JP2013071421A - Decorative film and method of manufacturing the same - Google Patents
Decorative film and method of manufacturing the same Download PDFInfo
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Abstract
Description
本発明は加飾フィルムおよびその製造方法に関する。 The present invention relates to a decorative film and a method for producing the same.
オパールのようにサブミクロンオーダーのシリカ粒子が規則配列した粒子配列体に対して、可視光がブラッグ反射を起こすことで、角度によって様々な色を呈する現象を遊色効果と呼んでいる。 A phenomenon in which visible light causes Bragg reflection to a particle array in which submicron-order silica particles are regularly arranged, such as opal, causes various colors depending on the angle is called a play color effect.
この遊色効果は、粒子配列体中に様々な結晶構造を有するために生じる。 This play-off effect is caused by having various crystal structures in the particle array.
このような粒子配列体は、例えばシリカ粒子の固−液分散系サスペンジョンを塗膜し乾燥させることによって得られ、自然光もしくは白色光の照射下で鮮明な有彩色を発色させることが開示されている（下記、特許文献１参照）。 Such a particle array is obtained, for example, by coating and drying a solid-liquid dispersion suspension of silica particles, and is disclosed to develop a clear chromatic color under natural light or white light irradiation. (See Patent Document 1 below).
また各種支持体上に粒子配列体を作製する方法や、支持体ごと破砕した粉砕フィルムを含有する組成物の提案もされており、例えば、支持体上に粘着剤を塗布し、その上に粒子分散液を塗布、乾燥したフィルムを作製すること、さらにそれを破砕して、別の樹脂中に入れて塗膜を作製することが開示されている（下記、特許文献２参照）。 In addition, a method for producing a particle array on various supports and a composition containing a pulverized film crushed together with the support have been proposed. For example, a pressure-sensitive adhesive is applied on a support and particles are formed thereon. It has been disclosed that a film coated with a dispersion and dried is further crushed and placed in another resin to produce a coating film (see Patent Document 2 below).
また亀裂を有するオパール素材の裏面側をシートに貼着し、表面側を透光性樹脂で被覆した装飾部材が開示されている（下記、特許文献３参照）。 Further, a decorative member is disclosed in which the back side of an opal material having cracks is attached to a sheet and the front side is covered with a translucent resin (see Patent Document 3 below).
しかし特許文献１記載の粒子配列体では、特定波長のみにおける遊色効果しか得られなかった。 However, in the particle array described in Patent Document 1, only a play-color effect at a specific wavelength was obtained.
また特許文献２記載の塗膜では、乾燥させただけのものであるため、大きな外力が働くと結晶構造が崩れて、遊色効果を示さなくなる。 In addition, since the coating film described in Patent Document 2 is only dried, when a large external force is applied, the crystal structure is destroyed and no play color effect is exhibited.
また特許文献３の装飾部材では、オパール素材をスライスする際に崩れてしまい、フィルム状の薄いものを作れない場合があった。 Moreover, in the decorative member of patent document 3, when slicing an opal material, it collapse | crumbled and there existed a case where a film-like thin thing could not be made.
上述のような問題点を解決するために、本発明の加飾フィルムは、基材フィルムと、該基材フィルム上に位置する、複数のシリカ粒子が規則配列してなる粒子配列体と、該粒子配列体の内部に充填されるとともに該粒子配列体を被覆している保形材とを有する加飾フィルムであって、前記シリカ粒子の屈折率をｎＡ（Ａ＝１．３５〜１．５５）とし、前記保形材の屈折率をｎＢとしたとき、ｎＡとｎＢとの差（｜ｎＡ−ｎＢ｜）が０．０２以下であることを特徴とする。 In order to solve the problems as described above, the decorative film of the present invention includes a base film, a particle array formed by regularly arranging a plurality of silica particles located on the base film, and And a shape-retaining film filled inside the particle array and covering the particle array, wherein the silica particles have a refractive index of nA (A = 1.35 to 1.55). ), And when the refractive index of the shape-retaining material is nB, the difference (| nA−nB |) between nA and nB is 0.02 or less.
また、本発明の加飾フィルムの製造方法は、基材フィルム上に、複数のシリカ粒子を含む分散液を塗布して前記シリカ粒子を沈殿させることで該シリカ粒子が規則配列してなる粒子配列体を形成する工程と、該粒子配列体の内部に保形材を充填するとともに、前記粒子配列体の表面を前記保形材で被覆して、該保形材を乾燥させる工程とを有することを特徴とする。 In addition, the method for producing a decorative film of the present invention is a particle arrangement in which a silica particle is regularly arranged by applying a dispersion containing a plurality of silica particles on a base film and precipitating the silica particles. Forming a body, filling the shape of the particle array with a shape-retaining material, covering the surface of the particle array with the shape-retaining material, and drying the shape-retaining material. It is characterized by.
本発明の加飾フィルムによれば、粒子配列体を安定に保持するとともに、シリカ粒子と保形材との屈折率を適正に合わせて界面反射を低減し、遊色効果を視認し易くする。 According to the decorative film of the present invention, the particle array is stably held, the refractive index between the silica particles and the shape-retaining material is appropriately adjusted, interface reflection is reduced, and the play color effect is easily recognized.
