JP5908257B2 - Manufacturing method of polarizing plate, polarizing plate, optical film, and image display device - Google Patents
Manufacturing method of polarizing plate, polarizing plate, optical film, and image display device Download PDFInfo
- Publication number
- JP5908257B2 JP5908257B2 JP2011245432A JP2011245432A JP5908257B2 JP 5908257 B2 JP5908257 B2 JP 5908257B2 JP 2011245432 A JP2011245432 A JP 2011245432A JP 2011245432 A JP2011245432 A JP 2011245432A JP 5908257 B2 JP5908257 B2 JP 5908257B2
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- JP
- Japan
- Prior art keywords
- polarizing plate
- adhesive
- polyvinyl alcohol
- producing
- polarizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000004519 manufacturing process Methods 0.000 title claims description 33
- 239000012788 optical film Substances 0.000 title claims description 16
- 229920005989 resin Polymers 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 68
- 239000000853 adhesive Substances 0.000 claims description 66
- 239000010408 film Substances 0.000 claims description 66
- 230000001070 adhesive effect Effects 0.000 claims description 59
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 55
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 53
- 230000001681 protective effect Effects 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 39
- 239000012790 adhesive layer Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 20
- 125000002339 acetoacetyl group Chemical group O=C([*])C([H])([H])C(=O)C([H])([H])[H] 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 15
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- 230000003287 optical effect Effects 0.000 claims description 14
- 239000003002 pH adjusting agent Substances 0.000 claims description 14
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 150000007526 arrhenius bases Chemical class 0.000 claims description 6
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- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 53
- 238000002834 transmittance Methods 0.000 description 35
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- -1 acrylamide alkyl sulfonic acid alkali salt Chemical class 0.000 description 9
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- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
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- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical group O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
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- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229960003080 taurine Drugs 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
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- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical group NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 235000002374 tyrosine Nutrition 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は、偏光板の製法方法に関する。また本発明は当該製造方法により得られた偏光板に関する。当該偏光板はこれ単独で、又はこれを積層した光学フィルムとして液晶表示装置、有機ＥＬ表示装置、ＰＤＰ等の画像表示装置を形成しうる。 The present invention relates to a method for producing a polarizing plate. Moreover, this invention relates to the polarizing plate obtained by the said manufacturing method. The polarizing plate can form an image display device such as a liquid crystal display device, an organic EL display device, and a PDP alone or as an optical film obtained by laminating the polarizing plate.
液晶表示装置には、その画像形成方式から液晶パネル表面を形成するガラス基板の両側に偏光子を配置することが必要不可欠である。偏光子は、一般的には、ポリビニルアルコール系フィルムをヨウ素などの二色性材料で染色した後、架橋剤を用いて架橋を行い、一軸延伸をすることにより製膜することにより得られる。前記偏光子は延伸により作成されるため、収縮し易い。またポリビニルアルコール系フィルムは親水性ポリマーを使用していることから、特に加湿条件下においては非常に変形し易い。またフィルム自体の機械的強度が弱いため、フィルムが裂けたりする問題がある。そのため、偏光子の両側又は片側にトリアセチルセルロースなどの透明保護フィルムを貼り合わせて、強度を補った偏光板が用いられている。前記偏光板は、偏光子と透明保護フィルムを接着剤で貼り合わせることにより製造されている。 In a liquid crystal display device, it is indispensable to dispose polarizers on both sides of a glass substrate on which a liquid crystal panel surface is formed because of its image forming method. In general, a polarizer is obtained by dyeing a polyvinyl alcohol film with a dichroic material such as iodine, cross-linking with a cross-linking agent, and forming a film by uniaxial stretching. Since the polarizer is made by stretching, it easily contracts. In addition, since the polyvinyl alcohol film uses a hydrophilic polymer, it is very easily deformed particularly under humidified conditions. Moreover, since the mechanical strength of the film itself is weak, there is a problem that the film is torn. Therefore, a polarizing plate is used in which a transparent protective film such as triacetyl cellulose is bonded to both sides or one side of the polarizer to supplement the strength. The polarizing plate is manufactured by bonding a polarizer and a transparent protective film with an adhesive.
近年、液晶表示装置の低消費電力化の観点から、液晶表示装置の白輝度の向上が望まれており、それに伴い透過率の高い偏光子の開発が望まれている。しかしながら、単に単体透過率を高くしようとすると、偏光度が低下し、表示コントラストの低下をまねくという問題がある。一方、偏光度を高くしようとすると、単体透過率が低下し、白輝度の低下を招くという問題がある。このように、偏光子の単体透過率と偏光度はトレードオフの関係にある。したがって、高透過率及び高偏光度を両立する偏光板の開発が求められている。 In recent years, from the viewpoint of reducing the power consumption of a liquid crystal display device, it has been desired to improve the white luminance of the liquid crystal display device, and accordingly, development of a polarizer having a high transmittance is desired. However, simply increasing the single transmittance has a problem in that the degree of polarization decreases and the display contrast decreases. On the other hand, when the degree of polarization is increased, there is a problem that the single transmittance decreases and white luminance decreases. Thus, the single transmittance of the polarizer and the degree of polarization are in a trade-off relationship. Therefore, development of a polarizing plate that achieves both high transmittance and high degree of polarization is required.
また、近年の液晶表示装置は用途が拡大し、携帯端末から家庭用の大型ＴＶまで幅広く展開が進んできており、各用途に応じて、それぞれの規格が設けられるようになってきている。特に携帯端末用途では、使用者が持ち歩くことが前提であるため、耐久性に対する要求は非常に厳しい。例えば、偏光板には、結露が生じるような加湿条件下においても特性、形状が変化しない加湿信頼性が求められている。 In recent years, the use of liquid crystal display devices has been expanded, and a wide range of development has been progressing from portable terminals to large-sized TVs for home use, and respective standards have been provided according to each application. Particularly in portable terminal applications, since it is assumed that the user carries around, the demand for durability is very strict. For example, a polarizing plate is required to have humidification reliability that does not change in characteristics and shape even under humidification conditions in which condensation occurs.
前記の通り偏光子は、透明保護フィルムにより強度を補強した偏光板として使用される。前記偏光子と透明保護フィルムの接着に用いる偏光板用接着剤としては、水系接着剤が好ましく、例えば、ポリビニルアルコール水溶液に架橋剤を混合したポリビニルアルコール系接着剤が使用されている。しかし、ポリビニルアルコール系接着剤は、加湿条件下では、偏光子と透明保護フィルムとの界面で剥がれが生じる場合がある。これは、前記接着剤の主成分であるポリビニルアルコール系樹脂が水溶性高分子であり、結露した状況下では接着剤の溶解が起こっている可能性が考えられる。上記問題に対して、アセトアセチル基を含有するポリビニルアルコール系樹脂と架橋剤を含有する偏光板用接着剤が提案されている（特許文献１）。また、ポリビニルアルコール樹脂、無水マレイン酸骨格を構造中に含む樹脂及び架橋剤を含有する偏光素子用水性接着剤が提案されている（特許文献２）。しかし、これらの偏光板用接着剤では、高透過率及び高偏光度を有し、かつ加湿信頼性の良好な偏光板は得られていない。 As described above, the polarizer is used as a polarizing plate whose strength is reinforced by a transparent protective film. As an adhesive for polarizing plates used for adhesion | attachment of the said polarizer and a transparent protective film, a water-system adhesive agent is preferable, for example, the polyvinyl alcohol-type adhesive agent which mixed the crosslinking agent in the polyvinyl alcohol aqueous solution is used. However, the polyvinyl alcohol-based adhesive may peel off at the interface between the polarizer and the transparent protective film under humidified conditions. This may be because the polyvinyl alcohol resin, which is the main component of the adhesive, is a water-soluble polymer, and the adhesive may be dissolved under the dew condensation condition. In order to solve the above problem, a polarizing plate adhesive containing a polyvinyl alcohol-based resin containing an acetoacetyl group and a crosslinking agent has been proposed (Patent Document 1). Moreover, the water-based adhesive for polarizing elements containing the polyvinyl alcohol resin, the resin which contains maleic anhydride frame | skeleton in a structure, and a crosslinking agent is proposed (patent document 2). However, with these polarizing plate adhesives, a polarizing plate having a high transmittance and a high degree of polarization and good humidification reliability has not been obtained.
本発明は、高透過率及び高偏光度を有し、かつ前記特性に加えて、加湿信頼性の良好な偏光板の製造方法を提供することを目的とする。 An object of this invention is to provide the manufacturing method of a polarizing plate which has a high transmittance | permeability and a high polarization degree, and has favorable humidification reliability in addition to the said characteristic.
