JP2013037071A - Near-infrared absorbing pressure-sensitive adhesive, and near-infrared shield film and display near-infrared shield using the same - Google Patents
Near-infrared absorbing pressure-sensitive adhesive, and near-infrared shield film and display near-infrared shield using the same Download PDFInfo
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- JP2013037071A JP2013037071A JP2011171059A JP2011171059A JP2013037071A JP 2013037071 A JP2013037071 A JP 2013037071A JP 2011171059 A JP2011171059 A JP 2011171059A JP 2011171059 A JP2011171059 A JP 2011171059A JP 2013037071 A JP2013037071 A JP 2013037071A
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- Prior art keywords
- infrared
- group
- sensitive adhesive
- infrared absorbing
- shielding film
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
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- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
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- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
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- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000090 poly(aryl ether) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
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- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 238000004381 surface treatment Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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Images
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、近赤外線吸収性粘着剤、該近赤外線吸収性粘着剤を用いた近赤外線遮蔽フィルム、並びに、該近赤外線遮蔽フィルムを用いたディスプレイ用近赤外線遮蔽体に関するものである。 The present invention relates to a near-infrared absorbing adhesive, a near-infrared shielding film using the near-infrared absorbing adhesive, and a near-infrared shielding for a display using the near-infrared shielding film.
プラズマディスプレイパネル（ＰＤＰ）においては、８００〜１１００ｎｍの波長の近赤外線が発生するため、近赤外線を使用する機器（例えば、家電用リモコン）に誤作動を生じさせるなどの問題を有していた。そこで、この問題に対して、上記のディスプレイの表面に近赤外線を遮蔽する部材が設けられてきた。また、これらのディスプレイ表面においては、ハードコート、反射防止、防眩等の機能層を設ける必要もあることから、近赤外線を吸収する近赤外線吸収色素を粘着剤に含有させて近赤外線遮蔽機能を粘着剤層に付与する技術も広く用いられている。このような近赤外線吸収色素としては、近赤外線の吸収能が高く、可視光領域での透明性が高いことから、ジイモニウム系色素がよく用いられている。 In the plasma display panel (PDP), near infrared rays having a wavelength of 800 to 1100 nm are generated, which causes problems such as causing malfunctions in devices using the near infrared rays (for example, a remote control for home appliances). In view of this problem, a member for shielding near infrared rays has been provided on the surface of the display. In addition, since it is necessary to provide a hard coat, antireflection, antiglare and other functional layers on the surface of these displays, a near infrared absorbing dye that absorbs near infrared rays is included in the adhesive to provide a near infrared shielding function. A technique for applying to the pressure-sensitive adhesive layer is also widely used. As such a near-infrared absorbing dye, a diimonium dye is often used because it has a high near-infrared absorptivity and high transparency in the visible light region.
ところが、ジイモニウム系色素は、粘着剤中では反応性が高く、アミニウム塩化合物に分解される。そのため、近赤外線の吸収能が低下するとともに、粘着剤が着色してしまい、ディスプレイ表面への用途においては実用に供し得ないものとなる。このような問題に対しては、ガラス転移温度が０℃以下である樹脂（Ｂ）及び溶剤（Ｄ）を含む組成物中にジイモニウム色素を溶剤中における分散体（Ａ）として分散させることにより、色素の耐久性を向上させた近赤外線吸収粘着剤組成物が知られている（例えば、特許文献１参照）。 However, the diimonium dye is highly reactive in the adhesive and is decomposed into an aminium salt compound. For this reason, near-infrared absorptivity is reduced, and the pressure-sensitive adhesive is colored, so that it cannot be put to practical use in applications to the display surface. For such a problem, by dispersing a diimonium dye as a dispersion (A) in a solvent in a composition containing a resin (B) having a glass transition temperature of 0 ° C. or less and a solvent (D), A near-infrared absorbing pressure-sensitive adhesive composition that improves the durability of a dye is known (for example, see Patent Document 1).
しかしながら、上記特許文献１における技術では、ジイモニウム色素の耐久性がある程度向上されるものの、実用的には十分な耐久性が得られていない。 However, with the technique in Patent Document 1, although the durability of the diimonium dye is improved to some extent, practically sufficient durability is not obtained.
本発明は、以上のような問題点に鑑みて成されたものであり、光学特性に優れることは勿論のこと、耐久性にも優れた近赤外線吸収性粘着剤並びにこれを用いた近赤外線遮蔽フィルム及びディスプレイ用近赤外線遮蔽体を提供することを目的とする。 The present invention has been made in view of the above-described problems, and has a near-infrared-absorbing pressure-sensitive adhesive having excellent optical properties as well as durability, and a near-infrared shielding using the same. It aims at providing the near-infrared shield for films and displays.
本発明の近赤外線吸収性粘着剤は、カルボキシル基のみを含有し、その酸価が５〜１５ｍｇＫＯＨ／ｇのアクリル系粘着剤と、近赤外線吸収色素として下記一般式（１）で表され、かつ、０．０１〜０．１μｍの微粒子分散状態で存在するジイモニウム塩化合物と、からなる近赤外線吸収性粘着剤であって、前記近赤外線吸収性粘着剤中において前記ジイモニウム塩化合物が３０μｍ以下の凝集体で存在し、前記ジイモニウム塩化合物は前記近赤外線吸収性粘着剤の固形分１００質量部に対して０．５〜３．０質量部含有していることを特徴としている。
本発明の近赤外線吸収性粘着剤は、前記近赤外線吸収性粘着剤に含まれるトルエンの量が５質量％以下であることが好ましい。また、本発明の近赤外線遮蔽フィルムは、上記の近赤外線吸収性粘着剤を透明基材の一方の面に設けてなることを特徴としている。さらに、本発明のディスプレイ用近赤外線遮蔽体は、上記の近赤外線遮蔽フィルムを基材に貼り合わせることで得られることを特徴としている。 In the near-infrared absorbing adhesive of the present invention, the amount of toluene contained in the near-infrared absorbing adhesive is preferably 5% by mass or less. Moreover, the near-infrared shielding film of this invention is characterized by providing said near-infrared absorptive adhesive on one surface of a transparent base material. Furthermore, the near-infrared shielding body for display of the present invention is characterized by being obtained by bonding the near-infrared shielding film to a substrate.
本発明の近赤外線吸収性粘着剤によれば、光学特性に優れることは勿論のこと、耐久性にも優れ、これを用いた近赤外線遮蔽フィルム及びディスプレイ用近赤外線遮蔽体においても、同様の効果を奏することができる。 According to the near-infrared absorbing pressure-sensitive adhesive of the present invention, it is excellent in optical properties as well as durability, and the same effect can be obtained in a near-infrared shielding film and a near-infrared shielding body for display using the same. Can be played.
次に、本発明の近赤外線吸収性粘着剤の実施形態について具体的に説明する。本発明の近赤外線吸収性粘着剤には、カルボキシル基のみを含有し、その酸価が５〜１５ｍｇＫＯＨ／ｇのアクリル系粘着剤と、後述する特定の構造を有し、０．０１〜０．１μｍの微粒子分散状態で存在するジイモニウム塩化合物とが含まれる。以下にこれらの構成要素について詳述する。 Next, an embodiment of the near-infrared absorbing adhesive of the present invention will be specifically described. The near-infrared absorbing pressure-sensitive adhesive of the present invention has only a carboxyl group and an acrylic pressure-sensitive adhesive having an acid value of 5 to 15 mgKOH / g and a specific structure described below, and has a specific structure of 0.01 to 0.00. And a diimonium salt compound existing in a fine particle dispersion state of 1 μm. Hereinafter, these components will be described in detail.
１．アクリル系粘着剤
本発明におけるアクリル系粘着剤は、側鎖の反応性官能基がカルボキシル基のみであり、その酸価が５〜１５ｍｇＫＯＨ／ｇであることが必須である。酸価は６〜１０ｍｇＫＯＨ／ｇであることが好ましい。なお、酸価とは、粘着剤１ｇを中和するのに必要な水酸化カリウムのｍｇ量である。本発明においては、アクリル系粘着剤の酸価が５ｍｇＫＯＨ／ｇ未満、および１５ｍｇＫＯＨ／ｇを超えるとジイモニウム塩化合物の分解現象や凝集が不安定状態となり耐久性（特に耐熱性）が低下してしまう。
1. Acrylic pressure-sensitive adhesive In the acrylic pressure-sensitive adhesive of the present invention, it is essential that the reactive functional group of the side chain is only a carboxyl group, and the acid value thereof is 5 to 15 mgKOH / g. The acid value is preferably 6 to 10 mgKOH / g. The acid value is the mg amount of potassium hydroxide required to neutralize 1 g of the pressure-sensitive adhesive. In the present invention, if the acid value of the acrylic pressure-sensitive adhesive is less than 5 mgKOH / g and more than 15 mgKOH / g, the decomposition phenomenon and aggregation of the diimonium salt compound become unstable and the durability (particularly heat resistance) decreases. .
側鎖の官能基をカルボキシル基のみとしたアクリル系粘着剤は、主に主鎖構造を形成するモノマー成分、官能基であるカルボキシル基を含有したモノマー成分及びその他の官能基を有さないモノマー成分を共重合させることにより得ることができる。 Acrylic pressure-sensitive adhesives that have only a carboxyl group as the side chain functional group are monomer components that mainly form a main chain structure, monomer components that contain a carboxyl group that is a functional group, and monomer components that do not have other functional groups. Can be obtained by copolymerization.
上記の主に主鎖構造を形成するモノマー成分は、炭素数が１以上１２以下であるアルキル基を有する（メタ）アクリル酸エステルであることが好ましい。また、このアルキル基は、直鎖型、分岐型、脂環式、多環性脂環式、芳香環式又は多環性芳香環式のアルキル基のいずれであってもよい。 The monomer component mainly forming the main chain structure is preferably a (meth) acrylic acid ester having an alkyl group having 1 to 12 carbon atoms. The alkyl group may be any of a linear, branched, alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic ring alkyl group.