また本発明の加飾フィルムの製造方法によれば、基材フィルム上の粒子配列体に保形材を浸透させて、乾燥、硬化させることにより、スライス等の加工性を向上させる。 Moreover, according to the manufacturing method of the decorating film of this invention, workability, such as a slice, is improved by making a shape retention material infiltrate into the particle | grain array body on a base film, and drying and hardening.
以下、本発明の一実施形態について説明する。 Hereinafter, an embodiment of the present invention will be described.
＜加飾フィルム＞
本実施形態は、基材フィルムと、基材フィルム上に位置する、複数のシリカ粒子が規則配列してなる粒子配列体と、粒子配列体の内部に充填されるとともに粒子配列体を被覆している保形材とを有する加飾フィルムであって、シリカ粒子の屈折率をｎＡ（Ａ＝１．３５〜１．５５）とし、保形材の屈折率をｎＢとしたとき、ｎＡとｎＢとの差（｜ｎＡ−ｎＢ｜）が０．０２以下である。
<Decorative film>
The present embodiment includes a base film, a particle array formed on a base film, in which a plurality of silica particles are regularly arranged, filled inside the particle array and covering the particle array. A shape-retaining material having a refractive index of silica particles of nA (A = 1.35 to 1.55) and a shape-retaining material of nB, nA and nB Difference (| nA−nB |) is 0.02 or less.
図１には、基材フィルム１上に粒子配列体４が形成され、粒子配列体４上およびシリカ粒子間空域４ｂに保形材３を配置した加飾フィルム１０の断面を示す。 FIG. 1 shows a cross section of a decorative film 10 in which a particle array 4 is formed on a base film 1 and a shape-retaining material 3 is arranged on the particle array 4 and in an inter-silica interparticle space 4b.
また図２には、基材フィルム１上に形成した粒子配列体４の表面を示す。 FIG. 2 shows the surface of the particle array 4 formed on the base film 1.
また図３には、基材フィルム１上に粒子配列体４に保形材３を配置した表面を示す。 FIG. 3 shows the surface on which the shape retaining material 3 is arranged on the particle array 4 on the base film 1.
保形材３が複数のシリカ粒子４ａを包含することによって、シリカ粒子４ａと保形材３との界面における反射を低減して、複数のシリカ粒子４ａによる遊色効果を視認し易くすることができる。 By including the plurality of silica particles 4 a in the shape retaining material 3, reflection at the interface between the silica particles 4 a and the shape retaining material 3 can be reduced, and the play-coloring effect by the plurality of silica particles 4 a can be easily recognized. it can.
保形材３は、粒子配列体４を包含するように形成したものであり、保形材３を設ける際に粒子配列体４の粒子間空域４ｂに樹脂を浸透させて固定する。 The shape-retaining material 3 is formed so as to include the particle array 4. When the shape-retaining material 3 is provided, the resin is infiltrated and fixed in the inter-particle space 4 b of the particle array 4.
これによって、粒子間の結合を強化して加飾フィルム１０の強度を保持できる。 Thereby, the intensity | strength of the decorating film 10 can be hold | maintained by strengthening the coupling | bonding between particle | grains.
ここで粒子配列体４には格子欠陥があってもよいが、好ましくは最密充填構造または面心立法構造の粒子配列体４とすることによって、ブラッグ反射を顕著にすることができる。 Here, the particle array 4 may have a lattice defect, but Bragg reflection can be made remarkable by using the particle array 4 having a close-packed structure or a face-centered structure.
さらに本実施形態は、保形材がセルロース系樹脂、ポリエステル系樹脂、ウレタン系樹脂、シリコン系樹脂およびエポキシ樹脂からなる群より選択される少なくとも１種からなり、基材フィルムがポリエステル系樹脂、アクリル系樹脂およびポリカーボネ―ト系樹脂からなる群より選択される少なくとも１種からなり、基材フィルムの屈折率をｎＣとしたとき、ｎＡとｎＣとの差（｜ｎＡ−ｎＣ｜）が０．０５以下である。 Further, in the present embodiment, the shape retaining material is at least one selected from the group consisting of a cellulose resin, a polyester resin, a urethane resin, a silicon resin, and an epoxy resin, and the base film is a polyester resin, an acrylic resin When the refractive index of the substrate film is nC, the difference between nA and nC (| nA−nC |) is 0.05. It is as follows.
これにより、基材フィルム１側については耐久性、保形材３については柔軟性を向上させるとともに、さらには基材フィルム１側からの視認性も確保することができる。 Thereby, while improving durability about the base film 1 side and a softness | flexibility about the shape-retaining material 3, the visibility from the base film 1 side is further securable.
保形材３の材質としては、樹脂分子鎖の長さ等を制御することで、屈折率を制御することができることが好ましい。 As the material of the shape retaining material 3, it is preferable that the refractive index can be controlled by controlling the length of the resin molecular chain and the like.
