TWI689755B - Polarizing plate and liquid crystal display device - Google Patents

Abstract

The present invention provides a polarizing plate and a liquid crystal display device having the same. The polarizing plate is a thin polarizing plate in which no protective film exist between an adhesive layer and a polarizer, which has a strong adhesion force between the protective layer formed on the polarizer surface and the adhesive layer, and has enhanced durability under a high-temperature and high humidity environment.

The present invention relates to a polarizing plate including a functional resin layer, a first adhesive layer, a first protective layer which is a cured product of a curable resin composition, and a polarizer laminated in the order set forth.

Description

偏光板及液晶顯示裝置 Polarizing plate and liquid crystal display device

本發明是有關偏光板及具有該偏光板之液晶顯示裝置。 The invention relates to a polarizing plate and a liquid crystal display device having the polarizing plate.

偏光板是適用於作為構成液晶顯示裝置之光學零組件之一者。偏光板通常是在偏光片的兩面，以積層有作為保護薄膜的透明樹脂薄膜之狀態組裝進液晶顯示裝置中而使用。近年來，液晶顯示裝置的薄型化持續進行中，關於被組裝進液晶顯示裝置中之偏光板，亦進一步要求薄型化。因此，有提案只在偏光片的單側積層有保護薄膜之偏光板(專利文獻1)。 The polarizing plate is suitable as one of the optical components constituting the liquid crystal display device. The polarizing plate is usually assembled into a liquid crystal display device in a state in which a transparent resin film as a protective film is laminated on both sides of the polarizer. In recent years, the thinning of liquid crystal display devices has continued, and the polarizing plates incorporated in liquid crystal display devices are also required to be thinner. Therefore, there is a proposal of a polarizing plate in which a protective film is laminated only on one side of the polarizer (Patent Document 1).

又，特別是在液晶顯示裝置中之光源側所配置之偏光板，為了謀求提昇液晶顯示裝置的亮度，隔著黏著劑層而積層反射型偏光薄膜(提昇亮度薄膜)。然後作為此種黏著劑層者，為了抑制在液晶顯示裝置之顯示部中產生的干涉條紋，大多使用擴散黏著劑層。 In addition, in particular, the polarizing plate disposed on the light source side of the liquid crystal display device, in order to improve the brightness of the liquid crystal display device, a reflective polarizing film (brightness enhancing film) is laminated via an adhesive layer. As such an adhesive layer, in order to suppress interference fringes generated in the display portion of the liquid crystal display device, a diffusion adhesive layer is often used.

只在單側積層有保護薄膜之偏光板中，隔著黏著劑層而積層上述提昇亮度薄膜的情形，與黏著劑層 鄰接之面是成為偏光片(專利文獻2)。在如此之層構成的偏光板中，有偏光片與黏著劑層的密著力小之問題。 Only in the case of a polarizing plate with a protective film laminated on one side, in the case where the above-mentioned brightness enhancement film is laminated via an adhesive layer, it is different from the adhesive layer. The adjacent surface becomes a polarizer (Patent Document 2). In the polarizing plate composed of such a layer, there is a problem that the adhesion between the polarizer and the adhesive layer is small.

再者，特別是在作為黏著劑層而使用擴散黏著劑的情形，於濕熱環境下之黏著劑層的耐久性低，在偏光板會有產生浮起或剝離之問題。 Furthermore, especially in the case of using a diffusion adhesive as the adhesive layer, the durability of the adhesive layer under a hot and humid environment is low, and the polarizing plate may have a problem of floating or peeling.

[先前技術文獻] [Prior Technical Literature] (專利文獻) (Patent Literature)

專利文獻1：日本特開平10-186133號公報 Patent Document 1: Japanese Patent Laid-Open No. 10-186133

專利文獻2：日本特開2010-39458號公報 Patent Document 2: Japanese Patent Laid-Open No. 2010-39458

本發明的目的是提供一種偏光板以及具有該偏光板之液晶顯示裝置，該偏光板係在偏光片的單側隔著黏著劑層而積層有如提昇亮度薄膜的機能性樹脂層，且偏光片與黏著劑層的密著力強，在濕熱環境下之耐久性會提昇之偏光板。 An object of the present invention is to provide a polarizing plate and a liquid crystal display device having the polarizing plate. The polarizing plate is formed by laminating a functional resin layer such as a brightness enhancement film with an adhesive layer on one side of the polarizing plate. The adhesive layer has strong adhesion, and the durability of the polarizing plate will be improved in a hot and humid environment.

[1]一種偏光板，其係依序積層有機能性樹脂層、第一黏著劑層、屬於硬化性樹脂組成物的硬化物之第一保護層、及偏光片，其中，硬化性樹脂組成物含有活性能量線硬化性化合物。 [1] A polarizing plate that sequentially laminates an organic resin layer, a first adhesive layer, a first protective layer that is a cured product of a curable resin composition, and a polarizer, wherein the curable resin composition Contains active energy ray hardening compounds.

[2]如[1]中記載的偏光板，其中，硬化性樹脂組成物含有光 擴散劑。 [2] The polarizing plate according to [1], wherein the curable resin composition contains light Diffusion agent.

[3]如[1]中記載的偏光板，其中，第一黏著劑層是擴散黏著劑層。 [3] The polarizing plate as described in [1], wherein the first adhesive layer is a diffusion adhesive layer.

[4]如[1]中記載的偏光板，其中，機能性樹脂層是具有亮度提昇薄膜之層。 [4] The polarizing plate as described in [1], wherein the functional resin layer is a layer having a brightness enhancement film.

[5]如[1]中記載的偏光板，其中，活性能量線硬化性化合物含有在分子內至少具有1個(甲基)丙烯醯氧基之(甲基)丙烯酸系化合物。 [5] The polarizing plate according to [1], wherein the active energy ray-curable compound contains a (meth)acrylic compound having at least one (meth)acryloyloxy group in the molecule.

[6]如[1]中記載的偏光板，其中，活性能量線硬化性化合物含有陽離子聚合性化合物。 [6] The polarizing plate according to [1], wherein the active energy ray-curable compound contains a cationically polymerizable compound.

[7]如[6]中記載的偏光板，其中，陽離子聚合性化合物含有在分子內至少具有1個環氧乙烷(oxirane)環之化合物。 [7] The polarizing plate according to [6], wherein the cationic polymerizable compound contains a compound having at least one oxirane ring in the molecule.

[8]如[1]中記載的偏光板，其中，第一黏著劑層的厚度，係0.1至10μm。 [8] The polarizing plate as described in [1], wherein the thickness of the first adhesive layer is 0.1 to 10 μm.

[9]如[1]中記載的偏光板，其係在偏光片之與積層有第一保護層之側為相反之側，具有第二保護層。 [9] The polarizing plate according to [1], which has a second protective layer on the opposite side of the polarizer from the side where the first protective layer is deposited.

[10]如[9]中記載的偏光板，其中，第二保護層是熱可塑性樹脂薄膜。 [10] The polarizing plate as described in [9], wherein the second protective layer is a thermoplastic resin film.

[11]如[9]中記載的偏光板，其係在第二保護層之與積層有偏光片之側為相反之側具有第二黏著劑層。 [11] The polarizing plate as described in [9], which has a second adhesive layer on the opposite side of the second protective layer from the side where the polarizer is laminated.

[12]如[11]中記載的偏光板，其係在第二黏著劑層之與積層有第二保護層之側為相反側之表面積層有剝離薄膜。 [12] The polarizing plate described in [11], which has a release film on the surface area layer of the second adhesive layer opposite to the side where the second protective layer is deposited.

[13]一種液晶顯示裝置，係具有如[1]至[11]的任何一項中記載的偏光板，與液晶單元。 [13] A liquid crystal display device having the polarizing plate as described in any one of [1] to [11] and a liquid crystal cell.

若依據本發明，可以提供一種偏光板以及具有該偏光板之液晶顯示裝置，該偏光板係在偏光片的單側隔著黏著劑層而積層有機能性樹脂層，且偏光片與黏著劑層的密著力強，濕熱環境下之耐久性經提昇者。 According to the present invention, a polarizing plate and a liquid crystal display device having the polarizing plate can be provided. The polarizing plate is formed by laminating an organic resin layer through an adhesive layer on one side of the polarizer, and the polarizer and the adhesive layer It has strong adhesion, and the durability under hot and humid environment has been improved.

1‧‧‧偏光片 1‧‧‧ Polarizer

4‧‧‧機能性樹脂薄膜 4‧‧‧Functional resin film

5‧‧‧液晶單元 5‧‧‧LCD unit

6‧‧‧偏光板 6‧‧‧ Polarizer

7‧‧‧背光帶 7‧‧‧Backlight

8‧‧‧背光單元 8‧‧‧Backlight unit

10‧‧‧偏光板 10‧‧‧ Polarizer

11‧‧‧液晶顯示裝置 11‧‧‧Liquid crystal display device

21‧‧‧第一保護層 21‧‧‧The first protective layer

22‧‧‧第二保護層 22‧‧‧Second protective layer

31‧‧‧第一黏著劑層 31‧‧‧The first adhesive layer

32‧‧‧第二黏著劑層 32‧‧‧Second adhesive layer

第1圖(a)及(b)係表示在本發明的偏光板中之層構成的一個例子之圖。 Fig. 1 (a) and (b) are diagrams showing an example of the layer configuration in the polarizing plate of the present invention.

第2圖係表示在本發明的液晶顯示裝置中之層構成的一個例子之圖。 FIG. 2 is a diagram showing an example of the layer configuration in the liquid crystal display device of the present invention.

本發明的偏光板，係依序積層有機能性樹脂層、第一黏著劑層、屬於硬化性樹脂組成物的硬化物之第一保護層、偏光片之偏光板。再者，前述硬化性樹脂組成物係含有活性能量線硬化性化合物。以下，有關各構件之說明。 The polarizing plate of the present invention is a polarizing plate in which an organic resin layer, a first adhesive layer, a first protective layer of a cured product of a curable resin composition, and a polarizer are sequentially stacked. In addition, the said curable resin composition system contains an active energy ray curable compound. The following is a description of each component.

[偏光片] [Polarizer]

偏光片是以具有會吸收具有平行於光學軸之振動面之直線偏光且會穿透具有垂直於光學軸之振動面之直線偏光的性質之光學薄膜為佳，具體上，可以列舉：已在聚乙烯醇系樹脂薄膜吸附配向有二色性色素(碘或是二色性有機染料)之偏光片。 The polarizer is preferably an optical film that has the property of absorbing linearly polarized light having a vibration plane parallel to the optical axis and penetrating linearly polarized light having a vibration plane perpendicular to the optical axis. Specifically, it can be listed as: The vinyl alcohol-based resin film absorbs and aligns polarizers with dichroic pigments (iodine or dichroic organic dyes).

偏光片的厚度，通常是30μm以下，較佳是25μm以下，更佳是15μm以下，再更佳是10μm以下，特佳是7μm以下。又，作為偏光片者，適用已在聚乙烯醇系樹脂層吸附配向有二色性色素者的情形，可以延伸聚乙烯醇系樹脂單體而得到偏光片，也可在基材等塗佈聚乙烯醇系樹脂的溶液並使其乾燥之後，與基材共同延伸，除去基材而得到偏光片。與基材共同延伸的情形，係容易製作厚度在7μm以下的偏光片。 The thickness of the polarizer is usually 30 μm or less, preferably 25 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, and particularly preferably 7 μm or less. In addition, as the polarizer, a case in which a dichroic dye has been adsorbed on the polyvinyl alcohol-based resin layer is applied, and the polyvinyl alcohol-based resin monomer can be extended to obtain a polarizer, or a polymer can be coated on a substrate, etc. After the solution of the vinyl alcohol-based resin is dried, it is coextensive with the base material, and the base material is removed to obtain a polarizer. In the case of co-extension with the base material, it is easy to make a polarizer with a thickness of 7 μm or less.

作為上述的基材者，可以列舉：聚對苯二甲酸乙二酯薄膜、聚碳酸酯薄膜、三醋酸纖維素薄膜、降冰片烯薄膜、聚酯薄膜、聚苯乙烯薄膜等。 Examples of the aforementioned substrate include polyethylene terephthalate film, polycarbonate film, cellulose triacetate film, norbornene film, polyester film, and polystyrene film.

作為構成聚乙烯醇系樹脂層之聚乙烯醇系樹脂者，可以使用將聚醋酸乙烯酯系樹脂經皂化者。作為聚醋酸乙烯酯系樹脂者，除了醋酸乙烯酯的均聚物之聚醋酸乙烯酯之外，尚可例示醋酸乙烯酯與可和此共聚合之其他單體之共聚合物。作為可和醋酸乙烯酯共聚合之其他單體者，可以列舉：不飽和羧酸、烯烴、乙烯基醚、不飽和磺酸、有銨基之丙烯醯胺等。 As the polyvinyl alcohol resin constituting the polyvinyl alcohol resin layer, a saponified polyvinyl acetate resin can be used. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can be exemplified. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and ammonium group-containing acrylic amides.

聚乙烯醇系樹脂的皂化度，通常是80莫耳%以上，較佳是90至99.5莫耳%，更佳是94至99莫耳%。皂化度未達80莫耳%時，得到的偏光板之耐水性及耐濕熱性會下降。皂化度超過99.5莫耳%時，染色速度會變緩慢，生產性會下降，同時有得不到具有充分的偏光性能之偏光片之情形。 The degree of saponification of the polyvinyl alcohol-based resin is usually 80 mol% or more, preferably 90 to 99.5 mol%, and more preferably 94 to 99 mol%. When the degree of saponification is less than 80 mol%, the water resistance and humidity resistance of the obtained polarizing plate will decrease. When the degree of saponification exceeds 99.5 mol%, the dyeing speed will be slow, the productivity will be reduced, and at the same time, a polarizer with sufficient polarizing performance may not be obtained.

聚乙烯醇系樹脂，也可以是一部分經改質之改質聚乙烯醇，例如，也可以使用：藉由乙烯及丙烯等之烯烴改質；藉由丙烯酸、甲基丙烯酸及巴豆酸等之不飽和羧酸改質；藉由不飽和羧酸的烷基酯、丙烯醯胺等改質者。聚乙烯醇系樹脂的改質比率，係以未達30莫耳%為佳，以未達10%為更佳。在進行超過30莫耳%之改質的情形中，二色性色素會有變得不容易吸附之傾向，有得不到具有充分的偏光性能之偏光片之情形。 The polyvinyl alcohol-based resin may also be a part of modified polyvinyl alcohol that has been modified, for example, it may also be used: by modifying olefins such as ethylene and propylene; by using acrylic acid, methacrylic acid, and crotonic acid, etc. Saturated carboxylic acid modification; modified by alkyl ester of unsaturated carboxylic acid, acrylamide, etc. The modification ratio of the polyvinyl alcohol-based resin is preferably less than 30 mol%, and more preferably less than 10%. In the case of modification of more than 30 mol%, the dichroic pigment tends to become difficult to be adsorbed, and a polarizer with sufficient polarizing performance may not be obtained.

聚乙烯醇系樹脂的平均聚合度，較佳是100至10000左右，更佳是1500至8000，再更佳是2000至5000。 The average degree of polymerization of the polyvinyl alcohol-based resin is preferably about 100 to 10,000, more preferably 1500 to 8000, and even more preferably 2000 to 5000.

平均聚合度未達100時，有變得難以得到較佳偏光性能之傾向，平均聚合度超過10000時，對溶劑的溶解性會變差，聚乙烯醇系樹脂層的形成會有變得困難之傾向。 When the average degree of polymerization is less than 100, it tends to be difficult to obtain better polarizing performance. When the average degree of polymerization exceeds 10,000, the solubility in solvents will be poor, and the formation of the polyvinyl alcohol-based resin layer may become difficult tendency.

作為聚乙烯醇系樹脂者，可以使用適當的市售品。作為適合的市售品者，皆以商品名表示，可以列舉：Kuraray公司(股)製的"PVA 124"及"PVA 117"(皂化度皆為：98至99莫耳%)、"PVA 624"(皂化度：95至96莫耳%)、"PVA 617"(皂化度：94.5至95.5莫耳%)；日本合成化學工業(股)製的"N-300"及"NH-18"(皂化度皆為：98至99莫耳%)、"AH-22"(皂化度：97.5至98.5莫耳%)、"AH-26"(皂化度：97至98.8莫耳%)；日本VAM & POVAL(股)的"JC-33"(皂化度：99莫耳%以上)，"JF-17"、"JF-17L"及"JF-20"(皂化度皆為：98至99莫耳%)，"JM-26"(皂化度：95.5至97.5莫耳%)、"JM-33"(皂化度：93.5至95.5莫耳%)、"JP-45"(皂 化度：86.5至89.5莫耳%)等。 As the polyvinyl alcohol-based resin, an appropriate commercially available product can be used. Suitable commercial products are all indicated by the trade name, and examples include "PVA 124" and "PVA 117" manufactured by Kuraray Co., Ltd. (both saponification degree: 98 to 99 mole %), "PVA 624 "(Saponification degree: 95 to 96 mol%), "PVA 617" (Saponification degree: 94.5 to 95.5 mol%); "N-300" and "NH-18" manufactured by Japan Synthetic Chemical Industry Co., Ltd. ( The saponification degree is: 98 to 99 mol%), "AH-22" (saponification degree: 97.5 to 98.5 mol%), "AH-26" (saponification degree: 97 to 98.8 mol%); Japan VAM & "JC-33" (saponification degree: 99 mol% or more), "JF-17", "JF-17L" and "JF-20" (all saponification degrees: 98 to 99 mol%) ), "JM-26" (saponification degree: 95.5 to 97.5 mol%), "JM-33" (saponification degree: 93.5 to 95.5 mol%), "JP-45" (soap Chemical degree: 86.5 to 89.5 mol%) etc.

在偏光片中所含有(吸附配向)的二色性色素，可以列舉碘或是二色性有機染料等。作為二色性有機染料者，可以列舉：紅BR、紅LR、紅R、粉紅色LB、玉紅(rubin)BL、棗紅(bordeaux)GS、天藍色LG、檸檬黃、藍BR、藍2R、海軍藍(navy)RY、綠LG、紫LB、紫B、黑H、黑B、黑GSP、黃3G，黃R、橙LR、橙3R、猩紅(scarlet)GL、猩紅KGL、剛果紅、明亮紫(Brilliant Violet)BK、跨藍(supra blue)G、跨藍GL、跨橙GL、直接天藍、直接堅牢橙(direct fast orange)S、堅牢黑。二色性色素可以只單獨使用1種，也可以併用2種以上。 The dichroic dye contained (adsorption alignment) in the polarizer may include iodine or a dichroic organic dye. Examples of dichroic organic dyes include red BR, red LR, red R, pink LB, rubin BL, bordeaux GS, sky blue LG, lemon yellow, blue BR, blue 2R, Navy RY, Green LG, Purple LB, Purple B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Bright Brilliant Violet BK, supra blue G, cross blue GL, cross orange GL, direct sky blue, direct fast orange S, fast black. Only one kind of dichroic pigment may be used alone, or two or more kinds may be used in combination.

