TWI494399B - Photo-cured adhesive composition, polarizing plate and producing method for the same, optical member and liquid crystal display device - Google Patents
Photo-cured adhesive composition, polarizing plate and producing method for the same, optical member and liquid crystal display device Download PDFInfo
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- TWI494399B TWI494399B TW099105772A TW99105772A TWI494399B TW I494399 B TWI494399 B TW I494399B TW 099105772 A TW099105772 A TW 099105772A TW 99105772 A TW99105772 A TW 99105772A TW I494399 B TWI494399 B TW I494399B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13356—Structural association of cells with optical devices, e.g. polarisers or reflectors characterised by the placement of the optical elements
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Polarising Elements (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Liquid Crystal (AREA)
Description
本發明係有關在偏光板中黏貼偏光件(polarizer)與保護膜時使用之光硬化性接著劑組成物、使用該接著劑組成物在偏光件黏貼保護膜之偏光板、及該偏光板之製造方法。又，本發明也有關使用該偏光板之光學構材及液晶顯示裝置。The present invention relates to a photocurable adhesive composition used for bonding a polarizer and a protective film in a polarizing plate, a polarizing plate using the adhesive composition to adhere a protective film to a polarizing member, and the manufacture of the polarizing plate method. Further, the present invention relates 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之光學零件之一。通常，偏光板是以在偏光件之兩面積層保護膜之狀態下，組裝到液晶顯示裝置中而使用。雖然也知道有只在偏光件之單面設置保護膜之情形，但大部分之情形，是在另一面上黏貼不僅作為保護膜且亦具有其他光學機能之層而兼作為保護膜。又，就偏光件之製造方法而言，廣為人知者有：將藉由二色性色素染色之單軸延伸聚乙烯醇樹脂薄膜經硼酸處理、水洗後，乾燥之方法。The polarizing plate is used as one of optical parts constituting a liquid crystal display device. Usually, the polarizing plate is used by being assembled in a liquid crystal display device in a state in which the protective film is applied to the two layers of the polarizing member. Although it is also known that a protective film is provided only on one side of the polarizing member, in most cases, a protective film is used as a protective film on the other surface not only as a protective film but also as a layer of other optical functions. Further, as a method for producing a polarizing material, a method of drying a uniaxially stretched polyvinyl alcohol resin film dyed with a dichroic dye by boric acid treatment, washing with water, and drying is widely known.
通常，偏光件是於上述水洗及乾燥之後，直接黏貼保護膜。此係由於乾燥後之偏光件的物理性強度弱，若暫時將其捲取，則在加工方向會發生破裂等問題之故。因而，通常乾燥後之偏光件是在直接塗布水系接著劑之後，隔著該接著劑而同時在兩面黏貼保護膜。通常作為保護膜者，係使用厚度30至120μm之三乙醯基纖維素薄膜。Usually, the polarizer is directly adhered to the protective film after the above washing and drying. This is because the physical strength of the polarizer after drying is weak, and if it is temporarily taken up, problems such as cracking occur in the machine direction. Therefore, in general, after drying the polarizer, the protective film is adhered to both surfaces of the polarizer after the direct application of the water-based adhesive. As a protective film, a triethylenesulfonated cellulose film having a thickness of 30 to 120 μm is used.
偏光件與保護膜的接著，尤其是與由三乙醯基纖維素薄膜所成之保護膜的接著，雖然很多是使用聚乙烯醇系之接著劑，但也有試著使用胺酯(urethane)系之接著劑以取代該接著劑。例如，在日本特開平7-120617號公報(專利文獻1)中，揭示以胺酯預聚物當作接著劑，將含水率高的偏光件與醋酸纖維素系保護膜(例如三乙醯基纖維素薄膜)予以接著。The polarizer and the protective film are followed by a protective film made of a triethylenesulfonated cellulose film. Although many of the polyvinyl alcohol-based adhesives are used, there are also attempts to use an urethane system. An adhesive is substituted for the adhesive. Japanese Patent Publication No. 7-120617 (Patent Document 1) discloses a polarizing member having a high water content and a cellulose acetate-based protective film (for example, triethylenesulfonyl group) using an amine ester prepolymer as an adhesive. The cellulose film) is followed.
另一方面，由於三乙醯基纖維素之透濕度高，將此樹脂薄膜當作保護膜而黏貼在兩面之偏光板，係在濕熱下，例如在如溫度70℃、相對濕度90%的條件下，會有引起劣化等之問題。在此，也有提案藉由以透濕度較三乙醯基纖維素薄膜更低之樹脂薄膜作為保護膜而解決該問題之方法，例如，已知有將非晶性聚烯烴系樹脂當作保護膜。具體上，在日本特開平6-51117號公報(專利文獻2)中揭示在偏光件之至少一面上，將熱可塑性飽和降冰片烯系樹脂薄片作為保護膜並加以積層。On the other hand, due to the high moisture permeability of the triethylenesulfonyl cellulose, the resin film is adhered to the polarizing plate on both sides as a protective film, under conditions of damp heat, for example, at a temperature of 70 ° C and a relative humidity of 90%. Underneath, there will be problems such as deterioration. Here, there has also been proposed a method of solving this problem by using a resin film having a lower moisture permeability than a triethylenesulfonated cellulose film as a protective film. 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), it is disclosed that a thermoplastic resin-borne norbornene-based resin sheet is used as a protective film on at least one surface of a polarizing member and laminated.
當使用以往之裝置黏貼此等透濕度低之保護膜時，在使用以水作為主溶劑的接著劑，例如聚乙烯醇水溶液，而於聚乙烯醇系的偏光件黏貼保護膜後，再將溶劑乾燥之所謂濕壓膜法(Wet Lamination)中，有得不到充分之接著強度、或外觀變得不良等問題。此係由於透濕度低之薄膜一般是較三乙醯基纖維素薄膜更為疏水性、或因為透濕度低，所以無法使作為溶劑之水充分乾燥等理由之故。When a protective film having a low moisture permeability is adhered by a conventional device, an adhesive agent using water as a main solvent, such as an aqueous solution of polyvinyl alcohol, is used, and after the polyvinyl alcohol-based polarizing member is adhered to the protective film, the solvent is further applied. In the so-called Wet Lamination method of drying, there is a problem that sufficient adhesive strength or poor appearance is not obtained. This is because the film having a low moisture permeability is generally more hydrophobic than the triethylenesulfonated cellulose film or because the moisture permeability is low, so that the water as a solvent cannot be sufficiently dried.
在此，日本特開2000-321432號公報(專利文獻3)中，提議將聚乙烯醇系的偏光件、與由熱可塑性飽和降冰片烯系樹脂所成之保護膜，藉由聚胺酯(polyurethane)系接著劑而予以接著。但是，聚胺酯系接著劑有硬化需要長時間之問題，又，接著力未必足夠。Japanese Laid-Open Patent Publication No. 2000-321432 (Patent Document 3) proposes a polyvinyl alcohol-based polarizer and a protective film made of a thermoplastic saturated norbornene-based resin, which is made of polyurethane. It is followed by an adhesive. However, the polyurethane adhesive has a problem that it takes a long time to harden, and the subsequent force is not necessarily sufficient.
另一方面，也已知有在偏光件之兩面黏貼不同種類之保護膜，例如，在日本特開2002-174729號公報(專利文獻4)中，揭示在由聚乙烯醇系樹脂薄膜所成的偏光件之一面上黏貼由非晶性聚烯烴系樹脂所成的保護膜，在另一面上黏貼與該非晶性聚烯烴系樹脂不同的樹脂，例如由三乙醯基纖維素所成之保護膜，在日本特開2005-208456號公報(專利文獻5)中，提議在由聚乙烯醇系樹脂所成之偏光薄膜的一面上，隔著含有特定胺酯樹脂之水系第一接著劑而積層環烯烴系樹脂薄膜，在另一面上，隔著與第一接著劑不同之水系第二接著劑，例如聚乙烯醇系樹脂之水溶液，而積層醋酸纖維素系樹脂薄膜。On the other hand, it is also known that a different type of protective film is adhered to both surfaces of a polarizing member, and it is disclosed in Japanese Laid-Open Patent Publication No. 2002-174729 (Patent Document 4). A protective film made of an amorphous polyolefin resin is adhered to one surface of the polarizing member, and a resin different from the amorphous polyolefin resin is adhered to the other surface, for example, a protective film made of triacetyl cellulose. In Japanese Laid-Open Patent Publication No. 2005-208456 (Patent Document 5), it is proposed to laminate a ring on one surface of a polarizing film made of a polyvinyl alcohol-based resin via a water-based first adhesive containing a specific amine ester resin. On the other surface, the olefin-based resin film is laminated with a water-based second adhesive different from the first adhesive, for example, an aqueous solution of a polyvinyl alcohol-based resin.
在上述專利文獻4中稱為非晶性聚烯烴系樹脂者，或在上述專利文獻5中稱為環烯烴系樹脂者，係指如降冰片烯或其衍生物、二甲橋八氫萘(dimethanooctahydronaphthalene)等具有由多環式環烯烴所成之單體單位，且在如開環聚合物般殘留有雙鍵時較佳是對其加氫的熱可塑性樹脂。In the case of the above-mentioned Patent Document 4, which is referred to as an amorphous polyolefin-based resin, or in the above-mentioned Patent Document 5, it is referred to as a cycloolefin-based resin, and means, for example, norbornene or a derivative thereof, or dimethyl bridge octahydronaphthalene ( A dimethanooctahydronaphthalene) or the like which has a monomer unit derived from a polycyclic cyclic olefin and which is preferably hydrogenated when a double bond remains as in the case of a ring-opening polymer.
又，在日本特開2004-245925號公報(專利文獻6)中揭示以不含芳香環之環氧樹脂作為主成分之接著劑，並提案對該接著劑照射活性能源線後藉由陽離子聚合而使偏光件與保護膜接著之方法。在此所揭示之環氧系接著劑，雖然是特別有效於將以非晶性聚烯烴系樹脂及纖維素系樹脂為首之各種透明樹脂薄膜黏貼在偏光件，但可知尤其是在以丙烯酸系樹脂作為保護膜時，其接著力不一定足夠。In JP-A-2004-245925 (Patent Document 6), an epoxy resin containing no aromatic ring as a main component is disclosed, and it is proposed to irradiate the active energy source to the adhesive and then carry out cationic polymerization. A method of causing a polarizer to follow a protective film. The epoxy-based adhesive disclosed herein is particularly effective for adhering various transparent resin films including amorphous polyolefin-based resins and cellulose-based resins to polarizers, but it is known that acrylic resins are used in particular. When it is a protective film, its adhesive force is not necessarily enough.
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 Laid-Open Patent Publication No. 2000-321432
專利文獻4：日本特開2002-174729號公報Patent Document 4: Japanese Laid-Open Patent Publication No. 2002-174729
專利文獻5：日本特開2005-208456號公報Patent Document 5: Japanese Laid-Open Patent Publication No. 2005-208456
專利文獻6：日本特開2004-245625號公報Patent Document 6: Japanese Laid-Open Patent Publication No. 2004-245625
為了解決聚乙烯醇系之偏光件與透濕度低之保護膜在藉由濕壓膜法黏貼時的問題，雖考慮增長黏貼後之乾燥爐長度以爭取乾燥時間，但若單純僅使乾燥爐長度增長，則會發生因偏光件的熱劣化而容易引起變色之問題。在此，考慮降低乾燥溫度以使偏光件的熱劣化不發生，但此時，為了充分乾燥就必需更增加乾燥爐長度，而有大幅增加設備投資之問題。又，在偏光件的兩面黏貼不同種類之保護膜時，因為該等保護膜之熱所致之收縮率不同，而變成在兩面保護膜之收縮量不同之狀態下與偏光件接著，乾燥後，回到常溫時會有偏光板容易產生捲曲之問題。In order to solve the problem of the polyvinyl alcohol-based polarizer and the low-humidity protective film being adhered by the wet-pressing method, it is considered to increase the length of the drying furnace after the adhesion to obtain the drying time, but if only the drying furnace length is simply When it grows, there is a problem that color change is easily caused by thermal deterioration of the polarizer. Here, it is considered that the drying temperature is lowered so that the thermal deterioration of the polarizer does not occur, but at this time, in order to sufficiently dry, it is necessary to increase the length of the drying furnace, which greatly increases the problem of equipment investment. Further, when different types of protective films are adhered to both surfaces of the polarizing member, the shrinkage ratios due to the heat of the protective films are different, and after the shrinkage amounts of the double-sided protective films are different, the polarizing members are followed by drying. When returning to normal temperature, there is a problem that the polarizing plate is liable to curl.
為了改善相關之問題而考慮採用藉由乾壓膜法之黏貼方法。然而，由於適於乾壓膜法之接著劑之黏度極高，而有所謂偏光件之物理強度弱之問題，所以，偏光件與保護膜之接著方法係限定於先在保護膜塗布接著劑，然後黏貼在偏光件之方法。在此方法中，當在黏貼前於接著劑之塗布面附著有雜質時，由於無法隱藏掩蔽雜質，黏貼後會以雜質為起點在接著層與偏光件之間產生氣泡，而成為亮點缺陷之原因。In order to improve the related problems, an adhesive method by a dry lamination method is considered. However, since the viscosity of the adhesive suitable for the dry film method is extremely high, and the physical strength of the so-called polarizer is weak, the subsequent method of the polarizer and the protective film is limited to the application of the adhesive on the protective film. Then stick the method on the polarizer. In this method, when impurities are adhered to the coated surface of the adhesive before the adhesion, since the masking impurities cannot be concealed, bubbles are generated between the adhesive layer and the polarizing member starting from the impurities after the bonding, which becomes a cause of the bright spot defect. .
本發明人等專心研究開發在將選自聚酯樹脂、聚碳酸酯樹脂及丙烯酸系樹脂中之透濕度低的樹脂薄膜作為保護膜時，在短時間內表現良好接著力之光硬化性硬化性接著劑，結果，發現藉由使用特定之光硬化性接著劑，即可在短時間內黏貼此等保護膜。並且，發現該接著劑即使在以丙烯酸系樹脂薄膜作為保護膜時，在其與偏光件之間也會賦予高的接著力，且在以聚酯樹脂薄膜或聚碳酸酯樹脂薄膜作為保護膜時也同樣地發揮優良之接著力。The inventors of the present invention have intensively studied and developed a photocurable hardenability which exhibits a good adhesion force in a short period of time when a resin film having a low moisture permeability selected from a polyester resin, a polycarbonate resin, and an acrylic resin is used as a protective film. As a result of the subsequent treatment, it was found that these protective films can be adhered in a short time by using a specific photocurable adhesive. Further, it has been found that even when an acrylic resin film is used as a protective film, the adhesive imparts a high adhesion force to the polarizer, and when a polyester resin film or a polycarbonate resin film is used as a protective film. We also exert excellent adhesions in the same way.
因此，本發明之目的係提供在以選自聚酯樹脂、聚碳酸酯樹脂及丙烯酸系樹脂中之透濕度低的樹脂薄膜作為保護膜時，也可在短時間內以充分之接著強度使其接著於偏光件，並且不會引起外觀不良等問題之光硬化性接著劑；以及使用該接著劑在偏光件黏貼保護膜之偏光板。本發明之另一目的係提供使用該偏光板而可形成可靠度優異之液晶顯示裝置的光學構材，以及使該光學構材適用在液晶顯示裝置中。Accordingly, an object of the present invention is to provide a resin film having a low moisture permeability selected from a polyester resin, a polycarbonate resin, and an acrylic resin as a protective film, and also to have sufficient adhesion strength in a short time. A photocurable adhesive which is then applied to the polarizing material without causing problems such as poor appearance; and a polarizing plate in which the protective film is adhered to the polarizing member using the adhesive. Another object of the present invention is to provide an optical member for forming a liquid crystal display device having excellent reliability by using the polarizing plate, and to apply the optical member to a liquid crystal display device.
亦即，依照本發明能提供一種光硬化性接著劑組成物，其係用以在由經單軸延伸且經吸附配向二色性色素之聚乙烯醇系樹脂薄膜所成之偏光件上，使由選自聚酯樹脂、聚碳酸酯樹脂及丙烯酸系樹脂所成群組中之透明樹脂薄膜所成之保護膜接著的接著劑組成物，該接著劑組成物含有(A)在分子內具有至少2個環氧基之環氧化合物、(B)在分子內具有至少1個氧雜環丁基(oxetanyl)之氧雜環丁烷(oxetane)化合物、及(C)光陽離子聚合起始劑，而前述環氧化合物(A)與前述氧雜環丁烷化合物(B)之重量比(A)/(B)為90/10至10/90左右，且前述光陽離子聚合起始劑(C)之量在組成物中約為0.5至20重量%。That is, according to the present invention, it is possible to provide a photocurable adhesive composition for use in a polarizing member made of a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed to a dichroic dye. a protective film formed of a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, and an acrylic resin, and an adhesive composition comprising (A) having at least a molecule in the molecule a two epoxy group epoxy compound, (B) an oxetane compound having at least one oxetanyl group in the molecule, and (C) a photocationic polymerization initiator; The weight ratio (A)/(B) of the epoxy compound (A) to the oxetane compound (B) is about 90/10 to 10/90, and the photocationic polymerization initiator (C) The amount is about 0.5 to 20% by weight in the composition.
此光硬化性接著劑組成物中，環氧化合物(A)包括在分子內具有至少2個環氧基與至少1個芳香環之化合物，具體上，以在分子內具有至少2個環氧基與至少1個芳香環之化合物，或是在分子內具有至少2個環氧基與至少1個芳香環之化合物以及在分子內具有至少2個環氧基但不具有芳香環之化合物的混合物為佳。又，該環氧化合物(A)包括選自由芳香族化合物之縮水甘油醚及縮水甘油酯所成群組中之1種以上，具體上，以選自由芳香族化合物之縮水甘油醚及縮水甘油酯所成群組中之1種以上，或是選自由芳香族化合物之縮水甘油醚化合物及縮水甘油酯化合物所成群組中之1個以上與其以外之環氧化合物(A)的混合物為更佳。In the photocurable adhesive composition, the epoxy compound (A) includes a compound having at least two epoxy groups and at least one aromatic ring in the molecule, specifically, having at least two epoxy groups in the molecule. a mixture of at least one aromatic ring compound, or a compound having at least two epoxy groups and at least one aromatic ring in the molecule, and a compound having at least two epoxy groups in the molecule but no aromatic ring good. In addition, the epoxy compound (A) includes one or more selected from the group consisting of glycidyl ethers and glycidyl esters of aromatic compounds, and specifically, glycidyl ether and glycidyl ester selected from aromatic compounds. It is more preferable that one or more of the groups are selected, or a mixture of one or more epoxy compounds (A) selected from the group consisting of an aromatic compound glycidyl ether compound and a glycidyl ester compound. .
另一方面，作為氧雜環丁烷化合物(B)之例子，較佳者為：在分子內具有1個氧雜環丁基與至少1個芳香環之化合物、在分子內具有1個氧雜環丁基與至少1個芳香環之化合物以及在分子內具有至少1個氧雜環丁基但不具有芳香環之化合物的混合物、在分子內具有2個氧雜環丁基之化合物、在分子內具有至少2個氧雜環丁基之化合物、在分子內具有2個氧雜環丁基之化合物與在分子內具有1個氧雜環丁基之化合物的混合物、在分子內具有至少2個氧雜環丁基之化合物與在分子內具有1個氧雜環丁基之化合物的混合物等。On the other hand, as an example of the oxetane compound (B), a compound having one oxetanyl group and at least one aromatic ring in the molecule and one oxa group in the molecule are preferable. a mixture of a cyclobutyl group and at least one aromatic ring compound, a compound having at least one oxetanyl group in the molecule but not having an aromatic ring, a compound having two oxetanyl groups in the molecule, and a molecule a compound having at least two oxetanyl groups, a compound having two oxetanyl groups in the molecule, and a compound having one oxetanyl group in the molecule, and having at least two in the molecule A mixture of a compound of oxetanyl and a compound having one oxetanyl group in the molecule.