さらに本実施形態は、基材フィルムの厚さが５〜５０μｍであり、シリカ粒子の平均粒子径が０．０１〜１０μｍであり、粒子配列体の厚さが０．２〜２０μｍであり、保形材を含めた厚さが０．４〜３０μｍである。 Furthermore, in this embodiment, the thickness of the base film is 5 to 50 μm, the average particle diameter of the silica particles is 0.01 to 10 μm, the thickness of the particle array is 0.2 to 20 μm, The thickness including the profile is 0.4 to 30 μm.
これにより、加飾フィルム１０全体での耐久性、柔軟性を維持するとともに、加飾フィルム１０内での光の干渉を抑えてブラッグ回折による遊色効果を最大限に発揮させる。 Thereby, while maintaining the durability and flexibility in the entire decorative film 10, the interference of light in the decorative film 10 is suppressed, and the play effect by Bragg diffraction is exhibited to the maximum.
シリカ粒子径を選択することによって色調を変えることができ、シリカ粒子径が０．０１〜１０μmであれば、光の波長とシリカ粒子径が近いため、シリカ粒子４ａの規則配列によるブラッグ反射が効率的に起こり、所望の構造色を得ることができる。 The color tone can be changed by selecting the silica particle diameter, and if the silica particle diameter is 0.01 to 10 μm, the wavelength of light and the silica particle diameter are close, so the Bragg reflection by the regular arrangement of the silica particles 4a is efficient. Occur, and the desired structural color can be obtained.
さらにシリカ粒子４ａの平均粒子径は０．０１〜２μｍで、球状かつ単分散であることが好ましく、特にシリカ粒子径が０．０５〜０．５μｍであれば、近紫外〜可視〜近赤外域で構造色を呈するものが得られるとともに、可視域の光散乱による粒子配列体４の白濁を低減する。 Further, the average particle diameter of the silica particles 4a is preferably 0.01 to 2 μm, and preferably spherical and monodispersed. Especially when the silica particle diameter is 0.05 to 0.5 μm, the near ultraviolet to visible to near infrared region. In addition to obtaining a structural color, the cloudiness of the particle array 4 due to light scattering in the visible range is reduced.
基材フィルムの厚さは、基材フィルム１側からの視認性も確保することができる点で、５〜５０μｍが好ましい。 The thickness of the base film is preferably 5 to 50 μm in that the visibility from the base film 1 side can be secured.
粒子配列体４の厚さは０．３〜２０μｍが、遊色効果を維持するとともに、保形材３で粒子配列体４を固定して界面剥離を低減できる点で好ましい。 The thickness of the particle array 4 is preferably 0.3 to 20 μm from the viewpoint of maintaining the play-color effect and fixing the particle array 4 with the shape-retaining material 3 to reduce interfacial peeling.
保形材３の厚さは、粒子配列体４の厚さよりも厚いことを前提として、乾燥状態で０．４μｍ〜３０μｍが好ましく、粒子配列体４を十分保護できるとともに、平滑性を維持して、延伸時のクラックを低減できる。より好ましくは、保形材３の厚さが安定しやすい１μｍ〜１０μｍが好ましい。 The thickness of the shape-retaining material 3 is preferably 0.4 μm to 30 μm in a dry state on the assumption that it is thicker than the thickness of the particle array 4, and can sufficiently protect the particle array 4 and maintain smoothness. Cracks during stretching can be reduced. More preferably, the thickness of the shape retaining material 3 is preferably 1 μm to 10 μm where the thickness is easily stabilized.
また、粒子配列体４に用いるシリカ粒子４ａの粒子径の変動係数が１０％未満であれば、粒子配列体４を効率的に形成できる。 Moreover, if the variation coefficient of the particle diameter of the silica particles 4a used for the particle array 4 is less than 10%, the particle array 4 can be formed efficiently.
さらに本実施形態は、保形材が、カーボンブラック、酸化鉄赤（弁柄）、フタロシアニンブルー、コバルトグリーン、コバルトブルーおよびクロムイエロー（黄鉛）からなる群より選択される少なくとも１種の色材を含む。 Furthermore, in this embodiment, the shape retaining material is at least one color material selected from the group consisting of carbon black, iron oxide red (valve), phthalocyanine blue, cobalt green, cobalt blue, and chrome yellow (yellow lead). including.
これにより、色剤が可視光を吸収して反射色を変化させ、加飾フィルム１０の全体的な色相を調整することができる。 Thereby, a coloring agent absorbs visible light, changes a reflective color, and can adjust the whole hue of the decoration film 10. FIG.
これらの色剤の平均粒子径は０．０１〜１μｍであることが好ましい。 The average particle diameter of these colorants is preferably 0.01 to 1 μm.
ここで金属フレーク等の輝度性の高い顔料等を含むものは、裏面反射が強くなり、粒子配列体４の構造色と打ち消しあってしまうため、好ましくない。 Here, those containing pigments with high luminance such as metal flakes are not preferable because back reflection becomes strong and cancels out with the structural color of the particle array 4.
