TWI448749B - Adhesive type optical film peeling method and adhesive type optical film - Google Patents
Adhesive type optical film peeling method and adhesive type optical film Download PDFInfo
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- TWI448749B TWI448749B TW098102254A TW98102254A TWI448749B TW I448749 B TWI448749 B TW I448749B TW 098102254 A TW098102254 A TW 098102254A TW 98102254 A TW98102254 A TW 98102254A TW I448749 B TWI448749 B TW I448749B
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- polarizing plate
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
- B29D11/00788—Producing optical films
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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
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
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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
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- G02B5/3083—Birefringent or phase retarding elements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ophthalmology & Optometry (AREA)
- Mechanical Engineering (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本發明係關於一種自附有光學膜之玻璃基板上剝離黏著型光學膜之黏著型光學膜之剝離方法、以及該剝離方法中所使用之黏著型光學膜。作為上述光學膜,可列舉:偏光板、相位差板、光學補償膜、增亮膜、視角擴大膜以及積層有該等者等。The present invention relates to a method for peeling off an adhesive optical film from which an adhesive optical film is peeled off from a glass substrate to which an optical film is attached, and an adhesive optical film used in the peeling method. Examples of the optical film include a polarizing plate, a phase difference plate, an optical compensation film, a brightness enhancement film, a viewing angle widening film, and the like.
液晶顯示器等由於其圖像形成方式之關係而必需於液晶單元之兩側配置偏光元件,通常係黏貼偏光板。又,為了提昇顯示器之顯示品質,亦於液晶面板上使用除偏光板以外之其他各種光學元件。例如使用用以防止著色之相位差板、用以改善液晶顯示器之視角之視角擴大膜、進而用以提高顯示器之對比度之增亮膜等。該等膜總稱為光學膜。In the liquid crystal display or the like, it is necessary to arrange a polarizing element on both sides of the liquid crystal cell due to the relationship between the image forming modes, and it is usually attached to the polarizing plate. Further, in order to improve the display quality of the display, various optical elements other than the polarizing plate are used on the liquid crystal panel. For example, a phase difference plate for preventing coloration, a viewing angle expansion film for improving the viewing angle of the liquid crystal display, and a brightness enhancement film for improving the contrast of the display are used. These films are collectively referred to as optical films.
於液晶單元上黏貼上述光學膜時,通常使用黏著劑。又,在將光學膜與液晶單元、以及將光學膜之間接著時,通常為了減少光之損失而使用黏著劑使各材料相互密著。於此種情形時,具有無需乾燥步驟以使光學膜固著等之優點,因此通常使用將黏著劑預先設置於光學膜之單面上而形成有黏著劑層的黏著型光學膜。When the above optical film is adhered to the liquid crystal cell, an adhesive is usually used. Further, when the optical film is bonded to the liquid crystal cell and the optical film is bonded, the materials are usually adhered to each other in order to reduce the loss of light. In such a case, there is an advantage that the drying step is not required to fix the optical film. Therefore, an adhesive type optical film in which an adhesive layer is formed on the single surface of the optical film in advance is usually used.
若在將黏著型光學膜貼合於液晶單元之表面時貼合位置偏移、或者齧入有異物,則會於液晶顯示方面產生問題,因此先前係將已貼附之黏著型光學膜剝離,然後再次於液晶單元之表面貼附新的黏著型光學膜。但是,由於液晶顯示器之大型化或液晶單元之薄型化,要將黏著型光學膜剝離變得越來越困難,尤其是於黏著劑層之黏著力較強之情形時剝離需要較大之力,因此存在作業性變差、液晶單元之單元間隙(cell gap)產生變化而導致顯示品質下降、或者損壞液晶單元等問題。又,為了抑制製造成本,要求對所剝離之黏著型光學膜進行再利用、以及可無糨糊殘餘地剝離之重工性。When the adhesive optical film is bonded to the surface of the liquid crystal cell, the bonding position is shifted or a foreign matter is caught, which causes a problem in liquid crystal display. Therefore, the adhesive optical film that has been attached is peeled off. Then, a new adhesive optical film is attached to the surface of the liquid crystal cell again. However, due to the enlargement of the liquid crystal display or the thinning of the liquid crystal cell, it is more and more difficult to peel off the adhesive optical film, especially when the adhesive force of the adhesive layer is strong, the peeling requires a large force. Therefore, there is a problem that the workability is deteriorated, the cell gap of the liquid crystal cell is changed, the display quality is deteriorated, or the liquid crystal cell is damaged. Further, in order to suppress the manufacturing cost, it is required to reuse the peeled adhesive optical film and to rework without peeling off the residue.
作為解決上述問題之方法,提出有:一面於液晶面板與光學膜之間***經加熱之電熱絲(electrically-heated wire)或切片機(slicer),一面使黏著劑軟化或熔融並剝離之方法(專利文獻1、2);以及於液晶面板上之光學膜上切出切口來加以分割,並剝離該分割片之方法(專利文獻3)。As a method for solving the above problems, there is proposed a method of softening or melting and peeling off an adhesive while inserting a heated electric-heated wire or a slicer between a liquid crystal panel and an optical film. Patent Documents 1 and 2); and a method of cutting a slit by cutting a slit on an optical film on a liquid crystal panel, and peeling off the split sheet (Patent Document 3).
又,提出有將經由黏著劑而黏貼有透明膜之顯示材料浸漬於鹼性溶液中後,自該顯示材料上剝離透明膜與黏著劑之方法(專利文獻4)。Further, a method of immersing a display material adhered with a transparent film via an adhesive in an alkaline solution and peeling off the transparent film and the adhesive from the display material has been proposed (Patent Document 4).
又,提出有:將剝離用片材貼合於欲剝離之光學構件上,將光學構件與該剝離用片材一同剝離之方法(專利文獻5);以及將偏光板黏著於黏著膠帶上後進行剝離之方法(專利文獻6)。Further, a method of bonding a release sheet to an optical member to be peeled off, peeling off the optical member together with the release sheet (Patent Document 5), and attaching the polarizing plate to the adhesive tape is proposed. Method of peeling (Patent Document 6).
又,提出有:藉由浸漬於濃硫酸中而將玻璃基板上所包含之偏光板等去除之方法(專利文獻7);藉由使用丙酮或三氯乙烯等溶劑將黏著劑溶解、去除而剝離偏光板之方法(專利文獻8);藉由對於偏光板具有可溶性之溶劑溶解偏光板而將其去除之方法(專利文獻9);以及於在黏著型光學膜之黏著劑層與基板之剝離界面上存在液體之狀態下進行剝離之方法(專利文獻10)。Further, a method of removing a polarizing plate or the like contained on a glass substrate by immersion in concentrated sulfuric acid has been proposed (Patent Document 7); the adhesive is dissolved and removed by using a solvent such as acetone or trichloroethylene to be stripped. Method of polarizing plate (Patent Document 8); a method of removing a polarizing plate by dissolving a polarizing plate in a solvent for a polarizing plate (Patent Document 9); and a peeling interface between the adhesive layer of the adhesive optical film and the substrate A method of performing peeling in the presence of a liquid (Patent Document 10).
但是,於上述方法中,需要進行於液晶面板與光學膜之間***剝離夾具,或者僅將液晶面板上之光學膜切斷等困難之作業。而且,存在會於液晶面板上產生大量糨糊殘餘,或者因溶劑而對液晶面板造成損害等之問題。However, in the above method, it is necessary to perform a work such as inserting a peeling jig between the liquid crystal panel and the optical film, or cutting only the optical film on the liquid crystal panel. Further, there is a problem that a large amount of paper residue is generated on the liquid crystal panel, or damage to the liquid crystal panel due to the solvent.
專利文獻1:日本專利特開平11-95210號公報Patent Document 1: Japanese Patent Laid-Open No. Hei 11-95210
專利文獻2:日本專利特開2002-350837號公報Patent Document 2: Japanese Patent Laid-Open Publication No. 2002-350837
專利文獻3:日本專利特開2001-242448號公報Patent Document 3: Japanese Patent Laid-Open Publication No. 2001-242448
專利文獻4:日本專利特開2001-328849號公報Patent Document 4: Japanese Patent Laid-Open Publication No. 2001-328849
專利文獻5:日本專利特開2002-40259號公報Patent Document 5: Japanese Patent Laid-Open Publication No. 2002-40259
專利文獻6:日本專利特開2002-159955號公報Patent Document 6: Japanese Patent Laid-Open Publication No. 2002-159955
專利文獻7:日本專利特開2001-305502號公報Patent Document 7: Japanese Patent Laid-Open Publication No. 2001-305502
專利文獻8:日本專利特開2001-337305號公報Patent Document 8: Japanese Patent Laid-Open Publication No. 2001-337305
專利文獻9:日本專利特開2005-224715號公報Patent Document 9: Japanese Patent Laid-Open Publication No. 2005-224715
專利文獻10:日本專利特開2005-148638號公報Patent Document 10: Japanese Patent Laid-Open Publication No. 2005-148638
本發明之目的在於提供一種黏著型光學膜之剝離方法以及該剝離方法中所使用之黏著型光學膜,該黏著型光學膜之剝離方法可自貼附有黏著型光學膜之玻璃基板上,不損傷玻璃基板、不於玻璃基板上產生糨糊殘餘且容易地剝離黏著型光學膜。尤其,本發明之目的在於提供一種即便於黏著型光學膜長時間貼合於玻璃基板上後接著力上升,重工作業變得極其困難之情形時,亦可無糨糊殘餘且容易地剝離黏著型光學膜之方法。An object of the present invention is to provide a method for peeling an adhesive optical film and an adhesive optical film used in the peeling method. The adhesive optical film can be peeled off from a glass substrate to which an adhesive optical film is attached. The glass substrate is damaged, and no adhesive residue is generated on the glass substrate, and the adhesive optical film is easily peeled off. In particular, it is an object of the present invention to provide an adhesive optical film which can be peeled off without sticking and can be easily peeled off even when the adhesive optical film is bonded to the glass substrate for a long period of time and the force is increased and the heavy work becomes extremely difficult. Membrane method.
本發明者等人為解決上述課題而努力研究,結果發現藉由下述剝離方法可達成上述目的,從而完成本發明。The inventors of the present invention have diligently studied to solve the above problems, and as a result, have found that the above object can be attained by the following peeling method, and the present invention has been completed.
即,本發明係關於一種黏著型光學膜之剝離方法,其係自於玻璃基板上貼附有黏著型光學膜的附有光學膜之玻璃基板上剝離黏著型光學膜者,其特徵在於:黏著型光學膜之黏著劑層由水分散型黏著劑形成,並且,該剝離方法係將附有光學膜之玻璃基板曝露於溫度為40℃以上且相對濕度為80%以上、或者溫度為50℃以上且相對濕度為70%以上之環境下後,自玻璃基板上剝離黏著型光學膜。That is, the present invention relates to a method for peeling an adhesive optical film which is obtained by peeling an adhesive optical film from a glass substrate with an optical film to which an adhesive optical film is adhered on a glass substrate, and is characterized in that: The adhesive layer of the optical film is formed of a water-dispersible adhesive, and the peeling method exposes the glass substrate with the optical film to a temperature of 40 ° C or higher and a relative humidity of 80% or more, or a temperature of 50 ° C or more. After the relative humidity is 70% or more, the adhesive optical film is peeled off from the glass substrate.
如上所述,藉由將附有光學膜之玻璃基板曝露於特定之環境下(曝露處理),可使黏著型光學膜之黏著劑層之接著力充分降低,從而可不損傷玻璃基板、無糨糊殘餘且重工性良好地自玻璃基板上剝離黏著型光學膜。藉由本發明之剝離方法,即便於液晶面板之尺寸較大時或液晶單元較薄時,重工性亦良好。又,藉由本發明之剝離方法,即便於黏著型光學膜長時間貼合於玻璃基板上後接著力升高之情形時,亦可無糨糊殘餘且容易地將其剝離。As described above, by exposing the glass substrate with the optical film to a specific environment (exposure treatment), the adhesion force of the adhesive layer of the adhesive optical film can be sufficiently reduced, so that the glass substrate can be not damaged, and no residual residue can be caused. The adhesive optical film is peeled off from the glass substrate with good workability. According to the peeling method of the present invention, even when the size of the liquid crystal panel is large or the liquid crystal cell is thin, the workability is good. Moreover, according to the peeling method of the present invention, even when the adhesive optical film is bonded to the glass substrate for a long period of time and the adhesive force is increased, the adhesive film can be peeled off without any residue.
又,藉由使用水分散型黏著劑來形成上述黏著型光學膜之黏著劑層,則利用上述曝露處理,黏著劑層吸水且水分向黏著劑層與玻璃基板之界面滲入,從而使黏著劑層之接著力充分降低,因此重工性得以提昇。進而,即便於曝露處理後恢復至室溫,接著力亦不會再次上升,於作業步驟方面較佳。Further, by forming the adhesive layer of the above-mentioned adhesive optical film by using a water-dispersible adhesive, the adhesive layer absorbs water by the above-mentioned exposure treatment, and moisture penetrates into the interface between the adhesive layer and the glass substrate, thereby making the adhesive layer The force is reduced sufficiently, so the reworkability is improved. Further, even if it returns to room temperature after the exposure treatment, the force does not rise again, which is preferable in terms of the working procedure.
上述黏著型光學膜較好的是於光學膜與黏著劑層之間具有增黏層。藉由設置增黏層,可將黏著型光學膜穩定性較佳地接著於玻璃基板上,而且於剝離黏著型光學膜時可無糨糊殘餘且容易地進行剝離。The above adhesive optical film preferably has an adhesion-promoting layer between the optical film and the adhesive layer. By providing the adhesion-promoting layer, the stability of the adhesive optical film can be preferably adhered to the glass substrate, and the peeling of the adhesive optical film can be carried out without peeling and easily peeling off.
又,本發明係關於一種黏著型光學膜,其係用於上述黏著型光學膜之剝離方法中,於光學膜之至少單面上具有由水分散型黏著劑所形成之黏著劑層者,其特徵在於:將該黏著型光學膜貼附於玻璃基板上,並且於溫度為60℃且相對濕度為30%之環境下曝露100小時後,其接著力為20N/25mm寬以上,曝露於溫度為40℃以上且相對濕度為80%以上、或者溫度為50℃以上且相對濕度為70%以上之環境下後,其接著力為10N/25mm寬以下。Further, the present invention relates to an adhesive optical film which is used in the above-mentioned method for peeling an adhesive optical film, and has an adhesive layer formed of a water-dispersible adhesive on at least one side of the optical film, The adhesive film is attached to a glass substrate, and after being exposed to an environment having a temperature of 60 ° C and a relative humidity of 30% for 100 hours, the adhesive force is 20 N/25 mm or more, and the temperature is exposed. After 40 ° C or more and a relative humidity of 80% or more, or a temperature of 50 ° C or more and a relative humidity of 70% or more, the adhesion is 10 N / 25 mm or less.
對於本發明之黏著型光學膜,即便於在高溫環境下與玻璃基板長時間貼合後接著力高達20N/25mm寬以上之情形時,藉由曝露於特定之環境下(曝露處理),亦可使黏著劑層之接著力充分降低,從而可不損傷玻璃基板、無糨糊殘餘且重工性良好地自玻璃基板上剝離該黏著型光學膜。本發明之黏著型光學膜即使於液晶面板之尺寸較大時或液晶單元較薄時亦可重工性良好地剝離。The adhesive optical film of the present invention can be exposed to a specific environment (exposure treatment) even when it is bonded to a glass substrate for a long time and then has a force of up to 20 N/25 mm or more in a high-temperature environment. The adhesion force of the adhesive layer is sufficiently lowered, so that the adhesive optical film can be peeled off from the glass substrate without damaging the glass substrate, without residue of the paste, and with good workability. The adhesive optical film of the present invention can be peeled off with good reworkability even when the size of the liquid crystal panel is large or when the liquid crystal cell is thin.
本發明之附有光學膜之玻璃基板係於玻璃基板上貼附有黏著型光學膜者,該黏著型光學膜之黏著劑層由水分散型黏著劑形成。The optical film-attached glass substrate of the present invention is obtained by attaching an adhesive optical film to a glass substrate, and the adhesive layer of the adhesive optical film is formed of a water-dispersible adhesive.
作為水分散型黏著劑,可使用橡膠系黏著劑、丙烯酸系黏著劑、矽氧系黏著劑等之各種水分散型黏著劑,較好的是無色透明,且與液晶單元(玻璃基板)之接著性良好的丙烯酸系黏著劑。As the water-dispersible pressure-sensitive adhesive, various water-dispersible pressure-sensitive adhesives such as a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive can be used, and it is preferably colorless and transparent, and is followed by a liquid crystal cell (glass substrate). A good acrylic adhesive.