此等光硬化性接著劑組成物，可復含有作為(D)成分之在分子內具有至少1個乙烯性不飽和鍵的不飽和化合物，此時，該不飽和化合物(D)之量在組成物中一般是在35重量%以下之比率，以5至25重量%左右為佳。該不飽和化合物(D)是以在分子內具有至少1個(甲基)丙烯醯基與至少1個脂環式骨幹或芳香環骨幹之(甲基)丙烯酸系化合物為佳，又，以具有三環癸烷骨幹之二(甲基)丙烯酸酯為更佳。The photocurable adhesive composition may further contain, as the component (D), an unsaturated compound having at least one ethylenically unsaturated bond in the molecule, and in this case, the amount of the unsaturated compound (D) is in composition. The content is generally in the range of 35% by weight or less, preferably about 5 to 25% by weight. The unsaturated compound (D) is preferably a (meth)acrylic compound having at least one (meth)acryl fluorenyl group and at least one alicyclic backbone or aromatic ring backbone in the molecule, and further having The tricyclodecane backbone di(meth)acrylate is more preferred.
當接著劑組成物含有上述之不飽和化合物(D)，尤其是含有(甲基)丙烯酸系化合物時，以含有作為(E)成分之光自由基聚合起始劑為佳。光自由基聚合起始劑(E)之量，在組成物中以10重量%以下左右之比率為佳。When the adhesive composition contains the above-mentioned unsaturated compound (D), particularly a (meth)acrylic compound, it is preferred to contain a photoradical polymerization initiator as the component (E). The amount of the photoradical polymerization initiator (E) is preferably in the composition of about 10% by weight or less.
再者，此等光硬化性接著劑組成物可含有作為(F)成分之無聚合性的其他成分，此時，其他成分(F)之量，在組成物中通常以10重量%以下左右之比率為佳。Further, the photocurable adhesive composition may contain other components which are non-polymerizable as the component (F). In this case, the amount of the other component (F) is usually about 10% by weight or less in the composition. The ratio is better.
又，依照本發明能提供一種偏光板，係在由經單軸延伸且經吸附配向二色性色素之聚乙烯醇系樹脂薄膜所成之偏光件上，隔著接著劑，將由選自聚酯樹脂、聚碳酸酯樹脂及丙烯酸系樹脂所成群組中之透明樹脂薄膜所構成的保護膜黏貼而成的偏光板，而該接著劑是由上述任何一種光硬化性接著劑組成物所形成者。Further, according to the present invention, it is possible to provide a polarizing plate which is formed of a polyester selected from a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed to a dichroic dye, and which is selected from a polyester via an adhesive. a polarizing plate in which a protective film made of a transparent resin film in a group of a resin, a polycarbonate resin, and an acrylic resin is adhered, and the adhesive is formed of any of the above-described photocurable adhesive compositions. .
該偏光板係可藉由包含下述步驟之方法而製造：在偏光件與保護膜之黏貼面中的至少一面上，塗布前述任何一種光硬化性接著劑組成物的接著劑塗布步驟；隔著所得之接著劑層而黏貼偏光件與保護膜的黏貼步驟；以及在隔著接著劑層而黏貼偏光件與保護膜之狀態下，使光硬化性接著劑組成物硬化的硬化步驟。具體上可採用下述方法：在偏光件塗布未硬化之上述光硬化性接著劑組成物之後，在該接著劑組成物塗布面黏貼保護膜，其次，使該接著劑組成物硬化而形成接著劑層之方法；在保護膜塗布未硬化之上述光硬化性接著劑組成物之後，在該接著劑組成物塗布面黏貼偏光件，然後使該接著劑組成物硬化而形成接著劑層之方法；在偏光件與保護膜之間使未硬化之上述光硬化性接著劑組成物流延，以輥筒等將偏光件與保護膜之黏貼物挾住，一邊均勻地擠壓擴展接著劑組成物一邊進行壓合後，使該接著劑組成物硬化而形成接著劑層之方法等。The polarizing plate can be manufactured by a method comprising the steps of: applying an adhesive coating step of coating any one of the photocurable adhesive compositions on at least one of the adhesive faces of the polarizing member and the protective film; The adhesive layer obtained by adhering the polarizer and the protective film to the adhesive layer obtained; and the hardening step of hardening the photocurable adhesive composition in a state where the polarizer and the protective film are adhered via the adhesive layer. Specifically, after the polarizing member is coated with the unhardened photocurable adhesive composition, the protective film is adhered to the coated surface of the adhesive composition, and secondly, the adhesive composition is cured to form an adhesive. a method of laminating a polarizing member on a coated surface of the adhesive composition after applying the unhardened photocurable adhesive composition as a protective film, and then curing the adhesive composition to form an adhesive layer; Between the polarizer and the protective film, the uncured composition of the photocurable adhesive is spread, and the adhesive of the polarizer and the protective film is caught by a roller or the like, and the adhesive composition is uniformly pressed while being pressed. After the combination, the adhesive composition is cured to form an adhesive layer.
又，依照本發明能提供一種光學構材，其係積層有上述偏光板與顯示其他光學機能的光學層者。此時之其他光學層是以包含相位差板為佳。又，本發明也提供一種液晶顯示裝置，其係在液晶胞(liquid crystal cell)之單側或兩側配置有該光學構材而成者。Further, according to the present invention, it is possible to provide an optical member which is provided with the above-mentioned polarizing plate and an optical layer which exhibits other optical functions. The other optical layer at this time is preferably a phase difference plate. Moreover, the present invention also provides a liquid crystal display device in which the optical member is disposed on one side or both sides of a liquid crystal cell.
本發明之光硬化性接著劑組成物是具有藉由照射紫外線等活性能源線而容易硬化，並可在短時間內使偏光件與保護膜鞏固地接著之優點。該接著劑組成物在以丙烯酸系樹脂構成保護膜時為特別有用。隔著該接著劑組成物將偏光件與保護膜黏貼而得到之偏光板，係由於該接著劑組成物可於短時間內硬化，所以可生產性良好地製造。再者，組合該偏光板與其他光學層而成之光學構材，能形成可靠度優異之液晶顯示裝置。The photocurable adhesive composition of the present invention has an advantage that it can be easily cured by irradiation with an active energy source such as ultraviolet rays, and the polarizer and the protective film can be consolidated in a short time. This adhesive composition is particularly useful when the protective film is formed of an acrylic resin. The polarizing plate obtained by adhering the polarizer to the protective film via the adhesive composition can be cured in a short time because the adhesive composition can be produced in a good manner. Further, an optical member obtained by combining the polarizing plate and other optical layers can form a liquid crystal display device having excellent reliability.
以下，詳細說明本發明。本發明中，是在由經單軸延伸且經吸附配向二色性色素之聚乙烯醇系樹脂薄膜所成之偏光件上接著由透明樹脂薄膜所成的保護膜時，使用特定組成之光硬化性接著劑組成物。將如此作成之偏光件與保護膜藉由隔著光硬化性接著劑組成物而黏貼，可得偏光板。將該偏光板與具有其他光學機能之光學層積層，可製成光學構材。又，將該光學構材配置在液晶胞之至少一側，可製成液晶顯示裝置。以下，依光硬化性接著劑組成物、偏光板、偏光板之製造方法、光學構材、液晶顯示裝置之順序逐項進行說明。Hereinafter, the present invention will be described in detail. In the present invention, when a protective film made of a transparent resin film is formed on a polarizing member made of a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed to a dichroic dye, a photohardening using a specific composition is used. Sexual binder composition. The polarizer and the protective film thus formed are adhered by a photocurable adhesive composition to obtain a polarizing plate. The polarizing plate and the optical layer having other optical functions can be laminated to form an optical member. Further, the optical member is 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 one by one.
本發明是使用特定組成之光硬化性接著劑組成物來黏貼偏光件與保護膜。以下，亦有將該光硬化性接著劑組成物簡稱為「光硬化性接著劑」之情形。In the present invention, a polarizing adhesive and a protective film are adhered using a photocurable adhesive composition having a specific composition. Hereinafter, the photocurable adhesive composition may be simply referred to as a "photocurable adhesive".
本發明之光硬化性接著劑必需是含有以下之(A)、(B)及(C)之3種成分者。The photocurable adhesive of the present invention must be one of the following three components (A), (B) and (C).
(A)在分子內具有至少2個環氧基之環氧化合物，(B)在分子內具有至少1個氧雜環丁基之氧雜環丁烷化合物，及(C)光陽離子聚合起始劑。(A) an epoxy compound having at least two epoxy groups in the molecule, (B) an oxetane compound having at least one oxetanyl group in the molecule, and (C) photocationic polymerization initiation Agent.
在本說明書中，亦將上述(A)之環氧化合物簡稱為「(A)成分」或「環氧化合物(A)」。同樣地，本說明書中，亦將(B)之氧雜環丁烷化合物簡稱為「(B)成分」或「雜環丁烷化合物(B)」，且亦將(C)之光陽離子聚合起始劑簡稱為「(C)成分」或「光陽離子聚合起始劑(C)」。In the present specification, the epoxy compound of the above (A) is also simply referred to as "(A) component" or "epoxy compound (A)". Similarly, in the present specification, the oxetane compound of (B) is also simply referred to as "(B) component" or "heterocyclic butane compound (B)", and the photocationic cation of (C) is also polymerized. The starting agent is simply referred to as "(C) component" or "photocationic polymerization initiator (C)".
(A)成分的環氧化合物與(B)成分的氧雜環丁烷化合物，係以(A)/(B)之重量比設成為90/10至10/90左右為佳，又，(C)成分的光陽離子聚合起始劑在組成物中以成為約0.5至20重量%之比率為佳。The epoxy compound of the component (A) and the oxetane compound of the component (B) are preferably a weight ratio of (A)/(B) of from about 90/10 to about 10/90, and further, (C) The photocationic polymerization initiator of the component is preferably present in the composition in a ratio of from about 0.5 to 20% by weight.
該光硬化性接著劑組成物可任意地含有作為(D)成分的在分子內具有至少1個乙烯性不飽和鍵的不飽和化合物，含有如此之不飽和化合物(D)時，以含有作為(E)成分的光自由基聚合起始劑為佳。再者，該光硬化性接著劑也可含有作為(F)成分的無聚合性之其他成分。The photocurable adhesive composition may optionally contain, as the component (D), an unsaturated compound having at least one ethylenically unsaturated bond in the molecule, and when such an unsaturated compound (D) is contained, A photoradical polymerization initiator of the component E) is preferred. Further, the photocurable adhesive may contain other components which are non-polymerizable as the component (F).
在本說明書中，亦將上述(D)的不飽和化合物簡稱為「(D)成分」或「不飽和化合物(D)」。同樣地，在本說明書中，亦將(E)之光自由基聚合起始劑稱為「(E)成分」或「光自由基聚合起始劑(E)」，且亦將(F)的無聚合性之其他成分 稱為「(F)成分」或「無聚合性之其他成分(F)」。In the present specification, the unsaturated compound of the above (D) is also simply referred to as "(D) component" or "unsaturated compound (D)". Similarly, in the present specification, the photoradical polymerization initiator of (E) is also referred to as "(E) component" or "photoradical polymerization initiator (E)", and also (F) Other components without polymerization It is called "(F) component" or "other component (F) without polymerization).
本發明之光硬化性接著劑中，成為(A)成分之環氧化合物只要是在分子內具有至少2個環氧基者即可而無特別之限定，可使用一般習知之各種硬化性環氧化合物。成為(A)成分之較佳的環氧化合物，可列舉如：在分子內具有至少2個環氧基與至少1個芳香環之化合物(以下，稱為「芳香族系環氧化合物」)、或在分子內具有至少2個環氧基且其中至少1個是在構成脂環式環之鄰接2個碳原子之間形成的化合物(以下，稱為「脂環式環氧化合物」)等。In the photocurable adhesive of the present invention, the epoxy compound which is the component (A) is not particularly limited as long as it has at least two epoxy groups in the molecule, and various conventional hardening epoxy resins can be used. Compound. Preferred examples of the epoxy compound which is the component (A) include a compound having at least two epoxy groups and at least one aromatic ring in the molecule (hereinafter referred to as "aromatic epoxy compound"). Or at least two epoxy groups in the molecule, and at least one of them is a compound formed between two adjacent carbon atoms constituting the alicyclic ring (hereinafter referred to as "alicyclic epoxy compound").
作為芳香族系環氧化合物者，只要是不妨礙本發明之效果者就無特別之限定，可列舉：如雙酚A之二縮水甘油醚、雙酚F之二縮水甘油醚、及溴化雙酚A之二縮水甘油醚等雙酚型環氧樹脂；如酚酚醛清漆(phenol novolac)型環氧樹脂、及甲酚酚醛清漆(cresol novolac)型環氧樹脂等酚醛清漆型環氧樹脂；其他可列舉：聯苯型環氧樹脂、對苯二酚二縮水甘油醚、間苯二酚二縮水甘油醚、對苯二甲酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯、苯乙烯-丁二烯共聚物之環氧化物、苯乙烯-異戊二烯共聚物之環氧化物、末端羧酸聚丁二烯與雙酚A型環氧樹脂之加成反應物等。The aromatic epoxy compound is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and brominated double a bisphenol type epoxy resin such as bisphenolate ether of phenol A; a phenol novolac type epoxy resin such as a phenol novolac type epoxy resin; and a cresol novolac type epoxy resin such as a phenol novolac type epoxy resin; For example, biphenyl type epoxy resin, hydroquinone diglycidyl ether, resorcinol diglycidyl ether, diglycidyl terephthalate, diglycidyl phthalate, styrene-butyl An epoxide of a diene copolymer, an epoxide of a styrene-isoprene copolymer, an addition reaction of a terminal carboxylic acid polybutadiene and a bisphenol A type epoxy resin, and the like.
在此，環氧樹脂是指在分子中具有平均2個以上之環氧基且會藉由反應而硬化之化合物或聚合物。依據該領域之慣例，於本說明書中，只要是在分子內具有2個以上硬化性環氧基者，即使是單體也稱為環氧樹脂。Here, the epoxy resin means a compound or a polymer having an average of two or more epoxy groups in a molecule and which is hardened by a reaction. According to the practice in the field, in the present specification, even if it is a monomer having two or more curable epoxy groups in the molecule, even a monomer is called an epoxy resin.
作為脂環式環氧化合物者，只要不妨礙本發明之效果就無特別之限定，可列舉：如二環戊二烯二氧化物、檸檬烯二氧化物、4-乙烯基環己烯二氧化物、3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯、及己二酸雙(3,4-環氧基環己基甲基)酯等具有至少1個環氧化環己基之化合物等。The alicyclic epoxy compound is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include dicyclopentadiene dioxide, limonene dioxide, and 4-vinylcyclohexene dioxide. 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, and bis(3,4-epoxycyclohexylmethyl) adipate have at least one ring A compound which oxidizes a cyclohexyl group or the like.
前述之外，(A)成分的環氧化合物亦可列舉：如1,6-己二醇二縮水甘油醚、三羥甲基丙烷三縮水甘油醚、季戊四醇四縮水甘油醚、及聚四亞甲基二醇二縮水甘油醚等脂肪族系環氧化合物；如氫化雙酚A之二縮水甘油醚等芳香環經氫化之環氧化合物；如兩末端羥基之聚丁二烯的兩末端被縮水甘油醚化的化合物、聚丁二烯的內部環氧化物、苯乙烯-丁二烯共聚物之雙鍵被部分性地環氧化的化合物[例如，Daicel化學工業股份公司製之"Epoblend"]、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被部分性地環氧化的化合物(例如，KRATON公司製之"L-207")等聚合物系的環氧化合物等。In addition to the above, the epoxy compound of the component (A) may also be exemplified by 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, and polytetramethylene. An aliphatic epoxy compound such as a diol diglycidyl ether; an aromatic ring hydrogenated epoxy compound such as hydrogenated bisphenol A diglycidyl ether; and both ends of the polybutadiene having a hydroxyl group at both terminals are glycidol An etherified compound, an internal epoxide of polybutadiene, a compound in which a double bond of a styrene-butadiene copolymer is partially epoxidized [for example, "Epoblend" manufactured by Daicel Chemical Industry Co., Ltd.], and A polymer-based ring of a compound in which an isoprene unit of an ethylene-butene copolymer and a polyisoprene block copolymer is partially epoxidized (for example, "L-207" manufactured by KRATON Co., Ltd.) Oxygen compounds, etc.
其中，芳香族系環氧化合物係因作成偏光板時之耐久性等優異，又尤其因為對偏光件及保護膜之接著性優異，故為佳者。再者，作為該芳香族系環氧化合物者，較佳例可列舉：芳香族化合物之縮水甘油醚或是芳香族化合物之縮水甘油酯等。芳香族化合物之縮水甘油醚的具體例，較佳者可列舉：如雙酚A之二縮水甘油醚、雙酚F之二縮水甘油醚、及溴化雙酚A之二縮水甘油醚等雙酚型環氧樹脂；如酚酚醛清漆型環氧樹脂、及甲酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂；聯苯型環氧樹脂；對苯二酚二縮水甘油醚；間苯二酚二縮水甘油醚等。又，芳香族化合物之縮水甘油酯之具體例，較佳者可列舉：對苯二甲酸二縮水甘油酯、鄰苯二甲酸二縮水甘油酯等。Among them, the aromatic epoxy compound is excellent in durability when it is used as a polarizing plate, and is particularly excellent in adhesion to a polarizer and a protective film. Further, as the aromatic epoxy compound, a glycidyl ether of an aromatic compound or a glycidyl ester of an aromatic compound may, for example, be mentioned. Specific examples of the glycidyl ether of the aromatic compound include bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and brominated bisphenol A diglycidyl ether. Type epoxy resin; such as phenol novolak type epoxy resin, and phenol novolak type epoxy resin and other novolac type epoxy resin; biphenyl type epoxy resin; hydroquinone diglycidyl ether; isophthalic acid Phenol diglycidyl ether and the like. Further, specific examples of the glycidyl ester of the aromatic compound include diglycidyl terephthalate and diglycidyl phthalate.
其中，芳香族化合物之二縮水甘油醚係因在接著偏光件及保護膜時之密著性或作成偏光板時之耐久性更優異，所以為特別良好。芳香族化合物之二縮水甘油醚中，特佳之化合物可列舉：雙酚A之二縮水甘油醚、雙酚F之二縮水甘油醚、及酚酚醛清漆型環氧樹脂。Among them, the diglycidyl ether of the aromatic compound is particularly excellent because it is excellent in adhesion at the time of following the polarizer and the protective film or when it is used as a polarizing plate. Among the diglycidyl ethers of the aromatic compound, particularly preferred are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and phenol novolac type epoxy resin.
(A)成分之環氧化合物可單獨使用1種，也可混合2種以上而使用。例如，可將2種以上之芳香族系環氧化合物混合而使用，亦可將芳香族系環氧化合物作為主體並與脂環式環氧化合物混合。The epoxy compound of the component (A) may be used singly or in combination of two or more. For example, two or more kinds of aromatic epoxy compounds may be used in combination, and an aromatic epoxy compound may be mainly used as a main component and mixed with an alicyclic epoxy compound.
在本發明之光硬化性接著劑中，成為(B)成分之氧雜環丁烷化合物，只要是在分子內具有至少1個氧雜環丁基者即可而無特別限定，可使用具有氧雜環丁基之各種化合物。作為氧雜環丁烷化合物(B)者，較佳例可列舉如：在分子內具有1個氧雜環丁基之化合物(以下簡稱為「單官能氧雜環丁烷」)、及在分子內具有2個以上氧雜環丁基之化合物(以下簡稱為「多官能氧雜環丁烷」)。In the photocurable adhesive of the present invention, the oxetane compound which is a component (B) is not particularly limited as long as it has at least one oxetanyl group in the molecule, and oxygen can be used. Various compounds of heterocyclic butyl groups. Preferred examples of the oxetane compound (B) include a compound having one oxetanyl group in the molecule (hereinafter simply referred to as "monofunctional oxetane"), and a molecule. A compound having two or more oxetanyl groups (hereinafter simply referred to as "polyfunctional oxetane").
