JP2007118270A - Manufacturing method of laminate, transparent conductive film and antenna film for non-contact ic card - Google Patents

Manufacturing method of laminate, transparent conductive film and antenna film for non-contact ic card Download PDF

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JP2007118270A
JP2007118270A JP2005310965A JP2005310965A JP2007118270A JP 2007118270 A JP2007118270 A JP 2007118270A JP 2005310965 A JP2005310965 A JP 2005310965A JP 2005310965 A JP2005310965 A JP 2005310965A JP 2007118270 A JP2007118270 A JP 2007118270A
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compound
film
metal foil
base film
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Masanori Matsuda
正則 松田
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SEKISUI FULLER KK
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a laminate which is used in a transparent conductive film or the like and capable of being manufactured without requiring the recovery labor of a solvent and applying load and energy cost to environment. <P>SOLUTION: An adhesive composition, which contains at least either one of a compound (A) having an unsaturated double bond, a compound (B) having the unsaturated double bond and an isocyanate group and a compound (C) having the unsaturated double bond and an epoxy group and a photo-radical polymerization initiator, is applied to at least one of a base material film and a metal foil, and the base material film and the metal foil are superposed one upon another so as to hold to composition. Then, the whole is irradiated with light through the base material film to subject at least one of the compounds (A), (B) and (C) to photopolymerization. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、プラズマディスプレイの電磁波シールド用フィルム等の透明導電性フィルムおよび非接触ICカード用アンテナフィルムなどとなる積層体の製造方法に関する。   The present invention relates to a method for producing a laminate that becomes a transparent conductive film such as an electromagnetic wave shielding film for a plasma display and an antenna film for a non-contact IC card.

非接触ICカードに用いられるアンテナ構成体(インレット)やプラズマディスプレイ(PDP)に用いられる電磁波シールドフィルム等にはポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネートなどからなる基材フィルムと金属箔とを接着剤を用いて貼り合わせた積層体が用いられている。
上記のような積層体は、一般に2液硬化型で溶剤タイプの接着剤を用いて製造されている(例えば、特許文献1参照)。
For electromagnetic shielding films used in antenna structures (inlets) used in non-contact IC cards and plasma displays (PDPs), a base film made of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, etc. and a metal foil are bonded with an adhesive. The laminated body bonded together using is used.
Such a laminate is generally manufactured using a two-component curable solvent-type adhesive (see, for example, Patent Document 1).

特開2002−7990号公報JP 2002-7990 A

しかしながら、上記2液硬化型で溶剤タイプの接着剤を用いた積層体の製造方法では、接着剤が2液硬化型であるため、接着剤の混合装置が必要であることや、溶剤タイプのため乾燥、回収工程が必要であり、環境への負荷が問題となっている。さらに、貼り合わせ後の反応には長時間高温での加熱が必要であるため、エネルギー消費が大きいという問題もある。   However, in the manufacturing method of the laminate using the above-described two-component curable solvent-type adhesive, since the adhesive is a two-component curable type, an adhesive mixing device is required, and the solvent type. Drying and recovery processes are necessary, and the burden on the environment is a problem. Furthermore, since the reaction after bonding requires heating at a high temperature for a long time, there is a problem that energy consumption is large.

一方、光硬化型の接着性組成物を用いれば、脱溶剤化できるとともに、短時間かつ低温で硬化して接着することができるのであるが、従来の光硬化型の接着性組成物を用いた場合、金属箔として主に使用されているアルミニウムや銅との接着性に問題があった。
そこで、本発明の発明者は、イソシアネート基あるいはエポキシ基を有する化合物がアルミニウムや銅に対して優れた接着性を示すことに着目し、鋭意検討を重ねた結果、本発明を完成するに到った。
On the other hand, if a photocurable adhesive composition is used, it can be removed with a solvent, and it can be cured and bonded at a low temperature in a short time, but a conventional photocurable adhesive composition was used. In this case, there was a problem in adhesiveness with aluminum or copper mainly used as a metal foil.
Therefore, the inventors of the present invention pay attention to the fact that the compound having an isocyanate group or an epoxy group exhibits excellent adhesion to aluminum and copper, and as a result of intensive studies, the inventors have completed the present invention. It was.

