TWI654273B - Photocurable adhesive, and polarizing plate, laminated optical member and liquid crystal display device using the same - Google Patents

Photocurable adhesive, and polarizing plate, laminated optical member and liquid crystal display device using the same

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TWI654273B
TWI654273B TW103105245A TW103105245A TWI654273B TW I654273 B TWI654273 B TW I654273B TW 103105245 A TW103105245 A TW 103105245A TW 103105245 A TW103105245 A TW 103105245A TW I654273 B TWI654273 B TW I654273B
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group
carbon atoms
weight
polarizer
adhesive
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TW103105245A
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TW201439261A (en
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久米悅夫
淺津悠司
高橋利行
本間英里
古川達也
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日商住友化學股份有限公司
日商艾迪科股份有限公司
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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
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106—Esters of polycondensation macromers
    • C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)
  • Liquid Crystal (AREA)

Abstract

本發明係提供一種光硬化性接著劑，其係用以對由吸附配向有二色性色素之聚乙烯醇系樹脂膜所構成的偏光器接著由透明樹脂膜所構成的保護膜，且含有：(A)光陽離子硬化性成分100重量份；以及(B)光陽離子聚合引發劑1至10重量份；光陽離子硬化性成分(A)係以既定量含有(A1)特定的脂環式二環氧化合物、(A2)特定的二環氧丙基化合物及(A3)特定的乙烯性不飽和單體所構成的重量平均分子量為5000至100000的聚合物。 The present invention provides a photo-curing adhesive, which is used for adhering a polarizer composed of a polyvinyl alcohol-based resin film having a dichroic pigment to a protective film composed of a transparent resin film, and containing: (A) 100 parts by weight of the photocationically curable component; and (B) 1 to 10 parts by weight of the photocationic polymerization initiator; the photocationically curable component (A) contains (A1) the specific alicyclic bicyclic ring in a predetermined amount. A polymer having a weight average molecular weight of 5,000 to 100,000 composed of an oxygen compound, (A2) a specific diglycidyl compound, and (A3) a specific ethylenically unsaturated monomer.

Description

光硬化性接著劑，以及使用該接著劑之偏光板、積層光學構件與液晶顯示裝置 Photocurable adhesive, and polarizing plate, laminated optical member and liquid crystal display device using the same

本發明係關於使由吸附配向有二色性色素的聚乙烯醇系樹脂薄膜所構成的偏光器與由透明樹脂薄膜所構成的保護膜貼合用之光硬化性接著劑，以及使用該接著劑之偏光板、積層光學構件與液晶顯示裝置。 The present invention relates to a light-curable adhesive for bonding a polarizer composed of a polyvinyl alcohol resin film having a dichroic pigment to an aligning dichroic pigment and a protective film composed of a transparent resin film, and to use the adhesive Polarizing plate, laminated optical member and liquid crystal display device.

偏光板係可用於構成液晶顯示裝置的光學零件之一。偏光板一般係具有於偏光器的兩面積層保護膜之構造，納入液晶顯示裝置。已知有只在偏光器的單面設置保護膜，大多於另一側的面，不只是保護膜，貼合具有其他光學功能的層兼作為保護膜。而且，作為偏光器的製造方法，廣泛採用藉由二色性色素染色的一軸延伸的聚乙烯醇系樹脂膜，進行硼酸處理、水洗後進行乾燥的方法。 A polarizing plate is one of optical components that can be used to constitute a liquid crystal display device. A polarizing plate generally has a structure of a two-area layer protective film on a polarizer, and is incorporated into a liquid crystal display device. It is known that a protective film is provided only on one side of a polarizer, and most of the surface is on the other side, and it is not only a protective film, but also a layer having other optical functions bonded together as a protective film. In addition, as a method for manufacturing a polarizer, a method in which a uniaxially stretched polyvinyl alcohol-based resin film dyed with a dichroic dye is subjected to boric acid treatment, and then washed with water and then dried.

一般於偏光器，上述水洗及乾燥後，立即貼合保護膜。此係因乾燥後的偏光器，物理上強度弱，一旦將其捲取時，有在加工方向容易破裂等的問題。因而，一般乾燥後的偏光器立 即塗佈聚乙烯醇系樹脂的水溶液之水系接著劑，經由該接著劑，在偏光器的兩面同時貼合保護膜。慣例上，使用厚度為30至100μm的三乙醯基纖維素膜作為保護膜。 Generally, in a polarizer, a protective film is attached immediately after the above water washing and drying. This is because the polarizer after drying is physically weak, and once it is wound up, there is a problem that it is easy to break in the processing direction. Therefore, in general, a polarizer immediately after drying is coated with an aqueous adhesive of an aqueous solution of a polyvinyl alcohol resin, and a protective film is simultaneously attached to both sides of the polarizer through the adhesive. Conventionally, a triethylfluorene-based cellulose film having a thickness of 30 to 100 μm is used as the protective film.

三乙醯基纖維素係透明性佳、容易形成各種表面處理層、光學功能層，而且透濕度高，使用如上述的水系接著劑貼合於偏光器後的乾燥可以順利地進行，具有作為保護膜優的優點，相反地起因於透濕度高，將其作為保護膜而貼合之偏光板，在濕熱下，例如溫度70℃、相對濕度90%的條件下，有容易引起劣化等的問題。因此，亦已知有比三乙醯基纖維素的透濕度更低，例如降莰烯(norbornene)系樹脂作為代表例之非結晶性聚烯烴系樹脂作為保護膜。具體地，將熱塑性飽和降莰烯系樹脂片積層於偏光器的至少一側的面作為保護膜，已被記載於日本特開平6-51117號公報(專利文獻1)。 Triethyl cellulose is excellent in transparency, easy to form various surface treatment layers and optical functional layers, and has high moisture permeability. Drying can be smoothly performed after bonding to a polarizer using the above-mentioned water-based adhesive, and it has protection The advantages of the excellent film, on the contrary, are due to the high permeability of the polarizing plate, which is bonded as a protective film. Under humid heat, for example, at a temperature of 70 ° C and a relative humidity of 90%, there is a problem that it easily causes degradation. Therefore, it is also known that the moisture permeability is lower than triethylfluorinated cellulose, and for example, a norbornene-based resin is a representative example of an amorphous polyolefin-based resin as a protective film. Specifically, a surface of at least one side of a polarizer, in which a thermoplastic saturated norbornene-based resin sheet is laminated as a protective film, has been described in Japanese Patent Application Laid-Open No. 6-51117 (Patent Document 1).

由透濕度低的樹脂所構成的保護膜貼合於聚乙烯醇系偏光器時，於以往聚乙烯醇系偏光器與三乙醯基纖維素膜之貼合若以一般所使用之聚乙烯醇系樹脂的水溶液作為接著劑，有接著強度不足，或所得之偏光板的外觀不佳等的問題。此係因透濕度低的樹脂膜一般為疏水性，或因透濕度低，作為溶劑的水無法充分乾燥等的原因所造成的。另一方面，亦已知有於偏光器的兩面貼合不同種類的保護膜。例如，日本特開2002-174729號公報(專利文獻2)，也有提出於偏光器的一側的面，貼合由非結晶性聚烯烴系樹脂等透濕度低的樹脂所構成的保護膜，於偏光器的另一側的面，係貼合以三乙醯基纖維素為首之纖維素系樹脂等透濕度高的樹脂所構成的保護膜。 When a protective film made of a resin having low moisture permeability is bonded to a polyvinyl alcohol-based polarizer, the conventional polyvinyl alcohol-based polarizer and a triethylfluorene-based cellulose film are bonded with a commonly used polyvinyl alcohol An aqueous solution of a resin as an adhesive has problems such as insufficient adhesion strength, or poor appearance of the obtained polarizing plate. This is because the resin film with low moisture permeability is generally hydrophobic, or the water used as a solvent cannot be dried sufficiently due to the low moisture permeability. On the other hand, it is also known that different types of protective films are bonded to both sides of the polarizer. For example, Japanese Patent Application Laid-Open No. 2002-174729 (Patent Document 2) also proposes that a protective film made of a resin having low moisture permeability, such as an amorphous polyolefin resin, be bonded to a surface on one side of a polarizer, and The other surface of the polarizer is a protective film composed of a resin having a high moisture permeability such as cellulose resin such as triethyl cellulose.

因此，作為在透濕度低的樹脂所構成的保護膜與聚乙烯醇系偏光器之間賦予高接著力，同時在纖維素系樹脂等的透濕度高的樹脂與聚乙烯醇系偏光器之間也賦予高接著力之接著劑，有嘗試使用光硬化性接著劑。例如，於日本特開2004-245925號公報(專利文獻3)，係揭露不含芳香環的環氧化合物為主成分之接著劑，提出藉由活性能量線的照射，具體地藉由紫外線的照射所產生之陽離子聚合，以使該接著劑硬化，接著偏光器與保護膜。而且，於日本特開2008-257199號公報(專利文獻4)，係已揭示組合脂環式環氧化合物以及不具有脂環式環氧基的環氧化合物，再調配光陽離子聚合引發劑之光硬化性接著劑，使用於偏光器與保護膜之接著。 Therefore, a high adhesion force is provided between a protective film made of a resin having a low moisture permeability and a polyvinyl alcohol-based polarizer, and a resin having a high moisture permeability, such as a cellulose resin, and a polyvinyl alcohol-based polarizer are simultaneously provided. Adhesives that impart high adhesive strength have also been tried using photocurable adhesives. For example, in Japanese Patent Application Laid-Open No. 2004-245925 (Patent Document 3), an adhesive agent containing an aromatic ring-free epoxy compound as a main component is disclosed, and irradiation with active energy rays, specifically, irradiation with ultraviolet rays is proposed The resulting cation is polymerized to harden the adhesive, followed by a polarizer and a protective film. Furthermore, in Japanese Patent Application Laid-Open No. 2008-257199 (Patent Document 4), it is disclosed that a combination of an alicyclic epoxy compound and an epoxy compound without an alicyclic epoxy group, and a photo-cationic polymerization initiator are blended. A hardening adhesive is used for bonding a polarizer and a protective film.

於日本特開2004-245925號公報(專利文獻3)，係揭露以不含芳香環的環氧化合物為主成分之接著劑，並提出該接著劑照射活性能量線，藉由陽離子聚合，接著偏光器與保護膜之方法。此處所揭露的環氧系接著劑，雖對以非結晶性聚烯烴系樹脂及纖維素系樹脂為首之各種透明樹脂膜貼合於偏光器者特別有效，但特別是以丙烯酸樹脂作為保護膜時，顯然其接著力未必充分。 In Japanese Patent Application Laid-Open No. 2004-245925 (Patent Document 3), an adhesive agent containing an epoxy compound containing no aromatic ring as a main component is disclosed, and it is proposed that the adhesive agent irradiates an active energy ray, undergoes cationic polymerization, and then polarizes light. Device and protective film method. The epoxy-based adhesives disclosed here are particularly effective in bonding various transparent resin films including amorphous polyolefin resins and cellulose resins to polarizers, but especially when acrylic resins are used as protective films. Obviously, its follow-up might not be sufficient.

於日本特開2012-172026號公報(專利文獻5)，係揭露在活性能量線硬化型化合物(A)100重量%中，包含：5至100重量%的具有環氧基或氧雜環丁烷基(oxetanyl)、不具有活性能量線自由基聚合性官能基之重量平均分子量未達5000之活性能量線陽離子硬化型化合物(a1)、以及0至95重量%的活性能量線自由基硬化型化合物(a2)，且相對於活性能量線硬化型化合物(A)100 重量份，含有0.0001至2重量份的重量平均分子量為5000至150000的丙烯酸樹脂(B)之光學膜用接著劑。但是，丙烯酸樹脂(B)的含量超過2重量份時，接著劑的黏度會上升，反而有塗佈面的平滑性變差之可能性(參考段落[0079])，設定丙烯酸樹脂(B)的含量為2重量份以下。 In Japanese Patent Application Laid-Open No. 2012-172026 (Patent Document 5), it is disclosed that 100% by weight of the active energy ray-curable compound (A) contains 5 to 100% by weight of an epoxy group or an oxetane group. Oxetanyl, active energy ray cation-curable compound (a1) without active energy ray radical polymerizable functional group having a weight average molecular weight of less than 5000, and 0 to 95% by weight of active energy ray radical-curable compound (a2) with respect to the active energy ray hardening compound (A) 100 The adhesive agent for optical films containing 0.0001 to 2 parts by weight of an acrylic resin (B) having a weight average molecular weight of 5000 to 150,000. However, when the content of the acrylic resin (B) exceeds 2 parts by weight, the viscosity of the adhesive may increase, and the smoothness of the coated surface may be deteriorated (see paragraph [0079]). The content is 2 parts by weight or less.

先前技術文獻 Prior art literature 專利文獻 Patent literature

專利文獻1：特開平6-51117號公報 Patent Document 1: Japanese Unexamined Patent Publication No. 6-51117

專利文獻2：特開2002-174729號公報 Patent Document 2: Japanese Patent Application Laid-Open No. 2002-174729

專利文獻3：特開2004-245925號公報 Patent Document 3: Japanese Unexamined Patent Publication No. 2004-245925

專利文獻4：特開2008-257199號公報 Patent Document 4: JP-A-2008-257199

專利文獻5：特開2012-172026號公報 Patent Document 5: JP 2012-172026

本發明的課題，係提供一種於偏光器貼合保護膜時，室溫下可能塗佈之具有充分低的黏度、而且亦賦予偏光器/保護膜間的接著力提高之偏光板的光硬化性接著劑。本發明的其他課題，係提供一種相位差板等的其他光學層積層於該偏光板，適合用於液晶顯示裝置之積層光學構件。 The subject of the present invention is to provide a light-hardening property of a polarizing plate that has a sufficiently low viscosity that can be applied at room temperature when a protective film is attached to a polarizer, and also provides an improved adhesion between the polarizer and the protective film. Then agent. Another object of the present invention is to provide another optical layer such as a retardation plate on the polarizing plate, which is suitable for a laminated optical member of a liquid crystal display device.

本發明人等，為了解決如此的課題，進行專心研究的結果，因而完成本發明。具體地，發現在使光陽離子硬化性成分與光陽離子聚合引發劑以既定量調配所成之光硬化性接著劑中，於作為主體之特定脂環式二環氧化合物，使用調配有於分子內具有2個不鍵結於脂環式環的環氧基、不具有芳香環的二環氧丙基化合物以及由特定的乙烯性不飽和單體所構成的聚合物之組成物作為其光陽離子硬化性成分為有效。亦即，具有如此的特定組成之光硬化性接著劑，係在室溫下顯示低黏度，可賦予良好的塗佈性，同時硬化後顯現高儲存彈性率，並牢固地接著偏光器與保護膜。 The present inventors have completed the present invention as a result of intensive studies in order to solve such problems. Specifically, it has been found that, in a photocurable adhesive prepared by mixing a photocationically hardening component and a photocationic polymerization initiator in a predetermined amount, a specific alicyclic diepoxy compound as a main component is used in a molecule to prepare the mixture. A composition having two epoxy groups not bonded to an alicyclic ring, a diglycidyl compound having no aromatic ring, and a polymer composed of a specific ethylenically unsaturated monomer as photocationic hardening Sexual ingredients are effective. That is, a light-curing adhesive having such a specific composition exhibits low viscosity at room temperature, can impart good coatability, and exhibits high storage elasticity after curing, and firmly adheres to a polarizer and a protective film. .

亦即，本發明係用以對於吸附配向有二色性色素之聚乙烯醇系樹脂膜所構成的偏光器接著由透明樹脂膜所構成的保護膜之光硬化性接著劑，其係含有：(A)光陽離子硬化性成分100重量份；以及(B)光陽離子聚合引發劑1至10重量份；光陽離子硬化性成分(A)係含有以下既定量的(A1)、(A2)及(A3)。 That is, the present invention is a light-curing adhesive for polarizers composed of a polyvinyl alcohol-based resin film having a dichroic pigment adsorbed and aligned, and a protective film composed of a transparent resin film, and contains: A) 100 parts by weight of the photocationically curable component; and (B) 1 to 10 parts by weight of the photocationic polymerization initiator; the photocationically curable component (A) contains the following predetermined amounts of (A1), (A2), and (A3) ).

(A1)以下式(I)所示之脂環式二環氧化合物10至60重量%(以光陽離子硬化性成分(A)的全部量作為基準) (A1) 10 to 60% by weight of the alicyclic diepoxy compound represented by the following formula (I) (based on the total amount of the photocationically curable component (A))

式中，R1及R2分別獨立表示氫原子或碳數1至6的烷基，烷基為碳數3以上的時，亦可具有脂環構造。X1為氧原子、碳數1至6的烷二基或以下式(Ia)至(Id)之任一者所示的2價基。 In the formula, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. When the alkyl group is 3 or more carbon atoms, it may have an alicyclic structure. X 1 is an oxygen atom, an alkanediyl group having 1 to 6 carbon atoms, or a divalent group represented by any one of the following formulae (Ia) to (Id).

式中，Y1至Y4分別獨立地表示碳數1至20的烷二基，於碳數3以上的時，亦可具有脂環構造。a及b分別獨立地表示0至20的整數。 In the formula, Y 1 to Y 4 each independently represent an alkanediyl group having 1 to 20 carbon atoms, and when the carbon number is 3 or more, it may have an alicyclic structure. a and b each independently represent an integer of 0 to 20.

(A2)以下式(II)所示之二環氧丙基化合物20至75重量%(以光陽離子硬化性成分(A)的全部量為基準) (A2) 20 to 75% by weight of the diepoxypropyl compound represented by the following formula (II) (based on the total amount of the photocationically curable component (A))

式中，Z表示碳數1至9的伸烷基、碳數3或4的亞烷基或2價脂環式烴基，該伸烷基中的亞甲基，係可被氧原子、-CO-O-、-O-CO-、-SO2-、-SO-或-CO-所示的2價基中斷。 In the formula, Z represents an alkylene group having 1 to 9 carbon atoms, an alkylene group having 3 or 4 carbon atoms, or a divalent alicyclic hydrocarbon group. The methylene group in the alkylene group may be an oxygen atom or -CO. The divalent radicals indicated by -O-, -O-CO-, -SO 2- , -SO-, or -CO- are interrupted.

(A3)選自以下式(III)或(IV)所示之單體中至少1種的乙烯性不飽和單體所構成的重量平均分子量5000至100000的聚合物5至50重量%(以光陽離子硬化性成分(A)的全部量為基準) (A3) a polymer having a weight average molecular weight of 5,000 to 100,000 composed of at least one ethylenically unsaturated monomer selected from the monomers represented by the following formula (III) or (IV), 5 to 50% by weight (in light (Based on the total amount of the cation-curable component (A))

式中，X2表示碳原子數1至7的烷基、碳原子數6至12的芳香基、碳原子數6至10的脂環式烴基或該些官能基的 一部份被選自由環氧基、氧雜環丁烷基、羥基及羧基所成之群之1種以上的基取代者。 In the formula, X 2 represents an alkyl group having 1 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms, an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a part of these functional groups is selected from a ring Those substituted with one or more types of groups consisting of oxy, oxetanyl, hydroxy and carboxyl.

式中，R3表示氫原子、甲基或鹵原子，X3係與上述式(III)中之X2相同。 In the formula, R 3 represents a hydrogen atom, a methyl group or a halogen atom, and X 3 is the same as X 2 in the above formula (III).

於前述聚合物(A3)中，前述乙烯性不飽和單體較佳係包含前述X2或X3為被選自由環氧基、氧雜環丁烷基、羥基所成之群之1種以上的基部分取代的甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以前述式(III)或(IV)所示的乙烯性不飽和單體。 In the polymer (A3), the ethylenically unsaturated monomer preferably includes the X 2 or X 3 being one or more selected from the group consisting of an epoxy group, an oxetanyl group, and a hydroxyl group. When the methyl group is substituted by a methyl group, a branched alkyl group having 2 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, the formula (III) or (IV) The ethylenically unsaturated monomer.

於上述(A3)中，前述乙烯性不飽和單體較佳係包含 (i)前述X2或X3為甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以前述式(III)或(IV)所示的乙烯性不飽和單體20至90重量%，以及(ii)前述X2或X3為被選自由環氧基、氧雜環丁烷基及羥基所成之群之1種以上的基部分取代的甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時以前述式(III)或(IV)所示的乙烯性不飽和單體10至80重量%。 In the above (A3), the ethylenically unsaturated monomer preferably contains (i) the above-mentioned X 2 or X 3 is a methyl group, a branched alkyl group having 2 to 7 carbon atoms, and 6 to 12 carbon atoms; In the case of an aromatic group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, 20 to 90% by weight of the ethylenically unsaturated monomer represented by the aforementioned formula (III) or (IV), and (ii) the aforementioned X 2 or X 3 is a methyl group substituted with one or more kinds of groups selected from the group consisting of an epoxy group, an oxetanyl group, and a hydroxyl group, a branched alkyl group having 2 to 7 carbon atoms, and 6 to 6 carbon atoms In the case of an aromatic group of 12 or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, the ethylenically unsaturated monomer represented by the aforementioned formula (III) or (IV) is 10 to 80% by weight.

