TWI844725B - Manufacturing method of polarizing film - Google Patents

Abstract

本發明提供一種偏光薄膜之製造方法，上述偏光薄膜在偏光件的至少一面隔著黏接劑層設置有透明保護薄膜，該方法包括：第一塗敷步驟，在透明保護薄膜的貼合面塗敷黏接劑組合物；貼合步驟，使偏光件及透明保護薄膜貼合；以及黏接步驟，從偏光件面側或透明保護薄膜面側照射活性能量射線，使黏接劑組合物固化而得到黏接劑層，從而隔著上述黏接劑層使偏光件及透明保護薄膜黏接，透明保護薄膜的SP值與上述黏接劑組合物的SP值之間的SP值距離為5.3以上。The present invention provides a method for manufacturing a polarizing film, wherein a transparent protective film is provided on at least one side of a polarizer via an adhesive layer, and the method comprises: a first coating step of coating an adhesive composition on the bonding surface of the transparent protective film; a bonding step of bonding the polarizer and the transparent protective film; and a bonding step of irradiating active energy rays from the side of the polarizer or the side of the transparent protective film to cure the adhesive composition to obtain an adhesive layer, thereby bonding the polarizer and the transparent protective film via the adhesive layer, and the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is greater than 5.3.

Description

偏光薄膜之製造方法Manufacturing method of polarizing film

發明領域Invention Field

本發明涉及在偏光件的至少一面隔著黏接劑層設置有透明保護薄膜的偏光薄膜之製造方法。該偏光薄膜可以單獨、或者以積層了該偏光薄膜的光學薄膜的形式，形成液晶顯示裝置(LCD)、有機EL顯示裝置、CRT、PDP等圖像顯示裝置。The present invention relates to a method for manufacturing a polarizing film having a transparent protective film disposed on at least one side of a polarizer via an adhesive layer. The polarizing film can be used alone or in the form of an optical film laminated with the polarizing film to form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, a PDP, etc.

發明背景Invention Background

鐘錶、手機、PDA、筆記型電腦、電腦用顯示器、DVD播放機、TV等中，液晶顯示裝置正在急劇地打開市場。液晶顯示裝置是使基於液晶的開關的偏光狀態可視化的裝置，從其顯示原理出發，使用偏光件。特別是在TV等的用途中，越來越要求高亮度、高對比、廣闊的視角，對於偏光薄膜也越來越要求高透射率、高偏光度、高顏色再現性等。Liquid crystal display devices are rapidly expanding in the market for watches, mobile phones, PDAs, laptops, computer monitors, DVD players, TVs, etc. Liquid crystal display devices are devices that visualize the polarization state of liquid crystal switches, and polarizers are used based on their display principles. In particular, in applications such as TVs, high brightness, high contrast, and wide viewing angles are increasingly required, and polarizing films are increasingly required to have high transmittance, high polarization degree, and high color reproducibility.

作為偏光件，從具有高透射率、高偏光度的方面出發，例如通常最廣泛使用的是使碘吸附於聚乙烯醇(以下，也簡稱為“PVA”)並進行了拉伸的結構的碘系偏光件。通常偏光薄膜使用在偏光件的兩面利用將聚乙烯醇類的材料溶於水而成的所謂水性黏接劑貼合有透明保護薄膜的偏光薄膜(下述專利文獻1)。作為透明保護薄膜，使用透濕度高的三乙酸纖維素等。在使用了上述水性黏接劑(所謂濕式層壓)的情況下，在將偏光件及透明保護薄膜貼合後，需要乾燥步驟。As a polarizer, from the aspect of high transmittance and high polarization degree, for example, the most widely used is an iodine-based polarizer having a structure in which iodine is adsorbed on polyvinyl alcohol (hereinafter, also referred to as "PVA") and stretched. Usually, a polarizing film is used in which a transparent protective film is bonded to both sides of the polarizer using a so-called aqueous adhesive made by dissolving a polyvinyl alcohol-based material in water (Patent Document 1 below). As the transparent protective film, cellulose triacetate with high moisture permeability is used. When the above-mentioned aqueous adhesive (so-called wet lamination) is used, a drying step is required after bonding the polarizer and the transparent protective film.

另一方面，代替上述水性黏接劑，提出了活性能量射線固化性黏接劑。使用活性能量射線固化性黏接劑製造偏光薄膜的情況下，由於不需要乾燥步驟，因此能夠提高偏光薄膜的生產率。例如，提出了使用N-取代醯胺類單體作為固化性成分的自由基聚合型的活性能量射線固化性黏接劑(下述專利文獻2)。 先行技術文獻 專利文獻On the other hand, active energy ray-curable adhesives have been proposed to replace the above-mentioned water-based adhesives. When a polarizing film is produced using an active energy ray-curable adhesive, since a drying step is not required, the productivity of the polarizing film can be improved. For example, a free radical polymerization type active energy ray-curable adhesive using an N-substituted amide monomer as a curing component has been proposed (Patent Document 2 below). Prior Art Documents Patent Documents

專利文獻1：日本特開2001-296427號公報 專利文獻2：日本特開2012-052000號公報Patent document 1: Japanese Patent Publication No. 2001-296427 Patent document 2: Japanese Patent Publication No. 2012-052000

發明所要解決的課題Problem to be solved by the invention

使用專利文獻2中記載的活性能量射線固化性黏接劑而形成的黏接劑層能夠充分耐受例如對在60℃溫水中浸漬6小時後有無脫色、剝落進行評價的耐水性試驗。但近年來，對於偏光薄膜用黏接劑，要求能夠耐受例如對在水中浸漬(飽和)後進行端部爪剝離時有無剝落進行評價的、更嚴酷的耐水性試驗的程度的進一步耐水性提高。因此，目前的情況是，包括專利文獻2中記載的利用了活性能量射線固化性黏接劑的偏光薄膜在內，目前為止彙報的偏光薄膜用黏接劑在黏接性方面還有進一步改良的餘地。The adhesive layer formed by using the active energy ray curing adhesive described in Patent Document 2 can fully withstand water resistance tests such as evaluating whether there is discoloration or peeling after immersion in 60°C warm water for 6 hours. However, in recent years, adhesives for polarizing films have been required to have further improved water resistance to the extent that they can withstand more severe water resistance tests such as evaluating whether there is peeling when the end claws are peeled off after immersion (saturation) in water. Therefore, the current situation is that there is still room for further improvement in the adhesion of the polarizing film adhesives reported so far, including the polarizing film using the active energy ray curing adhesive described in Patent Document 2.

另外，近年，偏光薄膜的薄型化正在進行，如果在偏光薄膜中存在氣泡等，則容易作為外觀缺點而引人注目，成為產品不良的情況較多。因此，例如抑制在構成偏光薄膜的透明保護薄膜的表面、或使透明保護薄膜與偏光件黏接的黏接劑層中產生氣泡是不可或缺的。然而，實際情況是，沒有對將透明保護薄膜與黏接劑層的親和性最適化、抑制偏光薄膜中的氣泡產生進行研究的彙報範例。In recent years, polarizing films have become thinner, and if bubbles exist in polarizing films, they are easily noticeable as appearance defects, and often become product defects. Therefore, it is essential to suppress the generation of bubbles on the surface of the transparent protective film constituting the polarizing film or in the adhesive layer that bonds the transparent protective film to the polarizer. However, in reality, there is no reported example of research on optimizing the affinity between the transparent protective film and the adhesive layer to suppress the generation of bubbles in the polarizing film.

本發明鑒於上述實際情況而開發，其目的在於，提供可以在提高偏光件與透明保護薄膜之間的黏接性的同時抑制偏光薄膜內的氣泡產生的偏光薄膜之製造方法。 解決課題的手段The present invention was developed in view of the above-mentioned actual situation, and its purpose is to provide a method for manufacturing a polarizing film that can improve the adhesion between the polarizer and the transparent protective film while suppressing the generation of bubbles in the polarizing film. Means for solving the problem

上述課題可以藉由下述構成來解決。即，本發明涉及一種偏光薄膜之製造方法，上述偏光薄膜在偏光件的至少一面隔著黏接劑層設置有透明保護薄膜，該方法包括：第一塗敷步驟，在上述透明保護薄膜的貼合面塗敷黏接劑組合物；貼合步驟，將上述偏光件及上述透明保護薄膜貼合；以及黏接步驟，從偏光件面側或透明保護薄膜面側照射活性能量射線，使上述黏接劑組合物固化而得到黏接劑層，從而隔著上述黏接劑層使上述偏光件及上述透明保護薄膜黏接，上述透明保護薄膜的SP值與上述黏接劑組合物的SP值之間的SP值距離為5.3以上。The above-mentioned problem can be solved by the following structure. That is, the present invention relates to a method for manufacturing a polarizing film, wherein the polarizing film is provided with a transparent protective film on at least one side of a polarizer via an adhesive layer, and the method comprises: a first coating step of coating an adhesive composition on the bonding surface of the transparent protective film; a bonding step of bonding the polarizer and the transparent protective film; and a bonding step of irradiating active energy rays from the side of the polarizer or the side of the transparent protective film to cure the adhesive composition to obtain an adhesive layer, thereby bonding the polarizer and the transparent protective film via the adhesive layer, and the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is 5.3 or more.

較佳在上述偏光薄膜之製造方法中進一步具有第二塗敷步驟，該第二塗敷步驟在上述偏光件的貼合面塗敷易黏接組合物，上述黏接步驟是隔著使上述黏接劑組合物及上述易黏接組合物固化而得到的黏接劑層使上述偏光件及上述透明保護薄膜黏接的步驟，上述透明保護薄膜的SP值與上述易黏接組合物的SP值之間的SP值距離為8.0以下。Preferably, the method for manufacturing the polarizing film further comprises a second coating step, wherein an easy-bonding composition is coated on the bonding surface of the polarizer, and the bonding step is a step of bonding the polarizer and the transparent protective film via an adhesive layer obtained by curing the adhesive composition and the easy-bonding composition, wherein the SP value distance between the SP value of the transparent protective film and the SP value of the easy-bonding composition is less than 8.0.

較佳在上述偏光薄膜之製造方法中，上述易黏接組合物含有下述通式(1)表示的化合物， [化學式1] (式中，X為包含反應性基團的官能團，R¹ 及R² 分別獨立地表示氫原子、可亦具有取代基的脂肪族烴基、芳基或雜環基。X所含的反應性基團為選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁基及巰基所構成組群中的至少1種反應性基團)。又，在本發明中，也將上述通式(1)中記載的化合物稱為“含硼化合物”。Preferably, in the method for producing the polarizing film, the easy-adhesion composition contains a compound represented by the following general formula (1): (In the formula, X is a functional group containing a reactive group, ^R1 and ^R2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may also have a substituent, an aryl group or a heterocyclic group. The reactive group contained in X is at least one reactive group selected from the group consisting of a vinyl group, a (meth)acryl group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxycyclobutyl group and an alkyl group). In the present invention, the compound described in the above general formula (1) is also referred to as a "boron-containing compound".

較佳在上述偏光薄膜之製造方法中，上述通式(1)表示的化合物為下述通式(1’)表示的化合物， [化學式2] (式中，Y為有機基團，X’為X所含的反應性基團，R¹ 及R² 與上述定義相同)。Preferably, in the method for producing the polarizing film, the compound represented by the general formula (1) is a compound represented by the following general formula (1'): [Chemical Formula 2] (wherein, Y is an organic group, X' is a reactive group contained in X, and ^R1 and ^R2 have the same meanings as defined above).

較佳在上述偏光薄膜之製造方法中，上述易黏接組合物含有下述通式(2)表示的自由基聚合性化合物， [化學式3] (式中，R³ 為氫原子或甲基，R⁴ 及R⁵ 分別獨立地為氫原子、烷基、羥基烷基、烷氧基烷基或環狀醚基，R⁴ 及R⁵ 可亦形成環狀雜環)。 發明的效果Preferably, in the method for producing the polarizing film, the easy-adhesion composition contains a radical polymerizable compound represented by the following general formula (2): [Chemical formula 3] (In the formula, R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or a cyclic ether group, and R ⁴ and R ⁵ may also form a cyclic heterocycle.) Effect of the invention

在本發明的偏光薄膜之製造方法中，將用於使偏光件與透明保護薄膜黏接的黏接劑組合物塗敷於透明保護薄膜的貼合面(與偏光件的貼合面)(第一塗敷步驟)。本發明中，以使透明保護薄膜的SP值與黏接劑組合物的SP值之間的SP值距離成為5.3以上的方式設計黏接劑組合物，因此，可以製造偏光件與透明保護薄膜之間的黏接性得到了提高、且內部的氣泡產生得到了抑制的偏光薄膜。在本發明的偏光薄膜之製造方法中，作為得到上述效果的理由，可以推定如下。In the manufacturing method of the polarizing film of the present invention, an adhesive composition for bonding the polarizer to the transparent protective film is applied to the bonding surface of the transparent protective film (the bonding surface with the polarizer) (first coating step). In the present invention, the adhesive composition is designed in such a way that the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition becomes 5.3 or more, so that the adhesion between the polarizer and the transparent protective film is improved and the generation of bubbles inside can be manufactured. In the manufacturing method of the polarizing film of the present invention, the reason for obtaining the above-mentioned effect can be inferred as follows.

為了提高黏接劑與被黏附物的黏接力，通常選擇與被黏附物的親和性優異的黏接劑。然而，本案發明人基於這樣的一般的見解製造偏光薄膜時查明，由於以下的現象，容易在偏光薄膜內產生氣泡。 (1)選擇對於透明保護薄膜的親和性過度優異的黏接劑組合物時，由於黏接劑組合物過度滲入透明保護薄膜，透明保護薄膜表面(黏接劑組合物的塗敷面)成為乾燥狀態。 (2)由於在成為乾燥狀態的透明保護薄膜表面殘存凹凸，因此表面粗糙度Ra變高。 (3)起因於殘存於透明保護薄膜表面的凹凸，在積層而得到的偏光薄膜內產生氣泡。In order to improve the adhesion between the adhesive and the adherend, an adhesive with excellent affinity for the adherend is usually selected. However, the inventors of this case found out that bubbles are easily generated in the polarizing film due to the following phenomena when manufacturing the polarizing film based on such general views. (1) When an adhesive composition with excessively excellent affinity for the transparent protective film is selected, the adhesive composition excessively penetrates into the transparent protective film, and the surface of the transparent protective film (the surface where the adhesive composition is applied) becomes dry. (2) Since unevenness remains on the surface of the transparent protective film in a dry state, the surface roughness Ra becomes higher. (3) Due to the unevenness remaining on the surface of the transparent protective film, bubbles are generated in the polarizing film obtained by lamination.

為了避免上述現象，在本發明中，為了抑制黏接劑組合物過度滲入透明保護薄膜，用黏接劑組合物填埋殘存於透明保護薄膜表面的凹凸，使其表面平滑，如下所述地設計黏接劑組合物：適度降低透明保護薄膜與使用的黏接劑組合物的親和性，具體而言使透明保護薄膜的SP值與黏接劑組合物的SP值之間的SP值距離成為5.3以上。由此，在本發明中，可以製造抑制了在透明保護薄膜表面及/或黏接劑層內的氣泡產生的偏光薄膜。In order to avoid the above phenomenon, in the present invention, in order to suppress the excessive penetration of the adhesive composition into the transparent protective film, the adhesive composition is used to fill the unevenness remaining on the surface of the transparent protective film to make the surface smooth, and the adhesive composition is designed as follows: the affinity between the transparent protective film and the adhesive composition used is appropriately reduced, specifically, the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is made to be 5.3 or more. As a result, in the present invention, a polarizing film in which the generation of bubbles on the surface of the transparent protective film and/or in the adhesive layer is suppressed can be manufactured.

又，在本發明中，SP值表示的是由Hansen等提出的溶解參數的含義，該SP值由三維空間中的1個點來表示。2個物質間(例如透明保護薄膜與黏接劑組合物)的親和性可以由2個SP值的距離(SP值距離)來評價，如果2個物質間的SP值距離小，則可以說親和性大。In the present invention, the SP value represents the meaning of the solubility parameter proposed by Hansen et al., and the SP value is represented by one point in three-dimensional space. The affinity between two substances (e.g., a transparent protective film and an adhesive composition) can be evaluated by the distance between the two SP values (SP value distance). If the SP value distance between the two substances is small, it can be said that the affinity is large.

在本發明的偏光薄膜之製造方法中，進一步具有第二塗敷步驟，該第二塗敷步驟在偏光件的貼合面塗敷易黏接組合物，黏接步驟是隔著使黏接劑組合物及易黏接組合物固化而得到的黏接劑層使偏光件及透明保護薄膜黏接的步驟，透明保護薄膜的SP值與易黏接組合物的SP值之間的SP值距離為8.0以下時，可以抑制偏光薄膜內部的氣泡產生，並且可以進一步提高偏光件與透明保護薄膜之間的黏接性，因而較佳。在該構成中，作為得到上述效果的理由，可以推定如下。In the manufacturing method of the polarizing film of the present invention, there is further a second coating step, in which an easy-adhesive composition is coated on the bonding surface of the polarizer, and the bonding step is a step of bonding the polarizer and the transparent protective film via an adhesive layer obtained by curing the adhesive composition and the easy-adhesive composition, and when the SP value distance between the SP value of the transparent protective film and the SP value of the easy-adhesive composition is 8.0 or less, the generation of bubbles inside the polarizing film can be suppressed, and the adhesion between the polarizer and the transparent protective film can be further improved, which is preferred. In this configuration, the reason for obtaining the above effect can be inferred as follows.

如上所述，為了提高黏接劑與透明保護薄膜的黏接力而選擇與透明保護薄膜的親和性優異的黏接劑時，氣泡產生的可能性提高。在本發明中，根據需要，為了抑制氣泡產生，可以以使透明保護薄膜的SP值與黏接劑組合物的SP值之間的SP值距離成為5.3以上的方式設計黏接劑組合物，並且進而在偏光件的貼合面塗敷易黏接組合物(第二塗敷步驟)。而且，以使透明保護薄膜的SP值與易黏接組合物的SP值之間的SP值距離成為8.0以下的方式設計上述易黏接組合物，在貼合步驟中，塗敷於透明保護薄膜的貼合面的未固化的黏接劑組合物與塗敷於偏光件的貼合面的未固化的易黏接組合物混合。由此，與透明保護薄膜的SP值距離接近的易黏接組合物中的成分轉移至透明保護薄膜側、並且固化而形成黏接劑層，因此，可以抑制偏光薄膜內部的氣泡產生，並且偏光件與透明保護薄膜之間的黏接性進一步提高。As described above, in order to improve the adhesive strength between the adhesive and the transparent protective film, when an adhesive with excellent affinity to the transparent protective film is selected, the possibility of bubble generation increases. In the present invention, if necessary, in order to suppress bubble generation, the adhesive composition can be designed in such a way that the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition becomes 5.3 or more, and further, the easy-bonding composition is applied to the bonding surface of the polarizer (second application step). Furthermore, the easy-adhesive composition is designed so that the SP value distance between the SP value of the transparent protective film and the SP value of the easy-adhesive composition is 8.0 or less, and in the laminating step, the uncured adhesive composition applied to the laminating surface of the transparent protective film is mixed with the uncured easy-adhesive composition applied to the laminating surface of the polarizer. As a result, the components in the easy-adhesive composition close to the SP value distance of the transparent protective film are transferred to the transparent protective film side and cured to form an adhesive layer, so that the generation of bubbles inside the polarizing film can be suppressed, and the adhesion between the polarizer and the transparent protective film is further improved.

如上所述，在本發明的偏光薄膜之製造方法中，可以製造提高了偏光件與透明保護薄膜之間的黏接性、並且抑制了在其內部的氣泡產生的偏光薄膜。因此，使用了本發明的偏光薄膜的圖像顯示裝置在要求黏接性及外觀性的用途中特別有用。As described above, in the manufacturing method of the polarizing film of the present invention, the polarizing film can be manufactured with improved adhesion between the polarizer and the transparent protective film and suppressed generation of bubbles inside the polarizing film. Therefore, the image display device using the polarizing film of the present invention is particularly useful in applications requiring adhesion and appearance.

具體實施方式Specific implementation methods

本發明是一種偏光薄膜之製造方法，該偏光薄膜在偏光件的至少一面隔著黏接劑層設置有透明保護薄膜，該方法包括：第一塗敷步驟，在透明保護薄膜的貼合面塗敷黏接劑組合物；貼合步驟，使偏光件及透明保護薄膜貼合；以及黏接步驟，從偏光件面側或透明保護薄膜面側照射活性能量射線，使黏接劑組合物固化而得到黏接劑層，從而隔著上述黏接劑層使偏光件及透明保護薄膜黏接。以下，對本發明具體地進行說明。The present invention is a method for manufacturing a polarizing film, wherein a transparent protective film is provided on at least one side of a polarizer via an adhesive layer, and the method comprises: a first coating step, coating an adhesive composition on the bonding surface of the transparent protective film; a bonding step, bonding the polarizer and the transparent protective film; and a bonding step, irradiating active energy rays from the side of the polarizer or the side of the transparent protective film to cure the adhesive composition to obtain an adhesive layer, thereby bonding the polarizer and the transparent protective film via the adhesive layer. The present invention is specifically described below.

＜黏接劑組合物＞ 將在本發明的偏光薄膜之製造方法中使用的黏接劑組合物設計為使透明保護薄膜的SP值與黏接劑組合物的SP值之間的SP值距離成為5.3以上。關於該SP值距離的上限，為了適度保持透明保護薄膜與黏接劑層的黏接力，較佳設為5.9以下、更佳設為5.8以下。需要說明的是，在本發明中，將構成黏接劑組合物的單體等的SP值作為參考，可以藉由適宜調整混合比例等而將黏接劑組合物的SP值調整為期望的範圍內。對於黏接劑組合物的SP值的測定方法，在後面敘述。<Adhesive composition> The adhesive composition used in the method for producing the polarizing film of the present invention is designed so that the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition is 5.3 or more. The upper limit of the SP value distance is preferably set to 5.9 or less, and more preferably set to 5.8 or less in order to appropriately maintain the adhesion between the transparent protective film and the adhesive layer. It should be noted that in the present invention, the SP value of the monomer constituting the adhesive composition is used as a reference, and the SP value of the adhesive composition can be adjusted to a desired range by appropriately adjusting the mixing ratio. The method for measuring the SP value of the adhesive composition will be described later.

作為黏接劑組合物固化的形態，可以大致分為熱固化及活性能量射線固化。作為構成熱固化性黏接劑組合物的樹脂，可列舉聚乙烯醇樹脂、環氧樹脂、不飽和聚酯、胺基甲酸酯樹脂、丙烯酸類樹脂、尿素樹脂、三聚氰胺樹脂、酚醛樹脂等，根據需要組合固化劑來使用。作為構成熱固性黏接劑組合物的樹脂，更佳使用聚乙烯醇樹脂、環氧樹脂。作為活性能量射線固化性黏接劑組合物，基於活性能量射線的分類可以大致分為電子束固化性、紫外線固化性、可見光固化性。另外，作為固化的形態，可以分為自由基聚合性黏接劑組合物及陽離子聚合性黏接劑組合物。在本發明中，可將波長範圍10nm~380nm的活性能量射線記載為紫外線、將波長範圍380nm~800nm的活性能量射線記載為可見光。As the curing form of the adhesive composition, it can be roughly divided into heat curing and active energy ray curing. As the resin constituting the heat curing adhesive composition, polyvinyl alcohol resin, epoxy resin, unsaturated polyester, urethane resin, acrylic resin, urea resin, melamine resin, phenolic resin, etc. can be listed, and the curing agent can be combined and used as needed. As the resin constituting the thermosetting adhesive composition, polyvinyl alcohol resin and epoxy resin are more preferably used. As the active energy ray curing adhesive composition, it can be roughly divided into electron beam curing, ultraviolet curing, and visible light curing based on the classification of active energy rays. In addition, as the form of curing, it can be divided into free radical polymerizable adhesive composition and cationic polymerizable adhesive composition. In the present invention, active energy rays with a wavelength range of 10nm to 380nm can be recorded as ultraviolet rays, and active energy rays with a wavelength range of 380nm to 800nm can be recorded as visible light.

在本發明的偏光薄膜的製造中，黏接劑組合物較佳為活性能量射線固化性。進一步，特佳為利用380nm~450nm的可見光的可見光固化性。In the production of the polarizing film of the present invention, the adhesive composition is preferably active energy ray curable, and more preferably visible light curable using visible light of 380 nm to 450 nm.

作為自由基聚合性黏接劑組合物所含有的固化性成分，可舉出例如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-碳雙鍵的自由基聚合性官能團的化合物。這些固化性成分可以使用單官能自由基聚合性化合物或二官能以上的多官能自由基聚合性化合物中的任一種。另外，這些自由基聚合性化合物可以單獨使用1種，或者組合使用2種以上。作為這些自由基聚合性化合物，較佳例如具有(甲基)丙烯醯基的化合物。需要說明的是，在本發明中，(甲基)丙烯醯基是指丙烯醯基及/或甲基丙烯醯基，“(甲基)”在以下是相同的含義。As the curable component contained in the free radical polymerizable adhesive composition, for example, free radical polymerizable compounds can be cited. The free radical polymerizable compounds can be compounds having free radical polymerizable functional groups of carbon-carbon double bonds such as (meth)acryl and vinyl. These curable components can use any of monofunctional free radical polymerizable compounds or polyfunctional free radical polymerizable compounds with more than two functions. In addition, these free radical polymerizable compounds can be used alone or in combination of two or more. As these free radical polymerizable compounds, compounds having (meth)acryl are preferred. It should be noted that in the present invention, (meth)acryl refers to acryl and/or methacryl, and "(meth)" has the same meaning below.

