JP5655660B2 - Near-infrared shielding film and near-infrared shielding body using the same - Google Patents
Near-infrared shielding film and near-infrared shielding body using the same Download PDFInfo
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- JP5655660B2 JP5655660B2 JP2011067542A JP2011067542A JP5655660B2 JP 5655660 B2 JP5655660 B2 JP 5655660B2 JP 2011067542 A JP2011067542 A JP 2011067542A JP 2011067542 A JP2011067542 A JP 2011067542A JP 5655660 B2 JP5655660 B2 JP 5655660B2
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Landscapes
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- Optical Filters (AREA)
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Description
本発明は、例えばプラズマディスプレイパネル（ＰＤＰ）等に適用され、優れた反射防止性能および近赤外線吸収能を有し、かつ帯電防止性能にも優れた近赤外線遮蔽フィルム及びこれを用いた近赤外線遮蔽体に関する。 The present invention is applied to, for example, a plasma display panel (PDP) and the like, and has a near-infrared shielding film having excellent antireflection performance and near-infrared absorption ability, and excellent in antistatic performance, and near-infrared shielding using the same. About the body.
近年の高度情報化社会において、電子ディスプレイ等の光エレクトロニクス機器はテレビジョンやパーソナルコンピュータのモニター用等として著しい進歩を遂げ、広く普及している。中でもプラズマディスプレイパネル（以下、ＰＤＰと称す）は電子ディスプレイパネルの大型化や薄型化に伴って注目を浴びているが、動作原理上発せられる近赤外線によってリモートコントロール機器等の周辺機器の誤動作を招くといった問題がある。また、近年、プラズマディスプレイパネル、液晶ディスプレイパネル等の電子画像表示装置（電子ディスプレイ）は、大型化に伴い、外光の映り込みによる表示される画像の視認性の低下が問題となっている。そのため、透明基材フィルムの表面に反射防止層を設けて形成された反射防止フィルムをディスプレイ表面に貼り合わせ、画像の視認性を高める方法が一般的に採用されている。さらに、静電気によるディスプレイ表面への塵埃などの付着を防止するために、これらの反射防止フィルムには帯電防止性能を有していることが求められている。 In an advanced information society in recent years, optoelectronic devices such as electronic displays have made remarkable progress and are widely used for monitors of televisions and personal computers. Among them, plasma display panels (hereinafter referred to as PDPs) are attracting attention as electronic display panels are becoming larger and thinner, but peripheral devices such as remote control devices can malfunction due to near-infrared rays generated by the operating principle. There is a problem. In recent years, electronic image display devices (electronic displays) such as a plasma display panel and a liquid crystal display panel have become problematic in that the visibility of displayed images is reduced due to the reflection of external light as the size increases. Therefore, a method is generally adopted in which an antireflection film formed by providing an antireflection layer on the surface of a transparent substrate film is bonded to the display surface to enhance the visibility of the image. Furthermore, in order to prevent dust and the like from adhering to the display surface due to static electricity, these antireflection films are required to have antistatic performance.
これらの問題を解決するために、反射防止層と、ジイモニウム系色素又はフタロシアニン系色素を含む近赤外線吸収性粘着層とを複合化した、ＰＤＰに用いられる近赤外線遮蔽フィルムが特許文献１に提案されている。 In order to solve these problems, Patent Document 1 proposes a near-infrared shielding film used in a PDP in which an antireflection layer and a near-infrared absorbing adhesive layer containing a diimonium dye or a phthalocyanine dye are combined. ing.
ところで、帯電防止性を付与するために、π共役系導電性高分子が帯電防止剤や電極材料等の工業材料として使用されている。このπ共役系導電性高分子は、ドーパントと呼ばれる物質をドーピングすることによって、高い導電性が付与される。例えば、π共役系導電性高分子とドーパントからなる複合体と多官能（メタ）アクリレートとを含有するコーティング剤組成物が、特許文献２に知られている。 By the way, in order to impart antistatic properties, π-conjugated conductive polymers are used as industrial materials such as antistatic agents and electrode materials. This π-conjugated conductive polymer is imparted with high conductivity by doping a substance called a dopant. For example, Patent Document 2 discloses a coating agent composition containing a complex composed of a π-conjugated conductive polymer and a dopant and a polyfunctional (meth) acrylate.
また、透明基材フィルム、ハードコート層、および低屈折率層からなる反射防止フィルムへ帯電防止性能を付与するために、π共役系導電性高分子とドーパントからなる複合体をハードコート層に添加する方法が、特許文献３に知られている。 In addition, in order to impart antistatic performance to an antireflection film consisting of a transparent base film, hard coat layer, and low refractive index layer, a composite comprising a π-conjugated conductive polymer and a dopant is added to the hard coat layer. A method for doing this is known from US Pat.
特許文献１に記載の近赤外線遮蔽フィルムは、帯電防止性能を発現するための帯電防止剤等の材料を含んでいないため、ディスプレイ表面に塵埃が付着しやすく、汚れが目立ってしまい、画像が見づらくなってしまう。さらに、ディスプレイ製造工程において、塵埃の混入により不具合が発生してしまうこともある。 Since the near-infrared shielding film described in Patent Document 1 does not contain a material such as an antistatic agent for exhibiting antistatic performance, dust tends to adhere to the display surface, dirt is noticeable, and images are difficult to see. turn into. In addition, in the display manufacturing process, problems may occur due to dust contamination.
特許文献２では、π共役系導電性高分子とドーパントからなる複合体の屈折率はおよそ１．５と高い。したがって、当該複合体を含む特許文献２のコーティング剤組成物をそのままＰＤＰ用の光学フィルムへ適用すると、外光の反射が問題となる。 In Patent Document 2, the refractive index of a complex composed of a π-conjugated conductive polymer and a dopant is as high as about 1.5. Therefore, when the coating agent composition of Patent Document 2 containing the composite is applied to an optical film for PDP as it is, reflection of external light becomes a problem.
特許文献３では、十分な帯電防止性能を得るために、π共役系導電性高分子とドーパントからなる複合体をハードコート層へ多量に含有させている。その結果、全光線透過率が低下したり、製造コストが高くなるといった問題がある。また、ハードコート層の耐熱性、耐擦傷性、鉛筆硬度等を低下させる問題が生じる。加えて、特許文献３に記載の反射防止フィルムには、近赤外線吸収性層が使用されていないため近赤外線を遮蔽することができない。 In Patent Document 3, in order to obtain sufficient antistatic performance, a complex composed of a π-conjugated conductive polymer and a dopant is contained in a large amount in the hard coat layer. As a result, there are problems that the total light transmittance is reduced and the manufacturing cost is increased. Further, there arises a problem that the heat resistance, scratch resistance, pencil hardness and the like of the hard coat layer are lowered. In addition, since the near-infrared absorbing layer is not used in the antireflection film described in Patent Document 3, the near-infrared rays cannot be shielded.
そこで、本発明は上記課題を解決するものであって、その目的とするところは、優れた反射防止性能及び帯電防止性能を有し、かつ近赤外線吸収能、耐熱性、耐擦傷性、及び鉛筆硬度にも優れる近赤外線遮蔽フィルムを提供することにある。 Therefore, the present invention solves the above-mentioned problems, and its object is to have excellent antireflection performance and antistatic performance, and near infrared absorption ability, heat resistance, scratch resistance, and pencil. It is providing the near-infrared shielding film which is excellent also in hardness.
そのための手段として、本発明は次の手段を採る。
（１）透明基材フィルムの一方面に、ハードコート層と、前記ハードコート層よりも屈折率の低い低屈折率層とがこの順に積層されており、前記透明基材フィルムの他方面に近赤外線吸収性粘着層が積層されている近赤外線遮蔽フィルムであって、前記低屈折率層は、(a)多官能（メタ）アクリレートと、(b)中空シリカ微粒子と、(c)π共役系導電性高分子とドーパントからなる複合体と、を含有する低屈折率層用塗液の硬化物であり、前記低屈折率層用塗液は、前記(a)多官能（メタ）アクリレート１００質量部あたり、前記(b)中空シリカ微粒子４０〜２５０質量部、前記(c)π共役系導電性高分子とドーパントからなる複合体１〜２５質量部を含み、前記(c)π共役系導電性高分子とドーパントからなる複合体中の、π共役系導電性高分子とドーパントの質量比が１：１〜１：５であり、前記近赤外線吸収性粘着層は、(d)（メタ）アクリル系粘着樹脂組成物と、(e)近赤外線吸収色素とを含み、前記(d)（メタ）アクリル系粘着樹脂組成物は、酸価が２０ｍｇＫＯＨ／ｇ以下の（メタ）アクリル系樹脂を含み、前記(e)近赤外線吸収色素は、ジイモニウム系色素又はフタロシアニン系色素である近赤外線遮蔽フィルム。
（２）（１）に記載の近赤外線遮蔽フィルムを、前記近赤外線吸収性粘着層を介して基材に貼り合わせてなる、プラズマディスプレイ用近赤外線遮蔽体。
For this purpose, the present invention adopts the following means.
(1) A hard coat layer and a low refractive index layer having a refractive index lower than that of the hard coat layer are laminated in this order on one side of the transparent base film, and close to the other side of the transparent base film. A near-infrared shielding film in which an infrared-absorbing adhesive layer is laminated, wherein the low refractive index layer comprises (a) a polyfunctional (meth) acrylate, (b) hollow silica fine particles, and (c) a π-conjugated system A cured product of a coating solution for a low refractive index layer containing a composite composed of a conductive polymer and a dopant, wherein the coating solution for a low refractive index layer is 100 masses of the (a) polyfunctional (meth) acrylate. Part (b) hollow silica fine particles 40 to 250 parts by mass, (c) 1 to 25 parts by mass of a composite comprising a π-conjugated conductive polymer and a dopant, and (c) π-conjugated conductive Π-Conjugated Conductive Polymer and Dopan in a Complex Containing Polymer and Dopant The near-infrared absorbing pressure-sensitive adhesive layer contains (d) a (meth) acrylic pressure-sensitive adhesive resin composition and (e) a near-infrared absorbing dye, d) The (meth) acrylic adhesive resin composition contains a (meth) acrylic resin having an acid value of 20 mgKOH / g or less, and the (e) near-infrared absorbing dye is a diimonium dye or a phthalocyanine dye. Infrared shielding film.
(2) A near-infrared shield for plasma display, comprising the near-infrared shielding film according to (1) attached to a substrate via the near-infrared absorbing adhesive layer.
本発明によれば、次のような効果を発揮することができる。本発明の近赤外線遮蔽フィルムは、低屈折率層にπ共役系導電性高分子とドーパントからなる複合体が含まれていることから、ハードコート層の物性を低下させることなく帯電防止作用を有し、ディスプレイ表面に貼られた近赤外線遮蔽フィルムへの静電気による塵埃などの付着を抑えることができる。さらに、近赤外線吸収性粘着層によって、モジュールから発せられる近赤外線によってリモートコントロールされる周辺機器の誤作動を防止できる。その上、低屈折率層においても、主に(a)多官能（メタ）アクリレートの硬化物のもつ性質に基づいて耐擦傷性を向上させることができる。加えて、(c)π共役系導電性高分子とドーパントからなる複合体中のπ共役系導電性高分子とドーパントの質量比が１：１〜１：５に設定されていることから、良好な導電性を発現できるとともに、良好な耐熱性を発揮することができる。 According to the present invention, the following effects can be exhibited. The near-infrared shielding film of the present invention has an antistatic action without degrading the physical properties of the hard coat layer, because the low refractive index layer contains a composite comprising a π-conjugated conductive polymer and a dopant. In addition, it is possible to suppress adhesion of dust and the like due to static electricity on the near-infrared shielding film attached to the display surface. Furthermore, the near-infrared absorbing adhesive layer can prevent malfunction of peripheral devices remotely controlled by near-infrared rays emitted from the module. In addition, even in the low refractive index layer, the scratch resistance can be improved mainly based on the properties of the cured product of (a) polyfunctional (meth) acrylate. In addition, (c) the mass ratio of the π-conjugated conductive polymer and the dopant in the complex composed of the π-conjugated conductive polymer and the dopant is set to 1: 1 to 1: 5, so that In addition to exhibiting excellent electrical conductivity, it is possible to exhibit good heat resistance.
以下、本発明を具体化した実施形態について詳細に説明する。本発明の近赤外線遮蔽フィルムは、テレビやモニター等の電子画像表示装置（電子ディスプレイ）におけるプラズマディスプレイパネル（ＰＤＰ）や液晶ディスプレイパネル等に適用されるものであって、透明基材フィルムの一方面にハードコート層と低屈折率層とがこの順に積層されており、透明基材フィルムの他方面に近赤外線吸収性粘着層が積層されている。 DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail. The near-infrared shielding film of the present invention is applied to a plasma display panel (PDP), a liquid crystal display panel or the like in an electronic image display device (electronic display) such as a television or a monitor. A hard coat layer and a low refractive index layer are laminated in this order, and a near-infrared absorbing adhesive layer is laminated on the other surface of the transparent substrate film.
＜透明基材フィルム＞
近赤外線遮蔽フィルムに用いられる透明基材フィルムは、透明性を有している限り特に制限されず、ポリエチレンテレフタレート（ＰＥＴ）で代表されるポリエステル系樹脂や、トリアセチルセルロース（ＴＡＣ）系樹脂など、従来からディスプレイ用フィルム基材として使用されている公知の透明樹脂を制限なく使用できる。
<Transparent substrate film>
The transparent base film used for the near-infrared shielding film is not particularly limited as long as it has transparency, such as a polyester resin represented by polyethylene terephthalate (PET), a triacetyl cellulose (TAC) resin, A known transparent resin conventionally used as a film substrate for a display can be used without limitation.