上述光硬化性接著劑，其25℃之黏度為2至300mPa．sec以下較佳。 The photocurable adhesive has a viscosity of 25 to 300 mPa at 25 ° C. sec or less is preferred.

前述表示二環氧丙基化合物(A2)之式(II)，Z為碳數3至10之分支狀烷基較佳。 The aforementioned formula (II) representing the diglycidyl compound (A2), and Z is preferably a branched alkyl group having 3 to 10 carbon atoms.

上述光硬化性接著劑，又包含0.5至4重量份的水分較佳。 The photocurable adhesive further preferably contains 0.5 to 4 parts by weight of water.

上述光硬化性接著劑，又包含0.5至8重量份的分子內具有2個羥基之二醇化合物較佳。 The photocurable adhesive further includes a diol compound having two hydroxyl groups in a molecule of 0.5 to 8 parts by weight.

上述光硬化性接著劑，於23℃，浸漬保護膜2天時，保護膜的溶解性為15至70重量%較佳。 When the photocurable adhesive is immersed in the protective film for 2 days at 23 ° C., the solubility of the protective film is preferably 15 to 70% by weight.

而且，本發明亦關於偏光板，其係具有由吸附配向有二色性色素之聚乙烯醇系樹脂膜所構成的偏光器，以及 經由上述任一光硬化性接著劑的硬化物而貼合於前述偏光器的至少一側的面之透明樹脂膜所構成的保護膜。 Further, the present invention also relates to a polarizing plate having a polarizer composed of a polyvinyl alcohol-based resin film having a dichroic pigment adsorbed and aligned, and A protective film made of a transparent resin film bonded to at least one surface of the polarizer via a cured product of any of the photocurable adhesives.

前述透明樹脂膜的主成分較佳為選自由纖維素系樹脂、丙烯酸系樹脂、非結晶性聚烯烴系樹脂、聚酯系樹脂以及聚碳酸酯系樹脂所成之群的至少1種樹脂。而且，前述透明樹脂膜以包含紫外線吸收劑較佳。 The main component of the transparent resin film is preferably at least one resin selected from the group consisting of a cellulose resin, an acrylic resin, an amorphous polyolefin resin, a polyester resin, and a polycarbonate resin. The transparent resin film preferably contains an ultraviolet absorber.

上述偏光板，係藉由180度剝離測試所測定之前述偏光器與前述保護膜之間的接著強度為0.5N/25mm以上較佳。 The above-mentioned polarizing plate preferably has a bonding strength between the polarizer and the protective film measured by a 180-degree peel test of 0.5 N / 25 mm or more.

而且，本發明亦關於上述偏光板與1層以上的其他光學層的積層體所構成的積層光學構件。前述其他光學層以包含相位差板較佳。 The present invention also relates to a laminated optical member composed of a laminated body of the polarizing plate and one or more other optical layers. It is preferable that the other optical layers include a retardation plate.

而且，本發明亦關於包含液晶胞以及配置於前述液晶胞的單側或兩側之上述積層光學構件之液晶顯示裝置。 Furthermore, the present invention also relates to a liquid crystal display device including a liquid crystal cell and the above-mentioned laminated optical member arranged on one side or both sides of the liquid crystal cell.

本發明的光硬化性接著劑，就光陽離子硬化性成分(A)而言，將特定的脂環式二環氧化合物(A1)、特定的二環氧丙基化合物(A2)以及特定的乙烯性不飽和單體所構成的重量平均分子量為5000至100000的聚合物(A3)以既定量分別調配，為低黏度，並可提高偏光器與保護膜間的接著強度。於該偏光板積層係其他光學層之積層光學構件，亦可充分發現偏光板的功能。 In the photocurable adhesive of the present invention, the photocationic curable component (A) includes a specific alicyclic diepoxy compound (A1), a specific diglycidyl compound (A2), and a specific ethylene. The polymer (A3) having a weight-average molecular weight of 5,000 to 100,000 composed of the unsaturated unsaturated monomer is separately formulated at a predetermined amount, has a low viscosity, and can improve the bonding strength between the polarizer and the protective film. The function of the polarizing plate can also be fully found in the laminated optical member of this polarizing plate being a laminated optical member of other optical layers.

以下，詳細說明本發明的實施態樣。本發明係提供一種用以對由聚乙烯醇系樹脂膜所構成的偏光器接著由透明樹脂所構成的保護膜之光硬化性接著劑。本發明又提供一種使用該光硬化性接著劑，於上述偏光器貼合有由透明樹脂所構成的保護膜之偏光板，再者於該偏光板積層有其他光學層之積層光學構件。對於該等的光硬化性接著劑、偏光板以及積層光學構件，隨著該順序而加以說明。 Hereinafter, embodiments of the present invention will be described in detail. The present invention provides a photocurable adhesive for polarizing a polarizer made of a polyvinyl alcohol resin film and then a protective film made of a transparent resin. The present invention also provides a polarizing plate using the photocurable adhesive, and a polarizer having a protective film made of a transparent resin bonded to the polarizer, and a laminated optical member in which other optical layers are laminated on the polarizer. These photocurable adhesives, polarizing plates, and laminated optical members will be described in this order.

[光硬化性接著劑] [Photocurable Adhesive]

於本發明中，用以對由聚乙烯醇系樹脂膜所構成的偏光器接著由透明樹脂所構成的保護膜之光硬化性接著劑，係含有(A)光陽離子硬化性成分以及(B)光陽離子聚合引發劑。 In the present invention, a photocurable adhesive for polarizing a polarizer composed of a polyvinyl alcohol resin film and a protective film composed of a transparent resin, contains (A) a photocationic curable component and (B) Photocationic polymerization initiator.

(A)光陽離子硬化性成分 (A) Photocationic hardening component

其係光硬化性接著劑的主成分，藉由聚合硬化賦予接著力之光陽離子硬化性成分(A)，含有以下之三種化合物。 The main component of the photocurable adhesive is a photocationic curable component (A) which imparts adhesive force by polymerization hardening, and contains the following three compounds.

(A1)上述式(I)所示的脂環式二環氧化合物 (A1) An alicyclic diepoxy compound represented by the above formula (I)

(A2)上述式(II)所示的二環氧丙基化合物以及 (A3)選自由以上述式(III)或(IV)所示的單體中之至少1種的乙烯性不飽和單體所構成的重量平均分子量5000至100000的聚合物。 (A2) a diglycidyl compound represented by the formula (II), and (A3) A polymer selected from the group consisting of at least one ethylenically unsaturated monomer represented by the above formula (III) or (IV) and having a weight average molecular weight of 5000 to 100,000.

(A1)脂環式二環氧化合物 (A1) Alicyclic diepoxy compound

光陽離子硬化性成分(A)之脂環式二環氧化合物(A1)的量，以光陽離子硬化性成分(A)全部量為基準，為10至60重量%。藉由光陽離子硬化性成分(A)中含有10重量%以上的脂環式二環氧化合物(A1)，陽離子聚合的反應性變高，硬化性佳。另一方面，該量為60重量%以上時，以下述的二環氧丙基化合物(A2)以及乙烯性不飽和單體所構成的聚合物(A3)的量相對變少，難以兼顧本發明企圖之光硬化性接著劑的低黏度化以及提高偏光器/保護膜間的密合力。 The amount of the alicyclic diepoxy compound (A1) of the photocationically curable component (A) is 10 to 60% by weight based on the total amount of the photocationically curable component (A). When the photocationic curable component (A) contains an alicyclic diepoxy compound (A1) in an amount of 10% by weight or more, the reactivity of cation polymerization is improved, and the curability is excellent. On the other hand, when the amount is 60% by weight or more, the amount of the polymer (A3) composed of the following diglycidyl compound (A2) and the ethylenically unsaturated monomer is relatively small, and it is difficult to balance the present invention. Attempt to reduce the viscosity of the photocurable adhesive and improve the adhesion between the polarizer and the protective film.

表示脂環式二環氧化合物(A1)之上述式(I)中，R1及R2分別獨立地表示氫原子或碳數1至6的烷基，烷基為碳數3以上時，亦可具有脂環構造。該烷基係於式(I)鍵結於X1之環己烷環的位置為1-位(因此，2個環己烷環之環氧基的位置皆為3,4-位)時，亦可鍵結於1-位至6-位的任一位置。該烷基係當然可為直鏈，於碳數3以上時亦可為分支狀。而且，如上述，於碳數3以上時，亦可具有脂環構造。作為具有脂環構造的烷基的典型例，可舉例如環戊基或環己基。 In the above formula (I) representing an alicyclic diepoxy compound (A1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and when the alkyl group is 3 or more carbon atoms, also It may have an alicyclic structure. The alkyl group is when the position of the cyclohexane ring bonded to X 1 in formula (I) is the 1-position (therefore, the positions of the epoxy groups of the two cyclohexane rings are both the 3,4-position), It can also be bonded at any position from 1-position to 6-position. The alkyl system may be a straight chain, and may be branched when the carbon number is 3 or more. Further, as described above, when the carbon number is 3 or more, it may have an alicyclic structure. Typical examples of the alkyl group having an alicyclic structure include a cyclopentyl group and a cyclohexyl group.

於相同的式(I)中，連結2個3,4-環氧基環己烷環之X1為氧原子、碳數1至6的烷二基或以下式(Ia)至(Id)之任一者所示的2價基。此處，烷二基係概念上包含伸烷基、或亞烷基，伸 烷基可為直鏈狀，於碳數3以上時亦可為分支狀。 In the same formula (I), X 1 connecting two 3,4-epoxycyclohexane rings is an oxygen atom, an alkanediyl group having 1 to 6 carbon atoms, or one of the following formulae (Ia) to (Id) Any of the divalent bases shown. Here, the alkanediyl system conceptually includes an alkylene group or an alkylene group. The alkylene group may be linear or branched when the number of carbon atoms is 3 or more.

而且，於X1為以上述式(Ia)至(Id)的任一者所示的2價基時，各式的連結基Y1、Y2、Y3及Y4分別為碳數1至20的烷二基，該烷二基為碳數3以上時，亦可具有脂環構造。該等烷二基，當然亦可為直鏈狀，於碳數3以上時，亦可為分支狀。如上述，碳數3以上時，亦可具有脂環構造。作為具有脂環構造的烷二基的典型例，例如環伸戊基、環伸己基。 When X 1 is a divalent group represented by any one of the formulae (Ia) to (Id), the linking groups Y 1 , Y 2 , Y 3, and Y 4 of each formula have a carbon number of 1 to If the alkanediyl group is 20 or more, the alkanediyl group may have an alicyclic structure. The alkanediyl group may, of course, be linear, and may be branched when the carbon number is 3 or more. As described above, when the carbon number is 3 or more, it may have an alicyclic structure. Typical examples of the alkanediyl group having an alicyclic structure include cyclopentyl and cyclohexyl.

具體地說明以式(I)所示的脂環式二環氧化合物(A1)時，於式(I)之X1為以上述式(Ia)所示的2價基，該式中的a為0之化合物為3,4-環氧基環己基甲醇(該環己烷環可鍵結有碳數1至6的烷基)與3,4-環氧基環己烷羧酸(該環己烷環可鍵結有碳數1至6的烷基)的酯化物。作為其具體例，例如3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯[於式(I)(其中，X1為a=0之式(Ia)所示的2價基)，R1=R2=H的化合物]、3,4-環氧基-6-甲基環己烷羧酸3,4-環氧基-6-甲基環己基甲酯[具有與上述相同的X1之式(I)，R1=6-甲基、R2=6-甲基的化合物]、3,4-環氧基-1-甲基環己基甲基-3,4-環氧基-1-甲基環己烷羧酸酯[具有與上述相同的X1之式(I)，R1=1-甲基、R2=1-甲基的化合物]、3,4-環氧基-3-甲基環己基甲基-3,4-環氧基-3-甲基環己烷羧酸酯[具有與上述相同的X1之式(I)，R1=3-甲基、R2=3-甲基的化合物]等。 Specifically, when an alicyclic diepoxy compound (A1) represented by the formula (I) is described, X 1 in the formula (I) is a divalent group represented by the formula (Ia), and a in the formula A compound of 0 is 3,4-epoxycyclohexylmethanol (the cyclohexane ring may be bonded to an alkyl group having 1 to 6 carbons) and 3,4-epoxycyclohexanecarboxylic acid (the ring The hexane ring may be bonded to an alkylate having 1 to 6 carbon atoms. As a specific example thereof, for example, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester [in formula (I) (where X 1 is a formula (Ia) where a = 0) Compound shown as divalent group), R 1 = R 2 = H compound], 3,4-epoxy-6-methylcyclohexanecarboxylic acid 3,4-epoxy-6-methylcyclohexylmethyl Esters [compounds of formula (I) having the same X 1 as above, R 1 = 6-methyl, R 2 = 6-methyl], 3,4-epoxy-1-methylcyclohexylmethyl -3,4-epoxy-1-methylcyclohexanecarboxylic acid ester [compound of formula (I) having the same X 1 as above, R 1 = 1-methyl, R 2 = 1-methyl ], 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate [Formula (I) having the same X 1 as above , R 1 = 3-methyl, R 2 = 3-methyl]] and the like.

式(I)之X1為上述式(Ib)所示的2價基之化合物，係烷二醇類與3,4-環氧基環己烷羧酸類(於該環己烷環可鍵結烷基)之酯化物。式(I)之X1為上述式(Ic)所示的2價基之化合物，係脂肪族二羧酸類與3,4-環氧基環己基甲醇(於該環己烷環可鍵結烷基) 的酯化物。而且，式(I)之X1為上述式(Id)所示的2價基之化合物，係3,4-環氧基環己基甲醇(於該環己烷環可鍵結烷基)的醚體(b=0時)或烷二醇類或聚烷二醇類與3,4-環氧基環己基甲醇(於該環己烷環可鍵結烷基)的醚化物(b>0的時)。 X 1 of the formula (I) is a divalent compound represented by the formula (Ib), and is an alkanediol and a 3,4-epoxycyclohexanecarboxylic acid (bondable to the cyclohexane ring) Alkyl) esters. X 1 of the formula (I) is a divalent compound represented by the above formula (Ic), which is an aliphatic dicarboxylic acid and 3,4-epoxycyclohexylmethanol (a cycloalkane-bondable alkane) Ester). In addition, X 1 of the formula (I) is a divalent compound represented by the formula (Id), and is an ether of 3,4-epoxycyclohexylmethanol (an alkyl group can be bonded to the cyclohexane ring). (B = 0) or an etherate of alkanediols or polyalkanediols with 3,4-epoxycyclohexylmethanol (alkyl groups can be bonded to the cyclohexane ring) (b> 0 Time).

(A2)二環氧丙基化合物 (A2) Diglycidyl compound

光陽離子硬化性成分(A)中之二環氧丙基化合物(A2)的量，以光陽離子硬化性成分(A)全部量為基準，為20至75重量%。藉由光陽離子硬化性成分(A)中調配20重量%以上的二環氧丙基化合物(A2)，光硬化性接著劑在25℃之黏度可調整為2至300mPa．sec。另一方面，其量為75重量%以上時，偏光器與保護膜間的密合力變得不足。 The amount of the diglycidyl compound (A2) in the photocationically curable component (A) is 20 to 75% by weight based on the total amount of the photocationically curable component (A). By blending 20% by weight or more of the diglycidyl compound (A2) in the photocationically curable component (A), the viscosity of the photocurable adhesive at 25 ° C can be adjusted to 2 to 300 mPa. sec. On the other hand, when the amount is 75% by weight or more, the adhesion between the polarizer and the protective film becomes insufficient.

從調整黏度的觀點，對於上述脂環式二環氧化合物(A1)與二環氧丙基化合物(A2)的合計量而言，二環氧丙基化合物(A2)的量超過50重量%較佳。 From the viewpoint of adjusting the viscosity, the total amount of the diepoxypropyl compound (A2) exceeds 50% by weight based on the total amount of the alicyclic diepoxy compound (A1) and the diepoxypropyl compound (A2). good.

表示二環氧丙基化合物(A2)的上述式(II)中，Z為碳數1至9的伸烷基、碳數3或4的亞烷基、2價脂環式烴基、SO2、SO或CO。作為2價脂環式烴基的典型例，有環伸戊基、環伸己基。 In the above formula (II) representing a diglycidyl compound (A2), Z is an alkylene group having 1 to 9 carbon atoms, an alkylene group having 3 or 4 carbon atoms, a divalent alicyclic hydrocarbon group, SO 2 , SO or CO. Typical examples of the divalent alicyclic hydrocarbon group include cyclopentyl and cyclohexyl.

於式(II)中，Z為伸烷基的化合物係烷二醇的二環氧丙基醚。舉其具體例時，有乙二醇二環氧丙基醚、丙二醇二環氧丙基醚、1,3-丙二醇二環氧丙基醚、1,4-丁二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚等。 In the formula (II), a diepoxypropyl ether of a compound-based alkanediol in which Z is an alkylene group. Specific examples include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,3-propylene glycol diglycidyl ether, and 1,4-butanediol diglycidyl ether , 1,6-hexanediol diglycidyl ether and the like.

(A3)由乙烯性不飽和單體所構成的聚合物 (A3) Polymer composed of ethylenically unsaturated monomer

由至少1種的乙烯性不飽和單體所構成的聚合物(A3)的量， 以光陽離子硬化性成分(A)全部量為基準，為5至50重量%，較佳為7至30重量%。藉由光陽離子硬化性成分(A)中調配5重量%以上的聚合物(A3)，可顯現偏光器與保護膜間的密合力提高的效果。另一方面，該量為50重量%以上時，黏度變高，所以不佳。未達5%時，因與丙烯酸系保護膜的密合性低，所以不佳。 The amount of the polymer (A3) composed of at least one ethylenically unsaturated monomer, It is 5 to 50% by weight, and preferably 7 to 30% by weight based on the entire amount of the photocationic curable component (A). By blending the polymer (A3) in an amount of 5% by weight or more in the photocationically curable component (A), the effect of improving the adhesion between the polarizer and the protective film can be exhibited. On the other hand, when the amount is 50% by weight or more, the viscosity becomes high, which is not preferable. When it is less than 5%, it is not preferable because the adhesion to the acrylic protective film is low.

由至少1種的乙烯性不飽和單體所構成的聚合物(A3)，可藉由選自上述式(III)或(IV)所示的單體中至少1種的乙烯性不飽和單體聚合而得到。而且，其重量平均分子量為5000至100000。 The polymer (A3) composed of at least one ethylenically unsaturated monomer can be selected from at least one ethylenically unsaturated monomer selected from the monomers represented by the formula (III) or (IV). Obtained by polymerization. Moreover, its weight average molecular weight is 5,000 to 100,000.

上述式(III)或(IV)中的X2或X3係表示 X 2 or X 3 in the formula (III) or (IV) is represented by

(i)碳原子數1至7的烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基或 (i) an alkyl group having 1 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms or

(ii)被選自由環氧基、氧雜環丁烷基、羥基及羧基所成之群之1種以上的基部分取代的碳原子數1至7的烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基。 (ii) an alkyl group having 1 to 7 carbon atoms and an alkyl group having 6 to 12 carbon atoms substituted with one or more types selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group and a carboxyl group; An aromatic group or an alicyclic hydrocarbon group having 6 to 10 carbon atoms.

作為碳原子數1至7(較佳為1至4)的烷基，例如甲基、乙基、丙基、異丙基、丁基、第2丁基、第3丁基、異丁基、戊基、異戊基、第3戊基、己基、2-己基、3-己基、環己基、4-甲基環己基、庚基、2-庚基、3-庚基、異庚基、第3庚基等。該些之中，甲基或碳數2至4的分支狀烷基、或選自由環氧基、氧雜環丁烷基、羥基及羧基所成群之1種以上的基部分取代的甲基或碳數2至4的分支狀烷基，從膜的耐久性的點，較佳。 Examples of the alkyl group having 1 to 7 carbon atoms (preferably 1 to 4) include methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, isobutyl, Pentyl, isopentyl, 3rd pentyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 4-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, 3 heptyl and the like. Among these, a methyl group or a branched alkyl group having 2 to 4 carbon atoms, or a methyl group substituted with one or more types selected from the group consisting of an epoxy group, an oxetanyl group, a hydroxyl group, and a carboxyl group. Or a branched alkyl group having 2 to 4 carbon atoms is preferred from the viewpoint of the durability of the film.

