JP2009178904A - Laminate comprising decorative printed film - Google Patents
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本発明は、加飾印刷フィルム積層体に関し、より詳しくは、ディスプレイ基板、タッチパネル、透明電極付きフィルム、レンズシート、光導波路、太陽電池基板、光ディスク、各種透明基板等の加飾フィルムとして有用な加飾印刷フィルム積層体に関する。 The present invention relates to a decorative printed film laminate, and more specifically, a decorative film useful as a decorative film for a display substrate, a touch panel, a film with a transparent electrode, a lens sheet, an optical waveguide, a solar cell substrate, an optical disk, various transparent substrates, and the like. The present invention relates to a decorative print film laminate.
加飾フィルムは、被覆体に意匠性や装飾性を付与するためのフィルムである。このような加飾フィルムにより意匠性や装飾性を付与する方法は、例えば塗装のような方法と比べて工程を少なくすることができ、生産性が高い方法である。そして、このような加飾フィルムは、例えば、ディスプレイ基板、タッチパネル、透明電極付きフィルム、レンズシート、光導波路、太陽電池基板、光ディスク、各種透明基板といった被覆体に意匠性や装飾性を付与するために用いられており、例えば、特開２００３−２５８９６８号公報（特許文献１）には、メタクリル樹脂中にゴム粒子が分散したアクリル系樹脂からなり、５０μｍ以上５００μｍ以下の厚みを有する加飾フィルムが開示されている。 The decorative film is a film for imparting design properties and decorative properties to the covering. The method of imparting designability and decorativeness with such a decorative film can reduce the number of steps as compared with a method such as painting, and is a method with high productivity. And such a decorative film, for example, in order to impart design properties and decorative properties to coverings such as display substrates, touch panels, films with transparent electrodes, lens sheets, optical waveguides, solar cell substrates, optical disks, and various transparent substrates For example, Japanese Patent Application Laid-Open No. 2003-258968 (Patent Document 1) discloses a decorative film made of an acrylic resin in which rubber particles are dispersed in a methacrylic resin and having a thickness of 50 μm or more and 500 μm or less. It is disclosed.
しかしながら、近年、加飾フィルムには、高水準の表面硬度、耐候性、耐薬品性、耐久性及び耐熱性を有することが要求されており、特許文献１に記載のような加飾フィルムはこれらの諸特性の点で未だ十分なものではなかった。 However, in recent years, decorative films have been required to have a high level of surface hardness, weather resistance, chemical resistance, durability, and heat resistance. In terms of various characteristics, it was not yet sufficient.
さらに、加飾フィルムには、被覆体の表面に意匠性や装飾性を付与するだけでなく、導電性やガスバリア性等の各種機能を付与することが求められている。そして、このような機能性を有する加飾フィルムに、ウェットまたはドライ成膜法により透明導電膜（ＩＴＯ膜）やガスバリア膜といった表面修飾膜を成膜した場合には、表面修飾膜の密着性不良や成膜時のインクの変色等による加飾性不良が発生するという問題があった。 Furthermore, the decorative film is required to have various functions such as conductivity and gas barrier properties as well as design and decoration on the surface of the covering. If a surface modification film such as a transparent conductive film (ITO film) or a gas barrier film is formed on the decorative film having such functionality by a wet or dry film formation method, the adhesion of the surface modification film is poor. In addition, there has been a problem in that poor decorating occurs due to discoloration of ink during film formation.
また、機能性を有する加飾フィルムを製造する方法として、表面修飾膜フィルムを作製し、そのフィルムと加飾フィルムとを接着剤等により貼り合わせる方法も検討されているが、このような方法では、接着剤層が必要となるだけでなく、生産性の観点から各フィルムにある程度の厚みが必要になることから、フィルムが厚くなってしまうという問題があった。
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、十分な表面硬度、耐候性、耐薬品性、耐久性及び耐熱性を有し、しかもフィルム表面に表面修飾膜を容易に成膜することが可能な加飾印刷フィルム積層体を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and has sufficient surface hardness, weather resistance, chemical resistance, durability, and heat resistance, and a surface modification film can be easily formed on the film surface. It aims at providing the decorative printed film laminated body which can form into a film.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、加飾印刷が施されたプラスチックフィルムの表面に、光硬化性を有する籠型シルセスキオキサン樹脂を含有する光硬化性樹脂組成物を塗布し硬化させて透明樹脂層を形成することにより、十分な表面硬度、耐候性、耐薬品性、耐久性及び耐熱性を有し、しかもフィルム表面に表面修飾膜を容易に成膜することが可能な加飾印刷フィルム積層体が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the inventors of the present invention have a photo-curing property containing a cage-type silsesquioxane resin having photo-curing property on the surface of a plastic film subjected to decorative printing. By applying and curing the resin composition to form a transparent resin layer, it has sufficient surface hardness, weather resistance, chemical resistance, durability and heat resistance, and a surface modification film can be easily formed on the film surface. The present inventors have found that a decorative printed film laminate that can be filmed is obtained, and have completed the present invention.
すなわち、本発明の加飾印刷フィルム積層体は、ガラス転移温度が７０℃以上であるプラスチックフィルムの少なくとも片面に加飾印刷が施された加飾印刷フィルム層と、前記加飾印刷フィルム層の少なくとも片面に積層された、波長５５０ｎｍでの光透過率が９０％以上であり、且つガラス転移温度が２５０℃以上である透明樹脂層とを備える加飾印刷フィルム積層体であって、
前記透明樹脂層の厚みが２０μｍ以上であり、且つ、前記透明樹脂層が光硬化性を有する籠型シルセスキオキサン樹脂を含有する光硬化性樹脂組成物を硬化させてなる層であることを特徴とするものである。
That is, the decorative printed film laminate of the present invention has a decorative printed film layer in which decorative printing is performed on at least one surface of a plastic film having a glass transition temperature of 70 ° C. or higher, and at least the decorative printed film layer. A decorative printed film laminate comprising a transparent resin layer laminated on one side and having a light transmittance at a wavelength of 550 nm of 90% or more and a glass transition temperature of 250 ° C. or more,
The thickness of the transparent resin layer is 20 μm or more, and the transparent resin layer is a layer formed by curing a photocurable resin composition containing a photocurable silsesquioxane resin. It is a feature.
また、本発明の加飾印刷フィルム積層体においては、前記透明樹脂層が前記加飾印刷フィルム層の両面に積層されていることが好ましい。 Moreover, in the decorative print film laminated body of this invention, it is preferable that the said transparent resin layer is laminated | stacked on both surfaces of the said decorative print film layer.
さらに、本発明の加飾印刷フィルム積層体においては、前記籠型シルセスキオキサン樹脂が、下記一般式（１）：
ＲＳｉＸ３ ・・・（１）
（式（１）中、Ｒは（メタ）アクリロイル基、グリシジル基及びビニル基のうちのいずれか一つの基を有する有機官能基を示し、Ｘは加水分解性基を示す。）
で表されるケイ素化合物を有機極性溶媒及び塩基性触媒存在下で加水分解反応させると共に一部縮合させ、得られた加水分解生成物を更に非極性溶媒及び塩基性触媒存在下で再縮合させてなるものであることが好ましい。
Furthermore, in the decorative printed film laminate of the present invention, the bowl-shaped silsesquioxane resin has the following general formula (1):
RSix 3 (1)
(In the formula (1), R represents an organic functional group having any one of (meth) acryloyl group, glycidyl group and vinyl group, and X represents a hydrolyzable group.)
The silicon compound represented by the formula is hydrolyzed in the presence of an organic polar solvent and a basic catalyst and partially condensed, and the resulting hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. It is preferable that
また、本発明の加飾印刷フィルム積層体においては、前記籠型シルセスキオキサン樹脂が、下記一般式（２）：
［ＲＳｉＯ３／２］ｎ ・・・（２）
（式（２）中、Ｒは（メタ）アクリロイル基、グリシジル基及びビニル基のうちのいずれか一つの基を有する有機官能基を示し、ｎは８、１０、１２又は１４を示す。）
で表される籠型シルセスキオキサン樹脂であることが好ましい。
Moreover, in the decorative printing film laminated body of this invention, the said cage silsesquioxane resin is the following general formula (2):
[RSiO 3/2 ] n (2)
(In the formula (2), R represents an organic functional group having any one of (meth) acryloyl group, glycidyl group and vinyl group, and n represents 8, 10, 12 or 14).
