TW201630744A - Polarization film having coating layer, polarization film having adhesive layer and image display device - Google Patents

Abstract

An objective of the invention is to provide a polarization film having coating layer. The polarization film having coating layer can restrain degradation of a transparent conductive layer and inhibit the rising of surface resistance value of the transparent conductive layer even if the adhesive layer is laminated on the transparent conductive layer; and has excellent adhesiveness for the polarization film even when the adhesive layer is formed. The polarization film having the coating layer of this invention sequentially comprises a transparent protection layer, an iodine based polarizer containing iodine and/or iodine ions and the coating layer, and is characterized in that the iodine based polarizer and/or the coating layer contains a phosphorus based compound.

Description

附有塗敷層之偏光膜、附有黏著劑層之偏光膜、及圖像顯示裝置 Polarizing film with coating layer, polarizing film with adhesive layer, and image display device

本發明係關於一種依序具有透明保護膜、碘系偏光子以及塗敷層之附有塗敷層之偏光膜、及具有該附有塗敷層之偏光膜及黏著劑層之附有黏著劑層之偏光膜。又，本發明係關於一種具有上述附有黏著劑層之偏光膜之液晶顯示裝置(LCD)、有機EL(Electroluminescence，電致發光)顯示裝置等圖像顯示裝置。 The present invention relates to a polarizing film having a coating layer with a transparent protective film, an iodine-based polarizer, and a coating layer, and an adhesive attached to the polarizing film and the adhesive layer with the coating layer Layer of polarizing film. Further, the present invention relates to an image display device such as a liquid crystal display device (LCD) or an organic EL (Electroluminescence) display device having the above-described polarizing film with an adhesive layer.

近年來，氧化銦錫(ITO)薄膜等透明導電膜於各種用途中被廣泛使用。例如已知上述透明導電膜形成於橫向電場效應(IPS)方式等之使用有液晶單元之液晶顯示裝置之與構成液晶單元之透明基板之液晶層接觸側之相反側，而作為抗靜電層。又，於透明樹脂膜上形成有上述透明導電膜之透明導電性膜被用於觸控面板之電極基板，例如將用於行動電話或攜帶用音樂播放器等中之液晶顯示裝置或圖像顯示裝置與該觸控面板組合而使用之輸入裝置逐漸廣泛普及。 In recent years, transparent conductive films such as indium tin oxide (ITO) films have been widely used in various applications. For example, it is known that the transparent conductive film is formed on the opposite side of the liquid crystal display device using a liquid crystal cell such as a transverse electric field effect (IPS) method and the liquid crystal layer of the transparent substrate constituting the liquid crystal cell, and functions as an antistatic layer. Moreover, the transparent conductive film in which the transparent conductive film is formed on the transparent resin film is used for the electrode substrate of the touch panel, and for example, it is used for a liquid crystal display device or image display in a mobile phone or a portable music player or the like. Input devices used in combination with the touch panel are gradually becoming widespread.

作為將觸控面板與圖像顯示裝置組合而使用之輸入裝置，先前將於包含玻璃板或透明樹脂膜之透明基材上形成有透明導電層之透明導電性膜設置於液晶顯示裝置上(較液晶顯示裝置之視認側偏光膜更上側)之Out-Cell型得到廣泛普及，但近年來，已知有將包含透明導電膜之電極形成於液晶單元之上玻璃基板上之On-Cell型、將包含透明導電膜之電極組裝至液晶單元內部之形式之In-Cell型等各種構成。又，亦已知藉由以作為圖像顯示裝置之抗靜電層之ITO層作為觸控感 測器並將其圖案化而實現觸控面板功能。 As an input device used in combination with a touch panel and an image display device, a transparent conductive film on which a transparent conductive layer is formed on a transparent substrate including a glass plate or a transparent resin film is previously disposed on a liquid crystal display device (more The Out-Cell type of the liquid crystal display device having the upper side of the viewing-side polarizing film is widely used. However, in recent years, an On-Cell type in which an electrode including a transparent conductive film is formed on a glass substrate above a liquid crystal cell is known. Various configurations such as an In-Cell type in which the electrode including the transparent conductive film is assembled to the inside of the liquid crystal cell. Further, it is also known to use the ITO layer as an antistatic layer of an image display device as a touch feeling. The sensor is patterned and patterned to implement the touch panel function.

有於此種ITO層上經由黏著劑層貼合偏光膜等光學構件之情形，但已知於黏著劑具有羧基之情形時，會腐蝕ITO層而使導電性降低，作為抑制該導電性降低之黏著劑，已知含有磷系抗氧化劑之黏著劑(例如參照專利文獻1)。 In the case where an optical member such as a polarizing film is bonded to the ITO layer via an adhesive layer, it is known that when the adhesive has a carboxyl group, the ITO layer is corroded to lower the conductivity, and the decrease in conductivity is suppressed. As the adhesive, an adhesive containing a phosphorus-based antioxidant is known (for example, see Patent Document 1).

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第5540383號說明書 [Patent Document 1] Japanese Patent No. 5540383

對於使用有上述透明導電膜之液晶顯示裝置、圖像顯示裝置等而言，近年來強烈要求輕量化、薄型化，對於該液晶顯示裝置等中所使用之偏光膜亦要求薄型化、輕量化。作為偏光膜之薄型化、輕量化之方法，例如已知有製成僅於偏光子之單面設置有透明保護膜之單面保護偏光膜之方法、或使偏光子自身之膜厚變薄之薄型偏光膜之製造方法等。 In the liquid crystal display device, the image display device, and the like using the above-described transparent conductive film, in recent years, weight reduction and thinning have been strongly demanded, and the polarizing film used in the liquid crystal display device or the like is also required to be thinner and lighter. As a method of reducing the thickness and weight of the polarizing film, for example, a method of forming a single-sided protective polarizing film provided with a transparent protective film on only one side of a polarizer, or thinning the film thickness of the polarizer itself is known. A method of manufacturing a thin polarizing film or the like.

例如於使用透明導電膜作為抗靜電層用途之情形時，通常於具有該抗靜電層之液晶單元上積層附有黏著劑層之偏光膜，經由黏著劑層而使包含透明導電膜之抗靜電層與偏光膜貼合。又，於使用透明導電膜作為觸控面板之電極用途之情形時，根據觸控面板之構成，有於上述電極用透明導電膜上積層附有黏著劑層之偏光膜，經由黏著劑層而使包含透明導電膜之抗靜電層與偏光膜貼合之情況。 For example, when a transparent conductive film is used as an antistatic layer, a polarizing film with an adhesive layer is usually laminated on a liquid crystal cell having the antistatic layer, and an antistatic layer containing a transparent conductive film is formed via an adhesive layer. Bonded to the polarizing film. Further, when a transparent conductive film is used as the electrode of the touch panel, the polarizing film with the adhesive layer laminated on the transparent conductive film for the electrode is formed by the adhesive layer according to the configuration of the touch panel. The antistatic layer containing the transparent conductive film is bonded to the polarizing film.

於偏光膜為碘系偏光膜之情形時，若如上述般使透明導電層與該碘系偏光膜貼合，並進行加濕耐久試驗(通常之耐久試驗)，則有透明導電層之電阻值上升之情況。已知上述電阻值上升之原因在於，因偏光子中所含之碘滲出至黏著劑層，該碘到達透明導電層而腐蝕透明 導電層。 When the polarizing film is an iodine-based polarizing film, if the transparent conductive layer is bonded to the iodine-based polarizing film as described above and subjected to a humidification endurance test (normal durability test), the resistance value of the transparent conductive layer is obtained. The situation of rising. It is known that the above resistance value rises because the iodine contained in the polarizer oozes out to the adhesive layer, and the iodine reaches the transparent conductive layer and is corroded and transparent. Conductive layer.

特別是關於厚度10μm以下之薄型碘系偏光子，已知為了具有與先前之偏光子同樣之偏光特性而必須提高偏光子中之碘濃度，於將包含上述碘濃度較高之偏光子之偏光膜與透明導電層貼合之情形時，容易產生透明導電層之由碘引起之腐蝕。又，已知於使用單面保護之碘系偏光膜之情形時，由於經由黏著劑層將透明導電層直接貼合於碘系偏光子上，因而亦容易產生透明導電層之腐蝕。 In particular, regarding a thin iodine-based polarizer having a thickness of 10 μm or less, it is known that it is necessary to increase the iodine concentration in the polarizer in order to have the same polarization characteristics as the previous polarizer, and to use a polarizing film containing a polarizer having a higher iodine concentration. In the case of bonding with a transparent conductive layer, iodine-induced corrosion of the transparent conductive layer is liable to occur. Further, in the case where a single-sided protected iodine-based polarizing film is used, since the transparent conductive layer is directly bonded to the iodine-based polarizer via the adhesive layer, corrosion of the transparent conductive layer is likely to occur.

又，專利文獻1中記載之由含有磷系抗氧化劑之黏著劑形成之黏著劑層無法充分確保對偏光膜之密接性。 Further, the adhesive layer formed of the adhesive containing a phosphorus-based antioxidant described in Patent Document 1 cannot sufficiently ensure the adhesion to the polarizing film.

因此，本發明之目的在於提供一種附有塗敷層之偏光膜，上述附有塗敷層之偏光膜即使於經由黏著劑層積層於透明導電層上之情形時，亦能夠抑制透明導電層之劣化，抑制透明導電層之表面電阻值上升，並且即使於形成有黏著劑層之情形時，對偏光膜之密接性亦優異。又，本發明之目的亦在於提供一種附有黏著劑層之偏光膜，其係於上述附有塗敷層之偏光膜上設置黏著劑層而成。進而，本發明之目的亦在於提供一種圖像顯示裝置，其包含上述附有黏著劑層之偏光膜之黏著劑層、及具有透明導電層之液晶面板。 Accordingly, it is an object of the present invention to provide a polarizing film with a coating layer which can suppress the transparent conductive layer even when a polarizing film having a coating layer is laminated on the transparent conductive layer via an adhesive. Deterioration suppresses an increase in the surface resistance value of the transparent conductive layer, and is excellent in adhesion to the polarizing film even in the case where the adhesive layer is formed. Further, another object of the present invention is to provide a polarizing film with an adhesive layer provided with an adhesive layer on the polarizing film with a coating layer. Further, another object of the present invention is to provide an image display device comprising the above-described adhesive layer having a polarizing film of an adhesive layer and a liquid crystal panel having a transparent conductive layer.

本案發明人等進行了深入研究，結果發現，藉由下述之附有塗敷層之偏光膜、附有黏著劑層之偏光膜等能夠解決上述課題，從而完成本發明。 As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by the following polarizing film with a coating layer and a polarizing film with an adhesive layer attached thereto, and the present invention has been completed.

即，本發明係關於一種附有塗敷層之偏光膜，其依序具有透明保護膜、含有碘及/或碘離子之碘系偏光子以及塗敷層，其特徵在於，上述碘系偏光子及/或上述塗敷層含有磷系化合物。 That is, the present invention relates to a polarizing film with a coating layer, which in turn has a transparent protective film, an iodine-based polarizer containing iodine and/or iodide ions, and a coating layer, characterized in that the iodine-based polarizer And/or the coating layer contains a phosphorus compound.

上述磷系化合物較佳為含有選自由下述通式(1)： The phosphorus compound preferably contains a compound selected from the following formula (1):

(式中，R¹及R²各自獨立地表示氫原子、或可含有氧原子之碳數1~18之烴殘基)所表示之化合物及上述通式(1)所表示之化合物之多聚物所組成之群中之1種以上之磷酸系化合物、及/或選自由下述通式(2)： (wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom) and a compound represented by the above formula (1) One or more phosphate compounds in the group consisting of the substances, and/or selected from the following formula (2):

(式中，R為氫原子、或可含有氧原子之碳數1~18之烴殘基)所表示之化合物及其鹽所組成之群中之1種以上之膦酸系化合物。 (In the formula, R is a hydrogen atom or a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom), and one or more phosphonic acid compounds in a group consisting of a salt thereof.

上述碘系偏光子之厚度較佳為10μm以下。 The thickness of the iodine-based polarizer is preferably 10 μm or less.

上述碘系偏光子中之上述碘及/或碘離子之含量可為3~12重量%。 The content of the iodine and/or iodide ion in the iodine-based polarizer may be 3 to 12% by weight.

於上述碘系偏光子與上述塗敷層之間可不具有透明保護膜。 A transparent protective film may not be provided between the iodine-based polarizer and the coating layer.

上述塗敷層較佳為由含有選自由聚胺基甲酸酯系樹脂、聚乙烯醇系樹脂及丙烯酸系樹脂所組成之群中之至少1種樹脂之樹脂組合物形成。 The coating layer is preferably formed of a resin composition containing at least one resin selected from the group consisting of a polyurethane resin, a polyvinyl alcohol resin, and an acrylic resin.

又，本發明係關於一種附有黏著劑層之偏光膜，其特徵在於，於上述附有塗敷層之偏光膜之塗敷層側具有黏著劑層。 Further, the present invention relates to a polarizing film with an adhesive layer, characterized in that an adhesive layer is provided on a side of a coating layer of the polarizing film with a coating layer.

上述黏著劑層較佳為含有離子性化合物。 The above adhesive layer preferably contains an ionic compound.

又，本發明之附有黏著劑層之偏光膜可以與具有透明導電層之透明導電性構件之透明導電層接觸之方式貼合附有黏著劑層之偏光膜之黏著劑層而使用。 Further, the polarizing film with an adhesive layer of the present invention can be used by bonding an adhesive layer of a polarizing film to which an adhesive layer is attached in contact with a transparent conductive layer of a transparent conductive member having a transparent conductive layer.

上述透明導電層較佳為由氧化銦錫形成。又，上述氧化銦錫較佳為非結晶性之氧化銦錫。 The transparent conductive layer is preferably formed of indium tin oxide. Further, the indium tin oxide is preferably amorphous indium tin oxide.

進而，本發明係關於一種圖像顯示裝置，其特徵在於，將上述附有黏著劑層之偏光膜之黏著劑層與具有透明導電層之液晶面板以使上述附有黏著劑層之偏光膜之黏著劑層與上述液晶面板之透明導電層接觸之方式貼合。 Furthermore, the present invention relates to an image display device characterized in that the adhesive layer of the polarizing film with an adhesive layer and the liquid crystal panel having a transparent conductive layer are used to make the polarizing film with the adhesive layer attached thereto. The adhesive layer is bonded to the transparent conductive layer of the liquid crystal panel.

本發明之附有塗敷層之偏光膜即使於經由黏著劑層積層於透明導電層上之情形時，亦能夠抑制透明導電層之劣化，抑制透明導電層之表面電阻值上升。認為其原因在於，藉由碘系偏光子及/或塗敷層中含有之磷系化合物之作用，能夠抑制碘系偏光子中含有之碘向透明導電層表面轉移，結果防止透明導電層之腐蝕。 When the polarizing film with a coating layer of the present invention is laminated on the transparent conductive layer via an adhesive, deterioration of the transparent conductive layer can be suppressed, and an increase in surface resistance of the transparent conductive layer can be suppressed. The reason for this is that the action of the iodine-based polarizer and/or the phosphorus-based compound contained in the coating layer can suppress the transfer of iodine contained in the iodine-based polarizer to the surface of the transparent conductive layer, thereby preventing corrosion of the transparent conductive layer. .

又，本發明之附有黏著劑層之偏光膜即使於如上所述地將黏著劑層貼合於透明導電層上之情形時，亦能夠抑制透明導電層之劣化。又，本發明之附有黏著劑層之偏光膜經由塗敷層將偏光膜與黏著劑層積層，並且於碘系偏光子及/或塗敷層中調配有磷系化合物，因此黏著劑層與偏光膜或塗敷層之密接性優異。其結果，能夠防止返工時之糊劑殘留、耐久性所致之剝離、加工時之糊劑不足等。進而，本發明能夠提供一種圖像顯示裝置，其包含上述附有黏著劑層之偏光膜之黏著劑層、及具有透明導電層之液晶面板。 Further, in the polarizing film with an adhesive layer of the present invention, even when the adhesive layer is bonded to the transparent conductive layer as described above, deterioration of the transparent conductive layer can be suppressed. Further, the polarizing film with an adhesive layer of the present invention laminates the polarizing film and the adhesive layer via the coating layer, and the phosphorus-based compound is blended in the iodine-based polarizer and/or the coating layer, so that the adhesive layer and the adhesive layer The polarizing film or the coating layer is excellent in adhesion. As a result, it is possible to prevent the residue of the paste at the time of rework, the peeling due to durability, the shortage of the paste during processing, and the like. Furthermore, the present invention can provide an image display device comprising the above-described adhesive layer having a polarizing film of an adhesive layer and a liquid crystal panel having a transparent conductive layer.

1‧‧‧附有塗敷層之偏光膜 1‧‧‧ polarizing film with coating

2‧‧‧碘系偏光子 2‧‧‧Iodine-based photon

3‧‧‧透明保護膜 3‧‧‧Transparent protective film

4‧‧‧塗敷層 4‧‧‧coating layer

5‧‧‧黏著劑層 5‧‧‧Adhesive layer

6‧‧‧附有黏著劑層之偏光膜 6‧‧‧ polarizing film with adhesive layer

圖1係本發明之附有塗敷層之偏光膜之概略剖視圖之一例。 Fig. 1 is a schematic cross-sectional view showing a polarizing film with a coating layer of the present invention.

圖2係本發明之附有黏著劑層之偏光膜之概略剖視圖之一例。 Fig. 2 is a schematic cross-sectional view showing a polarizing film with an adhesive layer of the present invention.

1.附有塗敷層之偏光膜 1. Polarized film with coating layer

本發明之附有塗敷層之偏光膜依序具有透明保護膜、含有碘及/或碘離子之碘系偏光子以及塗敷層，其特徵在於， 上述碘系偏光子及/或上述塗敷層含有磷系化合物。 The polarizing film with a coating layer of the present invention sequentially has a transparent protective film, an iodine-based polarizer containing iodine and/or iodide ions, and a coating layer, wherein The iodine-based polarizer and/or the coating layer contains a phosphorus-based compound.

以下，使用作為本發明之一實施形態之圖1，對本發明之附有塗敷層之偏光膜之構成進行說明。但是，本發明之附有塗敷層之偏光膜並不限定於圖1之形態。 Hereinafter, the configuration of the polarizing film with a coating layer of the present invention will be described with reference to Fig. 1 which is an embodiment of the present invention. However, the polarizing film with a coating layer of the present invention is not limited to the form of FIG.

本發明之附有塗敷層之偏光膜1依序具有透明保護膜3、碘系偏光子2及塗敷層4。雖未圖示，但碘系偏光子2與透明保護膜3通常經由接著劑層等進行積層。又，塗敷層4可直接設置於碘系偏光子2之不具有透明保護膜3之面。又，如後所述，塗敷層4可為1層亦可為2層以上，又，於碘系偏光子2與塗敷層4之間可具有透明保護膜，但對於本發明而言，於碘系偏光子2與塗敷層4直接進行積層之情形時，本發明之效果較為顯著。以下，對各自之材料進行說明。 The polarizing film 1 with a coating layer of the present invention has a transparent protective film 3, an iodine-based polarizer 2, and a coating layer 4 in this order. Although not shown, the iodine-based polarizer 2 and the transparent protective film 3 are usually laminated via an adhesive layer or the like. Further, the coating layer 4 can be directly provided on the surface of the iodine-based polarizer 2 which does not have the transparent protective film 3. Further, as described later, the coating layer 4 may be one layer or two or more layers, and may have a transparent protective film between the iodine-based polarizer 2 and the coating layer 4, but for the present invention, When the iodine-based polarizer 2 and the coating layer 4 are directly laminated, the effect of the present invention is remarkable. Hereinafter, each material will be described.

(1)碘系偏光子 (1) Iodine-based photon

作為碘系偏光子2，只要為含有碘及/或碘離子之偏光子，則可使用任意者，例如可列舉：使碘吸附於聚乙烯醇(PVA)系膜、部分縮甲醛化PVA系膜、乙烯-乙酸乙烯酯共聚物系部分皂化膜等親水性高分子膜上並進行單軸延伸而成者等。該等之中，較佳為包含PVA系膜及碘之偏光子。該等偏光子之厚度並無特別限定，通常為80μm以下左右。 The iodine-based polarizer 2 may be any one of iodine and/or iodide-containing polarizers. For example, iodine may be adsorbed on a polyvinyl alcohol (PVA) film or a partially formalized PVA film. A uniaxially stretched hydrophilic polymer film such as an ethylene-vinyl acetate copolymer-based partially saponified film. Among these, a PVA film and a iodine polarizer are preferable. The thickness of the polarizers is not particularly limited, and is usually about 80 μm or less.