作為碳原子數6至12(較佳為6至10)的芳香基，例如苯基、甲基苯基、萘基等。 Examples of the aromatic group having 6 to 12 carbon atoms (preferably 6 to 10) include a phenyl group, a methylphenyl group, and a naphthyl group.

作為碳原子數6至10的脂環式烴基，例如環己基、甲基環己基、降莰基、雙環戊基、雙環辛基、三甲基雙環庚基、三環辛基、三環癸基、螺環辛基、螺雙環戊基、金剛烷基、異莰基(isobornyl)等。 As the alicyclic hydrocarbon group having 6 to 10 carbon atoms, for example, cyclohexyl, methylcyclohexyl, norbornyl, dicyclopentyl, bicyclooctyl, trimethylbicycloheptyl, tricyclooctyl, tricyclodecyl , Spirooctyl, spirobicyclopentyl, adamantyl, isobornyl and the like.

於上述式(III)中，X2的一部分被環氧基或氧雜環丁烷基取代時以式(III)所示的乙烯性不飽和單體，例如下述式(1)至(3)表示的單體。 In the above formula (III), when a part of X 2 is substituted with an epoxy group or an oxetanyl group, an ethylenically unsaturated monomer represented by the formula (III), for example, the following formulae (1) to (3) ).

(式中，R4表示氫原子或碳原子數1至6的烷基，m為1至6的整數。) (In the formula, R 4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 1 to 6.)

(式中，R5表示氫原子或碳原子數1至6的烷基，n為1至6的整數。) (In the formula, R 5 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).

(式中，R6表示氫原子或碳原子數1至6的烷基，s為1至6的整數。) (In the formula, R 6 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and s is an integer of 1 to 6).

於上述式(IV)中，作為可以成為R3之鹵原子，例如氟、氯、溴、碘等。 Examples of the halogen atom that can be R 3 in the formula (IV) include fluorine, chlorine, bromine, and iodine.

於上述式(IV)中，X3的一部分被環氧基或氧雜環丁烷基取代時，以式(IV)所示的乙烯性不飽和單體，例如以下述式(4)至(6)表示者。 In the above formula (IV), when a part of X 3 is substituted with an epoxy group or an oxetanyl group, the ethylenically unsaturated monomer represented by the formula (IV) is, for example, the following formulae (4) to ( 6) The presenter.

(式中，R3與上述式(IV)相同，R7表示氫原子或碳原子數1至6的烷基，t為1至6的整數。) (In the formula, R 3 is the same as the above formula (IV), R 7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and t is an integer of 1 to 6).

(式中，R3與上述式(IV)相同，R8表示氫原子或碳原子數1至6的烷基，x為1至6的整數。) (In the formula, R 3 is the same as the above formula (IV), R 8 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and x is an integer of 1 to 6).

(式中，R3與上述式(IV)相同，R9表示氫原子或碳原子數1至6的烷基，y為1至6的整數。) (In the formula, R 3 is the same as the formula (IV), R 9 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and y is an integer of 1 to 6).

前述乙烯性不飽和單體，係包含 前述X2或X3為被選自由環氧基、氧雜環丁烷基及羥基所成群之1種以上的基部分取代的甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以前述式(III)或(IV)所示的乙烯性不飽和單體為較佳。 The ethylenically unsaturated monomer includes the methyl group and the number of carbon atoms in which X 2 or X 3 is substituted with one or more kinds of groups selected from the group consisting of an epoxy group, an oxetanyl group, and a hydroxyl group. When a branched alkyl group of 2 to 7, an aromatic group of 6 to 12 carbon atoms, or an alicyclic hydrocarbon group of 6 to 10 carbon atoms, the ethylenically unsaturated monomer represented by the aforementioned formula (III) or (IV) Body is better.

而且，上述乙烯性不飽和單體係包含 (i)上述X2或X3為甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以上述式(III)或(IV)所示的乙烯性不飽和單體20至90重量%，以及 (ii)上述X2或X3為被選自由環氧基、氧雜環丁烷基、羥基所成群之1種以上的基部分取代的甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以上述式(III)或(IV)所示的乙烯性不飽和單體10至80重量%為較佳。 The ethylenically unsaturated monosystem includes (i) the above X 2 or X 3 is a methyl group, a branched alkyl group having 2 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or 6 carbon atoms. When the alicyclic hydrocarbon group is 10 to 10, the ethylenically unsaturated monomer represented by the above formula (III) or (IV) is 20 to 90% by weight, and (ii) the above X 2 or X 3 is selected from epoxy Methyl groups, oxetanyl groups, methyl groups substituted with one or more types of groups, branched alkyl groups having 2 to 7 carbon atoms, aromatic groups having 6 to 12 carbon atoms or carbon atoms In the case of an alicyclic hydrocarbon group of 6 to 10, the ethylenically unsaturated monomer represented by the above formula (III) or (IV) is preferably 10 to 80% by weight.

上述聚合物(A3)的重量平均分子量為5000至100000，較佳為7000至70000。 The weight average molecular weight of the polymer (A3) is 5,000 to 100,000, and preferably 7,000 to 70,000.

上述聚合物(A3)的玻璃轉化溫度(Tg)為40℃以上， 從膜的耐久性的點，為較佳。 The glass transition temperature (Tg) of the polymer (A3) is 40 ° C or higher, From the point of the durability of a film, it is preferable.

構成光硬化性接著劑之光陽離子硬化性成分(A)，分別以上述比例含有上述脂環式二環氧化合物(A1)、二環氧丙基化合物(A2)及乙烯性不飽和單體所構成的聚合物(A3)。謀求更有效地使硬化前的光硬化性接著劑之低黏度化以及偏光器與保護膜間的密合力提高，以光硬化性接著劑的全部量為基準，由脂環式二環氧化合物(A1)與乙烯性不飽和單體所構成的聚合物(A3)的合計量為25重量%以上較佳。 The photocationically curable component (A) constituting the photocurable adhesive contains the alicyclic diepoxy compound (A1), the diglycidyl compound (A2), and the ethylenically unsaturated monomer in the above proportions, respectively. Composition of the polymer (A3). In order to more effectively reduce the viscosity of the photocurable adhesive before curing and improve the adhesion between the polarizer and the protective film, based on the total amount of the photocurable adhesive, an alicyclic diepoxy compound ( The total amount of the polymer (A3) composed of A1) and the ethylenically unsaturated monomer is preferably 25% by weight or more.

(其他光陽離子硬化性成分) (Other photocationically hardening ingredients)

光陽離子硬化性成分(A)係只要為由上述脂環式二環氧化合物(A1)、二環氧丙基化合物(A2)及乙烯性不飽和單體所構成的聚合物(A3)為上述的量，其他光陽離子硬化性成分相對於光陽離子硬化性成分100重量份可含有1至30重量份。 As long as the photocationically curable component (A) is a polymer (A3) composed of the above-mentioned alicyclic diepoxy compound (A1), diglycidyl compound (A2), and ethylenically unsaturated monomer, the above-mentioned The amount of the other photocationically curable component may be 1 to 30 parts by weight based on 100 parts by weight of the photocationically curable component.

作為其他光陽離子硬化性成分，例如(A1)至(A3)以外的環氧化合物、氧雜環丁烷化合物、環狀內酯化合物、環狀縮醛化合物、環狀硫醚化合物、縮環原酸酯(spiro orthoester)化合物、乙烯基化合物等。 As other photocationically hardening components, for example, epoxy compounds other than (A1) to (A3), oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, and cyclogens Spiro orthoester compounds, vinyl compounds and the like.

作為上述乙烯基化合物，例如脂肪族或脂環式乙烯基醚化合物，例如正-戊基乙烯基醚、異-戊基乙烯基醚、正-己基乙烯基醚、正-辛基乙烯基醚、2-乙基己基乙烯基醚、正-十二烷基乙烯基醚、硬脂基乙烯基醚、油基乙烯基醚等的碳數5至20的烷基或烯基醇的乙烯基醚類、2-羥基乙基乙烯基醚、3-羥基丙基乙烯基醚、4-羥基丁基乙烯基醚等含有羥基的乙烯基醚類、環己基乙烯基醚、2-甲基環己基乙烯基醚、環己基甲基乙烯基醚、苯甲 基乙烯基醚等具有脂肪族環或芳香族環之單醇的乙烯基醚類、甘油單乙烯基醚、1,4-丁二醇單乙烯基醚、1,4-丁二醇二乙烯基醚、1,6-己二醇二乙烯基醚、新戊二醇二乙烯基醚、季戊四醇二乙烯基醚、季戊四醇四乙烯基醚、三羥甲基丙烷二乙烯基醚、三羥甲基丙烷三乙烯基醚、1,4-二羥基環己烷單乙烯基醚、1,4-二羥基甲基環己烷二乙烯基醚、1,4-二羥基甲基環己烷單乙烯基醚、1,4-二羥基甲基環己烷二乙烯基醚等多價醇的單至多乙烯基醚類、二乙二醇二乙烯基醚、三乙二醇二乙烯基醚、二乙二醇單丁基單乙烯基醚等聚烷二醇單至二乙烯基醚類、環氧丙基乙烯基醚、乙二醇乙烯基醚甲基丙烯酸酯等其他乙烯基醚類。 As the above-mentioned vinyl compound, for example, an aliphatic or alicyclic vinyl ether compound such as n-pentyl vinyl ether, iso-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, Vinyl ethers of alkyl or alkenyl alcohols having 5 to 20 carbon atoms, such as 2-ethylhexyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether, oleyl vinyl ether, etc. -Hydroxyl-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexyl vinyl ether, 2-methylcyclohexyl vinyl Ether, cyclohexyl methyl vinyl ether, benzyl Vinyl ethers such as vinyl alcohols having aliphatic or aromatic rings, glyceryl monovinyl ether, 1,4-butanediol monovinyl ether, 1,4-butanediol divinyl Ether, 1,6-hexanediol divinyl ether, neopentyl glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropane Trivinyl ether, 1,4-dihydroxycyclohexane monovinyl ether, 1,4-dihydroxymethyl cyclohexane divinyl ether, 1,4-dihydroxymethyl cyclohexane monovinyl ether And polyvalent alcohols such as 1,4-dihydroxymethylcyclohexane divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, diethylene glycol Polyalkylene glycol mono- to divinyl ethers such as monobutyl monovinyl ether, other vinyl ethers such as epoxypropyl vinyl ether, ethylene glycol vinyl ether methacrylate, and the like.

(B)光陽離子聚合引發劑 (B) Photocationic polymerization initiator

於本發明中，因使如以上的陽離子聚合性化合物以活性能量線的照射所進行之陽離子聚合而硬化形成接著劑層，於光硬化性接著劑，係調配光陽離子聚合引發劑(B)。光陽離子聚合引發劑，係藉由如可見光線、紫外線、X射線、電子線之活性能量線的照射，產生陽離子物質或路易斯酸，引發光陽離子硬化性成分(A)的聚合反應者。光陽離子聚合引發劑，由於以光進行催化性作用，即使混合於光陽離子硬化性成分(A)，保存安定性、操作性亦佳。作為藉由活性能量線的照射產生陽離子物質或路易斯酸之化合物，例如芳香族重氮鹽；如芳香族錪鹽、芳香族鋶鹽之鎓鹽；鐵-芳烴(arene)錯合物等。 In the present invention, the above-mentioned cationic polymerizable compound is cured by cationic polymerization by irradiation with active energy rays to form an adhesive layer. The photo-curable adhesive is a photo-cationic polymerization initiator (B). A photocationic polymerization initiator is a person who generates a cationic substance or a Lewis acid by irradiation of active energy rays such as visible light, ultraviolet rays, X-rays, and electron rays, and initiates a polymerization reaction of the photocationic hardening component (A). Since the photocationic polymerization initiator performs photocatalytic action with light, even when mixed with the photocationic hardening component (A), it has excellent storage stability and workability. As a compound that generates a cationic substance or a Lewis acid by irradiation of an active energy ray, for example, an aromatic diazonium salt; for example, an onium salt of an aromatic sulfonium salt or an aromatic sulfonium salt; an iron-arene complex;

作為芳香族重氮鹽，例如重氮苯 六氟銻酸鹽、重氮苯 六氟磷酸鹽、 重氮苯 六氟硼酸鹽。 Examples of the aromatic diazonium salt include diazobenzene hexafluoroantimonate, diazobenzene hexafluorophosphate, Diazobenzene hexafluoroborate.

作為芳香族錪鹽，例如二苯基錪 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。 Examples of the aromatic phosphonium salt include diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, and bis (4-nonylphenyl) phosphonium. Hexafluorophosphate.

作為芳香族鋶鹽，例如 三苯基鋶 六氟磷酸鹽、三苯基鋶 六氟銻酸鹽、三苯基鋶 四(五氟苯基)硼酸鹽、4,4’-雙[二苯基鋶]二苯硫醚 雙六氟磷酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶]二苯硫醚 雙六氟銻酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶]二苯硫醚 雙六氟磷酸鹽、7-[二(對-甲苯基)鋶]-2-異丙基硫雜蒽酮 六氟銻酸鹽、7-[二(對-甲苯基)鋶]-2-異丙基硫雜蒽酮 肆(五氟苯基)硼酸鹽、4-苯基羰基-4’-二苯基鋶-二苯硫醚 六氟磷酸鹽、4-(對-第3丁基苯基羰基)-4’-二苯基鋶-二苯硫醚 六氟銻酸鹽、4-(對-第3丁基苯基羰基)-4’-二(對-甲苯基)鋶-二苯硫醚 肆(五氟苯基)硼酸鹽等。 As an aromatic sulfonium salt, for example Triphenylphosphonium hexafluorophosphate, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium tetrakis (pentafluorophenyl) borate, 4,4'-bis [diphenylphosphonium] diphenylsulfide bis Hexafluorophosphate, 4,4'-bis [bis (β-hydroxyethoxy) phenylfluorene] diphenylsulfide, dihexafluoroantimonate, 4,4'-bis [bis (β-hydroxyethoxylate) Phenyl) phenylfluorene] diphenylsulfide bishexafluorophosphate, 7- [bis (p-tolyl) fluorene] -2-isopropylthioanthrone hexafluoroantimonate, 7- [bis (p- -Tolyl) fluorene] -2-isopropylthioanthrone (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylfluorene-diphenylsulfide hexafluorophosphate, 4 -(P-third-butylphenylcarbonyl) -4'-diphenylfluorene-diphenylsulfide hexafluoroantimonate, 4- (p-third-butylphenylcarbonyl) -4'-bis ( P-tolyl) fluorene-diphenyl sulfide (pentafluorophenyl) borate and the like.

作為鐵-丙二烯錯合物，例如 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。 As an iron-propadiene complex, for example Xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron (II) ginseng ( Trifluoromethylsulfonyl) methane.

該等光陽離子聚合引發劑，可分別單獨使用，或混合2種以上使用。該等之中，特別是芳香族鋶鹽，由於即使在300nm附近的波長區域具有紫外線吸收特性，硬化性佳，可賦予具有良好的機械強度、接著強度之硬化物，適合使用。 These photocationic polymerization initiators can be used alone or in combination of two or more kinds. Among these, especially the aromatic sulfonium salt is suitable for use because it has a UV-absorbing property even in a wavelength region around 300 nm, has a good hardening property, and can give a hardened material having good mechanical strength and adhesive strength.

光陽離子聚合引發劑(B)的調配量，相對於光陽離子硬化性成分(A)全部100重量份，為1至10重量份。光陽離子硬化性成分(A)每100重量份，藉由調配1重量份以上的光陽離子聚合引發劑，可使光陽離子硬化性成分(A)充分硬化，對所得之偏光板賦予高機械強度及接著強度。另一方面，其量變多時，硬化物中的離子性物質增加，硬化物的吸濕性變高，因偏光板的耐久性能有降低的可能性，使光陽離子聚合引發劑(B)的量，對光陽離子硬化性成分(A)每100重量份為10重量份以下。光陽離子聚合引發劑(B)的調配量，對光陽離子硬化性成分(A)每100重量份為2重量份以上較佳，或6重量份以下較佳。 The blending amount of the photocationic polymerization initiator (B) is 1 to 10 parts by weight based on 100 parts by weight of the entire photocationic curable component (A). For every 100 parts by weight of the photocationically curable component (A), by blending more than 1 part by weight of a photocationic polymerization initiator, the photocationically curable component (A) can be sufficiently hardened, and the obtained polarizing plate can be given high mechanical strength and Then intensity. On the other hand, when the amount is increased, the amount of ionic substances in the hardened material increases, and the hygroscopicity of the hardened material becomes high. The durability of the polarizing plate may decrease, and the amount of the photocationic polymerization initiator (B) The photocationically curable component (A) is 10 parts by weight or less per 100 parts by weight. The blending amount of the photocationic polymerization initiator (B) is preferably 2 parts by weight or more, or 6 parts by weight or less per 100 parts by weight of the photocationic curable component (A).

(光增感劑) (Photosensitizer)

本發明的光硬化性接著劑，除包含如上述的環氧化合物之光陽離子硬化性成分(A)以及光陽離子聚合引發劑(B)，亦可含有光增感劑。上述光陽離子聚合引發劑(B)，雖在300nm附近或比其短的波長顯示最大吸收，感應該附近的波長的光，而產生陽離子物質或路易斯酸，引發光陽離子硬化性成分(A)的陽離子聚合，但也感應比其長的波長的光，光增感劑以在比380nm長的波長顯示 最大吸收之光增感劑為較佳。作為如此光增感劑，適合使用蒽系化合物。 The photocurable adhesive of the present invention may contain a photosensitizer in addition to the photocation-curable component (A) and the photocationic polymerization initiator (B) of the epoxy compound described above. Although the photocationic polymerization initiator (B) exhibits the maximum absorption near 300nm or a shorter wavelength, it induces light in the vicinity of the wavelength to generate a cationic substance or a Lewis acid, and triggers the photocationic hardening component (A). Cationic polymerization, but it also senses light with longer wavelengths, and the photosensitizer displays at a wavelength longer than 380nm A light sensitizer with maximum absorption is preferred. As such a photosensitizer, an anthracene-based compound is suitably used.

作為蒽系化合物的具體例，例如9,10-二甲氧基蒽、9,10-二乙氧基蒽、9,10-二丙氧基蒽、9,10-二異丙氧基蒽、9,10-二丁氧基蒽、9,10-二戊氧基蒽、9,10-二己氧基蒽、9,10-雙(2-甲氧基乙氧基)蒽、9,10-雙(2-乙氧基乙氧基)蒽、9,10-雙(2-丁氧基乙氧基)蒽、9,10-雙(3-丁氧基丙氧基)蒽、2-甲基或2-乙基-9,10-二甲氧基蒽、2-甲基或2-乙基-9,10-二乙氧基蒽、2-甲基或2-乙基-9,10-二丙氧基蒽、2-甲基或2-乙基-9,10-二異丙氧基蒽、2-甲基或2-乙基-9,10-二丁氧基蒽、2-甲基或2-乙基-9,10-二戊氧基蒽、2-甲基或2-乙基-9,10-二己氧基蒽。 Specific examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diisopropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-dipentoxyanthracene, 9,10-dihexyloxyanthracene, 9,10-bis (2-methoxyethoxy) anthracene, 9,10 -Bis (2-ethoxyethoxy) anthracene, 9,10-bis (2-butoxyethoxy) anthracene, 9,10-bis (3-butoxypropoxy) anthracene, 2- Methyl or 2-ethyl-9,10-dimethoxyanthracene, 2-methyl or 2-ethyl-9,10-diethoxyanthracene, 2-methyl or 2-ethyl-9, 10-dipropoxyanthracene, 2-methyl or 2-ethyl-9,10-diisopropoxyanthracene, 2-methyl or 2-ethyl-9,10-dibutoxyanthracene, 2 -Methyl or 2-ethyl-9,10-dipentoxyanthracene, 2-methyl or 2-ethyl-9,10-dihexyloxyanthracene.