透明基材フィルムの厚みは、好ましくは２５〜４００μｍ、さらに好ましくは５０〜２００μｍである。なお、透明基材フィルムには、各種の添加剤が含まれていてもよい。そのような添加剤としては例えば、紫外線吸収剤、帯電防止剤、安定剤、可塑剤、滑剤、難燃剤等が挙げられる。 The thickness of the transparent substrate film is preferably 25 to 400 μm, more preferably 50 to 200 μm. In addition, various additives may be contained in the transparent base film. Examples of such additives include ultraviolet absorbers, antistatic agents, stabilizers, plasticizers, lubricants, flame retardants, and the like.
＜ハードコート層＞
ハードコート層は、活性エネルギー線硬化性樹脂及び溶媒を含むハードコート層用塗液の硬化物である。活性エネルギー線硬化性樹脂とは、紫外線や電子線のような活性エネルギー線を照射することにより硬化反応を生じる樹脂であり、その種類は特に限定されない。具体的には、例えば単官能（メタ）アクリレート〔ここで、本明細書では（メタ）アクリレートとは、アクリレートとメタクリレートの双方を含む総称を意味する〕、多官能（メタ）アクリレート、又はテトラエトキシシラン等の反応性珪素化合物等の硬化物が挙げられる。ハードコート層の硬度を向上させるという観点より、活性エネルギー線硬化性の多官能（メタ）アクリレートを主成分として含む組成物が好ましい。
<Hard coat layer>
The hard coat layer is a cured product of a hard coat layer coating liquid containing an active energy ray-curable resin and a solvent. The active energy ray-curable resin is a resin that undergoes a curing reaction when irradiated with active energy rays such as ultraviolet rays and electron beams, and the type thereof is not particularly limited. Specifically, for example, monofunctional (meth) acrylate (here, (meth) acrylate means a generic name including both acrylate and methacrylate), polyfunctional (meth) acrylate, or tetraethoxy Examples include cured products such as reactive silicon compounds such as silane. From the viewpoint of improving the hardness of the hard coat layer, a composition containing an active energy ray-curable polyfunctional (meth) acrylate as a main component is preferable.
活性エネルギー線硬化性多官能（メタ）アクリレートとしては特に制限されず、例えばジペンタエリスリトールヘキサアクリレート、テトラメチロールメタンテトラアクリレート、テトラメチロールメタントリアクリレート、トリメチロールプロパントリアクリレート、１，６−ヘキサンジオールジアクリレート、１，６−ビス（３−アクリロイルオキシ−２−ヒドロキシプロピルオキシ）ヘキサン等の多官能アルコールのアクリル誘導体や、ポリエチレングリコールジアクリレート及びポリウレタンアクリレート等が好ましい。 The active energy ray-curable polyfunctional (meth) acrylate is not particularly limited. For example, dipentaerythritol hexaacrylate, tetramethylol methane tetraacrylate, tetramethylol methane triacrylate, trimethylol propane triacrylate, 1,6-hexanediol diacrylate. Acrylic derivatives of polyfunctional alcohols such as acrylate and 1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane, polyethylene glycol diacrylate and polyurethane acrylate are preferred.
ハードコート層用塗液には任意の溶媒を用いることができる。具体的には、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソブチルアルコール、メチルグリコール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ジアセトンアルコール等のケトン類、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類、プロピレングリコールモノメチルエーテル、テトラヒドロフラン、１，４−ジオキサン等のエーテル類等が挙げられる。 Any solvent can be used for the hard coat layer coating solution. Specifically, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, and methyl glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, and diacetone alcohol, methyl acetate, and ethyl acetate And esters such as butyl acetate, ethers such as propylene glycol monomethyl ether, tetrahydrofuran and 1,4-dioxane.
また、ハードコート層用塗液は、屈折率を調整するために金属酸化物微粒子を含むことができる。金属酸化物微粒子としては、例えば、シリカ（二酸化珪素、ＳｉＯ２）、ＩＴＯ（インジウムー錫複合酸化物、屈折率２．０）、ＡＴＯ（アンチモン−錫複合酸化物、屈折率２．１）、酸化錫（屈折率２．０）、酸化アンチモン（屈折率２．１）、アンチモン酸亜鉛（屈折率１．７）、酸化亜鉛（屈折率２．１）、酸化ジルコニウム（屈折率２．１）、酸化チタン（屈折率２．４）及び酸化アルミニウム（屈折率１．６）等が挙げられる。金属酸化物微粒子が含まれる場合の金属酸化物微粒子の添加量は、活性エネルギー線硬化性樹脂１００質量部に対して１〜４００質量部程度であることが好ましい。 The hard coat layer coating liquid may contain metal oxide fine particles in order to adjust the refractive index. Examples of the metal oxide fine particles include silica (silicon dioxide, S i O 2 ), ITO (indium-tin composite oxide, refractive index 2.0), ATO (antimony-tin composite oxide, refractive index 2.1). , Tin oxide (refractive index 2.0), antimony oxide (refractive index 2.1), zinc antimonate (refractive index 1.7), zinc oxide (refractive index 2.1), zirconium oxide (refractive index 2.1) ), Titanium oxide (refractive index 2.4), and aluminum oxide (refractive index 1.6). When the metal oxide fine particles are contained, the addition amount of the metal oxide fine particles is preferably about 1 to 400 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin.
さらに、本発明の効果を損なわない範囲において、その他の成分をハードコート層に添加することができる。そのようなその他の成分としては、例えば重合体、重合開始剤、重合禁止剤、酸化防止剤、分散剤、界面活性剤、光安定剤及びレベリング剤等の添加剤が挙げられる。 Furthermore, other components can be added to the hard coat layer as long as the effects of the present invention are not impaired. Examples of such other components include additives such as a polymer, a polymerization initiator, a polymerization inhibitor, an antioxidant, a dispersant, a surfactant, a light stabilizer, and a leveling agent.
また、透明基材フィルムとハードコートの密着性を高めるために、透明基材フィルムとハードコート層の間に公知の干渉防止層を設けてもよい。なお、干渉防止層は、透明基材フィルムの製造時に公知の方法で透明基材フィルム表面に形成することができる。 Moreover, in order to improve the adhesiveness of a transparent base film and a hard coat, you may provide a well-known interference prevention layer between a transparent base film and a hard coat layer. In addition, an interference prevention layer can be formed in the transparent base film surface by a well-known method at the time of manufacture of a transparent base film.
ハードコート層の膜厚は１μｍ〜２０μｍが好ましい。ハードコート層の膜厚が１μｍ未満の場合には、十分な鉛筆硬度が得られないため好ましくない。一方、膜厚が２０μｍを超える場合には、耐屈曲性の低下等の問題が生じるため好ましくない。 The film thickness of the hard coat layer is preferably 1 μm to 20 μm. When the film thickness of the hard coat layer is less than 1 μm, it is not preferable because sufficient pencil hardness cannot be obtained. On the other hand, when the film thickness exceeds 20 μm, problems such as a decrease in flex resistance occur, which is not preferable.
（ハードコート層の形成方法）
このようなハードコート層の形成方法は特に限定されるものではない。例えば、ロールコート法、コイルバー法、ダイコート法等、一般的なウェットコート法によりハードコート層用塗液が透明基材フィルム上に塗布され、乾燥させた後に、紫外線、電子線等の活性エネルギー線照射により硬化される。
(Method for forming hard coat layer)
The method for forming such a hard coat layer is not particularly limited. For example, a hard coat layer coating solution is applied onto a transparent substrate film by a general wet coating method such as a roll coating method, a coil bar method, a die coating method, and the like, and after drying, active energy rays such as ultraviolet rays and electron beams Cured by irradiation.
＜低屈折率層＞
低屈折率層は、(a)多官能（メタ）アクリレート、(b)中空シリカ微粒子、及び(c)π共役系導電性高分子とドーパントからなる複合体（導電性高分子、錯体）を含有する低屈折率層用塗液の硬化物であり、透明基材フィルムおよびハードコート層よりも低い屈折率を有する。低屈折率層の厚みは、ｋλ／４とすることが光の干渉作用により表面反射が減少し、透過率が向上するため好ましい。ここで、λは光の波長４００〜６５０ｎｍ、ｋは１又は３を表す。このように低屈折率層の厚みをｋλ／４とすることで反射防止の効果をより高めることができる。ｋが１の場合と３の場合とを比較すると、ｋが１のときには、反射防止性能が相対的に高く、ｋが３のときには耐擦傷性が高くなる。
<Low refractive index layer>
The low refractive index layer contains (a) polyfunctional (meth) acrylate, (b) hollow silica fine particles, and (c) composites composed of π-conjugated conductive polymers and dopants (conductive polymers, complexes) It is a cured product of the coating solution for the low refractive index layer, and has a lower refractive index than the transparent base film and the hard coat layer. The thickness of the low refractive index layer is preferably kλ / 4 because surface reflection is reduced by light interference and the transmittance is improved. Here, λ represents a wavelength of light of 400 to 650 nm, and k represents 1 or 3. Thus, the antireflection effect can be further enhanced by setting the thickness of the low refractive index layer to kλ / 4. When k is 1 and 3, the antireflection performance is relatively high when k is 1, and the scratch resistance is high when k is 3.
中空シリカ微粒子は、低屈折率層の屈折率を積極的に低下させるために添加され、当該中空シリカ微粒子の添加量によって低屈折率層の屈折率を調整できる。そのうえで、低屈折率層の屈折率は１．２０〜１．４４であることが好ましい。屈折率が１．２０未満の低屈折率層を形成する場合、多官能（メタ）アクリレートの含有率を相対的に低くしなければならないため、低屈折率層は十分な塗膜強度を有することが難しくなる。一方、屈折率が１．４４を超える場合には、ハードコート層との屈折率差が小さくなり、十分な反射防止性能が得られない。 The hollow silica fine particles are added to actively lower the refractive index of the low refractive index layer, and the refractive index of the low refractive index layer can be adjusted by the addition amount of the hollow silica fine particles. In addition, the refractive index of the low refractive index layer is preferably 1.20 to 1.44. When forming a low refractive index layer having a refractive index of less than 1.20, the content of polyfunctional (meth) acrylate must be relatively low, so that the low refractive index layer has sufficient coating strength. Becomes difficult. On the other hand, when the refractive index exceeds 1.44, the refractive index difference from the hard coat layer becomes small, and sufficient antireflection performance cannot be obtained.
（多官能（メタ）アクリレート）
多官能（メタ）アクリレートは、紫外線や電子線のような活性エネルギー線を照射することにより、硬化反応を生じる樹脂であり、その種類は特に制限されない。具体的材料としては、ハードコート層の説明で挙げたものを使用できる。使用される樹脂は単官能（メタ）アクリレートでもよいが、(c)π共役系導電性高分子とドーパントからなる複合体を含有するため、塗膜の強度や耐擦傷性を向上させるという観点から、多官能（メタ）アクリレートが用いられる。
(Multifunctional (meth) acrylate)
Polyfunctional (meth) acrylate is a resin that causes a curing reaction when irradiated with active energy rays such as ultraviolet rays and electron beams, and the type thereof is not particularly limited. As specific materials, those mentioned in the description of the hard coat layer can be used. Although the resin used may be a monofunctional (meth) acrylate, (c) from the viewpoint of improving the strength and scratch resistance of the coating film because it contains a composite composed of a π-conjugated conductive polymer and a dopant. Polyfunctional (meth) acrylates are used.
（中空シリカ微粒子）
中空シリカ微粒子は、シリカ（二酸化珪素、ＳｉＯ２）がほぼ球状に形成され、その外殻内に中空部を有する微粒子である。中空シリカ微粒子の平均粒子径は好ましくは１０〜１００ｎｍ、より好ましくは２０〜６０ｎｍである。中空シリカ微粒子の平均粒子径が１０ｎｍより小さい場合、中空シリカ微粒子の製造が難しくなって好ましくない。一方、平均粒子径が１００ｎｍより大きい場合には、低屈折率層の膜厚（約１００ｎｍ）よりも大きくなってしまうため、低屈折率層表面での光の散乱が大きくなり、近赤外線遮蔽フィルムの透明性が損なわれてしまう。
(Hollow silica fine particles)
The hollow silica fine particles are fine particles in which silica (silicon dioxide, S i O 2 ) is formed in a substantially spherical shape and has a hollow portion in the outer shell. The average particle diameter of the hollow silica fine particles is preferably 10 to 100 nm, more preferably 20 to 60 nm. When the average particle diameter of the hollow silica fine particles is smaller than 10 nm, it is not preferable because the production of the hollow silica fine particles becomes difficult. On the other hand, when the average particle diameter is larger than 100 nm, the film thickness becomes larger than the film thickness of the low refractive index layer (about 100 nm). Transparency is impaired.
この中空シリカ微粒子は、有機溶剤に分散して使用する。該中空シリカ微粒子は、例えば特開２００６−２１９３８号公報に開示された製造方法により合成することもできる。この方法に基づいて、後述する実施例の中空シリカ微粒子（ゾル）が製造されている。また、中空シリカ微粒子の表面を、重合性二重結合を有するシランカップリング剤によって変性した変性中空シリカ微粒子を使用することもできる。 The hollow silica fine particles are used by being dispersed in an organic solvent. The hollow silica fine particles can also be synthesized, for example, by a production method disclosed in JP-A-2006-21938. Based on this method, hollow silica fine particles (sol) of Examples described later are produced. In addition, modified hollow silica fine particles obtained by modifying the surface of the hollow silica fine particles with a silane coupling agent having a polymerizable double bond can also be used.
（π共役系導電性高分子とドーパントからなる複合体）
π共役系導電性高分子とドーパントからなる複合体とは、π共役系導電性高分子にドーパントをドーピングしたものを示す。その屈折率はおよそ１．４９〜１．５２である。π共役系導電性高分子を単独で用いても導電性は発現されないが、ドーパントをドーピングすることによって、π共役系導電性高分子上を自由に動くことが可能な電子が生じ、導電性が得られるようになる。
(Composite composed of π-conjugated conductive polymer and dopant)
A complex composed of a π-conjugated conductive polymer and a dopant refers to a compound obtained by doping a π-conjugated conductive polymer with a dopant. Its refractive index is approximately 1.49 to 1.52. Even if a π-conjugated conductive polymer is used alone, conductivity is not exhibited, but doping with a dopant generates electrons that can move freely on the π-conjugated conductive polymer, and the conductivity is low. It will be obtained.
