JP3608956B2 - Metal thin film laminate for molding - Google Patents
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- JP3608956B2 JP3608956B2 JP28350298A JP28350298A JP3608956B2 JP 3608956 B2 JP3608956 B2 JP 3608956B2 JP 28350298 A JP28350298 A JP 28350298A JP 28350298 A JP28350298 A JP 28350298A JP 3608956 B2 JP3608956 B2 JP 3608956B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、プラスチックの射出成形品および押出成形品等の分野において、特に成形物面が平面でない場合に良好な金属光沢をこれらの成形物（製品）表面に付与するための同時成形等に使用する成形用金属薄膜積層体に関する。
すなわち、本発明の成形用金属薄膜積層体を、例えば成形金型内にセットし、該金型を使用してＡＢＳ樹脂、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂等を射出成形することによって、成形と同時に成形品に金属光沢を付与することが出来る同時成形用金属薄膜積層体等の成形用金属薄膜積層体に関するものである。
【０００２】
【従来の技術】
従来、プラスチック成形品表面の金属加飾表面処理方法として、本発明と同様の同時成形転写方法は提案されている。例えば、アルミニウムやクロム等の金属薄膜層を有する転写材を使用して各種プラスチック成形製品に射出成形等と同時に全面もしくは部分的に金属光沢を付与している。
【０００３】
【発明が解決しようとする課題】
近年成形品の形状がより複雑になってきており、例えば射出成形時に樹脂が溶融し金型内に流入するゲート部分で、同時成形用転写箔の接着剤層の流動変形に伴い、そのことによって金属薄膜層にも歪みが起こり、歪みに追随変形し得ない金属薄膜層に亀裂などが発生し、得られた製品の金属光沢に欠陥を発生せしめることがしばしば見られる。
この対策として金属薄膜層をゲート部分には設けないなどのデザイン上の工夫をしたり、成形品そのもののデザインを犠牲にして複雑形状部を減少せしめるなどの工夫が講じられてきた。
また、金属薄膜層の厚さを小さくし、金属光沢性を犠牲にし金属薄膜の変形追随をえんとするものも提案されているが、折角の金属光沢性が不満足な場合がしばしば発生するものであった。
【０００４】
さらに、金属薄膜層の亀裂を予め覚悟して、特開平６−１３５１９８号公報に開示されているように、金属粉体層を以って亀裂による欠陥をカバーする方法も提案されているが金属層が二重になる等経済的にも有利とは言えないものであるし、金属薄膜の光沢を完全に補完しうる場合ばかりではないものであった。
また、特公昭６０−１１６３３号公報に開示のように金属薄膜層に特定の金属薄膜を使用することも提案されているが、該金属薄膜層が成形時に非平面表面への追随性を有してはいるが、該金属薄膜層を支持している基体そのものについての工夫が特になく通常ポリエチレンテレフタレートフイルム等を使用した時同時成形等に使用した時十分な効果が得られない。
本発明は、前記従来の成形用転写箔等の課題を解決し、射出成形時に同時成形用転写箔中の接着剤層の流動に伴う金属薄膜層の破壊や、成形時におこる金属薄膜層の変形追随性不足による金属薄膜層の亀裂発生を防止し、金属光沢に優れた金属調加飾成形性品を得るため等に、成形用金属薄膜積層体を提供するものである。
【０００５】
【課題を解決するための手段】
即ち本発明は、フイルム基材に、少なくとも金属薄膜層を形成・積層した積層体であって、金属薄膜層がインジウム又はインジウム系合金である金属または合金からなる厚さ１０〜３０ｎｍの金属薄膜層であり、フイルム基材がエチレンテレフタレート単位が８５ｍｏｌ％以上でエチレンテレフタレート以外の単位が３ｍｏｌ％以上であるポリエステル系フイルムである、ことを特徴とする成形用金属薄膜積層体であり、ポリエステル系フイルムの厚さが２０〜７５μｍである前記の成形用金属薄膜積層体であり、またフイルム基材が、融点２００〜２５０℃のエチレンテレフタレート単位が８５ｍｏｌ％以上でエチレンテレフタレート以外の単位が３ｍｏｌ％以上であるポリエステル系フイルムである前記の成形用金属薄膜積層体である。
