TWI404784B - Polarizing plate and photo-curable adhesive for formation of polarizing plate - Google Patents

Polarizing plate and photo-curable adhesive for formation of polarizing plate Download PDF

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Publication number
TWI404784B
TWI404784B TW099112470A TW99112470A TWI404784B TW I404784 B TWI404784 B TW I404784B TW 099112470 A TW099112470 A TW 099112470A TW 99112470 A TW99112470 A TW 99112470A TW I404784 B TWI404784 B TW I404784B
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polymerizable compound
mass
polarizing plate
adhesive layer
protective film
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TW099112470A
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Chinese (zh)
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TW201109404A (en
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Satoko Kagiyama
Shinji Ishizaki
Hidekazu Ikeda
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Toyo Ink Mfg Co
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Liquid Crystal (AREA)
  • Adhesive Tapes (AREA)

Abstract

The present invention provides a polarizing plate, wherein two surfaces of a polyvinyl alcohol series polarizer are respectively protected by a protecting film while the two surfaces are separated from the protecting films by adhesion layers. The adhesion layers are obtained through solidifying a photo-curing adhesive which comprises the following components: (a) 60-99.8wt% of free radical polymeric compound, (c) 0.02-40wt% of cation polymeric compound which comprises cation polymeric functional groups and does not comprise (methyl)acryloyl group, (d) an optical free radical initiating agent, and (e) an optical cation polymerization initiating agent.

Description

偏光板及偏光板形成用光硬化性接著劑 Photocurable adhesive for forming polarizing plate and polarizing plate

本發明係有關液晶顯示裝置等使用之偏光板及該偏光板形成用之光硬化性接著劑。 The present invention relates to a polarizing plate used in a liquid crystal display device or the like and a photocurable adhesive for forming the polarizing plate.

在鐘錶、手機、個人用攜帶型終端機(PDA，亦即個人數位助理)、筆記型電腦、個人電腦用顯示器、數位多功能光碟(DVD)播放器、電視(TV)等方面，液晶顯示裝置係在市場急速擴張。液晶顯示裝置為經由液晶之切換(switching)而使偏光狀態可視化者，從其顯示原理而言，係使用偏光件。尤其是在電視等之用途，越來越要求高亮度、高對比、廣視野角，在偏光板亦越來越要求高透過率、高偏光度、高色澤再顯性等。 Liquid crystal display device in watches, mobile phones, personal portable terminal devices (PDAs, that is, personal digital assistants), notebook computers, personal computer monitors, digital versatile discs (DVD) players, televisions (TVs), etc. It is rapidly expanding in the market. The liquid crystal display device visualizes a polarization state by switching through a liquid crystal, and a polarizer is used from the principle of display. Especially in the use of televisions, etc., high brightness, high contrast, wide viewing angle are increasingly required, and high transmittance, high polarization, high color reproducibility, etc. are increasingly required in polarizing plates.

液晶顯示關連領域等使用之偏光件，通常係由將在聚乙烯醇(PVA)中吸附碘或染料者進行一軸延伸而製造。該聚乙烯醇系偏光件係因熱或水分而收縮，導致偏光性能降低。此處，將在PVA系偏光件的表面黏貼保護薄膜者作為偏光板使用。 A polarizing member used in a liquid crystal display related field or the like is usually produced by one-axis stretching by adsorbing iodine or a dye in polyvinyl alcohol (PVA). The polyvinyl alcohol-based polarizer shrinks due to heat or moisture, resulting in a decrease in polarizing performance. Here, a person who adheres a protective film to the surface of a PVA-type polarizer is used as a polarizing plate.

作為用於在偏光件黏貼保護薄膜的接著劑，以往廣泛使用聚乙烯醇系樹脂的水溶液(PVA系接著劑)(參照專利文獻1、2)。 An aqueous solution (PVA-based adhesive) of a polyvinyl alcohol-based resin has been widely used as an adhesive for adhering a protective film to a polarizing material (see Patent Documents 1 and 2).

於專利文獻3揭示使用水性胺酯(urethane)系接著劑而形成的偏光板。 Patent Document 3 discloses a polarizing plate formed using an aqueous urethane-based adhesive.

不過，尤其是以電視為代表，近年來隨著畫像顯示裝 置之大畫面化的進展，連帶地對於偏光板亦提高要求大型化，成為重要的課題。 However, especially with TV as the representative, in recent years, with the image display In order to increase the size of the polarizing plate, it is an important issue to increase the size of the polarizing plate.

惟，使用上述水系接著劑的偏光板，由於背光的熱而使偏光板的尺寸產生變化，且肇因於該尺寸變化的變形係局部存在於畫面的一部分，結果，本來畫面全體應顯示全黑時，光會部分性地洩露，有所謂的光洩露(顏色不勻)變顯著的問題。 However, in the polarizing plate using the water-based adhesive, the size of the polarizing plate changes due to the heat of the backlight, and the deformation due to the dimensional change partially exists in a part of the screen, and as a result, the entire screen should be displayed entirely black. At the time, the light leaks partially, and there is a problem that the so-called light leakage (uneven color) becomes significant.

根據如上述的理由，有使用陽離子聚合性紫外線硬化型接著劑來取代水系接著劑的提案(參照專利文獻4)。 For the reason described above, there is a proposal to use a cationically polymerizable ultraviolet curable adhesive instead of a water-based adhesive (see Patent Document 4).

惟，使用陽離子聚合性紫外線硬化型接著劑時，由於在紫外線照射後會產生暗反應(後聚合)，故在將長狀的硬化物作成捲筒狀時，有在保管時容易產生捲褶的問題。並且，陽離子聚合性紫外線硬化型接著劑容易受到硬化時濕度的影響，有硬化狀態容易有變異的問題。於是，為了表現均一的硬化狀態，不只是環境濕度，PVA系偏光件的含水率亦需要嚴格管理。 However, when a cationically polymerizable ultraviolet curable adhesive is used, since a dark reaction (post-polymerization) occurs after ultraviolet irradiation, when a long-shaped cured product is formed into a roll shape, wrinkles are likely to occur during storage. problem. Further, the cationically polymerizable ultraviolet curable adhesive is likely to be affected by the humidity at the time of curing, and there is a problem that the cured state is likely to be mutated. Therefore, in order to exhibit a uniform hardened state, not only the environmental humidity, the moisture content of the PVA-based polarizer also needs to be strictly managed.

自由基聚合性紫外線硬化型接著劑有該等問題較少的優點。 The radical polymerizable ultraviolet curable adhesive has the advantage that these problems are less.

不過，液晶顯示裝置隨著其用途之擴大，而逐漸可在種種環境中使用，而對於構成液晶顯示裝置的偏光板要求高耐環境性。 However, the liquid crystal display device can be used in various environments as its use is expanded, and the polarizing plate constituting the liquid crystal display device is required to have high environmental resistance.

例如以手機為代表的移動用途之液晶顯示裝置係要求高耐濕熱耐久性。 For example, a liquid crystal display device for mobile use typified by a mobile phone is required to have high humidity and heat durability.

如上所述，自由基聚合性紫外線硬化型接劑相較於陽 離子聚合性硬化型接著劑，於種種特點上較優越。 As described above, the radical polymerizable ultraviolet curing type binder is comparable to the anode The ionic polymerizable hardening type adhesive is superior in various characteristics.

惟，使用自由基聚合性紫外線硬化型接著劑時，若長時間暴露在濕熱環境下，則偏光性能容易降低，有在切割端部用碘或染料著色的偏光件容易發生脫色的問題。 However, when a radical polymerizable ultraviolet curable adhesive is used, when exposed to a hot and humid environment for a long period of time, the polarizing performance is liable to lower, and there is a problem that the polarizing member colored with iodine or a dye at the cut end portion is likely to be decolored.

又，在比濕熱環境下更嚴苛的條件(例如浸漬於60℃的溫水)時，偏光件的脫色顯著發生。 Moreover, decolorization of the polarizer occurs remarkably under more severe conditions (for example, warm water immersed in 60 ° C) than in a hot and humid environment.

亦即，在偏光板之使用環境更嚴苛的今日，實情為期待比以往偏光板更具有耐濕熱性的偏光板。 In other words, in the case where the use environment of the polarizing plate is more severe, the polarizing plate which is more resistant to moist heat than the polarizing plate of the prior art is expected.

再者，為了簡便地將偏光板聚乙烯系薄膜與塑膠薄膜以充分的強度接著，提案將(甲基)丙烯酸系之自由基聚合性化合物與陽離子聚合性化合物併用的接著性組成物(專利文獻5)。惟，該技術更要求改善穿孔加工性。 In addition, in order to easily carry out the polarizing plate polyethylene film and the plastic film with sufficient strength, an adhesive composition using a (meth)acrylic radical polymerizable compound and a cationically polymerizable compound has been proposed (Patent Document) 5). However, this technology is more demanding to improve the piercing processability.

[先前技術文獻] [Previous Technical Literature]

[專利文獻1]日本特開平09-258023號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 09-258023

[專利文獻2]日本特開2005-208456號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-208456

[專利文獻3]日本特開2004-37841號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2004-37841

[專利文獻4]日本特開2008-233874號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-233874

[專利文獻5]日本特開2008-260879號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-260879

本發明係以提供將聚乙烯醇系偏光件與保護薄膜作為構成層，且保護薄膜與偏光件的接著性及穿孔加工性優越，並且耐水性亦優越的偏光板為目的。 The present invention has an object of providing a polarizing plate having a polyvinyl alcohol-based polarizing member and a protective film as a constituent layer, and having excellent adhesion and punching workability of the protective film and the polarizing member, and excellent water resistance.

本發明人等為了解決上述課題，經過不斷的深入研究，結果發現根據以下表示的偏光板可達成上述的目標， 因而完成本發明。 In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the above-described object can be achieved by the polarizing plate shown below. Thus the present invention has been completed.

亦即，本發明係有關一種偏光板，其係含有聚乙烯醇系偏光件、將光硬化性接著劑硬化而成之接著層、及保護薄膜，且分別藉由保護薄膜隔著上述接著層被覆上述偏光件之兩面而成的偏光板；其特徵為：上述光硬化性接著劑含有由自由基聚合性化合物及陽離子聚合性化合物所構成的主劑、光自由基聚合啟始劑、及光陽離子聚合啟始劑；就上述自由基聚合性化合物而言，形成玻璃轉移溫度為-80℃至0℃之均聚物的自由基聚合性化合物(a)在上述主劑中含有60至99.8質量%；就上述陽離子聚合性化合物而言，未具有(甲基)丙烯醯基之陽離子聚合性化合物(c)在上述主劑中含有0.02至40質量%；相對於上述主劑100質量份，分別含有上述光自由基聚合啟始劑1至10質量份、上述光陽離子聚合啟始劑0.5至5質量份。 That is, the present invention relates to a polarizing plate comprising a polyvinyl alcohol-based polarizing member, an adhesive layer obtained by curing a photocurable adhesive, and a protective film, and each of which is covered by the protective film via the above-mentioned adhesive layer A polarizing plate comprising two sides of the polarizer; wherein the photocurable adhesive contains a main component composed of a radical polymerizable compound and a cationically polymerizable compound, a photoradical polymerization initiator, and a photocation A radical polymerization agent (a) which forms a homopolymer having a glass transition temperature of -80 ° C to 0 ° C in the above radical polymerizable compound, and contains 60 to 99.8% by mass in the above-mentioned main component. In the above cationically polymerizable compound, the cationically polymerizable compound (c) having no (meth) acrylonitrile group is contained in the above-mentioned main component in an amount of 0.02 to 40% by mass, and is contained in 100 parts by mass of the above-mentioned main component. 1 to 10 parts by mass of the photoradical polymerization initiator and 0.5 to 5 parts by mass of the photocationic polymerization initiator.