このように本発明の加飾フィルムは、例えば熱プレス法および成形同時絵付け法、インモールド法などによって樹脂成形品や金属、木材、紙製品、ガラスなどに遊色性のパターンを加飾した加飾フィルムを提供するものであり、良好な遊色効果を発揮させるとともに、かつ結晶構造の保形性を確保する。 As described above, the decorative film of the present invention decorated a playful pattern on a resin molded product, metal, wood, paper product, glass, or the like by, for example, a hot press method, a simultaneous molding method, an in-mold method, or the like. The present invention provides a decorative film, exhibits a good play-color effect, and ensures shape retention of a crystal structure.
＜製造方法＞
本実施形態は、基材フィルム上に、複数のシリカ粒子を含む分散液を塗布して前記シリカ粒子を沈殿させることで該シリカ粒子が規則配列してなる粒子配列体を形成する工程と、該粒子配列体の内部に保形材を充填するとともに、前記粒子配列体の表面を前記保形材で被覆して、該保形材を乾燥させる工程とを有する。
<Manufacturing method>
In the present embodiment, a step of applying a dispersion containing a plurality of silica particles on a base film and precipitating the silica particles to form a particle array in which the silica particles are regularly arranged; and Filling the inside of the particle array with a shape-retaining material, covering the surface of the particle array with the shape-retaining material, and drying the shape-retaining material.
これにより、後加工時の加工性が向上してフィルムを薄くすることができる。 Thereby, the workability at the time of post-processing improves and a film can be made thin.
粒子配列体４、保形材３の形成方法は、グラビア印刷、シルク印刷、オフセット印刷、リップコーター、リバースコーター、グラビアコーターなどによる塗工が可能である。 The particle array 4 and the shape retaining material 3 can be formed by gravure printing, silk printing, offset printing, lip coater, reverse coater, gravure coater or the like.
必要に応じて基材フィルム１と粒子配列体４の間に剥離層や保護層を設けることも可能である。 It is also possible to provide a release layer or a protective layer between the base film 1 and the particle array 4 as necessary.
なお、加飾フィルム１０には、転写箔のほか、化粧シート、インサートフィルムなども含まれる。例えば転写箔の場合、基材フィルム１／離型層／剥離層／図柄層／保形材３／接着層からなる場合、粒子配列体４が図柄層またはその一部となる。 In addition to the transfer foil, the decorative film 10 includes a decorative sheet, an insert film, and the like. For example, in the case of a transfer foil, in the case of a substrate film 1 / release layer / release layer / design layer / shape retaining material 3 / adhesive layer, the particle array 4 is a design layer or a part thereof.
（実施例１）
まず、粒子配列体４の厚さ、保形材３の種類、厚さ、基材フィルム１の種類、厚さ、シリカ粒子径を固定して、シリカ粒子４ａの屈折率ｎＡと保形材３の屈折率ｎＢとを変更した試料について、遊色効果と耐久性を評価した結果を表１に示す。
Example 1
First, the refractive index nA of the silica particles 4a and the shape retaining material 3 are fixed by fixing the thickness of the particle array 4, the type and thickness of the shape retaining material 3, the type and thickness of the base film 1, and the silica particle diameter. Table 1 shows the results of evaluating the play-color effect and the durability of the samples with different refractive indexes nB.
＜試料作製＞
シリカ粒子４ａ中における炭素含有量および窒素含有量を適時調節することで、屈折率ｎＡを１．３〜１．６で変化させた。
<Sample preparation>
The refractive index nA was changed from 1.3 to 1.6 by appropriately adjusting the carbon content and nitrogen content in the silica particles 4a.
保形材３中における高屈折率フィラーおよび低屈折率フィラーの含有量を適時調整することで、屈折率ｎＢを１．２６〜１．６４で変化させた。 The refractive index nB was changed from 1.26 to 1.64 by adjusting the contents of the high refractive index filler and the low refractive index filler in the shape retaining material 3 in a timely manner.
粒子配列体４の厚さ１０μｍ、保形材３の種類はエポキシ樹脂、保形材３の厚さは１５μｍ、基材フィルム１の種類はポリエステル系樹脂、基材フィルム１の厚さは２５μｍ、シリカ粒子径は１μｍに固定した。 The particle array 4 has a thickness of 10 μm, the shape retaining material 3 is an epoxy resin, the shape retaining material 3 has a thickness of 15 μm, the base film 1 has a polyester resin, and the base film 1 has a thickness of 25 μm. The silica particle diameter was fixed at 1 μm.
＜評価方法＞
遊色効果は目視観察により、特許文献３に記載のオパール素材と比較して、優れているものは○、特に優れているものは◎、同等以下であれば×とした。
<Evaluation method>
The visual color effect was evaluated by visual observation as compared with the opal material described in Patent Document 3 as “Excellent”, “Excellent” as “Excellent”, and “X” when equal or lower.
耐久性は、基材フィルム１の反対側の面を不織布で擦り、剥がれ具合を目視観察して、特許文献３に記載のオパール素材と比較して、優れているものは○、特に優れているものは◎、同等以下であれば×とした。 As for the durability, the surface opposite to the base film 1 is rubbed with a non-woven fabric, the degree of peeling is visually observed, and is superior to the opal material described in Patent Document 3, particularly excellent. Goods were marked as ◎, and x if equal or less.