このような主に主鎖構造を形成するモノマー成分の具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、ｉ−オクチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ−ドデシル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート等が挙げられる。 Specific examples of the monomer component that mainly forms the main chain structure include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meta Acrylate, n-dodecyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( And (meth) acrylate.
また、上記の官能基であるカルボキシル基を含有したモノマー成分は、カルボキシル基含有（メタ）アクリルモノマーが好ましく、具体的には、アクリル酸及びメタクリル酸が挙げられる。このようなカルボキシル基含有（メタ）アクリルモノマーは、カルボキシル基が架橋点となるため、この配合量を制御することにより、粘着性や酸価を調整することが可能である。 Moreover, the monomer component containing the carboxyl group which is said functional group is preferably a carboxyl group-containing (meth) acrylic monomer, and specifically includes acrylic acid and methacrylic acid. In such a carboxyl group-containing (meth) acrylic monomer, the carboxyl group serves as a cross-linking point, and thus the adhesiveness and acid value can be adjusted by controlling the blending amount.
さらに、上記のその他の官能基を有さないモノマー成分は、本発明におけるアクリル系粘着剤の側鎖において反応性を有する官能基を形成させないものであることが必須である。反応性を有する官能基としては、水酸基、アミノ基、グリシジル基等が例示できる。官能基を有さないモノマー成分は具体的には、ベンジル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、トリシクロデカニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート等が挙げられ、さらには、メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート、エトキシエトキシエチル（メタ）アクリレート等の（メタ）アクリレート類；α−メチルスチレン、ビニルトルエン、スチレン等のスチレン系単量体；メチルビニルエーテル、エチルビニルエーテル、イソブチルビニルエーテル等のビニルエーテル系単量体；（メタ）アクリロニトリル；塩化ビニル；塩化ビニリデン；酢酸ビニル；ビニルケトン；ビニルピリジン；ビニルカルバゾール等も挙げることができる。 Furthermore, it is essential that the monomer component having no other functional group described above does not form a reactive functional group in the side chain of the acrylic pressure-sensitive adhesive in the present invention. Examples of the functional group having reactivity include a hydroxyl group, an amino group, and a glycidyl group. Specific examples of monomer components having no functional group include benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl ( (Meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and the like. Furthermore, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate ( (Meth) acrylates; styrene monomers such as α-methylstyrene, vinyltoluene and styrene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and isobutyl vinyl ether Mer; (meth) acrylonitrile, vinyl chloride; vinylidene chloride; vinyl acetate; vinyl ketones, vinyl pyridine, vinyl carbazole or the like can also be mentioned.
本発明における各モノマー成分の含有量は、主に主鎖構造を形成するモノマー成分が６０質量％以上９９．９質量％以下であり、官能基であるカルボキシル基を含有したモノマー成分が０．１質量％以上２０質量％以下であり、その他の官能基を有さないモノマー成分が０質量％以上３０質量％以下であることが好ましく、官能基であるカルボキシル基を含有したモノマー成分が０．１質量％以上１０質量％以下であることがより好ましい。 The content of each monomer component in the present invention is such that the monomer component mainly forming the main chain structure is 60% by mass or more and 99.9% by mass or less, and the monomer component containing a carboxyl group which is a functional group is 0.1%. It is preferable that the monomer component having no more than 20% by mass and no other functional group is 0% by mass or more and 30% by mass or less, and the monomer component containing a functional carboxyl group is 0.1%. More preferably, the content is from 10% by mass to 10% by mass.
また、本発明におけるアクリル系粘着剤の重合に使用される開始剤としては、過酸化物系、アゾ系等が挙げられ、過酸化物系の開始剤としては、パーブチルＯ、パーヘキシルＯ等のパーオキシエステル系；パーロイルＬ、パーロイルＯ等のパーオキシジカーボネート系；ナイパーＢＷ、ナイパーＢＭＴ等のジアシルパーオキサイド系；パーヘキサ３Ｍ、パーヘキサＭＣ等のパーオキシケタール系；パーブチルＰ、パークミルＤ等のジアルキルパーオキサイド系；パークミルＰ、パーメンタＨ等のハイドロパーオキサイド系等が挙げられ、いずれも日本油脂社から市販されている。また、アゾ系の開始剤としては、ＡＢＮ−Ｅ、ＡＢＮ−Ｒ、ＡＢＮ−Ｖ等が挙げられ、いずれも日本ヒドラジン工業社から市販されている。 In addition, examples of the initiator used for the polymerization of the acrylic pressure-sensitive adhesive in the present invention include peroxide-based and azo-based initiators, and examples of the peroxide-based initiator include perbutyl O and perhexyl O. Peroxydicarbonates such as Parroyl L and Parroyl O; Diacyl peroxides such as Nyper BW and Nyper BMT; Peroxyketals such as Perhexa 3M and Perhexa MC; Dialkyl pars such as Perbutyl P and Parkmill D Oxide type; Hydroperoxide type such as Park Mill P, Permenta H, and the like can be mentioned, all of which are commercially available from NOF Corporation. Examples of the azo initiator include ABN-E, ABN-R, ABN-V, and the like, all of which are commercially available from Nippon Hydrazine Kogyo.
さらに、アクリル系粘着剤の重合においては、必要に応じて連鎖移動剤を使用してもよく、具体的には、ノルマルドデシルメルカプタン、ジチオグリコール、チオグリコール酸オクチル、メルカプトエタノール等のチオール化合物等を使用することができる。また、アクリル系粘着剤の重合は無溶剤で行ってもよいし、有機溶剤中で行ってもよい。有機溶剤中で重合する際には、トルエン、キシレン等の芳香族系溶剤；酢酸エチル、酢酸ブチル等のエステル系溶剤；メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン（ＭＩＢＫ）等のケトン系溶剤；その他の公知の有機溶剤が使用できる。使用する有機溶剤の種類は得られる樹脂の溶解性、重合温度を考慮して決められるが、乾燥時の残存溶剤の残りにくさの点からトルエン、酢酸エチル、メチルエチルケトン等の沸点が１２０℃以下の有機溶剤が好ましい。さらに、アクリル系粘着剤中における凝集体の安定性の観点から、ジイモニウム色素の溶解性が５質量％以下の有機溶剤が好ましい。また、アクリル系粘着剤は単一の組成からなるものでもよいし、異なる組成のポリマーを複合化したポリマーアロイやポリマーブレンドであってもよい。 Further, in the polymerization of the acrylic pressure-sensitive adhesive, a chain transfer agent may be used as necessary. Specifically, thiol compounds such as normal dodecyl mercaptan, dithioglycol, octyl thioglycolate, mercaptoethanol, etc. Can be used. In addition, the polymerization of the acrylic pressure-sensitive adhesive may be performed without a solvent or in an organic solvent. When polymerizing in an organic solvent, aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone (MEK) and methyl isobutyl ketone (MIBK); A known organic solvent can be used. The type of organic solvent to be used is determined in consideration of the solubility of the obtained resin and the polymerization temperature, but the boiling point of toluene, ethyl acetate, methyl ethyl ketone, etc. is 120 ° C. or lower in terms of the difficulty of remaining the residual solvent during drying. Organic solvents are preferred. Furthermore, from the viewpoint of the stability of the aggregate in the acrylic pressure-sensitive adhesive, an organic solvent having a solubility of diimonium dye of 5% by mass or less is preferable. The acrylic pressure-sensitive adhesive may have a single composition, or may be a polymer alloy or polymer blend in which polymers having different compositions are combined.
２．ジイモニウム塩化合物
本発明における近赤外線吸収色素は、下記一般式（１）で表され、かつ、０．０１〜０．１μｍの微粒子分散状態で存在するジイモニウム塩化合物である。微粒子分散状態とは一次粒子の形態で分散している状態をいう。他の材料と混合する際に、ジイモニウム塩化合物が微粒子状態となっていればよい。例えば、粉体の状態で微粒子分散状態になっていてもよいし、溶媒中に微粒子分散状態にて存在していてもよい。溶媒中においてはジイモニウム塩化合物が凝集体を形成する場合があるため、微粒子分散状態にするために超音波処理等の処理を行うことが好ましい。
上記一般式（１）において、Ｘは、ジイモニウム塩化合物におけるアニオンであり、具体的には、ヘキサフルオロアンチモン酸イオン又はヘキサフルオロリン酸イオンである。また、Ｒ１〜Ｒ８は、アルキル基、環状アルキル基、環状アルキル基を有するアルキレン基、及びアルコキシ基を有するアルキレン基のいずれかであり、全てが同一であっても異なっていてもよいが、カチオン構造が対称となり、アクリル系粘着剤中において良好に凝集体を形成させるため、全て同じであることが好ましい。 In the general formula (1), X is an anion in the diimonium salt compound, specifically, hexafluoroantimonate ion or hexafluorophosphate ion. R 1 to R 8 are any one of an alkyl group, a cyclic alkyl group, an alkylene group having a cyclic alkyl group, and an alkylene group having an alkoxy group, all of which may be the same or different. In order to make the cation structure symmetrical and form an aggregate well in the acrylic pressure-sensitive adhesive, it is preferable that they are all the same.