本発明は、上記事情に鑑みて、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネートなどからなる樹脂基材フィルムと、アルミニウムあるいは銅製の金属箔とが接着層を介してしっかりと積層され、プラズマディスプレイの電磁波シールド用フィルム等の透明導電性フィルムおよび非接触ICカード用アンテナフィルムなどに用いる積層体を溶剤回収の手間がなく、環境に負荷およびエネルギーコストをかけずに製造することができる積層体の製造方法を提供することを目的としている。   In view of the above circumstances, the present invention has a resin base film made of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, etc., and a metal foil made of aluminum or copper, which are firmly laminated via an adhesive layer, and an electromagnetic wave shield for a plasma display. A method of manufacturing a laminate that can be used for transparent conductive films such as film for a film and antenna films for non-contact IC cards without the need for solvent recovery and without burdening the environment and energy costs It is intended to provide.

上記目的を達成するために、本発明にかかる積層体の製造方法は、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネートからなる群より選ばれた一種の樹脂からなる基材フィルムと、アルミニウムまたは銅からなる金属箔とを接着層を介して積層する工程を含む積層体の製造方法であって、前記接着層を、不飽和二重結合を有する化合物(A)と、不飽和二重結合とイソシアネート基を有する化合物(B)および不飽和二重結合とエポキシ基を有する化合物(C)の少なくともいずれかと、光ラジカル重合開始剤とを含む接着性組成物を前記基材フィルムおよび金属箔の少なくともいずれか一方に塗布したのち、前記組成物を間に挟んだ状態で前記基材フィルムと金属箔とを重ね合わせて基材フィルム越しに光を照射し、前記化合物(A)と、化合物(B)および化合物(C)の少なくともいずれかを光重合させて形成することを特徴としている。   In order to achieve the above-mentioned object, a method for producing a laminate according to the present invention includes a base film made of a resin selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, and a metal made of aluminum or copper. A process for producing a laminate comprising a step of laminating a foil with an adhesive layer, wherein the adhesive layer comprises a compound (A) having an unsaturated double bond, an unsaturated double bond and an isocyanate group. An adhesive composition containing at least one of compound (B) and compound (C) having an unsaturated double bond and an epoxy group, and a radical photopolymerization initiator is applied to at least one of the base film and metal foil. After coating, the base film and metal foil are overlapped with the composition sandwiched between them, and light is irradiated through the base film. The compound (A), is characterized in that at least one of the photopolymerized to form compound (B) and compound (C).

本発明の製造方法において、基材フィルムの厚さは、特に限定されないが、15〜100μm程度とすることが好ましい。
金属箔の厚さは、特に限定されないが、5〜60μm程度とすることが好ましい。
In the production method of the present invention, the thickness of the base film is not particularly limited, but is preferably about 15 to 100 μm.
Although the thickness of metal foil is not specifically limited, It is preferable to set it as about 5-60 micrometers.

上記化合物(A)としては、特に限定されないが、例えば、ラウリルアクリレート、メトキシ-トリエチレングリコールアクリレート、フェノキシ-ポリエチレングリコールアクリレート、2−ヒドロキシ−3−フェノキシプロピルアクリレート、2−アクリロイロキシエチル−フタル酸、2−アクリロイルオキシエチルアシッドホスフェート等の単官能アクリレートモノマー、2−ブチル2−エチル−1,3−プロパンジオールジアクリレート、1,9−ノナンジオールジアクリレート、ジメチロール-トリシクロデカンジアクリレート、ビスフェノールAのEO付加物ジアクリレート、トリメチロールプロパントリアクリレート等の多官能アクリレートモノマーが挙げられ、これらが単独であるいは複数混合して用いられる。また、これらのオリゴマーも用いることができる。   The compound (A) is not particularly limited. For example, lauryl acrylate, methoxy-triethylene glycol acrylate, phenoxy-polyethylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-phthalic acid Monofunctional acrylate monomers such as 2-acryloyloxyethyl acid phosphate, 2-butyl 2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, dimethylol-tricyclodecane diacrylate, bisphenol A EO adduct diacrylate, trimethylolpropane triacrylate, and other polyfunctional acrylate monomers may be used, and these may be used alone or in combination. These oligomers can also be used.