【０００６】
【発明の実施態様】
本発明は、上記したように、例えば同時成形転写時に金属薄膜層が、亀裂等の欠陥を発生する原因が、金属薄膜層構成の金属そのものが、変形追随性を成形時の変形に対して有していないこととそれを支持している基材フイルムの性状にあると考え、インジウム又はインジウム合金を使用して特定厚さの金属薄膜層を作製することと支持基体であるフイルム基材に特定のポリエステル系フイルムを使用することで課題を解決したものである。
本発明のフイルム基材としては、ポリエチレンテレフタレートに他のエステル形成性単量体を共重合して得られる共重合ポリエステルのポリエステル系フイルムが用いられる。
他のエステル形成性単量体としては特に限定される物ではなく、得られた共重合ポリエステルの融点が２００〜２５０℃のものであればよく、例として挙げれば、ジエチレングリコール、トリエチレングリコール等のポリオキシアルキレングリコール、ブタンジオール、シクロヘキサンジオール、等のエチレングリコール以外のジオール成分、イソフタル酸、ナフタレン酸、シクロヘキサンジカルボン酸、アジピン酸、等のテレフタル酸以外のジカルボン酸成分、更には、ジオール、ジカルボン酸以外の多官能エステル形成成分がある。
本願発明に使用されるポリエステル系フイルムは、エチレンテレフタレート単位が８５ｍｏｌ％以上で、エチレンテレフタレート以外の単位が３ｍｏｌ％以上であるポリエステル系フイルムであり、エチレンテレフタレート単位が８５ｍｏｌ％に未満のとき成形流動性においては満足できても、金属薄膜層形成時の熱などに耐えることに不充分であり、エチレンテレフタレート以外の単位が３ｍｏｌ％未満のときは、金属薄膜層形成時の熱などに耐えることに充分であっても、成形流動性においては不充分である。このエチレンテレフタレート単位は好ましくは９０ｍｏｌ％以上であり、エチレンテレフタレート以外の単位は好ましくは４．０ｍｏｌ％以上のポリエステル系フイルムであり、さらに好ましくはエチレンテレフタレート単位は好ましくは９０ｍｏｌ％以上であり、エチレンテレフタレート以外の単位は好ましくは５．０ｍｏｌ％以上のポリエステル系フイルムである。
本願発明に使用されるポリエステル系フイルムは、エチレンテレフタレート単位が８５ｍｏｌ％以上でエチレンテレフタレート以外の単位が３ｍｏｌ％以上であるポリエステルであって、その融点が２００〜２５０℃のものであることが望ましい。
また、本願発明に使用されるポリエステル系フイルムは、そのフイルムの性能が▲１▼破断強度が縦方向で１５〜２５ｋｇｆ／ｍｍ２、横方向で１５〜２５ｋｇｆ／ｍｍ２であり、▲２▼破断伸度が縦方向で１５０％以上、横方向で１５０％以上であり、▲３▼１５０℃３０分での熱収縮率が縦方向で１．５〜５．０％、横方向で１．２〜５．０％であるものが好ましい。
【０００７】
上記該基材フイルムの性能は、本願発明の金属薄膜層を該フイルム面上に形成するための手段、蒸着、スパッタリング、イオンプレーテイングなど乾式薄膜形成法における熱等に耐え得ることと、例えば非平面保有成形物の表面に本願発明の成形用金属薄膜積層体を接合する際の非平面への追随性との両者を同時に満足せしめるために必要なものである。
これらのフイルムの厚さは特に限定されるものではないが、金属薄膜層形成時の耐性と、成形物表面へ適用された時の金属薄膜層保持性等から、２０〜７５μｍであることが好ましい。
【０００８】
本発明に用いられる金属薄膜層形成は、インジウム金属、銀−インジウム合金、ビスマス−インジウム合金、銅−インジウム合金、インジウム−リチウム合金、インジウム−鉛合金、インジウム−アンチモン合金、インジウム−錫合金、インジウム−亜鉛合金等から選ばれる一種または二種以上である合金が好ましく使用される。
【０００９】
本発明における金属薄膜層の厚さは、好ましくは１０ｎｍ以上３０ｎｍ以下であり、更に好ましくは１４ｎｍ以上２２ｎｍ以下である。かかる範囲の膜厚さにすることで、金属光輝性が充分であり、薄膜にクラックが発生し難く、絶縁性をも保持し、経済的にも優れているものとなる。
