JP7405683B2 - Polarizing film, laminated polarizing film, image display panel, and image display device - Google Patents
Polarizing film, laminated polarizing film, image display panel, and image display device Download PDFInfo
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- JP7405683B2 JP7405683B2 JP2020077226A JP2020077226A JP7405683B2 JP 7405683 B2 JP7405683 B2 JP 7405683B2 JP 2020077226 A JP2020077226 A JP 2020077226A JP 2020077226 A JP2020077226 A JP 2020077226A JP 7405683 B2 JP7405683 B2 JP 7405683B2
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- polarizing film
- image display
- film
- adhesive layer
- layer
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
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- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
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Description
本発明は、偏光フィルム、積層偏光フィルム、画像表示パネル、および画像表示装置に関する。 The present invention relates to a polarizing film, a laminated polarizing film, an image display panel, and an image display device.
従来、液晶表示装置や有機EL表示装置等の各種画像表示装置に用いる偏光膜としては、高透過率と高偏光度を兼ね備えていることから、染色処理された(ヨウ素や二色性染料等の二色性物質を含有する)ポリビニルアルコール系フィルムが用いられている。当該偏光膜は、ポリビニルアルコール系フィルムに、浴中にて、例えば、膨潤、染色、架橋、延伸等の各処理を施した後に、洗浄処理を施してから、乾燥することにより製造される。また前記偏光膜は、通常、その片面または両面にトリアセチルセルロース等の保護フィルムが接着剤を用いて貼合された偏光フィルム(偏光板)として用いられている。 Conventionally, polarizing films used in various image display devices such as liquid crystal display devices and organic EL display devices have been dyed (using iodine, dichroic dyes, etc.) because they have both high transmittance and high degree of polarization. A polyvinyl alcohol film (containing a dichroic substance) is used. The polarizing film is manufactured by subjecting a polyvinyl alcohol film to various treatments such as swelling, dyeing, crosslinking, and stretching in a bath, followed by washing and drying. Further, the polarizing film is usually used as a polarizing film (polarizing plate) in which a protective film such as triacetyl cellulose is bonded to one or both sides of the polarizing film using an adhesive.
前記偏光フィルムは、必要に応じ、他の光学層を積層して積層偏光フィルム(光学積層体)として用いられ、前記偏光フィルムあるいは前記積層偏光フィルム(光学積層体)は、液晶セルや有機EL素子等の画像表示セルと、視認側における前面透明板(ウインドウ層)やタッチパネル等の前面透明部材との間に粘着剤層や接着剤層を介して貼合されて、上記の各種画像表示装置として用いられる。 The polarizing film is used as a laminated polarizing film (optical laminate) by laminating other optical layers as necessary, and the polarizing film or the laminated polarizing film (optical laminate) is used as a liquid crystal cell or an organic EL element. etc., and a front transparent member such as a front transparent plate (window layer) or a touch panel on the viewing side through an adhesive layer or an adhesive layer, and can be used as the various image display devices mentioned above. used.
近年、このような各種画像表示装置は、携帯電話やタブレット端末等のモバイル機器に加えて、カーナビゲーション装置やバックモニター等の車載用の画像表示装置としても使用される等、その用途は広がっている。これに伴い、前記偏光フィルムや前記積層偏光フィルムには、従来要求されてきたよりも、より過酷な環境下(例えば、高温環境下)における高い耐久性が求められており、そのような耐久性を確保することを目的とした偏光フィルムが提案されている(特許文献1)。 In recent years, the applications of these types of image display devices have been expanding, such as being used not only for mobile devices such as mobile phones and tablet terminals, but also for in-vehicle image display devices such as car navigation devices and rear view monitors. There is. Along with this, the polarizing film and the laminated polarizing film are required to have higher durability under harsher environments (e.g., high temperature environments) than was previously required. A polarizing film for the purpose of ensuring this has been proposed (Patent Document 1).
また、アゾ系化合物等の二色性染料を用いる染料系偏光膜は、一般に、ヨウ素系偏光膜(ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成される偏光膜)と比較して、高温且つ高湿条件下における耐光性が優れていることが知られており(特許文献2)、当該染料系偏光膜を有する偏光板の耐光性試験での色抜けを改善させるために、当該偏光板に使用する接着剤にヒンダードアミン系化合物を含有させることが開示されている(特許文献3)。 In addition, dye-based polarizing films that use dichroic dyes such as azo compounds generally require higher temperatures and It is known that the light resistance under high humidity conditions is excellent (Patent Document 2). It has been disclosed that the adhesive used contains a hindered amine compound (Patent Document 3).
一方、上記のように、染色系偏光膜よりも高温且つ高湿条件下における耐光性に劣ると言われるヨウ素系偏光膜を用いた偏光フィルムや積層偏光フィルムは、高温環境下に曝された場合に、偏光膜に着色が生じ、その単体透過率が低下する問題があった。とくに、上記の偏光フィルムや積層偏光フィルムを、画像表示セルと前面透明部材との間に粘着剤層または接着剤層を介して貼合することにより構成される画像表示装置は、偏光膜の着色が著しく、単体透過率の低下が顕著になる問題があった。 On the other hand, as mentioned above, polarizing films and laminated polarizing films using iodine-based polarizing films, which are said to have inferior light resistance under high-temperature and high-humidity conditions than dyed-based polarizing films, are Another problem is that the polarizing film becomes colored and its single transmittance decreases. In particular, an image display device constructed by laminating the above-mentioned polarizing film or laminated polarizing film between an image display cell and a front transparent member via an adhesive layer or an adhesive layer is suitable for coloring the polarizing film. There was a problem in that there was a significant decrease in single transmittance.
以上のような事情に鑑み、本発明は、高温環境下において、偏光膜の着色による単体透過率の低下の抑制効果に優れる偏光フィルムを提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide a polarizing film that is excellent in suppressing a decrease in single transmittance due to coloring of the polarizing film in a high-temperature environment.
また、本発明は、上記の偏光膜の着色による単体透過率の低下の抑制効果に優れる偏光フィルム、積層偏光フィルム、画像表示パネル、および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 film, a laminated polarizing film, an image display panel, and an image display device that are excellent in suppressing the reduction in unit transmittance due to coloring of the polarizing film.
すなわち、本発明は、偏光膜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貼り合わされた偏光フィルムであって、前記偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成されており、前記接着剤層は、ニトロキシラジカル、またはニトロキシド基を有する化合物を含む偏光フィルムに関する。 That is, the present invention provides a polarizing film in which a transparent protective film is bonded to at least one surface of a polarizing film via an adhesive layer, the polarizing film being formed by adsorbing and orienting iodine to a polyvinyl alcohol film. The adhesive layer relates to a polarizing film containing a compound having a nitroxy radical or a nitroxide group.
また、本発明は、前記偏光フィルムが光学層に貼り合わされている積層偏光フィルムに関する。 The present invention also relates to a laminated polarizing film in which the polarizing film is bonded to an optical layer.
また、本発明は、画像表示セルに、前記偏光フィルム、または前記積層偏光フィルムが貼り合わされている画像表示パネルに関する。 The present invention also relates to an image display panel in which the polarizing film or the laminated polarizing film is bonded to an image display cell.
また、本発明は、前記画像表示パネルの偏光フィルムまたは積層偏光フィルム側に、前面透明部材を備える画像表示装置に関する。 The present invention also relates to an image display device including a front transparent member on the polarizing film or laminated polarizing film side of the image display panel.
本発明の偏光フィルムにおける効果の作用メカニズムの詳細は不明な部分があるが、以下のように推定される。ただし、本発明は、この作用メカニズムに限定して解釈されなくてもよい。 Although the details of the working mechanism of the effect in the polarizing film of the present invention are partially unknown, it is estimated as follows. However, the present invention does not need to be interpreted as being limited to this mechanism of action.
本発明の偏光フィルムは、偏光膜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貼り合わされており、前記接着剤層がニトロキシラジカル、またはニトロキシド基を有する化合物を含有する。また、前記偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成される。上記の特許文献2および3の記載のとおり、一般的にヨウ素系偏光膜は染料系偏光膜よりも耐熱性等の耐久性に劣ると言われているが、この理由は、偏光膜中に含まれるヨウ素が、高温環境下でポリビニルアルコールの脱水反応で起きるポリエン化という劣化現象を促進させるためと推認される。 In the polarizing film of the present invention, a transparent protective film is bonded to at least one surface of the polarizing film via an adhesive layer, and the adhesive layer contains a nitroxy radical or a compound having a nitroxide group. Further, the polarizing film is formed by adsorbing and aligning iodine on a polyvinyl alcohol film. As described in Patent Documents 2 and 3 above, it is said that iodine-based polarizing films are generally inferior to dye-based polarizing films in terms of durability such as heat resistance. It is assumed that this is because the iodine contained in the polyvinyl alcohol accelerates the deterioration phenomenon called polyenation, which occurs due to the dehydration reaction of polyvinyl alcohol in a high-temperature environment.