[第一保護層] [First protective layer]

本發明的偏光板是在偏光片之單側積層有第一保護層。此種第一保護層，係將含有活性能量線硬化性化合物之硬化性樹脂組成物加以硬化而形成的硬化層。活性能量線硬化性化合物是指，可藉由活性能量線(例如，紫外線、可見光、電子束、X射線等)的照射而硬化的化合物之意思。活性能量線硬化性化合物，也可以是陽離子聚合性化合物，也可以是自由基聚合性化合物，也可以是含有陽離子聚合性化合物與自由基聚合性化合物兩者。 The polarizing plate of the present invention has a first protective layer laminated on one side of the polarizer. Such a first protective layer is a cured layer formed by curing a curable resin composition containing an active energy ray curable compound. The active energy ray-curable compound means a compound that can be hardened by irradiation with active energy rays (for example, ultraviolet rays, visible light, electron beams, X-rays, etc.). The active energy ray-curable compound may be a cation polymerizable compound, a radical polymerizable compound, or may contain both a cation polymerizable compound and a radical polymerizable compound.

第一保護層的玻璃轉移溫度(Tg)是以在23℃以上為佳，以40℃以上為較佳，以50℃以上為更佳，以60℃以上為特佳。又第一保護層的玻璃轉移溫度，通常是 200℃以下。第一保護層的玻璃轉移溫度未達23℃時，偏光片的光學性能會有容易下降之傾向。玻璃轉移溫度，可藉由示差掃描熱量計(DSC)而測定。 The glass transition temperature (Tg) of the first protective layer is preferably 23° C. or higher, preferably 40° C. or higher, more preferably 50° C. or higher, and particularly preferably 60° C. or higher. The glass transition temperature of the first protective layer is usually Below 200℃. When the glass transition temperature of the first protective layer does not reach 23°C, the optical performance of the polarizer tends to be easily reduced. The glass transition temperature can be measured by a differential scanning calorimeter (DSC).

第一保護層的厚度是以0.1至10μm為佳，以1至5μm為更佳。第一保護層的厚度未達0.1μm時，會有不能充分抑制光學性能的下降之情形，另一方面，超過10μm時，會有偏光板的薄型輕量化的效果變小之情形。 The thickness of the first protective layer is preferably 0.1 to 10 μm, more preferably 1 to 5 μm. When the thickness of the first protective layer is less than 0.1 μm, the degradation of optical performance may not be sufficiently suppressed. On the other hand, when it exceeds 10 μm, the effect of thinning and lightening the polarizing plate may be reduced.

[硬化性樹脂組成物] [Curable resin composition]

硬化性樹脂組成物是以含有自由基聚合性化合物或是陽離子聚合性化合物為佳，以含有自由基聚合性化合物及陽離子聚合性化合物為更佳。含有自由基聚合性化合物及陽離子聚合性化合物之情形，可以期待有提高第一保護層的硬度之效果，再者硬化性樹脂組成物的黏度或硬化速度等的調整變得更容易進行。 The curable resin composition preferably contains a radically polymerizable compound or a cationically polymerizable compound, and more preferably contains a radically polymerizable compound and a cationically polymerizable compound. When the radical polymerizable compound and the cation polymerizable compound are contained, the effect of increasing the hardness of the first protective layer can be expected, and the viscosity and curing speed of the curable resin composition can be adjusted more easily.

[活性能量線硬化性化合物(自由基聚合性化合物)] [Active energy ray-curable compound (radical polymerizable compound)]

作為自由基聚合性化合物者，可以列舉：在分子內至少具有1個(甲基)丙烯醯氧基之化合物(以下，有時稱為「(甲基)丙烯酸系化合物」)、在分子內至少具有1個(甲基)丙烯醯胺基之化合物(以下，有時稱為「(甲基)丙烯醯胺系化合物」)等。又，「(甲基)丙烯醯氧基」是指甲基丙烯醯氧基或是丙烯醯氧基之意思，(甲基)丙烯醯胺基是指甲基丙烯醯胺基或是丙烯醯胺基之意思。 Examples of radically polymerizable compounds include compounds having at least one (meth)acryloyloxy group in the molecule (hereinafter, sometimes referred to as "(meth)acrylic compound"), and at least one in the molecule. A compound having one (meth)acrylamide group (hereinafter, sometimes referred to as "(meth)acrylamide compound"), etc. In addition, "(meth)acryloyloxy" means methacryloyloxy or acryloyloxy, and (meth)acryloylamino means methacryloylamino or acryloylamine The meaning of base.

作為(甲基)丙烯酸系化合物者，可以列舉：在分子內至少具有1個(甲基)丙烯醯氧基之(甲基)丙烯酸酯單體，或在分子內至少具有2個(甲基)丙烯醯氧基之(甲基)丙烯酸酯寡聚物等。此等可以各別單獨使用，也可以併用2種以上。在併用2種以上的情形，可以是2種以上的(甲基)丙烯酸酯單體，也可以是2種以上的(甲基)丙烯酸酯寡聚物，當然也可以併用1種以上的(甲基)丙烯酸酯單體與1種以上的(甲基)丙烯酸酯寡聚物。 Examples of (meth)acrylic compounds include (meth)acrylate monomers having at least one (meth)acryloyloxy group in the molecule, or at least two (meth) groups in the molecule. (Meth)acrylate oligomers of acrylic acid. These can be used individually or in combination of two or more. When two or more types are used in combination, they may be two or more types of (meth)acrylate monomers, or two or more types of (meth)acrylate oligomers, and of course one or more types (meth Group) acrylate monomer and one or more (meth)acrylate oligomers.

作為上述的(甲基)丙烯酸酯單體者，可以列舉：在分子內具有1個(甲基)丙烯醯氧基之單官能(甲基)丙烯酸酯單體、在分子內具有2個(甲基)丙烯醯氧基之2官能(甲基)丙烯酸酯單體及在分子內具有3個以上的(甲基)丙烯醯氧基之多官能(甲基)丙烯酸酯單體。 Examples of the (meth)acrylate monomers mentioned above include monofunctional (meth)acrylate monomers having one (meth)acryloyloxy group in the molecule, and two (meth)acrylic acid monomers in the molecule. Group) a bifunctional (meth)acrylate monomer of acryloxy and a multifunctional (meth)acrylate monomer having more than three (meth)acryloxy groups in the molecule.

作為單官能(甲基)丙烯酸酯單體者，可以列舉：(甲基)丙烯酸四氫糠酯、(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-或3-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸環己酯、1,4-環己烷二甲醇單丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸異冰片酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸二環戊烯基氧基乙酯、(甲基) 丙烯酸二甲基胺基乙酯、乙基卡必醇(甲基)丙烯酸酯、三羥甲基丙烷單(甲基)丙烯酸酯、新戊四醇單(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯等。 Examples of monofunctional (meth)acrylate monomers include: tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate , 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, methyl (meth)acrylate, (A Group) ethyl acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, third butyl (meth) acrylate, 2-ethyl (meth) acrylate Hexyl ester, isononyl (meth)acrylate, cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol monoacrylate, dicyclopentyl (meth)acrylate, (meth)acrylic acid Dicyclopentenyl ester, benzyl (meth)acrylate, isobornyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, (methyl) Dimethylamino ethyl acrylate, ethyl carbitol (meth) acrylate, trimethylolpropane mono (meth) acrylate, neopentaerythritol mono (meth) acrylate, phenoxy poly Ethylene glycol (meth)acrylate, etc.

作為單官能(甲基)丙烯酸酯單體者，也可以使用含有羧基的(甲基)丙烯酸酯單體。作為含有羧基的單官能(甲基)丙烯酸酯單體者，可以列舉：2-(甲基)丙烯醯氧基乙基鄰苯二甲酸、2-(甲基)丙烯醯氧基乙基六氫鄰苯二甲酸、(甲基)丙烯酸羧基乙酯、2-(甲基)丙烯醯氧基乙基琥珀酸、N-(甲基)丙烯醯氧基-N’,N’-二羧基甲基-對-苯二胺、4-(甲基)丙烯醯氧基乙基偏苯三甲酸等。 As the monofunctional (meth)acrylate monomer, a (meth)acrylate monomer containing a carboxyl group can also be used. Examples of carboxyl group-containing monofunctional (meth)acrylate monomers include 2-(meth)acryloyloxyethyl phthalic acid and 2-(meth)acryloyloxyethylhexahydrogen Phthalic acid, carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, N-(meth)acryloyloxy-N',N'-dicarboxymethyl -P-phenylenediamine, 4-(meth)acryloxyethyl trimellitic acid, etc.

作為(甲基)丙烯醯胺系化合物者，可以列舉N-取代(甲基)丙烯醯胺化合物。N-取代(甲基)丙烯醯胺化合物，係在N-位具有取代基之(甲基)丙烯醯胺化合物。此取代基的典型例子是烷基。N-位的取代基也可以互相鍵結並形成環，構成此環的-CH₂-，可以被取代成氧原子。又，在構成此環之碳原子中，也可以鍵結如烷基或側氧基(=O)的取代基。N-取代(甲基)丙烯醯胺，一般是可藉由(甲基)丙烯酸或其氯化物與1級或是2級胺的反應而製造。 Examples of (meth)acrylamide-based compounds include N-substituted (meth)acrylamide compounds. The N-substituted (meth)acrylamide compound is a (meth)acrylamide compound having a substituent at the N-position. A typical example of this substituent is an alkyl group. The substituents at the N-position may also be bonded to each other to form a ring, and -CH ₂ -constituting this ring may be substituted with an oxygen atom. In addition, in the carbon atoms constituting the ring, a substituent such as an alkyl group or a pendant oxygen group (=O) may be bonded. N-substituted (meth)acrylamide is generally produced by the reaction of (meth)acrylic acid or its chloride with primary or secondary amines.

N-取代(甲基)丙烯醯胺化合物，係以下式(III)所示之化合物為佳。在下式(III)中，Q¹是表示氫原子或是甲基，Q²是表示氫原子或是碳數1至6的烷基，Q³是表示可以具有羥基或是胺基之碳數1至6的烷基，或是Q²與Q³是互相鍵結，並形成-CH₂-可以被取代成氧原子之5員環或是6員環。前述胺基的氫原子也可以被取代成烷基。 The N-substituted (meth)acrylamide compound is preferably a compound represented by the following formula (III). In the following formula (III), Q ¹ represents a hydrogen atom or a methyl group, Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q ³ represents a carbon number 1 which may have a hydroxyl group or an amine group The alkyl group up to 6, or Q ² and Q ³ are bonded to each other and form -CH ₂ -may be substituted into a 5-membered ring or 6-membered ring of an oxygen atom. The hydrogen atom of the aforementioned amine group may be substituted with an alkyl group.

作為Q³是具有羥基之烷基的例子者，可以列舉羥基烷基。作為Q³是具有胺基之烷基的例子者，可以列舉：胺基烷基、N-烷基胺基烷基及N,N-二烷基胺基烷基。Q²與Q³是互相鍵結，並形成-CH₂-可以被取代成氧原子之5員環或是6員環時，將此5員環或是6員環的例子以在N-位與羰基(C=O)連接之基的形態揭示時，可以列舉：1-吡咯啶基(C₄H₈N-)、2-

唑啉酮-3-基[C₂H₄OC(=O)N-]、N-哌啶基(C₅H₁₀N-)、N-嗎啉基(C₂H₄OC₂H₄N-)等。 As an example where Q ³ is an alkyl group having a hydroxy group, a hydroxyalkyl group may be mentioned. Examples of Q ³ being an alkyl group having an amino group include aminoalkyl groups, N-alkylaminoalkyl groups, and N,N-dialkylaminoalkyl groups. Q ² and Q ³ are bonded to each other and form -CH ₂ -which can be replaced by a 5-membered ring or 6-membered ring which can be replaced by an oxygen atom, an example of this 5-membered ring or 6-membered ring is at the N-position When the form of the group connected to the carbonyl group (C=O) is revealed, it may include 1-pyrrolidinyl (C ₄ H ₈ N-), 2-

Oxazolin-3-yl [C ₂ H ₄ OC(=O)N-], N-piperidinyl (C ₅ H ₁₀ N-), N-morpholinyl (C ₂ H ₄ OC ₂ H ₄ N -)Wait.

作為Q²是氫原子且Q³是烷基的N-取代(甲基)丙烯醯胺化合物者，可以列舉：N-甲基(甲基)丙烯醯胺、N-乙基(甲基)丙烯醯胺、N-異丙基(甲基)丙烯醯胺、N-丁基(甲基)丙烯醯胺、N-第三丁基(甲基)丙烯醯胺、N-己基(甲基)丙烯醯胺等。同樣的作為Q²及Q³都是烷基的N-取代(甲基)丙烯醯胺者，可以列舉：N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺等。 Examples of N-substituted (meth)acrylamide compounds in which Q ² is a hydrogen atom and Q ³ is an alkyl group include N-methyl (meth) acrylamide and N-ethyl (meth) acryl Acetamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-third butyl(meth)acrylamide, N-hexyl(meth)acryl Acylamine, etc. Similarly, as N-substituted (meth)acrylamide in which Q ² and Q ³ are both alkyl groups, N,N-dimethyl(meth)acrylamide, N,N-diethyl (Meth) acrylamide, etc.

作為Q²是氫原子且Q³是具有羥基之烷基的N-取代(甲基)丙烯醯胺化合物者，可以列舉：N-羥基甲基(甲基)丙烯醯胺、N-(2-羥基乙基)(甲基)丙烯醯胺、N-(2-羥基丙基)(甲基)丙烯醯胺等。作為Q²是氫原子且Q³是具有胺基的烷基之N-取代(甲基)丙烯醯胺化合物者，可以列 舉：N-[2-(N,N-二甲基胺基)乙基](甲基)丙烯醯胺、N-[2-(N,N-二乙基胺基)乙基](甲基)丙烯醯胺、N-[3-(N,N-二甲基胺基)丙基](甲基)丙烯醯胺、N-[1-甲基-1-(N,N-二甲基胺基)乙基](甲基)丙烯醯胺等。 Examples of N-substituted (meth)acrylamide compounds in which Q ² is a hydrogen atom and Q ³ is an alkyl group having a hydroxyl group include N-hydroxymethyl (meth)acrylamide and N-(2- Hydroxyethyl) (meth)acrylamide, N-(2-hydroxypropyl) (meth)acrylamide, etc. Examples of N-substituted (meth)acrylamide compounds in which Q ² is a hydrogen atom and Q ³ is an alkyl group having an amine group include N-[2-(N,N-dimethylamino) ethyl Group] (meth)acrylamide, N-[2-(N,N-diethylamino)ethyl](meth)acrylamide, N-[3-(N,N-dimethyl Amino)propyl](meth)acrylamide, N-[1-methyl-1-(N,N-dimethylamino)ethyl](meth)acrylamide, etc.

作為Q²與Q³是互相鍵結，並形成-CH₂-可以被取代成氧原子之5員環或是6員環的N-取代(甲基)丙烯醯胺化合物者，可以列舉：N-丙烯醯基吡咯啶、3-丙烯醯基-2-

唑啉酮、4-丙烯醯基嗎啉、N-丙烯醯基哌啶、N-甲基丙烯醯基哌啶等。 Examples of the N-substituted (meth)acrylamide compounds in which Q ² and Q ³ are bonded to each other and form a 5-membered ring or a 6-membered ring which can be substituted into an oxygen atom by -CH ₂ -may include: N -Acryloyl pyrrolidine, 3-propenyl-2-

Azolinone, 4-propenyl morpholine, N-propenyl piperidine, N-methacryl piperidine, etc.

在上述N-取代(甲基)丙烯醯胺化合物之中，係以如N-羥基甲基丙烯醯胺及N-(2-羥基乙基)丙烯醯胺等N-羥基烷基(甲基)丙烯醯胺、以及如N,N-二甲基丙烯醯胺及N,N-二乙基丙烯醯胺等N,N-二烷基(甲基)丙烯醯胺為佳，以N-(2-羥基乙基)丙烯醯胺或是N,N-二甲基丙烯醯胺為特佳。 Among the above-mentioned N-substituted (meth)acrylamide compounds, N-hydroxyalkyl (methyl) such as N-hydroxymethacrylamide and N-(2-hydroxyethyl)acrylamide are used Acrylamide, and N,N-dialkyl (meth)acrylamide such as N,N-dimethylacrylamide and N,N-diethylacrylamide, preferably N-(2 -Hydroxyethyl)acrylamide or N,N-dimethylacrylamide is particularly preferred.

其他，如N-十二烷基(甲基)丙烯醯胺等具有長鏈烷基之N-烷基(甲基)丙烯醯胺，或如N-(甲氧基甲基)丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(丙氧基甲基)丙烯醯胺及N-(丁氧基甲基)丙烯醯胺等N-(烷氧基烷基)(甲基)丙烯醯胺，可作為構成活性能量線硬化性化合物之N-取代(甲基)丙烯醯胺化合物而使用。 Others, such as N-alkyl (meth) acrylamide with long-chain alkyl groups such as N-dodecyl (meth) acrylamide, or N- (methoxymethyl) acrylamide, N-(Alkoxyalkyl) such as N-(ethoxymethyl)acrylamide, N-(propoxymethyl)acrylamide and N-(butoxymethyl)acrylamide Group) acrylamide can be used as an N-substituted (meth)acrylamide compound constituting an active energy ray-curable compound.

作為2官能(甲基)丙烯酸酯單體者，以：伸烷基二醇二(甲基)丙烯酸酯、聚氧伸烷基二醇二(甲基)丙烯酸酯、鹵取代伸烷基二醇二(甲基)丙烯酸酯、脂肪族多醇 的二(甲基)丙烯酸酯、氫化二環戊二烯或是三環癸烷二烷醇的二(甲基)丙烯酸酯、二

烷二醇或是二

烷二烷醇的二(甲基)丙烯酸酯、雙酚A或是雙酚F的環氧烷加成物的二(甲基)丙烯酸酯、雙酚A或是雙酚F的環氧基二(甲基)丙烯酸酯等為代表。 As bifunctional (meth)acrylate monomers, alkylene glycol di(meth)acrylate, polyoxyalkylene glycol di(meth)acrylate, halogen substituted alkylene glycol Di (meth) acrylate, di (meth) acrylate of aliphatic polyol, hydrogenated dicyclopentadiene or di (meth) acrylate of tricyclodecanediol, di

Alkanediol or di

Di(meth)acrylates of alkylenedikanol, bisphenol A or bisphenol F alkylene oxide adducts of di(meth)acrylates, bisphenol A or bisphenol F epoxy (Meth) acrylate etc. are representative.

