JP2016143751A - Electromagnetic wave shield sheet and printed wiring board - Google Patents
Electromagnetic wave shield sheet and printed wiring board Download PDFInfo
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- JP2016143751A JP2016143751A JP2015018094A JP2015018094A JP2016143751A JP 2016143751 A JP2016143751 A JP 2016143751A JP 2015018094 A JP2015018094 A JP 2015018094A JP 2015018094 A JP2015018094 A JP 2015018094A JP 2016143751 A JP2016143751 A JP 2016143751A
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Images
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- Non-Insulated Conductors (AREA)
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Structure Of Printed Boards (AREA)
Abstract
Description
本発明は、プリント配線板等の電子部品から発生する電磁波を遮蔽する電磁波シールドシートに関する。 The present invention relates to an electromagnetic wave shielding sheet that shields electromagnetic waves generated from electronic components such as printed wiring boards.
フレキシブルプリント配線板（以下、ＦＰＣという）は、屈曲性を有することから、近年のＯＡ機器、通信機器、携帯電話などの更なる高性能化、小型化の要請に応えるべく、その狭く複雑な構造からなる筐体内部に電子回路を組み込むために多用されている。そうした電子回路のダウンサイズ化・高周波化に伴い、そこから発生する不要な電磁ノイズに対する対策がますます重要になってきている。そこで、従来からＦＰＣに、電子回路から発生する電磁ノイズを遮蔽する電磁波シールドシートを積層することが行われている。この電磁波シールドシートは、電磁波シールド性に加えて、貼り合わせたＦＰＣ全体の耐屈曲性を損なわないよう、薄さと優れた耐屈曲性が要求される。そのため、電磁波シールドシートは、厚さの薄い基材フィルム上に導電層を設けた構成が広く知られている。 A flexible printed wiring board (hereinafter referred to as FPC) has flexibility, and its narrow and complex structure is required to meet the demand for higher performance and miniaturization of recent office automation equipment, communication equipment, mobile phones and the like. It is often used to incorporate an electronic circuit inside a casing made of With such downsizing and high frequency of electronic circuits, countermeasures against unnecessary electromagnetic noise generated therefrom are becoming more and more important. Thus, conventionally, an electromagnetic wave shielding sheet for shielding electromagnetic noise generated from an electronic circuit is laminated on the FPC. In addition to the electromagnetic wave shielding property, the electromagnetic wave shielding sheet is required to have thinness and excellent bending resistance so as not to impair the bending resistance of the bonded FPC as a whole. Therefore, the electromagnetic wave shield sheet is widely known to have a conductive layer provided on a thin base film.
例えば、特許文献１には、接着剤層、カバーフィルム、金属薄膜層、導電性接着剤層を順次積層した電磁波シールドシートが開示されている。また、特許文献２には、ベースフィルム、金属薄膜層、導電性接着剤層を順次積層した電磁波シールドシートが開示されている。また、特許文献３には、カバーフィルム、金属薄膜層、導電性接着剤層を順次積層した電磁波シールドシートが開示されている。
For example,
電磁波シールドフィルムを大判の配線板に貼り付けた後、所定の形にカットし、電子機器に搭載可能な大きさのプリント配線板を作成する。この場合、製造メーカーや生産ロットを把握するため、プリント配線板上の電磁波シールドフィルムの絶縁層上に、スクリーン印刷等により品名やロットナンバーが白色に印字される場合が多いところ、この印字面積が小さいため、文字の大きさも小さいのが通常である。 After the electromagnetic wave shielding film is attached to a large-sized wiring board, it is cut into a predetermined shape to produce a printed wiring board having a size that can be mounted on an electronic device. In this case, in order to grasp the manufacturer and production lot, the product name and lot number are often printed in white on the insulating layer of the electromagnetic shielding film on the printed wiring board by screen printing, etc. Since it is small, the size of characters is usually small.
ＦＰＣは、積層された電磁波シールドシートの最表面に製品番号やロット番号を印字することが行なわれているが、従来の電磁波シールドシートは、最表面が光沢を有するため、ＦＰＣを電子機器に搭載する作業者にとって印字の視認性が悪かった。また、特許文献１の電磁波シールドシートは、接着剤層を着色していたが、着色の色相が悪く、作業者が印字を視認しにくい問題があった。
FPC prints the product number and lot number on the outermost surface of the laminated electromagnetic shielding sheet, but the conventional electromagnetic shielding sheet has gloss on the outermost surface, so FPC is mounted on electronic equipment. The visibility of the print was poor for the workers who do. Moreover, although the electromagnetic wave shield sheet of
本発明は、印字の視認性に優れた絶縁層を有する電磁波シールドシートを提供することを目的とする。 An object of this invention is to provide the electromagnetic wave shield sheet which has an insulating layer excellent in the visibility of printing.
本発明の電磁波シールドシートは、導電層、および絶縁層を備え、
前記絶縁層が熱硬化性樹脂、硬化剤、および黒色系着色剤を含み、前記黒色系着色剤は、平均一次粒子径が２０〜１００ｎｍであることを特徴とする。
The electromagnetic wave shielding sheet of the present invention comprises a conductive layer and an insulating layer,
The insulating layer includes a thermosetting resin, a curing agent, and a black colorant, and the black colorant has an average primary particle diameter of 20 to 100 nm.
上記の本発明によれば絶縁層が平均一次粒子径２０〜１００ｎｍの黒色系着色剤を含むため、絶縁層に印字された文字の視認性が向上したことで、作業者がＦＰＣを選別し、電子機器に搭載するときの作業性が向上し、生産性も向上した。 According to the present invention, since the insulating layer contains a black colorant having an average primary particle diameter of 20 to 100 nm, the visibility of characters printed on the insulating layer is improved, so that the operator selects FPC, Workability when mounted on electronic equipment has improved, and productivity has also improved.
本発明により印字の視認性に優れた絶縁層を有する電磁波シールドシートを提供できる。 According to the present invention, an electromagnetic wave shielding sheet having an insulating layer excellent in printing visibility can be provided.
本発明の電磁波シールドシートは、導電層および絶縁層を備える。 The electromagnetic wave shielding sheet of the present invention includes a conductive layer and an insulating layer.
＜絶縁層＞
絶縁層は、熱硬化性樹脂、硬化剤、および黒色系着色剤を含む絶縁性樹脂組成物を成形することで得る。
<Insulating layer>
The insulating layer is obtained by molding an insulating resin composition containing a thermosetting resin, a curing agent, and a black colorant.
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。
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 is a resin having a plurality of functional groups that can be used for a crosslinking reaction by heating.
Examples of the functional group include a hydroxyl group, a phenolic hydroxyl group, a carboxyl group, an amino group, an epoxy group, an oxetanyl group, an oxazoline group, an oxazine group, an aziridine group, a thiol group, an isocyanate group, a blocked isocyanate group, and a silanol group. .
Examples of the thermosetting resin having the above functional group include acrylic resin, maleic acid resin, polybutadiene resin, polyester resin, condensation type polyester resin, addition type polyester resin, melamine resin, polyurethane resin, polyurethane urea resin, and epoxy resin. 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 resin, polyurethane urea resin, epoxy resin, addition type polyester resin, polyimide resin, polyamide resin, and polyamideimide resin are preferable from the viewpoint of surface resistance value and abrasion resistance.
本発明では熱硬化性樹脂に加え、熱可塑性樹脂を併用できる。
熱可塑性樹脂としては、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 the present invention, a thermoplastic resin can be used in combination with the thermosetting resin.
As thermoplastic resins, polyolefin resins, vinyl resins, styrene / acrylic resins, diene resins, terpene resins, petroleum resins, cellulose resins, polyamide resins, polyurethane resins, polyester resins that do not have the above curable functional groups. , Polycarbonate resin, polyimide resin, fluorine resin and the like.
The polyolefin resin is preferably a homopolymer or copolymer such as ethylene, propylene, and α-olefin compound. Specific examples include polyethylene propylene rubber, olefinic thermoplastic elastomer, α-olefin polymer, and the like.
The vinyl resin is preferably a polymer obtained by polymerization of vinyl ester such as vinyl acetate or a copolymer of vinyl ester and olefin compound such as ethylene. Specific examples include ethylene-vinyl acetate copolymer and partially saponified polyvinyl alcohol.
The styrene / acrylic resin is preferably a homopolymer or copolymer composed of styrene, (meth) acrylonitrile, acrylamides, (meth) acrylic acid esters, maleimides and the like. Specific examples include syndiotactic polystyrene, polyacrylonitrile, acrylic copolymer, ethylene-methyl methacrylate copolymer, and the like.