Ｒ１〜Ｒ８におけるアルキル基は、炭素数１〜１０の直鎖状又は分岐状のものが好ましく、具体的には、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−アミル基、ｉ−アミル基、１−メチルブチル基、２−メチルブチル基、１−エチルブチル基、２−エチルブチル基、２−ジメチルプロピル基、１−エチルプロピル基、１，２−ジメチルプロピル基、１，１−ジメチルプロピル基、ネオペンチル基、ｎ−ヘキシル基、４，４，４−トリフルオロブチル基、２，２，２−トリフルオロエチル基、パーフルオロブチル基等が挙げられる。これらの中でも、ｉ−プロピル基、ｉ−ブチル基、ｉ−アミル基等の炭素数３〜６の分岐状アルキル基が好ましい。また、Ｒ１〜Ｒ８における環状アルキル基は、炭素数３〜１２の環状のアルキル基が好ましく、具体的には、シクロペンチル基、シクロヘキシル基等が挙げられる。 The alkyl group in R 1 to R 8 is preferably a linear or branched group having 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- Butyl group, i-butyl group, s-butyl group, t-butyl group, n-amyl group, i-amyl group, 1-methylbutyl group, 2-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 2- Dimethylpropyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, 4,4,4-trifluorobutyl group, 2,2,2 -A trifluoroethyl group, a perfluorobutyl group, etc. are mentioned. Among these, branched alkyl groups having 3 to 6 carbon atoms such as i-propyl group, i-butyl group and i-amyl group are preferable. The cyclic alkyl group in R 1 to R 8 is preferably a cyclic alkyl group having 3 to 12 carbon atoms, and specific examples include a cyclopentyl group and a cyclohexyl group.
また、Ｒ１〜Ｒ８における環状アルキル基を有するアルキレン基は、炭素数１〜１０の直鎖状又は分岐状のアルキレン基であり、炭素数３〜１２の環状のアルキル基を有することが好ましく、アルキレン基の炭素数が１〜４であり、環状アルキル基の炭素数が５〜６であることがより好ましい。具体的には、シクロペンチルメチル基、シクロヘキシルメチル基、２−シクロペンチルエチル基、２−シクロペンチルプロピル基、３−シクロペンチルプロピル基、４−シクロペンチルブチル基、２−シクロヘキシルエチル基、２−シクロヘキシルプロピル基、３−シクロヘキシルプロピル基、４−シクロヘキシルブチル基等が挙げられる。これらの中でも、シクロペンチルメチル基、シクロヘキシルメチル基、２−シクロヘキシルエチル基、２−シクロヘキシルプロピル基、３−シクロヘキシルプロピル基及び４−シクロヘキシルブチル基が好ましく、シクロペンチルメチル基及びシクロヘキシルメチル基がより好ましく、シクロヘキシルメチル基が最も好ましい。さらに、Ｒ１〜Ｒ８におけるアルコキシ基を有するアルキレン基は、炭素数１〜１０の直鎖状又は分岐状のアルキレン基であり、炭素数１〜１０のアルコキシ基を有することが好ましく、具体的には、メトキシメチル基、エトキシメチル基、ｎ−プロポキシメチル基、２−イソプロポキシメチル基、イソブトキシメチル基、ｓｅｃ−ブトキシメチル基、ｔ−ブトキシメチル基、１−メトキシエチル基、２−メトキシエチル基、１−エトキシエチル基、２−エトキシエチル基、２−プロポキシエチル基、１−プロポキシエチル基、２−イソプロポキシエチル基、１−イソプロポキシエチル基、４−メトキシブチル基、３−メトキシブチル基、２−メトキシブチル基、４−エトキシブチル基、３−エトキシブチル基、２−メトキシ−１−メチルエチル基、２−エトキシ−１−メチルエチル基、テトラヒドロフラニル基、テトラヒドロピラニル基等が挙げられる。 Further, the alkylene group having a cyclic alkyl group in R 1 to R 8 is a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably has a cyclic alkyl group having 3 to 12 carbon atoms. More preferably, the alkylene group has 1 to 4 carbon atoms and the cyclic alkyl group has 5 to 6 carbon atoms. Specifically, cyclopentylmethyl group, cyclohexylmethyl group, 2-cyclopentylethyl group, 2-cyclopentylpropyl group, 3-cyclopentylpropyl group, 4-cyclopentylbutyl group, 2-cyclohexylethyl group, 2-cyclohexylpropyl group, 3 -A cyclohexylpropyl group, 4-cyclohexylbutyl group, etc. are mentioned. Among these, a cyclopentylmethyl group, a cyclohexylmethyl group, a 2-cyclohexylethyl group, a 2-cyclohexylpropyl group, a 3-cyclohexylpropyl group, and a 4-cyclohexylbutyl group are preferable, a cyclopentylmethyl group and a cyclohexylmethyl group are more preferable, and cyclohexyl A methyl group is most preferred. Furthermore, the alkylene group having an alkoxy group in R 1 to R 8 is a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably has an alkoxy group having 1 to 10 carbon atoms. Methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, 2-isopropoxymethyl group, isobutoxymethyl group, sec-butoxymethyl group, t-butoxymethyl group, 1-methoxyethyl group, 2-methoxy Ethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, 2-propoxyethyl group, 1-propoxyethyl group, 2-isopropoxyethyl group, 1-isopropoxyethyl group, 4-methoxybutyl group, 3-methoxy Butyl group, 2-methoxybutyl group, 4-ethoxybutyl group, 3-ethoxybutyl group, 2-methoxy-1-methyl Butyl group, 2-ethoxy-1-methylethyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like.
上記のような構造を有する本発明におけるジイモニウム塩化合物は、近赤外線吸収性粘着剤の固形分１００質量部に対して０．５〜３．０質量部となるように、前述のアクリル系粘着剤に混合・分散させることにより、近赤外線吸収遮蔽体として必要な機能を有することができる。本発明におけるジイモニウム塩化合物の凝集体とは、０．０１〜０．１μｍの分散状態となった微粒子ではなく、これらが多数集まって凝集されたものである。具体的なジイモニウム塩化合物の凝集体の大きさは、０．１μｍ超〜３０μｍ以下であり、１μｍ〜３０μｍの範囲にあることが好ましい。 The above-mentioned acrylic pressure-sensitive adhesive is used so that the diimonium salt compound in the present invention having the above structure is 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the solid content of the near-infrared absorbing adhesive. By mixing / dispersing into the near-infrared absorbing shield, it can have a necessary function as a near-infrared absorbing shield. The aggregate of the diimonium salt compound in the present invention is not a fine particle in a dispersed state of 0.01 to 0.1 μm, but a large number of these aggregated together. Specifically, the size of the aggregate of the diimonium salt compound is more than 0.1 μm to 30 μm, and preferably in the range of 1 μm to 30 μm.
上記のジイモニウム塩化合物の含有量が０．５質量部未満では、近赤外線吸収機能が発揮されず、一方、３．０質量部を超えると、オーバースペックとなりコスト的にも適切ではない。なお、本発明の近赤外線吸収性粘着剤においては、ジイモニウム塩化合物に良好に凝集体を形成させるために、近赤外線吸収性粘着剤に含まれるトルエンの量を５質量％以下とすることが好ましい。近赤外線吸収性粘着剤または近赤外線吸収性粘着剤に溶媒を加えた近赤外線吸収性粘着剤塗料において、それぞれトルエンの量が５質量％を超えると、ジイモニウム塩化合物の凝集が進みやすくなり、粗大な（３０μｍを超える）ジイモニウム塩化合物の凝集体が形成される。近赤外線吸収性粘着剤または近赤外線吸収性粘着剤塗料に含まれるトルエンの量を５質量％以下とすることで、ジイモニウム塩化合物の凝集径を適正化できるとともに、後述する近赤外線遮蔽フィルムを製造する際に、製造開始時と製造終了時において、品質を一定にすることができる。トルエン以外の溶媒としては、上述した芳香族系溶剤、エステル系溶剤、ケトン系溶剤等を使用することができる。 If the content of the dimonium salt compound is less than 0.5 parts by mass, the near-infrared absorbing function is not exhibited. On the other hand, if it exceeds 3.0 parts by mass, it becomes over-specification and is not appropriate in terms of cost. In the near-infrared absorbing adhesive of the present invention, the amount of toluene contained in the near-infrared absorbing adhesive is preferably 5% by mass or less in order to favorably form aggregates in the diimonium salt compound. . In the near-infrared-absorbing pressure-sensitive adhesive or near-infrared-absorbing pressure-sensitive adhesive paint, if the amount of toluene exceeds 5% by mass, diimonium salt compounds tend to aggregate and become coarse. Aggregates of dimonium salt compounds (over 30 μm) are formed. By adjusting the amount of toluene contained in the near-infrared absorbing adhesive or near-infrared absorbing adhesive paint to 5% by mass or less, the aggregate diameter of the diimonium salt compound can be optimized and a near-infrared shielding film described later is manufactured. In doing so, the quality can be made constant at the start of manufacture and at the end of manufacture. As the solvent other than toluene, the above-mentioned aromatic solvents, ester solvents, ketone solvents and the like can be used.
さらに、本発明の近赤外線吸収性粘着剤においては、上記ジイモニウム塩化合物に加えて、他の近赤外線吸収色素を添加することができる。添加可能な他の近赤外線吸収色素としては、公知のシアニン系色素、ポリメチン系色素、スクアリリウム系色素、ポルフィリン系色素、金属ジチオール錯体系色素、フタロシアニン系色素、ジイモニウム系色素、無機酸化物粒子等が挙げられる。これらの中でも、上記ジイモニウム塩化合物に対してクエンチャー効果を奏し得ることから、フタロシアニン系色素が好ましい。なお、クエンチャー効果とは、励起状態にある活性分子を脱励起させる効果である。 Furthermore, in the near-infrared absorbing pressure-sensitive adhesive of the present invention, other near-infrared absorbing dyes can be added in addition to the diimonium salt compound. Other near infrared absorbing dyes that can be added include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, and the like. Can be mentioned. Among these, phthalocyanine dyes are preferable because they can exhibit a quencher effect on the diimonium salt compound. The quencher effect is an effect of de-exciting active molecules in an excited state.
