TWI545356B - Method for producing polarizing plate - Google Patents

Method for producing polarizing plate Download PDF

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Publication number
TWI545356B
TWI545356B TW101136865A TW101136865A TWI545356B TW I545356 B TWI545356 B TW I545356B TW 101136865 A TW101136865 A TW 101136865A TW 101136865 A TW101136865 A TW 101136865A TW I545356 B TWI545356 B TW I545356B
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Taiwan
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film
active energy
energy ray
adhesive
polarizing plate
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TW101136865A
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Chinese (zh)
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TW201331638A (en
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古川淳
廣岩梓
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住友化學股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203—One or more of the layers being plastic
    • B32B37/206—Laminating a continuous layer between two continuous plastic layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Description

偏光板之製造方法 Method for manufacturing polarizing plate

本發明是有關偏光板的製造方法，該偏光板是構成液晶顯示器等有用的光學構件之一。 The present invention relates to a method of manufacturing a polarizing plate which is one of useful optical members constituting a liquid crystal display or the like.

偏光膜是以作為聚乙烯醇類樹脂膜中吸附配向二色性色素之膜而廣泛使用，已知者為以碘作為二色性色素的碘系偏光膜，或將二色性直接染料作為二色性色素的染料系偏光膜等。此等偏光膜，通常是在其單面或雙面經由接著劑而貼合三醋酸纖維素等透明膜，即可作為偏光板。 The polarizing film is widely used as a film for adsorbing and aligning a dichroic dye in a polyvinyl alcohol-based resin film, and is known as an iodine-based polarizing film containing iodine as a dichroic dye, or a dichroic direct dye as a second. A dye of a coloring dye is a polarizing film or the like. These polarizing films are usually used as a polarizing plate by laminating a transparent film such as cellulose triacetate on one or both sides via an adhesive.

作為在偏光膜的單面或雙面積層透明膜的方法，是預先在透明膜的表面塗布活性能量線硬化型樹脂之後，以一對壓輪(nip roller)(貼合滾輪)挾壓偏光膜與透明膜而貼合，接著照射活性能量線而使其接著硬化的方法(專利文獻1：日本特開2004-245925號公報、專利文獻2：日本特開2009-134190號公報、專利文獻3：日本特開2011-95560號公報)。 As a method of forming a single-sided or double-area transparent film on a polarizing film, after applying an active energy ray-curable resin to the surface of the transparent film in advance, the polarizing film is pressed by a pair of nip rollers (adhesive rollers). A method of bonding to a transparent film, followed by irradiation with an active energy ray, and then hardening it. (Patent Document 1: JP-A-2004-245925, Patent Document 2: JP-A-2009-134190, Patent Document 3: Japanese Laid-Open Patent Publication No. 2011-95560).

如此而製造的偏光板，如不使其成為適切的活性能量線硬化型樹脂時，將有偏光板如起波浪似的產生波浪捲的捲曲之情形。如在偏光板上產生波浪捲時，不僅外觀不良，將其貼合在液晶晶胞時，容易在接著面殘留氣泡或使作業性降低，同時也 是使液晶顯示器的顯示品質下降的原因。 When the polarizing plate manufactured in this manner is not made into a suitable active energy ray-curable resin, there is a case where the polarizing plate is curled like a wave. When a wave roll is generated on a polarizing plate, not only the appearance is poor, but when it is bonded to the liquid crystal cell, it is easy to leave bubbles on the adhesive surface or to reduce workability, and also This is the reason why the display quality of the liquid crystal display is lowered.

專利文獻3中所述，是在照射活性能量線而使活性能量線硬化型樹脂硬化之際，一邊使積層體密著在滾輪外緣面一邊使其硬化，而可抑制波浪捲等的發生。 In the case of the active energy ray-curable resin, the layered body is cured while being adhered to the outer surface of the roller, and the occurrence of a wave roll or the like can be suppressed.

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

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

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

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

至於具有藉由照射活性能量線而使活性能量線硬化型樹脂硬化的步驟之偏光板的製造方法，是如同在積層體的表面，產生起波浪似的起伏(以下稱為「波狀斑」)。在偏光板上產生波狀斑，與波浪捲相同，將因外觀不良而成為液晶顯示器中品質降低的原因。本發明的目的，是意圖抑制上述波狀斑的發生。 As for the method for producing a polarizing plate having a step of curing the active energy ray-curable resin by irradiating the active energy ray, a wave-like undulation (hereinafter referred to as "wavy plaque") is generated as on the surface of the laminated body. . A wavy spot is generated on the polarizing plate, which is the same as the wave roll, and causes deterioration in quality in the liquid crystal display due to poor appearance. It is an object of the present invention to suppress the occurrence of the aforementioned wavy spots.

本發明是在偏光膜的單面或雙面貼合透明膜而形成偏光板之製造方法，該方法依序具備：在上述透明膜的單面或上述偏光膜的單面或雙面塗布活性能量線硬化型接著劑之接著劑塗布步驟、對上述透明膜經由上述接著劑積層在前述偏光膜的單面或雙面所形成的積層體，施加壓力而使上述透明膜與上述偏光膜貼合的貼合步驟，使積層體以與在運送方向旋轉的滾輪密著之狀 態的運送之間，對上述積層體照射活性能量線而使上述接著劑硬化的第1活性能量線照射步驟，上述第1活性能量線照射步驟中，紫外線(UVB)的累積光量為10mJ/cm2以上且185mJ/cm2以下。上述滾輪，宜為冷卻滾輪。 The present invention relates to a method for producing a polarizing plate by laminating a transparent film on one surface or both surfaces of a polarizing film, and the method comprises sequentially applying active energy to one surface or both surfaces of the polarizing film on one side of the transparent film. An adhesive application step of a line-curable adhesive, a pressure applied to the laminate formed on one surface or both surfaces of the polarizing film via the adhesive layer, and the transparent film is bonded to the polarizing film In the bonding step, the first active energy ray irradiation step of irradiating the laminate with the active energy ray and curing the adhesive between the laminate and the roller in the state of being transported in the transport direction is performed, and the first active energy ray irradiation step, a cumulative light quantity of ultraviolet (UVB) is 2 or more and 185mJ / cm 2 or less 10mJ / cm. The above roller is preferably a cooling roller.

上述本發明中，上述透明膜的至少一方為醋酸纖維素系樹脂時，效果較高。 In the above invention, when at least one of the transparent films is a cellulose acetate-based resin, the effect is high.

上述本發明，在第1活性能量線照射步驟之後，也可再具備對前述積層體照射活性能量線而使前述接著劑硬化的第2活性能量線照射步驟。 In the above aspect of the invention, after the first active energy ray irradiation step, a second active energy ray irradiation step of irradiating the layered body with an active energy ray to cure the adhesive may be further provided.

在上述本發明的一實施形態中，第1活性能量線照射步驟中，可以數個光源進行活性能量線的照射。 In an embodiment of the present invention described above, in the first active energy ray irradiation step, the plurality of light sources may be used to irradiate the active energy ray.

根據本發明，即可製作波狀斑與波浪捲的發生受到抑制之外觀良好的偏光板。所以，如使用藉由本發明的製造方法而得的偏光板時，可提供防止對液晶晶胞貼合的作業性降低，同時高品質的液晶顯示器。 According to the present invention, it is possible to produce a polarizing plate having a good appearance in which the occurrence of wavy spots and wave rolls is suppressed. Therefore, when a polarizing plate obtained by the manufacturing method of the present invention is used, it is possible to provide a high-quality liquid crystal display while preventing workability in bonding liquid crystal cells.

1‧‧‧偏光膜 1‧‧‧ polarizing film

2、3‧‧‧透明膜 2, 3‧‧‧ transparent film

4‧‧‧積層體(偏光板) 4‧‧‧Laminated body (polarizer)

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

13‧‧‧滾輪(冷卻滾輪) 13‧‧‧Roller (cooling roller)

16、17、18、31、32、33‧‧‧活性能量線照射裝置 16, 17, 18, 31, 32, 33‧‧‧ active energy ray irradiation device

19‧‧‧運送用壓輪 19‧‧‧Loading wheel

20‧‧‧捲取滾輪 20‧‧‧Rolling wheel

51、52‧‧‧貼合滾輪 51, 52‧‧‧ fitted roller

第1圖表示本發明相關的偏光板之製造置之一實施形態的概略側面圖。 Fig. 1 is a schematic side view showing an embodiment of a manufacturing method of a polarizing plate according to the present invention.

第2圖表示本發明相關的偏光板之製造置之一實施形態的概略側面圖。 Fig. 2 is a schematic side view showing an embodiment of a manufacturing method of a polarizing plate according to the present invention.

本發明是在偏光膜的單面或雙面貼合透明膜而形成 偏光板之製造方法，其中依序具備：在透明膜的單面或偏光膜的單面或雙面塗布活性能量線硬化型接著劑之接著劑塗布步驟、對透明膜經由接著劑積層在偏光膜的單面或雙面所形成的積層體，施加壓力而使透明膜與偏光膜貼合之貼合步驟，使積層體以與在運送方向旋轉的滾輪密著之狀態的運送之間，對積層體照射活性能量線而使前述接著劑硬化的第1活性能量線照射步驟，在上述第1活性能量線照射步驟中，紫外線(UVB)的累積光量為10mJ/cm2以上且185mJ/cm2以下。 The present invention relates to a method for producing a polarizing plate by laminating a transparent film on one or both sides of a polarizing film, wherein the active energy ray-curing type is applied to one side or both sides of the transparent film. a step of applying an adhesive to the adhesive agent, and a step of applying a pressure to the laminate formed on one surface or both surfaces of the polarizing film via an adhesive layer to bond the transparent film and the polarizing film, so that the laminated body is laminated. The first active energy ray irradiation step of irradiating the laminated body with the active energy ray to cure the adhesive between the carrier in a state in which the roller rotating in the transport direction is adhered, and the ultraviolet ray irradiation step in the first active energy ray irradiation step (UVB) accumulated light amount of 2 or more and 185mJ / cm 2 or less 10mJ / cm.

首先，說明本發明的製造方法中使用的各項要素。 First, each element used in the production method of the present invention will be described.

(偏光膜) (polarized film)

本發明的偏光板的製造方法中使用的偏光膜，具體上是單軸延伸的聚乙烯醇系樹脂膜中已吸附配向二色性色素之膜。聚乙烯醇系樹脂膜，可由聚乙烯醋酸系樹脂皂化而得。作為聚乙烯醋酸系樹脂，可列舉：例如除了醋酸乙烯酯的單獨聚合物之聚醋酸乙烯酯之外，尚有醋酸乙烯酯與可與其共聚合的其他單體之共聚合物(例如，乙烯-醋酸乙烯酯共聚合物)等。作為可與醋酸乙烯酯共聚合之其他單體，另外可舉出不飽和羧酸類、烯烴類、乙烯醚類、不飽和磺酸類、具有銨基的丙烯醯胺類等。聚乙烯醇系樹脂的皂化度是85莫耳%以上，並宜為90莫耳%以上，而以98至100莫耳%更佳。聚乙烯醇系樹脂的平均聚合度，通常是1,000至10,000，並宜為1,500至5,000。此等聚乙烯醇系樹脂，可以是改質者，例如也可使用經醛類改質的聚乙烯甲醛、聚乙烯乙醛、聚乙烯丁醛等。 The polarizing film used in the method for producing a polarizing plate of the present invention is specifically a film in which a dichroic dye is adsorbed in a uniaxially stretched polyvinyl alcohol resin film. The polyvinyl alcohol-based resin film can be obtained by saponifying with a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, for example, in addition to polyvinyl acetate of a single polymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith (for example, ethylene- Vinyl acetate copolymer) and the like. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The degree of saponification of the polyvinyl alcohol-based resin is 85 mol% or more, and is preferably 90 mol% or more, more preferably 98 to 100 mol%. The average degree of polymerization of the polyvinyl alcohol-based resin is usually from 1,000 to 10,000, and preferably from 1,500 to 5,000. These polyvinyl alcohol-based resins may be modified, and for example, aldehyde-modified polyethylene formaldehyde, polyvinyl acetaldehyde, polyvinyl butyral or the like may be used.

使此種聚乙烯醇系樹脂製膜之膜，可使用作為偏光 膜之原材料膜。聚乙烯醇系樹脂的製膜方法，並無特別的限定，可以從來即知的適宜方法製膜。包含聚乙烯醇系樹脂的原材料膜之膜厚，並無特別的限定，例如大約是10至150μm。通常是以滾輪狀供應，厚度為20至100μm的範圍內，並宜為30至80μm的範圍內，同時，工業上實用的幅寬是在1,500至6,000mm的範圍內。 A film made of such a polyvinyl alcohol-based resin can be used as a polarizing film. The raw material film of the film. The film forming method of the polyvinyl alcohol-based resin is not particularly limited, and a film can be formed by a suitable method known per se. The film thickness of the raw material film containing a polyvinyl alcohol-based resin is not particularly limited, and is, for example, about 10 to 150 μm. It is usually supplied in the form of a roll having a thickness in the range of 20 to 100 μm, and preferably in the range of 30 to 80 μm, while the industrially practical width is in the range of 1,500 to 6,000 mm.

作為市售的聚乙烯醇系膜，可列舉：例如(Vinylon VF-PS#7500，Kuraray製/OPL膜M-7500，日本合成製)的原材料厚度為75μm、(Vinylon VF-PS#6000，Kuraray製與Vinylon VF-PE#6000，Kuraray、Vinylon VF-PE#5000，Kuraray製)的原材料厚度為60μm等。 As a commercially available polyvinyl alcohol-based film, for example, (Vinylon VF-PS #7500, Kuraray/OPL film M-7500, manufactured by Nippon Synthetic Co., Ltd.) has a raw material thickness of 75 μm (Vinylon VF-PS#6000, Kuraray). The raw material thickness of Vinnylon VF-PE #6000, Kuraray, Vinylon VF-PE #5000, manufactured by Kuraray is 60 μm.

偏光膜的製造，通常是經過：以二色性色素將聚乙烯醇系樹脂膜染色而使二色性色素吸附的步驟(染色處理步驟)、以硼酸水溶液處理經二色性色素經吸附的聚乙烯醇系樹脂膜之步驟(硼酸處理步驟)，以及經此硼酸水溶液處理後的水洗步驟(水洗處理步驟)。 The production of the polarizing film is usually carried out by dyeing a polyvinyl alcohol-based resin film with a dichroic dye to adsorb a dichroic dye (dyeing step), and treating the dichroic dye by a boric acid aqueous solution. A step of a vinyl alcohol resin film (boric acid treatment step), and a water washing step (water washing treatment step) after the aqueous boric acid treatment.

同時，在製造偏光膜之際，通常是使聚乙烯醇類樹脂膜單軸延伸，此單軸延伸可在染色處理步驟之前進行，也可在染色處理步驟中進行，也可在染色處理步驟之後進行。如使單軸延伸在染色處理步驟之後進行，此單軸延伸可在硼酸處理步驟之前進行，也可在硼酸處理步驟中進行。無論如何，均可以此等之複數階段進行單軸延伸。 Meanwhile, at the time of manufacturing the polarizing film, the polyvinyl alcohol-based resin film is usually uniaxially stretched, and the uniaxial stretching may be performed before the dyeing treatment step, or may be performed in the dyeing treatment step, or after the dyeing treatment step. get on. If the uniaxial extension is carried out after the dyeing treatment step, this uniaxial stretching can be carried out before the boric acid treatment step or in the boric acid treatment step. In any case, the uniaxial extension can be performed in the plural stages of this.