π共役系導電性高分子は、主鎖がπ共役系で構成されている有機高分子であれば特に限定されず公知のものを使用することができる。ここで、高分子化合物とは分子量が１０，０００以上の化合物のことを示す。π共役系導電性高分子は、例えば、ポリピロール類、ポリチオフェン類、ポリアニリン類、ポリフラン類、ポリアセチレン類、ポリフェニレン類、ポリフェニレンビニレン類、ポリアセン類ポリチオフェンビニレン類などを例示できる。これらは単独で用いてもよく、複数を混合して用いてもよい。中でも、導電性及び外部環境における安定性の点からポリチオフェン類、ポリピロール類又はポリアニリン類を用いるのが好ましく、特にポリチオフェン類を用いるのが好ましい。 The π-conjugated conductive polymer is not particularly limited as long as the main chain is an organic polymer having a π-conjugated system, and a known polymer can be used. Here, the polymer compound means a compound having a molecular weight of 10,000 or more. Examples of the π-conjugated conductive polymer include polypyrroles, polythiophenes, polyanilines, polyfurans, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyacenes polythiophene vinylenes, and the like. These may be used alone or in combination. Of these, polythiophenes, polypyrroles or polyanilines are preferred from the viewpoint of conductivity and stability in the external environment, and polythiophenes are particularly preferred.
ポリチオフェン類としては、例えば、ポリチオフェン、ポリ（３−メチルチオフェン）、ポリ（３−エチルチオフェン）、ポリ（３−ブロモチオフェン）、ポリ（３−クロロチオフェン）、ポリ（３−シアノチオフェン）、ポリ（３，４−ジメチルチオフェン）、ポリ（３−ヒドロキシチオフェン）、ポリ（３−メトキシチオフェン）、ポリ（３，４−ジメトキシチオフェン）などを例示できる。 Examples of polythiophenes include polythiophene, poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-bromothiophene), poly (3-chlorothiophene), poly (3-cyanothiophene), poly (3,4-dimethylthiophene), poly (3-hydroxythiophene), poly (3-methoxythiophene), poly (3,4-dimethoxythiophene) and the like can be exemplified.
ポリピロール類としては、例えば、ポリピロール、ポリ（３−メチルピロール）、ポリ（３−エチルピロール）、ポリ（３−ｎ−プロピルピロール）、ポリ（３，４−ジメチルピロール）、ポリ（３−カルボキシピロール）、ポリ（３−メチル−４−カルボキシピロール）などを例示できる。 Examples of the polypyrroles include polypyrrole, poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3,4-dimethylpyrrole), and poly (3-carboxyl). Pyrrole), poly (3-methyl-4-carboxypyrrole) and the like.
なお、π共役系導電性高分子は、非置換のままでも充分な導電性やバインダ樹脂への相溶性を得ることができるが、導電性をより高めるために、アルキル基、カルボキシ基、スルホン基、アルコキシ基、ヒロキシ基、シアノ基等の官能基を高分子中に導入しても良い。 In addition, the π-conjugated conductive polymer can obtain sufficient conductivity and compatibility with the binder resin even if it is not substituted, but in order to further increase the conductivity, an alkyl group, a carboxy group, a sulfone group In addition, a functional group such as an alkoxy group, a hydroxyl group, or a cyano group may be introduced into the polymer.
ドーパント（dopant）は、π共役系導電性高分子をドーピング（錯体形成）することにより、π共役系導電性高分子上を自由に動くことが可能な電子を生じさせ、π共役系導電性高分子に導電性を発現させる物質である。π共役系導電性高分子とドーパントの組み合わせは特に制限されないが、導電性及び外部環境における安定性の点からポリチオフェン類とポリアニオンの組み合わせが好ましい。 The dopant (dopant), by doping (complex formation) with a π-conjugated conductive polymer, generates electrons that can move freely on the π-conjugated conductive polymer, resulting in a high π-conjugated conductive conductivity. It is a substance that develops conductivity in molecules. The combination of the π-conjugated conductive polymer and the dopant is not particularly limited, but a combination of polythiophenes and polyanions is preferable from the viewpoint of conductivity and stability in the external environment.
ポリアニオンとは分子内にアニオン性基を有する化合物である。ポリアニオンの具体例としては、例えばポリビニルスルホン酸、ポリスチレンスルホン酸、ポリアクリル酸ブチルスルホン酸、ポリイソプレンスルホン酸、ポリアクリル酸等が挙げられる。これらの単独重合体であってもよいし、２種以上の共重合体であってもよい。 A polyanion is a compound having an anionic group in the molecule. Specific examples of the polyanion include polyvinyl sulfonic acid, polystyrene sulfonic acid, polybutyl acrylate sulfonic acid, polyisoprene sulfonic acid, polyacrylic acid and the like. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient.
π共役系導電性高分子とドーパントの質量比は１：１〜１：５であることが必要である。π共役系導電性高分子とドーパントの質量比が１：１よりも小さい場合には、π共役系導電性高分子が十分にドーピングされず、複合体の導電性が低下する。一方、１：５よりも大きい場合には、過剰に存在するドーパントの影響により、複合体の耐熱性が悪化する。π共役系導電性高分子とドーパントからなる複合体は、π共役系導電性高分子とドーパントからなる複合体の水分散体を有機溶剤で置き換えて使用してもよい。 The mass ratio between the π-conjugated conductive polymer and the dopant needs to be 1: 1 to 1: 5. When the mass ratio of the π-conjugated conductive polymer and the dopant is smaller than 1: 1, the π-conjugated conductive polymer is not sufficiently doped, and the conductivity of the composite is lowered. On the other hand, when it is larger than 1: 5, the heat resistance of the composite deteriorates due to the influence of an excessive dopant. The complex composed of the π-conjugated conductive polymer and the dopant may be used by replacing the aqueous dispersion of the complex composed of the π-conjugated conductive polymer and the dopant with an organic solvent.
低屈折率層用塗液における(a)多官能（メタ）アクリレート、(b)中空シリカ微粒子、および(c)π共役系導電性高分子とドーパントからなる複合体の各々の含有量は、(a)多官能（メタ）アクリレート１００質量部あたり、(b)中空シリカ微粒子４０〜２５０質量部、 (c)π共役系導電性高分子とドーパントからなる複合体１〜２５質量部である。中空シリカ微粒子の含有量が４０質量部よりも少ない場合には、近赤外線遮蔽フィルムの十分な反射防止性能が得られず、２５０質量部よりも多い場合には、多官能（メタ）アクリレートの含有率が低下するため近赤外線遮蔽フィルムの耐擦傷性が低下する。 The contents of (a) polyfunctional (meth) acrylate, (b) hollow silica fine particles, and (c) a complex composed of a π-conjugated conductive polymer and a dopant in the coating solution for the low refractive index layer are ( (a) 40 to 250 parts by mass of hollow silica fine particles per 100 parts by mass of polyfunctional (meth) acrylate, and (c) 1 to 25 parts by mass of a complex composed of a π-conjugated conductive polymer and a dopant. When the content of the hollow silica fine particles is less than 40 parts by mass, sufficient antireflection performance of the near-infrared shielding film cannot be obtained, and when the content is more than 250 parts by mass, the polyfunctional (meth) acrylate is contained. Since the rate decreases, the scratch resistance of the near-infrared shielding film decreases.
また、π共役系導電性高分子とドーパントからなる複合体の含有量が１質量部よりも少ない場合には、近赤外線遮蔽フィルムの十分な帯電防止性能が得られず、２５質量部よりも多い場合には、複合体に対する多官能（メタ）アクリレートの含有率が相対的に減少するために、近赤外線遮蔽フィルムの耐擦傷性が低下する。 Moreover, when the content of the complex composed of the π-conjugated conductive polymer and the dopant is less than 1 part by mass, sufficient antistatic performance of the near-infrared shielding film cannot be obtained, and more than 25 parts by mass. In this case, the content of polyfunctional (meth) acrylate with respect to the composite is relatively reduced, so that the scratch resistance of the near-infrared shielding film is lowered.
（希釈溶剤）
低屈折率層用塗液には任意の溶媒を用いることができる。溶媒として具体的には、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソブチルアルコール、メチルグリコール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ジアセトンアルコール等のケトン類、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル類、プロピレングリコールモノメチルエーテル、テトラヒドロフラン、１，４−ジオキサン等のエーテル類が挙げられる。
(Diluted solvent)
Any solvent can be used for the coating solution for the low refractive index layer. Specific examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol and methyl glycol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone and diacetone alcohol, methyl acetate, Examples thereof include esters such as ethyl acetate and butyl acetate, and ethers such as propylene glycol monomethyl ether, tetrahydrofuran and 1,4-dioxane.
（その他の成分）
また、本発明の効果を損なわない範囲において、その他の成分を低屈折率層用塗液に添加することができる。そのようなその他の成分としては、例えば重合体、重合開始剤、重合禁止剤、酸化防止剤、分散剤、界面活性剤、光安定剤及びレベリング剤等の添加剤が挙げられる。
(Other ingredients)
In addition, other components can be added to the coating solution for the low refractive index layer within a range not impairing the effects of the present invention. Examples of such other components include additives such as a polymer, a polymerization initiator, a polymerization inhibitor, an antioxidant, a dispersant, a surfactant, a light stabilizer, and a leveling agent.
（低屈折率層の形成方法）
低屈折率層を形成する方法は特に制限されないが、低屈折率層用塗液をロールコート法、スピンコート法、コイルバー法、ディップコート法、ダイコート法等の塗布方法により透明基材フィルム上に積層されたハードコート層の表面に塗布した後、紫外線を照射する方法が挙げられる。このような方法により、低屈折率層用塗液が硬化して硬化物が得られ、低屈折率層が形成される。低屈折率層用塗液の塗布方法としては、ロールコート法等の低屈折率層を連続的に形成できる方法が生産性の点より好ましい。
(Method for forming low refractive index layer)
The method for forming the low refractive index layer is not particularly limited, but the coating liquid for the low refractive index layer is applied to the transparent substrate film by a coating method such as a roll coating method, a spin coating method, a coil bar method, a dip coating method, or a die coating method. A method of irradiating with ultraviolet rays after being applied to the surface of the laminated hard coat layer can be mentioned. By such a method, the coating solution for the low refractive index layer is cured to obtain a cured product, and a low refractive index layer is formed. As a method for applying the coating solution for the low refractive index layer, a method capable of continuously forming the low refractive index layer such as a roll coating method is preferable from the viewpoint of productivity.
＜近赤外線吸収性粘着層＞
近赤外線吸収性粘着層は、近赤外線吸収機能と粘着機能を併せ持った機能層であり、透明基材に対して低屈折率層を積層した反対側の他方面に積層される。近赤外線吸収性粘着層は、（メタ）アクリル系粘着樹脂組成物と近赤外線吸収色素とを含む近赤外線吸収性粘着剤の硬化により形成される。
<Near-infrared absorbing adhesive layer>
The near-infrared absorbing adhesive layer is a functional layer having both a near-infrared absorbing function and an adhesive function, and is laminated on the other surface on the opposite side where a low refractive index layer is laminated on a transparent substrate. A near-infrared absorptive adhesive layer is formed by hardening of the near-infrared absorptive adhesive containing a (meth) acrylic-type adhesive resin composition and a near-infrared absorptive pigment | dye.
近赤外線吸収性粘着層を透明基材に設ける方法としては、近赤外線吸収性粘着剤をウェットコート法により塗布する方法であれば特に制限されず、例えばグラビアコート法、スピンコート法、ダイコート法等の従来公知の塗工方法を採用することができる。 The method for providing the near infrared absorbing pressure-sensitive adhesive layer on the transparent substrate is not particularly limited as long as the near infrared absorbing pressure-sensitive adhesive is applied by a wet coating method. For example, a gravure coating method, a spin coating method, a die coating method, etc. A conventionally known coating method can be employed.
（（メタ）アクリル系粘着樹脂組成物）
本発明における（メタ）アクリル系粘着樹脂組成物は、例えばメチル（メタ）アクリレート、ブチル（メタ）アクリレート等のアルキル（メタ）アクリレートと（メタ）アクリル酸とを重合した重合体等を用いることができる。（メタ）アクリル系粘着樹脂組成物を形成する単量体は特に制限されず、従来公知の重合体を用いることができる。
((Meth) acrylic adhesive resin composition)
The (meth) acrylic pressure-sensitive adhesive resin composition in the present invention uses, for example, a polymer obtained by polymerizing alkyl (meth) acrylate such as methyl (meth) acrylate and butyl (meth) acrylate and (meth) acrylic acid. it can. The monomer that forms the (meth) acrylic adhesive resin composition is not particularly limited, and a conventionally known polymer can be used.
（メタ）アクリル系粘着樹脂組成物の酸価は２０ｍｇＫＯＨ／ｇ以下であり、好ましくは１５ｍｇＫＯＨ／ｇ以下である。この酸価が２０ｍｇＫＯＨ／ｇより大きい場合には、（メタ）アクリル系粘着樹脂組成物に近赤外線吸収色素を添加した際に近赤外線吸収色素の劣化が促進され、さらには近赤外線吸収性粘着層を電磁波遮蔽層として使用される銅メッシュ等の金属メッシュ上に形成した際に金属メッシュの酸化劣化が促進されるため不適当である。 The acid value of the (meth) acrylic adhesive resin composition is 20 mgKOH / g or less, preferably 15 mgKOH / g or less. When this acid value is larger than 20 mgKOH / g, the deterioration of the near-infrared absorbing dye is promoted when the near-infrared absorbing dye is added to the (meth) acrylic adhesive resin composition, and further, the near-infrared absorbing pressure-sensitive adhesive layer Is formed on a metal mesh such as a copper mesh used as an electromagnetic wave shielding layer, which is inappropriate because oxidative degradation of the metal mesh is promoted.