作為單官能氧雜環丁烷者，較佳例可列舉：如3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷等含有烷氧基烷基之單官能氧雜環丁烷；如3-乙基-3-苯氧基甲基氧雜環丁烷等含有芳香族基之單官能氧雜環丁烷；如3-乙基-3-羥基甲基氧雜環丁烷等含有羥基之單官能氧雜環丁烷等。Preferred examples of the monofunctional oxetane include a monofunctional group containing an alkoxyalkyl group such as 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane or the like. An oxetane; an aromatic group-containing monofunctional oxetane such as 3-ethyl-3-phenoxymethyloxetane; such as 3-ethyl-3-hydroxymethyl oxygen A monofunctional oxetane having a hydroxyl group such as a heterocyclobutane or the like.
作為多官能氧雜環丁烷者，可列舉如以下之化合物：3-乙基-3-[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]氧雜環丁烷、1,4-雙[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]苯、1,4-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、1,3-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、1,2-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]苯、4,4’-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]聯苯、2,2’-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]聯苯、3,3’,5,5’-四甲基-4,4’-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]聯苯、2,7-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]萘、雙[4-{(3-乙基氧雜環丁烷-3-基)甲氧基]苯基}甲烷、雙[2-{(3-乙基氧雜環丁烷-3-基)甲氧基]苯基}甲烷、2,2-雙[4-{(3-乙基氧雜環丁烷-3-基)甲氧基]苯基}丙烷、酚醛清漆型酚-甲醛樹脂之3-氯甲基-3-乙基氧雜環丁烷的醚化改質物、3(4),8(9)-雙[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]-三環[5.2.1.02,6 ]癸烷、2,3-雙[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]降冰片烷、1,1,1-參[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]丙烷、1-丁氧基-2,2-雙[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]丁烷、1,2-雙[{2-(3-乙基氧雜環丁烷-3-基)甲氧基}乙硫基]乙烷、雙[{4-(3-乙基氧雜環丁烷-3-基)甲硫基}苯基]硫化物、1,6-雙[(3-乙基氧雜環丁烷-3-基)甲氧基]-2,2,3,3,4,4,5,5-八氟己烷、3-[(3-乙基氧雜環丁烷-3-基)甲氧基]丙基三乙氧基矽烷之水解縮合物、肆[(3-乙基氧雜環丁烷-3-基)甲基]矽酸酯之縮合物等。As the polyfunctional oxetane, a compound such as 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane can be exemplified. Alkane, 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene, 1,4-bis[(3-ethyloxetane-3- Methoxy]benzene, 1,3-bis[(3-ethyloxetan-3-yl)methoxy]benzene, 1,2-bis[(3-ethyloxetane) Alkyl-3-yl)methoxy]benzene, 4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl, 2,2'-bis[(3) -ethyloxetan-3-yl)methoxy]biphenyl, 3,3',5,5'-tetramethyl-4,4'-bis[(3-ethyloxetine) Alkyl-3-yl)methoxy]biphenyl, 2,7-bis[(3-ethyloxetan-3-yl)methoxy]naphthalene, bis[4-{(3-ethyl) Oxetane-3-yl)methoxy]phenyl}methane, bis[2-{(3-ethyloxetan-3-yl)methoxy]phenyl}methane, 2, 2-bis[4-{(3-ethyloxetan-3-yl)methoxy]phenyl}propane, 3-chloromethyl-3-ethyloxy of novolac type phenol-formaldehyde resin Etherification modification of heterocyclobutane, 3(4),8(9)-bis[(3-ethyloxetan-3-yl)methoxymethyl]-tricyclo[5.2.1.0 2,6] decane 2,3-bis[(3-ethyloxetan-3-yl)methoxymethyl]norbornane, 1,1,1-gin[(3-ethyloxetane- 3-yl)methoxymethyl]propane, 1-butoxy-2,2-bis[(3-ethyloxetan-3-yl)methoxymethyl]butane, 1, 2-bis[{2-(3-ethyloxetan-3-yl)methoxy}ethylthio]ethane, bis[{4-(3-ethyloxetane-3) -yl)methylthio}phenyl]sulfide, 1,6-bis[(3-ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4 , 5,5-octafluorohexane, 3-[(3-ethyloxetan-3-yl)methoxy]propyltriethoxydecane hydrolysis condensate, 肆[(3-B A condensate of oxetane-3-yl)methyl]decanoate or the like.
(B)成分之氧雜環丁烷化合物，從塗工性或作成偏光板時之對保護膜之密著性的觀點而言，以分子量500以下之在室溫中為液狀者為佳。再者，從偏光板成為耐久性優異者之觀點而言，以單官能氧雜環丁烷之在分子內有芳香環者、或是多官能氧雜環丁烷為更佳。作為如此特佳的氧雜環丁烷化合物之例者，可列舉如：3-乙基-3-苯氧基甲基氧雜環丁烷、3-乙基-3-[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]氧雜環丁烷、及1,4-雙[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]苯等。The oxetane compound of the component (B) is preferably a liquid having a molecular weight of 500 or less at room temperature from the viewpoints of workability or adhesion to a protective film when a polarizing plate is formed. Further, from the viewpoint that the polarizing plate is excellent in durability, it is more preferable that the monofunctional oxetane has an aromatic ring in the molecule or a polyfunctional oxetane. As an example of such a particularly preferred oxetane compound, for example, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-[(3-ethyl) Oxetane-3-yl)methoxymethyl]oxetane, and 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl] Benzene, etc.
(B)成分之氧雜環丁烷化合物可單獨使用1種，此外，亦可混合2種以上而使用。The oxetane compound of the component (B) may be used alone or in combination of two or more.
(A)成分之環氧化合物與(B)成分之氧雜環丁烷化合物使用比率係依(A)/(B)之重量比而為90/10至10/90。當此比率為過多與不足時，就不能充分發揮本發明之光硬化性接著劑的重要特性之一的於短時間硬化之效果。由於兩者的較佳重量比率可使硬化前於低黏度下為塗布性優異，於硬化後可表現充分之密著性與可撓性，所以兩者的較佳重量比率是70/30至20/80左右，更佳之重量比率是60/40至25/75左右。The use ratio of the epoxy compound of the component (A) to the oxetane compound of the component (B) is 90/10 to 10/90 by weight ratio of (A)/(B). When the ratio is too large or insufficient, the effect of short-time hardening which is one of the important characteristics of the photocurable adhesive of the present invention cannot be sufficiently exerted. Since the preferred weight ratio of the two is excellent in coatability at low viscosity before hardening and sufficient adhesion and flexibility after hardening, the preferred weight ratio of the two is 70/30 to 20 /80 or so, the better weight ratio is around 60/40 to 25/75.
本發明之光硬化性接著劑含有作為硬化成分之以上說明的環氧化合物(A)及氧雜環丁烷化合物(B)，由於該等皆為藉由陽離子聚合而硬化者，故摻配作為(C)成分之光陽離子聚合起始劑。該光陽離子聚合起始劑係藉由可見光線、紫外線、X線、電子射線等活性能源線之照射而產生陽離子種或路易斯酸，以開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) and the oxetane compound (B) described above as a curing component, and since these are all cured by cationic polymerization, blending is used as A photocationic polymerization initiator of the component (C). The photocationic polymerization initiator generates a cationic species or a Lewis acid by irradiation with an active energy source such as visible light, ultraviolet rays, X-rays, or electron beams to initiate polymerization of an epoxy group or an oxetane group.
藉由摻配作為(C)成分之光陽離子聚合起始劑，而可在常溫下硬化，因而可減少考慮偏光件之耐熱性或是膨脹或收縮所導致之歪斜的必要，並可使保護膜良好地接著。又，光陽離子聚合起始劑係由於照射活性能源線而有觸媒的作用，因此即使與環氧化合物(A)及氧雜環丁烷化合物(B)混合，保存安定性或作業性也優異。作為藉由照射活性能源線而產生陽離子種或路易斯酸之化合物者，可列舉：如芳香族重氮鎓鹽(diazonium salt)、芳香族錪鹽或芳香族鋶鹽等鎓鹽、鐵-丙二烯錯合物等。By blending the photocationic polymerization initiator as the component (C), it can be hardened at room temperature, thereby reducing the necessity of considering the heat resistance of the polarizer or the skew caused by expansion or contraction, and allowing the protective film to be provided. Good to follow. Further, since the photocationic polymerization initiator has a function as a catalyst by irradiation with an active energy source, it is excellent in storage stability and workability even when it is mixed with the epoxy compound (A) and the oxetane compound (B). . Examples of the compound which generates a cationic species or a Lewis acid by irradiation with an active energy source include a sulfonium salt such as an aromatic diazonium salt, an aromatic sulfonium salt or an aromatic sulfonium salt, and an iron-propylene hydride. Ole complex and the like.
作為芳香族重氮鎓鹽者，例如可列舉如下之化合物：六氟銻酸苯重氮鎓鹽、六氟磷酸苯重氮鎓鹽、六氟硼酸苯重氮鎓鹽等。Examples of the aromatic diazonium salt include compounds such as benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.
作為芳香族錪鹽者，例如可列舉如下之化合物：肆(五氟苯基)硼酸二苯基錪鹽、六氟磷酸二苯基錪鹽、六氟銻酸二苯基錪鹽、六氟磷酸二(4-壬基苯基)錪鹽等。Examples of the aromatic onium salt include compounds of diphenylphosphonium sulfonium (pentafluorophenyl)borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, and hexafluorophosphoric acid. Bis(4-nonylphenyl) phosphonium salt and the like.
作為芳香族鋶鹽者，例如可列舉如下之化合物：六氟磷酸三苯基鋶鹽、六氟銻酸三苯基鋶鹽、肆(五氟苯基)硼酸三苯基鋶鹽、六氟磷酸二苯基[4-(苯硫基)苯基]鋶鹽、六氟銻酸二苯基[4-(苯硫基)苯基]鋶鹽、4,4’-雙(二苯基鋶基)二苯基硫醚 雙六氟磷酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫醚 雙六氟銻酸鹽、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫醚 雙六氟磷酸鹽、7-[二(對甲苯基)鋶基]-2-異丙基噻噸酮 六氟銻酸鹽、7-[二(對甲苯基)鋶基]-2-異丙基噻噸酮 肆(五氟苯基)硼酸鹽、4-苯基羰基-4’-二苯基鋶基-二苯基硫醚 六氟磷酸鹽、4-(對-第三丁基苯基羰基)-4’-二苯基鋶基-二苯基硫醚 六氟銻酸鹽、4-(對-第三丁基苯基羰基)-4’-二(對甲苯基)鋶基-二苯基硫醚 肆(五氟苯基)硼酸鹽等。Examples of the aromatic onium salt include the following compounds: triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium sulfonate (pentafluorophenyl)borate, and hexafluorophosphoric acid. Diphenyl[4-(phenylthio)phenyl]phosphonium salt, diphenyl[4-(phenylthio)phenyl]phosphonium hexafluoroantimonate, 4,4'-bis(diphenylfluorenyl) Diphenyl sulfide dihexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluoroantimonate, 4,4'- Bis[di(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide dihexafluorophosphate, 7-[bis(p-tolyl)indolyl]-2-isopropylthioxanthone hexafluoro Citrate, 7-[bis(p-tolyl)indolyl]-2-isopropylthioxanthone oxime (pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylfluorenyl- Diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylindenyl-diphenyl sulfide hexafluoroantimonate, 4-(p-- Tributylphenylcarbonyl)-4'-bis(p-tolyl)indenyl-diphenyl sulfide quinone (pentafluorophenyl) borate.
作為鐵-丙烯錯合物者，例如可列舉如下之化合物：二甲苯-環戊二烯基鐵(II)六氟銻酸鹽、異丙苯-環戊二烯基鐵(II)六氟磷酸鹽、二甲苯-環戊二烯基鐵(II)-參(三氟甲基磺醯基)甲基化物等。As the iron-propylene complex, for example, the following compounds may be mentioned: xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate Salt, xylene-cyclopentadienyl iron (II)-parafic (trifluoromethylsulfonyl) methylate, and 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2種以上而使用。其中尤以芳香族鋶鹽因為即使在300nm以上之波長區域也具有紫外線吸收特性，故可賦予具有優異之硬化性、良好之機械強度或接著強度的硬化物，而適合使用。These photocationic polymerization initiators may be used alone or in combination of two or more. Among them, the aromatic sulfonium salt is particularly suitable for use because it has ultraviolet absorbing properties even in a wavelength region of 300 nm or more, and thus can be provided with a cured product having excellent hardenability, good mechanical strength, or adhesion strength.
光陽離子聚合起始劑可從市售品中容易取得，可分別以商品名列舉如："Kayarad PCI-220"、"Kayarad PCI-620"(以上，日本化藥(股)製)、"UVI-6992"(陶氏化學公司製)、"ADEKA OPTOMER SP-150"、"ADEKA OPTOMER SP-170"(以上，ADEKA(股)製)、"CI-5102"、"CIT-1370"、"CIT-1682"、"CIP-1866S"、"CIP-2048S"、"CIP-2064S"(以上，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，綠化學(股)製)、"PI-2074"(RHODIA公司製)、"Irgacure 250"、"Irgacure PAG 103"、"Irgacure PAG 108"、"Irgacure PAG 121"、"Irgacure PAG 203"(以上，汽巴公司製)、"CPI-100P"、"CPI-101A"、"CPI-200K"、"CPI-210S"(以上，San-Apro(股)製)等，尤其以含有二苯基[4-(苯硫基)苯基]鋶鹽作為陽離子成分的陶氏化學公司製之"UVI-6992"、San-Apro(股)製之"CPI-100P"、"CPI-101A"、"CPI-200K"、"CPI-210S"為佳。The photocationic polymerization initiator can be easily obtained from commercially available products, and can be listed by brand names such as "Kayarad PCI-220", "Kayarad PCI-620" (above, manufactured by Nippon Kayaku Co., Ltd.), "UVI". -6992" (made by Dow Chemical Co., Ltd.), "ADEKA OPTOMER SP-150", "ADEKA OPTOMER SP-170" (above, ADEKA (share) system), "CI-5102", "CIT-1370", "CIT -1682", "CIP-1866S", "CIP-2048S", "CIP-2064S" (above, 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, Green Chemical Co., Ltd.) "PI-2074" (made by RHODIA), "Irgacure 250", "Irgacure PAG 103", "Irgacure PAG 108", "Irgacure PAG 121", "Irgacure PAG 203" (above, Ciba) CPI-100P", "CPI-101A", "CPI-200K", "CPI-210S" (above, San-Apro), especially containing diphenyl[4-(phenylthio)benzene "UVI-6992" manufactured by The Dow Chemical Company, which is a cationic component, and made by San-Apro (share) CPI-100P", "CPI-101A", "CPI-200K", and "CPI-210S" are preferred.
以光硬化性接著劑全體為基準，(C)成分之光陽離子聚合起始劑的摻配比率係設為0.5至20重量%之範圍。該比率低於0.5重量%時，接著劑之硬化變得不充分，機械強度或接著強度下降，另一方面其比率超過20重量%時，硬化物中之離子性物質增加而導致硬化物之吸濕性變高，耐久性能有可能下降。The blending ratio of the photocationic polymerization initiator of the component (C) is in the range of 0.5 to 20% by weight based on the entire photocurable adhesive. When 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, when the ratio exceeds 20% by weight, the ionic substance in the cured product increases to cause the hardened material to be sucked. The wetness becomes high and the durability may be lowered.
本發明之光硬化性接著劑中，因應需要，可含有作為(D)成分之在分子內具有至少1個乙烯性不飽和鍵的不飽和化合物。該不飽和化合物(D)的典型例可列舉：在分子內具有至少1個(甲基)丙烯醯基之(甲基)丙烯酸系化合物。In the photocurable adhesive of the present invention, if necessary, an unsaturated compound having at least one ethylenically unsaturated bond in the molecule as the component (D) may be contained. A typical example of the unsaturated compound (D) is a (meth)acrylic compound having at least one (meth)acryl fluorenyl group in the molecule.
作為(甲基)丙烯酸系化合物者，雖無特別限定，但可列舉如(甲基)丙烯酸酯類、(甲基)丙烯醯胺類、(甲基)丙烯酸、(甲基)丙烯醯基嗎啉、(甲基)丙烯醛等。The (meth)acrylic compound is not particularly limited, and examples thereof include (meth)acrylates, (meth)acrylamides, (meth)acrylic acid, and (meth)acrylonitrile groups. Porphyrin, (meth)acrolein, and the like.
作為分子內具有1個(甲基)丙烯醯基之(甲基)丙烯酸酯類(以下，簡稱為單官能(甲基)丙烯酸酯)者，並無特別限定，例如可列舉如以下之化合物：如(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、及(甲基)丙烯酸硬脂酯等(甲基)丙烯酸烷酯類；如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、及(甲基)丙烯酸4-羥基丁酯等(甲基)丙烯酸羥基烷酯類；如(甲基)丙烯酸環己酯、(甲基)丙烯酸異冰片酯、1,4-環己烷二羥甲基單(甲基)丙烯酸酯、(甲基)丙烯酸二環戊酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯基氧基乙酯等脂環式單官能(甲基)丙烯酸酯類；如(甲基)丙烯酸苄酯、對異丙苯基酚環氧烷加成物之(甲基)丙烯酸酯、鄰苯基酚環氧烷加成物之(甲基)丙烯酸酯、酚環氧烷加成物之(甲基)丙烯酸酯、及壬基酚環氧烷加成物之(甲基)丙烯酸酯等具有芳香族環之單官能(甲基)丙烯酸酯類(在此，環氧烷可列舉環氧乙烷或環氧丙烷等)；如(甲基)丙烯酸2-甲氧基乙酯、(甲基)丙烯酸乙氧基甲酯、及2-乙基己基醇之環氧烷加成物之(甲基)丙烯酸酯等(甲基)丙烯酸烷氧基烷酯類；如乙二醇單(甲基)丙烯酸酯、丙二醇單(甲基)丙烯酸酯、戊二醇單(甲基)丙烯酸酯、及己二醇單(甲基)丙烯酸酯等二元醇單(甲基)丙烯酸酯類；如二乙二醇單(甲基)丙烯酸酯、三乙二醇單(甲基)丙烯酸酯、四乙二醇單(甲基)丙烯酸酯、多乙二醇單(甲基)丙烯酸酯、二丙二醇單(甲基)丙烯酸酯、三丙二醇單(甲基)丙烯酸酯、及多丙二醇單(甲基)丙烯酸酯等多烷二醇單(甲基)丙烯酸酯類；(甲基)丙烯酸縮水甘油酯；(甲基)丙烯酸四氫呋喃酯；如己內酯改質(甲基)丙烯酸四氫呋喃酯等(甲基)丙烯酸四氫呋喃酯類；(甲基)丙烯酸3,4-環氧基環己基甲酯；(甲基)丙烯酸N,N-二甲基胺基乙酯；異氰酸2-(甲基)丙烯醯基氧基乙酯等。The (meth) acrylate having one (meth) acrylonitrile group in the molecule (hereinafter, simply referred to as a monofunctional (meth) acrylate) is not particularly limited, and examples thereof include the following compounds: Such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate , 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate (A Alkyl acrylates; such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, etc. Such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 1,4-cyclohexanedimethylol mono(meth)acrylate, dicyclopentanyl (meth)acrylate, An alicyclic monofunctional (meth) acrylate such as dicyclopentenyl (meth) acrylate or dicyclopentenyloxyethyl (meth) acrylate; such as benzyl (meth) acrylate, dimorphism Propyl phenol epoxy (meth) acrylate of an adduct, (meth) acrylate of an o-phenylphenol alkylene oxide adduct, a (meth) acrylate of a phenol alkylene oxide adduct, and a nonyl phenol epoxy a monofunctional (meth) acrylate having an aromatic ring such as a (meth) acrylate of an alkane adduct (herein, an alkylene oxide may, for example, ethylene oxide or propylene oxide); a (meth)acrylic acid alkoxylate such as 2-methoxyethyl acrylate, ethoxymethyl (meth) acrylate, and (meth) acrylate of an alkylene oxide adduct of 2-ethylhexyl alcohol Alkyl esters; such as ethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, pentanediol mono(meth)acrylate, and hexanediol mono(meth)acrylate Monool (meth) acrylates; such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethyl Polyalkylene glycol mono(methyl) such as diol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate Acrylates; (methyl) propyl Acid glycidyl ester; (meth)acrylic acid tetrahydrofuran ester; such as caprolactone modified (meth)acrylic acid tetrahydrofuran ester (meth)acrylic acid tetrahydrofuran ester; (meth)acrylic acid 3,4-epoxycyclohexyl Methyl ester; N,N-dimethylaminoethyl (meth)acrylate; 2-(methyl)propenyloxyethyl isocyanate.