＜評価結果＞
比較例である試料１〜５では、屈折率ｎＡが低いので屈折率ｎＢの値に依らず遊色効果が悪かった。
<Evaluation results>
In samples 1 to 5 as comparative examples, since the refractive index nA was low, the play-color effect was bad regardless of the value of the refractive index nB.
試料６〜１０では、比較例である試料６、１０が屈折率ｎＡと屈折率ｎＢとの差が大きいため遊色効果が悪かったが、実施例である試料７〜９では良好であった。 In Samples 6 to 10, Samples 6 and 10 as comparative examples had a large difference between the refractive index nA and the refractive index nB, and thus the play-color effect was bad. However, Samples 7 to 9 as Examples were good.
試料１１〜１５では、比較例である試料１１、１５が屈折率ｎＡと屈折率ｎＢとの差が大きいため遊色効果が悪かったが、実施例である試料１２〜１４では良好であった。 In samples 11 to 15, samples 11 and 15 as comparative examples had a poor play-color effect because the difference between the refractive index nA and the refractive index nB was large, but samples 12 to 14 as examples were good.
試料１６〜２０では、比較例である試料１６、２０が屈折率ｎＡと屈折率ｎＢとの差が大きいため遊色効果が悪かったが、実施例である試料１７〜１９では良好であった。 In samples 16 to 20, samples 16 and 20 as comparative examples had a bad play effect because the difference between refractive index nA and refractive index nB was large, but samples 17 to 19 as examples were good.
比較例である試料２１〜２５では、屈折率ｎＡが高いので屈折率ｎＢの値に依らず遊色効果が悪かった。 In samples 21 to 25, which are comparative examples, the refractive index nA was high, so that the play-color effect was poor regardless of the value of the refractive index nB.
なお、耐久性については試料１〜２５いずれも優れた結果を示した。 In addition, as for durability, all the samples 1 to 25 showed excellent results.
このように、保形材３が粒子配列体４を包含することによって、シリカ粒子４ａと保形材３とでの界面反射を低減して、遊色効果を視認し易くすることがわかった。 Thus, it was found that the shape retaining material 3 including the particle array 4 reduces the interface reflection between the silica particles 4a and the shape retaining material 3 and makes it easy to visually recognize the play color effect.
（実施例２）
次に、シリカ粒子４ａの屈折率ｎＡと保形材３の屈折率ｎＢを固定して、粒子配列体４の厚さ、保形材３の種類、厚さ、基材フィルム１の種類、厚さ、シリカ粒子径の条件を変更した試料について、遊色効果と耐久性を評価した結果を表２に示す。
(Example 2)
Next, the refractive index nA of the silica particles 4a and the refractive index nB of the shape retaining material 3 are fixed, and the thickness of the particle array 4, the type and thickness of the shape retaining material 3, the type and thickness of the base film 1 are determined. Table 2 shows the results of evaluating the play-color effect and durability of the sample with the silica particle diameter condition changed.
＜試料作製＞
シリカ粒子４ａの屈折率ｎＡを１．４５、保形材３の屈折率ｎＢを１．４５で固定した。
<Sample preparation>
The refractive index nA of the silica particles 4a was fixed at 1.45, and the refractive index nB of the shape retaining material 3 was fixed at 1.45.
粒子配列体４の厚さ（０．１〜３０μｍ）、保形材３の種類、保形材３の厚さ（０．３〜４０μｍ）、基材フィルム１の種類、基材フィルム１の厚さ（３〜６０μｍ）、シリカ粒子径（０．００５〜２０μｍ）を変更した。 Thickness of particle array 4 (0.1 to 30 μm), shape retaining material 3, shape retaining material 3 thickness (0.3 to 40 μm), substrate film 1 type, substrate film 1 thickness (3-60 μm), the silica particle diameter (0.005-20 μm) was changed.
＜評価方法＞
評価方法は、実施例１と同様に行なった。
<Evaluation method>
The evaluation method was performed in the same manner as in Example 1.
＜評価結果＞
比較例である試料２６は、保形材３がないので耐久性が悪かった。
<Evaluation results>
Since the sample 26 which is a comparative example does not have the shape retaining material 3, the durability was poor.
実施例である試料２７〜３１では、粒子配列体４の厚さを変更し、特に試料２８〜３０では粒子配列体４の厚さが０．２〜２０μｍであり、遊色効果を呈する十分な厚さと、耐久性を維持する十分な薄さとを両立することができた。 In Samples 27 to 31, which are examples, the thickness of the particle array 4 is changed. In particular, in Samples 28 to 30, the thickness of the particle array 4 is 0.2 to 20 μm, which is sufficient to exhibit a play color effect. It was possible to achieve both thickness and sufficient thinness to maintain durability.
実施例である試料３２〜３６では、保形材３の種類を変更し、各保形材３で遊色効果と耐久性とを両立することができた。 In Samples 32 to 36 as examples, the type of the shape retaining material 3 was changed, and each of the shape retaining materials 3 was able to achieve both a play color effect and durability.
