TWI613084B - Method of manufacturing laminated film - Google Patents

Method of manufacturing laminated film Download PDF

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Publication number
TWI613084B
TWI613084B TW102121696A TW102121696A TWI613084B TW I613084 B TWI613084 B TW I613084B TW 102121696 A TW102121696 A TW 102121696A TW 102121696 A TW102121696 A TW 102121696A TW I613084 B TWI613084 B TW I613084B
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Taiwan
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film
adhesive
films
bonding
transparent
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TW102121696A
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Chinese (zh)
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TW201410473A (en
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古川淳
廣岩梓
竹內智康
久米悅夫
山根尙德
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住友化學股份有限公司
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    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements
    • G02B5/3025Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1207Heat-activated adhesive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1253Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives curable adhesive
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2309/00Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/08Dimensions, e.g. volume
    • B32B2309/10Dimensions, e.g. volume linear, e.g. length, distance, width
    • B32B2309/105Thickness
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00Treatment by energy or chemical effects
    • B32B2310/08Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00Treatment by energy or chemical effects
    • B32B2310/08Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203One or more of the layers being plastic
    • B32B37/206Laminating a continuous layer between two continuous plastic layers

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

一種方法,其係依照以下順序具備:接著劑塗布步驟,其係在複數片薄膜中之至少1片薄膜的一面或兩面,塗布活性能量線硬化型接著劑;貼合步驟,其係在前述接著劑介於相鄰薄膜之間的方式積層而成之狀態下,藉由在朝搬運方向旋轉的一對貼合輥之間將前述複數片薄膜夾住而予以互相貼合;以及活性能量線照射步驟,其係對互相貼合之前述複數片薄膜照射活性能量線,而使前述接著劑硬化;其中,在前述複數片薄膜中,在前述接著劑塗布步驟未塗布前述接著劑的面而在前述貼合步驟成為與前述接著劑相接的面之表面粗糙度為200nm以下。 A method comprising: an adhesive application step of applying an active energy ray-curable adhesive on one or both sides of at least one of a plurality of films; and a bonding step, which is followed by In a state in which the agent is interposed between adjacent films, the plurality of film rolls are sandwiched between a pair of bonding rolls that rotate in the conveying direction to adhere to each other; and active energy ray irradiation a step of curing the adhesive film by irradiating an active energy ray to the plurality of films bonded to each other; wherein, in the plurality of films, the surface of the adhesive is not applied in the adhesive coating step In the bonding step, the surface of the surface in contact with the above-mentioned adhesive has a surface roughness of 200 nm or less.

Description

積層膜的製造方法 Method for manufacturing laminated film

本發明係有關於一種使用在光學零件等的各種用途之積層膜的製造方法。 The present invention relates to a method for producing a laminated film which is used in various applications such as optical parts.

偏光薄膜係以使聚乙烯醇系樹脂薄膜吸附配向有二色性色素之方式而廣泛地被使用,已知將碘作為二色性色素之碘系偏光薄膜;以及將二色性直接染料作為二色性色素之染料系偏光薄膜等。該等偏光薄膜通常係在其一面或兩面透過接著劑而貼合三乙醯纖維素薄膜等的透明薄膜,而成為偏光板。 The polarizing film is widely used to adsorb and align a polyvinyl alcohol-based resin film with a dichroic dye. An iodine-based polarizing film containing iodine as a dichroic dye is known, and a dichroic direct dye is used as a second. The dye of a coloring pigment is a polarizing film or the like. These polarizing films are usually obtained by laminating a transparent film such as a triacetyl cellulose film through an adhesive on one or both sides thereof to form a polarizing plate.

作為在偏光薄膜的一面或兩面積層透明薄膜之方法,有預先在透明薄膜的表面塗布活性能量線硬化型樹脂之後,藉由使用一對貼合輥將偏光薄膜及透明薄膜夾住而貼合,其次,照射活性能量線而使其接著硬之方法(例如,參照日本特開2004-245925號公報(專利文獻1)、日本特開2009-134190號公報(專利文獻2)、日本特開2011-95560號公報(專利文獻3))。 As a method of forming a transparent film on one surface or two layers of a polarizing film, an active energy ray-curable resin is applied to the surface of the transparent film in advance, and then the polarizing film and the transparent film are sandwiched by a pair of bonding rolls to be bonded. Then, the method of irradiating the active energy ray to be hardened (for example, refer to Japanese Laid-Open Patent Publication No. 2004-245925 (Patent Document 1), JP-A-2009-134190 (Patent Document 2), and JP-A-2011- Japanese Patent Publication No. 95560 (Patent Document 3)).

如此,在複數片薄膜透過活性能量線硬化型接著劑互相貼合而成之積層膜的製造時,氣泡有混入薄 膜與薄膜之間之情形。這是使用以往的水系黏著劑等時不會產生的現象,咸認為這是由於使用活性能量線硬化型接著劑之特有的問題。近年來,積層膜係被要求進一步薄型化。因此,欲將活性能量線硬化型接著劑的厚度薄化時,特別容易存在有產生該氣泡混入之問題。 In this way, when a plurality of films are laminated with an active energy ray-curable adhesive, the bubbles are mixed. The situation between the film and the film. This is a phenomenon which does not occur when a conventional water-based adhesive or the like is used, and it is considered to be a peculiar problem of using an active energy ray-curable adhesive. In recent years, laminated film systems have been required to be further thinned. Therefore, when the thickness of the active energy ray-curable adhesive is to be thinned, there is a problem that the occurrence of the bubbles is particularly likely to occur.

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

[專利文獻1]日本特開2004-245925號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-245925

[專利文獻2]日本特開2009-134190號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-134190

[專利文獻3]日本特開2011-95560號公報 [Patent Document 3] Japanese Laid-Open Patent Publication No. 2011-95560

本發明之目的,係在複數片薄膜透過活性能量線硬化型接著劑互相貼合而成之積層膜的製造時,能夠抑制氣泡混入薄膜與薄膜之間。 In the production of a laminated film in which a plurality of sheets of film are bonded to each other by an active energy ray-curable adhesive, it is possible to suppress the incorporation of air bubbles between the film and the film.

本發明係提供一種方法,其係將複數片薄膜透過活性能量線硬化型接著劑互相貼合而成之積層膜的製造方法,其係依照下列順序具備:接著劑塗布步驟,其係在前述複數片薄膜中之至少1片薄膜的一面或兩面,塗布活性能量線硬化型接著劑;貼合步驟,其係在前述接著劑介於相鄰薄膜之間的方式積層而成之狀態下,藉由在朝搬運方向旋轉的一對貼合 輥之間將前述複數片薄膜夾住而予以互相貼合;以及活性能量線照射步驟,其係對互相貼合之前述複數片薄膜照射活性能量線,而使前述接著劑硬化;其中,在前述複數片薄膜中,在前述接著劑塗布步驟未塗布前述接著劑的面而在前述貼合步驟成為與前述接著劑相接的面之表面粗糙度為200nm以下。 The present invention provides a method for producing a laminated film obtained by laminating a plurality of sheets of a film through an active energy ray-curable adhesive, which is provided in the following order: an adhesive coating step, which is in the plural An active energy ray-curable adhesive is applied to one or both sides of at least one of the film films; and a bonding step is performed in a state in which the adhesive is laminated between adjacent films. a pair of fits that rotate in the carrying direction The plurality of sheets of film are sandwiched between the rolls to be bonded to each other; and the active energy ray irradiation step is performed by irradiating the plurality of sheets of the film to each other with an active energy ray to harden the adhesive; wherein, In the plurality of sheets, the surface of the adhesive is not applied to the surface of the adhesive in the adhesive application step, and the surface of the surface that is in contact with the adhesive in the bonding step has a surface roughness of 200 nm or less.

較佳是在前述接著劑塗布步驟,所塗布之前述接著劑的厚度為2μm以下。 Preferably, in the adhesive application step, the thickness of the adhesive to be applied is 2 μm or less.

較佳是前述複數片薄膜係含有光學薄膜及透明薄膜且前述積層膜係偏光板。 Preferably, the plurality of sheets of the film comprise an optical film and a transparent film, and the laminated film is a polarizing plate.

較佳是前述複數片薄膜係由1片光學薄膜及2片透明薄膜所構成,在前述接著劑塗布步驟中,在2片前述透明薄膜各自的一面塗布前述接著劑,在前述貼合步驟中,以2片前述透明薄膜的前述接著劑相接於前述光學薄膜的兩面的方式積層而成之狀態下,藉由在前述一對貼合輥之間將前述光學薄膜及前述透明薄膜夾住而予以互相貼合。 Preferably, the plurality of thin films are composed of one optical film and two transparent films, and in the adhesive application step, the adhesive is applied to one surface of each of the two transparent films, and in the bonding step, In a state in which the above-mentioned adhesives of the two transparent films are laminated on both surfaces of the optical film, the optical film and the transparent film are sandwiched between the pair of bonding rolls. Fit each other.

較佳是前述複數片薄膜係由1片光學薄膜及1片透明薄膜所構成,在前述接著劑塗布步驟中,在前述透明薄膜的一面塗布前述接著劑,在前述貼合步驟,以前述透明薄膜的前述接著劑相接於前述光學薄膜的一面的方式積層而成之狀態下,藉由在 前述一對貼合輥之間將前述光學薄膜及前述透明薄膜夾住而予以互相貼合。 Preferably, the plurality of sheets are composed of one optical film and one transparent film, and in the adhesive application step, the adhesive is applied to one surface of the transparent film, and the transparent film is applied to the bonding step. In a state in which the above-mentioned adhesive agent is laminated on one surface of the optical film, The optical film and the transparent film are sandwiched between the pair of bonding rolls and bonded to each other.

依照本發明,在複數片薄膜透過活性能量線硬化型接著劑互相貼合而成之積層膜的製造方法,能夠抑制氣泡混入薄膜與薄膜之間。 According to the present invention, in the method for producing a laminated film in which a plurality of sheets of film are bonded to each other by an active energy ray-curable adhesive, it is possible to suppress the incorporation of air bubbles between the film and the film.

1‧‧‧光學薄膜 1‧‧‧Optical film

2、3‧‧‧透明薄膜 2, 3‧‧‧ transparent film

4‧‧‧積層體 4‧‧‧Layered body

11、12‧‧‧接著劑塗布裝置 11, 12‧‧‧ adhesive coating device

13‧‧‧輥筒 13‧‧‧ Roller

14、15、16、17、18‧‧‧活性能量線照射裝置 14, 15, 16, 17, 18‧‧‧Active energy line irradiation device

19‧‧‧搬運用夾輥 19‧‧‧Carrying nip rollers

20‧‧‧捲起輥 20‧‧‧Rolling roll

51、52‧‧‧貼合輥 51, 52‧‧‧ affixing rolls

第1圖係顯示在實施形態1的製造方法所使用之裝置全體構成之示意圖。 Fig. 1 is a schematic view showing the overall configuration of a device used in the manufacturing method of the first embodiment.

第2圖係顯示在實施形態2的製造方法所使用之裝置全體構成之示意圖。 Fig. 2 is a schematic view showing the overall configuration of the apparatus used in the manufacturing method of the second embodiment.

第3圖係顯示在實施例2的製造方法所使用之裝置全體構成之示意圖。 Fig. 3 is a schematic view showing the overall configuration of the apparatus used in the manufacturing method of the second embodiment.

本發明係將複數片薄膜透過活性能量線硬化型接著劑互相貼合而成之積層膜的製造方法,其係依照下列順序具備:接著劑塗布步驟,其係在前述複數片薄膜中之至少1片薄膜的一面或兩面,塗布活性能量線硬化型接著劑;貼合步驟,其係在以前述接著劑為介於相鄰薄膜之間的方式積層而成之狀態下,藉由在朝搬運方向旋轉的一對貼合輥之間將前述複數片薄膜夾住而予以互相貼合;以及活性能量線照射步驟,其係對互相貼合之前述複數片 薄膜照射活性能量線,而使前述接著劑硬化。 The present invention provides a method for producing a laminated film obtained by laminating a plurality of sheets of film through an active energy ray-curable adhesive, which is provided in the following order: an adhesive application step of at least one of the plurality of films An active energy ray-curable adhesive is applied to one or both sides of the sheet film; and a bonding step is carried out in a state in which the adhesive is laminated between adjacent films, in a direction toward the conveyance direction a plurality of rotating sheets are sandwiched between the plurality of bonding rolls to adhere to each other; and an active energy ray irradiation step is to apply the plurality of sheets to each other The film is irradiated with an active energy ray to harden the aforementioned adhesive.

在本發明之前述複數片薄膜,在前述接著劑塗布步驟未塗布前述接著劑的面而在前述貼合步驟成為與前述接著劑相接的面之表面粗糙度為200nm以下。 In the above-mentioned plurality of sheets of the film of the present invention, the surface of the surface of the adhesive which is not coated with the adhesive in the adhesive application step is 200 nm or less in the surface where the bonding step is brought into contact with the adhesive.

在本發明之所謂表面粗糙度,係意指在2001年改訂版JIS B 0601之十點平均粗糙度(Rzjis;其中,將基準長度設為2.5mm,將評價長度設為12.5mm),以下有時簡寫為Rz。表面粗糙度(Rz)的單位為nm。該表面粗糙度(Rz)的測定,係例如使用東京精密(股)製「Handysurf E35A」作為測定裝置,將切斷(cut off)值(基準長度)設為2.5mm,將測定距離設為12.5mm,將上述測定裝置載至對象薄膜,而求取測定表面粗糙度10次時之平均值。該表面粗糙度大於200nm時,在前述貼合步驟,氣泡容易混入薄膜之間。表面粗糙度係以100nm以下為佳,較佳為80nm以下。具有此種表面粗糙度之薄膜,係能夠從市售品選擇。又,亦可以藉由在薄膜的表面塗布樹脂等來調整表面粗糙度。 The term "surface roughness" in the present invention means a ten point average roughness (Rzjis; wherein the reference length is set to 2.5 mm and the evaluation length is set to 12.5 mm) in the revised version of JIS B 0601 in 2001, and the following The time is abbreviated as Rz. The unit of surface roughness (Rz) is nm. For the measurement of the surface roughness (Rz), for example, "Handysurf E35A" manufactured by Tokyo Seimi Co., Ltd. is used as the measuring device, and the cut off value (reference length) is set to 2.5 mm, and the measurement distance is set to 12.5. In mm, the above-mentioned measuring device was carried on the target film, and the average value at which the surface roughness was measured 10 times was obtained. When the surface roughness is more than 200 nm, bubbles are easily mixed between the films in the bonding step. The surface roughness is preferably 100 nm or less, preferably 80 nm or less. A film having such a surface roughness can be selected from commercially available products. Further, the surface roughness can be adjusted by applying a resin or the like to the surface of the film.

