JP5308215B2 - Anti-glare hard coat film - Google Patents
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Description
本発明は、ノートパソコン、パソコン用モニタ、テレビ等の各種ディスプレイの表面に用いる防眩ハードコートフィルムに関する。 The present invention relates to an antiglare hard coat film used on the surface of various displays such as notebook computers, personal computer monitors, and televisions.
ノートパソコン、液晶モニタなどのディスプレイは、その表面の表面保護基材を通して画像を認識するようになっている。それらのディスプレイは本体内部にバックライトを用いるか、又は外部の光を利用して視認性を向上させている。これらのディスプレイは内部から発する光や外光の映り込みを軽減し、画像の視認性を向上するため、屈折率の異なる薄膜を形成して光学的に反射を防止するか、又は表面保護基材に防眩処理を施すことが行われている。光学的に反射を防止する方法は、フィルム又はハードコート処理されたフィルム表面に酸化チタンや酸化ジルコニウムなどの高屈折率材料とフッ化マグネシウム、有機フッ素化合物、酸化珪素などの低屈折率材料の薄膜を交互に形成して、多層薄膜とし、光の干渉により反射を防止する方法（特許文献１）が知られている。防眩処理は、二酸化珪素等の微粒子を含む樹脂塗膜をフィルム表面に形成し、塗膜表面の凹凸により反射光を拡散させる方法（特許文献２）が知られている。 A display such as a notebook personal computer or a liquid crystal monitor recognizes an image through a surface protective substrate on the surface thereof. These displays use a backlight inside the main body or use external light to improve visibility. These displays are designed to reduce reflection of light emitted from the inside and external light, and to improve image visibility, so that a thin film with a different refractive index is formed to prevent reflection optically, or a surface protection substrate. An anti-glare treatment has been performed. The method of optically preventing reflection is that a film or a hard-coated film surface has a high refractive index material such as titanium oxide or zirconium oxide and a thin film of a low refractive index material such as magnesium fluoride, an organic fluorine compound, or silicon oxide. A method of forming a multilayer thin film alternately to prevent reflection by light interference (Patent Document 1) is known. As the anti-glare treatment, there is known a method (Patent Document 2) in which a resin coating film containing fine particles such as silicon dioxide is formed on a film surface and reflected light is diffused by unevenness on the coating film surface.
しかし、特許文献１に記載されたような光学的に反射を防止する方法は、高価な材料を用いた多層膜を利用するため、コストが高くなってしまうという問題がある。また、特許文献２に記載されたような塗膜表面の凹凸により反射光の散乱を利用する防眩処理タイプの液晶ディスプレイの場合、ディスプレイの解像度が高いと、バックライト等からカラーフィルター画素を通過した光が、防眩層での表面散乱により混合するため、画面がギラツキ、著しく視認性を低下させるという問題がある。
However, the method of optically preventing reflection as described in Patent Document 1 uses a multilayer film using an expensive material, and thus has a problem of high cost. In addition, in the case of an anti-glare type liquid crystal display using scattering of reflected light due to unevenness of the coating film surface as described in
また、従来技術においては画像のギラツキを防止するためには、微粒子添加量を多量にして、ヘイズ度を高めなければならず、液晶パネルに装着し、画像を表示すると画面が白っぽくなり、特に、黒表示で画像品位が低下する問題があった。 In addition, in order to prevent glare in the image in the prior art, the amount of fine particles added must be increased to increase the haze degree, and the screen becomes whitish when mounted on a liquid crystal panel and displaying an image. There was a problem that the image quality deteriorated in black display.
そこで、本発明の目的は、このような従来の防眩フィルムに比べ、ヘイズ度が低く、透明性、耐擦傷性に優れ、画像のギラツキおよび白っぽさ（白ぼけ）を低減し、ディスプレイの視認性を向上させた表面保護用の防眩ハードコートフィルムを安価に製造し、提供することである。 Accordingly, the object of the present invention is to provide a display having a low haze degree, excellent transparency and scratch resistance, reducing glare and whitishness (white blurring) of the image compared with the conventional anti-glare film. An inexpensive antiglare hard coat film for surface protection with improved visibility is manufactured and provided.
本発明者らは、前記課題を解決するべく、鋭意検討した結果、透明フィルム上に、粒径と吸油量の異なる２種類の微粒子を含む樹脂塗膜を形成することで、前記課題を解決できることを見い出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by forming a resin coating film containing two kinds of fine particles having different particle diameters and oil absorption amounts on a transparent film. As a result, the present invention has been completed.
即ち、透明フィルム上に、粒径と吸油量の異なる２種類の微粒子及び樹脂から成る防眩層を設けてなる防眩ハードコートフィルムであって、第１種の微粒子は、その平均粒子径が３．５μｍ未満で、かつＪＩＳ Ｋ ５１０１に準じた吸油量が１５０ｍｌ／１００ｇ未満であり、第２種の微粒子は、その平均粒子径が３．５μｍ以上で、かつ前記吸油量が１５０ｍｌ／１００ｇ以上であり、前記２種類の微粒子の合計配合量が樹脂に対して６〜３０重量％で、さらに２種類の微粒子同士の重量配合割合が３０／７０〜７０／３０であることを特徴とする防眩ハードコートフィルムである。 That is, an anti-glare hard coat film in which an anti-glare layer comprising two kinds of fine particles having different particle diameters and oil absorption amounts and a resin is provided on a transparent film, and the first kind of fine particles has an average particle diameter of The oil absorption amount is less than 3.5 μm and the oil absorption amount according to JIS K 5101 is less than 150 ml / 100 g. The second type fine particles have an average particle diameter of 3.5 μm or more and the oil absorption amount is 150 ml / 100 g or more. The total blending amount of the two kinds of fine particles is 6 to 30% by weight with respect to the resin, and the weight blending ratio between the two kinds of fine particles is 30/70 to 70/30. It is a dazzling hard coat film.
