JP6465243B1 - Electromagnetic shielding film, printed wiring board and electronic equipment. - Google Patents
Electromagnetic shielding film, printed wiring board and electronic equipment. Download PDFInfo
- Publication number
- JP6465243B1 JP6465243B1 JP2018142190A JP2018142190A JP6465243B1 JP 6465243 B1 JP6465243 B1 JP 6465243B1 JP 2018142190 A JP2018142190 A JP 2018142190A JP 2018142190 A JP2018142190 A JP 2018142190A JP 6465243 B1 JP6465243 B1 JP 6465243B1
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- Prior art keywords
- shielding film
- electromagnetic wave
- wave shielding
- layer
- phosphorus
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Abstract
【課題】マイグレーション耐性、難燃性および屈曲性が良好な電磁波シールドフィルム付きのプリント配線板の提供すること。
【解決手段】導電層および保護層を有してなる電磁波シールドフィルムであって、 前記電磁波シールドフィルム０．１６質量部を、水１００質量部中、８５℃、７２時間の条件で抽出された抽出液中に含まれるリン元素の濃度が、３００ｍｇ／Ｌ以下である電磁波シールドフィルム。好ましくは、更に前記抽出液中に含まれる銅元素の濃度が、４００ｍｇ／Ｌ以下である電磁波シールドフィルム。
【選択図】図１An object of the present invention is to provide a printed wiring board with an electromagnetic wave shielding film having excellent migration resistance, flame retardancy and flexibility.
An electromagnetic wave shielding film having a conductive layer and a protective layer, wherein 0.16 parts by mass of the electromagnetic wave shielding film is extracted in 100 parts by mass of water at 85 ° C. for 72 hours. The electromagnetic wave shielding film whose density | concentration of the phosphorus element contained in a liquid is 300 mg / L or less. Preferably, the electromagnetic wave shielding film in which the concentration of the copper element contained in the extract is 400 mg / L or less.
[Selection] Figure 1
Description
本発明は、電磁波シールドフィルム、プリント配線板および電子機器に関する。 The present invention relates to an electromagnetic wave shielding film, a printed wiring board, and an electronic device.
近年では、小型化・薄型化が急速に進む携帯電話、ビデオカメラ、ノートパソコンなどの電子機器において、柔軟で可撓性のあるフレキシブルプリント基板（以下、ＦＰＣという）は必要不可欠となっている。さらに電子機器の高性能化に伴い内蔵される信号配線の狭ピッチ化・高周波化が進むため、電磁波ノイズに対する対策が重要度を増している。そのためＦＰＣには、信号配線から発生する電磁波ノイズを遮蔽もしくは吸収する電磁波シールド材を組み込むことが一般的になっている。
なおＦＰＣは、エッチング処理により回路形成した銅張積層版（ＣＣＬ）とカバーコート材から構成される。カバーコート材はカバーレイフィルム、感光性インク（ソルダーレジスト）、感光性フィルム（ドライレジストフィルム）等から選択するのが一般的であり、取り扱いの容易さ、耐久性、絶縁信頼性の高さから、カバーレイフィルムが多く使用されている。カバーレイフィルムとは絶縁性基材に熱硬化性接着剤を塗布した材料である。
そこで例えば、特許文献１には、ＦＰＣの絶縁層上に導電性接着剤層や金属薄膜層等を有するシールド層を貼り合せると共に、ＦＰＣのグランド配線に導電接着剤層を介して金属薄膜層を電気的に接続した電磁波シールド機能を有するＦＰＣが開示されている。
In recent years, flexible and flexible flexible printed boards (hereinafter referred to as FPCs) have become indispensable in electronic devices such as mobile phones, video cameras, and notebook personal computers that are rapidly becoming smaller and thinner. Furthermore, as the performance of electronic devices increases, the signal wiring built-in is becoming narrower and higher in frequency, and countermeasures against electromagnetic noise are becoming increasingly important. For this reason, an FPC is generally incorporated with an electromagnetic shielding material that shields or absorbs electromagnetic noise generated from signal wiring.
The FPC is composed of a copper clad laminate (CCL) formed by etching and a cover coat material. The cover coat material is generally selected from cover lay film, photosensitive ink (solder resist), photosensitive film (dry resist film), etc., because of easy handling, durability, and high insulation reliability. Many coverlay films are used. A coverlay film is a material obtained by applying a thermosetting adhesive to an insulating substrate.
Therefore, for example, in Patent Document 1, a shield layer having a conductive adhesive layer, a metal thin film layer, or the like is bonded to the insulating layer of the FPC, and a metal thin film layer is attached to the ground wiring of the FPC via the conductive adhesive layer. An FPC having an electrically connected electromagnetic shielding function is disclosed.
また、特許文献２には、熱硬化性樹脂、硬化剤、導電性フィラー、およびイオン捕集剤を含む導電層を有する電波波シールドフィルムが開示されている。一方、特許文献３にはエポキシ樹脂脂とカルボキシル基含有エラストマーとの硬化物と、有機リン系難燃剤と、導電性フィラーとを含有する電磁波 シールドフィルムが開示されている。 Patent Document 2 discloses a radio wave shield film having a conductive layer containing a thermosetting resin, a curing agent, a conductive filler, and an ion scavenger. On the other hand, Patent Document 3 discloses an electromagnetic wave shielding film containing a cured product of an epoxy resin fat and a carboxyl group-containing elastomer, an organic phosphorus flame retardant, and a conductive filler.
一方、従来はグランド配線とシールド層を電気的に接続するためカバーレイフィルムにドリル等で穴等を形成していた。しかし信号配線の狭ピッチ化に伴い、ドリルでは微細加工が出来ないため、ソルダーレジストまたはドライレジストフィルムを使用することで穴等を形成するようになってきた。そこで特許文献４および特許文献５には、一般的なポリイミドカバーレイフィルムに代えて感光性アルカリ現像型のソルダーレジストをカバーコート材として使用したＦＰＣが開示されている。 On the other hand, conventionally, holes or the like have been formed in the coverlay film with a drill or the like in order to electrically connect the ground wiring and the shield layer. However, along with the narrowing of the pitch of signal wiring, since drilling cannot be performed finely, holes or the like have been formed by using a solder resist or a dry resist film. Therefore, Patent Document 4 and Patent Document 5 disclose an FPC using a photosensitive alkali development type solder resist as a cover coating material instead of a general polyimide cover lay film.
しかし、このように感光性アルカリ現像型のソルダーレジストによってカバーコート層を形成した場合、カバーレイフィルムと比べ絶縁基材を有さない単層構成であり、且つ、フォトリソ工程由来のコンタミを含んでいるため絶縁信頼性が低く、このようなソルダーレジストまたはドライレジストフィルムから形成されてなるカバーコート層に従来の電磁波シールドフィルムを張り合わせたＦＰＣは、マイグレーション耐性が極端に悪化する問題があった。
具体的には、難燃性を付与するため電磁波シールドフィルムには難燃剤を添加するが、難燃剤から溶出するリンがマイグレーション耐性を極端に悪化させており、マイグレーション耐性と難燃性の両立が課題であった。加えて、電磁波シールドフィルムの導電層に使用する導電性フィラーや銅箔から溶出する銅もマイグレーション耐性を悪化させる原因となっておりこの抑制も課題となっていた。
However, when the cover coat layer is formed with a photosensitive alkali development type solder resist in this way, it has a single layer structure that does not have an insulating substrate as compared with the cover lay film, and includes contamination derived from the photolithography process. Therefore, the insulation reliability is low, and the FPC in which the conventional electromagnetic wave shielding film is bonded to the cover coat layer formed from such a solder resist or dry resist film has a problem that the migration resistance is extremely deteriorated.
Specifically, a flame retardant is added to the electromagnetic wave shielding film in order to impart flame retardancy, but phosphorus eluted from the flame retardant greatly deteriorates migration resistance, and both migration resistance and flame resistance are compatible. It was a challenge. In addition, the conductive filler used for the conductive layer of the electromagnetic wave shielding film and the copper eluted from the copper foil also cause the migration resistance to deteriorate, and this suppression has been a problem.
本発明が解決しようとする課題は、ソルダーレジストまたはドライレジストフィルムから形成されてなるカバーコート層を有する場合にも、マイグレーション耐性、難燃性および屈曲性が良好な電磁波シールドフィルムと、それを用いたプリント配線板および電子機器を提供することである。 The problem to be solved by the present invention is to provide an electromagnetic wave shielding film having good migration resistance, flame retardancy and flexibility, and to use the same even when it has a cover coat layer formed from a solder resist or a dry resist film. It is to provide a printed wiring board and an electronic device.
本発明者らは上記課題を解決するため、鋭意検討した結果、マイグレーション耐性を悪化させる原因が、電磁波シールドフィルム中に含まれるリン元素に起因していることを見出し、所定の条件下で電磁波シールドフィルムより抽出されたリン元素の濃度を一定濃度以下に制御することにより、マイグレーション耐性が著しく向上することを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that the cause of deterioration in migration resistance is due to the phosphorus element contained in the electromagnetic wave shielding film, and the electromagnetic wave shielding under predetermined conditions. The inventors have found that migration resistance is remarkably improved by controlling the concentration of the phosphorus element extracted from the film to a certain concentration or less, and the present invention has been completed.
すなわち本発明は、導電層および保護層を有してなる電磁波シールドフィルムであって、 前記電磁波シールドフィルム０．１６質量部を、水１００質量部中、８５℃、７２時間の条件で抽出された抽出液中に含まれるリン元素の濃度が、３００ｍｇ／Ｌ以下である電磁波シールドフィルムに関する。 That is, this invention is an electromagnetic wave shielding film which has a conductive layer and a protective layer, Comprising: 0.16 mass part of the said electromagnetic wave shielding film was extracted on conditions of 85 degreeC and 72 hours in 100 mass parts of water. It is related with the electromagnetic wave shielding film whose density | concentration of the phosphorus element contained in an extract is 300 mg / L or less.
すなわち本発明は、上記抽出液中に含まれる銅元素の濃度が、４００ｍｇ／Ｌ以下である上記電磁波シールドフィルムに関する。 That is, this invention relates to the said electromagnetic wave shielding film whose density | concentration of the copper element contained in the said extract is 400 mg / L or less.
すなわち本発明は、上記電磁波シールドフィルムと、カバーコート層と、信号配線および絶縁性基材を有する配線板とを具備する、プリント配線板に関する。 That is, the present invention relates to a printed wiring board comprising the electromagnetic wave shielding film, a cover coat layer, and a wiring board having a signal wiring and an insulating substrate.
すなわち本発明は、上記カバーコート層が、ソルダーレジストおよび／またはドライレジストフィルムから形成されてなる上記プリント配線板に関する。 That is, the present invention relates to the printed wiring board in which the cover coat layer is formed from a solder resist and / or a dry resist film.
すなわち本発明は、上記カバーコート層が、黒色である上記プリント配線板に関する。 That is, the present invention relates to the printed wiring board in which the cover coat layer is black.
すなわち本発明は、上記プリント配線板を備えた、電子機器に関する。 That is, this invention relates to the electronic device provided with the said printed wiring board.
本発明により、マイグレーション耐性、難燃性および屈曲性が良好な電波波シールドフィルムと、それを用いたプリント配線板および電子機器を提供できるようになった。 According to the present invention, it is possible to provide a radio wave shield film having good migration resistance, flame retardancy and flexibility, and a printed wiring board and electronic equipment using the same.
