TWI725957B - Liquid crystal display device and polarizing plate set - Google Patents

Abstract

本發明提供即使在應用於液晶面板的情況下也能抑制顯示不均或偏光板的翹曲、黃變，且還能防止在薄膜製膜時焦糊的液晶顯示裝置及偏光板套組。本發明液晶顯示裝置為具備對向偏光板的液晶顯示裝置，上述偏光板各自具備在聚乙烯醇系偏光件兩面隔著黏接劑層設置的透明保護薄膜，一面的第1透明保護薄膜含有(甲基)丙烯酸系樹脂，且具有紫外線吸收劑，所述(甲基)丙烯酸系樹脂具有不飽和羧酸烷基酯單元及通式(1)所示的戊二醯亞胺單元，並且醯亞胺化率為2.5~5.0%、酸值為0.10~0.50mmol/g的範圍，且丙烯酸酯單元不足1重量%，另一面的第2透明保護薄膜為含有纖維素酯而成，且為滿足nx>ny>nz關係的相位差板。 The present invention provides a liquid crystal display device and a polarizing plate set that can suppress display unevenness, warpage and yellowing of the polarizing plate even when applied to a liquid crystal panel, and also prevent burnt during film formation. The liquid crystal display device of the present invention is a liquid crystal display device provided with opposing polarizing plates, each of the polarizing plates having a transparent protective film provided on both sides of a polyvinyl alcohol-based polarizer via an adhesive layer, and the first transparent protective film on one side contains ( The meth)acrylic resin has an ultraviolet absorber, and the (meth)acrylic resin has an unsaturated carboxylic acid alkyl ester unit and a glutaric imine unit represented by the general formula (1), and The amination rate is 2.5~5.0%, the acid value is in the range of 0.10~0.50mmol/g, and the acrylate unit is less than 1% by weight. The second transparent protective film on the other side is made of cellulose ester, and meets nx >ny>nz phase difference plate.

Description

液晶顯示裝置及偏光板套組 Liquid crystal display device and polarizing plate set

本發明涉及液晶顯示裝置及偏光板套組。 The invention relates to a liquid crystal display device and a polarizing plate set.

背景技術 Background technique

液晶顯示裝置利用液晶的開關而使偏光狀態視覺化，根據其顯示原理，使用在偏光件兩面藉由黏接劑層貼合有透明保護薄膜的偏光板。作為偏光件，例如使碘吸附於聚乙烯醇並對其拉伸後結構的碘系偏光件因具有高透射率、高偏光度而作為最常用的偏光件被廣泛使用。作為透明保護薄膜，使用透濕度高的三乙醯纖維素等。 The liquid crystal display device uses the switch of the liquid crystal to visualize the polarization state. According to its display principle, it uses a polarizing plate in which a transparent protective film is attached to both sides of a polarizer through an adhesive layer. As the polarizer, for example, an iodine-based polarizer having a structure after absorbing iodine on polyvinyl alcohol and stretching the structure is widely used as the most commonly used polarizer because of its high transmittance and high degree of polarization. As the transparent protective film, triacetyl cellulose with high moisture permeability or the like is used.

應用上述偏光板的液晶顯示裝置等影像顯示裝置被用於各種環境下。因此，期望使上述偏光板具有在高溫環境下的耐熱性、在高濕環境下的耐濕性等耐久性。但是，作為透明保護薄膜，通常，所使用的三乙醯纖維素等存在於高濕環境下相位差發生大幅變化而在面板上產生顯示不均的問題。對此，提出了使用包含(甲基)丙烯酸系樹脂的透明保護薄膜而使透濕度降低，並抑制顯示不均的技術(參照專利文獻1)。 Image display devices such as liquid crystal display devices to which the above-mentioned polarizing plates are applied are used in various environments. Therefore, it is desired that the polarizing plate has durability such as heat resistance in a high-temperature environment and humidity resistance in a high-humidity environment. However, as a transparent protective film, in general, triacetyl cellulose or the like used has a problem that the phase difference changes significantly in a high-humidity environment, causing display unevenness on the panel. In response to this, a technique has been proposed that uses a transparent protective film containing a (meth)acrylic resin to reduce the moisture permeability and suppress display unevenness (see Patent Document 1).

先行技術文獻 Advanced technical literature 專利文獻 Patent literature

專利文獻1：日本特開2009-139720號公報 Patent Document 1: Japanese Patent Application Publication No. 2009-139720

但是，根據在影像顯示裝置中組合的偏光板，有時在過於嚴酷的環境下發生顯示不均、或發生偏光板的翹曲。 However, depending on the polarizing plate combined in the image display device, display unevenness or warping of the polarizing plate may occur in an excessively severe environment.

另外，近年來，謀求尤其手機等行動用途等的開展。就此等行動用途而言，由於大多被置於野外環境，因此即使是使用上述技術的液晶顯示裝置，有時也會因紫外線的影響而在顯示部產生黃變，期望滿足環境耐久性，尤其紫外線耐久性。 In addition, in recent years, the development of mobile applications such as mobile phones has been sought. For these mobile applications, most of them are placed in the outdoor environment. Therefore, even the liquid crystal display device using the above-mentioned technology may sometimes cause yellowing in the display part due to the influence of ultraviolet rays. It is desirable to meet environmental durability, especially ultraviolet rays. Durability.

為此，本案發明人等的黃變對策為在利用(甲基)丙烯酸系樹脂形成的透明保護薄膜中添加紫外線吸收劑來提高紫外線耐久性。但是，最新明確了添加了紫外線吸收劑的透明保護薄膜在薄膜製膜時引起焦糊(看似燒焦的黑色狀的微小斑點)等外觀不良。 For this reason, the inventors of the present application have taken a measure against yellowing by adding an ultraviolet absorber to a transparent protective film formed of a (meth)acrylic resin to improve the ultraviolet durability. However, it has recently been clarified that a transparent protective film to which an ultraviolet absorber has been added causes appearance defects such as burnt (black micro spots that appear to be burnt) during film formation.

本發明的目的在於提供即使在應用於液晶面板的情況下也能抑制顯示不均或偏光板的翹曲、黃變，且還能防止薄膜製膜時焦糊的液晶顯示裝置及偏光板套組。 The object of the present invention is to provide a liquid crystal display device and a polarizing plate set that can suppress display unevenness, warpage and yellowing of the polarizing plate even when applied to a liquid crystal panel, and prevent burnt during film formation .

本案發明人等為了解決上述課題而反覆進行深入研究，結果發現以下所示的偏光板，以至完成本發明。 In order to solve the above-mentioned problems, the inventors of the present application have conducted intensive studies, and as a result, discovered the polarizing plate shown below, and completed the present invention.

即，本發明涉及一種液晶顯示裝置，係具備對向偏光板的液晶顯示裝置， 所述偏光板各自具備在聚乙烯醇系偏光件兩面隔著黏接劑層設置的透明保護薄膜，一面的第1透明保護薄膜含有(甲基)丙烯酸系樹脂，且具有紫外線吸收劑，所述(甲基)丙烯酸系樹脂具有不飽和羧酸烷基酯單元及通式(1)所示的戊二醯亞胺單元，並且醯亞胺化率為2.5~5.0%、酸值為0.10~0.50mmol/g的範圍且丙烯酸酯單元不足1重量%，另一面的第2透明保護薄膜為含有纖維素酯而成，且為滿足nx>ny>nz(其中，將面內折射率達到最大的方向設為X軸，將與X軸垂直的方向設為Y軸，將厚度方向設為Z軸，並且將各軸方向的折射率設為nx、ny、nz)關係的相位差板。 That is, the present invention relates to a liquid crystal display device, which is a liquid crystal display device provided with an opposing polarizing plate, Each of the polarizing plates is provided with a transparent protective film provided on both sides of the polyvinyl alcohol-based polarizer via an adhesive layer, and the first transparent protective film on one side contains a (meth)acrylic resin and has an ultraviolet absorber, the The (meth)acrylic resin has an unsaturated carboxylic acid alkyl ester unit and a glutarimide unit represented by the general formula (1), and the imidization rate is 2.5 to 5.0%, and the acid value is 0.10 to 0.50 In the range of mmol/g and the acrylate unit is less than 1% by weight, the second transparent protective film on the other side is made of cellulose ester, and is to satisfy nx>ny>nz (wherein the direction where the in-plane refractive index reaches the maximum Let it be the X-axis, let the direction perpendicular to the X-axis be the Y-axis, let the thickness direction be the Z-axis, and let the refractive index of each axis direction be a phase difference plate of nx, ny, nz) relationship.

(其中，R¹及R²分別獨立地表示氫或碳數1~8的烷基，R³表示碳數1~18的烷基、碳數3~12的環烷基、或碳數6~10的芳基。) (Wherein, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbons, and R ³ represents an alkyl group having 1 to 18 carbons, a cycloalkyl group having 3 to 12 carbons, or a carbon number 6 to 10 of the aryl group.)

在該液晶顯示裝置中，作為偏光板一面的第1透明保護薄膜，使用含有具有不飽和羧酸烷基酯單元及戊二醯亞胺單元的(甲基)丙烯酸系樹脂而成的透明保護薄膜。該(甲基)丙烯酸系樹脂的透濕度低，可以滿足高溫環境下的耐 熱性、高濕環境下的耐濕性等耐久性。該液晶顯示裝置中，由於使如此的偏光板在上下配置，因此即使在將偏光板應用於液晶面板的情況下也能將顯示不均、翹曲抑制得較小。 In this liquid crystal display device, as the first transparent protective film on one side of the polarizing plate, a transparent protective film containing a (meth)acrylic resin having an unsaturated carboxylic acid alkyl ester unit and a glutarimide unit is used . The (meth)acrylic resin has low moisture permeability and can meet the high temperature resistance Durability such as heat resistance and humidity resistance in high humidity environments. In this liquid crystal display device, since such polarizing plates are arranged up and down, even when the polarizing plates are applied to a liquid crystal panel, display unevenness and warpage can be suppressed to be small.

另外，在上述偏光板中，第1透明保護薄膜具有紫外線吸收劑，因此可以適當防止在野外環境下的影響大的黃變。 In addition, in the above-mentioned polarizing plate, the first transparent protective film has an ultraviolet absorber, and therefore it is possible to appropriately prevent yellowing that has a large influence in the outdoor environment.

進而，在上述偏光板中，採用具有不飽和羧酸烷基酯單元及戊二醯亞胺單元的(甲基)丙烯酸系樹脂作為第1透明保護薄膜的形成材料，且將該(甲基)丙烯酸系樹脂的醯亞胺化率、酸值及丙烯酸酯單元的含量設定為規定範圍，因此能夠抑制因紫外線吸收劑的添加所致薄膜製膜時焦糊的產生，並且使偏光板的外觀良好。 Furthermore, in the above-mentioned polarizing plate, a (meth)acrylic resin having an unsaturated carboxylic acid alkyl ester unit and a glutarimide unit is used as a material for forming the first transparent protective film, and the (meth) The imidization rate, acid value, and acrylate unit content of the acrylic resin are set within the specified range, so it is possible to suppress the generation of scorch during film formation due to the addition of ultraviolet absorbers, and to improve the appearance of the polarizing plate .

此外，在該偏光板中，另一面側的第2透明保護薄膜兼作相位差板，因此可以實現作為光學薄膜的薄型化，進而實現液晶顯示裝置的薄型化。 In addition, in this polarizing plate, the second transparent protective film on the other side doubles as a phase difference plate, so that the thickness of the optical film can be reduced, and the thickness of the liquid crystal display device can be reduced.

上述第1透明保護薄膜的面內相位差及厚度方向相位差分別較佳為40nm以下。由此可以製成適合於液晶顯示裝置的偏光板用途的透明保護薄膜。 The in-plane retardation and the thickness direction retardation of the above-mentioned first transparent protective film are each preferably 40 nm or less. In this way, a transparent protective film suitable for use as a polarizing plate of a liquid crystal display device can be produced.

上述偏光板可以具有配置於上述第1透明保護薄膜的一面側的塗布層。另外，上述塗布層可以為硬塗層或防污層。由此，可以對偏光板賦予因應塗布層種類的機能。 The said polarizing plate may have the coating layer arrange|positioned on the one surface side of the said 1st transparent protective film. In addition, the above-mentioned coating layer may be a hard coat layer or an antifouling layer. As a result, the polarizing plate can be provided with a function according to the type of coating layer.

上述黏接劑層較佳包含水系黏接劑。水系黏接劑與聚乙烯醇系偏光件的親和性高，因此可以提高偏光件與透明保護薄膜的密合性。 The adhesive layer preferably contains an aqueous adhesive. The water-based adhesive has a high affinity with the polyvinyl alcohol-based polarizer, so it can improve the adhesion between the polarizer and the transparent protective film.

作為該液晶顯示裝置的構成，上述偏光板可以隔著黏合層貼合於液晶單元，上述黏合層設置於與上述透明保護薄膜之上述偏光件側的相反側。 As the structure of the liquid crystal display device, the polarizing plate may be bonded to the liquid crystal cell via an adhesive layer, and the adhesive layer may be provided on the side opposite to the polarizer side of the transparent protective film.

在該液晶顯示裝置中，可以在上述偏光板與上述黏合層之間設有錨固層。藉由設置錨固層，可以實現密合性的進一步提高。 In this liquid crystal display device, an anchor layer may be provided between the polarizing plate and the adhesive layer. By providing the anchor layer, the adhesion can be further improved.

在該液晶顯示裝置中，上述黏合層可以具有導電性，上述錨固層也可以具有導電性。由此，可以對偏光板、具備該偏光板的液晶顯示裝置賦予防靜電性。 In this liquid crystal display device, the adhesion layer may have conductivity, and the anchor layer may have conductivity. Thereby, it is possible to impart antistatic properties to the polarizing plate and the liquid crystal display device provided with the polarizing plate.

本發明亦包括一種偏光板套組，係在液晶顯示裝置中經對向配置的偏光板套組，所述偏光板各自具備在聚乙烯醇系偏光件兩面隔著黏接劑層設置的透明保護薄膜，一面的第1透明保護薄膜含有(甲基)丙烯酸系樹脂，且具有紫外線吸收劑，所述(甲基)丙烯酸系樹脂具有不飽和羧酸烷基酯單元及通式(1)所示的戊二醯亞胺單元，並且醯亞胺化率為2.5~5.0%、酸值為0.10~0.50mmol/g的範圍且丙烯酸酯單元不足1重量%，另一面的第2透明保護薄膜為含有纖維素酯而成，且為滿足nx>ny>nz(其中，將面內折射率達到最大的方向設為X軸，將與X軸垂直的方向設為Y軸，將厚度方向設為Z軸，並且將各軸方向的折射率設為nx、ny、nz)關係的相位差板，[化2]

The present invention also includes a polarizing plate set, which is a set of polarizing plates arranged in opposite directions in a liquid crystal display device, each of the polarizing plates is provided with a transparent protection provided on both sides of a polyvinyl alcohol-based polarizer via an adhesive layer The film, the first transparent protective film on one side contains a (meth)acrylic resin and has an ultraviolet absorber, and the (meth)acrylic resin has an unsaturated carboxylic acid alkyl ester unit and is represented by the general formula (1) The glutarimide unit, and the imidization rate is 2.5~5.0%, the acid value is in the range of 0.10~0.50mmol/g, and the acrylate unit is less than 1% by weight. The second transparent protective film on the other side contains It is made of cellulose ester, and to satisfy nx>ny>nz (wherein, the direction in which the in-plane refractive index reaches the maximum is the X axis, the direction perpendicular to the X axis is the Y axis, and the thickness direction is the Z axis , And set the refractive index in each axial direction as a retardation plate in the relationship of nx, ny, nz), [化2]

(此處，R¹及R²分別獨立地表示氫或碳數1~8的烷基，R³表示碳數1~18的烷基、碳數3~12的環烷基或者碳數6~10的芳基。) (Here, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbons, and R ³ represents an alkyl group having 1 to 18 carbons, a cycloalkyl group having 3 to 12 carbons, or a carbon number 6 to 10 of the aryl group.)

1‧‧‧偏光件 1‧‧‧Polarizer

3‧‧‧黏接劑層 3‧‧‧Adhesive layer

21‧‧‧第1透明保護薄膜 21‧‧‧The first transparent protective film

22‧‧‧第2透明保護薄膜 22‧‧‧Second transparent protective film

100‧‧‧液晶顯示裝置 100‧‧‧LCD device

C‧‧‧液晶單元 C‧‧‧LCD unit

P‧‧‧偏光板 P‧‧‧Polarizer

圖1為示意性地表示本發明一實施方式的液晶顯示裝置的剖面圖。 FIG. 1 is a cross-sectional view schematically showing a liquid crystal display device according to an embodiment of the present invention.

