of the aforementioned severe environment. In particular, from the viewpoint of thinning, the one-side protective polarizing film provided with only the protective film on one side of the polarizing member is provided with a difference in shrinkage stress of the polarizing member on the side of the protective film and a contraction stress of the polarizing member on the opposite side of the protective film. When a squeaking stress occurs inside the polarizer, there is a problem that various cracks such as a through crack such as a through crack appearing in the absorption axis direction of the polarizer easily occur in the absorption axis direction of the polarizer.
為了抑制前述裂紋發生,例如,已有一種附黏著劑層之偏光薄膜獲提出,其係在單側保護偏光薄膜上設置抗拉彈性率100MPa以上之保護層,且進一步在該保護層上設置黏著劑層(專利文獻1)。此外,也提出一種附黏著劑層之偏光薄膜,其係在厚度25μm以下之偏光件單面上具有硬化型樹脂組成物之硬化物所構成之保護層,且在偏光件之另一側單面上具有保護薄膜,並在前述保護層外側具有黏著劑層(專利文獻2)。前述專利文獻1、2所記載之附黏著劑層之偏光薄膜從抑制裂紋發生之觀點來看甚是有效。又,從抑制裂紋發生同時薄層化、輕量化之觀點出發,已提出可在偏光件之至少單面上設置由水溶性皮膜形成性組成物(聚乙烯醇系樹脂組成物)所構成之保護層(專利文獻3)。 In order to suppress the occurrence of the above-mentioned cracks, for example, a polarizing film with an adhesive layer has been proposed, which is provided with a protective layer having a tensile modulus of 100 MPa or more on the one-side protective polarizing film, and further adhesive is provided on the protective layer. Agent layer (Patent Document 1). Further, a polarizing film with an adhesive layer which has a protective layer composed of a cured product of a hardened resin composition on one surface of a polarizing member having a thickness of 25 μm or less and a single side on the other side of the polarizing member is also proposed. The protective film is provided thereon, and an adhesive layer is provided outside the protective layer (Patent Document 2). The polarizing film with an adhesive layer described in the above Patent Documents 1 and 2 is effective from the viewpoint of suppressing occurrence of cracks. In addition, from the viewpoint of suppressing the occurrence of cracks and reducing the thickness and weight, it has been proposed to provide a coating composed of a water-soluble film forming composition (polyvinyl alcohol resin composition) on at least one surface of the polarizing material. Layer (Patent Document 3).
【專利文獻1】日本特開2010-009027號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-009027
【專利文獻2】日本特開2013-160775號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-160775
【專利文獻3】日本特開2005-043858號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2005-043858
此外,依據專利文獻1至3,可藉由前述保護層使前述偏光件朝吸收軸方向之收縮控制到某種程度,而可抑制前述裂紋之發生。然而,即使利用前述保護層,偏光件因收縮應力所致尺寸變化仍難謂獲充分抑制。 Further, according to Patent Documents 1 to 3, the shrinkage of the polarizer in the absorption axis direction can be controlled to some extent by the protective layer, and the occurrence of the above-mentioned crack can be suppressed. However, even with the aforementioned protective layer, it is difficult to sufficiently suppress the dimensional change of the polarizer due to the shrinkage stress.
又,偏光件也正趨進行薄型化。使用於偏光薄膜之偏光件薄化時,偏光件之收縮應力變化會縮小。但因偏光件本身薄型化,即使施加較習知技術更弱之力,偏光件仍會破裂,因此即使利用薄型偏光件,耐裂紋性仍不充分。 Moreover, the polarizer is also becoming thinner. When the polarizing member used for the polarizing film is thinned, the change in the shrinkage stress of the polarizing member is reduced. However, since the polarizing member itself is thinned, the polarizing member is broken even if a force weaker than the conventional technique is applied, so that even with the thin polarizing member, the crack resistance is insufficient.
又,因偏光件具有諸如聚乙烯醇系薄膜之延伸步驟,即使是薄型偏光件,在延伸步驟中獲得之偏光件仍在內部具有殘留應力之狀態下進行製造。又,一般來說,偏光薄膜雖在偏光件之單面或兩面上貼合有各種保護薄膜等,但該偏光薄膜在前述熱衝撃試驗中前述各種保護薄膜之殘留應力與偏光件之殘留應力會以組合之形式表現,偏光薄膜以整體而言會顯示出收縮之動態。因此,即使是薄型偏光件,特別是在用以形成偏光件之聚乙烯醇樹脂之Tg附近及其以上之高溫試驗(例如85℃以上)時,並無法充分抑制偏光件因收縮應力引起之尺寸變化。 Further, since the polarizing member has an extending step such as a polyvinyl alcohol-based film, even in the case of the thin polarizing member, the polarizing member obtained in the extending step is manufactured with residual stress inside. Further, in general, the polarizing film has various protective films or the like adhered to one surface or both surfaces of the polarizing member, but the residual stress of the various protective films and the residual stress of the polarizing member in the thermal filming test of the polarizing film are In the form of a combination, the polarizing film shows the dynamics of shrinkage as a whole. Therefore, even in the case of a thin polarizing member, particularly in the vicinity of the Tg of the polyvinyl alcohol resin for forming the polarizing member and above (for example, 85 ° C or higher), the size of the polarizing member due to the shrinkage stress cannot be sufficiently suppressed. Variety.
本發明之目的在於提供一種偏光薄膜,其係於偏光件之至少單面上具有透明層,可於85℃以上之高溫環境下抑制裂紋發生,且可抑制偏光件之尺寸變化。此外,本發明之目的在於提供一種使用了前述偏光薄膜之附黏著劑層之偏光薄膜。本發明進一步有關於一種影像顯示裝 置,其具有前述偏光薄膜或附黏著劑層之偏光薄膜。 An object of the present invention is to provide a polarizing film which has a transparent layer on at least one surface of a polarizing member, can suppress crack occurrence in a high temperature environment of 85 ° C or higher, and can suppress dimensional change of the polarizer. Further, it is an object of the invention to provide a polarizing film using an adhesive layer of the above polarizing film. The invention further relates to an image display device The polarizing film of the foregoing polarizing film or adhesive layer is provided.
本案發明人經精心探究,結果發現可藉由下述偏光薄膜等來解決上述課題,而終至完成本發明。 As a result of intensive investigation, the inventors of the present invention have found that the above problems can be solved by the following polarizing film or the like, and the present invention is completed.
亦即,本發明有關於一種偏光薄膜,其係於偏光件之至少一面上具有透明層者,特徵在於:前述偏光件含有聚乙烯醇系樹脂,且厚度為15μm以下;前述偏光件之前述透明層側具有與前述透明層之相溶層;並且,前述偏光件之厚度A與前述相溶層之厚度B滿足通式:(100×B/A)≧1。 That is, the present invention relates to a polarizing film which has a transparent layer on at least one side of a polarizing member, wherein the polarizing member contains a polyvinyl alcohol resin and has a thickness of 15 μm or less; and the transparent portion of the polarizing member The layer side has a compatibility layer with the transparent layer; and the thickness A of the polarizer and the thickness B of the compatibility layer satisfy the general formula: (100 × B / A) ≧ 1.
於前述偏光薄膜中,相較於前述偏光件中前述相溶層以外之部分,前述相溶層宜具更低之硼酸濃度。 In the polarizing film, the phase of the phase of the polarizing member is preferably a lower concentration of boric acid than the portion of the polarizing member.
此外,本發明有關於一種偏光薄膜,其係於偏光件之至少一面上具有透明層,特徵在於:前述偏光件含有聚乙烯醇系樹脂,且厚度為15μm以下;前述偏光件中之前述透明層側具有硼酸低濃度層,其相較於前述偏光件其他部分硼酸濃度相對較低;並且,前述偏光件之厚度A與前述硼酸低濃度層之厚度C滿足通式:(100×C/A)≧1。 Further, the present invention relates to a polarizing film having a transparent layer on at least one surface of a polarizing member, wherein the polarizing member contains a polyvinyl alcohol-based resin and has a thickness of 15 μm or less; and the transparent layer in the polarizing member The side has a low concentration layer of boric acid, which is relatively low in boric acid concentration compared with the other portions of the polarizer; and the thickness A of the polarizer and the thickness C of the boric acid low concentration layer satisfy the general formula: (100×C/A) ≧1.
前述偏光薄膜中,前述透明層之厚度宜為0.2μm以上。又,前述透明層之厚度宜在6μm以下。 In the polarizing film, the thickness of the transparent layer is preferably 0.2 μm or more. Further, the thickness of the transparent layer is preferably 6 μm or less.
前述偏光薄膜中,前述透明層之配向性指數宜為0.05以下。 In the polarizing film, the alignment index of the transparent layer is preferably 0.05 or less.
前述偏光薄膜中,前述透明層宜為含聚乙烯醇系樹脂之形成材料之形成物。前述聚乙烯醇系樹脂宜皂化度為99莫耳%以上且平均聚合度為2000以上。 In the polarizing film, the transparent layer is preferably a formed product of a material containing a polyvinyl alcohol resin. The polyvinyl alcohol-based resin preferably has a degree of saponification of 99 mol% or more and an average degree of polymerization of 2,000 or more.
前述偏光薄膜中,前述偏光件之單體透光率T及偏光度P所示光學特性宜在下式所示之範圍內:P>-(100.929T-42.4-1)×100(但T<42.3);或P≧99.9(但T≧42.3)。 In the polarizing film, the optical characteristics of the polarizing element T and the degree of polarization P of the polarizing member are preferably in the range of the following formula: P>-(10 0.929T-42.4 -1)×100 (but T<42.3); or P≧99.9 (but T≧42.3).
前述偏光薄膜可具有保護薄膜。 The aforementioned polarizing film may have a protective film.
此外,本發明有關於一種附黏著劑層之偏光薄膜,其特徵在於具有前述偏光薄膜及黏著劑層。 Further, the present invention relates to a polarizing film with an adhesive layer characterized by comprising the above-mentioned polarizing film and an adhesive layer.
又,本發明有關於一種影像顯示裝置,其具有前述偏光薄膜或前述附黏著劑層之偏光薄膜。 Furthermore, the present invention relates to an image display device comprising the polarizing film or the polarizing film of the adhesive layer.
依據本發明之偏光薄膜,藉由在偏光件設置前述透明層,可在85℃以上高溫環境下抑制裂紋發生。又,本發明之偏光薄膜在前述偏光件之前述透明層側具有與前述透明層之相溶層。前述相溶層係藉由形成透明層之一部份材料滲入偏光件中且偏光件表面附近之成分滲出而形成於偏光件表面附近。可藉由使用可滲透到偏光件中之材料而在偏光件表面形成透明層以形成該相溶層。 According to the polarizing film of the present invention, by providing the transparent layer in the polarizing member, crack generation can be suppressed in a high temperature environment of 85 ° C or higher. Further, the polarizing film of the present invention has a compatibility layer with the transparent layer on the side of the transparent layer of the polarizing member. The phase of the foregoing phase is formed in the vicinity of the surface of the polarizer by a part of the material forming the transparent layer penetrating into the polarizer and oozing out of the component near the surface of the polarizer. A transparent layer may be formed on the surface of the polarizer by using a material permeable to the polarizing member to form the phase-soluble layer.
舉例來說,一般偏光件之製作係藉由對聚乙烯醇系樹脂(薄膜)施行延伸步驟來進行,因此所得偏光件中之 樹脂分子會呈現具某種程度規則性而定向之狀態。與其相對地,形成於偏光件表面之透明層例如係以塗布方式來形成。因此,透明層不會施行延伸步驟,形成透明層之分子不會規則地定向。本發明之相溶層如上述般係藉由使透明層之形成成分滲入偏光件中而形成。形成透明層之際,滲入偏光件之透明層成分具有將偏光件中之分子配向性予以部分緩和之功用。推定此種功用與偏光件殘留應力之緩和相關而抑制了偏光件之尺寸變化。又,本發明並不受此一推定機制所侷限。 For example, generally, the polarizing member is produced by performing an extending step on a polyvinyl alcohol-based resin (film), and thus the obtained polarizing member The resin molecules will assume a state of regularity and orientation. On the other hand, the transparent layer formed on the surface of the polarizer is formed, for example, by coating. Therefore, the transparent layer does not perform the stretching step, and the molecules forming the transparent layer are not regularly oriented. The phase-soluble layer of the present invention is formed by infiltrating a forming component of a transparent layer into a polarizing member as described above. When the transparent layer is formed, the transparent layer component penetrating into the polarizing member has a function of partially alleviating the molecular alignment in the polarizing member. It is presumed that such a function is related to the relaxation of the residual stress of the polarizer, and the dimensional change of the polarizer is suppressed. Moreover, the present invention is not limited by this presumptive mechanism.
此外,本發明之偏光薄膜使用厚度15μm以下之薄型偏光件。薄型偏光件中偏光件之收縮應力變化雖會變少,但因偏光件本身薄型化,耐裂紋性並不充分。若以本發明之偏光薄膜,即便使用薄型偏光件仍因具有透明層而可提升耐裂紋性。 Further, the polarizing film of the present invention uses a thin polarizing member having a thickness of 15 μm or less. Although the change in the shrinkage stress of the polarizer in the thin polarizer is small, the crack resistance is not sufficient because the polarizer itself is thinned. According to the polarizing film of the present invention, crack resistance can be improved by having a transparent layer even if a thin polarizing member is used.
1‧‧‧偏光件 1‧‧‧ polarizer
2‧‧‧透明層 2‧‧‧Transparent layer
3‧‧‧樹脂基材 3‧‧‧Resin substrate
4‧‧‧保護薄膜 4‧‧‧Protective film
10‧‧‧偏光薄膜 10‧‧‧Polarized film
11‧‧‧偏光薄膜 11‧‧‧ polarizing film
A‧‧‧偏光件厚度 A‧‧‧ polarizer thickness
B‧‧‧相溶層厚度 B‧‧‧Composition layer thickness
X‧‧‧相溶層 X‧‧‧compatible layer
圖1為本發明偏光薄膜之概略截面圖之一例。 Fig. 1 is a view showing an example of a schematic cross-sectional view of a polarizing film of the present invention.
圖2為本發明偏光薄膜之概略截面圖之一例。 Fig. 2 is a view showing an example of a schematic cross-sectional view of a polarizing film of the present invention.
圖3為測定相溶層之相關圖表。 Figure 3 is a graph showing the correlation of the dissolved layers.
以下一邊參照圖1、圖2一邊說明本發明之偏光薄膜10、11。偏光薄膜10、11具有偏光件1及透明層2。此外,本發明之偏光薄膜10、11如圖1、圖2所示,在前述偏光件1之前述透明層2側具有與前述透明層2之相溶層X。圖 1(A)雖僅顯示偏光件1、相溶層X及透明層2,但如圖1(B)所示,圖1(A)中偏光件1之側可設有樹脂基材3。樹脂基材3可舉例如製造薄型之偏光件1時所使用之樹脂基材。 Hereinafter, the polarizing films 10 and 11 of the present invention will be described with reference to Figs. 1 and 2 . The polarizing films 10 and 11 have a polarizer 1 and a transparent layer 2. Further, as shown in FIGS. 1 and 2, the polarizing films 10 and 11 of the present invention have a compatibility layer X with the transparent layer 2 on the side of the transparent layer 2 of the polarizer 1. Figure 1(A) shows only the polarizer 1, the compatibility layer X, and the transparent layer 2. However, as shown in Fig. 1(B), the resin substrate 3 may be provided on the side of the polarizer 1 in Fig. 1(A). The resin substrate 3 can be, for example, a resin substrate used in the production of the thin polarizer 1 .