一方、本発明の前記接着剤層に含まれるニトロキシラジカル、またはニトロキシド基を有する化合物は、高温環境下に曝された場合、当該ニトロキシラジカル、またはニトロキシド基を有する化合物の一部が接着剤層から溶出して、当該接着剤層に近接するヨウ素系偏光膜に染み入ることが推定される。とくに、前面透明部材、前記偏光フィルム、および画像表示セルが、この順に設けられて構成される画像表示装置において、前記接着剤層に含まれるニトロキシラジカル、またはニトロキシド基を有する化合物は、高温環境下に曝された場合、内部に存在する水分(粘着剤層や接着剤層等に存在する水分)とともに、画像表示装置内部を移動(滞留)するため、当該ニトロキシラジカル、またはニトロキシド基を有する化合物の一部は上記のヨウ素系偏光膜に染み入り易いことが推定される。その結果、偏光膜中のニトロキシラジカル、またはニトロキシド基を有する化合物が高温環境下での上記のポリエン化反応において発生するラジカルを効率よく捕捉できると推定されるため、本発明の偏光フィルムは、偏光膜の着色による単体透過率の低下を抑制できる。 On the other hand, when a compound having a nitroxy radical or a nitroxide group contained in the adhesive layer of the present invention is exposed to a high temperature environment, a part of the nitroxy radical or a compound having a nitroxide group becomes adhesive. It is estimated that it is eluted from the layer and seeps into the iodine-based polarizing film adjacent to the adhesive layer. In particular, in an image display device configured by providing a front transparent member, the polarizing film, and an image display cell in this order, the nitroxy radicals or the compound having a nitroxide group contained in the adhesive layer may be used in a high temperature environment. When exposed to water, the nitroxy radicals or nitroxide groups move (stay) inside the image display device together with the moisture present inside (the moisture present in the adhesive layer, adhesive layer, etc.). It is presumed that a part of the compound easily permeates into the above-mentioned iodine-based polarizing film. As a result, it is presumed that the nitroxy radicals or the compound having a nitroxide group in the polarizing film can efficiently capture the radicals generated in the above-mentioned polyenization reaction in a high-temperature environment. Decrease in single transmittance due to coloring of the polarizing film can be suppressed.
<ニトロキシラジカル、またはニトロキシド基を有する化合物>
本発明のニトロキシラジカル、またはニトロキシド基を有する化合物としては、室温、空気中で比較的に安定なラジカルを有する観点から、N-オキシル化合物(官能基として、C-N(-C)-O・を有する化合物(O・はオキシラジカルを示す))が挙げられ、公知のものが使用できる。N-オキシル化合物としては、例えば、以下の構造の有機基を有する化合物などが挙げられる。前記ニトロキシラジカル、またはニトロキシド基を有する化合物は、単独で用いてもよく2種類以上を併用してもよい。
As the nitroxy radical or nitroxide group-containing compound of the present invention, from the viewpoint of having a relatively stable radical in air at room temperature, N-oxyl compounds (C-N(-C)-O * (O * represents an oxy radical)), and known compounds can be used. Examples of the N-oxyl compound include compounds having an organic group having the following structure. The nitroxy radical or nitroxide group-containing compound may be used alone or in combination of two or more.
上記の有機基を有する化合物としては、例えば、以下の一般式(2)~(5)で表わされる化合物などが挙げられる。
前記一般式(1)~(5)中、R2からR5は、入手容易性の観点から、炭素原子数が1~6のアルキル基であることが好ましく、炭素原子数が1~3のアルキル基であることがより好ましい。また、前記一般式(2)中、入手容易性の観点から、R6は水素原子、または炭素原子数が1~10のアルキル基であることが好ましく、水素原子であることがより好ましい。また、前記一般式(3)中、入手容易性の観点から、R7およびR8は独立して水素原子、または炭素原子数が1~10のアルキル基であることが好ましく、水素原子であることがより好ましい。また、前記一般式(4)中、入手容易性の観点から、R9からR11は、水素原子、または炭素原子数が1~10のアルキル基であることが好ましい。また、前記一般式(5)中、入手容易性の観点から、R12は、ヒドロキシ基、アミノ基、またはアルコキシ基であることが好ましい。前記一般式(1)~(5)中、nは、入手容易性の観点から、1であることが好ましい。 In the general formulas (1) to (5), R 2 to R 5 are preferably an alkyl group having 1 to 6 carbon atoms from the viewpoint of availability, and an alkyl group having 1 to 3 carbon atoms. More preferably, it is an alkyl group. Further, in the general formula (2), from the viewpoint of availability, R 6 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom. In addition, in the general formula (3), from the viewpoint of availability, R 7 and R 8 are preferably independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; It is more preferable. Furthermore, in the general formula (4), from the viewpoint of availability, R 9 to R 11 are preferably hydrogen atoms or alkyl groups having 1 to 10 carbon atoms. Further, in the general formula (5), from the viewpoint of easy availability, R 12 is preferably a hydroxy group, an amino group, or an alkoxy group. In the general formulas (1) to (5), n is preferably 1 from the viewpoint of availability.
また、前記N-オキシル化合物としては、例えば、特開2003-64022号公報、特開平11-222462号公報、特開2002-284737号公報、国際公開第2016/047655号などに記載されたN-オキシル化合物が挙げられる。 Further, as the N-oxyl compound, for example, N- Examples include oxyl compounds.
また、前記ニトロキシラジカル、またはニトロキシド基を有する化合物としては、例えば、以下の化合物などが挙げられる。
また、前記ニトロキシラジカル、またはニトロキシド基を有する化合物は、ポリエン化反応において発生するラジカルを効率よく捕捉できる観点から、分子量が、1000以下であることが好ましく、500以下であることがより好ましく、300以下であることがさらに好ましい。 Further, the nitroxy radical or the compound having a nitroxide group preferably has a molecular weight of 1000 or less, more preferably 500 or less, from the viewpoint of efficiently capturing radicals generated in the polyenization reaction. More preferably, it is 300 or less.
<偏光フィルム>
本発明の偏光フィルムは、偏光膜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貼り合わされており、前記偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成されており、前記接着剤層は、前記ニトロキシラジカル、またはニトロキシド基を有する化合物を含む。
<Polarizing film>
In the polarizing film of the present invention, a transparent protective film is bonded to at least one surface of the polarizing film via an adhesive layer, and the polarizing film is formed by adsorbing and aligning iodine to a polyvinyl alcohol film. , the adhesive layer contains the nitroxy radical or a compound having a nitroxide group.
<偏光膜>
本発明の偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成される。前記ポリビニルアルコール(PVA)系フィルムは、可視光領域において透光性を有し、ヨウ素を分散吸着するものを特に制限なく使用できる。また、通常、原反として用いる、PVA系フィルムは、厚さが1~100μm程度であることが好ましく、1~50μm程度であることがより好ましい。
<Polarizing film>
The polarizing film of the present invention is formed by adsorbing and aligning iodine on a polyvinyl alcohol film. The polyvinyl alcohol (PVA) film has transparency in the visible light region and can disperse and adsorb iodine, and can be used without particular limitation. Further, the thickness of the PVA film used as the original film is preferably about 1 to 100 μm, more preferably about 1 to 50 μm.
前記ポリビニルアルコール系フィルムの材料としては、ポリビニルアルコールまたはその誘導体が挙げられる。前記ポリビニルアルコールの誘導体としては、例えば、ポリビニルホルマール、ポリビニルアセタール;エチレン、プロピレン等のオレフィン;アクリル酸、メタクリル酸、クロトン酸等の不飽和カルボン酸、およびそのアルキルエステル、アクリルアミド等で変性したもの等が挙げられる。前記ポリビニルアルコールは、平均重合度が100~10,000程度であることが好ましく、1,000~10,000程度であることがより好ましく、1,500~4,500程度であることがさらに好ましい。また、前記ポリビニルアルコールは、ケン化度が80~100モル%程度であることが好ましく、95モル%~99.95モル程度であることがより好ましい。なお、前記平均重合度および前記ケン化度は、JIS K 6726に準じて求めることができる。 Examples of the material for the polyvinyl alcohol film include polyvinyl alcohol or derivatives thereof. Examples of the polyvinyl alcohol derivatives include polyvinyl formal, polyvinyl acetal; olefins such as ethylene and propylene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and those modified with their alkyl esters, acrylamide, etc. can be mentioned. The average degree of polymerization of the polyvinyl alcohol is preferably about 100 to 10,000, more preferably about 1,000 to 10,000, and even more preferably about 1,500 to 4,500. . Further, the saponification degree of the polyvinyl alcohol is preferably about 80 to 100 mol%, more preferably about 95 mol% to 99.95 mol%. In addition, the said average polymerization degree and the said saponification degree can be calculated|required according to JISK6726.