單軸延伸可如同以周速不同的滾輪間在單軸延伸，也可如同使用熱滾輪的在單軸延伸。同時。可在大氣中行乾式延 伸，也可在溶劑中使其以膨脹狀態進行濕式延伸。延伸倍率，通常大約是3至8倍。 The uniaxial extension can be uniaxially extended as if the rollers are different at a peripheral speed, or can be uniaxially extended as with a hot roller. Simultaneously. Dry extension in the atmosphere Stretching, it is also possible to carry out wet stretching in an expanded state in a solvent. The stretching ratio is usually about 3 to 8 times.

染色處理步驟中以二色性色素使聚乙烯醇系樹脂膜的染色，例如是將聚乙烯醇系樹脂膜浸漬在含有二色性色素的水溶液中進行。作為二色性色素，例如可使用碘、二色性染料等。在二色性染料中，可包含例如C.I.直接紅(direct red)39等包含重氮基化合物的二色性直接染料、包含三氮基、四方氮基等化合物的二色性直接染料。而且，聚乙烯醇系樹脂膜，宜在染色處理之前使其施以水中的浸漬處理。 In the dyeing treatment step, the polyvinyl alcohol-based resin film is dyed with a dichroic dye, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye. As the dichroic dye, for example, iodine, a dichroic dye or the like can be used. The dichroic dye may include, for example, a dichroic direct dye containing a diazo compound such as C.I. direct red 39, or a dichroic direct dye containing a compound such as a trinitro group or a tetrakilyzide group. Further, the polyvinyl alcohol-based resin film is preferably subjected to an immersion treatment in water before the dyeing treatment.

在使用碘作為二色性色素時，通常採用的方法是將聚乙烯醇系樹脂膜浸漬在含有碘及碘化鉀的水溶液中而染色。此水溶液中的碘之含量，通常是相當於水100重量份時的0.01至1重量份，碘化鉀的含量，通常是相當於水100重量份時的0.5至20重量份。在使用碘作為二色性色素時，染色中使用的水溶液之溫度，通常是20至40℃，在此水溶液的浸漬時間(染色時間)，通常是20至1,800秒。 When iodine is used as the dichroic dye, a method is generally employed in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing iodine and potassium iodide to be dyed. The content of iodine in the aqueous solution is usually 0.01 to 1 part by weight based on 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight based on 100 parts by weight of water. When iodine is used as the dichroic dye, the temperature of the aqueous solution used for dyeing is usually 20 to 40 ° C, and the immersion time (dyeing time) of the aqueous solution is usually 20 to 1,800 seconds.

另一方面，使用二色性染料作為二色性色素時，通常採用的方法，是將聚乙烯醇系樹脂膜浸漬在含有二色性染料的水溶液中而染色。此水溶液中的二色性染料之含量，通常是相當於水100重量份時的1×10-4至10重量份，並宜為1×10-3至1重量份，而以1×10-3至1×10-2重量份尤佳。此水溶液也可含有硫酸鈉等無機鹽作為染色助劑。在使用二色性染料作為二色性色素時，染色中使用的染料水溶液之溫度，通常是20至80℃，又，在此水溶液的浸漬時間(染色時間)，通常是10至1,800秒。 On the other hand, when a dichroic dye is used as a dichroic dye, a method is generally employed in which a polyvinyl alcohol-based resin film is immersed in an aqueous solution containing a dichroic dye to be dyed. The content of the dichroic dye in the aqueous solution is usually from 1 × 10 -4 to 10 parts by weight, and preferably from 1 × 10 -3 to 1 part by weight, based on 100 parts by weight of water, and is 1 × 10 - It is particularly preferably 3 to 1 × 10 -2 parts by weight. The aqueous solution may also contain an inorganic salt such as sodium sulfate as a dyeing aid. When a dichroic dye is used as the dichroic dye, the temperature of the aqueous dye solution used in the dyeing is usually 20 to 80 ° C, and the immersion time (dyeing time) of the aqueous solution is usually 10 to 1,800 seconds.

硼酸處理步驟，是將經二色性色素染色的聚乙烯醇系樹脂膜浸漬在含有硼酸的水溶液中進行。含有硼酸的水溶液中硼酸之量，是相當於水100重量份時的2至15重量份，並宜為5至12重量份。在上述的染色處理步驟中使用碘作為二色性色素時，宜使此硼酸處理步驟中使用的含有硼酸的水溶液含有碘化鉀。此時，含有硼酸的水溶液中的碘化鉀之量，通常是相當於水100重量份時的0.1至15重量份，並宜為5至12重量份。在含有硼酸的水溶液中之浸漬時間，通常是60至1,200秒，並宜為150至600秒，而以200至400秒更佳。在含有硼酸的水溶液中的溫度，通常是40℃以上，並宜為50至85℃，而以55至75℃更佳。 In the boric acid treatment step, the polyvinyl alcohol-based resin film dyed with the dichroic dye is immersed in an aqueous solution containing boric acid. The amount of boric acid in the aqueous solution containing boric acid is 2 to 15 parts by weight, and preferably 5 to 12 parts by weight, based on 100 parts by weight of water. When iodine is used as the dichroic dye in the above dyeing treatment step, it is preferred that the aqueous solution containing boric acid used in the boric acid treatment step contains potassium iodide. At this time, the amount of potassium iodide in the aqueous solution containing boric acid is usually 0.1 to 15 parts by weight, and preferably 5 to 12 parts by weight, based on 100 parts by weight of water. The immersion time in the aqueous solution containing boric acid is usually 60 to 1,200 seconds, and preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature in the aqueous solution containing boric acid is usually 40 ° C or higher, and preferably 50 to 85 ° C, and more preferably 55 to 75 ° C.

在接著的水洗處理步驟中，是將上述硼酸處理後的聚乙烯醇系樹脂膜浸漬在例如水中的水洗處理。水洗處理中的水之溫度，通常是4至40℃，浸漬時間通常是1至120秒。水洗處理後，通常施以乾燥處理，即可得偏光膜。乾燥處理例如可適用熱風乾燥機、遠紅外線加熱器等。乾燥處理的溫度，通常是30至100℃，並宜為50至80℃。乾燥處理的時間，通常是60至600秒，並宜為120至600秒。 In the subsequent water washing treatment step, the polyvinyl alcohol-based resin film after the boric acid treatment is immersed in, for example, water washing treatment. The temperature of the water in the water washing treatment is usually 4 to 40 ° C, and the immersion time is usually 1 to 120 seconds. After the water washing treatment, a drying treatment is usually applied to obtain a polarizing film. For the drying treatment, for example, a hot air dryer, a far infrared heater, or the like can be applied. The temperature of the drying treatment is usually from 30 to 100 ° C, and preferably from 50 to 80 ° C. The drying treatment time is usually 60 to 600 seconds, and preferably 120 to 600 seconds.

如此的在聚乙烯醇系樹脂膜，施以單軸延伸、二色性色素的染色、硼酸處理及水洗處理後，即可得偏光膜。此偏光膜的厚度，通常是5至50μm的範圍。 Such a polyvinyl alcohol-based resin film is subjected to uniaxial stretching, dyeing of a dichroic dye, boric acid treatment, and water washing treatment to obtain a polarizing film. The thickness of this polarizing film is usually in the range of 5 to 50 μm.

(透明膜) (Transparent film)

本發明中，可使透明膜貼合在上述的偏光膜之單面或雙面。作為構成透明膜的材料，可列舉：例如環烯烴系樹脂、醋酸纖維素系樹脂、如聚對苯二甲酸乙二酯或聚萘二甲酸乙二 酯、聚對苯二甲酸丁二酯等聚酯系樹脂、聚碳酸酯系樹脂、如聚甲基丙烯酸甲酯(PMMA)等丙烯酸系樹脂、如聚丙烯等烯烴系樹脂等，以往即可在該領域中廣泛使用的膜材料。如使透明膜貼合在偏光膜的雙面時，雖然各個透明膜可以是相同，也可以是不同種類的膜，但至少一方是醋酸纖維素系樹脂時，效果較高。如使用醋酸纖維素系樹脂時作為透明膜時，容易產生波狀斑，因此應用本發明的偏光板之製造方法，可明顯見到波狀斑發生的抑制效果。 In the present invention, a transparent film can be bonded to one side or both sides of the above-mentioned polarizing film. Examples of the material constituting the transparent film include a cycloolefin resin, a cellulose acetate resin, such as polyethylene terephthalate or polyethylene naphthalate. A polyester resin such as an ester or a polybutylene terephthalate, a polycarbonate resin, an acrylic resin such as polymethyl methacrylate (PMMA), or an olefin resin such as polypropylene, etc. Membrane materials widely used in the field. When the transparent film is bonded to both surfaces of the polarizing film, the respective transparent films may be the same, and may be different types of films. However, when at least one of them is a cellulose acetate-based resin, the effect is high. When a cellulose acetate-based resin is used as the transparent film, wavy spots are likely to occur. Therefore, the method for producing a polarizing plate of the present invention can clearly exhibit the effect of suppressing the occurrence of wavy spots.

環烯烴系樹脂，是指例如降冰片烯、多環降冰片烯系單體，具有包含環狀烯烴(環烯烴)的單體的單元之熱可塑性樹脂(也可稱為熱可塑性環烯烴系樹脂)。環烯烴系樹脂，可以是使用上述環烯烴的開環聚合物或2種以上的環烯烴之開環共聚合物的氫化物，也可以是環烯烴與具有鏈狀烯烴、乙烯基的芳香族化合物等之加成聚合物。同時，導入極性基的聚合物也是有效。 The cycloolefin-based resin is, for example, a norbornene or a polycyclic norbornene-based monomer, and a thermoplastic resin having a unit of a monomer including a cyclic olefin (cycloolefin) (also referred to as a thermoplastic cycloolefin-based resin). ). The cycloolefin resin may be a hydrogenated product of a ring-opening polymer of the above cyclic olefin or a ring-opening copolymer of two or more kinds of cyclic olefins, or a cyclic olefin and an aromatic compound having a chain olefin or a vinyl group. Addition of the polymer. At the same time, it is also effective to introduce a polar group-containing polymer.

使用環烯烴與鏈狀烯烴或/及具有乙烯基的芳香族化合物之共聚合物時，作為鏈狀烯烴，可列舉：例如乙烯、丙烯等，又，作為具有乙烯基的芳香族化合物，可列舉苯乙烯、α-甲基苯乙烯、核烷基取代苯乙烯等。此等共聚合物中，包含環烯烴的單體單元可為50莫耳%以下(並宜為15至50莫耳%)。尤其是，使用環烯烴與鏈狀烯烴及具有乙烯基的芳香族化合物之三元共聚合物時，包含環烯烴的單體單元可較少於上述之量。這種三元共聚合物中，包含鏈狀烯烴的單體的單元通常是5至80莫耳%，包含具有乙烯基的芳香族化合物的單體的單元通常是5至80莫耳%。 When a copolymer of a cyclic olefin and a chain olefin or an aromatic compound having a vinyl group is used, examples of the chain olefin include, for example, ethylene and propylene, and examples of the aromatic compound having a vinyl group include Styrene, α-methylstyrene, nucleoalkyl-substituted styrene, and the like. In such a copolymer, the monomer unit containing a cyclic olefin may be 50 mol% or less (and preferably 15 to 50 mol%). In particular, when a ternary copolymer of a cyclic olefin and a chain olefin and an aromatic compound having a vinyl group is used, the monomer unit containing a cycloolefin may be less than the above amount. In such a ternary copolymer, the unit of the monomer containing a chain olefin is usually 5 to 80 mol%, and the unit of the monomer containing an aromatic compound having a vinyl group is usually 5 to 80 mol%.

環烯烴系樹脂，也可使用適宜的市售品，例如可適 用Topas(Ticona社製)、Arton(JSR(株)製)、ZEONOR(日本Zeon(株)製)、ZEONEX(日本Zeon(株)製)、Apel(三井化學(株)製、OXIS(大倉工業社製)等。在將此種環烯烴系樹脂製膜成膜之際，可適宜的使用溶劑鑄模法、熔融押出法等已周知的方法。同時，也可使用Esushina(積水化學工業(株)製)、SCA40(積水化學工業(株)製)、ZEONOR膜(Optes(株)製)等已預先製膜的環烯烴系樹脂製膜的市售品。 As the cycloolefin resin, a suitable commercial product can also be used, for example, suitable TOPIS (manufactured by Ticona Co., Ltd.), Arton (manufactured by JSR Corporation), ZEONOR (made by Japan Zeon Co., Ltd.), ZEONEX (made by Japan Zeon Co., Ltd.), Apel (manufactured by Mitsui Chemicals, Inc.), OXIS (Dakura Industry Co., Ltd.) In the case of forming a film of such a cycloolefin-based resin, it is possible to use a well-known method such as a solvent casting method or a melt-extrusion method, and it is also possible to use Esushina (Sekisui Chemical Industry Co., Ltd.). A commercially available product of a cycloolefin-based resin film which has been previously formed into a film, such as SCA40 (manufactured by Sekisui Chemical Co., Ltd.) and a ZEONOR film (manufactured by Optes Co., Ltd.).

環烯烴系樹脂膜，可以是單軸延伸或二軸延伸之膜。因延伸，而可在環烯烴系樹脂膜賦予任意的相位差值。延伸，通常是將膜輪狀物(film roll)捲出時一邊連續的進行，可在加熱爐中朝滾輪的進行方向(膜之長臂方向)、與該進行方向垂直的方向(膜之寬幅方向)，或其兩方延伸。加熱爐的溫度，通常是採用環烯烴系樹脂的玻璃轉移溫度附近至玻璃轉移溫度+100℃的範圍。延伸的倍率，通常是1.1至6倍，並宜為1.1至3.5倍。 The cycloolefin resin film may be a film which is uniaxially stretched or biaxially stretched. Any phase difference value can be imparted to the cycloolefin resin film by stretching. The stretching is usually carried out continuously while the film roll is wound out, and can be carried out in the direction of the progress of the roller (the long arm direction of the film) in the heating furnace, and the direction perpendicular to the direction of the film (the width of the film) Width direction), or both of them extend. The temperature of the heating furnace is usually in the range from the vicinity of the glass transition temperature of the cycloolefin resin to the glass transition temperature + 100 °C. The magnification of the extension is usually 1.1 to 6 times, and preferably 1.1 to 3.5 times.

環烯烴系樹脂膜如為滾輪捲狀態時，因將使膜之間接著而容易有產生堆積的傾向，故通常是貼合保護膜(protect film)之後使其輪捲。同時，環烯烴系樹脂膜，一般由於表面活性不佳，故宜對其與偏光膜接著的表面，進行電漿處理、電暈處理、紫外線照射處理、火焰處理、皂化處理等表面改質處理。其中，並以比較容易實施的電漿處理較為理想，尤其是大氣壓電漿處理、電暈處理。 When the cycloolefin-based resin film is in the state of a roller roll, the film tends to be deposited due to the subsequent adhesion between the films. Therefore, it is usually rolled up after bonding a protective film. At the same time, since the cycloolefin-based resin film generally has poor surface activity, it is preferable to carry out surface modification treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, and saponification treatment on the surface adjacent to the polarizing film. Among them, plasma treatment is relatively easy to implement, especially atmospheric piezoelectric slurry treatment and corona treatment.