此外,圖2之偏光薄膜11中,圖1(A)之偏光薄膜10上設有保護薄膜4。保護薄膜4可設在圖1(A)之偏光薄膜10之偏光薄膜單面或兩面上。圖2(A)中保護薄膜4僅設於偏光件1側,但保護薄膜4也可僅設於透明層2側。圖2(B)係在圖1(A)之偏光薄膜10兩側設置保護薄膜4。又,保護薄膜4也可積層2片以上使用。圖2(C)係在偏光件1之單側上積層有2片保護薄膜4之情況。另,雖未圖示於圖2中,偏光件1或透明層2與保護薄膜4可經由接著劑層、黏著劑層、下塗層(底漆層)等之中介層來積層。又,雖未圖示,也可對保護薄膜4設置易接著層或施加活性化處理,再積層該易接著層與接著劑層。 Further, in the polarizing film 11 of Fig. 2, the protective film 4 is provided on the polarizing film 10 of Fig. 1(A). The protective film 4 can be provided on one or both sides of the polarizing film of the polarizing film 10 of Fig. 1(A). In FIG. 2(A), the protective film 4 is provided only on the side of the polarizer 1, but the protective film 4 may be provided only on the side of the transparent layer 2. 2(B) is a protective film 4 provided on both sides of the polarizing film 10 of FIG. 1(A). Further, the protective film 4 may be used in two or more layers. Fig. 2(C) shows a case where two protective films 4 are laminated on one side of the polarizing member 1. Further, although not shown in FIG. 2, the polarizer 1, the transparent layer 2, and the protective film 4 may be laminated via an interposer such as an adhesive layer, an adhesive layer, or an undercoat layer (primer layer). Further, although not shown, an easy adhesion layer or an activation treatment may be provided on the protective film 4, and the easy-adhesion layer and the adhesive layer may be laminated.
又,雖未圖示,本發明之偏光薄膜10、11可設置黏著劑層。進一步來說,可在黏著劑層上設置分隔件。又,本發明之偏光薄膜10、11(尤其是具有保護薄膜4時)可設置表面保護薄膜。 Further, although not shown, the polarizing films 10 and 11 of the present invention may be provided with an adhesive layer. Further, a spacer may be provided on the adhesive layer. Further, the polarizing film 10, 11 of the present invention (especially when the protective film 4 is provided) may be provided with a surface protective film.
本發明之偏光薄膜10、11中,相溶層X係一透明層2之形成成分從偏光件1表面滲透到內部所形成之層,可藉由相溶層X來緩和偏光件1之殘留應力。其結果則是可抑制偏光件之尺寸變化。由此觀點出發,於本發明中,前述偏光件1之厚度A與前述相溶層之厚度B係調整成滿足通式:(100×B/A)≧1。相溶層X之厚度B係以與偏光件1之厚 度A的關係作調整。前述(100×B/A)之值從緩和偏光件之殘留應力之觀點來看以2以上為宜,且宜為2.5以上,以3以上為佳,4以上更佳,而以5以上尤佳。另一方面,前述(100×B/A)之值過大時,偏光件1之厚度A中相溶層X之比例過大而有損及光學特性之虞。從此觀點出發,前述(100×B/A)之值以10以下為宜,更宜為7以下。 In the polarizing film 10, 11 of the present invention, the phase forming layer X is a layer formed by a transparent layer 2 penetrating from the surface of the polarizing member 1 to the inside, and the residual stress of the polarizing member 1 can be alleviated by the phase-soluble layer X. . As a result, the dimensional change of the polarizer can be suppressed. From this point of view, in the present invention, the thickness A of the polarizer 1 and the thickness B of the compatibility layer are adjusted to satisfy the general formula: (100 × B / A) ≧ 1. The thickness B of the phase-soluble layer X is thicker than the polarizer 1 The relationship of degree A is adjusted. The value of (100 × B / A) is preferably 2 or more from the viewpoint of relaxing the residual stress of the polarizer, and is preferably 2.5 or more, preferably 3 or more, more preferably 4 or more, and more preferably 5 or more. . On the other hand, when the value of (100 × B / A) is too large, the ratio of the compatibility layer X in the thickness A of the polarizer 1 is too large to impair the optical characteristics. From this point of view, the value of (100 × B / A) is preferably 10 or less, more preferably 7 or less.
前述相溶層X之厚度B可按載於實施例之方法來測定。 The thickness B of the aforementioned phase-soluble layer X can be measured by the method described in the examples.
偏光件不特別受限,可使用各種。偏光件可舉例如:使聚乙烯醇系薄膜、部分縮甲醛化聚乙烯醇系薄膜及乙烯‧乙酸乙烯酯共聚物系部分皂化薄膜等之親水性高分子薄膜吸附碘或二色性染料之二色性物質並使其單軸延伸之物;及,聚乙烯醇之脫水處理物或聚氯乙烯之脫鹽酸處理物等多烯系定向薄膜等。於其等之中,以由聚乙烯醇系薄膜與碘等二色性物質所構成之偏光件為宜。 The polarizing member is not particularly limited, and various types can be used. The polarizing member may, for example, be a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene/vinyl acetate copolymer-based partially saponified film, or a dichroic dye. A coloring substance and a uniaxially stretched product thereof; and a polyene-based oriented film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among them, a polarizing member comprising a polyvinyl alcohol-based film and a dichroic material such as iodine is preferred.
將聚乙烯醇系薄膜以碘染色再單軸延伸而成之偏光件舉例來說可以下述方式製作:將聚乙烯醇薄膜浸漬到碘之水溶液藉此染色,再延伸到原長之3~7倍。亦可依需要而含有硼酸及硫酸鋅、氯化鋅等,亦可浸漬到碘化鉀等之水溶液。更可視需要而在染色前將聚乙烯醇系薄膜浸到水中進行水洗。水洗聚乙烯醇系薄膜除了可洗淨聚乙烯醇系薄膜表面之髒污及抗結塊劑之外,可使聚乙烯醇系薄膜膨潤,也有可防止染色不均等不均勻情況之效果。延伸可 在以碘染色後進行,亦可一邊染色一邊延伸,也可延伸後再以碘染色。也可以硼酸或碘化鉀等之水溶液或於水浴中進行延伸。 The polarizing member obtained by dyeing a polyvinyl alcohol-based film by iodine and then uniaxially stretching can be produced, for example, by dipping a polyvinyl alcohol film into an aqueous solution of iodine to be dyed, and then extending to the original length of 3 to 7. Times. The boric acid, zinc sulfate, zinc chloride or the like may be contained as needed, or may be immersed in an aqueous solution of potassium iodide or the like. The polyvinyl alcohol-based film may be immersed in water for washing with water before the dyeing as needed. The water-washed polyvinyl alcohol-based film can swell the polyvinyl alcohol-based film in addition to the dirt and anti-caking agent on the surface of the polyvinyl alcohol-based film, and can also prevent unevenness in dyeing unevenness. Extended After dyeing with iodine, it may be extended while dyeing, or may be extended with iodine. It is also possible to carry out the extension in an aqueous solution of boric acid or potassium iodide or in a water bath.
前述偏光件使用厚度15μm以下之薄型偏光件。偏光件之厚度從薄型化及對熱衝撃所致裂紋之耐性的觀點來看,以12μm為宜,且宜於10μm以下,更宜於8μm以下,更以7μm以下為佳,6μm以下尤佳。另一方面,偏光件厚度以2μm以上為宜,3μm以上更佳。此種薄型偏光件之厚度不均較少,具優異觀視性且尺寸變化較少,因此對於熱衝撃之耐久性優異。 As the polarizing member, a thin polarizing member having a thickness of 15 μm or less is used. The thickness of the polarizer is preferably 12 μm, more preferably 10 μm or less, more preferably 8 μm or less, still more preferably 7 μm or less, and particularly preferably 6 μm or less from the viewpoint of thickness reduction and resistance to cracking caused by thermal punching. On the other hand, the thickness of the polarizer is preferably 2 μm or more, more preferably 3 μm or more. Such a thin polarizer has a small thickness unevenness, excellent visibility, and small dimensional change, and therefore is excellent in durability against thermal punching.
從延伸安定性及光學耐久性之觀點出發,偏光件宜含有硼酸。此外,含於偏光件中之硼酸含量從抑制貫通裂紋等裂紋發生之觀點來看,相對於偏光件全量,宜在25重量%以下,且宜在20重量%以下,以18重量%以下為佳,16重量%以下更佳。含於偏光件中之硼酸含量超過20重量%時,即使在將偏光件厚度控制到10μm以下之情況,偏光件之收縮應力仍會提高而變得容易發生貫通裂紋等裂紋,因此並不理想。另一方面,從偏光件之延伸安定性及光學耐久性之觀點來看,相對於偏光件全量之硼酸含量以10重量%以上為宜,12重量%以上更佳。 The polarizer preferably contains boric acid from the viewpoint of elongation stability and optical durability. Further, the boric acid content contained in the polarizer is preferably 25% by weight or less, and preferably 20% by weight or less, and preferably 18% by weight or less, based on the total amount of the polarizer, from the viewpoint of suppressing occurrence of cracks such as through cracks. More preferably, it is 16% by weight or less. When the content of the boric acid contained in the polarizer is more than 20% by weight, even when the thickness of the polarizer is controlled to 10 μm or less, the shrinkage stress of the polarizer is increased, and cracks such as through cracks are likely to occur, which is not preferable. On the other hand, from the viewpoint of the stability of the polarizer and the optical durability, the total amount of boric acid relative to the polarizer It is preferably 10% by weight or more, more preferably 12% by weight or more.
厚度15μm以下之薄型偏光件可代表性地列舉如記載於日本特許第4751486號說明書、日本特許第4751481號說明書、日本特許第4815544號說明書、日本特許第5048120號說明書、日本特許第5587517號說明書、國際公 開第2014/077599號小冊、國際公開第2014/077636號小冊等之薄型偏光件或是由其等所載之製造方法製得之薄型偏光件。 The thin polarizer having a thickness of 15 μm or less is exemplified by the specification of Japanese Patent No. 4751486, Japanese Patent No. 4751481, Japanese Patent No. 4815544, Japanese Patent No. 5048120, and Japanese Patent No. 5587517. International public A thin polarizer such as a booklet of No. 2014/077599, a booklet of International Publication No. 2014/077636, or a thin polarizer made by the manufacturing method contained therein.
前述偏光件宜構造成以單體透光率T及偏光度P表示之光學特性會滿足後式P>-(100.929T-42.4-1)×100(但T<42.3)或P≧99.9(但T≧42.3)之條件。構造成滿足前述條件之偏光件無歧義地具有用作使用大型顯示元件之液晶電視用顯示器所需求之性能。具體來說,則是對比1000:1以上且最大亮度500cd/m2以上。就其他用途而言,例如可貼合於有機EL顯示裝置之觀視側。 The polarizing member is preferably configured such that the optical characteristics expressed by the monomer transmittance T and the degree of polarization P satisfy the following formula P>-(10 0.929T-42.4 -1)×100 (but T<42.3) or P≧99.9 ( But the conditions of T≧42.3). The polarizer configured to satisfy the aforementioned conditions unambiguously has the performance required for a display for a liquid crystal television using a large display element. Specifically, it is a comparison of 1000:1 or more and a maximum luminance of 500 cd/m 2 or more. For other uses, for example, it can be attached to the viewing side of the organic EL display device.
就前述薄型偏光件而言,從在包含積層體狀態下進行延伸步驟與染色步驟之製法中仍可高倍率延伸而提高偏光性能之觀點來看,以自下述製法製得者為佳:在日本特許第4751486號說明書、日本特許第4751481號說明書、日本特許第4815544號說明書有所記載,包含在硼酸水溶液中進行延伸之步驟的製法;尤其是,在日本特許第4751481號說明書、日本特許第4815544號說明書中有所記載,包含在硼酸水溶液中進行延伸前先輔助地進行空中延伸之步驟的製法。此等薄型偏光件可藉由包含下述步驟之製法來製得:使聚乙烯醇系樹脂(以下亦稱為PVA系樹脂)層與延伸用樹脂基材於積層體狀態下進行延伸之步驟以及染色步驟。若為此種製法,即使PVA系樹脂層較薄,藉由獲延伸用樹脂基材支持,可免於發生延伸所致斷裂等之不良情況來進行延伸。 In view of the fact that the thin polarizer is capable of extending at a high magnification and improving the polarizing performance in the method of performing the stretching step and the dyeing step in the state of including the laminated body, it is preferable to obtain the method from the following method: Japanese Patent No. 4751486, Japanese Patent No. 4751481, and Japanese Patent No. 4815544, including a method of performing a step of stretching in an aqueous boric acid solution; in particular, Japanese Patent No. 4751481, Japanese Patent No. There is a description in the specification of No. 4815544, which comprises a process for assisting in the air extension step before extending in a boric acid aqueous solution. These thin polarizers can be obtained by a method comprising the steps of: extending a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a resin substrate for stretching in a layered state; Dyeing step. According to this method, even if the PVA-based resin layer is thin, it can be stretched without being damaged by elongation or the like by being supported by the resin substrate for stretching.
另外,圖1(B)所示樹脂基材(延伸用樹脂基材)可使用已應用在製造前述薄型偏光件之物。樹脂基材之形成材料可使用各種熱可塑性樹脂。熱可塑性樹脂可舉例如聚對酞酸乙二酯系樹脂等之酯系樹脂、降莰烯系樹脂等之環烯烴系樹脂、聚丙烯等之烯烴系樹脂、聚醯胺系樹脂、聚碳酸酯系樹脂及其等之共聚物樹脂等。於其等之中,從製造容易度及成本減輕之觀點出發,以酯系樹脂為宜。酯系熱可塑性樹脂基材可使用非晶性酯系熱可塑性樹脂基材或結晶性酯系熱可塑性樹脂基材。 Moreover, the resin base material (resin base material for extension) shown in FIG. 1(B) can be used for the manufacture of the said thin type polarizer. A variety of thermoplastic resins can be used as the material for forming the resin substrate. The thermoplastic resin may, for example, be an ester resin such as a polyethylene terephthalate resin, a cycloolefin resin such as a norbornene resin, an olefin resin such as polypropylene, a polyamide resin, or a polycarbonate. Resin and its copolymer resin and the like. Among them, an ester resin is preferred from the viewpoints of ease of production and cost reduction. As the ester-based thermoplastic resin substrate, a non-crystalline ester-based thermoplastic resin substrate or a crystalline ester-based thermoplastic resin substrate can be used.
