JP6920796B2 - Conductive adhesive sheet for FPC and FPC - Google Patents

Conductive adhesive sheet for FPC and FPC Download PDF

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JP6920796B2
JP6920796B2 JP2016154562A JP2016154562A JP6920796B2 JP 6920796 B2 JP6920796 B2 JP 6920796B2 JP 2016154562 A JP2016154562 A JP 2016154562A JP 2016154562 A JP2016154562 A JP 2016154562A JP 6920796 B2 JP6920796 B2 JP 6920796B2
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conductive adhesive
fpc
phosphorus
adhesive sheet
silver
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JP2018022827A (en
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喬規 櫻木
喬規 櫻木
野村　直宏
直宏 野村
さなえ 竹山
さなえ 竹山
昌由 平野
昌由 平野
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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Priority to JP2016154562A priority Critical patent/JP6920796B2/en
Priority to CN201710617957.4A priority patent/CN107690222B/en
Priority to CN202111214169.3A priority patent/CN113939077A/en
Priority to KR1020170094552A priority patent/KR101970484B1/en
Priority to TW106125863A priority patent/TWI732917B/en
Priority to TW110123669A priority patent/TWI751959B/en
Publication of JP2018022827A publication Critical patent/JP2018022827A/en
Priority to KR1020190043437A priority patent/KR102088165B1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
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    • C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/02—Homopolymers or copolymers of monomers containing phosphorus
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    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
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    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Description

本発明は、ＦＰＣ用導電性接着シート、及びそれを用いたＦＰＣに関する。 The present invention relates to a conductive adhesive sheet for FPC and an FPC using the same.

携帯電話、タブレット端末などの携帯用の電子機器においては、筐体の外形寸法を小さく抑えて持ち運び易くするために、プリント基板の上に電子部品を集積させている。さらに、筐体の外形寸法を小さくするため、プリント基板を複数に分割し、その分割されたプリント基板間を、可撓性を有するＦＰＣを使用して接続配線することにより、プリント基板を折畳む、あるいは、スライドさせることが行われている。
また、近年では、電子機器の外部から受信する電磁波のノイズ、あるいは電子機器の内部に配設された電子部品の相互間で受信する電磁波のノイズの影響を受けて、電子機器が誤動作するのを防止するため、重要な電子部品やＦＰＣを電磁波シールド材で被覆することが行われている。
この電磁波シールド材とＦＰＣの導電回路との接続には導電性接着シートが用いられる。また、金属製の補強板に対して電磁波シールド性を付与するため、金属補強板とＦＰＣの導体回路との接続に、導電性接着シートが用いられる。 In portable electronic devices such as mobile phones and tablet terminals, electronic components are integrated on a printed circuit board in order to keep the external dimensions of the housing small and easy to carry. Further, in order to reduce the external dimensions of the housing, the printed circuit board is divided into a plurality of parts, and the divided printed circuit boards are connected and wired using a flexible FPC to fold the printed circuit board. Or, it is being slid.
Further, in recent years, the electronic device malfunctions due to the influence of the electromagnetic wave noise received from the outside of the electronic device or the electromagnetic wave noise received between the electronic components arranged inside the electronic device. In order to prevent this, important electronic components and FPCs are covered with an electromagnetic wave shielding material.
A conductive adhesive sheet is used to connect the electromagnetic wave shielding material to the conductive circuit of the FPC. Further, in order to impart electromagnetic wave shielding property to the metal reinforcing plate, a conductive adhesive sheet is used for connecting the metal reinforcing plate and the conductor circuit of the FPC.

上記のような導電性接着シートに関連する技術として、例えば特許文献１には、ポリウレタン樹脂と、エポキシ樹脂と、導電性フィラーと、添加剤と、を含有する硬化性導電性接着剤組成物が記載されている。特許文献１に記載の硬化性導電性接着剤組成物は、上記構成としたことにより、接着時に適度な流動性を付与でき、すぐれた接着性を確保できることが記載されている。 As a technique related to the above-mentioned conductive adhesive sheet, for example, Patent Document 1 describes a curable conductive adhesive composition containing a polyurethane resin, an epoxy resin, a conductive filler, and an additive. Have been described. It is described that the curable conductive adhesive composition described in Patent Document 1 can impart appropriate fluidity at the time of adhesion and can secure excellent adhesiveness by adopting the above configuration.

国際公開第２０１４／０１０５２４号International Publication No. 2014/010524

近年、ＦＰＣに用いられる導電性接着シートには良好な導電性に加え、高い難燃性が求められる。導電性接着シートに難燃性を付与するためには、導電性接着シートに用いられる導電性接着剤組成物に難燃剤を添加することが想起できる。
ところが、本発明者らが導電性接着剤組成物に難燃剤を添加したところ、導電性と難燃性の両立ができなくなることが判明した。
本発明は上記事情に鑑みてなされたものであって、導電性と難燃性をともに満たすことができ、さらに従来よりも高い難燃性を満たすことができるＦＰＣ用導電性接着シート、及び該ＦＰＣ用導電性接着シートを用いたＦＰＣを提供することを課題とする。 In recent years, the conductive adhesive sheet used for FPC is required to have high flame retardancy in addition to good conductivity. In order to impart flame retardancy to the conductive adhesive sheet, it can be recalled that a flame retardant is added to the conductive adhesive composition used for the conductive adhesive sheet.
However, when the present inventors added a flame retardant to the conductive adhesive composition, it was found that both conductivity and flame retardancy could not be achieved at the same time.
The present invention has been made in view of the above circumstances, and is a conductive adhesive sheet for FPC capable of satisfying both conductivity and flame retardancy, and further satisfying higher flame retardancy than before, and a conductive adhesive sheet for FPC. An object of the present invention is to provide an FPC using a conductive adhesive sheet for FPC.

本発明者らは上記目的を達成すべく検討を重ねた結果、樹脂材料と導電性材料とを特定の割合で含有する導電性接着剤組成物を用いることにより、導電性と難燃性をともに満たすＦＰＣ用導電性接着シートを得ることができることを見出した。 As a result of repeated studies to achieve the above object, the present inventors have achieved both conductivity and flame retardancy by using a conductive adhesive composition containing a resin material and a conductive material in a specific ratio. It has been found that a conductive adhesive sheet for FPC that satisfies the requirements can be obtained.

すなわち、本発明は以下の構成を採用した。
［１］支持体フィルムと、前記支持体フィルムの一方の面に積層された導電性接着剤層と、を有し、前記導電性接着剤層は、リン含有樹脂と、銀被覆銅粒子と、を含有する導電性接着剤組成物を形成材料とし、前記導電性接着剤組成物は、前記リン含有樹脂１００質量部に対し、前記銀被覆銅粒子を１００質量部以上２００質量部以下含有し、前記リン含有樹脂は、前記リン含有樹脂１００質量部に対し、リンを０．２質量部以上含み、前記銀被覆銅粒子は、銀被覆率が８０％以上であることを特徴とする、ＦＰＣ用導電性接着シート。
［２］下記条件で行う難燃性評価において、燃焼時間が５秒未満であることを特徴とする［１］に記載のＦＰＣ用導電性接着シート。
＜条件＞
≪測定サンプルの準備≫
ＦＰＣ用導電性接着シートを５０ｍｍ×２００ｍｍのサイズに１０枚を切り出し、２３℃湿度５０％の条件に４８時間置き、測定サンプルとする。
≪評価条件≫
前記方法により準備した測定サンプルを直径１２．７ｍｍの棒に巻きつける。その後、円筒状に巻きつけたサンプルのうち、上端から７５ｍｍ以内の部分内を感圧テープで留め、棒を引き抜く。その後、測定サンプルの上端は測定中に煙突効果がないように閉じる。その後、測定サンプルを垂直に配置し、その３００ｍｍ下方に脱脂綿を置く。その後、測定サンプルの下端から１０ｍｍのところにバーナーの筒が位置するように、バーナーを配置する。その後、サンプルの下端の中央に青色炎を３秒間接炎し、離炎後の測定サンプルの燃焼時間を測定する。１０枚の測定サンプルの燃焼時間を同様に行い、燃焼時間の平均値を算出する。
［３］前記銀被覆銅粒子の銀被覆率が、９５％以上である、［１］又は［２］に記載のＦＰＣ用導電性接着シート。
［４］前記銀被覆銅粒子が樹枝状である、［１］〜［３］のいずれか１項に記載のＦＰＣ用導電性接着シート。
［５］前記銀被覆銅粒子の平均粒径が、１５μｍ以上２０μｍ以下である、［１］〜［４］のいずれか１項に記載のＦＰＣ用導電性接着シート。
［６］前記リン含有樹脂は、リン含有ポリウレタン樹脂である、［１］〜［５］のいずれか１項に記載のＦＰＣ用導電性接着シート。
［７］前記リン含有ポリウレタン樹脂のリンの濃度が、前記リン含有ポリウレタン樹脂の全量中の１重量％以上である、［６］に記載のＦＰＣ用導電性接着シート。
［８］前記導電性接着剤樹脂組成物がシリカ粒子を含有する、［１］〜［７］のいずれか１項に記載のＦＰＣ用導電性接着シート。
［９］前記シリカ粒子の一次粒子径が、１０ｎｍ以上２０ｎｍ以下である、［１］〜［８］のいずれか１項に記載のＦＰＣ用導電性接着シート。
［１０］前記リン含有樹脂１００質量部に対し、前記シリカ粒子を１質量部以上１５質量部以下含有する、［１］〜［９］のいずれか１項に記載のＦＰＣ用導電性接着シート。
［１１］前記導電性接着剤樹脂組成物がシランカップリング剤を含有する、［１］〜［１０］のいずれか１項に記載のＦＰＣ用導電性接着シート。
［１２］［１］〜［１１］のいずれか１項に記載のＦＰＣ用導電性接着シートが、ＦＰＣの表面に金属補強板を貼り合わせるために使用されているＦＰＣ。 That is, the present invention has adopted the following configuration.
[1] The support film has a conductive adhesive layer laminated on one surface of the support film, and the conductive adhesive layer includes a phosphorus-containing resin, silver-coated copper particles, and the like. The conductive adhesive composition containing the above is used as a forming material, and the conductive adhesive composition contains 100 parts by mass or more and 200 parts by mass or less of the silver-coated copper particles with respect to 100 parts by mass of the phosphorus-containing resin. The phosphorus-containing resin contains 0.2 parts by mass or more of phosphorus with respect to 100 parts by mass of the phosphorus-containing resin, and the silver-coated copper particles have a silver coating ratio of 80% or more for FPC. Conductive adhesive sheet.
[2] The conductive adhesive sheet for FPC according to [1], wherein the combustion time is less than 5 seconds in the flame retardancy evaluation performed under the following conditions.
<Conditions>
≪Preparation of measurement sample≫
Ten conductive adhesive sheets for FPC are cut out to a size of 50 mm × 200 mm and placed at 23 ° C. and 50% humidity for 48 hours to prepare a measurement sample.
≪Evaluation conditions≫
The measurement sample prepared by the above method is wound around a rod having a diameter of 12.7 mm. Then, of the sample wound in a cylindrical shape, the inside of the portion within 75 mm from the upper end is fastened with pressure-sensitive tape, and the rod is pulled out. After that, the upper end of the measurement sample is closed so that there is no chimney effect during the measurement. Then, the measurement sample is placed vertically, and cotton wool is placed 300 mm below the measurement sample. After that, the burner is arranged so that the cylinder of the burner is located 10 mm from the lower end of the measurement sample. Then, a blue flame is indirectly flamed in the center of the lower end of the sample for 3 seconds, and the burning time of the measurement sample after deflaming is measured. The burning time of 10 measurement samples is performed in the same manner, and the average value of the burning time is calculated.
[3] The conductive adhesive sheet for FPC according to [1] or [2], wherein the silver coating ratio of the silver-coated copper particles is 95% or more.
[4] The conductive adhesive sheet for FPC according to any one of [1] to [3], wherein the silver-coated copper particles are dendritic.
[5] The conductive adhesive sheet for FPC according to any one of [1] to [4], wherein the silver-coated copper particles have an average particle size of 15 μm or more and 20 μm or less.
[6] The conductive adhesive sheet for FPC according to any one of [1] to [5], wherein the phosphorus-containing resin is a phosphorus-containing polyurethane resin.
[7] The conductive adhesive sheet for FPC according to [6], wherein the phosphorus concentration of the phosphorus-containing polyurethane resin is 1% by weight or more based on the total amount of the phosphorus-containing polyurethane resin.
[8] The conductive adhesive sheet for FPC according to any one of [1] to [7], wherein the conductive adhesive resin composition contains silica particles.
[9] The conductive adhesive sheet for FPC according to any one of [1] to [8], wherein the primary particle size of the silica particles is 10 nm or more and 20 nm or less.
[10] The conductive adhesive sheet for FPC according to any one of [1] to [9], which contains 1 part by mass or more and 15 parts by mass or less of the silica particles with respect to 100 parts by mass of the phosphorus-containing resin.
[11] The conductive adhesive sheet for FPC according to any one of [1] to [10], wherein the conductive adhesive resin composition contains a silane coupling agent.
[12] The FPC in which the conductive adhesive sheet for FPC according to any one of [1] to [11] is used to attach a metal reinforcing plate to the surface of the FPC.