水分散型丙烯酸系黏著劑含有藉由於乳化劑之存在下使(甲基)丙烯酸烷基酯乳化聚合而獲得之丙烯酸系聚合物乳液。再者,(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯,(甲基)之含義與此相同。(甲基)丙烯酸烷基酯之烷基之碳數為1~14左右,具體而言,可例示(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸異丁酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸異辛酯、(甲基)丙烯酸正壬酯、(甲基)丙烯酸異壬酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸異癸酯、(甲基)丙烯酸正十二烷基酯、(甲基)丙烯酸正十三烷基酯、(甲基)丙烯酸正十四烷基酯等,該等可單獨或組合使用。The water-dispersible acrylic pressure-sensitive adhesive contains an acrylic polymer emulsion obtained by emulsion polymerization of an alkyl (meth)acrylate in the presence of an emulsifier. Further, (meth) acrylate means acrylate and/or methacrylate, and (meth) has the same meaning. The alkyl group of the alkyl (meth)acrylate has a carbon number of about 1 to 14, and specifically, methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate are exemplified. , (3) butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( N-octyl methacrylate, isooctyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-decyl (meth) acrylate, (meth) acrylate An oxime ester, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. may be used singly or in combination.
為了調整丙烯酸系聚合物之玻璃轉移點或黏著劑層之黏著特性,亦可使用其他聚合性單體。尤其是為了提昇對於玻璃基板之接著力,或者為了導入用以使所獲得之共聚物進行後續交聯之交聯點,進而為了提高黏著劑之凝聚力,較好的是使用含有羧基之單體。In order to adjust the adhesion characteristics of the glass transition point or the adhesive layer of the acrylic polymer, other polymerizable monomers may also be used. In particular, in order to increase the adhesion to the glass substrate, or to introduce a crosslinking point for subsequent crosslinking of the obtained copolymer, and further to increase the cohesive force of the adhesive, it is preferred to use a monomer having a carboxyl group.
作為含有羧基之單體,例如可列舉:丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、衣康酸、順丁烯二酸、反丁烯二酸、丁烯酸等。其中,尤其可較好地使用丙烯酸及甲基丙烯酸。Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and fumaric acid. , butenoic acid, etc. Among them, acrylic acid and methacrylic acid are particularly preferably used.
含有羧基之單體之添加量相對於形成丙烯酸系聚合物之單體成分的總量較好的是0.1~10重量%,更好的是1~7重量%。The amount of the carboxyl group-containing monomer added is preferably from 0.1 to 10% by weight, more preferably from 1 to 7% by weight, based on the total amount of the monomer component forming the acrylic polymer.
又,作為其他聚合性單體,例如可適宜使用:含有磺酸基之單體、含有磷酸基之單體、含有氰基之單體、乙烯酯單體、芳香族乙烯基單體等提昇凝聚力、耐熱性之成分,或者含有酸酐基之單體、含有羥基之單體、含有醯胺基之單體、含有胺基之單體、含有環氧基之單體、N-丙烯醯嗎啉、乙烯醚單體等提昇接著力或具有作為交聯基點而發揮作用之官能基的成分。該等單體可單獨使用,亦可將兩種以上混合使用。Further, as the other polymerizable monomer, for example, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, a cyano group-containing monomer, a vinyl ester monomer, an aromatic vinyl monomer, or the like can be suitably used for enhancing cohesive force. a heat resistant component, or an acid anhydride group-containing monomer, a hydroxyl group-containing monomer, a guanamine group-containing monomer, an amine group-containing monomer, an epoxy group-containing monomer, N-propylene morpholine, A vinyl ether monomer or the like which enhances the adhesion or has a functional group that functions as a crosslinking point. These monomers may be used singly or in combination of two or more.
作為含有磺酸基之單體,例如可列舉:苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等。Examples of the sulfonic acid group-containing monomer include styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamido-2-methylpropanesulfonic acid, and (meth)acrylamide. Sulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid, and the like.
作為含有磷酸基之單體,例如可列舉:2-羥基乙基丙烯醯基磷酸酯、單[聚(氧化丙烯)(甲基)丙烯酸酯]磷酸酯。Examples of the phosphoric acid group-containing monomer include 2-hydroxyethyl acrylonitrile phosphate and mono [poly(oxypropylene) (meth) acrylate] phosphate.
作為含有氰基之單體,例如可列舉:丙烯腈、甲基丙烯腈等。Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
作為乙烯酯單體,例如可列舉:乙酸乙烯酯、丙酸乙烯酯、月桂酸乙烯酯等。Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl laurate.
作為芳香族乙烯基單體,例如可列舉:苯乙烯、氯苯乙烯、氯甲基苯乙烯、α-甲基苯乙烯等。Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, and α-methylstyrene.
作為含有酸酐基之單體,例如可列舉:順丁烯二酸酐、衣康酸酐等。Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride.
作為含有羥基之單體,例如可列舉:(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、丙烯酸(4-羥基甲基環己基)甲酯、N-羥甲基(甲基)丙烯醯胺、N-羥基(甲基)丙烯醯胺、乙烯醇、烯丙醇、2-羥基乙基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚等。Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid 6 -Hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl acrylate , N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethyl Glycol monovinyl ether and the like.
作為含有醯胺基之單體,例如可列舉:丙烯醯胺、二乙基丙烯醯胺等。Examples of the monomer containing a guanamine group include acrylamide, diethyl acrylamide, and the like.
作為含有胺基之單體,例如可列舉:(甲基)丙烯酸N,N-二甲基胺基乙酯、(甲基)丙烯酸N,N-二甲基胺基丙酯、N-(甲基)丙烯醯基嗎啉、(甲基)丙烯酸烷基胺基烷基酯等。Examples of the monomer having an amine group include N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N-(A). Base) acryloyl morpholine, alkylaminoalkyl (meth) acrylate, and the like.
作為含有環氧基之單體,例如可列舉:(甲基)丙烯酸縮水甘油酯、烯丙基縮水甘油醚等。Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate and allyl glycidyl ether.
作為乙烯醚單體,例如可列舉:甲基乙烯醚、乙基乙烯醚、異丁基乙烯醚等。Examples of the vinyl ether monomer include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
進而,作為上述以外之聚合性單體,可列舉含有矽原子之矽烷系單體。作為矽烷系單體,例如可列舉:3-(甲基)丙烯醯氧基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、4-乙烯基丁基三甲氧基矽烷、4-乙烯基丁基三乙氧基矽烷、8-乙烯基辛基三甲氧基矽烷、8-乙烯基辛基三乙氧基矽烷、10-甲基丙烯醯氧基癸基三甲氧基矽烷、10-丙烯醯氧基癸基三甲氧基矽烷、10-甲基丙烯醯氧基癸基三乙氧基矽烷、10-丙烯醯氧基癸基三乙氧基矽烷等。Further, examples of the polymerizable monomer other than the above include a decane-based monomer containing a ruthenium atom. Examples of the decane-based monomer include 3-(meth)acryloxypropyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, and 4-vinylbutyltrimethoxy. Baseline, 4-vinylbutyltriethoxydecane, 8-vinyloctyltrimethoxydecane, 8-vinyloctyltriethoxydecane, 10-methylpropenyloxydecyltrimethoxy Alkane, 10-propenyloxydecyltrimethoxydecane, 10-methylpropenyloxydecyltriethoxydecane, 10-propenyloxydecyltriethoxydecane, and the like.
上述矽烷系單體可單獨使用,亦可將兩種以上混合使用,該矽烷系單體之整體之含量相對於丙烯酸系聚合物100重量份較好的是0.01~3重量份,更好的是0.01~1重量份。使矽烷系單體進行共聚合於提昇耐久性方面而言較好。The decane-based monomer may be used singly or in combination of two or more. The content of the decane-based monomer is preferably 0.01 to 3 parts by weight based on 100 parts by weight of the acrylic polymer, more preferably 0.01 to 1 part by weight. It is preferred to copolymerize a decane-based monomer to improve durability.
丙烯酸系聚合物較理想的是,其溶劑可溶成分之重量平均分子量為50萬以上,較好的是100萬以上,更好的是180萬以上。於重量平均分子量小於50萬之情形時,存在因黏著劑組合物之凝聚力變小而產生糨糊殘餘之傾向。重量平均分子量係藉由GPC(Gel Permeation Chromatography,凝膠滲透層析法)測定而獲得者。The acrylic polymer preferably has a weight average molecular weight of a solvent-soluble component of 500,000 or more, preferably 1,000,000 or more, more preferably 1.8,000,000 or more. When the weight average molecular weight is less than 500,000, there is a tendency that the cohesive force of the adhesive composition becomes small to cause a residual of the paste. The weight average molecular weight is obtained by GPC (Gel Permeation Chromatography).
丙烯酸系聚合物係藉由乳液聚合(乳化聚合)來製備。又,所獲得之共聚物可為無規共聚物、嵌段共聚物等任意者。The acrylic polymer is prepared by emulsion polymerization (emulsification polymerization). Further, the copolymer obtained may be any of a random copolymer, a block copolymer and the like.
對於聚合起始劑、乳化劑等並無特別限定,可適宜地選擇使用。The polymerization initiator, the emulsifier and the like are not particularly limited, and can be appropriately selected and used.
作為聚合起始劑,例如可列舉:2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2-脒基丙烷)二鹽酸鹽、2,2'-偶氮雙[2-(5-甲基-2-咪唑啉-2-基)丙烷]二鹽酸鹽、2,2'-偶氮雙(2-甲基丙脒)二硫酸鹽、2,2'-偶氮雙(N,N'-二亞甲基異丁脒)、2,2'-偶氮雙[N-(2-羧乙基)-2-甲基丙脒]水合物(和光純藥公司製造,VA-057)等之偶氮系起始劑;過硫酸鉀、過硫酸銨等之過硫酸鹽;過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二-第二丁酯、過氧化新癸酸第三丁酯、過氧化特戊酸第三己酯、過氧化特戊酸第三丁酯、過氧化二月桂醯基、過氧化二正辛醯基、2-乙基過氧化己酸-1,1,3,3-四甲基丁酯、過氧化二(4-甲基苯甲醯)、過氧化二苯甲醯、過氧化異丁酸第三丁酯、1,1-雙(過氧化第三己基)環己烷、第三丁基過氧化氫、過氧化氫等之過氧化物系起始劑;過硫酸鹽與亞硫酸氫鈉之組合、過氧化物與抗壞血酸鈉之組合等將過氧化物與還原劑組合而形成之氧化還原系起始劑等,但並不限定於該等。Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, and 2,2'-azobis. [2-(5-Methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2'- Azobis(N,N'-dimethylideneisobutane), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine hydrate (Wako Pure Chemicals) Manufactured by the company, VA-057), etc.; azo-based initiator; potassium persulfate, ammonium persulfate, etc.; peroxydicarbonate di(2-ethylhexyl) ester, peroxydicarbonate di(4) -T-butylcyclohexyl)ester, di-second butyl peroxydicarbonate, tert-butyl peroxy neodecanoate, third hexyl peroxypivalate, tert-butyl peroxypivalate , dilauroyl peroxide, di-n-octyl peroxide, 2-ethylperoxyhexanoic acid-1,1,3,3-tetramethylbutyl ester, bis(4-methylbenzhydryl) peroxide, Peroxide system of benzamidine peroxide, tert-butyl peroxyisobutyrate, 1,1-bis(tetrahexyl peroxide)cyclohexane, tert-butyl hydroperoxide, hydrogen peroxide, etc. Starting agent; persulfate and sulfurous acid Combination of sodium, of sodium ascorbate in combination with a peroxide or the like formed by combining the peroxide with a reducing agent of a redox-based initiator and so forth, but are not limited to such.
聚合起始劑可單獨使用,亦可將兩種以上混合使用,該聚合起始劑整體之含量相對於單體100重量份較好的是0.002~0.5重量份,更好的是0.005~0.2重量份。The polymerization initiator may be used singly or in combination of two or more. The content of the polymerization initiator as a whole is preferably 0.002 to 0.5 part by weight, more preferably 0.005 to 0.2 part by weight based on 100 parts by weight of the monomer. Share.
作為乳化劑,例如可列舉:月桂基硫酸鈉、月桂基硫酸銨、十二烷基苯磺酸鈉、聚氧乙烯月桂基硫酸鈉、聚氧乙烯烷基醚硫酸鈉、聚氧乙烯烷基苯醚硫酸銨、聚氧乙烯烷基苯醚硫酸鈉、聚氧乙烯烷基磺基琥珀酸鈉等之陰離子系乳化劑;聚氧乙烯烷基醚、聚氧乙烯烷基苯醚、聚氧乙烯脂肪酸酯、聚氧乙烯-聚氧丙烯嵌段聚合物等之非離子系乳化劑等。該等乳化劑可單獨使用,亦可併用兩種以上。Examples of the emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium polyoxyethylene lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkylbenzene. Anionic emulsifier such as ammonium ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl sulfosuccinate; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fat A nonionic emulsifier such as an acid ester or a polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used singly or in combination of two or more.
進而,作為導入有丙烯基、烯丙基醚基等自由基聚合性官能基之反應性乳化劑,例如有AQUALON HS-10、HS-20、HS-1025、KH-10、BC-05、BC-10、BC-20(第一工業製藥公司製造),ADEKA REASOAP SE10N(旭電化公司製造)等。反應性乳化劑藉由聚合而導入至聚合物鏈中,因此耐水性變得較好,故較佳。Further, as a reactive emulsifier into which a radical polymerizable functional group such as a propenyl group or an allyl ether group is introduced, for example, AQUALON HS-10, HS-20, HS-1025, KH-10, BC-05, BC -10, BC-20 (manufactured by Daiichi Kogyo Co., Ltd.), ADEKA REASOAP SE10N (manufactured by Asahi Kasei Co., Ltd.), etc. Since the reactive emulsifier is introduced into the polymer chain by polymerization, water resistance is preferred, which is preferable.
就聚合穩定性、機械穩定性及接著性等之觀點而言,乳化劑之使用量相對於單體100重量份較好的是0.5~5重量份,更好的是1~4重量份。The amount of the emulsifier used is preferably 0.5 to 5 parts by weight, more preferably 1 to 4 parts by weight, per 100 parts by weight of the monomer, from the viewpoints of polymerization stability, mechanical stability, and adhesion.
又,聚合中亦可使用鏈轉移劑。藉由使用鏈轉移劑,可適宜地調整丙烯酸系聚合物之分子量。Further, a chain transfer agent can also be used in the polymerization. The molecular weight of the acrylic polymer can be suitably adjusted by using a chain transfer agent.
作為鏈轉移劑,例如可列舉:月桂硫醇、縮水甘油基硫醇、1-十二烷硫醇、巰基乙酸、2-巰基乙醇、硫乙醇酸、硫乙醇酸2-乙基己酯、2,3-二巰基-1-丙醇等。As the chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, 1-dodecanethiol, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, 2 , 3-dimercapto-1-propanol, and the like.
該等鏈轉移劑可單獨使用,亦可將兩種以上混合使用,該鏈轉移劑整體之含量相對於單體100重量份為0.001~0.5重量份左右。These chain transfer agents may be used singly or in combination of two or more kinds, and the content of the chain transfer agent as a whole is about 0.001 to 0.5 parts by weight based on 100 parts by weight of the monomer.
作為聚合操作之例,例如首先將上述單體或共聚單體混合,於其中調配乳化劑及水之後,進行乳化來製備乳液。此時之單體亦可調配所使用之總量之全部或者一部分,於聚合過程中滴加剩餘部分。然後,於該乳液中添加聚合起始劑及視需要之水來進行乳液聚合(乳化聚合)。As an example of the polymerization operation, for example, the above monomers or comonomers are first mixed, and an emulsifier and water are formulated therein, followed by emulsification to prepare an emulsion. At this time, the monomer may be blended with all or a part of the total amount used, and the remainder is added dropwise during the polymerization. Then, a polymerization initiator and optionally water are added to the emulsion to carry out emulsion polymerization (emulsification polymerization).
再者,水可僅於製備乳液時調配,或者亦可於製備後進一步調配。又,對水之調配量並無特別限定,較好的是以使乳液聚合(乳化聚合)後之丙烯酸系聚合物之固形物濃度達到30~75重量%的方式進行製備,更好的是35~60重量%。Further, the water may be formulated only when the emulsion is prepared, or may be further formulated after the preparation. Further, the amount of water to be added is not particularly limited, and it is preferably prepared so that the solid content of the acrylic polymer after emulsion polymerization (emulsification polymerization) is 30 to 75% by weight, more preferably 35. ~60% by weight.
