TWI671554B - Polarizer with less bubble deficiency - Google Patents

Polarizer with less bubble deficiency Download PDF

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TWI671554B
TWI671554B TW103141752A TW103141752A TWI671554B TW I671554 B TWI671554 B TW I671554B TW 103141752 A TW103141752 A TW 103141752A TW 103141752 A TW103141752 A TW 103141752A TW I671554 B TWI671554 B TW I671554B
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film
polarizer
layer
polyvinyl alcohol
resin
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TW201530200A (en
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河村真一
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日商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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/40Adhesives in the form of films or foils characterised by release liners
    • C09J7/401Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14Protective coatings, e.g. hard coatings

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

本發明係提供一種於吸收軸方向的長度為100μm以上的空隙為10個/m2以下之由聚乙烯醇系樹脂所構成之偏光片,於基材膜的至少一側之面,積層該偏光片之偏光性積層膜,於該偏光片的至少一側之面積層有透明保護膜之偏光板,及其製造方法。 The present invention provides a polarizer made of a polyvinyl alcohol-based resin with a length of 100 μm or more in the absorption axis direction and a gap of 10 / m 2 or less. The polarized light is laminated on at least one side of a base film. A polarizing laminated film of a sheet, a polarizing plate having a transparent protective film layered on an area of at least one side of the polarizing plate, and a method for manufacturing the same.

Description

氣泡缺陷少的偏光片 Polarizer with few bubble defects

本發明係關於氣泡缺陷少的偏光片及其製造方法。 The present invention relates to a polarizer with few bubble defects and a method for manufacturing the same.

近年來,偏光板作為液晶顯示裝置之光學元件,被廣泛裝設於液晶電視、行動電話或個人電腦之液晶顯示裝置使用。近來,為了該等液晶顯示裝置之小型化、輕量化,開發有薄型的偏光板。目前為止亦有提案其係在基材膜表面使用聚乙烯醇系樹脂的水溶液設置聚乙烯醇系樹脂層之後,進行延伸,接著染色而製造偏光片及偏光板的方法(專利文獻1及2)。 In recent years, as an optical element of a liquid crystal display device, a polarizing plate is widely used in a liquid crystal display device of a liquid crystal television, a mobile phone, or a personal computer. Recently, in order to reduce the size and weight of these liquid crystal display devices, a thin polarizing plate has been developed. So far, a method has been proposed in which a polyvinyl alcohol-based resin layer is provided on the surface of a base film using an aqueous solution of a polyvinyl alcohol-based resin, followed by stretching and then dyeing to produce polarizers and polarizers (Patent Documents 1 and 2). .

[先前技術文獻] [Prior technical literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開2000-338329號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2000-338329

[專利文獻2]日本特開2009-93074號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2009-93074

本案發明者發現,於製造偏光片及偏光板 之方法中,使用聚乙烯醇系樹脂的水溶液時,聚乙烯醇系樹脂容易在該水溶液的調製步驟中吸入氣泡,在形成聚乙烯醇系樹脂層時,於形成的聚乙烯醇系樹脂層表面會因為氣泡而造成圓形凹狀缺陷,或因為於延伸後的樹脂層之延伸方向產生的楕圓狀或線狀的氣泡缺陷而造成空隙。本發明者係提供一種前述氣泡缺陷所致之空隙少之偏光片及該偏光片所成之偏光性積層膜以及其製造方法。 The inventor of this case found that in manufacturing polarizers and polarizers In the method, when an aqueous solution of a polyvinyl alcohol resin is used, it is easy for the polyvinyl alcohol resin to suck air bubbles in the preparation step of the aqueous solution, and when the polyvinyl alcohol resin layer is formed, the surface of the formed polyvinyl alcohol resin layer is formed. It may cause round concave defects due to air bubbles, or voids due to round or linear air bubble defects generated in the extending direction of the stretched resin layer. The present inventors provide a polarizer having few voids caused by the aforementioned bubble defects, a polarizing laminated film formed by the polarizer, and a method for manufacturing the same.

本發明提供一種偏光片,其係於吸收軸方向的長度為100μm以上的空隙為10個/m2以下之由聚乙烯醇系樹脂所構成者。而且,本發明提供一種於基材膜的至少一側之面,積層該偏光片之偏光性積層膜、及於偏光片的至少單面積層透明保護膜之偏光板。 The present invention provides a polarizer made of a polyvinyl alcohol-based resin having a length of 100 μm or more in the absorption axis direction and 10 or less / m 2 voids. Furthermore, the present invention provides a polarizing plate on which at least one side of the base film is laminated a polarizing laminated film of the polarizer and at least a single-area transparent protective film on the polarizer.

偏光片之於吸收軸方向的長度為100μm以上的空隙為10個/m2以下之偏光性積層膜,典型係以包含以下(a)至(c)之步驟的製造方法來製作。 A polarizing laminated film having a length of 100 μm or more in the absorption axis direction and 10 or less / m 2 voids is typically produced by a manufacturing method including the following steps (a) to (c).

(a)樹脂層形成步驟:於基材膜的至少一側之面,塗裝經減壓脫泡之聚乙烯醇系樹脂的水溶液,得到於基材膜的至少一側之面形成有由聚乙烯醇系樹脂所成之樹脂層的積層膜;(b)延伸步驟:將積層膜延伸而得到延伸膜;(c)染色步驟:將延伸膜之由聚乙烯醇系樹脂所構成之樹脂層以二色性色素染色而形成偏光片層。 (a) Resin layer forming step: coating an aqueous solution of a polyvinyl alcohol-based resin that has been degassed under reduced pressure on at least one side of the base film to obtain a polymer film formed on at least one side of the base film. Laminated film of resin layer made of vinyl alcohol resin; (b) Stretching step: stretch the laminated film to obtain an stretched film; (c) Dyeing step: The resin layer of the stretched film composed of polyvinyl alcohol resin is used to The dichroic pigment is dyed to form a polarizer layer.

本發明提供一種於偏光片的一側之面設有 透明保護膜之偏光板之製造方法,其係包含:於該偏光性積層膜的偏光片層之與基材膜側為相反側之面貼合透明保護膜,而得到多層膜之步驟(貼合步驟);與由多層膜剝離基材膜之步驟(剝離步驟)。 The invention provides a surface provided on one side of a polarizer. A method for manufacturing a polarizing plate of a transparent protective film includes the steps of laminating a transparent protective film on a surface of a polarizer layer of the polarizing laminated film opposite to the substrate film side to obtain a multilayer film (adhesion Step); and a step of peeling the base film from the multilayer film (peeling step).

依據本發明,製造偏光片時,藉由將聚乙烯醇系樹脂的水溶液減壓、脫泡,在將聚乙烯醇系樹脂的水溶液作為塗裝液塗裝於基材膜而形成聚乙烯醇系樹脂層時,可減輕塗裝液中的氣泡破裂而於塗裝層產生圓形的凹狀缺陷。其結果為,即使將由塗裝後的基材膜及聚乙烯醇系樹脂層所構成之積層膜加以延伸,亦可提供於延伸方向所產生之由於氣泡缺陷所致之楕圓狀或線狀空隙的產生受到抑制之偏光片、及包含該偏光片所成之偏光性積層膜。 According to the present invention, when manufacturing a polarizer, the polyvinyl alcohol-based resin aqueous solution is decompressed and defoamed, and the polyvinyl alcohol-based resin aqueous solution is applied as a coating liquid to a base film to form a polyvinyl alcohol-based film. In the case of the resin layer, it is possible to reduce the occurrence of bubbles in the coating liquid and cause round concave defects in the coating layer. As a result, even if a laminated film composed of a base film and a polyvinyl alcohol-based resin layer after coating is extended, it is possible to provide round or linear voids due to bubble defects generated in the extending direction. A polarizing plate in which the occurrence of ZnO is suppressed, and a polarizing laminated film including the polarizing plate.

10‧‧‧偏光性積層膜 10‧‧‧Polarized laminated film

11‧‧‧基材膜 11‧‧‧ substrate film

12‧‧‧偏光片層 12‧‧‧ polarizer layer

13‧‧‧偏光板 13‧‧‧Polarizer

14‧‧‧透明保護膜 14‧‧‧ transparent protective film

第1圖係表示本發明之偏光性積層膜的基本層結構的一例之簡略剖面圖。 FIG. 1 is a schematic cross-sectional view showing an example of a basic layer structure of a polarizing laminated film of the present invention.

第2圖係表示本發明之偏光板的基本層結構的一例之簡略剖面圖。 Fig. 2 is a schematic cross-sectional view showing an example of a basic layer structure of a polarizing plate of the present invention.

第3圖係表示第1圖所示之偏光性積層膜之製造方法的一實施形態之流程圖。 Fig. 3 is a flowchart showing an embodiment of a method for manufacturing a polarizing laminated film shown in Fig. 1.

第4圖係表示第2圖所示之偏光板之製造方法的一實施形態之流程圖。 Fig. 4 is a flowchart showing an embodiment of a method for manufacturing a polarizing plate shown in Fig. 2.

以下,參照圖面詳細說明本發明的一實施形態。 Hereinafter, one embodiment of the present invention will be described in detail with reference to the drawings.

[偏光性積層膜之結構] [Structure of polarizing laminated film]

第1圖係表示本發明之偏光性積層膜的基本層結構的一例之簡略剖面圖。偏光性積層膜10,係具備:基材膜11、形成於基材膜11的一側之面之偏光片層12。偏光片層12為厚度10μm以下,係由吸附定向有二色性色素之聚乙烯醇系樹脂所形成。 FIG. 1 is a schematic cross-sectional view showing an example of a basic layer structure of a polarizing laminated film of the present invention. The polarizing laminated film 10 includes a base film 11 and a polarizer layer 12 formed on one surface of the base film 11. The polarizer layer 12 has a thickness of 10 μm or less, and is formed of a polyvinyl alcohol-based resin having a dichroic dye adsorbed and oriented.

以下詳細說明各結構要素。 Each constituent element is explained in detail below.

[基材膜] [Substrate film]

基材膜11的材料,可使用例如透明性、機械強度、熱安定性、延伸性等優異之熱可塑性樹脂。此種熱可塑性樹脂之具體例,可列舉:纖維素三乙酸酯等纖維素酯系樹脂、聚酯系樹脂、聚醚碸系樹脂、聚碸系樹脂、聚碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚烯烴系樹脂、(甲基)丙烯酸系樹脂、環狀聚烯烴系樹脂(降莰烯(norbornene)系樹脂)、聚烯丙酯(polyallylate)系樹脂、聚苯乙烯系樹脂、聚乙烯醇系樹脂、及該等之混合物等。 As the material of the base film 11, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, and extensibility can be used. Specific examples of such thermoplastic resins include cellulose ester resins such as cellulose triacetate, polyester resins, polyether fluorene resins, polyfluorene resins, polycarbonate resins, and polyamides. Resins, polyimide resins, polyolefin resins, (meth) acrylic resins, cyclic polyolefin resins (norbornene resins), polyallylate resins, Polystyrene resins, polyvinyl alcohol resins, and mixtures thereof.

基材膜的材料,較佳為包含選自纖維素酯系樹脂、聚烯烴系樹脂、環狀聚烯烴系樹脂及(甲基)丙烯酸系樹脂所成群中之至少1者。 The material of the base film is preferably at least one selected from the group consisting of a cellulose ester resin, a polyolefin resin, a cyclic polyolefin resin, and a (meth) acrylic resin.

本說明書中,「(甲基)丙烯酸」意指丙烯酸或甲基丙烯酸。 In this specification, "(meth) acrylic acid" means acrylic acid or methacrylic acid.

纖維素酯系樹脂,係纖維素與脂肪酸之 酯。此種纖維素酯系樹脂之具體例可列舉:纖維素三乙酸酯、纖維素二乙酸酯、纖維素三丙酸酯、纖維素二丙酸酯等。該等之中,尤佳為纖維素三乙酸酯。纖維素三乙酸酯係有多種市售製品,從容易取得性和成本之點而言亦屬有利。纖維素三乙酸酯的市售品之例可列舉:FUJITAC(註冊商標)TD80(FUJIFILM股份有限公司製)、FUJITAC(註冊商標)TD80UF(FUJIFILM股份有限公司製)、FUJITAC(註冊商標)TD80UZ(FUJIFILM股份有限公司製)、FUJITAC(註冊商標)TD40UZ(FUJIFILM股份有限公司製)、KC8UX2M(Konica Minolta Opto股份有限公司製)、KC4UY(Konica Minolta Opto股份有限公司製)等。 Cellulose ester resin ester. Specific examples of such a cellulose ester-based resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Among these, cellulose triacetate is particularly preferred. There are various commercially available products of cellulose triacetate, which is also advantageous from the viewpoint of easy availability and cost. Examples of commercially available products of cellulose triacetate include FUJITAC (registered trademark) TD80 (manufactured by FUJIFILM Co., Ltd.), FUJITAC (registered trademark) TD80UF (manufactured by FUJIFILM company), FUJITAC (registered trademark) TD80UZ ( FUJIFILM Co., Ltd.), FUJITAC (registered trademark) TD40UZ (FUJIFILM Co., Ltd.), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC4UY (Konica Minolta Opto Co., Ltd.), etc.

聚烯烴系樹脂,可列舉:聚乙烯、聚丙烯等。使用由聚丙烯所成之基材膜時,因容易安定的以高倍率延伸而為較佳。作為環狀聚烯烴系樹脂,較佳可使用降莰烯系樹脂。環狀聚烯烴系樹脂係以環狀烯烴為聚合單元而聚合之樹脂的總稱,可列舉例如:日本特開平1-240517號公報、日本特開平3-14882號公報、日本特開平3-122137號公報等所記載之樹脂。具體例可列舉:環狀烯烴之開環(共)聚合物,環狀烯烴之加成聚合物,環狀烯烴與乙烯、丙烯等α-烯烴之共聚物(代表者為無規共聚物),及該等經不飽和羧酸或其衍生物改質之接枝聚合物,以及該等之氫化物等。環狀烯烴之具體例可列舉降莰烯系單體。 Examples of the polyolefin-based resin include polyethylene and polypropylene. When a base film made of polypropylene is used, it is preferable because it can be easily stretched at a high rate. As the cyclic polyolefin-based resin, a norbornene-based resin can be preferably used. Cyclic polyolefin resin is a generic term for a resin polymerized by using a cyclic olefin as a polymerization unit, and examples thereof include Japanese Patent Laid-Open No. 1-240517, Japanese Patent Laid-Open No. 3-14882, and Japanese Patent Laid-Open No. 3-122137. Resin described in bulletins and the like. Specific examples include: ring-opened (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and α-olefins such as ethylene and propylene (represented as random copolymers), And these graft polymers modified by unsaturated carboxylic acids or their derivatives, and these hydrides. Specific examples of the cyclic olefin include a norbornene-based monomer.