醋酸纖維素系樹脂，是指纖維素的部份或完全酯化物，可列舉：例如包含纖維素的醋酸酯、丙酸酯、酪酸酯，此等酯之混合酯等的膜。更具體而言，可列舉：三乙醯基纖維素膜、 二乙醯基纖維素膜、纖維素醋酸酯丙酸酯膜、纖維素醋酸酯丁酸酯膜等。作為此種醋酸纖維素系樹脂膜，可適用適宜的市售品，例如Fujitac TD80(富士軟片(株)製)、Fujitac TD80UF(富士軟片(株)製)、Fujitac TD80UZ(富士軟片(株)製)、KC8UX2M(Konica Minolta Opto(株)製)、KC8UY(Konica Minolta Opto(株)製)、Fujitac TD60UF(富士軟片(株)製)、KC2UAW(Konica Minolta Opto(株)製)、KC4UYW(Konica Minolta Opto(株)製)、KC6UAW(Konica Minolta Opto(株)製)等。 The cellulose acetate-based resin refers to a partially or fully esterified cellulose, and examples thereof include a cellulose acetate-containing ester, a propionate, a tyrosyl ester, and a mixed ester of these esters. More specifically, a triethylenesulfonated cellulose film can be cited. A diethyl acetyl cellulose film, a cellulose acetate propionate film, a cellulose acetate butyrate film, or the like. For the cellulose acetate-based resin film, a commercially available product such as Fujitac TD80 (made by Fujifilm Co., Ltd.), Fujitac TD80UF (made by Fujifilm Co., Ltd.), and Fujitac TD80UZ (made by Fujifilm Co., Ltd.) can be used. ), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC8UY (Konica Minolta Opto Co., Ltd.), Fujitac TD60UF (made by Fujifilm Co., Ltd.), KC2UAW (Konica Minolta Opto Co., Ltd.), KC4UYW (Konica Minolta) Opto Co., Ltd., KC6UAW (Konica Minolta Opto Co., Ltd.), and the like.

同時，作為透明膜，宜適用經賦予相位差特性的醋 酸纖維素系樹脂膜。作為這種經賦予相位差特性的醋酸纖維素系樹脂膜之市售品，可列舉：例如WV BZ 438(富士軟片(株)製)、KC4FR-1(Konica Minolta Opto(株)製)、KC4CR-1(Konica Minolta Opto(株)製)、KC4AR-1(Konica Minolta Opto(株)製)等。醋酸纖維素也稱為乙醯基纖維素，也可稱為纖維素醋酸酯。 At the same time, as a transparent film, vinegar with phase difference characteristics should be applied. An acid cellulose resin film. For example, WV BZ 438 (made by Fujifilm Co., Ltd.), KC4FR-1 (Konica Minolta Opto Co., Ltd.), KC4CR, etc. are mentioned as a commercial item of the cellulose acetate- -1 (Konica Minolta Opto Co., Ltd.), KC4AR-1 (Konica Minolta Opto Co., Ltd.), etc. Cellulose acetate, also known as acetyl cellulose, may also be referred to as cellulose acetate.

此等醋酸纖維素系樹脂膜容易吸水，故有使偏光板 的水分率影響到偏光板之端部下垂的情形。製造偏光板時的水分率，宜越接近於偏光板的保管環境越好，例如在無塵室(clcan room)的製造線或輪捲保管倉庫的平衡水分率，也可受到積層膜之構成的影響，例如大約2.0至3.5%左右，並宜為2.5至3.0%。此偏光板的水分率數值因為是以乾燥重量法測定，故為105℃/120分鐘後的重量變化。 These cellulose acetate-based resin films are easy to absorb water, so there is a polarizing plate. The moisture rate affects the case where the end of the polarizing plate sags. The water content at the time of manufacturing the polarizing plate should be as close as possible to the storage environment of the polarizing plate. For example, the equilibrium moisture content in the manufacturing line of the clcan room or the storage warehouse of the coil can also be constituted by the laminated film. The influence is, for example, about 2.0 to 3.5%, and preferably 2.5 to 3.0%. The moisture content value of this polarizing plate was measured by the dry weight method, so it was a weight change after 105 ° C / 120 minutes.

本發明的偏光板之製造方法中使用的透明膜之厚度，雖然宜為薄者，但太過薄時，將使強度降低，使加工性劣化。另一方面，如太厚時將使透明性降低，而可能造成積層後必要的 熟成時間變長等問題。所以，透明膜的適當厚度，例如是5至200μm，並宜為10至150μm，而以10至100μm更佳。 The thickness of the transparent film used in the method for producing a polarizing plate of the present invention is preferably thin, but when it is too thin, the strength is lowered to deteriorate the workability. On the other hand, if it is too thick, the transparency will be lowered, which may cause the necessary after lamination. Mature time and other issues. Therefore, the appropriate thickness of the transparent film is, for example, 5 to 200 μm, and preferably 10 to 150 μm, and more preferably 10 to 100 μm.

如欲提高接著劑與偏光膜及/或與透明膜之間的接 著性時，也可對偏光膜及/或透明膜施予電暈處理、火焰處理、電漿處理、紫外線處理、底塗層塗布處理、皂化處理等表面改質處理。 If you want to improve the connection between the adhesive and the polarizing film and / or with the transparent film In the case of the properties, the polarizing film and/or the transparent film may be subjected to surface modification treatment such as corona treatment, flame treatment, plasma treatment, ultraviolet treatment, primer coating treatment, and saponification treatment.

同時，也可對透明膜，施以防眩處理、防反射處理、 保護塗層處理、防靜電處理、防污處理等表面處理，可單獨進行各別處理，或進行2種以上的組合。同時，透明膜及/或透明膜表面保護層，也可含有二苯甲酮系化合物、苯并***系化合物等紫外線吸收劑，或苯基磷酸酯系化合物、酞酸酯化合物等可塑劑。 At the same time, the transparent film can also be treated with anti-glare treatment and anti-reflection treatment. Surface treatment such as protective coating treatment, antistatic treatment, and antifouling treatment may be carried out separately or in combination of two or more. Meanwhile, the transparent film and/or the transparent film surface protective layer may contain a UV absorber such as a benzophenone compound or a benzotriazole compound, or a plasticizer such as a phenyl phosphate compound or a phthalate compound.

並且，在透明膜，也可持有作為相位差膜之機能、 作為亮度提高膜之機能、作為反射膜之機能、作為半透過反射膜之機能、作為擴散膜之機能、作為光學補償膜之機能等光學性機能。此時，除了例如可在透明膜的表面，藉由積層相位差膜、亮度提高膜、反射膜、半透過反射膜、擴散膜、光學補償膜等光學機能膜，而持有此種機能之外，也可對透明膜本身予有此等機能。同時，如同持有亮度提高膜之機能的擴散膜等，也可使透明膜中持有數種機能。 Moreover, in the transparent film, it is also possible to hold the function as a retardation film, The optical function of the function of the brightness enhancement film, the function as a reflection film, the function as a semi-transmissive reflection film, the function as a diffusion film, and the function as an optical compensation film. In this case, in addition to the optical functional film such as a laminated retardation film, a brightness enhancement film, a reflection film, a semi-transmissive reflection film, a diffusion film, and an optical compensation film, on the surface of the transparent film, for example, it is possible to hold such a function. It is also possible to have such a function on the transparent film itself. At the same time, as with a diffusion film or the like which holds the function of the brightness enhancement film, it is possible to hold several functions in the transparent film.

例如，對上述的透明膜，可藉由施予日本特許第 2841377號公報、日本特許第3094113號公報等所述之延伸處理，或施予日本特許第3168850號公報所述之延伸處理，而賦予作為相位差膜之機能。相位差膜中的相位差特性，例如可適宜的選擇正面相位差值為5至100nm，厚度方向的相位差值為40至300nm 之範圍等。同時，對上述的透明膜，可藉由日本特開2002-169025號公報或日本特開2003-29030號公報所述之方法形成微細孔，或使選擇反射的中心波長不同的2層以上之膽固醇型液晶層重疊，而賦予作為亮度提高膜的機能。 For example, the above transparent film can be given by the Japanese franchise In the extension process described in Japanese Patent No. 3,941, 850, or the extension process described in Japanese Patent No. 3,168,850, the function as a retardation film is imparted. The phase difference characteristic in the retardation film can be suitably selected, for example, from 5 to 100 nm in the frontal phase difference and from 40 to 300 nm in the thickness direction. The scope and so on. In the above-mentioned transparent film, fine pores can be formed by the method described in JP-A-2002-169025 or JP-A-2003-29030, or two or more layers of cholesterol having different center wavelengths of selective reflection can be formed. The liquid crystal layers are overlapped to impart a function as a brightness enhancement film.

只要對上述的透明膜以蒸鍍或濺鍍等形成金屬薄 膜，即可賦予作為反射膜或半透過反射膜的機能。在上述的透明膜塗布含有微粒子的樹脂溶液，即可賦予作為擴散膜的機能。又，在上述的透明膜塗布盤狀形(discotic)液晶性化合物等液晶性化合物而使其配向，即可賦予作為光學補償膜的機能。同時，也可使透明膜含有可顯現位相差的化合物。並且，也可使用適當的接著劑，使各種光學機能性膜直接貼合在偏光膜。作為光學機能性膜的市售品，可列舉：例如DBEF(3M公司製，在日本可購自住友3M(株))等亮度提高膜、WV膜(富士軟片(株)製)等視角改良膜、Arton膜(JSR(株)製)、ZEONOR膜((株)Optes製)、Esushina(積水化學工業(株)製)、VA-TAC(Konica Minolta Opto(株)製)、Sumicalite(住友化學(株)製)等相位差膜等。 As long as the above transparent film is formed by vapor deposition or sputtering, etc. The film can impart a function as a reflective film or a semi-transmissive reflective film. When a resin solution containing fine particles is applied to the above transparent film, the function as a diffusion film can be imparted. In addition, a liquid crystal compound such as a discotic liquid crystal compound is applied to the transparent film to be aligned, whereby the function as an optical compensation film can be imparted. At the same time, the transparent film may also contain a compound which exhibits a phase difference. Further, various optical functional films may be directly bonded to the polarizing film by using an appropriate adhesive. As a commercially available product of the optical functional film, for example, a brightness-enhancing film such as DBEF (available from 3M Company, available from Sumitomo 3M Co., Ltd.), or a WV film (made by Fujifilm Co., Ltd.) can be used. , Arton film (manufactured by JSR Corporation), ZEONOR film (manufactured by Optes Co., Ltd.), Esushina (manufactured by Sekisui Chemical Co., Ltd.), VA-TAC (manufactured by Konica Minolta Opto Co., Ltd.), Sumicalite (Sumitomo Chemical Co., Ltd.) A phase difference film or the like.

(活性能量線硬化型接著劑) (active energy ray hardening type adhesive)

偏光膜與透明膜，可經由活性能量線硬化型的接著劑而貼合。就耐候性或折射率或耐久性、陽離子聚合性等觀點而言，作為活性能量線硬化型的接著劑，可舉出含有可藉由活性能量線的照射而硬化之環氧樹脂的環氧系樹脂組成物所成的接著劑。但是，並不僅限於此接著劑，也可採用已往在製造偏光板中使用的各種活性能量線硬化型之接著劑(有機溶劑系接著劑、熱熔系接著劑、無溶劑型接著劑等)，例如可採用包含丙烯醯胺、丙烯 酸酯、胺酯丙烯酸酯、環氧丙烯酸酯等丙烯酸類樹脂組成物的接著劑。 The polarizing film and the transparent film can be bonded via an active energy ray-curable adhesive. From the viewpoints of weather resistance, refractive index, durability, cationic polymerizability, etc., as an active energy ray-curable adhesive, an epoxy resin containing an epoxy resin which can be cured by irradiation with an active energy ray is exemplified. An adhesive formed by the resin composition. However, it is not limited to this adhesive agent, and various active energy ray-curable adhesives (organic solvent-based adhesives, hot-melt adhesives, solventless adhesives, etc.) which have been used in the production of polarizing plates, may be used. For example, it can be used to contain acrylamide, propylene. An adhesive for an acrylic resin composition such as an acid ester, an amine ester acrylate or an epoxy acrylate.

環氧樹脂，是指分子內具有2個以上環氧基的化合 物。就耐候性、折射率、陽離子聚合性等觀點而言，作為接著劑的硬化性環氧樹脂組成物中含有的環氧樹脂，宜為分子內含有芳香環的環氧樹脂(例如，參照專利文獻1)。作為此種環氧樹脂，可例示如氫化環氧樹脂、脂環式環氧樹脂、脂肪族環氧樹脂等。 Epoxy resin refers to a combination of two or more epoxy groups in a molecule. Things. The epoxy resin contained in the curable epoxy resin composition as the adhesive agent is preferably an epoxy resin containing an aromatic ring in the molecule (for example, refer to the patent literature), from the viewpoint of the weather resistance, the refractive index, the cationic polymerizability, and the like. 1). Examples of such an epoxy resin include a hydrogenated epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin.

氫化環氧樹脂，是藉由使作為芳香族環氧樹脂的原 料的聚羥基化合物在觸媒的存在下，以加壓下選擇性的核氫化反應而得核氫化聚羥基化合物，使該核氫化聚羥基化合物去水甘油醚化的方法獲得。作為芳香族環氧樹脂，可列舉：例如雙酚A的二去水甘油醚、雙酚F的二去水甘油醚及雙酚S的二去水甘油醚等雙酚型環氧樹脂；酚酚醛環氧樹脂、甲酚酚醛環氧樹脂及羥基苯甲醛酚酚醛環氧樹脂等酚醛型環氧樹脂；四羥基苯基甲烷的去水甘油醚、四羥基二苯甲酮的去水甘油醚及環氧化聚乙烯酚等多官能型的環氧樹脂。氫化環氧樹脂之中，並宜為經氫化的雙酚A之去水甘油醚。 Hydrogenated epoxy resin by making the original as an aromatic epoxy resin The polyhydroxy compound of the material is obtained by a method in which a nuclear hydrogenation polyhydroxy compound is obtained by selective nuclear hydrogenation under pressure in the presence of a catalyst to dehydrate the nuclear hydrogenated polyhydroxy compound. Examples of the aromatic epoxy resin include bisphenol-type epoxy resins such as bisphenol A bis-glycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; Phenolic epoxy resin such as epoxy resin, cresol novolac epoxy resin and hydroxybenzaldehyde phenol novolac epoxy resin; dehydroglyceryl ether of tetrahydroxyphenylmethane, dehydroglyceryl ether of tetrahydroxybenzophenone and ring A polyfunctional epoxy resin such as oxidized polyvinylphenol. Among the hydrogenated epoxy resins, a hydrogenated bisphenol A deglycidyl ether is preferred.

脂環式環氧樹脂，是指分子內具有1個以上結合在 脂環式環的環氧基之環氧樹脂。「結合在脂環式環的環氧基」，是指下式表示的結構中交聯(架橋)的氧原子-O-。下式中，m是2至5的整數。 An alicyclic epoxy resin means that one or more molecules are combined in the molecule. An epoxy resin of an alicyclic ring. The "epoxy group bonded to the alicyclic ring" means an oxygen atom -O- which is crosslinked (bridged) in the structure represented by the following formula. In the following formula, m is an integer of 2 to 5.