実施例である試料３７〜４１では、保形材３の厚さを変更し、特に試料３８〜４０では保形材３の厚さが０．４〜３０μｍであり、遊色効果を呈する十分な薄さと、耐久性を維持する十分な厚さとを両立できた。 In the samples 37 to 41, which are examples, the thickness of the shape retaining material 3 is changed. In particular, in the samples 38 to 40, the thickness of the shape retaining material 3 is 0.4 to 30 μm, which is sufficient to exhibit a play color effect. It was possible to achieve both thinness and sufficient thickness to maintain durability.
実施例である試料４２〜４４では、基材フィルム１の種類を変更し、各基材フィルム１で遊色効果と耐久性とを両立することができた。 In samples 42 to 44 as examples, the type of the base film 1 was changed, and each base film 1 was able to achieve both a play-color effect and durability.
実施例である試料４５〜４９では基材フィルム１の厚さを変更し、特に試料４６〜４８では基材フィルム１の厚さが５〜５０μｍであり、基材フィルム１側における遊色効果を呈する十分な薄さと、基材フィルム１側における耐久性を維持する十分な厚さとを両立することができた。 In Samples 45 to 49, which are examples, the thickness of the base film 1 is changed. In particular, in Samples 46 to 48, the thickness of the base film 1 is 5 to 50 μm. It was possible to achieve both a sufficient thinness to be exhibited and a sufficient thickness to maintain durability on the base film 1 side.
実施例である試料５０〜５４では、シリカ粒子径を変更し、特に試料５１〜５３ではシリカ粒子径が０．１〜１０μｍであり、遊色効果と耐久性とを両立することができた。 In the samples 50 to 54 as examples, the silica particle diameter was changed. In particular, in the samples 51 to 53, the silica particle diameter was 0.1 to 10 μm, and both the play color effect and the durability could be achieved.
このように、実施例２７〜５４では、基材フィルム１全体での耐久性、柔軟性を維持するとともに、基材フィルム１内での光の干渉を抑えてブラッグ回折による遊色効果を最大限に発揮させることがわかった。 Thus, in Examples 27-54, while maintaining the durability and flexibility of the base film 1 as a whole, the interference of light in the base film 1 is suppressed and the play-color effect by Bragg diffraction is maximized. I found out that
（実施例３）
次に、シリカ粒子４ａの屈折率ｎＡと保形材３の屈折率ｎＢを固定して、基材フィルム１の屈折率ｎＣを変更した試料について表３に示す。
(Example 3)
Next, Table 3 shows samples in which the refractive index nA of the silica particles 4a and the refractive index nB of the shape retaining material 3 are fixed and the refractive index nC of the base film 1 is changed.
＜試料作製＞
実施例である試料５５〜５９では、屈折率ｎＡを１．４５、屈折率ｎＢを１．４５、粒
子配列体４の厚さを１０μｍ、保形材３の種類、保形材３の厚さを１５μｍ、基材フィルム１の種類、基材フィルム１の厚さを２５μｍ、シリカ粒子径を１μｍで固定して、屈折率Ｃを基材フィルム１中における高屈折率フィラーおよび低屈折率フィラーの含有量を適時調整することで変更した。
<Sample preparation>
In samples 55 to 59 as examples, the refractive index nA is 1.45, the refractive index nB is 1.45, the thickness of the particle array 4 is 10 μm, the type of the shape-retaining material 3, and the thickness of the shape-retaining material 3. Is 15 μm, the type of base film 1, the thickness of the base film 1 is fixed at 25 μm, the silica particle diameter is fixed at 1 μm, and the refractive index C is determined between the high refractive index filler and the low refractive index filler in the base film 1. The content was changed by timely adjustment.
＜評価方法＞
評価方法は、実施例１と同様に行なった。
<Evaluation method>
The evaluation method was performed in the same manner as in Example 1.
＜評価結果＞
実施例である試料５５〜５９では、基材フィルム１側での耐久性、保形材側での柔軟性を向上させるとともに、さらには基材フィルム１側からの視認性も確保することができた。
<Evaluation results>
In samples 55 to 59 as examples, durability on the base film 1 side and flexibility on the shape-retaining material side can be improved, and further visibility from the base film 1 side can be secured. It was.
特に、試料５６〜５８では、屈折率ｎＣが１．４〜１．５であり、優れた遊色効果を呈した。 In particular, Samples 56 to 58 had an index of refraction nC of 1.4 to 1.5 and exhibited an excellent play-color effect.
（実施例４）
次に、遊色効果の評価をＬａｂの値で評価した場合について説明する。
Example 4
Next, the case where the evaluation of the play color effect is evaluated with the value of Lab will be described.