環狀聚烯烴系樹脂係有各種製品於市面販售。具體例可列舉:Topas(註冊商標)(Ticona公司製)、 ARTON(註冊商標)(JSR股份有限公司製)、ZEONOR(註冊商標)(日本瑞翁股份有限公司製)、ZEONEX(註冊商標)(日本瑞翁股份有限公司製)、APEL(註冊商標)(三井化學股份有限公司製)。 Various products of cyclic polyolefin resins are commercially available. Specific examples include: Topas (registered trademark) (manufactured by Ticona), ARTON (registered trademark) (made by JSR Co., Ltd.), ZEONOR (registered trademark) (made by Japan Ruon Co., Ltd.), ZEONEX (registered trademark) (made by Japan Ruon Co., Ltd.), APEL (registered trademark) (Mitsui Chemical Co., Ltd.).

作為(甲基)丙烯酸系樹脂,可採用任意之合適的(甲基)丙烯酸系樹脂。可列舉例如:聚甲基丙烯酸甲酯等聚(甲基)丙烯酸酯、甲基丙烯酸甲酯-(甲基)丙烯酸共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸酯共聚物、甲基丙烯酸甲酯-丙烯酸酯-(甲基)丙烯酸共聚物、(甲基)丙烯酸甲酯-苯乙烯共聚物(MS樹脂等)、具有脂環族烴基之聚合物(例如:甲基丙烯酸甲酯-甲基丙烯酸環己酯之共聚物、甲基丙烯酸甲酯-(甲基)丙烯酸降莰酯之共聚物等)。較佳可列舉:聚(甲基)丙烯酸甲酯等聚(甲基)丙烯酸C1-6烷基酯。(甲基)丙烯酸系樹脂,更佳為使用以甲基丙烯酸甲酯為主成分(50至100重量%,較佳為70至100重量%)之甲基丙烯酸甲酯系樹脂。 As the (meth) acrylic resin, any appropriate (meth) acrylic resin can be used. Examples include poly (meth) acrylates such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic copolymer, methyl methacrylate- (meth) acrylate copolymer, and methyl Methyl acrylate-acrylate- (meth) acrylic copolymer, methyl (meth) acrylate-styrene copolymer (MS resin, etc.), polymers with alicyclic hydrocarbon groups (for example: methyl methacrylate- Copolymers of cyclohexyl methacrylate, copolymers of methyl methacrylate-norbornyl (meth) acrylate, etc.). Preferred examples include poly (meth) acrylate C 1-6 alkyl esters such as poly (meth) acrylate. The (meth) acrylic resin is more preferably a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight).

於基材膜11,在上述熱可塑性樹脂之外,亦可添加任意之合適的添加劑。此種添加劑,可列舉例如:紫外線吸收劑、抗氧化劑、潤滑劑、塑化劑、離型劑、抗著色劑、阻燃劑、核劑、抗靜電劑、顏料、及著色劑等。基材膜中之上述所例示之熱可塑性樹脂的含量,較佳為50至100重量%,更佳為50至99重量%,又更佳為60至98重量%,特佳為70至97重量%。此係因為當基材膜中之熱可塑性樹脂的含量未達50重量%時,會無法充分地表 現熱可塑性樹脂原本所具有的高透明性等之故。 Any appropriate additives may be added to the base film 11 in addition to the above-mentioned thermoplastic resin. Examples of such additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, release agents, anti-colorants, flame retardants, nuclear agents, antistatic agents, pigments, and coloring agents. The content of the thermoplastic resin exemplified above in the base film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. %. This is because when the content of the thermoplastic resin in the base film is less than 50% by weight, the surface cannot be sufficiently expressed. This is because of the high transparency of thermoplastic resins.

基材膜11的厚度係可適宜地決定,惟,一般就強度、處理性等作業性之點而言,係以1至500μm為較佳,1至300μm為更佳,5至200μm為又更佳。基材膜11的厚度最佳為5至150μm。 The thickness of the base film 11 can be appropriately determined, but generally, in terms of workability such as strength and handleability, 1 to 500 μm is preferred, 1 to 300 μm is more preferred, and 5 to 200 μm is more preferred. good. The thickness of the base film 11 is preferably 5 to 150 μm.

為使基材膜可在適於聚乙烯醇系樹脂的延伸之溫度範圍延伸,宜使用融點係110℃以上者。較佳為使用融點係130℃以上者。基材膜的融點若未達110℃,則在後述的延伸步驟(S20)中,會因基材膜容易融解而無法充分地提高延伸溫度,使難以延伸超過5倍。基材膜之融點,係依照ISO3146以昇溫速度10℃/分鐘測定之值。 In order that the base film can be extended in a temperature range suitable for the extension of the polyvinyl alcohol-based resin, it is preferable to use a melting point of 110 ° C or higher. The melting point is preferably 130 ° C or higher. If the melting point of the base film does not reach 110 ° C, the base film will easily melt in the stretching step (S20) described later, and the stretching temperature cannot be sufficiently increased, making it difficult to stretch more than 5 times. The melting point of the base film is a value measured at a temperature rise rate of 10 ° C / min in accordance with ISO3146.

基材膜11,亦可為了提高與偏光片層12之密著性,而至少於形成偏光片層12之側的表面,進行電暈放電處理(corona treatment)、電漿處理、火焰處理等。而且,為了提高密著性,亦可於基材膜11形成有偏光片層12之側的表面形成底塗(primer)層等薄層。 The base film 11 may be subjected to a corona treatment, a plasma treatment, a flame treatment, or the like on at least the surface on the side where the polarizer layer 12 is formed in order to improve the adhesion with the polarizer layer 12. In order to improve adhesion, a thin layer such as a primer layer may be formed on the surface of the base film 11 on which the polarizer layer 12 is formed.

[偏光片層] [Polarizer layer]

本發明之偏光片,係於吸收軸方向的長度為100μm以上的空隙為10個/m2以下之由聚乙烯醇系樹脂所構成之偏光片。該偏光片的厚度係10μm以下,亦可更薄而為7μm以下。可製作偏光片層12的厚度在10μm以下之薄型偏光性積層膜。 The polarizing plate of the present invention is a polarizing plate made of a polyvinyl alcohol resin having a length of 100 μm or more in the absorption axis direction and 10 or less / m 2 voids. The thickness of this polarizer is 10 μm or less, and it may be thinner and 7 μm or less. A thin polarizing laminated film having a thickness of 10 μm or less can be produced for the polarizer layer 12.

偏光片層12,具體而言,係於經單軸延伸之聚乙烯醇系樹脂層吸附定向有二色性色素者。作為聚乙 烯醇系樹脂,可使用將聚乙酸乙烯酯系樹脂皂化而得者。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,可例示與能和乙酸乙烯酯共聚合之其他單體之共聚物等。能和乙酸乙烯酯共聚合之其他單體,可列舉例如:不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、具有銨基之丙烯酸醯胺類等。 The polarizer layer 12 is, specifically, one in which a polyvinyl alcohol-based resin layer that is uniaxially stretched adsorbs and orients a dichroic dye. As polyethylene The enol-based resin may be obtained by saponifying a polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include copolymers of other monomers capable of copolymerizing with vinyl acetate in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate. Other monomers that can be copolymerized with vinyl acetate include, for example, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, ammonium acrylates, and the like.

聚乙烯醇系樹脂之皂化度係在99.0莫耳%以下。本發明中,因為皂化度為99.0莫耳%以下之聚乙烯醇系樹脂,即使在實施超過5倍的單軸延伸時亦可維持一定的染色速度,故有可以良好效率生產偏光性能高的薄型偏光性積層膜之優點。另一方面,於使用皂化度超過99.0莫耳%之聚乙烯醇系樹脂時,染色速度會明顯變慢,而有無法得到具有充分的偏光性能之偏光性積層膜之情形,而且,在製造時會有發生需費多達為通常數倍時間的不良情形。 The degree of saponification of polyvinyl alcohol resin is 99.0 mol% or less. In the present invention, since a polyvinyl alcohol-based resin having a degree of saponification of 99.0 mol% or less can maintain a constant dyeing speed even when uniaxial stretching of more than 5 times is performed, it is possible to produce thin types with high polarization performance with good efficiency. Advantages of polarizing laminated film. On the other hand, when a polyvinyl alcohol-based resin having a saponification degree of more than 99.0 mol% is used, the dyeing speed may be significantly slowed, and a polarizing laminated film having sufficient polarizing performance may not be obtained. In addition, at the time of manufacture, There are disadvantages that can take up to several times longer.

聚乙烯醇系樹脂的皂化度,係以90莫耳%以上為較佳,94莫耳%以上為更佳。皂化度若較90莫耳%小,則會有耐水性等強度不充分之情形。 The saponification degree of the polyvinyl alcohol resin is preferably 90 mol% or more, and more preferably 94 mol% or more. If the saponification degree is smaller than 90 mol%, the strength such as water resistance may be insufficient.

在此所謂之皂化度,係將聚乙烯醇系樹脂的原料之聚乙酸乙烯酯系樹脂所包含之乙酸基經皂化步驟而轉變為羥基之比例以單元比(莫耳%)表示者,為下述式所定義之數值。可以JIS K 6726(1994)所規定之方法求得。 The so-called saponification degree is the ratio of the acetic acid group contained in the polyvinyl acetate resin of the polyvinyl alcohol resin as a raw material to the hydroxyl group after the saponification step. The value defined by the formula. It can be determined by a method specified in JIS K 6726 (1994).

皂化度(莫耳%)=(羥基之數)÷(羥基之數+乙酸基之數)×100 Saponification degree (mol%) = (number of hydroxyl groups) ÷ (number of hydroxyl groups + number of acetate groups) × 100

皂化度越高,表示羥基的比例越高,亦即表示阻礙結晶化之乙酸基的比例越低。而且,本發明所使用之聚乙烯醇系樹脂只要皂化度為99.0莫耳%以下,即無特別限定,亦可為一部分經改質之改質聚乙烯醇。改質聚乙烯醇可列舉例如:將聚乙烯醇系樹脂以數%左右之乙烯、丙烯等烯烴,丙烯酸、甲基丙烯酸、巴豆酸等不飽和羧酸,不飽和羧酸之烷基酯、丙烯酸醯胺等改質者等。聚乙烯醇系樹脂之平均聚合度亦無特別限定,惟以100至10000為較佳,以1500至10000為更佳。 The higher the degree of saponification, the higher the proportion of hydroxyl groups, that is, the lower the proportion of acetic acid groups that hinder crystallization. In addition, the polyvinyl alcohol-based resin used in the present invention is not particularly limited as long as the saponification degree is 99.0 mol% or less, and a part of the modified polyvinyl alcohol may be modified. Examples of modified polyvinyl alcohols include polyvinyl alcohol resins containing olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and alkyl esters and acrylic acids of unsaturated carboxylic acids. Modifiers such as amidine. The average degree of polymerization of the polyvinyl alcohol-based resin is not particularly limited, but is preferably 100 to 10,000, and more preferably 1500 to 10,000.

作為具有此種特性之聚乙烯醇系樹脂,可列舉例如:Kuraray股份有限公司製之PVA124(皂化度:98.0至99.0莫耳%)、PVA117(皂化度:98.0至99.0莫耳%)、PVA624(皂化度:95.0至96.0莫耳%)及PVA617(皂化度:94.5至95.5莫耳%);例如日本合成化學工業股份有限公司製之AH-26(皂化度:97.0至98.8莫耳%)、AH-22(皂化度:97.5至98.5莫耳%)、NH-18(皂化度:98.0至99.0莫耳%)及N-300(皂化度:98.0至99.0莫耳%);例如JAPAN VAM & POVAL股份有限公司之JF-17(皂化度:98.0至99.0莫耳%)、JF-17L(皂化度:98.0至99.0莫耳%)及JF-20(皂化度:98.0至99.0莫耳%)等。 Examples of the polyvinyl alcohol resin having such characteristics include PVA124 (degree of saponification: 98.0 to 99.0 mol%), PVA117 (degree of saponification: 98.0 to 99.0 mol%), and PVA624 (made by Kuraray Co., Ltd.). Saponification degree: 95.0 to 96.0 mole%) and PVA617 (saponification degree: 94.5 to 95.5 mole%); for example, AH-26 (Saponification degree: 97.0 to 98.8 mole%), AH, manufactured by Japan Synthetic Chemical Industry Co., Ltd. -22 (degree of saponification: 97.5 to 98.5 mol%), NH-18 (degree of saponification: 98.0 to 99.0 mol%) and N-300 (degree of saponification: 98.0 to 99.0 mol%); for example, JAPAN VAM & POVAL Co., Ltd.'s JF-17 (degree of saponification: 98.0 to 99.0 mole%), JF-17L (degree of saponification: 98.0 to 99.0 mole%) and JF-20 (degree of saponification: 98.0 to 99.0 mole%), etc.

將該聚乙烯醇系樹脂塗裝於基材,而形成有樹脂層者可使用於本發明之偏光片層12的製作。形成聚乙烯醇系樹脂的樹脂層之方法,就容易得到所期望的厚度之偏光片層12之點而言,較佳為將聚乙烯醇系樹脂溶液塗 裝於基材膜11上而形成樹脂層之方法。偏光片層12,較佳為單軸延伸之延伸倍率係超過5倍,又更佳為超過5倍且於8倍以下。 The polyvinyl alcohol-based resin is coated on a base material, and a resin layer is formed, which can be used for production of the polarizer layer 12 of the present invention. The method for forming a resin layer of a polyvinyl alcohol-based resin is preferable in that the polyvinyl alcohol-based resin solution is applied because the polarizer layer 12 having a desired thickness is easily obtained. A method for forming a resin layer by mounting on the base film 11. The polarizer layer 12 preferably has a uniaxially-stretched stretching ratio of more than 5 times, and more preferably more than 5 times and 8 times or less.

以下說明「於基材膜的至少一側之面形成有由聚乙烯醇系樹脂所成之偏光片層,前述偏光片層之於吸收軸方向的長度為100μm以上的空隙為10個/m2以下之偏光性積層膜之製造方法」。 Hereinafter, "a polarizer layer made of a polyvinyl alcohol-based resin is formed on at least one side of the base film, and the length of the polarizer layer in the direction of the absorption axis is 100 μm or more is 10 holes / m 2. The manufacturing method of the following polarizing laminated film ".

