JP6516108B2 - Electromagnetic wave shield laminate for vacuum forming, and electromagnetic wave shield molded body using the same - Google Patents
Electromagnetic wave shield laminate for vacuum forming, and electromagnetic wave shield molded body using the same Download PDFInfo
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- JP6516108B2 JP6516108B2 JP2017155602A JP2017155602A JP6516108B2 JP 6516108 B2 JP6516108 B2 JP 6516108B2 JP 2017155602 A JP2017155602 A JP 2017155602A JP 2017155602 A JP2017155602 A JP 2017155602A JP 6516108 B2 JP6516108 B2 JP 6516108B2
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- resin
- electromagnetic wave
- layer
- laminate
- wave shield
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Description
本発明は真空成形用電磁波シールド積層体およびこれを用いた電磁波シールド成形体に関する。 The present invention relates to an electromagnetic shielding laminate for vacuum forming and an electromagnetic shielding molded article using the same.
近年、パーソナルコンピュータなどのデジタル電子機器の筐体に合成樹脂の射出成形品が多用されている。そして、合成樹脂の筐体内で発生した電磁波が外部へ漏出するため、この電磁波の漏出を防ぐために、導電性材料からなるシールド材を内部表面に密着させた筐体が用いられている。 2. Description of the Related Art In recent years, injection molded articles of synthetic resin are widely used in the housings of digital electronic devices such as personal computers. Then, since the electromagnetic wave generated in the case of the synthetic resin leaks to the outside, in order to prevent the leakage of the electromagnetic wave, a case in which a shielding material made of a conductive material is in close contact with the inner surface is used.
特許文献１には、電気部品を収容する植物繊維を加圧成形した筐体の表面にメッキ処理をすることで電磁波遮蔽機能を有するシールドケースが開示されている。
特許文献２には、メッキ処理や真空蒸着に代るシールド形成手法として、アルミ蒸着フィルムおよび接着層を積層したシールド転写材が開示されており、インモールド成形によって成形品の表面に電磁波シールド性を付与することで、コスト及び生産性を向上すると記載されている。
特許文献３には、インモールド成形または真空圧空成形に用いる転写材に関し、離型性を有する基体シートの表面に、保護層、絵柄層および接着層が形成された転写材において、透明性および柔軟性を有する電磁波シールド層を介在させたことを特徴とする転写材が開示されている。
Patent Document 1 discloses a shield case having an electromagnetic wave shielding function by plating a surface of a casing obtained by pressure molding a plant fiber containing an electrical component.
Patent Document 2 discloses a shield transfer material in which an aluminum vapor deposition film and an adhesive layer are laminated as a shield forming method instead of plating treatment and vacuum evaporation, and electromagnetic shielding properties are formed on the surface of a molded article by in-mold molding. It is stated that the application improves cost and productivity.
Patent Document 3 relates to a transfer material used for in-mold molding or vacuum pressure forming, and in the transfer material in which a protective layer, a picture layer and an adhesive layer are formed on the surface of a substrate sheet having releasability, Disclosed is a transfer material characterized in that an electromagnetic wave shielding layer having a property is interposed.
上述した成形法の中でも、真空成形および真空圧空成形（以下、真空成形と略す）はインモールド成形と比較して、筐体の必要な箇所に部分的にシールド性を付与できる点、凹型凸型のどちらの形状にも対応できる点、大型サイズの筐体にも好適である点から積極的に導入検討が進められている。しかし、従来の転写材を真空成形でシールド層を形成しようとすると、成形体の複雑な形状、特に凹凸の段差部で追従できず浮きが生じる問題があった（以下、高段差追従性）。また、成形時に電磁波シールド層が引き伸ばされるため、導電性が低下しシールド特性が劣化する問題があった。加えて、膜強度が低く、例えば搬送中に部品同士が擦れた際にシールド層が破壊されシールド性が低下する問題があった（以下、引っ掻き耐性と省略）。 Among the above-described molding methods, vacuum molding and vacuum pressure molding (hereinafter, abbreviated as vacuum molding) are capable of partially imparting shielding properties to the necessary places of the casing as compared to in-mold molding, concave convex The introduction and examination is actively advanced from the point that it can correspond to either of the above and the point that it is suitable also for a large-sized case. However, when forming a shield layer by vacuum molding of a conventional transfer material, there is a problem that it can not follow at the complicated shape of the molded body, particularly at the stepped portion of the unevenness, and floating occurs (hereinafter, high step following ability). In addition, since the electromagnetic wave shield layer is stretched at the time of molding, there is a problem that the conductivity is lowered and the shield property is deteriorated. In addition, there is a problem that the film strength is low, for example, when parts are rubbed during transportation, the shield layer is broken and the shieldability is reduced (hereinafter, scratch resistance is omitted).
本発明は、複雑な形状の成形体に対しても良好に追従密着し、耐摩耗性が優れ、成形体に高い電磁波シールド性を付与できる真空成形用電磁波シールド積層体および、電磁波シールド成形体を提供することを目的とする。 The present invention is an electromagnetic wave shield laminate for vacuum forming that adheres well to a complex shaped molded object, has excellent wear resistance, and can impart high electromagnetic wave shielding properties to the molded object, and an electromagnetic wave shield molded body Intended to be provided.
本発明者らが鋭意検討を重ねたところ、以下の態様において、本発明の課題を解決し得ることを見出し、本発明を完成するに至った。
即ち、本発明は、電磁波シールド層（Ａ）と、粘着層（Ｂ）とを有する真空成形用電磁波シールド積層体であって、前記電磁波シールド層（Ａ）は導電性樹脂層および金属層の少なくともいずれかであり、前記積層体のたて方向、またはよこ方向の少なくともいずれかの方向を、１５０℃で１．５倍の長さになるまで伸張したときのＫＥＣ法における周波数１ＧＨｚでの電磁波シールド性が４０〜９０ｄＢである真空成形用電磁波シールド積層体に関する。
As a result of intensive studies by the present inventors, the inventors have found that the problems of the present invention can be solved in the following embodiments, and have completed the present invention.
That is, the present invention is an electromagnetic shielding laminate for vacuum forming having an electromagnetic wave shielding layer (A) and an adhesive layer (B), wherein the electromagnetic wave shielding layer (A) is at least at least a conductive resin layer and a metal layer. It is an electromagnetic wave shield at a frequency of 1 GHz in the KEC method when any one of the longitudinal direction and / or the transverse direction of the laminate is stretched to 1.5 times the length at 150 ° C. The present invention relates to an electromagnetic shielding laminate for vacuum forming having an elasticity of 40 to 90 dB.
上記構成の本発明によれば、複雑な形状の成形体に対しても良好に追従密着し、成形体に高い電磁波シールド性を付与できる真空成形用電磁波シールド積層体および、電磁波シールド成形体を提供できる。 According to the present invention of the above configuration, there is provided an electromagnetic wave shielding laminate for vacuum forming, which adheres well to a complex shaped molded article and can impart high electromagnetic wave shielding properties to the molded article, and an electromagnetic wave shield molded article. it can.
以下、本発明を適用した実施形態の一例について説明する。尚、以降の図における各部材のサイズや比率は、説明の便宜上のものであり、これに限定されるものではない。また、本明細書において「任意の数Ａ〜任意の数Ｂ」なる記載は、当該範囲に数Ａが下限値として、数Ｂが上限値として含まれる。また、本明細書における「シート」とは、ＪＩＳにおいて定義される「シート」のみならず、「フィルム」も含むものとする。また、本明細書において特定する数値は、実施形態または実施例に開示した方法により求められる値である。 Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, the size and ratio of each member in subsequent figures are for convenience of description, and are not limited to this. Further, in the present specification, the description “arbitrary number A to arbitrary number B” includes the number A as the lower limit and the number B as the upper limit in the range. In addition, "sheet" in the present specification includes not only "sheet" defined in JIS but also "film". Also, the numerical values specified in the present specification are values obtained by the method disclosed in the embodiment or the example.
《真空成形用電磁波シールド積層体》
本発明に係る真空成形用電磁波シールド積層体は、図１に示すように、少なくとも粘着層（Ｂ）、および電磁波シールド層（Ａ）が積層された積層体である。真空成形用電磁波シールド積層体は、部品（不図示）上に粘着層（Ｂ）を配置し、接合処理により当該部品と接合することができる。接合処理は、真空成形によるものであり、本発明における真空成形とは、フィルムやシートを加熱して軟化させ真空引きすることで被着体の立体形状に沿うように張り付ける成型方法であり、真空引きのみで成形する真空成形及び真空引きと加圧を同時に行う真空圧空成形を含む。電磁波シールド層（Ａ）は、主として電磁波をシールドする役割を担う。プリント配線板においては、部品内部の信号配線等から発生する電磁ノイズをシールドしたり、外部からの信号を遮蔽する役割を担う。
<< Electromagnetic wave shield laminate for vacuum forming >>
The electromagnetic wave shielding laminate for vacuum forming according to the present invention is, as shown in FIG. 1, a laminated body in which at least an adhesive layer (B) and an electromagnetic wave shielding layer (A) are laminated. An adhesive layer (B) can be disposed on a component (not shown) for a vacuum forming electromagnetic wave shield laminate, and the component can be bonded to the component by a bonding process. The bonding process is performed by vacuum forming, and the vacuum forming in the present invention is a forming method in which the film or sheet is heated, softened, and vacuum drawn to adhere along the three-dimensional shape of the adherend, It includes vacuum forming that is formed only by vacuum drawing and vacuum pressure forming that is performed simultaneously with vacuum drawing and pressurization. The electromagnetic wave shielding layer (A) mainly plays a role of shielding electromagnetic waves. The printed wiring board plays a role of shielding electromagnetic noise generated from signal wiring and the like inside parts and shielding signals from the outside.
本発明の真空成形用電磁波シールド積層体は、導電性樹脂層および金属層の少なくともいずれかである電磁波シールド層（Ａ）と、粘着層（Ｂ）とを含む積層体であって、積層体に対して水平方向に、前記積層体のたて方向、またはよこ方向の少なくともいずれかの方向に、１５０℃で１．５倍の長さになるまで伸張したときのＫＥＣ法における周波数１ＧＨｚでの電磁波シールド性が４０〜９０ｄＢである。上記の条件で伸張したときの電磁波シールド性が４０〜９０ｄＢであることで、高段差に追従しつつ立体成形体の全面に高い電磁波シールド性が付与できる。伸張したときの電磁波シールド性は４５〜９０ｄＢが好ましく、５０〜９０ｄＢがより好ましい。 The electromagnetic wave shielding laminate for vacuum forming of the present invention is a laminate including an electromagnetic wave shielding layer (A) which is at least one of a conductive resin layer and a metal layer, and an adhesive layer (B), The electromagnetic wave at a frequency of 1 GHz in the KEC method when stretched to a length 1.5 times at 150 ° C. in the horizontal direction, in the vertical direction of the laminate, or in at least one of the horizontal directions. The shielding performance is 40 to 90 dB. When the electromagnetic wave shielding property when expanded under the above conditions is 40 to 90 dB, high electromagnetic wave shielding property can be imparted to the entire surface of the three-dimensional molded body while following the high level difference. 45-90 dB is preferable and 50-90 dB is more preferable for electromagnetic wave shielding property when extending | stretching.