また、前記２種類の微粒子はともにシリカ微粒子であることが好ましい。
また、前記２種類の微粒子の比表面積がともに７００ｍ２／ｇ未満であることが好ましい。なお、この場合の比表面積は、簡易ＢＥＴ法に基づいて測定される。
また、前記２種類の微粒子の屈折率がともに１．４０〜１．５５の範囲であることが好ましい。
また、前記樹脂は電離放射線硬化型樹脂であることが好ましい。
The two kinds of fine particles are preferably silica fine particles.
The specific surface areas of the two kinds of fine particles are both preferably less than 700 m 2 / g. In this case, the specific surface area is measured based on a simple BET method.
Moreover, it is preferable that the refractive indexes of the two kinds of fine particles are both in the range of 1.40 to 1.55.
The resin is preferably an ionizing radiation curable resin.
本発明の防眩ハードコートフィルムは、従来の防眩ハードコートフィルムに比べて、ヘイズ度が低く、透明性に優れ、画像のギラツキおよび白っぽさ（白ぼけ）などの視認性に優れかつ耐擦傷性の高い表面保護フィルムであり、安価に製造することができる。 The antiglare hard coat film of the present invention has a low haze degree, excellent transparency, and excellent visibility such as image glare and whitishness (white blur), as compared with conventional antiglare hard coat films. It is a surface protective film having high scratch resistance and can be produced at low cost.
以下、本発明の実施の形態について詳述する。
本発明の防眩ハードコートフィルムの断面を図１に示す。透明フィルム１上に、平均粒子径と吸油量の異なる２種類の微粒子、すなわち第１種の微粒子３と第２種の微粒子４を含む樹脂５を所定の厚さで塗工して防眩層２としたものである。
Hereinafter, embodiments of the present invention will be described in detail.
A cross section of the antiglare hard coat film of the present invention is shown in FIG. On the transparent film 1, an antiglare layer is formed by coating a resin 5 containing two kinds of fine particles having different average particle diameters and oil absorption amounts, that is, a first kind of fine particles 3 and a second kind of fine particles 4 with a predetermined thickness. 2.
本発明に用いることのできる透明フィルムは特に限定はないが、たとえば、ポリエチレンテレフタレートフィルム（ＰＥＴ）、ポリエチレンナフタレートフィルム（ＰＥＮ）、ポリカーボネートフィルム（ＰＣ）、トリアセチルセルロースフィルム（ＴＡＣ）、ノルボルネンフィルム（ＮＢ）などが使用でき、フィルム厚さは２５μｍ〜２５０μｍ程度が使用可能である。 The transparent film that can be used in the present invention is not particularly limited. For example, a polyethylene terephthalate film (PET), a polyethylene naphthalate film (PEN), a polycarbonate film (PC), a triacetyl cellulose film (TAC), a norbornene film ( NB) can be used, and a film thickness of about 25 μm to 250 μm can be used.
第１種の微粒子は、好ましくは不定形、即ち、粒子の形状が特定されない微粒子であれば材質に特に限定はなく、具体的には、シリカゲル、湿式法シリカ、乾式法シリカ等のシリカ微粒子、マイカ、酸化チタン、炭酸カルシウム、タルク、金属酸化物微粒子などを挙げることができる。特に、屈折率が１．４４ほどであり、コスト的に有利な不定形疎水化シリカが好ましい。第１種の微粒子としてこれらの１種類を用いてもよいし、２種類以上を混合して用いてもよい。この第１種の微粒子は、塗膜中に沈み易くすることで画像のギラツキと白っぽさ（白ぼけ）を低減しつつある程度のヘイズを発現させることを目的とし、平均粒径３．５μｍ未満、好ましくは２．０〜３．０μｍ、またＪＩＳ Ｋ ５１０１に準じた吸油量が１５０ｍｌ／１００ｇ未満、好ましくは１３０ｍｌ／１００ｇ未満のものを使用する。 The first type of fine particles are preferably amorphous, that is, there are no particular limitations on the material as long as the shape of the particles is not specified. Specifically, silica fine particles such as silica gel, wet silica, dry silica, Examples thereof include mica, titanium oxide, calcium carbonate, talc, and metal oxide fine particles. In particular, amorphous hydrophobic silica having a refractive index of about 1.44 and advantageous in cost is preferable. One type of these may be used as the first type of fine particles, or two or more types may be mixed and used. This first type of fine particles is intended to cause a certain amount of haze while reducing glare and whitishness (white blurring) of the image by facilitating sinking in the coating film, and has an average particle size of 3.5 μm. Or less, preferably 2.0 to 3.0 μm, and the oil absorption according to JIS K 5101 is less than 150 ml / 100 g, preferably less than 130 ml / 100 g.