構成前述保護薄膜之材料以具有優異透明性、機械強度、熱安定性、水分障蔽性及等向性等之物為佳。例如聚對酞酸乙二酯或聚萘二甲酸乙二酯等聚酯系聚合物、二乙醯基纖維素或三乙醯基纖維素等纖維素系聚合物、聚甲基丙烯酸甲酯等丙烯酸系聚合物、聚苯乙烯或丙烯腈‧苯乙烯共聚物(AS樹脂)等之苯乙烯系聚合物、聚碳酸酯系聚合物等。此外,聚乙烯、聚丙烯、具有環系乃至於降莰烯結構之聚烯烴、諸如乙烯‧丙烯共聚物之聚烯烴系聚合物、氯乙烯系聚合物、耐倫或芳香族聚醯胺等之醯胺系聚合物、醯亞胺系聚合物、碸系聚合物、聚醚碸系聚合物、聚醚醚酮系聚合物、聚伸苯硫系聚合物、乙烯醇系聚合物、氯化亞乙烯系聚合物、聚乙烯丁醛系聚合物、芳基化物系聚合物、聚甲醛系聚合物、環氧系聚合物或上述聚合物之摻合 物等均可作為形成上述保護薄膜之聚合物之例。 The material constituting the protective film is preferably one having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropic properties. For example, a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose-based polymer such as diethyl cellulose or triethyl fluorenyl cellulose, or polymethyl methacrylate. A styrene-based polymer such as an acrylic polymer, a polystyrene or an acrylonitrile/styrene copolymer (AS resin), or a polycarbonate-based polymer. Further, polyethylene, polypropylene, polyolefin having a ring system or a norbornene structure, a polyolefin polymer such as an ethylene/propylene copolymer, a vinyl chloride polymer, a lanthanum or an aromatic polyamide, or the like Amidoxime polymer, quinone-based polymer, fluorene-based polymer, polyether fluorene-based polymer, polyetheretherketone-based polymer, polyphenylene sulfide-based polymer, vinyl alcohol-based polymer, and chloride Blending of a vinyl polymer, a polyvinyl butyral polymer, an arylate polymer, a polyoxymethylene polymer, an epoxy polymer or the above polymer The article or the like can be exemplified as a polymer which forms the above protective film.
另,保護薄膜中也可含有1種以上之任意適切添加劑。添加劑可舉例如紫外線吸收劑、抗氧化劑、滑劑、可塑劑、脫模劑、著色防止劑、阻燃劑、核劑、帶電防止劑、顏料及著色劑等。保護薄膜中之上述熱可塑性樹脂含量以50~100重量%為宜,且以50~99重量%為佳,更宜為60~98重量%且尤宜為70~97重量%。保護薄膜中之上述熱可塑性樹脂含量為50重量%以下時,會有熱可塑性樹脂無法充分表現原有之高透明性等之虞。 Further, the protective film may contain one or more optional additives. Examples of the additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, mold release agents, coloring inhibitors, flame retardants, nucleating agents, charging inhibitors, pigments, and color formers. The content of the thermoplastic resin in the protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight and particularly preferably 70 to 97% by weight. When the content of the thermoplastic resin in the protective film is 50% by weight or less, the thermoplastic resin may not sufficiently exhibit the original high transparency and the like.
前述保護薄膜也可使用相位差薄膜、提高亮度薄膜及擴散薄膜等。相位差薄膜可列舉如具有正面相位差40nm以上及/或厚度方向相位差80nm以上之相位差者。正面相位差通常控制在40~200nm範圍內,厚度方向相位差通常控制在80~300nm範圍內。保護薄膜使用相位差薄膜時,該相位差薄膜也會作為偏光件保護薄膜發揮功能,因此可謀求薄型化。 As the protective film, a retardation film, a brightness film, a diffusion film, or the like can be used. Examples of the retardation film include those having a front phase difference of 40 nm or more and/or a thickness direction retardation of 80 nm or more. The front phase difference is usually controlled within the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled within the range of 80 to 300 nm. When a retardation film is used as the protective film, the retardation film also functions as a polarizer protective film, so that it can be made thinner.
相位差薄膜可列舉如將熱可塑性樹脂薄膜施行單軸或二軸延伸處理所構成之雙折射性薄膜。上述延伸溫度及延伸倍率等可視相位差值、薄膜材料及厚度來適當設定。 The retardation film may, for example, be a birefringent film formed by subjecting a thermoplastic resin film to uniaxial or biaxial stretching treatment. The visible phase difference such as the extension temperature and the stretching ratio, the film material, and the thickness are appropriately set.
保護薄膜之厚度可適當決定,但一般因強度及處置性等作業性、薄層性等觀點,為1~500μm程度。特別是以1~300μm為宜,5~200μm為佳,5~150μm更佳,尤以20~100μm在薄型之情況下特別合適。 The thickness of the protective film can be appropriately determined, but it is generally about 1 to 500 μm from the viewpoints of workability such as strength and handleability, and thin layer properties. In particular, it is preferably 1 to 300 μm, preferably 5 to 200 μm, more preferably 5 to 150 μm, and particularly preferably 20 to 100 μm in the case of a thin type.
前述保護薄膜之不使其接著偏光件之面(尤其是圖1之態樣)上可設置硬塗層、抗反射層、抗黏層、擴散層乃至於防眩層等之機能層。另,上述硬塗層、抗反射層、抗黏層、擴散層及防眩層等之機能層除了可設在保護薄膜本身之外,亦可與保護薄膜分設而另為其他個體。 The protective film may be provided with a functional layer such as a hard coat layer, an antireflection layer, an anti-adhesion layer, a diffusion layer or an anti-glare layer on the surface of the polarizer (especially in the aspect of FIG. 1). Further, the functional layers such as the hard coat layer, the antireflection layer, the anti-adhesion layer, the diffusion layer, and the anti-glare layer may be provided separately from the protective film in addition to the protective film itself, and may be other individuals.
前述保護薄膜與偏光件係經由接著劑層、黏著劑層、下塗層(底漆層)等之中介層來積層。此時,宜透過中介層以無空氣間隙之方式積層兩者。 The protective film and the polarizer are laminated via an interposer such as an adhesive layer, an adhesive layer, or an undercoat layer (primer layer). At this time, it is preferable to laminate both layers through the interposer in the manner of no air gap.
接著劑層係由接著劑形成。接著劑之種類並未特別受限,可使用各種之物。前述接著劑層只要是光學上透明即不特別受限,接著劑可使用水系、溶劑系、熱熔系、活性能量線硬化型等各種形態之物,但以水系接著劑或活性能量線硬化型接著劑為宜。 The layer of the agent is then formed from an adhesive. The kind of the subsequent agent is not particularly limited, and various materials can be used. The adhesive layer is not particularly limited as long as it is optically transparent, and various materials such as an aqueous system, a solvent system, a hot melt system, and an active energy ray-curing type can be used as the adhesive, but a water-based adhesive or an active energy ray-curable type can be used. The subsequent agent is preferably.
水系接著劑可例示如異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯基系乳膠系、水系聚酯等。水系接著劑通常係以水溶液所構成之接著劑的形式使用,通常含有0.5~60重量%之固體成分。 The water-based adhesive agent may, for example, be an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, or an aqueous polyester. The aqueous binder is usually used in the form of an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of a solid component.
活性能量線硬化型接著劑係藉由電子射線、紫外線(自由基硬化型、陽離子硬化型)等活性能量線來進行硬化的接著劑,例如可以電子線硬化型、紫外線硬化型之態樣作使用。活性能量線硬化型接著劑可使用如光自由基硬化型接著劑。使用光自由基硬化型活性能量線硬化型接著劑作為紫外線硬化型時,該接著劑含有自由基聚合性化合 物及光聚合引發劑。 The active energy ray-curable adhesive is an adhesive which is cured by an active energy ray such as an electron beam or an ultraviolet ray (radical hardening type or cation hardening type), and can be used, for example, in an electron beam curing type or an ultraviolet curing type. . As the active energy ray-curable adhesive, for example, a photo-radical hardening type adhesive can be used. When a photoradical-curable active energy ray-curable adhesive is used as the ultraviolet curing type, the adhesive contains a radical polymerizable compound And photopolymerization initiator.
接著劑之塗佈方式可按接著劑的黏度及目標厚度來適當選擇。塗佈方式之例示可舉例如:逆轉式塗佈機、凹版塗佈機(直接、逆轉或平版)、棒逆轉式塗佈機、輥塗佈機、鑄模塗佈機、棒塗佈機、刮棒式塗佈機等。除此之外,塗佈尚可適當使用浸塗法等方式。 The coating method of the subsequent agent can be appropriately selected depending on the viscosity of the adhesive and the target thickness. Examples of the coating method include, for example, a reverse coater, a gravure coater (direct, reverse or lithographic), a bar reverse coater, a roll coater, a die coater, a bar coater, and a scraper. Bar coater, etc. In addition to this, the coating may be suitably carried out by a dip coating method or the like.
又,前述接著劑之塗佈在使用水系接著劑等時,宜以使最終形成之接著劑層厚度呈30~300nm的方式進行。前述接著劑層的厚度更宜為60~250nm。另一方面,使用活性能量線硬化型接著劑時,宜以使前述接著劑層的厚度為0.1~200μm的方式進行。且以0.5~50μm為宜,0.5~10μm更佳。 Further, when the application of the above-mentioned adhesive agent is carried out using a water-based adhesive or the like, it is preferred to carry out the thickness of the finally formed adhesive layer to be 30 to 300 nm. The thickness of the above adhesive layer is more preferably 60 to 250 nm. On the other hand, when an active energy ray-curable adhesive is used, it is preferred to carry out the thickness of the adhesive layer to be 0.1 to 200 μm. It is preferably 0.5 to 50 μm, more preferably 0.5 to 10 μm.
此外,在積層偏光件與透明保護薄膜時,透明保護薄膜與接著劑層之間可設置易接著層。易接著層可由具有諸如下述骨架的各種樹脂來形成:聚酯骨架、聚醚骨架、聚碳酸酯骨架、聚胺甲酸乙酯骨架、聚矽氧系、聚醯胺骨架、聚醯亞胺骨架、聚乙烯醇骨架等。該等聚合物樹脂可單獨使用1種,或組合2種以上來使用。又,形成易接著層時可加入其他的添加劑。具體而言,可進一步使用黏著性賦予劑、紫外線吸收劑、抗氧化劑、耐熱安定劑等安定劑等等。 In addition, when the polarizing member and the transparent protective film are laminated, an easy-adhesion layer may be disposed between the transparent protective film and the adhesive layer. The easy-adhesion layer may be formed of various resins having a skeleton such as a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a polyoxyn oxide system, a polyamine skeleton, a polyimine skeleton. , polyvinyl alcohol skeleton, and the like. These polymer resins may be used alone or in combination of two or more. Further, other additives may be added when the easy-to-adhere layer is formed. Specifically, a stabilizer such as an adhesion-imparting agent, an ultraviolet absorber, an antioxidant, a heat-resistant stabilizer, or the like can be further used.
易接著層通常預先設在透明保護薄膜上,且藉由接著劑層來積層該透明保護薄膜之易接著層側與偏光件。易接著層之形成係藉由將易接著層的形成材料以習知 技術塗佈在透明保護薄膜上並進行乾燥來實施。易接著層的形成材料通常會以溶液形式進行調整,即,考量乾燥後之厚度及塗佈之流暢性等而稀釋成適當濃度的溶液。易接著層乾燥後之厚度宜為0.01~5μm,且以0.02~2μm為宜,0.05~1μm更佳。另,易接著層雖可設置多層,但此時仍宜使易接著層的總厚度在上述範圍內。 The easy-adhesion layer is usually disposed on the transparent protective film in advance, and the easy-contact layer side of the transparent protective film and the polarizing member are laminated by an adhesive layer. The formation of the easy-adhesion layer is known by the formation of the easy-to-adhere layer. The technique is applied to a transparent protective film and dried to carry out. The material for forming the easy-adhesion layer is usually adjusted in the form of a solution, that is, a solution which is diluted to a suitable concentration in consideration of the thickness after drying and the smoothness of coating. The thickness of the adhesive layer after drying is preferably 0.01 to 5 μm, preferably 0.02 to 2 μm, more preferably 0.05 to 1 μm. Further, although the easy-adhesion layer may be provided with a plurality of layers, it is preferable at this time that the total thickness of the easy-adhesion layer is within the above range.
黏著劑層係由黏著劑所形成。黏著劑可使用各種黏著劑,可舉例如橡膠系黏著劑、丙烯醯系黏著劑、聚矽氧系黏著劑、胺甲酸乙酯系黏著劑、乙烯基烷基醚系黏著劑、聚乙烯吡咯啶酮系黏著劑、聚丙烯醯胺系黏著劑、纖維素系黏著劑等。可因應前述黏著劑的種類來選擇黏著性的基底聚合物。前述黏著劑之中,就光學透明性優異且可展現適當濕潤性、凝聚性及接著性之黏著特性並且具優異耐候性及耐熱性等觀點來看,丙烯酸系黏著劑可適於使用。 The adhesive layer is formed by an adhesive. Various adhesives can be used for the adhesive, and examples thereof include a rubber-based adhesive, an acrylic-based adhesive, a polyoxygen-based adhesive, an urethane-based adhesive, a vinyl alkyl ether adhesive, and polyvinylpyrrolidine. A ketone-based adhesive, a polypropylene amide-based adhesive, a cellulose-based adhesive, or the like. The adhesive base polymer can be selected in accordance with the type of the aforementioned adhesive. Among the above-mentioned adhesives, acrylic adhesives can be suitably used from the viewpoints of excellent optical transparency, adhesion properties exhibiting appropriate wettability, cohesiveness, and adhesion, and excellent weather resistance and heat resistance.
下塗層(底漆層)係為了使偏光件與保護薄膜的密著性提升而形成者。就構成底漆層的材料而言,只要是可對基材薄膜與聚乙烯醇系樹脂層兩者發揮達一定程度之強密著力的材料即可,並無特別限定。例如,可使用具優異透明性、熱安定性及延伸性等之熱可塑性樹脂等等。熱可塑性樹脂可舉例如丙烯醯系樹脂、聚烯烴系樹脂、聚酯系樹脂、聚乙烯醇系樹脂或其等之混合物。 The undercoat layer (primer layer) is formed to improve the adhesion between the polarizer and the protective film. The material constituting the primer layer is not particularly limited as long as it can exert a certain degree of strong adhesion to both the base film and the polyvinyl alcohol-based resin layer. For example, a thermoplastic resin or the like which is excellent in transparency, thermal stability, and elongation can be used. The thermoplastic resin may, for example, be a mixture of an acryl resin, a polyolefin resin, a polyester resin, a polyvinyl alcohol resin or the like.
透明層可由各種形成材料形成。透明層之形成材料可 舉例如聚酯系樹脂、聚醚系樹脂、聚碳酸酯系樹脂、聚胺甲酸乙酯系樹脂、聚矽氧系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、PVA系樹脂、丙烯酸系樹脂等。該等樹脂材料可單獨使用1種亦可組合2種以上使用,但其中以選自聚胺甲酸酯系樹脂及PVA系樹脂所構成群組中之1種以上為佳,PVA系樹脂更佳。又,前述樹脂形態可為水系或溶劑系中之任一者。前述樹脂形態宜為水系樹脂,且以PVA系樹脂為宜。又,水系樹脂可使用丙烯酸樹脂水溶液或胺甲酸乙酯樹脂水溶液。 The transparent layer can be formed from a variety of forming materials. The transparent layer forming material can be For example, a polyester resin, a polyether resin, a polycarbonate resin, a polyurethane resin, a polyoxyn resin, a polyamine resin, a polyimine resin, a PVA resin, and acrylic acid Resin or the like. These resin materials may be used alone or in combination of two or more. Among them, one or more selected from the group consisting of a polyurethane resin and a PVA resin is preferred, and a PVA resin is more preferable. . Further, the resin form may be either a water system or a solvent system. The resin form is preferably a water-based resin, and a PVA-based resin is preferred. Further, as the aqueous resin, an aqueous acrylic acid solution or an aqueous solution of an urethane resin can be used.
