JP2007181950A - Biaxially oriented polyester film - Google Patents
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本発明は、ポリエステルフィルムの表面に接着剤層や紫外線硬化樹脂層などを設けて使用される、艶消し性を必要とするガラスや成形体と貼り合わされる用途、ラベル用途や蒸着包装用途、また液晶ディスプレイの構成部品、例えばバックライトユニットの拡散板やプリズムシート、またプロジェクター用のスクリーンのレンズシートなどの基材フィルムとして使用することのできる、易接着を有する光散乱性の二軸延伸ポリエステルフィルムに関する。 The present invention is used by providing an adhesive layer, an ultraviolet curable resin layer or the like on the surface of a polyester film, used for bonding with glass or a molded product requiring matting properties, label use, vapor deposition packaging use, Light-scattering biaxially stretched polyester film with easy adhesion that can be used as a base film for liquid crystal display components, such as diffuser plates and prism sheets for backlight units, and lens sheets for projector screens. About.
光拡散剤を含有させた二軸延伸ポリエステルフィルムとして、特許文献1または特許文献2には、平均粒子径が数μmの無機粒子を数%含有させたポリエステルフィルムが提案されているが、樹脂押し出しラインでのフィルター圧力上昇が起こりやすく、生産性が悪いという問題がある。また、無機粒子は有機粒子よりもフィルム樹脂との熱膨張係数差が大きいため、環境温度変化が大きいところでフィルム基材が使用される場合、フィルム表面の突起に異常が発生し、脱落しやすくなることがある。 As a biaxially stretched polyester film containing a light diffusing agent, Patent Document 1 or Patent Document 2 proposes a polyester film containing several percent of inorganic particles having an average particle diameter of several μm. There is a problem that the filter pressure rises easily in the line and the productivity is poor. In addition, since inorganic particles have a larger difference in thermal expansion coefficient from the film resin than organic particles, when a film substrate is used at a large environmental temperature change, abnormalities occur in projections on the film surface, and it tends to drop off. Sometimes.
また、従来の光散乱性の二軸延伸ポリエステルフィルムは、光拡散剤とフィルム樹脂の屈折率の差で光散乱性の機能を持たせる設計としている。しかし空気とフィルム樹脂界面のほうが屈折率差は大きいため、表面に凹凸を持たせる設計にした方がフィルムの艶消し効果が大きい。さらに、多くのポリエステルフィルムには、用途に応じた様々な機能を持たせるためにフィルム表面に接着剤層や蒸着層を設けること、また様々な形状の凹凸を賦型することもある。その場合、基材フィルム表面との接着性が良好であることが望まれるが、それらを満足するフィルムが得られていないのが実情である。 Moreover, the conventional light-scattering biaxially stretched polyester film is designed to have a light-scattering function due to the difference in refractive index between the light diffusing agent and the film resin. However, since the difference in refractive index is larger at the interface between air and the film resin, the matte effect of the film is greater when the surface is designed to have irregularities. Furthermore, many polyester films may be provided with an adhesive layer or a vapor deposition layer on the surface of the film in order to have various functions depending on the application, and irregularities having various shapes may be formed. In that case, it is desired that the adhesiveness with the surface of the base film is good, but the actual situation is that a film satisfying them is not obtained.
本発明は、上記実情に鑑みなされたものであり、その解決課題は、環境温度変化で変質しにくい粗面を有し、艶消し性に優れ、易接着の光散乱性二軸延伸ポリエステルフィルムを提供することにある。 The present invention has been made in view of the above circumstances, and the problem to be solved is a light-scattering biaxially stretched polyester film having a rough surface that is difficult to change due to changes in environmental temperature, excellent matting properties, and easy adhesion. It is to provide.
本発明者は、上記課題に鑑み鋭意検討した結果、特定の構成を有する二軸延伸ポリエステルフィルムによれば、上記課題を容易に解決できることを見いだし、本発明を完成するに至った。 As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be easily solved by a biaxially stretched polyester film having a specific configuration, and have completed the present invention.
すなわち、本発明の要旨は、一方の表層を構成するポリエステル層に有機粒子を含有し、当該表層の表面粗さ(Ra)が0.08μm以上であり、当該表層の厚み(L)と前記有機粒子の平均粒径(R)との比(L/R)が4.0以下であり、いずれかのフィルム表面に易接着塗布層を有することを特徴とする二軸延伸ポリエステルフィルムに存する。 That is, the gist of the present invention is that the polyester layer constituting one surface layer contains organic particles, the surface layer has a surface roughness (Ra) of 0.08 μm or more, the surface layer thickness (L) and the organic layer. The ratio (L / R) to the average particle size (R) of the particles is 4.0 or less, and the present invention resides in a biaxially stretched polyester film characterized by having an easily adhesive coating layer on any film surface.
以下、本発明を詳細に説明する。
本発明におけるポリエステルとは、テレフタル酸、イソフタル酸、ナフタレン−2,6−ジカルボン酸等のような芳香族ジカルボン酸と、エチレングリコール、ジエチレングリコール、トリメチレングリコール、テトラメチレングリコール、ネオペンチルグリコール、1,4−シクロヘキサンジメタノール等のようなグリコールとのエステルを主たる成分とするポリエステルである。当該ポリエステルは、芳香族ジカルボン酸とグリコールとを直接重合させて得られるほか、芳香族ジカルボン酸ジアルキルエステルとグリコールとをエステル交換反応させた後、重縮合させる方法、あるいは芳香族ジカルボン酸のジグリコールエステルを重縮合させる等の方法によっても得られる。当該ポリエステルの代表的なものとしては、ポリエチレンテレフタレート、ポリエチレン−2,6−ナフタレンジカルボキシレート(PEN)、ボリブチレンテレフタレート等が例示される。かかるポリエステルは、共重合されないホモポリマーであってもよく、またジカルボン酸成分の40モル%以下が主成分以外のジカルボン酸成分であり、ジオール成分の40モル%以下が主成分以外のジオール成分であるような共重合ポリエステルであってもよく、またそれらの混合物であってもよい。
Hereinafter, the present invention will be described in detail.