It is preferable that it is a cage-type silsesquioxane resin represented by these.
さらに、本発明の加飾印刷フィルム積層体においては、前記Ｒが、下記一般式（３）、（４）又は（５）： Furthermore, in the decorative print film laminate of the present invention, the R is represented by the following general formula (3), (4) or (5):
（式（３）中、Ｒ１は水素原子又はメチル基を示し、式（３）及び（４）中、ｍは１〜３の整数を示す。）
で表される有機官能基であることが好ましい。
(In Formula (3), R 1 represents a hydrogen atom or a methyl group, and in Formulas (3) and (4), m represents an integer of 1 to 3.)
It is preferable that it is an organic functional group represented by these.
さらに、本発明の加飾印刷フィルム積層体は、前記透明樹脂層の表面に積層された表面修飾膜層を更に備えていてもよい。 Furthermore, the decorative printed film laminate of the present invention may further include a surface modification film layer laminated on the surface of the transparent resin layer.
なお、一般に、シートとは薄くその厚さが長さと幅と比べて小さい平らなものをいい、フィルムとは長さ及び幅に比べて厚さが極めて小さく最大厚さが任意に限定されている薄い平らなものであって、通例、ロールの形で供給されるものをいう。従って、シートの中でも厚さの特に薄いものがフィルムであるといえるが、シートとフィルムの境界は定かではなく明確に区別しにくい。そこで、本明細書においては、シートとフィルムの両方を含めて「フィルム」と定義する。 In general, a sheet is a thin sheet whose thickness is small compared to its length and width, and a film is extremely small compared to its length and width and the maximum thickness is arbitrarily limited. Thin and flat, usually supplied in the form of a roll. Therefore, it can be said that a sheet having a particularly small thickness among the sheets is a film, but the boundary between the sheet and the film is not clear and is difficult to distinguish clearly. Therefore, in the present specification, both the sheet and the film are defined as “film”.
本発明によれば、十分な表面硬度、耐候性、耐薬品性、耐久性及び耐熱性を有し、しかもフィルム表面に表面修飾膜を容易に成膜することが可能な加飾印刷フィルム積層体を提供することが可能となる。 According to the present invention, a decorative printed film laminate having sufficient surface hardness, weather resistance, chemical resistance, durability, and heat resistance and capable of easily forming a surface modification film on the film surface. Can be provided.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
本発明の加飾印刷フィルム積層体は、ガラス転移温度が７０℃以上であるプラスチックフィルムの少なくとも片面に加飾印刷が施された加飾印刷フィルム層と、前記加飾印刷フィルム層の少なくとも片面に積層された、波長５５０ｎｍでの光透過率が９０％以上であり、且つガラス転移温度が２５０℃以上である透明樹脂層とを備える加飾印刷フィルム積層体であって、
前記透明樹脂層の厚みが２０μｍ以上であり、且つ、前記透明樹脂層が光硬化性を有する籠型シルセスキオキサン樹脂を含有する光硬化性樹脂組成物を硬化させてなる層であることを特徴とするものである。
The decorative printed film laminate of the present invention has a decorative printed film layer on which at least one surface of a plastic film having a glass transition temperature of 70 ° C. or higher is subjected to decorative printing, and at least one surface of the decorative printed film layer. A laminated printed film laminate comprising a laminated transparent resin layer having a light transmittance at a wavelength of 550 nm of 90% or more and a glass transition temperature of 250 ° C. or more,
The thickness of the transparent resin layer is 20 μm or more, and the transparent resin layer is a layer formed by curing a photocurable resin composition containing a photocurable silsesquioxane resin. It is a feature.
本発明にかかる加飾印刷フィルム層は、ガラス転移温度が７０℃以上であるプラスチックフィルムの少なくとも片面に加飾印刷が施された層である。このようにプラスチックフィルムガラス転移温度は７０℃以上（好ましくは、７０〜２２０℃の範囲）であることが必要である。ガラス転移温度が７０℃未満では車載用等の高温となる使用環境下において熱によるうねりやそりが発生するおそれがある。また、このようにプラスチックフィルムに加飾印刷を施す際に用いるインクとしては、顔料系及び染料系のいずれのインクでもよく、特に限定されないが、プラスチックフィルム表面での精密印刷が可能な馴染みの良いインクを用いることが好ましい。さらに、このようにプラスチックフィルムに加飾印刷を施す際の印刷方法についても特に限定されず、適宜公知の装置による印刷方法を採用することできるが、例えば、凸版印刷法、凹版印刷法、平版印刷法、孔版印刷法を採用することができる。 The decorative printed film layer according to the present invention is a layer in which decorative printing is performed on at least one surface of a plastic film having a glass transition temperature of 70 ° C. or higher. Thus, the plastic film glass transition temperature needs to be 70 ° C. or higher (preferably in the range of 70 to 220 ° C.). If the glass transition temperature is less than 70 ° C., there is a risk that undulation or warpage due to heat occurs in a use environment where the temperature is high, such as in-vehicle use. In addition, the ink used for decorative printing on the plastic film as described above may be either pigment-based or dye-based ink, and is not particularly limited. However, the ink is familiar so that precise printing on the surface of the plastic film is possible. It is preferable to use ink. Further, the printing method for performing decorative printing on the plastic film is not particularly limited, and a printing method using a known apparatus can be appropriately employed. For example, a relief printing method, an intaglio printing method, a lithographic printing can be used. The stencil printing method can be employed.
また、このようなプラスチックフィルムの材質としては、例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ＰＢＴ（ポリブチレンフタレート）、ＣＯＰ（シクロオレフィンポリマー）、ＣＯＣ（シクロオレフィンコポリマー）、ＰＣ（ポリカーボネート）、アセテート系樹脂、アクリル系樹脂、フッ化ビニル系樹脂、ポリアミド、ポリアリレート、セロファン、ポリエーテルスルホン、ノルボルネン系樹脂等のプラスチックが挙げられる。これらのプラスチックの中でも、特に耐熱性と透明性に優れ、諸特性のバランスのとれているという観点から、ＰＥＴ、ＰＥＮ、ＣＯＰ、ＣＯＣが好ましい。これらのプラスチックは、１種を単独で又は２種以上を組み合わせて使用することができる。さらに、このようなプラスチックフィルムとしては、後述する透明樹脂層との密着性に優れたフィルムを使用することが望ましいが、後述する透明樹脂層との密着性をより向上させるために、例えばフィルムの表面にコロナ放電処理、紫外線照射処理、プラズマ処理等の表面活性処理を施したものを用いることが好ましい。 Examples of the material of such a plastic film include PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene phthalate), COP (cycloolefin polymer), COC (cycloolefin copolymer), and PC ( Polycarbonate), acetate resin, acrylic resin, vinyl fluoride resin, polyamide, polyarylate, cellophane, polyethersulfone, norbornene resin and the like. Among these plastics, PET, PEN, COP, and COC are particularly preferable from the viewpoint of excellent heat resistance and transparency and a good balance of various properties. These plastics can be used singly or in combination of two or more. Furthermore, as such a plastic film, it is desirable to use a film excellent in adhesiveness with a transparent resin layer described later, but in order to further improve the adhesiveness with a transparent resin layer described later, for example, It is preferable to use a surface subjected to surface activation treatment such as corona discharge treatment, ultraviolet irradiation treatment, plasma treatment or the like.
このような加飾印刷フィルム層の厚みは、０．０５ｍｍ以上であることが好ましく、０．０５〜０．５ｍｍの範囲であることがより好ましい。厚みが０．０５ｍｍに満たない場合には、透明樹脂層の硬化時の収縮による変形が発生しやすくなると共に塗工時の張力による変形が発生しやすくなる傾向にある。他方、厚みが前記上限を超えると、フィルムの厚さにより、透明樹脂層の連続塗工が困難となり、生産性が悪化しやすくなる傾向にある。 The thickness of such a decorative printed film layer is preferably 0.05 mm or more, and more preferably in the range of 0.05 to 0.5 mm. When the thickness is less than 0.05 mm, deformation due to shrinkage at the time of curing of the transparent resin layer tends to occur and deformation due to tension at the time of coating tends to occur. On the other hand, when the thickness exceeds the above upper limit, continuous coating of the transparent resin layer becomes difficult due to the thickness of the film, and the productivity tends to deteriorate.
