TWI607074B - Photocurable adhesive composition, polarizing adhesive and manufacturing method therefor, optical member and liquid crystal display device - Google Patents

Photocurable adhesive composition, polarizing adhesive and manufacturing method therefor, optical member and liquid crystal display device Download PDF

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TWI607074B
TWI607074B TW102136674A TW102136674A TWI607074B TW I607074 B TWI607074 B TW I607074B TW 102136674 A TW102136674 A TW 102136674A TW 102136674 A TW102136674 A TW 102136674A TW I607074 B TWI607074 B TW I607074B
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film
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weight
acrylate
resin
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TW201422749A (en
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稻田和正
米田智
佐內康之
市原正寬
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東亞合成股份有限公司
住友化學股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333Constructional arrangements; Manufacturing methods
    • G02F1/1335Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528Polarisers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3083Birefringent or phase retarding elements

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

Description

光硬化性接著劑組成物、偏光板及其製造方法、光學構件及液晶顯示裝置 Photocurable adhesive composition, polarizing plate, manufacturing method thereof, optical member, and liquid crystal display device

本發明係關於偏光板中的偏光膜與保護膜之貼合所使用的光硬化性接著劑組成物、使用該接著劑組成物而於偏光膜貼合保護膜之偏光板及該偏光板之製造方法。本發明又有關使用該偏光板的光學構件及液晶顯示裝置。 The present invention relates to a photocurable adhesive composition used for bonding a polarizing film and a protective film in a polarizing plate, a polarizing plate in which a protective film is bonded to a polarizing film using the adhesive composition, and the production of the polarizing plate. method. The present invention is also related to an optical member and a liquid crystal display device using the polarizing plate.

偏光板係有用於作為構成液晶顯示裝置的光學零件之一。偏光板一般係於在偏光膜之兩面積層保護膜的狀態而被組裝在液晶顯示裝置使用。亦已知僅在偏光膜之單面設置保護膜,惟在大部分情況下,係於另一面貼合其他具有光學機能的層兼作保護膜,而非僅作為單純的保護膜。又作為偏光膜之製造方法,將藉由二色性色素染色之單軸延伸聚乙烯醇樹脂薄膜硼酸處理並於水洗後乾燥之方法既已廣為所知。 The polarizing plate is used as one of optical parts constituting a liquid crystal display device. The polarizing plate is generally used in a liquid crystal display device in a state in which the protective film is applied to the two-layer protective film of the polarizing film. It is also known that a protective film is provided only on one side of the polarizing film, but in most cases, the other layer having the optical function is bonded to the other surface as a protective film, not just as a simple protective film. Further, as a method for producing a polarizing film, a method of treating a uniaxially stretched polyvinyl alcohol resin film dyed with a dichroic dye with boric acid and drying it after washing with water is widely known.

一般而言,係在經上述之水洗及乾燥後,立即在偏光膜貼合保護膜。此係因乾燥後之偏光膜其物理強度較弱,一旦予以捲取,便會發生在加工方向裂開等問題之故。因此,乾燥後之偏光膜通常立即塗布水系接著劑後,隔在該接著劑而在兩面同時貼合保護膜。通常 作為保護膜係使用厚30~120μm之三乙酸纖維素薄膜。 In general, the protective film is bonded to the polarizing film immediately after washing and drying as described above. This is because the polarized film after drying has a weak physical strength, and once it is taken up, it may cause problems such as cracking in the processing direction. Therefore, the polarizing film after drying is usually applied with a water-based adhesive immediately, and then the protective film is bonded to both surfaces simultaneously with the adhesive. usually As the protective film, a cellulose triacetate film having a thickness of 30 to 120 μm was used.

偏光膜與保護膜,尤為包含三乙酸纖維素薄膜之保護膜的接著係大多使用聚乙烯醇系接著劑,然取而代之亦有嘗試使用胺基甲酸酯系接著劑。例如,日本特開平7-120617號公報(專利文獻1)中記載以胺基甲酸酯預聚合物作為接著劑來接著含水率高之偏光膜與乙酸纖維素系保護膜,如三乙酸纖維素薄膜。 In the polarizing film and the protective film, in particular, a polyvinyl alcohol-based adhesive is often used as the adhesive film of the protective film containing the cellulose triacetate film, and an amine-based adhesive is also tried. Japanese Patent Publication No. 7-120617 (Patent Document 1) discloses a polarizing film having a high water content and a cellulose acetate-based protective film, such as cellulose triacetate, using a urethane prepolymer as an adhesive. film.

另一方面,由於三乙酸纖維素其透濕度高,貼合有該樹脂薄膜作為保護膜的偏光板在濕熱下,例如溫度70℃、相對濕度90%之類的條件下有引起劣化等問題。所以,亦有人提案將透濕度較三乙酸纖維素薄膜低的樹脂薄膜作為保護膜來解決所述問題之方法,例如已知有將非晶性聚烯烴系樹脂作為保護膜。具體而言,日本特開平6-51117號公報(專利文獻2)中記載在偏光膜之至少其中一面積層熱塑性飽和降莰烯系樹脂片作為保護膜。 On the other hand, the cellulose triacetate has a high moisture permeability, and the polarizing plate to which the resin film is bonded as a protective film causes problems such as deterioration under conditions of moist heat such as a temperature of 70 ° C and a relative humidity of 90%. Therefore, a method of solving the above problem by using a resin film having a lower moisture permeability than a cellulose triacetate film as a protective film has been proposed. For example, an amorphous polyolefin resin is known as a protective film. In the above-mentioned Japanese Patent Publication No. Hei 6-51117 (Patent Document 2), a thermoplastic saturated norbornene-based resin sheet having at least one area of a polarizing film is used as a protective film.

在習知裝置貼合此種低透濕度保護膜時,於所謂的濕式積層,即使用以水為主溶媒的接著劑,例如聚乙烯醇水溶液在聚乙烯醇系偏光膜貼合保護膜後將溶媒乾燥時,會有未能獲得充分的接著強度或外觀不良等問題。此係由於透濕度低之薄膜一般而言較三乙酸纖維素薄膜更呈疏水性、或因透濕度低而無法將作為溶媒的水充分乾燥等原因。 When such a low moisture permeability protective film is bonded to a conventional device, even a water-based solvent, such as an aqueous solution of polyvinyl alcohol, is applied to the protective film of the polyvinyl alcohol-based polarizing film after the protective film is applied to the so-called wet laminate. When the solvent is dried, problems such as insufficient adhesion strength or poor appearance may not be obtained. This is because the film having a low moisture permeability is generally more hydrophobic than the cellulose triacetate film or has a low moisture permeability, and the water as a solvent cannot be sufficiently dried.

所以,日本特開2000-321432號公報(專利文獻3)中提出將聚乙烯醇系偏光膜與包含熱塑性飽和降莰 烯系樹脂之保護膜,藉由聚胺基甲酸酯系接著劑接著。然而,聚胺基甲酸酯系接著劑有硬化需耗費長時間的問題,且接著力也未必充分。 Therefore, Japanese Laid-Open Patent Publication No. 2000-321432 (Patent Document 3) proposes a polyvinyl alcohol-based polarizing film and a thermoplastic saturated hail. The protective film of the olefinic resin is followed by a polyurethane-based adhesive. However, the polyurethane adhesive has a problem that it takes a long time to harden, and the adhesive force is not necessarily sufficient.

在另一方面,亦已知有在偏光膜之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4)提出,在包含聚乙烯醇系樹脂薄膜之偏光膜之一面貼合包含非晶性聚烯烴系樹脂之保護膜,而在另一面貼合包含與該非晶性聚烯烴系樹脂不同的樹脂,例如三乙酸纖維素之保護膜,日本特開2005-208456號公報(專利文獻5)則提出,在包含聚乙烯醇系樹脂之偏光薄膜之一面,隔著含有特定胺基甲酸酯樹脂的水系第一接著劑積層環烯烴系樹脂薄膜,而在另一面隔著與第一接著劑相異的水系第二接著劑,例如聚乙烯醇系樹脂的水溶液積層乙酸纖維素系樹脂薄膜。 On the other hand, it is also known to apply a different type of protective film to both surfaces of a polarizing film. For example, Japanese Laid-Open Patent Publication No. 2002-174729 (Patent Document 4) proposes a polarizing film comprising a polyvinyl alcohol resin film. A protective film containing an amorphous polyolefin-based resin is bonded to one surface, and a resin different from the amorphous polyolefin-based resin, for example, a protective film of cellulose triacetate, is bonded to the other surface. Japanese Patent Laid-Open No. 2005-208456 In the case of one of the polarizing films containing a polyvinyl alcohol-based resin, it is proposed that a water-based first adhesive layer-containing cycloolefin-based resin film containing a specific urethane resin is interposed on the other side. A water-based second adhesive different from the first adhesive, for example, an aqueous solution of a polyvinyl alcohol-based resin, is laminated with a cellulose acetate-based resin film.

在上述專利文獻4中稱之為「非晶性聚烯烴系樹脂」、又於上述專利文獻5中稱之為「環烯烴系樹脂」者為具有包含如降莰烯或其衍生物、二甲橋八氫萘(dimethanooctahydronaphthalene)之類的多環式環烯烴之單體單元,且在如開環聚合物般殘留有雙鍵時,較佳為對其施以氫化的熱塑性樹脂。 In the above-mentioned Patent Document 4, it is referred to as "amorphous polyolefin-based resin", and in the above-mentioned Patent Document 5, it is referred to as "cycloolefin-based resin", and it is intended to contain, for example, norbornene or a derivative thereof. When a monomer unit of a polycyclic cyclic olefin such as dimethanoocta hydronaphthalene is used, and a double bond remains as in the case of a ring-opening polymer, a hydrogenated thermoplastic resin is preferably used.

再者,日本特開2004-245925號公報(專利文獻6)中揭露一種以不含芳香環之環氧樹脂為主成分的接著劑,並提出一種藉由對該接著劑照射活性能量線使陽離子聚合而接著偏光膜與保護膜之方法。此處所揭示之環氧系接著劑雖對於在偏光膜貼合以非晶性聚烯烴系樹 脂及纖維素系樹脂為首的各種透明樹脂薄膜特別有效,然而特別是在以丙烯酸樹脂為保護膜時,已知其接著力未必充分。 Further, Japanese Laid-Open Patent Publication No. 2004-245925 (Patent Document 6) discloses an adhesive containing an epoxy resin containing no aromatic ring as a main component, and proposes a cation by irradiating the adhesive with an active energy ray. A method of polymerizing followed by a polarizing film and a protective film. The epoxy-based adhesive disclosed herein is suitable for bonding to a polarizing film to form an amorphous polyolefin tree. Various types of transparent resin films, such as fats and cellulose-based resins, are particularly effective. However, in the case where an acrylic resin is used as a protective film, it is known that the adhesion is not necessarily sufficient.

所以,本發明人等進行了在以選自丙烯酸樹脂、聚酯樹脂、聚碳酸酯樹脂及非晶性聚烯烴系樹脂之透濕度低的樹脂薄膜為偏光膜的保護膜時,於短時間的步驟展現良好接著力之低黏度的光硬化性接著劑的開發。其結果發現,含有具芳香環之環氧丙基醚型環氧樹脂與環氧丙烷化合物的組成物係賦予良好的接著力,特別是在含有具脂環族骨架的(甲基)丙烯酸酯系單體5~25重量%時,可展現高接著力與耐久性(專利文獻7)。然而,此接著劑,其生產步驟本身雖係以照光之短時間的步驟完成,但有在薄膜捲取後,若未經過一段時間後就不能展現充分的接著力之問題。因此,便會有生產步驟中之照光後的薄膜的處理困難之問題。 Therefore, the inventors of the present invention performed a protective film having a low moisture permeability of a resin film selected from the group consisting of an acrylic resin, a polyester resin, a polycarbonate resin, and an amorphous polyolefin resin as a polarizing film in a short period of time. The procedure demonstrates the development of a low adhesion, photocurable adhesive with good adhesion. As a result, it has been found that a composition containing a epoxidized propyl ether epoxy resin having an aromatic ring and a propylene oxide compound imparts a good adhesion, particularly in a (meth) acrylate system having an alicyclic skeleton. When the monomer is 5 to 25% by weight, high adhesion and durability can be exhibited (Patent Document 7). However, in this adhesive agent, the production step itself is completed in a short-time step of illuminating, but there is a problem that a sufficient adhesive force cannot be exhibited after a film is taken up without a lapse of a period of time. Therefore, there is a problem that handling of the film after illumination in the production step is difficult.

本發明人等為解決前述課題而進行各種研究的結果,發現了包含脂環族環氧化合物、特定聚(甲基)丙烯酸酯、光陽離子聚合起始劑及環氧丙醇(oxetane alcohol)的光硬化性接著劑組成物係為有效(專利文獻8)。 As a result of various studies to solve the above problems, the present inventors have found that an alicyclic epoxy compound, a specific poly(meth)acrylate, a photocationic polymerization initiator, and an oxetane alcohol are contained. The photocurable adhesive composition is effective (Patent Document 8).

該接著劑組成物不僅是接著力與耐久性優良,係生產性亦優良的偏光板用光硬化性接著劑。 This adhesive composition is not only a photocurable adhesive for polarizing plates, but also excellent in adhesion and durability, and excellent in productivity.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平7-120617號公報 [Patent Document 1] Japanese Patent Laid-Open No. Hei 7-120617

[專利文獻2]日本特開平6-51117號公報 [Patent Document 2] Japanese Patent Laid-Open No. Hei 6-51117

[專利文獻3]日本特開2000-321432號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-321432

[專利文獻4]日本特開2002-174729號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2002-174729

[專利文獻5]日本特開2005-208456號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2005-208456

[專利文獻6]日本特開2004-245925號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-245925

[專利文獻7]日本特開2010-209126號公報 [Patent Document 7] Japanese Patent Laid-Open Publication No. 2010-209126

[專利文獻8]日本特開2012-140610號公報 [Patent Document 8] Japanese Laid-Open Patent Publication No. 2012-140610

然而,已確認前述專利文獻8之接著劑,在高溫高濕環境下(如60℃ 90%)實施耐濕熱試驗後,回至一般環境(如23℃ 50%)隨後之剝離接著力極低。 However, it has been confirmed that the adhesive of the aforementioned Patent Document 8 is subjected to a moist heat resistance test in a high-temperature and high-humidity environment (e.g., 60% at 60 ° C), and returned to a general environment (e.g., 23 ° C, 50%), and then the peeling force is extremely low.

對此接著力之下降,若於一般環境放置15小時,剝離接著力將回復至使保護薄膜發生材料破壞之程度。又,即便是在耐濕熱試驗結束隨後,由於施加在將偏光板黏貼於玻璃之製品形態的力(剪切方向或垂直方向的力),係不會發生保護薄膜的剝離。然而,若假設在偏光板輸送中暴露於高溫高濕環境後,隨即進入加工步驟之最差的情況,係企望亦使耐濕熱試驗結束隨後之剝離強度提升。 In response to this decrease in force, if placed in a general environment for 15 hours, the peeling adhesion force will return to the extent that the protective film is damaged by the material. Further, even after the end of the moist heat resistance test, the force applied to the form of the product in which the polarizing plate is adhered to the glass (the force in the shearing direction or the vertical direction) does not cause peeling of the protective film. However, if it is assumed that after exposure to a high-temperature and high-humidity environment in the transport of the polarizing plate, the worst case of the processing step is immediately entered, and it is expected that the peeling strength will be improved after the end of the moist heat resistance test.

本發明所欲解決之課題在於提供一種光硬化性接著劑,其係即使在以選自聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之透濕度低的樹脂薄膜為保護膜時,於照光後可迅速展現接著力,經過一 定時間後之最終接著力亦良好,且耐久試驗後也不會引起外觀不良等問題,耐濕熱試驗結束隨後之接著力亦良好,且硬化前的黏度低。又在於提供一種使用該接著劑而在偏光膜貼合有保護膜的偏光板。本發明之另一目的在於提供一種光學構件,其係使用該偏光板,而能夠形成可靠度優良的液晶顯示裝置,並在於進一步將其應用於液晶顯示裝置。 An object of the present invention is to provide a photocurable adhesive which is a resin film having a low moisture permeability selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin. When the film is protected, the adhesion force can be quickly expressed after the light is irradiated. After the time limit, the final adhesion was also good, and the endurance test did not cause problems such as poor appearance, and the adhesion after the end of the damp heat test was good, and the viscosity before hardening was low. Further, a polarizing plate in which a protective film is bonded to a polarizing film using the adhesive is provided. Another object of the present invention is to provide an optical member which can form a liquid crystal display device having excellent reliability by using the polarizing plate, and further applies the same to a liquid crystal display device.

即,本發明之光硬化性接著劑組成物係用於在偏光膜接著保護膜,而該偏光膜係包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系樹脂薄膜,該保護膜係包括選自包含聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之群組中的透明樹脂薄膜,該接著劑組成物之特徵為含有:(A)分子內具有至少2個下式(1)所示之脂環族環氧基的環氧化合物; That is, the photocurable adhesive composition of the present invention is used for a polarizing film followed by a protective film, and the polarizing film comprises a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed and has a dichroic dye. The film system includes a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin, and the adhesive composition is characterized by: (A) having intramolecular At least two epoxy compounds of the alicyclic epoxy group represented by the following formula (1);

(B)具碳數2~15個之多元醇的聚(甲基)丙烯酸酯;(C)光陽離子聚合起始劑;(D)下式(2)所示之環氧丙烷化合物;及 (B) a poly(meth)acrylate having a carbon number of 2 to 15 polyols; (C) a photocationic polymerization initiator; (D) a propylene oxide compound represented by the following formula (2);

(E)以(甲基)丙烯酸烷基酯為必須組成單體單元的聚合物,且在組成物中前述(A)~(E)成分之含有比例係 (E) a polymer having a (meth)acrylic acid alkyl ester as an essential constituent monomer unit, and the content ratio of the above components (A) to (E) in the composition is

(A)成分:10~65重量% (A) Composition: 10 to 65 wt%

(B)成分:10~55重量% (B) Composition: 10 to 55% by weight

(C)成分:0.5~10重量% (C) Component: 0.5 to 10% by weight

(D)成分:1~25重量% (D) Composition: 1 to 25% by weight

(E)成分:0.1~25重量%。 (E) component: 0.1 to 25% by weight.

本發明之組成物中,作為(A)成分,較佳為下式(4)所示之環氧化合物。 In the composition of the present invention, the component (A) is preferably an epoxy compound represented by the following formula (4).

作為(B)成分,更佳為具碳數5~10個之二醇的二(甲基)丙烯酸酯。又作為(甲基)丙烯酸酯,更佳為丙烯酸酯。 The component (B) is more preferably a di(meth)acrylate having a diol having 5 to 10 carbon atoms. Further, as the (meth) acrylate, it is more preferably an acrylate.

(A)成分及(B)成分之較佳含有比例係於組成物中分別為10~50重量%及20~45重量%。 The preferred content ratio of the component (A) and the component (B) is 10 to 50% by weight and 20 to 45% by weight, respectively, based on the composition.

作為(E)成分,較佳為含有以含有含碳數1~10之烷基的(甲基)丙烯酸烷基酯作為組成單體單元,且重量平均分子量為1,000~500,000的聚合物。 The component (E) preferably contains a polymer having an alkyl (meth)acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit and having a weight average molecular weight of 1,000 to 500,000.

作為該聚合物,較佳為含有60重量%以上之甲基丙 烯酸甲酯作為組成單體單元,且重量平均分子量為1,000~200,000的聚合物[以下亦稱為「(E1)成分」]、含有60重量%以上之含碳數1~10之烷基的丙烯酸烷基酯作為組成單體單元,且重量平均分子量為1,000~200,000的聚合物[以下亦稱為「(E2)成分」]。 The polymer preferably contains 60% by weight or more of methyl propyl group. Methyl enoate as a constituent monomer unit, and a polymer having a weight average molecular weight of 1,000 to 200,000 (hereinafter also referred to as "(E1) component"], and containing 60% by weight or more of an alkyl group having 1 to 10 carbon atoms The alkyl acrylate is a polymer constituting a monomer unit and having a weight average molecular weight of 1,000 to 200,000 [hereinafter also referred to as "(E2) component").

作為(E2)成分,更佳為以高溫聚合所得之聚合物,而含有60重量%以上之含碳數1~10之烷基的丙烯酸烷基酯作為組成單體單元,且重量平均分子量為1,000~200,00的聚合物。 The (E2) component is more preferably a polymer obtained by polymerization at a high temperature, and an alkyl acrylate containing 60% by weight or more of an alkyl group having 1 to 10 carbon atoms is used as a constituent monomer unit, and the weight average molecular weight is 1,000. ~200,00 polymer.

更者,本發明之組成物中,較佳為在組成物中含有1~30重量%之下式(3)所示之環氧丙烷化合物作為(F)成分。 Furthermore, in the composition of the present invention, it is preferred that the composition contains 1 to 30% by weight of the propylene oxide compound represented by the formula (3) as the component (F).

此等光硬化性接著劑組成物所含之(B)成分等的自由基聚合性成分,雖可藉由在(C)成分被光分解時所產生的自由基而使其硬化,但為了以較少的照射量來獲得充分的反應率,較佳為以10重量%以下之比例含有(G)成分的光自由基聚合起始劑。 The radically polymerizable component such as the component (B) contained in the photocurable adhesive composition can be cured by the radical generated when the component (C) is photodecomposed, but A sufficient amount of irradiation is obtained to obtain a sufficient reaction rate, and a photoradical polymerization initiator containing the component (G) in a proportion of 10% by weight or less is preferable.

作為(G)成分,醯基膦氧化物化合物係以接著力優良而較佳。 As the component (G), the mercaptophosphine oxide compound is preferred because it has excellent adhesion.

再者,為獲得平滑性優良的塗布面,此等光硬化性接著劑組成物較佳在組成物中含有0.01~0.5重量%之屬(H)成分的調平劑。 Further, in order to obtain a coated surface having excellent smoothness, the photocurable adhesive composition preferably contains 0.01 to 0.5% by weight of a leveling agent of the component (H) in the composition.

又本發明之偏光板係隔著接著劑而於偏光膜貼合保護膜而成之偏光板,該接著劑係包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系樹脂薄膜,該保護膜係包括選自聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂的透明樹脂薄膜,而該接著劑由上述任一種光硬化性接著劑組成物所形成的偏光板。 Further, the polarizing plate of the present invention is a polarizing plate obtained by laminating a protective film on a polarizing film via an adhesive, and the adhesive comprises a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed and has a dichroic dye. The protective film includes a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin, and the adhesive is polarized by any of the above photocurable adhesive compositions. board.

該偏光板可藉由包含以下步驟之方法來製造:接著劑塗布步驟,在偏光膜與保護膜之貼合面中的至少一面塗布前述任一種光硬化性接著劑組成物;貼合步驟,隔著所得接著劑層貼合偏光膜與保護膜;及硬化步驟,在隔著該接著劑層貼合偏光膜與保護膜的狀態下使光硬化性接著劑組成物硬化。具體而言,可採用在偏光膜塗敷未硬化之上述光硬化性接著劑組成物後,在該接著劑組成物塗敷面貼合保護膜,接著使該接著劑組成物硬化而形成接著劑層的方法;在保護膜塗敷未硬化之上述光硬化性接著劑組成物後,在該接著劑組成物塗敷面貼合偏光膜,接著使該接著劑組成物硬化而形成接著劑層的方法;在偏光膜與保護膜之間流延未硬化之上述光硬化性接著劑組成物,並用輥等夾持偏光膜與保護膜之貼合物,將接著劑組成物一面均勻地延展而壓接後,使該接著劑組成物硬化而形成接著劑層的方法等。 The polarizing plate can be manufactured by a method comprising the steps of: applying an adhesive coating step to coating at least one of the bonding surfaces of the polarizing film and the protective film, and coating the photocurable adhesive composition; The obtained adhesive layer is bonded to the polarizing film and the protective film, and the curing step is to cure the photocurable adhesive composition in a state where the polarizing film and the protective film are bonded to each other via the adhesive layer. Specifically, after applying the photocurable adhesive composition which is not cured to the polarizing film, the protective film may be bonded to the adhesive composition application surface, and then the adhesive composition may be cured to form an adhesive. a method of laminating a photocurable adhesive composition on a surface of the adhesive composition, applying a polarizing film to the adhesive composition coating surface, and then curing the adhesive composition to form an adhesive layer. a method of casting an unhardened photocurable adhesive composition between a polarizing film and a protective film, and holding a laminate of a polarizing film and a protective film with a roller or the like, and uniformly stretching the adhesive composition on one side After the connection, the adhesive composition is cured to form an adhesive layer or the like.