又，作為分子內具有2個以上(甲基)丙烯醯基之(甲基)丙烯酸酯類者，並無特別限定，例如可列舉下述之化合物：如三環癸烷二羥甲基二(甲基)丙烯酸酯、1,4-環己烷二羥甲基二(甲基)丙烯酸酯、降冰片烷二羥甲基二(甲基)丙烯酸酯、及氫化雙酚A之二(甲基)丙烯酸酯等具有脂環式環的二(甲基)丙烯酸酯類；如包含雙酚A環氧乙烷加成物之二(甲基)丙烯酸酯及雙酚A環氧丙烷加成物之二(甲基)丙烯酸酯的雙酚A環氧烷加成物之二(甲基)丙烯酸酯，以及雙酚A二縮水甘油基醚之二(甲基)丙烯酸酯等具有芳香族環的二(甲基)丙烯酸酯類；如乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、戊二醇二(甲基)丙烯酸酯、及己二醇二(甲基)丙烯酸酯等烷二醇二(甲基)丙烯酸酯類；二乙二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、多乙二醇二(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、及多丙二醇二(甲基)丙烯酸酯等多烷二醇二(甲基)丙烯酸酯類；甘油之二或三(甲基)丙烯酸酯、及二甘油之二或三(甲基)丙烯酸酯等甘油類之二或三(甲基)丙烯酸酯類；甘油類之環氧烷加成物之二或三(甲基)丙烯酸酯類；如雙酚A環氧烷加成物之二(甲基)丙烯酸酯、及雙酚F環氧烷加成物之二(甲基)丙烯酸酯等雙酚環氧烷加成物之二(甲基)丙烯酸酯類；如三羥甲基丙烷三(甲基)丙烯酸酯、二(三羥甲基丙烷)三(甲基)丙烯酸酯、二(三羥甲基丙烷)四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等多元醇多(甲基)丙烯酸酯類；此等多元醇之環氧烷加成物之多(甲基)丙烯酸酯類；異三聚氰酸環氧烷加成物之二或三(甲基)丙烯酸酯類；1,3,5-三(甲基)丙烯醯基六氫-s-三等。Further, the (meth) acrylate having two or more (meth) acryl fluorenyl groups in the molecule is not particularly limited, and examples thereof include compounds such as tricyclodecane dimethylol bis ( Methyl) acrylate, 1,4-cyclohexane dimethylol di(meth) acrylate, norbornane dimethylol di(meth) acrylate, and hydrogenated bisphenol A bis (methyl) a di(meth)acrylate having an alicyclic ring such as an acrylate; such as a di(meth)acrylate containing a bisphenol A ethylene oxide adduct and a bisphenol A propylene oxide adduct a di(meth)acrylate of a bisphenol A alkylene oxide adduct of di(meth)acrylate, and a di(meth)acrylate of bisphenol A diglycidyl ether, etc. (meth)acrylates; such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, pentanediol di(meth)acrylate, and hexanediol di(meth)acrylic acid Alkylene glycol di(meth)acrylates such as esters; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, Polyethylene glycol II Polyalkylene glycol di(meth)acrylates such as acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; glycerin Di- or tri(meth)acrylates of glycerol such as di- or tri-(meth)acrylate, di- or tri-(tri)glycerol; glycerol-based alkylene oxide adduct Or tris(meth)acrylates; bisphenols such as bis(meth)acrylates of bisphenol A alkylene oxide adducts and bis(meth)acrylates of bisphenol F alkylene oxide adducts Dialkyl (meth) acrylates of alkylene oxide adducts; such as trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tri(meth)acrylate, di(tris) Methylpropane) tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Polyol (meth) acrylates; poly(meth) acrylates of alkylene oxide adducts of such polyols; diisocyanate alkylene oxide adducts Or tris(meth)acrylates; 1,3,5-tris(meth)acrylamidohexahydro-s-three Wait.
作為(甲基)丙烯醯胺類者，可列舉如：(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-二甲基胺基丙基)(甲基)丙烯醯胺、亞甲基雙(甲基)丙烯醯胺、伸乙基雙(甲基)丙烯醯胺等。Examples of the (meth)acrylamides include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, and N,N-diethyl(meth)propene. Indoleamine, N-methylol (meth) acrylamide, N-(3-N,N-dimethylaminopropyl)(methyl) acrylamide, methylene bis(methyl) propylene Indoleamine, ethyl bis(methyl) acrylamide and the like.
又，亦可使用如胺酯(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯及環氧基(甲基)丙烯酸酯等寡聚物作為(甲基)丙烯酸系化合物。Further, an oligomer such as an amine ester (meth) acrylate, a polyester (meth) acrylate or an epoxy (meth) acrylate may be used as the (meth)acrylic compound.
進一步，同時具有(甲基)丙烯醯基及其外之乙烯性不飽和鍵的化合物，也可作為(甲基)丙烯酸系化合物使用，其具體例可列舉：(甲基)丙烯酸烯丙酯、N,N-二烯丙基(甲基)丙烯醯胺等。Further, a compound having a (meth)acryloyl group and an ethylenically unsaturated bond at the same time may be used as the (meth)acrylic compound, and specific examples thereof include allyl (meth)acrylate. N,N-diallyl (meth) acrylamide and the like.
作為(D)成分者並無特別限定，除了以上之(甲基)丙烯酸系化合物之外，也可使用如：N-乙烯基-2-吡咯烷酮、己二酸二乙烯酯及癸二酸二乙烯酯等乙烯基化合物；如異三聚氰酸三烯丙酯、三烯丙基胺、均苯四甲酸四烯丙酯、N,N,N’ N’-四烯丙基-1,4-二胺基丁烷、四烯丙基銨鹽及烯丙基胺等烯丙基化合物；如馬來酸及衣康酸(itaconic acid)等不飽和羧酸等。The component (D) is not particularly limited, and other than the above (meth)acrylic compound, for example, N-vinyl-2-pyrrolidone, divinyl adipate, and diammonium dicarboxylate may be used. a vinyl compound such as an ester; such as triallyl cyanurate, triallylamine, tetraallyl pyromellitate, N, N, N' N'-tetraallyl-1,4- An allyl compound such as a diaminobutane, a tetraallyl ammonium salt or an allylamine; an unsaturated carboxylic acid such as maleic acid or itaconic acid.
即使在此等(D)成分之不飽和化合物中，也以(甲基)丙烯酸系化合物為佳。進一步，當隔著含該化合物之接著劑而將偏光件與保護膜接著以作成偏光板時，從提高耐熱性等耐久性之觀點而言，以在分子內具有至少1個脂環式骨幹或芳香環骨幹之(甲基)丙烯酸系化合物為較佳。該分子內具有至少1個脂環式骨幹或芳香環骨幹之(甲基)丙烯酸系化合物之具體例，較佳者可列舉如：前述之脂環式單官能(甲基)丙烯酸酯類、具有芳香族環之單官能(甲基)丙烯酸酯類、具有脂環式環之二(甲基)丙烯酸酯類、及具有芳香族環之二(甲基)丙烯酸酯類。此等之中，也以具有三環癸烷骨幹之二(甲基)丙烯酸酯為佳，此等特佳的(甲基)丙烯酸系化合物之具體例可列舉如三環癸烷二羥甲基二(甲基)丙烯酸酯等。Even in the unsaturated compound of the component (D), a (meth)acrylic compound is preferred. Further, when the polarizer and the protective film are subsequently formed as a polarizing plate via an adhesive containing the compound, at least one alicyclic skeleton is contained in the molecule from the viewpoint of improving durability such as heat resistance. A (meth)acrylic compound of an aromatic ring backbone is preferred. Specific examples of the (meth)acrylic compound having at least one alicyclic backbone or aromatic ring backbone in the molecule, and preferred examples thereof include the aforementioned alicyclic monofunctional (meth)acrylates, and A monofunctional (meth) acrylate of an aromatic ring, a di(meth) acrylate having an alicyclic ring, and a di(meth) acrylate having an aromatic ring. Among these, a di(meth)acrylate having a tricyclodecane backbone is also preferred, and specific examples of such a particularly preferred (meth)acrylic compound include tricyclodecane dimethylol. Di(meth)acrylate and the like.
為了調節硬化速度、偏光件與保護膜之密著性、接著層之彈性率、或接著物之耐久性等，而可使用(D)成分之不飽和化合物。(D)成分之不飽和化合物可單獨使用1種，亦可混合2種以上而使用。In order to adjust the curing rate, the adhesion between the polarizer and the protective film, the elastic modulus of the adhesive layer, or the durability of the adhesive, an unsaturated compound of the component (D) can be used. The unsaturated compound of the component (D) may be used singly or in combination of two or more.
摻配(D)成分之不飽和化合物時，以組成物全體作為基準，其摻配比率係以在35重量%以下為佳。藉此，可做成偏光件與保護膜之密著性優良者。不飽和化合物(D)之量超過35重量%時，則與偏光件不容易得到充分的接著強度。因此，不飽和化合物(D)之摻配比率係以在30重量%以下為較佳，以在5至25重量%為更佳，進一步以10至20重量%為特佳。When the unsaturated compound of the component (D) is blended, the blending ratio is preferably 35% by weight or less based on the entire composition. Thereby, it is excellent in the adhesiveness of a polarizer and a protective film. When the amount of the unsaturated compound (D) exceeds 35% by weight, sufficient adhesion strength is not easily obtained with the polarizer. Therefore, the blending ratio of the unsaturated compound (D) is preferably 30% by weight or less, more preferably 5 to 25% by weight, still more preferably 10 to 20% by weight.
當本發明之光硬化性接著劑含有(D)成分之不飽和化合物時，為了促進其自由基聚合性並使硬化速度充分，以摻配作為(E)成分之光自由基聚合起始劑為佳。When the photocurable adhesive of the present invention contains the unsaturated compound of the component (D), in order to promote the radical polymerizability and to sufficiently accelerate the curing rate, the photoradical polymerization initiator as the component (E) is blended. good.
(E)成分之光自由基聚合起始劑的具體例並無特別限定，例如，可列舉如下述之化合物：如4’-苯氧基-2,2-二氯苯乙酮、4’-第三丁基-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-嗎啉基丙烷-1-酮、1-羥基環己基苯基酮、α,α-二乙氧基苯乙酮、2-羥基-2-甲基-1-苯基丙烷-1-酮、1-(4-異丙基苯基)-2-羥基-2-甲基丙烷-1-酮、1-(4-十二烷基苯基)-2-羥基-2-甲基丙烷-1-酮、1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基丙烷-1-酮、及2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)丁烷-1-酮等苯乙酮系光聚合起始劑；如苯偶因、苯偶因甲基醚、苯偶因乙基醚、苯偶因異丙基醚、及苯偶因異丁基醚等苯偶因醚系光聚合起始劑；如二苯甲酮、鄰-苯甲醯基安息香酸甲酯、4-苯基二苯甲酮、4-苯甲醯基-4’-甲基二苯基硫化物、及2,4,6-三甲基二苯甲酮等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、2,4-二環噻噸酮、及1-氯-4-丙氧基噻噸酮等噻噸酮(thioxanthone)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)苯基膦氧化物等醯基膦氧化物系光聚合起始劑；如1,2-辛烷二酮,1-[4-(苯硫基苯基)]-,2-(O-苯甲醯基肟)(1,2-octanedione,1-[4-(phenylthiophenyl)]-,2-(O-benzoyloxime))等肟‧酯系光聚合起始劑；樟腦醌等。The specific example of the photoradical polymerization initiator of the component (E) is not particularly limited, and examples thereof include compounds such as 4'-phenoxy-2,2-dichloroacetophenone and 4'-. Third butyl-2,2-dichloroacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-methyl-1-(4-methylthiophenyl)-2 -morpholinylpropan-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-methylpropane-1 -ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methylpropan-1-one, and 2-benzyl-2-dimethylamino-1- Acetophenone photopolymerization initiator such as (4-morpholinylphenyl)butan-1-one; such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl a phenylene ether ether photopolymerization initiator such as phenyl ether and benzoin isobutyl ether; such as benzophenone, methyl o-benzhydryl benzoate, 4-phenylbenzophenone, 4 a benzophenone-based photopolymerization initiator such as benzhydryl-4'-methyldiphenyl sulfide or 2,4,6-trimethylbenzophenone; Such as 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-bicyclothioxanthone, and 1-chloro-4-propoxythioxanthone and other thioxanthone (thioxanthone) a photopolymerization initiator; such as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4 - a mercaptophosphine oxide photopolymerization initiator such as trimethylpentylphosphine oxide or bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide; such as 1,2- Octanedione, 1-[4-(phenylthiophenyl)]-, 2-(O-benzylidene fluorene), 1,2-octanedione, 1-[4-(phenylthiophenyl)]-, 2 -(O-benzoyloxime)) is an oxime ester photopolymerization initiator; camphorquinone and the like.
(E)成分之光自由基聚合起始劑可單獨使用1種，亦可因應所期望之性能而摻配2種以上使用。摻配(E)成分之光自由基聚合起始劑時，以組成物全體作為基準，其配合比率係以10重量%以下為佳，以0.1至3重量%更佳。光自由基聚合起始劑(E)之量太多時，得不到充分之強度，又該量不足時，接著劑不會充分地硬化。The photoradical polymerization initiator of the component (E) may be used singly or in combination of two or more kinds depending on the desired properties. When the photo-radical polymerization initiator of the component (E) is blended, the blending ratio is preferably 10% by weight or less, and more preferably 0.1% to 3% by weight based on the entire composition. When the amount of the photoradical polymerization initiator (E) is too large, sufficient strength cannot be obtained, and when the amount is insufficient, the binder is not sufficiently cured.
進一步，本發明之光硬化性接著劑中，在不損及本發明之效果之範圍內，可任意摻配與前述(A)成分至(E)成分不同之其他成分。屬於如此之其他成分之一的類型者，可列舉：(A)成分之環氧化合物或(B)成分之氧雜環丁烷化合物以外之具有陽離子聚合性的化合物。其具體例並無特別之限定，可列舉如在分子內具有1個環氧基之環氧化合物等。又，屬於其他成分之另外之類型者，可列舉如無聚合性之其他成分(F)。摻配無聚合性之其他成分(F)時，以組成物全體作為基準，其配合比率係以10重量%以下左右為佳。Further, in the photocurable adhesive of the present invention, other components different from the components (A) to (E) described above may be optionally blended insofar as the effects of the present invention are not impaired. The type which is one of such other components may be a compound having a cationic polymerizable property other than the epoxy compound of the component (A) or the oxetane compound of the component (B). The specific example is not particularly limited, and examples thereof include an epoxy compound having one epoxy group in the molecule. Further, as another type of other components, other components (F) which are not polymerizable may be mentioned. When the other component (F) having no polymerizable property is blended, the blending ratio is preferably about 10% by weight or less based on the entire composition.
作為無聚合性之其他成分(F)之例者，並無特別限定，可列舉如光增感劑。藉由摻配光增感劑，可提高反應性，並可提高硬化物之機械強度或接著強度。作為光增感劑者可列舉例如：羰基化合物、有機硫化合物、過硫化物、氧化還原系化合物、偶氮及重氮化合物、鹵化合物、光還原性色素等。The example of the other component (F) which is not polymerizable is not particularly limited, and examples thereof include a photosensitizer. By blending a light sensitizer, the reactivity can be improved and the mechanical strength or strength of the cured product can be increased. Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo and a diazo compound, a halogen compound, and a photoreductive dye.
作為具體之光增感劑者，並無特別限定，可列舉如下述之化合物：如苯偶因甲基醚、苯偶因異丙基醚、及α,α-二甲氧基-α-苯基苯乙酮等苯偶因衍生物；如二苯甲酮、2,4-二氯二苯甲酮、鄰-苯甲醯基安息香酸甲酯、4,4’-雙(二甲基胺基)二苯甲酮、及4,4’-雙(二乙基胺基)二苯甲酮等二苯甲酮衍生物；如2-氯噻噸酮、及2-異丙基噻噸酮等噻噸酮衍生物；如2-氯蒽醌、及2-甲基蒽醌等蒽醌衍生物；其他如α,α-二乙氧基苯乙酮、聯苯甲醯(benzil)、茀酮、氧雜蒽酮(xanthone)、鈾醯(uranyl)化合物、鹵化合物等。The specific light sensitizer is not particularly limited, and examples thereof include compounds such as benzoin methyl ether, benzoin isopropyl ether, and α,α-dimethoxy-α-benzene. Benzoin derivatives such as acetophenone; such as benzophenone, 2,4-dichlorobenzophenone, o-benzhydryl benzoic acid methyl ester, 4,4'-bis(dimethylamine) a benzophenone derivative such as benzophenone and 4,4'-bis(diethylamino)benzophenone; such as 2-chlorothioxanthone and 2-isopropylthioxanthone a thioxanthone derivative; an anthracene derivative such as 2-chloroindole and 2-methylindole; others such as α,α-diethoxyacetophenone, benzil, and hydrazine Ketone, xanthone, uranyl compound, halogen compound, and the like.
其中，雖然亦有相當於前述(E)成分之光自由基聚合起始劑的化合物，但在此所謂的光增感劑只要係相對於(C)成分之光陽離子聚合起始劑而具有作為增感劑之機能者即可，並無特別限定。該等可分別單獨使用，亦可混合2種以上而使用。In addition, although the compound corresponding to the photo-radical polymerization initiator of the above-mentioned (E) component is also used, the photo-sensitizer as described above has a photocationic polymerization initiator as the component (C). The function of the sensitizer is not particularly limited. These may be used alone or in combination of two or more.
當以本發明之光硬化性接著劑中之陽離子性單體[含有前述之環氧化合物(A)與氧雜環丁烷化合物(B)，且當摻配有上述其他之具有陽離子性之化合物時亦含有該化合物]之總量當作100重量份時，以0.1至20重量份之範圍含有光增感劑為佳。a cationic monomer in the photocurable adhesive of the present invention [containing the aforementioned epoxy compound (A) and oxetane compound (B), and when blended with the other compound having the above cationicity When the total amount of the compound is also included as 100 parts by weight, it is preferred to contain the photosensitizer in an amount of 0.1 to 20 parts by weight.