The polyester in the present invention is an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, 1, This polyester is mainly composed of an ester with glycol such as 4-cyclohexanedimethanol. The polyester can be obtained by directly polymerizing an aromatic dicarboxylic acid and a glycol, or by a transesterification reaction between an aromatic dicarboxylic acid dialkyl ester and a glycol, followed by polycondensation, or an aromatic dicarboxylic acid diglycol. It can also be obtained by a method such as polycondensation of an ester. Typical examples of the polyester include polyethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate (PEN), boribylene terephthalate, and the like. Such a polyester may be a homopolymer that is not copolymerized, 40 mol% or less of the dicarboxylic acid component is a dicarboxylic acid component other than the main component, and 40 mol% or less of the diol component is a diol component other than the main component. It may be a certain copolyester or a mixture thereof.
本発明では、光を散乱させる粗面を形成するために、少なくとも一方の表層に有機粒子を配合する。本発明で用いる有機粒子の平均粒子径は、好ましくは2〜40μm、さらに好ましくは2〜30μm、特に好ましくは3〜20μmの範囲である。平均粒子径が2μm未満では、フィルム表面に大きな突起が形成され、光散乱性が劣る傾向がある。一方、平均粒子径が40μmを超える場合は、フィルターの圧力上昇が大きくなるので、生産性が劣る傾向がある。また、用いるフィルターの目を大きくするとフィルム中の異物が増加する場合がある。 In this invention, in order to form the rough surface which scatters light, an organic particle is mix | blended with at least one surface layer. The average particle size of the organic particles used in the present invention is preferably 2 to 40 μm, more preferably 2 to 30 μm, and particularly preferably 3 to 20 μm. When the average particle diameter is less than 2 μm, large protrusions are formed on the film surface, and the light scattering property tends to be inferior. On the other hand, when the average particle diameter exceeds 40 μm, the increase in the pressure of the filter becomes large, so that the productivity tends to be inferior. Moreover, when the filter eyes used are enlarged, foreign matter in the film may increase.
本発明のフィルム全体に対する有機粒子の含有量は、好ましくは0.02〜2重量%、さらに好ましくは0.04〜1重量%の範囲である。有機粒子含有量が0.02重量%未満では、本発明が意図する光散乱性を得ることができない場合がある。一方、含有量が2重量%を超えても光散乱性を大きく改善することはなく、無駄な添加を行うことになる。 The content of organic particles in the entire film of the present invention is preferably in the range of 0.02 to 2% by weight, more preferably 0.04 to 1% by weight. If the organic particle content is less than 0.02% by weight, the light scattering property intended by the present invention may not be obtained. On the other hand, even if the content exceeds 2% by weight, the light scattering property is not greatly improved, and useless addition is performed.
本発明で使用する有機粒子については、熱重量分析計により測定される、不活性雰囲気下の5%熱分解温度が通常300℃以上であり、好ましくは310℃以上である。熱分解温度が300℃未満では、熱劣化物の発生によってフィルムの透過光が黄色味を帯びて外観品質の低下が起こることがある。 For the organic particles used in the present invention, the 5% pyrolysis temperature under an inert atmosphere as measured by a thermogravimetric analyzer is usually 300 ° C or higher, preferably 310 ° C or higher. When the thermal decomposition temperature is less than 300 ° C., the transmitted light of the film is yellowish due to the generation of a thermally deteriorated product, and the appearance quality may be deteriorated.
また、本発明で使用する有機粒子は、二軸延伸の条件で変形する程度の硬さを有することが好ましく、具体的には、その変形度が1.1〜5.0の範囲が好ましく、1.2〜4.0の範囲がさらに好ましい。変形度が1.1未満の有機粒子では、ポリエステル樹脂溶解温度の250〜350℃の高温下でせん断応力を受けたときに弾性変形の程度が小さくなり、フィルターの寿命が低下することがある。一方、変形度が5.0を超えると突起の高さが小さくなり、光散乱性が低下する傾向がある。 In addition, the organic particles used in the present invention preferably have a hardness that can be deformed under biaxial stretching conditions. Specifically, the degree of deformation is preferably in the range of 1.1 to 5.0. A range of 1.2 to 4.0 is more preferable. In the case of organic particles having a degree of deformation of less than 1.1, the degree of elastic deformation is reduced when subjected to shear stress at a polyester resin dissolution temperature of 250 to 350 ° C., and the life of the filter may be reduced. On the other hand, when the degree of deformation exceeds 5.0, the height of the protrusion is reduced, and the light scattering property tends to be lowered.
また本発明で用いる有機粒子は、表面に官能基を有することが好ましい。官能基を有する粒子は帯電しやすく粒子間の静電的な反発力が働き分散性が向上する。官能基を有しないと粒子間で凝集しやすくなり、フィルター寿命が低下する傾向がある。さらにポリエステルとの親和性が低下し、粒子周りに大きなボイドを形成し、フィルム製造工程やフィルムの加工工程で粒子が脱落しやすくなり、その結果、フィルム自身にキズが発生し、外観品質の低下を起こすおそれがある。好ましい官能基としてはカルボン酸基、水酸基、エポキシ基、エステル基である。 The organic particles used in the present invention preferably have a functional group on the surface. The particles having a functional group are easily charged, and an electrostatic repulsive force between the particles acts to improve dispersibility. If there is no functional group, it tends to aggregate between particles and the filter life tends to be reduced. In addition, the affinity with polyester decreases, forming large voids around the particles, making it easier for the particles to fall off during the film manufacturing process and film processing process, resulting in scratches on the film itself and deterioration in appearance quality. There is a risk of causing. Preferred functional groups are a carboxylic acid group, a hydroxyl group, an epoxy group, and an ester group.
なお本発明で使用する有機粒子は、単成分でもよく、また、2成分以上を同時に用いてもよい。具体的な有機粒子の例としては、メラミン樹脂、ポリスチレン、有機シリコーン樹脂、アクリル−スチレン共重合体等の有機粒子が挙げられる。 The organic particles used in the present invention may be a single component, or two or more components may be used simultaneously. Specific examples of organic particles include organic particles such as melamine resin, polystyrene, organic silicone resin, and acrylic-styrene copolymer.