第２種の微粒子は、好ましくは不定形、即ち、粒子の形状が特定されない微粒子であれば材質に特に限定はなく、具体的には、シリカゲル、湿式法シリカ、乾式法シリカ等のシリカ微粒子、マイカ、酸化チタン、炭酸カルシウム、タルク、金属酸化物微粒子などを挙げることができる。特に、屈折率が１．４４ほどであり、コスト的に有利な不定形疎水化シリカが好ましい。第２種の微粒子としてこれらの１種類を用いてもよいし、２種類以上を混合して用いてもよい。この第２種の微粒子は、塗膜表面に存在させ易くすることで、ある程度の防眩性を発現させることを目的とし、平均粒径３．５μｍ以上、好ましくは３．８〜６．５μｍ、またＪＩＳＫ ５１０１に準じた吸油量が１５０ｍｌ／１００ｇ以上、好ましくは１５０ｍｌ／１００ｇ〜２５０ｍｌ／１００ｇのものを使用する。 The second type of fine particles are preferably amorphous, that is, there are no particular limitations on the material as long as the shape of the particles is not specified. Specifically, silica fine particles such as silica gel, wet silica, dry silica, Examples thereof include mica, titanium oxide, calcium carbonate, talc, and metal oxide fine particles. In particular, amorphous hydrophobic silica having a refractive index of about 1.44 and advantageous in cost is preferable. One kind of these may be used as the second kind of fine particles, or two or more kinds may be mixed and used. The second type of fine particles are intended to be present on the surface of the coating film so as to develop a certain degree of antiglare property, and have an average particle size of 3.5 μm or more, preferably 3.8 to 6.5 μm, The oil absorption amount according to JISK 5101 is 150 ml / 100 g or more, preferably 150 ml / 100 g to 250 ml / 100 g.
これら第１の微粒子及び第２の微粒子の平均粒径はレーザー回折・散乱法で測定することができる。この方法では、粒子を分散した液にレーザー光を当てたときに回折・散乱する光の強度変化により粒子径を測定する。 The average particle diameter of the first fine particles and the second fine particles can be measured by a laser diffraction / scattering method. In this method, the particle diameter is measured by a change in the intensity of light that is diffracted and scattered when laser light is applied to a liquid in which particles are dispersed.
本発明では、低ヘイズにおける画像のギラツキと白っぽさ（白ぼけ）を両立するため、２種類の微粒子の合計配合量が樹脂に対して６〜３０重量％であることが必要で、好ましくは６〜２０重量％の割合である。また２種類の微粒子の重量配合割合が、第1種／第２種＝３０／７０〜７０／３０であることを必要とする。また、２種類の微粒子の比表面積がともに７００ｍ２／ｇ未満であることが好ましく、特に好ましくは５５０ｍ２／ｇ未満である。 In the present invention, it is necessary that the total blending amount of the two kinds of fine particles is 6 to 30% by weight with respect to the resin in order to achieve both glare and whitishness (white blur) of the image at low haze. Is a ratio of 6 to 20% by weight. In addition, it is necessary that the blending ratio of the two kinds of fine particles is first type / second type = 30/70 to 70/30. Moreover, it is preferable that the specific surface area of two types of microparticles | fine-particles is both less than 700 m < 2 > / g, Most preferably, it is less than 550 m < 2 > / g.
本発明に用いる樹脂としては、乾燥後に被膜を形成する樹脂であれば特に制限はないが、特に耐擦傷性を付与するという点で、電離放射線効果型樹脂（例えば紫外線硬化型樹脂）を用いることが好ましい。紫外線硬化型樹脂は、アクリレート系の官能基を有するポリエステル樹脂、アクリル樹脂、ウレタン樹脂などとこれらのオリゴマーおよびプレポリマーを主成分とした樹脂が使用できる。また、これらの樹脂を紫外線照射により架橋するため、光重合開始剤としてアセトフェノン類、ベンゾフェノン類等を混合することが望ましい。更に、防眩層は、本発明の効果を変えない範囲で、消泡剤、レベリング剤、酸化防止剤、紫外線吸収剤、光安定剤、重合禁止剤等を含有してもよい。 The resin used in the present invention is not particularly limited as long as it is a resin that forms a film after drying, but an ionizing radiation effect type resin (for example, an ultraviolet curable resin) is used particularly in terms of imparting scratch resistance. Is preferred. As the ultraviolet curable resin, a polyester resin, an acrylic resin, a urethane resin or the like having an acrylate functional group, and a resin mainly composed of these oligomers and prepolymers can be used. Moreover, in order to crosslink these resins by ultraviolet irradiation, it is desirable to mix acetophenones, benzophenones, etc. as photopolymerization initiators. Furthermore, the antiglare layer may contain an antifoaming agent, a leveling agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a polymerization inhibitor and the like as long as the effects of the present invention are not changed.
防眩層は、前記樹脂と微粒子等を溶剤に溶解、分散した塗料を透明フィルム上に塗工乾燥して形成することができる。塗料に用いることのできる溶剤は、ヘキサン、オクタンなどの脂肪族炭化水素、トルエン、キシレンなどの芳香族炭化水素、エタノール、１−プロパノール、イソプロパノール、１−ブタノールなどのアルコール類、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、酢酸エチル、酢酸ブチルなどのエステル類、セロソルブ類などから適宜選択して用いることができ、これらの数種類を混合して用いてもよい。塗工乾燥を行うため沸点が７０℃〜２００℃の範囲であることが望ましい。 The antiglare layer can be formed by applying and drying a paint in which the resin and fine particles are dissolved and dispersed in a solvent on a transparent film. Solvents that can be used for the paint include aliphatic hydrocarbons such as hexane and octane, aromatic hydrocarbons such as toluene and xylene, alcohols such as ethanol, 1-propanol, isopropanol, and 1-butanol, methyl ethyl ketone, and methyl isobutyl ketone. Can be appropriately selected from ketones such as ethyl acetate, esters such as ethyl acetate and butyl acetate, cellosolves and the like, and several of these may be used in combination. In order to perform coating drying, the boiling point is preferably in the range of 70 ° C to 200 ° C.