本発明によれば、導電性と難燃性をともに満たすことができるＦＰＣ用導電性接着シート、及び該ＦＰＣ用導電性接着シートを用いたＦＰＣを提供することができる。 According to the present invention, it is possible to provide a conductive adhesive sheet for FPC capable of satisfying both conductivity and flame retardancy, and an FPC using the conductive adhesive sheet for FPC.

本発明に係わるＦＰＣ用導電性接着シートの一例を示す、概略断面図である。It is schematic cross-sectional view which shows an example of the conductive adhesive sheet for FPC which concerns on this invention. 本発明に係わるＦＰＣ用導電性接着シートを介して、補強板がＦＰＣに貼り付けられた一例を示す、概略断面図である。It is schematic cross-sectional view which shows an example which the reinforcing plate was attached to FPC via the conductive adhesive sheet for FPC which concerns on this invention. 本発明のＦＰＣ用導電性接着シートが、導電性接着剤層を介して金属補強板に積層された、金属補強板付き導電性接着シートを示す、概略断面図である。FIG. 5 is a schematic cross-sectional view showing a conductive adhesive sheet with a metal reinforcing plate, in which the conductive adhesive sheet for FPC of the present invention is laminated on a metal reinforcing plate via a conductive adhesive layer. （ａ）は、導電性の評価方法において使用される、模擬的なフレキシブル基板の概略平面図であり、（ｂ）は、図４（ａ）のＡ−Ａ矢視断面図である。(A) is a schematic plan view of a simulated flexible substrate used in the method for evaluating conductivity, and (b) is a cross-sectional view taken along the line AA of FIG. 4 (a). （ａ）は、導電性の評価方法において使用される、導電性の評価用試験片の概略平面図であり、（ｂ）は、図５（ａ）のＢ−Ｂ矢視断面図である。(A) is a schematic plan view of a test piece for evaluating conductivity used in the method for evaluating conductivity, and (b) is a cross-sectional view taken along the line BB of FIG. 5 (a). 難燃性評価に用いる測定サンプルを示す模式図である。It is a schematic diagram which shows the measurement sample used for flame retardancy evaluation. 難燃性評価を行うための試験台の模式図である。It is a schematic diagram of the test table for performing flame retardancy evaluation.

以下、好適な実施の形態に基づき、本発明を説明する。 Hereinafter, the present invention will be described based on preferred embodiments.

＜ＦＰＣ用導電性接着シート＞
本発明の、ＦＰＣに使用されるＦＰＣ用導電性接着シートは、支持体フィルムと、前記支持体フィルムの一方の面に積層された導電性接着剤層と、を有し、前記導電性接着剤層は、リン含有樹脂と、銀被覆銅粒子と、を含有する導電性接着剤組成物（以下、「接着剤組成物」と記載する）を形成材料とし、前記導電性接着剤組成物は、前記リン含有樹脂１００質量部に対し、前記銀被覆銅粒子を１００質量部以上２００質量部以下含有し、前記リン含有樹脂は、前記リン含有樹脂１００質量部に対し、リンを０．２質量部以上含み、前記銀被覆銅粒子は、銀被覆率が８０％以上であることを特徴とする。
本発明のＦＰＣ用導電性接着シートは、リン含有樹脂を含む接着剤組成物を用いて形成されるため、高い難燃性を有する。また、銀被覆率が８０％以上と、高い被覆率の銀被覆銅粒子を用いているため、高い導電性を有する。さらに、リン含有樹脂と、銀被覆銅粒子とを特定の割合で含有するため、難燃性と導電性とをともに満たすＦＰＣ用導電性接着シートを提供することができる。 <Conductive adhesive sheet for FPC>
The conductive adhesive sheet for FPC used in FPC of the present invention has a support film and a conductive adhesive layer laminated on one surface of the support film, and the conductive adhesive. The layer uses a conductive adhesive composition containing phosphorus-containing resin and silver-coated copper particles (hereinafter, referred to as "adhesive composition") as a forming material, and the conductive adhesive composition is The silver-coated copper particles are contained in an amount of 100 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the phosphorus-containing resin, and the phosphorus-containing resin contains 0.2 parts by mass of phosphorus with respect to 100 parts by mass of the phosphorus-containing resin. Including the above, the silver-coated copper particles are characterized by having a silver coating ratio of 80% or more.
Since the conductive adhesive sheet for FPC of the present invention is formed by using an adhesive composition containing a phosphorus-containing resin, it has high flame retardancy. Further, since silver-coated copper particles having a high coating ratio of 80% or more are used, they have high conductivity. Further, since the phosphorus-containing resin and the silver-coated copper particles are contained in a specific ratio, it is possible to provide a conductive adhesive sheet for FPC that satisfies both flame retardancy and conductivity.

図１は、本発明に係わるＦＰＣ用導電性接着シートの一例を示す、概略断面図である。
図２は、本発明に係わるＦＰＣ用導電性接着シートを介して、補強板がＦＰＣに貼り付けられた一例を示す、概略断面図である。
図３は、本発明のＦＰＣ用導電性接着シートが、導電性接着剤層を介して金属補強板に積層された、金属補強板付き導電性接着シートを示す、概略断面図である。 FIG. 1 is a schematic cross-sectional view showing an example of a conductive adhesive sheet for FPC according to the present invention.
FIG. 2 is a schematic cross-sectional view showing an example in which a reinforcing plate is attached to an FPC via a conductive adhesive sheet for FPC according to the present invention.
FIG. 3 is a schematic cross-sectional view showing a conductive adhesive sheet with a metal reinforcing plate in which the conductive adhesive sheet for FPC of the present invention is laminated on a metal reinforcing plate via a conductive adhesive layer.