本発明の真空成形用電磁波シールド積層体の伸張の上限は、立体成型体の電磁波シールド性を高める観点から１５０℃で５倍以下が好ましく、３倍以下がより好ましい。 The upper limit of the expansion of the electromagnetic shielding laminate for vacuum forming of the present invention is preferably 5 times or less at 150 ° C., more preferably 3 times or less, from the viewpoint of enhancing the electromagnetic wave shielding property of the three-dimensional molded body.
＜電磁波シールド層（Ａ）＞
電磁波シールド層（Ａ）は、層内において導電性を示し、電磁波を遮蔽する層であり、導電性樹脂層または金属層であって、導電性樹脂層および金属層を有していてもよい。
電磁波シールド層（Ａ）に金属層を用いる場合、引っ掻き耐性に優れる。一方導電性樹脂層を用いる場合、高段差追従性に優れる。
導電性接着剤層および金属層の積層構成とする場合、粘着層（Ｂ）はどちらの層に積層されてもよい。
<Electromagnetic wave shield layer (A)>
The electromagnetic wave shielding layer (A) is a layer which exhibits conductivity in the layer and shields an electromagnetic wave, may be a conductive resin layer or a metal layer, and may have a conductive resin layer and a metal layer.
When a metal layer is used for the electromagnetic wave shielding layer (A), the scratch resistance is excellent. On the other hand, when using a conductive resin layer, it is excellent in high level difference followability.
In the case of the laminated constitution of the conductive adhesive layer and the metal layer, the pressure-sensitive adhesive layer (B) may be laminated on either layer.
［導電性樹脂層］
導電性樹脂層はバインダー樹脂および導電性フィラーを含む層であって、熱によって硬化する層である。また導電性樹脂層は等方性の導電性を示す層である。等方性とは、電磁波シールド層を水平に置いた状態で、上下方向および水平方向に導電性を有する物である。
[Conductive resin layer]
The conductive resin layer is a layer containing a binder resin and a conductive filler, and is a layer which is cured by heat. The conductive resin layer is a layer exhibiting isotropic conductivity. Isotropic is a substance having conductivity in the vertical direction and in the horizontal direction with the electromagnetic wave shielding layer placed horizontally.
導電性樹脂層の２５〜１５０℃での線膨張係数は、１００〜７００ｐｐｍ／℃の範囲とすることが好ましい。この範囲とすることにより、段差でのクラックを効果的に防止し、且つ、高段差追従性を向上できる。より好ましい範囲は１２５〜６５０ｐｐｍ／℃であり、さらに好ましい範囲は１５０〜６００ｐｐｍ／℃であり、特に好ましい範囲は１７５〜５５０ｐｐｍ／℃である。 The linear expansion coefficient at 25 to 150 ° C. of the conductive resin layer is preferably in the range of 100 to 700 ppm / ° C. By setting it as this range, the crack in a level | step difference can be prevented effectively and high level | step difference followability can be improved. A more preferable range is 125 to 650 ppm / ° C., a further preferable range is 150 to 600 ppm / ° C., and a particularly preferable range is 175 to 550 ppm / ° C.
導電性樹脂層は、引張破断歪が５０〜１５００％であることが好ましい。引張破断歪が上記範囲であることで、真空成形時の凹凸形状への追従性を高め、段差による導電性樹脂層の破断を効果的に防止し、且つ段差部分での導電性樹脂層の伸びを良好にすることができる。引張破断歪のより好ましい範囲は１００〜１４００％であり、さらに好ましい範囲は１５０〜１３００％であり、特に好ましい範囲は２００〜１０００％である。 The conductive resin layer preferably has a tensile strain at break of 50 to 1,500%. When the tensile breaking strain is in the above-mentioned range, the followability to the concavo-convex shape at the time of vacuum molding is improved, the fracture of the conductive resin layer due to the step is effectively prevented, and the elongation of the conductive resin layer at the step portion Can be good. The more preferable range of the tensile strain at break is 100 to 1,400%, the more preferable range is 150 to 1,300%, and the particularly preferable range is 200 to 1,000%.
導電性樹脂層におけるバインダー樹脂は、熱硬化性樹脂を使用できる。
熱硬化性樹脂は、加熱による架橋反応に利用できる官能基を複数有する樹脂である。
官能基は、例えば、水酸基、フェノール性水酸基、カルボキシル基、アミノ基、エポキシ基、オキセタニル基、オキサゾリン基、オキサジン基、アジリジン基、チオール基、イソシアネート基、ブロック化イソシアネート基、シラノール基等が挙げられる。
A thermosetting resin can be used as a binder resin in the conductive resin layer.
The thermosetting resin is a resin having a plurality of functional groups that can be used for the crosslinking reaction by heating.
Examples of functional groups include hydroxyl group, phenolic hydroxyl group, carboxyl group, amino group, epoxy group, oxetanyl group, oxazoline group, oxazine group, oxazine group, aziridine group, thiol group, isocyanate group, blocked isocyanate group, silanol group and the like. .
上記の官能基を有する熱硬化性樹脂は、例えば、アクリル樹脂、マレイン酸樹脂、ポリブタジエン系樹脂、ポリエステル樹脂、縮合型ポリエステル樹脂、付加型ポリエステル樹脂、メラミン樹脂、ポリウレタン樹脂、ポリウレタンウレア樹脂、エポキシ樹脂、オキセタン樹脂、フェノキシ樹脂、ポリイミド樹脂、ポリアミド樹脂、フェノール系樹脂、アルキド樹脂、アミノ樹脂、ポリ乳酸樹脂、オキサゾリン樹脂、ベンゾオキサジン樹脂、シリコーン樹脂、フッ素樹脂等が挙げられる。これらの中でも表面抵抗値と耐摩耗性の点から、ポリウレタン樹脂、ポリウレタンウレア樹脂、エポキシ樹脂、付加型ポリエステル樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂が好ましい。 The thermosetting resin having the above functional group includes, for example, acrylic resin, maleic acid resin, polybutadiene resin, polyester resin, condensation type polyester resin, addition type polyester resin, melamine resin, polyurethane resin, polyurethane urea resin, epoxy resin And oxetane resin, phenoxy resin, polyimide resin, polyamide resin, phenol resin, alkyd resin, amino resin, polylactic acid resin, oxazoline resin, benzoxazine resin, silicone resin, fluorine resin and the like. Among these, polyurethane resins, polyurethane urea resins, epoxy resins, addition type polyester resins, polyimide resins, polyamide resins and polyamide imide resins are preferable from the viewpoint of surface resistance value and abrasion resistance.
熱硬化性樹脂を用いる場合硬化剤を併用することが好ましい。硬化剤は、熱硬化性樹脂中の官能基と反応可能な官能基を複数有している。硬化剤は、エポキシ化合物、酸無水物基含有化合物、イソシアネート化合物、アジリジン化合物、ジシアンジアミド、芳香族ジアミン等のアミン化合物、フェノールノボラック樹脂等のフェノール化合物等が好ましい。 When using a thermosetting resin, it is preferable to use a curing agent in combination. The curing agent has a plurality of functional groups capable of reacting with the functional groups in the thermosetting resin. The curing agent is preferably an epoxy compound, an acid anhydride group-containing compound, an isocyanate compound, an aziridine compound, an amine compound such as dicyandiamide or an aromatic diamine, or a phenol compound such as a phenol novolac resin.
硬化剤は、熱硬化性樹脂１００質量部に対して１〜５０質量部含むことが好ましく、３〜３０質量部がより好ましく、３〜２０質量部がさらに好ましい。 The curing agent is preferably contained in an amount of 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the thermosetting resin.
また熱硬化性樹脂に熱可塑性樹脂を併用することもできる。
熱可塑性樹脂は、前記硬化性官能基を有しないポリオレフィン系樹脂、ビニル系樹脂、スチレン・アクリル系樹脂、ジエン系樹脂、テルペン樹脂、石油樹脂、セルロース系樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリイミド系樹脂、フッ素樹脂などが挙げられる。
ポリオレフィン系樹脂は、エチレン、プロピレン、α−オレフィン化合物などのホモポリマーまたはコポリマーが好ましい。具体的には、例えば、ポリエチレンプロピレンゴム、オレフィン系熱可塑性エラストマー、α−オレフィンポリマー等が挙げられる。
ビニル系樹脂は、酢酸ビニルなどのビニルエステルの重合により得られるポリマーおよびビニルエステルとエチレンなどのオレフィン化合物とのコポリマーが好ましい。具体的には、例えば、エチレン−酢酸ビニル共重合体、部分ケン化ポリビニルアルコール等が挙げられる。
スチレン・アクリル系樹脂は、スチレンや（メタ）アクリロニトリル、アクリルアミド類、（メタ）アクリル酸エステル、マレイミド類などからなるホモポリマーまたはコポリマーが好ましい。具体的には、例えば、シンジオタクチックポリスチレン、ポリアクリロニトリル、アクリルコポリマー、エチレン−メタクリル酸メチル共重合体等が挙げられる。
ジエン系樹脂は、ブタジエンやイソプレン等の共役ジエン化合物のホモポリマーまたはコポリマーおよびそれらの水素添加物が好ましい。具体的には、例えば、スチレン−ブタジエンゴム、スチレン−イソプレンブロックコポリマー等が挙げられる。
テルペン樹脂は、テルペン類からなるポリマーまたはその水素添加物が好ましい。具体的には、例えば、芳香族変性テルペン樹脂、テルペンフェノール樹脂、水添テルペン樹脂が挙げられる。
石油系樹脂は、ジシクロペンタジエン型石油樹脂、水添石油樹脂が好ましい。
セルロース系樹脂は、セルロースアセテートブチレート樹脂が好ましい。
ポリカーボネート樹脂は、ビスフェノールＡポリカーボネートが好ましい。
ポリイミド系樹脂は、熱可塑性ポリイミド、ポリアミドイミド樹脂、ポリアミック酸型ポリイミド樹脂が好ましい。
In addition, a thermoplastic resin can be used in combination with a thermosetting resin.