また本発明は前記製造方法により得られて偏光板を提供することを目的とする。さらに本発明は、当該偏光板を積層した光学フィルムを提供すること、さらには、当該偏光板、光学フィルムを用いた液晶表示装置等の画像表示装置を提供することを目的とする。 Another object of the present invention is to provide a polarizing plate obtained by the above production method. Furthermore, an object of the present invention is to provide an optical film in which the polarizing plate is laminated, and to provide an image display device such as a liquid crystal display device using the polarizing plate and the optical film.
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、以下に示す偏光板の製造方法等により前記目的に達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by a method for producing a polarizing plate shown below, and have completed the present invention.
即ち、本発明は、偏光子及び／又は透明保護フィルムに偏光板用接着剤を塗布する工程（１）、前記接着剤により偏光子と透明保護フィルムとを貼り合わせる工程（２）、並びに前記接着剤を乾燥して接着剤層を形成する乾燥工程（３）を含む、偏光子の少なくとも一方の面に接着剤層を介して透明保護フィルムが設けられている偏光板の製造方法であって、
前記偏光板用接着剤は、ポリビニルアルコール系樹脂及びｐＨ調整剤を含有し、かつ、ｐＨが８．０〜１０．５に調整された樹脂水溶液であり、
前記乾燥工程（３）の乾燥条件が、乾燥温度２５〜５０℃で、乾燥時間８分間以上であることを特徴とする偏光板の製造方法、に関する。
That is, the present invention includes a step (1) of applying a polarizing plate adhesive to a polarizer and / or a transparent protective film, a step (2) of bonding the polarizer and the transparent protective film with the adhesive, and the bonding. A method for producing a polarizing plate comprising a drying step (3) for drying an agent to form an adhesive layer, wherein a transparent protective film is provided on at least one surface of the polarizer via the adhesive layer,
The polarizing plate adhesive is a resin aqueous solution containing a polyvinyl alcohol-based resin and a pH adjuster and having a pH adjusted to 8.0 to 10.5.
It is related with the manufacturing method of the polarizing plate characterized by the drying conditions of the said drying process (3) being the drying temperature of 25-50 degreeC, and drying time 8 minutes or more.
前記偏光板の製造方法において、前記ｐＨ調整剤としては、アレニウス塩基及び／又はブレンステッド塩基に関わるアルカリ剤を用いることができる。 In the method for producing the polarizing plate, as the pH adjuster, an alkaline agent related to Arrhenius base and / or Bronsted base can be used.
前記偏光板の製造方法において、前記ｐＨ調整剤としては、水溶性珪酸塩を用いることができる。前記水溶性珪酸塩としては、珪酸リチウム、珪酸ナトリウム及び珪酸カリウムからなる群より選択される少なくとも１種が好適である。 In the method for producing the polarizing plate, a water-soluble silicate can be used as the pH adjuster. The water-soluble silicate is preferably at least one selected from the group consisting of lithium silicate, sodium silicate, and potassium silicate.
前記偏光板の製造方法において、前記ポリビニルアルコール系樹脂としては、アセトアセチル基を含有するポリビニルアルコール系樹脂が好適である。 In the method for producing a polarizing plate, the polyvinyl alcohol resin is preferably a polyvinyl alcohol resin containing an acetoacetyl group.
前記偏光板の製造方法において、前記接着剤層の厚みは、１０〜３００ｎｍであることが好適である。 In the method for manufacturing the polarizing plate, it is preferable that the adhesive layer has a thickness of 10 to 300 nm.
また本発明は、前記製造方法により得られた偏光板、に関する。 Moreover, this invention relates to the polarizing plate obtained by the said manufacturing method.
また本発明は、前記偏光板が、少なくとも１枚積層されている光学フィルム、に関する。 The present invention also relates to an optical film in which at least one polarizing plate is laminated.
さらに本発明は、前記偏光板又は前記光学フィルムを含む画像表示装置、に関する。 Furthermore, this invention relates to the image display apparatus containing the said polarizing plate or the said optical film.
本発明の偏光板の製法方法では、偏光板用接着剤として、ｐＨを弱アルカリ〜アルカリの８．０〜１０．５に調整した樹脂水溶液を用い、かつ、偏光子と透明保護フィルムを前記接着剤により貼り合わせた後の乾燥工程（３）では、乾燥温度２５〜５０℃で、乾燥時間８分間以上の乾燥条件で乾燥処理を行っている。このように、弱アルカリ〜アルカリに調整された樹脂水溶液を偏光板接着剤として用いて、比較的に低温の所定温度で、じっくりと所定時間の乾燥処理を施すことで、接着剤中のアルカリがゆっくりと偏光子へ働きかけることができる。こうした状態によって、例えば、偏光子中に存在しているＩ−イオンがＩ３−錯体を効率的に形成されて、偏光子の光学特性（高透過率、高偏光度）の良好な偏光板を得ることができたものと考えられる。得られた偏光板は、広帯域において、直交透過率が低いものが得られ、特に、黒表示が好適である。また、本発明の製造方法で得られた偏光板は加湿環境下において光透過率が低下しにくく、加湿信頼性が良好である。 In the method for producing a polarizing plate of the present invention, an aqueous resin solution having a pH adjusted to 8.0 to 10.5 of weak alkali to alkali is used as the polarizing plate adhesive, and the polarizer and the transparent protective film are bonded. In the drying step (3) after bonding with the agent, the drying process is performed at a drying temperature of 25 to 50 ° C. under a drying condition of 8 minutes or more. In this way, by using a resin aqueous solution adjusted to weak alkali to alkali as a polarizing plate adhesive, by subjecting it to a drying process for a predetermined time at a relatively low temperature, the alkali in the adhesive is reduced. You can work on the polarizer slowly. By such state, eg, I present in the polarizer - ions are formed a I 3- complexes efficiently, the optical properties (high transmittance, high polarization degree) of the polarizer good polarizing plate It is thought that it was possible to obtain. The obtained polarizing plate has a low orthogonal transmittance in a wide band, and black display is particularly preferable. In addition, the polarizing plate obtained by the production method of the present invention is less likely to decrease light transmittance in a humidified environment and has good humidification reliability.
本発明の偏光板の製造方法では、偏光板用接着剤として、ポリビニルアルコール系樹脂及びｐＨ調整剤を含有し、かつ、ｐＨが８．０〜１０．５に調整された樹脂水溶液を用いる。 In the method for producing a polarizing plate of the present invention, a resin aqueous solution containing a polyvinyl alcohol resin and a pH adjuster and having a pH adjusted to 8.0 to 10.5 is used as the adhesive for the polarizing plate.
ポリビニルアルコール系樹脂としては、ポリビニルアルコール樹脂や、アセトアセチル基を有するポリビニルアルコール樹脂が挙げられる。アセトアセチル基を有するポリビニルアルコール樹脂は、反応性の高い官能基を有するポリビニルアルコール系接着剤であり、偏光板の耐久性が向上し好ましい。 Examples of the polyvinyl alcohol resin include polyvinyl alcohol resins and polyvinyl alcohol resins having an acetoacetyl group. The polyvinyl alcohol resin having an acetoacetyl group is a polyvinyl alcohol-based adhesive having a highly reactive functional group, and is preferable because the durability of the polarizing plate is improved.
前記偏光板用接着剤において、ポリビニルアルコール系樹脂として、アセトアセチル基を含有するポリビニルアルコール系樹脂を用いる場合に本発明は特に好適である。アセトアセチル基を含有するポリビニルアルコール系樹脂を用いた接着剤は、耐水性に優れる接着剤層を形成することができる。 In the adhesive for polarizing plates, the present invention is particularly suitable when a polyvinyl alcohol resin containing an acetoacetyl group is used as the polyvinyl alcohol resin. An adhesive using a polyvinyl alcohol-based resin containing an acetoacetyl group can form an adhesive layer having excellent water resistance.
ポリビニルアルコール系樹脂は、ポリ酢酸ビニルをケン化して得られたポリビニルアルコール；その誘導体；更に酢酸ビニルと共重合性を有する単量体との共重合体のケン化物；ポリビニルアルコールをアセタール化、ウレタン化、エーテル化、グラフト化、リン酸エステル化等した変性ポリビニルアルコールが挙げられる。前記単量体としては、（無水）マレイン酸、フマール酸、クロトン酸、イタコン酸、（メタ）アクリル酸等の不飽和カルボン酸及びそのエステル類；エチレン、プロピレン等のα−オレフィン、（メタ）アリルスルホン酸（ソーダ）、スルホン酸ソーダ（モノアルキルマレート）、ジスルホン酸ソーダアルキルマレート、Ｎ−メチロールアクリルアミド、アクリルアミドアルキルスルホン酸アルカリ塩、Ｎ−ビニルピロリドン、Ｎ−ビニルピロリドン誘導体等が挙げられる。これらポリビニルアルコール系樹脂は一種を単独で又は二種以上を併用することができる。 Polyvinyl alcohol resin is polyvinyl alcohol obtained by saponifying polyvinyl acetate; a derivative thereof; a saponified product of a copolymer of vinyl acetate and a monomer having copolymerizability; Examples thereof include modified polyvinyl alcohols that have been converted into ethers, ethers, grafts, or phosphoric esters. Examples of the monomer include unsaturated carboxylic acids such as (anhydrous) maleic acid, fumaric acid, crotonic acid, itaconic acid, (meth) acrylic acid, and esters thereof; α-olefins such as ethylene and propylene, (meth) Examples include allyl sulfonic acid (soda), sulfonic acid soda (monoalkyl malate), disulfonic acid soda alkyl maleate, N-methylol acrylamide, acrylamide alkyl sulfonic acid alkali salt, N-vinyl pyrrolidone, N-vinyl pyrrolidone derivatives, and the like. . These polyvinyl alcohol resins can be used alone or in combination of two or more.