図１に示した、本発明のＦＰＣ用導電性接着シート５は、片面が剥離処理された支持体フィルム１の剥離処理面に、導電性接着剤層４を積層してなる。導電性接着剤層４は、リン含有樹脂２と、銀被覆銅粒子３とを含む。また、図３に示したように、ＦＰＣ用導電性接着シート５は、導電性接着剤層４を介して金属補強板６に積層された後、所定の寸法に切断され、金属補強板付き導電性接着シート３０として、支持体フィルム１を取り除いた状態で積み重ねて保管される。この金属補強板付き導電性接着シート３０は、金属補強板６と導電性接着剤層４との積層体であり、図２の態様にて、ＦＰＣ用電磁波シールド性補強板として使用することができる。図２において、ＦＰＣ２０は、基板フィルム８上に実装部品７とアース回路９を有し、絶縁フィルム１１上に絶縁性接着剤層１０を設けたカバーレイ１２により、アース回路９が保護された構成である。カバーレイ１２にはスルーホール１４が設けられ、金属補強板付き導電性接着シート３０の導電性接着剤層４が、スルーホール１４を通じてアース回路９と接触することにより、金属補強板６が電磁波シールド材として機能する。 The conductive adhesive sheet 5 for FPC of the present invention shown in FIG. 1 is formed by laminating the conductive adhesive layer 4 on the peeled surface of the support film 1 whose one side has been peeled. The conductive adhesive layer 4 contains a phosphorus-containing resin 2 and silver-coated copper particles 3. Further, as shown in FIG. 3, the conductive adhesive sheet 5 for FPC is laminated on the metal reinforcing plate 6 via the conductive adhesive layer 4, then cut to a predetermined size, and is conductive with the metal reinforcing plate. As the sex-adhesive sheet 30, the support film 1 is removed and stored in a stacked state. The conductive adhesive sheet 30 with a metal reinforcing plate is a laminate of the metal reinforcing plate 6 and the conductive adhesive layer 4, and can be used as an electromagnetic wave shielding reinforcing plate for FPC in the embodiment of FIG. .. In FIG. 2, the FPC 20 has a mounting component 7 and a ground circuit 9 on a substrate film 8, and the ground circuit 9 is protected by a coverlay 12 provided with an insulating adhesive layer 10 on the insulating film 11. Is. A through hole 14 is provided in the coverlay 12, and the conductive adhesive layer 4 of the conductive adhesive sheet 30 with a metal reinforcing plate comes into contact with the ground circuit 9 through the through hole 14, whereby the metal reinforcing plate 6 shields the electromagnetic wave. Functions as a material.

本発明のＦＰＣ用導電性接着シートは、高い難燃性を有する。
具体的には、下記条件で行う難燃性評価において、燃焼時間が５秒未満であることが好ましい。
＜条件＞
≪測定サンプルの準備≫
ＦＰＣ用導電性接着シートを５０ｍｍ×２００ｍｍのサイズに１０枚を切り出し、２３℃湿度５０％の条件に４８時間置き、測定サンプルとした。
≪評価条件≫
前記方法により準備した測定サンプルを直径１２．７ｍｍの棒に巻きつける。
その後、円筒状に巻きつけたサンプルのうち、上端から７５ｍｍ以内の部分内を感圧テープで留め、棒を引き抜く。
その後、測定サンプルの上端は測定中に煙突効果がないように閉じる。
その後、測定サンプルを垂直に配置し、その３００ｍｍ下方に脱脂綿を置く。
その後、測定サンプルの下端から１０ｍｍのところにバーナーの筒が位置するように、バーナーを配置する。
その後、サンプルの下端の中央に青色炎を３秒間接炎し、離炎後の測定サンプルの燃焼時間を測定する。
１０枚の測定サンプルの燃焼時間を同様に行い、燃焼時間の平均値を算出する。 The conductive adhesive sheet for FPC of the present invention has high flame retardancy.
Specifically, in the flame retardancy evaluation performed under the following conditions, the combustion time is preferably less than 5 seconds.
<Conditions>
≪Preparation of measurement sample≫
Ten conductive adhesive sheets for FPC were cut out to a size of 50 mm × 200 mm and placed under the condition of 23 ° C. and 50% humidity for 48 hours to prepare a measurement sample.
≪Evaluation conditions≫
The measurement sample prepared by the above method is wound around a rod having a diameter of 12.7 mm.
Then, of the sample wound in a cylindrical shape, the inside of the portion within 75 mm from the upper end is fastened with pressure-sensitive tape, and the rod is pulled out.
After that, the upper end of the measurement sample is closed so that there is no chimney effect during the measurement.
Then, the measurement sample is placed vertically, and cotton wool is placed 300 mm below the measurement sample.
After that, the burner is arranged so that the cylinder of the burner is located 10 mm from the lower end of the measurement sample.
Then, a blue flame is indirectly flamed in the center of the lower end of the sample for 3 seconds, and the burning time of the measurement sample after deflaming is measured.
The burning time of 10 measurement samples is performed in the same manner, and the average value of the burning time is calculated.

難燃性評価の評価方法について、図面を参照して説明する。
図６に、難燃性評価に用いる測定サンプルの模式図を示す。ＦＰＣ用導電性接着シートを５０ｍｍ×２００ｍｍのサイズに切りだし、測定サンプル６１を１０枚準備する。測定サンプル６１は、縦１２５ｍｍの位置にマーク６２を記載しておくことが好ましい。このようにして準備した測定サンプルを、２３℃湿度５０％の条件に４８時間置き、測定サンプル６１とする。
図６に示すように、符号６４に示す直径が１２．７ｍｍの棒６３に測定サンプルをしっかりと円筒状に巻きつける。
このようにして得た円筒状の測定サンプル６１の上端から７５ｍｍの部分内を感圧テープ７４でしっかりと留め、その後、棒６３を引き抜く。測定サンプル６１の上端は測定中に煙突効果がないように閉じる。 The evaluation method of flame retardancy evaluation will be described with reference to the drawings.
FIG. 6 shows a schematic diagram of a measurement sample used for flame retardancy evaluation. A conductive adhesive sheet for FPC is cut into a size of 50 mm × 200 mm, and 10 measurement samples 61 are prepared. It is preferable that the mark 62 is marked on the measurement sample 61 at a position 125 mm in length. The measurement sample prepared in this manner is placed under the condition of 23 ° C. and 50% humidity for 48 hours to be used as the measurement sample 61.
As shown in FIG. 6, the measurement sample is firmly wound in a cylindrical shape around the rod 63 having a diameter of 12.7 mm indicated by reference numeral 64.
The inside of the portion 75 mm from the upper end of the cylindrical measurement sample 61 thus obtained is firmly fastened with the pressure-sensitive tape 74, and then the rod 63 is pulled out. The upper end of the measurement sample 61 is closed so that there is no chimney effect during the measurement.

図７に難燃性評価を行うための試験台７１の模式図を示す。アーム７３の先端に位置するクランプ７２に、円筒状の測定サンプルを垂直に設置する。
測定サンプル６１の３００ｍｍ下方に脱脂綿７８を置き、測定サンプル６１の下端から１０ｍｍの位置（図７の符号７６に示す位置）にバーナーの筒が位置するように、バーナー７５を配置し、サンプルの下端の中央に青色炎を３秒間接炎する。
その後、離炎し、離炎後の測定サンプルの燃焼時間を測定した。１０枚の測定サンプルの燃焼時間を同様に行い、燃焼時間の平均値を算出する。 FIG. 7 shows a schematic view of the test table 71 for performing flame retardancy evaluation. A cylindrical measurement sample is vertically placed on the clamp 72 located at the tip of the arm 73.
The absorbent cotton 78 is placed 300 mm below the measurement sample 61, and the burner 75 is placed so that the burner cylinder is located 10 mm from the lower end of the measurement sample 61 (the position indicated by reference numeral 76 in FIG. 7), and the lower end of the sample is placed. Indirect flame of blue flame for 3 seconds in the center of.
Then, the flame was released, and the burning time of the measurement sample after the flame was released was measured. The burning time of 10 measurement samples is performed in the same manner, and the average value of the burning time is calculated.

本発明においては、上記方法により測定した燃焼時間が５秒間以内であることが好ましい。
より高い難燃性を達成する観点から、前記消炎までの時間が４秒間以内であることがより好ましく、３秒間以内であることが特に好ましい。
この評価方法により算出される難燃性の結果は、ＵＬ９４規格に準ずる難燃性の判断基準であるＶＴＭ−０よりも高い難燃性であることを示す。 In the present invention, the burning time measured by the above method is preferably within 5 seconds.
From the viewpoint of achieving higher flame retardancy, the time until extinguishing the flame is more preferably within 4 seconds, and particularly preferably within 3 seconds.
The result of flame retardancy calculated by this evaluation method indicates that the flame retardancy is higher than that of VTM-0, which is a criterion for determining flame retardancy according to the UL94 standard.

以下、本発明のＦＰＣ用導電性接着シートに用いる各材料について説明する。 Hereinafter, each material used for the conductive adhesive sheet for FPC of the present invention will be described.

（支持体フィルム）
本発明に使用する支持体フィルム１としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリプロピレンやポリエチレン等のポリオレフィンフィルムが挙げられる。
支持体フィルム１が、例えば、ポリエチレンテレフタレートなどであって、支持体フィルム自体に、ある程度の剥離性を有している場合には、支持体フィルム１の上に、剥離処理を施さなくて、直接に、導電性接着剤層４を積層してもよい。また、支持体フィルム１から、導電性接着剤層４を、より剥離し易くするための剥離処理を、支持体フィルム１の表面に施してもよい。
また、上記の支持体フィルム１として用いる樹脂フィルムが、剥離性を有していない場合には、アミノアルキッド樹脂やシリコーン樹脂等の剥離剤を塗布した後、加熱乾燥することにより、剥離処理が施される。本発明のＦＰＣ用導電性接着シート５は、ＦＰＣに貼り合わされるので、この剥離剤には、シリコーン樹脂を使用しないことが望ましい。なぜなら、シリコーン樹脂を剥離剤として用いると、支持体フィルム１の表面に接触した導電性接着剤層４の表面に、シリコーン樹脂の一部が移行し、さらに導電性接着剤層４の内部を通じて導電性接着剤層４のもう一方の面へと移行する恐れがあるためである。この導電性接着剤層４の表面に移行したシリコーン樹脂が、金属補強板６に対する導電性接着剤層４の接着力を弱める恐れがある。
本発明に使用される支持体フィルム１の厚みは、ＦＰＣに貼着して使用する際の、導電性接着剤層４の厚みからは除外されるので、特に限定されないが、通常１２μｍ〜１５０μｍ程度である。 (Support film)
Examples of the support film 1 used in the present invention include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
When the support film 1 is, for example, polyethylene terephthalate and the support film itself has a certain degree of peelability, the support film 1 is directly peeled off without being subjected to a peeling treatment. The conductive adhesive layer 4 may be laminated on the surface. Further, the surface of the support film 1 may be subjected to a peeling treatment for making it easier to peel the conductive adhesive layer 4 from the support film 1.
When the resin film used as the support film 1 does not have peelability, a peeling treatment is performed by applying a peeling agent such as an amino alkyd resin or a silicone resin and then heating and drying. Will be done. Since the conductive adhesive sheet 5 for FPC of the present invention is bonded to FPC, it is desirable not to use a silicone resin as this release agent. This is because when the silicone resin is used as the release agent, a part of the silicone resin is transferred to the surface of the conductive adhesive layer 4 in contact with the surface of the support film 1, and further, it is conductive through the inside of the conductive adhesive layer 4. This is because there is a risk of migrating to the other surface of the sex adhesive layer 4. The silicone resin transferred to the surface of the conductive adhesive layer 4 may weaken the adhesive force of the conductive adhesive layer 4 to the metal reinforcing plate 6.
The thickness of the support film 1 used in the present invention is not particularly limited because it is excluded from the thickness of the conductive adhesive layer 4 when it is attached to the FPC and used, but it is usually about 12 μm to 150 μm. Is.