作為單官能自由基聚合性化合物，可列舉例如下述通式(2)表示的化合物。 [化學式4] (式中，R³ 氫原子或甲基，R⁴ 及R⁵ 分別獨立地為氫原子、烷基、羥基烷基、烷氧基烷基或環狀醚基，R⁴ 及R⁵ 可亦形成環狀雜環)。烷基、羥基烷基、及/或烷氧基烷基的烷基部分的碳原子數沒有特別限定，可示例出例如1~4個。另外，R⁴ 及R⁵ 可亦形成的環狀雜環可列舉例如N-丙烯醯基嗎啉等。Examples of monofunctional radical polymerizable compounds include compounds represented by the following general formula (2). [Chemical formula 4] (wherein, ^R3 is a hydrogen atom or a methyl group, ^R4 and ^R5 are independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or a cyclic ether group, and ^R4 and ^R5 may also form a cyclic heterocycle.) The number of carbon atoms in the alkyl group, the hydroxyalkyl group, and/or the alkoxyalkyl group is not particularly limited, and examples thereof include 1 to 4. In addition, examples of the cyclic heterocycle that may be formed by ^R4 and ^R5 include N-acryloylmorpholine and the like.

作為通式(2)所示的化合物的具體例，例如可列舉：N-甲基(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(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺等含N-烷基(甲基)丙烯醯胺衍生物；N-羥甲基(甲基)丙烯醯胺、N-羥乙基(甲基)丙烯醯胺、N-羥甲基-N-丙基(甲基)丙烯醯胺等含N-羥基烷基(甲基)丙烯醯胺衍生物；N-甲氧基甲基丙烯醯胺、N-乙氧基甲基丙烯醯胺等含N-烷氧基(甲基)丙烯醯胺衍生物等。另外，作為含環狀醚基(甲基)丙烯醯胺衍生物，可列舉(甲基)丙烯醯胺基的氮原子形成了雜環的含雜環(甲基)丙烯醯胺衍生物，例如可列舉N-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶、N-丙烯醯基吡咯烷等。這些當中，從反應性優異的方面、得到高彈性模量的固化物的方面、對偏光件的黏接性優異的方面出發，可適宜地使用N-羥乙基丙烯醯胺、N-丙烯醯基嗎啉。Specific examples of the compound represented by the general formula (2) include: N-methyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-hexyl(meth)acrylamide and the like; N-hydroxymethyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxymethyl-N-propyl(meth)acrylamide and the like; N-alkoxy(meth)acrylamide derivatives such as N-methoxymethylacrylamide and N-ethoxymethylacrylamide and the like. In addition, as the cyclic ether group-containing (meth)acrylamide derivative, there can be listed a heterocyclic (meth)acrylamide derivative in which the nitrogen atom of the (meth)acrylamide group forms a heterocyclic ring, for example, N-acryloylmorpholine, N-acryloylpiperidine, N-methylacryloylpiperidine, N-acryloylpyrrolidine, etc. Among these, N-hydroxyethylacrylamide and N-acryloylmorpholine can be suitably used from the aspects of excellent reactivity, the aspect of obtaining a cured product with a high elastic modulus, and the aspect of excellent adhesion to a polarizer.

從隔著黏接劑層使偏光件及透明保護薄膜黏接的情況下的黏接性及耐水性提高的觀點出發，在黏接劑組合物中，通式(2)記載的化合物的含量較佳為0.01~80質量%、更佳為5~60質量%。From the viewpoint of improving the adhesion and water resistance when the polarizer and the transparent protective film are bonded via the adhesive layer, the content of the compound represented by the general formula (2) in the adhesive composition is preferably 0.01 to 80 mass %, more preferably 5 to 60 mass %.

另外，在本發明所使用的黏接劑組合物中，除通式(2)所示的化合物以外，也可以含有其它單官能自由基聚合性化合物作為固化性成分。作為單官能自由基聚合性化合物，可列舉例如具有(甲基)丙烯醯氧基的各種(甲基)丙烯酸衍生物。具體而言，可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-甲基-2-硝基丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸三級戊酯、(甲基)丙烯酸3-戊酯、(甲基)丙烯酸2,2-二甲基丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸十六烷基酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸4-甲基-2-丙基戊酯、(甲基)丙烯酸正十八烷基酯等(甲基)丙烯酸(碳原子數1-20)烷基酯類。In addition, the adhesive composition used in the present invention may contain other monofunctional radical polymerizable compounds as curable components in addition to the compound represented by general formula (2). Examples of monofunctional radical polymerizable compounds include various (meth)acrylic acid derivatives having a (meth)acryloyloxy group. Specifically, for example, alkyl (meth)acrylates (having 1 to 20 carbon atoms) such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, tertiary butyl (meth)acrylate, n-pentyl (meth)acrylate, tertiary pentyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, n-hexyl (meth)acrylate, hexadecyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate and n-octadecyl (meth)acrylate may be cited.

另外，作為上述(甲基)丙烯酸衍生物，可列舉例如：(甲基)丙烯酸環己酯、(甲基)丙烯酸酯環戊酯等(甲基)丙烯酸環烷基酯；(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯；(甲基)丙烯酸2-異冰片酯、(甲基)丙烯酸2-降冰片基甲酯、(甲基)丙烯酸2-降冰片基甲酯、(甲基)丙烯酸5-降冰片烯-2-基甲酯、(甲基)丙烯酸3-甲基-2-降冰片基甲酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、(甲基)丙烯酸二環戊酯等多環式(甲基)丙烯酸酯；(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-甲氧基甲氧基乙酯、(甲基)丙烯酸3-甲氧基丁酯、(甲基)丙烯酸乙基卡必醇酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸烷基苯氧基聚乙二醇酯等含烷氧基或苯氧基的(甲基)丙烯酸酯；等等。這些當中，從與各種保護薄膜的黏接性優異方面出發，較佳為丙烯酸二環戊烯氧基乙酯、丙烯酸苯氧基乙酯。In addition, examples of the (meth)acrylic acid derivatives include: cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate and cyclopentyl (meth)acrylate; aralkyl (meth)acrylates such as benzyl (meth)acrylate; 2-isobornyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 2-norbornyl methyl (meth)acrylate, 5-norbornene-2-yl methyl (meth)acrylate, 3-methyl-2-norbornyl methyl (meth)acrylate, Polycyclic (meth)acrylates such as dicyclopentenyl acrylate, dicyclopentenyloxyethyl (meth)acrylate, and dicyclopentanyl (meth)acrylate; (meth)acrylates containing alkoxy groups or phenoxy groups such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, and alkylphenoxypolyethylene glycol (meth)acrylate; etc. Among these, dicyclopentenyloxyethyl acrylate and phenoxyethyl acrylate are preferred because of their excellent adhesion to various protective films.

另外，作為上述(甲基)丙烯酸衍生物，可列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(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-羥基月桂酯等(甲基)丙烯酸羥基烷基酯、丙烯酸[4-(羥基甲基)環己基]甲酯、環己烷二甲醇單(甲基)丙烯酸酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯等含羥基(甲基)丙烯酸酯；(甲基)丙烯酸縮水甘油酯、4-羥基丁基(甲基)丙烯酸酯縮水甘油醚等含環氧基(甲基)丙烯酸酯；(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,2-三氟乙基乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸十七氟癸酯、(甲基)丙烯酸3-氯-2-羥基丙酯等含鹵素(甲基)丙烯酸酯；(甲基)丙烯酸二甲基胺基乙酯等(甲基)丙烯酸烷基胺基烷基酯；(甲基)丙烯酸3-氧雜環丁基甲酯、(甲基)丙烯酸3-甲基氧雜環丁基甲酯、(甲基)丙烯酸3-乙基氧雜環丁基甲酯、(甲基)丙烯酸3-丁基氧雜環丁基甲酯、(甲基)丙烯酸3-己基氧雜環丁基甲酯等含氧雜環丁基(甲基)丙烯酸酯；(甲基)丙烯酸四氫糠酯、丁內酯(甲基)丙烯酸酯等具有雜環的(甲基)丙烯酸酯、羥基特戊酸新戊二醇(甲基)丙烯酸加成物、對苯基苯酚(甲基)丙烯酸酯等。這些當中，丙烯酸2-羥基-3-苯氧基丙酯由於與各種保護薄膜的黏接性優異，因而較佳。In addition, examples of the (meth)acrylic acid derivatives include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and the like. Hydroxyl (meth)acrylates such as hydroxyalkyl (meth)acrylate, [4-(hydroxymethyl)cyclohexyl]methyl acrylate, cyclohexanedimethanol mono(meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; epoxy (meth)acrylates such as glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether; 2,2,2-trifluoroethyl (meth)acrylate, Halogen-containing (meth)acrylates such as 2,2,2-trifluoroethyl ethyl ester, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, and 3-chloro-2-hydroxypropyl (meth)acrylate; alkylaminoalkyl (meth)acrylates such as dimethylaminoethyl (meth)acrylate; 3-oxacyclobutylmethyl (meth)acrylate, 3-methyloxycyclobutylmethyl (meth)acrylate, Oxygen-containing heterocyclobutyl (meth)acrylates such as heterocyclobutyl methyl ester, 3-ethyloxyheterocyclobutyl methyl (meth)acrylate, 3-butyloxyheterocyclobutyl methyl (meth)acrylate, and 3-hexyloxyheterocyclobutyl methyl (meth)acrylate; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and butyrolactone (meth)acrylate, hydroxypivalic acid neopentyl glycol (meth)acrylate adduct, and p-phenylphenol (meth)acrylate. Among these, 2-hydroxy-3-phenoxypropyl acrylate is preferred because of its excellent adhesion to various protective films.

另外，作為單官能自由基聚合性化合物，可列舉出：(甲基)丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、衣康酸、馬來酸、富馬酸、巴豆酸、異巴豆酸等含羧基單體。Examples of the monofunctional radical polymerizable compound include carboxyl group-containing monomers such as (meth)acrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid.

另外，作為單官能自由基聚合性化合物，例如可列舉出：N-乙烯基吡咯烷酮、N-乙烯基-ε-己內醯胺、甲基乙烯基吡咯烷酮等內醯胺類乙烯基單體；乙烯基吡啶、乙烯基哌啶酮、乙烯基嘧啶、乙烯基哌嗪、乙烯基吡嗪、乙烯基吡咯、乙烯基咪唑、乙烯基噁唑、乙烯基嗎啉等具有含氮雜環的乙烯基類單體等。In addition, as monofunctional free radical polymerizable compounds, for example, there can be listed: vinyl monomers of lactams such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; vinyl monomers having nitrogen-containing heterocyclic rings such as vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, and vinylmorpholine; and the like.

在本發明中使用的黏接劑組合物中，含有單官能自由基聚合性化合物中具有高極性的含羥基(甲基)丙烯酸酯、含羧基(甲基)丙烯酸酯、含磷酸基(甲基)丙烯酸酯等時，對各種基材的密合力提高。作為含羥基(甲基)丙烯酸酯的含量，較佳相對於樹脂組合物為1質量%~30質量%，在其含量過多的情況下，固化物的吸水率變高，存在耐水性惡化的情況。作為含羧基(甲基)丙烯酸酯的含量，較佳相對於樹脂組合物為1質量%~20質量%，在其含量過多的情況下，偏光薄膜的光學耐久性降低，因而不為所欲。作為含磷酸基(甲基)丙烯酸酯，可舉出2-(甲基)丙烯醯氧基乙基酸式磷酸酯，作為其含量，較佳相對於樹脂組合物為0.1質量%~10質量%，在其含量過多的情況下，偏光薄膜的光學耐久性降低，因而不為所欲。When the adhesive composition used in the present invention contains a hydroxyl (meth)acrylate, a carboxyl (meth)acrylate, a phosphoric acid (meth)acrylate, etc. having high polarity among monofunctional free radical polymerizable compounds, the adhesion to various substrates is improved. The content of the hydroxyl (meth)acrylate is preferably 1% to 30% by mass relative to the resin composition. If the content is too high, the water absorption rate of the cured product increases, and there is a possibility of deterioration of water resistance. The content of the carboxyl (meth)acrylate is preferably 1% to 20% by mass relative to the resin composition. If the content is too high, the optical durability of the polarizing film decreases, which is not desirable. As the phosphoric acid group-containing (meth)acrylate, 2-(meth)acryloxyethyl acid phosphate can be cited. Its content is preferably 0.1 mass % to 10 mass % relative to the resin composition. If its content is too high, the optical durability of the polarizing film is reduced, which is not desirable.

另外，作為單官能自由基聚合性化合物，可以使用具有活性亞甲基的自由基聚合性化合物。具有活性亞甲基的自由基聚合性化合物為末端或分子中具有(甲基)丙烯酸基等活性雙鍵基團、且具有活性亞甲基的化合物。作為活性亞甲基，可列舉例如：乙醯乙醯基、烷氧基丙二醯基、或氰基乙醯基等。上述活性亞甲基較佳為乙醯乙醯基。作為具有活性亞甲基的自由基聚合性化合物的具體例，可列舉例如：(甲基)丙烯酸2-乙醯乙醯氧基乙酯、(甲基)丙烯酸2-乙醯乙醯氧基乙基丙酯、(甲基)丙烯酸2-乙醯乙醯氧基乙基-1-甲基乙酯等(甲基)丙烯酸乙醯乙醯氧基乙基烷基酯；(甲基)丙烯酸2-乙氧基丙二醯氧基乙酯、(甲基)丙烯酸2-氰基乙醯氧基乙酯、N-(2-氰基乙醯氧基乙基)丙烯醯胺、N-(2-丙醯基乙醯氧基丁基)丙烯醯胺、N-(4-乙醯乙醯氧基乙基甲基苄基)丙烯醯胺、N-(2-乙醯乙醯基胺基乙基)丙烯醯胺等。具有活性亞甲基的自由基聚合性化合物較佳為(甲基)丙烯酸乙醯乙醯氧基乙基烷基酯。In addition, as a monofunctional free radical polymerizable compound, a free radical polymerizable compound having an active methylene group can be used. The free radical polymerizable compound having an active methylene group is a compound having an active double bond group such as a (meth) acrylic group at the end or in the molecule and having an active methylene group. Examples of the active methylene group include acetoacetyl, alkoxypropanoyl, or cyanoacetyl. The above-mentioned active methylene group is preferably acetoacetyl. Specific examples of free radical polymerizable compounds having an active methylene group include acetyloxyethyl (meth)acrylate 2-acetyloxyethyl propyl (meth)acrylate, 2-acetyloxyethyl 1-methylethyl (meth)acrylate and other acetyloxyethyl alkyl (meth)acrylates; 2-ethoxypropanoyloxyethyl (meth)acrylate, 2-cyanoacetyloxyethyl (meth)acrylate, N-(2-cyanoacetyloxyethyl)acrylamide, N-(2-propionylacetyloxybutyl)acrylamide, N-(4-acetylacetyloxyethylmethylbenzyl)acrylamide, N-(2-acetylacetylaminoethyl)acrylamide and the like. The free radical polymerizable compound having an active methylene group is preferably acetylacetyloxyethyl alkyl (meth)acrylate.

另外，作為二官能以上的多官能自由基聚合性化合物，可列舉例如：作為多官能(甲基)丙烯酰胺衍生物的N,N’-亞甲基雙(甲基)丙烯酰胺、三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、1,10-癸二醇二丙烯酸酯、2-乙基-2-丁基丙二醇二(甲基)丙烯酸酯、雙酚A二(甲基)丙烯酸酯、雙酚A環氧乙烷加成物二(甲基)丙烯酸酯、雙酚A環氧丙烷加成物二(甲基)丙烯酸酯、雙酚A二縮水甘油醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、環狀三羥甲基丙烷甲縮醛(甲基)丙烯酸酯(Cyclic Trimethylolpropane formal(meth)Acrylate)、二噁烷二醇二(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、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、EO改性二甘油四(甲基)丙烯酸酯等(甲基)丙烯酸與多元醇的酯化物、9,9-雙[4-(2-(甲基)丙烯醯氧基乙氧基)苯基]芴。作為具體例，較佳為ARONIX M-220(東亞合成株式會社製)、LIGHT ACRYLATE 1,9ND-A(共榮社化學株式會社製)、LIGHT ACRYLATE DGE-4A(共榮社化學株式會社製)、LIGHT ACRYLATE DCP-A(共榮社化學株式會社製)、SR-531(Sartomer公司製)、CD-536(Sartomer公司製)等。另外，根據需要，可列舉出：各種環氧(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、各種(甲基)丙烯酸酯類單體等。需要說明的是，多官能(甲基)丙烯醯胺衍生物由於不僅聚合速度快、生產率優異，而且將黏接劑組合物製成固化物時的交聯性優異，因而較佳包含於黏接劑組合物中。Examples of the polyfunctional radical polymerizable compound having two or more functional groups include N,N′-methylenebis(meth)acrylamide, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol diacrylate, 2-ethyl- 2-Butylpropylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate, bisphenol A ethylene oxide adduct di(meth)acrylate, bisphenol A propylene oxide adduct di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, cyclotrihydroxymethylpropane methyl acetal (meth)acrylate (Cyclic Esterification products of (meth)acrylic acid and polyols such as trimethylolpropane formal(meth)Acrylate), dioxanediol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, EO-modified diglycerol tetra(meth)acrylate, and 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]fluorene. Specific examples thereof are preferably ARONIX M-220 (manufactured by Toagosei Co., Ltd.), LIGHT ACRYLATE 1,9ND-A (manufactured by Kyoeisha Chemical Co., Ltd.), LIGHT ACRYLATE DGE-4A (manufactured by Kyoeisha Chemical Co., Ltd.), LIGHT ACRYLATE DCP-A (manufactured by Kyoeisha Chemical Co., Ltd.), SR-531 (manufactured by Sartomer Co., Ltd.), CD-536 (manufactured by Sartomer Co., Ltd.), etc. In addition, various epoxy (meth)acrylates, urethane (meth)acrylates, polyester (meth)acrylates, various (meth)acrylate monomers, etc. can be cited as needed. It should be noted that the multifunctional (meth)acrylamide derivative is preferably included in the adhesive composition because it not only has a fast polymerization speed and excellent productivity, but also has excellent crosslinking properties when the adhesive composition is made into a cured product.

從兼顧與偏光件、各種透明保護薄膜的黏接性及嚴苛環境下的光學耐久性的觀點出發，自由基聚合性化合物較佳組合使用單官能自由基聚合性化合物及多官能自由基聚合性化合物。需要說明的是，由於單官能自由基聚合性化合物的液體黏度較低，因此藉由在樹脂組合物中含有單官能自由基聚合性化合物，可以降低樹脂組合物的液體黏度。另外，單官能自由基聚合性化合物多數情況下具有表現出各種功能的官能團，藉由在樹脂組合物中含有單官能自由基聚合性化合物，可以在樹脂組合物及/或樹脂組合物的固化物中表現出各種功能。多官能自由基聚合性化合物由於可使樹脂組合物的固化物三維交聯，因而較佳在樹脂組合物中含有。對於單官能自由基聚合性化合物與多官能自由基聚合性化合物之比而言，相對於單官能自由基聚合性化合物100質量份，較佳將多官能自由基聚合性化合物以10質量份~1000質量份的範圍混合。From the perspective of taking into account the adhesion to polarizers and various transparent protective films and the optical durability in harsh environments, the free radical polymerizable compound is preferably used in combination with a monofunctional free radical polymerizable compound and a polyfunctional free radical polymerizable compound. It should be noted that since the liquid viscosity of the monofunctional free radical polymerizable compound is relatively low, the liquid viscosity of the resin composition can be reduced by including the monofunctional free radical polymerizable compound in the resin composition. In addition, the monofunctional free radical polymerizable compound has a functional group that exhibits various functions in most cases. By including the monofunctional free radical polymerizable compound in the resin composition, various functions can be exhibited in the resin composition and/or the cured product of the resin composition. The polyfunctional free radical polymerizable compound is preferably contained in the resin composition because it can three-dimensionally crosslink the cured product of the resin composition. As for the ratio of the monofunctional free radical polymerizable compound to the polyfunctional free radical polymerizable compound, it is preferred to mix the polyfunctional free radical polymerizable compound in a range of 10 to 1000 parts by mass relative to 100 parts by mass of the monofunctional free radical polymerizable compound.

在活性能量射線使用電子束等的情況下，自由基聚合性黏接劑組合物不需要含有光聚合引發劑，但在活性能量射線使用紫外線或可見光的情況下，較佳黏接劑組合物含有光聚合引發劑。When electron beams or the like are used as the active energy ray, the radical polymerizable adhesive composition does not need to contain a photopolymerization initiator, but when ultraviolet rays or visible light are used as the active energy ray, it is preferred that the adhesive composition contain a photopolymerization initiator.

使用自由基聚合性化合物的情況下的光聚合引發劑可根據活性能量射線而適宜選擇。在藉由紫外線或可見光固化的情況下，使用紫外線或可見光裂解的光聚合引發劑。作為上述光聚合引發劑，例如可列舉出：苯偶醯、二苯甲酮、苯甲醯苯甲酸、3,3’-二甲基-4-甲氧基二苯甲酮等二苯甲酮類化合物；4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α’-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、α-羥基環己基苯基酮等芳香族酮化合物；甲氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉代丙烷-1-酮等苯乙酮類化合物；苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻異丙基醚、苯偶姻丁基醚、茴香偶姻甲基醚等苯偶姻醚類化合物；苯偶醯二甲基縮酮等芳香族縮酮類化合物；2-萘磺醯氯等芳香族磺醯氯類化合物；1-苯基-1,1-丙二酮-2-(鄰乙氧基羰基)肟等光活性肟類化合物；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮、十二烷基噻噸酮等噻噸酮類化合物；樟腦醌；鹵代酮；醯基氧化膦；醯基膦酸酯等。When a radical polymerizable compound is used, the photopolymerization initiator can be appropriately selected according to the active energy ray. When curing by ultraviolet light or visible light, a photopolymerization initiator that is cleaved by ultraviolet light or visible light is used. Examples of the photopolymerization initiator include benzoyl, benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone and the like benzophenone compounds; aromatic ketone compounds such as 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, α-hydroxycyclohexylphenylketone and the like; acetophenone compounds such as methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one and the like; and benzoin methyl ether. , benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, anisolein methyl ether and other benzoin ether compounds; aromatic ketal compounds such as benzoyl dimethyl ketal; aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; optically active oxime compounds such as 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)oxime; thiothione compounds such as thiothione, 2-chlorothiothione, 2-methylthiothione, 2,4-dimethylthiothione, isopropylthiothione, 2,4-dichlorothiothione, 2,4-diethylthiothione, 2,4-diisopropylthiothione, dodecylthiothione; camphorquinone; halogenated ketones; acyl phosphine oxides; acyl phosphonates, etc.

相對於黏接劑組合物的總量，上述光聚合引發劑的摻合量為20質量%以下。光聚合引發劑的摻合量較佳為0.01~20質量%、更佳為0.05~10質量%、進一步更佳為0.1~5質量%。The amount of the photopolymerization initiator blended is 20% by mass or less relative to the total amount of the adhesive composition. The amount of the photopolymerization initiator blended is preferably 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, and even more preferably 0.1 to 5% by mass.

另外，在以含有自由基聚合性化合物作為固化性成分的可見光固化性使用本發明中使用的黏接劑組合物的情況下，特別是以使用對380nm以上的光為高靈敏度的光聚合引發劑為佳。關於對380nm以上的光為高靈敏度的光聚合引發劑，後面進行敘述。In addition, when the adhesive composition used in the present invention is used as a visible light curable adhesive containing a free radical polymerizable compound as a curable component, it is particularly preferred to use a photopolymerization initiator that is highly sensitive to light of 380 nm or more. The photopolymerization initiator that is highly sensitive to light of 380 nm or more will be described later.

作為上述光聚合引發劑，較佳單獨使用下述通式(3)所示的化合物；或者組合使用通式(3)所示的化合物及後面敘述的對380nm以上的光高靈敏度的光聚合引發劑。 [化學式5] (式中，R⁶ 及R⁷ 表示-H、-CH₂ CH₃ 、-iPr或Cl，R⁶ 及R⁷ 可以相同或不同)。使用通式(3)所示的化合物的情況下，與單獨使用對380nm以上的光具有高靈敏度的光聚合引發劑的情況相比，黏接性優異。通式(3)所示的化合物中，特佳R⁶ 及R⁷ 為-CH₂ CH₃ 的二乙基噻噸酮。相對於固化性樹脂組合物的總量，固化性樹脂組合物中的通式(3)所示的化合物的組成比率較佳為0.1~5質量%、更佳為0.5~4質量%、進一步更佳為0.9~3質量%。As the above-mentioned photopolymerization initiator, it is preferred to use the compound represented by the following general formula (3) alone; or to use the compound represented by the general formula (3) in combination with the photopolymerization initiator with high sensitivity to light above 380 nm described later. [Chemical Formula 5] (In the formula, ^R6 and ^R7 represent -H, _-CH2CH3 , _-iPr or Cl, and ^R6 and ^R7 may be the same or different). When the compound represented by the general formula (3) is used, the adhesion is excellent compared to the case where a photopolymerization initiator having high sensitivity to light of 380 nm or more is used alone. Among the compounds represented by the general formula (3), _{diethylthiothione} in which ^R6 and ^R7 are _-CH2CH3 is particularly preferred. The composition ratio of the compound represented by the general formula (3) in the curable resin composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and even more preferably 0.9 to 3% by mass, relative to the total amount of the curable resin composition.

另外，較佳根據需要添加聚合引發助劑。作為聚合引發助劑，可列舉出：三乙胺、二乙胺、N-甲基二乙醇胺、乙醇胺、4-二甲基胺基苯甲酸、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯等，特佳為4-二甲基胺基苯甲酸乙酯。在使用聚合引發助劑的情況下，其添加量相對於固化性樹脂組合物的總量通常為0~5質量%、較佳為0~4質量%、最佳為0~3質量%。In addition, it is preferred to add a polymerization initiation aid as needed. Examples of the polymerization initiation aid include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and the like, with ethyl 4-dimethylaminobenzoate being particularly preferred. When a polymerization initiation aid is used, the amount added is generally 0 to 5% by mass, preferably 0 to 4% by mass, and most preferably 0 to 3% by mass relative to the total amount of the curable resin composition.

另外，可以根據需要組合使用公知的光聚合引發劑。具有UV吸收能力的透明保護薄膜由於不透過380nm以下的光，因此，作為光聚合引發劑，較佳使用對380nm以上的光為高靈敏度的光聚合引發劑。具體而言，可列舉出：2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-1-丁酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮、2,4,6-三甲基苯甲醯基二苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、雙(η5-2,4-環戊二烯-1-基)雙(2,6-二氟-3-(1H-吡咯-1-基)苯基)鈦等。In addition, a known photopolymerization initiator may be used in combination as needed. Since the transparent protective film having UV absorption ability does not transmit light below 380 nm, it is preferred to use a photopolymerization initiator that is highly sensitive to light above 380 nm as the photopolymerization initiator. Specifically, there can be cited: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.