上記のフタロシアニン系色素、シアニン系色素及び金属ジチオール錯体系色素の最大吸収波長が８００〜９５０ｎｍであるため、これらを本発明の近赤外線吸収性粘着に添加し、この近赤外線吸収性粘着を用いて薄型ディスプレイ用光学フィルターを作製した場合には、上記ジイモニウム塩化合物のみを用いた場合に比べて、より広範囲な８００〜１１００ｎｍの近赤外線を効果的に吸収することができる。 Since the maximum absorption wavelength of the above phthalocyanine dye, cyanine dye and metal dithiol complex dye is 800 to 950 nm, these are added to the near infrared absorbing adhesive of the present invention, and this near infrared absorbing adhesive is used. When an optical filter for a thin display is produced, a wider range of near infrared rays of 800 to 1100 nm can be effectively absorbed as compared with the case where only the dimonium salt compound is used.
また、本発明の近赤外線吸収性粘着剤においては、必要に応じて可視光を吸収する色素を添加することもできる。このような可視光を吸収する色素としては、シアニン系、フタロシアニン系、ナフタロシアニン系、ポルフィリン系、テトラアザポルフィリン系、金属ジチオール錯体系、スクアリリウム系、アズレニウム系、ジフェニルメタン系、トリフェニルメタン系、オキサジン系、アジン系、チオピリリウム系、ビオローゲン系、アゾ系、アゾ金属錯体系、ビスアゾ系、アントラキノン系、ペリレン系、インダンスロン系、ニトロソ系、インジコ系、アゾメチン系、キサンテン系、オキサノール系、インドアニリン系、キノリン系、ジケトピロロピロール系等、従来公知の色素を広く使用することができる。 Moreover, in the near-infrared absorptive adhesive of this invention, the pigment | dye which absorbs visible light can also be added as needed. Examples of dyes that absorb visible light include cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metal dithiol complex, squarylium, azurenium, diphenylmethane, triphenylmethane, and oxazine. , Azine, thiopyrylium, viologen, azo, azo metal complex, bisazo, anthraquinone, perylene, indanthrone, nitroso, indico, azomethine, xanthene, oxanol, indoaniline Conventionally known dyes such as quinoline, quinoline, and diketopyrrolopyrrole can be widely used.
さらに、本発明の近赤外線吸収性粘着剤を用いてＰＤＰ用近赤外線遮蔽体を作製する場合には、不要なネオン発光を吸収するために、最大吸収波長が５５０〜６５０ｎｍである可視吸収色素を併用することが好ましい。このようなネオン発光を吸収する色素としては、シアニン色素、テトラアザポルフィリン色素等を用いることができ、具体的には、旭電化工業社製の商品名：アデカアークルズＴＹ−１０２、アデカアークルズＴＹ−１４及びアデカアークルズＴＹ−１５、山田化学工業社製の商品名：ＴＡＰ−２、ＴＡＰ−１８及びＴＡＰ−４５、山本化成製の商品名：ＰＤ３２０、ＰＤ３１９、林原生物化学研究所製の商品名：ＮＫ−５４５１、ＮＫ−５５３２及びＮＫ−５４５０等が挙げられる。ネオン発光を吸収するための色素の添加量は、色素の種類によって異なるが、最大吸収波長での透過率が２０〜８０％程度になるように添加することが好ましい。 Furthermore, when producing a near-infrared shield for PDP using the near-infrared absorbing adhesive of the present invention, in order to absorb unnecessary neon light emission, a visible absorption dye having a maximum absorption wavelength of 550 to 650 nm is used. It is preferable to use together. As such a dye that absorbs neon light emission, a cyanine dye, a tetraazaporphyrin dye, and the like can be used. Specifically, trade names: Adeka Arcles TY-102, Adeka Arcles manufactured by Asahi Denka Kogyo Co., Ltd. TY-14 and Adeka Arcles TY-15, trade names made by Yamada Chemical Co., Ltd .: TAP-2, TAP-18 and TAP-45, trade names made by Yamamoto Kasei: PD320, PD319, manufactured by Hayashibara Biochemical Research Institute Product names: NK-5451, NK-5532, NK-5450 and the like. The addition amount of the dye for absorbing neon emission varies depending on the kind of the dye, but it is preferable to add the dye so that the transmittance at the maximum absorption wavelength is about 20 to 80%.
また、本発明の近赤外線吸収性粘着剤を透明基材の一方の面に設けてなる近赤外線遮蔽フィルムにおいては、色調を調整するために、調色用の可視光吸収色素を添加してもよい。このような調色用の色素としては、１：２クロム錯体、１：２コバルト錯体、銅フタロシアニン、アントラキノン、ジケトピロロピロール等が使用でき、具体的には、チバ・スペシャリティ・ケミカルズ製の商品名：オラゾールブルーＧＮ、オラゾールブルーＢＬ、オラゾールレッド２Ｂ、オラゾールレッドＧ、オラゾールブラックＣＮ、オラゾールイエロー２ＧＬＮ、オラゾールイエロー２ＲＬＮ、マイクロリスＤＰＰレッドＢ−Ｋ等が挙げられる。 Moreover, in the near infrared ray shielding film in which the near infrared ray absorbing pressure-sensitive adhesive of the present invention is provided on one surface of the transparent substrate, a visible light absorbing dye for toning may be added to adjust the color tone. Good. Examples of such toning pigments include 1: 2 chromium complex, 1: 2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole, and the like. Specifically, products manufactured by Ciba Specialty Chemicals Name: Orazole Blue GN, Orazole Blue BL, Orazole Red 2B, Orazole Red G, Orazole Black CN, Orazole Yellow 2GLN, Orazole Yellow 2RLN, Microlith DPP Red BK and the like.
さらに、本発明の近赤外線吸収性粘着剤には、その性能を損なわない範囲で、種々の添加剤を加えることができる。このような添加剤としては、フィルムやコーティング膜等を形成する樹脂組成物に使用される従来公知の添加剤を用いることができ、具体的には、分散剤、レベリング剤、消泡剤、粘性調整剤、つや消し剤、粘着付与剤、帯電防止剤、酸化防止剤、紫外線吸収材、光安定化剤、消光剤、硬化剤、アンチブロッキング剤等が挙げられる。なお、硬化剤としては、イソシアネート化合物、チオール化合物、エポキシ化合物、アミン系化合物、イミン系化合物、オキサゾリン化合物、シランカップリング剤、ＵＶ硬化剤等を使用することができる。 Furthermore, various additives can be added to the near-infrared absorbing pressure-sensitive adhesive of the present invention as long as the performance is not impaired. As such an additive, a conventionally known additive used in a resin composition for forming a film, a coating film or the like can be used. Specifically, a dispersant, a leveling agent, an antifoaming agent, a viscosity Examples of the adjusting agent, matting agent, tackifier, antistatic agent, antioxidant, ultraviolet absorber, light stabilizer, quencher, curing agent, and antiblocking agent. As the curing agent, an isocyanate compound, a thiol compound, an epoxy compound, an amine compound, an imine compound, an oxazoline compound, a silane coupling agent, a UV curing agent, or the like can be used.
３．近赤外線遮蔽フィルム
本発明の近赤外線遮蔽フィルムは、上記の近赤外線吸収性粘着剤を透明基材の一方の面に設けてなるものである。透明基材としては、一般に光学材に使用し得るものであって、実質的に透明であれば特に制限はなく、具体的には、ガラス；シクロポリオレフィン、非晶質ポリオレフィン等のオレフィン系ポリマー；ポリメチルメタクリレート等のメタクリル系ポリマー；酢酸ビニルやハロゲン化ビニル等のビニル系ポリマー；ＰＥＴ等のポリエステル；ポリカーボネート、ブチラール樹脂等のポリビニルアセタール；ポリアリールエーテル系樹脂；ラクトン環含有樹脂フィルム等が挙げられる。
3. Near-infrared shielding film The near-infrared shielding film of this invention provides said near-infrared absorptive adhesive in one surface of a transparent base material. The transparent substrate is generally usable as an optical material and is not particularly limited as long as it is substantially transparent. Specifically, glass; olefin polymers such as cyclopolyolefin and amorphous polyolefin; Methacrylic polymers such as polymethyl methacrylate; Vinyl polymers such as vinyl acetate and vinyl halides; Polyesters such as PET; Polyvinyl acetals such as polycarbonate and butyral resins; Polyaryl ether resins; Lactone ring-containing resin films .
さらに、透明基材には、コロナ放電処理、火炎処理、プラズマ処理、グロー放電処理、粗面化処理、薬品処理等の従来公知の方法による表面処理や、アンカーコート剤やプライマー等のコーティングが施されてもよい。また、上記透明基材を構成する基材樹脂には、公知の添加剤、耐熱老化防止剤、滑剤、帯電防止剤等の配合が可能である。上記透明基材は、公知の射出成形、Ｔダイ成形、カレンダー成形、圧縮成形等の方法や、有機溶剤に溶融させてキャスティングする方法などを用い、フィルムまたはシート状に成形される。かかる透明基材を構成する基材は、未延伸でも延伸されていてもよく、また他の基材と積層されていてもよい。 Further, the transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, or coating with an anchor coating agent or a primer. May be. The base resin constituting the transparent base material can be blended with known additives, heat aging inhibitors, lubricants, antistatic agents, and the like. The transparent substrate is formed into a film or a sheet using a known method such as injection molding, T-die molding, calendar molding, compression molding, or a method of casting by melting in an organic solvent. The base material constituting the transparent base material may be unstretched or stretched, and may be laminated with another base material.
コーティング法によって近赤外線遮蔽フィルムを作製する場合には、透明基材はＰＥＴフィルムであることが好ましく、特に易接着処理をしたＰＥＴフィルムが好適である。具体的には、コスモシャインＡ４３００（東洋紡績製）、ルミラーＵ３４（東レ製）、メリネックス７０５（帝人デュポン製）等が挙げられる。また、ＴＡＣ（トリアセチルセルロース）フィルム、反射防止フィルム、ぎらつき防止フィルム、衝撃吸収フィルム、電磁波シールドフィルム、紫外線吸収フィルムなどの機能性フィルムも透明基材として使用できる。これにより、簡便に薄型ディスプレイ用や光半導体素子用の光学フィルターを作製することができる。透明基材は、フィルムであることが好ましい。 When producing a near-infrared shielding film by a coating method, the transparent substrate is preferably a PET film, and a PET film subjected to an easy adhesion treatment is particularly suitable. Specifically, Cosmo Shine A4300 (manufactured by Toyobo), Lumirror U34 (manufactured by Toray), Melinex 705 (manufactured by Teijin DuPont) and the like can be mentioned. Functional films such as a TAC (triacetylcellulose) film, an antireflection film, an antiglare film, an impact absorbing film, an electromagnetic wave shielding film, and an ultraviolet absorbing film can also be used as the transparent substrate. Thereby, the optical filter for thin displays and optical semiconductor elements can be produced simply. The transparent substrate is preferably a film.