（剥離フィルム）
図１に示した本発明に係わるＦＰＣ用導電性接着シート５は、支持体フィルム１の一方の面に、導電性接着剤層４が積層されている。また、本発明に係わるＦＰＣ用導電性接着シート５は、支持体フィルム１の一方の面に、導電性接着剤層４が積層され、基材の片面に剥離剤層を積層した剥離フィルムが、該剥離剤層を介して導電性接着剤層４に貼り合わされている構成であってもよい。
剥離フィルムの基材としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリプロピレンやポリエチレン等のポリオレフィンフィルムが挙げられる。これらの樹脂フィルムに、アミノアルキッド樹脂やシリコーン樹脂等の剥離剤を塗布した後、加熱乾燥することにより、剥離処理が施される。本発明のＦＰＣ用導電性接着シートは、ＦＰＣに貼り合わされるので、この剥離剤には、シリコーン樹脂を使用しないことが望ましい。なぜならシリコーン樹脂を剥離剤として用いると、剥離フィルムの表面に接触した導電性接着剤層の表面に、シリコーン樹脂の一部が移行し、さらにＦＰＣ用導電性接着シートの内部を通じて導電性接着剤層から支持体フィルム１へと移行する恐れがあるためである。この導電性接着剤層の表面に移行したシリコーン樹脂が導電性接着剤層の接着力を弱める恐れがある。本発明に使用される剥離フィルムの厚みは、特に限定されないが、通常１２μｍ〜１５０μｍ程度である。 (Release film)
In the conductive adhesive sheet 5 for FPC according to the present invention shown in FIG. 1, a conductive adhesive layer 4 is laminated on one surface of a support film 1. Further, the conductive adhesive sheet 5 for FPC according to the present invention is a release film in which a conductive adhesive layer 4 is laminated on one surface of a support film 1 and a release agent layer is laminated on one surface of a base material. The structure may be such that the conductive adhesive layer 4 is bonded to the conductive adhesive layer 4 via the release agent layer.
Examples of the base material of the release film include polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. A release agent such as an aminoalkyd resin or a silicone resin is applied to these resin films and then heat-dried to perform a release treatment. Since the conductive adhesive sheet for FPC of the present invention is bonded to FPC, it is desirable not to use a silicone resin as this release agent. This is because when the silicone resin is used as the release agent, a part of the silicone resin is transferred to the surface of the conductive adhesive layer in contact with the surface of the release film, and further, the conductive adhesive layer is passed through the inside of the conductive adhesive sheet for FPC. This is because there is a risk of shifting from the support film 1 to the support film 1. The silicone resin transferred to the surface of the conductive adhesive layer may weaken the adhesive force of the conductive adhesive layer. The thickness of the release film used in the present invention is not particularly limited, but is usually about 12 μm to 150 μm.

≪導電性接着剤組成物≫
本発明のＦＰＣ用導電性接着シートの導電性接着剤層を形成するために使用する、導電性接着剤組成物について説明する。接着剤組成物は、リン含有樹脂と、銀被覆銅粒子と、を特定の割合で含有する。 ≪Conductive adhesive composition≫
The conductive adhesive composition used for forming the conductive adhesive layer of the conductive adhesive sheet for FPC of the present invention will be described. The adhesive composition contains a phosphorus-containing resin and silver-coated copper particles in a specific ratio.

［リン含有樹脂］
本発明に用いるリン含有樹脂は、リンを分子中に含有するリン含有樹脂（以下、「導入型」と記載する）であってもよく、低分子量のリン含有化合物を樹脂に添加したリン含有樹脂（以下、「ブレンド型」と記載する）であってもよい。
導入型のリン含有樹脂とは、主鎖構造又は側鎖構造の中に、リン原子を導入した構造を有する樹脂を意味する。
例えば、リンを構造中に含む化合物から誘導される、リン含有ポリエステル樹脂、リン含有ポリウレタン樹脂、リン含有エポキシ樹脂等が挙げられる。これらの中では、リン含有ポリウレタン樹脂が好ましい。 [Phosphorus-containing resin]
The phosphorus-containing resin used in the present invention may be a phosphorus-containing resin containing phosphorus in the molecule (hereinafter, referred to as “introduction type”), and a phosphorus-containing resin obtained by adding a low molecular weight phosphorus-containing compound to the resin. (Hereinafter, referred to as "blend type") may be used.
The introduction-type phosphorus-containing resin means a resin having a structure in which a phosphorus atom is introduced into a main chain structure or a side chain structure.
For example, phosphorus-containing polyester resin, phosphorus-containing polyurethane resin, phosphorus-containing epoxy resin and the like derived from a compound containing phosphorus in the structure can be mentioned. Among these, a phosphorus-containing polyurethane resin is preferable.

導入型のリン含有樹脂は、より高い難燃性を得る観点から、リン含有樹脂１００質量部に対し、リンを０．２質量部以上含み、リン含有樹脂１００質量部中の１重量％以上であることが好ましく、１．５重量％以上であることがより好ましく、２．０重量％以上であることが特に好ましい。また、上限値としては１０重量％以下であることが好ましく、５％以下であることがさらに好ましい。リンの含有量が上記下限値未満であると、難燃性を充分に発揮できず、難燃性のＦＰＣ用導電性接着シートを得ることが困難となる。
本明細書において、「リン含有量」とは、樹脂中のリン元素自体の重量割合を意味する。 From the viewpoint of obtaining higher flame retardancy, the introduction type phosphorus-containing resin contains 0.2 parts by mass or more of phosphorus with respect to 100 parts by mass of the phosphorus-containing resin, and is 1% by weight or more in 100 parts by mass of the phosphorus-containing resin. It is preferably 1.5% by mass or more, and particularly preferably 2.0% by mass or more. The upper limit is preferably 10% by weight or less, and more preferably 5% or less. If the phosphorus content is less than the above lower limit, flame retardancy cannot be sufficiently exhibited, and it becomes difficult to obtain a flame retardant conductive adhesive sheet for FPC.
As used herein, the term "phosphorus content" means the weight ratio of the phosphorus element itself in the resin.

ブレンド型のリン含有樹脂としては、エポキシ樹脂、アクリル樹脂、ポリエステル樹脂、ポリイミド樹脂、ポリウレタン樹脂、等の樹脂に、リン系難燃剤を添加したものが挙げられ、これらの中ではポリウレタン樹脂のリン系難燃剤を添加したリン含有樹脂が好ましい。
本発明においては、より高い難燃性を付与できることから、リンを分子中に含有するリン含有樹脂が好ましく、この中でもリン含有ポリウレタン樹脂が特に好ましい。 Examples of the blend type phosphorus-containing resin include resins such as epoxy resin, acrylic resin, polyester resin, polyimide resin, and polyurethane resin to which a phosphorus-based flame retardant is added, and among these, phosphorus-based polyurethane resin is used. A phosphorus-containing resin to which a flame retardant is added is preferable.
In the present invention, a phosphorus-containing resin containing phosphorus in the molecule is preferable, and a phosphorus-containing polyurethane resin is particularly preferable, because higher flame retardancy can be imparted.

ブレンド型のリン含有樹脂は、より高い難燃性を得る観点から、リン含有樹脂１００質量部に対し、リン系難燃剤を０．２質量部以上含み、リン含有樹脂１００質量部中の１重量％以上であることが好ましく、１．５重量％以上であることがより好ましく、２．０重量％以上であることが特に好ましい。リン系難燃剤の含有量が上記下限値未満であると、難燃性を充分に発揮できず、難燃性のＦＰＣ用導電性接着シートを得ることが困難となる。 From the viewpoint of obtaining higher flame retardancy, the blend type phosphorus-containing resin contains 0.2 parts by mass or more of a phosphorus-based flame retardant with respect to 100 parts by mass of the phosphorus-containing resin, and 1 weight in 100 parts by mass of the phosphorus-containing resin. % Or more, more preferably 1.5% by mass or more, and particularly preferably 2.0% by mass or more. If the content of the phosphorus-based flame retardant is less than the above lower limit value, the flame retardant cannot be sufficiently exhibited, and it becomes difficult to obtain a flame-retardant conductive adhesive sheet for FPC.