The thermoplastic resin is a polyolefin resin having no curable functional group, a vinyl resin, a styrene-acrylic resin, a diene resin, a terpene resin, a petroleum resin, a cellulose resin, a polyamide resin, a polyurethane resin, a polyester resin, Polycarbonate resin, polyimide resin, fluorine resin, etc. may be mentioned.
The polyolefin resin is preferably a homopolymer or copolymer such as ethylene, propylene and an α-olefin compound. Specifically, for example, polyethylene propylene rubber, olefin-based thermoplastic elastomer, α-olefin polymer and the like can be mentioned.
The vinyl resin is preferably a polymer obtained by the polymerization of a vinyl ester such as vinyl acetate and a copolymer of a vinyl ester and an olefin compound such as ethylene. Specifically, for example, ethylene-vinyl acetate copolymer, partially saponified polyvinyl alcohol and the like can be mentioned.
The styrene / acrylic resin is preferably a homopolymer or copolymer comprising styrene, (meth) acrylonitrile, acrylamides, (meth) acrylic acid esters, maleimides and the like. Specifically, for example, syndiotactic polystyrene, polyacrylonitrile, acrylic copolymer, ethylene-methyl methacrylate copolymer and the like can be mentioned.
The diene resin is preferably a homopolymer or copolymer of a conjugated diene compound such as butadiene or isoprene and a hydrogenated product thereof. Specifically, for example, styrene-butadiene rubber, styrene-isoprene block copolymer and the like can be mentioned.
The terpene resin is preferably a polymer of terpenes or a hydrogenated product thereof. Specifically, for example, aromatic modified terpene resin, terpene phenol resin, hydrogenated terpene resin can be mentioned.
The petroleum resin is preferably a dicyclopentadiene type petroleum resin or a hydrogenated petroleum resin.
The cellulose resin is preferably a cellulose acetate butyrate resin.
The polycarbonate resin is preferably bisphenol A polycarbonate.
The polyimide resin is preferably a thermoplastic polyimide, a polyamideimide resin, or a polyamic acid type polyimide resin.
導電性フィラーは、金属フィラー、導電性セラミックス粒子およびそれらの混合物が例示できる。金属フィラーは、金、銀、銅、ニッケル等の金属粉、ハンダ等の合金粉、銀コート銅粉、金コート銅粉、銀コートニッケル粉、金コートニッケル粉のコアシェル型粒子が例示できる。優れた導電特性を得る観点から、銀を含有する導電性フィラーが好ましい。コストの観点からは、銀コート銅粉が特に好ましい。銀コート銅における銀の含有量は、１〜２０質量％が好ましく、より好ましくは２〜１５質量％であり、更に好ましくは３〜１０質量％である。コアシェル型粒子の場合、コア部に対するコート層の被覆率は、平均で６０％以上が好ましく、７０％以上がより好ましく、８０％以上がさらに好ましい。コア部は非金属でもよいが、導電性の観点からは導電性物質が好ましく、金属粒子がより好ましい。 The conductive filler can be exemplified by metal fillers, conductive ceramic particles and mixtures thereof. Examples of the metal filler include core-shell particles of metal powder such as gold, silver, copper and nickel, alloy powder such as solder, silver-coated copper powder, gold-coated copper powder, silver-coated nickel powder and gold-coated nickel powder. Silver-containing conductive fillers are preferred from the viewpoint of obtaining excellent conductive properties. Silver-coated copper powder is particularly preferred from the viewpoint of cost. The content of silver in the silver-coated copper is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and still more preferably 3 to 10% by mass. In the case of the core-shell type particles, the coverage of the coating layer on the core portion is preferably 60% or more on average, more preferably 70% or more, and still more preferably 80% or more. The core portion may be nonmetal, but from the viewpoint of conductivity, a conductive material is preferable, and metal particles are more preferable.
導電性フィラーとして、電磁波吸収フィラーを用いてもよい。例えば、鉄、Ｆｅ−Ｎｉ合金、Ｆｅ−Ｃｏ合金、Ｆｅ−Ｃｒ合金、Ｆｅ−Ｓｉ合金、Ｆｅ−Ａｌ合金、Ｆｅ−Ｃｒ−Ｓｉ合金、Ｆｅ−Ｃｒ−Ａｌ合金、Ｆｅ−Ｓｉ−Ａｌ合金等の鉄合金、Ｍｇ−Ｚｎフェライト、Ｍｎ−Ｚｎフェライト、Ｍｎ−Ｍｇフェライト、Ｃｕ−Ｚｎフェライト、Ｍｇ−Ｍｎ−Ｓｒフェライト、Ｎｉ−Ｚｎフェライト等のフェライト系物質が例示できる。 An electromagnetic wave absorbing filler may be used as the conductive filler. For example, iron, Fe-Ni alloy, Fe-Co alloy, Fe-Cr alloy, Fe-Si alloy, Fe-Al alloy, Fe-Cr-Si alloy, Fe-Cr-Al alloy, Fe-Si-Al alloy, etc. Iron-based alloys, Mg-Zn ferrites, Mn-Zn ferrites, Mn-Mg ferrites, Cu-Zn ferrites, Mg-Mn-Sr ferrites, Ni-Zn ferrites and the like.
導電性フィラーの形状は、引っ掻き耐性と段差追従性を高める観点からフレーク状が好ましい。加えて、フレーク状粒子を用いることで、導電性フィラー同士の接触を良好とし、立体成形体の段差における抵抗値を良好にすることができる。その結果、被覆性を良好にし、シールド性を高めることができる。また、フレーク状粒子と他の形状の粒子を併用してもよい。併用する粒子形状は特に限定されないが、樹枝（デンドライト）状粒子、繊維状粒子、針状粒子および球状粒子からなる群から選択される粒子が好ましい。併用する粒子は、単独または混合して用いられる。併用する場合、フレーク状粒子および樹枝状粒子の組み合わせ、フレーク状粒子、樹枝状粒子および球状粒子の組み合わせ、フレーク状粒子および球状粒子の組み合わせが例示できる。これらのうち、電磁波シールド層の被覆性を高め、且つシールド性を高める観点から、フレーク状粒子単独またはフレーク状粒子と樹枝状粒子を組み合わせがより好ましい。 The shape of the conductive filler is preferably flake from the viewpoint of enhancing scratch resistance and step followability. In addition, by using flake-like particles, the contact between the conductive fillers can be improved, and the resistance value at the step of the three-dimensional molded object can be improved. As a result, coverage can be improved and shielding can be enhanced. In addition, flaky particles and particles of other shapes may be used in combination. The shape of the particles to be used in combination is not particularly limited, but particles selected from the group consisting of dendrite-like particles, fibrous particles, needle-like particles and spherical particles are preferable. The particles used in combination may be used alone or in combination. When used in combination, a combination of flake-like particles and dendritic particles, a combination of flake-like particles, dendritic particles and spherical particles, and a combination of flake-like particles and spherical particles can be exemplified. Among these, flake-like particles alone or a combination of flake-like particles and dendritic particles are more preferable from the viewpoint of enhancing the covering property of the electromagnetic wave shielding layer and enhancing the shielding property.
フレーク状粒子は、下記数式（１）から求められる円径度係数が０．１５以上、０．４以下である導電性フィラーを好適に用いることができる。このような導電性フィラーとしては、例えば、国際公開ＷＯ２０１３／００１３５１号に記載の粒子が例示できる。
ここでいう円径度係数は、Mac-View Ver.4（マウンテック社）の解析ソフトを用いて、導電性フィラーの電子顕微鏡画像（千倍〜１万倍程度）を読み込み、手動認識モードで導電性粒子を約２０個選択する。葉状やフレーク状の粒子を選択する際は、粒子同士が重なっていない粒子形状全体が確認できるものであって、観察視点から平面板が垂直になる角度のものを抽出して選択する。粒子基準データは、投影面積円相当径、分布は体積分布の設定として、円径度係数と円形係数を算出し、２０個の平均値を求める。上記数式（１）において面積は、二次元に投影した時の外周を形成する線の内部の面積を平板面とし、この平板面を二次元に投影したときの導電性フィラーの外周長さを周囲長とする。
As the flake-like particles, a conductive filler having a circle diameter coefficient obtained from the following formula (1) of 0.15 or more and 0.4 or less can be suitably used. As such a conductive filler, for example, particles described in International Publication WO 2013/001351 can be exemplified.
The circle diameter factor referred to here reads the electron microscopic image (about 1000 times to 10000 times) of the conductive filler using analysis software of Mac-View Ver. 4 (Muntech Co., Ltd.), and conducts the conduction in the manual recognition mode. Select approximately 20 sexual particles. When selecting leaf-like or flake-like particles, it is possible to confirm the whole particle shape in which the particles do not overlap, and the one having an angle at which the flat plate is perpendicular from the observation viewpoint is extracted and selected. The particle reference data is a projected area equivalent circle diameter, and the distribution is a volume distribution setting, and a circle diameter factor and a circle coefficient are calculated to obtain an average value of 20 pieces. In the above equation (1), the area is the area inside the line forming the outer periphery when projected in two dimensions as a flat plate surface, and the outer peripheral length of the conductive filler when this flat plate surface is projected in two dimensions Take the lead.
このような粒子を用いることにより、導電特性をより優れたものとし、且つ薄膜化が可能となる。更に、熱硬化性樹脂、硬化性化合物等のバインダー成分との接触面積が大きくなるので、引張破断歪を効果的に向上できるというメリットを有する。また、コアシェル型の導電性フィラーを用いることによりコストダウンを図ることができる。上記数式（１）から求められる円径度係数の平均値は、０．１５以上、０．３未満がより好ましい。 By using such particles, the conductive characteristics can be further improved and a thin film can be formed. Furthermore, since the contact area with a binder component such as a thermosetting resin and a curable compound is increased, there is an advantage that tensile strain at break can be effectively improved. In addition, cost reduction can be achieved by using a core-shell type conductive filler. As for the average value of the circle diameter degree coefficient calculated | required from the said Numerical formula (1), 0.15 or more and less than 0.3 are more preferable.
導電性フィラーの配合量は、バインダー樹脂１００質量部に対して、１００〜１５００質量部を配合することが好ましく、１００〜１０００質量部がより好ましい。 It is preferable to mix | blend 100-1500 mass parts with respect to 100 mass parts of binder resin, and, as for the compounding quantity of a conductive filler, 100-1000 mass parts is more preferable.