１０ｎｍに満たないときは、光輝性（金属光沢性）において、その性能は乏しく、３０ｎｍを超えるときは、金属光沢性はこれ以上厚さを大きくしても影響が少ない上に経済的にも得策ではなく、クラックの発生が起こり易くなる。
この金属薄膜層のフイルム基材上への形成は、その方法において特に限定されるものではなく、蒸着、スパッタリング、イオンプレーテイングなど乾式薄膜形成法が適宜使用される。合金薄膜層の形成には合金組成を均一に保つためにスパッタリング法が好ましい。
【００１０】
本願発明の、成形用金属薄膜積層体は、特定性能を保有するポリエステル系フイルム基材に、インジウム又はインジウム系合金である金属または合金からなる金属薄膜層を積層したものを基本とするものであるが、特定性能を保有するポリエステル系フイルム基材をＡとし、インジウム又はインジウム系合金である金属または合金からなる金属薄膜層をＢとしたとき、Ａ／Ｂの構成に剥離層（Ｃ）、着色層（Ｄ）、絵柄層（Ｅ）、保護層（Ｆ）、や他のオリゴマー防止層や密着向上層や背面強化層や装飾層等を適宜付加せしめてもよいものである。
【００１１】
例えば、転写材としての本願発明の応用例の場合は、フイルム基材に金属薄膜層形成に先立って、離型層、保護層を形成し、金属薄膜層形成後、接着剤層を形成することを基本とするものである。離型層は、転写後にフイルム基材を成形品から剥離する場合には必要な場合がありその時には、フイルム基材に離型層を形成するが、フイルム基材が離型性がある場合またはフイルム基材を転写後も剥離しない時には形成しなくてもよいものであり、その形成は、アクリル系樹脂、塩素化オレフィン樹脂、パラフィンワックス、合成ワックスを使用して、グラビア印刷法、スクリーン印刷法等印刷法やロールコーター法等で実施される。保護層は、本発明の金属薄膜層を保護するためのものであり例えば、アクリルウレタン樹脂、アクリルビニル樹脂、アクリル樹脂、ビニルウレタン樹脂等を使用し、必要に応じて着色材で着色してもよく、また形成時に模様を印刷したものでもよい。
本発明における接着剤層は、成形時の加熱、加圧により転写材を成形製品の表面に接着固定するためのものであり、感熱溶融性接着剤が好ましく使用される。この感熱溶融性接着剤は同時成形するプラスチックの種類に応じて、特に転写材と接する最外層のプラスチックの種類に応じて、適宜より好ましいものを選択し使用する。
たとえばＡＢＳ樹脂、ポリカーボネート樹脂と同時成形するときはアクリル樹脂を、相手がポリオレフィンの場合は塩素化ポリオレフィン樹脂、塩素化エチレン・酢ビ樹脂を使用する。
またＡ／Ｂの構成に保護層（Ｆ）を形成したＡ／Ｂ／Ｆの構成でＡ側に、成形物構成素材との接着性に優れた接着剤層を塗布して成形物に圧着成形してもよい。
本願発明は、Ａ／Ｂの構成を基本とするものであり、他の応用例を制限するものではない。
【００１２】
【実施例】
＊＊実施例１
厚さ３０μｍ（ミクロン）の▲１▼破断強度が縦方向で２０．５ｋｇｆ／ｍｍ２、横方向で１９．９ｋｇｆ／ｍｍ２であり、▲２▼破断伸度が縦方向で１８０％、横方向で１８７％であり、▲３▼１５０℃３０分での熱収縮率が縦方向で２．４％、横方向で１．５％である、イソフタル酸３．５モル％とナフタレンジカルボン酸１．５モル％を共重合した共重合ポリエステルからの、ポリエステル系フイルム（結果的に重合時に生成するジエチレングリコールが１．０％含有され、該フイルムは、エチレンテレフタレート単位が９４ｍｏｌ％含有され、エチレンテレフタレート単位以外の単位が６ｍｏｌ％含有されたものである）に、アクリル樹脂溶液（ＮＶ＝２５％）をグラビヤコーテイングにより乾燥膜厚約１μｍ（ミクロン）に塗布形成して離型層を設けた。該離型層上にアクリルウレタン樹脂溶液（ＮＶ＝３０％）をグラビヤコーテイングにより乾燥膜厚約１μｍ（ミクロン）に塗布形成して保護層を設けた。該保護層上に、インジウムを真空蒸着法によって２０ｎｍの膜厚になるように金属薄膜層を形成した。該金属薄膜層上にアクリル樹脂をリバースコーテイングにより接着剤層を３μｍ（ミクロン）厚で形成し成形用金属薄膜積層体転写箔を得た。
【００１３】
＊＊実施例２