上記接着性組成物中の化合物(A)の配合割合は、特に限定されないが、80〜95重量%程度が好ましい。すなわち、化合物(A)の配合割合が80重量%未満では、硬化性が悪くなる可能性があり、95重量%を超えると、接着性が低下する虞がある。   Although the compounding ratio of the compound (A) in the adhesive composition is not particularly limited, it is preferably about 80 to 95% by weight. That is, if the compounding ratio of the compound (A) is less than 80% by weight, the curability may be deteriorated, and if it exceeds 95% by weight, the adhesiveness may be lowered.

上記化合物(B)としては、特に限定されないが、例えば、1級もしくは2級の水酸基を含む(メタ)アクリレートモノマー(オリゴマー)とジイソシアネート化合物(MDI、TDI、HDI等)を反応させて得られるものが好適に用いられる。これらは単独で用いても2種以上を併用してもよい。
上記接着性組成物中の化合物(B)の配合割合は、特に限定されないが、化合物(A)の0.5〜10重量%が好ましく、0.5〜5重量%がより好ましい。すなわち、化合物(B)の配合割合が0.5重量%未満では、イソシアネート基の密着性寄与効果が少なく、10重量%を超えると、イソシアネート基同士の反応により密着性が低下する場合がある。
Although it does not specifically limit as said compound (B), For example, what is obtained by making the (meth) acrylate monomer (oligomer) containing a primary or secondary hydroxyl group react with diisocyanate compounds (MDI, TDI, HDI, etc.). Are preferably used. These may be used alone or in combination of two or more.
Although the compounding ratio of the compound (B) in the said adhesive composition is not specifically limited, 0.5 to 10 weight% of a compound (A) is preferable and 0.5 to 5 weight% is more preferable. That is, if the compounding ratio of the compound (B) is less than 0.5% by weight, the adhesive contribution effect of the isocyanate group is small, and if it exceeds 10% by weight, the adhesion may decrease due to the reaction between the isocyanate groups.

上記化合物(C)としては、特に限定されないが、例えば、脂環式エポキシアクリレート、グリシジルアクリレート等が挙げられ、市販品ではダイセル化学社製脂環式エポキシアクリレート「サイクロマーA−200」や日本化成社製グリシジルアクリレート「4−HBAGE」などが挙げられる。これらは単独で用いても2種以上を併用してもよい。
上記接着性組成物中の化合物(C)の配合割合は、特に限定されないが、化合物(A)の0.5〜10重量%が好ましく、0.5〜5重量%がより好ましい。すなわち、化合物(C)の配合割合が0.5重量%未満では、エポキシ基の密着性寄与効果が少なく、10重量%を超えると、エポキシ基同士の反応により密着性が低下する場合がある。
上記化合物(B)及び上記化合物(C)は、それぞれ単独で用いても併用してもよい。
Although it does not specifically limit as said compound (C), For example, alicyclic epoxy acrylate, glycidyl acrylate, etc. are mentioned, Daicel Chemical Industries alicyclic epoxy acrylate "Cyclomer A-200" and Nippon Kasei are a commercial item. Examples thereof include glycidyl acrylate “4-HBAGE”. These may be used alone or in combination of two or more.
Although the compounding ratio of the compound (C) in the said adhesive composition is not specifically limited, 0.5 to 10 weight% of a compound (A) is preferable and 0.5 to 5 weight% is more preferable. That is, if the compounding ratio of the compound (C) is less than 0.5% by weight, the adhesion contribution effect of the epoxy group is small, and if it exceeds 10% by weight, the adhesion may be lowered due to the reaction between the epoxy groups.
The compound (B) and the compound (C) may be used alone or in combination.