＜試料作製＞
実施例として試料６０では、厚さ２５μｍのＰＥＴフィルムを基材フィルム１とし、処理面に離型層、粒子径０．２７０μｍの球状シリカ粒子４ａからなる粒子配列体４（５μｍ）、エチルセルロースの保形材３（１０μm）を順に塗布、乾燥することによって形成し、加飾フィルム１０を得た。
<Sample preparation>
As an example, in Sample 60, a PET film having a thickness of 25 μm is used as the base film 1, a release layer is formed on the treated surface, a particle array 4 (5 μm) composed of spherical silica particles 4a having a particle diameter of 0.270 μm, and ethyl cellulose. Form 3 (10 μm) was applied in order and dried to obtain a decorative film 10.
実施例として試料６１では、厚さ２５μｍのＰＥＴフィルムを基材フィルム１とし、処理面に離型層、粒子径０．２２５μmの球状シリカ粒子４ａからなる粒子配列体４（５μｍ）、エチルセルロースの保形材３（１０μm）を順に塗布、乾燥することによって形成し、加飾フィルム１０を得た。 As an example, in Sample 61, a PET film having a thickness of 25 μm was used as the base film 1, a release layer on the treated surface, a particle array 4 (5 μm) composed of spherical silica particles 4a having a particle diameter of 0.225 μm, and ethyl cellulose. Form 3 (10 μm) was applied in order and dried to obtain a decorative film 10.
実施例として試料６２では、厚さ２５μｍのＰＥＴフィルムを基材フィルム１とし、処理面に離型層、粒子径０．２７０μｍの球状シリカ粒子４ａからなる粒子配列体４（５μｍ）、カーボンブラックで黒色着色をしたアクリル−シリコン樹脂の保形材３（１０μｍ）を順に塗布、乾燥することによって形成し、加飾フィルム１０を得た。 As an example, in sample 62, a PET film having a thickness of 25 μm is used as the base film 1, a release layer on the treated surface, a particle array 4 (5 μm) composed of spherical silica particles 4a having a particle diameter of 0.270 μm, and carbon black. The decorative film 10 was obtained by applying and drying the black-colored acrylic-silicone resin shape-retaining material 3 (10 μm) in order.
実施例として試料６３では、厚さ２５μｍのＰＥＴフィルムを基材フィルム１とし、処理面に離型層、粒子径０．２７０μｍの球状シリカ粒子４ａからなる粒子配列体４（５μｍ）、カーボンブラック、アルミフレークで銀色着色をしたアクリル−シリコン樹脂の保形材３（１０μｍ）を順に塗布、乾燥することによって形成し、加飾フィルム１０を得た。 As an example, in sample 63, a PET film having a thickness of 25 μm was used as the base film 1, a release layer on the treated surface, a particle array 4 (5 μm) composed of spherical silica particles 4a having a particle diameter of 0.270 μm, carbon black, The decorative film 10 was obtained by applying and drying the acrylic-silicone resin shape-retaining material 3 (10 μm) colored in silver with aluminum flakes in order.
比較例として試料６４では、厚さ２５μｍのＰＥＴフィルムを基材フィルム１とし、処理面に離型層、粒子径０．２７０μｍの球状シリカ粒子４ａからなる粒子配列体４（１０μｍ）を塗布、乾燥することによって形成し、加飾フィルム１０を得た。 As a comparative example, in sample 64, a PET film having a thickness of 25 μm was used as the base film 1, and a release layer and a particle array 4 (10 μm) composed of spherical silica particles 4a having a particle diameter of 0.270 μm were applied to the treated surface and dried. The decorative film 10 was obtained.
＜評価方法＞
実施例１〜実施例４、比較例１について、変角測色計（カラーテクノシステム）を用いて、入射角を３０°、光源をＤ６５、視野角を１０°、測定角度を−８５°〜＋８５°で測定した結果を図４に示す。
<Evaluation method>
For Example 1 to Example 4 and Comparative Example 1, using an angle change colorimeter (color techno system), the incident angle is 30 °, the light source is D65, the viewing angle is 10 °, and the measurement angle is −85 ° to The results measured at + 85 ° are shown in FIG.
＜評価結果＞
図４より、実施例である試料６０〜６３は、測定する角度によって異なる色を呈し、遊色効果を有する加飾フィルム１０としての機能が確認できる。
<Evaluation results>
From FIG. 4, the samples 60 to 63 as examples show different colors depending on the angle to be measured, and the function as the decorative film 10 having a play color effect can be confirmed.
ここでＬ、ａ、ｂの各値としては、Ｌ値を３０以上、角度によるa値の変化量△ａを２０以上、角度によるｂ値の変化量△ｂを２０以上とすることが遊色効果を顕著にできる点で好ましいことがわかった。 Here, as the values of L, a, and b, it is assumed that the L value is 30 or more, the a value change Δa due to the angle is 20 or more, and the b value change Δb due to the angle is 20 or more. It turned out that it is preferable at the point which can make an effect remarkable.
一方、比較例である試料６４も遊色効果を示したが、不織布でこすると保形材３がないため、粒子配列体４が崩れてしまった。 On the other hand, the sample 64 which is a comparative example also showed a play-color effect, but the particle array 4 collapsed because there was no shape-retaining material 3 when rubbed with a nonwoven fabric.