（メタ）アクリル系粘着樹脂組成物を形成する単量体は特に制限されず、例えばメチル（メタ）アクリレート、ブチル（メタ）アクリレート等のアルキル（メタ）アクリレートと（メタ）アクリル酸とを重合した重合体を用いることができる。また、（メタ）アクリレートの他に、例えばエチレン、酢酸ビニル、スチレン等の不飽和二重結合を有するオレフィン系単量体、ビニル系単量体との共重合体も用いることができる。 The monomer that forms the (meth) acrylic pressure-sensitive adhesive resin composition is not particularly limited. For example, alkyl (meth) acrylate such as methyl (meth) acrylate and butyl (meth) acrylate and (meth) acrylic acid are polymerized. A polymer can be used. In addition to (meth) acrylate, for example, an olefin monomer having an unsaturated double bond such as ethylene, vinyl acetate, styrene, or a copolymer with a vinyl monomer can also be used.
（メタ）アクリル系粘着樹脂組成物は、（メタ）アクリル酸のほか、例えば２−ヒドロキシエチル（メタ）アクリレート等の水酸基を有する単量体や、マレイン酸、イタコン酸、クロトン酸等のカルボキシル基を有する単量体等のイソシアネート系架橋剤のイソシアネート基と反応する官能基を有する単量体を含有させて形成されていても良い。これにより、該官能基を有する単量体が（メタ）アクリル酸と共重合して官能基を有する（メタ）アクリル系樹脂を得ることができ、この官能基がイソシアネート系架橋剤のイソシアネート基と反応して架橋構造を形成し、近赤外線吸収性粘着層の機械的強度等を高めることができる。 In addition to (meth) acrylic acid, the (meth) acrylic adhesive resin composition is a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, or a carboxyl group such as maleic acid, itaconic acid or crotonic acid. It may be formed by containing a monomer having a functional group that reacts with an isocyanate group of an isocyanate-based cross-linking agent such as a monomer having. Thereby, the monomer which has this functional group can be copolymerized with (meth) acrylic acid, and the (meth) acrylic-type resin which has a functional group can be obtained, and this functional group and the isocyanate group of an isocyanate type crosslinking agent are obtained. It reacts to form a crosslinked structure, and the mechanical strength and the like of the near infrared absorbing adhesive layer can be increased.
（メタ）アクリル系粘着樹脂組成物に使用される架橋剤は特に限定されないが、例えばイソシアネート系架橋剤等が好適に用いられる。粘着樹脂組成物には本発明の機能を損なわない限りにおいて、その他の添加剤が添加されていても良い。その他の添加剤としては、例えば酸化防止剤、紫外線吸収剤等が挙げられるが、これらに制限されない。また、その他の添加剤は従来公知の化合物を用いることができる。 Although the crosslinking agent used for a (meth) acrylic-type adhesive resin composition is not specifically limited, For example, an isocyanate type crosslinking agent etc. are used suitably. Other additives may be added to the adhesive resin composition as long as the functions of the present invention are not impaired. Examples of other additives include, but are not limited to, antioxidants and ultraviolet absorbers. Moreover, a conventionally well-known compound can be used for another additive.
（近赤外線吸収色素）
本発明における近赤外線吸収色素はジイモニウム系色素又はフタロシアニン系色素より選ばれる。これらの近赤外線吸収色素は光の波長８００〜１１００ｎｍに極大吸収波長を有するため可視光線を不必要に吸収することがなく、ＰＤＰに使用する上で十分な近赤外線吸収能を発揮することができる。
(Near-infrared absorbing dye)
The near-infrared absorbing dye in the present invention is selected from a diimonium dye or a phthalocyanine dye. Since these near-infrared absorbing dyes have a maximum absorption wavelength at a light wavelength of 800 to 1100 nm, they do not unnecessarily absorb visible light, and can exhibit sufficient near-infrared absorbing ability for use in PDPs. .
このようなジイモニウム系色素の市販品としては、例えばＣＩＲ−１０８５、ＣＩＲ−ＲＬ〔以上、日本カーリット（株）製のジイモニウム系色素の商品名〕、ＩＲＧ−０２２、ＩＲＧ−０６７〔以上、日本化薬（株）製のジイモニウム系色素の商品名〕等、フタロシアニン系色素としては、例えばイーエクスカラーＩＲ−１０Ａ、イーエクスカラーＩＲ−１２、イーエクスカラーＩＲ−１４、ＴＸ−ＥＸ−８２０、ＴＸ−ＥＸ−９０６Ｂ、ＴＸ−ＥＸ−９１０Ｂ、ＴＸ−ＥＸ−９１５〔以上、（株）日本触媒製のフタロシアニン系色素の商品名〕等がそれぞれ挙げられる。これらの中でも、ジイモニウム系色素が可視光領域の透過率を高く保てることにより色設計が容易となるため好ましい。 Examples of such commercially available dimonium dyes include CIR-1085, CIR-RL [above, trade names of diimonium dyes manufactured by Nippon Carlit Co., Ltd.], IRG-022, IRG-067 [above, Nippon Kayaku Co., Ltd.] Examples of phthalocyanine dyes such as EEXCOLOR IR-10A, EEXCOLOR IR-12, EEXCOLOR IR-14, TX-EX-820, TX, etc. -EX-906B, TX-EX-910B, TX-EX-915 [above, trade names of phthalocyanine dyes manufactured by Nippon Shokubai Co., Ltd.] and the like. Among these, diimonium dyes are preferable because color design is facilitated by maintaining high transmittance in the visible light region.
近赤外線吸収色素の含有量は、（メタ）アクリル系樹脂１００質量部に対して０．５〜３．０質量部が好ましい。該近赤外線吸収色素の含有量が０．５〜３．０質量部であれば実用上近赤外線吸収能と可視光線の透過率が十分な近赤外線吸収性粘着層を得ることができる。近赤外線吸収色素の含有量が０．５質量部より少ない場合、近赤外線吸収能を十分に発揮することができず、可視光線の透過率も低下する傾向を示す。一方、その含有量が３．０質量部より多い場合、近赤外線吸収性粘着層の粘着性能が低下するなどの傾向を示す。 As for content of a near-infrared absorption pigment | dye, 0.5-3.0 mass parts is preferable with respect to 100 mass parts of (meth) acrylic-type resin. When the content of the near-infrared absorbing dye is 0.5 to 3.0 parts by mass, a near-infrared-absorbing pressure-sensitive adhesive layer having practically sufficient near-infrared absorbing ability and visible light transmittance can be obtained. When the content of the near-infrared absorbing dye is less than 0.5 parts by mass, the near-infrared absorbing ability cannot be sufficiently exhibited, and the visible light transmittance tends to decrease. On the other hand, when the content is more than 3.0 parts by mass, the adhesive performance of the near infrared absorbing adhesive layer tends to decrease.
近赤外線吸収色素は有機溶剤に溶解させて用いるが、耐久性能を高めるために微粒子分散状態で用いても良い。この場合、平均粒子径が０．００１〜０．１μｍの微粒子分散状態で存在することが好ましく、平均粒子径が０．００５〜０．０３０μｍの微粒子分散状態で存在することがさらに好ましい。平均粒子径が０．１μｍを超えると光の散乱により白ボケを生ずるため不適当であり、平均粒子径が０．００１μｍ未満であると溶解により耐久性能を十分に発現することができないという弊害がある。尚、本発明における平均粒子径とは、ｎａｎｏｔｒａｃＵＰＡ−ＥＸ１５０〔日機装（株）製の粒度分布測定機〕を用いて動的光散乱理論／周波数マトリックス解析法（ＦＦＴ法）により測定した値のことをいう。 The near-infrared absorbing dye is used after being dissolved in an organic solvent, but may be used in a fine particle dispersed state in order to improve durability. In this case, it is preferably present in a fine particle dispersed state having an average particle diameter of 0.001 to 0.1 μm, and more preferably present in a fine particle dispersed state having an average particle diameter of 0.005 to 0.030 μm. If the average particle size exceeds 0.1 μm, white blurring occurs due to light scattering, which is inappropriate. If the average particle size is less than 0.001 μm, the durability cannot be sufficiently exhibited by dissolution. is there. In addition, the average particle diameter in this invention is the value measured by the dynamic light scattering theory / frequency matrix analysis method (FFT method) using nanotracUPA-EX150 [The particle size distribution measuring machine by Nikkiso Co., Ltd.]. Say.
近赤外線吸収色素の分散方法は特に限定されず、従来公知の分散方法を用いることができる。例えば、有機溶剤にジイモニウム塩化合物を少量ずつ撹拌しながら添加してゆき、ガラスビーズを加えてペイントシェイカーで物理的に粉砕する方法が挙げられるが、これに限定されるものではない。 The dispersion method of the near infrared absorbing dye is not particularly limited, and a conventionally known dispersion method can be used. For example, a method of adding a diimonium salt compound to an organic solvent while stirring little by little, adding glass beads and physically pulverizing with a paint shaker can be mentioned, but is not limited thereto.
また、近赤外線吸収性粘着層には、光の波長３８０〜７８０ｎｍ（可視光線の波長域）の領域に極大吸収波長を有する色補正色素を含有させることができる。この色補正色素を含むことにより、近赤外線吸収性粘着層をＰＤＰに使用した際に色再現性を向上させることができる。光の波長３８０〜７８０ｎｍの領域に極大吸収波長を有する色補正色素は特に制限されず、例えばアザポルフィリン系化合物、シアニン系化合物、その他スクアリリウム系化合物、アゾメチン系化合物、ポリメチン系化合物、キサンテン系化合物、ピロメテン系化合物、イソインドリノン系化合物、キナクリドン系化合物、ジケトピロロピロール系化合物、アントラキノン系化合物、ジオキサジン系化合物等、従来公知の化合物を用いることができるが、耐久性能の良好なアザポルフィリン系化合物が好ましい。アザポルフィリン系化合物の中では、吸収特性の良好なテトラアザポルフィリン系化合物が好ましく、例えばＴＡＰ‐２、ＴＡＰ‐１８（山田化学工業(株)製テトラアザポリフィリン化合物）、ＰＤ‐３２０、ＰＤ‐３２１（山本化成(株)製テトラアザポリフィリン化合物）等が用いられる。 Moreover, the near-infrared absorptive pressure-sensitive adhesive layer can contain a color correction dye having a maximum absorption wavelength in a region of light wavelength of 380 to 780 nm (visible light wavelength region). By including this color correction pigment, color reproducibility can be improved when the near-infrared absorbing adhesive layer is used in a PDP. The color correction dye having a maximum absorption wavelength in the light wavelength region of 380 to 780 nm is not particularly limited, and examples thereof include azaporphyrin compounds, cyanine compounds, other squarylium compounds, azomethine compounds, polymethine compounds, xanthene compounds, Conventionally known compounds such as pyromethene compounds, isoindolinone compounds, quinacridone compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, dioxazine compounds can be used, but azaporphyrin compounds with good durability performance Is preferred. Among the azaporphyrin compounds, tetraazaporphyrin compounds having good absorption characteristics are preferable. For example, TAP-2, TAP-18 (tetraazaporphyrin compound manufactured by Yamada Chemical Co., Ltd.), PD-320, PD-321. (Tetraazaporphyrin compound manufactured by Yamamoto Kasei Co., Ltd.) and the like are used.
＜近赤外線遮蔽体＞
本発明の近赤外線遮蔽体は、上記近赤外線遮蔽フィルムを、近赤外線吸収性粘着層を介して基材に貼り合わせて成る。ここでの基材としては、透明であれば特に制限されず、例えばポリエチレンテレフタレート（ＰＥＴ）フィルム、トリアセチルセルロース（ＴＡＣ）フィルム等の透明樹脂フィルム等のほか、ガラス板やアクリル板等を用いることができる。また、本発明の効果を阻害しない範囲で、透明基材上に防汚層、耐指紋性層、反射防止層、アンチグレア層、透明導電層、書味向上性層、接着性改良層、屈折率調整層等の機能層を設けてもよい。これにより、近赤外線遮蔽体は近赤外線吸収性能に加えて、様々な機能を発揮することが可能になる
<Near-infrared shield>
The near-infrared shielding body of the present invention is formed by bonding the near-infrared shielding film to a substrate via a near-infrared absorbing adhesive layer. As a base material here, if it is transparent, it will not restrict | limit in particular, For example, in addition to transparent resin films, such as a polyethylene terephthalate (PET) film and a triacetyl cellulose (TAC) film, a glass plate, an acrylic board, etc. are used. Can do. In addition, the antifouling layer, the fingerprint-resistant layer, the antireflection layer, the antiglare layer, the transparent conductive layer, the writing quality improving layer, the adhesion improving layer, the refractive index on the transparent substrate as long as the effects of the present invention are not impaired. A functional layer such as an adjustment layer may be provided. Thereby, in addition to the near-infrared absorption performance, the near-infrared shield can exhibit various functions.
以下に、実施例及び比較例を挙げて本発明の実施形態をさらに具体的に説明する。なお、各例における部は質量部を示し、％は質量％を表す。 The embodiments of the present invention will be described more specifically below with reference to examples and comparative examples. In addition, the part in each example shows a mass part and% represents the mass%.
〔ハードコート層用塗液の製造〕
（ハードコート層用塗液ＨＣ−１の製造）
光重合性ウレタンアクリレート[日本合成化学工業（株）製、商品名：紫光ＵＶ７６００Ｂ]５０質量部、ジペンタエリスリトールヘキサアクリレート[日本化薬（株）製、商品名：ＤＰＨＡ]２０質量部、光重合開始剤[チバスペシャリティケミカル（株）製、商品名：ＩＲＧＡＣＵＲＥ１８４]３質量部及びイソプロピルアルコール３０質量部を混合して、ハードコート層用塗液ＨＣ−１を得た。
[Manufacture of coating liquid for hard coat layer]
(Manufacture of coating liquid HC-1 for hard coat layer)
50 parts by mass of photopolymerizable urethane acrylate [manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name: Purple light UV7600B], 20 parts by mass of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA], photopolymerization 3 parts by mass of an initiator [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGACURE184] and 30 parts by mass of isopropyl alcohol were mixed to obtain a coating liquid HC-1 for a hard coat layer.