［銀被覆銅粒子］
本発明に用いる銀被覆銅粒子は、銀被覆率が８０％以上であり、より高い導電性を得る観点から、９０％以上であることが好ましく、９５％以上であることがより好ましい。
ここで、用語「銀被覆銅粒子」とは、本発明では、コア−シェル構造を有する粒子であって、コアは銀を実質的には含有しない一方でシェルが銀からなる粒子を意味する。銀被覆銅粒子において、銀のシェルは、コアを少なくとも部分的には覆う被膜または層である。
本発明において使用される銀被覆銅粒子は、導電性粒子状材料であり、球状、平状、フレーク状、樹枝状のような様々な形状を有し得る。本発明においては、銀被覆銅粒子は、樹枝状であることが好ましい。 [Silver-coated copper particles]
The silver-coated copper particles used in the present invention have a silver coating ratio of 80% or more, and are preferably 90% or more, more preferably 95% or more, from the viewpoint of obtaining higher conductivity.
Here, the term "silver-coated copper particles" means particles having a core-shell structure in the present invention, in which the core does not substantially contain silver while the shell is made of silver. In silver-coated copper particles, the silver shell is a coating or layer that at least partially covers the core.
The silver-coated copper particles used in the present invention are conductive particulate materials and can have various shapes such as spherical, flat, flake-like, and dendritic-like. In the present invention, the silver-coated copper particles are preferably dendritic.

銀被覆銅粒子の銀被覆率を上記特定の範囲とする方法としては、上記特定の銀被覆率を達成する銀被覆銅粒子材料を購入してもよいし、銅粒子を銀で被覆する際の銀の析出時間を制御することにより、上記特定の銀被覆率を達成する銀被覆銅粒子を得てもよい。 As a method of setting the silver coverage of the silver-coated copper particles in the above-mentioned specific range, a silver-coated copper particle material that achieves the above-mentioned specific silver coverage may be purchased, or when the copper particles are coated with silver. By controlling the silver precipitation time, silver-coated copper particles that achieve the above-mentioned specific silver coverage may be obtained.

本発明において、前記銀被覆銅粒子の平均粒径は、１５μｍ以上２０μｍ以下であることが好ましい。
本発明において、「平均粒径」とは、銀被覆銅粒子の懸濁液またはエマルション中の粒子の大きさを、レーザー光線の回折を用いて測定した値である。
銀被覆銅粒子が球状の場合には、球の直径を測定した値から平均粒径を算出でき、平状、フレーク状、樹枝状のような形状の場合には、最長径を測定した値から平均粒径を算出できる。 In the present invention, the average particle size of the silver-coated copper particles is preferably 15 μm or more and 20 μm or less.
In the present invention, the "average particle size" is a value obtained by measuring the size of particles in a suspension or emulsion of silver-coated copper particles using diffraction of a laser beam.
When the silver-coated copper particles are spherical, the average particle size can be calculated from the measured value of the diameter of the sphere, and when the silver-coated copper particles are shaped like flat, flake, or dendritic, the longest diameter is measured. The average particle size can be calculated.

本発明においては、前記接着剤組成物は、前記リン含有樹脂１００質量部に対し、前記銀被銅覆粒子を１００質量部以上２００質量部以下含有し、１１０質量部以上１９０質量部以下がより好ましく、１１５質量部以上１８５質量部以下が特に好ましい。
本発明のＦＰＣ用導電性接着シートは、リン含有樹脂と銀被覆銅粒子との配合割合が、上記特定の範囲の接着剤組成物を用いたことにより、導電性と難燃性とを両立することができる。 In the present invention, the adhesive composition contains 100 parts by mass or more and 200 parts by mass or less of the silver-coated particles with respect to 100 parts by mass of the phosphorus-containing resin, and 110 parts by mass or more and 190 parts by mass or less. It is preferably 115 parts by mass or more and 185 parts by mass or less.
The conductive adhesive sheet for FPC of the present invention has both conductivity and flame retardancy by using an adhesive composition in which the ratio of the phosphorus-containing resin and the silver-coated copper particles is in the above-mentioned specific range. be able to.

［シリカ粒子］
本発明においては、前記接着剤樹脂組成物がシリカ粒子を含有することが好ましい。接着剤樹脂組成物がシリカ粒子を含有することにより、前記銀被覆銅粒子が沈降することを防止できる。また、接着剤樹脂組成物の凝集力を向上させることができるため、ＦＰＣ用導電性接着シートの耐熱性や、基板との密着性も向上させることができる。
本発明においては、シリカ粒子の一次粒子径が、１０ｎｍ以上２０ｎｍ以下であることが好ましく、１２ｎｍ以上１８ｎｍ以下であることがより好ましい。 [Silica particles]
In the present invention, it is preferable that the adhesive resin composition contains silica particles. When the adhesive resin composition contains silica particles, it is possible to prevent the silver-coated copper particles from settling. Further, since the cohesive force of the adhesive resin composition can be improved, the heat resistance of the conductive adhesive sheet for FPC and the adhesion to the substrate can also be improved.
In the present invention, the primary particle size of the silica particles is preferably 10 nm or more and 20 nm or less, and more preferably 12 nm or more and 18 nm or less.

接着剤組成物中のシリカ粒子の含有量は、前記リン含有樹脂１００質量部に対し、１質量部以上１５質量部以下が好ましく、５質量部以上１４質量部以下がより好ましい。 The content of silica particles in the adhesive composition is preferably 1 part by mass or more and 15 parts by mass or less, and more preferably 5 parts by mass or more and 14 parts by mass or less with respect to 100 parts by mass of the phosphorus-containing resin.

［シランカップリング剤］
本発明においては、接着剤樹脂組成物がシランカップリング剤を含有することが好ましい。接着剤樹脂組成物がシランカップリング剤を含有することにより、接着性能を向上させることができる。 [Silane coupling agent]
In the present invention, it is preferable that the adhesive resin composition contains a silane coupling agent. When the adhesive resin composition contains a silane coupling agent, the adhesive performance can be improved.

［その他の成分］
本発明においては、前記各成分に加えて、他の熱硬化性樹脂、熱可塑性樹脂等を添加することが可能である。また硬化促進剤、重合抑制剤、増感剤、難燃化剤、チキソトロピック剤等の添加剤を含有しても良い。
上記の中でも、架橋剤としては、２官能以上のエポキシ樹脂が好ましい。そのようなエポキシ樹脂には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、グリシジルアミン型などが挙げられる。その中でも多官能エポキシ樹脂が耐熱性の観点で好ましい。そのような多官能エポキシ樹脂としては、例えばｊＥＲ（登録商標）１５４、ｊＥＲ１５７、ｊＥＲ１０３１、ｊＥＲ１０３２（三菱化学（株））、ＥＰＩＣＬＯＮ（登録商標） Ｎ−７４０、ＥＰＩＣＬＯＮ Ｎ−７７０（ＤＩＣ（株））、ＹＤＰＮ−６３８、ＹＤＣＮ−７００、ＹＨ−４３４（新日鉄住金化学（株））、ＴＥＴＲＡＤ（登録商標）―Ｘ、ＴＥＴＲＡＤ―Ｃ（三菱瓦斯化学（株））などが挙げられるが、特に限定されない。 [Other ingredients]
In the present invention, other thermosetting resins, thermoplastic resins and the like can be added in addition to the above-mentioned components. Further, additives such as a curing accelerator, a polymerization inhibitor, a sensitizer, a flame retardant, and a thixotropic agent may be contained.
Among the above, as the cross-linking agent, a bifunctional or higher functional epoxy resin is preferable. Examples of such an epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, and a glycidylamine type. Among them, a polyfunctional epoxy resin is preferable from the viewpoint of heat resistance. Examples of such a polyfunctional epoxy resin include jER (registered trademark) 154, jER157, jER1031, jER1032 (Mitsubishi Chemical Co., Ltd.), EPICLON (registered trademark) N-740, and EPICLON N-770 (DIC Corporation). , YDPN-638, YDCN-700, YH-434 (Nippon Steel & Sumikin Chemical Co., Ltd.), TETRAD (registered trademark) -X, TETRAD-C (Mitsubishi Gas Chemical Co., Ltd.), and the like, but are not particularly limited.

＜ＦＰＣ＞
本発明のＦＰＣは、前記本発明のＦＰＣ用導電性接着シートが、ＦＰＣの表面に金属補強板を貼り合わせるために使用されている。
本発明のＦＰＣ用導電性接着シートは、ＦＰＣに、金属補強板付き導電性接着シートを貼合する作業工程の効率向上を図ることができ、生産性の向上に寄与することができ、産業上の利用価値が大である。 <FPC>
In the FPC of the present invention, the conductive adhesive sheet for FPC of the present invention is used to attach a metal reinforcing plate to the surface of the FPC.
The conductive adhesive sheet for FPC of the present invention can improve the efficiency of the work process of attaching the conductive adhesive sheet with a metal reinforcing plate to the FPC, and can contribute to the improvement of productivity, and is industrially effective. The utility value of is great.

以下、実施例により本発明をさらに詳細に説明するが、本発明はこれらの例によって限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these examples.

＜導電性接着剤組成物の調製＞
下記表１に示す各成分を混合し、組成物１〜９、比較組成物１〜４の導電性接着剤組成物を得た。
具体的には、リン含有樹脂の４０％溶液２５０質量部（樹脂成分は１００質量部）に対し、表１に示す各配合比の銀被覆銅粒子、シランカップリング剤、シリカ粒子及び架橋剤を加え、メチルエチルケトン及びトルエンで希釈し、撹拌混合して導電性接着剤組成物を得た。 <Preparation of conductive adhesive composition>
Each component shown in Table 1 below was mixed to obtain a conductive adhesive composition of Compositions 1 to 9 and Comparative Compositions 1 to 4.
Specifically, the silver-coated copper particles, the silane coupling agent, the silica particles, and the cross-linking agent of each compounding ratio shown in Table 1 are added to 250 parts by mass of a 40% solution of the phosphorus-containing resin (resin component is 100 parts by mass). In addition, it was diluted with methyl ethyl ketone and toluene and mixed with stirring to obtain a conductive adhesive composition.