厚さ５０μｍの▲１▼破断強度が縦方向で２１．５ｋｇｆ／ｍｍ２、横方向で２０．９ｋｇｆ／ｍｍ２であり、▲２▼破断伸度が縦方向で１６８％、横方向で１７２％であり、▲３▼１５０℃３０分での熱収縮率が縦方向で２．６％、横方向で１．３％である、ブタンジオール２．０モル％とシクロヘキサンジメタノールを３．０モル％共重合した共重合ポリエステルからのポリエステルフイルム（結果的に重合時に生成するジエチレングリコールが１．０％含有され、該フイルムは、エチレンテレフタレート単位が９４ｍｏｌ％含有され、エチレンテレフタレート単位以外の単位が６ｍｏｌ％含有されたものである）に、ニトロセルロース樹脂溶液（ＮＶ＝１０％）をグラビヤコーテイングにより乾燥膜厚約１μｍに塗布形成して離型層を設けた。該離型層上にアクリルウレタン樹脂溶液（ＮＶ＝２５％）をグラビヤコーテイングにより乾燥膜厚約２μｍに塗布形成して保護層を設けた。該保護層上に、銀−インジウム合金（融点２８０℃）をスパッタリング法によって１８．５ｎｍの膜厚になるように金属薄膜層を形成した。該金属薄膜層上にアクリル樹脂をリバースコーテイングにより接着剤層を２μｍ厚で形成し成形用金属薄膜積層体転写箔を得た。
【００１４】
＊＊比較例１
実施例１での、フイルム基材を、厚さ３０μｍ（ミクロン）の▲１▼破断強度が縦方向で２２．５ｋｇｆ／ｍｍ２、横方向で２１．９ｋｇｆ／ｍｍ２であり、▲２▼破断伸度が縦方向で１１０％、横方向で１２７％であり、▲３▼１５０℃３０分での熱収縮率が縦方向で１．１％、横方向で−０．４％であるポリエチレンテレフタレートフイルム（結果的に重合時に生成するジエチレングリコールが１．０％含有され、該フイルムは、エチレンテレフタレート単位が９９ｍｏｌ％含有され、エチレンテレフタレート単位以外の単位が１ｍｏｌ％含有されたものである）を用いた以外は同じようにして、成形用金属薄膜積層体転写箔を得た。
上記の実施例１、２と比較例１の成形用金属薄膜積層体転写箔をそれぞれ表面が平面でない湾曲部を有する三次元成形品用成形金型内にセットし、ＡＢＳ樹脂を射出圧着成形し、成形後基材フイルムを剥離したところ、実施例１、２共良好な金属調光沢を有する三次元成形性品が得られた。比較例１の場合は金属薄膜の一部に亀裂が見られた。
【００１５】
【発明の効果】
プラスチックの射出成形品および押出成形品等の分野において、本発明の成形用金属薄膜積層体を使用して同時成形したときに、金属薄膜の亀裂等の発生がなく、成形品に安定して金属光沢を付与することができた。[0001]
BACKGROUND OF THE INVENTION
The present invention is used in the field of plastic injection molded products and extrusion molded products, etc., particularly for simultaneous molding for imparting a good metallic luster to the surfaces of these molded products (products) especially when the molded product surface is not flat. The present invention relates to a forming metal thin film laminate.
That is, the molding metal thin film laminate of the present invention is set in, for example, a molding die, and by using the die, an ABS resin, an acrylic resin, a polycarbonate resin, a polyester resin, and the like are injection-molded. The present invention relates to a metal thin film laminate for molding such as a metal thin film laminate for simultaneous molding capable of imparting metallic luster to a molded product at the same time.