本発明のフィルムにおいて、有機粒子を含有する表層の厚み(L)と当該有機粒子の平均粒径(R)との比(L/R)は4.0以下であり、好ましくは3.0以下、特に好ましくは2.5以下である。有機粒子含有層の厚みが用いる有機粒子の平均粒子径の4.0倍を超えると、フィルム表面の突起形成に寄与する有機粒子の割合が低下するため、粒子添加に対する光散乱の効率が低下し、また艶消し性も低下する。一方、有機粒子含有層の厚みは、用いる有機粒子の平均粒子径の0.1倍以上であることが好ましい。0.1倍未満では表面の突起密度が小さくなり光散乱性が低下する傾向がある。 In the film of the present invention, the ratio (L / R) of the thickness (L) of the surface layer containing organic particles to the average particle size (R) of the organic particles is 4.0 or less, preferably 3.0 or less. Particularly preferably, it is 2.5 or less. If the thickness of the organic particle-containing layer exceeds 4.0 times the average particle diameter of the organic particles used, the ratio of organic particles contributing to the formation of protrusions on the film surface decreases, so the efficiency of light scattering with respect to particle addition decreases. Also, the matte property is reduced. On the other hand, the thickness of the organic particle-containing layer is preferably at least 0.1 times the average particle diameter of the organic particles used. If it is less than 0.1 times, the protrusion density on the surface becomes small and the light scattering property tends to be lowered.
また本発明のフィルムにおいて、有機粒子含有層の表面粗さ(Ra)は0.08μm以上であり、粗面化されている必要があり、好ましくは0.09μm以上、特に好ましくは0.10μm以上である。当該粗面の表面粗さRaが0.08μm未満では、光散乱性や艶消し性が劣る。 In the film of the present invention, the organic particle-containing layer has a surface roughness (Ra) of 0.08 μm or more, and needs to be roughened, preferably 0.09 μm or more, particularly preferably 0.10 μm or more. It is. When the surface roughness Ra of the rough surface is less than 0.08 μm, the light scattering property and the matte property are inferior.
本発明において、粗面の反対面の表面粗さ(Ra)は、0.008μm以上の平坦面であることが好ましく、さらに好ましくは0.008μm以上である。Raが0.008μm未満では、フィルム生産工程またはフィルム加工工程でフィルム平滑面にキズが発生しやすい傾向があり、一方、0.04μmを超えると、フィルム用途によっては加工特性や蒸着特性が低下することがある。なお、平坦面のRaを0.008μm以上にするために粗面の反対面を構成する層に微量の不活性粒子を含有することが好ましい。不活性粒子の種類は、無機粒子、有機粒子のいずれでもよい。 In the present invention, the surface roughness (Ra) of the surface opposite to the rough surface is preferably a flat surface of 0.008 μm or more, more preferably 0.008 μm or more. If Ra is less than 0.008 μm, scratches tend to occur on the smooth surface of the film in the film production process or film processing step. On the other hand, if it exceeds 0.04 μm, the processing characteristics and vapor deposition characteristics may deteriorate depending on the film application. Sometimes. In addition, in order to make Ra of a flat surface 0.008 micrometer or more, it is preferable to contain a trace amount of inert particle in the layer which comprises the surface opposite to a rough surface. The kind of the inert particles may be either inorganic particles or organic particles.
また本発明のフィルムの光沢度は、好ましくは80%以下、さらに好ましくは70%以下、特に好ましくは60%以下である。光沢度が80%を超えると艶消し性が劣る傾向がある。 The gloss of the film of the present invention is preferably 80% or less, more preferably 70% or less, and particularly preferably 60% or less. When the glossiness exceeds 80%, the matte property tends to be inferior.
また本発明のフィルムのヘーズは、20%以上が好ましく、さらに好ましくは30%以上、特に好ましくは35%以上である。ヘーズが20%未満では、光散乱性の点で劣る傾向がある。 The haze of the film of the present invention is preferably 20% or more, more preferably 30% or more, and particularly preferably 35% or more. If the haze is less than 20%, the light scattering property tends to be inferior.
本発明のフィルム中には必要に応じて、アンチブロッキング剤、紫外線吸収剤、帯電防止剤、酸化防止剤、蛍光増白剤等の添加剤を含有してもよい。 The film of the present invention may contain additives such as an anti-blocking agent, an ultraviolet absorber, an antistatic agent, an antioxidant, and a fluorescent brightening agent as necessary.
本発明のフィルムは、その上に存在する各種機能層との接着性を向上させるために少なくとも一方の表面に塗布層を設ける。易接着性塗布層は、通常、ポリマーおよび架橋剤を主成分として構成される。ポリマーは、例えば、水性ポリウレタン、水性ポリエステルおよび水性アクリル樹脂の少なくとも1つからなり、好ましくは、ガラス転移温度(Tg)が0℃以上、さらには40℃以上のものであり、さらに好ましくはポリウレタンの中でもポリエステルポリウレタンであり、カルボン酸残基を持ち、その少なくとも一部はアミンまたはアンモニアを用いて水性化されているものである。また架橋剤は、メラミン系、エポキシ系、オキサゾリン系樹脂が一般に用いられるが、塗布性、耐久接着性の点で、メラミン系樹脂が好ましい。 The film of the present invention is provided with a coating layer on at least one surface in order to improve adhesion with various functional layers present thereon. The easy-adhesion coating layer is usually composed mainly of a polymer and a crosslinking agent. The polymer comprises, for example, at least one of water-based polyurethane, water-based polyester, and water-based acrylic resin, and preferably has a glass transition temperature (Tg) of 0 ° C. or higher, more preferably 40 ° C. or higher, more preferably polyurethane. Among them, a polyester polyurethane has a carboxylic acid residue, and at least a part thereof is made water-based using an amine or ammonia. As the cross-linking agent, melamine-based, epoxy-based, and oxazoline-based resins are generally used, but melamine-based resins are preferable in terms of coating properties and durable adhesiveness.
塗布剤の塗布方法としては、例えば、原崎勇次著、槙書店、1979年発行、「コーティング方式」に示されるような、リバースロールコーター、グラビアコーター、ロッドコーター、エアドクターコーターまたはこれら以外の塗布装置を使用することができる。塗布層は、ポリエステルフィルムの片面だけに形成してもよいし、両面に形成してもよい。片面にのみ形成した場合、その反対面には必要に応じて上記の塗布層と異なる塗布層を形成して他の特性を付与することもできる。なお、塗布剤のフィルムへの塗布性や接着性を改良するため、塗布前にフィルムに化学処理や放電処理を施してもよい。また、表面特性をさらに改良するため、塗布層形成後に放電処理を施してもよい。 As a coating method of the coating agent, for example, a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or a coating apparatus other than these as shown in Yuji Harasaki, Tsuji Shoten, published in 1979, “Coating Method” Can be used. The coating layer may be formed only on one side of the polyester film or on both sides. When formed only on one side, other characteristics can be imparted by forming a coating layer different from the above-mentioned coating layer on the opposite surface as necessary. In addition, in order to improve the applicability | paintability and adhesiveness to the film of a coating agent, you may give a chemical process and an electrical discharge process to a film before application | coating. Further, in order to further improve the surface characteristics, a discharge treatment may be performed after the coating layer is formed.
