JP4036465B1 - Insulating material with excellent metallic luster and molded product using the same - Google Patents
Insulating material with excellent metallic luster and molded product using the same Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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Abstract
絶縁性金属薄膜の少なくとも片面を、亜鉛化合物微粒子を含む絶縁性樹脂層で覆うことにより、金属薄膜を安定に保ち、高温高湿条件下でも、実質的に金属光沢に変化のない絶縁性材料の提供を可能とする。この絶縁性材料は、プラスチックフィルム上に、少なくとも、絶縁性金属薄膜、及び亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層を順次形成したもの、又はプラスチックフィルム上に、離型層、保護層、絶縁性金属薄膜、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層、及び接着層を順次形成したものであり、後者は、転写絶縁性材料として有用である。かかる絶縁性材料を、プラスチック基材表面に貼着又は転写することにより、安定して金属光沢に優れた成形品を得ることができる。
【選択図】なしBy covering at least one surface of the insulating metal thin film with an insulating resin layer containing zinc compound fine particles, the metal thin film can be kept stable, and an insulating material that does not substantially change its metallic luster even under high temperature and high humidity conditions. It can be provided. This insulating material is obtained by sequentially forming at least an insulating metal thin film and an insulating resin layer containing zinc compound fine particles and a resin on a plastic film, or a release layer, a protective layer, an insulating layer on a plastic film. The conductive metal thin film, the insulating resin layer containing the zinc compound fine particles and the resin, and the adhesive layer are sequentially formed. The latter is useful as a transfer insulating material. By sticking or transferring such an insulating material onto the surface of a plastic substrate, a molded product having a stable and excellent metallic luster can be obtained.
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Description
本発明は、スズ等の金属薄膜を用いた絶縁性材料、及びそれを用いた成形品に関する。 The present invention relates to an insulating material using a metal thin film such as tin and a molded article using the same.
絶縁性材料に金属光沢を有する絶縁被膜を形成するため、スズ等の絶縁性金属薄膜を形成することは知られている（特許文献１〜３参照）。しかし、単にスズ等の絶縁性金属薄膜を形成しただけでは、例えば６０℃×９５％×９６時間というような高温高湿条件下では、スズ等の絶縁性金属薄膜の腐食により全光線透過率が６０％を越えてしまい、外観変化が激しく、携帯電話などに実用化できるものではなかった。特に全光線透過率の高い絶縁性材料は、上記条件下では絶縁性金属薄膜の金属光沢がなくなり、透明に近くなる。また、スズ等の絶縁性金属薄膜は不連続な島状構造をなすため、こすれに対して弱く、キズが非常に入りやすく、外観のよい絶縁性材料を得ることが困難であった。 In order to form an insulating film having a metallic luster on an insulating material, it is known to form an insulating metal thin film such as tin (see Patent Documents 1 to 3). However, by simply forming an insulating metal thin film such as tin, the total light transmittance is reduced due to corrosion of the insulating metal thin film such as tin under high temperature and high humidity conditions such as 60 ° C. × 95% × 96 hours. It exceeded 60%, and the appearance change was so severe that it could not be put to practical use in mobile phones. In particular, an insulating material having a high total light transmittance loses the metallic luster of the insulating metal thin film under the above conditions and becomes nearly transparent. Further, since an insulating metal thin film such as tin has a discontinuous island-like structure, it is difficult to obtain an insulating material having a good appearance because it is vulnerable to rubbing and is easily damaged.
そこで、特許文献４では、金属蒸着層の表面に酸化防止層として、メラミン樹脂、又はアクリルポリオール/イソシアネート二液硬化型樹脂の層を設けることを開示しているが、かかる酸化防止層を設けても、高温高湿条件下に十分耐えることができず、全光線透過率を５０％以下にすることは困難であった。
本発明は、絶縁性金属薄膜を使用し、金属光沢、及び絶縁性に優れた耐久性ある絶縁性材料、特に、高温高湿条件下でも実質的に金属光沢に変化はなく、全光線透過率を５０％以下に保つことができる絶縁性材料とそれを用いた成形品を提供することを課題とする。 The present invention uses an insulating metal thin film and has a metallic luster and a durable insulating material excellent in insulation, in particular, the metallic luster is substantially unchanged even under high temperature and high humidity conditions, and the total light transmittance It is an object of the present invention to provide an insulating material capable of maintaining the content of 50% or less and a molded product using the same.
本発明では、絶縁性金属薄膜の少なくとも片面を、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層で覆うことにより、前記課題を解決した。 In the present invention, the problem is solved by covering at least one surface of the insulating metal thin film with an insulating resin layer containing zinc compound fine particles and a resin.
本発明の第一の絶縁性材料は、プラスチックフィルム上に、少なくとも、絶縁性金属薄膜、及び亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層を順次形成したものであり、プラスチックフィルムと絶縁性金属薄膜の間に保護層を形成してもよく、また絶縁性樹脂層上に接着層を形成してもよい。
この絶縁性材料は、携帯電話やオーディオ製品等の筐体、家電等のリモコン用赤外線透過カバーパネル、自動車用ミリ波透過カバーパネル、その他のプラスチック基材に使用するインサートフィルムとして有用であり、その他電子レンジ用食品の容器、包装材、農園芸用反射テープ、金銀糸等としても有用である。The first insulating material of the present invention is obtained by sequentially forming at least an insulating metal thin film and an insulating resin layer containing zinc compound fine particles and a resin on a plastic film. The plastic film and the insulating metal thin film A protective layer may be formed between them, and an adhesive layer may be formed on the insulating resin layer.
This insulating material is useful as an insert film for casings for mobile phones, audio products, etc., infrared transmission cover panels for remote controls such as home appliances, millimeter wave transmission cover panels for automobiles, and other plastic substrates. It is also useful as a container for food for microwave ovens, packaging materials, reflective tapes for agriculture and horticulture, gold and silver threads, and the like.
また、本発明の第二の絶縁性材料は、プラスチックフィルム上に、離型層、保護層、絶縁性金属薄膜、及び亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層を順次形成し、更に前記絶縁性樹脂層上に接着層を形成した、転写絶縁性材料である。プラスチックフィルムと離型層の間には、下塗層を形成してもよい。
この絶縁性材料は、プラスチック基材表面に転写することにより、容易に、安定して金属光沢ある成形品を得ることを可能とするものであり、携帯電話やオーディオ製品等の筐体、家電等のリモコン用赤外線透過カバーパネル、自動車用ミリ波透過カバーパネル、その他のプラスチック基材に金属光沢ある外観を付与するための転写フィルムとして有用である。Further, the second insulating material of the present invention is formed by sequentially forming a release layer, a protective layer, an insulating metal thin film, and an insulating resin layer containing zinc compound fine particles and a resin on a plastic film. A transfer insulating material in which an adhesive layer is formed on the conductive resin layer. An undercoat layer may be formed between the plastic film and the release layer.