導電性フィラーの平均粒子径Ｄ５０は、２〜１００μｍが好ましく、２〜８０μｍがより好ましい。更に好ましくは３〜５０μｍであり、特に好ましくは５〜２０μｍである。
なお、Ｄ５０平均粒子径は、レーザー回折・散乱法により測定することができる。
具体的には、レーザー回折・散乱法粒度分布測定装置ＬＳ１３３２０（ベックマン・コールター社製）を使用し、トルネードドライパウダーサンプルモジュールにて、導電性微粒子を測定して得た数値であり、粒子径累積分布における累積値が５０％の粒子径である。なお、屈折率の設定は１．６として求められる。
2-100 micrometers is preferable and, as for the average particle diameter D50 of a conductive filler, 2-80 micrometers is more preferable. More preferably, it is 3 to 50 μm, and particularly preferably 5 to 20 μm.
The D50 average particle diameter can be measured by a laser diffraction / scattering method.
Specifically, it is a numerical value obtained by measuring conductive fine particles with a tornado dry powder sample module using a laser diffraction / scattering particle size distribution measuring apparatus LS13320 (manufactured by Beckman Coulter Co., Ltd.) The cumulative value in the distribution is 50% of the particle size. The setting of the refractive index is determined as 1.6.
マイクロサイズのフレーク状粒子とナノサイズの球状粒子の混合系を用いる態様も好適である。なお、導電性フィラーは、特に粒子サイズが小さい場合などにおいて、加熱圧着により溶融して他の導電性フィラーと溶融する場合がある。 An embodiment using a mixed system of micro-sized flake-like particles and nano-sized spherical particles is also suitable. In addition, especially when particle | grain size is small etc., a conductive filler may be fuse | melted by thermocompression bonding and may fuse | melt with another conductive filler.
導電性樹脂層は、例えば導電性フィラーを含有した導電性樹脂組成物を剥離性シート上に塗工・乾燥をすることで形成できる。または、導電性フィラーを含有した導電性樹脂組成物を例えばＴダイのような押出成形機により、シート状に押し出すことで形成できる。 The conductive resin layer can be formed, for example, by coating and drying a conductive resin composition containing a conductive filler on a peelable sheet. Alternatively, it can be formed by extruding a conductive resin composition containing a conductive filler into a sheet by an extruder such as a T-die.
塗工は、例えば、グラビアコート方式、キスコート方式、ダイコート方式、リップコート方式、コンマコート方式、ブレード方式、ロールコート方式、ナイフコート方式、スプレーコート方式、バーコート方式、スピンコート方式、ディップコート方式等の公知の塗工方法を使用できる。塗工の際、必要に応じて乾燥工程を設けてもよい。前記乾燥は、熱風乾燥機および赤外線ヒーター等公知の乾燥装置が使用できる。 Coating is carried out, for example, by gravure coating, kiss coating, die coating, lip coating, comma coating, blade coating, blade coating, blade coating, knife coating, knife coating, spray coating, bar coating, spin coating, dip coating. Known coating methods such as can be used. In the case of coating, you may provide a drying process as needed. The said drying can use well-known drying apparatuses, such as a hot-air dryer and an infrared heater.
［金属層］
電磁波シールド層（Ａ）に金属層を用いる場合、金属層は真空蒸着、スパッタリング、ＣＶＤ法、ＭＯ（メタルオーガニック）、メッキ、金属箔等で形成する。これらの中でも引っ掻き耐性とエッジ部割れ耐性および電磁波シールド性の観点から、真空蒸着またはメッキが好ましい。金属層は、単層でもよいし、同一または異なる種類を複数層積したものでもよい。
[Metal layer]
When a metal layer is used for the electromagnetic shielding layer (A), the metal layer is formed by vacuum evaporation, sputtering, CVD, MO (metal organic), plating, metal foil or the like. Among these, vacuum evaporation or plating is preferred from the viewpoints of scratch resistance, edge crack resistance and electromagnetic wave shielding properties. The metal layer may be a single layer or multiple layers of the same or different types.
真空蒸着により得られる金属層の好適な例として、アルミニウム、銅、銀、金が例示できる。これらのうち、銅、銀がより好ましい。また、スパッタにより得られる金属層の好適な例として、アルミニウム、銅、銀、クロム、金、鉄、パラジウム、ニッケル、白金、銀、亜鉛、酸化インジウム、アンチモンドープ酸化錫が例示できる。これらのうち、銅、銀がより好ましい。真空蒸着およびスパッタにより得られる金属層の厚みの下限は、０．００５μｍ以上が好ましく、０．１μｍ以上がより好ましく、上限は、３μｍ以下が好ましい。 Preferred examples of the metal layer obtained by vacuum deposition include aluminum, copper, silver and gold. Among these, copper and silver are more preferable. Further, as preferable examples of the metal layer obtained by sputtering, aluminum, copper, silver, chromium, gold, iron, palladium, nickel, platinum, silver, zinc, indium oxide, antimony-doped tin oxide can be exemplified. Among these, copper and silver are more preferable. The lower limit of the thickness of the metal layer obtained by vacuum deposition and sputtering is preferably 0.005 μm or more, more preferably 0.1 μm or more, and the upper limit is preferably 3 μm or less.
金属箔の好適な例として、アルミニウム、銅、銀、金等が例示できる。シールド性、接続信頼性およびコストの面から銅、銀、アルミニウムがより好ましく、銅が更に好ましい。銅は、例えば、圧延銅箔または電解銅箔を使用することが好ましく、電解銅箔を使用すると電磁波シールド層（Ａ）をより薄くできるためより好ましい。また、金属箔はメッキで形成したものでもよい。金属箔の厚みの下限は０．１μｍ以上が好ましく、０．５μｍ以上がより好ましい。一方、金属箔の厚みの上限は、１０μｍ以下が好ましく、５μｍ以下がより好ましい。 Preferred examples of the metal foil include aluminum, copper, silver, gold and the like. Copper, silver, and aluminum are more preferable, and copper is more preferable, in terms of shielding property, connection reliability and cost. It is preferable to use copper, for example, a rolled copper foil or an electrolytic copper foil, and using an electrolytic copper foil is more preferable because the electromagnetic wave shielding layer (A) can be made thinner. The metal foil may be formed by plating. 0.1 micrometer or more is preferable and, as for the minimum of thickness of metal foil, 0.5 micrometer or more is more preferable. On the other hand, 10 micrometers or less are preferable and, as for the upper limit of the thickness of metal foil, 5 micrometers or less are more preferable.
＜粘着層（Ｂ）＞
本発明の真空成形用電磁波シールド積層体はさらに粘着層（Ｂ）を有する。粘着剤層（Ｂ）は常温でタック性を示すものであり、熱硬化後もタック性を有し、粘着性を有する層である。粘着層（Ｂ）は、例えば、一般的な天然ゴム、合成イソプレンゴム、再生ゴム、スチレン−ブタジエンゴム、ポリイソプレンゴム、スチレン−イソプレン−スチレンゴム等を主成分とするゴム系粘着剤、アクリル系粘着剤、ウレタン系粘着剤およびシリコン系粘着剤等を用いることができる。
<Adhesive layer (B)>
The vacuum molding electromagnetic wave shield laminate of the present invention further has an adhesive layer (B). The pressure-sensitive adhesive layer (B) exhibits tackiness at normal temperature, has tackiness even after heat curing, and is tacky. The adhesive layer (B) is, for example, a general natural rubber, a synthetic isoprene rubber, a regenerated rubber, a styrene-butadiene rubber, a polyisoprene rubber, a rubber-based pressure-sensitive adhesive containing styrene-isoprene-styrene rubber, etc., an acrylic type A pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicon-based pressure-sensitive adhesive and the like can be used.
粘着層（Ｂ）は絶縁性でも導電性を有していても良い。粘着層（Ｂ）が導電性を有すると、立体成形体にグランド用の端子がある場合、電磁波シールド層（Ａ）のグランド接地が容易となる。導電性を有する粘着層（Ｂ）は、電磁波シールド層（Ａ）で記載した導電性フィラーを含むことで導電性を付与することができる。
導電性フィラーは樹枝状または球状の導電性フィラーを含むことが好ましい。上記の形状の導電性フィラーを含むことでグランド設置の接続信頼性がより向上する。
The adhesive layer (B) may be either insulating or conductive. When the adhesive layer (B) has conductivity, when there is a terminal for grounding in the three-dimensional molded body, grounding of the electromagnetic wave shielding layer (A) is facilitated. The adhesive layer (B) having conductivity can be provided with conductivity by including the conductive filler described in the electromagnetic wave shielding layer (A).
The conductive filler preferably contains a dendritic or spherical conductive filler. The connection reliability of the ground installation is further improved by including the conductive filler in the above shape.
導電性フィラーの配合量は、粘着層（Ｂ）の固形分中に３〜８０質量％配合することがグランド接続性と密着性を向上する観点から好ましい。好ましくは、５〜７５質量％である。 It is preferable to mix | blend 3-80 mass% in the solid content of an adhesion layer (B) as a compounding quantity of a conductive filler from a viewpoint of improving grand | ground connectivity and adhesiveness. Preferably, it is 5 to 75% by mass.
＜支持層（Ｃ）＞
本発明の真空成形用電磁波シールド積層体は、電磁波シールド層（Ａ）と粘着層（Ｂ）に、さらに支持層（Ｃ）を有することが好ましい。支持層（Ｃ）は、真空成形において電磁波シールド層（Ａ）の強度を向上し破断を抑制し、引っ掻き耐性を向上する機能を有する。
<Support layer (C)>
The electromagnetic wave shielding laminate for vacuum forming of the present invention preferably further has a support layer (C) on the electromagnetic wave shielding layer (A) and the adhesive layer (B). The support layer (C) has a function of improving the strength of the electromagnetic wave shield layer (A) and suppressing breakage in vacuum forming, and improving scratch resistance.
熱可塑性樹脂の具体例として、例えばポリウレタン樹脂、ポリメチルメタクリレート樹脂、アクリロニトリル−ブタジエン−スチレン樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリプロピレン樹脂、ポリエチレン樹脂、ポリ塩化ビニル樹脂、フッ素樹脂等が挙げられる。この中でもポリ塩化ビニル樹脂、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂またはポリオレフィン樹脂が好ましい。
特に好ましくは、ポリ塩化ビニル樹脂、ポリウレタン樹脂、ポリメチルメタクリレート樹脂、またはポリカーボネート樹脂である。
熱可塑性樹脂は、硬化性官能基を有しない樹脂である。
Specific examples of the thermoplastic resin include polyurethane resin, polymethyl methacrylate resin, acrylonitrile-butadiene-styrene resin, polycarbonate resin, polyethylene terephthalate resin, polypropylene resin, polyethylene resin, polyvinyl chloride resin, fluorine resin and the like. Among these, polyvinyl chloride resin, polymethyl methacrylate resin, polycarbonate resin or polyolefin resin is preferable.