本発明にかかる透明樹脂層は、前記加飾印刷フィルム層の少なくとも片面に積層される層である。そして、このような透明樹脂層においては、波長５５０ｎｍでの光透過率が９０％以上であり、且つガラス転移温度（耐熱温度）が２５０℃以上であることが必要である。波長５５０ｎｍでの光透過率が９０％未満では、得られる加飾印刷フィルム積層体において、加飾印刷の視認性が不十分となり、またタッチパネル等の電子機器に透明フィルムとして用いる場合において光透過性が不十分となり、画像の視認性等に問題が生じる。また、ガラス転移温度が２５０℃未満では、得られる加飾印刷フィルム積層体をタッチパネル等の電子機器に用いる場合において耐熱性が不十分となる。なお、このような透明樹脂層のガラス転移温度は高いほど好ましく、透明樹脂層の他の品質である透明性、高表面硬度性、耐候性、耐薬品性及び耐久性を阻害しない範囲（例えば、ガラス転移温度が３００〜４００℃の範囲）であればよい。 The transparent resin layer concerning this invention is a layer laminated | stacked on the at least single side | surface of the said decorative printing film layer. In such a transparent resin layer, it is necessary that the light transmittance at a wavelength of 550 nm is 90% or more and the glass transition temperature (heat resistant temperature) is 250 ° C. or more. If the light transmittance at a wavelength of 550 nm is less than 90%, the resulting decorative printed film laminate has insufficient decorative print visibility, and light transparency when used as a transparent film in electronic devices such as touch panels. Becomes insufficient, causing a problem in image visibility. Moreover, when glass transition temperature is less than 250 degreeC, when using the obtained decorative printed film laminated body for electronic devices, such as a touchscreen, heat resistance becomes inadequate. In addition, the glass transition temperature of such a transparent resin layer is so preferable that it is high, and the range which does not inhibit the transparency which is other quality of a transparent resin layer, high surface hardness, a weather resistance, chemical resistance, and durability (for example, The glass transition temperature may be in the range of 300 to 400 ° C.
このような透明樹脂層は、光硬化性を有する籠型シルセスキオキサン樹脂を含有する光硬化性樹脂組成物を硬化させてなる層である。このような光硬化性樹脂組成物における前記籠型シルセスキオキサン樹脂の含有量は、光硬化性樹脂組成物の質量に対して、３質量％以上となる量であることが好ましく、５〜３０質量％の範囲内となる量であることがより好ましい。前記含有量が３質量％未満では、得られる加飾印刷フィルム積層体において、透明樹脂層のガラス転移温度が低くなる傾向にあるため表面成膜時の加熱プロセスでの耐熱性が不十分となりやすく、特にタッチパネル等の電子機器に透明フィルムとして用いる場合において耐熱性が不十分となりやすい傾向にある。他方、前記含有量が前記上限を超えると、透明樹脂層の靭性が損なわれ、ハンドリングにより表面にクラック発生等の外観不良が発生しやすい傾向にある。このように籠型シルセスキオキサン樹脂の含有量を調節することにより、透明樹脂層のガラス転移温度を調節することができ、例えば、前記籠型シルセスキオキサン樹脂の含有量が同じ場合でも、前記籠型シルセスキオキサン樹脂と併用する他の樹脂等のガラス転移温度により変動するため、前記籠型シルセスキオキサン樹脂の含有量を適宜調節することにより、透明樹脂層のガラス転移温度を調節することができる。 Such a transparent resin layer is a layer formed by curing a photocurable resin composition containing a photocurable siliceous silsesquioxane resin. The content of the cage silsesquioxane resin in such a photocurable resin composition is preferably an amount of 3% by mass or more based on the mass of the photocurable resin composition, The amount is more preferably in the range of 30% by mass. When the content is less than 3% by mass, the resulting decorative printed film laminate tends to have a low glass transition temperature of the transparent resin layer, so that the heat resistance in the heating process during surface film formation tends to be insufficient. In particular, heat resistance tends to be insufficient when used as a transparent film in electronic devices such as touch panels. On the other hand, when the content exceeds the upper limit, the toughness of the transparent resin layer is impaired, and there is a tendency that appearance defects such as cracks are easily generated on the surface by handling. Thus, by adjusting the content of the cage silsesquioxane resin, the glass transition temperature of the transparent resin layer can be adjusted, for example, even when the content of the cage silsesquioxane resin is the same. The glass transition temperature of the transparent resin layer is appropriately adjusted by adjusting the content of the cage silsesquioxane resin, because it varies depending on the glass transition temperature of other resins used in combination with the cage silsesquioxane resin. Can be adjusted.
本発明にかかる籠型シルセスキオキサン樹脂は、光硬化性を有する籠型のシルセスキオキサン樹脂である。このような籠型シルセスキオキサン樹脂としては、例えば、下記一般式（１）：
ＲＳｉＸ３ ・・・（１）
で表されるケイ素化合物を有機極性溶媒及び塩基性触媒存在下で加水分解反応させると共に一部縮合させ、得られた加水分解生成物を更に非極性溶媒及び塩基性触媒存在下で再縮合させてなるものが挙げられる。なお、前記一般式（１）において、Ｒは（メタ）アクリロイル基、グリシジル基及びビニル基のうちのいずれか一つの基を有する有機官能基を示し、Ｘはアルコキシ基、アセトキシ基等の加水分解性基を示す。
The vertical silsesquioxane resin according to the present invention is a vertical silsesquioxane resin having photocurability. Examples of such cage silsesquioxane resins include the following general formula (1):
RSix 3 (1)
The silicon compound represented by the formula is hydrolyzed in the presence of an organic polar solvent and a basic catalyst and partially condensed, and the resulting hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. The thing which becomes. In the general formula (1), R represents an organic functional group having any one of a (meth) acryloyl group, a glycidyl group, and a vinyl group, and X represents a hydrolysis of an alkoxy group, an acetoxy group, or the like. Represents a sex group.
また、本発明においては、このような籠型シルセスキオキサン樹脂が、下記一般式（２）：
［ＲＳｉＯ３／２］ｎ ・・・（２）
で表される籠型シルセスキオキサン樹脂であることが好ましい。なお、前記一般式（２）において、Ｒは（メタ）アクリロイル基、グリシジル基及びビニル基のうちのいずれか一つの基を有する有機官能基を示し、ｎは８、１０、１２又は１４を示す。
In the present invention, such a cage silsesquioxane resin is represented by the following general formula (2):
[RSiO 3/2 ] n (2)
It is preferable that it is a cage-type silsesquioxane resin represented by these. In the general formula (2), R represents an organic functional group having any one of a (meth) acryloyl group, a glycidyl group and a vinyl group, and n represents 8, 10, 12 or 14. .
さらに、本発明においては、前記Ｒが、下記一般式（３）、（４）又は（５）： Furthermore, in the present invention, the R is represented by the following general formula (3), (4) or (5):
で表される有機官能基であることが好ましい。なお、前記一般式（３）において、Ｒ１は水素原子又はメチル基を示す。また、前記一般式（３）及び（４）において、ｍは１〜３の整数を示す。 It is preferable that it is an organic functional group represented by these. In the general formula (3), R 1 represents a hydrogen atom or a methyl group. Moreover, in the said General formula (3) and (4), m shows the integer of 1-3.
このような籠型シルセスキオキサン樹脂は、樹脂中のケイ素原子全てに（メタ）アクリロイル基、グリシジル基又はビニル基を有する有機官能基からなる反応性官能基を有し、且つ、分子量分布及び分子構造の制御された籠型シルセスキオキサン樹脂であることが好ましいが、一部の有機官能基がアルキル基、フェニル基等に置き換わっているものであってもよい。また、このような籠型シルセスキオキサン樹脂の分子構造は、完全に閉じた多面体構造でなくてもよく、例えば、一部が開裂したような構造であってもよい。また、このような籠型シルセスキオキサン樹脂の平均分子量も特に限定されず、このような籠型シルセスキオキサン樹脂がオリゴマーであってもよい。 Such a cage silsesquioxane resin has a reactive functional group composed of an organic functional group having a (meth) acryloyl group, a glycidyl group or a vinyl group on all silicon atoms in the resin, and has a molecular weight distribution and A cage silsesquioxane resin having a controlled molecular structure is preferred, but some organic functional groups may be replaced with alkyl groups, phenyl groups, or the like. Further, the molecular structure of such a cage silsesquioxane resin may not be a completely closed polyhedral structure, for example, a structure in which a part thereof is cleaved. Moreover, the average molecular weight of such cage-type silsesquioxane resin is not particularly limited, and such cage-type silsesquioxane resin may be an oligomer.