更且,係對本發明之液晶顯示裝置提供積層有上述偏光板與其他顯示光學機能之光學層的光學構件。此時之其他的光學層較佳包含相位差板。本發明之液晶顯示裝置係該光學構件配置於液晶胞之單側或兩側而 成。 Further, an optical member in which an optical layer of the above-described polarizing plate and other display optical functions is laminated is provided to the liquid crystal display device of the present invention. The other optical layers at this time preferably include a phase difference plate. In the liquid crystal display device of the present invention, the optical member is disposed on one side or both sides of the liquid crystal cell to make.

本發明之光硬化性接著劑組成物,係即便在以選自聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之透濕度低的樹脂薄膜為保護膜時,於照光後亦可迅速展現接著力,經過一定時間後之最終接著力亦良好,且耐久試驗後也不會引起外觀不良等問題,甚而耐濕熱試驗結束隨後之接著力優良。該接著劑組成物在保護膜係以丙烯酸樹脂構成時係特別有用。又,本發明之接著劑組成物由於其黏度極低,容易塗布得較薄而無缺陷地貼合。隔著該接著劑組成物而貼合偏光膜與保護膜所得之偏光板,不僅是該接著劑組成物係於所謂照光之短時間的步驟硬化,由照光隨後亦可獲得一定強度之接著力,而得以生產性良好地製造。更者,將該偏光板與其他的光學層組合而成的光學構件係可形成可靠度優良的液晶顯示裝置。 In the photocurable adhesive composition of the present invention, when a resin film having a low moisture permeability selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin is used as a protective film, After that, the adhesion force can be quickly expressed. After a certain period of time, the final adhesion force is also good, and the endurance test does not cause problems such as poor appearance, and even the endurance of the damp heat resistance test is excellent. This adhesive composition is particularly useful when the protective film is composed of an acrylic resin. Further, since the adhesive composition of the present invention has an extremely low viscosity, it is easy to apply it thinly and adhere without defects. The polarizing plate obtained by laminating the polarizing film and the protective film via the adhesive composition not only cures the adhesive composition in a short-time step, but also obtains a bonding strength of a certain strength by illumination. It can be manufactured with good productivity. Further, an optical member in which the polarizing plate is combined with another optical layer can form a liquid crystal display device having excellent reliability.

[實施發明之形態] [Formation of the Invention]

以下,對本發明詳細加以說明。本發明係於偏光膜接著保護膜之際使用特定組成之光硬化性接著劑組成物,該偏光膜係包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系樹脂薄膜,該保護膜係包括透明樹脂薄膜。藉由如此地隔著光硬化性接著劑組成物貼合偏 光膜與保護膜,而可得到偏光板。該偏光板可與具其他光學機能的光學層積層而作成光學構件。又該光學構件可配置於液晶胞之至少其中一側,而作成液晶顯示裝置。以下,依光硬化性接著劑組成物、偏光板、偏光板之製造方法、光學構件、液晶顯示裝置之順序進行說明。 Hereinafter, the present invention will be described in detail. In the present invention, when a polarizing film and a protective film are used, a photocurable adhesive composition having a specific composition containing a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed and has a dichroic dye is used. The film system includes a transparent resin film. By adhering to the photocurable adhesive composition in this way A light film and a protective film are used to obtain a polarizing plate. The polarizing plate can be laminated with an optical layer having other optical functions to form an optical member. Further, the optical member may be disposed on at least one side of the liquid crystal cell to form a liquid crystal display device. Hereinafter, the order of the photocurable adhesive composition, the polarizing plate, the method of producing the polarizing plate, the optical member, and the liquid crystal display device will be described.

[光硬化性接著劑組成物] [Photocurable adhesive composition]

本發明中,為貼合偏光膜與保護膜,係使用特定組成之光硬化性接著劑組成物。以下,有時僅將該光硬化性接著劑組成物稱為「光硬化性接著劑」或「組成物」。本發明之光硬化性接著劑係必須含有以下(A)、(B)、(C)、(D)及(E)此5成分:(A)分子內具有至少2個後式(1)所示之脂環族環氧基的環氧化合物;(B)具碳數2~15個之多元醇的聚(甲基)丙烯酸酯;(C)光陽離子聚合起始劑;(D)後式(2)所示之環氧丙烷化合物;(E)以(甲基)丙烯酸烷基酯為必須組成單體單元的聚合物。 In the present invention, in order to bond the polarizing film and the protective film, a photocurable adhesive composition having a specific composition is used. Hereinafter, only the photocurable adhesive composition may be referred to as a "photocurable adhesive" or a "composition". The photocurable adhesive of the present invention must contain the following five components (A), (B), (C), (D), and (E): (A) having at least two formulas (1) in the molecule. An epoxy compound of an alicyclic epoxy group; (B) a poly(meth)acrylate having a carbon number of 2 to 15; (C) a photocationic polymerization initiator; (D) (2) a propylene oxide compound shown; (E) a polymer having an alkyl (meth) acrylate as an essential constituent monomer unit.

本說明書中,將上述(A)之環氧化合物亦稱為「(A)成分」或「環氧化合物(A)」;將(B)之聚(甲基)丙烯酸酯亦稱為「(B)成分」或「聚(甲基)丙烯酸酯(B)」;將(C)之光陽離子聚合起始劑亦稱為「(C)成分」或「光陽離子聚合起始劑(C)」;將上述(D)之環氧丙烷化合物亦稱為「(D)成分」或「環氧丙烷化合物(D)」;將上述(E)之以(甲基)丙烯酸烷基酯為必須組成單體單元的聚合 物亦稱為「(E)成分」。 In the present specification, the epoxy compound of the above (A) is also referred to as "(A) component" or "epoxy compound (A)"; and the poly(meth)acrylate of (B) is also referred to as "(B) "Component" or "poly(meth)acrylate (B)"; the photocationic polymerization initiator of (C) is also referred to as "(C) component" or "photocationic polymerization initiator (C)"; The propylene oxide compound of the above (D) is also referred to as "(D) component" or "propylene oxide compound (D)"; the (E) alkyl (meth) acrylate is an essential constituent monomer Unit aggregation Also known as "(E) ingredient."

以組成物全體為基準,係使(A)~(E)成分之組成物中的含有比例成為(A)成分為10~65重量%、(B)成分為10~55重量%、(C)成分為0.5~10重量%、(D)成分為1~25重量%及(E)成分為0.1~25重量%。 The content of the components in the components (A) to (E) is 10 to 65 wt% of the component (A) and 10 to 55 wt% of the component (B), based on the entire composition. (C) The component is 0.5 to 10% by weight, the component (D) is 1 to 25% by weight, and the component (E) is 0.1 to 25% by weight.

該光硬化性接著劑可任意含有後式(3)所示之環氧丙烷化合物作為(F)成分,較佳成為1~30重量%之含有比例。可含有光自由基聚合起始劑作為(G)成分、可含有調平劑作為(H)成分。 The photocurable adhesive may optionally contain a propylene oxide compound represented by the following formula (3) as the component (F), and preferably has a content ratio of 1 to 30% by weight. A photoradical polymerization initiator may be contained as the component (G), and a leveling agent may be contained as the component (H).

本說明書中,將上述(F)之環氧丙烷化合物亦稱為「(F)成分」或「環氧丙烷化合物(F)」;將(G)之光自由基聚合起始劑亦稱為「(G)成分」或「光自由基聚合起始劑(G)」;將(H)之調平劑亦稱為「(H)成分」或「調平劑(H)」。 In the present specification, the propylene oxide compound of the above (F) is also referred to as "(F) component" or "propylene oxide compound (F)"; and the photoradical polymerization initiator of (G) is also referred to as " (G) component or "photoradical polymerization initiator (G)"; the leveling agent of (H) is also referred to as "(H) component" or "leveling agent (H)".

<環氧化合物(A)> <epoxy compound (A)>

於本發明之光硬化性接著劑中,成為(A)成分的環氧化合物係分子內具有至少2個下式(1)所示之脂環族環氧基的環氧化合物,可採用一般所周知的各種硬化性環氧化合物。再者,式(1)中,波線部分係表示與其他結構的鍵結位置。 In the photocurable adhesive of the present invention, the epoxy compound having the (A) component has at least two epoxy compounds having an alicyclic epoxy group represented by the following formula (1) in the molecule, and a general compound can be used. Various hardening epoxy compounds are known. Further, in the formula (1), the wave line portion indicates the bonding position with other structures.

作為(A)成分之具體例,可列舉3,4-環氧環己 基甲基-3,4-環氧環己烷羧酸酯、雙(3,4-環氧環己基甲基)己二酸酯、3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯之己內酯改質物、多元羧酸與3,4-環氧環己基甲醇之酯化物或己內酯改質物、末端具有上式(1)所示之脂環族環氧基的矽氧系化合物等。 Specific examples of the component (A) include 3,4-epoxycyclohexane. Methyl-3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxycyclohexylmethyl-3,4- a caprolactone modification of an epoxycyclohexane carboxylate, an esterified product of a polycarboxylic acid and 3,4-epoxycyclohexylmethanol or a caprolactone modification, and an alicyclic ring represented by the above formula (1) An epoxy group-based compound such as an epoxy group.

又,(A)成分之式(1)所示之脂環族環氧基的數目,於低黏度、硬化性、接著力及耐久性優良觀點,係較佳為2~10個,更佳為2~6個,再佳為2個。 Further, the number of the alicyclic epoxy groups represented by the formula (1) of the component (A) is preferably from 2 to 10, more preferably from the viewpoint of excellent low viscosity, hardenability, adhesion and durability. 2~6, then 2 is better.

作為(A)成分,下式(4)所示之環氧化合物於低黏度、硬化性、接著力及耐久性優良而較佳。 As the component (A), the epoxy compound represented by the following formula (4) is preferable because it is excellent in low viscosity, hardenability, adhesion and durability.

(A)成分之環氧化合物可單獨使用1種,亦可混合使用2種以上。 The epoxy compound of the component (A) may be used singly or in combination of two or more.

(A)成分之環氧化合物之含有比例,係以組成物全體為基準而設為10~65重量%之範圍。藉由設為此範圍,而可使照光隨後之接著力、最終接著力及耐久性成為良好。又藉由將(A)成分之含有比例設為10~50重量%之範圍,而可使接著力更為良好。 The content ratio of the epoxy compound of the component (A) is in the range of 10 to 65% by weight based on the entire composition. By setting it as this range, the subsequent adhesive force, final adhesive force, and durability of the illuminating light can be made good. Further, by setting the content ratio of the component (A) to a range of 10 to 50% by weight, the adhesion can be further improved.

<聚(甲基)丙烯酸酯(B)> <Poly(meth)acrylate (B)>

於本發明之光硬化性接著劑中,成為(B)成分的聚(甲基)丙烯酸酯係具碳數2~15個之多元醇的聚(甲基)丙烯酸酯。 In the photocurable adhesive of the present invention, the poly(meth)acrylate which is the component (B) is a poly(meth)acrylate having a polyhydric alcohol having 2 to 15 carbon atoms.

分子內之(甲基)丙烯醯基數為1之(甲基)丙烯酸酯係容易變得冷熱循環耐性等之耐久性不足。 The (meth) acrylate having a (meth) acrylonitrile group number of 1 in the molecule is less likely to have insufficient durability such as cold cycle resistance.

藉由使用(B)成分,而可一面降低組成物之黏度,且成為對偏光膜之接著性及耐久性優異之物。於此,作為(B)成分,於低黏度、接著力、耐久性觀點,更佳為具碳數5~10個之二醇的二(甲基)丙烯酸酯。又作為(甲基)丙烯酸酯,丙烯酸酯係於硬化性觀點為較佳。 By using the component (B), the viscosity of the composition can be lowered, and it is excellent in adhesion to the polarizing film and durability. Here, as the component (B), a di(meth)acrylate having a diol having 5 to 10 carbon atoms is more preferable from the viewpoint of low viscosity, adhesion, and durability. Further, as the (meth) acrylate, the acrylate is preferred from the viewpoint of curability.

作為(B)成分之具體例,可列舉新戊二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、3-甲基-1,5-戊二醇二(甲基)丙烯酸酯、環己烷二羥甲基二(甲基)丙烯酸酯、2-丁基-2-乙基-1,3-丙二醇二(甲基)丙烯酸酯、1,9-壬二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、伸丁二醇二(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、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、三環癸烷二羥甲基二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、二-三羥甲基丙烷四(甲基)丙烯酸酯、新戊四醇三或四(甲基)丙烯酸酯、二新戊四醇五或六(甲基)丙烯酸酯及氫化雙酚A之二(甲基)丙烯酸酯等。 Specific examples of the component (B) include neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and 3-methyl-1,5-pentanediol. Di(meth)acrylate, cyclohexanedimethylol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9- Decanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, diethylene glycol di(a) Acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tricyclodecane dimethylol di(methyl) Acrylate, trimethylolpropane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tri- or tetra(meth)acrylate, dipentaerythritol Five or six (meth) acrylates and hydrogenated bisphenol A bis (meth) acrylates.

(B)成分亦可具有酯骨架或異三聚氰酸酯骨架。作為具有酯骨架的化合物之具體例,可舉出新戊二醇與羥基三甲基乙酸與(甲基)丙烯酸之酯化反應生成物等;作為具有異三聚氰酸酯骨架的化合物之例,可舉出異三聚氰酸環氧烷加成物之二或三(甲基)丙烯酸酯等。 The component (B) may also have an ester skeleton or an isomeric cyanate skeleton. Specific examples of the compound having an ester skeleton include an esterification reaction product of neopentyl glycol with hydroxytrimethylacetic acid and (meth)acrylic acid, and the like, and examples of the compound having an isomeric cyanate skeleton. Examples of the di- or tris(meth)acrylate of the isomeric cyanuric acid alkylene oxide adduct can be mentioned.

此等當中,1,6-己二醇二(甲基)丙烯酸酯及新戊二醇與羥基三甲基乙酸與(甲基)丙烯酸之酯化反應生成物,於低黏度化、接著性及耐久性優良、低臭味之觀點為特佳。 Among these, the esterification reaction product of 1,6-hexanediol di(meth)acrylate and neopentyl glycol with hydroxytrimethylacetic acid and (meth)acrylic acid has low viscosity and adhesion. The viewpoint of excellent durability and low odor is particularly preferable.

(B)成分之含有比例,係以組成物全體為基準,而設為10~55重量%之範圍。藉由設為此比例,可使照光隨後之接著力、最終接著力及耐久性成為良好。又藉由將(B)成分之含有比例設為20~45重量%之範圍,可使接著力更為良好。 The content ratio of the component (B) is in the range of 10 to 55% by weight based on the entire composition. By setting this ratio, the subsequent adhesion force, final adhesion force, and durability of the illumination can be made good. Further, by setting the content ratio of the component (B) to a range of 20 to 45% by weight, the adhesion can be further improved.

<光陽離子聚合起始劑(C)> <Photocationic polymerization initiator (C)>

本發明之光硬化性接著劑係含有以上說明之環氧化合物(A)、環氧丙烷化合物(D)及視需求之後述環氧丙烷化合物作為硬化成分,而由於該等之任一種均為藉由陽離子聚合而硬化者,因此摻混光陽離子聚合起始劑作為(C)成分。該光陽離子聚合起始劑係藉由照射可見光線、紫外線、X光、電子束等活性能量線而產生陽離子種或路易士酸,而起始環氧基或氧雜環丁烷基之聚合反應。 The photocurable adhesive of the present invention contains the epoxy compound (A), the propylene oxide compound (D), and the propylene oxide compound described later as a curing component, and any of these may be used. It is hardened by cationic polymerization, and thus a photocationic polymerization initiator is blended as the component (C). The photocationic polymerization initiator generates a cationic species or a Lewis acid by irradiating an active energy ray such as visible light, ultraviolet light, X-ray or electron beam, and starts the polymerization of an epoxy group or an oxetane group. .

藉由摻混光陽離子聚合起始劑作為(C)成分,於常溫可硬化,需考量偏光膜之耐熱性或膨脹或收縮所生之應力的必要性減少,可良好地接著保護膜。又,由於光陽離子聚合起始劑係以活性能量線照射而可觸媒性地作用,縱使摻混於環氧化合物(A)及環氧丙烷化合物(D),亦為保存穩定性或作業性優良。作為藉由照射活性能量線而產生陽離子種或路易士酸之化合物,可列舉例如芳香族重氮鹽、芳香族錪鹽或芳香族鋶鹽之類的鎓鹽 、鐵-芳烴錯合物等。 By blending the photocationic polymerization initiator as the component (C), it is hardenable at room temperature, and the necessity of considering the heat resistance of the polarizing film or the stress generated by the expansion or contraction is reduced, and the film can be favorably adhered. Further, since the photocationic polymerization initiator is photocatalytically irradiated by the active energy ray, it is also stable in storage stability or workability even when it is blended with the epoxy compound (A) and the propylene oxide compound (D). excellent. Examples of the compound which generates a cationic species or a Lewis acid by irradiation of an active energy ray include a sulfonium salt such as an aromatic diazonium salt, an aromatic sulfonium salt or an aromatic sulfonium salt. , iron-arene complexes, and the like.

作為芳香族重氮鹽,可列舉例如以下化合物:苯重氮六氟銻酸鹽、苯重氮六氟磷酸鹽、苯重氮六氟硼酸鹽等。 Examples of the aromatic diazonium salt include the following compounds: benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

作為芳香族錪鹽,可列舉例如以下化合物:二苯基錪四(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-壬苯基)錪六氟磷酸鹽等。 Examples of the aromatic onium salt include the following compounds: diphenylphosphonium tetrakis(pentafluorophenyl)borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, and di(4-anthracene). Phenyl) quinone hexafluorophosphate.

作為芳香族鋶鹽,可列舉例如以下化合物: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(二苯基二氫硫基)二苯硫醚雙六氟磷酸鹽、4,4’-雙[二(β-羥乙氧基)苯基二氫硫基二苯硫醚雙六氟銻酸鹽、4,4’-雙[二(β-羥乙氧基)苯基二氫硫基]二苯硫醚雙六氟磷酸鹽、7-[二(對甲苯基)二氫硫基]-2-異丙基噻噸酮六氟銻酸鹽、7-[二(對甲苯基)二氫硫基]-2-異丙基噻噸酮四(五氟苯基)硼酸鹽、4-苯基羰基-4’-二苯基二氫硫基-二苯硫醚六氟磷酸 鹽、4-(對三級丁基苯基羰基)-4’-二苯基二氫硫基-二苯硫醚六氟銻酸鹽、4-(對三級丁基苯基羰基)-4’-二(對甲苯基)二氫硫基-二苯硫醚四(五氟苯基)硼酸鹽等。 Examples of the aromatic onium salt include the following compounds: triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'- Bis(diphenyldihydrothio)diphenyl sulfide dihexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrothiodiphenyl sulfide dihexafluoroantimony Acid salt, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrothio]diphenyl sulfide dihexafluorophosphate, 7-[bis(p-tolyl)dihydrothio] 2-isopropyl thioxanthone hexafluoroantimonate, 7-[bis(p-tolyl)dihydrothio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4- Phenylcarbonyl-4'-diphenyldihydrothio-diphenyl sulfide hexafluorophosphate Salt, 4-(p-tert-butylphenylcarbonyl)-4'-diphenyldihydrothio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4 '-Di(p-tolyl)dihydrothio-diphenyl sulfide tetrakis(pentafluorophenyl)borate.

作為鐵-芳烴錯合物,可列舉例如以下化合物:二甲苯-環戊二烯鐵(II)六氟銻酸鹽、異丙苯-環戊二烯鐵(II)六氟磷酸鹽、二甲苯-環戊二烯鐵(II)-三(三氟甲磺醯基)甲烷化物等。 Examples of the iron-aromatic complex include the following compounds: xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene. - cyclopentadienyl iron (II)-tris(trifluoromethanesulfonyl) methanide or the like.

此等光陽離子聚合起始劑可分別單獨使用1種,亦可混合使用2種以上。由於此等當中,特別是芳香族鋶鹽即便是在300nm以上之波長範圍亦具有紫外線吸收特性,因此可提供硬化性優良、具良好機械強度或接著強度的硬化物,而可較佳地使用。 These photocationic polymerization initiators may be used alone or in combination of two or more. Among these, in particular, the aromatic onium salt has an ultraviolet absorbing property even in a wavelength range of 300 nm or more, and therefore, a cured product having excellent curability and good mechanical strength or adhesion strength can be provided, and can be preferably used.

(C)成分可容易地獲得其市售品,例如分別以商品名稱可列舉“KAYARAD PCI-220”、“KAYARAD PCI-620”(以上係日本化藥(股)製)、“UVI-6992”(Dow Chemical公司製)、“ADEKA OPTOMER SP-150”、“ADEKA OPTOMER SP-160”(以上係ADEKA(股)製)、“CI-5102”、“CIT-1370”、“CIT-1682”、“CIP-1866S”、“CIP-2048S”、“CIP-2064S”(以上係日本曹達(股)製)、“DPI-101”、“DPI-102”、“DPI-103”、“DPI-105”、“MPI-103”、“MPI-105”、“BBI-101”、“BBI-102”、“BBI-103”、“BBI-105”、 “TPS-101”、“TPS-102”、“TPS-103”、“TPS-105”、“MDS-103”、“MDS-105”、“DTS-102”、“DTS-103”(以上係Midori化學(股)製)、“PI-2074”(Rhodia公司製)、“IRGACURE 250”、“IRGACURE PAG103”、“IRGACURE PAG108”、“IRGACURE PAG121”、“IRGACURE PAG203”(以上係BASF公司製)、“CPI-100P”、“CPI-101A”、“CPI-210S”、“CPI-110P”(以上係San-Apro(股)製)等。尤其是San-Apro(股)製“CPI-100P”及“CPI-110P”,係於硬化性及接著性觀點為特佳。 (C) component can be easily obtained as a commercial item, for example, "KAYARAD PCI-220", "KAYARAD PCI-620" (the above is manufactured by Nippon Kayaku Co., Ltd.), "UVI-6992", respectively, by the trade name. (made by Dow Chemical Co., Ltd.), "ADEKA OPTOMER SP-150", "ADEKA OPTOMER SP-160" (above, ADEKA Co., Ltd.), "CI-5102", "CIT-1370", "CIT-1682", “CIP-1866S”, “CIP-2048S”, “CIP-2064S” (above is Japanese Soda (share) system), “DPI-101”, “DPI-102”, “DPI-103”, “DPI-105” ", MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102", "DTS-103" (above Midori Chemical Co., Ltd., "PI-2074" (manufactured by Rhodia Co., Ltd.), "IRGACURE 250", "IRGACURE PAG103", "IRGACURE PAG108", "IRGACURE PAG121", and "IRGACURE PAG203" (all manufactured by BASF Corporation) "CPI-100P", "CPI-101A", "CPI-210S", "CPI-110P" (the above is a San-Apro system). In particular, the "CPI-100P" and "CPI-110P" manufactured by San-Apro Co., Ltd. are particularly excellent in terms of hardenability and adhesion.

(C)成分之含有比例,係以組成物全體為基準,而設為0.5~10重量%之範圍。若該比例若低於0.5重量%,則接著劑之硬化變得不充分,而機械強度或接著強度下降;另一方面若該比例超過10重量%,則因硬化物中的離子性物質增加,而會有硬化物之吸濕性變高、耐久性能下降之事而不佳。又,就(C)成分之含有比例而言,較佳為1~5重量%,藉由設為此範圍,可使透明性等光學特性或耐久性能更為良好。 The content ratio of the component (C) is in the range of 0.5 to 10% by weight based on the entire composition. If the ratio is less than 0.5% by weight, the hardening of the adhesive becomes insufficient, and the mechanical strength or the subsequent strength decreases. On the other hand, if the ratio exceeds 10% by weight, the ionic substance in the cured product increases. On the other hand, there is a case where the hygroscopic property of the cured product becomes high and the durability can be lowered. In addition, the content ratio of the component (C) is preferably from 1 to 5% by weight, and by setting it as such a range, optical properties such as transparency and durability can be further improved.

<環氧丙烷化合物(D)> <propylene oxide compound (D)>

於本發明之光硬化性接著劑中,係摻混下式(2)所示之環氧丙烷化合物作為(D)成分。而藉由含有(D)成分,得以提升照光後之接著力展現速度。又,得以提升塗敷環境之相對濕度為約45%時的最終接著力。更者,在可能變動之塗敷環境的相對濕度中,藉由含有(D)成分,即使塗敷環境的相對濕度些許變動也亦能展現接著力。 In the photocurable adhesive of the present invention, a propylene oxide compound represented by the following formula (2) is blended as the component (D). By containing the (D) component, it is possible to enhance the speed of the adhesion after illumination. Moreover, the final adhesion force when the relative humidity of the coating environment is about 45% is improved. Further, in the relative humidity of the coating environment which may be changed, by containing the component (D), the adhesion can be exhibited even if the relative humidity of the coating environment is slightly changed.