用以實施發明的方式 Ways to implement the invention

以下，參照附圖對本發明一實施方式的液晶顯示裝置進行說明。但是，在圖的一部分或全部中省略不需要說明的部分，另外，為了易於說明，有放大或縮小等而圖示的部分。 Hereinafter, a liquid crystal display device according to an embodiment of the present invention will be described with reference to the drawings. However, parts that do not need to be explained are omitted in part or all of the drawings, and for ease of explanation, there are parts that are enlarged or reduced in the drawings.

<液晶顯示裝置> <Liquid crystal display device>

圖1是示意性地表示本發明一實施方式的液晶顯示裝置的剖面圖。液晶顯示裝置100中，在液晶單元C兩側配置有同一構成的偏光板P。除此以外，在形成液晶顯示裝置時，可以在適當位置配置1層或2層以上例如擴散板、防眩層、防反射膜、保護板、稜鏡陣列、透鏡陣列片、光擴散 板、背光燈等適當的部件。 FIG. 1 is a cross-sectional view schematically showing a liquid crystal display device according to an embodiment of the present invention. In the liquid crystal display device 100, polarizing plates P of the same configuration are arranged on both sides of the liquid crystal cell C. In addition, when forming a liquid crystal display device, one layer or two or more layers such as diffuser, anti-glare layer, anti-reflection film, protective plate, scallop array, lens array sheet, and light diffusion can be arranged at an appropriate position. Appropriate components such as boards, backlights, etc.

能根據習知來進行液晶顯示裝置的形成。即液晶顯示裝置通常藉由適當組裝液晶單元、偏光板及根據需要的照明系統等構成部件並組裝驅動電路等而形成，但本實施方式中除了使用規定的偏光板以外沒有特別限定，能根據習知進行。關於液晶單元，也能使用例如TN型或STN型、π型、VA型、IPS型等任意類型的液晶單元。 The formation of the liquid crystal display device can be performed according to conventional knowledge. That is, a liquid crystal display device is usually formed by appropriately assembling constituent parts such as a liquid crystal cell, a polarizing plate, and an illumination system as required, and assembling a driving circuit, etc. However, in this embodiment, there is no particular limitation except for the use of a predetermined polarizing plate, and it can be formed according to conventional Know to proceed. Regarding the liquid crystal cell, any type of liquid crystal cell, such as TN type, STN type, π type, VA type, and IPS type, can also be used.

<偏光板> <Polarizer>

如圖1所示，在各偏光板P中，在聚乙烯醇系偏光件1兩面隔著黏接劑層3分別設有第1透明保護薄膜21、第2透明保護薄膜22。第1透明保護薄膜21含有具有不飽和羧酸烷基酯單元及戊二醯亞胺單元的(甲基)丙烯酸系樹脂及紫外線吸收劑。另一方面，第2透明保護薄膜22為含有纖維素酯的相位差板。 As shown in FIG. 1, in each polarizing plate P, a first transparent protective film 21 and a second transparent protective film 22 are respectively provided on both surfaces of the polyvinyl alcohol-based polarizer 1 with an adhesive layer 3 interposed therebetween. The first transparent protective film 21 contains a (meth)acrylic resin having an unsaturated carboxylic acid alkyl ester unit and a glutarimide unit, and an ultraviolet absorber. On the other hand, the second transparent protective film 22 is a phase difference plate containing cellulose ester.

(聚乙烯醇系偏光件) (Polyvinyl alcohol polarizer)

偏光件1並無特別限制，可以使用各種偏光件。作為偏光件，例如可列舉使碘、二色性染料等二色性材料吸附於聚乙烯醇系薄膜、部分縮甲醛化聚乙烯醇系薄膜、乙烯-乙酸乙烯酯共聚物系部分皂化薄膜等親水性高分子薄膜並進行單軸拉伸而成的偏光件、聚乙烯醇的脫水處理物、聚氯乙烯的脫鹽酸處理物等多烯系配向薄膜等。其中以包含聚乙烯醇系薄膜及碘等二色性物質的偏光件為佳。此等偏光件的厚度並無特別限制，但通常為5~80μm左右。 The polarizer 1 is not particularly limited, and various polarizers can be used. Examples of polarizers include hydrophilic materials such as iodine, dichroic dyes and other dichroic materials adsorbed on polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, ethylene-vinyl acetate copolymer-based partially saponified films, etc. Polyene-based alignment films, such as polarizers formed by uniaxially stretched flexible polymer films, dehydrated polyvinyl alcohol, and dehydrated polyvinyl chloride. Among them, polarizers containing dichroic substances such as polyvinyl alcohol-based films and iodine are preferred. The thickness of these polarizers is not particularly limited, but is usually about 5 to 80 μm.

例如可以藉由將聚乙烯醇浸漬於碘的水溶液進 行染色、並將其拉伸至原長的3~7倍，由此來製作用碘將聚乙烯醇系薄膜染色並進行單軸拉伸而成的偏光件。根據需要，也可以浸漬於硼酸、碘化鉀等的水溶液。而且，可以根據需要在染色前將聚乙烯醇系薄膜浸漬於水中進行水洗。藉由將聚乙烯醇系薄膜進行水洗，能夠清洗聚乙烯醇系薄膜表面的污物、抗阻塞劑，並且藉由使聚乙烯醇系薄膜溶脹，還具有防止染色不均等不均勻的效果。拉伸可以在用碘染色後進行，也可以邊染色邊進行拉伸，另外，也可以在拉伸後用碘進行染色。也可以在硼酸、碘化鉀等的水溶液中或水浴中進行拉伸。 For example, by immersing polyvinyl alcohol in an aqueous solution of iodine It is dyed and stretched to 3 to 7 times its original length, thereby fabricating a polarizer obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching it. If necessary, it may be immersed in an aqueous solution such as boric acid and potassium iodide. In addition, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing if necessary. By washing the polyvinyl alcohol-based film with water, the dirt and anti-blocking agent on the surface of the polyvinyl alcohol-based film can be cleaned, and by swelling the polyvinyl alcohol-based film, it also has the effect of preventing unevenness such as uneven dyeing. Stretching may be performed after dyeing with iodine, or stretching may be performed while dyeing, or it may be dyed with iodine after stretching. Stretching can also be performed in an aqueous solution such as boric acid and potassium iodide or in a water bath.

液晶顯示裝置100的偏光板P、P以一偏光件1(例如，圖1中上側)的偏光軸與另一偏光件1(例如，圖1中下側)的偏光軸正交的方式配置。 The polarizing plates P and P of the liquid crystal display device 100 are arranged such that the polarization axis of one polarizer 1 (for example, the upper side in FIG. 1) is orthogonal to the polarization axis of the other polarizer 1 (for example, the lower side in FIG. 1 ).

(第1透明保護薄膜) (First transparent protective film)

第1透明保護薄膜21含有具有不飽和羧酸烷基酯單元及戊二醯亞胺單元的(甲基)丙烯酸系樹脂、以及紫外線吸收劑。上述(甲基)丙烯酸系樹脂較佳具有下述通式(1)所示的戊二醯亞胺單元及下述通式(2)所示的不飽和羧酸烷基酯單元的結構單元。 The first transparent protective film 21 contains a (meth)acrylic resin having an unsaturated carboxylic acid alkyl ester unit and a glutarimide unit, and an ultraviolet absorber. The (meth)acrylic resin preferably has a structural unit of a glutarimide unit represented by the following general formula (1) and an unsaturated carboxylic acid alkyl ester unit represented by the following general formula (2).

[化3]

[化3]

通式(1)中，R¹及R²分別獨立地表示氫或碳數1~8的烷基，R³表示碳數1~18的烷基、碳數3~12的環烷基或者碳數6~10的芳基。 In the general formula (1), R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 8 carbons, and R ³ represents an alkyl group having 1 to 18 carbons, a cycloalkyl group having 3 to 12 carbons, or carbon The number of aryl groups from 6 to 10.

通式(2)中，R⁴表示氫原子或碳數1~5的烷基。R⁵表示氫原子或者碳數1~6的脂肪族或脂環式烴基。 In the general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R ⁵ represents a hydrogen atom or an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms.

上述通式(1)中，較佳R¹及R²分別獨立地為氫或甲基、且R³為氫、甲基、丁基或環己基，更佳R¹為甲基、R²為氫且R³為甲基。 In the above general formula (1), preferably R ¹ and R ² are each independently hydrogen or methyl, and R ³ is hydrogen, methyl, butyl or cyclohexyl, more preferably R ¹ is methyl and R ² is Hydrogen and R ³ is methyl.

上述戊二醯(甲基)丙烯酸系樹脂可以含有僅單一種類的戊二醯亞胺單元，也可以含有上述通式(1)中的R¹、R²及R³不同的多種類的戊二醯亞胺單元。 The glutaric (meth)acrylic resin may contain only a single type of glutarimide unit, or may contain multiple types of glutaric acid having different R ¹ , R ² and R ^{3 in the general formula (1).} The imine unit.

上述(甲基)丙烯酸系樹脂中之通式(1)所示的戊二醯亞胺單元的含有比例較佳為5~50莫耳%、更佳為10~45莫耳%、進一步更佳為15~40莫耳%、特佳為20~35莫耳%、最佳為25~35莫耳%。若上述含有比例少於5莫耳%，則可能無法充分發揮由通式(1)所示的戊二酸酐單元所體現的效果，例如高光學特性、高機械強度、與偏光件的優異的黏接性、薄型化。若上述含有比例多於50莫耳%，則可能無法充分發揮例如高耐熱性、高透明性。 The content of the pentadiimide unit represented by the general formula (1) in the above-mentioned (meth)acrylic resin is preferably 5-50 mol%, more preferably 10-45 mol%, and still more preferably It is 15-40 mol%, particularly preferably 20-35 mol%, and most preferably 25-35 mol%. If the above content is less than 5 mol%, the effects of the glutaric anhydride unit represented by the general formula (1) may not be fully exhibited, such as high optical properties, high mechanical strength, and excellent adhesion to polarizers. Connectivity and thinness. If the above-mentioned content ratio is more than 50 mol%, for example, high heat resistance and high transparency may not be sufficiently exhibited.

上述(甲基)丙烯酸系樹脂中之通式(2)所示的不飽和羧酸烷基酯單元的含有比例較佳為50~95莫耳%、更佳為55~90莫耳%、進一步更佳為60~85莫耳%、特佳為65~80莫耳%、最佳為65~75莫耳%。若上述含有比例少於50莫耳%，則可能無法充分發揮由通式(2)所示的不飽和羧酸烷基酯單元體現的效果、例如高耐熱性、高透明性。若上述含有比例多於95莫耳%，則樹脂脆而容易破裂，無法充分發揮高機械強度，可能使生產率劣化。 The content ratio of the unsaturated carboxylic acid alkyl ester unit represented by the general formula (2) in the (meth)acrylic resin is preferably 50 to 95 mol%, more preferably 55 to 90 mol%, and further More preferably, it is 60~85 mol%, particularly preferably is 65~80 mol%, and most preferably is 65~75 mol%. If the above-mentioned content ratio is less than 50 mol%, the effect exhibited by the unsaturated carboxylic acid alkyl ester unit represented by the general formula (2), such as high heat resistance and high transparency, may not be sufficiently exhibited. If the above-mentioned content ratio is more than 95 mol%, the resin is brittle and easily cracked, and the high mechanical strength cannot be sufficiently exhibited, possibly deteriorating productivity.

具有通式(1)所示的戊二醯亞胺單元及通式(2)所示的不飽和羧酸烷基酯單元的(甲基)丙烯酸系樹脂基本上可以利用以下所示的方法來製造。 The (meth)acrylic resin having the glutaric imine unit represented by the general formula (1) and the unsaturated carboxylic acid alkyl ester unit represented by the general formula (2) can basically be obtained by the method shown below manufacture.

即，使與通式(2)所示的不飽和羧酸烷基酯單元對應的不飽和羧酸烷基酯單體、與不飽和羧酸單體及/或其前體單體共聚而得到共聚物(a)後，利用醯亞胺化劑對該共聚物(a)進行處理，從而進行該共聚物(a)中的不飽和羧酸烷基酯單體單元與不飽和羧酸單體及/或其前體單體單元的 分子內醯亞胺化反應，將通式(1)所示的戊二醯亞胺單元導入到共聚物中，由此可以得到上述(甲基)丙烯酸系樹脂。 That is, the unsaturated carboxylic acid alkyl ester monomer corresponding to the unsaturated carboxylic acid alkyl ester unit represented by the general formula (2) is copolymerized with the unsaturated carboxylic acid monomer and/or its precursor monomer. After copolymer (a), the copolymer (a) is treated with an imidizing agent, so that the unsaturated carboxylic acid alkyl ester monomer unit and the unsaturated carboxylic acid monomer in the copolymer (a) And/or its precursor monomer unit In the intramolecular imidization reaction, the glutarimide unit represented by the general formula (1) is introduced into the copolymer, thereby obtaining the above-mentioned (meth)acrylic resin.

作為不飽和羧酸烷基酯，例如可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸氯甲酯、(甲基)丙烯酸2-氯乙酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸3-羥基丙酯、(甲基)丙烯酸2,3,4,5,6-五羥基己酯及(甲基)丙烯酸2,3,4,5-四羥基戊酯等。其等可以僅使用1種，也可以並用2種以上。其中，在熱穩定性優異的方面，更佳為(甲基)丙烯酸甲酯，特佳為甲基丙烯酸甲酯。即，通式(1)中，特佳R⁴為甲基、且R⁵為甲基。 Examples of unsaturated carboxylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, (meth) T-butyl acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, chloromethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 2-(meth)acrylate Hydroxyethyl, 3-hydroxypropyl (meth)acrylate, 2,3,4,5,6-pentahydroxyhexyl (meth)acrylate and 2,3,4,5-tetrahydroxy (meth)acrylate Amyl ester and so on. These etc. may use only 1 type, and may use 2 or more types together. Among them, in terms of excellent thermal stability, methyl (meth)acrylate is more preferred, and methyl methacrylate is particularly preferred. That is, in the general formula (1), it is particularly preferable that R ⁴ is a methyl group and R ⁵ is a methyl group.

作為不飽和羧酸單體，例如可列舉丙烯酸、甲基丙烯酸、巴豆酸、α-取代丙烯酸、α-取代甲基丙烯酸等，作為其前體單體，可列舉丙烯醯胺、甲基丙烯醯胺等。此等不飽和羧酸單體或其前體單體可以僅使用1種，也可以並用2種以上。其中，尤其在使本發明的效果充分發揮的點來看，作為不飽和羧酸單體，較佳為丙烯酸、甲基丙烯酸，作為上述前體單體，較佳為丙烯醯胺。 Examples of unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, α-substituted acrylic acid, and α-substituted methacrylic acid. Examples of the precursor monomers include acrylamide and methacrylic acid. Amine etc. These unsaturated carboxylic acid monomers or their precursor monomers may be used alone or in combination of two or more kinds. Among them, particularly from the viewpoint of fully exerting the effects of the present invention, the unsaturated carboxylic acid monomer is preferably acrylic acid and methacrylic acid, and the precursor monomer is preferably acrylamide.

利用醯亞胺化劑對共聚物(a)進行處理的方法並無特別限定，可以使用習知公知的所有方法。例如利用使用擠出機、間歇式反應槽(壓力容器)等的方法，由此可以使上述共聚物(a)醯亞胺化。在使用擠出機進行加熱熔融、並利用醯亞胺化劑進行處理的情況下，所使用的擠出機並無 特別限定，可以使用各種擠出機。具體而言，例如可以使用單螺桿擠出機、雙螺桿擠出機或多螺桿擠出機等。另外，在使用間歇式反應槽(壓力容器)進行上述共聚物(a)的基於醯亞胺化劑的處理的情況下，該間歇式反應槽(壓力容器)的結構並無特別限定。 The method of treating the copolymer (a) with an imidizing agent is not particularly limited, and all conventionally known methods can be used. For example, by a method using an extruder, a batch reaction tank (pressure vessel), etc., the above-mentioned copolymer (a) can be imidized. In the case of using an extruder for heating and melting and treatment with an imidizing agent, the extruder used does not In particular, various extruders can be used. Specifically, for example, a single-screw extruder, a twin-screw extruder, or a multi-screw extruder can be used. In addition, when a batch-type reaction tank (pressure vessel) is used to perform the above-mentioned copolymer (a) treatment with an imidizing agent, the structure of the batch-type reaction tank (pressure vessel) is not particularly limited.

醯亞胺化劑並無特別限定，只要是能夠生成上述通式(1)所示的戊二醯亞胺單元的醯亞胺化劑即可。具體而言，例如可列舉：甲胺、乙胺、正丙胺、異丙胺、正丁胺、異丁胺、第三丁胺、正己胺等含脂肪族烴基的胺；苯胺、苄胺、甲苯胺、三氯苯胺等含芳香族烴基的胺；環己胺等含脂環式烴基的胺。 The imidizing agent is not particularly limited, as long as it is capable of producing the glutarimide unit represented by the above-mentioned general formula (1). Specifically, for example, aliphatic hydrocarbon group-containing amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, and n-hexylamine; aniline, benzylamine, toluidine Amines containing aromatic hydrocarbon groups such as trichloroaniline; amines containing alicyclic hydrocarbon groups such as cyclohexylamine.