又，本發明係有關一種偏光板形成用光硬化性接著劑，其含有由自由基聚合性化合物及陽離子聚合性化合物所構成之主劑、光自由基聚合啟始劑及光陽離子聚合啟始劑；就上述自由基聚合性化合物而言，形成玻璃轉移溫度為-80℃至0℃之均聚物的自由基聚合性化合物(a)在上述主劑中含有60至99.8質量%； 就上述陽離子聚合性化合物而言，未具有(甲基)丙烯醯基之陽離子聚合性化合物(c)在上述主劑中含有0.02至40質量%；相對於上述主劑100質量份，分別含有上述光自由基聚合啟始劑1至10質量份、上述光陽離子聚合啟始劑0.5至5質量份。 Moreover, the present invention relates to a photocurable adhesive for forming a polarizing plate, which comprises a main component comprising a radical polymerizable compound and a cationically polymerizable compound, a photoradical polymerization initiator, and a photocationic polymerization initiator. The radically polymerizable compound (a) which forms a homopolymer of a glass transition temperature of -80 ° C to 0 ° C in the above radical polymerization compound contains 60 to 99.8% by mass in the above main agent; In the cationically polymerizable compound, the cationically polymerizable compound (c) having no (meth) acrylonitrile group is contained in the above-mentioned main component in an amount of 0.02 to 40% by mass, and the above-mentioned main component is contained in 100 parts by mass of the above-mentioned main component. 1 to 10 parts by mass of the photoradical polymerization initiator and 0.5 to 5 parts by mass of the above photocationic polymerization initiator.

以下，對於本發明之較佳實施形態加以說明。根據本發明，可提供將聚乙烯醇系偏光件及保護薄膜作為構成層之偏光板，其為接著性、穿孔加工性及耐水性優越之偏光板。 Hereinafter, preferred embodiments of the present invention will be described. According to the present invention, it is possible to provide a polarizing plate having a polyvinyl alcohol-based polarizing member and a protective film as a constituent layer, which is a polarizing plate excellent in adhesion, piercing processability, and water resistance.

[接著層] [Next layer]

以下，對於構成本發明偏光板的接著層(或接著劑層)加以說明。 Hereinafter, an adhesive layer (or an adhesive layer) constituting the polarizing plate of the present invention will be described.

接著層(於第1圖及第2圖中之符號2、4)為將光硬化性接著劑硬化而成之層。 The next layer (symbols 2 and 4 in FIGS. 1 and 2) is a layer obtained by curing a photocurable adhesive.

光硬化性接著劑含有由光硬化性化合物所構成之主劑及聚合啟始劑。主劑包含自由基聚合性成分(自由基聚合性化合物)及陽離子聚合性成分(陽離子聚合性化合物)。 The photocurable adhesive contains a main component composed of a photocurable compound and a polymerization initiator. The main component contains a radical polymerizable component (radical polymerizable compound) and a cationic polymerizable component (cationic polymerizable compound).

自由基聚合性成分係將可形成玻璃轉移溫度為-80℃至0℃之均聚物的自由基聚合性化合物(a)(以下，亦稱為「自由基聚合性化合物(a)」或「低Tg自由基聚合性化合物(a)」)作為必須成分，且另可含有可形成玻璃轉移溫度為60℃至250℃之均聚物的自由基聚合性化合物(b)(以 下，亦稱為「自由基聚合性化合物(b)」或「高Tg自由基聚合性化合物(b)」)。亦即，就自由基聚合性成分而言，係含有其均聚物的玻璃轉移溫度為-80℃至0℃之自由基聚合性化合物(a)，且任意地含有其均聚物的玻璃轉移溫度為60℃至250℃之自由基聚合性化合物(b)。 The radical polymerizable component is a radically polymerizable compound (a) which can form a homopolymer having a glass transition temperature of -80 ° C to 0 ° C (hereinafter also referred to as "radical polymerizable compound (a)" or " The low Tg radical polymerizable compound (a)") is an essential component, and may further contain a radical polymerizable compound (b) capable of forming a homopolymer having a glass transition temperature of 60 ° C to 250 ° C ( Hereinafter, it is also referred to as "radical polymerizable compound (b)" or "high Tg radical polymerizable compound (b)"). In other words, the radical polymerizable component is a radically polymerizable compound (a) having a glass transition temperature of -80 ° C to 0 ° C containing a homopolymer thereof, and optionally contains a glass transition of its homopolymer. The radically polymerizable compound (b) having a temperature of from 60 ° C to 250 ° C.

低Tg自由基聚合性化合物(a)中，單官能者可列舉例如：丙烯酸2-羥基乙酯(均聚物之Tg：-9℃，以下亦相同)、丙烯酸2-羥基丙酯(-7℃)及丙烯酸4-羥基丁酯(-55℃) In the low Tg radical polymerizable compound (a), for example, 2-hydroxyethyl acrylate (Tg of homopolymer: -9 ° C, the same applies hereinafter), 2-hydroxypropyl acrylate (-7) may be mentioned. °C) and 4-hydroxybutyl acrylate (-55 ° C)

所代表之(甲基)丙烯酸羥基末端烷酯；丙烯酸2-甲氧基乙酯(-43℃)、丙烯酸3-甲氧基丁酯(-47℃)、丙烯酸十三烷酯(-65℃)及甲基丙烯酸十三烷酯(-37℃) Representative of hydroxy terminal alkyl (meth) acrylate; 2-methoxyethyl acrylate (-43 ° C), 3-methoxybutyl acrylate (-47 ° C), tridecyl acrylate (-65 ° C ) and tridecyl methacrylate (-37 ° C)

所代表之(甲基)丙烯酸烷基末端烷酯；二乙二醇單***丙烯酸酯(-54℃)、乙氧基二乙二醇丙烯酸酯(-51℃)、甲氧基聚乙二醇(n=9)丙烯酸酯(-71℃)及甲氧基三縮三丙二醇丙烯酸酯(-75℃) Representative alkyl terminal alkyl (meth)acrylate; diethylene glycol monoethyl ether acrylate (-54 ° C), ethoxy diethylene glycol acrylate (-51 ° C), methoxy polyethylene glycol (n=9) acrylate (-71 ° C) and methoxytripropylene glycol acrylate (-75 ° C)

所代表之烷基末端(聚)烷二醇系(甲基)丙烯酸酯；丙烯酸苯氧基乙酯(-15℃)、丙烯酸三氟乙酯(-10℃)、ω-羧基-聚己內酯丙烯酸酯(-46℃)等。 Representative alkyl end (poly)alkylene glycol (meth) acrylate; phenoxyethyl acrylate (-15 ° C), trifluoroethyl acrylate (-10 ° C), ω-carboxy-poly Ester acrylate (-46 ° C) and the like.

又，低Tg自由基聚合性化合物(a)中，多官能者可列舉如：聚乙二醇(400)二丙烯酸酯(-28℃)、聚乙二醇(600)二丙烯酸酯(-42℃)、三乙二醇二甲基丙烯酸酯(-5℃)、乙氧化(9)三羥甲基丙烷三丙烯酸酯(-19℃)等。 Further, in the low Tg radical polymerizable compound (a), polyfunctional examples include polyethylene glycol (400) diacrylate (-28 ° C) and polyethylene glycol (600) diacrylate (-42). °C), triethylene glycol dimethacrylate (-5 ° C), ethoxylated (9) trimethylolpropane triacrylate (-19 ° C) and the like.

本發明之光硬化性接著劑可將該等材料適當組合使用。 The photocurable adhesive of the present invention can be used in combination as appropriate.

低Tg自由基聚合性化合物(a)較好為單官能者。即使為低Tg自由基聚合性化合物(a)，若只使用多官能者，則在後述之切割試驗性能之觀點上有不佳的情形。因此，為了作成該切割試驗性能亦良好者，在併用多官能者作為低Tg自由基聚合性化合物(a)時，在低Tg自由基聚合性化合物(a)(作為100質量%)中係控制在未達40質量%的程度，較好係控制在未達10質量%的程度。 The low Tg radical polymerizable compound (a) is preferably monofunctional. Even if it is a low Tg radically polymerizable compound (a), if only a polyfunctional group is used, it will be inferior in the viewpoint of the cutting test performance mentioned later. Therefore, in order to obtain the low-Tg radically polymerizable compound (a) in combination with a polyfunctional person, it is preferable to control the low Tg radically polymerizable compound (a) (as 100% by mass). In the case of less than 40% by mass, it is preferably controlled to a level of less than 10% by mass.

又，使用後述之高Tg自由基聚合性化合物(b)時，該高Tg自由基聚合性化合物(b)之較好例不是多官能而是單官能。換言之，當使用多官能自由基聚合性化合物作為自由基聚合性化合物((a)或(a)+(b))時，該比例在主劑(作為100質量%)中係未達40質量%的程度，較好為未達10質量%的程度。 When a high Tg radically polymerizable compound (b) to be described later is used, a preferred example of the high Tg radically polymerizable compound (b) is not polyfunctional but monofunctional. In other words, when a polyfunctional radically polymerizable compound is used as the radically polymerizable compound ((a) or (a) + (b)), the ratio is less than 40% by mass in the main component (as 100% by mass) The degree is preferably less than 10% by mass.

或者是，自由基聚合性化合物中之單官能自由基聚合性化合物(單官能之自由基聚合性化合物(a)、或單官能之自由基聚合性化合物(a)及(b)之合計)的比例較好在60質 量%以上，更好在70質量%以上，最好在90質量%以上。 Or a monofunctional radically polymerizable compound (monofunctional radically polymerizable compound (a) or monofunctional radically polymerizable compound (a) and (b) in a radically polymerizable compound) Proportion is better at 60 quality The amount is at least 70% by mass, more preferably at least 90% by mass.

該自由基聚合性化合物(a)更好為均聚物的玻璃轉移溫度為-60℃至-20℃者，最好為均聚物的玻璃轉移溫度為-60℃至-40℃者。 The radical polymerizable compound (a) is more preferably a homopolymer having a glass transition temperature of from -60 ° C to -20 ° C, and preferably a homopolymer having a glass transition temperature of from -60 ° C to -40 ° C.

該等低Tg自由基聚合性化合物(a)中，從提昇與PVA系偏光件之接著性之觀點而言，較好為(甲基)丙烯酸羥基烷酯等具有羥基者，其中較好為丙烯酸4-羥基丁酯。從硬化物的Tg不易變低之觀點而言，即使為具有羥基者，亦以不使用丙烯酸2-羥基乙酯、丙烯酸2-羥基丙酯為佳。亦即，(甲基)丙烯酸羥基烷酯之烷基之碳原子數較好為約4至40。 In the low Tg radically polymerizable compound (a), from the viewpoint of improving the adhesion to the PVA-based polarizer, it is preferably a hydroxyl group such as a hydroxyalkyl (meth)acrylate, and among them, acrylic acid is preferred. 4-hydroxybutyl ester. From the viewpoint that the Tg of the cured product is not easily lowered, it is preferred to use 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate even if it has a hydroxyl group. That is, the alkyl group of the hydroxyalkyl (meth) acrylate preferably has a carbon number of about 4 to 40.