This insulating material can be easily and stably obtained a molded product with metallic luster by transferring it onto the surface of a plastic substrate. It is useful as a transfer film for imparting a metallic luster appearance to infrared transmission cover panels for remote controls, millimeter wave transmission cover panels for automobiles, and other plastic substrates.
なお、第一、及び第二の絶縁性材料のいずれにおいても、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層は、亜鉛化合物微粒子と樹脂以外に、例えば染料等の着色剤やシリカ等の滑剤を含んでいてもよい。また、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層の厚さは、０．０１〜５μｍ程度であるのが好ましく、絶縁性樹脂層中の亜鉛化合物微粒子の含有量は、１〜３０重量％程度でよい。 In any of the first and second insulating materials, the insulating resin layer containing the zinc compound fine particles and the resin includes a colorant such as a dye or a lubricant such as silica in addition to the zinc compound fine particles and the resin. May be included. The thickness of the insulating resin layer containing the zinc compound fine particles and the resin is preferably about 0.01 to 5 μm, and the content of the zinc compound fine particles in the insulating resin layer is about 1 to 30% by weight. It's okay.
また、絶縁性樹脂層中の亜鉛化合物微粒子は、微粒子状とできる亜鉛化合物であればよく、酸化亜鉛、硫化亜鉛、及び炭酸亜鉛等の微粒子がいずれも使用できる。 The zinc compound fine particles in the insulating resin layer may be any zinc compound that can be made into fine particles, and any fine particles such as zinc oxide, zinc sulfide, and zinc carbonate can be used.
亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層を形成する樹脂としては、フェノール系樹脂、エポキシ系樹脂、メラミン系樹脂、尿素系樹脂、ポリエステル系樹脂、アルキド系樹脂、アクリル系樹脂、ウレタン系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリスチレン系樹脂、ポリ酢酸ビニル系樹脂、ＡＢＳ(アクリロニトリルブタジエンスチレン)系樹脂、ＡＳ(アクリルスチレン)系樹脂などがいずれも使用できる。また、これらの樹脂は単独で使用しても、二種以上混合使用してもよく、イソシアネートなどの架橋剤と組み合わせて使用してもよい。 As resin which forms the insulating resin layer containing zinc compound fine particles and resin, phenol resin, epoxy resin, melamine resin, urea resin, polyester resin, alkyd resin, acrylic resin, urethane resin, Polyethylene resin, polypropylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, ABS (acrylonitrile butadiene styrene) resin, AS (acryl styrene) resin, etc. Can be used. In addition, these resins may be used alone or in combination of two or more, or may be used in combination with a crosslinking agent such as isocyanate.
また、ここに絶縁性金属薄膜とは、金属光沢と絶縁性を兼ね備えた金属薄膜のことで、従来技術に従って蒸着法で形成することができる。通常、島のサイズが１０Å〜２μｍ（１ｎｍ〜２μm）で、島の間隔が２０Å〜５０００Å（２ｎｍ〜５００ｎｍ）である島状構造となるような薄膜とするのがよく、絶縁性金属薄膜を形成する金属としては、スズ、インジウム、鉛、亜鉛、ビスマス、チタン、クロム、鉄、コバルト、ニッケル、珪素、ゲルマニウム又はこれらの合金からなる群から選ばれるものが使用できるが、スズ又はインジウムであるのが好ましく、特にスズであるのがよい。絶縁性金属薄膜を上記の島状構造とするには、例えば転写絶縁性材料の場合、プラスチックフィルム／離型層／保護層／絶縁性金属薄膜からなる積層体の全光線透過率を１０〜５０％とするのがよい。また、ここに絶縁性とは、絶縁破壊電圧が１０００Ｖ以上であることをいう。 In addition, here, the insulating metal thin film is a metal thin film having both metallic luster and insulating properties, and can be formed by vapor deposition according to the prior art. Usually, the island size is 10 to 2 μm (1 nm to 2 μm) and the distance between the islands is 20 to 5000 mm (2 nm to 500 nm). The metal to be used can be selected from the group consisting of tin, indium, lead, zinc, bismuth, titanium, chromium, iron, cobalt, nickel, silicon, germanium or alloys thereof, but tin or indium. Is preferable, and tin is particularly preferable. In order for the insulating metal thin film to have the above-mentioned island-like structure, for example, in the case of a transfer insulating material, the total light transmittance of the laminate composed of plastic film / release layer / protective layer / insulating metal thin film is set to 10 to 50. % Is good. Further, here, the insulating property means that the dielectric breakdown voltage is 1000 V or more.
絶縁性金属薄膜、及び絶縁性樹脂層は、必ずしも全面に形成せずに、同一の図柄状に積層形成しておいてもよい。ここで、絶縁性金属薄膜、及び絶縁性樹脂層を同一の図柄状に積層形成するとは、絶縁性金属薄膜、及び絶縁性樹脂層を同一の図柄で、かつ絶縁性金属薄膜の真上に絶縁性樹脂層を積層形成することをいう。 The insulating metal thin film and the insulating resin layer are not necessarily formed on the entire surface, and may be laminated in the same pattern. Here, the insulating metal thin film and the insulating resin layer are laminated in the same pattern shape means that the insulating metal thin film and the insulating resin layer are insulated with the same pattern and directly above the insulating metal thin film. It means that a conductive resin layer is laminated.
なお、絶縁性金属薄膜、及び絶縁性樹脂層を同一の図柄状に積層形成するには、例えば転写絶縁性材料の場合、プラスチックフィルム上に離型層、及び保護層を形成し、その上に、図柄状（所望図柄の陰型）に水溶性塗料（ポリビニルアルコール等の水溶性物質からなる塗料であり、必要により体質顔料等を混入した塗料）を塗布して水溶性塗料層を形成した後に、絶縁性金属薄膜、及び絶縁性樹脂層を順次形成し、水洗して、前記水溶性塗料層、及び前記水溶性塗料層上に積層された前記絶縁性金属薄膜、及び絶縁性樹脂層を除去するとともに、前記水溶性塗料層が存在しない部分の前記絶縁性金属薄膜、及び絶縁性樹脂層を残存させるという方法をとるのがよい。かかる方法で、絶縁性金属薄膜をきれいに除去するためには、絶縁性樹脂層の厚さは、０．０１〜０．４μｍ程度であるのが好ましい。 In addition, in order to laminate the insulating metal thin film and the insulating resin layer in the same pattern, for example, in the case of a transfer insulating material, a release layer and a protective layer are formed on a plastic film, and on that, After forming a water-soluble paint layer by applying a water-soluble paint (a paint made of a water-soluble substance such as polyvinyl alcohol and, if necessary, a paint containing a body pigment, etc.) to the pattern (negative pattern of the desired pattern) Then, an insulating metal thin film and an insulating resin layer are sequentially formed and washed to remove the water-soluble paint layer and the insulating metal thin film and the insulating resin layer laminated on the water-soluble paint layer. In addition, it is preferable to take a method in which the insulating metal thin film and the insulating resin layer in a portion where the water-soluble paint layer does not exist are left. In order to cleanly remove the insulating metal thin film by this method, the thickness of the insulating resin layer is preferably about 0.01 to 0.4 μm.