塗布層の厚みは、最終的な乾燥厚さとして、通常0.02〜0.5μm、好ましくは0.03〜0.3μmの範囲である。塗布層の厚さが0.02μm未満の場合は、接着性が劣る傾向がある。一方、塗布層の厚さが0.5μmを超える場合は、フィルムが相互に固着しやすくなる。 The thickness of the coating layer is usually in the range of 0.02 to 0.5 μm, preferably 0.03 to 0.3 μm, as the final dry thickness. When the thickness of the coating layer is less than 0.02 μm, the adhesion tends to be inferior. On the other hand, when the thickness of the coating layer exceeds 0.5 μm, the films are easily fixed to each other.
さらに易滑性、離型性、帯電防止性を付与する目的のコーティング処理をフィルムの他面に行うこともできる。 Furthermore, the other surface of the film can be subjected to a coating treatment for the purpose of imparting easy slipping, releasability and antistatic properties.
本発明のフィルムの厚みは、通常20〜300μmの範囲である。フィルム厚みが20μm未満では、加工作業性が悪いことがある。一方、フィルム厚みが300μmを超えると、重量増加や取り扱い性の悪化が起こる場合がある。 The thickness of the film of the present invention is usually in the range of 20 to 300 μm. If the film thickness is less than 20 μm, the workability may be poor. On the other hand, when the film thickness exceeds 300 μm, the weight may increase or the handleability may deteriorate.
次に本発明のフィルムの製造方法を具体的に説明するが、本発明の構成要件を満足する限り、以下の例示に特に限定されるものではない。 Next, although the manufacturing method of the film of this invention is demonstrated concretely, as long as the structural requirements of this invention are satisfied, it is not specifically limited to the following illustrations.
本発明のフィルムを製造するときには、ポリエステルを少なくとも2台の押出機に供給し、各ポリエステルの融点以上の温度に加熱してそれぞれ溶融させる。次いで、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取りポンプとフィルターを介してTダイから溶融シートとして押出す。続いて、溶融シートを回転冷却ドラム上でガラス転位温度未満にまで急冷し、非晶質の未延伸フィルムを得る。このとき、未延伸フィルムの平面性を向上させるために、静電印加密着法や液体塗布密着法等によって、未延伸フィルムと回転冷却ドラムとの密着性を向上させてもよい。そして、ロール延伸機を用いて、未延伸フィルムをその長手方向に延伸(縦延伸)することにより一軸延伸フィルムを得る。このときの延伸温度は、原料レジンのガラス転移温度(Tg)のマイナス10℃からプラス40℃の温度範囲で延伸する。また、延伸倍率は、好ましくは2.5〜7.0倍、さらに好ましくは3.0〜6.0倍である。さらに、縦延伸を一段階のみで行ってもよいし、二段階以上に分けて行ってもよい。次いで、易接着層を設けるためコーターにより水性塗布剤を塗布する。その後、テンターに導きテンター延伸機を用いて、一軸延伸フィルムをその幅方向に延伸(横延伸)することにより二軸延伸フィルムを得る。このときの延伸温度は、原料レジンのガラス転移温度(Tg)からプラス50℃の温度範囲で延伸する。また、延伸倍率は、好ましくは2.5〜7.0倍、さらに好ましくは3.5〜6.0倍である。さらに、横延伸を一段階のみで行ってもよいし、二段以上に分けて行ってもよい。また縦と横を同時に行う同時二軸延伸を行ってもよい。そして二軸延伸フィルムを熱処理することにより積層フィルムが製造される。このときの熱処理温度は、130〜250℃である。二軸延伸フィルムを熱処理するときには、二軸延伸フィルムに対して20%以内の弛緩を行ってもよい。 When the film of the present invention is produced, the polyester is supplied to at least two extruders, heated to a temperature equal to or higher than the melting point of each polyester, and melted. Next, the molten polymer from each extruder is merged in a feed block through a gear pump and a filter, taken through a die to a casting drum, and extruded as a molten sheet from a T die through a pump and a filter. Subsequently, the molten sheet is rapidly cooled to below the glass transition temperature on a rotary cooling drum to obtain an amorphous unstretched film. At this time, in order to improve the flatness of the unstretched film, the adhesion between the unstretched film and the rotating cooling drum may be improved by an electrostatic application adhesion method, a liquid application adhesion method, or the like. And a uniaxially stretched film is obtained by extending | stretching an unstretched film in the longitudinal direction (longitudinal stretching) using a roll stretching machine. The stretching temperature at this time is stretched in a temperature range of minus 10 ° C. to plus 40 ° C. of the glass transition temperature (Tg) of the raw material resin. The draw ratio is preferably 2.5 to 7.0 times, more preferably 3.0 to 6.0 times. Furthermore, longitudinal stretching may be performed in only one stage, or may be performed in two or more stages. Next, an aqueous coating agent is applied by a coater to provide an easy adhesion layer. Then, it leads to a tenter and a biaxially stretched film is obtained by extending | stretching a uniaxially stretched film in the width direction (lateral stretching) using a tenter stretching machine. The stretching temperature at this time is stretched in a temperature range of + 50 ° C. from the glass transition temperature (Tg) of the raw material resin. The draw ratio is preferably 2.5 to 7.0 times, more preferably 3.5 to 6.0 times. Further, the transverse stretching may be performed only in one stage, or may be performed in two or more stages. Moreover, you may perform simultaneous biaxial stretching which performs vertical and horizontal simultaneously. And a laminated film is manufactured by heat-processing a biaxially stretched film. The heat processing temperature at this time is 130-250 degreeC. When the biaxially stretched film is heat-treated, the biaxially stretched film may be relaxed within 20%.
本発明によれば、環境温度変化によって変質することのない粗面を有する艶消し性に優れた易接着性の光散乱性二軸延伸ポリエステルフィルムを提供することができ、本発明の工業的価値は高い。 ADVANTAGE OF THE INVENTION According to this invention, the easily adhesive light-scattering biaxially stretched polyester film excellent in the matte property which has the rough surface which does not change with environmental temperature changes can be provided, and industrial value of this invention Is expensive.