使上述式中的(CH2)m中去除1個或複數個氫原子後 之形式的基，結合在另外的化學結構上之化合物，可作為脂環式環氧樹脂。(CH2)m中的1個或複數個氫原子，也可以甲基或乙基等直鏈狀烷基適宜的取代。脂環式環氧樹脂之中，並宜使用具有雜氧環己烷環(上述中的m=3者)或雜氧環庚烷環(上述中的m=4者)的環氧樹脂，因其可顯示優異的接著性。以下，雖然適宜使用的脂環式環氧樹脂之具體例示，但並不侷限於此等化合物。 A compound in which a group in which one or a plurality of hydrogen atoms are removed from (CH 2 ) m in the above formula is bonded to another chemical structure can be used as the alicyclic epoxy resin. One or a plurality of hydrogen atoms in (CH 2 ) m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group. Among the alicyclic epoxy resins, an epoxy resin having a heteroxia cyclohexane ring (m=3 in the above) or a hetero-oxocycloheptane ring (m=4 in the above) is preferably used. It can exhibit excellent adhesion. Hereinafter, although the alicyclic epoxy resin which is suitably used is specifically exemplified, it is not limited to these compounds.

下式(I)表示的環氧環己基甲基環氧環己烷羧酸酯 類： Epoxycyclohexylmethylepoxycyclohexanecarboxylate represented by the following formula (I):

(式中，R1及R2相互獨立地表示氫原子或碳數1至5的直鏈狀烷基)。 (wherein R 1 and R 2 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(b)下式(Ⅱ)表示的烷二醇之環氧環己烷羧酸酯類： (b) an epoxycyclohexane carboxylate of an alkanediol represented by the following formula (II):

(式中，R3及R4相互獨立地表示氫原子或碳數1至5的直鏈狀烷基，n表示2至20的整數)。 (wherein R 3 and R 4 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and n represents an integer of 2 to 20).

(c)下式(Ⅲ)表示的二羧酸的環氧環己基甲酯類： (c) Epoxycyclohexylmethyl esters of dicarboxylic acids represented by the following formula (III):

(式中，R5及R6相互獨立地表示氫原子或碳數1至5的直鏈狀烷基，p表示2至20的整數) (wherein R 5 and R 6 independently of each other represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, and p represents an integer of 2 to 20)

(d)下式(Ⅳ)表示的聚乙二醇的環氧環己基甲基醚類： (d) Epoxycyclohexylmethyl ether of polyethylene glycol represented by the following formula (IV):

(式中，R7及R8相互獨立地表示氫原子或碳數1至5的直鏈狀烷基，q表示2至10的整數) (Wherein, R 7 and R 8 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms, q represents an integer of 2 to 10)

(e)下式(V)表示的烷二醇的環氧環己基甲基醚類： (e) Epoxycyclohexylmethyl ether of an alkanediol represented by the following formula (V):

(式中，R9及R10相互獨立地表示氫原子或碳數1至5的直鏈狀烷基，r表示2至20的整數)。 (Wherein, R 9 and R 10 each independently represent a hydrogen atom or a linear alkyl group of 1 to 5 carbon atoms, r represents an integer of 2 to 20).

(f)下式(Ⅵ)表示的二環氧三螺化合物： (f) a diepoxy trispirate compound represented by the following formula (VI):

(式中，R11及R12相互獨立地表示氫原子或碳數1至5的直鏈狀烷基)。 (wherein R 11 and R 12 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(g)下式(Ⅶ)表示的二環氧單螺化合物： (g) a diepoxy single spiro compound represented by the following formula (VII):

(式中，R13及R14相互獨立地表示氫原子或碳數1至5的直鏈狀烷基)。 (Wherein, R 13 and R 14 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(h)下式(Ⅷ)表示的乙烯基環己烯環氧類： (h) Vinylcyclohexene epoxy represented by the following formula (VIII):

(式中，R15表示氫原子或碳數1至5的直鏈狀烷基)。 (wherein R 15 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(i)下式(Ⅸ)表示的環氧環戊基醚類： (i) Epoxycyclopentyl ethers represented by the following formula (IX):

(式中，R16及R17相互獨立地表示氫原子或碳數1至5的直鏈狀烷基)。 (wherein R 16 and R 17 each independently represent a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

(j)下式(X)表示的二環氧三環十烷類： (式中，R18表示氫原子或碳數1至5的直鏈狀烷基)。 (j) Diepylene tricyclodecanes represented by the following formula (X): (wherein R 18 represents a hydrogen atom or a linear alkyl group having 1 to 5 carbon atoms).

上述例示的脂環式環氧樹脂之中，市面上已有下述脂環式環氧樹脂或類似物質，以其比較容易購得等理由而較為適用。 Among the alicyclic epoxy resins exemplified above, the following alicyclic epoxy resins or the like are commercially available, and are preferably used because they are relatively easy to purchase.

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

同時，作為脂環式環氧樹脂，可舉出脂肪族多元醇或其伸烷氧化物加成物的聚去水甘油醚。更為具體時，可列舉：例如在1,4-丁二醇的二去水甘油醚；1,6-己二醇的二去水甘油醚；甘油的三去水甘油醚；三羥甲基丙烷的三去水甘油醚；聚乙二醇的二去水甘油醚；丙二醇的二去水甘油醚；乙二醇、丙二醇及甘油等脂肪族多元醇，加成1種或2種以上的伸烷氧化物(環氧乙 烷、環氧丙烷)而可得的聚醚多元醇之聚去水甘油醚等。 Meanwhile, as the alicyclic epoxy resin, a polyglycidyl ether of an aliphatic polyol or an alkylene oxide adduct thereof may be mentioned. More specifically, for example, diglycidyl ether of 1,4-butanediol; diglycidyl ether of 1,6-hexanediol; triglycidyl ether of glycerol; trimethylol Triglycidyl ether of propane; didehydroglyceryl ether of polyethylene glycol; didehydroglyceryl ether of propylene glycol; aliphatic polyol such as ethylene glycol, propylene glycol and glycerin, one or more kinds of extension Alkoxide Polyglycidyl ether of a polyether polyol obtainable by alkane or propylene oxide.

構成包含環氧系樹脂組成物的接著劑之環氧樹脂，可單獨使用1種或同時使用2種以上。此組成物中使用的環氧樹脂之環氧當量，通常是30至3,000g/當量，並宜為50至1,500g/當量的範圍內。如環氧當量少於30g/當量時，有可能使硬化後的複合偏光板之可撓性降低，或使接著強度降低。另一方面，如超過3,000g/當量時，有可能使其與含在接著劑中的其他成分之相溶性降低。 The epoxy resin constituting the adhesive containing the epoxy resin composition may be used alone or in combination of two or more. The epoxy equivalent of the epoxy resin used in the composition is usually from 30 to 3,000 g/equivalent, and preferably from 50 to 1,500 g/equivalent. When the epoxy equivalent is less than 30 g/equivalent, the flexibility of the cured composite polarizing plate may be lowered or the bonding strength may be lowered. On the other hand, when it exceeds 3,000 g/eq, it is possible to lower the compatibility with other components contained in the adhesive.

就反應性的觀點而言，此接著劑中宜使用陽離子聚合作為環氧樹脂的硬化反應。因此，在作為活性能量線硬化型接著劑的硬化性環氧樹脂組成物中，宜摻配陽離子聚合起始劑。陽離子聚合起始劑，可因可見光、紫外線、X線、電子束等活性能量線的照射，而產生陽離子種或路易斯酸，進而開始環氧基的聚合反應。以下，將藉由活性能量線的照射而產生陽離子種或路易斯酸，而使環氧基的聚合開始反應的陽離子聚合起始劑稱為「光陽離子聚合起始劑」。 From the viewpoint of reactivity, cationic polymerization is preferably used as the hardening reaction of the epoxy resin in the adhesive. Therefore, in the curable epoxy resin composition as the active energy ray-curable adhesive, it is preferred to incorporate a cationic polymerization initiator. The cationic polymerization initiator can generate a cationic species or a Lewis acid by irradiation with an active energy ray such as visible light, ultraviolet rays, X-rays, or electron beams, thereby starting the polymerization of the epoxy group. Hereinafter, a cationic polymerization initiator which initiates a reaction of polymerization of an epoxy group by a cationic species or a Lewis acid by irradiation with an active energy ray is referred to as a "photocationic polymerization initiator".

使用光陽離子聚合起始劑，以活性能量線的照射而進行接著劑之硬化的方法，可以在常溫中硬化，可減少偏光膜的耐熱性或因膨脹而歪斜之必要考量，而有利於膜間良好的接著。同時，由於光陽離子聚合起始劑是以光為觸媒作用，故即使混合在環氧樹脂中也有優異的保存安定性或作業性。 The method of curing the adhesive by irradiation with an active energy ray using a photocationic polymerization initiator can be cured at room temperature, and the heat resistance of the polarizing film or the skew due to expansion can be reduced, which is advantageous for the film. Good next. At the same time, since the photocationic polymerization initiator acts on light as a catalyst, it has excellent storage stability or workability even when mixed in an epoxy resin.

作為光陽離子聚合起始劑，可列舉：例如芳香族二氮鎓鹽；芳香族碘鎓鹽或芳香族硫鎓鹽等鎓鹽；鐵-重烯錯合物等。 Examples of the photocationic polymerization initiator include an aromatic diazonium salt; an onium salt such as an aromatic iodonium salt or an aromatic sulfonium salt; and an iron-heavy olefin complex.

作為芳香族二氮鎓鹽，可列舉：例如苯二氮鎓 六氟 銻酸鹽、苯二氮鎓 六氟磷酸鹽、苯二氮鎓 六氟硼酸鹽等。同時，作為芳香族碘鎓鹽，可列舉：例如二苯基碘鎓 四(五氟苯基)硼酸鹽、二苯基碘鎓 六氟磷酸鹽、二苯基碘鎓 六氟銻酸鹽、二(4-壬基苯基)碘鎓 六氟磷酸鹽等。 As the aromatic diazonium salt, for example, benzodiazepine hexafluoride Citrate, benzodiazepine hexafluorophosphate, benzodiazepine hexafluoroborate, and the like. Meanwhile, examples of the aromatic iodonium salt include diphenyl iodonium tetrakis(pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, and (4-nonylphenyl) iodonium hexafluorophosphate or the like.

作為芳香族硫鎓鹽，可列舉：例如三苯基硫鎓 六氟 磷酸鹽、三苯基硫鎓 六氟銻酸鹽、三苯基硫鎓 四(五氟苯基)硼酸鹽、4,4’-雙(二苯基硫鎓基)二苯基硫化物、4,4’-雙[二(β-羥基乙氧基)苯基硫鎓基]二苯基硫化物 雙(六氟磷酸鹽)、4,4’-雙[二(β-羥基乙氧基)苯基硫鎓基]二苯基硫化物 雙(六氟銻酸鹽)、7-[二(對-甲苯基)硫鎓基]-2-異丙基噻吨酮 六氟銻酸鹽、7-[二(對-甲苯基)硫鎓基]-2-異丙基噻吨酮 四(五氟苯基)硼酸鹽、4-苯基羰基-4’-二苯基硫鎓基-二苯基硫化物 六氟磷酸鹽、4-(對-第三丁基苯基羰基)-4’-二苯基硫鎓基-二苯基硫化物 六氟銻酸鹽、4-(對-第三丁基苯基羰基)-4’-二(對-甲苯基)硫鎓基-二苯基硫化物 四(五氟苯基)硼酸鹽等。 As the aromatic sulfonium salt, for example, triphenylsulfonium hexafluoride Phosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, 4,4'-bis(diphenylsulfanyl)diphenyl sulfide, 4 , 4'-bis[bis(β-hydroxyethoxy)phenylsulfonyl]diphenyl sulfide bis(hexafluorophosphate), 4,4'-bis[bis(β-hydroxyethoxy) Phenylthioindolyl]diphenyl sulfide bis(hexafluoroantimonate), 7-[bis(p-tolyl)thiol]-2-isopropylthioxanthone hexafluoroantimonate, 7 -[bis(p-tolyl)thiol]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylthioindenyl-diphenyl Base sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfanyl-diphenyl sulfide hexafluoroantimonate, 4-(p-third Butylphenylcarbonyl)-4'-bis(p-tolyl)thiol-diphenyl sulfide tetrakis(pentafluorophenyl)borate.

同時，作為鐵-重烯錯合物，可列舉：例如二甲苯- 環戊二烯基鐵(Ⅱ)六氟銻酸鹽、異丙苯-環戊二烯基鐵(Ⅱ)六氟磷酸鹽、二甲苯-環戊二烯基鐵(Ⅱ)-三(三氟甲基磺醯基)甲烷化物等。 Meanwhile, as the iron-heavy olefin complex, for example, xylene- Cyclopentadienyl iron(II) hexafluoroantimonate, cumene-cyclopentadienyl iron(II) hexafluorophosphate, xylene-cyclopentadienyl iron(II)-tris(trifluoro Methylsulfonyl) methanide and the like.

此等光陽離子聚合起始劑的市售品，可輕易的購 得，各別的商品名可列舉：例如「Kayarad PCI-220」及「Kayarad PCI-620」(以上，日本化藥(株)製)、「UVI-6990」(聯合碳素(Union Carbide)公司製)、「Adeka Optomer SP-150」及「Adeka Optomer SP-170」(以上，ADEKA製)、「CI-5102」、「CIT-1370」、「CIT-1682」、「CIP-1866S」、「CIP-2048S」及「CIP-2064S」(以上，日本曹達(株) 製)、「DPI-101」、「DPI-102」、「DPI-103」、「DPI-105」、「MPI-103」、「MPI-105」、「BBI-101」、「BBI-102」、「BBI-103」、「BBI-105」、「TPS-101」、「TPS-102」、「TPS-103」、「TPS-105」、「MDS-103」、「MDS-105」、「DTS-102」及「DTS-103」(以上，Midori化學(株)製)、「PI-2074」(Rhodia公司製)等。 Commercially available as such photocationic polymerization initiators, which can be easily purchased For example, "Kayarad PCI-220" and "Kayarad PCI-620" (above, Nippon Kayaku Co., Ltd.) and "UVI-6990" (Union Carbide) are listed. System, "Adeka Optomer SP-150" and "Adeka Optomer SP-170" (above, made by ADEKA), "CI-5102", "CIT-1370", "CIT-1682", "CIP-1866S", " CIP-2048S" and "CIP-2064S" (above, Japan Soda Corporation) System), "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102" "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS-103", "MDS-105", " DTS-102" and "DTS-103" (above, manufactured by Midori Chemical Co., Ltd.) and "PI-2074" (manufactured by Rhodia Co., Ltd.).

光陽離子聚合起始劑可僅單獨使用1種，也可將2 種以上混合後使用。其中，並宜使用芳香族硫鎓鹽，因其即使在300nm以上的波長域中，也具有紫外線吸收特性，而可提供具有硬化性優異、良好機械強度或接著強度的硬化物。 The photocationic polymerization initiator may be used alone or in combination of two or two. The above is mixed and used. Among them, an aromatic sulfonium salt is preferably used because it has ultraviolet absorbing properties even in a wavelength region of 300 nm or more, and can provide a cured product having excellent hardenability, good mechanical strength, or adhesion strength.

相對於環氧樹脂100重量份，光陽離子聚合起始劑 之調配量通常是0.5至20重量份，並宜為1重量份以上，而以15重量份以下更佳。對於環氧樹脂100重量份，如光陽離子聚合起始劑之調配量少於0.5重量份時，將有硬化不足、機械強度或接著強度降低的傾向。又，對於環氧樹脂100重量份，如光陽離子聚合起始劑之調配量超過20重量份時，有可能因硬化物中的離子性物質增加，而使硬化物的吸濕性變高、耐久性降低。 Photocationic polymerization initiator relative to 100 parts by weight of epoxy resin The blending amount is usually 0.5 to 20 parts by weight, and is preferably 1 part by weight or more, more preferably 15 parts by weight or less. When the compounding amount of the photocationic polymerization initiator is less than 0.5 part by weight based on 100 parts by weight of the epoxy resin, there is a tendency that the hardening is insufficient, the mechanical strength or the subsequent strength is lowered. In addition, when the compounding amount of the photocationic polymerization initiator is more than 20 parts by weight based on 100 parts by weight of the epoxy resin, the ionic substance in the cured product may increase, and the hygroscopic property of the cured product becomes high and durable. Reduced sex.