上記光ラジカル重合開始剤としては、特に限定されないが、例えば、α−ヒドロキシ−α,α′−ジメチル−アセトフェノン、4−(2−ヒドロキシエトキシ)フェニル(2−ヒドロキシ−2−プロピル)ケトン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1−ヒドロキシ−シクロヘキシル−フェニル−ケトン、2−メチル−1[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オン等が挙げられる。また、α−ヒドロキシ−α,α′−ジメチル−アセトフェノンの市販品としては、例えば、メルク社製のダロキュア−1173が挙げられ、4−(2−ヒドロキシエトキシ)フェニル(2−ヒドロキシ−2−プロピル)ケトンの市販品としては、例えば、メルク社製のダロキュア−2959が挙げられ、2,2-ジメトキシ−1,2−ジフェニルエタン−1−オンの市販品としては、例えば、チバスペシャルティケミカルズ社製のイルガキュア651が挙げられ、1−ヒドロキシ−シクロヘキシル−フェニル−ケトンの市販品としては、例えば、チバスペシャルティケミカルズ社製のイルガキュア184が挙げられ、2−メチル−1[4−(メチルチオ)フェニル]−2−モルフォリノプロパン−1−オンの市販品としては、例えば、チバスペシャルティケミカルズ社製のイルガキュア907が挙げられる。   Although it does not specifically limit as said radical photopolymerization initiator, For example, (alpha) -hydroxy-alpha, alpha'-dimethyl-acetophenone, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, 2 , 2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc. Is mentioned. Moreover, as a commercial item of α-hydroxy-α, α′-dimethyl-acetophenone, for example, Darocur-1173 manufactured by Merck & Co., Ltd. can be mentioned, and 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) is available. ) Examples of commercially available ketones include Darocur-2959 manufactured by Merck & Co., Ltd., and examples of commercially available 2,2-dimethoxy-1,2-diphenylethane-1-one include, for example, Ciba Specialty Chemicals Irgacure 651, and commercially available products of 1-hydroxy-cyclohexyl-phenyl-ketone include Irgacure 184 manufactured by Ciba Specialty Chemicals, Inc., and 2-methyl-1 [4- (methylthio) phenyl]- Examples of commercially available 2-morpholinopropan-1-one include Irga manufactured by Ciba Specialty Chemicals. Interview A 907, and the like.

上記接着性組成物中の光ラジカル重合開始剤の配合割合は、特に限定されないが、0.5〜5重量%程度がこのましい。すなわち、光ラジカル重合開始剤の配合割合が0.5重量%未満では、効果が小さく、5重量%を超えても硬化性が向上することはない。
なお、光ラジカル重合開始剤は、化合物(A)とあらかじめ混合されていても構わない。
The blending ratio of the radical photopolymerization initiator in the adhesive composition is not particularly limited, but about 0.5 to 5% by weight is preferable. That is, when the blending ratio of the radical photopolymerization initiator is less than 0.5% by weight, the effect is small, and even when it exceeds 5% by weight, the curability is not improved.
The radical photopolymerization initiator may be preliminarily mixed with the compound (A).

また、上記接着性組成物には、さらに、必要に応じて、増感剤、重合禁止剤、酸化防止剤、紫外線吸収剤、光安定剤、消泡剤、レベリング剤、顔料などを含んでいても差し支えない。   The adhesive composition further contains a sensitizer, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a leveling agent, a pigment, and the like as necessary. There is no problem.

上記接着性組成物の基材フィルムあるいは金属箔への塗布方法は、特に限定されないが、例えば、ディップコート法、グラビアコート法、ロールコーター、コンマコーター、スクリーン印刷、ディスペンサー、バーコーター等が挙げられる。
塗布時の条件としては、特に限定されないが、粘度変化を避けるために出来るだけ15〜40℃の範囲で一定温度保持することが好ましい。
A method for applying the adhesive composition to the base film or metal foil is not particularly limited, and examples thereof include a dip coating method, a gravure coating method, a roll coater, a comma coater, screen printing, a dispenser, and a bar coater. .
The conditions at the time of application are not particularly limited, but it is preferable to maintain a constant temperature in the range of 15 to 40 ° C. as much as possible in order to avoid a change in viscosity.

上記接着性組成物に照射される光としては、使用する樹脂の反応性基の種類や量、層の厚さ、含有されるフィラー等の添加剤、触媒の種類や量等により適宜選択され、化合物(A)、及び、化合物(B)及び/又は化合物(C)が光重合すれば、特に限定されないが、請求項4の製造方法のように、100〜3000mJ/cm2(好ましくは100〜2000mJ/cm2)の照射量となるように波長200〜800nmの光を基材フィルム越しに照射することが好ましい。 The light irradiated to the adhesive composition is appropriately selected depending on the type and amount of the reactive group of the resin to be used, the thickness of the layer, additives such as fillers contained, the type and amount of the catalyst, Although it will not specifically limit if a compound (A) and a compound (B) and / or a compound (C) photopolymerize, 100-3000 mJ / cm < 2 > (preferably 100-3000) like the manufacturing method of Claim 4. It is preferable to irradiate light having a wavelength of 200 to 800 nm through the base film so that the irradiation amount is 2000 mJ / cm 2 .