以碘對PVA系膜進行染色並進行單軸延伸而成之偏光子例如可藉由如下方式製作：藉由將PVA浸漬於碘之水溶液中而進行染色，並延伸至原長度之3~7倍。根據需要亦可浸漬於硼酸或可包含硫酸鋅、氯 化鋅等之碘化鉀等之水溶液中。進而，根據需要亦可於染色前將PVA系膜浸漬於水中而進行水洗。藉由對PVA系膜進行水洗，能夠將PVA系膜表面之污垢或抗黏連劑洗淨，此外，藉由使PVA系膜膨潤，亦有防止染色不均等不均一之效果。延伸可於利用碘進行染色後進行，亦可一面染色一面延伸，又，亦可於延伸後利用碘進行染色。亦可於硼酸、碘化鉀等之水溶液或水浴中進行延伸。 A polarizer obtained by dyeing a PVA film with iodine and uniaxially stretching can be produced, for example, by immersing PVA in an aqueous solution of iodine, and extending it to 3 to 7 times the original length. . It may also be immersed in boric acid or may contain zinc sulfate or chlorine as needed. An aqueous solution of potassium iodide or the like such as zinc. Further, if necessary, the PVA-based film may be immersed in water and washed with water before dyeing. By washing the PVA film with water, the dirt or the anti-blocking agent on the surface of the PVA film can be washed, and the PVA film can be swollen to prevent unevenness in dyeing unevenness. The extension may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution or a water bath of boric acid, potassium iodide or the like.

又，於本發明中，亦可較佳地使用厚度為10μm以下之薄型碘系偏光子。就薄型化之觀點而言，上述碘系偏光子之厚度較佳為1~7μm。此種薄型碘系偏光子於以下方面較佳：厚度不均較少，視認性優異，又，由於尺寸變化較少而耐久性優異，進而作為偏光膜之厚度亦實現薄型化。 Further, in the present invention, a thin iodine-based polarizer having a thickness of 10 μm or less can also be preferably used. The thickness of the iodine-based polarizer is preferably from 1 to 7 μm from the viewpoint of thinning. Such a thin iodine-based polarizer is preferable in that the thickness is less uneven, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film is also reduced.

作為薄型偏光子，可代表性地列舉：日本專利特開昭51-069644號公報、日本專利特開2000-338329號公報、國際公開第2010/100917號說明書、國際公開第2010/100917號說明書、或者日本專利4751481號說明書或日本專利特開2012-073563號公報中所記載之薄型偏光膜。該等薄型偏光膜可藉由包括於積層體之狀態下對PVA系樹脂層及延伸用樹脂基材進行延伸之步驟及染色之步驟之製法而獲得。根據該製法，即使PVA系樹脂層較薄，亦可藉由被延伸用樹脂基材支持而於並無由延伸所引起之斷裂等不良之情況下進行延伸。 The thin-type polarizer can be exemplified by Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, and International Publication No. 2010/100917. A thin polarizing film described in Japanese Patent No. 4751481 or Japanese Patent Laid-Open Publication No. 2012-073563. These thin polarizing films can be obtained by a method of extending the PVA-based resin layer and the extending resin substrate in a state of being laminated, and a step of dyeing. According to this production method, even if the PVA-based resin layer is thin, it can be extended by the resin substrate for stretching and without defects such as breakage due to stretching.

作為上述薄型偏光膜，於包括於積層體之狀態下進行延伸之步驟及染色之步驟之製法中，就可高倍率地延伸而能夠提昇偏光性能之方面而言，較佳為藉由如國際公開第2010/100917號說明書、國際公開第2010/100917號說明書、或者日本專利4751481號說明書或日本專利特開2012-073563號公報中所記載之包括於硼酸水溶液中進行延伸之步驟之製法而獲得者，特佳為藉由日本專利4751481號說明書或日本專利特開2012-073563號公報中所記載之包括於硼酸水溶液中進行 延伸之前輔助性地進行空中延伸之步驟之製法而獲得者。 In the method of forming the thin polarizing film in the step of extending in the state of being laminated, and the step of dyeing, it is preferable to extend the film at a high magnification and to improve the polarizing performance. The method of the method of performing the step of extending in an aqueous solution of boric acid described in the specification of the International Publication No. 2010/100917, the specification of the International Publication No. 2010/100917, or the specification of Japanese Patent No. 4751481, or the Japanese Patent Laid-Open Publication No. 2012-073563 In particular, it is included in an aqueous solution of boric acid as described in Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563. The winner is obtained by extending the method of assisting the steps of aerial extension.

藉由在利用上述方法獲得之碘系偏光子2上積層含有下述之磷系化合物之塗敷層等，而有磷系化合物自該塗敷層等轉移至碘系偏光子2中，從而於碘系偏光子2中含有磷系化合物之情形。如此般於碘系偏光子2中含有磷系化合物之情形時，亦能夠抑制透明導電層之腐蝕，故而較佳。作為可於上述碘系偏光子2中含有之磷系化合物，可列舉與下述之磷系化合物同等者。 By coating a coating layer containing the following phosphorus-based compound on the iodine-based polarizer 2 obtained by the above method, the phosphorus-based compound is transferred from the coating layer or the like to the iodine-based polarizer 2, thereby The case where the iodine-based polarizer 2 contains a phosphorus-based compound. When the iodine-based polarizer 2 contains a phosphorus-based compound as described above, corrosion of the transparent conductive layer can be suppressed, which is preferable. The phosphorus-based compound which can be contained in the iodine-based polarizer 2 is equivalent to the phosphorus-based compound described below.

於碘系偏光子2含有磷系化合物之情形時，作為其含量，於碘系偏光子2中較佳為3重量%以下，更佳為0.01~1重量%，進而更佳為0.02~0.6重量%。 When the iodine-based polarizer 2 contains a phosphorus-based compound, the content of the iodine-based polarizer 2 is preferably 3% by weight or less, more preferably 0.01 to 1% by weight, still more preferably 0.02 to 0.6% by weight. %.

又，關於本發明中使用之碘系偏光子2之碘及/或碘離子之含量(以下，有時亦稱為碘含量)，於偏光子中可為3~12重量%，亦可為4~7.5重量%。對於本發明之附有塗敷層之偏光膜1而言，即使碘系偏光子2中之碘含量如上述範圍般多，亦能夠抑制積層於本發明之偏光膜1之透明導電層之表面電阻上升。認為其原因在於，藉由碘系偏光子2及/或下述之塗敷層4中含有之磷系化合物之作用，能夠抑制碘系偏光子中含有之碘轉移至透明導電層表面，結果防止透明導電層之腐蝕。 In addition, the content of iodine and/or iodide ion (hereinafter, also referred to as iodine content) of the iodine-based polarizer 2 used in the present invention may be 3 to 12% by weight or 4 in the polarizer. ~7.5% by weight. In the polarizing film 1 with a coating layer of the present invention, even if the iodine content in the iodine-based polarizer 2 is as large as the above range, the surface resistance of the transparent conductive layer laminated on the polarizing film 1 of the present invention can be suppressed. rise. It is considered that the iodine-based polarizer 2 and/or the phosphorus-based compound contained in the coating layer 4 described below can suppress the transfer of iodine contained in the iodine-based polarizer to the surface of the transparent conductive layer, and as a result, it is prevented. Corrosion of a transparent conductive layer.

(2)透明保護膜 (2) Transparent protective film

作為形成透明保護膜3之材料，較佳為透明性、機械強度、熱穩定性、水分阻斷性、各向同性等優異者。例如可列舉：聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯等聚酯系聚合物、二乙醯纖維素或三乙醯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)等苯乙烯系聚合物、聚碳酸酯系聚合物等。又，作為形成上述透明保護膜3之聚合物之例，亦可列舉：聚乙烯、聚丙烯、環系或具有降烯結構之聚烯烴、乙烯-丙 烯共聚物等聚烯烴系聚合物、氯乙烯系聚合物、尼龍或芳香族聚醯胺等醯胺系聚合物、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、聚苯硫醚系聚合物、乙烯醇系聚合物、偏二氯乙烯系聚合物、乙烯縮丁醛系聚合物、芳酯系聚合物、聚甲醛系聚合物、環氧系聚合物或上述聚合物之共混物等。透明保護膜3亦可以丙烯酸系、胺基甲酸酯系、丙烯酸胺基甲酸酯系、環氧系、矽酮系等之熱硬化型、紫外線硬化型樹脂之硬化層之形式形成。 The material for forming the transparent protective film 3 is preferably excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like. For example, a polyester-based polymer such as polyethylene terephthalate or polyethylene naphthalate, a cellulose-based polymer such as diethyl phthalocyanine or triethylene fluorene cellulose, or polymethyl methacrylate may be mentioned. An acrylic polymer such as an ester, a styrene polymer such as polystyrene or an acrylonitrile-styrene copolymer (AS resin), or a polycarbonate polymer. Further, examples of the polymer forming the transparent protective film 3 include polyethylene, polypropylene, ring system or have a drop. a polyolefin polymer such as an olefin structure or a polyolefin polymer such as an ethylene-propylene copolymer; a vinyl chloride polymer; a guanamine polymer such as nylon or an aromatic polyamine; a ruthenium-based polymer; Polyether oxime polymer, polyetheretherketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer , a polyoxymethylene polymer, an epoxy polymer or a blend of the above polymers, and the like. The transparent protective film 3 may be formed as a hardened layer of a thermosetting type or an ultraviolet curable resin such as an acrylic type, an urethane type, an acrylamide type, an epoxy type or an anthrone type.

上述透明保護膜3之厚度可適當地決定，通常就強度或操作性等作業性、薄膜性等方面而言，為1~500μm左右，較佳為1~300μm，更佳為5~200μm，進而更佳為5~150μm，特佳為20~100μm。 The thickness of the transparent protective film 3 can be appropriately determined, and it is usually about 1 to 500 μm, preferably 1 to 300 μm, more preferably 5 to 200 μm, in terms of workability and film properties such as strength and workability. More preferably, it is 5 to 150 μm, and particularly preferably 20 to 100 μm.

上述透明保護膜3可僅配置於上述碘系偏光子2之單面(單面保護偏光膜)，亦可配置於上述碘系偏光子2之雙面(雙面保護偏光膜)。於使用單面保護偏光膜之情形時(即，於碘系偏光子2與塗敷層4之間不具有透明保護膜之情形時)，本發明之效果較為顯著。又，即使為雙面保護偏光膜，於與上述塗敷層4接觸一側之透明保護膜(未圖示)之厚度較薄(例如為25μm以下)之情形時，本發明之效果亦較為顯著。 The transparent protective film 3 may be disposed only on one side (single-sided protective polarizing film) of the iodine-based polarizer 2, or may be disposed on both sides (double-sided protective polarizing film) of the iodine-based polarizer 2. When the one-side protective polarizing film is used (that is, when there is no transparent protective film between the iodine-based polarizer 2 and the coating layer 4), the effect of the present invention is remarkable. Further, even when the thickness of the transparent protective film (not shown) on the side in contact with the coating layer 4 is thin (for example, 25 μm or less), the effect of the present invention is remarkable even in the case of the double-sided protective polarizing film. .

上述碘系偏光子2與透明保護膜3通常經由水系接著劑等而密接。作為水系接著劑，可例示：異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯系、膠乳系、水系聚胺基甲酸酯、水系聚酯等。除上述以外，作為碘系偏光子2與透明保護膜3之接著劑，亦可列舉紫外線硬化型接著劑、電子束硬化型接著劑等。電子束硬化型偏光膜用接著劑對於上述各種透明保護膜3顯示出較佳之接著性。又，於本發明中使用之接著劑中，可含有金屬化合物填料。 The iodine-based polarizer 2 and the transparent protective film 3 are usually adhered to each other via a water-based adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, an ethylene-based, a latex-based, an aqueous polyurethane, and an aqueous polyester. In addition to the above, examples of the binder of the iodine-based polarizer 2 and the transparent protective film 3 include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for an electron beam curing type polarizing film exhibits good adhesion to the above various transparent protective films 3. Further, the binder used in the present invention may contain a metal compound filler.

於上述透明保護膜3之未接著碘系偏光子2之面可設置硬塗層、抗反射層、抗黏附層、擴散層或防眩層等功能層。再者，上述功能層可設置於透明保護膜3本身，亦可另外作為與透明保護膜3不同體者而 進行設置。 A functional layer such as a hard coat layer, an antireflection layer, an anti-adhesion layer, a diffusion layer or an anti-glare layer may be provided on the surface of the transparent protective film 3 which is not followed by the iodine-based polarizer 2. Furthermore, the functional layer may be disposed on the transparent protective film 3 itself, or may be different from the transparent protective film 3 Make settings.

(3)塗敷層 (3) coating layer

於僅於碘系偏光子2之單面設置透明保護膜3之情形時，塗敷層4設置於碘系偏光子2之另一單面(未積層透明保護膜3之面)，於在碘系偏光子2之兩面設置透明保護膜3之情形時，塗敷層4可設置於其中一透明保護膜上，於2片透明保護膜之厚度不同之情形時，較佳為設置於較薄之透明保護膜側。 In the case where the transparent protective film 3 is provided only on one side of the iodine-based polarizer 2, the coating layer 4 is provided on the other side of the iodine-based polarizer 2 (the surface of the transparent protective film 3 is not laminated) in the iodine When the transparent protective film 3 is provided on both sides of the polarizer 2, the coating layer 4 may be disposed on one of the transparent protective films. When the thickness of the two transparent protective films is different, it is preferably disposed on a thinner one. Transparent protective film side.

塗敷層4之厚度並無特別限制，就薄層化及光學可靠性之觀點而言，較佳為10μm以下，更佳為5μm以下，進而更佳為3μm以下。又，塗敷層4可為1層，亦可為2層以上，於為2層以上之情形時，較佳為複數層塗敷層整體滿足上述厚度。於塗敷層4為2層以上之情形時，只要至少1層中含有磷系化合物即可。 The thickness of the coating layer 4 is not particularly limited, and is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less from the viewpoint of thinning and optical reliability. Further, the coating layer 4 may be one layer or two or more layers. When two or more layers are used, it is preferable that the plurality of coating layers as a whole satisfy the above thickness. When the coating layer 4 is two or more layers, the phosphorus compound may be contained in at least one layer.

塗敷層4可由各種材料形成，例如可藉由將塗敷層形成用樹脂組合物塗佈於碘系偏光子2而形成。作為上述塗敷層形成用樹脂組合物中含有之樹脂材料，例如可列舉：聚酯系樹脂、聚醚系樹脂、聚碳酸酯系樹脂、聚胺基甲酸酯系樹脂、矽酮系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、PVA系樹脂、丙烯酸系樹脂等各種聚合物類、或者金屬氧化物之溶膠、二氧化矽溶膠等。該等樹脂中可適當地調配交聯劑。該等樹脂材料可單獨使用1種，或組合使用2種以上，其中就與碘系偏光子之密接性或光學可靠性之觀點而言，較佳為選自由聚胺基甲酸酯系樹脂、PVA系樹脂、丙烯酸系樹脂所組成之群中之1種以上，更佳為PVA系樹脂。又，上述樹脂之形態可為水系、溶劑系中之任意一種。 The coating layer 4 can be formed of various materials, and can be formed, for example, by applying a resin composition for forming a coating layer to the iodine-based polarizer 2 . Examples of the resin material contained in the resin composition for forming a coating layer include a polyester resin, a polyether resin, a polycarbonate resin, a polyurethane resin, and an anthrone resin. Various polymers such as a polyamine-based resin, a polyimide-based resin, a PVA-based resin, and an acrylic resin, or a sol of a metal oxide, a cerium oxide sol or the like. A crosslinking agent can be suitably formulated among these resins. These resin materials may be used alone or in combination of two or more. From the viewpoint of adhesion to an iodine-based polarizer or optical reliability, it is preferably selected from a polyurethane resin. One or more of the group consisting of a PVA resin and an acrylic resin is more preferably a PVA resin. Further, the form of the resin may be any one of a water system and a solvent system.

再者，於黏著劑層含有酸成分之情形時(例如於含有丙烯酸等含羧基單體作為(甲基)丙烯酸系聚合物之單體單元之情形時)，就確保密接性之觀點而言，黏著劑層側之塗敷層較佳為含有具備與上述酸成分 具有反應性之官能基(例如唑啉基等)之化合物。例如，於塗敷層為2層以上之情形時，最靠近黏著劑層側之塗敷層較佳為包含含有唑啉基之聚合物。 In the case where the adhesive layer contains an acid component (for example, when a carboxyl group-containing monomer such as acrylic acid is used as a monomer unit of a (meth)acrylic polymer), from the viewpoint of ensuring adhesion, The coating layer on the side of the adhesive layer preferably contains a functional group having reactivity with the above acid component (for example, a compound of oxazoline or the like. For example, when the coating layer is two or more layers, the coating layer closest to the side of the adhesive layer preferably contains An oxazoline-based polymer.

(含有PVA系樹脂之塗敷層形成用樹脂組合物) (Resin composition for forming a coating layer containing a PVA resin)

作為上述PVA系樹脂，例如可列舉PVA。PVA可藉由將聚乙酸乙烯酯皂化而獲得。又，作為PVA系樹脂，可列舉乙酸乙烯酯及與其具有共聚性之單體之共聚物之皂化物。於上述具有共聚性之單體為乙烯之情形時，可獲得乙烯-乙烯醇共聚物。又，作為上述具有共聚性之單體，可列舉：馬來酸(酸酐)、富馬酸、巴豆酸、伊康酸、(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)烯丙基磺酸(鈉)、磺酸鈉(單烷基馬來酸酯)、二磺酸鈉烷基馬來酸酯、N-羥甲基丙烯醯胺、丙烯醯胺烷基磺酸鹼鹽、N-乙烯基吡咯啶酮、N-乙烯基吡咯啶酮衍生物等。該等PVA系樹脂可單獨使用1種，亦可併用2種以上。該等之中，較佳為將聚乙酸乙烯酯皂化而獲得之PVA。 As the PVA-based resin, for example, PVA is exemplified. PVA can be obtained by saponifying polyvinyl acetate. Further, examples of the PVA-based resin include a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability. In the case where the above 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, and (meth)acrylic acid, and esters thereof; ethylene and propylene. And other α-olefins; (meth)allylsulfonic acid (sodium), sodium sulfonate (monoalkyl maleate), sodium disulfonate alkyl maleate, N-methylol acrylamide And acrylamide alkyl sulfonate alkali salt, N-vinyl pyrrolidone, N-vinyl pyrrolidone derivative and the like. These PVA-based resins may be used alone or in combination of two or more. Among these, PVA obtained by saponifying polyvinyl acetate is preferred.

又，作為上述PVA系樹脂，可使用於上述PVA或其共聚物之側鏈具有親水性官能基之改性PVA系樹脂。作為上述親水性官能基，例如可列舉乙醯乙醯基、羰基等。此外，可使用將PVA系樹脂縮醛化、胺基甲酸酯化、醚化、接枝化、磷酸酯化等而成之改性PVA。 Further, as the PVA-based resin, a modified PVA-based resin having a hydrophilic functional group in the side chain of the PVA or the copolymer thereof can be used. Examples of the hydrophilic functional group include an ethyl acetyl group, a carbonyl group and the like. Further, a modified PVA obtained by acetalizing, urethane-forming, etherifying, grafting, or phosphoridating a PVA-based resin can be used.

本發明中使用之塗敷層4可由含有上述PVA系樹脂作為主成分、且含有下述之磷系化合物之塗敷層形成用樹脂組合物形成，於上述樹脂組合物中可含有硬化性成分(交聯劑)等。塗敷層4或樹脂組合物(固形物成分)中之PVA系樹脂之比率較佳為80重量%以上，更佳為90重量%以上，進而更佳為95重量%以上。 The coating layer 4 used in the present invention may be formed of a resin composition for forming a coating layer containing the PVA-based resin as a main component and containing the phosphorus-based compound described below, and may contain a curable component in the resin composition ( Crosslinking agent) and the like. The ratio of the PVA-based resin in the coating layer 4 or the resin composition (solid content component) is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more.