本発明にかかる光硬化性樹脂組成物は、前記籠型シルセスキオキサン樹脂を含有するものである。また、本発明でいう光硬化性樹脂組成物とは、活性エネルギー線を照射して硬化可能な樹脂組成物あればよく、特に制限されない。このような光硬化性樹脂組成物には、前記籠型シルセスキオキサン樹脂以外に他の樹脂が含まれていてもよい。このように籠型シルセスキオキサン樹脂と混合して用いることができる他の樹脂としては、籠型シルセスキオキサン樹脂と相溶性及び反応性を有する樹脂であればよく、特に限定されないが、例えば、（メタ）アクリレート、エポキシ樹脂等が挙げられる。また、このような光硬化性樹脂組成物は、光硬化性を阻害しない範囲であれば、フィラー系添加物を更に含有していてもよい。 The photocurable resin composition according to the present invention contains the cage silsesquioxane resin. Moreover, the photocurable resin composition referred to in the present invention is not particularly limited as long as it is a resin composition that can be cured by irradiation with active energy rays. Such a photocurable resin composition may contain other resins in addition to the cage silsesquioxane resin. As other resins that can be used by mixing with the cage silsesquioxane resin in this way, any resin having compatibility and reactivity with the cage silsesquioxane resin may be used, and is not particularly limited. For example, (meth) acrylate, an epoxy resin, etc. are mentioned. Moreover, such a photocurable resin composition may further contain a filler-based additive as long as it does not inhibit photocurability.
また、このような光硬化性樹脂組成物は、通常、光重合開始剤を更に含有するものである。このような光重合開始剤としては、市販されているものを適宜選択して使用することができる。また、このような光重合開始剤としては、例えば、アルキンフェノン系、アシルフォスフィンオキサイド系、チタノセン系等の光重合開始剤が挙げられる。なお、このような光硬化性樹脂組成物としては、粘度調整等のために、公知の溶媒を希釈剤として含有しているものを使用してもよいが、溶媒の揮発除去工程を考慮すると時間を要し生産効率が低下するという観点、並びに硬化フィルム内部に残留溶媒等が存在し成形フィルムの特性低下につながるという観点から、溶媒の含有量が５％以下のものを使用することが好ましく、溶媒を含有していないものを使用することがより好ましい。 Moreover, such a photocurable resin composition usually further contains a photopolymerization initiator. As such a photoinitiator, what is marketed can be selected suitably, and can be used. Examples of such a photopolymerization initiator include alkynephenone-based, acylphosphine oxide-based, and titanocene-based photopolymerization initiators. In addition, as such a photocurable resin composition, what contains a well-known solvent as a diluent may be used for viscosity adjustment etc., but time is considered when the devolatilization removal process of a solvent is considered. It is preferable to use a solvent having a content of 5% or less from the viewpoint that production efficiency is reduced and that the residual solvent is present inside the cured film and leads to deterioration of the properties of the molded film, It is more preferable to use one that does not contain a solvent.
本発明にかかる透明樹脂層は、前記光硬化性樹脂組成物を硬化させてなる層である。そして、本発明においては、このような透明樹脂層の厚みが２０μｍ以上（好ましくは、２０〜４００μｍの範囲）であることが必要である。厚みが２０μｍ未満では、光硬化性樹脂組成物の特徴である高耐熱性の効果が十分に発揮されず、得られる加飾印刷フィルム積層体の耐熱性が不十分となる。他方、厚みが前記上限を超えると、透明樹脂層の硬化収縮による影響が大きくなり、形状不良となりやすい傾向にある。 The transparent resin layer concerning this invention is a layer formed by hardening | curing the said photocurable resin composition. In the present invention, the thickness of such a transparent resin layer needs to be 20 μm or more (preferably in the range of 20 to 400 μm). When the thickness is less than 20 μm, the effect of high heat resistance, which is a feature of the photocurable resin composition, is not sufficiently exhibited, and the resulting decorative printed film laminate has insufficient heat resistance. On the other hand, when the thickness exceeds the upper limit, the effect of curing shrinkage of the transparent resin layer is increased, and the shape tends to be poor.
本発明の加飾印刷フィルム積層体は、前記加飾印刷フィルム層と、前記透明樹脂層とを備えるものである。また、本発明においては、前記透明樹脂層が前記加飾印刷フィルム層の両面に積層されていることが好ましい。このように前記透明樹脂層を前記加飾印刷フィルム層の両面に積層させて、「透明樹脂層−加飾印刷フィルム層−透明樹脂層」の三層構造からなる加飾印刷フィルム積層体にすることにより、透明樹脂層を片面にのみに積層させた「樹脂層−加飾印刷フィルム層」の二層構造からなる加飾印刷フィルム積層体に比べて加飾印刷フィルム積層体の反りや変形等を更に低減させることができる。また、このように前記透明樹脂層を前記加飾印刷フィルム層の両面に積層する場合には、前記光硬化性樹脂組成物として同一の組成のものを用いてもよく、また、片面毎に異なる組成のものを用いてもよい。 The decorative printed film laminate of the present invention comprises the decorative printed film layer and the transparent resin layer. Moreover, in this invention, it is preferable that the said transparent resin layer is laminated | stacked on both surfaces of the said decorative printing film layer. Thus, the said transparent resin layer is laminated | stacked on both surfaces of the said decorative printing film layer, and it is set as the decorative printing film laminated body which consists of a three-layer structure of "transparent resin layer-decorative printing film layer-transparent resin layer". As a result, the decorative printed film laminate is warped or deformed as compared to the decorative printed film laminate having a two-layer structure of “resin layer-decorative printed film layer” in which the transparent resin layer is laminated only on one side. Can be further reduced. Moreover, when laminating | stacking the said transparent resin layer on both surfaces of the said decorative printing film layer in this way, you may use the thing of the same composition as the said photocurable resin composition, and it differs for every single side | surface. You may use the thing of a composition.
本発明の加飾印刷フィルム積層体は、十分な表面硬度、耐候性、耐薬品性、耐久性及び耐熱性を有しているだけでなく、そのフィルム表面に表面修飾膜を容易に成膜することが可能なものである。そして、本発明の加飾印刷フィルム積層体は、前記透明樹脂層の表面に積層された表面修飾膜層を更に備えるものであってもよい。このような表面修飾膜の種類としては、例えば、透明導電膜（ＩＴＯ膜）、ガスバリア膜、アンチグレア膜、反射防止膜、ＤＬＣ膜、防汚膜、ハードコート膜が挙げられる。また、このような表面修飾膜の成膜方法は特に限定されず、適宜公知の成膜方法を採用することができる。このような成膜方法としては、例えば、光硬化、熱硬化、二液混合硬化等のウェット成膜法；スパッタ法、蒸着法、ＣＶＤ法等のドライ成膜法を採用することができる。 The decorative printed film laminate of the present invention not only has sufficient surface hardness, weather resistance, chemical resistance, durability and heat resistance, but also easily forms a surface modification film on the film surface. Is possible. And the decorative print film laminated body of this invention may further be equipped with the surface modification film layer laminated | stacked on the surface of the said transparent resin layer. Examples of the surface modification film include a transparent conductive film (ITO film), a gas barrier film, an antiglare film, an antireflection film, a DLC film, an antifouling film, and a hard coat film. Moreover, the film-forming method of such a surface modification film | membrane is not specifically limited, A well-known film-forming method is employable suitably. As such a film formation method, for example, wet film formation methods such as photocuring, thermal curing, two-component mixed curing, and the like; dry film formation methods such as sputtering, vapor deposition, and CVD can be employed.