另外，也可以使用像脲、1,3-二甲基脲、1,3-二乙基脲、1,3-二丙基脲藉由加熱產生上述例示的胺的脲系化合物。 In addition, urea compounds such as urea, 1,3-dimethylurea, 1,3-diethylurea, 1,3-dipropylurea, which generate the amines exemplified above by heating, can also be used.

在上述例示的醯亞胺化劑中，從成本、物性的方面來看，較佳使用甲胺、氨、環己胺，特佳使用甲胺。 Among the imidinating agents exemplified above, from the viewpoint of cost and physical properties, methylamine, ammonia, and cyclohexylamine are preferably used, and methylamine is particularly preferably used.

另外，在該醯亞胺化的步驟中，除了上述醯亞胺化劑外，還可以根據需要添加閉環促進劑。 In addition, in the step of the imidization, in addition to the above-mentioned imidization agent, a ring-closure accelerator may be added as necessary.

在該醯亞胺化的步驟中，相對於共聚物(a)100重量份，醯亞胺化劑較佳為0.5~10重量份、更佳為0.5~6重量份。若醯亞胺化劑的添加量低於0.5重量份，則使最終得到的樹脂組合物的醯亞胺化率變低，因此會使其耐熱性顯著降低，誘發成形後的焦糊等外觀缺陷。另外，若醯亞胺化劑的添加量高於10重量份，則會在樹脂中殘存醯亞胺化 劑，誘發成形後的焦糊等外觀缺陷、發泡。 In the step of the imidization, relative to 100 parts by weight of the copolymer (a), the imidization agent is preferably 0.5-10 parts by weight, more preferably 0.5-6 parts by weight. If the addition amount of the imidizing agent is less than 0.5 parts by weight, the resin composition finally obtained will have a low imidization rate, thereby significantly reducing its heat resistance and inducing appearance defects such as burnt after molding. . In addition, if the addition amount of the imidizing agent is more than 10 parts by weight, the imidization will remain in the resin It can induce appearance defects such as burnt paste and foaming after molding.

在本實施方式的製造方法中，除了上述醯亞胺化步驟外，也可以包括利用酯化劑進行處理的步驟。 In the production method of this embodiment, in addition to the above-mentioned imidization step, a step of treatment with an esterification agent may also be included.

作為酯化劑，例如可列舉：碳酸二甲酯、2,2-二甲氧基丙烷、二甲基亞碸、原甲酸三乙酯、原乙酸三甲酯、原甲酸三甲酯、碳酸二苯酯、硫酸二甲酯、甲苯磺酸甲酯、三氟甲基磺酸甲酯、乙酸甲酯、甲醇、乙醇、異氰酸甲酯、異氰酸對氯苯酯、二甲基碳二醯亞胺、二甲基第三丁基氯矽烷、乙酸異丙烯酯、二甲基脲、四甲基氫氧化銨、二甲基二乙氧基矽烷、四-N-丁氧基矽烷、二甲基(三甲基矽烷)亞磷酸酯、亞磷酸三甲基酯、磷酸三甲酯、磷酸三甲苯酯、重氮甲烷、環氧乙烷、環氧丙烷、氧化環己烯、2-乙基己基縮水甘油基醚、苯基縮水甘油基醚、苄基縮水甘油基醚等。其中，從成本、反應性等點來看，較佳為碳酸二甲酯。 As the esterification agent, for example, dimethyl carbonate, 2,2-dimethoxypropane, dimethyl sulfide, triethyl orthoformate, trimethyl orthoacetate, trimethyl orthoformate, dicarbonate Phenyl ester, dimethyl sulfate, methyl toluenesulfonate, methyl trifluoromethanesulfonate, methyl acetate, methanol, ethanol, methyl isocyanate, p-chlorophenyl isocyanate, dimethyl carbon two Amide, dimethyl tert-butyl chlorosilane, isopropenyl acetate, dimethyl urea, tetramethyl ammonium hydroxide, dimethyl diethoxy silane, tetra-N-butoxy silane, two Methyl (trimethylsilane) phosphite, trimethyl phosphite, trimethyl phosphate, tricresyl phosphate, diazomethane, ethylene oxide, propylene oxide, cyclohexene oxide, 2-ethyl Hexyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, etc. Among them, from the viewpoints of cost and reactivity, dimethyl carbonate is preferred.

作為酯化劑的添加量，並無特別限制，可以按照使(甲基)丙烯酸系樹脂的酸值達到期望值的方式來進行設定。 The addition amount of the esterification agent is not particularly limited, and it can be set so that the acid value of the (meth)acrylic resin reaches a desired value.

本實施方式的(甲基)丙烯酸系樹脂含有上述通式(1)所示的戊二醯亞胺單元及不飽和羧酸烷基酯單元，且具有特定的醯亞胺化率、酸值、丙烯酸酯單元含量。 The (meth)acrylic resin of the present embodiment contains the glutaric imine unit and the unsaturated carboxylic acid alkyl ester unit represented by the general formula (1), and has a specific imidization rate, acid value, Acrylate unit content.

上述(甲基)丙烯酸系樹脂中的醯亞胺化率以戊二醯亞胺單元與不飽和羧酸烷基酯單元的比來表示。因此，“醯亞胺化率”是指全部羰基中的醯亞胺羰基所佔據的比例。該比例如可利用(甲基)丙烯酸系樹脂的NMR光譜、IR 光譜或其他方法來測定，本實施方式的醯亞胺化率係使用¹HNMR BRUKER AvanceIII(400MHz)進行樹脂的¹H-NMR測定來求得。將3.5~3.8ppm附近的來自不飽和羧酸烷基酯的O-CH₃質子的峰面積設為A，將3.0~3.3ppm附近的來自戊二醯亞胺的N-CH₃質子的峰面積設為B，並利用下式求得。 The rate of imidization in the (meth)acrylic resin is represented by the ratio of the glutaric imine unit to the unsaturated carboxylic acid alkyl ester unit. Therefore, the "amidization rate" refers to the proportion occupied by the amide carbonyl group in all carbonyl groups. This ratio can be utilized such as (meth) acrylic resin NMR spectrum, the IR spectrum measurement, or other methods, (PEI) rate-based embodiment of the present embodiment using ¹ HNMR BRUKER ^AvanceIII (400MHz) measured by ¹ HNMR resin Come get it. _{Set the peak area of O-CH 3} protons derived from unsaturated carboxylic acid alkyl esters near 3.5 to 3.8 ppm as A, and set the peak area of N-CH ₃ protons derived from glutarimide near 3.0 to 3.3 ppm Set it to B, and use the following equation to find it.

Im%={B/(A+B)}×100 Im%={B/(A+B)}×100

上述醯亞胺化率需要設為2.5~5.0%。若醯亞胺化率為上述範圍內，則不會使所得的(甲基)丙烯酸系樹脂的耐熱性及透明性降低、或者不會使成形加工性降低、不會產生加工為薄膜時的焦糊、不會使機械強度降低。另一方面，若醯亞胺化率少於上述範圍，則存在如下傾向：在第1透明保護薄膜的薄膜製膜時產生焦糊，或者使所得的(甲基)丙烯酸系樹脂的耐熱性不足，或者使透明性受損。另外，若醯亞胺化率多於上述範圍，則存在如下傾向：產生焦糊，或使耐熱性及熔融黏度不必要地提高，成形加工性變差，或者薄膜加工時的機械強度變得極脆，或者使透明性受損。 The above-mentioned imidization rate needs to be 2.5 to 5.0%. If the imidization rate is within the above range, the heat resistance and transparency of the obtained (meth)acrylic resin will not be reduced, or the molding processability will not be reduced, and the burnt during processing into a film will not occur. Paste, will not reduce the mechanical strength. On the other hand, if the imidization rate is less than the above range, there is a tendency that burns are generated during the film formation of the first transparent protective film, or the heat resistance of the obtained (meth)acrylic resin is insufficient , Or impair transparency. In addition, if the imidization rate is more than the above range, there is a tendency that scorch is generated, heat resistance and melt viscosity are unnecessarily increased, the molding processability is deteriorated, or the mechanical strength during film processing becomes extremely high. Brittle, or impaired transparency.

本實施方式的(甲基)丙烯酸系樹脂的酸值表示(甲基)丙烯酸系樹脂中的羧酸單元、羧酸酐單元的含量。酸值可以利用例如WO2005-054311中記載的滴定法、日本特開2005-23272號公報中記載的滴定法等來計算。 The acid value of the (meth)acrylic resin of the present embodiment represents the content of the carboxylic acid unit and the carboxylic anhydride unit in the (meth)acrylic resin. The acid value can be calculated by, for example, the titration method described in WO2005-054311, the titration method described in JP 2005-23272 A, and the like.

上述(甲基)丙烯酸系樹脂的酸值需要為0.10~0.50mmol/g。若酸值為上述範圍內，則可以得到耐熱性、機械物性、成形加工性的平衡優異的(甲基)丙烯酸系樹脂。另一方面，例如，若酸值大於上述範圍，則存在如下傾向： 容易引起熔融擠出時的樹脂的發泡，使成形加工性降低，成形品的生產率降低。若酸值小於上述範圍，則需要更多地消耗用於調整到該酸值的變性劑，因此有時會使成本升高，或者誘發因變性劑的殘存所致的凝膠狀物的產生，故不為所欲。 The acid value of the (meth)acrylic resin needs to be 0.10 to 0.50 mmol/g. If the acid value is within the above range, a (meth)acrylic resin having an excellent balance of heat resistance, mechanical properties, and moldability can be obtained. On the other hand, for example, if the acid value is greater than the above range, the following tendencies exist: It is easy to cause foaming of the resin during melt extrusion, which reduces the molding processability and reduces the productivity of molded products. If the acid value is less than the above range, the denaturant used to adjust the acid value needs to be consumed more, which may increase the cost or induce the generation of gel due to the residual denaturant. Therefore, do not do what you want.

本實施方式的(甲基)丙烯酸系樹脂中所含的丙烯酸酯單元不足1重量%，較佳不足0.5重量%。若丙烯酸酯單元為上述範圍內，則(甲基)丙烯酸系樹脂的熱穩定性優異，但是，若丙烯酸酯單元超過上述範圍，則存在如下傾向：熱穩定性變差，在樹脂製造時或成形加工時樹脂的分子量降低、黏度降低，物性變差。 The acrylate unit contained in the (meth)acrylic resin of this embodiment is less than 1% by weight, preferably less than 0.5% by weight. If the acrylate unit is within the above range, the (meth)acrylic resin has excellent thermal stability. However, if the acrylate unit exceeds the above range, the thermal stability tends to deteriorate, which may result in poor thermal stability during resin production or molding. During processing, the molecular weight and viscosity of the resin decrease, and the physical properties deteriorate.

在上述(甲基)丙烯酸系樹脂中，還可以包含除通式(1)所示的戊二醯亞胺單元及通式(2)所示的不飽和羧酸烷基酯單元以外的其他單元。 The above-mentioned (meth)acrylic resin may also contain other units other than the glutarimide unit represented by the general formula (1) and the unsaturated carboxylic acid alkyl ester unit represented by the general formula (2) .

在上述(甲基)丙烯酸系樹脂中，例如可以含有不參與上述分子內醯亞胺化反應的來自不飽和羧酸單體的單元0~10重量%。來自不飽和羧酸的單元的比例更佳為0~5重量%、進一步更佳為0~1重量%。藉由使上述(甲基)丙烯酸系樹脂中的來自不飽和羧酸單體的單元為10重量%以下，可以維持無色透明性、滯留穩定性、耐濕性。 The (meth)acrylic resin may contain, for example, 0 to 10% by weight of units derived from unsaturated carboxylic acid monomers that do not participate in the intramolecular imidization reaction. The ratio of the unit derived from an unsaturated carboxylic acid is more preferably 0 to 5% by weight, and still more preferably 0 to 1% by weight. By making the unit derived from the unsaturated carboxylic acid monomer in the (meth)acrylic resin 10% by weight or less, colorless transparency, retention stability, and moisture resistance can be maintained.

另外，本發明的(甲基)丙烯酸系樹脂可以含有除上述以外的能夠共聚的其他乙烯基系單體單元。作為其他的乙烯基系單體，例如可列舉丙烯腈、甲基丙烯腈、乙基丙烯腈、烯丙基縮水甘油基醚、馬來酸酐、衣康酸酐、N- 甲基馬來醯亞胺、N-乙基馬來醯亞胺、N-環己基馬來醯亞胺、丙烯酸胺基乙酯、丙烯酸丙基胺基乙酯、甲基丙烯酸二甲基胺基乙酯、甲基丙烯酸乙基胺基丙酯、甲基丙烯酸環己基胺基乙酯、N-乙烯基二乙基胺、N-乙醯乙烯基胺、烯丙基胺、甲基烯丙基胺、N-甲基烯丙基胺、2-異丙烯基噁唑啉、2-乙烯基噁唑啉、2-丙烯醯基噁唑啉、N-苯基馬來醯亞胺、甲基丙烯酸苯基胺基乙酯、苯乙烯、α-甲基苯乙烯、對縮水甘油基苯乙烯、對胺基苯乙烯、2-苯乙烯基噁唑啉等。其等可以僅使用1種，也可以並用2種以上。 In addition, the (meth)acrylic resin of the present invention may contain other copolymerizable vinyl monomer units other than the above. As other vinyl monomers, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, allyl glycidyl ether, maleic anhydride, itaconic anhydride, N- Methyl maleimide, N-ethyl maleimide, N-cyclohexyl maleimide, amino ethyl acrylate, propyl amino ethyl acrylate, dimethyl amino methacrylate Ethyl, ethylaminopropyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallyl Amine, N-methallylamine, 2-isopropenyloxazoline, 2-vinyloxazoline, 2-propenyloxazoline, N-phenylmaleimide, methacrylic acid Phenylaminoethyl, styrene, α-methylstyrene, p-glycidyl styrene, p-aminostyrene, 2-styryl oxazoline, etc. These etc. may use only 1 type, and may use 2 or more types together.

在上述的其他乙烯基系單體中，苯乙烯、α-甲基苯乙烯等苯乙烯系結構單元的含有比例較佳為0~1重量%、更佳為0~0.1重量%。藉由使苯乙烯系結構單元的含有濃度為0~1重量%，可以防止相位差變差及透明性降低。 In the above-mentioned other vinyl monomers, the content of styrene structural units such as styrene and α-methylstyrene is preferably 0 to 1% by weight, more preferably 0 to 0.1% by weight. By setting the content concentration of the styrene-based structural unit to 0 to 1% by weight, it is possible to prevent the retardation from deteriorating and the transparency from decreasing.

上述(甲基)丙烯酸系樹脂的重量平均分子量較佳為1000~2000000、更佳為5000~1000000、進一步更佳為10000~500000、特佳為50000~500000、最佳為60000~150000。若重量平均分子量落在上述範圍外，則可能無法充分發揮本發明的效果。重量平均分子量採用凝膠滲透色譜(GPC系統，東曹製)並利用聚苯乙烯換算而求得。溶劑使用四氫呋喃。 The weight average molecular weight of the (meth)acrylic resin is preferably 1,000 to 2,000,000, more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably 50,000 to 500,000, and most preferably 60,000 to 150,000. If the weight average molecular weight falls outside the above range, the effects of the present invention may not be fully exhibited. The weight average molecular weight was obtained by gel permeation chromatography (GPC system, manufactured by Tosoh) and converted into polystyrene. Tetrahydrofuran was used as the solvent.

上述(甲基)丙烯酸系樹脂的Tg(玻璃化轉變溫度)較佳為110℃以上、更佳為115℃以上、進一步更佳為120℃以上、特佳為125℃以上、最佳為130℃以上。藉由使Tg為110℃以上，例如在最終裝入偏光板時，耐久性容易變得優 異。上述(甲基)丙烯酸系樹脂的Tg的上限值並無特別限定，從成形性等點來看，較佳為300℃以下、更佳為290℃以下、進一步更佳為285℃以下、特佳為200℃以下、最佳為160℃以下。 The Tg (glass transition temperature) of the (meth)acrylic resin is preferably 110°C or higher, more preferably 115°C or higher, still more preferably 120°C or higher, particularly preferably 125°C or higher, most preferably 130°C the above. By setting the Tg to 110°C or higher, for example, when the polarizing plate is finally installed, the durability is easily improved. different. The upper limit of the Tg of the (meth)acrylic resin is not particularly limited, but from the viewpoint of moldability and the like, it is preferably 300°C or lower, more preferably 290°C or lower, and still more preferably 285°C or lower. It is preferably below 200°C, most preferably below 160°C.