(含有丙烯酸系樹脂之塗敷層形成用樹脂組合物) (Resin composition for forming a coating layer containing an acrylic resin)

作為上述丙烯酸系樹脂，較佳為含有以下之硬化性成分之硬化型形成材料。作為硬化性成分，可大致分為電子束硬化型、紫外線硬 化型、可見光線硬化型等活性能量射線硬化型及熱硬化型。進而，紫外線硬化型、可見光線硬化型可分為自由基聚合硬化型及陽離子聚合硬化型。本發明中，將波長範圍為10nm以上且未達380nm之活性能量射線表示為紫外線，將波長範圍380nm~800nm之活性能量射線表示為可見光線。上述自由基聚合硬化型之硬化性成分可作為熱硬化型之硬化性成分使用。 The acrylic resin is preferably a curable forming material containing the following curable component. As a curable component, it can be roughly classified into an electron beam curing type and an ultraviolet curing method. Active energy ray hardening type and thermosetting type such as chemical type and visible light hardening type. Further, the ultraviolet curing type and the visible light curing type are classified into a radical polymerization curing type and a cationic polymerization curing type. In the present invention, an active energy ray having a wavelength range of 10 nm or more and less than 380 nm is represented as ultraviolet light, and an active energy ray having a wavelength range of 380 nm to 800 nm is represented as visible light. The above-mentioned radical polymerization hardening type curable component can be used as a thermosetting type curable component.

(自由基聚合硬化型形成材料) (radical polymerization hardening type forming material)

作為上述硬化性成分，例如可列舉自由基聚合性化合物。自由基聚合性化合物可列舉具有(甲基)丙烯醯基、乙烯基等碳-碳雙鍵之自由基聚合性官能基之化合物。該等硬化性成分可使用單官能自由基聚合性化合物或二官能以上之多官能自由基聚合性化合物中之任意一種。又，該等自由基聚合性化合物可單獨使用1種，或組合使用2種以上。作為該等自由基聚合性化合物，例如適合為具有(甲基)丙烯醯基之化合物。再者，本發明中，所謂(甲基)丙烯醯基係指丙烯醯基及/或甲基丙烯醯基，以下(甲基)具有同樣之含義。 The curable component is, for example, a radical polymerizable compound. The radical polymerizable compound may, for example, be a compound having a radical polymerizable functional group having a carbon-carbon double bond such as a (meth)acryl fluorenyl group or a vinyl group. As the curable component, any of a monofunctional radical polymerizable compound or a difunctional or higher polyfunctional radical polymerizable compound can be used. In addition, these radically polymerizable compounds may be used alone or in combination of two or more. As such a radically polymerizable compound, for example, a compound having a (meth) acrylonitrile group is suitable. In the present invention, the (meth)acrylonitrile group means a propylene group and/or a methacryl group, and the following (meth) has the same meaning.

(自由基聚合硬化型形成材料之態樣) (The aspect of the radical polymerization hardening type forming material)

自由基聚合硬化型形成材料可作為活性能量射線硬化型或熱硬化型之形成材料使用。於活性能量射線使用電子束等之情形時，該活性能量射線硬化型形成材料無需含有光聚合起始劑，但於活性能量射線使用紫外線或可見光線之情形時，較佳為含有光聚合起始劑。另一方面，於使用上述硬化性成分作為熱硬化性成分之情形時，該形成材料較佳為含有熱聚合起始劑。 The radical polymerization hardening type forming material can be used as a forming material of an active energy ray hardening type or a heat curing type. When the active energy ray is an electron beam or the like, the active energy ray-curable forming material does not need to contain a photopolymerization initiator, but in the case where the active energy ray uses ultraviolet rays or visible rays, it preferably contains a photopolymerization initiation. Agent. On the other hand, when the curable component is used as the thermosetting component, the forming material preferably contains a thermal polymerization initiator.

利用上述硬化型形成材料之塗敷層之形成係藉由在碘系偏光子(或透明保護膜)之面上塗敷硬化型形成材料，其後實施硬化而進行。又，碘系偏光子(或透明保護膜)亦可於塗敷上述硬化型形成材料之前進行表面改質處理。作為具體之處理，可列舉利用電暈處理、電漿處 理、皂化處理之處理等。 The formation of the coating layer using the above-mentioned hardening type forming material is carried out by applying a curing-type forming material to the surface of the iodine-based polarizer (or transparent protective film), followed by curing. Further, the iodine-based polarizer (or a transparent protective film) may be subjected to surface modification treatment before the application of the above-mentioned hardening-type forming material. As a specific treatment, it can be exemplified by corona treatment and plasma treatment. Treatment, saponification treatment, etc.

硬化型形成材料之塗敷方式可根據該硬化型形成材料之黏度或目標厚度適當選擇。作為塗敷方式之例，例如可列舉：反向塗佈機、凹版塗佈機(直接型、反向型、平版(offset)印刷型)、棒式反向塗佈機、輥式塗佈機、模嘴塗佈機、棒式塗佈機、桿式塗佈機(rod coater)等。此外，塗敷可適當使用浸塗方式等方式。 The coating method of the hardening type forming material can be appropriately selected depending on the viscosity or the target thickness of the hardening type forming material. Examples of the coating method include a reverse coater and a gravure coater (direct type, reverse type, offset printing type), a bar type reverse coater, and a roll coater. , a die coater, a bar coater, a rod coater, and the like. Further, the coating can be suitably carried out by a dip coating method or the like.

形成材料之硬化可以如下方式進行。 The hardening of the forming material can be carried out in the following manner.

(活性能量射線硬化型) (active energy ray hardening type)

關於活性能量射線硬化型形成材料，對碘系偏光子(或透明保護膜)塗敷活性能量射線硬化型形成材料後，照射活性能量射線(電子束、紫外線、可見光線等)，使活性能量射線硬化型形成材料硬化，形成塗敷層。關於活性能量射線(電子束、紫外線、可見光線等)之照射方向，可自任意適當之方向進行照射。較佳為自塗敷層側進行照射。 In the active energy ray-curable forming material, an active energy ray-curable forming material is applied to an iodine-based polarizer (or a transparent protective film), and then an active energy ray (electron beam, ultraviolet ray, visible light, or the like) is irradiated to cause an active energy ray. The hardening type forming material is hardened to form a coating layer. The irradiation direction of the active energy ray (electron beam, ultraviolet ray, visible light, etc.) can be irradiated from any appropriate direction. It is preferred to irradiate from the side of the coating layer.

(熱硬化型) (thermosetting type)

另一方面，關於熱硬化型形成材料，將偏光子與透明保護膜貼合後進行加熱，藉此利用熱聚合起始劑使聚合開始，形成硬化物層。加熱溫度根據熱聚合起始劑而設定，為60~200℃左右，較佳為80~150℃。 On the other hand, in the thermosetting type forming material, the polarizer is bonded to the transparent protective film and then heated, whereby the polymerization is started by the thermal polymerization initiator to form a cured layer. The heating temperature is set according to the thermal polymerization initiator, and is about 60 to 200 ° C, preferably 80 to 150 ° C.

(含有聚胺基甲酸酯系樹脂之塗敷層形成用樹脂組合物) (Resin composition for forming a coating layer containing a polyurethane resin)

作為本發明中使用之聚胺基甲酸酯系樹脂，為可藉由使多元醇與聚異氰酸酯反應而獲得者，具體而言，作為較佳地使用之聚胺基甲酸酯系樹脂，例如可列舉長瀨化成公司製之Denatron系列等。 The polyurethane resin used in the present invention is obtained by reacting a polyhydric alcohol with a polyisocyanate, and specifically, a polyurethane resin which is preferably used, for example. The Denatron series manufactured by Nagase Chemical Co., Ltd., and the like can be cited.

於利用水系材料形成塗敷層之情形時，使用水分散型聚合物。作為水分散型聚合物，可列舉：使用乳化劑將聚胺基甲酸酯、聚酯等各種樹脂乳液化而成者、於上述樹脂中導入水分散性之陰離子基、陽 離子基、或非離子基進行自乳化而成者等。 In the case where a coating layer is formed using a water-based material, a water-dispersible polymer is used. The water-dispersible polymer may be obtained by emulsifying various resins such as polyurethane and polyester with an emulsifier, and introducing an anionic group and a water-dispersible anion group into the resin. The ionic group or the nonionic group is self-emulsified.

(磷系化合物) (phosphorus compound)

本發明中，上述碘系偏光子及上述塗敷層中之任意一者或兩者含有磷系化合物。作為磷系化合物，例如可列舉磷酸系化合物、膦酸系化合物、磷系抗氧化劑，本發明中，該等可單獨使用，或組合使用二種以上。該等之中，較佳為磷酸系化合物或膦酸系化合物。 In the present invention, either or both of the iodine-based polarizer and the coating layer contain a phosphorus-based compound. Examples of the phosphorus-based compound include a phosphoric acid-based compound, a phosphonic acid-based compound, and a phosphorus-based antioxidant. In the present invention, these may be used alone or in combination of two or more. Among these, a phosphate compound or a phosphonic acid compound is preferred.

作為磷酸系化合物，例如可列舉選自由下述通式(1)： The phosphoric acid-based compound is, for example, selected from the following formula (1):

(式中，R¹及R²各自獨立地表示氫原子、或可含有氧原子之碳數1~18之烴殘基)所表示之化合物及上述通式(1)所表示之化合物之多聚物所組成之群中之磷酸系化合物。 (wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom) and a compound represented by the above formula (1) a phosphate compound in a group consisting of substances.

作為上述磷酸系化合物，如後所述，可列舉磷酸、磷酸酯、或者該等之鹽或二聚物、三聚物等。以下，對該等進行詳細說明。 Examples of the phosphoric acid-based compound include phosphoric acid, a phosphate ester, or a salt or a dimer or a trimer thereof. Hereinafter, the details will be described.

通式(1)中，R¹及R²各自獨立地為氫原子、或可含有氧原子之碳數1~18之烴殘基。作為可含有氧原子之碳數1~18之烴殘基，可列舉：碳數1~18之烷基、碳數1~18之烯基、碳數6~18之芳基、-(CH₂CH₂O)_nR³(R³為碳數1~18之烷基、碳數1~18之烯基、或碳數6~18之芳基，n為0~15之整數)等。又，烷基、烯基可為直鏈狀，亦可為支鏈狀。該等之中，作為上述碳數1~18之烴殘基，較佳為碳數1~10之直鏈或支鏈之烷基、碳數6~18之芳基，更佳為碳數2~6之直鏈或支鏈之烷基。 In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and -CH ₂ CH ₂ O) _n R ³ (R ³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is an integer of 0 to 15). Further, the alkyl group and the alkenyl group may be linear or branched. Among these, as the hydrocarbon residue having 1 to 18 carbon atoms, a linear or branched alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, and more preferably a carbon number of 2 are preferable. a straight or branched alkyl group of ~6.

本發明中，亦可適合地使用通式(1)之R¹及R²中之任一者為氫原子之磷酸(H₃PO₄)。又，亦可適合地使用上述磷酸之鹽(鈉、鉀及鎂等金屬鹽、銨鹽等)。 In the present invention, phosphoric acid (H ₃ PO ₄ ) in which any one of R ¹ and R ² in the formula (1) is a hydrogen atom can be suitably used. Further, a salt of the above phosphoric acid (a metal salt such as sodium, potassium or magnesium, or an ammonium salt) may be suitably used.

又，本發明中，通式(1)所表示之化合物較佳為酸性磷酸酯。此處，所謂酸性磷酸酯，係指通式(1)之R¹及R²均為可含有氧原子之碳數1~18之烴殘基之情況(二酯體)、或R¹、R²中之任一者為氫原子而另一者為可含有氧原子之碳數1~18之烴殘基之情況(單酯體)，例如可列舉以下之通式(1')： Further, in the present invention, the compound represented by the formula (1) is preferably an acid phosphate. Here, the acid phosphate refers to a case where both R ¹ and R ² in the formula (1) are hydrocarbon residues having 1 to 18 carbon atoms which may contain an oxygen atom (diester), or R ¹ and R. ^{In the case} where one of the two is a hydrogen atom and the other is a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom (monoester), for example, the following formula (1') is exemplified:

(式中，R¹與上述同樣，R³為碳數1~18之烷基、碳數1~18之烯基、或碳數6~18之芳基，n為0~15之整數)所表示之磷酸酯系化合物。 (wherein R ¹ is the same as above, and R ³ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and n is an integer of 0 to 15) A phosphate compound represented by the compound.

通式(1')之R¹與通式(1)之R¹同樣，為氫原子或可含有氧原子之碳數1~18之烴殘基。作為可含有氧原子之碳數1~18之烴殘基，可列舉與上述同樣者。作為通式(1')之R¹，較佳為氫原子、碳數1~18之直鏈或支鏈之烷基、或碳數6~18之芳基，更佳為氫原子、或碳數1~10之直鏈或支鏈之烷基，進而更佳為氫原子、或碳數2~6之直鏈或支鏈之烷基。作為R³，可列舉碳數1~18之烷基、碳數1~18之烯基、或碳數6~18之芳基，較佳為碳數1~18之烷基、碳數6~18之芳基，更佳為碳數1~10之烷基，進而更佳為碳數2~6之烷基。又，n為0~15之整數，較佳為0~10之整數。又，本發明中，就防止劣化之觀點而言， 較佳為不含有聚環氧乙烷結構(CH₂CH₂O)(即，式(1')中，n=0)。 R R Formula (1 ') of ^a general formula (1) of the same ^one, is a hydrogen atom or may contain carbon atoms, oxygen atoms of the hydrocarbon residue of 1 to 18. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include the same as described above. R ^{1 of the} formula (1') is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, more preferably a hydrogen atom or carbon. The linear or branched alkyl group of 1 to 10 is more preferably a hydrogen atom or a linear or branched alkyl group having 2 to 6 carbon atoms. Examples of R ³ include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms, preferably an alkyl group having 1 to 18 carbon atoms and a carbon number of 6~. The aryl group of 18 is more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 2 to 6 carbon atoms. Further, n is an integer of 0 to 15, preferably an integer of 0 to 10. Further, in the present invention, from the viewpoint of preventing deterioration, it is preferred that the polyethylene oxide structure (CH ₂ CH ₂ O) is not contained (that is, n = 0 in the formula (1').

作為通式(1')所表示之磷酸酯系化合物，就對被黏著體之吸附效果之觀點而言，較佳為R¹為氫原子、R³為碳數1~18之直鏈或支鏈之烷基之磷酸單酯，更佳為R¹為氫原子、R³為碳數1~10之直鏈或支鏈之烷基之磷酸單酯，進而更佳為R¹為氫原子、R³為碳數2~6之直鏈或支鏈之烷基之磷酸單酯。 As a phosphate ester compound represented by the formula (1'), from the viewpoint of the adsorption effect on the adherend, R ¹ is a hydrogen atom, and R ³ is a linear or branched carbon number of 1 to 18. a monoester of a chain alkyl group, more preferably a phosphate monoester in which R ¹ is a hydrogen atom, R ³ is a linear or branched alkyl group having 1 to 10 carbon atoms, and even more preferably R ¹ is a hydrogen atom. R ³ is a phosphoric acid monoester of a linear or branched alkyl group having 2 to 6 carbon atoms.

又，本發明中，可將通式(1')所表示之化合物混合2種以上使用，又，可使用通式(1')所表示之化合物與上述磷酸之混合物。又，通常通式(1')所表示之磷酸酯系化合物多作為單酯與二酯之混合物獲得，較佳為於上述單酯與二酯之混合物中進而加入上述磷酸而使用。 Further, in the present invention, a compound represented by the formula (1') may be used in combination of two or more kinds, and a mixture of the compound represented by the formula (1') and the above phosphoric acid may be used. Further, in general, the phosphate ester compound represented by the formula (1') is usually obtained as a mixture of a monoester and a diester, and it is preferred to further use the above phosphoric acid in a mixture of the above monoester and diester.

本發明中，亦可適合地使用通式(1')所表示之化合物之鹽(鈉、鉀及鎂等金屬鹽、銨鹽等)。 In the present invention, a salt of a compound represented by the formula (1') (a metal salt such as sodium, potassium or magnesium, or an ammonium salt) can be suitably used.