透明層厚度宜為0.2μm以上。可藉由具該厚度之透明層來抑制裂紋發生。前述透明層之厚度宜為0.5μm以上,更宜為0.7μm以上。另一方面,透明層若過厚,光學可靠性與耐水性會降低,透明層之厚度一般而言雖在8μm以下,但以6μm以下為宜,5μm以下為佳且3μm以下更佳。另,透明層之厚度指形成在前述相溶層上之厚度。 The thickness of the transparent layer is preferably 0.2 μm or more. Crack generation can be suppressed by a transparent layer having this thickness. The thickness of the transparent layer is preferably 0.5 μm or more, and more preferably 0.7 μm or more. On the other hand, when the transparent layer is too thick, the optical reliability and the water resistance are lowered, and the thickness of the transparent layer is generally 8 μm or less, preferably 6 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. Further, the thickness of the transparent layer means the thickness formed on the aforementioned compatible layer.
以耐裂紋性之觀點來看,宜縮小前述透明層之定向性指數。前述定向性指數宜控制在0.05以下,且以0.02以下為宜,無定向(定向性指數為0.01以下)尤佳。透明層之定向性指數可按實施例所載方法測定。 From the viewpoint of crack resistance, it is preferable to reduce the orientation index of the aforementioned transparent layer. The orientation index is preferably controlled to be 0.05 or less, and preferably 0.02 or less, and no orientation (orientation index of 0.01 or less) is particularly preferable. The orientation index of the transparent layer can be determined by the method set forth in the examples.
形成透明層之材料宜使用可滲透至偏光件中之者。舉例來說,形成透明層之材料以水溶性聚乙烯醇系樹脂為主成分之形成材料為宜。 The material forming the transparent layer is preferably one which is permeable to the polarizing member. For example, it is preferred that the material forming the transparent layer is formed of a water-soluble polyvinyl alcohol-based resin as a main component.
前述聚乙烯醇系樹脂可舉例如聚乙烯醇。聚乙烯醇可藉由令聚乙酸乙烯酯皂化來製得。此外,聚乙烯醇 系樹脂可列舉如乙酸乙烯酯與具共聚性單體之共聚物的皂化物。前述具共聚性之單體為乙烯時,可得乙烯-乙烯醇共聚物。又,前述具共聚性之單體可列舉如順丁烯二酸(酐)、延胡索酸、巴豆酸、衣康酸、(甲基)丙烯酸等不飽和羧酸及其酯類、乙烯、丙烯等α-烯烴、(甲基)丙烯磺酸(鈉)、磺酸鈉(單烷基蘋果酸酯)、二磺酸鈉烷基蘋果酸酯、N-羥甲基丙烯醯胺、丙烯醯胺烷基磺酸鹼金屬鹽、N-乙烯基吡咯啶酮、N-乙烯基吡咯啶酮衍生物等。此等聚乙烯醇系樹脂可單獨使用亦可併用二種以上。從滿足耐濕熱性及耐水性之觀點來看,以令聚乙酸乙烯酯皂化而得之聚乙烯醇為佳 The polyvinyl alcohol-based resin may, for example, be polyvinyl alcohol. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. In addition, polyvinyl alcohol The resin may, for example, be a saponified product of a copolymer of vinyl acetate and a copolymerizable monomer. When the copolymerizable monomer is ethylene, an ethylene-vinyl alcohol copolymer can be obtained. Further, examples of the copolymerizable monomer include unsaturated carboxylic acids such as maleic acid (anhydride), fumaric acid, crotonic acid, itaconic acid, (meth)acrylic acid, and esters thereof, and ethylene, propylene, and the like. - olefin, (meth) propylene sulfonic acid (sodium), sodium sulfonate (monoalkyl malate), sodium dialkyl sulfonate, N-methylol acrylamide, acrylamide alkyl An alkali metal sulfonate, an N-vinylpyrrolidone, an N-vinylpyrrolidone derivative or the like. These polyvinyl alcohol-based resins may be used alone or in combination of two or more. From the viewpoint of satisfying the heat and humidity resistance and the water resistance, it is preferred to use a polyvinyl alcohol obtained by saponifying polyvinyl acetate.
前述聚乙烯醇系樹脂之皂化度舉例來說可使用95莫耳%以上者,但從滿足耐濕熱性及耐水性之觀點來看,皂化度以99莫耳%以上為宜,且以99.7莫耳%以上為佳。皂化度表示:在可藉由皂化而轉換為乙烯基醇單元之單元當中,實際上皂化為乙烯基醇單元之單化的比例,殘基則為乙烯酯單元。皂化度可按JIS K 6726-1994為準來求得。 The degree of saponification of the polyvinyl alcohol-based resin may be, for example, 95% by mole or more, but from the viewpoint of satisfying moist heat resistance and water resistance, the degree of saponification is preferably 99% by mole or more, and 99.7%. More than % of the ear is preferred. The degree of saponification means that among the units which can be converted into vinyl alcohol units by saponification, the saponification is actually a ratio of singulation of vinyl alcohol units, and the residue is a vinyl ester unit. The degree of saponification can be determined in accordance with JIS K 6726-1994.
前述聚乙烯醇系樹脂之平均聚合度例如可使用500以上者,但從滿足耐濕熱性及耐水性之觀點來看,平均聚合度以1000以上為宜且1500以上為佳,2000以上更佳。聚乙烯醇系樹脂之平均聚合度係按JIS-K6726進行測定。 The average degree of polymerization of the polyvinyl alcohol-based resin may be, for example, 500 or more. From the viewpoint of satisfying the moist heat resistance and the water resistance, the average degree of polymerization is preferably 1,000 or more, more preferably 1,500 or more, and still more preferably 2,000 or more. The average degree of polymerization of the polyvinyl alcohol-based resin was measured in accordance with JIS-K6726.
此外,前述聚乙烯醇系樹脂可使用前述聚乙烯醇或在其共聚物之側鏈上具有親水性官能基之改質聚乙烯醇系樹脂。前述親水性官能基可舉例如乙醯乙醯基及羰基 等。除此之外,可使用令聚乙烯醇系樹脂縮經醛化、胺甲酸乙酯化、醚化、接枝化及磷酸酯化等而成之改質聚乙烯醇。 Further, as the polyvinyl alcohol-based resin, the above polyvinyl alcohol or a modified polyvinyl alcohol-based resin having a hydrophilic functional group in a side chain of the copolymer may be used. The hydrophilic functional group may, for example, be an ethyl acetyl group or a carbonyl group. Wait. In addition, a modified polyvinyl alcohol obtained by subjecting a polyvinyl alcohol-based resin to hydroformylation, urethane, etherification, grafting, and phosphorylation can be used.
透明層可由不含硬化性成分之形成材料形成。例如,可由含有前述聚乙烯醇系樹脂(PVA系樹脂)作為主成分之形成材料來形成。只要形成透明層之聚乙烯醇系樹脂為「聚乙烯醇系樹脂」,其與偏光件所含聚乙烯醇系樹脂相同或相異皆可。 The transparent layer may be formed of a forming material that does not contain a hardenable component. For example, it can be formed from a material containing a polyvinyl alcohol-based resin (PVA-based resin) as a main component. The polyvinyl alcohol-based resin forming the transparent layer is a "polyvinyl alcohol-based resin", and may be the same as or different from the polyvinyl alcohol-based resin contained in the polarizer.
含有前述聚乙烯醇系樹脂作為主成分之形成材料可含有硬化性成分(交聯劑)等。透明層或形成材料(固體成分)中聚乙烯醇系樹脂之比例宜為80重量%以上,更宜為90重量%以上,且以95重量%以上尤佳。但前述形成材料以不含硬化性成分(交聯劑)而宜。 The forming material containing the polyvinyl alcohol-based resin as a main component may contain a curable component (crosslinking agent) or the like. The proportion of the polyvinyl alcohol-based resin in the transparent layer or the forming material (solid content) is preferably 80% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight or more. However, the aforementioned forming material is preferably free of a curable component (crosslinking agent).
交聯劑可使用至少具有2個與聚乙烯醇系樹脂具反應性之官能基的化合物。可舉例如:乙二胺、三乙二胺、己二胺等具有伸烷基及2個胺基之伸烷基二胺類;甲苯二異氰酸酯、氫化甲苯二異氰酸酯、三羥甲基丙烷甲苯二異氰酸酯加成物、三苯基甲烷三異氰酸酯、亞甲基雙(4-苯基甲烷三異氰酸酯、異佛酮二異氰酸酯及其等的酮肟嵌段物或酚嵌段等異氰酸酯類;乙二醇二環氧丙基醚、聚乙二醇二環氧丙基醚、丙三醇二或三環氧丙基醚、1,6-己烷二元醇二環氧丙基醚、三羥甲基丙烷三環氧丙基醚、二環氧丙基苯胺、二環氧丙基胺等環氧化物類;甲醛、乙醛、丙醛、丁醛等單醛類;乙二醛、丙二醛、丁二醛、戊二醛、順丁 烯二醛、酞二醛等二醛類;羥甲基尿素、羥甲基三聚氰胺、烷基化羥甲基尿素、烷基化羥甲基化三聚氰胺、乙醯胍胺、苯并胍胺與甲醛的縮合物等胺基-甲醛樹脂;己二酸二醯肼、草酸二醯肼、丙二酸二醯肼、琥珀酸二醯肼、戊二酸二醯肼、異苯二甲酸二醯肼、癸二酸二醯肼、馬來酸二醯肼、延胡索酸二醯肼、伊康酸二醯肼等二羧酸二醯肼;乙烯-1,2-二肼、丙烯-1,3-二肼、丁烯-1,4-二肼等水溶性二肼;以及鈉、鉀、鎂、鈣、鋁、鐵、鎳等二價金屬或三價金屬之鹽及其氧化物。其等之中,係以胺基-甲醛樹脂及水溶性二肼為佳。胺基-甲醛樹脂宜為具有羥甲基的化合物。其等之中,以屬於具羥甲基之化合物的羥甲基三聚氰胺尤為適宜。 As the crosslinking agent, a compound having at least two functional groups reactive with a polyvinyl alcohol-based resin can be used. For example, ethylene diamines having an alkylene group and two amine groups such as ethylenediamine, triethylenediamine, hexamethylenediamine, etc.; toluene diisocyanate, hydrogenated toluene diisocyanate, trimethylolpropane toluene Isocyanate adduct, triphenylmethane triisocyanate, methylene bis(4-phenylmethane triisocyanate, isophorone diisocyanate and the like ketone oxime block or isocyanate such as phenol block; ethylene glycol Diepoxypropyl ether, polyethylene glycol diglycidyl ether, glycerol di or triepoxypropyl ether, 1,6-hexane diol diepoxypropyl ether, trimethylol Ethylene oxides such as propane triepoxypropyl ether, diepoxypropyl aniline, diepoxypropylamine; monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde; glyoxal, malondialdehyde, Succinic aldehyde, glutaraldehyde, cis-butane Dialdehydes such as enedilaldehyde and sebacaldehyde; methylol urea, methylol melamine, alkylated methylol urea, alkylated methylolated melamine, acetamide, benzoguanamine and formaldehyde Amine-formaldehyde resin such as condensate; diterpene adipate, diterpene oxalate, diammonium malonate, diterpene succinate, diammonium glutarate, diammonium phthalate, Bismuth azelaic acid, diterpene maleate, diterpenoid fumarate, diconazole dioxonium dicarboxylate, ethylene-1,2-diindole, propylene-1,3-dioxene a water-soluble diterpene such as butene-1,4-dioxane; and a divalent metal such as sodium, potassium, magnesium, calcium, aluminum, iron or nickel or a salt of a trivalent metal and an oxide thereof. Among them, an amine-formaldehyde resin and a water-soluble diterpene are preferred. The amine-formaldehyde resin is preferably a compound having a methylol group. Among them, methylol melamine which is a compound having a methylol group is particularly preferable.
從提升耐水性的觀點,可使用前述硬化性成分(交聯劑),惟其比率相對於聚乙烯醇系樹脂100重量份宜為20重量份以下、10重量份以下、5重量份以下。 The curable component (crosslinking agent) can be used from the viewpoint of improving water resistance, and the ratio thereof is preferably 20 parts by weight or less, 10 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the polyvinyl alcohol-based resin.
前述形成材料係以溶液的形式來調整,即令前述聚乙烯醇系樹脂溶解於溶劑而成之溶液。溶劑可舉例如水、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺-N-甲基吡咯啶酮、各種二醇類、醇類、乙二胺、二乙烯三胺等胺類。其等可單獨使用,或組合二種以上來使用。此等之中,宜採用溶劑使用水之水溶液。前述形成材料(例如水溶液)之中,前述聚乙烯醇系樹脂的濃度雖無特別限制,但若考量塗佈性及放置安定性等,則為0.1~15重量%,且宜為0.5~10重量%。 The above-mentioned forming material is adjusted in the form of a solution, that is, a solution obtained by dissolving the polyvinyl alcohol-based resin in a solvent. Examples of the solvent include water, dimethyl hydrazine, dimethylformamide, dimethylacetamide-N-methylpyrrolidone, various glycols, alcohols, ethylenediamine, diethylenetriamine, and the like. Amines. These may be used singly or in combination of two or more. Among these, it is preferred to use an aqueous solution of water as a solvent. In the above-mentioned forming material (for example, an aqueous solution), the concentration of the polyvinyl alcohol-based resin is not particularly limited, but is 0.1 to 15% by weight, and preferably 0.5 to 10%, in consideration of coatability, stability, and the like. %.
另外,亦可於前述形成材料(例如水溶液)中適度加入添加劑。添加劑可舉例如可塑劑及界面活性劑等。可塑劑可舉例如乙二醇及丙三醇等多元醇。界面活性劑可舉例如非離子性界面活性劑。再者,亦可進一步搭配矽烷偶合劑、鈦偶合劑等偶合劑、各種黏著性賦與劑、紫外線吸收劑、抗氧化劑、耐熱安定劑、耐水解安定劑等安定劑等等。 Further, an additive may be appropriately added to the aforementioned forming material (for example, an aqueous solution). The additive may, for example, be a plasticizer, a surfactant, or the like. The plasticizer may, for example, be a polyol such as ethylene glycol or glycerin. The surfactant may, for example, be a nonionic surfactant. Further, a coupling agent such as a decane coupling agent or a titanium coupling agent, various adhesive agents, an ultraviolet absorber, an antioxidant, a heat stabilizer, a stabilizer such as a hydrolysis stabilizer, and the like can be further used.