上述(甲基)丙烯酸系樹脂的藉由注射成形所得到的成形品的、利用基於ASTM-D-1003的方法測定的總透光率越高越佳，較佳為85%以上、更佳為88%以上、進一步更佳為90%以上。若總透光率不足85%，則透明性降低，可能無法用於原本的目的用途。 The higher the total light transmittance of the molded article obtained by injection molding of the above-mentioned (meth)acrylic resin, measured by a method based on ASTM-D-1003, the better, preferably 85% or more, more preferably 88% or more, more preferably 90% or more. If the total light transmittance is less than 85%, the transparency is reduced, and it may not be used for the original purpose.

第1透明保護薄膜中之上述(甲基)丙烯酸系樹脂的含量較佳為50~100重量%、更佳為60~100重量%、進一步更佳為70~100重量%、特佳為80~100重量%。在本發明的透明保護薄膜中之上述(甲基)丙烯酸系樹脂的含量不足50重量%的情況下，可能無法充分反映上述(甲基)丙烯酸系樹脂原本具有的高耐熱性、高透明性。 The content of the (meth)acrylic resin in the first transparent protective film is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight, particularly preferably 80 to 100% by weight. When the content of the (meth)acrylic resin in the transparent protective film of the present invention is less than 50% by weight, the high heat resistance and high transparency inherently possessed by the (meth)acrylic resin may not be fully reflected.

另外，本實施方式的第1透明保護薄膜中，作為能夠與上述(甲基)丙烯酸系樹脂並用的樹脂，可列舉聚乙烯、聚丙烯、聚醯胺、聚苯硫醚、聚醚醚酮、聚酯、聚碸、聚苯醚、聚縮醛、聚醯亞胺、聚醚醯亞胺等其他熱塑性樹脂、酚醛系樹脂、密胺系樹脂、聚酯系樹脂、矽酮系樹脂、環氧系樹脂等熱固化性樹脂。其等可以在不損害本發明目的範圍內配合。 In addition, in the first transparent protective film of the present embodiment, examples of resins that can be used in combination with the above-mentioned (meth)acrylic resin include polyethylene, polypropylene, polyamide, polyphenylene sulfide, polyether ether ketone, Other thermoplastic resins such as polyester, polyether, polyphenylene ether, polyacetal, polyimide, polyetherimide, phenolic resin, melamine resin, polyester resin, silicone resin, epoxy Thermosetting resins such as resins. They can be combined within a range that does not impair the purpose of the present invention.

第1透明保護薄膜包含上述(甲基)丙烯酸系樹脂以及紫外線吸收劑。本實施方式的第1透明樹脂薄膜具備特 定的結構單元及特定的醯亞胺化率、酸值、丙烯酸酯單元含量，因此能夠防止由本案發明人等新發現的由紫外線吸收劑引起的薄膜製膜時的焦糊，並且可以抑制偏光板的黃變。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系化合物、苯並***系化合物、水楊酸酯系化合物、二苯甲酮系化合物、氰基丙烯酸酯系化合物、鎳絡鹽系化合物、三嗪系化合物等。作為對第1透明保護薄膜賦予紫外線吸收劑的方法，可列舉使透明保護薄膜中含有紫外線吸收劑的方法、使作為透明保護薄膜的構成層的含有紫外線吸收劑的層進行積層的方法。 The first transparent protective film contains the above-mentioned (meth)acrylic resin and an ultraviolet absorber. The first transparent resin film of this embodiment has characteristics The specific structural unit and specific imidization rate, acid value, and acrylate unit content can prevent burnt during film formation caused by the ultraviolet absorber newly discovered by the inventors of this case, and can suppress polarized light Yellowing of the board. Specific examples of ultraviolet absorbers include, for example, conventionally known oxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, and cyanoacrylate compounds. , Nickel complex salt compounds, triazine compounds, etc. As a method of applying an ultraviolet absorber to the first transparent protective film, a method of including an ultraviolet absorber in a transparent protective film and a method of laminating a layer containing an ultraviolet absorber as a constituent layer of the transparent protective film can be cited.

第1透明保護薄膜中的紫外線吸收劑的含量只要按照得到目的黃變防止效果的方式進行適當調整即可。若紫外線吸收劑的含量過少，則有時使黃變防止效果變得不充分，相反，若紫外線吸收劑的含量過多，則有時變得難以充分抑制焦糊，或者產生紫外線吸收劑的滲出。 The content of the ultraviolet absorber in the first transparent protective film may be appropriately adjusted so as to obtain the desired yellowing prevention effect. If the content of the ultraviolet absorber is too small, the yellowing prevention effect may become insufficient. On the contrary, if the content of the ultraviolet absorber is too large, it may become difficult to sufficiently suppress burnout or bleed out of the ultraviolet absorber may occur.

另外，上述的其他樹脂、上述添加劑配合於用於形成上述(甲基)丙烯酸系樹脂的原料，可以在製造(甲基)丙烯酸系樹脂時進行配合，也可以在製造(甲基)丙烯酸系樹脂後進行配合。 In addition, the above-mentioned other resins and the above-mentioned additives are blended with the raw materials used to form the (meth)acrylic resin, and may be blended when the (meth)acrylic resin is manufactured, or may be used when the (meth)acrylic resin is manufactured Cooperate afterwards.

本發明的含有上述(甲基)丙烯酸系樹脂的透明保護薄膜通常藉由將上述(甲基)丙烯酸系樹脂利用流延法、注射成形法、熔融擠出成形法進行薄膜化而得到。為了提高薄膜強度，可以對所得的薄膜進行單軸或雙軸拉伸。 The transparent protective film containing the (meth)acrylic resin of the present invention is usually obtained by forming the (meth)acrylic resin into a film by a casting method, an injection molding method, or a melt extrusion molding method. In order to increase the strength of the film, the resulting film may be uniaxially or biaxially stretched.

含有上述(甲基)丙烯酸系樹脂的透明保護薄膜 在未拉伸的狀態下幾乎不體現相位差，但是，若對其進行拉伸，則產生相位差。在進行拉伸的情況下，藉由拉伸倍率及相位差控制劑的添加，可以控制相位差。作為相位差控制劑，較佳為苯乙烯系樹脂，特佳為丙烯腈-苯乙烯共聚物。 Transparent protective film containing the above (meth)acrylic resin In the unstretched state, the phase difference hardly appears, but when it is stretched, the phase difference occurs. In the case of stretching, the retardation can be controlled by the addition of the stretching ratio and the retardation control agent. As the retardation control agent, a styrene resin is preferred, and an acrylonitrile-styrene copolymer is particularly preferred.

本實施方式的第1透明保護薄膜較佳為光學各向異性小。特佳為不僅薄膜的面內方向(長度方向、寬度方向)的光學各向異性小，而且厚度方向的光學各向異性也小。換言之，以面內相位差及厚度方向相位差均小為佳。 The first transparent protective film of the present embodiment preferably has low optical anisotropy. It is particularly preferable that not only the optical anisotropy in the in-plane direction (length direction, width direction) of the film is small, but also the optical anisotropy in the thickness direction is small. In other words, it is preferable that both the in-plane retardation and the thickness direction retardation are small.

具體而言，第1透明保護薄膜的面內相位差及厚度方向相位差分別較佳為40nm以下、更佳為20nm以下。若為具有此種光學特性的構成，則可以將本實施方式的透明保護薄膜適當地用作液晶顯示裝置的偏光板所具備的偏光件保護薄膜。另一方面，若薄膜的面內相位差超過40nm、或者厚度方向相位差超過40nm，則在將本實施方式的透明保護薄膜裝入液晶顯示裝置的偏光板而使用的情況下，有時在液晶顯示裝置中產生對比度降低等問題。 Specifically, the in-plane retardation and the thickness direction retardation of the first transparent protective film are each preferably 40 nm or less, and more preferably 20 nm or less. If it is a structure which has such an optical characteristic, the transparent protective film of this embodiment can be used suitably as a polarizer protective film with which the polarizing plate of a liquid crystal display device is equipped. On the other hand, if the in-plane retardation of the film exceeds 40nm, or the thickness direction retardation exceeds 40nm, when the transparent protective film of this embodiment is incorporated into the polarizing plate of a liquid crystal display device and used, the liquid crystal may The display device has problems such as a decrease in contrast.

另外，面內相位差(Re)及厚度方向相位差(Rth)分別可以利用以下的式子來計算。即，在三維方向為完全光學各向同性的理想的薄膜中，面內相位差Re、厚度方向相位差Rth均為0。 In addition, the in-plane retardation (Re) and the thickness direction retardation (Rth) can be calculated by the following equations, respectively. That is, in an ideal film that is completely optically isotropic in the three-dimensional direction, both the in-plane retardation Re and the thickness direction retardation Rth are zero.

Re=(nx-ny)×d Re=(nx-ny)×d

Rth=(nx-nz)×d Rth=(nx-nz)×d

另外，上述式中，將面內折射率達到最大的方向設為X 軸，將與X軸垂直的方向設為Y軸，將薄膜的厚度方向設為Z軸，並且將各軸方向的折射率表示為nx、ny及nz。另外，d表示薄膜的厚度(nm)。 In addition, in the above formula, the direction in which the in-plane refractive index reaches the maximum is X As for the axis, the direction perpendicular to the X axis is set to the Y axis, the thickness direction of the film is set to the Z axis, and the refractive index in each axis direction is expressed as nx, ny, and nz. In addition, d represents the thickness (nm) of the film.

本實施方式的含有具有不飽和羧酸烷基酯單元及戊二酸酐單元的(甲基)丙烯酸系樹脂的透明保護薄膜可以滿足透濕度為300g/m²以下，在耐久性的方面較佳。透濕度更佳為250g/m²以下，更進一步以200g/m²以下為佳。 The transparent protective film containing the (meth)acrylic resin having the unsaturated carboxylic acid alkyl ester unit and the glutaric anhydride unit of the present embodiment can satisfy the moisture permeability of 300 g/m ² or less, and is preferable in terms of durability. The water vapor transmission rate is more preferably 250 g/m ² or less, and still more preferably 200 g/m ² or less.

另外，在本實施方式所使用的第1透明保護薄膜中可以包含1種以上的任意的適當的添加劑。作為其他添加劑，例如可列舉：受阻酚系、磷系、硫系等的抗氧化劑；耐光穩定劑、耐候穩定劑、熱穩定劑等穩定劑；玻璃纖維、碳纖維等增強材料；近紅外線吸收劑；三(二溴丙基)磷酸酯、三烯丙基磷酸酯、氧化銻等阻燃劑；陰離子系、陽離子系、非離子系的表面活性劑等防靜電劑；無機顏料、有機顏料、染料等著色劑；有機填料或無機填料；樹脂改性劑；有機填充劑或無機填充劑；增塑劑；潤滑劑；防靜電劑；阻燃劑；等。 In addition, the first transparent protective film used in this embodiment may contain one or more arbitrary appropriate additives. Examples of other additives include: hindered phenol-based, phosphorus-based, sulfur-based antioxidants; stabilizers such as light-resistant stabilizers, weather-resistant stabilizers, and heat stabilizers; reinforcing materials such as glass fibers and carbon fibers; near-infrared absorbers; Tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide and other flame retardants; anionic, cationic, non-ionic surfactants and other antistatic agents; inorganic pigments, organic pigments, dyes, etc. Colorants; organic fillers or inorganic fillers; resin modifiers; organic fillers or inorganic fillers; plasticizers; lubricants; antistatic agents; flame retardants; etc.

本實施方式第1透明保護薄膜中之添加劑的含有比例較佳為0~5重量%、更佳為0~2重量%、進一步更佳為0~0.5重量%。 The content ratio of the additive in the first transparent protective film of this embodiment is preferably 0 to 5% by weight, more preferably 0 to 2% by weight, and still more preferably 0 to 0.5% by weight.

(第2透明保護薄膜) (Second transparent protective film)

本實施方式中，作為相位差板使用的第2透明保護薄膜含有纖維素酯作為主原料。纖維素酯可以採用任意的適當材料。較佳地，纖維素酯是纖維素的碳原子數為6以下的低 級脂肪酸酯。作為具體例，可列舉：纖維素乙酸酯、纖維素丙酸酯、纖維素丁酸酯等纖維素的羥基被相同的低級脂肪酸酯化後的物質；纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等纖維素的羥基被不同的低級脂肪酸酯化後的物質，特佳為纖維素的羥基被乙醯基及/或丙醯基取代後的纖維素酯。其等可以單獨使用1種或並用2種以上。纖維素酯可以藉由改變低級脂肪酸的取代基的種類、低級脂肪酸的取代度來控制所得的相位差板的相位差值。另外，為了控制相位差，也可以含有相位差提高劑、相位差控制劑。上述纖維素酯可以利用任意的適當方法、例如日本特開2001-188128號公報中記載的方法來製造。另外，就纖維素酯而言，市售有大量的製品，在獲得容易性、成本的方面也是有利的。作為纖維素酯的市售品的例子，可列舉富士膠片公司製的商品名“UV-50”、“UV-80”、“SH-80”、“TD-80U”、“TD-TAC”、“UZ-TAC”、柯尼卡公司製的“KC系列”等。 In this embodiment, the second transparent protective film used as a phase difference plate contains cellulose ester as a main raw material. Any appropriate material can be used for the cellulose ester. Preferably, the cellulose ester has a low carbon number of 6 or less. Grade fatty acid esters. Specific examples include: cellulose acetate, cellulose propionate, cellulose butyrate, and other cellulose hydroxyl groups are esterified with the same lower fatty acid; cellulose acetate propionate, Cellulose hydroxyl groups such as cellulose acetate butyrate are esterified with different lower fatty acids, particularly preferably cellulose esters in which the cellulose hydroxyl groups are substituted with acetyl and/or propylene groups. These can be used individually by 1 type or in combination of 2 or more types. The cellulose ester can control the retardation value of the obtained retardation plate by changing the type of the substituent of the lower fatty acid and the degree of substitution of the lower fatty acid. In addition, in order to control the retardation, a retardation improving agent and a retardation controlling agent may be contained. The above-mentioned cellulose ester can be produced by any appropriate method, for example, the method described in JP 2001-188128 A. In addition, cellulose esters are commercially available in a large number of products, and they are also advantageous in terms of ease of availability and cost. As examples of commercially available cellulose esters, Fujifilm’s trade names "UV-50", "UV-80", "SH-80", "TD-80U", "TD-TAC", "UZ-TAC", "KC series" manufactured by Konica Corporation, etc.

在上述纖維素酯包含乙醯基作為低級脂肪酸的取代基的情況下，該乙醯基的取代度較佳為3以下、更佳為0.5~3、特佳為1~3。在上述纖維素酯包含丙醯基作為低級脂肪酸的取代基的情況下，該丙醯基的取代度較佳為3以下、更佳為0.5~3、特佳為1~3。另外，在上述纖維素酯為纖維素的羥基的一部分被乙醯基取代、另一部分被丙醯基取代的混合脂肪酸酯的情況下，乙醯基的取代度與丙醯基的取代度的總和較佳為1~3、更佳為2~3。此時，乙醯 基的取代度較佳為0.5~2.5，丙醯基的取代度較佳為0.3~1.5。 In the case where the above-mentioned cellulose ester contains an acetyl group as a substituent of the lower fatty acid, the degree of substitution of the acetyl group is preferably 3 or less, more preferably 0.5 to 3, and particularly preferably 1 to 3. In the case where the above-mentioned cellulose ester contains a propyl group as a substituent of a lower fatty acid, the substitution degree of the propyl group is preferably 3 or less, more preferably 0.5 to 3, and particularly preferably 1 to 3. In addition, when the above-mentioned cellulose ester is a mixed fatty acid ester in which a part of the hydroxyl group of cellulose is substituted with an acetyl group and the other part is substituted with a propyl group, the degree of substitution of the acetyl group is less than that of the propyl group. The sum is preferably 1-3, more preferably 2-3. At this time, Acetate The degree of substitution of the group is preferably 0.5 to 2.5, and the degree of substitution of the propyl group is preferably 0.3 to 1.5.

另外，乙醯基的取代度(或丙醯基的取代度)表示纖維素骨架中之位於2、3、6位碳的羥基被乙醯基(或丙醯基)取代的數量。乙醯基(或丙醯基)可以偏在於纖維素骨架中之2、3、6位碳的任意一者上，也可以平均地存在。上述乙醯基的取代度可以利用ASTM-D817-91(纖維素乙酸酯等的試驗法)來求得。另外，上述丙醯基的取代度可以利用ASTM-D817-96(纖維素乙酸酯等的試驗法)來求得。 In addition, the degree of substitution of the acetyl group (or the degree of substitution of the propionyl group) indicates the number of substitutions of the hydroxyl group at the 2, 3, and 6-position carbons in the cellulose skeleton by the acetyl group (or the propionyl group). Acetyl (or propionyl) may be located on any one of the 2, 3, and 6 carbons in the cellulose skeleton, or it may exist evenly. The degree of substitution of the acetyl group can be determined by ASTM-D817-91 (testing method for cellulose acetate etc.). In addition, the degree of substitution of the propyl group can be determined by ASTM-D817-96 (testing method for cellulose acetate etc.).