在前述接著劑塗布步驟,所塗布之前述接著劑的厚度係以2μm以下為佳。在所塗布的接著劑的厚度為2μm以下之時,特別是在前述貼合步驟,因為氣泡容易混入薄膜之間,使得依照本發明所達成之抑制氣泡混入之效果尤為顯著。又,在複數片薄膜所塗布的接著劑之中,至少一接著劑的厚度為2μm以時,能夠顯著地達成本發明的效果。 In the above-described adhesive application step, the thickness of the above-mentioned adhesive to be applied is preferably 2 μm or less. When the thickness of the applied adhesive is 2 μm or less, particularly in the above-mentioned bonding step, since bubbles are easily mixed between the films, the effect of suppressing the incorporation of bubbles in accordance with the present invention is particularly remarkable. Further, among the adhesives applied to the plurality of sheets, when the thickness of at least one of the adhesives is 2 μm, the effects of the present invention can be remarkably achieved.

作為在本發明所製造的積層膜,例如可舉出偏光板。製造積層膜時,複數片薄膜例如可含有光學薄膜及透明薄膜。 As a laminated film manufactured by this invention, a polarizing plate is mentioned, for example. When the laminated film is produced, the plurality of sheets may contain, for example, an optical film and a transparent film.

(光學薄膜) (optical film)

所謂的光學薄膜,係例如偏光薄膜、相位差薄膜、3D電視用的圖案相位差薄膜(Patterned Retarder Film),可為1片薄膜,亦可為複數片薄膜的積層體。 The optical film is, for example, a polarizing film, a retardation film, or a patterned retarder film for 3D television, and may be one film or a laminate of a plurality of films.

在本發明,以積層膜的方式製造偏光板時,所使用的偏光薄膜係例如為使單軸延伸而成之聚乙烯醇系樹脂薄膜吸附配向有二色性色素者。聚乙烯醇系樹脂係能夠藉由將聚乙酸乙烯酯系樹脂皂化而得到。作為聚乙酸乙烯酯系樹脂,除了乙酸乙烯酯的同元聚合物之聚乙酸乙烯酯之外,可舉出乙酸乙烯酯與能夠與其共聚合的其他單體之共聚物(例如,乙烯-乙酸乙烯酯共聚物)等。作為能夠與乙酸乙烯酯共聚合的其他單體,另可舉出不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、具有銨基之丙烯醯胺類等。聚乙烯醇系樹脂的皂化度係85莫耳%以上,以90莫耳%以上為佳,較佳為98至100莫耳%。聚乙烯醇系樹脂的平均聚合度係通常為1000至10000,較佳為1500至5000。該等聚乙烯醇系樹脂,係亦以經改性者為佳,例如亦能夠使用經醛類改性而成之聚乙烯甲醛(polyvinyl formal)、聚乙烯縮醛、聚乙烯縮醛(polyvinyl acetal)、聚乙烯丁醛(polyvinyl butyral)等。 In the present invention, when a polarizing plate is produced by laminating a film, the polarizing film to be used is, for example, a polyvinyl alcohol-based resin film which is uniaxially stretched and adsorbed to have a dichroic dye. The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to the polyvinyl acetate of the homopolymer of vinyl acetate, a copolymer of vinyl acetate and another monomer copolymerizable therewith (for example, ethylene-vinyl acetate) may be mentioned. Ester copolymer) and the like. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The degree of saponification of the polyvinyl alcohol-based resin is 85 mol% or more, preferably 90 mol% or more, preferably 98 to 100 mol%. The average degree of polymerization of the polyvinyl alcohol-based resin is usually from 1,000 to 10,000, preferably from 1,500 to 5,000. These polyvinyl alcohol-based resins are preferably modified, and for example, polyvinyl formal, polyvinyl acetal, or polyvinyl acetal modified with an aldehyde can also be used. ), polyvinyl butyral (polyvinyl butyral) and the like.

將此種聚乙烯醇系樹脂製膜而成者係能夠 使用作為偏光薄膜的坯膜。將聚乙烯醇系樹脂製膜之方法,係無特別限定,能夠使用以往眾所周知的適當方法進行製膜。由聚乙烯醇系樹脂所構成之坯膜的膜厚係無特別限定,例如10至150μm左右。通常係以捲物狀供給且厚度為20至100μm的範圍內,較佳為30至80μm的範圍內,又,在工業上實用的寬度為1500至6000mm的範圍內。 The film made of such a polyvinyl alcohol-based resin can be A green film as a polarizing film was used. The method of forming a film of a polyvinyl alcohol-based resin is not particularly limited, and it can be formed into a film by a suitable method known in the art. The film thickness of the green film made of a polyvinyl alcohol-based resin is not particularly limited, and is, for example, about 10 to 150 μm. It is usually supplied in the form of a roll and has a thickness in the range of 20 to 100 μm, preferably 30 to 80 μm, and industrially practical width in the range of 1500 to 6000 mm.

作為市售的聚乙烯醇系樹脂薄膜,例如可舉出VINYLON VF-PS#7500(KURARAY製、坯膜厚度為75μm)、OPL薄膜M-7500(日本合成製、坯膜厚度為75μm)、VINYLON VF-PS#6000(KURARAY製、坯膜厚度為60μm)、VINYLON VF-PE#6000(KURARAY製、坯膜厚度為60μm)、VINYLON VF-PE#5000(KURARAY製、坯膜厚度為50μm)等。 The commercially available polyvinyl alcohol-based resin film is, for example, VINYLON VF-PS #7500 (manufactured by KURARAY, the thickness of the green film is 75 μm), OPL film M-7500 (manufactured by Nippon Seiki Co., Ltd., thickness: 75 μm), VINYLON VF-PS#6000 (KURARAY, billet thickness 60μm), VINYLON VF-PE#6000 (KURARAY, billet thickness 60μm), VINYLON VF-PE#5000 (KURARAY, billet thickness 50μm), etc. .

偏光薄膜係通常經過以下步驟來製造:染色處理步驟,其係使用二色性色素將聚乙烯醇系樹脂薄膜染色而使其吸附二色性色素之步驟;硼酸處理步驟,其係將吸附有二色性色素之聚乙烯醇系樹脂薄膜使用硼酸水溶液進行處理之步驟;以及水洗處理步驟,其係在使用該硼酸水溶液處理後,進行水洗之步驟。 The polarizing film is usually produced by the following steps: a dyeing treatment step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye to adsorb a dichroic dye; and a boric acid treatment step of adsorbing two The polyvinyl alcohol-based resin film of the coloring matter is treated with a boric acid aqueous solution; and the water washing treatment step is a step of washing with water after the boric acid aqueous solution is used.

又,在製造偏光薄膜時,通常,聚乙烯醇系樹脂薄膜係經單軸延伸,該單軸延伸係可以在染色處理步驟之前進行,亦可以在染色處理步驟中進行,且亦可以在染色處理步驟之後進行。在染色處理步驟之後,進行單軸延伸時,該單軸延伸係可以在硼酸處理步驟之前進行, 亦可以在硼酸處理步驟中進行。當然,亦能夠在該等複數階段進行單軸延伸。 Further, in the production of a polarizing film, generally, the polyvinyl alcohol-based resin film is uniaxially stretched, and the uniaxial stretching system may be carried out before the dyeing treatment step, or may be carried out in the dyeing treatment step, and may also be dyed. After the step. After uniaxial stretching after the dyeing treatment step, the uniaxial extension can be performed before the boric acid treatment step, It can also be carried out in a boric acid treatment step. Of course, uniaxial stretching can also be performed at these complex stages.

單軸延伸係可以在周速不同的輥之間,單軸地進行延伸,亦可以使用熱輥而單軸地進行延伸。又,亦可以是在大氣中進行延伸之乾式延伸,亦可以是在使用溶劑使其膨潤的狀態下進行延伸之濕式延伸。延伸倍率係通常為3至8倍左右。 The uniaxial stretching system may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially extended using a heat roll. Further, it may be a dry stretching which is extended in the air, or may be a wet stretching which is extended in a state where it is swollen with a solvent. The stretching ratio is usually about 3 to 8 times.

在染色處理步驟,聚乙烯醇系樹脂薄膜使用二色性色素之染色,係例如能夠藉由將聚乙烯醇系樹脂薄膜浸漬在含有二色性色素之水溶液來進行。作為二色性色素,例如能夠使用碘、二色性染料等。二色性染料係例如包含由C.I.DIRECT RED 39等的重氮化合物所構成之二色性直接染料;及由三偶氮、四偶氮等的化合物所構成之二色性直接染料。又,聚乙烯醇系樹脂薄膜係在染色處理之前,以預先施行在水中之浸漬處理為佳。 In the dyeing treatment step, the polyvinyl alcohol-based resin film is dyed with a dichroic dye, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye. As the dichroic dye, for example, iodine, a dichroic dye, or the like can be used. The dichroic dye includes, for example, a dichroic direct dye composed of a diazo compound such as C.I. DIRECT RED 39; and a dichroic direct dye composed of a compound such as trisazo or tetrazo. Further, the polyvinyl alcohol-based resin film is preferably subjected to immersion treatment in water beforehand before the dyeing treatment.

使用碘作為二色性色素時,通常係採用在含有碘及碘化鉀之水溶液,浸漬聚乙烯醇系樹脂薄膜而染色之方法。在該水溶液之碘的含量,係通常每100重量份的水,為0.01至1重量份,碘化鉀的含量係通常每100重量份的水,為0.5至20重量份。使用碘作為二色性色素時,在染色所使用之水溶液的溫度,係通常為20至40℃,在該水溶液的浸漬時間(染色時間)係通常為20至1800秒。 When iodine is used as the dichroic dye, a method in which a polyvinyl alcohol-based resin film is impregnated and dyed in an aqueous solution containing iodine and potassium iodide is usually used. The content of iodine in the aqueous solution is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight per 100 parts by weight of water. When iodine is used as the dichroic dye, the temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C, and the immersion time (dyeing time) of the aqueous solution is usually 20 to 1800 seconds.

另一方面,使用二色性染料作為二色性色素時,通常係採用在含有二色性染料水溶液,浸漬聚乙烯 醇系樹脂薄膜而染色之方法。在該水溶液之二色性染料的含量,係通常每100重量份的水,為1×10-4至10重量份,較佳為1×10-3至1重量份,特佳為1×10-3至1×10-2重量份。該水溶液亦可含有硫酸鈉等的無機鹽作為染色助劑。使用二色性染料作為二色性色素時,在染色所使用之染料水溶液的溫度係通常為20至80℃,又,在該水溶液的浸漬時間(染色時間)係通常為10至1800秒。 On the other hand, when a dichroic dye is used as the dichroic dye, a method of dyeing by impregnating a polyvinyl alcohol-based resin film with a dichroic dye aqueous solution is usually employed. The content of the dichroic dye in the aqueous solution is usually 1 × 10 -4 to 10 parts by weight, preferably 1 × 10 -3 to 1 part by weight, particularly preferably 1 × 10, per 100 parts by weight of water. -3 to 1 × 10 -2 parts by weight. The aqueous solution may also contain an inorganic salt such as sodium sulfate as a dyeing assistant. When a dichroic dye is used as the dichroic dye, the temperature of the dye aqueous solution used for dyeing is usually 20 to 80 ° C, and the immersion time (dyeing time) of the aqueous solution is usually 10 to 1800 seconds.

硼酸處理步驟,係藉由將經二色性色素染色後之聚乙烯醇系樹脂薄膜浸漬在含硼酸的水溶液來進行。在含硼酸的水溶液之硼酸的量,係每100重量份的水,通常為2至15重量份,較佳為5至12重量份。在上述的染色處理步驟使用碘作為二色性色素時,在該硼酸處理步驟所使用之含硼酸的水溶液係以含有碘化鉀為佳。此時,在含硼酸的水溶液之碘化鉀的量,係每100重量份的水,通常為0.1至15重量份,較佳為5至12重量份。在含硼酸的水溶液之浸漬時間,通常為60至1200秒,較佳為150至600秒,更佳為200至400秒。含硼酸的水溶液之溫度係通常為40℃以上,以50至85℃為佳,較佳為55至75℃。 The boric acid treatment step is carried out by immersing the polyvinyl alcohol-based resin film dyed with the dichroic dye in an aqueous solution containing boric acid. The amount of boric acid in the aqueous solution containing boric acid is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water. When iodine is used as the dichroic dye in the above dyeing treatment step, the aqueous solution containing boric acid used in the boric acid treatment step preferably contains potassium iodide. At this time, the amount of potassium iodide in the aqueous solution containing boric acid is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight per 100 parts by weight of water. The immersion time in the aqueous solution containing boric acid is usually 60 to 1200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually 40 ° C or higher, preferably 50 to 85 ° C, preferably 55 to 75 ° C.

接著的水洗處理步驟,係例如藉由將上述之硼酸處理後的聚乙烯醇系樹脂薄膜,浸漬在水中而水洗處理。於水洗處理之水的溫度,通常為4至40℃,浸漬時間通常為1至120秒。水洗處理後係通常施予乾燥處理而得到偏光薄膜。乾燥處理係適合使用例如熱風乾燥機、遠 紅外線加熱器等而進行。乾燥處理的溫度通常為30至100℃,較佳為50至80℃。乾燥處理時間係通常為60至600秒,較佳為120至600秒。 The subsequent washing step is performed by, for example, immersing the above-described boric acid-treated polyvinyl alcohol-based resin film in water and washing with water. The temperature of the water to be washed is usually 4 to 40 ° C, and the immersion time is usually 1 to 120 seconds. After the water washing treatment, the drying treatment is usually carried out to obtain a polarizing film. Drying treatment is suitable for use, for example, hot air dryer, far It is carried out by an infrared heater or the like. The temperature of the drying treatment is usually from 30 to 100 ° C, preferably from 50 to 80 ° C. The drying treatment time is usually from 60 to 600 seconds, preferably from 120 to 600 seconds.