又，作為無聚合性之其他成分(F)者，也可使用熱陽離子聚合起始劑。作為熱陽離子聚合起始劑者，可列舉：苄基鋶鹽、噻吩鎓(thiophenium)鹽、四氫噻吩鎓(thiolanium)鹽、苄基銨鹽、吡啶鎓鹽、肼鎓(hydrazinium)鹽、羧酸酯、磺酸酯、胺醯亞胺等。此等起始劑可從市售品中容易取得，例如，皆以商名品表示，可列舉如"ADEKA OPTON CP77"及"ADEKA OPTON CP66"(以上，ADEKA(股)製)、"CI-2639"、及"CI-2624"(以上，日本曹達(股)製)、"San aid SI-60L"、"San aid SI-80L"、及"San aid SI-100L"(以上，三新化學工業(股)製)等。Further, as the other component (F) having no polymerizable property, a thermal cationic polymerization initiator can also be used. Examples of the thermal cationic polymerization initiator include a benzyl sulfonium salt, a thiophenium salt, a thiolanium salt, a benzyl ammonium salt, a pyridinium salt, a hydrazinium salt, and a carboxy group. Acid esters, sulfonates, amine imines, and the like. Such a starter can be easily obtained from a commercially available product, and is, for example, a trade name product, and examples thereof include "ADEKA OPTON CP77" and "ADEKA OPTON CP66" (above, ADEKA (share) system), "CI-2639" ", and "CI-2624" (above, Japan's Soda (share) system), "San Aid SI-60L", "San Aid SI-80L", and "San Aid SI-100L" (above, Sanxin Chemical Industry) (share) system, etc.
多元醇類因為有促進陽離子聚合之性質，故也可作為無聚合性之其他成分(F)使用。多元醇類係以不存有酚性羥基以外之酸性基者為佳，可列舉例如不具有羥基以外之官能基的多元醇化合物、聚酯多元醇化合物、聚己內酯多元醇化合物、具有酚性羥基之多元醇化合物、聚碳酸酯多元醇化合物等。Since the polyol has a property of promoting cationic polymerization, it can also be used as the other component (F) having no polymerizability. The polyol is preferably an acid group other than the phenolic hydroxyl group, and examples thereof include a polyol compound having no functional group other than a hydroxyl group, a polyester polyol compound, a polycaprolactone polyol compound, and a phenol. A polyol compound of a hydroxyl group, a polycarbonate polyol compound, or the like.
再者，在不損及本發明之效果之範圍內，可摻配下述者作為無聚合性之其他成分(F)：矽烷偶合劑、離子捕捉劑、抗氧化劑、光安定劑、鍵轉移劑、增感劑、黏著賦予劑、熱可塑性樹脂、充填劑、流動調整劑、可塑劑、消泡劑、塗平劑、色素、有機溶劑等。在更提高與保護膜之密著性之目的下，摻配熱可塑性樹脂作為無聚合性之其他成分(F)亦為有效。從提高偏光件之耐久性的觀點而言，熱可塑性樹脂係以玻璃轉移溫度在70℃以上者為佳，特佳之例子是甲基丙烯酸甲酯系聚合物等。Further, insofar as the effects of the present invention are not impaired, the following may be blended as the other component (F) having no polymerizability: a decane coupling agent, an ion scavenger, an antioxidant, a photostabilizer, a bond transfer agent, Sensitizer, adhesion-imparting agent, thermoplastic resin, filler, flow regulator, plasticizer, antifoaming agent, coating agent, coloring matter, organic solvent, and the like. It is also effective to blend a thermoplastic resin as the other component (F) having no polymerity for the purpose of further improving the adhesion to the protective film. From the viewpoint of improving the durability of the polarizing material, the thermoplastic resin is preferably a glass transition temperature of 70 ° C or higher, and a particularly preferable example is a methyl methacrylate polymer.
以上說明之光硬化性接著劑係為了在由經單軸延伸且經吸附配向二色性色素之聚乙烯醇系樹脂薄膜所成之偏光件上接著保護膜而使用，在如此之偏光件上黏貼保護膜而成為偏光板。亦即，本發明之偏光板只要是在由經單軸延伸且經吸附配向二色性色素之聚乙烯醇系樹脂薄膜所成之偏光件上黏貼保護膜者即可，而無特別限定。保護膜可只黏貼在偏光件之單面，亦可黏貼在偏光件之兩面。在偏光件之兩面黏貼保護膜時，各個保護膜可由相同種類之樹脂做成，亦可由不同種類之樹脂做成。The photocurable adhesive agent described above is used for adhering a protective film to a polarizing member made of a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed to a dichroic dye, and is pasted on such a polarizing member. The protective film becomes a polarizing plate. In other words, the polarizing plate of the present invention is not particularly limited as long as it is adhered to a polarizing member made of a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed to the dichroic dye. The protective film can be adhered only to one side of the polarizing member or to both sides of the polarizing member. When the protective film is adhered to both sides of the polarizing member, each of the protective films may be made of the same kind of resin or may be made of different kinds of resins.
構成偏光件之聚乙烯醇系樹脂，係藉由將聚醋酸乙烯酯系樹脂予以皂化而得。作為聚醋酸乙烯酯系樹脂者，除了醋酸乙烯酯之單獨聚合物的聚醋酸乙烯酯以外，可例示：醋酸乙烯酯及可與其共聚合之其他單體的共聚合體等。作為可與醋酸乙烯酯共聚合之其他單體者，列舉如：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並無特別限定，通常是85至100莫耳%，以98至100莫耳%之範圍為佳。該聚乙烯醇系樹脂亦可進一步改質，例如，亦可使用經醛類改質之聚乙烯甲醛(polyvinyl formal)或聚乙烯縮醛(polyvinyl acetal)等。聚乙烯醇系樹脂之聚合度並無特別限定，通常是1,000至10,000，而以1,500至10,000之範圍為佳。The polyvinyl alcohol-based resin constituting the polarizer is obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, a polyvinyl acetate of a vinyl acetate alone polymer, a copolymer of vinyl acetate and another monomer copolymerizable therewith, and the like can be exemplified. Examples of other monomers copolymerizable 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 not particularly limited and is usually from 85 to 100 mol%, preferably from 98 to 100 mol%. The polyvinyl alcohol-based resin may be further modified. For example, polyvinyl formal or polyvinyl acetal modified with an aldehyde may be used. The degree of polymerization of the polyvinyl alcohol-based resin is not particularly limited, but is usually from 1,000 to 10,000, and preferably from 1,500 to 10,000.
偏光板係經由下述步驟而製造：將如此之聚乙烯醇系樹脂薄膜予以單軸延伸的步驟；將聚乙烯醇系樹脂薄膜以二色性色素染色，並吸附該二色性色素的步驟；將己吸附二色性色素之聚乙烯醇系樹脂薄膜以硼酸水溶液處理的步驟；在經由硼酸水溶液處理後進行水洗之步驟；及在實施該等步驟後，於經吸附配向二色性色素且經單軸延伸之聚乙烯醇系樹脂薄膜上黏貼保護膜之步驟。The polarizing plate is produced by a step of uniaxially stretching the polyvinyl alcohol-based resin film, a step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye, and adsorbing the dichroic dye; a step of treating a polyvinyl alcohol-based resin film having a dichroic dye adsorbed thereon with a boric acid aqueous solution; a step of washing with water after treatment with an aqueous solution of boric acid; and, after performing the steps, adsorbing and aligning the dichroic dye A step of adhering a protective film to a uniaxially stretched polyvinyl alcohol resin film.
單軸延伸可在藉由二色性色素染色之前進行，亦可與藉由二色性色素染色同時進行，亦可在藉由二色性色素染色之後進行。當在藉由二色性色素染色之後進行單軸延伸時，該單軸延伸可在硼酸處理之前進行，亦可在硼酸處理中進行。此外，當然亦可在此等複數個階段中進行單軸延伸。單軸延伸係可在周速不同之輥筒間往單軸延伸，也可使用熱輥筒而往單軸延伸。又，可為在大氣中進行延伸之乾式延伸，亦可為在藉由溶劑膨潤之狀態下進行延伸之濕式延伸。延伸倍率並無特別限定，通常是4至8倍左右。The uniaxial stretching may be carried out before the dyeing by the dichroic dye, or simultaneously by the dyeing with the dichroic dye, or after the dyeing by the dichroic dye. When uniaxial stretching is performed after dyeing by a dichroic dye, the uniaxial stretching can be carried out before the boric acid treatment, or in the boric acid treatment. In addition, it is of course also possible to perform uniaxial stretching in these plurality of stages. The uniaxial extension can be uniaxially extended between rolls having different peripheral speeds, or can be uniaxially extended using a hot 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 not particularly limited and is usually about 4 to 8 times.
若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在含有二色性色素之水溶液中即可，二色性色素具體上是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, and the dichroic dye is specifically iodine or two. Color dyes.
使用碘作為二色性色素時，通常是採用在含有碘及碘化鉀之水溶液中浸漬聚乙烯醇系樹脂薄膜並染色之方法。在該水溶液中，碘之含量並無特別限定，通常是每100重量份水中有0.01至0.5重量份左右，碘化鉀之含量並無特別限定，通常是每100重量份水中有0.5至10重量份左右。該水溶液之溫度並無特別限定，通常是20至40℃左右，又，對該水溶液之浸漬時間並無特別限定，通常是30至300秒鐘左右。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 usually used. The content of iodine in the aqueous solution is not particularly limited, and is usually about 0.01 to 0.5 parts by weight per 100 parts by weight of water, and the content of potassium iodide is not particularly limited, and is usually about 0.5 to 10 parts by weight per 100 parts by weight of water. . The temperature of the aqueous solution is not particularly limited, but is usually about 20 to 40 ° C. Further, the immersion time of the aqueous solution is not particularly limited, but is usually about 30 to 300 seconds.
另一方面，使用二色性染料作為二色性色素時，通常是採用在含有水溶性二色性染料之水溶液中浸漬聚乙烯醇系樹脂薄膜並染色之方法。在該水溶液中，二色性染料之含量並無特別限定，通常是每100重量份水有1×10-3 至1×10-2 重量份左右。該水溶液亦可含有硫酸鈉等無機鹽。該水溶液之溫度並無特別限定，通常是20至80℃左右，又，對該水溶液之浸漬時間並無特別限定，通常是30至300秒鐘左右。On the other hand, when a dichroic dye is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing it is usually employed. The content of the dichroic dye in the aqueous solution is not particularly limited, but is usually 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 not particularly limited, but is usually about 20 to 80 ° C. Further, the immersion time of the aqueous solution is not particularly limited, but is usually about 30 to 300 seconds.
在經由二色性色素染色後之硼酸處理，係藉由將經染色之聚乙烯醇系樹脂薄膜浸漬在硼酸水溶液中來進行。硼酸水溶液中硼酸之含量並無特別限定，通常每100重量份水有2至15重量份左右，較佳是5至12重量份左右。使用碘作為二色性色素時，該硼酸水溶液以含有碘化鉀為佳。硼酸水溶液中碘化鉀之含量並無特別限定，通常每100重量份水有2至20重量份左右，較佳是5至15重量份左右。對硼酸水溶液之浸漬時間並無特別限定，通常是100至1,200秒鐘左右，較佳是150至600秒鐘左右，更佳是200至400秒鐘左右。硼酸水溶液之溫度並無特別限定，通常是50℃以上，較佳是50至85℃左右。The boric acid treatment after dyeing through 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 not particularly limited, but is usually about 2 to 15 parts by weight, 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 not particularly limited, but is usually about 2 to 20 parts by weight, preferably about 5 to 15 parts by weight, per 100 parts by weight of water. The immersion time of the aqueous boric acid solution is not particularly limited, but is usually about 100 to 1,200 seconds, preferably about 150 to 600 seconds, more preferably about 200 to 400 seconds. The temperature of the aqueous boric acid solution is not particularly limited, and is usually 50 ° C or higher, preferably about 50 to 85 ° C.
硼酸處理後之聚乙烯醇系樹脂薄膜，通常會施以水洗處理。水洗處理係例如藉由將經硼酸處理後之聚乙烯醇系樹脂薄膜浸漬在水中而進行。水洗後，實施乾燥處理而得偏光件。在水洗處理中，水之溫度並無特別限定，通常是5℃至40℃左右。浸漬時間並無特別限定，通常是2至120秒鐘左右，其後進行之乾燥處理通常是使用熱風乾燥機或遠紅外線加熱器而進行。乾燥溫度並無特別限定，通常是40℃至100℃。乾燥處理之處理時間並無特別限定，通常是120至600秒鐘左右。The polyvinyl alcohol-based resin film after boric acid treatment is usually subjected to a water washing treatment. The water washing treatment is performed, for example, by immersing a boric acid-treated polyvinyl alcohol-based resin film in water. After washing with water, drying treatment was carried out to obtain a polarizing member. In the water washing treatment, the temperature of the water is not particularly limited, but is usually about 5 ° C to 40 ° C. The immersion time is not particularly limited, but is usually about 2 to 120 seconds, and the drying treatment thereafter is usually carried out using a hot air dryer or a far infrared ray heater. The drying temperature is not particularly limited and is usually from 40 ° C to 100 ° C. The treatment time of the drying treatment is not particularly limited and is usually about 120 to 600 seconds.
因此，獲得由經吸附配向作為二色性色素之碘或二色性染料的聚乙烯醇系樹脂薄膜所構成的偏光件。Therefore, a polarizer comprising a polyvinyl alcohol-based resin film which is adsorbed and aligned as an iodine or a dichroic dye of a dichroic dye is obtained.
其次，該偏光件係使用先前說明之光硬化性接著劑而在其單面或兩面黏貼保護膜。作為偏光件之保護膜而自以往以來一直廣泛採用之三乙醯基纖維素薄膜係大致上有400g/m2 /24小時左右之透濕度，但在本發明中，偏光件之至少一面所黏貼之保護膜係採用顯示較該三乙醯基纖維素更低之透濕度的樹脂，其為聚酯樹脂、聚碳酸酯樹脂或丙烯酸系樹脂。Next, the polarizing member is adhered to the protective film on one or both sides thereof using the photocurable adhesive described above. The triethylenesulfonyl cellulose film which has been widely used as a protective film for a polarizer has a moisture permeability of about 400 g/m 2 /24 hours, but in the present invention, at least one side of the polarizing member is pasted. The protective film is a resin which exhibits a lower moisture permeability than the triacetyl cellulose, and is a polyester resin, a polycarbonate resin or an acrylic resin.
保護膜所使用之聚酯樹脂之種類並無特別限定者，在機械性質、耐溶劑性、耐擦傷性、成本等方面而言，以聚對苯二甲酸乙二酯(polyethylene terephthalate)為特佳。聚對苯二甲酸乙二酯是指由重複單元的80莫耳%以上為對苯二甲酸乙二酯所構成之樹脂，也可含有源自其他共聚合成分之構成單元。作為其他共聚合成分者，較佳例係列舉：如間苯二甲酸、對-β-羥基乙氧基安息香酸、4,4’-二羧基二苯基、4,4’-二羧基二苯甲酮、雙(4-羧基苯基)乙烷、己二酸、癸二酸、5-磺酸基間苯二甲酸鈉、及1,4-二羧基環己烷等二羧酸成分；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、聚丙二醇及聚四亞甲基二醇等二醇(diol)成分等。此等二羧酸成分或二醇成分，因應需要可分別組合2種以上而使用。又，亦可併用上述二羧酸成分或二醇成分、與對-羥基安息香酸等羥基羧酸。也可少量使用具有醯胺鍵、胺酯鍵、醚鍵、碳酸酯鍵等之二羧酸成分及/或二醇成分以作為其他共聚合成分。The type of the polyester resin used for the protective film is not particularly limited, and 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 repeating units of ethylene terephthalate, and may also contain constituent units derived from other copolymerized components. As other copolymerization components, preferred examples are: isophthalic acid, p-β-hydroxyethoxybenzoic acid, 4,4'-dicarboxydiphenyl, 4,4'-dicarboxydiphenyl a dicarboxylic acid component such as ketone, bis(4-carboxyphenyl)ethane, adipic acid, sebacic acid, sodium 5-sulfoisophthalate, and 1,4-dicarboxycyclohexane; such as propylene glycol Butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, ethylene oxide adduct of bisphenol A, diols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol (diol) component, etc. These dicarboxylic acid components or diol components can be used in combination of two or more types as needed. Further, the above dicarboxylic acid component, diol component, and hydroxycarboxylic acid such as p-hydroxybenzoic acid may be used in combination. A dicarboxylic acid component and/or a diol component having a guanamine bond, an amine ester bond, an ether bond, a carbonate bond or the like may be used in a small amount as another copolymerization component.
聚酯樹脂之製造方法，可採用下述之任一方法：使對苯二甲酸與乙二醇(進一步因應需求之其他二羧酸成分及/或二醇成分)直接反應的所謂直接聚合法、使對苯二甲酸之二甲基酯與乙二醇(進一步因應需求之其他二羧酸成分之二甲基酯及/或其他二醇成分)進行酯交換反應的所謂酯交換反應法等。又，聚酯樹脂中因應需求也可含有習知之添加劑。作為可含有之添加劑者並無特別限定，例如可列舉如：潤滑劑、抗結塊劑(antiblocking agent)、熱安定劑、抗氧化劑、抗靜電劑、耐光劑、耐衝擊性改良劑等。但是，由於在偏光薄膜上積層之保護薄膜需要透明性，所以該等添加劑之量以止於最小限度為佳。The method for producing the polyester resin may be any one of the following methods: a direct polymerization method in which terephthalic acid and ethylene glycol (further depending on other dicarboxylic acid components and/or diol components required) are directly reacted, A so-called transesterification reaction method in which a dimethyl ester of terephthalic acid is subjected to a transesterification reaction with ethylene glycol (further depending on a desired dimethyl ester of a dicarboxylic acid component and/or other diol component). Further, the polyester resin may contain a conventional additive as needed. The additive which can be contained is not particularly limited, and examples thereof include a lubricant, an antiblocking agent, a thermal stabilizer, an antioxidant, an antistatic agent, a light stabilizer, and an impact resistance improver. However, since the protective film laminated on the polarizing film requires transparency, the amount of such additives is preferably minimized.
使上述原料樹脂成形為薄膜狀，藉由實施單軸延伸或雙軸延伸處理，可製作由已延伸之聚酯樹脂所成的保護薄膜。藉由實施延伸處理，可得到機械強度高之薄膜。製作經延伸之聚酯樹脂薄膜的方法為任意而無特別限定，可列舉如：將熔融上述原料樹脂並擠壓成形為薄片狀之無配向薄膜，在玻璃轉移溫度以上的溫度中以拉幅機(tenter)進行橫向延伸後，實施熱固定處理之方法。The raw material resin is formed into a film shape, and by performing uniaxial stretching or biaxial stretching treatment, a protective film made of the stretched polyester resin can be produced. By performing the stretching treatment, a film having high mechanical strength can be obtained. The method of producing the stretched polyester resin film is not particularly limited, and examples thereof include an unaligned film in which the raw material resin is melted and extruded into a sheet shape, and a tenter is used at a temperature higher than the glass transition temperature. (tenter) A method of performing a heat setting treatment after performing lateral stretching.
保護膜所使用之聚碳酸酯樹脂，較佳例可列舉如由碳酸與甘醇(glycol)或雙酚所形成之聚酯。其中，在分子鏈中具有二苯基烷烴之芳香族聚碳酸酯係由於在耐熱性、耐候性及耐酸性方面優異，故而適合使用。作為如此之聚碳酸酯者，可例示：由如2,2-雙(4-羥基苯基)丙烷(別名雙酚A)、2,2-雙(4-羥基苯基)丁烷、1,1-雙(4-羥基苯基)環己烷、1,1-雙(4-羥基苯基)異丁烷、或1,1-雙(4-羥基苯基)乙烷等雙酚類所衍生之聚碳酸酯。Preferred examples of the polycarbonate resin used for the protective film include polyesters formed of carbonic acid and a glycol or bisphenol. Among them, an aromatic polycarbonate having a diphenyl alkane in a molecular chain is preferably used because it is excellent in 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, Bisphenols such as 1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)isobutane, or 1,1-bis(4-hydroxyphenyl)ethane Derived polycarbonate.