上述纖維素酯的利用基於四氫呋喃溶劑的凝膠滲透色譜(GPC)法測定的重量平均分子量(Mw)較佳為30,000~500,000、更佳為50,000~400,000、最佳為80,000~300,000。若重量平均分子量為上述的範圍，則可以使機械強度優異，且溶解性、成形性、流延的操作性良好。 The weight average molecular weight (Mw) of the above-mentioned cellulose ester determined by the gel permeation chromatography (GPC) method based on tetrahydrofuran solvent is preferably 30,000 to 500,000, more preferably 50,000 to 400,000, and most preferably 80,000 to 300,000. If the weight average molecular weight is in the above range, the mechanical strength can be excellent, and the solubility, moldability, and casting workability can be good.

另外，上述纖維素酯的分子量分佈(重量平均分子量Mw/數均分子量Mn)較佳為1.5~5.5、更佳為2~5。 In addition, the molecular weight distribution (weight average molecular weight Mw/number average molecular weight Mn) of the cellulose ester is preferably 1.5 to 5.5, more preferably 2 to 5.

第2透明保護薄膜滿足nx>ny>nz的關係。該相位差板的面內相位差通常被控制在40~300nm的範圍，厚度方向相位差通常被控制在80~320nm的範圍。進而，較佳使面內相位差為40~100nm、厚度方向相位差為100~320nm，Nz係數較佳滿足1.8~4.5。Nz係數代表性地為3.5~4.5左右。藉由採用該相位差板，可以改善斜視方向的視角特性。特別適合應用於IPS模式、VA模式的液晶顯示裝置的情況。另外，Nz係數以Nz=(nx-nz)/(nx-ny)來表示(nx、 ny、nz的定義與面內相位差及厚度方向相位差相同)。 The second transparent protective film satisfies the relationship of nx>ny>nz. The in-plane phase difference of the phase difference plate is usually controlled in the range of 40 to 300 nm, and the thickness direction phase difference is usually controlled in the range of 80 to 320 nm. Furthermore, it is preferable that the in-plane retardation is 40 to 100 nm, the thickness direction retardation is 100 to 320 nm, and the Nz coefficient preferably satisfies 1.8 to 4.5. The Nz coefficient is typically about 3.5 to 4.5. By using the phase difference plate, the viewing angle characteristics in the oblique direction can be improved. It is particularly suitable for use in IPS mode and VA mode liquid crystal display devices. In addition, the Nz coefficient is represented by Nz=(nx-nz)/(nx-ny) (nx, The definitions of ny and nz are the same as in-plane retardation and thickness direction retardation).

作為被用作上述相位差板的第2透明保護薄膜，可以使用例如滿足nx>ny>nz的折射率關係的二軸性相位差板(富士膠片公司製“WVBZ4A6”、柯尼卡公司製“KC4DR-1”等)。此等相位差的控制可以藉由將包含纖維素酯的高分子薄膜沿著縱向或橫向單軸拉伸或雙軸拉伸而得。 As the second transparent protective film used as the above-mentioned retardation film, for example, a biaxial retardation film satisfying the refractive index relationship of nx>ny>nz ("WVBZ4A6" manufactured by Fuji Photo Film Co., Ltd., "manufactured by Konica Corporation") can be used. KC4DR-1” etc.). The phase difference can be controlled by uniaxially or biaxially stretching the polymer film containing cellulose ester in the longitudinal or transverse direction.

另外，上述相位差板可以為例如各種波長板、以基於液晶層的雙折射的著色、補償視角等為目的的相位差板等具有與使用目的對應的適宜的相位差的相位差板，也可以為積層2種以上的相位差板來控制相位差等光學特性的相位差板。 In addition, the above-mentioned retardation plate may be, for example, various wavelength plates, a retardation plate for the purpose of coloration based on the birefringence of the liquid crystal layer, compensation of viewing angle, etc., a retardation plate having a suitable retardation corresponding to the purpose of use, or may be It is a retardation plate that laminates two or more types of retardation plates to control optical characteristics such as retardation.

在本實施方式中使用的第2透明保護薄膜中可以包含1種以上的任意適當的添加劑。作為其他添加劑(包括紫外線吸收劑。)及其含量，可以適合使用第1透明保護薄膜一項中所示的添加劑及其含量。 The second transparent protective film used in this embodiment may contain one or more arbitrary appropriate additives. As other additives (including ultraviolet absorbers) and their contents, the additives and their contents shown in the section of the first transparent protective film can be suitably used.

本實施方式的第1透明保護薄膜及第2透明保護薄膜的厚度可以適當確定，但是通常出於強度、處理性等操作性、薄層性等方面，分別獨立為1~500μm左右。尤其較佳1~300μm，更佳5~200μm。 The thickness of the first transparent protective film and the second transparent protective film of the present embodiment can be appropriately determined, but generally, they are independently about 1 to 500 μm in view of handling properties such as strength and handling properties, and thin layer properties. It is particularly preferably 1 to 300 μm, and more preferably 5 to 200 μm.

(塗布層) (Coating layer)

在上述透明保護薄膜的未黏接偏光件的面可以設置硬塗層、防污層、防反射層、防黏連層、擴散層或防眩層等各種塗布層。 Various coating layers such as hard coat, anti-fouling layer, anti-reflection layer, anti-adhesion layer, diffusion layer or anti-glare layer can be provided on the surface of the transparent protective film that is not adhered to the polarizer.

硬塗層為以防止偏光板表面的損傷等為目的實施的塗布層，例如可以以在透明保護薄膜的表面附加由丙烯酸系、矽酮系等適當的紫外線固化型樹脂形成的硬度、潤滑特性等優異的固化被膜的方式等來形成。防污層以防止偏光板表面的污漬為目的。防反射層為以防止在偏光板表面的外光反射為目的實施的塗布層，可以利用基於以往的防反射膜等的形成來實現。另外，防黏連層以防止與相鄰層的密合為目的而實施。 The hard coat layer is a coating layer implemented for the purpose of preventing damage to the surface of the polarizing plate. For example, the surface of the transparent protective film can be added with the hardness and lubricating properties of an appropriate ultraviolet curable resin such as acrylic or silicone. It is formed by an excellent curing film method. The antifouling layer aims to prevent stains on the surface of the polarizing plate. The anti-reflection layer is a coating layer implemented for the purpose of preventing the reflection of external light on the surface of the polarizing plate, and can be realized by the formation of a conventional anti-reflection film or the like. In addition, the anti-adhesion layer is implemented for the purpose of preventing adhesion with adjacent layers.

另外，防眩層為以防止因外光在偏光板的表面反射而阻礙偏光板透射光的觀察等為目的實施的塗布層，可以藉由例如基於噴砂方式、印花加工方式的粗面化方式、透明微粒的配合方式等適宜的方式對透明保護薄膜的表面賦予微細凹凸結構來形成。作為在上述表面微細凹凸結構的形成中所含有的微粒，可以使用例如：平均粒徑為0.5~50μm的包括二氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等的也有時具有導電性的無機系微粒、包括交聯或未交聯的聚合物等的有機系微粒等透明微粒。在形成表面微細凹凸結構的情況下，微粒的使用量相對於要形成表面微細凹凸結構的透明樹脂100重量份通常為2~50重量份左右，較佳為5~25重量份。防眩層也可以兼作用於使偏光板透射光擴散而擴大視角等的擴散層(視角擴大機能等)。 In addition, the anti-glare layer is a coating layer implemented for the purpose of preventing obstruction of the observation of transmitted light of the polarizing plate due to the reflection of external light on the surface of the polarizing plate. The transparent protective film is formed by imparting a fine uneven structure to the surface of the transparent protective film in an appropriate manner, such as the compounding method of the transparent fine particles. As the fine particles contained in the formation of the above-mentioned surface fine concavo-convex structure, for example, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, cadmium oxide, etc. having an average particle diameter of 0.5-50 μm can be used. Transparent particles such as inorganic particles such as antimony oxide and organic particles including crosslinked or uncrosslinked polymers and the like that have conductivity. In the case of forming the surface fine concavo-convex structure, the amount of particles used is usually about 2-50 parts by weight, preferably 5-25 parts by weight relative to 100 parts by weight of the transparent resin to form the surface fine concavo-convex structure. The anti-glare layer may also function as a diffusion layer (a viewing angle expansion function, etc.) that diffuses the light transmitted by the polarizing plate to expand the viewing angle.

另外，上述防反射層、防黏連層、拡散層、防眩層等除了可以設於透明保護薄膜本身以外，也可以以另外 的光學層的方式作為與透明保護薄膜不同的層來設置。 In addition, the above-mentioned anti-reflection layer, anti-adhesion layer, diffusion layer, anti-glare layer, etc. can be provided in addition to the transparent protective film itself, or other The optical layer is set as a layer different from the transparent protective film.

(黏接劑層) (Adhesive layer)

上述偏光件與透明保護薄膜的貼合中使用的黏接劑層只要在光學性上透明，則並無特別限制，可以使用水系、溶劑系、熱熔系、自由基固化型的各種形態的黏接劑，但較佳為水系黏接劑或自由基固化型黏接劑。 The adhesive layer used for bonding the above-mentioned polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various forms of adhesives such as water-based, solvent-based, hot-melt-based, and radical-curing types can be used. Adhesives, but preferably water-based adhesives or radical curing adhesives.

作為形成黏接劑層的水系黏接劑，並無特別限定，例如可例示乙烯基聚合物系、明膠系、乙烯基系膠乳系、聚胺酯系、異氰酸酯系、聚酯系、環氧系等。 The water-based adhesive forming the adhesive layer is not particularly limited, and examples thereof include vinyl polymer systems, gelatin systems, vinyl latex systems, polyurethane systems, isocyanate systems, polyester systems, and epoxy systems.

作為自由基固化型黏接劑，可例示電子射線固化型、紫外線固化型等活性能量射線固化型、熱固化型等的各種黏接劑，較佳能夠在短時間內固化的活性能量射線固化型。特佳為電子射線固化型。可以使用電子射線固化型黏接劑。藉由在為了使偏光件與透明保護薄膜貼合而使用的黏接劑的固化方法中採用電子射線(即乾式積層)，可以像紫外線固化法不需要加熱步驟，使生產率非常高。 As the radical curing adhesive, various adhesives such as electron beam curing type and ultraviolet curing type, active energy ray curing type, heat curing type, etc. can be exemplified, and active energy ray curing type that can be cured in a short time is preferred. . Particularly preferred is an electron beam curing type. An electron beam curing adhesive can be used. By using electron beams (ie, dry lamination) in the curing method of the adhesive used for bonding the polarizer and the transparent protective film, it is possible to eliminate the need for a heating step like the ultraviolet curing method, resulting in very high productivity.

另外，具有(甲基)丙烯醯基的化合物、尤其是具有芳香環及羥基的單官能的(甲基)丙烯酸酯、含氮(甲基)丙烯酸酯、含羧基(甲基)丙烯酸酯適合作為電子射線固化型黏接劑，藉由使用該黏接劑，可以得到對偏光件及透明保護薄膜具有良好黏接性的偏光板。例如，在使用低水分率的偏光件的情況、以及使用透濕度低的材料作為透明保護薄膜的情況下，本實施方式的黏接劑對其等顯示良好的黏接性，結果可以得到尺寸穩定性良好的偏光板。 In addition, compounds having (meth)acrylic groups, especially monofunctional (meth)acrylates having aromatic rings and hydroxyl groups, nitrogen-containing (meth)acrylates, and carboxyl-containing (meth)acrylates are suitable as Electron beam curing adhesive, by using the adhesive, a polarizing plate with good adhesion to polarizers and transparent protective films can be obtained. For example, in the case of using a polarizer with a low moisture content and in the case of using a material with low moisture permeability as a transparent protective film, the adhesive of this embodiment shows good adhesion to it, and as a result, dimensional stability can be obtained. Polarizing plate with good performance.

另外，可以使上述黏接劑中含有金屬化合物填料。利用金屬化合物填料，可以控制黏接劑層的流動性，使膜厚穩定化，從而得到具有良好外觀、面內均勻且無黏接性偏差的偏光板。 In addition, a metal compound filler may be contained in the above-mentioned adhesive. Using metal compound fillers, the fluidity of the adhesive layer can be controlled, the film thickness can be stabilized, and a polarizing plate with good appearance, uniform in-plane and no adhesion deviation can be obtained.

上述偏光板可以藉由在偏光件的兩面隔著黏接劑層貼合透明保護薄膜而得到，在黏接劑層與透明保護薄膜或偏光件之間可以設置底塗層或易黏接處理層等。作為易黏接處理，可列舉：等離子體處理、電暈處理等乾式處理；鹼處理(皂化處理)等化學處理；形成易黏接劑層的塗布處理等。其中，較佳形成易黏接劑層的塗布處理、鹼處理。在易黏接劑層的形成中可以使用多元醇樹脂、多羧酸樹脂、聚酯樹脂等各種易黏接材料。另外，易黏接劑層的厚度通常較佳為0.001~10μm左右、更佳為0.001~5μm左右、特佳為0.001~1μm左右。 The above-mentioned polarizing plate can be obtained by laminating a transparent protective film on both sides of the polarizer through an adhesive layer. A primer layer or an easy-adhesion treatment layer can be provided between the adhesive layer and the transparent protective film or the polarizer. Wait. Examples of the easy-adhesion treatment include dry treatments such as plasma treatment and corona treatment; chemical treatments such as alkali treatment (saponification treatment); and coating treatment to form an easy-adhesive layer. Among them, coating treatment and alkali treatment for forming an easy-adhesive layer are preferred. Various easy-adhesive materials such as polyol resins, polycarboxylic acid resins, and polyester resins can be used in the formation of the easy-adhesive agent layer. In addition, the thickness of the adhesive layer is generally preferably about 0.001 to 10 μm, more preferably about 0.001 to 5 μm, particularly preferably about 0.001 to 1 μm.

在上述黏接劑層利用水系黏接劑等來形成的情況下，該黏接劑層的厚度為10~300nm左右。從得到均一的面內厚度及得到充分的黏接力的點來看，黏接劑層的厚度更佳為10~200nm、進一步更佳為20~150nm。 When the adhesive layer is formed using an aqueous adhesive or the like, the thickness of the adhesive layer is about 10 to 300 nm. From the viewpoint of obtaining a uniform in-plane thickness and obtaining sufficient adhesive force, the thickness of the adhesive layer is more preferably 10 to 200 nm, and still more preferably 20 to 150 nm.

作為調整黏接劑層的厚度的方法，並無特別限制，例如可列舉調整黏接劑溶液的固體成分濃度、黏接劑的塗布裝置的方法。作為此種黏接劑層厚度的測定方法，並無特別限制，可較佳使用基於SEM(Scanning Electron Microscopy)、TEM(Transmission Electron Microscopy)的剖面觀察測定。黏接劑的塗布操作並無特別限制，可以採用 輥法、噴霧法、浸漬法等各種手段。 The method of adjusting the thickness of the adhesive layer is not particularly limited. For example, a method of adjusting the solid content concentration of the adhesive solution and the method of applying the adhesive may be mentioned. The method for measuring the thickness of the adhesive layer is not particularly limited, and cross-sectional observation measurement by SEM (Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy) can be preferably used. There are no special restrictions on the coating operation of the adhesive, and it can be used Various methods such as roll method, spray method, dipping method, etc.

塗布水系黏接劑後，將偏光件及透明保護薄膜用輥層壓機等進行貼合。上述黏接劑的塗布可以對透明保護薄膜、偏光件中的任一者進行，也可以對兩者進行。在貼合後，實施乾燥步驟，形成包含塗布乾燥層的黏接劑層。乾燥溫度為5~150℃左右、較佳為30~120℃，乾燥時間為120秒以上、更佳為300秒以上。 After the water-based adhesive is applied, the polarizer and the transparent protective film are laminated with a roll laminator. The application of the above-mentioned adhesive may be applied to either of the transparent protective film and the polarizing material, or may be applied to both. After bonding, a drying step is performed to form an adhesive layer including a coated dry layer. The drying temperature is about 5 to 150°C, preferably 30 to 120°C, and the drying time is 120 seconds or more, more preferably 300 seconds or more.

另一方面，在上述黏接劑層利用固化型黏接劑(電子射線固化型黏接劑)形成的情況下，上述黏接層的厚度較佳為0.1~20μm、更佳為0.2~10μm、進一步更佳為0.3~8μm。在厚度薄的情況下，可能無法得到黏接力自身的凝聚力、無法得到黏接強度。若黏接劑層的厚度超過20μm，則出現成本提高及黏接劑自身的固化收縮的影響，可能對偏光板的光學特性產生不良影響。 On the other hand, when the adhesive layer is formed with a curable adhesive (electron beam curable adhesive), the thickness of the adhesive layer is preferably 0.1 to 20 μm, more preferably 0.2 to 10 μm, It is more preferably 0.3 to 8 μm. In the case of thin thickness, the cohesive force of the adhesive force itself may not be obtained, and the adhesive strength may not be obtained. If the thickness of the adhesive layer exceeds 20 μm, the effects of cost increase and curing shrinkage of the adhesive itself may occur, which may adversely affect the optical properties of the polarizing plate.