如此進行而對聚乙烯醇系樹脂薄膜施行單軸延伸、使用二色性色素之染色、硼酸處理及水洗處理,能夠得到偏光薄膜。該偏光薄膜的厚度通常為5至50μm的範圍內。 In this manner, the polyvinyl alcohol-based resin film is subjected to uniaxial stretching, dyeing with a dichroic dye, boric acid treatment, and water washing treatment to obtain a polarizing film. The thickness of the polarizing film is usually in the range of 5 to 50 μm.

(透明薄膜) (transparent film)

在本發明,以積層膜的方式製造偏光板時,係在上述之光學薄膜的一面或兩面貼合透明薄膜。在光學薄膜的兩面貼合透明薄膜時,各自的透明薄膜係可為相同者,亦可為不同種類的薄膜。 In the present invention, when a polarizing plate is produced as a laminated film, a transparent film is bonded to one surface or both surfaces of the above optical film. When the transparent film is bonded to both surfaces of the optical film, the respective transparent films may be the same or different types of films.

作為構成透明薄膜的材料,例如能夠舉出如環烯烴系樹脂、乙酸纖維素系樹脂、聚對酞酸乙二酯、聚萘二甲酸乙二酯、聚對酞酸丁二酯之聚酯系樹脂、聚碳酸酯系樹脂、丙烯酸系樹脂、聚丙烯等先前以來在該領域被廣泛地使用之薄膜材料。 Examples of the material constituting the transparent film include a cycloolefin resin, a cellulose acetate resin, polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate. A film material which has been widely used in the field such as a resin, a polycarbonate resin, an acrylic resin, or a polypropylene.

所謂環烯烴系樹脂,係例如降莰烯、多環降莰烯系單體之具有由環狀烯烴(環烯烴)所構成單體的單元之熱可塑性樹脂(亦稱為熱可塑性環烯烴系樹脂)。環烯烴系樹脂係可以是使用上述環烯烴的開環聚合物或使用2種以上的環烯烴之開環共聚物的氫化物;亦可以是環烯烴與鏈狀烯烴、具有乙烯基的芳香族化合物等之加成聚合物。又,導入有極性基者亦為有效。 The cycloolefin-based resin is a thermoplastic resin having a unit of a monomer composed of a cyclic olefin (cycloolefin), such as a norbornene or a polycyclic norbornene-based monomer (also referred to as a thermoplastic cycloolefin resin). ). The cycloolefin resin may be a ring-opening polymer using the above cyclic olefin or a hydrogenated product using a ring-opening copolymer of two or more kinds of cyclic olefins; or a cyclic olefin and a chain olefin, and an aromatic compound having a vinyl group; Addition of the polymer. Moreover, it is also effective to introduce a polar base.

使用環烯烴與鏈狀烯烴或/及具有乙烯基的芳香族化合物之共聚物時,作為鏈狀烯烴,可舉出乙烯、丙烯等,又,作為具有乙烯基之芳香族化合物,可舉出苯乙烯、α-甲基苯乙烯、核烷基取代苯乙烯等。在此種共聚物,由環烯烴所構成之單體的單元可為50莫耳%以下(較佳為15至50莫耳%)。特別是使用環烯烴、鏈狀烯烴及具有乙烯基的芳香族化合物之三元共聚物時,如上述,由環烯烴所構成之單體的單元係能夠設為比較少的量。在此種三元共聚物,由鏈狀烯烴所構成之單體的單元,係通常為5至80莫耳%,由具有乙烯基的芳香族化合物所構成之單體的單元,係通常為5至80莫耳%。 When a copolymer of a cyclic olefin and a chain olefin or an aromatic compound having a vinyl group is used, examples of the chain olefin include ethylene and propylene, and examples of the aromatic compound having a vinyl group include benzene. Ethylene, α-methylstyrene, nuclear alkyl-substituted styrene, and the like. In such a copolymer, the unit of the monomer composed of the cyclic olefin may be 50 mol% or less (preferably 15 to 50 mol%). In particular, when a terpolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group is used, as described above, a unit cell of a monomer composed of a cyclic olefin can be set to a relatively small amount. In such a terpolymer, a unit of a monomer composed of a chain olefin is usually 5 to 80 mol%, and a unit of a monomer composed of an aromatic compound having a vinyl group is usually 5 Up to 80% by mole.

環烯烴系樹脂係能夠適合使用適當的市售品、例如,Topas(Ticona公司製)、ARTON(JSR(股)製)、ZEONOR(日本ZEON(股)製)、ZEONEX(日本ZEON(股)製)、APEL(三井化學(股)製)、OXIS(大倉工業公司製)等。將此種環烯烴系樹脂製膜而作為薄膜時,能夠適當地使用溶劑流延法、熔融擠製法等的眾所周知的方法。 For the cycloolefin resin, for example, Topas (manufactured by Ticona Co., Ltd.), ARTON (made by JSR Co., Ltd.), ZEONOR (made by Japan ZEON Co., Ltd.), and ZEONEX (made by Japan ZEON Co., Ltd.) can be suitably used. ), APEL (Mitsui Chemical Co., Ltd.), OXIS (manufactured by Okura Industrial Co., Ltd.), and the like. When such a cycloolefin-based resin is formed into a film, a well-known method such as a solvent casting method or a melt extrusion method can be suitably used.

又,亦可使用例如S-SINA(積水化學工業(股)製)、SCA40(積水化學工業(股)製)、ZEONOR薄膜((股)OPTES製)等預先製膜而成之環烯烴系樹脂製薄膜的市售品。 Further, for example, a cycloolefin-based resin obtained by preliminarily forming a film such as S-SINA (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (manufactured by Sekisui Chemical Co., Ltd.), or ZEONOR film (manufactured by OPTES) may be used. A commercially available product of a film.

環烯烴系樹脂薄膜係可以是經單軸延伸或雙軸延伸者。藉由延伸,能夠對環烯烴系樹脂薄膜賦予任意的相位差值。延伸係通常邊將薄膜捲物捲出邊連續地進行,且使用加熱爐在往輥的前進方向(薄膜的長度方向)、 與其前進方向垂直的方向(薄膜的寬度方向)、或其兩方被延伸。加熱爐的溫度係通常採用從環烯烴系樹脂的玻璃轉移溫度附近至玻璃轉移溫度+100℃的範圍。延伸的倍率係通常為1.1至6倍,較佳為1.1至3.5倍。 The cycloolefin-based resin film may be one which is uniaxially stretched or biaxially stretched. By extending, it is possible to impart an arbitrary retardation value to the cycloolefin-based resin film. The extension system is generally continuously performed while winding up the film roll, and using a heating furnace in the advancing direction of the roll (the length direction of the film), The direction perpendicular to the advancing direction (the width direction of the film), or both of them are extended. The temperature of the heating furnace is usually in the range from the vicinity of the glass transition temperature of the cycloolefin resin to the glass transition temperature + 100 °C. The extension ratio is usually 1.1 to 6 times, preferably 1.1 to 3.5 times.

因為環烯烴系樹脂薄膜處於捲狀物狀態時,薄膜之間接著而有容易產生黏結之傾向,通常係在貼合保護薄膜之後,被製成捲狀物。又,因為環烯烴系樹脂薄膜係通常表面活性差,使其與光學薄膜接著之表面係以進行電漿處理、電暈處理、紫外線照射處理、火焰處理、皂化處理等的表面處理為佳。尤其是能夠比較容易實施之電漿處理、特別是大氣壓電漿處理、電暈處理係適合的。 When the cycloolefin-based resin film is in a rolled state, the film tends to be easily adhered to each other, and is usually formed into a roll after bonding the protective film. Further, since the cycloolefin resin film is generally inferior in surface activity, it is preferred to carry out surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, saponification treatment or the like on the surface of the optical film. In particular, plasma treatment, particularly atmospheric piezoelectric slurry treatment and corona treatment, which are relatively easy to implement, are suitable.

所謂乙酸纖維素系樹脂,係纖維素的部分或完全酯化物,例如能夠舉出由纖維素的乙酸酯、丙酸酯、丁酸酯、其等的混合酯等所構成之薄膜。更具體地,可舉出三乙醯纖維素薄膜、二乙醯纖維素薄膜、乙酸丙酸纖維素薄膜、乙酸丁酸纖維素薄膜薄膜等。作為此種纖維素酯系樹脂薄膜,能夠適合使用適當的市售品,例如FUJITAC TD80(富士軟片(股)製)、FUJITAC TD80UF(富士軟片(股)製)、FUJITAC TD80UZ(富士軟片(股)製)、KC8UX2M(Konica Minolta Opto(股)製)、KC8UY(Konica Minolta Opto(股)製)FUJITAC TD60UL(富士軟片(股)製)、KC4UYW(Konica Minolta Opto(股)製)、KC6UAW(Konica Minolta Opto(股)製)等。 The cellulose acetate-based resin is a partial or complete esterified product of cellulose, and examples thereof include a film composed of cellulose acetate, propionate, butyrate, or a mixed ester thereof. More specifically, a triethylene fluorene cellulose film, a diethyl fluorene cellulose film, a cellulose acetate propionate film, a cellulose acetate butyrate film film, or the like can be given. As such a cellulose ester-based resin film, an appropriate commercial product such as FUJITAC TD80 (Fuji Film Co., Ltd.), FUJITAC TD80UF (Fuji Film Co., Ltd.), and FUJITAC TD80UZ (Fuji Film Co., Ltd.) can be suitably used. System), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC8UY (Konica Minolta Opto Co., Ltd.) FUJITAC TD60UL (Fuji Film Co., Ltd.), KC4UYW (Konica Minolta Opto Co., Ltd.), KC6UAW (Konica Minolta) Opto (share) system, etc.

又,作為透明薄膜,亦能夠適合使用經賦 予相位差特性之乙酸纖維素系樹脂薄膜。作為經賦予種相位差特性之乙酸纖維素系樹脂薄膜的市售品,可舉出WV BZ 438(富士軟片(股)製)、KC4FR-1(Konica Minolta Opto(股)製)、KC4CR-1(Konica Minolta Opto(股)製)、KC4AR-1(Konica Minolta Opto(股)製)等。乙酸纖維素亦稱為乙醯纖維素、纖維素乙酸酯。 Moreover, as a transparent film, it can also be used as a transparent film. A cellulose acetate resin film having a phase difference characteristic. The commercially available product of the cellulose acetate-based resin film to which the phase difference property is imparted is WV BZ 438 (made by Fujifilm Co., Ltd.), KC4FR-1 (made by Konica Minolta Opto Co., Ltd.), and KC4CR-1. (Konica Minolta Opto Co., Ltd.), KC4AR-1 (Konica Minolta Opto Co., Ltd.), and the like. Cellulose acetate is also known as acetaminophen, cellulose acetate.

該等乙酸纖維素系樹脂薄膜係容易吸水,偏光板的水分率有對偏光板的端部鬆弛造成影響之情形。製造偏光板時的水分率係以越接近在偏光板的保管環境、例如潔淨室的製造線、捲狀物保管倉庫之平衡水分率為越佳,雖然亦取決於積層膜的構成,例如2.0至3.5%左右,更佳為2.5%至3.0%。該偏光板之水分率的數值係使用乾燥重量法測定,係使用恆溫槽且於105℃的溫度乾燥120分鐘後之處理前後的重量變化。 These cellulose acetate-based resin films are likely to absorb water, and the moisture content of the polarizing plate may affect the relaxation of the end portion of the polarizing plate. The water content at the time of producing the polarizing plate is preferably as close as possible to the storage environment of the polarizing plate, for example, the manufacturing line of the clean room, and the storage area of the roll storage, and the moisture content is better depending on the structure of the laminated film, for example, 2.0 to About 3.5%, more preferably 2.5% to 3.0%. The numerical value of the moisture content of the polarizing plate was measured by a dry weight method, and was a change in weight before and after the treatment using a constant temperature bath and drying at a temperature of 105 ° C for 120 minutes.

在本發明的偏光板所使用之透明薄膜的厚度係以較薄者為佳,太薄時強度低落,而成為加工性差者。另一方面,太厚時產生透明性低落,或是在積層後必要的硬化時間變長等之問題。因此,透明薄膜之適當的厚度係例如5至200μm,以10至150μm為佳,較佳為10至100μm。 The thickness of the transparent film used in the polarizing plate of the present invention is preferably as thin as possible, and when the thickness is too thin, the strength is low, and the workability is poor. On the other hand, when it is too thick, there is a problem that the transparency is low, or the hardening time required after the lamination is lengthened. Therefore, a suitable thickness of the transparent film is, for example, 5 to 200 μm, preferably 10 to 150 μm, preferably 10 to 100 μm.

為了提升接著劑與光學薄膜及/或透明薄膜的接著性,亦可對光學薄膜及/或透明薄膜施行電暈處理、火炎處理、電漿處理、紫外線處理、底漆塗布處理、皂化處理等的表面處理。 In order to improve the adhesion between the adhesive and the optical film and/or the transparent film, the optical film and/or the transparent film may be subjected to corona treatment, flame treatment, plasma treatment, ultraviolet treatment, primer coating treatment, saponification treatment, and the like. Surface treatment.

又,透明薄膜係可以各自單獨或組合2種以上而施行抗眩處理、抗反射處理、硬塗處理、抗靜電處理、防污處理等的表面處理。又,透明薄膜及/或透明薄膜表面保護層亦可含有二苯基酮系化合物、苯并三唑系化合物等的紫外線吸收劑;及磷酸苯酯系化合物、酞酸酯化合物等的塑化劑。 Further, the transparent film may be subjected to surface treatment such as anti-glare treatment, anti-reflection treatment, hard coating treatment, antistatic treatment, antifouling treatment, or the like, alone or in combination of two or more. Further, the transparent film and/or the transparent film surface protective layer may contain a UV absorber such as a diphenylketone compound or a benzotriazole compound; and a plasticizer such as a phenyl phosphate compound or a phthalate compound. .

而且,亦能夠使透明薄膜具有作為相位差薄膜之功能、作為亮度提升薄膜之功能、作為反射薄膜之功能、作為半透射反射薄膜之功能、作為擴散薄膜之功能、作為光學補償薄膜之功能等光學功能。此時,除了例如藉由在透明薄膜的表面,積層相位差薄膜、亮度提升薄膜、反射薄膜、半透射反射薄膜、擴散薄膜、光學補償薄膜等光學功能性薄膜,使其具有此種功能以外,亦能夠對透明薄膜本身賦予此種功能。又,如具有亮度提升薄膜的功能之擴散薄膜等,亦可使透明薄膜具有複數功能。 Further, the transparent film can also function as a retardation film, a function as a brightness enhancement film, a function as a reflective film, a function as a semi-transmissive film, a function as a diffusion film, and an optical compensation function. Features. In this case, in addition to the optical functional film such as a laminated retardation film, a brightness enhancement film, a reflective film, a transflective film, a diffusion film, or an optical compensation film, on the surface of the transparent film, for example, It is also possible to impart such a function to the transparent film itself. Further, the transparent film may have a plurality of functions such as a diffusion film having a function of a brightness enhancement film.