從使硬化後之接著劑層的凝集力提高且提昇接著力之觀點而言，低Tg自由基聚合性化合物(a)係以使用ω-羧基-聚己內酯單(甲基)丙烯酸酯更佳。惟，ω-羧基-聚己內酯單(甲基)丙烯酸酯之硬化性不佳，故可經由適當選擇自由基聚合啟始劑之種類或量、適當選擇紫外線照射裝置之燈、適當選擇照射強度或曝光量等硬化條件、適當選擇保護薄膜之種類或厚度等，而彌補硬化性。ω-羧基-聚己內酯單(甲基)丙烯酸酯之己內酯聚合度(n)並無特別限制，較好為n=2至20之程度。 From the viewpoint of improving the cohesive force of the adhesive layer after hardening and improving the adhesion, the low Tg radical polymerizable compound (a) is more preferably ω-carboxy-polycaprolactone mono(meth)acrylate. good. However, since the ω-carboxy-polycaprolactone mono(meth)acrylate has poor hardenability, the type or amount of the radical polymerization initiator can be appropriately selected, the lamp of the ultraviolet irradiation device can be appropriately selected, and the irradiation can be appropriately selected. The curing property such as the strength or the exposure amount, the type or thickness of the protective film, and the like are appropriately selected to compensate for the hardenability. The degree of polymerization (n) of the caprolactone of the ω-carboxy-polycaprolactone mono(meth)acrylate is not particularly limited, and is preferably about n=2 to 20.

例如，以主劑合計當作100質量%時為60至99.8質量%之自由基聚合性化合物(a)，較好係將丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷酯在10至99.8質量%、ω-羧基-聚己內酯單(甲基)丙烯酸酯在0至50質量%之各範圍中加 以組合。 For example, the radically polymerizable compound (a) is preferably from 60 to 99.8% by mass in terms of 100% by mass of the total amount of the main component, and is preferably a hydroxyalkyl (meth)acrylate such as 4-hydroxybutyl acrylate. 99.8 mass%, ω-carboxy-polycaprolactone mono(meth)acrylate is added in each range of 0 to 50% by mass In combination.

又，調配ω-羧基-聚己內酯單(甲基)丙烯酸酯時，更好係將(甲基)丙烯酸羥基烷酯在10至99.7質量%、ω-羧基-聚己內酯單(甲基)丙烯酸酯在0.01至50質量%的範圍中使用。 Further, when the ω-carboxy-polycaprolactone mono(meth)acrylate is blended, it is more preferred to use a hydroxyalkyl (meth)acrylate at 10 to 99.7% by mass, ω-carboxy-polycaprolactone mono(A) The acrylate is used in the range of 0.01 to 50% by mass.

任意調配之高Tg自由基聚合性化合物(b)較好係使用例如：甲基丙烯酸二環戊烯酯(均聚物之Tg：180℃，以下亦相同)、甲基丙烯酸三氟乙酯(81℃)、甲基丙烯酸第三丁酯(113℃)、甲基丙烯酸乙酯(65℃)、甲基丙烯酸四氫糠酯(68℃)、丙烯酸異冰片酯(85℃)及丙烯醯基嗎啉(106℃)等。其中，從耐熱性之觀點而言，較好係使用丙烯酸異冰片酯、丙烯醯基嗎啉。 The highly-adjusted high-Tg radical polymerizable compound (b) is preferably, for example, dicyclopentenyl methacrylate (Tg of homopolymer: 180 ° C, the same applies hereinafter), trifluoroethyl methacrylate ( 81 ° C), butyl methacrylate (113 ° C), ethyl methacrylate (65 ° C), tetrahydrofurfuryl methacrylate (68 ° C), isobornyl acrylate (85 ° C) and acrylonitrile Morpholine (106 ° C) and the like. Among them, isobornyl acrylate and acryloyl morpholine are preferably used from the viewpoint of heat resistance.

該自由基聚合性化合物(b)以均聚物的玻璃轉移溫度為60℃至200℃者較佳，以均聚物的玻璃轉移溫度為80℃至150℃者更佳。 The radical polymerizable compound (b) is preferably a glass transition temperature of the homopolymer of from 60 ° C to 200 ° C, and more preferably a glass transition temperature of the homopolymer of from 80 ° C to 150 ° C.

本發明之光硬化性接著劑可將該等材料適當組合使用。 The photocurable adhesive of the present invention can be used in combination as appropriate.

可由上述之低Tg自由基聚合性化合物(3)、高Tg自由基聚合性化合物(b)所形成之各均聚物之Tg係依以下的操作求得之值。 The Tg of each homopolymer formed from the low Tg radical polymerizable compound (3) and the high Tg radical polymerizable compound (b) described above can be obtained by the following operation.

將各化合物及啟始劑放入適當容量之塑膠製容器中，將照射紫外線而硬化者10mg作為測定用試料，使用示差掃瞄熱量計(DSC)，以10℃/分鐘或20℃/分鐘的昇溫速度測定。 Each compound and the starter were placed in a plastic container of a suitable capacity, and 10 mg of the cured material was irradiated with ultraviolet rays as a sample for measurement, and a differential scanning calorimeter (DSC) was used at 10 ° C / min or 20 ° C / min. The heating rate was measured.

未具有(甲基)丙烯醯基之陽離子聚合性化合物(c)(以下，將此稱為「陽離子聚合性化合物(c)」)為具有陽離子聚合性官能基且未具有(甲基)丙烯醯基之化合物，列舉例如3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間-二烷、雙(3,4-環氧基環己基甲基)己二酸酯、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯、乙烯基環己烯一氧化物、1,2-環氧基-4-乙烯基環己烷等1分子中具有1個以上脂環式環氧基之化合物或具有氧雜環丁基之化合物。陽離子聚合性化合物(c)擔任提昇經硬化之接著層之耐水性的任務。 The cationically polymerizable compound (c) having no (meth) acrylonitrile group (hereinafter referred to as "cationic polymerizable compound (c)") has a cationically polymerizable functional group and does not have (meth)acryl oxime Examples of the compound include, for example, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3 , 4-epoxy)cyclohexane-inter-di Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, vinylcyclohexene A compound having one or more alicyclic epoxy groups or a compound having an oxetanyl group in one molecule such as monooxyl or 1,2-epoxy-4-vinylcyclohexane. The cationically polymerizable compound (c) serves as a task for improving the water resistance of the hardened adhesive layer.

具有脂環式環氧基之化合物中，從反應性之觀點而言，較好係使用3,4-環氧基環己基甲基-3,4-環氧基環己烷羧酸酯。 Among the compounds having an alicyclic epoxy group, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferably used from the viewpoint of reactivity.

於本發明，從確保接著力及穿孔加工性良好之觀點而言，陽離子聚合性化合物(c)較好係選擇未具有(甲基)丙烯醯基者。雖可將具有(甲基)丙烯醯基之陽離子聚合性化合物與上述(c)併用，惟，此時之具有(甲基)丙烯醯基之陽離子聚合性化合物之調配量在主劑100質量%中，必需控制在未達20質量%之程度，較好為控制在未達10質量%之程度。 In the present invention, the cationically polymerizable compound (c) is preferably selected from those having no (meth) acrylonitrile group from the viewpoint of ensuring good adhesion and puncture workability. The cationically polymerizable compound having a (meth) acrylonitrile group may be used in combination with the above (c), but the amount of the cationically polymerizable compound having a (meth) acrylonitrile group at this time is 100% by mass of the main component. In the case, it is necessary to control the degree to less than 20% by mass, preferably to the extent of not more than 10% by mass.

或是，在陽離子聚合性化合物全體中，未具有(甲基)丙烯醯基之陽離子聚合性化合物(c)占有之比例較好在50質量%以上，更好在75質量%以上。 In addition, in the entire cationically polymerizable compound, the ratio of the cationically polymerizable compound (c) having no (meth) acrylonitrile group is preferably 50% by mass or more, more preferably 75% by mass or more.

光硬化性接著劑的主劑係含有自由基聚合性化合物(a)60至99.9質量%、陽離子聚合性化合物(c)0.02至40質量%，較好係自由基聚合性化合物(a)：60至99質量%、陽離子聚合性化合物(c)：1至40質量%，更好係自由基聚合性化合物(a)：90至99質量%、陽離子聚合性化合物(c)：1至10質量%。 The main component of the photocurable adhesive contains 60 to 99.9% by mass of the radical polymerizable compound (a) and 0.02 to 40% by mass of the cationically polymerizable compound (c), preferably a radical polymerizable compound (a): 60 To 99% by mass, the cationically polymerizable compound (c): 1 to 40% by mass, more preferably a radical polymerizable compound (a): 90 to 99% by mass, and a cationically polymerizable compound (c): 1 to 10% by mass .

低Tg自由基聚合性化合物(a)若少於60質量%，則形成之接著層太硬，不僅不能確保接著力，還會導致穿孔加工性惡化。 When the amount of the low Tg radically polymerizable compound (a) is less than 60% by mass, the formed underlayer is too hard, and not only the adhesion is not ensured, but also the piercing processability is deteriorated.

另一方面，低Tg自由基聚合性化合物(a)若比99.8質量%多，亦即幾乎不含有陽離子聚合性化合物(c)時，所形成之接著層的耐水性惡化，若將偏光板浸漬在溫水中，則PVA偏光件的顏色會脫落。 On the other hand, when the amount of the low Tg radically polymerizable compound (a) is more than 99.8% by mass, that is, when the cationically polymerizable compound (c) is hardly contained, the water resistance of the formed subsequent layer is deteriorated, and the polarizing plate is impregnated. In warm water, the color of the PVA polarizer will fall off.

若使用三乙醯纖維素等乙醯纖維素系樹脂薄膜作為保護薄膜時，高Tg自由基聚合性化合物(b)有助於提昇接著力。 When an acetonitrile cellulose resin film such as triacetonitrile cellulose is used as the protective film, the high Tg radical polymerizable compound (b) contributes to the improvement of the adhesion.

使用高Tg自由基聚合性化合物(b)時，較好係低Tg自由基聚合性化合物(a)：60至75質量%、高Tg自由基聚合性化合物(b)：0.01至39.98質量%、陽離子聚合性化合物(c)：0.02至24.99質量%，更好係低Tg自由基聚合性化合物(a)：60至70質量%、高Tg自由基聚合性化合物 (b)：10至35質量%、陽離子聚合性化合物(c)：5至20質量%。 When the high Tg radical polymerizable compound (b) is used, the Tg radical polymerizable compound (a) is preferably 60 to 75 mass%, and the high Tg radical polymerizable compound (b) is 0.01 to 39.98 mass%. Cationic polymerizable compound (c): 0.02 to 24.99% by mass, more preferably low Tg radical polymerizable compound (a): 60 to 70% by mass, high Tg radical polymerizable compound (b): 10 to 35 mass%, cationically polymerizable compound (c): 5 to 20% by mass.