作為2官能(甲基)丙烯酸酯單體者，可以列舉：乙二醇二(甲基)丙烯酸酯、1,3-丁烷二醇二(甲基)丙烯酸酯、1,4-丁烷二醇二(甲基)丙烯酸酯、1,6-己烷二醇二(甲基)丙烯酸酯、1,9-壬烷二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇二(甲基)丙烯酸酯、二三羥甲基丙烷二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、聚四亞甲基二醇二(甲基)丙烯酸酯、矽酮(silicone)二(甲基)丙烯酸酯、羥基三甲基乙酸新戊二醇酯的二(甲基)丙烯酸酯、2,2-雙[4-(甲基)丙烯醯氧基乙氧基乙氧基苯基]丙烷、2,2-雙[4-(甲基)丙烯醯氧基乙氧基乙氧基環己基]丙烷、二(甲基)丙烯酸氫化二環戊二烯基酯、三環癸烷二甲醇二(甲基)丙烯酸酯、二(甲基)丙烯酸1,3-二

烷-2,5-二基酯[別名：二

烷二醇二(甲基)丙烯酸酯]、羥基三甲基乙醛與三羥甲基丙烷的縮醛化合物[化學名：2-(2-羥基-1,1-二甲基乙基)-5-乙基-5-羥基甲基-1,3-二

烷]的二(甲基)丙烯酸酯、參(羥基乙基)異三聚氰酸酯二(甲基)丙烯酸酯等。 Examples of bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, and 1,4-butanedione. Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth) Acrylate, trimethylolpropane di(meth)acrylate, neopentyl alcohol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, diethylene glycol di(meth)acrylate ) Acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, silicone di (meth) acrylate, hydroxy trimethyl acetate neopentyl glycol bis (meth) Group) acrylate, 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxy Ethoxycyclohexyl]propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, di(meth)acrylic acid 1,3-di

Alkane-2,5-diyl ester [alias: di

Alkanediol di(meth)acrylate], acetal compound of hydroxytrimethylacetaldehyde and trimethylolpropane [chemical name: 2-(2-hydroxy-1,1-dimethylethyl)- 5-ethyl-5-hydroxymethyl-1,3-di

Alkane] di(meth)acrylate, ginseng (hydroxyethyl) isocyanurate di(meth)acrylate, etc.

作為3官能以上的多官能(甲基)丙烯酸酯單體者，可以列舉：如三(甲基)丙烯酸甘油酯、三羥甲基丙烷三(甲基)丙烯酸酯、二三羥甲基丙烷三(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯及二新戊四醇六(甲基)丙烯酸酯等3官能以上之脂肪族多醇的聚(甲基)丙烯酸酯。其他，可以列舉：3官能以上的鹵取代多醇之聚(甲基)丙烯酸酯、甘油的環氧烷加成物的三(甲基)丙烯酸酯、三羥甲基丙烷的環氧烷加成物的三(甲基)丙烯酸酯、1,1,1-參[(甲基)丙烯醯氧基乙氧基乙氧基]丙烷、參(羥基乙基)異三聚氰酸酯三(甲基)丙烯酸酯類等。 Examples of trifunctional or more polyfunctional (meth)acrylate monomers include triglyceride (meth)acrylate, trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane trioxide. (Meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, neopentaerythritol tri(meth)acrylate, neopentaerythritol tetra(meth)acrylate, dipentaerythritol Poly(meth)acrylates of 3 or more aliphatic polyols such as tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate . Others include: poly(meth)acrylates of halogen-substituted polyols with more than 3 functions, tri(meth)acrylates of alkylene oxide adducts of glycerin, and alkylene oxide addition of trimethylolpropane Tri(meth)acrylate, 1,1,1-ginseng[(meth)acrylic ethoxyethoxyethoxy]propane, ginseng (hydroxyethyl)isocyanurate tri(meth) Radicals) acrylic esters, etc.

作為(甲基)丙烯酸酯寡聚物者，可以列舉：胺酯(甲基)丙烯酸酯寡聚物、聚酯(甲基)丙烯酸酯寡聚物、環氧基(甲基)丙烯酸酯寡聚物等。 Examples of (meth)acrylate oligomers include amine ester (meth)acrylate oligomers, polyester (meth)acrylate oligomers, and epoxy (meth)acrylate oligomers. Things.

胺酯(甲基)丙烯酸酯寡聚物是指，在分子內具有胺酯鍵(-NHCOO-)及至少2個(甲基)丙烯醯氧基之化合物。具體上，可以列舉：在分子內具有至少1個(甲基)丙烯醯氧基及至少1個羥基之含有羥基之(甲基)丙烯酸酯單體與聚異氰酸酯的胺酯化反應之生成物，或將多醇與聚異氰酸酯反應而可得到的含有末端異氰酸基之胺酯化合物，與在分子內分別具有至少1個(甲基)丙烯醯氧基及至少1個羥基之(甲基)丙烯酸酯單體的胺酯化反應之生成物等。 The amine ester (meth)acrylate oligomer refers to a compound having an amine ester bond (-NHCOO-) and at least two (meth)acryloyloxy groups in the molecule. Specifically, it can be exemplified by the product of the amine esterification reaction of a hydroxyl-containing (meth)acrylate monomer having at least one (meth)acryloyloxy group and at least one hydroxyl group in the molecule and a polyisocyanate, Or an amine ester compound containing terminal isocyanate group obtained by reacting polyol with polyisocyanate, and a (methyl) group having at least one (meth)acryloyloxy group and at least one hydroxyl group in the molecule, respectively The product of the amine esterification reaction of the acrylate monomer, etc.

作為在胺酯化反應中使用的含有羥基之(甲基)丙烯酸酯單體者，可以列舉：(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸2-羥基丁酯、(甲基)丙烯酸2-羥基-3-苯氧基丙酯、二(甲基)丙烯酸甘油酯、三羥甲基丙烷二(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯等。 Examples of the (meth)acrylate monomers containing hydroxyl groups used in the amine esterification reaction include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (methyl ) 2-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane di(meth)acrylate, neopentyl Alcohol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc.

作為供應至與此種含有羥基之(甲基)丙烯酸酯單體之胺酯化反應中之聚異氰酸酯者，可以列舉：六亞甲基二異氰酸酯、離胺酸二異氰酸酯、異佛爾酮二異氰酸酯、二環己基甲烷二異氰酸酯、甲苯二異氰酸酯、苯二甲基二異氰酸酯、將此等二異氰酸酯之中芳香族的異氰酸酯類氫化而可得到之二異氰酸酯(例如，氫化甲苯二異氰酸酯、氫化苯二甲基二異氰酸酯等)、三苯基甲烷三異氰酸酯、二苯甲基苯三異氰酸酯等二-或是三-異氰酸酯及上述的二異氰酸酯多量化而可得到的聚異氰酸酯等。 Examples of the polyisocyanate supplied to the amine esterification reaction with such hydroxyl-containing (meth)acrylate monomers include hexamethylene diisocyanate, urethane diisocyanate, and isophorone diisocyanate. , Dicyclohexylmethane diisocyanate, toluene diisocyanate, xylylene diisocyanate, diisocyanate obtained by hydrogenating aromatic isocyanates among these diisocyanates (for example, hydrogenated toluene diisocyanate, hydrogenated xylylene Diisocyanate, etc.), di- or tri-isocyanate such as triphenylmethane triisocyanate, benzylbenzene triisocyanate, and polyisocyanate obtained by quantifying the above-mentioned diisocyanate.

又，作為用以藉由與聚異氰酸酯的反應而成為含有末端異氰酸基胺酯化合物之多醇類者，除了芳香族、脂肪族及脂環式的多醇之外，還可以列舉：聚酯多醇、聚醚多醇等。作為芳香族的多醇者，可以列舉：1,4-苯二甲醇、1,3-苯二甲醇、1,2-苯二甲醇、4,4’-萘二甲醇、3,4’-萘二甲醇等。作為脂肪族及脂環式的多醇者，可以列舉：1,4-丁烷二醇、1,6-己烷二醇、乙二醇、二乙二醇、三乙二醇、丙二醇、新戊二醇、三羥甲基乙烷、三羥甲基丙烷、二三羥甲基丙烷、新戊四醇、二新戊四醇、二羥甲基庚烷、 二羥甲基丙酸、二羥甲基丁酸、甘油、氫化雙酚A等。 In addition, as the polyols used to become terminal isocyanatoamine compounds by reaction with polyisocyanates, in addition to aromatic, aliphatic, and alicyclic polyols, polyhydric alcohols may also be mentioned: Ester polyol, polyether polyol, etc. Examples of aromatic polyols include 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalene dimethanol, and 3,4'-naphthalene. Dimethanol, etc. Examples of aliphatic and alicyclic polyols include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and new Pentylene glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, neopentaerythritol, dipentaerythritol, dimethylolheptane, Dimethylolpropionic acid, dimethylolbutyric acid, glycerin, hydrogenated bisphenol A, etc.

聚酯多醇，係藉由上述之多醇類與多元羧酸或是其酸酐的脫水縮合反應而得到者。作為多元羧酸或是其酸酐者，有：琥珀酸、琥珀酸酐、己二酸、馬來酸、馬來酸酐、衣康酸、衣康酸酐、偏苯三甲酸、偏苯三甲酸酐、均苯四甲酸、均苯四甲酸酐、鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸、六氫鄰苯二甲酸、六氫鄰苯二甲酸酐等。 Polyester polyols are obtained by the dehydration condensation reaction of the above-mentioned polyols with polycarboxylic acids or their anhydrides. As the polycarboxylic acid or its anhydride, there are: succinic acid, succinic anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, trimellitic acid, trimellitic anhydride, homobenzene Tetracarboxylic acid, pyromellitic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, etc.

聚醚多醇，除了聚伸烷基二醇之外，尚可以列舉：藉由上述多醇類或是二羥基苯類與環氧烷的反應而可得到的聚氧伸烷基改質多醇等。 In addition to polyalkylene glycols, polyether polyols include polyoxyalkylene-modified polyols obtainable by the reaction of the above-mentioned polyols or dihydroxybenzenes with alkylene oxide Wait.

聚酯(甲基)丙烯酸酯寡聚物，係在分子內具有至少2個酯鍵與至少2個(甲基)丙烯醯氧基之化合物。具體上，可以藉由(甲基)丙烯酸、多元羧酸或是其酸酐，及多醇的脫水縮合反應而得到。作為在脫水縮合反應中使用的多元羧酸或是其酸酐者，可以列舉：琥珀酸、琥珀酸酐、己二酸、馬來酸、馬來酸酐、衣康酸、衣康酸酐、偏苯三甲酸、偏苯三甲酸酐、均苯四甲酸、均苯四甲酸酐、六氫鄰苯二甲酸、六氫鄰苯二甲酸酐、鄰苯二甲酸、鄰苯二甲酸酐、間苯二甲酸、對苯二甲酸等。又，作為在脫水縮合反應中使用的多醇者，可以列舉：1,4-丁烷二醇、1,6-己烷二醇、乙二醇、二乙二醇、三乙二醇、丙二醇、新戊二醇、三羥甲基乙烷、三羥甲基丙烷、二三羥甲基丙烷、新戊四醇、二新戊四醇、二羥甲基庚烷、二羥甲基丙酸、 二羥甲基丁酸、甘油、氫化雙酚A等。 Polyester (meth)acrylate oligomer is a compound having at least 2 ester bonds and at least 2 (meth)acryloyloxy groups in the molecule. Specifically, it can be obtained by dehydration condensation reaction of (meth)acrylic acid, polycarboxylic acid or its anhydride, and polyol. Examples of the polycarboxylic acid or its anhydride used in the dehydration condensation reaction include succinic acid, succinic anhydride, adipic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, trimellitic acid , Trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, isophthalic acid, p-benzene Dicarboxylic acid and so on. In addition, examples of the polyol used in the dehydration condensation reaction include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol. , Neopentyl glycol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, neopentaerythritol, dipentaerythritol, dimethylolheptane, dimethylolpropionic acid , Dimethylol butyric acid, glycerin, hydrogenated bisphenol A, etc.

環氧基(甲基)丙烯酸酯寡聚物，係在分子內至少具有2個(甲基)丙烯醯氧基，且可以藉由聚縮水甘油醚與(甲基)丙烯酸的加成反應而得到者。作為在加成反應中使用的聚縮水甘油醚者，可以列舉：乙二醇二縮水甘油醚、丙二醇二縮水甘油醚、三丙二醇二縮水甘油醚、1,6-己烷二醇二縮水甘油醚、雙酚A二縮水甘油醚等。 Epoxy (meth)acrylate oligomers, which have at least two (meth)acryloyloxy groups in the molecule, and can be obtained by the addition reaction of polyglycidyl ether and (meth)acrylic acid By. Examples of the polyglycidyl ether used in the addition reaction include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and 1,6-hexanediol diglycidyl ether. , Bisphenol A diglycidyl ether, etc.

硬化性樹脂組成物含有自由基聚合性化合物時，自由基聚合性化合物的含量，相對於硬化性組成物100重量份，通常是1至70重量份，較佳是10至60重量份。 When the curable resin composition contains a radically polymerizable compound, the content of the radically polymerizable compound is usually 1 to 70 parts by weight, preferably 10 to 60 parts by weight relative to 100 parts by weight of the curable composition.

[活性能量線硬化性化合物(陽離子聚合性化合物)] [Active energy ray-curable compound (cationically polymerizable compound)]

作為陽離子聚合性化合物者，可以列舉：在分子內至少具有1個氧雜環丁烷環(4員環醚)之化合物(以下，有時簡稱為「氧雜環丁烷化合物」)、在分子內至少具有1個環氧乙烷環(3員環醚)之化合物(以下，有時簡稱為「環氧化合物」)等。 Examples of the cationic polymerizable compound include compounds having at least one oxetane ring (4-membered cyclic ether) in the molecule (hereinafter, sometimes simply referred to as "oxetane compound"), and molecules Compounds having at least one ethylene oxide ring (3-membered cyclic ether) (hereinafter, sometimes simply referred to as "epoxy compounds"), etc.

作為氧雜環丁烷化合物者，可以列舉：3-乙基-3-羥基甲基氧雜環丁烷、1,4-雙[(3-乙基-3-氧雜環丁基)甲氧基甲基]苯、3-乙基-3-(苯氧基甲基)氧雜環丁烷、二[(3-乙基-3-氧雜環丁基)甲基]醚、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷、苯酚酚醛清漆(phenol novolac)氧雜環丁烷等。此等氧雜環丁烷化合物，可容易地取得市售品，作 為市售品者，下述者都是從東亞合成(股)公司所銷售的，以商品名表示，可以列舉："Aron oxetane(註冊商標)OXT-101"、"Aron oxetane(註冊商標)OXT-121"、"Aron oxetane(註冊商標)OXT-211"、"Aron oxetane(註冊商標)OXT-221"、"Aron oxetane(註冊商標)OXT-212"等。 Examples of oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxy Methyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl Yl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac oxetane, etc. These oxetane compounds can be easily obtained from commercially available products. For commercial products, the following are all sold by East Asia Synthetic Co., Ltd. and are represented by trade names, including: "Aron oxetane (registered trademark) OXT-101", "Aron oxetane (registered trademark) OXT -121", "Aron oxetane (registered trademark) OXT-211", "Aron oxetane (registered trademark) OXT-221", "Aron oxetane (registered trademark) OXT-212", etc.

又，硬化性樹脂組成物，除了上述的氧雜環丁烷化合物之外，也可以含有環氧化合物。從第一保護層與偏光片的密著性變得較良好之觀點而言，硬化性樹脂組成物是以含有環氧化合物者為佳。 In addition, the curable resin composition may contain an epoxy compound in addition to the oxetane compound described above. From the viewpoint that the adhesion between the first protective layer and the polarizer becomes better, the curable resin composition preferably contains an epoxy compound.

作為環氧化合物者，可以列舉：芳香族環氧化合物、有脂環式環之多醇的縮水甘油醚、脂肪族環氧化合物、脂環式環氧化合物等。 Examples of the epoxy compound include aromatic epoxy compounds, glycidyl ethers of alicyclic polyhydric alcohols, aliphatic epoxy compounds, and alicyclic epoxy compounds.

作為芳香族環氧化合物者，可以列舉：如雙酚A的二縮水甘油醚、雙酚F的二縮水甘油醚及雙酚S的二縮水甘油醚等雙酚型環氧樹脂；如苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂及羥基苯甲醛苯酚酚醛清漆環氧樹脂等酚醛清漆型環氧樹脂；如四羥基苯基甲烷的縮水甘油醚、四羥基二苯甲酮的縮水甘油醚及環氧化聚乙烯基酚等多官能型的環氧樹脂等。 Examples of aromatic epoxy compounds include bisphenol-type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; such as phenol novolac. Novolac-type epoxy resins such as epoxy resins, cresol novolac epoxy resins and hydroxybenzaldehyde phenol novolac epoxy resins; such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone And multifunctional epoxy resins such as epoxidized polyvinylphenol.

作為有脂環式環之多醇的縮水甘油醚者，可以列舉：將藉由在觸媒的存在下，將芳香族多醇於加壓下選擇性地對芳香環進行氫化反應而得到之核氫化聚羥基化合物，經縮水甘油醚化者。作為芳香族多醇者，可以列舉：如雙酚A、雙酚F、雙酚S等雙酚型化合物；如苯酚 酚醛清漆樹脂、甲酚酚醛清漆樹脂、羥基苯甲醛苯酚酚醛清漆樹脂等酚醛清漆型樹脂；如四羥基二苯基甲烷、四羥基二苯甲酮、聚乙烯基酚等多官能型化合物等。藉由對此等芳香族多醇的芳香環進行氫化反應而得到的脂環式多醇，與環氧氯丙烷反應，可以作成縮水甘油醚。如此之具有脂環式環的多醇之縮水甘油醚中，作為理想者，可列舉經氫化之雙酚A的二縮水甘油醚。 Examples of glycidyl ethers of polyalcohols having an alicyclic ring include a core obtained by selectively hydrogenating an aromatic ring under pressure in the presence of a catalyst under aromatic pressure Hydrogenated polyhydroxy compounds, etherified by glycidol. Examples of aromatic polyols include bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S; such as phenol Novolak resins such as novolak resins, cresol novolak resins, hydroxybenzaldehyde phenol novolak resins; polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone, polyvinylphenol, etc. The alicyclic polyol obtained by hydrogenating the aromatic rings of these aromatic polyols reacts with epichlorohydrin to make glycidyl ether. Among such glycidyl ethers of polyalcohols having an alicyclic ring, ideally, diglycidyl ethers of hydrogenated bisphenol A can be cited.

作為脂肪族環氧化合物者，可以列舉：脂肪族多元醇或是其環氧烷加成物的聚縮水甘油醚等。具體上，可以列舉：1,4-丁烷二醇的二縮水甘油醚；1,6-己烷二醇的二縮水甘油醚；甘油的三縮水甘油醚；三羥甲基丙烷的三縮水甘油醚；聚乙二醇的二縮水甘油醚；丙二醇的二縮水甘油醚；新戊二醇的二縮水甘油醚；藉由對如乙二醇、丙二醇或是甘油等脂肪族多元醇加成1種或是2種以上的環氧烷(環氧乙烷或環氧丙烷)而得到的聚醚多醇之聚縮水甘油醚等。 Examples of aliphatic epoxy compounds include aliphatic polyhydric alcohols or polyglycidyl ethers of alkylene oxide adducts thereof. Specific examples include: diglycidyl ether of 1,4-butanediol; diglycidyl ether of 1,6-hexanediol; triglycidyl ether of glycerol; triglycidyl ether of trimethylolpropane Ether; diglycidyl ether of polyethylene glycol; diglycidyl ether of propylene glycol; diglycidyl ether of neopentyl glycol; by adding an aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol, or glycerin Or polyglycidyl ethers of polyether polyols obtained from two or more kinds of alkylene oxides (ethylene oxide or propylene oxide).

又，下式(I)所示之單官能環氧化合物也可例舉作為脂肪族環氧化合物。R¹是可分枝的碳數1至15的烷基。烷基的碳數是以6以上為佳，以6至10為更佳。其中是以分枝的烷基為佳。作為式(I)所示之單官能環氧化合物者，可以列舉：2-乙基己基縮水甘油醚。 In addition, the monofunctional epoxy compound represented by the following formula (I) may also be exemplified as the aliphatic epoxy compound. R ¹ is a branchable alkyl group having 1 to 15 carbon atoms. The carbon number of the alkyl group is preferably 6 or more, more preferably 6 to 10. Among them, branched alkyl groups are preferred. Examples of the monofunctional epoxy compound represented by formula (I) include 2-ethylhexyl glycidyl ether.