特別地，作為光聚合引發劑，較佳除通式(3)的光聚合引發劑以外進一步含有下述通式(4)表示的化合物， [化學式6] (式中，R⁸ 、R⁹ 及R¹⁰ 表示-H、-CH₃ 、-CH₂ CH₃ 、-iPr或Cl，R⁸ 、R⁹ 及R¹⁰ 可以相同或不同)。作為通式(4)所示的化合物，可以適宜使用作為市售品的2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙烷-1-酮(商品名：IRGACURE907、製造商：BASF)。此外，2-苄基-2-二甲基胺基-1-(4-嗎啉代苯基)-1-丁酮(商品名：IRGACURE369、製造商：BASF)、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮(商品名：IRGACURE379、製造商：BASF)由於靈敏度高，因而較佳。In particular, as the photopolymerization initiator, it is preferred that the photopolymerization initiator further contains a compound represented by the following general formula (4) in addition to the photopolymerization initiator of the general formula (3): [Chemical Formula 6] (wherein, R ⁸ , R ⁹ and R ¹⁰ represent -H, -CH ₃ , -CH ₂ CH ₃ , -iPr or Cl, and may be the same or ^different .) As the compound represented by the general formula ( ⁴ ), commercially available ² -methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (trade name: IRGACURE 907, manufacturer: BASF) can be suitably used. In addition, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone (trade name: IRGACURE 369, manufacturer: BASF) and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone (trade name: IRGACURE 379, manufacturer: BASF) are preferred because of their high sensitivity.

在上述黏接劑組合物中，使用具有活性亞甲基的自由基聚合性化合物作為自由基聚合性化合物時，較佳與具有奪氫作用的自由基聚合引發劑組合使用。根據該構成，特別是即使剛從高濕度環境中或水中取出後(非乾燥狀態)，偏光薄膜所具有的黏接劑層的黏接性也顯著提高。其理由尚未明確，但認為是以下的原因。也就是說，具有活性亞甲基的自由基聚合性化合物與構成黏接劑層的其它自由基聚合性化合物一起聚合，進入到黏接劑層中的基礎聚合物的主鏈及/或側鏈，形成黏接劑層。在該聚合過程中，如果存在具有奪氫作用的自由基聚合引發劑，則形成構成黏接劑層的基礎聚合物，並從具有活性亞甲基的自由基聚合性化合物中奪取氫，在亞甲基中產生自由基。而且，產生自由基的亞甲基與PVA等偏光件的羥基反應，在黏接劑層與偏光件之間形成共價鍵。其結果，推測特別是即使在非乾燥狀態下，偏光薄膜所具有的黏接劑層的黏接性也顯著提高。In the above-mentioned adhesive composition, when a radical polymerizable compound having an active methylene group is used as the radical polymerizable compound, it is preferably used in combination with a radical polymerization initiator having a hydrogen-scavenging effect. According to this structure, the adhesion of the adhesive layer possessed by the polarizing film is significantly improved, especially even just after being taken out of a high humidity environment or water (non-dry state). The reason is not yet clear, but it is believed to be the following. That is, the radical polymerizable compound having an active methylene group is polymerized together with other radical polymerizable compounds constituting the adhesive layer, and enters into the main chain and/or side chain of the base polymer in the adhesive layer to form an adhesive layer. In the polymerization process, if there is a radical polymerization initiator with hydrogen abstraction, a base polymer constituting the adhesive layer is formed, and hydrogen is abstracted from the radical polymerizable compound having an active methylene group to generate a free radical in the methylene group. Furthermore, the methylene group generated with the free radical reacts with the hydroxyl group of the polarizer such as PVA to form a covalent bond between the adhesive layer and the polarizer. As a result, it is estimated that the adhesiveness of the adhesive layer of the polarizing film is significantly improved even in a non-dried state.

在本發明中，作為具有奪氫作用的自由基聚合引發劑，可列舉例如：噻噸酮類自由基聚合引發劑、二苯甲酮類自由基聚合引發劑等。上述自由基聚合引發劑較佳為噻噸酮類自由基聚合引發劑。作為噻噸酮類自由基聚合引發劑，可列舉例如上述通式(3)所示的化合物。作為通式(3)所示的化合物的具體例，可列舉例如：噻噸酮、二甲基噻噸酮、二乙基噻噸酮、異丙基噻噸酮、氯噻噸酮等。通式(3)所示的化合物中，特佳R⁶ 及R⁷ 為-CH₂ CH₃ 的二乙基噻噸酮。In the present invention, as the free radical polymerization initiator having a hydrogen abstracting effect, for example, thiothione free radical polymerization initiators, benzophenone free radical polymerization initiators, etc. can be listed. The above-mentioned free radical polymerization initiator is preferably a thiothione free radical polymerization initiator. As the thiothione free radical polymerization initiator, for example, the compound represented by the above general formula (3) can be listed. As specific examples of the compound represented by the general formula (3), for example, thiothione, dimethylthiothione, diethylthiothione, isopropylthiothione, chlorothiothione, etc. can be listed. Among the compounds represented by the general formula (3), diethylthiothione wherein R ⁶ and R ⁷ are -CH ₂ CH ₃ is particularly preferred.

在上述黏接劑組合物中含有具有活性亞甲基的自由基聚合性化合物及具有奪氫作用的自由基聚合引發劑的情況下，將固化性成分的總量設為100質量%時，相對於固化性樹脂組合物的總量，較佳含有上述具有活性亞甲基的自由基聚合性化合物1~50質量%、及自由基聚合引發劑0.1~10質量%。When the above-mentioned adhesive composition contains a free radical polymerizable compound having an active methylene group and a free radical polymerization initiator having a hydrogen abstracting effect, when the total amount of the curable component is set to 100 mass %, it is preferred that the free radical polymerizable compound having an active methylene group and the free radical polymerization initiator are contained in an amount of 1 to 50 mass % and 0.1 to 10 mass % respectively relative to the total amount of the curable resin composition.

如上所述，在本發明中，在具有奪氫作用的自由基聚合引發劑的存在下，使具有活性亞甲基的自由基聚合性化合物的亞甲基產生自由基，該亞甲基與PVA等偏光件的羥基反應，形成共價鍵。因此，為了使具有活性亞甲基的自由基聚合性化合物的亞甲基產生自由基，充分形成該共價鍵，將固化性成分的總量設為100質量%時，較佳含有具有活性亞甲基的自由基聚合性化合物1~50質量%，更佳含有3~30質量%。為了充分提高耐水性、提高在非乾燥狀態下的黏接性，較佳將具有活性亞甲基的自由基聚合性化合物設為1質量%以上。另一方面，如果超過50質量%，則存在發生黏接劑層的固化不良的情況。另外，相對於黏接劑組合物的總量，較佳含有具有奪氫作用的自由基聚合引發劑0.1~10質量%，更佳含有0.3~9質量%。為了使奪氫反應充分進行，較佳使用自由基聚合引發劑0.1質量%以上。另一方面，如果大於10質量%，則有時在組合物中不完全溶解。As described above, in the present invention, in the presence of a radical polymerization initiator having a hydrogen-scavenging effect, a free radical is generated from the methylene group of a radical polymerizable compound having an active methylene group, and the methylene group reacts with a hydroxyl group of a polarizer such as PVA to form a covalent bond. Therefore, in order to generate a free radical from the methylene group of a radical polymerizable compound having an active methylene group and fully form the covalent bond, when the total amount of the curable component is set to 100% by mass, it is preferred that 1 to 50% by mass of a radical polymerizable compound having an active methylene group is contained, and more preferably 3 to 30% by mass. In order to fully improve water resistance and improve adhesion in a non-dry state, it is preferred that the radical polymerizable compound having an active methylene group is set to 1% by mass or more. On the other hand, if it exceeds 50% by mass, there is a possibility that the adhesive layer is poorly cured. In addition, relative to the total amount of the adhesive composition, it is preferred to contain 0.1 to 10% by weight of a free radical polymerization initiator having a hydrogenation effect, and more preferably 0.3 to 9% by weight. In order to allow the hydrogenation reaction to proceed sufficiently, it is preferred to use more than 0.1% by weight of the free radical polymerization initiator. On the other hand, if it is greater than 10% by weight, it may not be completely dissolved in the composition.

本發明中使用的黏接劑組合物根據需要較佳進一步含有下述成分。The adhesive composition used in the present invention preferably further contains the following components as necessary.

在本發明中，可以在黏接劑組合物中摻合上述通式(1)中記載的化合物、較佳摻合上述通式(1’)中記載的化合物、更佳摻合後面敘述的通式(1a)~(1d)記載的化合物。在黏接劑組合物中摻合這些化合物時，與偏光件、透明保護薄膜的黏接性有時會提高，因而較佳。從提高偏光件與透明保護薄膜的黏接性及耐水性的觀點考慮，在黏接劑組合物中，上述通式(1)記載的化合物的含量較佳為0.001~50質量%、更佳為0.1~30質量%、最佳為1~10質量%。In the present invention, the compound described in the general formula (1) can be blended into the adhesive composition, preferably the compound described in the general formula (1'), and more preferably the compound described in the general formula (1a) to (1d) described later. When these compounds are blended into the adhesive composition, the adhesion with the polarizer and the transparent protective film is sometimes improved, which is preferred. From the perspective of improving the adhesion and water resistance of the polarizer and the transparent protective film, the content of the compound described in the general formula (1) in the adhesive composition is preferably 0.001~50 mass%, more preferably 0.1~30 mass%, and most preferably 1~10 mass%.

氣泡抑制劑是藉由摻合到黏接劑組合物中而能夠降低表面張力的化合物，從而具有減少與待貼合的被黏附物之間的氣泡的效果。作為氣泡抑制劑，可使用例如：聚二甲基矽氧烷等具有聚矽氧烷骨架的有機矽類氣泡抑制劑、使(甲基)丙烯酸酯等聚合而成的具有(甲基)丙烯醯骨架的(甲基)丙烯酸類氣泡抑制劑、使乙烯基醚、環狀醚等聚合而成的聚醚類氣泡抑制劑、由具有全氟烷基的含氟化合物形成的氟性氣泡抑制劑等、在添加到黏接劑組合物中時具有減少其表面張力的效果的氣泡抑制劑。Bubble suppressors are compounds that can reduce surface tension by being mixed into adhesive compositions, thereby having the effect of reducing bubbles between the adhesive composition and the adherend to be bonded. Examples of bubble suppressors that can be used include organic silicon bubble suppressors having a polysiloxane skeleton such as polydimethylsiloxane, (meth) acrylic bubble suppressors having a (meth) acrylic skeleton formed by polymerizing (meth) acrylic esters, polyether bubble suppressors formed by polymerizing vinyl ethers, cyclic ethers, and the like, and fluorine bubble suppressors formed by fluorine-containing compounds having perfluoroalkyl groups, which have the effect of reducing surface tension when added to adhesive compositions.

氣泡抑制劑較佳在化合物中具有反應性基團。在該情況下，將偏光件及透明保護薄膜貼合時，可以減少層壓氣泡的產生。作為氣泡抑制劑所具有的反應性基團，可列舉聚合性官能團，具體而言，可列舉例如(甲基)丙烯醯基、乙烯基、烯丙基等具有烯屬雙鍵的自由基聚合性官能團、縮水甘油基等環氧基、氧雜環丁基、乙烯基醚基、環狀醚基、環狀硫醚基、內酯基等陽離子聚合性官能團等。從在黏接劑組合物中的反應性的觀點出發，較佳具有雙鍵作為反應性基團的氣泡抑制劑，更佳具有(甲基)丙烯醯基的氣泡抑制劑。The bubble suppressant preferably has a reactive group in the compound. In this case, when the polarizer and the transparent protective film are bonded together, the generation of lamination bubbles can be reduced. As the reactive group possessed by the bubble suppressant, there can be listed polymerizable functional groups, specifically, free radical polymerizable functional groups having olefinic double bonds such as (meth)acryl, vinyl, and allyl, epoxide groups such as glycidyl, cyclobutylene, vinyl ether, cyclic ether, cyclic thioether, and lactone groups, etc., cationic polymerizable functional groups, etc. From the viewpoint of reactivity in the adhesive composition, a bubble suppressant having a double bond as a reactive group is preferred, and a bubble suppressant having a (meth)acryloyl group is more preferred.

在考慮層壓氣泡抑制效果及黏接性提高效果的情況下，在上述氣泡抑制劑中，較佳有機矽類氣泡抑制劑。另外，在氣泡抑制劑中，在考慮黏接劑層的黏接性的情況下，較佳在主鏈骨架或側鏈中含有胺基甲酸酯鍵、異氰脲酸酯環結構的氣泡抑制劑。作為有機矽類氣泡抑制劑，也可以適宜地使用市售品，可列舉例如作為丙烯醯基改性聚二甲基矽氧烷的“BYK-UV3505” (BYK-Chemie Japan公司製)。In consideration of the bubble suppression effect of layer pressure and the effect of improving adhesion, among the bubble suppressants, organic silicon bubble suppressants are preferred. In addition, among the bubble suppressants, in consideration of the adhesion of the adhesive layer, bubble suppressants containing a urethane bond or an isocyanurate ring structure in the main chain skeleton or the side chain are preferred. As the organic silicon bubble suppressant, commercially available products can also be appropriately used, for example, "BYK-UV3505" (manufactured by BYK-Chemie Japan Co., Ltd.) which is an acryl-modified polydimethylsiloxane can be cited.

為了兼備得到的黏接劑層的黏接力及層壓氣泡的減少效果，將黏接劑組合物的總量設為100質量%時，氣泡抑制劑的含量較佳為0.01~0.6質量%。In order to achieve both the adhesive strength of the obtained adhesive layer and the effect of reducing the pressure bubbles, the content of the bubble inhibitor is preferably 0.01 to 0.6 mass % when the total amount of the adhesive composition is 100 mass %.

在本發明使用的黏接劑組合物中，除上述自由基聚合性化合物的固化性成分以外，還可以含有使(甲基)丙烯酸單體聚合而成的丙烯酸類低聚物。藉由在黏接劑組合物中含有該丙烯酸類低聚物，可以降低對該組合物照射活性能量射線並使其固化時的固化收縮，從而減少黏接劑與偏光件及透明保護薄膜等被黏附物的界面應力。其結果，可抑制黏接劑層與被黏附物的黏接性降低。為了充分抑制固化物層(黏接劑層)的固化收縮，相對於黏接劑組合物的總量，丙烯酸類低聚物的含量較佳為20質量%以下、更佳為15質量%以下。黏接劑組合物中的丙烯酸類低聚物的含量過多時，存在對該組合物照射活性能量射線時的反應速度急劇降低而變得固化不良的情況。另一方面，相對於黏接劑組合物的總量，較佳含有丙烯酸類低聚物3質量%以上、更佳含有5質量%以上。In the adhesive composition used in the present invention, in addition to the curing component of the free radical polymerizable compound, an acrylic oligomer formed by polymerizing a (meth) acrylic acid monomer may also be contained. By containing the acrylic oligomer in the adhesive composition, the curing shrinkage when the composition is irradiated with active energy rays and cured can be reduced, thereby reducing the interfacial stress between the adhesive and the adherends such as polarizers and transparent protective films. As a result, the reduction in adhesion between the adhesive layer and the adherend can be suppressed. In order to fully suppress the curing shrinkage of the cured layer (adhesive layer), the content of the acrylic oligomer is preferably less than 20% by mass, and more preferably less than 15% by mass, relative to the total amount of the adhesive composition. When the content of the acrylic oligomer in the adhesive composition is too high, the reaction rate when the composition is irradiated with active energy rays is rapidly reduced, resulting in poor curing. On the other hand, the acrylic oligomer is preferably contained in an amount of 3% by mass or more, more preferably 5% by mass or more, relative to the total amount of the adhesive composition.

在考慮塗敷時的作業性、均勻性的情況下，較佳黏接劑組合物為低黏度，因此，(甲基)丙烯酸類單體聚合而成的丙烯酸類低聚物也較佳為低黏度。作為能夠防止黏接劑層的固化收縮的低黏度的丙烯酸類低聚物，其重均分子量(Mw)較佳為15000以下、更佳為10000以下、特佳為5000以下。另一方面，為了充分抑制固化物層(黏接劑層)的固化收縮，丙烯酸類低聚物的重均分子量(Mw)較佳為500以上、更佳為1000以上、特佳為1500以上。作為構成丙烯酸類低聚物的(甲基)丙烯酸類單體，具體可列舉例如：(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸2-甲基-2-硝基丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸三級戊酯、(甲基)丙烯酸3-戊酯、(甲基)丙烯酸2,2-二甲基丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸鯨蠟酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸4-甲基-2-丙基戊酯、(甲基)丙烯酸正十八烷基酯等(甲基)丙烯酸(碳原子數1-20)烷基酯類、以及例如：(甲基)丙烯酸環烷基酯(例如(甲基)丙烯酸環己酯、(甲基)丙烯酸酯環戊酯等)、(甲基)丙烯酸芳烷基酯(例如(甲基)丙烯酸苄酯等)、多環式(甲基)丙烯酸酯(例如(甲基)丙烯酸2-異冰片酯、(甲基)丙烯酸-2-降冰片基甲酯、(甲基)丙烯酸5-降冰片烯-2-基甲酯、(甲基)丙烯酸3-甲基-2-降冰片基甲酯等)、含羥基(甲基)丙烯酸酯類(例如(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2,3-二羥基丙基甲基丁酯等)、含烷氧基或苯氧基(甲基)丙烯酸酯類((甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸2-乙氧基乙酯、(甲基)丙烯酸2-甲氧基甲氧基乙酯、(甲基)丙烯酸3-甲氧基丁酯、(甲基)丙烯酸乙基卡必醇酯、(甲基)丙烯酸苯氧基乙酯等)、含環氧基(甲基)丙烯酸酯類(例如(甲基)丙烯酸縮水甘油酯等)、含鹵素(甲基)丙烯酸酯類(例如(甲基)丙烯酸2,2,2-三氟乙酯、(甲基)丙烯酸2,2,2-三氟乙基乙酯、(甲基)丙烯酸四氟丙酯、(甲基)丙烯酸六氟丙酯、(甲基)丙烯酸八氟戊酯、(甲基)丙烯酸十七氟癸酯等)、(甲基)丙烯酸烷基胺基烷基酯(例如，(甲基)丙烯酸二甲基胺基乙酯等)等。這些(甲基)丙烯酸酯可以單獨使用或組合使用2種以上。作為丙烯酸類低聚物的具體例，可列舉東亞合成株式會社製“ARUFON”、綜研化學株式會社製“ACTFLOW”、BASF Japan Ltd.製“JONCRYL”等。In consideration of workability and uniformity during application, the adhesive composition preferably has a low viscosity, and therefore, the acrylic oligomer obtained by polymerization of the (meth)acrylic monomer also preferably has a low viscosity. As a low-viscosity acrylic oligomer capable of preventing the curing shrinkage of the adhesive layer, its weight average molecular weight (Mw) is preferably 15,000 or less, more preferably 10,000 or less, and particularly preferably 5,000 or less. On the other hand, in order to fully suppress the curing shrinkage of the cured product layer (adhesive layer), the weight average molecular weight (Mw) of the acrylic oligomer is preferably 500 or more, more preferably 1,000 or more, and particularly preferably 1,500 or more. Specific examples of the (meth)acrylic monomer constituting the acrylic oligomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-methyl-2-nitropropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, dibutyl (meth)acrylate, tertiary butyl (meth)acrylate, n-pentyl (meth)acrylate, tertiary pentyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, n-butyl (meth)acrylate, tertiary ... (meth)acrylate (carbon number 1-20) alkyl esters such as 2-hexyl (meth)acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate, and n-octadecyl (meth)acrylate, and cycloalkyl (meth)acrylates (e.g., cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, etc.), aralkyl (meth)acrylates (e.g., benzyl (meth)acrylate, etc.), polycyclic (meth)acrylates (e.g., 2-isobornyl (meth)acrylate, -2-norbornyl methyl (meth)acrylate, 5-norbornene-2-yl methyl (meth)acrylate, 3-methyl-2-norbornyl methyl (meth)acrylate, etc.), hydroxyl-containing (meth)acrylates (e.g., hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl methylbutyl (meth)acrylate, etc.), alkoxy- or phenoxy-containing (meth)acrylates (2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxymethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, The (meth)acrylates may be ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, etc.), epoxy-containing (meth)acrylates (e.g., glycidyl (meth)acrylate, etc.), halogen-containing (meth)acrylates (e.g., 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl ethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, hexafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, etc.), alkylaminoalkyl (meth)acrylates (e.g., dimethylaminoethyl (meth)acrylate, etc.). These (meth)acrylates may be used alone or in combination of two or more. Specific examples of acrylic oligomers include "ARUFON" manufactured by Toagosei Co., Ltd., "ACTFLOW" manufactured by Soken Chemical Co., Ltd., and "JONCRYL" manufactured by BASF Japan Ltd.

可以在上述黏接劑組合物中含有光產酸劑。在上述黏接劑組合物中含有光產酸劑的情況下，可大幅提高黏接劑層的耐水性及耐久性。光產酸劑可以由下述通式(5)表示。The adhesive composition may contain a photoacid generator. When the adhesive composition contains a photoacid generator, the water resistance and durability of the adhesive layer can be greatly improved. The photoacid generator can be represented by the following general formula (5).

通式(5) [化學式7] (其中，L^＋ 表示任意的鎓陽離子。另外，X^- 表示選自於由PF₆ ^- 、SbF₆ ^- 、AsF₆ ^- 、SbCl₆ ^- 、BiCl₅ ^- 、SnCl₆ ^- 、ClO₄ ^- 、二硫代胺基甲酸鹽陰離子、SCN^- 所構成組群中的抗衡陰離子。)General formula (5) [Chemical formula 7] (Wherein, L ⁺ represents an arbitrary onium cation. In addition, X ^- represents a counter anion selected from the group consisting of PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- , dithiocarbamate anions, and SCN ^- .)

接下來，對通式(5)中的抗衡陰離子X^- 進行說明。Next, the counter anion ^X- in the general formula (5) will be described.

原理上對通式(5)中的抗衡陰離子X^- 沒有特殊限定，較佳非親核性陰離子。抗衡陰離子X為非親核性陰離子的情況下，由於不易引起分子內共存的陽離子、組合使用的各種材料的親核反應，結果能夠提高由通式(5)表示的光產酸劑自身、使用其的組合物的經時穩定性。這裡所說的非親核性陰離子是指引起親核反應的能力低的陰離子。作為這樣的陰離子，可列舉：PF₆ ^- 、SbF₆ ^- 、AsF₆ ^- 、SbCl₆ ^- 、BiCl₅ ^- 、SnCl₆ ^- 、ClO₄ ^- 、二硫代胺基甲酸鹽陰離子、SCN^- 等。In principle, there is no particular limitation on the counter anion ^X- in the general formula (5), and a non-nucleophilic anion is preferred. When the counter anion X is a non-nucleophilic anion, it is less likely to cause a nucleophilic reaction with coexisting cations in the molecule or with various materials used in combination, and as a result, the stability over time of the photoacid generator represented by the general formula (5) itself and the composition using the same can be improved. The non-nucleophilic anion mentioned here refers to an anion with a low ability to cause a nucleophilic reaction. Examples of such anions include PF ₆ ^- , SbF ₆ ^- , AsF ₆ ^- , SbCl ₆ ^- , BiCl ₅ ^- , SnCl ₆ ^- , ClO ₄ ^- , dithiocarbamate anions, and SCN ^- .

具體而言，作為本發明的光產酸劑的較佳具體例，可以舉出：“CYRACURE UVI-6992”、“CYRACURE UVI-6974”(以上，Dow ChemicalJapan Limited製)、“Adekaoptomer SP150”、“Adekaoptomer SP152”、“AdekaoptomerSP170”、“Adekaoptomer SP172”(以上，株式會社ADEKA製)、“IRGACURE250”(CibaSpecialty Chemicals Inc.制)、“CI-5102”、“CI-2855”(以上，Nippon Soda Co.,Ltd.製)、“San-Aid SI-60L”、“San-Aid SI-80L”、“San-Aid SI-100L”、“San-Aid SI-110L”、“San-Aid SI-180L”(以上，三新化學株式會社製)、“CPI-100P”、“CPI-100A”(以上，San-Apro Ltd.製)、“WPI-069”、“WPI-113”、“WPI-116”、“WPI-041”、“WPI-044”、“WPI-054”、“WPI-055”、“WPAG-281”、“WPAG-567”、“WPAG-596”(以上，和光純藥株式會社製)。Specifically, preferred specific examples of the photoacid generator of the present invention include: "CYRACURE UVI-6992", "CYRACURE UVI-6974" (above, manufactured by Dow Chemical Japan Limited), "Adekaoptomer SP150", "Adekaoptomer SP152", "Adekaoptomer SP170", "Adekaoptomer SP172" (above, manufactured by ADEKA Co., Ltd.), "IRGACURE 250" (manufactured by Ciba Specialty Chemicals Inc.), "CI-5102", "CI-2855" (above, manufactured by Nippon Soda Co., Ltd.), "San-Aid SI-60L", "San-Aid SI-80L", "San-Aid SI-100L", "San-Aid SI-110L", "San-Aid SI-180L" (above, manufactured by Sanshin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (above, manufactured by San-Apro Ltd.), "WPI-069", "WPI-113", "WPI-116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG-567", "WPAG-596" (above, manufactured by Wako Junyaku Co., Ltd.).

相對於黏接劑組合物的總量，光產酸劑的含量為10質量%以下、較佳為0.01~10質量%、更佳為0.05~5質量%、特佳為0.1~3質量%。The content of the photoacid generator is 10% by mass or less, preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and particularly preferably 0.1 to 3% by mass, relative to the total amount of the adhesive composition.