使用光陽離子聚合起始劑時，硬化性環氧樹脂組成 物，可視需要進一步含有光增感劑。因使用光增感劑，而可使陽離子聚合的反應性提高，使硬化物的機械強度或接著強度提高。作為光增感劑，可列舉：例如羰基化合物、有機硫化合物、過硫化物、氧化還原類化合物、偶氮及重氮化合物、鹵素化合物、光還原性色素等。 Curing epoxy resin composition when using photocationic polymerization initiator The material may further contain a photosensitizer as needed. By using a photosensitizer, the reactivity of cationic polymerization can be improved, and the mechanical strength or the subsequent strength of the cured product can be improved. Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfide compound, a redox compound, an azo and a diazo compound, a halogen compound, and a photoreductive dye.

光增感劑的更具體之例，可列舉：例如安息香甲醚、 安息香異丙醚及α,α-二甲氧基-α-苯基苯乙酮等安息香衍生物； 二苯甲酮、2,4-二氯二苯甲酮、鄰-苯甲醯基苯甲酸甲酯、4,4’-雙(二甲基胺基)二苯甲酮及4,4’-雙(二乙基胺基)二苯甲酮等二苯甲酮衍生物；2-氯噻吨酮及2-異丙基噻吨酮等噻吨酮衍生物；2-氯蒽醌及2-甲基蒽醌等蒽醌衍生物；N-甲基吖啶酮及N-丁基吖啶酮等吖啶酮衍生物；其他如α,α-二乙氧基苯乙酮、聯苯甲醯(benzil)、茀酮、氧蒽酮、鈾化合物、鹵素化合物等。光增感劑可僅單獨使用1種，也可同時使用2種以上。在硬化性環氧樹脂組成物100重量份中，光增感劑的含量宜為0.1至20重量份的範圍內。 More specific examples of the photosensitizer include, for example, benzoin methyl ether, Benzoin isopropyl ether and benzoin derivatives such as α,α-dimethoxy-α-phenylacetophenone; Benzophenone, 2,4-dichlorobenzophenone, methyl o-benzhydrylbenzoate, 4,4'-bis(dimethylamino)benzophenone and 4,4'- a benzophenone derivative such as bis(diethylamino)benzophenone; a thioxanthone derivative such as 2-chlorothioxanthone or 2-isopropylthioxanthone; 2-chloroindole and 2- Anthracene derivatives such as methyl hydrazine; acridone derivatives such as N-methylacridone and N-butylacridone; others such as α,α-diethoxyacetophenone and benzamidine (benzil), anthrone, oxone, uranium compound, halogen compound, and the like. The photosensitizer may be used alone or in combination of two or more. The content of the photosensitizer is preferably in the range of 0.1 to 20 parts by weight based on 100 parts by weight of the curable epoxy resin composition.

接著劑含有的環氧樹脂，雖然可藉由光陽離子聚合 而硬化，但也可藉由光陽離子聚合及熱陽離子聚合的二種方式硬化。如為後者時，宜同時使用光陽離子聚合起始劑與熱陽離子聚合起始劑。 The epoxy resin contained in the subsequent agent, although photocationic polymerization It is hardened, but it can also be hardened by photocationic polymerization and thermal cationic polymerization. In the latter case, it is preferred to use both a photocationic polymerization initiator and a thermal cationic polymerization initiator.

作為熱陽離子聚合起始劑，可列舉：例如苯甲硫鎓 鹽、噻吩鎓鹽、硫雜五員環鎓(thiolanium)鹽、苯甲銨、吡啶鎓鹽、肼鎓鹽、羧酸酯、磺酸酯、胺醯亞胺等。此等熱陽離子聚合起始劑，可容易取得其市售品，例如，均為商品名的「Adekaopton CP77」及「Adekaopton CP66」(以上，株式會社Adeka製)、「CI-2639」及「CI-2624」(以上，日本曹達株式會社製)、「Sanaid SI-60L」、「Sanaid SI-80L」及「Sanaid SI-100L」(以上，三新化學工業株式會社製)等。 As the thermal cationic polymerization initiator, for example, benzomethazine a salt, a thiophene sulfonium salt, a thiolanium salt, a benzalkonium salt, a pyridinium salt, a phosphonium salt, a carboxylic acid ester, a sulfonate, an amine imine or the like. For example, "Adekaopton CP77" and "Adekaopton CP66" (above, Adeka Co., Ltd.), "CI-2639" and "CI" are commercially available as such a thermal cationic polymerization initiator. -2624 (above, manufactured by Nippon Soda Co., Ltd.), "Sanaid SI-60L", "Sanaid SI-80L", and "Sanaid SI-100L" (above, Sanshin Chemical Industry Co., Ltd.).

活性能量線硬化型的接著劑，並且也可含有環氧丙 烷(oxetane)類或多元醇類等可促進陽離子聚合的化合物。 Active energy ray-curable adhesive, and may also contain propylene oxide A compound which promotes cationic polymerization, such as an oxetane or a polyhydric alcohol.

環氧丙烷類，是分子內具有4員環醚的化合物，可 列舉：例如3-乙基-3-羥基甲基環氧丙烷、1,4-雙[(3-乙基-3-環氧丙烷基)甲氧基甲基]苯、3-乙基-3-(苯氧基甲基)環氧丙烷、二[(3-乙基-3-環氧丙烷基)甲基]醚、3-乙基-3-(2-乙基己氧基甲基)環氧丙烷、酚酚醛環氧丙烷等。此等環氧丙烷類可作為市售品而輕易購得，例如均為商品名的「ARONE OXETANE OXT-101」、「ARONE OXETANE OXT-121」、「ARONE OXETANE OXT-211」、「ARONE OXETANE OXT-221」及「ARONE OXETANE OXT-212」(以上，東亞合成(株)製)等。在硬化性環氧樹脂組成物中，此等環氧丙烷類通常含有的比例為5至95重量%，並宜為30至70重量%。 A propylene oxide compound is a compound having 4 members of a cyclic ether in the molecule. For example: 3-ethyl-3-hydroxymethyl propylene oxide, 1,4-bis[(3-ethyl-3-epoxypropenyl)methoxymethyl]benzene, 3-ethyl-3 -(phenoxymethyl) propylene oxide, bis[(3-ethyl-3-epoxypropenyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl) Propylene oxide, phenol novolac propylene oxide, and the like. These propylene oxides are commercially available as "ARONE OXETANE OXT-101", "ARONE OXETANE OXT-121", "ARONE OXETANE OXT-211", "ARONE OXETANE OXT". -221" and "ARONE OXETANE OXT-212" (above, manufactured by Toagosei Co., Ltd.). In the curable epoxy resin composition, these propylene oxides are usually contained in a proportion of 5 to 95% by weight, and preferably 30 to 70% by weight.

作為多元醇類，宜為不存在酚性羥基以外的酸性基 的化合物，可列舉：例如不具有羥基以外的官能基之多元醇化合物、聚酯多元醇化合物、聚己內酯多元醇化合物、具有酚性羥基的多元醇化合物、聚碳酸酯多元醇化合物等。此等多元醇類的分子量，通常是48以上，並宜為62以上，而以100以上更佳，而以1,000以下又更佳。在硬化性環氧樹脂組成物中，此等多元醇類通常含有的比例為50重量%以下，並宜為30重量%以下。 As the polyol, it is preferred that there is no acidic group other than the phenolic hydroxyl group. Examples of the compound include a polyol compound having no functional group other than a hydroxyl group, a polyester polyol compound, a polycaprolactone polyol compound, a polyol compound having a phenolic hydroxyl group, and a polycarbonate polyol compound. The molecular weight of these polyols is usually 48 or more, and is preferably 62 or more, more preferably 100 or more, and still more preferably 1,000 or less. In the curable epoxy resin composition, these polyols are usually contained in a proportion of 50% by weight or less, and preferably 30% by weight or less.

在活性能量線硬化型的接著劑中，並且可調配離子 阱劑、抗氧化劑、鏈移動劑、黏著賦予劑、熱可塑性樹脂、充填劑、流動調整劑、整平劑、可塑劑、消泡劑等添加劑。作為離子阱劑，可列舉：例如粉末狀的鉍系、銻系、鎂系、鋁系、鈣系、鈦系及此等的混合系等無機化合物，作為抗氧化劑，可舉出受阻酚系抗氧化劑等。 In active energy line hardening type of adhesive, and adjustable ion Additives such as a well agent, an antioxidant, a chain shifting agent, an adhesion-imparting agent, a thermoplastic resin, a filler, a flow regulator, a leveling agent, a plasticizer, and an antifoaming agent. Examples of the ion-trapping agent include inorganic compounds such as powdered lanthanoid, lanthanide, magnesium, aluminum, calcium, titanium, and the like. Examples of the antioxidant include hindered phenolic antioxidants. Oxidizing agents, etc.

活性能量線硬化型的接著劑，雖然可使用作為實質 上不含溶劑成分的無溶劑型接著劑，但因塗布方式有各別最適的 黏度範圍，故在調整黏度時也可使其含有溶劑。作為溶劑，宜使用不使偏光膜之光學性能降低，可良好的溶解環氧樹脂組成物之溶劑，可列舉：例如以甲苯為代表的烴類、以醋酸乙酯為代表的酯類等有機溶劑。本發明中可使用的活性能量線硬化型的接著劑之黏度，例如大約5至1,000mPa‧s的範圍，並宜為10至200mPa‧s，而以20至100mPa‧s更佳。 Active energy ray-curable adhesive, although it can be used as a substance A solvent-free adhesive that does not contain a solvent component, but the coating method has its own optimum The viscosity range, so it can also contain solvent when adjusting the viscosity. The solvent is preferably a solvent which can dissolve the epoxy resin composition without lowering the optical performance of the polarizing film, and examples thereof include an organic solvent such as a hydrocarbon represented by toluene and an ester represented by ethyl acetate. . The viscosity of the active energy ray-curing type adhesive which can be used in the present invention is, for example, in the range of about 5 to 1,000 mPa ‧ and preferably 10 to 200 mPa ‧ s, and more preferably 20 to 100 mPa ‧ s

<偏光板之製造方法> <Method of Manufacturing Polarizing Plate>

其次，一邊參照圖面一邊說明本發明的偏光板之製造裝置及製造方法。第1圖是表示本發明的偏光板之製造裝置的一實施形態之概略圖。 Next, a manufacturing apparatus and a manufacturing method of the polarizing plate of the present invention will be described with reference to the drawings. Fig. 1 is a schematic view showing an embodiment of a manufacturing apparatus of a polarizing plate of the present invention.

第1圖中表示的偏光板之製造裝置30，是沿著運送方向依序在透明膜2、3的單面設置用於塗布接著劑的接著劑塗布裝置11、12，用於貼合透明膜2、3與偏光膜1而得積層體4的貼合滾輪(壓輪)51與52、已密著積層體4的滾輪13與該滾輪13的外緣面相對位置而設置的第1活性能量線照射裝置31、32，設置於比此等運送方向的下流側的第2活性能量線照射裝置16至18與運送用壓輪19。 The polarizing plate manufacturing apparatus 30 shown in FIG. 1 is provided with an adhesive application device 11 and 12 for applying an adhesive on one surface of the transparent films 2 and 3 in order along the transport direction, for bonding a transparent film. The first active energy provided by the bonding rollers (pressure rollers) 51 and 52 of the laminated body 4 and the roller 13 of the laminated body 4 and the outer peripheral surface of the roller 13 in contact with the polarizing film 1 The line irradiation devices 31 and 32 are provided in the second active energy ray irradiation devices 16 to 18 and the transportation pressure roller 19 on the downstream side in the transport direction.

首先，使用接著劑塗布裝置11、12將活性能量線硬化型的接著劑，塗布在以由滾輪狀捲出的狀態連續捲出之透明膜2、3的單面(接著劑塗布步驟)。 First, an active energy ray-curable adhesive is applied to one surface of the transparent films 2 and 3 which are continuously wound up in a roll shape by using the adhesive application devices 11 and 12 (adhesive application step).

然後，在由滾輪狀捲出的狀態連續捲出之偏光膜1的雙面，經由接著劑將已塗布接著劑的透明膜2、3積層而成的積層體，以挾持在朝運送方向旋轉的一對貼合滾輪51、52之間的狀態，以至少一方的貼合滾輪按壓另一方貼合滾輪的方向而對積層 體施加壓力，使偏光膜1與透明膜2、3貼合而形成積層體4(貼合步驟)。 Then, the laminated body in which the transparent films 2 and 3 to which the adhesive has been applied is laminated on both sides of the polarizing film 1 which is continuously wound up in a state of being rolled up in a roll shape, is held in a direction of rotation in the conveyance direction. In a state between the pair of bonding rollers 51 and 52, the lamination is performed by pressing at least one of the bonding rollers to press the other roller. Pressure is applied to the body to bond the polarizing film 1 and the transparent films 2 and 3 to form a layered body 4 (bonding step).

接著，以使此積層體4密著在滾輪13的外緣面同時運送的過程中，由第1活性能量線照射裝置31、32使對向滾輪13的外緣面照射活性能量線，使接著劑聚合硬化(第1活性能量線照射步驟)。 Then, in the process of transporting the laminated body 4 on the outer peripheral surface of the roller 13, the active energy lines are irradiated to the outer peripheral surface of the opposing roller 13 by the first active energy ray irradiation devices 31 and 32, and then Polymerization hardening (first active energy ray irradiation step).

而且，可配置在運送方向下流處的第2活性能量線照射裝置16至18，是為了使接著劑完全聚合硬化的裝置(第2活性能量線照射步驟)，雖然可視需要而追加或省略，但因可藉由第2活性能量線照射步驟而使接著劑完全的聚合硬化，故在第1活性能量線照射步驟中，即不必使接著劑完全的聚合硬化，如同可抑制波浪捲之發生似的容易控制活性能量線的積光量，因此宜具有第2活性能量線照射步驟。最後是使積層體4通過運送用壓輪19後，由捲取滾輪20捲取作成偏光板。以下，詳細說明各步驟。 Further, the second active energy ray irradiation devices 16 to 18 which are disposed downstream in the transport direction are devices for completely curing and curing the adhesive (second active energy ray irradiation step), and may be added or omitted as necessary. Since the adhesive is completely polymer-hardened by the second active energy ray irradiation step, in the first active energy ray irradiation step, it is not necessary to completely cure the adhesive, as if the occurrence of the wave roll can be suppressed. Since it is easy to control the amount of light accumulated by the active energy ray, it is preferable to have the second active energy ray irradiation step. Finally, the laminated body 4 is passed through the transporting roller 19, and then taken up by the take-up reel 20 to form a polarizing plate. Hereinafter, each step will be described in detail.