或者是，較佳之一實施形態之光硬化性接著劑中，作為主劑者係含有形成玻璃轉移溫度為-80℃至0℃之均聚物的單官能自由基聚合性化合物(a)：60至99.8質量%、形成玻璃轉移溫度為60℃至250℃之均聚物的單官能自由基聚合性化合物(b)：0至39.98質量%、及具有陽離子聚合性官能基且未具有(甲基)丙烯醯基之陽離子聚合性化合物(c)：0.02至40質量%(惟，上述(a)至(c)合計為100質量%)，作為聚合啟始劑者係含有光自由基聚合啟始劑(d)：1至10質量份(相對於上述(a)至(c)合計100質量份)及光陽離子聚合啟始劑(e)：0.5至5質量份(相對於上述(a)至(c)合計100質量份)。 In the photocurable adhesive according to the preferred embodiment, the monofunctional radical polymerizable compound (a) having a glass transition temperature of -80 ° C to 0 ° C is contained as a main component: 60 Monofunctional radically polymerizable compound (b) which forms a homopolymer of a glass transition temperature of 60 ° C to 250 ° C to 99.8 mass%: 0 to 39.98 mass%, and has a cationically polymerizable functional group and does not have (methyl group) The cationically polymerizable compound (c) of the acrylonitrile group: 0.02 to 40% by mass (except that the above (a) to (c) are 100% by mass in total), and the polymerization initiator is included in the photoradical polymerization. Agent (d): 1 to 10 parts by mass (100 parts by mass relative to the above (a) to (c)) and photocationic polymerization initiator (e): 0.5 to 5 parts by mass (relative to (a) above (c) Total 100 parts by mass).

更好係含有低Tg自由基聚合性化合物(a)：60至99質量%、高Tg自由基聚合性化合物(b)：0至39質量%及陽離子聚合性化合物(c)：1至40質量%。 More preferably, it contains a low Tg radical polymerizable compound (a): 60 to 99% by mass, a high Tg radical polymerizable compound (b): 0 to 39% by mass, and a cationically polymerizable compound (c): 1 to 40 mass %.

本發明之光硬化性接著劑中，除了低Tg自由基聚合性化合物(a)或高Tg自由基聚合性化合物(b)之外，亦可添加其他的自由基聚合性化合物。其他之自由基聚合性化合物可列舉如胺酯丙烯酸酯、環氧基丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯。惟，如上所述，自由基聚合性化合物較好係在限定的調配範圍使用。 In the photocurable adhesive of the present invention, in addition to the low Tg radical polymerizable compound (a) or the high Tg radical polymerizable compound (b), another radical polymerizable compound may be added. Other radical polymerizable compounds include, for example, an amine ester acrylate, an epoxy acrylate, a polyester acrylate, and a polyether acrylate. However, as described above, the radically polymerizable compound is preferably used in a defined blending range.

本發明之光硬化性接著劑中，必要時可添加適當的添 加劑。從可增大與保護薄膜的接著力、可抑制偏光板的收縮之觀點而言，添加劑較好為矽烷偶合劑。矽烷偶合劑較好為具有丙烯醯基者。 In the photocurable adhesive of the present invention, an appropriate addition may be added as necessary Additives. The additive is preferably a decane coupling agent from the viewpoint of increasing the adhesion to the protective film and suppressing shrinkage of the polarizing plate. The decane coupling agent is preferably one having an acrylonitrile group.

本發明之光硬化性接著劑含有光自由基聚合啟始劑(d)。 The photocurable adhesive of the present invention contains a photoradical polymerization initiator (d).

光自由基聚合啟始劑(d)並無特別限制，列舉例如依卡求亞(IRGACURE)-184、907、651、1700、1800、819、369、261；DAROCUR-TPO(汽巴精化公司製造)、塔羅求亞(DAROCUR)-1173(默克(Merck)公司製造)、耶薩求亞(Esacure)-KIP150、TZT(日本謝貝海克那公司製造)、卡亞求亞(KAYACURE)BMS、卡亞求亞DMBI(日本化藥公司製造)等。 The photoradical polymerization initiator (d) is not particularly limited, and examples thereof include IRGACURE-184, 907, 651, 1700, 1800, 819, 369, 261; DAROCUR-TPO (Ciba Specialty Chemicals Co., Ltd. Manufacturing), DAROCUR-1173 (Merck), Esacure-KIP150, TZT (made by Japan Sheikhecken), KAYACURE BMS Kayaqia DMBI (manufactured by Nippon Kayaku Co., Ltd.).

該等中，在提高光硬化後之接著劑層的透明性之觀點，較好係使用光致漂白(Photobleach)之DAROCUR-TPO。 Among these, from the viewpoint of improving the transparency of the adhesive layer after photohardening, photobleaching of DAROCUR-TPO is preferably used.

光自由基聚合啟始劑(d)之調配比率，相對於上述自由基聚合性化合物(a)、(b)及陽離子聚合性化合物(c)之合計100質量份，為1至10質量份，較好為1至5質量份。 The blending ratio of the photoradical polymerization initiator (d) is 1 to 10 parts by mass based on 100 parts by mass of the total of the radical polymerizable compounds (a) and (b) and the cationically polymerizable compound (c). It is preferably from 1 to 5 parts by mass.

本發明之光硬化性接著劑含有光陽離子聚合啟始劑(e)。 The photocurable adhesive of the present invention contains a photocationic polymerization initiator (e).

光陽離子聚合啟始劑(e)可列舉例如UVACURE1590(大協．賽提克(daicel-cytec)公司製造)、CPI-110P(桑阿普洛(San-apro)公司製造)等鋶鹽或IRGACURE250(汽巴精化公司製造)、WPI-113(和光純藥公司製造)、RP-2074(羅迪亞．日本公司製造)等錪鹽等。 The photocationic polymerization initiator (e) may, for example, be a barium salt such as UVACURE 1590 (manufactured by Daicel-Cytec Co., Ltd.) or CPI-110P (manufactured by San-apro Co., Ltd.) or IRGACURE 250. (manufactured by Ciba Specialty Chemicals Co., Ltd.), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), RP-2074 (manufactured by Rodia Co., Ltd.), etc.

光陽離子聚合啟始劑(e)之調配比率，相對於上述自由基聚合性化合物(a)、(b)及陽離子聚合性化合物(c)之合計100質量份，為0.5至10質量份，較好為0.5至5質量份。 The compounding ratio of the photo-cationic polymerization initiator (e) is 0.5 to 10 parts by mass based on 100 parts by mass of the total of the radical polymerizable compounds (a) and (b) and the cationically polymerizable compound (c). It is preferably from 0.5 to 5 parts by mass.

光硬化性接著劑除了上述主劑及聚合啟始劑之外，必要時，在不阻礙本發明效果的範圍內可含有聚合抑制劑、聚合引發助劑、紫外線吸收劑、增塑劑、著色劑、抗氧化劑、消泡劑、可塑劑等各種公知的添加劑。 The photocurable adhesive may contain, in addition to the above-mentioned main component and a polymerization initiator, a polymerization inhibitor, a polymerization initiator, a UV absorber, a plasticizer, and a colorant, as long as the effects of the present invention are not inhibited. Various known additives such as antioxidants, antifoaming agents, and plasticizers.

[偏光件] [Polarizer]

對於本發明偏光板使用之聚乙烯醇系偏光件(第1、2圖中的符號3)加以說明。 The polyvinyl alcohol-based polarizer (reference numeral 3 in Figs. 1 and 2) used in the polarizing plate of the present invention will be described.

形成偏光件，亦即作為偏光件基材的聚乙烯醇系樹脂可列舉聚乙烯醇、乙烯．乙烯醇共聚物等，從耐水性之觀點而言，較好為乙烯．乙烯醇共聚物。聚乙烯醇可列舉如乙酸基有數十%殘存的部分經皂化之聚乙烯醇、乙酸基未殘存而全部皂化之聚乙烯醇、或羥基經改性之改性聚乙烯醇等，惟，並無特別限定。聚乙烯醇系樹脂可單獨使用1種，或亦可將2種以上併用。 The polarizing member is formed, that is, the polyvinyl alcohol-based resin as the substrate of the polarizing member is exemplified by polyvinyl alcohol and ethylene. The vinyl alcohol copolymer or the like is preferably ethylene from the viewpoint of water resistance. Vinyl alcohol copolymer. Examples of the polyvinyl alcohol include, for example, a saponified polyvinyl alcohol having a residual amount of tens of % of an acetic acid group, a polyvinyl alcohol which is not saponified by remaining an acetic acid group, or a modified polyvinyl alcohol modified with a hydroxyl group, etc. There is no special limit. One type of the polyvinyl alcohol-based resin may be used alone or two or more types may be used in combination.

上述聚乙烯醇的具體例可列舉克拉雷(Kuraray)(股)公司製造的RS聚合物之RS-110(皂化度=99%，聚合度=1,000)、同公司製造的克拉雷普巴魯LM20SO(皂化度=40%，聚合度=2,000)、日本合成化學工業(股)公司製造的勾協諾魯NM-14(皂化度=99%，聚合度=1,400)等。聚乙烯醇可藉由例如將乙酸乙烯酯、丙酸乙烯酯、三甲基乙酸乙烯酯等脂肪酸乙烯酯的聚合物使用鹼觸媒等進行皂化而獲 得。 Specific examples of the polyvinyl alcohol include RS-110 (saponification degree = 99%, polymerization degree = 1,000) of RS polymer manufactured by Kuraray Co., Ltd., and Klarip Baru LM20SO manufactured by the same company. (Saponification degree = 40%, degree of polymerization = 2,000), and Kosho Noro NM-14 (saponification degree = 99%, degree of polymerization = 1,400) manufactured by Japan Synthetic Chemical Industry Co., Ltd., and the like. The polyvinyl alcohol can be obtained by, for example, saponifying a polymer of a fatty acid vinyl ester such as vinyl acetate, vinyl propionate or trimethyl vinyl acetate with a base catalyst or the like. Got it.

上述乙烯．乙烯醇共聚物為將乙烯及乙酸乙烯酯之共聚物之皂化物，亦即乙烯-乙酸乙烯酯無規共聚物予以皂化而獲得者，包含從乙酸基有數十莫耳%殘存的部分皂化物到乙酸基僅數莫耳%殘存或乙酸基未殘存之完全皂化物，並無特別限制。 The above ethylene. The vinyl alcohol copolymer is obtained by saponifying a saponified product of a copolymer of ethylene and vinyl acetate, that is, an ethylene-vinyl acetate random copolymer, and contains a partial saponified product having tens of moles of residual from the acetic acid group. There is no particular limitation on the complete saponification in which only a few moles of the acetic acid group remains or the acetate group does not remain.

偏光件係藉由依照公知的方法將上述之聚乙烯醇系樹脂以鑄塑成形法等方法予以薄膜化，並使碘或二色染料(二色性色素)吸附定向而獲得。上述偏光件亦可為經由硼酸等進行交聯或經延伸者。進行延伸時，可在染色前/與染色同時/染色後之任何一個階段進行。偏光件的形狀並無特別限制，可列舉例如薄膜等。又，於本說明書，「薄膜(film)」除了厚度小者(厚度未達1mm者)之外，亦包含厚片(sheet)(例如厚度為1至5mm者)。偏光件的厚度並無特別限制，較好為例如約10至40μm。 The polarizing material is obtained by thin-filming the above polyvinyl alcohol-based resin by a method such as a cast molding method according to a known method, and adsorbing orienting iodine or a dichroic dye (dichroic dye). The polarizer may be crosslinked or extended via boric acid or the like. When stretching is carried out, it can be carried out before or at the same time as dyeing/staining. The shape of the polarizer is not particularly limited, and examples thereof include a film. Further, in the present specification, the "film" includes a sheet (for example, a thickness of 1 to 5 mm) in addition to a small thickness (thickness of less than 1 mm). The thickness of the polarizing member is not particularly limited, and is preferably, for example, about 10 to 40 μm.