可藉由將前述形成材料塗佈在偏光件的另一面(不具透明保護薄膜之面)並進行乾燥而形成前述透明層。前述形成材料之塗布係以使乾燥後厚度為0.2μm以上的方式來實施。塗佈操作沒有特別限制,可採用任意之適當方法。例如,可採用輥塗法、旋塗法、線棒塗佈法、浸塗法、模具塗佈法、淋幕式塗佈法、噴塗法、刮刀式塗佈法(逗形刮刀式塗佈法等)等各種手段。乾燥溫度通常宜為60~120℃,且以70~100℃為佳。乾燥時間宜為10~300秒,且更宜為20~120秒。 The transparent layer can be formed by applying the above-mentioned forming material to the other surface of the polarizing member (the surface without the transparent protective film) and drying. The coating of the above-mentioned forming material is carried out so that the thickness after drying is 0.2 μm or more. The coating operation is not particularly limited, and any appropriate method can be employed. For example, a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, or a knife coating method (sweet blade coating method) may be employed. Etc.) and other means. The drying temperature is usually preferably from 60 to 120 ° C, and preferably from 70 to 100 ° C. The drying time should be 10 to 300 seconds, and more preferably 20 to 120 seconds.
可在前述偏光薄膜設置黏著劑層而用作附黏著劑層之偏光薄膜。黏著劑層係在偏光薄膜之透明層或偏光件側,又,具有保護薄膜時,可設在保護薄膜上。附黏著劑層之偏光薄膜之黏著劑層可設置分隔件。 An adhesive layer may be provided on the polarizing film to be used as a polarizing film with an adhesive layer. The adhesive layer is on the transparent layer or the polarizer side of the polarizing film, and when it has a protective film, it can be provided on the protective film. The adhesive layer of the polarizing film with the adhesive layer may be provided with a separator.
黏著劑層之形成可使用適當之黏著劑,其種類並無特別限制。黏著劑可列舉如橡膠系黏著劑、丙烯酸系黏著劑、聚矽氧系黏著劑、胺甲酸乙酯系黏著劑、乙烯基 烷基醚系黏著劑、聚乙烯醇系黏著劑、聚乙烯吡咯啶酮系黏著劑、聚丙烯醯胺系黏著劑、纖維素系黏著劑等。 A suitable adhesive can be used for the formation of the adhesive layer, and the kind thereof is not particularly limited. Examples of the adhesive include a rubber-based adhesive, an acrylic adhesive, a polyoxygen adhesive, an urethane adhesive, and a vinyl. An alkyl ether-based adhesive, a polyvinyl alcohol-based adhesive, a polyvinylpyrrolidone-based adhesive, a polypropylene amide-based adhesive, or a cellulose-based adhesive.
該等黏著劑中,宜使用光學透明性佳、展現適當濕潤性、凝聚性及接著性之黏著特性且具優異耐候性及耐熱性等者。就顯示出此種特徵而言,以使用丙烯酸系黏著劑為佳。 Among these adhesives, those having excellent optical transparency, exhibiting appropriate wettability, cohesiveness, and adhesion properties, and having excellent weather resistance and heat resistance are preferably used. In order to exhibit such characteristics, it is preferred to use an acrylic adhesive.
就形成黏著劑層之方法而言,例如可藉由下述方法來進行製作:將前述黏著劑塗佈於經剝離處理之分離件等,將聚合溶劑等乾燥除去形成黏著劑層後,以圖2(A)、(B)之態樣轉印至透明層或保護薄膜(或者以圖2(C)的態樣,即保護薄膜)的方法,或者,以圖2(A)、(B)的態樣,將前述黏著劑層塗佈到透明層或保護薄膜(或者以圖2(C)的態樣,即保護薄膜)後,乾燥除去聚合溶劑等而使黏著劑層形成於偏光件的方法。另,塗佈黏著劑時可適當另行加入聚合溶劑以外的一種以上溶劑。 The method of forming the pressure-sensitive adhesive layer can be carried out, for example, by applying the pressure-sensitive adhesive to a release-treated separator or the like, and drying the polymerization solvent or the like to form an adhesive layer. 2(A), (B) is transferred to a transparent layer or a protective film (or in the form of FIG. 2(C), that is, a protective film), or, as shown in FIG. 2(A), (B) In the aspect, the adhesive layer is applied to a transparent layer or a protective film (or in the form of FIG. 2(C), that is, a protective film), and then the polymerization solvent or the like is removed to form an adhesive layer on the polarizing member. method. Further, when the adhesive is applied, one or more solvents other than the polymerization solvent may be appropriately added.
經剝離處理之分離件宜使用聚矽氧剝離襯墊。於此種襯墊上塗佈本發明之黏著劑並使其乾燥而形成黏著劑層的步驟中,就使黏著劑乾燥之方法而言,可因應目的採用適宜且適切的方法。宜使用將上述塗佈膜加熱乾燥之方法。加熱乾燥溫度宜為40℃~200℃,更宜為50℃~180℃,70℃~170℃尤佳。藉由將加熱溫度設成上述範圍,可獲得具有優異黏著特性的黏著劑。 Preferably, the release treated release member is a polyoxynitride release liner. In the step of applying the adhesive of the present invention to such a liner and drying it to form an adhesive layer, a suitable and suitable method can be employed for the purpose of drying the adhesive. A method of heating and drying the above coating film is preferably used. The heating and drying temperature should be 40 ° C ~ 200 ° C, more preferably 50 ° C ~ 180 ° C, 70 ° C ~ 170 ° C is particularly good. By setting the heating temperature to the above range, an adhesive having excellent adhesive properties can be obtained.
乾燥時間可採用適宜且適切的時間。上述乾燥時間宜為5秒~20分鐘,更宜為5秒~10分鐘,10秒~5分鐘尤 佳。 The drying time can be suitably and suitably used. The drying time should be 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, 10 seconds to 5 minutes. good.
黏著劑層之形成方法可使用各種方法。具體上,可舉例如輥塗法、接觸上膠輥塗佈法、凹版塗佈法、反向塗佈法、輥刷法、噴塗法、浸漬輥塗法、棒塗法、刀塗法、氣刀塗佈法、淋幕式塗佈法、唇模塗佈法、利用鑄模塗佈機等之擠壓塗佈法等方法。 Various methods can be used to form the adhesive layer. Specifically, for example, a roll coating method, a contact top coat coating method, a gravure coating method, a reverse coating method, a roll brush method, a spray coating method, a dip roll coating method, a bar coating method, a knife coating method, and a gas method are mentioned. A knife coating method, a curtain coating method, a lip mold coating method, a method using a die coating method such as a die coater, or the like.
黏著劑層的厚度無特別限制,例如為1~100μm左右。宜為2~50μm,且以2~40μm為佳,5~35μm更佳。 The thickness of the adhesive layer is not particularly limited and is, for example, about 1 to 100 μm. It is preferably 2 to 50 μm, preferably 2 to 40 μm, and more preferably 5 to 35 μm.
前述黏著劑層露出時,在供予實用前,亦可以經剝離處理之片材(分隔件)來保護黏著劑層。 When the adhesive layer is exposed, the adhesive layer may be protected by a release-treated sheet (separator) before being supplied for practical use.
分隔件之構成材料可舉例如聚乙烯、聚丙烯、聚對酞酸乙二酯、聚酯薄膜等塑膠薄膜;紙、布、不織布等多孔質材料;網狀物、發泡片材、金屬箔及其等之層合體等適當的薄片物等等,惟,從表面平滑性優良之觀點來看,宜採用塑膠薄膜。 The constituent material of the separator may, for example, be a plastic film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film; a porous material such as paper, cloth or non-woven fabric; mesh, foamed sheet, metal foil A suitable thin film or the like, such as a laminate thereof, is preferably a plastic film from the viewpoint of excellent surface smoothness.
就該塑膠薄膜而言,只要是可保護前述黏著劑層的薄膜,即無不受特別限制,可舉例如聚乙烯薄膜、聚丙烯薄膜、聚丁烯薄膜、聚丁二烯薄膜、聚甲基戊烯薄膜、聚氯乙烯薄膜、氯乙烯共聚物薄膜、聚對酞酸乙二酯薄膜、聚對酞酸丁二酯薄膜、聚胺甲酸乙酯薄膜、乙烯-乙酸乙烯酯共聚物薄膜等。 The plastic film is not particularly limited as long as it is a film capable of protecting the above-mentioned adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, and a polymethyl group. A pentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate film, or the like.
前述分離件的厚度一般為5~200μm且宜為5~100μm左右。對於前述分離件亦可視需要而進行利用聚矽氧系、氟系、長鏈烷基系或脂肪酸醯胺系脫模劑以及氧 化矽粉等之脫模及防污處理,及塗佈型、捏合型、蒸鍍型等抗靜電處理。尤其,可藉由對前述分隔件表面適當實施聚矽氧處理、長鏈烷基處理、氟處理等之剝離處理來進一步提高自前述黏著劑層剝離之剝離性。 The thickness of the separator is generally 5 to 200 μm and preferably about 5 to 100 μm. The above-mentioned separator may also be subjected to a polyfluorene-based, fluorine-based, long-chain alkyl-based or fatty acid-amide-based release agent and oxygen as needed. Release and antifouling treatment of bismuth powder, and antistatic treatment such as coating type, kneading type, and vapor deposition type. In particular, the peeling property from the adhesion of the above-mentioned adhesive layer can be further improved by appropriately performing a release treatment such as polyfluorination treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
可於偏光薄膜上設置表面保護薄膜。表面保護薄膜通常具有基材薄膜及黏著劑層,並隔著該黏著劑層保護偏光件。 A surface protective film can be provided on the polarizing film. The surface protective film usually has a substrate film and an adhesive layer, and the polarizer is protected by the adhesive layer.
從檢查性及管理性等觀點來看,表面保護薄膜之基材薄膜係選自具等向性或近似等向性的薄膜材料。該薄膜材料可舉例如:如同聚對酞酸乙二酯薄膜等聚酯系樹脂、纖維素系樹脂、乙酸酯系樹脂、聚醚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂及丙烯醯系樹脂般之透明聚合物。其等之中尤以聚酯系樹脂為宜。基材薄膜亦可使用1種或2種以上之薄膜材料的層合體,亦可使用前述薄膜的延伸物。基材薄膜的厚度通常為500μm以下,宜為10~200μm。 The base film of the surface protective film is selected from the group consisting of isotropic or nearly isotropic film materials from the viewpoints of inspection property and management. The film material may, for example, be a polyester resin such as a polyethylene terephthalate film, a cellulose resin, an acetate resin, a polyether oxime resin, a polycarbonate resin, or a polyamide resin. A transparent polymer such as a polyimide resin, a polyolefin resin or an acryl resin. Among them, polyester resins are preferred. A laminate of one type or two or more types of film materials may be used as the base film, and an extension of the film may be used. The thickness of the base film is usually 500 μm or less, preferably 10 to 200 μm.
就形成表面保護薄膜之黏著劑層的黏著劑而言,可適當選擇以(甲基)丙烯酸系聚合物、聚矽氧系聚合物、聚酯、聚胺甲酸乙酯、聚醯胺、聚醚、氟系及橡膠系等聚合物作為基底聚合物的黏著劑來予以使用。從透明性、耐候性及耐熱性等觀點來看,以丙烯醯系聚合物作為基底聚合物的丙烯酸系黏著劑為佳。黏著劑層厚度(乾燥膜厚)視所需黏著力來決定。通常為1~100μm左右,且宜為 5~50μm。 As the adhesive for forming the adhesive layer of the surface protective film, a (meth)acrylic polymer, a polyoxymethylene polymer, a polyester, a polyurethane, a polyamide or a polyether can be appropriately selected. A polymer such as a fluorine-based or rubber-based polymer is used as an adhesive for the base polymer. From the viewpoints of transparency, weather resistance, heat resistance and the like, an acrylic adhesive having an acrylonitrile-based polymer as a base polymer is preferred. The thickness of the adhesive layer (dry film thickness) is determined by the desired adhesive force. Usually about 1~100μm, and should be 5~50μm.
此外,對於表面保護薄膜,可以在基材薄膜之設有黏著劑層之面的相反面,利用聚矽氧處理、長鏈烷基處理、氟處理等低接著性材料來設置剝離處理層。 Further, in the surface protective film, the release treatment layer may be provided by a low adhesion material such as polyfluorination treatment, long-chain alkyl treatment or fluorine treatment on the opposite side of the surface of the base film on which the pressure-sensitive adhesive layer is provided.
本發明之偏光薄膜在實際使用時可使用已與其他光學層積層而成之光學薄膜。該光學層並無特別限定,可使用1層或2層以上之諸如反射板及半透射板、相位差板(包含1/2及1/4等波長板)、視角補償薄膜等曾用於形成液晶顯示裝置等的光學層。尤為理想的是,於本發明之偏光薄膜上更積層反射板或半透射反射板而成的反射型偏光薄膜或半透射型偏光薄膜、於偏光薄膜上更積層相位差板而成的楕圓偏光薄膜或圓偏光薄膜、於偏光薄膜上更積層視角補償薄膜而成的廣視野角偏光薄膜、或者是於偏光薄膜上更積層增亮薄膜而成的偏光薄膜。 In the actual use of the polarizing film of the present invention, an optical film which has been laminated with other optical layers can be used. The optical layer is not particularly limited, and one or two or more layers such as a reflecting plate and a semi-transmissive plate, a phase difference plate (including 1/2 and 1/4 wavelength plates), a viewing angle compensation film, and the like may be used for formation. An optical layer such as a liquid crystal display device. In particular, a reflective polarizing film or a semi-transmissive polarizing film in which a reflecting plate or a semi-transmissive reflecting plate is laminated on the polarizing film of the present invention, and a polarizing film formed by laminating a phase difference plate on the polarizing film is particularly preferable. A film or a circularly polarizing film, a wide viewing angle polarizing film formed by laminating a viewing angle compensation film on a polarizing film, or a polarizing film formed by laminating a brightening film on a polarizing film.
在偏光薄膜上積層有上述光學層的光學薄膜亦可在液晶顯示裝置等之製造過程中以依序個別積層之方式來形成,但預先積層而製成光學薄膜者具優異之品質穩定性及組裝作業等,具有能提升液晶顯示裝置等製程之優點。積層時可使用黏著層等適當的接著手段。上述偏光薄膜及其他光學層在接著時,其等之光學軸可因應目的之相位差特性等來設成適當的配置角度。 The optical film in which the optical layer is laminated on the polarizing film may be formed by sequentially laminating in a process of manufacturing a liquid crystal display device or the like, but the optical film is laminated in advance to have excellent quality stability and assembly. Work, etc., have the advantage of improving the process of liquid crystal display devices. An appropriate bonding means such as an adhesive layer can be used for lamination. When the polarizing film and the other optical layer are in the following state, the optical axis thereof may be set to an appropriate arrangement angle in accordance with the phase difference characteristic of the object or the like.
本發明之偏光薄膜或光學薄膜可適宜使用在液晶顯示裝置等各種裝置之形成等。液晶顯示裝置之形成可 依習知技術來實施。即,一般而言,係將液晶晶胞、偏光薄膜或光學薄膜以及依需求而定之照明系統等構成零件適當組裝並安裝驅動電路等來形成液晶顯示裝置,在本發明中,除使用本發明之偏光薄膜或光學薄膜之外,則無特別限定,可按習知技術。就液晶晶胞而言,可使用例如IPS型、VA型等任意類型,惟以IPS型尤為理想。 The polarizing film or the optical film of the present invention can be suitably used in the formation of various devices such as a liquid crystal display device. The liquid crystal display device can be formed Implemented according to the know-how. In other words, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film, an optical film, and an illumination system as required, and mounting a driving circuit or the like. In the present invention, in addition to using the present invention, The polarizing film or the optical film is not particularly limited, and may be a conventional technique. As the liquid crystal cell, any type such as an IPS type or a VA type can be used, but an IPS type is particularly preferable.