(接著劑塗布步驟) (adhesive coating step)

雖然無特別的限定對透明膜2、3塗布接著劑的方法，但可利用例如刮片塗布法、線棒塗布器、鑄模塗布器、刮刀塗布器、凹板塗布器等各種塗布方式。其中，如考量薄膜塗工、路徑線的自由度、幅寬的對應等時，則宜以凹板塗布器作為接著劑塗布裝置11、12。 Although the method of applying the adhesive to the transparent films 2 and 3 is not particularly limited, various coating methods such as a blade coating method, a wire bar coater, a die coater, a knife coater, and a gravure coater can be used. Among them, in consideration of the film coating, the degree of freedom of the path line, the correspondence of the width, and the like, it is preferable to use the concave applicator as the adhesive application devices 11, 12.

在使用凹板塗布器作為接著劑塗布裝置11、12進行接著劑的塗布時，塗布接著劑的厚度(塗布厚)宜大約為0.1至10μm，並以0.2至4μm更佳。接著劑的塗布厚度，可藉由凹板滾輪相對於透明膜的直線速度之拖伸比調整。一般是，使拖伸比(凹 板滾輪速度/直線速度)調整為0.5至10時，即可使接著劑塗布厚調整至0.1至10μm。更具體而言，將透明膜2、3之直線速度設為10至100m/分鐘時，可使凹板滾輪朝透明膜2、3的運送方向之逆向旋轉，因將凹板滾輪的速度設為5至1,000m/分鐘，故可使接著劑的塗布厚調整至0.1至10μm。 When the application of the adhesive is carried out using the gravure coater as the adhesive applying means 11, 12, the thickness (coating thickness) of the coating adhesive is preferably about 0.1 to 10 μm, more preferably 0.2 to 4 μm. The coating thickness of the subsequent agent can be adjusted by the draw ratio of the linear speed of the concave plate roller relative to the transparent film. Generally, the draw ratio (concave When the plate roller speed/linear speed is adjusted to 0.5 to 10, the adhesive coating thickness can be adjusted to 0.1 to 10 μm. More specifically, when the linear velocity of the transparent films 2 and 3 is 10 to 100 m/min, the concave roller can be reversely rotated in the conveying direction of the transparent films 2 and 3, and the speed of the concave roller is set. From 5 to 1,000 m/min, the coating thickness of the adhesive can be adjusted to 0.1 to 10 μm.

調製接著劑後，通常是調整在15至45℃的範圍內 之設定溫度±5℃(例如，設定溫度為30℃時，為30℃±5℃)的環境下塗布，並宜為±3℃，而以±1℃更佳。 After the adhesive is prepared, it is usually adjusted within the range of 15 to 45 ° C. The coating temperature is ±5 ° C (for example, 30 ° C ± 5 ° C when the temperature is 30 ° C), and is preferably ± 3 ° C, and more preferably ± 1 ° C.

(貼合步驟) (Fitting step)

在本步驟中，可使上述步驟經塗布接著劑的透明膜2、3，經由接著劑而在由捲成滾輪狀態連續捲出的偏光膜1之兩面積層。使此積層體以挾持在運送方向旋轉的一對貼合滾輪51、52之間的狀態，例如，因將貼合滾輪51朝貼合滾輪52的方向按壓，而使偏光膜1與透明膜2、3貼合，而形成積層體4。此時，如同形成面對貼合滾輪的按壓方向之垂直面的±3°範圍內之角度，並宜為±1°的角度範圍內，尤其良好的是使偏光膜的運送方向，如同與貼合滾輪的按壓方向之垂直面重疊似的，將偏光膜在貼合滾輪之間運送。因如此的進行，即可使偏光膜與透明膜面對著貼合滾輪接觸而不致產生氣泡。 In this step, the transparent film 2, 3 coated with the above-mentioned step can be passed through the two-area layer of the polarizing film 1 continuously wound up by the roll in the state of being wound by the adhesive. In the state in which the laminated body is held between the pair of bonding rollers 51 and 52 that are rotated in the transport direction, for example, the polarizing film 1 and the transparent film 2 are pressed by pressing the bonding roller 51 in the direction of the bonding roller 52. And 3 are bonded together to form a laminated body 4. At this time, as in the angle range of ±3° which forms the vertical direction of the pressing direction of the bonding roller, and preferably within an angle range of ±1°, it is particularly preferable to make the traveling direction of the polarizing film as if The polarizing film is transported between the bonding rollers in such a manner that the vertical faces of the pressing directions of the rollers overlap. By doing so, the polarizing film and the transparent film can be brought into contact with the bonding roller without causing bubbles.

同時，在第1圖中，雖然是表示在透明膜2、3的單面上均勻的塗布接著劑，藉由貼合滾輪51、52，將偏光膜1重疊在已塗布接著劑的透明膜2、3之面而貼合的方法，但也可在偏光膜1之雙面均勻塗布接著劑，藉由貼合滾輪51、52，使透明膜2、3重疊在已塗布接著劑的偏光膜1之雙面而貼合。 Meanwhile, in FIG. 1, the adhesive agent is uniformly applied to one surface of the transparent films 2 and 3, and the polarizing film 1 is superposed on the transparent film 2 to which the adhesive has been applied by bonding the rollers 51 and 52. a method of bonding to the surface of the third surface, but the adhesive may be uniformly applied to both surfaces of the polarizing film 1, and the transparent film 2, 3 may be laminated on the polarizing film 1 to which the adhesive is applied by bonding the rollers 51 and 52. It is fitted on both sides.

作為貼合滾輪51、52的材質，可舉出金屬滾輪與橡膠滾輪。宜使一對貼合滾輪51、52的一方為金屬滾輪，另一方為橡膠滾輪。作為金屬滾輪的母材，雖然可使用各種已知的材質，但宜為SUS304，而以在其表面上施予鍍鉻處理者更佳。同時，橡膠貼合滾輪的材質，並無特別的限定，可列舉：例如EPDM、NBR、胺酯、鈦、矽酮等。橡膠滾輪之硬度並無特別的限定，通常是60至100°，並宜為85至95°。而且，橡膠滾輪的硬度可以依照JIS K6253的硬度計測定。作為市售的硬度計，可使用：例如明日香社製的橡膠硬度計「A型」等。具體上，以如同以棒狀物按壓表面時，以硬度計測定橡膠滾輪的表面阻抗。 As a material of the bonding rollers 51 and 52, a metal roller and a rubber roller are mentioned. It is preferable that one of the pair of bonding rollers 51 and 52 is a metal roller and the other is a rubber roller. As the base material of the metal roller, although various known materials can be used, it is preferably SUS304, and it is more preferable to apply chrome plating on the surface thereof. Meanwhile, the material of the rubber bonding roller is not particularly limited, and examples thereof include EPDM, NBR, amine ester, titanium, anthrone, and the like. The hardness of the rubber roller is not particularly limited and is usually from 60 to 100 ° and preferably from 85 to 95 °. Further, the hardness of the rubber roller can be measured in accordance with the hardness meter of JIS K6253. As a commercially available hardness meter, for example, a rubber hardness meter "A type" manufactured by Asuka Co., Ltd., or the like can be used. Specifically, the surface resistance of the rubber roller was measured by a durometer when the surface was pressed like a rod.

金屬滾輪與橡膠滾輪的押附壓，宜為富士軟片製的二片型感壓紙(two sheet type prsacale)(超低壓用)中之瞬間壓為0.5至3.0MPa，並以0.7至2.3MPa更佳。貼合滾輪51、52的直徑，並無特別的限定，通常是50至400mm。同時，二支(一對)貼合滾輪51、52的直徑，可以是相同，也可相異。 The urging pressure of the metal roller and the rubber roller should be 0.5 to 3.0 MPa in the two sheet type prsacale (Ultra Low Pressure) made of Fujifilm, and 0.7 to 2.3 MPa. good. The diameter of the bonding rollers 51 and 52 is not particularly limited and is usually 50 to 400 mm. At the same time, the diameters of the two (one pair) bonding rollers 51, 52 may be the same or different.

(第1活性能量線照射步驟) (first active energy ray irradiation step)

滾輪13是由外緣面為鏡面修飾的凸球面構成，在其表面使積層體4密著時同時運送，在其過程中可藉由活性能量線照射裝置31、32而使接著劑聚合硬化。因使接著劑聚合硬化，只要可使積層體4充分密著，不特別限定滾輪13的直徑。滾輪13可配合線速度的回轉速度而旋轉驅動。同時，在照射活性能量線而聚合硬化時，也可使滾輪13作用為可使積層體4產生的熱放熱時的冷卻滾輪。此時，冷卻滾輪的表面溫度宜設定在4至30℃。 The roller 13 is composed of a convex spherical surface whose outer peripheral surface is mirror-finished, and is transported at the same time when the laminated body 4 is adhered to the surface thereof. In the process, the adhesive is polymerized and hardened by the active energy ray irradiation devices 31 and 32. The adhesive agent is hardened by polymerization, and the diameter of the roller 13 is not particularly limited as long as the laminated body 4 can be sufficiently adhered. The roller 13 can be rotationally driven in accordance with the rotational speed of the linear velocity. At the same time, when the active energy ray is irradiated and the polymer is hardened, the roller 13 can also act as a cooling roller for allowing the heat generated by the laminated body 4 to be released. At this time, the surface temperature of the cooling roller should be set at 4 to 30 °C.

藉由活性能量線的照射而進行接著劑的聚合硬化時 使用的光源，雖然無特別的限定，但宜為具有波長400nm以下的發光分布之光源。作為此種光源，可列舉：例如低壓水銀燈、中壓水銀燈、高壓水銀燈、超高壓水銀燈、化學燈、黑光燈、微波激發水銀燈、金屬鹵化物燈(鹵素燈)。第1活性能量線照射步驟中，宜分成複數次進行活性能量線的照射。在第1圖中，活性能量線的照射是分成2次進行，即雖然是沿著積層體的運送方向配置2個光源(活性能量線照射裝置31及32)，但並不限定於2次，也可分成3次進行。 When the polymerization of the adhesive is performed by irradiation of an active energy ray The light source to be used is preferably a light source having a light-emitting distribution having a wavelength of 400 nm or less, although it is not particularly limited. Examples of such a light source include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, and a metal halide lamp (halogen lamp). In the first active energy ray irradiation step, it is preferable to perform irradiation of the active energy ray in plural times. In the first drawing, the irradiation of the active energy ray is performed twice, that is, although two light sources (the active energy ray irradiation devices 31 and 32) are arranged along the transport direction of the laminated body, the present invention is not limited to two times. It can also be divided into 3 times.

第2圖是表示使第1活性能量線照射步驟中的光 源，是沿著積層體的運送方向配置3個的偏光板之製造裝置。第2圖中表示的製造裝置，是在第1圖中所示的製造置中，除了活性能量線照射裝置31及32作為第1活性能量線照射步驟中使用光源之外，僅因配置上活性能量線照射裝置33，故可省略說明其他的構成要件。 Fig. 2 is a view showing light in the step of irradiating the first active energy ray The source is a manufacturing apparatus in which three polarizing plates are arranged along the transport direction of the laminated body. The manufacturing apparatus shown in Fig. 2 is in the manufacturing apparatus shown in Fig. 1, except that the active energy ray irradiation apparatuses 31 and 32 are used as the light source in the first active energy ray irradiation step, and only the configuration is active. Since the energy ray irradiation device 33 is omitted, other constituent elements can be omitted.

在第1活性能量線照射步驟中，以通過滾輪13間的 紫外線(UVB)之累積光量為10mJ/cm2以上且185mJ/cm2以下之方式，對積層體4照射活性能量線。並宜以紫外線(UVB)之累積光量為60mJ/cm2以上且175mJ/cm2以下之方式照射活性能量線。如累積光量超過185mJ/cm2時，將成為偏光板產生波狀斑的原因。又，如累積光量未達10mJ/cm2時，將使其後以水平狀態照射活性能量線的步驟(第2活性能量線照射步驟)中，使活性能量線的累積光量變大而容易產生硬化收縮，以致容易造成波浪捲。 In the first step of irradiating an active energy ray, the cumulative amount of light through the roller 13 of ultraviolet (UVB) is 2 or more and 185mJ / cm 2 or less of the embodiment 10mJ / cm, laminated on the active energy rays 4 thereof. The active energy ray is preferably irradiated so that the cumulative amount of ultraviolet light (UVB) is 60 mJ/cm 2 or more and 175 mJ/cm 2 or less. When the cumulative amount of light exceeds 185 mJ/cm 2 , it causes a wavy spot on the polarizing plate. In addition, when the cumulative amount of light is less than 10 mJ/cm 2 , the step of irradiating the active energy ray in a horizontal state (the second active energy ray irradiation step) is performed to increase the cumulative amount of the active energy ray and to cause hardening. Shrinking, so that it is easy to cause a wave roll.

對於活性能量線硬化型接著劑每次的光照射強度， 雖然是包括接著劑的組成而決定，並無特別的限定，但宜為10至 5,000mW/cm2。如對於樹脂組成物的光照射強度未達10mW/cm2時，將使反應時間變得太長，如其超過5,000mW/cm2時，將因來自光源的輻射熱及組成物聚合時的放熱，而有可能使接著劑的構成材料之環氧樹脂組成物等產生黃變或偏光板的劣化。而且，照射強度宜為對於光陽離子聚合起始劑的活性化有效的強度，並以400nm以下的波長域更佳，而以波長280至320nm的波長域中的強度又更佳。 The light irradiation intensity per active energy ray-curable adhesive is determined not only because it is a composition including an adhesive, but is preferably 10 to 5,000 mW/cm 2 . When the light irradiation intensity of the resin composition is less than 10 mW/cm 2 , the reaction time becomes too long, and if it exceeds 5,000 mW/cm 2 , the radiant heat from the light source and the exothermic heat when the composition is polymerized, There is a possibility that yellowing of the epoxy resin composition or the like of the constituent material of the adhesive or deterioration of the polarizing plate is caused. Further, the irradiation intensity is preferably an intensity effective for activation of the photocationic polymerization initiator, and is preferably in a wavelength region of 400 nm or less, and is more preferably in a wavelength region of a wavelength of 280 to 320 nm.

如活性能量線為紫外線時，對積體層4照射活性能量線的步驟中，宜為在積層體4的長臂方向(運送方向)施加100至800N/m的張力，同時以照射時間為0.1秒以上的線速度使積層體4運送。 When the active energy ray is ultraviolet ray, in the step of irradiating the active layer with the active energy ray, it is preferable to apply a tension of 100 to 800 N/m in the long arm direction (transport direction) of the laminated body 4 while the irradiation time is 0.1 second. The above linear velocity transports the laminated body 4.

(第2活性能量線的照射步驟) (Step of irradiating the second active energy ray)

如來自活性能量線照射裝置31、32的活性能量線之累積光量不足時，宜設置第2之後的活性能量線照射裝置16至18，以追加照射活性能量線，以促進積層體4的接著劑之硬化。與第1活性能量線的照射步驟合計的全步驟中的紫外線(UVB)之累積光量為10mJ/cm2以上，並以設定成可使其成為60至5,000mJ/cm2時尤佳。如對上述接著劑的累積光量未達10mJ/cm2時，將使來自起始劑的活性種之產生不足，而使接著劑的硬化不充分。另一方面，如該累積光量超過5,000mJ/cm2時，將使照射時間變非常長，而不利於產率的提高。此時，可因使用的膜或接著劑的組合等，而使何者波長域(UVA(320至390nm)或UVB(280至320nm)等)中的必要累積光量不同。 When the accumulated light amount of the active energy ray from the active energy ray irradiation devices 31 and 32 is insufficient, it is preferable to provide the second active energy ray irradiation devices 16 to 18 to additionally illuminate the active energy ray to promote the adhesive of the laminated body 4. Hardening. The total amount of the whole integrated light irradiation step of the first step of the active energy ray in the ultraviolet (UVB) is of 10mJ / cm 2 or more, and is set so it can be made 60 to 5,000mJ / cm 2 when a plus. When the cumulative amount of light of the above-mentioned adhesive is less than 10 mJ/cm 2 , the production of the active species from the initiator is insufficient, and the curing of the adhesive is insufficient. On the other hand, if the accumulated light amount exceeds 5,000 mJ/cm 2 , the irradiation time becomes extremely long, which is disadvantageous for the improvement of the yield. At this time, the necessary accumulated light amount in the wavelength range (UVA (320 to 390 nm) or UVB (280 to 320 nm), etc.) may be different depending on the combination of the film or the adhesive to be used and the like.