また、絶縁性材料、及び転写絶縁性材料で使用するプラスチックフィルムとしては、例えば、ポリエチレンテレフタレートフィルム、ポリプロピレンフィルム、ポリカーボネートフィルム、ポリエチレンフィルム、ポリスチレンフィルム、ポリアミドフィルム、ポリブチルアクリレートフィルム等がいずれも使用できる。 Examples of the plastic film used for the insulating material and the transfer insulating material include polyethylene terephthalate film, polypropylene film, polycarbonate film, polyethylene film, polystyrene film, polyamide film, and polybutyl acrylate film. .
更に、第一、及び第二の絶縁性材料で使用する保護層、及び第二の絶縁性材料で使用する離型層、接着層、及び下塗層としても、従来の一般的な転写フィルム等と同様のものがいずれも適用可能である。 Furthermore, as a protective layer used in the first and second insulating materials, a release layer, an adhesive layer, and an undercoat layer used in the second insulating material, a conventional general transfer film, etc. Any of the same can be applied.
例えば、離型層としては、エーテル系、エステル系、エポキシ系、アクリル系、シリコン系、ワックス系等の樹脂、及び共重合体を一種又は二種以上使用するのが好ましい。 For example, as the release layer, it is preferable to use one or more of ether-based, ester-based, epoxy-based, acrylic-based, silicon-based, wax-based resins, and copolymers.
保護層としては、エーテル系、エステル系、エポキシ系、アクリル系、ウレタン系等の樹脂、及び共重合体を一種又は二種以上使用するのが好ましく、接着層としては、エーテル系、エステル系、アクリル系、塩化ビニル、酢酸ビニル等の樹脂、及び共重合体を一種又は二種以上使用するのが好ましい。なお、絶縁性金属薄膜と接する保護層に、亜鉛化合物微粒子を添加してもよい。 As the protective layer, it is preferable to use one or two or more resins such as ether, ester, epoxy, acrylic, urethane, and copolymers, and as the adhesive layer, ether, ester, It is preferable to use one type or two or more types of resins and copolymers such as acrylic, vinyl chloride and vinyl acetate. Incidentally, zinc compound fine particles may be added to the protective layer in contact with the insulating metal thin film.
本発明は、プラスチック基材表面に接着層を介して、第一の絶縁性材料の絶縁性樹脂層面を貼着してなるものであって、少なくともプラスチック基材上に、接着層、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層、絶縁性金属薄膜、必要により保護層、及びプラスチックフィルムを順次形成した成形品をも対象とするものである。この成形品は、携帯電話やオーディオ製品等の筐体、家電等のリモコン用赤外線透過カバーパネル、自動車用ミリ波透過カバーパネル、その他のプラスチック成形品、モール材等として有用である。なお、接着層は、予め、絶縁性材料の絶縁性樹脂層に形成しても、プラスチック基材に形成しても良い。 The present invention is obtained by attaching an insulating resin layer surface of a first insulating material to a plastic substrate surface via an adhesive layer, and at least an adhesive layer, zinc compound fine particles on the plastic substrate And a molded product in which an insulating resin layer containing a resin, an insulating metal thin film, a protective layer, and a plastic film, if necessary, are sequentially formed. This molded product is useful as a casing for a mobile phone or an audio product, an infrared transmission cover panel for remote control of home appliances, a millimeter wave transmission cover panel for automobiles, other plastic molded products, a molding material, and the like. Note that the adhesive layer may be formed in advance on an insulating resin layer of an insulating material or may be formed on a plastic substrate.
更に、本発明は、プラスチック基材表面に、第二の絶縁性材料である転写絶縁性材料を転写して得られる、プラスチック基材上に、接着層、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層、絶縁性金属薄膜、保護層、及び離型層を順次形成した成形品をも対象とする。この成形品も、携帯電話やオーディオ製品等の筐体、家電等のリモコン用赤外線透過カバーパネル、自動車用ミリ波透過カバーパネル、その他のプラスチック成形品等として有用である。 Furthermore, the present invention provides an insulating resin containing an adhesive layer, zinc compound fine particles and a resin on a plastic substrate obtained by transferring a transfer insulating material as a second insulating material onto the surface of the plastic substrate. A molded product in which a layer, an insulating metal thin film, a protective layer, and a release layer are sequentially formed is also an object. This molded product is also useful as a casing for mobile phones, audio products, etc., an infrared transmission cover panel for remote control of home appliances, a millimeter wave transmission cover panel for automobiles, and other plastic molded products.
また、本発明の転写絶縁性材料を使用してインモールド成形により、表面に金属光沢ある成形品を得ることも可能であるが、この場合、プラスチックフィルムと離型層との離型性を向上し、転写時にプラスチックフィルムの剥離不良や破れの発生を防止する目的で、プラスチックフィルムと離型層との間に、下塗層を形成するのが好ましく、該下塗層の形成により、金属光沢ある、複雑な形状の成形品を安定して得ることが可能となる。下塗層に使用する樹脂は、メラミン系樹脂、アミノアルキッド系樹脂、エポキシ系樹脂、アクリル系樹脂、シリコーン系樹脂等の熱硬化性樹脂やワックス等が使用できるが、特にメラミン系樹脂が好ましい。 It is also possible to obtain a molded product with a metallic luster on the surface by in-mold molding using the transfer insulating material of the present invention. In this case, the mold release property between the plastic film and the release layer is improved. For the purpose of preventing the occurrence of defective peeling or tearing of the plastic film during transfer, it is preferable to form an undercoat layer between the plastic film and the release layer. It becomes possible to stably obtain a molded product having a certain complicated shape. As the resin used for the undercoat layer, thermosetting resins such as melamine resins, aminoalkyd resins, epoxy resins, acrylic resins, and silicone resins, waxes, and the like can be used, and melamine resins are particularly preferable.