上記光照射に用いられる光源としては、照射により、化合物(A)、及び、化合物(B)及び/又は化合物(C)が光重合可能であれば特に限定されないが、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ブラックライトランプ、マイクロウェーブ励起水銀灯、メタルハライドランプ、ナトリウムランプ、蛍光灯等の各種ランプや太陽光のような自然光が挙げられる。   The light source used for the light irradiation is not particularly limited as long as the compound (A) and the compound (B) and / or the compound (C) can be photopolymerized by irradiation. Examples include mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, fluorescent lamps, and other natural light such as sunlight.

得られる積層体の接着層の厚さは、特に限定されることなく、対象物体の種類や用途によって適宜決定するとよい。
そして、本発明の製造方法で得られる積層体は、特に限定されないが、例えば、プラズマディスプレイの電磁波シールド用フィルムなどの透明導電性フィルムや、非接触ICカード用アンテナフィルムとして好適である。
The thickness of the adhesive layer of the obtained laminate is not particularly limited, and may be appropriately determined depending on the type and application of the target object.
And the laminated body obtained with the manufacturing method of this invention is although it does not specifically limit, For example, it is suitable as transparent conductive films, such as an electromagnetic wave shielding film of a plasma display, and an antenna film for non-contact IC cards.

上記透明導電性フィルムや、非接触ICカード用アンテナフィルムは、特に限定されないが、一般的には、本発明の製造方法で得られた積層体の金属箔の不要部分をフォトレジスト法等により除去することによって製造することができる。   The transparent conductive film and the non-contact IC card antenna film are not particularly limited, but generally, unnecessary portions of the metal foil of the laminate obtained by the production method of the present invention are removed by a photoresist method or the like. Can be manufactured.

本発明にかかる積層体の製造方法は、以上のように、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネートからなる群より選ばれた一種の樹脂からなる基材フィルムと、アルミニウムまたは銅からなる金属箔とを接着層を介して積層する工程を含む積層体の製造方法であって、前記接着層を、不飽和二重結合を有する化合物(A)と、不飽和二重結合とイソシアネート基を有する化合物(B)および不飽和二重結合とイソシアネート基を有する化合物(C)の少なくともいずれかと、光ラジカル重合開始剤とを含む接着性組成物を前記基材フィルムおよび金属箔の少なくともいずれか一方に塗布したのち、前記組成物を間に挟んだ状態で前記基材フィルムと金属箔とを重ね合わせて基材フィルム越しに光を照射し、前記化合物(A)と、化合物(B)および化合物(C)の少なくともいずれかを光重合させて形成するようにしたので、樹脂基材フィルムと、金属箔とが接着層を介してしっかりと積層され、接着層が末端にアルミニウムおよび銅との接着性に優れたイソシアネート基および/またはエポキシ基を備えた重合体から構成され、プラズマディスプレイの電磁波シールド用フィルムなどの透明導電性フィルムや、非接触ICカード用アンテナフィルムとして有効に用いることができる積層体を得ることができる。   As described above, the method for producing a laminate according to the present invention comprises a base film made of a resin selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polycarbonate, and a metal foil made of aluminum or copper. A method for producing a laminate comprising a step of laminating via an adhesive layer, wherein the adhesive layer comprises a compound (A) having an unsaturated double bond, a compound having an unsaturated double bond and an isocyanate group (B ) And at least one of the compound (C) having an unsaturated double bond and an isocyanate group, and a radical photopolymerization initiator are applied to at least one of the base film and the metal foil. The base film and the metal foil are overlapped with the composition sandwiched between them and irradiated with light through the base film. Since the compound (A) is formed by photopolymerization of at least one of the compound (B) and the compound (C), the resin base film and the metal foil are firmly laminated via the adhesive layer. The adhesive layer is composed of a polymer having an isocyanate group and / or an epoxy group excellent in adhesion to aluminum and copper at the end, and is a transparent conductive film such as an electromagnetic wave shielding film for plasma display, or a non-contact IC A laminate that can be used effectively as an antenna film for a card can be obtained.