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 the following drawings are for convenience of explanation, and are not limited to this. In the present specification, the description “any number A to any number B” includes the number A as a lower limit and the number B as an upper limit in the range. The “sheet” in this specification includes not only “sheet” defined in JIS but also “film”. Moreover, the numerical value specified in this specification is a value calculated | required by the method disclosed by embodiment or an Example.
本発明の電磁波シールドフィルムは、導電層および保護層を有してなる電磁波シールドフィルムであって、前記電磁波シールドフィルム０．１６質量部を、水１００質量部中、８５℃、７２時間の条件で抽出された抽出液中に含まれるリン元素の濃度（以下、電磁波シールドフィルムのリン抽出濃度と省略）が、３００ｍｇ／Ｌ以下であることを特徴とする。 The electromagnetic wave shielding film of this invention is an electromagnetic wave shielding film which has a conductive layer and a protective layer, Comprising: 0.16 mass part of said electromagnetic wave shielding film is 100 mass parts of water on condition of 85 degreeC and 72 hours. The concentration of the phosphorus element contained in the extracted extract (hereinafter abbreviated as the phosphorus extraction concentration of the electromagnetic shielding film) is 300 mg / L or less.
＜導電層＞
電磁波シールドフィルム中の導電層は、電磁波等のノイズをシールドし、主にＦＰＣのカバーコート層に貼り付ける層である。
導電層は、導電性接着剤から形成した導電層の第一の態様、および金属層と導電性接着剤から形成した導電層とを有する第二の態様の２つの態様が好ましい。第二の態様を採用するとシールド効果がさらに向上する。また、導電層は、等方導電性または異方導電性を有することが好ましい。等方導電性とは、電磁波シールドフィルムを水平に置いたときに垂直方向（縦方向）と水平方向（面方向）に導電することをいう。また異方導電とは、電磁波シールドフィルムを水平に置いたときに垂直方向（縦方向）に導電することをいう。等方導電性は、フレーク状や樹枝状の導電性フィラーを使用する方法等公知の方法で得られる。また、異方導電性は、球状または樹枝状の導電性フィラーを使用する方法等で得られる。なお、導電層が樹枝状の導電性フィラーを大量に含む場合、等方導電性が得られる。また導電層が樹枝状の導電性フィラーを少量含む場合、異方導電性が得られる。
<Conductive layer>
The conductive layer in the electromagnetic wave shielding film is a layer that shields noise such as electromagnetic waves and is mainly attached to the cover coat layer of the FPC.
The conductive layer is preferably a first embodiment of a conductive layer formed of a conductive adhesive and a second embodiment of a second embodiment having a metal layer and a conductive layer formed of a conductive adhesive. Employing the second aspect further improves the shielding effect. The conductive layer preferably has isotropic conductivity or anisotropic conductivity. Isotropic conductivity means conducting in the vertical direction (longitudinal direction) and the horizontal direction (plane direction) when the electromagnetic shielding film is placed horizontally. The anisotropic conduction means conducting in the vertical direction (longitudinal direction) when the electromagnetic wave shielding film is placed horizontally. The isotropic conductivity can be obtained by a known method such as a method using a flaky or dendritic conductive filler. The anisotropic conductivity is obtained by a method using a spherical or dendritic conductive filler. Note that isotropic conductivity is obtained when the conductive layer contains a large amount of dendritic conductive filler. Further, when the conductive layer contains a small amount of dendritic conductive filler, anisotropic conductivity can be obtained.
導電層は、導電性接着剤を使用して形成できる。導電性接着剤は、導電性を有する層を形成できる接着剤であれば特に制限はないが、熱硬化性樹脂、硬化剤、および導電性フィラーを含むことが好ましい。 The conductive layer can be formed using a conductive adhesive. The conductive adhesive is not particularly limited as long as it is an adhesive that can form a conductive layer, but preferably contains a thermosetting resin, a curing agent, and a conductive filler.
［熱硬化性樹脂］
本発明で使用する熱硬化性樹脂とは、硬化剤と反応可能な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、メトキシメチル基、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、ブロック化カルボキシル基、シラノール基等が挙げられる。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、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、ポリアミドイミド樹脂、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、フッ素樹脂等の公知の樹脂が挙げられる。これらの中でも屈曲性と絶縁信頼性の点から、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、フェノキシ樹脂、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。熱硬化性樹脂は、単独または２種類以上併用できる。
[Thermosetting resin]
The thermosetting resin used in the present invention is a resin having a plurality of functional groups capable of reacting with a curing agent. Functional groups include, for example, hydroxyl group, phenolic hydroxyl group, methoxymethyl group, carboxyl group, amino group, epoxy group, oxetanyl group, oxazoline group, oxazine group, aziridine group, thiol group, isocyanate group, blocked isocyanate group, blocked A carboxyl group, a silanol group, etc. are mentioned. Thermosetting resins include, for example, acrylic resins, maleic resins, polybutadiene resins, polyester resins, polyurethane resins, polyurethane urea resins, epoxy resins, oxetane resins, phenoxy resins, polyimide resins, polyamide resins, polyamideimide resins, phenolic resins. Known resins such as resins, alkyd resins, amino resins, polylactic acid resins, oxazoline resins, benzoxazine resins, silicone resins, and fluorine resins can be used. Among these, polyurethane resin, polyurethane urea resin, epoxy resin, phenoxy resin, polyimide resin, polyamide resin, and polyamideimide resin are preferable from the viewpoint of flexibility and insulation reliability. Thermosetting resins can be used alone or in combination of two or more.
［硬化剤］
硬化剤は、熱硬化性樹脂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、例えば、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、アミン化合物、フェノール化合物等の公知の化合物が挙げられる。硬化剤は、単独または２種類以上併用できる。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。
[Curing agent]
The curing agent has a plurality of functional groups that can react with the functional groups of the thermosetting resin. Examples of the curing agent include known compounds such as an epoxy compound, an acid anhydride group-containing compound, an isocyanate compound, an aziridine compound, an amine compound, and a phenol compound. A hardening | curing agent can be used individually or in combination with 2 or more types. It is preferable that 1-50 mass parts is contained with respect to 100 mass parts of thermosetting resins, 3-30 mass parts is more preferable, and 3-20 mass parts is further more preferable.
［導電性フィラー］
導電性フィラーは、導電特性を有し、電磁波シールド性を発揮できれば、特に限定されないが、金属フィラー、導電性セラミックス粒子、カーボンフィラーおよびそれらの混合物が挙げられる。金属フィラーとしては、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等がある。カーボンフィラーとしては、アセチレンブラック、ケッチェンブラック、ファーネスブラック、カーボンブラック、カーボンファイバー、カーボンナノナノチューブからなる粒子、グラフェン粒子、グラファイト粒子、カーボンナノウォール等が例示できる。銀を含有することにより、より優れた導電性が得られる。これらのうちでは、コストの観点から、銀コート銅粉が特に好ましい。金属粉に対するコート層の被覆率は、被覆層による平均被覆率を６０％以上とすることが好ましく、７０％以上とすることがより好ましく、８０％以上とすることがさらに好ましい。平均被覆率を６０％以上とすることで銅の溶出を抑制しマイグレーション耐性が向上する。
[Conductive filler]
The conductive filler is not particularly limited as long as it has conductive properties and can exhibit electromagnetic wave shielding properties, and examples thereof include metal fillers, conductive ceramic particles, carbon fillers, and mixtures thereof. Examples of the metal filler include 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. Examples of the carbon filler include acetylene black, ketjen black, furnace black, carbon black, carbon fiber, particles made of carbon nano-nanotubes, graphene particles, graphite particles, and carbon nanowalls. By containing silver, more excellent conductivity can be obtained. Of these, silver-coated copper powder is particularly preferable from the viewpoint of cost. The coverage of the coating layer with respect to the metal powder is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more. By controlling the average coverage to 60% or more, elution of copper is suppressed and migration resistance is improved.
導電性フィラーの形状は、特に限定されないが、好ましくは鱗片状粒子、デンドライト（樹枝）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である。これらは、単独でも混合して用いてもよい。 The shape of the conductive filler is not particularly limited, but is preferably a particle selected from the group consisting of scaly particles, dendritic (dendritic) particles, fibrous particles, acicular particles, and spherical particles. These may be used alone or in combination.
本明細書における導電性フィラーの平均粒子径は、レーザー回折・散乱法によって測定された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。 The average particle diameter of the conductive filler in the present specification is a D50 average particle diameter measured by a laser diffraction / scattering method, preferably 1 to 100 μm, and more preferably 3 to 50 μm.
導電性フィラーは、熱硬化性樹脂１００質量部に対して、５０〜１５００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 50-1500 mass parts with respect to 100 mass parts of thermosetting resins, and a conductive filler has more preferable 100-1000 mass parts.
導電層に加えて、保護層と導電層の間に金属層を設けても良い。導電層と金属層とを積層する方法は公知の方法を使用できる。方法は、例えば、剥離性シート上に金属層を形成する。さらに、別途、剥離性シート上に形成した導電層を、前記金属層とラミネートする方法等が挙げられる。 In addition to the conductive layer, a metal layer may be provided between the protective layer and the conductive layer. A known method can be used for laminating the conductive layer and the metal layer. For example, the method forms a metal layer on a peelable sheet. Furthermore, a method of laminating a conductive layer separately formed on a peelable sheet with the metal layer can be used.
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、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電解銅がより好ましい。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が好ましい。金属箔以外の金属層の厚みは、通常０．００５〜１０μｍ程度である。
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 in terms of shielding properties, connection reliability, and cost. For example, rolled copper foil or electrolytic copper foil is preferably used as copper, and electrolytic copper is more preferable when the thickness of the metal layer is pursued. 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 may be formed by vacuum deposition, sputtering, CVD, MO (metal organic), plating, or the like. Among these, vacuum deposition is preferable in view of mass productivity. The thickness of the metal layer other than the metal foil is usually about 0.005 to 10 μm.
導電性接着剤は、他に任意成分として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、難燃剤などを配合できる。 Conductive adhesives include silane coupling agents, rust inhibitors, reducing agents, antioxidants, pigments, dyes, tackifying resins, plasticizers, UV absorbers, antifoaming agents, leveling regulators as optional components. Fillers and flame retardants can be blended.
導電性接着剤は、これまで説明した材料を混合し攪拌して得ることができる。攪拌は、例えばディスパーマット、ホモジナイザー等に公知の攪拌装置を使用できる。 The conductive adhesive can be obtained by mixing and stirring the materials described so far. For the stirring, for example, a known stirring device can be used for a disperse mat, a homogenizer or the like.
＜保護層＞
保護層は、絶縁性樹脂組成物を使用して形成できる。絶縁性樹脂組成物は、絶縁性を有する層を形成できる組成物であれば特に制限はないが、導電性接着剤で説明した熱硬化性樹脂、硬化剤および上記任意成分を含むことができる。なお、保護層および導電層に使用する熱硬化性樹脂、硬化剤は、同一、または異なっていてもよい。絶縁性樹脂組成物は、導電性接着剤と同様の方法で得ることが出来る。
<Protective layer>
The protective layer can be formed using an insulating resin composition. The insulating resin composition is not particularly limited as long as it is a composition capable of forming an insulating layer, but can contain the thermosetting resin, the curing agent, and the above-described optional components described in the conductive adhesive. The thermosetting resin and the curing agent used for the protective layer and the conductive layer may be the same or different. The insulating resin composition can be obtained by the same method as that for the conductive adhesive.