在使偏光件與透明保護薄膜貼合後，照射電子射線等，使黏接劑固化。電子射線的照射方向可以從任意的適當方向進行照射。較佳從透明保護薄膜側進行照射。若從偏光件側照射，則偏光件可能會因電子射線而劣化。 After bonding the polarizer and the transparent protective film, electron beams or the like are irradiated to cure the adhesive. The irradiation direction of the electron beam can be irradiated from any appropriate direction. It is preferable to irradiate from the side of the transparent protective film. If irradiated from the side of the polarizer, the polarizer may be degraded by electron beams.

電子射線的照射條件只要是能夠固化上述黏接劑的條件，則可以採用任意的適當條件。例如，電子射線照射的加速電壓較佳為5kV~300kV、更佳為10kV~250kV。在加速電壓不足5kV的情況下，可能會使電子射線無法到達黏接劑而有固化不足之虞，若加速電壓超過300kV，則可能通過試樣的滲透力過強而使電子射線彈回， 而有對透明保護薄膜、偏光件造成損傷之虞。作為照射線量，較佳為5~100kGy、更佳為10~75kGy。在照射線量不足5kGy的情況下，黏接劑變得固化不足，若照射線量超過100kGy，則對透明保護薄膜及偏光件造成損傷，產生機械強度的降低及黃變，無法得到規定的光學特性。 As long as the electron beam irradiation conditions are conditions that can cure the above-mentioned adhesive, any appropriate conditions can be adopted. For example, the acceleration voltage of electron beam irradiation is preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. If the acceleration voltage is less than 5kV, the electron beams may not reach the adhesive and may be insufficiently cured. If the acceleration voltage exceeds 300kV, the penetration force of the sample may be too strong to cause the electron beams to bounce back. And there is a risk of causing damage to the transparent protective film and the polarizer. The amount of irradiation is preferably 5 to 100 kGy, more preferably 10 to 75 kGy. When the irradiation dose is less than 5 kGy, the adhesive becomes insufficiently cured. When the irradiation dose exceeds 100 kGy, the transparent protective film and the polarizer will be damaged, resulting in a decrease in mechanical strength and yellowing, and the prescribed optical properties cannot be obtained.

電子射線照射通常在不活潑氣體中進行照射，若需要，也可以在大氣中或少量導入氧的條件下進行。雖然由透明保護薄膜的材料來決定，但是藉由適當導入氧，在最初電子射線所碰到的透明保護薄膜面反而產生氧阻礙，可以防止對透明保護薄膜的損傷，可以僅對黏接劑有效地照射電子射線。 The electron beam irradiation is usually carried out in an inert gas, and if necessary, it can also be carried out in the atmosphere or under the condition of introducing a small amount of oxygen. Although it is determined by the material of the transparent protective film, by appropriately introducing oxygen, oxygen will be blocked on the surface of the transparent protective film that the electron beam first hits, which can prevent damage to the transparent protective film and can only be effective for adhesives. To irradiate electron beams.

在以連續生產線進行上述製造方法的情況下，生產線速度雖然取決於黏接劑的固化時間，但較佳為1~500m/min、更佳為5~300m/min、進一步更佳為10~100m/min。生產線速度過小時，缺乏生產率，或對透明保護薄膜造成的損傷過大，無法製作出能夠耐受耐久性試驗等的偏光板。生產線速度過大時，有時黏接劑的固化變得不充分、無法得到目的黏接性。 In the case of performing the above manufacturing method on a continuous production line, although the production line speed depends on the curing time of the adhesive, it is preferably 1~500m/min, more preferably 5~300m/min, and still more preferably 10~100m /min. The production line speed is too low, lack of productivity, or the damage caused to the transparent protective film is too large, and it is impossible to produce a polarizing plate that can withstand durability tests, etc. When the line speed is too high, the curing of the adhesive may become insufficient, and the desired adhesiveness may not be obtained.

將偏光板P配置於液晶單元C時，該偏光板P較佳以使第2透明保護薄膜(相位差板)22側成為液晶單元C側的方式配置。因此，在液晶單元C的兩側配置上述偏光板P時，較佳兩側的偏光板都以使第2透明保護薄膜(相位差板)22側成為液晶單元C側的方式配置。圖1中示出如此配置的情況。 When the polarizing plate P is arranged on the liquid crystal cell C, the polarizing plate P is preferably arranged so that the second transparent protective film (phase difference plate) 22 side becomes the liquid crystal cell C side. Therefore, when the above-mentioned polarizing plates P are arranged on both sides of the liquid crystal cell C, it is preferable that the polarizing plates on both sides are arranged so that the second transparent protective film (phase difference plate) 22 side becomes the liquid crystal cell C side. This configuration is shown in FIG. 1.

<偏光板的其他實施方式> <Other embodiments of polarizing plate>

本實施方式的偏光板在實際使用時也可以以與其他光學層積層而成的光學薄膜的形式使用。該光學層沒有特別限定，例如可以使用1層或2層以上的反射板、半透射板、相位差板(包括1/2、1/4等波長板)、視角補償薄膜等形成液晶顯示裝置等時使用的光學層。特佳為在本實施方式的偏光板上進一步積層反射板或半透射反射板而成的反射型偏光板或半透射型偏光板、在偏光板上進一步積層相位差板而成的橢圓偏光板或圓偏光板、在偏光板上進一步積層視角補償薄膜而成的廣視角偏光板、或者在偏光板上進一步積層增亮薄膜而成的偏光板。 The polarizing plate of this embodiment can also be used in the form of an optical film laminated with other optical layers in actual use. The optical layer is not particularly limited. For example, one layer or two or more layers of reflective plates, semi-transmissive plates, retardation plates (including 1/2, 1/4 wavelength plates), viewing angle compensation films, etc. can be used to form liquid crystal display devices, etc. When using the optical layer. Particularly preferred is a reflective polarizer or a semi-transmissive polarizer formed by further laminating a reflective plate or a semi-transmissive reflector on the polarizing plate of the present embodiment, an elliptical polarizer formed by further laminating a phase difference plate on a polarizer, or Circular polarizing plate, wide viewing angle polarizing plate formed by further laminating viewing angle compensation film on polarizing plate, or polarizing plate formed by further laminating brightness enhancement film on polarizing plate.

反射型偏光板為在偏光板上設有反射層的偏光板，其用於形成使來自觀察側(顯示側)的入射光反射而進行顯示的類型的液晶顯示裝置等，可以省略內含的背光等光源，具有容易實現液晶顯示裝置的薄型化等優點。反射型偏光板的形成可以藉由根據需要隔著透明保護層等在偏光板的單面附設包含金屬等的反射層的方式等適當方式來進行。 The reflective polarizing plate is a polarizing plate provided with a reflective layer on the polarizing plate. It is used to form a liquid crystal display device that reflects incident light from the observation side (display side) to perform display. The built-in backlight can be omitted. It has advantages such as easy realization of thinning of the liquid crystal display device and other advantages. The formation of the reflective polarizer can be performed by an appropriate method such as a method in which a reflective layer including metal or the like is attached to one side of the polarizer via a transparent protective layer or the like as needed.

(黏合層) (Adhesive layer)

在上述的偏光板、具備至少1層偏光板的光學薄膜(以下，只要無特別說明，將偏光板及光學薄膜合稱為“偏光板”。)中也可以設置用於與液晶單元等其他構件黏接的黏合層。形成黏合層的黏合劑並無特別限制，可以適當選擇使用例如丙烯酸系聚合物、矽酮系聚合物、聚酯、聚胺酯、聚醯胺、聚醚、氟系或橡膠系等的聚合物作為基底聚合物的黏合劑。尤其可較佳使用像丙烯酸系黏合劑光學透明性 優異、顯示適度的潤濕性、凝聚性及黏接性的黏合特性且耐候性、耐熱性等優異的黏合劑。 The above-mentioned polarizing plate and the optical film provided with at least one layer of polarizing plate (hereinafter, unless otherwise specified, the polarizing plate and the optical film are collectively referred to as "polarizing plate".) can also be provided with other members such as liquid crystal cells Adhesive bonding layer. The adhesive forming the adhesive layer is not particularly limited. For example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine-based or rubber-based polymers can be appropriately selected and used as the base. Polymer binder. In particular, it can be better to use optical transparency like acrylic adhesive An excellent adhesive that exhibits moderate wettability, cohesiveness, and adhesive properties, as well as excellent weather resistance and heat resistance.

另外，除上述以外，從防止因吸濕所致的發泡現象、剝離現象，防止因熱膨脹差等所致的光學特性的降低及液晶單元的翹曲，以及高品質且耐久性優異的液晶顯示裝置的形成性等的點來看，較佳吸濕率低且耐熱性優異的黏合層。 In addition, in addition to the above, it prevents foaming and peeling caused by moisture absorption, and prevents degradation of optical properties and warpage of liquid crystal cells due to thermal expansion differences, as well as high-quality and excellent durability liquid crystal displays In terms of device formability, etc., an adhesive layer having a low moisture absorption rate and excellent heat resistance is preferred.

上述黏合層可以具有導電性。藉由對黏合層賦予導電性，可以提高防靜電性，以此為目的也可適合添加防靜電劑。作為防靜電劑，可列舉離子性表面活性劑系、聚苯胺、聚噻吩、聚吡咯、聚喹喔啉等導電性聚合物系、氧化錫、氧化銻、氧化銦等金屬氧化物系等，尤其從光學特性、外觀、防帶電效果以及防帶電效果在加熱、加濕時的穩定性的觀點出發，較佳使用導電性聚合物系。其中，特佳為使用聚苯胺、聚噻吩等水溶性導電性聚合物、或水分散性導電性聚合物。在使用水溶性導電性聚合物或水分散性導電性聚合物作為防靜電層的形成材料的情況下，可以抑制在塗敷時由有機溶劑所致的偏光板的改性。 The adhesive layer may have conductivity. By imparting conductivity to the adhesive layer, antistatic properties can be improved, and an antistatic agent can also be suitably added for this purpose. Examples of the antistatic agent include ionic surfactants, conductive polymer systems such as polyaniline, polythiophene, polypyrrole, and polyquinoxaline, and metal oxide systems such as tin oxide, antimony oxide, and indium oxide. In particular, From the viewpoint of optical properties, appearance, antistatic effect, and stability of the antistatic effect during heating and humidification, a conductive polymer system is preferably used. Among them, it is particularly preferable to use water-soluble conductive polymers such as polyaniline and polythiophene, or water-dispersible conductive polymers. When a water-soluble conductive polymer or a water-dispersible conductive polymer is used as the material for forming the antistatic layer, modification of the polarizing plate due to an organic solvent during coating can be suppressed.

黏合層可以含有例如：天然物、合成物的樹脂類，尤其增黏樹脂；包含玻璃纖維、玻璃珠、金屬粉、其他無機粉末等的填充劑；顏料、著色劑、抗氧化劑等添加於黏合層的添加劑。另外，也可以為含有微粒而顯示光擴散性的黏合層等。 The adhesive layer may contain, for example, natural and synthetic resins, especially tackifying resins; fillers including glass fibers, glass beads, metal powder, other inorganic powders, etc.; pigments, colorants, antioxidants, etc. added to the adhesive layer Of additives. In addition, it may be an adhesive layer that contains fine particles and exhibits light diffusibility, or the like.

黏合層對偏光板的單面或兩面的附設可以以適 宜的方式來進行。作為其例子，可列舉例如：製備使基底聚合物或其組合物溶解或分散於由甲苯、乙酸乙酯等適宜的溶劑的單獨物或混合物形成的溶劑而得的10~40重量%左右的黏合劑溶液，並將其以流延方式或塗敷方式等適宜的展開方式直接附設於偏光板上的方式；或者基於上述而在隔片上形成黏合層而將其轉移至偏光板上的方式等。 The adhesive layer can be attached to one side or both sides of the polarizer. In an appropriate way. Examples thereof include, for example, preparation of a 10-40% by weight bond obtained by dissolving or dispersing the base polymer or its composition in a solvent formed of a suitable solvent such as toluene and ethyl acetate or a mixture thereof. A method of directly attaching it to the polarizing plate in a suitable spreading method such as a casting method or a coating method; or a method of forming an adhesive layer on the separator and transferring it to the polarizing plate based on the above.

黏合層也可以以不同組成或種類等的層的重疊層的形式設置於偏光板的單面或兩面。另外，在設置於兩面時，也可以設為在偏光板的正反為不同組成、種類、厚度等的黏合層。黏合層的厚度可以根據使用目的、黏接力等來適宜確定，通常為1~40μm、較佳為5~30μm、特佳為10~25μm。若黏合層的厚度薄於1μm，則耐久性變差，另外，若黏合層的厚度厚於40μm，則容易產生由發泡等所致的浮起或剝離，使外觀不良。 The adhesive layer may be provided on one side or both sides of the polarizing plate in the form of a superposed layer of layers of different compositions or types. In addition, when it is installed on both sides, it may be an adhesive layer having different compositions, types, thicknesses, etc. on the front and back of the polarizing plate. The thickness of the adhesive layer can be appropriately determined according to the purpose of use, adhesion, etc., and is usually 1-40 μm, preferably 5-30 μm, particularly preferably 10-25 μm. If the thickness of the adhesive layer is thinner than 1 μm, the durability will deteriorate, and if the thickness of the adhesive layer is thicker than 40 μm, floating or peeling due to foaming or the like is likely to occur, resulting in poor appearance.

對於黏合層的露出面，在直至供與實際使用前的期間，出於防止其污染等目的而暫時黏貼隔片來進行覆蓋。由此，可以防止在常規的操作狀態下與黏合層接觸的情形。作為隔片，除上述厚度條件以外，可以使用例如將塑膠薄膜、橡膠片、紙、布、無紡布、網、發泡片、金屬箔、其等的積層體等適宜的薄片體根據需要用矽酮系、長鏈烷基系、氟系、硫化鉬等適宜的剝離劑進行塗布處理而成的隔片等基於以往的適宜的隔片。 The exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing its contamination, etc., until it is used for actual use. As a result, it is possible to prevent contact with the adhesive layer under normal operating conditions. As the separator, in addition to the above-mentioned thickness conditions, for example, plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets, metal foils, laminates such as plastic films, rubber sheets, paper, cloth, metal foil, etc. can be used as needed. A separator obtained by coating a suitable release agent such as a silicone-based, a long-chain alkyl-based, a fluorine-based, and molybdenum sulfide, etc., is based on a conventional suitable separator.

(錨固層) (Anchor layer)

為了提高偏光板與黏合劑層之間的密合性，也可以在 其層間設置錨固層。 In order to improve the adhesion between the polarizing plate and the adhesive layer, you can also An anchor layer is set between the layers.

作為上述錨固層的形成材料，較佳使用選自聚胺酯、聚酯、分子中包含胺基的聚合物類中的錨固劑，特佳為分子中包含胺基的聚合物類。就分子中包含胺基的聚合物類而言，由於分子中的胺基與黏合劑中的羧基等顯示出反應或離子性相互作用等相互作用，因此可以確保良好的密合性。 As the material for forming the anchor layer, it is preferable to use an anchoring agent selected from polyurethanes, polyesters, and polymers containing an amine group in the molecule, and particularly preferably polymers containing an amine group in the molecule. In the case of polymers containing an amine group in the molecule, the amine group in the molecule and the carboxyl group in the binder exhibit a reaction or an ionic interaction, etc., so that good adhesion can be ensured.

作為分子中包含胺基的聚合物類，例如可列舉聚亞乙基亞胺、聚烯丙基胺、聚乙烯基胺、聚乙烯基吡啶、聚乙烯基吡咯烷、丙烯酸二甲基胺基乙酯等含胺基單體的聚合物等。 Examples of polymers containing amine groups in the molecule include polyethyleneimine, polyallylamine, polyvinylamine, polyvinylpyridine, polyvinylpyrrolidine, and dimethylaminoethyl acrylate. Amino group-containing monomer polymers such as esters, etc.

上述錨固層可以具有導電性。藉由對錨固層賦予導電性，可以提高防靜電性，以此為目的也可以適當添加防靜電劑。作為防靜電劑，可以適當使用上述的能包含於黏合層中的防靜電劑。 The anchor layer described above may have conductivity. By imparting conductivity to the anchor layer, antistatic properties can be improved, and an antistatic agent may be appropriately added for this purpose. As the antistatic agent, the above-mentioned antistatic agent that can be contained in the adhesive layer can be suitably used.

另外，本實施方式中，錨固層可以為藉由以用於第1透明保護薄膜的紫外線吸收劑進行處理的方式等方式帶來紫外線吸收能力的錨固層等。 In addition, in the present embodiment, the anchor layer may be an anchor layer that imparts ultraviolet absorbing ability by a method such as treatment with an ultraviolet absorber used for the first transparent protective film.