所謂的脂環式環氧化合物，係在分子內至少具有1個與脂環式環的碳原子一起形成環氧乙烷環之結構的化合物。在此，「與脂環式環的碳原子一起形成環氧乙烷環之結構」是指下式(II)所示的結構之意思。式中的n是2至5的整數。 The so-called alicyclic epoxy compound is a compound having at least one structure in the molecule which forms an ethylene oxide ring together with the carbon atom of the alicyclic ring. Here, "the structure which forms an ethylene oxide ring together with the carbon atom of an alicyclic ring" means the structure shown by following formula (II). N in the formula is an integer of 2 to 5.

已除去此式(II)中之(CH₂)_n中的1個或是複數個氫原子之形態之基與其他的化學結構鍵結之化合物，變成脂環式環氧化合物。又，形成脂環式環之(CH₂)_n中的1個或是複數個氫原子，也可經如甲基或乙基等直鏈狀烷基所取代。 The compound in which the form of one or a plurality of hydrogen atoms in (CH ₂ ) _n in this formula (II) has been removed is bonded to another chemical structure to become an alicyclic epoxy compound. In addition, one or a plurality of hydrogen atoms in (CH ₂ ) _n forming an alicyclic ring may be substituted with a linear alkyl group such as methyl or ethyl.

作為環氧化合物者是以脂環式環氧化合物為佳，從藉由與偏光片的密著性而可容易得到優良之保護層的觀點而言，以具有環氧基環己烷[在上述式(II)中n=4者]或是環氧基環庚烷[在上述式(II)中n=5者]之環氧化合物為更佳。以下揭示，脂環式環氧化合物的具體例。 The epoxy compound is preferably an alicyclic epoxy compound. From the viewpoint that an excellent protective layer can be easily obtained by adhesion to the polarizer, it has an epoxycyclohexane [in the above The epoxy compound of formula (II) where n=4] or epoxycycloheptane [n=5 in formula (II) above] is more preferable. Specific examples of alicyclic epoxy compounds are disclosed below.

在硬化性樹脂組成物中，環氧化合物可以只單獨使用1種，也可以併用2種以上。 In the curable resin composition, only one type of epoxy compound may be used alone, or two or more types may be used in combination.

硬化性樹脂組成物含有氧雜環丁烷化合物 時，氧雜環丁烷化合物的含量，相對於硬化性組成物100重量份，通常是1至50重量份，較佳是10至40重量份。當硬化性樹脂組成物含有環氧化合物時，環氧化合物的含量，相對於硬化性組成物100重量份，通常是1至90重量份，較佳是20至80重量份。 The curable resin composition contains an oxetane compound At this time, the content of the oxetane compound is usually 1 to 50 parts by weight, preferably 10 to 40 parts by weight with respect to 100 parts by weight of the curable composition. When the curable resin composition contains an epoxy compound, the content of the epoxy compound is usually 1 to 90 parts by weight, preferably 20 to 80 parts by weight with respect to 100 parts by weight of the curable composition.

又，當硬化性樹脂組成物含有陽離子聚合性化合物時，陽離子聚合性化合物的含量，相對於硬化性組成物100重量份，通常是10至99重量份，較佳是40至99重量份。 In addition, when the curable resin composition contains a cationically polymerizable compound, the content of the cationically polymerizable compound is usually 10 to 99 parts by weight, preferably 40 to 99 parts by weight with respect to 100 parts by weight of the curable composition.

[自由基聚合起始劑] [Free radical polymerization initiator]

硬化性樹脂組成物，當含有自由基聚合性化合物作為活性能量線硬化性化合物時，硬化性樹脂組成物是以含有自由基聚合起始劑者為佳。自由基聚合起始劑只要是可藉由照射活性能量線，使(甲基)丙烯酸系化合物等自由基聚合性化合物開始進行聚合者即可，可以使用公知者。作為自由基聚合起始劑者，可以列舉：如苯乙酮、3-甲基苯乙酮、苯甲基二甲基縮酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、2-甲基-1-[4-(甲基硫基)苯基-2-嗎啉基丙烷-1-酮、以及2-羥基-2-甲基-1-苯基丙烷-1-酮等苯乙酮系起始劑；如二苯甲酮、4-氯二苯甲酮及4,4’-二胺基二苯甲酮等二苯甲酮系起始劑；如安息香丙基醚及安息香乙基醚等安息香醚系起始劑；如4-異丙基噻噸酮等噻噸酮系起始劑；其他，呫噸酮、茀酮、樟腦醌、苯甲醛、蒽酮等。 When the curable resin composition contains a radically polymerizable compound as the active energy ray curable compound, the curable resin composition preferably contains a radical polymerization initiator. The radical polymerization initiator may be any one that can start the polymerization of a radically polymerizable compound such as a (meth)acrylic compound by irradiating an active energy ray, and a known one can be used. Examples of radical polymerization initiators include acetophenone, 3-methylacetophenone, benzyldimethyl ketal, and 1-(4-isopropylphenyl)-2-hydroxy- 2-methylpropane-1-one, 2-methyl-1-[4-(methylthio)phenyl-2-morpholinylpropane-1-one, and 2-hydroxy-2-methyl- Acetophenone series initiators such as 1-phenylpropane-1-one; such as benzophenone series such as benzophenone, 4-chlorobenzophenone and 4,4'-diaminobenzophenone Starters; benzoin ether-based starters such as benzoin propyl ether and benzoin ethyl ether; thioxanthone-based starters such as 4-isopropyl thioxanthone; others, xanthone, crotonone, camphor Quinone, benzaldehyde, anthrone, etc.

自由基聚合起始劑可容易地取得市售品， 例如，分別以商品名表示，可以列舉：BASF公司製的"IRGACURE(註冊商標)184"、"IRGACURE(註冊商標)907"、"DAROCUR(註冊商標)1173"、"Lucirin(註冊商標)TPO"等。 Free radical polymerization initiators can easily obtain commercially available products, For example, they are represented by trade names, respectively: "IRGACURE (registered trademark) 184", "IRGACURE (registered trademark) 907", "DAROCUR (registered trademark) 1173", "Lucirin (registered trademark) TPO" manufactured by BASF Corporation Wait.

自由基聚合起始劑的含量，相對於(甲基)丙烯酸系化合物等自由基聚合性化合物的全量100重量份，通常是0.5至20重量份，較佳是1至6重量份。自由基聚合起始劑的調配量少時，硬化會變得不充分，第一保護層與偏光片層的密著性會有下降之傾向。又，當自由基聚合起始劑的調配量太多時，在硬化性樹脂組成物中之活性能量線硬化性化合物會相對地變少，得到的偏光板之光學特性的耐久性會有下降之可能性。 The content of the radical polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 to 6 parts by weight, relative to 100 parts by weight of the total amount of radical polymerizable compounds such as (meth)acrylic compounds. When the amount of the radical polymerization initiator is small, curing becomes insufficient, and the adhesion between the first protective layer and the polarizer layer tends to decrease. In addition, when the amount of the radical polymerization initiator is too large, the active energy ray-curable compound in the curable resin composition will be relatively small, and the durability of the optical characteristics of the obtained polarizing plate will be reduced. possibility.

[陽離子聚合起始劑] [Cationic polymerization initiator]

硬化性樹脂組成物，含有氧雜環丁烷化合物或環氧化合物等陽離子聚合性化合物作為活性能量線硬化性化合物時，在其硬化性樹脂組成物中，通常是調配陽離子聚合起始劑。使用陽離子聚合起始劑時，在第一保護層形成時可使必須的溫度上昇幅度較小。因此，即使不考慮到偏光片的耐熱性或偏光片的膨脹所致之扭曲，仍可形成與偏光片的密著性更良好的保護層。 When the curable resin composition contains a cationic polymerizable compound such as an oxetane compound or an epoxy compound as an active energy ray curable compound, a cationic polymerization initiator is usually blended in the curable resin composition. When a cationic polymerization initiator is used, the necessary temperature increase can be made smaller when the first protective layer is formed. Therefore, even without considering the heat resistance of the polarizer or the distortion caused by the expansion of the polarizer, a protective layer with better adhesion to the polarizer can be formed.

陽離子聚合起始劑，係藉由照射可見光線、紫外線、X射線、電子束等活性能量線而會產生陽離子種或是路易斯酸，而開始陽離子聚合性化合物的聚合反應。作為陽離子聚合起始劑者，可以列舉：如芳香族重氮 鹽；芳香族錪鹽及芳香族鋶鹽等鎓鹽；鐵-芳烴錯合物等。 The cationic polymerization initiator generates a cationic species or a Lewis acid by irradiating active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams to start the polymerization reaction of the cationic polymerizable compound. As the cationic polymerization initiator, there may be mentioned: aromatic diazo Salts; onium salts such as aromatic tungsten salts and aromatic osmium salts; iron-aromatic complexes, etc.

作為芳香族重氮鹽者，可以列舉如下所述之化合物。 Examples of aromatic diazonium salts include the following compounds.

苯重氮 六氟銻酸鹽、苯重氮 六氟磷酸鹽、苯重氮 六氟硼酸鹽等。 Benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, etc.

作為芳香族錪鹽者，可以列舉如下所述之化合物。 Examples of the aromatic tungsten salts include the following compounds.

二苯基錪 肆(五氟苯基)硼酸鹽、二苯基錪 六氟磷酸鹽、二苯基錪 六氟銻酸鹽、二(4-壬基苯基)錪 六氟磷酸鹽等。 Diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, bis(4-nonylphenyl) hexafluorophosphate, etc.

作為芳香族鋶鹽者，可以列舉如下所述之化合物。 Examples of the aromatic osmium salts include the following compounds.

三苯基鋶 六氟磷酸鹽、三苯基鋶 六氟銻酸鹽、三苯基鋶 肆(五氟苯基)硼酸鹽、4,4’-雙[二苯基鋶基]二苯基硫化物 雙六氟磷酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫化物 雙六氟銻酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫化物 雙六氟磷酸鹽、7-[二(對-甲苯基)鋶基]-2-異丙基噻噸酮 六氟銻酸鹽、7-[二(對-甲苯基)鋶基]-2-異丙基噻噸酮 肆(五氟苯基)硼酸鹽、4-苯基羰基-4’-二苯基鋶基-二苯基硫化物 六氟磷酸鹽、4-(對-第三丁基苯基羰基)-4’-二苯基鋶基-二苯基硫化物 六氟銻酸鹽、4-(對-第三丁基苯基羰基)-4’-二(對-甲苯基)鋶基-二苯基硫化物 肆(五氟苯基)硼酸鹽等。 Triphenylammonium hexafluorophosphate, triphenylammonium hexafluoroantimonate, triphenylammonium (pentafluorophenyl) borate, 4,4'-bis[diphenylamyl]diphenyl sulfide Bis-hexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenyl alkynyl]diphenyl sulfide bishexafluoroantimonate, 4,4'-bis[bis(β -Hydroxyethoxy)phenyl alkynyl]diphenyl sulfide bishexafluorophosphate, 7-[bis(p-tolyl)amyl]-2-isopropylthioxanthone hexafluoroantimonate, 7-[bis(p-tolyl)amyl]-2-isopropylthioxanthone (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylamyl-diphenyl Sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylamyl-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butyl) Phenylcarbonyl)-4'-bis(p-tolyl)amyl-diphenyl sulfide (pentafluorophenyl) borate, etc.

作為鐵-芳烴錯合物者，可以列舉如下所述 之化合物。 Examples of iron-aromatic hydrocarbon complexes include the following Of compounds.

二甲苯-環戊二烯基鐵(II)六氟銻酸鹽、異丙苯-環戊二烯基鐵(II)六氟磷酸鹽、二甲苯-環戊二烯基鐵(II)參(三氟甲基磺醯基)甲烷化物(methaneide)等。 Xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) ginseng ( Trifluoromethylsulfonyl) methaneide, etc.

此等陽離子聚合起始劑可以容易地取得市售品，例如，分別以商品名表示，可以列舉：由日本化藥(股)所銷售之"KAYARAD(註冊商標)PCI-220"及"KAYARAD(註冊商標)PCI-620"、由陶氏化學公司所販售的"UVI-6990"、由Daicel Cytec(股)所販售的"UVACURE(註冊商標)1590"、由ADEKA(股)所販售的"Adeka optomer(註冊商標)SP-150"及"Adeka optomer(註冊商標)SP-170"、由日本曹達(股)所販售的"CI-5102"、"CIT-1370"、"CIT-1682"、"CIP-1866S"、"CIP-2048S"及"CIP-2064S"，由綠(MIDORI)化學(股)所販售的"DPI-101"、"DPI-102"、"DPI-103"、"DPI-105"、"MPI-103"、"MPI-105"、"BBI-101"、"BBI-102"、"BBI-103"、"BBI-105"、"TPS-101"、"TPS-102"、"TPS-103"、"TPS-105"、"MDS-103"、"MDS-105"、"DTS-102"及"DTS-103"、由Rhodia公司所販售的"PI-2074"等。 These cationic polymerization initiators can be easily obtained from commercially available products. For example, they are indicated by their trade names. Examples include: "KAYARAD (registered trademark) PCI-220" and "KAYARAD (registered trademark) sold by Nippon Kayaku Co., Ltd." (Registered trademark) PCI-620", "UVI-6990" sold by Dow Chemical Company, "UVACURE (registered trademark) 1590" sold by Daicel Cytec (shared), sold by ADEKA (shared) "Adeka optomer (registered trademark) SP-150" and "Adeka optomer (registered trademark) SP-170", "CI-5102", "CIT-1370", "CIT- "1682", "CIP-1866S", "CIP-2048S" and "CIP-2064S", "DPI-101", "DPI-102", "DPI-103" sold by Midori Chemicals Co., Ltd. ", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102" and "DTS-103", sold by Rhodia PI-2074" etc.

此等陽離子聚合起始劑，可以各別單獨使用，也可以混合2種以上而使用。因為在300nm以上的波長區域也有紫外線吸收特性，故硬化性優良，從可以得到有良好的機械強度、密著性之硬化性樹脂組成物的硬化層之觀點而言，係以芳香族鋶鹽為佳。 These cationic polymerization initiators may be used individually or in combination of two or more. Because it also has ultraviolet absorption characteristics in the wavelength region of 300 nm or more, it has excellent curability, and from the viewpoint of obtaining a cured layer of a curable resin composition with good mechanical strength and adhesion, an aromatic saline salt is used as good.

陽離子聚合起始劑的含量，相對於環氧化 合物或氧雜環丁烷化合物等陽離子聚合性化合物之合計100重量份，通常是0.5至20重量份，較佳是1至6重量份。陽離子聚合起始劑的含量少時，硬化變得不充分，且機械強度或第一保護層的接著性會有下降之傾向。另一方面，陽離子聚合起始劑的含量過多時，偏光片的光學性能有下降之可能性。 The content of cationic polymerization initiator, relative to epoxidation The total amount of the cationic polymerizable compound such as the compound or oxetane compound is 100 parts by weight, usually 0.5 to 20 parts by weight, preferably 1 to 6 parts by weight. When the content of the cationic polymerization initiator is small, the hardening becomes insufficient, and the mechanical strength or the adhesion of the first protective layer tends to decrease. On the other hand, if the content of the cationic polymerization initiator is too large, the optical performance of the polarizer may decrease.

[光擴散劑] [Light diffusing agent]

硬化性樹脂組成物是以含有光擴散劑者為佳。光擴散劑是具有擴散光的機能。藉由在形成第一保護層之硬化性樹脂組成物中含有光擴散劑，當第一黏著劑層為含有光擴散劑之擴散黏著劑層時，可以使光擴散劑的含有率變小，可以更提昇偏光板的濕熱耐久性。光擴散劑是以粒子為佳，構成硬化性樹脂組成物的基本聚合物(base polymer)是以折射率不同之粒子為更佳。作為光擴散劑者，可以列舉：由無機化合物所成的粒子或由有機化合物(聚合物)所成的粒子。由於包含丙烯酸系聚合物，構成黏著劑層之基本聚合物，很多顯示有1.4左右的折射率，故在此調配的光擴散劑，只要由其折射率是在1至2左右者中適當選擇就可以。構成第一黏著劑層的基本聚合物與光擴散劑的折射率差，通常是0.01以上，又從液晶顯示裝置的明亮度與辨識性的觀點而言，以設成0.01至0.5為佳。作為光擴散劑而使用之粒子是以球形者為佳，接近單分散者為更佳，平均粒徑在2至6μm左右範圍內的粒子為再更佳。 The curable resin composition preferably contains a light diffusing agent. The light diffusing agent has a function of diffusing light. By including a light diffusing agent in the curable resin composition forming the first protective layer, when the first adhesive layer is a diffusion adhesive layer containing a light diffusing agent, the content rate of the light diffusing agent can be reduced, and Improve the moisture and heat durability of the polarizer. The light diffusing agent is preferably particles, and the base polymer constituting the curable resin composition is preferably particles having different refractive indexes. Examples of the light diffusing agent include particles made of inorganic compounds or particles made of organic compounds (polymers). Since it contains an acrylic polymer and the basic polymer constituting the adhesive layer, many show a refractive index of about 1.4, so the light diffusing agent formulated here can be selected as long as its refractive index is about 1 to 2 can. The refractive index difference between the basic polymer constituting the first adhesive layer and the light diffusing agent is usually 0.01 or more, and it is preferably set to 0.01 to 0.5 from the viewpoint of the brightness and visibility of the liquid crystal display device. The particles used as the light diffusing agent are preferably spherical ones, more preferably near monodisperse ones, and particles having an average particle diameter in the range of about 2 to 6 μm are even better.

作為由無機化合物所成的粒子者，可以列舉：氧化鋁(折射率1.76)、氧化矽(折射率1.45)等。 Examples of particles made of inorganic compounds include alumina (refractive index 1.76), silicon oxide (refractive index 1.45), and the like.

作為由有機化合物(聚合物)所成的粒子者，可以列舉：三聚氰胺小珠(折射率1.57)、聚甲基丙烯酸甲酯小珠(折射率1.49)、甲基丙烯酸甲酯/苯乙烯共聚合物樹脂小珠(折射率1.50至1.59)、聚碳酸酯小珠(折射率1.55)、聚乙烯小珠(折射率1.53)、聚苯乙烯小珠(折射率1.6)、聚氯乙烯小珠(折射率1.46)、矽酮樹脂小珠(折射率1.46)等。 Examples of particles made of organic compounds (polymers) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), and methyl methacrylate/styrene copolymerization. Resin beads (refractive index 1.50 to 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index) Refractive index 1.46), silicone resin beads (refractive index 1.46), etc.

光擴散劑的調配量，係考慮調配有光擴散劑的第一保護層所需之霧度值、或具有第一保護層之偏光板所適用的液晶顯示裝置之明亮度等，而適當決定，但一般，相對於硬化性樹脂組成物的基本聚合物100重量份，係3至50重量份，較佳是5至45重量份。 The amount of light diffusing agent to be prepared is appropriately determined considering the haze value required for the first protective layer equipped with the light diffusing agent or the brightness of the liquid crystal display device to which the polarizing plate having the first protective layer is applied. However, in general, it is 3 to 50 parts by weight, preferably 5 to 45 parts by weight with respect to 100 parts by weight of the basic polymer of the curable resin composition.