The diene resin is preferably a homopolymer or copolymer of a conjugated diene compound such as butadiene or isoprene and a hydrogenated product thereof. Specific examples include styrene-butadiene rubber and styrene-isoprene block copolymer. The terpene resin is preferably a polymer composed of terpenes or a hydrogenated product thereof. Specific examples include aromatic modified terpene resins, terpene phenol resins, and hydrogenated terpene resins.
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.
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。 The curing agent has a plurality of functional groups that can react 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, an aromatic diamine, or a phenol compound such as a phenol novolac resin.
硬化剤は、熱硬化性樹脂１００重量部に対して１〜５０重量部含むことが好ましく、３〜３０重量部がより好ましく、３〜２０重量部がさらに好ましい。 It is preferable that 1-50 weight part is contained with respect to 100 weight part of thermosetting resins, as for a hardening | curing agent, 3-30 weight part is more preferable, and 3-20 weight part is further more preferable.
絶縁層は、黒色系着色剤を含むことで印字された文字の視認性を向上できる。黒色系着色剤は、黒色顔料、ならびに赤色、緑色、青色、黄色、紫色、シアンおよびマゼンタ等の顔料を複数含む混合系着色剤が好ましい。混合系着色剤は、複数の顔料を減色混合することで黒色を得ることができる。
黒色顔料は、例えばカーボンブラック、ケッチェンブラック、カーボンナノチューブ（ＣＮＴ）、ペリレンブラック、チタンブラック、鉄黒、アニリンブラック等が挙げられる。
The insulating layer can improve the visibility of the printed character by including a black colorant. The black colorant is preferably a black color pigment and a mixed colorant containing a plurality of pigments such as red, green, blue, yellow, purple, cyan and magenta. The mixed colorant can obtain black color by subtractive color mixing of a plurality of pigments.
Examples of the black pigment include carbon black, ketjen black, carbon nanotube (CNT), perylene black, titanium black, iron black, and aniline black.
黒色系着色剤は、平均一次粒子径が２０〜１００ｎｍであることが必要である。前記平均一次粒子径の黒色系着色剤を用いることで絶縁層は、色ムラのない鮮明な黒色に着色でき、文字の視認性がより向上する。平均一次粒子径を２０ｎｍ以上にすることで絶縁性樹脂組成物の粘度を塗工に適した水準に維持しやすい。また平均一次粒子径を１００ｎｍ以下にすることで絶縁層の黒色度が向上し、印字視認性がより向上する。なお、黒色系着色剤の粒子形状が、１．５以上の平均アスペクト比（長軸長さ／短軸長さ）を有する場合、平均一次粒子径は、長軸長さを平均して求める。 The black colorant needs to have an average primary particle size of 20 to 100 nm. By using the black colorant having the average primary particle size, the insulating layer can be colored in clear black without color unevenness, and the visibility of characters is further improved. By setting the average primary particle diameter to 20 nm or more, the viscosity of the insulating resin composition can be easily maintained at a level suitable for coating. Moreover, the blackness of an insulating layer improves by making an average primary particle diameter 100 nm or less, and printing visibility improves more. In addition, when the particle shape of the black colorant has an average aspect ratio (major axis length / minor axis length) of 1.5 or more, the average primary particle diameter is obtained by averaging the major axis lengths.
なお、黒色系着色剤の平均一次粒子径は透過型電子顕微鏡（ＴＥＭ）により５万倍〜１００万倍程度に拡大した画像から観察できる２０個程度の一次粒子の平均値から求めることができる。 The average primary particle diameter of the black colorant can be determined from an average value of about 20 primary particles that can be observed from an image enlarged to about 50,000 to 1,000,000 times with a transmission electron microscope (TEM).
混合系着色剤は、以下の顔料を使用できる。なお、「Ｃ．Ｉ．」は、カラーインデックス（Ｃ．Ｉ．）を意味する。 The following pigments can be used as the mixed colorant. “CI” means a color index (CI).
赤色顔料およびマゼンタ顔料は、例えばＣ．Ｉ．ピグメントレッド ７、１４、４１、４８：１、４８：２、４８：３、４８：４、５７：１、８１、８１：１、８１：２、８１：３、８１：４、１２２、１４６、１６８、１７６、１７７、１７８、１８４、１８５、１８７、２００、２０２、２０８、２１０、２４２、２４６、２５４、２５５、２６４、２７０、２７２および２７９等が挙げられる。 Examples of red pigments and magenta pigments include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168, 176, 177, 178, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, and 279.
緑顔料は、例えばＣ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５および５８等が挙げられる。
Examples of the green pigment include C.I. I.
青顔料およびシアン顔料は、例えばＣ．Ｉ．ピグメントブルー１、１：２、９、１４、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、１９、２５、２７、２８、２９、３３、３５、３６、５６、５６：１、６０、６１、６１：１、６２、６３、６６、６７、６８、７１、７２、７３、７４、７５、７６、７８および７９等が挙げられる。
Blue pigments and cyan pigments are exemplified by C.I. I.
黄顔料は、例えばＣ．Ｉ．ピグメントイエロー１、２、３、４、５、６、１０、１２、１３、１４、１５、１６、１７、１８、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４２、４３、５３、５５、６０、６１、６２、６３、６５、７３、７４、７７、８１、８３、９３、９４、９５、９７、９８、１００、１０１、１０４、１０６、１０８、１０９、１１０、１１３、１１４、１１５、１１６、１１７、１１８、１１９、１２０、１２３、１２６、１２７、１２８、１２９、１３８、１３９、１４７、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１６１、１６２、１６４、１６６、１６７、１６８、１６９、１７０、１７１、１７２、１７３、１７４、１７５、１７６、１７７、１７９、１８０、１８１、１８２、１８４、１８５、１８７、１８８、１９３、１９４、１９８、１９９、２１３および２１４等が挙げられる。
Examples of yellow pigments include C.I. I.
紫顔料としては、例えばＣ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９および５０等が挙げられる。
Examples of purple pigments include C.I. I.
黒色系着色剤は、絶縁層１００重量％中に０．５〜４０重量％含むことが好ましく、１〜３０重量％がより好ましい。黒色系着色剤を０．５〜４０重量％含むことで絶縁層は、良好な印字視認性と、絶縁性を両立し易くなる。 The black colorant is preferably contained in an amount of 0.5 to 40% by weight, more preferably 1 to 30% by weight, in 100% by weight of the insulating layer. By including 0.5 to 40% by weight of the black colorant, the insulating layer can easily achieve both good print visibility and insulating properties.
絶縁性樹脂組成物は、必要に応じて黒色系着色剤以外の顔料および染料、ならびにシランカップリング剤、酸化防止剤、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤，充填剤，難燃剤等を含むことができる。 Insulating resin compositions include pigments and dyes other than black colorants as necessary, silane coupling agents, antioxidants, tackifier resins, plasticizers, ultraviolet absorbers, antifoaming agents, leveling regulators, Fillers, flame retardants and the like can be included.
絶縁性樹脂組成物は、熱硬化性樹脂、硬化剤、および黒色系着色剤を混合し攪拌して得ることができる。攪拌は、公知の攪拌装置を使用でき、ディスパーマットやホモジナイザー等が好ましい。 The insulating resin composition can be obtained by mixing and stirring a thermosetting resin, a curing agent, and a black colorant. For the stirring, a known stirring device can be used, and a disperse mat or a homogenizer is preferable.
絶縁層は、例えば絶縁性樹脂組成物を剥離性シート上に塗工することで形成できる。または、絶縁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 insulating layer can be formed, for example, by applying an insulating resin composition onto a peelable sheet. Alternatively, the insulating resin composition can be formed by extruding it 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, for example, gravure coating method, kiss coating method, die coating method, lip coating method, comma coating method, blade method, roll coating method, knife coating method, spray coating method, bar coating method, spin coating method, dip coating method A known coating method such as can be used. When applying, a drying step may be provided as necessary. For the drying, a known drying device such as a hot air dryer or an infrared heater can be used.
絶縁層の厚みは、用途に応じて適宜設計可能であるが、約０．５μｍ〜２５μｍ程度が好ましく、２μｍ〜１５μｍ程度がより好ましい。 The thickness of the insulating layer can be appropriately designed according to the use, but is preferably about 0.5 μm to 25 μm, and more preferably about 2 μm to 15 μm.