＜電磁波シールドフィルムのリン抽出濃度＞
本発明の電磁波シールドフィルムは、０．１６質量部を、水１００質量部中、８５℃、７２時間の条件で抽出された抽出液中に含まれるリン元素の濃度（「リン抽出濃度」と略記することがある）が、３００ｍｇ／Ｌ以下であって、２４０ｍｇ／Ｌ以下が好ましく、１８０ｍｇ／Ｌ以下がより好ましい。リン抽出濃度を３００ｍｇ／Ｌ以下とすることで電磁波シールドフィルムを貼り付けたプリント配線板が高い難燃性を有しながらマイグレーション耐性を向上できる。
リン抽出濃度は、導電層および／または保護層に含まれるリン系化合物に由来する。より具体的には専らリン系難燃剤に由来する。リン系難燃剤は少量の添加で高い難燃性を付与する反面、マイグレーション試験のような高湿高温環境下外部に溶出しマイグレーション耐性を大幅に悪化させることが検討の末判明した。このような溶出を抑制する方策としてはリン系難燃剤を表面処理することで抑制できる。また、耐水性の高い熱硬化性樹脂や硬化剤を選定し、熱硬化後の架橋密度を上げることによっても調整できる。尚、本明細書におけるリン抽出濃度は、誘導結合プラズマ（ＩＣＰ）発光分光分析によって求めた数値であり、具体的な測定方法は実施例で後述する。すなわち本発明の電磁波シールドフィルムは高い難燃性を付与するため一定量のリン系難燃剤を含有しつつも、溶出するりん元素の濃度が低いため、貼り付けたプリント配線板のマイグレーションが発生しにくい。
<Phosphorus extraction concentration of electromagnetic shielding film>
In the electromagnetic wave shielding film of the present invention, 0.16 parts by mass of phosphorus element contained in 100 parts by mass of water and extracted at 85 ° C. for 72 hours (abbreviated as “phosphorus extraction concentration”). May be 300 mg / L or less, preferably 240 mg / L or less, and more preferably 180 mg / L or less. By setting the phosphorus extraction concentration to 300 mg / L or less, migration resistance can be improved while the printed wiring board on which the electromagnetic wave shielding film is attached has high flame retardancy.
The phosphorus extraction concentration is derived from a phosphorus compound contained in the conductive layer and / or the protective layer. More specifically, it is exclusively derived from phosphorus flame retardants. Phosphorus flame retardant imparts high flame retardancy when added in a small amount, but on the other hand, it has been clarified after examination that it elutes to the outside in a high humidity and high temperature environment such as a migration test and greatly deteriorates the migration resistance. As a measure for suppressing such elution, it can be suppressed by surface-treating a phosphorus-based flame retardant. It can also be adjusted by selecting a thermosetting resin or curing agent having high water resistance and increasing the crosslink density after thermosetting. The phosphorus extraction concentration in the present specification is a numerical value obtained by inductively coupled plasma (ICP) emission spectroscopic analysis, and a specific measuring method will be described later in Examples. That is, the electromagnetic wave shielding film of the present invention contains a certain amount of phosphorus-based flame retardant to impart high flame retardancy, but the concentration of the eluted phosphorus element is low, and migration of the attached printed wiring board occurs. Hateful.
［リン系難燃剤］
リン系難燃剤について説明する。リン系難燃剤としては、リン酸メラミン、ポリリン酸メラミン、リン酸グアニジン、ポリリン酸グアニジン、リン酸アンモニウム、ポリリン酸アンモニウム、リン酸アミドアンモニウム、ポリリン酸アミドアンモニウム、リン酸カルバメート、ポリリン酸カルバメート等の（ポリ）リン酸塩系化合物、有機リン酸エステル化合物、ホスファゼン化合物、ホスホン酸化合物、ジエチルホスフィン酸アルミニウム、メチルエチルホスフィン酸アルミニウム、ジフェニルホスフィン酸アルミニウム、エチルブチルホスフィン酸アルミニウム、メチルブチルホスフィン酸アルミニウム、ポリエチレンホスフィン酸アルミニウム等のホスフィン酸化合物、ホスフィンオキシド化合物、ホスホラン化合物、ホスホルアミド化合物等が好ましく、ホスファゼン化合物、ホスフィン化合物、ポリリン酸メラミン、ポリリン酸アンモニウム、を用いることがより好ましく、特にホスフィン化合物のうちホスフィン酸塩が好ましく、ホスフィン酸アルミニウムがさらに好ましい。
[Phosphorus flame retardant]
The phosphorus flame retardant will be described. Phosphorus flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amidophosphate, ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate, etc. (Poly) phosphate compounds, organophosphate compounds, phosphazene compounds, phosphonic acid compounds, aluminum diethylphosphinate, aluminum methylethylphosphinate, aluminum diphenylphosphinate, aluminum ethylbutylphosphinate, aluminum methylbutylphosphinate, Preferred are phosphinic acid compounds such as polyethylene phosphinate, phosphine oxide compounds, phosphorane compounds, phosphoramide compounds, etc. Compounds, phosphine compounds, melamine polyphosphate, ammonium polyphosphate, is more preferably used, particularly preferably phosphinic acid salt of the phosphine compound, aluminum phosphinate is more preferred.
リン系難燃剤に加え、炭酸アンモニウム、メラミンシアヌレート等の窒素系難燃剤や、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム、等の無機難燃剤を併用することができる。これらの中でもメラミンシアヌレート、水酸化化合物等を用いることが好ましい。 In addition to phosphorus flame retardants, use nitrogen flame retardants such as ammonium carbonate and melamine cyanurate, and inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, etc. Can do. Among these, it is preferable to use melamine cyanurate, a hydroxide compound, or the like.
これら難燃剤を粒子状で使用する場合、粒子の平均粒子径は、０．１〜２５μｍであることが好ましい。０．１μｍに近い平均粒子径を示す難燃剤を用いた場合、難燃剤による改質効果が得やすく、さらに分散性や分散液の安定性が向上しやすい。また、２５μｍに近い平均粒子径を示す難燃剤を用いた場合、硬化物の機械特性が向上しやすくなる。
なお、本発明でいう難燃剤の平均粒子径Ｄ９５は、粒度分布において体積積算値９５％が含まれる時の粒径を示す。
When these flame retardants are used in the form of particles, the average particle size of the particles is preferably 0.1 to 25 μm. When a flame retardant having an average particle diameter close to 0.1 μm is used, a modification effect by the flame retardant is easily obtained, and dispersibility and dispersion stability are easily improved. Moreover, when the flame retardant which shows the average particle diameter near 25 micrometers is used, it becomes easy to improve the mechanical characteristic of hardened | cured material.
In addition, the average particle diameter D95 of the flame retardant referred to in the present invention indicates a particle diameter when a volume integrated value of 95% is included in the particle size distribution.
上記難燃剤は表面処理されていることが、電磁波シールドフィルムのリン抽出濃度を３００ｍｇ／Ｌ以下にし、マイグレーション耐性を向上する点から好ましい。 The flame retardant is preferably surface-treated from the viewpoint of improving the migration resistance by setting the phosphorus extraction concentration of the electromagnetic wave shielding film to 300 mg / L or less.
表面処理難燃剤は、難燃剤の表面の少なくとも一部に、無機酸化物を付着させたものである。付着させる無機酸化物としては、シリカ、アルミナ、チタニア、ジルコニアが好ましく、シリカおよびジルコニアがより好ましい。 The surface-treated flame retardant is obtained by attaching an inorganic oxide to at least a part of the surface of the flame retardant. As the inorganic oxide to be deposited, silica, alumina, titania and zirconia are preferable, and silica and zirconia are more preferable.
付着させる無機酸化物の量は、前記の難燃剤１００質量部に対し、０．０１〜１０質量部であることが好ましく、より好ましくは０．１質量部〜１０質量部、さらに好ましくは０．１質量部〜５質量部であることがより好ましい。０．０１質量部以上とすることによりリン抽出濃度を抑制しマイグレーション耐性を向上できる。また１０質量部以下とすることにより難燃性が優れる。 The amount of the inorganic oxide to be deposited is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.00 to 100 parts by mass of the flame retardant. It is more preferably 1 part by mass to 5 parts by mass. By setting it as 0.01 mass part or more, a phosphorus extraction density | concentration can be suppressed and migration tolerance can be improved. Moreover, a flame retardance is excellent by setting it as 10 mass parts or less.
難燃剤の表面の少なくとも一部に、無機酸化物を付着させる方法としては特に限定されないが、噴霧法、ゾルゲル法等が用いられる。例えば、無機酸化物の原料を表面処理の対象である難燃剤に噴霧したり、無機酸化物の原料と表面処理の対象である難燃剤とを混合しスラリーにしたりした後に、無機酸化物の原料を加水分解したり焼成したりすることによって、難燃剤の表面の少なくとも一部に無機酸化物を付着することができる。前記スラリーは、融解状態の無機酸化物の原料と表面処理の対象である難燃剤とを混合することによって得ることもできるし、いわゆる有機溶媒中に無機酸化物の原料と表面処理の対象である難燃剤とを分散することによって得ることもできる。 A method for attaching the inorganic oxide to at least a part of the surface of the flame retardant is not particularly limited, and a spray method, a sol-gel method, or the like is used. For example, after spraying the inorganic oxide raw material onto the flame retardant that is the target of surface treatment, or mixing the inorganic oxide raw material and the flame retardant that is the target of surface treatment into a slurry, the raw material of the inorganic oxide The inorganic oxide can be attached to at least a part of the surface of the flame retardant by hydrolyzing or baking. The slurry can be obtained by mixing the raw material of the inorganic oxide in a molten state and the flame retardant that is the target of surface treatment, or the target of the inorganic oxide raw material and the surface treatment in a so-called organic solvent. It can also be obtained by dispersing a flame retardant.
本発明では、難燃剤の表面の少なくとも一部に、無機酸化物を付着させた表面処理難燃剤の表面に、さらにシランカップリング剤を付着させたものを用いることが好ましい。シランカップリング剤を付着させたものを用いることによって、難燃剤表面の疎水性が向上し、さらにマイグレーション耐性を上げることができる。 In the present invention, it is preferable to use a surface-treated flame retardant obtained by attaching an inorganic oxide to at least a part of the surface of the flame retardant and further attaching a silane coupling agent to the surface. By using the silane coupling agent attached, the hydrophobicity of the flame retardant surface can be improved and the migration resistance can be further increased.
上述のシランカップリング剤は特に限定されないが、例えば、ビニルメトキシシラン、ビニルエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル−ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ−（ビニルベンジル）−２−アミノエチル−３−アミノプロピルトリメトキシシランの塩酸塩、トリス−（トリメトキシシリルプロピル）イソシアヌレート、３−ウレイドプロピルトリアルコキシシラン、３−イソシアネートプロピルトリエトキシシラン、３−フェニルアミノプロピルトリメトキシシラン、１，２−エタンジアミン，Ｎ−｛３−（トリメトキシシリル）プロピル｝−，Ｎ−｛（エテニルフェニル）メチル｝誘導体・塩酸塩、ビニルトリアセトキシシラン、アリルトリメトキシシランに加え、官能基がアルコキシ基で保護されたシランカップリング剤や、スルフィド・ポリスルフィド系のシランカップリング剤、ポリマー型のアルコキシオリゴマータイプや多官能基タイプシランカップリング剤などを用いることができる。 The above-mentioned silane coupling agent is not particularly limited, and examples thereof include vinyl methoxy silane, vinyl ethoxy silane, 2- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropylmethyl dimethoxy silane, 3-glycol. Sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Ethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopro Rutrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) 2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-isocyanatopropyltriethoxysilane, 3-phenylaminopropyltri In addition to methoxysilane, 1,2-ethanediamine, N- {3- (trimethoxysilyl) propyl}-, N-{(ethenylphenyl) methyl} derivatives / hydrochloride, vinyltriacetoxysilane, allyltrimethoxysilane , The functional group is alkoxy In and protected silane coupling agent, a sulfide-polysulfide silane coupling agent, such as a polymer type alkoxy oligomer type or multifunctional type silane coupling agent can be used.