前記ポリビニルアルコール系樹脂は特に限定されないが、接着性の点からは、平均重合度１００〜５０００程度、好ましくは１０００〜４０００、平均ケン化度８５〜１００モル％程度、好ましくは９０〜１００モル％である。 The polyvinyl alcohol-based resin is not particularly limited, but from the viewpoint of adhesiveness, the average degree of polymerization is about 100 to 5000, preferably 1000 to 4000, the average saponification degree is about 85 to 100 mol%, preferably 90 to 100 mol%. It is.
アセトアセチル基を含有するポリビニルアルコール系樹脂は、ポリビニルアルコール系樹脂とジケテンとを公知の方法で反応して得られる。例えば、ポリビニルアルコール系樹脂を酢酸等の溶媒中に分散させておき、これにジケテンを添加する方法、ポリビニルアルコール系樹脂をジメチルホルムアミド又はジオキサン等の溶媒にあらかじめ溶解しておき、これにジケテンを添加する方法等が挙げられる。またポリビニルアルコールにジケテンガス又は液状ジケテンを直接接触させる方法が挙げられる。 A polyvinyl alcohol-based resin containing an acetoacetyl group is obtained by reacting a polyvinyl alcohol-based resin with diketene by a known method. For example, a method in which a polyvinyl alcohol resin is dispersed in a solvent such as acetic acid and diketene is added thereto. A polyvinyl alcohol resin is previously dissolved in a solvent such as dimethylformamide or dioxane, and diketene is added thereto. And the like. Moreover, the method of making diketene gas or liquid diketene contact directly to polyvinyl alcohol is mentioned.
アセトアセチル基を含有するポリビニルアルコール系樹脂のアセトアセチル基変性度は、０．１モル％以上であれば特に制限はなない。０．１モル％未満では接着剤層の耐水性が不充分であり不適当である。アセトアセチル基変性度は、好ましくは０．１〜４０モル％程度、さらに好ましくは１〜２０モル％、特に好ましくは２〜７モル％である。アセトアセチル基変性度が４０モル％を超えると、耐水性の向上効果が小さい。アセトアセチル基変性度はＮＭＲにより測定した値である。 The degree of acetoacetyl group modification of the polyvinyl alcohol-based resin containing an acetoacetyl group is not particularly limited as long as it is 0.1 mol% or more. If it is less than 0.1 mol%, the water resistance of the adhesive layer is insufficient and unsuitable. The degree of acetoacetyl group modification is preferably about 0.1 to 40 mol%, more preferably 1 to 20 mol%, and particularly preferably 2 to 7 mol%. When the acetoacetyl group modification degree exceeds 40 mol%, the effect of improving water resistance is small. The degree of acetoacetyl modification is a value measured by NMR.
樹脂水溶液中には架橋剤を添加してもよい。架橋剤としては、ポリビニルアルコール系接着剤に用いられているものを特に制限なく使用できる。前記ポリビニルアルコール系樹脂と反応性を有する官能基を少なくとも２つ有する化合物を使用できる。例えば、エチレンジアミン、トリエチレンジアミン、ヘキサメチレンジアミン等のアルキレン基とアミノ基を２個有するアルキレンジアミン類；トリレンジイソシアネート、水素化トリレンジイソシアネート、トリメチロールプロパントリレンジイソシアネートアダクト、トリフェニルメタントリイソシアネート、メチレンビス（４−フェニルメタントリイソシアネート）、イソホロンジイソシアネート及びこれらのケトオキシムブロック物又はフェノールブロック物等のイソシアネート類；エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジ又はトリグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジグリシジルアミン等のエポキシ類；ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド等のモノアルデヒド類；グリオキザール、マロンジアルデヒド、スクシンジアルデヒド、グルタルジアルデヒド、マレインジアルデヒド、フタルジアルデヒド等のジアルデヒド類；メチロール尿素、メチロールメラミン、アルキル化メチロール尿素、アルキル化メチロール化メラミン、アセトグアナミン、ベンゾグアナミンとホルムアルデヒドとの縮合物等のアミノ−ホルムアルデヒド樹脂；酢酸ジルコニウム、硝酸ジルコニウム、炭酸ジルコニウム、水酸化ジルコニウム、酸塩化ジルコニウム等のジルコニウム化合物；グリオキシル酸金属塩（金属としては、例えば、リチウム、ナトリウム、カリウムなどのアルカリ金属、マグネシウム、カルシウムなどのアルカリ土類金属、チタン、ジルコニウム、クロム、マンガン、鉄、コバルト、ニッケル、銅などの遷移金属、亜鉛、アルミニウムなどが挙げられる。）、グリオキシル酸アミン塩（アミンとしては、例えば、アンモニア、モノメチルアミン、ジメチルアミン、トリメチルアミンなどが挙げられる。）などのグリオキシル酸塩；１つ以上の塩基性基と１つ以上の酸性基とを有するアミノ酸又は含硫アミノ酸；ジメトキシエタナール、ジエトキシエタナール、ジアルコキシエタナール等のアセタール化合物；更にナトリウム、カリウム、マグネシウム、カルシウム、アルミニウム、鉄、ニッケル等の二価金属、又は三価金属の塩及びその酸化物が挙げられる。これらは一種単独で又は二種以上を併用することができる。これらのなかでも１つ以上の塩基性基と１つ以上の酸性基とを有するアミノ酸又は含硫アミノ酸を用いることが好ましい。塩基性基としてはアミノ基が好ましく、酸性基としてはカルボキシル基又はスルホ基が好ましい。前記アミノ酸としては、例えば、グリシン、アラニン、フェニルアラニン、バリン、ロイシン、イソロイシン、リシン、プロリン、セリン、トレオニン、トリプトファン、ヒスチジン、チロシン、アルギニン、アスパラギン、アスパラギン酸、アスパルテーム、グルタミン、グルタミン酸、及びこれらアミノ酸と（メタ）アクリル酸との共重合体などが挙げられる。前記含硫アミノ酸としては、例えば、メチオニン、システイン、シスチン、及びタウリンなどが挙げられる。これらのなかでも特に、タウリンなどのスルホ基を有する含硫アミノ酸を用いることが好ましい。また、架橋剤としては、シランカップリング剤、チタンカップリング剤などのカップリング剤を用いることができる。 A crosslinking agent may be added to the aqueous resin solution. As a crosslinking agent, what is used for the polyvinyl alcohol-type adhesive agent can be especially used without a restriction | limiting. A compound having at least two functional groups having reactivity with the polyvinyl alcohol resin can be used. For example, alkylene diamines having two alkylene groups and two amino groups such as ethylene diamine, triethylene diamine and hexamethylene diamine; tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis (4-phenylmethane triisocyanate), isophorone diisocyanate and isocyanates such as ketoxime block product or phenol block product thereof; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether, 1,6- Hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycy Epoxys such as ruaniline and diglycidylamine; monoaldehydes such as formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde; dialdehydes such as glyoxal, malondialdehyde, succindialdehyde, glutardialdehyde, maleidialdehyde and phthaldialdehyde Amino-formaldehyde resins such as methylol urea, methylol melamine, alkylated methylol urea, alkylated methylol melamine, acetoguanamine, condensate of benzoguanamine and formaldehyde; zirconium acetate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, acid Zirconium compounds such as zirconium chloride; metal glyoxylate (metals include, for example, lithium, sodium, potassium Alkaline earth metals such as magnesium, calcium, transition metals such as titanium, zirconium, chromium, manganese, iron, cobalt, nickel, copper, zinc, aluminum, etc.), glyoxylic acid amine salts (amines) Examples thereof include glyoxylates such as ammonia, monomethylamine, dimethylamine, trimethylamine, etc .; amino acids or sulfur-containing amino acids having one or more basic groups and one or more acidic groups; dimethoxy Acetal compounds such as ethanal, diethoxyethanal, dialkoxyethanal; and divalent metals such as sodium, potassium, magnesium, calcium, aluminum, iron, nickel, and salts of trivalent metals and oxides thereof . These can be used alone or in combination of two or more. Among these, it is preferable to use an amino acid or sulfur-containing amino acid having one or more basic groups and one or more acidic groups. The basic group is preferably an amino group, and the acidic group is preferably a carboxyl group or a sulfo group. Examples of the amino acids include glycine, alanine, phenylalanine, valine, leucine, isoleucine, lysine, proline, serine, threonine, tryptophan, histidine, tyrosine, arginine, asparagine, aspartic acid, aspartame, glutamine, glutamic acid, and these amino acids. Examples include copolymers with (meth) acrylic acid. Examples of the sulfur-containing amino acid include methionine, cysteine, cystine, and taurine. Among these, it is particularly preferable to use a sulfur-containing amino acid having a sulfo group such as taurine. Moreover, as a crosslinking agent, coupling agents, such as a silane coupling agent and a titanium coupling agent, can be used.