前記偏光膜は、前記ヨウ素の含有量が1重量%以上15重量%以下であることが好ましい。前記偏光膜は、前記ヨウ素の含有量が、耐久性試験時の色抜けを抑制する観点から、1.5重量%以上であることが好ましく、2重量%以上であることがより好ましく、そして、ポリエン化を防止する観点から、12重量%以下であることが好ましく、10重量%以下であることがより好ましい。 The content of iodine in the polarizing film is preferably 1% by weight or more and 15% by weight or less. In the polarizing film, the iodine content is preferably 1.5% by weight or more, more preferably 2% by weight or more, from the viewpoint of suppressing color fading during a durability test, and From the viewpoint of preventing polyenization, the content is preferably 12% by weight or less, more preferably 10% by weight or less.
前記偏光膜は、例えば、前記ポリビニルアルコール系フィルム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製することができる。必要に応じてホウ酸やヨウ化カリウム等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等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いし、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等の水溶液中や水浴中でも延伸することができる。 The polarizing film can be produced, for example, by dyeing the polyvinyl alcohol film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. If necessary, it can also be immersed in an aqueous solution of boric acid, potassium iodide, or the like. Furthermore, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. Washing a polyvinyl alcohol film with water not only removes dirt and anti-blocking agents from the surface of the polyvinyl alcohol film, but also swells the polyvinyl alcohol film to prevent uneven dyeing and other unevenness. be. Stretching may be carried out after dyeing with iodine, stretching may be carried out while dyeing, or stretching may be carried out before dyeing with iodine. Stretching can be performed in an aqueous solution of boric acid, potassium iodide, etc. or in a water bath.
前記偏光膜は、厚みが、1~50μm程度であることが好ましく、1~25μm程度であることがより好ましい。とくに、厚みが8μm以下の偏光膜を得るためには、上述した特開2009-098653号公報、特開2012-073580号公報、特開2013-238640号公報、特許第4691205号明細書、特許第4751481号明細書等に開示された、前記ポリビニルアルコール系フィルムとして、熱可塑性樹脂等の樹脂基材上に製膜されたポリビニルアルコール系樹脂層を含む積層体を用いる薄型の偏光膜の製造方法が適用できる。 The thickness of the polarizing film is preferably about 1 to 50 μm, more preferably about 1 to 25 μm. In particular, in order to obtain a polarizing film with a thickness of 8 μm or less, the above-mentioned JP 2009-098653, JP 2012-073580, JP 2013-238640, Patent No. 4691205, and Patent No. No. 4751481, etc., discloses a method for manufacturing a thin polarizing film using a laminate including a polyvinyl alcohol resin layer formed on a resin base material such as a thermoplastic resin as the polyvinyl alcohol film. Applicable.
<接着剤層>
本発明の接着剤層は、接着剤により形成される。前記接着剤としては、偏光フィルムに用いられている各種の接着剤を適用でき、例えば、イソシアネート系接着剤、ポリビニルアルコール系接着剤、ゼラチン系接着剤、ビニル系ラテックス系、水系ポリエステル等が挙げられる。これら接着剤は、通常、水溶液からなる接着剤(水系接着剤)として用いられ、0.5~60重量%の固形分を含有してなる。これらの中でも、ポリビニルアルコール系接着剤が好ましく、アセトアセチル基含有ポリビニルアルコール系接着剤がより好ましい。
<Adhesive layer>
The adhesive layer of the present invention is formed of an adhesive. As the adhesive, various adhesives used for polarizing films can be used, such as isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latex adhesives, water-based polyesters, etc. . These adhesives are usually used as adhesives made of an aqueous solution (aqueous adhesives), and contain a solid content of 0.5 to 60% by weight. Among these, polyvinyl alcohol adhesives are preferred, and acetoacetyl group-containing polyvinyl alcohol adhesives are more preferred.
前記水系接着剤は、架橋剤を含んでいてもよい。前記架橋剤としては、通常、接着剤を構成するポリマー等の成分と反応性を有する官能基を1分子中に少なくとも2つ有する化合物が用いられ、例えば、アルキレンジアミン類;イソシアネート類;エポキシ類;アルデヒド類;メチロール尿素、メチロールメラミン等のアミノ-ホルムアルデヒド等が挙げられる。接着剤中の架橋剤の配合量は、接着剤を構成するポリマー等の成分100重量部に対して、通常、10~60重量部程度である。 The water-based adhesive may contain a crosslinking agent. As the crosslinking agent, a compound having at least two functional groups in one molecule that is reactive with components such as polymers constituting the adhesive is usually used, such as alkylene diamines; isocyanates; epoxies; Aldehydes; examples include amino-formaldehydes such as methylol urea and methylol melamine. The amount of the crosslinking agent in the adhesive is usually about 10 to 60 parts by weight per 100 parts by weight of components such as polymers constituting the adhesive.
前記接着剤としては、上記の他、紫外線硬化型接着剤、電子線硬化型接着剤等の活性エネルギー線硬化型接着剤が挙げられる。前記活性エネルギー線硬化型接着剤としては、例えば、(メタ)アクリレート系接着剤が挙げられる。前記(メタ)アクリレート系接着剤における硬化性成分としては、例えば、(メタ)アクリロイル基を有する化合物、ビニル基を有する化合物が挙げられる。(メタ)アクリロイル基を有する化合物としては、例えば、炭素数が1~20の鎖状アルキル(メタ)アクリレート、脂環式アルキル(メタ)アクリレート、多環式アルキル(メタ)アクリレート等のアルキル(メタ)アクリレート;ヒドロキシル基含有(メタ)アクリレート;グリシジル(メタ)アクリレート等のエポキシ基含有(メタ)アクリレート等が挙げられる。(メタ)アクリレート系接着剤は、ヒドロキシエチル(メタ)アクリルアミド、N‐メチロール(メタ)アクリルアミド、N‐メトキシメチル(メタ)アクリルアミド、N‐エトキシメチル(メタ)アクリルアミド、(メタ)アクリルアミド、(メタ)アクリロイルモルホリン等の窒素含有モノマーを含んでいてもよい。(メタ)アクリレート系接着剤は、架橋成分として、トリプロピレングリコールジアクリレート、1,9-ノナンジオールジアクリレート、トリシクロデカンジメタノールジアクリレート、環状トリメチロールプロパンフォルマルアクリレート、ジオキサングリコールジアクリレート、EO変性ジグリセリンテトラアクリレート等の多官能モノマーを含んでいてもよい。また、カチオン重合硬化型接着剤としてエポキシ基やオキセタニル基を有する化合物も使用することができる。エポキシ基を有する化合物は、分子内に少なくとも2個のエポキシ基を有するものであれば特に限定されず、一般に知られている各種の硬化性エポキシ化合物を用いることができる。 In addition to the above adhesives, examples of the adhesive include active energy ray curable adhesives such as ultraviolet ray curable adhesives and electron beam curable adhesives. Examples of the active energy ray-curable adhesive include (meth)acrylate adhesives. Examples of the curable component in the (meth)acrylate adhesive include a compound having a (meth)acryloyl group and a compound having a vinyl group. Examples of compounds having a (meth)acryloyl group include alkyl (meth)acrylates having 1 to 20 carbon atoms, alicyclic alkyl (meth)acrylates, and polycyclic alkyl (meth)acrylates. ) acrylate; hydroxyl group-containing (meth)acrylate; epoxy group-containing (meth)acrylate such as glycidyl (meth)acrylate; and the like. (Meth)acrylate adhesives include hydroxyethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, (meth)acrylamide, and (meth)acrylate. It may also contain a nitrogen-containing monomer such as acryloylmorpholine. The (meth)acrylate adhesive contains tripropylene glycol diacrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, cyclic trimethylolpropane formal acrylate, dioxane glycol diacrylate, EO as a crosslinking component. It may also contain a polyfunctional monomer such as modified diglycerol tetraacrylate. Moreover, a compound having an epoxy group or an oxetanyl group can also be used as a cationic polymerization-curable adhesive. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various commonly known curable epoxy compounds can be used.