聚碳酸酯樹脂薄膜之製造法，可使用流延製膜法、熔融擠壓法等之任一種方法。具體之製造方法例可列舉：使聚碳酸酯樹脂溶解到適當之有機溶劑中而作為聚碳酸酯樹脂溶液，將其在金屬支持體上流延而形成網狀物，自前述金屬支持體上剝離取得該網狀物後，將該剝取之網狀物經熱風乾燥而獲得薄膜之方法。As a method of producing the polycarbonate resin film, any one of a casting film forming method and a melt extrusion method can be used. Specific examples of the production method include dissolving a polycarbonate resin in a suitable organic solvent as a polycarbonate resin solution, casting it on a metal support to form a network, and peeling off from the metal support. After the web, the stripped web is dried by hot air to obtain a film.
保護膜所使用之丙烯酸系樹脂也無特別限定，一般是以將甲基丙烯酸酯當作主成分單體並使其與少量之其他共單體成分共聚合而成的共聚合物為佳。作為丙烯酸系樹脂的主成分之甲基丙烯酸酯，以列舉甲基丙烯酸烷酯為佳，尤其適合使用甲基丙烯酸甲酯。又，作為共單體成分者並無特別限定，一般是使用丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等。進一步，也可將如苯乙烯等芳香族乙烯化合物、或如丙烯腈等乙烯氰化合物等當作共單體成分。The acrylic resin to be used for the protective film is not particularly limited, and a copolymer of methacrylate as a main component monomer and a small amount of other comonomer components is generally preferred. The methacrylate which is a main component of the acrylic resin is preferably an alkyl methacrylate, and methyl methacrylate is particularly preferably used. Further, the comonomer component is not particularly limited, and generally, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate or the like is used. Further, an aromatic vinyl compound such as styrene or an ethylene cyanide compound such as acrylonitrile may be used as a comonomer component.
丙烯酸系樹脂之製造法，可採用通常之塊狀聚合、懸濁聚合、乳化聚合等任意方法。其中尤其以採用在聚合系內不存在有水溶性成分之塊狀聚合為佳。此外，為了得到適合之玻璃移轉溫度，又為了得到顯示較佳之薄膜成形性的黏度，故在聚合時以使用鏈轉移劑為佳。鏈轉移劑之量，只要因應單體之種類及組成而適當決定即可。又，丙烯酸系樹脂因應需求亦可含有習知之添加劑。習知之添加劑可列舉如：潤滑劑、防結塊劑、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。但是，由於在偏光薄膜上積層之保護薄膜需要透明性，所以該等添加劑之量以止於最小限度為佳。The method for producing the acrylic resin can be any conventional method such as bulk polymerization, suspension polymerization, or emulsion polymerization. Among them, in particular, block polymerization in which no water-soluble component is present in the polymerization system is preferred. Further, in order to obtain a suitable glass transition temperature and to obtain a viscosity which exhibits good film formability, it is preferred to use a chain transfer agent during polymerization. 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 contain a conventional additive as needed. The conventional additives may, for example, be a lubricant, an anti-caking agent, a thermal stabilizer, an antioxidant, an antistatic agent, a light stabilizer, an impact modifier, a surfactant, and the like. However, since the protective film laminated on the polarizing film requires transparency, the amount of such additives is preferably minimized.
丙烯酸系樹脂薄膜之製造法，可使用如熔融流延法、T模具(T-die)法或吹塑薄膜法(inflation method)等熔融擠壓法、壓延法(calender method)等之任一種方法。其中，將原料樹脂從例如T模具熔融擠壓出並將所得膜狀物之至少單面與輥筒或輸送帶(belt)接觸而製膜之方法，係從得到表面性狀良好之薄膜之觀點而言為佳者。As a method of producing the acrylic resin film, any one of a melt extrusion method such as a melt casting method, a T-die method, or an inflation method, or a calender method can be used. . Among them, a method in which a raw material resin is melt-extruded from, for example, a T-die, and at least one side of the obtained film is brought into contact with a roll or a belt to form a film is obtained from the viewpoint of obtaining a film having a good surface property. The words are good.
從薄膜之製膜性或薄膜之耐衝擊性等之觀點而言，丙烯酸系樹脂亦可含有作為衝擊性改良劑之丙烯酸系橡膠粒子。在此，所謂丙烯酸系橡膠粒子只要是以將丙烯酸酯當作主體之彈性聚合物作為必需成分之粒子即可，而無特別限定，實質上可列舉只由該彈性聚合物所成之單層結構者、或將該彈性聚合物當作1層之多層結構者。該彈性聚合物之例可列舉如：以丙烯酸烷酯作為主成分，並與可與其共聚合之其他乙烯單體以及交聯性單體進行共聚合而成之交聯彈性共聚物。作為彈性聚合物之主成分的丙烯酸烷酯可列舉如：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至8左右者，尤其以使用具有碳數4以上之烷基的丙烯酸酯為佳。可與該丙烯酸烷酯共聚合之其他乙烯單體可列舉如在分子內具有1個聚合性碳-碳雙鍵之化合物，更具體而言可列舉：如甲基丙烯酸甲酯等甲基丙烯酸酯、如苯乙烯等芳香族乙烯化合物、如丙烯腈等乙烯氰化合物等。又，交聯性單體可列舉在分子內具有至少2個聚合性碳-碳雙鍵之交聯性化合物，更具體而言可列舉：如乙二醇二(甲基)丙烯酸酯及丁二醇二(甲基)丙烯酸酯等多元醇的(甲基)丙烯酸酯類、如(甲基)丙烯酸烯丙酯等(甲基)丙烯酸的烯基酯、二乙烯基苯等。The acrylic resin may contain acrylic rubber particles as an impact modifier, from the viewpoint of film forming properties of the film, impact resistance of the film, and the like. Here, the acrylic rubber particles are not particularly limited as long as they are an elastic polymer having an acrylate as a main component, and are not particularly limited, and a single layer structure composed only of the elastic polymer is substantially exemplified. Or the elastic polymer as a one-layer multilayer structure. Examples of the elastic polymer include a crosslinked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component and another ethylene monomer and a crosslinkable monomer copolymerizable therewith. The alkyl acrylate which is a main component of the elastic polymer may, for example, be an alkyl group such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate having a carbon number of from 1 to 8, especially in use. An acrylate having an alkyl group having 4 or more carbon atoms is preferred. Other ethylene monomers copolymerizable with the alkyl acrylate may, for example, be 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 or an ethylene cyanide compound such as acrylonitrile. Further, the crosslinkable monomer may be 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 dibutyl A (meth) acrylate of a polyhydric alcohol such as an alcohol di(meth)acrylate, an alkenyl ester of (meth)acrylic acid such as (meth)acrylic acid acrylate, or divinylbenzene.
進一步，亦可將由不含有橡膠粒子之丙烯酸系樹脂所成的薄膜、與由含有橡膠粒子之丙烯酸系樹脂所成的薄膜之積層物當作保護膜。Further, a laminate of a film made of an acrylic resin not containing rubber particles and a film made of an acrylic resin containing rubber particles may be used as a protective film.
在液晶顯示裝置之視認側使用之偏光板中，對於其視認側，亦即在與液晶胞相反側配置之保護膜，可賦予防眩性。此時，在成為保護膜之視認側的表面，亦即在與黏貼於偏光件之面相反側之面，一般設置具有表面凹凸之防眩層。防眩層一般是藉由下述方法而形成：對於活性能源線硬化性樹脂以壓花法賦予凹凸，或是於活性能源線硬化性樹脂中摻配具有與其不同之折射率的微粒子並使其硬化而賦予凹凸之方法。又，當以丙烯酸系樹脂構成保護膜時，使用下述積層薄膜來構成保護膜係亦為有效：在成為黏結劑(binder)的丙烯酸系樹脂中摻配具有與其不同之折射率的微粒子而成的光擴散層、與由沒有摻配該微粒子之丙烯酸系樹脂所成的透明層之積層薄膜。此時，可採用下述型態：將由上述光擴散層與上述透明層之2層所成的積層薄膜，以其光擴散層側黏貼在偏光件之形態；或是將上述光擴散層之兩面以上述透明層挾住的3層結構的積層薄膜，以其一邊的透明層黏貼在偏光件之形態等。進一步，將因含有如此之光擴散層而賦予防眩性之丙烯酸系樹脂積層薄膜當作保護膜時，在作為其視認側之表面，亦即在與黏貼於偏光件之面相反側之面，設置如上述之防眩層，即亦可更有效地提高防眩性能。In the polarizing plate used for the viewing side of the liquid crystal display device, the protective film disposed on the side opposite to the liquid crystal cell can be imparted with anti-glare properties. At this time, an anti-glare layer having surface irregularities is generally provided on the surface on the viewing side of the protective film, that is, on the surface opposite to the surface to be adhered to the polarizing material. The antiglare layer is generally formed by imparting irregularities to the active energy ray-curable resin by embossing, or by doping fine particles having refractive indices different from those of the active energy ray-curable resin. A method of hardening to impart unevenness. Further, when the protective film is made of an acrylic resin, it is also effective to form a protective film by using the laminated film described below: a fine resin having a refractive index different from that of the acrylic resin to be a binder is blended. A laminated film of a light diffusion layer and a transparent layer made of an acrylic resin to which the fine particles are not blended. In this case, a laminated film formed by the two layers of the light-diffusing layer and the transparent layer may be attached to the light-diffusing layer side in the form of a polarizing member, or both sides of the light-diffusing layer may be used. The laminated film of the three-layer structure which is sandwiched by the transparent layer is adhered to the form of a polarizer by a transparent layer on one side. Further, when the acrylic resin laminated film which is provided with such a light-diffusing layer and which has an anti-glare property is used as a protective film, the surface on the side of the viewing side, that is, the surface opposite to the surface to be adhered to the polarizing member, By providing the anti-glare layer as described above, it is also possible to more effectively improve the anti-glare property.
如前述，尤其以丙烯酸系樹脂薄膜作為保護膜時，在先前之專利文獻6(日本特開2004-245925號公報)所揭示之不含芳香環的環氧樹脂單體之接著性係不一定充分，而本發明之光硬化性接著劑，即使在將該丙烯酸系樹脂薄膜作為保護膜時也可賦予良好之接著力。因此，本發明係在將丙烯酸系樹脂薄膜作為保護膜時為特別有用。此時，在光硬化性接著劑中若含有先前說明之(D)成分的不飽和化合物，尤其是丙烯酸系化合物，則會更佳。As described above, in particular, when an acrylic resin film is used as the protective film, the adhesiveness of the epoxy resin-free epoxy resin disclosed in the prior patent document 6 (JP-A-2004-245925) is not necessarily sufficient. Further, the photocurable adhesive of the present invention can impart a good adhesion even 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. In this case, it is more preferable that the photocurable adhesive contains an unsaturated compound of the component (D) described above, particularly an acrylic compound.
在本發明中，於偏光件之至少一面上，由選自上述說明之聚酯樹脂、聚碳酸酯樹脂、及丙烯酸系樹脂之透明樹脂薄膜所成的保護膜係係隔著先前說明之光硬化性接著劑而黏貼。當只在偏光件之單面黏貼保護膜時，亦可採取例如在偏光件之另一面，直接設置用以與液晶胞等其他構材黏貼之黏著劑層等之形態。In the present invention, the protective film formed of a transparent resin film selected from the above-described polyester resin, polycarbonate resin, and acrylic resin is bonded to at least one surface of the polarizer via the photohardening described above. Adhered to the adhesive. When the protective film is adhered to only one side of the polarizing member, for example, an adhesive layer or the like which is adhered to other members such as liquid crystal cells may be directly provided on the other surface of the polarizing member.
另一方面，於偏光件之兩面黏貼保護膜時，各個保護膜可為相同種類者，亦可為不同種類者。具體上，例如以採用下述型態為佳：在偏光件之兩面上，以聚酯樹脂薄膜作為保護膜而黏貼之形態；在偏光件之兩面上，以聚碳酸酯樹脂作為保護膜而黏貼之形態；在偏光件之兩面上，以丙烯酸系樹脂作為保護膜而黏貼之形態；在偏光件之單面上，以選自聚酯樹脂、聚碳酸酯樹脂、及丙烯酸系樹脂之任一透明樹脂薄膜作為保護膜而黏貼，並在偏光件之另一面上，以選自聚酯樹脂、聚碳酸酯樹脂、及丙烯酸系樹脂之任一種且與上述單面之保護膜不同的透明樹脂薄膜作為保護膜而黏貼之形態等。再者，亦可採用下述型態：在偏光件之單面上，以選自聚酯樹脂、聚碳酸酯樹脂、及丙烯酸系樹脂之任一透明樹脂薄膜作為保護膜而黏貼，並在偏光件之另一面上，以與聚酯樹脂、聚碳酸酯樹脂、及丙烯酸系樹脂之任一種皆不同的透明樹脂薄膜作為保護膜而黏貼之形態。在偏光件之兩面黏貼保護膜時，可將2片保護膜以階段性之方式一面一面逐次黏貼，亦可將兩面以一階段進行黏貼。On the other hand, when the protective film is adhered to both surfaces of the polarizer, the respective protective films may be of the same type or different types. Specifically, for example, it is preferable to adopt a form in which a polyester resin film is adhered as a protective film on both sides of the polarizing member, and a polycarbonate resin is used as a protective film on both sides of the polarizing member. a form in which an acrylic resin is adhered to a protective film on both sides of a polarizing member; and one of a polyester resin, a polycarbonate resin, and an acrylic resin is transparent on one side of the polarizing member. The resin film is adhered as a protective film, and a transparent resin film selected from the group consisting of a polyester resin, a polycarbonate resin, and an acrylic resin and different from the one-side protective film is used as the other surface of the polarizing member. The shape of the protective film and the like. Furthermore, it is also possible to adopt a pattern in which a transparent resin film selected from a polyester resin, a polycarbonate resin, and an acrylic resin is applied as a protective film on one side of the polarizing member, and is polarized. On the other side of the article, a transparent resin film which is different from any one of a polyester resin, a polycarbonate resin, and an acrylic resin is used as a protective film. When the protective film is adhered to both sides of the polarizing member, the two protective films may be adhered one by one in a stepwise manner, or both sides may be adhered in one stage.
在偏光件之兩面黏貼保護膜時，並且將其中之一邊做成與聚酯樹脂、聚碳酸酯樹脂、及丙烯酸系樹脂不同之其他樹脂薄膜時，該其他樹脂之適當例可列舉如纖維素系樹脂或非晶性聚烯烴系樹脂。又，在偏光件之一面所黏貼之由聚酯樹脂、聚碳酸酯樹脂、或丙烯酸系樹脂所成之保護膜，係依照本發明隔著先前說明之光硬化性接著劑而接著，但在偏光件之另一面所黏貼之保護膜則亦可隔著其他接著劑而接著。例如，當在偏光件之一面設置由如纖維素樹脂薄膜般透濕度較高之樹脂薄膜所成之保護膜時，在該透濕度高之樹脂薄膜之黏貼面，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因為對於此處例示之纖維素樹脂薄膜或非晶性聚烯烴素樹脂薄膜亦賦予高的接著力，故在偏光件之兩面使用相同接著劑係因操作簡單而為較有利。When the protective film is adhered to both surfaces of the polarizing member, and one of the other resins is made of a polyester resin, a polycarbonate resin, or an acrylic resin, a suitable example of the other resin may be, for example, a cellulose system. Resin or amorphous polyolefin resin. Further, a protective film made of a polyester resin, a polycarbonate resin, or an acrylic resin adhered to one surface of the polarizer is adhered to the photocurable adhesive described above according to the present invention, but is polarized. The protective film adhered to the other side of the piece may be followed by another adhesive. For example, when a protective film made of a resin film having a high moisture permeability such as a cellulose resin film is provided on one surface of the polarizing member, a polyvinyl alcohol-based adhesive film may be used for the adhesive film having a high moisture permeability. An adhesive other than an epoxy resin. However, since the photocurable adhesive of the present invention imparts a high adhesion to the cellulose resin film or the amorphous polyolefin resin film exemplified herein, the use of the same adhesive on both sides of the polarizer is simple in operation. It is more advantageous.
可作為其中一邊之保護膜而使用之纖維素樹脂薄膜，係纖維素之部分或完全之酯化物，例如可列舉：纖維素之乙酸酯、丙酸酯、丁酸酯、該等之混合酯等。具體上可列舉：三乙醯基纖維素、二乙醯基纖維素、纖維素乙酸酯丙酸酯、纖維素乙酸酯丁酸酯等。由如此之纖維素酯系樹脂所成之薄膜的市售品之例並無特別限定，可列舉如：富士薄膜(股)製之"Fujitac TD80"、"Fujitac TD80UF"、及"Fujitac TD80UZ"、Konicaminolta Opto(股)製之"KC8UX2M"及"KC8UY"等。又，也可使用賦予光學補償機能之纖維素系樹脂薄膜。該光學補償薄膜並無特別之限定，可列舉如：在纖維素系樹脂中含有具有相位差調整機能之化合物的薄膜、在纖維素系樹脂表面塗布具有相位差調整機能之化合物者、將纖維素系樹脂往單軸或雙軸延伸而得之薄膜等。市售之纖維素系之光學補償薄膜者之例較佳可列舉如：富士薄膜(股)製之"Wide view Film WV BZ 438"及"Wide view Film WV EA"、Konicaminolta Opto(股)製之"KC4FR-1"及"KC4HR-1"等。A cellulose resin film which can be used as a protective film on one side, and is a partial or complete esterified product of cellulose, and examples thereof include cellulose acetate, propionate, butyrate, and mixed esters thereof. Wait. Specific examples thereof include triethyl fluorenyl cellulose, diethyl acetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate. An example of a commercially available product of a film made of such a cellulose ester-based resin is not particularly limited, and examples thereof include "Fujitac TD80", "Fujitac TD80UF", and "Fujitac TD80UZ" manufactured by Fuji Film Co., Ltd. "KC8UX2M" and "KC8UY" made by Konicaminolta Opto. Further, a cellulose resin film which imparts an optical compensation function can also be used. The optical compensation film is not particularly limited, and examples thereof include a film containing a compound having a phase difference adjustment function in a cellulose resin, and a compound having a phase difference adjustment function applied to a surface of a cellulose resin. A film obtained by stretching a resin into a uniaxial or biaxial direction. Examples of the commercially available cellulose-based optical compensation film are, for example, "Wide view Film WV BZ 438" manufactured by Fuji Film Co., Ltd., and "Wide view Film WV EA", manufactured by Konicaminolta Opto Co., Ltd. "KC4FR-1" and "KC4HR-1", etc.
作為與聚酯樹脂、聚碳酸酯樹脂及丙烯酸系樹脂不同之其他樹脂且作為一邊之保護膜使用的透濕度低之透明樹脂之例並無特別限定，可列舉如：非晶性聚烯烴系樹脂、聚碸樹脂、脂環式聚醯亞胺樹脂等。其中，由非晶性聚烯烴系樹脂所成之薄膜是機械性質、耐溶劑性、耐擦傷性、成本等優異之薄膜，特別適合使用。The transparent resin having a low moisture permeability, which is used as a protective film for one side, which is different from the polyester resin, the polycarbonate resin, and the acrylic resin, is not particularly limited, and examples thereof include amorphous polyolefin resins. , polyfluorene resin, alicyclic polyimide resin, and the like. Among them, the film made of the amorphous polyolefin resin is a film excellent in mechanical properties, solvent resistance, scratch resistance, cost, and the like, and is particularly suitable for use.
非晶性聚烯烴系樹脂通常以具有從如降冰片烯或其衍生物、二甲橋八氫萘等多環式之環狀烯烴所導出之聚合單元，並在如開環聚合物般殘留雙鍵時對其加氫之熱可塑性樹脂為佳。非晶性聚烯烴系樹脂可為環狀烯烴與鏈狀烯烴之共聚合物，又，亦可導入極性基。其中，作為代表例者可列舉熱可塑性飽和降冰片烯系樹脂。市售之非晶性聚烯烴系樹脂之例可列舉如：JSR(股)之"ARTON"、日本Zeon(股)製之"ZEONEX"以及"ZEONOR"、三井化學(股)製之"APO"及"APPEL"等。在將非晶性聚烯烴系樹脂製膜而形成薄膜時，製膜可適當使用溶劑鑄模法、熔融擠壓法等習知之方法。The amorphous polyolefin-based resin generally has a polymerized unit derived from a polycyclic cyclic olefin such as norbornene or a derivative thereof, or a dicyclic octahydronaphthalene, and remains as a ring-like polymer. When the bond is used, it is preferred to hydrogenate the thermoplastic resin. 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 resin saturated norbornene-based resin is exemplified as a representative example. Examples of the commercially available amorphous polyolefin-based resin include "ARTON" of JSR (share), "ZEONEX" by Japan Zeon Co., and "ZEONOR", and "APO" by Mitsui Chemicals Co., Ltd. And "APPEL" and so on. When a film is formed by forming a film of the amorphous polyolefin resin, a conventional method such as a solvent molding method or a melt extrusion method can be suitably used for the film formation.