光產鹼劑是藉由紫外線、可見光等的光照射而使分子結構變化或者分子裂解而生成1種以上可作為自由基聚合性化合物、環氧樹脂的聚合反應的催化劑發揮功能的鹼性物質的化合物。作為鹼性物質，可列舉例如二級胺、三級胺。作為光產鹼劑，可列舉例如上述α-胺基苯乙酮化合物、上述肟酯化合物、具有醯氧基亞胺基、N-甲醯化芳香族胺基、N-醯基化芳香族胺基、硝基苄基胺基甲酸酯基、烷氧基苄基胺基甲酸酯基等取代基的化合物。其中較佳為肟酯化合物。Photoalkali generators are compounds that change their molecular structure or break down their molecules by irradiation with ultraviolet light, visible light, etc., to generate one or more alkaline substances that can function as catalysts for polymerization reactions of free radical polymerizable compounds and epoxy resins. Examples of alkaline substances include diamines and tertiary amines. Examples of photoalkali generators include the above-mentioned α-aminoacetophenone compounds, the above-mentioned oxime ester compounds, compounds having substituents such as acyloxyimino groups, N-formylated aromatic amine groups, N-acylated aromatic amine groups, nitrobenzylcarbamate groups, and alkoxybenzylcarbamate groups. Oxime ester compounds are preferred.

作為具有醯氧基亞胺基的化合物，可列舉例如：O,O’-琥珀酸二苯乙酮肟、O,O’-琥珀酸二萘並苯酮肟、二苯甲酮肟丙烯酸酯-苯乙烯共聚物。Examples of the compound having an acyloxyimino group include O,O'-succinic acid dibenzoacetophenone oxime, O,O'-succinic acid dinaphthobenzophenone oxime, and benzophenone oxime acrylate-styrene copolymer.

作為具有N-甲醯化芳香族胺基、N-醯基化芳香族胺基的化合物，可列舉例如：二-N-(對甲醯基胺基)二苯基甲烷、二-N-(對乙醯基胺基)二苯基甲烷、二-N-(對苯甲醯胺基)二苯基甲烷、4-甲醯胺基二苯乙烯、4-乙醯胺基二苯乙烯、2,4-二甲醯基胺基二苯乙烯、1-甲醯基胺基萘、1-乙醯基胺基萘、1,5-二甲醯基胺基萘、1-甲醯基胺基蒽、1,4-二甲醯基胺基蒽、1-乙醯基胺基蒽、1,4-二甲醯基胺基蒽醌、1,5-二甲醯基胺基蒽醌、3,3’-二甲基-4,4’-二甲醯基胺基聯苯、4,4’-二甲醯基胺基二苯甲酮。Examples of the compound having an N-formylated aromatic amine group or an N-acylated aromatic amine group include di-N-(p-formylamino)diphenylmethane, di-N-(p-acetylamino)diphenylmethane, di-N-(p-benzylamino)diphenylmethane, 4-formylaminostilbene, 4-acetylaminostilbene, 2,4-diformylaminostilbene, , 1-methylaminonaphthalene, 1-acetylaminonaphthalene, 1,5-dimethylaminonaphthalene, 1-methylaminoanthracene, 1,4-dimethylaminoanthracene, 1-acetylaminoanthracene, 1,4-dimethylaminoanthraquinone, 1,5-dimethylaminoanthraquinone, 3,3'-dimethyl-4,4'-dimethylaminobiphenyl, 4,4'-dimethylaminobenzophenone.

作為具有硝基苄基胺基甲酸酯基、烷氧基苄基胺基甲酸酯基的化合物，可列舉例如：雙{{(2-硝基苄基)氧基}羰基}二胺基二苯基甲烷、2,4-二{(2-硝基苄基)氧基}二苯乙烯、雙{(2-硝基苄基氧基)羰基}己烷-1,6-二胺、鄰二甲代苯胺{{(2-硝基-4-氯苄基)氧基}醯胺}。Examples of the compound having a nitrobenzylcarbamate group or an alkoxybenzylcarbamate group include bis{{(2-nitrobenzyl)oxy}carbonyl}diaminodiphenylmethane, 2,4-bis{(2-nitrobenzyl)oxy}stilbene, bis{(2-nitrobenzyloxy)carbonyl}hexane-1,6-diamine, and o-xylidine{{(2-nitro-4-chlorobenzyl)oxy}amide.

光產鹼劑較佳為選自肟酯化合物及α-胺基苯乙酮化合物中的至少任1種，更佳為肟酯化合物。作為α-胺基苯乙酮化合物，特別是以具有2個以上氮原子的α-胺基苯乙酮化合物為佳。The photobase generator is preferably at least one selected from an oxime ester compound and an α-aminoacetophenone compound, and is more preferably an oxime ester compound. As the α-aminoacetophenone compound, an α-aminoacetophenone compound having two or more nitrogen atoms is particularly preferred.

作為其它光產鹼劑，可使用WPBG-018(商品名，9-蒽基甲基-N,N’-二乙基胺基甲酸酯(9-anthrylmethyl N,N’-diethylcarbamate))、WPBG-027(商品名，(E)-1-[3-(2-羥基苯基)-2-丙烯醯基]哌啶((E)-1-[3-(2-hydroxyphenyl) -2-propenoyl]piperidine))、WPBG-082(商品名，2-(3-苯甲醯基苯基)丙酸胍鹽(guanidinium2-(3-benzoylphenyl)propionate))、WPBG-140(商品名，1-(蒽醌-2-基)乙基咪唑羧酸鹽(1-(anthraquinon-2-yl)ethyl imidazolecarboxylate))等光產鹼劑。As other photoalkalizers, WPBG-018 (trade name, 9-anthrylmethyl N,N’-diethylcarbamate), WPBG-027 (trade name, (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl]piperidine), WPBG-082 (trade name, guanidinium2-(3-benzoylphenyl)propionate), WPBG-140 (trade name, 1-(anthraquinon-2-yl)ethylimidazolecarboxylate) and the like can be used.

在上述黏接劑組合物中，可以在黏接劑組合物中組合使用光產酸劑及含有烷氧基、環氧基中的任一基團的化合物。In the above adhesive composition, a photoacid generator and a compound containing either an alkoxy group or an epoxy group may be used in combination.

在使用分子內具有1個以上環氧基的化合物或分子內具有2個以上環氧基的高分子(環氧樹脂)的情況下，可以組合使用分子內具有兩個以上與環氧基具有反應性的官能團的化合物。其中，與環氧基具有反應性的官能團例如可列舉：羧基、酚羥基、巰基、一級或二級芳香族胺基等。考慮到三維固化性，特佳為一分子中具有2個以上這些官能團。When using a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule, a compound having two or more functional groups reactive with the epoxy groups in the molecule may be used in combination. Examples of the functional groups reactive with the epoxy groups include carboxyl groups, phenolic hydroxyl groups, hydroxyl groups, primary or secondary aromatic amine groups, etc. In view of three-dimensional curability, it is particularly preferred to have two or more of these functional groups in one molecule.

作為分子內具有1個以上環氧基的高分子，例如可列舉環氧樹脂，包括由雙酚A及環氧氯丙烷衍生的雙酚A型環氧樹脂、由雙酚F及環氧氯丙烷衍生的雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、脂環式環氧樹脂、二苯基醚型環氧樹脂、氫醌型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、芴型環氧樹脂、3官能型環氧樹脂、4官能型環氧樹脂等多官能型環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環氧樹脂、異氰脲酸酯型環氧樹脂、脂肪族鏈狀環氧樹脂等，這些環氧樹脂可以被鹵化、也可以被氫化。作為市售的環氧樹脂製品，例如可列舉：Japan Epoxy Resin製造的JER code 828、1001、801N、806、807、152、604、630、871、YX8000、YX8034、YX4000、DIC株式會社製造的EPICLON830、EXA835LV、HP4032D、HP820、株式會社ADEKA製造的EP4100系列、EP4000系列、EPU系列、Daicel Chemical Industries, Ltd.製造的CELLOXIDE系列(2021、2021P、2083、2085、3000等)、Epolead系列、EHPE系列、新日鐵化學株式會社製造的YD系列、YDF系列、YDCN系列、YDB系列、苯氧基樹脂(是由雙酚類及環氧氯丙烷合成且兩末端具有環氧基的多羥基聚醚；YP系列等)、Nagase ChemteX Corporation製造的Denacol系列、共榮社化學株式會社製造的Epolight系列等，但不限於這些。這些環氧樹脂可以組合使用2種以上。Examples of polymers having one or more epoxy groups in the molecule include epoxy resins, including bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy resins derived from bisphenol F and epichlorohydrin, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, alicyclic epoxy resins, , diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional epoxy resin, quadrifunctional epoxy resin and other multifunctional epoxy resins, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, aliphatic chain epoxy resin, etc. These epoxy resins may be halogenated or hydrogenated. Examples of commercially available epoxy resin products include: JER code 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin, EPICLON830, EXA835LV, HP4032D, HP820 manufactured by DIC Corporation, EP4100 series, EP4000 series, EPU series manufactured by ADEKA Corporation, Daicel Chemical Industries, Ltd. Ltd., CELLOXIDE series (2021, 2021P, 2083, 2085, 3000, etc.), Epolead series, EHPE series, YD series, YDF series, YDCN series, YDB series, phenoxy resins (polyhydroxy polyethers synthesized from bisphenols and epichlorohydrin and having epoxy groups at both ends; YP series, etc.) manufactured by Nippon Steel Chemical Co., Ltd., Denacol series manufactured by Nagase ChemteX Corporation, Epolight series manufactured by Kyoeisha Chemical Co., Ltd., but not limited to these. These epoxy resins may be used in combination of two or more.

作為分子內具有烷氧基的化合物，只要其分子內具有1個以上烷氧基，就沒有特殊限制，可以使用公知的化合物。作為這樣的化合物，可以列舉出三聚氰胺化合物、胺基樹脂、矽烷偶聯劑等作為代表。The compound having an alkoxy group in the molecule is not particularly limited as long as it has one or more alkoxy groups in the molecule, and known compounds can be used. Representative examples of such compounds include melamine compounds, amino resins, and silane coupling agents.

相對於黏接劑組合物的總量，含有烷氧基、環氧基中的任一者的化合物的摻合量通常為30質量%以下，如果組合物中的化合物的含量過多，則黏接性降低，會有對落錘試驗的耐衝擊性惡化的情況。組合物中的化合物的含量更佳為20質量%以下。另一方面，從耐水性方面出發，較佳在組合物中含有化合物2質量%以上、更佳含有5質量%以上。The amount of the compound containing either an alkoxy group or an epoxy group is usually 30% by mass or less relative to the total amount of the adhesive composition. If the content of the compound in the composition is too high, the adhesiveness decreases and the impact resistance in the hammer test may deteriorate. The content of the compound in the composition is more preferably 20% by mass or less. On the other hand, from the perspective of water resistance, the compound is preferably contained in the composition at 2% by mass or more, more preferably at 5% by mass or more.

在本發明使用的黏接劑組合物為活性能量射線固化性的情況下，矽烷偶聯劑較佳使用活性能量射線固化性的化合物，但即使不是活性能量射線固化性，也可以賦予同樣的耐水性。When the adhesive composition used in the present invention is active energy ray curable, it is preferred that the silane coupling agent be an active energy ray curable compound. However, even if it is not active energy ray curable, the same water resistance can be imparted.

作為矽烷偶聯劑的具體例，可列舉作為活性能量射線固化性的化合物的乙烯基三氯矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、3-環氧丙氧基丙基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷等。Specific examples of the silane coupling agent include active energy ray-curable compounds such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-phenylenediyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

較佳為3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-丙烯醯氧基丙基三甲氧基矽烷。Preferred are 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane.

作為非活性能量射線固化性的矽烷偶聯劑的具體例，較佳具有胺基的矽烷偶聯劑。作為具有胺基的矽烷偶聯劑的具體例，可列舉：γ-胺基丙基三甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三異丙氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基甲基二乙氧基矽烷、γ-(2-胺基乙基)胺基丙基三甲氧基矽烷、γ-(2-胺基乙基)胺基丙基甲基二甲氧基矽烷、γ-(2-胺基乙基)胺基丙基三乙氧基矽烷、γ-(2-胺基乙基)胺基丙基甲基二乙氧基矽烷、γ-(2-胺基乙基)胺基丙基三異丙氧基矽烷、γ-(2-(2-胺基乙基)胺基乙基)胺基丙基三甲氧基矽烷、γ-(6-胺基己基)胺基丙基三甲氧基矽烷、3-(N-乙基胺基)-2-甲基丙基三甲氧基矽烷、γ-脲基丙基三甲氧基矽烷、γ-脲基丙基三乙氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-苄基-γ-胺基丙基三甲氧基矽烷、N-乙烯基苄基-γ-胺基丙基三乙氧基矽烷、N-環己基胺基甲基三乙氧基矽烷、N-環己基胺基甲基二乙氧基甲基矽烷、N-苯基胺基甲基三甲氧基矽烷、(2-胺基乙基)胺基甲基三甲氧基矽烷、N,N’-雙[3-(三甲氧基甲矽烷基)丙基]乙二胺等含胺基矽烷類；N-(1,3-二甲基亞丁基)-3-(三乙氧基甲矽烷基)-1-丙胺等酮亞胺型矽烷類。As a specific example of the non-active energy radiation curable silane coupling agent, a silane coupling agent having an amino group is preferred. As specific examples of the silane coupling agent having an amino group, there can be listed: γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl triisopropoxysilane, γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyl diethoxysilane, γ-(2-aminoethyl)aminopropyl trimethoxysilane, γ-(2-aminoethyl)aminopropyl γ-(2-aminoethyl)aminopropyl triethoxysilane, γ-(2-aminoethyl)aminopropyl methyldiethoxysilane, γ-(2-aminoethyl)aminopropyl triisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyl trimethoxysilane, γ-(6-aminohexyl)aminopropyl trimethoxysilane 、3-(N-ethylamino)-2-methylpropyltrimethoxysilane、γ-ureidopropyltrimethoxysilane、γ-ureidopropyltriethoxysilane、N-phenyl-γ-aminopropyltrimethoxysilane、N-benzyl-γ-aminopropyltrimethoxysilane、N-vinylbenzyl-γ-aminopropyltriethoxysilane、N-cyclohexylaminomethyltriethoxysilane、N - Cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine and other amino-containing silanes; N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine and other ketimine-type silanes.

具有胺基的矽烷偶聯劑可以僅使用1種，也可以組合使用多種。這些當中，為了確保良好的黏接性，較佳為γ-胺基丙基三甲氧基矽烷、γ-(2-胺基乙基)胺基丙基三甲氧基矽烷、γ-(2-胺基乙基)胺基丙基甲基二甲氧基矽烷、γ-(2-胺基乙基)胺基丙基三乙氧基矽烷、γ-(2-胺基乙基)胺基丙基甲基二乙氧基矽烷、N-(1,3-二甲基亞丁基)-3-(三乙氧基甲矽烷基)-1-丙胺。The silane coupling agent having an amino group may be used alone or in combination. Among these, γ-aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, and N-(1,3-dimethylbutylene)-3-(triethoxysilyl)-1-propylamine are preferred in order to ensure good adhesion.

相對於黏接劑組合物的總量，矽烷偶聯劑的摻合量較佳為0.01~20質量%的範圍、更佳為0.05~15質量%、進一步更佳為0.1~10質量%。這是因為在大於20質量%的摻合量的情況下，黏接劑組合物的保存穩定性會惡化，另外，在小於0.1質量%的情況下，難以充分發揮黏接耐水性的效果。The blending amount of the silane coupling agent relative to the total amount of the adhesive composition is preferably in the range of 0.01 to 20 mass %, more preferably 0.05 to 15 mass %, and further preferably 0.1 to 10 mass %. This is because when the blending amount is greater than 20 mass %, the storage stability of the adhesive composition deteriorates, and when the blending amount is less than 0.1 mass %, it is difficult to fully exert the effect of water resistance of the adhesive.

作為除上述以外的非活性能量射線固化性的矽烷偶聯劑的具體例，可列舉：3-脲基丙基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、3-巰基丙基甲基二甲氧基矽烷、3-巰基丙基三甲氧基矽烷、雙(三乙氧基甲矽烷基丙基)四硫化物、3-異氰酸酯基丙基三乙氧基矽烷、咪唑矽烷等。Specific examples of the non-active energy radiation curable silane coupling agent other than the above include 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-butylpropylmethyldimethoxysilane, 3-butylpropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, imidazole silane, and the like.

在本發明中使用的黏接劑組合物含有具有乙烯基醚基的化合物的情況下，偏光件與黏接劑層的黏接耐水性提高，因而較佳。得到該效果的理由尚不明確，但推測理由之一是藉由化合物所具有的乙烯基醚基與偏光件相互作用，偏光件與黏接劑層的黏接力提高。為了進一步提高偏光件與黏接劑層的黏接耐水性，化合物較佳為具有乙烯基醚基的自由基聚合性化合物。另外，對於化合物的含量而言，相對於黏接劑組合物的總量，較佳含有0.1~19質量%。When the adhesive composition used in the present invention contains a compound having a vinyl ether group, the water resistance of the bonding between the polarizer and the adhesive layer is improved, which is preferred. The reason for this effect is not clear, but one of the reasons is speculated to be that the bonding force between the polarizer and the adhesive layer is improved by the interaction between the vinyl ether group of the compound and the polarizer. In order to further improve the water resistance of the bonding between the polarizer and the adhesive layer, the compound is preferably a free radical polymerizable compound having a vinyl ether group. In addition, the content of the compound is preferably 0.1 to 19 mass % relative to the total amount of the adhesive composition.

可以在本發明使用的黏接劑組合物中含有產生酮-烯醇互變異構性的化合物。例如，在含有交聯劑的黏接劑組合物或能夠摻合交聯劑而使用的黏接劑組合物中，可較佳採用包含上述產生酮-烯醇互變異構性的化合物的方式。由此，可抑制有機金屬化合物摻合後的黏接劑組合物的過度黏度上升、凝膠化、以及微凝膠物的生成，可實現延長該組合物的適用期的效果。The adhesive composition used in the present invention may contain a compound that produces keto-enol tautomerism. For example, in an adhesive composition containing a crosslinking agent or an adhesive composition that can be used by mixing a crosslinking agent, it is preferable to use a method that contains the above-mentioned compound that produces keto-enol tautomerism. In this way, the excessive viscosity increase, gelation, and formation of microgels of the adhesive composition after the organic metal compound is mixed can be suppressed, and the effect of extending the applicable period of the composition can be achieved.

作為上述產生酮-烯醇互變異構性的化合物，可以使用各種β-二羰基化合物。作為具體例，可列舉：乙醯丙酮、2,4-己二酮、3,5-庚二酮、2-甲基己烷-3,5-二酮、6-甲基庚烷-2,4-二酮、2,6-二甲基庚烷-3,5-二酮等β-二酮類；乙醯乙酸甲酯、乙醯乙酸乙酯、乙醯乙酸異丙酯、乙醯乙酸三級丁酯等乙醯乙酸酯類；丙醯基乙酸乙酯、丙醯基乙酸乙酯、丙醯基乙酸異丙酯、丙醯基乙酸三級丁酯等丙醯基乙酸酯類；異丁醯基乙酸乙酯、異丁醯基乙酸乙酯、異丁醯基乙酸異丙酯、異丁醯基乙酸三級丁酯等異丁醯基乙酸酯類；丙二酸甲酯、丙二酸乙酯等丙二酸酯類；等等。其中，作為適宜的化合物，可列舉乙醯丙酮及乙醯乙酸酯類。上述產生酮-烯醇互變異構性的化合物可以單獨使用，也可以組合使用2種以上。As the compound that produces the keto-enol tautomerism, various β-dicarbonyl compounds can be used. Specific examples include β-diketones such as acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, and 2,6-dimethylheptane-3,5-dione; acetylacetic acid methyl ester, ethyl acetylacetate, isopropyl acetylacetate, and tertiary butyl acetylacetate; Acid esters; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, tertiary butyl propionyl acetate and the like propionyl acetate; ethyl isobutyryl acetate, ethyl isobutyryl acetate, isopropyl isobutyryl acetate, tertiary butyl isobutyryl acetate and the like isobutyryl acetate; malonic acid esters such as methyl malonate and ethyl malonate; and the like. Among them, acetylacetone and acetylacetic acid esters can be cited as suitable compounds. The above compounds producing keto-enol tautomerism can be used alone or in combination of two or more.

產生酮-烯醇互變異構性的化合物的用量例如相對於有機金屬化合物1質量份可以設為0.05質量份~10質量份、較佳設為0.2質量份~3質量份(例如0.3質量份~2質量份)。如果上述化合物的用量相對於有機金屬化合物1質量份為小於0.05質量份，則有時難以發揮充分的使用效果。另一方面，如果相對於有機金屬化合物1質量份該化合物的用量大於10質量份，則有時與有機金屬化合物過度地相互作用而變得難以表現出目標的耐水性。The amount of the compound that produces keto-enol tautomerism can be set to, for example, 0.05 to 10 parts by mass, preferably 0.2 to 3 parts by mass (e.g., 0.3 to 2 parts by mass) relative to 1 part by mass of the organic metal compound. If the amount of the compound used is less than 0.05 parts by mass relative to 1 part by mass of the organic metal compound, it may be difficult to fully exert the effect of use. On the other hand, if the amount of the compound used is greater than 10 parts by mass relative to 1 part by mass of the organic metal compound, it may be difficult to express the target water resistance due to excessive interaction with the organic metal compound.

也可以在本發明的黏接劑組合物中含有聚輪烷。上述聚輪烷具有環狀分子、貫通該環狀分子的開口部的直鏈狀分子、以及配置於該直鏈狀分子的兩端使得該環狀分子不從該直鏈狀分子脫離的封鏈基。較佳為環狀分子具有活性能量射線固化性的官能團。The adhesive composition of the present invention may also contain a polyrotaxane. The polyrotaxane has a cyclic molecule, a linear molecule penetrating the opening of the cyclic molecule, and a capping group disposed at both ends of the linear molecule so that the cyclic molecule does not detach from the linear molecule. Preferably, the cyclic molecule has an active energy ray-curable functional group.

作為環狀分子，只要是其開口部以串狀包合直鏈狀分子、並能夠在直鏈狀分子上移動、且具有活性能量射線聚合性基團的分子，就沒有特別限定。需要說明的是，在本說明書中，“環狀分子”的“環狀”是指實質上為“環狀”。即，只要能夠在直鏈狀分子上移動，環狀分子也可以不完全閉環。The cyclic molecule is not particularly limited as long as its opening includes a linear molecule in a string shape, can move on the linear molecule, and has an active energy ray polymerizable group. It should be noted that in this specification, the "cyclic" of "cyclic molecule" means substantially "cyclic". That is, as long as it can move on the linear molecule, the cyclic molecule does not have to be completely closed.

作為環狀分子的具體例，可列舉環狀聚醚、環狀聚酯、環狀聚醚胺、環狀聚胺等環狀聚合物、及α-環糊精、β-環糊精、γ-環糊精等環糊精。其中、較佳為比較容易獲取、且能夠選擇多數封鏈基的種類的α-環糊精、β-環糊精、γ-環糊精等環糊精。環狀分子可以在聚輪烷中或黏接劑中混合存在2種以上。Specific examples of cyclic molecules include cyclic polymers such as cyclic polyethers, cyclic polyesters, cyclic polyetheramines, and cyclic polyamines, and cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin. Among them, cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin are preferred because they are relatively easy to obtain and can have a variety of capping groups. Two or more cyclic molecules may be mixed in the polyrotaxane or the adhesive.

在本發明所使用的聚輪烷中，上述環狀分子具有活性能量射線聚合性基團。由此，聚輪烷與活性能量射線固化性成分反應，可得到即使在固化後交聯點也可動的黏接劑。環狀分子所具有的活性能量射線聚合性基團只要是能與上述活性能量射線固化性化合物聚合的基團即可，可舉出例如(甲基)丙烯醯基、(甲基)丙烯醯氧基等自由基聚合性基團。In the polyrotaxane used in the present invention, the above-mentioned cyclic molecule has an active energy radiation polymerizable group. Thus, the polyrotaxane reacts with the active energy radiation curable component to obtain an adhesive whose crosslinking points are movable even after curing. The active energy radiation polymerizable group possessed by the cyclic molecule can be any group that can polymerize with the above-mentioned active energy radiation curable compound, and examples thereof include free radical polymerizable groups such as (meth)acryloyl and (meth)acryloyloxy groups.

在使用環糊精作為環狀分子的情況下，較佳透過任意適當的連接體將活性能量射線聚合性基團導入到環糊精的羥基上。1分子聚輪烷中具有的活性能量射線聚合性基團的數量較佳為2個~1280個、更佳為50個~1000個、進一步更佳為90個~900個。When cyclodextrin is used as the cyclic molecule, the active energy radiation polymerizable group is preferably introduced into the hydroxyl group of cyclodextrin via any appropriate linker. The number of active energy radiation polymerizable groups in one molecule of polyrotaxane is preferably 2 to 1280, more preferably 50 to 1000, and even more preferably 90 to 900.

較佳為在環狀分子中導入疏水性修飾基團。藉由導入疏水性修飾基團，可提高與活性能量射線固化性成分的相容性。另外，由於賦予了疏水性，因此，在用於偏光薄膜的情況下，可防止水浸入黏接劑層與偏光件的界面，可更進一步提高耐水性。作為疏水性修飾基團，可列舉聚酯鏈、聚醯胺鏈、烷基鏈、氧化烯鏈、醚鏈等。作為具體例，可列舉WO2009/145073的[0027]~[0042]段落所記載的基團。It is preferred to introduce a hydrophobic modifying group into the cyclic molecule. By introducing a hydrophobic modifying group, the compatibility with the active energy radiation curable component can be improved. In addition, since the hydrophobicity is imparted, when used in a polarizing film, water can be prevented from penetrating into the interface between the adhesive layer and the polarizer, and the water resistance can be further improved. As the hydrophobic modifying group, polyester chains, polyamide chains, alkyl chains, oxyalkylene chains, ether chains, etc. can be listed. As specific examples, the groups described in paragraphs [0027] to [0042] of WO2009/145073 can be listed.