これらの中で、ガラス、ＰＥＴフィルム、ラクトン環含有樹脂フィルム、易接着性ＰＥＴフィルム、ＴＡＣフィルム、反射防止フィルム及び電磁波シールドフィルムが透明基材として好ましく使用される。透明基材として、ガラス等の無機基材を使用する場合には、アルカリ成分が少ないものが近赤外線吸収色素の耐久性の観点から好ましい。 Among these, glass, PET film, lactone ring-containing resin film, easy-adhesive PET film, TAC film, antireflection film and electromagnetic wave shielding film are preferably used as the transparent substrate. When an inorganic base material such as glass is used as the transparent base material, a material having a small alkali component is preferable from the viewpoint of durability of the near-infrared absorbing dye.
本発明の近赤外線遮蔽フィルムの作製方法としては、本発明の近赤外線吸収性粘着剤を透明基材上にコーティングする方法や、本発明の近赤外線吸収性粘着剤を微粒子に固定化し、該微粒子を分散させた塗料を透明基材上にコーティングする方法等がある。透明基材への近赤外線吸収性粘着剤の塗布には、コンマコーター等のナイフコーター、スロットダイコーター、リップコーター等のファウンテンコーター、マイクログラビアコーター等のキスコーター、グラビアコーター、リバースロールコーター等のロールコーター、フローコーター、スプレーコーター、バーコーター等の公知の塗工機を使用することができる。乾燥・硬化方法としては、熱風、遠赤外線、ＵＶ硬化等公知の方法が使用できる。乾燥・硬化後は公知の保護フィルムとともに巻き取ってもよい。 As a method for producing the near-infrared shielding film of the present invention, a method of coating the near-infrared absorbing adhesive of the present invention on a transparent substrate, or fixing the near-infrared absorbing adhesive of the present invention to fine particles, the fine particles For example, there is a method of coating a transparent substrate with a paint having dispersed therein. For application of near-infrared absorbing adhesive to transparent substrates, rolls such as knife coaters such as comma coaters, fountain coaters such as slot die coaters and lip coaters, kiss coaters such as micro gravure coaters, gravure coaters, reverse roll coaters, etc. A known coating machine such as a coater, a flow coater, a spray coater, or a bar coater can be used. As a drying / curing method, a known method such as hot air, far-infrared ray or UV curing can be used. You may wind up with a well-known protective film after drying and hardening.
本発明の近赤外線遮蔽フィルムにおいては、上記の近赤外線吸収性粘着剤を用いることにより、可視領域の透明性及び近赤外線の遮蔽能に優れるとともに、従来の近赤外線吸収材料よりも耐熱性及び耐湿熱性にも優れるという効果を奏する。また、本発明の近赤外線遮蔽フィルムは、後述のディスプレイ用近赤外線遮蔽体のみならず、農業用フィルム、断熱フィルム、サングラス、光記録材料等の近赤外線を遮蔽するフィルターやフィルムにも適用可能である。 In the near-infrared shielding film of the present invention, by using the above-mentioned near-infrared absorbing pressure-sensitive adhesive, it is excellent in transparency in the visible region and near-infrared shielding ability, and heat resistance and moisture resistance than conventional near-infrared absorbing materials. The effect is also excellent in heat. The near-infrared shielding film of the present invention can be applied not only to the near-infrared shielding for displays described later, but also to filters and films that shield near-infrared rays such as agricultural films, heat-insulating films, sunglasses, and optical recording materials. is there.
４．ディスプレイ用近赤外線遮蔽体
本発明のディスプレイ用近赤外線遮蔽体は、上記の近赤外線遮蔽フィルムを基材に貼り合わせることで得られるものである。本発明のディスプレイ用近赤外線遮蔽体によれば、ＰＤＰ等の薄型ディスプレイにおける可視領域の透明性を維持しつつ近赤外線を良好に遮蔽することができるのは勿論のこと、優れた耐熱性及び耐湿熱性を発揮する。なお、本発明のディスプレイ用近赤外線遮蔽体をディスプレイ表面に直接張り合わせる場合には、ディスプレイ表面に強化ガラスを使用するか、衝撃吸収層を設けることが好ましい。
4). Near-infrared shield for display The near-infrared shield for display of the present invention is obtained by bonding the near-infrared shielding film to a substrate. According to the near-infrared shield for a display of the present invention, it is possible to satisfactorily shield near-infrared while maintaining transparency in a visible region in a thin display such as a PDP, as well as excellent heat resistance and moisture resistance. Demonstrate heat. When the near-infrared shield for display of the present invention is directly bonded to the display surface, it is preferable to use tempered glass or provide an impact absorbing layer on the display surface.
次に、本発明の近赤外線吸収性粘着剤、近赤外線遮蔽フィルム及びディスプレイ用近赤外線遮蔽体について、実施例を用いてさらに詳細に説明する。
１．近赤外線遮蔽フィルムの光学特性
（１）近赤外線吸収性粘着剤の調製
＜近赤外線吸収性粘着剤ａ＞
モノマーとしてブチルアクリレート（５６７．５ｇ）、アクリル酸（３２．５ｇ）を秤量し、十分に混合して重合性モノマー混合物（ａ１）を得た。次いで、この重合性モノマー混合物（ａ１）３００ｇと酢酸エチル１６０ｇとをフラスコに入れた。また、滴下ロートに３００ｇの重合性モノマー混合物（ａ１）、１６ｇの酢酸エチル及び０．１５ｇの２，２’−アゾビス（４−メトキシ−２，４−ジメチル）バレロニトリルを入れ、よく混合して滴下用混合物（ａ２）を調製した。
Next, the near-infrared absorbing adhesive, the near-infrared shielding film, and the near-infrared shielding for display according to the present invention will be described in more detail with reference to examples.
1. Optical properties of near-infrared shielding film (1) Preparation of near-infrared absorbing adhesive <Near-infrared absorbing adhesive a>
Butyl acrylate (567.5 g) and acrylic acid (32.5 g) were weighed as monomers and mixed thoroughly to obtain a polymerizable monomer mixture (a1). Next, 300 g of this polymerizable monomer mixture (a1) and 160 g of ethyl acetate were placed in a flask. Also, add 300 g of the polymerizable monomer mixture (a1), 16 g of ethyl acetate and 0.15 g of 2,2′-azobis (4-methoxy-2,4-dimethyl) valeronitrile in the dropping funnel and mix well. A dropping mixture (a2) was prepared.
次に、窒素ガスを２０ｍｌ／分で流通させながら、上記フラスコの内温を９５℃まで上昇させ、重合開始剤である２，２’−アゾビス（４−メトキシ−２，４−ジメチル）バレロニトリル（０．１５ｇ）をフラスコに投入し、重合反応を開始させた。そして、このフラスコに滴下ロートから滴下用混合物（ａ２）を９０分掛けて滴下した。滴下用混合物（ａ２）の滴下終了後、粘度の上昇に応じて酢酸エチルで希釈を行いながら、６時間の熟成を行った。反応終了後、重量平均分子量６０万、酸価２５ｍｇＫＯＨ／ｇのアクリル系粘着剤ａ３を得た。 Next, while flowing nitrogen gas at a rate of 20 ml / min, the internal temperature of the flask was raised to 95 ° C., and 2,2′-azobis (4-methoxy-2,4-dimethyl) valeronitrile as a polymerization initiator. (0.15 g) was charged into the flask to initiate the polymerization reaction. And the mixture (a2) for dripping was dripped at this flask over 90 minutes from the dropping funnel. After completion of the dropwise addition of the mixture for dropping (a2), the mixture was aged for 6 hours while being diluted with ethyl acetate as the viscosity increased. After completion of the reaction, an acrylic pressure-sensitive adhesive a3 having a weight average molecular weight of 600,000 and an acid value of 25 mgKOH / g was obtained.
また、下記一般式（１）で表される近赤外線吸収色素としてビス（ヘキサフルオロリン酸）−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス［ｐ−ジ（シクロヘキシルメチル）アミノフェニル］−ｐ−フェニレンジアミン（一般式（１）におけるＲ１〜Ｒ８は全てシクロヘキシルメチル、Ｘはヘキサフルオロリン酸）（これを色素Ａと称す）を固形分２％となるようＭＩＢＫと混合した混合液を調製し、この混合液を発振周波数３６ＫＨｚの超音波分散槽にて３０分超音波にかけて色素溶液ａ４を調製し、微粒子分散状態となった近赤外線吸収色素を得た。さらに、架橋剤としてＮ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミンをＭＥＫに溶解し、固形分１％の架橋剤溶液ａ５を調製した。そして、これらの色素溶液ａ４と架橋剤溶液ａ５を上記のアクリル系粘着剤ａ３中に固形分比でそれぞれ１．６５質量部、０．０５質量部となる様に添加・混合し、近赤外線吸収性粘着剤ａを得た。
＜近赤外線吸収性粘着剤ｂ＞
モノマーとしてブチルアクリレート（４２７．３ｇ）、エチルアクリレート（１７１．２ｇ）、４−ヒドロキシブチル（メタ）アクリレート（１．５ｇ）を秤量し、十分に混合して重合性モノマー混合物（ｂ１）を得た。次いで、この重合性モノマー混合物（ｂ１）３００ｇと酢酸エチル１６０ｇとをフラスコに入れた。また、滴下ロートに３００ｇの重合性モノマー混合物（ｂ１）、１６ｇの酢酸エチル及び０．１５ｇの２，２’−アゾビス（４−メトキシ−２，４−ジメチル）バレロニトリルを入れ、よく混合して滴下用混合物（ｂ２）を調製した。
<Near-infrared absorbing adhesive b>
As monomers, butyl acrylate (427.3 g), ethyl acrylate (171.2 g), 4-hydroxybutyl (meth) acrylate (1.5 g) were weighed and mixed thoroughly to obtain a polymerizable monomer mixture (b1). . Next, 300 g of this polymerizable monomer mixture (b1) and 160 g of ethyl acetate were placed in a flask. Also, add 300 g of the polymerizable monomer mixture (b1), 16 g of ethyl acetate and 0.15 g of 2,2′-azobis (4-methoxy-2,4-dimethyl) valeronitrile in the dropping funnel and mix well. A dropping mixture (b2) was prepared.