就(D)成分之含有比例而言,以組成物全體為基準,有必要設為1~25重量%,較佳為1~18重量%。藉由以1~25重量%之比例含有(D)成分,可提升照光後之接著力展現速度、與塗敷環境之相對濕度為約45%時的最終接著力。又,藉由較佳係以18重量%以下含有,而即使塗敷環境之相對濕度成為約65%,亦不會惡化最終接著力,且得以提升塗敷環境之相對濕度為約45%時的最終接著力、與兩濕度條件下的接著力展現速度。(D)成分之含有比例,更佳為1~12重量%。 The content ratio of the component (D) is preferably 1 to 25% by weight, preferably 1 to 18% by weight based on the entire composition. By containing the component (D) in a ratio of 1 to 25% by weight, the final adhesion force when the adhesion force after the illuminating is exhibited and the relative humidity with the coating environment is about 45% can be improved. Moreover, by preferably containing 18% by weight or less, even if the relative humidity of the coating environment is about 65%, the final adhesion is not deteriorated, and the relative humidity of the coating environment is raised to about 45%. The final adhesion force and the adhesion force under the two humidity conditions show the speed. The content of the component (D) is more preferably from 1 to 12% by weight.

<以(甲基)丙烯酸烷基酯為必須組成單體單元的聚合物(E)> <A polymer (E) having a (meth)acrylic acid alkyl ester as an essential constituent monomer unit>

於本發明之光硬化性接著劑中,藉由含有(E)成分,可使耐濕熱試驗結束隨後之接著力良好。此外,本發明中,「以(甲基)丙烯酸烷基酯為必須組成單體單元的」聚合物係與「至少具有源自(甲基)丙烯酸烷基酯之組成單體單元的」聚合物係同義。 In the photocurable adhesive of the present invention, by containing the component (E), the heat resistance test can be completed and the subsequent adhesive force is good. Further, in the present invention, the "polymer of (meth)acrylic acid alkyl ester is an essential constituent monomer unit" and the "polymer having at least a constituent monomer unit derived from an alkyl (meth)acrylate) Synonymous.

作為(E)成分,只要是以(甲基)丙烯酸烷基酯為必須組成單體單元的聚合物,可使用各種聚合物。作為(E)成分,較佳為含有50莫耳%以上(甲基)丙烯酸烷基酯作為組成單體單元的聚合物,更佳為含有80莫耳%以上的聚合物。 As the component (E), various polymers can be used as long as the (meth)acrylic acid alkyl ester is a polymer which is an essential constituent monomer unit. The component (E) is preferably a polymer containing 50 mol% or more of an alkyl (meth)acrylate as a constituent monomer unit, and more preferably a polymer containing 80 mol% or more.

作為(甲基)丙烯酸烷基酯,可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲 基)丙烯酸二級丁酯、(甲基)丙烯酸三級丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二酯、(甲基)丙烯酸正十三酯及(甲基)丙烯酸正十四酯等。 Examples of the (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate. Base) butyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate 2 -ethylhexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate And isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-tridecyl (meth)acrylate, and n-tetradecyl (meth)acrylate.

此等化合物當中,較佳為含碳數1~10之烷基的(甲基)丙烯酸烷基酯,更佳為具碳數1~4之低級烷基的(甲基)丙烯酸烷基酯。 Among these compounds, an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl (meth)acrylate having a lower alkyl group having 1 to 4 carbon atoms is more preferred.

作為(E)成分,除(甲基)丙烯酸烷基酯外,亦可為可與(甲基)丙烯酸酯共聚合之乙烯性不飽和單體(以下稱為「其他單體」)的共聚物。 The (E) component may be a copolymer of an ethylenically unsaturated monomer (hereinafter referred to as "another monomer") copolymerizable with a (meth) acrylate in addition to an alkyl (meth)acrylate. .

作為其他單體之具體例,可列舉(甲基)丙烯酸等含羧基單體;丙烯醯胺2-甲基丙磺酸及苯乙烯磺酸等含磺酸基單體;含磷酸基單體;(甲基)丙烯腈等含氰基單體、乙烯酯;苯乙烯及α-甲基苯乙烯等芳香族乙烯化合物;含酸酐基單體;(甲基)丙烯酸羥乙酯、(甲基)丙烯酸羥乙酯及(甲基)丙烯酸羥丁酯等(甲基)丙烯酸羥烷基酯等含羥基單體;丙烯醯胺、二甲基丙烯醯胺、二乙基丙烯醯胺等含醯胺基單體;含胺基單體;含醯亞胺基單體;(甲基)丙烯酸環氧丙酯等含環氧基單體;(甲基)丙烯醯基啉;以及乙烯醚等。 Specific examples of the other monomer include a carboxyl group-containing monomer such as (meth)acrylic acid; a sulfonic acid group-containing monomer such as acrylamide 2-methylpropanesulfonic acid or styrenesulfonic acid; and a phosphate group-containing monomer; a cyano group-containing monomer such as (meth)acrylonitrile or a vinyl ester; an aromatic vinyl compound such as styrene or α-methylstyrene; an acid anhydride group-containing monomer; hydroxyethyl (meth)acrylate; a hydroxyl group-containing monomer such as hydroxyethyl acrylate or hydroxybutyl (meth) acrylate such as hydroxyalkyl (meth) acrylate; decylamine such as acrylamide, dimethyl acrylamide or diethyl acrylamide Base monomer; amine group-containing monomer; quinone imine group-containing monomer; epoxy group-containing (meth)acrylic acid propyl acrylate; (meth) acrylonitrile group Porphyrin; and vinyl ether and the like.

作為(E)成分,可從前述聚合物使用各種聚合物。 As the component (E), various polymers can be used from the above polymer.

若以改善接著性、以及與組成物之溶解性為目的,較佳為(甲基)丙烯酸烷基酯與含酸性基單體的共聚物。 For the purpose of improving the adhesion and the solubility of the composition, a copolymer of an alkyl (meth)acrylate and an acid group-containing monomer is preferred.

作為含酸性基單體,可列舉含羧基單體、含磺酸基單體、含酸酐基單體及含磷酸基單體等,較佳為含羧基單體。 Examples of the acid group-containing monomer include a carboxyl group-containing monomer, a sulfonic acid group-containing monomer, an acid anhydride group-containing monomer, and a phosphoric acid group-containing monomer, and a carboxyl group-containing monomer is preferable.

就該共聚物而言,出於使組成物之保存穩定性良好之理由,較佳為酸價為20mgKOH/g以下之共聚物,更佳為15mgKOH/g以下。 The copolymer is preferably a copolymer having an acid value of 20 mgKOH/g or less, more preferably 15 mgKOH/g or less, for the reason that the storage stability of the composition is good.

就(E)成分之分子量而言,以重量平均分子量(以下為「Mw」)計較佳為1,000~500,000,更佳為1,000~200,000。 The molecular weight of the component (E) is preferably from 1,000 to 500,000, more preferably from 1,000 to 200,000, based on the weight average molecular weight (hereinafter referred to as "Mw").

再者,於本發明中,Mw係指將藉由凝膠滲透層析法(以下亦稱為「GPC」)所測得之分子量換算成聚苯乙烯者。 In the present invention, Mw means that the molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") is converted into polystyrene.

作為(E)成分,係可從前述聚合物使用各種聚合物,惟較佳為含有含碳數1~10之烷基的(甲基)丙烯酸烷基酯作為組成單體單元,且重量平均分子量為1,000~500,000的聚合物。 As the component (E), various polymers may be used from the above polymer, and it is preferred to use an alkyl (meth)acrylate having an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit, and a weight average molecular weight. It is a polymer of 1,000 to 500,000.

作為該聚合物之更佳實例,可列舉例如下述2種聚合物: As a more preferable example of the polymer, for example, the following two polymers are exemplified:

‧(E1)成分:含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元,且Mw為1,000~200,000的聚合物 ‧ (E1) component: a polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit and having a Mw of 1,000 to 200,000

‧(E2)成分:含有60重量%以上之含碳數1~10之烷基的丙烯酸烷基酯作為組成單體單元,且Mw為1,000~200,000的聚合物。 ‧ (E2) component: a polymer containing 60% by weight or more of an alkyl acrylate having an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit and having a Mw of 1,000 to 200,000.

(E1)成分係含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元,且Mw為1,000~200,000的聚合物,係出於對丙烯酸樹脂之接著力優良的理由而較佳。 The component (E1) is a polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit and having a Mw of 1,000 to 200,000, which is preferable for the reason that the adhesion to the acrylic resin is excellent.

(E1)成分可為與含酸性基單體的共聚物,作為含酸性基單體可舉出與前述相同之單體,較佳為含羧基單體。 The component (E1) may be a copolymer with an acid group-containing monomer, and examples of the acid group-containing monomer include the same monomers as described above, and a carboxyl group-containing monomer is preferred.

就該共聚物而言,係以與前述相同之理由,較佳為酸價為20mgKOH/g以下之共聚物,更佳為15mgKOH/g以下。 The copolymer is preferably a copolymer having an acid value of 20 mgKOH/g or less, more preferably 15 mgKOH/g or less, for the same reason as described above.

(E1)成分係有市售,可列舉例如三菱RAYON(股)製Dianal BR-80(含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元、Mw95,000、酸價0mgKOH/g之PMMA系聚合物)、同BR-83(含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元、Mw40,000、酸價2mgKOH/g之PMMA系聚合物)及同BR-87(含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元、Mw25,000、酸價10.5mgKOH/g之PMMA系聚合物)等。 The component (E1) is commercially available, and, for example, Dianal BR-80 manufactured by Mitsubishi Rayon Co., Ltd. (containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 95,000, and an acid value of 0 mgKOH/g) PMMA-based polymer), with BR-83 (containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 40,000, an acid value of 2 mgKOH/g of PMMA-based polymer) and the same BR-87 (including 60% by weight or more of methyl methacrylate is used as a constituent monomer unit, Mw 25,000, a PMMA-based polymer having an acid value of 10.5 mgKOH/g, and the like.

作為(E1)成分,亦可為以後述之高溫聚合,較佳為高溫連續聚合所製造者。 The (E1) component may be a high-temperature polymerization described later, and is preferably a high-temperature continuous polymerization.

(E2)成分係含有60重量%以上之含碳數1~10之烷基的丙烯酸烷基酯作為組成單體單元,且Mw為1,000~200,000,係出於對偏光膜或丙烯酸樹脂等的保護薄膜之接著力優良的理由而較佳。 The component (E2) is an alkyl acrylate containing 60% by weight or more of an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit, and Mw is 1,000 to 200,000, which is for protection of a polarizing film or an acrylic resin. The reason why the adhesion of the film is excellent is preferable.

作為含碳數1~10之烷基的丙烯酸烷基酯,可舉出與前述相同之化合物。 Examples of the alkyl acrylate having an alkyl group having 1 to 10 carbon atoms include the same compounds as described above.

作為(E2)成分,只要是含有60重量%以上之含碳數1~10之烷基的丙烯酸烷基酯作為組成單體單元,亦可為與甲基丙烯酸烷基酯或其他單體的共聚物。 The (E2) component may be an alkyl acrylate containing 60% by weight or more of an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit, and may be copolymerized with an alkyl methacrylate or other monomer. Things.

(E2)成分亦可為含碳數1~10之烷基的丙烯酸烷基酯、與甲基丙烯酸烷基酯或其他單體的嵌段共聚物[以下稱為「(E2-1)成分」]。 The component (E2) may be an alkyl acrylate having an alkyl group having 1 to 10 carbon atoms, a block copolymer with an alkyl methacrylate or another monomer (hereinafter referred to as "(E2-1) component"). ].

作為(E2-1)成分中之單體的較佳組合,可舉出具有聚丙烯酸酯嵌段單元與聚甲基丙烯酸酯嵌段單元的嵌段聚合物、及具有聚丙烯酸酯嵌段單元與其他單體之聚合物之嵌段單元的嵌段聚合物等。 Preferred examples of the monomer in the component (E2-1) include a block polymer having a polyacrylate block unit and a polymethacrylate block unit, and a polyacrylate block unit and A block polymer or the like of a block unit of a polymer of another monomer.

此等當中,又以具有聚丙烯酸酯系嵌段單元與聚甲基丙烯酸酯系嵌段單元的嵌段聚合物、甚或含有聚丙烯酸丁酯與聚甲基丙烯酸甲酯作為嵌段單元的嵌段聚合物為較佳。 Among these, block polymers having polyacrylate block units and polymethacrylate block units, or even blocks containing polybutyl acrylate and polymethyl methacrylate as block units are used. Polymers are preferred.

作為(E2-1)成分,可使用依習知方法之聚合使用前述單體而製造者,可列舉例如自由基聚合法、活性陰離子聚合法、活性自由基聚合法等。又,作為聚合之形態,可列舉例如溶液聚合法、乳液聚合法、懸浮聚合法及塊狀聚合法等。 The component (E2-1) can be produced by polymerization using a conventional method, and examples thereof include a radical polymerization method, a living anionic polymerization method, and a living radical polymerization method. Moreover, examples of the form of polymerization include a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.

(E2-1)成分係有市售,可列舉Kuraray(股)製KURARITY(LA1114、LA2140e、LA2330、LA2250)等。 The component (E2-1) is commercially available, and KURARITY (LA1114, LA2140e, LA2330, LA2250) manufactured by Kuraray Co., Ltd. may be mentioned.

(E2)成分係Mw為1,000~200,000的聚合物,惟較佳為Mw為1,000~100,000的聚合物,更佳為1,000~20,000。此係出於具該Mw的聚合物為低黏度、所得組成物亦為低黏度且容易塗敷之理由;或是即使有組成物之 低黏度化之限制卻仍可增加摻混份數,而作為結果可提升接著力之理由而較佳。 The component (E2) is a polymer having a Mw of 1,000 to 200,000, preferably a polymer having a Mw of 1,000 to 100,000, more preferably 1,000 to 20,000. This is because the polymer having the Mw is low in viscosity, the resulting composition is also low in viscosity and easy to apply; or even if there is a composition The limitation of low viscosity can still increase the number of blends, and as a result, the reason for the adhesion can be improved.

如欲以通常之聚合方法製造該低分子量聚合物,一般係有必要增加鏈轉移劑或聚合起始劑。若使用大量地使用鏈轉移劑的聚合物,則組成物之陽離子硬化性或接著力變得容易下降;若使用大量地使用聚合起始劑的聚合物,則組成物之保存穩定性變得容易下降。 If the low molecular weight polymer is to be produced by a usual polymerization method, it is generally necessary to add a chain transfer agent or a polymerization initiator. When a polymer using a chain transfer agent in a large amount is used, the cationic hardenability or the bonding force of the composition is liable to lower; if a polymer using a polymerization initiator in a large amount is used, the storage stability of the composition becomes easy. decline.

從而,較佳為藉由不需大量鏈轉移劑或聚合起始劑之高溫聚合所製成之聚合物,且含有60重量%以上之含碳數1~10之烷基的丙烯酸烷基酯作為組成單體單元,而Mw為1,000~20,000的聚合物[以下稱為「(E2-2)成分」]。 Therefore, it is preferred to use a polymer prepared by high-temperature polymerization which does not require a large amount of a chain transfer agent or a polymerization initiator, and which contains 60% by weight or more of an alkyl acrylate having an alkyl group having 1 to 10 carbon atoms as A polymer which constitutes a monomer unit and has a Mw of 1,000 to 20,000 [hereinafter referred to as "(E2-2) component").

尚且,於本發明中,Mw係指將藉由GPC所測得之分子量換算成聚苯乙烯者。 Further, in the present invention, Mw means that the molecular weight measured by GPC is converted into polystyrene.

作為高溫聚合之溫度,較佳為160~350℃,更佳為180~300℃。 The temperature for high-temperature polymerization is preferably 160 to 350 ° C, more preferably 180 to 300 ° C.

在高溫聚合當中,由於高溫連續聚合不僅是生產性優良,且難得共聚物製品中的組成分布,而具有相溶性優良等的優點。 Among the high-temperature polymerizations, continuous polymerization at a high temperature is not only excellent in productivity, but also has a composition distribution in a copolymer product, and has an advantage of excellent compatibility.

高溫連續聚合可依周知方法來實施(例如日本特表昭57-502171號公報、日本特開昭59-6207號公報及日本特開昭60-215007號公報等)。 The high-temperature continuous polymerization can be carried out by a known method (for example, JP-A-57-502171, JP-A-59-6207, JP-A-60-215007, and the like).

具體而言,可舉出以溶媒裝滿可加壓之反應器,並於加壓下設定為既定溫度後,以一定的供給速度對反應器供給包含單體、或是因應需求之聚合溶媒、聚合起始 劑的單體混合物,而抽出與單體混合物之供給量相符量的反應液之方法。 Specifically, a reactor that can be pressurized by a solvent is used, and after setting to a predetermined temperature under pressure, a reactor containing a monomer or a polymerization solvent according to a demand is supplied at a constant supply rate. Aggregation start A monomer mixture of the agent, and a method of extracting a reaction liquid in an amount corresponding to the supply amount of the monomer mixture.

就(E2-2)成分之玻璃轉移溫度而言,較佳為20℃以下,更佳為-90~0℃。 The glass transition temperature of the component (E2-2) is preferably 20 ° C or lower, more preferably -90 to 0 ° C.

尚且,本發明中,玻璃轉移溫度係指利用示差掃描熱量分析儀(DSC),以2℃/分鐘之升溫速度所測得之值。 Further, in the present invention, the glass transition temperature means a value measured by a differential scanning calorimeter (DSC) at a temperature elevation rate of 2 ° C /min.

本發明之(E)成分亦可為在聚合物中導入(甲基)丙烯醯基等自由基聚合性官能基、環氧基或氧雜環丁烷基等陽離子聚合性官能基者。作為此等官能基之導入方法,可列舉例如在活性陰離子聚合或活性自由基聚合之末端導入的方法、於聚合物中之官能基加成具有聚合性官能基之化合物的方法等。又,在導入環氧基或氧雜環丁烷基等陽離子聚合性官能基之情形,亦可共聚合具此等官能基的(甲基)丙烯酸酯。 The component (E) of the present invention may be a cationically polymerizable functional group such as a radical polymerizable functional group such as a (meth)acrylinyl group or an epoxy group or an oxetanyl group. Examples of the method of introducing such a functional group include a method of introducing a terminal at the end of living anionic polymerization or living radical polymerization, a method of adding a compound having a polymerizable functional group to a functional group in a polymer, and the like. Further, in the case of introducing a cationically polymerizable functional group such as an epoxy group or an oxetanyl group, a (meth) acrylate having such a functional group may be copolymerized.

就(E)成分而言,可僅使用前述化合物的1種,亦可併用2種以上。 The component (E) may be used alone or in combination of two or more.

作為(E)成分之較佳組合,於與不同種類基材之接著性優良之觀點,較佳組合使用(E1)成分與(E2)成分,更佳為組合使用(E1)成分與(E2-2)成分。 As a preferred combination of the component (E), it is preferred to use the (E1) component and the (E2) component in combination with the other types of substrates, and it is more preferable to use the (E1) component in combination with (E2-). 2) Ingredients.

作為(E1)成分與(E2)成分之併用比例,較佳為1/9~7/3。 The ratio of the combination of the (E1) component and the (E2) component is preferably from 1/9 to 7/3.

就(E)成分之含有比例而言,以組成物全體為基準,係有設為0.1~25重量%之必要,較佳為1~20重量%。藉由以0.1~25重量%之比例含有(E)成分,可使耐濕熱試驗結束隨後之接著力良好。 The content ratio of the component (E) is required to be 0.1 to 25% by weight, preferably 1 to 20% by weight, based on the entire composition. By containing the component (E) in a ratio of 0.1 to 25% by weight, the endurance of the damp heat resistance test can be made good.

<環氧丙烷化合物(F)> <propylene oxide compound (F)>

於本發明之光硬化性接著劑中,可摻混下式(3)所示之環氧丙烷化合物作為(F)成分。藉由含有(F)成分,得以進一步提升照光後之接著力展現速度或最終接著力。 In the photocurable adhesive of the present invention, a propylene oxide compound represented by the following formula (3) may be blended as the component (F). By containing the (F) component, it is possible to further enhance the adhesion force or the final adhesion force after the illumination.

(F)成分之含有比例係較佳設為1~30重量%。藉由設為此範圍,得以進一步提升照光後之接著力展現速度或最終接著力。就(F)成分之含有比例而言,更佳為1~20重量%。 The content ratio of the component (F) is preferably from 1 to 30% by weight. By setting this range, it is possible to further enhance the adhesion force or the final adhesion force after the illumination. The content ratio of the component (F) is more preferably from 1 to 20% by weight.

<光自由基聚合起始劑(G)> <Photoradical polymerization initiator (G)>

本發明之光硬化性接著劑所含的(B)成分等之自由基硬化性成分雖可藉由以光分解(C)成分時所產生的自由基而硬化,而為了以較少的照射量獲得充分的反應率,係較佳為摻混光自由基聚合起始劑作為(G)成分。(G)成分之摻混比例,係較佳為以組成物全體為基準為10重量%以下,更佳為0.1~3重量%。若摻混量為10重量%以上,則會引起耐久性之下降而不佳。 The radical curable component such as the component (B) contained in the photocurable adhesive of the present invention can be cured by radicals generated by photodecomposition of the component (C), and in order to reduce the amount of irradiation. In order to obtain a sufficient reaction rate, it is preferred to incorporate a photoradical polymerization initiator as the component (G). The blending ratio of the component (G) is preferably 10% by weight or less, and more preferably 0.1 to 3% by weight based on the entire composition. When the blending amount is 10% by weight or more, the deterioration of durability is not preferable.

作為(G)成分之具體例,可列舉例如以下化合物:如4’-苯氧基-2,2-二氯苯乙酮、4’-三級丁基-2,2-二氯苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2-甲基-1-(4-甲硫基苯基)-2-啉丙-1-酮、1-羥環己基苯基酮、α,α-二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙-1-酮、 1-(4-異丙基苯基)-2-羥基-2-甲基丙-1-酮、1-(4-十二基苯基)-2-羥基-2-甲基丙-1-酮、1-[4-(2-羥乙氧基)苯基]-2-羥基-2-甲基丙-1-酮及2-苯甲基-2-二甲胺基-1-(4-啉苯基)丁-1-酮之苯乙酮系光聚合起始劑;如安息香、安息香甲醚、安息香乙醚、安息香異丙醚及安息香異丁醚之安息香醚系光聚合起始劑;如二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4’-甲基二苯硫醚及2,4,6-三甲基二苯甲酮之二苯甲酮系光聚合起始劑;如2-異丙基噻噸酮、2,4-二乙基噻噸酮、2,4-二氯噻噸酮及1-氯-4-丙氧基噻噸酮之噻噸酮系光聚合起始劑;如2,4,6-三甲基苯甲醯基二苯基膦氧化物、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基膦氧化物及雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物之醯基膦氧化物系光聚合起始劑;如1,2-辛二酮,1-[4-(苯硫基苯基)]-,2-(O-苯甲醯基肟)之肟酯系光聚合起始劑;樟腦醌等。 Specific examples of the component (G) include, for example, the following compounds: 4'-phenoxy-2,2-dichloroacetophenone, 4'-tertiary butyl-2,2-dichloroacetophenone 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-(4-methylthiophenyl)-2- Phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, α,α-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-( 4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one and 2-benzyl-2-dimethylamino-1-(4- An acetophenone photopolymerization initiator of phenyl phenyl)butan-1-one; a benzoin ether photopolymerization initiator such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide and 2,4,6-trimethyl a benzophenone photopolymerization initiator of benzophenone; such as 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro a thioxanthone photopolymerization initiator of -4-propoxythioxanthone; such as 2,4,6-trimethylbenzhydryldiphenylphosphine oxide, bis(2,6-dimethoxy Benzophosphonium oxide of bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide Photopolymerization initiator; such as 1,2-octanedione, 1-[4-(phenylthiophenyl)]-, 2-(O-benzylidenehydrazide) oxime ester photopolymerization initiator ; cerebral palsy and so on.

(G)成分可單獨使用1種、或視所欲性能而摻混2種以上來使用。 The component (G) can be used singly or in combination of two or more kinds depending on the desired properties.

當摻混(G)成分之光自由基聚合起始劑時,其含有比例以組成物全體為基準,較佳為10重量%以下,更佳為0.1~3重量%。若光自由基聚合起始劑(G)之含有比例為上述範圍,則可獲得充分的強度,且硬化性優良。 When the photoradical polymerization initiator of the component (G) is blended, the content thereof is preferably 10% by weight or less, and more preferably 0.1 to 3% by weight based on the entire composition. When the content ratio of the photoradical polymerization initiator (G) is in the above range, sufficient strength can be obtained and the curability is excellent.