使用含有聚輪烷的樹脂組合物作為黏接劑的偏光薄膜的耐水性優異。偏光薄膜的耐水性提高的理由尚未確定，但推測如下所述。即，認為由於聚輪烷的環狀分子的可動性，交聯點能夠移動(所謂的滑輪效應)，由此對固化後的黏接劑賦予柔軟性，對偏光件的表面凹凸的密合性增加，其結果，防止水侵入偏光件與黏接劑層的界面。此外，認為藉由使聚輪烷具有疏水性修飾基團，可對黏接劑賦予疏水性，這也有助於防止水侵入偏光件與黏接劑層的界面。相對於樹脂組合物，聚輪烷的含量較佳為2質量%~50質量%。Polarizing films using a resin composition containing a polyrotaxane as an adhesive have excellent water resistance. The reason for the improved water resistance of polarizing films has not yet been determined, but it is speculated as follows. That is, it is believed that due to the mobility of the cyclic molecules of the polyrotaxane, the cross-linking points can move (the so-called pulley effect), thereby imparting flexibility to the cured adhesive and increasing the adhesion to the surface unevenness of the polarizer. As a result, water is prevented from invading the interface between the polarizer and the adhesive layer. In addition, it is believed that by giving the polyrotaxane a hydrophobic modifying group, the adhesive can be imparted with hydrophobicity, which also helps to prevent water from invading the interface between the polarizer and the adhesive layer. The content of the polyrotaxane relative to the resin composition is preferably 2% by mass to 50% by mass.

在本發明中，為了形成黏接劑層，可以使用陽離子聚合性黏接劑組合物。作為在陽離子聚合性黏接劑組合物中使用的陽離子聚合性化合物，可分類為分子內具有1個陽離子聚合性官能團的單官能陽離子聚合性化合物、及分子內具有2個以上陽離子聚合性官能團的多官能陽離子聚合性化合物。由於單官能陽離子聚合性化合物的液體黏度較低，因此，藉由在樹脂組合物中含有單官能陽離子聚合性化合物，可以降低樹脂組合物的液體黏度。另外，單官能陽離子聚合性化合物多數情況下具有表現出各種功能的官能團，藉由在樹脂組合物中含有單官能陽離子聚合性化合物，可以在樹脂組合物及/或樹脂組合物的固化物中表現出各種功能。多官能陽離子聚合性化合物由於可使樹脂組合物的固化物三維交聯，因而較佳在樹脂組合物中含有。對於單官能陽離子聚合性化合物與多官能陽離子聚合性化合物之比而言，相對於單官能陽離子聚合性化合物100質量份，較佳將多官能陽離子聚合性化合物以10質量份~1000質量份的範圍混合。作為陽離子聚合性官能團，可列舉環氧基、氧雜環丁基、乙烯基醚基。作為具有環氧基的化合物，可列舉脂肪族環氧化合物、脂環式環氧化合物、芳香族環氧化合物，由於固化性、黏接性優異，特佳為以含有脂環式環氧化合物作為本發明的陽離子聚合性黏接劑組合物。作為脂環式環氧化合物，可列舉3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯的己內酯改性物、三甲基己內酯改性物、戊內酯改性物等，具體而言，可列舉CELLOXIDE 2021、CELLOXIDE 2021A、CELLOXIDE 2021P、CELLOXIDE 2081、CELLOXIDE 2083、CELLOXIDE 2085(以上為大賽璐化學工業株式會社製)、Cyracure UVR-6105、Cyracure UVR-6107、Cyracure 30、R-6110(以上為Dow Chemical Japan Ltd.製)等。由於具有改善本發明的陽離子聚合性黏接劑組合物的固化性、降低該組合物的液體黏度的效果，較佳含有具有氧雜環丁基的化合物。作為具有氧雜環丁基的化合物，可列舉3-乙基-3-羥基甲基氧雜環丁烷、1,4-雙[(3-乙基-3-氧雜環丁基)甲氧基甲基]苯、3-乙基-3-(苯氧基甲基)氧雜環丁烷、二[(3-乙基-3-氧雜環丁基)甲基]醚、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷、酚醛清漆氧雜環丁烷等，市售有ARON OXETANE OXT-101、ARON OXETANE OXT-121、ARON OXETANE OXT-211、ARON OXETANE OXT-221、ARON OXETANE OXT-212(以上為東亞合成株式會社製)等。由於具有改善本發明的陽離子聚合性黏接劑組合物的固化性、降低該組合物的液體黏度的效果，較佳含有具有乙烯基醚基的化合物。作為具有乙烯基醚基的化合物，可列舉2-羥乙基乙烯基醚、二乙二醇單乙烯基醚、4-羥基丁基乙烯基醚、二乙二醇單乙烯基醚、三乙二醇二乙烯基醚、環己烷二甲醇二乙烯基醚、環己烷二甲醇單乙烯基醚、三環癸烷乙烯基醚、環己基乙烯基醚、甲氧基乙基乙烯基醚、乙氧基乙基乙烯基醚、季戊四醇型四乙烯基醚等。In the present invention, a cationically polymerizable adhesive composition can be used to form an adhesive layer. The cationically polymerizable compound used in the cationically polymerizable adhesive composition can be classified into a monofunctional cationically polymerizable compound having one cationically polymerizable functional group in the molecule and a polyfunctional cationically polymerizable compound having two or more cationically polymerizable functional groups in the molecule. Since the liquid viscosity of the monofunctional cationically polymerizable compound is low, the liquid viscosity of the resin composition can be reduced by including the monofunctional cationically polymerizable compound in the resin composition. In addition, monofunctional cationic polymerizable compounds often have functional groups that express various functions. By including monofunctional cationic polymerizable compounds in a resin composition, various functions can be expressed in the resin composition and/or the cured product of the resin composition. Polyfunctional cationic polymerizable compounds are preferably included in the resin composition because they can three-dimensionally crosslink the cured product of the resin composition. As for the ratio of monofunctional cationic polymerizable compounds to polyfunctional cationic polymerizable compounds, it is preferred to mix the polyfunctional cationic polymerizable compounds in a range of 10 to 1000 parts by mass relative to 100 parts by mass of the monofunctional cationic polymerizable compounds. Examples of the cationically polymerizable functional group include epoxy groups, cyclobutylene oxide groups, and vinyl ether groups. Examples of compounds having an epoxy group include aliphatic epoxy compounds, alicyclic epoxy compounds, and aromatic epoxy compounds. The cationically polymerizable adhesive composition of the present invention preferably contains alicyclic epoxy compounds because of their excellent curability and adhesiveness. Examples of the alicyclic epoxy compound include 3,4-epoxyepoxyhexylmethyl-3,4-epoxyepoxyhexanecarboxylate, caprolactone-modified products, trimethylcaprolactone-modified products, and valerolactone-modified products of 3,4-epoxyepoxyhexylmethyl-3,4-epoxyepoxyhexanecarboxylate. Specifically, examples include CELLOXIDE 2021, CELLOXIDE 2021A, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, and CELLOXIDE 2085 (all manufactured by Daicellu Chemical Industries, Ltd.), Cyracure UVR-6105, Cyracure UVR-6107, Cyracure 30, and R-6110 (all manufactured by Dow Chemical Japan Ltd.). Since the cationically polymerizable adhesive composition of the present invention has the effect of improving the curability and reducing the liquid viscosity of the composition, it is preferred to contain a compound having an oxacyclobutyl group. Examples of the compound having an oxetane butyl group include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanebutyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, di[(3-ethyl-3-oxetanebutyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, and novolac oxetane. Commercially available products include ARON OXETANE OXT-101, ARON OXETANE OXT-121, ARON OXETANE OXT-211, ARON OXETANE OXT-221, and ARON OXETANE OXT-212 (all manufactured by Toagosei Co., Ltd.). Since the cationically polymerizable adhesive composition of the present invention has the effect of improving the curability and reducing the liquid viscosity of the composition, it is preferred to contain a compound having a vinyl ether group. Examples of the compound having a vinyl ether group include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexanedimethanol divinyl ether, cyclohexanedimethanol monovinyl ether, tricyclodecane vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, pentaerythritol tetravinyl ether, and the like.

陽離子聚合性黏接劑組合物含有選自以上說明的具有環氧基的化合物、具有氧雜環丁烷基的化合物、具有乙烯基醚基的化合物中的至少1種化合物作為固化性成分、它們都是藉由陽離子聚合而固化的物質，因此摻合光陽離子聚合引發劑。該光陽離子聚合引發劑藉由可見光、紫外線、X射線、電子束等活性能量射線的照射產生陽離子種或路易斯酸，從而引發環氧基、氧雜環丁基的聚合反應。作為光陽離子聚合引發劑，可使用光產酸劑及光產鹼劑，可適宜地使用後面敘述的光產酸劑。另外，在使用本發明中使用的黏接劑組合物作為可見光固化性的情況下，特別是以使用對380nm以上的光具有高靈敏度的光陽離子聚合引發劑為佳，但光陽離子聚合引發劑為通常在300nm附近或比300nm短的波長區域顯示出極大吸收的化合物，因此，藉由摻合在比其更長的波長區域、具體而言比380nm更長的波長的光下顯示出極大吸收的光敏劑，可以感應其附近的波長的光，促進來自光陽離子聚合引發劑的陽離子種或酸的產生。作為光敏劑，可列舉例如：蒽化合物、芘化合物、羰基化合物、有機硫化合物、過硫化物、氧化還原類化合物、偶氮及重氮化合物、鹵素化合物、光還原性色素等，它們也可以混合2種以上使用。特別是蒽化合物的光敏效果優異，因而較佳，具體可列舉Anthracure UVS-1331、Anthracure UVS-1221(川崎化成株式會社制)。光敏劑的含量較佳為0.1質量%~5質量%、更佳為0.5質量%~3質量%。The cationic polymerizable adhesive composition contains at least one compound selected from the above-described compounds having an epoxy group, a compound having an oxycyclobutyl group, and a compound having a vinyl ether group as a curable component, and all of them are substances that are cured by cationic polymerization, so a photo-cationic polymerization initiator is mixed. The photo-cationic polymerization initiator generates cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, thereby initiating polymerization reactions of epoxy groups and oxycyclobutyl groups. As the photo-cationic polymerization initiator, a photoacid generator and a photoalkali generator can be used, and the photoacid generator described later can be used appropriately. In addition, when the adhesive composition used in the present invention is used as a visible light curable adhesive, it is particularly preferred to use a photocationic polymerization initiator that has high sensitivity to light of 380 nm or above, but the photocationic polymerization initiator is a compound that generally shows extreme absorption in the wavelength region near 300 nm or shorter than 300 nm. Therefore, by mixing a photosensitizer that shows extreme absorption under light of a longer wavelength region, specifically, longer than 380 nm, it is possible to sense light of a wavelength near it and promote the generation of cationic species or acids from the photocationic polymerization initiator. As photosensitizers, for example, anthracene compounds, pyrene compounds, carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, photoreduction pigments, etc., and two or more of them can also be used in combination. In particular, anthracene compounds are excellent in photosensitizing effect and are therefore preferred. Specifically, Anthracure UVS-1331 and Anthracure UVS-1221 (manufactured by Kawasaki Chemical Co., Ltd.) can be cited. The content of the photosensitizer is preferably 0.1% by mass to 5% by mass, and more preferably 0.5% by mass to 3% by mass.

＜黏接劑層＞ 在將上述黏接劑組合物、後面敘述的易黏接組合物塗敷於偏光件的貼合面的情況下，黏接劑層藉由將黏接劑組合物及易黏接組合物固化而形成。在將易黏接組合物塗敷於偏光件的貼合面的情況下，在貼合步驟中，塗敷於透明保護薄膜的貼合面的未固化的黏接劑組合物與塗敷於偏光件的貼合面的未固化的易黏接組合物混合。然後，在之後的黏接步驟中，藉由照射活性能量射線，使黏接劑組合物及易黏接組合物在混合的狀態下固化，形成黏接劑層。黏接劑層的厚度較佳為0.01~3.0μm。在黏接劑層的厚度過薄的情況下，黏接劑層的凝聚力不足，剝離力降低，因而不為所欲。在黏接劑層的厚度過厚的情況下，對偏光薄膜的截面施加應力時容易引起剝離，發生由衝擊導致的剝離不良，因而不為所欲。黏接劑層的厚度更佳為0.1~2.5μm、最佳為0.5~1.5μm。<Adhesive layer> When the above-mentioned adhesive composition and the easy-adhesive composition described later are applied to the bonding surface of the polarizer, the adhesive layer is formed by curing the adhesive composition and the easy-adhesive composition. When the easy-adhesive composition is applied to the bonding surface of the polarizer, in the bonding step, the uncured adhesive composition applied to the bonding surface of the transparent protective film is mixed with the uncured easy-adhesive composition applied to the bonding surface of the polarizer. Then, in the subsequent bonding step, the adhesive composition and the easy-adhesive composition are cured in a mixed state by irradiating active energy rays to form an adhesive layer. The thickness of the adhesive layer is preferably 0.01 to 3.0 μm. If the thickness of the adhesive layer is too thin, the cohesive force of the adhesive layer is insufficient, and the peeling force is reduced, which is not desirable. If the thickness of the adhesive layer is too thick, it is easy to cause peeling when stress is applied to the cross section of the polarizing film, and peeling failure caused by impact occurs, which is not desirable. The thickness of the adhesive layer is more preferably 0.1 to 2.5 μm, and the most preferably 0.5 to 1.5 μm.

＜易黏接組合物＞ 為了進一步提高偏光件與透明保護薄膜之間的黏接性，在本發明中，較佳在偏光件的貼合面(與透明保護薄膜的貼合面)塗敷易黏接組合物。較佳上述易黏接組合物含有下述通式(1)表示的化合物， [化學式8] (式中，X為包含反應性基團的官能團，R¹ 及R² 分別獨立地表示氫原子、可亦具有取代基的脂肪族烴基、芳基或雜環基)。藉由將含有上述通式(1)表示的含硼化合物的易黏接組合物塗敷於偏光件的貼合面，特別地，偏光薄膜的耐水黏接性提高，因而較佳。表現出上述效果的理由尚未明確，但可以推定出以下的理由。<Easy-adhesion composition> In order to further improve the adhesion between the polarizer and the transparent protective film, in the present invention, it is preferred to apply an easy-adhesion composition on the bonding surface of the polarizer (the bonding surface with the transparent protective film). Preferably, the easy-adhesion composition contains a compound represented by the following general formula (1): [Chemical formula 8] (wherein X is a functional group containing a reactive group, and ^R1 and ^R2 are independently a hydrogen atom, an aliphatic hydrocarbon group which may also have a substituent, an aromatic group or a heterocyclic group.) By applying the easy-adhesion composition containing the boron-containing compound represented by the general formula (1) to the bonding surface of the polarizer, the water-resistant adhesion of the polarizing film is particularly improved, and thus it is better. The reason for the above effect is not yet clear, but the following reasons can be inferred.

在易黏接組合物中，上述式(1)記載的含硼化合物可以與偏光件所具有的羥基等官能團反應，由此能夠提高偏光件與黏接劑層的黏接性，其結果，可發揮提高偏光薄膜的耐水黏接性的效果。In the easy-adhesion composition, the boron-containing compound described in the above formula (1) can react with the functional groups such as hydroxyl groups of the polarizer, thereby improving the adhesion between the polarizer and the adhesive layer, and as a result, can exert the effect of improving the water-resistant adhesion of the polarizing film.

上述通式(1)中，作為上述脂肪族烴基，可列舉碳原子數1~20的可亦具有取代基的直鏈或支化的烷基、碳原子數3~20的可亦具有取代基的環狀烷基、碳原子數2~20的烯基，作為芳基，可列舉碳原子數6~20的可亦具有取代基的苯基、碳原子數10~20的可亦具有取代基的萘基等，作為雜環基，可列舉例如至少含有一個雜原子且可亦具有取代基的5元環或6元環的基團。它們可以相互連結而形成環。通式(1)中，作為R¹ 及R² ，較佳為氫原子、碳原子數1~3的直鏈或支化的烷基，最佳為氫原子。需要說明的是，在最終製造的偏光薄膜中，通式(1)表示的化合物可以在未反應的狀態下存在於偏光件與黏接劑層之間的易黏接層中，也可以在各官能團反應後的狀態下存在於其中。另外，在本發明中，可以藉由在偏光件的黏接劑層形成面側的整個面塗敷易黏接組合物而形成易黏接層，也可以藉由在至少一部分的面塗敷易黏接組合物而形成易黏接層。In the above general formula (1), the above aliphatic alkyl group includes a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cyclic alkyl group having 3 to 20 carbon atoms which may have a substituent, and an alkenyl group having 2 to 20 carbon atoms. The aryl group includes a phenyl group having 6 to 20 carbon atoms which may have a substituent, a naphthyl group having 10 to 20 carbon atoms which may have a substituent, and the like. The heterocyclic group includes, for example, a 5-membered or 6-membered ring group which contains at least one heteroatom and may have a substituent. These may be linked to each other to form a ring. In the general formula (1), ^R1 and ^R2 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, and most preferably a hydrogen atom. It should be noted that, in the polarizing film finally manufactured, the compound represented by the general formula (1) may be present in the easy-adhesion layer between the polarizer and the adhesive layer in an unreacted state, or may be present therein after the functional groups have reacted. In addition, in the present invention, the easy-adhesion layer may be formed by applying the easy-adhesion composition to the entire surface of the adhesive layer forming surface of the polarizer, or may be formed by applying the easy-adhesion composition to at least a portion of the surface.

通式(1)表示的化合物所具有的X是含有反應性基團的官能團，是能與構成黏接劑層的固化性成分反應的官能團，作為X所含的反應性基團，可列舉例如：羥基、胺基、醛基、羧基、乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁基、α,β-不飽和羰基、巰基、鹵素基團等。在構成黏接劑層的固化性樹脂組合物為活性能量射線固化性的情況下，X所含的反應性基團較佳為選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁基及巰基所構成組群中的至少1種反應性基團，特別是在構成黏接劑層的黏接劑組合物為自由基聚合性的情況下，X所含的反應性基團較佳為選自於由(甲基)丙烯醯基、苯乙烯基及(甲基)丙烯醯胺基所構成組群中的至少1種反應性基團，在通式(1)表示的化合物具有(甲基)丙烯醯胺基的情況下，反應性高，與活性能量射線固化性樹脂組合物的共聚率提高，因而更佳。另外，(甲基)丙烯醯胺基的極性高，黏接性優異，因此，從高效地得到本發明效果的方面考慮也較佳。在構成黏接劑層的固化性樹脂組合物為陽離子聚合性的情況下，X所含的反應性基團較佳具有選自羥基、胺基、醛基、羧基、乙烯基醚基、環氧基、氧雜環丁基、巰基中的至少1種官能團，特別是在具有環氧基的情況下，得到的固化性樹脂層與被黏附物的密合性優異，因而較佳，在具有乙烯基醚基的情況下，固化性樹脂組合物的固化性優異，因而較佳。X in the compound represented by the general formula (1) is a functional group containing a reactive group, and is a functional group that can react with the curable component constituting the adhesive layer. Examples of the reactive group contained in X include a hydroxyl group, an amino group, an aldehyde group, a carboxyl group, a vinyl group, a (meth)acryl group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxycyclobutyl group, an α,β-unsaturated carbonyl group, a hydroxyl group, a halogen group, and the like. When the curable resin composition constituting the adhesive layer is active energy ray curable, the reactive group contained in X is preferably at least one reactive group selected from the group consisting of vinyl, (meth)acryl, styryl, (meth)acrylamide, vinyl ether, epoxy, cyclobutyl and butyl. In the case of free radical polymerizability, the reactive group contained in X is preferably at least one reactive group selected from the group consisting of a (meth)acryl group, a styryl group and a (meth)acrylamide group. When the compound represented by the general formula (1) has a (meth)acrylamide group, the reactivity is high and the copolymerization rate with the active energy ray curable resin composition is improved, which is more preferred. In addition, the (meth)acrylamide group has high polarity and excellent adhesiveness, and is therefore preferred from the viewpoint of efficiently obtaining the effect of the present invention. When the curable resin composition constituting the adhesive layer is cationically polymerizable, the reactive group contained in X preferably has at least one functional group selected from a hydroxyl group, an amine group, an aldehyde group, a carboxyl group, a vinyl ether group, an epoxy group, an oxycyclobutyl group, and an alkyl group. In particular, when the reactive group has an epoxy group, the obtained curable resin layer has excellent adhesion to the adherend, which is preferred. When the reactive group has a vinyl ether group, the curable resin composition has excellent curability, which is preferred.

作為通式(1)表示的化合物的較佳的具體例，可列舉下述通式(1’)表示的化合物， [化學式9] (式中，Y為有機基團，X’為X所含的反應性基團，R¹ 及R² 與上述定義相同)。進一步可適宜列舉以下的化合物(1a)~(1d)。As a preferred specific example of the compound represented by the general formula (1), there can be cited the compound represented by the following general formula (1'): [Chemical Formula 9] (In the formula, Y is an organic group, X' is a reactive group contained in X, and ^R1 and ^R2 have the same meanings as defined above.) Further, the following compounds (1a) to (1d) can be suitably listed.

[化學式10] [Chemical formula 10]

在本發明中，通式(1)表示的化合物可以是反應性基團與硼原子直接鍵合而成的化合物，但如上述具體例中所示那樣，通式(1)表示的化合物較佳為反應性基團與硼原子透過有機基團鍵合而成的化合物，也就是較佳為通式(1’)表示的化合物。通式(1)表示的化合物為例如透過與硼原子鍵合的氧原子與反應性基團鍵合的化合物的情況下，係有偏光薄膜的黏接耐水性惡化的傾向。另一方面，通式(1)表示的化合物不具有硼-氧鍵，而藉由硼原子與有機基團鍵合，具有硼-碳鍵，並且含有反應性基團時(為通式(1’)時)，偏光薄膜的黏接耐水性提高，因而較佳。上述有機基團具體是指可亦具有取代基的碳原子數1~20的有機基團，更具體而言，可列舉例如：碳原子數1~20的可亦具有取代基的直鏈或支化的伸烷基、碳原子數3~20的可亦具有取代基的環狀伸烷基、碳原子數6~20的可亦具有取代基的伸苯基、碳原子數10~20的可亦具有取代基的伸萘基等。In the present invention, the compound represented by the general formula (1) may be a compound in which a reactive group and a boron atom are directly bonded, but as shown in the above specific examples, the compound represented by the general formula (1) is preferably a compound in which a reactive group and a boron atom are bonded via an organic group, that is, preferably a compound represented by the general formula (1'). When the compound represented by the general formula (1) is a compound in which a reactive group is bonded via an oxygen atom bonded to a boron atom, for example, the adhesive water resistance of the polarizing film tends to deteriorate. On the other hand, when the compound represented by the general formula (1) does not have a boron-oxygen bond, but has a boron-carbon bond via a boron atom and an organic group bonded thereto, and contains a reactive group (when it is the general formula (1')), the adhesive water resistance of the polarizing film is improved, and thus it is preferred. The organic group specifically refers to an organic group having 1 to 20 carbon atoms which may have a substituent. More specifically, for example, a linear or branched alkylene group having 1 to 20 carbon atoms which may have a substituent, a cyclic alkylene group having 3 to 20 carbon atoms which may have a substituent, a phenylene group having 6 to 20 carbon atoms which may have a substituent, and a naphthylene group having 10 to 20 carbon atoms which may have a substituent.

作為通式(1)表示的化合物，除上述示例的化合物以外，可示例出羥基乙基丙烯醯胺與硼酸形成的酯、羥甲基丙烯醯胺與硼酸形成的酯、丙烯酸羥基乙酯與硼酸形成的酯、及丙烯酸羥基丁酯與硼酸形成的酯等(甲基)丙烯酸酯與硼酸形成的酯。Examples of the compound represented by the general formula (1) include, in addition to the compounds exemplified above, esters of (meth)acrylic acid esters with boric acid, such as esters of hydroxyethylacrylamide with boric acid, esters of hydroxymethylacrylamide with boric acid, esters of hydroxyethyl acrylate with boric acid, and esters of hydroxybutyl acrylate with boric acid.

在易黏接組合物中，通式(1)表示的化合物的含量過少時，會有存在於易黏接層表面的通式(1)表示的化合物的比例降低、易黏接效果變低的情況。因此，在易黏接組合物中，通式(1)表示的化合物的含量較佳為0.01質量%以上、更佳為0.05質量%以上、進一步更佳為0.1質量%以上。If the content of the compound represented by the general formula (1) in the easy-adhesion composition is too low, the proportion of the compound represented by the general formula (1) present on the surface of the easy-adhesion layer may decrease, and the easy-adhesion effect may decrease. Therefore, in the easy-adhesion composition, the content of the compound represented by the general formula (1) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more.

在本發明中，特別是為了提高透明保護薄膜與黏接劑層的黏接性，可以使用以使透明保護薄膜的SP值與易黏接組合物的SP值之間的SP值距離為較佳成為8.0以下、更佳成為7.5以下、進一步更佳成為7.3以下的方式設計的易黏接組合物。作為如此地進行設計的方法，可舉出例如將可摻合於黏接劑組合物中的上述通式(2)表示的化合物摻合於易黏接組合物中的方法。特別是在易黏接組合物中摻合N-丙烯醯基嗎啉的情況下，通式(1)表示的化合物的溶解性高，可以使通式(1)表示的化合物充分地分散於易黏接組合物中，因而較佳。另外，可以明顯有助於將與透明保護薄膜的SP值距離設為8.0以下，因而較佳。需要說明的是，對於透明保護薄膜的SP值與易黏接組合物的SP值之間的SP值距離的下限而言，從有效地抑制偏光薄膜內的氣泡產生的觀點考慮，可示例出例如5.3以上。關於易黏接組合物的SP值的測定方法，在後面敘述。In the present invention, in particular, in order to improve the adhesion between the transparent protective film and the adhesive layer, an easy-adhesion composition designed in such a manner that the SP value distance between the SP value of the transparent protective film and the SP value of the easy-adhesion composition is preferably 8.0 or less, more preferably 7.5 or less, and further preferably 7.3 or less can be used. As a method for such design, for example, a method of blending the compound represented by the above-mentioned general formula (2) that can be blended in the adhesive composition into the easy-adhesion composition can be cited. In particular, when N-acryloylmorpholine is blended in the easy-adhesion composition, the compound represented by the general formula (1) has high solubility, and the compound represented by the general formula (1) can be fully dispersed in the easy-adhesion composition, which is preferred. In addition, it is preferable because it can significantly contribute to setting the SP value distance with the transparent protective film to 8.0 or less. It should be noted that, from the perspective of effectively suppressing the generation of bubbles in the polarizing film, the lower limit of the SP value distance between the SP value of the transparent protective film and the SP value of the easy-adhesion composition can be 5.3 or more. The method for measuring the SP value of the easy-adhesion composition will be described later.