Particularly preferred are polyvinyl chloride resin, polyurethane resin, polymethyl methacrylate resin, or polycarbonate resin.
The thermoplastic resin is a resin having no curable functional group.
支持層（Ｃ）の厚みは２０μｍ以上２００μｍ以下が好ましく、２５μｍ以上１００μｍ以下がより好ましい。 20 micrometers or more and 200 micrometers or less are preferable, and, as for the thickness of a support layer (C), 25 micrometers or more and 100 micrometers or less are more preferable.
また、支持層（Ｃ）は、導電性樹脂層で説明した熱硬化性樹脂を使用することができる。 熱硬化性樹脂は、加熱による架橋反応に利用できる官能基を複数有する樹脂であり、熱硬化性樹脂を使用する場合、導電性樹脂層で説明した硬化剤を含有することが好ましい。支持層（Ｃ）の形成に熱硬化性樹脂を用いる場合、あらかじめ熱硬化する温度でエージングし、硬化させてから使用しても良い。
熱硬化性樹脂として好ましくは、ポリ塩化ビニル樹脂、ポリウレタン樹脂、ポリメチルメタクリレート樹脂、またはポリカーボネート樹脂である。
Moreover, the thermosetting resin demonstrated by the conductive resin layer can be used for a support layer (C). The thermosetting resin is a resin having a plurality of functional groups that can be used for the crosslinking reaction by heating, and when using a thermosetting resin, it is preferable to contain the curing agent described in the conductive resin layer. When using a thermosetting resin for formation of a support layer (C), you may use, making it age at the temperature which carries out thermosetting beforehand and hardening it.
The thermosetting resin is preferably a polyvinyl chloride resin, a polyurethane resin, a polymethyl methacrylate resin, or a polycarbonate resin.
支持層（Ｃ）は、電磁波シールド層（Ａ）との密着性を向上させる目的で易接着層を備えることができる。易接着層はコロナ処理やプラズマ処理等の乾式処理、または易接着樹脂を使用した湿式処理が好ましいが、密着性の観点から湿式処理がより好ましい。前記易接着樹脂としては例えばウレタン樹脂、アクリル樹脂、ポリエステル樹脂、ビニル系樹脂等が挙げられる。これら易接着層は１層で形成してもよく、または２層以上を積層して形成しても良い。易接着層の形成方法については特に限定されるものではなく、例えばグラビアコート法、リバースコート法等の従来公知の方法を用いることができる。また易接着層の厚みとしては、密着性、伸張性の観点から０．１μｍ〜５μｍが好ましく、０．３μｍ〜３μｍがさらに好ましい。 A support layer (C) can be provided with an easily bonding layer in order to improve adhesiveness with an electromagnetic wave shield layer (A). The easy adhesion layer is preferably a dry treatment such as corona treatment or plasma treatment, or a wet treatment using an easy adhesion resin, but a wet treatment is more preferable from the viewpoint of adhesion. Examples of the easy adhesion resin include urethane resin, acrylic resin, polyester resin, vinyl resin and the like. These easy adhesion layers may be formed of one layer or may be formed by laminating two or more layers. It does not specifically limit about the formation method of an easily bonding layer, For example, conventionally well-known methods, such as a gravure coat method and a reverse coat method, can be used. The thickness of the easy adhesion layer is preferably 0.1 μm to 5 μm, and more preferably 0.3 μm to 3 μm from the viewpoints of adhesion and extensibility.
図１（ａ）は、電磁波シールド層（Ａ）と粘着層（Ｂ）を基本構成要素とする真空成形用電磁波シールド積層体を示すもので、この真空成形用電磁波シールド積層体に支持層（Ｃ）を付加した形態を図１（ｂ）、（ｃ）、（ｄ）を用いて説明する。第１の形態として、粘着層（Ｂ）／電磁波シールド層（Ａ）／支持層（Ｃ）の順に積層した積層体（図１（ｂ））、第２の形態として、粘着層（Ｂ）／支持層（Ｃ）／電磁波シールド層（Ａ）の順に積層した積層体（図１（ｃ））、第３の形態として、支持層（Ｃ）が電磁波シールド層（Ａ）に挟み込まれた積層体（図１（ｄ））の積層構造等をとることができる。この中でも電磁波シールド層（Ａ）が最外層となる積層体（図１（ｂ））のような形態は、最表面から容易にグランド接地が可能となるため好ましい。 FIG. 1 (a) shows a vacuum forming electromagnetic wave shield laminate having an electromagnetic wave shielding layer (A) and an adhesive layer (B) as basic components, and a support layer (C) is shown on the vacuum forming electromagnetic wave shield laminate. The form which added) is demonstrated using FIG.1 (b), (c), (d). As a first embodiment, a laminate (FIG. 1 (b)) in which an adhesive layer (B) / electromagnetic wave shield layer (A) / support layer (C) is laminated in order; as a second embodiment, an adhesive layer (B) / Laminated body laminated in order of support layer (C) / electromagnetic wave shield layer (A) (FIG. 1 (c)) As a third embodiment, laminated body in which the support layer (C) is sandwiched between electromagnetic wave shield layers (A) The laminated structure (FIG. 1 (d)) or the like can be taken. Among them, a form such as a laminate (FIG. 1B) in which the electromagnetic wave shielding layer (A) is the outermost layer is preferable because ground can be easily ground from the outermost surface.
《電磁波シールド成形体》
本願における電磁波シールド成形体は、本発明の真空成形用電磁波シールド積層体と立体成形体とを一体成形したものである。一体成形は、真空成形法または真空圧空成形法によって行う。
<< Electromagnetic wave shield molded body >>
The electromagnetic wave shield molded body in the present application is obtained by integrally molding the electromagnetic wave shield laminate for vacuum forming of the present invention and a three-dimensional molded body. The integral molding is performed by a vacuum forming method or a vacuum pressure forming method.
立体成形体は、ポリエチレン、ポリプロピレン、ＡＢＳ（アクリロニトリルブタジエンスチレン共重合体）、ポリアセタール、ポリアミド、ポリカーボネートや、ＰＰＳ（ポリフェニレンサルファイド）、ＰＢＴ（ポリブチレンテレフタレート）などの熱可塑性樹脂並びに、ポリウレタン系樹脂、フェノール樹脂、不飽和ポリエステルなどの熱硬化性樹脂等からなり、射出成形、モールド成形、熱プレス成形によって立体的に成形されたものである。
立体成形体は用途に応じて様々な形状に成形されるため、凹凸を有する形状となる。本発明における立体成形体は凹凸の段差部が少なくとも５ｍｍ以上を有する物であり、電磁波シールド成形体はこの凹凸部に対して真空成形用電磁波シールド積層体によってシールド層が形成されたものである。
The three-dimensional molded articles are polyethylene, polypropylene, ABS (acrylonitrile butadiene styrene copolymer), polyacetal, polyamide, polycarbonate, thermoplastic resins such as PPS (polyphenylene sulfide), PBT (polybutylene terephthalate), etc., polyurethane resin, phenol It is made of a resin, a thermosetting resin such as unsaturated polyester, and the like, and is three-dimensionally formed by injection molding, mold molding, and heat press molding.
Since a three-dimensional molded object is shape | molded in various shapes according to a use, it becomes a shape which has an unevenness | corrugation. The three-dimensional molded article in the present invention is a product in which the step portion of the unevenness has at least 5 mm or more, and the electromagnetic wave shield molded body is the one in which a shield layer is formed by the electromagnetic wave shielding laminate for vacuum forming on the uneven portion.
［電磁波シールド成形体の製造方法］
本発明の電磁波シールド成形体の製造方法について説明する。まず上記で説明した立体成形体を作製する。次いで立体成形体に対し、電磁波シールド積層体を真空成形法、真空圧空成形法によって立体成形体にシールド層を成形することができる。真空成形法及び真空圧空成形法とは、まず真空成形用電磁波シールド積層体を成形機の所定の位置に設置し、真空成形用電磁波シールド積層体の軟化温度まで加熱軟化させ、立体成形体を下から送り込み、真空に引いて立体成形体に密着させ（真空成形法）、または真空に引くと共に反対側から圧縮空気で押して型に密着させ（真空圧空成形法）、成形体を冷却後に型から外して成形体を得る成形法である。
[Method of manufacturing an electromagnetic wave shield molded article]
The manufacturing method of the electromagnetic wave shielding molded object of this invention is demonstrated. First, the three-dimensional molded body described above is manufactured. Next, for the three-dimensional molded article, the shield layer can be formed into a three-dimensional molded article by vacuum molding or vacuum pressure molding of the electromagnetic wave shield laminate. With the vacuum forming method and vacuum pressure forming method, first, the electromagnetic wave shielding laminate for vacuum forming is installed at a predetermined position of the forming machine, heat softened to the softening temperature of the electromagnetic shielding shield for vacuum forming, and The product is sent from the inside, drawn to vacuum and brought into intimate contact with the three-dimensional molded body (vacuum forming method) or drawn in vacuum and pressed from the opposite side by compressed air to be in close contact with the mold (vacuum pressure air forming method). Molding method to obtain a molded body.
以下、本発明を実施例によりさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例中の「部」とあるのは「質量部」を、「％」とあるのは「質量％」をそれぞれ表すものとする。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. In the examples, "part" means "part by mass", and "%" means "% by mass".
また、導電性フィラーの平均粒子径Ｄ５０および円径度係数と、樹脂の酸価および質量平均分子量（Ｍｗ）と、の測定方法は以下の通りである。 Moreover, the measuring method of the average particle diameter D50 and circular diameter degree coefficient of a conductive filler, and the acid value and mass mean molecular weight (Mw) of resin is as follows.
＜導電性フィラーの平均粒子径Ｄ５０＞
平均粒子径は、レーザー回折・散乱法粒度分布測定装置ＬＳ１３３２０（ベックマン・コールター社製）を使用し、トルネードドライパウダーサンプルモジュールにて、導電性複合微粒子を測定して得た平均粒子径Ｄ５０の数値であり、粒子径累積分布における累積値が５０％の粒子径である。分布は体積分布、屈折率の設定は１．６とした。当該粒子径であればよく、一次粒子でも二次粒子でもよい。
<Average particle diameter D50 of conductive filler>
The average particle size is a numerical value of the average particle size D50 obtained by measuring the conductive composite fine particles with a tornado dry powder sample module using a laser diffraction / scattering particle size distribution analyzer LS13320 (manufactured by Beckman Coulter Inc.) The particle size is 50% of the cumulative value in the particle size cumulative distribution. The distribution was volume distribution, and the setting of the refractive index was 1.6. It may be any particle size, and may be primary particles or secondary particles.