次に、以上説明した本発明の加飾印刷フィルム積層体を製造する方法について説明する。本発明の加飾印刷フィルム積層体は、例えば、プラスチックフィルムの少なくとも片面に加飾印刷を施したもの（加飾印刷フィルム層）を予め準備し、前記加飾印刷フィルム層の表面に前記光硬化性樹脂組成物を塗布した後に硬化せしめて前記透明樹脂層を形成させることにより製造することができる。 Next, a method for producing the decorative print film laminate of the present invention described above will be described. The decorative print film laminate of the present invention is prepared in advance, for example, by decorating at least one surface of a plastic film (decorative print film layer), and the photocuring is applied to the surface of the decorative print film layer. It can manufacture by making it harden | cure after apply | coating an adhesive resin composition, and forming the said transparent resin layer.
このように光硬化性樹脂組成物を塗布する方法としては、特に限定されず適宜公知の方法を採用することができる。塗布装置としては、公知の塗布装置を採用することができるが、塗布ヘッドを用いて硬化反応を起こすとゲル状の付着物が筋や異物の原因となるため、望ましくは塗布ヘッドには紫外線が当たらないようにすることが好ましい。また、塗布方式としては、グラビアコート、ロールコート、リバースコート、ナイフコート、ダイコート、リップコート、ドクターコート、エクストルージョンコート、スライドコート、ワイヤーバーコート、カーテンコート、押出コート、スピナーコート等の公知の塗布方式を採用することができる。また、厚み制御が容易であるという観点から、いったん別の支持体上に透明樹脂層を形成してから加飾印刷フィルム層上に転写により透明樹脂層を形成する方法を採用してもよい。 Thus, it does not specifically limit as a method of apply | coating a photocurable resin composition, A well-known method is employable suitably. As the coating device, a known coating device can be adopted. However, when a curing reaction is caused by using the coating head, gel-like deposits cause streaks and foreign matters. It is preferable not to hit. In addition, as a coating method, known methods such as gravure coating, roll coating, reverse coating, knife coating, die coating, lip coating, doctor coating, extrusion coating, slide coating, wire bar coating, curtain coating, extrusion coating, spinner coating, etc. A coating method can be adopted. From the viewpoint of easy thickness control, a method may be employed in which a transparent resin layer is once formed on another support and then the transparent resin layer is formed on the decorative print film layer by transfer.
また、光硬化性樹脂組成物を塗布した後に硬化せしめる方法としては、例えば、塗布後の光硬化性樹脂組成物上に紫外線を発生させて照射して光硬化させるという紫外線照射法を採用することができる。このような方法に用いる紫外線ランプにとして、例えば、メタルハライドランプ、高圧水銀ランプ、低圧水銀ランプ、パルス型キセノンランプ、キセノン／水銀混合ランプ、低圧殺菌ランプ、無電極ランプが挙げられる。これらの紫外線ランプの中でも、メタルハライドランプ又は高圧水銀ランプを用いることが好ましい。また、照射条件はそれぞれのランプ条件によって異なるが、照射露光量は２０〜１００００ｍＪ／ｃｍ２の範囲であればよく、１００〜１００００ｍＪ／ｃｍ２での範囲であることが好ましい。また、光エネルギーの有効利用の観点から、紫外線ランプには楕円型、放物線型、拡散型等の反射板を取り付けることが好ましく、さらには、冷却対策として熱カットフィルター等を取り付けてもよい。 In addition, as a method of curing after applying the photocurable resin composition, for example, an ultraviolet irradiation method in which ultraviolet rays are generated and irradiated on the photocurable resin composition after application to be photocured is adopted. Can do. Examples of the ultraviolet lamp used in such a method include a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a pulse type xenon lamp, a xenon / mercury mixed lamp, a low-pressure sterilization lamp, and an electrodeless lamp. Among these ultraviolet lamps, it is preferable to use a metal halide lamp or a high-pressure mercury lamp. The irradiation conditions vary depending on individual lamps conditions, irradiation exposure may be in the range of 20~10000mJ / cm 2, preferably in the range of at 100~10000mJ / cm 2. Further, from the viewpoint of effective use of light energy, it is preferable to attach an elliptical, parabolic, or diffusive reflector to the ultraviolet lamp, and a heat cut filter or the like may be attached as a cooling measure.
また、紫外線ランプの照射箇所には、冷却装置を取り付けることが好ましい。このような冷却装置により、紫外線ランプからの発生する熱に誘発される加飾印刷フィルム積層体の熱変形を抑制することができる。このような冷却装置の冷却方式としては、空冷方式、水冷方式等の公知の方法を採用することができる。 Moreover, it is preferable to attach a cooling device to the irradiation location of the ultraviolet lamp. With such a cooling device, it is possible to suppress the thermal deformation of the decorative printed film laminate induced by the heat generated from the ultraviolet lamp. As a cooling method of such a cooling device, a known method such as an air cooling method or a water cooling method can be employed.
なお、このように紫外線照射法により光硬化性樹脂組成物を硬化せしめる場合には、紫外線硬化反応はラジカル反応であるため酸素による反応阻害を受ける。そのため、光硬化性樹脂組成物の硬化反応における酸素による反応阻害を抑制するという観点から、光硬化性樹脂組成物を塗布した後にその表面を透明カバーフィルムで覆うことが好ましい。また、このように光硬化性樹脂組成物の表面を透明カバーフィルムで覆うことより、光硬化性樹脂組成物の表面における酸素濃度を１％以下にすることが好ましく、０．１％以下にすることがより好ましい。このように酸素濃度を小さくするためには、表面に空孔がなく、酸素透過率の小さい透明カバーフィルムを採用することが好ましい。このような透明カバーフィルムの材質としては、例えば、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ＰＢＴ（ポリブチレンフタレート）、ＰＣ（ポリカーボネート）、ポリプロピレン、ポリエチレン、アセテート系樹脂、アクリル系樹脂、フッ化ビニル系樹脂、ポリアミド、ポリアリレート、セロファン、ポリエーテルスルホン、ノルボルネン系樹脂等のプラスチックが挙げられる。これらのプラスチックは、１種を単独で又は２種以上を組み合わせて使用することができる。なお、このような透明カバーフィルムは硬化後の光硬化性樹脂組成物（透明樹脂層）との剥離が可能でなければならないため、透明カバーフィルムの表面にシリコン塗布、フッ素塗布等の易剥離処理が施されているものを用いることが好ましい。 When the photocurable resin composition is cured by the ultraviolet irradiation method as described above, the ultraviolet curing reaction is a radical reaction, and thus is hindered by oxygen. Therefore, from the viewpoint of suppressing reaction inhibition by oxygen in the curing reaction of the photocurable resin composition, it is preferable to cover the surface with a transparent cover film after applying the photocurable resin composition. Moreover, it is preferable to make oxygen concentration in the surface of a photocurable resin composition into 1% or less from covering the surface of a photocurable resin composition with a transparent cover film in this way, and to 0.1% or less. It is more preferable. In order to reduce the oxygen concentration in this way, it is preferable to employ a transparent cover film having no voids on the surface and low oxygen permeability. As a material of such a transparent cover film, for example, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PBT (polybutylene phthalate), PC (polycarbonate), polypropylene, polyethylene, acetate resin, acrylic resin, Examples thereof include plastics such as vinyl fluoride resin, polyamide, polyarylate, cellophane, polyethersulfone, and norbornene resin. These plastics can be used singly or in combination of two or more. In addition, since such a transparent cover film must be peelable from the photocurable resin composition (transparent resin layer) after curing, easy peeling treatment such as silicon coating or fluorine coating on the surface of the transparent cover film It is preferable to use those to which is applied.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
（実施例１）
トリメチロールプロパントリアクリレート（日本化薬社製、商品名「ＫＳ−ＴＭＰＡ」）８０部、下記構造式（６）で表されるシルセスキオキサンオリゴマー２０部、ヒドロキシシクロヘキシルフェニルケトン（チバ・スペシャルティ・ケミカルズ社製、商品名「ＩＲＧＡＣＵＲＥ１８４」）２．５部を均一に攪拌混合した後、脱泡して液状の光硬化性樹脂組成物を得た。また、ＰＥＴフィルム（ポリエチレンテレフタレートフィルム、幅３００ｍｍ、厚さ０．１ｍｍ、波長５５０ｎｍでの光透過率９０％以上）の表面に加飾印刷を施して加飾印刷されたＰＥＴフィルムを得た。
Example 1
80 parts of trimethylolpropane triacrylate (trade name “KS-TMPA” manufactured by Nippon Kayaku Co., Ltd.), 20 parts of silsesquioxane oligomer represented by the following structural formula (6), hydroxycyclohexyl phenyl ketone (Ciba Specialty) After 2.5 parts of Chemicals Co., Ltd., trade name “IRGACURE184”) were uniformly stirred and mixed, defoaming was performed to obtain a liquid photocurable resin composition. Also, the surface of a PET film (polyethylene terephthalate film, width 300 mm, thickness 0.1 mm, light transmittance 90% or more at a wavelength of 550 nm) was subjected to decorative printing to obtain a decorative printed PET film.