可形成下述的液晶顯示裝置:在液晶胞的單側或兩側配置有偏光薄膜或光學薄膜的液晶顯示裝置;或,照明系統使用背光或反射板者等之適當的液晶顯示裝置。此時,本發明之偏光薄膜或光學薄膜可設置在液晶胞的單側或兩側。於兩側設置偏光薄膜或光學薄膜時,其等可相同亦可互異。此外,於形成液晶顯示裝置時,可在適當位置上配置1層或2層以上之諸如擴散板、防眩層、抗反射膜、保護板、稜鏡陣列、透鏡陣列片、光擴散板、背光等之適當零件。 A liquid crystal display device in which a liquid crystal display device in which a polarizing film or an optical film is disposed on one side or both sides of a liquid crystal cell or a liquid crystal display device such as a backlight or a reflector is used in the illumination system can be formed. At this time, the polarizing film or the optical film of the present invention may be disposed on one side or both sides of the liquid crystal cell. When polarizing films or optical films are provided on both sides, they may be the same or different. Further, when forming a liquid crystal display device, one or more layers such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a tantalum array, a lens array sheet, a light diffusing plate, and a backlight may be disposed at appropriate positions. Wait for the appropriate parts.
以下,列舉實施例來說明本發明,惟本發明不受下述實施例所侷限。此外,各例中的份及%均為重量基準。以下,沒有特別規定之室溫放置條件皆為23℃ 65%RH。 The invention is illustrated by the following examples, but the invention is not limited by the following examples. In addition, parts and % in each case are based on weight. Hereinafter, room temperature conditions which are not specifically specified are 23 ° C 65% RH.
於吸水率0.75%、Tg75℃之非晶質異苯二甲酸-共聚-聚對酞酸乙二酯(IPA-共聚-PET)薄膜(厚度:100μm)基材的單面上施加電暈處理,於25℃下在該電暈處理面上塗佈以9:1之比含有聚乙烯醇(聚合度4200,皂化度99.2莫耳%) 及乙醯乙醯基改質PVA(聚合度1200,乙醯乙醯基改質度4.6%,皂化度99.0莫耳%以上,日本合成化學工業公司製,商品名「Gohsefimer Z200」)的水溶液並使其乾燥,形成厚度11μm的PVA系樹脂層,製出積層體。 Corona treatment was applied to one side of a substrate of an amorphous isophthalic acid-co-polyethylene terephthalate (IPA-co-PET) film (thickness: 100 μm) having a water absorption of 0.75% and a Tg of 75 ° C. Coating on the corona-treated surface at 25 ° C in a ratio of 9:1 containing polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) And an aqueous solution of PVA (polymerization degree 1200, acetylation degree 4.6%, saponification degree 99.0 mol% or more, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gohsefimer Z200") This was dried to form a PVA-based resin layer having a thickness of 11 μm to prepare a laminate.
在120℃烘箱內,使所得積層體在周速相異的輥筒間以縱向(長向)進行自由端單軸延伸(空中輔助延伸處理)至2.0倍。 In the oven at 120 ° C, the obtained laminate was subjected to free end uniaxial stretching (air assisted elongation treatment) to 2.0 times in the longitudinal direction (long direction) between rolls having different circumferential speeds.
接著,於液溫30℃的不溶化浴(相對於100重量份水,摻混4重量份硼酸而得的硼酸水溶液)中將積層體浸漬30秒(不溶化處理)。 Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 30 ° C (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) (insolubilization treatment).
接著,於液溫30℃的染色浴中一邊進行浸漬一邊調整碘濃度及浸漬時間,使偏光板達所定的透光率。本實施例中,係於碘水溶液中浸漬60秒(染色處理),該碘水溶液係相對於100重量份水摻混0.2重量份碘並摻混1.0重量份碘化鉀而得。 Next, the iodine concentration and the immersion time were adjusted while immersing in a dye bath at a liquid temperature of 30 ° C to bring the polarizing plate to a predetermined light transmittance. In the present embodiment, it was immersed in an aqueous iodine solution for 60 seconds (dyeing treatment) obtained by blending 0.2 part by weight of iodine with 100 parts by weight of water and blending 1.0 part by weight of potassium iodide.
接著,使其於液溫30℃的交聯浴(相對於100重量份水,摻混3重量份碘化鉀並摻混3重量份硼酸而獲得之硼酸水溶液)中浸漬30秒(交聯處理)。 Subsequently, it was immersed in a crosslinking bath at a liquid temperature of 30 ° C (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and mixing 3 parts by weight of boric acid with respect to 100 parts by weight of water) (crosslinking treatment).
然後,一邊使積層體浸漬於液溫70℃的硼酸水溶液(相對於100重量份水,摻混4重量份硼酸並摻混5重量份碘化鉀而獲得之水溶液),一邊在周速相異的輥筒間進行單軸延伸,使縱向(長向)總延伸倍率達5.5倍(水中延伸處理)。 Then, the laminate was immersed in a boric acid aqueous solution having a liquid temperature of 70 ° C (an aqueous solution obtained by blending 4 parts by weight of boric acid with 5 parts by weight of potassium iodide with respect to 100 parts by weight of water), and the rolls were different at a peripheral speed. The uniaxial extension between the cylinders makes the longitudinal (longitudinal) total extension ratio 5.5 times (water extension treatment).
然後,將積層體浸漬於液溫30℃的洗淨浴(相對於100重量份水摻混4重量份碘化鉀而獲得之水溶液)(洗淨處 理)。 Then, the laminate was immersed in a washing bath at a liquid temperature of 30 ° C (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) (washing place) Reason).
經由上述,獲得含厚度5μm偏光件之光學薄膜積層體A0。 Through the above, an optical film laminate A0 having a polarizing member having a thickness of 5 μm was obtained.
於製作光學薄膜積層體A0之過程中,除了將水中延伸處理之硼酸水溶液所摻合的硼酸變更為3.5重量份之外,與光學薄膜積層體A0之製作方法同樣地製得光學薄膜積層體A1。所得偏光件之厚度為5μm。 In the process of producing the optical film laminate A0, the optical thin film laminate A1 was produced in the same manner as in the production method of the optical thin film laminate A0 except that the boric acid blended with the aqueous boric acid solution in the water-extended treatment was changed to 3.5 parts by weight. . The thickness of the obtained polarizer was 5 μm.
於製作光學薄膜積層體A0之過程中,除了將水中延伸處理之硼酸水溶液所摻合的硼酸變更為4.5重量份之外,與光學薄膜積層體A0之製作方法同樣地製得光學薄膜積層體A2。所得偏光件之厚度為5μm。 In the process of producing the optical film laminate A0, the optical thin film laminate A2 was produced in the same manner as in the production method of the optical thin film laminate A0 except that the boric acid blended with the aqueous solution of the boric acid in the water-extended treatment was changed to 4.5 parts by weight. . The thickness of the obtained polarizer was 5 μm.
於製作光學薄膜積層體A0之過程中,除了形成厚度15μm之PVA系樹脂層之外,與光學薄膜積層體A0之製作方法同樣地製得光學薄膜積層體D。所得偏光件之厚度為7μm。 In the process of producing the optical film laminate A0, an optical film laminate D was produced in the same manner as in the production method of the optical film laminate A0 except that a PVA-based resin layer having a thickness of 15 μm was formed. The thickness of the obtained polarizer was 7 μm.
將平均聚合度2400、皂化度99.9莫耳%且厚度30μm之聚乙烯醇薄膜浸漬於30℃溫水中60秒使其膨潤。接著,浸漬到碘/碘化鉀(重量比=0.5/8)濃度0.3%之水溶液中,一邊使其延伸到3.5倍一邊將薄膜染色。之後,於65℃硼酸酯水溶液中進行延伸至總延伸倍率達6倍。延伸後,於40℃之烘箱 中進行3分鐘乾燥,製得PVA系偏光件E。所得偏光件之厚度為12μm。 A polyvinyl alcohol film having an average degree of polymerization of 2,400, a degree of saponification of 99.9 mol%, and a thickness of 30 μm was immersed in warm water of 30 ° C for 60 seconds to swell. Subsequently, the film was immersed in an aqueous solution of 0.3% by weight of iodine/potassium iodide (weight ratio = 0.5/8), and the film was dyed while being extended to 3.5 times. Thereafter, the solution was extended to a total stretching ratio of 6 times in a 65 ° C aqueous solution of borate. After extension, oven at 40 ° C The film was dried for 3 minutes to obtain a PVA-based polarizer E. The thickness of the obtained polarizer was 12 μm.
將平均聚合度2400、皂化度99.9莫耳%且厚度75μm之聚乙烯醇薄膜浸漬於30℃溫水中60秒使其膨潤。接著,浸漬到碘/碘化鉀(重量比=0.5/8)濃度0.3%之水溶液中,一邊使其延伸到3.5倍一邊將薄膜染色。之後,於65℃硼酸酯水溶液中進行延伸至總延伸倍率達6倍。延伸後,於40℃之烘箱中進行3分鐘乾燥,製得PVA系偏光件F。所得偏光件之厚度為23μm。 A polyvinyl alcohol film having an average degree of polymerization of 2,400, a degree of saponification of 99.9 mol%, and a thickness of 75 μm was immersed in warm water of 30 ° C for 60 seconds to swell. Subsequently, the film was immersed in an aqueous solution of 0.3% by weight of iodine/potassium iodide (weight ratio = 0.5/8), and the film was dyed while being extended to 3.5 times. Thereafter, the solution was extended to a total stretching ratio of 6 times in a 65 ° C aqueous solution of borate. After stretching, it was dried in an oven at 40 ° C for 3 minutes to obtain a PVA-based polarizer F. The thickness of the obtained polarizer was 23 μm.
保護薄膜:對厚度40μm且具有內酯環結構之(甲基)丙烯酸樹脂薄膜的易接著處理面上施加電暈處理後使用之。 Protective film: It was used after corona treatment was applied to the easily-treated surface of a (meth)acrylic resin film having a thickness of 40 μm and having a lactone ring structure.
將N-羥乙基丙烯醯胺(HEAA)40重量份與丙烯醯基啉(ACMO)60重量份與光聚合引發劑「IRGACURE 819」(BASF社製)3重量份混合,調製出紫外線硬化型接著劑。 40 parts by weight of N-hydroxyethyl acrylamide (HEAA) with acrylonitrile 60 parts by weight of the morpholine (ACMO) was mixed with 3 parts by weight of a photopolymerization initiator "IRGACURE 819" (manufactured by BASF Corporation) to prepare an ultraviolet curable adhesive.
將聚合度2500且皂化度99.0莫耳%之聚乙烯醇樹脂溶解於純水中,調製出固體成分濃度為4重量%之水溶液。 A polyvinyl alcohol resin having a degree of polymerization of 2,500 and a degree of saponification of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid concentration of 4% by weight.
將聚合度500且皂化度99.0莫耳%之聚乙烯醇樹脂溶解於純水中,調製出固體成分濃度為4重量%之水溶液。 A polyvinyl alcohol resin having a polymerization degree of 500 and a degree of saponification of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid concentration of 4% by weight.
將聚合度2500且皂化度89.0莫耳%之聚乙烯醇樹脂溶解於純水中,調製出固體成分濃度為4重量%之水溶液。 A polyvinyl alcohol resin having a degree of polymerization of 2,500 and a degree of saponification of 89.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid concentration of 4% by weight.
將聚合度2500且皂化度99.7莫耳%之聚乙烯醇樹脂溶解於純水中,調製出固體成分濃度為4重量%之水溶液。 A polyvinyl alcohol resin having a degree of polymerization of 2,500 and a degree of saponification of 99.7 mol% was dissolved in pure water to prepare an aqueous solution having a solid concentration of 4% by weight.
將聚合度2500且皂化度99.7莫耳%之聚乙烯醇樹脂100份與添加劑之羥甲基三聚氰胺(DIC公司製,商品名「WATER SOL:S-695」)5份溶解於純水中,調製出固體成分濃度為4重量%之水溶液。 100 parts of a polyvinyl alcohol resin having a degree of polymerization of 2,500 and a degree of saponification of 99.7 mol%, and 5 parts of an additive methylol melamine (manufactured by DIC Corporation, "WATER SOL: S-695") were dissolved in pure water to prepare An aqueous solution having a solid concentration of 4% by weight was obtained.
N-羥乙基丙烯醯胺(興人公司製,商品名「HEAA」)20份 N-hydroxyethyl acrylamide (manufactured by Xingren Co., Ltd., trade name "HEAA") 20 parts
胺甲酸乙酯丙烯酸酯(日本合成化學公司製,商品名「UV-1700B」)80份 Ethyl urethane acrylate (manufactured by Nippon Synthetic Chemical Co., Ltd., trade name "UV-1700B") 80 parts
光自由基聚合引發劑(2-甲基-1-(4-甲基硫代苯基)-2-啉基丙烷-1-酮,BASF公司製,商品名「IRGACURE907」)3份 Photoradical polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one, manufactured by BASF Corporation, trade name "IRGACURE 907") 3 parts
光增感劑(二乙基9-氧硫,日本化藥公司製,商品名「KAYACURE DETX-S」)2份 Photosensitizer (diethyl 9-oxosulfur , manufactured by Nippon Kayaku Co., Ltd., trade name "KAYACURE DETX-S")
將上述丙烯酸系形成材料混合並於50℃下攪拌1小時,調製出各種活性能量線硬化型形成材料。 The acrylic forming material was mixed and stirred at 50 ° C for 1 hour to prepare various active energy ray-curable forming materials.
活性能量線使用可見光(封入鎵之金屬鹵化物燈)照射裝置:Fusion UV Systems,Inc公司製Light HAMMER10,閥:V閥,尖峰照度:1600mW/cm2,積算照射量1000/mJ/cm2(波長380~440nm)。此外,可見光之照度係使用Solatell社製Sola-Check系統來測得。 The active energy ray is irradiated with visible light (a metal halide lamp sealed with gallium): Light HAMMER 10 manufactured by Fusion UV Systems, Inc., valve: V valve, peak illuminance: 1600 mW/cm 2 , and integrated irradiation amount 1000/mJ/cm 2 ( Wavelength 380~440nm). In addition, the illuminance of visible light was measured using a Sola-Check system manufactured by Solatell.
於上述光學薄膜積層體A0之偏光件表面上,以硬化後之接著劑層厚度會成為0.5μm之方式塗佈上述紫外線硬化型接著劑,在此同時,貼合上述保護薄膜後,接著照射活性能量線使接著劑硬化。接著,剝離非晶性PET基材,製作出使用了薄型偏光件之單側保護偏光薄膜A0。所得單側保護偏光薄膜A0之光學特性為透光率42.8%、偏光度99.99%。 The ultraviolet curable adhesive is applied to the surface of the polarizer of the optical film laminate A0 so that the thickness of the adhesive layer after curing is 0.5 μm, and the protective film is bonded thereto, followed by irradiation activity. The energy line hardens the adhesive. Next, the amorphous PET substrate was peeled off to produce a one-side protective polarizing film A0 using a thin polarizer. The optical characteristics of the obtained one-side protective polarizing film A0 were 42.8% of light transmittance and 99.99% of polarization degree.