對乳液聚合(乳化聚合)之方法並無特別限定,可自一次性聚合法、總量滴加法、將該等組合之兩階段聚合法等中適宜地選擇。The method of the emulsion polymerization (emulsification polymerization) is not particularly limited, and can be appropriately selected from a one-time polymerization method, a total amount of addition method, a two-stage polymerization method in which these are combined, and the like.
於一次性聚合法中,例如將單體混合物、乳化劑及水裝入至反應容器中,藉由攪拌混合使該等乳化而製備乳液之後,進而於該反應容器中添加聚合起始劑及視需要之水來進行乳液聚合(乳化聚合)。In the disposable polymerization method, for example, a monomer mixture, an emulsifier, and water are charged into a reaction vessel, and the emulsion is prepared by emulsification by stirring and mixing, and then a polymerization initiator and a reaction are added to the reaction vessel. The required water is used for emulsion polymerization (emulsification polymerization).
又,於總量滴加法中,首先添加單體混合物、乳化劑及水,藉由攪拌混合使該等乳化而製備滴加液,並且預先將聚合起始劑及水裝入至反應容器中,然後將滴加液滴加於反應容器內進行乳液聚合(乳化聚合)。Further, in the total amount dropping method, a monomer mixture, an emulsifier, and water are first added, and the dropwise addition liquid is prepared by emulsification by stirring and mixing, and the polymerization initiator and water are charged into the reaction container in advance. Then, the dropwise addition was added to the reaction vessel to carry out emulsion polymerization (emulsification polymerization).
對於乳液粒子之平均粒徑,只要機械穩定性或塗佈性等良好則並無特別限制,通常為0.07~3μm,較好的是0.07~1μm。於平均粒徑未滿0.07μm之情形時,存在黏著劑之黏度變得過高之傾向,於超過3μm之情形時,存在乳液粒子間之融著性下降從而導致凝聚力下降之傾向。The average particle diameter of the emulsion particles is not particularly limited as long as it is excellent in mechanical stability and coatability, and is usually 0.07 to 3 μm, preferably 0.07 to 1 μm. When the average particle diameter is less than 0.07 μm, the viscosity of the adhesive tends to be too high, and when it exceeds 3 μm, the meltability between the emulsion particles is lowered to cause a decrease in cohesive force.
水分散型丙烯酸系黏著劑將上述丙烯酸系聚合物乳液作為主劑成分,視需要可含有交聯劑。作為交聯劑,可列舉:碳二醯亞胺化合物、含有唑啉基之化合物、聚異氰酸酯化合物、聚胺化合物、三聚氰胺樹脂、脲樹脂、環氧樹脂等。交聯劑之添加量只要為不妨礙黏著特性之範圍則無特別限制,通常於黏著劑之固形物中占0.01~10重量%,較好的是0.05~5重量%。於交聯劑之添加量較多之情形時,存在黏著劑層之彈性模數過高之傾向,有時會導致接著力下降。進而,可調配賦黏成分或其他各種添加劑。The water-dispersible acrylic pressure-sensitive adhesive contains the above-mentioned acrylic polymer emulsion as a main component, and may contain a crosslinking agent as needed. Examples of the crosslinking agent include a carbodiimide compound and a An oxazoline group compound, a polyisocyanate compound, a polyamine compound, a melamine resin, a urea resin, an epoxy resin, or the like. The amount of the crosslinking agent to be added is not particularly limited as long as it does not impair the adhesion characteristics, and is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the solid content of the adhesive. When the amount of the crosslinking agent added is large, the elastic modulus of the adhesive layer tends to be too high, and the adhesion may be lowered. Further, an adhesive component or other various additives can be added.
進而,亦可於水分散型丙烯酸系黏著劑中添加其他公知之添加劑,例如可適宜地添加賦黏劑、增塑劑、填充劑、抗氧化劑、紫外線吸收劑、矽烷偶合劑等。Further, other known additives may be added to the water-dispersible acrylic pressure-sensitive adhesive. For example, a tackifier, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a decane coupling agent, or the like may be added as appropriate.
黏著型光學膜係於光學膜之至少單面上藉由上述黏著劑而形成有黏著劑層者。The adhesive optical film is formed by forming an adhesive layer on at least one side of the optical film by the above-mentioned adhesive.
作為形成黏著劑層之方法,例如可列舉:將水分散型黏著劑塗佈於經剝離處理之分離膜(separator)等上,乾燥去除聚合溶劑等而形成黏著劑層,之後將該黏著劑層轉印至光學膜上之方法;或者將水分散型黏著劑塗佈於光學膜上,乾燥去除聚合溶劑等而形成黏著劑層之方法等。As a method of forming the pressure-sensitive adhesive layer, for example, a water-dispersible pressure-sensitive adhesive is applied onto a separation-treated separator or the like, and a polymerization solvent or the like is dried to form an adhesive layer, and then the adhesive layer is formed. A method of transferring onto an optical film; or a method of applying a water-dispersible pressure-sensitive adhesive to an optical film, drying and removing a polymerization solvent or the like to form an adhesive layer, and the like.
作為黏著劑層之形成方法,可採用各種方法。例如可列舉使用刮刀式塗佈機(comma coater)、噴射式塗佈機(fountain die coater)、唇口式塗佈機(lip coater)、狹縫擠壓式塗佈機(slot die coater)等塗佈機之方法。As a method of forming the adhesive layer, various methods can be employed. For example, a comma coater, a fountain die coater, a lip coater, a slot die coater, or the like can be used. The method of the coater.
對黏著劑層之厚度並無特別限制,通常為3~500μm左右。較好的是5~100μm,更好的是5~40μm。The thickness of the adhesive layer is not particularly limited and is usually about 3 to 500 μm. It is preferably 5 to 100 μm, more preferably 5 to 40 μm.
黏著型光學膜較好的是於光學膜與黏著劑層之間具有增黏層。The adhesive optical film preferably has a tackifying layer between the optical film and the adhesive layer.
作為增黏層之形成材料,較好的是使用具有與黏著劑層之聚合物反應之官能基的聚合物,例如可列舉含有唑啉基之聚合物、含有胺基之聚合物。As a material for forming the adhesion-promoting layer, a polymer having a functional group reactive with the polymer of the adhesive layer is preferably used, and for example, it may be mentioned An oxazoline-based polymer or an amine-containing polymer.
增黏層可藉由將含有上述聚合物之溶液或水分散液直接塗佈於光學膜之單面或兩面上,並加以乾燥而形成。The adhesion-promoting layer can be formed by directly applying a solution or an aqueous dispersion containing the above polymer to one side or both surfaces of the optical film and drying it.
乾燥後之增黏層之厚度通常為1~500nm,較好的是10~450nm,更好的是15~400nm。若增黏層為上述範圍之厚度,則可充分提高光學膜與黏著劑層之密著力。The thickness of the tackified layer after drying is usually from 1 to 500 nm, preferably from 10 to 450 nm, more preferably from 15 to 400 nm. If the adhesion-promoting layer has a thickness in the above range, the adhesion between the optical film and the adhesive layer can be sufficiently increased.
作為黏著型光學膜中所使用之光學膜,例如可列舉偏光板。偏光板通常使用於偏光片之單面或兩面上具有透明保護膜者。As an optical film used for the adhesive optical film, a polarizing plate is mentioned, for example. The polarizing plate is generally used for a transparent protective film on one side or both sides of the polarizer.
對偏光片並無特別限定,可使用各種偏光片。偏光片例如可列舉:使聚乙烯醇系膜、部分縮甲醛化聚乙烯醇系膜、乙烯‧乙酸乙烯酯共聚物系部分皂化膜等之親水性高分子膜吸附碘或二色性染料之二色性物質,然後進行單軸延伸所得者;以及聚乙烯醇之脫水處理物或聚氯乙烯之脫氯化氫處理物等多烯系配向膜等。該等之中,較好的是由聚乙烯醇系膜與碘等二色性物質所形成之偏光片。對該等偏光片之厚度並無特別限制,通常為5~80μm左右。The polarizer is not particularly limited, and various polarizers can be used. Examples of the polarizer include a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene/vinyl acetate copolymer partial saponified film, which adsorbs iodine or a dichroic dye. The coloring matter is then obtained by uniaxial stretching; and a polyene-based alignment film such as a dehydrated material of polyvinyl alcohol or a dehydrochlorination product of polyvinyl chloride. Among these, a polarizer formed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferred. The thickness of the polarizer is not particularly limited and is usually about 5 to 80 μm.
用碘將聚乙烯醇系膜染色並單軸延伸之偏光片例如可藉由如下方法來製作:將聚乙烯醇膜浸漬於碘之水溶液中進行染色,並使該聚乙烯醇膜延伸至原長之3~7倍。亦可將聚乙烯醇系膜浸漬於碘化鉀等之水溶液中,且該水溶液視需要亦可含有硼酸、硫酸鋅、氯化鋅等。進而,視需要亦可於染色之前將聚乙烯醇系膜浸漬於水中進行水洗。藉由對聚乙烯醇系膜進行水洗,可將聚乙烯醇系膜表面之污垢或抗結塊劑清洗掉,除此以外,藉此亦可使聚乙烯醇系膜膨潤,從而具有防止染色不均等不均一之效果。延伸可於用碘進行染色之後進行,亦可一面染色一面延伸,亦可於延伸之後利用碘進行染色。亦可於硼酸或碘化鉀等之水溶液或者水浴中進行延伸。A polarizer in which a polyvinyl alcohol-based film is dyed and uniaxially stretched with iodine can be produced, for example, by immersing a polyvinyl alcohol film in an aqueous solution of iodine for dyeing, and extending the polyvinyl alcohol film to the original length. 3 to 7 times. The polyvinyl alcohol-based film may be immersed in an aqueous solution of potassium iodide or the like, and the aqueous solution may contain boric acid, zinc sulfate, zinc chloride or the like as needed. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the dirt or the anti-caking agent on the surface of the polyvinyl alcohol-based film can be washed away, and in addition, the polyvinyl alcohol-based film can be swollen to prevent dyeing. Equal uneven effect. The extension may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. It can also be extended in an aqueous solution or a water bath such as boric acid or potassium iodide.
作為構成透明保護膜之材料,例如可使用透明性、機械強度、熱穩定性、水分阻隔性、等向性等優異之熱塑性樹脂。作為此種熱塑性樹脂之具體例,可列舉:三乙酸纖維素等之纖維素樹脂、聚酯樹脂、聚醚碸樹脂、聚碸樹脂、聚碳酸酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚烯烴樹脂、(甲基)丙烯酸系樹脂、環狀聚烯烴樹脂(降烯系樹脂)、聚芳酯樹脂、聚苯乙烯樹脂、聚乙烯醇樹脂以及該等之混合物。再者,於偏光片之一側藉由接著劑層而貼合有透明保護膜,於另一側,可使用(甲基)丙烯酸系、胺基甲酸酯系、丙烯酸胺基甲酸酯系、環氧系、矽氧系等之熱硬化性樹脂或紫外線硬化型樹脂作為透明保護膜。透明保護膜中亦可含有一種以上任意適當之添加劑。作為添加劑,例如可列舉:紫外線吸收劑、抗氧化劑、潤滑劑、增塑劑、脫模劑、防著色劑、阻燃劑、成核劑、抗靜電劑、顏料、著色劑等。透明保護膜中之上述熱塑性樹脂之含量較好的是50~100重量%,更好的是50~99重量%,進而更好的是60~98重量%,特別好的是70~97重量%。於透明保護膜中之上述熱塑性樹脂之含量為50重量%以下之情形時,熱塑性樹脂原本所具有之高透明性等有可能無法充分地表現出來。As the material constituting the transparent protective film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, moisture barrier property, and isotropic property can be used. Specific examples of such a thermoplastic resin include cellulose resins such as cellulose triacetate, polyester resins, polyether oxime resins, polyfluorene resins, polycarbonate resins, polyamide resins, and polyimide resins. , polyolefin resin, (meth)acrylic resin, cyclic polyolefin resin An olefinic resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and a mixture thereof. Further, a transparent protective film is bonded to one side of the polarizer by an adhesive layer, and (meth)acrylic, urethane-based or urethane-based acrylate is used on the other side. A thermosetting resin such as an epoxy resin or an anthracene oxygen resin or an ultraviolet curable resin is used as a transparent protective film. The transparent protective film may also contain one or more of any suitable additives. Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color preventive agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like. The content of the above thermoplastic resin in the transparent protective film is preferably from 50 to 100% by weight, more preferably from 50 to 99% by weight, still more preferably from 60 to 98% by weight, particularly preferably from 70 to 97% by weight. . When the content of the thermoplastic resin in the transparent protective film is 50% by weight or less, the high transparency and the like which the thermoplastic resin originally has may not be sufficiently exhibited.
又,作為透明保護膜,可列舉日本專利特開2001-343529號公報(WO 01/37007)中所揭示之聚合物膜,例如含有(A)側鏈上具有取代及/或非取代醯亞胺基之熱塑性樹脂、與(B)側鏈上具有取代及/或非取代苯基及腈基之熱塑性樹脂的樹脂組合物。作為具體例,可列舉含有包含異丁烯與N-甲基順丁烯二醯亞胺之交替共聚物、與丙烯腈-苯乙烯共聚物之樹脂組合物的膜。膜可使用由樹脂組合物之混合擠出品等所形成之膜。該等膜之相位差較小,且光彈性係數較小,因此可消除因偏光板之應變而產生之不均等之不良情況,而且,該等膜之透濕度較小,因此加濕耐久性優異。Further, as the transparent protective film, a polymer film disclosed in Japanese Patent Laid-Open Publication No. 2001-343529 (WO 01/37007), for example, contains (A) a substituted and/or unsubstituted quinone imine on the side chain. A resin composition based on a thermoplastic resin and a thermoplastic resin having a substituted and/or unsubstituted phenyl group and a nitrile group in (B) a side chain. Specific examples include a film containing a resin composition comprising an alternating copolymer of isobutylene and N-methylbutyleneimine and an acrylonitrile-styrene copolymer. As the film, a film formed of a mixed extrusion of a resin composition or the like can be used. Since the phase difference of the films is small and the photoelastic coefficient is small, the unevenness due to the strain of the polarizing plate can be eliminated, and the moisture permeability of the films is small, so that the humidifying durability is excellent. .
透明保護膜之厚度可適宜地確定,就強度或操作性等之作業性、薄層性等觀點而言,該膜之厚度通常為1~500μm左右。特別好的是1~300μm,更好的是5~200μm。透明保護膜為5~150μm時特別合適。The thickness of the transparent protective film can be appropriately determined, and the thickness of the film is usually about 1 to 500 μm from the viewpoints of workability such as strength and workability, and thin layer properties. Particularly preferably, it is 1 to 300 μm, more preferably 5 to 200 μm. It is particularly suitable when the transparent protective film is 5 to 150 μm.
再者,當於偏光片之兩側設置透明保護膜時,可於其表面及背面使用由相同聚合物材料所形成之保護膜,亦可使用由不同聚合物材料等所形成之保護膜。Further, when a transparent protective film is provided on both sides of the polarizer, a protective film formed of the same polymer material may be used on the front and back surfaces thereof, and a protective film formed of a different polymer material or the like may be used.
作為透明保護膜,較好的是使用選自纖維素樹脂、聚碳酸酯樹脂、環狀聚烯烴樹脂及(甲基)丙烯酸系樹脂中之任意的至少一種。As the transparent protective film, at least one selected from the group consisting of a cellulose resin, a polycarbonate resin, a cyclic polyolefin resin, and a (meth)acrylic resin is preferably used.
纖維素樹脂係纖維素與脂肪酸之酯。作為此種纖維素酯系樹脂之具體例,可列舉:三乙酸纖維素、二乙酸纖維素、三丙酸纖維素、二丙酸纖維素等。該等之中,特別好的是三乙酸纖維素。三乙酸纖維素市售有較多產品,就獲得容易性或成本之觀點而言亦較為有利。作為三乙酸纖維素之市售品之例,可列舉:富士軟片(Fuji Film)公司製造之商品名「UV-50」、「UV-80」、「SH-80」、「TD-80U」、「TD-TAC」、「UZ-TAC」或柯尼卡(Konica)公司製造之「KC Series」等。通常,該等三乙酸纖維素之面內相位差(Re)幾乎為零,厚度方向相位差(Rth)為~60nm左右。The cellulose resin is an ester of cellulose and a fatty acid. Specific examples of such a cellulose ester-based resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Among these, cellulose triacetate is particularly preferred. Cellulose triacetate is commercially available with more products and is also advantageous from the standpoint of availability or cost. Examples of the commercially available product of cellulose triacetate include "UV-50", "UV-80", "SH-80", and "TD-80U" manufactured by Fuji Film Co., Ltd. "TD-TAC", "UZ-TAC" or "KC Series" manufactured by Konica Corporation. Usually, the in-plane retardation (Re) of the cellulose triacetate is almost zero, and the phase difference (Rth) in the thickness direction is about ~60 nm.