＜絶縁層の光沢＞
本発明の電磁波シールドシートは、絶縁層表面の８５°光沢度が１５〜５０であることが好ましい。光沢度が１５〜５０であることで光は絶縁層表面で適度に散乱され、光沢感が適度に抑制される。そのため、絶縁層に印字された文字は、様々な角度から見易くなるため視認性が向上する。さらに光沢度が１５〜５０になると絶縁層表面の凹凸度合いが適度に大きくなり、接触する実質的な面積が減少するため耐摩耗性が向上する。
光沢度が１５以上になることで剥離性シートと絶縁層との間の剥離が容易になる。また光沢度が５０以下になると印字の視認性がより向上する。なお、光沢度の測定方法は後述する。
<Gloss of insulating layer>
In the electromagnetic wave shielding sheet of the present invention, the 85 ° glossiness of the insulating layer surface is preferably 15 to 50. When the glossiness is 15 to 50, light is appropriately scattered on the surface of the insulating layer, and glossiness is moderately suppressed. Therefore, the characters printed on the insulating layer are easy to see from various angles, so the visibility is improved. Further, when the glossiness is 15 to 50, the degree of unevenness on the surface of the insulating layer is appropriately increased, and the substantial area of contact is reduced, so that the wear resistance is improved.
When the glossiness is 15 or more, peeling between the peelable sheet and the insulating layer becomes easy. Further, when the glossiness is 50 or less, the visibility of printing is further improved. A method for measuring the gloss level will be described later.
絶縁層表面に所定の光沢値を付与するためには、例えば、以下のような方法によることができる。
剥離性シートの剥離処理面にあらかじめ、サンドブラスト処理等によって凹凸を形成する。この表面に絶縁性樹脂組成物を塗工することで、剥離性シートの凹凸が絶縁層に転写され、適度な光沢度を付与することができる。
また別の方法として、剥離性シート上に形成した導電層に、絶縁性樹脂組成物を塗工し、機械研磨などの処理を施すことによって光沢度を調整できる。
または、これらの方法によらずとも、適当な艶消し剤や無機フィラー等の添加剤を絶縁性樹脂組成物に添加することで、絶縁層表面に凹凸を形成することも可能である。
In order to give a predetermined gloss value to the surface of the insulating layer, for example, the following method can be used.
Unevenness is formed in advance on the release surface of the release sheet by sandblasting or the like. By coating the surface with the insulating resin composition, the unevenness of the peelable sheet is transferred to the insulating layer, and appropriate glossiness can be imparted.
As another method, the glossiness can be adjusted by applying an insulating resin composition to a conductive layer formed on a peelable sheet and performing a process such as mechanical polishing.
Alternatively, it is also possible to form irregularities on the surface of the insulating layer by adding an additive such as a suitable matting agent or inorganic filler to the insulating resin composition, regardless of these methods.
＜絶縁層のＬ＊値＞
本発明の電磁波シールドシートは、絶縁層表面のＬ＊ａ＊ｂ＊表色系におけるＬ＊値が２０〜３０であることが好ましい。Ｌ＊値を２０〜３０にすると絶縁層表面で光が吸収され、例えば、白色で印字した文字をよりはっきりと視認できる。
また、Ｌ＊値を上記範囲にすることで、表面の一部がこすれて摩耗した場合、外観の黒色度は大きく変わらず、外観不良が起きにくくなる。すなわち耐摩耗性を向上することができる。なお、Ｌ＊ａ＊ｂ＊値は色空間を表す座標軸である。Ｌ＊は、明度を意味する次元、ａ＊およびｂ＊は、補色次元を意味する。Ｌ＊値が高い場合漆黒性は低く。逆にＬ＊値が低い場合漆黒性が高いため、印字視認性が良好となる。
<L * value of insulating layer>
In the electromagnetic wave shielding sheet of the present invention, the L * value in the L * a * b * color system on the surface of the insulating layer is preferably 20-30. When the L * value is 20 to 30, light is absorbed on the surface of the insulating layer, and for example, characters printed in white can be visually recognized more clearly.
Further, by setting the L * value within the above range, when a part of the surface is rubbed and worn, the blackness of the appearance does not change greatly, and appearance defects are less likely to occur. That is, wear resistance can be improved. The L * a * b * value is a coordinate axis representing the color space. L * is a dimension meaning lightness, and a * and b * are complementary color dimensions. When L * value is high, jetness is low. On the other hand, when the L * value is low, the print visibility is good because the jetness is high.
このようなＬ＊値を得るためには、例えば、平均一次粒子径が２０〜１００ｎｍである黒色系着色剤を、形成される絶縁層中に０．５〜４０重量％配合することが好ましく、１〜３０重量％配合することがより好ましい。なお、Ｌ＊値を２０〜３０に調整する手段が黒色系着色剤に限定されないことはいうまでもない。黒色系着色剤に２次凝集が生じた場合は、必要に応じてサンドミル等で解砕処理を行うことでＬ値を２０〜３０に調整できる。 In order to obtain such an L * value, for example, it is preferable to mix 0.5 to 40% by weight of a black colorant having an average primary particle diameter of 20 to 100 nm in the formed insulating layer. It is more preferable to add 1 to 30% by weight. Needless to say, the means for adjusting the L * value to 20 to 30 is not limited to the black colorant. When secondary aggregation occurs in the black colorant, the L value can be adjusted to 20 to 30 by performing a crushing treatment with a sand mill or the like as necessary.
Ｌ値が２０以上にすることで絶縁信頼性をより向上できる。またＬ値が３０以下になることで印字視認性がより向上する。 When the L value is 20 or more, the insulation reliability can be further improved. Further, when the L value is 30 or less, the print visibility is further improved.
＜絶縁層の表面抵抗値＞
本発明の電磁波シールドシートは、絶縁層の表面抵抗値が１×１０5〜１×１０14Ω／□であることが好ましい。絶縁層の表面抵抗値が１×１０5Ω／□以上になることで絶縁性がより向上する。また表面抵抗値が１×１０14Ω／□以下になることで、例えば、絶縁層を絶縁性樹脂組成物の塗工で形成する場合の塗工性がより向上する。
<Surface resistance value of insulating layer>
In the electromagnetic wave shielding sheet of the present invention, the surface resistance value of the insulating layer is preferably 1 × 10 5 to 1 × 10 14 Ω / □. When the surface resistance value of the insulating layer is 1 × 10 5 Ω / □ or more, the insulation is further improved. Further, when the surface resistance value is 1 × 10 14 Ω / □ or less, for example, the coating property when the insulating layer is formed by coating the insulating resin composition is further improved.
＜導電層＞
導電層は、バインダー樹脂および導電性微粒子を含む導電性樹脂組成物から形成することが好ましい。また、導電層は、プリント配線板上に形成されたカバーフィルムや絶縁基材等に貼付されるため接着性を有する。
<Conductive layer>
The conductive layer is preferably formed from a conductive resin composition containing a binder resin and conductive fine particles. Moreover, since a conductive layer is affixed on the cover film, insulation base material, etc. which were formed on the printed wiring board, it has adhesiveness.
導電層は、等方導電層または異方導電層から適宜選択できる。当方導電層は、電磁波シールドシート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。また、異方導電層は、電磁波シールドシートを水平に置いた状態で、上下方向のみに導電性を有する。 The conductive layer can be appropriately selected from an isotropic conductive layer or an anisotropic conductive layer. This conductive layer has conductivity in the vertical direction and the horizontal direction with the electromagnetic wave shielding sheet placed horizontally. The anisotropic conductive layer is conductive only in the vertical direction with the electromagnetic wave shielding sheet placed horizontally.
バインダー樹脂は、絶縁層で説明した熱硬化性樹脂、熱可塑性樹脂から適宜選択して使用できる。熱硬化性樹脂を使用する場合、絶縁層で説明した硬化剤を併用することが好ましい。 The binder resin can be appropriately selected from the thermosetting resins and thermoplastic resins described in the insulating layer. When using a thermosetting resin, it is preferable to use together the curing agent described in the insulating layer.
バインダー樹脂は、ガラス転移温度（Ｔｇ）が−２０〜１００℃が好ましく、０〜８０℃がより好ましい。バインダー樹脂は、１種類を用いても複数種類を併用してもよい。複数種類を用いる場合は、混合前のＴｇが上記範囲に含まれているものを主成分とすることが好ましい。なおＴｇは、メトラー・トレド社製「ＤＳＣ−１」を用いて測定した。 The binder resin preferably has a glass transition temperature (Tg) of -20 to 100 ° C, more preferably 0 to 80 ° C. One type of binder resin may be used or a plurality of types may be used in combination. In the case of using a plurality of types, it is preferable that the main component is Tg before mixing included in the above range. Tg was measured using “DSC-1” manufactured by METTLER TOLEDO.