[保護薄膜] [Protective film]

對於本發明偏光板使用的保護薄膜(第1、2圖中的符號1、5)加以說明。 The protective film (symbols 1 and 5 in the first and second figures) used in the polarizing plate of the present invention will be described.

保護薄膜並無特別限制，具體而言，可使用現在作為偏光板的保護薄膜最廣泛使用的三乙醯纖維素(TAC)等乙醯纖維素系樹脂薄膜、或透濕度比三乙醯纖維素低的透明樹脂薄膜。 The protective film is not particularly limited, and specifically, an acetaminocellulose-based resin film such as triethyl fluorene cellulose (TAC) which is most widely used as a protective film of a polarizing plate, or a moisture permeability ratio of triacetonitrile cellulose can be used. Low transparent resin film.

構成透濕度比三乙醯纖維素低的保護薄膜的材料，係使用例如透明性、機械強度、熱安定性、水分遮斷性、各 向同性等優越的熱可塑性樹脂。該等熱可塑性樹脂的具體例可列舉環烴烯系樹脂、丙烯酸系樹脂。 A material constituting a protective film having a lower moisture permeability than triethyl hydrazine cellulose is used, for example, for transparency, mechanical strength, thermal stability, moisture barrier property, and each Superior thermoplastic resin such as homosexuality. Specific examples of the thermoplastic resin include a cyclic hydrocarbon-based resin and an acrylic resin.

環烯烴系樹脂為將環狀烯烴作為聚合單位並進行聚合而成的樹脂的總稱。具體例可列舉環狀烴烯之開環(共)聚物、環狀烯烴之加成聚合物、環狀烯烴與乙烯、丙烯等α-烯烴之共聚物(具代表性者為無規共聚物)、及將該等以不飽和羧酸或其衍生物改性之接枝共聚物及該等之氫化物等，較好為降冰片烯(norbornene)系樹脂。降冰片烯系樹脂薄膜可經由日本特開2005-164632號公報、日本特開2006-201736號公報、日本特開2008-233279號公報等記載的公知方法獲得。 The cycloolefin type resin is a general term for a resin obtained by polymerizing a cyclic olefin as a polymerization unit. Specific examples thereof include a ring-opening (co)polymer of a cyclic hydrocarbon, an addition polymer of a cyclic olefin, a copolymer of a cyclic olefin and an α-olefin such as ethylene or propylene (typically a random copolymer) And a graft copolymer which is modified with an unsaturated carboxylic acid or a derivative thereof, and such a hydride or the like are preferably a norbornene-based resin. The norbornene-based resin film can be obtained by a known method described in JP-A-2005-164632, JP-A-2006-201736, JP-A-2008-233279, and the like.

環烯烴系樹脂有種種市售製品。具體例可列舉日本傑旺(ZEON)(股)公司製造之商品名「傑歐諾亞(ZEONOR)」、JSR(股)公司製造之商品名「亞棟(ARTON)」、TICONA公司製造之商品名「特巴斯(TOPAS)」、三井化學(股)公司製造之商品名「APEL」。 There are various commercially available products of cycloolefin resins. Specific examples include the product name "ZEONOR" manufactured by ZEON Co., Ltd., the product name "ARTON" manufactured by JSR Co., Ltd., and the product manufactured by TICONA. The product name "APEL" manufactured by the company "TOPAS" and Mitsui Chemicals Co., Ltd.

丙烯酸系樹脂以聚甲基丙烯酸甲酯為代表，為將甲基丙烯酸甲酯或甲基丙烯酸丁酯等烷基酯類之(甲基)丙烯酸酯作為主成分之樹脂(=共聚物)。根據場合，與其他的樹脂摻合、薄膜化。丙烯酸系薄膜可經由日本特開2002-361712號公報等記載的公知方法獲得。 The acrylic resin is represented by polymethyl methacrylate, and is a resin (= copolymer) containing a (meth) acrylate of an alkyl ester such as methyl methacrylate or butyl methacrylate as a main component. According to the case, it is blended and thinned with other resins. The acrylic film can be obtained by a known method described in JP-A-2002-361712.

丙烯酸系薄膜有種種市售製品。具體例列舉三菱嫘縈公司製造之商品名「阿克利普連(Acryplen)」或卡聶卡(Kaneka)公司製造之商品名「桑迪連(Sunduren)」。 Acrylic films are available in various commercial products. Specific examples include the trade name "Acryplen" manufactured by Mitsubishi Industries Corporation or the trade name "Sunduren" manufactured by Kaneka Corporation.

本發明之偏光板使用的保護薄膜(1)、(5)的兩面可為同一組成，亦可為不同的組成。例如即使(1)使用環烯烴系樹脂薄膜，(5)使用丙烯酸系樹脂薄膜亦沒有任何問題。 The protective films (1) and (5) used in the polarizing plate of the present invention may have the same composition or may have different compositions. For example, even if (1) a cycloolefin-based resin film is used, (5) an acrylic resin film is used without any problem.

保護薄膜的厚度可適當決定，通常從強度、操作性等作業性、薄層性等之觀點而言，為約1至500μm。較好為1至300μm，更好為5至200μm。保護薄膜(1)及(5)的厚度可相同或不同。 The thickness of the protective film can be appropriately determined, and is usually from about 1 to 500 μm from the viewpoints of workability such as strength and workability, and thin layer properties. It is preferably from 1 to 300 μm, more preferably from 5 to 200 μm. The thickness of the protective films (1) and (5) may be the same or different.

又，於偏光件之兩側設置保護薄膜時，其裏外可使用由同一聚合物材料所構成的保護薄膜，亦可使用由不同聚合物材料等所構成的保護薄膜。例如，在偏光件之兩面使用丙烯酸系薄膜時，丙烯酸系聚合物的種類可互相不同，調配的添加劑亦可互相不同，並無任何限制。 Further, when a protective film is provided on both sides of the polarizing member, a protective film made of the same polymer material may be used inside and outside, and a protective film composed of a different polymer material or the like may be used. For example, when an acrylic film is used on both sides of the polarizer, the types of the acrylic polymers may be different from each other, and the formulated additives may be different from each other without any limitation.

本發明的偏光板可經由以下的操作獲得。 The polarizing plate of the present invention can be obtained by the following operations.

亦即，較佳係經由下述操作而製造：在第1保護薄膜(1)之一面塗覆第1光硬化性接著劑，形成第1硬化性接著劑層(2’)；在第2保護薄膜(5)之一面塗覆第2光硬化性接著劑，形成第2硬化性接著劑層(4’)；然後，在聚乙烯醇系偏光件(3)的各面將第1硬化性接著劑層(2’)及第2硬化性接著劑層(4’)同時/或依序重疊；從第2保護薄膜(5)側照射活性能量線，使第1硬化性接著劑層(2’)及第2硬化性接著劑層(4’)硬化。 That is, it is preferably produced by applying a first photocurable adhesive to one surface of the first protective film (1) to form a first curable adhesive layer (2'), and a second protection. The second photocurable adhesive is applied to one surface of the film (5) to form a second curable adhesive layer (4'). Then, the first hardenability is applied to each surface of the polyvinyl alcohol-based polarizer (3). The agent layer (2') and the second curable adhesive layer (4') are simultaneously and/or sequentially overlapped; the active energy ray is irradiated from the side of the second protective film (5) to make the first hardenable adhesive layer (2' And the second hardenable adhesive layer (4') is cured.

上述硬化性接著劑層(2’)及(4’)、保護薄膜(1)及(5) 各自可相同或不同。亦即，硬化性接著劑層(2’)及硬化性接著劑層(4’)(換言之，為第1光硬化性接著劑及第2光硬化性接著劑)可為相同的組成，亦可為不同的組成。形成的接著劑層(2)及(4)的厚度可相同或不同，並無特別限制，通常較好為0.1μm至50μm，更好為0.5μm至20μm。 The above-mentioned curable adhesive layers (2') and (4'), protective films (1) and (5) Each may be the same or different. In other words, the curable adhesive layer (2') and the curable adhesive layer (4') (in other words, the first photocurable adhesive and the second photocurable adhesive) may have the same composition. For different compositions. The thickness of the formed adhesive layers (2) and (4) may be the same or different, and is not particularly limited, and is usually preferably from 0.1 μm to 50 μm, more preferably from 0.5 μm to 20 μm.

以下，以第2圖為基礎，對每個步驟加以說明。 Hereinafter, each step will be described based on Fig. 2 .

[步驟(a)] [Step (a)]

步驟(a)係如第2圖之(a)所示，在保護薄膜(1)及(5)之各個單面塗覆接著劑層形成用的光硬化性接著劑，必要時進行乾燥等，獲得具備硬化性接著劑層(2’)、(4’)之層壓體(1’)、(5’)的步驟。 In the step (a), as shown in FIG. 2(a), a photocurable adhesive for forming an adhesive layer is applied to each of the protective films (1) and (5), and if necessary, drying is performed. A step of obtaining the laminates (1') and (5') having the curable adhesive layers (2') and (4') is obtained.

光硬化性接著劑的塗覆方法並無特別限制，可列舉例如模頭塗覆法(die coating)、滾筒塗覆法、凹版塗覆法、旋轉塗覆法等。 The coating method of the photocurable adhesive is not particularly limited, and examples thereof include a die coating method, a roll coating method, a gravure coating method, a spin coating method, and the like.

[步驟(b)] [Step (b)]

步驟(b)係如第2圖之(b)所示，在聚乙烯醇系偏光件(3)之一面(在圖中為上面)將具備保護薄膜(1)及硬化性接著劑層(2’)之層壓體(1’)疊合，並在聚乙烯醇系偏光件(3)之另一面(在圖中為下面)將具備保護薄膜(5)及硬化性接著劑層(4’)之層壓體(5’)疊合的步驟。 Step (b) is as shown in Fig. 2(b), and a protective film (1) and a curable adhesive layer (2) are provided on one surface (upper side in the figure) of the polyvinyl alcohol-based polarizing member (3). The laminate (1') of ') is laminated, and on the other side (below in the figure) of the polyvinyl alcohol-based polarizing member (3), a protective film (5) and a hardenable adhesive layer (4') are provided. The step of laminating the laminate (5').

[步驟(c)] [Step (c)]

步驟(c)係如第2圖之(c)所示，經由照射活性能量線(6)，使被保護薄膜(1)、(5)及聚乙烯醇系偏光件(3)所挾 住之硬化性接著劑層(2’)、(4’)硬化，形成接著劑層(2)、(4)的步驟。 Step (c) is carried out by irradiating the active energy ray (6) to the protected film (1), (5) and the polyvinyl alcohol-based polarizing member (3) as shown in Fig. 2(c). The step of hardening the adhesive layers (2') and (4') is cured to form the adhesive layers (2) and (4).

於圖中雖表示從保護薄膜(5)側照射活性能量線(6)的情形，惟，亦可從保護薄膜(1)側照射活性能量線(6)，亦可從兩側同時或從兩側依序照射活性能量線(6)。 Although the active energy ray (6) is irradiated from the protective film (5) side in the figure, the active energy ray (6) may be irradiated from the side of the protective film (1), or may be simultaneously or from both sides. The active energy lines (6) are sequentially irradiated on the side.