前記架橋剤の配合量は、ポリビニルアルコール系樹脂の種類等に応じて適宜設計できるが、ポリビニルアルコール系樹脂１００重量部に対して、通常、０．１〜５０重量部程度、好ましくは０．２〜４０重量部である。かかる範囲において、良好な接着性が得られる。 The amount of the crosslinking agent can be appropriately designed according to the type of polyvinyl alcohol resin, etc., but is usually about 0.1 to 50 parts by weight, preferably 0.2 to 100 parts by weight of the polyvinyl alcohol resin. ~ 40 parts by weight. In such a range, good adhesiveness can be obtained.
耐久性を向上させるには、アセトアセチル基を含有するポリビニルアルコール系樹脂を用いる。この場合にも、架橋剤の配合量は前記と同様である。架橋剤の配合量が多くなりすぎると、液安定性が低下し、接着剤としての可使時間（ポットライフ）が短くなり、工業的な使用が困難になる。 In order to improve the durability, a polyvinyl alcohol resin containing an acetoacetyl group is used. Also in this case, the amount of the crosslinking agent is the same as described above. When the amount of the crosslinking agent is too large, the liquid stability is lowered, the pot life as an adhesive is shortened, and industrial use becomes difficult.
前記樹脂水溶液は、ｐＨ調整剤により、ｐＨが８．０〜１０．５に調整されたものを用いる。前記樹脂水溶液のｐＨが１０．５を超えると、接着剤中のアルカリが多くなり、加湿条件下で光学特性が低下する。一方、ｐＨが８．０未満では、接着剤中のアルカリが少なく、光学特性の向上効果が十分得られない。本発明では、ｐＨを前記範囲に調整した樹脂水溶液を偏光板用接着剤に用いることにより、高透過率及び高偏光度の光学特性を満足させ、かつ、加湿信頼性の良好な偏光板を得ることができる。加湿信頼性における、光学特性の低下の抑制の観点から、前記樹脂水溶液のｐＨは８〜１０であることが好ましく、さらには８〜９．５であることが好ましい。 As the resin aqueous solution, one having a pH adjusted to 8.0 to 10.5 with a pH adjusting agent is used. When the pH of the aqueous resin solution exceeds 10.5, the alkali in the adhesive increases, and the optical characteristics deteriorate under humid conditions. On the other hand, when the pH is less than 8.0, there are few alkalis in the adhesive, and the effect of improving optical properties cannot be obtained sufficiently. In the present invention, by using a resin aqueous solution whose pH is adjusted within the above range as an adhesive for polarizing plate, a polarizing plate satisfying optical characteristics of high transmittance and high degree of polarization and having good humidification reliability is obtained. be able to. From the viewpoint of suppressing deterioration of optical properties in humidification reliability, the pH of the aqueous resin solution is preferably 8 to 10, and more preferably 8 to 9.5.
前記ｐＨ調整剤としては、例えば、アレニウス塩基及び／又はブレンステッド塩基に関わるアルカリ剤を用いることができる。アレニウス塩基に関わるアルカリ剤としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、水酸化マグネシウム等の水酸化アルカリ；アンモニア水等が挙げられる。ブレンステッド塩基に関わるアルカリ剤としては、例えば、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムｎ‐ブトキシド、ナトリウムｔ‐ブトキシド、カリウムメトキシド、カリウムエトキシド、カリウムｎ‐ブトキシド、カリウムｔ‐ブトキシド、リチウムメトキシド、リチウムエトキシド、リチウムｎ‐ブトキシド、リチウムｔ‐ブトキシド等の炭素数１〜１０の金属アルコキシド；水素化ナトリウム、水素化カリウム、水素化リチウム、水素化カルシウム等の水素化アルカリ；ピリジン、トリエチルアミン、ＤＢＵ（１，８‐ジアザビシクロ[５．４．０]‐７‐ウンデセン）、ＤＢＮ（１，５‐ジアザビシクロ[４．３．０]ノナ‐５‐エン）等の有機塩基；他の別の金属塩、例えば、炭酸リチウム、炭酸カルシウム、炭酸ナトリウム、炭酸セシウム、炭酸バリウム、炭酸水素カルシウム、炭酸水素ナトリウム等の炭酸塩等が挙げられる。これらアルカリ剤は、１種を単独で、または２種以上を組み合わせて用いることができる。上記アルカリ剤のなかでも、ｐＨの調整が容易なことからアレニウス塩基に関わるアルカリ剤が好ましく、特に水酸化アルカリが好ましい。 As the pH adjuster, for example, an alkaline agent related to Arrhenius base and / or Bronsted base can be used. Examples of the alkaline agent related to Arrhenius base include alkali hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide; ammonia water. Examples of alkaline agents related to Bronsted base include sodium methoxide, sodium ethoxide, sodium n-butoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium n-butoxide, potassium t-butoxide, and lithium methoxy. Metal alkoxides having 1 to 10 carbon atoms such as lithium, ethoxide, lithium n-butoxide, lithium t-butoxide; alkali hydrides such as sodium hydride, potassium hydride, lithium hydride, calcium hydride; pyridine, triethylamine , Organic bases such as DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DBN (1,5-diazabicyclo [4.3.0] non-5-ene); Metal salts such as lithium carbonate, calcium carbonate, carbonate Examples thereof include carbonates such as sodium, cesium carbonate, barium carbonate, calcium hydrogen carbonate and sodium hydrogen carbonate. These alkali agents can be used alone or in combination of two or more. Among the alkali agents, an alkali agent relating to Arrhenius base is preferable because pH can be easily adjusted, and alkali hydroxide is particularly preferable.
アレニウス塩基及び／又はブレンステッド塩基に関わるアルカリ剤の配合量は、樹脂水溶液が、ｐＨが８．０〜１０．５になるように、アルカリ剤の種類に応じて配合量が適宜に決定される。 The blending amount of the alkaline agent related to the Arrhenius base and / or the Bronsted base is appropriately determined according to the type of the alkaline agent so that the resin aqueous solution has a pH of 8.0 to 10.5. .
また前記ｐＨ調整剤としては、水溶性珪酸塩を用いることができる。水溶性珪酸塩は、一般式Ｍ２Ｏ・ｎＳｉＯ２で表わされる化合物であり、Ｍは、アルカリ金属、有機塩基などである。アルカリ金属としては、例えばリチウム、ナトリウム、及びカリウムなどが挙げられ、有機塩基としては、例えば第３級アンモニウム、第４級アンモニウム、及びグアニジウムなどが挙げられる。ｎは２〜８であることが好ましい。 As the pH adjuster, a water-soluble silicate can be used. The water-soluble silicate is a compound represented by the general formula M 2 O · nSiO 2 , where M is an alkali metal, an organic base, or the like. Examples of the alkali metal include lithium, sodium, and potassium, and examples of the organic base include tertiary ammonium, quaternary ammonium, and guanidinium. n is preferably 2 to 8.
前記水溶性珪酸塩としては、珪酸リチウム、珪酸ナトリウム、及び珪酸カリウムからなる群より選択される少なくとも１種を用いることが好ましい。珪酸リチウムは、ＳｉＯ２／Ｌｉ２Ｏのモル比が２〜８であることが好ましい。前記モル比が２未満の場合には接着剤層のアルカリ性が高くなり、加湿環境下において偏光板の光透過率が低下する傾向にある。一方、前記モル比が８を超える場合には水溶性の珪酸塩にならない。珪酸ナトリウムは、ＳｉＯ２／Ｎａ２Ｏのモル比が２〜５であることが好ましく、より好ましくは２．５〜５である。珪酸カリウムは、ＳｉＯ２／Ｋ２Ｏのモル比が２〜５であることが好ましく、より好ましくは２．５〜５である。前記モル比が２未満の場合には接着剤層のアルカリ性が高くなり、加湿環境下において偏光板の光透過率が低下する傾向にある。一方、前記モル比が５を超える場合には水溶性の珪酸塩にならない。 As the water-soluble silicate, it is preferable to use at least one selected from the group consisting of lithium silicate, sodium silicate, and potassium silicate. Lithium silicate preferably has a SiO 2 / Li 2 O molar ratio of 2 to 8. If the molar ratio is less than 2, the alkalinity of the adhesive layer becomes high, and the light transmittance of the polarizing plate tends to decrease in a humidified environment. On the other hand, when the molar ratio exceeds 8, it does not become a water-soluble silicate. Sodium silicate preferably has a SiO 2 / Na 2 O molar ratio of 2 to 5, more preferably 2.5 to 5. The potassium silicate preferably has a SiO 2 / K 2 O molar ratio of 2 to 5, more preferably 2.5 to 5. If the molar ratio is less than 2, the alkalinity of the adhesive layer becomes high, and the light transmittance of the polarizing plate tends to decrease in a humidified environment. On the other hand, when the molar ratio exceeds 5, it does not become a water-soluble silicate.