塗工方法は特に限定しないが、グラビア塗工、マイクログラビア塗工、バー塗工、スライドダイ塗工、スロットダイ塗工、デイップコートなど、塗膜厚さの調整が容易な方式で塗工が可能である。防眩層の膜厚は、第２種の微粒子の平均粒径よりも大きくしなければならない。この膜厚がこの平均粒径よりも小さいとこの微粒子が塗膜表面に突出し表面ヘイズが高まり、光の散乱により表面が白くなりディスプレイの視認性を著しく低下させるからである。一方、この膜厚が大きすぎると防眩性が低下する傾向にある。このため、好ましくは膜厚が第２種の微粒子の平均粒子径の３倍以下、より好ましくは１．５〜２．５倍となるように防眩層を設ける。 The coating method is not particularly limited, but it can be applied with a method that allows easy adjustment of the coating thickness, such as gravure coating, micro gravure coating, bar coating, slide die coating, slot die coating, and dip coating. Is possible. The film thickness of the antiglare layer must be larger than the average particle size of the second kind of fine particles. If the film thickness is smaller than the average particle diameter, the fine particles protrude from the surface of the coating film, the surface haze increases, the surface becomes white due to light scattering, and the visibility of the display is significantly reduced. On the other hand, when this film thickness is too large, the antiglare property tends to be lowered. For this reason, the antiglare layer is preferably provided so that the film thickness is 3 times or less, more preferably 1.5 to 2.5 times the average particle diameter of the second type fine particles.
本発明においては、フィルム上に前記被膜塗布液を塗布し、加熱・乾燥して設けた被膜層（防眩層）に、ハロゲンランプ等の公知の光源を用いて更に紫外線を照射することにより、該被膜層を光硬化させる。このようにして光硬化させた被膜は極めて硬度が高い。硬化は、例えば、出力１２０〜２４０Ｗ／ｃｍのハロゲンランプを、１０〜２０ｃｍの距離から数秒間照射することによって容易に行うことができる。 In the present invention, by applying the coating solution on the film, heating and drying, the coating layer (antiglare layer) is further irradiated with ultraviolet rays using a known light source such as a halogen lamp, The coating layer is photocured. The film thus photocured has extremely high hardness. Curing can be easily performed, for example, by irradiating a halogen lamp with an output of 120 to 240 W / cm for several seconds from a distance of 10 to 20 cm.
以下、実施例にて本発明を例証するが、本発明を限定することを意図するものではない。
なお、微粒子の平均粒子径は、レーザー回折粒度測定器ＳＡＬＤ２２００（島津製作所製）で測定した。又、特に断らない限り、以下に記載する「部」及び「％」は、それぞれ「重量部」及び「重量％」を表す。
The following examples illustrate the invention, but are not intended to limit the invention.
The average particle size of the fine particles was measured with a laser diffraction particle size analyzer SALD2200 (manufactured by Shimadzu Corporation). Unless otherwise specified, “parts” and “%” described below represent “parts by weight” and “% by weight”, respectively.
［実施例１］
＜塗料調製＞
Ｎｉｐｓｉｌ Ｅ−７５（シリカ微粒子、東ソー・シリカ（株）社製、平均粒子径２．４μｍ、吸油量１２０ｍｌ／１００ｇ、非表面積５０ｍ２／ｇ）３．２ｇとＭｉｚｕｋａｓｉｌＰ−７３（シリカ微粒子、水澤化学工業（株）社製、平均粒子径４．０μｍ、吸油量１８０ｍｌ／１００ｇ、非表面積３３０ｍ２／ｇ）２．２ｇをトルエン４６．０ｇに混合し十分攪拌した。この液に、アートレジンＵＮ−３３２０ＨＡ（電離放射線硬化型樹脂、根上（株）社製）４６．１ｇ、イルガキュア１８４（光重合開始剤、（株）チバスペシャリティーケミカル社製）２．４ｇ、ＢＹＫ３２０（レベリング剤、ビックケミー（株）社製）０．１ｇを添加し塗料を調製した。
[Example 1]
<Preparation of paint>
Nipsil E-75 (silica fine particles, manufactured by Tosoh Silica Co., Ltd., average particle size 2.4 μm, oil absorption 120 ml / 100 g, non-surface area 50 m 2 / g) and 3.2 g Mizukasil P-73 (silica fine particles, Mizusawa Chemical) Industrial Co., Ltd. product, average particle size 4.0 μm, oil absorption 180 ml / 100 g, non-surface area 330 m 2 / g) 2.2 g was mixed with toluene 46.0 g and sufficiently stirred. In this solution, Art Resin UN-3320HA (ionizing radiation curable resin, manufactured by Negami Co., Ltd.) 46.1 g, Irgacure 184 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 2.4 g, BYK320 A coating material was prepared by adding 0.1 g (leveling agent, manufactured by Big Chemie Co., Ltd.).