作為(G)成分,以接著力優良觀點較佳為醯基膦氧化 物系化合物。 As the component (G), it is preferred that the mercaptophosphine is oxidized from the viewpoint of excellent adhesion. Compounds.

<調平劑(H)> <Leveling agent (H)>

於本發明之光硬化性接著劑中,以獲得平滑性優良的塗布面為目的,較佳為含有(H)成分之調平劑。 In the photocurable adhesive of the present invention, for the purpose of obtaining a coated surface having excellent smoothness, a leveling agent containing the component (H) is preferred.

作為(H)成分,可舉出矽氧系調平劑及氟系調平劑等,可以使用市售的各種調平劑。此等當中,以耐濕熱試驗結束隨後之接著力優良觀點,特佳為具(甲基)丙烯醯基之矽氧系調平劑。 Examples of the component (H) include a ruthenium-based leveling agent and a fluorine-based leveling agent, and various commercially available leveling agents can be used. Among these, a (meth)acrylonitrile-based oxime-based leveling agent is particularly preferred from the viewpoint of the end of the heat-resistant test and the subsequent adhesion.

(H)成分之較佳含有比例以組成物全體為基準係為0.01~0.5重量%。若添加比例處於上述範圍,則可充分獲得調平劑之添加效果,且接著性優良。 The content ratio of the component (H) is preferably 0.01 to 0.5% by weight based on the entire composition. When the addition ratio is in the above range, the effect of adding the leveling agent can be sufficiently obtained, and the adhesion is excellent.

<其他的硬化性成分> <Other hardening ingredients>

本發明之光硬化性接著劑除上述(A)~(H)成分外,還可含有其他的陽離子硬化性成分或自由基硬化性成分。 The photocurable adhesive of the present invention may contain other cationic hardening components or radical curable components in addition to the above components (A) to (H).

作為(A)成分、(D)成分及(F)成分以外之陽離子硬化性成分,可舉出各種的環氧化合物或環氧丙烷化合物及乙烯醚化合物。 Examples of the cationically curable component other than the component (A), the component (D) and the component (F) include various epoxy compounds, propylene oxide compounds and vinyl ether compounds.

作為(A)成分以外之環氧化合物之具體例,可列舉雙酚A之二環氧丙基醚、雙酚F之二環氧丙基醚、溴化雙酚A之二環氧丙基醚、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、聯苯型環氧樹脂、對苯二酚二環氧丙基醚、間苯二酚二環氧丙基醚、對酞酸二環氧丙酯、酞酸二環氧丙酯、末端羧酸聚丁二烯與雙酚A型環氧樹脂之加成反應物、二環戊二烯二氧化物、檸檬烯二氧化物、4- 乙烯環己烯二氧化物、1,6-己二醇二環氧丙基醚、三羥甲基丙烷三環氧丙基醚、新戊四醇四環氧丙基醚、聚伸丁二醇二環氧丙基醚、氫化雙酚A二環氧丙基醚、環氧化植物油、2-(3,4-環氧環己基)乙基三甲氧基矽烷、2-(3,4-環氧環己基)乙基三乙氧基矽烷、3-環氧丙氧丙基三甲氧基矽烷、3-環氧丙氧丙基甲基二甲氧基矽烷、兩末端羧基之聚丁二醇二環氧丙基醚、聚丁二醇之內部環氧化物、苯乙烯-丁二烯共聚物之雙鍵一部分經環氧化之化合物[例如DAICEL化學工業(股)製“Epofriend”]、及乙烯-丁烯共聚物與聚異戊二烯之嵌段共聚物之異戊二烯單元一部分經環氧化之化合物(例如KRATON公司製“L-207”)等。 Specific examples of the epoxy compound other than the component (A) include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of brominated bisphenol A. , phenol novolak type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcinol diepoxypropyl ether, p-nonanoic acid bicyclo Oxypropyl propyl ester, diglycidyl citrate, addition reaction of terminal carboxylic acid polybutadiene with bisphenol A type epoxy resin, dicyclopentadiene dioxide, limonene dioxide, 4- Ethylene cyclohexene dioxide, 1,6-hexanediol diepoxypropyl ether, trimethylolpropane triepoxypropyl ether, pentaerythritol tetraepoxypropyl ether, polybutanediol Diepoxypropyl ether, hydrogenated bisphenol A diglycidyl ether, epoxidized vegetable oil, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 2-(3,4-epoxy Cyclohexyl)ethyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, polybutanediol bicyclic ring at both terminal carboxyl groups Oxypropyl propyl ether, internal epoxide of polytetramethylene glycol, a part of the double bond of styrene-butadiene copolymer, epoxidized compound [for example, "Epofriend" by DAICEL Chemical Industry Co., Ltd.], and ethylene-butyl A compound in which a part of the isoprene unit of the block copolymer of the olefin copolymer and the polyisoprene is epoxidized (for example, "L-207" manufactured by KRATON Co., Ltd.) or the like.

作為(D)成分及(F)成分以外之環氧丙烷化合物之具體例,可列舉如3-乙基-3-(2-乙基己氧基甲基)環氧丙烷之含烷氧基烷基之單官能環氧丙烷、如3-乙基-3-苯氧基甲基環氧丙烷之含芳香族基之單官能環氧丙烷、1,4-雙[(3-乙基環氧丙烷-3-基)甲氧基甲基]苯、1,4-雙[(3-乙基環氧丙烷-3-基)甲氧基]苯、1,3-雙[(3-乙基環氧丙烷-3-基)甲氧基]苯、1,2-雙[(3-乙基環氧丙烷-3-基)甲氧基]苯、4,4’-雙[(3-乙基環氧丙烷-3-基)甲氧基]聯苯、2,2’-雙[(3-乙基環氧丙烷-3-基)甲氧基]聯苯、3,3’,5,5’-四甲基-4,4’-雙[(3-乙基環氧丙烷-3-基)甲氧基]聯苯、2,7-雙[(3-乙基環氧丙烷-3-基)甲氧基]萘、雙[4-{(3-乙基環氧丙烷-3-基)甲氧基}苯基]甲烷、雙[2-{(3-乙基環氧丙烷-3-基)甲氧基}苯基]甲烷、2,2-雙[4-{(3-乙基環氧丙烷-3-基)甲氧基}苯基]丙烷、酚醛型酚-甲醛樹脂之藉由3-氯甲基 -3-乙基環氧丙烷的醚化改質物、3(4),8(9)-雙[(3-乙基環氧丙烷-3-基)甲氧基甲基]-三環[5.2.1.02,6]癸烷、2,3-雙[(3-乙基環氧丙烷-3-基)甲氧基甲基]降莰烷、1,1,1-三[(3-乙基環氧丙烷-3-基)甲氧基甲基]丙烷、1-丁氧基-2,2-雙[(3-乙基環氧丙烷-3-基)甲氧基甲基]丁烷、1,2-雙[{2-(3-乙基環氧丙烷-3-基)甲氧基}乙硫基]乙烷、雙[{4-(3-乙基環氧丙烷-3-基)甲硫基}苯基]硫化物、1,6-雙[(3-乙基環氧丙烷-3-基)甲氧基]-2,2,3,3,4,4,5,5-八氟己烷、3-[(3-乙基環氧丙烷-3-基)甲氧基]丙基三甲氧基矽烷、3-[(3-乙基環氧丙烷-3-基)甲氧基]丙基三乙氧基矽烷、3-[(3-乙基環氧丙烷-3-基)甲氧基]丙基三烷氧基矽烷之水解縮合物、四[(3-乙基環氧丙烷-3-基)甲基]矽酸酯、3-乙基環氧丙烷-3-基甲醇與矽烷四醇聚縮合物之縮合反應生成物等。 Specific examples of the propylene oxide compound other than the component (D) and the component (F) include an alkoxyalkyl group such as 3-ethyl-3-(2-ethylhexyloxymethyl) propylene oxide. Monofunctional propylene oxide, aromatic group-containing monofunctional propylene oxide such as 3-ethyl-3-phenoxymethyl propylene oxide, 1,4-bis[(3-ethyl propylene oxide) 3-yl)methoxymethyl]benzene, 1,4-bis[(3-ethylepoxypropan-3-yl)methoxy]benzene, 1,3-bis[(3-ethylcyclo) Oxypropan-3-yl)methoxy]benzene, 1,2-bis[(3-ethylepoxypropan-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyl) Propylene oxide-3-yl)methoxy]biphenyl, 2,2'-bis[(3-ethylepoxypropan-3-yl)methoxy]biphenyl, 3,3',5,5 '-Tetramethyl-4,4'-bis[(3-ethylepoxypropan-3-yl)methoxy]biphenyl, 2,7-bis[(3-ethylepoxypropane-3- Methoxy]naphthalene, bis[4-{(3-ethyl propylene oxide-3-yl)methoxy}phenyl]methane, bis[2-{(3-ethyl propylene oxide-3) -yl)methoxy}phenyl]methane, 2,2-bis[4-{(3-ethylepoxypropan-3-yl)methoxy}phenyl]propane, phenolic phenol-formaldehyde resin Etherification modification by 3-chloromethyl-3-ethyl propylene oxide, 3(4), 8 (9)-bis[(3-ethylepoxypropan-3-yl)methoxymethyl]-tricyclo[5.2.1.0 2,6 ]decane, 2,3-bis[(3-ethyl) Propylene oxide-3-yl)methoxymethyl]norbornane, 1,1,1-tris[(3-ethylepoxypropan-3-yl)methoxymethyl]propane, 1-butyl Oxy-2,2-bis[(3-ethylepoxypropan-3-yl)methoxymethyl]butane, 1,2-bis[{2-(3-ethyl propylene oxide-3) -yl)methoxy}ethylthio]ethane, bis[{4-(3-ethyl propylene oxide-3-yl)methylthio}phenyl] sulfide, 1,6-bis[(3) -ethyl propylene oxide-3-yl)methoxy]-2,2,3,3,4,4,5,5-octafluorohexane, 3-[(3-ethyl propylene oxide-3 -yl)methoxy]propyltrimethoxydecane, 3-[(3-ethylepoxypropan-3-yl)methoxy]propyltriethoxydecane, 3-[(3-ethyl Hydrolyzed condensate of propylene oxide-3-yl)methoxy]propyltrialkoxydecane, tetrakis[(3-ethylepoxypropan-3-yl)methyl]decanoate, 3-ethyl A condensation reaction product of propylene oxide-3-ylmethanol and a decane tetraol polycondensate.

作為乙烯醚化合物之具體例,可列舉環己基乙烯醚、2-乙基己基乙烯醚、十二基乙烯醚、4-羥丁基乙烯醚、二乙二醇單乙烯醚、三乙二醇二乙烯醚、環己二甲醇二乙烯醚等。 Specific examples of the vinyl ether compound include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and triethylene glycol. Vinyl ether, cyclohexanedimethanol divinyl ether, and the like.

(A)成分、(D)成分及(F)成分以外之陽離子硬化性成分的含有比例以組成物全體為基準,較佳為未滿20重量%,更佳為未滿10重量%,尤佳為未滿5重量%。 The content ratio of the cationically curable component other than the component (A), the component (D), and the component (F) is preferably less than 20% by weight, more preferably less than 10% by weight, based on the entire composition. It is less than 5% by weight.

作為(B)成分以外之自由基硬化性成分,可舉出各種的化合物,可列舉例如(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、順丁烯二醯亞胺類、(甲基)丙烯酸、順丁烯二酸、依康酸、(甲基)丙烯醛、(甲基)丙烯醯基啉、 N-乙烯-2-吡咯烷酮、異三聚氰酸烯丙酯、己二酸二乙烯酯、乙烯三甲氧基矽烷等。 Examples of the radical curable component other than the component (B) include various compounds, and examples thereof include (meth)acrylates, (meth)acrylamides, and maleimide. Methyl)acrylic acid, maleic acid, isaconic acid, (meth)acrolein, (meth)acrylonitrile Porphyrin, N-vinyl-2-pyrrolidone, allyl isocyanurate, divinyl adipate, ethylene trimethoxydecane, and the like.

作為分子內具有1個(甲基)丙烯醯基的(甲基)丙烯酸酯類之具體例,可列舉(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂醯酯、(甲基)丙烯酸2-羥乙酯、(甲基)丙烯酸2-羥丙酯、(甲基)丙烯酸4-羥丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異莰酯、1,4-環己烷二羥甲基單(甲基)丙烯酸酯、(甲基)丙烯酸二環戊烷酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧乙酯、(甲基)丙烯酸苯甲酯、酚環氧烷加成物之(甲基)丙烯酸酯、對異丙苯酚環氧烷加成物之(甲基)丙烯酸酯、鄰苯酚環氧烷加成物之(甲基)丙烯酸酯、壬酚環氧烷加成物之(甲基)丙烯酸酯、(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸乙氧乙氧基乙酯2-乙基己醇之環氧烷加成物之(甲基)丙烯酸酯、戊二醇單(甲基)丙烯酸酯、己二醇單(甲基)丙烯酸酯、二乙二醇之單(甲基)丙烯酸酯、三乙二醇之單(甲基)丙烯酸酯、四乙二醇之單(甲基)丙烯酸酯、聚乙二醇之單(甲基)丙烯酸酯、二丙二醇之單(甲基)丙烯酸酯、三丙二醇之單(甲基)丙烯酸酯、聚丙二醇之單(甲基)丙烯酸酯、2-羥基-3-苯氧基丙基(甲基)丙烯酸酯、2-羥基-3-丁氧基丙基(甲基)丙烯酸酯、(甲基)丙烯酸四氫呋喃酯、己內酯改質(甲基)丙烯酸四氫呋喃酯、(2-乙 基-2-甲基-1,3-二-4-基)甲基(甲基)丙烯酸酯、(2-異丁基-2-甲基-1,3-二-4-基)甲基(甲基)丙烯酸酯、(1,4-二氧雜螺[4,5]癸-2-基)甲基(甲基)丙烯酸酯、(甲基)丙烯酸環氧丙酯、3,4-環氧環己基甲基(甲基)丙烯酸酯、(3-乙基環氧丙烷-3-基)甲基(甲基)丙烯酸酯、異氰酸2-(甲基)丙烯醯氧乙酯、(甲基)丙烯酸烯丙酯、N-(甲基)丙烯醯氧乙基六氫酞醯亞胺、N-(甲基)丙烯醯氧乙基四氫酞醯亞胺、六氫酞酸2-(甲基)丙烯醯氧乙酯、琥珀酸2-(甲基)丙烯醯氧乙酯、ω-羧基-聚己內酯單(甲基)丙烯酸酯、磷酸2-(甲基)丙烯醯氧乙酯、3-(甲基)丙烯醯氧丙基三甲氧基矽烷、3-(甲基)丙烯醯氧丙基二甲氧基甲基矽烷、3-(甲基)丙烯醯氧丙基三乙氧基矽烷等。 Specific examples of the (meth) acrylate having one (meth) acryl fluorenyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. , isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, (methyl) ) isooctyl acrylate, lauryl (meth) acrylate, stearyl methacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (methyl) 4-hydroxybutyl acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, 1,4-cyclohexane dimethylol mono (meth) acrylate, (meth) acrylate Cyclopentyl ester, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, benzyl (meth)acrylate, phenol alkylene oxide adduct (methyl) (Meth) acrylate, p-isopropylphenol alkylene oxide adduct (meth) acrylate, o-phenol alkylene oxide adduct (meth) acrylate, nonylphenol alkylene oxide adduct (methyl) Acrylate, 2-methoxyethyl (meth)acrylate, (A Ethylene oxide ethoxy acrylate 2-ethylhexanol alkylene oxide adduct (meth) acrylate, pentanediol mono (meth) acrylate, hexane diol mono (meth) acrylate Monoester (meth) acrylate of ester, diethylene glycol, mono (meth) acrylate of triethylene glycol, mono (meth) acrylate of tetraethylene glycol, mono (methyl) of polyethylene glycol Acrylate, mono (meth) acrylate of dipropylene glycol, mono (meth) acrylate of tripropylene glycol, mono (meth) acrylate of polypropylene glycol, 2-hydroxy-3-phenoxypropyl (a) Acrylate, 2-hydroxy-3-butoxypropyl (meth) acrylate, (meth) acrylate tetrahydrofuran ester, caprolactone modified (meth) acrylate tetrahydrofuran ester, (2-ethyl- 2-methyl-1,3-di 4-yl)methyl(meth)acrylate, (2-isobutyl-2-methyl-1,3-di 4-yl)methyl(meth)acrylate, (1,4-dioxaspiro[4,5]indol-2-yl)methyl(meth)acrylate, (meth)acrylic acid epoxy Propyl ester, 3,4-epoxycyclohexylmethyl (meth) acrylate, (3-ethyl propylene oxide-3-yl) methyl (meth) acrylate, 2-(methyl) isocyanate ) propylene oxime ethyl ester, allyl (meth) acrylate, N-(methyl) propylene oxiranyl hexahydro quinone imine, N-(methyl) propylene oxy oxyethyl tetrahydro fluorene Amine, 2-(methyl)propene oxime ethyl hexahydrophthalate, 2-(methyl) propylene oxime ethyl succinate, ω-carboxy-polycaprolactone mono(meth) acrylate, phosphoric acid 2 -(Methyl) propylene oxime ethyl ester, 3-(methyl) propylene oxypropyl trimethoxy decane, 3-(methyl) propylene oxypropyl dimethoxy methyl decane, 3- (A Base) propylene oxypropyl triethoxy decane, and the like.

又作為分子內具有2個以上(甲基)丙烯醯基的(B)成分以外之(甲基)丙烯酸酯類[以下稱為「多官能(甲基)丙烯酸酯」]之具體例,可列舉聚乙二醇二(甲基)丙烯酸酯(碳數15以下之多元醇除外)、聚丙二醇二(甲基)丙烯酸酯(碳數15以下之多元醇除外)、雙酚A環氧烷加成物之二(甲基)丙烯酸酯、胺基甲酸酯(甲基)丙烯酸酯、碳數16以上之聚酯多元醇之(甲基)丙烯酸酯及環氧(甲基)丙烯酸酯等。作為具有3個以上(甲基)丙烯醯基的聚酯(甲基)丙烯酸酯,則可舉出樹枝狀聚合物型(甲基)丙烯酸酯等。 Further, specific examples of the (meth) acrylates (hereinafter referred to as "polyfunctional (meth) acrylates)" other than the component (B) having two or more (meth) acrylonitrile groups in the molecule are exemplified. Polyethylene glycol di(meth)acrylate (excluding polyols having 15 or less carbon atoms), polypropylene glycol di(meth)acrylate (excluding polyols having 15 or less carbon atoms), and bisphenol A alkylene oxide addition The (meth) acrylate, the urethane (meth) acrylate, the (meth) acrylate of the polyester polyol having a carbon number of 16 or more, and the epoxy (meth) acrylate. The polyester (meth) acrylate having three or more (meth) acrylonitrile groups may, for example, be a dendrimer type (meth) acrylate.

作為多官能(甲基)丙烯酸酯之摻混比例,較佳為在組成物中2~20重量%。 The blending ratio of the polyfunctional (meth) acrylate is preferably 2 to 20% by weight in the composition.

作為(甲基)丙烯醯胺類之具體例,可列舉(甲 基)丙烯醯胺、N,N-二甲基(甲基)丙烯醯胺、N,N-二乙基(甲基)丙烯醯胺、N-羥甲基(甲基)丙烯醯胺、N-(3-N,N-二甲胺基丙基)(甲基)丙烯醯胺、亞甲基雙(甲基)丙烯醯胺、伸乙基雙(甲基)丙烯醯胺、N,N-二烯丙基(甲基)丙烯醯胺等。 Specific examples of the (meth) acrylamide are exemplified (A Acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N -(3-N,N-dimethylaminopropyl)(meth)acrylamide, methylenebis(meth)acrylamide, ethyl bis(methyl)propenamide, N,N - Diallyl (meth) acrylamide or the like.

作為順丁烯二醯亞胺類之具體例,可列舉N-甲基順丁烯二醯亞胺、N-羥乙基順丁烯二醯亞胺、N-羥乙基甲順丁烯二醯胺、N-羥乙基甲順丁烯二醯胺與異佛酮二異氰酸酯之胺基甲酸酯化反應物等。 Specific examples of the maleimide group include N-methylbutyleneimine, N-hydroxyethyl maleimide, and N-hydroxyethylmethoxide. a urethane-reacting reaction of decylamine, N-hydroxyethylmethyl maleimide and isophorone diisocyanate.

(B)成分以外之自由基硬化性成分之含有比例以組成物全體為基準,較佳為未滿20重量%。 The content ratio of the radical curable component other than the component (B) is preferably less than 20% by weight based on the entire composition.

<不具硬化性的其他成分> <Other ingredients that are not hardenable>

進而,本發明之光硬化性接著劑中,在不損及本發明效果之範圍內,可任意摻混不具硬化性的其他成分,具體而言可列舉光敏化劑、熱陽離子聚合起始劑、多元醇化合物、水等。 Further, in the photocurable adhesive of the present invention, other components having no curability can be optionally blended insofar as the effects of the present invention are not impaired, and specific examples thereof include a photosensitizer and a thermal cationic polymerization initiator. A polyol compound, water, or the like.

作為光敏化劑之具體例,可列舉二苯甲酮、鄰苯甲醯基苯甲酸甲酯、2-異丙基噻噸酮、9,10-二丁氧基蒽等。此等當中亦有屬於前述(G)成分之光自由基聚合起始劑的化合物,惟此處之所謂「光敏化劑」,係指作為對(C)成分之光陽離子聚合起始劑之敏化劑而作用者。此等可分別單獨使用,亦可混合使用2種以上。 Specific examples of the photosensitizer include benzophenone, methyl ortho-benzoylbenzoate, 2-isopropylthioxanthone, and 9,10-dibutoxyfluorene. Among these, there are also compounds which are photoradical polymerization initiators of the above (G) component, but the term "photosensitizer" as used herein means sensitivity as a photocationic polymerization initiator for the component (C). The agent acts. These may be used alone or in combination of two or more.

光敏化劑之含有比例以組成物全體為基準,較佳為未滿3重量%。 The content ratio of the photosensitizer is preferably less than 3% by weight based on the entire composition.

作為熱陽離子聚合起始劑之具體例,可列舉 苯甲基鋶鹽、四氫噻吩鎓鹽、硫代呋喃鎓鹽、苯甲基銨鹽、吡啶鎓鹽、聯氨鎓鹽、羧酸酯、磺酸酯、胺基醯亞胺等。此等起始劑可容易獲得其市售品,可列舉例如均以商品名所示之“ADEKA OPTON CP77”及“ADEKA OPTON CP66”(以上係ADEKA(股)製)、“CI-2639”及“CI-2624”(以上係日本曹達(股)製)、“SUNAID SI-60L”、“SUNAID SI-80L”及“SUNAID SI-100L”(以上係三新化學工業(股)製)等。 Specific examples of the thermal cationic polymerization initiator include a benzyl sulfonium salt, a tetrahydrothiophene sulfonium salt, a thiofuranium salt, a benzylammonium salt, a pyridinium salt, a hydrazine salt, a carboxylic acid ester, a sulfonate, an amine quinone, or the like. Such a starting agent can be easily obtained as a commercially available product, and examples thereof include "ADEKA OPTON CP77" and "ADEKA OPTON CP66" (the above are manufactured by ADEKA Co., Ltd.) and "CI-2639", both of which are represented by the trade names. "CI-2624" (the above is manufactured by Japan Soda Co., Ltd.), "SUNAID SI-60L", "SUNAID SI-80L", and "SUNAID SI-100L" (the above is manufactured by Sanshin Chemical Industry Co., Ltd.).

熱陽離子聚合起始劑之含有比例以組成物全體為基準,較佳為未滿3重量%。 The content of the thermal cationic polymerization initiator is preferably less than 3% by weight based on the entire composition.

作為多元醇化合物之具體例,可列舉乙二醇、丙二醇、聚醚多元醇化合物、聚酯多元醇化合物、聚己內酯多元醇化合物、聚碳酸酯多元醇化合物等。 Specific examples of the polyol compound include ethylene glycol, propylene glycol, a polyether polyol compound, a polyester polyol compound, a polycaprolactone polyol compound, and a polycarbonate polyol compound.

多元醇化合物之摻混比例以組成物全體為基準,較佳為未滿10重量%。 The blending ratio of the polyol compound is preferably less than 10% by weight based on the entire composition.

本發明光硬化性接著劑之黏度,為了獲得在偏光板之製造步驟能夠使用的塗布性,亦即縱使為薄膜亦為平滑性優良的塗布面,較佳為25℃下的黏度為150mPa‧s以下,更佳為100mPa‧s以下。再佳為50mPa‧s以下。 The viscosity of the photocurable adhesive of the present invention is preferably a coating surface which is excellent in smoothness even when the film is applied, in order to obtain a coating property which can be used in the production step of the polarizing plate. The viscosity at 25 ° C is preferably 150 mPa ‧ s Hereinafter, it is more preferably 100 mPa‧s or less. It is preferably 50mPa‧s or less.