以下、本発明を実施例によりさらに詳細に説明するが、本発明はその要旨を越えない限り、以下の実施例に限定されるものではない。なお、実施例および本発明で用いた測定法および用語の定義は次のとおりである。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded. The measurement methods and terms used in the examples and the present invention are defined as follows.
(1)添加粒子平均粒子径
電子顕微鏡を用いて粒子を観察して最大径と最小径を求め、その平均を粒子1個の粒径とした。フィルム中の少なくとも100個の粒子についてこれを行う。粒子群の平均粒子径は、これらの粒子の重量平均径とする。
(1) Added particle average particle diameter The particles were observed using an electron microscope to determine the maximum diameter and the minimum diameter, and the average was defined as the particle diameter of one particle. This is done for at least 100 particles in the film. The average particle diameter of the particle group is the weight average diameter of these particles.
(2)変形度
フィルム小片をエポキシ樹脂にて固定成形した後、フィルム切断面が分子鎖配向の主軸方向と平行になるようにミクロトームで切断し、切断面を走査型電子顕微鏡にて観察する。粒子毎に平均粒径の±10%に入る少なくとも50個の粒子について、最大径と最小径の比を算出し、その相加平均を変形度とする。
(2) Deformation After fixing the film piece with an epoxy resin, it is cut with a microtome so that the cut surface of the film is parallel to the principal axis direction of the molecular chain orientation, and the cut surface is observed with a scanning electron microscope. For at least 50 particles that fall within ± 10% of the average particle size for each particle, the ratio of the maximum diameter to the minimum diameter is calculated, and the arithmetic average is taken as the degree of deformation.
(3)ヘーズ
分球式濁度計NDH−300A(日本電色工業株式会社製)を用いてその値を測定する。
(3) The value is measured using a haze-dividing turbidimeter NDH-300A (manufactured by Nippon Denshoku Industries Co., Ltd.).
(4)光沢度
JIS Z−8741−1983の方法3(60゜光沢度)によって、粗面のフィルムの縦延伸方向に光を入射して測定する。
(4) Glossiness Measured by incident light in the longitudinal stretching direction of the rough film according to method 3 (60 ° glossiness) of JIS Z-8741-1983.
(5)表面粗さRa
小坂研究所社製表面粗さ測定機(SE−3F)を用い、JIS−B−0601−1982に準じて測定する。ただし、カットオフ値80μm、測定長2.5mmとする。
(5) Surface roughness Ra
It measures according to JIS-B-0601-1982 using the surface roughness measuring machine (SE-3F) by Kosaka Laboratory. However, the cut-off value is 80 μm and the measurement length is 2.5 mm.
(6)有機粒子の熱分解温度
有機粒子を60℃で4時間減圧乾燥後、窒素ガス雰囲気下、昇温速度20℃/分の条件で熱天秤(理学電気社、TAS100型)を用いて測定した5%減量時点の温度を測定する。
(6) Thermal decomposition temperature of organic particles After drying organic particles under reduced pressure at 60 ° C. for 4 hours, measurement was performed using a thermobalance (Rigaku Denki, TAS100 type) under a nitrogen gas atmosphere at a temperature rising rate of 20 ° C./min Measure the temperature at the 5% weight loss.
(7)光散乱性
蛍光灯下の机にMSゴシックの書体で大きさが8ポイントの1から9の数字を印刷した紙を置き、試験フィルムを通して30cmの距離から観察して、数字が判別できなくなるフィルムと紙の間の距離を測定する。 光散乱性は以下のように評価する。
○:数字が見えなくなる距離が5cm以下、光散乱性が良好
×:数字が見えなくなる距離が5cmを超える、光散乱性不良
(7) Light-scattering property Place a paper with MS Gothic font printed with numbers 1 to 9 with 8 points on a desk under fluorescent light, and observe the distance from a distance of 30 cm through the test film to distinguish the numbers. Measure the distance between the missing film and the paper. The light scattering property is evaluated as follows.
○: Distance at which numbers cannot be seen is 5 cm or less, light scattering is good ×: Distance at which numbers cannot be seen exceeds 5 cm, poor light scattering
(8)光硬化性樹脂との接着性
易接着面の表面にアクリル系光硬化樹脂(日本化薬製KAYANOVA FOP−1700)を硬化後の厚さが6μmになるように塗布し、120W/cmのエネルギーの高圧水銀灯を使用し、照射距離100mmにて約10秒間照射して、表面硬化フィルムを得る。アクリル系光硬化層形成直後、当該層に1インチ幅に碁盤目が100個になるようクロスカットを入れ、直ちに、同一箇所について3回セロテープ(登録商標)急速剥離テストを実施し、剥離面積により評価する。判定基準は以下のとおりである。
◎:碁盤目剥離個数=0
○:1≦碁盤目剥離個数≦10
△:11≦碁盤目剥離個数≦20
×:21<碁盤目剥離個数
(8) Adhesiveness with photo-curing resin An acrylic photo-curing resin (KAYANOVA FOP-1700 manufactured by Nippon Kayaku Co., Ltd.) was applied to the surface of the easy-adhesion surface so that the thickness after curing was 6 μm, and 120 W / cm. A surface-cured film is obtained by irradiating at an irradiation distance of 100 mm for about 10 seconds using a high-pressure mercury lamp having the following energy. Immediately after the acrylic photocured layer is formed, a crosscut is made on the layer so that there are 100 grids in a 1-inch width, and a cellotape (registered trademark) rapid peel test is performed three times at the same location. evaluate. The judgment criteria are as follows.
A: Number of cross-cuts = 0
○: 1 ≦ Number of cross cuts ≦ 10
Δ: 11 ≦ number of cross-cuts ≦ 20
×: 21 <Number of cross-cuts peeled
(9)環境温度変化による粗面の突起状態
ドライアイスで冷やされた容器に試験フィルムを3分間入れ、その後ただちに60℃のオーブンに3分間入れる。その後、ドライアイスで冷やされた容器にただちに戻す。この操作を10回繰り返したあと、試験フィルム表面の突起状態を電子顕微鏡で観察する。図1のように粒子を覆うレジンの膜が破れた突起や、図2のように突起を覆う樹脂の破片が無数観察される突起(以下、異常突起と記す)の数を10mm2の範囲で調べる。
○:異常突起個数が1個/mm2以下
△:異常突起個数が1〜5個/mm2
×:異常突起個数が5個/mm2を超える
(9) Protruding state of rough surface due to environmental temperature change Place the test film in a container cooled with dry ice for 3 minutes, and then immediately place it in an oven at 60 ° C. for 3 minutes. Then immediately return to a container chilled with dry ice. After repeating this operation 10 times, the protrusion state on the surface of the test film is observed with an electron microscope. Protrusions or a film of resin covering the particles is broken as shown in FIG. 1, projection pieces of the resin covering the protrusions are innumerable observed as (hereinafter referred to as abnormal protrusions) 2 in a range the number of 10 mm 2 of Investigate.