作為上述通式(1')所表示之磷酸酯系化合物之市售品，可列舉：東邦化學工業股份有限公司製之「Phosphanol SM-172」(通式(1')之R¹=R³=C₈H₁₇，n=0，單/二混合物(單酯體：二酯體=5：5(重量比)，酸值：219mgKOH/g)、「Phosphanol GF-185」(通式(1')之R¹=R³=C₁₃H₂₇，n=0，單/二混合物，酸值：158mgKOH/g)、「Phosphanol BH-650」(通式(1')之R¹=R³=C₄H₉，n=1，單/二混合物，酸值：388mgKOH/g)、「Phosphanol RS-410」(通式(1')之R¹=R³=C₁₃H₂₇，n=4，單/二混合物(單酯體：二酯體=5：5(重量比)，酸值：105mgKOH/g)、「Phosphanol RS-610」(通式(1')之R¹=C₁₃H₂₇，R³=C₁₃H₂₇，n=6，單/二混合物，酸值：82mgKOH/g)、「Phosphanol RS-710」(通式(1')之R¹=C₁₃H₂₇，R³=C₁₃H₂₇，n=10，單/二混合物(單酯體：二酯體=5：5(重量比))，酸值：62mgKOH/g)、「Phosphanol ML-220」(通式(1')之R¹=R³=C₁₂H₂₅，n=2，單/二混合物)、「Phosphanol ML-200」(通式(1')之R¹=R³=C₁₂H₂₅，n=0，單/二混合物)、 「Phosphanol ED-200」(通式(1')之R¹=R³=C₈H₁₇，n=1，單/二混合物)、「Phosphanol RL-210」((1')之R¹=R³=C₁₈H₃₇，n=2，單/二混合物)、「Phosphanol GF-339(通式(1')之R¹=R³=C₆H₁₃~C₁₀H₂₁之混合，n=0，單/二混合物)、「Phosphanol GF-199」(通式(1')之R¹=R³=C₁₂H₂₅，n=0，單/二混合物)、「Phosphanol RL-310」(通式(1')之R¹=R³=C₁₈H₃₇，n=3，單/二混合物)、「Phosphanol LP-700」(通式(1')之R¹=R³=C₆H₅，n=6，單/二混合物)，大八化學工業股份有限公司製之「AP-1」(通式(1')之R¹=R³=CH₃，n=0，單/二混合物，酸值：650mgKOH/g以上)、「AP-4」(通式(1')之R¹=R³=C₄H₉，n=0，單/二混合物，酸值：452mgKOH/g)、「DP-4」(通式(1')之R¹=R³=C₄H₉，n=0，二酯體，酸值：292mgKOH/g)、「MP-4」(通式(1')之R¹=H，R³=C₄H₉，n=0，單/二混合物(單酯體：二酯體=8：2(重量比))，酸值：670mgKOH/g)、「AP-8」(通式(1')之R¹=R³=C₈H₁₇，n=0，單/二混合物，酸值：306mgKOH/g)、「AP-10」(通式(1')之R¹=R³=C₁₀H₂₁，n=0，單/二混合物，酸值：263mgKOH/g)、「MP-10」(通式(1')之R¹=H，R³=C₁₀H₂₁，n=0，單酯體，酸值：400mgKOH/g)，城北化學股份有限公司製之「JP-508」(通式(1')之R¹=R³=C₈H₁₇，n=0，單/二混合物，酸值：288mgKOH/g)、「JP-513」(通式(1')之R¹=R³=C₁₃H₂₇，n=0，單/二混合物)、「JP-524R」(通式(1')之R¹=R³=C₂₄H₄₉，n=0，單/二混合物)、「DBP」(通式(1')之R¹=R³=C₄H₉，n=0，單/二混合物(單酯體：二酯體=1：9(重量比))，酸值：266mgKOH/g)、「LB-58」(通式(1')之R¹=R³=C₈H₁₇，n=0，二酯體，酸值：173mgKOH/g)，日光化學股份有限公司製之「Nikkol DDP-2」(通式(1')之R¹=R³=C₁₂H₂₅~C₁₅H₃₁之混合物、n=2)等以及該等之鹽。再者，上述所謂「單/二混合物」，係表示為單酯(R¹=H)與二酯(R¹=可含有氧原子之碳數1~18之烴殘基)之混合物，例如於為 Phosphanol SM-172之情形時，表示為單酯(通式(1')之R¹=H，R³=C₈H₁₇，n=0)與二酯(通式(1')之R¹=R³=C₈H₁₇，n=0)之混合物。 As a commercial product of the phosphate ester compound represented by the above formula (1'), "Phosphanol SM-172" manufactured by Toho Chemical Industry Co., Ltd. (R ¹ = R ^{3 of the} formula (1')) =C ₈ H ₁₇ , n=0, single/dimixture (monoester: diester = 5:5 (weight ratio), acid value: 219 mg KOH/g), "Phosphanol GF-185" (formula (1) ') R ¹ = R ³ = C ₁₃ H ₂₇ , n = 0, single/dimixture, acid value: 158 mg KOH/g), "Phosphanol BH-650" (R ¹ = R ^{3 of the} formula (1') =C ₄ H ₉ , n=1, single/two mixture, acid value: 388 mgKOH/g), "Phosphanol RS-410" (R ¹ = R ³ = C ₁₃ H _{27 of the} formula (1'), n = 4, single/dimixture (monoester: diester = 5:5 (weight ratio), acid value: 105 mgKOH/g), "Phosphanol RS-610" (R ¹ = C _{13 of the} formula (1') H ₂₇ , R ³ = C ₁₃ H ₂₇ , n = 6, single/dimixture, acid value: 82 mg KOH/g), "Phosphanol RS-710" (R ¹ = C ₁₃ H _{27 of the} formula (1'), R ³ =C ₁₃ H ₂₇ , n=10, single/dimixture (monoester:diester = 5:5 (weight ratio), acid value: 62 mgKOH/g), "Phosphanol ML-220" (pass R of formula (1 ') of _{^{1 = R 3 = C 12 H}} 25, n = 2, mono / di mixture), Phosphanol ML-200 "(the general formula (1 ') of _{^{R 1 = R 3 = C 12}} H 25, n = 0, mono / di mixture)," Phosphanol ED-200 "(the general formula (1') of ^a R & lt =R ³ =C ₈ H ₁₇ ,n=1, single/two mixture), "Phosphanol RL-210" (R ¹ =R ³ =C ₁₈ H ₃₇ , n=2, single/two mixture of (1') ), "Phosphanol GF-339 (R ¹ = R ³ = C ₆ H ₁₃ ~ C ₁₀ H ₂₁ mixture, n = 0, single / two mixture), "Phosphanol GF-199" ( R ¹ = R ³ = C ₁₂ H ₂₅ , n = 0, single/dimixture) of the formula (1'), "Phosphanol RL-310" (R ¹ = R ³ = C _{18 of the} formula (1') H ₃₇ , n=3, single/two mixture), “Phosphanol LP-700” (R ¹ =R ³ =C ₆ H _{5 of} formula (1'), n=6, single/two mixture), big eight "AP-1" manufactured by Chemical Industry Co., Ltd. (R ¹ = R ³ = CH _{3 of the} formula (1'), n = 0, single/two mixture, acid value: 650 mgKOH/g or more), "AP- 4" (R ¹ = R ³ = C ₄ H _{9 of the} formula (1'), n = 0, single/dimixture, acid value: 452 mgKOH/g), "DP-4" (formula (1') R ¹ = R ³ = C ₄ H ₉ , n = 0, diester, acid value: 292 mg KOH / g), "MP-4" (R ¹ = H of the formula (1'), R ³ = C ₄ H _9, n = 0, mono / di mixture (mono Body: diester = 8: 2 (weight ratio)), acid value: 670mgKOH / g), "AP-8" (general formula (1 ') of _{^{R 1 = R 3 = C 8}} H 17, n = 0 , single/two mixture, acid value: 306 mgKOH/g), "AP-10" (R ¹ = R ³ = C ₁₀ H _{21 of the} formula (1'), n = 0, single/two mixture, acid value: 263 mgKOH/g), "MP-10" (R ¹ =H of the formula (1'), R ³ =C ₁₀ H ₂₁ , n=0, monoester body, acid value: 400 mgKOH/g), Chengbei Chemical Co., Ltd. "JP-508" manufactured by the company (R ¹ = R ³ = C ₈ H _{17 of the} formula (1'), n = 0, single/two mixture, acid value: 288 mg KOH / g), "JP-513" (R ¹ = R ³ = C ₁₃ H _{27 of the} formula (1'), n = 0, single/dimixture), "JP-524R" (R ¹ = R ³ = C _{24 of the} formula (1') H ₄₉ , n = 0, single/two mixture), "DBP" (R ¹ = R ³ = C ₄ H _{9 of the} formula (1'), n = 0, single/dimixture (monoester: diester) Body = 1:9 (weight ratio), acid value: 266 mg KOH / g), "LB-58" (R ¹ = R ³ = C ₈ H _{17 of the} formula (1'), n = 0, diester body , acid value: 173 mg KOH / g), "Nikkol DDP-2" manufactured by Nikko Chemical Co., Ltd. (R ¹ = R ³ = a mixture of C ₁₂ H ₂₅ ~ C ₁₅ H ₃₁ of the formula (1'), n = 2) Etc. and the salts of these. In addition, the above-mentioned "single/di-mixture" is a mixture of a monoester (R ¹ =H) and a diester (R ¹ = a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom), for example, In the case of Phosphanol SM-172, it is represented as a monoester (R ¹ =H of the formula (1'), R ³ =C ₈ H ₁₇ , n=0) and a diester (R of the formula (1') A mixture of ¹ = R ³ = C ₈ H ₁₇ , n = 0).

作為本發明中使用之磷酸系化合物，可將選自由通式(1)所表示之化合物(或通式(1')所表示之化合物)、或者該等之鹽或多聚物所組成之群中之化合物單獨使用1種，亦可混合2種以上使用，較佳為選自由磷酸、磷酸單酯、及磷酸二酯所組成之群中之2種以上之混合物，更佳為包含磷酸單酯及磷酸之混合物。此處，所謂磷酸單酯，係指通式(1)之R¹及R²中之任一者為氫原子、而另一者為可含有氧原子之碳數1~18之烴殘基之化合物(於通式(1')之情形時，R¹為氫原子之化合物)，所謂磷酸二酯，係指通式(1)之R¹及R²為可含有氧原子之碳數1~18之烴殘基之化合物(於通式(1')之情形時，R¹為可含有氧原子之碳數1~18之烴殘基之化合物)。 The phosphate-based compound used in the present invention may be a group selected from the group consisting of a compound represented by the formula (1) (or a compound represented by the formula (1')) or a salt or a polymer thereof. The compound may be used singly or in combination of two or more. It is preferably a mixture of two or more selected from the group consisting of phosphoric acid, a phosphoric acid monoester, and a phosphoric acid diester, and more preferably a phosphate monoester. And a mixture of phosphoric acid. Here, the term "phosphoric acid monoester" means that any of R ¹ and R ² in the formula (1) is a hydrogen atom, and the other is a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. The compound (in the case of the formula (1'), the compound wherein R ¹ is a hydrogen atom), the term "phosphoric acid diester" means that R ¹ and R ² of the formula (1) are carbon atoms which may contain an oxygen atom. A compound of a hydrocarbon residue of 18 (in the case of the formula (1'), R ¹ is a compound which may contain a hydrocarbon residue having 1 to 18 carbon atoms of an oxygen atom).

又，本發明中使用之磷酸化合物之酸值較佳為900mgKOH/g以下，更佳為50~800mgKOH/g，較佳為10~700mgKOH/g。又，就生產上之操作之觀點而言，上述磷酸化合物之酸值較佳為400mgKOH/g以下，更佳為50~400mgKOH/g，進而更佳為50~350mgKOH/g，特佳為100~300mgKOH/g。於形成塗敷層4之組合物中含有交聯劑之情形時，磷酸化合物根據該交聯劑之種類(例如異氰酸酯系交聯劑)而有作為交聯反應之反應觸媒發揮作用之情況，於此情形時，有作為形成塗敷層4之組合物之適用期變短之情況，且有於操作性方面變差之情況。藉由將磷酸化合物之酸值設為上述範圍，能夠抑制作為反應觸媒之作用，因此就形成塗敷層4之組合物之適用期之觀點而言較佳。又，就能夠有效地發揮效果之觀點而言，較佳為將具有上述範圍之酸值之磷酸化合物以下述之添加量進行添加。 Further, the acid value of the phosphoric acid compound used in the present invention is preferably 900 mgKOH/g or less, more preferably 50 to 800 mgKOH/g, and more preferably 10 to 700 mgKOH/g. Further, from the viewpoint of production operation, the acid value of the phosphoric acid compound is preferably 400 mgKOH/g or less, more preferably 50 to 400 mgKOH/g, still more preferably 50 to 350 mgKOH/g, and particularly preferably 100~. 300 mg KOH / g. When the composition for forming the coating layer 4 contains a crosslinking agent, the phosphoric acid compound may function as a reaction catalyst for the crosslinking reaction depending on the type of the crosslinking agent (for example, an isocyanate crosslinking agent). In this case, there is a case where the pot life of the composition for forming the coating layer 4 is shortened, and there is a case where the workability is deteriorated. By setting the acid value of the phosphoric acid compound to the above range, the action as a reaction catalyst can be suppressed, and therefore it is preferable from the viewpoint of the application period of the composition of the coating layer 4. Further, from the viewpoint of effectively exhibiting an effect, it is preferred to add a phosphoric acid compound having an acid value within the above range in the following addition amount.

又，作為上述通式(1)所表示之化合物之多聚物，可列舉上述通式(1)所表示之化合物之二聚物、三聚物等。 In addition, examples of the polymer of the compound represented by the above formula (1) include a dimer and a trimer of the compound represented by the above formula (1).

又，作為磷系化合物，可列舉膦酸系化合物。作為膦酸系化合物，例如可列舉選自由下述通式(2)： Further, examples of the phosphorus compound include a phosphonic acid compound. The phosphonic acid-based compound is, for example, selected from the following formula (2):

(式中，R為氫原子、或可含有氧原子之碳數1~18之烴殘基)所表示之化合物及其鹽所組成之群中之膦酸系化合物。 (in the formula, R is a hydrogen atom or a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom) and a phosphonic acid compound in a group consisting of a salt thereof.

通式(2)中，R為氫原子、或可含有氧原子之碳數1~18之烴殘基。作為可含有氧原子之碳數1~18之烴殘基，可列舉碳數1~18之烷基、碳數1~18之烯基、碳數6~18之芳基等。又，烷基、烯基可為直鏈狀，亦可為支鏈狀。 In the formula (2), R is a hydrogen atom or a hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom. Examples of the hydrocarbon residue having 1 to 18 carbon atoms which may contain an oxygen atom include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 1 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms. Further, the alkyl group and the alkenyl group may be linear or branched.

可為通式(2)之R為氫原子之膦酸(HP(=O)(OH)₂)。又，亦可較佳地使用上述膦酸之鹽(鈉、鉀及鎂等金屬鹽、銨鹽等)。 It may be a phosphonic acid (HP(=O)(OH) ₂ ) wherein R of the formula (2) is a hydrogen atom. Further, a salt of the above phosphonic acid (a metal salt such as sodium, potassium or magnesium, or an ammonium salt) can be preferably used.

作為上述通式(2)所表示之膦酸系化合物，具體而言，可列舉：膦酸、甲基膦酸、乙基膦酸、正丙基膦酸、異丙基膦酸、正丁基膦酸、第三丁基膦酸、第二丁基膦酸、異丁基膦酸、正戊基膦酸、正己基膦酸、異己基膦酸、正庚基膦酸、正辛基膦酸、異辛基膦酸、第三辛基膦酸、正壬基膦酸、正癸基膦酸、異癸基膦酸、正十二烷基膦酸、異十二烷基膦酸、正十四烷基膦酸、正十六烷基膦酸、正十八烷基膦酸、正二十烷基膦酸、環丁基膦酸、環戊基膦酸、環己基膦酸、降基膦酸、苯基膦酸、萘基膦酸、聯苯基膦酸、甲氧基苯基膦酸、乙氧基苯基膦酸及該等之鹽。本發明中，該等可單獨使用，或組合使用二種以上。 Specific examples of the phosphonic acid compound represented by the above formula (2) include phosphonic acid, methylphosphonic acid, ethylphosphonic acid, n-propylphosphonic acid, isopropylphosphonic acid, and n-butyl group. Phosphonic acid, tert-butylphosphonic acid, second butylphosphonic acid, isobutylphosphonic acid, n-pentylphosphonic acid, n-hexylphosphonic acid, isohexylphosphonic acid, n-heptylphosphonic acid, n-octylphosphonic acid , isooctylphosphonic acid, trioctylphosphonic acid, n-decylphosphonic acid, n-decylphosphonic acid, isodecylphosphonic acid, n-dodecylphosphonic acid, isododecylphosphonic acid, positive ten Tetraalkylphosphonic acid, n-hexadecylphosphonic acid, n-octadecylphosphonic acid, n-icosylphosphonic acid, cyclobutylphosphonic acid, cyclopentylphosphonic acid, cyclohexylphosphonic acid, descending Phosphonic acid, phenylphosphonic acid, naphthylphosphonic acid, biphenylphosphonic acid, methoxyphenylphosphonic acid, ethoxyphenylphosphonic acid, and the like. In the present invention, these may be used alone or in combination of two or more.

又，作為磷系化合物，可列舉磷系抗氧化劑。作為磷系抗氧化 劑之具體例，可列舉：亞磷酸三辛酯、亞磷酸三月桂酯、亞磷酸三(十三烷基)酯、亞磷酸三異癸酯、亞磷酸苯酯二異辛酯、亞磷酸苯酯二異癸酯、亞磷酸苯酯二(十三烷基)酯、亞磷酸二苯酯異辛酯、亞磷酸二苯酯異癸酯、亞磷酸二苯酯十三烷基酯、亞磷酸三苯酯、亞磷酸三(壬基苯基)酯、亞磷酸三(2,4-二-第三丁基苯基)酯、亞磷酸三(丁氧基乙基)酯、四(十三烷基)-4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)-二亞磷酸酯、4,4'-亞異丙基-二苯酚烷基亞磷酸酯(其中，烷基為碳數12~15左右)、4,4'-亞異丙基雙(2-第三丁基苯酚)/二(壬基苯基)亞磷酸酯、亞磷酸三(聯苯基)酯、四(十三烷基)-1,1,3-三(2-甲基-5-第三丁基-4-羥基苯基)丁烷二亞磷酸酯、亞磷酸三(3,5-二-第三丁基-4-羥基苯基)酯、氫化-4,4'-亞異丙基二苯酚聚亞磷酸酯、雙(辛基苯基)/雙[4,4'-亞丁基雙(3-甲基-6-第三丁基苯酚)]/1,6-己二醇二亞磷酸酯、六(十三烷基)-1,1,3-三(2-甲基-4-羥基-5-第三丁基苯酚)二亞磷酸酯、三[4,4'-亞異丙基雙(2-第三丁基苯酚)]亞磷酸酯、亞磷酸三(1,3-二硬脂醯氧基異丙基)酯、9,10-二氫-9-磷雜菲-10-氧化物、四(2,4-二-第三丁基苯基)-4,4'-伸聯苯基二亞膦酸酯、二硬脂基季戊四醇二亞磷酸酯、二(壬基苯基)季戊四醇二亞磷酸酯、苯基/4,4'-亞異丙基二苯酚/季戊四醇二亞磷酸酯、雙(2,4-二-第三丁基苯基)季戊四醇二亞磷酸酯、雙(2,6-二-第三丁基-4-甲基苯基)季戊四醇二亞磷酸酯及苯基雙酚-A-季戊四醇二亞磷酸酯等。 Further, examples of the phosphorus-based compound include phosphorus-based antioxidants. Phosphorus-based antioxidant Specific examples of the agent include trioctyl phosphite, trilauryl phosphite, tris(tridecyl) phosphite, triisodecyl phosphite, diisooctyl phosphite, and phenyl phosphite. Diisodecyl ester, phenyl bis(tridecyl) phosphite, isooctyl phosphite, isodecyl phosphite, tridecyl phosphite, phosphorous acid Triphenyl ester, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(butoxyethyl) phosphite, tetra (thirteen) Alkyl)-4,4'-butylene bis(3-methyl-6-tert-butylphenol)-diphosphite, 4,4'-isopropylidene-diphenol alkyl phosphite ( Wherein, the alkyl group is a carbon number of 12 to 15), 4,4'-isopropylidene bis(2-tert-butylphenol) / bis(nonylphenyl) phosphite, and bisphosphite tris(biphenyl) Ester, tetrakis(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tris(3) ,5-di-t-butyl-4-hydroxyphenyl)ester, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, bis(octylphenyl)/bis[4,4' - Butylene bis(3-methyl-6-tert-butylphenol) ]/1,6-hexanediol diphosphite, hexatridecyl-1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenol) diphosphoric acid Ester, tris[4,4'-isopropylidenebis(2-tert-butylphenol)]phosphite, tris(1,3-bisstearyloxyisopropyl) phosphite, 9, 10-Dihydro-9-phosphaphenanthrene-10-oxide, tetrakis(2,4-di-t-butylphenyl)-4,4'-extended biphenyl diphosphinate, distearyl Pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, phenyl/4,4'-isopropylidenediphenol/pentaerythritol diphosphite, bis(2,4-di- Tributylphenyl)pentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite and phenylbisphenol-A-pentaerythritol diphosphite Wait.

上述磷系化合物之添加量相對於塗敷層形成用樹脂組合物中含有之樹脂成分100重量份，較佳為0.01~10重量份，更佳為0.01~5重量份，進而更佳為0.1~5重量份。藉由使磷系化合物之添加量處於上述範圍內，能夠抑制透明導電層之表面電阻值上升，故而較佳。又，本發明中，如上所述，可併用2種以上之磷系化合物，於此情形時可以使合計量達到上述範圍之方式進行添加。 The amount of the phosphorus-based compound to be added is preferably 0.01 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, even more preferably 0.1 to 100 parts by weight based on 100 parts by weight of the resin component contained in the resin composition for forming a coating layer. 5 parts by weight. When the amount of the phosphorus-based compound added is in the above range, the surface resistance value of the transparent conductive layer can be suppressed from increasing, which is preferable. In the present invention, as described above, two or more kinds of phosphorus-based compounds may be used in combination, and in this case, the total amount may be added to the above range.

又，塗敷層之形成材料中可含有抗靜電劑。抗靜電劑只要為能夠賦予導電性之材料，則並無特別限定，例如可列舉：離子性界面活性劑、導電性聚合物、金屬氧化物、碳黑、及碳奈米材料等，該等之中，較佳為導電性聚合物，更佳為水分散性導電聚合物。 Further, an antistatic agent may be contained in the material for forming the coating layer. The antistatic agent is not particularly limited as long as it can impart conductivity, and examples thereof include an ionic surfactant, a conductive polymer, a metal oxide, carbon black, and a carbon nanomaterial. Among them, a conductive polymer is preferred, and a water-dispersible conductive polymer is more preferred.

作為水溶性導電性聚合物，可列舉聚苯胺磺酸(經聚苯乙烯換算之重量平均分子量150000，三菱麗陽股份有限公司製造)等，作為水分散性導電聚合物，可列舉聚噻吩系導電性聚合物(長瀨化成公司製造，Denatron系列)等。 Examples of the water-soluble conductive polymer include polyaniline sulfonic acid (weight average molecular weight of 150,000 in terms of polystyrene, manufactured by Mitsubishi Rayon Co., Ltd.), and the like. Examples of the water-dispersible conductive polymer include polythiophene-based conductive materials. Polymer (manufactured by Changchun Chemical Co., Ltd., Denatron series) and the like.

上述抗靜電劑之調配量例如相對於塗敷層之形成材料中使用之上述聚合物類100重量份，為70重量份以下，較佳為50重量份以下。就抗靜電效果之方面而言，較佳為設為10重量份以上，進而設為20重量份以上。 The amount of the antistatic agent to be added is, for example, 70 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the polymer used in the material for forming the coating layer. In terms of the antistatic effect, it is preferably 10 parts by weight or more, and further preferably 20 parts by weight or more.

又，於塗敷層之形成材料中，可為了抑制與塗敷層接觸時產生之黏著劑層或碘系偏光子之劣化等而調配各種添加劑，又，可為了對塗敷層賦予功能而調配各種添加劑。例如，可添加抗氧化劑(磷系以外)、抗劣化劑、紫外線吸收劑、螢光增白劑等。 Further, in the material for forming the coating layer, various additives may be blended in order to suppress deterioration of the adhesive layer or the iodine-based polarizer which is generated when the coating layer is brought into contact with the coating layer, and may be formulated to impart a function to the coating layer. Various additives. For example, an antioxidant (other than phosphorus), an anti-deterioration agent, an ultraviolet absorber, a fluorescent whitening agent, or the like can be added.