藉由於光硬化性接著劑中調配如上述的光增感劑，與不調配時比較，可提高接著劑的硬化性。藉由相對於構成光硬化性接著劑的光陽離子硬化性成分(A)100重量份，光增感劑的調 配量為0.1重量份以上，可顯現如此的效果。另一方面，光增感劑的調配量變得多時，由於會產生低溫保管時析出等問題，其量相對於光陽離子硬化性成分(A)100重量份，為2重量份以下。從維持偏光板的中性灰色的觀點，偏光器與保護膜的接著力可保持在適度的範圍下，光增感劑的調配量愈少愈有利，例如相對於光陽離子硬化性成分(A)100重量份，光增感劑的量為0.1至0.5重量份，又以0.1至0.3重量份的範圍較佳。 By blending the photosensitizer as described above in the photocurable adhesive, the curability of the adhesive can be improved compared to when the photosensitizer is not blended. The photosensitizer is adjusted by 100 parts by weight of the photocationically curable component (A) constituting the photocurable adhesive. Such an effect can be exhibited when the compounding quantity is 0.1 weight part or more. On the other hand, when the amount of the photosensitizer is increased, problems such as precipitation during low-temperature storage may occur, and the amount thereof is 2 parts by weight or less based on 100 parts by weight of the photocationic curable component (A). From the viewpoint of maintaining the neutral gray of the polarizing plate, the bonding force between the polarizer and the protective film can be maintained in a moderate range, and the smaller the amount of the light sensitizer, the more advantageous, for example, compared to the photocationic hardening component (A) 100 parts by weight, and the amount of the photosensitizer is preferably 0.1 to 0.5 parts by weight, and more preferably 0.1 to 0.3 parts by weight.

(光增感助劑) (Photosensitizer)

本發明的光硬化性接著劑，除包含如上述的環氧化合物之光陽離子硬化性成分(A)、光陽離子聚合引發劑(B)以及光增感劑外，尚可含有光增感助劑。光增感助劑較佳為萘系光增感助劑。 The photocurable adhesive of the present invention may contain a photosensitizing aid in addition to the photocation-curable component (A) of the epoxy compound, the photocationic polymerization initiator (B), and a photosensitizer. . The photosensitizing aid is preferably a naphthalene-based photosensitizing aid.

作為萘系光增感助劑的具體例，例如4-甲氧基-1-萘酚、4-乙氧基-1-萘酚、4-丙氧基-1-萘酚、4-丁氧基-1-萘酚、4-己氧基-1-萘酚、1,4-二甲氧基萘、1-乙氧基-4-甲氧基萘、1,4-二乙氧基萘、1,4-二丙氧基萘、1,4-二丁氧基萘。 Specific examples of the naphthalene-based photosensitizing aid include 4-methoxy-1-naphthol, 4-ethoxy-1-naphthol, 4-propoxy-1-naphthol, and 4-butoxy 1-naphthol, 4-hexyloxy-1-naphthol, 1,4-dimethoxynaphthalene, 1-ethoxy-4-methoxynaphthalene, 1,4-diethoxynaphthalene , 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene.

藉由光硬化性接著劑中調配萘系光增感助劑，與不調配時比較，可提高接著劑的硬化性。藉由相對於構成光硬化性 接著劑的光陽離子硬化性成分(A)100重量份，萘系光增感助劑的調配量為0.1重量份以上，可顯現如此的效果。另一方面，萘系光增感助劑的調配量變多時，由於會產生低溫保管時析出等問題，其量相對於光陽離子硬化性成分(A)100重量份，為5重量份以下。萘系光增感助劑的調配量，相對於光陽離子硬化性成分(A)100重量份，為3重量份以下較佳。 By blending a naphthalene-based photosensitizing aid in a photocurable adhesive, the hardenability of the adhesive can be improved as compared with when it is not blended. Photo-hardenability Such an effect is exhibited by 100 parts by weight of the photocationically curable component (A) of the adhesive, and the blending amount of the naphthalene-based photosensitizing aid is 0.1 parts by weight or more. On the other hand, when the blending amount of the naphthalene-based photosensitizing aid is increased, problems such as precipitation during low-temperature storage may occur, and the amount thereof is 5 parts by weight or less based on 100 parts by weight of the photocationically curable component (A). The blending amount of the naphthalene-based photosensitizing aid is preferably 3 parts by weight or less based on 100 parts by weight of the photocationically curable component (A).

再者，於本發明的光硬化性接著劑，只要無損本發明的效果，可含有添加劑成分，作為任意成分之其他成分。作為添加劑成分，可調配熱陽離子聚合引發劑、多元醇類、離子捕捉劑、抗氧化劑、光安定劑、鏈轉移劑、黏著賦予劑、熱塑性樹脂、填充劑、流動調整劑、可塑劑、消泡劑、流平劑、色素、有機溶劑等。 Moreover, the photocurable adhesive agent of this invention may contain an additive component as another component of arbitrary components, as long as the effect of this invention is not impaired. As an additive component, thermal cationic polymerization initiators, polyols, ion trapping agents, antioxidants, light stabilizers, chain transfer agents, adhesion-imparting agents, thermoplastic resins, fillers, flow regulators, plasticizers, and defoamers can be blended. Agents, leveling agents, pigments, organic solvents, etc.

含有添加劑成分時，添加劑成分的使用量，相對於前述光陽離子硬化性成分(A)100重量份，為1000重量份以下較佳。該使用量為1000重量份以下時，作為本發明的光硬化性接著劑之必要成分之光陽離子硬化性成分(A)以及光陽離子聚合引發劑(B)的組合，可良好地發揮所謂保存安定性之提高、防止變色、硬化速度的提高、確保良好的接著性之效果。 When the additive component is contained, the use amount of the additive component is preferably 1,000 parts by weight or less based on 100 parts by weight of the photocationically curable component (A). When the used amount is 1,000 parts by weight or less, the combination of the photocationic curable component (A) and the photocationic polymerization initiator (B), which are essential components of the photocurable adhesive of the present invention, can exhibit the so-called storage stability well. The effect of improving the properties, preventing discoloration, increasing the curing speed, and ensuring good adhesion.

(水分) (Moisture)

本發明的光硬化性接著劑，除包含如上述的環氧化合物之光陽離子硬化性成分(A)以及光陽離子聚合引發劑(B)外，尚可含有水分。藉由調配水分，可進一步提高偏光器與保護膜之間的接著力。藉由相對於構成光硬化性接著劑的光陽離子硬化性成分(A)100重量份，水分的調配量為0.5重量份以上，更佳為1重量 份以上，可顯現接著力上升的效果。另一方面，水分的調配量變多時，引起光硬化性接著劑與水分的分離，因光硬化性接著劑變得無法均勻地塗佈於偏光器、保護膜的表面，光硬化性接著劑的硬化性變差，故相對於構成光硬化性接著劑的光陽離子硬化性成分(A)100重量份，水分的調配量為4重量份以下，更佳為未達3重量份。水分的種類，無特別限制，例如可使用如蒸餾水、純水的精製水。 The photocurable adhesive of the present invention may contain water in addition to the photocation-curable component (A) and the photocationic polymerization initiator (B) of the epoxy compound described above. By adjusting the moisture content, the adhesion between the polarizer and the protective film can be further improved. With respect to 100 parts by weight of the photocationically curable component (A) constituting the photo-curable adhesive, the amount of water formulated is 0.5 part by weight or more, and more preferably 1 part by weight If it is at least 1 part, the effect of increasing the adhesive force can be exhibited. On the other hand, when the amount of water is increased, the photocurable adhesive is separated from the water, and the photocurable adhesive cannot be uniformly coated on the surface of the polarizer and the protective film. Since the hardenability is deteriorated, the amount of water to be formulated is 4 parts by weight or less, and more preferably less than 3 parts by weight, based on 100 parts by weight of the photocationic hardening component (A) constituting the photocurable adhesive. The type of water is not particularly limited, and for example, purified water such as distilled water and pure water can be used.

(二醇化合物) (Diol compound)

本發明的光硬化性接著劑，除包含如上述的環氧化合物之光陽離子硬化性成分(A)以及光陽離子聚合引發劑(B)外，尚可含有二醇化合物。藉由調配二醇化合物，可提高接著力，特別是偏光器與保護膜間的接著力。 The photocurable adhesive of the present invention may contain a diol compound in addition to the photocation-curable component (A) and the photocationic polymerization initiator (B) of the epoxy compound described above. By blending a diol compound, the adhesion force can be improved, especially the adhesion force between the polarizer and the protective film.

二醇化合物係分子內具有2個羥基的化合物，典型地為下式(V)所示的化合物。 The diol compound is a compound having two hydroxyl groups in the molecule, and is typically a compound represented by the following formula (V).

HO-A-OH (V) HO-A-OH (V)

式中的A，可為亦可被氧原子中斷之總碳數2至8的伸烷基。 A in the formula may be an alkylene group having a total carbon number of 2 to 8 which may also be interrupted by an oxygen atom.

作為二醇化合物的具體例，例如寡聚烷二醇、1,2-丙二醇、1,3-丙二醇、1,2-丁二醇、1,3-丁二醇、2,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,7-庚二醇、1,8-辛二醇等。 Specific examples of the diol compound include oligomeric alkanediol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 2,3-butanediol , 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and the like.

寡聚烷二醇為以下式(Va)表示的寡聚烷二醇較佳。 The oligoalkanediol is preferably an oligoalkanediol represented by the following formula (Va).

HO-(CmH2m-O)n-H (Va) HO- (C m H 2m -O) n -H (Va)

式中m為2或3，n為1以上的整數，m×n為8以下。 In the formula, m is 2 or 3, n is an integer of 1 or more, and m × n is 8 or less.

作為以式(Va)所示的寡聚烷二醇，例如乙二醇、二乙二醇、三乙二醇，其中因容易取得，對於聚乙烯醇系樹脂的親和性高等的理由，較佳為乙二醇。 As the oligomeric alkanediol represented by the formula (Va), for example, ethylene glycol, diethylene glycol, and triethylene glycol are preferable because they are easily available and have high affinity for polyvinyl alcohol resins. Is ethylene glycol.

相對於構成光硬化性接著劑的光陽離子硬化性成分(A)100重量份，二醇化合物的調配量為0.5重量份以上，較佳為1重量份以上，可顯現接著力之提升效果。另一方面，二醇化合物的調配量變多時，引起光硬化性接著劑與二醇化合物的分離，因無法使光硬化性接著劑均勻地塗佈於偏光器、保護膜的表面，故相對於構成光硬化性接著劑的光陽離子硬化性成分(A)100重量份，二醇化合物的調配量為8重量份以下較佳，更佳為6重量份以下。 The blending amount of the diol compound is 0.5 part by weight or more, and preferably 1 part by weight or more with respect to 100 parts by weight of the photocationically curable component (A) constituting the photocurable adhesive, and the effect of improving the adhesion can be exhibited. On the other hand, when the amount of the diol compound is increased, the photocurable adhesive is separated from the diol compound, and the photocurable adhesive cannot be uniformly applied to the surface of the polarizer and the protective film. 100 parts by weight of the photocationically curable component (A) constituting the photocurable adhesive is preferably 8 parts by weight or less, and more preferably 6 parts by weight or less.

[偏光器] [Polarizer]

偏光器係由吸附配向有二色性色素之聚乙烯醇系樹脂膜所構成。構成偏光器的聚乙烯醇系樹脂，可藉由聚乙酸乙烯酯系樹脂皂化而得。作為聚乙酸乙烯酯系樹脂，除乙酸乙烯酯的同元聚合物之聚乙酸乙烯酯外，可舉例如乙酸乙烯酯以及可與其聚合的其他單體的共聚物等。作為可與乙酸乙烯酯聚合的其他單體，例如不飽和羧酸類、烯烴類、乙烯基醚類、不飽和磺酸類等。聚乙烯醇系樹脂的皂化度，一般為85至100莫耳%，較佳為98至100莫耳%的範圍。聚乙烯醇系樹脂，可再被改性，亦可使用例如以醛類改性之聚乙烯醇縮甲醛、聚乙烯醇縮乙醛等。聚乙烯醇系樹脂的聚合度，一般為1,000至10,000，較佳為1,500至5,000的範圍。 The polarizer is composed of a polyvinyl alcohol-based resin film having a dichroic pigment adsorbed and aligned. The polyvinyl alcohol-based resin constituting the polarizer can be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include, in addition to polyvinyl acetate, a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers that can be polymerized therewith. Examples of other monomers that can be polymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The degree of saponification of the polyvinyl alcohol resin is generally in the range of 85 to 100 mol%, and preferably in the range of 98 to 100 mol%. The polyvinyl alcohol-based resin may be further modified, and for example, polyvinyl acetal and polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol-based resin is generally in the range of 1,000 to 10,000, and preferably in the range of 1,500 to 5,000.

偏光器係可經過：如聚乙烯醇系樹脂膜進行一軸延 伸的步驟、將聚乙烯醇系樹脂膜以二色性色素染色而使該二色性色素吸附的步驟、將二色性色素吸附的聚乙烯醇系樹脂膜以硼酸水溶液處理的步驟而製造。 The polarizer can pass through: such as polyvinyl alcohol resin film for an axial extension A step of stretching, a step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye and adsorbing the dichroic dye, and a step of treating a polyvinyl alcohol-based resin film having the dichroic dye adsorbed with a boric acid aqueous solution are produced.

一軸延伸係可在藉由二色性色素之染色前進行，亦可與藉由二色性色素之染色同時進行，亦可在藉由二色性色素之染色後進行。於一軸延伸在藉由二色性色素之染色後進行時，該一軸延伸係可在硼酸處理前進行，亦可在硼酸處理中進行。而且，當然亦可在該等的複數階段進行一軸延伸。於一軸延伸係可在轉速相異的滾輪間進行一軸延伸，亦可使用熱滾輪進行一軸延伸。而且，可為在大氣中進行延伸的乾式延伸，亦可為藉由溶劑在膨潤的狀態下進行延伸之濕式延伸。延伸倍率一般為4至8倍。 The uniaxial extension can be performed before dyeing with a dichroic pigment, or simultaneously with dyeing with a dichroic pigment, or after dyeing with a dichroic pigment. When the uniaxial extension is performed after dyeing with a dichroic pigment, the uniaxial extension may be performed before or during the boric acid treatment. Moreover, it is of course possible to perform one-axis extension in such plural stages. In the one-axis extension system, one-axis extension can be performed between rollers with different rotation speeds, and one-axis extension can also be performed using hot rollers. In addition, it may be dry stretching in the atmosphere, or wet stretching in a swollen state by a solvent. The stretching ratio is generally 4 to 8 times.

於聚乙烯醇系樹脂膜以二色性色素染色，例如只要將聚乙烯醇系樹脂膜浸漬於含有二色性色素的溶液即可。作為二色性色素，具體地可使用碘或二色性有機染料。 The polyvinyl alcohol-based resin film is dyed with a dichroic dye. For example, the polyvinyl alcohol-based resin film may be dipped in a solution containing a dichroic dye. As the dichroic dye, specifically, iodine or a dichroic organic dye can be used.

使用碘作為二色性色素時，一般採用於含有碘及碘化鉀的水溶液中浸漬聚乙烯醇系樹脂膜而染色的方法。該水溶液中之碘的含量，一般相對於水每100重量份為0.01至0.5重量份左右，碘化鉀的含量一般相對於水每100重量份為0.5至10重量份左右。該水溶液的溫度，一般為20至40℃左右，而且對該水溶液的浸漬時間(染色時間)，一般為30至300秒左右。 When iodine is used as a dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is generally adopted. The content of iodine in the aqueous solution is generally about 0.01 to 0.5 parts by weight per 100 parts by weight of water, and the content of potassium iodide is generally about 0.5 to 10 parts by weight per 100 parts by weight of water. The temperature of the aqueous solution is generally about 20 to 40 ° C, and the immersion time (dyeing time) of the aqueous solution is generally about 30 to 300 seconds.

另一方面，於使用二色性有機染料作為二色性色素時，一般採用包含水溶性的二色性有機染料之水溶液中，浸漬聚乙烯醇系樹脂膜而染色的方法。該水溶液之二色性有機染料的含量，一般相對於水每100重量份為1×10-3至1×10-2重量份左右。該 水溶液係亦可含有硫酸鈉等的無機鹽。該水溶液的溫度，一般為20至80℃左右，而且對該水溶液的浸漬時間(染色時間)，一般為30至300秒左右。 On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic organic dye is generally adopted. The content of the dichroic organic dye in the aqueous solution is generally about 1 × 10 -3 to 1 × 10 -2 parts by weight per 100 parts by weight of water. The aqueous solution may contain an inorganic salt such as sodium sulfate. The temperature of the aqueous solution is generally about 20 to 80 ° C, and the immersion time (dyeing time) of the aqueous solution is generally about 30 to 300 seconds.

藉由二色性色素之染色後的硼酸處理，可藉由浸漬被染色的聚乙烯醇系樹脂膜於硼酸水溶液而進行。硼酸水溶液之硼酸的含量，一般對水每100重量份為2至15重量份左右度，較佳為5至12重量份。於使用碘作為二色性色素時，該硼酸水溶液含有碘化鉀為較佳。硼酸水溶液之碘化鉀的含量，一般相對於水每100重量份為2至20重量份左右，較佳為5至15重量份。對硼酸水溶液的浸漬時間，一般為100至1,200秒左右，較佳為150至600秒左右，更佳為200至400秒左右。硼酸水溶液的溫度，一般為50℃以上，較佳為50至85℃。 The boric acid treatment after the dichroic dye is dyed can be performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in the boric acid aqueous solution is generally about 2 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. When using iodine as a dichroic dye, it is preferable that the boric acid aqueous solution contains potassium iodide. The content of potassium iodide in the boric acid aqueous solution is generally about 2 to 20 parts by weight, preferably 5 to 15 parts by weight, per 100 parts by weight of water. The immersion time for the boric acid aqueous solution is generally about 100 to 1,200 seconds, preferably about 150 to 600 seconds, and more preferably about 200 to 400 seconds. The temperature of the boric acid aqueous solution is generally 50 ° C or higher, and preferably 50 to 85 ° C.

硼酸處理後的聚乙烯醇系樹脂膜，一般進行水洗處理。水洗處理係例如藉由將硼酸處理過的聚乙烯醇系樹脂膜浸漬於水而進行。水洗後，施以乾燥處理，得到偏光器。水洗處理之水的溫度，一般為5至40℃左右，浸漬時間一般為2至120秒左右。其後進行的乾燥處理，一般使用熱風乾燥機、遠紅外線加熱器進行。乾燥溫度，一般為40至100℃。而且，乾燥處理的時間，一般為120至600秒左右。 The polyvinyl alcohol-based resin film after the boric acid treatment is generally subjected to a water washing treatment. The water washing treatment is performed, for example, by immersing a boric acid-treated polyvinyl alcohol-based resin film in water. After washing with water, a drying process was performed to obtain a polarizer. The temperature of the water for water washing treatment is generally about 5 to 40 ° C, and the immersion time is generally about 2 to 120 seconds. The subsequent drying treatment is generally performed using a hot-air dryer and a far-infrared heater. The drying temperature is generally 40 to 100 ° C. In addition, the time of the drying process is generally about 120 to 600 seconds.

由此所得到之聚乙烯醇系樹脂膜所構成的偏光器的厚度，可為10至50μm左右。 The thickness of the polarizer made of the polyvinyl alcohol-based resin film thus obtained may be about 10 to 50 μm .

[保護膜] [Protective film]

本發明的偏光板，係於先前所說明的聚乙烯醇系樹脂膜所構成的偏光器，經由上述說明的光硬化性接著劑，積層由透明樹脂 膜所構成的保護膜，藉由使光硬化性接著劑硬化而得。 The polarizing plate of the present invention is a polarizer made of the polyvinyl alcohol resin film described above, and is laminated with a transparent resin through the photocurable adhesive described above. A protective film made of a film is obtained by curing a photocurable adhesive.

構成保護膜的透明樹脂膜，可為未被延伸的膜或被一軸或二軸延伸的膜之任一種。 The transparent resin film constituting the protective film may be either an unstretched film or a film stretched uniaxially or biaxially.

透明樹脂膜的主成分，較佳為選自由纖維素系樹脂、丙烯酸系樹脂、非結晶性聚烯烴系樹脂、聚酯系樹脂以及聚碳酸酯系樹脂所成之群的至少1種樹脂。 The main component of the transparent resin film is preferably at least one resin selected from the group consisting of a cellulose resin, an acrylic resin, an amorphous polyolefin resin, a polyester resin, and a polycarbonate resin.