本發明之光硬化性接著劑中,為使對於乾燥度高之偏光膜的接著力為良好,亦可添加少量的水。此時,水的添加量以組成物全體為基準,較佳為未滿3重量%,更佳為未滿1重量%。 In the photocurable adhesive of the present invention, a small amount of water may be added in order to improve the adhesion to the polarizing film having a high degree of dryness. In this case, the amount of water added is preferably less than 3% by weight, and more preferably less than 1% by weight based on the entire composition.

除此等外,只要無損本發明之效果,尚可摻 混離子捕捉劑、抗氧化劑、光安定劑、鏈轉移劑、賦黏劑、熱塑性樹脂、金屬氧化物微粒、消泡劑、色素、有機溶劑等。 In addition to these, as long as the effect of the invention is not impaired, it can be blended Mixed ion trapping agent, antioxidant, light stabilizer, chain transfer agent, tackifier, thermoplastic resin, metal oxide fine particles, antifoaming agent, coloring matter, organic solvent, and the like.

[偏光板] [Polarizer]

以上說明之光硬化性接著劑係用於將保護膜接著在偏光膜,而該偏光膜係包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系樹脂薄膜,保護膜係如此地貼合在偏光膜而成為偏光板。亦即,本發明之偏光板係將保護膜貼合在包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系樹脂薄膜的偏光膜者。保護膜可僅貼合於偏光膜之單面,亦可貼合於偏光膜之兩面。在將保護膜貼合於偏光膜之兩面時,各保護膜可為包含同種樹脂者,也可為包含不同種類之樹脂者。 The photocurable adhesive agent described above is for applying a protective film to a polarizing film, and the polarizing film comprises a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed and has a dichroic dye, and the protective film is thus It is bonded to the polarizing film to form a polarizing plate. In other words, in the polarizing plate of the present invention, the protective film is bonded to a polarizing film comprising a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed and has a dichroic dye. The protective film may be attached only to one side of the polarizing film, or may be attached to both sides of the polarizing film. When the protective film is bonded to both surfaces of the polarizing film, each of the protective films may be one containing the same kind of resin, or may be a resin containing different types.

<偏光膜> <polarized film>

構成偏光膜之聚乙烯醇系樹脂係可藉由將聚乙酸乙烯酯系樹脂皂化而得。作為聚乙酸乙烯酯系樹脂,除乙酸乙烯酯之均聚物的聚乙酸乙烯酯外,可例示乙酸乙烯酯及可與其共聚合之其他單體的共聚物等。作為與乙酸乙烯酯共聚合的其他單體,可列舉例如不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類等。聚乙烯醇系樹脂之皂化度較佳為85~100莫耳%,更佳為98~100莫耳%之範圍。該聚乙烯醇系樹脂可進一步經改質,亦可使用例如經醛類改質的聚乙烯縮甲醛或聚乙烯縮醛等。聚乙烯醇系樹脂之聚合度較佳為1,000~10,000,更佳為1,500~10,000之範圍。 The polyvinyl alcohol-based resin constituting the polarizing film can be obtained by saponifying a polyvinyl acetate-based resin. The polyvinyl acetate-based resin may, for example, be a copolymer of vinyl acetate and another monomer copolymerizable therewith, in addition to polyvinyl acetate of a homopolymer of vinyl acetate. Examples of the other monomer copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The degree of saponification of the polyvinyl alcohol-based resin is preferably from 85 to 100 mol%, more preferably from 98 to 100 mol%. The polyvinyl alcohol-based resin may be further modified, and for example, an aldehyde-modified polyvinyl formal or a polyvinyl acetal may be used. The degree of polymerization of the polyvinyl alcohol-based resin is preferably from 1,000 to 10,000, more preferably from 1,500 to 10,000.

偏光板係經由以下步驟而製造:在此種聚乙烯醇系樹脂薄膜單軸延伸之步驟;將聚乙烯醇系樹脂薄膜以二色性色素染色,使其吸附該二色性色素之步驟;將吸附有二色性色素的聚乙烯醇系樹脂薄膜以硼酸水溶液處理之步驟;在以硼酸水溶液處理後水洗之步驟;及在實施過此等步驟而吸附配向有二色性色素的單軸延伸聚乙烯醇系樹脂薄膜貼合保護膜之步驟。 The polarizing plate is produced by a step of uniaxially stretching the polyvinyl alcohol-based resin film, and a step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye; a step of treating a polyvinyl alcohol-based resin film having a dichroic dye adsorbed with an aqueous solution of boric acid; a step of washing with water after treatment with an aqueous solution of boric acid; and a step of uniaxially stretching the adsorption of a dichroic dye by performing such steps The step of bonding a vinyl alcohol resin film to a protective film.

單軸延伸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,也可在藉由二色性色素之染色後進行。在藉由二色性色素之染色後進行單軸延伸時,該單軸延伸可於硼酸處理之前進行,亦可於硼酸處理中進行。又當然亦可於此等之多個階段中進行單軸延伸。單軸延伸係可於周速不同的輥之間在單軸延伸,亦可利用熱輥在單軸延伸。又,可為在大氣中進行延伸的乾式延伸,亦可為在藉由溶劑而膨潤之狀態下進行延伸的濕式延伸。延伸倍率較佳為4~8倍左右。 The uniaxial stretching may be carried out before the dyeing by the dichroic dye, or simultaneously with the dyeing by the dichroic dye, or after the dyeing by the dichroic dye. When uniaxially stretching is carried out by dyeing with a dichroic dye, the uniaxial stretching can be carried out before the boric acid treatment or in the boric acid treatment. It is of course also possible to carry out a uniaxial extension in several stages of this. The uniaxial extension can be uniaxially stretched between rolls having different peripheral speeds, or can be uniaxially extended by a heat roll. Further, it may be a dry stretching which is extended in the atmosphere, or may be a wet stretching which is extended in a state of being swollen by a solvent. The stretching ratio is preferably about 4 to 8 times.

要將聚乙烯醇系樹脂薄膜以二色性色素染色,例如只要將聚乙烯醇系樹脂薄膜浸漬於含有二色性色素的水溶液即可。作為二色性色素,具體上可使用碘或二色性染料。 When the polyvinyl alcohol-based resin film is dyed with a dichroic dye, for example, the polyvinyl alcohol-based resin film may be immersed in an aqueous solution containing a dichroic dye. As the dichroic dye, iodine or a dichroic dye can be specifically used.

使用碘作為二色性色素時,較佳採用將聚乙烯醇系樹脂薄膜浸漬於含有碘及碘化鉀的水溶液而染色之方法。該水溶液中之碘的含量較佳對每100重量份的水為0.01~0.5重量份左右,碘化鉀的含量較佳對每100重量 份的水為0.5~10重量份左右。該水溶液之溫度較佳為20~40℃左右,又對該水溶液之浸漬時間較佳為30~300秒左右。 When iodine is used as the dichroic dye, a method in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing iodine and potassium iodide and dyed is preferably used. The content of iodine in the aqueous solution is preferably about 0.01 to 0.5 parts by weight per 100 parts by weight of water, and the content of potassium iodide is preferably per 100 parts by weight. The water content is about 0.5 to 10 parts by weight. The temperature of the aqueous solution is preferably about 20 to 40 ° C, and the immersion time of the aqueous solution is preferably about 30 to 300 seconds.

另一方面,使用二色性染料作為二色性色素時,較佳採用將聚乙烯醇系樹脂薄膜浸漬於含有水溶性二色性染料的水溶液而染色之方法。該水溶液中之二色性染料的含量較佳對每100重量份的水為1×10-3~1×10-2重量份左右。該水溶液亦可含有硫酸鈉等無機鹽。該水溶液之溫度較佳為20~80℃左右,又對該水溶液之浸漬時間較佳為30~300秒左右。 On the other hand, when a dichroic dye is used as the dichroic dye, a method in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing a water-soluble dichroic dye and dyed is preferably used. The content of the dichroic dye in the aqueous solution is preferably from about 1 × 10 -3 to 1 × 10 -2 parts by weight per 100 parts by weight of water. The aqueous solution may also contain an inorganic salt such as sodium sulfate. The temperature of the aqueous solution is preferably about 20 to 80 ° C, and the immersion time of the aqueous solution is preferably about 30 to 300 seconds.

藉由二色性色素之染色後的硼酸處理係藉由將染色之聚乙烯醇系樹脂薄膜浸漬於硼酸水溶液而進行。硼酸水溶液中之硼酸的含量較佳對每100重量份的水為2~15重量份左右,更佳為5~12重量份左右。使用碘作為二色性色素時,該硼酸水溶液較佳含有碘化鉀。硼酸水溶液中之碘化鉀的含量較佳對每100重量份的水為2~20重量份左右,更佳為5~15重量份。對硼酸水溶液之浸漬時間較佳為100~1,200秒左右,更佳為150~600秒左右,再佳為200~400秒左右。硼酸水溶液之溫度較佳為50℃以上,更佳為50~85℃。 The boric acid treatment by dyeing the dichroic dye is carried out by immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The content of boric acid in the aqueous boric acid solution is preferably about 2 to 15 parts by weight, more preferably about 5 to 12 parts by weight, per 100 parts by weight of water. When iodine is used as the dichroic dye, the aqueous boric acid solution preferably contains potassium iodide. The content of potassium iodide in the aqueous boric acid solution is preferably from 2 to 20 parts by weight, more preferably from 5 to 15 parts by weight, per 100 parts by weight of water. Immersion time for boric acid aqueous solution It is preferably about 100 to 1,200 seconds, more preferably about 150 to 600 seconds, and preferably about 200 to 400 seconds. The temperature of the aqueous boric acid solution is preferably 50 ° C or higher, more preferably 50 to 85 ° C.

硼酸處理後之聚乙烯醇系樹脂薄膜係經水洗處理。水洗處理係例如藉由將經硼酸處理的聚乙烯醇系樹脂薄膜浸漬於水而適當地進行。水洗後實施乾燥處理,而得到偏光膜。水洗處理中之水的溫度較佳為5~40℃左右,浸漬時間較佳為2~120秒左右。其後所進行之乾 燥處理較佳利用熱風乾燥機或遠紅外線加熱器來進行。乾燥溫度較佳為40~100℃。乾燥處理中之處理時間較佳為120~600秒左右。 The polyvinyl alcohol-based resin film after the boric acid treatment is subjected to a water washing treatment. The water washing treatment is suitably carried out, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. After washing with water, drying treatment was carried out to obtain a polarizing film. The temperature of the water in the water washing treatment is preferably about 5 to 40 ° C, and the immersion time is preferably about 2 to 120 seconds. Afterwards The drying treatment is preferably carried out using a hot air dryer or a far infrared heater. The drying temperature is preferably from 40 to 100 °C. The treatment time in the drying treatment is preferably about 120 to 600 seconds.

如此,即得到一種偏光膜,其係包含吸附配向有二色性色素之碘或二色性染料的聚乙烯醇系樹脂薄膜。 Thus, a polarizing film comprising a polyvinyl alcohol-based resin film which adsorbs iodine or a dichroic dye having a dichroic dye is obtained.

<保護膜> <Protective film>

其次,該偏光膜係使用先前說明之光硬化性接著劑而於其單面或兩面貼合有保護膜。作為偏光膜之保護膜以往所廣泛採用的三乙酸纖維素薄膜係具有約400g/m2/24hr左右之透濕度,惟本發明中,作為貼合於偏光膜之至少一面的保護膜,係採用顯示低於所述三乙酸纖維素之透濕度的樹脂,即聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂或非晶性聚烯烴系樹脂。 Next, the polarizing film is bonded to the one surface or both surfaces of the protective film by using the photocurable adhesive described above. The cellulose triacetate film widely used as a protective film for a polarizing film has a moisture permeability of about 400 g/m 2 /24 hr. However, in the present invention, a protective film which is bonded to at least one side of the polarizing film is used. A resin exhibiting a moisture permeability lower than that of the cellulose triacetate, that is, a polyester resin, a polycarbonate resin, an acrylic resin or an amorphous polyolefin resin.

保護膜所使用之聚酯樹脂的種類不特別限定,但在機械性質、耐溶劑性、刮痕抗性、成本等方面,以聚酞酸乙二酯尤佳。聚酞酸乙二酯係指重複單元的80莫耳%以上以酞酸乙二酯所構成之樹脂,亦可含有源自其他的共聚合成分的構成單元。作為其他的共聚合成分,可列舉如異酞酸、對-β-羥乙氧基苯甲酸、4,4’-二羧基二苯酯、4,4’-二羧基二苯甲酮、雙(4-羧苯基)乙烷、己二酸、癸二酸、5-鈉磺酸基異酞酸及1,4-二羧基環己烷之二羧酸成分;如丙二醇、丁二醇、新戊二醇、二乙二醇、環己二醇、雙酚A之環氧乙烷加成物、聚乙二醇、聚丙二醇及聚伸丁二醇之二醇成分。此等二羧酸成分或二醇 成分亦可視需求分別組合2種以上來使用。又,還可與上述二羧酸成分或二醇成分同時併用如對羥基苯甲酸之羥基羧酸。作為其他的共聚合成分,亦可使用少量具醯胺鍵、胺基甲酸酯鍵、醚鍵、碳酸酯鍵等的二羧酸成分及/或二醇成分。 The type of the polyester resin used for the protective film is not particularly limited, but polyethylene terephthalate is particularly preferable in terms of mechanical properties, solvent resistance, scratch resistance, cost, and the like. The polyethylene terephthalate refers to a resin composed of 80 mol% or more of a repeating unit of ethylene phthalate, and may contain a constituent unit derived from another copolymerized component. Examples of the other copolymerization component include isodecanoic acid, p-β-hydroxyethoxybenzoic acid, 4,4′-dicarboxydiphenyl ester, 4,4′-dicarboxybenzophenone, and bis ( 4-carboxyphenyl)ethane, adipic acid, sebacic acid, 5-sodium sulfonate isophthalic acid and 1,4-dicarboxycyclohexane dicarboxylic acid components; such as propylene glycol, butanediol, new A diol component of pentanediol, diethylene glycol, cyclohexanediol, an ethylene oxide adduct of bisphenol A, polyethylene glycol, polypropylene glycol, and polybutanediol. These dicarboxylic acid components or diols The components may be used in combination of two or more types as needed. Further, a hydroxycarboxylic acid such as p-hydroxybenzoic acid may be used in combination with the above dicarboxylic acid component or diol component. As the other copolymerization component, a small amount of a dicarboxylic acid component and/or a diol component having a guanamine bond, a urethane bond, an ether bond, or a carbonate bond may be used.

作為聚酯樹脂之製造法,可採用使酞酸與乙二醇(進一步視需求之其他的二羧酸及/或其他的二醇)直接反應,即所謂的直接聚合法;使酞酸之二甲酯與乙二醇(進一步視需求之其他的二羧酸之二甲酯及/或其他的二醇)進行酯交換反應,即所謂的酯交換反應法等任意方法。又,聚酯樹脂還可視需求含有周知之添加劑。作為可含有之添加劑,可列舉例如滑劑、抗結塊劑、熱安定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝擊性改良劑等。惟,由於作為積層於偏光薄膜的保護薄膜需具透明性,較佳為此等添加劑的量係控制於最小限度。 As a method for producing the polyester resin, a direct reaction of citric acid with ethylene glycol (further depending on other dicarboxylic acids and/or other diols as required), that is, a so-called direct polymerization method; The methyl ester is subjected to a transesterification reaction with ethylene glycol (further, other dimethyl dicarboxylates and/or other diols as required), that is, any method such as a so-called transesterification reaction. Further, the polyester resin may contain a known additive as needed. Examples of the additives which may be contained include a lubricant, an anti-caking agent, a thermal stabilizer, an antioxidant, an antistatic agent, a light stabilizer, and an impact resistance improver. However, since it is required to have transparency as a protective film laminated on the polarizing film, it is preferable to control the amount of the additive to a minimum.

藉由將上述原料樹脂成形為薄膜狀,並實施單軸延伸或雙軸延伸處理,可製作包含延伸聚酯樹脂的保護薄膜。藉著實施延伸處理,可獲得機械強度高的薄膜。延伸聚酯樹脂薄膜之製作方法係任意,而未特別限定,惟可舉出將使上述原料樹脂熔融並擠製成形為片狀的未配向薄膜,在玻璃轉移溫度以上的溫度以拉幅機橫向延伸後實施熱固定處理之方法。 By forming the raw material resin into a film shape and performing uniaxial stretching or biaxial stretching treatment, a protective film containing an extended polyester resin can be produced. By performing the stretching treatment, a film having high mechanical strength can be obtained. The method for producing the stretched polyester resin film is not particularly limited, and an unaligned film in which the raw material resin is melted and extruded into a sheet shape is used, and the tenter is transversely formed at a temperature higher than the glass transition temperature. The method of performing heat setting treatment after extension.

使用聚酯樹脂作為保護膜時,為獲得良好的接著性,較佳為在塗布接著劑前實施電暈處理、或使用具表面易接著處理層的聚酯樹脂薄膜。 When a polyester resin is used as the protective film, in order to obtain good adhesion, it is preferred to carry out corona treatment before applying the adhesive or to use a polyester resin film having a surface easily treated layer.

保護膜所使用之聚碳酸酯樹脂係由碳酸與二醇或雙酚所形成之聚酯。其中又以分子鏈上具有二苯基烷之芳香族聚碳酸酯係由於耐熱性、耐候性及耐酸性優良,而較佳使用。作為此類聚碳酸酯,可例示衍生自如2,2-雙(4-羥苯基)丙烷(別名雙酚A)、2,2-雙(4-羥苯基)丁烷、1,1-雙(4-羥苯基)環己烷、1,1-雙(4-羥苯基)異丁烷、或1,1-雙(4-羥苯基)乙烷之雙酚類的聚碳酸酯。 The polycarbonate resin used for the protective film is a polyester formed of carbonic acid and a diol or bisphenol. Among them, an aromatic polycarbonate having a diphenyl alkane in a molecular chain is preferably used because of its excellent heat resistance, weather resistance, and acid resistance. As such a polycarbonate, it can be exemplified by, for example, 2,2-bis(4-hydroxyphenyl)propane (alias bisphenol A), 2,2-bis(4-hydroxyphenyl)butane, 1,1-double Polycarbonate of (4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane, or 1,1-bis(4-hydroxyphenyl)ethane .

作為聚碳酸酯樹脂薄膜之製造法,可採用流延製膜法、熔融擠製法等任一種方法。作為具體的製造法之例,可舉出將聚碳酸酯樹脂溶解於適當的有機溶劑而製成聚碳酸酯樹脂溶液,將其在金屬支持體上流延形成網狀物(web),將該網狀物由前述金屬支持體剝離後,熱風乾燥所剝離之網狀物而得到薄膜之方法。 As a method of producing the polycarbonate resin film, any one of a casting film forming method and a melt extrusion method can be employed. As an example of a specific production method, a polycarbonate resin solution is prepared by dissolving a polycarbonate resin in an appropriate organic solvent, and casting it on a metal support to form a web. After the metal material is peeled off from the metal support, the peeled web is dried by hot air to obtain a film.

保護膜所使用之丙烯酸樹脂亦無特別限定,但一般而言係為甲基丙烯酸酯為主要單體的聚合物,較佳為於其中共聚合有少量其他的共單體成分之共聚物。作為丙烯酸樹脂之主成分的甲基丙烯酸酯,較佳為甲基丙烯酸烷基酯,特佳為使用甲基丙烯酸甲酯。又作為共單體成分,一般使用丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基-己酯等。更者,有時亦將如苯乙烯之芳香族乙烯化合物、如丙烯腈之氰乙烯化合物等作為共單體成分。 The acrylic resin to be used for the protective film is not particularly limited, but is generally a polymer in which methacrylate is a main monomer, and a copolymer in which a small amount of other comonomer components are copolymerized is preferable. The methacrylate which is a main component of the acrylic resin is preferably an alkyl methacrylate, and particularly preferably methyl methacrylate. Further, as the comonomer component, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or the like is generally used. Further, an aromatic vinyl compound such as styrene, a cyanoethylene compound such as acrylonitrile, or the like is sometimes used as a comonomer component.

作為丙烯酸樹脂之製造法,可採用一般的塊狀聚合、懸浮聚合、乳化聚合等任意方法。此等當中又特佳採用聚合系統內不存在水溶性成分的塊狀聚合。又 ,為得到適宜的玻璃轉移溫度、或為得到顯示適宜的對薄膜之成形性的黏度,較佳在聚合時使用鏈轉移劑。鏈轉移劑的量只要依據單體之種類及組成來適當決定即可。再者,丙烯酸樹脂亦可視需求含有周知之添加劑。作為周知之添加劑,可列舉例如滑劑、抗結塊劑、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。惟,由於作為積層於偏光薄膜的保護薄膜需具透明性,較佳為此等添加劑的量係控制於最小限度。 As a method of producing the acrylic resin, any method such as general bulk polymerization, suspension polymerization, or emulsion polymerization can be employed. Among these, it is particularly preferable to use a bulk polymerization in which no water-soluble component is present in the polymerization system. also It is preferred to use a chain transfer agent in the polymerization in order to obtain a suitable glass transition temperature or to obtain a viscosity which exhibits a suitable formability to the film. The amount of the chain transfer agent may be appropriately determined depending on the type and composition of the monomer. Further, the acrylic resin may also contain well-known additives as needed. As a known additive, a slip agent, an anti-caking agent, a thermal stabilizer, an antioxidant, an antistatic agent, a light stabilizer, an impact resistance improver, a surfactant, etc. are mentioned, for example. However, since it is required to have transparency as a protective film laminated on the polarizing film, it is preferable to control the amount of the additive to a minimum.

作為丙烯酸樹脂薄膜之製造方法,可採用熔融流延法、T字模法或充氣法等的熔融擠製法、壓光法等任一種方法。其中又以將原料樹脂從例如T字模熔融擠製,使所得之薄膜狀物的至少單面與輥或條帶接觸而製膜之方法,係在可獲得表面性狀良好之薄膜觀點為較佳。 As a method for producing the acrylic resin film, any one of a melt extrusion method, a T-die method, an inflation method, and the like, a melt extrusion method, a calender method, or the like can be employed. Further, a method of forming a film by melt-extruding a raw material resin from, for example, a T-shaped mold, and bringing at least one side of the obtained film material into contact with a roll or a strip is preferable from the viewpoint of obtaining a film having a good surface property.

丙烯酸樹脂,由對薄膜之製膜性或薄膜之耐衝擊性等觀點,亦可含有係衝擊性改良劑之丙烯酸系橡膠粒子。此處之所謂丙烯酸系橡膠粒子,係指以將丙烯酸酯為主體之彈性聚合物作為必須成分的粒子,可舉出實質上僅包含該彈性聚合物之單層結構者、以該彈性聚合物為一層之多層結構者。作為所述彈性聚合物之例,可舉出以丙烯酸烷基酯為主成分,並使可與其共聚合的其他乙烯單體及交聯性單體共聚合的交聯彈性共聚物。作為係為彈性聚合物之主成分的丙烯酸烷基酯,可列舉例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等烷基之碳數為1~8左右者,特佳使用具碳數4 以上之烷基的丙烯酸酯。作為可與該丙烯酸烷基酯共聚合的其他乙烯單體,可舉出分子內具有1個聚合性碳-碳雙鍵的化合物,更具體地可列舉如甲基丙烯酸甲酯之甲基丙烯酸酯、如苯乙烯之芳香族乙烯化合物、如丙烯腈之氰乙烯化合物等。又作為交聯性單體,可舉出分子內具有至少2個聚合性碳-碳雙鍵的交聯性化合物,更具體地可列舉如乙二醇二(甲基)丙烯酸酯及丁二醇二(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)丙烯酸之烯基酯、二乙烯苯等。 The acrylic resin may contain acrylic rubber particles which are impact modifiers, from the viewpoints of film forming properties of the film or impact resistance of the film. The term "acrylic rubber particles" as used herein refers to particles having an elastomeric polymer mainly composed of an acrylate as an essential component, and examples thereof include a single layer structure including substantially only the elastic polymer. A multi-layer structure of one layer. Examples of the elastic polymer include a crosslinked elastic copolymer in which an alkyl acrylate is used as a main component and another ethylene monomer and a crosslinkable monomer copolymerizable therewith are copolymerized. Examples of the alkyl acrylate which is a main component of the elastic polymer include those having an alkyl group such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate having a carbon number of about 1 to 8. Excellent use with carbon number 4 The above alkyl acrylate. Examples of the other ethylene monomer copolymerizable with the alkyl acrylate include a compound having one polymerizable carbon-carbon double bond in the molecule, and more specifically, a methacrylate such as methyl methacrylate. For example, an aromatic vinyl compound such as styrene, a cyanoethylene compound such as acrylonitrile, or the like. Further, examples of the crosslinkable monomer include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, for example, ethylene glycol di(meth)acrylate and butylene glycol. A (meth) acrylate of a di(meth) acrylate polyol, an alkenyl (meth) acrylate such as (meth) acrylate, divinyl benzene or the like.