說明「於基材膜的至少一側之面塗裝經減壓脫泡之聚乙烯醇系樹脂的水溶液,而得到於基材膜的至少一側之面形成有由聚乙烯醇系樹脂所成之樹脂層的積層膜之樹脂層形成步驟」。 Description "The coating of at least one side of the base film with an aqueous solution of a polyvinyl alcohol-based resin that has been degassed under reduced pressure is performed, and the surface of at least one side of the base film is formed with a polyvinyl alcohol-based resin. The resin layer forming step of the laminated film of the resin layer. "

塗裝於基材膜之聚乙烯醇系樹脂的水溶液,通常係包含4wt%至10wt%聚乙烯醇系樹脂者,較佳為6wt%至9wt%。若為4wt%以下,則由於在乾燥時更需要熱量而有需降低產線速度(line speed)導致生產性劣化之虞。若為10wt%以上,則由於變得容易產生膠化而有保管性劣化之虞。作為聚乙烯醇系樹脂,可使用於偏光片之說明中所例示者。 The aqueous solution of the polyvinyl alcohol-based resin applied to the base film is usually a solution containing 4 to 10% by weight of the polyvinyl alcohol-based resin, and preferably 6 to 9% by weight. If it is 4 wt% or less, since heat is more required during drying, there is a possibility that the line speed needs to be lowered and productivity may deteriorate. When it is 10% by weight or more, gelation tends to occur and storage stability may deteriorate. As the polyvinyl alcohol-based resin, those exemplified in the description of the polarizer can be used.

作為聚乙烯醇系樹脂的水溶液,較佳為經脫泡之聚乙烯醇系樹脂的水溶液,脫泡的方法,就氣泡的去除效率之良好度而言,較佳為藉由減壓脫泡。由於PVA水溶液非常容易起泡,所產生的氣泡不易破泡,故更佳為藉由減壓將起泡所產生的氣泡再度混入液中,並以靜置之狀態減壓,維持減壓狀態,等待氣泡由水溶液中被去除之 The aqueous solution of the polyvinyl alcohol resin is preferably an aqueous solution of the polyvinyl alcohol resin which has been defoamed. The defoaming method is preferably defoaming under reduced pressure in terms of a good degree of bubble removal efficiency. Since the PVA aqueous solution is very easy to foam, and the generated bubbles are not easy to break, it is more preferable to re-blend the bubbles generated by the foaming into the liquid by reducing the pressure, and reduce the pressure in a static state to maintain the reduced pressure. Wait for the bubbles to be removed from the aqueous solution

方法 method

於本發明之脫泡步驟,可使用以真空泵(vacuum pump)吸氣而減壓之方法。脫泡用的容器並無特別指定,只要是可耐受減壓之容器即可,可簡便地實施。減壓,通常是盡量降低容器內的壓力(計示壓),降得越低,處理時間變得越短,故為較適合。容器內的壓力(計示壓),通常設定於-0.04Mpa以下,較佳為-0.05Mpa以下,又更佳為-0.08Mpa以下,特佳為-0.09Mpa以下。處理時間,典型為30分鐘以上,較佳為60分鐘以上,又更佳為120分鐘或120分鐘以上,亦可於不損及生產性之範圍內延長。 In the defoaming step of the present invention, a method of decompressing by suction with a vacuum pump can be used. The container for defoaming is not particularly specified, and any container that can withstand decompression can be used easily. Decompression is usually performed by reducing the pressure (gauge pressure) in the container as much as possible. The lower the pressure is, the shorter the processing time is, which is more suitable. The pressure (gauge pressure) in the container is usually set to -0.04Mpa or less, preferably -0.05Mpa or less, more preferably -0.08Mpa or less, and particularly preferably -0.09Mpa or less. The processing time is typically 30 minutes or more, preferably 60 minutes or more, and more preferably 120 minutes or more, and can also be extended within a range that does not impair productivity.

塗裝經脫泡之聚乙烯醇系樹脂的水溶液(亦記為PVA水溶液或塗裝液)時,所送液之塗裝液的溫度,係以塗裝液接觸基材時不會使基材鬆弛、不會影響所形成之聚乙烯醇系樹脂層的膜厚精度之方式設定上限,另一方面,只要以PVA水溶液不會發生膠化之方式設定下限即可。塗裝液的溫度通常為10至80℃,較佳為15至60℃,更佳為20℃至40℃。 When coating an aqueous solution of a defoamed polyvinyl alcohol-based resin (also referred to as a PVA aqueous solution or a coating liquid), the temperature of the coating liquid to be sent is such that the substrate does not make the substrate when the coating liquid contacts the substrate The upper limit is set so as not to affect the film thickness accuracy of the polyvinyl alcohol-based resin layer that is formed loosely. On the other hand, the lower limit may be set so that the PVA aqueous solution does not gel. The temperature of the coating liquid is usually 10 to 80 ° C, preferably 15 to 60 ° C, and more preferably 20 to 40 ° C.

本發明中,PVA水溶液之製造與塗裝步驟不需為連續,亦可將聚乙烯醇系樹脂溶解於水後,將產生之PVA水溶液一度移至筒形容器(drum can)或貯藏容器(container)等輸送用的容器中,再運輸供給PVA水溶液供到塗裝步驟。亦可藉由將此種溶解聚乙烯醇系樹脂的設備(溶解設備)與塗裝聚乙烯醇系樹脂至基材之設備(塗裝設備)分開,使各個設備可以小型化(compact)之形態實施。 In the present invention, the manufacturing and coating steps of the PVA aqueous solution need not be continuous. After the polyvinyl alcohol-based resin is dissolved in water, the generated PVA aqueous solution is once moved to a drum can or a container. ), Etc., and then transported and supplied the PVA aqueous solution to the coating step. The equipment for dissolving polyvinyl alcohol resin (dissolving equipment) and the equipment for coating polyvinyl alcohol resin to the substrate (painting equipment) can be separated, so that each equipment can be compacted. Implementation.

[樹脂層形成步驟(S10)] [Resin layer forming step (S10)]

在此,係於基材膜的一表面上形成由聚乙烯醇系樹脂所成之樹脂層(亦記為聚乙烯醇系樹脂層或樹脂層)。 Here, a resin layer (also referred to as a polyvinyl alcohol-based resin layer or a resin layer) made of a polyvinyl alcohol-based resin is formed on one surface of the base film.

適於基材膜之材料,係如於上述偏光性積層膜的結構之說明所述。又,本實施形態中,適於形成樹脂層之聚乙烯醇系樹脂的材料,係如於偏光性積層膜的結構之說明所述。 The material suitable for the base film is as described in the structure of the polarizing laminated film. In this embodiment, the material of the polyvinyl alcohol-based resin suitable for forming the resin layer is as described in the description of the structure of the polarizing laminated film.

聚乙烯醇系樹脂的樹脂層,通常係將聚乙烯醇系樹脂的水溶液塗裝於基材膜的一表面上,使水等溶劑蒸發、乾燥而形成。藉此方式形成樹脂層,可形成較薄者。將聚乙烯醇系樹脂的水溶液塗裝於基材膜之方法,可由線棒塗佈法、反向塗佈、凹版塗佈等輥塗佈法,模塗(die coat)法、缺角輪塗佈(comma coat)法、唇塗(lip coat)法、旋塗(spin coat)法、網版塗佈法、噴塗(fountain coat)法、浸漬法、噴霧(spray)法等公知的方法適宜選擇而採用。較佳為缺角輪塗佈法(刀式塗佈機(knife coater))、模塗法、唇塗法。乾燥溫度係例如50℃至200℃,較佳為60℃至150℃。乾燥時間係例如2分鐘至20分鐘。 The resin layer of a polyvinyl alcohol-based resin is usually formed by coating an aqueous solution of a polyvinyl alcohol-based resin on one surface of a substrate film, and evaporating and drying a solvent such as water. By forming the resin layer in this way, a thinner one can be formed. The method for applying an aqueous solution of a polyvinyl alcohol resin to a substrate film may be a roll coating method such as a wire rod coating method, a reverse coating, a gravure coating, a die coat method, or a notched wheel coating. A well-known method such as a comma coat method, a lip coat method, a spin coat method, a screen coating method, a spray coat method, a dipping method, and a spray method is suitably selected. Instead. The corner wheel coating method (knife coater), die coating method, and lip coating method are preferred. The drying temperature is, for example, 50 ° C to 200 ° C, and preferably 60 ° C to 150 ° C. The drying time is, for example, 2 minutes to 20 minutes.

形成之樹脂層的厚度,若考慮到延伸後的染色性,則下限通常係超過3μm之厚度。最終所得之偏光片層的厚度為10μm以下時,形成之樹脂層的厚度通常為30μm以下。形成之樹脂層的厚度,較佳為5μm至20μm。 When the thickness of the resin layer to be formed is taken into consideration, the lower limit is usually a thickness exceeding 3 μm. When the thickness of the finally obtained polarizer layer is 10 μm or less, the thickness of the resin layer to be formed is usually 30 μm or less. The thickness of the formed resin layer is preferably 5 μm to 20 μm.

而且,為了提高基材膜與聚乙烯醇系樹脂 層之密著性,亦可於基材膜與樹脂層之間設置底塗層。從密著性的觀點來看,底塗層較佳為由含有聚乙烯醇系樹脂與交聯劑之組成物所形成。 In addition, in order to improve the base film and polyvinyl alcohol resin The adhesion of the layer may also be provided between the base film and the resin layer. From the viewpoint of adhesion, the undercoat layer is preferably formed of a composition containing a polyvinyl alcohol-based resin and a crosslinking agent.

[延伸步驟(S20)] [Extended step (S20)]

以下說明「將於如此所得之基材膜積層有聚乙烯醇系樹脂層之積層膜延伸,而得到延伸膜之延伸步驟」。將由基材膜及樹脂層所成之積層膜,以成為相對於積層膜的延伸步驟前的長度成為超過5倍的延伸倍率之方式進行單軸延伸,得到延伸膜。較佳係以成為超過5倍且於8倍以下的延伸倍率之方式進行單軸延伸。延伸倍率若為5倍以下,則由於由聚乙烯醇系樹脂所成之樹脂層未充分定向,故就結果而言,為無法充分地提高偏光片層的偏光度。另一方面,若延伸倍率為超過8倍,則延伸時積層膜容易產生破裂,同時延伸膜的厚度變得薄於所需厚度,而有後續步驟之加工性/處理性降低之虞。延伸步驟(S20)之延伸處理,並不限定為一階段延伸,亦可分為多階段進行。以多階段進行時,係以延伸處理之全部階段合計之延伸倍率超過5倍之方式進行延伸處理。 The following describes "the stretching step of obtaining a stretched film by stretching the laminated film having the polyvinyl alcohol-based resin layer laminated on the substrate film thus obtained." A laminated film made of a base film and a resin layer is uniaxially stretched so as to have an extension ratio of more than 5 times the length before the extension step of the laminated film to obtain an extended film. The uniaxial stretching is preferably performed so that the stretching ratio is more than 5 times and 8 times or less. If the stretching ratio is 5 times or less, the resin layer made of a polyvinyl alcohol-based resin is not sufficiently oriented, and as a result, the degree of polarization of the polarizer layer cannot be sufficiently increased. On the other hand, if the stretching ratio exceeds 8 times, the laminated film is likely to be cracked during stretching, and at the same time, the thickness of the stretched film becomes thinner than required, and the workability / handling property of the subsequent steps may be reduced. The stretching process of the stretching step (S20) is not limited to one-stage stretching, and may be divided into multiple stages. When it is performed in multiple stages, the stretching process is performed in such a way that the total stretching ratio of all stages of the stretching process exceeds 5 times.

本實施形態之延伸步驟(S20)中,較佳為對於積層膜的長度方向進行縱向延伸處理,當不求如此程度之偏光性能時,為藉由拉幅法(tenter method)之橫向單軸延伸等所代表之固定端單軸延伸亦無妨。縱向延伸方式可列舉:輥間延伸方法、壓縮延伸方法、使用拉幅機(tenter)延伸之方法等。延伸處理並不限定為縱向延伸處理,亦可為 斜向延伸處理等。而且,較佳為自由端單軸延伸。 In the stretching step (S20) of this embodiment, it is preferable to perform longitudinal stretching processing on the longitudinal direction of the laminated film. When such a degree of polarizing performance is not required, it is transverse uniaxial stretching by the tenter method. The uniaxial extension of the fixed end, etc., is not a problem. Examples of the longitudinal stretching method include a roll-to-roll stretching method, a compression stretching method, and a method using a tenter to stretch. The stretching process is not limited to the longitudinal stretching process, and may be Oblique extension processing, etc. Moreover, it is preferable that the free end extends uniaxially.

而且,延伸處理亦可採用濕式延伸方法、乾式延伸方法中之任一者,使用乾式延伸方法者,就可由較廣範圍選擇延伸積層膜時的溫度之點而言,係屬較佳。 In addition, the stretching treatment may be performed by any of a wet stretching method and a dry stretching method. A dry stretching method is preferable in that a temperature at which the laminated film is stretched can be selected from a wide range.

於本實施形態,較佳為於基材膜的融點-30℃至+5℃之溫度範圍進行延伸處理。又更佳為於基材膜的融點-25℃至融點之溫度範圍進行延伸處理。延伸溫度若是低於基材膜11的融點-30℃,則會超過5倍之高倍率延伸變得困難。延伸溫度若超過基材膜的融點+5℃,則會因為基材膜融解而變得難以延伸。又,延伸溫度係於上述範圍內,又更佳為120℃以上。這是因為當延伸溫度為120℃以上時,即使為超過5倍之高延伸倍率,也不會伴隨有延伸處理困難性之故。延伸處理的溫度調整,通常係藉由調整加熱爐的溫度而進行。 In this embodiment, it is preferable to perform the extension treatment at a temperature range of -30 ° C to + 5 ° C, which is the melting point of the base film. It is more preferable to perform the extension treatment in a temperature range from the melting point of the base film to -25 ° C to the melting point. If the stretching temperature is -30 ° C lower than the melting point of the base film 11, it will be difficult to stretch at a high rate exceeding 5 times. If the elongation temperature exceeds the melting point of the base material film by + 5 ° C, it becomes difficult to extend the base material film due to melting. The elongation temperature is within the above range, and more preferably 120 ° C or higher. This is because when the stretching temperature is 120 ° C. or higher, even if the stretching ratio is higher than 5 times, the difficulty in stretching processing is not accompanied. The temperature adjustment of the stretching treatment is usually performed by adjusting the temperature of the heating furnace.