[0002]
[Prior art]
Conventionally, a simultaneous molding transfer method similar to that of the present invention has been proposed as a metal decorative surface treatment method for the surface of a plastic molded product. For example, using a transfer material having a metal thin film layer such as aluminum or chrome, various plastic molded products are given a metallic luster in whole or in part at the same time as injection molding.
[0003]
[Problems to be solved by the invention]
In recent years, the shape of molded products has become more complicated, for example, at the gate part where the resin melts during injection molding and flows into the mold, along with the flow deformation of the adhesive layer of the simultaneous molding transfer foil, It is often observed that the metal thin film layer is also distorted, cracks are generated in the metal thin film layer that cannot be deformed following the distortion, and defects are generated in the metallic luster of the obtained product.
As countermeasures, there have been devised design measures such as not providing a metal thin film layer at the gate portion, or reducing complex shape portions at the expense of the design of the molded product itself.
In addition, there have been proposals to reduce the thickness of the metal thin film layer and to follow the deformation of the metal thin film at the expense of the metal gloss, but the metal gloss at the corner is often unsatisfactory. there were.
[0004]
Furthermore, as disclosed in Japanese Patent Application Laid-Open No. 6-135198, a method for covering defects due to cracks with a metal powder layer has been proposed in preparation for cracks in the metal thin film layer. It cannot be said that it is economically advantageous because the layers are doubled, and it is not only when the gloss of the metal thin film can be completely complemented.
In addition, as disclosed in Japanese Patent Publication No. 60-11633, it has been proposed to use a specific metal thin film for the metal thin film layer, but the metal thin film layer has a followability to a non-planar surface during molding. However, there is no particular idea about the substrate itself supporting the metal thin film layer, and when a polyethylene terephthalate film or the like is usually used, sufficient effects cannot be obtained when used for simultaneous molding.
The present invention solves the problems of the conventional molding transfer foil and the like, breaks the metal thin film layer due to the flow of the adhesive layer in the simultaneous molding transfer foil during injection molding, and deforms the metal thin film layer during molding. The present invention provides a metal thin film laminate for forming in order to prevent the occurrence of cracks in the metal thin film layer due to insufficient followability and to obtain a metal-like decorative moldability product having excellent metallic luster.
[0005]
[Means for Solving the Problems]
That is, the present invention is a laminate in which at least a metal thin film layer is formed and laminated on a film substrate, and the metal thin film layer is made of a metal or an alloy that is indium or an indium alloy and has a thickness of 10 to 30 nm. The film base material is a polyester film having an ethylene terephthalate unit of 85 mol% or more and a unit other than ethylene terephthalate of 3 mol% or more. The molding metal thin film laminate having a thickness of 20 to 75 μm, and the film base has an ethylene terephthalate unit having a melting point of 200 to 250 ° C. of 85 mol% or more and a unit other than ethylene terephthalate is 3 mol% or more. It is the said metal thin film laminated body for shaping | molding which is a polyester-type film.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
As described above, according to the present invention, for example, the metal thin film layer has a defect such as a crack at the time of simultaneous molding and transfer. It is considered to be the property of the substrate film supporting it and the film film supporting it, and using indium or an indium alloy to produce a metal thin film layer of a specific thickness and specifying the film substrate as a supporting substrate The problem has been solved by using a polyester film.
As the film substrate of the present invention, a polyester film of a copolymerized polyester obtained by copolymerizing polyethylene terephthalate with another ester-forming monomer is used.
The other ester-forming monomer is not particularly limited, and it is sufficient that the obtained copolymer polyester has a melting point of 200 to 250 ° C. Examples include diethylene glycol and triethylene glycol. Diol components other than ethylene glycol such as polyoxyalkylene glycol, butanediol and cyclohexanediol, dicarboxylic acid components other than terephthalic acid such as isophthalic acid, naphthalene acid, cyclohexanedicarboxylic acid and adipic acid, and diols and dicarboxylic acids There are other polyfunctional ester forming components.