<偏光板套组> <Polarizing Plate Set>

作為本發明的一實施方式，也可以適當採用將上述偏光板設置為2片1組的偏光板套組。該套組在裝入液晶顯示裝置時，以一偏光板的偏光件的偏光軸與另一偏光件的偏光軸正交的方式構成。例如，偏光板的俯視形狀為矩形時，可舉出一偏光板的偏光件的偏光軸與矩形的長邊方向平 行、另一偏光板的偏光件的偏光軸與矩形的短邊方向平行的構成等。當然不限於此，偏光軸的配置可以為上下相反，偏光軸也可以不與矩形的長邊方向或短邊方向平行。 As an embodiment of the present invention, a polarizing plate set in which the above-mentioned polarizing plates are provided as two pieces in one group can also be suitably used. When the set is installed in the liquid crystal display device, the polarization axis of the polarizer of one polarizer and the polarization axis of the other polarizer are orthogonal to each other. For example, when the planar shape of the polarizing plate is rectangular, it can be mentioned that the polarization axis of the polarizing member of the polarizing plate is flat with the long side direction of the rectangle. A configuration in which the polarization axis of the polarizer of the other polarizer is parallel to the short side direction of the rectangle, etc. Of course, it is not limited to this, and the arrangement of the polarization axis may be up and down, and the polarization axis may not be parallel to the long side direction or the short side direction of the rectangle.

實施例 Example

以下，對具體示出本發明的構成及效果的實施例等進行說明，但是本發明並不受此等實施例的限定。另外，各例中，只要無特別說明，份及%為重量基準。 Hereinafter, examples and the like which specifically show the configuration and effects of the present invention will be described, but the present invention is not limited to these examples. In addition, in each example, unless otherwise specified, parts and% are based on weight.

(醯亞胺化率的計算) (Calculation of imidization rate)

使用¹H-NMR BRUKER AvanceIII(400MHz)，進行樹脂的¹H-NMR測定。由3.5~3.8ppm附近的來自甲基丙烯酸甲酯的O-CH₃質子的峰面積A及3.0~3.3ppm附近的來自戊二醯亞胺的N-CH₃質子的峰的面積B按照下式求得。 ¹ H-NMR BRUKER Avance III (400 MHz) was used to perform ¹ H-NMR measurement of the resin. _{From the peak area A of the O-CH 3} proton derived from methyl methacrylate near 3.5 to 3.8 ppm and the peak area B _{of the N-CH 3} proton derived from glutarimide near 3.0 to 3.3 ppm, the following formula Find.

Im%={B/(A+B)}×100此外，“醯亞胺化率”是指全部羰基中醯亞胺羰基所占的比例。 Im%={B/(A+B)}×100 In addition, the "imination rate" refers to the proportion of the amide carbonyl group in all carbonyl groups.

(酸值) (Acid value)

酸值表示醯亞胺樹脂中的羧酸單元、羧酸酐單元的含量。將0.3g的聚合物試樣在37.5ml的二氯甲烷及37.5ml的甲醇的混合溶劑中溶解，滴加2滴酚酞乙醇溶液後，加入5ml 0.1N的氫氧化鈉水溶液。用0.1N鹽酸滴定過量的鹼，以與直至達到與所添加的鹼中和為止所使用的鹽酸之間的以毫當量所示的差值計算酸值。 The acid value represents the content of the carboxylic acid unit and the carboxylic anhydride unit in the imine resin. 0.3 g of the polymer sample was dissolved in a mixed solvent of 37.5 ml of dichloromethane and 37.5 ml of methanol, 2 drops of phenolphthalein ethanol solution were added dropwise, and 5 ml of 0.1N sodium hydroxide aqueous solution was added. The excess alkali was titrated with 0.1N hydrochloric acid, and the acid value was calculated as the difference in milliequivalents between the hydrochloric acid used until neutralization with the added alkali was reached.

(偏光件的製作) (Making of polarizing parts)

將平均聚合度2400、皂化度99.9莫耳%、厚度75μm的聚乙烯醇薄膜在28℃的溫水中浸漬60秒，使其溶脹。接著， 邊在3.2重量%(重量比：碘/碘化鉀=1/10)的30℃的碘溶液中染色1分鐘，邊拉伸至3.3倍。接著，邊在60℃的3重量%的硼酸、2重量%的碘化鉀水溶液中浸漬10秒邊拉伸至3.6倍。之後，邊在60℃的4重量%的硼酸、3重量%的碘化鉀水溶液中浸漬0.5分鐘邊拉伸至總拉伸倍率為6倍。進而，在5重量%的碘化鉀水溶液中浸漬10秒，進行碘離子浸滲處理。之後，用40℃的烘箱進行3分鐘乾燥，得到厚度30μm的偏光件。 A polyvinyl alcohol film with an average degree of polymerization of 2400, a degree of saponification of 99.9 mol%, and a thickness of 75 μm was immersed in warm water at 28° C. for 60 seconds to swell. then, Stretching to 3.3 times while dyeing in a 30°C iodine solution of 3.2% by weight (weight ratio: iodine/potassium iodide = 1/10) for 1 minute. Next, it was stretched to 3.6 times while being immersed in an aqueous solution of 3% by weight of boric acid and 2% by weight of potassium iodide at 60°C for 10 seconds. After that, it was stretched to a total stretch ratio of 6 times while being immersed in a 4 wt% boric acid and 3 wt% potassium iodide aqueous solution at 60°C for 0.5 minutes. Furthermore, it was immersed in a 5 wt% potassium iodide aqueous solution for 10 seconds to perform an iodine ion impregnation treatment. After that, it was dried in an oven at 40° C. for 3 minutes to obtain a polarizer with a thickness of 30 μm.

(透明保護薄膜的製作) (Production of transparent protective film)

透明保護薄膜A(含有戊二醯亞胺單元)：將MS樹脂(MS-200；甲基丙烯酸甲酯/苯乙烯(莫耳比)=80/20的共聚物，新日鐵化學(株)製)用單甲胺進行醯亞胺化(醯亞胺化率：5%)。所得的醯亞胺化的MS樹脂具有通式(1)所示的戊二醯亞胺單元(式中，R¹及R³為甲基、R²為氫原子)、通式(2)所示的(甲基)丙烯酸酯單元(R⁴為氫原子、R⁵及R⁶為甲基)及苯乙烯單元。另外，在上述醯亞胺化中使用口徑15mm的咬合型同向旋轉式雙螺桿擠出機。擠出機的各溫調區的設定溫度為230℃、螺桿轉速為150rpm，以2.0kg/hr供給MS樹脂，單甲胺的供給量相對於MS樹脂100重量份為2重量份。從料斗投入MS樹脂，利用捏合塊使樹脂熔融、充滿後，從噴嘴注入單甲胺。在反應區的末端裝入密封環，充滿樹脂。將排氣口的壓力減壓至-0.08Mpa來脫揮反應後的副產物及過量的甲胺。從設置於擠出機出口的模頭以線料形式出來的樹脂在水槽中冷卻後，用造粒機將其顆粒化。將上述醯 亞胺化的MS樹脂進行熔融擠出製膜。此時，相對於MS樹脂100重量份供給0.66重量份的紫外線吸收劑(ADEKA公司製、“T-712”)。接著，製作雙軸拉伸至縱2倍、橫2倍的透明保護薄膜(厚度40μm，Re=2nm，Rth=2nm)。 Transparent protective film A (containing glutarimide unit): MS resin (MS-200; methyl methacrylate/styrene (mole ratio) = 80/20 copolymer, Nippon Steel Chemical Co., Ltd.) (Preparation) Use monomethylamine for imidization (imidization rate: 5%). The resulting imidized MS resin has a glutarimide unit represented by the general formula (1) (wherein R ¹ and R ³ are methyl groups, and R ² is a hydrogen atom), which is represented by the general formula (2) The shown (meth)acrylate unit (R ⁴ is a hydrogen atom, R ⁵ and R ⁶ are methyl) and a styrene unit. In addition, an interlocking co-rotating twin-screw extruder with a diameter of 15 mm was used for the above-mentioned imidization. The set temperature of each temperature adjustment zone of the extruder was 230° C., the screw rotation speed was 150 rpm, and the MS resin was supplied at 2.0 kg/hr. The supply amount of monomethylamine was 2 parts by weight with respect to 100 parts by weight of the MS resin. The MS resin is poured from the hopper, and the resin is melted and filled with a kneading block, and then monomethylamine is injected from the nozzle. A seal ring is installed at the end of the reaction zone and filled with resin. Reduce the pressure of the exhaust port to -0.08Mpa to devolatilize the by-products and excess methylamine after the reaction. The resin in the form of strands from the die set at the exit of the extruder is cooled in a water tank and then pelletized by a pelletizer. The above-mentioned imidized MS resin was melt-extrusioned to form a film. At this time, 0.66 parts by weight of an ultraviolet absorber (manufactured by ADEKA Corporation, "T-712") was supplied with respect to 100 parts by weight of MS resin. Next, a transparent protective film (thickness 40 μm, Re=2nm, Rth=2nm) biaxially stretched to twice the length and twice the width was produced.

透明保護薄膜B(含有戊二醯亞胺單元)：調整反應時間及溫度，使醯亞胺化率為2.5%，除此以外，按照與透明保護薄膜A同樣的步驟來製作。 Transparent protective film B (containing glutarimide unit): The reaction time and temperature were adjusted so that the imidization rate was 2.5%, and other than that, it was produced in the same procedure as the transparent protective film A.

透明保護薄膜C(含有戊二醯亞胺單元)：調整反應時間及溫度，使醯亞胺化率為10%，除此以外，按照與透明保護薄膜A同樣的步驟來製作。 Transparent protective film C (containing glutarimide unit): The reaction time and temperature were adjusted so that the imidization rate was 10%, and the transparent protective film A was produced according to the same procedure except that.

透明保護薄膜D(含有戊二醯亞胺單元)：調整反應時間及溫度，使酸值為0.1mmol/g，除此以外，按照與透明保護薄膜A同樣的步驟來製作。 Transparent protective film D (contains glutarimide unit): The reaction time and temperature were adjusted so that the acid value was 0.1 mmol/g, except that the transparent protective film A was produced according to the same procedure.

透明保護薄膜E(含有戊二醯亞胺單元)：未配合紫外線吸收劑，除此以外，與透明保護薄膜D同樣地來製作。 Transparent protective film E (containing glutarimide unit): It was produced in the same manner as the transparent protective film D except that no ultraviolet absorber was blended.

透明保護薄膜F：使用厚度60μm且含有紫外線吸收劑的三乙醯纖維素薄膜(富士膠片(株)製，“TD60UL”，Re=10nm，Rth=50nm，透濕度600g/m²．24hr)。 Transparent protective film F: A triacetyl cellulose film (manufactured by Fuji Photo Film Co., Ltd., "TD60UL", Re=10nm, Rth=50nm, and moisture permeability of 600g/m ² .24hr) with a thickness of 60 μm and containing an ultraviolet absorber was used.

透明保護薄膜G：使用厚度80μm且含有紫外線吸收劑的聚對苯二甲酸乙二醇酯(PET)薄膜(東洋紡公司製，“TA010”，Re=8400nm，Rth=11500nm，透濕度10g/m²．24hr)。 Transparent protective film G: Use a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., "TA010", Re=8400nm, Rth=11500nm, and moisture permeability 10g/m ^{2) with a thickness of 80 μm and containing ultraviolet absorbers.} .24hr).

透明保護薄膜H(含有戊二酸酐單元)：使將甲基丙烯酸甲酯20重量份與丙烯醯胺80重量份共聚而得的共聚 物進一步與甲基丙烯酸27重量份及甲基丙烯酸甲酯73重量份反應，得到共聚物(a)，之後，對該共聚物(a)加熱，由此進行分子內環化反應，將戊二酸酐單元導入共聚物中。以該共聚物的全部單元作為基準，不飽和羧酸烷基酯單體單元：戊二酸酐單體單元：不飽和羧酸單體單元的比例為71：28：1(莫耳比)。作為所得的結構單元，上述通式(2)中，R¹及R²為甲基，下述通式(3)中，R⁶及R⁷為甲基。另外，不飽和羧酸單體單元為來自甲基丙烯酸的結構單元。重量平均分子量為13萬。 Transparent protective film H (containing glutaric anhydride unit): The copolymer obtained by copolymerizing 20 parts by weight of methyl methacrylate and 80 parts by weight of acrylamide is further combined with 27 parts by weight of methacrylic acid and 73 parts by weight of methyl methacrylate. Parts by weight are reacted to obtain a copolymer (a), and then the copolymer (a) is heated to proceed an intramolecular cyclization reaction to introduce glutaric anhydride units into the copolymer. Based on all units of the copolymer, the ratio of unsaturated carboxylic acid alkyl ester monomer unit: glutaric anhydride monomer unit: unsaturated carboxylic acid monomer unit is 71:28:1 (molar ratio). As the resultant structural unit, in the above general formula (2), R ¹ and R ² are methyl groups, and in the following general formula (3), R ⁶ and R ⁷ are methyl groups. In addition, the unsaturated carboxylic acid monomer unit is a structural unit derived from methacrylic acid. The weight average molecular weight is 130,000.

在具備攪拌機的300ml可拆分燒瓶中加入所得的共聚物(a)50g、2-丁酮150g，用雙螺旋帶攪拌葉片攪拌24小時。將所得的溶液用截止值為1μm的玻璃濾器過濾，得到丙烯酸系樹脂溶液。取丙烯酸系樹脂溶液的一部分置於固定有聚對苯二甲酸乙二醇酯薄膜(厚度100μm)的玻璃板上，使用棒塗機形成均一的膜，接著，在50℃加熱10分鐘，得到丙烯酸系樹脂薄膜。將所得的丙烯酸系樹脂薄膜從聚對苯二甲酸乙二醇酯薄膜剝離，在100℃加熱10分鐘，在120℃加熱20分鐘，在140℃加熱20分鐘，再在170℃加熱40分鐘，得到透明保護薄膜F(厚度40μm，Re=0nm，Rth= 0nm)。 In a 300 ml separable flask equipped with a stirrer, 50 g of the obtained copolymer (a) and 150 g of 2-butanone were added, and the mixture was stirred for 24 hours with a double-spiral stirring blade. The obtained solution was filtered with a glass filter with a cut-off value of 1 μm to obtain an acrylic resin solution. A part of the acrylic resin solution was placed on a glass plate fixed with a polyethylene terephthalate film (thickness 100μm), and a bar coater was used to form a uniform film, and then heated at 50°C for 10 minutes to obtain acrylic Department of resin film. The obtained acrylic resin film was peeled from the polyethylene terephthalate film, heated at 100°C for 10 minutes, 120°C for 20 minutes, 140°C for 20 minutes, and 170°C for 40 minutes to obtain Transparent protective film F (thickness 40μm, Re=0nm, Rth= 0nm).

透明保護薄膜I：使用三乙醯纖維素薄膜(富士膠片公司製，WVBZ4A6)的滿足nx>ny>nz關係的二軸性相位差薄膜(厚度60μm，Re=55nm，Rth=125nm)。 Transparent protective film I: A biaxial retardation film (thickness 60 μm, Re=55nm, Rth=125nm) that satisfies the relationship nx>ny>nz using a triacetyl cellulose film (manufactured by Fujifilm Corporation, WVBZ4A6).

透明保護薄膜J：使用三乙醯纖維素薄膜(柯尼卡公司製，KC4DR-1)的滿足nx>ny>nz的關係的二軸性相位差薄膜(厚度40μm，Re=52nm，Rth=125nm)。 Transparent protective film J: A biaxial retardation film (thickness 40μm, Re=52nm, Rth=125nm that satisfies the relationship nx>ny>nz using a triacetyl cellulose film (manufactured by Konica Corporation, KC4DR-1) ).

(黏接劑的製備) (Preparation of adhesive)

黏接劑A(水系)：相對於含有乙醯乙醯基的聚乙烯醇系樹脂(平均聚合度：1200，皂化度：98.5莫耳%，乙醯乙醯化度：5莫耳%)100份，將羥甲基密胺50份在30℃的溫度條件下溶解於純水中，製備固體成分濃度調整為3.7%的水溶液。相對於上述水溶液100份，添加氧化鋁膠體水溶液(平均粒徑15nm，固體成分濃度10%，正電荷)18份，製備黏接劑水溶液。黏接劑水溶液的黏度為9.6mPa．s。黏接劑水溶液的pH為4-4.5的範圍。將其作為黏接劑。 Adhesive A (aqueous): Relative to polyvinyl alcohol resin containing acetyl acetyl group (average degree of polymerization: 1200, saponification degree: 98.5 mol%, acetylation degree: 5 mol%) 100 Part, 50 parts of methylol melamine was dissolved in pure water under a temperature condition of 30°C to prepare an aqueous solution whose solid content was adjusted to 3.7%. To 100 parts of the above-mentioned aqueous solution, 18 parts of an alumina colloidal aqueous solution (average particle size 15 nm, solid content concentration 10%, positive charge) was added to prepare an adhesive aqueous solution. The viscosity of the adhesive aqueous solution is 9.6mPa. s. The pH of the adhesive aqueous solution is in the range of 4-4.5. Use it as an adhesive.