再者,厚度方向相位差較小之纖維素樹脂膜例如可藉由對上述纖維素樹脂進行處理而獲得。例如可列舉如下方法:將塗佈有環戊酮、甲基乙基酮等溶劑之聚對苯二甲酸乙二酯、聚丙烯、不鏽鋼等之基材膜貼合於普通的纖維素系膜上,加熱乾燥(例如於80~150℃下加熱乾燥3~10分鐘左右)之後將基材膜剝離;將降烯系樹脂、(甲基)丙烯酸系樹脂等溶解於環戊酮、甲基乙基酮等溶劑中,將得之溶液塗佈於普通的纖維素樹脂膜上,加熱乾燥(例如於80~150℃下加熱乾燥3~10分鐘左右)之後將塗佈膜剝離等。Further, the cellulose resin film having a small retardation in the thickness direction can be obtained, for example, by treating the above cellulose resin. For example, a method in which a base film such as polyethylene terephthalate coated with a solvent such as cyclopentanone or methyl ethyl ketone, polypropylene or stainless steel is bonded to a common cellulose film can be mentioned. After heating and drying (for example, drying at 80 to 150 ° C for 3 to 10 minutes), the substrate film is peeled off; The olefin resin or the (meth)acrylic resin is dissolved in a solvent such as cyclopentanone or methyl ethyl ketone, and the obtained solution is applied onto a common cellulose resin film and dried by heating (for example, 80 to 150). After heating and drying at ° C for about 3 to 10 minutes, the coating film is peeled off and the like.
又,作為厚度方向相位差較小之纖維素樹脂膜,可使用脂肪酸取代度得到控制之脂肪酸纖維素系樹脂膜。通常所使用之三乙酸纖維素之乙醯取代度為2.8左右,可藉由將乙醯取代度控制為較好之1.8~2.7來減小Rth。可藉由於上述脂肪酸取代纖維素系樹脂中添加鄰苯二甲酸二丁酯、對甲苯磺醯苯胺、乙醯檸檬酸三乙酯等之增塑劑來將Rth控制為較小。增塑劑之添加量相對於脂肪酸纖維素系樹脂100重量份較好的是40重量份以下,更好的是1~20重量份,進而更好的是1~15重量份。Further, as the cellulose resin film having a small phase difference in the thickness direction, a fatty acid cellulose resin film having a controlled degree of substitution of a fatty acid can be used. Generally, the cellulose triacetate used has a degree of substitution of about 2.8, and Rth can be reduced by controlling the degree of substitution of acetamidine to preferably 1.8 to 2.7. Rth can be controlled to be small by adding a plasticizer such as dibutyl phthalate, p-toluenesulfonanilide or triethyl citrate to the cellulose-based resin. The amount of the plasticizer added is preferably 40 parts by weight or less, more preferably 1 to 20 parts by weight, still more preferably 1 to 15 parts by weight, per 100 parts by weight of the fatty acid cellulose-based resin.
作為環狀聚烯烴樹脂之具體例,較好的是降烯系樹脂。環狀烯烴系樹脂係以環狀烯烴作為聚合單元聚合而成之樹脂的總稱,例如可列舉:日本專利特開平1-240517號公報、日本專利特開平3-14882號公報、日本專利特開平3-122137號公報等中所揭示之樹脂。作為具體例,可列舉:環狀烯烴之開環(共)聚合物,環狀烯烴之加成聚合物,環狀烯烴與乙烯、丙烯等之α-烯烴之共聚物(具有代表性的是無規共聚物),利用不飽和羧酸或其衍生物對該等進行改性所形成之接枝聚合物,以及該等之氫化物等。作為環狀烯烴之具體例,可列舉降烯系單體。As a specific example of the cyclic polyolefin resin, it is preferred to lower An olefinic resin. The cyclic olefin-based resin is a general term for a resin obtained by polymerizing a cyclic olefin as a polymerization unit, and examples thereof include a Japanese Patent Laid-Open No. Hei No. 1-240517, Japanese Patent Laid-Open No. Hei No. Hei No. Hei No. Hei No. Hei. A resin disclosed in Japanese Patent Publication No. 122137 or the like. Specific examples thereof include a ring-opening (co)polymer of a cyclic olefin, an addition polymer of a cyclic olefin, a copolymer of a cyclic olefin and an α-olefin such as ethylene or propylene (typically, a copolymer, a graft polymer formed by modifying an unsaturated carboxylic acid or a derivative thereof, and a hydride or the like. Specific examples of the cyclic olefin include a descending An olefinic monomer.
作為環狀聚烯烴樹脂,市售有各種產品。具體例可列舉:日本ZEON股份有限公司製造之商品名「ZEONEX」、「ZEONOR」,JSR股份有限公司製造之商品名「ARTON」,TICONA公司製造之商品名「TOPAS」,三井化學股份有限公司製造之商品名「APEL」。As the cyclic polyolefin resin, various products are commercially available. Specific examples include the product name "ZEONEX" manufactured by Japan ZEON Co., Ltd., "ZEONOR", the product name "ARTON" manufactured by JSR Co., Ltd., and the product name "TOPAS" manufactured by TICONA, manufactured by Mitsui Chemicals Co., Ltd. The product name is "APEL".
作為(甲基)丙烯酸系樹脂,其Tg(玻璃轉移溫度)較好的是115℃以上,更好的是120℃以上,進而更好的是125℃以上,特別好的是130℃以上。藉由使Tg為115℃以上,可使偏光板之耐久性優異。對上述(甲基)丙烯酸系樹脂之Tg之上限值並無特別限定,就成形性等之觀點而言,較好的是170℃以下。可由(甲基)丙烯酸系樹脂獲得面內相位差(Re)、厚度方向相位差(Rth)幾乎為零之膜。The (meth)acrylic resin preferably has a Tg (glass transition temperature) of 115 ° C or more, more preferably 120 ° C or more, still more preferably 125 ° C or more, and particularly preferably 130 ° C or more. When the Tg is 115 ° C or more, the durability of the polarizing plate can be excellent. The upper limit of the Tg of the (meth)acrylic resin is not particularly limited, and is preferably 170 ° C or less from the viewpoint of moldability and the like. A film having an in-plane retardation (Re) and a thickness direction retardation (Rth) of almost zero can be obtained from a (meth)acrylic resin.
作為(甲基)丙烯酸系樹脂,可於不損及本發明之效果之範圍內,採用任意適當之(甲基)丙烯酸系樹脂。例如可列舉:聚甲基丙烯酸甲酯等之聚(甲基)丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等)、具有脂環族烴基之聚合物(例如甲基丙烯酸甲酯-甲基丙烯酸環己酯共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸降酯共聚物等)。較好者可列舉聚(甲基)丙烯酸甲酯等之聚(甲基)丙烯酸C1-6烷基酯。更好者可列舉以甲基丙烯酸甲酯作為主成分(50~100重量%,較好的是70~100重量%)之甲基丙烯酸甲酯系樹脂。As the (meth)acrylic resin, any suitable (meth)acrylic resin can be used without departing from the effects of the present invention. For example, poly(meth)acrylate, polymethyl methacrylate-(meth)acrylic acid copolymer, methyl methacrylate-(meth)acrylate copolymer, A Methyl acrylate-acrylate-(meth)acrylic acid copolymer, methyl (meth)acrylate-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate - Cyclohexyl methacrylate copolymer, methyl methacrylate-(meth)acrylic acid Ester copolymers, etc.). Preferably, a poly(meth)acrylic acid C1-6 alkyl ester such as poly(methyl) acrylate is used. More preferably, methyl methacrylate-based resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) is used.
作為(甲基)丙烯酸系樹脂之具體例,例如可列舉:三菱麗陽(MITSUBISHI RAYON)股份有限公司製造之ACRYPET VH或ACRYPET VRL20A、日本專利特開2004-70296號公報中所揭示之分子內具有環結構之(甲基)丙烯酸系樹脂、藉由分子內交聯或分子內環化反應所獲得之高Tg之(甲基)丙烯酸系樹脂。Specific examples of the (meth)acrylic resin include, for example, those disclosed in Mitsubishi Rayon (MITSUBISHI RAYON) Co., Ltd., ACRYPET VH or ACRYPET VRL20A, and Japanese Patent Laid-Open No. 2004-70296. A (meth)acrylic resin having a ring structure, a high Tg (meth)acrylic resin obtained by intramolecular crosslinking or intramolecular cyclization.
作為(甲基)丙烯酸系樹脂,亦可使用具有內酯環結構之(甲基)丙烯酸系樹脂。其原因在於,該具有內酯環結構之(甲基)丙烯酸系樹脂具有高耐熱性、高透明性且可藉由雙軸延伸而具有高機械強度。As the (meth)acrylic resin, a (meth)acrylic resin having a lactone ring structure can also be used. The reason for this is that the (meth)acrylic resin having a lactone ring structure has high heat resistance, high transparency, and can have high mechanical strength by biaxial stretching.
作為具有內酯環結構之(甲基)丙烯酸系樹脂,可列舉:日本專利特開2000-230016號公報、日本專利特開2001-151814號公報、日本專利特開2002-120326號公報、日本專利特開2002-254544號公報、日本專利特開2005-146084號公報等中所揭示的具有內酯環結構之(甲基)丙烯酸系樹脂。Examples of the (meth)acrylic resin having a lactone ring structure include JP-A-2000-230016, JP-A-2001-151814, JP-A-2002-120326, and JP-A. A (meth)acrylic resin having a lactone ring structure disclosed in JP-A-2005-146084, and the like.
具有內酯環結構之(甲基)丙烯酸系樹脂較好的是具有以下述通式(化1)所表示之環狀結構。The (meth)acrylic resin having a lactone ring structure preferably has a cyclic structure represented by the following formula (Chemical Formula 1).
式中,R1 、R2 及R3 分別獨立地表示氫原子或碳原子數為1~20之有機殘基。再者,有機殘基可含有氧原子。In the formula, R 1 , R 2 and R 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. Further, the organic residue may contain an oxygen atom.
具有內酯環結構之(甲基)丙烯酸系樹脂之結構中的以通式(化1)所表示之內酯環結構的含有比例較好的是5~90重量%,更好的是10~70重量%,進而更好的是10~60重量%,特別好的是10~50重量%。若具有內酯環結構之(甲基)丙烯酸系樹脂之結構中的以通式(化1)所表示之內酯環結構的含有比例少於5重量%,則該(甲基)丙烯酸系樹脂之耐熱性、耐溶劑性、表面硬度有可能變得不充分。若具有內酯環結構之(甲基)丙烯酸系樹脂之結構中的以通式(化1)所表示之內酯環結構的含有比例多於90重量%,則該(甲基)丙烯酸系樹脂有可能缺乏成形加工性。The content of the lactone ring structure represented by the formula (Chemical Formula 1) in the structure of the (meth)acrylic resin having a lactone ring structure is preferably from 5 to 90% by weight, more preferably from 10 to 8% by weight. 70% by weight, further preferably 10 to 60% by weight, particularly preferably 10 to 50% by weight. When the content ratio of the lactone ring structure represented by the formula (Chemical Formula 1) in the structure of the (meth)acrylic resin having a lactone ring structure is less than 5% by weight, the (meth)acrylic resin The heat resistance, solvent resistance, and surface hardness may be insufficient. When the content ratio of the lactone ring structure represented by the formula (Chemical Formula 1) in the structure of the (meth)acrylic resin having a lactone ring structure is more than 90% by weight, the (meth)acrylic resin There may be a lack of formability.
具有內酯環結構之(甲基)丙烯酸系樹脂之質量平均分子量(有時亦稱為重量平均分子量)較好的是1000~2000000,更好的是5000~1000000,進而更好的是10000~500000,特別好的是50000~500000。若質量平均分子量在上述範圍之外,則就成形加工性之觀點而言不佳。The mass average molecular weight (sometimes referred to as a weight average molecular weight) of the (meth)acrylic resin having a lactone ring structure is preferably from 1,000 to 2,000,000, more preferably from 5,000 to 1,000,000, and even more preferably from 10,000 to 10,000. 500000, especially good is 50000~500000. When the mass average molecular weight is outside the above range, it is not preferable from the viewpoint of moldability.
具有內酯環結構之(甲基)丙烯酸系樹脂之Tg較好的是115℃以上,更好的是120℃以上,進而更好的是125℃以上,特別好的是130℃以上。由於該(甲基)丙烯酸系樹脂之Tg為115℃以上,因此例如當製成透明保護膜組並組入至偏光板中時,耐久性優異。對上述具有內酯環結構之(甲基)丙烯酸系樹脂之Tg的上限值並無特別限定,就成形性等之觀點而言,較好的是170℃以下。The Tg of the (meth)acrylic resin having a lactone ring structure is preferably 115 ° C or more, more preferably 120 ° C or more, still more preferably 125 ° C or more, and particularly preferably 130 ° C or more. Since the (meth)acrylic resin has a Tg of 115° C. or higher, it is excellent in durability when it is formed into a transparent protective film group and incorporated into a polarizing plate. The upper limit of the Tg of the (meth)acrylic resin having a lactone ring structure is not particularly limited, and is preferably 170 ° C or less from the viewpoint of moldability and the like.
對於具有內酯環結構之(甲基)丙烯酸系樹脂而言,藉由對其進行射出成形而獲得之成形品的利用以ASTM-D-1003為依據之方法所測定的全光線透過率越高越好,較好的是85%以上,更好的是88%以上,進而更好的是90%以上。全光線透過率係透明性之標準,若全光線透過率未滿85%,則透明性有可能會下降。For a (meth)acrylic resin having a lactone ring structure, the use of a molded article obtained by injection molding has a higher total light transmittance measured by the method based on ASTM-D-1003. The better, the better is 85% or more, more preferably 88% or more, and even more preferably 90% or more. The total light transmittance is a standard of transparency. If the total light transmittance is less than 85%, the transparency may be lowered.
上述透明保護膜通常使用正面相位差未滿40nm,且厚度方向相位差未滿80nm者。正面相位差Re以Re=(nx-ny)×d表示。厚度方向相位差Rth以Rth=(nx-nz)×d表示。又,Nz係數以Nz=(nx-nz)/(nx-ny)表示。[其中,將膜之慢軸方向、快軸方向及厚度方向之折射率分別設為nx、ny、nz,d(nm)為膜之厚度。慢軸方向為膜面內之折射率最大之方向]。再者,透明保護膜較好的是儘可能地無著色。可較好地使用厚度方向之相位差值為-90nm~+75nm之保護膜。藉由使用該厚度方向之相位差值(Rth)為-90nm~+75nm者,可幾乎消除由透明保護膜所引起之偏光板之著色(光學著色)。厚度方向相位差值(Rth)更好的是-80nm~+60nm,特別好的是-70nm~+45nm。The transparent protective film is generally used in which the front phase difference is less than 40 nm and the thickness direction retardation is less than 80 nm. The front phase difference Re is represented by Re = (nx - ny) × d. The thickness direction phase difference Rth is represented by Rth = (nx - nz) × d. Further, the Nz coefficient is expressed by Nz = (nx - nz) / (nx - ny). [The refractive index of the slow axis direction, the fast axis direction, and the thickness direction of the film is set to nx, ny, nz, and d (nm), respectively, to the thickness of the film. The direction of the slow axis is the direction in which the refractive index in the film plane is the largest]. Further, the transparent protective film is preferably as colorless as possible. A protective film having a phase difference in the thickness direction of -90 nm to +75 nm can be preferably used. By using the phase difference (Rth) in the thickness direction of -90 nm to +75 nm, the coloring (optical coloring) of the polarizing plate caused by the transparent protective film can be almost eliminated. The phase difference (Rth) in the thickness direction is more preferably -80 nm to +60 nm, and particularly preferably -70 nm to +45 nm.
另一方面,作為上述透明保護膜,可使用具有正面相位差為40nm以上及/或厚度方向相位差為80nm以上之相位差的相位差板。通常將正面相位差控制於40~200nm之範圍內,且通常將厚度方向相位差控制於80~300nm之範圍內。當使用相位差板作為透明保護膜時,由於該相位差板亦作為透明保護膜而發揮功能,因此可實現薄型化。On the other hand, as the transparent protective film, a phase difference plate having a front phase difference of 40 nm or more and/or a thickness direction retardation of 80 nm or more can be used. Generally, the front phase difference is controlled within a range of 40 to 200 nm, and the thickness direction phase difference is usually controlled within a range of 80 to 300 nm. When a retardation film is used as the transparent protective film, since the retardation film also functions as a transparent protective film, it can be made thinner.