Figure 0006920796
Figure 0006920796

表１中、各成分は以下の材料を意味する。表１中［ ］内の数値は配合比（質量部）である。表１中、「リン含有量」とは、リン含有ポリウレタン樹脂の全量に対するリン元素自体の重量割合である。
・（Ａ）−１：リン含有ポリウレタン（東洋紡（株）製、商品名「ＵＲ−３５７５」（難燃性ポリウレタン樹脂、リン含有濃度：２．５％、酸価：１０ＫＯＨｍｇ/ｇ））。
・（Ａ）−２：ポリウレタンにリン系難燃剤を添加したリン含有樹脂。
・（Ａ）−３：ポリウレタン。
・銀被覆銅粒子：銀コート銅（戸田工業（株）製、品名：ＲＭ−Ｄ１０）。
・シランカップリング剤： 信越化学製ＫＢＭ−４０３
・シリカ粒子：日本アエロジル（株）製、商品名「Ｒ９７２」（疎水性フュームドシリカ）
・架橋剤：東洋紡製、商品名「ＨＹ−３０」。 In Table 1, each component means the following materials. The values in [] in Table 1 are the compounding ratio (parts by mass). In Table 1, the "phosphorus content" is the weight ratio of the phosphorus element itself to the total amount of the phosphorus-containing polyurethane resin.
(A) -1: Phosphorus-containing polyurethane (manufactured by Toyobo Co., Ltd., trade name "UR-3575" (flame-retardant polyurethane resin, phosphorus-containing concentration: 2.5%, acid value: 10 KOHmg / g)).
-(A) -2: Phosphorus-containing resin obtained by adding a phosphorus-based flame retardant to polyurethane.
-(A) -3: Polyurethane.
-Silver-coated copper particles: Silver-coated copper (manufactured by Toda Kogyo Co., Ltd., product name: RM-D10).
・ Silane coupling agent: KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.
-Silica particles: manufactured by Nippon Aerosil Co., Ltd., trade name "R972" (hydrophobic fumed silica)
-Crosslinking agent: Toyobo, trade name "HY-30".

＜ＦＰＣ用導電性接着シートの製造＞
片面に剥離処理を施した、厚みが５０μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムを、支持体フィルム１として用いた。
上記で得た、組成物１〜９、比較組成物１〜４の各導電性接着剤組成物を、前記支持体フィルム１の剥離処理面の上に、乾燥後の厚みがダイヤルゲージで測定して４０μｍとなるようにそれぞれ塗布し、１５０℃、３分間加熱乾燥して、半硬化させ、実施例１〜９、比較例１〜４のＦＰＣ用導電性接着シートを得た。 <Manufacturing of conductive adhesive sheets for FPC>
A polyethylene terephthalate (PET) film having a thickness of 50 μm, which had been peeled off on one side, was used as the support film 1.
The thickness of each of the conductive adhesive compositions of Compositions 1 to 9 and Comparative Compositions 1 to 4 obtained above was measured on the peeling-treated surface of the support film 1 with a dial gauge after drying. The film was applied so as to have a thickness of 40 μm, dried by heating at 150 ° C. for 3 minutes, and semi-cured to obtain conductive adhesive sheets for FPC of Examples 1 to 9 and Comparative Examples 1 to 4.

≪ＦＰＣ用導電性接着シートの評価≫
得られた実施例１〜９、比較例１〜４のＦＰＣ用導電性接着シートについて、下記の評価を行った。 ≪Evaluation of conductive adhesive sheet for FPC≫
The obtained conductive adhesive sheets for FPC of Examples 1 to 9 and Comparative Examples 1 to 4 were evaluated as follows.

［難燃性評価］
実施例１〜９、比較例１〜４のＦＰＣ用導電性接着シートについて燃焼試験を行った。
ＦＰＣ用導電性接着シートを図６に示すように５０ｍｍ×２００ｍｍのサイズに切りだし、測定サンプル６１を１０枚準備した。測定サンプル６１は、縦１２５ｍｍの位置にマーク６２を記載した。準備した測定サンプルを、２３℃湿度５０％の条件に４８時間置き、測定サンプル６１とした。
図６に示すように、符号６４に示す直径が１２．７ｍｍの棒６３に測定サンプルをしっかりと円筒状に巻きつけた。
円筒状の測定サンプル６１の上端から７５ｍｍの部分内を感圧テープ７４でしっかりと留め、その後、棒６３を引き抜いた。測定サンプル６１の上端は測定中に煙突効果がないように閉じた。 [Flame retardation evaluation]
Combustion tests were carried out on the conductive adhesive sheets for FPC of Examples 1 to 9 and Comparative Examples 1 to 4.
As shown in FIG. 6, the conductive adhesive sheet for FPC was cut into a size of 50 mm × 200 mm, and 10 measurement samples 61 were prepared. The measurement sample 61 has a mark 62 at a position 125 mm in length. The prepared measurement sample was placed at 23 ° C. and 50% humidity for 48 hours to prepare a measurement sample 61.
As shown in FIG. 6, the measurement sample was firmly wound around a rod 63 having a diameter of 12.7 mm indicated by reference numeral 64 in a cylindrical shape.
The inside of the portion 75 mm from the upper end of the cylindrical measurement sample 61 was firmly fastened with the pressure-sensitive tape 74, and then the rod 63 was pulled out. The upper end of the measurement sample 61 was closed so that there was no chimney effect during the measurement.

図７に示す、試験台７１のアーム７３の先端に位置するクランプ７２に、円筒状の測定サンプルを垂直に設置した。
測定サンプル６１の３００ｍｍ下方に脱脂綿７８を置き、測定サンプル６１の下端から１０ｍｍの位置（図７の符号７６に示す位置）にバーナーの筒が位置するように、バーナー７５を配置し、サンプルの下端の中央に青色炎を３秒間接炎した。
その後、離炎し、離炎後の測定サンプルの燃焼時間を測定した。１０枚の測定サンプルの燃焼時間を同様に行い、燃焼時間の平均値を算出し、下記の評価基準に従って評価した。
〇：燃焼時間の平均値が３秒以下であった。
△：燃焼時間の平均値が３秒より長く、５秒以下であった。
×：燃焼時間の平均値が５秒より長かった。 A cylindrical measurement sample was vertically placed on the clamp 72 located at the tip of the arm 73 of the test table 71 shown in FIG.
The absorbent cotton 78 is placed 300 mm below the measurement sample 61, and the burner 75 is placed so that the burner cylinder is located 10 mm from the lower end of the measurement sample 61 (the position indicated by reference numeral 76 in FIG. 7), and the lower end of the sample is placed. A blue flame was indirectly burned in the center of the body for 3 seconds.
Then, the flame was released, and the burning time of the measurement sample after the flame was released was measured. The burning time of 10 measurement samples was performed in the same manner, the average value of the burning time was calculated, and the evaluation was performed according to the following evaluation criteria.
〇: The average value of the burning time was 3 seconds or less.
Δ: The average value of the burning time was longer than 3 seconds and 5 seconds or less.
X: The average value of the burning time was longer than 5 seconds.

［密着性］
厚さ３０μｍのＳＵＳ箔（日新製鋼（株）製、材質：ＳＵＳ３０４）からなる金属補強板に、ＦＰＣ用導電性接着シートの導電性接着剤層４側を対向させて重ね、１４０℃、１ｍ／分の条件で熱ラミネートした後、支持体フィルム１を剥離し、ＦＰＣ用導電性接着シートを５０ｍｍ×１２０ｍｍの寸法に裁断した。裁断した金属補強板付き導電性接着シートの導電性接着剤層側と対向させて、厚さ５０μｍのポリイミドフィルム（東レデュポン株式会社製、品番：２００Ｈ）を重ね、１６０℃、２．５ＭＰａで６０分間熱プレスして試験片を得た。ＪＩＳ−Ｃ−６４７１「フレキシブルプリント配線板用銅張積層板試験方法」の８．１．１の方法Ａ（９０°方向引きはがし）に準じて、厚さ３０μｍのＳＵＳ箔側を支持金具に固定し、後から接着した厚さ５０μｍのポリイミドフィルムを引き剥がして剥離力（Ｎ／ｃｍ）を測定し、剥離力が１０Ｎ／ｃｍ以上のサンプルを「○」、５Ｎ／ｃｍ以上、１０Ｎ／ｃｍ未満のサンプルを「△」、５Ｎ／ｃｍ未満のサンプルを「×」として、表２に記載した。 [Adhesion]
A metal reinforcing plate made of SUS foil (manufactured by Nissin Steel Co., Ltd., material: SUS304) having a thickness of 30 μm is laminated with the conductive adhesive layer 4 side of the conductive adhesive sheet for FPC facing each other at 140 ° C., 1 m. After heat laminating under the condition of / min, the support film 1 was peeled off, and the conductive adhesive sheet for FPC was cut into dimensions of 50 mm × 120 mm. A polyimide film with a thickness of 50 μm (manufactured by Toray DuPont Co., Ltd., product number: 200H) was laminated so as to face the conductive adhesive layer side of the cut conductive adhesive sheet with a metal reinforcing plate, and 60 at 160 ° C. and 2.5 MPa. Specimens were obtained by hot pressing for minutes. Fix the SUS foil side with a thickness of 30 μm to the support bracket according to Method A (90 ° direction peeling) of 8.1.1 of JIS-C-6471 "Copper-clad laminate test method for flexible printed wiring board". Then, the polyimide film having a thickness of 50 μm that was adhered later was peeled off and the peeling force (N / cm) was measured. The sample of (Δ) was designated as “Δ”, and the sample of less than 5 N / cm was designated as “x”, and the samples were shown in Table 2.