（ハードコート層用塗液ＨＣ−２の製造）
中空シリカ微粒子（ＳｉＯ２、平均粒子径：１０ｎｍ）３５質量部、ジペンタエリスリトールヘキサアクリレート[日本化薬（株）製、商品名：ＤＰＨＡ]２５質量部、光重合開始剤[チバスペシャリティケミカル（株）製、商品名：ＩＲＧＡＣＵＲＥ１８４]５質量部及びメチルエチルケトン４０質量部を混合して、ハードコート層用塗液ＨＣ−２を得た。
(Manufacture of hard coat layer coating liquid HC-2)
Hollow silica fine particles (SiO 2 , average particle diameter: 10 nm) 35 parts by mass, dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA] 25 parts by mass, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd. ), Trade name: IRGACURE 184] and 5 parts by mass of methyl ethyl ketone were mixed to obtain a hard coat layer coating solution HC-2.
（ハードコート層用塗液ＨＣ−３の製造）
酸化ジルコニウム微粒子（平均粒子径：３０ｎｍ）４６質量部、ジペンタエリスリトールヘキサアクリレート[日本化薬（株）製、商品名：ＤＰＨＡ]３１質量部、光重合開始剤[チバスペシャリティケミカル（株）製、商品名：ＩＲＧＡＣＵＲＥ１８４]５質量部及びイソブチルアルコール２３質量部を混合して、ハードコート層用塗液ＨＣ−３を得た。
(Manufacture of hard coat layer coating liquid HC-3)
Zirconium oxide fine particles (average particle diameter: 30 nm) 46 parts by mass, dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA] 31 parts by mass, photopolymerization initiator [manufactured by Ciba Specialty Chemicals, Product name: IRGACURE184] 5 parts by mass and isobutyl alcohol 23 parts by mass were mixed to obtain a hard coat layer coating solution HC-3.
（ハードコート層用塗液ＨＣ−４の製造）
アンチモン酸亜鉛微粒子（平均粒子径：３０ｎｍ）５質量部、ジペンタエリスリトールヘキサアクリレート[日本化薬（株）製、商品名：ＤＰＨＡ]６５質量部、光重合開始剤[チバスペシャリティケミカル（株）製、商品名：ＩＲＧＡＣＵＲＥ１８４]５質量部及びメチルエチルケトン３０質量部を混合して、ハードコート層用塗液ＨＣ−４を得た。
(Manufacture of hard coat layer coating liquid HC-4)
Zinc antimonate fine particles (average particle size: 30 nm) 5 parts by mass, dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA] 65 parts by mass, photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd. , Trade name: IRGACURE 184] and 5 parts by mass of methyl ethyl ketone were mixed to obtain a hard coat layer coating solution HC-4.
〔変性中空シリカ微粒子（ゾル）の製造〕
第１工程として、平均粒子径５ｎｍ、シリカ（ＳｉＯ２）濃度２０％のシリカゾルと純水とを混合して反応母液を調製し、８０℃に加温した。この反応母液のｐＨは１０．５であり、同反応母液にＳｉＯ２として１．１７％の珪酸ナトリウム水溶液と、アルミナ（Ａｌ２Ｏ３）として０．８３％のアルミン酸ナトリウム水溶液とを同時に添加した。その間、反応液の温度を８０℃に保持した。反応液のｐＨは、珪酸ナトリウム及びアルミン酸ナトリウムの添加直後１２．５に上昇し、その後ほとんど変化しなかった。添加終了後、反応液を室温まで冷却し、限外濾過膜で洗浄して固形分濃度２０％のＳｉＯ２・Ａｌ２Ｏ３一次粒子分散液（核粒子分散液）を調製した。
[Production of modified hollow silica fine particles (sol)]
As a first step, a silica sol having an average particle diameter of 5 nm and a silica (SiO 2 ) concentration of 20% and pure water were mixed to prepare a reaction mother liquor, which was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 1.17% sodium silicate aqueous solution as SiO 2 and 0.83% sodium aluminate aqueous solution as alumina (Al 2 O 3 ) were simultaneously added to the reaction mother liquor. did. Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition of sodium silicate and sodium aluminate and remained almost unchanged thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to prepare a SiO 2 .Al 2 O 3 primary particle dispersion (core particle dispersion) having a solid concentration of 20%.
次いで、第２工程として、このＳｉＯ２・Ａｌ２Ｏ３一次粒子分散液を採取し、純水を加えて９８℃に加温し、この温度を保持しながら、濃度０．５％の硫酸ナトリウムを添加した。続いて、ＳｉＯ２として濃度１．１７％の珪酸ナトリウム水溶液と、Ａｌ２Ｏ３として濃度０．５％のアルミン酸ナトリウム水溶液とを添加して複合酸化物微粒子分散液（核粒子に第１シリカ被覆層を形成した微粒子分散液）を得た。そして、これを限外濾過膜で洗浄して固形分濃度１３％の複合酸化物微粒子分散液とした。 Next, as a second step, this SiO 2 · Al 2 O 3 primary particle dispersion is collected, pure water is added and heated to 98 ° C., and while maintaining this temperature, sodium sulfate having a concentration of 0.5% Was added. Subsequently, an aqueous solution of sodium silicate having a concentration of 1.17% as SiO 2 and an aqueous solution of sodium aluminate having a concentration of 0.5% as Al 2 O 3 were added to form a composite oxide fine particle dispersion (first silica as a core particle). A fine particle dispersion having a coating layer was obtained. And this was wash | cleaned with the ultrafiltration membrane, and it was set as the complex oxide fine particle dispersion liquid of solid content concentration 13%.
第３工程として、この複合酸化物微粒子分散液に純水を加え、さらに濃塩酸（３５．５％）を滴下してｐＨ１．０とし、脱アルミニウム処理を行った。次いで、ｐＨ３の塩酸水溶液１０Ｌと純水５Ｌとを加えながら限外濾過膜で溶解したアルミニウム塩を分離し、洗浄して固形分濃度２０％のシリカ系微粒子（１）の水分散液を得た。 As a third step, pure water was added to the composite oxide fine particle dispersion, and concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0, followed by dealumination. Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and washed to obtain an aqueous dispersion of silica-based fine particles (1) having a solid content concentration of 20%. .
第４工程として、前記固形分濃度２０％のシリカ系微粒子（１）の水分散液と、純水、エタノール及び２８％アンモニア水との混合液を３５℃に加温した後、エチルシリケート（ＳｉＯ２が２８％）を添加してシリカ被膜（第２シリカ被覆層）を形成した。続いて、純水５Ｌを加えながら、限外濾過膜で洗浄して固形分濃度２０％のシリカ系微粒子（２）の分散液を調製した。 As a fourth step, a mixture of an aqueous dispersion of silica-based fine particles (1) having a solid content concentration of 20%, pure water, ethanol and 28% aqueous ammonia is heated to 35 ° C., and then ethyl silicate (SiO 2 2 was 28%) to form a silica coating (second silica coating layer). Subsequently, while adding 5 L of pure water, it was washed with an ultrafiltration membrane to prepare a dispersion of silica-based fine particles (2) having a solid concentration of 20%.
最後に第５工程として、再びシリカ系微粒子（２）の分散液を２００℃にて１１時間水熱処理した。その後、純水５Ｌを加えながら限外濾過膜で洗浄して固形分濃度２０％に調整した。そして、限外濾過膜を用いて、この分散液の分散媒をエタノールに置換し、固形分濃度２０％のオルガノゾルを得た。このオルガノゾルは、平均粒子径が６０ｎｍで、比表面積が１１０ｍ２／ｇの中空シリカ微粒子が分散されたオルガノゾル（以下、「中空シリカゾルＡ」と称する。）であった。 Finally, as a fifth step, the dispersion of silica-based fine particles (2) was hydrothermally treated again at 200 ° C. for 11 hours. Thereafter, it was washed with an ultrafiltration membrane while adding 5 L of pure water to adjust the solid content concentration to 20%. Then, using an ultrafiltration membrane, the dispersion medium of this dispersion was replaced with ethanol to obtain an organosol having a solid content concentration of 20%. This organosol was an organosol in which hollow silica fine particles having an average particle diameter of 60 nm and a specific surface area of 110 m 2 / g were dispersed (hereinafter referred to as “hollow silica sol A”).
該中空シリカゾルＡ（シリカ固形分濃度２０％）２００ｇを用意し、限外濾過膜にて、メタノールへの溶媒置換を行い、ＳｉＯ２分が２０％のオルガノゾル１００ｇ（水分量はＳｉＯ２分に対して０．５％）を調製した。そこへ２８％アンモニア水溶液を前記オルガノゾル１００ｇに対してアンモニアとして１００ｐｐｍとなるように加え、十分に混合し、次にγ−アクリロイルオキシプロピルトリメトキシシラン〔商品名：ＫＢＭ５１０３、信越化学（株）製〕３．６ｇを添加し、反応液とした。 Providing a hollow silica sol A (silica solid concentration of 20%) 200 g, an ultrafiltration membrane, subjected to solvent substitution to methanol, SiO 2 minutes 20% of the organosol 100 g (water content relative to SiO 2 minutes 0.5%). Thereto, 28% aqueous ammonia solution was added to 100 g of the organosol so as to be 100 ppm as ammonia, and mixed well, and then γ-acryloyloxypropyltrimethoxysilane [trade name: KBM5103, manufactured by Shin-Etsu Chemical Co., Ltd.] 3.6 g was added to prepare a reaction solution.
これを５０℃に加温し、撹拌しながら５０℃で６時間加熱を行った。加熱終了後、反応液を常温まで冷却し、さらにロータリーエバポレーターでイソプロピルアルコールへ溶媒置換を行い、ＳｉＯ２濃度２０％の被覆中空微粒子からなるオルガノゾルを得た。このオルガノゾルは、平均粒子径が６０ｎｍ、屈折率１．２５、空隙率４０〜４５％で、比表面積が１３０ｍ２／ｇ、熱質量測定法（ＴＧ）による質量減少割合が３．６％の変性中空シリカ微粒子が分散されたオルガノゾル（変性中空シリカ微粒子ゾル）であった。 This was heated to 50 ° C. and heated at 50 ° C. for 6 hours with stirring. After completion of the heating, the reaction solution was cooled to room temperature, and further the solvent was replaced with isopropyl alcohol by a rotary evaporator to obtain an organosol composed of coated hollow fine particles having a SiO 2 concentration of 20%. This organosol has an average particle size of 60 nm, a refractive index of 1.25, a porosity of 40 to 45%, a specific surface area of 130 m 2 / g, and a mass reduction ratio by thermal mass measurement (TG) of 3.6%. It was an organosol (modified hollow silica fine particle sol) in which hollow silica fine particles were dispersed.
〔低屈折率層用塗液の調製〕
（低屈折率層用塗液Ｌ−１の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で１部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを４３０８部混合して低屈折率層用塗液Ｌ−１を調製した。
(Preparation of coating solution for low refractive index layer)
(Preparation of coating liquid L-1 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) 1 part of a composite of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: 12.5 parts of Irgacure 907] and 4308 parts of isopropyl alcohol were mixed to prepare a coating solution L-1 for a low refractive index layer.
（低屈折率層用塗液Ｌ−２の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３−メチルチオフェン）／ポリビニルスルホン酸＝１／２．５の複合体を固形分換算で２．５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを４１８８部混合して低屈折率層用塗液Ｌ−２を調製した。
(Preparation of coating liquid L-2 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 3-methylthiophene) / polyvinylsulfonic acid = 1 / 2.5 composite in terms of solid content, 2.5 parts, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] 12.5 parts and 4188 parts of isopropyl alcohol were mixed to prepare a coating solution L-2 for a low refractive index layer.
（低屈折率層用塗液Ｌ−３の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−３を調製した。
(Preparation of coating liquid L-3 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) 5 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 composite in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: 12.5 parts of Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-3 for a low refractive index layer.
（低屈折率層用塗液Ｌ−４の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３−ヘキシルオキシチオフェン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で７．５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３７８８部混合して低屈折率層用塗液Ｌ−４を調製した。
(Preparation of coating liquid L-4 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 3-hexyloxythiophene) / polystyrene sulfonic acid = 1 / 2.5 complex in terms of solid content, 7.5 parts, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] 12.5 parts and 3788 parts of isopropyl alcohol were mixed to prepare a coating solution L-4 for a low refractive index layer.
（低屈折率層用塗液Ｌ−５の調製）
(a)ペンタエリスリトールトリアクリレート〔共栄社化学（株）製、商品名：ライトアクリレートＰＥ−３Ａ、３官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３−メチル−４−メトキシチオフェン）／ポリアクリル酸エチルスルホン酸＝１／２．５の複合体を固形分換算で１０部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３５８８部混合して低屈折率層用塗液Ｌ−５を調製した。
(Preparation of coating liquid L-5 for low refractive index layer)
(a) 100 parts of pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, c) 10 parts of poly (3-methyl-4-methoxythiophene) / polyethyl acrylate sulfonate = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd. Manufactured product name: Irgacure 907] and 3588 parts of isopropyl alcohol were mixed to prepare a coating solution L-5 for a low refractive index layer.
（低屈折率層用塗液Ｌ−６の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリビニルスルホン酸＝１／２．５の複合体を固形分換算で１２．５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３３８８部混合して低屈折率層用塗液Ｌ−６を調製した。
(Preparation of coating liquid L-6 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) 12.5 parts of poly (3,4-ethylenedioxythiophene) / polyvinylsulfonic acid = 1 / 2.5 composite in terms of solid content, photopolymerization initiator [product of Ciba Specialty Chemicals Co., Ltd., product Name: Irgacure 907] and 1388 parts of isopropyl alcohol were mixed to prepare a coating solution L-6 for a low refractive index layer.