更者,亦能將包含不含橡膠粒子之丙烯酸樹脂的薄膜與包含含橡膠粒子之丙烯酸樹脂的薄膜之積層物作為保護膜。 Further, a laminate of a film containing an acrylic resin containing no rubber particles and a film containing an acrylic resin containing rubber particles can also be used as a protective film.

使用丙烯酸樹脂作為保護膜時,若使用本發明之組成物,則即使無電暈處理亦可獲得良好的接著性,惟在使接著劑之塗布性為良好、或使接著性更良好之目的,亦可於塗布接著劑前實施電暈處理。 When an acrylic resin is used as the protective film, if the composition of the present invention is used, good adhesion can be obtained without corona treatment, but the coating property of the adhesive is good or the adhesion is further improved. Corona treatment can be performed prior to application of the adhesive.

保護膜所使用之非晶性聚烯烴系樹脂通常具有降莰烯或其衍生物、二甲橋八氫萘之類的衍生自多環式的環狀烯烴之聚合單元,如開環聚合物般殘留有雙鍵時,較佳為氫化該處之熱塑性樹脂。非晶性聚烯烴系樹脂可為環狀烯烴與鏈狀烯烴的共聚物,亦可導入極性基。其中又以熱塑性飽和降莰烯系樹脂為代表性之物。如舉出市售非晶性聚烯烴系樹脂之例,係有JSR(股)之“ARTON”、日本ZEON(股)之“ZEONEX”及“ZEONOR”、三井化學(股)之“APO”及“APEL”等。將非晶性聚烯烴系 樹脂製膜而作成薄膜時,製膜適合使用溶劑流延法、熔融擠製法等周知方法。 The amorphous polyolefin-based resin used for the protective film usually has a polymerized unit derived from a polycyclic cyclic olefin such as a norbornene or a derivative thereof, such as a dicyclic octahydronaphthalene, such as a ring-opening polymer. When a double bond remains, it is preferred to hydrogenate the thermoplastic resin there. The amorphous polyolefin-based resin may be a copolymer of a cyclic olefin and a chain olefin, or may be a polar group. Among them, a thermoplastic saturated decene-based resin is representative. Examples of commercially available amorphous polyolefin-based resins include "ARTON" of JSR (shares), "ZEONEX" and "ZEONOR" of Japan's ZEON (shares), and "APO" of Mitsui Chemicals Co., Ltd. "APEL" and so on. Amorphous polyolefin When the resin is formed into a film to form a film, a known method such as a solvent casting method or a melt extrusion method is preferably used for the film formation.

使用非晶性聚烯烴系樹脂作為保護膜時,為獲得良好的接著性,較佳為塗布接著劑前實施電暈處理。 When an amorphous polyolefin-based resin is used as the protective film, in order to obtain good adhesion, it is preferred to carry out corona treatment before applying the adhesive.

就液晶顯示裝置之視覺辨識側所使用的偏光板而言,可對配置於其視覺辨識側,即液晶胞之相反側的保護膜賦予防眩性。此時,一般係在成為保護膜之視覺辨識側的表面,即與貼合於偏光膜的面為相反側的面上設置具表面凹凸的防眩層。防眩層一般係以對活性能量線硬化性樹脂以壓花法(emboss method)賦予凹凸、或藉由在活性能量線硬化性樹脂中摻混具有與其相異之折射率的微粒並使之硬化來賦予凹凸之方法所形成。又,以丙烯酸樹脂構成保護膜時,以光擴散層與透明層之積層薄膜來構成保護膜亦為有效,其中該光擴散層係在成為黏著劑的丙烯酸樹脂中摻混具有與其相異之折射率的微粒,而該透明層係包含未摻混該所述微粒的丙烯酸樹脂。此時,可採用將包含上述光擴散層與上述透明層之2層的積層薄膜以其光擴散層側貼合於偏光膜之形態;將上述光擴散層之兩面以上述透明層夾持之3層結構的積層薄膜,以其中一透明層貼合於偏光膜之形態等。甚者,即使是將包含此種光擴散層來以賦予防眩性的丙烯酸樹脂積層薄膜作為保護膜時,在其視覺辨識側的表面,即與貼合於偏光膜之面為相反側的面上,設置如上述之防眩層而進一步提高防眩性能亦為有效。 In the polarizing plate used for the visual recognition side of the liquid crystal display device, the anti-glare property can be imparted to the protective film disposed on the opposite side of the liquid crystal cell. In this case, an anti-glare layer having surface irregularities is generally provided on the surface on the side of the visibility side of the protective film, that is, on the surface opposite to the surface to be bonded to the polarizing film. The antiglare layer is generally provided with an embossing method for imparting irregularities to an active energy ray-curable resin, or by hardening and mixing a particle having a refractive index different therefrom in an active energy ray-curable resin. The method of imparting unevenness is formed. Further, when the protective film is made of an acrylic resin, it is also effective to form a protective film by laminating a film of a light-diffusing layer and a transparent layer, wherein the light-diffusing layer is blended in an acrylic resin to be an adhesive to have a refractive index different therefrom. The particles are at a rate, and the transparent layer comprises an acrylic resin that is not blended with the particles. In this case, a laminated film including two layers of the light-diffusing layer and the transparent layer may be bonded to the polarizing film with the light-diffusing layer side; and both surfaces of the light-diffusing layer may be sandwiched by the transparent layer. The laminated film of the layer structure is in the form of a transparent layer attached to the polarizing film or the like. In addition, even when an acrylic resin laminated film including such a light-diffusing layer is provided as an anti-glare property as a protective film, the surface on the side of the visibility side, that is, the surface opposite to the surface to be bonded to the polarizing film Further, it is also effective to provide the antiglare layer as described above to further improve the antiglare property.

如前述,特別是在以丙烯酸樹脂薄膜為保護膜時,先前的專利文獻6(日本特開2004-245925號公報)所示之不含芳香環的環氧樹脂單體,其接著性未必充分,而本發明之組成物,在以所述丙烯酸樹脂薄膜為保護膜時亦可賦予良好的接著力。所以,本發明係在以丙烯酸樹脂薄膜為保護膜時特別有用。 As described above, in particular, when an acrylic resin film is used as a protective film, the epoxy resin-free epoxy resin monomer shown in the prior patent document 6 (JP-A-2004-245925) is not necessarily sufficient. Further, the composition of the present invention can impart a good adhesion when the acrylic resin film is used as a protective film. Therefore, the present invention is particularly useful when an acrylic resin film is used as a protective film.

本發明中,係在偏光膜之至少其中一面,隔著先前所說明之光硬化性接著劑貼合包含選自以上說明之聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之透明樹脂薄膜的保護膜。僅在偏光膜之單面貼合保護膜時,亦可採用例如在偏光膜之另一面直接設置用以貼合於液晶胞等其他的構件的黏著劑層等之形態。 In the present invention, a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin selected from the above-described ones are bonded to at least one of the polarizing films via a photocurable adhesive described above. A protective film of a resin transparent resin film. When the protective film is bonded to one surface of the polarizing film, for example, an adhesive layer or the like for bonding to another member such as a liquid crystal cell may be directly provided on the other surface of the polarizing film.

另一方面,若在偏光膜之兩面貼合保護膜時,各保護膜可為同一種類或亦可為不同種類。具體而言,可採用例如在偏光膜之兩面將聚酯樹脂薄膜作為保護膜而貼合之形態;在偏光膜之兩面將聚碳酸酯樹脂作為保護膜而貼合之形態;在偏光膜之兩面將丙烯酸樹脂作為保護膜而貼合之形態;在偏光膜之兩面將非晶性聚烯烴系樹脂作為保護膜而貼合之形態;在偏光膜之單面將選自聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂的任一種透明樹脂薄膜作為保護膜而貼合,並在偏光膜之另一面,將選自聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂的任一種與上述單面之保護膜不同的透明樹脂薄膜作為保護膜而貼合之形 態等。更且,尚可採用在偏光膜之單面,將選自聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂的任一種透明樹脂薄膜作為保護膜而貼合,並於偏光膜之另一面,將與聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之任一種不同的透明樹脂薄膜作為保護膜而貼合之形態。在偏光膜之兩面貼合保護膜時,可階段性地將2片保護膜單面逐次貼合,亦能將兩面以一階段貼合。 On the other hand, when the protective film is bonded to both surfaces of the polarizing film, the protective films may be of the same type or different types. Specifically, for example, a form in which a polyester resin film is bonded as a protective film on both surfaces of a polarizing film; a form in which a polycarbonate resin is bonded as a protective film on both surfaces of the polarizing film; and both sides of the polarizing film are used a form in which an acrylic resin is bonded as a protective film; an amorphous polyolefin-based resin is bonded as a protective film on both surfaces of the polarizing film; and a single side of the polarizing film is selected from a polyester resin and a polycarbonate. Any of a transparent resin film of a resin, an acrylic resin, and an amorphous polyolefin resin is bonded as a protective film, and is selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous film on the other side of the polarizing film. Any of the transparent polyolefin-based resins and the transparent resin film different from the one-sided protective film as a protective film State and so on. Furthermore, it is also possible to apply a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin as a protective film on one side of the polarizing film, and On the other side of the polarizing film, a transparent resin film different from any one of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin is bonded as a protective film. When the protective film is bonded to both surfaces of the polarizing film, the two protective films can be laminated one by one in a stepwise manner, and the both faces can be bonded in one step.

在偏光膜之兩面貼合保護膜時,使其中之一為與聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂不同的其他的樹脂薄膜時,作為該其他的樹脂之適宜例,可舉出纖維素系樹脂。又,貼合於偏光膜之其中一面的包含聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之保護膜,依本發明,係隔著先前所說明之光硬化性接著劑而接著,但貼合於偏光膜之另一面的保護膜亦可隔著其他的接著劑而接著。舉例來說,在偏光膜之其中一面設置包含纖維素系樹脂薄膜之類的透濕度較高的樹脂薄膜之保護膜時,所述透濕度較高的樹脂薄膜之貼合面亦可使用聚乙烯醇系接著劑等環氧系以外之接著劑。惟,本發明之光硬化性接著劑亦可對此處所例示之纖維素系樹脂薄膜賦予高接著力,因此,在偏光膜之兩面使用同樣的接著劑,係因操作簡單而有利。 When one of the protective films is bonded to both surfaces of the polarizing film, when one of them is a resin film different from the polyester resin, the polycarbonate resin, the acrylic resin, and the amorphous polyolefin resin, the other resin is used. A cellulose resin is mentioned as a suitable example. Further, a protective film comprising a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin bonded to one surface of the polarizing film is subjected to the photocurability described above in accordance with the present invention. Next, the protective film attached to the other surface of the polarizing film may be followed by another adhesive. For example, when a protective film containing a resin film having a high moisture permeability such as a cellulose resin film is provided on one surface of the polarizing film, the bonding surface of the resin film having a high moisture permeability may be polyethylene. An adhesive other than an epoxy type such as an alcohol-based adhesive. However, the photocurable adhesive of the present invention can impart a high adhesion to the cellulose-based resin film exemplified herein. Therefore, it is advantageous to use the same adhesive on both surfaces of the polarizing film because of simple operation.

可使用作為其中一方之保護膜的纖維素系樹脂係纖維素之部分或完全酯化物,可列舉例如纖維素之 乙酸酯、丙酸酯、丁酸酯、彼等之混合酯等。具體地可舉出三乙酸纖維素、二乙酸纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等。若列舉包含此類纖維素酯系樹脂之薄膜的市售品之例,則有富士FILM(股)製“FUJITAC TD80”、“FUJITAC TD80UF”及“FUJITAC TD80UZ”、Konica Minolta Opto(股)製“KC8UX2M”及“KC8UY”等。又,亦可使用經賦予光學補償機能的纖維素系樹脂薄膜。作為所述光學補償薄膜,可列舉例如使纖維素系樹脂含有具相位差調整機能之化合物的薄膜、在纖維素系樹脂薄膜表面塗布有具相位差調整機能之化合物者、將纖維素系樹脂薄膜朝單軸或雙軸延伸所得之薄膜等。若列舉市售纖維素系光學補償薄膜之例,則有富士FILM(股)製“廣視角膜WV BZ 438”及“廣視角膜WV EA”、Konica Minolta Opto(股)製“KC4FR-1”及“KC4HR-1”等。 A part or a complete esterified product of cellulose-based resin-based cellulose as a protective film of one of them may be used, and for example, cellulose may be mentioned. Acetate, propionate, butyrate, mixed esters thereof, and the like. Specific examples thereof include cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, and the like. In the case of a commercially available product including a film of such a cellulose ester resin, there are "FUJITAC TD80", "FUJITAC TD80UF", and "FUJITAC TD80UZ" and "Konica Minolta Opto" ("K") manufactured by Fuji FILM Co., Ltd. KC8UX2M" and "KC8UY" and so on. Further, a cellulose resin film to which an optical compensation function is imparted can also be used. The optical compensation film may, for example, be a film containing a compound having a phase difference adjustment function in a cellulose resin, a compound having a phase difference adjustment function applied to a surface of a cellulose resin film, or a cellulose resin film. The resulting film or the like is extended toward a single axis or a biaxial direction. In the case of a commercially available cellulose-based optical compensation film, there are "wide viewing angle film WV BZ 438" and "wide viewing angle film WV EA" manufactured by Fuji FILM Co., Ltd., and "KC4FR-1" manufactured by Konica Minolta Opto Co., Ltd. And "KC4HR-1" and so on.

作為與聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂不同的其他的樹脂,即可使用作為其中一保護膜之透濕度較低的透明樹脂之例,可列舉聚碸樹脂、脂環族聚醯亞胺樹脂等。 As another resin different from the polyester resin, the polycarbonate resin, the acrylic resin, and the amorphous polyolefin resin, an example of a transparent resin having a low moisture permeability of one of the protective films can be used, and examples thereof include polyfluorene. Resin, alicyclic polyimine resin, and the like.

保護膜係在對偏光膜之貼合前,可在其貼合面實施皂化處理、電暈處理、底塗處理、錨式塗布(anchor coating)處理等的易接著處理。又,在保護膜之與對偏光膜之貼合面為相反側的表面亦可具備硬塗層、抗反射層、防眩層等的各種處理層。保護膜之厚度較佳為5~200μm左右之範圍,更佳為10~120μm,再佳為10~85μm。 The protective film may be subjected to an easy subsequent treatment such as saponification treatment, corona treatment, primer treatment, anchor coating treatment, or the like on the bonding surface before bonding to the polarizing film. Further, the surface of the protective film opposite to the bonding surface to the polarizing film may be provided with various treatment layers such as a hard coat layer, an antireflection layer, and an antiglare layer. The thickness of the protective film is preferably in the range of about 5 to 200 μm, more preferably 10 to 120 μm, and still more preferably 10 to 85 μm.

[偏光板之製造方法] [Method of Manufacturing Polarizing Plate]

本發明之偏光板可藉由包含下列步驟之方法來製造:在先前所說明之偏光膜,與包含選自聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之透明樹脂薄膜的保護膜之貼合面當中的至少一面,塗布先前所說明之光硬化性接著劑的接著劑塗布步驟;隔著所得接著劑層貼合偏光膜與保護膜的貼合步驟;在隔著該接著劑層而貼合偏光膜與保護膜之狀態下使光硬化性接著劑硬化的硬化步驟。 The polarizing plate of the present invention can be produced by a method comprising the steps of: the polarizing film previously described, and a transparent resin comprising a resin selected from the group consisting of polyester resin, polycarbonate resin, acrylic resin, and amorphous polyolefin resin. At least one of the bonding surfaces of the protective film of the film, an adhesive application step of applying the photocurable adhesive described above; a bonding step of bonding the polarizing film and the protective film via the obtained adhesive layer; In the adhesive layer, the photocurable adhesive is cured in a state in which the polarizing film and the protective film are bonded together.

<接著劑塗布步驟> <Binder coating step>

於接著劑塗布步驟中,係在偏光膜與保護膜之貼合面當中的至少一面塗布先前所說明之光硬化性接著劑。對偏光膜或保護膜之表面直接塗布光硬化性接著劑時,其塗布方法無特殊限定。例如可利用刮刀塗布、線棒塗布、模頭塗布、點觸式塗布(comma coating)、凹版塗布等各種塗敷方式。又,亦可利用在偏光膜與保護膜之間使先前所說明之光硬化性接著劑流延後,用輥等加壓而均勻地延展之方法。 In the adhesive application step, the photocurable adhesive described above is applied to at least one of the bonding surfaces of the polarizing film and the protective film. When the photocurable adhesive is directly applied to the surface of the polarizing film or the protective film, the coating method is not particularly limited. For example, various coating methods such as blade coating, wire bar coating, die coating, comma coating, and gravure coating can be used. Further, a method in which the photocurable adhesive described above is cast between the polarizing film and the protective film, and then uniformly pressed by a roller or the like may be used.

接著劑塗布步驟之環境溫度較佳為15~30℃,尤佳為20~25℃。此外,塗布環境之相對濕度較佳為80%以下,更佳為70%以下,再佳為30~70%,尤佳為40~60%。藉由將接著劑塗布步驟之環境溫度與濕度調節於上述範圍,可使接著力展現速度或最終接著力穩定地成為良好。 The ambient temperature of the subsequent coating step is preferably 15 to 30 ° C, and more preferably 20 to 25 ° C. Further, the relative humidity of the coating environment is preferably 80% or less, more preferably 70% or less, still more preferably 30 to 70%, and particularly preferably 40 to 60%. By adjusting the ambient temperature and humidity of the adhesive application step to the above range, the adhesion force display speed or the final adhesion force can be stably made stable.

尚且,環境溫度之外,塗布時之接著劑的溫度,在 藉由低黏度化而改善塗敷性或後述之提升接著力的目的,亦可進行加溫或加熱。此時之加溫或加熱溫度較佳為80℃以下,更佳為20~60℃之範圍。惟,在塗布於薄膜後到進入貼合步驟的期間,使接著劑塗膜暴露於15~30℃、濕度80%以下之環境,在使接著力展現速度或最終接著力成為良好之觀點係較佳。 Moreover, outside the ambient temperature, the temperature of the adhesive at the time of coating is Heating or heating may be performed for the purpose of improving the coating property or the adhesion improving force described later by low viscosity. The heating or heating temperature at this time is preferably 80 ° C or lower, more preferably 20 to 60 ° C. However, after applying the film to the bonding step, the adhesive coating film is exposed to an environment of 15 to 30 ° C and a humidity of 80% or less, and the viewpoint of the adhesion force display speed or the final adhesion force is good. good.

<貼合步驟> <Fitting step>

如此地塗布光硬化性接著劑後,供予貼合步驟。於此貼合步驟中,例如先前之塗布步驟中係在偏光膜表面塗布光硬化性接著劑之情形,則於其疊合保護膜;而先前之塗布步驟中係在保護膜表面塗布光硬化性接著劑的情形,則於其疊合偏光膜。又,在偏光膜與保護膜之間流延光硬化性接著劑的情形,係於該狀態下疊合偏光膜與保護膜。在偏光膜之兩面貼合保護膜的情形,且兩面均使用本發明之光硬化性接著劑之情形,係分別在偏光膜之兩面隔著光硬化性接著劑而疊合保護膜。而且,一般而言,係於此狀態下從兩面(在偏光膜之單面疊合保護膜的情形,係為偏光膜側與保護膜側;而在偏光膜之兩面疊合保護膜時,則為其兩面之保護膜側)用輥等夾持並加壓。此處輥之材質可採用金屬或橡膠等。配置於兩面的輥可為同一材質或不同材質。 After the photocurable adhesive is applied in this manner, a bonding step is provided. In the bonding step, for example, in the case where the photo-curable adhesive is applied to the surface of the polarizing film in the previous coating step, the protective film is laminated thereon; and in the previous coating step, the photo-curing property is applied to the surface of the protective film. In the case of the subsequent agent, the polarizing film is laminated thereon. Further, in the case where the photocurable adhesive is cast between the polarizing film and the protective film, the polarizing film and the protective film are laminated in this state. In the case where the protective film is bonded to both surfaces of the polarizing film, and the photocurable adhesive of the present invention is used on both surfaces, the protective film is laminated on both surfaces of the polarizing film via a photocurable adhesive. Further, in general, in this state, from both sides (in the case where the protective film is superposed on one side of the polarizing film, the polarizing film side and the protective film side are formed; and when the protective film is laminated on both sides of the polarizing film, The protective film side on both sides thereof is sandwiched and pressurized by a roller or the like. Here, the material of the roller may be metal or rubber. The rollers disposed on both sides can be the same material or different materials.

<硬化步驟> <hardening step>

如上述般,呈經由隔著未硬化之光硬化性接著劑而偏光膜與保護膜為貼合狀態者,係接著供予硬化步驟。於此硬化步驟中,係對光硬化性接著劑照射活性能量線 ,使含環氧化合物、(甲基)丙烯酸酯及環氧丙烷化合物等的接著劑層硬化,而接著偏光膜與保護膜。在偏光膜之單面貼合保護膜的情形,活性能量線可自偏光膜側、保護膜側的任一處照射。又,在偏光膜之兩面貼合保護膜的情形,係於偏光膜之兩面分別隔著光硬化性接著劑貼合保護膜之狀態下,自任一保護膜側照射活性能量線而使兩面之光硬化性接著劑同時硬化為有利。惟,當任一保護膜中摻混有紫外線吸收劑的情形(例如以摻混有紫外線吸收劑的纖維素系樹脂薄膜為其中一保護膜時),且活性能量線為紫外線的情形,一般係自另一未摻混紫外線吸收劑的保護膜側照射紫外線。 As described above, the polarizing film and the protective film are bonded to each other via the uncured photocurable adhesive, and the curing step is followed. In this hardening step, the photocurable adhesive is irradiated with an active energy ray. The adhesive layer containing an epoxy compound, a (meth) acrylate, a propylene oxide compound, etc. is hardened, and a polarizing film and a protective film are followed. In the case where the protective film is bonded to one side of the polarizing film, the active energy ray can be irradiated from either the polarizing film side or the protective film side. In the case where the protective film is bonded to both surfaces of the polarizing film, the active energy rays are irradiated from either of the protective film sides in a state in which the protective film is bonded to each other via the photocurable adhesive on both surfaces of the polarizing film. It is advantageous for the hardenable adhesive to harden at the same time. However, when any of the protective films is doped with an ultraviolet absorber (for example, when a cellulose resin film in which an ultraviolet absorber is blended is one of the protective films), and the active energy ray is ultraviolet rays, it is generally Ultraviolet rays are irradiated from the side of the protective film which is not blended with the ultraviolet absorber.

作為活性能量線,可採用可見光線、紫外線、X光、電子束等,惟由處理容易且硬化速度亦充分而言之,一般較佳使用紫外線。活性能量線之光源不特別限定,可採用於波長400nm以下具有發光分布之例如低壓水銀燈、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、LED燈等。 As the active energy ray, visible light, ultraviolet light, X-ray, electron beam or the like can be used. However, since the treatment is easy and the curing speed is sufficient, ultraviolet rays are generally preferably used. The light source of the active energy ray is not particularly limited, and may be used for, for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black light, a microwave-excited mercury lamp, a metal halide lamp, or an LED having a light-emitting distribution with a wavelength of 400 nm or less. Lights, etc.

對光硬化性接著劑之照光強度可按每種目的之組成物來決定,也未特別予以限定,但較佳為聚合起始劑的活性化之有效波長區的照射強度以UV-B(280~320nm之中波長域紫外線)表示係成為1~3,000mW/cm2。若照射強度為上述範圍,則反應時間適當,並可抑制由燈具放射的熱及光硬化性接著劑聚合時的發熱所導致之光硬化性接著劑的黃變或偏光膜的劣化。 The light intensity of the photocurable adhesive can be determined according to the composition of each purpose, and is not particularly limited, but it is preferred that the irradiation intensity of the active wavelength region of the polymerization initiator is UV-B (280). The wavelength of ~320 nm medium wavelength region indicates that the system is 1 to 3,000 mW/cm 2 . When the irradiation intensity is in the above range, the reaction time is appropriate, and yellowing of the photocurable adhesive or deterioration of the polarizing film due to heat emitted from the lamp and heat generated during polymerization of the photocurable adhesive can be suppressed.