作為上述塗敷層之形成方法，並無特別限定，可藉由通常公知之方法而進行。又，於形成塗敷層時，可對上述偏光膜1實施活化處理。活化處理可採用各種方法，例如可採用電暈處理、低壓UV處理、電漿處理等。 The method for forming the coating layer is not particularly limited, and it can be carried out by a generally known method. Further, when the coating layer is formed, the polarizing film 1 can be subjected to an activation treatment. The activation treatment can be carried out by various methods such as corona treatment, low pressure UV treatment, plasma treatment, and the like.

本發明中，藉由製成具有由含有上述磷酸系化合物之樹脂組合物形成之塗敷層4之附有塗敷層之偏光膜，即使將該附有塗敷層之偏光膜經由黏著劑層積層於透明導電層上，亦能夠抑制透明導電層之表面電阻上升。 In the present invention, a polarizing film having a coating layer having a coating layer 4 formed of a resin composition containing the above-described phosphoric acid compound is formed, even if the coating layer-attached polarizing film is passed through an adhesive layer. Lamination on the transparent conductive layer also suppresses an increase in surface resistance of the transparent conductive layer.

2.附有黏著劑層之偏光膜 2. Polarized film with adhesive layer

本發明之附有黏著劑層之偏光膜之特徵在於，於上述附有塗敷 層之偏光膜之塗敷層側具有黏著劑層。 The polarizing film with an adhesive layer of the present invention is characterized in that it is coated with the above The coating layer side of the polarizing film of the layer has an adhesive layer.

以下，使用作為本發明之一實施形態之圖2對本發明之附有黏著劑層之偏光膜之構成進行說明。但是，本發明之附有黏著劑層之偏光膜並不限定於圖2之形態。 Hereinafter, the configuration of the polarizing film with an adhesive layer of the present invention will be described with reference to Fig. 2 which is an embodiment of the present invention. However, the polarizing film with an adhesive layer of the present invention is not limited to the form of Fig. 2 .

關於本發明之附有黏著劑層之偏光膜6，如圖2所示，於上述附有塗敷層之偏光膜1之塗敷層4側具有黏著劑層5。可於本發明之附有黏著劑層之偏光膜6之黏著劑層5設置隔離件(未圖示)，於供於實用之前保護黏著劑層5。又，可於附有黏著劑層之偏光膜6之透明保護膜3側設置表面保護膜(未圖示)。以下，對各自之材料進行說明。 As shown in FIG. 2, the polarizing film 6 with an adhesive layer of the present invention has an adhesive layer 5 on the side of the coating layer 4 on which the coating layer-attached polarizing film 1 is attached. A spacer (not shown) may be provided on the adhesive layer 5 of the polarizing film 6 with the adhesive layer of the present invention to protect the adhesive layer 5 before being used for practical use. Further, a surface protective film (not shown) may be provided on the side of the transparent protective film 3 of the polarizing film 6 to which the adhesive layer is attached. Hereinafter, each material will be described.

黏著劑層5之形成中可使用適當之黏著劑，其種類並無特別限制。作為黏著劑，例如可列舉：橡膠系黏著劑、丙烯酸系黏著劑、矽酮系黏著劑、胺基甲酸酯系黏著劑、乙烯基烷基醚系黏著劑、聚乙烯醇系黏著劑、聚乙烯基吡咯啶酮系黏著劑、聚丙烯醯胺系黏著劑、纖維素系黏著劑等，該等之中，就光學透明性優異、顯示出適當之密接性、凝聚性及接著性之黏著特性、且耐候性或耐熱性等優異之觀點而言，較佳為使用丙烯酸系黏著劑。 A suitable adhesive can be used in the formation of the adhesive layer 5, and the kind thereof is not particularly limited. Examples of the adhesive include a rubber-based adhesive, an acrylic adhesive, an anthrone-based adhesive, a urethane-based adhesive, a vinyl alkyl ether-based adhesive, a polyvinyl alcohol-based adhesive, and a poly A vinylpyrrolidone-based adhesive, a polypropylene amide-based adhesive, a cellulose-based adhesive, etc., among these, excellent in optical transparency, and exhibiting adhesive properties of appropriate adhesion, cohesiveness, and adhesion. In view of excellent weather resistance and heat resistance, an acrylic adhesive is preferably used.

作為上述丙烯酸系黏著劑，可列舉含有(甲基)丙烯酸系聚合物者。作為上述(甲基)丙烯酸系聚合物，並無特別限制，例如較佳為使含有(甲基)丙烯酸烷基酯之單體成分聚合而獲得者，較佳為使含有(甲基)丙烯酸烷基酯及含羥基單體之單體成分聚合而獲得者。再者，(甲基)丙烯酸烷基酯係指丙烯酸烷基酯及/或甲基丙烯酸烷基酯，與本發明之(甲基)具有同樣之含義。 Examples of the acrylic pressure-sensitive adhesive include those containing a (meth)acrylic polymer. The (meth)acrylic polymer is not particularly limited. For example, it is preferred to obtain a monomer component containing an alkyl (meth)acrylate, and it is preferred to contain an alkyl (meth)acrylate. The monomer component of the base ester and the hydroxyl group-containing monomer is obtained by polymerization. Further, the alkyl (meth)acrylate means an alkyl acrylate and/or an alkyl methacrylate, and has the same meaning as the (meth) of the present invention.

作為(甲基)丙烯酸烷基酯之烷基，可使用直鏈狀或支鏈狀之各種者。作為上述(甲基)丙烯酸烷基酯之具體例，例如可例示：(甲基)丙烯酸丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正戊酯、(甲基) 丙烯酸異戊酯(isopentyl ester)、(甲基)丙烯酸異戊酯(isoamyl ester)、(甲基)丙烯酸正己酯、(甲基)丙烯酸庚酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸異肉豆蔻酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸十四烷基酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸十八烷基酯、或(甲基)丙烯酸十二烷基酯等。該等可單獨或組合使用。該等之中，較佳為具有碳數4~18之烷基之(甲基)丙烯酸烷基酯，更佳為具有碳數4~10之烷基之(甲基)丙烯酸酯，進而更佳為(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯，特佳為(甲基)丙烯酸正丁酯。 As the alkyl group of the alkyl (meth)acrylate, a linear or branched form can be used. Specific examples of the alkyl (meth)acrylate include, for example, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid. Dibutyl ester, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, (methyl) Isopentyl ester, isoamyl ester, n-hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, Isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, (meth)acrylic acid N-dodecyl ester, isomyristyl (meth)acrylate, n-tridecyl (meth)acrylate, tetradecyl (meth)acrylate, stearyl (meth)acrylate, ( Octadecyl methyl methacrylate or dodecyl (meth) acrylate. These may be used singly or in combination. Among these, an alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms is preferred, and a (meth) acrylate having an alkyl group having 4 to 10 carbon atoms is more preferred. It is n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, and particularly preferably n-butyl (meth)acrylate.

又，作為含羥基之單體，可無特別限定地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有羥基者。作為含羥基之單體，例如可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥基甲基環己基)甲酯等，該等可單獨使用1種，或混合2種以上使用。該等之中，較佳為丙烯酸4-羥基丁酯。又，於使用異氰酸酯系交聯劑作為下述之交聯劑之情形時，藉由使用丙烯酸4-羥基丁酯作為含羥基之單體，能夠高效率地確保與異氰酸酯系交聯劑之異氰酸酯基之交聯點，因而較佳。 In addition, as the hydroxyl group-containing monomer, a polymerizable functional group having an unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 6 -Hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (meth)acrylic acid (4-hydroxymethyl ring The hexyl)methyl ester or the like may be used alone or in combination of two or more. Among these, 4-hydroxybutyl acrylate is preferred. Further, when an isocyanate crosslinking agent is used as the crosslinking agent described below, by using 4-hydroxybutyl acrylate as a hydroxyl group-containing monomer, the isocyanate group with the isocyanate crosslinking agent can be efficiently ensured. The cross-linking point is therefore preferred.

於形成本發明中使用之(甲基)丙烯酸系聚合物之單體成分中，可含有上述具有碳數4~18之烷基之(甲基)丙烯酸烷基酯、任意之上述含羥基之單體等，除該等單體以外，亦可使用含羧基之單體、含芳基之單體、其他共聚單體作為單體成分。 The monomer component of the (meth)acrylic polymer used in the formation of the present invention may contain the alkyl (meth)acrylate having an alkyl group having 4 to 18 carbon atoms, and any of the above-mentioned hydroxyl group-containing monomers. In addition to the monomers, a carboxyl group-containing monomer, an aryl group-containing monomer, and other comonomer may be used as the monomer component.

作為含羧基單體，可無特別限定地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有羧基者。作為含羧基單 體，例如可列舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、馬來酸、富馬酸、巴豆酸等，該等可單獨或組合使用。 As the carboxyl group-containing monomer, a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group and having a carboxyl group can be used without particular limitation. As a carboxyl group Examples of the body include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc., which may be used alone. Or use in combination.

作為含芳基單體，可無特別限定地使用具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基且具有芳基者。作為含芳基單體，例如可列舉(甲基)丙烯酸苯酯、(甲基)丙烯酸苄酯等(甲基)丙烯酸芳基酯。 As the aryl group-containing monomer, a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group and having an aryl group can be used without particular limitation. Examples of the aryl group-containing monomer include aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate.

作為其他共聚單體，只要為具有(甲基)丙烯醯基或乙烯基等具有不飽和雙鍵之聚合性官能基者，則並無特別限定，可列舉：例如(甲基)丙烯酸環己酯、(甲基)丙烯酸酯、(甲基)丙烯酸異酯等(甲基)丙烯酸脂環式烴酯；例如乙酸乙烯酯、丙酸乙烯酯等乙烯酯類；例如苯乙烯等苯乙烯系單體；例如(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸甲基縮水甘油酯等含環氧基之單體；例如(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等含烷氧基之單體；例如丙烯腈、甲基丙烯腈等含氰基之單體；例如異氰酸2-甲基丙烯醯氧基乙酯等官能性單體；例如乙烯、丙烯、異戊二烯、丁二烯、異丁烯等烯烴系單體；例如乙烯醚等乙烯醚系單體；例如氯乙烯等含鹵素原子之單體等。 The other comonomer is not particularly limited as long as it has a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and examples thereof include cyclohexyl (meth)acrylate. ,(Methacrylate Ester, (meth)acrylic acid a (meth) acrylate cyclic hydrocarbon ester such as an ester; a vinyl ester such as vinyl acetate or vinyl propionate; a styrene monomer such as styrene; for example, glycidyl (meth)acrylate, (methyl) An epoxy group-containing monomer such as methyl glycidyl acrylate; an alkoxy group-containing monomer such as methoxyethyl (meth)acrylate or ethoxyethyl (meth)acrylate; for example, acrylonitrile a cyano group-containing monomer such as methacrylonitrile; a functional monomer such as 2-methylpropenyloxyethyl isocyanate; an olefin such as ethylene, propylene, isoprene, butadiene or isobutylene; A monomer; for example, a vinyl ether monomer such as vinyl ether; a halogen atom-containing monomer such as vinyl chloride or the like.

又，作為共聚性單體，可列舉：例如N-環己基馬來醯亞胺、N-異丙基馬來醯亞胺、N-月桂基馬來醯亞胺、N-苯基馬來醯亞胺等馬來醯亞胺系單體；例如N-甲基伊康醯亞胺、N-乙基伊康醯亞胺、N-丁基伊康醯亞胺、N-辛基伊康醯亞胺、N-2-乙基己基伊康醯亞胺、N-環己基伊康醯亞胺、N-月桂基伊康醯亞胺等伊康醯亞胺系單體；例如N-(甲基)丙烯醯氧基亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-6-氧基六亞甲基琥珀醯亞胺、N-(甲基)丙烯醯基-8-氧基八亞甲基琥珀醯亞胺等琥珀醯亞胺系單體；例如苯乙烯磺酸、烯丙磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基) 丙烯醯氧基萘磺酸等含磺酸基單體。 Further, examples of the copolymerizable monomer include N-cyclohexylmaleimide, N-isopropylmaleimide, N-lauryl maleimide, and N-phenyl malazone. A maleimide monomer such as an imine; for example, N-methyliconazole, N-ethyliconazole, N-butyliconazole, N-octylkononium Ikonide imine monomer such as imine, N-2-ethylhexylkamponium imine, N-cyclohexylkkonium imine, N-lauryl Icinoimide; for example, N-(A) Acryloxymethylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) propylene fluorenyl-8-oxygen An amber quinone imine monomer such as octamethylmethylene succinimide; for example, styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide phthalamide-2-methylpropane sulfonic acid, (methyl ) acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, (methyl) A sulfonic acid group-containing monomer such as acryloxynaphthalenesulfonic acid.

又，作為共聚性單體，可列舉含醯胺基單體。含醯胺基單體係於其結構中含有醯胺基且含有(甲基)丙烯醯基、乙烯基等聚合性不飽和雙鍵之化合物。作為含醯胺基單體之具體例，可列舉：(甲基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-異丙基丙烯醯胺、N-甲基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-羥甲基-N-丙烷(甲基)丙烯醯胺、胺基甲基(甲基)丙烯醯胺、胺基乙基(甲基)丙烯醯胺、巰基甲基(甲基)丙烯醯胺、巰基乙基(甲基)丙烯醯胺等丙烯醯胺系單體；N-(甲基)丙烯醯基啉、N-(甲基)丙烯醯基哌啶、N-(甲基)丙烯醯基吡咯啶等N-丙烯醯基雜環單體；N-乙烯基吡咯啶酮、N-乙烯基-ε-己內醯胺等含有N-乙烯基之內醯胺系單體等。含醯胺基單體就滿足耐久性之方面而言較佳，含醯胺基單體之中，特別是含有N-乙烯基之內醯胺系單體就滿足對透明導電層之耐久性之方面而言較佳。 Further, examples of the copolymerizable monomer include a guanamine-containing monomer. A compound containing a mercapto group-containing single system having a mercaptoamine group in its structure and containing a polymerizable unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group. Specific examples of the mercapto group-containing monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)acrylonitrile. Amine, N-isopropyl acrylamide, N-methyl (meth) acrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-hydroxyl (meth) acrylamide, N-methylol-N-propane (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, Acrylamide monomer such as mercaptomethyl (meth) acrylamide or mercaptoethyl (meth) acrylamide; N-(methyl) propylene fluorenyl N-propylene fluorenyl heterocyclic monomer such as porphyrin, N-(meth)acrylopylpiperidine or N-(methyl)propenylpyrrolidin; N-vinylpyrrolidone, N-vinyl-ε An internal amide-based monomer containing an N-vinyl group such as caprolactam. The mercapto group-containing monomer is preferable in terms of durability, and among the mercapto group-containing monomers, particularly the N-vinyl indoleamine monomer satisfies the durability to the transparent conductive layer. It is better in terms of aspects.

又，作為共聚性單體，可列舉：例如聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等二醇系丙烯酸酯單體；此外，例如(甲基)丙烯酸四氫糠酯、氟(甲基)丙烯酸酯等含有雜環或鹵素原子之丙烯酸酯系單體等。 Further, examples of the copolymerizable monomer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy ethylene glycol (meth) acrylate, and methoxy polypropylene glycol. A diol-based acrylate monomer such as (meth) acrylate; and an acrylate-based monomer containing a heterocyclic ring or a halogen atom, such as tetrahydrofurfuryl (meth) acrylate or fluorine (meth) acrylate.

進而，作為共聚性單體，可使用多官能性單體。作為多官能性單體，可列舉具有2個以上之(甲基)丙烯醯基、乙烯基等不飽和雙鍵之化合物等。例如可列舉：乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯等(單或聚)乙二醇二(甲基)丙烯酸酯，丙二醇二(甲基)丙烯酸酯等(單或聚)丙二醇二(甲基)丙烯酸酯等(單或聚)伸烷基二醇二(甲基)丙烯酸酯；此外可列舉：新戊二醇二 (甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇之酯化物；二乙烯基苯等多官能乙烯基化合物；(甲基)丙烯酸烯丙酯、(甲基)丙烯酸乙烯酯等具有反應性不飽和雙鍵之化合物等。又，作為多官能性單體，亦可使用於聚酯、環氧化合物、胺基甲酸酯等骨架上加成2個以上之作為與單體成分相同之官能基之(甲基)丙烯醯基、乙烯基等不飽和雙鍵而成之聚酯(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯等。 Further, as the copolymerizable monomer, a polyfunctional monomer can be used. The polyfunctional monomer may, for example, be a compound having two or more unsaturated double bonds such as a (meth)acryl fluorenyl group or a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth)acrylic acid Ester, tetraethylene glycol di(meth)acrylate, etc. (mono or poly)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, etc. (mono or poly)propylene glycol di(methyl) Acrylate or the like (mono or poly) alkyl diol di(meth) acrylate; furthermore: neopentyl glycol (Meth) acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(methyl) An ester of (meth)acrylic acid and a polyhydric alcohol such as acrylate, dipentaerythritol hexa(meth)acrylate, or a polyfunctional vinyl compound such as divinylbenzene; allyl (meth)acrylate and (meth)acrylic acid A compound having a reactive unsaturated double bond such as vinyl ester or the like. Further, as the polyfunctional monomer, two or more (meth)acryl oximes which are the same functional groups as the monomer components may be added to a skeleton such as a polyester, an epoxy compound or a urethane. Polyester (meth) acrylate, epoxy (meth) acrylate, (meth) acrylate urethane, etc., which are unsaturated double bonds such as a vinyl group or a vinyl group.

此種(甲基)丙烯酸系聚合物之製造可適當選擇溶液聚合、塊狀聚合、乳化聚合、各種自由基聚合等公知之製造方法，並無特別限定。又，所獲得之(甲基)丙烯酸系聚合物可為無規共聚物、嵌段共聚物、接枝共聚物等中之任一種。 A known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected from the production of such a (meth)acrylic polymer, and is not particularly limited. Further, the obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like.

於溶液聚合中，例如使用乙酸乙酯、甲苯等作為聚合溶劑。作為具體之溶液聚合例，反應係於氮氣等惰性氣體氣流下添加聚合起始劑且通常於50~70℃左右、5~30小時左右之反應條件下進行。 In the solution polymerization, for example, ethyl acetate, toluene or the like is used as a polymerization solvent. As a specific example of solution polymerization, the reaction is carried out by adding a polymerization initiator under an inert gas flow such as nitrogen gas, and is usually carried out under the reaction conditions of about 50 to 70 ° C for about 5 to 30 hours.

自由基聚合中所使用之聚合起始劑、鏈轉移劑、乳化劑等並無特別限定，可適當選擇使用。再者，(甲基)丙烯酸系聚合物之重量平均分子量可根據聚合起始劑、鏈轉移劑之使用量、反應條件而加以控制，根據該等之種類而調整其適當之使用量。 The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. Further, the weight average molecular weight of the (meth)acrylic polymer can be controlled according to the amount of the polymerization initiator, the chain transfer agent used, and the reaction conditions, and the appropriate amount can be adjusted according to the types thereof.