付着させるシランカップリング剤の量は、前記の難燃剤１００質量部に対し、０，００５〜５質量部であることが好ましく、０．０１〜０．５質量部であることがより好ましい。付着させるシランカップリング剤量が０．００５質量部以上であることによってマイグレーション耐性が向上する。また付着量が５質量部以下であることによって難燃性が優れる。 The amount of the silane coupling agent to be attached is preferably 0.005 to 5 parts by mass and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the flame retardant. When the amount of the silane coupling agent to be adhered is 0.005 parts by mass or more, the migration resistance is improved. Moreover, a flame retardance is excellent because an adhesion amount is 5 mass parts or less.
表面処理難燃剤の表面にさらにシランカップリング剤を付着させる方法としては特に限定されないが、乾式法もしくは高精度な処理が可能である湿式法が好適に利用される。この湿式法は無機酸化物の付着した表面処理難燃剤を分散させた分散液中にシランカップリング剤を添加し、表面処理難燃剤の表面にシランカップリング剤を結合させ、その後分散媒を除去して乾燥させる方法である。 The method for further attaching the silane coupling agent to the surface of the surface-treated flame retardant is not particularly limited, but a dry method or a wet method capable of high-precision treatment is preferably used. In this wet method, a silane coupling agent is added to a dispersion in which a surface-treated flame retardant with an inorganic oxide is dispersed, and the silane coupling agent is bonded to the surface of the surface-treated flame retardant, and then the dispersion medium is removed. And drying.
リン系難燃剤は導電層、保護層のいずれに含有してもよいが、難燃性を向上する点から最外層となる保護層に含有することが好ましい。 The phosphorus-based flame retardant may be contained in either the conductive layer or the protective layer, but is preferably contained in the protective layer that is the outermost layer from the viewpoint of improving flame retardancy.
リン系難燃剤は導電層または、保護層の固形分中それぞれにおいて３〜２６質量％含有することが好ましく、５〜２２質量％がより好ましく、７〜２０質量％がさらに好ましい。３質量％以上とすることで難燃性を高めることができる。２６質量％以下とすることでマイグレーション耐性及び屈曲性を良好なものとすることができる。 The phosphorus-based flame retardant is preferably contained in the solid content of the conductive layer or the protective layer in an amount of 3 to 26% by mass, more preferably 5 to 22% by mass, and even more preferably 7 to 20% by mass. Flame retardance can be improved by setting it as 3 mass% or more. By setting the content to 26% by mass or less, migration resistance and flexibility can be improved.
＜電磁波シールドフィルムの銅抽出濃度＞
本発明の電磁波シールドフィルムは０．１６質量部を、水１００質量部中、８５℃、７２時間の条件で抽出された抽出液中に含まれる銅元素の濃度（「銅抽出濃度」と略記することがある）が、４００ｍｇ／Ｌ以下が好ましく、３００ｍｇ／Ｌ以下がより好ましく、２００ｍｇ／Ｌ以下がさらに好ましい。銅抽出濃度を４００ｍｇ／Ｌ以下とすることで電磁波シールドフィルムを貼り付けたプリント配線板のマイグレーション耐性および屈曲性を向上できる。
銅抽出濃度は主に導電層の銅を主剤とする導電性フィラー並びに銅系の金属層に由来するものであり、導電性フィラーは銅が溶出しないよう、銅とは異なる金属で被覆率が７０％以上となるように被覆された導電性フィラーを使用することが好ましい。また、導電層に銅系の金属層を積層する場合には金属層の表面を銅以外の金属で表面保護することによって、銅抽出濃度を抑制できる。また、リン抽出濃度と同様に、疎水性の高い熱硬化性樹脂や硬化剤を配合したり、熱硬化後の架橋密度をコントロールすることによっても調整できる。
<Copper extraction concentration of electromagnetic shielding film>
In the electromagnetic wave shielding film of the present invention, 0.16 parts by mass is abbreviated as a concentration of copper element contained in an extract extracted under conditions of 85 ° C. and 72 hours in 100 parts by mass of water (“copper extraction concentration”). May be 400 mg / L or less, more preferably 300 mg / L or less, and even more preferably 200 mg / L or less. By setting the copper extraction concentration to 400 mg / L or less, it is possible to improve the migration resistance and flexibility of the printed wiring board to which the electromagnetic wave shielding film is attached.
The copper extraction concentration is mainly derived from the conductive filler mainly composed of copper in the conductive layer and the copper-based metal layer. The conductive filler is a metal different from copper so that the copper does not elute, and the coverage is 70. It is preferable to use a conductive filler coated so as to be at least%. Further, when a copper-based metal layer is laminated on the conductive layer, the copper extraction concentration can be suppressed by protecting the surface of the metal layer with a metal other than copper. Further, similarly to the phosphorus extraction concentration, it can also be adjusted by blending a highly hydrophobic thermosetting resin or curing agent, or controlling the crosslinking density after thermosetting.
銅抽出濃度はリン抽出濃度と同様の方法で測定し、銅元素の定量分析を行うことで得ることができる。 The copper extraction concentration can be obtained by measuring in the same manner as the phosphorus extraction concentration and performing quantitative analysis of the copper element.
電磁波シールドフィルムの作製方法を説明する。まず導電層の作製は、公知の方法を使用できる。例えば、導電性接着剤を剥離性シート上に塗工して乾燥することで導電層を形成する方法、または、Ｔダイのような押出成形機を使用して導電性接着剤をシート状に押し出すことで形成することもできる。 A method for producing an electromagnetic wave shielding film will be described. First, a known method can be used for producing the conductive layer. For example, a method of forming a conductive layer by applying a conductive adhesive on a peelable sheet and drying, or extruding the conductive adhesive into a sheet using an extruder such as a T-die It can also be formed.
塗工方法は、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。塗工に際して、乾燥工程を行うことが好ましい。乾燥工程は、例えば、熱風乾燥機、赤外線ヒーター等の公知の乾燥装置を使用できる。 Coating methods include, 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. A known coating method such as a method can be used. In coating, it is preferable to perform a drying step. In the drying step, for example, a known drying device such as a hot air dryer or an infrared heater can be used.
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、その他の物性とのバランスを取り易くなる。 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. When the thickness is in the range of 1 to 100 μm, it becomes easy to balance the conductivity and other physical properties.
保護層は、絶縁性樹脂組成物を使用して導電層と同様の方法で作成することができる。または、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絶縁性樹脂を成形したフィルムを使用することもできる。保護層の厚みは、通常２〜１２μｍ程度である。 The protective layer can be formed in the same manner as the conductive layer using the insulating resin composition. Alternatively, a film obtained by molding an insulating resin such as polyester, polycarbonate, polyimide, polyphenylene sulfide, or the like can be used. The thickness of the protective layer is usually about 2 to 12 μm.
電磁波シールドフィルムは、例えば、導電層と保護層と貼り合わせて作製できる。なお、前記したとおり、保護層と導電層との間には、公知の方法で金属層を設けてもよい。 The electromagnetic wave shielding film can be produced, for example, by laminating a conductive layer and a protective layer. As described above, a metal layer may be provided between the protective layer and the conductive layer by a known method.
電磁波シールドフィルムは、導電層に含まれる熱硬化性樹脂と硬化剤が未硬化状態で存在し、配線板と加熱圧着により硬化することで、所望の接着強度を得ることが出来る。なお、前記未硬化状態は、硬化剤の一部が硬化した半硬化状態を含む。 In the electromagnetic wave shielding film, the thermosetting resin and the curing agent contained in the conductive layer exist in an uncured state, and a desired adhesive strength can be obtained by being cured by thermocompression bonding with the wiring board. The uncured state includes a semi-cured state in which a part of the curing agent is cured.
剥離性シートは、紙やプラスチック等の基材に公知の剥離処理を行ったシートである。 The peelable sheet is a sheet obtained by performing a known peeling treatment on a substrate such as paper or plastic.
なお、電磁波シールドフィルムは、異物の付着を防止するため、導電層および保護層に剥離性シートを貼り付けた状態で保存することが一般的である。 Note that the electromagnetic wave shielding film is generally stored in a state where a peelable sheet is attached to the conductive layer and the protective layer in order to prevent adhesion of foreign matters.
電磁波シールドフィルムは、導電層および保護層のほかに、他の機能層を備えることができる。他の機能層とは、ハードコート性、水蒸気バリア性、酸素バリア性、熱伝導性、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。 The electromagnetic wave shielding film can include other functional layers in addition to the conductive layer and the protective layer. The other functional layer is a layer having functions such as hard coat property, water vapor barrier property, oxygen barrier property, thermal conductivity, low dielectric constant, high dielectric constant or heat resistance.
本発明の電磁波シールドフィルムは、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、フレキシブルプリント配線板は元より、リジッドプリント配線板、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。 The electromagnetic wave shielding film of the present invention can be used in various applications where electromagnetic waves need to be shielded. For example, flexible printed wiring boards can be used for rigid printed wiring boards, COFs, TABs, flexible connectors, liquid crystal displays, touch panels, and the like.
《プリント配線板》
続いて、本発明のプリント配線板について説明する。
本発明のプリント配線板は、電磁波シールドフィルムと、カバーコート層と、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。
<Printed wiring board>
Then, the printed wiring board of this invention is demonstrated.
The printed wiring board of the present invention includes an electromagnetic wave shielding film, a cover coat layer, and a wiring board including a signal wiring and an insulating substrate.
＜カバーコート層＞
カバーコート層は、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。本発明のプリント配線板におけるカバーコート層は、紫外線硬化型のソルダーレジスト、ドライレジストフィルムから形成されてなることが好ましく、プリント配線板の製造コストダウンの点からドライレジストフィルムがより好ましい。このようなソルダーレジストまたはドライレジストフィルムから形成されてなるカバーコート層を用いることで、信号配線の狭ピッチ化に対応した、微細な穴の形成が可能である。
<Cover coat layer>
The cover coat layer is an insulating material that covers the signal wiring of the wiring board and protects it from the external environment. The cover coat layer in the printed wiring board of the present invention is preferably formed of an ultraviolet curable solder resist or a dry resist film, and a dry resist film is more preferable from the viewpoint of reducing the manufacturing cost of the printed wiring board. By using a cover coat layer formed from such a solder resist or a dry resist film, it is possible to form fine holes corresponding to the narrow pitch of the signal wiring.
カバーコート層は意匠性を高め、信号回路の設計情報の流出を防止する観点から、黒色とすることが好ましい。この場合、ソルダーレジストおよびドライレジストフィルムは黒色系着色剤を含有する。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。 The cover coat layer is preferably black from the viewpoint of enhancing the design and preventing leakage of design information of the signal circuit. In this case, the solder resist and the dry resist film contain 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.