作為相位差板,可列舉:對高分子素材進行單軸或雙軸延伸處理所形成之雙折射膜、液晶聚合物之配向膜、以膜支持液晶聚合物之配向層者等。對相位差板之厚度亦並無特別限制,通常為20~150μm左右。Examples of the retardation film include a birefringent film formed by subjecting a polymer material to uniaxial or biaxial stretching treatment, an alignment film of a liquid crystal polymer, and an alignment layer supporting a liquid crystal polymer by a film. The thickness of the phase difference plate is also not particularly limited, and is usually about 20 to 150 μm.
作為高分子素材,例如可列舉:聚乙烯醇、聚乙烯丁醛、聚甲基乙烯醚、聚丙烯酸羥基乙酯、羥基乙基纖維素、羥基丙基纖維素、甲基纖維素、聚碳酸酯、聚芳酯、聚碸、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚醚碸、聚苯硫醚、聚苯醚、聚烯丙基碸、聚醯胺、聚醯亞胺、聚烯烴、聚氯乙烯、纖維素樹脂、環狀聚烯烴樹脂(降烯系樹脂)或該等之二元系、三元系之各種共聚物、接枝共聚物、摻合物等。該等高分子素材藉由延伸等而形成配向物(延伸膜)。Examples of the polymer material include polyvinyl alcohol, polyvinyl butyral, polymethyl vinyl ether, polyhydroxyethyl acrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, and polycarbonate. , polyarylate, polyfluorene, polyethylene terephthalate, polyethylene naphthalate, polyether oxime, polyphenylene sulfide, polyphenylene ether, polyallyl fluorene, polyamine, polyfluorene Imine, polyolefin, polyvinyl chloride, cellulose resin, cyclic polyolefin resin An olefinic resin) or various binary or ternary copolymers, graft copolymers, blends, and the like. These polymer materials form an alignment (stretching film) by stretching or the like.
作為液晶聚合物,例如可列舉於聚合物之主鏈或側鏈上導入有賦予液晶配向性之共軛性之直線狀原子團(液晶原基)的主鏈型或側鏈型之各種液晶聚合物。作為主鏈型液晶聚合物之具體例,可列舉:於賦予彎曲性之間隔基部鍵結液晶原基之結構的例如向列配向性之聚酯系液晶聚合物、圓盤型聚合物或膽固醇型聚合物等。作為側鏈型液晶聚合物之具體例,可列舉如下:以聚矽氧烷、聚丙烯酸酯、聚甲基丙烯酸酯或聚丙二酸酯作為主鏈骨架,且經由包含共軛性原子團之間隔基部而具有包含向列配向賦予性之對位取代環狀化合物單元的液晶原基部來作為側鏈者等。對於該等液晶聚合物,例如將液晶聚合物之溶液展開於對玻璃板上所形成之聚醯亞胺或聚乙烯醇等之簿膜之表面進行摩擦處理所得者、以及斜向蒸鍍有氧化矽者等的配向處理面上,然後進行熱處理而獲得相位差板。Examples of the liquid crystal polymer include various liquid crystal polymers of a main chain type or a side chain type in which a linear atomic group (liquid crystal priming group) which imparts a conjugate property to a liquid crystal alignment property is introduced into a main chain or a side chain of a polymer. . Specific examples of the main chain type liquid crystal polymer include, for example, a nematic alignment polyester liquid crystal polymer, a disc type polymer, or a cholesterol type which is a structure in which a liquid crystal priming unit is bonded to a spacer having a bending property. Polymers, etc. Specific examples of the side chain type liquid crystal polymer include polysiloxane, polyacrylate, polymethacrylate or polymalonate as a main chain skeleton, and via a spacer base containing a conjugated atomic group. On the other hand, a liquid crystal original base having a para-substituted cyclic compound unit containing a nematic alignment imparting property is used as a side chain or the like. For the liquid crystal polymer, for example, a solution of a liquid crystal polymer is developed by rubbing a surface of a film of a polyimide film or a polyvinyl alcohol formed on a glass plate, and is oxidized by oblique vapor deposition. The alignment treatment surface of the latter or the like is then subjected to heat treatment to obtain a phase difference plate.
相位差板例如可為各種波片、或者以對由液晶層之雙折射所引起之著色或視角等進行補償為目的者等具有與使用目的相對應之適宜的相位差者,亦可為將兩種以上之相位差板積層而對相位差等光學特性加以控制者等。The retardation plate may be, for example, a variety of wave plates or a suitable phase difference corresponding to the purpose of use, for the purpose of compensating for coloring or viewing angle caused by birefringence of the liquid crystal layer, or may be two The above-described phase difference plate is laminated to control optical characteristics such as phase difference.
相位差板可對應於各種用途而選擇使用滿足nx=ny>nz'nx>ny>nz、nx>ny=nz、nx>nz>ny、nz=nx>ny、nz>nx>ny、nz>nx=ny之關係者。再者,所謂ny=nz,不僅指ny與nz完全相同之情形,亦包括ny與nz實質上相同之情形。The phase difference plate can be selected and used corresponding to various uses to satisfy nx=ny>nz'nx>ny>nz, nx>ny=nz, nx>nz>ny, nz=nx>ny, nz>nx>ny, nz> Nx=ny relationship. Furthermore, the so-called ny=nz means not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.
例如於滿足nx>ny>nz之相位差板中,較好的是使用正面相位差滿足40~100nm,厚度方向相位差滿足100~320nm,Nz係數滿足1.8~4.5者。例如於滿足nx>ny=nz之相位差板(陽極A板)中,較好的是使用正面相位差滿足100~200nm者。例如於滿足nz=nx>ny之相位差板(陰極A板)中,較好的是使用正面相位差滿足100~200nm者。例如於滿足nx>nz>ny之相位差板中,較好的是使用正面相位差為150~300nm,Nz係數滿足超過0而為0.7以下者。又,如上所述,例如可使用滿足nz=ny>nz、nz>nx>ny或nz>nx=ny者。For example, in a phase difference plate satisfying nx>ny>nz, it is preferable to use a front phase difference of 40 to 100 nm, a thickness direction phase difference of 100 to 320 nm, and an Nz coefficient of 1.8 to 4.5. For example, in a phase difference plate (anode A plate) satisfying nx>ny=nz, it is preferable to use a front phase difference of 100 to 200 nm. For example, in a phase difference plate (cathode A plate) satisfying nz=nx>ny, it is preferable to use a front phase difference of 100 to 200 nm. For example, in a phase difference plate satisfying nx>nz>ny, it is preferable to use a front phase difference of 150 to 300 nm, and an Nz coefficient of more than 0 and 0.7 or less. Further, as described above, for example, nz=ny>nz, nz>nx>ny, or nz>nx=ny can be used.
透明保護膜可對應於應用其之液晶顯示裝置而適宜選擇。例如,於VA(垂直配向(Vertical Alignment),包括MVA(Multi-Domain Vertical Alignment,多象限垂直配向)、PVA(Patterned Vertical Alignment,圖形化垂直配向))之情形時,較理想的是偏光板之至少一方(液晶單元側)之透明保護膜具有相位差。作為具體的相位差,較理想的是Re=0~240nm,Rth=0~500nm之範圍。若以三維折射率而言,較理想的是nx>ny=nz、nx>ny>nz、nx>nz>ny、nx=ny>nz(陽極A板、雙軸、陰極C板)之情形。於VA型液晶顯示裝置中,較好的是陽極A板與陰極C板之組合、或使用1片雙軸膜。當於液晶單元之上下使用偏光板時,可使液晶單元上下均具有相位差、或者使上下之任一透明保護膜具有相位差。The transparent protective film can be suitably selected corresponding to the liquid crystal display device to which it is applied. For example, in the case of VA (Vertical Alignment, including MVA (Multi-Domain Vertical Alignment), PVA (Patterned Vertical Alignment)), it is preferable to use a polarizing plate. The transparent protective film of at least one (liquid crystal cell side) has a phase difference. As a specific phase difference, Re = 0 to 240 nm and Rth = 0 to 500 nm are preferable. In the case of a three-dimensional refractive index, it is preferable that nx>ny=nz, nx>ny>nz, nx>nz>ny, nx=ny>nz (anode A plate, biaxial, cathode C plate). In the VA type liquid crystal display device, a combination of an anode A plate and a cathode C plate or a single biaxial film is preferably used. When the polarizing plate is used above and below the liquid crystal cell, the liquid crystal cell can have a phase difference both above and below, or any of the upper and lower transparent protective films can have a phase difference.
例如於IPS(橫向電場切換(In-Plane Switching),包括FFS(Fringe Field Switching,邊緣電場切換))之情形時,可使用偏光板之一方之透明保護膜具有相位差或不具有相位差之情形中之任一者。例如,於不具有相位差之情形時,較理想的是液晶單元之上下(液晶單元側)均不具有相位差之情形。於具有相位差之情形時,較理想的是液晶單元之上下均具有相位差之情形、或上下之任一者具有相位差之情形(例如上側為滿足nx>na>ny之關係之雙軸膜,下側不具有相位差之情形,或者上側為陽極A板,下側為陽極C板之情形)。於具有相位差之情形時,較理想的是Re=-500~500nm,Rth=-500~500nm之範圍。若以三維折射率而言,較理想的是nx>ny=nz、nx>nz>ny、nz>nx=ny、nz>nx>ny(陽極A板、雙軸、陽極C板)。For example, in the case of IPS (In-Plane Switching, including FFS (Fringe Field Switching)), one of the polarizing plates can be used with a phase difference or no phase difference. Any of them. For example, in the case where there is no phase difference, it is desirable that the liquid crystal cell does not have a phase difference above (the liquid crystal cell side). In the case of having a phase difference, it is preferable that the liquid crystal cell has a phase difference between the upper and lower sides, or that both of the upper and lower sides have a phase difference (for example, the upper side is a biaxial film satisfying the relationship of nx>na>ny). The lower side does not have a phase difference, or the upper side is the anode A plate and the lower side is the anode C plate). In the case of having a phase difference, it is preferable that Re = -500 to 500 nm and Rth = -500 to 500 nm. In terms of three-dimensional refractive index, it is preferable that nx>ny=nz, nx>nz>ny, nz>nx=ny, nz>nx>ny (anode A plate, biaxial, anode C plate).
再者,可另外將上述具有相位差之膜貼合於不具有相位差之透明保護膜上,而賦予透明保護膜上述功能。Further, the film having the phase difference described above may be bonded to a transparent protective film having no phase difference to impart the above-described function to the transparent protective film.
對於上述透明保護膜,為了提昇其與偏光片之接著性,可於塗佈接著劑之前進行表面改質處理。作為具體的處理,可列舉:電暈處理、電漿處理、火焰處理、臭氧處理、底塗處理、輝光處理、皂化處理、利用偶合劑之處理等。又,可適宜地形成抗靜電層。In order to improve the adhesion to the polarizer, the transparent protective film may be subjected to surface modification treatment before the application of the adhesive. Specific examples of the treatment include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, saponification treatment, and treatment with a coupling agent. Further, an antistatic layer can be suitably formed.
對於上述透明保護膜之未接著有偏光片之面,可形成硬塗層或者實施抗反射處理,以及以防黏、擴散或防眩為目的之處理。For the surface of the transparent protective film which is not followed by the polarizer, a hard coat layer may be formed or an anti-reflection treatment may be performed, and a treatment for preventing adhesion, diffusion or anti-glare may be employed.
硬塗處理係為了防止偏光板表面受損等而實施者,硬塗層例如可藉由將由丙烯酸系、矽氧系等適宜之紫外線硬化型樹脂所形成的硬度或滑動特性等優異之硬化皮膜,附加於透明保護膜之表面而形成。抗反射處理係為了防止偏光板表面之外部光線反射而實施者,可依據先前藉由形成抗反射膜等而達成。又,防黏處理係為了防止與相鄰接之層(例如背光側之擴散板)密著而實施者。In order to prevent the surface of the polarizing plate from being damaged or the like, the hard coat layer may be a hardened film which is excellent in hardness or sliding properties such as an ultraviolet curable resin such as an acrylic or an oxime. It is formed by being attached to the surface of the transparent protective film. The antireflection treatment is carried out in order to prevent reflection of external light on the surface of the polarizing plate, and can be achieved by forming an antireflection film or the like. Further, the anti-adhesive treatment is performed to prevent adhesion to an adjacent layer (for example, a diffusing plate on the backlight side).
又,防眩處理係為了防止外部光線於偏光板之表面上反射而阻礙偏光板透過光之視認等而實施者,其例如可由如下方法形成:藉由利用噴砂方式或壓紋加工方式之粗面化方式、或者調配透明微粒子之方式等適宜之方式,對透明保護膜之表面賦予微細凹凸結構。為形成上述表面微細凹凸結構而含有之微粒子例如可使用平均粒徑為0.5~20μm之包含二氧化矽、氧化鋁、氧化鈦、氧化鋯、氧化錫、氧化銦、氧化鎘、氧化銻等的亦可具有導電性之無機系微粒子,由交聯或未交聯之聚合物等所形成之有機系微粒子等透明微粒子。於形成表面微細凹凸結構之情形時,微粒子之使用量相對於形成表面微細凹凸結構之透明樹脂100重量份,通常為2~70重量份左右,較好的是5~50重量份。防眩層亦可兼作為用以使偏光板透過光擴散從而擴大視角等之擴散層(視角擴大功能等)。Further, the anti-glare treatment is carried out in order to prevent external light from being reflected on the surface of the polarizing plate and to hinder the visibility of the light transmitted through the polarizing plate, and the like, for example, may be formed by a method of sandblasting or embossing. A fine concavo-convex structure is imparted to the surface of the transparent protective film in a suitable manner such as a method of dispersing or a method of blending transparent fine particles. For the fine particles contained in the surface fine uneven structure, for example, cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, tin oxide, indium oxide, cadmium oxide, or cerium oxide having an average particle diameter of 0.5 to 20 μm can be used. Inorganic fine particles having conductivity, transparent fine particles such as organic fine particles formed of a crosslinked or uncrosslinked polymer. In the case where the surface fine uneven structure is formed, the amount of the fine particles used is usually from 2 to 70 parts by weight, preferably from 5 to 50 parts by weight, per 100 parts by weight of the transparent resin forming the surface fine uneven structure. The anti-glare layer can also serve as a diffusion layer (such as a viewing angle expansion function) for diffusing the polarizing plate through light to expand the viewing angle or the like.
再者,上述抗反射層、防黏層、擴散層或防眩層等可設置於透明保護膜本身上,另外亦可作為與透明保護膜不同之單獨之光學層而另行設置。Further, the antireflection layer, the anti-adhesion layer, the diffusion layer or the anti-glare layer may be provided on the transparent protective film itself, or may be separately provided as a separate optical layer different from the transparent protective film.
於上述偏光片與透明保護膜之接著處理中使用接著劑。作為接著劑,可例示:異氰酸酯系接著劑、聚乙烯醇系接著劑、明膠系接著劑、乙烯系乳膠系、水系聚酯等。上述接著劑通常製成包含水溶液之接著劑而使用,且通常含有0.5~60重量%之固形物。除上述以外,偏光片與透明保護膜之接著劑亦可列舉紫外線硬化型接著劑、電子束硬化型接著劑等。電子束硬化型偏光板用接著劑對上述各種透明保護膜表現出較佳之接著性。又,本發明中所使用之接著劑中可含有金屬化合物填料。An adhesive is used in the subsequent treatment of the above polarizer and the transparent protective film. Examples of the adhesive agent include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, an ethylene-based latex, and an aqueous polyester. The above-mentioned adhesive is usually used as an adhesive containing an aqueous solution, and usually contains 0.5 to 60% by weight of a solid. In addition to the above, examples of the adhesive for the polarizer and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The electron beam-curable polarizing plate exhibits excellent adhesion to the above various transparent protective films by an adhesive. Further, the adhesive used in the present invention may contain a metal compound filler.
又,作為光學膜,例如可列舉反射板或反射透過板、上述相位差板(包括1/2或1/4等之波片)、視覺補償膜、增亮膜等在形成液晶顯示裝置等時使用過之作為光學層者。該等可單獨用作光學膜,除此以外,亦可於實際使用時積層在上述偏光板上,使用一層或兩層以上。In addition, examples of the optical film include a reflector or a reflection-transmissive plate, the retardation plate (including a wave plate of 1/2 or 1/4 or the like), a visual compensation film, a brightness enhancement film, and the like, when a liquid crystal display device or the like is formed. Used as an optical layer. These may be used alone as an optical film, or may be laminated on the above-mentioned polarizing plate in actual use, and one layer or two or more layers may be used.