例如,能夠藉由對如上述的透明薄膜,施行在日本特許第2841377號公報、日本特許第3094113號公報等所記載的延伸處理,或施行在日本特許第3168850號公報所記載的處理,來賦予作為相位差薄膜之功能。在相位差薄膜之相位差特性,係能夠適當地選擇例如正面相位差值為5至100nm,厚度方向相位差值為40至300nm的範圍等。又,能夠藉由在上述的透明薄膜,使用在日本特開2002-169025號公報、日本特開2003-29030號公報所記載的方法形成微細孔,或是藉由將選擇不同反射中心波長 之2層以上的膽固醇型液晶層重疊,來賦予作為亮度提升薄膜之功能。 For example, the transparent film described in Japanese Patent No. 2841377, Japanese Patent No. 3094113, or the like, or the process described in Japanese Patent No. 3168850 can be used. As a function of the phase difference film. In the phase difference characteristic of the retardation film, for example, a range in which the front phase difference value is 5 to 100 nm, a thickness direction retardation value is 40 to 300 nm, or the like can be appropriately selected. Further, it is possible to form fine pores by the method described in JP-A-2002-169025, JP-A-2003-29030, or to select different reflection center wavelengths by using the transparent film described above. Two or more layers of the cholesteric liquid crystal layers are superposed to impart a function as a brightness enhancement film.

在上述的透明薄膜藉由蒸鍍、濺鍍等形成金屬薄膜時,能夠賦予作為反射薄膜或半透射反射薄膜之功能。藉由在上述的透明薄膜塗布含有微粒子的樹脂溶液,能夠賦予作為擴散薄膜之功能。又,藉由在上述的透明薄膜,塗布盤形液晶性化合物等的液晶性化合物且使其配向,能夠賦予作為光學補償薄膜之功能。又,亦可使透明薄膜含有顯現相位差之化合物。而且,亦可使用適當的接著劑將各種光學功能性薄膜直接貼合在光學薄膜。作為光學功能性薄膜的市售品,例如能夠舉出DBEF(3M公司製,在日本係能夠從住友3M(股)取得)等的亮度提升薄膜、WV薄膜(富士軟片(股)製)等的視野角改良薄膜、ARTON薄膜(JSR(股)製)、ZEONOR薄膜((股)OPTES製)、S-SINA(積水化學工業(股)製)、VA-TAC(Konica Minolta(股)製)、Sumikalight(住友化學(股)製)等的相位差薄膜等。 When the transparent film described above is formed into a metal thin film by vapor deposition, sputtering, or the like, it can provide a function as a reflective film or a semi-transmissive reflective film. By applying a resin solution containing fine particles to the above transparent film, it is possible to impart a function as a diffusion film. In addition, by applying a liquid crystal compound such as a discotic liquid crystalline compound to the transparent film described above and aligning it, it is possible to impart a function as an optical compensation film. Further, the transparent film may contain a compound exhibiting a phase difference. Further, various optical functional films may be directly bonded to the optical film using a suitable adhesive. As a commercially available product of the optical functional film, for example, a brightness enhancement film such as DBEF (made by the 3M company, which can be obtained from Sumitomo 3M), and a WV film (made by Fujifilm Co., Ltd.), etc. Viewing angle improved film, ARTON film (made by JSR), ZEONOR film (made by OPTES), S-SINA (made by Sekisui Chemical Industry Co., Ltd.), VA-TAC (made by Konica Minolta Co., Ltd.), A retardation film such as Sumikalight (Sumitomo Chemical Co., Ltd.).

(活性能量線硬化型接著劑)作為在本發明能夠使用之活性能量線硬化型接著劑,從耐候性、折射率、陽離子聚合性等的觀點,例如可舉出由含有藉由照射活性能量線而硬化的環氧樹脂之環氧系樹脂組成物所構成之接著劑。但是不被此限定,亦能夠採用先前以來在製造偏光板所使用之各種活性能量線硬化型接著劑(有機溶劑系接著劑、熱熔系接著劑、無溶劑型接著劑等)。 (Active energy ray-curable adhesive) As an active energy ray-curable adhesive which can be used in the present invention, from the viewpoints of weather resistance, refractive index, cationic polymerizability and the like, for example, irradiation with an active energy ray is included An adhesive composed of an epoxy resin composition of a cured epoxy resin. However, it is not limited thereto, and various active energy ray-curable adhesives (organic solvent-based adhesives, hot-melt adhesives, solventless adhesives, and the like) used in the production of polarizing plates can be used.

所謂環氧樹脂,係意指在分子內具有2個以 上環氧基之化合物。從耐候性、折射率、陽離子聚合性等的觀點,在接著劑之硬化性環氧樹脂組成物所含有的環氧樹脂,係以在分子內不含有芳香環之環氧樹脂(例如,專利文獻1參照)為佳。作為此種環氧樹脂,能夠例示氫化環氧樹脂、脂環族環氧樹脂、脂肪族環氧樹脂等。 The term "epoxy resin" means having 2 in the molecule. A compound of an epoxy group. From the viewpoints of weather resistance, refractive index, cationic polymerizability, and the like, the epoxy resin contained in the curable epoxy resin composition of the adhesive is an epoxy resin which does not contain an aromatic ring in the molecule (for example, Patent Literature) 1 reference) is better. As such an epoxy resin, a hydrogenated epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, etc. can be illustrated.

氫化環氧樹脂係能夠將核氫化多羥基化合物,藉由進行環氧丙基醚化之方法來得到,其中,該核氫化多羥基化合物係藉由在觸媒的存在下且加壓下,將芳香族環氧樹脂的原料之多羥基化合物,選擇地進行核氫化反應而得到。作為芳香族環氧樹脂,例如可舉出雙酚A的二環氧丙基醚、雙酚F的二環氧丙基醚、及雙酚S的二環氧丙基醚等的雙酚型環氧樹脂;苯酚酚醛清漆環氧樹脂、甲酚酚醛清漆環氧樹脂、及羥基苯甲醛苯酚酚醛清漆環氧樹脂等的酚醛清漆型的環氧樹脂;四羥苯基甲烷的環氧丙基醚、四羥基二苯基酮的環氧丙基醚、及環氧化聚乙烯基苯酚等的多官能型的環氧樹脂等。氫化環氧樹脂之中,以經氫化之雙酚A的環氧丙基醚為佳。 The hydrogenated epoxy resin is capable of obtaining a nuclear hydrogenated polyhydroxy compound by a method of performing epoxy propyl etherification, wherein the nuclear hydrogenated polyhydroxy compound is used in the presence of a catalyst and under pressure. The polyhydroxy compound of the raw material of the aromatic epoxy resin is obtained by selectively performing a nuclear hydrogenation reaction. Examples of the aromatic epoxy resin include a bisphenol ring such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diepoxypropyl ether of bisphenol S. Oxygen resin; phenol novolak epoxy resin, cresol novolac epoxy resin, and phenol novolak epoxy resin such as novolac type epoxy resin; epoxypropyl ether of tetrahydroxyphenylmethane; A polyfunctional epoxy resin such as a glycidyl ether of tetrahydroxydiphenyl ketone or an epoxidized polyvinyl phenol. Among the hydrogenated epoxy resins, a hydrogenated bisphenol A epoxidized propyl ether is preferred.

所謂脂環族環氧樹脂,係意味著在分子內具有1個以上之鍵結於脂環族環的環氧基之環氧樹脂。所謂「鍵結於脂環族環的環氧基」,係意味著在下式表示的構造之交聯的氧原子-O-。下式中,m係2至5的整數。 The alicyclic epoxy resin means an epoxy resin having one or more epoxy groups bonded to an alicyclic ring in the molecule. The "epoxy group bonded to the alicyclic ring" means an oxygen atom -O- which is crosslinked by a structure represented by the following formula. In the following formula, m is an integer of 2 to 5.

Figure TWI613084BD00001
Figure TWI613084BD00001

將在上述式之(CH2)m中的1個或複數個氫原子除去後的形式之基,其鍵結於其他的化學結構之化合物係能夠成為脂環族環氧樹脂。(CH2)m中1個或複數個氫原子亦可適當地被甲基、乙基等直鏈狀烷基取代。脂環族環氧樹脂之中,因為具有氧雜二環己烷環(在上述式,m=3者)、氧雜二環庚烷環(在上述式,m=4者)之環氧樹脂係顯示優越的接著性而夠適合使用。以下,具體地例示能夠適合使用的脂環族環氧樹脂,但是不限定於該等化合物。 A group in which one or a plurality of hydrogen atoms in the above formula (CH 2 ) m are removed, and a compound which is bonded to another chemical structure can be an alicyclic epoxy resin. One or a plurality of hydrogen atoms in (CH 2 ) m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among the alicyclic epoxy resins, epoxy resins having an oxabicyclohexane ring (in the above formula, m=3) and an oxabicycloheptane ring (in the above formula, m=4) It shows superior adhesion and is suitable for use. Hereinafter, an alicyclic epoxy resin which can be suitably used is specifically exemplified, but it is not limited to these compounds.

(a)以下式(I)表示之環氧環己基甲基環氧環己烷羧酸酯類:

Figure TWI613084BD00002
(a) Epoxycyclohexylmethylepoxycyclohexanecarboxylate represented by the following formula (I):
Figure TWI613084BD00002

(式中,R1及R2係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基)。 (Wherein, R 1 is and R 2 represent lines each independently a linear alkyl group and a hydrogen atom or a C 1 to 5).

(b)以下式(II)表示之烷二醇的環氧環己烷羧酸酯類:

Figure TWI613084BD00003
(b) an epoxycyclohexane carboxylate of an alkanediol represented by the following formula (II):
Figure TWI613084BD00003

(式中,R3及R4係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基,n係表示2至20的整數)。 (wherein R 3 and R 4 are each independently a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and n is an integer of 2 to 20).

(c)以下式(III)表示之二羧酸的環氧環己基甲酯類:

Figure TWI613084BD00004
(c) Epoxycyclohexylmethyl esters of dicarboxylic acids represented by the following formula (III):
Figure TWI613084BD00004

(式中,R5及R6係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基,p係表示2至20的整數)。 (Wherein, R 5 and R 6 each independently lines represent the hydrogen atom or a linear alkyl group of 1 to 5 carbon atoms, p is an integer of 2 lines to 20).

(d)以下式(IV)表示之聚乙二醇的環氧環己基甲醚類:

Figure TWI613084BD00005
(d) Epoxycyclohexyl methyl ether of polyethylene glycol represented by the following formula (IV):
Figure TWI613084BD00005

(式中,R7及R8係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基,q係表示2至10的整數)。 (wherein R 7 and R 8 are each independently a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and q is an integer of 2 to 10).

(e)以下式(V)表示之烷二醇的環氧環己基甲醚類:

Figure TWI613084BD00006
(e) Epoxycyclohexyl methyl ether of an alkanediol represented by the following formula (V):
Figure TWI613084BD00006

(式中,R9及R10係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基,r係表示2至20的整數)。 (wherein R 9 and R 10 are each independently a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and r is an integer of 2 to 20).

(f)以下式(VI)表示之二環氧三螺化合物:

Figure TWI613084BD00007
(f) a diepoxide trispirate compound represented by the following formula (VI):
Figure TWI613084BD00007

(式中,R11及R12係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基)。 (wherein R 11 and R 12 are each independently a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(g)以下式(VII)表示之二環氧一螺化合物:

Figure TWI613084BD00008
(g) a diepene-spiro compound represented by the following formula (VII):
Figure TWI613084BD00008

(式中,R13及R14係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基)。 (wherein R 13 and R 14 are each independently a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(h)以下式(VIII)表示之二環氧化乙烯基環己烯類:

Figure TWI613084BD00009
(h) a bicyclic oxyethylene cyclohexene represented by the following formula (VIII):
Figure TWI613084BD00009

(式中,R15係表示氫原子或碳數1至5的直鏈狀烷基)。 (Wherein, R 15 represents a straight-chain alkyl-based hydrogen atom or a C 1 to 5).

(i)以下式(IX)表示之環氧環戊醚類:

Figure TWI613084BD00010
(i) Epoxycyclopentyl ethers represented by the following formula (IX):
Figure TWI613084BD00010

(式中,R16及R17係互相獨立而表示氫原子或碳數1至5的直鏈狀烷基)。 (Wherein, R 16 and R 17 independently of one another and lines represent a hydrogen atom or a linear alkyl group of 1 to 5 carbon atoms).

(j)以下式(X)表示之二環氧三環癸烷類:

Figure TWI613084BD00011
(j) Diepylene tricyclodecane represented by the following formula (X):
Figure TWI613084BD00011

(式中,R18係表示氫原子或碳數1至5的直鏈狀烷基)。 (Wherein, R 18 represents a straight-chain alkyl-based hydrogen atom or a C 1 to 5).

上述所例示的脂環族環氧樹脂之中,以下的脂環族環氧樹脂係可為市售者或其類似物,從比較容易取得等的理由,更能夠適合使用。 Among the alicyclic epoxy resins exemplified above, the following alicyclic epoxy resins may be commercially available or the like, and may be suitably used because they are relatively easy to obtain.