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。これらの中でも漆黒性とマイグレーション耐性を向上する観点から、ペリレンブラック、チタンブラック、鉄黒および、混合系着色剤が好ましく、ペリレンブラックおよびチタンブラックがより好ましい。特に好ましくは、チタンブラックである。 Examples of the black pigment include carbon black, ketjen black, carbon nanotube (CNT), perylene black, titanium black, iron black, and aniline black. Among these, from the viewpoint of improving jetness and migration resistance, perylene black, titanium black, iron black, and mixed colorants are preferable, and perylene black and titanium black are more preferable. Particularly preferred is titanium black.
黒色系着色剤は、ドライレジストフィルム１００質量％中に０．５〜４０質量％含むことが好ましく、１〜３０質量％がより好ましい。黒色系着色剤を０．５〜４０質量％含むことで、高い漆黒性と、マイグレーション試験耐性を両立し易くなる。 The black colorant is preferably contained in an amount of 0.5 to 40% by mass and more preferably 1 to 30% by mass in 100% by mass of the dry resist film. By including 0.5 to 40% by mass of the black colorant, it becomes easy to achieve both high jetness and migration test resistance.
ソルダーレジストおよびドライレジストフィルムは、従来公知のものを用いることができ、通常、熱硬化性樹脂、感光性樹脂、モノマー、光開始剤および増感剤等を含む。 A conventionally well-known thing can be used for a soldering resist and a dry resist film, Usually, a thermosetting resin, a photosensitive resin, a monomer, a photoinitiator, a sensitizer, etc. are included.
ドライレジストフィルムによりカバーコート層を形成する場合、絶縁性基材の信号配線上に真空ラミネーターによってドライレジストフィルムを貼り合わせる。その後、ドライレジストフィルムに紫外線を照射し光硬化させた後、アルカリ水溶液によって現像することで、未照射部が洗い流される。現像後ドライレジストフィルムを１３０〜１９０℃でキュアし硬化させてカバーコート層を形成する。
ソルダーレジストを使用する場合は、ソルダーレジストを信号配線上にコーティングし乾燥させる。その後の工程はドライレジストフィルムと同様の手順でカバーコート層を形成する。
When the cover coat layer is formed from a dry resist film, the dry resist film is bonded to the signal wiring of the insulating substrate by a vacuum laminator. Thereafter, the dry resist film is irradiated with ultraviolet rays to be photocured, and then developed with an alkaline aqueous solution, whereby unirradiated portions are washed away. After development, the dry resist film is cured at 130 to 190 ° C. and cured to form a cover coat layer.
When using a solder resist, the solder resist is coated on the signal wiring and dried. Subsequent processes form a cover coat layer in the same procedure as the dry resist film.
カバーコート層の厚みは１０〜７０μｍが好ましく、２０〜５０μｍがより好ましい。カバーコート層の厚みを１０〜７０μｍの範囲にすることで、プリント配線板の屈曲性とマイグレーション耐性を向上することができる。 The thickness of the cover coat layer is preferably 10 to 70 μm, and more preferably 20 to 50 μm. By setting the thickness of the cover coat layer in the range of 10 to 70 μm, the flexibility and migration resistance of the printed wiring board can be improved.
カバーコート層のガラス転移温度（Ｔｇ）は４０℃〜１２０℃が好ましく、５０℃〜１００℃がより好ましい。カバーコート層のガラス転移温度（Ｔｇ）を４０℃〜１２０℃にすることで、屈曲性とマイグレーション耐性を向上することができる。 The glass transition temperature (Tg) of the cover coat layer is preferably 40 ° C to 120 ° C, more preferably 50 ° C to 100 ° C. Flexibility and migration resistance can be improved by setting the glass transition temperature (Tg) of the cover coat layer to 40 ° C to 120 ° C.
＜信号配線および絶縁性基材を含む配線板＞
信号配線は、アースを取るグランド配線、電子部品に電気信号を送る配線回路を含み、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。
絶縁性基材は、ポリエステル、ポリカーボネート、ポリイミド、液晶ポリマー、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、液晶ポリマーがより好ましい。
<Wiring board including signal wiring and insulating base>
The signal wiring includes a ground wiring for grounding and a wiring circuit for sending an electric signal to the electronic component, and is generally formed by etching a copper foil.
The insulating substrate is preferably a bendable plastic such as polyester, polycarbonate, polyimide, liquid crystal polymer, or polyphenylene sulfide, and more preferably polyimide or liquid crystal polymer.
カバーコート層を形成した配線板と、電磁波シールドフィルムとの加熱圧着は、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分ポストキュアを行う場合もある。なお、電磁波シールドフィルムは、加熱圧着後に電磁波シールド層ということがある。 The thermocompression bonding between the wiring board on which the cover coat layer is formed and the electromagnetic wave shielding film is generally 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 thermosetting resin and the curing agent react by thermocompression bonding. In order to accelerate curing, post-curing may be performed at 150 to 190 ° C. for 30 to 90 minutes after thermocompression bonding. In addition, an electromagnetic wave shielding film may be called an electromagnetic wave shielding layer after thermocompression bonding.
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、比較例を挙げて本発明を詳細に説明するが、本発明は以下の実施例のみに限定されるものではない。なお、以下の「部」及び「％」とは、それぞれ「質量部」及び「質量％」に基づく値である。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited only to a following example. In addition, the following “parts” and “%” are values based on “parts by mass” and “mass%”, respectively.
＜平均粒子径Ｄ５０およびＤ９５＞
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。難燃剤の平均粒子径Ｄ９５は平均粒子径Ｄ５０と同様に測定して得た平均粒子径Ｄ９５の数値であり、粒子径累積分布における累積値が９５％の粒子径である。
<Average particle diameter D50 and D95>
The average particle diameter is a numerical value of the average particle diameter D50 obtained by measuring conductive composite fine particles with a tornado dry powder sample module using a laser diffraction / scattering particle size distribution measuring device LS13320 (manufactured by Beckman Coulter). The cumulative value in the cumulative particle size distribution is a particle size of 50%. The distribution was volume distribution, and the refractive index was set to 1.6. Any particle size may be used, and either primary particles or secondary particles may be used. The average particle diameter D95 of the flame retardant is a numerical value of the average particle diameter D95 obtained by measurement in the same manner as the average particle diameter D50, and the cumulative value in the particle diameter cumulative distribution is a particle diameter of 95%.
＜酸価の測定＞
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
<Measurement of acid value>
About 1 g of thermosetting resin is precisely weighed in a conical flask with a stopper, and 50 mL of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1) is added and dissolved. To this is added phenolphthalein reagent as an indicator and held for 30 seconds. Thereafter, the solution is titrated with a 0.1 mol / L alcoholic potassium hydroxide solution until the solution becomes light red. The acid value was determined by the following formula. The acid value is a numerical value of the dry state of the resin.
Acid value (mgKOH / g) = (a × F × 56.1 × 0.1) / S
S: Amount of sample collected x (solid content of sample / 100) (g)
a: Titration volume of 0.1 mol / L alcoholic potassium hydroxide solution (mL)
F: Potency of 0.1 mol / L alcoholic potassium hydroxide solution
＜被覆率＞
被覆率は、Ｘ線光電子分光分析（ＥＳＣＡ）により求めた。専用の台に両面粘着テープを貼り、両面粘着テープ上に導電性フィラーを落とした後、圧縮空気で余分な導電性フィラーを飛ばした。そして、Ｘ線光電子分光分析装置（ＥＳＣＡ ＡＸＩＳ-ＨＳ、島津製作所社製）にて、異なる５箇所を測定した。そして、解析ソフト（Ｋｒａｔｏｓ社製）により被覆層（銀）と核体（銅）のピーク面積から算出される、被覆層（銀）の質量濃度％の平均値を銀の被覆率とした。詳細な条件は、ＡＸＩＳ−ＨＳ（島津製作所社製／Ｋｒａｔｏｓ）、Ｘ線源：Ｄｕａｌ（Ｍｇ）１５ｋＶ，１０ｍＡ Ｐａｓｓ ｅｎｅｒｇｙ ８０ｅＶ、Ｓｔｅｐ：０．１ ｅＶ／Ｓｔｅｐ、Ｓｐｅｅｄ：１２０秒／元素、Ｄｅｌｌ：３００、積算回数：８の条件でＡｇ３ｄ：２とＣｕ２Ｐ：１のピーク面積から銀と銅の質量濃度を求め、銀の質量濃度の割合を被覆率とした。
<Coverage>
The coverage was determined by X-ray photoelectron spectroscopy (ESCA). A double-sided adhesive tape was affixed to a dedicated stand, the conductive filler was dropped on the double-sided adhesive tape, and then the excess conductive filler was blown away with compressed air. And five different places were measured with the X-ray photoelectron spectroscopy analyzer (ESCA AXIS-HS, Shimadzu Corp. make). And the average value of mass concentration% of a coating layer (silver) calculated from the peak area of a coating layer (silver) and a nucleus (copper) with analysis software (made by Kratos) was made into the silver coverage. Detailed conditions are: AXIS-HS (manufactured by Shimadzu Corporation / Kratos), X-ray source: Dual (Mg) 15 kV, 10 mA Pass energy 80 eV, Step: 0.1 eV / Step, Speed: 120 seconds / element, Dell: The mass concentration of silver and copper was determined from the peak areas of Ag3d: 2 and Cu2P: 1 under the conditions of 300 and the number of integrations: 8, and the ratio of the silver mass concentration was defined as the coverage.
以下、実施例で使用した材料を示す。
熱硬化性樹脂１：ポリウレタン系樹脂 酸価１０［ｍｇＫＯＨ／ｇ］（トーヨーケム社製）
熱硬化性樹脂２：ポリカーボネート系樹脂 酸価５［ｍｇＫＯＨ／ｇ］（トーヨーケム社製）
熱硬化性樹脂３：スチレン系樹脂 酸価１１［ｍｇＫＯＨ／ｇ］（トーヨーケム社製）
熱硬化性樹脂４：フェノキシ系樹脂 酸価１５［ｍｇＫＯＨ／ｇ］（トーヨーケム社製）
硬化剤１：エポキシ樹脂、「デナコールＥＸ８３０」（２官能エポキシ樹脂 エポキシ当量＝２６８ｇ／ｅｑ）ナガセケムテックス社製
硬化剤２：エポキシ樹脂、「ＹＸ８０００」（水添ビスフェノールエポキシ樹脂 エポキシ当量＝２１０ｇ／ｅｑ）三菱化学社製
硬化剤３：エポキシ樹脂、「ｊＥＲ１５７Ｓ７０」（ビスフェノールＡノボラック型エポキシ樹脂 エポキシ当量＝２０８ｇ／ｅｑ）三菱化学社製
硬化剤４：アジリジン化合物、「ケミタイト ＰＺ−３３」（日本触媒社製）
The materials used in the examples are shown below.