特別好的是:於偏光板上進一步積層反射板或半透過反射板所形成之反射型偏光板或半透過型偏光板、於偏光板上進一步積層相位差板所形成之橢圓偏光板或圓偏光板、於偏光板上進一步積層視覺補償膜所形成之廣視角偏光板、或者於偏光板上進一步積層增亮膜所形成之偏光板。Particularly preferred is a reflective polarizing plate or a semi-transmissive polarizing plate formed by further laminating a reflecting plate or a semi-transmissive reflecting plate on a polarizing plate, and an elliptically polarizing plate or circularly polarized light formed by further laminating a phase difference plate on the polarizing plate. The plate is further provided with a wide viewing angle polarizing plate formed by a visual compensation film on the polarizing plate, or a polarizing plate formed by further accumulating a brightness enhancing film on the polarizing plate.
反射型偏光板係於偏光板上設置反射層所得者,其係用以形成使來自視認側(顯示側)之入射光反射而進行顯示之類型的液晶顯示裝置等者,具有可省略內藏背光等光源,從而使液晶顯示裝置容易實現薄型化等優點。反射型偏光板可藉由視需要經由透明保護層等,於偏光板之單面上附設包含金屬等之反射層的方式等適宜的方式而形成。The reflective polarizing plate is obtained by providing a reflective layer on a polarizing plate, and is used to form a liquid crystal display device of a type that reflects incident light from a viewing side (display side) for display, and has a built-in backlight The light source is used to make the liquid crystal display device easy to be thinned. The reflective polarizing plate can be formed by a suitable method such as a method of providing a reflective layer containing a metal or the like on one surface of the polarizing plate via a transparent protective layer or the like.
作為反射型偏光板之具體例,可列舉:於視需要經實施消光處理之透明保護膜之單面上,附設包含鋁等之反射性金屬之箔或蒸鍍膜而形成反射層者等。又,亦可列舉:使上述透明保護膜含有微粒子而形成表面微細凹凸結構,並於其上具有微細凹凸結構之反射層者等。上述微細凹凸結構之反射層具有可藉由漫反射使入射光擴散,從而防止指向性或耀眼之外觀,抑制明暗不均等之優點。又,含有微粒子之保護膜亦具有當入射光及其反射光透過該保護膜時,使該等光擴散從而可進一步抑制明暗不均等之優點。反映透明保護膜之表面微細凹凸結構的微細凹凸結構之反射層,例如可藉由以真空蒸鍍方式、離子電鍍方式、濺鍍方式或電鍍方式等適宜之方式,將金屬直接附設於透明保護層之表面等方法來形成。Specific examples of the reflective polarizing plate include a foil containing a reflective metal such as aluminum or a vapor deposited film on one surface of a transparent protective film subjected to a matte treatment, as needed, to form a reflective layer. In addition, the transparent protective film may be formed by containing fine particles to form a fine uneven structure on the surface, and a reflective layer having a fine uneven structure thereon. The reflective layer of the fine uneven structure has the advantage of being able to diffuse incident light by diffuse reflection, thereby preventing directivity or glare, and suppressing unevenness in brightness and the like. Further, the protective film containing fine particles has an advantage that when the incident light and the reflected light thereof are transmitted through the protective film, the light is diffused, and the unevenness of light and dark can be further suppressed. The reflective layer of the fine uneven structure reflecting the fine uneven structure on the surface of the transparent protective film can be directly attached to the transparent protective layer by a vacuum evaporation method, an ion plating method, a sputtering method, or a plating method, for example, in a suitable manner. The surface is formed by methods.
反射板亦可不採用直接設置於上述偏光板之透明保護膜上之方式,而於依據上述透明膜之適宜之膜上設置反射層,製成反射片材等而使用。再者,由於反射層通常包含金屬,因此就防止因氧化而引起反射率下降,進而長期維持初始反射率之觀點或者避免另外附設保護層之觀點等而言,更好的是其反射面由透明保護膜或偏光板等被覆之狀態之使用形態。The reflecting plate may be used by providing a reflecting layer on a suitable film of the transparent film instead of being directly provided on the transparent protective film of the polarizing film. Further, since the reflective layer usually contains a metal, it is preferable to prevent the reflectance from being lowered by oxidation, thereby maintaining the initial reflectance for a long period of time, or avoiding the viewpoint of additionally providing a protective layer, etc., and more preferably, the reflective surface is transparent. A form of use in which a protective film, a polarizing plate, or the like is covered.
再者,半透過型偏光板可藉由將於上述中反射光之反射層更換成反射且透過光之半反射鏡等半透過型的反射層而獲得。半透過型偏光板通常設置於液晶單元之背面側,可形成下述類型之液晶顯示裝置等:當於比較明亮之環境中使用液晶顯示裝置等時,該半透過型偏光板使來自視認側(顯示側)之入射光反射而顯示圖像,於比較暗之環境中,使用內藏於半透過型偏光板之背面側之背光等內藏電源來顯示圖像。即,半透過型偏光板對於形成下述類型之液晶顯示裝置等較為有用,即該液晶顯示裝置等於比較明亮之環境下,可節約使用背光等光源之能源,於比較暗之環境下亦可使用內置電源來進行顯示。Further, the semi-transmissive polarizing plate can be obtained by replacing a semi-transmissive reflective layer such as a half mirror which reflects the reflected light in the above-described reflection light and reflects the light. The transflective polarizing plate is usually disposed on the back side of the liquid crystal cell, and can form a liquid crystal display device or the like of the following type: when a liquid crystal display device or the like is used in a relatively bright environment, the transflective polarizing plate is brought from the viewing side ( The incident light is reflected on the display side to display an image, and in a relatively dark environment, an image is displayed using a built-in power source such as a backlight built in the back side of the semi-transmissive polarizing plate. In other words, the semi-transmissive polarizing plate is useful for forming a liquid crystal display device of the type described below, that is, the liquid crystal display device is equivalent to a relatively bright environment, and energy of a light source such as a backlight can be saved, and can be used in a relatively dark environment. Built-in power supply for display.
就於偏光板上進一步積層相位差板而形成之橢圓偏光板或圓偏光板加以說明。於將直線偏光轉換成橢圓偏光或圓偏光、將橢圓偏光或圓偏光轉換成直線偏光、或者改變直線偏光之偏光方向之情形時,係使用相位差板等。尤其是,作為將直線偏光轉換成圓偏光、或將圓偏光轉換成直線偏光之相位差板,係使用所謂之1/4波片(亦稱為λ/4片)。1/2波片(亦稱為λ/2片)通常用於改變直線偏光之偏光方向之情形。An elliptically polarizing plate or a circularly polarizing plate formed by further laminating a phase difference plate on a polarizing plate will be described. When a linearly polarized light is converted into elliptically polarized or circularly polarized light, elliptically polarized or circularly polarized light is converted into linearly polarized light, or a polarized direction of linearly polarized light is changed, a phase difference plate or the like is used. In particular, as a phase difference plate that converts linearly polarized light into circularly polarized light or circularly polarized light into linearly polarized light, a so-called quarter-wave plate (also referred to as λ/4 plate) is used. A 1/2 wave plate (also known as a λ/2 plate) is commonly used to change the direction of polarization of linearly polarized light.
橢圓偏光板可有效地用於補償(防止)超扭曲向列(STN,Super Twisted Nematic)型液晶顯示裝置因液晶層之雙折射而產生之著色(藍或黃),從而進行無上述著色之黑白顯示之情形等。進而,三維折射率得到控制之橢圓偏光板亦可補償(防止)自斜方向上觀看液晶顯示裝置之畫面時所產生的著色,故而較好。圓偏光板可有效地用於例如對圖像為彩色顯示之反射型液晶顯示裝置的圖像色調進行調整的情形等,而且亦具有抗反射之功能。The elliptically polarizing plate can be effectively used to compensate (prevent) the coloring (blue or yellow) of the super-twisted nematic (STN) type liquid crystal display device due to the birefringence of the liquid crystal layer, thereby performing black and white without the above coloring. The situation shown, etc. Further, the elliptically polarizing plate whose three-dimensional refractive index is controlled can also compensate (prevent) the coloring which occurs when the screen of the liquid crystal display device is viewed from the oblique direction, which is preferable. The circularly polarizing plate can be effectively used, for example, in the case of adjusting the color tone of an image of a reflective liquid crystal display device in which an image is displayed in color, and also has an anti-reflection function.
又,上述橢圓偏光板或反射型橢圓偏光板係將偏光板或反射型偏光板與相位差板以適宜之組合積層而成者。該橢圓偏光板等亦可藉由以形成(反射型)偏光板與相位差板之組合之方式,於液晶顯示裝置之製造過程中將該等依序分別積層而形成,但是如上所述,預先形成橢圓偏光板等光學膜時,具有品質穩定性或積層作業性等優異且可提昇液晶顯示裝置等之製造效率的優點。Further, the elliptically polarizing plate or the reflective elliptically polarizing plate is obtained by laminating a polarizing plate, a reflective polarizing plate, and a phase difference plate in an appropriate combination. The elliptically polarizing plate or the like may be formed by sequentially laminating the liquid crystal display devices in a manufacturing process of a liquid crystal display device by forming a combination of a (reflective) polarizing plate and a phase difference plate, but as described above, When an optical film such as an elliptically polarizing plate is formed, it is excellent in quality stability, laminating workability, and the like, and the manufacturing efficiency of a liquid crystal display device or the like can be improved.
視覺補償膜係用以擴大視角之膜,以使得即便自並非與液晶顯示裝置之畫面垂直而稍微傾斜之方向上觀看畫面時,圖像看上去亦比較清晰。此種視覺補償相位差板例如包括相位差板、液晶聚合物等之配向膜、或者將液晶聚合物等之配向層支持於透明基材上所成者等。普通之相位差板係使用於面方向上進行單軸延伸所得之具有雙折射的聚合物膜,與此相對,用作視覺補償膜之相位差板係使用:於面方向上進行雙軸延伸所得之具有雙折射的聚合物膜;或者於面方向上進行單軸延伸,且亦於厚度方向上進行延伸所得的厚度方向上之折射率得到控制的具有雙折射之聚合物或傾斜配向膜等雙向延伸膜等。作為傾斜配向膜,例如可列舉:於聚合物膜上接著熱收縮膜,於藉由加熱而產生之收縮力之作用下對聚合物膜進行延伸處理或/及收縮處理而形成者,或者將液晶聚合物傾斜配向所形成者等。相位差板之素材原料聚合物係使用與上文之相位差板中所說明之聚合物相同者,可使用以防止由基於液晶單元之相位差的視認角變化所引起之著色等、或擴大視認性良好之視角等為目的之適宜者。The visual compensation film is used to enlarge the film of the viewing angle so that the image looks clear even when the picture is viewed from a direction that is not slightly inclined perpendicular to the screen of the liquid crystal display device. Such a visual compensation retardation plate includes, for example, an alignment film such as a retardation film or a liquid crystal polymer, or an alignment layer in which a liquid crystal polymer or the like is supported on a transparent substrate. A common phase difference plate is a polymer film having birefringence obtained by uniaxially extending in the plane direction, and a phase difference plate used as a visual compensation film is used for biaxial stretching in the plane direction. a polymer film having birefringence; or a biaxially polarized polymer or a tilted alignment film, which is uniaxially stretched in the plane direction and also has a refractive index in the thickness direction which is extended in the thickness direction. Stretch film and the like. Examples of the oblique alignment film include a method in which a polymer film is followed by a heat shrink film, and a polymer film is stretched or/or shrunk by a contraction force generated by heating, or a liquid crystal is formed. The formation of the polymer oblique alignment, and the like. The material raw material polymer of the phase difference plate is the same as the polymer described in the above retardation plate, and can be used to prevent coloring or the like caused by a change in the viewing angle based on the phase difference of the liquid crystal cell, or to enlarge the visual recognition. A good perspective, etc., is suitable for the purpose.
又,就達成視認性良好之廣視角等觀點而言,可較好地使用以三乙酸纖維素膜來支持包含液晶聚合物之配向層,尤其是圓盤型液晶聚合物之傾斜配向層之光學異向性層的光學補償相位差板。Further, from the viewpoint of achieving a wide viewing angle of good visibility, it is possible to preferably use an optical alignment film comprising a liquid crystal polymer, particularly an optical fiber of a tilted alignment layer of a disc-type liquid crystal polymer. An optically compensated phase difference plate of the anisotropic layer.
將偏光板與增亮膜貼合而成之偏光板通常設置於液晶單元之背面側而使用。增亮膜係表現出如下特性者,即若液晶顯示裝置等之背光射入時、或者自然光藉由自背面側反射等而射入時,增亮膜使特定偏光軸之直線偏光或特定方向之圓偏光反射,而使其他光透過;將增亮膜與偏光板積層所形成之偏光板使來自背光等光源之光射入而獲得特定偏光狀態之透過光,並且使上述特定偏光狀態以外之光反射而不透過。於該增亮膜面上反射之光,進一步經由設置於其後側之反射層等而反轉後再次射入至增亮膜中,該增亮膜使該射入之光之一部分或全部形成為特定偏光狀態而透過,從而使透過增亮膜之光量增加,並且係供給難以被偏光片吸收之偏光,從而使液晶顯示圖像顯示等可利用之光量增加,藉此可提昇亮度。即,於不使用增亮膜之情況下,使用背光等自液晶單元之背面側通過偏光片而射入光之情形時,偏光方向與偏光片之偏光軸不一致之光大部分被偏光片吸收,而不能透過偏光片。即,雖然根據所使用之偏光片之特性之不同亦有所不同,但通常約50%之光被偏光片吸收,液晶圖像顯示等可利用之光量相應地減少,導致圖像變暗。增亮膜使具有會被偏光片吸收之偏光方向之光不射入至偏光片中,而使其於增亮膜上反射一次,進而經由設置於該增亮膜之後側之反射層等而使該光反轉後再次射入至增亮膜中,增亮膜反覆進行上述動作,從而僅使於上述兩者間反射、反轉之光中的偏光方向變成能夠通過偏光片之偏光方向的偏光透過增亮膜並供給至偏光片,因此可高效率地將背光等之光用於液晶顯示裝置之圖像顯示中,從而可使畫面變得明亮。A polarizing plate in which a polarizing plate and a brightness enhancing film are bonded together is usually used on the back side of the liquid crystal cell. The brightness enhancement film exhibits characteristics such as that when a backlight of a liquid crystal display device or the like is incident, or when natural light is incident from the back side, the brightness enhancement film polarizes a specific polarization axis or a specific direction. Circular light is reflected to transmit other light; a polarizing plate formed by laminating a brightness enhancement film and a polarizing plate emits light from a light source such as a backlight to obtain transmitted light of a specific polarization state, and causes light other than the specific polarization state Reflect without passing through. The light reflected on the brightness enhancement film surface is further inverted by a reflection layer or the like provided on the rear side thereof, and then incident into the brightness enhancement film again, and the brightness enhancement film forms part or all of the incident light. By transmitting in a specific polarization state, the amount of light transmitted through the brightness enhancement film is increased, and the polarization which is hard to be absorbed by the polarizer is supplied, so that the amount of light available for liquid crystal display image display or the like is increased, whereby the brightness can be improved. In other words, when a brightness enhancement film is not used, when light is incident from the back side of the liquid crystal cell through the polarizer, the light whose polarization direction does not coincide with the polarization axis of the polarizer is mostly absorbed by the polarizer. Cannot pass the polarizer. That is, although the characteristics of the polarizer used differ depending on the characteristics of the polarizer used, generally about 50% of the light is absorbed by the polarizer, and the amount of light available for liquid crystal image display or the like is correspondingly reduced, resulting in darkening of the image. The brightness enhancement film allows light having a polarization direction that is absorbed by the polarizer to be incident on the polarizer, and is reflected once on the brightness enhancement film, and further through a reflective layer or the like provided on the rear side of the brightness enhancement film. After the light is inverted, the light is incident on the brightness enhancement film again, and the brightness enhancement film repeats the above operation, so that only the polarization direction of the light reflected and inverted between the two becomes a polarization that can pass through the polarization direction of the polarizer. Since the brightness enhancement film is supplied to the polarizer, the light such as a backlight can be efficiently used for image display of the liquid crystal display device, and the screen can be made bright.