只要將易黏接組合物中的通式(2)表示的化合物的含量以透明保護薄膜的SP值與易黏接組合物的SP值之間的SP值距離成為8.0以下的方式進行調整即可，例如在易黏接組合物中，通式(2)表示的化合物的含量較佳為1~80質量%。The content of the compound represented by the general formula (2) in the easy-adhesion composition can be adjusted so that the SP value distance between the SP value of the transparent protective film and the SP value of the easy-adhesion composition becomes 8.0 or less. For example, in the easy-adhesion composition, the content of the compound represented by the general formula (2) is preferably 1 to 80 mass %.

除了上述通式(1)記載的化合物、及上述通式(2)記載的化合物以外，在易黏接組合物中還可以含有溶劑。作為易黏接組合物(A)中可以含有的溶劑，較佳能夠將通式(1)表示的化合物穩定地溶解或分散的溶劑。該溶劑可使用有機溶劑、水、或它們的混合溶劑。作為上述溶劑，例如可以從下述中選擇：乙酸乙酯、乙酸丁酯、乙酸2-羥基乙酯等酯類；甲乙酮、丙酮、環己酮、甲基異丁基酮、二乙基酮、甲基正丙基酮、乙醯丙酮等酮類；四氫呋喃(THF)、二噁烷等環狀醚類；正己烷、環己烷等脂肪族或脂環族烴類；甲苯、二甲苯等芳香族烴類；甲醇、乙醇、正丙醇、異丙醇、環己醇等脂肪族或脂環族醇類；乙二醇單甲醚、乙二醇單***、二乙二醇單***等二醇醚類；二乙二醇單甲醚乙酸酯、二乙二醇單***乙酸酯等二醇醚乙酸酯類；等等。In addition to the compound represented by the general formula (1) and the compound represented by the general formula (2), the easy-adhesion composition may further contain a solvent. As the solvent that may be contained in the easy-adhesion composition (A), a solvent that can stably dissolve or disperse the compound represented by the general formula (1) is preferred. The solvent may be an organic solvent, water, or a mixed solvent thereof. The above-mentioned solvent can be selected from the following, for example: esters such as ethyl acetate, butyl acetate, and 2-hydroxyethyl acetate; ketones such as methyl ethyl ketone, acetone, cyclohexanone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, and acetylacetone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, and cyclohexanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol monoethyl ether; glycol ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate; and the like.

此外，在本發明中，使用易黏接組合物時，也可以含有其它添加劑、例如增黏劑、紫外線吸收劑、抗氧劑、耐熱穩定劑等穩定劑等。Furthermore, in the present invention, when the easy-adhesion composition is used, other additives such as a thickener, an ultraviolet absorber, an antioxidant, a stabilizer such as a heat-resistant stabilizer, etc. may be contained.

＜易黏接層＞ 在本發明的偏光薄膜之製造方法中，藉由在偏光件的貼合面塗敷易黏接組合物的第二塗敷步驟之後根據需要設置乾燥步驟等，可以形成易黏接層。在本發明中，在偏光件所具備的易黏接層的厚度過厚的情況下，存在易黏接層的凝聚力降低、易黏接效果變低的情況。因此，易黏接層的厚度較佳為300nm以下、更佳為200nm以下，從生產性的觀點考慮，進一步更佳為100nm以下。另一方面，作為用於使易黏接層充分發揮效果的厚度的最下限，可舉出至少通式(1)表示的化合物的單分子膜的厚度，通常為0.1nm以上、較佳為1nm以上、更佳為2nm以上。<Easy-adhesive layer> In the manufacturing method of the polarizing film of the present invention, the easy-adhesive layer can be formed by providing a drying step as needed after the second coating step of applying the easy-adhesive composition on the bonding surface of the polarizer. In the present invention, if the thickness of the easy-adhesive layer of the polarizer is too thick, the cohesive force of the easy-adhesive layer is reduced and the easy-adhesive effect is reduced. Therefore, the thickness of the easy-adhesive layer is preferably 300nm or less, more preferably 200nm or less, and from the perspective of productivity, it is further preferably 100nm or less. On the other hand, the minimum thickness limit for the adhesion-promoting layer to fully exert its effect is that the thickness of the monomolecular film of at least the compound represented by the general formula (1) is usually 0.1 nm or more, preferably 1 nm or more, and more preferably 2 nm or more.

＜偏光件＞ 在本發明中，從提高高溫高濕下的嚴苛環境中的光學耐久性的觀點考慮，作為偏光件，較佳使用厚度為3μm以上且15μm以下的薄型偏光件。特別地，較佳為12μm以下、更佳為10μm以下、特佳為8μm以下。這樣的薄型的偏光件的厚度不均少，視覺辨認性優異，而且尺寸變化少，因此，對於熱衝擊的耐久性優異。<Polarizer> In the present invention, from the perspective of improving optical durability in a harsh environment under high temperature and high humidity, a thin polarizer with a thickness of 3 μm or more and 15 μm or less is preferably used as a polarizer. In particular, it is preferably 12 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less. Such a thin polarizer has less uneven thickness, excellent visual recognition, and less dimensional change, so it has excellent durability against thermal shock.

偏光件利用使用了聚乙烯醇類樹脂的偏光件。作為偏光件，可列舉例如使碘、二色性染料的二色性物質吸附於聚乙烯醇類薄膜、部分縮甲醛化聚乙烯醇類薄膜、乙烯-乙酸乙烯酯共聚物類部分皂化薄膜等親水性高分子薄膜並進行單軸拉伸而得到的薄膜、聚乙烯醇的脫水處理物、聚氯乙烯的脫鹽酸處理物等多烯類配向薄膜等。這些中，較佳由聚乙烯醇類薄膜及碘等二色性物質形成的偏光件。The polarizer uses a polarizer using a polyvinyl alcohol resin. Examples of the polarizer include films obtained by adsorbing dichroic substances such as iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and partially saponified films of ethylene-vinyl acetate copolymers and then uniaxially stretching them, and polyene-oriented films such as dehydrated polyvinyl alcohol and dehydrogenated polyvinyl chloride. Among these, a polarizer formed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferred.

用碘將聚乙烯醇類薄膜染色且進行了單軸拉伸而成的偏光件例如可以如下來製作：藉由將聚乙烯醇浸漬於碘的水溶液而進行染色，並拉伸至初始長度的3~7倍。根據需要，可亦含有硼酸、硫酸鋅、氯化鋅，也可以浸漬於碘化鉀等的水溶液中。此外，根據需要，也可以在染色前將聚乙烯醇類薄膜浸漬於水中而進行水洗。藉由對聚乙烯醇類薄膜進行水洗，不僅能夠清洗聚乙烯醇類薄膜表面的污漬、抗黏連劑，還具有藉由使聚乙烯醇類薄膜溶脹而防止染色不均等不均勻的效果。拉伸可以在用碘進行了染色之後進行，也可以邊進行染色邊進行拉伸，另外，也可以在拉伸後用碘進行染色。還可以在硼酸、碘化鉀等的水溶液、水浴中進行拉伸。A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching can be produced, for example, as follows: dyeing is performed by immersing polyvinyl alcohol in an aqueous solution of iodine, and stretching to 3 to 7 times the initial length. As required, it may also contain boric acid, zinc sulfate, zinc chloride, or may be immersed in an aqueous solution of potassium iodide or the like. In addition, as required, the polyvinyl alcohol film may be immersed in water and washed before dyeing. By washing the polyvinyl alcohol film with water, not only can the stains and anti-adhesive agents on the surface of the polyvinyl alcohol film be cleaned, but also the effect of preventing uneven dyeing, such as uneven dyeing, can be prevented by swelling the polyvinyl alcohol film. Stretching can be performed after dyeing with iodine, or while dyeing, or after stretching, dyeing with iodine. Stretching can also be performed in an aqueous solution of boric acid, potassium iodide, or the like, or in a water bath.

從拉伸穩定性、加濕可靠性的方面考慮，較佳偏光件含有硼酸。另外，從抑制貫穿裂紋的發生的觀點考慮，相對於偏光件總量，偏光件中所含的硼酸含量較佳為22質量%以下、更佳為20質量%以下。從拉伸穩定性、加濕可靠性的觀點考慮，相對於偏光件總量，硼酸含量較佳為10質量%以上、更佳為12質量%以上。From the perspective of tensile stability and humidification reliability, the polarizer preferably contains boric acid. In addition, from the perspective of suppressing the occurrence of through cracks, the boric acid content in the polarizer is preferably 22% by mass or less, and more preferably 20% by mass or less relative to the total amount of the polarizer. From the perspective of tensile stability and humidification reliability, the boric acid content is preferably 10% by mass or more, and more preferably 12% by mass or more relative to the total amount of the polarizer.

作為代表性的薄型偏光件，可列舉在日本專利第4751486號說明書、日本專利第4751481號說明書、日本專利第4815544號說明書、日本專利第5048120號說明書、國際公開第2014/077599號小冊子、國際公開第2014/077636號小冊子等中記載的薄型偏光件或由這些文獻中記載的製造方法得到的薄型偏光件。Representative thin polarizers include those described in Japanese Patent No. 4751486, Japanese Patent No. 4751481, Japanese Patent No. 4815544, Japanese Patent No. 5048120, International Publication No. 2014/077599, International Publication No. 2014/077636, etc., or those obtained by the manufacturing methods described in these documents.

作為上述薄型偏光件，在包括以積層體的狀態進行拉伸的步驟及進行染色的步驟的制法中，從能夠拉伸至高倍率而使偏光性能提高的觀點出發，較佳利用如日本專利第4751486號說明書、日本專利第4751481號說明書、日本專利4815544號說明書中記載那樣的包括在硼酸水溶液中進行拉伸的步驟的製法而得到的薄型偏光件，特別是以記載於日本專利第4751481號說明書、日本專利4815544號說明書中的包括在硼酸水溶液中進行拉伸之前輔助性地進行氣體氛圍中拉伸的步驟的製法而得到的薄型偏光件為佳。這些薄型偏光薄膜可以藉由包括將聚乙烯醇類樹脂(以下，也稱為PVA類樹脂)層及拉伸用樹脂基材以積層體的狀態進行拉伸的步驟及進行染色的步驟的制法來獲得。如果是該製法，則即使PVA類樹脂層薄，也能夠藉由被拉伸用樹脂基材支撐來進行拉伸而不發生由拉伸導致的斷裂等不良情況。As the above-mentioned thin polarizer, in the method including the steps of stretching in the state of a laminate and dyeing, from the viewpoint of being able to stretch to a high ratio to improve the polarization performance, it is preferred to use a thin polarizer obtained by a method including the step of stretching in an aqueous boric acid solution as described in Japanese Patent No. 4751486, Japanese Patent No. 4751481, and Japanese Patent No. 4815544, especially a thin polarizer obtained by a method including the step of auxiliary stretching in a gas atmosphere before stretching in an aqueous boric acid solution as described in Japanese Patent No. 4751481 and Japanese Patent No. 4815544. These thin polarizing films can be obtained by a method including stretching a polyvinyl alcohol resin (hereinafter, also referred to as PVA resin) layer and a stretching resin substrate in a laminated state and dyeing the laminated state. According to this method, even if the PVA resin layer is thin, it can be stretched without causing problems such as breakage due to stretching by being supported by the stretching resin substrate.

＜透明保護薄膜＞ 作為本發明中使用的透明保護薄膜，使用具有黏接劑組合物的SP值之間的SP值距離成為5.3以上的SP值的透明保護薄膜。另外，較佳使用易黏接組合物的SP值之間的SP值距離成為8.0以下的透明保護薄膜。需要說明的是，關於透明保護薄膜的SP值的測定方法，在後面敘述。本發明中使用的透明保護薄膜較佳透明性、機械強度、熱穩定性、水分阻隔性、各向同性等優異者。例如可列舉：聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等聚酯類聚合物、二乙酸纖維素、三乙酸纖維素等纖維素類聚合物、聚甲基丙烯酸甲酯等丙烯酸類聚合物、聚苯乙烯、丙烯腈-苯乙烯共聚物(AS樹脂)等苯乙烯類聚合物、聚碳酸酯類聚合物等。另外，聚乙烯、聚丙烯、具有環類或降冰片烯結構的聚烯烴、乙烯-丙烯共聚物這樣的聚烯烴類聚合物、氯乙烯類聚合物、尼龍、芳香族聚醯胺等醯胺類聚合物、醯亞胺類聚合物、碸類聚合物、聚醚碸類聚合物、聚醚醚酮類聚合物、聚苯硫醚類聚合物、乙烯醇類聚合物、偏氯乙烯類聚合物、乙烯基縮丁醛類聚合物、聚芳酯類聚合物、聚甲醛類聚合物、環氧類聚合物、或上述聚合物的混合物等。透明保護薄膜中可以含有1種以上任意適當的添加劑。作為添加劑，例如可列舉：紫外線吸收劑、抗氧劑、潤滑劑、增塑劑、脫模劑、防著色劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。透明保護薄膜中的上述熱塑性樹脂的含量較佳為50~100質量%、更佳為50~99質量%、進一步更佳為60~98質量%、特佳為70~97質量%。在透明保護薄膜中的上述熱塑性樹脂的含量為50質量%以下的情況下，存在不能充分表現出熱塑性樹脂本來具有的高透明性等之虞。<Transparent protective film> As the transparent protective film used in the present invention, a transparent protective film having an SP value of 5.3 or more between the SP values of the adhesive composition is used. In addition, a transparent protective film having an SP value of 8.0 or less between the SP values of the easy-to-adhesive composition is preferably used. It should be noted that the method for measuring the SP value of the transparent protective film will be described later. The transparent protective film used in the present invention is preferably excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as cellulose diacetate and cellulose triacetate, acrylic polymers such as polymethyl methacrylate, polystyrene polymers such as acrylonitrile-styrene copolymer (AS resin), polycarbonate polymers, etc. In addition, polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, polyolefin polymers such as ethylene-propylene copolymer, vinyl chloride polymers, nylon, amide polymers such as aromatic polyamide, imide polymers, sulfonium polymers, polyethersulfonium polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers, polyarylate polymers, polyoxymethylene polymers, epoxy polymers, or mixtures of the above polymers, etc. can be cited. The transparent protective film may contain one or more of any appropriate additives. Examples of the additives include: ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, coloring agents, etc. The content of the above-mentioned thermoplastic resin in the transparent protective film is preferably 50-100% by mass, more preferably 50-99% by mass, further preferably 60-98% by mass, and particularly preferably 70-97% by mass. When the content of the above-mentioned thermoplastic resin in the transparent protective film is less than 50% by mass, there is a risk that the high transparency inherent in the thermoplastic resin cannot be fully exhibited.

另外，作為透明保護薄膜，可列舉日本特開2001-343529號公報(WO01/37007)中記載的聚合物薄膜，例如(A)含有側鏈具有取代及/或未取代醯亞胺基的熱塑性樹脂及側鏈具有取代及/或未取代苯基及腈基的熱塑性樹脂的樹脂組合物。作為具體例，可列舉含有由異丁烯與N-甲基馬來醯亞胺形成的交替共聚物及丙烯腈-苯乙烯共聚物的樹脂組合物的薄膜。薄膜可以使用由樹脂組合物的混合擠出品等形成的薄膜。這些薄膜的相位差小、光彈性係數小，因此能夠消除由偏光薄膜的應變導致的不均等不良情況，另外，透濕度小，因此加濕耐久性優異。In addition, as the transparent protective film, there can be cited polymer films described in Japanese Patent Publication No. 2001-343529 (WO01/37007), for example, (A) a resin composition containing a thermoplastic resin having a substituted and/or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted and/or unsubstituted phenyl and nitrile group in the side chain. As a specific example, there can be cited a film containing a resin composition of an alternating copolymer formed of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. The film can be formed of a mixed extrusion product of the resin composition. These films have a small phase difference and a small optical elastic coefficient, so they can eliminate the unevenness caused by the strain of the polarizing film. In addition, they have a low moisture permeability, so they have excellent humidification durability.

另外，在本發明中使用的透明保護薄膜的透濕度較佳為150g/m² /24h以下。根據該構成，空氣中的水分不易進入偏光薄膜中，可以抑制偏光薄膜本身的水分率變化。其結果，可以抑制因保存環境而產生的偏光薄膜的捲曲、尺寸變化。In addition, the moisture permeability of the transparent protective film used in the present invention is preferably 150 g/m ² /24h or less. According to this structure, moisture in the air is not easy to enter the polarizing film, and the change of the moisture content of the polarizing film itself can be suppressed. As a result, the curling and dimensional change of the polarizing film caused by the storage environment can be suppressed.

作為設置於偏光件的單面或兩面的透明保護薄膜，較佳透明性、機械強度、熱穩定性、水分阻隔性、各向同性等優異的透明保護薄膜，特別是透濕度更佳為150g/m² /24h以下、特佳為120g/m² /24h以下、再進一步更佳為5~70g/m² /24h以下。As a transparent protective film disposed on one or both sides of a polarizer, a transparent protective film having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc. is preferred, and in particular, a moisture permeability is preferably 150 g/m ² /24h or less, particularly preferably 120 g/m ² /24h or less, and further preferably 5-70 g/m ² /24h or less.

作為滿足上述低透濕度的透明保護薄膜的形成材料，例如可以使用聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯等聚酯樹脂；聚碳酸酯樹脂；聚芳酯類樹脂；尼龍、芳香族聚醯胺等醯胺類樹脂；聚乙烯、聚丙烯、乙烯-丙烯共聚物這樣的聚烯烴類聚合物、具有環類或降冰片烯結構的環狀烯烴類樹脂、(甲基)丙烯酸類樹脂、或它們的混合體。上述樹脂中，較佳為聚碳酸酯類樹脂、環狀聚烯烴類樹脂、(甲基)丙烯酸類樹脂，特別是以環狀聚烯烴類樹脂、(甲基)丙烯酸類樹脂為佳。As the material for forming the transparent protective film satisfying the above-mentioned low moisture permeability, for example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; polyarylate resins; amide resins such as nylon and aromatic polyamide; polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; cyclic olefin resins having a cyclic or norbornene structure, (meth)acrylic resins, or mixtures thereof can be used. Among the above-mentioned resins, polycarbonate resins, cyclic polyolefin resins, and (meth)acrylic resins are preferred, and cyclic polyolefin resins and (meth)acrylic resins are particularly preferred.

透明保護薄膜的厚度可以適宜地決定，一般來說，從強度、處理性等操作性、薄層性等方面出發，較佳5~100μm。特佳10~60μm、再更佳13~40μm。The thickness of the transparent protective film can be appropriately determined. Generally speaking, from the perspectives of strength, handling properties, thinness, etc., 5 to 100 μm is preferred, 10 to 60 μm is particularly preferred, and 13 to 40 μm is even more preferred.

上述透明保護薄膜通常使用正面相位差小於40nm、且厚度方向相位差小於80nm的透明保護薄膜。正面相位差Re由Re＝(nx－ny)×d表示。厚度方向相位差Rth由Rth＝(nx－nz)×d表示。另外，Nz係數由Nz＝(nx－nz)/(nx－ny)表示。[其中，將薄膜的遲相軸方向、進相軸方向及厚度方向的折射率分別設為nx、ny、nz，將d(nm)設為薄膜的厚度。遲相軸方向設為薄膜面內的折射率達到最大的方向。]。需要說明的是，透明保護薄膜較佳盡可能無著色。較佳使用厚度方向的相位差值為-90nm~＋75nm的保護薄膜。藉由使用上述厚度方向的相位差值(Rth)為-90nm~＋75nm的保護薄膜，能夠基本消除起因於透明保護薄膜的偏光薄膜的著色(光學著色)。厚度方向相位差值(Rth)更佳為-80nm~＋60nm、特佳為-70nm~＋45nm。The above-mentioned transparent protective film usually uses a transparent protective film with a front phase difference of less than 40nm and a thickness direction phase difference of less than 80nm. The front phase difference Re is represented by Re = (nx-ny) × d. The thickness direction phase difference Rth is represented by Rth = (nx-nz) × d. In addition, the Nz coefficient is represented by Nz = (nx-nz) / (nx-ny). [Wherein, the refractive index of the film in the direction of the slow axis, the direction of the fast axis and the thickness direction is set to nx, ny, nz respectively, and d (nm) is set to the thickness of the film. The slow axis direction is set to the direction in which the refractive index in the film plane reaches the maximum. ]. It should be noted that the transparent protective film is preferably as non-colored as possible. It is better to use a protective film with a phase difference value in the thickness direction of -90nm~+75nm. By using the protective film having a thickness direction retardation value (Rth) of -90nm to +75nm, the coloring (optical coloring) of the polarizing film caused by the transparent protective film can be basically eliminated. The thickness direction retardation value (Rth) is more preferably -80nm to +60nm, and particularly preferably -70nm to +45nm.

另一方面，作為上述透明保護薄膜，可使用具有正面相位差為40nm以上及/或厚度方向相位差為80nm以上的相位差板。通常將正面相位差控制為40~200nm的範圍，通常將厚度方向相位差控制為80~300nm的範圍。使用相位差板作為透明保護薄膜時，該相位差板也作為透明保護薄膜發揮作用，因此能實現薄型化。On the other hand, as the above-mentioned transparent protective film, a phase difference plate having a front phase difference of 40 nm or more and/or a thickness direction phase difference of 80 nm or more can be used. The front phase difference is usually controlled to be in the range of 40 to 200 nm, and the thickness direction phase difference is usually controlled to be in the range of 80 to 300 nm. When a phase difference plate is used as a transparent protective film, the phase difference plate also acts as a transparent protective film, so that thinning can be achieved.

作為相位差板，可列舉出：對高分子原材料進行單軸或雙軸拉伸處理而成的雙折射性薄膜、液晶聚合物的配向薄膜、以薄膜支撐液晶聚合物的配向層而成的相位差板等。相位差板的厚度也沒有特殊限制，通常為20~150μm左右。作為高分子原料，可列舉出例如：聚乙烯醇、聚乙烯基縮丁醛、聚甲基乙烯基醚、聚丙烯酸羥基乙酯、羥乙基纖維素、羥丙基纖維素、甲基纖維素、聚碳酸酯、聚丙烯酸酯、聚碸、聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯、聚醚碸、聚苯硫醚、聚苯醚、聚烯丙基磺酸、聚醯胺、聚醯亞胺、聚烯烴、聚氯乙烯、纖維素樹脂、環狀聚烯烴樹脂(降冰片烯類樹脂)、或它們的二元系、三元系各種共聚物、接枝共聚物、混合物等。這些高分子原料藉由拉伸等而成為配向物(拉伸薄膜)。As the phase difference plate, there are: birefringent film formed by uniaxial or biaxial stretching of polymer raw materials, liquid crystal polymer alignment film, phase difference plate formed by film supporting liquid crystal polymer alignment layer, etc. There is no special restriction on the thickness of the phase difference plate, which is usually about 20~150μm. Examples of polymer raw materials include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, polycarbonate, polyacrylate, polysulfone, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyphenylene sulfide, polyphenylene ether, polyallyl sulfonic acid, polyamide, polyimide, polyolefin, polyvinyl chloride, cellulose resin, cyclic polyolefin resin (norbornene resin), or various binary and ternary copolymers, graft copolymers, and mixtures thereof. These polymer raw materials are formed into oriented materials (stretched films) by stretching or the like.

作為液晶聚合物，可列舉出例如：將賦予液晶配向性的共軛性的直線狀原子團(介晶)導入至聚合物的主鏈、側鏈的主鏈型、側鏈型的各種液晶聚合物等。作為主鏈型的液晶聚合物的具體例，可列舉出以賦予彎曲性的間隔部使介晶基(Mesogen group)鍵合的結構的、例如向列配向性的聚酯類液晶性聚合物、盤狀聚合物、膽甾型聚合物等。作為側鏈型的液晶聚合物的具體例，可列舉出以聚矽氧烷、聚丙烯酸酯、聚甲基丙烯酸酯或聚丙二酸酯為主鏈骨架、隔著由共軛性原子團構成的間隔部具有由向列配向賦予性的對位取代環狀化合物單元構成的介晶部作為側鏈的液晶聚合物。這些液晶聚合物是例如對在玻璃板上形成的聚醯亞胺、聚乙烯醇等薄膜的表面進行了研磨處理而成的液晶聚合物、對氧化矽進行了斜向蒸鍍而成的液晶聚合物等，在其配向處理面上展開液晶性聚合物的溶液並進行熱處理而進行。Examples of liquid crystal polymers include various liquid crystal polymers of the main chain type and side chain type in which conjugated linear atomic groups (mesogens) imparting liquid crystal alignment are introduced into the main chain and side chain of the polymer. Specific examples of main chain type liquid crystal polymers include polyester liquid crystal polymers of the type having a structure in which mesogen groups are bonded with spacers imparting curvature, such as nematic alignment, discotic polymers, and cholesteric polymers. As specific examples of side chain type liquid crystal polymers, there can be cited liquid crystal polymers having polysiloxane, polyacrylate, polymethacrylate or polymalonate as the main chain skeleton, and having a mesogen composed of a para-substituted cyclic compound unit that imparts nematic alignment via a spacer composed of a conjugated atomic group as the side chain. These liquid crystal polymers are, for example, liquid crystal polymers obtained by polishing the surface of a film of polyimide, polyvinyl alcohol or the like formed on a glass plate, liquid crystal polymers obtained by obliquely evaporating silicon oxide, and the like, and are produced by spreading a solution of a liquid crystal polymer on the alignment treated surface and performing a heat treatment.

相位差板可以是例如各種波片、根據使用目的具有適宜相位差的相位差板，該使用目的為利用液晶層的雙折射的著色、視角等的補償的目的等，也可以是積層2種以上相位差板從而控制了相位差等光學特性的相位差板。The phase difference plate can be, for example, various wave plates, a phase difference plate with an appropriate phase difference depending on the purpose of use, such as coloring and compensation for the viewing angle of the double refraction of the liquid crystal layer, or a phase difference plate in which optical properties such as phase difference are controlled by stacking two or more phase difference plates.