Thermosetting resin 1: Polyurethane resin Acid value 10 [mgKOH / g] (Toyochem)
Thermosetting resin 2: Polycarbonate-based resin Acid value 5 [mgKOH / g] (Toyochem)
Thermosetting resin 3: Styrene resin Acid value 11 [mgKOH / g] (Toyochem)
Thermosetting resin 4: Phenoxy resin Acid value 15 [mg KOH / g] (Toyochem)
Curing agent 1: Epoxy resin, “Denacol EX830” (bifunctional epoxy resin, epoxy equivalent = 268 g / eq) Curing agent manufactured by Nagase ChemteX Corporation: Epoxy resin, “YX8000” (hydrogenated bisphenol epoxy resin, epoxy equivalent = 210 g / eq) ) Hardener made by Mitsubishi Chemical Co., Ltd .: Epoxy resin, “jER157S70” (bisphenol A novolac type epoxy resin epoxy equivalent = 208 g / eq) Hardener made by Mitsubishi Chemical Co., Ltd. 4: Aziridine compound, “Chemite PZ-33” (Nippon Shokubai Co. Made)
導電性フィラー１：「核体に銅、被覆層に銀を使用した樹枝状粒子Ｄ５０平均粒子径＝ １１．０μｍ、銀の被覆率＝７０％」（ 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Ｄ５０平均粒子径＝ １１．０μｍ、銀の被覆率＝８０％」（ 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樹枝状粒子Ｄ５０平均粒子径＝ １１．０μｍ、銀の被覆率＝９０％」（ 福田金属箔粉工業社製）
導電性フィラー４：「核体に銅、被覆層に銀を使用した樹枝状粒子Ｄ５０平均粒子径＝ １１．０μｍ、銀の被覆率＝１００％」（ 福田金属箔粉工業社製）
＜銅箔＞
キャリア付き電解銅箔：１８μｍのキャリア銅箔に３μｍの電解銅箔（電解銅箔部は、開口部面積１５９０μｍ2、開口部数６００個/ｃｍ2、 開口率１％が形成されている）
剥離性シート：表面にシリコーン離型剤をコーティングした厚みが５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルム
Conductive filler 1: “dendritic particles D50 using copper as the core and silver as the coating layer D50 average particle size = 11.0 μm, silver coverage = 70%” (Fukuda Metal Foil Co., Ltd.)
Conductive filler 2: “Dendrite-like particles D50 using copper as the core and silver as the coating layer D50 average particle size = 11.0 μm, silver coverage = 80%” (Fukuda Metal Foil Co., Ltd.)
Conductive filler 3: “dendritic particles D50 using copper as the core and silver as the coating layer D50 average particle size = 11.0 μm, silver coverage = 90%” (Fukuda Metal Foil Powder Industries, Ltd.)
Conductive filler 4: “dendritic particles D50 using copper as the core and silver as the coating layer D50 average particle diameter = 11.0 μm, silver coverage = 100%” (Fukuda Metal Foil Powder Industries, Ltd.)
<Copper foil>
Electrolytic copper foil with carrier: 3 μm electrolytic copper foil on 18 μm carrier copper foil (the electrolytic copper foil portion has an opening area of 1590 μm 2 , the number of openings of 600 pieces / cm 2 , and an opening ratio of 1%)
Peelable sheet: Polyethylene terephthalate (PET) film having a thickness of 50 μm and a surface coated with a silicone release agent
［リン系難燃剤１］
表面処理がなされていない平均粒子径Ｄ９５が５μｍのホスフィン酸アルミニウムを用いた。
[Phosphorus flame retardant 1]
Aluminum phosphinate having an average particle diameter D95 of 5 μm and not subjected to surface treatment was used.
［リン系難燃剤２］
オルトケイ酸テトラエチル（以下、ＴＥＯＳともいう）のエタノール溶液（濃度：０．４％）８００ｍｌに、後述する方法で求めたＤ９５粒子径が５μｍのホスフィン酸アルミニウムを１０ｇ加え、濃ＮＨ3水でｐＨを１２に調整した後、３時間撹拌し、ろ過、エタノールで洗浄することで、ホスフィン酸アルミニウム１の表面にシリカが付着しているリン系難燃剤２を得た。
表面に付着しているシリカの量を、後述するＩＣＰ発光分光分析法により求めたところ、ホスフィン酸アルミニウム１が１００部に対し、０．０１部であった。
[Phosphorus flame retardant 2]
To 800 ml of an ethanol solution (concentration: 0.4%) of tetraethyl orthosilicate (hereinafter also referred to as TEOS), 10 g of aluminum phosphinate having a D95 particle diameter of 5 μm obtained by the method described later is added, and the pH is adjusted with concentrated NH 3 water. After adjusting to 12, the mixture was stirred for 3 hours, filtered, and washed with ethanol to obtain a phosphorus-based flame retardant 2 in which silica was adhered to the surface of the aluminum phosphinate 1.
When the amount of silica adhering to the surface was determined by ICP emission spectroscopic analysis described later, aluminum phosphinate 1 was 0.01 part with respect to 100 parts.
［リン系難燃剤３］
ＴＥＯＳのエタノール溶液に加えるホスフィン酸アルミニウムの量を代えた以外は合成例１と同様にして、ホスフィン酸アルミニウムが１００部に対し、表面に付着しているシリカの量が０．１部であるリン系難燃剤３を調整した。
[Phosphorus flame retardant 3]
Except for changing the amount of aluminum phosphinate added to the TEOS ethanol solution, in the same manner as in Synthesis Example 1, 100 parts of aluminum phosphinate and 0.1 parts of silica adhering to the surface are phosphorous. System flame retardant 3 was prepared.
［リン系難燃剤４、５］
リン系難燃剤２を１００部ミキサーに入れ、窒素雰囲気下で撹拌しながら、シランカップリング剤である東レ・ダウコーニング（株）製のＺ−６６１０を１０部、エタノール１０部を噴霧し、１５０℃で２時間加熱撹拌し、溶剤を除去して冷却した。このようにして前記リン系難燃剤２の表面にさらにシランカップリング剤が付着したリン系難燃剤４を得た。噴霧に使うシランカップリング剤の量を変更する以外は同様にして、リン系難燃剤５を調整した。リン系難燃剤４およびリン系難燃剤５中のシランカップリング剤の量は、ホスフィン酸アルミニウム１００部に対して、それぞれ０．０１および０．５部であった。
[Phosphorus flame retardants 4, 5]
Phosphoric flame retardant 2 is put into a 100-part mixer, and while stirring in a nitrogen atmosphere, 10 parts of Z-6610 made by Toray Dow Corning Co., Ltd., which is a silane coupling agent, and 10 parts of ethanol are sprayed. The mixture was heated and stirred at 0 ° C. for 2 hours, and the solvent was removed to cool. In this way, a phosphorus flame retardant 4 having a silane coupling agent attached to the surface of the phosphorus flame retardant 2 was obtained. The phosphorus-based flame retardant 5 was adjusted in the same manner except that the amount of the silane coupling agent used for spraying was changed. The amount of the silane coupling agent in the phosphorus-based flame retardant 4 and the phosphorus-based flame retardant 5 was 0.01 and 0.5 parts, respectively, with respect to 100 parts of aluminum phosphinate.
［リン系難燃剤６］
平均粒子径Ｄ９５が２０μｍのホスフィン酸マグネシウム６水和物を用いた。
[Phosphorus flame retardant 6]
Magnesium phosphinate hexahydrate having an average particle diameter D95 of 20 μm was used.
［リン系難燃剤７］
平均粒子径Ｄ９５が１７μｍのポリリン酸メラミンを用いた。
[Phosphorus flame retardant 7]
Melamine polyphosphate having an average particle diameter D95 of 17 μm was used.
［リン系難燃剤８］
平均粒子径Ｄ９５が２０μｍの赤リンを用いた。
[Phosphorus flame retardant 8]
Red phosphorus having an average particle diameter D95 of 20 μm was used.
＜ＩＣＰ発光分光分析法によるシリカ表面処理の定量＞
表面処理難燃剤０．２５ｇを精秤し、硝酸７ｍｌを加え、マイクロウェーブ型湿式分解装置を用い、１５０℃で２分、１８０℃で２分、２１０℃で１０分と段階的に続けて加熱し、硝酸で分解処理した後、蒸留水で５０ｍｌ定溶とし室温にてＩＣＰ測定（装置名：ＩＣＰ発光分光分析装置 ＳＰＥＣＴＲＯ ＡＲＣＯＳ アメテック社製）を行った。
<Quantification of silica surface treatment by ICP emission spectroscopy>
0.25 g of the surface-treated flame retardant is precisely weighed, 7 ml of nitric acid is added, and it is heated continuously in steps of 150 ° C. for 2 minutes, 180 ° C. for 2 minutes, and 210 ° C. for 10 minutes using a microwave type wet decomposition apparatus. Then, after decomposing with nitric acid, it was dissolved in 50 ml with distilled water, and ICP measurement was performed at room temperature (device name: ICP emission spectroscopic analyzer SPECTRO ARCOS manufactured by Ametech Co., Ltd.).
［実施例１］
熱硬化性樹脂１を１００部、導電性フィラー１を３２０部、硬化剤１を３０部、硬化剤２を１０部および硬化促進剤を１部容器に仕込み、不揮発分濃度が４０％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 thermosetting resin 1, 320 parts of conductive filler 1, 30 parts of curing agent 1, 10 parts of curing agent 2 and 1 part of curing accelerator are charged into a container so that the non-volatile content concentration becomes 40%. A conductive resin composition was obtained by adding a mixed solvent of toluene: isopropyl alcohol (mass ratio 2: 1) and stirring with a disper for 10 minutes. 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、熱硬化性樹脂１を１００部、硬化剤１を３０部、硬化剤２を１０部、リン系難燃剤２を３部および硬化促進剤を１部容器に仕込み、不揮発分濃度が４０％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分攪拌することで絶縁性性樹脂組成物を得た。この絶縁性樹脂組成物を剥離性シートにバーコーターを用いて乾燥厚みが１０μｍになるように塗工し、さらに１００℃の電気オーブンで２分間乾燥し保護層を得た。この保護層をキャリア付き電解銅箔の電解銅箔側に貼り合せた後、キャリア銅箔を剥がし、保護層上に電解銅箔を積層した。次に、電解銅箔面に導電層を貼り合わせることで、「剥離性シート／保護層／電解銅箔／導電層／剥離性シート」からなる電磁波シールドフィルムを得た。 Separately, 100 parts of thermosetting resin 1, 30 parts of curing agent 1, 10 parts of curing agent 2, 3 parts of phosphorus flame retardant 2 and 1 part of curing accelerator are charged in a container, and the nonvolatile content concentration is 40%. An insulating resin composition was obtained by adding a mixed solvent of toluene: isopropyl alcohol (mass ratio 2: 1) and stirring with a disper for 10 minutes. This insulating resin composition was applied to 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 protective layer. After this protective layer was bonded to the electrolytic copper foil side of the electrolytic copper foil with carrier, the carrier copper foil was peeled off, and the electrolytic copper foil was laminated on the protective layer. Next, the electromagnetic wave shielding film which consists of "peelable sheet / protective layer / electrolytic copper foil / conductive layer / peelable sheet" was obtained by bonding a conductive layer on the electrolytic copper foil surface.
［実施例２〜１９、比較例１］
組成を表１に記載した通りに変更した以外は、実施例１と同様に行うことで実施例２〜１９、比較例１の電磁波シールドフィルムをそれぞれ得た。尚、表中の数値は特に断りのない限り部を表し、空欄は使用していないことを表す。
[Examples 2 to 19, Comparative Example 1]
Except having changed the composition as described in Table 1, the electromagnetic shielding films of Examples 2 to 19 and Comparative Example 1 were obtained by carrying out in the same manner as in Example 1. In addition, the numerical value in a table | surface represents a part unless there is particular notice, and the blank represents that it is not using.