前記接着剤は、必要に応じて適宜の添加剤を含んでいてもよい。前記添加剤としては、例えば、シランカップリング剤、チタンカップリング剤等のカップリング剤、エチレンオキシド等の接着促進剤、紫外線吸収剤、劣化防止剤、染料、加工助剤、イオントラップ剤、酸化防止剤、粘着付与剤、充填剤、可塑剤、レベリング剤、発泡抑制剤、帯電防止剤、耐熱安定剤、耐加水分解安定剤等が挙げられる。 The adhesive may contain appropriate additives as necessary. Examples of the additives include coupling agents such as silane coupling agents and titanium coupling agents, adhesion promoters such as ethylene oxide, ultraviolet absorbers, deterioration inhibitors, dyes, processing aids, ion trapping agents, and antioxidants. agents, tackifiers, fillers, plasticizers, leveling agents, foaming inhibitors, antistatic agents, heat stabilizers, hydrolysis stabilizers, and the like.
前記接着剤の塗布は、後述する透明保護フィルム側(または後述する機能層側)、前記偏光膜側のいずれに行ってもよく、両者に行ってもよい。貼り合わせ後には、乾燥工程を施し、塗布乾燥層からなる接着剤層を形成する。前記乾燥工程の後には、必要に応じ、紫外線や電子線を照射することができる。前記接着剤層の厚さは、特に制限されず、水系接着剤等を用いる場合には、30~5000nm程度であることが好ましく、100~1000nm程度であることがより好ましく、紫外線硬化型接着剤、電子線硬化型接着剤等を用いる場合には、0.1~100μm程度であることが好ましく、0.5~10μm程度であることがより好ましい。 The adhesive may be applied to either the transparent protective film side (or the functional layer side described later), the polarizing film side, or both. After bonding, a drying process is performed to form an adhesive layer consisting of a coated and dried layer. After the drying step, ultraviolet rays or electron beams can be irradiated if necessary. The thickness of the adhesive layer is not particularly limited, and when a water-based adhesive or the like is used, it is preferably about 30 to 5000 nm, more preferably about 100 to 1000 nm. When using an electron beam curing adhesive or the like, the thickness is preferably about 0.1 to 100 μm, more preferably about 0.5 to 10 μm.
前記接着剤層は、接着剤層中、前記ニトロキシラジカル、またはニトロキシド基を有する化合物の含有量が70重量%以下であることが好ましい。前記接着剤層は、高温環境下における偏光膜の着色による単体透過率の低下を抑制する観点から、接着剤層中、1重量%以上であることが好ましく、5重量%以上であることがより好ましく、10重量%以上であることがさらに好ましく、そして、60重量%以下であることが好ましく、50重量%以下であることがより好ましい。 The content of the nitroxy radical or nitroxide group-containing compound in the adhesive layer is preferably 70% by weight or less. The adhesive layer preferably accounts for 1% by weight or more, more preferably 5% by weight or more in the adhesive layer, from the viewpoint of suppressing a decrease in single transmittance due to coloring of the polarizing film in a high-temperature environment. It is preferably 10% by weight or more, more preferably 60% by weight or less, and more preferably 50% by weight or less.
<透明保護フィルム>
本発明の透明保護フィルムは、特に制限されず、偏光フィルムに用いられている各種の透明保護フィルムを用いることができる。前記透明保護フィルムを構成する材料としては、例えば、透明性、機械的強度、熱安定性、水分遮断性、等方性等に優れる熱可塑性樹脂が用いられる。前記熱可塑性樹脂としては、例えば、トリアセチルセルロール等のセルロールエステル系樹脂、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樹脂、ポリエーテルスルホン系樹脂、ポリスルホン系樹脂、ポリカーボネート系樹脂、ナイロンや芳香族ポリアミド等のポリアミド系樹脂、ポリイミド系樹脂、ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体の如きポリオレフィン系樹脂、(メタ)アクリル系樹脂、シクロ系ないしはノルボルネン構造を有する環状ポリオレフィン系樹脂(ノルボルネン系樹脂)、ポリアリレート系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、およびこれらの混合物があげられる。また、前記透明保護フィルムは、(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または紫外線硬化型樹脂から形成される硬化層を用いることができる。これらの中でも、セルロールエステル系樹脂、ポリカーボネート系樹脂、(メタ)アクリル系樹脂、環状ポリオレフィン系樹脂、ポリエステル系樹脂が好適である。
<Transparent protective film>
The transparent protective film of the present invention is not particularly limited, and various transparent protective films used for polarizing films can be used. As the material constituting the transparent protective film, for example, a thermoplastic resin having excellent transparency, mechanical strength, thermal stability, moisture barrier properties, isotropy, etc. is used. Examples of the thermoplastic resin include cellulose ester resins such as triacetyl cellulose, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone resins, polysulfone resins, polycarbonate resins, nylon, and aromatic resins. Polyamide resins such as group polyamides, polyimide resins, polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymers, (meth)acrylic resins, cyclic polyolefin resins having a cyclo- or norbornene structure (norbornene resins) ), polyarylate resins, polystyrene resins, polyvinyl alcohol resins, and mixtures thereof. Further, the transparent protective film may include a cured layer formed from a thermosetting resin or an ultraviolet curable resin such as (meth)acrylic, urethane, acrylic urethane, epoxy, or silicone resin. Among these, cellulose ester resins, polycarbonate resins, (meth)acrylic resins, cyclic polyolefin resins, and polyester resins are preferred.
前記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、薄層性等の観点から、1~500μm程度であることが好ましく、1~300μm程度あることがより好ましく、5~100μm程度であることがさらに好ましい。 The thickness of the transparent protective film can be determined as appropriate, but in general, from the viewpoint of workability such as strength and handleability, thin layer property, etc., it is preferably about 1 to 500 μm, and about 1 to 300 μm. The thickness is more preferably about 5 to 100 μm.
前記透明保護フィルムを、前記偏光膜の両面に貼り合わせる場合、その両面の透明保護フィルムは、同じものであってもよく、異なっていてもよい。 When the transparent protective films are attached to both sides of the polarizing film, the transparent protective films on both sides may be the same or different.
前記透明保護フィルムは、正面位相差が40nm以上および/または、厚み方向位相差が80nm以上の位相差を有する位相差板を用いることができる。正面位相差は、通常、40~200nmの範囲に、厚み方向位相差は、通常、80~300nmの範囲に制御される。前記透明保護フィルムとして位相差板を用いる場合には、当該位相差板が透明保護フィルムとしても機能するため、薄型化を図ることができる。 As the transparent protective film, a retardation plate having a front retardation of 40 nm or more and/or a thickness direction retardation of 80 nm or more can be used. The frontal retardation is usually controlled in the range of 40 to 200 nm, and the thickness direction retardation is usually controlled in the range of 80 to 300 nm. When a retardation plate is used as the transparent protective film, the retardation plate also functions as a transparent protective film, so that it is possible to reduce the thickness.
前記位相差板としては、例えば、高分子素材を一軸または二軸延伸処理してなる複屈折性フィルム、液晶ポリマーの配向フィルム、液晶ポリマーの配向層をフィルムにて支持したもの等が挙げられる。位相差板の厚さは特に制限されないが、20~150μm程度が一般的である。なお、位相差を有しない透明保護フィルムに前記位相板を貼り合わせて使用してもよい。 Examples of the retardation plate include a birefringent film formed by uniaxially or biaxially stretching a polymer material, an oriented film of a liquid crystal polymer, and a film in which an oriented layer of a liquid crystal polymer is supported by a film. The thickness of the retardation plate is not particularly limited, but is generally about 20 to 150 μm. Note that the phase plate may be used by bonding it to a transparent protective film that does not have a phase difference.
前記透明保護フィルムには、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、帯電防止剤、顔料、着色剤等の任意の適切な添加剤を含んでいてもよい。とくに、前記透明保護フィルムに紫外線吸収剤を含む場合、偏光フィルムの耐光性を向上できる。 The transparent protective film may contain any suitable additives such as ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, color inhibitors, flame retardants, antistatic agents, pigments, colorants, etc. You can stay there. In particular, when the transparent protective film contains an ultraviolet absorber, the light resistance of the polarizing film can be improved.
前記透明保護フィルムの偏光膜を貼り合わせない面には、ハードコート層、反射防止層、スティッキング防止層、拡散層ないしアンチグレア層等の機能層を設けることができる。なお、上記ハードコート層、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の機能層は、保護フィルムそのものに設けることができるほか、別途、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。 A functional layer such as a hard coat layer, an anti-reflection layer, an anti-sticking layer, a diffusion layer or an anti-glare layer can be provided on the surface of the transparent protective film on which the polarizing film is not bonded. Note that the functional layers such as the hard coat layer, antireflection layer, antisticking layer, diffusion layer, and antiglare layer can be provided on the protective film itself, or may be provided separately from the protective film. can.