[染色步驟(S30)] [Dyeing step (S30)]

以下說明「將所得之延伸膜的樹脂層以二色性色素染色而形成偏光片層之染色步驟」。在此,係將延伸膜之聚乙烯醇系樹脂層以二色性色素染色。二色性色素可列舉例如、碘、有機染料等。有機染料可使用例如:Red BR、Red LR、Red R、Pink LB、Rubin BL、Bordeaux GS、Sky Blue LG、Lemon Yellow、Blue BR、Blue 2R、Navy RY、Green LG、Violet LB、Violet B、Black H、Black B、Black GSP、Yellow 3G、Yellow R、Orange LR、Orange 3R、Scarlet GL、Scarlet KGL、Congo Red、Brilliant Violet BK、Supra Blue G、Supra Blue GL、Supra Orange GL、Direct Sky Blue、Direct Fast Orange S、Fast Black等。該等二色性物質可使用單一種,亦可將二種以上併用。 The "dyeing step of forming a polarizer layer by dyeing the resin layer of the obtained stretched film with a dichroic dye" will be described below. Here, the polyvinyl alcohol-based resin layer of the stretched film is dyed with a dichroic dye. Examples of the dichroic dye include iodine and organic dyes. Organic dyes can be used: Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Supra Blue G, Supra Blue GL, Supra Orange GL, Direct Sky Blue, Direct Fast Orange S, Fast Black, etc. These dichroic substances may be used singly or in combination of two or more kinds.

染色步驟,係例如藉由將延伸膜整體浸漬於含有上述二色性色素之溶液(染色溶液)中而進行。染色溶液可使用將上述二色性色素溶解於溶媒中之溶液。染色溶液之溶媒,一般係可使用水,亦可進一步添加能與水相溶的有機溶媒。二色性色素的濃度較佳為0.01重量%至10重量%,更佳為0.02重量%至7重量%,尤佳為0.025重量%至5重量%。 The dyeing step is performed, for example, by immersing the entire stretched film in a solution (dyeing solution) containing the dichroic pigment. As the dyeing solution, a solution obtained by dissolving the dichroic pigment in a solvent can be used. The solvent of the dyeing solution is generally water, and an organic solvent compatible with water can be further added. The concentration of the dichroic pigment is preferably 0.01% by weight to 10% by weight, more preferably 0.02% by weight to 7% by weight, and even more preferably 0.025% by weight to 5% by weight.

使用碘作為二色性色素時,可更加提高染色效率,因此較佳為進一步添加碘化物。該碘化物可列舉例如:碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦等。該等碘化物之添加比例,較佳為於染色溶液中係0.01重量%至20重量%。碘化物之中,較佳為添加碘化鉀。添加碘化鉀時,碘與碘化鉀的比例以重量比計,較佳為於1:5至1:100之範圍,更佳為於1:6至1:80之範圍,尤佳為於1:7至1:70之範圍。 When iodine is used as a dichroic dye, the dyeing efficiency can be further improved. Therefore, it is preferable to further add iodide. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. The addition ratio of these iodides is preferably 0.01% to 20% by weight in the dyeing solution. Among the iodides, potassium iodide is preferably added. When potassium iodide is added, the ratio of iodine to potassium iodide is based on weight ratio, preferably in the range of 1: 5 to 1: 100, more preferably in the range of 1: 6 to 1:80, and particularly preferably in the range of 1: 7 to The range of 1:70.

延伸膜浸漬於染色溶液的時間並無特別限定,通常以於15秒鐘至15分鐘之範圍為較佳,以1分至3分鐘為更佳。而且,染色溶液的溫度係以於10℃至60℃之範圍為較佳,以於20℃至40℃之範圍為更佳。染色步驟中,亦可以純水洗去餘量的染色溶液。 The time during which the stretched film is immersed in the dyeing solution is not particularly limited, but is usually preferably in the range of 15 seconds to 15 minutes, and more preferably 1 minute to 3 minutes. The temperature of the dyeing solution is preferably in the range of 10 ° C to 60 ° C, and more preferably in the range of 20 ° C to 40 ° C. In the dyeing step, the remaining dyeing solution may be washed away with pure water.

染色步驟中,係可繼染色而接著進行交聯處理。交聯處理例如可藉由將延伸膜浸漬於包含交聯劑之溶液(交聯溶液)中而進行。交聯劑可使用以往公知的物質。可列舉例如:硼酸、硼砂等硼化合物,或乙二醛、戊二醛等。該等可使用單一種類,亦可將二種以上併用。 In the dyeing step, the lines may be dyed and then cross-linked. The crosslinking treatment can be performed, for example, by immersing the stretched film in a solution (crosslinking solution) containing a crosslinking agent. As the crosslinking agent, conventionally known ones can be used. Examples include boron compounds such as boric acid and borax, or glyoxal and glutaraldehyde. These may be used singly or in combination of two or more.

交聯溶液可使用將交聯劑溶解於溶媒中之溶液。溶媒例如可使用水,亦可進一步包含能與水相溶的有機溶媒。交聯溶液之交聯劑的濃度並不限定為下述者,惟較佳為於1重量%至20重量%之範圍,更佳為6重量%至15重量%。 As the crosslinking solution, a solution in which a crosslinking agent is dissolved in a solvent can be used. The solvent may be, for example, water, and may further include an organic solvent compatible with water. The concentration of the crosslinking agent in the crosslinking solution is not limited to the following, but it is preferably in the range of 1% to 20% by weight, and more preferably in the range of 6% to 15% by weight.

交聯溶液中亦可添加碘化物。藉由添加碘化物,可使聚乙烯醇系樹脂層的面內之偏光特性更加均勻化。碘化物可列舉例如:碘化鉀、碘化鋰、碘化鈉、碘化鋅、碘化鋁、碘化鉛、碘化銅、碘化鋇、碘化鈣、碘化錫、碘化鈦。碘化物的含量通常為0.05重量%至15重量%,更佳為0.5重量%至8重量%。 Iodide can also be added to the crosslinking solution. By adding iodide, the in-plane polarization characteristics of the polyvinyl alcohol-based resin layer can be made more uniform. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. The content of iodide is usually 0.05 to 15% by weight, and more preferably 0.5 to 8% by weight.

延伸膜浸漬於交聯溶液之時間,通常以15秒鐘至20分鐘為較佳,30秒鐘至15分鐘為更佳。而且,交聯溶液的溫度較佳為於10至80℃之範圍。 The time for which the stretched film is immersed in the crosslinking solution is usually 15 seconds to 20 minutes, more preferably 30 seconds to 15 minutes. The temperature of the crosslinking solution is preferably in the range of 10 to 80 ° C.

較佳為於最後進行洗淨步驟及乾燥步驟。洗淨步驟可施行水洗淨處理。水洗淨處理,通常可藉由將延伸膜浸漬於離子交換水、蒸餾水等純水而進行。水洗淨溫度通常為3℃至50℃,較佳為於4℃至20℃之範圍。浸漬時間通常為2秒鐘至300秒鐘,較佳為3秒鐘至240秒 鐘。 Preferably, the washing step and the drying step are performed at the end. The washing step may be performed with a water washing treatment. The water washing treatment is usually performed by immersing the stretched film in pure water such as ion-exchanged water or distilled water. The water washing temperature is usually 3 ° C to 50 ° C, preferably 4 ° C to 20 ° C. The dipping time is usually from 2 seconds to 300 seconds, preferably from 3 seconds to 240 seconds bell.

洗淨步驟,係可將經由碘化物溶液之洗淨處理與水洗淨處理組合,亦可使用適宜地調配有甲醇、乙醇、異丙醇、丁醇、丙醇等液體醇之溶液。 The washing step may be a combination of washing treatment with an iodide solution and water washing treatment, and a solution prepared with liquid alcohols such as methanol, ethanol, isopropanol, butanol, and propanol may be suitably used.

洗淨步驟後,較佳為施行乾燥步驟。乾燥步驟可採用合適的任意方法(例如,自然乾燥、送風乾燥、加熱乾燥)。例如,加熱乾燥時之乾燥溫度通常為20℃至95℃,乾燥時間通常為1分至15分鐘左右。藉由以上染色步驟(S30),可使聚乙烯醇系樹脂層具有作為偏光片之功能。本說明書中,係將具有作為偏光片功能之聚乙烯醇系樹脂層稱為偏光片層,將於基材膜上具備偏光片層之積層物稱為偏光性積層膜。 After the washing step, a drying step is preferably performed. The drying step can be performed by any appropriate method (for example, natural drying, air drying, and heating drying). For example, the drying temperature during heating and drying is usually 20 ° C to 95 ° C, and the drying time is usually about 1 minute to 15 minutes. Through the above dyeing step (S30), the polyvinyl alcohol-based resin layer can be made to function as a polarizer. In this specification, a polyvinyl alcohol-based resin layer having a function as a polarizer is referred to as a polarizer layer, and a laminate having a polarizer layer on a base film is referred to as a polarizing multilayer film.

本實施形態中,因為聚乙烯醇系樹脂層係使用皂化度為99.0莫耳%以下、經減壓脫泡之聚乙烯醇系樹脂的水溶液,而且,延伸步驟(S20)中,係以超過5倍之延伸倍率進行單軸延伸,故在染色步驟(S30)可維持良好的染色速度。又,使用皂化度高之聚乙烯醇系樹脂的樹脂層,則在染色步驟(S30)之染色速度降低,染色容易變得不充分。 In this embodiment, the polyvinyl alcohol-based resin layer is an aqueous solution of a polyvinyl alcohol-based resin having a degree of saponification of 99.0 mol% or less and degassing under reduced pressure, and in the extension step (S20), it is more than 5 The stretching ratio is uniaxially extended, so a good dyeing speed can be maintained in the dyeing step (S30). In addition, when a resin layer of a polyvinyl alcohol-based resin having a high degree of saponification is used, the dyeing speed in the dyeing step (S30) is reduced, and dyeing tends to be insufficient.

[偏光板之結構] [Structure of polarizing plate]

第2圖表示本發明偏光板的基本層結構的一例之簡略剖面圖。偏光板13具備透明保護膜14、與形成於透明保護膜14的一側之面之偏光片層12。偏光片層12之厚度為10μm以下,係由吸附定向有二色性色素之聚乙烯醇系樹脂所形成。聚乙烯醇系樹脂的皂化度在99.0莫耳%以下。 Fig. 2 is a schematic cross-sectional view showing an example of a basic layer structure of a polarizing plate of the present invention. The polarizing plate 13 includes a transparent protective film 14 and a polarizer layer 12 formed on one surface of the transparent protective film 14. The polarizer layer 12 has a thickness of 10 μm or less, and is formed of a polyvinyl alcohol-based resin having a dichroic dye oriented. The degree of saponification of the polyvinyl alcohol resin is 99.0 mol% or less.

偏光板13中,透明保護膜14與偏光片層12係例如以黏著劑或接著劑層貼合。以下詳細說明各結構要素。 In the polarizing plate 13, the transparent protective film 14 and the polarizer layer 12 are bonded by, for example, an adhesive or an adhesive layer. Each constituent element is explained in detail below.

[透明保護膜] [Transparent protective film]

透明保護膜14可為不具光學功能之單純的透明保護膜,為所謂相位差膜或增亮膜之同時具有光學功能的透明保護膜亦無妨。透明保護膜14的材料並無特別限定,可列舉例如:如由環狀聚烯烴系樹脂膜、三乙酸纖維素、二乙酸纖維素類樹脂所成之乙酸纖維素系樹脂膜,如由聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚對苯二甲酸丁二酯的樹脂所成之聚酯系樹脂膜,聚碳酸酯系樹脂膜,(甲基)丙烯酸系樹脂膜,聚丙烯系樹脂膜等,以往廣泛使用於該領域之膜。 The transparent protective film 14 may be a simple transparent protective film having no optical function, and it may be a transparent protective film having both an optical function and a so-called retardation film or a brightness enhancement film. The material of the transparent protective film 14 is not particularly limited, and examples thereof include, for example, a cellulose acetate resin film made of a cyclic polyolefin resin film, cellulose triacetate, and cellulose diacetate resin. Polyester resin film, polycarbonate resin film, (meth) acrylic resin film made of resins of ethylene phthalate, polyethylene naphthalate, and polybutylene terephthalate, Polypropylene-based resin films and the like have conventionally been widely used in this field.

作為環狀聚烯烴系樹脂,可適合使用適宜的市售品,例如:Topas(註冊商標)(Ticona公司製)、ARTON(註冊商標)(JSR股份有限公司製)、ZEONOR(註冊商標)(日本瑞翁(Zeon)股份有限公司製)、ZEONEX(註冊商標)(日本瑞翁股份有限公司製)、APEL(註冊商標)(三井化學股份有限公司製)。將此種環狀聚烯烴系樹脂進行製膜而成膜時,可適宜使用溶劑澆鑄法、熔融擠出法等公知的方法。而且,亦可使用Escena(註冊商標)(積水化學工業股份有限公司製)、SCA40(積水化學工業股份有限公司製)、ZEONOR(註冊商標)FILM(OPTES股份有限公司製)等預製成膜之環狀聚烯烴系樹脂製的膜之市售品。 As the cyclic polyolefin resin, suitable commercially available products can be suitably used, for example, Topas (registered trademark) (manufactured by Ticona), ARTON (registered trademark) (manufactured by JSR Corporation), ZEONOR (registered trademark) (Japan) (Made by Zeon Co., Ltd.), ZEONEX (registered trademark) (made by Japan Ruon Co., Ltd.), APEL (registered trademark) (made by Mitsui Chemicals Co., Ltd.). When such a cyclic polyolefin resin is formed into a film, a known method such as a solvent casting method or a melt extrusion method can be suitably used. In addition, pre-made membrane rings such as Escena (registered trademark) (made by Sekisui Chemical Industry Co., Ltd.), SCA40 (made by Sekisui Chemical Industry Co., Ltd.), and Zeonor (registered trademark) FILM (made by OPTES Co., Ltd.) can also be used. A commercially available product of a film made of a polyolefin resin.

環狀聚烯烴系樹脂膜亦可為經單軸延伸或經二軸延伸者。藉由進行延伸,可賦予環狀聚烯烴系樹脂膜任意的相位差值。延伸通常係一邊將膜由捲軸捲出一邊連續進行,於加熱爐,朝捲軸的行進方向、朝與其行進方向垂直的方向、或朝這兩個方向延伸。加熱爐的溫度通常是在環狀聚烯烴系樹脂之玻璃轉移溫度附近至玻璃轉移溫度+100℃為止之範圍。延伸的倍率,通常在一個方向為1.1至6倍、較佳為1.1至3.5倍。 The cyclic polyolefin resin film may be uniaxially stretched or biaxially stretched. By stretching, an arbitrary retardation value can be given to the cyclic polyolefin resin film. Stretching is usually carried out continuously while rolling the film out of the reel, and in the heating furnace, it extends in the direction of the reel, in a direction perpendicular to the direction of the reel, or in both directions. The temperature of the heating furnace is usually in the range from the glass transition temperature of the cyclic polyolefin resin to the glass transition temperature + 100 ° C. The stretching magnification is usually 1.1 to 6 times in one direction, preferably 1.1 to 3.5 times.