前記水溶性珪酸塩の配合量は、樹脂水溶液が、ｐＨが８．０〜１０．５になるように、水溶性珪酸塩の種類に応じて配合量が適宜に決定される。前記水溶性珪酸塩の配合量は、ポリビニルアルコール系樹脂１００重量部に対して、１〜１００重量部であることが好ましく、より好ましくは１〜５０重量部であり、さらに好ましくは１〜３０重量部である。前記水溶性珪酸塩の配合量が１重量部未満の場合には、ｐＨを８．０以上にすることが難しく、また接着剤層の屈折率が高くなりすぎるため偏光子と接着剤層の間及び透明保護フィルムと接着剤層の間の各層間で光の界面反射が起こりやすくなり、偏光板の光透過率が低下する傾向にある。一方、１００重量部を超える場合には、ｐＨを１０．５以下にすることが難しく、また接着剤層の接着力が低下したり、接着剤層の屈折率が低くなりすぎるため偏光子と接着剤層の間及び透明保護フィルムと接着剤層の間の各層間で光の界面反射が起こりやすくなり、偏光板の光透過率が低下する傾向にある。 The amount of the water-soluble silicate is appropriately determined according to the type of the water-soluble silicate so that the resin aqueous solution has a pH of 8.0 to 10.5. The amount of the water-soluble silicate is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and further preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin. Part. When the blending amount of the water-soluble silicate is less than 1 part by weight, it is difficult to set the pH to 8.0 or more, and the refractive index of the adhesive layer becomes too high, so that between the polarizer and the adhesive layer. In addition, interfacial reflection of light is likely to occur between each layer between the transparent protective film and the adhesive layer, and the light transmittance of the polarizing plate tends to decrease. On the other hand, when it exceeds 100 parts by weight, it is difficult to make the pH 10.5 or less, and the adhesive strength of the adhesive layer is lowered, or the refractive index of the adhesive layer is too low, so that the polarizer is bonded. Interfacial reflection of light tends to occur between the agent layers and between the transparent protective film and the adhesive layer, and the light transmittance of the polarizing plate tends to decrease.
前記工程（１）で用いる、偏光板用接着剤は、ポリビニルアルコール系樹脂及びｐＨ調整剤を含有する樹脂水溶液であり、樹脂水溶液の固形分濃度はｐＨが８．０〜１０．５に制御されていれば、特に制限はない。前記樹脂水溶液の固形分濃度は、塗工性や放置安定性等を考慮すると０．１〜１５重量％であることが好ましく、より好ましくは０．５〜１０重量％である。 The polarizing plate adhesive used in the step (1) is an aqueous resin solution containing a polyvinyl alcohol resin and a pH adjuster, and the solid content concentration of the aqueous resin solution is controlled to a pH of 8.0 to 10.5. If there is, there is no restriction in particular. The solid content concentration of the aqueous resin solution is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight in consideration of coating properties and storage stability.
樹脂水溶液の粘度は特に制限されないが、通常１〜５０ｍＰａ・ｓの範囲のものが用いられる。 The viscosity of the aqueous resin solution is not particularly limited, but a resin in the range of 1 to 50 mPa · s is usually used.
偏光板用接着剤である前記樹脂水溶液の調製法は特に制限されない。通常は、ポリビニルアルコール系樹脂及び架橋剤を混合し、適宜に濃度を調製したものに、ｐＨ調整剤を配合してｐＨが８．０〜１０．５の樹脂水溶液を調製する。また、ポリビニルアルコール系樹脂として、アセトアセチル基を含有するポリビニルアルコール系樹脂を用いたり、架橋剤の配合量が多い場合には、樹脂水溶液の安定性を考慮して、ポリビニルアルコール系樹脂とｐＨ調整剤を混合した後に、得られる樹脂水溶液の使用時期等を考慮しながら架橋剤を混合してもよい。なお、偏光板用接着剤である樹脂水溶液の濃度は、樹脂水溶液を調製した後に、ｐＨが８．０〜１０．５になるように適宜に調整することもできる。 The method for preparing the aqueous resin solution that is an adhesive for polarizing plates is not particularly limited. Usually, a polyvinyl alcohol-based resin and a crosslinking agent are mixed, and a pH adjuster is blended into a mixture whose concentration is appropriately adjusted to prepare a resin aqueous solution having a pH of 8.0 to 10.5. In addition, when polyvinyl alcohol resin containing acetoacetyl groups is used as the polyvinyl alcohol resin, or when the amount of the crosslinking agent is large, pH adjustment with polyvinyl alcohol resin is performed in consideration of the stability of the resin aqueous solution. After mixing the agent, the crosslinking agent may be mixed while taking into consideration the use timing of the resulting aqueous resin solution. In addition, the concentration of the resin aqueous solution that is an adhesive for the polarizing plate can be appropriately adjusted so that the pH becomes 8.0 to 10.5 after the resin aqueous solution is prepared.
なお、偏光板用接着剤には、各種粘着付与剤、紫外線吸収剤、酸化防止剤、耐熱安定剤、耐加水分解安定剤などの安定剤等を配合することもできる。 The polarizing plate adhesive may contain various tackifiers, ultraviolet absorbers, antioxidants, heat stabilizers, hydrolysis stabilizers, and other stabilizers.
本発明の偏光板の製造方法は、偏光子及び／又は透明保護フィルムに偏光板用接着剤を塗布する工程（１）、前記接着剤により偏光子と透明保護フィルムとを貼り合わせる工程（２）、並びに前記接着剤を乾燥して接着剤層を形成する乾燥工程（３）を含む。かかる製造方法により、偏光子の少なくとも一方の面に接着剤層を介して透明保護フィルムが設けられている偏光板が得られる。 The manufacturing method of the polarizing plate of this invention is the process (1) of apply | coating the adhesive for polarizing plates to a polarizer and / or a transparent protective film, and the process of bonding a polarizer and a transparent protective film with the said adhesive (2). And a drying step (3) of drying the adhesive to form an adhesive layer. By this manufacturing method, a polarizing plate in which a transparent protective film is provided on at least one surface of the polarizer via an adhesive layer is obtained.
前記工程（１）では、偏光子及び／又は透明保護フィルムに前記樹脂水溶液に係る偏光板用接着剤を塗布して接着剤層を形成する。 In the step (1), an adhesive layer is formed by applying a polarizing plate adhesive relating to the resin aqueous solution to a polarizer and / or a transparent protective film.
前記接着剤の塗布は、透明保護フィルム、偏光子のいずれに行ってもよく、両者に行ってもよい。前記接着剤の塗布は、乾燥工程（３）後の接着剤層の厚みが１０〜３００ｎｍ程度になるように行なうのが好ましい。接着剤層の厚みは、均一な面内厚みを得ることと、十分な接着力を得る観点から１０〜２００ｎｍであることがより好ましく、特に好ましくは２０〜１５０ｎｍである。接着剤層の厚みが１０ｎｍ未満の場合には接着力が十分でなく、３００ｎｍを超える場合には光学信頼性及び耐湿接着力が低下する傾向にある。 Application | coating of the said adhesive agent may be performed to any of a transparent protective film and a polarizer, and may be performed to both. The adhesive is preferably applied so that the thickness of the adhesive layer after the drying step (3) is about 10 to 300 nm. The thickness of the adhesive layer is more preferably from 10 to 200 nm, particularly preferably from 20 to 150 nm, from the viewpoint of obtaining a uniform in-plane thickness and obtaining sufficient adhesive strength. When the thickness of the adhesive layer is less than 10 nm, the adhesive force is not sufficient, and when it exceeds 300 nm, the optical reliability and the moisture-resistant adhesive force tend to decrease.