The polyester-based film used in the present invention is a polyester-based film having an ethylene terephthalate unit of 85 mol% or more and a unit other than ethylene terephthalate of 3 mol% or more. When the ethylene terephthalate unit is less than 85 mol%, molding fluidity is obtained. However, when the unit other than ethylene terephthalate is less than 3 mol%, it is sufficient to withstand the heat at the time of forming the metal thin film layer. However, the molding fluidity is insufficient. The ethylene terephthalate unit is preferably 90 mol% or more, the unit other than ethylene terephthalate is preferably 4.0 mol% or more of a polyester film, more preferably the ethylene terephthalate unit is preferably 90 mol% or more, and ethylene terephthalate. The unit other than is preferably a polyester film of 5.0 mol% or more.
The polyester film used in the present invention is a polyester having an ethylene terephthalate unit of 85 mol% or more and a unit other than ethylene terephthalate of 3 mol% or more, and preferably has a melting point of 200 to 250 ° C.
Moreover, polyester films for use in the present invention, 15~25kgf / mm 2 performance of the film is ▲ 1 ▼ breaking strength in the longitudinal direction, in the transverse direction was 15~25kgf / mm 2, ▲ 2 ▼ break The elongation is 150% or more in the longitudinal direction and 150% or more in the transverse direction. (3) The thermal shrinkage at 150 ° C. for 30 minutes is 1.5 to 5.0% in the longitudinal direction and 1.2 in the transverse direction. What is -5.0% is preferable.
[0007]
The performance of the substrate film can withstand the heat in the dry thin film forming method such as means for forming the metal thin film layer of the present invention on the film surface, vapor deposition, sputtering, ion plating, etc. This is necessary in order to satisfy both the followability to a non-planar surface at the same time when the metal thin film laminate for molding of the present invention is joined to the surface of the flat holding molded product.
Although the thickness of these films is not particularly limited, it is preferably 20 to 75 μm from the standpoint of resistance when forming a metal thin film layer and retention of the metal thin film layer when applied to the surface of a molded product. .
[0008]
The metal thin film layer used in the present invention is formed of indium metal, silver-indium alloy, bismuth-indium alloy, copper-indium alloy, indium-lithium alloy, indium-lead alloy, indium-antimony alloy, indium-tin alloy, indium. -One or more alloys selected from zinc alloys and the like are preferably used.
[0009]
The thickness of the metal thin film layer in the present invention is preferably 10 nm or more and 30 nm or less, and more preferably 14 nm or more and 22 nm or less. By setting the film thickness within such a range, the metal glitter is sufficient, cracks are not easily generated in the thin film, the insulating property is maintained, and the cost is excellent.
When the thickness is less than 10 nm, the performance of the luster (metal gloss) is poor. When the thickness exceeds 30 nm, the metal gloss has little effect even if the thickness is increased further, and it is economically advantageous. Instead, cracks are likely to occur.
The formation of the metal thin film layer on the film substrate is not particularly limited in the method, and a dry thin film forming method such as vapor deposition, sputtering, or ion plating is appropriately used. For forming the alloy thin film layer, a sputtering method is preferable in order to keep the alloy composition uniform.
[0010]
The metal thin film laminate for molding of the present invention is based on a laminate of a metal thin film layer made of a metal or alloy that is indium or an indium alloy on a polyester film substrate having specific performance. However, when the polyester film base material having specific performance is A and the metal thin film layer made of indium or an indium alloy metal or alloy is B, the peeling layer (C) is colored in the structure of A / B. A layer (D), a pattern layer (E), a protective layer (F), other oligomer prevention layers, adhesion improving layers, back reinforcing layers, decorative layers, and the like may be appropriately added.
[0011]
For example, in the case of the application example of the present invention as a transfer material, a release layer and a protective layer are formed on the film substrate prior to the formation of the metal thin film layer, and an adhesive layer is formed after the metal thin film layer is formed. It is based on. The release layer may be necessary when the film substrate is peeled off from the molded product after the transfer.At that time, the release layer is formed on the film substrate. When the film substrate is not peeled off after transfer, it does not need to be formed. For the formation, gravure printing method, screen printing method using acrylic resin, chlorinated olefin resin, paraffin wax, synthetic wax It is carried out by an equal printing method or a roll coater method. The protective layer is for protecting the metal thin film layer of the present invention. For example, an acrylic urethane resin, an acrylic vinyl resin, an acrylic resin, a vinyl urethane resin, or the like may be used, and the protective layer may be colored with a coloring material as necessary. The pattern may be printed at the time of formation.