＜防眩フィルム作製＞
Ｆｕｊｉ ＴＡＣ（トリアセチルセルロースフィルム、富士フィルム（株）社製）に上記塗料をマイヤーバー＃８（ＲＤＳ社製）で塗工し、７０℃で１分間乾燥後、３００ｍＪ／ｃｍ２の紫外線（光源：ＦｕｓｉｏｎＪａｐａｎ社製ＵＶランプ）を照射し硬化した。得られた塗膜の厚さは７μｍほどであった。
<Preparation of antiglare film>
The above-mentioned paint was applied to Fuji TAC (triacetylcellulose film, manufactured by Fuji Film Co., Ltd.) with Meyer bar # 8 (manufactured by RDS), dried at 70 ° C. for 1 minute, and then 300 mJ / cm 2 ultraviolet light (light source) : UV lamp manufactured by Fusion Japan) and cured. The thickness of the obtained coating film was about 7 μm.
［実施例２］
＜塗料調製＞
Ｎｉｐｓｉｌ Ｅ−７５（シリカ微粒子、東ソー・シリカ（株）社製、平均粒子径２．４μｍ、吸油量１２０ｍｌ／１００ｇ、非表面積５０ｍ２／ｇ）１．６ｇとファインシールＸ−４５（シリカ微粒子、（株）トクヤマ社製、平均粒子径４．３μｍ、吸油量２４０ｍｌ／１００ｇ、非表面積３００ｍ２／ｇ）１．２ｇをトルエン５７．２ｇと混合し十分攪拌した。この液に、アロニックスＭ−４００（電離放射線硬化型樹脂、東亜合成化学工業（株）社製）３２．３ｇ、イルガキュア１８４（光重合開始剤、（株）チバスペシャリティーケミカル社製）２．２ｇ、ＢＹＫＵＶ３５１０（レベリング剤、ビックケミー（株）社製）０．１ｇを添加し塗料を調製した。
[Example 2]
<Preparation of paint>
Nipsil E-75 (silica fine particles, manufactured by Tosoh Silica Co., Ltd., average particle size 2.4 μm, oil absorption 120 ml / 100 g, non-surface area 50 m 2 / g) 1.6 g and fine seal X-45 (silica fine particles, 1.2 g of Tokuyama Corporation average particle size 4.3 μm, oil absorption 240 ml / 100 g, non-surface area 300 m 2 / g) was mixed with 57.2 g of toluene and sufficiently stirred. To this solution, 32.3 g of Aronix M-400 (ionizing radiation curable resin, manufactured by Toagosei Chemical Co., Ltd.), Irgacure 184 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2.2 g BYKUV3510 (leveling agent, manufactured by Big Chemie Co., Ltd.) 0.1 g was added to prepare a paint.
＜防眩フィルム作製＞
Ｆｕｊｉ ＴＡＣ（トリアセチルセルロースフィルム、富士フィルム（株）社製）に上記塗料をマイヤーバー＃１４（ＲＤＳ社製）で塗工し、７０℃で１分間乾燥後、３００ｍＪ／ｃｍ２の紫外線（光源：ＦｕｓｉｏｎＪａｐａｎ社製ＵＶランプ）を照射し硬化した。得られた塗膜の厚さは７μｍほどであった。
<Preparation of antiglare film>
The above-mentioned paint was applied to Fuji TAC (triacetyl cellulose film, manufactured by Fuji Film Co., Ltd.) with Meyer bar # 14 (manufactured by RDS), dried at 70 ° C. for 1 minute, and then 300 mJ / cm 2 ultraviolet light (light source) : UV lamp manufactured by Fusion Japan) and cured. The thickness of the obtained coating film was about 7 μm.
［実施例３］
＜塗料調製＞
アドマファインＳＯ−０６（球形疎水化シリカ微粒子、アドマテックス（株）社製、平均粒子径２．２μｍ、吸油量数十ｍｌ／１００ｇ、非表面積５００ｍ２／ｇ）２．４ｇとＭｉｚｕｋａｓｉｌＰ−７３（シリカ微粒子、水澤化学工業（株）社製、平均粒子径４．０μｍ、吸油量１８０ｍｌ／１００ｇ、非表面積３３０ｍ２／ｇ）１．６ｇをトルエン６０．０ｇと混合し十分攪拌した。この液に、Ｅｂｅｃｒｙｌ２００（電離放射線硬化型樹脂、ダイセル・ユーシービー（株）社製）３４．０ｇ、イルガキュア１８４（光重合開始剤、（株）チバスペシャリティーケミカル社製）１．９ｇ、ＢＹＫ３２５（レベリング剤、ビックケミー（株）社製）０．１ｇを添加し塗料を調製した。
[Example 3]
<Preparation of paint>
Admafine SO-06 (spherical hydrophobized silica fine particles, manufactured by Admatechs Co., Ltd., average particle size 2.2 μm, oil absorption tens ml / 100 g, non-surface area 500 m 2 / g) 2.4 g and Mizukasil P-73 ( Silica fine particles, manufactured by Mizusawa Chemical Co., Ltd., average particle size 4.0 μm, oil absorption 180 ml / 100 g, non-surface area 330 m 2 / g) 1.6 g were mixed with toluene 60.0 g and sufficiently stirred. In this solution, Ebecryl 200 (ionizing radiation curable resin, manufactured by Daicel UC Co., Ltd.) 34.0 g, Irgacure 184 (photopolymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd.) 1.9 g, BYK325 ( 0.1 g of a leveling agent (manufactured by Big Chemie Co., Ltd.) was added to prepare a paint.