接着剤層の厚みを調整する方法としては、特に制限されるものではないないが、例えば、接着剤溶液の固形分濃度や接着剤の塗布装置を調整する方法が挙げられる。このような接着剤層厚みの測定方法としては、特に制限されるものではないが、ＳＥＭ（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｙ）や、ＴＥＭ（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｙ）による断面観察測定が好ましく用いられる。接着剤の塗布操作は特に制限されず、ロール法、噴霧法、浸漬法等の各種手段を採用できる。 The method of adjusting the thickness of the adhesive layer is not particularly limited, and examples thereof include a method of adjusting the solid content concentration of the adhesive solution and an adhesive application device. The method for measuring the thickness of the adhesive layer is not particularly limited, but cross-sectional observation measurement using SEM (Scanning Electron Microscopy) or TEM (Transmission Electron Microscopy) is preferably used. The application operation of the adhesive is not particularly limited, and various means such as a roll method, a spray method, and an immersion method can be employed.
また、接着剤層の屈折率は１．４７〜１．５４であることが好ましい。接着剤層の屈折率が１．４７〜１．５４の範囲外の場合には、接着剤層の屈折率が低く又は高くなりすぎるため偏光子と接着剤層の間及び透明保護フィルムと接着剤層の間の各層間で光の界面反射が起こりやすくなり、偏光板の光透過率が低下する傾向にある。なお、ｐＨ調整剤として水溶性珪酸塩を含有する偏光板用接着剤からなる接着剤層は、偏光子との屈折率差及び透明保護フィルムとの屈折率差が小さいため、偏光子と接着剤層の間及び透明保護フィルムと接着剤層の間の各層間で光の界面反射が起こりにくく、偏光板の光透過率の低下を防止することができる。 Further, the refractive index of the adhesive layer is preferably 1.47 to 1.54. When the refractive index of the adhesive layer is outside the range of 1.47 to 1.54, the refractive index of the adhesive layer is too low or too high, and therefore between the polarizer and the adhesive layer and between the transparent protective film and the adhesive. Interfacial reflection of light tends to occur between the layers between the layers, and the light transmittance of the polarizing plate tends to decrease. In addition, since the adhesive layer made of the adhesive for polarizing plates containing a water-soluble silicate as a pH adjuster has a small difference in refractive index with the polarizer and a difference in refractive index with the transparent protective film, the polarizer and the adhesive. Interfacial reflection of light hardly occurs between the layers and between each layer between the transparent protective film and the adhesive layer, and a decrease in light transmittance of the polarizing plate can be prevented.
前記工程（１）により、偏光子及び／又は透明保護フィルムに接着剤を塗布した後は、前記接着剤により偏光子と透明保護フィルムを貼り合わせる工程（２）を施す。貼り合わせ工程（２）は、特に限定されないが、例えば、ロールラミネーター等により貼り合わせを行うことができる。 After apply | coating an adhesive agent to a polarizer and / or a transparent protective film by the said process (1), the process (2) which bonds a polarizer and a transparent protective film with the said adhesive agent is given. Although the bonding step (2) is not particularly limited, for example, the bonding can be performed using a roll laminator or the like.
次いで、貼り合わせ工程（２）の後には、前記接着剤を乾燥して接着剤層を形成する乾燥工程（３）を施す。乾燥工程（３）によって、塗布乾燥層からなる接着剤層が形成され、偏光子の少なくとも一方の面に接着剤層を介して透明保護フィルムが設けられている偏光板が得られる。 Next, after the bonding step (2), a drying step (3) is performed in which the adhesive is dried to form an adhesive layer. By the drying step (3), an adhesive layer composed of a dried coating layer is formed, and a polarizing plate is obtained in which a transparent protective film is provided on at least one surface of the polarizer via the adhesive layer.
前記乾燥工程（３）の乾燥条件は、乾燥温度２５〜５０℃で、乾燥時間８分間以上である。乾燥温度は３０〜５０℃であることが好ましく、さらには３５〜５０℃であることが好ましい。また乾燥時間は１０分間以上であることが好ましい。一方、乾燥時間は光学特性の低下の観点から２５分間以下とすることが好ましい。乾燥温度が２５℃未満では、十分な高透過率及び高偏光度を有する偏光板が得られない。一方、乾燥温度が８０℃を超える場合にも、十分な高透過率及び高偏光度を有する偏光板が得られない。また、乾燥時間が８分間未満では、十分な高透過率及び高偏光度を有する偏光板が得られない。 The drying conditions in the drying step (3) are a drying temperature of 25 to 50 ° C. and a drying time of 8 minutes or more. The drying temperature is preferably 30 to 50 ° C, more preferably 35 to 50 ° C. The drying time is preferably 10 minutes or longer. On the other hand, the drying time is preferably 25 minutes or less from the viewpoint of deterioration of optical properties. When the drying temperature is less than 25 ° C., a polarizing plate having a sufficiently high transmittance and a high degree of polarization cannot be obtained. On the other hand, even when the drying temperature exceeds 80 ° C., a polarizing plate having a sufficiently high transmittance and a high degree of polarization cannot be obtained. Moreover, if the drying time is less than 8 minutes, a polarizing plate having a sufficiently high transmittance and a high degree of polarization cannot be obtained.
偏光子は、特に制限されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料等の二色性材料を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらのなかでもポリビニルアルコール系フィルムとヨウ素などの二色性物質からなる偏光子が好適である。これら偏光子の厚さは特に制限されないが、一般的に、５〜８０μｍ程度である。 The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include hydrophilic polymers such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and two colors such as iodine and dichroic dye. Examples include polyene-based oriented films such as those obtained by adsorbing a functional material and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic material such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.
ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、例えば、ポリビニルアルコールをヨウ素の水溶液に浸漬することによって染色し、元長の３〜７倍に延伸することで作成することができる。必要に応じてホウ酸やヨウ化カリウムなどの水溶液に浸漬することもできる。さらに必要に応じて染色の前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール系フィルム表面の汚れやブロッキング防止剤を洗浄することができるほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラなどの不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸してもよし、また延伸してからヨウ素で染色してもよい。ホウ酸やヨウ化カリウムなどの水溶液中や水浴中でも延伸することができる。 A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be prepared, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution of boric acid or potassium iodide. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched in an aqueous solution of boric acid or potassium iodide or in a water bath.
前記偏光子の片面又は両面に設けられる透明保護フィルムを形成する材料としては、透明性、機械的強度、熱安定性、水分遮断性、等方性などに優れるものが好ましい。例えば、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル系ポリマー、ジアセチルセルロースやトリアセチルセルロース等のセルロース系ポリマー、ポリメチルメタクリレート等のアクリル系ポリマー、ポリスチレンやアクリロニトリル・スチレン共重合体（ＡＳ樹脂）等のスチレン系ポリマー、ポリカーボネート系ポリマーなどが挙げられる。また、ポリエチレン、ポリプロピレン、シクロ系ないしはノルボルネン構造を有するポリオレフィン、エチレン・プロピレン共重合体の如きポリオレフィン系ポリマー、塩化ビニル系ポリマー、ナイロンや芳香族ポリアミド等のアミド系ポリマー、イミド系ポリマー、スルホン系ポリマー、ポリエーテルスルホン系ポリマー、ポリエーテルエーテルケトン系ポリマー、ポリフェニレンスルフィド系ポリマー、ビニルアルコール系ポリマー、塩化ビニリデン系ポリマー、ビニルブチラール系ポリマー、アリレート系ポリマー、ポリオキシメチレン系ポリマー、エポキシ系ポリマー、又は前記ポリマーのブレンド物なども前記透明保護フィルムを形成するポリマーの例として挙げられる。なお、偏光子には、通常、透明保護フィルムが接着剤層により貼り合わされるが、透明保護フィルムとして、（メタ）アクリル系、ウレタン系、アクリルウレタン系、エポキシ系、シリコーン系等の熱硬化性樹脂又は紫外線硬化型樹脂を用いることができる。透明保護フィルム中には任意の適切な添加剤が１種類以上含まれていてもよい。添加剤としては、例えば、紫外線吸収剤、酸化防止剤、滑剤、可塑剤、離型剤、着色防止剤、難燃剤、核剤、帯電防止剤、顔料、着色剤などが挙げられる。透明保護フィルム中の上記熱可塑性樹脂の含有量は、好ましくは５０〜１００重量％、より好ましくは５０〜９９重量％、さらに好ましくは６０〜９８重量％、特に好ましくは７０〜９７重量％である。透明保護フィルム中の上記熱可塑性樹脂の含有量が５０重量％以下の場合、熱可塑性樹脂が本来有する高透明性等が十分に発現できないおそれがある。 As a material for forming the transparent protective film provided on one side or both sides of the polarizer, a material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like is preferable. For example, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, styrene such as polystyrene and acrylonitrile / styrene copolymer (AS resin) And polymers based on polycarbonate and polycarbonate. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or the above Examples of the polymer that forms the transparent protective film include polymer blends. In addition, a transparent protective film is usually bonded to the polarizer by an adhesive layer. As the transparent protective film, thermosetting such as (meth) acrylic, urethane-based, acrylurethane-based, epoxy-based, silicone-based, etc. Resin or ultraviolet curable resin can be used. One or more kinds of arbitrary appropriate additives may be contained in the transparent protective film. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97% by weight. . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.