活性能量線的照射量並無特別限制，較好係將波長200至450nm、照度1至500mW/cm2的光以使照射量成為10至5000mJ/cm2之方式進行照射而進行曝光。照射量若比10mJ/cm2低，則不能促進紫外線硬化性組成物的硬化，不能發揮所希望的性能，照射量若比5000mJ/cm2高，則照射時間變非常長，有生產性的問題。照射之活性能量線的種類可列舉如可見光、紫外線、X線、α線、β線、γ線等，以紫外線較佳。光的照射裝置較好係使用例如高壓水銀燈、低壓水銀燈、鹵化金屬燈、準分子燈(Excimer lamp)等。 The amount of irradiation of the active energy ray is not particularly limited, and it is preferred to irradiate light having a wavelength of 200 to 450 nm and an illuminance of 1 to 500 mW/cm 2 so as to have an irradiation amount of 10 to 5000 mJ/cm 2 . When the irradiation amount is less than 10 mJ/cm 2 , the ultraviolet curable composition cannot be cured, and the desired performance cannot be exhibited. When the irradiation amount is higher than 5000 mJ/cm 2 , the irradiation time becomes extremely long, and there is a problem of productivity. . Examples of the type of the active energy ray to be irradiated include visible light, ultraviolet ray, X-ray, α-line, β-line, γ-ray, etc., and ultraviolet rays are preferred. The light irradiation device is preferably, for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp or the like.

照射活性能量線(6)後，亦可在室溫進行約1週的老化(aging)。 After the active energy ray (6) is irradiated, aging may be performed at room temperature for about one week.

經由步驟(c)，使硬化性接著劑層(2’)、(4’)硬化而製成接著劑層(2)、(4)，並完成使偏光件(3)、保護薄膜(1)及(5)藉由接著劑層(2)、(4)而接著成的偏光板(參照第1圖、第2圖中的(d))。 By the step (c), the curable adhesive layers (2'), (4') are cured to form the adhesive layers (2), (4), and the polarizing member (3) and the protective film (1) are completed. And (5) a polarizing plate which is formed by the adhesive layers (2) and (4) (see FIG. 1 and (d) of FIG. 2).

本發明的偏光板亦可藉由下述操作而製造：在聚乙烯醇系偏光件(3)之一面塗抹光硬化性接著劑而形成第1硬化性接著劑層(2’)，並將形成的第1硬化性接著劑層(2’) 的表面用第1保護薄膜(1)被覆，其次，在聚乙烯醇系偏光件(3)之另一面塗抺光硬化性接著劑而形成第2硬化性接著劑層(4’)，並將形成的第2硬化性接著劑層(4’)的表面用第2保護薄膜(5)被覆，然後，從第2保護薄膜(5)側照射活性能量線，使第1硬化性接著劑層(2’)及第2硬化性接著劑層(4’)硬化。 The polarizing plate of the present invention can also be produced by applying a photocurable adhesive to one side of a polyvinyl alcohol-based polarizing member (3) to form a first curable adhesive layer (2'), and will form First hardenable adhesive layer (2') The surface is covered with the first protective film (1), and secondly, the second curable adhesive layer (4') is formed by applying a photocurable adhesive to the other surface of the polyvinyl alcohol-based polarizer (3), and The surface of the formed second curable adhesive layer (4') is covered with the second protective film (5), and then the active energy ray is irradiated from the side of the second protective film (5) to form the first curable adhesive layer ( 2') and the second hardenable adhesive layer (4') are hardened.

偏光板係如上所述，為含有偏光件、接著層及保護薄膜作為必需構成者，但亦可含有其他之任意構成。例如在任意位置，必要時可含有反射層、抗反射層、硬塗膜層、防污層、防霧層、防黏附(anti-sticking)層等。 As described above, the polarizing plate is an essential component including a polarizing material, an adhesive layer, and a protective film, but may have any other configuration. For example, at any position, if necessary, a reflective layer, an antireflection layer, a hard coat layer, an antifouling layer, an antifogging layer, an anti-sticking layer, or the like may be contained.

(實施例) (Example) [聚乙烯醇系偏光件]的製造例 [Production Example of [Polyvinyl Alcohol Polarizer]

將硼酸20質量份、碘0.2質量份、碘化鉀0.5質量份溶解於水480質量份，調製染色液。將PVA薄膜(維尼綸(vinylon)薄膜#40，愛謝羅(AICELLO)公司製造)浸漬在該染色液30秒後，將薄膜朝一方向延伸2倍，使其乾燥，獲得膜厚30μm的PVA偏光件。 20 parts by mass of boric acid, 0.2 parts by mass of iodine, and 0.5 part by mass of potassium iodide were dissolved in 480 parts by mass of water to prepare a dyeing liquid. After immersing the PVA film (vinylon film #40, manufactured by AICELLO Co., Ltd.) in the dyeing solution for 30 seconds, the film was stretched twice in one direction and dried to obtain a PVA polarized film having a film thickness of 30 μm. Pieces.

[實施例1] [Example 1]

保護薄膜(1)係使用三菱嫘縈(股)公司製造的含有紫外線吸收劑之丙烯酸系薄膜：HBD-002(50μm)，保護薄膜(5)係使用日本傑旺公司製造的未含有紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「ZF-14」(100μm)，對各自的表面以300W．分鐘/m2的放電量進行電暈處理。在表面處理後1小時以內，對保護薄膜(1)及(5)分別使用線棒塗覆機 #3塗抹表1表示的光聚合組成物，形成硬化性接著劑層(2’)、(4’)，在該硬化性接著劑層(2’)與(4’)之間挾住上述PVA偏光件，獲得由保護薄膜(1)/硬化性接著劑層(2’)/PVA系偏光件(3)/硬化性接著劑層(4’)/保護薄膜(5)所構成的層壓體。 The protective film (1) was an acrylic film containing an ultraviolet absorber manufactured by Mitsubishi Rayon Co., Ltd.: HBD-002 (50 μm), and the protective film (5) was made of a UV-absorbing agent manufactured by Japan Jiewang Co., Ltd. The cycloolefin film, Geono's film "ZF-14" (100μm), is 300W for each surface. The discharge amount in minutes/m 2 was subjected to corona treatment. The photopolymerizable composition shown in Table 1 was applied to the protective films (1) and (5) using a wire bar coater #3 within 1 hour after the surface treatment to form a curable adhesive layer (2'), (4). '), the PVA polarizer is sandwiched between the curable adhesive layers (2') and (4') to obtain a protective film (1) / a curable adhesive layer (2') / PVA polarizer (3) A laminate comprising a curable adhesive layer (4') / a protective film (5).

以使保護薄膜(1)相接於馬口鐵板(tinplate)之方式，將該層壓體之四方用玻璃膠帶固定，固定於馬口鐵板上。 The protective film (1) was attached to a tinplate, and the square of the laminate was fixed with a glass tape and fixed to a tinplate.

用UV照射裝置(東芝公司製造，高壓水銀燈)從保護薄膜(5)側照射最大照度500mW/cm2、積分光量800mJ/cm2的紫外線，製作偏光板。形成之各接著劑層的厚度為3至4μm。 A polarizing plate was produced by irradiating ultraviolet rays having a maximum illuminance of 500 mW/cm 2 and an integrated light amount of 800 mJ/cm 2 from the protective film (5) side by a UV irradiation device (manufactured by Toshiba Corporation, a high-pressure mercury lamp). Each of the adhesive layers formed has a thickness of 3 to 4 μm.

[實施例2至8、比較例1至7] [Examples 2 to 8 and Comparative Examples 1 to 7]

除了將光硬化性聚合組成物變更為如表1及表2所示者以外，經由與實施例1相同的操作而製作偏光板，並根據後述的方法評估其性能。 A polarizing plate was produced by the same operation as in Example 1 except that the photocurable polymer composition was changed to the one shown in Table 1 and Table 2, and the performance was evaluated according to the method described later.

[實施例9及10] [Examples 9 and 10]

除了在實施例9中之保護薄膜(1)改用富士薄膜(股)公司製造的含有紫外線吸收劑之三乙醯纖維素系薄膜：商品台「富士達克」(80μm)，在實施例10中之保護薄膜(1)改用日本傑旺公司製造的未含有紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「ZF-14」(100μm)以外，進行與實施例3相同的操作而獲得偏光板，並進行相同之評估。 In addition to the protective film (1) in the ninth embodiment, a triethylene phthalocyanine-based film containing a UV absorber manufactured by Fujifilm Co., Ltd. was used: a product table "Fujidak" (80 μm), in Example 10 In the same manner as in Example 3, the protective film (1) was obtained by the same operation as in Example 3 except that the cycloolefin film (ZF-14) (100 μm) which is not contained in the ultraviolet absorber and which was produced by Japan Jiewang Co., Ltd. was used. Polarizers and the same evaluation.

[實施例11] [Example 11]

除了保護薄膜(1)改用富士薄膜(股)公司製造的含有 紫外線吸收劑之三乙醯纖維素系薄膜：商品名「富士達克」(80μm)，且保護薄膜(5)改用未含有紫外線吸收劑之三乙醯纖維素系薄膜：商品名「TACPHAN N828GL」(80μm)以外，進行與實施例3相同的操作而獲得偏光板，並進行相同之評估。 In addition to the protective film (1), it is replaced by Fujifilm Co., Ltd. A triethylene glycol cellulose film of the ultraviolet absorber: trade name "Fujidak" (80 μm), and the protective film (5) is changed to a triacetyl cellulose film which does not contain a UV absorber: trade name "TACPHAN N828GL" The same operation as in Example 3 was carried out except for (80 μm) to obtain a polarizing plate, and the same evaluation was performed.

[實施例12] [Embodiment 12]

保護薄膜(1)、(5)係與實施例11相同，並使用如表1表示之含有高Tg自由基聚合性化合物(b)之光硬化性接著劑，進行與實施例3相同的操作而獲得偏光板，並進行相同之評估。 The protective films (1) and (5) were the same as in Example 11, and the same operation as in Example 3 was carried out using the photocurable adhesive containing the high Tg radical polymerizable compound (b) shown in Table 1. A polarizing plate was obtained and the same evaluation was performed.

[實施例13] [Example 13]

除了保護薄膜(1)、(5)使用日本傑旺公司製造的未含有紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「ZF-14」(100μm)以外，使用與實施例12相同的光硬化性接著劑，獲得偏光板，進行相同的評估。 The same light as in Example 12 was used except that the protective films (1) and (5) were made of a cycloolefin film not containing an ultraviolet absorber manufactured by Japan Jiewang Co., Ltd., and a Zeonoa film "ZF-14" (100 μm). A hardening adhesive was used to obtain a polarizing plate, and the same evaluation was performed.

[實施例14及15] [Examples 14 and 15]

保護薄膜(1)、(5)係與實施例13相同，並使用如表1表示之含有多官能丙烯酸酯(b)或具有丙烯醯基之陽離子聚合性化合物(x)的光硬化性接著劑，進行與實施例13相同的操作，獲得偏光板，進行相同之評估。 The protective films (1) and (5) were the same as in Example 13, and a photocurable adhesive containing a polyfunctional acrylate (b) or a cationically polymerizable compound (x) having an acrylonitrile group as shown in Table 1 was used. The same operation as in Example 13 was carried out to obtain a polarizing plate, and the same evaluation was carried out.