作為聚酯系樹脂，無特別限制，在機械性質、耐溶劑性、耐刮傷性、成本等的方面，特別佳為聚對苯二甲酸乙二酯。所謂聚對苯二甲酸乙二酯，係指重複單元的80莫耳%以對苯二甲酸乙二酯所構成之樹脂，亦可含有來自其他共聚合成分的構成單元。 The polyester resin is not particularly limited. In terms of mechanical properties, solvent resistance, scratch resistance, cost, etc., polyethylene terephthalate is particularly preferred. The so-called polyethylene terephthalate refers to a resin composed of 80 mol% of repeating units made of ethylene terephthalate, and may also contain a structural unit derived from other copolymerization components.

作為其他共聚合成分，例如二羧酸成分、二醇成分。作為二羧酸成分係例如間苯二甲酸、對-β-羥基乙氧基安息香酸、4,4’-二羧基聯苯、4,4’-二羧基二苯基酮、雙(4-羧基苯基)乙烷、己二酸、癸二酸、5-磺基間苯二甲酸鈉以及1,4-二羧基環己烷等。作為二醇成分，例如丙二醇、丁二醇、新戊二醇、二乙二醇、環己二醇、雙酚A的環氧乙烷加成物、聚乙二醇、聚丙二醇以及聚丁二醇等。該等二羧酸成分、二醇成分，可依據需要，分別組合2種以上使用。而且，與上述二羧酸成分、二醇成分同時，可併用如對-羥基安息香酸的羥基羧酸。作為其他共聚合成分，可少量使用具有醯胺鍵結、胺基甲酸乙酯鍵結、醚鍵結、碳酸酯鍵結等的二羧酸成分及/或二醇成分。 Examples of the other copolymerization component include a dicarboxylic acid component and a diol component. Examples of the dicarboxylic acid component are isophthalic acid, p-β-hydroxyethoxybenzoic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenylketone, and bis (4-carboxyl). Phenyl) ethane, adipic acid, sebacic acid, sodium 5-sulfoisophthalate, and 1,4-dicarboxycyclohexane. Examples of the diol component include propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adducts of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutadiene Alcohol and so on. These dicarboxylic acid components and diol components can be used in combination of two or more kinds, respectively, as needed. In addition to the dicarboxylic acid component and the diol component, a hydroxycarboxylic acid such as p-hydroxybenzoic acid may be used in combination. As other copolymerization components, a dicarboxylic acid component and / or a diol component having a amine bond, a urethane bond, an ether bond, a carbonate bond, or the like can be used in a small amount.

聚對苯二甲酸乙二酯系樹脂，係指重複單元的80莫耳%以對苯二甲酸乙二酯所構成之樹脂，亦可含有來自其他共聚 合成分的構成單元。作為其他共聚合成分，例如間苯二甲酸、4,4’-二羧基聯苯、4,4’-二羧基二苯基酮、雙(4-羧基苯基)乙烷、己二酸、癸二酸、5-磺基間苯二甲酸鈉、1,4-二羧基環己烷等的二羧酸成分；丙二醇、丁二醇、新戊二醇、二乙二醇、環己二醇、雙酚A的環氧乙烷加成物、聚乙二醇、聚丙二醇、聚丁二醇等的二醇成分。該等二羧酸成分、二醇成分，可依據需要，分別組合2種以上使用。而且，與上述二羧酸成分、二醇成分同時，可併用如對-羥基安息香酸、對-β-羥基乙氧基安息香酸等的羥基羧酸。作為其他共聚合成分，可使用少量的具有醯胺鍵結、胺基甲酸乙酯鍵結、醚鍵結、碳酸酯鍵結等的二羧酸成分及/或二醇成分。 Polyethylene terephthalate resin refers to a resin composed of 80 mol% of repeating units made of terephthalate. It may also contain other copolymers. The building blocks of a synthetic component. As other copolymerization components, for example, isophthalic acid, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ketone, bis (4-carboxyphenyl) ethane, adipic acid, decyl Dicarboxylic acid components such as diacid, sodium 5-sulfoisophthalate, 1,4-dicarboxycyclohexane; propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, bis Glycol components such as ethylene oxide adducts of phenol A, polyethylene glycol, polypropylene glycol, and polybutylene glycol. These dicarboxylic acid components and diol components can be used in combination of two or more kinds, respectively, as needed. In addition to the dicarboxylic acid component and the diol component, hydroxycarboxylic acids such as p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid can be used in combination. As other copolymerization components, a small amount of a dicarboxylic acid component and / or a diol component having a amine bond, a urethane bond, an ether bond, a carbonate bond, or the like can be used.

使用上述聚對苯二甲酸乙二酯系樹脂薄膜化後，施以如上述的延伸處理者，作為保護膜，藉此，機械性質、耐溶劑性、耐刮傷性、成本等佳，同時可得到厚度減少的捲狀偏光板。 After using the polyethylene terephthalate-based resin to form a thin film, the above-mentioned extension treatment is used as a protective film, whereby mechanical properties, solvent resistance, scratch resistance, cost, etc. are improved, and at the same time, A rolled polarizer having a reduced thickness was obtained.

使用於保護膜的聚碳酸酯系樹脂，係由碳酸與二醇或雙酚所形成的聚酯。其中，於分子鏈具有二苯基烷的芳香族聚碳酸酯，因耐熱性、耐候性及耐酸性佳，故適合使用。作為如此的聚碳酸酯，例如從如2,2-雙(4-羥基苯基)丙烷(別名雙酚A)、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)異丁烷或1,1-雙(4-羥基苯基)乙烷的雙酚類所衍生的聚碳酸酯。 The polycarbonate-based resin used for the protective film is a polyester formed of carbonic acid and a diol or bisphenol. Among them, an aromatic polycarbonate having diphenylalkane in its molecular chain is suitable for use because of its excellent heat resistance, weather resistance, and acid resistance. As such a polycarbonate, for example, 2,2-bis (4-hydroxyphenyl) propane (alias bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis Polycarbonates derived from bisphenols of (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) isobutane or 1,1-bis (4-hydroxyphenyl) ethane ester.

作為聚碳酸酯系樹脂膜的製造方法，亦可使用流延製膜法、熔融擠出法等任一種方法。作為具體的製造方法之例，例如將聚碳酸酯系樹脂溶解於適當的有機溶劑，而成為聚碳酸酯系樹脂溶液，將其流注於金屬支持體上，形成薄板條(web)，將薄板條從金屬支持體剝下後，剝下後的薄板條進行熱風乾燥而得到 薄膜的方法。 As a method for producing a polycarbonate-based resin film, any method such as a casting film forming method and a melt extrusion method may be used. As an example of a specific manufacturing method, for example, a polycarbonate-based resin is dissolved in an appropriate organic solvent to form a polycarbonate-based resin solution, which is poured onto a metal support to form a thin web (web), and the thin plate After stripping from the metal support, the strip after stripping is dried by hot air to obtain Thin film method.

使用於保護膜的丙烯酸系樹脂，無特別限制，一般為甲基丙烯酸酯為主的單體之聚合物，較佳為其與少量的其他共聚單體成分共聚合之共聚物。該共聚物一般可將包含甲基丙烯酸甲酯以及丙烯酸甲酯的單官能基單體，在自由基聚合引發劑及鏈轉移劑的共存下聚合而得。而且，丙烯酸系樹脂可使第三單官能基單體共聚合。 The acrylic resin used for the protective film is not particularly limited. Generally, it is a polymer of monomers mainly composed of methacrylate, preferably a copolymer copolymerized with a small amount of other comonomer components. The copolymer is generally obtained by polymerizing a monofunctional monomer containing methyl methacrylate and methyl acrylate in the coexistence of a radical polymerization initiator and a chain transfer agent. In addition, the acrylic resin can copolymerize the third monofunctional monomer.

作為可與甲基丙烯酸甲酯以及丙烯酸甲酯共聚合之第三單官能基單體，例如甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸環己酯、甲基丙烯酸苯酯、甲基丙烯酸苯甲酯、甲基丙烯酸2-乙基己酯以及甲基丙烯酸2-羥基乙酯等甲基丙烯酸甲酯以外的甲基丙烯酸酯類；丙烯酸乙酯、丙烯酸丁酯、丙烯酸環己酯、丙烯酸苯酯、丙烯酸苯甲酯、丙烯酸2-乙基己酯以及丙烯酸2-羥基乙酯等的丙烯酸酯類；2-(羥基甲基)丙烯酸甲酯、2-(1-羥基乙基)丙烯酸甲酯、2-(羥基甲基)丙烯酸乙酯以及2-(羥基甲基)丙烯酸丁酯等的羥基烷基丙烯酸酯類；甲基丙烯酸及丙烯酸等的不飽和酸類；氯苯乙烯以及溴苯乙烯等鹵化苯乙烯類；乙烯基甲苯以及α-甲基苯乙烯等取代苯乙烯類；丙烯腈及甲基丙烯腈等不飽和腈類；順丁烯二酸酐及甲基順丁烯二酸酐等不飽和酸酐類；苯基馬來醯亞胺以及環己基馬來醯亞胺等不飽和醯亞胺類等。該等可分別單獨使用，可併用不同的複數種。 As the third monofunctional monomer that can be copolymerized with methyl methacrylate and methyl acrylate, such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, Methacrylates other than methyl methacrylate, such as benzyl acrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate; ethyl acrylate, butyl acrylate, cyclohexyl acrylate Acrylates, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; 2- (hydroxymethyl) acrylate, 2- (1-hydroxyethyl) Hydroxyalkyl acrylates such as methyl acrylate, ethyl 2- (hydroxymethyl) acrylate, and butyl 2- (hydroxymethyl) acrylate; unsaturated acids such as methacrylic acid and acrylic acid; chlorostyrene and bromine Halogenated styrenes such as styrene; substituted styrenes such as vinyl toluene and α-methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; maleic anhydride and methyl maleic anhydride Unsaturated acid anhydrides; phenylmaleimide Cyclohexylmaleimide and unsaturated acyl imine (PEI) and the like. These can be used individually or in combination.

使多官能基單體共聚合時，作為可與甲基丙烯酸甲酯以及丙烯酸甲酯共聚合之多官能基單體，例如乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸 酯、四乙二醇二(甲基)丙烯酸酯、九乙二醇二(甲基)丙烯酸酯以及十四乙二醇二(甲基)丙烯酸酯等乙二醇或其寡聚物的兩末端羥基以丙烯酸或甲基丙烯酸酯化者；丙二醇或其寡聚物的兩末端羥基以丙烯酸或甲基丙烯酸酯化者；新戊二醇二(甲基)丙烯酸酯、己二醇二(甲基)丙烯酸酯及丁二醇二(甲基)丙烯酸酯等2價醇的羥基以丙烯酸或甲基丙烯酸酯化者；雙酚A、雙酚A的環氧乙烷加成物或該等鹵素取代物的兩末端羥基以丙烯酸或甲基丙烯酸酯化者；三羥甲基丙烷及季戊四醇等的多價醇以丙烯酸或甲基丙烯酸酯化者以及於該等末端羥基，使環氧丙基丙烯酸酯或環氧丙基甲基丙烯酸酯的環氧基開環加成者；琥珀酸、己二酸、對苯二甲酸、鄰苯二甲酸、該等的鹵素取代物等的二元酸以及於該等的環氧烷加成物等，使環氧丙基丙烯酸酯或環氧丙基甲基丙烯酸酯的環氧基開環加成者；芳香基(甲基)丙烯酸酯；二乙烯基苯等芳香族二乙烯基化合物等。其中，適合使用乙二醇二甲基丙烯酸酯、四乙二醇二甲基丙烯酸酯以及新戊二醇二甲基丙烯酸酯。 When copolymerizing a polyfunctional monomer, as the polyfunctional monomer that can be copolymerized with methyl methacrylate and methyl acrylate, for example, ethylene glycol di (meth) acrylate, diethylene glycol bis (methyl) Base) acrylate, triethylene glycol di (meth) acrylic acid Ester, tetraethylene glycol di (meth) acrylate, nonethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate such as ethylene glycol or both ends of the oligomer Hydroxyl esterified with acrylic acid or methacrylic acid; propylene glycol or its oligomers are esterified with acrylic acid or methacrylic acid; neopentyl glycol di (meth) acrylate, hexanediol di (methyl) ) The hydroxyl groups of divalent alcohols such as acrylate and butanediol di (meth) acrylate are esterified with acrylic acid or methacrylic acid; bisphenol A, ethylene oxide adduct of bisphenol A or these halogens are substituted The two terminal hydroxyl groups of the product are esterified with acrylic acid or methacrylic acid; the polyhydric alcohols such as trimethylolpropane and pentaerythritol are esterified with acrylic acid or methacrylic acid; Or epoxy ring-opening addition of epoxy propyl methacrylate; dibasic acids such as succinic acid, adipic acid, terephthalic acid, phthalic acid, such halogen substitution products, and the like And other alkylene oxide adducts, etc. Group by ring-opening addition; (meth) acrylate, an aromatic group; divinylbenzene, divinyl aromatic compounds and the like. Among them, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol dimethacrylate are suitably used.

如此的組成所構成的丙烯酸系樹脂，再者可進行共聚物具有的官能基間的反應，並改性者。就該反應而言，例如丙烯酸甲酯的甲酯基與2-(羥基甲基)丙烯酸甲酯的羥基之高分子鏈內去甲醇的縮合反應、丙烯酸的羧基與2-(羥基甲基)丙烯酸甲酯的羥基之高分子鏈內脫水縮合反應等。 The acrylic resin having such a composition can be further modified by the reaction between the functional groups of the copolymer. For this reaction, for example, the condensation reaction of methyl ester group of methyl acrylate with the hydroxyl group of methyl 2- (hydroxymethyl) acrylate in the polymer chain is de-methanol, Dehydration condensation reaction of the hydroxyl group of the methyl ester in the polymer chain.

上述丙烯酸系樹脂的玻璃轉化溫度，較佳為80至120℃的範圍。於丙烯酸系樹脂的玻璃轉化溫度調整為上述範圍，一般可採用適當選擇甲基丙烯酸酯系單體與丙烯酸酯系單體的聚合比、各別的酯基之碳鏈長及其具有的官能基的種類以及相對於 單體全部之多官能基丙烯酸單體的聚合比之方法。 The glass transition temperature of the acrylic resin is preferably in a range of 80 to 120 ° C. The glass transition temperature of the acrylic resin is adjusted to the above range. Generally, the polymerization ratio of the methacrylate monomer to the acrylate monomer, the carbon chain length of each ester group, and the functional groups thereof can be appropriately selected. Kind and relative to Method of polymerization ratio of polyfunctional acrylic monomer of all monomers.

丙烯酸系樹脂，依據需要，亦可含有習知的添加劑。作為習知的添加劑，例如滑劑、抗壓黏劑、熱安定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝擊性改良劑、界面活性劑等。但是，作為積層於偏光膜的保護膜，因必須為透明性，該等添加劑的量係以最小限的量較佳。 The acrylic resin may contain conventional additives as necessary. As conventional additives, for example, a slip agent, a pressure-resistant adhesive, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, an impact resistance improver, a surfactant and the like. However, as a protective film laminated on a polarizing film, since the transparency must be provided, the amount of these additives is preferably a minimum amount.

作為丙烯酸系樹脂膜的製造方法，亦可使用熔融流延法、T型模頭法、如膨脹法的熔融擠出法、壓延法等的任一種方法。其中，將原料樹脂例如從T型模頭熔融擠出，所得之膜狀物的至少單面與滾輪或皮帶接觸而製膜之方法，在可得到表面性質形狀良好的膜之點，較佳。 As a method for producing the acrylic resin film, any method such as a melt casting method, a T-die method, a melt extrusion method such as an expansion method, or a calender method may be used. Among them, a method of forming a film by melting and extruding a raw material resin from a T-die, and at least one side of the obtained film-like material is in contact with a roller or a belt to form a film having a good surface property shape.

丙烯酸系樹脂，從對膜的製膜性、膜的耐衝擊性等的觀點，可含有作為衝擊性改良劑的丙烯酸系橡膠粒子。此處所謂之丙烯酸系橡膠粒子，係以丙烯酸酯為主體的聚合彈性體為必要成分之粒子，實質上例如只由該聚合彈性體構成的單層構造者、或該聚合彈性體為1層之多層構造者。作為如此的聚合彈性體之例，例如以丙烯酸烷酯為主成分，使可與其共聚合的其他乙烯基單體及交聯性單體共聚合之交聯彈性共聚物。作為聚合彈性體的主成分之丙烯酸烷酯，例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等的烷基的碳數為1至8左右者，特別是可使用具有碳數4以上的烷基之丙烯酸酯較佳。作為該可與丙烯酸烷酯共聚合的其他乙烯基單體，例如於分子內具有1個聚合性碳-碳雙鍵之化合物，更具體地，如甲基丙烯酸甲酯之甲基丙烯酸酯、苯乙烯的芳香族乙烯基化合物、如丙烯腈的乙烯基氰化 合物等。又，作為交聯性單體，例如於分子內具有至少2個聚合性碳-碳雙鍵之交聯性化合物，更具體地例如乙二醇二(甲基)丙烯酸酯以及丁二醇二(甲基)丙烯酸酯之多元醇的(甲基)丙烯酸酯類、如(甲基)丙烯酸烯丙酯之(甲基)丙烯酸的烯基酯、二乙烯基苯等。 The acrylic resin may contain acrylic rubber particles as an impact modifier from the viewpoints of film-forming properties of the film, impact resistance of the film, and the like. The so-called acrylic rubber particles here are particles having a polymer elastomer mainly composed of acrylate as an essential component. For example, a polymer having a single-layer structure consisting of the polymer elastomer alone, or a polymer having a single layer Multi-layer constructor. As an example of such a polymerized elastomer, for example, a crosslinked elastic copolymer containing alkyl acrylate as a main component and copolymerized with other vinyl monomers and crosslinkable monomers which can be copolymerized therewith. As the main component of the polymer elastomer, alkyl acrylates, such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, have a carbon number of about 1 to 8, and are particularly useful. An acrylate having an alkyl group having 4 or more carbon atoms is preferred. As the other vinyl monomer copolymerizable with the alkyl acrylate, for example, a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methyl methacrylate, benzene Aromatic vinyl compounds of ethylene, such as vinyl cyanidation of acrylonitrile 组合 等。 And other. Further, as the crosslinkable monomer, for example, a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate and butanediol di ( (Meth) acrylates of poly (meth) acrylate polyols, such as alkenyl (meth) acrylate of allyl (meth) acrylate, divinylbenzene, and the like.

再者，不含橡膠粒子的丙烯酸系樹脂所構成的膜與包含橡膠粒子的丙烯酸系樹脂所構成的積層物，亦可作為保護膜。丙烯酸系樹脂係可以市售品容易地取得，例如以分別的商品名，SUMIPEX(住友化學股份公司製)、ACRYPET(三菱RAYON股份公司製)、DELPET(旭化成股份公司製)、PARAPET(Kuraray股份公司製)、ACRYVIEWA(日本觸媒股份公司製)等。 Furthermore, a laminate of a film made of an acrylic resin containing no rubber particles and an acrylic resin containing rubber particles can also be used as a protective film. Acrylic resins can be easily obtained on the market. For example, under the respective trade names, SUMIPEX (manufactured by Sumitomo Chemical Co., Ltd.), ACRYPET (manufactured by Mitsubishi Rayon Co., Ltd.), DELPET (manufactured by Asahi Kasei Co., Ltd.), PARAPET (Kuraray Co., Ltd. System), ACRYVIEWA (manufactured by Japan Catalyst Corporation), etc.

使用於保護膜的非結晶性聚烯烴系樹脂，例如由環戊二烯與烯烴類藉由狄爾斯-阿爾德(Diels-Alder)反應所得之降莰烯或其衍生物作為單體，進行開環移位聚合，接著藉由氫化所得之樹脂；由二環戊二烯與烯烴類或甲基丙烯酸酯類藉由狄爾斯-阿爾德反應所得之四環十二烯或其衍生物作為單體，進行開環移位聚合，接著藉由氫化所得之樹脂；使用選自降莰烯、四環十二烯及該等的衍生物類以及其他環狀聚烯烴單體中2種以上，同樣地進行開環移位共聚合，接著藉由氫化所得之樹脂；於降莰烯、四環十二烯或該等的衍生物類，加成共聚合具有乙烯基的芳香族化合物等所得之樹脂等。列舉市售的非結晶性聚烯烴系樹脂之例時，有JSR(股)的「ARTON」、日本ZEON(股)的「ZEONEX」以及「ZEONOR」、三井化學(股)的「APO」以及「APEL」等。將非結晶性聚烯烴系樹脂製膜成為薄膜時，於製膜，可適合使用溶劑澆 鑄法、熔融擠出法等習知的方法。 The amorphous polyolefin resin used for the protective film is, for example, norbornene or a derivative thereof obtained by reacting cyclopentadiene with an olefin through a Diels-Alder reaction as a monomer. Ring-opening shift polymerization followed by hydrogenation of the resin; tetracyclododecene or its derivative obtained from Dicyclopentadiene and olefins or methacrylates by Diels-Alder reaction Monomer, subject to ring-opening shift polymerization, and then a resin obtained by hydrogenation; using two or more kinds selected from norbornene, tetracyclododecene and derivatives thereof, and other cyclic polyolefin monomers, The ring-opening shift copolymerization is carried out in the same manner, and then the resin obtained by hydrogenation is added; the resin obtained by adding norbornene, tetracyclododecene, or the like, is copolymerized with an aromatic compound having a vinyl group, etc. Resin, etc. Examples of commercially available non-crystalline polyolefin-based resins include "ARTON" by JSR, "ZEONEX" and "ZEONOR" by ZEON, and "APO" and "APO" by Mitsui Chemicals. APEL "and so on. When a film made of an amorphous polyolefin resin is formed into a thin film, the film can be formed by using a solvent. A known method such as a casting method or a melt extrusion method.