導電性微粒子は、金、白金、銀、銅およびニッケル等の導電性金属、ならびにその合金、ならびに導電性ポリマーの微粒子が好ましい。また単一組成の微粒子ではなく金属や樹脂を核体とし、前記核体の表面を被覆する被覆層を核体よりも導電性が高い素材で形成した複合微粒子がコストダウンの観点から好ましい。
核体は、ニッケル、シリカ、銅および樹脂から選択することが好ましく、導電性の金属およびその合金がより好ましい。
被覆層は、導電性が優れる素材であればよく、導電性金属または導電性ポリマーが好ましい。導電性金属は、例えば、金、白金、銀、錫、マンガン、およびインジウム等、ならびにその合金が挙げられる。また導電性ポリマーは、ポリアニリン、ポリアセチレン等が挙げられる。これらの中でも導電性の面から銀が好ましい。
The conductive fine particles are preferably conductive metals such as gold, platinum, silver, copper and nickel, and alloys thereof, and conductive polymer fine particles. In addition, composite fine particles in which a metal or resin is used as a nucleus instead of fine particles having a single composition and a coating layer covering the surface of the nucleus is formed of a material having higher conductivity than the nucleus are preferable from the viewpoint of cost reduction.
The nucleus is preferably selected from nickel, silica, copper and resin, and more preferably a conductive metal and an alloy thereof.
The covering layer may be a material having excellent conductivity, and is preferably a conductive metal or a conductive polymer. Examples of the conductive metal include gold, platinum, silver, tin, manganese, indium, and the like, and alloys thereof. Examples of the conductive polymer include polyaniline and polyacetylene. Among these, silver is preferable from the viewpoint of conductivity.
複合微粒子は、核体１００重量部に対して、１〜４０重量部の割合で被覆層を有することが好ましく、５〜３０重量部がより好ましい。１〜４０重量部で被覆すると、導電性を維持しながら、よりコストダウンができる。なお複合微粒子は、被覆層が核体を完全に覆うことが好ましい。しかし、実際には、核体の一部が露出する場合がある。このような場合でも核体表面面積の７０％以上を導電性物質が覆っていれば、導電性を維持しやすい。 The composite fine particles preferably have a coating layer at a ratio of 1 to 40 parts by weight, and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the nucleus. Covering with 1 to 40 parts by weight can further reduce the cost while maintaining conductivity. In the composite fine particles, it is preferable that the coating layer completely covers the core. However, in practice, a part of the nucleus may be exposed. Even in such a case, if the conductive material covers 70% or more of the core surface area, the conductivity is easily maintained.
導電性微粒子の形状は、所望の導電性が得られればよく形状は限定されない。具体的には、例えば、球状、フレーク状、葉状、樹枝状、プレート状、針状、棒状、ブドウ状が好ましい。なお、導電性微粒子は、一般にフレーク状の微粒子を使用すると等方導電性が得られ、球状または樹枝状の微粒子を使用すると異方導電性が得られる。 The shape of the conductive fine particles is not limited as long as desired conductivity is obtained. Specifically, for example, a spherical shape, a flake shape, a leaf shape, a dendritic shape, a plate shape, a needle shape, a rod shape, and a grape shape are preferable. The conductive fine particles generally have isotropic conductivity when flaky fine particles are used, and anisotropic conductivity is obtained when spherical or dendritic fine particles are used.
導電性微粒子の平均粒子径は、Ｄ５０平均粒子径であり、１〜１００μｍが好ましく、３〜５０μｍがより好ましい。
なお、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とした。
The average particle diameter of the conductive fine particles is D50 average particle diameter, preferably 1 to 100 μm, more preferably 3 to 50 μm.
The D50 average particle size 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 device LS13320 (manufactured by Beckman Coulter, Inc.). The cumulative value in the cumulative particle size distribution is a particle size of 50%. The refractive index was set to 1.6.
導電性微粒子は、単独または２種類以上を併用できる。 The conductive fine particles can be used alone or in combination of two or more.
導電性微粒子は、バインダー樹脂１００重量部に対して、５０〜１５００重量部を配合することが好ましく、１００〜１０００重量部がより好ましい。 The conductive fine particles are preferably blended in an amount of 50 to 1500 parts by weight, more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the binder resin.
導電性樹脂組成物は、さらにイオンキャッチャー剤を含むことが好ましい。イオンキャッチャー剤を配合すると、導電性微粒子が金属微粒子である場合、金属イオンに起因した導電性および密着性の経時低下を抑制できる。
イオンキャッチャー剤は、例えば、アセチルアセトン、アセト酢酸エチル、Ｎ−サリシロイル−Ｎ’−アルデヒドラジン、Ｎ，Ｎ−ジベンザル（オキザルヒドラジド）、イソフタリック酸ビス（２−フェノキシプロピオニルヒドラジン）[３−（Ｎ−サリチロイル）アミノ−１，２，４−ヒドロキシフェニル）プロピオニル］ヒドラジン、デカメチレンカルボン酸ジサリチロイルヒドラジド、Ｎ，Ｎ’−ビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニル］ヒドラジン等が挙げられる。これらの中でもデカメチレンカルボン酸ジサリチロイルヒドラジドおよびＮ，Ｎ’−ビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニル］ヒドラジンはイオン捕捉効果が高いため好ましい。
The conductive resin composition preferably further contains an ion catcher agent. When the ion catcher agent is blended, when the conductive fine particles are metal fine particles, it is possible to suppress a decrease in conductivity and adhesion due to metal ions over time.
Examples of the ion catcher agent include acetylacetone, ethyl acetoacetate, N-salicyloyl-N′-aldehyderazine, N, N-dibenzal (oxalhydrazide), bis (2-phenoxypropionylhydrazine) isophthalic acid [3- (N— Salicyloyl) amino-1,2,4-hydroxyphenyl) propionyl] hydrazine, decamethylenecarboxylic acid disalicyloylhydrazide, N, N′-bis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionyl] hydrazine and the like. Among these, decamethylene carboxylic acid disalicyloyl hydrazide and N, N′-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine are preferable because of their high ion scavenging effect.
イオンキャッチャー剤は、導電性微粒子１００重量部に対して、０．５〜３０重量部配合することが好ましく、１〜２０重量部がより好ましい。０．５〜３０重量部配合することで導電性および耐熱性の経時低下をより抑制できる。 The ion catcher agent is preferably blended in an amount of 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the conductive fine particles. By blending 0.5 to 30 parts by weight, the deterioration of conductivity and heat resistance with time can be further suppressed.
また、導電性樹脂組成物は、さらに増粘剤を含むことが好ましい。増粘剤を含むことで導電性樹脂組成物は導電性微粒子の分散安定性が向上する。増粘剤は、例えばシリカ粉末、有機ベントナイト、ポリカルボン酸化合物、ポリウレタン化合物、ウレア化合物、ポリアミド化合物等が好ましい。 Moreover, it is preferable that a conductive resin composition contains a thickener further. By including the thickener, the conductive resin composition improves the dispersion stability of the conductive fine particles. As the thickener, for example, silica powder, organic bentonite, polycarboxylic acid compound, polyurethane compound, urea compound, polyamide compound and the like are preferable.
導電性樹脂組成物は、さらにシランカップリング剤、防錆剤、還元剤、酸化防止剤、顔料、染料、粘着付与樹脂、可塑剤、紫外線吸収剤、消泡剤、レベリング調整剤、充填剤、難燃剤等を配合できる。 The conductive resin composition further includes a silane coupling agent, a rust inhibitor, a reducing agent, an antioxidant, a pigment, a dye, a tackifier resin, a plasticizer, an ultraviolet absorber, an antifoaming agent, a leveling regulator, a filler, A flame retardant etc. can be mix | blended.
導電性樹脂組成物は、導電性微粒子とバインダー樹脂とを混合し攪拌して得ることができる。攪拌は、公知の攪拌装置を使用でき、ディスパーマットやホモジナイザー等が好ましい。 The conductive resin composition can be obtained by mixing and stirring the conductive fine particles and the binder resin. For the stirring, a known stirring device can be used, and a disperse mat or a homogenizer is preferable.