於參考例1中,除了使用光學薄膜積層體A1、A2或D來取代光學薄膜積層體A0之外,與單側保護偏光薄膜A0之製作方法同樣地製得單側保護偏光薄膜A1、A2或D。所得單側保護偏光薄膜A1、A2或D之光學特性為透光率42.8%、偏光度99.99%。 In Reference Example 1, a single-sided protective polarizing film A1, A2 or the like was produced in the same manner as in the production method of the one-side protective polarizing film A0 except that the optical film laminates A1, A2 or D were used instead of the optical film laminate A0. D. The optical characteristics of the obtained one-side protective polarizing film A1, A2 or D were 42.8% of light transmittance and 99.99% of polarization degree.
於偏光件E之單側表面上,以硬化後之接著劑層厚度會成為0.5μm之方式塗佈上述紫外線硬化型接著劑,在此同時 貼合上述保護薄膜,之後接著照射活性能量線使接著劑硬化,製得單側保護偏光薄膜E。所得單側保護偏光薄膜E之光學特性為透光率42.8%、偏光度99.99%。 On the one side surface of the polarizer E, the ultraviolet curable adhesive is applied so that the thickness of the adhesive layer after hardening becomes 0.5 μm. The protective film was bonded, and then the active energy ray was irradiated to harden the adhesive to obtain a one-side protective polarizing film E. The optical characteristics of the obtained one-side protective polarizing film E were 42.8% of light transmittance and 99.99% of polarization degree.
於參考例5中,除了使用偏光件F來取代偏光件E之外,與參考例5同樣地製得單側保護偏光薄膜F。所得單側保護偏光薄膜F之光學特性為透光率42.8%、偏光度99.99%。 In Reference Example 5, a one-side protective polarizing film F was produced in the same manner as in Reference Example 5 except that the polarizer F was used instead of the polarizer E. The optical characteristics of the obtained one-side protective polarizing film F were 42.8% of light transmittance and 99.99% of polarization degree.
在參考例1所得上述單側保護偏光薄膜A0之偏光件面(未設置透明保護薄膜之偏光件面)上,以乾燥後厚度(不含相溶層)會成為0.8μm的方式,利用線棒塗佈機塗佈已調整成25℃之上述聚乙烯純係形成材料A後,於80℃下熱風乾燥30秒,製出附透明層之單側保護偏光薄膜A0。 In the polarizing surface of the one-side protective polarizing film A0 obtained in Reference Example 1 (the polarizing surface on which the transparent protective film is not provided), the thickness (excluding the compatible layer) after drying is 0.8 μm, and the wire rod is used. After coating the polyethylene pure-form forming material A adjusted to 25 ° C by a coater, it was dried by hot air at 80 ° C for 30 seconds to prepare a one-side protective polarizing film A0 with a transparent layer.
於實施例1中,除了將透明層之形成材料種類及透明層厚度變更如表1所示之外,與實施例1同樣地製出附透明層之單側保護偏光薄膜A0、A1或A2。 In the first embodiment, the one-side protective polarizing film A0, A1 or A2 with a transparent layer was produced in the same manner as in Example 1 except that the material of the transparent layer and the thickness of the transparent layer were changed as shown in Table 1.
另,比較例2之透明層係如下述。 Further, the transparent layer of Comparative Example 2 is as follows.
使用線棒塗佈機將上述活性能量線硬化型形成材料(丙烯酸系形成材料A)以會成為厚度1μm之方式進行塗佈後,於氮氣環境下照射活性能量線,製出附透明層之單側保護偏光薄膜A0。所得附透明層之單側保護偏光薄膜A0之 光學特性均為透光率42.8%、偏光度99.99%。 The active energy ray-curable forming material (acrylic forming material A) was applied to a thickness of 1 μm using a wire bar coater, and then irradiated with an active energy ray under a nitrogen atmosphere to produce a single layer with a transparent layer. Side protection polarizing film A0. The obtained one-side protective polarizing film A0 with a transparent layer The optical characteristics were 42.8% transmittance and 99.99% polarization.
於實施例1中,除了將單側保護偏光薄膜之種類、透明層形成材料之種類、透明層厚度變更如表1所示之外,與實施例1同樣地製出附透明層之單側保護偏光薄膜D至F。所得附透明層之單側保護偏光薄膜D至F之光學特性為透光率42.8%、偏光度99.99%。 In the first embodiment, the one-side protection with a transparent layer was produced in the same manner as in Example 1 except that the type of the one-side protective polarizing film, the type of the transparent layer forming material, and the thickness of the transparent layer were changed as shown in Table 1. Polarized film D to F. The optical characteristics of the obtained one-side protective polarizing films D to F with a transparent layer were 42.8% of light transmittance and 99.99% of polarization degree.
於30℃之溫度條件下,將相對於含乙醯乙醯基之聚乙烯醇系樹脂(平均聚合度:1200,皂化度:98.5莫耳%,乙醯乙醯基化度:5莫耳%)100份為50份之羥甲基三聚氰胺溶解於純水中,調製出固體成分已調整至濃度3.7%之水溶液。對於前述水溶液100份,添加氧化鋁膠體水溶液(平均粒徑15nm,固體成分濃度10%,正電荷)18份,調製出水系接著劑。 At a temperature of 30 ° C, the polyvinyl alcohol-based resin with respect to the ethyl acetonitrile group (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetylation: 5 mol%) 100 parts of 50 parts of methylol melamine were dissolved in pure water to prepare an aqueous solution having a solid content adjusted to a concentration of 3.7%. To 100 parts of the aqueous solution, 18 parts of an aqueous alumina colloid solution (having an average particle diameter of 15 nm and a solid concentration of 10% and a positive charge) was added to prepare a water-based adhesive.
於吸水率0.75%、Tg75℃之非晶質異苯二甲酸-共聚-聚對酞酸乙二酯(IPA共聚PET)薄膜(厚度:100μm)基材的單面上施加電暈處理,於25℃下在該電暈處理面上塗佈含聚乙烯醇(聚合度2500,皂化度99.0莫耳%)之水溶液並使其乾燥,形成厚度1μm的PVA系樹脂層,製出積層體。接著,於單側保護偏光薄膜A0之偏光件面(未設保護薄膜之 偏光件面)上以膜厚會成為0.1μm之方式塗佈上述水系接著劑,貼合到上述積層體之PVA樹脂層面後,於60℃下乾燥1分鐘。之後,將基材之PET薄膜剝離,製出附透明層之單側保護偏光薄膜。 Corona treatment was applied to one side of a substrate of a crystalline isophthalic acid-co-polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 μm) having a water absorption of 0.75% and a Tg of 75 ° C. An aqueous solution containing polyvinyl alcohol (degree of polymerization: 2,500, saponification degree: 99.0 mol%) was applied to the corona-treated surface at ° C and dried to form a PVA-based resin layer having a thickness of 1 μm to prepare a laminate. Next, the polarizer surface of the polarizing film A0 is protected on one side (the protective film is not provided) The water-based adhesive was applied to the surface of the polarizer so that the film thickness was 0.1 μm, and the film was bonded to the PVA resin layer of the laminate, and then dried at 60 ° C for 1 minute. Thereafter, the PET film of the substrate was peeled off to prepare a one-side protective polarizing film with a transparent layer.
於上述光學薄膜積層體A0之偏光件表面上,一邊以硬化後接著劑層之厚度會成為0.5μm之方式塗佈上述紫外線硬化型接著劑,一邊貼合上述保護薄膜。更進一步於前述保護薄膜表面上一邊以硬化後接著劑層之厚度會成為0.5μm之方式塗佈上述紫外線硬化型接著劑,一邊貼合上述保護薄膜後,照射紫外線作為活性能量線以使接著劑硬化。 On the surface of the polarizer of the optical film laminate A0, the ultraviolet curable adhesive was applied so that the thickness of the adhesive layer after curing was 0.5 μm, and the protective film was bonded thereto. Further, the ultraviolet curable adhesive is applied to the surface of the protective film so that the thickness of the adhesive layer after curing is 0.5 μm, and after bonding the protective film, ultraviolet rays are applied as an active energy ray to make an adhesive. hardening.
接著,剝離非晶性PET基材,製出使用了薄型偏光件之單側保護偏光薄膜(積層)B。所得單側保護偏光薄膜(積層)B之光學特性為透光率42.8%、偏光度99.99%。 Next, the amorphous PET substrate was peeled off to produce a one-side protective polarizing film (layered) B using a thin polarizer. The optical characteristics of the obtained one-side protective polarizing film (layered layer) B were 42.8% of light transmittance and 99.99% of polarization degree.
於參考例7所得上述單側保護偏光薄膜(積層)B之偏光件面(未設保護薄膜之偏光件面)上,利用線棒塗佈機以乾燥後厚度會成為0.7μm之方式塗佈已調整至25℃之上述聚乙烯醇系形成材料A後,於60℃下熱風乾燥1分鐘,製出附透明層之單側保護偏光薄膜(積層)B。所得附透明層之單側保護偏光薄膜(積層)B之光學特性均為透光率42.8%、偏光度99.99%。 The polarizer surface of the one-side protective polarizing film (layer) B obtained in Reference Example 7 (the polarizer surface on which the protective film is not provided) was coated by a wire bar coater so as to have a thickness of 0.7 μm after drying. After the polyvinyl alcohol-based material A was adjusted to 25 ° C, it was dried by hot air at 60 ° C for 1 minute to prepare a one-side protective polarizing film (layered) B with a transparent layer. The optical characteristics of the obtained one-side protective polarizing film (layered layer) B with a transparent layer were 42.8% of light transmittance and 99.99% of polarization degree.
於參考例1所得上述單側保護偏光薄膜A0之偏光件面(未設保護薄膜之偏光件面)上,利用線棒塗佈機以乾燥後厚度會成為0.7μm之方式塗佈已調整至25℃之上述聚乙烯醇系形成材料A後,於60℃下熱風乾燥1分鐘,製出附透明層之單側保護偏光薄膜A0。 The polarizer surface of the one-side protective polarizing film A0 obtained in Reference Example 1 (the polarizer surface on which the protective film is not provided) was coated to have a thickness of 0.7 μm after drying by a wire bar coater. After the polyvinyl alcohol-based material A was formed at ° C, it was dried by hot air at 60 ° C for 1 minute to prepare a one-side protective polarizing film A0 having a transparent layer.
於上述附透明層之單側保護偏光薄膜A0之透明層表面上,一邊以硬化後接著劑層之厚度會成為0.5μm之方式塗佈上述紫外線硬化型接著劑,一邊貼合上述保護薄膜後,照射紫外線作為活性能量線以使接著劑硬化。所得附透明層之雙側保護偏光薄膜C之光學特性為透光率42.8%、偏光度99.99%。 On the surface of the transparent layer of the one-side protective polarizing film A0 having the transparent layer, the ultraviolet curable adhesive is applied so that the thickness of the adhesive layer after curing is 0.5 μm, and the protective film is bonded thereto. Ultraviolet rays are irradiated as an active energy ray to harden the adhesive. The optical characteristics of the obtained double-sided protective polarizing film C with a transparent layer were 42.8% of light transmittance and 99.99% of polarization degree.
於參考例1所得上述單側保護偏光薄膜A0之偏光件面(未設保護薄膜之偏光件面)上,一邊以硬化後接著劑層之厚度會成為0.5μm之方式塗佈上述紫外線硬化型接著劑,一邊貼合上述保護薄膜後,照射紫外線作為活性能量線以使接著劑硬化。所得附透明層之雙側保護偏光薄膜C之光學特性為透光率42.8%、偏光度99.99%。 In the polarizing surface of the one-side protective polarizing film A0 obtained in Reference Example 1 (the polarizing surface of the protective film), the ultraviolet curing type was applied so that the thickness of the adhesive layer after curing was 0.5 μm. After bonding the protective film, the ultraviolet rays are irradiated as an active energy ray to cure the adhesive. The optical characteristics of the obtained double-sided protective polarizing film C with a transparent layer were 42.8% of light transmittance and 99.99% of polarization degree.
針對上述實施例及比較例所得偏光薄膜進行下述評價。茲將結果示於表1。評價係針對所製成之附黏著劑層之偏光薄膜按下述方式進行。 The polarizing films obtained in the above examples and comparative examples were subjected to the following evaluations. The results are shown in Table 1. The evaluation was carried out in the following manner with respect to the polarizing film of the prepared adhesive layer.
針對實施例及比較例所得偏光件,使用傅立葉轉換紅外線分光光度計(FTIR)(Perkin Elmer公司製,商品名「SPECTRUM 2000」),以偏振光為測定光之全反射衰減分光(ATR)測定法來測定硼酸尖峰(665cm-1)之強度及參照尖峰(2941cm-1)之強度。以下式從所得硼酸尖峰強度及參照尖峰強度算出硼酸量指數,再透過下式而從算出之硼酸量指數決定硼酸含量(重量%)。 For the polarizers obtained in the examples and the comparative examples, a Fourier transform infrared spectrophotometer (FTIR) (trade name "SPECTRUM 2000" manufactured by Perkin Elmer Co., Ltd.) was used, and the total reflection attenuation spectrometry (ATR) measurement method using the polarized light as the measurement light was used. The intensity of the boric acid spike (665 cm -1 ) and the intensity of the reference peak (2941 cm -1 ) were measured. The boric acid amount index was calculated from the obtained boric acid spike intensity and the reference peak intensity, and the boric acid content (% by weight) was determined from the calculated boric acid amount index by the following formula.
(硼酸量指數)=(硼酸尖峰665cm-1之強度)/(參照尖峰2941cm-1之強度) (boric acid amount index) = (strength of boric acid spike 665 cm -1 ) / (reference intensity of peak 2941 cm -1 )
(硼酸含量(重量%))=(硼酸量指數)×5.54+4.1 (Boronic acid content (% by weight)) = (boric acid amount index) × 5.54 + 4.1
於設有攪拌葉片、溫度計、氮氣導入管及冷卻器之4口燒瓶中饋入丙烯酸丁酯99份及甲基丙烯酸4-羥丁酯1份之單體混合物。進一步對前述單體混合物(固體成分)100份,將聚合引發劑之2,2'-偶氮二異丁腈0.1份與乙酸乙酯一同饋入,一邊徐徐攪拌一邊導入氮氣進行氮置換後,使燒瓶內之液溫維持在60℃左右並進行7小時聚合反應。之後,於所得反應液中加入乙酸乙酯,調製出固體成分已調整成濃度30%且重量平均分子量140萬之丙烯酸系聚合物溶液。 A monomer mixture of 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl methacrylate was fed into a 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a cooler. Further, 100 parts of the monomer mixture (solid content), 0.1 part of 2,2 ' -azobisisobutyronitrile of a polymerization initiator, and ethyl acetate were fed together, and nitrogen gas was introduced and nitrogen substitution was carried out while stirring slowly. The liquid temperature in the flask was maintained at about 60 ° C and polymerization was carried out for 7 hours. Thereafter, ethyl acetate was added to the obtained reaction liquid to prepare an acrylic polymer solution having a solid content of 30% and a weight average molecular weight of 1.4 million.