すなわち、接着性組成物は、化合物(A)、化合物(B)および/または化合物(C)の不飽和二重結合が光の照射で光重合して重合体となり硬化して基材フィルムをしっかりと接着するとともに、この重合体がイソシアネート基および/またはエポキシ基を備えているので、イソシアネート基および/またはエポキシ基が金属箔をしっかりと接着する。   That is, in the adhesive composition, the unsaturated double bond of the compound (A), the compound (B) and / or the compound (C) is photopolymerized by light irradiation to become a polymer and harden the substrate film firmly. Since the polymer has isocyanate groups and / or epoxy groups, the isocyanate groups and / or epoxy groups firmly adhere the metal foil.

以下に、本発明の具体的な実施例をその比較例と対比させて詳しく説明する。なお、本発明は、以下の実施例に限定されるものではない。   Hereinafter, specific examples of the present invention will be described in detail in comparison with comparative examples. The present invention is not limited to the following examples.

(実施例1)
2-ヒドロキシプロピルアクリレート(共栄社化学社製水酸基含有単官能アクリレート「HOP-A」)100gと、4,4'-ジフェニルメタンジイソシアネート(住化バイエル社製)20gとを窒素下で約45℃で1時間反応させて化合物(B)となる化合物Iを得た。
約200mLのサンプル瓶内で、化合物(A)としての2-ヒドロキシ-3フェノキシプロピルアクリレート(共栄社化学社製エポキシエステルM-600A)50g、化合物(A)としてのリン酸系エポキシアクリレート(ダイセルサイテック社製RDX63182)50g、化合物(A)としての2-アクリロイロキシエチルフタル酸(共栄社化学社製HOA-MPL単官能フタル酸系ラジカル重合性物質)25g、光ラジカル重合開始剤(チバスペシャルティケミカルズ社製イルガキュア651)2g、化合物(B)としての上記化合物I6gを混合し、接着性組成物を得た。
Example 1
2-Hydroxypropyl acrylate (Kyoeisha Chemical Co., Ltd., hydroxyl-containing monofunctional acrylate "HOP-A") and 4,4'-diphenylmethane diisocyanate (Sumika Bayer) 20g under nitrogen at about 45 ° C for 1 hour The compound I which becomes a compound (B) by reacting was obtained.
In a sample bottle of about 200 mL, 50 g of 2-hydroxy-3phenoxypropyl acrylate (epoxy ester M-600A manufactured by Kyoeisha Chemical Co., Ltd.) as compound (A), and phosphoric acid epoxy acrylate (Daicel Cytec Co., Ltd.) as compound (A) RDX63182) 50g, 2-acryloyloxyethylphthalic acid (25%) as a compound (A) (HOA-MPL monofunctional phthalic acid radical polymerizable substance manufactured by Kyoeisha Chemical Co., Ltd.), photo radical polymerization initiator (Ciba Specialty Chemicals) 2 g of Irgacure 651) and 6 g of the above compound I as compound (B) were mixed to obtain an adhesive composition.

(実施例2)
化合物Iに代えて、化合物(C)としてのグリシジルアクリレート(日本化成社製「4−HBAGE」)を用いた以外は実施例1と同様にして接着性組成物を得た。
(Example 2)
An adhesive composition was obtained in the same manner as in Example 1, except that glycidyl acrylate (“4-HBAGE” manufactured by Nippon Kasei Co., Ltd.) as the compound (C) was used in place of the compound I.

(比較例1)
化合物Iを除外した以外は実施例1と同様にして接着性組成物を得た。
(Comparative Example 1)
An adhesive composition was obtained in the same manner as in Example 1 except that Compound I was excluded.

上記実施例1,2および比較例1で得た接着性組成物を、それぞれコロナ処理PETフィルム(約100μ厚)に塗布するとともに、アルミニウム箔(約30μm厚)の間で厚さ約10μmになるよう調整して貼り合わせ、高圧水銀灯を用い、1200mJ/cm2 の照射量となるように光線を照射したのち、室温で48時間放置して、積層体を得た。
つぎに、得られた積層体についてそれぞれ180°剥離で50mm/minの速度で引っ張り、接着強度を測定し、その結果を表1に示した。
Each of the adhesive compositions obtained in Examples 1 and 2 and Comparative Example 1 was applied to a corona-treated PET film (about 100 μm thick), and the thickness was about 10 μm between aluminum foils (about 30 μm thick). After adjusting and sticking together, using a high-pressure mercury lamp, irradiating with a light beam so that the irradiation amount was 1200 mJ / cm 2 , it was left at room temperature for 48 hours to obtain a laminate.
Next, each of the obtained laminates was pulled at a rate of 50 mm / min at 180 ° peeling, and the adhesive strength was measured. The results are shown in Table 1.