次に、窒素ガスを２０ｍｌ／分で流通させながら、上記フラスコの内温を９５℃まで上昇させ、重合開始剤である２，２’−アゾビス（４−メトキシ−２，４−ジメチル）バレロニトリル（０．１５ｇ）をフラスコに投入し、重合反応を開始させた。そして、このフラスコに滴下ロートから滴下用混合物（ｂ２）を９０分掛けて滴下した。滴下用混合物（ｂ２）の滴下終了後、粘度の上昇に応じて酢酸エチルで希釈を行いながら、６時間の熟成を行った。反応終了後、重量平均分子量６０万、酸価０ｍｇＫＯＨ／ｇのアクリル系粘着剤ｂ３を得た。 Next, while flowing nitrogen gas at a rate of 20 ml / min, the internal temperature of the flask was raised to 95 ° C., and 2,2′-azobis (4-methoxy-2,4-dimethyl) valeronitrile as a polymerization initiator. (0.15 g) was charged into the flask to initiate the polymerization reaction. And the mixture (b2) for dripping was dripped at this flask over 90 minutes from the dropping funnel. After completion of the dropwise addition of the mixture for dropping (b2), aging was performed for 6 hours while diluting with ethyl acetate in accordance with the increase in viscosity. After completion of the reaction, an acrylic pressure-sensitive adhesive b3 having a weight average molecular weight of 600,000 and an acid value of 0 mgKOH / g was obtained.
また、近赤外線吸収色素（色素Ａ）を固形分２％となるようＭＩＢＫと混合した混合液を調製し、この混合液を発振周波数３６ＫＨｚの超音波分散槽にて３０分超音波にかけて色素溶液ｂ４を調製し、微粒子分散状態となった近赤外線吸収色素を得た。さらに、架橋剤としてイソシアネート系硬化剤コロネートＬ（日本ポリウレタン工業製）をＭＥＫに溶解し、固形分９％の架橋剤溶液ｂ５を調製した。そして、これらの色素溶液ｂ４と架橋剤溶液ｂ５を上記のアクリル系粘着剤ｂ３中に固形分比でそれぞれ１．６５質量部、０．９質量部となる様に添加・混合し、近赤外線吸収性粘着剤ｂを得た。 Further, a mixed solution in which near-infrared absorbing pigment (Dye A) is mixed with MIBK so as to have a solid content of 2% is prepared, and this mixed solution is subjected to ultrasonic waves for 30 minutes in an ultrasonic dispersion tank having an oscillation frequency of 36 KHz. And a near-infrared absorbing dye in a fine particle dispersed state was obtained. Furthermore, an isocyanate curing agent Coronate L (manufactured by Nippon Polyurethane Industry) was dissolved in MEK as a crosslinking agent to prepare a crosslinking agent solution b5 having a solid content of 9%. Then, these dye solution b4 and crosslinking agent solution b5 are added and mixed in the acrylic pressure-sensitive adhesive b3 so as to have a solid content ratio of 1.65 parts by mass and 0.9 parts by mass, respectively, to absorb near infrared rays. Adhesive b was obtained.
＜近赤外線吸収性粘着剤ｃ＞
モノマーとしてブチルアクリレート（４５８．６ｇ）、メチルアクリレート（１３１．０ｇ）、アクリル酸（１０．４ｇ）を秤量し、十分に混合して重合性モノマー混合物（ｃ１）を得た。次いで、この重合性モノマー混合物（ｃ１）３００ｇと酢酸エチル１６０ｇとをフラスコに入れた。また、滴下ロートに３００ｇの重合性モノマー混合物（ｃ１）、１６ｇの酢酸エチル及び０．１５ｇの２，２’−アゾビス（４−メトキシ−２，４−ジメチル）バレロニトリルを入れ、よく混合して滴下用混合物（ｃ２）を調製した。
<Near-infrared absorbing adhesive c>
As monomers, butyl acrylate (458.6 g), methyl acrylate (131.0 g) and acrylic acid (10.4 g) were weighed and mixed thoroughly to obtain a polymerizable monomer mixture (c1). Next, 300 g of this polymerizable monomer mixture (c1) and 160 g of ethyl acetate were placed in a flask. Also, add 300 g of the polymerizable monomer mixture (c1), 16 g of ethyl acetate and 0.15 g of 2,2′-azobis (4-methoxy-2,4-dimethyl) valeronitrile in the dropping funnel and mix well. A dropping mixture (c2) was prepared.
次に、窒素ガスを２０ｍｌ／分で流通させながら、上記フラスコの内温を９５℃まで上昇させ、重合開始剤である２，２’−アゾビス（４−メトキシ−２，４−ジメチル）バレロニトリル（０．１５ｇ）をフラスコに投入し、重合反応を開始させた。そして、このフラスコに滴下ロートから滴下用混合物（ｃ２）を９０分掛けて滴下した。滴下用混合物（ｃ２）の滴下終了後、粘度の上昇に応じて酢酸エチルで希釈を行いながら、６時間の熟成を行った。反応終了後、重量平均分子量６０万、酸価８ｍｇＫＯＨ／ｇのアクリル系粘着剤ｃ３を得た。 Next, while flowing nitrogen gas at a rate of 20 ml / min, the internal temperature of the flask was raised to 95 ° C., and 2,2′-azobis (4-methoxy-2,4-dimethyl) valeronitrile as a polymerization initiator. (0.15 g) was charged into the flask to initiate the polymerization reaction. And the mixture (c2) for dripping was dripped at this flask over 90 minutes from the dropping funnel. After completion of the dropwise addition of the mixture for dropping (c2), the mixture was aged for 6 hours while being diluted with ethyl acetate as the viscosity increased. After completion of the reaction, an acrylic pressure-sensitive adhesive c3 having a weight average molecular weight of 600,000 and an acid value of 8 mgKOH / g was obtained.
また、近赤外線吸収色素（色素Ａ）を固形分２％となるようＭＩＢＫと混合した混合液を調製し、この混合液を発振周波数３６ＫＨｚの超音波分散槽にて３０分超音波にかけて色素溶液ｃ４を調製し、微粒子分散状態となった近赤外線吸収色素を得た。さらに、架橋剤としてＮ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミンをＭＥＫに溶解し、固形分１％の架橋剤溶液ｃ５を調製した。そして、これらの色素溶液ｃ４と架橋剤溶液ｃ５を上記のアクリル系粘着剤ｃ３中に固形分比でそれぞれ１．６５質量部、０．０２５質量部となる様に添加・混合し、近赤外線吸収性粘着剤ｃを得た。 Further, a mixed solution in which near-infrared absorbing pigment (Dye A) is mixed with MIBK so as to have a solid content of 2% is prepared, and this mixed solution is subjected to ultrasonic waves for 30 minutes in an ultrasonic dispersion tank having an oscillation frequency of 36 KHz to prepare a dye solution c4. And a near-infrared absorbing dye in a fine particle dispersed state was obtained. Further, N, N, N ′, N′-tetraglycidyl-m-xylylenediamine as a crosslinking agent was dissolved in MEK to prepare a crosslinking agent solution c5 having a solid content of 1%. Then, these dye solution c4 and crosslinking agent solution c5 are added and mixed in the acrylic pressure-sensitive adhesive c3 so as to have a solid content ratio of 1.65 parts by mass and 0.025 parts by mass, respectively. Adhesive c was obtained.
（２）近赤外線遮蔽フィルムの作製
＜近赤外線遮蔽フィルムＡ＞
上記のようにして調製された近赤外線吸収性粘着剤ａをアプリケーターにて剥離ＰＥＴ（リンテック製、商品名：ＰＥＴ３８Ｃ）に塗工した。塗工時の厚みは乾燥後の粘着剤厚みが２５μｍになる様に調整した。次いで、８０℃のオーブン中にて２分間乾燥させた。この近赤外線吸収性粘着剤ａからなる層に剥離フィルム（リンテック製、商品名：ＰＥＴ３８０１）を貼り合せ、常温で７日間養生させ、近赤外線遮蔽フィルムＡを作製した。
(2) Production of near-infrared shielding film <Near-infrared shielding film A>
The near-infrared absorbing pressure-sensitive adhesive a prepared as described above was applied to peeled PET (manufactured by Lintec, trade name: PET38C) with an applicator. The thickness at the time of coating was adjusted so that the thickness of the adhesive after drying was 25 μm. Subsequently, it was dried in an oven at 80 ° C. for 2 minutes. A release film (manufactured by Lintec, trade name: PET3801) was bonded to the layer made of this near-infrared absorbing pressure-sensitive adhesive a, and cured at room temperature for 7 days to produce a near-infrared shielding film A.
その後、近赤外線遮蔽フィルムＡの軽剥離側剥離ＰＥＴを剥がし、易接着処理光学ＰＥＴ（東洋紡社製、商品名：コスモシャインＡ４３００）に貼り合せ、さらに重剥離側剥離ＰＥＴを剥がし、評価試験用の近赤外線遮蔽フィルムＡとした。 Thereafter, the lightly peeled side peeled PET of the near-infrared shielding film A is peeled off, bonded to easy-adhesion treated optical PET (trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.), and the heavyly peeled side peeled PET is peeled off for evaluation test. It was set as the near-infrared shielding film A.