相位差板可以根据各种用途选择使用满足nx＝ny＞nz、nx＞ny＞nz、nx＞ny＝nz、nx＞nz＞ny、nz＝nx＞ny、nz＞nx＞ny、nz＞nx＝ny的關系的相位差板。需要說明的是，ny＝nz不僅包括ny與nz完全相同的情況，也包括ny與nz實質上相同的情況。The phase difference plate can be selected to use a phase difference plate that satisfies the relationship of nx＝ny＞nz, nx＞ny＞nz, nx＞ny＝nz, nx＞nz＞ny, nz＝nx＞ny, nz＞nx＞ny, nz＞nx＝ny according to various uses. It should be noted that ny＝nz includes not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.

例如滿足nx＞ny＞nz的相位差板中，較佳使用正面相位差滿足40~100nm、厚度方向相位差滿足100~320nm、Nz係數滿足1.8~4.5的相位差板。例如對於滿足nx＞ny＝nz的相位差板(正A板)而言，較佳使用正面相位差滿足100~200nm的相位差板。例如對於滿足nz＝nx＞ny的相位差板(負A板)而言，較佳使用正面相位差滿足100~200nm的相位差板。例如對於滿足nx＞nz＞ny的相位差板而言，較佳使用正面相位差滿足150~300nm、Nz係數滿足大於0且小於0.7的相位差板。另外，如上所述，可使用例如滿足nx＝ny＞nz、nz＞nx＞ny、或nz＞nx＝ny的相位差板。For example, among the phase difference plates satisfying nx＞ny＞nz, it is preferred to use a phase difference plate having a front phase difference satisfying 40~100nm, a thickness direction phase difference satisfying 100~320nm, and an Nz coefficient satisfying 1.8~4.5. For example, for the phase difference plate satisfying nx＞ny＝nz (positive A plate), it is preferred to use a phase difference plate having a front phase difference satisfying 100~200nm. For example, for the phase difference plate satisfying nz＝nx＞ny (negative A plate), it is preferred to use a phase difference plate having a front phase difference satisfying 100~200nm. For example, for the phase difference plate satisfying nx＞nz＞ny, it is preferred to use a phase difference plate having a front phase difference satisfying 150~300nm, and an Nz coefficient satisfying a phase difference greater than 0 and less than 0.7. In addition, as described above, for example, a phase difference plate satisfying nx=ny>nz, nz>nx>ny, or nz>nx=ny can be used.

透明保護薄膜可以根據要應用的液晶顯示裝置來適宜選擇。例如VA(Vertical Alignment，包括MVA、PVA)的情況下，較佳偏光薄膜的至少單側(單元側)的透明保護薄膜具有相位差。作為具體的相位差，較佳為Re＝0~240nm、Rth＝0~500nm的範圍。以三維折射率記載時，較佳nx＞ny＝nz、nx＞ny＞nz、nx＞nz＞ny、nx＝ny＞nz(正A板、雙軸、負C板)的情況。VA型中，較佳以正A板與負C板的組合、或1張雙軸薄膜的形式使用。在液晶單元的上下使用偏光薄膜時，液晶單元的上下可以都具有相位差、或上下中的任一透明保護薄膜具有相位差。The transparent protective film can be appropriately selected according to the liquid crystal display device to be applied. For example, in the case of VA (Vertical Alignment, including MVA, PVA), it is preferred that the transparent protective film on at least one side (unit side) of the polarizing film has a phase difference. As a specific phase difference, the preferred range is Re = 0 ~ 240nm, Rth = 0 ~ 500nm. When recorded in three-dimensional refractive index, it is preferred that nx > ny = nz, nx > ny > nz, nx > nz > ny, nx = ny > nz (positive A plate, biaxial, negative C plate). In the VA type, it is preferably used in the form of a combination of a positive A plate and a negative C plate, or a single biaxial film. When polarizing films are used on the upper and lower sides of the liquid crystal unit, both the upper and lower sides of the liquid crystal unit may have a phase difference, or any one of the upper and lower transparent protective films may have a phase difference.

例如可以在IPS(In-Plane Switching，包括FFS)的情况，偏光薄膜的單側的透明保護薄膜具有相位差的情况、不具有相位差的情况中的任一情況下使用。例如不具有相位差的情況較佳為液晶單元的上下(單元側)也不具有相位差的情況。具有相位差的情況較佳為液晶單元的上下都具有相位差的情況、上下中的任一者具有相位差的情況(例如上側具有滿足nx＞nz＞ny關係的雙軸薄膜、下側無相位差的情況、上側具有正A板、下側具有正C板的情況)。具有相位差的情況下，較佳Re＝-500~500nm、Rth＝-500~500nm的範圍。以三維折射率記載時，較佳nx＞ny＝nz、nx＞nz＞ny、nz＞nx＝ny、nz＞nx＞ny(正A板、雙軸、正C板)。For example, in the case of IPS (In-Plane Switching, including FFS), the transparent protective film on one side of the polarizing film can be used in any of the cases where it has a phase difference or does not have a phase difference. For example, the case where there is no phase difference is preferably a case where the upper and lower sides (sides of the unit) of the liquid crystal unit do not have a phase difference. The case where there is a phase difference is preferably a case where both the upper and lower sides of the liquid crystal unit have a phase difference, or a case where either the upper and lower sides have a phase difference (for example, the upper side has a biaxial film satisfying the relationship nx＞nz＞ny, and the lower side has no phase difference, or the upper side has a positive A plate and the lower side has a positive C plate). In the case where there is a phase difference, the preferred range is Re=-500~500nm and Rth=-500~500nm. When recorded in three-dimensional refractive index, it is better to have nx＞ny＝nz, nx＞nz＞ny, nz＞nx＝ny, nz＞nx＞ny (positive A plate, biaxial, positive C plate).

對於透明保護薄膜，為了彌補其機械強度、操作性，可以進一步積層剝離性基材。剝離性基材可以在將透明保護薄膜及偏光件貼合前或者貼合後，在步驟中或者其它步驟中從含有透明保護薄膜及偏光件的積層體中剝離。For the transparent protective film, in order to supplement its mechanical strength and operability, a peelable substrate can be further laminated. The peelable substrate can be peeled off from the laminate containing the transparent protective film and the polarizer before or after laminating the transparent protective film and the polarizer in the step or in other steps.

以下，對本發明的偏光薄膜的製造方法中的各步驟進行說明。Hereinafter, each step in the method for manufacturing the polarizing film of the present invention will be described.

本發明的偏光薄膜的製造方法具有：第一塗敷步驟，在透明保護薄膜的貼合面塗敷黏接劑組合物；貼合步驟，使偏光件及透明保護薄膜貼合；以及黏接步驟，從偏光件面側或透明保護薄膜面側照射活性能量射線，使黏接劑組合物固化而得到黏接劑層，從而隔著上述黏接劑層使偏光件及上述透明保護薄膜黏接。較佳在上述貼合步驟之前進一步具有第二塗敷步驟，該第二塗敷步驟在偏光件的貼合面塗敷易黏接組合物。在具有第二塗敷步驟的情況下，在黏接步驟中，隔著使黏接劑組合物及易黏接組合物固化而得到的黏接劑層使偏光件及上述透明保護薄膜黏接。The manufacturing method of the polarizing film of the present invention comprises: a first coating step of coating an adhesive composition on the bonding surface of the transparent protective film; a bonding step of bonding the polarizer and the transparent protective film; and a bonding step of irradiating active energy rays from the side of the polarizer or the side of the transparent protective film to cure the adhesive composition to obtain an adhesive layer, thereby bonding the polarizer and the transparent protective film through the adhesive layer. Preferably, a second coating step is further provided before the bonding step, wherein the easy-bonding composition is coated on the bonding surface of the polarizer. When the second coating step is included, in the bonding step, the polarizer and the transparent protective film are bonded to each other via an adhesive layer obtained by curing the adhesive composition and the easy-bonding composition.

需要說明的是，可以在塗敷步驟前對偏光件及透明保護薄膜進行表面改性處理。特別是以對偏光件的表面進行表面改性處理為佳。作為表面改性處理，可列舉電暈處理、等離子體處理、準分子處理及火焰處理等，特別是以電暈處理為佳。藉由進行電暈處理，在偏光件表面生成羰基、胺基等反應性官能團，與黏接劑層的密合性提高。另外，可以藉由灰化效果去除表面的雜質、或者減輕表面的凹凸，從而製成外觀特性優異的偏光薄膜。It should be noted that the polarizer and the transparent protective film may be subjected to surface modification treatment before the coating step. In particular, it is preferred to perform surface modification treatment on the surface of the polarizer. Examples of surface modification treatments include corona treatment, plasma treatment, excimer treatment, and flame treatment, and corona treatment is particularly preferred. By performing the corona treatment, reactive functional groups such as carbonyl and amine groups are generated on the surface of the polarizer, and the adhesion with the adhesive layer is improved. In addition, impurities on the surface can be removed or surface irregularities can be reduced by the ashing effect, thereby producing a polarizing film with excellent appearance characteristics.

＜黏接劑組合物的塗敷步驟＞ 作為在透明保護薄膜的貼合面塗敷黏接劑組合物的方法，可以根據組合物的黏度、目標厚度適宜選擇，從透明保護薄膜表面的異物除去、塗敷性的觀點考慮，較佳使用後測量塗敷方式。作為後測量塗敷方式的具體例，可列舉凹版輥塗敷方式、正向輥塗敷方式、氣刀塗敷方式、桿/棒塗敷方式等。這些當中，從透明保護薄膜表面的異物除去、塗敷性的觀點考慮，特別是以凹版輥塗敷方式為佳。<Adhesive composition application step> As a method for applying the adhesive composition to the bonding surface of the transparent protective film, it can be appropriately selected according to the viscosity and target thickness of the composition. From the perspective of removing foreign matter on the surface of the transparent protective film and coating properties, it is preferable to use a post-measurement coating method. Specific examples of the post-measurement coating method include a gravure roller coating method, a forward roller coating method, an air knife coating method, and a rod/stick coating method. Among these, the gravure roller coating method is particularly preferable from the perspective of removing foreign matter on the surface of the transparent protective film and coating properties.

＜易黏接組合物的塗敷步驟＞ 本發明中，可以在偏光件的一面塗敷易黏接組合物，也可以在偏光件的兩面塗敷易黏接組合物。作為在偏光件的貼合面塗敷易黏接組合物的方法，從發揮與黏接劑組合物的塗敷步驟同樣的效果方面考慮，較佳利用後測量塗敷方式。<Application step of easy-adhesive composition> In the present invention, the easy-adhesive composition can be applied to one side of the polarizer or to both sides of the polarizer. As a method of applying the easy-adhesive composition to the bonding surface of the polarizer, it is preferable to use the post-measurement application method in order to achieve the same effect as the application step of the adhesive composition.

在凹版輥塗敷方式中，可以在凹版輥的表面形成各種圖案，例如，可以形成蜂窩網圖案、梯形圖案、格子圖案、錐形圖案或斜線圖案等。為了有效地防止最終得到的偏光薄膜產生外觀缺點，較佳形成於上述凹版輥的表面的圖案為蜂窩網圖案。在蜂窩網圖案的情況下，為了提高黏接劑組合物或塗敷易黏接組合物後的塗敷面的面精度，單元容積較佳為1~5cm³ /m² 、更佳為2~3cm³ /m² 。同樣地，為了提高黏接劑組合物或塗敷易黏接組合物後的塗敷面的面精度，每1英寸的輥的單元線數較佳為200~3000條線/英寸。另外，相對於偏光件的行進速度，上述凹版輥的轉速比較佳為100~300%。In the gravure roller coating method, various patterns can be formed on the surface of the gravure roller, for example, a honeycomb pattern, a trapezoidal pattern, a lattice pattern, a pyramidal pattern or a diagonal pattern. In order to effectively prevent the appearance defects of the polarizing film finally obtained, the pattern formed on the surface of the gravure roller is preferably a honeycomb pattern. In the case of the honeycomb pattern, in order to improve the surface accuracy of the coating surface after the adhesive composition or the easy-bonding composition is applied, the unit volume is preferably 1-5 cm ³ /m ² , more preferably 2-3 cm ³ /m ² . Similarly, in order to improve the surface accuracy of the adhesive composition or the coated surface after the easy-bonding composition is applied, the number of unit lines per inch of the roller is preferably 200 to 3000 lines/inch. In addition, the rotation speed of the gravure roller is preferably 100 to 300% relative to the travel speed of the polarizer.

＜易黏接組合物的乾燥步驟＞ 在本發明的偏光薄膜的製造方法中，可以藉由在偏光件的貼合面塗敷易黏接組合物而形成帶易黏接層的偏光件，也可以藉由在易黏接組合物的塗敷步驟之後根據需要設置乾燥步驟而形成帶易黏接層的偏光件。乾燥步驟可以使用本領域技術人員公知的步驟，例如風乾步驟、加熱步驟、熱風風乾步驟。<Drying step of the easy-adhesive composition> In the manufacturing method of the polarizing film of the present invention, a polarizing element with an easy-adhesive layer can be formed by applying an easy-adhesive composition on the bonding surface of the polarizing element, or a polarizing element with an easy-adhesive layer can be formed by providing a drying step as needed after the application step of the easy-adhesive composition. The drying step can use a step known to those skilled in the art, such as an air drying step, a heating step, or a hot air drying step.

＜貼合步驟＞ 透過如上述那樣塗布的黏接劑組合物或黏接劑組合物、及易黏接組合物，將偏光件及透明保護薄膜貼合。在貼合步驟中，黏接劑組合物及易黏接組合物均未固化，因此，藉由貼合而相互混合，在該狀態下在接下來的黏接步驟中固化，從而形成黏接劑層。偏光件及透明保護薄膜的貼合可以利用輥式層壓機等來進行。<Laminating step> The polarizer and the transparent protective film are laminated together using the adhesive composition or the adhesive composition and the easy-bonding composition applied as described above. In the laminating step, the adhesive composition and the easy-bonding composition are not cured, so they are mixed with each other by laminating, and in this state, they are cured in the next laminating step to form an adhesive layer. The laminating of the polarizer and the transparent protective film can be performed using a roll laminating machine or the like.

＜黏接步驟＞ 將偏光件及透明保護薄膜貼合後，照射活性能量射線(電子束、紫外線、可見光等)，使黏接劑組合物、或者使黏接劑組合物及易黏接組合物固化，從而形成黏接劑層。活性能量射線(電子束、紫外線、可見光等)的照射方向可從任意適當的方向照射。較佳從透明保護薄膜側照射。如果從偏光件側照射，則存在偏光件因活性能量射線(電子束、紫外線、可見光等)而劣化之虞。<Bonding step> After the polarizer and the transparent protective film are bonded together, active energy rays (electron beam, ultraviolet rays, visible light, etc.) are irradiated to cure the adhesive composition, or the adhesive composition and the easy-bonding composition, thereby forming an adhesive layer. The irradiation direction of the active energy rays (electron beam, ultraviolet rays, visible light, etc.) can be irradiated from any appropriate direction. It is preferably irradiated from the transparent protective film side. If irradiated from the polarizer side, there is a risk that the polarizer will be degraded by the active energy rays (electron beam, ultraviolet rays, visible light, etc.).

照射電子束的情況下的照射條件只要是能使上述黏接劑組合物固化的條件即可，可以採用任意適當的條件。例如，電子束照射的加速電壓較佳為5kV~300kV、更佳為10kV~250kV。加速電壓小於5kV時，有電子束不能達到黏接劑、變得固化不充分之虞，如果加速電壓大於300kV，則有穿過試樣的浸透力過強而對透明保護薄膜、偏光件帶來損傷之虞。作為照射線量，為5~100kGy、更佳為10~75kGy。照射線量小於5kGy時，黏接劑的固化不充分，如果大於100kGy，則對透明保護薄膜、偏光件帶來損傷，發生機械強度的降低、黃變，無法得到給定的光學特性。When irradiating with electron beams, any appropriate irradiation conditions may be used as long as the above-mentioned adhesive composition can be cured. For example, the accelerating voltage of electron beam irradiation is preferably 5kV~300kV, and more preferably 10kV~250kV. When the accelerating voltage is less than 5kV, there is a risk that the electron beam cannot reach the adhesive and the curing is insufficient. If the accelerating voltage is greater than 300kV, there is a risk that the penetration through the sample is too strong and the transparent protective film and polarizer are damaged. The irradiation dose is 5~100kGy, and more preferably 10~75kGy. When the irradiation dose is less than 5 kGy, the adhesive will not be cured sufficiently. When it is greater than 100 kGy, the transparent protective film and polarizer will be damaged, the mechanical strength will be reduced, yellowing will occur, and the given optical properties will not be obtained.

電子束照射通常在非活性氣體中進行照射，可以根據需要在大氣中、少量導入了氧的條件下進行。根據透明保護薄膜的材料的不同，適宜導入氧，與最初電子束接觸的透明保護薄膜面接觸，發生氧阻礙，可防止對透明保護薄膜的損傷，可以僅對黏接劑高效地照射電子束。Electron beam irradiation is usually performed in an inert gas, but can be performed in the atmosphere with a small amount of oxygen introduced if necessary. Depending on the material of the transparent protective film, oxygen can be introduced appropriately to contact the transparent protective film surface that first contacts the electron beam, creating an oxygen barrier, thereby preventing damage to the transparent protective film and allowing the electron beam to be efficiently irradiated only to the adhesive.

在本發明的偏光薄膜之製造方法中，作為活性能量射線，較佳使用包含波長範圍380nm~450nm的可見光的活性能量射線、特別是波長範圍380nm~450nm的可見光的照射量最多的活性能量射線。在使用紫外線、可見光、且使用賦予了紫外線吸收能力的透明保護薄膜(紫外線不透射型透明保護薄膜)的情況下，吸收大約比380nm短波長的光，因此，比380nm短波長的光不會到達黏接劑組合物，對其聚合反應沒有貢獻。此外，由透明保護薄膜吸收的比380nm短波長的光轉化成熱，透明保護薄膜自身發熱，成為偏光薄膜捲曲/褶皺等不良的原因。因此，在本發明中，在採用紫外線、可見光的情況下，較佳使用不發出比380nm短波長的光的裝置作為活性能量射線發生裝置，更具體而言，波長範圍380~440nm的累積照度與波長範圍250~370nm的累積照度之比較佳為100:0~100:50、更佳為100:0~100:40。在本發明的偏光薄膜之製造方法中，作為活性能量射線，較佳封入有鎵的金屬鹵化物燈、發出波長範圍380~440nm的光的LED光源。或者可以使用低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、白熾燈、氙燈、鹵素燈、碳弧燈、金屬鹵化物燈、螢光燈、鎢燈、鎵燈、準分子鐳射或太陽光等包含紫外線及可見光的光源，也可以用帶通濾波器將比380nm短的波長的紫外線阻斷後使用。為了提高偏光件與透明保護薄膜之間的黏接劑層的黏接性能，並防止偏光薄膜的捲曲，較佳使用封入有鎵的金屬鹵化物燈，且使用透過可阻斷比380nm短波長的光的帶通濾波器得到的活性能量射線、或使用LED光源得到的波長405nm的活性能量射線。In the method for manufacturing the polarizing film of the present invention, as the active energy ray, it is preferred to use active energy ray including visible light in the wavelength range of 380nm to 450nm, especially active energy ray with the largest irradiation amount of visible light in the wavelength range of 380nm to 450nm. When ultraviolet light, visible light, and a transparent protective film endowed with ultraviolet light absorption ability (ultraviolet light non-transmissive transparent protective film) are used, light with a wavelength shorter than about 380nm is absorbed, so light with a wavelength shorter than 380nm does not reach the adhesive composition and does not contribute to its polymerization reaction. In addition, the light with a wavelength shorter than 380nm absorbed by the transparent protective film is converted into heat, and the transparent protective film itself generates heat, which becomes the cause of defects such as curling/wrinkling of the polarizing film. Therefore, in the present invention, when ultraviolet rays or visible light are used, it is preferred to use a device that does not emit light with a wavelength shorter than 380nm as the active energy ray generating device. More specifically, the ratio of the accumulated illuminance in the wavelength range of 380-440nm to the accumulated illuminance in the wavelength range of 250-370nm is preferably 100:0-100:50, more preferably 100:0-100:40. In the method for manufacturing a polarizing film of the present invention, as the active energy ray, a metal halide lamp enclosed in gallium or an LED light source that emits light in the wavelength range of 380-440nm is preferred. Alternatively, a light source containing ultraviolet and visible light, such as a low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, incandescent lamp, xenon lamp, halogen lamp, carbon arc lamp, metal halide lamp, fluorescent lamp, tungsten lamp, gallium lamp, excimer laser or sunlight, may be used. Ultraviolet light with a wavelength shorter than 380 nm may also be blocked by a bandpass filter. In order to improve the bonding performance of the adhesive layer between the polarizer and the transparent protective film and prevent the polarizing film from curling, it is preferred to use a metal halide lamp enclosed in gallium and use active energy rays obtained through a bandpass filter that blocks light with a wavelength shorter than 380nm, or active energy rays with a wavelength of 405nm obtained using an LED light source.

較佳在照射紫外線或可見光前對黏接劑組合物進行加熱(照射前加熱)，該情況下，較佳加熱至40℃以上、更佳加熱至50℃以上。另外，亦較佳在照射紫外線或可見光後對活性能量射線固化型黏接劑組合物進行加熱(照射後加熱)，該情況下，較佳加熱至40℃以上、更佳加熱至50℃以上。The adhesive composition is preferably heated before irradiation with ultraviolet rays or visible light (heating before irradiation), and in this case, it is preferably heated to 40°C or higher, and more preferably heated to 50°C or higher. In addition, the active energy ray-curable adhesive composition is also preferably heated after irradiation with ultraviolet rays or visible light (heating after irradiation), and in this case, it is preferably heated to 40°C or higher, and more preferably heated to 50°C or higher.

本發明中使用的黏接劑組合物特別是在形成將偏光件與波長365nm的透光率小於5%的透明保護薄膜黏接而成的黏接劑層的情況下可以適宜使用。此處，本發明使用的黏接劑組合物藉由含有上述的通式(3)的光聚合引發劑，能夠隔著具有UV吸收能力的透明保護薄膜照射紫外線而固化形成黏接劑層。因此，即使對於在偏光件的兩面積層有具有UV吸收能力的透明保護薄膜的偏光薄膜，也能夠使黏接劑層固化。但是，當然，對於積層有不具有UV吸收能力的透明保護薄膜的偏光薄膜，也能夠使黏接劑層固化。需要說明的是，具有UV吸收能力的透明保護薄膜是指對380nm的光的透射率小於10%的透明保護薄膜。The adhesive composition used in the present invention can be particularly suitably used in the case of forming an adhesive layer formed by bonding a polarizer to a transparent protective film having a transmittance of less than 5% at a wavelength of 365 nm. Here, the adhesive composition used in the present invention can be cured to form an adhesive layer by irradiating ultraviolet rays through a transparent protective film having UV absorption ability by containing the photopolymerization initiator of the above-mentioned general formula (3). Therefore, even for a polarizing film in which a transparent protective film having UV absorption ability is laminated on both sides of the polarizer, the adhesive layer can be cured. However, of course, for a polarizing film in which a transparent protective film without UV absorption ability is laminated, the adhesive layer can also be cured. It should be noted that the transparent protective film having UV absorption capability refers to a transparent protective film having a transmittance of less than 10% for light at 380 nm.

作為對透明保護薄膜賦予UV吸收能力的方法，可列舉：使透明保護薄膜中含有紫外線吸收劑的方法、在透明保護薄膜表面積層含有紫外線吸收劑的表面處理層的方法。As a method for imparting UV absorption capability to the transparent protective film, there are two methods: a method of making the transparent protective film contain an ultraviolet absorber, and a method of laminating a surface treatment layer containing an ultraviolet absorber on the surface of the transparent protective film.

作為紫外線吸收劑的具體例，例如可列舉：以往公知的氧基二苯甲酮類化合物、苯并***類化合物、水楊酸酯類化合物、二苯甲酮類化合物、氰基丙烯酸酯類化合物、鎳絡鹽類化合物、三嗪類化合物等。Specific examples of the ultraviolet absorber include conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel salt compounds, triazine compounds, and the like.

在以連續生產線製造本發明的偏光薄膜時，線速度因黏接劑組合物的固化時間而異，較佳為1~500m/min、更佳為5~300m/min、進一步更佳為10~100m/min。線速度過小時，生產性不足，或者對透明保護薄膜的損傷過大，無法製作能耐受耐久性試驗等的偏光薄膜。線速度過大時，有時固化性樹脂組合物的固化變得不充分，得不到目標黏接性。When the polarizing film of the present invention is manufactured by a continuous production line, the line speed varies depending on the curing time of the adhesive composition, and is preferably 1 to 500 m/min, more preferably 5 to 300 m/min, and even more preferably 10 to 100 m/min. When the line speed is too low, productivity is insufficient, or damage to the transparent protective film is too great, and a polarizing film that can withstand durability tests, etc. cannot be manufactured. When the line speed is too high, the curing of the curable resin composition may become insufficient, and the target adhesion cannot be obtained.

＜光學薄膜＞ 藉由本發明的製造方法製造的偏光薄膜在實用時可以製成與其它光學層積層而成的光學薄膜來使用。對於該光學層，沒有特別限定，可列舉例如：相位差薄膜(包括1/2、1/4等波片)、視覺補償薄膜、亮度提高薄膜、反射板、反透射板等成為會在液晶顯示裝置等的形成時使用的光學層的光學薄膜。<Optical film> The polarizing film produced by the manufacturing method of the present invention can be used as an optical film laminated with other optical layers when it is practical. There is no particular limitation on the optical layer, and examples thereof include: phase difference film (including 1/2, 1/4 wave plates), visual compensation film, brightness enhancement film, reflective plate, anti-transmission plate, etc., which are optical films that are used in the formation of liquid crystal display devices, etc.

作為上述相位差薄膜，可以使用具有正面相位差為40nm以上及/或厚度方向相位差為80nm以上的相位差薄膜。通常將正面相位差控制為40~200nm的範圍，通常將厚度方向相位差控制為80~300nm的範圍。As the above-mentioned retardation film, a retardation film having a front retardation of 40 nm or more and/or a thickness direction retardation of 80 nm or more can be used. The front retardation is usually controlled to be in the range of 40 to 200 nm, and the thickness direction retardation is usually controlled to be in the range of 80 to 300 nm.