對上述丙烯酸系聚合物溶液之固體成分100份,摻合三羥甲基丙烷二甲苯二異氰酸酯(三井化學公司製:Takenate D110N)0.1份、過氧化二苯甲醯0.3份及γ-環氧丙氧基丙基甲 氧基矽烷(信越化學工業公司製:KBM-403)0.075份,調製出丙烯酸系黏著劑溶液。 100 parts of the solid component of the above acrylic polymer solution, blended with trimethylolpropane xylene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.: Takenate D110N) 0.1 part, 0.3 parts of dibenzoguanidine peroxide, and γ-glycidyl Oxypropylpropyl 0.075 parts of oxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403) was prepared to prepare an acrylic adhesive solution.
接著,以噴注式刮刀塗佈機將上述丙烯酸系黏著劑溶液均勻塗佈在經聚矽氧系剝離劑處理之聚對酞酸乙二酯薄膜(分隔件薄膜)表面,並以155℃之空氣循環式恒溫烘箱乾燥2分鐘,於分隔件薄膜之表面形成厚度20μm之黏著劑層。 Next, the acrylic adhesive solution was uniformly applied onto the surface of a polyethylene terephthalate film (separator film) treated with a polyfluorene-based release agent by a jet knife coater at 155 ° C. The air circulating type constant temperature oven was dried for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the separator film.
接著,將各例所得偏光薄膜之透明層(但參考例1~7為偏光件側,參考例8為一側之保護薄膜)上貼合已形成在上述脫模片(分隔件)之剝離處理面的黏著劑層,製出附黏著劑層之偏光薄膜。 Next, the transparent layer of the polarizing film obtained in each example (but the reference examples 1 to 7 are the polarizer side, and the reference example 8 is the protective film on one side) were bonded to the release treatment formed on the release sheet (separator). The adhesive layer of the surface is used to form a polarizing film with an adhesive layer.
相溶層厚度係以搭載有氣體團簇離子槍之TOF-SIMS來測定。偏光薄膜(樣本)之透明層(不含相溶層)之膜厚使用了預先以掃描型電子顯微鏡算出之正確膜厚數值。從偏光薄膜(樣本)之透明層側起朝偏光件側,一邊以氬團簇蝕刻一邊觀察深度剖面,抽出源自偏光件之「BO2 -離子」(離子強度)。針對自透明層側起算之深度(nm)與「BO2 -離子」(離子強度),製作如圖3所示之圖表。令得自電子顯微鏡之透明層膜厚為「B」、自偏光件側朝透明層側「BO2 -離子」開始減少處為「A」且「A-B間距離」為相溶層厚度。就實施例1以掃描型電子顯微鏡計測膜厚之結果,相對於偏光件厚為5.0μm,透明層厚度為0.8μm。此外,以TOF-SIMS從透明層 側起一邊蝕刻一邊測定離子強度,結果獲得如圖3所示之圖表。相對於圖3之透明層中之「BO2 -離子」強度為0.8,偏光件中之「BO2 -離子」強度為3.5。此外,如圖3所示,A-B間形成了「BO2 -離子」強度之梯度。若從氬團簇之蝕刻速率換算「A-B間距離」,則相溶層之厚度為0.12μm。又,若使用實施例所載FTIR來測定透明層側「BO2 -離子」強度為0.8之部分的硼酸含量,則硼酸含量為4%。另一方面,TOF-SIMS中「BO2 -離子」強度為3.5之偏光件中的硼酸含量係在形成透明層前以FTIR求出,硼酸含量為16%。由此顯示,偏光件之相溶層中,硼酸係以具梯度之形式存在(即,相溶層相當於硼酸濃度較偏光件之其他部分相對更低之硼酸低濃度層)。 The thickness of the compatible layer was measured by TOF-SIMS equipped with a gas cluster ion gun. The film thickness of the transparent layer (excluding the phase of the polarizing layer) of the polarizing film (sample) was calculated from the correct film thickness calculated in advance by a scanning electron microscope. From the transparent layer side of the polarizing film (sample) toward the polarizer side, the depth profile was observed while etching with argon clusters, and "BO 2 - ions" (ion intensity) derived from the polarizer were extracted. A graph as shown in Fig. 3 was prepared for the depth (nm) and "BO 2 - ion" (ion intensity) from the side of the transparent layer. So that the film thickness of the transparent layer is obtained from the electron microscope as "B", from the side of a polarizer "BO 2 - ion" begins to decrease toward the side of the transparent layer is "A" and "distance between AB" is the thickness of the compatible layer. As a result of measuring the film thickness by a scanning electron microscope in Example 1, the thickness of the polarizing member was 5.0 μm, and the thickness of the transparent layer was 0.8 μm. Further, the ionic strength was measured while etching from the side of the transparent layer by TOF-SIMS, and as a result, a graph as shown in Fig. 3 was obtained. FIG 3 with respect to the transparent layer in the "BO 2 - ionic" strength of 0.8, the polarizer member "BO 2 - ionic" strength of 3.5. Further, as shown in FIG. 3, a gradient of "BO 2 - ion" intensity is formed between ABs. When the "inter-AB distance" is converted from the etching rate of the argon cluster, the thickness of the phase-soluble layer is 0.12 μm. Further, when using FTIR examples contained in the transparent layer side measurement "BO 2 - ionic" strength of 0.8 parts of boric acid, the boric acid content of 4%. On the other hand, TOF-SIMS in "BO 2 - ionic" strength of a boric acid content of 3.5 based polarizer obtained in FTIR prior to forming the transparent layer, a boric acid content of 16%. It is thus shown that in the phase of the polarizer, the boric acid is present in the form of a gradient (i.e., the phase of the soluble layer corresponds to a lower concentration of boric acid having a lower concentration of boric acid than other portions of the polarizer).
測定裝置使用傅立葉轉換紅外線分光光度計(FT-IR)(Perkin Elmer公司製,商品名「SPECTRUM 2000」)。以偏振光為測定光,並利用全反射衰減分光(ATR:attenuated total reflection)測定法來進行透明層表面之評價。定向函數之算出係以下述順序進行。於令測定偏振光相對於偏光件之延伸方向呈0°與90°之狀態下實施測定。使用所得光譜2941cm-1處之強度係依下述(式)算出。此外,下述強度I係以3330cm-1為參照尖峰,使用了2941cm-1/3330cm-1之值。另,f=1時會完全定向,f=0時會變得無規。又,2941cm-1之尖峰據說為「-CH2-」振動起因之吸收。用於透明層之材料的主鏈中,在無「-CH2-」時,可 取代為主鏈之振動起因之光譜來進行評價。 The measurement apparatus used was a Fourier transform infrared spectrophotometer (FT-IR) (manufactured by Perkin Elmer Co., Ltd., trade name "SPECTRUM 2000"). The polarized light was used as the measurement light, and the surface of the transparent layer was evaluated by an ATR (Attenuated Total Reflection) measurement method. The calculation of the orientation function is performed in the following order. The measurement was carried out in a state where the measured polarized light was 0° and 90° with respect to the extending direction of the polarizing member. The intensity at which the obtained spectrum was 2941 cm -1 was calculated according to the following formula. Further, the intensity I of the following line as the reference peak at 3330cm -1, a value used 2941cm -1 / 3330cm -1 of. In addition, when f=1, it will be completely oriented, and when f=0, it will become random. Further, the peak of 2941 cm -1 is said to be the absorption of the vibration of "-CH 2 -". In the main chain of the material for the transparent layer, when there is no "-CH 2 -", it can be evaluated in place of the spectrum of the vibration of the main chain.
(式)f=(3<cos2θ>-1)/2=(1-D)/[c(2D+1)] (formula) f=(3<cos 2 θ>-1)/2=(1-D)/[c(2D+1)]
但,c=(3cos2β-1)/2β=90degf=-2×(1-D)/(2D+1)θ:分子鏈‧延伸方向β:分子鏈‧躍遷偶極矩D=(I⊥)/(I ∥ ) However, c=(3cos 2 β-1)/2β=90deg f=-2×(1-D)/(2D+1)θ: molecular chain ‧ extension direction β: molecular chain ‧ transition dipole moment D=(I ⊥ )/(I ∥ )
(PVA越定向,D值越大。) (The more PVA is oriented, the larger the D value.)
I⊥:使偏振光入射延伸方向與垂直方向並測定時之強度;I ∥ :使偏振光入射與延伸方向平行之方向並測定時之強度。 I ⊥ : The intensity at which the polarized light is incident and measured in the vertical direction; I ∥ : the intensity at which the polarized light is incident in the direction parallel to the extending direction and measured.
以所得附黏著劑層之偏光薄膜之吸收軸方向為縱向,裁切到縱100mm×100mm大小尺寸並貼到厚度1.3mm之無鹼玻璃後,於85℃環境下投入500小時。之後,測定偏光薄膜之大小。依下式從所得結果算出吸收軸方向之尺寸變化率%。 The direction of the absorption axis of the obtained polarizing film with the adhesive layer was longitudinally cut, cut to a length of 100 mm × 100 mm, and attached to an alkali-free glass having a thickness of 1.3 mm, and then placed in an environment of 85 ° C for 500 hours. Thereafter, the size of the polarizing film was measured. The dimensional change rate % in the absorption axis direction was calculated from the obtained result according to the following formula.
{(投入後之長度)-(投入前之長度)}/(投入前之長度)×100(%) {(length after input) - (length before input)} / (length before input) × 100 (%)
尺寸變化率係以未設透明層之情況(參考例1~8)為基準,利用以下所示基準來判斷具相同結構之偏光薄膜之尺寸變化率的減少比例。尺寸變化抑制效果可依下式算出。 The dimensional change rate is based on the case where no transparent layer is provided (Reference Examples 1 to 8), and the reduction ratio of the dimensional change ratio of the polarizing film having the same structure is determined by the following criteria. The dimensional change suppression effect can be calculated according to the following formula.
100-{(尺寸變化率)/(基準尺寸變化率)×100}(%)基準対 100-{(dimension change rate) / (reference Dimensional change rate) × 100} (%) benchmark 対
×:尺寸變化之抑制效果小於10%。 ×: The suppression effect of the dimensional change is less than 10%.
△:尺寸變化之抑制效果為10%以上且小於15%。 △: The suppression effect of the dimensional change was 10% or more and less than 15%.
○:尺寸變化之抑制效果為15%以上且小於20%。 ○: The suppression effect of the dimensional change was 15% or more and less than 20%.
◎:尺寸變化之抑制效果為20%以上。 ◎: The suppression effect of the dimensional change was 20% or more.
將所得附黏著劑層之偏光薄膜裁切為長400mm×寬708mm尺寸(吸收軸方向為400mm)與長708mm×寬400mm尺寸(吸收軸方向為708mm),再朝正交偏光鏡之方向貼合到長402mm×寬710mm×厚度1.3mm之無鹼玻璃兩面而製出樣本。將該樣本投入95℃烘箱計250小時後,取出並以目測確認附黏著劑層之偏光薄膜是否發生裂紋。該試驗係就1樣本進行10片,計數發生裂紋之樣本片數並按以下判斷基準進行判斷。 The polarizing film of the obtained adhesive layer was cut into a length of 400 mm × a width of 708 mm (absorption axis direction of 400 mm) and a length of 708 mm × width of 400 mm (absorption axis direction of 708 mm), and then attached to the direction of the orthogonal polarizer. A sample was prepared on both sides of an alkali-free glass having a length of 402 mm × a width of 710 mm and a thickness of 1.3 mm. After the sample was placed in an oven at 95 ° C for 250 hours, it was taken out and visually confirmed whether or not cracks occurred in the polarizing film of the adhesive layer. In this test, 10 samples were taken for one sample, and the number of cracked samples was counted and judged based on the following criteria.
×:裂紋發生片數達6片以上。 ×: The number of crack occurrences was six or more.
△:裂紋發生片數為3~5片。 △: The number of crack occurrences is 3 to 5 pieces.
○:裂紋發生片數為1~2片。 ○: The number of crack occurrences is 1 to 2 pieces.
◎:未發生裂紋。 ◎: No crack occurred.
將所得附黏著劑層之偏光薄膜裁切為25mm×50mm尺寸(吸收軸方向為50mm)。將該單側保護偏光薄膜(樣本)投入85℃/85%RH之恒溫恒濕機計150小時。使用附積分球支分光透光率測定器(村上色彩技術研究所之Dot-3c),測定投入前與投入後之單側保護偏光薄膜之偏光度,求出偏光度之變化率(%)=(1-(投入後之偏光度/投入前之偏光度))。 The obtained polarizing film with the adhesive layer was cut into a size of 25 mm × 50 mm (the absorption axis direction was 50 mm). The one-side protective polarizing film (sample) was placed in a constant temperature and humidity machine at 85 ° C / 85% RH for 150 hours. The polarization degree of the unilateral protective polarizing film before and after the input was measured using an integral sphere-branch spectroscopic transmittance measuring instrument (Dot-3c of Murakami Color Technology Research Institute), and the rate of change of the degree of polarization (%) was determined. (1-(polarization after input/polarization before input)).
另,偏光度P係藉由將下述透光率運用到下式來求得者,即:將2片相同之偏光薄膜以兩者之透射軸呈平行之方式貼合時的透光率(平行透光率:Tp);及,以兩者之透射 軸呈直交之方式疊合時的透光率(直交透光率:Tc)。 Further, the degree of polarization P is obtained by applying the following light transmittance to the following formula, that is, the light transmittance when two identical polarizing films are bonded in such a manner that the transmission axes of the two are parallel. Parallel transmittance: Tp); and, by transmission of both The transmittance of the axis when it is superposed (straight transmittance: Tc).
偏光度P(%)={(Tp-Tc)/(Tp+Tc)}1/2×100 Polarization P(%)={(Tp-Tc)/(Tp+Tc)} 1/2 ×100
各透光率係以通過格蘭泰勒稜鏡偏光件所得完全偏振光為100%,利用JIS Z8701之2度視野(C光源)修正視感度所得之Y值來表示。 Each light transmittance is represented by a Y value obtained by correcting the visual sensitivity by a 2 degree field of view (C light source) of JIS Z8701 by using 100% of fully polarized light obtained by a Glan Taylor polarizer.
表1在記載偏光度之變化率之同時,並以下述基準來判斷該變化率。 Table 1 shows the rate of change of the degree of polarization while determining the rate of change based on the following criteria.
○:偏光度之變化率為0.5%以下。 ○: The rate of change in the degree of polarization was 0.5% or less.
△:偏光度之變化率大於0.5%且在5.0%以下。 △: The rate of change in the degree of polarization is more than 0.5% and is 5.0% or less.
×:偏光度之變化率大於5.0%。 ×: The rate of change in the degree of polarization is greater than 5.0%.
表1中,WS表示羥甲基三聚氰胺:Water Sol S-695(DIC公司製))。 In Table 1, WS represents methylol melamine: Water Sol S-695 (manufactured by DIC Corporation).
1‧‧‧偏光件 1‧‧‧ polarizer
2‧‧‧透明層 2‧‧‧Transparent layer
3‧‧‧樹脂基材 3‧‧‧Resin substrate
10‧‧‧偏光薄膜 10‧‧‧Polarized film
A‧‧‧偏光件厚度 A‧‧‧ polarizer thickness
B‧‧‧相溶層厚度 B‧‧‧Composition layer thickness
X‧‧‧相溶層 X‧‧‧compatible layer
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