調配有光擴散劑之第一保護層，從確保組裝有偏光板之液晶顯示裝置的明亮度，同時不容易發生顯像的輪廓不清或模糊之觀點而言，第一保護層的霧度是以10至80%為佳，20至60%為更佳。霧度是依JIS K 7105所規定，以(擴散穿透率/全光線穿透率)×100(%)所表示的值。 The first protective layer with a light diffusing agent is blended. From the viewpoint of ensuring the brightness of the liquid crystal display device equipped with a polarizing plate, and at the same time, it is not easy to produce unclear or blurring of the developed image, the haze of the first protective layer is 10 to 80% is better, and 20 to 60% is better. The haze is a value expressed by (diffused transmittance/full light transmittance)×100(%) in accordance with JIS K 7105.

[其他的成分] [Other ingredients]

硬化性樹脂組成物，可依需要而進一步含有光增感劑為佳。藉由含有光增感劑，陽離子聚合及/或是自由基聚合的反應性提高，可以提昇第一保護層的機械強度或第一保護層的密著性。作為光增感劑者，可以列舉：羰基化合 物、有機硫化合物、過硫化物、氧化還原系化合物、偶氮化合物、重氮化合物、鹵素化合物、光還原性色素等。 The curable resin composition may further contain a photosensitizer if necessary. By containing a light sensitizer, the reactivity of cationic polymerization and/or radical polymerization is improved, and the mechanical strength of the first protective layer or the adhesion of the first protective layer can be improved. Examples of photosensitizers include carbonyl compounds Compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, photoreducible dyes, etc.

硬化性樹脂組成物中，也可以添加通常使用在高分子中的公知之高分子添加劑。作為高分子添加劑者，例如，可以列舉：如酚系或胺系的一次抗氧化劑、硫系的二次抗氧化劑、受阻胺系光安定劑(HALS)、二苯甲酮系、苯并***系及苯甲酸酯系的紫外線吸收劑等。 To the curable resin composition, a well-known polymer additive usually used for polymers may be added. Examples of polymer additives include, for example, phenol-based or amine-based primary antioxidants, sulfur-based secondary antioxidants, hindered amine-based light stabilizers (HALS), benzophenone-based, and benzotriazole And benzoate-based ultraviolet absorbers.

硬化性樹脂組成物，也可以含有溶劑。溶劑是考慮到構成硬化性樹脂組成物之成分的溶解性而適當選擇。作為溶劑者，有：如正己烷或環己烷等脂肪族烴類；如甲苯或二甲苯等芳香族烴類；如甲醇、乙醇、丙醇、異丙醇及正丁醇等醇類；丙酮、甲基乙基酮、甲基異丁基酮及環己酮等酮類；如醋酸甲酯、醋酸乙酯及醋酸丁酯等酯類；如甲基溶纖劑、乙基溶纖劑及丁基溶纖劑等溶纖劑(cellosolve)類；如二氯甲烷或氯仿等鹵化烴類等。溶劑的含量是以成為硬化性樹脂組成物容易塗布的黏度之方式而適當決定。 The curable resin composition may contain a solvent. The solvent is appropriately selected in consideration of the solubility of the components constituting the curable resin composition. As the solvent, there are: aliphatic hydrocarbons such as n-hexane or cyclohexane; aromatic hydrocarbons such as toluene or xylene; alcohols such as methanol, ethanol, propanol, isopropanol and n-butanol; acetone , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; such as methyl acetate, ethyl acetate and butyl acetate and other esters; such as methyl cellosolve, ethyl cellosolve and Cellosolves such as butyl cellosolve; halogenated hydrocarbons such as dichloromethane or chloroform. The content of the solvent is appropriately determined in such a way that it becomes a viscosity that is easy to apply to the curable resin composition.

硬化性樹脂組成物，也可以含有調平劑。在偏光片或基材上塗布硬化性樹脂組成物之際，當對偏光片或基材上的濕潤性缺乏的情形、或硬化性樹脂組成物的硬化層表面之均勻性差的情形，可藉由添加調平劑，而改善此等情形。作為調平劑者，可以使用矽酮系、氟系、聚醚系、丙烯酸共聚合物系、鈦酸鹽系等各種化合物。此等調平劑，可以分別單獨使用，也可以混合2種以上而使用。 The curable resin composition may contain a leveling agent. When coating a polarizer or substrate with a curable resin composition, when the wettability to the polarizer or substrate is lacking, or the uniformity of the surface of the cured layer of the curable resin composition is poor, the Add leveling agents to improve these situations. As the leveling agent, various compounds such as silicone-based, fluorine-based, polyether-based, acrylic copolymer-based, and titanate-based compounds can be used. These leveling agents may be used alone or in combination of two or more.

調平劑的含量，相對於活性能量線硬化性化合物100重量份，係以0.01至1重量份為佳，以0.1至0.7重量份為較佳，以0.2至0.5重量份為更佳。含量未達0.01重量份時，濕潤性或表面的均勻性之改善有不充分之傾向，又，此之添加量超過1重量份時，第一保護層的密著性有下降之傾向。 The content of the leveling agent is preferably 0.01 to 1 part by weight, preferably 0.1 to 0.7 part by weight, and more preferably 0.2 to 0.5 part by weight with respect to 100 parts by weight of the active energy ray-curable compound. When the content is less than 0.01 parts by weight, the improvement in wettability or surface uniformity tends to be insufficient, and when the amount added exceeds 1 part by weight, the adhesion of the first protective layer tends to decrease.

[第二保護層] [Second protective layer]

本發明的偏光板中，是以在偏光片中之與積層有第一保護層之側為相反側之側具有第二保護層者為佳。第二保護層是以積層在偏光片者為佳。作為第二保護層者，可以列舉：與上述的第一保護層同樣為將硬化性樹脂組成物硬化而得到之層，或是熱可塑性樹脂薄膜。當第二保護層，係與上述的第一保護層同樣為將硬化性樹脂組成物硬化而得到之層的情形，形成第一保護層及第二保護層之硬化性樹脂組成物，可以是相同之硬化性樹脂組成物，也可以是不同之硬化性樹脂組成物。第二保護層，係將硬化性樹脂組成物硬化而得到之層的情形，偏光板是在兩面無保護薄膜的偏光板，第二保護層是熱可塑性樹脂薄膜的情形，偏光板是在單面具有保護薄膜之偏光板。本發明的偏光板中，第二保護層是以熱可塑性樹脂薄膜為佳。 In the polarizing plate of the present invention, it is preferable that the polarizer has a second protective layer on the side opposite to the side where the first protective layer is deposited. The second protective layer is preferably laminated on the polarizer. Examples of the second protective layer include a layer obtained by curing the curable resin composition as in the first protective layer described above, or a thermoplastic resin film. When the second protective layer is a layer obtained by curing the curable resin composition in the same way as the first protective layer described above, the curable resin composition forming the first protective layer and the second protective layer may be the same The curable resin composition may be a different curable resin composition. The second protective layer is a layer obtained by hardening the curable resin composition. The polarizing plate is a polarizing plate without protective films on both sides. The second protective layer is a thermoplastic resin film. The polarizing plate is on one side. Polarizing plate with protective film. In the polarizing plate of the present invention, the second protective layer is preferably a thermoplastic resin film.

作為熱可塑性樹脂薄膜者，可以使用：醋酸纖維素系樹脂、環烯烴系樹脂、聚烯烴系樹脂、丙烯酸系樹脂、聚醯亞胺系樹脂、聚碳酸酯系樹脂、聚酯系樹脂等，可以使 用在該領域中以往以來作為保護薄膜的形成材料而廣範使用之材料所形成的薄膜。從量產性及接著性的觀點而言，熱可塑性樹脂薄膜是以醋酸纖維素系樹脂薄膜或是環烯烴系樹脂薄膜為佳。又，從設置表面處理層的容易性及光學特性為良好者之觀點而言，以醋酸纖維素系樹脂薄膜為更佳。 As the thermoplastic resin film, cellulose acetate resin, cycloolefin resin, polyolefin resin, acrylic resin, polyimide resin, polycarbonate resin, polyester resin, etc. can be used. Make A thin film formed of materials widely used in the field as a protective film forming material in the past. From the viewpoint of mass productivity and adhesiveness, the thermoplastic resin film is preferably a cellulose acetate-based resin film or a cycloolefin-based resin film. In addition, from the viewpoint of ease of providing the surface treatment layer and good optical characteristics, a cellulose acetate-based resin film is more preferable.

醋酸纖維素系樹脂薄膜，係由纖維素的部分或是完全醋酸酯化物所成的薄膜，可以列舉：三醋酸纖維素薄膜、二乙醯纖維素薄膜等。 The cellulose acetate-based resin film is a film made of a part of cellulose or a complete acetate, and examples thereof include a cellulose triacetate film and a diacetyl cellulose film.

在醋酸纖維素系樹脂薄膜中，可以使用市售品。作為適合的市售品者，可以列舉：富士FILM(股)公司所販售的"FUJITAC(註冊商標)TD 80"、"FUJITAC(註冊商標)TD 80UF"、"FUJITAC(註冊商標)TD 80 UZ"、柯尼卡美能達精密光學(股)公司所販售的"KC8UX 2M"、"KC8UY"(以上，都是商品名)等。 A commercially available product can be used for the cellulose acetate resin film. Examples of suitable commercial products include "FUJITAC (registered trademark) TD 80", "FUJITAC (registered trademark) TD 80UF" and "FUJITAC (registered trademark) TD 80 UZ sold by Fuji FILM Corporation. ", "KC8UX 2M", "KC8UY" (the above are all brand names) sold by Konica Minolta Precision Optics Co., Ltd.

環烯烴系樹脂，係指含有源自如降冰片烯、多環降冰片烯系單體等具有環狀烯烴(環烯烴)之單體的單元之熱可塑性的樹脂。環烯烴系樹脂，可以係上述的環烯烴之開環聚合物、使用2種以上的環烯烴之開環共聚合物的氫化物，也可以是環烯烴與鏈狀烯烴、具有乙烯基等之芳香族化合物等的加成聚合物。又，熱可塑性樹脂薄膜是貼合在偏光片時，從提高與偏光片的密著性之觀點而言，導入極性基者也是有效。 The cycloolefin-based resin refers to a thermoplastic resin containing a unit derived from a monomer having a cyclic olefin (cycloolefin) such as norbornene, polycyclic norbornene-based monomer. Cycloolefin-based resins, which may be the above-mentioned ring-opening polymers of cycloolefins, hydrogenated products of ring-opening copolymers using two or more types of cycloolefins, or aromatics such as cycloolefins and chain olefins, and having vinyl groups Addition polymers of family compounds, etc. In addition, when the thermoplastic resin film is bonded to the polarizer, it is also effective to introduce a polar group from the viewpoint of improving the adhesion with the polarizer.

環烯烴、與鏈狀烯烴及/或是具有乙烯基之 芳香族化合物的共聚合物構成保護薄膜時，作為鏈狀烯烴者，可以列舉：乙烯，丙烯等，作為具有乙烯基的芳香族化合物者，可以列舉：苯乙烯、α-甲基苯乙烯、核烷基取代苯乙烯等。在如此之共聚合物中，由環烯烴所成單體的單元可以是在50莫耳%以下(較佳是15至50莫耳%)。在此種三元共聚合物中，相對於構成聚合物之全單元數100莫耳%，由鏈狀烯烴所成的單體之單元，通常是5至80莫耳%，由具有乙烯基之芳香族化合物而成的單體之單元，通常是5至80莫耳%。 Cyclic olefins, and chain olefins and/or vinyl When the copolymer of the aromatic compound constitutes the protective film, examples of the chain olefin include ethylene and propylene, and examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, and core Alkyl substituted styrene, etc. In such a copolymer, the unit of the monomer made from cycloolefin may be 50 mol% or less (preferably 15 to 50 mol%). In such a ternary copolymer, the unit of the monomer composed of chain olefin is usually 5 to 80 mol% relative to 100 mol% of the total units constituting the polymer. Units of monomers made from aromatic compounds are usually 5 to 80 mol%.

環烯烴系樹脂中，可以使用市售品，可以適當地使用："TOPAS(註冊商標)"[Topas Advanced Polymers GmbH公司製]、"ARTON(註冊商標)"[JSR(股)製]、"ZEONOR(註冊商標)"、"ZEONEX(註冊商標)"[以上，日本ZEON(股)製]、"APEL(註冊商標)”[三井化學(股)製](以上，都是商品名)等。在將如此之環烯烴系樹脂製膜而作成薄膜之際，可適當使用溶劑鑄造法、溶融擠壓法等公知方法。也可以使用"Escena(註冊商標)"、"SCA 40"[以上，積水化學工業(股)製]，"Zeonor Film(註冊商標)"[日本ZEON(股)公司製]等市售品的薄膜。 Among cycloolefin-based resins, commercially available products can be used, and can be appropriately used: "TOPAS (registered trademark)" [manufactured by Topas Advanced Polymers GmbH], "ARTON (registered trademark)" [manufactured by JSR (stock)], "ZEONOR" (Registered trademark)", "ZEONEX (registered trademark)" [above, Japan ZEON (stock) system], "APEL (registered trademark)" [Mitsui Chemical (stock) system] (above, are trade names), etc. When such a cycloolefin-based resin is formed into a film, a known method such as a solvent casting method and a melt extrusion method can be suitably used. Films of commercially available products such as "Escena (registered trademark)", "SCA 40" [above, manufactured by Sekisui Chemical Industry Co., Ltd.], and "Zeonor Film (registered trademark)" [made by Japan Zeon Corporation] can also be used. .

上述的環烯烴系樹脂薄膜，可以是經單軸延伸或是雙軸延伸者。此情形的延伸倍率，通常是1.1至5倍，較佳是1.1至3倍。 The above-mentioned cycloolefin-based resin film may be uniaxially stretched or biaxially stretched. The extension magnification in this case is usually 1.1 to 5 times, preferably 1.1 to 3 times.

聚烯烴系樹脂，係將如乙烯或丙烯等鏈狀烯烴當作主要單體之聚合物，可以是均聚物，也可以是共 聚合物。其中，以丙烯的均聚物或丙烯與少量的乙烯共聚合之共聚合物為佳。 Polyolefin-based resins are polymers that use chain olefins such as ethylene or propylene as the main monomers, either homopolymers or co-polymers polymer. Among them, a homopolymer of propylene or a copolymer of propylene copolymerized with a small amount of ethylene is preferred.

丙烯酸系樹脂，係將甲基丙烯酸甲酯當作主要單體之聚合物，可以是甲基丙烯酸甲酯的均聚物，也可以是甲基丙烯酸甲酯與如丙烯酸甲酯等丙烯酸酯的共聚合物。 Acrylic resin is a polymer that uses methyl methacrylate as the main monomer. It can be a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and acrylates such as methyl acrylate. polymer.

聚醯亞胺系樹脂，係在主鏈中具有醯亞胺鍵之聚合物，可以列舉：將四羧酸二酐與二胺聚合，作成聚醯亞胺的前驅物之聚醯胺酸(polyamic acid)之後，藉由脫水/環化(醯亞胺化)反應而得到者。 Polyimide resin is a polymer having an amide imide bond in the main chain. Examples include: polyamic acid (polyamic acid) which is a precursor of polyimide by polymerizing tetracarboxylic dianhydride and diamine. After acid), it is obtained by dehydration/cyclization (amidation) reaction.

聚碳酸酯系樹脂，係在主鏈中具有羧酸酯鍵之聚合物，可以列舉：藉由雙酚A與光氣的縮合聚合而得到者。 The polycarbonate-based resin is a polymer having a carboxylate bond in the main chain, and examples thereof include those obtained by condensation polymerization of bisphenol A and phosgene.

聚酯系樹脂，係藉由二元酸與二元醇的縮聚合而得到之聚合物，可以列舉聚對苯二甲酸乙二酯等。 The polyester resin is a polymer obtained by polycondensation polymerization of a dibasic acid and a glycol, and polyethylene terephthalate and the like can be mentioned.

又，熱可塑性樹脂薄膜中之遠離偏光片之側的面，可以實施防眩處理、硬塗處理、抗靜電處理、抗反射處理等表面處理，也可以形成由液晶性化合物、其他的高分子量化合物等而成之塗布層。 In addition, the surface of the thermoplastic resin film away from the polarizer can be subjected to surface treatments such as anti-glare treatment, hard coating treatment, antistatic treatment, and anti-reflection treatment. It can also be formed of liquid crystal compounds and other high molecular weight compounds. The coating layer.

作為第二保護層者，當採用將硬化性樹脂組成物硬化而得到之層時，第二保護層的厚度，係以0.1至10μm為佳，以1至5μm為更佳。第二保護層的厚度未達0.1μm時，會有變得不能充分抑制光學性能的下降之情形，另一方面，超過10μm時，有偏光板的薄型輕量化 的效果會變小之情形。 As the second protective layer, when a layer obtained by curing a curable resin composition is used, the thickness of the second protective layer is preferably 0.1 to 10 μm, more preferably 1 to 5 μm. When the thickness of the second protective layer is less than 0.1 μm, the deterioration of optical performance may not be sufficiently suppressed. On the other hand, when it exceeds 10 μm, the thin and light polarizing plate is reduced The effect will become smaller.

作為第二保護層者，當採用熱可塑性樹脂薄膜時，通常是5至100μm，較佳是10至80μm，更佳是50μm以下。熱可塑性樹脂薄膜的厚度，太薄時強度會下降，加工性有變差的傾向，太厚時，有透明性下降，或偏光板的重量變大之傾向。 As the second protective layer, when a thermoplastic resin film is used, it is usually 5 to 100 μm, preferably 10 to 80 μm, and more preferably 50 μm or less. When the thickness of the thermoplastic resin film is too thin, the strength decreases, and the processability tends to be deteriorated. When it is too thick, the transparency decreases, or the weight of the polarizing plate tends to increase.

[黏著劑層] [Adhesive layer]

本發明的偏光板，在第一保護層中之遠離偏光片之側的面積層有第一黏著劑層。又本發明的偏光板，係以在第二保護層中之遠離偏光片之側具有第二黏著劑層為佳。第二黏著劑層是以積層在第二保護層為更佳。具有第二黏著劑層之偏光板，係可隔著此種第二黏著劑層，而直接貼合在液晶單元。本說明書中，有時將第一黏著劑層與第二黏著劑層一同稱作黏著劑層。 The polarizing plate of the present invention has a first adhesive layer on the area layer of the first protective layer on the side away from the polarizer. In addition, the polarizing plate of the present invention preferably has a second adhesive layer on the side of the second protective layer away from the polarizer. The second adhesive layer is preferably laminated on the second protective layer. The polarizing plate with the second adhesive layer can be directly attached to the liquid crystal cell via this second adhesive layer. In this specification, the first adhesive layer and the second adhesive layer are sometimes referred to as an adhesive layer.

形成黏著劑層之黏著劑組成物，係以含有丙烯酸系聚合物、矽酮系聚合物、聚酯、聚胺酯、聚醚等基本聚合物者為佳。 The adhesive composition forming the adhesive layer is preferably one containing basic polymers such as acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers.