保護膜在黏貼於偏光件之前，亦可對於黏貼面實施皂化處理、電暈處理、底漆(primer)處理、錨塗層(anchor coating)處理等易接著處理。又，在保護膜之對偏光件黏貼面的相反側之表面，亦可具有硬塗層、抗反射層、防眩層等各種處理層。保護膜之厚度並無特別限定，通常是5至200μm左右的範圍，較佳是10至120μm，更佳是10至85μm。The protective film may be subjected to a saponification treatment, a corona treatment, a primer treatment, an anchor coating treatment, or the like, before being adhered to the polarizing member. Further, various treatment layers such as a hard coat layer, an antireflection layer, and an antiglare layer may be provided on the surface of the protective film opposite to the surface to which the polarizer is adhered. The thickness of the protective film is not particularly limited and is usually in the range of about 5 to 200 μm, preferably 10 to 120 μm, more preferably 10 to 85 μm.
本發明之偏光板可藉由包含下述步驟之方法而製造：在先前說明之偏光件與由選自聚酯樹脂、聚碳酸酯樹脂及丙烯酸系樹脂之透明樹脂薄膜所成之保護膜的黏貼面中的至少一邊，塗布先前說明之光硬化性接著劑之接著劑塗布步驟；隔著所得之接著劑層而黏貼偏光件與保護膜之黏貼步驟；以及在已隔著該接著劑層黏貼偏光件與保護膜之狀態下，使光硬化性接著劑硬化之硬化步驟。The polarizing plate of the present invention can be produced by a method comprising the steps of: bonding a polarizing member previously described and a protective film made of a transparent resin film selected from the group consisting of polyester resin, polycarbonate resin and acrylic resin. At least one side of the surface, an adhesive application step of applying a photocurable adhesive as described above; a bonding step of adhering the polarizer to the protective film via the obtained adhesive layer; and a polarizing having been adhered to the adhesive layer A hardening step of hardening the photocurable adhesive in the state of the member and the protective film.
接著劑塗布步驟是在偏光件與保護膜之黏貼面中的至少一邊，塗布先前說明之光硬化性接著劑。在偏光件或保護膜之表面直接塗布光硬化性接著劑時，其塗布方法並無特別限定。例如可利用：刮刀、線棒、模具塗布機、逗點式塗布機(comma coater)、凹版塗布機等各種塗布方式。又，也可利用在偏光件與保護膜之間使先前說明之光硬化性接著劑流延之後，以輥筒等進行加壓而均勻地擠壓擴展之方法。The subsequent coating step is to apply the photocurable adhesive described above to at least one of the adhesive faces of the polarizer and the protective film. When the photocurable adhesive is directly applied to the surface of the polarizer or the protective film, the coating method is not particularly limited. For example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Further, a method in which the photocurable adhesive described above is cast between the polarizer and the protective film, and then pressurized by a roller or the like to uniformly expand and expand may be used.
在如此塗布光硬化性接著劑之後，供於黏貼步驟。在該黏貼步驟中，例如，在先前之塗布步驟中於偏光件之表面塗布光硬化性接著劑時，則在該處疊合保護膜，在先前之塗布步驟中於保護膜之表面塗布光硬化性接著劑時，則在該處疊合偏光件。又，當在偏光件與保護膜之間使光硬化性接著劑流延時，則在此狀態下疊合偏光件與保護膜。在偏光件之兩面黏貼保護膜時且兩面都使用本發明之光硬化性接著劑時，則在偏光件之兩面分別隔著光硬化性接著劑而疊合保護膜。於是，通常係在此狀態下從兩面(在偏光件之單面疊合保護膜時，則是偏光件側與保護膜側，又，在偏光件之兩面疊合保護膜時，則是其兩面之保護膜側)以輥筒等挾住並進行加壓。在此，輥筒之材質可使用金屬或橡膠等。在兩面所配置之輥筒可為相同之材質，亦可為相異之材質。After the photocurable adhesive is applied as described above, it is supplied to the pasting step. In the pasting step, for example, when a photocurable adhesive is applied to the surface of the polarizing member in the previous coating step, the protective film is laminated there, and the surface of the protective film is coated with light hardening in the previous coating step. When the adhesive is applied, the polarizer is superposed there. Further, when the photocurable adhesive is delayed between the polarizer and the protective film, the polarizer and the protective film are laminated in this state. When the protective film is adhered to both surfaces of the polarizer and the photocurable adhesive of the present invention is used on both surfaces, the protective film is laminated on both surfaces of the polarizer via a photocurable adhesive. Therefore, it is usually in this state from both sides (when the protective film is superposed on one side of the polarizing member, the polarizer side and the protective film side are overlapped, and when the protective film is laminated on both sides of the polarizing member, the two sides thereof are The protective film side) is caught by a roller or the like and pressurized. Here, the material of the roller can be metal or rubber. The rollers arranged on both sides can be of the same material or different materials.
如上述，隔著未硬化之光硬化性接著劑而黏貼偏光件與保護膜之狀態者，其次是供於硬化步驟。在該硬化步驟中，對於光硬化性接著劑照射活性能源線，使含有環氧化合物或氧雜環丁烷化合物之接著劑層硬化，而使偏光件與保護膜接著。在偏光件之單面黏貼保護膜時，活性能源線可從偏光件側、保護膜側之任意一側照射。又，在偏光件之兩面黏貼保護膜時，在偏光件之兩面分別隔著光硬化性接著劑黏貼保護膜之狀態下，以從任一邊之保護膜側照射活性能源線而使兩面之光硬化性接著劑同時硬化為有利。但是，當在任一邊之保護膜中摻配紫外線吸收劑時(例如，以摻配有紫外線吸收劑之纖維素系樹脂薄膜作為一邊之保護膜時)且活性能源線為紫外線時，通常是從另一邊未摻配紫外線吸收劑之保護膜側照射紫外線。As described above, the state in which the polarizer and the protective film are adhered via the uncured photocurable adhesive is followed by the hardening step. In the hardening step, the photocurable adhesive is applied to the active energy source to cure the adhesive layer containing the epoxy compound or the oxetane compound, and the polarizer and the protective film are followed. When the protective film is adhered to one side of the polarizing member, the active energy source can be irradiated from either the polarizer side or the protective film side. Further, when the protective film is adhered to both surfaces of the polarizer, the active light rays are irradiated from the side of the protective film on either side of the polarizer with the photocurable adhesive adhered to the protective film, and the light of both sides is hardened. It is advantageous for the adhesive to harden at the same time. However, when a UV absorber is blended in the protective film on either side (for example, when a cellulose resin film blended with a UV absorber is used as a protective film on one side) and the active energy source is ultraviolet rays, it is usually from another The side of the protective film which is not blended with the ultraviolet absorber is irradiated with ultraviolet rays.
活性能源線雖可使用可見光線、紫外線、X線、電子束等，但從容易處理且硬化速度也十分快之觀點而言，一般以使用紫外線為佳。活性能源線之光源並無特別限定，可使用在波長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(black light lamp)、微波激發水銀燈、金屬鹵素燈、LED燈等。Although the visible light rays, ultraviolet rays, X-rays, electron beams, and the like can be used as the active energy source, it is generally preferable to use ultraviolet rays from the viewpoint of easy handling and fast curing speed. The light source of the active energy source is not particularly limited, and 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 lamp, a microwave-excited mercury lamp having a light-emitting distribution at a wavelength of 400 nm or less can be used. Metal halide lamps, LED lamps, etc.
對光硬化性接著劑之光照射強度係依各個作為目的之組成物而分別決定者，雖無特別限定，但聚合起始劑之活性化的有效波長區域的照射強度就UV-B(280至320nm之中波長區域紫外線)而言以達到1至3,000 mW/cm2 為佳。照射強度低於1 mW/cm2 時，反應時間變得過長，另一方面，該照射強度超過3,000 mW/cm2 時，由於燈所發射的熱及光硬化性接著劑的聚合時所致之發熱，而有發生光硬化性接著劑之黃變或偏光件之劣化的可能性。The light irradiation intensity of the photocurable adhesive is determined depending on each of the intended compositions, and is not particularly limited, but the irradiation intensity in the effective wavelength region in which the polymerization initiator is activated is UV-B (280 to It is preferable to achieve 1 to 3,000 mW/cm 2 in terms of ultraviolet light in the wavelength region of 320 nm. When the irradiation intensity is less than 1 mW/cm 2 , the reaction time becomes too long. On the other hand, when the irradiation intensity exceeds 3,000 mW/cm 2 , the heat emitted by the lamp and the polymerization of the photocurable adhesive are caused. The heat is generated, and there is a possibility that yellowing of the photocurable adhesive or deterioration of the polarizer occurs.
對光硬化性接著劑之光照射時間係由各個硬化之組成物所控制，雖無特別限定，但以設定成使照射強度與照射時間之積所表示之累計光量成為10至5,000 mJ/cm2 為佳。累計光量為10 mJ/cm2 以下時，則源自聚合起始劑之活性種的產生就不充分，接著劑之硬化可能變得不足，另一方面，累計光量超過5,000 mJ/cm2 時，則照射時間變得非常長，不利於生產性之提高。The light irradiation time of the photocurable adhesive is controlled by each hardened composition, and is not particularly limited. However, the integrated light amount expressed by the product of the irradiation intensity and the irradiation time is 10 to 5,000 mJ/cm 2 . It is better. When the total amount of light is 10 mJ/cm 2 or less, the generation of the active species derived from the polymerization initiator is insufficient, and the curing of the binder may become insufficient. On the other hand, when the cumulative amount of light exceeds 5,000 mJ/cm 2 , The irradiation time becomes very long, which is not conducive to the improvement of productivity.
當照射活性能源線而使光硬化性接著劑硬化時，以在偏光件之偏光度、透過率及色相、以及保護膜之透過性等偏光板之各種機能不降低的條件下使其硬化為佳。When the photocurable adhesive is cured by irradiation of the active energy source, it is preferable to harden the polarizing plate such as the polarizing degree, the transmittance, the hue, and the permeability of the protective film. .
在如此所得之偏光板中，接著劑層之厚度並無特別限定，通常是在50μm以下，以20μm以下為佳，以10μm以下更佳。In the polarizing plate thus obtained, the thickness of the adhesive layer is not particularly limited, but is usually 50 μm or less, preferably 20 μm or less, and more preferably 10 μm or less.
當使用偏光板時，亦可製成於其之一邊側積層顯示偏光機能以外之光學機能的光學層之光學構材。以形成光學構材作為目的而積層於偏光板之光學層，並無特別限定，例如可列舉如反射層、半透過型反射層、光擴散層、相位差板、集光板、提高亮度之薄膜等在形成液晶顯示裝置等時所使用的各種光學層。前述之反射層、半透過型反射層、及光擴散層是在形成由反射型乃至半透過型或擴散型、該等之兩用型的偏光板所成之光學構材時使用者。When a polarizing plate is used, an optical member which is formed on one side of the optical layer and which exhibits an optical function other than the optical function of the polarizing function can be formed. The optical layer laminated on the polarizing plate for the purpose of forming an optical member is not particularly limited, and examples thereof include a reflective layer, a semi-transmissive reflective layer, a light diffusion layer, a phase difference plate, a light collecting plate, and a film for improving brightness. Various optical layers used in forming a liquid crystal display device or the like. The reflective layer, the semi-transmissive reflective layer, and the light-diffusing layer are used for forming an optical member made of a polarizing plate of a reflective type or a transflective type or a diffused type.
反射型的偏光板係使用於使來自視認側之入射光反射而顯示之類型的液晶顯示裝置中，因為可省略背光等光源，故可容易使液晶顯示裝置薄型化。又，半透過型的偏光板係使用於在亮處則作為反射型顯示，在暗處則使用背光等光源而顯示之類型的液晶顯示裝置中。作為反射型偏光板之光學構材，係例如可在偏光件上之保護膜附設由鋁等金屬所構成的箔或蒸鍍膜而形成反射層。作為半透過型偏光板之光學構材，係可藉由將前述反射層作為半鏡(half mirror)，或是將含有珍珠顏料等且顯示光透過性的反射板接著於偏光板而形成之。另一方面，作為擴散型偏光板之光學構材，係使用例如對於偏光板上之保護膜實施消光處理之方法、塗布含有微粒子之樹脂之方法、使含有微粒子之薄膜接著之方法等各種方法，而在表面形成微細凹凸結構。The reflective polarizing plate is used in a liquid crystal display device of a type that reflects incident light from the viewing side. Since a light source such as a backlight can be omitted, the liquid crystal display device can be easily made thinner. Further, the semi-transmissive polarizing plate is used in a liquid crystal display device of a type that is displayed in a bright place as a reflective display and in a dark place using a light source such as a backlight. As an optical member of the reflective polarizing plate, for example, a foil made of a metal such as aluminum or a vapor deposited film may be attached to the protective film on the polarizer to form a reflective layer. The optical member of the semi-transmissive polarizing plate can be formed by using the reflective layer as a half mirror or a reflecting plate containing a pearl pigment or the like and exhibiting light transmittance in a polarizing plate. On the other hand, as the optical member of the diffusing type polarizing plate, for example, a method of performing a matting treatment on a protective film on a polarizing plate, a method of applying a resin containing fine particles, and a method of forming a film containing fine particles are used. On the surface, a fine uneven structure is formed.
進一步，作為反射擴散兩用之偏光板的光學構材之形成，例如，可藉由在擴散型偏光板之微細凹凸結構面上設置反映該凹凸結構之反射層等之方法而進行。微細凹凸結構之反射層係使入射光藉由亂反射而擴散，具有可防止指向性(directivity)或眩光、抑制明暗不均之優點等。又，含有微粒子之樹脂層或薄膜係使入射光及其反射光在透過含有微粒子之層時擴散，而有更加抑制明暗不均等之優點。反映表面微細凹凸結構之反射層，係可藉由例如真空蒸鍍、離子電鍍、濺鍍等蒸鍍或電鍍等方法，使金屬直接附設在微細凹凸結構之表面而形成。為了形成表面微細凹凸結構而摻配之微粒子，例如可利用由平均粒徑0.1至30μm之二氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等所成的無機系微粒子、由交聯或末交聯之聚合物等所成的有機系微粒子等。Further, the formation of the optical member as the polarizing plate for reflection and diffusion can be performed, for example, by providing a reflecting layer or the like reflecting the uneven structure on the fine uneven structure surface of the diffusing type polarizing plate. The reflective layer of the fine uneven structure diffuses incident light by random reflection, and has the advantages of preventing directivity or glare, suppressing unevenness of light and dark, and the like. Further, the resin layer or the film containing the fine particles diffuses the incident light and the reflected light thereof while passing through the layer containing the fine particles, and has an advantage of further suppressing unevenness in brightness and the like. 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 vapor deposition or plating such as vacuum deposition, ion plating or sputtering. The fine particles blended to form the fine uneven structure on the surface can be formed, for example, from cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, cadmium oxide, or cerium oxide having an average particle diameter of 0.1 to 30 μm. Inorganic fine particles, organic fine particles formed by crosslinking or terminally crosslinked polymers, and the like.
另一方面，作為上述光學層的相位差板，係以將液晶胞所致之相位差予以補償等作為目的而使用。其例並無特別限定，可列舉如：由各種塑膠之延伸薄膜等所成之雙折射性薄膜、配向固定有盤狀液晶(discotic liquid crystal)或向列相液晶(nematic liquid crystal)之薄膜、在薄膜基材上形成有上述液晶層者等。此時，支持配向液晶層之薄膜基材並無特別限定，以使用三乙醯基纖維素等纖維素系薄膜為佳。On the other hand, the phase difference plate as the optical layer is used for the purpose of compensating for the phase difference caused by the liquid crystal cell. The examples thereof are not particularly limited, and examples thereof include a birefringent film formed of a stretched film of various plastics, a film in which a discotic liquid crystal or a nematic liquid crystal is fixed, and a film which is fixed to a discotic liquid crystal or a nematic liquid crystal. The liquid crystal layer or the like is formed on the film substrate. In this case, the film substrate supporting the alignment liquid crystal layer is not particularly limited, and a cellulose film such as triethylenesulfonyl cellulose is preferably used.
形成雙折射性薄膜之塑膠並無特別限定，可列舉：如聚碳酸酯、聚乙烯醇、聚苯乙烯、聚甲基丙烯酸甲酯、聚丙烯等聚烯烴、聚芳酸酯(polyarylate)、聚醯胺、非晶性聚烯烴系樹脂等。延伸薄膜可為經單軸或雙軸等適當方式處理者。又，也可為在與熱收縮性薄膜之接著下施加收縮力及/或延伸力而控制薄膜之厚度方向之折射率的雙折射性薄膜。又，以控制廣帶域化等光學特性為目的，相位差板亦可組合2片以上而使用。The plastic forming the birefringent film is not particularly limited, and examples thereof include polyolefins such as polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, and polypropylene, polyarylate, and poly Amidoxime, an amorphous polyolefin resin, or the like. The stretch film can be handled by a suitable method such as uniaxial or biaxial. Further, a birefringent film which controls the refractive index in the thickness direction of the film by applying a shrinking force and/or an extending force to the heat-shrinkable film may be used. Further, for the purpose of controlling optical characteristics such as wide banding, the phase difference plate may be used in combination of two or more.
集光板是以控制光路等為目的而使用者，可形成而作為稜鏡陣列薄片、透鏡陣列薄片、或附設點之薄片等。The light collecting plate is a user for controlling the optical path or the like, and can be formed as a tantalum array sheet, a lens array sheet, or a sheet of attachment dots.
提高亮度之薄膜係以提高液晶顯示裝置等中之亮度為目的而使用者，其例可列舉如：將複數片折射率之異向性互為不同之薄膜加以積層而以使反射率產生異向性之方式設計的反射型直線偏光分離薄片、將膽固醇液晶聚合物之配向薄膜或其配向液晶層支撐在薄膜基材上的圓偏光分離薄片等。The film for improving the brightness is used for the purpose of improving the brightness in a liquid crystal display device or the like. For example, a film in which the refractive indices of the plurality of refractive indexes are different from each other is laminated to cause anisotropy of the reflectance. A reflective linear polarizing separation sheet designed in a sexual manner, a alignment film of a cholesteric liquid crystal polymer or a circularly polarizing separation sheet supporting the liquid crystal layer on a film substrate.
光學構材係可將偏光板，與從前述反射層乃至半透過型反射層、光擴散層、相位差板、集光板、提高亮度之薄膜等中因應使用目的而選擇1層或2層以上之光學層予以組合，而作成2層或3層以上之積層體。此時，光擴散層或相位差板、集光板或提高亮度之薄膜等光學層亦可分別配置2層以上。同時，各光學層之配置並無特別限定。In the optical member, one or two or more layers of the polarizing plate and the semi-transmissive reflective layer, the light-diffusing layer, the retardation plate, the light-concentrating plate, and the film for improving brightness can be selected for the purpose of use. The optical layers are combined to form a laminate of two or more layers. In this case, two or more optical layers such as a light diffusion layer, a phase difference plate, a light concentrating plate, or a film for improving brightness may be disposed. Meanwhile, the arrangement of the optical layers is not particularly limited.