○: The number of abnormal projections is 1 / mm 2 or less Δ: The number of abnormal projections is 1 to 5 / mm 2
×: The number of abnormal protrusions exceeds 5 / mm 2
(原料の調整)
・ポリエステルa
常法の重縮合で合成された極限粘度0.65、融点253℃のポリエチレンテレフタレート
(Raw material adjustment)
・ Polyester a
Polyethylene terephthalate synthesized by conventional polycondensation and having an intrinsic viscosity of 0.65 and a melting point of 253 ° C.
・ポリエステルb
常法の重縮合で合成された極限粘度0.68、融点253℃のポリエチレンテレフタレート樹脂に平均粒径6μm、5%熱分解温度が329℃の粒子表面に水酸基を有する架橋スチレン-アクリル有機粒子を練り込み10重量%含有させたもの
・ Polyester b
Crosslinked styrene-acrylic organic particles having a hydroxyl group on the surface of a polyethylene terephthalate resin having an intrinsic viscosity of 0.68 and a melting point of 253 ° C. synthesized by a conventional polycondensation and having an average particle size of 6 μm and a thermal decomposition temperature of 329 ° C. Kneaded 10% by weight
・ポリエステルc
常法の重縮合で合成された極限粘度0.68、融点253℃のポリエチレンテレフタレート樹脂に平均粒径10μm、5%熱分解温度が331℃の粒子表面にグリシジル基を有する架橋スチレン-アクリル有機粒子を練り込み10重量%含有させたもの
・ Polyester c
Crosslinked styrene-acrylic organic particles having a glycidyl group on the surface of a polyethylene terephthalate resin synthesized by a conventional polycondensation having an intrinsic viscosity of 0.68 and a melting point of 253 ° C., an average particle size of 10 μm, and a 5% thermal decomposition temperature of 331 ° C. Kneaded with 10% by weight
ポリエステルd
常法の重縮合で合成された極限粘度0.68、融点253℃のポリエチレンテレフタレート樹脂に平均粒径4μm、5%熱分解温度が325℃の粒子表面に水酸基を有する架橋スチレン-アクリル有機粒子を練り込み10重量%含有させたもの
Polyester d
Crosslinked styrene-acrylic organic particles having a hydroxyl group on the surface of particles having an average particle size of 4 μm and a 5% thermal decomposition temperature of 325 ° C. are synthesized in a polyethylene terephthalate resin having an intrinsic viscosity of 0.68 and a melting point of 253 ° C. synthesized by a conventional polycondensation Kneaded 10% by weight
・ポリエステルe
常法の重縮合で合成された極限粘度0.68、融点253℃のポリエチレンテレフタレート樹脂に平均粒径1.7μm、粒子表面にカルボン酸基を有する5%熱分解温度が290℃の架橋アクリル有機粒子を練り込み4重量%含有させたもの
・ Polyester e
Cross-linked acrylic organic having an intrinsic viscosity of 0.68 synthesized by a conventional polycondensation, a polyethylene terephthalate resin having a melting point of 253 ° C., an average particle diameter of 1.7 μm, a 5% thermal decomposition temperature of 290 ° C. having a carboxylic acid group on the particle surface Kneaded particles containing 4% by weight
・ポリエステルf
常法の重縮合で合成された極限粘度0.68、融点253℃のポリエチレンテレフタレート樹脂に平均粒径4μm、不定形シリカ粒子を練り込み10重量%含有させたもの
・ Polyester f
A polyethylene terephthalate resin synthesized by a conventional polycondensation with an intrinsic viscosity of 0.68 and a melting point of 253 ° C., kneaded with 10% by weight of amorphous silica particles with an average particle diameter of 4 μm.
・ポリエステルg
ポリエステルdが10重量%とポリエステルaが90重量%とを練り込んだ混合物
・ Polyester g
Mixture in which 10% by weight of polyester d and 90% by weight of polyester a are kneaded
・水性塗布剤A
水性塗布剤は下記a、b、c、dの化合物を47/20/30/3の重量比で混合した混合物である。
a:テレフタル酸/イソフタル酸/5−ソジウムスルホイソフタル酸/エチレングリコール/1.4−ブタンジオール/ジエチレングリコールを各々28/20/2/35/10/5のモル比で反応させたポリエステル水分散体
b:メチルメタクリレート/エチルアクリレート/アクリロニトリル/N−メチロールメタアクリルアミドを各々45/45/5/5のモル比で重合された重合物水分散体(乳化剤:アニオン系界面活性剤)
c:メラミン系架橋剤(ヘキサメトキシメチルメラミン)
d:平均粒径0.06μmの酸化ケイ素の水分散体
・ Water-based coating agent A
The aqueous coating agent is a mixture in which the following compounds a, b, c and d are mixed at a weight ratio of 47/20/30/3.
a: Polyester aqueous dispersion obtained by reacting terephthalic acid / isophthalic acid / 5-sodiumsulfoisophthalic acid / ethylene glycol / 1.4-butanediol / diethylene glycol in a molar ratio of 28/20/2/35/10/5, respectively Body b: Polymer aqueous dispersion obtained by polymerizing methyl methacrylate / ethyl acrylate / acrylonitrile / N-methylol methacrylamide in a molar ratio of 45/45/5/5 (emulsifier: anionic surfactant)
c: Melamine-based crosslinking agent (hexamethoxymethyl melamine)
d: An aqueous dispersion of silicon oxide having an average particle size of 0.06 μm
実施例1:
表層(A層)を形成するポリエステルaが85重量%とポリエステルbが15重量%の混合物をベント付き2軸押出機(サブ)に供給し、中間層(B層)を構成するポリエステルaを別のベント付き2軸押出機(メイン)に供給して溶融温度280℃で溶融したあと、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取り2種3層の未延伸フィルムを得た。かくして得られた未延伸フィルムを縦延伸ロールに送り込み、まずフィルム温度83℃で3.7倍延伸した後、片面に水性塗布剤Aを塗布し、テンターに導き95℃で横方向に4.0倍延伸して二軸配向フィルムを得た。次いで、得られた二軸配向フィルムを熱固定ゾーンに導き、230℃で5秒間幅方向に3%弛緩させながら熱固定し、下記表1に記載した厚みのポリエステルフィルムを得た。
Example 1:
A mixture of 85% by weight of polyester a forming the surface layer (A layer) and 15% by weight of polyester b is supplied to the vented twin-screw extruder (sub), and the polyester a constituting the intermediate layer (B layer) is separated. After being melted at a melt temperature of 280 ° C., the melted polymer from each extruder is merged with a feed block through a gear pump and a filter, and taken up by a casting drum through a die. A three-layer unstretched film was obtained. The unstretched film thus obtained was fed into a longitudinal stretching roll and first stretched 3.7 times at a film temperature of 83 ° C., and then an aqueous coating agent A was applied on one side, led to a tenter, and 4.0 sideways at 95 ° C. The film was stretched twice to obtain a biaxially oriented film. Next, the obtained biaxially oriented film was introduced into a heat setting zone, and heat-set while being relaxed by 3% in the width direction at 230 ° C. for 5 seconds to obtain a polyester film having a thickness described in Table 1 below.