亦可於增亮膜與上述反射層等之間設置擴散板。由增亮膜反射之偏光狀態之光朝向上述反射層等前進,所設置之擴散板使所通過之光均一地擴散,同時消除其偏光狀態而變成非偏光狀態。即,反覆進行下述動作:自然光狀態之光朝向反射層等前進,經由反射層等反射,再次通過擴散板而再次射入至增亮膜中。如此,藉由於增亮膜與上述反射層等之間,設置使偏光恢復至原先之自然光的擴散板,可維持顯示畫面之亮度,同時可減少顯示畫面之亮度不均,從而提供均一且明亮之畫面。一般認為藉由設置該擴散板,初次之入射光之反射的反覆次數適度增加,並與擴散板之擴散功能互相結合,從而可提供均一且明亮之顯示畫面。A diffusion plate may be provided between the brightness enhancement film and the reflective layer or the like. The light in a polarized state reflected by the brightness enhancement film advances toward the reflection layer or the like, and the diffusing plate is provided to uniformly diffuse the passed light while eliminating the polarization state thereof to become a non-polarized state. In other words, the operation is performed in such a manner that the light in the natural light state advances toward the reflective layer or the like, is reflected by the reflective layer or the like, and is again incident on the brightness enhancement film through the diffusion plate. In this manner, by providing a diffusing plate that restores the polarized light to the original natural light between the brightness enhancing film and the reflective layer, the brightness of the display screen can be maintained, and the brightness unevenness of the display screen can be reduced, thereby providing uniformity and brightness. Picture. It is considered that by providing the diffusing plate, the number of times of reflection of the initial incident light is moderately increased, and the diffusing function of the diffusing plate is combined with each other, thereby providing a uniform and bright display screen.
作為上述增亮膜,例如可使用如下等適宜者:如介電體之多層薄膜或折射率異向性不同之薄膜的多層積層體般,表現出使特定偏光軸之直線偏光透過而使其他光反射之特性者;以及如膽固醇型液晶聚合物之配向膜或將其配向液晶層支持於膜基材上所成者般,表現出使左旋或右旋中之任一種圓偏光反射而使其他光透過之特性者。As the brightness enhancement film, for example, a multilayer film of a dielectric or a multilayer laminate of a film having a different refractive index anisotropy may be used, and a linear polarized light of a specific polarization axis may be transmitted to allow other light to be transmitted. a characteristic of reflection; and an alignment film such as a cholesteric liquid crystal polymer or a aligning liquid crystal layer supported on the film substrate, exhibiting polarization reflection of any of left-handed or right-handed rotation to make other light Through the characteristics of the person.
因此,上述使特定偏光軸之直線偏光透過之類型的增亮膜,可使該透過光與偏光板之偏光軸一致地直接射入至偏光板中,藉此可抑制偏光板所引起之吸收損失,使該透過光高效率地透過。另一方面,如膽固醇型液晶層般使圓偏光透過之類型之增亮膜亦可使圓偏光直接射入至偏光片中,但就抑制吸收損失之觀點而言,較好的是經由相位差板將該圓偏光轉換成直線偏光後再射入至偏光板中。再者,藉由使用1/4波片作為該相位差板,可將圓偏光轉換成直線偏光。Therefore, the brightness enhancement film of the type that transmits the linearly polarized light of the specific polarization axis can directly inject the transmitted light into the polarizing plate in accordance with the polarization axis of the polarizing plate, thereby suppressing the absorption loss caused by the polarizing plate. The transmitted light is transmitted efficiently. On the other hand, a brightness enhancement film of a type that transmits circularly polarized light like a cholesteric liquid crystal layer can also directly emit circularly polarized light into the polarizer, but from the viewpoint of suppressing absorption loss, it is preferable to pass the phase difference. The plate converts the circularly polarized light into a linearly polarized light and then injects it into the polarizing plate. Further, by using a quarter-wave plate as the phase difference plate, circularly polarized light can be converted into linearly polarized light.
於可見光區域等廣波長區域中作為1/4波片而發揮功能之相位差板例如可藉由如下方式獲得:將對波長為550nm之淡色光發揮1/4波片之功能的相位差板與表現出其他相位差特性之相位差層,例如發揮1/2波片之功能之相位差層重疊等。因此,配置於偏光板與增亮膜之間之相位差板亦可為包含一層或兩層以上之相位差層者。A phase difference plate that functions as a quarter-wave plate in a wide-wavelength region such as a visible light region can be obtained, for example, by a phase difference plate that functions as a quarter-wave plate for light-colored light having a wavelength of 550 nm. A phase difference layer exhibiting other phase difference characteristics, for example, a phase difference layer overlapping function which functions as a 1/2 wave plate. Therefore, the phase difference plate disposed between the polarizing plate and the brightness enhancement film may also be a phase difference layer including one or two or more layers.
再者,對於膽固醇型液晶層,藉由組合反射波長不同者而形成重疊兩層或三層以上之配置結構,可獲得於可見光區域等廣波長範圍內反射圓偏光者,且基於此可獲得廣波長範圍之透過圓偏光。Further, in the cholesteric liquid crystal layer, by combining the reflection wavelengths to form an arrangement structure in which two or more layers are overlapped, it is possible to obtain a circularly polarized light in a wide wavelength range such as a visible light region, and it is possible to obtain a wide range based on this. The wavelength range is transmitted through circular polarization.
又,偏光板亦可如上述偏光分離型偏光板般,由將偏光板與兩層或三層以上之光學層積層者所構成。因此,亦可為將上述反射型偏光板或半透過型偏光板與相位差板組合而形成之反射型橢圓偏光板或半透過型橢圓偏光板等。Further, the polarizing plate may be formed by laminating a polarizing plate and two or more optical layers as in the above-described polarization separating type polarizing plate. Therefore, a reflective elliptically polarizing plate or a semi-transmissive elliptically polarizing plate formed by combining the above-described reflective polarizing plate or semi-transmissive polarizing plate and a retardation plate may be used.
於偏光板上積層上述光學層而形成之光學膜亦可藉由於液晶顯示裝置等之製造過程中依序分別積層該等之方式而形成,但當預先積層而形成光學膜時,具有品質穩定性或組裝作業性等優異,可改善液晶顯示裝置等之製造步驟之優點。積層時可使用黏著層等適宜之接著機構。當將上述偏光板與其他光學層接著時,可根據目標之相位差特性等而使其等之光學軸形成適宜之配置角度。The optical film formed by laminating the optical layer on the polarizing plate may be formed by sequentially laminating these layers in a manufacturing process of a liquid crystal display device or the like, but having quality stability when an optical film is formed by laminating in advance. It is excellent in assembly workability and the like, and can improve the manufacturing steps of a liquid crystal display device or the like. A suitable attachment mechanism such as an adhesive layer can be used for lamination. When the polarizing plate is connected to another optical layer, an optical axis such as a target can be formed into an appropriate arrangement angle according to the phase difference characteristic of the target.
本發明之附有光學膜之玻璃基板係於玻璃基板(液晶單元)上貼附有黏著型光學膜者。黏著型光學膜之黏著劑層係由含有乳化劑之水分散型黏著劑所形成,當貼合於玻璃基板上時,黏貼後立刻發揮出高接著性,並且即便於高溫高濕環境下亦發揮出優異之耐久性。The optical film-attached glass substrate of the present invention is attached to a glass substrate (liquid crystal cell) to which an adhesive optical film is attached. The adhesive layer of the adhesive optical film is formed of a water-dispersible adhesive containing an emulsifier, and when bonded to a glass substrate, it exhibits high adhesion immediately after adhesion, and is exhibited even in a high-temperature and high-humidity environment. Excellent durability.
本發明之黏著型光學膜之剝離方法之特徵在於:將上述附有光學膜之玻璃基板曝露於溫度為40℃以上且相對濕度為80%以上(條件1)、或者溫度為50℃以上且相對濕度為70%以上(條件2)之環境下後,自玻璃基板上剝離黏著型光學膜。The peeling method of the adhesive optical film of the present invention is characterized in that the glass substrate with the optical film is exposed to a temperature of 40 ° C or higher, a relative humidity of 80% or more (condition 1), or a temperature of 50 ° C or more and relative After the humidity is 70% or more (Condition 2), the adhesive optical film is peeled off from the glass substrate.
於將附有光學膜之玻璃基板曝露於條件1或條件2之環境下之情形時,黏著劑層與玻璃基板之界面上之接著力下降,從而可容易地剝離黏著型光學膜。又,即便由於黏著型光學膜於高溫環境下長時間貼合於玻璃基板上而使接著力達到20N/25mm寬以上時,藉由曝露於條件1或條件2之環境下,亦可使接著力下降至10N/25mm寬以下。因此,對於大型尺寸之玻璃基板亦可重工性良好且容易地剝離。曝露處理之較佳條件為,溫度為80℃以上且相對濕度為80%以上。又,曝露處理之溫度較好的是100℃以下。若曝露處理之溫度超過100℃,則作為被黏附體之液晶顯示器等有可能損壞。When the glass substrate with the optical film is exposed to the environment of Condition 1 or Condition 2, the adhesion at the interface between the adhesive layer and the glass substrate is lowered, so that the adhesive optical film can be easily peeled off. Further, even when the adhesive optical film is bonded to the glass substrate for a long time in a high-temperature environment and the adhesion force is 20 N/25 mm or more, the adhesion can be made by exposure to the conditions of Condition 1 or Condition 2. Drop to below 10N/25mm width. Therefore, the glass substrate of a large size can also be excellent in workability and peeling easily. The preferred conditions for the exposure treatment are a temperature of 80 ° C or higher and a relative humidity of 80% or more. Further, the temperature of the exposure treatment is preferably 100 ° C or lower. If the temperature of the exposure treatment exceeds 100 ° C, the liquid crystal display or the like as the adherend may be damaged.
曝露處理之時間較好的是1小時以上,更好的是2小時以上。於未滿1小時之情形時,黏著劑層不能充分地吸水,黏著劑層與玻璃基板之界面上之接著力不能充分地降低,因此剝離時會使玻璃基板受損或產生較多之糨糊殘餘,導致重工性下降。另一方面,曝露處理之時間通常為48小時以下。由於即便超過48小時效果亦幾乎無變化,因此就製造效率之觀點而言並不佳。The exposure treatment time is preferably 1 hour or more, more preferably 2 hours or more. When the temperature is less than one hour, the adhesive layer does not sufficiently absorb water, and the adhesion at the interface between the adhesive layer and the glass substrate cannot be sufficiently lowered, so that the glass substrate is damaged or more residual residue is generated during peeling. , resulting in a decline in heavy work. On the other hand, the exposure treatment time is usually 48 hours or less. Since the effect is hardly changed even if it exceeds 48 hours, it is not preferable from the viewpoint of manufacturing efficiency.
以下,藉由實施例對本發明加以具體說明,但本發明並不限定於該等實施例。再者,各例中之份及%均為重量基準。Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited to the examples. Furthermore, the parts and % in each case are based on weight.
製造例1Manufacturing example 1
(單體預製乳液之製備)(Preparation of monomer pre-emulsion)
於容器中加入丙烯酸丁酯88份、甲基丙烯酸N-環己酯5份、丙烯酸5份、單[聚(氧化丙烯)甲基丙烯酸酯]磷酸酯(氧化丙烯之平均聚合度約為5.0)2份及3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學(股),KBM-503)0.03份並混合,製備單體混合物。然後,於單體混合物500g中加入反應性乳化劑(第一工業製藥(股),AQUALON HS-1025)20g及離子交換水446g,使用均質機(特殊機化(股)),以5000(rpm)之轉速攪拌5分鐘而進行乳化,藉此製備單體預製乳液。88 parts of butyl acrylate, 5 parts of N-cyclohexyl methacrylate, 5 parts of acrylic acid, and mono [poly(oxypropylene) methacrylate] phosphate (the average degree of polymerization of propylene oxide is about 5.0) is added to the vessel. Two parts and 0.03 parts of 3-methacryloxypropyltrimethoxydecane (Shin-Etsu Chemical Co., KBM-503) were mixed and mixed to prepare a monomer mixture. Then, 20 g of a reactive emulsifier (First Industrial Pharmaceutical Co., Ltd., AQUALON HS-1025) and 446 g of ion-exchanged water were added to 500 g of the monomer mixture, and a homogenizer (specialized machine) was used at 5000 (rpm). The temperature was stirred for 5 minutes to carry out emulsification, thereby preparing a monomer pre-emulsion.
(水分散型丙烯酸系黏著劑之製備)(Preparation of water-dispersed acrylic adhesive)
於具備攪拌翼、溫度計、氮氣導入管、冷凝器之反應容器中,加入單體預製乳液96g、離子交換水275g及反應性乳化劑AQUALON HS-1025(40g),並對反應容器進行氮氣置換。其後,添加過硫酸銨0.05g並於65℃下進行1小時聚合反應。繼而,將反應容器內之溫度升溫至75℃,添加過硫酸銨0.35g。其後,歷時3小時將單體預製乳液869g滴加於反應容器內,滴加後進行3小時聚合反應。其後,一面進行氮氣置換一面於75℃下進行3小時聚合反應,製成固形物為40%之乳液。然後,將所獲得之乳液冷卻至室溫,添加10%之氨水將pH值調整為8,藉此製備水分散型丙烯酸系黏著劑。Into a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser, 96 g of a monomer pre-emulsion, 275 g of ion-exchanged water, and a reactive emulsifier AQUALON HS-1025 (40 g) were placed, and the reaction vessel was purged with nitrogen. Thereafter, 0.05 g of ammonium persulfate was added and polymerization was carried out at 65 ° C for 1 hour. Then, the temperature in the reaction vessel was raised to 75 ° C, and 0.35 g of ammonium persulfate was added. Thereafter, 869 g of the monomer pre-emulsion was dropwise added to the reaction vessel over 3 hours, and the polymerization was carried out for 3 hours after the dropwise addition. Thereafter, the mixture was subjected to a polymerization reaction at 75 ° C for 3 hours while performing nitrogen substitution to obtain an emulsion having a solid content of 40%. Then, the obtained emulsion was cooled to room temperature, and the pH was adjusted to 8 by adding 10% aqueous ammonia, thereby preparing a water-dispersed acrylic adhesive.
(黏著劑層之形成)(formation of adhesive layer)
將上述水分散型丙烯酸系黏著劑,以使乾燥後之黏著劑層之厚度達到23μm之方式塗佈於脫模膜(三菱化學聚酯(Mitsubishi Chemical Polyester Film)(股),DIAFOIL MRF38,PET膜)之單面上,並於120℃下乾燥2分鐘,形成黏著劑層。The water-dispersible acrylic pressure-sensitive adhesive was applied to a release film (Mitsubishi Chemical Polyester Film), DIAFOIL MRF38, PET film so that the thickness of the adhesive layer after drying became 23 μm. On one side, and dried at 120 ° C for 2 minutes to form an adhesive layer.
(偏光板之製作)(production of polarizing plate)
將厚度為80μm之聚乙烯醇膜,於40℃之碘溶液中延伸至5倍。其後,將聚乙烯醇膜自碘溶液中撈起,於50℃下乾燥4分鐘而獲得偏光片。使用聚乙烯醇系接著劑於該偏光片之兩面上貼合三乙酸纖維素膜,藉此製作偏光板。A polyvinyl alcohol film having a thickness of 80 μm was stretched to 5 times in an iodine solution at 40 °C. Thereafter, the polyvinyl alcohol film was picked up from the iodine solution, and dried at 50 ° C for 4 minutes to obtain a polarizer. A polarizing plate was produced by laminating a cellulose triacetate film on both surfaces of the polarizer using a polyvinyl alcohol-based adhesive.
(黏著型偏光板A之製作)(Production of Adhesive Polarizing Plate A)
以水/異丙醇(重量比為1/1)混合溶液將含有唑啉基之丙烯酸系聚合物(日本觸媒(股),EPOCROS WS-700)稀釋至固形物為0.25%來製備增黏塗層劑。使用Meyer bar #5將增黏塗層劑塗佈於上述偏光板之單面上,並於40℃下乾燥2分鐘而形成增黏層。然後,將上述黏著劑層轉印至增黏層上而製作黏著型偏光板A。The water/isopropyl alcohol (1/1 by weight) mixed solution will contain The oxazolyl-based acrylic polymer (Nippon Catalyst (EP), EPOCROS WS-700) was diluted to a solid content of 0.25% to prepare a tackifying coating agent. The adhesion-promoting coating agent was applied to one surface of the above polarizing plate using Meyer bar #5, and dried at 40 ° C for 2 minutes to form a tackified layer. Then, the above adhesive layer was transferred onto the adhesion-promoting layer to form an adhesive polarizing plate A.
(接著力之測定)(Continues the measurement of force)
以下述方法來測定黏著型偏光板A之初始接著力、及60℃/100小時後之接著力。其結果,初始接著力為7.8(N/25mm),60℃/100小時後之接著力為36.0(N/25mm)。The initial adhesion force of the pressure-sensitive polarizing plate A and the adhesion force after 60 ° C / 100 hours were measured by the following methods. As a result, the initial adhesion force was 7.8 (N/25 mm), and the adhesion force after 60 ° C / 100 hours was 36.0 (N / 25 mm).