為能確實進行偏光板(積層體)端部的接著劑之硬化 時，可列舉：例如無電極D閥燈(valve lamp)的FUSION製「Light Hammer 10」對於膜行進是橫切的排列的方法等。 Hardening of the adhesive for the end of the polarizing plate (layered body) For example, a method in which "Light Hammer 10" manufactured by FUSION, which is an electrodeless D valve lamp, is arranged transversely to the film travel, and the like.

活性能量線硬化型樹脂硬化的比例，即反應率，宜為90%以上，並以95%以上更佳。 The ratio of the active energy ray-curable resin hardening, that is, the reaction rate is preferably 90% or more, and more preferably 95% or more.

(偏光板捲取步驟) (Polarizing plate winding step)

使積層體(偏光板)4的捲取張力為30N/cm2至150N/cm2。並宜為30N/cm2至120N/cm2。如其未達30N/cm2時，將使移送長臂的滾輪捲之際，造成捲取位移而不佳。如其大於150N/cm2時，將使捲束較強，而容易產生下垂。 The winding tension of the laminate (polarizing plate) 4 is from 30 N/cm 2 to 150 N/cm 2 . It is preferably from 30 N/cm 2 to 120 N/cm 2 . If it is less than 30 N/cm 2 , it will cause the winding displacement of the long arm to be poor. If it is larger than 150 N/cm 2 , the bundle will be made stronger, and sag is likely to occur.

而且，因捲曲長度越長時，以相同張力越容易造成捲束(捲出時不易回到平坦狀態的現象)，故也可在將偏光板朝軸心捲取時，同時使張力連續或階段性的下降。如此的所謂施加斜度(taper)以降低張力的方法，也可使其時的張力成為150N/cm2以下。 Further, as the curl length is longer, the curl is more likely to be caused by the same tension (a phenomenon in which it is difficult to return to a flat state at the time of winding out), so that the tension can be continuously or at the same time when the polarizing plate is taken up toward the axis. Sexual decline. Such a method of applying a taper to reduce the tension may be such that the tension at the time is 150 N/cm 2 or less.

朝軸心捲取的偏光板之長度，雖然無特別的限定，但宜為100m以上4,000m以下。 The length of the polarizing plate taken up to the axis is not particularly limited, but is preferably 100 m or more and 4,000 m or less.

圓筒狀的軸心之直徑，宜為6英寸至12英寸。軸心的直徑是越大越好，是以11英寸、12英寸等更佳，但過大時則不易移送或保管。 The diameter of the cylindrical shaft is preferably 6 inches to 12 inches. The larger the diameter of the shaft, the better, 11 inches, 12 inches, etc., but when it is too large, it is difficult to transfer or store.

圓筒狀軸心的材質，因是在無塵室中使用，故只要其自身不易產生灰塵，如同可捲取廣幅的偏光板似的確保適切的強度，即無特別的限定，可選擇FRP(玻璃纖維強化塑膠)等。 Since the material of the cylindrical shaft is used in a clean room, it is easy to generate dust as it is, and it is suitable for winding a wide polarizing plate to ensure appropriate strength, that is, there is no particular limitation, and FRP can be selected. (glass fiber reinforced plastic) and so on.

[實施例] [Examples]

以下，列舉實施例以更詳細說明本發明，但本發明 並不侷限於此等實施例之範圍。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention It is not limited to the scope of these embodiments.

[實施例1](偏光膜之製作) [Example 1] (Production of polarizing film)

使用聚合度2,400、皂化度99.9莫耳%、厚度75μm、寬幅3,000m的長形聚乙烯醇膜「OPL膜M-7500(日本合成製)」，作為聚乙烯醇的原材料膜。延伸，是在處理槽前後的驅動壓輪上附加周速差而進行。 An elongated polyvinyl alcohol film "OPL film M-7500 (manufactured by Nippon Synthetic Co., Ltd.) having a polymerization degree of 2,400, a degree of saponification of 99.9 mol%, a thickness of 75 μm, and a width of 3,000 m was used as a raw material film of polyvinyl alcohol. The extension is performed by adding a peripheral speed difference to the driving pressure rollers before and after the processing tank.

首先，如同不使原材料膜鬆弛的就保持在膜的緊張狀態，浸漬在已加入30℃的純水之膨脹槽中80秒，使膜充分的膨脹。伴隨膨脹槽中膨脹的入口與出口之滾輪速度比為1.2。以壓輪將水份去除之後，在已加入30℃的純水之浸漬槽中浸漬160秒。將此水槽中的機械方向之延伸倍率設為1.09倍。 First, the film was kept in a state of tension as if the film of the raw material was not relaxed, and it was immersed in an expansion tank to which pure water of 30 ° C was added for 80 seconds to sufficiently expand the film. The speed ratio of the inlet to the outlet with the expansion in the expansion tank was 1.2. After the water was removed by a pressure roller, it was immersed in a dipping tank to which pure water having been added at 30 ° C for 160 seconds. The extension ratio of the mechanical direction in the water tank was set to 1.09 times.

接著，浸漬在已加入重量比：0.02/2.0/100的碘/碘化鉀/水之水溶液的染色槽中，進行延伸倍率大約1.5倍的單軸延伸。然後，以55.5℃在已加入重量比為12/3.7/100的碘化鉀/硼酸/水之水溶液的硼酸槽中浸漬130秒，進行由原材料膜的累積延伸倍率至5.7倍的單軸延伸。然後，以40℃在已加入重量比為9/2.4/100的碘化鉀/硼酸/水之水溶液的硼酸槽中浸漬60秒。 Next, immersion in a dyeing bath to which an aqueous solution of iodine/potassium iodide/water having a weight ratio of 0.02/2.0/100 was added was carried out, and a uniaxial stretching of about 1.5 times of the stretching ratio was carried out. Then, it was immersed in a boric acid bath to which an aqueous solution of potassium iodide/boric acid/water having a weight ratio of 12/3.7/100 was added at 55.5 ° C for 130 seconds to carry out uniaxial stretching from the cumulative stretching ratio of the raw material film to 5.7 times. Then, it was immersed in a boric acid bath to which an aqueous solution of potassium iodide/boric acid/water in a weight ratio of 9/2.4/100 had been added at 40 ° C for 60 seconds.

並且，在水洗槽中以80℃的純水清洗大約16秒，然後，使其依序通過大約60℃的乾燥爐、其次約85℃的乾燥爐，在此等乾燥爐中進行滯留時間合計160秒的乾燥。如此之後，獲得厚度28μm的已吸附配向碘之偏光膜。 Further, it was washed with pure water at 80 ° C for about 16 seconds in a water washing tank, and then passed through a drying furnace of about 60 ° C and a drying furnace of about 85 ° C in that order, and the total residence time was 160 in these drying furnaces. Seconds of drying. After that, a polarizing film of adsorbed orientated iodine having a thickness of 28 μm was obtained.

(偏光板之製作) (production of polarizing plate)

準備已賦與相位差特性的厚度40μm之醋酸纖維素系樹脂膜「KC4CR-1(Konica Minolta公司製)」作為透明膜，與厚 度80μm的三乙醯基纖維素膜「KC8UX2MW」。 A cellulose acetate-based resin film "KC4CR-1 (manufactured by Konica Minolta Co., Ltd.) having a thickness of 40 μm which has a phase difference characteristic is prepared as a transparent film, and is thick. A 80 μm triethylenesulfonated cellulose film "KC8UX2MW".

接著，在上述已賦予相位差特性之醋酸纖維素系樹脂膜「KC4CR-1」之單面上，利用接著劑塗布裝置(微室刮刀：富士機械社製)塗布紫外線(UVB)硬化型的接著劑之環氧樹脂組成物「KR系列」(ADEKA公司製，含陽離子聚合起始劑)。同時，在上述三乙醯基纖維素膜「KC8UX2MW」之單面，利用相同的接著劑塗布裝置塗布紫外線(UVB)硬化型的接著劑之環氧樹脂組成物「KR系列」(ADEKA公司製，含陽離子聚合起始劑)。此時，將接著劑塗布裝置中的偏光膜積層體之線速度設為25m/分鐘，使凹板滾輪朝積層材的運送方向之逆向旋轉，使醋酸纖維素系樹脂膜「KC4CR-1」上之接著劑層的厚度約作為4.0μm，而三乙醯基纖維素膜「KC8UX2MW」之接著劑層的厚度作為約3.3μm(合計大約7.3μm)。 Then, on the single side of the cellulose acetate-based resin film "KC4CR-1" to which the phase difference characteristics were applied, an ultraviolet ray (UVB) curing type was applied by an adhesive application device (micro chamber squeegee: manufactured by Fuji Machinery Co., Ltd.). The epoxy resin composition "KR series" (manufactured by ADEKA Co., Ltd., containing a cationic polymerization initiator). At the same time, the epoxy resin composition "KR series" (manufactured by Adeka Co., Ltd.) of an ultraviolet (UVB)-curable adhesive was applied to the single side of the above-mentioned triacetonitrile-based cellulose film "KC8UX2MW". Containing a cationic polymerization initiator). At this time, the linear velocity of the polarizing film laminate in the adhesive application device was set to 25 m/min, and the concave roller was rotated in the direction in which the laminate was conveyed to make the cellulose acetate resin film "KC4CR-1". The thickness of the adhesive layer was approximately 4.0 μm, and the thickness of the adhesive layer of the triethylenesulfonated cellulose film "KC8UX2MW" was about 3.3 μm (a total of about 7.3 μm).

接著，在上述偏光膜之雙面，經由上述環氧樹脂組成物(紫外線硬化型接著劑)，以壓輪貼合上述醋酸纖維素系樹脂膜「KC4CR-1」與三乙醯基纖維素膜「KC8UX2MW」(貼合力1.5MPa)。 Then, the cellulose acetate-based resin film "KC4CR-1" and the triacetyl cellulose film are bonded to the both surfaces of the polarizing film via the epoxy resin composition (ultraviolet curing type adhesive) by a pressure roller. "KC8UX2MW" (applying force 1.5MPa).

使經貼合上述2種透明膜之偏光膜，以與在長臂方向施加600N/m的張力之冷卻滾輪，同時以線速度25m/分鐘移送，使其通過金屬鹵化物燈2盞(GS-YUASA社製，1盞的電力量30W/cm)照射的紫外線中，進行第1活性能量線照射步驟，然後，使其通過設置的無電極D閥燈3盞(Fusion社製「Light Hammer 10」，盞支的電力量216W/cm)照射的紫外線中，進行第2活性能量線照射步驟後，製作成偏光板。 The polarizing film to which the above two kinds of transparent films were bonded was transferred to a cooling roller having a tension of 600 N/m in the direction of the long arm, and simultaneously transferred at a linear velocity of 25 m/min to pass through a metal halide lamp 2 (GS- The first active energy ray irradiation step was carried out in the ultraviolet ray irradiated by the YUASA system, and the first active energy ray irradiation step was carried out, and then the electrodeless D-valve lamp 3 (the "Light Hammer 10" manufactured by Fusion Co., Ltd.) was passed. In the ultraviolet ray irradiated by the electric power of 216 W/cm, the second active energy ray irradiation step was performed, and then a polarizing plate was produced.

上述的無電極D閥燈3盞，是使膜的寬幅方向並列無電極D閥燈6台形成的單元，在膜的長方向配置3列者。 The above-mentioned electrodeless D-valve lamp 3 is a unit in which six electrodes of the electrodeless D-valve lamp are arranged in parallel in the wide direction of the film, and three rows are arranged in the longitudinal direction of the film.

通過金屬鹵化物燈時，是使經貼合在上述偏光膜的三乙醯基纖維素膜「KC8UX2MW」接觸在已設定於23℃的冷卻滾輪之外緣面，由醋酸纖維素系樹脂膜「KC4CR-1」側照射紫外線。藉此，即可抑制受到第1活性能量線照射步驟中的熱之影響而造成接著劑或偏光膜之劣化。 When the metal halide lamp is passed, the triacetyl cellulose film "KC8UX2MW" bonded to the polarizing film is brought into contact with the outer surface of the cooling roller which has been set at 23 ° C, and the cellulose acetate resin film is " The KC4CR-1" side is irradiated with ultraviolet light. Thereby, deterioration of the adhesive or the polarizing film can be suppressed by the influence of heat in the first active energy ray irradiation step.

本實施例中的的第1活性能量線照射步驟中，金屬鹵化物燈合計2盞的紫外線之累積光量的合計量為172mJ/cm2。同時，其後設置的第2活性能量線照射步驟中，無電極D閥燈3盞的紫外線之累積光量的合計量為296mJ/cm2。由上述，照射活性能量線的全步驟(第1及第2活性能量線照射步驟)中的紫外線之累積光量的合計量為468mJ/cm2。此處的累積光量，是依照波長280至320nm的波長域(UVB)中的光照射強度的測定器(Fusion UV公司製UV Power Puck Ⅱ)之測定值。以上製作的偏光板的密著性方面沒有問題。 In the first active energy ray irradiation step in the present embodiment, the total amount of accumulated ultraviolet light of the metal halide lamp in a total of 2 盏 is 172 mJ/cm 2 . At the same time, in the second active energy ray irradiation step, the total amount of accumulated ultraviolet light of the electrodeless D-valve lamp 3 为 was 296 mJ/cm 2 . The total amount of accumulated ultraviolet light in the entire step of irradiating the active energy rays (the first and second active energy ray irradiation steps) is 468 mJ/cm 2 . The cumulative amount of light here is a measured value of a measuring instrument (UV Power Puck II manufactured by Fusion UV Co., Ltd.) in accordance with the light irradiation intensity in the wavelength range (UVB) of 280 to 320 nm. There is no problem in the adhesion of the polarizing plate produced above.

(外觀評估) (Appearance evaluation)

對於由上述製作的偏光板，經螢光燈照射以反射檢查進行波狀斑及波浪捲的發生狀況的評估。具體上，可確認偏光板的表面有起伏時，評估為「有」波狀斑，不可確認起伏時，評估為「無」波狀斑。同時，可確認偏光板整體有起波浪時，評估為「有」波浪捲，不可確認起波浪時，評估為「無」波浪捲。 The polarizing plate produced as described above was irradiated with a fluorescent lamp to reflect the occurrence of wavy spots and wave rolls by reflection inspection. Specifically, when it was confirmed that the surface of the polarizing plate had undulations, it was evaluated as "having" wavy spots, and when undulations were not confirmed, it was evaluated as "no" wavy spots. At the same time, it can be confirmed that when the polarizing plate as a whole has a wave, the wave roll is evaluated as "having", and when the wave is not confirmed, the "no" wave roll is evaluated.