對光硬化性接著劑之照光時間可按每種硬化之組成物來控制,亦未特別予以限定,但較佳為以照射強度與照射時間的積所表示之積算光量以UV-B表示係成為10~5,000mJ/cm2。若積算光量為上述範圍,則源自聚合起始劑之活性物種充分產生,接著劑層係充分硬化,且照射時間短、生產性優良。 The illuminating time of the photocurable adhesive can be controlled for each hardened composition, and is not particularly limited. However, it is preferable that the integrated light amount expressed by the product of the irradiation intensity and the irradiation time is expressed by UV-B. 10~5,000mJ/cm 2 . When the integrated light amount is in the above range, the active species derived from the polymerization initiator are sufficiently generated, and the adhesive layer is sufficiently cured, and the irradiation time is short and the productivity is excellent.

當照射活性能量線使光硬化性接著劑硬化之際,較佳係在使偏光膜之偏光度、穿透率及色相及保護膜之透明性等的偏光板之各機能不降低的條件下使之硬化。 When the active energy ray is irradiated to cure the photocurable adhesive, it is preferred that the function of the polarizing plate such as the degree of polarization of the polarizing film, the transmittance, and the transparency of the hue and the protective film are not lowered. Hardening.

如此所得之偏光板中,接著劑層之厚度較佳為50μm以下,更佳為20μm以下,再佳為10μm以下,尤佳為5μm以下。 In the polarizing plate thus obtained, the thickness of the adhesive layer is preferably 50 μm or less, more preferably 20 μm or less, still more preferably 10 μm or less, and still more preferably 5 μm or less.

作為進一步增強本發明接著劑與保護薄膜之接著力的較佳方法,亦可於使用接著劑貼合偏光膜與保護薄膜後,照射活性能量線之前,在不損及偏光膜之光學特性的範圍內加入加熱步驟。作為此時之加熱條件,較佳為設於不發生偏光膜的收縮或光學特性的劣化的範圍內。適宜的加熱條件也會隨丙烯酸樹脂之分子量等而改變,惟可舉出如60℃下1~10秒、40℃下5~30秒等。在加熱後,到照射活性能量線的期間,縱使接著劑之溫度冷卻至40℃以下,亦無損接著力提升效果。 As a preferred method for further enhancing the adhesion between the adhesive of the present invention and the protective film, it is also possible to apply the polarizing film and the protective film after using the adhesive to irradiate the active energy ray without impairing the optical characteristics of the polarizing film. A heating step is added to the inside. The heating condition at this time is preferably set within a range in which shrinkage of the polarizing film or deterioration of optical characteristics does not occur. Suitable heating conditions may vary depending on the molecular weight of the acrylic resin, etc., and may be, for example, 1 to 10 seconds at 60 ° C and 5 to 30 seconds at 40 ° C. After heating, until the temperature of the adhesive is cooled to 40 ° C or less during the irradiation of the active energy ray, the force-improving effect is not impaired.

再者,作為提升本發明接著劑與保護薄膜之接著力的其他較佳方法,尚可舉出縱使不加熱,即縱使在20~25℃下延長貼合偏光膜與保護薄膜後到照射活性能量線 之製造線的長度,而使接著劑與丙烯酸樹脂相接後的時間延長為60秒左右。 Further, as another preferred method for improving the adhesion between the adhesive of the present invention and the protective film, it is possible to illuminate the active energy even after the polarizing film and the protective film are stretched at a temperature of 20 to 25 ° C even without heating. line The length of the manufacturing line is increased by about 60 seconds after the adhesive is brought into contact with the acrylic resin.

[光學構件] [Optical member]

使用偏光板時,也可作成一種光學構件係對其中一側積層顯示偏光機能以外之光學機能的光學層。以形成光學構件為目的而積層於偏光板的光學層,係有例如反射層、半穿透型反射層、光擴散層、相位差板、聚光板、輝度提升薄膜等用於形成液晶顯示裝置等的各種之物。前述之反射層、半穿透型反射層及光擴散層係形成包含反射型或半穿透型、擴散型、此等兩用型偏光板之光學構件時所使用者。 When a polarizing plate is used, it is also possible to form an optical member in which an optical layer other than the optical function of the polarizing function is laminated on one side. An optical layer laminated on the polarizing plate for the purpose of forming an optical member, for example, a reflective layer, a semi-transmissive reflective layer, a light diffusing layer, a phase difference plate, a concentrating plate, a brightness enhancement film, or the like for forming a liquid crystal display device. Various things. The reflective layer, the semi-transmissive reflective layer, and the light-diffusing layer are used to form an optical member including a reflective or semi-transmissive type, a diffusion type, and the like.

反射型偏光板係用於反射來自視覺辨識側的入射光而顯示之類型的液晶顯示裝置,由於可省略背光燈等的光源,易使液晶顯示裝置薄型化。又,半穿透型偏光板係用於在亮處作為反射型顯示、在暗處使用背光燈等的光源而顯示之類型的液晶顯示裝置。作為反射型偏光板之光學構件例如可在偏光膜上的保護膜附設包含鋁等金屬的箔或蒸鍍膜,來形成反射層。作為半穿透型偏光板之光學構件可藉由使前述之反射層為半鏡、或將含有珍珠顏料等而顯示光穿透性的反射板接著於偏光板來形成。另一方面,作為擴散型偏光板之光學構件可採用例如對偏光板上的保護膜實施糙化處理(mat treatment)之方法、塗布含微粒樹脂之方法、接著含微粒薄膜之方法等的各種方法,於表面形成微細凹凸結構。 The reflective polarizing plate is a liquid crystal display device of a type that is used to reflect incident light from the visual recognition side. Since the light source such as a backlight can be omitted, the liquid crystal display device can be made thinner. Further, the semi-transmissive polarizing plate is a liquid crystal display device of a type that is displayed as a reflective display in a bright place and a light source such as a backlight in a dark place. As the optical member of the reflective polarizing plate, for example, a foil containing a metal such as aluminum or a vapor deposited film may be attached to the protective film on the polarizing film to form a reflective layer. The optical member as the semi-transmissive polarizing plate can be formed by subjecting the above-mentioned reflective layer to a half mirror or a reflecting plate which exhibits light transmittance by containing a pearl pigment or the like, followed by a polarizing plate. On the other hand, as the optical member of the diffusing type polarizing plate, for example, a method of performing a mat treatment on a protective film on a polarizing plate, a method of applying a microparticle-containing resin, a method of subsequently including a microparticle-containing film, and the like can be employed. A fine uneven structure is formed on the surface.

更者,作為反射擴散兩用之偏光板之光學構 件的形成係可藉由例如在擴散型偏光板之微細凹凸結構面設置反映該凹凸結構的反射層等的方法來進行。微細凹凸結構之反射層係具有可藉由散射反射使入射光擴散、防止指向性或盲炫、抑制明暗不均之優點等。再者,含有微粒的樹脂層或薄膜還具有使入射光及其反射光在穿透含微粒層時擴散,而能進一步抑制明暗不均等優點。反映表面微細凹凸結構的反射層可藉由真空蒸鍍、離子鍍、濺鍍等蒸鍍或鍍敷等的方法,將金屬直接附設於微細凹凸結構的表面來形成。作為用於形成表面微細凹凸結構而摻混之微粒,可利用例如包含平均粒徑0.1~30μm之氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦等的無機系微粒、包含交聯或未交聯之聚合物等的有機系微粒等。 Moreover, as an optical structure of a polarizing plate for reflection and diffusion The formation of the member can be performed by, for example, providing a reflective layer or the like reflecting the uneven structure on the fine uneven structure surface of the diffusion type polarizing plate. The reflective layer of the fine uneven structure has the advantages of being able to diffuse incident light by scattering reflection, preventing directivity or blindness, and suppressing unevenness of light and dark. Further, the resin layer or film containing fine particles also has the advantage that the incident light and the reflected light thereof are diffused while penetrating the particle-containing layer, and the unevenness of light and dark can be further suppressed. The reflective layer reflecting the fine uneven structure on the surface can be formed by directly attaching a metal to the surface of the fine uneven structure by a method such as vapor deposition or plating such as vacuum deposition, ion plating, or sputtering. As the fine particles to be blended for forming the surface fine uneven structure, for example, inorganic fine particles containing cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, or the like having an average particle diameter of 0.1 to 30 μm can be used. Organic fine particles such as a polymer which is or is not crosslinked.

另一方面,作為上述之光學層的相位差板係以液晶胞所導致之相位差的補償等為目的而使用。作為其例,可列舉包含各種塑膠之延伸薄膜等的雙折射性薄膜、配向固定有盤形液晶或向列型液晶的薄膜、於薄膜基材上形成有上述液晶層者等。此時,作為支持配向液晶層之薄膜基材,較佳使用三乙酸纖維素等纖維素系薄膜。 On the other hand, the phase difference plate as the optical layer described above is used for the purpose of compensating for the phase difference caused by the liquid crystal cell. Examples thereof include a birefringent film including a stretched film of various plastics, a film in which a discotic liquid crystal or a nematic liquid crystal is fixed, and a liquid crystal layer formed on the film substrate. In this case, as the film substrate supporting the alignment liquid crystal layer, a cellulose-based film such as cellulose triacetate is preferably used.

作為形成雙折射性薄膜之塑膠,可列舉例如聚碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚丙烯之類的聚烯烴、聚芳香酯、聚醯胺、非晶性聚烯烴系樹脂等。延伸薄膜係可為以單軸或雙軸等適當之方式處理者。又,亦可為藉由在與熱收縮性薄膜之接著下 附加收縮力及/或延伸力,而控制薄膜的厚度方向之折射率的雙折射性薄膜。再者,相位差板亦可以控制寬頻帶化等的光學特性為目的,而組合使用2片以上。 Examples of the plastic forming the birefringent film include polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, polyolefin such as polypropylene, polyarylate, polyamine, and amorphous. A polyolefin resin or the like. The stretch film system can be treated in a suitable manner such as uniaxial or biaxial. Also, by being followed by a heat shrinkable film A birefringent film that has a contraction force and/or an extension force and controls the refractive index in the thickness direction of the film. Further, the phase difference plate can also control the optical characteristics such as the wide band, and two or more pieces can be used in combination.

聚光板係以控制光路等為目的而使用,能作為稜鏡陣列片、透鏡陣列片或者附圓點片等而形成。 The concentrating sheet is used for the purpose of controlling the optical path and the like, and can be formed as a ytterbium array sheet, a lens array sheet, or a dotted sheet.

輝度提升薄膜係以提升液晶顯示裝置等的輝度為目的而使用,作為其例,可列舉設計成積層多片折射率之各向異性彼此相異的薄膜,而使反射率產生各向異性的反射型直線偏光分離片、於薄膜基材上支持膽固醇型液晶聚合物之配向薄膜或其配向液晶層之圓偏光分離片等。 The luminance-increasing film is used for the purpose of improving the luminance of a liquid crystal display device or the like, and examples thereof include a film in which a plurality of layers of refractive index have different anisotropy, and anisotropic reflection of reflectance. The linear polarizing separation sheet supports an alignment film of a cholesteric liquid crystal polymer or a circularly polarizing separator of the alignment liquid crystal layer on the film substrate.

光學構件,可組合偏光板與視使用目的而選自前述之反射層至半穿透型反射層、光擴散層、相位差板、聚光板、輝度提升薄膜等的1層或2層以上之光學層,作成2層或3層以上之積層體。此時,光擴散層或相位差板、聚光板或輝度提升薄膜等的光學層可分別置配2層以上。此外,各光學層之配置不特別限定。 The optical member may be a combination of a polarizing plate and one or more layers selected from the above-mentioned reflective layer to the semi-transmissive reflective layer, the light diffusing layer, the phase difference plate, the concentrating plate, the luminance lifting film, etc., depending on the purpose of use. The layer is formed into a laminate of 2 or more layers. In this case, two or more optical layers such as a light diffusion layer, a phase difference plate, a concentrating plate, or a brightness enhancement film may be disposed. Further, the arrangement of the respective optical layers is not particularly limited.

形成光學構件的各種光學層係使用接著劑而與偏光板一體化,為此所用之接著劑只要可良好地形成接著層者則不特別限定。由接著作業之簡便性或防止光學應變的產生等觀點,較佳使用黏著劑(亦稱之為「感壓接著劑」)。黏著劑可採用以丙烯酸系聚合物或矽氧系聚合物、聚酯、聚胺基甲酸酯、聚醚等為基底聚合物者。其中又較佳選擇使用如丙烯酸系黏著劑般光學透明性優良、可保持適度的濡濕性或凝聚力、與基材之接著性亦 優異,進而具有耐候性或耐熱性等,且在加熱或加濕條件下不會發生浮起或剝落等剝離問題者。丙烯酸系黏著劑中,摻混具有如甲基或乙基、丁基之碳數為20以下之烷基的(甲基)丙烯酸之烷基酯,與包含(甲基)丙烯酸或(甲基)丙烯酸羥乙酯等的含官能基丙烯酸系單體,並使其聚合成為玻璃轉移溫度較佳為25℃以下,更佳為0℃以下,而重量平均分子量為10萬以上之丙烯酸系共聚物,係有用於作為基底聚合物。 The various optical layers forming the optical member are integrated with the polarizing plate using an adhesive, and the adhesive used for this purpose is not particularly limited as long as the adhesive layer can be favorably formed. Adhesives (also referred to as "pressure-sensitive adhesives") are preferably used from the viewpoint of the convenience of the work or the prevention of the occurrence of optical strain. As the adhesive, an acrylic polymer or a fluorene-based polymer, a polyester, a polyurethane, a polyether or the like can be used as the base polymer. Among them, it is preferable to use an acrylic adhesive such as an optical adhesive, to maintain a moderate wettability or cohesive force, and to adhere to a substrate. It is excellent, and has weather resistance, heat resistance, etc., and does not cause peeling problems such as lifting or peeling under heating or humidification conditions. In the acrylic adhesive, an alkyl ester of (meth)acrylic acid having an alkyl group having a carbon number of 20 or less such as a methyl group or an ethyl group or a butyl group, and (meth)acrylic acid or (meth) group are contained. A functional group-containing acrylic monomer such as hydroxyethyl acrylate is polymerized to obtain 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. It is used as a base polymer.

對偏光板之黏著劑層的形成,可藉由例如使黏著劑組成物溶解或分散於如甲苯或乙酸乙酯之有機溶劑而調製成固體成分濃度10~40重量%的液體,並將其直接塗敷於偏光板上而形成黏著劑層之方式;預先在隔離板薄膜上形成黏著劑層,再將其轉移接著至偏光板上而形成黏著劑層之方式等來進行。黏著劑層之厚度係依據其接著力等來決定,惟1~50μm左右之範圍較為適當。 The formation of the adhesive layer of the polarizing plate can be prepared into a liquid having a solid concentration of 10 to 40% by weight, for example, by dissolving or dispersing the adhesive composition in an organic solvent such as toluene or ethyl acetate, and directly A method of forming an adhesive layer by applying it on a polarizing plate; forming an adhesive layer on the separator film in advance, transferring it to a polarizing plate to form an adhesive layer, or the like. The thickness of the adhesive layer is determined according to the adhesion force, etc., but the range of about 1 to 50 μm is appropriate.

又,黏著層中,還可視需求摻混包含玻璃纖維或玻璃珠、樹脂珠、金屬粉末或其他的無機粉末等的填充劑、顏料或著色劑、抗氧化劑、紫外線吸收劑等。紫外線吸收劑係有水楊酸酯系化合物或二苯甲酮系化合物、苯并三唑系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物等。 Further, in the adhesive layer, a filler, a pigment or a coloring agent, an antioxidant, an ultraviolet absorber, or the like containing glass fibers, glass beads, resin beads, metal powder or other inorganic powder may be blended as needed. The ultraviolet absorber is a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, or a nickel-salted salt-based compound.

[液晶顯示裝置] [Liquid Crystal Display Device]

如以上所述之光學構件可配置於液晶胞之單側或兩側而作成液晶顯示裝置。所使用之液晶胞係任意者,可 使用例如薄膜電晶體型所代表之主動矩陣驅動型、超扭轉向列型所代表之單純矩陣驅動型等的各種液晶胞來形成液晶顯示裝置。設於液晶胞兩側的光學構件可相同,亦可相異。 The optical member as described above can be disposed on one side or both sides of the liquid crystal cell to form a liquid crystal display device. Any of the liquid crystal cell systems used, The liquid crystal display device is formed using various liquid crystal cells such as an active matrix drive type represented by a thin film transistor type and a simple matrix drive type represented by a super twisted nematic type. The optical members disposed on both sides of the liquid crystal cell may be the same or different.

[實施例] [Examples]

以下示出實施例及比較例,更具體地說明本發明,惟本發明不因此等實例所限定。例中,表示用量或含有比例的%,只要未特別記述則為重量基準。又,濕度的%係表示23℃下的相對濕度。再者,「份」如未特別敘明,則意指「重量份」。 The present invention will be more specifically illustrated by the following examples and comparative examples, but the present invention is not limited by the examples. In the examples, the amount used or the % of the content is expressed as a weight basis unless otherwise specified. Further, the % moisture indicates the relative humidity at 23 °C. In addition, "parts" means "parts by weight" unless otherwise stated.

實施例及比較例中,用於光硬化性接著劑組成物的調製之各成分如下所示。以下,茲以化合物名稱或其代號(商品名本身或其一部分)表示。 In the examples and comparative examples, the components used for the preparation of the photocurable adhesive composition are as follows. Hereinafter, it is represented by the compound name or its code (the trade name itself or a part thereof).

(A)成分:環氧化合物(A) component: epoxy compound

CEL-2021:前述式(4)所示之脂環族環氧化合物、DAICEL化學工業(股)製“Celloxide 2021P”。 CEL-2021: an alicyclic epoxy compound represented by the above formula (4), "Celloxide 2021P" manufactured by DAICEL Chemical Industry Co., Ltd.

(B)成分:聚(甲基)丙烯酸酯化合物(B) component: poly(meth) acrylate compound

HDDA:1,6-己二醇二丙烯酸酯、共榮社化學(股)製“輕丙烯酸酯1,6HX-A”。 HDDA: 1,6-hexanediol diacrylate, "light acrylate 1,6HX-A" manufactured by Kyoeisha Chemical Co., Ltd.

(B)’成分:(B)成分以外之(甲基)丙烯酸酯化合物(B)' component: (meth) acrylate compound other than (B) component

M-7100:以3官能以上之聚酯丙烯酸酯為主成分的丙烯酸酯混合物、東亞合成(股)製“ARONIX M-7100”。 M-7100: an acrylate mixture containing a trifunctional or higher polyester acrylate as a main component, and "ARONIX M-7100" manufactured by Toagosei Co., Ltd.

V#1000:樹枝狀聚合物型聚酯丙烯酸酯、大阪有機化學工業(股)製“VISCOAT #1000”。 V#1000: Dendritic polyester acrylate, "VISCOAT #1000" manufactured by Osaka Organic Chemical Industry Co., Ltd.

(C)成分:光陽離子聚合起始劑(C) component: photocationic polymerization initiator

CPI-100P:以三芳基鋶六氟磷酸鹽為主成分的有效成分50%之碳酸丙烯酯溶液、San-Apro(股)製“CPI-100P”。表中係記載有效成分之份數。 CPI-100P: a 50% propylene carbonate solution containing triarylsulfonium hexafluorophosphate as a main component and a "CPI-100P" manufactured by San-Apro Co., Ltd. The table shows the number of parts of the active ingredient.

CPI-110P:三芳基鋶六氟磷酸鹽(有效成分100%)、San-Apro(股)製“CPI-110P”。相當於CPI-100P中的有效成分。 CPI-110P: triarylsulfonium hexafluorophosphate (100% active ingredient), "CPI-110P" manufactured by San-Apro Co., Ltd. It is equivalent to the active ingredient in CPI-100P.

(D)成分:前述式(2)所示之環氧丙烷化合物(D) component: propylene oxide compound represented by the above formula (2)

OXT-101:3-乙基-3-羥甲基環氧丙烷、東亞合成(股)製“ARONE OXETANE OXT-101”。 OXT-101: 3-ethyl-3-hydroxymethyl propylene oxide, "ARONE OXETANE OXT-101" manufactured by Toago Corporation.

(E)成分:(甲基)丙烯酸系聚合物(E) component: (meth)acrylic polymer

BR-80:含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元,Mw95,000、酸價0mgKOH/g之PMMA系聚合物、三菱RAYON(股)製“Dianal BR-80”。 BR-80: a PMMA-based polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 95,000, an acid value of 0 mgKOH/g, and "Dianal BR-80" manufactured by Mitsubishi Rayon Co., Ltd.

BR-83:含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元,Mw40,000、酸價2mgKOH/g之PMMA系聚合物、三菱RAYON(股)製“Dianal BR-83”。 BR-83: a PMMA-based polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 40,000, an acid value of 2 mgKOH/g, and "Dianal BR-83" manufactured by Mitsubishi Rayon Co., Ltd.

BR-87:含有60重量%以上之甲基丙烯酸甲酯作為組成單體單元,Mw25,000、酸價10.5mgKOH/g之PMMA系聚合物、三菱RAYON(股)製“Dianal BR-87”。 BR-87: a PMMA-based polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 25,000, an acid value of 10.5 mgKOH/g, and "Dianal BR-87" manufactured by Mitsubishi Rayon Co., Ltd.

LA2140:Mw80,000、酸價0mgKOH/g。甲基丙烯酸甲酯與丙烯酸丁酯之嵌段共聚物、含有60重量%以上之丙烯酸丁酯作為組成單體單元,兩末端PMMA。Kuraray(股)製“KURARITY LA2140e”。 LA2140: Mw 80,000, acid value 0 mgKOH/g. A block copolymer of methyl methacrylate and butyl acrylate, containing 60% by weight or more of butyl acrylate as a constituent monomer unit, and both ends of PMMA. Kuraray ("KURARITY LA2140e").

LA1114:Mw80,000、酸價0mgKOH/g。甲基丙烯酸 甲酯與丙烯酸丁酯之嵌段共聚物、含有60重量%以上之丙烯酸丁酯作為組成單體單元,單末端PMMA。Kuraray(股)製“KURARITY LA1114”。 LA1114: Mw 80,000, acid value 0 mgKOH/g. Methacrylate A block copolymer of a methyl ester and butyl acrylate, containing 60% by weight or more of butyl acrylate as a constituent monomer unit, and a single-end PMMA. Kuraray ("KURARITY LA1114").

聚合物A:後述製造例1中所得之聚合物。 Polymer A: The polymer obtained in Production Example 1 described later.

(F)成分:前述式(3)所示之環氧丙烷化合物(F) component: propylene oxide compound represented by the above formula (3)

OXT-221:3-乙基-3-[(3-乙基環氧丙烷-3-基)甲氧基甲基]環氧丙烷、東亞合成(股)製“ARONE OXETANE OXT-221”。 OXT-221: 3-ethyl-3-[(3-ethyl propylene oxide-3-yl)methoxymethyl] propylene oxide, "ARONE OXETANE OXT-221" manufactured by Toagos Corporation.

(G)成分:光自由基聚合起始劑(G) component: photoradical polymerization initiator

Irg-184:1-羥基-環己基-苯基-酮、BASF公司製“IRGACURE 184”。 Irg-184: 1-hydroxy-cyclohexyl-phenyl-ketone, "IRGACURE 184" manufactured by BASF Corporation.

Irg-819:雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物、BASF公司製“IRGACURE 819”。 Irg-819: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, "IRGACURE 819" manufactured by BASF Corporation.

(H)成分:調平劑(H) component: leveling agent

BYK-UV3500:BYK(股)製之分子內具有丙烯醯基的矽氧系調平劑“BYK-UV3500”。 BYK-UV3500: BYK-UV3500, a fluorene-based oxime-based leveling agent in the molecule of BYK.

SH-28:DOW CORNING TORAY(股)製之分子內不具丙烯醯基的矽氧系調平劑“DOW CORNING TORAY SH 28 PAINT ADDITIVE”。 SH-28: Dow CORNING TORAY (DOW CORNING TORAY SH 28 PAINT ADDITIVE) which does not have an acrylonitrile group in the molecule.

其他的成分Other ingredients

OXT-212:3-乙基-3-(2-乙基己氧甲基)環氧丙烷、東亞合成(股)製“ARONE OXETANE OXT-212”。 OXT-212: 3-ethyl-3-(2-ethylhexyloxymethyl) propylene oxide, "ARONE OXETANE OXT-212" manufactured by Toagos Corporation.