纖維素系樹脂係纖維素中之羥基的至少一部分被乙酸酯化之樹脂，亦可為一部分被乙酸酯化，一部分被其他酸酯化之混合酯。纖維素系樹脂較佳為纖維素酯系樹脂，更佳為乙醯基纖維素系樹脂。作為乙醯基纖維素系樹脂的具體例，例如三乙醯基纖維素、二乙醯基纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等。作為如此的乙醯基纖維素系樹脂所構成的膜之市售品，例如富士薄膜(股)製「FUJITAC TD80」、「FUJITAC TD80UF」以及「FUJITAC TD80UZ」、柯尼卡美能達精密光學(Konica Minolta Opto)(股)製「KC8UX2M」以及「KC8UY」。 The cellulose-based resin is a resin in which at least a part of hydroxyl groups in the cellulose is esterified with acetate, and may be a mixed ester in which a part is esterified with acetic acid and a part is esterified with other acids. The cellulose-based resin is preferably a cellulose ester-based resin, and more preferably an acetyl cellulose-based resin. Specific examples of the ethyl cellulose-based resin include triethyl cellulose, diethyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like. Commercially available films of such ethyl acetate cellulose resins include, for example, "FUJITAC TD80", "FUJITAC TD80UF" and "FUJITAC TD80UZ" made by Fuji Film (Korea), Konica Minolta Precision Optics Minolta Opto (KC8UX2M) and "KC8UY".

亦可使用賦予光學補償功能的纖維素系樹脂膜。作為如此的光學補償膜，例如於纖維素系樹脂含有具有調整相位差功能的化合物之膜、於纖維素系樹脂的表面塗佈有具有調整相位差功能的化合物者、使纖維素系樹脂進行一軸或二軸延伸所得的膜等。列舉市售的纖維素矽樹脂的光學補償膜之例時，有富士薄膜(股)製「WIDE VIEW FILM WV BZ 438」以及「WIDE VIEW FILM WV EA」、柯尼卡美能達精密光學(股)製「KC4FR-1」以及「KC4HR-1」等。 A cellulose-based resin film that provides an optical compensation function may also be used. As such an optical compensation film, for example, a film containing a compound having a retardation-adjusting function on a cellulose-based resin, a compound having a retardation-adjusting function being coated on the surface of the cellulose-based resin, and the cellulose-based resin being subjected to one axis Or biaxially stretched film. Examples of commercially available cellulose silicone optical compensation films include "WIDE VIEW FILM WV BZ 438" and "WIDE VIEW FILM WV EA" manufactured by Fujifilm, and Konica Minolta Precision Optics (stock) "KC4FR-1" and "KC4HR-1".

貼合於偏光器的一側的面之保護膜(透明樹脂膜)，亦可含有紫外線吸收劑。含有紫外線吸收劑的保護膜，藉由配置於液晶胞的辨識側，可用以保護液晶胞不受紫外線而造成劣化。 The protective film (transparent resin film) laminated on one side of the polarizer may contain an ultraviolet absorber. The protective film containing an ultraviolet absorber can be arranged on the identification side of the liquid crystal cell to protect the liquid crystal cell from being deteriorated by ultraviolet rays.

於本發明，於偏光器的至少一側的面，使用上述光硬化性接著劑，貼合由上述透明樹脂膜所構成的保護膜。只於偏光器的單面貼合保護膜時，於偏光器的另一面，為了貼合於液晶 胞等的其他構件，亦可為直接設置黏著劑層的形態。 In the present invention, a protective film made of the transparent resin film is bonded to at least one surface of the polarizer using the photocurable adhesive. Only when the protective film is laminated on one side of the polarizer, on the other side of the polarizer, in order to adhere to the liquid crystal Other components such as cells may be in the form of directly providing an adhesive layer.

另一方面，於偏光器的兩面貼合保護膜時，各別的保護膜可為相同種類，亦可為不同種類。 On the other hand, when a protective film is laminated on both surfaces of a polarizer, the respective protective films may be the same type or different types.

貼合於偏光器的一側的面之保護膜，使用上述光硬化性接著劑而接著，貼合於偏光器的另一側的面之保護膜，亦可使用其他接著劑接著。 The protective film adhered to one surface of the polarizer may be adhered using the above-mentioned photocurable adhesive, and the protective film adhered to the other surface of the polarizer may be adhered using another adhesive.

保護膜係在對偏光器貼合前，於貼合面，可實施皂化處理、電暈處理、底塗(primer)處理、錨定塗佈(anchor coating)處理等的易接著處理。又，於保護膜對偏光器的貼合面之相反側的表面，可具有硬塗層、抗反射層、抗眩層等的各種處理層。保護膜的厚度，一般為5至200μm程度的範圍，較佳為10至120μm，更佳為10至85μm。 Before the polarizer is bonded to the protective film, a saponification treatment, a corona treatment, a primer treatment, an anchor coating treatment, or the like can be easily adhered to the bonding surface. The surface on the side opposite to the bonding surface of the protective film to the polarizer may have various treatment layers such as a hard coat layer, an anti-reflection layer, and an anti-glare layer. The thickness of the protective film is generally in the range of about 5 to 200 μm, preferably 10 to 120 μm, and more preferably 10 to 85 μm.

[偏光器與保護膜的接著] [Adhesion of polarizer and protective film]

當偏光器與保護膜接著時，係將上述說明的光硬化性接著劑的塗佈層，形成於偏光器與保護膜的貼合面之一者或兩者，經由該塗佈層，貼合偏光器與保護膜，如此形成的未硬化的光硬化性接著劑的塗佈層，藉由活性能量線的照射，使其硬化，使保護膜固定於偏光器上。光硬化性接著劑的塗佈層，可形成於偏光器的貼合面，亦可形成於保護膜的貼合面。於塗佈層的形成，可利用例如刮刀法、繞線棒法、狹縫塗佈法、缺角輪塗佈法、凹版塗佈法等各種塗佈方式。而且，亦可採用一邊連續供應偏光器與保護膜，以使兩者的貼合面成為內側，於其中間垂流接著劑之方式。於各塗佈方式，因有分別適合的黏度範圍，使用溶劑進行黏度的調整亦為有用的技術。基於此原因之溶劑，可使用不降低偏光器 的光學性能、可良好地溶解光硬化性接著劑者，其種類無特別限制。例如，可使用甲苯為代表之烴類、乙酸乙酯為代表的酯類等有機溶劑。膜厚係依偏光板的特性設計，可任意設定，但從接著劑材料費降低的觀點，以小者較佳，從貼合時抑制氣泡、異物等的缺陷之觀點，大者較佳，從密合性、耐久性的觀點，在被接著物與接著劑的組合所決定之最佳範圍實施較佳。一般為0.01至20μm，較佳為0.1至10μm，更佳為0.5至5μm。 When the polarizer and the protective film are bonded, the coating layer of the photocurable adhesive described above is formed on one or both of the bonding surfaces of the polarizer and the protective film, and bonded through the coating layer. The polarizer and the protective film, and the coating layer of the uncured photocurable adhesive formed in this way are hardened by irradiation with active energy rays, and the protective film is fixed to the polarizer. The coating layer of the photocurable adhesive may be formed on the bonding surface of the polarizer or on the bonding surface of the protective film. For the formation of the coating layer, various coating methods such as a doctor blade method, a wire rod method, a slit coating method, a notch wheel coating method, and a gravure coating method can be used. Furthermore, a method of continuously supplying a polarizer and a protective film on one side so that the bonding surface of the two becomes the inner side, and a method of vertical flow of an adhesive in the middle may be adopted. For each coating method, there is a suitable viscosity range, and it is also a useful technique to adjust the viscosity using a solvent. The solvent for this reason can be used without deteriorating the optical performance of the polarizer and can dissolve the photocurable adhesive well, and the type is not particularly limited. For example, organic solvents such as hydrocarbons typified by toluene and esters typified by ethyl acetate can be used. The film thickness is designed according to the characteristics of the polarizing plate and can be arbitrarily set, but from the viewpoint of reducing the cost of the adhesive material, the smaller one is preferred, and from the viewpoint of suppressing defects such as bubbles and foreign matter during bonding, the larger one is preferred. From the viewpoint of adhesiveness and durability, it is preferable to implement it in an optimal range determined by the combination of the adherend and the adhesive. It is generally 0.01 to 20 μm , preferably 0.1 to 10 μm , and more preferably 0.5 to 5 μm .

偏光器與保護膜接著時，兩者的貼合面的一者或兩者，形成接著劑的塗佈層前，可實施如電暈處理、電漿處理、火焰處理、底塗處理、錨塗處理之易接著處理。 When the polarizer and the protective film are bonded, one or both of the bonding surfaces of the two can be subjected to, for example, corona treatment, plasma treatment, flame treatment, primer treatment, and anchor coating before forming a coating layer of the adhesive. The ease of processing continues.

於光硬化性接著劑的塗佈層，為了照射活性能量線所使用的光源，只要是可產生紫外線、電子線、X射線等即可。特別是適合使用於波長400nm以下具有發光分佈，例如低壓水銀燈、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、金屬鹵化物燈等。 In order to irradiate the light source used for an active energy ray with the coating layer of a photocurable adhesive agent, what is necessary is just to generate | occur | produce ultraviolet rays, an electron beam, an X-ray, etc. It is particularly suitable for use with a light emission distribution below 400 nm, such as 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, metal halide lamps, and the like.

對光硬化性接著劑的活性能量線照射強度，係可對每一成為硬化對象的接著劑來決定，無特別限制，但引發劑的活性化有效的波長範圍之照射強度為0.1至3000mW/cm2較佳。對光硬化性接著劑的光照射強度未達0.1mW/cm2時，反應時間變得太長，超過3000mW/cm2時，受來自燈具輻射的熱以及光硬化性接著劑的聚合時產生的熱，有可能產生光硬化性接著劑的黃變、偏光器的劣化。 The intensity of irradiation of the active energy ray of the photocurable adhesive can be determined for each of the adhesives to be cured. There is no particular limitation, but the irradiation intensity in the wavelength range in which the activation of the initiator is effective is 0.1 to 3000 mW / cm 2 is better. When the light irradiation intensity of the light-curing adhesive is less than 0.1 mW / cm 2 , the reaction time becomes too long. When it exceeds 3000 mW / cm 2 , it is generated by the heat from the lamp and the polymerization of the light-curing adhesive. Heat may cause yellowing of the photocurable adhesive and deterioration of the polarizer.

對光硬化性接著劑的光照射時間，受每一成為硬化對象的接著劑所控制者，依然沒有特別限制，但就照射強度與照 射時間的乘積所表示之累積光量，設定為10至5,000mJ/cm2較佳。對光硬化性接著劑的累積光量未達10mJ/cm2時，來自引發劑的活性物質的產生不足，所得之接著劑層的硬化可能變得不足，另一方面，其累積光量超過5,000mJ/cm2時，照射時間變得非常長，對生產性提高不利。 The light irradiation time of the photocurable adhesive is not particularly limited by each of the adhesives to be hardened. However, the cumulative light amount expressed by the product of the irradiation intensity and the irradiation time is set to 10 to 5,000 mJ. / cm 2 is preferred. When the cumulative light amount of the photocurable adhesive is less than 10 mJ / cm 2 , the generation of the active material from the initiator is insufficient, and the hardening of the resulting adhesive layer may become insufficient. On the other hand, the cumulative light amount thereof exceeds 5,000 mJ / At cm 2 , the irradiation time becomes very long, which is disadvantageous for improving productivity.

於偏光器的兩面貼合保護膜時，活性能量線的照射，可從任一保護膜側進行，例如一側的保護膜含有紫外線吸收劑，另一側的保護膜不含紫外線吸收劑時，從不含紫外線吸收劑的保護膜側進行照射活性能量線，有效地利用所照射的活性能量線，在提高硬化速度上較佳。 When a protective film is attached to both sides of the polarizer, the irradiation of active energy rays can be performed from any protective film side. For example, when the protective film on one side contains a UV absorber and the protective film on the other side does not contain a UV absorber, It is preferable to irradiate active energy rays from the side of the protective film that does not contain an ultraviolet absorber, to effectively use the radiated active energy rays, and to improve the curing speed.

[積層光學構件] [Laminated Optical Component]

本發明的偏光板，可積層偏光板以外的具有光學功能的光學層，成為積層光學構件。典型上，於偏光板的保護膜，經由接著劑、或黏著劑而積層貼合光學層，藉此，成為積層光學構件，但其他例如，亦可於偏光器的一側的面，依據本發明而經由光硬化性接著劑，貼合保護膜，於偏光器的另一側的面，經由接著劑、或黏著劑，積層貼合光學層。於後者時，作為用以貼合偏光器與光學層的接著劑，使用本發明規定的光硬化性接著劑時，該光學層可同時成為本發明規定的保護膜。 The polarizing plate of the present invention can be laminated with an optical layer having an optical function other than the polarizing plate, and becomes a laminated optical member. Typically, a protective film on a polarizing plate is laminated and bonded to an optical layer through an adhesive or an adhesive, thereby becoming a laminated optical member. However, for example, it may be on one side of a polarizer according to the present invention. A protective film is attached via a photocurable adhesive, and an optical layer is laminated and laminated on the other surface of the polarizer via an adhesive or an adhesive. In the latter case, when the photocurable adhesive specified in the present invention is used as an adhesive for bonding a polarizer and an optical layer, the optical layer can simultaneously serve as a protective film specified in the present invention.

作為積層於偏光板的光學層之例，相對於配置於液晶胞的背面側之偏光板，例如積層於與面對該偏光板的液晶胞的側相反側之反射層、半透過反射層、光擴散層、聚光板、增亮膜等。而且，對於配置於液晶胞的前面側之偏光板以及/或配置於液晶胞的背面側之偏光板，例如積層於面對該偏光板的液晶胞的側之相 位差板等。 As an example of an optical layer laminated on a polarizing plate, for a polarizing plate disposed on the back side of a liquid crystal cell, for example, a reflective layer, a semi-transmissive reflecting layer, and a light layer laminated on the opposite side of the liquid crystal cell facing the polarizing plate. Diffusion layer, condenser plate, brightness enhancement film, etc. Moreover, for a polarizing plate arranged on the front side of the liquid crystal cell and / or a polarizing plate arranged on the back side of the liquid crystal cell, for example, a phase laminated on the side facing the liquid crystal cell of the polarizing plate. Parallax board and so on.

反射層、半透過反射層或光擴散層，係為了分別成為反射型偏光板(光學構件)、半透過反射型偏光板(光學構件)或擴散型偏光板(光學構件)而設置。反射型之偏光板係用於反射從辨識側的入射光顯示之型體的液晶顯示裝置，因可省略背光等的光源，容易使液晶顯示裝置薄型化。而且，半透過型之偏光板，係用於在亮處為反射型，在暗處為來自背光的光顯示之型體的液晶顯示裝置。作為反射型偏光板的光學構件，例如於偏光器上的保護膜，附設由鋁等金屬所構成的箔或蒸鍍膜，可形成反射層。作為半透過型之偏光板的光學構件，可以上述反射層作為半反射鏡，或使含有珍珠顏料等而顯示光穿透性之反射板接著於偏光板而形成。另一方面，作為擴散型偏光板的光學構件，例如對偏光板上的保護膜施以霧面(matt)處理之方法、塗佈含有微粒子的樹脂之方法、接著含有微粒子的膜之方法等各種方法，而於表面形成細微凹凸構造。 The reflective layer, the transflective reflective layer, or the light diffusing layer is provided so as to be a reflective polarizer (optical member), a transflective reflective polarizer (optical member), or a diffusive polarizer (optical member). The reflective polarizing plate is a liquid crystal display device for reflecting an incident light displayed from the recognition side. Since a light source such as a backlight can be omitted, the liquid crystal display device can be easily made thinner. In addition, the semi-transmissive polarizing plate is a liquid crystal display device which is a reflective type in a bright place and a light display from a backlight in a dark place. As the optical member of the reflective polarizing plate, for example, a protective film on a polarizer is attached with a foil or a vapor-deposited film made of a metal such as aluminum to form a reflective layer. As the optical member of the semi-transmissive polarizing plate, the above-mentioned reflecting layer may be used as a semi-reflecting mirror, or a reflecting plate containing a pearl pigment or the like and exhibiting light transmittance may be formed next to the polarizing plate. On the other hand, as the optical member of the diffusion-type polarizing plate, there are various methods such as a method of applying a matt treatment to a protective film on the polarizing plate, a method of applying a resin containing fine particles, and a method of subsequently attaching a film containing fine particles. Method to form a fine uneven structure on the surface.

再者，亦可形成作為反射擴散兩用的偏光板之光學構件，於該情況，例如可採用於擴散型偏光板的細微凹凸構造面，設置反映該凹凸構造的反射層等之方法。細微凹凸構造的反射層，係將入射光藉由散射而使之擴散，防止指向性或眩光，具有可抑制明暗不均勻等的優點。而且，含有微粒子的樹脂層或膜，係亦具有使入射光及其反射光穿過含有微粒子的層時被擴散、可抑制明暗不均勻等的優點。可反映表面細微凹凸構造之反射層，例如藉由真空蒸鍍、離子鍍、濺鍍之蒸鍍或電鍍等的方法，使金屬直接附設於細微凹凸構造的表面來形成。為了形成表面細微凹 凸構造而調配之微粒子，例如平均粒徑為0.1至30μm之如氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻之無機系微粒子、如交聯或未交聯的聚合物之有機系微粒子等。 Furthermore, an optical member that is a polarizing plate for both reflection and diffusion can also be formed. In this case, for example, a method of providing a fine uneven structure surface of a diffusion-type polarizer and providing a reflective layer reflecting the uneven structure can be used. The reflective layer with a fine uneven structure diffuses incident light to diffuse it, prevents directivity or glare, and has the advantages of suppressing uneven brightness. In addition, the resin layer or film containing fine particles has advantages such that incident light and reflected light are diffused when passing through the layer containing fine particles, and unevenness in light and dark can be suppressed. The reflective layer that can reflect the fine uneven structure on the surface is formed by directly attaching a metal to the surface of the fine uneven structure by a method such as vacuum evaporation, ion plating, sputtering, or electroplating. Fine particles prepared to form a fine uneven structure on the surface, for example, inorganic fine particles having an average particle diameter of 0.1 to 30 μm such as silicon oxide, aluminum oxide, titanium oxide, zirconia, tin oxide, indium oxide, cadmium oxide, and antimony oxide , Such as organic particles of crosslinked or uncrosslinked polymers.

聚光板因係以控制光路徑為目的所使用者，可形成為稜鏡陣列薄片、透鏡陣列薄片或附設點的薄片。 Since the light collecting plate is used for the purpose of controlling the light path, the light collecting plate can be formed as a hologram array sheet, a lens array sheet, or a sheet with attached points.

增亮膜因係以提高液晶顯示裝置的亮度為目的所使用者，其例係可舉例如設計成折射率的異向性互為相異的薄膜積層複數片而於反射率產生異向性之反射型偏光分離片、膽固醇液晶聚合物的配向膜、於膜基材上支撐有該配向液晶層之圓偏光分離片等。 The brightness-enhancing film is used by the user for the purpose of improving the brightness of a liquid crystal display device. For example, the brightness-enhancing film may be a multilayer film having a refractive index anisotropy that is different from each other, and an anisotropy in the reflectivity. A reflective polarizing separation sheet, an alignment film of a cholesteric liquid crystal polymer, a circularly polarizing separation sheet supporting the alignment liquid crystal layer on a film substrate, and the like.