The adhesive layer in the present invention is for adhering and fixing the transfer material to the surface of the molded product by heating and pressurization during molding, and a heat-sensitive melt adhesive is preferably used. As the heat-meltable adhesive, a more preferable one is appropriately selected according to the type of plastic to be molded at the same time, particularly according to the type of the outermost plastic layer in contact with the transfer material.
For example, an acrylic resin is used when co-molding with an ABS resin or a polycarbonate resin, and a chlorinated polyolefin resin or a chlorinated ethylene / vinyl acetate resin is used when the partner is a polyolefin.
In addition, an A / B / F configuration in which a protective layer (F) is formed on the A / B configuration is coated on the A side with an adhesive layer that is excellent in adhesion to the molded component material, and is pressure-bonded to the molded product. May be.
The present invention is based on the A / B configuration and does not limit other application examples.
[0012]
【Example】
** Example 1
Thickness 30μm of (microns) ▲ 1 ▼ breaking strength in the longitudinal direction 20.5kgf / mm 2, in the transverse direction was 19.9kgf / mm 2, ▲ 2 ▼ 180% elongation at break in the longitudinal direction, transverse direction (3) Thermal shrinkage at 150 ° C. for 30 minutes is 2.4% in the vertical direction and 1.5% in the horizontal direction, 3.5 mol% of isophthalic acid and naphthalene dicarboxylic acid 1. Polyester film from a copolymerized polyester copolymerized with 5 mol% (resulting in 1.0% of diethylene glycol formed during polymerization, which contains 94 mol% of ethylene terephthalate units, other than ethylene terephthalate units) The acrylic resin solution (NV = 25%) is applied to a dry film thickness of about 1 μm (micron) by gravure coating. And a release layer was provided. An acrylic urethane resin solution (NV = 30%) was applied and formed on the release layer to a dry film thickness of about 1 μm (micron) by gravure coating to provide a protective layer. A metal thin film layer was formed on the protective layer so that indium had a thickness of 20 nm by vacuum deposition. On the metal thin film layer, an acrylic resin was reverse coated to form an adhesive layer with a thickness of 3 μm (micron) to obtain a metal thin film laminate transfer foil for molding.
[0013]
** Example 2
Thickness 50μm ▲ 1 ▼ 21.5kgf / mm 2 breaking strength in the longitudinal direction, a 20.9kgf / mm 2 in the transverse direction, ▲ 2 ▼ 168% elongation at break in the longitudinal direction, in the transverse direction 172% (3) The heat shrinkage at 150 ° C. for 30 minutes is 2.6% in the vertical direction and 1.3% in the horizontal direction, and 2.0 mol% of butanediol and 3.0 mol of cyclohexanedimethanol. % Polyester film from copolymerized polyester (resulting in 1.0% diethylene glycol produced during polymerization, which contains 94 mol% ethylene terephthalate units and 6 mol% units other than ethylene terephthalate units) The release layer is formed by applying a nitrocellulose resin solution (NV = 10%) to a dry film thickness of about 1 μm by gravure coating. Provided. On the release layer, an acrylic urethane resin solution (NV = 25%) was applied and formed in a dry film thickness of about 2 μm by gravure coating to provide a protective layer. On the protective layer, a metal thin film layer was formed by sputtering a silver-indium alloy (melting point: 280 ° C.) to a thickness of 18.5 nm. On the metal thin film layer, an acrylic resin was reverse-coated to form an adhesive layer with a thickness of 2 μm to obtain a metal thin film laminate transfer foil for molding.
[0014]
** Comparative example 1
In Example 1, a film substrate, the thickness 30μm of the (microns) ▲ 1 ▼ 22.5kgf / mm 2 breaking strength in the longitudinal direction, a 21.9kgf / mm 2 in the transverse direction, ▲ 2 ▼ break Polyethylene terephthalate having an elongation of 110% in the machine direction and 127% in the transverse direction, and (3) heat shrinkage at 150 ° C. for 30 minutes of 1.1% in the machine direction and −0.4% in the transverse direction. A film (consequently containing 1.0% of diethylene glycol produced during polymerization, the film containing 99 mol% of ethylene terephthalate units and 1 mol% of units other than ethylene terephthalate units) was used. Except for the above, a metal thin film laminate transfer foil for molding was obtained in the same manner.