［実施例２０］
熱硬化性樹脂１を１００部、導電性フィラー４を３２０部、硬化剤１を３０部、硬化剤２を１０部および硬化促進剤を１部容器に仕込み、不揮発分濃度が４０％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 20]
100 parts of thermosetting resin 1, 320 parts of conductive filler 4, 30 parts of curing agent 1, 10 parts of curing agent 2 and 1 part of curing accelerator are charged into a container so that the non-volatile concentration is 40%. A conductive resin composition was obtained by adding a mixed solvent of toluene: isopropyl alcohol (mass ratio 2: 1) and stirring with a disper for 10 minutes. 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、熱硬化性樹脂１を１００部、硬化剤１を３０部、硬化剤２を１０部、リン系難燃剤２を３部および硬化剤４を１部容器に仕込み、不揮発分濃度が４０％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分攪拌することで絶縁性樹脂組成物を得た。
この絶縁性樹脂組成物を剥離性シートにバーコーターを用いて乾燥厚みが１０μｍになるように塗工し、さらに１００℃の電気オーブンで２分間乾燥し保護層を得た。さらに導電層と保護層をラミネーターで張り合わせることで実施例１の電磁波シールドフィルムを得た。
Separately, 100 parts of thermosetting resin 1, 30 parts of curing agent 1, 10 parts of curing agent 2, 3 parts of phosphorus flame retardant 2 and 1 part of curing agent 4 are charged into a container, and the non-volatile content concentration is 40%. An insulating resin composition was obtained by adding a mixed solvent of toluene: isopropyl alcohol (mass ratio 2: 1) and stirring with a disper for 10 minutes.
This insulating resin composition was applied to 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 protective layer. Furthermore, the electromagnetic wave shielding film of Example 1 was obtained by bonding together a conductive layer and a protective layer with a laminator.
得られた電磁波シールドフィルムについて以下の物性を評価した。 The following physical properties of the obtained electromagnetic wave shielding film were evaluated.
＜電磁波シールドフィルムのリン抽出濃度＞
１０ｃｍ×１０ｃｍのサイズにカットした電磁波シールドフィルムを用意した。電磁波シールドフィルムの保護層および導電層面にはそれぞれ剥離性シートが貼り付けてあり、これをそのまま１５０℃、２ＭＰａ、３０分の条件で熱プレスし、保護層および導電層を熱硬化させた試験片を得た。試験片の両面の剥離性シートを剥がした後、試験片０．１６部を切り取って、イオン交換水１００部に浸した。次いで、これを８５℃、７２時間の条件で静置し、ろ過処理することで抽出液を得た。抽出液を超純水で１〜１００倍に希釈し、ＩＣＰ発光分光分析装置（ＡＭＥＴＥＫ社製「ＳＰＥＣＴＲＯ ＡＲＣＯＳ（登録商標）；ＦＨＳ１２」）によってリン元素の定量分析を行うことでリン抽出濃度を測定した。定量分析の際には７２時間８５℃加熱したイオン交換水をブランクとして測定し、抽出液中に含まれる正味のリン抽出濃度を求めた。
<Phosphorus extraction concentration of electromagnetic shielding film>
An electromagnetic wave shielding film cut to a size of 10 cm × 10 cm was prepared. A test piece in which a peelable sheet is attached to each of the protective layer and the conductive layer surface of the electromagnetic shielding film, and this is heat-pressed as it is at 150 ° C., 2 MPa, for 30 minutes to thermally cure the protective layer and the conductive layer. Got. After peeling off the peelable sheets on both sides of the test piece, 0.16 part of the test piece was cut out and immersed in 100 parts of ion-exchanged water. Next, this was allowed to stand at 85 ° C. for 72 hours and filtered to obtain an extract. The extract is diluted 1 to 100 times with ultrapure water, and the phosphorus extraction concentration is measured by quantitative analysis of phosphorus elements using an ICP emission spectrophotometer ("SPECTRO ARCOS (registered trademark); FHS12" manufactured by AMETEK) did. In quantitative analysis, ion-exchanged water heated at 85 ° C. for 72 hours was measured as a blank, and the net phosphorus extraction concentration contained in the extract was determined.
＜電磁波シールドフィルムの銅抽出濃度＞
リン抽出濃度と同様の方法で銅抽出濃度を決定した。
<Copper extraction concentration of electromagnetic shielding film>
The copper extraction concentration was determined in the same manner as the phosphorus extraction concentration.
＜マイグレーション試験＞
カルボキシル基含有感光性ウレタン樹脂（トーヨーケム株式会社製：酸価＝６７ｍｇＫＯＨ／ｇ、エチレン性不飽和基当量＝７６５ｇ／ｅｑ）の固形分１００部に対して、硬化剤として、エピコート１０３１Ｓ（三菱化学株式会社製：多官能グリシジルエーテル型エポキシ樹脂）；１０部、ＢＬ３１７５（住化バイエルウレタン株式会社製：イソシアヌレート型ブロックイソシアネート）１０部、難燃剤としてホスフィン酸アルミニウムＥＸＯＬＩＴＯＰ−９３５（クラリアントジャパン株式会社製）；２０部、着色剤として銅フタロシアニン顔料ＬＩＯＮＯＬ ＢＬＵＥ ＦＧ７３５０（トーヨーカラー株式会社製）；１部、光重合開始剤としてイルガキュアー９０７（チバ・スペシャルティ・ケミカルズ製：２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−１−プロパン）；５部、光増感剤としてＤＥＴＸ−Ｓ（日本化薬株式会社製：２，４−ジエチルチオキサントン）；０．５部を均一に溶解・混合し、横型サンドミルＤＹＮＯ−ＭＩＬＬ（株式会社シンマルエンタープライズ製）を使用して、グラインドゲージによる粒子径が１０μｍ未満になるまで分散し、感光性樹脂組成物を得た。
<Migration test>
Epicoat 1031S (Mitsubishi Chemical Corporation) as a curing agent for 100 parts of a solid content of carboxyl group-containing photosensitive urethane resin (manufactured by Toyochem Co., Ltd .: acid value = 67 mg KOH / g, ethylenically unsaturated group equivalent = 765 g / eq) 10 parts, BL3175 (manufactured by Sumika Bayer Urethane Co., Ltd .: isocyanurate type block isocyanate), aluminum phosphinate EXOLITOP-935 (made by Clariant Japan Co., Ltd.) as a flame retardant 20 parts, copper phthalocyanine pigment LIONOL BLUE FG7350 (manufactured by Toyocolor Co., Ltd.) as a colorant; 1 part, Irgacure 907 (manufactured by Ciba Specialty Chemicals: 2-methyl-1- [4- ( Mechi Thio) phenyl] -2-morpholino-1-propane); 5 parts, DETX-S as a photosensitizer (manufactured by Nippon Kayaku Co., Ltd .: 2,4-diethylthioxanthone); The mixture was mixed and dispersed using a horizontal sand mill DYNO-MILL (manufactured by Shinmaru Enterprise Co., Ltd.) until the particle diameter by a grind gauge was less than 10 μm to obtain a photosensitive resin composition.
上記で得られた感光性樹脂組成物を、ドクターブレードを使用して乾燥後の厚さが４０μｍとなるようにポリエチレンテレフタレート（ＰＥＴ）フィルム（Ｓ-１２ 厚さ１２μｍ 東レ・デュポン社製）上に均一塗工して１００℃で５分乾燥させた後、室温まで冷却し被膜を形成した。さらに得られた被膜を二軸延伸ポリプロピレンフィルム（ＯＰＰフィルム）製の剥離性フィルムに貼り合わせることで感光性カバーレイフィルムを得た。 The photosensitive resin composition obtained above is used on a polyethylene terephthalate (PET) film (S-12 thickness 12 μm, manufactured by Toray DuPont) so that the thickness after drying using a doctor blade is 40 μm. After uniform coating and drying at 100 ° C. for 5 minutes, the coating was formed by cooling to room temperature. Furthermore, the obtained coating was bonded to a peelable film made of a biaxially stretched polypropylene film (OPP film) to obtain a photosensitive coverlay film.
図１を参照してマイグレーション試験を説明する。厚さ１６μｍの銅箔と厚さ２５μｍポリイミドフィルムの積層体をエッチング処理することで図１（１）の平面図に示した通り、ポリイミドフィルム１上にライン／スペース＝０．０５ｍｍ／０．０５ｍｍの、カソード電極接続点２’を備えたカソード電極用櫛型信号配線２と、アノード電極接続点３’を備えたアノード電極用櫛型信号配線３とをそれぞれ形成した。次いで感光性カバーレイフィルムから、ＯＰＰフィルムを剥がし、図１（２）の平面図に示した通り、カソード電極用櫛型信号配線２およびアノード電極用櫛型信号配線３を覆い、カソード電極接続点２’付近およびアノード電極接続点３’付近が露出する程度の大きさに感光性カバーレイフィルを重ね、真空ラミネートすることで感光性カバーレイフィルムを積層体に貼り合わせた。なお真空ラミネート条件は加熱温度６０℃、真空時間６０秒、真空到達圧２ｈＰａ、圧力０．４ＭＰａ、加圧時間６０秒であった。さらに積層体の感光性カバーレイフィルムの上に厚さ１２０μｍのＰＥＴマイラーシートを重ね、その上方から水銀ショートアークアンプ（５ｋＷ）を使用して５分間露光した。次いで、ＰＥＴマイラーシートを剥がし、現像機で４０秒間現像（現像液：濃度１％の炭酸ナトリウム水溶液、液温３０℃、スプレー圧０．２ ＭＰａ）した。現像後、１５０℃の熱風乾燥器で感光性カバーレイフィルムを１時間熱硬化（ポストキュア）することでカバーコート層４付き配線板を得た。
さらに得られた電磁波シールドフィルムの導電層側から剥離性シートを剥がし、露出した導電層面をカバーコート層４の上に貼り合わせることで図１（３）に示す平面図の通りに積層した試料を得た。得られた試料は、図１（４）に示す試料のＡ−Ａ’断面図に記載した通り導電層５ｂはカソード電極用櫛型信号配線２と電気的に接続している。５ａは導電層５ｂの表面に積層された保護層である。
The migration test will be described with reference to FIG. By etching a laminate of a 16 μm thick copper foil and a 25 μm thick polyimide film, line / space = 0.05 mm / 0.05 mm on the polyimide film 1 as shown in the plan view of FIG. The cathode electrode comb signal wiring 2 having the cathode electrode connection point 2 'and the anode electrode comb signal wiring 3 having the anode electrode connection point 3' were formed. Next, the OPP film is peeled off from the photosensitive cover lay film, and as shown in the plan view of FIG. 1 (2), the cathode electrode comb signal wiring 2 and the anode electrode comb signal wiring 3 are covered, and the cathode electrode connection point The photosensitive coverlay film was laminated in such a size that the vicinity of 2 ′ and the vicinity of the anode electrode connection point 3 ′ were exposed, and the photosensitive coverlay film was bonded to the laminate by vacuum lamination. The vacuum lamination conditions were a heating temperature of 60 ° C., a vacuum time of 60 seconds, a vacuum ultimate pressure of 2 hPa, a pressure of 0.4 MPa, and a pressurization time of 60 seconds. Further, a PET mylar sheet having a thickness of 120 μm was placed on the photosensitive coverlay film of the laminate, and exposed for 5 minutes from above using a mercury short arc amplifier (5 kW). Next, the PET mylar sheet was peeled off and developed for 40 seconds with a developing machine (developer: sodium carbonate aqueous solution with a concentration of 1%, liquid temperature 30 ° C., spray pressure 0.2 MPa). After development, the photosensitive coverlay film was heat-cured (postcure) for 1 hour with a hot air dryer at 150 ° C. to obtain a wiring board with a cover coat layer 4.