(A)7-氧雜二環[4.1.0]庚烷-3-羧酸與(7-氧雜-二環[4.1.0]庚-3-基)甲醇之酯化物[在式(I),R1=R2=H的化合物]、(B)4-甲基-7-氧雜二環[4.1.0]庚烷-3-羧酸與(4-甲基-7-氧雜-二環[4.1.0]庚-3-基)甲醇之酯化物[在式(I),R1=4-CH3、R2=4-CH3的化合物]、(C)7-氧雜二環[4.1.0]庚烷-3-羧酸與1,2-乙二醇之酯化物[在式(II),R3=R4=H、n=2的化合物]、(D)(7-氧雜二環[4.1.0]庚-3-基)甲醇與己二酸之酯化物 [在式(III),R5=R6=H、p=4的化合物]、(E)(4-甲基-7-氧雜二環[4.1.0]庚-3-基)甲醇與己二酸之酯化物[在式(III),R5=4-CH3、R6=4-CH3、p=4的化合物]、(F)(7-氧雜二環[4.1.0]庚-3-基)甲醇與1,2-乙二醇之醚化物[在式(V),R9=R10=H、r=2的化合物]。 (A) an ester of 7-oxabicyclo[4.1.0]heptane-3-carboxylic acid with (7-oxa-bicyclo[4.1.0]heptan-3-yl)methanol [in formula (I) ), R 1 = R 2 = H compound], (B) 4- methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid (4-methyl-7-oxa - an ester of bicyclo [4.1.0]heptan-3-yl)methanol [in the formula (I), a compound of R 1 =4-CH 3 , R 2 =4-CH 3 ], (C) 7-oxygen An esterified product of a heterobicyclo[4.1.0]heptane-3-carboxylic acid with 1,2-ethanediol [a compound of the formula (II), R 3 =R 4 =H, n=2], (D ) (7-oxabicyclo [4.1.0] hept-3-yl) methanol esterified with adipic acid [in the formula (III), R 5 = R 6 = H, p = 4 the compound], ( E) an ester of (4-methyl-7-oxabicyclo[4.1.0]heptan-3-yl)methanol with adipic acid [in formula (III), R 5 =4-CH 3 , R 6 =4-CH 3 , p=4 compound], (F) (7-oxabicyclo[4.1.0]heptan-3-yl)methanol and 1,2-ethanediol etherate [in formula ( V), R 9 = R 10 = H, compound of r = 2].

又,作為脂肪族環氧樹脂,能夠舉出脂肪族多元醇或其環氧烷加成物的聚環氧丙基醚。更具體地,可舉出1,4-丁二醇的二環氧丙基醚;1,6-己二醇的二環氧丙基醚;甘油的三環氧丙基醚;三羥甲基丙烷的三環氧丙基醚;聚乙二醇的二環氧丙基醚;丙二醇的二環氧丙基醚;藉由在乙二醇、丙二醇、及甘油等的脂肪族多元醇附加1種或2種以上的環氧烷(環氧乙烷、環氧丙烷)而得到之聚醚多元醇的聚環氧丙基醚等。 Further, examples of the aliphatic epoxy resin include a polyepoxypropyl ether of an aliphatic polyol or an alkylene oxide adduct thereof. More specifically, it may be exemplified by diethylene oxide propyl ether of 1,4-butanediol; diepoxypropyl ether of 1,6-hexanediol; triepoxypropyl ether of glycerin; trimethylol a tri-epoxypropyl ether of propane; a di-epoxypropyl ether of polyethylene glycol; a di-epoxypropyl ether of propylene glycol; one of an aliphatic polyol such as ethylene glycol, propylene glycol, or glycerin Or a polyepoxypropyl ether of a polyether polyol obtained by using two or more kinds of alkylene oxides (ethylene oxide or propylene oxide).

構成由環氧系樹脂組成物所構成的接著劑之環氧樹脂,係可單獨只有使用1種,亦可併用2種以上。在該組成物所使用的環氧樹脂之環氧當量,係通常為30至3,000g/當量,較佳為50至1,500g/當量的範圍內。環氧當量低於30g/當量時,有硬化後之複合偏光板的可撓性低落、或接著強度低落之可能性。另一方面,大於3,000g/當量時,與在接著劑所含有的其他成分之相溶性有低落之可能性。 The epoxy resin constituting the adhesive composition of the epoxy resin composition may be used alone or in combination of two or more. The epoxy equivalent of the epoxy resin used in the composition is usually in the range of 30 to 3,000 g / equivalent, preferably 50 to 1,500 g / equivalent. When the epoxy equivalent is less than 30 g/equivalent, the flexibility of the composite polarizing plate after curing may be lowered or the strength may be lowered. On the other hand, when it is more than 3,000 g/eq, the compatibility with other components contained in the adhesive may be lowered.

在該接著劑,從反應性的觀點,能夠適合使用陽離子聚合作為環氧樹脂的硬化反應。因此,活性能量線硬化型接著劑之硬化性環氧樹脂組成物係以調配陽離 子聚合起始劑為佳。陽離子聚合起始劑係藉由照射可見光線、紫外線、X射線、電子射線等的活性能量線來產生陽離子種或路易斯酸而使環氧基開始聚合反應。以下,將藉由照射活性能量線來產生陽離子種或路易斯酸且使環氧基開始聚合反應之陽離子聚合起始劑稱為「光陽離子聚合起始劑」。 In the adhesive, from the viewpoint of reactivity, cationic polymerization can be suitably used as the curing reaction of the epoxy resin. Therefore, the curable epoxy resin composition of the active energy ray-curable adhesive is formulated to disperse the cation A sub-polymerization initiator is preferred. The cationic polymerization initiator activates the epoxy group by irradiating an active energy ray such as visible light, ultraviolet light, X-rays, or electron beams to generate a cationic species or a Lewis acid. Hereinafter, a cationic polymerization initiator which generates a cationic species or a Lewis acid by irradiation of an active energy ray and starts an polymerization reaction of an epoxy group is referred to as a "photocationic polymerization initiator".

使用光陽離子聚合起始劑且藉由照射活性能量線來進行接著劑的硬化之方法係能夠在常溫硬化,考慮光學薄膜的耐熱性或膨脹引起變形之必要性減少且在能夠使薄膜之間良好地接著方面係有利的。又,因為光陽離子聚合起始劑係藉由光線而觸媒性地起作用,所以即便與環氧樹脂混合,保存安定性和作業性亦優越。 The method of using a photocationic polymerization initiator and curing the adhesive by irradiation of an active energy ray can be hardened at room temperature, and the necessity of deformation due to heat resistance or expansion of the optical film is reduced and the film can be made good between the films. The ground connection aspect is advantageous. Further, since the photocationic polymerization initiator acts catalytically by light, it is excellent in storage stability and workability even when mixed with an epoxy resin.

作為光陽離子聚合起始劑,例如能夠舉出芳香族重氮鎓鹽;芳香族錪鹽、芳香族鋶鹽等的鎓鹽;鐵-芳烴錯合物等。 Examples of the photocationic polymerization initiator include an aromatic diazonium salt; an onium salt such as an aromatic onium salt or an aromatic onium salt; and an iron-aromatic hydrocarbon complex.

作為芳香族重氮鎓鹽,例如可舉出苯重氮鎓六氟銻酸鹽、苯重氮鎓六氟磷酸鹽、苯重氮鎓六氟硼酸鹽等。又,作為芳香族錪鹽,例如可舉出二苯基錪肆(五氟苯基)硼酸鹽、二苯基錪六氟磷酸鹽、二苯基錪六氟銻酸鹽、二(4-壬基苯基)錪六氟磷酸鹽等。 Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate. Further, examples of the aromatic onium salt include diphenylphosphonium (pentafluorophenyl) borate, diphenylphosphonium hexafluorophosphate, diphenylphosphonium hexafluoroantimonate, and di(4-anthracene). Phenyl phenyl) hexafluorophosphate and the like.

作為芳香族鋶鹽,例如可舉出三苯基鋶六氟磷酸鹽、三苯基鋶六氟銻酸鹽、三苯基鋶肆(五氟苯基)硼酸鹽、4,4’-雙(二苯基鋶基)二苯基硫醚雙(六氟磷酸鹽)、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫醚雙(六氟 銻酸鹽)、4,4’-雙[二(β-羥基乙氧基)苯基鋶基]二苯基硫醚雙(六氟磷酸鹽)、7-[二(對甲苯甲醯基)鋶基]-2-異丙基硫雜蒽酮(thioxanthone)氟銻酸鹽、7-[二(對甲苯甲醯基)鋶基]-2-異丙基硫雜蒽酮肆(五氟苯基)硼酸鹽、4-苯基羰基-4’-二苯基鋶基-二苯基硫醚六氟磷酸鹽、4-(對第三丁基苯基羰基)-4’-二苯基鋶基-二苯基硫醚六氟銻酸鹽、4-(對第三丁基苯基羰基)-4’-二(對甲苯甲醯基)鋶基-二苯基硫醚肆(五氟苯基)硼酸鹽等。 Examples of the aromatic onium salt include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium (pentafluorophenyl) borate, and 4,4'-bis ( Diphenylmercapto)diphenyl sulfide bis(hexafluorophosphate), 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide bis(hexafluoro) Citrate), 4,4'-bis[bis(β-hydroxyethoxy)phenylindenyl]diphenyl sulfide bis(hexafluorophosphate), 7-[bis(p-tolylmethyl) Thio[an]thiocyanate, 7-[bis(p-tolylmethyl)indolyl]-2-isopropylthioxanthone oxime (pentafluorobenzene) Borate, 4-phenylcarbonyl-4'-diphenylindenyl-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylanthracene Base-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-tolylmethyl) fluorenyl-diphenyl sulfide quinone (pentafluorobenzene) Base) borate and the like.

又,作為鐵-芳烴錯合物,例如可舉出二甲苯-環戊二烯基鐵(II)六氟銻酸鹽、異丙苯-環戊二烯基鐵(II)六氟磷酸鹽、二甲苯-環戊二烯基鐵(II)-參(三氟甲基磺醯基)甲基化物(xylene-cyclopentadienyliron(II))等。 Further, examples of the iron-aromatic complex include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, and Xylene-cyclopentadienyl iron (II)-xyl-cyclopentadienyliron (II) or the like.

該等光陽離子聚合起始劑的市售品係能夠容易地取得,例如各自以商品名的方式能夠舉出「KAYARAD PCI-220」及「KAYARAD PCI-620」(以上係日本化藥(股)製)、「UVI-6990」(Union Carbide公司製)、「ADEKA OPTOMER SP-150」及「ADEKA OPTOMER SP-170」(以上係(股)ADEKA製)、「CI-5102」、「CIT-1370」、「CIT-1682」、「CIP-1866S」、「CIP-2048S」及「CIP-2064S」(以上係日本曹達(股)製)、「DPI-101」、「DPI-102」、「DPI-103」、「DPI-105」、「MPI-103」、「MPI-105」、「BBI-101」、「BBI-102」、「BBI-103」、「BBI-105」、「TPS-101」、「TPS-102」、「TPS-103」、「TPS-105」、「MDS-103」、「MDS-105」、「DTS-102」及「DTS-103」(以 上係MIDORI化學(股)製)、「PI-2074」(Rhodia公司製)等。 Commercially available products of such photo-cationic polymerization initiators can be easily obtained. For example, "KAYARAD PCI-220" and "KAYARAD PCI-620" can be exemplified by the brand names (the above are Japanese chemical companies). System, "UVI-6990" (manufactured by Union Carbide), "ADEKA OPTOMER SP-150" and "ADEKA OPTOMER SP-170" (the above system is manufactured by ADEKA), "CI-5102", "CIT-1370" "CIT-1682", "CIP-1866S", "CIP-2048S" and "CIP-2064S" (above are Japanese Soda Co., Ltd.), "DPI-101", "DPI-102", "DPI" -103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101" "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", "DTS-102" and "DTS-103" The above system is MIDORI Chemical Co., Ltd., and "PI-2074" (manufactured by Rhodia Co., Ltd.).

光陽離子聚合起始劑係可單獨只有使用1種,亦可混合2種以上而使用。其中,芳香族鋶鹽因為即便在300nm以上的波長區域亦具有紫外線吸收特性,所以硬化性優越,能夠提供具有良好的機械強度和接著強度之硬化物而適合使用。 The photocationic polymerization initiator may be used alone or in combination of two or more. Among them, the aromatic onium salt has ultraviolet light absorption characteristics even in a wavelength region of 300 nm or more, and therefore has excellent curability, and can be suitably used because it can provide a cured product having good mechanical strength and adhesion strength.

光陽離子聚合起始劑的調配量,係相對於100重量份的環氧樹脂,通常為0.5至20重量份,以1重量份以上為佳,又,較佳為15重量份以下。光陽離子聚合起始劑的調配量係相對於100重量份的環氧樹脂,低於0.5重量份時,硬化變得不充分,致使機械強度、接著強度有低落之傾向。又,光陽離子聚合起始劑的調配量係相對於100重量份的環氧樹脂,大於20重量份時,由於硬化物中的離子性物質増加,致使硬化物的吸濕性變高,而有耐久性能低落之可能性。 The compounding amount of the photocationic polymerization initiator is usually 0.5 to 20 parts by weight, more preferably 1 part by weight or more, and still more preferably 15 parts by weight or less based on 100 parts by weight of the epoxy resin. When the amount of the photo-cationic polymerization initiator is less than 0.5 part by weight based on 100 parts by weight of the epoxy resin, the curing is insufficient, and the mechanical strength and the subsequent strength tend to be low. Further, the amount of the photocationic polymerization initiator is more than 20 parts by weight based on 100 parts by weight of the epoxy resin, and the ionic substance in the cured product is increased, so that the hygroscopic property of the cured product becomes high, and The possibility of low durability.

使用光陽離子聚合起始劑時,硬化性環氧樹脂組成物係按照必要而能夠進一步含有光増感劑。藉由使用光増感劑,陽離子聚合的反應性提升,能夠使硬化物的機械強度和接著強度提升。作為光増感劑,例如,可舉出羰基化合物、有機硫化合物、過硫化物、氧化還原系化合物、偶氮及重氮化合物、鹵素化合物、光還原性色素等。 When a photocationic polymerization initiator is used, the curable epoxy resin composition can further contain a photosensitizer as needed. By using a photosensitizer, the reactivity of the cationic polymerization is improved, and the mechanical strength and the bonding strength of the cured product can be improved. Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo and a diazo compound, a halogen compound, and a photoreductive dye.