（低屈折率層用塗液Ｌ−７の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３−メチルチオフェン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で２５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを２３８８部混合して低屈折率層用塗液Ｌ−７を調製した。
(Preparation of coating liquid L-7 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 11. 25 parts of a composite of 3-methylthiophene) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, a photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] 5 parts and 2388 parts of isopropyl alcohol were mixed to prepare a coating solution L-7 for a low refractive index layer.
（低屈折率層用塗液Ｌ−８の調製）
(a)ペンタエリスリトールトリアクリレート〔共栄社化学（株）製、商品名：ライトアクリレートＰＥ−３Ａ、３官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを４３８８部混合して低屈折率層用塗液Ｌ−８を調製した。
(Preparation of coating liquid L-8 for low refractive index layer)
(a) 100 parts of pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, light A coating liquid L-8 for low refractive index layer was prepared by mixing 12.5 parts of a polymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 4388 parts of isopropyl alcohol.
（低屈折率層用塗液Ｌ−９の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３―ヘキシルオキシチオフェン）／ポリビニルスルホン酸＝１／２．５の複合体を固形分換算で３７．５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを１３８８部混合して低屈折率層用塗液Ｌ−９を調製した。
(Preparation of coating liquid L-9 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) 37.5 parts of a poly (3-hexyloxythiophene) / polyvinylsulfonic acid = 1 / 2.5 composite in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 1388 parts of isopropyl alcohol were mixed to prepare a coating solution L-9 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１０の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で２３３部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で１０部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１６．７部及びイソプロピルアルコールを４９１１部混合して低屈折率層用塗液Ｌ−１０を調製した。
(Preparation of coating liquid L-10 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: purple light UV7600B, hexafunctional urethane acrylate], (b) 233 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 complex in terms of solid content, 10 parts by photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907 16.7 parts and 4911 parts of isopropyl alcohol were mixed to prepare a coating solution L-10 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１１の調製）
(a)ペンタエリスリトールトリアクリレート〔共栄社化学（株）製、商品名：ライトアクリレートＰＥ−３Ａ、３官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１００部、(c)ポリ（３−ヘキシルオキシチオフェン）／ポリビニルスルホン酸＝１／２．５の複合体を固形分換算で６部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１０部及びイソプロピルアルコールを３１１０部混合して低屈折率層用塗液Ｌ−１１を調製した。
(Preparation of coating liquid L-11 for low refractive index layer)
(a) 100 parts of pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) 100 parts of the modified hollow silica fine particle sol in terms of solid content, c) 6 parts of poly (3-hexyloxythiophene) / polyvinyl sulfonic acid = 1 / 2.5 composite in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] and 3110 parts of isopropyl alcohol were mixed to prepare a coating solution L-11 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１２の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で６７部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を８．４部及びイソプロピルアルコールを２６６４部混合して低屈折率層用塗液Ｌ−１２を調製した。
(Preparation of coating liquid L-12 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 67 parts of the modified hollow silica fine particle sol in terms of solid content, (c) 5 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 2.5 composite in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: 8.4 parts of Irgacure 907] and 2664 parts of isopropyl alcohol were mixed to prepare a coating solution L-12 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１３の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で４３部、(c)ポリ（３―メチルチオフェン）／ポリビニルスルホン酸＝１／２．５の複合体を固形分換算で４．３部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を７．２部及びイソプロピルアルコールを２３３７部混合して低屈折率層用塗液Ｌ−１３を調製した。
(Preparation of coating liquid L-13 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: purple light UV7600B, hexafunctional urethane acrylate], (b) 43 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 3-methylthiophene) / polyvinylsulfonic acid = 1 / 2.5 composite in terms of solid content, 4.3 parts, a photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] 7.2 parts and 2337 parts of isopropyl alcohol were mixed to prepare a coating solution L-13 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１４の調製）
(a)ペンタエリスリトールトリアクリレート〔共栄社化学（株）製、商品名：ライトアクリレートＰＥ−３Ａ、３官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で２５部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリビニルスルホン酸＝１／２．５の複合体を固形分換算で３．８部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を６．３部及びイソプロピルアルコールを２０９０部混合して低屈折率層用塗液Ｌ−１４を調製した。
(Preparation of coating liquid L-14 for low refractive index layer)
(a) 100 parts of pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) 25 parts of the modified hollow silica fine particle sol in terms of solid content, c) 3.8 parts of poly (3,4-ethylenedioxythiophene) / polyvinylsulfonic acid = 1 / 2.5 composite in terms of solid content, photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd. , Trade name: Irgacure 907] and 2090 parts of isopropyl alcohol were mixed to prepare a coating solution L-14 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１５の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で４００部、(c)ポリ（３―メチルー４−メトキシチオフェン）／ポリアクリル酸エチルスルホン酸＝１／２．５の複合体を固形分換算で１５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を２５部及びイソプロピルアルコールを７１７５部混合して低屈折率層用塗液Ｌ−１５を調製した。
(Preparation of coating liquid L-15 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 400 parts of the modified hollow silica fine particle sol in terms of solid content, (c) Poly (3-methyl-4-methoxythiophene) / polyacrylic acid ethylsulfonic acid = 1 / 2.5 complex in terms of solid content, 15 parts, photopolymerization initiator [manufactured by Ciba Specialty Chemicals, Inc. Name: Irgacure 907] and 7175 parts of isopropyl alcohol were mixed to prepare a coating solution L-15 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１６の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（２―メチルアニリン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−１６を調製した。
(Preparation of coating liquid L-16 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 12. 2-methylaniline) / polystyrene sulfonic acid = 1 / 2.5 composite in terms of solid content, 5 parts of photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] 5 parts and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-16 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１７の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３―イソブチルアニリン）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−１７を調製した。
(Preparation of coating liquid L-17 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) 5 parts of a composite of poly (3-isobutylaniline) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] 12.5 parts and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-17 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１８の調製）
(a)ペンタエリスリトールトリアクリレート〔共栄社化学（株）製、商品名：ライトアクリレートＰＥ−３Ａ、３官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３―ブチルピロール）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−１８を調製した。
(Preparation of coating liquid L-18 for low refractive index layer)
(a) 100 parts of pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, c) 5 parts of a composite of poly (3-butylpyrrole) / polystyrene sulfonic acid = 1 / 2.5 in terms of solid content, photopolymerization initiator [trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals Co., Ltd. 12.5 parts and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-18 for a low refractive index layer.
（低屈折率層用塗液Ｌ−１９の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３―メチル−４−ヘキシルオキシピロール）／ポリスチレンスルホン酸＝１／２．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−１９を調製した。
(Preparation of coating liquid L-19 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) Poly (3-methyl-4-hexyloxypyrrole) / polystyrene sulfonic acid = 1 / 2.5 composite in terms of solid content, 5 parts, photopolymerization initiator [trade name, manufactured by Ciba Specialty Chemicals Co., Ltd. : Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-19 for a low refractive index layer.
（低屈折率層用塗液Ｌ−２０の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／１の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−２０を調製した。
(Preparation of coating liquid L-20 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1/1 composite in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907] 12.5 parts and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-20 for a low refractive index layer.
（低屈折率層用塗液Ｌ−２１の調製）
(a)ペンタエリスリトールトリアクリレート〔共栄社化学（株）製、商品名：ライトアクリレートＰＥ−３Ａ、３官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−２１を調製した。
(Preparation of coating liquid L-21 for low refractive index layer)
(a) 100 parts of pentaerythritol triacrylate [manufactured by Kyoeisha Chemical Co., Ltd., trade name: Light acrylate PE-3A, trifunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, c) 5 parts of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1/5 in terms of solid content, photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: 12.5 parts of Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-21 for a low refractive index layer.
（低屈折率層用塗液Ｌ−２２の調製）
(a)ＵＶ７６００Ｂ〔日本合成化学（株）製、商品名：紫光ＵＶ７６００Ｂ、６官能ウレタンアクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／０．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−２２を調製した。
(Preparation of coating liquid L-22 for low refractive index layer)
100 parts of (a) UV7600B [manufactured by Nippon Synthetic Chemical Co., Ltd., trade name: Violet UV7600B, hexafunctional urethane acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) poly ( 3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 0.5 complex in terms of solid content, 5 parts, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 907 12.5 parts and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-22 for a low refractive index layer.
（低屈折率層用塗液Ｌ−２３の調製）
(a)ジペンタエリスリトールヘキサアクリレート〔日本化薬（株）製、商品名：ＤＰＨＡ、６官能アクリレート〕を１００部、(b)前記変性中空シリカ微粒子ゾルを固形分換算で１５０部、(c)ポリ（３，４−エチレンジオキシチオフェン）／ポリスチレンスルホン酸＝１／６．５の複合体を固形分換算で５部、光重合開始剤〔チバ・スペシャリティ・ケミカルズ（株）製、商品名：イルガキュア９０７〕を１２．５部及びイソプロピルアルコールを３９８８部混合して低屈折率層用塗液Ｌ−２３を調製した。
(Preparation of coating liquid L-23 for low refractive index layer)
(a) 100 parts of dipentaerythritol hexaacrylate [manufactured by Nippon Kayaku Co., Ltd., trade name: DPHA, hexafunctional acrylate], (b) 150 parts of the modified hollow silica fine particle sol in terms of solid content, (c) 5 parts of a composite of poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid = 1 / 6.5 in terms of solid content, photopolymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: 12.5 parts of Irgacure 907] and 3988 parts of isopropyl alcohol were mixed to prepare a coating solution L-23 for a low refractive index layer.
＜近赤外線吸収性粘着剤Ｂ−１の調製＞
ｎ‐ブチルアクリレート９４．６質量部、アクリル酸４．４質量部、２‐ヒドロキシエチルメタクリレート１質量部、アゾビスイソブチロニトリル０．４質量部、酢酸エチル９０質量部、トルエン６０質量部を混合し、窒素雰囲気下で混合物を６５℃に加温して１０時間重合反応を行い、アクリル樹脂組成物（酸価９ｍｇＫＯＨ／ｇ）を調製した。このアクリル樹脂組成物にコロネートＬ〔日本ポリウレタン（株）製ポリイソシアネート〕１質量部、および固形分濃度が２０質量％となるように酢酸エチルを加えることにより、粘着樹脂組成物の固形分濃度２０質量％溶液ａ−１を得た。次に、ガラス容器にジイモニウム系色素であるビス［ビス（トリフルオロメタンスルホン）イミド酸］‐Ｎ，Ｎ，Ｎ’，Ｎ’‐テトラキス［ｐ‐ジ（イソプロピルオキシエチル）アミノフェニル］‐ｐ‐フェニレンジアミン０．２質量部、トルエン３．８質量部、および粒径０．８ｍｍのガラスビーズをそれぞれ加えてペイントシェイカーで３時間撹拌振とうした後、ガラスビーズを濾別して、ジイモニウム系色素の微粒子分散液ｂ−１（固形分濃度５質量％、平均粒子径０．０１５μｍ）を得た。なお、近赤外線吸収色素の平均粒子径は、ｎａｎｏｔｒａｃＵＰＡ‐ＥＸ１５０（日機装(株)製粒度分布測定機）を用いて動的光散乱理論／周波数マトリックス解析法（ＦＦＴ法）により測定した。続いて、粘着樹脂組成物の固形分濃度２０質量％溶液ａ−１５００質量部に上記微粒子分散液ｂ−１を２６質量部（固形分換算１．３質量部）加えて撹拌混合することにより、近赤外線吸収性粘着剤Ｂ−１を得た。
<Preparation of near-infrared absorbing adhesive B-1>
94.6 parts by mass of n-butyl acrylate, 4.4 parts by mass of acrylic acid, 1 part by mass of 2-hydroxyethyl methacrylate, 0.4 parts by mass of azobisisobutyronitrile, 90 parts by mass of ethyl acetate, 60 parts by mass of toluene The mixture was mixed, and the mixture was heated to 65 ° C. under a nitrogen atmosphere to carry out a polymerization reaction for 10 hours to prepare an acrylic resin composition (acid value: 9 mgKOH / g). By adding 1 part by mass of coronate L [polyisocyanate manufactured by Nippon Polyurethane Co., Ltd.] to this acrylic resin composition and ethyl acetate so that the solid content concentration becomes 20% by mass, the solid content concentration of the adhesive resin composition is 20 A mass% solution a-1 was obtained. Next, bis [bis (trifluoromethanesulfone) imidic acid] -N, N, N ′, N′-tetrakis [p-di (isopropyloxyethyl) aminophenyl] -p-phenylene, which is a diimonium dye, is placed in a glass container. Add 0.2 parts by weight of diamine, 3.8 parts by weight of toluene, and glass beads with a particle size of 0.8 mm, and stir and shake with a paint shaker for 3 hours. Then, the glass beads are separated by filtration to disperse fine particles of diimonium dye. A liquid b-1 (solid content concentration 5 mass%, average particle diameter 0.015 μm) was obtained. The average particle size of the near-infrared absorbing dye was measured by a dynamic light scattering theory / frequency matrix analysis method (FFT method) using nanotracUPA-EX150 (a particle size distribution measuring machine manufactured by Nikkiso Co., Ltd.). Subsequently, by adding 26 parts by mass (1.3 parts by mass in terms of solids) of the fine particle dispersion b-1 to a solution having a solids concentration of 20% by mass of the adhesive resin composition a-1500 parts by mass and stirring and mixing, Near-infrared absorbing adhesive B-1 was obtained.