環狀聚烯烴系樹脂膜,由於一般而言其表面活性較差,故較佳係在與偏光膜接著之表面進行電漿處理、電暈放電處理、紫外線照射處理、火焰(flame)處理、皂化處理等表面處理。其中,以較容易實施之電漿處理、電暈放電處理為較適合。 Cyclic polyolefin resin film is generally poor in surface activity, so it is preferable to perform plasma treatment, corona discharge treatment, ultraviolet irradiation treatment, flame treatment, saponification treatment on the surface next to the polarizing film. And other surface treatment. Among them, plasma treatment and corona discharge treatment which are relatively easy to implement are more suitable.

乙酸纖維素系樹脂膜,可適合使用適宜的市售品,例如:FUJITAC(註冊商標)TD80(FUJIFILM股份有限公司製)、FUJITAC(註冊商標)TD80UF(FUJIFILM股份有限公司製)、FUJITAC(註冊商標)TD80UZ(FUJIFILM股份有限公司製)、FUJITAC(註冊商標)TD40UZ(FUJIFILM股份有限公司製)、KC8UX2M(Konica Minolta Opto股份有限公司製)、KC4UY(Konica Minolta Opto股份有限公司製)。 The cellulose acetate-based resin film can be suitably used with commercially available products, such as: FUJITAC (registered trademark) TD80 (manufactured by FUJIFILM Co., Ltd.), FUJITAC (registered trademark) TD80UF (manufactured by FUJIFILM company), FUJITAC (registered trademark) ) TD80UZ (made by FUJIFILM Co., Ltd.), FUJITAC (registered trademark) TD40UZ (made by FUJIFILM Co., Ltd.), KC8UX2M (made by Konica Minolta Opto Co., Ltd.), and KC4UY (made by Konica Minolta Opto Co., Ltd.).

於乙酸纖維素系樹脂膜的表面,亦可形成用以改良視角特性之液晶層等。而且,為了賦予相位差亦可為經延伸之乙酸纖維素系樹脂膜。乙酸纖維素系樹脂膜為了提高與偏光膜之接著性,通常會施行皂化處理。皂化 處理可採用浸漬於如氫氧化鈉或氫氧化鉀之鹼性水溶液的方法。 A liquid crystal layer or the like can be formed on the surface of the cellulose acetate resin film to improve viewing angle characteristics. In order to impart a retardation, a stretched cellulose acetate resin film may be used. In order to improve the adhesion to a polarizing film, a cellulose acetate-based resin film is usually subjected to a saponification treatment. Saponification The treatment can be performed by immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.

於如上述之透明保護膜14的表面,亦可形成硬塗層、防眩層、抗反射層等光學層。於透明保護膜表面形成該等光學層的方法並無特別限定,可使用公知的方法。 An optical layer such as a hard coat layer, an anti-glare layer, or an anti-reflection layer may be formed on the surface of the transparent protective film 14 as described above. The method of forming these optical layers on the surface of a transparent protective film is not specifically limited, A well-known method can be used.

當欲滿足薄型化的要求時,透明保護膜14的厚度以盡可能地薄者為宜,以88μm以下為較佳,以48μm以下為更佳。若考慮到加工性,則以5μm以上為較佳。 When it is desired to meet the requirements for thinness, the thickness of the transparent protective film 14 is preferably as thin as possible, more preferably 88 μm or less, and even more preferably 48 μm or less. When considering workability, it is more preferable that it is 5 micrometers or more.

[偏光片層] [Polarizer layer]

偏光片層12可為與上述偏光性積層膜10之偏光片層12相同的結構。 The polarizer layer 12 may have the same structure as the polarizer layer 12 of the polarizing laminated film 10 described above.

[黏著劑層] [Adhesive layer]

可用於貼合透明保護膜14與偏光片層12之黏著劑,通常係藉由以丙烯酸系樹脂、苯乙烯系樹脂、聚矽氧系樹脂等作為基質聚合物,而於其中添加異氰酸酯化合物、環氧化合物、氮丙啶(aziridine)化合物等交聯劑所成之組成物。 Adhesives that can be used for bonding the transparent protective film 14 and the polarizer layer 12 are usually made of acrylic resin, styrene resin, silicone resin, etc. as the matrix polymer, and an isocyanate compound, a ring, etc. are added thereto. A composition made of a crosslinking agent such as an oxygen compound and an aziridine compound.

亦可進一步含有微粒子而作為表現光散射之黏著劑層。 It may further contain fine particles as an adhesive layer expressing light scattering.

若考慮到加工性、耐久性之特性,黏著劑層的厚度較佳為1μm至40μm。黏著劑層的厚度為3μm至35μm時,因為亦可抑制偏光膜的尺寸變化,故為更佳。 In consideration of processability and durability characteristics, the thickness of the adhesive layer is preferably 1 μm to 40 μm. When the thickness of the adhesive layer is 3 μm to 35 μm, it is more preferable because the dimensional change of the polarizing film can also be suppressed.

藉由黏著劑將透明保護膜14貼合於偏光片層12之方法中,可在透明保護膜14之面設置黏著劑層後,貼合於偏光片層12,亦可在偏光片層12的表面設置黏著劑層後,於其中貼合透明保護膜14。 In the method of bonding the transparent protective film 14 to the polarizer layer 12 by using an adhesive, an adhesive layer may be provided on the surface of the transparent protective film 14 and then bonded to the polarizer layer 12. After an adhesive layer is provided on the surface, the transparent protective film 14 is stuck thereon.

形成黏著劑層的方法並無特別限定,可於透明保護膜14之面、或偏光片層12之面塗佈以包含上述基質聚合物為主之各成分的溶液,乾燥而形成黏著劑層後,貼合透明保護膜14與偏光片層12,亦可於分隔件(separator)上形成黏著劑層後,轉印而積層於透明保護膜14之面或偏光片層12之面。而且,將黏著劑層形成於透明保護膜14之面或偏光片層12之面時,視所需亦可於透明保護膜14之面或偏光片層12之面、或是於黏著劑層的一面或是雙面施行密著處理,例如施行電暈放電處理等。 The method for forming the adhesive layer is not particularly limited, and the surface of the transparent protective film 14 or the surface of the polarizer layer 12 may be coated with a solution containing the above-mentioned matrix polymer as the main component and dried to form the adhesive layer. The transparent protective film 14 and the polarizer layer 12 are bonded together, or an adhesive layer is formed on a separator, and then transferred and laminated on the surface of the transparent protective film 14 or the surface of the polarizer layer 12. In addition, when the adhesive layer is formed on the surface of the transparent protective film 14 or the surface of the polarizer layer 12, if necessary, it may be on the surface of the transparent protective film 14 or the surface of the polarizer layer 12, or on the surface of the adhesive layer. Adhesive treatment is performed on one or both sides, such as corona discharge treatment.

[接著劑層] [Adhesive layer]

可用於貼合透明保護膜14與偏光片層12之接著劑,可列舉例如使用聚乙烯醇系樹脂水溶液、水系二液型胺酯系乳劑型接著劑等水系接著劑。使用經皂化處理等親水化處理之乙酸纖維素系膜作為透明保護膜14時,作為貼合偏光片層12用之水系接著劑,可適合使用聚乙烯醇系樹脂水溶液。就使用作為接著劑之聚乙烯醇系樹脂而言,除了將為乙酸乙烯酯同元聚合物之聚乙酸乙烯酯進行皂化處理而得之乙烯醇均聚物之外,亦有將乙酸乙烯酯和能與之共聚合的其他單體之共聚物進行皂化處理而得之乙烯醇系共聚物、進一步將該等之部分經基進行改質的改質聚乙烯醇系 聚合物等。水系接著劑中,亦可添加多元醛、水溶性環氧化合物、三聚氰胺系化合物、氧化鋯化合物、鋅化合物等作為添加劑。使用此種水系接著劑時,由該方式所得之接著劑層,通常為1μm以下,即使以通常的光學顯微鏡觀察剖面,事實上也還是觀察不到該接著劑層。 An adhesive that can be used for bonding the transparent protective film 14 and the polarizer layer 12 includes, for example, an aqueous adhesive such as a polyvinyl alcohol-based resin aqueous solution and an aqueous two-liquid amine ester emulsion-based adhesive. When a cellulose acetate-based film that has been subjected to a hydrophilization treatment such as saponification treatment is used as the transparent protective film 14, a polyvinyl alcohol-based resin aqueous solution can be suitably used as an aqueous adhesive for bonding the polarizer layer 12. In the case of using a polyvinyl alcohol-based resin as an adhesive, in addition to a vinyl alcohol homopolymer obtained by saponifying a polyvinyl acetate which is a vinyl acetate homopolymer, there are also vinyl acetate and A vinyl alcohol-based copolymer obtained by saponifying a copolymer of other monomers that can be copolymerized therewith, and a modified polyvinyl alcohol-based copolymer further modified by partially modifying these groups. Polymer, etc. Polyvalent aldehydes, water-soluble epoxy compounds, melamine-based compounds, zirconia compounds, zinc compounds, and the like may be added to the water-based adhesive as additives. When such an aqueous adhesive is used, the adhesive layer obtained by this method is usually 1 μm or less, and even if the cross section is observed with a general optical microscope, the adhesive layer is not actually observed.

使用水系接著劑貼合偏光片層12與透明保護膜14之方法並無特別限定,可列舉例如:將接著劑均勻塗佈於偏光片層12及/或透明保護膜14的表面,於塗佈面重疊另一膜並藉由輥等貼合、乾燥之方法等。通常,接著劑係於其調製之後,在15至40℃的溫度下塗佈,貼合溫度通常於15℃至30℃之範圍。 The method of bonding the polarizer layer 12 and the transparent protective film 14 with an aqueous adhesive is not particularly limited, and examples thereof include uniformly coating the adhesive on the surface of the polarizer layer 12 and / or the transparent protective film 14 and applying The other film is laminated on the surface, and the film is bonded and dried by a roller or the like. Usually, the adhesive is applied at a temperature of 15 to 40 ° C after the preparation thereof, and the bonding temperature is usually in a range of 15 to 30 ° C.

使用水系接著劑時,是在貼合偏光片層12與透明保護膜14之後,為了去除水系接著劑中所包含的水而乾燥之。乾燥爐的溫度較佳為30℃至90℃。若未達30℃,則偏光片層12與透明保護膜14的接著面有變得容易剝離之傾向。若為90℃以上,則有因熱造成光學性能劣化之虞。乾燥時間可為10秒鐘至1000秒鐘,尤其從生產性的觀點來看,較佳為60秒鐘至750秒鐘,更佳為150秒鐘至600秒鐘。 When the water-based adhesive is used, it is dried after removing the water contained in the water-based adhesive after bonding the polarizer layer 12 and the transparent protective film 14 together. The temperature of the drying furnace is preferably 30 ° C to 90 ° C. If it does not reach 30 degreeC, the adhesive surface of the polarizer layer 12 and the transparent protective film 14 will tend to peel easily. If it is 90 ° C or higher, there is a possibility that the optical performance is deteriorated due to heat. The drying time may be from 10 seconds to 1000 seconds, and particularly from the viewpoint of productivity, preferably 60 seconds to 750 seconds, and more preferably 150 seconds to 600 seconds.

乾燥後,亦可進一步以室溫或略高於室溫之溫度,例如以20℃至45℃左右的溫度固化12小時至600小時左右。固化時的溫度,一般係設定於較乾燥時採用的溫度更低之溫度。 After drying, it can be further cured at room temperature or slightly higher than room temperature, for example, at a temperature of about 20 ° C to 45 ° C for about 12 hours to about 600 hours. The temperature during curing is generally set to a lower temperature than the temperature used during drying.

而且,作為貼合偏光片層12與透明保護膜 14時之接著劑,亦可使用光硬化性接著劑。光硬化性接著劑可列舉例如光硬化性環氧樹脂與光陽離子聚合起始劑之混合物等。 In addition, as a polarizer sheet 12 and a transparent protective film At 14 o'clock, a photocurable adhesive can also be used. Examples of the photocurable adhesive include a mixture of a photocurable epoxy resin and a photocationic polymerization initiator.

以光硬化性接著劑貼合偏光片層12與透明保護膜14之方法,可列舉例如:藉由流佈法、梅耶棒(Meyer bar)塗佈法、凹版塗佈法、缺角輪塗佈機法、刮刀(doctor blade)法、模塗法、浸塗法、噴霧法等,將接著劑塗佈於偏光片層12及/或透明保護膜14的接著面,使兩者疊合之方法。流佈法,係將被塗佈物之偏光片層12或透明保護膜14一邊朝大致垂直的方向、大致水平的方向、或兩者之間的傾斜方向移動,一邊於其表面流下並廣佈接著劑之方法。 Examples of a method for bonding the polarizer layer 12 and the transparent protective film 14 with a photocurable adhesive include, for example, a flow method, a Meyer bar coating method, a gravure coating method, and a corner wheel coating method. A method in which an adhesive is applied to the adhering surface of the polarizer layer 12 and / or the transparent protective film 14 by a mechanical method, a doctor blade method, a die coating method, a dip coating method, a spray method, or the like, and the two are superposed. . The streamer method involves moving the polarizer layer 12 or the transparent protective film 14 of the object to be coated in a substantially vertical direction, a horizontal direction, or an inclined direction therebetween, while flowing down the surface and spreading it.剂 的 方法。 Agent method.

於偏光片層12或透明保護膜14的表面塗佈接著劑後,藉由將偏光片層12及透明保護膜14經由接著劑塗佈面以夾輥(nip roll)等夾持貼合而接著。而且,亦可適合使用於偏光片層12與透明保護膜14疊合之狀態下,於偏光片層12與透明保護膜14間滴下接著劑之後,以輥等加壓該積層物而均勻地加壓延展之方法。此時,輥的材質係可使用金屬或橡膠等。此外,亦宜採用於偏光片層12與透明保護膜14之間滴下接著劑後,使該積層物通過輥與輥之間,進行加壓而擠壓延展之方法。此時,該等輥可為相同材質,亦可為不同材質。使用上述夾輥等而經貼合後的接著劑層之乾燥或硬化前的厚度較佳為0.01μm至5μm。 After the adhesive is applied to the surface of the polarizer layer 12 or the transparent protective film 14, the polarizer layer 12 and the transparent protective film 14 are sandwiched and bonded by a nip roll or the like through the adhesive application surface, and then bonded. . Moreover, it can also be suitably used in a state where the polarizer layer 12 and the transparent protective film 14 are superimposed, and after the adhesive is dropped between the polarizer layer 12 and the transparent protective film 14, the laminate is pressurized with a roller or the like and uniformly applied. Rolling method. In this case, the material of the roller may be metal, rubber, or the like. In addition, it is also suitable to use a method in which after the adhesive is dropped between the polarizer layer 12 and the transparent protective film 14, the laminate is passed between the rollers and pressurized to be stretched. At this time, the rollers may be the same material or different materials. The thickness of the adhesive layer after lamination using the nip roller or the like before drying or curing is preferably 0.01 μm to 5 μm.