なお、本発明では、前述した如き、絶縁性金属薄膜、及び絶縁性樹脂層を同一の図柄状に積層形成した絶縁性材料又は転写絶縁性材料を使用することにより、金属光沢ある図柄を有する成形品を得ることができる。例えば、プラスチック基材表面に接着層を介して、絶縁性金属薄膜、及び絶縁性樹脂層を同一の図柄状に積層形成した絶縁性材料の絶縁性樹脂層面側を貼着し、プラスチック基材上に、接着層、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層、絶縁性金属薄膜、及びプラスチックフィルムを順次形成し、かつ前記絶縁性樹脂層、及び前記絶縁性金属薄膜を同一の図柄状に積層形成した成形品としたり、又は、絶縁性金属薄膜、及び絶縁性樹脂層を同一の図柄状に積層形成した転写絶縁性材料を、プラスチック基材表面に転写し、プラスチック基材上に、接着層、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層、絶縁性金属薄膜、保護層、及び離型層を順次形成し、かつ前記絶縁性樹脂層、及び前記絶縁性金属薄膜を同一の図柄状に積層形成した成形品とすることができるのである。 In the present invention, as described above, by using an insulating material or a transfer insulating material in which an insulating metal thin film and an insulating resin layer are laminated in the same pattern shape, a molding having a metallic glossy pattern is used. Goods can be obtained. For example, the insulating resin layer side of an insulating material formed by laminating an insulating metal thin film and an insulating resin layer in the same pattern on the surface of a plastic substrate is bonded to the plastic substrate via an adhesive layer. In addition, an adhesive layer, an insulating resin layer containing zinc compound fine particles and a resin, an insulating metal thin film, and a plastic film are sequentially formed, and the insulating resin layer and the insulating metal thin film are laminated in the same pattern. A transfer insulating material, which is a molded product formed or laminated with an insulating metal thin film and an insulating resin layer in the same pattern, is transferred to the surface of the plastic substrate, and an adhesive layer is formed on the plastic substrate. Insulating resin layer containing zinc compound fine particles and resin, insulating metal thin film, protective layer, and release layer are sequentially formed, and the insulating resin layer and the insulating metal thin film are laminated in the same pattern Formed It is possible to goods.
本発明の絶縁性材料、及び成形品は、下記の効果を有する。
１）絶縁性金属薄膜が島状構造であるため、絶縁性材料の製造時に、通常は絶縁性金属薄膜表面にキズが入り易いが、亜鉛化合物微粒子と樹脂を含む絶縁性樹脂層を有する本発明の絶縁性材料は、絶縁性金属薄膜表面にキズのない、非常に美麗なものとなる。
２）インモールド成形等により成形品を製造する場合にも、絶縁性金属薄膜にクラックが出難く、絶縁性金属薄膜と絶縁性樹脂層の層間密着性が良い。
３）本発明の成形品は、携帯電話やオーディオ製品等の耐久性についての評価基準である６０℃×９５％×９６時間という高温高湿試験でも、全光線透過率が５０％を超えず、また該試験の前後の全光線透過率の差(変化度）が１０％以下であり、腐食により絶縁性金属薄膜が消失することがないので、非常に広範な用途に適用できるものである。The insulating material and molded product of the present invention have the following effects.
1) Since the insulating metal thin film has an island-like structure, the surface of the insulating metal thin film is usually easily scratched during the production of the insulating material, but has an insulating resin layer containing zinc compound fine particles and a resin. This insulating material is very beautiful with no scratches on the surface of the insulating metal thin film.
2) Even when a molded product is manufactured by in-mold molding or the like, the insulating metal thin film is hardly cracked, and the interlayer adhesion between the insulating metal thin film and the insulating resin layer is good.
3) The molded article of the present invention has a total light transmittance of not exceeding 50% even in a high temperature and high humidity test of 60 ° C. × 95% × 96 hours, which is an evaluation standard for durability of mobile phones, audio products and the like. In addition, the difference (degree of change) in total light transmittance before and after the test is 10% or less, and the insulating metal thin film does not disappear due to corrosion, so that it can be applied to a very wide range of applications.
以下、本発明を実施例に従って説明する。
＜実施例１＞
厚さ２５μｍのポリエチレンテレフタレートフィルム（三菱化学ポリエステルフィルム社製の「ダイアホイルＧ１００」）の片面に、アクリル系樹脂（日立化成工業社製の「ヒタロイドＨＡ３００４」）、及びイソシアネート（日本ポリウレタン工業社製の「コロネート２０３０」）からなる厚さ１μｍの保護層を形成し、該保護層上に真空蒸着法で厚さ１３ｎｍの島状構造で絶縁性のスズ薄膜を形成して、ポリエチレンテレフタレートフィルム／保護層／スズ薄膜からなる積層フィルム（Ａ）を得た。
次いで、この積層フィルム（Ａ）のスズ薄膜上にリバースコート法にて、酸化亜鉛微粒子（テイカ社製の「酸化亜鉛スラリー７５０Ｚ」）、ウレタン系樹脂（三井武田ケミカル社製の「タケラックＡ−３１０」）、及びイソシアネート（三井武田ケミカル社製の「タケネートＡ−３」）よりなる厚さ２μｍの絶縁性樹脂層（酸化亜鉛微粒子の含有量：６重量％）を形成し、さらに該絶縁性樹脂層上に、アクリル系樹脂（コニシ社製の「ＫＴ５９５クリアー」）よりなる厚さ１μｍの接着層を形成して、本発明の絶縁性材料を得た。
次に、上記絶縁性材料の接着層面とプラスチック基材である厚さ２ｍｍの透明アクリル樹脂板とを熱ロールによりラミネートして、透明アクリル樹脂板／接着層／絶縁性樹脂層／スズ薄膜／保護層／ポリエチレンテレフタレートフィルムを順次形成した本発明の成形品を得た。
得られた成形品は、高温高湿試験（６０℃×９５％×９６時間）において、金属光沢に変化は見られなかった（全光線透過率：試験前３０％、試験後３１％）。Hereinafter, the present invention will be described according to examples.
<Example 1>
On one side of a 25 μm thick polyethylene terephthalate film (“Diafoil G100” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), an acrylic resin (“Hitaroid HA3004” manufactured by Hitachi Chemical Co., Ltd.) and isocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) A protective layer having a thickness of 1 μm made of “Coronate 2030”), an insulating tin thin film having an island-like structure with a thickness of 13 nm formed by vacuum deposition on the protective layer, and a polyethylene terephthalate film / protective layer / The laminated film (A) which consists of a tin thin film was obtained.