其中，如同將丙烯酸系聚合物當作基本聚合物之黏著劑(丙烯酸系黏著劑)，更佳係選擇並使用光學透明性或接著性優異，且保持有適度的濕濡性或凝集力，並具有耐候性或耐熱性等，在加熱或加濕的條件下不會產生有浮起或剝離等剝離問題者。作為丙烯酸系黏著劑者，將甲基、乙基及丁基等碳數為20以下的烷基鍵結於(甲基)丙烯酸的氧 基而成之烷酯、與(甲基)丙烯酸或(甲基)丙烯酸羥基乙酯等丙烯酸系單體調配且聚合而成之丙烯酸系共聚合物，係有用於作為基本聚合物。作為基本聚合物的玻璃轉移溫度者，係以25℃以下為佳，以0℃以下為更佳。又，基本聚合物的重量平均分子量是以100000以上為佳。 Among them, as an adhesive (acrylic adhesive) that uses an acrylic polymer as a basic polymer, it is more preferable to select and use an optical transparency or excellent adhesion, and maintain a moderate wettability or cohesion, and It has weather resistance, heat resistance, etc., and does not cause peeling problems such as floating or peeling under heating or humidification. As an acrylic adhesive, a methyl group, an ethyl group, a butyl group and the like having a carbon number of 20 or less are bonded to the oxygen of (meth)acrylic acid Acrylic copolymers prepared by blending and polymerizing alkyl esters and acrylic monomers such as (meth)acrylic acid or hydroxyethyl (meth)acrylate are useful as basic polymers. The glass transition temperature of the basic polymer is preferably 25°C or lower, and more preferably 0°C or lower. In addition, the weight average molecular weight of the basic polymer is preferably 100,000 or more.

黏著劑層，係可藉由在如甲苯或醋酸乙酯等有機溶劑中將黏著劑組成物溶解或是分散並調製成10至40重量%的溶液，事先在剝離薄膜上形成黏著劑層後，將其移附到保護薄膜上而形成黏著劑層。在黏著劑組成物中，除了上述基本聚合物之外，一般是調配有交聯劑。亦以調配矽烷偶合劑為佳。黏著劑層的厚度，雖因應其接著力等而決定，但通常是1至50μm。 The adhesive layer can be prepared by dissolving or dispersing the adhesive composition in an organic solvent such as toluene or ethyl acetate and preparing a solution of 10 to 40% by weight. After forming the adhesive layer on the release film in advance, Attach it to the protective film to form an adhesive layer. In the adhesive composition, in addition to the above basic polymer, a crosslinking agent is generally blended. It is also better to prepare silane coupling agent. Although the thickness of the adhesive layer is determined by its adhesive force, etc., it is usually 1 to 50 μm.

第一黏著劑層，係以含有光擴散劑之擴散黏著劑層為佳。作為光擴散劑者，可以列舉：與第一保護層可含有之光擴散劑同樣者。 The first adhesive layer is preferably a diffusion adhesive layer containing a light diffusing agent. Examples of the light diffusing agent include the same as the light diffusing agent that can be contained in the first protective layer.

當第一黏著劑層是擴散黏著劑層時，光擴散劑的含有率，可考慮到調配有光擴散劑的第一保護層中所需之霧度值、或具有第一保護層之偏光板適用的液晶顯示裝置之明亮度等而適當決定，但一般而言，相對於黏著劑組成物的基本聚合物100重量份，光擴散劑是3至50重量份，較佳是5至45重量份。 When the first adhesive layer is a diffusion adhesive layer, the content rate of the light diffusing agent can be taken into account the required haze value in the first protective layer equipped with the light diffusing agent, or the polarizing plate with the first protective layer The brightness of the applicable liquid crystal display device is appropriately determined, etc., but generally speaking, the light diffusing agent is 3 to 50 parts by weight, preferably 5 to 45 parts by weight relative to 100 parts by weight of the basic polymer of the adhesive composition .

從在確保組裝有偏光板之液晶顯示裝置的明亮度，同時不易產生顯像的輪廓不清或模糊之觀點而言，黏著劑層的霧度是以10至80%為佳，以20至60%為 更佳。 From the viewpoint of ensuring the brightness of a liquid crystal display device equipped with a polarizing plate, and at the same time, it is not easy to produce unclear or blurred contours of the developed image, the haze of the adhesive layer is preferably 10 to 80%, preferably 20 to 60 %for Better.

黏著劑組成物，也可以含有：顏料、著色劑、抗氧化劑、紫外線吸收劑等。作為紫外線吸收劑者，可以列舉：水楊酸酯系化合物、二苯甲酮系化合物、苯并***系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物等。 The adhesive composition may also contain pigments, colorants, antioxidants, and ultraviolet absorbers. Examples of the ultraviolet absorber include salicylate-based compounds, benzophenone-based compounds, benzotriazole-based compounds, cyanoacrylate-based compounds, and nickel complex-based compounds.

[偏光片與第二保護層的接著] [Continuation of polarizer and second protective layer]

採用熱可塑性樹脂薄膜作為第二保護層之情形，且積層有第二保護層與偏光片之情形，偏光片與第二保護層，通常是藉由接著劑或是黏著劑貼合。在貼合此等薄膜之際，為了提昇接著性，在偏光片及/或是第二保護層的貼合面，可以適當地實施：電漿處理、電暈處理、紫外線照射處理、火焰處理、皂化處理、溶劑處理等表面處理。作為皂化處理者，可以列舉：在如氫氧化鈉或氫氧化鉀等鹼性水溶液中浸漬之方法。 In the case where a thermoplastic resin film is used as the second protective layer, and the second protective layer and the polarizer are laminated, the polarizer and the second protective layer are usually bonded by an adhesive or an adhesive. When bonding these films, in order to improve the adhesion, the bonding surface of the polarizer and/or the second protective layer can be appropriately implemented: plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, Surface treatment such as saponification treatment and solvent treatment. As the saponification treatment person, a method of immersion in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide can be cited.

作為在偏光片與第二保護層的貼合中所使用之黏著劑者，可以列舉：與在上述黏著劑層中所使用的黏著劑同樣的黏著劑。 Examples of the adhesive used in the bonding of the polarizer and the second protective layer include the same adhesives as those used in the adhesive layer.

作為在偏光片與第二保護層的貼合中所使用之接著劑者，可以列舉：含有活性能量線硬化性化合物之硬化性樹脂組成物(活性能量線硬化性接著劑)，或在水中溶解或是分散有接著劑成分之水系接著劑(水系接著劑)。 Examples of the adhesive used in the bonding of the polarizer and the second protective layer include a curable resin composition (active energy ray-curable adhesive) containing an active energy ray-curable compound, or dissolve in water Or a water-based adhesive (water-based adhesive) in which an adhesive component is dispersed.

作為活性能量線硬化性接著劑者，可以使用與形成前述保護層之硬化性樹脂組成物同樣者。在保護層的形成中使用之硬化性樹脂組成物、與偏光片和第二保護層的貼合中使用之活性能量線硬化性接著劑，可以是相同者，也可以是相異者。 As the active energy ray-curable adhesive, the same as the curable resin composition forming the protective layer can be used. The curable resin composition used for forming the protective layer and the active energy ray curable adhesive used for bonding the polarizer and the second protective layer may be the same or different.

作為水系接著劑者，可以列舉：含有作為主成分的聚乙烯醇系樹脂或胺酯樹脂之接著劑組成物。 Examples of the water-based adhesive include an adhesive composition containing a polyvinyl alcohol-based resin or urethane resin as a main component.

當水系接著劑含有聚乙烯醇系樹脂作為主成分時，作為聚乙烯醇系樹脂者，除了將醋酸乙烯酯的均聚物之聚醋酸乙烯酯經皂化處理而得到之乙烯醇均聚物之外，尚可以列舉：醋酸乙烯酯與可和其共聚合之其他單體的共聚合物等。作為和醋酸乙烯酯共聚合之其他單體者，可以列舉：不飽和羧酸、不飽和磺酸、烯烴、乙烯基醚、具有銨基之丙烯醯胺等。含有水系接著劑之聚乙烯醇系樹脂，係以有適度的聚合度者為佳，例如，當設為4重量%濃度的水溶液時，黏度是以4至50mPa．sec為佳，以6至30mPa．sec為更佳。 When the water-based adhesive contains a polyvinyl alcohol-based resin as the main component, as the polyvinyl alcohol-based resin, in addition to the vinyl alcohol homopolymer obtained by saponification of polyvinyl acetate homopolymer polyvinyl acetate It can also be exemplified by copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamide having an ammonium group. The polyvinyl alcohol-based resin containing the water-based adhesive is preferably one having a moderate degree of polymerization. For example, when it is set to a 4% by weight aqueous solution, the viscosity is 4 to 50 mPa. sec is better, 6 to 30mPa sec is better.

又，水系接著劑亦以含有經改質的聚乙烯醇系樹脂為佳。作為改質聚乙烯醇系樹脂者，可以列舉：經乙醯乙醯基改質的聚乙烯醇系樹脂、經陰離子改質的聚乙烯醇系樹脂、經陽離子改質的聚乙烯醇系樹脂等。水系接著劑含有如此之經改質的聚乙烯醇系樹脂時，容易得到提昇接著劑層的耐水性之效果。 In addition, the water-based adhesive preferably contains a modified polyvinyl alcohol-based resin. Examples of modified polyvinyl alcohol-based resins include polyvinyl alcohol-based resins modified with acetylacetoyl groups, polyvinyl alcohol-based resins modified with anions, and polyvinyl alcohol-based resins modified with cations. . When the water-based adhesive contains such a modified polyvinyl alcohol-based resin, the effect of improving the water resistance of the adhesive layer is easily obtained.

水系接著劑，也可以含有2種以上之上述改 質聚乙烯醇系樹脂，又，也可以含有未改質的聚乙烯醇系樹脂(具體上，聚醋酸乙烯酯的完全或是部分皂化物)及上述改質聚乙烯醇系樹脂之兩者。 Water-based adhesives may also contain two or more of the above The quality polyvinyl alcohol-based resin may also contain both the unmodified polyvinyl alcohol-based resin (specifically, completely or partially saponified polyvinyl acetate) and the above-mentioned modified polyvinyl alcohol-based resin.

構成水系接著劑之聚乙烯醇系樹脂，係可以使用市售品。例如，可以列舉：由Kuraray(股)公司所販售的"PVA-117H"、"KL-318"、"KM-118"及"CM-318"、由日本合成化學工業(股)所販售的"Gohsenol(註冊商標)NH-20"、"Gohsefimer(註冊商標)Z"系列、"Gohsefimer(註冊商標)K-210"及"Gohsenal(註冊商標)T-330"(以上，都是商品名)等。 As the polyvinyl alcohol resin constituting the water-based adhesive, a commercially available product can be used. For example, "PVA-117H", "KL-318", "KM-118", and "CM-318" sold by Kuraray Co., Ltd., and sold by Japan Synthetic Chemical Industry Co., Ltd. "Gohsenol (registered trademark) NH-20", "Gohsefimer (registered trademark) Z" series, "Gohsefimer (registered trademark) K-210" and "Gohsenal (registered trademark) T-330" (the above are all trade names )Wait.

含有聚乙烯醇系樹脂當作主成分的水系接著劑，也可以含有交聯劑。將可作為交聯劑之化合物依官能基類別而揭示時，有：在分子內至少具有2個異氰酸基(-NCO)之異氰酸酯化合物；在分子內至少具有2個環氧基之環氧化合物；單-或是雙-醛；有機鈦化合物；如鎂、鈣、鐵、鎳、鋅及鋁等二價或是三價金屬之無機鹽；乙醛酸的金屬鹽；羥甲基三聚氰胺等。 A water-based adhesive containing a polyvinyl alcohol-based resin as a main component may also contain a cross-linking agent. When the compound that can be used as a crosslinking agent is disclosed according to the functional group type, there are: an isocyanate compound having at least 2 isocyanate groups (-NCO) in the molecule; an epoxy having at least 2 epoxy groups in the molecule Compounds; mono- or di-aldehydes; organic titanium compounds; inorganic salts of divalent or trivalent metals such as magnesium, calcium, iron, nickel, zinc, and aluminum; metal salts of glyoxylic acid; methylolmelamine, etc. .

此等交聯劑之中，可適當使用以水溶性的聚醯胺環氧樹脂為首的環氧化合物、或醛類、羥甲基三聚氰胺、乙醛酸的鹼金屬或是鹼土族金屬鹽等。 Among these crosslinking agents, an epoxy compound headed by a water-soluble polyamide epoxy resin, or an aldehyde, methylolmelamine, an alkali metal of glyoxylic acid, or an alkaline earth metal salt or the like can be suitably used.

交聯劑，係以與聚乙烯醇系樹脂一起溶解在水中而形成接著劑者為佳。但是，因水溶液中的交聯劑量只要有極少量即可，故相對於水，只要係至少具有0.1重量%左右的溶解度者，就可以作為交聯劑而使用。 The crosslinking agent is preferably one that is dissolved in water together with the polyvinyl alcohol-based resin to form an adhesive. However, since the amount of the crosslinking agent in the aqueous solution should be a very small amount, it can be used as a crosslinking agent as long as it has a solubility of at least about 0.1% by weight relative to water.

交聯劑的含量，雖為因應聚乙烯醇系樹脂的種類等而適當設計者，但相對於聚乙烯醇系樹脂100重量份，通常是5至60重量份，較佳是10至50重量份。在此範圍調配交聯劑時，可得到良好之接著性。交聯劑的調配量太多時，交聯劑的反應在短時間內進行，接著劑有早期膠化之傾向，結果，適用期(pot life)變成極短，在工業使用上有困難。 Although the content of the cross-linking agent is appropriately designed according to the type of the polyvinyl alcohol resin, etc., it is usually 5 to 60 parts by weight, preferably 10 to 50 parts by weight relative to 100 parts by weight of the polyvinyl alcohol resin. . When the crosslinking agent is formulated within this range, good adhesion can be obtained. When the formulation amount of the crosslinking agent is too large, the reaction of the crosslinking agent proceeds in a short time, and the adhesive tends to gel at an early stage. As a result, the pot life becomes extremely short, which makes it difficult for industrial use.

水系接著劑，在不防礙本發明的效果之範圍，可以含有矽烷偶合劑、可塑劑、抗靜電劑、微粒子等以往公知的適當之添加劑。 The water-based adhesive may contain a conventionally known appropriate additive such as a silane coupling agent, a plasticizer, an antistatic agent, and fine particles within a range that does not hinder the effects of the present invention.

乾燥或是硬化後得到的接著劑層之厚度，通常是0.01至5μm，但當使用水系接著劑時，係可以設成1μm以下。另一方面，即使當使用活性能量線硬化性接著劑時，以設成2μm以下為佳，以設成1μm以下為更佳。接著劑層太薄時，有接著變不充分之虞，接著劑層太厚時，偏光板的外觀有產生不良之可能性。 The thickness of the adhesive layer obtained after drying or hardening is usually 0.01 to 5 μm, but when an aqueous adhesive is used, it can be set to 1 μm or less. On the other hand, even when the active energy ray-curable adhesive is used, it is preferably set to 2 μm or less, and more preferably set to 1 μm or less. If the adhesive layer is too thin, the adhesive may become insufficient, and if the adhesive layer is too thick, the appearance of the polarizing plate may be defective.

[機能性樹脂層] [Functional resin layer]

本發明的偏光板，係在前述第一黏著劑層中之與第一保護層側為相反側的面積層有機能性樹脂層。機能性樹脂層，係以成為本發明的偏光板之最外層為佳。機能性樹脂層，係指含有對偏光板賦予各種光學機能之樹脂薄膜之層，作為此種樹脂薄膜者，可以列舉：相位差薄膜、亮度提昇薄膜等。機能性樹脂層是以提昇亮度薄膜為佳。 The polarizing plate of the present invention is an organic resin layer having an area layer on the side opposite to the first protective layer side of the first adhesive layer. The functional resin layer is preferably the outermost layer of the polarizing plate of the present invention. The functional resin layer refers to a layer containing a resin film that imparts various optical functions to the polarizing plate. Examples of such resin films include retardation films and brightness enhancement films. The functional resin layer is preferably a brightness enhancement film.

相位差薄膜是以由液晶單元所致之相位差的補償等當作目的來使用。作為相位差薄膜者，可以列舉：由經延伸的樹脂薄膜而成的雙折射性薄膜、配向固定有盤狀液晶或向列型液晶之薄膜、在薄膜基材上所形成之上述的液晶層等。作為支撐液晶層之薄膜基材者，係以三醋酸纖維素等纖維素系薄膜為佳。 The retardation film is used for the purpose of compensation of the retardation caused by the liquid crystal cell. Examples of the retardation film include a birefringent film made of an extended resin film, a film in which a discotic liquid crystal or a nematic liquid crystal is fixed, and the above-mentioned liquid crystal layer formed on a film substrate, etc. . As the film substrate supporting the liquid crystal layer, a cellulose-based film such as cellulose triacetate is preferable.

作為形成雙折射性薄膜之樹脂者，可以列舉：聚碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、如聚丙烯等聚烯烴、聚對苯二甲酸乙二酯、聚芳酯、聚醯胺等。延伸是以單軸或雙軸等適當方式而處理即可。又，可以是已藉由在與熱收縮性薄膜的接著下施加收縮力及/或是延伸力而控制薄膜的厚度方向之折射率的雙折射性薄膜。又，相位差板，係可將控制寬頻帶化等光學特性當作目的，而組合並使用2片以上者。 Examples of resins that form birefringent films include polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polyolefins such as polypropylene, polyethylene terephthalate, and polyaromatic Ester, polyamide, etc. The extension can be processed in an appropriate manner such as uniaxial or biaxial. In addition, it may be a birefringent film in which the refractive index in the thickness direction of the film has been controlled by applying shrinkage force and/or elongation force under the heat shrinkable film. In addition, the phase difference plate can be used in combination with two or more for the purpose of controlling optical characteristics such as widening of the band.

亮度提昇薄膜是以提昇亮度為目的而組裝到液晶顯示裝置中。作為亮度提昇薄膜者，可以列舉：將複數片折射率的異向性互不相同之薄膜積層，並以於反射率產生異向性之方式而設計的反射型偏光分離薄片、在薄膜基材上支撐有膽固醇型液晶聚合物的配向薄膜或其配向液晶層之圓偏光分離薄片等。 The brightness enhancement film is assembled into the liquid crystal display device for the purpose of improving brightness. Examples of the brightness enhancement film include a reflective polarizing separation sheet designed by laminating a plurality of thin films with different refractive index anisotropies and designed to generate anisotropy in reflectivity, and on a film substrate An alignment film supporting a cholesterol-type liquid crystal polymer or a circularly polarized separation sheet of the alignment liquid crystal layer, etc.

本發明的偏光板中，可以積層1種機能性樹脂薄膜，也可以積層2種以上的機能性樹脂薄膜。積層2種以上的機能性樹脂薄膜之際的順序是無特別限制。 In the polarizing plate of the present invention, one kind of functional resin film may be laminated, or two or more kinds of functional resin films may be laminated. The order of stacking two or more types of functional resin films is not particularly limited.

[偏光板的製造方法] [Manufacturing method of polarizing plate]

本發明的偏光板，可以藉由含有以下的步驟(i)至(iii)之方法而製造。又，步驟(i)及步驟(ii)的順序是無限制，也可以先進行步驟(ii)，也可以同時進行此等步驟。 The polarizing plate of the present invention can be manufactured by the method including the following steps (i) to (iii). In addition, the order of step (i) and step (ii) is not limited, and step (ii) may be performed first, or these steps may be performed simultaneously.