＜導電性フィラーの円径度係数＞
明細内に記載の方法で求めた。
<Circular diameter factor of conductive filler>
It was determined by the method described in the specification.
＜樹脂の酸価＞
共栓付き三角フラスコ中に熱硬化性樹脂を約１ｇ精密に量り採り、トルエン／エタノール（容量比：トルエン／エタノール＝２／１）混合液５０ｍＬを加えて溶解する。これに、フェノールフタレイン試液を指示薬として加え、３０秒間保持する。その後、溶液が淡紅色を呈するまで０．１ｍｏｌ／Ｌアルコール性水酸化カリウム溶液で滴定する。酸価は次式により求めた。酸価は樹脂の乾燥状態の数値とした。
酸価（ｍｇＫＯＨ／ｇ）＝（ａ×Ｆ×５６．１×０．１）／Ｓ
Ｓ：試料の採取量×（試料の固形分／１００）（ｇ）
ａ：０．１ｍｏｌ／Ｌアルコール性水酸化カリウム溶液の滴定量（ｍＬ）
Ｆ：０．１ｍｏｌ／Ｌアルコール性水酸化カリウム溶液の力価
<Acid number of resin>
Approximately 1 g of a thermosetting resin is accurately weighed into a stoppered Erlenmeyer flask, and 50 mL of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1) is dissolved. To this, add phenolphthalein TS as an indicator and hold for 30 seconds. Then, it titrates with 0.1 mol / L alcoholic potassium hydroxide solution until the solution becomes pinkish. The acid value was determined by the following equation. The acid value is a numerical value of the dry state of the resin.
Acid value (mg KOH / g) = (a × F × 56.1 × 0.1) / S
S: amount of sample collected × (solid content of sample / 100) (g)
a: Titrate (mL) of 0.1 mol / L alcoholic potassium hydroxide solution
F: titer of 0.1 mol / L alcoholic potassium hydroxide solution
＜樹脂の質量平均分子量（Ｍｗ）＞
Ｍｗの測定は東ソ−社製ＧＰＣ（ゲルパーミエーションクロマトグラフィ）「ＨＰＣ−８０２０」を用いた。ＧＰＣは溶媒（ＴＨＦ；テトラヒドロフラン）に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィ−である。測定は、カラムに「ＬＦ−６０４」（昭和電工社製：迅速分析用ＧＰＣカラム：６ｍｍＩＤ×１５０ｍｍサイズ）を直列に２本接続して用い、流量０．６ｍL／ｍｉｎ、カラム温度４０℃の条件で行い、質量平均分子量（Ｍｗ）の決定はポリスチレン換算で行った。
<Mass average molecular weight of resin (Mw)>
The measurement of Mw used GPC (gel permeation chromatography) "HPC-8020" made by Higashi sour company. GPC is a liquid chromatography that separates and determines a substance dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. Measurement is performed by connecting two “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) in series to the column, using a flow rate of 0.6 mL / min and a column temperature of 40 ° C. The weight average molecular weight (Mw) was determined in terms of polystyrene.
以下、実施例で使用した材料を示す。
導電性フィラー１：「核体に銅、被覆層に銀を使用したフレーク状粒子、平均粒子径Ｄ５０＝１１．０μｍ、厚み１．１μｍ、円形度係数＝０．２３」（福田金属箔粉工業社製）
導電性フィラー２：「核体に銅、被覆層に銀を使用した樹枝状粒子、平均粒子径Ｄ５０＝１５．０μｍ、円形度係数＝０．１２」（福田金属箔粉工業社製）
導電性フィラー３：「核体に銅、被覆層に銀を使用した球状粒子、平均粒子径Ｄ５０＝１６．０μｍ、円形度係数＝０．９４」（福田金属箔粉工業社製）
熱硬化性樹脂１：ウレタンウレア樹脂 酸価５［ｍｇＫＯＨ／ｇ］（トーヨーケム社製）
硬化剤１：エポキシ化合物、「ＪＥＲ８２８」（ビスフェノールＡ型エポキシ樹脂 エポキシ当量＝１８９ｇ／ｅｑ）三菱化学社製
硬化剤２：エポキシ化合物、「デナコールＥＸ２１２」（２官能エポキシ樹脂 エポキシ当量＝１５１ｇ／ｅｑ）ナガセケムテックス社製
硬化剤３：エポキシ化合物「Ｅ−５Ｃ」（綜研化学社製）
粘着剤１：アクリル系粘着剤「ＳＫ-１９８６Ｈ」（綜研化学社製）
離型性基材：表面にシリコン離型剤をコーティングした厚みが５０μｍのＰＥＴフィルム
支持層１：厚みが７５μｍ、軟化温度９０℃のポリメチルメタクリレート樹脂基材
支持層２：厚みが７５μｍ、軟化温度１３０℃のポリカーボネート樹脂基材
支持層３：厚みが７５μｍ、軟化温度８０℃のポリ塩化ビニル樹脂基材
支持層４：厚みが７５μｍ、軟化温度１６０℃のポリオレフィン樹脂基材
支持層５：厚みが７５μｍ、軟化温度２００℃のポリエチレンテレフタレート樹脂基材
The materials used in the examples are shown below.
Conductive filler 1: "Flake-like particles using copper as core and silver as coating layer, average particle diameter D50 = 11.0 μm, thickness 1.1 μm, circularity coefficient = 0.23" (Fukuda metal foil powder industry) Company-made)
Conductive filler 2: “Dendrite particles using copper as core and silver as coating layer, average particle diameter D50 = 15.0 μm, circularity coefficient = 0.12” (manufactured by Fukuda Metal Foil & Powder Co., Ltd.)
Conductive filler 3: "Spherical particles using copper as core and silver as coating layer, average particle diameter D50 = 16.0 μm, circularity coefficient = 0.94" (manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.)
Thermosetting resin 1: Urethane urea resin Acid value 5 [mg KOH / g] (made by Toyochem Co., Ltd.)
Curing agent 1: Epoxy compound, "JER 828" (bisphenol A type epoxy resin epoxy equivalent = 189 g / eq) Curing agent manufactured by Mitsubishi Chemical Co., Ltd. 2: epoxy compound, "Denacole EX 212" (bifunctional epoxy resin epoxy equivalent = 151 g / eq) Nagase ChemteX curing agent 3: Epoxy compound "E-5C" (Saken Chemical Co., Ltd.)
Adhesive 1: Acrylic adhesive "SK-1986H" (manufactured by Soken Chemical Co., Ltd.)
Releasable base material: PET film support layer 1 having a thickness of 50 μm coated with a silicon release agent on the surface: polymethyl methacrylate resin base support layer 2 having a thickness of 75 μm and softening temperature 90 ° C .: thickness 75 μm, softening temperature 130 ° C. polycarbonate resin substrate support layer 3: thickness 75 μm, polyvinyl chloride resin substrate support layer 4 with softening temperature 80 ° C .: thickness 75 μm, polyolefin resin substrate support layer 5 with softening temperature 160 ° C .: thickness 75 μm And polyethylene terephthalate resin base material with a softening temperature of 200 ° C
［実施例１］
熱硬化性樹脂１（固形分）１００部と、硬化剤２を５０部と、導電性フィラー１を１８５部と、導電性フィラー２を１８５部と、を容器に仕込み、不揮発分濃度が４５質量％になるようトルエン：イソプロピルアルコール（質量比２：１）の混合溶剤を加えディスパーで１０分攪拌することで樹脂組成物を得た。
この樹脂組成物を乾燥厚みが６０μｍになるようにドクターブレードを使用して離形性基材に塗工した。そして、１００℃で２分間乾燥することで、離型性基材の一方の面上に電磁波シールド層が積層された離型性基材付電磁波シールド層を得た。
別途、粘着剤１（固形分）１００部と、硬化剤３を０．５部とを容器に仕込み、不揮発分濃度が４５質量％になるよう酢酸エチルを加え、ディスパーで１０分攪拌することで粘着剤樹脂組成物を得た。
次いで、離形シートの一方の面に、乾燥後の厚みが２０μｍになるようドクターブレードで粘着剤組成物を塗工し、１００℃で２分乾燥することで粘着層が一方に形成された粘着層付き離形シートを得た。
前記離型性基材付電磁波シールド層の電磁波シールド層面と前記粘着層付き離形シートの粘着層をラミネーターで貼り合わせ、真空成形用電磁波シールド積層体を得た。
Example 1
100 parts of thermosetting resin 1 (solid content), 50 parts of curing agent 2, 185 parts of conductive filler 1, 185 parts of conductive filler 2 are charged in a container, and the non-volatile content concentration is 45 mass A mixed solvent of toluene: isopropyl alcohol (mass ratio 2: 1) was added so as to obtain%, and the resin composition was obtained by stirring with a disper for 10 minutes.
The resin composition was applied to a releasing substrate using a doctor blade so that the dry thickness was 60 μm. And by drying for 2 minutes at 100 degreeC, the electromagnetic wave shielding layer with a releasable base material in which the electromagnetic wave shielding layer was laminated | stacked on one surface of the releasable base material was obtained.
Separately, 100 parts of adhesive 1 (solid content) and 0.5 parts of curing agent 3 are charged in a container, ethyl acetate is added so that the nonvolatile content concentration is 45% by mass, and stirring is performed for 10 minutes with a disper An adhesive resin composition was obtained.
Then, a pressure-sensitive adhesive composition is applied to one side of the release sheet with a doctor blade so that the thickness after drying is 20 μm, and the adhesive layer is formed on one side by drying at 100 ° C. for 2 minutes A layered release sheet was obtained.
The electromagnetic wave shield layer surface of the electromagnetic wave shield layer with the releasable substrate and the adhesive layer of the releasable sheet with the adhesive layer were bonded with a laminator to obtain an electromagnetic shield laminate for vacuum forming.
［実施例２〜７および比較例１〜２］
各成分およびその配合量（質量部）を表１に示すように変更した以外は、実施例１と同様にして、真空成形用電磁波シールド積層体を作製した。なお、表１に示す配合量はすべて、固形分質量である。
[Examples 2 to 7 and Comparative Examples 1 to 2]
An electromagnetic shielding laminate for vacuum forming was produced in the same manner as in Example 1 except that each component and the compounding amount (parts by mass) thereof were changed as shown in Table 1. In addition, all the compounding quantities shown in Table 1 are solid content mass.