[實施例2] [Embodiment 2]

使其通過金屬鹵化物燈3盞(GS-YUASA社製，1盞 的電力量60W/cm)進行第1活性能量線照射步驟，然後，使其通過設置的無電極D閥燈1盞(Fusion社製「Light Hammer 10」，1盞的電力量180W/cm)，進行第2活性能量線照射步驟。此外，進行與實施例1相同的步驟，製作成偏光板。 It is passed through a metal halide lamp 3 (manufactured by GS-YUASA, 1盏) The electric energy is 60 W/cm, and the first active energy ray irradiation step is performed, and then the electrodeless D-valve lamp 1 盏 ("Light Hammer 10" manufactured by Fusion Co., Ltd., electric power 180 W/cm) is passed through the set. A second active energy ray irradiation step is performed. Further, the same procedure as in Example 1 was carried out to prepare a polarizing plate.

本實施例中的的第1活性能量線照射步驟中，金屬 鹵化物燈合計3盞的紫外線之累積光量的合計量為173mJ/cm2。同時，其後設置的第2活性能量線照射步驟中，無電極D閥燈1盞的紫外線之累積光量的合計量為63mJ/cm2。由上述，照射活性能量線的全步驟(第1及第2活性能量線照射步驟)中的紫外線之累積光量的合計量為236mJ/cm2。此處的累積光量，是依照波長280至320nm的波長域(UVB)中的光照射強度的測定器(Fusion UV公司製UV Power Puck Ⅱ)之測定值。以上製作的偏光板的密著性方面沒有問題。 In the first active energy ray irradiation step in the present embodiment, the total amount of accumulated ultraviolet light of the metal halide lamp in a total of 3 Å was 173 mJ/cm 2 . At the same time, in the second active energy ray irradiation step provided thereafter, the total amount of accumulated ultraviolet light of the electrodeless D-valve lamp 1 为 was 63 mJ/cm 2 . The total amount of accumulated ultraviolet light in the entire step of irradiating the active energy rays (the first and second active energy ray irradiation steps) is 236 mJ/cm 2 . The cumulative amount of light here is a measured value of a measuring instrument (UV Power Puck II manufactured by Fusion UV Co., Ltd.) in accordance with the light irradiation intensity in the wavelength range (UVB) of 280 to 320 nm. There is no problem in the adhesion of the polarizing plate produced above.

對於實施例2的偏光板，也進行與實施例1相同的 外觀評估。結果如表1中所示。 The same applies to the polarizing plate of the second embodiment as in the first embodiment. Appearance assessment. The results are shown in Table 1.

[實施例3] [Example 3]

除了使其通過金屬鹵化物燈1盞(GS-YUASA社製，1盞的電力量60W/cm，附50%減光濾光片)之外，進行與實施例1相同的步驟，製作成偏光板。 The same procedure as in Example 1 was carried out to produce polarized light, except that it was passed through a metal halide lamp (manufactured by GS-YUASA Co., Ltd., a power of 60 W/cm, and a 50% light-reducing filter). board.

本實施例中的的第1活性能量線照射步驟中，金屬 鹵化物燈合計1盞的紫外線之累積光量的合計量為20mJ/cm2。同時，其後設置的第2活性能量線照射步驟中，無電極D閥燈3盞的紫外線之累積光量的合計量為296mJ/cm2。由上述，照射活性能量線的全步驟(第1及第2活性能量線照射步驟)中的紫外線之累 積光量的合計量為316mJ/cm2。此處的累積光量，是依照波長280至320nm的波長域(UVB)中的光照射強度的測定器(Fusion UV公司製UV Power Puck Ⅱ)之測定值。以上製作的偏光板的密著性方面沒有問題。 In the first active energy ray irradiation step in the present embodiment, the total amount of accumulated ultraviolet light of the metal halide lamp in a total of 1 Å is 20 mJ/cm 2 . At the same time, in the second active energy ray irradiation step, the total amount of accumulated ultraviolet light of the electrodeless D-valve lamp 3 为 was 296 mJ/cm 2 . The total amount of accumulated ultraviolet light in the entire step of irradiating the active energy rays (the first and second active energy ray irradiation steps) is 316 mJ/cm 2 . The cumulative amount of light here is a measured value of a measuring instrument (UV Power Puck II manufactured by Fusion UV Co., Ltd.) in accordance with the light irradiation intensity in the wavelength range (UVB) of 280 to 320 nm. There is no problem in the adhesion of the polarizing plate produced above.

對於實施例3的偏光板，也進行與實施例1相同的 外觀評估。結果如表1中所示。 The polarizing plate of Example 3 was also subjected to the same operation as in Example 1. Appearance assessment. The results are shown in Table 1.

[比較例1] [Comparative Example 1]

除了使其通過金屬鹵化物燈2盞(GS-YUASA社製，1盞的電力量140W/cm)之外，其餘進行與實施例1相同的步驟，製作成偏光板。 The same procedure as in Example 1 was carried out except that the metal halide lamp 2 (manufactured by GS-YUASA Co., Ltd., electric power: 140 W/cm) was used to prepare a polarizing plate.

本實施例中的的第1活性能量線照射步驟中，金屬 鹵化物燈合計2盞的紫外線之累積光量的合計量為191mJ/cm2。同時，其後設置的第2活性能量線照射步驟中，無電極D閥燈3盞的紫外線之累積光量的合計量為296mJ/cm2。由上述，照射活性能量線的全步驟(第1及第2活性能量線照射步驟)中的紫外線之累積光量的合計量為487mJ/cm2。此處的累積光量，是依照波長280至320nm的波長域(UVB)中的光照射強度的測定器(Fusion UV公司製UV Power Puck Ⅱ)之測定值。以上製作的偏光板的密著性方面沒有問題。 In the first active energy ray irradiation step in the present embodiment, the total amount of accumulated ultraviolet light of the metal halide lamp in a total of 2 Å was 191 mJ/cm 2 . At the same time, in the second active energy ray irradiation step, the total amount of accumulated ultraviolet light of the electrodeless D-valve lamp 3 为 was 296 mJ/cm 2 . The total amount of accumulated ultraviolet light in the entire step of irradiating the active energy rays (the first and second active energy ray irradiation steps) is 487 mJ/cm 2 . The cumulative amount of light here is a measured value of a measuring instrument (UV Power Puck II manufactured by Fusion UV Co., Ltd.) in accordance with the light irradiation intensity in the wavelength range (UVB) of 280 to 320 nm. There is no problem in the adhesion of the polarizing plate produced above.

對於比較例1的偏光板，也進行與實施例1相同的 外觀評估。結果如表1中所示。 The polarizing plate of Comparative Example 1 was also subjected to the same operation as in Example 1. Appearance assessment. The results are shown in Table 1.

[比較例2] [Comparative Example 2]

除了使其通過金屬鹵化物燈3盞(GS-YUASA社製，1盞的電力量100W/cm)之外，其餘進行與實施例2相同的步驟， 製作成偏光板。 The same procedure as in Example 2 was carried out except that the metal halide lamp 3 (manufactured by GS-YUASA Co., Ltd., 100 W/cm) was used. Made into a polarizing plate.

本比較例中的的第1活性能量線照射步驟中，金屬 鹵化物燈合計3盞的紫外線之累積光量的合計量為289mJ/cm2。同時，其後設置的第2活性能量線照射步驟中，無電極D閥燈1盞的紫外線之累積光量的合計量為63mJ/cm2。由上述，照射活性能量線的全步驟(第1及第2活性能量線照射步驟)中的紫外線之累積光量的合計量為352mJ/cm2。此處的累積光量，是依照波長280至320nm的波長域(UVB)中的光照射強度的測定器(Fusion UV公司製UV Power Puck Ⅱ)之測定值。以上製作的偏光板的密著性方面沒有問題。 In the first active energy ray irradiation step in the comparative example, the total amount of accumulated ultraviolet light of the metal halide lamp in a total of 3 Å was 289 mJ/cm 2 . At the same time, in the second active energy ray irradiation step provided thereafter, the total amount of accumulated ultraviolet light of the electrodeless D-valve lamp 1 为 was 63 mJ/cm 2 . The total amount of accumulated ultraviolet light in the entire step of irradiating the active energy rays (the first and second active energy ray irradiation steps) is 352 mJ/cm 2 . The cumulative amount of light here is a measured value of a measuring instrument (UV Power Puck II manufactured by Fusion UV Co., Ltd.) in accordance with the light irradiation intensity in the wavelength range (UVB) of 280 to 320 nm. There is no problem in the adhesion of the polarizing plate produced above.

對於比較例2的偏光板，也進行與實施例1相同的 外觀評估。結果如表1中所示。 The polarizing plate of Comparative Example 2 was also subjected to the same operation as in Example 1. Appearance assessment. The results are shown in Table 1.

[比較例3] [Comparative Example 3]

不進行第1活性能量線照射步驟，而使其通過設置的無電極D閥燈3盞(Fusion社製「Light Hammer 10」，1盞的電力量216W/cm)，進行第2活性能量線照射步驟。此外，進行與實施例1相同的步驟，製作成偏光板。 The first active energy ray irradiation step is performed without passing through the electrodeless D-valve lamp 3 ("Light Hammer 10" manufactured by Fusion Co., Ltd., electric power 216 W/cm). step. Further, the same procedure as in Example 1 was carried out to prepare a polarizing plate.

本比較例中的的第2活性能量線照射步驟中，無電 極D閥燈3盞的紫外線之累積光量的合計量為296mJ/cm2，照射活性能量線的全步驟(第1及第2活性能量線照射步驟)中的紫外線之累積光量的合計量也為296mJ/cm2。此處的累積光量，是依照波長280至320nm的波長域(UVB)中的光照射強度的測定器(Fusion UV公司製UV Power Puck Ⅱ)之測定值。以上製作的偏光板的密著性方面沒有問題。 In the second active energy ray irradiation step in the comparative example, the total amount of accumulated ultraviolet light of the electrodeless D-valve lamp 3 为 is 296 mJ/cm 2 , and the entire steps of irradiating the active energy ray (first and second activities) The total amount of accumulated ultraviolet light in the energy ray irradiation step) was also 296 mJ/cm 2 . The cumulative amount of light here is a measured value of a measuring instrument (UV Power Puck II manufactured by Fusion UV Co., Ltd.) in accordance with the light irradiation intensity in the wavelength range (UVB) of 280 to 320 nm. There is no problem in the adhesion of the polarizing plate produced above.

對於比較例3的偏光板，也進行與實施例1相同的 外觀評估。結果如表1中所示。 The polarizing plate of Comparative Example 3 was also subjected to the same operation as in Example 1. Appearance assessment. The results are shown in Table 1.

表1中，空欄(「-」)是表示”無”。如表1中示，對於實施例1至3的偏光板，均無密著性的問題，同時也確認無波狀斑及波浪捲的發生。另一方面，對於比較例1、2，可確認有波狀斑的發生，對於比較例3，可確認有波浪捲的發生。由以上結果可知，藉由第1活性能量線照射射步驟中的累積光量為10mJ/cm2以上且185mJ/cm2以下，即可防止波狀斑及波浪捲的發生。 In Table 1, the empty column ("-") means "none". As shown in Table 1, the polarizing plates of Examples 1 to 3 had no problem of adhesion, and it was confirmed that no wavy spots and wave rolls occurred. On the other hand, in Comparative Examples 1 and 2, the occurrence of wavy spots was confirmed, and in Comparative Example 3, the occurrence of a wave roll was confirmed. From the above results, the integrated light quantity by the first emitting active energy ray irradiation step is 2 or more and 185mJ / cm 2 or less, can be prevented, and a wavy wavy plaque volume occurs 10mJ / cm.

[產業上應用之可能性] [The possibility of industrial application]

本發明的偏光板，可有效適用於以液晶顯示器為首的各種顯示器上。 The polarizing plate of the present invention can be effectively applied to various displays including liquid crystal displays.

1‧‧‧偏光膜 1‧‧‧ polarizing film

2、3‧‧‧透明膜 2, 3‧‧‧ transparent film

4‧‧‧積層體(偏光板) 4‧‧‧Laminated body (polarizer)

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

13‧‧‧滾輪(冷卻滾輪) 13‧‧‧Roller (cooling roller)

16、17、18、31、32‧‧‧活性能量線照射裝置 16, 17, 18, 31, 32‧‧‧Active energy line irradiation device

19‧‧‧運送用壓輪 19‧‧‧Loading wheel

20‧‧‧捲取滾輪 20‧‧‧Rolling wheel

51、52‧‧‧貼合滾輪 51, 52‧‧‧ fitted roller

Claims (5)

一種偏光板之製造方法，此方法係在偏光膜的單面或雙面貼合透明膜而形成偏光板之製造方法，此方法包括依序進行下列步驟：在前述透明膜的單面或前述偏光膜的單面或雙面，塗布活性能量線硬化型接著劑之接著劑塗布步驟、對前述透明膜經由前述接著劑積層在前述偏光膜的單面或雙面所形成的積層體施加壓力，而使前述透明膜與前述偏光膜貼合的貼合步驟，與在前述積層體以與向運送方向旋轉的滾輪密著之狀態運送之期間，對前述積層體照射活性能量線，而使前述接著劑硬化的第1活性能量線照射步驟，對前述積層體照射活性能量線，而使前述接著劑硬化的第2活性能量線照射步驟；前述第1活性能量線照射步驟中，紫外線(UVB)的累積光量為10mJ/cm2以上且185mJ/cm2以下，前述第2活性能量線照射步驟中，紫外線(UVB)的累積光量為63mJ/cm2以上且296mJ/cm2以下。 A method for producing a polarizing plate, which is a method for manufacturing a polarizing plate by laminating a transparent film on one or both sides of a polarizing film, the method comprising the steps of: performing single-sided or polarized light on the transparent film Applying an adhesive coating step of an active energy ray-curable adhesive on one or both sides of the film, and applying pressure to the laminate formed on one or both sides of the polarizing film via the adhesive layer, The bonding step of bonding the transparent film to the polarizing film is performed by irradiating the laminated body with an active energy ray while the laminated body is transported in a state of being adhered to the roller rotating in the transport direction, and the adhesive is applied to the adhesive. a first active energy ray irradiation step of curing, a second active energy ray irradiation step of irradiating the active energy ray to the laminate, and curing the adhesive; and an accumulation of ultraviolet ray (UVB) in the first active energy ray irradiation step light amount of 10mJ / cm 2 or more and 185mJ / cm 2 or less, the second step of irradiating the active energy ray, the cumulative dose of ultraviolet radiation (UVB) is 63mJ / cm 2 or more and 296mJ / cm 2 to under. 如申請專利範圍第1項中所述之偏光板的製造方法，其中前述滾輪為冷卻滾輪。 The method of manufacturing a polarizing plate according to claim 1, wherein the roller is a cooling roller. 如申請專利範圍第1或2項中所述之偏光板的製造方法，其中前述透明膜之至少一方為醋酸纖維素系樹脂膜。 The method for producing a polarizing plate according to the first or second aspect of the invention, wherein at least one of the transparent films is a cellulose acetate resin film. 如申請專利範圍第1或2項所述之偏光板的製造方法，其中前述第2活性能量線照射步驟中，前述活性能量線的照射是以複數個光源進行。 The method for producing a polarizing plate according to claim 1 or 2, wherein in the second active energy ray irradiation step, the irradiation of the active energy ray is performed by a plurality of light sources. 如申請專利範圍第1或2項所述之偏光板的製造方法，其中前述第1活性能量線照射步驟中，前述活性能量線的照射是以複數個光源進行。 The method for producing a polarizing plate according to claim 1, wherein in the first active energy ray irradiation step, the irradiation of the active energy ray is performed by a plurality of light sources.
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