実施例2:
表層(A層)を形成するポリエステルaが50重量%とポリエステルcが50重量%の混合物をベント付き2軸押出機(サブ)に供給し、中間層(B層)を構成するポリエステルaを別のベント付き2軸押出機(メイン)に供給して溶融温度280℃で溶融したあと、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取り2種2層の未延伸フィルムを得た。その後は実施例1と同じく、片面に水性塗布剤Aを塗布し、テンターに導き延伸し熱固定し表1に記載した厚み構成のフィルムを得た。
Example 2:
A mixture of 50% by weight of polyester a forming the surface layer (A layer) and 50% by weight of polyester c is supplied to a vented twin screw extruder (sub), and polyester a constituting the intermediate layer (B layer) is separated. After being melted at a melt temperature of 280 ° C., the melted polymer from each extruder is merged with a feed block through a gear pump and a filter, and taken up by a casting drum through a die. A two-layer unstretched film was obtained. Thereafter, as in Example 1, aqueous coating agent A was applied on one side, led to a tenter, stretched, and heat-set to obtain a film having a thickness structure described in Table 1.
実施例3:
表層(A層)を形成するポリエステルaが50重量%とポリエステルdが50重量%の混合物をベント付き2軸押出機(サブ)に供給し、中間層(B層)を構成するポリエステルaが90重量%とポリエステルgが10重量%の混合物を別のベント付き2軸押出機(メイン)に供給して溶融温度280℃で溶融したあと、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取り2種2層の未延伸フィルムを得た。その後は実施例1と同じく、片面に水性塗布剤Aを塗布し、テンターに導き延伸し熱固定し表1に記載した厚み構成のフィルムを得た。
Example 3:
A mixture of 50% by weight of polyester a forming the surface layer (A layer) and 50% by weight of polyester d is supplied to a vented twin-screw extruder (sub), and the polyester a constituting the intermediate layer (B layer) is 90%. A mixture of 10% by weight of polyester and 10% by weight of polyester was supplied to another vented twin-screw extruder (main) and melted at a melting temperature of 280 ° C., and then the molten polymer from each extruder was passed through a gear pump and a filter. They were merged in a feed block, taken up on a casting drum through a die, and two types and two layers of unstretched films were obtained. Thereafter, as in Example 1, aqueous coating agent A was applied on one side, led to a tenter, stretched, and heat-set to obtain a film having a thickness structure described in Table 1.
比較例1:
表層(A層)を形成するポリエステルaが70重量%とポリエステルfが30重量%の混合物をベント付き2軸押出機(サブ)に供給し、中間層(B層)を構成するポリエステルaを別のベント付き2軸押出機(メイン)に供給して溶融温度280℃で溶融したあと、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取り2種2層の未延伸フィルムを得た。その後は実施例1と同じく、片面に水性塗布剤Aを塗布し、テンターに導き延伸し熱固定し下記表2に記載した厚み構成のフィルムを得た。
Comparative Example 1:
A mixture of 70% by weight of polyester a forming the surface layer (A layer) and 30% by weight of polyester f is supplied to the vented twin screw extruder (sub), and the polyester a constituting the intermediate layer (B layer) is separated. After being melted at a melt temperature of 280 ° C., the melted polymer from each extruder is merged with a feed block through a gear pump and a filter, and taken up by a casting drum through a die. A seed 2 layer unstretched film was obtained. Thereafter, as in Example 1, aqueous coating agent A was applied on one side, led to a tenter, stretched, and heat-set to obtain a film having a thickness structure described in Table 2 below.
比較例2:
中間層(B層)を構成するポリエステルaが92重量%とポリエステルdが8重量%の混合物をベント付き2軸押出機(メイン)に供給し、表層(A層)を形成するポリエステルaを別のベント付き2軸押出機(サブ)に供給して溶融温度280℃で溶融したあと、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取り2種3層の未延伸フィルムを得た。その後は実施例1と同じく、片面に水性塗布剤Aを塗布し、テンターに導き延伸し熱固定し表2に記載した厚み構成のフィルムを得た。
Comparative Example 2:
A mixture of 92% by weight of polyester a constituting the intermediate layer (B layer) and 8% by weight of polyester d is fed to the vented twin-screw extruder (main), and the polyester a forming the surface layer (A layer) is separated. After being melted at a melt temperature of 280 ° C., the melted polymer from each extruder is merged by a feed block through a gear pump and a filter, and taken up by a casting drum through a die. A three-layer unstretched film was obtained. Thereafter, as in Example 1, aqueous coating agent A was applied on one side, led to a tenter, stretched and heat-fixed to obtain a film having a thickness structure described in Table 2.
比較例3:
易接着層を設けなかったほかは実施例1と同じ条件でフィルムを得た。
Comparative Example 3:
A film was obtained under the same conditions as in Example 1 except that the easy adhesion layer was not provided.