<初始接著力><initial adhesion>
將黏著型偏光板A裁剪成25mm寬獲得樣品,利用2kg之輥,於玻璃基板(Corning(股),Corning #1737)上對該樣品往返壓接一次而使其貼附於玻璃基板上,然後於50℃、5個大氣壓之高壓釜中放置15分鐘,其後冷卻至25℃。然後,使用拉伸試驗機,以剝離角度為180°、剝離速度為300mm/min之條件自玻璃基板上剝離樣品,測定此時之接著力(N/25mm)。The adhesive polarizing plate A was cut into a width of 25 mm to obtain a sample, and the sample was crimped to the glass substrate once on the glass substrate (Corning (Corning #1737) by a 2 kg roller, and then attached to the glass substrate, and then It was placed in an autoclave at 50 ° C and 5 atm for 15 minutes, and then cooled to 25 ° C. Then, the sample was peeled from the glass substrate under the conditions of a peeling angle of 180° and a peeling speed of 300 mm/min using a tensile tester, and the adhesion (N/25 mm) at this time was measured.
<60℃/100小時後之接著力><60 ° C / adhesion after 100 hours >
將黏著型偏光板A裁剪成25mm寬獲得樣品,利用2kg之輥,於玻璃基板(Corning(股),Corning #1737)上對該樣品往返壓接一次而使其貼附於玻璃基板上,然後於50℃、5個大氣壓之高壓釜中放置15分鐘,其後於60℃、相對濕度為30%之環境下放置100小時,之後冷卻至25℃。然後,使用拉伸試驗機,以剝離角度為180°、剝離速度為300mm/min之條件自玻璃基板上剝離樣品,測定此時之接著力(N/25mm)。The adhesive polarizing plate A was cut into a width of 25 mm to obtain a sample, and the sample was crimped to the glass substrate once on the glass substrate (Corning (Corning #1737) by a 2 kg roller, and then attached to the glass substrate, and then The mixture was placed in an autoclave of 5 atm at 50 ° C for 15 minutes, and then allowed to stand at 60 ° C and a relative humidity of 30% for 100 hours, and then cooled to 25 ° C. Then, the sample was peeled from the glass substrate under the conditions of a peeling angle of 180° and a peeling speed of 300 mm/min using a tensile tester, and the adhesion (N/25 mm) at this time was measured.
製造例2Manufacturing Example 2
(丙烯酸系聚合物溶液之製備)(Preparation of acrylic polymer solution)
於具備攪拌翼、溫度計、氮氣導入管、冷凝器之反應容器中,加入丙烯酸丁酯100份、丙烯酸5份、過氧化苯甲醯0.1份及乙酸乙酯,製備單體濃度為80%之單體溶液。一面攪拌該單體溶液一面導入氮氣1小時進行氮氣置換後,將反應容器內之液溫保持於60℃附近並進行6小時聚合反應,藉此製備丙烯酸系聚合物溶液。丙烯酸系聚合物之重量平均分子量為160萬。In a reaction vessel equipped with a stirring blade, a thermometer, a nitrogen introduction tube, and a condenser, 100 parts of butyl acrylate, 5 parts of acrylic acid, 0.1 part of benzoyl peroxide and ethyl acetate were added to prepare a monomer concentration of 80%. Body solution. While stirring the monomer solution, nitrogen gas was introduced for 1 hour to carry out nitrogen substitution, and then the liquid temperature in the reaction vessel was maintained at around 60 ° C and polymerization reaction was carried out for 6 hours to prepare an acrylic polymer solution. The weight average molecular weight of the acrylic polymer was 1.6 million.
(丙烯酸系黏著劑之製備)(Preparation of acrylic adhesive)
於上述丙烯酸系聚合物溶液100份(固形物)中,加入多官能異氰酸酯化合物(日本聚胺酯(Nippon Polyurethane),CORONET L)0.8份來製備丙烯酸系黏著劑。An acrylic pressure-sensitive adhesive was prepared by adding 0.8 parts of a polyfunctional isocyanate compound (Nippon Polyurethane, CORONET L) to 100 parts (solid content) of the above acrylic polymer solution.
(黏著劑層之形成)(formation of adhesive layer)
將上述丙烯酸系黏著劑,以使乾燥後之黏著劑層之厚度達到21μm之方式塗佈於脫模膜(三菱化學聚酯(股),DIAFOIL MRF38,PET膜)之單面上,於150℃下乾燥3分鐘形成黏著劑層。The acrylic adhesive was applied to one side of a release film (Mitsubishi Chemical Polyester, DIAFOIL MRF38, PET film) at a temperature of 150 ° C so that the thickness of the adhesive layer after drying became 21 μm. Dry for 3 minutes to form an adhesive layer.
(黏著型偏光板B之製作)(Production of Adhesive Polarizing Plate B)
將上述黏著劑層轉印於偏光板上,製作黏著型偏光板B。The adhesive layer was transferred onto a polarizing plate to form an adhesive polarizing plate B.
(接著力之測定)(Continues the measurement of force)
以與上述相同之方法測定黏著型偏光板B之初始接著力、及60℃/100小時後之接著力。具結果,初始接著力為14,8(N/25mm),60℃/100小時後之接著力為31.0(N/25mm)。The initial adhesion force of the adhesive polarizing plate B and the adhesion force after 60 ° C / 100 hours were measured in the same manner as above. As a result, the initial adhesion force was 14,8 (N/25 mm), and the adhesion after 60 ° C / 100 hours was 31.0 (N / 25 mm).
製造例3Manufacturing Example 3
(黏著劑層之形成)(formation of adhesive layer)
於製造例1之水分散型丙烯酸系黏著劑中,加入作為交聯劑之碳二醯亞胺化合物(日清紡織(股),CARBODILITE E-04),獲得黏著劑組合物。再者,交聯劑之添加量於水分散型丙烯酸系黏著劑之固形物中占0.4重量%。然後,將該黏著劑組合物,以使乾燥後之黏著劑層之厚度達到23μm之方式塗佈於脫模膜(三菱化學聚酯(股),DIAFOIL MRF38,PET膜)之單面上,於120℃下乾燥2分鐘,形成黏著劑層。In the water-dispersible acrylic pressure-sensitive adhesive of Production Example 1, a carbodiimide compound (Nippon Textile Co., Ltd., CARBODILITE E-04) as a crosslinking agent was added to obtain an adhesive composition. Further, the amount of the crosslinking agent added was 0.4% by weight based on the solid content of the water-dispersible acrylic pressure-sensitive adhesive. Then, the adhesive composition was applied to one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., DIAFOIL MRF38, PET film) so that the thickness of the adhesive layer after drying became 23 μm. Dry at 120 ° C for 2 minutes to form an adhesive layer.
(黏著型偏光板C之製作)(Production of Adhesive Polarizing Plate C)
除使用上述黏著劑層以外,以與製造例1相同之方法製作黏著型偏光板C。An adhesive polarizing plate C was produced in the same manner as in Production Example 1 except that the above adhesive layer was used.
(接著力之測定)(Continues the measurement of force)
以與上述相同之方法測定黏著型偏光板C之初始接著力、及60℃/100小時後之接著力。具結果,初始接著力為2.3(N/25mm),60℃/100小時後之接著力為30(N/25mm)以上。The initial adhesion force of the adhesive polarizing plate C and the adhesion force after 60 ° C / 100 hours were measured in the same manner as above. As a result, the initial adhesion force was 2.3 (N/25 mm), and the adhesion after 60 ° C / 100 hours was 30 (N / 25 mm) or more.
製造例4Manufacturing Example 4
(黏著劑層之形成)(formation of adhesive layer)
於製造例1之水分散型丙烯酸系黏著劑中,加入作為交聯劑之碳二醯亞胺化合物(日清紡織(股),CARBODILITE E-04)而獲得黏著劑組合物。再者,交聯劑之添加量於水分散型丙烯酸系黏著劑之固形物中占1.0重量%。然後,將該黏著劑組合物,以使乾燥後之黏著劑層之厚度達到23μm之方式塗佈於脫模膜(三菱化學聚酯(股),DIAFOIL MRF38,PET膜)之單面上,於120℃下乾燥2分鐘,形成黏著劑層。In the water-dispersible acrylic pressure-sensitive adhesive of Production Example 1, a carbodiimide compound (Nissin Textile Co., Ltd., CARBODILITE E-04) as a crosslinking agent was added to obtain an adhesive composition. Further, the amount of the crosslinking agent added was 1.0% by weight based on the solid content of the water-dispersible acrylic pressure-sensitive adhesive. Then, the adhesive composition was applied to one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., DIAFOIL MRF38, PET film) so that the thickness of the adhesive layer after drying became 23 μm. Dry at 120 ° C for 2 minutes to form an adhesive layer.
(黏著型偏光板D之製作)(Production of Adhesive Polarizing Plate D)
除使用上述黏著劑層以外,以與製造例1相同之方法製作黏著型偏光板D。An adhesive polarizing plate D was produced in the same manner as in Production Example 1 except that the above adhesive layer was used.
(接著力之測定)(Continues the measurement of force)
以與上述相同之方法測定黏著型偏光板D之初始接著力、及60℃/100小時後之接著力。其結果,初始接著力為2.1(N/25mm),60℃/100小時後之接著力為30(N/25mm)以上。The initial adhesion force of the pressure-sensitive polarizing plate D and the adhesion force after 60 ° C / 100 hours were measured in the same manner as above. As a result, the initial adhesion force was 2.1 (N/25 mm), and the adhesion force after 60 ° C / 100 hours was 30 (N/25 mm) or more.
製造例5Manufacturing Example 5
(黏著劑層之形成)(formation of adhesive layer)
於製造例1之水分散型丙烯酸系黏著劑中,加入作為交聯劑之碳二醯亞胺化合物(日清紡織(股),CARBODILITE E-04)而獲得黏著劑組合物。再者,交聯劑之添加量於水分散型丙烯酸系黏著劑之固形物中占1.0重量%。然後,將該黏著劑組合物,以使乾燥後之黏著劑層之厚度達到30μm之方式塗佈於脫模膜(三菱化學聚酯(股),DIAFOIL MRF38,PET膜)之單面上,於120℃下乾燥2分鐘,形成黏著劑層。In the water-dispersible acrylic pressure-sensitive adhesive of Production Example 1, a carbodiimide compound (Nissin Textile Co., Ltd., CARBODILITE E-04) as a crosslinking agent was added to obtain an adhesive composition. Further, the amount of the crosslinking agent added was 1.0% by weight based on the solid content of the water-dispersible acrylic pressure-sensitive adhesive. Then, the adhesive composition was applied to one side of a release film (Mitsubishi Chemical Polyester Co., Ltd., DIAFOIL MRF38, PET film) so that the thickness of the adhesive layer after drying became 30 μm. Dry at 120 ° C for 2 minutes to form an adhesive layer.
(黏著型偏光板E之製作)(Production of Adhesive Polarizing Plate E)
除使用上述黏著劑層以外,以與製造例1相同之方法製作黏著型偏光板E。An adhesive polarizing plate E was produced in the same manner as in Production Example 1 except that the above adhesive layer was used.
(接著力之測定)(Continues the measurement of force)
以與上述相同之方法測定黏著型偏光板E之初始接著力、及60℃/100小時後之接著力。其結果,初始接著力為2,.6(N/25mm),60℃/100小時後之接著力為30(N/25mm)以上。The initial adhesion force of the pressure-sensitive polarizing plate E and the adhesion force after 60 ° C / 100 hours were measured in the same manner as above. As a result, the initial adhesion force was 2,6 (N/25 mm), and the adhesion force after 60 ° C / 100 hours was 30 (N/25 mm) or more.
實施例1~12、比較例1~3Examples 1 to 12 and Comparative Examples 1 to 3
將黏著型偏光板A裁剪成25mm寬獲得樣品,利用2kg之輥,於玻璃基板(Corning(股),Corning #1737)上對該樣品往返壓接一次使其貼附於玻璃基板上,然後於50℃、5個大氣壓之高壓釜中放置15分鐘,其後於60℃,相對濕度為30%之環境下放置100小時,之後冷卻至25℃。然後,以表1中所揭示之各條件進行曝露處理,冷卻至25℃。然後,使用拉伸試驗機,以剝離角度為180°、剝離速度為300mm/min之條件自玻璃基板上剝離樣品,分別測定剝離時之接著力(N/25mm)。The adhesive polarizing plate A was cut into a width of 25 mm to obtain a sample, and the sample was re-attached to the glass substrate on a glass substrate (Corning (Corning #1737) by a 2 kg roller, and then attached to the glass substrate, and then The autoclave was placed at 50 ° C for 5 minutes in an autoclave at 15 ° C for 15 minutes, and then left at 60 ° C for 30 hours in a relative humidity of 30%, and then cooled to 25 ° C. Then, the exposure treatment was carried out under the conditions disclosed in Table 1, and cooled to 25 °C. Then, the sample was peeled from the glass substrate under the conditions of a peeling angle of 180° and a peeling speed of 300 mm/min using a tensile tester, and the adhesion force (N/25 mm) at the time of peeling was measured.
比較例4及5Comparative Examples 4 and 5
除使用黏著型偏光板B以外,以與上述相同之方法分別測定接著力(N/25mm)。The adhesion force (N/25 mm) was measured in the same manner as above except that the adhesive polarizing plate B was used.
實施例13、14Example 13, 14
除使用黏著型偏光板C以外,以與上述相同之方法分別測定接著力(N/25mm)。The adhesion force (N/25 mm) was measured in the same manner as above except that the adhesive polarizing plate C was used.
實施例15、16Examples 15, 16
除使用黏著型偏光板D以外,以與上述相同之方法分別測定接著力(N/25mm)。The adhesion force (N/25 mm) was measured in the same manner as above except that the adhesive polarizing plate D was used.
實施例17、18Examples 17, 18
除使用黏著型偏光板E以外,以與上述相同之方法分別測定接著力(N/25mm)。The adhesion force (N/25 mm) was measured in the same manner as above except that the adhesive polarizing plate E was used.
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JP5336323B2 (en) * | 2009-10-23 | 2013-11-06 | 日東電工株式会社 | Adhesive layer for optical film, adhesive optical film, and image display device |
KR101771758B1 (en) * | 2009-12-09 | 2017-08-25 | 닛토덴코 가부시키가이샤 | Adhesive layer for optical film, adhesive optical film, process for production of the adhesive optical film, and image display device |
JP2012087290A (en) * | 2010-09-21 | 2012-05-10 | Nitto Denko Corp | Self-adhesive layer for optical film and method for producing the same, optical film with self-adhesive layer, and image display |
JP2015196313A (en) * | 2014-03-31 | 2015-11-09 | ソニー株式会社 | Protective film, laminate, display device, and film-attaching unit |
WO2018003838A1 (en) * | 2016-06-30 | 2018-01-04 | 日本化薬株式会社 | Highly durable polarizing plate, image display device using same, and method for producing polarizing plate |
KR20180129653A (en) * | 2017-05-25 | 2018-12-05 | 스미또모 가가꾸 가부시키가이샤 | Polarizing plate |
JP7190268B2 (en) | 2018-06-26 | 2022-12-15 | 日東電工株式会社 | Polarizing film with adhesive layer, method for peeling the same, and image display device |
JP7273472B2 (en) * | 2018-08-27 | 2023-05-15 | 日東電工株式会社 | laminate |
JP7388814B2 (en) * | 2018-10-29 | 2023-11-29 | リンテック株式会社 | Shatterproof adhesive sheet |
CN212460999U (en) | 2020-05-27 | 2021-02-02 | 合肥京东方显示技术有限公司 | Display module assembly and transparent display device |
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JP2006099018A (en) * | 2004-09-30 | 2006-04-13 | Kyokuhei Glass Kako Kk | Polarizing plate stripping system of liquid crystal display panel and recycling method of liquid crystal display panel |
JP2007070610A (en) * | 2005-08-08 | 2007-03-22 | Nitto Denko Corp | Aqueous dispersion type pressure-sensitive adhesive composition, pressure-sensitive adhesive optical film, and image display unit |
JP2007118486A (en) * | 2005-10-31 | 2007-05-17 | Toshiba Matsushita Display Technology Co Ltd | Optical film and display device provided with the same |
JP2007186661A (en) * | 2005-01-26 | 2007-07-26 | Nitto Denko Corp | Adhesive composition, adhesive type optical film and image display device |
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JP2006099018A (en) * | 2004-09-30 | 2006-04-13 | Kyokuhei Glass Kako Kk | Polarizing plate stripping system of liquid crystal display panel and recycling method of liquid crystal display panel |
JP2007186661A (en) * | 2005-01-26 | 2007-07-26 | Nitto Denko Corp | Adhesive composition, adhesive type optical film and image display device |
JP2007070610A (en) * | 2005-08-08 | 2007-03-22 | Nitto Denko Corp | Aqueous dispersion type pressure-sensitive adhesive composition, pressure-sensitive adhesive optical film, and image display unit |
JP2007118486A (en) * | 2005-10-31 | 2007-05-17 | Toshiba Matsushita Display Technology Co Ltd | Optical film and display device provided with the same |
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