［導電性］
厚さ３０μｍのＳＵＳ箔（日新製鋼（株）製、材質：ＳＵＳ３０４）からなる金属補強板６の片面に、ＦＰＣ用導電性接着シート５の導電性接着剤層４側を対向させて重ね、１４０℃、１ｍ／分の条件で熱ラミネートした後、幅１５ｍｍ×長さ１００ｍｍの寸法に裁断してから支持体フィルム１を剥離し、金属補強板付き導電性接着シート３０を得た。
次に、図４に示したように、ポリイミドフィルムからなる基板フィルム８上に、幅５ｍｍ×長さ５０ｍｍの短冊状の銅箔片９を、３０ｍｍのピッチ間隔で一列に並べて、複数の銅箔片を配置して、模擬的なフレキシブル基板を作成した。
次に、図５に示したように、その模擬的なフレキシブル基板の短冊状の銅箔片９の一部分を、直径１．５ｍｍのスルーホール１４を有するカバーレイフィルム１２で覆い、さらに、スルーホール１４を覆うように、導電性接着剤層４を介して金属補強板付き導電性接着シート３０を仮固定し、１６０℃、２．５ＭＰａで６０分間熱プレスして、導電性の評価用試験片を得た。次に、前記模擬的なフレキシブル基板の銅箔片９が露出した部分と、金属補強板付き導電性接着シート３０の金属補強板６との間の電気抵抗を、デジタルマルチメーター（株式会社ＴＦＦケースレーインスツルメンツ社製、型式：２１００／１００）で測定し、電気抵抗が０．５Ω未満のサンプルを（○）、０．５Ω以上〜１．０Ω未満のサンプルを（△）、１．０Ω以上のサンプルを（×）とした。 [Conductivity]
A metal reinforcing plate 6 made of SUS foil (manufactured by Nissin Steel Co., Ltd., material: SUS304) having a thickness of 30 μm is overlaid with the conductive adhesive layer 4 side of the conductive adhesive sheet 5 for FPC facing each other. After heat laminating under the conditions of 140 ° C. and 1 m / min, it was cut into dimensions of width 15 mm × length 100 mm, and then the support film 1 was peeled off to obtain a conductive adhesive sheet 30 with a metal reinforcing plate.
Next, as shown in FIG. 4, strip-shaped copper foil pieces 9 having a width of 5 mm and a length of 50 mm are arranged in a row at a pitch interval of 30 mm on a substrate film 8 made of a polyimide film, and a plurality of copper foils are arranged. The pieces were placed to create a simulated flexible substrate.
Next, as shown in FIG. 5, a part of the strip-shaped copper foil piece 9 of the simulated flexible substrate is covered with a coverlay film 12 having a through hole 14 having a diameter of 1.5 mm, and further, the through hole is further covered. A conductive adhesive sheet 30 with a metal reinforcing plate is temporarily fixed via a conductive adhesive layer 4 so as to cover 14, and heat-pressed at 160 ° C. and 2.5 MPa for 60 minutes to evaluate conductivity. Got Next, the electrical resistance between the exposed portion of the copper foil piece 9 of the simulated flexible substrate and the metal reinforcing plate 6 of the conductive adhesive sheet 30 with the metal reinforcing plate is measured by a digital multimeter (TFF Caseley Co., Ltd.). Measured with Instruments, model: 2100/100), samples with electrical resistance of less than 0.5Ω (○), samples of 0.5Ω or more and less than 1.0Ω (△), samples of 1.0Ω or more Was (x).

［樹脂流れ性］
前記導電性の評価により得られた模擬的なフレキシブル基板の端部から樹脂流れが無いかどうかを倍率２００倍の顕微鏡を使って確認を行った。樹脂の流れによるはみ出しが１００μｍ未満であるサンプルを（〇）、樹脂の流れによるはみ出し１００μｍ以上１５０μ未満であるサンプルを（△）、樹脂の流れによるはみ出しが１５０μｍ以上であったサンプルを（×）とした。 [Resin flowability]
Whether or not there was resin flow from the end of the simulated flexible substrate obtained by the evaluation of conductivity was confirmed using a microscope at a magnification of 200 times. Samples with a resin flow protrusion of less than 100 μm (○), samples with a resin flow protrusion of 100 μm or more and less than 150 μm (Δ), and samples with a resin flow protrusion of 150 μm or more (×) bottom.

［耐ブロッキング性］
厚さ２５μｍのポリイミドフィルム（東レデュポン株式会社製、品番：１００Ｈ）に、ＦＰＣ用導電性接着シートの導電性接着剤層４側を対向させて重ね、１４０℃、１ｍ／分の条件で熱ラミネートした後、支持体フィルム１を剥離し、９０ｍｍ×１４０ｍｍの寸法に裁断した。裁断したポリイミドフィルム付き導電性接着シートをＳＵＳ板に固定し５ｋｇの重しを載せて、常温で１時間放置しサンプルを作成した。ＪＩＳ−Ｃ−６４７１「フレキシブルプリント配線板用銅張積層板試験方法」の８．１．１の方法Ｂ（１８０°方向引きはがし）に準じて、ＳＵＳ板からポリイミドフィルム付き導電性接着シートを引き剥がして剥離力（ｍＮ／５０ｍｍ）を測定した。剥離力が１００ｍＮ／５０ｍｍ未満のサンプルを○とし、それ以上を×とした。
この評価方法は、２つの金属補強板付き導電性接着シートを積み重ねたときに引き起こされる、ブロッキング現象のモデルとして、１つの金属補強板付き導電性接着シート（導電性接着剤層の側）を、ポリイミドフィルム付き導電性接着シートで代用し、もう１つの金属補強板付き導電性接着シート（金属補強板の側）を、ＳＵＳ板で代用したものである。 [Blocking resistance]
A polyimide film with a thickness of 25 μm (manufactured by Toray DuPont Co., Ltd., product number: 100H) is laminated with the conductive adhesive layer 4 side of the conductive adhesive sheet for FPC facing each other, and heat-laminated at 140 ° C. and 1 m / min. After that, the support film 1 was peeled off and cut into a size of 90 mm × 140 mm. A conductive adhesive sheet with a cut polyimide film was fixed to a SUS plate, a weight of 5 kg was placed on it, and the mixture was left at room temperature for 1 hour to prepare a sample. Draw a conductive adhesive sheet with a polyimide film from the SUS plate according to Method B (180 ° direction peeling) of 8.1.1 of JIS-C-6471 "Copper-clad laminate test method for flexible printed wiring board". It was peeled off and the peeling force (mN / 50 mm) was measured. A sample having a peeling force of less than 100 mN / 50 mm was marked with ◯, and a sample having a peeling force of less than 100 mN / 50 mm was marked with x.
In this evaluation method, as a model of the blocking phenomenon caused when two conductive adhesive sheets with metal reinforcing plates are stacked, one conductive adhesive sheet with metal reinforcing plates (on the side of the conductive adhesive layer) is used. A conductive adhesive sheet with a polyimide film is used as a substitute, and another conductive adhesive sheet with a metal reinforcing plate (on the side of the metal reinforcing plate) is replaced by a SUS plate.

Figure 0006920796
Figure 0006920796

上記結果に示したとおり、本発明を適用した実施例１〜９のＦＰＣ用導電性接着シートは、難燃性と導電性を両立しており、さらに、密着性も良好であった。
実施例８は、評価を行うことはできたが、銀被覆銅粒子の粒子径が大きく、形成した接着剤層が空気を含んでしまったため、総合評価を「△」とした。
ポリウレタンにリン系難燃剤を添加したリン含有樹脂を用いた実施例９よりも、分子中にリンを含むリン含有ポリウレタンを用いた実施例１〜８のほうが、高い難燃性を示した。
これに対し、比較例１は、銀被覆銅粒子の配合量が多く、密着性が著しく不良であった。また、比較例２〜４は、難燃性が良好ではなかった。本発明を適用しない比較例１〜４は、いずれも難燃性と導電性を両立させることができなかった。 As shown in the above results, the conductive adhesive sheets for FPCs of Examples 1 to 9 to which the present invention was applied had both flame retardancy and conductivity, and also had good adhesion.
Although the evaluation could be performed in Example 8, the overall evaluation was set to "Δ" because the particle size of the silver-coated copper particles was large and the formed adhesive layer contained air.
Examples 1 to 8 using phosphorus-containing polyurethane containing phosphorus in the molecule showed higher flame retardancy than Example 9 using a phosphorus-containing resin in which a phosphorus-based flame retardant was added to polyurethane.
On the other hand, in Comparative Example 1, the amount of silver-coated copper particles blended was large, and the adhesion was remarkably poor. Further, Comparative Examples 2 to 4 did not have good flame retardancy. In Comparative Examples 1 to 4 to which the present invention is not applied, both flame retardancy and conductivity could not be achieved at the same time.

１…支持体フィルム、２…リン含有樹脂、３…銀被覆銅粒子、４…導電性接着剤層、５…ＦＰＣ用導電性接着シート、６…金属補強板、７…実装部品、８…基板フィルム、９…アース回路（銅箔片）、１０…絶縁性接着剤層、１１…絶縁フィルム、１２…カバーレイ、１４…スルーホール、２０…ＦＰＣ、３０…金属補強板付き導電性接着シート、６１…測定サンプル、６２…マーク、６３…棒、６４…棒の直径、７４…感圧テープ、７１…試験台、７２…クランプ、７３…アーム、７８…脱脂綿、７６…接炎位置、７５…バーナー。 1 ... Support film, 2 ... Phosphorus-containing resin, 3 ... Silver-coated copper particles, 4 ... Conductive adhesive layer, 5 ... Conductive adhesive sheet for FPC, 6 ... Metal reinforcing plate, 7 ... Mounting parts, 8 ... Substrate Film, 9 ... Earth circuit (copper foil piece), 10 ... Insulating adhesive layer, 11 ... Insulating film, 12 ... Coverlay, 14 ... Through hole, 20 ... FPC, 30 ... Conductive adhesive sheet with metal reinforcing plate, 61 ... Measurement sample, 62 ... Mark, 63 ... Rod, 64 ... Rod diameter, 74 ... Pressure sensitive tape, 71 ... Test table, 72 ... Clamp, 73 ... Arm, 78 ... Degreased cotton, 76 ... Flame contact position, 75 ... burner.