比較例4:
表層(A層)を形成するポリエステルaが94重量%とポリエステルbが6重量%の混合物をベント付き2軸押出機(サブ)に供給し、中間層(B層)を構成するポリエステルaを別のベント付き2軸押出機(メイン)に供給して溶融温度280℃で溶融したあと、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取り2種3層の未延伸フィルムを得た。その後は実施例1と同じく、片面に水性塗布剤Aを塗布し、テンターに導き延伸し熱固定し表2に記載した厚み構成のフィルムを得た。
Comparative Example 4:
A mixture of 94% by weight of polyester a forming the surface layer (A layer) and 6% by weight of polyester b is fed to a vented twin-screw extruder (sub), and the polyester a constituting the intermediate layer (B layer) is separated. After being melted at a melt temperature of 280 ° C., the melted polymer from each extruder is merged with a feed block through a gear pump and a filter, and taken up by a casting drum through a die. A three-layer unstretched film was obtained. Thereafter, as in Example 1, aqueous coating agent A was applied on one side, led to a tenter, stretched and heat-fixed to obtain a film having a thickness structure described in Table 2.
比較例5:
表層(A層)を形成するポリエステルaが50重量%とポリエステルeが50重量%の混合物をベント付き2軸押出機(サブ)に供給し、中間層(B層)を構成するポリエステルaを別のベント付き2軸押出機(メイン)に供給して溶融温度280℃で溶融したあと、各押出機からの溶融ポリマーをギヤポンプとフィルターを介してフィードブロックで合流させ、ダイを通してキャスティングドラムに引き取り2種3層の未延伸フィルムを得た。その後は実施例1と同じく、片面に水性塗布剤Aを塗布し、テンターに導き延伸し熱固定し表2に記載した厚み構成のフィルムを得た。
Comparative Example 5:
A mixture of 50% by weight of polyester a forming the surface layer (A layer) and 50% by weight of polyester e is fed to a vented twin-screw extruder (sub), and polyester a constituting the intermediate layer (B layer) is separated. After being melted at a melt temperature of 280 ° C., the melted polymer from each extruder is merged with a feed block through a gear pump and a filter, and taken up by a casting drum through a die. A three-layer unstretched film was obtained. Thereafter, as in Example 1, aqueous coating agent A was applied on one side, led to a tenter, stretched and heat-fixed to obtain a film having a thickness structure described in Table 2.
以上、得られた結果をまとめて下記表1および2に示す。 The obtained results are summarized in Tables 1 and 2 below.
実施例1〜3においては、環境温度変化による突起の異常もなく、艶消し性や光散乱性に優れた易接着性フィルムで、特に実施例2と実施例3は艶消し性に優れる。一方、比較例1は、無機粒子を用いているため異常な突起が観察された。比較例2は、表層を形成する層に粒子が添加されていないため、艶消し性が劣った。比較例3は、易接着塗布層がないため、アクリル系光硬化樹脂と接着性が劣った。比較例4は、粗面の表面粗さRaが0.08μm未満のため、艶消し性や光散乱性に劣った。比較例5は、粗面を形成する共押し出し層の厚みLと有機粒子の平均粒子径Rの比率(L/R)が4.0を超えるため、光散乱性や艶消し性が劣った。 In Examples 1 to 3, there is no abnormality of protrusions due to environmental temperature changes, and an easily adhesive film having excellent matting properties and light scattering properties. In particular, Examples 2 and 3 are excellent in matting properties. On the other hand, in Comparative Example 1, abnormal projections were observed because inorganic particles were used. In Comparative Example 2, the matte property was inferior because no particles were added to the layer forming the surface layer. Since Comparative Example 3 did not have an easy-adhesion coating layer, the adhesiveness with the acrylic photocurable resin was inferior. In Comparative Example 4, since the surface roughness Ra of the rough surface was less than 0.08 μm, the matte property and the light scattering property were inferior. In Comparative Example 5, since the ratio (L / R) of the thickness L of the coextruded layer forming the rough surface to the average particle diameter R of the organic particles exceeded 4.0, the light scattering property and the matte property were inferior.
本発明のフィルムは、例えば、艶消し性を必要とするガラスや成形体と貼り合わされる用途、ラベル用途や蒸着包装用途、また液晶ディスプレイの構成部品、例えばバックライトユニットの拡散板やプリズムシート、またプロジェクター用のスクリーンのレンズシートなどの基材フィルムとして好適に利用することができる。 The film of the present invention is, for example, an application to be bonded to glass or a molded product that requires matting properties, a label application or a vapor deposition packaging application, or a liquid crystal display component, such as a diffusion plate or prism sheet of a backlight unit, Moreover, it can utilize suitably as base film, such as a lens sheet of the screen for projectors.
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Cited By (4)
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WO2010001492A1 (en) * | 2008-07-02 | 2010-01-07 | 帝人デュポンフィルム株式会社 | Anti-glare laminate |
JP2014024341A (en) * | 2013-09-13 | 2014-02-06 | Mitsubishi Plastics Inc | Polyester film for in-mold transfer |
WO2018062397A1 (en) * | 2016-09-30 | 2018-04-05 | ユニチカ株式会社 | Polyester film |
WO2021131814A1 (en) * | 2019-12-24 | 2021-07-01 | ユニチカ株式会社 | Film and laminate comprising same |
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JP2005181648A (en) * | 2003-12-19 | 2005-07-07 | Mitsubishi Polyester Film Copp | Light scattering polyester film for prism sheet |
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JP2002254583A (en) * | 2001-03-02 | 2002-09-11 | Mitsubishi Polyester Film Copp | Laminated polyester film |
JP2004255581A (en) * | 2003-02-24 | 2004-09-16 | Mitsubishi Polyester Film Copp | Biaxially stretched laminated polyester film for reflection film |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2010001492A1 (en) * | 2008-07-02 | 2010-01-07 | 帝人デュポンフィルム株式会社 | Anti-glare laminate |
JP2014024341A (en) * | 2013-09-13 | 2014-02-06 | Mitsubishi Plastics Inc | Polyester film for in-mold transfer |
WO2018062397A1 (en) * | 2016-09-30 | 2018-04-05 | ユニチカ株式会社 | Polyester film |
KR20190063462A (en) * | 2016-09-30 | 2019-06-07 | 유니띠까 가부시키가이샤 | Polyester film |
JPWO2018062397A1 (en) * | 2016-09-30 | 2019-07-11 | ユニチカ株式会社 | Polyester film |
JP7129084B2 (en) | 2016-09-30 | 2022-09-01 | ユニチカ株式会社 | Adhesive layer laminated polyester film |
KR102491329B1 (en) | 2016-09-30 | 2023-01-26 | 유니띠까 가부시키가이샤 | polyester film |
WO2021131814A1 (en) * | 2019-12-24 | 2021-07-01 | ユニチカ株式会社 | Film and laminate comprising same |
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