PC:碳酸丙烯酯(由上述CPI-100P帶入之溶劑) PC: propylene carbonate (solvent brought in by the above CPI-100P)

[製造例1] [Manufacturing Example 1]

使具備滑油套之容量1,000mL之加壓式攪拌槽型反 應器的外套溫度保持於181℃。接著,一面使反應器之壓力保持一定,而開始將包含丙烯酸丁酯(45份)、丙烯酸2-乙基己酯(45份)、甲基丙烯酸甲酯(10份)、作為聚合溶媒之異丙醇(9份)、甲基乙基酮(9份)、作為聚合起始劑之二(三級丁基)過氧化物(0.25份)的單體混合物,以一定的供給速度(48g/分鐘、滯留時間:12分鐘)從原料槽連續供給至反應器,並從出口連續地抽出相當於單體混合物之供給量的反應液。確認了在反應開始後隨即反應溫度暫時下降後,因聚合熱而溫度上升,惟藉由控制滑油套溫度以使反應器之內溫保持於183~185℃。以反應器內溫穩定後36分鐘後之時間點作為反應液之開始採取點,由此起持續反應25分鐘的結果,係供給1.2kg的單體混合液並回收1.2kg的反應液。其後將反應液導入至薄膜蒸發器,分離未反應單體等的揮發成分而去除未反應單體等的揮發成分,得到聚合物「聚合物A」。測定GPC的結果,聚苯乙烯換算之數量平均分子量(Mn)為2,500、重量平均分子量(Mw)為7,500、25℃下之黏度為20,000mPa‧s。 A pressurized stirred tank type with a capacity of 1,000 mL with a lubricating oil jacket The jacket temperature of the reactor was maintained at 181 °C. Next, while maintaining the pressure of the reactor constant, the butyl acrylate (45 parts), 2-ethylhexyl acrylate (45 parts), methyl methacrylate (10 parts), and the polymerization solvent were started. a monomer mixture of propanol (9 parts), methyl ethyl ketone (9 parts), bis(tri-butyl) peroxide (0.25 parts) as a polymerization initiator, at a certain supply rate (48 g/ Minute, residence time: 12 minutes) Continuously supplied to the reactor from the raw material tank, and the reaction liquid corresponding to the supply amount of the monomer mixture was continuously withdrawn from the outlet. It was confirmed that after the reaction was started immediately after the reaction temperature was temporarily lowered, the temperature rose due to the heat of polymerization, but the temperature of the oil jacket was controlled to maintain the internal temperature of the reactor at 183 to 185 °C. The time point after 36 minutes after the internal temperature of the reactor was stabilized was taken as the starting point of the reaction liquid, and as a result of continuing the reaction for 25 minutes, 1.2 kg of the monomer mixture was supplied and 1.2 kg of the reaction liquid was recovered. Thereafter, the reaction liquid is introduced into a thin film evaporator, and volatile components such as unreacted monomers are separated to remove volatile components such as unreacted monomers, thereby obtaining a polymer "polymer A". As a result of measuring GPC, the number average molecular weight (Mn) in terms of polystyrene was 2,500, the weight average molecular weight (Mw) was 7,500, and the viscosity at 25 ° C was 20,000 mPa·s.

[光硬化性接著劑組成物的調製] [Modulation of photocurable adhesive composition]

以各種比例摻混表1及表2所示各成分,依習知方法攪拌混合,而調製成光硬化性接著劑組成物。此外,如前述,由於使用作為(C)成分的“CPI-100P”係含有50%有效成分的碳酸丙烯酯溶液,在表中係將(C)成分與碳酸丙烯酯分開表示。即,表中之“CPI-100P”之摻混量係指有效成分之比例,“CPI-100P”其自身之摻混量則為(C)成分之欄所表示的量與碳酸丙烯酯之欄所表示的量之合計量。 Each component shown in Table 1 and Table 2 was blended in various ratios, and stirred and mixed by a conventional method to prepare a photocurable adhesive composition. Further, as described above, since "CPI-100P" which is a component (C) is used, a propylene carbonate solution containing 50% of an active ingredient is used, and in the table, the component (C) is separately shown from propylene carbonate. That is, the blending amount of "CPI-100P" in the table means the ratio of the active ingredient, and the blending amount of "CPI-100P" itself is the amount indicated by the column of the component (C) and the column of propylene carbonate. The sum of the quantities indicated.

所得之組成物的25℃下之黏度係利用東機產業(股)製E型黏度計來測定。 The viscosity of the obtained composition at 25 ° C was measured by an E-type viscometer manufactured by Toki Sangyo Co., Ltd.

[偏光板的製作] [Production of polarizing plate]

於此,係使用以下的2種薄膜作為保護膜。 Here, the following two types of films are used as a protective film.

延伸降莰烯系樹脂薄膜:厚70μm、商品名“ZEONOR薄膜”、日本ZEON(股)製。對該薄膜實施電暈放電處理後供予與偏光膜貼合。 The decene-based resin film was stretched to a thickness of 70 μm, traded under the trade name “ZEONOR film”, and manufactured by Japan ZEON Co., Ltd. The film is subjected to a corona discharge treatment and then applied to the polarizing film.

丙烯酸樹脂薄膜:厚80μm、商品名“Technolloy S001”、住友化學(股)製。該薄膜亦於實施電暈放電處理後,供予與偏光膜貼合。 Acrylic resin film: 80 μm thick, trade name "Technolloy S001", Sumitomo Chemical Co., Ltd. The film is also applied to the polarizing film after the corona discharge treatment.

在上述延伸降莰烯系樹脂薄膜之電暈放電處理面及丙烯酸樹脂薄膜之電暈放電處理面,以棒塗布機塗敷以上調製之組成物為3μm厚。接著,使於此2片薄膜之間,以夾住聚乙烯醇上吸附配向有碘的偏光膜之方式,用輥同時貼合3片薄膜。對如此而在兩面貼合有保護膜的偏光膜,利用附有帶式輸送機的紫外線照射裝置(燈具係使用EYE GRAPHICS(股)製高壓水銀燈),由延伸降莰烯系樹脂薄膜表面以積算光量250mJ/cm2(UV-B)照射紫外線,使接著劑組成物硬化。 On the corona discharge treated surface of the above-described extended decene-based resin film and the corona discharge treated surface of the acrylic resin film, the composition prepared by the above application was applied to a bar coater to a thickness of 3 μm. Next, three sheets of the film were simultaneously bonded to each other by sandwiching the polarizing film having iodine adsorbed on the polyvinyl alcohol. In this way, the polarizing film to which the protective film is bonded on both sides is formed by extending the surface of the terpene-based resin film by using an ultraviolet irradiation device (a high-pressure mercury lamp made of EYE GRAPHICS) equipped with a belt conveyor. The amount of light of 250 mJ/cm 2 (UV-B) was irradiated with ultraviolet rays to harden the composition of the adhesive.

該實驗係於23℃、相對濕度50%之條件下實施。 The experiment was carried out at 23 ° C and a relative humidity of 50%.

[評定試驗] [assessment test]

對紫外線照射後之偏光板,依以下方法評定接著力展現速度、最終接著力、冷熱循環試驗、耐濕熱試驗及耐濕熱試驗後之接著力,將結果彙整於表1及表2。 For the polarizing plate after the ultraviolet irradiation, the adhesion force, the final adhesion force, the hot and cold cycle test, the damp heat resistance test, and the heat resistance after the damp heat resistance test were evaluated by the following methods, and the results were summarized in Tables 1 and 2.

<接著力展現速度> <Continue force display speed>

照射紫外線後3分鐘後,用手將丙烯酸樹脂薄膜與偏光膜間剝離,此時之接著力愈強,則評定為接著力展現速度愈優良。接著力係基於用手剝離時之情況及力道,依以下4水準判定。 Three minutes after the irradiation of the ultraviolet rays, the acrylic resin film and the polarizing film were peeled off by hand, and at this time, the stronger the force, the better the adhesion speed was evaluated. Then, the force is determined based on the following four levels based on the condition and force of the hand peeling.

◎:丙烯酸樹脂薄膜發生材料破壞。 ◎: Material damage occurred in the acrylic resin film.

○:若緩慢留意地剝離則材料不會破壞,但為強接著力。 ○: The material is not broken if it is slowly peeled off, but it is a strong adhesive force.

△:無發生材料破壞之強度,但未弱到以些微的力道即可剝離之程度。 △: There is no strength at which material damage occurs, but it is not weak to the extent that it can be peeled off with a slight force.

×:以些微的力道即可剝離之非常弱的程度。 ×: A very weak degree can be peeled off with a slight force.

<最終接著力/刀具插入試驗> <Final adhesion/tool insertion test>

照射紫外線後1日後,將美工刀之刀刃由丙烯酸樹脂薄膜上方傾斜插入,由此時之情況及力道,依以下4水準判定。 One day after the irradiation of the ultraviolet ray, the blade of the utility knife was obliquely inserted from above the acrylic resin film, and the situation and force at the time were determined according to the following four levels.

◎:刀刃無法插入、或即使插入時亦有強度,丙烯酸樹脂薄膜破裂。 ◎: The blade cannot be inserted, or has strength even when inserted, and the acrylic film is broken.

○:刀刃可插入但有抵抗力,丙烯酸樹脂薄膜在界面處被切開。 ○: The blade is insertable but resistant, and the acrylic film is cut at the interface.

△:刀刃可插入,但未弱到在界面處僅以些微的力道即可使刀刃前進的程度。 △: The blade can be inserted, but it is not weak enough to advance the blade with only a slight force at the interface.

×:刀刃可插入,且弱到在界面處僅以些微的力道即可使刀刃前進的程度。 ×: The blade can be inserted and weakened to the extent that the blade advances with only a slight force at the interface.

<冷熱循環試驗> <Cold and heat cycle test>

對於照射紫外線後經過2日以上的偏光板實施重複300次放置於-35℃ 60分鐘,接著放置於+70℃ 60分鐘之循 環的冷熱衝擊循環試驗。以目視觀察冷熱循環試驗後之偏光板,依以下3水準判定。 For the polarizing plate after 2 days or more after the irradiation of ultraviolet rays, it was repeatedly placed 300 times at -35 ° C for 60 minutes, and then placed at +70 ° C for 60 minutes. The thermal shock cycle test of the ring. The polarizing plate after the hot and cold cycle test was visually observed and judged according to the following three levels.

○:未確認外觀不良。 ○: The appearance was not confirmed to be defective.

△:確認些許外觀不良。 △: It was confirmed that the appearance was poor.

×:確認外觀不良。 ×: The appearance was poor.

<耐濕熱試驗> <Damp heat resistance test>

將照射紫外線後經過2日以上的偏光板裁切成寬1cm、長6cm,放置於60℃、相對濕度90%之高溫高濕環境下500小時。針對耐濕熱試驗後之偏光板,以目視觀察剝離或變色,依以下3水準判定。 The polarizing plate which had been irradiated with ultraviolet rays for 2 days or more was cut into a width of 1 cm and a length of 6 cm, and placed in a high-temperature and high-humidity environment of 60 ° C and a relative humidity of 90% for 500 hours. For the polarizing plate after the damp heat resistance test, peeling or discoloration was visually observed, and it was judged by the following three levels.

○:未見剝離或變色。 ○: No peeling or discoloration was observed.

△:確認些許剝離或變色。 △: A slight peeling or discoloration was confirmed.

×:確認剝離或變色。 ×: Peeling or discoloration was confirmed.

<耐濕熱試驗後之端部接著性評定> <End-end evaluation after moisture and heat resistance test>

耐濕熱試驗結束後,迅速地移動至23℃、相對濕度50%之環境,藉由拉引偏光板的角部來由評定由高溫高濕環境取出5分鐘後之接著性。此時,使丙烯酸樹脂於內側而用手將角部5mm 90°彎曲後,瞬間將手放開,評定是否發生剝離10次以上,依以下3水準判定。 After the end of the damp heat resistance test, the environment was quickly moved to 23 ° C and a relative humidity of 50%, and the adhesion of the polarizing plate was pulled to evaluate the adhesion after 5 minutes from the high temperature and high humidity environment. At this time, the acrylic resin was bent inside and the corners were bent by 5 mm by 90°, and then the hands were released, and it was evaluated whether or not peeling occurred 10 times or more, and the following three levels were determined.

○:在10次以上未見剝離。 ○: No peeling was observed 10 times or more.

△:平均在3次~9次間可見剝離。 △: Peeling was observed on average between 3 and 9 times.

×:在2次以下可見剝離。 ×: Peeling was observed twice or less.

<耐濕熱試驗後之丙烯酸樹脂彎曲接著力> <Acrylic resin bending adhesion force after moisture resistance test>

耐濕熱試驗結束後,迅速地移動至23℃、相對濕度50%之環境,使丙烯酸樹脂朝上而將偏光板黏貼於玻璃 板,在由高溫高濕環境取出5分鐘後及15小時後,以拉伸速度60mm/分鐘180°剝離丙烯酸樹脂而測定接著力。由此時之強度及丙烯酸樹脂材料破化之情況,依下述4水準判定。 After the end of the damp heat test, quickly move to an environment of 23 ° C and a relative humidity of 50%, and make the acrylic resin face up and stick the polarizing plate to the glass. After the plate was taken out from a high-temperature and high-humidity environment for 5 minutes and 15 hours, the acrylic resin was peeled off at a tensile speed of 60 mm/min and 180°, and the adhesion was measured. The strength at this time and the breakage of the acrylic resin material were determined according to the following four levels.

◎:6N/cm以上或無法剝離 ◎: 6N/cm or more or cannot be peeled off

○:3N/cm以上或於剝離中途丙烯酸樹脂發生材料破壞 ○: 3 N/cm or more or material destruction of acrylic resin during peeling

△:0.1N/cm以上且未滿3N/cm △: 0.1 N/cm or more and less than 3 N/cm

×:未滿0.1N/cm ×: less than 0.1 N/cm

表1及表2之摻混組成中之各數值的單位係重量%。 The unit of each numerical value in the blending composition of Tables 1 and 2 is % by weight.

首先,就實施例1~實施例9加以說明。 First, the first embodiment to the ninth embodiment will be described.

作為本發明接著劑組成物的實施例1~實施例9之組成物,係不僅是黏度、接著力展現速度、最終接著力、冷熱循環試驗、耐濕熱試驗及耐濕熱試驗結束後15小時後之接著力優良,耐濕熱試驗結束後,取出5分鐘後之接著力亦良好。因此,不僅作為偏光板用接著劑之基本性 能優異,在高溫高濕環境下運送隨後之可靠度亦得以提升。 The compositions of Examples 1 to 9 which are the composition of the adhesive of the present invention are not only the viscosity, the adhesion display speed, the final adhesion force, the hot and cold cycle test, the damp heat resistance test, and the heat and humidity test after 15 hours. Then, the force was excellent, and after the end of the moist heat resistance test, the adhesion force after taking out for 5 minutes was also good. Therefore, not only as the basicity of the adhesive for polarizing plates Excellent performance, and the reliability of transportation in high temperature and high humidity environment is also improved.

此等當中,實施例7~實施例9之組成物,若欲在耐濕熱試驗結束後彎曲剝離丙烯酸樹脂,則丙烯酸樹脂立即發生破壞而無法剝離。亦即,耐濕熱試驗結束隨後之接著力係更進一步提升。 Among these, in the compositions of Examples 7 to 9, if the acrylic resin was bent and peeled off after the endurance test, the acrylic resin immediately broke and could not be peeled off. That is, the end of the heat and humidity resistance test is further enhanced.

更者,使用聚合物A之實施例9之組成物其25℃下之黏度為50mPa‧s以下,塗敷性亦優良。 Further, the composition of Example 9 using the polymer A had a viscosity at 25 ° C of 50 mPa ‧ s or less, and was excellent in coatability.

其次,對比較例1加以說明。 Next, Comparative Example 1 will be described.

不含(E)成分之比較例1的組成物,係黏度、接著力展現速度、最終接著力、冷熱循環試驗及耐濕熱試驗優良之物,且耐濕熱試驗結束後15小時後之接著力亦優異,惟耐濕熱試驗結束後5分鐘後之接著力大幅下降。 The composition of Comparative Example 1 containing no (E) component was excellent in viscosity, adhesion display speed, final adhesion, cold cycle test, and damp heat resistance test, and the adhesion force after 15 hours after the end of the damp heat test was also Excellent, but the adhesion after 5 minutes after the end of the damp heat test was greatly reduced.

[產業上之可利用性] [Industrial availability]

本發明之光硬化性接著劑組成物係低黏度且容易塗敷為薄膜狀,照光後之偏光膜與保護膜之接著力展現速度及最終接著力優良、耐濕熱試驗結束隨後之接著力亦優良,而因所得之偏光板的耐久性亦優異,可適宜地使用於偏光板的製造。 The photocurable adhesive composition of the present invention has a low viscosity and is easily applied as a film, and the adhesion speed and final adhesion of the polarizing film and the protective film after illumination are excellent, and the adhesion resistance is excellent after the end of the moist heat test. Further, since the obtained polarizing plate is excellent in durability, it can be suitably used for the production of a polarizing plate.

Claims (17)

一種光硬化性接著劑組成物,係用於在偏光膜接著保護膜之接著劑組成物,其中該偏光膜係包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系樹脂薄膜,該保護膜係包括選自包含聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之群組中的透明樹脂薄膜,該光硬化性接著劑組成物之特徵為含有:(A)分子內具有至少2個下式(1)所示之脂環族環氧基的環氧化合物; (B)具碳數2~15個之多元醇的聚(甲基)丙烯酸酯;(C)光陽離子聚合起始劑;(D)下式(2)所示之環氧丙烷化合物;及 (E)以(甲基)丙烯酸烷基酯為必須組成單體單元的聚合物,且在組成物中該(A)~(E)成分之含有比例為(A)成分:10~65重量%(B)成分:10~55重量%(C)成分:0.5~10重量%(D)成分:1~25重量%(E)成分:0.1~25重量%。 A photocurable adhesive composition for use in an adhesive composition of a polarizing film followed by a protective film, wherein the polarizing film comprises a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed and has a dichroic dye, The protective film includes a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin, and the photocurable adhesive composition is characterized by containing: A) an epoxy compound having at least two alicyclic epoxy groups represented by the following formula (1) in the molecule; (B) a poly(meth)acrylate having a carbon number of 2 to 15 polyols; (C) a photocationic polymerization initiator; (D) a propylene oxide compound represented by the following formula (2); (E) A polymer having a (meth)acrylic acid alkyl ester as an essential constituent monomer unit, and the content ratio of the component (A) to (E) in the composition is (A) component: 10 to 65 wt% (B) Component: 10 to 55% by weight (C) Component: 0.5 to 10% by weight (D) Component: 1 to 25% by weight (E) Component: 0.1 to 25% by weight. 如請求項1之光硬化性接著劑組成物,其中(A)成分係 下式(4)所示之環氧化合物: The photocurable adhesive composition of claim 1, wherein the component (A) is an epoxy compound represented by the following formula (4): 如請求項1之光硬化性接著劑組成物,其中(B)成分係二(甲基)丙烯酸酯,其係具碳數5~10個之二醇,但是環氧烷單元之重複數為3以上的聚醚二醇除外。 The photocurable adhesive composition according to claim 1, wherein the component (B) is a di(meth)acrylate having a carbon number of 5 to 10, but the repeating number of the alkylene oxide unit is 3. Except for the above polyether diol. 如請求項1之光硬化性接著劑組成物,其中(A)成分及(B)成分之含有比例係於組成物中分別為10~50重量%及20~45重量%。 The photocurable adhesive composition according to claim 1, wherein the content ratio of the component (A) and the component (B) is 10 to 50% by weight and 20 to 45% by weight, respectively, based on the composition. 如請求項1之光硬化性接著劑組成物,其中(E)成分係包含:含有含碳數1~10之烷基的(甲基)丙烯酸烷基酯作為組成單體單元,且重量平均分子量為1,000~500,000的聚合物。 The photocurable adhesive composition of claim 1, wherein the component (E) comprises: an alkyl (meth)acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit, and a weight average molecular weight It is a polymer of 1,000 to 500,000. 如請求項5之光硬化性接著劑組成物,其中(E)成分係包含:含有60重量%以上100重量%以下之甲基丙烯酸甲酯作為組成單體單元,且重量平均分子量為1,000~200,000的聚合物。 The photocurable adhesive composition according to claim 5, wherein the component (E) comprises: 60% by weight or more and 100% by weight or less of methyl methacrylate as a constituent monomer unit, and a weight average molecular weight of 1,000 to 200,000 Polymer. 如請求項5之光硬化性接著劑組成物,其中(E)成分係包含:含有60重量%以上100重量%以下之含碳數1~10之烷基的丙烯酸烷基酯作為組成單體單元,且重量平均分子量為1,000~200,000的聚合物。 The photocurable adhesive composition according to claim 5, wherein the component (E) comprises: an alkyl acrylate containing 60% by weight or more and 100% by weight or less of an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit; And a polymer having a weight average molecular weight of 1,000 to 200,000. 如請求項7之光硬化性接著劑組成物,其中(E)成分係包含以高溫聚合所得之聚合物,該聚合物係含有60重量%以上100重量%以下之含碳數1~10之烷基的丙烯酸烷 基酯作為組成單體單元,且重量平均分子量為1,000~20,000。 The photocurable adhesive composition according to claim 7, wherein the component (E) comprises a polymer obtained by high temperature polymerization, and the polymer contains 60% by weight or more and 100% by weight or less of a carbon number of 1 to 10 carbon atoms. Acrylate The base ester is a constituent monomer unit and has a weight average molecular weight of 1,000 to 20,000. 如請求項1之光硬化性接著劑組成物,其中進一步在組成物中以1~30重量%之含有比例含有下式(3)所示之環氧丙烷化合物作為(F)成分: The photocurable adhesive composition according to claim 1, wherein the propylene oxide compound represented by the following formula (3) is further contained in the composition in an amount of from 1 to 30% by weight as the component (F): 如請求項1之光硬化性接著劑組成物,其中進一步在組成物中以0.1~10重量%之比例含有(G)光自由基聚合起始劑。 The photocurable adhesive composition according to claim 1, wherein the (G) photoradical polymerization initiator is further contained in the composition in an amount of 0.1 to 10% by weight. 如請求項10之光硬化性接著劑組成物,其中(G)成分係含有醯基膦氧化物化合物。 The photocurable adhesive composition of claim 10, wherein the component (G) contains a mercaptophosphine oxide compound. 如請求項1之光硬化性接著劑組成物,其中進一步在組成物中含有0.01~0.5重量%之(H)調平劑。 The photocurable adhesive composition of claim 1, wherein the composition further contains 0.01 to 0.5% by weight of a (H) leveling agent. 一種偏光板,其係經由接著劑而於偏光膜貼合保護膜而成之偏光板,其中該偏光膜係包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系樹脂薄膜,該保護膜係包括選自包含聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之群組中的透明樹脂薄膜,該偏光板之特徵為該接著劑係由如請求項1至12中任一項之光硬化性接著劑組成物形成。 A polarizing plate comprising a polarizing film in which a protective film is bonded to a polarizing film via an adhesive, wherein the polarizing film comprises a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed and has a dichroic dye. The protective film system includes a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin-based resin, and the polarizing plate is characterized in that the adhesive is as claimed in claim 1 The photocurable adhesive composition of any one of 12 is formed. 一種偏光板之製造方法,其係經由接著劑而於偏光膜貼合保護膜來製造偏光板之方法,其中該偏光膜係包含經單軸延伸且吸附配向有二色性色素之聚乙烯醇系 樹脂薄膜,該保護膜係包括選自包含聚酯樹脂、聚碳酸酯樹脂、丙烯酸樹脂及非晶性聚烯烴系樹脂之群組中的透明樹脂薄膜,該製造方法之特徵為包含:接著劑塗布步驟,係在該偏光膜與該保護膜之貼合面中的至少一面塗布如請求項1至12中任一項之光硬化性接著劑組成物;貼合步驟,係隔著所得之接著劑層貼合該偏光膜與該保護膜;及硬化步驟,係使該光硬化性接著劑組成物在偏光膜與保護膜隔著該接著劑層而貼合的狀態下硬化。 A method for producing a polarizing plate, which is a method for producing a polarizing plate by bonding a protective film to a polarizing film via an adhesive, wherein the polarizing film comprises a polyvinyl alcohol-based uniaxially stretched and adsorbed dichroic dye a resin film comprising a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin, the manufacturing method characterized by: an adhesive coating a step of applying a photocurable adhesive composition according to any one of claims 1 to 12 on at least one of a bonding surface of the polarizing film and the protective film; and a bonding step of separating the obtained adhesive The polarizing film and the protective film are bonded to the layer; and the curing step is performed by bonding the photocurable adhesive composition to a state in which the polarizing film and the protective film are bonded to each other via the adhesive layer. 一種光學構件,其特徵為在如請求項13之偏光板積層有其他的光學層。 An optical member characterized by having another optical layer laminated on a polarizing plate as claimed in claim 13. 如請求項15之光學構件,其中其他的光學層係包含相位差板。 The optical member of claim 15, wherein the other optical layers comprise phase difference plates. 一種液晶顯示裝置,其特徵為使如請求項15之光學構件配置於液晶胞之單側或兩側而成。 A liquid crystal display device characterized in that an optical member as claimed in claim 15 is disposed on one side or both sides of a liquid crystal cell.
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