Claims (11)

支持体フィルムと、前記支持体フィルムの一方の面に積層された導電性接着剤層と、を有し、前記導電性接着剤層は、リン含有樹脂と、銀被覆銅粒子と、を含有する導電性接着剤組成物を形成材料とし、前記導電性接着剤組成物は、前記リン含有樹脂１００質量部に対し、前記銀被覆銅粒子を１００質量部以上２００質量部以下含有し、前記リン含有樹脂は、前記リン含有樹脂１００質量部に対し、リンを０．２質量部以上含み、前記銀被覆銅粒子は、銀被覆率が８０％以上であり、下記条件で行う難燃性評価において、燃焼時間が５秒未満であることを特徴とするＦＰＣ用導電性接着シート。
＜条件＞
≪測定サンプルの準備≫
ＦＰＣ用導電性接着シートを５０ｍｍ×２００ｍｍのサイズに１０枚を切り出し、２３℃湿度５０％の条件に４８時間置き、測定サンプルとする。
≪評価条件≫
前記方法により準備した測定サンプルを直径１２．７ｍｍの棒に巻きつける。
その後、円筒状に巻きつけたサンプルのうち、上端から７５ｍｍ以内の部分内を感圧テープで留め、棒を引き抜く。
その後、測定サンプルの上端は測定中に煙突効果がないように閉じる。
その後、測定サンプルを垂直に配置し、その３００ｍｍ下方に脱脂綿を置く。
その後、測定サンプルの下端から１０ｍｍのところにバーナーの筒が位置するように、バーナーを配置する。
その後、サンプルの下端の中央に青色炎を３秒間接炎し、離炎後の測定サンプルの燃焼時間を測定する。
１０枚の測定サンプルの燃焼時間を同様に行い、燃焼時間の平均値を算出する。 It has a support film and a conductive adhesive layer laminated on one surface of the support film, and the conductive adhesive layer contains a phosphorus-containing resin and silver-coated copper particles. The conductive adhesive composition is used as a forming material, and the conductive adhesive composition contains 100 parts by mass or more and 200 parts by mass or less of the silver-coated copper particles with respect to 100 parts by mass of the phosphorus-containing resin, and contains the phosphorus. The resin contains 0.2 parts by mass or more of phosphorus with respect to 100 parts by mass of the phosphorus-containing resin, and the silver-coated copper particles have a silver coating ratio of 80% or more. A conductive adhesive sheet for FPC, characterized in that the burning time is less than 5 seconds.
<Conditions>
≪Preparation of measurement sample≫
Ten conductive adhesive sheets for FPC are cut out to a size of 50 mm × 200 mm and placed at 23 ° C. and 50% humidity for 48 hours to prepare a measurement sample.
≪Evaluation conditions≫
The measurement sample prepared by the above method is wound around a rod having a diameter of 12.7 mm.
Then, of the sample wound in a cylindrical shape, the inside of the portion within 75 mm from the upper end is fastened with pressure-sensitive tape, and the rod is pulled out.
After that, the upper end of the measurement sample is closed so that there is no chimney effect during the measurement.
Then, the measurement sample is placed vertically, and cotton wool is placed 300 mm below the measurement sample.
After that, the burner is arranged so that the cylinder of the burner is located 10 mm from the lower end of the measurement sample.
Then, a blue flame is indirectly flamed in the center of the lower end of the sample for 3 seconds, and the burning time of the measurement sample after deflaming is measured.
The burning time of 10 measurement samples is performed in the same manner, and the average value of the burning time is calculated. 前記銀被覆銅粒子の銀被覆率が、９５％以上である、請求項１に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to claim 1, wherein the silver coating ratio of the silver-coated copper particles is 95% or more. 前記銀被覆銅粒子が樹枝状である、請求項１又は２に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to claim 1 or 2 , wherein the silver-coated copper particles are dendritic. 前記銀被覆銅粒子の平均粒径が、１５μｍ以上２０μｍ以下である、請求項１〜３のいずれか１項に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to any one of claims 1 to 3 , wherein the silver-coated copper particles have an average particle size of 15 μm or more and 20 μm or less. 前記リン含有樹脂は、リン含有ポリウレタン樹脂である、請求項１〜４のいずれか１項に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to any one of claims 1 to 4 , wherein the phosphorus-containing resin is a phosphorus-containing polyurethane resin. 前記リン含有ポリウレタン樹脂のリンの濃度が、前記リン含有ポリウレタン樹脂の全量中の１重量％以上である、請求項５に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to claim 5 , wherein the phosphorus concentration of the phosphorus-containing polyurethane resin is 1% by weight or more based on the total amount of the phosphorus-containing polyurethane resin. 前記導電性接着剤樹脂組成物がシリカ粒子を含有する、請求項１〜６のいずれか１項に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to any one of claims 1 to 6 , wherein the conductive adhesive resin composition contains silica particles. 前記シリカ粒子の一次粒子径が、１０ｎｍ以上２０ｎｍ以下である、請求項７に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to claim 7 , wherein the primary particle size of the silica particles is 10 nm or more and 20 nm or less. 前記リン含有樹脂１００質量部に対し、前記シリカ粒子を１質量部以上１５質量部以下含有する、請求項１〜８のいずれか１項に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to any one of claims 1 to 8 , wherein the silica particles are contained in an amount of 1 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the phosphorus-containing resin. 前記導電性接着剤樹脂組成物がシランカップリング剤を含有する、請求項１〜９のいずれか１項に記載のＦＰＣ用導電性接着シート。 The conductive adhesive sheet for FPC according to any one of claims 1 to 9 , wherein the conductive adhesive resin composition contains a silane coupling agent. 請求項１〜１０のいずれか１項に記載のＦＰＣ用導電性接着シートが、ＦＰＣの表面に金属補強板を貼り合わせるために使用されているＦＰＣ。 The FPC in which the conductive adhesive sheet for FPC according to any one of claims 1 to 10 is used for adhering a metal reinforcing plate to the surface of the FPC.
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CN110505767B (en) * 2019-07-08 2021-03-30 苏州固泰新材股份有限公司 Flexible copper foil base material and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4425118B2 (en) * 2003-12-03 2010-03-03 株式会社有沢製作所 Flame retardant resin composition, metal-clad laminate for flexible printed wiring board using the composition, coverlay, adhesive sheet, and flexible printed wiring board
SG155084A1 (en) * 2008-02-28 2009-09-30 Sumitomo Bakelite Singapore Pt Thermally and electrically conductive and adhesive composition for semiconductor packaging
JP4825830B2 (en) * 2008-03-11 2011-11-30 住友電気工業株式会社 Flexible printed circuit board with metal reinforcement
JP5257125B2 (en) * 2009-02-20 2013-08-07 東洋インキＳｃホールディングス株式会社 Curable flame retardant electromagnetic shielding film
JP2010195887A (en) * 2009-02-24 2010-09-09 Sumitomo Electric Ind Ltd Adhesive resin composition, and laminate and flexible printed wiring board using the same
JP5385635B2 (en) * 2009-02-24 2014-01-08 住友電気工業株式会社 Adhesive resin composition, laminate using the same, and flexible printed wiring board
JP2011151095A (en) * 2010-01-20 2011-08-04 Toyo Ink Sc Holdings Co Ltd Flame retardant electromagnetic wave shielding adhesive film and method for manufacturing the same
JP5528857B2 (en) * 2010-03-11 2014-06-25 タツタ電線株式会社 Electromagnetic wave shielding film, flexible substrate using the same, and method for producing the same
JP5405383B2 (en) * 2010-05-07 2014-02-05 アキレス株式会社 Flame retardant urethane resin and flame retardant synthetic leather
JP5736046B2 (en) * 2010-06-23 2015-06-17 インクテック カンパニー リミテッド Method for producing electromagnetic wave shielding film and electromagnetic wave shielding film produced thereby
CN101950598A (en) * 2010-09-29 2011-01-19 彩虹集团公司 Conductor pulp for printed circuit board and preparation method thereof
CN104024338A (en) * 2011-06-03 2014-09-03 Frx聚合物股份有限公司 Fire-retardant resin composition, metal-clad base laminate for flexible printed circuit board utilizing said composition, cover lay, adhesive sheet for flexible printed circuit board and flexible printed circuit board
KR101361533B1 (en) * 2012-04-12 2014-02-13 한화엘앤씨 주식회사 Method for manufacturing electromagnetic wave shield film
WO2014007353A1 (en) * 2012-07-05 2014-01-09 リンテック株式会社 Pressure-sensitive adhesive sheet
CN104487534B (en) 2012-07-11 2016-11-09 大自达电线股份有限公司 Hardening conductive adhesive composition, electromagnetic shielding film, conductive adhesive film, adhesive method and circuit base plate
JP6081819B2 (en) * 2013-02-28 2017-02-15 藤森工業株式会社 Electromagnetic wave shielding material for FPC
JP6287430B2 (en) * 2014-03-25 2018-03-07 東洋インキＳｃホールディングス株式会社 Conductive adhesive sheet, electromagnetic shielding sheet, and printed wiring board
JP2016048746A (en) * 2014-08-28 2016-04-07 住友電気工業株式会社 Shield tape
JP2016060966A (en) * 2014-09-12 2016-04-25 住友金属鉱山株式会社 Silver coat copper powder and conductive paste using the same, conductive coating and conductive sheet
JPWO2016084855A1 (en) * 2014-11-26 2017-08-31 日立化成株式会社 Photosensitive resin composition, photosensitive element, cured product, semiconductor device, resist pattern forming method, and circuit substrate manufacturing method
JP5892282B1 (en) * 2015-04-27 2016-03-23 東洋インキＳｃホールディングス株式会社 Conductive adhesive, conductive adhesive sheet, and wiring device
JP2016054312A (en) * 2015-11-30 2016-04-14 日立化成株式会社 Element and solar cell

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KR101970484B1 (en) 2019-04-19
JP2018022827A (en) 2018-02-08

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