舉出光増感劑之更具體的例子時,例如,有苯偶姻甲基醚、苯偶姻異丙基醚、及α,α-二甲氧基-α-苯基苯乙酮等的苯偶姻衍生物;二苯基酮、2,4-二氯二苯 基酮、鄰苯甲醯基苯甲酸甲酯、4,4’-雙(二甲胺基)二苯基酮、及4,4’-雙(二乙胺基)二苯基酮等的二苯基酮衍生物;2-氯硫雜蒽酮、及2-異丙基硫雜蒽酮等的硫雜蒽酮衍生物;2-氯蒽醌、及2-甲基蒽醌等的蒽醌衍生物;N-甲基吖啶酮、及N-丁基吖啶酮等的吖啶酮衍生物;以及α,α-二乙氧基苯乙酮、苄基、茀酮、氧雜蒽酮、鈾化合物(uranyl compounds)、鹵素化合物等。光増感劑係可單獨只有使用1種,亦可併用2種以上。光増感劑係在硬化性環氧樹脂組成物100重量份中,以在0.1至20重量份的範圍內含有為佳。 More specific examples of the photosensitizer include, for example, benzoin methyl ether, benzoin isopropyl ether, and α,α-dimethoxy-α-phenylacetophenone. Benzoin derivatives; diphenyl ketone, 2,4-dichlorodiphenyl a ketone, a methyl phthalate, a 4,4'-bis(dimethylamino)diphenyl ketone, and a 4,4'-bis(diethylamino)diphenyl ketone a phenyl ketone derivative; a thioxanthone derivative such as 2-chlorothiazinone or 2-isopropyl thioxanthone; a hydrazine such as 2-chloroindole or 2-methylindole; a derivative; an acridone derivative such as N-methylacridone or N-butylacridone; and α,α-diethoxyacetophenone, benzyl, anthrone, xanthone , uranyl compounds, halogen compounds, and the like. The photosensor may be used alone or in combination of two or more. The photosensitizer is preferably contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the curable epoxy resin composition.

在接著劑所含有的環氧樹脂,係藉由光陽離子聚合來硬化,但是亦可藉由光陽離子聚合及熱陽離子聚合兩者來硬化。後者的情況,以併用光陽離子聚合起始劑及熱陽離子聚合起始劑為佳。 The epoxy resin contained in the adhesive is cured by photocationic polymerization, but it can be cured by both photocationic polymerization and thermal cationic polymerization. In the latter case, a photocationic polymerization initiator and a thermal cationic polymerization initiator are preferably used in combination.

作為熱陽離子聚合起始劑,能夠舉出苄基鋶鹽、噻吩鎓鹽、四氫噻吩鎓、苄基銨、吡啶鎓鹽、肼鎓鹽、羧酸酯、磺酸酯、胺醯亞胺(aminimide)等。該等熱陽離子聚合起始劑係能夠容易地以市售品的方式取得,例如,任一者均是以商品名的方式,可舉出「ADEKAOPTON CP77」及「ADEKAOPTON CP66」(以上係ADEKA股份公司製)、「CI-2639」及「CI-2624」(以上係日本曹達股份公司製)、「SANEIDO SI-60L」、「SANEIDO SI-80L」及「SANEIDO SI-100L」(以上係三新化學工業股份公司製)等。 Examples of the thermal cationic polymerization initiator include a benzyl sulfonium salt, a thiophene sulfonium salt, a tetrahydrothiophene hydrazine, a benzylammonium salt, a pyridinium salt, a phosphonium salt, a carboxylic acid ester, a sulfonic acid ester, and an amine quinone imide ( Aminimide) and so on. These thermal cationic polymerization initiators can be easily obtained as commercially available products. For example, any of them is a brand name, and "ADEKAOPTON CP77" and "ADEKAOPTON CP66" (the above are ADEKA shares) Company system), "CI-2639" and "CI-2624" (above is made by Japan Soda Co., Ltd.), "SANEIDO SI-60L", "SANEIDO SI-80L" and "SANEIDO SI-100L" Chemical Industry Co., Ltd.).

活性能量線硬化型接著劑亦可進一步含有 氧雜環丁烷類、多元醇類等促進陽離子聚合之化合物。 The active energy ray-curable adhesive may further contain A compound which promotes cationic polymerization such as oxetane or polyol.

氧雜環丁烷類係在分子內具有4員環醚之化合物,例如,可舉出3-乙基-3-羥甲基氧雜環丁烷、1,4-雙[(3-乙基-3-氧雜環丁烷基)甲氧基甲基]苯、3-乙基-3-(苯氧基甲基)氧雜環丁烷、二[(3-乙基-3-氧雜環丁烷基)甲基]醚、3-乙基-3-(2-乙基己氧基甲基)氧雜環丁烷、苯酚酚醛清漆氧雜環丁烷等。該等的氧雜環丁烷類係能夠容易地以市售品的方式取得,例如,任一者均是以商品名的方式,能夠舉出「ARON OXETANE OXT-101」、「ARON OXETANE OXT-121」、「ARON OXETANE OXT-211」、「ARON OXETANE OXT-221」及「ARON OXETANE OXT-212」(以上,東亞合成(股)製)等。該等氧雜環丁烷類係在硬化性環氧樹脂組成物中,通常為5至95重量%,較佳是以30至70重量%的比率含有。 The oxetane is a compound having a 4-membered cyclic ether in the molecule, and examples thereof include 3-ethyl-3-hydroxymethyloxetane and 1,4-bis[(3-ethyl) 3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, bis[(3-ethyl-3-oxa) Cyclobutane)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, phenol novolac oxetane, and the like. The oxetane type can be easily obtained as a commercially available product. For example, any one of them is a brand name, and "ARON OXETANE OXT-101" and "ARON OXETANE OXT-" can be mentioned. 121", "ARON OXETANE OXT-211", "ARON OXETANE OXT-221" and "ARON OXETANE OXT-212" (above, East Asia Synthetic Co., Ltd.). These oxetane are usually contained in the curable epoxy resin composition in an amount of from 5 to 95% by weight, preferably from 30 to 70% by weight.

作為多元醇類,係以不存在酚性羥基以外的酸性基者為佳,例如,能夠舉出不具有羥基以外的官能基之多元醇化合物、聚酯多元醇化合物、聚己內酯多元醇化合物、具有酚性羥基之多元醇化合物、聚碳酸酯多元醇等。該等多元醇類的分子量係通常為48以上,較佳為62以上,更佳為100以上,又,較佳為1,000以下。該等多元醇類係在硬化性環氧樹脂組成物中、通常為50重量%以下,較佳是以30重量%以下的比率含有。 The polyol is preferably an acidic group other than a phenolic hydroxyl group, and examples thereof include a polyol compound having no functional group other than a hydroxyl group, a polyester polyol compound, and a polycaprolactone polyol compound. A polyol compound having a phenolic hydroxyl group, a polycarbonate polyol, or the like. The molecular weight of the polyols is usually 48 or more, preferably 62 or more, more preferably 100 or more, and still more preferably 1,000 or less. These polyols are usually contained in the curable epoxy resin composition in an amount of 50% by weight or less, preferably 30% by weight or less.

活性能量線硬化型接著劑係能夠進一步調配離子捕捉劑、抗氧化劑、鏈轉移劑、黏著賦予劑、熱可 塑性樹脂、填充劑、流動調整劑、調平劑、塑化劑、消泡劑等的添加劑。作為離子捕集劑,可舉出粉末狀的鉍系、銻系、鎂系、鋁系、鈣系、鈦系及該等的混合系等的無機化合物,作為抗氧化劑,可舉出受阻酚系抗氧化劑等。 The active energy ray-curable adhesive can further prepare an ion trapping agent, an antioxidant, a chain transfer agent, an adhesion-imparting agent, and a heat-receiving agent. Additives such as plastic resins, fillers, flow regulators, leveling agents, plasticizers, defoamers, and the like. Examples of the ion trapping agent include inorganic compounds such as powdered lanthanoid, lanthanide, magnesium, aluminum, calcium, titanium, and such mixed systems. Examples of the antioxidant include hindered phenolic compounds. Antioxidants, etc.

活性能量線硬化型接著劑,係能夠以實質上不含有溶劑成分的無溶劑型接著劑的方式使用,但因為各塗布方式係有其各自最適合的黏度範圍,所以亦可使其含有用以調整黏度之溶劑。作為溶劑,以使用不會使光學薄膜的光學性能降低且能夠使環氧樹脂組成物等良好地溶解者為佳,例如,能夠舉出以甲苯為代表之烴類;及以乙酸乙酯為代表之酯類等的有機溶劑。在本發明所使用之活性能量線硬化型接著劑的黏度,係例如5至1000mPa.s左右的範圍,以10至200mPa.s為佳,較佳為20至100mPa.s。 The active energy ray-curable adhesive can be used as a solventless adhesive which does not substantially contain a solvent component. However, since each coating method has its most suitable viscosity range, it may be used to contain Adjust the viscosity of the solvent. The solvent is preferably used in order to reduce the optical performance of the optical film and to dissolve the epoxy resin composition or the like. For example, a hydrocarbon represented by toluene may be mentioned; and An organic solvent such as an ester. The viscosity of the active energy ray-curable adhesive used in the present invention is, for example, 5 to 1000 mPa. The range around s, from 10 to 200 mPa. s is preferred, preferably 20 to 100 mPa. s.

以下,針對製造積層膜之實施形態,使用圖式而詳細地說明。 Hereinafter, an embodiment for producing a laminated film will be described in detail using a drawing.

(實施形態1) (Embodiment 1)

在本實施形態,積層膜係由1片光學薄膜及2片透明薄膜所製造。而且,在前述接著劑塗布步驟,係各自在2片前述透明薄膜的一面塗布前述接著劑,在前述貼合步驟,係在前述光學薄膜的兩面與2片前述透明薄膜的前述接著劑以相接的方式積層而成之狀態下,藉由在前述一對貼合輥之間將前述光學薄膜及前述透明薄膜夾住而互相貼合。 In the present embodiment, the laminated film is produced from one optical film and two transparent films. Further, in the adhesive application step, the adhesive is applied to one surface of each of the two transparent films, and the bonding step is performed on the both surfaces of the optical film and the adhesive of the two transparent films. In a state in which the layers are laminated, the optical film and the transparent film are sandwiched between the pair of bonding rolls to bond each other.

其次,邊參照圖式邊說明本實施形態的製造方法。第1圖係顯示使用本實施形態的製造方法之裝置全體的構成之示意圖。 Next, the manufacturing method of this embodiment will be described with reference to the drawings. Fig. 1 is a schematic view showing the configuration of the entire apparatus using the manufacturing method of the embodiment.

在第1圖所顯示之積層膜的製造裝置,係沿著搬運方向依照順序設置:接著劑塗布裝置11、12,其係用以在透明薄膜2、3的一面塗布接著劑;貼合輥(夾輥)51、52,其係用以將透明薄膜2、3與光學薄膜1貼合而得到積層體4;輥筒13,其係用以使在積層體4之透明薄膜2、3與光學薄膜1密著;第1活性能量線照射裝置14、15,其係設置在與該輥筒13的外周面相對之設置;第2以後的活性能量線照射裝置16至18,其相較於第1活性能量線照射裝置14、15,係設置在搬運方向之更下游側;以及搬運用夾輥19。 The apparatus for manufacturing a laminated film shown in Fig. 1 is provided in order along the conveyance direction: an adhesive application device 11 and 12 for applying an adhesive to one surface of the transparent films 2 and 3; and a bonding roller ( Clamping rolls 51, 52 for bonding the transparent films 2, 3 to the optical film 1 to obtain a laminated body 4; a roll 13 for making the transparent films 2, 3 and the optical body in the laminated body 4 The film 1 is adhered to each other; the first active energy ray irradiation devices 14 and 15 are provided to face the outer circumferential surface of the roller 13; and the second and subsequent active energy ray irradiation devices 16 to 18 are compared with the first The active energy ray irradiation devices 14 and 15 are disposed on the downstream side in the conveyance direction, and the nip roller 19 for conveyance.

首先,在從被捲繞成為捲物狀之狀態下連續地被捲出之透明薄膜2、3的一面,藉由接著劑塗布裝置11、12,塗布活性能量線硬化型接著劑<接著劑塗布步驟>。 First, an active energy ray-curable adhesive <adhesive coating is applied to one surface of the transparent films 2 and 3 which are continuously wound up in a state of being wound into a roll shape by the adhesive application devices 11 and 12. Step>.

然後,塗布有接著劑之透明薄膜2、3係透過接著劑而被積層在從被捲繞成為捲物狀之狀態續地被捲出之光學薄膜1的兩面,在其等係被夾住在往搬運方向旋轉之一對貼合輥51、52之間之狀態下,藉由將至少一方的貼合輥往他方的貼合輥方向推壓而將光學薄膜1與透明薄膜2、3貼合,來形成積層體4<貼合步驟>。 Then, the transparent films 2 and 3 coated with the adhesive are laminated on both surfaces of the optical film 1 which is continuously wound up from the state of being wound into a roll, and are sandwiched therebetween. In a state where one of the pair of bonding rollers 51 and 52 is rotated in the conveyance direction, the optical film 1 is bonded to the transparent films 2 and 3 by pressing at least one of the bonding rollers in the direction of the bonding roller. To form a laminate 4 <a bonding step>.

其次,在邊使該積層體4密著在輥筒13的外周面邊搬運之過程,從第1活性能量線照射裝置14、15 朝向輥筒13的外周面照射活性能量線來使接著劑聚合硬化<活性能量線照射步驟>。 Next, the first active energy ray irradiation device 14 and 15 are transported while the laminated body 4 is placed on the outer peripheral surface of the roll 13 while being adhered thereto. The outer peripheral surface of the roller 13 is irradiated with an active energy ray to cure the adhesive polymerization <active energy ray irradiation step>.

又,被配置在搬運方向下游側之第2以後的活性能量線照射裝置16至18,係用以使接著劑完全地聚合硬化之裝置,能夠視需要而追加/省略。最後,積層體4係通過搬運用夾輥19而被捲取在輥20作為積層膜。以下,詳細地說明各步驟。 In addition, the second and subsequent active energy ray irradiation devices 16 to 18 disposed on the downstream side in the transport direction are devices for completely polymerizing and curing the adhesive, and may be added or omitted as necessary. Finally, the laminated body 4 is wound up on the roll 20 as a laminated film by the nip roller 19 for conveyance. Hereinafter, each step will be described in detail.

<接著劑塗布步驟> <Binder coating step>

在透明薄膜2、3塗布接著劑之方法係沒有特別限定,例如能夠利用刮刀(doctor blade)、繞線棒、模塗布機(die coater)、刮刀式塗布機(comma coater)、凹版塗布機等各種的塗布方式。其中,考慮薄膜塗布、通過線(pass line)的自由度、對廣闊寬度的適應等時,作為接著劑塗布裝置11、12,係以凹版輥為佳。 The method of applying the adhesive to the transparent films 2 and 3 is not particularly limited, and for example, a doctor blade, a wire bar, a die coater, a comma coater, a gravure coater, or the like can be used. Various coating methods. Among them, in consideration of film coating, degree of freedom of pass line, adaptation to a wide width, etc., it is preferable to use a gravure roll as the adhesive application devices 11 and 12.