導電層は、導電性樹脂組成物を使用して絶縁層での説明と同様に作製できる。 The conductive layer can be manufactured using the conductive resin composition as described in the insulating layer.
導電層の厚みは、１〜１００μｍが好ましく、３〜５０μｍがより好ましく、４〜１５μｍがさらに好ましい。厚みが１〜１００μｍの範囲にあることで導電性と、その他の物性を両立しやすくなる。 1-100 micrometers is preferable, as for the thickness of a conductive layer, 3-50 micrometers is more preferable, and 4-15 micrometers is further more preferable. It becomes easy to make electroconductivity and other physical properties compatible because thickness exists in the range of 1-100 micrometers.
＜電磁波シールドシート＞
本発明の電磁波シールドシートは、絶縁層および導電層を備えた第一の実施態様、絶縁層、金属薄膜層および導電層を備えた第二の実施態様が好ましい。
第一の実施態様の場合、導電層は、等方導電層である。また第二の実施態様の場合、導電層は、等方導電層および異方導電層から適宜選択できるところ、異方導電層を使用するとコストダウンが容易になる。
<Electromagnetic wave shield sheet>
The electromagnetic shielding sheet of the present invention is preferably a first embodiment provided with an insulating layer and a conductive layer, and a second embodiment provided with an insulating layer, a metal thin film layer and a conductive layer.
In the case of the first embodiment, the conductive layer is an isotropic conductive layer. In the second embodiment, the conductive layer can be appropriately selected from an isotropic conductive layer and an anisotropic conductive layer. However, the use of the anisotropic conductive layer facilitates cost reduction.
第一の実施態様の作製は、既に説明したように予め作製した導電層、絶縁層を貼り合わせることで得られる。または、公知の方法で作製できる。 The production of the first embodiment can be obtained by laminating a conductive layer and an insulating layer produced in advance as already described. Or it can produce by a well-known method.
第二の実施態様の作製は、例えば、剥離性シート上に金属層を形成し、別途、剥離性シート上に異方導電層を形成したものを、金属薄膜面にラミネートして製造できる。 The production of the second embodiment can be produced, for example, by forming a metal layer on a peelable sheet and separately laminating an anisotropic conductive layer on the peelable sheet on the metal thin film surface.
金属層は、例えばアルミニウム、銅、銀、金等の導電性の金属箔が好ましく、シールド性、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、銅がさらに好ましい。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、金属層の薄さを追及すると圧延銅箔をエッチング処理したものや電解銅箔がより好ましい。金属箔の場合、厚みは０．１〜１０μｍが好ましく、０．５〜５μｍがより好ましい。
また、金属層は、金属箔以外に真空蒸着、スパッタリング、ＣＶＤ法、ＭＯ（メタルオーガニック）、メッキ等で形成しても良い。これらの中でも量産性を考慮すれば真空蒸着およびメッキが好ましい。金属箔以外の金属層の厚みは、通常０．００５〜５μｍ程度である。なお、金属蒸着膜の厚みは、０．１〜３μｍが好ましい。スパッタリングの厚みは、１０〜１０００ｎｍが好ましい。
The metal layer is preferably, for example, a conductive metal foil such as aluminum, copper, silver, or gold, more preferably copper, silver, or aluminum, and even more preferably copper from the viewpoint of shielding properties and cost. For example, rolled copper foil or electrolytic copper foil is preferably used as the copper, and when the thickness of the metal layer is pursued, a rolled copper foil or an electrolytic copper foil is more preferable. In the case of a metal foil, the thickness is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.
In addition to the metal foil, the metal layer may be formed by vacuum deposition, sputtering, CVD, MO (metal organic), plating, or the like. Among these, vacuum deposition and plating are preferable in consideration of mass productivity. The thickness of the metal layer other than the metal foil is usually about 0.005 to 5 μm. In addition, as for the thickness of a metal vapor deposition film, 0.1-3 micrometers is preferable. The thickness of sputtering is preferably 10 to 1000 nm.
本発明の電磁波シールドシートは、上記層構成に加えて、導電性・絶縁性以外の他の機能層を積層することもできる。
他の機能層は、例えばハードコート性、水蒸気バリア性、酸素バリア性、低誘電率、高誘電率性または耐熱性等の機能を有する層である。
In addition to the above layer structure, the electromagnetic wave shielding sheet of the present invention can also be laminated with other functional layers other than conductivity and insulation.
The other functional layer is a layer having functions such as hard coat property, water vapor barrier property, oxygen barrier property, low dielectric constant, high dielectric constant property, and heat resistance.
また、本発明の電磁波シールドシートは、熱硬化性樹脂を使用した場合、熱硬化性樹脂の架橋性官能基と硬化剤の官能基が一部反応した状態（半硬化状態）で存在するのが好ましい。そして、電磁波シールドシートを使用する際、例えばＦＰＣ（フレキシブルプリント配線板）に重ね、または貼り付けた後に加熱圧着工程により十分に硬化することで所望の接着強度が得られる場合が多い。 In addition, when the thermosetting resin is used, the electromagnetic wave shielding sheet of the present invention exists in a state where the crosslinkable functional group of the thermosetting resin and the functional group of the curing agent are partially reacted (semi-cured state). preferable. And when using an electromagnetic wave shield sheet, for example, it piles on or attaches to FPC (flexible printed wiring board), and after that, it is often hardened by a thermocompression bonding process, and desired adhesive strength is often obtained.
剥離性シートは、紙またはプラスチックの基材を使用することが好ましく、基材の一方の面に公知の剥離処理がされているシート、または剥離処理に代えて、微粘着力の粘着剤層が形成されたシートである。 The peelable sheet preferably uses a paper or plastic substrate, and a sheet having a known release treatment on one side of the substrate or a pressure sensitive adhesive layer instead of the release treatment is used. It is a formed sheet.
なお電磁波シールドシートは、導電層または絶縁層の保護および取り扱いを容易にするため、使用する直前まで剥離性シートを貼り付けた状態で保存する場合が多い。 Note that the electromagnetic wave shielding sheet is often stored in a state where a peelable sheet is pasted until just before use, in order to facilitate protection and handling of the conductive layer or the insulating layer.
本発明の電磁波シールドシートは、電磁波をシールドする必要がある様々な用途に使用できる。例えば、リジッドプリント配線板は元より、フレキシブルプリント配線板、ＣＯＦ、ＴＡＢ、フレキシブルコネクタ、液晶ディスプレイ、タッチパネル等に使用できる。また、パソコンのケース、建材の壁および窓ガラス等の建材、車両、船舶、航空機等の電磁波を遮蔽する部材としても使用できる。 The electromagnetic wave shielding sheet of the present invention can be used for various applications where electromagnetic waves need to be shielded. For example, rigid printed wiring boards can be used for flexible printed wiring boards, COFs, TABs, flexible connectors, liquid crystal displays, touch panels, and the like. Moreover, it can also be used as a member for shielding electromagnetic waves from a case of a personal computer, a building material such as a wall of a building material and a window glass, a vehicle, a ship, and an aircraft.
本発明のプリント配線板は、電磁波シールドシートと、カバーコート層ならびに信号配線および絶縁性基材を含む配線板とを備えている。 The printed wiring board of the present invention includes an electromagnetic wave shielding sheet, and a wiring board including a cover coat layer, signal wiring, and an insulating substrate.
本発明のプリント配線板について、図２を参照して説明する。
電磁波シールドシート４は、絶縁層１、金属層３、導電層２を含む構成である。なお図示しないが、電磁波シールドシートは、絶縁層１、導電層２を含む構成も好ましい。
The printed wiring board of the present invention will be described with reference to FIG.