［実施例８］
熱硬化性樹脂１（固形分）１００部と、硬化剤１を２５部と、硬化剤２を２５部と、導電性フィラー１を３７０部と、を容器に仕込み、不揮発分濃度が４５質量％になるようトルエン：イソプロピルアルコール（質量比２：１）の混合溶剤を加えディスパーで１０分攪拌することで樹脂組成物を得た。
この樹脂組成物を乾燥厚みが６０μｍになるようにドクターブレードを使用して支持層１に塗工した。そして、８０℃で３分間乾燥することで、支持層の一方の面上に電磁波シールド層が積層された多層体を得た。
別途、粘着剤１（固形分）１００部と、架橋剤を０．５部とを容器に仕込み、不揮発分濃度が４５質量％になるよう酢酸エチルを加えディスパーで１０分攪拌することで粘着剤樹脂組成物を得た。
次いで、離形シートの一方の面に、乾燥後の厚みが２０μｍになるようドクターブレードで粘着剤組成物を塗工し、１００℃で２分乾燥することで粘着性樹脂層が一方に形成された粘着性樹脂層付き離形シートを得た。
前記多層体の支持層と前記粘着性樹脂層付き離形シートの粘着性樹脂層をラミネーターで貼り合わせることで、粘着層／支持層／電磁波シールド層の順に積層された真空成形用電磁波シールド積層体を得た。
[Example 8]
100 parts of thermosetting resin 1 (solid content), 25 parts of curing agent 1, 25 parts of curing agent 2, and 370 parts of conductive filler 1 are charged in a container, and the nonvolatile content concentration is 45% by mass A mixed solvent of toluene: isopropyl alcohol (mass ratio 2: 1) was added to obtain a resin composition by stirring for 10 minutes with a disper.
The resin composition was applied to the support layer 1 using a doctor blade so as to have a dry thickness of 60 μm. And it dried at 80 degreeC for 3 minutes, and obtained the multilayer body by which the electromagnetic wave shield layer was laminated | stacked on one surface of a support layer.
Separately, 100 parts of adhesive 1 (solid content) and 0.5 parts of a crosslinking agent are charged in a container, ethyl acetate is added so that the concentration of non-volatile components becomes 45% by mass, and the mixture is stirred for 10 minutes with a disper A resin composition was obtained.
Next, a pressure-sensitive adhesive composition is applied to one side of the release sheet with a doctor blade so that the thickness after drying is 20 μm, and the adhesive resin layer is formed on one side by drying at 100 ° C. for 2 minutes. A release sheet with a tacky resin layer was obtained.
An electromagnetic wave shield laminate for vacuum forming, in which an adhesive layer / support layer / electromagnetic wave shield layer is laminated in this order by laminating a support layer of the multilayer body and an adhesive resin layer of the release sheet with the adhesive resin layer with a laminator. I got
［実施例９〜１２］
各成分およびその配合量（質量部）を表１に示すように変更した以外は、実施例８と同様にして、真空成形用電磁波シールド積層体を作製した。
[Examples 9 to 12]
An electromagnetic shielding laminate for vacuum forming was produced in the same manner as in Example 8 except that each component and the compounding amount (parts by mass) thereof were changed as shown in Table 1.
［実施例２２］
支持層１の片面に真空蒸着によって厚みが０．１μｍの銅を形成した積層体を得た。
別途、粘着剤（固形分）１００部と、架橋剤を０．５部とを容器に仕込み、不揮発分濃度が４５質量％になるよう酢酸エチルを加えディスパーで１０分攪拌することで粘着剤樹脂組成物を得た。
次いで、離形シートの一方の面に、乾燥後の厚みが２０μｍになるようドクターブレードで粘着剤組成物を塗工し、１００℃で２分乾燥することで粘着性樹脂層が一方に形成された粘着性樹脂層付き離形シートを得た。
前記積層体の銅層と前記粘着性樹脂層付き離形シートの粘着性樹脂層をラミネーターで貼り合わせることで、真空成形用電磁波シールド積層体を得た。
Example 22
A laminate having a thickness of 0.1 μm formed on one surface of the support layer 1 by vacuum deposition was obtained.
Separately, 100 parts of an adhesive (solid content) and 0.5 parts of a crosslinking agent are charged in a container, ethyl acetate is added so that the concentration of non-volatile components is 45 mass%, and the adhesive resin is stirred for 10 minutes with a disper The composition was obtained.
Next, a pressure-sensitive adhesive composition is applied to one side of the release sheet with a doctor blade so that the thickness after drying is 20 μm, and the adhesive resin layer is formed on one side by drying at 100 ° C. for 2 minutes. A release sheet with a tacky resin layer was obtained.
The electromagnetic wave shield laminate for vacuum forming was obtained by bonding the copper layer of the laminate and the adhesive resin layer of the release sheet with the adhesive resin layer with a laminator.
［実施例２３、比較例３］
支持層１の片面に無電解メッキによって厚みが１μｍの銅を形成した積層体を得た。以降は実施例２２と同様にして、実施例２３の真空成形用電磁波シールド積層体を作製した。
ただし、実施例６、７、２２、および２３は参考例である。
[Example 23, Comparative Example 3]
A laminate was obtained in which copper having a thickness of 1 μm was formed on one surface of the support layer 1 by electroless plating. After that, in the same manner as in Example 22, a vacuum forming electromagnetic wave shield laminate of Example 23 was produced.
However, Examples 6, 7, 22, and 23 are reference examples.
［比較例３］
銀ナノインキ「ＳＡＮＴＥ」（Ｃｉｍａ Ｎａｎｏ Ｔｃｅｈ Ｉｎｃ．社製）を支持層１の片面に塗布し焼結することで網目状の銀膜を形成した積層体を得た。以降は実施例２２と同様にして、比較例３の真空成形用電磁波シールド積層体を作製した。
Comparative Example 3
A silver nanoink "SANTE" (manufactured by Cima Nano Tceh Inc.) was applied to one side of the support layer 1 and sintered to obtain a laminate having a mesh-like silver film formed. Thereafter, in the same manner as in Example 22, a vacuum forming electromagnetic wave shield laminate of Comparative Example 3 was produced.
上記実施例および比較例について、以下の測定方法および評価基準にて物性値の測定と評価とを行った。 About the said Example and comparative example, measurement and evaluation of the physical-property value were performed with the following measuring method and evaluation criteria.
＜試験基板の作製方法＞
ガラスエポキシからなり、内部にグランド端子１１を有する基板１０上に、モールド封止された電子部品をアレイ状に搭載した基板を用意した。基板の厚みは０．３ｍｍであり、モールド封止厚、即ち基板上面からモールド封止材の頂面までの高さ（部品高さ）Ｈは５ｍｍである。その後、部品同士の間隙である溝に添ってハーフダイシングを行い、試験基板を得た（図２参照）。ハーフダイシング溝に露出したグランド端子１１の高さは５０μｍである。
<Method of preparing test substrate>
A substrate was prepared in which mold-sealed electronic components were mounted in an array on a substrate 10 made of glass epoxy and having a ground terminal 11 inside. The thickness of the substrate is 0.3 mm, and the mold sealing thickness, that is, the height (part height) H from the upper surface of the substrate to the top surface of the mold sealing material is 5 mm. Thereafter, half dicing was performed along a groove which is a gap between parts to obtain a test substrate (see FIG. 2). The height of the ground terminal 11 exposed to the half dicing groove is 50 μm.
＜線膨張係数＞
線膨張係数は、ＪＩＳ−Ｋ７１９７に記載のプラスチックの熱機械分析による線膨張率試験方法により測定された値を用いる。
<Linear expansion coefficient>
As the linear expansion coefficient, a value measured by a linear expansion coefficient test method by thermal mechanical analysis of plastic described in JIS-K7197 is used.
＜引張破断歪＞
以下の方法によって求めた引張破断歪（％）を引張破断歪とした。得られた離型性基材付電磁波シールド層を、幅２００ｍｍ×長さ６００ｍｍの大きさに切断した後、離型性基材付電磁波シールド層から剥離基材を剥がして測定試料とした。測定試料について小型卓上試験機ＥＺ−ＴＥＳＴ（島津製作所社製）を用いて、温度２５℃、相対湿度５０％の条件下で引っ張り試験（試験速度５０ｍｍ／ｍｉｎ）を実施した。得られたＳ−Ｓ曲線（Ｓｔｒｅｓｓ−Ｓｔｒａｉｎ曲線）から導電性樹脂層の引張破断歪（％）を算出した。
<Tension fracture strain>
The tensile breaking strain (%) determined by the following method was taken as the tensile breaking strain. The obtained electromagnetic shielding layer with release substrate was cut into a size of width 200 mm × length 600 mm, and then the release substrate was peeled off from the electromagnetic shield layer with release substrate to obtain a measurement sample. A tensile test (testing speed: 50 mm / min) was carried out under the conditions of a temperature of 25 ° C. and a relative humidity of 50% using a small desktop tester EZ-TEST (manufactured by Shimadzu Corporation) for the measurement sample. The tensile breaking strain (%) of the conductive resin layer was calculated from the obtained SS curve (Stress-Strain curve).
＜伸長後の積層体の電磁波シールド性＞
幅２０ｃｍ、長さ２０ｍｍの真空成形用電磁波シールド積層体を用意し、１５０℃環境下で幅が１．５倍となる３０ｃｍまで引き延ばした。その後室温に冷却し、引き伸ばした状態の真空成型用電磁波シールドフィルムをＫＥＣ法により電磁波シールド性（電界）測定を行った。
<Electromagnetic wave shielding property of laminate after extension>
A 20 cm wide, 20 mm long electromagnetic wave shield laminate for vacuum forming was prepared, and stretched to 30 cm in which the width became 1.5 times under a 150 ° C. environment. Thereafter, the film was cooled to room temperature, and the electromagnetic shielding film for vacuum forming in a stretched state was subjected to the measurement of the electromagnetic shielding property (electric field) by the KEC method.
＜立体成型体のシールド性評価＞
得られた真空成形用電磁波シールド積層体を、３０×３０ｃｍにカットした。次いで、ポリカーボネートで形成した一辺が１０ｃｍの立方体である立体成型体を用意し、真空成形機「ＦＯＲＭＥＣＨ３００Ｘ」（成光産業株式会社製）を用いて、盤面温度１５０℃で真空成形し、立体成型体の上面および側面にシールド層が形成された電磁波シールド成形体を得た。
上記電磁波シールド成型体の側面を切り出し、ＫＥＣ法により電磁波シールド性（電界）測定を行い、立体成型体のシールド性を評価した。
評価基準は以下の通りである。
+ +：電磁波シールド性が５０ｄＢ以上。良好な結果である。
+ ：電磁波シールド性が４０ｄＢ以上、５０ｄＢ未満。実用上問題ない。
NG：電磁波シールド性が４０ｄＢ未満。実用不可。
<Shielding evaluation of three-dimensional molding>
The obtained vacuum forming electromagnetic wave shield laminate was cut into 30 × 30 cm. Then, a cubic molded body having a side of 10 cm and made of polycarbonate is prepared, and vacuum molded at a surface temperature of 150 ° C. using a vacuum molding machine “FORMECH 300X” (manufactured by Seimitsu Sangyo Co., Ltd.) The electromagnetic wave shield molding in which the shield layer was formed in the upper surface and the side of the above was obtained.