[比較例8至11] [Comparative Examples 8 to 11]

保護薄膜(1)、(5)係使用日本傑旺公司製造的未含有紫外線吸收劑之環烯烴薄膜、傑歐諾亞薄膜「ZF-14」(100μm)，並使用表2記載的光硬化性接著劑，獲得偏光板， 進行相同之評估。 The protective films (1) and (5) were made of a cycloolefin film (ZF-14) (100 μm) which was not contained in the ultraviolet absorber, and which was produced by the Japan Jiewang Co., Ltd., and the photocurability described in Table 2 was used. Following the agent, a polarizing plate is obtained, Make the same assessment.

<接著力(剝離強度)> <Continuity force (peel strength)>

將獲得的偏光板用切割機切成25mm×150mm的大小，作為試樣。將試樣以雙面黏著膠帶(東洋油墨製造(股)公司製造之DF8712S)貼附在金屬板上。對於試樣(偏光板)，在保護薄膜與偏光件之間預先設置剝離的記號，於23℃、50%RH環境下，以剝離速度：300mm/分鐘測定接著力。表中的接著力係根據以下的基準評估。 The obtained polarizing plate was cut into a size of 25 mm × 150 mm by a cutter to obtain a sample. The sample was attached to a metal plate with a double-sided adhesive tape (DF8712S manufactured by Toyo Ink Co., Ltd.). For the sample (polarizing plate), a peeling mark was previously provided between the protective film and the polarizer, and the adhesion was measured at a peeling speed of 300 mm/min in an environment of 23° C. and 50% RH. The adhesion force in the table is evaluated based on the following criteria.

2.5(N/25mm)以上．．．◎ 2.5 (N/25mm) or more. . . ◎

1.5(N/25mm)以上至未達2.5(N/25mm)．．．○ 1.5 (N/25mm) or more to less than 2.5 (N/25mm). . . ○

1.0(N/25mm)以上至未達1.5(N/25mm)．．．△ 1.0 (N/25mm) or more to less than 1.5 (N/25mm). . . △

未達1.0(N/25mm)．．．× Not up to 1.0 (N/25mm). . . ×

<切割試驗(密著力試驗)> <Cutting test (tightness test)>

在獲得的偏光板之保護薄膜與偏光件之間劃入切割機的刀刃，將刀刃推進時，刀刃的進入形式用以下的基準進行評估。 When the blade of the cutter was cut between the protective film of the obtained polarizing plate and the polarizer, and the blade was advanced, the entry form of the blade was evaluated by the following criteria.

切割機的刀刃不容易進入薄膜間．．．◎ The cutting edge of the cutting machine does not easily enter the film. . . ◎

將切割機的刀刃推進時，刀刃在進入薄膜間4至5mm處停止．．．○ When the cutting edge of the cutting machine is advanced, the cutting edge stops between 4 and 5 mm between the films. . . ○

切割機的刀刃順利地進入薄膜間．．．× The cutting edge of the cutting machine smoothly enters the film. . . ×

<穿孔加工性> <Perforation processability>

使用菪貝魯(Dumbbel)公司製造的100mm×100mm的刀，從保護薄膜(1)側將製作的偏光板穿孔。 The produced polarizing plate was perforated from the side of the protective film (1) using a 100 mm × 100 mm knife manufactured by Dumbbel Co., Ltd.

用目視觀察經穿孔的偏光板周邊的剝離狀態。 The peeling state around the perforated polarizing plate was visually observed.

相對於偏光板的面積(100cm2)，剝離面積的比例(%)未達0至1%者為◎，未達1至2%者為○，未達2至3%者為△，剝離面積在3%以上者為×。 With respect to the area of the polarizing plate (100 cm 2 ), the ratio (%) of the peeling area is less than 0 to 1%, which is ◎, when it is less than 1 to 2%, it is ○, and when it is less than 2 to 3%, it is Δ, and the peeling area is Those who are above 3% are ×.

<溫水浸漬試驗(耐水性)> <Warm water immersion test (water resistance)>

將獲得的偏光板用切割機切成25mm×50mm的大小，作為試樣，將該試樣在恆溫水(60℃)中分別浸漬24小時及72小時後，用目視觀察試樣(偏光板)的脫色程度。 The obtained polarizing plate was cut into a size of 25 mm × 50 mm by a cutter, and the sample was immersed in constant temperature water (60 ° C) for 24 hours and 72 hours, respectively, and the sample (polarizing plate) was visually observed. The degree of bleaching.

相對於偏光板的面積，脫色面積的比例(%)未達0至10%者為◎，未達10至30%者為○，在30%以上者為×。 The ratio (%) of the decolorizing area is less than 0 to 10% with respect to the area of the polarizing plate, ◎ is less than 10 to 30%, and × is 30% or more.

評估結果表示於表1及表2。使用之化合物及保護薄膜係詳細記載於表1的下面。 The evaluation results are shown in Tables 1 and 2. The compound to be used and the protective film are described in detail below in Table 1.

如表1所示，在任何一個實施例中，皆可形成接著性、穿孔加工性及耐水性優越的偏光件。 As shown in Table 1, in any of the examples, a polarizer having excellent adhesion, puncture processability, and water resistance can be formed.

實施例3及實施例6係任一例都為使用未含高Tg自由基聚合性化合物(b)，且低Tg自由基聚合性化合物(a)之含量為90質量%的光硬化性接著劑的情形，低Tg自由基聚合性化合物(a)除了丙烯酸4-羥基丁酯之外亦併用ω-羧基-聚己內酯丙烯酸酯的實施例3，係凝集力比實施例6高，在接著力之特點上為優越。 In any of the examples 3 and 6, a photocurable adhesive containing no high Tg radical polymerizable compound (b) and having a low Tg radical polymerizable compound (a) content of 90% by mass is used. In the case where the low Tg radical polymerizable compound (a) is used in addition to 4-hydroxybutyl acrylate, ω-carboxy-polycaprolactone acrylate is used in the same manner as in Example 3, and the cohesive force is higher than that in the case of Example 6, It is superior in character.

實施例12為使用含有高Tg自由基聚合性化合物(b)的光硬化性接著劑的情形，與未含有高Tg自由基聚合性化合物(b)之實施例11相比，由於對於保護薄膜之三乙醯纖維素系薄膜的接著性優越，所以在接著力及耐水性之特點上為優越。 Example 12 is a case where a photocurable adhesive containing a high Tg radical polymerizable compound (b) is used, as compared with Example 11 which does not contain a high Tg radical polymerizable compound (b), Since the triacetyl cellulose film is excellent in adhesion, it is superior in characteristics of adhesion and water resistance.

再者，實施例13在與實施例12相比時，為保護薄膜使用透濕性較低之環烯烴薄膜的情形，在耐水性之特點上為更優越。 Further, in the case of Example 13, when a cycloolefin film having a low moisture permeability was used as the protective film in comparison with Example 12, it was superior in water resistance.

另一方面，使用未含陽離子聚合性化合物(c)之光硬化性接著劑之比較例1，即使是24小時的耐水性亦不佳。 On the other hand, in Comparative Example 1 using a photocurable adhesive which does not contain the cationically polymerizable compound (c), the water resistance was not good even for 24 hours.

又，低Tg自由基聚合性化合物(a)含量少之比較例2至5及10係任一例之經硬化之接著層皆變得太硬，故接著力小，穿孔加工性亦不佳。 Further, in the comparative examples 2 to 5 and the 10 examples in which the content of the low Tg radical polymerizable compound (a) is small, the cured adhesive layer is too hard, so that the bonding force is small and the punching workability is also poor.

並且，比較例6、7為低Tg自由基聚合性化合物(a)之含量少，且使用3官能之自由基聚合性化合物替代單官能高Tg自由基聚合性化合物(b)，並使用具有陽離子聚合 性官能基及(甲基)丙烯醯基之化合物替代陽離子聚合性化合物(c)的情形，其接著力極小。 Further, in Comparative Examples 6 and 7, the content of the low Tg radical polymerizable compound (a) is small, and a trifunctional radical polymerizable compound is used in place of the monofunctional high Tg radical polymerizable compound (b), and a cation is used. polymerization In the case where a compound having a functional group and a (meth) acrylonitrile group is substituted for the cationically polymerizable compound (c), the bonding force is extremely small.

比較例8及9為低Tg自由基聚合性化合物(a)之含量不充分，且使用具有陽離子聚合性官能基及(甲基)丙烯醯基之化合物替代陽離子聚合性化合物(c)的情形，其接著力極小。 In Comparative Examples 8 and 9, in the case where the content of the low Tg radical polymerizable compound (a) is insufficient, and the compound having a cationically polymerizable functional group and a (meth)acryl fluorenyl group is used instead of the cationically polymerizable compound (c), Its subsequent force is extremely small.

又，比較例4至9儘管接著力極小，但卻耐水性佳，認為切割試驗之黏合性良好係原因之一。 Further, in Comparative Examples 4 to 9, although the adhesion was extremely small, the water resistance was good, and it was considered that the adhesion of the cutting test was good.

1、5‧‧‧保護薄膜 1, 5‧‧‧ Protective film

1’‧‧‧保護薄膜(1)與由硬化性組成物所構成之層(2’)的層壓體 1'‧‧‧Layer of protective film (1) and layer (2') composed of a hardenable composition

2‧‧‧第1接著劑層 2‧‧‧1st adhesive layer

2’‧‧‧第1硬化性接著劑層 2'‧‧‧1st hardened adhesive layer

3‧‧‧聚乙烯醇系偏光件 3‧‧‧Polyvinyl alcohol polarizer

4‧‧‧第2接著劑層 4‧‧‧2nd adhesive layer

4’‧‧‧第2硬化性接著劑層 4'‧‧‧2nd hardened adhesive layer

5’‧‧‧保護薄膜(5)與由硬化性組成物所構成之層(4’)的層壓體 5' ‧ ‧ laminate of protective film (5) and layer (4') composed of hardenable composition

6‧‧‧活性能量線 6‧‧‧Active energy line

第1圖為表示本發明偏光板之一例之剖面圖(示意圖)。 Fig. 1 is a cross-sectional view (schematic diagram) showing an example of a polarizing plate of the present invention.

第2圖(a)至(d)為表示本發明偏光板之製造方法之一例之流程圖(示意圖)。 Fig. 2 (a) to (d) are flowcharts (schematic diagrams) showing an example of a method of producing a polarizing plate of the present invention.