於本發明中使用之丙烯酸系黏著劑組合物中，可為了提昇高溫多濕條件下之密接性而添加各種矽烷偶合劑。作為矽烷偶合劑，可使用具有任意適當之官能基者。作為官能基，例如可列舉：乙烯基、環氧基、胺基、巰基、(甲基)丙烯醯氧基、乙醯乙醯基、異氰酸酯基、苯乙烯基、多硫基等。具體而言，例如可列舉：乙烯基三乙氧基矽烷、乙烯基三丙氧基矽烷、乙烯基三異丙氧基矽烷、乙烯基三丁氧基 矽烷等含乙烯基之矽烷偶合劑；γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三乙氧基矽烷、3-縮水甘油氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷等含環氧基之矽烷偶合劑；γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)3-胺基丙基甲基二甲氧基矽烷、γ-三乙氧基矽烷基-N-(1,3-二甲基亞丁基)丙胺、N-苯基-γ-胺基丙基三甲氧基矽烷等含胺基之矽烷偶合劑；γ-巰基丙基甲基二甲氧基矽烷等含巰基之矽烷偶合劑；對苯乙烯基三甲氧基矽烷等含苯乙烯基之矽烷偶合劑；γ-丙烯醯氧基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三乙氧基矽烷等含(甲基)丙烯醯基之矽烷偶合劑；3-異氰酸酯基丙基三乙氧基矽烷等含異氰酸酯基之矽烷偶合劑；雙(三乙氧基矽烷基丙基)四硫化物等含多硫基之矽烷偶合劑等。 In the acrylic pressure-sensitive adhesive composition used in the present invention, various decane coupling agents can be added in order to improve the adhesion under high temperature and high humidity conditions. As the decane coupling agent, those having any appropriate functional group can be used. Examples of the functional group include a vinyl group, an epoxy group, an amine group, a mercapto group, a (meth)acryloxy group, an ethyl oxime group, an isocyanate group, a styryl group, and a polysulfide group. Specific examples include: vinyltriethoxysilane Silane, Silane vinyl tripropoxysilane, vinyl triisopropoxysilane Silane, vinyltriisopropoxysilane Silane coupling agent Silane-containing vinyl group; gamma] - glycidoxypropyltrimethoxydecane, gamma -glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-ring An epoxy group-containing decane coupling agent such as oxycyclohexyl)ethyltrimethoxydecane; γ -aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-aminopropylmethyl Dimethoxydecane, N-(2-aminoethyl) 3-aminopropylmethyldimethoxydecane, γ -triethoxydecyl-N-(1,3-dimethylarylene) An amine group-containing decane coupling agent such as propylamine or N-phenyl-γ-aminopropyltrimethoxydecane; a decyl group-containing decane coupling agent such as γ -mercaptopropylmethyldimethoxydecane; a styrene-based decane coupling agent such as vinyltrimethoxydecane; γ -acryloxypropyltrimethoxydecane, γ -methylpropenyloxypropyltriethoxydecane, etc. (methyl) Propylene decyl decane Mixture; 3-isocyanate propyl triethoxy silane-containing coupling agents, etc. Silane isocyanate group of; bis (triethoxysilylpropyl silicon alkyl) tetrasulfide polysulfide group-containing silane-coupling agent of.

進而，藉由在本發明中使用之丙烯酸系黏著劑組合物中添加交聯劑，能夠賦予與黏著劑之耐久性相關之凝聚力，故而較佳。 Further, by adding a crosslinking agent to the acrylic pressure-sensitive adhesive composition used in the present invention, it is possible to impart a cohesive force with respect to the durability of the pressure-sensitive adhesive, which is preferable.

作為交聯劑，可使用多官能性之化合物，可列舉有機系交聯劑或多官能性金屬螯合物。作為有機系交聯劑，可列舉：環氧系交聯劑、異氰酸酯系交聯劑、碳二醯亞胺系交聯劑、亞胺系交聯劑、唑啉系交聯劑、氮丙啶系交聯劑、過氧化物系交聯劑等。多官能性金屬螯合物為多價金屬原子與有機化合物共價鍵結或配位鍵結而成者。作為多價金屬原子，可列舉：Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。作為共價鍵結或配位鍵結之有機化合物中之原子，可列舉氧原子等，作為有機化合物，可列舉烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。該等交聯劑可單獨使用1種，或組合2種以上使用。該等之中，較佳為過氧化物系交聯劑、異氰酸酯系交聯劑，更佳為組合該等使用。 As the crosslinking agent, a polyfunctional compound can be used, and examples thereof include an organic crosslinking agent or a polyfunctional metal chelate compound. Examples of the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, and an imide crosslinking agent. An oxazoline crosslinking agent, an aziridine crosslinking agent, a peroxide crosslinking agent, and the like. The polyfunctional metal chelate is a combination of a polyvalent metal atom and an organic compound covalently bonded or coordinately bonded. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Wait. Examples of the atom in the organic compound which is a covalent bond or a coordinate bond include an oxygen atom and the like. Examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents may be used alone or in combination of two or more. Among these, a peroxide-based crosslinking agent and an isocyanate-based crosslinking agent are preferable, and it is more preferable to use them in combination.

異氰酸酯系交聯劑係指於1分子中具有2個以上異氰酸酯基(包括藉由封端劑或多聚物化等而暫時保護異氰酸酯基之異氰酸酯再生型官能基)之化合物。 The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups (including an isocyanate-regenerating functional group that temporarily protects an isocyanate group by a blocking agent or a polymerization agent) in one molecule.

作為異氰酸酯系交聯劑，可列舉：甲苯二異氰酸酯、二甲苯二異氰酸酯等芳香族異氰酸酯、異佛爾酮二異氰酸酯等脂環族異氰酸酯、六亞甲基二異氰酸酯等脂肪族異氰酸酯等。 Examples of the isocyanate crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.

作為過氧化物系交聯劑，使用各種過氧化物。作為過氧化物，可列舉：過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二第二丁酯、過氧化新癸酸第三丁酯、過氧化特戊酸第三己酯、過氧化特戊酸第三丁酯、過氧化二月桂醯、過氧化二正辛醯、過氧化異丁酸1,1,3,3-四甲基丁酯、過氧化2-乙基己酸1,1,3,3-四甲基丁酯、過氧化二(4-甲基苯甲醯)、過氧化二苯甲醯、過氧化異丁酸第三丁酯等。該等之中，可較佳地使用特別是交聯反應效率優異之過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二月桂醯、過氧化二苯甲醯。 As the peroxide-based crosslinking agent, various peroxides are used. Examples of the peroxide include di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxydicarbonate, and dibutyl butyl peroxydicarbonate. Oxidized neodecanoic acid tert-butyl ester, peroxidic pivalic acid trihexyl ester, peroxidic pivalic acid tert-butyl ester, dilaurin peroxide, di-n-octyl peroxide, isobutyric acid peroxide 1,1 ,3,3-tetramethylbutyl ester, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, bis(4-methylbenzhydryl) peroxide, diphenyl peroxide Formamidine, third butyl peroxybutyrate, and the like. Among these, bis(4-t-butylcyclohexyl)peroxydicarbonate diperoxide, dilaurinium peroxide, and dibenzoyl guanidinium peroxide which are excellent in cross-linking reaction efficiency can be preferably used.

又，藉由在本發明中使用之丙烯酸系黏著劑組合物中添加離子性化合物，就不僅賦予抗靜電功能、而且抑制透明導電層之表面電阻上升之觀點而言較佳。 Further, by adding an ionic compound to the acrylic pressure-sensitive adhesive composition used in the present invention, it is preferable to impart not only an antistatic function but also an increase in the surface resistance of the transparent conductive layer.

作為離子性化合物，可較佳地使用鹼金屬鹽及/或有機陽離子-陰離子鹽。鹼金屬鹽可使用鹼金屬之有機鹽、及無機鹽。再者，所謂本發明中所述之「有機陽離子-陰離子鹽」，係指為有機鹽且其陽離子部由有機物所構成之化合物，陰離子部可為有機物，亦可為無機物。「有機陽離子-陰離子鹽」亦稱為離子性液體、離子性固體。 As the ionic compound, an alkali metal salt and/or an organic cation-anion salt can be preferably used. As the alkali metal salt, an organic salt of an alkali metal and an inorganic salt can be used. In addition, the "organic cation-anion salt" as used in the present invention means a compound which is an organic salt and whose cation part is composed of an organic substance, and the anion portion may be an organic substance or an inorganic substance. "Organic cation-anion salts" are also known as ionic liquids and ionic solids.

又，作為離子性化合物，除上述鹼金屬鹽、有機陽離子-陰離子鹽以外，亦可列舉：氯化銨、氯化鋁、氯化銅、氯化亞鐵、氯化鐵、硫酸銨等無機鹽。該等離子性化合物可單獨使用或併用複數種。 Further, examples of the ionic compound include inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, iron chloride, and ammonium sulfate, in addition to the above-mentioned alkali metal salt and organic cation-anion salt. . The plasma compound may be used singly or in combination of plural kinds.

進而，於本發明中使用之丙烯酸系黏著劑組合物中，根據需要亦可於不脫離本發明目的之範圍內適當使用黏度調整劑、剝離調整劑、黏度賦予劑、塑化劑、軟化劑、包含玻璃纖維、玻璃珠、金屬粉、其他無機粉末等之填充劑、顏料、著色劑(顏料、染料等)、pH值調整劑(酸或鹼)、抗氧化劑、紫外線吸收劑等各種添加劑。該等添加劑亦可以乳液之形式調配。 Further, in the acrylic pressure-sensitive adhesive composition used in the present invention, a viscosity adjuster, a peeling adjuster, a viscosity imparting agent, a plasticizer, a softener, or the like may be appropriately used as long as it does not deviate from the object of the present invention. Various additives such as fillers such as glass fibers, glass beads, metal powders, and other inorganic powders, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, and ultraviolet absorbers are included. These additives can also be formulated in the form of an emulsion.

又，本發明中使用之丙烯酸系黏著劑組合物中亦可含有本說明書中記載之磷系化合物，但就與偏光膜或塗敷層之密接性之觀點而言，較佳為不含有。 Moreover, the phosphorus-based compound described in the present specification may be contained in the acrylic pressure-sensitive adhesive composition used in the present invention, but it is preferably not contained in view of the adhesion to the polarizing film or the coating layer.

上述黏著劑層5之形成方法並無特別限定，可為於各種基材上塗佈上述丙烯酸系黏著劑組合物，利用熱烘箱等乾燥器進行乾燥，使溶劑等揮散而形成黏著劑層，將該黏著劑層轉印於上述附有塗敷層之偏光膜1之塗敷層側之方法，亦可於上述附有塗敷層之偏光膜1之塗敷層上直接塗佈上述丙烯酸系黏著劑組合物而形成黏著劑層5。 The method for forming the pressure-sensitive adhesive layer 5 is not particularly limited, and the acrylic pressure-sensitive adhesive composition may be applied to various base materials, dried by a dryer such as a hot oven, and a solvent or the like may be volatilized to form an adhesive layer. The adhesive layer is transferred onto the coating layer side of the polarizing film 1 with the coating layer, and the acrylic adhesive layer may be directly coated on the coating layer of the polarizing film 1 with the coating layer. The adhesive composition 5 forms the adhesive layer 5.

作為上述基材，並無特別限定，例如可列舉脫模膜、透明樹脂膜基材等各種基材。 The substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate.

作為對上述基材或偏光膜之塗佈方法，可使用各種方法。具體而言，例如可列舉：噴注式塗佈機、輥式塗佈、接觸輥式塗佈、凹版塗佈、反向塗佈、輥式刷塗、噴塗、浸輥式塗佈、棒式塗佈、刮刀塗佈、氣刀塗佈、淋幕式塗佈、模唇塗佈、利用模嘴塗佈機等之擠出塗佈法等方法。 As a method of applying the above substrate or a polarizing film, various methods can be used. Specific examples thereof include a spray coater, roll coating, contact roll coating, gravure coating, reverse coating, roll coating, spray coating, dip coating, and rod type. Coating, knife coating, air knife coating, curtain coating, lip coating, extrusion coating method using a die coater or the like.

乾燥條件(溫度、時間)並無特別限定，可根據丙烯酸系黏著劑組合物之組成、濃度等而適當設定，例如溫度為80~170℃左右，較佳為90~200℃，時間為1~60分鐘，較佳為2~30分鐘。 The drying conditions (temperature, time) are not particularly limited, and may be appropriately set depending on the composition, concentration, and the like of the acrylic pressure-sensitive adhesive composition. For example, the temperature is about 80 to 170 ° C, preferably 90 to 200 ° C, and the time is 1 to 60 minutes, preferably 2 to 30 minutes.

黏著劑層5之厚度(乾燥後)例如較佳為5~100μm，更佳為10~60μm，進而更佳為12~40μm。若黏著劑層5之厚度未達10μm，則有對 被黏著體之密接性欠缺，高溫、高溫多濕下之耐久性不充分之傾向。另一方面，於黏著劑層5之厚度超過100μm之情形時，存在形成黏著劑層5時之丙烯酸系黏著劑組合物之塗佈、乾燥時未充分地乾燥而殘留氣泡，或者於黏著劑層之面產生厚度不均，或者外觀上之問題易變得明顯之傾向。 The thickness (after drying) of the adhesive layer 5 is, for example, preferably 5 to 100 μm, more preferably 10 to 60 μm, still more preferably 12 to 40 μm. If the thickness of the adhesive layer 5 is less than 10 μm, there is a pair The adhesiveness of the adherend is insufficient, and the durability at high temperature, high temperature and high humidity is insufficient. On the other hand, when the thickness of the adhesive layer 5 exceeds 100 μm, there is a case where the acrylic adhesive composition is formed when the adhesive layer 5 is formed, and when it is dried, it is not sufficiently dried to leave bubbles, or in the adhesive layer. The surface is uneven in thickness, or the appearance problem tends to become obvious.

作為上述脫模膜之構成材料，例如可列舉聚乙烯、聚丙烯、聚對苯二甲酸乙二酯、聚酯膜等樹脂膜、紙、布、不織布等多孔質材料、網狀物、發泡片、金屬箔、及該等之層壓體等適當之薄片體等，就表面平滑性優異之方面而言，可較佳地使用樹脂膜。 Examples of the constituent material of the release film include a resin film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film, a porous material such as paper, cloth or nonwoven fabric, a mesh, and foaming. A resin film can be preferably used in terms of excellent surface smoothness, such as a sheet, a metal foil, and a suitable sheet such as the laminate.

作為該樹脂膜，例如可列舉：聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚對苯二甲酸乙二酯膜、聚對苯二甲酸丁二酯膜、聚胺基甲酸酯膜、乙烯-乙酸乙烯酯共聚物膜等。 Examples of the resin film include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, and a polyparaphenylene. A formic acid ethylene glycol film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like.

上述脫模膜之厚度通常為5~200μm，較佳為5~100μm左右。對於上述脫模膜，根據需要亦可進行利用矽酮系、氟系、長鏈烷基系或脂肪醯胺系之脫模劑、二氧化矽粉末等之脫模及防污處理、或塗佈型、混練型、蒸鍍型等之抗靜電處理。特別是藉由對上述脫模膜之表面適當進行矽酮處理、長鏈烷基處理、氟處理等剝離處理，能夠進一步提高自上述黏著劑層之剝離性。 The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. The release film may be subjected to mold release, antifouling treatment, or coating using an anthrone, a fluorine-based, a long-chain alkyl or a fatty amide-based release agent, a cerium oxide powder, or the like, as needed. Antistatic treatment of type, kneading type, vapor deposition type, etc. In particular, by appropriately performing a release treatment such as an anthrone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the release film, the peeling property from the pressure-sensitive adhesive layer can be further improved.

作為上述透明樹脂膜基材，並無特別限定，可使用具有透明性之各種樹脂膜。該樹脂膜可藉由1層膜而形成。例如作為其材料，可列舉：聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂、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、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚苯硫醚系樹脂等。該等之中，特佳為聚酯系樹脂、聚醯亞胺 系樹脂及聚醚碸系樹脂。 The transparent resin film substrate is not particularly limited, and various resin films having transparency can be used. The resin film can be formed by a single film. For example, examples thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether oxime resins, polycarbonate resins, and polyfluorenes. An amine resin, a polyimide resin, a polyolefin resin, a (meth)acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl alcohol resin, A polyarylate resin, a polyphenylene sulfide resin, or the like. Among these, polyester resin and polyimine are particularly preferred. Resin and polyether oxime resin.

上述膜基材之厚度較佳為15~200μm。 The thickness of the film substrate is preferably 15 to 200 μm.

上述附有塗敷層之偏光膜1之塗敷層上之黏著劑層之形成方法如上所述。 The method of forming the adhesive layer on the coating layer of the polarizing film 1 with the coating layer described above is as described above.

又，於本發明之附有黏著劑層之偏光膜之黏著劑層露出之情形時，亦可於供於實用之前利用脫模膜(隔離件)保護黏著劑層。作為脫模膜，可列舉如上所述者。於製作上述黏著劑層時使用脫模膜作為基材之情形時，將脫模膜上之黏著劑層與碘系偏光膜貼合，藉此該脫模膜可用作附有黏著劑層之偏光膜之黏著劑層之脫模膜，而能夠進行步驟上之簡化。 Further, in the case where the adhesive layer of the polarizing film with the adhesive layer of the present invention is exposed, the adhesive layer may be protected by a release film (separator) before being used for practical use. As a release film, the above is mentioned. When a release film is used as the substrate in the production of the above adhesive layer, the adhesive layer on the release film is bonded to the iodine-based polarizing film, whereby the release film can be used as an adhesive layer. The release film of the adhesive layer of the polarizing film can be simplified in steps.

本發明之上述附有黏著劑層之偏光膜可以使附有黏著劑層之偏光膜之黏著劑層與具有透明導電層之構件之透明導電層接觸之方式貼合而使用。 The above polarizing film with an adhesive layer of the present invention can be used by bonding an adhesive layer of a polarizing film with an adhesive layer in contact with a transparent conductive layer of a member having a transparent conductive layer.

作為具有透明導電層之構件，並無特別限定，可使用公知者，可列舉於透明膜等透明基材上具有透明導電層者、或具有透明導電層及液晶單元之構件。 The member having a transparent conductive layer is not particularly limited, and a known one may be used, and those having a transparent conductive layer on a transparent substrate such as a transparent film or a member having a transparent conductive layer and a liquid crystal cell may be used.

作為透明基材，只要為具有透明性者即可，例如可列舉樹脂膜或包含玻璃等之基材(例如片狀或膜狀、板狀之基材等)等，特佳為樹脂膜。透明基材之厚度並無特別限定，較佳為10~200μm左右，更佳為15~150μm左右。 The transparent substrate may be a resin film or a substrate including glass (for example, a sheet-like or film-like or plate-shaped substrate), and a resin film is particularly preferable. The thickness of the transparent substrate is not particularly limited, but is preferably about 10 to 200 μm, more preferably about 15 to 150 μm.

作為上述樹脂膜之材料，並無特別限定，可列舉具有透明性之各種塑膠材料。例如作為其材料，可列舉：聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯系樹脂、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、(甲基)丙烯酸系樹脂、聚氯乙烯系樹脂、聚偏二氯乙烯系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、聚芳酯系樹脂、聚苯硫醚系樹脂等。該 等之中，特佳為聚酯系樹脂、聚醯亞胺系樹脂及聚醚碸系樹脂。 The material of the resin film is not particularly limited, and various plastic materials having transparency can be cited. For example, examples thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyether oxime resins, polycarbonate resins, and polyfluorenes. An amine resin, a polyimide resin, a polyolefin resin, a (meth)acrylic resin, a polyvinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl alcohol resin, A polyarylate resin, a polyphenylene sulfide resin, or the like. The Among them, polyester resins, polyamidene resins, and polyether oxime resins are particularly preferred.

又，對於上述透明基材，亦可對表面預先實施濺鍍、電暈放電、火焰、紫外線照射、電子束照射、化學處理、氧化等蝕刻處理或底塗處理而提昇設置於其上之透明導電層對於上述透明基材之密接性。又，於設置透明導電層之前，根據需要亦可利用溶劑洗淨、超音波洗淨等進行除塵、清潔化。 Further, in the transparent substrate, the surface may be subjected to an etching treatment or a primer treatment such as sputtering, corona discharge, flame, ultraviolet ray irradiation, electron beam irradiation, chemical treatment, oxidation, etc., to enhance the transparent conductive layer provided thereon. The adhesion of the layer to the above transparent substrate. Further, before the transparent conductive layer is provided, it is also possible to perform dust removal and cleaning by solvent washing, ultrasonic cleaning, or the like as needed.

作為上述透明導電層之構成材料，並無特別限定，使用選自由銦、錫、鋅、鎵、銻、鈦、矽、鋯、鎂、鋁、金、銀、銅、鈀、鎢所組成之群中之至少1種金屬之金屬氧化物。於該金屬氧化物中，根據需要亦可進而含有上述群中所示之金屬原子。例如可較佳地使用含有氧化錫之氧化銦(ITO)、含有銻之氧化錫等，可特佳地使用ITO。作為ITO，較佳為含有氧化銦80~99重量%及氧化錫1~20重量%。 The constituent material of the transparent conductive layer is not particularly limited, and a group selected from the group consisting of indium, tin, zinc, gallium, germanium, titanium, lanthanum, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten is used. a metal oxide of at least one metal. The metal oxide may further contain a metal atom as shown in the above group as needed. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, or the like can be preferably used, and ITO can be particularly preferably used. The ITO preferably contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

又，作為上述ITO，可列舉晶質ITO、非晶質(amorphous)ITO。晶質ITO可藉由在濺鍍時施加高溫、或進而加熱非晶質ITO而獲得。上述由碘所引起之劣化會於非晶質ITO上明顯地產生，故而本發明之附有黏著劑層之偏光膜對於非晶質ITO特別有效。 Further, examples of the ITO include crystalline ITO and amorphous ITO. Crystalline ITO can be obtained by applying a high temperature during sputtering or heating amorphous ITO. The above-mentioned deterioration caused by iodine is remarkably generated on the amorphous ITO, and therefore, the polarizing film with the adhesive layer of the present invention is particularly effective for amorphous ITO.