Subsequently, zinc oxide fine particles (“Zinc oxide slurry 750Z” manufactured by Takeka) and urethane resin (“Takelac A-310 manufactured by Mitsui Takeda Chemical Co., Ltd.) are formed on the tin thin film of the laminated film (A) by reverse coating. )) And an isocyanate (“Takenate A-3” manufactured by Mitsui Takeda Chemical Co., Ltd.) and having a thickness of 2 μm, an insulating resin layer (content of zinc oxide fine particles: 6% by weight) is further formed. On the layer, an adhesive layer having a thickness of 1 μm made of an acrylic resin (“KT595 Clear” manufactured by Konishi Co., Ltd.) was formed to obtain an insulating material of the present invention.
Next, the adhesive layer surface of the insulating material and a transparent acrylic resin plate having a thickness of 2 mm, which is a plastic substrate, are laminated by a hot roll, and the transparent acrylic resin plate / adhesive layer / insulating resin layer / tin thin film / protection are laminated. A molded article of the present invention in which a layer / polyethylene terephthalate film was sequentially formed was obtained.
The obtained molded article showed no change in metallic luster in the high temperature and high humidity test (60 ° C. × 95% × 96 hours) (total light transmittance: 30% before the test, 31% after the test).
＜実施例２＞
厚さ２５μｍのポリエチレンテレフタレートフィルム（三菱化学ポリエステルフィルム社製の「ダイアホイルＧ１００」）の片面に、グラビアコート法にて、アクリル・メラミン系樹脂（大日精化工業社製の「ＥＸ−１１４メヂウム」）よりなる厚さ０．５μｍの下塗層を形成し、その上にアクリル系樹脂（大日本インキ化学工業社製の「ＴＲ−１６ニス」）よりなる厚さ１μｍの離型層、アクリル系樹脂（日立化成工業社製の「ヒタロイドＨＡ３００４」）、及びイソシアネート（三井武田ケミカル社製の「タケネートＤ−１１０Ｎ」）からなる厚さ１μｍの保護層、ポリビニルアルコールと体質顔料（昭和インク工業社製の「水洗プライマー」）よりなる厚さ１μｍの水溶性塗料層（所望図柄の陰型）を順次形成し、その上に、真空蒸着法で厚さ２０ｎｍの島状構造で絶縁性を備えたスズ薄膜を形成して、ポリエチレンテレフタレートフィルム／下塗層／離型層／保護層／水溶性塗料層（所望図柄の陰型）／スズ薄膜からなる積層フィルム（Ｂ）を得た。
次いで、この積層フィルム（Ｂ）のスズ薄膜上にリバースコート法にて、酸化亜鉛微粒子（テイカ社製の「酸化亜鉛スラリー７５０Ｚ」）、メラミン系樹脂（日立化成工業社製の「メラン２７」）、及びアクリル系樹脂（日立化成工業社製の「ヒタロイドＨＡ３００４」）よりなる厚さ０．２μｍの絶縁性樹脂層（酸化亜鉛微粒子の含有量：６重量％）を形成し、その後、水洗して、前記水溶性塗料層と共に、その上に積層されたスズ薄膜と絶縁性樹脂層を除去し、前記水溶性塗料層が存在しない部分のスズ薄膜、及び絶縁性樹脂層を残存させ、所望の図柄に積層形成し、その上にグラビアコート法にて、アクリル系樹脂（コニシ社製の「ＫＴ５９５クリアー」）よりなる厚さ1μｍの接着層を形成し、本発明の転写絶縁性材料を得た。
次に、プラスチック基材として透明アクリル樹脂を用いたインモールド成形法にて、上記転写絶縁性材料を転写して、透明アクリル基材に、接着層／保護層／離型層を順次形成した透明部分と、接着層／酸化亜鉛微粒子と樹脂を含む絶縁性樹脂層／スズ薄膜／保護層／離型層を順次形成した金属光沢を有する図柄部分が混在する美麗な外観を有する本発明の成形品を得た。
得られた成形品の層間密着性は良好で、セロテープ（登録商標）剥離試験で何ら剥離されることなく、金属光沢を有する部分に傷もなかった。また、高温高湿試験（６０℃×９５％×９６時間）においても、金属光沢に変化は見られなかった（全光線透過率：試験前１５％、試験後１６％）。<Example 2>
Acrylic / melamine resin (EX-114 Medium manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied to one side of a 25 μm thick polyethylene terephthalate film (“Diafoil G100” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) by gravure coating. ) And a 1 μm thick release layer made of acrylic resin (“TR-16 varnish” manufactured by Dainippon Ink & Chemicals, Inc.) 1 μm thick protective layer made of resin (“Hitaroid HA3004” manufactured by Hitachi Chemical Co., Ltd.) and isocyanate (“Takenate D-110N” manufactured by Takeda Chemicals, Ltd.), polyvinyl alcohol and extender (made by Showa Ink Industries, Ltd.) 1 μm thick water-soluble coating layer (desired pattern of desired pattern) is sequentially formed, and then vacuum-deposited on it. Forming a tin thin film with insulating properties with an island-like structure with a thickness of 20 nm, from polyethylene terephthalate film / undercoat layer / release layer / protective layer / water-soluble paint layer (negative pattern of desired pattern) / tin thin film A laminated film (B) was obtained.
Next, on the tin thin film of this laminated film (B), zinc oxide fine particles (“Zinc Oxide Slurry 750Z” manufactured by Teika) and melamine resin (“Melan 27” manufactured by Hitachi Chemical Co., Ltd.) are applied by reverse coating. And 0.2 μm thick insulating resin layer (content of zinc oxide fine particles: 6% by weight) made of acrylic resin (“Hitaroid HA3004” manufactured by Hitachi Chemical Co., Ltd.), and then washed with water. In addition to the water-soluble paint layer, the tin thin film and the insulating resin layer laminated thereon are removed, and the tin thin film and the insulating resin layer in a portion where the water-soluble paint layer does not exist are left to have a desired pattern. A 1 μm-thick adhesive layer made of an acrylic resin (“KT595 Clear” manufactured by Konishi Co., Ltd.) was formed thereon by a gravure coating method to obtain a transfer insulating material of the present invention.
Next, the transfer insulating material is transferred by an in-mold molding method using a transparent acrylic resin as a plastic substrate, and an adhesive layer / protective layer / release layer is sequentially formed on the transparent acrylic substrate. The molded product of the present invention having a beautiful appearance in which a portion having a metallic luster in which an adhesive layer / insulating resin layer containing zinc oxide fine particles and a resin / tin thin film / protective layer / release layer are sequentially formed is mixed Got.