The electromagnetic wave shielding sheet 4 includes an insulating
カバーコート層６は、配線板の信号配線を覆い外部環境から保護する絶縁材料である。カバーコート層６は、熱硬化型または紫外線硬化型のソルダーレジスト、感光性カバーレイフィルムが好ましく、微細加工をするためには感光性カバーレイフィルムがより好ましい。
The
信号配線は、アースを取るグランド配線８、電子部品に電気信号を送る配線回路９を含む。両者は銅箔をエッチング処理することで形成することが一般的である。
絶縁性基材７は、配線板がフレキシブルプリント配線板（ＦＰＣ）である場合、ポリエステル、ポリカーボネート、ポリイミド、ポリフェニレンサルファイド等の屈曲可能なプラスチックが好ましく、ポリイミドがより好ましい。また、配線板がリジッド配線板の場合、絶縁性基材７の構成材料は、ガラスエポキシが好ましい。これらのような絶縁性基材７を備えることで配線板は高い耐熱性が得られる。
The signal wiring includes a
When the insulating
電磁波シールドシート４と、配線板との加熱圧着は、温度１５０〜１９０℃程度、圧力１〜３ＭＰａ程度、時間１〜６０分程度の条件で行うことが一般的である。加熱圧着により導電層２とカバーコート層６が密着するとともに、導電層２が流動して穴１０を埋めることでグランド配線８との間で導通が取れる。さらに熱硬化性樹脂を使用した場合、加熱圧着により熱硬化性樹脂と硬化剤が反応する。なお、硬化を促進させるため、加熱圧着後に１５０〜１９０℃で３０〜９０分間ポストキュアを行う場合もある。なお、電磁波シールドシートは、加熱圧着後に電磁波シールド層ということがある。
Generally, the thermocompression bonding between the electromagnetic wave shielding sheet 4 and the wiring board is performed under conditions of a temperature of about 150 to 190 ° C., a pressure of about 1 to 3 MPa, and a time of about 1 to 60 minutes. The
本発明のプリント配線板は、液晶ディスプレイ、タッチパネル等のほか、ノートＰＣ、携帯電話、スマートフォン、タブレット端末等の電子機器に備えることが好ましい。 The printed wiring board of the present invention is preferably provided in an electronic device such as a notebook PC, a mobile phone, a smartphone, and a tablet terminal in addition to a liquid crystal display and a touch panel.
以下、実施例により本発明をさらに具体的に説明するが、実施例は本発明の権利範囲を何ら制限するものではない。なお、実施例における「部」は「重量部」、「％」は「重量％」を表す。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.
実施例で使用した導電性微粒子、バインダー樹脂、エポキシ化合物を以下に示す。
・導電性微粒子：複合微粒子（核体：銅、被覆層：銀）平均粒径Ｄ５０：１１.０μｍ 福田金属箔粉工業社製）
・バインダー樹脂：熱硬化性ウレタン樹脂（酸価＝５ｍｇＫＯＨ/ｇ）トーヨーケム社製
・エポキシ化合物：ビスフェノールＡ型エポキシ樹脂「ＪＥＲ８２８」（エポキシ当量＝１８９ｇ／ｅｑ）三菱化学社製
アジリジン化合物：「ケミタイトＰＺ−３３」日本触媒社製
The conductive fine particles, binder resin, and epoxy compound used in the examples are shown below.
Conductive fine particles: composite fine particles (nucleus: copper, coating layer: silver) average particle diameter D50: 11.0 μm, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.)
-Binder resin: Thermosetting urethane resin (acid value = 5 mg KOH / g) manufactured by Toyochem Co., Ltd.-Epoxy compound: bisphenol A type epoxy resin "JER828" (epoxy equivalent = 189 g / eq), manufactured by Mitsubishi Chemical Corporation Aziridine compound: "Chemite PZ -33 "manufactured by Nippon Shokubai Co., Ltd.
黒色系着色剤を表１に示す。 Table 1 shows the black colorants.
＜実施例１＞
バインダー樹脂を１００部、導電性微粒子を４５０部、硬化剤としてエポキシ化合物１５部およびアジリジン化合物２．０部を容器に仕込み、不揮発分濃度が４０重量％になるようトルエン：イソプロピルアルコール（重量比２：１）の混合溶剤を加えディスパーで１０分攪拌することで導電性樹脂組成物を得た。次いで、導電性樹脂組成物を剥離性シート上に、乾燥厚みが１０μｍになるようにバーコーターを使用して塗工し、さらに１００℃の電気オーブンで２分間乾燥することで導電層を得た。
<Example 1>
100 parts of binder resin, 450 parts of conductive fine particles, 15 parts of an epoxy compound as a curing agent and 2.0 parts of an aziridine compound are charged into a container, and toluene: isopropyl alcohol (weight ratio: 2) so that the nonvolatile content concentration becomes 40% by weight. 1) was added, and the mixture was stirred with a disper for 10 minutes to obtain a conductive resin composition. Next, the conductive resin composition was coated on a peelable sheet using a bar coater so that the dry thickness was 10 μm, and further dried in an electric oven at 100 ° C. for 2 minutes to obtain a conductive layer. .
別途、バインダー樹脂１００部、黒色系着色剤として旭カーボン社製「ＲＣＦ／ＳＢ２００」１４．８部にメチルエチルケトンを加えて、不揮発分濃度を３０．０重量％に調製した。この混合物をディスパーで攪拌した後にジルコニアビーズを用いてアイガーミル（アイガージャパン社製）で分散することで分散液を得た。得られた分散液中のバインダー樹脂分１００部に対して硬化剤としてエポキシ樹脂３．７部、艶消し剤の「ＣＥＲＡＦＬＯＵＲ９２９」（ポリエチレン粒子入りワックス ビックケミー社製）１部を加えて絶縁性樹脂組成物を得た。この絶縁性樹脂組成物を得られた導電層表面に、バーコーターを用いて乾燥厚みが１５μｍになるように塗工し、さらに１００℃の電気オーブンで３分間乾燥することで電磁波シールドシートを得た。なお、絶縁層側には異物付着防止のため微粘着剥離性シートを貼り合わせた。 Separately, methyl ethyl ketone was added to 100 parts of a binder resin and 14.8 parts of “RCF / SB200” manufactured by Asahi Carbon Co., Ltd. as a black colorant to prepare a nonvolatile content concentration of 30.0% by weight. The mixture was stirred with a disper and then dispersed with an Eiger mill (manufactured by Eiger Japan) using zirconia beads to obtain a dispersion. Insulating resin composition by adding 3.7 parts of an epoxy resin as a curing agent and 1 part of a matting agent “CERAFLOUR929” (manufactured by Wax Big Chemie with polyethylene particles) to 100 parts of a binder resin component in the obtained dispersion. I got a thing. This insulating resin composition was coated on the surface of the conductive layer using a bar coater so that the dry thickness was 15 μm, and further dried in an electric oven at 100 ° C. for 3 minutes to obtain an electromagnetic wave shielding sheet. It was. Note that a slightly adhesive peelable sheet was bonded to the insulating layer side to prevent foreign matter adhesion.
＜実施例２〜１３、比較例１〜３＞
実施例１の原料の種類・配合量を表２のように変更した以外は実施例１と同様に行うことで、電磁波シールドシートを得た。なお比較例２は、絶縁性樹脂組成物が増粘しゲル化したことで塗工により絶縁性が形成できなかったため物性評価を行わなかった。
<Examples 2 to 13 and Comparative Examples 1 to 3>
An electromagnetic wave shielding sheet was obtained in the same manner as in Example 1 except that the type and amount of the raw material in Example 1 were changed as shown in Table 2. In Comparative Example 2, physical properties were not evaluated because insulating properties could not be formed by coating because the insulating resin composition thickened and gelled.
［実施例１５］
バインダー樹脂を１００部、導電性微粒子を７５部、硬化剤としてエポキシ化合物１５部およびアジリジン化合物２．０部を容器に仕込み、不揮発分濃度が４０重量％になるようトルエン：イソプロピルアルコール（重量比２：１）の混合溶剤を加えディスパーで１０分攪拌することで導電性樹脂組成物を得た。次いで、導電性樹脂組成物を剥離性シート上に、乾燥厚みが１０μｍになるようにバーコーターを使用して塗工し、さらに１００℃の電気オーブンで２分間乾燥することで導電層を得た。次いで、ラミネーターを使用して厚さ３μｍの電解銅箔の一方の面に得られた導電層を貼り合わせた。
[Example 15]
100 parts of a binder resin, 75 parts of conductive fine particles, 15 parts of an epoxy compound as a curing agent and 2.0 parts of an aziridine compound are charged into a container, and toluene: isopropyl alcohol (weight ratio: 2) so that the nonvolatile content concentration becomes 40% by weight. 1) was added, and the mixture was stirred with a disper for 10 minutes to obtain a conductive resin composition. Next, the conductive resin composition was coated on a peelable sheet using a bar coater so that the dry thickness was 10 μm, and further dried in an electric oven at 100 ° C. for 2 minutes to obtain a conductive layer. . Subsequently, the obtained conductive layer was bonded to one surface of a 3 μm thick electrolytic copper foil using a laminator.