步驟(i)在偏光片的單面積層第一保護層的步驟，步驟(ii)在機能性樹脂層的單面積層第一黏著劑層的步驟，步驟(iii)將前述第一保護層與前述第一黏著劑層貼合的步驟。 Step (i) the step of layering the first protective layer on the single area of the polarizer, step (ii) the step of layering the first adhesive layer on the single area of the functional resin layer, step (iii) The aforementioned step of bonding the first adhesive layer.

又，也可在偏光片的一側之面，依序積層第一保護層、第一黏著劑層及機能性樹脂層，而製造本發明的偏光板。以下，主要是說明藉由依序含有步驟(i)至(iii)之方法而製造本發明的偏光板之方法，但製造方法並不限於此方法。 In addition, the polarizing plate of the present invention may be manufactured by sequentially laminating a first protective layer, a first adhesive layer, and a functional resin layer on one side of the polarizer. The following mainly describes the method of manufacturing the polarizing plate of the present invention by sequentially including the steps (i) to (iii), but the manufacturing method is not limited to this method.

[步驟(i)] [Step (i)]

上述的步驟(i)中，係藉由包含對基材形成塗布層的步驟、塗布層貼合步驟、塗布層硬化步驟及除去基材之步驟，而在偏光片層的單面積層保護層。 In the above step (i), a protective layer is formed on the single-area layer of the polarizer layer by including a step of forming a coating layer on the substrate, a coating layer bonding step, a coating layer curing step, and a substrate removing step.

對基材形成塗布層的步驟中，首先在基材上，塗佈會形成第一保護層之含有活性能量線硬化性化合物的硬化性樹脂組成物。因應需要而進行乾燥，在基材表面設置硬化性樹脂組成物的塗布層。在此，作為基材者， 除了前述基材之外，也可以使用金屬帶、玻璃板等。又基材的硬化性樹脂組成物所塗佈之表面，可以預先實施剝離處理。作為形成第一保護層之含有活性能量線硬化性化合物的硬化性樹脂組成物之塗佈方法者，可以列舉：藉由刮刀(doctor blade)、線桿、模具塗布機、逗號塗布機(comma coater)、凹版塗佈機等而塗佈之方法。作為與上述的塗佈方法不同之其他的方法者，可以列舉：在偏光片與基材之間，滴下上述硬化性樹脂組成物之後，以滾筒等而加壓並均勻地擠壓擴展的方法。在此方法之中，作為滾筒的材質者，可以使用金屬或橡膠等。 In the step of forming a coating layer on a substrate, first, a curable resin composition containing an active energy ray-curable compound that will form a first protective layer is coated on the substrate. If necessary, drying is performed, and a coating layer of the curable resin composition is provided on the surface of the base material. Here, as the substrate, In addition to the aforementioned base materials, metal tapes, glass plates, and the like can also be used. In addition, the surface to which the curable resin composition of the base material is applied may be subjected to a peeling treatment in advance. Examples of a method for applying the curable resin composition containing the active energy ray-curable compound to form the first protective layer include doctor blade, wire rod, die coater, and comma coater. ), gravure coater and other methods of coating. As another method different from the above-mentioned coating method, a method in which the curable resin composition is dropped between the polarizer and the base material, and then pressed with a roller or the like and uniformly squeezed and spread. In this method, as the material of the drum, metal, rubber, or the like can be used.

塗布層貼合步驟，係將上述的塗佈層形成步驟中在基材上所形成之塗布層與偏光片貼合，製作依偏光片/塗布層/基材的順序所積層之積層體。 In the coating layer bonding step, the coating layer formed on the substrate in the coating layer forming step and the polarizer are bonded together to produce a layered body stacked in the order of polarizer/coating layer/substrate.

塗布層硬化步驟中，針對此積層體，例如，藉由從基材側照射可見光線、紫外線、X射線、電子束等活性能量線或是加熱，而使硬化性樹脂組成物的塗布層硬化並形成保護層。藉由照射活性能量線而進行會形成保護層之硬化性樹脂組成物之硬化時，作為所利用的光源者，係以使用在波長400nm以下有發光分布者為佳。作為此種光源者，可以列舉：低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵素燈等。活性能量線的光照射強度，係可以依照射之組成物的不同而異，但對光自由基聚合起始劑及/或是光陽離子聚合起始劑的活性化有效的波長區域之照射強度是 以10至2500mW/cm²為佳。光照射強度未達10mW/cm²時，反應時間會變太長，又，超過2500mW/cm²時，由於來自燈的輻射熱及硬化性樹脂組成物或接著劑組成物的聚合時之發熱，而會有產生硬化性樹脂組成物或接著劑組成物之黃變或偏光片之劣化之可能性。 In the coating layer curing step, for this laminate, for example, by irradiating active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams from the substrate side or heating, the coating layer of the curable resin composition is cured and cured Form a protective layer. When curing the curable resin composition that will form a protective layer by irradiating active energy rays, it is preferable to use a light emission distribution at a wavelength of 400 nm or less as the light source to be used. Examples of such light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halogen lamps. The light irradiation intensity of the active energy rays may vary according to the composition of the irradiation, but the irradiation intensity in the wavelength region effective for activation of the photo radical polymerization initiator and/or photo cationic polymerization initiator is It is preferably 10 to 2500 mW/cm ² . When the light irradiation intensity is less than 10mW/cm ² , the reaction time becomes too long, and when it exceeds 2500mW/cm ² , due to the radiant heat from the lamp and the heat generated during the polymerization of the curable resin composition or the adhesive composition, and There is a possibility of yellowing of the curable resin composition or adhesive composition or deterioration of the polarizer.

對於硬化性樹脂組成物或接著劑組成物的光照射時間，可以依照射之組成物不同而異，但以作為照射強度與照射時間的積而表示的累積光量成為10至2500mJ/cm²之方式設定為佳。此累積光量未達10mJ/cm²時，源自聚合起始劑的活性種之產生會不充分，且可得到的保護層及接著劑層之硬化有變得不充分之可能性。又，累積光量超過2500mJ/cm²時，照射時間會變成非常長，在提高生產性上是不利者。又，活性能量線的照射，是以在偏光片的偏光度及穿透率等各種性能不下降之範圍中進行為佳。 The light irradiation time of the curable resin composition or the adhesive composition may vary depending on the composition irradiated, but the cumulative light amount expressed as the product of irradiation intensity and irradiation time becomes 10 to 2500 mJ/cm ² The setting is better. When the accumulated light amount is less than 10 mJ/cm ² , the generation of the active species derived from the polymerization initiator may be insufficient, and the hardening of the available protective layer and the adhesive layer may become insufficient. In addition, when the accumulated light amount exceeds 2500 mJ/cm ² , the irradiation time becomes very long, which is disadvantageous in improving productivity. In addition, the irradiation of the active energy ray is preferably performed in a range where various performances such as polarization degree and transmittance of the polarizer are not deteriorated.

後續之除去基材之步驟，係除去保護層上的基材。 The subsequent step of removing the substrate removes the substrate on the protective layer.

又，作為進行步驟(i)的其他方法者，也可以列舉：將形成第一保護層之硬化性樹脂組成物直接塗佈在偏光片，藉由照射活性能量線或加熱，而使由硬化性樹脂組成物所成的塗布層硬化，並形成第一保護層之方法。 In addition, as another method of performing step (i), it may also be mentioned that the curable resin composition forming the first protective layer is directly coated on the polarizer, and the curable resin can be cured by irradiating active energy rays or heating. The method of hardening the coating layer formed by the resin composition and forming the first protective layer.

[步驟(ii)] [Step (ii)]

步驟(ii)是在機能性樹脂層積層第一黏著劑層。首先，第一黏著劑層的積層可藉由使用剝離薄膜的方法、在機能 性樹脂層上塗布黏著劑組成物之方法等而進行。使用剝離薄膜之方法，係可藉由在經實施離型處理之剝離薄膜的離型處理面，塗佈黏著劑組成物並形成黏著劑層，將得到之黏著劑層與機能性樹脂層積層而進行。又，在保護薄膜上塗布黏著劑組成物之方法，係可藉由在機能性樹脂層上塗佈黏著劑組成物並形成黏著劑層而進行。此方法是以在得到的黏著劑層積層剝離薄膜而保護第一黏著劑層之表面為佳。 Step (ii) is to laminate the first adhesive layer on the functional resin layer. First, the lamination of the first adhesive layer can be performed by using The method of applying the adhesive composition on the resin layer is performed. The method of using a peeling film can be achieved by applying an adhesive composition on the release processing surface of the peeling film subjected to the release treatment and forming an adhesive layer, and laminating the obtained adhesive layer and a functional resin layer get on. In addition, the method of applying the adhesive composition on the protective film can be performed by applying the adhesive composition on the functional resin layer and forming an adhesive layer. In this method, it is preferable to peel off the film on the obtained adhesive layer to protect the surface of the first adhesive layer.

[步驟(iii)] [Step (iii)]

步驟(iii)是貼合前述第一保護層與前述第一黏著劑層而得到偏光板。又，本發明的偏光板中，以進一步在偏光片中之與第一保護層側為相反側之側依序具有第二保護層及第二黏著劑層為佳。採用硬化性樹脂組成物作為第二保護層時，係可以與形成前述第一保護層之方法同樣的方法，形成第二保護層。又，作為第二保護層而採用熱可塑性樹脂薄膜時，在熱硬化性樹脂薄膜及/或是偏光片的貼合面塗佈上述接著劑，將兩者貼合而可以形成第二保護層。作為積層第二黏著劑層的方法者，可以列舉與積層前述第一黏著劑層之方法同樣的方法。 Step (iii) is to bond the first protective layer and the first adhesive layer to obtain a polarizing plate. In addition, in the polarizing plate of the present invention, it is preferable that the polarizer further has a second protective layer and a second adhesive layer on the side opposite to the first protective layer side. When the curable resin composition is used as the second protective layer, the second protective layer can be formed in the same manner as the method for forming the first protective layer. In addition, when a thermoplastic resin film is used as the second protective layer, the adhesive may be applied to the bonding surface of the thermosetting resin film and/or the polarizer, and the two may be bonded to form the second protective layer. As a method of laminating the second adhesive layer, the same method as the method of laminating the aforementioned first adhesive layer can be cited.

本發明的偏光板是可以適用在液晶單元等而構成液晶顯示裝置。偏光板有第二黏著劑層時，直到使用時為止，在第二黏著劑層側積層上述的剝離薄膜，並保護為佳。作為在此使用之剝離薄膜者，可以列舉：將由聚 對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚碳酸酯、聚芳酯等各種樹脂而成的薄膜當作基材，在與此基材薄膜的黏著劑層之貼合面，經實施如矽酮處理等離型處理者等。在偏光板積層有剝離薄膜時，只要由偏光板將剝離薄膜剝離，並貼合在液晶單元即可。 The polarizing plate of the present invention can be applied to a liquid crystal cell or the like to constitute a liquid crystal display device. When the polarizing plate has a second adhesive layer, it is preferable to deposit the above-mentioned release film on the side of the second adhesive layer until it is used and protect it. As the peeling film used here, there may be cited: Films made of various resins such as ethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, etc. are used as substrates, and are bonded to the adhesive layer of the substrate film , After implementing release treatment such as silicone treatment. When a peeling film is laminated on the polarizing plate, the peeling film is peeled off by the polarizing plate and bonded to the liquid crystal cell.

參照第1圖(a)及第1圖(b)，說明有關本發明的偏光板之層構成的一個例子。第1圖(a)及第1圖(b)是表示本發明之偏光板之一個例子的示意圖。第1圖(a)是依序具有偏光片1、第一保護層21、第一黏著劑層31及機能性樹脂層4之偏光板10。第1圖(b)是依序具有第二黏著劑層32、第二保護層22、偏光片1、第一保護層21、第一黏著劑層31及機能性樹脂層4之偏光板。 An example of the layer configuration of the polarizing plate of the present invention will be described with reference to FIGS. 1(a) and 1(b). Fig. 1 (a) and Fig. 1 (b) are schematic views showing an example of the polarizing plate of the present invention. FIG. 1(a) shows a polarizing plate 10 having a polarizer 1, a first protective layer 21, a first adhesive layer 31, and a functional resin layer 4 in this order. FIG. 1(b) is a polarizing plate having a second adhesive layer 32, a second protective layer 22, a polarizer 1, a first protective layer 21, a first adhesive layer 31, and a functional resin layer 4 in this order.

從在確保組裝有偏光板之液晶顯示裝置的明亮度，同時不容易產生顯像之輪廓不清或模糊之觀點而言，本發明的偏光板的霧度是以10至80%為佳，以20至60%為更佳。本發明的偏光板之霧度，係可藉由適當地選擇第一黏著劑層、第一保護層等組裝進偏光板中之構件的霧度，而調節。 From the viewpoint of ensuring the brightness of the liquid crystal display device equipped with a polarizing plate, and at the same time, it is not easy to produce unclear contours or blurring of the developed image, the haze of the polarizing plate of the present invention is preferably from 10 to 80%. 20 to 60% is better. The haze of the polarizing plate of the present invention can be adjusted by appropriately selecting the haze of the components assembled into the polarizing plate such as the first adhesive layer and the first protective layer.

[液晶顯示裝置] [Liquid crystal display device]

本發明的偏光板可以適合作為構成液晶顯示裝置之偏光板來使用。通常，在液晶顯示裝置中，一對的偏光板是貼合在液晶單元的辨識側與光源側。本發明的液晶顯示裝置所具備的偏光板之至少1個係本發明的偏光板。又， 一對偏光板之中，本發明的偏光板係以配置在光源側的偏光板為佳。在此情形，另一個偏光板係可以使用公知的偏光板。在本發明的偏光板中，藉由於偏光片與第一黏著劑層之間具有第一保護層，變得可提昇密著力。 The polarizing plate of the present invention can be suitably used as a polarizing plate constituting a liquid crystal display device. Generally, in a liquid crystal display device, a pair of polarizing plates are attached to the identification side and the light source side of the liquid crystal cell. At least one of the polarizing plates included in the liquid crystal display device of the present invention is the polarizing plate of the present invention. also, Among the pair of polarizing plates, the polarizing plate of the present invention is preferably a polarizing plate disposed on the light source side. In this case, another polarizing plate system can use a known polarizing plate. In the polarizing plate of the present invention, by having the first protective layer between the polarizer and the first adhesive layer, it becomes possible to improve the adhesion.

又，具有第二黏著劑層之本發明的偏光板，係由於可隔著第二黏著劑層而直接貼附在構成液晶單元之玻璃基板，故有用。欲將具有第二黏著劑層及剝離薄膜之偏光板積層在玻璃基板，只要由該偏光板將剝離薄膜剝離，並將露出之第二黏著劑層面貼合在玻璃基板的表面即可。 In addition, the polarizing plate of the present invention having the second adhesive layer is useful because it can be directly attached to the glass substrate constituting the liquid crystal cell via the second adhesive layer. To laminate a polarizing plate having a second adhesive layer and a peeling film on the glass substrate, the polarizing plate peels off the peeling film, and the exposed second adhesive layer is attached to the surface of the glass substrate.

參照第2圖，更詳細說明本發明的液晶顯示裝置。第2圖是表示本發明的液晶顯示裝置之一個例子的示意圖。第2圖所示之液晶顯示裝置，係背光8與偏光板10隔著背光帶(back light tape)7而貼合。又偏光板10與液晶單元5是隔著偏光板10的圖式中未顯示之第二黏著劑層32而貼合。又，第2圖所示之偏光板6，可以是本發明的偏光板，也可以是公知的偏光板。 The liquid crystal display device of the present invention will be described in more detail with reference to FIG. 2. Fig. 2 is a schematic diagram showing an example of the liquid crystal display device of the present invention. In the liquid crystal display device shown in FIG. 2, the backlight 8 and the polarizing plate 10 are bonded via a back light tape 7. In addition, the polarizing plate 10 and the liquid crystal cell 5 are bonded via a second adhesive layer 32 not shown in the drawings of the polarizing plate 10. In addition, the polarizing plate 6 shown in FIG. 2 may be the polarizing plate of the present invention or a known polarizing plate.

以下，列舉實施例而具體地說明本發明，但本發明是不侷限於以下的實施例。例中，表示使用量乃至含量的份及%，無特別論述時為重量基準。 Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited to the following examples. In the examples, it indicates the amount of use and even the parts and% of the content, and it is based on weight unless otherwise specified.

首先，例示調製硬化性樹脂組成物之例。在硬化性樹脂組成物的調製中，係使用下述的化合物。 First, an example of preparing a curable resin composition will be exemplified. In preparing the curable resin composition, the following compounds are used.

〈活性能量線硬化性化合物〉 <Active Energy Ray Curing Compound>

"CELLOXIDE(註冊商標)2021P"：3,4-環氧基環己烷羧 酸3,4-環氧基環己基甲基酯，由Daicel化學(股)公司取得。 "CELLOXIDE (registered trademark) 2021P": 3,4-epoxycyclohexane carboxyl Acid 3,4-epoxycyclohexyl methyl ester, obtained from Daicel Chemical Co., Ltd.

"OXT-221"：雙(3-乙基-3-氧雜環丁基甲基)醚，由東亞合成(股)公司取得。 "OXT-221": bis(3-ethyl-3-oxetanylmethyl) ether, obtained from East Asia Synthetic Co., Ltd.

"A-DCP"：三環癸烷二甲醇二丙烯酸酯，由新中村化學(股)公司取得。 "A-DCP": Tricyclodecane dimethanol diacrylate, obtained by Shin Nakamura Chemical Co., Ltd.

〈光陽離子聚合起始劑〉 <Photo-cationic polymerization initiator>

"Adeka optomer(註冊商標)SP-150"：4,4’-雙[二苯基鋶基]二苯基硫化物雙六氟磷酸鹽系的光陽離子聚合起始劑，以碳酸丙烯酯溶液的形態由ADEKA(股)取得。 "Adeka optomer (registered trademark) SP-150": 4,4'-bis[diphenylamyl]diphenyl sulfide bishexafluorophosphate-based photocationic polymerization initiator, based on propylene carbonate solution The form is acquired by ADEKA (shares).

〈光自由基聚合起始劑〉 <Optical radical polymerization initiator>

"IRGACURE(註冊商標)907"：2-甲基-1-[4-(甲基硫基)苯基]-2-嗎啉基丙烷-1-酮，由BASF日本(股)公司取得。 "IRGACURE (registered trademark) 907": 2-methyl-1-[4-(methylsulfanyl)phenyl]-2-morpholinylpropane-1-one, obtained from BASF Japan Corporation.

"DAROCUR(註冊商標)1173"：2-羥基-2-甲基-1-苯基-丙烷-1-酮，由BASF日本(股)公司取得。 "DAROCUR (registered trademark) 1173": 2-hydroxy-2-methyl-1-phenyl-propane-1-one, obtained by BASF Japan Corporation.

〈擴散粒子〉 <Diffusion Particles>

"ART PEARL(註冊商標)SE-006T"：丙烯酸小珠，粒徑6μm，由根上工業(股)公司取得。 "ART PEARL (registered trademark) SE-006T": Acrylic beads, with a particle size of 6 μm, obtained by Genshang Industry Co., Ltd.