作為相位差板，可列舉：對高分子原料進行單軸或雙軸拉伸處理而成的雙折射性薄膜、液晶聚合物的配向薄膜、以薄膜支撐液晶聚合物的配向層而成的相位差板等。相位差薄膜的厚度也沒有特別限制，一般為20~150μm左右。As the phase difference plate, there are: birefringent film formed by uniaxial or biaxial stretching of polymer raw materials, liquid crystal polymer alignment film, phase difference plate formed by film supporting liquid crystal polymer alignment layer, etc. There is no particular restriction on the thickness of the phase difference film, which is generally about 20~150μm.

作為相位差薄膜，可以使用滿足下述式(1)~(3)的逆波長分散型的相位差薄膜： 0.70＜Re[450]/Re[550]＜0.97・・・(1) 1.5×10^-3 ＜Δn＜6×10^-3 ・・・(2) 1.13＜NZ＜1.50・・・(3) (式中，Re[450]及Re[550]分別為在23℃下用波長450nm及550nm的光測定的相位差薄膜的面內的相位差值，Δn為將相位差薄膜的遲相軸方向、進相軸方向的折射率分別設為nx、ny時的nx－ny即面內雙折射，NZ為將nz設為相位差薄膜的厚度方向的折射率時的nx－nz與nx－ny之比，其中nx－nz為厚度方向雙折射、nx－ny為面內雙折射)。As the retardation film, a reverse wavelength dispersion type retardation film satisfying the following formulas (1) to (3) can be used: 0.70＜Re[450]/Re[550]＜0.97・・・(1) 1.5×10 ^-3 ＜Δn＜6×10 ^-3・・・(2) 1.13＜NZ＜1.50・・・(3) (Wherein, Re[450] and Re[550] are the in-plane phase difference values of the phase difference film measured at 23°C using light of wavelengths of 450nm and 550nm, respectively; Δn is nx-ny, i.e., in-plane birefringence, when the refractive indices in the late phase axis direction and the advanced phase axis direction of the phase difference film are set to nx and ny, respectively; NZ is the ratio of nx-nz to nx-ny when nz is set to the refractive index in the thickness direction of the phase difference film, wherein nx-nz is birefringence in the thickness direction and nx-ny is in-plane birefringence).

上述偏光薄膜、積層有至少1層偏光薄膜的光學薄膜上也可以設置用於與液晶單元等其它構件黏接的黏合層。形成黏合層的黏合劑沒有特殊限制，可以適宜地選擇將例如丙烯酸類聚合物、有機矽類聚合物、聚酯、聚胺酯、聚醯胺、聚醚、氟類、橡膠類等聚合物作為基礎聚合物的黏合劑來使用。特別是以可使用丙烯酸類黏合劑那樣的光學透明性優異、顯示出適度的潤濕性、聚集性及黏接性這種黏合特性，耐候性、耐熱性等優異的物質為佳。The polarizing film or the optical film having at least one layer of polarizing film laminated thereon may also be provided with an adhesive layer for bonding to other components such as a liquid crystal unit. There is no particular limitation on the adhesive forming the adhesive layer, and an adhesive having a base polymer such as acrylic polymer, organic silicon polymer, polyester, polyurethane, polyamide, polyether, fluorine, rubber, etc. may be appropriately selected and used. In particular, a material having excellent optical transparency, such as that which can be used with an acrylic adhesive, exhibiting adhesive properties such as appropriate wettability, aggregation and adhesion, and having excellent weather resistance, heat resistance, etc. is preferred.

黏合層可以以不同的組成或種類等的層的重疊層的形式設置於偏光薄膜、光學薄膜的單面或兩面上。另外，設置於兩面的情況下，也可以在偏光薄膜、光學薄膜的表面及背面上形成不同的組成、種類、厚度等的黏合層。黏合層的厚度可以根據使用目的、黏接力等來適宜決定，通常為1~500μm、較佳為1~200μm、特佳為1~100μm。The adhesive layer can be provided on one or both sides of the polarizing film or optical film in the form of a stack of layers of different compositions or types. In addition, when provided on both sides, adhesive layers of different compositions, types, thicknesses, etc. can be formed on the surface and back of the polarizing film or optical film. The thickness of the adhesive layer can be appropriately determined according to the purpose of use, adhesive strength, etc., and is usually 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

黏合層的露出面在直到供於實際使用為止的期間，出於防止其污染等目的，暫時黏接隔膜將其覆蓋。由此，能夠防止在通常的處理狀態下與黏合層接觸。作為隔膜，可以使用除了上述厚度條件以外，根據需要以有機矽類、長鏈烷基類、氟類、硫化鉬等適宜的剝離劑對例如塑膠薄膜、橡膠片、紙、布、無紡布、網、發泡片、金屬箔、它們的層壓體等適宜的薄層體進行塗布處理而成的隔膜等以往規定的適宜的隔膜。The exposed surface of the adhesive layer is temporarily covered with an adhesive diaphragm for the purpose of preventing contamination until it is actually used. This prevents contact with the adhesive layer under normal handling. As a diaphragm, in addition to the above-mentioned thickness conditions, a diaphragm can be used, such as a diaphragm obtained by coating a suitable thin layer such as a plastic film, a rubber sheet, paper, cloth, a non-woven fabric, a net, a foam sheet, a metal foil, a laminate thereof, etc. with a suitable stripping agent such as an organic silane, a long-chain alkyl, a fluorine, or molybdenum sulfide as needed. Suitable diaphragms specified in the past can be used.

＜圖像顯示裝置＞ 本發明的偏光薄膜或光學薄膜可以較佳用於液晶顯示裝置等各種裝置的形成等。液晶顯示裝置的形成可以根據以往的方式來進行。即，液晶顯示裝置通常藉由將液晶單元與偏光薄膜或光學薄膜、及根據需要使用的照明系統等構成部件適宜組裝並將驅動電路裝入等來形成，在本發明中，除了使用本發明的偏光薄膜或光學薄膜這一點以外，沒有特別限定，可以根據以往的方式來進行。關於液晶單元，可以使用例如TN型、STN型、π型等任意類型的液晶單元。<Image display device> The polarizing film or optical film of the present invention can be preferably used for the formation of various devices such as liquid crystal display devices. The formation of the liquid crystal display device can be carried out according to the conventional method. That is, the liquid crystal display device is usually formed by appropriately assembling the liquid crystal unit and the polarizing film or optical film, and the components such as the lighting system used as needed, and installing the driving circuit, etc. In the present invention, except for the use of the polarizing film or optical film of the present invention, there is no special limitation, and it can be carried out according to the conventional method. Regarding the liquid crystal unit, any type of liquid crystal unit such as TN type, STN type, π type, etc. can be used.

可以形成在液晶單元的單側或兩側配置有偏光薄膜或光學薄膜的液晶顯示裝置、在照明系統中使用了背光燈或反射板的液晶顯示裝置等適宜的液晶顯示裝置。在這種情況下，本發明的偏光薄膜或光學薄膜可以配置在液晶單元的單側或兩側。在兩側設置偏光薄膜或光學薄膜的情況下，它們可以相同，也可以不同。進而，在液晶顯示裝置的形成時，可以在適宜的位置配置1層或2層以上的例如擴散板、防眩層、防反射膜、保護板、稜鏡陣列、透鏡陣列片、光擴散板、背光燈等適宜的部件。 實施例Suitable liquid crystal display devices such as a liquid crystal display device with a polarizing film or an optical film disposed on one side or both sides of a liquid crystal unit, and a liquid crystal display device using a backlight or a reflector in a lighting system can be formed. In this case, the polarizing film or the optical film of the present invention can be disposed on one side or both sides of the liquid crystal unit. When polarizing films or optical films are disposed on both sides, they can be the same or different. Furthermore, when forming a liquid crystal display device, one or more layers of suitable components such as a diffusion plate, an anti-glare layer, an anti-reflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, etc. can be disposed at a suitable position. Implementation Example

以下記載本發明的實施例，但本發明的實施方式並不限定於這些。The following describes embodiments of the present invention, but the implementation of the present invention is not limited to these.

＜起偏镜＞ 首先，對非晶性PET基材上成膜有9μm厚的PVA層的積層體藉由拉伸溫度130℃的氣體氛圍中輔助拉伸形成拉伸積層體，接下來，對拉伸積層體藉由染色而形成著色積層體，進一步對著色積層體藉由拉伸溫度65度的硼酸水溶液中拉伸以總拉伸倍率成為5.94倍的方式與非晶性PET基材一體地進行拉伸，形成包含5μm厚的PVA層的光學薄膜積層體。藉由這樣的2步拉伸，可得到構成薄型偏光件的包含厚度5μm的PVA層的光學薄膜積層體，該薄型偏光件在非晶性PET基材上成膜的PVA層的PVA分子發生了高次配向，且藉由染色吸附的碘以聚碘離子絡合物的形式在一個方向上發生了高次配向。<Polarizer> First, a laminate having a 9μm thick PVA layer formed on an amorphous PET substrate was subjected to auxiliary stretching in a gas atmosphere at a stretching temperature of 130°C to form a stretched laminate. Next, the stretched laminate was dyed to form a colored laminate. The colored laminate was further stretched in a boric acid aqueous solution at a stretching temperature of 65°C to a total stretching ratio of 5.94 times, and was stretched together with the amorphous PET substrate to form an optical thin film laminate including a 5μm thick PVA layer. By such two-step stretching, an optical thin film laminate including a PVA layer with a thickness of 5 μm constituting a thin polarizer can be obtained. The PVA molecules in the PVA layer formed on the amorphous PET substrate undergo high-order orientation, and the iodine adsorbed by dyeing undergoes high-order orientation in one direction in the form of a polyiodine ion complex.

＜透明保護薄膜＞ 作為透明保護薄膜，使用了柯尼卡美能達株式會社製造的三乙酸纖維素(TAC)薄膜(產品名：KC2UA、厚度：25μm)。<Transparent protective film> As the transparent protective film, a triacetate cellulose (TAC) film (product name: KC2UA, thickness: 25μm) manufactured by Konica Minolta, Inc. was used.

＜活性能量射線＞ 作為活性能量射線，使用了可見光(封入有鎵的金屬鹵化物燈)照射裝置：Fusion UV Systems，Inc.製Light HAMMER10、閥：V閥、峰值照度：1600mW/cm² 、累積照射量1000/mJ/cm² (波長380~440nm)。需要說明的是，使用Solatell公司製造的Sola-Check系統測定了可見光的照度。<Active energy ray> As active energy ray, visible light (metal halide lamp enclosed in gallium) irradiation device: Light HAMMER10 manufactured by Fusion UV Systems, Inc., valve: V valve, peak illuminance: 1600mW/cm ² , cumulative irradiation dose 1000/mJ/cm ² (wavelength 380~440nm) was used. It should be noted that the illuminance of visible light was measured using the Sola-Check system manufactured by Solatell.

(黏接劑組合物的製備) 將組合物中的自由基聚合性化合物的總量設為100質量%時，將作為自由基聚合性化合物的丙烯醯基嗎啉(商品名“ACMO”、興人株式會社製)、作為自由基聚合性化合物的1,9-壬二醇二丙烯酸酯(商品名“LIGHT ACRYLATE 1,9-NDA(表1中記載為“1,9-NDA”)”、共榮社化學株式會社製)、作為光聚合引發劑的二乙基噻噸酮(通式(3)記載的化合物、商品名“KAYACURE DETX-S(表1中記載為“DETX-S”)”、日本化藥株式會社製)、作為光聚合引發劑的2-甲基-1-(4-甲硫基苯基)-2-嗎啉代丙烷-1-酮(通式(4)記載的化合物、商品名“IRGACURE 907(表1中記載為“907”)”、BASF公司製)以表1中記載的摻合量比進行混合，接下來在50℃下攪拌1小時，從而製備了實施例及比較例中使用的黏接劑組合物。關於黏接劑組合物的SP值的推定方法，在後面敘述。(Preparation of adhesive composition) When the total amount of the radical polymerizable compound in the composition is set to 100% by mass, acrylamide morpholine (trade name "ACMO", manufactured by Kojin Co., Ltd.) as a radical polymerizable compound, 1,9-nonanediol diacrylate (trade name "LIGHT ACRYLATE 1,9-NDA (represented as "1,9-NDA" in Table 1)", manufactured by Kyoeisha Chemical Co., Ltd.) as a radical polymerizable compound, diethylthiothione (compound represented by general formula (3), trade name "KAYACURE DETX-S (described as "DETX-S" in Table 1) and manufactured by Nippon Kayaku Co., Ltd.) and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one (a compound described by the general formula (4) and a trade name "IRGACURE 907 (described as "907" in Table 1)" and manufactured by BASF) as a photopolymerization initiator were mixed in the blending ratio described in Table 1, and then stirred at 50°C for 1 hour to prepare an adhesive composition used in the Examples and Comparative Examples. The method for estimating the SP value of the adhesive composition will be described later.

(易黏接組合物的製備) 將組合物的總量設為100質量%時，將作為通式(1)記載的化合物的4-乙烯基苯硼酸(純正化學株式會社製)、作為自由基聚合性化合物的丙烯醯基嗎啉(商品名“ACMO”、興人株式會社製)及純水以表1中記載的摻合量比進行混合，接下來，在50℃下攪拌1小時，從而製備了實施例及比較例中使用的易黏接組合物。關於易黏接組合物的SP值的推定方法，在後面敘述。(Preparation of easy-adhesion composition) When the total amount of the composition is set to 100% by mass, 4-vinylphenylboronic acid (manufactured by Junsei Chemical Co., Ltd.) as a compound represented by general formula (1), acrylamide morpholine (trade name "ACMO", manufactured by Kojin Co., Ltd.) as a radical polymerizable compound, and pure water were mixed at the blending ratio shown in Table 1, and then stirred at 50°C for 1 hour to prepare an easy-adhesion composition used in Examples and Comparative Examples. The method for estimating the SP value of the easy-adhesion composition will be described later.

(易黏接組合物的塗敷步驟) 使用具備凹版輥的凹版輥塗敷方式，在上述偏光件的包含厚度5μm的PVA層的光學薄膜積層體的PVA面塗敷表1中記載的易黏接組合物，在25℃下熱風乾燥1分鐘，從而製作了帶易黏接層的偏光件。在各實施例及比較例的塗敷步驟中，將塗敷易黏接組合物時的乾燥前厚度(WET厚度(nm))示於表1。(Coating step of easy-adhesion composition) The easy-adhesion composition listed in Table 1 was applied to the PVA surface of the optical film laminate including a 5μm thick PVA layer of the above-mentioned polarizer using a gravure roller coating method, and hot air dried at 25°C for 1 minute to produce a polarizer with an easy-adhesion layer. In the coating step of each embodiment and comparative example, the thickness before drying (WET thickness (nm)) when the easy-adhesion composition was applied is shown in Table 1.

(偏光薄膜的製造) 實施例1~2及比較例1 使用MCD塗布機(富士機械株式會社製)(單元形狀：蜂窩、凹版輥線數：1000條/英寸、轉速140%/對線速)，在透明保護薄膜的貼合面側塗敷上述黏接劑組合物，使其成為表1中記載的乾燥前厚度(WET厚度(nm))，形成了未固化的黏接劑層。接下來，使用輥機從上述帶易黏接層的偏光件的易黏接層面側與透明保護薄膜進行了貼合。然後，利用活性能量射線照射裝置，從貼合後的透明保護薄膜側照射上述可見光，使偏光件與透明保護薄膜黏接後，在70℃下熱風乾燥3分鐘，將積層於偏光件的另一側的非晶性PET基材剝離除去，從而得到了在偏光件的一側具有透明保護薄膜的偏光薄膜。貼合以25m/min的線速度進行。(Manufacturing of polarizing film) Examples 1-2 and Comparative Example 1 Using an MCD coating machine (manufactured by Fuji Machinery Co., Ltd.) (unit shape: honeycomb, gravure roller line number: 1000 lines/inch, rotation speed 140%/line speed), the above-mentioned adhesive composition was applied to the bonding side of the transparent protective film to a pre-drying thickness (WET thickness (nm)) as shown in Table 1, thereby forming an uncured adhesive layer. Next, the easy-bonding layer side of the above-mentioned polarizer with an easy-bonding layer was bonded to the transparent protective film using a roller. Then, the above-mentioned visible light was irradiated from the laminated transparent protective film side using an active energy ray irradiation device to bond the polarizer and the transparent protective film, and then hot air dried at 70°C for 3 minutes to peel off and remove the amorphous PET substrate laminated on the other side of the polarizer, thereby obtaining a polarizing film having a transparent protective film on one side of the polarizer. The lamination was performed at a line speed of 25m/min.

＜黏接劑組合物及易黏接組合物的SP值的推定方法＞ 黏接劑組合物及易黏接組合物的SP值如下所述地求出：對於組合物的構成材料分別藉由Hansen Solubility Parameter in Practice(HSPiP)的Y-MB法計算漢森溶解度参數(SP值)，根據組合物中的體積比取平均值而求出。需要說明的是，關於易黏接組合物，對除純水以外的其它構成材料計算出SP值。<Method for estimating the SP value of adhesive composition and easy-bonding composition> The SP value of the adhesive composition and easy-bonding composition is determined as follows: The Hansen solubility parameter (SP value) is calculated for each constituent material of the composition by the Y-MB method of Hansen Solubility Parameter in Practice (HSPiP), and the average value is calculated based on the volume ratio in the composition. It should be noted that for the easy-bonding composition, the SP value is calculated for constituent materials other than pure water.

＜透明保護薄膜的SP值的測定方法＞ 將透明保護薄膜浸漬於溶解度不同的14種溶劑，即水、丙酮、環戊酮、異丙醇、乙醇、甲醇、甲苯、對二甲苯、環己烷、正己烷、乙酸乙酯、三氯苯、苯甲醚及它們的混合溶劑中10分鐘。將10分鐘浸漬後的透明保護薄膜的情況分類為(1)溶解、(2)溶脹、(3)不溶這3個等級。基於這樣得到的對各溶劑的溶解度的資訊，根據Hansen Solubility Parameter in Practice(HSPiP) ver.4.1.07(http：//www.hansen-solubility.com/index.php)計算出漢森溶解度參數(SP值)。<Method for determining the SP value of a transparent protective film> The transparent protective film was immersed in 14 solvents with different solubility, namely water, acetone, cyclopentanone, isopropyl alcohol, ethanol, methanol, toluene, p-xylene, cyclohexane, n-hexane, ethyl acetate, trichlorobenzene, anisole, and a mixed solvent thereof for 10 minutes. The transparent protective film after 10 minutes of immersion was classified into three categories: (1) dissolved, (2) swollen, and (3) insoluble. Based on the information on the solubility in each solvent obtained in this way, the Hansen Solubility Parameter (SP value) was calculated according to Hansen Solubility Parameter in Practice (HSPiP) ver.4.1.07 (http://www.hansen-solubility.com/index.php).

＜透明保護薄膜的SP值與黏接劑組合物(或易黏接組合物)的SP值之間的SP值距離＞ 將透明保護薄膜的漢森溶解度參數的分散項設為σd、將極性項設為σp、將氫鍵項設為σh、將黏接劑組合物的漢森的溶解度參數的分散項設為σAd、將極性項設為σAp、將氫鍵項設為σAh時，將下述數學式：Ra＝[4×(σd－σAd)² ＋2×(σp－σAp)² ＋2×(σh－σAh)² ]^1/2 ＝[4×(σd－σAd)² ＋2×(σp－σAp)² ＋2×(σh－σAh)² ]^1/2 定義為“透明保護薄膜的SP值黏接劑組合物(或易黏接組合物)的SP值之間的SP值距離”。使用由上述方法計算出的透明保護薄膜及黏接劑組合物(或易黏接組合物)的漢森的溶解度參數進行了計算。<SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition (or easy-adhesion composition)> When the dispersion term of the Hansen solubility parameter of the transparent protective film is σd, the polar term is σp, and the hydrogen bond term is σh, and the dispersion term of the Hansen solubility parameter of the adhesive composition is σAd, the polar term is σAp, and the hydrogen bond term is σAh, the following mathematical formula: Ra = [4×(σd-σAd) ² +2×(σp-σAp) ² +2×(σh-σAh) ² ] ^1/2 = [4×(σd-σAd) ² +2×(σp-σAp) ² +2×(σh-σAh) ² ] ^1/2 is defined as "the SP value distance between the SP value of the transparent protective film and the SP value of the adhesive composition (or the easy-adhesion composition)". The calculation was performed using the Hansen solubility parameters of the transparent protective film and the adhesive composition (or the easy-adhesion composition) calculated by the above method.

(剝離力(初始黏接力)) 將得到的偏光薄膜在與偏光件的拉伸方向平行的方向切出200mm、在正交方向切出15mm的大小，將偏光薄膜貼合於玻璃板。然後，用切刀在透明保護薄膜與偏光件之間切出切口，採用萬能拉力機、向90度方向將保護薄膜及偏光件以剝離速度300m/min剝離，測定了其剝離強度(N/15mm)。(Peeling force (initial adhesion)) The obtained polarizing film was cut into 200mm in a direction parallel to the stretching direction of the polarizer and 15mm in a direction perpendicular to the polarizer, and the polarizing film was bonded to a glass plate. Then, a cutter was used to cut a notch between the transparent protective film and the polarizer, and the protective film and the polarizer were peeled off at a peeling speed of 300m/min in a 90-degree direction using a universal tensile tester, and the peeling strength (N/15mm) was measured.

(偏光薄膜內有無氣泡的觀察) 對偏光薄膜照射螢光燈，以肉眼觀察有無氣泡。如表1所記載那樣，在實施例1~2中製造的偏光薄膜中未觀察到氣泡，但在比較例1中，在偏光薄膜整個面觀察到大量氣泡。本發明之液狀吸濕劑(本發明吸濕劑)特徵在於，(Observation of bubbles in polarizing film) The polarizing film was illuminated with a fluorescent light and observed with the naked eye for bubbles. As shown in Table 1, no bubbles were observed in the polarizing films produced in Examples 1 and 2, but in Comparative Example 1, a large number of bubbles were observed on the entire surface of the polarizing film. The liquid desiccant of the present invention (the desiccant of the present invention) is characterized in that,

表1 Table 1

(無)(without)

Claims (3)

一種偏光薄膜之製造方法，所述偏光薄膜在偏光件的至少一面隔著黏接劑層設置有透明保護薄膜，該方法包括：第一塗敷步驟，在所述透明保護薄膜的貼合面塗敷黏接劑組合物；貼合步驟，使所述偏光件及所述透明保護薄膜貼合；以及黏接步驟，從偏光件面側或透明保護薄膜面側照射活性能量射線，使所述黏接劑組合物固化而得到黏接劑層，從而隔著所述黏接劑層使所述偏光件及所述透明保護薄膜黏接，所述透明保護薄膜的SP值與所述黏接劑組合物的SP值之間的SP值距離為5.3以上；該方法進一步具有第二塗敷步驟，該第二塗敷步驟在所述偏光件的貼合面塗敷易黏接組合物，所述黏接步驟是隔著使所述黏接劑組合物及所述易黏接組合物固化而得到的黏接劑層使所述偏光件及所述透明保護薄膜黏接的步驟，所述透明保護薄膜的SP值與所述易黏接組合物的SP值之間的SP值距離為8.0以下；所述易黏接組合物含有下述通式(1)表示的化合物：

式中，X為包含反應性基團的官能團，R¹及R²分別獨立地表示氫原子、可亦具有取代基的脂肪族烴基、芳基或雜環基，X所含的反應性基團為選自於由乙烯基、(甲基)丙烯醯基、苯乙烯基、(甲基)丙烯醯胺基、乙烯基醚基、環氧基、氧雜環丁基及巰基所構成組群中的至少1種反應性基團。 A method for manufacturing a polarizing film, wherein the polarizing film is provided with a transparent protective film on at least one side of a polarizer via an adhesive layer, the method comprising: a first coating step, coating an adhesive composition on the bonding surface of the transparent protective film; a bonding step, bonding the polarizer and the transparent protective film; and a bonding step, irradiating active energy rays from the side of the polarizer or the side of the transparent protective film to cure the adhesive composition to obtain an adhesive layer, thereby bonding the polarizer and the transparent protective film via the adhesive layer, and the SP value of the transparent protective film is The distance between the SP value of the polarizer and the SP value of the adhesive composition is 5.3 or more; the method further comprises a second coating step, wherein the easy-bonding composition is coated on the bonding surface of the polarizer, the bonding step is a step of bonding the polarizer and the transparent protective film via an adhesive layer obtained by curing the adhesive composition and the easy-bonding composition, and the distance between the SP value of the transparent protective film and the SP value of the easy-bonding composition is 8.0 or less; the easy-bonding composition contains a compound represented by the following general formula (1):

In the formula, X is a functional group containing a reactive group, ^R1 and ^R2 each independently represent a hydrogen atom, an aliphatic hydrocarbon group which may also have a substituent, an aryl group or a heterocyclic group, and the reactive group contained in X is at least one reactive group selected from the group consisting of a vinyl group, a (meth)acryl group, a styryl group, a (meth)acrylamide group, a vinyl ether group, an epoxy group, an oxycyclobutyl group and an alkyl group. 如請求項1之偏光薄膜之製造方法，其中，所述通式(1)表示的化合物為下述通式(1’)表示的化合物：

式中，Y為有機基團，X’為X所含的反應性基團，R¹及R²與上述定義相同。 The method for producing a polarizing film according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1'):

In the formula, Y is an organic group, X' is a reactive group contained in X, and ^R1 and ^R2 have the same meanings as defined above. 如請求項1或2之偏光薄膜之製造方法，其中，所述易黏接組合物含有下述通式(2)表示的自由基聚合性化合物：

式中，R³為氫原子或甲基，R⁴及R⁵分別獨立地為氫原子、烷基、羥基烷基、烷氧基烷基或環狀醚基，R⁴及R⁵可亦形成環狀雜環。 The method for producing a polarizing film according to claim 1 or 2, wherein the easy-adhesion composition contains a radical polymerizable compound represented by the following general formula (2):

In the formula, R ³ is a hydrogen atom or a methyl group, R ⁴ and R ⁵ are independently a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group or a cyclic ether group, and R ⁴ and R ⁵ may also form a cyclic heterocycle.