The side surface of the electromagnetic wave shield molded body was cut out, and the electromagnetic wave shielding property (electric field) measurement was performed by the KEC method to evaluate the shield property of the three-dimensional molded body.
Evaluation criteria are as follows.
+ +: 50 dB or more of electromagnetic shielding. It is a good result.
+: The electromagnetic wave shielding property is 40 dB or more and less than 50 dB. There is no problem in practical use.
NG: The electromagnetic wave shielding property is less than 40 dB. Not practical.
＜高段差追従性評価＞
得られた真空成形用電磁波シールド積層体を、１０×１０ｃｍにカットし、真空成形用電磁波シールド積層体の面が試験基板に接するように載置し、仮貼付した。次いで真空成形機「ＦＯＲＭＥＣＨ３００Ｘ」（成光産業株式会社製） を用いて、盤面温度１５０℃で真空成形し、図３に示す電磁波シールド成形体を得た。
図３の断面図に示す底部のグランド端子１１ａ‐１１ｂ間の接続抵抗値をＨＩＯＫＩ社製ＲＭ３５４４とピン型リードプローブを用いて測定することにより、高段差追従性を評価した。
評価基準は以下の通りである。
+ +：接続抵抗値が２００ｍΩ未満。良好な結果である。
+ ：接続抵抗値が２００ｍΩ以上、１０００ｍΩ未満。実用上問題ない。
NG：接続抵抗値が１０００ｍΩ以上。実用不可。
<High step follow-up evaluation>
The obtained vacuum forming electromagnetic wave shield laminate was cut into 10 × 10 cm, and placed so that the surface of the vacuum forming electromagnetic wave shield laminate was in contact with the test substrate, and was temporarily attached. Then, vacuum molding was performed at a panel surface temperature of 150 ° C. using a vacuum molding machine “FORMECH 300X” (manufactured by Shiromitsu Sangyo Co., Ltd.) to obtain an electromagnetic wave shield molded body shown in FIG.
The high step followability was evaluated by measuring the connection resistance value between the ground terminals 11a and 11b at the bottom shown in the cross-sectional view of FIG. 3 using RM3544 manufactured by HIOKI and a pin type lead probe.
Evaluation criteria are as follows.
+ +: Connection resistance value is less than 200 mΩ. It is a good result.
+: Connection resistance value is 200 mΩ or more and less than 1000 mΩ. There is no problem in practical use.
NG: Connection resistance value is 1000 mΩ or more. Not practical.
＜引っ掻き耐性＞
段差追従性評価で得られた電磁波シールド成形体の図３の電磁波遮蔽層の表面ｅ部における鉛筆硬度をＪＩＳ Ｋ５６００−５−４に準拠して荷重７５０ｇにて鉛筆硬度試験を実施した。評価基準は以下の通りである。
+ +： ＨＢ以上 良好な結果である。
+ ： Ｂ 実用上問題ない。
NG： Ｂ未満 実用不可。
<Scratch resistance>
The pencil hardness test was conducted under a load of 750 g in accordance with JIS K5600-5-4 in accordance with JIS K5600-5-4 for pencil hardness at the surface e of the electromagnetic wave shielding layer of FIG. 3 of the molded electromagnetic wave shield obtained in step difference followability evaluation. Evaluation criteria are as follows.
+ +: More than HB Good results.
+: B There is no problem in practical use.
NG: less than B not practical.
＜密着性＞
得られた電磁波シールド成形体のｅ面（図３参照）に、ＪＩＳＫ５４００に準じてクロスカットガイドを使用し、間隔が１ｍｍの碁盤目を２５個作成した。その後、碁盤目部に粘着テープを強く圧着させ、テープの端を４５°の角度で一気に引き剥がし、碁盤目の状態を下記の基準で判断した。
+ +：どの格子の目も剥がれない。
+ ：塗膜がカットの線に沿って部分的に剥がれている。剥がれ率１５％以上３５％未満。
NG：塗膜がカットの線に沿って部分的に若しくは全面的に剥がれている。剥がれ率３５％以上。
<Adhesiveness>
A cross cut guide was used on the surface e (see FIG. 3) of the obtained electromagnetic wave shield molded body according to JIS K 5400, and 25 grids with a distance of 1 mm were formed. Thereafter, an adhesive tape was strongly pressed to the grid portion, the end of the tape was peeled off at a stretch of 45 ° at once, and the grid state was judged according to the following criteria.
+ +: The eyes of any grid do not peel off.
+: The coating film is partially peeled off along the cut line. Peeling rate 15% or more and less than 35%.
NG: The coating film is partially or completely peeled off along the cut line. Peeling rate 35% or more.
＜エッジ部破れ耐性＞
図３に示す真空成形用電磁波シールド積層体のエッジ部の破れを顕微鏡によって観察し評価した。観察は異なる４カ所のエッジ部を評価した。
評価基準は以下の通りである。
+ +：破れ無し。良好な結果である。
+ ：一部破れ電子部品が露出しているが、実用上問題ない。
NG：上記＋の評価未満、若しくはエッジ全体で破れ発生し電子部品が全域露出。実用不可。
<Edge tear resistance>
The breakage of the edge portion of the vacuum forming electromagnetic wave shield laminate shown in FIG. 3 was observed and evaluated by a microscope. Observation evaluated four different edge parts.
Evaluation criteria are as follows.
+ +: There is no tear. It is a good result.
+: Partially broken The electronic component is exposed, but there is no problem in practical use.
NG: The above-mentioned evaluation of + or tearing occurs at the entire edge and the electronic component is exposed to the whole area. Not practical.
＜グランド接続評価＞
実施例１５〜２１を用いて得た、電磁波シールド成型体を、図３の断面図に示す底部のグランド端子１１ｂ‐１１ｃ間の接続抵抗値をＨＩＯＫＩ社製ＲＭ３５４４とピン型リードプローブを用いて測定することにより、グランド接続性を評価した。
評価基準は以下の通りである。
+ + ：接続抵抗値が１０００ｍΩ未満。良好な結果である。
+ ：接続抵抗値が１０００ｍΩ以上、３０００ｍΩ未満。実用上問題ない。
NG ：接続抵抗値が３０００ｍΩ以上。実用不可。
<Ground connection evaluation>
The electromagnetic wave shield molded body obtained by using Examples 15 to 21 was measured for the connection resistance value between the ground terminals 11b and 11c at the bottom shown in the sectional view of FIG. 3 using RM3544 manufactured by HIOKI and a pin type lead probe. The ground connectivity was evaluated by doing.
Evaluation criteria are as follows.
+ +: Connection resistance value is less than 1000 mΩ. It is a good result.
+: Connection resistance value is 1000 mΩ or more and less than 3000 mΩ. There is no problem in practical use.
NG: Connection resistance value is 3000 mΩ or more. Not practical.
実施例および比較例に係る真空成形用電磁波シールド積層体の評価結果を表１に示す。
なお、実施例１５〜２１のグランド接続性評価結果も表２に示した。
The evaluation results of the vacuum forming electromagnetic wave shield laminate according to the example and the comparative example are shown in Table 1.
The ground connectivity evaluation results of Examples 15 to 21 are also shown in Table 2.
本発明の真空成形用電磁波シールド積層体は、電磁波（電界波および磁界波）を放出する部品の輻射電磁波防止および外部からの磁場や電波による誤動作防止に好適なものである。部品としては、携帯電話、電話、パソコン、オーディオ機器、家電機器、無線通信機器、車載部分、建築材料、ゲーム機、アミューズメント機器、包装容器等が例示できる。 The electromagnetic wave shielding laminate for vacuum forming of the present invention is suitable for preventing radiation electromagnetic waves of parts emitting electromagnetic waves (electric field waves and magnetic field waves) and preventing malfunction due to external magnetic fields or radio waves. Examples of components include mobile phones, telephones, personal computers, audio devices, home appliances, wireless communication devices, in-vehicle parts, building materials, game machines, amusement devices, packaging containers, and the like.
１ 電磁波シールド層
２ 粘着層
３ 支持層
１０ 基板
１１ グランド端子
１２ ハーフダイシング溝
１３ 電子部品
１４ 真空成形用電磁波シールド積層体
Reference Signs List 1 electromagnetic wave shield layer 2 adhesive layer 3 support layer 10 substrate 11 ground terminal 12 half dicing groove 13 electronic component 14 electromagnetic wave shield laminate for vacuum forming
Claims (7)
粘着層（Ｂ）とを有する真空成形用電磁波シールド積層体であって、
前記電磁波シールド層（Ａ）を最外層に有し、
前記電磁波シールド層（Ａ）は、引張破断歪が９０〜１５００％である導電性樹脂層であり、
前記積層体を、積層体に対して水平方向に、１５０℃で１．５倍の長さになるまで伸張したときのＫＥＣ法における周波数１ＧＨｚでの電磁波シールド性が４０〜９０ｄＢであることを特徴とする真空成形用電磁波シールド積層体。 An electromagnetic wave shield layer (A),
An electromagnetic shielding laminate for vacuum forming having an adhesive layer (B),
The electromagnetic wave shielding layer (A) is provided on the outermost layer,
The electromagnetic wave shielding layer (A) is a conductive resin layer having a tensile breaking strain of 90 to 1500%,
It is characterized in that the electromagnetic wave shielding property at a frequency of 1 GHz in the KEC method is 40 to 90 dB when the laminate is stretched to a length 1.5 times at 150 ° C. in the horizontal direction with respect to the laminate. An electromagnetic wave shield laminate for vacuum forming.
立体成形体とが一体成形されてなり、
前記真空成形用電磁波シールド積層体の電磁波シールド層（Ａ）が最表面であることを特徴とする電磁波シールド成形体。 An electromagnetic shielding laminate for vacuum forming according to any one of claims 1 to 6,
Ri name and three-dimensional molded body is integrally formed,
An electromagnetic wave shield molded article, wherein the electromagnetic wave shield layer (A) of the electromagnetic wave shield laminate for vacuum forming is the outermost surface .
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| JPH0360099A (en) * | 1989-07-28 | 1991-03-15 | Idemitsu Petrochem Co Ltd | Film or sheet using metal fiber |
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