＜防眩フィルム作製＞
Ｆｕｊｉ ＴＡＣ（トリアセチルセルロースフィルム、富士フィルム（株）社製）に上記塗料をマイヤーバー＃１２（ＲＤＳ社製）で塗工し、７０℃で１分間乾燥後、３００ｍＪ／ｃｍ２の紫外線（光源：ＦｕｓｉｏｎＪａｐａｎ社製ＵＶランプ）を照射し硬化した。得られた塗膜の厚さは８μｍほどであった。
<Preparation of antiglare film>
The above-mentioned paint was applied to Fuji TAC (triacetylcellulose film, manufactured by Fuji Film Co., Ltd.) with Meyer bar # 12 (manufactured by RDS), dried at 70 ° C. for 1 minute, and then 300 mJ / cm 2 ultraviolet light (light source) : UV lamp manufactured by Fusion Japan) and cured. The thickness of the obtained coating film was about 8 μm.
［比較例１］
実施例２のＮｉｐｓｉｌ Ｅ−７５及びファインシール Ｘ−４５をすべてＭｉｚｕｋａｓｉｌ Ｐ−５０（シリカ微粒子、水澤化学工業（株）社製、平均粒子径１０．０μｍ、吸油量１７０ｍｌ／１００ｇ、非表面積３３０ｍ２／ｇ）に変えた以外は実施例２と同様にして防眩フィルムを作製した。得られた塗膜の厚さは８μｍほどであった。
[Comparative Example 1]
Nipsil E-75 and Fine Seal X-45 of Example 2 were all prepared by Mizukasil P-50 (silica fine particles, manufactured by Mizusawa Chemical Industry Co., Ltd., average particle size 10.0 μm, oil absorption 170 ml / 100 g, non-surface area 330 m 2. An anti-glare film was produced in the same manner as in Example 2 except that the amount was changed to / g). The thickness of the obtained coating film was about 8 μm.
［比較例２］
実施例２のＮｉｐｓｉｌ Ｅ−７５及びファインシール Ｘ−４５をすべてＮｉｐｇｅｌ ＣＸ−２００（シリカ微粒子、東ソー・シリカ（株）社製、平均粒子径２．１μｍ、吸油量１１５ｍｌ／１００ｇ、非表面積７５０ｍ２／ｇ）に変えた以外は実施例２と同様にして防眩フィルムを作製した。得られた塗膜の厚さは８μｍほどであった。
[Comparative Example 2]
Nipsil CX-200 (silica fine particles, manufactured by Tosoh Silica Co., Ltd., average particle size 2.1 μm, oil absorption 115 ml / 100 g, non-surface area 750 m 2) An anti-glare film was produced in the same manner as in Example 2 except that the amount was changed to / g). The thickness of the obtained coating film was about 8 μm.
［比較例３］
実施例２のＮｉｐｓｉｌ Ｅ−７５及びファインシール Ｘ−４５をすべてＳＹＬＹＳＩＡ ３１０Ｐ（シリカ微粒子、富士シリシア（株）社製、平均粒子径２．７μｍ、吸油量３１０ｍｌ／１００ｇ、非表面積３００ｍ２／ｇ）に変えた以外は実施例２と同様にして防眩フィルムを作製した。得られた塗膜の厚さは８μｍほどであった。
[Comparative Example 3]
Nipsil E-75 and Fine Seal X-45 of Example 2 were all SYLYSIA 310P (silica fine particles, manufactured by Fuji Silysia Co., Ltd., average particle size 2.7 μm, oil absorption 310 ml / 100 g, non-surface area 300 m 2 / g) An antiglare film was produced in the same manner as in Example 2 except that The thickness of the obtained coating film was about 8 μm.
［比較例４］
実施例１のＮｉｐｓｉｌ Ｅ−７５（３．２ｇ）、Ｍｉｚｕｋａｓｉｌ Ｐ−７３（２．２ｇ）、アートレジンＵＮ−３３２０ＨＡ（４６．１ｇ）及びイルガキュア１８４（２．４ｇ）をＮｉｐｓｉｌＥ−７５（７．８ｇ）、Ｍｉｚｕｋａｓｉｌ Ｐ−７３（５．２ｇ）、アートレジンＵＮ−３３２０ＨＡ（３８．９ｇ）及びイルガキュア１８４（２．０ｇ）に変えた以外は、実施例１と同様にして防眩フィルムを作製した。得られた塗膜の厚さは８μｍほどであった。
[Comparative Example 4]
Example 1 Nipsil E-75 (3.2 g), Mizukasil P-73 (2.2 g), Art Resin UN-3320HA (46.1 g) and Irgacure 184 (2.4 g) were replaced with Nipsil E-75 (7.8 g). ), Mizukasil P-73 (5.2 g), Art Resin UN-3320HA (38.9 g) and Irgacure 184 (2.0 g), an antiglare film was produced in the same manner as in Example 1. The thickness of the obtained coating film was about 8 μm.