本発明の偏光フィルムは、前記偏光膜の少なくとも一方の面が、前記接着剤層を介して前記透明保護フィルムに貼り合わされていればよく、前記偏光膜の他面(他方の面)と前記透明保護フィルム、あるいは前記偏光膜の他面(他方の面)と前記機能層は、通常、粘着剤層または前記接着剤層を介して貼り合わされる。また、前記偏光膜の他面(他方の面)には、前記接着剤層を介して、後述する画像表示セルや前面透明部材を直接貼り合わせることもできる。 In the polarizing film of the present invention, it is sufficient that at least one surface of the polarizing film is bonded to the transparent protective film via the adhesive layer, and the other surface (the other surface) of the polarizing film and the transparent The protective film or the other surface of the polarizing film and the functional layer are usually bonded together via an adhesive layer or the adhesive layer. Further, an image display cell or a front transparent member, which will be described later, can be directly bonded to the other surface (the other surface) of the polarizing film via the adhesive layer.
前記粘着剤層を形成する粘着剤としては、偏光フィルムに用いられている各種の粘着剤を適用でき、例えば、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルポロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤等が挙げられる。これらの中でも、アクリル系粘着剤が好適である。前記アクリル系粘着剤は、ベースポリマーとしてアクリル系ポリマーを含有するものであり、例えば、特開2017-75998号公報等に記載のアクリル系粘着剤が例示できる。 As the adhesive forming the adhesive layer, various adhesives used in polarizing films can be used, such as rubber adhesives, acrylic adhesives, silicone adhesives, urethane adhesives, vinyl adhesives, etc. Examples include alkyl ether adhesives, polyvinyl alcohol adhesives, polyvinylporolidone adhesives, polyacrylamide adhesives, cellulose adhesives, and the like. Among these, acrylic adhesives are preferred. The acrylic adhesive contains an acrylic polymer as a base polymer, and examples thereof include the acrylic adhesive described in JP-A No. 2017-75998.
粘着剤層を形成する方法としては、例えば、前記粘着剤を剥離処理したセパレータ等に塗布し、乾燥して粘着剤層を形成した後に、偏光膜等に転写する方法、または前記粘着剤を偏光膜等に塗布し、乾燥して粘着剤層を形成する方法等が例示できる。前記粘着剤層の厚さは、特に制限されず、例えば、1~100μm程度であり、2~50μm程度であることが好ましい。 The adhesive layer can be formed by, for example, applying the adhesive to a release-treated separator, drying it to form an adhesive layer, and then transferring it to a polarizing film or the like, or applying the adhesive to a polarizing film, etc. Examples include a method of applying the adhesive onto a film or the like and drying it to form an adhesive layer. The thickness of the adhesive layer is not particularly limited, and is, for example, about 1 to 100 μm, preferably about 2 to 50 μm.
前記透明保護フィルムと前記偏光膜、あるいは前記偏光膜と前記機能層は、表面改質処理層、易接着剤層、ブロック層、屈折率調整層等の介在層を介して積層されていてもよい。 The transparent protective film and the polarizing film, or the polarizing film and the functional layer may be laminated via an intervening layer such as a surface modification treatment layer, an adhesive layer, a block layer, a refractive index adjustment layer, etc. .
前記表面改質層を形成する表面改質処理としては、例えば、コロナ処理、プラズマ処理、プライマー処理、ケン化処理等が挙げられる。 Examples of the surface modification treatment for forming the surface modification layer include corona treatment, plasma treatment, primer treatment, and saponification treatment.
前記易接着層を形成する易接着剤としては、例えば、ポリエステル骨格、ポリエーテル骨格、ポリカーボネート骨格、ポリウレタン骨格、シリコーン系、ポリアミド骨格、ポリイミド骨格、ポリビニルアルコール骨格等を有する各種樹脂を含む形成材が挙げられる。前記易接着層は、通常、保護フィルムに予め設けておき、当該保護フィルムの易接着層側と偏光膜とを、前記粘着剤層または前記接着剤層により積層する。 Examples of the easy-adhesive agent forming the easy-adhesive layer include forming materials containing various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone system, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, etc. Can be mentioned. The easily bonding layer is usually provided in advance on a protective film, and the easily bonding layer side of the protective film and the polarizing film are laminated using the pressure-sensitive adhesive layer or the adhesive layer.
前記ブロック層は、透明保護フィルム等から溶出されるオリゴマーやイオン等の不純物が偏光膜中に移行(侵入)することを防止するため機能を有する層である。前記ブロック層は、透明性を有し、かつ透明保護フィルム等から溶出される不純物が防止できる層であればよく、ブロック層を形成する材としては、例えば、ウレタンプレポリマー系形成材、シアノアクリレート系形成材、エポキシ系形成材等が挙げられる。 The blocking layer is a layer having a function of preventing impurities such as oligomers and ions eluted from the transparent protective film from migrating (invading) into the polarizing film. The block layer may be any layer as long as it has transparency and can prevent impurities leached from a transparent protective film, etc. Materials for forming the block layer include, for example, urethane prepolymer-based forming materials, cyanoacrylates, etc. Examples include system forming materials, epoxy forming materials, and the like.
前記屈折率調整層は、前記透明保護フィルムと偏光膜等屈折率の異なる層間での反射に伴う透過率の低下を抑制するために設けられる層である。前記屈折率調整層を形成する屈折率調整材としては、例えば、シリカ系、アクリル系、アクリル-スチレン系、メラミン系等を有する各種樹脂及び添加剤を含む形成剤が挙げられる。 The refractive index adjusting layer is a layer provided to suppress a decrease in transmittance due to reflection between layers having different refractive indexes, such as the transparent protective film and the polarizing film. Examples of the refractive index adjusting material forming the refractive index adjusting layer include forming agents containing various resins and additives, such as silica-based, acrylic-based, acrylic-styrene-based, and melamine-based resins.
<積層偏光フィルム>
本発明の積層偏光フィルム(光学積層体)は、前記偏光フィルムが光学層に貼り合わされているものである。前記光学層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)、視角補償フィルム等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層または2層以上用いることができる。前記積層偏光フィルムとしては、特に、前記偏光フィルムに更に反射板または半透過反射板が積層されてなる反射型偏光フィルムまたは半透過型偏光フィルム、前記偏光フィルムに更に位相差板が積層されてなる楕円偏光フィルムまたは円偏光フィルム、前記偏光フィルム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フィルム、あるいは前記偏光フィルムに更に輝度向上フィルムが積層されてなる偏光フィルムが挙げられる。
<Laminated polarizing film>
The laminated polarizing film (optical laminate) of the present invention has the polarizing film bonded to an optical layer. The optical layer is not particularly limited, but may be used, for example, in the formation of a liquid crystal display device such as a reflective plate, a semi-transmissive plate, a retardation plate (including a 1/2 or 1/4 wavelength plate), a viewing angle compensation film, etc. One or more optical layers that are sometimes used can be used. The laminated polarizing film is particularly a reflective polarizing film or a semi-transmissive polarizing film in which a reflective plate or a transflective plate is further laminated on the polarizing film, and a retardation plate is further laminated in the polarizing film. Examples include an elliptical polarizing film or a circularly polarizing film, a wide viewing angle polarizing film in which a viewing angle compensation film is further laminated on the polarizing film, or a polarizing film in which a brightness enhancement film is further laminated on the polarizing film.
前記偏光フィルム、あるいは前記積層偏光フィルムの一方の面あるいは両方の面には、液晶セルや有機EL素子等の画像表示セルと、視認側における前面透明板やタッチパネル等の前面透明部材等の他の部材を貼り合わせるための接着剤層が付設されてもよい。当該接着剤層としては、粘着剤層が好適である。前記粘着剤層を形成する粘着剤は特に制限されないが、例えば、アクリル系重合体、シリコーン系ポリマー、ポリエステル、ポリウレタン、ポリアミド、ポリエーテル、フッ素系やゴム系等のポリマーをベースポリマーとするものを適宜に選択して用いることができる。特に、アクリル系重合体を含む粘着剤のように、光学的透明性に優れ、適度な濡れ性と凝集性と接着性を示し、耐候性や耐熱性等に優れるものが好ましく用いられる。 On one or both sides of the polarizing film or the laminated polarizing film, an image display cell such as a liquid crystal cell or an organic EL element, and other front transparent members such as a front transparent plate or a touch panel on the viewing side are provided. An adhesive layer for bonding the members together may be provided. A pressure-sensitive adhesive layer is suitable as the adhesive layer. The adhesive forming the adhesive layer is not particularly limited, but examples include those having a base polymer such as an acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based polymer, or a rubber-based polymer. It can be selected and used as appropriate. In particular, pressure-sensitive adhesives containing acrylic polymers that have excellent optical transparency, exhibit appropriate wettability, cohesiveness, and adhesive properties, and are excellent in weather resistance, heat resistance, etc. are preferably used.