次に、得られた液状の光硬化性樹脂組成物を塗工装置へ投入し、毎分１ｍの速度で巻き出した加飾印刷されたＰＥＴフィルムの表面上へスロットダイコーター法にて、硬化後の厚みがそれぞれ０．０５ｍｍとなるように両面に塗布した。そして、透明カバーフィルム（材質：ポリエチレンテレフタレート、幅３００ｍｍ、厚さ０．１ｍｍ、波長５５０ｎｍでの光透過率９０％以上）を塗工した光硬化性樹脂へ両面から圧着した後、メタルハライドランプにて紫外線を５００ｍＪ／ｃｍ２の照射露光量で両面から照射して透明樹脂層を硬化せしめた。その後、硬化後の透明樹脂層から透明カバーフィルムを剥離除去し、「透明樹脂層（厚み：０．０５ｍｍ）−加飾印刷フィルム層（材質：ＰＥＴ、厚み：０．１ｍｍ）−透明樹脂層（厚み：０．０５ｍｍ）」の三層構造からなる加飾印刷フィルム積層体（合計厚さ：０．２ｍｍ）を得た。なお、得られた加飾印刷フィルム積層体の透明樹脂層における光硬化性樹脂組成物の硬化反応率を測定したところ、結果は８５％以上であった。 Next, the obtained liquid photocurable resin composition is put into a coating apparatus and cured by a slot die coater method on the surface of a decoratively printed PET film unwound at a speed of 1 m / min. It apply | coated to both surfaces so that subsequent thickness might be 0.05 mm, respectively. Then, after pressure-bonding from both sides to a photo-curing resin coated with a transparent cover film (material: polyethylene terephthalate, width 300 mm, thickness 0.1 mm, light transmittance 90% or more at a wavelength of 550 nm), a metal halide lamp The transparent resin layer was cured by irradiating ultraviolet rays from both sides with an irradiation exposure amount of 500 mJ / cm 2 . Thereafter, the transparent cover film is peeled off from the cured transparent resin layer, and “transparent resin layer (thickness: 0.05 mm) —decorative printing film layer (material: PET, thickness: 0.1 mm) —transparent resin layer ( A decorative print film laminate (total thickness: 0.2 mm) having a three-layer structure of “thickness: 0.05 mm)” was obtained. In addition, when the curing reaction rate of the photocurable resin composition in the transparent resin layer of the obtained decorative printed film laminate was measured, the result was 85% or more.
また、得られた加飾印刷フィルム積層体の表面にスパッタ法により、防汚膜を成膜し、防汚性を有する高機能加飾印刷フィルム積層体を得た。したがって、本発明の加飾印刷フィルム積層体の表面には防汚膜等の表面修飾膜を容易に成膜できることが確認された。 Moreover, the antifouling film | membrane was formed into a film by the sputtering method on the surface of the obtained decorative printed film laminated body, and the highly functional decorated printed film laminated body which has antifouling property was obtained. Therefore, it was confirmed that a surface modification film such as an antifouling film can be easily formed on the surface of the decorative print film laminate of the present invention.
（実施例２）
ＰＥＴフィルムに代えてＣＯＣフィルム（シクロオレフィンコポリマーフィルム、幅３００ｍｍ、厚さ０．１ｍｍ、波長５５０ｎｍでの光透過率８５％以上）を用いた以外は実施例１と同様にして、「透明樹脂層（厚み：０．０５ｍｍ）−加飾印刷フィルム層（材質：ＣＯＣ、厚み：０．１ｍｍ）−透明樹脂層（厚み：０．０５ｍｍ）」の三層構造からなる加飾印刷フィルム積層体（合計厚さ：０．２ｍｍ）を得た。なお、得られた加飾印刷フィルム積層体の透明樹脂層における光硬化性樹脂組成物の硬化反応率を測定したところ、結果は８５％以上であった。
(Example 2)
In the same manner as in Example 1 except that a COC film (cycloolefin copolymer film, width 300 mm, thickness 0.1 mm, light transmittance 85% or more at a wavelength of 550 nm) was used instead of the PET film, “transparent resin layer” (Thickness: 0.05 mm) -decorative printing film layer (material: COC, thickness: 0.1 mm) -transparent resin layer (thickness: 0.05 mm) "decorative printing film laminate (total Thickness: 0.2 mm) was obtained. In addition, when the curing reaction rate of the photocurable resin composition in the transparent resin layer of the obtained decorative printed film laminate was measured, the result was 85% or more.
また、得られた加飾印刷フィルム積層体の表面にスパッタ法により、５００Ω／□の透明導電膜（ＩＴＯ膜）を成膜し、導電性を有する高機能加飾印刷フィルム積層体を得た。したがって、本発明の加飾印刷フィルム積層体の表面には透明導電膜等の表面修飾膜を容易に成膜できることが確認された。 In addition, a transparent conductive film (ITO film) of 500Ω / □ was formed on the surface of the obtained decorative printed film laminate by sputtering to obtain a highly functional decorative printed film laminate having conductivity. Therefore, it was confirmed that a surface modification film such as a transparent conductive film can be easily formed on the surface of the decorative printed film laminate of the present invention.
（実施例３）
ＰＥＴフィルムに代えてＰＥＮフィルム（ポリエチレンナフタレートフィルム、幅３００ｍｍ、厚さ０．１ｍｍ、波長５５０ｎｍでの光透過率８５％以上）を用いた以外は実施例１と同様にして、「透明樹脂層（厚み：０．０５ｍｍ）−加飾印刷フィルム層（材質：ＰＥＮ、厚み：０．１ｍｍ）−透明樹脂層（厚み：０．０５ｍｍ）」の三層構造からなる加飾印刷フィルム積層体（合計厚さ：０．２ｍｍ）を得た。なお、得られた加飾印刷フィルム積層体の透明樹脂層における光硬化性樹脂組成物の硬化反応率を測定したところ、結果は８５％以上であった。
(Example 3)
In the same manner as in Example 1 except that a PEN film (polyethylene naphthalate film, width 300 mm, thickness 0.1 mm, light transmittance 85% or more at a wavelength of 550 nm) was used instead of the PET film, a “transparent resin layer” (Thickness: 0.05 mm) -decorative printing film layer (material: PEN, thickness: 0.1 mm) -transparent resin layer (thickness: 0.05 mm) "decorative printing film laminate (total) Thickness: 0.2 mm) was obtained. In addition, when the curing reaction rate of the photocurable resin composition in the transparent resin layer of the obtained decorative printed film laminate was measured, the result was 85% or more.
また、得られた加飾印刷フィルム積層体の表面にスパッタ法により、ガスバリア膜を成膜し、ガスバリア性を有する高機能加飾印刷フィルム積層体を得た。したがって、本発明の加飾印刷フィルム積層体の表面にはガスバリア膜等の表面修飾膜を容易に成膜できることが確認された。 Moreover, the gas barrier film was formed into a film by the sputtering method on the surface of the obtained decorative printed film laminated body, and the highly functional decorated printed film laminated body which has gas barrier property was obtained. Therefore, it was confirmed that a surface modification film such as a gas barrier film can be easily formed on the surface of the decorative print film laminate of the present invention.