Further, the peelable sheet was peeled off from the conductive layer side of the obtained electromagnetic wave shielding film, and the exposed conductive layer surface was bonded onto the cover coat layer 4 to laminate a sample laminated as shown in the plan view of FIG. Obtained. In the obtained sample, the conductive layer 5b is electrically connected to the comb signal wiring 2 for the cathode electrode as described in the AA ′ sectional view of the sample shown in FIG. 5a is a protective layer laminated on the surface of the conductive layer 5b.
得られた試料を１５０℃、２．０ＭＰａ、３０ｍｉｎの条件で熱プレスすることで熱硬化性樹脂を硬化させた。次いで、試料を８５℃−８５％ＲＨ（相対湿度）の雰囲気下で、アノード電極接続点３’にアノード電極を接続し、カソード電極接続点２’にカソード電極を接続した上で、電圧５０Ｖを印加し５００時間継続した。そして５００時間を経過するまでの抵抗値の変化を継続して測定した。なお下記「リークタッチ」とは、短絡による絶縁破壊があり、瞬間的に抵抗が低下し電流が流れることをいう。リークタッチがない場合は絶縁性が低下しない。評価基準は以下の通りである。
◎：５００時間経過後の抵抗値が１×１０7Ω以上、かつリークタッチ無し。極めて良好。
○：５００時間経過後の抵抗値が１×１０7Ω以上、かつリークタッチ１回有り。良好。
△：５００時間経過後の抵抗値が１×１０7Ω以上、かつリークタッチ２回有り。実用上問題ない。
×：５００時間経過後の抵抗値が１×１０7Ω未満、または、
５００時間経過後の抵抗値が１×１０7Ω以上、かつリークタッチ３回以上有り。実用不可。
The obtained sample was hot-pressed under the conditions of 150 ° C., 2.0 MPa, and 30 min to cure the thermosetting resin. Next, the anode was connected to the anode electrode connection point 3 ′ and the cathode electrode was connected to the cathode electrode connection point 2 ′ in an atmosphere of 85 ° C. to 85% RH (relative humidity). Application was continued for 500 hours. And the change of the resistance value until 500 hours passed was measured continuously. The “leak touch” described below means that there is a dielectric breakdown due to a short circuit, the resistance decreases instantaneously, and a current flows. If there is no leak touch, insulation does not decrease. The evaluation criteria are as follows.
A: Resistance value after 500 hours is 1 × 10 7 Ω or more and no leak touch. Very good.
○: Resistance value after 500 hours is 1 × 10 7 Ω or more, and there is one leak touch. Good.
Δ: Resistance value after 500 hours is 1 × 10 7 Ω or more, and there are two leak touches. There is no problem in practical use.
×: Resistance value after 500 hours is less than 1 × 10 7 Ω, or
The resistance after 500 hours is 1 × 10 7 Ω or more and there are 3 or more leak touches. Not practical.
＜屈曲性＞
屈曲性をＪＩＳ Ｃ６４７１に準拠して屈曲性についてＭＩＴ試験にて測定した。
電磁波シールドフィルムを幅１５ｍｍ、長さ１２０ｍｍの大きさに準備した。また、電磁波シールドフィルムを貼り付ける被着体は、ポリイミドフィルム（厚さ１２．５μｍ）と銅箔（厚さ１８μｍ）とを積層した２層ＣＣＬを元に、ＪＩＳ Ｃ６４７１に基づく形状に配線を形成した。次いで配線上に上記マイグレーション試験と同様に感光性カバーレイフィルムを貼付、露光、現像後、にポストキュアを行なうことでカバーコート層を形成した。さらに、電磁波シールドフィルムの導電層側の剥離性シートを剥離して露出した導電層をカバーコート層に対して、１５０℃、３０分間、２．０ＭＰａの条件で圧着することで試料を得た。得られた試料についてＰＣＴ試験（条件：１２１℃、１００％ＲＨ、２気圧、２４時間）を行った。ＰＣＴ試験後の試料について、温度２５℃、湿度５０％雰囲気下で、曲率半径０．３８ｍｍ、荷重５００ｇ、速度１８０回／ｍｉｎの条件でＭＩＴ試験機を使用して屈曲性を測定した。評価は、屈曲を３０００回行い配線が断線するまでの屈曲回数を測定した。評価基準は以下の通りである。
◎：３０００回以上で断線しなかった。 極めて良好。
○：断線までに２７００回以上、３０００回未満 良好
△：断線までに２５００回以上、２７００回未満 実用上問題ない。
×：２５００回未満で断線した。 実用不可。
<Flexibility>
Flexibility was measured by a MIT test for flexibility according to JIS C6471.
An electromagnetic wave shielding film was prepared to have a width of 15 mm and a length of 120 mm. In addition, the adherend to which the electromagnetic wave shielding film is attached is formed in a shape based on JIS C6471, based on a two-layer CCL in which a polyimide film (thickness 12.5 μm) and a copper foil (thickness 18 μm) are laminated. did. Next, a cover coat layer was formed by pasting a photosensitive coverlay film on the wiring in the same manner as in the migration test, post-curing after exposure and development. Furthermore, the sample was obtained by pressure-bonding the conductive layer exposed by peeling off the peelable sheet on the conductive layer side of the electromagnetic wave shielding film to the cover coat layer at 150 ° C. for 30 minutes at 2.0 MPa. The obtained sample was subjected to a PCT test (conditions: 121 ° C., 100% RH, 2 atmospheres, 24 hours). For the sample after the PCT test, the flexibility was measured using an MIT tester under the conditions of a radius of curvature of 0.38 mm, a load of 500 g, and a speed of 180 times / min in an atmosphere of a temperature of 25 ° C. and a humidity of 50%. In the evaluation, the number of bending until the wiring was broken after 3000 times of bending was measured. The evaluation criteria are as follows.
(Double-circle): It was not disconnected by 3000 times or more. Very good.
○: 2700 times or more and less than 3000 times before disconnection Good Δ: 2500 times or more and less than 2700 times before disconnection No problem in practical use.
X: Disconnected in less than 2500 times. Not practical.
＜難燃性＞
（２）難燃性試験
剥離性シート２を剥がした電磁波シールドフィルムを用意し、露出した導電性接着剤層に、厚さが１２．５μｍのポリイミドフィルム（東レ・デュポン社製「カプトン５０Ｈ」）を１５０℃、１ＭＰａ、３０ｍｉｎの条件で圧着し、「電磁波シールドフィルム／カプトン５０Ｈ／電磁波シールドフィルム」の難燃性試験用試料を得た。ＵＬ９４規格Ｖ−０、ＶＴＭ−０グレードを達成できるか否かにより難燃性を評価した。
◎：ＵＬ９４規格Ｖ−０グレードを達成できる。極めて良好。
○：ＵＬ９４規格ＶＴＭ−０グレード試験で、試験片１０本中 全て燃焼せず。良好。
△：ＵＬ９４規格ＶＴＭ−０グレード試験で、試験片１０本中１本 燃焼。実用上問題ない。
×：ＵＬ９４規格ＶＴＭ−０グレード試験で、試験片１０本中２本以上燃焼。実用不可。
<Flame retardance>
(2) Flame Retardancy Test An electromagnetic wave shielding film from which the peelable sheet 2 has been peeled off is prepared, and a polyimide film having a thickness of 12.5 μm (“Kapton 50H” manufactured by Toray DuPont) is used on the exposed conductive adhesive layer. Was pressure-bonded under the conditions of 150 ° C., 1 MPa, 30 min to obtain a sample for flame resistance test of “electromagnetic wave shielding film / Kapton 50H / electromagnetic wave shielding film”. Flame retardancy was evaluated based on whether UL94 standard V-0 and VTM-0 grades could be achieved.
A: UL94 standard V-0 grade can be achieved. Very good.
○: In the UL94 standard VTM-0 grade test, all 10 specimens did not burn. Good.
Δ: 1 out of 10 test pieces burned in UL94 standard VTM-0 grade test. There is no problem in practical use.
X: In the UL94 standard VTM-0 grade test, 2 or more of 10 test pieces burned. Not practical.
１ ポリイミドフィルム
２ カソード電極用櫛形信号配線
２’ カソード電極接続点
３ アノード電極用櫛形信号配線
３’ アノード電極接続点
４ カバーコート層
５ 電磁波シールドフィルム
５ａ 保護層
５ｂ 導電層
DESCRIPTION OF SYMBOLS 1 Polyimide film 2 Comb signal wiring 2 'for cathode electrodes Cathode electrode connection point 3 Comb signal wiring 3' for anode electrodes Anode electrode connection point 4 Cover coat layer 5 Electromagnetic wave shielding film 5a Protective layer 5b Conductive layer
Claims (7)
前記金属層は、銅箔であり、
前記導電層は、熱硬化性樹脂、硬化剤および銀コート銅を含有し、
前記熱硬化性樹脂は、２種類以上含有し、
前記保護層は、リン系難燃剤を含有し、
前記リン系難燃剤は、表面に無機酸化物が付着されており、
前記電磁波シールドフィルム０．１６質量部を、水１００質量部中、８５℃、７２時間の条件で抽出された抽出液中に含まれるリン元素の濃度が、３００ｍｇ／Ｌ以下であり、
前記抽出液中に含まれる銅元素の濃度が、４００ｍｇ／Ｌ以下である
電磁波シールドフィルム。 An electromagnetic wave shielding film comprising a conductive layer , a metal layer, and a protective layer, (paragraph 0027)
The metal layer is a copper foil ,
The conductive layer contains a thermosetting resin, a curing agent and silver-coated copper,
The thermosetting resin contains two or more types,
The protective layer contains a phosphorus-based flame retardant,
The phosphorus-based flame retardant has an inorganic oxide attached to the surface,
Wherein the electromagnetic wave shielding film 0.16 parts by weight, in 100 parts by mass of water, 85 ° C., the concentration of phosphorus element contained in the extract has been extracted under conditions of 72 hours, 300 mg / L Ri der below,
The electromagnetic wave shielding film, wherein the concentration of copper element contained in the extract is 400 mg / L or less .
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| JP2017092415A (en) * | 2015-11-17 | 2017-05-25 | 信越ポリマー株式会社 | Electromagnetic wave shield film and electromagnetic wave shield film-attached printed wiring board |
| JP2018060987A (en) * | 2016-01-21 | 2018-04-12 | 東洋インキＳｃホールディングス株式会社 | Electromagnetic wave shielding sheet and printed wiring board |
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2018
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|---|---|---|---|---|
| JP2002309257A (en) * | 2001-04-12 | 2002-10-23 | Asahi Kasei Corp | Surface-crosslinked melamine polyphosphate flame retardant |
| WO2007119513A1 (en) * | 2006-03-29 | 2007-10-25 | Tatsuta System Electronics Co., Ltd. | Shield film and shield printed wiring board |
| JP2008257045A (en) * | 2007-04-06 | 2008-10-23 | Taiyo Ink Mfg Ltd | Black solder resist composition and cured product thereof |
| JP2009044069A (en) * | 2007-08-10 | 2009-02-26 | Nec Tokin Corp | Electromagnetic interference suppressor |
| JP2010283175A (en) * | 2009-06-05 | 2010-12-16 | Toyo Ink Mfg Co Ltd | Flame-resistant electromagnetic wave shielding adhesive film and method for manufacturing the same |
| JP2017092415A (en) * | 2015-11-17 | 2017-05-25 | 信越ポリマー株式会社 | Electromagnetic wave shield film and electromagnetic wave shield film-attached printed wiring board |
| JP2018060987A (en) * | 2016-01-21 | 2018-04-12 | 東洋インキＳｃホールディングス株式会社 | Electromagnetic wave shielding sheet and printed wiring board |
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