〈其他的成分〉 <Other ingredients>

"SH710"：矽酮系調平劑，由東麗．道康寧(股)公司取得。 "SH710": Silicone leveling agent, by Toray. Obtained by Dow Corning Corporation.

[製造例1]硬化性樹脂組成物A至F的調製 [Production Example 1] Preparation of curable resin compositions A to F

混合以下的各成分，分別調製硬化性樹脂組成物A至F者，但光陽離子聚合起始劑"Adeka optomer SP-150"是使用碳酸丙烯酯溶液者，以下是表示其有效成分量。 The following components are mixed to prepare the curable resin compositions A to F, but the photo-cationic polymerization initiator "Adeka optomer SP-150" uses propylene carbonate solution, and the following is the effective component amount.

〈硬化性樹脂組成物A〉 <Curable resin composition A>

〈硬化性樹脂組成物B〉 <Curable resin composition B>

〈硬化性樹脂組成物C〉 <Curable resin composition C>

〈硬化性樹脂組成物D〉 <Curable resin composition D>

〈硬化性樹脂組成物E〉 <Curable resin composition E>

[製造例2]偏光片的製作 [Manufacture example 2] Production of polarizer

將平均聚合度約2400、皂化度99.9莫耳%以上且厚度20μm的聚乙烯醇薄膜，以乾式單軸延伸成約4倍，更保持緊張狀態下，在40℃的純水浸漬1分鐘之後，在碘/碘化鉀/水的重量比為0.05/10/100的水溶液中，於28℃浸漬60秒鐘。之後，於碘化鉀/硼酸/水的重量比為8.5/7.5/100的水溶液中，於68℃浸漬300秒鐘。接著，以10℃的純水洗淨20秒鐘之後，於65℃乾燥，製作於經單軸延伸之聚乙烯醇薄膜中吸附配向有碘之偏光片。偏光片的厚度是7μm。 The polyvinyl alcohol film with an average polymerization degree of about 2400, a saponification degree of 99.9 mol% or more, and a thickness of 20 μm is uniaxially stretched by dry-type to approximately 4 times, while maintaining tension, after immersion in pure water at 40°C for 1 minute, after In an aqueous solution with a weight ratio of iodine/potassium iodide/water of 0.05/10/100, immerse at 28°C for 60 seconds. Thereafter, it was immersed in an aqueous solution having a weight ratio of potassium iodide/boric acid/water of 8.5/7.5/100 at 68°C for 300 seconds. Next, after washing with pure water at 10°C for 20 seconds, it was dried at 65°C to produce a polarizer having iodine adsorbed and aligned in a uniaxially stretched polyvinyl alcohol film. The thickness of the polarizer is 7 μm.

其次，例示調製接著劑之例子。在聚乙烯醇及環氧交聯劑中，係使用下述的化合物。 Next, an example of preparing an adhesive is exemplified. Among the polyvinyl alcohol and epoxy crosslinking agents, the following compounds are used.

〈聚乙烯醇〉 <polyvinyl alcohol>

"Kuraray Poval(註冊商標)KL 318"：羧基改質聚乙烯醇，由Kuraray(股)公司取得。 "Kuraray Poval (registered trademark) KL 318": carboxy-modified polyvinyl alcohol, obtained by Kuraray Corporation.

〈環氧系交聯劑〉 <Epoxy Crosslinking Agent>

"Sumirez Resin(註冊商標)650"：水溶性聚醯胺環氧樹脂(固形分濃度30%的水溶液)，由Sumika Chemtex(股)公司取得。 "Sumirez Resin (registered trademark) 650": water-soluble polyamide epoxy resin (aqueous solution with a solid concentration of 30%), obtained from Sumika Chemtex Corporation.

[製造例3]水系接著劑的調製 [Production Example 3] Preparation of water-based adhesive

混合以下的各成分，調製水系接著劑，但環氧系交聯劑"Sumirez Resin 650"使用水溶液者，以下是表示其有效成分 量。 The following components are mixed to prepare an aqueous adhesive, but the epoxy-based cross-linking agent "Sumirez Resin 650" uses an aqueous solution. The following are the effective ingredients. the amount.

〈水系接著劑〉 <Aqueous Adhesive>

[製造例4]偏光板A的製作 [Manufacture example 4] Production of polarizing plate A

在製造例2製作的偏光片之單面，塗布製造例3所調製之水系接著劑，貼合由三醋酸纖維素系薄膜作成的保護層[Konica Minolta Opto(股)公司製，KC2UA，厚度25μm，稱為第二保護層]，在另一側的面塗布純水，貼合聚乙烯系薄膜[東麗Film加工(股)公司製，TORETEC(註冊商標)7332，厚度30μm]。將此在60℃乾燥3分鐘之後，將聚乙烯系薄膜剝離，製作在單面具有第二保護層之偏光板A。 On one side of the polarizer produced in Production Example 2, the water-based adhesive prepared in Production Example 3 was applied, and a protective layer made of triacetate cellulose film [Konica Minolta Opto Co., Ltd. product, KC2UA, thickness 25 μm , Referred to as the second protective layer], coated with pure water on the other side, and laminated with a polyethylene film [Toray Film Processing Co., Ltd. product, TORETEC (registered trademark) 7332, thickness 30 μm]. After drying this at 60 degreeC for 3 minutes, the polyethylene film was peeled off, and the polarizing plate A which has the 2nd protective layer on one side was produced.

[實施例1] [Example 1] (1)偏光板的製作 (1) Production of polarizing plate

將製造例1所調製的硬化性樹脂組成物A，藉由棒塗佈機以使硬化後的膜厚成為約5μm之方式塗佈在厚度50μm的環烯烴系薄膜[日本ZEON(股)製的商品名"ZEONOR"]的單面。在此塗佈面，以製造例4所製作的偏光板A之偏光片側貼合，製作積層體。由此積層體的環烯烴系薄膜側藉由附輸送帶之紫外線照射裝置[燈是使用 Fusion UV Systems公司製的"D燈泡"]以使累積光量成為500mJ/cm²的方式照射紫外線，使硬化性樹脂組成物硬化，之後由積層體將環烯烴系薄膜剝離。如是，製作由第一保護層(硬化性樹脂組成物的硬化物)/偏光片/接著劑層/第二保護層而成的偏光板。 The curable resin composition A prepared in Production Example 1 was applied to a 50 μm-thick cycloolefin-based film [manufactured by Japan Zeon Co., Ltd.] with a bar coater so that the cured film thickness became approximately 5 μm. One side of the brand name "ZEONOR"]. On this coated surface, the polarizing plate A of the polarizing plate A produced in Production Example 4 was bonded to produce a laminate. In this way, the cycloolefin film side of the laminate was irradiated with ultraviolet rays with a conveyor belt [the lamp is a "D bulb" manufactured by Fusion UV Systems] so that the accumulated light amount became 500 mJ/cm ² to cure. The curable resin composition is cured, and then the cycloolefin-based film is peeled off from the laminate. If so, a polarizing plate made of a first protective layer (cured product of curable resin composition)/polarizer/adhesive layer/second protective layer is produced.

其次，在(1)所製作的偏光板之第一保護層側，設置作為第一黏著劑層之厚度5μm的丙烯酸系黏著劑A之層(黏著劑層A，霧度值0%)之後，在前述丙烯酸系黏著劑的與第一保護層為相反側之側，積層厚度26μm的亮度提昇薄膜[3M(股)製的商品名"Advanced Polarized Film，Version 3(APF-V3)"]。又，第一保護層與第一黏著劑層的貼合面之外，在貼合前實施電暈處理。 Next, on the side of the first protective layer of the polarizing plate produced in (1), a layer of acrylic adhesive A (adhesive layer A, haze value 0%) with a thickness of 5 μm as the first adhesive layer was provided, On the side of the acrylic adhesive opposite to the first protective layer, a brightness enhancement film with a thickness of 26 μm was laminated [3M (trade name) "Advanced Polarized Film, Version 3 (APF-V3)"]. In addition, a corona treatment is performed before the bonding, except for the bonding surface of the first protective layer and the first adhesive layer.

[實施例2至5] [Examples 2 to 5]

在實施例1中，除了變更為表1中記載的硬化性樹脂組成物之外，其餘是與實施例1同樣地操作而製作偏光板。 In Example 1, a polarizing plate was produced in the same manner as in Example 1, except that it was changed to the curable resin composition described in Table 1.

[實施例6] [Example 6]

在實施例2中，除了使用厚度15μm、霧度36%之擴散黏著劑層B作為第一黏著劑層之外，其餘是與實施例2同樣地操作而製作偏光板。 In Example 2, except that the diffusion adhesive layer B having a thickness of 15 μm and a haze of 36% was used as the first adhesive layer, the polarizing plate was produced in the same manner as in Example 2.

[實施例7] [Example 7]

在實施例3中，除了使用擴散黏著劑層B作為第一黏 著劑層之外，其餘是與實施例3同樣地操作而製作偏光板。 In Example 3, except that the diffusion adhesive layer B is used as the first adhesive The polarizing plate was produced in the same manner as in Example 3 except for the adhesive layer.

[實施例8] [Example 8]

在實施例4中，除了使用擴散黏著劑層B作為第一黏著劑層之外，其餘是與實施例4同樣地操作而製作偏光板。 In Example 4, a polarizing plate was produced in the same manner as in Example 4 except that the diffusion adhesive layer B was used as the first adhesive layer.

[實施例9] [Example 9]

在實施例5中，除了使用擴散黏著劑層B作為第一黏著劑層之外，其餘是與實施例5同樣地操作而製作偏光板。 In Example 5, a polarizing plate was produced in the same manner as in Example 5 except that the diffusion adhesive layer B was used as the first adhesive layer.

[實施例10] [Example 10]

在實施例2中，除了使用厚度15μm、霧度50%的擴散黏著劑層C作為第一黏著劑層之外，其餘是與實施例2同樣地操作而製作偏光板。 In Example 2, except that the diffusion adhesive layer C having a thickness of 15 μm and a haze of 50% was used as the first adhesive layer, a polarizing plate was produced in the same manner as in Example 2.

[實施例11] [Example 11]

在實施例3中，除了使用擴散黏著劑層C作為第一黏著劑層之外，其餘是與實施例3同樣地操作而製作偏光板。 In Example 3, except that the diffusion adhesive layer C was used as the first adhesive layer, the polarizing plate was produced in the same manner as in Example 3.

[實施例12] [Example 12]

在實施例4中，除了使用擴散黏著劑層C作為第一黏著劑層之外，其餘是與實施例4同樣地操作而製作偏光板。 In Example 4, a polarizing plate was produced in the same manner as in Example 4 except that the diffusion adhesive layer C was used as the first adhesive layer.

[實施例13] [Example 13]

在實施例5中，除了使用擴散黏著劑層C作為第一黏著劑層之外，其餘是與實施例5同樣地操作而製作偏光板。 In Example 5, a polarizing plate was produced in the same manner as in Example 5 except that the diffusion adhesive layer C was used as the first adhesive layer.

[比較例1] [Comparative Example 1]

除了未積層第一保護層之外，即除了在偏光片直接積層第一黏著劑層之外，其餘是與實施例1同樣地操作而製作偏光板。 A polarizing plate was produced in the same manner as in Example 1 except that the first protective layer was not laminated, that is, the first adhesive layer was directly laminated on the polarizer.

[比較例2] [Comparative Example 2]

除了未積層第一保護層之外，即除了在偏光片直接積層第一黏著劑層之外，其餘是與實施例9同樣地操作而製作偏光板。 A polarizing plate was produced in the same manner as in Example 9 except that the first protective layer was not laminated, that is, the first adhesive layer was directly laminated on the polarizer.

[比較例3] [Comparative Example 3]

除了未積層第一保護層之外，即除了在偏光片直接積層第一黏著劑層之外，其餘是與實施例13同樣地操作而製作偏光板。 A polarizing plate was produced in the same manner as in Example 13 except that the first protective layer was not laminated, that is, the first adhesive layer was directly laminated on the polarizer.

〈偏光板的光學耐久性之評估〉 <Evaluation of the optical durability of polarizing plates>

在(1)所製作的偏光板之第二保護層的與偏光片為相反側之側，設置作為第二黏著劑層的厚度20μm之丙烯酸系黏著劑層。此時，對第二保護層與第二黏著劑層的各貼合面實施電暈處理。此後，以與偏光片的吸收軸平行方向成為長邊之方式，裁切成60mm×110mm的大小，以其第二 黏著劑層側貼合於無鹼玻璃[康寧公司製的商品名"EAGLE XG"]。對此樣品，於溫度50℃、壓力5kg/cm²(490.3kPa)實施1小時之高壓釜處理之後，於溫度23℃、相對濕度55%的環境下放置24小時。針對此樣品，在溫度65℃、相對濕度90%的環境下放置100小時，觀察外觀的變化。此時，將無變化者設為○，看到剝離或浮起等者設成×，將結果在表1的「濕熱耐久性」欄表示。 On the side of the second protective layer of the polarizing plate produced in (1) opposite to the polarizer, an acrylic adhesive layer with a thickness of 20 μm as a second adhesive layer was provided. At this time, corona treatment is applied to each bonding surface of the second protective layer and the second adhesive layer. After that, it is cut into a size of 60 mm × 110 mm so that it is parallel to the absorption axis of the polarizer, and is attached to the alkali-free glass with its second adhesive layer side [trade name "EAGLE XG" by Corning) "]. This sample was subjected to an autoclave treatment at a temperature of 50°C and a pressure of 5 kg/cm ² (490.3 kPa) for 1 hour, and then placed in an environment at a temperature of 23°C and a relative humidity of 55% for 24 hours. For this sample, let it stand for 100 hours in an environment with a temperature of 65°C and a relative humidity of 90%, and observe the change in appearance. At this time, those with no change were set to ○, those who saw peeling or floating, etc. were set to ×, and the results are shown in the column of “damp heat durability” in Table 1.

〈偏光板的霧度評估〉 <Haze evaluation of polarizing plate>

將上述(1)所製作的偏光板，藉由根據JIS K 7136之霧度儀(HM-150型，村上色彩技術研究所(股)製)，以由第二保護層側入射之方式設置偏光板，測定偏光板的霧度。 The polarizing plate produced in (1) above is polarized by a haze meter (HM-150 type, manufactured by Murakami Color Technology Research Institute Co., Ltd.) according to JIS K 7136 so as to be incident from the second protective layer side Plate, and measure the haze of the polarizing plate.

由表1可知，相對於無第一保護層的比較例 1至3在溫度65℃相對濕度90%的濕熱環境下會發生剝離，具有第一保護層之實施例都沒有剝離。又，可知藉由在第一保護層中放入粒子，可與擴散黏著劑層一同調整霧度。 As can be seen from Table 1, compared to the comparative example without the first protective layer 1 to 3 will peel off in a hot and humid environment with a temperature of 65°C and a relative humidity of 90%. None of the examples with the first protective layer peeled off. In addition, it can be seen that by putting particles in the first protective layer, the haze can be adjusted together with the diffusion adhesive layer.

[產業上的可利用性] [Industry availability]

若依據本發明，可以提供一種偏光板以及具有該偏光板之液晶顯示裝置，該偏光板係在黏著劑層與偏光片之間無保護薄膜之薄型偏光板，且在偏光片的表面所形成之保護層與黏著劑層的密著力強，在濕熱環境下之耐久性經提昇。 According to the present invention, a polarizing plate and a liquid crystal display device having the polarizing plate can be provided. The polarizing plate is a thin polarizing plate without a protective film between the adhesive layer and the polarizing plate and formed on the surface of the polarizing plate The adhesion of the protective layer and the adhesive layer is strong, and the durability in a hot and humid environment is improved.

1‧‧‧偏光片 1‧‧‧ Polarizer

4‧‧‧機能性樹脂薄膜 4‧‧‧Functional resin film

10‧‧‧偏光板 10‧‧‧ Polarizer

21‧‧‧第一保護層 21‧‧‧The first protective layer

22‧‧‧第二保護層 22‧‧‧Second protective layer

31‧‧‧第一黏著劑層 31‧‧‧The first adhesive layer

32‧‧‧第二黏著劑層 32‧‧‧Second adhesive layer

Claims (12)

一種偏光板，係依序積層有機能性樹脂層、第一黏著劑層、屬於硬化性樹脂組成物的硬化物之第一保護層、及偏光片，其中，硬化性樹脂組成物含有活性能量線硬化性化合物、及光擴散劑。 A polarizing plate is formed by sequentially stacking an organic energy resin layer, a first adhesive layer, a first protective layer which is a hardened product of a hardenable resin composition, and a polarizer, wherein the hardenable resin composition contains active energy rays Hardening compound and light diffusing agent. 如申請專利範圍第1項所述之偏光板，其中，第一黏著劑層是擴散黏著劑層。 The polarizing plate as described in item 1 of the patent application, wherein the first adhesive layer is a diffusion adhesive layer. 如申請專利範圍第1項所述之偏光板，其中，機能性樹脂層是具有亮度提昇薄膜之層。 The polarizing plate as described in item 1 of the patent application, wherein the functional resin layer is a layer having a brightness enhancement film. 如申請專利範圍第1項所述的偏光板，其中，活性能量線硬化性化合物含有在分子內至少具有1個(甲基)丙烯醯氧基之(甲基)丙烯酸系化合物。 The polarizing plate according to item 1 of the patent application range, wherein the active energy ray-curable compound contains a (meth)acrylic compound having at least one (meth)acryloyloxy group in the molecule. 如申請專利範圍第1項所述之偏光板，其中，活性能量線硬化性化合物含有陽離子聚合性化合物。 The polarizing plate as described in item 1 of the patent application range, wherein the active energy ray-curable compound contains a cationic polymerizable compound. 如申請專利範圍第5項所述之偏光板，其中，陽離子聚合性化合物含有在分子內至少具有1個環氧乙烷環之化合物。 The polarizing plate as described in item 5 of the patent application range, wherein the cationic polymerizable compound contains a compound having at least one ethylene oxide ring in the molecule. 如申請專利範圍第1項所述之偏光板，其中，第一黏著劑層的厚度是0.1至10μm。 The polarizing plate as described in item 1 of the patent application, wherein the thickness of the first adhesive layer is 0.1 to 10 μm. 如申請專利範圍第1項所述之偏光板，其係在偏光片之與積層有第一保護層之側為相反之側具有第二保護層。 The polarizing plate as described in item 1 of the patent application scope has a second protective layer on the opposite side of the polarizer from the side where the first protective layer is deposited. 如申請專利範圍第8項所述之偏光板，其中，第二保護層是熱可塑性樹脂薄膜。 The polarizing plate as described in item 8 of the patent application, wherein the second protective layer is a thermoplastic resin film. 如申請專利範圍第8項所述之偏光板，其係在第二保護層之與積層有偏光片之側為相反之側具有第二黏著劑層。 The polarizing plate as described in item 8 of the patent application scope has a second adhesive layer on the opposite side of the second protective layer from the side where the polarizer is laminated. 如申請專利範圍第10項所述之偏光板，其係在第二黏著劑層之與積層有第二保護層之側為相反側之表面積層有剝離薄膜。 The polarizing plate as described in item 10 of the patent application scope has a release film on the surface area layer of the second adhesive layer opposite to the side where the second protective layer is deposited. 一種液晶顯示裝置，其係具有申請專利範圍第1至10項中任一項所述之偏光板，與液晶單元。 A liquid crystal display device is provided with the polarizing plate described in any one of claims 1 to 10, and a liquid crystal cell.

Images