於偏光片層12及/或透明保護膜14的接著表面,為了提高接著性,亦可適宜施行電漿處理、電暈放 電處理、紫外線照射處理、火焰(flame)處理、皂化處理等表面處理。皂化處理,可列舉浸漬於如氫氧化鈉或氫氧化鉀之鹼性水溶液之方法。 On the adhering surface of the polarizer layer 12 and / or the transparent protective film 14, in order to improve adhesion, plasma treatment and corona discharge may be suitably performed. Surface treatments such as electric treatment, ultraviolet irradiation treatment, flame treatment, saponification treatment, and the like. Examples of the saponification treatment include a method of immersion in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide.

使用光硬化性樹脂作為接著劑時,係於接合偏光片層12與透明保護膜14後,再照射活性能量射線,藉此使光硬化性接著劑硬化。活性能量射線的光源並無特別限定,惟以具有波長400nm以下之發光分布的活性能量射線為較佳,具體而言,較佳可使用低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、化學燈(chemical lamp)、黑光燈(black-light lamp)、微波激發汞燈、金屬鹵素燈等。 When a photocurable resin is used as the adhesive, the photocurable adhesive is cured by bonding the polarizer layer 12 and the transparent protective film 14 and then irradiating active energy rays. The source of the active energy ray is not particularly limited, but an active energy ray having a light emission distribution of a wavelength of 400 nm or less is preferred, and specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, and an ultrahigh voltage Mercury lamps, chemical lamps, black-light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

對於光硬化性接著劑之光照強度,係依光硬化性接著劑的組成適宜決定,而無特別限定,對聚合起始劑之活性化有效之波長領域的照射強度較佳為0.1至6000mW/cm2。照射強度為0.1mW/cm2以上時,反應時間不會變得過長,為6000mW/cm2以下時,發生光源所輻射的熱及光硬化性接著劑硬化時之發熱所致之環氧樹脂的黃變或偏光膜的劣化之疑慮較少。對於光硬化性接著劑之光照時間,只要視硬化對象之光硬化性接著劑而適用者即可,並無特別限定,惟以上述照射強度與照射時間之乘積表示之積算光量,較佳為以成為10至10000mJ/cm2之方式設定。對於光硬化性接著劑之積算光量為10mJ/cm2以上時,可產生充分量之源自聚合起始劑之活性種,而更確實地進行硬化反應,為10000mJ/cm2以下時,照射時間不會變得過長,可維持良好的生產性。又,活性能量射線照射後的 接著劑層的厚度,通常為0.001μm至5μm左右,較佳為0.01μm至2μm,更佳為0.01μm至1μm。 The light intensity of the photocurable adhesive is appropriately determined depending on the composition of the photocurable adhesive, and is not particularly limited. The irradiation intensity in the wavelength range effective for the activation of the polymerization initiator is preferably 0.1 to 6000 mW / cm 2 . When the irradiation intensity of 0.1mW / cm 2 or more, the reaction time does not become excessively long, is 6000mW / cm 2 or less, occurrence of heat radiated by a light source and a light-curing and then heat-induced hardening of the epoxy resin when There is less concern about yellowing or deterioration of the polarizing film. The light time of the light-curing adhesive is not particularly limited as long as it is applicable depending on the light-curing adhesive of the object to be cured, but the cumulative light amount expressed as the product of the above-mentioned irradiation intensity and irradiation time is preferably It is set to be 10 to 10000 mJ / cm 2 . When the total light amount of the photocurable adhesive is 10 mJ / cm 2 or more, a sufficient amount of active species derived from the polymerization initiator can be generated, and the curing reaction proceeds more reliably. When the light curing time is 10,000 mJ / cm 2 or less, the irradiation time Does not become too long, and maintains good productivity. The thickness of the adhesive layer after active energy ray irradiation is usually about 0.001 μm to 5 μm, preferably 0.01 μm to 2 μm, and more preferably 0.01 μm to 1 μm.

藉由照射活性能量射線使光硬化性接著劑硬化時,較佳為於偏光片層12之偏光度、穿透率及色相、以及透明保護膜14的透明性等偏光板之各種功能不會降低的條件下進行硬化。 When the photo-curable adhesive is hardened by irradiating active energy rays, it is preferable that the polarizer, the transmittance and the hue of the polarizer layer 12 and the various functions of the polarizer such as the transparency of the transparent protective film 14 are not reduced. Harden under the conditions.

[其他的光學層] [Other optical layers]

以上方式所製造的本發明之偏光板,在實際使用時可作成積層有其他光學層之偏光板使用。而且,上述透明保護膜14亦可具有該等光學層之功能。其他的光學層之例可列舉:能穿透某種偏光光且反射顯示與該種偏光光相反性質之偏光光之反射型偏光膜、於表面具有凹凸形狀之附有防眩功能的膜、附有表面抗反射功能的膜、於表面具有反射功能的反射膜、同時具有反射功能與穿透功能的半穿透反射膜、視角補償膜。 The polarizing plate of the present invention manufactured in the above manner can be used as a polarizing plate with other optical layers laminated in actual use. Moreover, the above-mentioned transparent protective film 14 may also function as these optical layers. Examples of other optical layers include reflective polarizing films that can penetrate a certain type of polarized light and reflect and display polarized light having properties opposite to that of the polarized light, a film having an uneven shape on the surface, and an anti-glare function. Film with surface anti-reflection function, reflection film with reflection function on the surface, semi-transmission reflection film with both reflection function and transmission function, and viewing angle compensation film.

相當於能穿透某種偏光光且反射顯示與該種偏光光相反性質之偏光光之反射型偏光膜的市售品,可列舉例如:DBEF(3M公司製,可由住友3M股份有限公司取得)、APF(3M公司製,可由住友3M股份有限公司取得)。視角補償膜可列舉:於基材表面塗佈有液晶性化合物且經定向的光學補償膜、由聚碳酸酯系樹脂所成之相位差膜、由環狀聚烯烴系樹脂所成之相位差膜。相當於於基材表面塗佈有液晶性化合物且經定向的光學補償膜之市售品,可列舉:WV膜(FUJIFILM股份有限公司製)、NH膜(新日本 石油股份有限公司製)、NR膜(新日本石油股份有限公司製)等。此外,相當於由環狀聚烯烴系樹脂所成之相位差膜之市售品,可列舉:ARTON(註冊商標)膜(JSR股份有限公司製)、Escena(註冊商標)(積水化學工業股份有限公司製)、ZEONOR(註冊商標)FILM(OPTES股份有限公司製)等。 A commercially available reflective polarizing film that is equivalent to polarized light that can penetrate a certain type of polarized light and reflect and display properties opposite to this type of polarized light. For example, DBEF (manufactured by 3M Corporation, available from Sumitomo 3M Co., Ltd.) APF (3M company system, can be obtained from Sumitomo 3M Co., Ltd.). Examples of the viewing angle compensation film include an optical compensation film coated with a liquid crystal compound on the surface of the substrate and oriented, a retardation film made of a polycarbonate resin, and a retardation film made of a cyclic polyolefin resin. . Examples of commercially available products that are equivalent to an oriented optical compensation film coated with a liquid crystal compound on the substrate surface include a WV film (manufactured by FUJIFILM Co., Ltd.) and an NH film (new Japan (Produced by Petroleum Corporation), NR membrane (produced by New Japan Petroleum Corporation), etc. In addition, commercially available products equivalent to a retardation film made of a cyclic polyolefin resin include: ARTON (registered trademark) film (manufactured by JSR Corporation), Escena (registered trademark) (Sekisui Chemical Industry Co., Ltd. Company), ZEONOR (registered trademark) FILM (manufactured by OPTES Co., Ltd.), etc.

[偏光性積層膜之製造方法] [Manufacturing method of polarizing laminated film]

第3圖係表示第1圖所示之偏光性積層膜10之製造方法的一種實施形態之流程圖。據此,偏光性積層膜10之製造方法係依序實施下述步驟者:樹脂層形成步驟(S10),其係於基材膜11的一表面上形成皂化度為99.0莫耳%以下、經減壓脫泡之聚乙烯醇系樹脂層而成為積層膜;延伸步驟(S20),其係對上述積層膜以超過5倍之延伸倍率施行單軸延伸處理,成為延伸膜;染色步驟(S30),其係將上述樹脂層以二色性色素染色,得到作為偏光片層12之偏光性積層膜10。 Fig. 3 is a flowchart showing an embodiment of a method for manufacturing the polarizing laminated film 10 shown in Fig. 1. According to this, the method for manufacturing the polarizing laminated film 10 sequentially performs the following steps: a resin layer forming step (S10), which forms a saponification degree of 99.0 mol% or less on one surface of the substrate film 11 and The polyvinyl alcohol-based resin layer that is degassed under reduced pressure becomes a laminated film; the stretching step (S20) is a uniaxial stretching treatment of the laminated film at an extension ratio of more than 5 times, and becomes a stretched film; a dyeing step (S30) It is obtained by dyeing the resin layer with a dichroic dye to obtain a polarizing laminated film 10 as a polarizer layer 12.

藉此製造方法所得之偏光性積層膜10,係成為於經延伸之基材膜11上具備厚度10μm以下的偏光片層12之偏光性積層膜10。該偏光性積層膜10可直接使用作為偏光板,亦可如後述般作為將偏光片層12轉印至透明保護膜用之中間產物使用。 The polarizing multilayer film 10 obtained by this manufacturing method is a polarizing multilayer film 10 having a polarizer layer 12 having a thickness of 10 μm or less on the stretched base film 11. The polarizing laminated film 10 may be used as a polarizing plate as it is, or may be used as an intermediate product for transferring the polarizer layer 12 to a transparent protective film as described later.

所得偏光片之發光因子修正單體穿透率(Ty),通常為40%以上,發光因子修正偏光度(Py)通常為99.9%以上。較佳係Ty為41.0%以上,且Py為99.9%以上。又更佳係Ty為42.5%以上,且Py為99.9%以上。 The luminous factor modified monomer transmittance (Ty) of the obtained polarizer is usually 40% or more, and the luminous factor modified polarization (Py) is usually 99.9% or more. Preferably, Ty is 41.0% or more, and Py is 99.9% or more. Still more preferably, Ty is 42.5% or more, and Py is 99.9% or more.

偏光片之發光因子修正單體穿透率(Ty)及發光因子修正偏光度(Py)係以附積分球之分光光度計(日本分光股份有限公司製,V7100)測定。於波長380nm至780nm之範圍求出MD穿透率與TD穿透率,依式(1)、式(2)算出各波長之單體穿透率、偏光度,進一步藉由JIS Z 8701之2度視野(℃光源)進行發光因子修正,求出發光因子修正單體穿透率(Ty)及發光因子修正偏光度(Py)。其中,「MD穿透率」係由格蘭-湯姆森稜鏡(Glan-Thompson prism)射出的偏光之方向與偏光板試樣的穿透軸平行時之穿透率,於式(1)、式(2)中係以「MD」表示。而且,「TD穿透率」係由格蘭-湯姆森稜鏡射出的偏光之方向與偏光板試樣的穿透軸垂直相交時之穿透率,於式(1)、式(2)中係以「TD」表示。 The luminous factor-corrected monomer transmittance (Ty) and the luminous factor-corrected polarization (Py) of the polarizer were measured using a spectrophotometer with an integrating sphere (manufactured by JASCO Corporation, V7100). Calculate the MD transmittance and TD transmittance in the range of 380nm to 780nm, and calculate the individual transmittance and polarization of each wavelength according to formula (1) and formula (2), and further apply JIS Z 8701-2 Luminance factor correction is performed in a field of view (° C light source), and the luminous factor correction unit transmittance (Ty) and luminous factor correction polarization (Py) are obtained. Among them, "MD transmittance" is the transmittance when the direction of polarized light emitted from Glan-Thompson prism is parallel to the transmission axis of the polarizer sample. In the formula (2), "MD" is used. Moreover, the "TD transmittance" is the transmittance when the direction of the polarized light emitted by Glan-Thomson 稜鏡 perpendicularly intersects the transmission axis of the polarizer sample, and is expressed in equations (1) and (2). It is indicated by "TD".

單體穿透率(%)=(MD+TD)/2 式(1) Cell Transmittance (%) = (MD + TD) / 2 Formula (1)

偏光度(%)={(MD-TD)/(MD+TD)}1/2×100 式(2) Polarization (%) = ((MD-TD) / (MD + TD)) 1/2 × 100 Formula (2)

[偏光板之製造方法] [Manufacturing method of polarizing plate]

第4圖表示第2圖所示之偏光板13之製造方法的一種實施形態之流程圖。據此,偏光板13之製造方法係依序實施下述步驟:樹脂層形成步驟(S10),其係於基材膜的一表面上形成皂化度為99.0莫耳%以下、經減壓脫泡之由聚乙烯醇系樹脂所成的樹脂層而成為積層膜;延伸步驟(S20),其係對上述積層膜以超過5倍之延伸倍率施行單軸延伸處理而成為延伸膜;染色步驟(S30),其係以二色性色素染色 得到作為偏光片層12之偏光性積層膜;之後,依序具備下述步驟:貼合步驟(S40),其係於上述偏光性積層膜的偏光片層12的基材膜11側之面為相反側之面貼合透明保護膜14,得到多層膜;剝離步驟(S50),由上述多層膜剝離基材膜11。 Fig. 4 is a flowchart showing an embodiment of a method of manufacturing the polarizing plate 13 shown in Fig. 2. According to this, the manufacturing method of the polarizing plate 13 sequentially performs the following steps: a resin layer forming step (S10), which forms a saponification degree of 99.0 mol% or less on one surface of the base film, and defoams under reduced pressure. The resin layer made of polyvinyl alcohol resin becomes a laminated film; the stretching step (S20), which is a uniaxial stretching treatment of the laminated film at an extension ratio of more than 5 times to become a stretched film; the dyeing step (S30 ), Which is dyed with dichroic pigments A polarizing laminated film as the polarizer layer 12 is obtained; thereafter, the following steps are sequentially provided: a laminating step (S40), which is on the side of the base film 11 of the polarizing layer 12 of the polarizing laminated film as follows: The transparent protective film 14 is bonded to the opposite surface to obtain a multilayer film. In the peeling step (S50), the base film 11 is peeled from the multilayer film.