（実施例４）
ＰＥＴフィルムの厚みを０．２ｍｍとし、光硬化性樹脂組成物の塗布量を硬化後の透明樹脂層の厚みが０．０２ｍｍとなるように変更した以外は実施例１と同様にして、「透明樹脂層（厚み：０．０２ｍｍ）−加飾印刷フィルム層（材質：ＰＥＴ、厚み：０．２ｍｍ）−透明樹脂層（厚み：０．０２ｍｍ）」の三層構造からなる加飾印刷フィルム積層体（合計厚さ：０．２４ｍｍ）を得た。なお、得られた加飾印刷フィルム積層体の透明樹脂層における光硬化性樹脂組成物の硬化反応率を測定したところ、結果は８５％以上であった。
Example 4
In the same manner as in Example 1, except that the thickness of the PET film was changed to 0.2 mm and the coating amount of the photocurable resin composition was changed so that the thickness of the transparent resin layer after curing was 0.02 mm, Decorative print film laminate having a three-layer structure of “resin layer (thickness: 0.02 mm) —decorative print film layer (material: PET, thickness: 0.2 mm) —transparent resin layer (thickness: 0.02 mm)” (Total thickness: 0.24 mm) was obtained. In addition, when the curing reaction rate of the photocurable resin composition in the transparent resin layer of the obtained decorative printed film laminate was measured, the result was 85% or more.
また、得られた加飾印刷フィルム積層体の表面にスパッタ法により、アンチグレア膜（ＡＧ膜）を成膜し、アンチグレア膜を備える高機能加飾印刷フィルム積層体を得た。したがって、本発明の加飾印刷フィルム積層体の表面にはアンチグレア膜等の表面修飾膜を容易に成膜できることが確認された。 Moreover, the anti-glare film (AG film) was formed into a film by the sputtering method on the surface of the obtained decorative printed film laminated body, and the highly functional decorated printed film laminated body provided with the anti-glare film was obtained. Therefore, it was confirmed that a surface modification film such as an antiglare film can be easily formed on the surface of the decorative print film laminate of the present invention.
（実施例５）
光硬化性樹脂組成物の塗布量を硬化後の透明樹脂層の厚みが０．５ｍｍとなるように変更した以外は実施例１と同様にして、「透明樹脂層（厚み：０．５ｍｍ）−加飾印刷フィルム層（材質：ＰＥＴ、厚み：０．１ｍｍ）−透明樹脂層（厚み：０．５ｍｍ）」の三層構造からなる加飾印刷フィルム積層体（合計厚さ：１．１ｍｍ）を得た。なお、得られた加飾印刷フィルム積層体の透明樹脂層における光硬化性樹脂組成物の硬化反応率を測定したところ、結果は８５％以上であった。
(Example 5)
“Transparent resin layer (thickness: 0.5 mm) −” in the same manner as in Example 1 except that the coating amount of the photocurable resin composition was changed so that the thickness of the transparent resin layer after curing was 0.5 mm. A decorative print film laminate (total thickness: 1.1 mm) having a three-layer structure of “decorative print film layer (material: PET, thickness: 0.1 mm) −transparent resin layer (thickness: 0.5 mm)”. Obtained. In addition, when the curing reaction rate of the photocurable resin composition in the transparent resin layer of the obtained decorative printed film laminate was measured, the result was 85% or more.
また、得られた加飾印刷フィルム積層体の表面にスパッタ法により、反射防止膜を成膜し、反射防止膜を備える高機能加飾印刷フィルム積層体を得た。したがって、本発明の加飾印刷フィルム積層体の表面には反射防止膜等の表面修飾膜を容易に成膜できることが確認された。 In addition, an antireflection film was formed on the surface of the obtained decorative print film laminate by a sputtering method to obtain a high-function decorative print film laminate provided with the antireflection film. Therefore, it was confirmed that a surface modification film such as an antireflection film can be easily formed on the surface of the decorative print film laminate of the present invention.
（実施例６）
前記構造式（６）で表されるシルセスキオキサンオリゴマー２０部に代えて下記構造式（７）で表されるシルセスキオキサンオリゴマー２０部を用いて光硬化性樹脂組成物を作製した以外は実施例１と同様にして、「透明樹脂層（厚み：０．０５ｍｍ）−加飾印刷フィルム層（材質：ＰＥＴ、厚み：０．１ｍｍ）−透明樹脂層（厚み：０．０５ｍｍ）」の三層構造からなる加飾印刷フィルム積層体（合計厚さ：０．２ｍｍ）を得た。なお、得られた加飾印刷フィルム積層体の透明樹脂層における光硬化性樹脂組成物の硬化反応率を測定したところ、結果は８５％以上であった。
(Example 6)
Except that 20 parts of silsesquioxane oligomer represented by the following structural formula (7) was used instead of 20 parts of silsesquioxane oligomer represented by the structural formula (6), a photocurable resin composition was prepared. In the same manner as in Example 1, “transparent resin layer (thickness: 0.05 mm) —decorative printed film layer (material: PET, thickness: 0.1 mm) —transparent resin layer (thickness: 0.05 mm)”. A decorative printed film laminate (total thickness: 0.2 mm) having a three-layer structure was obtained. In addition, when the curing reaction rate of the photocurable resin composition in the transparent resin layer of the obtained decorative printed film laminate was measured, the result was 85% or more.
また、得られた加飾印刷フィルム積層体の表面にスパッタ法により、５００Ω／□の透明導電膜（ＩＴＯ膜）を成膜し、導電性を有する高機能加飾印刷フィルム積層体を得た。したがって、本発明の加飾印刷フィルム積層体の表面には透明導電膜等の表面修飾膜を容易に成膜できることが確認された。 In addition, a transparent conductive film (ITO film) of 500Ω / □ was formed on the surface of the obtained decorative printed film laminate by sputtering to obtain a highly functional decorative printed film laminate having conductivity. Therefore, it was confirmed that a surface modification film such as a transparent conductive film can be easily formed on the surface of the decorative printed film laminate of the present invention.
＜加飾印刷フィルム積層体の諸特性の評価＞
実施例１〜６で得られた加飾印刷フィルム積層体の諸特性（表面硬度、耐候性、耐薬品性、耐久性及び耐熱性）を評価した。すなわち、加飾印刷フィルム積層体の諸特性〔表面硬度（ＪＩＳ Ｋ５６００）、耐候性（ＪＩＳ Ｋ５６５８）、耐薬品性（ＪＩＳ Ａ１４５４、薬品：トルエン、キシレン、アセトン、１０％ＮａＯＨ、１０％Ｈ２ＳＯ４、１０％ＨＣｌ、１０％Ｈ３ＰＯ４、浸漬時間：２４ｈｒ）、耐久性（ＪＩＳ Ｋ７１２８）及び耐熱性（ＪＩＳ Ｋ７２０６）〕を、それぞれ日本工業規格等に記載された方法に準拠して評価したところ、本発明の加飾印刷フィルム積層体（実施例１〜６）は、十分な表面硬度、耐候性、耐薬品性、耐久性及び耐熱性を有していることが確認された。
<Evaluation of properties of decorative print film laminate>
Various characteristics (surface hardness, weather resistance, chemical resistance, durability, and heat resistance) of the decorative printed film laminate obtained in Examples 1 to 6 were evaluated. That is, various properties of the decorative printed film laminate [surface hardness (JIS K5600), weather resistance (JIS K5658), chemical resistance (JIS A1454, chemicals: toluene, xylene, acetone, 10% NaOH, 10% H 2 SO 4 , 10% HCl, 10% H 3 PO 4 , immersion time: 24 hr), durability (JIS K7128) and heat resistance (JIS K7206)] were evaluated in accordance with methods described in Japanese Industrial Standards, etc. As a result, it was confirmed that the decorative printed film laminates (Examples 1 to 6) of the present invention have sufficient surface hardness, weather resistance, chemical resistance, durability, and heat resistance.
以上説明したように、本発明によれば、十分な表面硬度、耐候性、耐薬品性、耐久性及び耐熱性を有し、しかもフィルム表面に表面修飾膜を容易に成膜することが可能な加飾印刷フィルム積層体を提供することが可能となる。 As described above, according to the present invention, sufficient surface hardness, weather resistance, chemical resistance, durability, and heat resistance can be obtained, and a surface modification film can be easily formed on the film surface. It becomes possible to provide a decorative printed film laminate.