形成光學構材之各種光學層係使用接著劑而與偏光板一體化，因此而使用之接著劑只要是可良好地形成接著層者即可，而無特別限定。從接著作業之簡便性或防止光學變形之發生等的觀點而言，以使用黏著劑(亦稱為感壓接著劑)為佳。黏著劑可使用以丙烯酸系聚合物、或聚矽氧(silicone)系聚合物、聚酯、聚胺酯、聚醚等作為原料聚合物(base polymer)者。其中，以選擇使用如丙烯酸系黏著劑般光學透明性優異，維持適度之濡濕性或凝集力，與基材之接著性也優異，並且有耐候性或耐熱性等，在加熱或加濕之條件下不會產生浮起或剝落等剝離問題者為佳。丙烯酸系黏著劑中，係以下述丙烯酸系共聚合物可作為有用的原料聚合物：將具有如甲基、乙基或丁基等碳數為20以下的烷基之(甲基)丙烯酸烷酯，與由(甲基)丙烯酸或(甲基)丙烯酸羥基乙酯等所成之含有官能基的丙烯酸系單體，以玻璃轉移溫度在25℃以下為佳，進一步以在0℃以下為更佳而摻配並聚合，而獲得重量平均分子量為10萬以上之丙烯酸系共聚合物。Since the various optical layers forming the optical member are integrated with the polarizing plate using an adhesive, the adhesive to be used may be any one as long as it can form the adhesive layer well, and is not particularly limited. It is preferable to use an adhesive (also referred to as a pressure-sensitive adhesive) from the viewpoint of ease of handling, prevention of occurrence of optical deformation, and the like. As the adhesive, an acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyether or the like can be used as a base polymer. Among them, the use of an acrylic adhesive is excellent in optical transparency, maintains moderate wettability or cohesive force, and is excellent in adhesion to a substrate, and has weather resistance, heat resistance, etc., under heating or humidification conditions. It is preferable that there is no peeling problem such as floating or peeling. In the acrylic adhesive, the following acrylic copolymer can be used as a useful base polymer: an alkyl (meth)acrylate having an alkyl group having a carbon number of 20 or less, such as a methyl group, an ethyl group or a butyl group. The acrylic monomer containing a functional group derived from (meth)acrylic acid or hydroxyethyl (meth)acrylate may preferably have a glass transition temperature of 25 ° C or less, more preferably 0 ° C or less. While blending and polymerizing, an acrylic copolymer having a weight average molecular weight of 100,000 or more is obtained.
於偏光板形成黏著劑層時可藉由下述方式而進行：例如在如甲苯或乙酸乙酯等有機溶劑中，使黏著劑組成物溶解或分散而調製成固形分濃度10至40重量%的液體，將其直接塗布在偏光板上而形成黏著劑層之方式；或是預先在分離薄膜上形成黏著劑層，然後將其移到偏光板上而形成黏著劑層之方式等。黏著劑層之厚度係因應其接著力等來決定，而以1至50μm左右之範圍為適當。The formation of the adhesive layer on the polarizing plate can be carried out by, for example, dissolving or dispersing the adhesive composition in an organic solvent such as toluene or ethyl acetate to prepare a solid concentration of 10 to 40% by weight. A liquid, which is applied directly to a polarizing plate to form an adhesive layer, or a method in which an adhesive layer is formed on a separation film in advance, and then moved to a polarizing plate to form an adhesive layer. The thickness of the adhesive layer is determined depending on the adhesion and the like, and is preferably in the range of about 1 to 50 μm.
又，在黏著劑中，因應需求亦可摻配由玻璃纖維或玻璃小球、樹脂小球、金屬粉或其他之無機粉末等所成的充填劑、顏料或著色劑、抗氧化劑、紫外線吸收劑等。作為紫外線吸收劑者並無特別限定，可列舉如：水楊酸酯系化合物或二苯甲酮系化合物、苯并***系化合物、氰基丙烯酸酯系化合物、鎳錯鹽系化合物等。Further, in the adhesive, a filler, a pigment or a colorant, an antioxidant, an ultraviolet absorber, which is formed of glass fiber or glass pellet, resin pellet, metal powder or other inorganic powder may be blended according to requirements. Wait. The ultraviolet absorber is not particularly limited, and examples thereof include a salicylate-based compound, a benzophenone-based compound, a benzotriazole-based compound, a cyanoacrylate-based compound, and a nickel-salted salt-based compound.
以上之光學構材可配置在液晶胞之單側或兩側而作成液晶顯示裝置。使用之液晶胞可為任意者，例如，可使用薄膜電晶體型所代表之主動式矩陣驅動型者、超扭轉向列型所代表之單純矩陣驅動型者等各種液晶胞而形成液晶顯示裝置。在液晶胞之兩側設置之光學構材可為相同者，亦可為相異者。The above optical member can be disposed on one side or both sides of the liquid crystal cell to form a liquid crystal display device. The liquid crystal cell to be used may be any one. For example, a liquid crystal display device may be formed by 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.
以下，揭示實施例及比較例而更具體說明本發明，但本發明並不侷限於該等實施例，例中表示使用量乃至含量之%在無特別限定時即為重量基準。Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. However, the present invention is not limited to the examples, and the examples show that the amount of use or the content is based on the weight unless otherwise specified.
在實施例及比較例中，接著劑組成物之調製所使用之各成分如下所述，以下，以各個記號(商品名本身或其之一部份)來表示。In the examples and comparative examples, the components used for the preparation of the adhesive composition are as follows, and are hereinafter referred to as individual symbols (the product name itself or a part thereof).
jER-828：雙酚A型環氧樹脂，Japan Epoxy Resins(股)製之"jER-828"。jER-828: bisphenol A type epoxy resin, "jER-828" made by Japan Epoxy Resins Co., Ltd.
jER-152：酚酚醛清漆型環氧樹脂，Japan Epoxy Resins(股)製之"jER-152"。jER-152: Phenolic novolac type epoxy resin, "jER-152" manufactured by Japan Epoxy Resins Co., Ltd.
ECC：3,4-環氧基環己烷羧酸3,4-環氧基環己基甲酯。ECC: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylic acid.
OXT-211：3-乙基-3-苯氧基甲基氧雜環丁烷，東亞合成(股)製之"Aronoxetane OXT-211"。OXT-211: 3-ethyl-3-phenoxymethyloxetane, "Aronoxetane OXT-211" manufactured by East Asia Synthetic Co., Ltd.
OXT-221：3-乙基-3-[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]氧雜環丁烷，東亞合成(股)製之"Aronoxetane OXT-221"。OXT-221: 3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane, manufactured by East Asia Synthetic Co., Ltd. "Aronoxetane OXT- 221".
OXT-121：以1,4-雙[(3-乙基氧雜環丁烷-3-基)甲氧基甲基]苯為主成分之具有伸苯二甲基(xylylene)骨幹的二官能氧雜環丁烷化合物，東亞合成(股)製之"Aronoxetane OXT-121"OXT-121: Difunctional with 1,4-bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene as the main component of xylylene backbone Oxetane compound, "Aronoxetane OXT-121" made by East Asia Synthetic Co., Ltd.
此等氧雜環丁烷化合物的結構如以下所示。The structures of these oxetane compounds are shown below.
UVI-6992：以六氟磷酸三芳基鋶鹽作為主成分的有效成分50%之碳酸伸丙酯(propylene carbonate)溶液，陶氏化學公司製之"UVI-6992"UVI-6992: a 50% propylene carbonate solution containing a triarylsulfonium hexafluorophosphate as a main component, "UVI-6992" manufactured by The Dow Chemical Company.
M-203S：三環癸烷二羥甲基二丙烯酸酯，東亞合成(股)製之"Aronix M-203S"M-203S: Tricyclodecane Dihydroxymethyl Diacrylate, "Aronix M-203S" made by East Asia Synthetic Co., Ltd.
Irg 184：1-羥基環己基苯基酮，汽巴公司製之"Irgacure 184"。Irg 184: 1-hydroxycyclohexyl phenyl ketone, "Irgacure 184" manufactured by Ciba.
BR-60：甲基丙烯酸甲酯系共聚物，三菱Rayon(股)製之"Dianal BR-60"。BR-60: a methyl methacrylate copolymer, "Dianal BR-60" manufactured by Mitsubishi Rayon Co., Ltd.
將表1及表2所示之各成分以其各自之比率摻配，依照常法攪拌混合，調製光硬化性接著劑組成物。又，由於作為(C)成分使用之"UVI-6992"是含有50%有效成分的碳酸伸丙酯溶液，故在表中，(C)成分與碳酸伸丙酯係分開表示。亦即，表中之"UVI-6992"的摻配量是指固形分的比率，"UVI-6992"本身之摻配量係將(C)成分欄中所示之量與碳酸伸丙酯欄中所示之量合併而為6%。The components shown in Tables 1 and 2 were blended at their respective ratios, and stirred and mixed in accordance with a usual method to prepare a photocurable adhesive composition. Further, since "UVI-6992" used as the component (C) is a propylene carbonate solution containing 50% of an active ingredient, in the table, the component (C) is shown separately from the propylene carbonate. That is, the blending amount of "UVI-6992" in the table means the ratio of the solid fraction, and the blending amount of "UVI-6992" itself is the amount shown in the column of (C) component and the propyl carbonate column. The amounts shown are combined to be 6%.
在此，保護膜者係使用下述2種薄膜。Here, the following two types of films are used for the protective film.
延伸降冰片烯系樹脂薄膜：厚度70μm，商品名"ZEONOR薄膜"，日本Zeon(股)公司製。對該薄膜實施電暈放電處理後，供於與偏光件結合。The norbornene-based resin film was stretched to a thickness of 70 μm, and the product name was "ZEONOR film" manufactured by Zeon Co., Ltd., Japan. After the film is subjected to a corona discharge treatment, it is supplied to be combined with a polarizing member.
雙軸延伸聚對苯二甲酸乙二酯薄膜：厚度50μm，商品名"E5001"，東洋紡績(股)公司製。對該薄膜實施電暈放電處理後，供於與偏光件結合。Biaxially stretched polyethylene terephthalate film: 50 μm thick, trade name "E5001", manufactured by Toyobo Co., Ltd. After the film is subjected to a corona discharge treatment, it is supplied to be combined with a polarizing member.
在上述延伸降冰片烯系樹脂薄膜之電暈放電處理面，將上述調製之接著劑組成物以棒塗布機塗布成3μm，並在其上黏貼由聚乙烯醇吸附配向碘而成之偏光件。另外，在上述雙軸延伸聚對苯二甲酸乙二酯薄膜也以棒塗布機將相同接著劑塗布成3μm厚，並且黏貼在先經降冰片烯系樹脂薄膜黏貼之偏光件的與降冰片烯系樹脂薄膜相反側之面上。對於如此兩面黏貼有保護膜的偏光件，藉由附有帶式輸送機(Belt conveyor)的紫外線照射裝置(燈係使用Fusion公司製的"Fusion H燈")，從一邊之表面以累計光量300 mJ/cm2 照射紫外線後，在室溫放置1小時，並在單面黏貼由聚對苯二甲酸乙二酯薄膜所成之保護膜，而製作成在另一面黏貼有延伸降冰片烯系樹脂薄膜之偏光板(1)。On the corona discharge treated surface of the above-mentioned extended norbornene-based resin film, the above-mentioned prepared adhesive composition was applied to a thickness of 3 μm by a bar coater, and a polarizer obtained by adsorbing and absorbing iodine from polyvinyl alcohol was adhered thereto. Further, in the above biaxially-oriented polyethylene terephthalate film, the same adhesive was applied to a thickness of 3 μm by a bar coater, and the norbornene adhered to the polarizer of the norbornene-based resin film was adhered. On the opposite side of the resin film. For the polarizer to which the protective film is adhered on both sides, the ultraviolet light irradiation device (the "Fusion H lamp" manufactured by Fusion Co., Ltd.) equipped with a belt conveyor is used, and the integrated light amount 300 is obtained from the surface of one side. After mJ/cm 2 was irradiated with ultraviolet rays, it was allowed to stand at room temperature for 1 hour, and a protective film made of a polyethylene terephthalate film was adhered to one side, and an extended norbornene-based resin was adhered to the other side. Thin film polarizing plate (1).
將雙軸延伸聚對苯二甲酸乙二酯薄膜改成丙烯酸系樹脂薄膜[厚度80μm，商品名"Technoloy S001"，住友化學(股)製]，其他則與偏光板(1)之製作同樣操作，在單面黏貼由丙烯酸系樹脂薄膜所成之保護膜，而製作在另一面黏貼有延伸降冰片烯系樹脂薄膜之偏光板(2)。The biaxially stretched polyethylene terephthalate film was changed to an acrylic resin film [thickness 80 μm, trade name "Technoloy S001", manufactured by Sumitomo Chemical Co., Ltd.], and the others were operated in the same manner as the polarizing plate (1). A protective film made of an acrylic resin film was adhered to one side, and a polarizing plate (2) having an extended norbornene-based resin film adhered to the other surface was formed.
對於所得之各個偏光板，用以下之方法評估硬化性、接著性及耐久性，結果示於表1及表2。The obtained polarizing plates were evaluated for hardenability, adhesion, and durability by the following methods, and the results are shown in Tables 1 and 2.
用手嘗試剝離偏光件與聚對苯二甲酸乙二酯薄膜或丙烯酸系樹脂薄膜之間，將完全硬化而無法剝離者、或是即使剝離但在該部份也未殘留黏性(tack)(未硬化接著劑而引起之黏著性)者評估為「○」，將剝離且在該部份會殘留黏性者評估為「X」。Try to peel off between the polarizer and the polyethylene terephthalate film or the acrylic resin film by hand, and it will be completely hardened and cannot be peeled off, or even if it is peeled off, no stick remains in the part ( Those who are not cured by the adhesive are evaluated as "○", and those who will be peeled off and have residual stickiness in this part are evaluated as "X".
當將裁切刀之刀刃從聚對苯二甲酸乙二酯薄膜或丙烯酸系樹脂薄膜之上以斜向***時，將薄膜會從偏光件剝離且刀刃切入聚對苯二甲酸乙二酯薄膜或丙烯酸系樹脂薄膜與偏光件之間者評估為最差之「X」。當在此試驗中沒有剝離時，則進一步進行下述評估。亦即，將偏光板以延伸方向當作長邊而將其切成寬1cm的長方形狀，從聚對苯二甲酸乙二酯薄膜或丙烯酸系樹脂薄膜之表面，於與延伸方向垂直之方向用切刀淺淺切入，將該切入處作為外側並彎折成「ㄑ」字形時，觀察端部之剝離程度。在此，當端部剝離時，則從剝離部分以手來嘗試剝離，以是否有進行剝離、薄膜是否材料破壞(material failure)而予以評估。因應評估結果而進行下述之判定。When the cutting blade is inserted obliquely from the polyethylene terephthalate film or the acrylic resin film, the film is peeled off from the polarizing member and the blade is cut into the polyethylene terephthalate film or The difference between the acrylic resin film and the polarizer was evaluated as the worst "X". When there was no peeling in this test, the following evaluation was further carried out. That is, the polarizing plate is cut into a rectangular shape having a width of 1 cm in the extending direction as a long side, and is used in a direction perpendicular to the extending direction from the surface of the polyethylene terephthalate film or the acrylic resin film. When the cutter was cut shallowly, and the cut-out portion was taken as the outer side and bent into a "ㄑ" shape, the degree of peeling of the end portion was observed. Here, when the end portion was peeled off, peeling was attempted by hand from the peeling portion, and it was evaluated whether or not peeling occurred and the film was material failure. The following judgments are made based on the results of the evaluation.
△：彎折時端部之剝離大，容易用手進行剝離。△: The peeling of the end portion at the time of bending is large, and it is easy to peel off by hand.
○：彎折時端部剝離1 mm左右，而再用手嘗試剝離時，薄膜會材料破壞。○: When the bent portion is peeled off by about 1 mm, the film may be broken when the peeling is attempted by hand.
◎：彎折時幾乎不剝離，再用手進行剝離時，薄膜會材料破壞。◎: When the bending is hardly peeled off, and the peeling is performed by hand, the film may be broken.
對於接著性在「○」以上的良好試樣，將在-35℃放置60分鐘且其次在+70℃放置60分鐘而重覆循環300次的冷熱衝擊循環試驗，以對角15英吋(約38cm)與對角5英吋(約13cm)的2種類的試樣大小來實施，並做下述之評估。For a good sample having an adhesion of "○" or more, a thermal shock cycle test was repeated at -35 ° C for 60 minutes and then at +70 ° C for 60 minutes, and repeated for 300 cycles, at a diagonal of 15 inches (about 15 inches). 38 cm) was carried out with two types of sample sizes of 5 inches (about 13 cm) diagonally and evaluated as follows.
○：在15英吋之外觀沒有不良。○: There is no defect in the appearance of 15 inches.
△：在15英吋有一部分外觀不良，但在5英吋之外觀則沒有不良。△: There is a partial appearance defect at 15 inches, but there is no defect in the appearance of 5 inches.
X：即使在5英吋之外觀也都不良。X: Even in the appearance of 5 inches, it is not good.
如表1所示，使用本發明之光硬化性接著劑組成物而製作之實施例1至7的偏光板係偏光件與保護膜之接著性良好，硬化性也良好。其中，在(B)成分的氧雜環丁烷化合物係使用分子內具有1個氧雜環丁基與1個芳香環的"OXT-211"之實施例1至3中，接著性為特別良好。在含有18%之具有脂環式骨幹的丙烯酸系不飽和化合物"M-203S"作為(D)成分的實施例3中，除了有良好之接著性之外，耐久性也良好。又，使用分子內具有2個氧雜環丁基且在室溫中為液狀之分子量為500以下之氧雜環丁烷化合物"OXT-221"的實施例4至7中(實施例4是與"OXT-121"併用)，接著性與耐久性之平衡優異。其中，含有18%之丙烯酸系不飽和化合物"M-203S"的實施例4及5係接著性特別良好。As shown in Table 1, the polarizing plate-based polarizers of Examples 1 to 7 produced by using the photocurable adhesive composition of the present invention have good adhesion to the protective film and good curability. In the examples 1 to 3 in which the oxetane compound of the component (B) is "OXT-211" having one oxetanyl group and one aromatic ring in the molecule, the adhesion is particularly good. . In Example 3 containing 18% of the acrylic unsaturated compound "M-203S" having an alicyclic backbone as the component (D), durability was good in addition to good adhesion. Further, in Examples 4 to 7 in which the oxetane compound "OXT-221" having two oxetanyl groups in the molecule and having a liquid molecular weight of 500 or less at room temperature was used (Example 4 is Used in combination with "OXT-121"), the balance between adhesion and durability is excellent. Among them, Examples 4 and 5 containing 18% of the acrylic unsaturated compound "M-203S" were particularly excellent in adhesion.
另一方面，如表2所示，不含(B)成分的氧雜環丁烷化合物的比較例1及2缺乏接著性。尤其在將(D)成分的的丙烯酸系不飽和化合物摻配成43%的比較例2中，對於聚對苯二甲酸乙二酯薄膜及對於丙烯酸系樹脂薄膜之接著性皆差。又，不含(A)成分之環氧化合物的比較例3係硬化性及接著性皆差。On the other hand, as shown in Table 2, Comparative Examples 1 and 2 which do not contain the (B) component oxetane compound lacked the adhesiveness. In particular, in Comparative Example 2 in which the acrylic unsaturated compound of the component (D) was blended to 43%, the polyethylene terephthalate film and the acrylic resin film were inferior in adhesion. Further, Comparative Example 3, which does not contain the epoxy compound of the component (A), was inferior in both curability and adhesion.
本發明之光硬化性接著劑組成物係藉由紫外線等活性能源線的照射而容易硬化，使偏光件與保護膜在短時間內牢固地接著，故有可利用性。The photocurable adhesive composition of the present invention is easily cured by irradiation with an active energy source such as ultraviolet rays, and the polarizer and the protective film are firmly adhered in a short time, so that the usability is available.
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