The obtained molded article had good interlaminar adhesion, was not peeled off at all in the cello tape (registered trademark) peel test, and there were no scratches on the part having metallic luster. Further, even in the high temperature and high humidity test (60 ° C. × 95% × 96 hours), no change was observed in the metallic luster (total light transmittance: 15% before the test, 16% after the test).
＜実施例３〜９、及び比較例１〜６＞
厚さ２５μｍのポリエチレンテレフタレートフィルム（三菱化学ポリエステルフィルム社製の「ダイアホイルＧ１００」）の片面に、グラビアコート法にて、アクリル系樹脂（大日本インキ化学工業社製の「ＴＲ−１６ニス」）よりなる厚さ1μｍの離型層、アクリル系樹脂（日立化成工業社製の「ヒタロイドＨＡ３００４」）、及びイソシアネート（三井武田ケミカル社製の「タケネートＤ−１１０Ｎ」）からなる厚さ１μｍの保護層を形成し、この保護層上に真空蒸着法で厚さ１３ｎｍの島状構造で絶縁性を備えたスズ薄膜を形成して、ポリエチレンテレフタレートフィルム／離型層／保護層／スズ薄膜からなる積層フィルム（Ｃ）を得た。
次いで、この積層フィルム（Ｃ）のスズ薄膜上にリバースコート法にて、表１の実施例３〜９に示す酸化亜鉛微粒子と樹脂を含む絶縁性樹脂層−厚さ０．２μｍ−を形成し、その後、アクリル系樹脂（コニシ社製の「ＫＴ５９５クリアー」）よりなる厚さ２μｍの接着層を形成し、実施例３〜９の本発明の転写絶縁性材料を得た。
また、上記積層フィルム（Ｃ）のスズ薄膜上に、前記絶縁性樹脂層、及び樹脂層のいずれも形成せずに、直接アクリル系樹脂（コニシ社製の「ＫＴ５９５クリアー」）よりなる厚さ２μｍの接着層を形成した比較例１の転写絶縁性材料を得た。更に、上記積層フィルム（Ｃ）のスズ薄膜上にリバースコート法にて、表１の比較例２〜６に示す酸化亜鉛微粒子を含有していない樹脂のみからなる樹脂層−厚さ０．２μｍ−を形成し、その後、アクリル系樹脂（コニシ社製の「ＫＴ５９５クリアー」）よりなる厚さ２μｍの接着層を形成した比較例２〜６の転写絶縁性材料を得た。
次に、ロール転写法で、上記実施例３〜９の本発明の転写絶縁性材料、及び比較例１〜６の転写絶縁性材料をプラスチック基材である厚さ２ｍｍの透明アクリル樹脂板に転写して、透明アクリル樹脂板／接着層／酸化亜鉛微粒子と樹脂を含む絶縁性樹脂層／スズ薄膜／保護層／離型層を順次形成した実施例３〜９の本発明の成形品、透明アクリル樹脂板／接着層／スズ薄膜／保護層／離型層を順次形成した比較例１の成形品、及び透明アクリル樹脂板／接着層／樹脂層／スズ薄膜／保護層／離型層を順次形成した比較例２〜６の成形品を得た。
得られた上記各成形品の全光線透過率を測定し、それぞれ高温高湿試験（６０℃×９５％×９６時間）した後の全光線透過率と比較した。その結果を表１に示す。
なお、実施例３〜９、及び比較例２〜６で絶縁性樹脂層、又は樹脂層に使用したウレタン系樹脂は三井武田ケミカル社製の「タケラックＡ−３１０」であり、それと混合使用したイソシアネートは三井武田ケミカル社製の「タケネートＡ−３」である。また、アクリル系樹脂は日立化成工業社製の「ヒタロイドＨＡ３００４」であり、それと混合使用したイソシアネートは三井武田ケミカル社製の「タケネートＤ−１１０Ｎ」である。また、メラミン系樹脂（イソブチル化メラミン）は日立化成工業社製の「メラン２７」であり、酸化亜鉛微粒子はテイカ社製の「酸化亜鉛スラリー７５０Ｚ」である。<Examples 3-9 and Comparative Examples 1-6>
Acrylic resin ("TR-16 varnish" manufactured by Dainippon Ink & Chemicals, Inc.) is coated on one side of a 25 μm thick polyethylene terephthalate film ("Diafoil G100" manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) by gravure coating. 1 μm thick protective layer comprising a 1 μm thick release layer, an acrylic resin (“Hitaroid HA3004” manufactured by Hitachi Chemical Co., Ltd.), and an isocyanate (“Takenate D-110N” manufactured by Takeshi Mitsui Chemicals). And forming a tin thin film having an insulating property with an island-like structure having a thickness of 13 nm on the protective layer by a vacuum deposition method, and forming a laminated film composed of polyethylene terephthalate film / release layer / protective layer / tin thin film (C) was obtained.
Next, an insulating resin layer including the zinc oxide fine particles and resin shown in Examples 3 to 9 in Table 1 having a thickness of 0.2 μm was formed on the tin thin film of the laminated film (C) by reverse coating. Thereafter, an adhesive layer having a thickness of 2 μm made of an acrylic resin (“KT595 Clear” manufactured by Konishi Co., Ltd.) was formed, and the transfer insulating material of Examples 3 to 9 of the present invention was obtained.
Further, on the tin thin film of the laminated film (C), a thickness of 2 μm made of an acrylic resin (“KT595 clear” manufactured by Konishi Co., Ltd.) directly without forming any of the insulating resin layer and the resin layer. A transfer insulating material of Comparative Example 1 having the above adhesive layer was obtained. Furthermore, on the tin thin film of the laminated film (C), a resin layer composed of only a resin not containing the zinc oxide fine particles shown in Comparative Examples 2 to 6 in Table 1 by the reverse coating method—thickness 0.2 μm— Thereafter, transfer insulating materials of Comparative Examples 2 to 6 were obtained in which an adhesive layer having a thickness of 2 μm made of acrylic resin (“KT595 Clear” manufactured by Konishi Co., Ltd.) was formed.
Next, the transfer insulating material of the present invention of Examples 3 to 9 and the transfer insulating material of Comparative Examples 1 to 6 are transferred to a transparent acrylic resin plate having a thickness of 2 mm which is a plastic substrate by a roll transfer method. Then, the molded article of the present invention of Examples 3 to 9, in which a transparent acrylic resin plate / adhesive layer / insulating resin layer containing zinc oxide fine particles and resin / tin thin film / protective layer / release layer were formed in sequence, transparent acrylic Molded product of Comparative Example 1 in which resin plate / adhesive layer / tin thin film / protective layer / release layer are sequentially formed, and transparent acrylic resin plate / adhesive layer / resin layer / tin thin film / protective layer / release layer are sequentially formed The molded products of Comparative Examples 2 to 6 were obtained.