したがって、本発明の加飾印刷フィルム積層体は、表面硬度、耐候性、耐薬品性、耐久性及び耐熱性に優れるため、ディスプレイ基板、タッチパネル、透明電極付きフィルム、レンズシート、光導波路、太陽電池基板、光ディスク、各種透明基板等の加飾フィルムとして有用である。 Therefore, since the decorative printed film laminate of the present invention is excellent in surface hardness, weather resistance, chemical resistance, durability and heat resistance, a display substrate, a touch panel, a film with a transparent electrode, a lens sheet, an optical waveguide, and a solar cell. It is useful as a decorative film for substrates, optical disks, various transparent substrates and the like.
Claims (6)
前記透明樹脂層の厚みが２０μｍ以上であり、且つ、前記透明樹脂層が光硬化性を有する籠型シルセスキオキサン樹脂を含有する光硬化性樹脂組成物を硬化させてなる層であることを特徴とする加飾印刷フィルム積層体。 A decorative printed film layer on which at least one side of a plastic film having a glass transition temperature of 70 ° C. or more is subjected to decorative printing, and a light transmittance at a wavelength of 550 nm laminated on at least one side of the decorative printed film layer. Is a decorative printing film laminate comprising 90% or more and a transparent resin layer having a glass transition temperature of 250 ° C. or more,
The thickness of the transparent resin layer is 20 μm or more, and the transparent resin layer is a layer formed by curing a photocurable resin composition containing a photocurable silsesquioxane resin. A decorative print film laminate.
ＲＳｉＸ３ ・・・（１）
（式（１）中、Ｒは（メタ）アクリロイル基、グリシジル基及びビニル基のうちのいずれか一つの基を有する有機官能基を示し、Ｘは加水分解性基を示す。）
で表されるケイ素化合物を有機極性溶媒及び塩基性触媒存在下で加水分解反応させると共に一部縮合させ、得られた加水分解生成物を更に非極性溶媒及び塩基性触媒存在下で再縮合させてなるものであることを特徴とする請求項１又は２に記載の加飾印刷フィルム積層体。 The cage silsesquioxane resin has the following general formula (1):
RSix 3 (1)
(In the formula (1), R represents an organic functional group having any one of (meth) acryloyl group, glycidyl group and vinyl group, and X represents a hydrolyzable group.)
The silicon compound represented by the formula is hydrolyzed in the presence of an organic polar solvent and a basic catalyst and partially condensed, and the resulting hydrolysis product is further recondensed in the presence of a nonpolar solvent and a basic catalyst. The decorative printed film laminate according to claim 1 or 2, wherein
［ＲＳｉＯ３／２］ｎ ・・・（２）
（式（２）中、Ｒは（メタ）アクリロイル基、グリシジル基及びビニル基のうちのいずれか一つの基を有する有機官能基を示し、ｎは８、１０、１２又は１４を示す。）
で表される籠型シルセスキオキサン樹脂であることを特徴とする請求項１〜３のうちのいずれか一項に記載の加飾印刷フィルム積層体。 The cage silsesquioxane resin has the following general formula (2):
[RSiO 3/2 ] n (2)
(In the formula (2), R represents an organic functional group having any one of (meth) acryloyl group, glycidyl group and vinyl group, and n represents 8, 10, 12 or 14).
The decorative printed film laminate according to any one of claims 1 to 3, wherein the decorative printed film laminate is a cage-type silsesquioxane resin represented by formula (1).
で表される有機官能基であることを特徴とする請求項３又は４に記載の加飾印刷フィルム積層体。 R is the following general formula (3), (4) or (5):
The decorative print film laminate according to claim 3, wherein the decorative print film laminate is an organic functional group represented by:
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012063637A1 (en) * | 2010-11-10 | 2012-05-18 | 新日鐵化学株式会社 | Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film |
| JP2012116183A (en) * | 2010-11-10 | 2012-06-21 | Nippon Steel Chem Co Ltd | Injection-molding hard coat film laminate and its manufacturing method |
| JP2012183818A (en) * | 2011-02-17 | 2012-09-27 | Nippon Steel Chem Co Ltd | Method of manufacturing injection-molded body using hardcoat film laminate for injection molding |
| JP2013035274A (en) * | 2011-07-13 | 2013-02-21 | Kansai Paint Co Ltd | Laminate and method of manufacturing the same |
| CN103201080A (en) * | 2010-11-10 | 2013-07-10 | 新日铁住金化学株式会社 | Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film |
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| WO2022168804A1 (en) | 2021-02-05 | 2022-08-11 | 東亞合成株式会社 | Undercoat agent composition for inorganic substance layer lamination, cured product thereof, and method for producing same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004123936A (en) * | 2002-10-03 | 2004-04-22 | Nippon Steel Chem Co Ltd | Silicone resin composition and silicone resin molded form |
| JP2004143449A (en) * | 2002-09-30 | 2004-05-20 | Nippon Steel Chem Co Ltd | Cage-type silsesquioxan resin with functional group and method for producing the same |
| JP2005254541A (en) * | 2004-03-10 | 2005-09-22 | Fuji Photo Film Co Ltd | Gas-barrier laminated film, its production method, and image display element using the film |
| JP2006089685A (en) * | 2004-09-27 | 2006-04-06 | Nippon Steel Chem Co Ltd | Silicone resin composition and molding |
| JP2006095783A (en) * | 2004-09-29 | 2006-04-13 | Dainippon Printing Co Ltd | Transparent gas barrier film and substrate for display using it |
| JP2006175719A (en) * | 2004-12-22 | 2006-07-06 | Toyo Ink Mfg Co Ltd | Decorative paper and decorative material |
| JP2007001111A (en) * | 2005-06-23 | 2007-01-11 | Riken Technos Corp | High gloss decorative sheet |
-
2008
- 2008-01-30 JP JP2008019167A patent/JP5036060B2/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004143449A (en) * | 2002-09-30 | 2004-05-20 | Nippon Steel Chem Co Ltd | Cage-type silsesquioxan resin with functional group and method for producing the same |
| JP2004123936A (en) * | 2002-10-03 | 2004-04-22 | Nippon Steel Chem Co Ltd | Silicone resin composition and silicone resin molded form |
| JP2005254541A (en) * | 2004-03-10 | 2005-09-22 | Fuji Photo Film Co Ltd | Gas-barrier laminated film, its production method, and image display element using the film |
| JP2006089685A (en) * | 2004-09-27 | 2006-04-06 | Nippon Steel Chem Co Ltd | Silicone resin composition and molding |
| JP2006095783A (en) * | 2004-09-29 | 2006-04-13 | Dainippon Printing Co Ltd | Transparent gas barrier film and substrate for display using it |
| JP2006175719A (en) * | 2004-12-22 | 2006-07-06 | Toyo Ink Mfg Co Ltd | Decorative paper and decorative material |
| JP2007001111A (en) * | 2005-06-23 | 2007-01-11 | Riken Technos Corp | High gloss decorative sheet |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012063637A1 (en) * | 2010-11-10 | 2012-05-18 | 新日鐵化学株式会社 | Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film |
| JP2012116183A (en) * | 2010-11-10 | 2012-06-21 | Nippon Steel Chem Co Ltd | Injection-molding hard coat film laminate and its manufacturing method |
| CN103201080A (en) * | 2010-11-10 | 2013-07-10 | 新日铁住金化学株式会社 | Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film |
| CN103201080B (en) * | 2010-11-10 | 2016-01-20 | 新日铁住金化学株式会社 | Injection moulding hard coat film duplexer, its manufacture method and make use of the manufacture method of injection molded article of this hard coat film duplexer |
| KR101902492B1 (en) * | 2010-11-10 | 2018-09-28 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Multilayered hardcoat film for injection molding, process for producing same, and process for producing injection-molded object using the multilayered hardcoat film |
| JP2012183818A (en) * | 2011-02-17 | 2012-09-27 | Nippon Steel Chem Co Ltd | Method of manufacturing injection-molded body using hardcoat film laminate for injection molding |
| JP2013035274A (en) * | 2011-07-13 | 2013-02-21 | Kansai Paint Co Ltd | Laminate and method of manufacturing the same |
| CN110696149A (en) * | 2018-07-10 | 2020-01-17 | 琳得科株式会社 | Release film for ceramic green sheet production process |
| WO2022168804A1 (en) | 2021-02-05 | 2022-08-11 | 東亞合成株式会社 | Undercoat agent composition for inorganic substance layer lamination, cured product thereof, and method for producing same |
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