前記偏光フィルムや前記積層偏光フィルムの片面または両面への粘着剤層の付設は、適宜な方式で行いうる。粘着剤層の付設としては、例えば、粘着剤溶液を調製し、それを流延方式や塗布方式等の適宜な展開方式で前記偏光フィルムや前記積層偏光フィルム上に直接付設する方式、あるいは、セパレータ上に粘着剤層を形成して、それを前記偏光フィルムや前記積層偏光フィルム上に移着する方式等が挙げられる。前記粘着剤層の厚さは、使用目的や接着力等に応じて適宜に決定でき、一般には1~500μmであり、5~200μmであることが好ましく、10~100μmであることがより好ましい。このように、前記偏光フィルムや前記積層偏光フィルムの少なくとも一方の面に粘着剤層が設けられたものを、粘着剤層付き偏光フィルム、または粘着剤層付き積層偏光フィルムという。 The adhesive layer can be attached to one or both sides of the polarizing film or the laminated polarizing film by any appropriate method. For attaching the adhesive layer, for example, a method of preparing an adhesive solution and applying it directly onto the polarizing film or the laminated polarizing film using an appropriate developing method such as a casting method or a coating method, or a method of applying the adhesive solution directly onto the polarizing film or the laminated polarizing film, or using a separator. Examples include a method of forming an adhesive layer thereon and transferring it onto the polarizing film or the laminated polarizing film. The thickness of the adhesive layer can be determined as appropriate depending on the purpose of use, adhesive strength, etc., and is generally 1 to 500 μm, preferably 5 to 200 μm, and more preferably 10 to 100 μm. In this way, the polarizing film or the laminated polarizing film in which an adhesive layer is provided on at least one surface is referred to as a polarizing film with an adhesive layer or a laminated polarizing film with an adhesive layer.
前記粘着剤層の露出面に対しては、実用に供するまでの間、その汚染防止等を目的にセパレータが仮着されてカバーされることが好ましい。これにより、通例の取扱状態で粘着剤層の汚染等が防止できる。前記セパレータとしては、例えば、プラスチックフィルム、ゴムシート、紙、布、不織布、ネット、発泡シートや金属箔、それらのラミネート体等の適宜な薄葉体を、必要に応じシリコーン系や長鎖アルキル系、フッ素系や硫化モリブデン等の適宜な剥離剤でコート処理したもの等が用いられる。 It is preferable that the exposed surface of the adhesive layer is temporarily covered with a separator for the purpose of preventing contamination until it is put into practical use. This can prevent contamination of the adhesive layer under normal handling conditions. As the separator, for example, appropriate thin materials such as plastic films, rubber sheets, paper, cloth, non-woven fabrics, nets, foam sheets, metal foils, laminates thereof, silicone-based, long-chain alkyl-based, etc. A material coated with an appropriate release agent such as fluorine-based or molybdenum sulfide is used.
<画像表示パネルおよび画像表示装置>
本発明の画像表示パネルは、画像表示セルに、前記偏光フィルム、または前記積層偏光フィルムが貼り合わされているものである。また、本発明の画像表示装置は、前記画像表示パネルの偏光フィルムまたは積層偏光フィルム側(視認側)に、前面透明部材を備えるものである。
<Image display panel and image display device>
In the image display panel of the present invention, the polarizing film or the laminated polarizing film is bonded to an image display cell. Further, the image display device of the present invention includes a front transparent member on the polarizing film or laminated polarizing film side (viewing side) of the image display panel.
前記画像表示セルとしては、例えば、液晶セルや有機ELセル等が挙げられる。前記液晶セルとしては、例えば、外光を利用する反射型液晶セル、バックライト等の光源からの光を利用する透過型液晶セル、外部からの光と光源からの光の両者を利用する半透過半反射型液晶セルのいずれを用いてもよい。前記液晶セルが光源からの光を利用するものである場合、画像表示装置(液晶表示装置)は、画像表示セル(液晶セル)の視認側と反対側にも偏光フィルムが配置され、さらに光源が配置される。当該光源側の偏光フィルムと液晶セルとは、適宜の接着剤層を介して貼り合せられていることが好ましい。前記液晶セルの駆動方式としては、例えば、VAモード、IPSモード、TNモード、STNモードやベンド配向(π型)等の任意なタイプのものを用いうる。 Examples of the image display cell include a liquid crystal cell and an organic EL cell. Examples of the liquid crystal cell include a reflective liquid crystal cell that uses external light, a transmissive liquid crystal cell that uses light from a light source such as a backlight, and a transflective liquid crystal cell that uses both external light and light from a light source. Any semi-reflective liquid crystal cell may be used. When the liquid crystal cell uses light from a light source, the image display device (liquid crystal display device) includes a polarizing film on the side opposite to the viewing side of the image display cell (liquid crystal cell), and further includes a light source. Placed. It is preferable that the polarizing film on the light source side and the liquid crystal cell are bonded together via a suitable adhesive layer. As a driving method for the liquid crystal cell, any type of driving method can be used, such as VA mode, IPS mode, TN mode, STN mode, or bend alignment (π type).
前記有機ELセルとしては、例えば、透明基板上に透明電極と有機発光層と金属電極とを順に積層して発光体(有機エレクトロルミネセンス発光体)を形成したもの等が好適に用いられる。前記有機発光層は、種々の有機薄膜の積層体であり、例えば、トリフェニルアミン誘導体等からなる正孔注入層と、アントラセン等の蛍光性の有機固体からなる発光層との積層体や、これらの発光層とペリレン誘導体等からなる電子注入層の積層体、あるいは正孔注入層、発光層、および電子注入層の積層体等、種々層構成が採用され得る。 As the organic EL cell, for example, a cell in which a transparent electrode, an organic light-emitting layer, and a metal electrode are sequentially laminated on a transparent substrate to form a light-emitting body (organic electroluminescence light-emitting body) is preferably used. The organic light emitting layer is a laminate of various organic thin films, such as a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene; Various layer configurations may be adopted, such as a laminate of a light emitting layer and an electron injection layer made of a perylene derivative, or a laminate of a hole injection layer, a light emitting layer, and an electron injection layer.
前記画像表示セルの視認側に配置される前面透明部材としては、例えば、前面透明板(ウインドウ層)やタッチパネル等が挙げられる。前記前面透明板としては、適宜の機械強度および厚みを有する透明板が用いられる。このような透明板としては、例えば、アクリル系樹脂やポリカーボネート系樹脂のような透明樹脂板、あるいはガラス板等が用いられる。前記タッチパネルとしては、例えば、抵抗膜方式、静電容量方式、光学方式、超音波方式等の各種タッチパネルや、タッチセンサー機能を備えるガラス板や透明樹脂板等が用いられる。前記前面透明部材として静電容量方式のタッチパネルが用いられる場合、タッチパネルよりもさらに視認側に、ガラスや透明樹脂板からなる前面透明板が設けられることが好ましい。 Examples of the front transparent member disposed on the viewing side of the image display cell include a front transparent plate (window layer), a touch panel, and the like. As the front transparent plate, a transparent plate having appropriate mechanical strength and thickness is used. As such a transparent plate, for example, a transparent resin plate such as acrylic resin or polycarbonate resin, or a glass plate is used. As the touch panel, for example, various touch panels such as a resistive film type, a capacitance type, an optical type, an ultrasonic type, etc., a glass plate, a transparent resin plate, etc. having a touch sensor function are used. When a capacitive touch panel is used as the front transparent member, it is preferable that a front transparent plate made of glass or a transparent resin plate is provided further on the viewing side than the touch panel.
以下に実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.