別途、バインダー樹脂１００部、黒色系着色剤として旭カーボン社製「ＲＣＦ／ＳＢ２００」１４．８部にメチルエチルケトンを加えて、不揮発分濃度を３０．０重量％に調製した。この混合物をディスパーで攪拌した後にジルコニアビーズを用いてアイガーミル（アイガージャパン社製）で分散することで分散液を得た。得られた分散液中のバインダー樹脂分１００部に対して硬化剤としてエポキシ樹脂３．７部、艶消し剤の「ＣＥＲＡＦＬＯＵＲ９２９」１部を加えて絶縁性樹脂組成物を得た。この絶縁性樹脂組成物を得られた導電層と電解銅箔積層体の電解銅箔側に、バーコーターを用いて乾燥厚みが１５μｍになるように塗工し、さらに１００℃の電気オーブンで３分間乾燥することで、電磁波シールドシートを得た。なお、絶縁層側には異物付着防止のため微粘着剥離性シートを貼り合わせた。 Separately, methyl ethyl ketone was added to 100 parts of a binder resin and 14.8 parts of “RCF / SB200” manufactured by Asahi Carbon Co., Ltd. as a black colorant to prepare a nonvolatile content concentration of 30.0% by weight. The mixture was stirred with a disper and then dispersed with an Eiger mill (manufactured by Eiger Japan) using zirconia beads to obtain a dispersion. An insulating resin composition was obtained by adding 3.7 parts of an epoxy resin as a curing agent and 1 part of a “CERAFLOUR929” matting agent to 100 parts of the binder resin in the obtained dispersion. This insulating resin composition was applied to the electroconductive copper foil side of the conductive layer and the electro-deposited copper foil laminate using a bar coater so as to have a dry thickness of 15 μm. An electromagnetic wave shielding sheet was obtained by drying for a minute. Note that a slightly adhesive peelable sheet was bonded to the insulating layer side to prevent foreign matter adhesion.
［実施例１６］
バインダー樹脂を１００部、導電性微粒子を４５０部、硬化剤としてエポキシ化合物１５部およびアジリジン化合物２．０部を容器に仕込み、不揮発分濃度が４０重量％になるようトルエン：イソプロピルアルコール（重量比２：１）の混合溶剤を加えディスパーで１０分攪拌することで導電性樹脂組成物を得た。次いで、導電性樹脂組成物を剥離性シート上に、乾燥厚みが１０μｍになるようにバーコーターを使用して塗工し、さらに１００℃の電気オーブンで２分間乾燥することで導電層を得た。
[Example 16]
100 parts of binder resin, 450 parts of conductive fine particles, 15 parts of an epoxy compound as a curing agent and 2.0 parts of an aziridine compound are charged into a container, and toluene: isopropyl alcohol (weight ratio: 2) so that the nonvolatile content concentration becomes 40% by weight. 1) was added, and the mixture was stirred with a disper for 10 minutes to obtain a conductive resin composition. Next, the conductive resin composition was coated on a peelable sheet using a bar coater so that the dry thickness was 10 μm, and further dried in an electric oven at 100 ° C. for 2 minutes to obtain a conductive layer. .
別途、バインダー樹脂１００部、「ＲＣＦ／ＳＢ２００」１４．８部にメチルエチルケトンを加えて、不揮発分濃度を３０．０重量％に調製した。この混合物をディスパーで攪拌した後にジルコニアビーズを用いてアイガーミル（アイガージャパン社製）で分散することで分散液を得た。得られた分散液中のバインダー樹脂分１００部に対して硬化剤としてエポキシ樹脂３．７部を加えて絶縁性樹脂組成物を得た。この絶縁性樹脂組成物を表面に凹凸を形成した剥離性シート（厚さ５０μｍのポリエチレンテレフタレートフィルム 剥離処理面の表面粗さＲａ＝０．１μｍ）の剥離処理面に、バーコーターを用いて乾燥厚みが１５μｍになるように塗工し、さらに１００℃の電気オーブンで３分間乾燥した後、前記導電層と貼り合わせることで、電磁波シールドシートを得た。 Separately, methyl ethyl ketone was added to 100 parts of a binder resin and 14.8 parts of “RCF / SB200” to prepare a nonvolatile content concentration of 30.0% by weight. The mixture was stirred with a disper and then dispersed with an Eiger mill (manufactured by Eiger Japan) using zirconia beads to obtain a dispersion. An insulating resin composition was obtained by adding 3.7 parts of an epoxy resin as a curing agent to 100 parts of the binder resin in the obtained dispersion. The insulating resin composition is formed on the surface with a release sheet (50 μm thick polyethylene terephthalate film surface roughness Ra = 0.1 μm) on the surface of the release treatment using a bar coater. Was coated in an electric oven at 100 ° C. for 3 minutes, and then bonded to the conductive layer to obtain an electromagnetic wave shielding sheet.
本発明で規定する表面粗さＲａは、ＪＩＳ−Ｂ０６０１で定義されたものであり、表面粗さ計サーフコム５９０Ａ（東京精密社製）で測定した。 The surface roughness Ra specified in the present invention is defined by JIS-B0601, and was measured with a surface roughness meter Surfcom 590A (manufactured by Tokyo Seimitsu Co., Ltd.).
＜比較例４＞
バインダー樹脂を１００部、硬化剤としてエポキシ化合物１０部、アジリジン化合物を１０部および艶消し剤を１部加えディスパーで攪拌した後、剥離性シートに、乾燥厚みが１０μｍになるようにバーコーターを使用して塗工し、１００℃の電気オーブンで２分間乾燥することで絶縁層を得た。そして、実施例１と同様にして形成した導電層に前記絶縁層を貼り合わせることで電磁波シールドシートを得た。
<Comparative example 4>
100 parts of binder resin, 10 parts of epoxy compound as curing agent, 10 parts of aziridine compound and 1 part of matting agent are added and stirred with a disper, and then a bar coater is used on the peelable sheet so that the dry thickness is 10 μm And an insulating layer was obtained by drying in an electric oven at 100 ° C. for 2 minutes. And the electromagnetic wave shielding sheet was obtained by bonding the said insulating layer to the conductive layer formed like Example 1. FIG.
下記評価項目に従い物性を測定した。結果を表１示す。 Physical properties were measured according to the following evaluation items. The results are shown in Table 1.
＜テストピース作製＞
得られた電磁波シールドシートを幅６０ｍｍ・長さ６０ｍｍの大きさに準備し、次いで導電層側の剥離性シートを剥がして露出した導電層と、厚さ１２５μｍのポリイミドフィルム（東レ・デュポン社製「カプトン５００Ｈ」）とを１５０℃、２ＭＰａ、３０ｍｉｎの条件で加熱圧着した。次に、絶縁層側の剥離性シートを剥がし、これをテストピースとした。
<Test piece production>
The obtained electromagnetic shielding sheet was prepared in a size of 60 mm in width and 60 mm in length, and then the conductive layer exposed by peeling off the peelable sheet on the conductive layer side and a polyimide film having a thickness of 125 μm (“Toray DuPont” And Kapton 500H ") under the conditions of 150 ° C., 2 MPa, and 30 min. Next, the peelable sheet on the insulating layer side was peeled off, and this was used as a test piece.
＜８５°光沢度＞
テストピースの絶縁層面の８５°光沢度をＢＹＫ.ＧＡＲＤＮＥＲ社のｍｉｃｒｏ-ＴＲＩ-ｇｌｏｓｓ表面光沢度計を用いて８５°の測定角度で測定した。
<85 ° glossiness>
The 85 ° glossiness of the insulating layer surface of the test piece was measured at a measurement angle of 85 ° using a micro-TRI-gloss surface glossmeter manufactured by BYK.GARDNER.
＜Ｌ＊値測定＞
テストピースの絶縁層面のＬ＊値をＫＯＮＩＣＡ ＭＩＮＯＬＴＡ社製「色彩色差計ＣＲ-４００」を用いて測定した。
<L * value measurement>
The L * value of the insulating layer surface of the test piece was measured using “Color Difference Meter CR-400” manufactured by KONICA MINOLTA.