＜近赤外線吸収性粘着剤Ｂ−２の調製＞
ｎ‐ブチルアクリレート９５．４質量部、２‐ヒドロキシエチルメタクリレート４．６質量部、アゾビスイソブチロニトリル０．２質量部、酢酸エチル９０質量部、トルエン６０質量部を混合し、窒素雰囲気下で混合物を６５℃に加温して１４時間重合反応を行い、アクリル樹脂組成物（酸価０ｍｇＫＯＨ／ｇ）を調製した。このアクリル樹脂組成物にＢＨＳ８５１５〔東洋インキ製造（株）製ポリイソシアネート〕１質量部、および固形分濃度が２０質量％となるように酢酸エチルを加えることにより、粘着樹脂組成物の固形分濃度２０質量％溶液ａ−２を得た。次に、ガラス容器にジイモニウム系色素であるビス（ヘキサフルオロアンチモン酸）‐Ｎ，Ｎ，Ｎ’，Ｎ’‐テトラキス［ｐ‐ジ（シクロヘキシルエチル）アミノフェニル］‐ｐ‐フェニレンジアミン０．２質量部、トルエン３．８質量部、および粒径０．８ｍｍのガラスビーズをそれぞれ加えてペイントシェイカーで４時間撹拌振とうした後、ガラスビーズを濾別して、ジイモニウム系色素の微粒子分散液ｂ−２（固形分濃度５質量％、平均粒子径０．０１０μｍ）を得た。続いて、粘着樹脂組成物の固形分濃度２０質量％溶液ａ−２５００質量部に上記微粒子分散液ｂ−２を２６質量部（固形分換算１．３質量部）、ＰＤ‐３２０〔山本化成（株）製テトラアザポルフィリン化合物〕０．１１質量部を加えて撹拌混合することにより、近赤外線吸収性粘着剤Ｂ−２を得た。
<Preparation of near-infrared absorbing adhesive B-2>
Mix 95.4 parts by weight of n-butyl acrylate, 4.6 parts by weight of 2-hydroxyethyl methacrylate, 0.2 parts by weight of azobisisobutyronitrile, 90 parts by weight of ethyl acetate, and 60 parts by weight of toluene, under a nitrogen atmosphere. The mixture was heated to 65 ° C. and polymerized for 14 hours to prepare an acrylic resin composition (acid value 0 mgKOH / g). By adding 1 part by weight of BHS8515 [polyisocyanate manufactured by Toyo Ink Manufacturing Co., Ltd.] to this acrylic resin composition and adding ethyl acetate so that the solid content concentration becomes 20% by mass, the solid content concentration of the pressure-sensitive adhesive resin composition is 20 A mass% solution a-2 was obtained. Next, bis (hexafluoroantimonic acid) -N, N, N ′, N′-tetrakis [p-di (cyclohexylethyl) aminophenyl] -p-phenylenediamine, 0.2 mass, which is a diimonium dye, is placed in a glass container. Parts, 3.8 parts by mass of toluene, and glass beads having a particle diameter of 0.8 mm were added and shaken with a paint shaker for 4 hours, and then the glass beads were separated by filtration to obtain a fine particle dispersion b-2 ( A solid content concentration of 5% by mass and an average particle size of 0.010 μm) were obtained. Subsequently, 26 parts by mass of the fine particle dispersion b-2 (1.3 parts by mass in terms of solids) and PD-320 [Yamamoto Chemical ( Co., Ltd. Tetraazaporphyrin Compound] By adding 0.11 part by mass and stirring and mixing, near-infrared absorbing adhesive B-2 was obtained.
＜近赤外線吸収性粘着剤Ｂ−３の調製＞
上記粘着樹脂組成物の固形分濃度２０質量％溶液ａ−１（５００質量部）に赤外線吸収色素としてＩＲ−１４〔（株）日本触媒製フタロシアニン化合物〕０．３質量部、ＴＸＥＸ８２０〔（株）日本触媒製フタロシアニン化合物〕０．５５質量部、ＴＸＥＸ９１５〔（株）日本触媒製フタロシアニン化合物〕０．５８質量部、ＴＡＰ‐２〔山田化学工業（株）製テトラアザポルフィリン化合物〕０．１２質量部を加えて撹拌混合することにより、近赤外線吸収性粘着剤Ｂ−３を得た。
<Preparation of near-infrared absorbing adhesive B-3>
Infrared absorbing dye, IR-14 [Phthalocyanine compound manufactured by Nippon Shokubai Co., Ltd.] 0.3 part by mass, TXEX820 [Co., Ltd.] Nippon Shokubai Phthalocyanine Compound] 0.55 parts by mass, TXEX915 [Nippon Shokubai Phthalocyanine Compound] 0.58 parts by mass, TAP-2 [Yamada Chemical Industries Ltd. tetraazaporphyrin compound] 0.12 parts by mass Was added and stirred and mixed to obtain a near-infrared absorbing adhesive B-3.
（実施例１−１）
厚み１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム〔東洋紡績（株）製、商品名：Ａ４３００〕の上に前記ハードコート層用塗液ＨＣ−１を乾燥膜厚１．１μｍ程度になるようにグラビアコート法で塗布し、乾燥後、４００ｍＪ／ｃｍ２の紫外線を照射して硬化させることにより、ハードコート層を得た。次に、このハードコート層上に、前記低屈折率層用塗液Ｌ−１を、硬化後の光学膜厚がｋλ/４（ｋ：１、λ：５５０ｎｍ）になるようにグラビアコート法で塗布し、乾燥後、窒素雰囲気下で４００ｍＪ／ｃｍ２の紫外線を照射して硬化させた。続いて、近赤外線吸収性粘着剤Ｂ−１をＰＥＴ製のセパレートフィルム上に乾燥後の厚みが２５μｍとなるようにオートアプリケーターを用いて塗布し、９０℃で２分間乾燥後、前記ポリエステルフィルムの低屈折率層を形成した面とは反対の他方面に貼合して３０℃で５日間保存することにより、近赤外線遮蔽フィルム１を得た。当該近赤外線遮蔽フィルム１の視感度反射率は０．９％、８５０ｎｍ透過率は１２％、９５０ｎｍ透過率は５％であった。続いて、近赤外線遮蔽フィルム１のセパレートフィルムを剥離してガラスに貼合することにより、実施例１の近赤外線遮蔽体を得た。得られた近赤外線遮蔽体について、視感度反射率、表面抵抗率、表面硬度、耐熱性及び耐擦傷性の評価を以下に記載する方法で行い、それらの評価結果を表１に示した。
(Example 1-1)
A gravure coating method on the polyethylene terephthalate (PET) film (trade name: A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm so that the coating liquid HC-1 for hard coat layer has a dry film thickness of about 1.1 μm. After coating and drying, a hard coat layer was obtained by irradiating and curing 400 mJ / cm 2 ultraviolet rays. Next, on the hard coat layer, the low refractive index layer coating liquid L-1 is subjected to a gravure coating method so that the optical film thickness after curing is kλ / 4 (k: 1, λ: 550 nm). After applying and drying, it was cured by irradiation with ultraviolet rays of 400 mJ / cm 2 under a nitrogen atmosphere. Subsequently, the near-infrared absorbing adhesive B-1 was applied onto a PET-made separate film using an auto applicator so that the thickness after drying was 25 μm, dried at 90 ° C. for 2 minutes, The near-infrared shielding film 1 was obtained by pasting on the other surface opposite to the surface on which the low refractive index layer was formed and storing at 30 ° C. for 5 days. The near infrared shielding film 1 had a visibility reflectance of 0.9%, an 850 nm transmittance of 12%, and a 950 nm transmittance of 5%. Then, the near-infrared shielding body of Example 1 was obtained by peeling the separate film of the near-infrared shielding film 1 and bonding it to glass. About the obtained near-infrared shield, evaluation of the visibility reflectance, surface resistivity, surface hardness, heat resistance and scratch resistance was performed by the methods described below, and the evaluation results are shown in Table 1.
（視感度反射率）
測定面の裏面反射を除くため、裏面をサンドペーパーで粗し、黒色塗料で塗りつぶしたものを分光光度計〔日本分光（株）製、商品名：Ｕ−ｂｅｓｔ５６０〕により、光の波長３８０ｎｍ〜７８０ｎｍの５°、−５°正反射スペクトルを測定した。得られる３８０ｎｍ〜７８０ｎｍの分光反射率と、ＣＩＥ標準イルミナントＤ６５の相対分光分布を用いて、ＪＩＳ Ｚ８７０１で想定されているＸＹＺ表色系における、反射による物体色の三刺激値Ｙを視感度反射率（％）とした。
(Visibility reflectance)
In order to remove the back surface reflection of the measurement surface, the back surface was roughened with sandpaper and painted with black paint, and a spectrophotometer [trade name: U-best 560, manufactured by JASCO Corporation] was used, and the light wavelength was 380 nm to 780 nm. The 5 ° and −5 ° specular reflection spectra were measured. Using the obtained spectral reflectance of 380 nm to 780 nm and the relative spectral distribution of the CIE standard illuminant D65, the tristimulus value Y of the object color due to reflection in the XYZ color system assumed in JIS Z8701 is obtained as the luminous reflectance. (%).
（表面抵抗率）
デジタル絶縁計〔東亜ＤＫＫ（株）製、商品名：ＳＭ−８２２０〕を用いて、近赤外線遮蔽体の表面抵抗率（Ω／□）を測定した。なお、表１〜表３において、「RANGE OVER」は表面抵抗率が測定限界を超えるほど高くなったことを意味する。
(Surface resistivity)
The surface resistivity (Ω / □) of the near-infrared shield was measured using a digital insulation meter [trade name: SM-8220, manufactured by Toa DKK Co., Ltd.]. In Tables 1 to 3, “RANGE OVER” means that the surface resistivity increased as it exceeded the measurement limit.
（鉛筆硬度）
安田精機（株）製鉛筆硬度試験機を用いてＪＩＳ Ｋ５６００−５−４に従って、鉛筆硬度を測定した。
(Pencil hardness)
The pencil hardness was measured according to JIS K5600-5-4 using a Yasuda Seiki Co., Ltd. pencil hardness tester.
（耐熱性）
近赤外線遮蔽体を８０℃に設定された恒温槽の中に放置し、１０００時間後に恒温槽から取り出して表面抵抗率を測定した。恒温槽に入れる前に測定した表面抵抗率と比較して、表面抵抗率の上昇が２桁以内に抑えられていれば○、表面抵抗率が３桁以上上昇した場合には×とした。
(Heat-resistant)
The near-infrared shield was left in a thermostat set at 80 ° C., taken out of the thermostat after 1000 hours, and the surface resistivity was measured. Compared with the surface resistivity measured before putting in the thermostatic bath, it was marked with ○ when the increase in surface resistivity was suppressed within 2 digits, and when the surface resistivity was increased by 3 digits or more.
（耐擦傷性）
（株）本光製作所製消しゴム摩耗試験機の先端に、＃００００のスチールウールを固定し、２．５Ｎ（２５０ｇｆ）及び１Ｎ（１００ｇｆ）の荷重をかけて、近赤外線遮蔽体の表面上を１０回往復摩擦したあとの表面の傷を目視で観察し、以下のＡ〜Ｅの６段階で評価した。
Ａ：傷なし、Ａ'：傷１〜３本、Ｂ：傷４〜１０本、Ｃ：傷１１〜２０本、Ｄ：傷２１〜３０本、Ｅ：３１本以上
(Abrasion resistance)
# 0000 steel wool is fixed to the tip of an eraser abrasion tester manufactured by Honko Seisakusho Co., Ltd., and a load of 2.5 N (250 gf) and 1 N (100 gf) is applied to the surface of the near-infrared shield 10 The scratches on the surface after the reciprocating friction were visually observed and evaluated according to the following 6 grades A to E.
A: No scratch, A ': 1-3 scratches, B: 4-10 scratches, C: 11-20 scratches, D: 21-30 scratches, E: 31 or more
（近赤外線透過率の測定）
近赤外線透過率はＵＶ‐１６００ＰＣ（(株)島津製作所製分光光度計の製品名）を用いて測定した。尚、各例においては、波長８５０ｎｍ、及び９５０ｎｍにおける近赤外線透過率がいずれも１５％以下となるように設計を行った。
(Measurement of near infrared transmittance)
Near-infrared transmittance was measured using UV-1600PC (product name of spectrophotometer manufactured by Shimadzu Corporation). In each example, the near infrared transmittance at wavelengths of 850 nm and 950 nm was designed to be 15% or less.
（実施例１−２〜実施例１−７）
実施例１−１のハードコート層用塗液として、表１に示すハードコート層用塗液ＨＣ−１〜ＨＣ−４を用い、低屈折率層用塗液として、低屈折率層用塗液Ｌ−２〜Ｌ−７を用い、近赤外線吸収粘着剤としてＢ−１〜Ｂ−３を用いた以外は実施例１−１と同様にして、近赤外線遮蔽体を得た。得られた近赤外線遮蔽体について、視感度反射率、表面抵抗率、鉛筆硬度、耐熱性及び耐擦傷性の評価結果を表１に示す。
(Example 1-2 to Example 1-7)
The hard coat layer coating liquids HC-1 to HC-4 shown in Table 1 were used as the hard coat layer coating liquid of Example 1-1, and the low refractive index layer coating liquid was used as the low refractive index layer coating liquid. A near-infrared shield was obtained in the same manner as Example 1-1 except that L-2 to L-7 were used and B-1 to B-3 were used as the near-infrared absorbing adhesives. Table 1 shows the evaluation results of visibility reflectance, surface resistivity, pencil hardness, heat resistance and scratch resistance of the obtained near-infrared shield.