＜近赤外線遮蔽フィルムＢ＞
上記のようにして調製された近赤外線吸収性粘着剤ｂをアプリケーターにて剥離ＰＥＴ（リンテック製、商品名：ＰＥＴ３８Ｃ）に塗工した。塗工時の厚みは乾燥後の粘着剤厚みが２５μｍになる様に調整した。次いで、８０℃のオーブン中にて２分間乾燥させた。この近赤外線吸収性粘着剤ｂからなる層に剥離フィルム（リンテック製、商品名：ＰＥＴ３８０１）を貼り合せ、常温で７日間養生させ、近赤外線遮蔽フィルムＢを作製した。
<Near-infrared shielding film B>
The near-infrared absorbing adhesive b prepared as described above was applied to release PET (product name: PET38C, manufactured by Lintec) with an applicator. The thickness at the time of coating was adjusted so that the thickness of the adhesive after drying was 25 μm. Subsequently, it was dried in an oven at 80 ° C. for 2 minutes. A release film (manufactured by Lintec, trade name: PET3801) was bonded to the layer made of this near-infrared absorbing adhesive b, and cured at room temperature for 7 days to produce a near-infrared shielding film B.
その後、近赤外線遮蔽フィルムＢの軽剥離側剥離ＰＥＴを剥がし、易接着処理光学ＰＥＴ（東洋紡社製、商品名：コスモシャインＡ４３００）に貼り合せ、さらに重剥離側剥離ＰＥＴを剥がし、評価試験用の近赤外線遮蔽フィルムＢとした。 Thereafter, the light release side peeled PET of the near-infrared shielding film B is peeled off and bonded to an easy adhesion treated optical PET (manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4300), and the heavy peel side peeled PET is further peeled off for evaluation test. It was set as the near-infrared shielding film B.
＜近赤外線遮蔽フィルムＣ＞
上記のようにして調製された近赤外線吸収性粘着剤ｃをアプリケーターにて剥離ＰＥＴ（リンテック製、商品名：ＰＥＴ３８Ｃ）に塗工した。塗工時の厚みは乾燥後の粘着剤厚みが２５μｍになる様に調整した。次いで、８０℃のオーブン中にて２分間乾燥させた。この近赤外線吸収性粘着剤ｃからなる層に剥離フィルム（リンテック製、商品名：ＰＥＴ３８０１）を貼り合せ、常温で７日間養生させ、近赤外線遮蔽フィルムＣを作製した。
<Near-infrared shielding film C>
The near-infrared absorbing pressure-sensitive adhesive c prepared as described above was applied to release PET (product name: PET38C, manufactured by Lintec) with an applicator. The thickness at the time of coating was adjusted so that the thickness of the adhesive after drying was 25 μm. Subsequently, it was dried in an oven at 80 ° C. for 2 minutes. A release film (manufactured by Lintec, trade name: PET3801) was bonded to the layer made of this near-infrared-absorbing pressure-sensitive adhesive c and cured at room temperature for 7 days to produce a near-infrared shielding film C.
その後、近赤外線遮蔽フィルムＣの軽剥離側剥離ＰＥＴを剥がし、易接着処理光学ＰＥＴ（東洋紡社製、商品名：コスモシャインＡ４３００）に貼り合せ、さらに重剥離側剥離ＰＥＴを剥がし、評価試験用の近赤外線遮蔽フィルムＣとした。 Thereafter, the lightly peeled side peeled PET of the near-infrared shielding film C is peeled off and bonded to an easy-adhesion treated optical PET (manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4300), and the heavyly peeled side peeled PET is peeled off for evaluation test. A near-infrared shielding film C was obtained.
（３）評価
得られた評価試験用の近赤外線遮蔽フィルムＡ、Ｂ及びＣに対して、分光光度計（島津製作所製、商品名：ＵＶ３１５０）により透過スペクトル及び色調を測定し、ヘイズメーター（日本電色製、商品名：ＮＤＨ２０００）によりヘイズを測定し、それぞれの測定結果を図１及び表１に示した。
(3) Evaluation With respect to the obtained near-infrared shielding films A, B and C for evaluation tests, a transmission spectrum and a color tone were measured with a spectrophotometer (manufactured by Shimadzu Corporation, trade name: UV3150), and a haze meter (Japan) The haze was measured by Denshoku (trade name: NDH2000), and the measurement results are shown in FIG. 1 and Table 1.
その結果、図１及び表１から明らかなように、酸価が２５ｍｇＫＯＨ／ｇである近赤外線吸収性粘着剤ａを使用した近赤外線遮蔽フィルムＡでは、近赤外線領域の透過率が非常に高いことが確認され、実用に供し得ないことが示された。これに対し、酸価が０及び８ｍｇＫＯＨ／ｇである近赤外線吸収性粘着剤ｂ及びｃを使用した近赤外線遮蔽フィルムＢ及びＣでは、近赤外線領域における遮蔽が良好であることが示された。 As a result, as is apparent from FIG. 1 and Table 1, the near-infrared shielding film A using the near-infrared absorbing adhesive a having an acid value of 25 mgKOH / g has a very high transmittance in the near-infrared region. It was confirmed that it was not practically usable. On the other hand, it was shown that the near-infrared shielding films B and C using the near-infrared absorbing pressure-sensitive adhesives b and c having acid values of 0 and 8 mgKOH / g have good shielding in the near-infrared region.
２．ディスプレイ用近赤外線遮蔽体の耐久性
（１）ディスプレイ用近赤外線遮蔽体の作製
＜ディスプレイ用近赤外線遮蔽体Ｂ’＞
上記で作製された評価用の近赤外線遮蔽フィルムＢをガラス板に貼りあわせることでディスプレイ用近赤外線遮蔽体Ｂ’を作製した。
2. Durability of near-infrared shield for display (1) Production of near-infrared shield for display <Near-infrared shield for display B '>
The near-infrared shielding body B ′ for display was produced by laminating the near-infrared shielding film B for evaluation prepared above on a glass plate.
＜ディスプレイ用近赤外線遮蔽体Ｃ’＞
上記で作製された評価用の近赤外線遮蔽フィルムＣをガラス板に貼りあわせることでディスプレイ用近赤外線遮蔽体Ｃ’を作製した。
<Near-infrared shielding for display C '>
The near-infrared shielding body C ′ for display was produced by pasting the evaluation near-infrared shielding film C produced above on a glass plate.
（２）評価
得られたディスプレイ用近赤外線遮蔽体Ｂ’及びＣ’に対して、分光光度計（島津製作所製、商品名：ＵＶ３１５０）により透過スペクトル及び色調を測定し、ヘイズメーター（日本電色製、商品名：ＮＤＨ２０００）によりヘイズを測定した。次に、ディスプレイ用近赤外線遮蔽体Ｂ’及びＣ’を８０℃オーブン及び６０℃／９０％恒温高湿層にそれぞれ投入し、１０００時間放置した後、上記と同様に透過スペクトル、色調及びヘイズを測定した。それぞれの測定結果は図２〜５及び表２に示した。図２はディスプレイ用近赤外線遮蔽体Ｂ’に対する８０℃耐熱性試験の変化を示したグラフであり、図３は６０℃／９０％耐湿熱試験の変化を示したグラフである。また、図４はディスプレイ用近赤外線遮蔽体Ｃ’に対する８０℃耐熱性試験の変化を示したグラフであり、図５は６０℃／９０％耐湿熱試験の変化を示したグラフである。
(2) Evaluation With respect to the obtained near-infrared shields B ′ and C ′ for display, a transmission spectrum and a color tone were measured with a spectrophotometer (manufactured by Shimadzu Corporation, trade name: UV3150), and a haze meter (Nippon Denshoku) was measured. (Trade name: NDH2000), and haze was measured. Next, the near-infrared shields B ′ and C ′ for display were put into an 80 ° C. oven and a 60 ° C./90% constant temperature and high humidity layer, respectively, and allowed to stand for 1000 hours, and then the transmission spectrum, color tone and haze were changed in the same manner as described above. It was measured. The respective measurement results are shown in FIGS. FIG. 2 is a graph showing changes in the 80 ° C. heat resistance test for the near-infrared shield B ′ for display, and FIG. 3 is a graph showing changes in the 60 ° C./90% wet heat resistance test. FIG. 4 is a graph showing changes in the 80 ° C. heat resistance test for the near-infrared shield C ′ for display, and FIG. 5 is a graph showing changes in the 60 ° C./90% wet heat resistance test.
その結果、図２〜５及び表２から明らかなように、酸価が０ｍｇＫＯＨ／ｇである近赤外線吸収性粘着剤ｂを使用したディスプレイ用近赤外線遮蔽体Ｂ’では、耐久性試験後に近赤外線領域における透過率が上昇しており、耐久性に劣ることが確認された。これに対し、酸価が８ｍｇＫＯＨ／ｇである近赤外線吸収性粘着剤ｃを使用したディスプレイ用近赤外線遮蔽体Ｃ’では、耐久性試験後においても近赤外線領域の遮蔽が良好であることが示された。 As a result, as is apparent from FIGS. 2 to 5 and Table 2, the near-infrared shielding body B ′ for display using the near-infrared absorbing adhesive b having an acid value of 0 mgKOH / g is used for the near-infrared ray after the durability test. It was confirmed that the transmittance in the region was increased and the durability was inferior. In contrast, the near-infrared shielding body C ′ for display using the near-infrared absorbing adhesive c having an acid value of 8 mgKOH / g shows good shielding in the near-infrared region even after the durability test. It was done.