［比較例５］
実施例１のＮｉｐｓｉｌ Ｅ−７５（３．２ｇ）、Ｍｉｚｕｋａｓｉｌ Ｐ−７３（２．２ｇ）、アートレジンＵＮ−３３２０ＨＡ（４６．１ｇ）及びイルガキュア１８４（２．４ｇ）をＮｉｐｓｉｌＥ−７５（１．６ｇ）、Ｍｉｚｕｋａｓｉｌ Ｐ−７３（１．１ｇ）、アートレジンＵＮ−３３２０ＨＡ（４８．６ｇ）及びイルガキュア１８４（２．６ｇ）に変えた以外は、実施例１と同様にして防眩フィルムを作製した。得られた塗膜の厚さは７μｍほどであった。
[Comparative Example 5]
Nipsil E-75 (3.2 g), Mizukasil P-73 (2.2 g), Art Resin UN-3320HA (46.1 g) and Irgacure 184 (2.4 g) of Example 1 were replaced with Nipsil E-75 (1.6 g). ), Mizukasil P-73 (1.1 g), Art Resin UN-3320HA (48.6 g) and Irgacure 184 (2.6 g), an antiglare film was produced in the same manner as in Example 1. The thickness of the obtained coating film was about 7 μm.
［比較例６］
実施例１のＮｉｐｓｉｌ Ｅ−７５（３．２ｇ）及びＭｉｚｕｋａｓｉｌ Ｐ−７３（２．２ｇ）をＮｉｐｓｉｌＥ−７５（４．４ｇ）及びＭｉｚｕｋａｓｉｌ Ｐ−７３（１．０ｇ）に変えた以外は、実施例１と同様にして防眩フィルムを作製した。得られた塗膜の厚さは７μｍほどであった。
[Comparative Example 6]
Example 1 except that Nipsil E-75 (3.2 g) and Mizukasil P-73 (2.2 g) in Example 1 were replaced with Nipsil E-75 (4.4 g) and Mizukasil P-73 (1.0 g). In the same manner as in Example 1, an antiglare film was produced. The thickness of the obtained coating film was about 7 μm.
［比較例７］
実施例１のＮｉｐｓｉｌ Ｅ−７５（３．２ｇ）及びＭｉｚｕｋａｓｉｌ Ｐ−７３（２．２ｇ）をＮｉｐｓｉｌＥ−７５（１．０ｇ）及びＭｉｚｕｋａｓｉｌ Ｐ−７３（４．４ｇ）に変えた以外は、実施例１と同様にして防眩フィルムを作製した。得られた塗膜の厚さは７μｍほどであった。
[Comparative Example 7]
Example 1 except that Nipsil E-75 (3.2 g) and Mizukasil P-73 (2.2 g) in Example 1 were replaced with Nipsil E-75 (1.0 g) and Mizukasil P-73 (4.4 g). In the same manner as in Example 1, an antiglare film was produced. The thickness of the obtained coating film was about 7 μm.
以上の各実施例及び比較例で得られた防眩ハードコートフィルムについて、下記項目の試験を行った。なお、耐擦傷性及び視認性等の項目に関してはハードコート面について試験を行った。その試験結果を後記表１にまとめる。 About the anti-glare hard coat film obtained by the above each Example and the comparative example, the test of the following item was done. Note that the hard coat surface was tested for items such as scratch resistance and visibility. The test results are summarized in Table 1 below.
１）透過率およびヘイズ度：村上色彩技術研究所製ヘイズメーターＨＭ１５０を用いて測定した。
２）耐擦傷性：防眩層表面に＃００００のスチールウールを置き、半径１．２５ｃｍに１０００ｇの加重で防眩層上を１０回往復させた後の防眩層表面の傷の本数を目視で数えた。防眩層に傷が無いものを○、傷１０本未満を△、傷１０本以上を×とした。
３）防眩性：防眩フィルムの防眩層において蛍光灯からの反射光を目視で評価した。反射光が眩しくないものを○、少し眩しいものを△、眩しいものを×とした。
４）ギラツキ：全面緑色表示させたＬＣＤ（液晶表示体）の上に各防眩フィルムを重ね、画面のちらつきの度合いを目視で評価した。なお、ＬＣＤ表面には予めクリアタイプのハードコートフィルムが設置されている。ギラツキが見られないもの及びギラツキがわずかであるものを○、ちらつきが大きいものを×とした。
５）白ぼけ：塗工反対面に黒色のビニールテープ（日東ビニールテープ、ＰＲＯＳＥＬＦ Ｎｏ．２１（幅広））を貼りマクベス濃度計で黒濃度を測定した。２．１０以上を○、２．１０〜２．００を△、２．００未満を×とした。
1) Transmittance and haze degree: Measured using a haze meter HM150 manufactured by Murakami Color Research Laboratory.
2) Scratch resistance: Place # 0000 steel wool on the surface of the antiglare layer and visually check the number of scratches on the surface of the antiglare layer after reciprocating 10 times on the antiglare layer with a load of 1000 g at a radius of 1.25 cm. I counted. The case where the antiglare layer was not scratched was rated as ◯, the number of less than 10 scratches as Δ, and the number of scratches as 10 or more as X.
3) Antiglare property: Reflected light from a fluorescent lamp was visually evaluated in the antiglare layer of the antiglare film. The case where the reflected light was not dazzled was rated as “◯”, the case where the reflected light was slightly dazzled as “Δ”, and the dazzled one as “x”.
4) Glare: Each anti-glare film was layered on an LCD (liquid crystal display) that was displayed in green on the entire surface, and the degree of flickering on the screen was visually evaluated. A clear type hard coat film is installed on the LCD surface in advance. The case where no glare was observed and the case where the glare was slight was rated as ◯, and the case where flicker was large as x.