Each of the molding metal thin film laminate transfer foils of Examples 1 and 2 and Comparative Example 1 described above is set in a molding die for a three-dimensional molded product having a curved portion whose surface is not flat, and an ABS resin is injection-bonded and molded. When the base film was peeled off after molding, a three-dimensional formable product having good metallic gloss was obtained in both Examples 1 and 2. In the case of Comparative Example 1, a crack was observed in a part of the metal thin film.
[0015]
【The invention's effect】
In the fields of plastic injection molded products and extrusion molded products, when the metal thin film laminate for molding of the present invention is used for simultaneous molding, there is no occurrence of cracks in the metal thin film, and the molded product is stable. Glossiness could be imparted.
Claims (1)
前記金属薄膜層が、
インジウム又はインジウム系合金である金属又は合金からなり、また厚さが１０ｎｍ〜３０ｎｍであり、
前記フィルム基材が、
融点２００〜２５０℃のエチレンテレフタレート単位が８５ｍｏｌ％以上で、エチレンテレフタレート以外の単位が３ｍｏｌ％以上であり、
また厚さが２０ｎｍ〜７５μｍである、ポリエステル系フィルムであること、
を特徴とする、成型用金属薄膜積層体。A laminate in which at least a metal thin film layer is formed and laminated on a film substrate,
The metal thin film layer is
It consists of a metal or alloy that is indium or an indium-based alloy, and has a thickness of 10 nm to 30 nm,
The film substrate is
The ethylene terephthalate unit having a melting point of 200 to 250 ° C. is 85 mol% or more, and the units other than ethylene terephthalate are 3 mol% or more,
Moreover, it is a polyester-type film whose thickness is 20 nm-75 micrometers,
A metal thin film laminate for molding, characterized by
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| Application Number | Priority Date | Filing Date | Title |
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| JP28350298A JP3608956B2 (en) | 1998-09-18 | 1998-09-18 | Metal thin film laminate for molding |
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| Application Number | Priority Date | Filing Date | Title |
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| JP28350298A JP3608956B2 (en) | 1998-09-18 | 1998-09-18 | Metal thin film laminate for molding |
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| JP2000094575A JP2000094575A (en) | 2000-04-04 |
| JP3608956B2 true JP3608956B2 (en) | 2005-01-12 |
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| JP28350298A Expired - Fee Related JP3608956B2 (en) | 1998-09-18 | 1998-09-18 | Metal thin film laminate for molding |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6942911B2 (en) | 2000-04-27 | 2005-09-13 | 3M Innovative Properties Company | Display member having metallic luster |
| JP2001312232A (en) * | 2000-04-27 | 2001-11-09 | Three M Innovative Properties Co | Display body having metallic luster |
| JP2006264593A (en) * | 2005-03-25 | 2006-10-05 | Toyota Motor Corp | Shaped article of luminosity ornament used in beam path of radar device |
| JP4667923B2 (en) | 2005-03-25 | 2011-04-13 | トヨタ自動車株式会社 | Brightening molded parts for radar device beam path |
| KR101248299B1 (en) * | 2005-03-28 | 2013-03-27 | 도레이 카부시키가이샤 | Biaxially oriented polyester film and metal-like laminated films |
| JP2006297853A (en) * | 2005-04-25 | 2006-11-02 | Teijin Dupont Films Japan Ltd | Film for use in molding |
| JP4826200B2 (en) * | 2005-10-18 | 2011-11-30 | 東レ株式会社 | Biaxially oriented polyester film for molded parts |
| JP4668771B2 (en) * | 2005-11-14 | 2011-04-13 | 小島プレス工業株式会社 | Touch switch with a metal-finished design surface |
| CN101426646B (en) | 2006-04-19 | 2013-10-09 | 东丽株式会社 | Biaxially oriented polyester film for molded part |
| JP2021074978A (en) * | 2019-11-11 | 2021-05-20 | 尾池工業株式会社 | Layered film, metallic tone product, and metallic signage |
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