３．近赤外線吸収性粘着剤におけるトルエン含有量
（１）近赤外線遮蔽フィルムの作製
＜近赤外線遮蔽フィルムＤ１＞
近赤外線吸収色素（色素Ａ）を固形分２％となるようＭＩＢＫと混合した混合液を調製し、この混合液を発振周波数３６ＫＨｚの超音波分散槽にて３０分超音波にかけて色素溶液ｄ１を調製した。そして、この色素溶液ｄ１を上記のアクリル系粘着剤ｃ３中に固形分比でそれぞれ１．６５部となる様に添加・混合し、さらに、塗料中の含有量が質量比５％となるようトルエンを添加・混合し、近赤外線吸収性粘着剤ｄを得た。
3. Toluene content in near-infrared absorbing adhesive (1) Production of near-infrared shielding film <Near-infrared shielding film D1>
A mixed solution prepared by mixing near-infrared absorbing dye (Dye A) with MIBK so as to have a solid content of 2% is prepared, and this mixed solution is subjected to ultrasonic waves for 30 minutes in an ultrasonic dispersion tank having an oscillation frequency of 36 KHz to prepare a dye solution d1. did. Then, this pigment solution d1 is added and mixed in the acrylic pressure-sensitive adhesive c3 so as to have a solid content ratio of 1.65 parts, respectively. Further, toluene is added so that the content in the paint becomes 5% by mass. Were added and mixed to obtain a near-infrared absorbing adhesive d.
上記のようにして調製された近赤外線吸収性粘着剤ｄを一定時間静置後、アプリケーターにて剥離ＰＥＴ（リンテック製、商品名：ＰＥＴ３８Ｃ）に塗工した。塗工時の厚みは乾燥後の粘着剤厚みが２５μｍになる様に調整した。次いで、８０℃のオーブン中にて２分間乾燥させ、剥離フィルム（リンテック製、商品名：ＰＥＴ３８０１）を貼り合せ、近赤外線遮蔽フィルムＤ１を作製した。 The near-infrared absorbing pressure-sensitive adhesive d prepared as described above was allowed to stand for a certain period of time, and then applied to release PET (product name: PET38C, manufactured by Lintec) with an applicator. The thickness at the time of coating was adjusted so that the thickness of the adhesive after drying was 25 μm. Subsequently, it was dried in an oven at 80 ° C. for 2 minutes, and a release film (manufactured by Lintec, trade name: PET3801) was bonded to produce a near-infrared shielding film D1.
その後、近赤外線遮蔽フィルムＤ１の軽剥離側剥離ＰＥＴを剥がし、易接着処理光学ＰＥＴ（東洋紡社製、商品名：コスモシャインＡ４３００）に貼り合せ、さらに重剥離側剥離ＰＥＴを剥がし、評価試験用の近赤外線遮蔽フィルムＤ１とした。 Thereafter, the light release side release PET of the near-infrared shielding film D1 is peeled off and bonded to an easy-adhesion treated optical PET (manufactured by Toyobo Co., Ltd., trade name: Cosmo Shine A4300), and the heavy release side release PET is further peeled off for evaluation test. It was set as the near-infrared shielding film D1.
＜近赤外線遮蔽フィルムＤ２＞
近赤外線吸収性粘着剤ｄにおけるトルエンの含有量を７質量％とした以外は、近赤外線遮蔽フィルムＤ１と同様にして、近赤外線遮蔽フィルムＤ２を作製した。
<Near-infrared shielding film D2>
A near-infrared shielding film D2 was produced in the same manner as the near-infrared shielding film D1, except that the content of toluene in the near-infrared absorbing adhesive d was 7% by mass.
＜近赤外線遮蔽フィルムＤ３＞
近赤外線吸収性粘着剤ｄにおけるトルエンの含有量を８質量％とした以外は、近赤外線遮蔽フィルムＤ１と同様にして、近赤外線遮蔽フィルムＤ３を作製した。
<Near-infrared shielding film D3>
A near-infrared shielding film D3 was produced in the same manner as the near-infrared shielding film D1, except that the content of toluene in the near-infrared absorbing adhesive d was 8% by mass.
＜近赤外線遮蔽フィルムＤ４＞
近赤外線吸収性粘着剤ｄにおけるトルエンの含有量を９質量％とした以外は、近赤外線遮蔽フィルムＤ１と同様にして、近赤外線遮蔽フィルムＤ４を作製した。
<Near-infrared shielding film D4>
A near-infrared shielding film D4 was produced in the same manner as the near-infrared shielding film D1, except that the content of toluene in the near-infrared absorbing adhesive d was 9% by mass.
＜近赤外線遮蔽フィルムＤ５＞
近赤外線吸収性粘着剤ｄにおけるトルエンの含有量を１０質量％とした以外は、近赤外線遮蔽フィルムＤ１と同様にして、近赤外線遮蔽フィルムＤ５を作製した。
<Near-infrared shielding film D5>
A near-infrared shielding film D5 was produced in the same manner as the near-infrared shielding film D1, except that the content of toluene in the near-infrared absorbing adhesive d was 10% by mass.
＜近赤外線遮蔽フィルムＤ６＞
近赤外線吸収性粘着剤ｄにおけるトルエンの含有量を１５質量％とした以外は、近赤外線遮蔽フィルムＤ１と同様にして、近赤外線遮蔽フィルムＤ６を作製した。
<Near-infrared shielding film D6>
A near-infrared shielding film D6 was produced in the same manner as the near-infrared shielding film D1, except that the content of toluene in the near-infrared absorbing adhesive d was 15% by mass.
＜近赤外線遮蔽フィルムＤ７＞
近赤外線吸収性粘着剤ｄにおけるトルエンを添加・混合していない以外は、近赤外線遮蔽フィルムＤ１と同様にして、近赤外線遮蔽フィルムＤ７を作製した（トルエンの含有量０質量％）。
<Near-infrared shielding film D7>
A near-infrared shielding film D7 was produced in the same manner as the near-infrared shielding film D1 except that toluene in the near-infrared absorbing adhesive d was not added / mixed (
（２）評価
上記のようにして得られた近赤外線遮蔽フィルムＤ１〜Ｄ７に対して、光学顕微鏡により露出した近赤外線吸収粘着層側から当該近赤外線吸収粘着層の様子を観察し、長径３０μｍ超の色素凝集物の有無を確認した。また、長径３０μｍ超の色素凝集物が確認された際の、トルエンを添加・混合した後の静置時間を表３に示した。なお、凝集物の長径が３０μｍ超の場合、肉眼で視認できることから外観欠点として判定される。
(2) Evaluation For the near-infrared shielding films D1 to D7 obtained as described above, the state of the near-infrared absorbing adhesive layer is observed from the near-infrared absorbing adhesive layer side exposed by the optical microscope, and the major axis exceeds 30 μm. The presence or absence of dye aggregates was confirmed. Table 3 shows the standing time after addition and mixing of toluene when a dye aggregate having a major axis exceeding 30 μm was confirmed. In addition, when the long diameter of an aggregate is more than 30 micrometers, since it can visually recognize with the naked eye, it is determined as an external appearance defect.
その結果、表３から明らかなように、トルエン含有量が７質量％以上である場合、８時間以内に色素凝集物が確認され、実用に供し得ない。この理由は、近赤外線吸収性粘着剤を透明基材の一方の面に設けて近赤外線遮蔽フィルムを製造する際に、製造開始時と製造終了時において、品質が変化してしまうからである。一方、塗料中のトルエン含有量を５質量％以下とすることで、近赤外線吸収性粘着剤の製造後８時間を超えて安定な状態を維持することができる。これによって、近赤外線遮蔽フィルムの製造開始時と製造終了時において、品質の一定な近赤外線遮蔽フィルムを提供することができる。 As a result, as is apparent from Table 3, when the toluene content is 7% by mass or more, dye aggregates are confirmed within 8 hours and cannot be put to practical use. The reason for this is that when a near-infrared absorbing adhesive is provided on one side of a transparent substrate to produce a near-infrared shielding film, the quality changes at the start of manufacture and at the end of manufacture. On the other hand, when the content of toluene in the coating is 5% by mass or less, a stable state can be maintained for more than 8 hours after the production of the near-infrared absorbing adhesive. This makes it possible to provide a near-infrared shielding film with a constant quality at the start of production and the end of production of the near-infrared shielding film.
Claims (4)
前記近赤外線吸収性粘着剤中において前記ジイモニウム塩化合物が３０μｍ以下の凝集体で存在し、前記ジイモニウム塩化合物は前記近赤外線吸収性粘着剤の固形分１００質量部に対して０．５〜３．０質量部含有されていることを特徴とする近赤外線吸収性粘着剤。
In the near-infrared absorbing pressure-sensitive adhesive, the diimonium salt compound is present in an aggregate of 30 μm or less, and the diimonium salt compound is 0.5 to 3.3 based on 100 parts by mass of the solid content of the near-infrared absorbing pressure-sensitive adhesive. A near-infrared absorbing pressure-sensitive adhesive containing 0 part by mass.
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| KR20200023949A (en) * | 2018-08-27 | 2020-03-06 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009013200A (en) * | 2007-06-29 | 2009-01-22 | Toyo Ink Mfg Co Ltd | Near-infrared absorbing pressure-sensitive adhesive and near-infrared absorbing pressure-sensitive adhesive sheet |
| JP2010018773A (en) * | 2008-06-12 | 2010-01-28 | Nippon Shokubai Co Ltd | Near-infrared ray absorbing pressure-sensitive adhesive composition |
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| JP2009013200A (en) * | 2007-06-29 | 2009-01-22 | Toyo Ink Mfg Co Ltd | Near-infrared absorbing pressure-sensitive adhesive and near-infrared absorbing pressure-sensitive adhesive sheet |
| JP2010018773A (en) * | 2008-06-12 | 2010-01-28 | Nippon Shokubai Co Ltd | Near-infrared ray absorbing pressure-sensitive adhesive composition |
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| KR20200023949A (en) * | 2018-08-27 | 2020-03-06 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
| KR102293085B1 (en) * | 2018-08-27 | 2021-08-23 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer using the same and color filter |
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