使用凹版輥作為接著劑塗布裝置11、12而進行塗布接著劑時,被塗布的接著劑之厚度(塗布厚度),係以約0.1至10μm為佳,較佳為0.2μm至4μm。接著劑的塗布厚度係能夠藉由凹版輥的速度對透明薄膜的生產線速度之比(亦即拉伸比)來調整。通常係藉由將拉伸比(凹版輥的速度/生產線速度)調整為0.5至10,能夠將接著劑的塗布厚度調整為約0.1至10μm。更具體地,能夠藉由將透明薄膜2、3的生產線速度設為10至100m/分鐘,使凹版輥在與透明薄膜2、3的搬運方向相反方向地旋轉,且將凹版輥的速度設為5至1000m/分鐘,能夠將接著劑的塗 布厚度調整為約0.1至10μm。 When the adhesive is applied as the adhesive application means 11 and 12 by using the gravure roll, the thickness (coating thickness) of the applied adhesive is preferably from about 0.1 to 10 μm, preferably from 0.2 μm to 4 μm. The coating thickness of the subsequent agent can be adjusted by the ratio of the speed of the gravure roll to the production line speed of the transparent film (i.e., the draw ratio). The coating thickness of the adhesive can be adjusted to about 0.1 to 10 μm by adjusting the draw ratio (speed of the gravure roll/line speed) to 0.5 to 10. More specifically, by setting the production linear velocity of the transparent films 2, 3 to 10 to 100 m/min, the gravure roll can be rotated in the opposite direction to the conveyance direction of the transparent films 2, 3, and the speed of the gravure roll can be set to 5 to 1000 m / min, capable of coating the adhesive The cloth thickness is adjusted to be about 0.1 to 10 μm.

接著劑係在調製後,通常是在15至40℃的範圍內之預定溫度±5℃(例如預定溫度為30℃時,30℃±5℃),以±3℃為佳,較佳是在經調整為±1℃的環境下塗布。 The subsequent agent is usually prepared at a predetermined temperature within a range of 15 to 40 ° C ± 5 ° C (for example, 30 ° C ± 5 ° C when the predetermined temperature is 30 ° C), preferably ± 3 ° C, preferably in It is coated in an environment adjusted to ±1 °C.

<貼合步驟> <Fitting step>

在本步驟,藉由上述步驟而塗布有接著劑之透明薄膜2、3係透過接著劑而被積層在從被捲繞成為捲物狀之狀態續地被捲出之光學薄膜1的兩面。在搬運方向旋轉之一對貼合輥51、52之間夾住該積層體之狀態下,例如藉由在貼合輥52的方向推壓貼合輥51,而將光學薄膜1與透明薄膜2、3貼合來形成積層體4。 In this step, the transparent films 2 and 3 to which the adhesive is applied by the above-described steps are passed through the adhesive and laminated on both surfaces of the optical film 1 which is continuously wound up from the state of being wound into a roll. In a state in which the laminated body is sandwiched between the pair of bonding rollers 51 and 52 in the conveyance direction, the optical film 1 and the transparent film 2 are pressed by, for example, pressing the bonding roller 51 in the direction of the bonding roller 52. And 3 are bonded together to form the laminated body 4.

又,第1圖係顯示將接著劑均勻地塗布在透明薄膜2、3的一面,將光學薄膜1重疊在透明薄膜2、3之塗布有接著劑的面且使用貼合輥51、52進行貼合之方法,但是亦可以將接著劑均勻地塗布在光學薄膜1的兩面,將透明薄膜2、3重疊在光學薄膜1之塗布有接著劑的面且使用貼合輥51、52進行貼合。 Moreover, the first figure shows that the adhesive agent is uniformly applied to one surface of the transparent films 2 and 3, and the optical film 1 is superposed on the surface of the transparent films 2 and 3 coated with the adhesive, and is pasted using the bonding rolls 51 and 52. Although the method is combined, the adhesive may be uniformly applied to both surfaces of the optical film 1, and the transparent films 2 and 3 may be superposed on the surface of the optical film 1 coated with the adhesive and bonded using the bonding rolls 51 and 52.

藉由推壓而被施加在積層體之壓力,係沒有特別限定,使用金屬製輥及橡膠製輥時,在富士軟片製二片式感壓紙(Two-sheet type prescale)之瞬間壓力,係以0.2至3.0MPa為佳,較佳為0.5至2.3MPa。對該貼合輥之推壓的外力,係通常被施加在貼合輥的兩端之軸承構件。 The pressure applied to the laminated body by pressing is not particularly limited, and when a metal roll or a rubber roll is used, the pressure at the instant of the two-sheet type prescale of Fujifilm is It is preferably 0.2 to 3.0 MPa, more preferably 0.5 to 2.3 MPa. The external force to which the bonding roller is pressed is a bearing member that is usually applied to both ends of the bonding roller.

一對貼合輥係可以是一方的貼合輥與另一方的貼合輥之周速度有所差異。例如,在積層體4之貼合 液晶面板的面側所設置的貼合輥(第1貼合輥)的周速度係相較於相反側的貼合輥(第2貼合輥)之周速度,以較快者為佳。藉此,所得到的積層膜為偏光板時,能夠提供偏光板之貼合液晶面板的面為凸起,且其相反側的面為凹下之卷曲(正卷曲)。在所得到的偏光板,賦予被貼合在液晶面板的面為凹下,且其相反側的面為凸起之卷曲(逆卷曲)時,將偏光板貼合在液晶胞時,在中央部變得容易產生咬進氣泡等的缺陷。又,此時,以使用金屬製輥作為第1貼合輥且使用橡膠製輥作為第2貼合輥為佳。 The pair of bonding rolls may have a difference in the peripheral speed of one of the bonding rolls and the other of the bonding rolls. For example, the bonding of the laminated body 4 The peripheral speed of the bonding roller (first bonding roller) provided on the surface side of the liquid crystal panel is preferably faster than the circumferential speed of the bonding roller (second bonding roller) on the opposite side. Therefore, when the obtained laminated film is a polarizing plate, the surface of the polarizing plate to which the liquid crystal panel is bonded can be convex, and the surface on the opposite side is concave (positive curl). In the obtained polarizing plate, when the surface to be bonded to the liquid crystal panel is recessed and the surface on the opposite side is a convex curl (reverse curl), the polarizing plate is bonded to the liquid crystal cell at the center portion. It becomes easy to cause defects such as biting bubbles. Moreover, in this case, it is preferable to use a metal roll as the first bonding roll and a rubber roll as the second bonding roll.

而且,將第2貼合輥的周速度設為1時,第1貼合輥的周速度比係以1.0050至1.0200為較佳。第1貼合輥的周速度比該範圍更快時,因為正卷曲的卷曲量係變得太大,將偏光板貼合在液晶胞時,在端部容易產生咬進氣泡等的缺陷,而且被放置在嚴酷的環境下時,進一進助長正卷曲,致使偏光板的端部有從液晶胞剝落之可能性。 Further, when the peripheral speed of the second bonding roller is 1, the peripheral speed ratio of the first bonding roller is preferably from 1.050 to 1.0200. When the circumferential speed of the first bonding roll is faster than the range, the amount of crimping of the positive curl becomes too large, and when the polarizing plate is attached to the liquid crystal cell, defects such as biting bubbles are likely to occur at the end portion, and When placed in a harsh environment, the feed length is curled, causing the end of the polarizing plate to peel off from the liquid crystal cell.

輥筒13之外周面係構成經鏡面拋光的凸曲面,邊在其表面使積層體4密著邊進行搬運,在其過程,藉由活性能量線照射裝置14、15使接著劑聚合硬化。就藉由使接著劑聚合硬化且使其充分地密著在積層體4而言,輥筒13的直徑係沒有特別限定。接著劑為未硬化狀態之積層體4,係以通過輥筒13之期間的累計光量為10mJ/cm2以上的方式照射活性能量線為佳。輥筒13係可使其對積層體4的生產線移的移動進行從動或旋轉驅動,或者亦可使其固定而以積層體4在表面滑行的方式進行。又,藉由照 射活性能量線來聚合硬化時,為了使在積層體4所產的熱散熱,亦可使輥筒13具有作為冷卻輥之作用。此時,冷卻輥的表面溫度係以被設定在20至30℃為佳。 The outer peripheral surface of the drum 13 constitutes a mirror-polished convex curved surface, and the laminated body 4 is conveyed while being adhered to the surface thereof. In the process, the adhesive is polymerized and hardened by the active energy ray irradiation devices 14 and 15. The diameter of the roll 13 is not particularly limited as long as the adhesive is polymerized and hardened and sufficiently adhered to the laminated body 4. Adhesive is uncured state of the layered body 4, the amount of light integrated by the system to the roller 13 during the above manner is 2 10mJ / cm active energy rays is preferred. The roller 13 is configured to be driven or rotationally driven by the movement of the production line of the laminated body 4, or it may be fixed so that the laminated body 4 is slid on the surface. Further, when the polymer is hardened by irradiation with an active energy ray, the roller 13 may function as a cooling roller in order to dissipate heat generated in the laminated body 4. At this time, the surface temperature of the cooling roll is preferably set to 20 to 30 °C.

(實施形態2) (Embodiment 2)

在本實施形態,積層膜係由1片光學薄膜及1片透明薄膜所製造。而且,在前述接著劑塗布步驟,在前述透明薄膜的一面塗布前述接著劑,在前述貼合步驟,在前述光學薄膜的一面與前述透明薄膜的前述接著劑以相接的方式積層之狀態下,藉由在前述一對貼合輥之間將前述光學薄膜及前述透明薄膜夾住而互相貼合。 In the present embodiment, the laminated film is produced from one optical film and one transparent film. Further, in the adhesive application step, the adhesive is applied to one surface of the transparent film, and in the bonding step, in a state in which one surface of the optical film and the adhesive of the transparent film are laminated in contact with each other, The optical film and the transparent film are sandwiched between the pair of bonding rolls to be bonded to each other.

其次,邊參照圖式邊說明本實施形態的製造方法。第2圖係顯示在本實施形態的製造方法所使用的裝置全體構成之示意圖。 Next, the manufacturing method of this embodiment will be described with reference to the drawings. Fig. 2 is a schematic view showing the overall configuration of a device used in the manufacturing method of the embodiment.

在第2圖所顯示之積層膜的製造裝置,係沿著搬運方向依照順序設置:接著劑塗布裝置11,其係用以在透明薄膜2一面塗布接著劑;貼合輥(夾輥)51、52,其係用以將透明薄膜2與光學薄膜1貼合而得到積層體4;輥筒13,其係用以使在積層體4之透明薄膜2與光學薄膜1密著;第1活性能量線照射裝置14、15,其係設置在與該輥筒13的外周面相對之設置;第2以後的活性能量線照射裝置16至18,其相較於第1活性能量線照射裝置14、15,係設置在搬運方向之更下游側;以及搬運用夾輥19。 The apparatus for manufacturing a laminated film shown in Fig. 2 is provided in order along the conveyance direction: an adhesive application device 11 for applying an adhesive to one side of the transparent film 2; a bonding roll (nip roll) 51, 52, which is used to bond the transparent film 2 and the optical film 1 to obtain a laminated body 4; a roll 13 for adhering the transparent film 2 of the laminated body 4 to the optical film 1; the first active energy The line irradiation devices 14 and 15 are provided to face the outer circumferential surface of the roller 13; the second and subsequent active energy ray irradiation devices 16 to 18 are compared with the first active energy ray irradiation devices 14 and 15 It is provided on the downstream side of the conveyance direction; and the conveyance nip roller 19.

首先,在從被捲繞成為捲物狀之狀態下,連續地被捲出之透明薄膜2的一面,藉由接著劑塗布裝置 11,塗布活性能量線硬化型接著劑<接著劑塗布步驟>。 First, one side of the transparent film 2 which is continuously wound up in a state of being wound into a roll shape, by means of an adhesive application device 11. Coating active energy ray-curable adhesive <adhesive coating step>.

然後,塗布有接著劑之透明薄膜2係透過接著劑而被積層在從被捲繞成為捲物狀之狀態續地被捲出之光學薄膜1的一面,在其等係被夾住在往搬運方向旋轉之一對貼合輥51、52之間之狀態下,藉由將至少一方的貼合輥往他方的貼合輥方向推壓而將光學薄膜1與透明薄膜2貼合,來形成積層體4<貼合步驟>。 Then, the transparent film 2 coated with the adhesive is laminated on the side of the optical film 1 which is continuously wound up from the state of being wound into a roll, and is sandwiched and carried by the adhesive film 2 In a state in which one of the direction rotations is between the bonding rollers 51 and 52, the optical film 1 and the transparent film 2 are bonded together by pressing at least one bonding roller in the direction of the bonding roller, thereby forming a laminate. Body 4 <Finishing step>.

其次,在邊使該積層體4密著在輥筒13的外周面邊搬運之過程,從第1活性能量線照射裝置14、15朝向輥筒13的外周面照射活性能量線來使接著劑聚合硬化<活性能量線照射步驟>。 Then, while the laminated body 4 is conveyed while being adhered to the outer peripheral surface of the roll 13, the active energy lines are irradiated from the first active energy ray irradiation devices 14 and 15 toward the outer peripheral surface of the roll 13 to polymerize the adhesive. Hardening <Active Energy Ray Irradiation Step>.

又,被配置在搬運方向下游側之第2以後的活性能量線照射裝置16至18,係用以使接著劑完全地聚合硬化之裝置,能夠按照必要而追加/省略。針對各步驟的詳細,因為係與實施形態1同樣,故而省略。 In addition, the second or subsequent active energy ray irradiation devices 16 to 18 disposed on the downstream side in the conveyance direction are devices for completely polymerizing and curing the adhesive, and can be added or omitted as necessary. Since the details of each step are the same as those of the first embodiment, they are omitted.

[實施例] [Examples]

以下,舉出實施例而更詳細地說明本發明,但是本發明係不限定於該等實施例。 Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

<實施例1> <Example 1>

在本實施例,係使用如在上述實施形態2所說明的第2圖之裝置,來製造2片薄膜貼合而成之積層膜。 In the present embodiment, a laminate film in which two sheets of film are bonded is produced by using the apparatus shown in Fig. 2 described in the second embodiment.