1、5‧‧‧保護薄膜 1, 5‧‧‧ Protective film

2‧‧‧第1接著劑層 2‧‧‧1st adhesive layer

3‧‧‧聚乙烯醇系偏光件 3‧‧‧Polyvinyl alcohol polarizer

4‧‧‧第2接著劑層 4‧‧‧2nd adhesive layer

Claims (11)

一種偏光板，其係含有聚乙烯醇系偏光件、將光硬化性接著劑硬化而成的接著層、及保護薄膜，且分別藉由保護薄膜隔著上述接著層被覆上述偏光件之兩面而成的偏光板；其特徵為：上述光硬化性接著劑含有由自由基聚合性化合物及陽離子聚合性化合物所構成的主劑、光自由基聚合啟始劑、及光陽離子聚合啟始劑；就上述自由基聚合性化合物而言，選自丙烯酸4-羥基丁酯、丙烯酸2-甲氧基乙酯、丙烯酸3-甲氧基丁酯、甲基丙烯酸十三烷酯、二乙二醇單***丙烯酸酯、丙烯酸三氟乙酯、ω-羧基-聚己內酯丙烯酸酯及乙氧化(9)三羥甲基丙烷三丙烯酸酯所成群組之形成玻璃轉移溫度為-80℃至0℃的均聚物的自由基聚合性化合物(a)在上述主劑中含有60至99.8質量%，並且，前述自由基聚合性化合物(a)中的單官能自由基聚合性化合物的比例為90質量%以上；就上述陽離子聚合性化合物而言，選自3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間-二烷、雙(3,4-環氧基環己基甲基)己二酸酯、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯及1,2-環氧基-4-乙烯基環己烷所成群組的未具有(甲基)丙烯醯基之陽離子聚合性化合物(c)在上述主劑中含有0.02至40質量%； 相對於上述主劑100質量份，分別含有上述光自由基聚合啟始劑1至10質量份、上述光陽離子聚合啟始劑0.5至5質量份。 A polarizing plate comprising a polyvinyl alcohol-based polarizer, an adhesive layer obtained by curing a photocurable adhesive, and a protective film, wherein each of the polarizing members is coated with a protective film via the adhesive layer; The polarizing plate is characterized in that the photocurable adhesive contains a main component composed of a radical polymerizable compound and a cationically polymerizable compound, a photoradical polymerization initiator, and a photocationic polymerization initiator; The radically polymerizable compound is selected from the group consisting of 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, tridecyl methacrylate, and diethylene glycol monoethyl acrylate. The glass transition temperature of the ester, the trifluoroethyl acrylate, the ω-carboxy-polycaprolactone acrylate and the ethoxylated (9) trimethylolpropane triacrylate is from -80 ° C to 0 ° C. The radically polymerizable compound (a) of the polymer contains 60 to 99.8% by mass of the main component, and the ratio of the monofunctional radically polymerizable compound in the radically polymerizable compound (a) is 90% by mass or more. On the above yang In the case of a polymerizable compound, it is selected from 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro -3,4-epoxy)cyclohexane-inter-di Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate and 1,2-ring The cationically polymerizable compound (c) having no (meth) acrylonitrile group in the group of oxy-4-vinylcyclohexane is contained in the above-mentioned main component in an amount of 0.02 to 40% by mass; relative to the above-mentioned main agent 100 The parts by mass contain 1 to 10 parts by mass of the above photoradical polymerization initiator and 0.5 to 5 parts by mass of the photocationic polymerization initiator. 如申請專利範圍第1項之偏光板，其中，上述自由基聚合性化合物(a)係選自丙烯酸4-羥基丁酯及ω-羧基-聚己內酯單丙烯酸酯所成群組，上述陽離子聚合性化合物(c)係3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯。 The polarizing plate of claim 1, wherein the radical polymerizable compound (a) is selected from the group consisting of 4-hydroxybutyl acrylate and ω-carboxy-polycaprolactone monoacrylate, and the cation The polymerizable compound (c) is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylic acid. 如申請專利範圍第1項之偏光板，其中，在上述主劑中含有丙烯酸4-羥基丁酯：10至99.8質量%及ω-羧基-聚己內酯單丙烯酸酯：0至50質量%作為上述自由基聚合性化合物(a)。 The polarizing plate of claim 1, wherein the main agent contains 4-hydroxybutyl acrylate: 10 to 99.8% by mass and ω-carboxy-polycaprolactone monoacrylate: 0 to 50% by mass. The above radical polymerizable compound (a). 如申請專利範圍第1項之偏光板，其中，上述光硬化性接著劑另含有形成玻璃轉移溫度為60至250℃之均聚物的自由基聚合性化合物(b)。 The polarizing plate of claim 1, wherein the photocurable adhesive further contains a radically polymerizable compound (b) which forms a homopolymer having a glass transition temperature of 60 to 250 °C. 如申請專利範圍第1項之偏光板，其中，上述陽離子聚合性化合物(c)在上述陽離子聚合性化合物中占有的比例在75質量%以上。 The polarizing plate of the first aspect of the invention, wherein the ratio of the cationically polymerizable compound (c) to the cationically polymerizable compound is 75% by mass or more. 一種偏光板形成用光硬化性接著劑，其含有由自由基聚合性化合物及陽離子聚合性化合物所構成之主劑、光自由基聚合啟始劑、及光陽離子聚合啟始劑；其中，就上述自由基聚合性化合物而言，選自丙烯酸4-羥基丁酯、丙烯酸2-甲氧基乙酯、丙烯酸3-甲氧基丁酯、甲基丙烯酸十三烷酯、二乙二醇單***丙烯酸酯、 丙烯酸三氟乙酯、ω-羧基-聚己內酯丙烯酸酯及乙氧化(9)三羥甲基丙烷三丙烯酸酯所成群組之形成玻璃轉移溫度為-80℃至0℃之均聚物的自由基聚合性化合物(a)在上述主劑中含有60至99.8質量%，並且，前述自由基聚合性化合物(a)中的單官能自由基聚合性化合物的比例為90質量%以上；就上述陽離子聚合性化合物而言，選自3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間-二烷、雙(3,4-環氧基環己基甲基)己二酸酯、雙(3,4-環氧基-6-甲基環己基甲基)己二酸酯及1,2-環氧基-4-乙烯基環己烷所成群組的未具有(甲基)丙烯醯基之陽離子聚合性化合物(c)在上述主劑中含有0.02至40質量%；相對於上述主劑100質量份，分別含有上述光自由基聚合啟始劑1至10質量份、上述光陽離子聚合啟始劑0.5至5質量份。 A photocurable adhesive for forming a polarizing plate, comprising a main component comprising a radical polymerizable compound and a cationically polymerizable compound, a photoradical polymerization initiator, and a photocationic polymerization initiator; The radically polymerizable compound is selected from the group consisting of 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, tridecyl methacrylate, and diethylene glycol monoethyl acrylate. The glass transition temperature of the group of ester, trifluoroethyl acrylate, ω-carboxy-polycaprolactone acrylate and ethoxylated (9) trimethylolpropane triacrylate is -80 ° C to 0 ° C The radically polymerizable compound (a) of the polymer contains 60 to 99.8% by mass of the main component, and the ratio of the monofunctional radically polymerizable compound in the radically polymerizable compound (a) is 90% by mass or more. In the above cationically polymerizable compound, it is selected from 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylic acid, 2-(3,4-epoxycyclohexyl-5) ,5-spiro-3,4-epoxy)cyclohexane-inter-di Alkane, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate and 1,2-ring The cationically polymerizable compound (c) having no (meth) acrylonitrile group in the group of oxy-4-vinylcyclohexane is contained in the above main component in an amount of 0.02 to 40% by mass; relative to the above-mentioned main agent 100 The parts by mass contain 1 to 10 parts by mass of the above photoradical polymerization initiator and 0.5 to 5 parts by mass of the photocationic polymerization initiator. 如申請專利範圍第6項之偏光板形成用光硬化性接著劑，其中，上述自由基聚合性化合物(a)係選自丙烯酸4-羥基丁酯及ω-羧基-聚己內酯單丙烯酸酯所成群組，上述陽離子聚合性化合物(c)係3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯。 The photocurable adhesive for forming a polarizing plate according to the sixth aspect of the invention, wherein the radical polymerizable compound (a) is selected from the group consisting of 4-hydroxybutyl acrylate and ω-carboxy-polycaprolactone monoacrylate. In the group, the above cationically polymerizable compound (c) is 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylic acid. 如申請專利範圍第6項或第7項之偏光板形成用光硬化性接著劑，其中，含有丙烯酸4-羥基丁酯：10至99.8質量%及ω-羧基-聚己內酯單丙烯酸酯：0至50質量% 作為上述自由基聚合性化合物(a)。 The photocurable adhesive for forming a polarizing plate according to claim 6 or 7, wherein the 4-hydroxybutyl acrylate is contained in an amount of 10 to 99.8% by mass and the ω-carboxy-polycaprolactone monoacrylate: 0 to 50% by mass The radical polymerizable compound (a) is used. 如申請專利範圍第6項或第7項之偏光板形成用光硬化性接著劑，其中，另含有形成玻璃轉移溫度為60至250℃之均聚物的自由基聚合性化合物(b)。 The photocurable adhesive for forming a polarizing plate of claim 6 or 7, wherein the radically polymerizable compound (b) which forms a homopolymer having a glass transition temperature of 60 to 250 ° C is further contained. 一種申請專利範圍第1至5項中任一項之偏光板的製造方法，其中，前述偏光板包含：前述偏光件、將前述光硬化性接著劑硬化而成的第1接著層及第2接著層、以及第1保護薄膜及第2保護薄膜；該製造方法之特徵為：將前述光硬化性接著劑分別塗覆於第1保護薄膜及第2保護薄膜之各一面，而形成第1光硬化性接著劑層及第2光硬化性接著劑層；在前述偏光件之兩面，以使前述第1光硬化性接著劑層及第2光硬化性接著劑層成為內側之方式積層前述第1保護薄膜及第2保護薄膜；透過前述第1保護薄膜及/或第2保護薄膜照射活性能量線，使前述第1光硬化性接著劑層及第2光硬化性接著劑層硬化而形成第1接著層及第2接著層。 The method for producing a polarizing plate according to any one of the first to fifth aspect, wherein the polarizing plate includes: the polarizer; and a first adhesive layer and a second adhesive layer obtained by curing the photocurable adhesive; And a first protective film and a second protective film; wherein the photocurable adhesive is applied to each of the first protective film and the second protective film to form a first photohardenable layer. The first adhesive layer and the second photocurable adhesive layer are laminated on the both surfaces of the polarizer so that the first photocurable adhesive layer and the second photocurable adhesive layer are inside. a film and a second protective film; the first protective film and/or the second protective film are irradiated with an active energy ray to cure the first photocurable adhesive layer and the second photocurable adhesive layer to form a first Layer and second layer. 一種申請專利範圍第1至5項中任一項之偏光板的製造方法，其中，前述偏光板包含：前述偏光件、將前述光硬化性接著劑硬化而成的第1接著層及第2接著層、以及第1保護薄膜及第2保護薄膜；該製造方法之特徵為：在前述偏光件之一面塗覆前述光硬化性接著劑而 形成第1光硬化性接著劑層，並於前述第1光硬化性接著劑層之表面積層第1保護薄膜；在前述偏光件之另一面塗覆前述光硬化性接著劑而形成第2光硬化性接著劑層，並於前述第2光硬化性接著劑層之表面積層第2保護薄膜；透過前述第1保護薄膜及/或第2保護薄膜照射活性能量線，使前述第1光硬化性接著劑層及第2光硬化性接著劑層硬化而形成第1接著層及第2接著層。 The method for producing a polarizing plate according to any one of the first to fifth aspect, wherein the polarizing plate includes: the polarizer; and a first adhesive layer and a second adhesive layer obtained by curing the photocurable adhesive; a layer, and a first protective film and a second protective film; the method of manufacturing the method of applying the photocurable adhesive to one surface of the polarizer a first photocurable adhesive layer is formed on the surface layer of the first photocurable adhesive layer, and a photocurable adhesive is applied to the other surface of the polarizer to form a second photocuring layer. a second adhesive film on the surface layer of the second photocurable adhesive layer; and the first protective film and/or the second protective film are irradiated with the active energy ray to cause the first photocurability to proceed The agent layer and the second photocurable adhesive layer are cured to form a first adhesive layer and a second adhesive layer.
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