上述透明導電層之厚度並無特別限定，較佳為設為7nm以上，更佳為設為10nm以上，進而更佳為設為12~60nm，進而更佳為設為15~45nm，進而更佳為設為18~45nm，特佳為設為20~30nm。若透明導電層之厚度未達7nm，則有容易產生由碘所引起之透明導電層之劣化，透明導電層之電阻值之變化增大之傾向。另一方面，於超過60nm之情形時，有透明導電層之生產性降低，成本亦上升，進而光學特性亦降低之傾向。 The thickness of the transparent conductive layer is not particularly limited, but is preferably 7 nm or more, more preferably 10 nm or more, still more preferably 12 to 60 nm, still more preferably 15 to 45 nm, and still more preferably It is set to 18 to 45 nm, and particularly preferably set to 20 to 30 nm. When the thickness of the transparent conductive layer is less than 7 nm, deterioration of the transparent conductive layer caused by iodine is likely to occur, and the change in the resistance value of the transparent conductive layer tends to increase. On the other hand, in the case of more than 60 nm, the productivity of the transparent conductive layer is lowered, the cost is also increased, and the optical characteristics are also lowered.

作為上述透明導電層之形成方法，並無特別限定，可採用先前公知之方法。具體而言，例如可例示真空蒸鍍法、濺鍍法、離子鍍覆法。又，亦可根據所需之膜厚而採用適當之方法。 The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, or an ion plating method can be exemplified. Further, an appropriate method may be employed depending on the desired film thickness.

作為具有上述透明導電層之基材之厚度，可列舉15~200μm。進而，就薄膜化之觀點而言，較佳為15~150μm，更佳為15~50μm。於以電阻膜方式使用具有上述透明導電層之基材之情形時，例如可列舉100~200μm之厚度。又，於以靜電電容方式使用之情形時，例如較佳為15~100μm之厚度，特別是伴隨於近年來之進一步之薄膜化要求，更佳為15~50μm之厚度，進而更佳為20~50μm之厚度。 The thickness of the substrate having the above transparent conductive layer is, for example, 15 to 200 μm. Further, from the viewpoint of film formation, it is preferably 15 to 150 μm, more preferably 15 to 50 μm. When the substrate having the above transparent conductive layer is used as a resistive film, for example, a thickness of 100 to 200 μm can be mentioned. Further, when it is used in the form of a capacitance, for example, it is preferably a thickness of 15 to 100 μm, particularly in the case of further thin film formation in recent years, more preferably 15 to 50 μm, and still more preferably 20 to 20 50 μm thickness.

又，於透明導電層與透明基材之間，根據需要可設置底塗層、低聚物防止層等。 Further, an undercoat layer, an oligomer blocking layer, or the like may be provided between the transparent conductive layer and the transparent substrate as needed.

又，作為具有透明導電層及液晶單元之構件，可列舉各種液晶顯示裝置等圖像顯示裝置中所使用之於包含基板(例如玻璃基板等)/液晶層/基板之構成之液晶單元之該基板之不與液晶層接觸之側具有透明導電層者。又，於液晶單元上設置彩色濾光片基板之情形時，亦可於該彩色濾光片上具有透明導電層。於液晶單元之基板上形成透明導電層之方法與上述相同。 In addition, as a member having a transparent conductive layer and a liquid crystal cell, the substrate used in an image display device such as a liquid crystal display device, which is a liquid crystal cell including a substrate (for example, a glass substrate) or a liquid crystal layer/substrate, can be used. Those having no transparent conductive layer on the side not in contact with the liquid crystal layer. Further, when a color filter substrate is provided on the liquid crystal cell, a transparent conductive layer may be provided on the color filter. The method of forming a transparent conductive layer on the substrate of the liquid crystal cell is the same as described above.

3.圖像顯示裝置 3. Image display device

本發明之附有黏著劑層之偏光膜如上所述，即使於該附有黏著劑層之偏光膜之黏著劑層上積層透明導電層之情形時，亦能夠抑制透明導電層之腐蝕，而能夠抑制透明導電層之表面電阻上升。因此，只要為具有附有黏著劑層之偏光膜之黏著劑層與透明導電層接觸之構成之圖像顯示裝置，則可較佳地使用本發明之附有黏著劑層之偏光膜。例如可將本發明之附有黏著劑層之偏光膜與具有透明導電層之液晶面板以上述附有黏著劑層之偏光膜之黏著劑層與上述液晶面板之透明導電層接觸之方式貼合而製作圖像顯示裝置。 As described above, the polarizing film with the adhesive layer of the present invention can suppress the corrosion of the transparent conductive layer even when a transparent conductive layer is laminated on the adhesive layer of the polarizing film with the adhesive layer. The surface resistance of the transparent conductive layer is suppressed from rising. Therefore, as long as the image display device having the adhesive layer having the polarizing film with the adhesive layer in contact with the transparent conductive layer is used, the polarizing film with the adhesive layer of the present invention can be preferably used. For example, the polarizing film with the adhesive layer of the present invention and the liquid crystal panel having the transparent conductive layer are bonded to each other by the adhesive layer of the polarizing film with the adhesive layer and the transparent conductive layer of the liquid crystal panel. Create an image display device.

進而具體而言，可列舉使用透明導電層作為抗靜電層用途之圖像顯示裝置、或使用透明導電層作為觸控面板之電極用途之圖像顯示 裝置。作為使用透明導電層作為抗靜電層用途之圖像顯示裝置，具體而言，例如可列舉：為包含偏光膜/黏著劑層/抗靜電層/玻璃基板/液晶層/驅動電極/玻璃基板/黏著劑層/偏光膜之構成且上述抗靜電層、驅動電極由透明導電層形成之圖像顯示裝置。可使用本發明之附有黏著劑層之偏光膜作為該圖像顯示裝置之上側(視認側)之附有黏著劑層之偏光膜。又，作為使用透明導電層作為觸控面板之電極用途之圖像顯示裝置，例如可列舉：為偏光膜/黏著劑層/兼作抗靜電層之感測器層/玻璃基板/液晶層/兼作驅動電極之感測器層/玻璃基板/黏著劑層/偏光膜之構成(In-Cell型觸控面板)、或偏光膜/黏著劑層/兼作抗靜電層之感測器層/感測器層/玻璃基板/液晶層/驅動電極/玻璃基板/黏著劑層/偏光膜之構成(On-Cell型觸控面板)且兼作抗靜電層之感測器層、感測器層、驅動電極由透明導電層形成之圖像顯示裝置。可使用本發明之附有黏著劑層之偏光膜作為該圖像顯示裝置之上側(視認側)之附有黏著劑層之偏光膜。 More specifically, an image display device using a transparent conductive layer as an antistatic layer or an image display using a transparent conductive layer as an electrode for a touch panel can be used. Device. As an image display device using a transparent conductive layer as an antistatic layer, specifically, for example, a polarizing film/adhesive layer/antistatic layer/glass substrate/liquid crystal layer/drive electrode/glass substrate/adhesion is included. An image display device in which the agent layer/polarizing film is configured and the antistatic layer and the driving electrode are formed of a transparent conductive layer. The polarizing film with an adhesive layer of the present invention can be used as a polarizing film with an adhesive layer attached to the upper side (viewing side) of the image display device. Further, as an image display device using a transparent conductive layer as an electrode for a touch panel, for example, a polarizing film/adhesive layer/a sensor layer/a glass substrate/liquid crystal layer/both as an antistatic layer can be cited. Sensor layer/glass substrate/adhesive layer/polarizing film composition (In-Cell type touch panel), or polarizing film/adhesive layer/sensor layer/sensor layer serving as antistatic layer /glass substrate/liquid crystal layer/drive electrode/glass substrate/adhesive layer/polarizing film (On-Cell type touch panel) and the sensor layer, sensor layer, and driving electrode that double as the antistatic layer are transparent An image display device formed by a conductive layer. The polarizing film with an adhesive layer of the present invention can be used as a polarizing film with an adhesive layer attached to the upper side (viewing side) of the image display device.

[實施例] [Examples]

以下，使用實施例對本發明進行詳細說明，但只要不超出其主旨，則本發明並不限定於以下之實施例。 Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples below.

<偏光子中之碘含量> <Iodine content in polarized photons>

偏光子中之碘含量(碘及/或碘離子之含量)係按照以下之順序進行測定。 The iodine content (the content of iodine and/or iodide ions) in the polarizer was measured in the following order.

1)對複數個包含特定量碘化鉀之偏光子測定螢光X射線強度，導出碘含量與螢光X射線強度之關係式。2)測定碘含量未知之碘系偏光子之螢光X射線，由該數值並使用上述關係式計算碘量。 1) The fluorescence X-ray intensity is measured for a plurality of polarizers containing a specific amount of potassium iodide, and the relationship between the iodine content and the intensity of the fluorescent X-rays is derived. 2) The fluorescent X-ray of the iodine-based polarizer having an unknown iodine content is measured, and the amount of iodine is calculated from the value and using the above relational expression.

<丙烯酸系聚合物之重量平均分子量(Mw)之測定> <Measurement of Weight Average Molecular Weight (Mw) of Acrylic Polymer>

所製作之丙烯酸系聚合物之重量平均分子量係藉由GPC(凝膠滲透層析法)進行測定。 The weight average molecular weight of the produced acrylic polymer was measured by GPC (gel permeation chromatography).

裝置：東曹公司製，HLC-8220GPC Device: manufactured by Tosoh Corporation, HLC-8220GPC

管柱： Column:

樣品管柱：東曹公司製，TSKguardcolumn Super HZ-H(1根)+TSKgel Super HZM-H(2根) Sample column: made by Tosoh Corporation, TSKguardcolumn Super HZ-H (1) + TSKgel Super HZM-H (2)

參考管柱：東曹公司製，TSKgel Super H-RC(1根) Reference column: made by Tosoh Corporation, TSKgel Super H-RC (1 root)

流量：0.6mL/min Flow rate: 0.6mL/min

注入量：10μL Injection volume: 10 μ L

管柱溫度：40℃ Column temperature: 40 ° C

溶離液：THF Dissolution: THF

注入試樣濃度：0.2重量% Injection sample concentration: 0.2% by weight

檢測器：示差折射計 Detector: differential refractometer

再者，重量平均分子量係藉由聚苯乙烯換算而算出。 Further, the weight average molecular weight was calculated by conversion in terms of polystyrene.

製造例1(單面保護偏光膜之製作) Production Example 1 (Production of single-sided protective polarizing film)

使於非晶質PET基材上製膜9μm厚之PVA層而成之積層體藉由延伸溫度130℃之空中輔助延伸而生成延伸積層體。繼而，將延伸積層體於相對於水100重量份而含有碘0.1重量份、碘化鉀0.7重量份之染色液中浸漬60秒鐘而生成著色積層體。進而，藉由延伸溫度65℃之硼酸水中延伸以總延伸倍率成為5.94倍之方式使著色積層體與非晶質PET基材一體延伸而生成包含4μm厚之PVA層之光學膜積層體。藉由上述2段延伸，能夠生成構成高功能偏光層之包含厚度4μm之PVA層之光學膜積層體，上述高功能偏光層使於非晶質PET基材上所製膜之PVA層之PVA分子高度地配向，使藉由染色而吸附之碘以聚碘離子錯合物之形式高度地配向於一個方向。進而，於該光學膜積層體之偏光層之表面塗佈PVA系接著劑，並且貼合經皂化處理之40μm厚之丙烯酸系樹脂膜(透明保護膜)後，將非晶質PET基材剝離而製作僅於使用了薄型碘系偏光子之單側具有透明保護膜之單面保護偏光膜。以下，將其 稱為單面保護偏光膜(1)。單面保護偏光膜(1)之碘含量為5.1重量%。 A laminate in which a PVA layer having a thickness of 9 μm was formed on an amorphous PET substrate was stretched by an extension temperature of 130 ° C to form an extended laminate. Then, the extended laminate was immersed in a dyeing liquid containing 0.1 part by weight of iodine and 0.7 part by weight of potassium iodide in 100 parts by weight of water to form a colored layered body. Further, the colored laminate was integrally extended with the amorphous PET substrate so that the total stretch ratio was 5.94 times extended by boiling water at an elongation temperature of 65 ° C to form an optical film laminate including a PVA layer having a thickness of 4 μm. By the above-described two-stage extension, it is possible to form an optical film laminate including a PVA layer having a thickness of 4 μm constituting the high-functional polarizing layer, and the high-functional polarizing layer is a PVA molecule of a PVA layer formed on the amorphous PET substrate. Highly aligned, the iodine adsorbed by dyeing is highly aligned in one direction in the form of a polyiodide complex. Furthermore, a PVA-based adhesive is applied to the surface of the polarizing layer of the optical film laminate, and a 40 μm thick acrylic resin film (transparent protective film) is bonded to the saponified film, and then the amorphous PET substrate is peeled off. A one-side protective polarizing film having a transparent protective film on one side of a thin iodine-based polarizer was used. Following, put it It is called single-sided protective polarizing film (1). The iodine content of the one-sided protective polarizing film (1) was 5.1% by weight.

製造例2(塗敷層形成用樹脂組合物(A1)之製備) Production Example 2 (Preparation of Coating Composition (A1) for Coating Layer Formation)

將聚合度2500、皂化度99.0莫耳%之PVA樹脂溶解於純水中，製備固形物成分濃度4重量%之水溶液，進而相對於該水溶液中之上述聚乙烯醇樹脂之固形物成分100重量份，添加作為磷系化合物之2重量份之磷酸單丁酯(商品名：MP-4，大八化學工業股份有限公司製)，獲得塗敷層形成用樹脂組合物(A1)。 A PVA resin having a polymerization degree 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 content concentration of 4% by weight, and further 100 parts by weight relative to the solid content of the polyvinyl alcohol resin in the aqueous solution. In addition, 2 parts by weight of a monobutyl phosphate (trade name: MP-4, manufactured by Daiha Chemical Industry Co., Ltd.) was added as a phosphorus-based compound to obtain a resin composition for forming a coating layer (A1).

製造例3(塗敷層形成用樹脂組合物(A2)之製備) Production Example 3 (Preparation of Coating Composition (A2) for Coating Layer Formation)

將聚合度2500、皂化度99.0莫耳%之PVA樹脂溶解於純水中，製備固形物成分濃度4重量%之水溶液，將其作為塗敷層形成用樹脂組合物(A2)。 A PVA resin having a polymerization degree of 2,500 and a saponification degree of 99.0 mol% was dissolved in pure water to prepare an aqueous solution having a solid content concentration of 4% by weight, and this was used as a coating layer-forming resin composition (A2).

製造例4(塗敷層形成用樹脂組合物(A3)之製備) Production Example 4 (Preparation of Resin Composition for Coating Layer Formation (A3))

將N-羥基乙基丙烯醯胺(商品名：HEAA，興人股份有限公司製)12.5份、丙烯醯基啉(商品名：ACMO(註冊商標)，興人股份有限公司製)25份、二羥甲基三環癸烷二丙烯酸酯(商品名：Light Acrylate DCP-A，共榮社化學股份有限公司製)62.5份、光自由基聚合起始劑(2-甲基-1-(4-甲硫基苯基)-2-啉基丙烷-1-酮，商品名：IRGACURE907，BASF公司製)2份、光增感劑(二乙基-9-氧硫，商品名：KAYACURE DETX-S，日本化藥股份有限公司製)2份加以混合，於50℃下攪拌1小時，獲得混合物。進而，相對於上述混合物之固形物成分100重量份，添加作為磷系化合物之2重量份之磷酸單丁酯(商品名：MP-4，大八化學工業股份有限公司製)，獲得塗敷層形成用樹脂組合物(A3)。 N-hydroxyethyl acrylamide (trade name: HEAA, manufactured by Xingren Co., Ltd.) 12.5 parts, acrylonitrile (2), dimethylol tricyclodecane diacrylate (trade name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) 62.5 parts, photoradical polymerization initiator (2-methyl-1-(4-methylthiophenyl)-2- Lolinylpropan-1-one, trade name: IRGACURE 907, manufactured by BASF) 2 parts, photosensitizer (diethyl-9-oxygen sulfide) The product name: KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.) was mixed and stirred at 50 ° C for 1 hour to obtain a mixture. Furthermore, 2 parts by weight of monobutyl phosphate (trade name: MP-4, manufactured by Daiha Kagaku Kogyo Co., Ltd.) as a phosphorus compound was added to 100 parts by weight of the solid content of the mixture to obtain a coating layer. The resin composition for formation (A3).

製造例5(塗敷層形成用樹脂組合物(A4)之製備) Production Example 5 (Preparation of Resin Composition for Coating Layer Formation (A4))

除不添加磷系化合物以外，以與製造例4同樣之方法獲得塗敷層形成用樹脂組合物(A4)。 A resin composition for forming a coating layer (A4) was obtained in the same manner as in Production Example 4 except that the phosphorus compound was not added.

製造例6(塗敷層形成用樹脂組合物(A5)之製備) Production Example 6 (Preparation of Coating Composition (A5) for Coating Layer Formation)

將聚合度2500、皂化度99.0莫耳%之PVA樹脂溶解於純水中，製備固形物成分濃度4重量%之水溶液，進而相對於該水溶液中之上述聚乙烯醇樹脂之固形物成分100重量份，添加作為磷系化合物之5重量份之苯基膦酸(和光純藥工業股份有限公司製之試劑)，獲得塗敷層形成用樹脂組合物(A5)。 A PVA resin having a polymerization degree 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 content concentration of 4% by weight, and further 100 parts by weight relative to the solid content of the polyvinyl alcohol resin in the aqueous solution. 5 parts by weight of phenylphosphonic acid (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added as a phosphorus-based compound to obtain a resin composition for forming a coating layer (A5).

製造例7(塗敷層形成用樹脂組合物(B1)之製備) Production Example 7 (Preparation of Coating Composition (B1) for Coating Layer Formation)

將以固形物成分計包含胺基甲酸酯系聚合物30~90重量%、及聚噻吩系聚合物(導電性材料)10~50重量%之溶液(商品名：Denatron P-580W，長瀨化成股份有限公司製)、及以固形物成分計包含含有唑啉基之丙烯酸系聚合物10~70重量%之溶液(商品名：Epocros WS-700，日本觸媒股份有限公司製)添加至水100重量%之(混合)溶液中，以固形物成分濃度(基礎(base)濃度)達到0.4重量%之方式進行製備，獲得塗敷層形成用樹脂組合物(B1)。 A solution containing 30 to 90% by weight of the urethane-based polymer and 10 to 50% by weight of the polythiophene-based polymer (conductive material) in terms of the solid content (trade name: Denatron P-580W, long 濑Chemical Co., Ltd.) and containing solid content 10 to 70% by weight of an oxazolyl-based acrylic polymer solution (trade name: Epocros WS-700, manufactured by Nippon Shokubai Co., Ltd.) is added to a (mixed) solution of 100% by weight of water to determine the concentration of solid components. (The base concentration) was prepared so as to be 0.4% by weight to obtain a resin composition for forming a coating layer (B1).

製造例8(塗敷層形成用樹脂組合物(B2)之製備) Production Example 8 (Preparation of resin composition for forming a coating layer (B2))

使用不包含聚噻吩系聚合物之胺基甲酸酯系聚合物溶液代替製造例7之Denatron P-580W(商品名：Denatron B-510C，長瀨化成股份有限公司製)，除此以外，以與製造例7同樣之方法獲得塗敷層形成用樹脂組合物(B2)。 A urethane-based polymer solution containing no polythiophene-based polymer was used instead of Denatron P-580W (trade name: Denatron B-510C, manufactured by Nagase Chemical Co., Ltd.) of Production Example 7, except A resin composition for forming a coating layer (B2) was obtained in the same manner as in Production Example 7.