5) White blur: A black vinyl tape (Nitto vinyl tape, PROSELF No. 21 (wide)) was applied to the opposite surface of the coating, and the black density was measured with a Macbeth densitometer. 2.10 or more was set as (circle), 2.10-2.00 were set as (triangle | delta), and less than 2.00 was set as x.
以上の表１の結果から明らかなように、２種類の微粒子の平均粒子径、吸油量をそれぞれ特定の範囲内としたものを、樹脂に対する特定の合計配合量、２種類の微粒子同士の特定の配合割合で組み合わせた実施例１〜３では、良好な透過率、ヘイズ度、耐擦傷性、視認性（防眩性、ギラツキ、白ぼけ）が得られた。 As is apparent from the results of Table 1 above, the average particle diameter and the oil absorption amount of the two types of fine particles are within the specific ranges, respectively, the specific total blending amount for the resin, and the specific types of the two types of fine particles. In Examples 1 to 3 combined at a blending ratio, good transmittance, haze degree, scratch resistance, and visibility (antiglare, glare, white blur) were obtained.
これに対して、微粒子の平均粒子径及び吸油量が大きい（本発明の第１種の微粒子に相当する微粒子が含まれていない）比較例１では、ヘイズが高く、透過率が低く、耐擦傷性が悪く、ギラツキと白ぼけも顕著であった。また、本発明の第２種の微粒子に相当する微粒子が含まれておらず、また微粒子の比表面積が大きい比較例で２は、ヘイズが高く、若干防眩性が弱く、ギラツキも発生した。また、第１種の微粒子の吸油量が大きく、しかも第２種の微粒子の粒子径が小さい比較例３では、耐擦傷性が若干劣り、白ぼけが悪かった。また、樹脂に対する微粒子の配合量が多い比較例４では、ヘイズが高く、耐擦傷性が若干劣り、ギラツキと白ぼけも顕著であった。逆に樹脂に対する微粒子の配合量が少ない比較例５では、防眩性が顕著に弱く外光の映り込みがあった。また、第１種の微粒子の配合割合が多い比較例６では、若干防眩性が弱く外光の映り込みがわずかにあった。逆に第１種の微粒子の配合割合が少ない（第２種の微粒子の配合割合が多い）比較例７では、ギラツキが発生した。 On the other hand, in Comparative Example 1 in which the average particle diameter and oil absorption amount of the fine particles are large (no fine particles corresponding to the first type fine particles of the present invention are included), the haze is high, the transmittance is low, and the scratch resistance is high. The nature was poor, and glare and white blur were also noticeable. Further, Comparative Example 2, which does not contain fine particles corresponding to the second type of fine particles of the present invention and has a large specific surface area, has high haze, slightly weak antiglare property, and glare. In Comparative Example 3 where the oil absorption of the first type of fine particles was large and the particle size of the second type of fine particles was small, the scratch resistance was slightly inferior and white blurring was poor. Further, in Comparative Example 4 in which the blending amount of the fine particles with respect to the resin was large, the haze was high, the scratch resistance was slightly inferior, and glare and white blur were also remarkable. On the contrary, in Comparative Example 5 where the blending amount of the fine particles with respect to the resin is small, the antiglare property is remarkably weak and there is reflection of external light. Further, in Comparative Example 6 in which the proportion of the first type fine particles was large, the antiglare property was slightly weak and the reflection of external light was slight. On the contrary, glare occurred in Comparative Example 7 in which the blending ratio of the first type of fine particles was small (the blending ratio of the second type of microparticles was large).
１ 透明フィルム
２ 防眩層
３ 第１種の微粒子
４ 第２種の微粒子
５ 樹脂
DESCRIPTION OF SYMBOLS 1
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| JP6255748B2 (en) | 2013-07-02 | 2018-01-10 | 東洋製罐グループホールディングス株式会社 | Resin molded body having a surface excellent in water slidability |
| KR102087194B1 (en) * | 2013-08-09 | 2020-03-11 | 삼성디스플레이 주식회사 | Display device and manufacturing method thereof |
| JP6884045B2 (en) * | 2017-06-13 | 2021-06-09 | リンテック株式会社 | Manufacturing method of anti-glare hard coat film and anti-glare hard coat film |
| JP6579185B2 (en) * | 2017-12-06 | 2019-09-25 | 東洋製罐グループホールディングス株式会社 | Resin molding having a surface excellent in water slidability |
| KR102621489B1 (en) * | 2021-02-26 | 2024-01-09 | 율촌화학 주식회사 | Low-reflection film comprising low-reflection coating layer and the method for manufacturing the same |
| JP2023146802A (en) | 2022-03-29 | 2023-10-12 | リンテック株式会社 | anti-glare film |
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| JPH1144805A (en) * | 1997-07-28 | 1999-02-16 | Denso Corp | Antidazzle transparent resin molding |
| JP3931408B2 (en) * | 1997-12-25 | 2007-06-13 | 凸版印刷株式会社 | Anti-glare hard coat film |
| JP4776150B2 (en) * | 2002-04-24 | 2011-09-21 | 大日本印刷株式会社 | Anti-glare film, polarizing element, and image display device |
| JP2008119867A (en) * | 2006-11-09 | 2008-05-29 | Lintec Corp | Anti-glaring hard coat film |
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