準備厚度60μm的環烯烴系樹脂薄膜「ZEONOR(ZEONOR)」(日本ZEON(股)製)、厚度80μm的 三乙酸纖維素薄膜「KC8UX2MW」(Konica Minolta公司製)。使用東京精密(股)製「Handysurf E35A」測定環烯烴系樹脂薄膜的表面粗糙度(Rz)時,為30nm。又,該值係將測定距離設定為12.5mm,將上述測定裝置載置在對象薄膜而測定表面粗糙度10次時所得之平均值。 A cycloolefin resin film "ZEONOR (ZEONOR)" (manufactured by Japan ZEON Co., Ltd.) having a thickness of 60 μm and a thickness of 80 μm were prepared. Cellulose triacetate film "KC8UX2MW" (manufactured by Konica Minolta Co., Ltd.). When the surface roughness (Rz) of the cycloolefin-based resin film was measured by "Handysurf E35A" manufactured by Tokyo Seimi Co., Ltd., it was 30 nm. In addition, this value is an average value obtained by setting the measurement distance to 12.5 mm, and measuring the surface roughness of the target film by 10 times.

在三乙酸纖維素薄膜的一面,使用接著劑塗布裝置塗布紫外線硬化型接著劑之環氧樹脂組成物「KR-70T」(ADEKA公司製、黏度:44mPa.s)。此時,將在接著劑塗布裝置之薄膜積層體的生產線速度設為25m/分鐘,使凹版輥與積層材的搬運方向相反方向地旋轉,且以厚度成為2.0μm的方式塗布接著劑(又,硬化後的接著劑之厚度係2.0μm)。 An epoxy resin composition "KR-70T" (manufactured by Adeka Co., Ltd., viscosity: 44 mPa.s) of an ultraviolet curable adhesive was applied to one surface of the cellulose triacetate film using an adhesive coating apparatus. At this time, the production line speed of the film laminate in the adhesive application device was set to 25 m/min, and the gravure roll was rotated in the opposite direction to the conveyance direction of the laminate, and the adhesive was applied so as to have a thickness of 2.0 μm (again, The thickness of the cured adhesive was 2.0 μm).

其次,以直徑均為250mm之一對夾輥(貼合輥)夾住與在三乙酸纖維素薄膜所塗布的接著劑以相接的方式積層有環烯烴系樹脂薄膜之積層體,且藉由以1.0MPa的壓力推壓,而使上述環烯烴系樹脂薄膜與上述三乙酸纖維素薄膜貼合。 Next, a laminate of a cycloolefin-based resin film is laminated on the nip roll (bonding roll) with a nip roller (bonding roll) in a manner of being attached to the film coated with the cellulose triacetate film, and by laminating The cycloolefin-based resin film was bonded to the cellulose triacetate film by pressing at a pressure of 1.0 MPa.

將貼合有上述2種的薄膜之積層體,邊在長度方向施加600N/m的張力邊以生產線速度25m/分鐘移送,且對積層體照射總累計光量(在波長280至320nm的波長區域之光照射強度的累計量)為約250mJ/cm2(測定器:使用FusionUV公司製UV Power PuckII之測定值)之紫外線(UVB),而得到積層膜。 The laminate of the above-mentioned two kinds of thin films was transferred while being applied with a tension of 600 N/m in the longitudinal direction at a production linear velocity of 25 m/min, and the laminated body was irradiated with a total integrated light amount (in a wavelength region of a wavelength of 280 to 320 nm). The cumulative amount of light irradiation intensity was about 250 mJ/cm 2 (measuring device: measured using UV Power Puck II manufactured by FusionUV Co., Ltd.) ultraviolet rays (UVB) to obtain a laminated film.

針對所得到的積層膜,在薄膜之間藉由目 視無法觀察到氣泡。 For the obtained laminated film, between the films by the mesh No bubbles can be observed.

<實施例2> <Example 2>

在本實施例,係使用如第3圖的裝置來製造2片薄膜貼合而成之積層膜。在第3圖所顯示的裝置,係在上述實施形態2已說明之第2圖所顯示的裝置,將冷卻輥筒13等省略者,詳細說明係省略。又,在第3圖之參照符號,係以與第2圖相同意思使用。 In the present embodiment, a laminate film in which two sheets of film were bonded was produced by using the apparatus shown in Fig. 3. The apparatus shown in Fig. 3 is the apparatus shown in Fig. 2 described in the second embodiment, and the cooling roller 13 and the like are omitted, and detailed description thereof will be omitted. In addition, the reference numerals in Fig. 3 are used in the same meaning as in Fig. 2.

準備厚度40μm的三乙酸纖維素薄膜「KC4CR-1」(Konica Minolta公司製)及厚度135μm的複合薄膜積層體。使用東京精密製「Handysurf E35A」測定KC4CR-1的表面粗糙度(Rz)時,為50nm。又,該值係將測定距離設定為12.5mm,將上述測定裝置載置在對象薄膜而測定表面粗糙度10次時所得之平均值。 A cellulose triacetate film "KC4CR-1" (manufactured by Konica Minolta Co., Ltd.) having a thickness of 40 μm and a composite film laminate having a thickness of 135 μm were prepared. When the surface roughness (Rz) of KC4CR-1 was measured by Tokyo Precision "Handysurf E35A", it was 50 nm. In addition, this value is an average value obtained by setting the measurement distance to 12.5 mm, and measuring the surface roughness of the target film by 10 times.

在複合薄膜積層體的一面,使用接著劑塗布裝置塗布紫外線硬化型接著劑之環氧樹脂組成物「KR-70T」(ADEKA公司製、黏度:44mPa.s)。此時,將在接著劑塗布裝置之薄膜積層體的生產線速度設為25m/分鐘,使凹版輥與積層材的搬運方向相反方向地旋轉,且以厚度成為1.0μm的方式塗布接著劑(又,硬化後的接著劑之厚度係1.0μm)。 An epoxy resin composition "KR-70T" (manufactured by Adeka Co., Ltd., viscosity: 44 mPa.s) of an ultraviolet curable adhesive was applied to one surface of the composite film laminate using an adhesive coating apparatus. At this time, the production line speed of the film laminate in the adhesive application device was set to 25 m/min, the gravure roll was rotated in the opposite direction to the conveyance direction of the laminate, and the adhesive was applied so as to have a thickness of 1.0 μm (again, The thickness of the cured adhesive was 1.0 μm).

將貼合有上述2種的薄膜之積層體,邊在長度方向施加600N/m的張力邊以生產線速度25m/分鐘移送,且對積層體照射總累計光量(在波長280至320nm的波長區域之光照射強度的累計量)為約250mJ/cm2(測定器:使 用FusionUV公司製UV Power PuckII之測定值)之紫外線(UVB),而得到積層膜。 The laminate of the above-mentioned two kinds of thin films was transferred while being applied with a tension of 600 N/m in the longitudinal direction at a production linear velocity of 25 m/min, and the laminated body was irradiated with a total integrated light amount (in a wavelength region of a wavelength of 280 to 320 nm). The cumulative amount of light irradiation intensity was about 250 mJ/cm 2 (measuring device: measured using UV Power Puck II manufactured by FusionUV Co., Ltd.) ultraviolet rays (UVB) to obtain a laminated film.

針對所得到的積層膜,在薄膜之間藉由目視無法觀察到氣泡。 With respect to the obtained laminated film, bubbles were not observed between the films by visual observation.

<比較例1> <Comparative Example 1>

除了使用表面粗糙度(Rz)為280nm之聚乙烯醇系薄膜(KURARAY製的VINYLON VF-PS#7500、坯膜厚度為75μm)代替環烯烴系薄膜以外,係與實施例1同樣地進行而製造積層膜。針對所得到的積層膜,在薄膜之間藉由目視能夠觀察到氣泡。 A polyvinyl alcohol-based film having a surface roughness (Rz) of 280 nm (VINYLON VF-PS #7500 manufactured by KURARAY, a thickness of a film of 75 μm) was used in the same manner as in Example 1 except that a cycloolefin film was used. Laminated film. With respect to the obtained laminated film, bubbles were observed by visual observation between the films.

從以上的結果,得知在構成積層膜之薄膜,在接著劑塗布步驟,未塗布接著劑的面而在貼合步驟與接著劑相接的面之表面粗糙度為200nm以下之實施例1,氣泡未混入薄膜之間,而使用本發明範圍外的表面粗糙度之薄膜之比較例1,氣泡混入薄膜之間。 From the above results, it is understood that in the film constituting the laminated film, in the adhesive application step, the surface roughness of the surface on which the surface of the adhesive is not applied and the surface where the bonding step is in contact with the adhesive is 200 nm or less is obtained. In Comparative Example 1 in which bubbles were not mixed between the films and the film having a surface roughness outside the range of the present invention was used, bubbles were mixed between the films.

又,在實施例1,作為表面粗糙度為30nm之薄膜,係使用環烯烴系薄膜,而在比較例,作為表面粗糙度為280nm之薄膜,係使用聚乙烯醇系薄膜,這只是為了從市售的薄膜選擇不同表面粗糙度的薄膜而使用了不同材質的薄膜。亦即,認為即便將相同材質的薄膜而只有表面粗糙度不同之薄膜進行比較時,亦能夠觀察到同樣的效果差異。因而,在本發明,構成積層膜之各薄膜,係不被在上述實施例所記載的材質限定,而能夠使用由各種的材質所構成之薄膜來製造積層膜。 Further, in Example 1, a cycloolefin-based film was used as the film having a surface roughness of 30 nm, and a polyvinyl alcohol-based film was used as a film having a surface roughness of 280 nm in the comparative example. The films sold were selected from films of different surface roughness and films of different materials were used. That is, it is considered that even when films of the same material are used and only films having different surface roughness are compared, the same effect difference can be observed. Therefore, in the present invention, the respective films constituting the laminated film are not limited to the materials described in the above embodiments, and a laminated film can be produced using a film composed of various materials.

1‧‧‧光學薄膜 1‧‧‧Optical film

2、3‧‧‧透明薄膜 2, 3‧‧‧ transparent film

4‧‧‧積層體 4‧‧‧Layered body

11、12‧‧‧接著劑塗布裝置 11, 12‧‧‧ adhesive coating device

13‧‧‧輥筒 13‧‧‧ Roller

14、15、16、17、18‧‧‧活性能量線照射裝置 14, 15, 16, 17, 18‧‧‧Active energy line irradiation device

19‧‧‧搬運用夾輥 19‧‧‧Carrying nip rollers

20‧‧‧捲起輥 20‧‧‧Rolling roll

51、52‧‧‧貼合輥 51, 52‧‧‧ affixing rolls

Claims (5)

一種積層膜的製造方法,其係將複數片薄膜透過活性能量線硬化型接著劑互相貼合而成之積層膜的製造方法,其係依照下列順序具備:接著劑塗布步驟,其係在前述複數片薄膜中之至少1片薄膜的一面或兩面,塗布活性能量線硬化型接著劑;貼合步驟,其係在前述接著劑介於相鄰薄膜之間的方式積層而成之狀態下,藉由在朝搬運方向旋轉的一對貼合輥之間將前述複數片薄膜夾住而予以互相貼合;以及活性能量線照射步驟,其係對互相貼合之前述複數片薄膜照射活性能量線,而使前述接著劑硬化;其中,在前述複數片薄膜中,在前述接著劑塗布步驟未塗布前述接著劑的面而在前述貼合步驟成為與前述接著劑相接的面之表面粗糙度為200nm以下。 A method for producing a laminated film, which is a method for producing a laminated film obtained by bonding a plurality of thin films through an active energy ray-curable adhesive, and is provided in the following order: an adhesive application step, which is in the plural An active energy ray-curable adhesive is applied to one or both sides of at least one of the film films; and a bonding step is performed in a state in which the adhesive is laminated between adjacent films. The plurality of sheets of film are sandwiched between the pair of bonding rolls that rotate in the conveying direction to be bonded to each other; and the active energy ray irradiation step irradiates the plurality of sheets of the film to each other with an active energy ray. In the above-mentioned plurality of sheets, the surface of the adhesive is not applied to the surface of the adhesive in the adhesive application step, and the surface of the surface that is in contact with the adhesive in the bonding step has a surface roughness of 200 nm or less. . 如申請專利範圍第1項所述之製造方法,其中,在前述接著劑塗布步驟,所塗布之前述接著劑的厚度為2μm以下。 The production method according to the first aspect of the invention, wherein, in the adhesive application step, the thickness of the adhesive to be applied is 2 μm or less. 如申請專利範圍第1或2項所述之製造方法,其中,前述複數片薄膜係含有光學薄膜及透明薄膜,且前述積層膜係偏光板。 The manufacturing method according to the first or second aspect of the invention, wherein the plurality of sheets of the film comprise an optical film and a transparent film, and the laminated film is a polarizing plate. 如申請專利範圍第3項所述之製造方法,其中,前述複數片薄膜係由1片光學薄膜及2片透明薄膜所構成, 在前述接著劑塗布步驟中,在2片前述透明薄膜各自的一面塗布前述接著劑,在前述貼合步驟中,以2片前述透明薄膜的前述接著劑相接於前述光學薄膜的兩面的方式積層而成之狀態下,藉由在前述一對貼合輥之間將前述光學薄膜及前述透明薄膜夾住而予以互相貼合。 The manufacturing method according to claim 3, wherein the plurality of films are composed of one optical film and two transparent films. In the adhesive application step, the adhesive is applied to one surface of each of the two transparent films, and in the bonding step, the adhesive of the two transparent films is laminated on both surfaces of the optical film. In the formed state, the optical film and the transparent film are sandwiched between the pair of bonding rolls to be bonded to each other. 如申請專利範圍第3項所述之製造方法,其中,前述複數片薄膜係由1片光學薄膜及1片透明薄膜所構成,在前述接著劑塗布步驟中,在前述透明薄膜的一面塗布前述接著劑,在前述貼合步驟中,以前述透明薄膜的前述接著劑相接於前述光學薄膜的一面的方式積層而成之狀態下,藉由在前述一對貼合輥之間將前述光學薄膜及前述透明薄膜夾住而予以互相貼合。 The manufacturing method according to claim 3, wherein the plurality of sheets are composed of one optical film and one transparent film, and in the adhesive application step, the one surface of the transparent film is coated on the surface. In the bonding step, the optical film and the optical film are interposed between the pair of bonding rollers in a state in which the adhesive of the transparent film is laminated on one surface of the optical film. The transparent films are sandwiched and bonded to each other.
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