藉由此種製造方法所得之偏光板13,係成為於透明保護膜14上具備厚度10μm以下的偏光片層12之偏光板13。此種偏光板13,例如可經由感壓式接著劑貼合於其他的光學膜或液晶單元等而使用。 The polarizing plate 13 obtained by such a manufacturing method is a polarizing plate 13 provided with a polarizer layer 12 having a thickness of 10 μm or less on the transparent protective film 14. Such a polarizing plate 13 can be used, for example, by bonding it to another optical film, a liquid crystal cell, etc. via a pressure-sensitive adhesive.

以下詳細說明第4圖之S40至S50的各步驟。又,第4圖之S10至S30的各步驟係與第3圖之S10至S30的各步驟相同的步驟。 Each step of S40 to S50 in FIG. 4 will be described in detail below. The steps S10 to S30 in FIG. 4 are the same steps as the steps S10 to S30 in FIG. 3.

[貼合步驟(S40)] [Laminating step (S40)]

在此,係於與偏光片層的基材膜側之面為相反側之面貼合透明保護膜而得到多層膜。貼合透明保護膜的方法可列舉:以黏著劑貼合偏光片層12與透明保護膜14之方法、以接著劑貼合偏光片層12之面與透明保護膜14之方法。適合作為透明保護膜之材料係如上述偏光板的結構之說明所述。適合使用之接著劑、黏著劑的材料、及使用該等以貼合偏光片層12與透明保護膜14之較佳方法係如上述偏光板的結構之說明所述。 Here, a multilayer protective film is obtained by laminating a transparent protective film on a surface opposite to the surface on the base film side of the polarizer layer. The method of bonding the transparent protective film includes a method of bonding the polarizer layer 12 and the transparent protective film 14 with an adhesive, and a method of bonding the surface of the polarizer layer 12 and the transparent protective film 14 with an adhesive. A material suitable as a transparent protective film is as described in the structure of the above-mentioned polarizing plate. Suitable adhesives, adhesive materials, and the preferred methods of using these to adhere the polarizer layer 12 and the transparent protective film 14 are as described in the structure of the polarizing plate described above.

[剝離步驟(S50)] [Stripping step (S50)]

本實施形態的偏光板之製造方法如第4圖所示,係在將透明保護膜貼合於偏光片層12的貼合步驟(S40)之後, 再進行基材膜之剝離步驟(S50)。基材膜之剝離步驟(S50),係由多層膜剝離基材膜。基材膜之剝離方法並無特別限定,可以與通常於附有黏著劑的偏光板進行之剝離膜的剝離步驟相同的方法剝離。可以在透明保護膜之貼合步驟(S40)後直接立即剝離,亦可在一度捲取成為捲軸狀之後,另行設置剝離步驟而剝離。 As shown in FIG. 4, the method for manufacturing a polarizing plate in this embodiment is after the step (S40) of bonding a transparent protective film to the polarizer layer 12. Then, the base film peeling step (S50) is performed. The substrate film peeling step (S50) is to peel the substrate film from the multilayer film. The peeling method of the base film is not particularly limited, and it can be peeled in the same manner as the peeling step of a peeling film usually performed on a polarizing plate with an adhesive. It can be peeled off immediately after the step (S40) of laminating the transparent protective film, or it can be peeled off by setting a peeling step after being rolled up into a reel shape once.

以下表示實施例及比較例,以進一步具體說明本發明,惟本發明不限定於該等例。 Examples and comparative examples are shown below to further specifically describe the present invention, but the present invention is not limited to these examples.

(實施例) (Example)

[實施例1] [Example 1]

(1)基材膜的製作 (1) Production of substrate film

藉由使用多層擠出成形機之共擠出成形而製作基材膜,該基材膜係:於由約含5重量%乙烯單元之丙烯/乙烯之無規共聚物(住友化學股份有限公司製之「住友NOBLEN W151」,融點Tm=138℃)所成之樹脂層的兩面配置有由丙烯的同元聚合物(住友化學股份有限公司製之「住友NOBLENFLX80E4」,融點Tm=163℃)所成之樹脂層的3層構造之長尺狀基材膜。基材膜的合計厚度為100μm,各層的厚度比(FLX80E4/W151/FLX80E4)為3/4/3。 A base film is produced by co-extrusion molding using a multi-layer extrusion molding machine, which is a random copolymer of propylene / ethylene containing about 5 wt% of ethylene units (manufactured by Sumitomo Chemical Co., Ltd.) "Sumitomo NOBLEN W151", melting point Tm = 138 ° C) The resin layer formed from both sides is a homopolymer of propylene ("Sumitomo NOBLENFLX80E4" manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 163 ° C) A three-layer long base film with a resin layer formed. The total thickness of the base film is 100 μm, and the thickness ratio (FLX80E4 / W151 / FLX80E4) of each layer is 3/4/3.

(2)塗裝液的調製 (2) Preparation of coating liquid

將聚乙烯醇粉末(日本合成化學工業股份有限公司製之「Z-200」,平均聚合度1100,平均皂化度99.5莫耳%)溶解於95℃的熱水,調製濃度3重量%之聚乙烯醇水溶液。於所得之水溶液中,以相對於聚乙烯醇粉末2重量份為1 重量份之比例混合交聯劑(田岡化學工業股份有限公司製之「Sumirez Resin650」),得到底塗層形成用塗裝液。 Polyvinyl alcohol powder ("Z-200" manufactured by Nippon Synthetic Chemical Industry Co., Ltd., with an average degree of polymerization of 1100 and an average degree of saponification of 99.5 mole%) was dissolved in hot water at 95 ° C to prepare polyethylene having a concentration of 3% by weight. Alcohol solution. In the obtained aqueous solution, 1 part by weight based on 2 parts by weight of the polyvinyl alcohol powder was used. A cross-linking agent ("Sumirez Resin 650" manufactured by Taoka Chemical Industry Co., Ltd.) was mixed in a proportion by weight to obtain a coating liquid for forming an undercoat layer.

將所得之底塗層形成用塗裝液移至30L(公升)之不鏽鋼容器,移送至塗裝設備。 The obtained coating liquid for forming the undercoat layer was transferred to a 30 L (liter) stainless steel container, and transferred to a coating facility.

又,將聚乙烯醇粉末(Kuraray股份有限公司製之「PVA124」、平均聚合度2400、平均皂化度98.0至99.0莫耳%)溶解於95℃的熱水,調製濃度8重量%之聚乙烯醇水溶液,將此作為聚乙烯醇系樹脂層形成用塗裝液。 Also, polyvinyl alcohol powder ("PVA124" manufactured by Kuraray Co., Ltd., average degree of polymerization of 2400, average degree of saponification 98.0 to 99.0 mole%) was dissolved in hot water at 95 ° C to prepare a polyvinyl alcohol having a concentration of 8% by weight An aqueous solution was used as a coating liquid for forming a polyvinyl alcohol-based resin layer.

將所得之聚乙烯醇系樹脂層形成用塗裝液移至30L之不鏽鋼容器,移送至塗裝設備。 The obtained coating liquid for forming a polyvinyl alcohol-based resin layer was transferred to a 30 L stainless steel container and transferred to a coating facility.

(3)實施減壓脫泡 (3) Decompression defoaming

將(2)所調製的聚乙烯醇系樹脂層形成用塗裝液放入處理容器中,以-0.04Mpa(計示壓)處理120分鐘。此時容器係持續吸氣。脫泡處理後的液溫係加溫於26.0℃左右,不實施冷卻而用於塗裝。 The coating liquid for forming a polyvinyl alcohol-based resin layer prepared in (2) was put into a processing container and treated at -0.04 MPa (gauge pressure) for 120 minutes. The container is continuously inhaling. The temperature of the liquid after the defoaming treatment is increased to about 26.0 ° C, and it is used for painting without cooling.

(4)底塗層及聚乙烯醇系樹脂層之形成 (4) Formation of undercoat layer and polyvinyl alcohol resin layer

一邊連續地運送上述(1)所製作的基材膜,一邊於該基材膜的單面施行電暈放電處理,於該經電暈放電處理的面使用微凹版塗佈機連續地塗裝上述(2)所作成的底塗層形成用塗裝液,並於60℃乾燥3分鐘,藉此形成厚度0.2μm之底塗層。繼而,一邊運送膜,一邊使用於塗裝頭填充有聚乙烯醇系樹脂層形成用塗裝液之上述缺角輪式塗佈機,將該塗裝液連續地塗裝於底塗層上,於90℃乾燥1分鐘、於70℃乾燥3分鐘、接著於60℃乾燥4分鐘,藉此於底塗 層上形成厚度11.0μm之聚乙烯醇系樹脂層。 While continuously carrying the base film produced in the above (1), a corona discharge treatment is performed on one side of the base film, and the corona discharge-treated surface is continuously coated with the micro gravure coater. (2) The prepared coating liquid for forming an undercoat layer was dried at 60 ° C. for 3 minutes, thereby forming an undercoat layer having a thickness of 0.2 μm. Next, while the film is being transported, the coating wheel is filled with a coating liquid for forming a polyvinyl alcohol-based resin layer, and the above-mentioned notch wheel coater is used to continuously coat the coating liquid on the undercoat layer. Dry at 90 ° C for 1 minute, at 70 ° C for 3 minutes, and then at 60 ° C for 4 minutes. A polyvinyl alcohol-based resin layer having a thickness of 11.0 μm was formed on the layer.

進一步,於與形成有聚乙烯醇系樹脂層之面為相反側之基材膜面施行與上述相同的處理,依序形成底塗層及聚乙烯醇系樹脂層,於基材膜的兩面形成厚度0.2μm的底塗層及厚度11.0μm的聚乙烯醇系樹脂層,得到由聚乙烯醇系樹脂層/底塗層/基材膜/底塗層/聚乙烯醇系樹脂層的層結構所成之積層膜。 Further, the same treatment as described above is performed on the substrate film surface opposite to the surface on which the polyvinyl alcohol-based resin layer is formed, and an undercoat layer and a polyvinyl alcohol-based resin layer are sequentially formed, and formed on both surfaces of the substrate film. An undercoat layer having a thickness of 0.2 μm and a polyvinyl alcohol-based resin layer having a thickness of 11.0 μm are obtained from a layer structure of a polyvinyl alcohol-based resin layer / undercoat layer / substrate film / undercoat layer / polyvinyl alcohol-based resin layer. Into a laminated film.

(5)積層膜之延伸 (5) Extension of laminated film

一邊連續地輸送上述(4)所得之積層膜,一邊於夾輥間延伸之方式,以160℃之延伸溫度朝縱向(膜輸送方向)以5.5倍之倍率進行自由端單軸延伸,藉此成為延伸膜。延伸膜之聚乙烯醇系樹脂層的厚度,一者為5.5μm,另一者為5.9μm。 While continuously conveying the laminated film obtained in the above (4), while extending between the nip rolls, the free-end uniaxial extension was performed at a stretching temperature of 160 ° C in the longitudinal direction (film conveying direction) at a factor of 5.5 times, thereby becoming Stretch film. The thickness of the polyvinyl alcohol-based resin layer of the stretched film is 5.5 μm in one and 5.9 μm in the other.

(6)偏光性積層膜之製作 (6) Fabrication of polarizing laminated film

一邊連續地輸送上述(5)所製作的延伸膜,一邊以滯留時間為60秒鐘之方式浸漬於60℃的溫水浴中之後,以滯留時間為150秒鐘左右之方式浸漬於包含碘與碘化鉀之30℃的染色溶液中,進行聚乙烯醇系樹脂層的染色處理,接著,以10℃的純水洗去餘量的染色溶液。繼而,以滯留時間為600秒鐘之方式浸漬於包含硼酸與碘化鉀之76℃的交聯溶液中,進行交聯處理。之後,以10℃的純水洗淨4秒鐘,以80℃乾燥300秒鐘,藉此製作偏光性積層膜。 While continuously conveying the stretched film prepared in (5) above, immersed in a warm water bath at 60 ° C so that the retention time is 60 seconds, and then immersed in a solution containing iodine and potassium iodide so that the retention time is about 150 seconds In the dyeing solution at 30 ° C, the polyvinyl alcohol-based resin layer was dyed, and then the remaining dyeing solution was washed with pure water at 10 ° C. Then, it was immersed in a cross-linking solution at 76 ° C. containing boric acid and potassium iodide so that the retention time was 600 seconds, and subjected to a cross-linking treatment. Thereafter, it was washed with pure water at 10 ° C. for 4 seconds, and dried at 80 ° C. for 300 seconds to prepare a polarizing laminated film.

於所得之偏光性積層膜中,積層於基材兩面之偏光片的厚度分別為5.8μm、6.0μm。 In the obtained polarizing laminated film, the thicknesses of the polarizers laminated on both sides of the substrate were 5.8 μm and 6.0 μm, respectively.

(7)觀察長度100μm以上之空隙 (7) Observation of voids with a length of 100 μm or more

剝離所得之偏光性積層膜中厚度為6.0μm之偏光片層,作成由基材膜與厚度5.8μm的偏光片層所成之單面積層膜。 Among the obtained polarizing laminated films, a polarizer layer having a thickness of 6.0 μm was used to form a single-area layer film composed of a base film and a polarizer layer having a thickness of 5.8 μm.

將所得之單面積層膜裁切成吸收軸方向為300mm、與吸收軸垂直的方向為200mm之尺寸,於平面光源上使用放大倍率為10倍的附比例尺之放大鏡進行目視觀察。共計確認20片(1.2m2)積層膜,吸收軸方向的長度為100μm以上的空隙有8個,每單位面積之數為6.7個/m2The obtained single-area layer film was cut into a size of 300 mm in the absorption axis direction and 200 mm in the direction perpendicular to the absorption axis, and visually observed on a flat light source using a magnifying glass with a scale of 10 times and a scale. A total of 20 laminated films (1.2 m 2 ) were confirmed. There were 8 voids having a length in the absorption axis direction of 100 μm or more, and the number per unit area was 6.7 pieces / m 2 .

以附積分球之分光光度計(日本分光股份有限公司製,V7100)測定所得之單面積層膜(由基材膜與厚度5.8μm的偏光片層所成之單面積層膜)於波長380nm至780nm的範圍之MD穿透率與TD穿透率,依照前述式(1)、式(2)算出各波長之單體穿透率、偏光度,進一步依JIS Z 8701之2度視野(℃光源)進行發光因子修正,求出發光因子修正單體穿透率(Ty)及發光因子修正偏光度(Py),為Ty:42.9%、Py:99.92%。 The single-area layer film (single-area layer film made of a base film and a polarizer layer with a thickness of 5.8 μm) measured by a spectrophotometer with a integrating sphere (manufactured by JASCO Corporation, V7100) has a wavelength of The MD transmittance and TD transmittance in the range of 780nm are calculated according to the aforementioned formulas (1) and (2) for the individual transmittance and polarization of each wavelength, and further according to JIS Z 8701's 2-degree field of view (° C light source ) The luminous factor correction is performed, and the luminous factor corrected monomer transmittance (Ty) and the luminous factor corrected polarization (Py) are obtained, which are Ty: 42.9% and Py: 99.92%.