（比較例１−１〜比較例１−３）
実施例１−１の低屈折率層用塗液Ｌ−１の代わりに、比較例１−１では低屈折率層用塗液Ｌ−８を用い、比較例１−２では低屈折率層用塗液Ｌ−９を用い、比較例１−３ではポリエチレンテレフタレート（ＰＥＴ）フィルムの上に直接低屈折率層用塗液Ｌ−１を塗布し、近赤外線吸収粘着剤としてＢ−１〜Ｂ−３を用いた以外は、実施例１−１と同様にして近赤外線遮蔽体を得た。得られた近赤外線遮蔽体について、視感度反射率、表面抵抗率、鉛筆硬度、耐熱性及び耐擦傷性の評価結果を表１に示す。
(Comparative Example 1-1 to Comparative Example 1-3)
Instead of the low refractive index layer coating liquid L-1 of Example 1-1, the comparative example 1-1 uses the low refractive index layer coating liquid L-8, and the comparative example 1-2 uses the low refractive index layer coating liquid L-1. The coating liquid L-9 was used, and in Comparative Example 1-3, the coating liquid L-1 for the low refractive index layer was applied directly on the polyethylene terephthalate (PET) film, and B-1 to B- were used as near-infrared absorbing adhesives. A near-infrared shield was obtained in the same manner as in Example 1-1 except that 3 was used. Table 1 shows the evaluation results of visibility reflectance, surface resistivity, pencil hardness, heat resistance and scratch resistance of the obtained near-infrared shield.
（比較例１−４）
実施例１−１における近赤外線吸収性粘着剤を使用しなかった以外は実施例１−１と同様にして近赤外線遮蔽体を得た。
(Comparative Example 1-4)
A near-infrared shield was obtained in the same manner as in Example 1-1 except that the near-infrared absorbing adhesive in Example 1-1 was not used.
表１に示したように、実施例１−１〜実施例１−７では、反射防止性能を有し、帯電防止性能にも優れ、かつ耐熱性、鉛筆硬度及び耐擦傷性も良好な反射防止フィルムを得ることができた。一方、比較例１−１では、π共役系導電性高分子とドーパントからなる複合体を有していないことから、帯電防止性能が発現されないという結果であった。また、比較例１−２では、π共役系導電性高分子とドーパントからなる複合体の含有量が多いため、複合体に対する多官能（メタ）アクリレートの含有率が相対的に減少し、耐擦傷性が悪化するという結果であった。また、比較例１−３では、ポリエチレンテレフタレート（ＰＥＴ）フィルムの上に直接低屈折率層を積層しているため、鉛筆硬度が悪化するという結果であった。また、比較例１−４では近赤外線吸収性粘着剤を積層していないため近赤外線吸収能を発現することができなかった。 As shown in Table 1, Examples 1-1 to 1-7 have antireflection performance, excellent antistatic performance, and good antireflection properties such as heat resistance, pencil hardness, and scratch resistance. A film could be obtained. On the other hand, Comparative Example 1-1 did not have a composite composed of a π-conjugated conductive polymer and a dopant, and thus the antistatic performance was not exhibited. Moreover, in Comparative Example 1-2, since the content of the complex composed of the π-conjugated conductive polymer and the dopant is large, the content of polyfunctional (meth) acrylate with respect to the complex is relatively reduced, and the scratch resistance is increased. It was the result that sex deteriorated. Moreover, in Comparative Example 1-3, since the low refractive index layer was laminated | stacked directly on the polyethylene terephthalate (PET) film, it was a result that pencil hardness deteriorated. Moreover, in Comparative Example 1-4, since the near-infrared absorptive adhesive was not laminated | stacked, the near-infrared absorptivity was not able to be expressed.
（実施例２−１〜実施例２−４）
実施例１−１のハードコート層用塗液として、表２に示すハードコート層用塗液ＨＣ−１〜ＨＣ−４を用い、低屈折率層用塗液Ｌ−１の代わりに、低屈折率層用塗液Ｌ−１０〜Ｌ−１３を用い、近赤外線吸収粘着剤としてＢ−１〜Ｂ−３を用いた以外は実施例１−１と同様にして近赤外線遮蔽体を得た。得られた近赤外線遮蔽体について、視感度反射率、表面抵抗率、鉛筆硬度、耐熱性及び耐擦傷性の評価結果を表２に示す。
(Example 2-1 to Example 2-4)
As the hard coat layer coating liquid of Example 1-1, the hard coat layer coating liquids HC-1 to HC-4 shown in Table 2 were used, and instead of the low refractive index layer coating liquid L-1, a low refractive index was used. A near-infrared shield was obtained in the same manner as in Example 1-1 except that the rate layer coating liquids L-10 to L-13 were used and B-1 to B-3 were used as the near-infrared absorbing adhesives. Table 2 shows the evaluation results of visibility reflectance, surface resistivity, pencil hardness, heat resistance and scratch resistance of the obtained near-infrared shield.
（比較例２−１、比較例２−２）
実施例１−１の低屈折率層用塗液Ｌ−１の代わりに、比較例２−１では低屈折率層用塗液Ｌ−１４を用い、比較例２−２では低屈折率層用塗液Ｌ−１５を用い、近赤外線吸収粘着剤としてＢ−１〜Ｂ−３を用いた以外は実施例１−１と同様にして近赤外線遮蔽体を得た。得られた近赤外線遮蔽体について、視感度反射率、表面抵抗率、鉛筆硬度、耐熱性及び耐擦傷性の評価結果を表２に示す。
(Comparative Example 2-1 and Comparative Example 2-2)
Instead of the low refractive index layer coating liquid L-1 of Example 1-1, Comparative Example 2-1 uses the low refractive index layer coating liquid L-14, and Comparative Example 2-2 uses the low refractive index layer coating liquid L-1. A near-infrared shield was obtained in the same manner as in Example 1-1 except that the coating liquid L-15 was used and B-1 to B-3 were used as the near-infrared absorbing adhesive. Table 2 shows the evaluation results of visibility reflectance, surface resistivity, pencil hardness, heat resistance and scratch resistance of the obtained near-infrared shield.
表２に示したように、実施例２−１〜実施例２−４では、反射防止性能を有し、帯電防止性能にも優れ、かつ耐熱性、鉛筆硬度及び耐擦傷性も良好な反射防止フィルムを得ることができた。一方、比較例２−１では、中空シリカ微粒子の含有量が少ないため、低屈折率層の屈折率が十分に低下せず、反射防止性能が劣るという結果であった。また、比較例２−２では、中空シリカ微粒子の含有量が多いため、相対的に多官能（メタ）アクリレートの含有量が減少し、耐擦傷性が悪化するという結果であった。 As shown in Table 2, Examples 2-1 to 2-4 have antireflection performance, excellent antistatic performance, and good antireflection properties such as heat resistance, pencil hardness, and scratch resistance. A film could be obtained. On the other hand, in Comparative Example 2-1, since the content of the hollow silica fine particles was small, the refractive index of the low refractive index layer was not sufficiently lowered, resulting in poor antireflection performance. Moreover, in Comparative Example 2-2, since the content of the hollow silica fine particles was large, the content of the polyfunctional (meth) acrylate was relatively decreased, and the scratch resistance was deteriorated.
（実施例３−１〜実施例３−６）
実施例１−１のハードコート層用塗液として、表３に示すハードコート層用塗液ＨＣ−１〜ＨＣ−４を用い、実施例１−１の低屈折率層用塗液Ｌ−１の代わりに、低屈折率層用塗液Ｌ−１６〜Ｌ−２１を用い、近赤外線吸収粘着剤としてＢ−１〜Ｂ−３を用いた以外は実施例１−１と同様にして近赤外線遮蔽体を得た。得られた近赤外線遮蔽体について、視感度反射率、表面抵抗率、耐熱性及び耐擦傷性の評価結果を表３に示す。
(Example 3-1 to Example 3-6)
As the hard coat layer coating liquid of Example 1-1, the hard coat layer coating liquids HC-1 to HC-4 shown in Table 3 were used, and the low refractive index layer coating liquid L-1 of Example 1-1 was used. In the same manner as in Example 1-1 except that the coating liquids L-16 to L-21 for the low refractive index layer were used instead of B-1, and B-1 to B-3 were used as the near infrared absorbing adhesives. A shield was obtained. Table 3 shows the evaluation results of the visibility reflectance, surface resistivity, heat resistance and scratch resistance of the obtained near-infrared shield.
（比較例３−１、比較例３−２）
実施例１−１の低屈折率層用塗液Ｌ−１の代わりに、比較例３−１では低屈折率層用塗液Ｌ−２２を用い、比較例３−２では低屈折率層用塗液Ｌ−２３を用い、近赤外線吸収粘着剤としてＢ−１〜Ｂ−３を用いた以外は実施例１−１と同様にして近赤外線遮蔽体を得た。得られた近赤外線遮蔽体について、視感度反射率、表面抵抗率、耐熱性及び耐擦傷性の評価結果を表３に示す。
(Comparative Example 3-1 and Comparative Example 3-2)
Instead of the coating solution L-1 for the low refractive index layer of Example 1-1, the coating solution L-22 for the low refractive index layer was used in Comparative Example 3-1, and for the low refractive index layer in Comparative Example 3-2. A near-infrared shield was obtained in the same manner as in Example 1-1 except that the coating liquid L-23 was used and B-1 to B-3 were used as near-infrared absorbing adhesives. Table 3 shows the evaluation results of the visibility reflectance, surface resistivity, heat resistance and scratch resistance of the obtained near-infrared shield.
表３に示したように、実施例３−１〜実施例３−６では、反射防止性能を有し、帯電防止性能にも優れ、かつ耐熱性、鉛筆硬度及び耐擦傷性も良好な反射防止フィルムを得ることができた。一方、比較例３−１では、π共役系導電性高分子に対してドーパントの量が少ないため、π共役系導電性高分子が十分にドーピングされず、導電性が低下した。また、比較例３−２では、π共役系導電性高分子に対してドーパントの量が多いため、過剰に存在するドーパントの影響により、耐熱性が低下した。
As shown in Table 3, Examples 3-1 to 3-6 have antireflection performance, excellent antistatic performance, and good antireflection properties such as heat resistance, pencil hardness, and scratch resistance. A film could be obtained. On the other hand, in Comparative Example 3-1, since the amount of the dopant was small with respect to the π-conjugated conductive polymer, the π-conjugated conductive polymer was not sufficiently doped and the conductivity was lowered. Moreover, in Comparative Example 3-2, since the amount of the dopant was large with respect to the π-conjugated conductive polymer, the heat resistance was lowered due to the influence of the excessive dopant.
Claims (2)
前記低屈折率層は、(a)多官能（メタ）アクリレートと、(b)中空シリカ微粒子と、(c)π共役系導電性高分子とドーパントからなる複合体と、を含有する低屈折率層用塗液の硬化物であり、
前記低屈折率層用塗液は、前記(a)多官能（メタ）アクリレート１００質量部あたり、前記(b)中空シリカ微粒子４０〜２５０質量部、前記(c)π共役系導電性高分子とドーパントからなる複合体１〜２５質量部を含み、
前記(c)π共役系導電性高分子とドーパントからなる複合体中の、π共役系導電性高分子とドーパントの質量比が１：１〜１：５であり、
前記近赤外線吸収性粘着層は、(d)（メタ）アクリル系粘着樹脂組成物と、(e)近赤外線吸収色素とを含み、
前記(d)（メタ）アクリル系粘着樹脂組成物は、酸価が２０ｍｇＫＯＨ／ｇ以下の（メタ）アクリル系樹脂を含み、
前記(e)近赤外線吸収色素は、ジイモニウム系色素又はフタロシアニン系色素である近赤外線遮蔽フィルム。 A hard coat layer and a low refractive index layer having a refractive index lower than that of the hard coat layer are laminated in this order on one side of the transparent base film, and a near infrared absorptivity is provided on the other side of the transparent base film. A near-infrared shielding film in which an adhesive layer is laminated,
The low refractive index layer comprises (a) polyfunctional (meth) acrylate, (b) hollow silica fine particles, and (c) a complex composed of a π-conjugated conductive polymer and a dopant. It is a cured product of the coating liquid for the layer,
The coating liquid for the low refractive index layer comprises (b) 40 to 250 parts by mass of hollow silica fine particles, (c) a π-conjugated conductive polymer per 100 parts by mass of the (a) polyfunctional (meth) acrylate. Including 1 to 25 parts by mass of a composite comprising a dopant,
(C) The mass ratio of the π-conjugated conductive polymer and the dopant in the complex composed of the π-conjugated conductive polymer and the dopant is 1: 1 to 1: 5,
The near-infrared absorbing pressure-sensitive adhesive layer includes (d) a (meth) acrylic pressure-sensitive adhesive resin composition, and (e) a near-infrared absorbing dye,
The (d) (meth) acrylic adhesive resin composition includes a (meth) acrylic resin having an acid value of 20 mgKOH / g or less,
(E) The near-infrared absorbing film, wherein the near-infrared absorbing dye is a diimonium dye or a phthalocyanine dye.
The near-infrared shielding body for plasma displays formed by bonding the near-infrared shielding film of Claim 1 to a base material through the said near-infrared absorptive adhesive layer.
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| JP6284762B2 (en) * | 2013-12-18 | 2018-02-28 | 富士フイルム株式会社 | Heat shield and window glass |
| US11267973B2 (en) | 2014-05-12 | 2022-03-08 | Corning Incorporated | Durable anti-reflective articles |
| US9790593B2 (en) | 2014-08-01 | 2017-10-17 | Corning Incorporated | Scratch-resistant materials and articles including the same |
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| JP7128571B2 (en) * | 2017-02-07 | 2022-08-31 | 大日本印刷株式会社 | Composition for low refractive index layer |
| EP3837223A1 (en) | 2018-08-17 | 2021-06-23 | Corning Incorporated | Inorganic oxide articles with thin, durable anti-reflective structures |
| CN111394002B (en) * | 2020-03-27 | 2022-04-05 | 宁波华显智能科技有限公司 | Transparent display film containing silicon dioxide hollow spheres and preparation method and application thereof |
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| US20090081469A1 (en) * | 2005-05-10 | 2009-03-26 | Nippon Shokubai Co., Ltd. | Pressure-sensitive adhesive composition containing near infrared ray absorption agent |
| JP2009015289A (en) * | 2007-06-06 | 2009-01-22 | Hitachi Maxell Ltd | Antireflection film and display front plate using the same |
| JP2011048359A (en) * | 2009-07-31 | 2011-03-10 | Fujifilm Corp | Antireflective film, polarizing plate, and image display device |
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