＜印字の視認性＞
テストピースの絶縁層面に白色インキ（東洋インキ社製）を用いてスクリーン印刷で印字した。印字のサイズは１ポイントとした。暗室内にて印字部に６０ＷのＬＥＤライトを照射し、水平面を基準として２０°、４５°、９０°の角度から印字から５０ｃｍの距離を開けて目視で印字が視認可能かを確認した。なお評価基準は以下の通りである。
○：２０°、４５°、９０°すべて視認可能 良好な結果である。
△：４５°、９０°で視認可能 実用上問題ない。
×：すべての角度で視認不可能 実用不可
<Visibility of printing>
Printing was performed by screen printing on the insulating layer surface of the test piece using white ink (manufactured by Toyo Ink Co., Ltd.). The printing size was 1 point. A 60 W LED light was applied to the printing unit in the dark room, and a distance of 50 cm from the printing was opened at an angle of 20 °, 45 °, and 90 ° with respect to the horizontal plane, and it was confirmed whether the printing was visible. The evaluation criteria are as follows.
○: Visible at 20 °, 45 °, and 90 ° All results are good.
Δ: Visible at 45 ° and 90 ° No problem in practical use.
×: Not visible at all angles Not practical
＜表面抵抗値＞
テストピースの絶縁層の表面抵抗値を三菱化学アナリテック社製「ハイレスタＵＰ」のリングプローブＵＲＳを用いて測定した。評価基準は以下の通りである。
○ ： １×１０8Ω／□以上、１×１０14Ω／□以下 良好な結果である。
△ ： １×１０5Ω／□以上、１×１０8Ω／□未満 実用上問題ない。
× ： １×１０5Ω／□未満、または１×１０15Ω／□よりも高い。 実用不可。
<Surface resistance value>
The surface resistance value of the insulating layer of the test piece was measured using a ring probe URS of “HIRESTA UP” manufactured by Mitsubishi Chemical Analytech. The evaluation criteria are as follows.
○: 1 × 10 8 Ω / □ or more, 1 × 10 14 Ω / □ or less Good results.
Δ: 1 × 10 5 Ω / □ or more and less than 1 × 10 8 Ω / □ There is no practical problem.
×: Less than 1 × 10 5 Ω / □, or higher than 1 × 10 15 Ω / □. Not practical.
＜耐摩耗性＞
得られた電磁波シールドシートを幅４０ｍｍ・長さ１５０ｍｍの大きさに準備した。次いで、その導電層側から剥離性シートを剥がし、露出した導電層に、厚さ７５μｍのポリイミドフィルム（「カプトン３００Ｈ」東レ・デュポン社製）を１５０℃、２ＭＰａ、３０ｍｉｎの条件で圧着した。圧着後、絶縁層側の剥離性シートを除去し、露出した絶縁層に対して、別途準備した電磁波シールドシートをセットした学振磨耗試験機（テスター産業社製）を使用して、荷重２００ｇｆ、往復速度３０回／ｍｉｎ、ストローク１２０ｍｍの条件下で、絶縁層同士を擦り合わせ、その外観不良が発生するまでの往復回数を測定した。評価基準は以下の通りである。
○：２００００回以上 良好な結果である。
△：１００００回以上２００００回未満 実用上問題ない。
×：１００００回未満 実用不可
<Abrasion resistance>
The obtained electromagnetic wave shielding sheet was prepared to have a width of 40 mm and a length of 150 mm. Next, the peelable sheet was peeled off from the conductive layer side, and a 75 μm thick polyimide film (“Kapton 300H” manufactured by Toray DuPont) was pressure-bonded to the exposed conductive layer under the conditions of 150 ° C., 2 MPa, and 30 min. After crimping, the peelable sheet on the insulating layer side is removed, and a load of 200 gf is applied using a Gakushin Abrasion Tester (manufactured by Tester Sangyo Co., Ltd.) with an electromagnetic shielding sheet prepared separately for the exposed insulating layer. The insulating layers were rubbed together under conditions of a reciprocating speed of 30 times / min and a stroke of 120 mm, and the number of reciprocations until the appearance defect occurred was measured. The evaluation criteria are as follows.
○: 20000 times or more Good results.
Δ: 10000 times or more and less than 20000 times No problem in practical use.
×: Less than 10,000 times
１ 絶縁層
２ 導電層
３ 金属層
４ 電磁波シールドシート
５ プリント配線板
６ カバーコート層
７ 絶縁性基材
８ グランド配線
９ 配線回路
１０ 穴
DESCRIPTION OF
本発明の電磁波シールドシートは、導電層、および絶縁層を備え、前記絶縁層が熱硬化性樹脂、硬化剤、および黒色系着色剤を含み、前記黒色系着色剤は、平均一次粒子径が２０〜１００ｎｍであり、前記黒色系着色剤の含有量が、絶縁層１００重量％中、１２．２〜４０重量％であり、さらに絶縁層の８５°光沢度が１５〜５０、かつＬ＊ａ＊ｂ＊表色系におけるＬ＊値が２０〜３０であることを特徴とする。
The electromagnetic wave shielding sheet of the present invention includes a conductive layer and an insulating layer, and the insulating layer contains a thermosetting resin, a curing agent, and a black colorant, and the black colorant has an average primary particle size of 20. ~100nm der is, the content of the black-based colorant, an insulating layer 100 wt%, a 12.2 to 40 wt%, still has 85 ° gloss of the insulating layer 15 to 50, and L * a The L * value in the * b * color system is 20-30 .
上記の本発明によれば絶縁層が平均一次粒子径２０〜１００ｎｍの黒色系着色剤を含み、前記黒色系着色剤の含有量が、絶縁層１００重量％中、１２．２〜４０重量％であり、さらに絶縁層の８５°光沢度が１５〜５０、かつＬ＊ａ＊ｂ＊表色系におけるＬ＊値が２０〜３０であるため、絶縁層に印字された文字の視認性が向上したことで、作業者がＦＰＣを選別し、電子機器に搭載するときの作業性が向上し、生産性も向上した。
Look containing a black coloring agent of the present invention in accordance if the insulating layer is an average primary particle diameter of 20 to 100 nm, the content of the black-based colorant, an insulating layer 100 wt%, 12.2 to 40 wt% Furthermore, since the 85 ° glossiness of the insulating layer is 15 to 50 and the L * value in the L * a * b * color system is 20 to 30, the visibility of characters printed on the insulating layer is improved. As a result, the workability when the operator selects the FPC and mounts it on the electronic device is improved, and the productivity is also improved.
＜実施例２〜１３、比較例１〜３＞
実施例１の原料の種類・配合量を表２のように変更した以外は実施例１と同様に行うことで、電磁波シールドシートを得た。なお比較例２は、絶縁性樹脂組成物が増粘しゲル化したことで塗工により絶縁性が形成できなかったため物性評価を行わなかった。
ただし、実施例１２は参考例である。
<Examples 2 to 13 and Comparative Examples 1 to 3>
An electromagnetic wave shielding sheet was obtained in the same manner as in Example 1 except that the type and amount of the raw material in Example 1 were changed as shown in Table 2. In Comparative Example 2, physical properties were not evaluated because insulating properties could not be formed by coating because the insulating resin composition thickened and gelled.
However, Example 12 is a reference example.
Claims (7)
前記絶縁層が熱硬化性樹脂、硬化剤、および黒色系着色剤を含み、
前記黒色系着色剤は、平均一次粒子径が２０〜１００ｎｍであることを特徴とする電磁波シールドシート。 A conductive layer and an insulating layer;
The insulating layer includes a thermosetting resin, a curing agent, and a black colorant;
The black colorant has an average primary particle diameter of 20 to 100 nm.
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| KR1020160009793A KR101862121B1 (en) | 2015-02-02 | 2016-01-27 | Electromagnetic wave shielding sheet, printed wiring board and electronic devices |
| TW105102977A TWI628999B (en) | 2015-02-02 | 2016-01-30 | Electromagnetic wave shielding sheet, printed wiring board and electronic equipment |
| CN201610069199.2A CN105848407B (en) | 2015-02-02 | 2016-02-01 | Electromagnetic wave shielding sheet, printing distributing board and e-machine |
| CN201910098668.7A CN110049665B (en) | 2015-02-02 | 2016-02-01 | Electromagnetic wave shielding sheet, printed wiring board, and electronic device |
| KR1020180058180A KR102291975B1 (en) | 2015-02-02 | 2018-05-23 | Electromagnetic wave shielding sheet, printed wiring board and electronic devices |
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| JP2022094372A (en) * | 2020-12-15 | 2022-06-27 | 東洋インキＳｃホールディングス株式会社 | Thermosetting resin composition and use thereof |
| WO2022265101A1 (en) * | 2021-06-18 | 2022-12-22 | タツタ電線株式会社 | Electromagnetic wave shield film |
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