The total light transmittance of each of the obtained molded products was measured and compared with the total light transmittance after each high temperature and high humidity test (60 ° C. × 95% × 96 hours). The results are shown in Table 1.
In addition, the urethane type resin used for the insulating resin layer or the resin layer in Examples 3 to 9 and Comparative Examples 2 to 6 is “Takelac A-310” manufactured by Mitsui Takeda Chemical Co., Ltd. Is "Takenate A-3" manufactured by Mitsui Takeda Chemical Company. The acrylic resin is “Hitaroid HA3004” manufactured by Hitachi Chemical Co., Ltd., and the isocyanate used in combination with it is “Takenate D-110N” manufactured by Mitsui Takeda Chemical. The melamine resin (isobutylated melamine) is “Melan 27” manufactured by Hitachi Chemical Co., Ltd., and the zinc oxide fine particles are “Zinc oxide slurry 750Z” manufactured by Teika.
絶縁性樹脂層として酸化亜鉛微粒子と樹脂を含む絶縁性樹脂層を形成した実施例３〜９の本発明の成形品は全て、高温高湿試験によっても、金属光沢に変化のない、非常に安定した品質のよいものとなったが、絶縁性樹脂層、及び樹脂層のいずれも形成していない比較例１の成形品、及び酸化亜鉛微粒子を含有していない樹脂層を形成した比較例２〜６の成形品では、高温高湿試験で、全光線透過度が著しく変化し、安定して使用可能な成形品を得ることができなかった。 All the molded products of the present invention of Examples 3 to 9 in which an insulating resin layer containing zinc oxide fine particles and a resin was formed as an insulating resin layer were all very stable with no change in metallic luster even in a high temperature and high humidity test. Comparative Example 2 in which the molded product of Comparative Example 1 in which neither the insulating resin layer nor the resin layer was formed, and the resin layer containing no zinc oxide fine particles were formed. In the molded product of No. 6, the total light transmittance changed remarkably in the high temperature and high humidity test, and a molded product that could be used stably could not be obtained.
＜実施例１０＞
実施例３〜９、及び比較例１〜６で得た積層フィルム（Ｃ）のスズ薄膜上にリバースコート法にて、硫化亜鉛微粒子、及びアクリル系樹脂（日立化成工業社製の「ヒタロイドＨＡ３００４」）よりなる厚さ０．５μｍの絶縁性樹脂層（硫化亜鉛微粒子の含有量：８重量％）を形成し、その後、アクリル系樹脂（コニシ社製の「ＫＴ５９５クリアー」）よりなる厚さ１μｍの接着層を形成して、本発明の転写絶縁性材料を得た。
次に、ロール転写法で、上記転写絶縁性材料をプラスチック基材である厚さ２ｍｍの透明アクリル樹脂板に転写して、透明アクリル樹脂板／接着層／硫化亜鉛微粒子と樹脂を含む絶縁性樹脂層／スズ薄膜／保護層／離型層を順次形成した金属光沢ある本発明の成形品を得た。
得られた成形品の層間密着性は良好で、セロテープ（登録商標）剥離試験で何ら剥離は認められなかった。また、高温高湿試験（６０℃×９５％×９６時間）においても、金属光沢に変化は見られなかった（全光線透過率：試験前３０％、試験後３３％）。<Example 10>
Zinc sulfide fine particles and acrylic resin ("Hitaroid HA3004" manufactured by Hitachi Chemical Co., Ltd.) were applied on the thin tin films of the laminated films (C) obtained in Examples 3 to 9 and Comparative Examples 1 to 6 by reverse coating. ) And a 0.5 μm thick insulating resin layer (content of zinc sulfide fine particles: 8 wt%), and then a 1 μm thick acrylic resin (“KT595 Clear” manufactured by Konishi Co., Ltd.) An adhesive layer was formed to obtain the transfer insulating material of the present invention.
Next, the transfer insulating material is transferred to a transparent acrylic resin plate having a thickness of 2 mm which is a plastic substrate by a roll transfer method, and an insulating resin containing a transparent acrylic resin plate / adhesive layer / zinc sulfide fine particles and resin is transferred. A molded product of the present invention having a metallic luster in which layers / tin thin films / protective layers / release layers were sequentially formed was obtained.
The obtained molded article had good interlayer adhesion, and no peeling was observed in the cello tape (registered trademark) peeling test. Further, even in the high temperature and high humidity test (60 ° C. × 95% × 96 hours), no change was observed in the metallic luster (total light transmittance: 30% before the test, 33% after the test).
＜比較例７＞−絶縁性樹脂層でなく離型層に酸化亜鉛微粒子を添加した場合−
厚さ２５μｍのポリエチレンテレフタレートフィルム（三菱化学ポリエステルフィルム社製の「ダイアホイルＧ１００」）の片面に、酸化亜鉛微粒子（テイカ社製の「酸化亜鉛スラリー７５０Ｚ」）、及びアクリル系樹脂（日立化成工業社製の「ヒタロイドＨＡ３００４」）よりなる厚さ１μｍの離型層（酸化亜鉛微粒子の含有量：８重量％）をグラビアコート法にて形成した。該離型層上にアクリル系樹脂（日立化成工業社製の「ヒタロイドＨＡ３００４」）、及びイソシアネート（三井武田ケミカル社製の「タケネートＤ−１１０Ｎ」）からなる厚さ１μｍの保護層を形成し、該保護層上に真空蒸着法で厚さ１３ｎｍの島状構造で絶縁性のスズ薄膜を形成して、ポリエチレンテレフタレートフィルム／酸化亜鉛微粒子と樹脂を含む離型層／保護層／スズ薄膜からなる積層フィルム（Ｄ）を得た。次いで、この積層フィルム（Ｄ）のスズ薄膜上にリバースコート法にて、アクリル系樹脂（コニシ社製の「ＫＴ５９５クリアー」）よりなる厚さ１μｍの接着層を形成して、転写絶縁性材料を得た。
次に、ロール転写法で、上記転写絶縁性材料をプラスチック基材である厚さ２ｍｍの透明アクリル樹脂板に転写して、透明アクリル樹脂板／接着層／スズ薄膜／保護層／酸化亜鉛微粒子と樹脂を含む離型層を順次形成した金属光沢ある成形品を得た。
得られた成形品の層間密着性は良好で、セロテープ（登録商標）剥離試験で何ら剥離は認められなかった。しかし、高温高湿試験（６０℃×９５％×９６時間）にて、金属光沢は消失した（全光線透過率：試験前３０．５％、試験後９１．０％）。<Comparative Example 7>-When zinc oxide fine particles are added to the release layer instead of the insulating resin layer-
On one side of a 25 μm thick polyethylene terephthalate film (“Diafoil G100” manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.), zinc oxide fine particles (“Zinc Oxide Slurry 750Z” manufactured by Teika), and acrylic resin (Hitachi Chemical Industry Co., Ltd.) A release layer (content of zinc oxide fine particles: 8% by weight) having a thickness of 1 μm made of “Hitaroid HA3004” manufactured by the company was formed by a gravure coating method. On the release layer, a protective layer having a thickness of 1 μm made of acrylic resin (“Hitaroid HA3004” manufactured by Hitachi Chemical Co., Ltd.) and isocyanate (“Takenate D-110N” manufactured by Mitsui Takeda Chemical Co., Ltd.) is formed. An insulating tin thin film having an island-like structure with a thickness of 13 nm is formed on the protective layer by a vacuum deposition method, and a laminate composed of a polyethylene terephthalate film / a release layer containing zinc oxide fine particles and a resin / protective layer / tin thin film. A film (D) was obtained. Next, an adhesive layer having a thickness of 1 μm made of an acrylic resin (“KT595 Clear” manufactured by Konishi Co., Ltd.) is formed on the tin thin film of the laminated film (D) by a reverse coating method. Obtained.