另一方面，作為上述光學層之相位差板，係以液晶胞所造成之相位差的補償等為目的而被使用。其例係可舉例如各種塑膠的延伸膜等所構成的複折射性膜、配向固定有碟狀液晶、向列型液晶的膜、膜基材上形成有上述液晶層者等。於膜基材上形成液晶層的時，作為膜基材，以使用三乙醯基纖維素等纖維素系樹脂膜為較佳。 On the other hand, the retardation plate of the optical layer is used for the purpose of compensating a retardation caused by a liquid crystal cell and the like. Examples thereof include birefringent films composed of various plastic stretch films, films in which dish-shaped liquid crystals, nematic liquid crystals are fixed in alignment, and those in which the liquid crystal layer is formed on a film substrate. When forming a liquid crystal layer on a film substrate, it is preferable to use a cellulose-based resin film such as triethylfluorene cellulose as the film substrate.

作為形成雙折射性膜的塑膠，可舉例如非結晶性聚烯烴系樹脂、聚碳酸酯系樹脂、丙烯酸系樹脂、如聚丙烯的鏈狀聚烯烴系樹脂、聚乙烯醇、聚苯乙烯、聚丙烯酸酯、聚醯胺等。延伸膜可為以一軸或二軸等適當方式處理者。再者，相位差板係就控制寬頻化等光學特性為目的下，亦可組合2片以上而使用。 Examples of the plastic forming the birefringent film include an amorphous polyolefin resin, a polycarbonate resin, an acrylic resin, a chain polyolefin resin such as polypropylene, polyvinyl alcohol, polystyrene, and poly Acrylate, Polyamine, etc. The stretched film may be treated in a suitable manner such as one axis or two axes. In addition, a retardation plate may be used in combination of two or more for the purpose of controlling optical characteristics such as widening.

於積層光學構件中，包含相位差板作為偏光板以外的光學層者，因應用於液晶顯示裝置時可有效地光學補償，故適合使用。相位差板的相位差值(面內及厚度方向)，依據所適用的 液晶胞，只要選擇最適者即可。 The laminated optical member includes a retardation plate as an optical layer other than the polarizing plate, and is suitable for use because it can effectively optically compensate when applied to a liquid crystal display device. The retardation value of the retardation plate (in-plane and thickness direction), according to the applicable As for the liquid crystal cell, it is only necessary to select the most suitable one.

積層光學構件係組合偏光板、以及依據使用目的而從上述各種光學層所選擇之1層或2層以上，可成為2層或3層以上的積層體。其時，形成積層光學構件之各種光學層，係使用接著劑或黏著劑而與偏光板形成一體，因此，所使用的接著劑或黏著劑，只要是可形成良好的接著劑層、或黏著劑層者即可，無特別限制。從接著操作的簡易性、或防止光學扭曲的產生等之觀點，以使用黏著劑(亦稱為感壓接著劑)較佳。於黏著劑係可使用丙烯酸系聚合物、聚矽氧樹脂系聚合物、聚酯、聚胺基甲酸乙酯、聚醚等作為基質聚合物者。其中，選擇使用如丙烯酸系黏著劑般具光學透明性佳、保持適度潤濕性或凝聚力、與基材的接著性亦佳，又具有耐候性或耐熱性等，且在加熱或加濕的條件下不會產生浮出或剝離等的剝離問題者較佳。於丙烯酸系黏著劑中，可調配具有甲基、乙基、或丁基等碳數20以下的烷基之(甲基)丙烯酸的烷酯與含有(甲基)丙烯酸或(甲基)丙烯酸羥基乙酯等所構成的官能基之丙烯酸系單體，以使玻璃轉化溫度較佳為25℃以下，更佳為0℃以下，且重量平均分子量為10萬以上的丙烯酸系共聚物作為基質聚合物。 The laminated optical member is a combination of a polarizing plate and one or two or more layers selected from the various optical layers described above depending on the purpose of use, and can be a laminated body of two or more layers. At this time, various optical layers forming a laminated optical member are integrated with the polarizing plate by using an adhesive or an adhesive. Therefore, as long as the adhesive or the adhesive used can form a good adhesive layer or adhesive, There is no particular limitation as long as it is a layer. It is preferable to use an adhesive (also referred to as a pressure-sensitive adhesive) from the viewpoints of simplicity of subsequent operations, prevention of occurrence of optical distortion, and the like. For the adhesive system, acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers can be used as the matrix polymer. Among them, choose to use conditions such as acrylic adhesives that have good optical transparency, maintain moderate wetting or cohesion, have good adhesion to the substrate, and have weather resistance or heat resistance. Those who do not cause peeling problems such as floating or peeling are preferred. In acrylic adhesives, alkyl (meth) acrylic acid alkyls having alkyl groups having a carbon number of 20 or less such as methyl, ethyl, or butyl can be blended with hydroxyl groups containing (meth) acrylic or (meth) acrylic acid Acrylic monomers having functional groups composed of ethyl ester, etc., have an acrylic copolymer having a glass transition temperature of preferably 25 ° C or lower, more preferably 0 ° C or lower, and a weight average molecular weight of 100,000 or more as a matrix polymer. .

於偏光板形成黏著劑層係例如可藉由於甲苯或乙酸乙酯等的有機溶劑，使黏著劑組成物溶解或分散而調製10至40重量%的溶液，再直接塗佈於偏光板上之方式；或藉由預先於保護膜上形成黏著劑層，再轉移至偏光板上的方式等進行。黏著劑層的厚度，可依據其接著力等而決定，但以1至50μm程度的範圍為適當。 The formation of the adhesive layer on the polarizing plate is a method in which a 10 to 40% by weight solution can be prepared by dissolving or dispersing the adhesive composition due to an organic solvent such as toluene or ethyl acetate, and then directly coating the polarizing plate. ; Or by forming an adhesive layer on the protective film in advance, and then transferring it to a polarizing plate. The thickness of the adhesive layer can be determined depending on its adhesion, etc., but it is appropriate to be in the range of about 1 to 50 μm .

而且，於黏著劑層，係依據需要，亦可調配玻璃纖維、玻璃珠、樹脂粒、金屬粉、或其他無機粉末等所構成的填充劑、顏料、或著色劑、抗氧化劑、紫外線吸收劑等。於紫外線吸收劑係有水楊酸酯系化合物、二苯基酮系化合物、苯並***系化合物、氰基丙烯酸酯系化合物、及鎳錯鹽系化合物等。 In addition, in the adhesive layer, fillers, pigments, colorants, antioxidants, ultraviolet absorbers made of glass fibers, glass beads, resin particles, metal powders, or other inorganic powders can be blended as required. . Examples of the ultraviolet absorber include a salicylate-based compound, a diphenyl ketone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, and a nickel salt-based compound.

積層光學構件係可配置於液晶胞的單側或兩側。所使用的液晶胞為任意，例如可使用以薄膜電晶體型為代表之主動矩陣驅動型者、以超扭曲向列型為代表的單純矩陣驅動型者等各種液晶胞而形成液晶顯示裝置。積層光學構件與液晶胞的接著，一般可使用黏著劑。 The laminated optical member can be arranged on one side or both sides of the liquid crystal cell. The liquid crystal cell to be used is arbitrary, and for example, various types of liquid crystal cells such as an active matrix driving type represented by a thin film transistor type and a simple matrix driving type represented by a super twisted nematic type may be used to form a liquid crystal display device. Adhesives are generally used for bonding the laminated optical member to the liquid crystal cell.

實施例 Examples

以下顯示實施例，更具體地說明本發明，但本發明不受限於該等實施例。例中，表示含量至使用量的%以及份，在沒有特別記載下為重量基準。而且，以下之例所使用的(A)光陽離子硬化性成分以及(B)光陽離子聚合引發劑係如下述。 Examples are shown below to explain the present invention more specifically, but the present invention is not limited to these examples. In the examples, the content and the percentage used are shown in% and parts. Unless otherwise specified, they are based on weight. The (A) photocationically curable component and (B) photocationic polymerization initiator used in the following examples are as follows.

(A)光陽離子硬化性成分：(A1)脂環式二環氧化合物：(a1)3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯[於上述式(I)，R1=R2=H，X1=-COOCH2-的化合物] (A) Photocationically curable component: (A1) alicyclic diepoxy compound: (a1) 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester [in the above formula (I), R 1 = R 2 = H, X 1 = -COOCH 2 -compound]

(A2)二環氧丙基化合物：(a2)新戊基二環氧丙基醚[於上述式(II)，Z=-CH2C(CH3)2CH2-的化合物] (A2) Diglycidyl compound: (a2) neopentyl diglycidyl ether [compound of the above formula (II), Z = -CH 2 C (CH 3 ) 2 CH 2- ]

(a2’)2-乙基己基環氧丙基醚 (a2 ’) 2-ethylhexyl glycidyl ether

(A3)由乙烯性不飽和單體所構成的聚合物： (A3) Polymer composed of ethylenically unsaturated monomer:

(a3-I)使環氧丙基甲基丙烯酸酯(GMA)25份、苯乙烯75份所構成的單體進行自由基聚合之重量平均分子量15000的聚合物(GMA-PS(聚苯乙烯)共聚物) (a3-I) A polymer (GMA-PS (polystyrene) having a weight-average molecular weight of 15,000 by radical polymerization of a monomer composed of 25 parts of glycidyl methacrylate (GMA) and 75 parts of styrene Copolymer)

(a3-II)使由環氧丙基甲基丙烯酸酯25份、甲基丙烯酸甲酯75份所構成的單體進行自由基聚合之重量平均分子量15000的聚合物(GMA-PMMA(聚甲基丙烯酸甲酯)共聚物) (a3-II) A polymer (GMA-PMMA (polymethyl) having a weight-average molecular weight of 15,000 by radical polymerization of a monomer composed of 25 parts of glycidyl methacrylate and 75 parts of methyl methacrylate. Methyl acrylate) copolymer)

(a3-III)使由環氧丙基甲基丙烯酸酯25份、甲基丙烯酸甲酯75份所構成的單體進行自由基聚合之重量平均分子量30000的聚合物(分子量30000之GMA-PMMA共聚物) (a3-III) A polymer having a weight average molecular weight of 30,000 (a GMA-PMMA copolymer having a molecular weight of 30,000) obtained by radically polymerizing a monomer composed of 25 parts of glycidyl methacrylate and 75 parts of methyl methacrylate. Thing)

(a4-I)2-乙基己基乙烯基醚 (a4-I) 2-ethylhexyl vinyl ether

(a4-II)羥基丁基乙烯基醚 (a4-II) Hydroxybutyl vinyl ether

(B)光陽離子聚合引發劑： (B) Photocationic polymerization initiator:

(b1)三芳香基鋶六氟磷酸酯 (b1) Triarylphosphonium hexafluorophosphate

[實施例1至14以及比較例1] [Examples 1 to 14 and Comparative Example 1]

(1)光硬化性接著劑的調製 (1) Preparation of photocurable adhesive

混合上述各成分後，進行脫泡，調製實施例1至14以及比較例1的光硬化性接著劑(液狀)。於表1，使用記號，表示各成分的調配比例(單位為份)。再者，光陽離子聚合引發劑(b1)，實際上調配為50%碳酸丙烯酯溶液，於表1中，依據其固體成分量，表示調配比例。 After mixing each of the above components, defoaming was performed to prepare the photocurable adhesives (liquid) of Examples 1 to 14 and Comparative Example 1. In Table 1, symbols are used to indicate the blending ratio of each component (unit is part). In addition, the photocationic polymerization initiator (b1) is actually prepared as a 50% propylene carbonate solution. In Table 1, the formulation ratio is shown based on the solid content.

(2)測定光硬化性接著劑在25℃之黏度 (2) Measure the viscosity of photocuring adhesive at 25 ℃

對於上述調製的各光硬化性接著劑(接著劑溶液)，使用東機產業(股)製的E型黏度計”TVE-25L”，測定溫度25℃之黏度。結果表示於表2。 For each of the photocurable adhesives (adhesive solutions) prepared as described above, the viscosity was measured at a temperature of 25 ° C. using an E-type viscometer “TVE-25L” manufactured by Toki Sangyo Co., Ltd. The results are shown in Table 2.

(3)保護膜的溶解性 (3) Solubility of protective film

準備所需要的片數之20g的10mm×40mm厚度為80μm的丙烯酸系樹脂(PMMA)[商品名“Technolloy S001”、住友化學(股)製]作為保護膜。將該保護膜於室溫(23℃)下浸漬於上述(1)調製的各實施例及比較例的光硬化性接著劑(接著劑溶液)中2天。然後，將保護膜從接著劑溶液取出，以棉花棒擦拭附著於保護膜的接著 劑溶液後，測定該保護膜的重量。 An acrylic resin (PMMA) [trade name "Technolloy S001", manufactured by Sumitomo Chemical Co., Ltd.] with a thickness of 80 g and a thickness of 10 g x 40 mm with a required number of 20 g was prepared as a protective film. This protective film was immersed in the photocurable adhesive (adhesive solution) of each of the examples and comparative examples prepared in the above (1) at room temperature (23 ° C) for 2 days. Then, the protective film was taken out from the adhesive solution, and the adhesive adhered to the protective film was wiped with a cotton swab. After the agent solution, the weight of the protective film was measured.

溶解率係由下述式求得。 The dissolution rate is determined by the following formula.

溶解率(重量%)=(1-浸漬後的保護膜之重量/浸漬前的保護膜的重量(20g))×100 Dissolution rate (% by weight) = (1-weight of protective film after immersion / weight of protective film before immersion (20g)) × 100

若該溶解率大到一定程度，對保護膜的密合性會變佳，另一方面，若該溶解率太大，保護膜顯著地溶解，於接著部分產生氣泡等的缺陷之可能性變高。所以，該溶解率為適當的範圍較佳，該範圍例如為15至70重量%左右。 If the dissolution rate is large to a certain degree, the adhesiveness to the protective film will be improved. On the other hand, if the dissolution rate is too large, the protection film will dissolve significantly, and the possibility of defects such as air bubbles in the subsequent portion becomes high. . Therefore, a suitable range of the dissolution rate is preferable, and the range is, for example, about 15 to 70% by weight.

(4)包含丙烯酸系樹脂的偏光板之製作 (4) Fabrication of polarizing plate containing acrylic resin

包含紫外線吸收劑的厚度80μm之丙烯酸系樹脂(PMMA)[商品名”Technolloy S001”、住友化學(股)製]的表面，施以電暈放電處理，於該電暈放電處理的面，使用棒塗器塗佈上述調製的各接著劑溶液，以使硬化後的膜厚約成為3μm。對該接著劑層貼合厚度25μm之聚乙烯醇(PVA)-碘系偏光器。 The surface of the acrylic resin (PMMA) [trade name “Technolloy S001”, manufactured by Sumitomo Chemical Co., Ltd.] containing a UV absorber and having a thickness of 80 μm is subjected to a corona discharge treatment. The applicator applied each of the prepared adhesive solutions so that the film thickness after curing became about 3 μm . A polyvinyl alcohol (PVA) -iodine-based polarizer having a thickness of 25 μm was bonded to the adhesive layer.

而且，對降莰烯系樹脂(COP：環烯烴聚合物)所構成的厚度50μm之相位差膜[商品名“ZEONOR”、日本ZEON(股)製]的表面，施以電暈放電處理，於該電暈放電處理面，使用棒塗器塗佈上述相同的接著劑溶液，以使硬化後的膜厚約成為3μm。於該接著劑層貼合上述製作的單面貼合有丙烯酸系樹脂的偏光器之偏光器側，製作積層物。 Furthermore, the surface of a 50 μm- thick retardation film [trade name "ZEONOR", manufactured by Japan Zeon Co., Ltd.] made of norbornene-based resin (COP: cycloolefin polymer) was subjected to a corona discharge treatment. On the corona discharge treated surface, the same adhesive solution as described above was applied using a bar coater so that the film thickness after curing was about 3 μm . The polarizer side of the polarizer on which the acrylic resin was bonded on one side was fabricated on the adhesive layer to produce a laminate.

從該積層物的相位差膜側，使用附有皮帶輸送機之紫外線照射裝置(燈為Fusion UV system公司製的“D bulb”)，照射紫外線，以使累積光量成為250mJ/cm2(UVB)，並使接著劑硬化。如此一來，製作包含丙烯酸系樹脂的偏光板(丙烯酸系樹脂/ 偏光器/降莰烯系樹脂)。 From the retardation film side of the laminate, an ultraviolet irradiation device ("D bulb" manufactured by Fusion UV system) with a belt conveyor was used to irradiate ultraviolet rays so that the cumulative light amount was 250 mJ / cm 2 (UVB) And harden the adhesive. In this way, a polarizing plate (acrylic resin / polarizer / norbornene resin) containing an acrylic resin was produced.

(5)包含三乙醯基纖維素系樹脂的偏光板之製作 (5) Fabrication of polarizing plate containing triethylfluorinated cellulose resin

包含紫外線吸收劑的厚度80μm之三乙醯基纖維素系樹脂)[商品名"Konicatac KC8UX2MW"、柯尼卡美能達(Konica Minolta)精密光學(股)製]的表面，施以電暈放電處理，於該電暈放電處理面，使用棒塗器塗佈上述調製的各接著劑溶液，以使硬化後的膜厚約成為3μm。於該接著劑層貼合厚度25μm之聚乙烯醇-碘系偏光器。 A triethylammonium cellulose resin with a thickness of 80 μm containing an ultraviolet absorber) [trade name "Konicatac KC8UX2MW", Konica Minolta Precision Optics Co., Ltd.] The surface is corona-treated In the discharge treatment, each of the adhesive solution prepared above was applied to the corona discharge treated surface with a bar coater so that the film thickness after curing became about 3 μm . A polyvinyl alcohol-iodine-based polarizer having a thickness of 25 μm was attached to the adhesive layer.

而且，由降莰烯系樹脂(COP：環烯烴聚合物)所構成的厚度50μm之相位差膜[商品名"ZEONOR"、日本ZEON(股)製]的表面，施以電暈放電處理，於該電暈放電處理面，使用棒塗器塗佈上述相同的接著劑溶液，以使硬化後的膜厚約成為3μm。於該接著劑層，貼合上述製作的單面貼合有三乙醯基纖維素樹脂的偏光器的偏光器側，製作積層物。 In addition, the surface of a 50 μm- thick retardation film [trade name "ZEONOR", manufactured by Japan Zeon Co., Ltd.] made of norbornene-based resin (COP: cycloolefin polymer) was subjected to a corona discharge treatment. On the corona discharge treated surface, the same adhesive solution as described above was applied using a bar coater so that the film thickness after curing was about 3 μm . On the adhesive layer, the polarizer side of the polarizer on which the triethylfluorene-based cellulose resin was single-sidedly bonded as described above was bonded to produce a laminate.

從該積層物的降莰烯系相位差膜側，使用附有皮帶輸送機之紫外線照射裝置(燈為Fusion UV system公司製的"D bulb")，照射紫外線，以使累積光量成為250mJ/cm2(UVB)，並使接著劑硬化。如此，製作包含三乙醯基纖維素系樹脂的偏光板(三乙醯基纖維素系樹脂/偏光器/降莰烯系樹脂)。 From the norbornene-based retardation film side of this laminate, an ultraviolet irradiation device (a lamp is "D bulb" manufactured by Fusion UV system) with a belt conveyor was used to irradiate ultraviolet rays so that the accumulated light amount was 250 mJ / cm 2 (UVB) and harden the adhesive. In this way, a polarizing plate (triethylfluorene-based cellulose resin / polarizer / norbornene-based resin) containing a triethylfluorene-based cellulose resin was produced.

(6)包含丙烯酸系樹脂的偏光板之180度剝離測試 (6) 180-degree peel test of polarizing plate containing acrylic resin

將上述(4)製作的偏光板裁切成長度200mm×寬度25mm的大小。繼而，在厚度80μm之丙烯酸系樹脂側，設置丙烯酸系的黏著劑層，作為用以測定該丙烯酸系樹脂與偏光器之間的剝離強度的測試片。與其不同地，於厚度50μm之降莰烯系相位差膜側， 設置丙烯酸系的黏著劑層，作為丙烯酸系樹脂與偏光器間的剝離強度用的測試片。 The polarizing plate produced in the above (4) was cut into a size of 200 mm in length × 25 mm in width. Then, an acrylic adhesive layer was provided on the acrylic resin side with a thickness of 80 μm as a test piece for measuring the peel strength between the acrylic resin and the polarizer. In contrast, an acrylic adhesive layer was provided on the norbornene-based retardation film side with a thickness of 50 μm as a test piece for peel strength between the acrylic resin and the polarizer.