<實施例1> <Example 1>

(液晶顯示裝置樣品的製作) (Production of sample of liquid crystal display device)

在上述透明保護薄膜A的單面以使乾燥後的黏接劑層的厚度達到80nm的方式塗布上述黏接劑A，備用。在上述透明保護薄膜H的單面以使乾燥後的黏接劑層的厚度達到80nm的方式塗布上述黏接劑A，備用。另外，在自上述製備起的30分鐘後在23℃的溫度條件下進行黏接劑的塗布。接著，在23℃的溫度條件下，用輥機在偏光件的兩面貼合 上述帶黏接劑的透明保護薄膜A及H後，在55℃乾燥6分鐘，製作設想好觀察側的偏光板。 The adhesive A was applied to one side of the transparent protective film A so that the thickness of the adhesive layer after drying reached 80 nm, and it was ready for use. The adhesive A is applied to one side of the transparent protective film H so that the thickness of the adhesive layer after drying reaches 80 nm, and it is ready for use. In addition, the adhesive was applied under a temperature condition of 23° C. after 30 minutes from the above preparation. Next, under the temperature condition of 23°C, the two sides of the polarizer are bonded with a roller machine After the above-mentioned transparent protective films A and H with adhesives, they were dried at 55°C for 6 minutes to produce a polarizing plate with a good observation side.

以與觀察側的偏光板同樣的步驟製作設想好背光側的偏光板。由此，製作在觀察側及背光燈側同一構成的偏光板。 In the same procedure as the polarizing plate on the observation side, a polarizing plate on the conceivable backlight side is produced. In this way, a polarizing plate having the same configuration on the observation side and the backlight side was produced.

將製作的偏光板以偏光件的偏光軸相對於長邊為45°的方式切成160mm×90mm。在該偏光板的第2透明保護薄膜側(相位差薄膜側)黏貼丙烯酸系黏合劑層。將該帶黏合劑層的偏光板在厚度0.5mm的亞克力玻璃的兩面以使偏光板(偏光件)的偏光軸正交的方式黏貼，將所得的物品模擬性地作為液晶顯示裝置樣品。 The produced polarizing plate was cut into 160 mm×90 mm so that the polarization axis of the polarizer was 45° with respect to the long side. The acrylic adhesive layer was stuck on the second transparent protective film side (retardation film side) of the polarizing plate. The polarizing plate with the adhesive layer was stuck on both sides of acrylic glass with a thickness of 0.5 mm so that the polarization axis of the polarizing plate (polarizer) was orthogonal to each other, and the obtained article was simulated as a liquid crystal display device sample.

<實施例2~5、比較例1~7> <Examples 2 to 5, Comparative Examples 1 to 7>

實施例1中，在製作觀察側及背光側的偏光板時，除了將透明保護薄膜的種類等變為如表1所示以外與實施例1同樣地製作液晶顯示裝置樣品。 In Example 1, when producing polarizing plates on the observation side and the backlight side, a liquid crystal display device sample was produced in the same manner as in Example 1, except that the type of the transparent protective film and the like were changed to those shown in Table 1.

另外，實施例2的偏光板表面的塗布層藉由以下的步驟來形成。準備紫外線固化型胺基甲酸酯丙烯酸酯樹脂(日本合成化學工業(株)製、商品名“UV1700B”、固體成分100%)50重量份、及以季戊四醇三丙烯酸酯為主成分的多官能丙烯酸酯(大阪有機化學工業(株)製、商品名“VISCOAT # 300”、固體成分100%)50重量份。相對於上述樹脂的樹脂固體成分100重量份，混合作為粒子的丙烯酸類樹脂與苯乙烯的共聚粒子(積水化成品工業(株)製、商品名“Techpolymer”、重量平均粒徑：3.0μm、折射率：1.520)2 重量份、作為觸變性賦予劑的有機黏土即合成膨潤石(Co-op Chemical(株)製、商品名“Lucent tight SAN”)1.5重量份、光聚合引發劑(BASF公司製、商品名“Irgacure 907”)3重量份、流平劑(DIC(株)製、商品名“PC4100”、固體成分10%)0.2份。另外，上述有機黏土用甲苯稀釋成固體成分為6.0%後再使用。將該混合物以使固體成分濃度達到40重量%的方式用甲苯/MIBK(甲基異丁基酮)混合溶劑(重量比80/20)稀釋，製備塗敷液。將塗敷液使用逗點塗布機進行塗布，形成塗膜。然後，邊將形成有該塗膜的薄膜以約30°的角度傾斜，邊運送至乾燥步驟。乾燥步驟中，以100℃加熱2分鐘，由此使上述塗膜乾燥。之後，用高壓汞燈照射累積光量為300mJ/cm²的紫外線，將上述塗膜進行固化處理，形成厚度7.5μm的塗布層。 In addition, the coating layer on the surface of the polarizing plate of Example 2 was formed by the following steps. Prepare 50 parts by weight of UV-curable urethane acrylate resin (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., brand name "UV1700B", solid content 100%), and polyfunctional acrylic acid mainly composed of pentaerythritol triacrylate 50 parts by weight of ester (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name "VISCOAT # 300", solid content 100%). With respect to 100 parts by weight of the resin solid content of the above resin, copolymerized particles of acrylic resin and styrene (manufactured by Sekisui Chemical Industry Co., Ltd., trade name "Techpolymer", weight average particle size: 3.0 μm, refraction Rate: 1.520) 2 parts by weight, 1.5 parts by weight of synthetic bentonite (manufactured by Co-op Chemical Co., Ltd., trade name "Lucent tight SAN") as a thixotropy imparting agent, organic clay, and photopolymerization initiator (manufactured by BASF) , Brand name "Irgacure 907") 3 parts by weight, and leveling agent (manufactured by DIC Co., Ltd., brand name "PC4100", solid content 10%) 0.2 part. In addition, the above-mentioned organoclay was diluted with toluene to a solid content of 6.0% before use. This mixture was diluted with a toluene/MIBK (methyl isobutyl ketone) mixed solvent (weight ratio 80/20) so that the solid content concentration became 40% by weight, to prepare a coating liquid. The coating liquid was applied using a comma coater to form a coating film. Then, the thin film on which the coating film was formed was tilted at an angle of about 30°, and was transported to the drying step. In the drying step, heating is performed at 100°C for 2 minutes, thereby drying the above-mentioned coating film. After that, a high-pressure mercury lamp was used to irradiate ^{ultraviolet rays with a cumulative light amount of 300 mJ/cm 2} to cure the coating film to form a coating layer with a thickness of 7.5 μm.

(評價) (Evaluation)

對所得的偏光板進行下述評價。將結果示於表1。 The following evaluation was performed on the obtained polarizing plate. The results are shown in Table 1.

(外觀評價：焦糊) (Appearance evaluation: burnt)

以目視確認所製作的偏光板，確認焦糊(黑斑點狀的外觀不良)的有無。將未產生焦糊的情況評價為“○”，將產生焦糊的情況評價為“×”。 The produced polarizing plate was visually confirmed, and the presence or absence of burnt (black spot-like appearance defects) was confirmed. The case where scorching did not occur was evaluated as "○", and the case where scorching occurred was evaluated as "x".

(翹曲及顯示不均) (Warpage and uneven display)

對樣品進行加熱試驗(60℃，240小時)、加濕試驗(60℃，90%RH，240小時)。試驗後，按照以下的步驟進行翹曲及顯示不均的評價。 The samples were subjected to heating test (60°C, 240 hours) and humidification test (60°C, 90%RH, 240 hours). After the test, the evaluation of warpage and display unevenness was performed according to the following procedure.

(翹曲) (Warpage)

測定以向下凸起的方式將偏光板載置於平台時的端部的翹曲量，利用以下的基準進行了評價。 The amount of warpage of the end when the polarizing plate was placed on the platform so as to be convex downward was measured, and the following criteria were used for evaluation.

○：3mm以下 ○: Below 3mm

×：超過3mm且為6mm以下 ×: more than 3mm and less than 6mm

××：超过6mm ××: more than 6mm

(顯示不均) (Uneven display)

由SONY公司製BRAVIA 920A以再加工將偏光板剝離而取出液晶單元，在得到的液晶單元的兩面黏貼實施例、比較例的偏光板並再次組裝，將所得到的物品作為液晶顯示裝置樣品來製作。對於顯示不均的評價，確認在黏貼偏光板並組裝時因邊框(bezel)接觸而產生的偏差的有無及起因於偏光板而產生的偏差的有無，按照以下的基準進行。 BRAVIA 920A made by SONY Corporation peeled off the polarizing plate to take out the liquid crystal cell, and pasted the polarizing plates of the examples and comparative examples on both sides of the obtained liquid crystal cell and assembled again. The obtained article was produced as a sample of a liquid crystal display device. . For the evaluation of display unevenness, the presence or absence of the deviation caused by the contact of the bezel when the polarizing plate is attached and assembled and the presence or absence of the deviation caused by the polarizing plate are confirmed according to the following criteria.

○：既沒有邊框接觸偏差也沒有起因於偏光板的偏差 ○: There is neither frame contact deviation nor deviation caused by polarizing plate

×：僅發生邊框接觸偏差或起因於偏光板的偏差的任一者 ×: Either only the frame contact deviation or the deviation caused by the polarizing plate occurs

××：發生邊框接觸偏差及起因於偏光板的偏差的兩者 ××: Both the frame contact deviation and the deviation caused by the polarizing plate occurred

(外觀評價：黃變) (Appearance evaluation: yellowing)

將偏光板切割成1000mm×1000mm，製備樣品。將樣品的偏光板置於依據JIS K 7350-2確定的耐光試驗的環境下，確認此時的偏光板有無黃變。將未發生黃變的情況評價為“○”，將發生黃變的情況評價為“×”。 The polarizing plate is cut into 1000mm×1000mm, and the sample is prepared. The polarizing plate of the sample is placed in an environment of a light resistance test determined in accordance with JIS K 7350-2, and it is confirmed whether the polarizing plate at this time has yellowing. The case where yellowing did not occur was evaluated as "○", and the case where yellowing occurred was evaluated as "×".

1‧‧‧偏光件 1‧‧‧Polarizer

3‧‧‧黏接劑層 3‧‧‧Adhesive layer

21‧‧‧第1透明保護薄膜 21‧‧‧The first transparent protective film

22‧‧‧第2透明保護薄膜 22‧‧‧Second transparent protective film

100‧‧‧液晶顯示裝置 100‧‧‧LCD device

C‧‧‧液晶單元 C‧‧‧LCD unit

P‧‧‧偏光板 P‧‧‧Polarizer

Claims (10)

一種液晶顯示裝置，係具備對向偏光板的液晶顯示裝置，前述偏光板各自具備在聚乙烯醇系偏光件兩面隔著黏接劑層設置的透明保護薄膜，一面的第1透明保護薄膜含有(甲基)丙烯酸系樹脂，且具有紫外線吸收劑，該(甲基)丙烯酸系樹脂具有不飽和羧酸烷基酯單元及通式(1)所示的戊二醯亞胺單元，並且醯亞胺化率為2.5~5.0%、酸值為0.10~0.50mmol/g的範圍，且丙烯酸酯單元不足1重量%，另一面的第2透明保護薄膜為含有纖維素酯而成，且為滿足nx>ny>nz關係的相位差板，其中，將面內折射率達到最大的方向設為X軸，將與X軸垂直的方向設為Y軸，將厚度方向設為Z軸，並且將各軸方向的折射率設為nx、ny、nz，

此處，R¹及R²分別獨立地表示氫或碳數1~8的烷基，R³表示碳數1~18的烷基、碳數3~12的環烷基或者碳 數6~10的芳基。 A liquid crystal display device is a liquid crystal display device provided with opposing polarizing plates, each of the polarizing plates having a transparent protective film provided on both sides of a polyvinyl alcohol-based polarizer via an adhesive layer, and a first transparent protective film on one side contains ( The meth)acrylic resin has an ultraviolet absorber, and the (meth)acrylic resin has an unsaturated carboxylic acid alkyl ester unit and a glutarimide unit represented by the general formula (1), and an imine The conversion rate is 2.5~5.0%, the acid value is in the range of 0.10~0.50mmol/g, and the acrylic acid ester unit is less than 1% by weight. The second transparent protective film on the other side is made of cellulose ester, and satisfies nx>ny>nz phase difference plate, in which the direction in which the in-plane refractive index reaches the maximum is set to the X axis, the direction perpendicular to the X axis is set to the Y axis, the thickness direction is set to the Z axis, and the directions of each axis The refractive index of is set to nx, ny, nz,

Here, R ¹ and R ² each independently represent hydrogen or an alkyl group with 1 to 8 carbons, and R ³ represents an alkyl group with 1 to 18 carbons, a cycloalkyl group with 3 to 12 carbons, or 6 to 10 carbons.的aryl. 如請求項1之液晶顯示裝置，其中前述第1透明保護薄膜的面內相位差及厚度方向相位差分別為40nm以下。 The liquid crystal display device of claim 1, wherein the in-plane phase difference and the thickness direction phase difference of the first transparent protective film are each 40 nm or less. 如請求項1或2之液晶顯示裝置，其具有配置於前述第1透明保護薄膜的一面側的塗布層。 The liquid crystal display device of claim 1 or 2, which has a coating layer disposed on one side of the first transparent protective film. 如請求項3之液晶顯示裝置，其中前述塗布層為硬塗層或防污層。 The liquid crystal display device of claim 3, wherein the aforementioned coating layer is a hard coat layer or an antifouling layer. 如請求項1或2之液晶顯示裝置，其中前述黏接劑層包含水系黏接劑。 The liquid crystal display device of claim 1 or 2, wherein the adhesive layer includes an aqueous adhesive. 如請求項1或2之液晶顯示裝置，其中前述偏光板隔著黏合層貼合於液晶單元，前述黏合層設置於與前述透明保護薄膜之前述偏光件側的相反側。 The liquid crystal display device of claim 1 or 2, wherein the polarizing plate is attached to the liquid crystal cell via an adhesive layer, and the adhesive layer is provided on the side opposite to the polarizer side of the transparent protective film. 如請求項6之液晶顯示裝置，其在前述偏光板與前述黏合層之間設有錨固層。 Such as the liquid crystal display device of claim 6, which is provided with an anchor layer between the polarizing plate and the adhesive layer. 如請求項6之液晶顯示裝置，其中前述黏合層具有導電性。 The liquid crystal display device of claim 6, wherein the adhesive layer has conductivity. 如請求項7之液晶顯示裝置，其中前述錨固層具有導電性。 The liquid crystal display device of claim 7, wherein the anchor layer has conductivity. 一種偏光板套組，係在液晶顯示裝置中經對向配置的偏光板套組，前述偏光板各自具備在聚乙烯醇系偏光件兩面隔著黏接劑層設置的透明保護薄膜，一面的第1透明保護薄膜含有(甲基)丙烯酸系樹脂，且具有紫外線吸收劑，該(甲基)丙烯酸系樹脂具有 不飽和羧酸烷基酯單元及通式(1)所示的戊二醯亞胺單元，並且醯亞胺化率為2.5~5.0%、酸值為0.10~0.50mmol/g的範圍，且丙烯酸酯單元不足1重量%，另一面的第2透明保護薄膜為含有纖維素酯而成，且為滿足nx>ny>nz關係的相位差板，其中，將面內折射率達到最大的方向設為X軸，將與X軸垂直的方向設為Y軸，將厚度方向設為Z軸，並且將各軸方向的折射率設為nx、ny、nz，

此處，R¹及R²分別獨立地表示氫或碳數1~8的烷基，R³表示碳數1~18的烷基、碳數3~12的環烷基或者碳數6~10的芳基。 A polarizing plate set is a set of polarizing plates arranged in opposite directions in a liquid crystal display device. Each of the aforementioned polarizing plates is provided with a transparent protective film on both sides of a polyvinyl alcohol-based polarizer via an adhesive layer. 1 The transparent protective film contains a (meth)acrylic resin and has an ultraviolet absorber. The (meth)acrylic resin has an unsaturated carboxylic acid alkyl ester unit and glutarimide represented by the general formula (1) Unit, and the imidization rate is 2.5~5.0%, the acid value is in the range of 0.10~0.50mmol/g, and the acrylate unit is less than 1% by weight. The second transparent protective film on the other side is made of cellulose ester , And is a phase difference plate that satisfies the relationship nx>ny>nz, in which the direction in which the in-plane refractive index reaches the maximum is set to the X axis, the direction perpendicular to the X axis is set to the Y axis, and the thickness direction is set to the Z axis , And set the refractive index of each axis direction as nx, ny, nz,

Here, R ¹ and R ² each independently represent hydrogen or an alkyl group with 1 to 8 carbons, and R ³ represents an alkyl group with 1 to 18 carbons, a cycloalkyl group with 3 to 12 carbons, or 6 to 10 carbons.的aryl.

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