Figure 2007118270
Figure 2007118270

表1から、本発明の製造方法のように、接着性組成物として、不飽和二重結合を有する化合物(A)と、不飽和二重結合とイソシアネート基を有する化合物(B)および不飽和二重結合とエポキシ基を有する化合物(C)の少なくともいずれかと、光ラジカル重合開始剤とを含むものを用いれば、金属箔に対して高い接着性を発現でき、プラズマディスプレイの電磁波シールド用フィルム等の透明導電性フィルムおよび非接触ICカード用アンテナフィルムなどに好適な積層体を得られることがよくわかる。 From Table 1, as in the production method of the present invention, as the adhesive composition, the compound (A) having an unsaturated double bond, the compound (B) having an unsaturated double bond and an isocyanate group and If a compound containing at least one of the compound (C) having a heavy bond and an epoxy group and a radical photopolymerization initiator is used, high adhesion to a metal foil can be exhibited, such as an electromagnetic wave shielding film for a plasma display. It can be seen that a laminate suitable for a transparent conductive film, a non-contact IC card antenna film, and the like can be obtained.

Claims (7)

ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリカーボネートからなる群より選ばれた一種の樹脂からなる基材フィルムと、
アルミニウムまたは銅からなる金属箔とを接着層を介して積層する工程を含む積層体の製造方法であって、
前記接着層を、不飽和二重結合を有する化合物(A)と、不飽和二重結合とイソシアネート基を有する化合物(B)および不飽和二重結合とエポキシ基を有する化合物(C)の少なくともいずれかと、光ラジカル重合開始剤とを含む接着性組成物を前記基材フィルムおよび金属箔の少なくともいずれか一方に塗布したのち、前記組成物を間に挟んだ状態で前記基材フィルムと金属箔とを重ね合わせて基材フィルム越しに光を照射し、前記化合物(A)と、化合物(B)および化合物(C)の少なくともいずれかを光重合させて形成することを特徴とする積層体の製造方法。
A base film made of a kind of resin selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, and polycarbonate;
A method for producing a laminate including a step of laminating a metal foil made of aluminum or copper via an adhesive layer,
The adhesive layer is composed of at least one of a compound (A) having an unsaturated double bond, a compound (B) having an unsaturated double bond and an isocyanate group, and a compound (C) having an unsaturated double bond and an epoxy group. And an adhesive composition containing a radical photopolymerization initiator is applied to at least one of the base film and the metal foil, and then the base film and the metal foil are sandwiched between the compositions. Is produced by irradiating light through a base film and photopolymerizing at least one of the compound (A), the compound (B) and the compound (C). Method.
基材フィルムの厚さが15〜100μmである請求項1に記載の積層体の製造方法。   The manufacturing method of the laminated body of Claim 1 whose thickness of a base film is 15-100 micrometers. 金属箔の厚さが5〜60μmである請求項1または請求項2に記載の積層体の製造方法。   The manufacturing method of the laminated body of Claim 1 or Claim 2 whose thickness of metal foil is 5-60 micrometers. 100〜3000mJ/cm2の照射量となるように波長200〜800nmの光を基材フィルム越しに照射する請求項1〜請求項3のいずれかに記載の積層体の製造方法。 The manufacturing method of the laminated body in any one of Claims 1-3 which irradiates light with a wavelength of 200-800 nm through a base film so that it may become an irradiation amount of 100-3000mJ / cm < 2 >. 請求項1〜請求項4のいずれかに記載の積層体の製造方法によって得られることを特徴とする透明導電性フィルム。   The transparent conductive film obtained by the manufacturing method of the laminated body in any one of Claims 1-4. プラズマディスプレイの電磁波シールド用フィルムである請求項5に記載の透明導電性フィルム。   The transparent conductive film according to claim 5, which is an electromagnetic wave shielding film for a plasma display. 請求項1〜請求項4のいずれかに記載の積層体の製造方法によって得られることを特徴とする非接触ICカード用アンテナフィルム。   An antenna film for a non-contact IC card obtained by the method for producing a laminate according to any one of claims 1 to 4.
JP2005310965A 2005-10-26 2005-10-26 Manufacturing method of laminate, transparent conductive film and antenna film for non-contact ic card Withdrawn JP2007118270A (en)

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