將各測試片的黏著劑層黏貼於玻璃板，偏光器與黏著劑側的保護膜(丙烯酸系樹脂或降莰烯系相位差膜)之間，放入切刀的刃，於長度方向從端部剝開30mm，該剝開部分以測試機的夾具部夾住。該狀態的測試片，在溫度23℃以及相對濕度55%的環境中，依據JIS K 6854-2：1999「接著劑-剝離接著強度測試方法-第2部：180度剝離測試」，以夾具部移動速度300mm/分，進行180度剝離測試，求出除了夾具部的30mm之涵蓋170mm長度之平均剝離力。再者，測定時，係製作偏光板後24小時之後。結果表示於表2。 Adhere the adhesive layer of each test piece to the glass plate, place the polarizer and the protective film (acrylic resin or norbornene retardation film) on the adhesive side, put the blade of the cutter, and run it from the end in the longitudinal direction. The part was peeled off by 30 mm, and the peeled part was clamped by the clamp part of the testing machine. The test piece in this state was subjected to a jig section in an environment of a temperature of 23 ° C and a relative humidity of 55% in accordance with JIS K 6854-2: 1999 "Adhesive-Peel Adhesion Test Method-Part 2: 180-degree Peel Test". The moving speed was 300 mm / min, and a 180-degree peel test was performed to find an average peel force covering a length of 170 mm except for the 30 mm of the jig portion. The measurement was performed 24 hours after the polarizing plate was produced. The results are shown in Table 2.

再者，表2的180度剝離測試項目中，「PMMA/PVA」的欄，表示上述丙烯酸系樹脂膜與偏光器之間的剝離強度，「COP/PVA」的欄，係表示上述降莰烯系相位差膜與偏光器之間的剝離強度。 In the 180-degree peel test items in Table 2, the column "PMMA / PVA" indicates the peel strength between the acrylic resin film and the polarizer, and the column "COP / PVA" indicates the norbornene. The peeling strength between the retardation film and the polarizer.

(7)包含三乙醯基纖維素系樹脂的偏光板之180度剝離測試 (7) 180-degree peel test of polarizing plate containing triethylfluorene-based cellulose resin

將上述(5)製作的偏光板裁切為長度200mm×寬度25mm的大小。於是，在厚度80μm之三乙醯基纖維素系樹脂側，設置丙烯酸系的黏著劑層，作為該三乙醯基纖維素系樹脂與偏光器間的剝離強度用的測試片。 The polarizing plate produced in the above (5) was cut into a size of 200 mm in length × 25 mm in width. Then, an acrylic adhesive layer was provided on the triethyl cellulose-based resin side having a thickness of 80 μm as a test piece for peel strength between the triethyl cellulose-based resin and the polarizer.

將各測試片的黏著劑層黏貼於玻璃板，偏光器與黏著劑側的保護膜(丙烯酸系樹脂)之間，放入切刀的刃，於長度方向從端部剝開30mm，該剝開部分用測試機的夾具部夾住。與 上述180度剝離測試同樣地，求出平均剝離力。再者，測定時，係製作偏光板後24小時之後。結果表示於表2。 The adhesive layer of each test piece was adhered to a glass plate, between the polarizer and the protective film (acrylic resin) on the adhesive side, the blade of a cutter was placed, and 30 mm was peeled from the end in the longitudinal direction. A part is clamped by the clamp part of a testing machine. versus In the same manner as the 180-degree peel test, the average peel force was determined. The measurement was performed 24 hours after the polarizing plate was produced. The results are shown in Table 2.

再者，表2的180度剝離測試項目中，「TAC/PVA」的欄，表示上述三乙醯基纖維素系樹脂膜與偏光器之間的剝離強度。 In the 180-degree peel test items in Table 2, the column "TAC / PVA" indicates the peel strength between the triethylfluorene-based cellulose resin film and the polarizer.

由表1及表2得知，使用含有作為由乙烯性不飽和單體所構成的聚合物(A3)之(a3-II)或(a3-III)之接著劑的實施例7及8中，剝離力全部為0.5N/25mm以上。另一方面，於使用不含聚合物(A3)之接著劑的比較例1、以及光陽離子硬化性成分(A)中聚合物(A3)的含量未達5%之接著劑的比較例2至5中，PMMA/PVA 的剝離力為極低至0.15至0.03N/25mm。而且，保護膜的溶解性，實施例7及8為15%以上，但比較例1至3為小至10至11%。 As can be seen from Tables 1 and 2, in Examples 7 and 8 using an adhesive containing (a3-II) or (a3-III) as a polymer (A3) composed of an ethylenically unsaturated monomer, All peeling forces are 0.5 N / 25 mm or more. On the other hand, in Comparative Example 1 using a polymer-free adhesive (A3) -free adhesive, and Comparative Examples 2 to 2 in a photo-cationically curable component (A) with a polymer (A3) content of less than 5%. 5, PMMA / PVA The peeling force is extremely low as low as 0.15 to 0.03N / 25mm. Moreover, the solubility of the protective film was 15% or more in Examples 7 and 8, but as small as 10 to 11% in Comparative Examples 1 to 3.

從實施例1及、2的結果，均使用重量平均分子量15000的聚合物(A3)之(a3-I)及(a3-II)時，剝離力為相同。而且，從實施例2及3的結果，聚合物(A3)為GMA-PMMA共聚物時，使其重量平均分子量為30000者，剝離力會提高。 From the results of Examples 1 and 2, when (a3-I) and (a3-II) of the polymer (A3) having a weight average molecular weight of 15,000 were used, the peeling force was the same. Further, from the results of Examples 2 and 3, when the polymer (A3) is a GMA-PMMA copolymer, the weight average molecular weight is 30,000, and the peeling force is improved.

而且，從實施例3、6、8、11及13的結果，與使用由(a1)、(a2)、(a3-III)所構成的接著劑時(實施例3)相比較，再使用含有5%的(a2’)、(a4-I)、(a4-II)之任一者的接著劑時(實施例6、8、11及13)，亦對於PMMA之剝離性沒有改變。另一方面，對於COP及TAC之剝離力，使用含有(a4-II)的接著劑者時，為良好。 The results of Examples 3, 6, 8, 11, and 13 were compared with those obtained when using an adhesive consisting of (a1), (a2), and (a3-III) (Example 3), and then using When 5% of (a2 '), (a4-I), or (a4-II) was used as an adhesive (Examples 6, 8, 11, and 13), the peelability of PMMA was not changed. On the other hand, the peeling force of COP and TAC is good when using the adhesive containing (a4-II).

[實施例15至25以及比較例6至7] [Examples 15 to 25 and Comparative Examples 6 to 7]

然後，表示使用(A)光陽離子硬化性成分以及(B)光陽離子聚合引發劑中添加水分或二醇化合物之接著劑溶液而製作偏光板之實施例15至25以及比較例6至7。再者，即使於實施例15至25以及比較例6至7中，(A)光陽離子硬化性成分以及(B)光陽離子聚合引發劑係使用與先前表示者相同者。而且，實施例15至25以及比較例6至7所使用的水分及二醇化合物係如下述。 Next, Examples 15 to 25 and Comparative Examples 6 to 7 in which polarizing plates were produced using (A) a photocationic curable component and (B) a photocationic polymerization initiator with an adhesive solution containing water or a diol compound were prepared. In addition, even in Examples 15 to 25 and Comparative Examples 6 to 7, (A) a photocationic curable component and (B) a photocationic polymerization initiator are the same as those shown previously. The moisture and diol compounds used in Examples 15 to 25 and Comparative Examples 6 to 7 are as follows.

〈水分) <Moisture)

精製水 Refined water

〈二醇化合物〉 <Diol compound>

(c1)乙二醇 (c1) ethylene glycol

(c2)1,2-丙二醇 (c2) 1,2-propanediol

(c3)1,4-丁二醇 (c3) 1,4-butanediol

(1)光硬化性接著劑的調製 (1) Preparation of photocurable adhesive

混合上述各成分後，進行脫泡，調製實施例15至25以及比較例6至7的光硬化性接著劑(液狀)。於表3，使用記號，表示各成分的調配比例(單位為份)。再者，光陽離子聚合引發劑(b1)，實際上係調配為50%碳酸丙烯酯溶液，但於表3，係依據其固體成分量，表示調配比例。 After mixing each of the above components, defoaming was performed to prepare the photocurable adhesives (liquid) of Examples 15 to 25 and Comparative Examples 6 to 7. In Table 3, a symbol is used to indicate the blending ratio of each component (unit is part). In addition, the photocationic polymerization initiator (b1) is actually formulated as a 50% propylene carbonate solution. However, Table 3 shows the formulation ratio based on the solid content.

(2)接著劑溶液的均勻性 (2) Homogeneity of the adhesive solution

上述(1)所調製的接著劑溶液的狀態以目視確認之，以如下的基準分類。結果表示於表3。 The state of the adhesive solution prepared in the above (1) was visually confirmed, and classified according to the following criteria. The results are shown in Table 3.

〈接著劑溶液的均勻性之評價基準〉 <Evaluation Criteria for Uniformity of Adhesive Solution>

A：接著劑溶液沒有層分離 A: Adhesive solution without layer separation

B：接著劑溶液有層分離 B: Adhesive solution has layer separation

(3)含有丙烯酸系樹脂的偏光板之製作 (3) Fabrication of polarizing plate containing acrylic resin

使用所得之接著劑溶液，以與實施例1至14以及比較例1~5的(4)表示者相同的方法，製作含有丙烯酸系樹脂的偏光板。 Using the obtained adhesive solution, a polarizing plate containing an acrylic resin was produced in the same manner as that shown in (4) of Examples 1 to 14 and Comparative Examples 1 to 5.

(4)含有丙烯酸系樹脂的180度剝離測試 (4) 180-degree peel test containing acrylic resin

對於所得之偏光板，以與實施例1至14以及比較例1~5的(6)表示者相同的方法，測定丙烯酸系樹脂與偏光器之間的剝離強度。結果表示於表3。 About the obtained polarizing plate, the peeling strength between an acrylic resin and a polarizer was measured by the same method as that shown by (6) of Examples 1 to 14 and Comparative Examples 1 to 5. The results are shown in Table 3.

由表3得知，於使用含有既定量水分之接著劑的實施例15至18中，與使用不含水分之接著劑的實施例10比較，剝離力進一步提高。而且，於使用含有既定量二醇化合物之接著劑的實施例19至25中，與使用不含二醇化合物之接著劑的實施例10相比較，剝離力進一步提高。 As can be seen from Table 3, in Examples 15 to 18 in which an adhesive containing a predetermined amount of moisture was used, the peeling force was further improved compared to Example 10 using an adhesive containing no moisture. Further, in Examples 19 to 25 in which an adhesive containing a predetermined amount of a diol compound was used, the peeling force was further improved compared to Example 10 in which an adhesive containing no diol compound was used.

Claims (14)

一種光硬化性接著劑，其係用以對由吸附配向有二色性色素之聚乙烯醇系樹脂膜所構成的偏光器接著由透明樹脂膜所構成的保護膜，其25℃之黏度為2至300mPa．sec以下，並含有：(A)光陽離子硬化性成分100重量份；以及(B)光陽離子聚合引發劑1至10重量份；前述光陽離子硬化性成分(A)係含有(A1)以下式(I)所示之脂環式二環氧化合物10至60重量%(式中，R1及R2分別獨立表示氫原子或碳數1至6的烷基，烷基為碳數3以上時，亦可具有脂環構造；X1為氧原子、碳數1至6的烷二基或以下式(Ia)至(Id)之任一者所示的2價基) (式中，Y1至Y4分別獨立表示碳數1至20的烷二基，於碳數3以上時，亦可具有脂環構造；a及b分別獨立表示0至20的整數)；(A2)以下式(II)所示之二環氧丙基化合物20至75重量%(式中，Z表示碳數1至9的伸烷基、碳數3或4的亞烷基或2價脂環式烴基，該伸烷基中的亞甲基亦可被氧原子、-CO-O-、-O-CO-、-SO2-、-SO-或-CO-所示的2價基中斷)；(A3)選自以下式(III)或(IV)所示之單體中至少1種的乙烯性不飽和單體所構成的重量平均分子量為5000至100000的聚合物5至50重量%(式中，X2為(i)碳原子數1至7的烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基、或者(ii)被選自由環氧基、氧雜環丁烷基、羥基及羧基所成之群中之1種以上的基部分取代之碳原子數1至7的烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基)(式中，R3表示氫原子、甲基或鹵原子，X3係與上述式(III)中之X2相同)。A light-curing adhesive, which is used to polarize a polarizer composed of a polyvinyl alcohol resin film having a dichroic pigment and align it to a protective film composed of a transparent resin film. The viscosity at 25 ° C is 2 Up to 300mPa. sec or less and (A) 100 parts by weight of the photocationically curable component; and (B) 1 to 10 parts by weight of the photocationic polymerization initiator; the photocationically curable component (A) contains (A1) the following formula ( I) 10 to 60% by weight of the alicyclic diepoxy compound shown (In the formula, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. When the alkyl group is 3 or more carbon atoms, it may have an alicyclic structure; X 1 is an oxygen atom and 1 to 6 carbon atoms. (Alkanediyl of 6 or a divalent group represented by any one of the following formulae (Ia) to (Id)) (In the formula, Y 1 to Y 4 each independently represent an alkanediyl group having 1 to 20 carbon atoms, and may have an alicyclic structure when the carbon number is 3 or more; a and b each independently represent an integer from 0 to 20); A2) 20 to 75% by weight of the diepoxypropyl compound represented by the following formula (II) (In the formula, Z represents an alkylene group having 1 to 9 carbon atoms, an alkylene group having 3 or 4 carbon atoms, or a divalent alicyclic hydrocarbon group. The methylene group in the alkylene group may also be an oxygen atom or -CO. -O-, -O-CO-, -SO 2- , -SO-, or -CO- is interrupted by a divalent radical); (A3) is selected from monomers represented by the following formula (III) or (IV) 5 to 50% by weight of a polymer having a weight average molecular weight of 5,000 to 100,000 composed of at least one of ethylenically unsaturated monomers (Wherein X 2 is (i) an alkyl group having 1 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, or (ii) selected from the group consisting of a ring An alkyl group having 1 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a carbon atom having at least one type of group partially substituted by an oxy group, an oxetanyl group, a hydroxyl group, and a carboxyl group (6 to 10 alicyclic hydrocarbon groups) (In the formula, R 3 represents a hydrogen atom, a methyl group or a halogen atom, and X 3 is the same as X 2 in the above formula (III)). 如申請專利範圍第1項所述之光硬化性接著劑，其中，於前述聚合物(A3)中，前述乙烯性不飽和單體係包含，前述X2或X3為被選自由環氧基、氧雜環丁烷基及羥基所成之群中之1種以上的基部分取代的甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以前述式(III)或(IV)所示的乙烯性不飽和單體。The photocurable adhesive according to item 1 of the scope of application for a patent, wherein in the polymer (A3), the ethylenically unsaturated monosystem includes, and the X 2 or X 3 is selected from an epoxy group 2, oxetanyl and hydroxy groups substituted by one or more types of methyl groups, branched alkyl groups having 2 to 7 carbon atoms, aromatic groups having 6 to 12 carbon atoms or carbon atoms In the case of an alicyclic hydrocarbon group of 6 to 10, an ethylenically unsaturated monomer represented by the aforementioned formula (III) or (IV). 如申請專利範圍第1項所述之光硬化性接著劑，其中，於上述聚合物(A3)中，前述乙烯性不飽和單體係包含(i)前述X2或X3為甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以前述式(III)或(IV)所示的乙烯性不飽和單體20至90重量%，以及(ii)前述X2或X3為被由選自環氧基、氧雜環丁烷基及羥基所成之群中之1種以上的基部分取代的甲基、碳原子數2至7的分支狀烷基、碳原子數6至12的芳香基或碳原子數6至10的脂環式烴基時，以前述式(III)或(IV)所示的乙烯性不飽和單體10至80重量%。The photocurable adhesive according to item 1 of the scope of the patent application, wherein in the polymer (A3), the ethylenically unsaturated monosystem includes (i) the above-mentioned X 2 or X 3 is a methyl group, a carbon When a branched alkyl group having 2 to 7 atoms, an aromatic group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms, the ethylenic property represented by the aforementioned formula (III) or (IV) 20 to 90% by weight of the saturated monomer, and (ii) the aforementioned X 2 or X 3 is substituted with one or more kinds of moieties selected from the group consisting of an epoxy group, an oxetanyl group, and a hydroxyl group When a methyl group, a branched alkyl group having 2 to 7 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an alicyclic hydrocarbon group having 6 to 10 carbon atoms is represented by the aforementioned formula (III) or (IV) 10 to 80% by weight of ethylenically unsaturated monomers. 如申請專利範圍第1項所述之光硬化性接著劑，其中於表示前述二環氧丙基化合物(A2)之式(II)中，Z為碳數3至10之分支狀烷基。The photocurable adhesive according to item 1 of the scope of the patent application, wherein in the formula (II) representing the aforementioned diepoxypropyl compound (A2), Z is a branched alkyl group having 3 to 10 carbon atoms. 如申請專利範圍第1項所述之光硬化性接著劑，更包含0.5至4重量份的水分。The photocurable adhesive as described in item 1 of the patent application range further contains 0.5 to 4 parts by weight of water. 如申請專利範圍第1項所述之光硬化性接著劑，更包含於分子內具有2個羥基之二醇化合物0.5至8重量份。The photocurable adhesive as described in item 1 of the scope of patent application, further comprising 0.5 to 8 parts by weight of a diol compound having two hydroxyl groups in the molecule. 如申請專利範圍第1項所述之光硬化性接著劑，其中，於23℃，浸漬保護膜2天時，保護膜的溶解性為15至70重量%。The photocurable adhesive according to item 1 of the scope of patent application, wherein when the protective film is immersed at 23 ° C. for 2 days, the solubility of the protective film is 15 to 70% by weight. 一種偏光板，係具備：由吸附配向有二色性色素之聚乙烯醇系樹脂膜所構成的偏光器，以及經由如申請專利範圍第1項至第7項中任一項所述之光硬化性接著劑的硬化物而貼合於前述偏光器的至少一面之由透明樹脂膜所構成的保護膜。A polarizing plate is provided with a polarizer composed of a polyvinyl alcohol-based resin film having a dichroic pigment adsorbed and aligned, and photocuring as described in any one of claims 1 to 7 of the scope of patent application. The hardened | cured material of the adhesive is bonded to the protective film which consists of a transparent resin film on at least one surface of the said polarizer. 如申請專利範圍第8項所述之偏光板，其中，前述透明樹脂膜的主成分為選自由纖維素系樹脂、丙烯酸系樹脂、非結晶性聚烯烴系樹脂、聚酯系樹脂以及聚碳酸酯系樹脂所成之群的至少1種樹脂。The polarizing plate according to item 8 of the scope of patent application, wherein the main component of the transparent resin film is selected from the group consisting of cellulose resin, acrylic resin, amorphous polyolefin resin, polyester resin, and polycarbonate. At least one resin in the group of resins. 如申請專利範圍第8項所述之偏光板，其中，前述透明樹脂膜包含紫外線吸收劑。The polarizing plate according to item 8 of the scope of patent application, wherein the transparent resin film contains an ultraviolet absorber. 如申請專利範圍第8項所述之偏光板，其中，藉由180度剝離試驗所測定之前述偏光器與前述保護膜之間的接著強度為0.5N/25mm以上。The polarizing plate according to item 8 of the scope of patent application, wherein the adhesion strength between the polarizer and the protective film measured by a 180-degree peel test is 0.5 N / 25 mm or more. 一種積層光學構件，係包含如申請專利範圍第8項至第11項中任一項所述之偏光板以及1層以上的其他光學層之積層體。A laminated optical member is a laminated body including the polarizing plate according to any one of items 8 to 11 of the scope of patent application and one or more other optical layers. 如申請專利範圍第12項所述之積層光學構件，其中，前述其他之光學層包含相位差板。The laminated optical member according to item 12 of the scope of patent application, wherein the other optical layers include a retardation plate. 一種液晶顯示裝置，係包含液晶胞，以及配置於前述液晶胞的單側或兩側之如申請專利範圍第12或13項所述之積層光學構件。A liquid crystal display device comprises a liquid crystal cell and a laminated optical component according to item 12 or 13 of the scope of application for a patent, which is arranged on one or both sides of the liquid crystal cell.
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