<実施例1>
<偏光膜の作製>
平均重合度が2,400、ケン化度が99.9モル%、厚みが45μmであるポリビニルアルコールフィルムを用意した。ポリビニルアルコールフィルムを、周速比の異なるロール間で、20℃の膨潤浴(水浴)中に30秒間浸漬して膨潤しながら搬送方向に2.2倍に延伸し(膨潤工程)、続いて、30℃の染色浴(水100重量部に対して、ヨウ素とヨウ化カリウムを1:7の重量比で配合して得られたヨウ素水溶液)中で最終的に得られる偏光膜のヨウ素濃度が3.60重量%となるように濃度を調整しながら30秒間浸漬して染色しながら元のポリビニルアルコールフィルム(搬送方向に全く延伸していないポリビニルアルコールフィルム)を基準にして搬送方向に3.3倍に延伸した(染色工程)。次いで、染色したポリビニルアルコールフィルムを、40℃の架橋浴(ホウ酸濃度が3.0重量%、ヨウ化カリウム濃度が3.0重量%である水溶液)中で28秒間浸漬して元のポリビニルアルコールフィルムを基準にして搬送方向に3.6倍まで延伸した(架橋工程)。さらに、得られたポリビニルアルコールフィルムを、61℃の延伸浴(ホウ酸濃度が4.0重量%、ヨウ化カリウム濃度が5.0重量%である水溶液)中で60秒間浸漬して元のポリビニルアルコールフィルムを基準にして搬送方向に6.0倍まで延伸した(延伸工程)後、35℃の洗浄浴(ヨウ化カリウム濃度が2.0重量%である水溶液)中で10秒間浸漬した(洗浄工程)。洗浄したポリビニルアルコールフィルムを、40℃で30秒間乾燥して偏光膜を作製した。偏光膜の厚みは18μmであった。
<Example 1>
<Preparation of polarizing film>
A polyvinyl alcohol film having an average degree of polymerization of 2,400, a degree of saponification of 99.9 mol%, and a thickness of 45 μm was prepared. The polyvinyl alcohol film was immersed in a 20°C swelling bath (water bath) for 30 seconds between rolls with different circumferential speed ratios to stretch it 2.2 times in the transport direction while swelling (swelling step), and then, The iodine concentration of the final polarizing film obtained in a dyeing bath at 30°C (an aqueous iodine solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) is 3. While adjusting the concentration to .60% by weight and dyeing by dipping for 30 seconds, it is 3.3 times the original polyvinyl alcohol film (polyvinyl alcohol film that has not been stretched in the transport direction at all) in the transport direction. (dying process). Next, the dyed polyvinyl alcohol film was immersed for 28 seconds in a 40°C crosslinking bath (an aqueous solution with a boric acid concentration of 3.0% by weight and a potassium iodide concentration of 3.0% by weight) to restore the original polyvinyl alcohol. The film was stretched up to 3.6 times in the transport direction (crosslinking step). Furthermore, the obtained polyvinyl alcohol film was immersed for 60 seconds in a 61°C stretching bath (an aqueous solution with a boric acid concentration of 4.0% by weight and a potassium iodide concentration of 5.0% by weight) to restore the original polyvinyl alcohol film. After stretching the alcohol film to 6.0 times in the transport direction (stretching step), the film was immersed for 10 seconds in a 35°C cleaning bath (an aqueous solution with a potassium iodide concentration of 2.0% by weight) (cleaning). process). The washed polyvinyl alcohol film was dried at 40° C. for 30 seconds to produce a polarizing film. The thickness of the polarizing film was 18 μm.
[偏光膜中のヨウ素含有量(重量%)の測定方法]
偏光膜について、蛍光X線分析装置(リガク社製、商品名「ZSX-PRIMUS IV」、測定径:ψ20mm)を用いて、下記式を用いてヨウ素濃度(重量%)を求めた。
ヨウ素濃度(wt%)=14.474×(蛍光X線強度)/(フィルム厚み)(kcps/μm)なお、濃度を算出する際の係数は測定装置によって異なるが、当該係数は適切な検量線を用いて求めることができる。
[Method for measuring iodine content (wt%) in polarizing film]
Regarding the polarizing film, the iodine concentration (weight %) was determined using the following formula using a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., trade name "ZSX-PRIMUS IV", measurement diameter: ψ 20 mm).
Iodine concentration (wt%) = 14.474 x (fluorescent X-ray intensity) / (film thickness) (kcps/μm) The coefficient for calculating the concentration differs depending on the measuring device, but the coefficient can be calculated using an appropriate calibration curve. It can be found using
<偏光フィルムの作製>
接着剤として、アセトアセチル基を含有するポリビニルアルコール樹脂(平均重合度が1,200、ケン化度が98.5モル%、アセトアセチル化度が5モル%)とメチロールメラミンと一般式(9)で示されるニトロキシラジカル、またはニトロキシド基を有する化合物とを重量比3:1:4で含有する水溶液を用いた。この接着剤を用いて、上記で得られた偏光膜の両面に、透明保護フィルムとして、ハードコート層を有する厚み47μmのトリアセチルセルロースフィルム(透湿度が342g/(m2・24h)、コニカミノルタ製、商品名「KC4UYW」)をロール貼合機で貼り合わせた後、引き続きオーブン内で加熱乾燥(温度が60℃、時間が4分間)させて、偏光膜の両面に透明保護フィルムが貼り合わせられた偏光フィルムを作製した。偏光フィルムの単体透過率は39.7%であった。
As an adhesive, a polyvinyl alcohol resin containing an acetoacetyl group (average degree of polymerization 1,200, degree of saponification 98.5 mol%, degree of acetoacetylation 5 mol%), methylolmelamine, and general formula (9) An aqueous solution containing a nitroxy radical or a compound having a nitroxide group in a weight ratio of 3:1:4 was used. Using this adhesive, a 47 μm thick triacetyl cellulose film (moisture permeability 342 g/(m 2 24 h), Konica Minolta After laminating the film using a roll laminating machine, the transparent protective film was laminated to both sides of the polarizing film by heating and drying in an oven (temperature: 60°C, time: 4 minutes). A polarizing film was produced. The single transmittance of the polarizing film was 39.7%.
<アクリル系粘着剤の調製>
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた4つ口フラスコに、ブチルアクリレート99部、4-ヒドロキシブチルアクリレート1部を含有するモノマー混合物を仕込んだ。さらに、前記モノマー混合物(固形分)100部に対して、重合開始剤として2,2’-アゾビスイソブチロニトリル0.1部を酢酸エチル100部と共に仕込み、緩やかに攪拌しながら窒素ガスを導入して窒素置換した後、フラスコ内の液温を55℃付近に保って8時間重合反応を行って、重量平均分子量(Mw)180万のアクリル系ポリマーの溶液を調製した。その後、得られたアクリル系ポリマーの溶液の固形分100部に対して、イソシアネート架橋剤(東ソー社製、商品名「タケネートD110N」、トリメチロールプロパン/キシリレンジイソシアネート付加物)0.02部、シランカップリング剤(信越化学工業社製、商品名「X-41-1056」)0.2部を配合して、アクリル系粘着剤組成物の溶液を調製した。次いで、上記で得られたアクリル系粘着剤組成物の溶液を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム(三菱化学ポリエステルフィルム製、商品名「MRF38」、セパレータフィルム)の片面に、乾燥後の粘着剤層の厚さが20μmになるように塗布し、90℃で1分間乾燥を行い、セパレータフィルムの表面に粘着剤層を形成した。次いで、上記で作製した偏光フィルムの一方の面に、セパレータフィルム上に形成した粘着剤層を転写して、粘着剤層付き偏光フィルムを作製した。
<Preparation of acrylic adhesive>
A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. Furthermore, to 100 parts of the monomer mixture (solid content), 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was charged together with 100 parts of ethyl acetate, and nitrogen gas was added while stirring gently. After introducing the flask and purging it with nitrogen, a polymerization reaction was carried out for 8 hours while maintaining the liquid temperature in the flask at around 55° C. to prepare a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.8 million. Thereafter, based on 100 parts of the solid content of the obtained acrylic polymer solution, 0.02 part of an isocyanate crosslinking agent (manufactured by Tosoh Corporation, trade name "Takenate D110N", trimethylolpropane/xylylene diisocyanate adduct), silane A solution of an acrylic adhesive composition was prepared by adding 0.2 part of a coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "X-41-1056"). Next, the solution of the acrylic adhesive composition obtained above was applied to one side of a polyethylene terephthalate film (manufactured by Mitsubishi Chemical Polyester Film, trade name "MRF38", separator film) treated with a silicone release agent, after drying. was applied so that the thickness of the adhesive layer was 20 μm, and dried at 90° C. for 1 minute to form an adhesive layer on the surface of the separator film. Next, the adhesive layer formed on the separator film was transferred to one side of the polarizing film produced above to produce a polarizing film with an adhesive layer.
<疑似画像表示装置(積層体)の作製>
上記で得られた粘着剤層付き偏光フィルムを、偏光膜の吸収軸が長辺となるように45×40mmのサイズに切断し、粘着剤層を介してガラス板(疑似画像表示セル)を貼り合わせ、偏光フィルムの他方の面に厚み200μmのアクリル酸モノマーフリー粘着剤(日東電工(株)製、商品名「LUCIACS CS9868」)を介して別のガラス板(疑似前面透明部材)を貼り合わせて、疑似画像表示装置(積層体)を作製した。
<Production of pseudo image display device (laminate)>
The polarizing film with the adhesive layer obtained above was cut into a size of 45 x 40 mm so that the absorption axis of the polarizing film was the long side, and a glass plate (pseudo image display cell) was pasted through the adhesive layer. Then, another glass plate (pseudo front transparent member) was attached to the other side of the polarizing film with a 200 μm thick acrylic acid monomer-free adhesive (manufactured by Nitto Denko Corporation, product name ``LUCIACS CS9868''). , a pseudo image display device (laminate) was produced.