透明保護フィルムの厚さは、適宜に決定しうるが、一般には強度や取扱性等の作業性、薄層性などの点より１〜５００μｍ程度である。特に１〜３００μｍが好ましく、５〜２００μｍがより好ましい。 Although the thickness of a transparent protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin layer property. 1-300 micrometers is especially preferable, and 5-200 micrometers is more preferable.
なお、偏光子の両側に透明保護フィルムを設ける場合、その表裏で同じポリマー材料からなる保護フィルムを用いてもよく、異なるポリマー材料等からなる透明保護フィルムを用いてもよい。 In addition, when providing a transparent protective film on both sides of a polarizer, the protective film which consists of the same polymer material may be used by the front and back, and the transparent protective film which consists of a different polymer material etc. may be used.
透明保護フィルムの偏光子と接着する面には、易接着処理を施すことができる。易接着処理としては、プラズマ処理、コロナ処理等のドライ処理、アルカリ処理（ケン化処理）等の化学処理、易接着剤層を形成するコーティング処理等が挙げられる。これらのなかでも、易接着剤層を形成するコーティング処理やアルカリ処理が好適である。易接着剤層の形成には、ポリオール樹脂、ポリカルボン酸樹脂、ポリエステル樹脂等の各種の易接着材料を使用することができる。なお、易接着剤層の厚みは、通常、０．００１〜１０μｍ程度、さらには０．００１〜５μｍ程度、特に０．００１〜１μｍ程度とするのが好ましい。 The surface of the transparent protective film that adheres to the polarizer can be subjected to an easy adhesion treatment. Examples of the easy adhesion treatment include dry treatment such as plasma treatment and corona treatment, chemical treatment such as alkali treatment (saponification treatment), and coating treatment for forming an easy adhesive layer. Among these, a coating treatment or an alkali treatment for forming an easy-adhesive layer is preferable. For the formation of the easy-adhesive layer, various easy-adhesive materials such as polyol resin, polycarboxylic acid resin, and polyester resin can be used. The thickness of the easy-adhesive layer is usually about 0.001 to 10 μm, more preferably about 0.001 to 5 μm, and particularly preferably about 0.001 to 1 μm.
前記透明保護フィルムの偏光子を接着させない面には、ハードコート層や反射防止処理、スティッキング防止や、拡散ないしアンチグレアを目的とした処理を施したものであってもよい。 The surface of the transparent protective film to which the polarizer is not adhered may be subjected to a hard coat layer, an antireflection treatment, an antisticking treatment, or a treatment for diffusion or antiglare.
なお、前記反射防止層、スティッキング防止層、拡散層やアンチグレア層等は、透明保護フィルムそのものに設けることができるほか、別途光学層として透明保護フィルムとは別体のものとして設けることもできる。 The antireflection layer, antisticking layer, diffusion layer, antiglare layer, and the like can be provided on the transparent protective film itself, or can be provided separately from the transparent protective film as an optical layer.
本発明の偏光板は、実用に際して他の光学層と積層した光学フィルムとして用いることができる。その光学層については特に限定はないが、例えば反射板や半透過板、位相差板（１／２や１／４等の波長板を含む）、視角補償フィルムなどの液晶表示装置等の形成に用いられることのある光学層を１層又は２層以上用いることができる。特に、本発明の偏光板に更に反射板又は半透過反射板が積層されてなる反射型偏光板又は半透過型偏光板、偏光板に更に位相差板が積層されてなる楕円偏光板又は円偏光板、偏光板に更に視角補償フィルムが積層されてなる広視野角偏光板、あるいは偏光板に更に輝度向上フィルムが積層されてなる偏光板が好ましい。 The polarizing plate of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited. For example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including wavelength plates such as 1/2 and 1/4), and a viewing angle compensation film. One or two or more optical layers that may be used can be used. In particular, a reflective polarizing plate or a semi-transmissive polarizing plate in which a polarizing plate or a semi-transmissive reflecting plate is further laminated on the polarizing plate of the present invention, an elliptical polarizing plate or a circularly polarizing plate in which a retardation plate is further laminated on the polarizing plate. A wide viewing angle polarizing plate obtained by further laminating a viewing angle compensation film on a plate or a polarizing plate, or a polarizing plate obtained by further laminating a brightness enhancement film on the polarizing plate is preferable.
本発明の偏光板又は光学フィルムは液晶表示装置等の各種装置の形成などに好ましく用いることができる。液晶表示装置の形成は、従来に準じて行いうる。すなわち液晶表示装置は一般に、液晶セルと偏光板又は光学フィルム、及び必要に応じての照明システム等の構成部品を適宜に組立てて駆動回路を組込むことなどにより形成されるが、本発明においては本発明による偏光板又は光学フィルムを用いる点を除いて特に限定はなく、従来に準じうる。液晶セルについても、例えばＴＮ型やＳＴＮ型、π型などの任意なタイプのものを用いうる。 The polarizing plate or the optical film of the present invention can be preferably used for forming various devices such as a liquid crystal display device. The liquid crystal display device can be formed according to the conventional method. That is, a liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing plate or an optical film, and an illumination system as necessary, and incorporating a drive circuit. There is no limitation in particular except the point which uses the polarizing plate or optical film by invention, According to the past. As the liquid crystal cell, any type such as a TN type, an STN type, or a π type can be used.
液晶セルの片側又は両側に偏光板又は光学フィルムを配置した液晶表示装置や、照明システムにバックライトあるいは反射板を用いたものなどの適宜な液晶表示装置を形成することができる。その場合、本発明による偏光板又は光学フィルムは液晶セルの片側又は両側に設置することができる。両側に偏光板又は光学フィルムを設ける場合、それらは同じものであってもよいし、異なるものであってもよい。さらに、液晶表示装置の形成に際しては、例えば拡散板、アンチグレア層、反射防止膜、保護板、プリズムアレイ、レンズアレイシート、光拡散板、バックライトなどの適宜な部品を適宜な位置に１層又は２層以上配置することができる。 An appropriate liquid crystal display device such as a liquid crystal display device in which a polarizing plate or an optical film is disposed on one side or both sides of a liquid crystal cell, or a backlight or a reflector used in an illumination system can be formed. In that case, the polarizing plate or optical film by this invention can be installed in the one side or both sides of a liquid crystal cell. When providing a polarizing plate or an optical film on both sides, they may be the same or different. Further, when forming a liquid crystal display device, for example, a single layer or a suitable part such as a diffusing plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusing plate, a backlight, etc. Two or more layers can be arranged.
以下、本発明の構成と効果を具体的に示す実施例等について説明する。なお、各例中、部及び％は特記ない限り重量基準である。 Examples and the like specifically showing the configuration and effects of the present invention will be described below. In each example, parts and% are based on weight unless otherwise specified.
＜ｐＨの測定方法＞
調整した接着剤水溶液のｐＨを、Ｅｕｔｅｃｈ Ｉｎｓｔｒｕｍｅｎｔｓ社製のｐＨメーター（ＥＣ−ＰＨ５）を用いて測定した。
<Measurement method of pH>
The pH of the adjusted adhesive aqueous solution was measured using a pH meter (EC-PH5) manufactured by Eutech Instruments.
＜粘度の測定＞
調整した接着剤水溶液の粘度を、レオメーターＲＳ１（Ｈａａｋｅ社製）、共軸円筒として型式２２２−１２６７及び２２２−１５４９を用いて、２３℃の液温及び気温にて測定した。
<Measurement of viscosity>
The viscosity of the adjusted aqueous adhesive solution was measured at a liquid temperature and an air temperature of 23 ° C. using a rheometer RS1 (manufactured by Haake) and models 222-1267 and 222-1549 as coaxial cylinders.
実施例１
（偏光子）
平均重合度２４００、ケン化度９９．９モル％の厚み７５μｍのポリビニルアルコールフィルムを、３０℃の温水中に６０秒間浸漬し膨潤させた。次いで、ヨウ素／ヨウ化カリウム（重量比＝０．５／８）の濃度０．３％の水溶液に浸漬し、３．５倍まで延伸させながらフィルムを染色した。その後、６５℃のホウ酸エステル水溶液中で、トータルの延伸倍率が６倍となるように延伸を行った。延伸後に、４０℃のオーブンにて３分間乾燥を行い、偏光子を得た。偏光子の単体透過率（Ｔｓ）は、４２．５０％であった。
Example 1
(Polarizer)
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was immersed in warm water at 30 ° C. for 60 seconds to swell. Next, the film was dyed while being immersed in an aqueous solution of 0.3% concentration of iodine / potassium iodide (weight ratio = 0.5 / 8) and stretched to 3.5 times. Then, it extended | stretched so that the total draw ratio might be 6 times in 65 degreeC borate ester aqueous solution. After extending | stretching, it dried for 3 minutes in 40 degreeC oven, and obtained the polarizer. The single transmittance (Ts) of the polarizer was 42.50%.