(8)偏光板之製作 (8) Production of polarizing plate

將聚乙烯醇粉末(Kuraray股份有限公司製之「KL-318」、平均聚合度1800)溶解於95℃的熱水,調製濃度3重量%之聚乙烯醇水溶液。於所得之水溶液中以相對於聚乙烯醇粉末2重量份為1重量份之比例混合交聯劑(田岡化學工業股份有限公司製之「Sumirez Resin650」),作為接著劑水溶液。 Polyvinyl alcohol powder ("KL-318" manufactured by Kuraray Co., Ltd., average polymerization degree: 1800) was dissolved in hot water at 95 ° C to prepare a 3% by weight polyvinyl alcohol aqueous solution. A cross-linking agent ("Sumirez Resin 650" manufactured by Taoka Chemical Industry Co., Ltd.) was mixed in the obtained aqueous solution in a proportion of 1 part by weight based on 2 parts by weight of the polyvinyl alcohol powder as an adhesive solution.

繼而,一邊連續地輸送上述(6)所製作的偏光性積層膜,一邊於兩面之偏光片層上塗裝上述接著劑水溶液之後,於偏光片層上貼合在貼合面經施行皂化處理的透明保護膜[由三乙酸纖維素(TAC)所成之透明保護膜(Konica Minolta Opto股份有限公司製之「KC4UY」),厚度40μm],藉由通過一對貼合輥之間而壓著,製作由TAC/偏光片層/底塗層/基材膜/底塗層/偏光片層/TAC的層結構所成之貼合膜。 Next, while continuously transporting the polarizing laminated film produced in the above (6), coating the above-mentioned adhesive aqueous solution on the polarizer layers on both sides, and then bonding the polarizer layer to the bonding surface and performing the saponification treatment. Transparent protective film [transparent protective film made of cellulose triacetate (TAC) ("KC4UY" manufactured by Konica Minolta Opto Co., Ltd., thickness 40 [mu] m]) is pressed between a pair of laminating rollers, An adhesive film made of a layer structure of TAC / polarizer layer / undercoat layer / base film / undercoat layer / polarizer layer / TAC is produced.

繼而,於基材膜與底塗層之界面剝離分割貼合膜,得到由TAC/偏光片層(5.8μm)/底塗層/基材膜所成之膜與由底塗層/偏光片層(6.0μm)/TAC所成之偏光板後,進一步由前者之膜剝離去除基材膜,得到另一片偏光板。於剝離基材膜之步驟中,未發生膜的破裂等不良情況。 Then, the separation and lamination film was peeled off at the interface between the base film and the undercoat layer to obtain a film made of TAC / polarizer layer (5.8 μm) / undercoat layer / base film and an undercoat layer / polarizer layer After the polarizing plate made of (6.0 μm) / TAC, the base film was further removed from the former film to obtain another polarizing plate. In the step of peeling the base film, no defects such as cracking of the film occurred.

(8)黏著劑層積層步驟 (8) Laminating step of adhesive

於所得之偏光片層的厚度為5.8μm的偏光板之底塗層側之表面施行電暈放電處理,於經施行離型處理之PET膜(分隔膜)貼附積層有厚度25μm的丙烯酸系黏著劑之薄片(sheet)狀黏著劑,作成由「分隔膜/黏著劑/底塗層/偏光片層/TAC」所成之附有黏著劑的偏光板。 A corona discharge treatment was performed on the surface of the undercoat layer side of the obtained polarizer with a thickness of 5.8 μm, and a laminated film with a thickness of 25 μm was attached to the PET film (separation film) subjected to the release treatment. The sheet-like adhesive of the adhesive is made of a polarizing plate with an adhesive made of "separating film / adhesive / undercoat layer / polarizer layer / TAC".

(9)評估用試樣之作成 (9) Preparation of evaluation samples

將所得之附黏著劑的偏光板以吸收軸相對於邊呈0°之方式,裁切成60mm×60mm之尺寸,剝離分隔膜,將黏著面貼合於玻璃。以此作為評估試樣。 The obtained polarizing plate with an adhesive was cut into a size of 60 mm × 60 mm so that the absorption axis was 0 ° with respect to the side, the separation film was peeled off, and the adhesive surface was bonded to the glass. This was used as an evaluation sample.

(10)熱衝撃試驗(HS試驗) (10) Thermal shock test (HS test)

於試驗槽中放入24片評估試樣,重複於-40℃ 30分 鐘、於85℃ 30分鐘之循環400次,於偏光片的吸收軸方向產生裂隙。 Put 24 evaluation samples in the test tank, and repeat at -40 ℃ for 30 minutes A cycle of 400 cycles of 30 minutes at 85 ° C for 30 minutes produced cracks in the direction of the absorption axis of the polarizer.

(11)觀察裂隙中的空隙 (11) Observe voids in cracks

使用光學顯微鏡(KEYENCE股份有限公司製之VHX-500)以穿透方式觀察所產生的裂隙,觀察到於所產生的裂隙之中,於1道裂隙內具有看起來像微小氣泡(微泡)所造成之於吸收軸方向未達100μm的微小空隙。微小的空隙,其在厚度方向的長度為偏光片的厚度以下係非常地小,而且與氣泡造成的空隙不同,係包埋於偏光片層中。因此,藉由通常的目視或顯微鏡難以發現及觀察到此種微小的氣泡,惟如前述在裂隙中可被觀察到,而可視為是因裂隙才得以發現者。 An optical microscope (VHX-500 manufactured by KEYENCE Corporation) was used to observe the generated cracks in a penetrating manner. Among the generated cracks, there was a microbubble (microbubble) that looked like one of the cracks. This results in minute voids up to 100 μm in the absorption axis direction. The minute voids, whose length in the thickness direction is smaller than the thickness of the polarizer, are very small, and are different from the voids caused by bubbles, and are embedded in the polarizer layer. Therefore, it is difficult to find and observe such tiny bubbles by ordinary visual inspection or a microscope, but it can be observed in the fissures as described above, and can be regarded as the discoverer due to the fissures.

此種微小的空隙之大小係於吸收軸方向未達100μm,另外,觀察將微小的空隙部分由中央朝吸收軸方向垂直地切斷之剖面,其厚度方向的長度為3μm左右。 The size of such minute voids is less than 100 μm in the direction of the absorption axis, and the cross-section of the minute void portion perpendicularly cut from the center to the direction of the absorption axis is observed, and the length in the thickness direction is about 3 μm.

[實施例2] [Example 2]

除了將實施例1之(3)的減壓處理之計示壓設為-0.09Mpa以外,係與實施例1以相同方式製作試樣而實施評估。處理後的液溫為24.7℃。所得之脫泡處理後的液體系未經實施加溫、冷卻等操作而使用於塗裝。 A sample was produced and evaluated in the same manner as in Example 1 except that the gauge pressure of the reduced-pressure treatment of Example 1 (3) was set to -0.09 MPa. The liquid temperature after the treatment was 24.7 ° C. The obtained liquid system after the defoaming treatment is used for coating without performing operations such as heating and cooling.

此時所評估之偏光片層的厚度為5.2μm。對於由單面積層膜製作之試樣確認吸收軸方向的長度為100μm以上的空隙,空隙的數量為1個,每單位面積之空隙的數量為0.83個/m2The thickness of the polarizer layer evaluated at this time was 5.2 μm. For a sample made of a single-area layer film, it was confirmed that the length of the absorption axis direction was 100 μm or more, the number of voids was one, and the number of voids per unit area was 0.83 per m 2 .

於HS試驗所產生的裂隙之中,於裂隙內觀察到前述微小的空隙者為1個。 Among the cracks generated in the HS test, one of the aforementioned minute voids was observed in the cracks.

此單面積層膜之發光因子修正單體穿透率(Ty)及發光因子修正偏光度(Py)為Ty:42.5%,Py:99.93%。 The luminous factor modified monomer transmittance (Ty) and luminous factor modified polarization (Py) of this single-area layer film were Ty: 42.5% and Py: 99.93%.

[比較例1] [Comparative Example 1]

未實施實施例1之(3)的減壓脫泡處理,而以相同方式作成偏光性積層膜時,一側之面的偏光片層的厚度為5.8μm,另一面的偏光片層的厚度為5.1μm。 When the reduced pressure defoaming treatment of (1) of Example 1 was not performed, and the polarizing laminated film was made in the same manner, the thickness of the polarizer layer on one side was 5.8 μm, and the thickness of the polarizer layer on the other side was 5.1 μm.

此時,厚度為5.8μm的面於長度方向的長度為100μm以上的空隙係44個/m2At this time, there were 44 voids / m 2 in a plane having a thickness of 5.8 μm in a longitudinal direction with a length of 100 μm or more.

對於厚度5.8μm之面以與實施例1以相同方式作成評估試樣並進行評估,因熱衝撃試驗(HS試驗)所產生的裂隙之中,所觀察到的被視為係裂隙內產生裂隙主因之微小的空隙為14個。 An evaluation sample was prepared and evaluated for a surface having a thickness of 5.8 μm in the same manner as in Example 1. Among the cracks generated by the thermal shock test (HS test), the observed causes were considered to be the main causes of cracks in the system cracks. There are 14 tiny gaps.

空隙:吸收軸方向的長度為100μm以上的 空隙的數量(個/m2) Voids: The number of voids with a length in the absorption axis direction of 100 μm or more (pieces / m 2 )

熱衝撃試驗:所觀察到的裂隙內於吸收軸方向未達100μm之微小空隙的裂隙數(道) Thermal shock test: The number of cracks (tracks) in the micro-voids in the observed cracks that do not reach 100 μm in the direction of the absorption axis

(產業上之可利用性) (Industrial availability)

依據本發明之製造方法,可製造氣泡缺陷少、減低產生裂隙的風險之偏光片及包含該偏光片之偏光性積層物以及偏光板。包含該偏光片之偏光板,即使供於考慮到裝設於液晶顯示裝置使用時的溫度變化之熱衝撃試驗,亦較少產生被認為是源自殘留於聚乙烯醇系樹脂層中的微小氣泡(微泡)之空隙所致之裂隙。 According to the manufacturing method of the present invention, it is possible to manufacture a polarizer having fewer bubble defects and reducing the risk of cracks, and a polarizing laminate and a polarizing plate including the polarizer. The polarizing plate including the polarizer, even when subjected to a thermal shock test that takes into consideration the temperature change when used in a liquid crystal display device, generates little bubbles thought to originate from the polyvinyl alcohol-based resin layer. (Microbubbles) caused by voids.

Claims (6)

一種偏光片,其係以二色性色素將延伸後之聚乙烯醇系樹脂層染色而形成者,該偏光片之於吸收軸方向之長度為100μm以上的空隙為0.83個/m2以上10個/m2以下,並且該偏光片的厚度為10μm以下。A polarizer formed by dyeing a stretched polyvinyl alcohol-based resin layer with a dichroic pigment. The length of the polarizer in the direction of the absorption axis is 100 μm or more, and the number of voids is 0.83 / m 2 or more. / m 2 or less, and the thickness of the polarizer is 10 μm or less. 一種偏光性積層膜,其係將申請專利範圍第1項所述之偏光片設於基材膜的至少一側之面。A polarizing laminated film is provided with a polarizer described in item 1 of the scope of patent application on at least one side of a base film. 一種偏光板,其係於申請專利範圍第1項所述之偏光片的至少一側之面,積層透明保護膜。A polarizing plate is formed by laminating a transparent protective film on at least one side of the polarizer described in item 1 of the scope of patent application. 一種偏光性積層膜之製造方法,該偏光性積層膜係於基材膜的至少一側之面形成有由聚乙烯醇系樹脂所成之偏光片層,該偏光片層之於吸收軸方向的長度為100μm以上的空隙為10個/m2以下,並且該偏光片層的厚度為10μm以下;前述製造方法包含下述步驟:於基材膜的至少一側之面塗裝經減壓脫泡之聚乙烯醇系樹脂的水溶液,得到於基材膜的至少一側之面形成有由聚乙烯醇系樹脂所構成之樹脂層的積層膜之步驟;延伸積層膜而得到延伸膜之步驟;以二色性色素將延伸膜之前述樹脂層染色而形成偏光片層之步驟。A method of manufacturing a polarizing laminated film, the polarizing laminated film is formed on at least one side of a base film with a polarizer layer made of a polyvinyl alcohol resin, and the polarizer layer is formed in a direction of an absorption axis. The gap having a length of 100 μm or more is 10 / m 2 or less, and the thickness of the polarizer layer is 10 μm or less; the aforementioned manufacturing method includes the following steps: coating on at least one side of the base film and defoaming under reduced pressure An aqueous solution of a polyvinyl alcohol-based resin to obtain a laminated film having a resin layer composed of a polyvinyl alcohol-based resin formed on at least one side of the base film; a step of extending the laminated film to obtain an extended film; A step of forming a polarizer layer by dyeing the resin layer of the stretched film with a dichroic dye. 如申請專利範圍第4項所述之偏光性積層膜之製造方法,其中,經減壓脫泡之聚乙烯醇系樹脂的水溶液係藉由將計示壓減壓至-0.04MPa以下進行脫泡所得之聚乙烯醇系樹脂的水溶液。The method for producing a polarizing laminated film according to item 4 of the scope of the patent application, wherein the aqueous solution of the polyvinyl alcohol-based resin that has been degassed under reduced pressure is degassed by reducing the gauge pressure to -0.04 MPa or less An aqueous solution of the obtained polyvinyl alcohol-based resin. 一種偏光板之製造方法,其係包含下述步驟:於以申請專利範圍第4項或第5項所述之偏光性積層膜之製造方法所得之偏光性積層膜中的偏光片層之與基材膜側為相反側之面貼合透明保護膜,得到多層膜之貼合步驟;由多層膜剝離前述基材膜之剝離步驟。A method for manufacturing a polarizing plate, comprising the steps of: and a base of a polarizer layer in a polarizing laminated film obtained by the method for manufacturing a polarizing laminated film described in item 4 or 5 of the scope of patent application. A transparent protective film is laminated on the opposite side of the material film side to obtain a laminating step of a multilayer film; and a peeling step of peeling the base film from the multilayer film.
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