Next, by the roll transfer method, the transfer insulating material is transferred to a transparent acrylic resin plate having a thickness of 2 mm, which is a plastic substrate, and the transparent acrylic resin plate / adhesive layer / tin thin film / protective layer / zinc oxide fine particles A metallic glossy molded article in which a release layer containing a resin was sequentially formed was obtained.
The obtained molded article had good interlayer adhesion, and no peeling was observed in the cello tape (registered trademark) peeling test. However, in the high temperature and high humidity test (60 ° C. × 95% × 96 hours), the metallic luster disappeared (total light transmittance: 30.5% before the test, 91.0% after the test).
本発明の第一、及び第二の絶縁性材料は、金属光沢に優れ、しかも耐久性ある絶縁性被膜を有するので、各種物品の表面を絶縁性を有する状態で、金属光沢に優れたものとすることができるものであり、携帯電話の筺体、オーディオ製品の筺体、家電等のリモコン用赤外線透過カバーパネル、自動車用ミリ波透過カバーパネル、モール材、電子レンジ用食品の容器・包装材、電子レンジ用容器の蓋材、電子部品用包装材、金属蒸着フィルム製風船、鳥追用、誘引用、防虫用などの農園芸用反射テープ、絶縁性の金銀糸、該金銀糸を使用したカーペット、カーマットなどと非常に広範に使用できる。 The first and second insulating materials of the present invention have an excellent metallic luster and have a durable insulating coating, so that the surface of various articles is excellent in metallic luster in a state having insulating properties. Mobile phone housings, audio product housings, infrared transmission cover panels for remote control of household appliances, automotive millimeter wave transmission cover panels, molding materials, food containers and packaging materials for microwave ovens, electronics Covers for range containers, packaging materials for electronic components, balloons made of metal-deposited films, reflections for agricultural and horticultural use such as bird followers, invitations, and insect prevention, insulating gold and silver threads, carpets and car mats using the gold and silver threads It can be used very widely.
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| PCT/JP2006/316245 WO2008020482A1 (en) | 2006-08-18 | 2006-08-18 | Insulating material excelling in metallic gloss and molded article making use of the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102094175B (en) * | 2010-12-30 | 2012-11-21 | 沈阳金锋特种刀具有限公司 | Powder sintering multicomponent alloy coated target adopting direct water cooling and preparation method thereof |
| JP2017177612A (en) * | 2016-03-30 | 2017-10-05 | 大日本印刷株式会社 | Hard coat film for transfer to electromagnetic wave transmissive decorative member, hard coat layer laminate having base material film, electromagnetic wave transmissive decorative member, and manufacturing method thereof |
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| JP5401132B2 (en) * | 2009-01-20 | 2014-01-29 | 信越ポリマー株式会社 | Radio wave transmitting decorative member and manufacturing method thereof |
| JP5402109B2 (en) | 2009-02-27 | 2014-01-29 | デクセリアルズ株式会社 | Anisotropic conductive film and light emitting device |
| JP5346632B2 (en) | 2009-03-17 | 2013-11-20 | 信越ポリマー株式会社 | Radio wave transmitting decorative film and decorative member using the same |
| JP5970914B2 (en) * | 2012-03-29 | 2016-08-17 | 大日本印刷株式会社 | Three-dimensional decorative film |
| JP6593701B2 (en) * | 2016-02-16 | 2019-10-23 | 株式会社豊田中央研究所 | Dielectric thin film |
| WO2020066597A1 (en) * | 2018-09-26 | 2020-04-02 | 富士フイルム株式会社 | Layered body |
| JP7316671B2 (en) * | 2020-11-17 | 2023-07-28 | 尾池工業株式会社 | Scale-like pigment, paint, and painted object having millimeter wave transparency |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS62174189A (en) * | 1985-10-21 | 1987-07-30 | Reiko Co Ltd | Insulating transfer material |
| JP3788101B2 (en) * | 1998-04-24 | 2006-06-21 | 凸版印刷株式会社 | Transparent gas barrier composite film material having UV-cutting property and package using the same |
| JP3877318B2 (en) * | 2004-01-19 | 2007-02-07 | 株式会社麗光 | Iris color transfer film and iris color molded product obtained using the same |
| JP2005212339A (en) * | 2004-01-30 | 2005-08-11 | Reiko Co Ltd | Iridescent transfer film and iridescent molded article obtained by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102094175B (en) * | 2010-12-30 | 2012-11-21 | 沈阳金锋特种刀具有限公司 | Powder sintering multicomponent alloy coated target adopting direct water cooling and preparation method thereof |
| JP2017177612A (en) * | 2016-03-30 | 2017-10-05 | 大日本印刷株式会社 | Hard coat film for transfer to electromagnetic wave transmissive decorative member, hard coat layer laminate having base material film, electromagnetic wave transmissive decorative member, and manufacturing method thereof |
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| TW200810948A (en) | 2008-03-01 |
| JPWO2008020482A1 (en) | 2010-01-07 |
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| WO2008020482A1 (en) | 2008-02-21 |
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