製造例9(丙烯酸系黏著劑層(C1)之製作) Production Example 9 (Production of Acrylic Adhesive Layer (C1))

於具備冷凝管、氮氣導入管、溫度計及攪拌裝置之反應容器中，與乙酸乙酯一起添加丙烯酸丁酯99份、丙烯酸4-羥基丁酯1份、及相對於上述單體合計(固形物成分)100份為0.3份之2,2'-偶氮二異丁腈，於氮氣氣流下且於60℃下反應4小時後，於該反應液中添加乙酸乙酯而獲得含有重量平均分子量165萬之丙烯酸系聚合物(a1)之聚合物溶液(固形物成分濃度30重量%)。相對於上述丙烯酸系聚合物溶液 之固形物成分100份，調配作為交聯劑之0.3份之過氧化二苯甲醯(商品名：NYPER BMT，日本油脂股份有限公司製)、0.1份之三羥甲基丙烷苯二甲基二異氰酸酯(商品名：Takenate D110N，三井武田化學股份有限公司製)、0.2份之含有乙醯乙醯基之矽烷偶合劑(商品名：A-100，綜研化學股份有限公司製)、及作為磷系化合物之0.1份之磷酸單丁酯(商品名：MP-4，大八化學工業股份有限公司製)，獲得丙烯酸系黏著劑溶液。將上述丙烯酸系黏著劑溶液(C1)以乾燥後之厚度達到25μm之方式塗佈於經剝離處理之包含聚對苯二甲酸乙二酯膜(厚度：38μm)之脫模片(隔離件)之表面，進行乾燥形成黏著劑層(C1)。 In a reaction vessel equipped with a condenser, a nitrogen gas introduction tube, a thermometer, and a stirring device, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and a total of the above monomers (solid content) are added together with ethyl acetate. 100 parts of 0.3 parts of 2,2'-azobisisobutyronitrile, after reacting under nitrogen gas at 60 ° C for 4 hours, adding ethyl acetate to the reaction liquid to obtain a weight average molecular weight of 1.65 million A polymer solution of the acrylic polymer (a1) (solid content concentration: 30% by weight). Relative to the above acrylic polymer solution 100 parts of the solid content component, and 0.3 parts of dibenzoguanidine peroxide (trade name: NYPER BMT, manufactured by Nippon Oil & Fat Co., Ltd.) and 0.1 part of trimethylolpropane phthalate were added as a crosslinking agent. Isocyanate (trade name: Takenate D110N, manufactured by Mitsui Takeda Chemical Co., Ltd.), 0.2 parts of decane coupling agent containing ethyl acetonitrile (trade name: A-100, manufactured by Soken Chemical Co., Ltd.), and phosphorus system 0.1 part of monobutyl butyl phosphate (trade name: MP-4, manufactured by Daiba Chemical Industry Co., Ltd.) was used to obtain an acrylic adhesive solution. The acrylic adhesive solution (C1) was applied to a release-treated release sheet (separator) containing a polyethylene terephthalate film (thickness: 38 μm) so as to have a thickness of 25 μm after drying. The surface is dried to form an adhesive layer (C1).

製造例10(丙烯酸系黏著劑層(C2)之製作) Production Example 10 (Production of Acrylic Adhesive Layer (C2))

於黏著劑溶液之製備時不添加磷系化合物，除此以外，與製造例9同樣地形成丙烯酸系黏著劑層(C2)。 An acrylic pressure-sensitive adhesive layer (C2) was formed in the same manner as in Production Example 9 except that the phosphorus-based compound was not added to the preparation of the adhesive solution.

製造例11(丙烯酸系黏著劑層(C3)之製作) Production Example 11 (Production of Acrylic Adhesive Layer (C3))

於黏著劑溶液之製備時進而添加作為導電性材料之1-甲基-1-乙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺(岸田化學股份有限公司製)0.5份，除此以外，與製造例9同樣地形成丙烯酸系黏著劑層(C3)。 In the preparation of the adhesive solution, 0.5 parts of 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Kishida Chemical Co., Ltd.) as a conductive material was further added. Otherwise, an acrylic pressure-sensitive adhesive layer (C3) was formed in the same manner as in Production Example 9.

製造例12(丙烯酸系黏著劑層(C4)之製作) Production Example 12 (Production of Acrylic Adhesive Layer (C4))

於黏著劑溶液之製備時不添加磷系化合物，除此以外，與製造例11同樣地形成丙烯酸系黏著劑層(C4)。 An acrylic pressure-sensitive adhesive layer (C4) was formed in the same manner as in Production Example 11 except that the phosphorus-based compound was not added to the preparation of the pressure-sensitive adhesive solution.

製造例13(丙烯酸系黏著劑層(C5)之製作) Production Example 13 (Production of Acrylic Adhesive Layer (C5))

於具備冷凝管、氮氣導入管、溫度計及攪拌裝置之反應容器中，與乙酸乙酯一起添加丙烯酸丁酯95份、丙烯酸4-羥基丁酯1份、丙烯酸4份及相對於上述單體合計(固形物成分)100份為1份之作為起始劑之2,2'-偶氮二異丁腈，於氮氣氣流下且於60℃下反應7小時。其後，於該反應液中添加乙酸乙酯而獲得含有重量平均分子量155萬之丙烯酸系聚合物(a2)之溶液(固形物成分濃度30重量%)。 In a reaction vessel equipped with a condenser, a nitrogen gas introduction tube, a thermometer, and a stirring device, 95 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, 4 parts of acrylic acid, and a total of the above monomers were added together with ethyl acetate ( Solid content) 100 parts of 1 part of 2,2'-azobisisobutyronitrile as a starter was reacted under a nitrogen gas stream at 60 ° C for 7 hours. Then, ethyl acetate was added to the reaction liquid to obtain a solution (solid content concentration: 30% by weight) containing an acrylic polymer (a2) having a weight average molecular weight of 1.55 million.

於製造例9中使用上述含有丙烯酸系聚合物(a2)之溶液代替含有丙烯酸系聚合物(a1)之溶液，除此以外，與製造例9同樣地調配交聯劑、矽烷偶合劑、磷系化合物，獲得丙烯酸系黏著劑溶液。又，使用上述丙烯酸系黏著劑溶液與製造例9同樣地形成黏著劑層(C5)。 A crosslinking agent, a decane coupling agent, and a phosphorus system were prepared in the same manner as in Production Example 9 except that the solution containing the acrylic polymer (a2) was used in the production example 9 instead of the solution containing the acrylic polymer (a1). Compound, an acrylic adhesive solution was obtained. Further, an adhesive layer (C5) was formed in the same manner as in Production Example 9 using the above acrylic pressure-sensitive adhesive solution.

製造例14(丙烯酸系黏著劑層(C6)之製作) Production Example 14 (Production of Acrylic Adhesive Layer (C6))

於黏著劑溶液之製備時不添加磷系化合物，除此以外，與製造例13同樣地形成丙烯酸系黏著劑層(C6)。 An acrylic pressure-sensitive adhesive layer (C6) was formed in the same manner as in Production Example 13 except that the phosphorus-based compound was not added to the preparation of the adhesive solution.

製造例15(丙烯酸系黏著劑層(C7)之製作) Production Example 15 (Production of Acrylic Adhesive Layer (C7))

於黏著劑溶液之製備時進而添加作為導電性材料之1-甲基-1-乙基吡咯烷鎓雙(三氟甲磺醯基)醯亞胺(岸田化學股份有限公司製)0.5份，除此以外，與製造例9同樣地形成丙烯酸系黏著劑層(C7)。 In the preparation of the adhesive solution, 0.5 parts of 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) phthalimide (manufactured by Kishida Chemical Co., Ltd.) as a conductive material was further added. Otherwise, an acrylic pressure-sensitive adhesive layer (C7) was formed in the same manner as in Production Example 9.

製造例16(丙烯酸系黏著劑層(C8)之製作) Production Example 16 (Production of Acrylic Adhesive Layer (C8))

於黏著劑溶液之製備時不添加磷系化合物，除此以外，與製造例15同樣地形成丙烯酸系黏著劑層(C8)。 An acrylic pressure-sensitive adhesive layer (C8) was formed in the same manner as in Production Example 15 except that the phosphorus-based compound was not added to the preparation of the pressure-sensitive adhesive solution.

實施例1 Example 1

使用線棒塗佈機，於製造例1中獲得之單面保護偏光膜(1)之偏光子之面(未設置透明保護膜之偏光子面)上，以乾燥後之厚度達到1μm之方式塗佈調整為25℃之塗敷層形成用樹脂組合物(A1)，然後於60℃下熱風乾燥1分鐘，形成塗敷層1，製作附有1層塗敷層之單面保護偏光膜。 The surface of the polarizer of the one-side protective polarizing film (1) obtained in Production Example 1 (the polarizing surface of the transparent protective film was not provided) was applied by a wire bar coater to a thickness of 1 μm after drying. The coating composition-forming resin composition (A1) was adjusted to 25 ° C, and then dried by hot air at 60 ° C for 1 minute to form a coating layer 1 to prepare a one-side protective polarizing film having one coating layer.

繼而，使用線棒塗佈機，於上述中獲得之附有1層塗敷層之單面保護偏光膜之塗敷層1上，以乾燥後之厚度達到1μm之方式進而塗佈調整為25℃之塗敷層用組合物(B1)，然後於60℃下熱風乾燥1分鐘，形成塗敷層2，製作附有2層塗敷層之偏光膜。 Then, using a wire bar coater, the coating layer 1 of the one-side protective polarizing film having the one coating layer obtained above was applied and adjusted to 25 ° C in a thickness of 1 μm after drying. The coating layer composition (B1) was dried by hot air at 60 ° C for 1 minute to form a coating layer 2, and a polarizing film having two coating layers was formed.

繼而，於上述中獲得之附有2層塗敷層之偏光膜之塗敷層2上貼合形成於上述脫模片(隔離件)之剝離處理面之黏著劑層(C2)，製作附 有黏著劑層之偏光膜。 Then, the adhesive layer (C2) formed on the release-treated surface of the release sheet (separator) is bonded to the coating layer 2 of the polarizing film having the two-layer coating layer obtained as described above, and attached. A polarizing film with an adhesive layer.

實施例2~11、比較例1~12 Examples 2 to 11 and Comparative Examples 1 to 12

於實施例1中將塗敷層形成用樹脂組合物、黏著劑層如表1、2所示地進行變化，除此以外，與實施例1同樣地形成附有黏著劑層之偏光膜。 In the same manner as in Example 1, except that the resin composition for forming a coating layer and the pressure-sensitive adhesive layer were changed as shown in Tables 1 and 2, a polarizing film with an adhesive layer was formed.

以下對上述實施例及比較例中獲得之附有黏著劑層之偏光膜進行評價。結果如表1、2所示。 The polarizing film with the adhesive layer obtained in the above examples and comparative examples was evaluated below. The results are shown in Tables 1 and 2.

<電阻值變化率> <resistance change rate>

將於表面形成有ITO層之導電性膜(商品名：Elecrysta(P400L)，日東電工股份有限公司製造)切斷成15mm×15mm，將實施例及比較例中獲得之附有黏著劑層之偏光膜切斷成8mm×8mm，剝離隔離件膜而貼合於該導電性膜上之中央部後，於50℃、5atm下實施15分鐘高壓釜處理，將所獲得之樣品作為耐腐蝕性測定樣品。使用下述測定裝置測定所獲得之測定用樣品之電阻值，將其設為「初始電阻值」。 A conductive film (trade name: Elecrysta (P400L), manufactured by Nitto Denko Corporation) having an ITO layer formed on the surface thereof was cut into 15 mm × 15 mm, and polarized light having an adhesive layer obtained in Examples and Comparative Examples was obtained. The film was cut into 8 mm × 8 mm, and the separator film was peeled off and bonded to the central portion of the conductive film, and then autoclaved at 50 ° C and 5 atm for 15 minutes, and the obtained sample was used as a sample for corrosion resistance measurement. . The resistance value of the obtained sample for measurement was measured using the following measuring apparatus, and this was made into the " initial resistance value."

其後，將測定用樣品投入於溫度60℃、濕度95%之環境下500小時後，測定電阻值，設為「濕熱後之電阻值」。再者，上述電阻值係使用Accent Optical Technologies公司製造之HL5500PC進行測定。由以上述方式測得之「初始電阻值」及「濕熱後之電阻值」並根據下式而算出各自為濕熱狀態之情形時之電阻值變化率(%)。 Thereafter, the sample for measurement was placed in an environment of a temperature of 60 ° C and a humidity of 95% for 500 hours, and then the resistance value was measured and referred to as "resistance value after moist heat". Further, the above resistance value was measured using HL5500PC manufactured by Accent Optical Technologies. From the "initial resistance value" and the "resistance value after wet heat" measured as described above, the resistance value change rate (%) in the case where each of them is in a wet heat state is calculated from the following equation.

電阻值變化率未達150%之情形表示由濕熱所引起之電阻值之上升幅度較小，耐腐蝕性良好。 When the rate of change of the resistance value is less than 150%, the increase in the resistance value caused by the moist heat is small, and the corrosion resistance is good.

<密接力> <Close contact>

將實施例及比較例中獲得之附有黏著劑層之偏光膜切割為25mm×150mm之大小，以使其黏著劑層面與於50μm厚之聚對苯二甲酸乙二酯膜表面蒸鍍有銦-氧化錫之蒸鍍膜之蒸鍍面接觸之方式進行貼合。其後，將上述聚對苯二甲酸乙二酯膜之端部用手剝離，確認黏著劑層附著於聚對苯二甲酸乙二酯膜側後，使用島津製作所股份有限公司製之拉伸試驗機AG-1，測定(25℃)沿180°方向以300mm/min之速度進行剝離時之應力(N/25mm)。 The polarizing film with the adhesive layer obtained in the examples and the comparative examples was cut into a size of 25 mm × 150 mm so that the adhesive layer and the surface of the 50 μm thick polyethylene terephthalate film were vapor-deposited with indium. - The vapor deposition surface of the deposited film of tin oxide is bonded in such a manner as to be in contact with each other. Then, the end portion of the polyethylene terephthalate film was peeled off by hand, and it was confirmed that the adhesive layer adhered to the polyethylene terephthalate film side, and a tensile test by Shimadzu Corporation was used. Machine AG-1, measured (25 ° C) stress (N / 25 mm) when peeling at a speed of 300 mm / min in the 180 ° direction.

密接力為15N/25mm以上之情形表示不存在返工時之糊劑殘留、或加工時之糊劑不足，較為良好。 The case where the adhesion is 15 N/25 mm or more indicates that there is no residue remaining during rework or that the paste at the time of processing is insufficient, which is good.

表中之簡稱分別如下所示。 The abbreviations in the table are as follows.

(A1)~(A4)：塗敷層形成用樹脂組合物(A1)~(A4) (A1) to (A4): resin composition for forming a coating layer (A1) to (A4)

(B1)、(B2)：增黏層(anchor layer)用組合物(B1)、(B2) (B1), (B2): composition for anchor layer (B1), (B2)

(C1)~(C8)：黏著劑層(C1)~(C8) (C1)~(C8): Adhesive layer (C1)~(C8)

又，記載為「有無」之項目中，「○」表示「含有」，「-」表示「不含有」。 In addition, in the item described as "there is no", "○" means "include" and "-" means "not included".

1‧‧‧附有塗敷層之偏光膜 1‧‧‧ polarizing film with coating

2‧‧‧碘系偏光子 2‧‧‧Iodine-based photon

3‧‧‧透明保護膜 3‧‧‧Transparent protective film

4‧‧‧塗敷層 4‧‧‧coating layer

Claims (12)

一種附有塗敷層之偏光膜，其依序具有透明保護膜、含有碘及/或碘離子之碘系偏光子以及塗敷層，其特徵在於：上述碘系偏光子及/或上述塗敷層含有磷系化合物。 A polarizing film with a coating layer, which in turn has a transparent protective film, an iodine-based polarizer containing iodine and/or iodide ions, and a coating layer, characterized in that the iodine-based polarizer and/or the coating described above The layer contains a phosphorus compound. 如請求項1之附有塗敷層之偏光膜，其中上述磷系化合物含有選自由下述通式(1)： (式中，R¹及R²各自獨立地表示氫原子、或可含有氧原子之碳數1~18之烴殘基)所表示之化合物及上述通式(1)所表示之化合物之多聚物所組成之群中之1種以上之磷酸系化合物、及/或選自由下述通式(2)： (式中，R為氫原子、或可含有氧原子之碳數1~18之烴殘基)所表示之化合物及其鹽所組成之群中之1種以上之膦酸系化合物。 A polarizing film with a coating layer as claimed in claim 1, wherein the phosphorus compound is selected from the group consisting of the following formula (1): (wherein R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom) and a compound represented by the above formula (1) One or more phosphate compounds in the group consisting of the substances, and/or selected from the following formula (2): (In the formula, R is a hydrogen atom or a hydrocarbon residue having a carbon number of 1 to 18 which may contain an oxygen atom), and one or more phosphonic acid compounds in a group consisting of a salt thereof. 如請求項1或2之附有塗敷層之偏光膜，其中上述碘系偏光子之厚度為10μm以下。 A polarizing film having a coating layer as claimed in claim 1 or 2, wherein the iodine-based polarizer has a thickness of 10 μm or less. 如請求項1至3中任一項之附有塗敷層之偏光膜，其中上述碘系 偏光子中之上述碘及/或碘離子之含量為3~12重量%。 The coating film-attached polarizing film according to any one of claims 1 to 3, wherein the iodine system is The content of the above iodine and/or iodide ion in the polarizer is 3 to 12% by weight. 如請求項1至4中任一項之附有塗敷層之偏光膜，其中於上述碘系偏光子與上述塗敷層之間不具有透明保護膜。 The coating film-attached polarizing film according to any one of claims 1 to 4, wherein a transparent protective film is not provided between the iodine-based polarizer and the coating layer. 如請求項1至5中任一項之附有塗敷層之偏光膜，其中上述塗敷層係由含有選自由聚胺基甲酸酯系樹脂、聚乙烯醇系樹脂及丙烯酸系樹脂所組成之群中之至少1種樹脂之樹脂組合物形成。 The polarizing film with a coating layer according to any one of claims 1 to 5, wherein the coating layer is composed of a material selected from the group consisting of a polyurethane resin, a polyvinyl alcohol resin, and an acrylic resin. A resin composition of at least one resin in the group is formed. 一種附有黏著劑層之偏光膜，其特徵在於：於如請求項1至6中任一項之附有塗敷層之偏光膜之塗敷層側具有黏著劑層。 A polarizing film with an adhesive layer, characterized in that the coating layer side of the polarizing film with a coating layer as claimed in any one of claims 1 to 6 has an adhesive layer. 如請求項7之附有黏著劑層之偏光膜，其中上述黏著劑層含有離子性化合物。 A polarizing film with an adhesive layer as claimed in claim 7, wherein the above adhesive layer contains an ionic compound. 如請求項7或8之附有黏著劑層之偏光膜，其係以與具有透明導電層之透明導電性構件之透明導電層接觸之方式貼合如請求項7或8之附有黏著劑層之偏光膜之黏著劑層而使用。 A polarizing film with an adhesive layer as claimed in claim 7 or 8, which is adhered to the transparent conductive layer of the transparent conductive member having a transparent conductive layer, and has an adhesive layer as claimed in claim 7 or 8. It is used as an adhesive layer of a polarizing film. 如請求項9之附有黏著劑層之偏光膜，其中上述透明導電層係由氧化銦錫形成。 A polarizing film with an adhesive layer attached to claim 9, wherein the transparent conductive layer is formed of indium tin oxide. 如請求項10之附有黏著劑層之偏光膜，其中上述氧化銦錫為非晶質之氧化銦錫。 A polarizing film with an adhesive layer as claimed in claim 10, wherein the indium tin oxide is amorphous indium tin oxide. 一種圖像顯示裝置，其特徵在於：將如請求項7至11中任一項之附有黏著劑層之偏光膜之黏著劑層與具有透明導電層之液晶面板，以使上述附有黏著劑層之偏光膜之黏著劑層與上述液晶面板之透明導電層接觸之方式貼合。 An image display device comprising: an adhesive layer of a polarizing film with an adhesive layer attached thereto according to any one of claims 7 to 11 and a liquid crystal panel having a transparent conductive layer, so that the above-mentioned adhesive is attached The adhesive layer of the polarizing film of the layer is bonded to the transparent conductive layer of the liquid crystal panel.