[高温環境下における単体透過率の評価]
上記で得られた疑似画像表示装置(積層体)を、温度105℃の熱風オーブン内に48時間静置し、投入(加熱)前後の単体透過率(ΔTs)を測定した。単体透過率は、分光光度計(村上色彩技術研究所(株)製、製品名「DOT-3」)を用いて測定し、以下の基準で評価した。当該単体透過率は、JlS Z 8701-1982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。なお、測定波長は、380~700nm(10nm毎)である。結果を表1に示す。
ΔTs(%)=Ts48-Ts0
ここで、Ts0は加熱前の疑似画像表示装置(積層体)の単体透過率であり、Ts48は48時間加熱後の疑似画像表示装置(積層体)の単体透過率である。
○:5≧ΔTs(%)≧0
×:ΔTs(%)>5、あるいはΔTs(%)<0
[Evaluation of single transmittance in high temperature environment]
The pseudo image display device (laminate) obtained above was left in a hot air oven at a temperature of 105° C. for 48 hours, and the single transmittance (ΔTs) before and after being put in (heated) was measured. Single transmittance was measured using a spectrophotometer (manufactured by Murakami Color Research Institute Co., Ltd., product name "DOT-3") and evaluated based on the following criteria. The single transmittance is a Y value corrected for visual sensitivity using the 2-degree field of view (C light source) of JIS Z 8701-1982. Note that the measurement wavelength is 380 to 700 nm (every 10 nm). The results are shown in Table 1.
ΔTs (%) = Ts 48 - Ts 0
Here, Ts 0 is the single transmittance of the pseudo image display device (laminate) before heating, and Ts 48 is the single transmittance of the pseudo image display device (laminate) after heating for 48 hours.
○: 5≧ΔTs (%)≧0
×: ΔTs (%) > 5, or ΔTs (%) < 0
前記ΔTs(%)は、5≧ΔTs(%)≧0であることが好ましく、4≧ΔTs(%)≧0であることがより好ましい。 The ΔTs (%) preferably satisfies 5≧ΔTs (%)≧0, and more preferably satisfies 4≧ΔTs (%)≧0.
<実施例2>
<偏光膜、偏光フィルム、疑似画像表示装置(積層体)の作製>
偏光フィルムの作製において、使用する両方の接着剤に一般式(10)で示されるニトロキシラジカル、またはニトロキシド基を有する化合物をポリビニルアルコール樹脂との重量比で4:3となるように添加し、接着剤の硬化反応に影響を与えないように、ニトロキシラジカル、またはニトロキシド基を有する化合物に対してモル比で1:1となるように水酸化カリウムを添加して、pHを調整したこと(中和したこと)以外は、実施例1と同様の操作にて、偏光膜、両面保護偏光フィルム、および疑似画像表示装置(積層体)を作製した。偏光フィルムの単体透過率は40.0%であった。
<Production of polarizing film, polarizing film, and pseudo image display device (laminate)>
In the production of a polarizing film, a compound having a nitroxy radical represented by general formula (10) or a nitroxide group is added to both adhesives used so that the weight ratio with the polyvinyl alcohol resin is 4:3, In order not to affect the curing reaction of the adhesive, potassium hydroxide was added at a molar ratio of 1:1 to the compound having a nitroxy radical or nitroxide group to adjust the pH ( A polarizing film, a double-sided protective polarizing film, and a pseudo image display device (laminate) were produced in the same manner as in Example 1, except that the polarizing film was neutralized. The single transmittance of the polarizing film was 40.0%.
<実施例3>
<偏光膜、偏光フィルム、疑似画像表示装置(積層体)の作製>
偏光フィルムの作製において、使用する両方の接着剤に一般式(9)の代わりに、一般式(8)で示されるニトロキシラジカル、またはニトロキシド基を有する化合物を使用したこと以外は、実施例1と同様の操作にて、偏光膜、両面保護偏光フィルム、および疑似画像表示装置(積層体)を作製した。偏光フィルムの単体透過率は39.6%であった。
<Example 3>
<Production of polarizing film, polarizing film, and pseudo image display device (laminate)>
Example 1 except that in producing the polarizing film, a compound having a nitroxy radical represented by general formula (8) or a nitroxide group was used instead of general formula (9) for both adhesives used. A polarizing film, a double-sided protective polarizing film, and a pseudo image display device (laminate) were produced in the same manner as above. The single transmittance of the polarizing film was 39.6%.
<実施例4>
<偏光膜、偏光フィルム、疑似画像表示装置(積層体)の作製>
偏光フィルムの作製において、接着剤として、アセトアセチル基を含有するポリビニルアルコール樹脂とメチロールメラミンと一般式(6)で示されるニトロキシラジカル、またはニトロキシド基を有する化合物とを重量比7:2:1で含有する水溶液を用いたこと以外は、実施例1と同様の操作にて、偏光膜、両面保護偏光フィルム、および疑似画像表示装置(積層体)を作製した。偏光フィルムの単体透過率は39.7%であった。
<Example 4>
<Production of polarizing film, polarizing film, and pseudo image display device (laminate)>
In producing a polarizing film, as an adhesive, a polyvinyl alcohol resin containing an acetoacetyl group, methylol melamine, and a nitroxy radical represented by general formula (6) or a compound having a nitroxide group are used in a weight ratio of 7:2:1. A polarizing film, a double-sided protective polarizing film, and a pseudo image display device (laminate) were produced in the same manner as in Example 1, except that an aqueous solution containing . The single transmittance of the polarizing film was 39.7%.
<比較例1>
<偏光膜、偏光フィルム、疑似画像表示装置(積層体)の作製>
偏光フィルムの作製において、一般式(9)で示されるニトロキシラジカル、またはニトロキシド基を有する化合物を添加しなかったこと以外は、実施例1と同様の操作にて、偏光膜、偏光フィルム、および疑似画像表示装置(積層体)を作製した。偏光フィルムの単体透過率は39.6%であった。
<Comparative example 1>
<Production of polarizing film, polarizing film, and pseudo image display device (laminate)>
In producing the polarizing film, a polarizing film, a polarizing film, and A pseudo image display device (laminate) was produced. The single transmittance of the polarizing film was 39.6%.
上記で得られた実施例および比較例の疑似画像表示装置(積層体)を用い、上記の[高温環境下における単体透過率の評価]を行った。結果を表1に示す。 Using the pseudo image display devices (laminates) of the Examples and Comparative Examples obtained above, the above [Evaluation of single transmittance in a high temperature environment] was performed. The results are shown in Table 1.
Claims (6)
前記偏光膜は、ポリビニルアルコール系フィルムにヨウ素が吸着配向して形成されており、
前記接着剤層は、ニトロキシラジカル、またはニトロキシド基を有する化合物を含み、かつ水系接着剤から形成される層であることを特徴とする偏光フィルム。 A polarizing film in which a transparent protective film is bonded to at least one surface of the polarizing film via an adhesive layer,
The polarizing film is formed by adsorbing and orienting iodine on a polyvinyl alcohol film,
The polarizing film is characterized in that the adhesive layer contains a compound having a nitroxy radical or a nitroxide group and is formed from a water-based adhesive .
An image display device comprising a front transparent member on the polarizing film or laminated polarizing film side of the image display panel according to claim 5.
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- 2019-11-12 KR KR1020207024312A patent/KR102266082B1/en active IP Right Grant
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TW202030081A (en) | 2020-08-16 |
WO2020100845A1 (en) | 2020-05-22 |
JPWO2020100843A1 (en) | 2021-02-15 |
KR102266082B1 (en) | 2021-06-17 |
CN113031145A (en) | 2021-06-25 |
CN111819259A (en) | 2020-10-23 |
CN113031145B (en) | 2023-01-17 |
CN111819259B (en) | 2021-03-16 |
JP7399807B2 (en) | 2023-12-18 |
WO2020100843A1 (en) | 2020-05-22 |
KR102268257B1 (en) | 2021-06-23 |
JP6732157B1 (en) | 2020-07-29 |
JP2020126264A (en) | 2020-08-20 |
KR20200105724A (en) | 2020-09-08 |
TW202023831A (en) | 2020-07-01 |
KR20200106979A (en) | 2020-09-15 |
JP2020194166A (en) | 2020-12-03 |
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