また例示していないが、保形材３にカーボンブラック、酸化鉄赤（弁柄）、フタロシアニンブルー、コバルトグリーン、コバルトブルーおよびクロムイエロー（黄鉛）をそれぞれ色材として添加した場合、可視光を吸収して基材フィルム１の全体的な色相を調整することができた。 Although not illustrated, when carbon black, iron oxide red (valve), phthalocyanine blue, cobalt green, cobalt blue and chrome yellow (yellow lead) are added to the shape retaining material 3 as color materials, visible light is not emitted. The overall hue of the substrate film 1 was able to be adjusted by absorption.
特に、色剤の粒子径は０．０１〜１μｍであることが、色相を向上させることができる点で好ましいことがわかった。 In particular, it was found that the particle diameter of the colorant is preferably 0.01 to 1 μm from the viewpoint that the hue can be improved.
１：基板フィルム
３：保形材
４：粒子配列体
４ａ：シリカ粒子
４ｂ：シリカ粒子間空域
１０：加飾フィルム
1: Substrate film 3: Shape retaining material 4: Particle array 4a: Silica particles 4b: Space between silica particles 10: Decorating film
Claims (5)
該基材フィルム上に位置する、複数のシリカ粒子が規則配列してなる粒子配列体と、
該粒子配列体の内部に充填されるとともに該粒子配列体を被覆している保形材とを有する加飾フィルムであって、
前記シリカ粒子の屈折率をｎＡ（Ａ＝１．３５〜１．５５）とし、前記保形材の屈折率をｎＢとしたとき、ｎＡとｎＢとの差（｜ｎＡ−ｎＢ｜）が０．０２以下である加飾フィルム。 A base film;
A particle array in which a plurality of silica particles are regularly arranged on the base film;
A decorative film having a shape-retaining material filled inside the particle array and covering the particle array,
When the refractive index of the silica particles is nA (A = 1.35 to 1.55) and the refractive index of the shape retaining material is nB, the difference between nA and nB (| nA−nB |) is 0. A decorative film that is 02 or less.
前記基材フィルムがポリエステル系樹脂、アクリル系樹脂およびポリカーボネ―ト系樹脂からなる群より選択される少なくとも１種からなり、
前記基材フィルムの屈折率をｎＣとしたとき、
前記ｎＡとｎＣとの差（｜ｎＡ−ｎＣ｜）が０．０５以下である請求項１に記載の加飾フィルム。 The shape-retaining material comprises at least one selected from the group consisting of a cellulose resin, a polyester resin, a urethane resin, a silicon resin, and an epoxy resin,
The base film comprises at least one selected from the group consisting of a polyester resin, an acrylic resin, and a polycarbonate resin,
When the refractive index of the base film is nC,
The decorative film according to claim 1, wherein a difference (| nA−nC |) between the nA and nC is 0.05 or less.
該粒子配列体の内部に保形材を充填するとともに、前記粒子配列体の表面を前記保形材で被覆して、該保形材を乾燥させる工程とを有する加飾フィルムの製造方法。
Forming a particle array in which the silica particles are regularly arranged by applying a dispersion containing a plurality of silica particles and precipitating the silica particles on a base film;
A method for producing a decorative film, comprising filling a shape-retaining material inside the particle array, covering the surface of the particle array with the shape-retaining material, and drying the shape-retaining material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104150788A (en) * | 2014-07-23 | 2014-11-19 | 大连理工大学 | Hydrophobic photon crystal-structure color-producing material and preparation method thereof |
| JP2014234393A (en) * | 2013-05-30 | 2014-12-15 | 京セラ株式会社 | Decorative member, lamination structure using the same, and display device |
| JP2016196131A (en) * | 2015-04-03 | 2016-11-24 | アルプス電気株式会社 | Decorative laminate structure, housing and electronic apparatus |
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| JP2007327042A (en) * | 2006-05-11 | 2007-12-20 | Sk Kaken Co Ltd | Method for producing colored structure |
| JP2009228003A (en) * | 2008-02-29 | 2009-10-08 | Nagoya City Univ | Epoxy resin composition, and construction material and body accessory formed by using the same |
| JP2010060974A (en) * | 2008-09-05 | 2010-03-18 | Konica Minolta Business Technologies Inc | Display member |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007327042A (en) * | 2006-05-11 | 2007-12-20 | Sk Kaken Co Ltd | Method for producing colored structure |
| JP2009228003A (en) * | 2008-02-29 | 2009-10-08 | Nagoya City Univ | Epoxy resin composition, and construction material and body accessory formed by using the same |
| JP2010060974A (en) * | 2008-09-05 | 2010-03-18 | Konica Minolta Business Technologies Inc | Display member |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014234393A (en) * | 2013-05-30 | 2014-12-15 | 京セラ株式会社 | Decorative member, lamination structure using the same, and display device |
| CN104150788A (en) * | 2014-07-23 | 2014-11-19 | 大连理工大学 | Hydrophobic photon crystal-structure color-producing material and preparation method thereof |
| JP2016196131A (en) * | 2015-04-03 | 2016-11-24 | アルプス電気株式会社 | Decorative laminate structure, housing and electronic apparatus |
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