（透明保護フィルム）
厚さ８０μｍのトリアセチルセルロース（ＴＡＣ）フィルムを用いた。
(Transparent protective film)
A 80 μm thick triacetyl cellulose (TAC) film was used.
（接着剤水溶液の調製）
アセトアセチル（ＡＡ）基を含有するポリビニルアルコール（ＰＶＡ）系樹脂（平均重合度：１２００，ケン化度：９８．５モル％，アセトアセチル化度：５モル％）１００部に対し、架橋剤としてタウリンを３０部、ｐＨ調整剤として珪酸ナトリウム珪酸ソーダ４号（ＳｉＯ２／Ｎａ２Ｏのモル比４）１０部を、３０℃の温度条件下で純水に溶解し、固形分濃度４％に調整して、ｐＨ８．５に調整した樹脂水溶液からなる接着剤水溶液を得た。当該接着剤水溶液の粘度は９．０ｍＰａ・ｓであった。
(Preparation of adhesive aqueous solution)
As a crosslinking agent for 100 parts of polyvinyl alcohol (PVA) -based resin (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) containing acetoacetyl (AA) groups 30 parts of taurine and 10 parts of sodium silicate sodium silicate No. 4 (SiO 2 / Na 2 O molar ratio 4) as a pH adjuster were dissolved in pure water under a temperature condition of 30 ° C. to a solid content concentration of 4%. The adhesive aqueous solution which consists of the resin aqueous solution adjusted and adjusted to pH8.5 was obtained. The viscosity of the aqueous adhesive solution was 9.0 mPa · s.
（偏光板の作成）
上記透明保護フィルムの片面に、上記接着剤水溶液を乾燥後の接着剤層の厚みが８０ｎｍとなるように塗布した。次いで、２３℃の温度条件下で、上記偏光子の両面に接着剤付きの透明保護フィルムをロール機で貼り合せた。その後、６０℃で７分間の乾燥工程を施して偏光板を作成した。
(Creation of polarizing plate)
The adhesive aqueous solution was applied to one side of the transparent protective film so that the thickness of the adhesive layer after drying was 80 nm. Next, a transparent protective film with an adhesive was bonded to both sides of the polarizer under a temperature condition of 23 ° C. by a roll machine. Then, the drying process for 7 minutes was performed at 60 degreeC, and the polarizing plate was created.
実施例２〜５及び比較例１〜７
実施例１において、珪酸ナトリウムの添加量を調整することによって、表１に示すように、調製した接着剤水溶液のｐＨを制御したこと以外は実施例１と同様の方法で接着剤水溶液を調製した。また、実施例１において、表１に示すように、乾燥工程における乾燥条件（乾燥温度、乾燥時間）を変えたこと以外は、実施例１と同様にして、偏光板を作成した。
Examples 2-5 and Comparative Examples 1-7
In Example 1, an aqueous adhesive solution was prepared in the same manner as in Example 1 except that the pH of the prepared aqueous adhesive solution was controlled as shown in Table 1 by adjusting the amount of sodium silicate added. . In Example 1, as shown in Table 1, a polarizing plate was produced in the same manner as in Example 1 except that the drying conditions (drying temperature and drying time) in the drying step were changed.
上記実施例および比較例で得られた、偏光板について以下の評価を行った。評価結果を表１に示す。 The following evaluation was performed about the polarizing plate obtained by the said Example and comparative example. The evaluation results are shown in Table 1.
＜光学特性の測定＞
偏光板の光学特性（単体透過率（Ｔｓ）、偏光度）は、３８０〜７８０ｎｍの波長光における分光透過率を積分球付き分光光度計（日本分光株式会社製のＶ７１００）を用いて測定した。
なお、偏光度は、２枚の同じ偏光板を両者の透過軸が平行となるように重ね合わせた場合の透過率（平行透過率：Ｔｐ）および、両者の透過軸が直交するように重ね合わせた場合の透過率（直交透過率：Ｔｃ）を以下の式に適用することにより求められるものである。
偏光度（％）＝｛（Ｔｐ−Ｔｃ）／（Ｔｐ＋Ｔｃ）｝１／２×１００
各透過率は、グランテラープリズム偏光子を通して得られた完全偏光を１００％として測定し、測定された分光透過率よりＣＩＥ１９３１ Ｙｘｙ表色系に従い、２度視野（Ｃ光源）により視感度補整したＹ値で示したものである。
<Measurement of optical properties>
The optical properties (single transmittance (Ts), polarization degree) of the polarizing plate were measured by using a spectrophotometer with an integrating sphere (V7100 manufactured by JASCO Corporation) for spectral transmittance at a wavelength of 380 to 780 nm.
Note that the degree of polarization is such that two identical polarizing plates are superposed such that both transmission axes are parallel to each other so that both transmission axes are parallel (parallel transmittance: Tp), and the two transmission axes are orthogonal to each other. In this case, the transmittance (orthogonal transmittance: Tc) is determined by applying the transmittance to the following equation.
Polarization degree (%) = {(Tp−Tc) / (Tp + Tc)} 1/2 × 100
Each transmittance is measured with the complete polarization obtained through the Granteller prism polarizer as 100%, and the measured spectral transmittance is used to adjust the visibility with a 2 degree visual field (C light source) according to the CIE1931 Yxy color system. It is indicated by value.
＜加温信頼性＞
偏光板を６０℃、９５％Ｒ.Ｈ．の条件下に５００時間放置した。その放置前と放置後の単体透過率（Ｔｓ）の変化量を下記式により求めた。
単体透過率の変化量（％）＝｛（放置後の単体透過率）−（放置前の単体透過率）｝／（放置前の単体透過率）×１００
なお、単体透過率は、分光光度計（村上色彩技術研究所製，ＤＯＴ−３）を用いて、ＪＩＳ Ｚ ８７０１の２度視野（Ｃ光源）により視感度補正を行ったＹ値である。
<Heating reliability>
The polarizing plate was heated at 60 ° C. and 95% RH. For 500 hours. The amount of change in single transmittance (Ts) before and after the standing was determined by the following formula.
Change amount of single transmittance (%) = {(single transmittance after leaving) − (single transmittance before leaving)} / (single transmittance before leaving) × 100
The single transmittance is a Y value obtained by correcting the visibility using a spectrophotometer (DOT-3, manufactured by Murakami Color Research Laboratory Co., Ltd.) with a two-degree field (C light source) of JIS Z 8701.
表１から、実施例では、偏光度が９９.９９％の偏光板が得られており、かつ、加湿信頼性を満足している。一方、比較例１〜５では、接着剤水溶液が、本発明のｐＨを満足していても、乾燥条件を満足しないため、偏光度が９９.９９％の偏光板が得られていない。また、比較例６では接着剤水溶液のｐＨが強アルカリであるため加湿信頼性を満足できず、比較例７では接着剤水溶液のｐＨが酸性側にあるため偏光度が９９.９９％の偏光板が得られていない。 From Table 1, in the Examples, a polarizing plate having a polarization degree of 99.99% is obtained, and the humidification reliability is satisfied. On the other hand, in Comparative Examples 1-5, since the adhesive aqueous solution does not satisfy the drying conditions even when the pH of the present invention is satisfied, a polarizing plate having a polarization degree of 99.99% is not obtained. In Comparative Example 6, the pH of the aqueous adhesive solution is strong alkali, so that the reliability of humidification cannot be satisfied. In Comparative Example 7, the pH of the aqueous adhesive solution is on the acidic side, so that the polarization degree is 99.99%. Is not obtained.
Claims (10)
前記偏光板用接着剤は、ポリビニルアルコール系樹脂及びｐＨ調整剤を含有し、かつ、ｐＨが８．０〜１０．５に調整された樹脂水溶液であり、
前記乾燥工程（３）の乾燥条件が、乾燥温度２５〜５０℃で、乾燥時間８分間以上であることを特徴とする偏光板の製造方法。 A step of applying a polarizing plate adhesive to the polarizer and / or transparent protective film (1), a step of bonding the polarizer and the transparent protective film with the adhesive (2), and drying and bonding the adhesive A method for producing a polarizing plate comprising a drying step (3) for forming an agent layer, wherein a transparent protective film is provided on at least one surface of a polarizer via an adhesive layer,
The polarizing plate adhesive is a resin aqueous solution containing a polyvinyl alcohol-based resin and a pH adjuster and having a pH adjusted to 8.0 to 10.5.
The drying condition of the said drying process (3) is the drying temperature of 25-50 degreeC, and the drying time is 8 minutes or more, The manufacturing method of the polarizing plate characterized by the above-mentioned.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |