JP3835090B2 - Adhesive for flexible printed wiring boards - Google Patents

Adhesive for flexible printed wiring boards Download PDF

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JP3835090B2
JP3835090B2 JP34967499A JP34967499A JP3835090B2 JP 3835090 B2 JP3835090 B2 JP 3835090B2 JP 34967499 A JP34967499 A JP 34967499A JP 34967499 A JP34967499 A JP 34967499A JP 3835090 B2 JP3835090 B2 JP 3835090B2
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Japan
Prior art keywords
adhesive
flexible printed
weight
printed wiring
parts
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JP34967499A
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Japanese (ja)
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JP2001164226A (en
Inventor
和信 丹治
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Nippon Mektron KK
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Nippon Mektron KK
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  • Adhesives Or Adhesive Processes (AREA)
  • Manufacturing Of Printed Wiring (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、フレキシブル印刷配線板用接着剤に関する。更に詳しくは、カバーレイ用接着剤などとして効果的に用いられるフレキシブル印刷配線板用接着剤に関する。
【0002】
【従来の技術】
近年の電子機器の高密度化や多様化に伴ない、そこに搭載される回路基板としては、軽量化、小型化、薄型化などの点で非常に有利なフレキシブル印刷回路が益々多く使用されるようになってきており、その回路はより高密度化、複雑化している。この高密度化、複雑化は、回路パターンの線幅および線間隔の狭小化やランドの狭小化を促している。
【0003】
また、カバーレイは、フレキシブル印刷回路の金属導体の腐食や汚染からの保護、回路間の絶縁性の確保、折曲性や屈曲性の向上などを目的として使用されており、ポリイミドフィルム等の耐熱性フィルムに接着剤層を形成させたものが用いられている。このような接着剤層を形成させたカバーレイは、その接着剤層がフレキシブル銅張板の銅回路と接する状態で用いられ、フレキシブル印刷配線板を形成する。
【0004】
このような目的で用いられるカバーレイには、すぐれた接着性および耐銅マイグレーション性などの電気的特性ばかりではなく、ランド部への流れ出し量が少なく、かつパターンへの埋込性を低下させることなく、長期にわたって一定の流れ出し量をコントロールすることのできる保存安定性が益々要求されるようになってきている。
【0005】
また、回路に部品を搭載する工程の生産性の向上のために、高温高速で半田付けが行われるので、すぐれた半田耐熱性も要求される。特に、近年は搭載される部品が高価となっているので、半田付け時の不良率の低下が強く求められている。
【0006】
一般に、フレキシブル印刷配線用接着剤としては、耐熱性および電気絶縁性にすぐれているエポキシ樹脂が多く用いられているが、それ単独で用いられることはなく、ポリエステル、ポリビニルブチラール、ポリアミド、ポリイミド、アクリルゴム、NBR等の高分子物質が、接着剤層に可撓性を付与するために添加されて用いられている。しかしながら、合成ゴム系以外の高分子物質は、樹脂が有する吸水性のために半田耐熱性が低く、ふくれや剥れなどの不具合を生じ易い。このような不具合は、特に高温高速での半田付けにおいて生じ易い。
【0007】
一方、合成ゴム系の高分子物質としては、一般に接着性にすぐれているカルボキシル変性合成ゴムが用いられているが、これらは保存安定性を欠いているため、長期にわたってその性能を維持させるために、B-ステージでの輸送および保管に際して低温装置等の高価な設備を必要としたり、あるいは低温保管であるが故に作業前に室温に戻すなどの工程を必要としている。
【0008】
特開平2-187485号公報には、合成ゴム、エポキシ樹脂、分子内に少くとも2個のフェノール性水酸基を有するフェノール変性キシレン樹脂硬化剤および硬化促進剤を必須成分とするフレキシブル印刷配線板用接着剤(カバーレイ用接着剤)が記載されている。そこには、接着性、タック性および線間絶縁抵抗についての具体的な記載は示されているものの、半田耐熱性およびB-ステージでの保存安定性についての具体的な記載はみられない。
【0009】
また、フェノール変性キシレン樹脂硬化物を用いることにより、B-ステージでのベトツキが少なく、作業性の良いフレキシブル印刷配線板用接着剤が得られると記載されており、溶媒に対する溶解性の点からは、三次元構造ではなく直線構造を有するノボラック型のものが好ましいと述べられているが、ノボラック型のものはB-ステージでの保存安定性は改善されない。
【0010】
【発明が解決しようとする課題】
本発明の目的は、カバーレイ用接着剤として用いられたとき、接着性、半田耐熱性、耐銅マイグレーション性、保存安定性などの点をいずれも満足させるフレキシブル印刷配線板用接着剤を提供することにある。
【0011】
【課題を解決するための手段】
かかる本発明の目的は、エポキシ樹脂100重量部、カルボキシル変性合成ゴム20〜110重量部、レゾール変性フェノール樹脂1〜50重量部、芳香族ジアミン2〜20重量部および三フッ化ホウ素錯体0.02〜2.5重量部を必須成分として含有してなるフレキシブル印刷配線板用接着剤によって達成される。
【0012】
【発明の実施の形態】
エポキシ樹脂としては、1分子中に2個以上のエポキシ基を有するものであれば任意のものを用いることができ、例えばビスフェノールA型、低または高臭素化ビスフェノールA型、ビスフェノールF型、フェノールノボラック型、臭素化フェノールノボラック型、クレゾールノボラック型等のグリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂等の少くとも一種が用いられる。
【0013】
カルボキシル変性合成ゴムとしては、SBRまたはNBR中に少量の(メタ)アクリル酸(エステル)単量体を共重合させたカルボキシル化SBRまたはNBR、エチレン-アクリル酸メチル-(メタ)アクリル酸3元共重合ゴム、無水マレイン酸付加ゴム等の少くとも一種が用いられ、実際には市販品、例えば日本ゼオン製品ニポール1072、日本合成ゴム製品PNR-1H、N-632S、デュポン社製品Vamac G等をそのまま用いることができる。
【0014】
これらのカルボキシル変性合成ゴムは、エポキシ樹脂100重量部当り約20〜110重量部、好ましくは約25〜100重量部の割合で用いられる。使用割合がこれよりも少ないと、十分なる接着性を付与することができず、一方これ以上の割合で用いられると、耐銅マイグレーション性が低下するようになる。
【0015】
レゾール変性フェノール樹脂としては、1分子中に少くとも2個の芳香族環に直結したメチロール基を有する樹脂、例えば塩基性触媒の存在下でp-位をアルキル化したフェノールから調製されたアルキルフェノール樹脂、トルエン、キシレン、メシチレン等とホルムアルデヒドとを反応させて得られた芳香族炭化水素樹脂、それをフェノールまたはアルキルフェノールで変性した変性芳香族炭化水素樹脂等が用いられる。実際には、市販品、例えば住友デュレス製品PR-22193、PR-50702、PR-50530、三菱ガス化学製品PR-1440M、PR-1440、PR-1540、PR-GR-L、日立化成製品ヒタノール643KN、2180、2400、2410等をそのまま用いることができる。
【0016】
これらのレゾール変性フェノール樹脂は、エポキシ樹脂100重量部当り約1〜50重量部、好ましくは約2〜30重量部の割合で用いられる。これよりも少ない使用割合では、保存安定性が低下するようになり、一方これよりも多い割合で使用されると、接着性が低下するようになる。
【0017】
芳香族ジアミンとしては、4,4′-ジアミノジフェニルメタン、3,3′-ジアミノジフェニルスルホン、4,4′-ジアミノジフェニルスルホン、4,4′-ジアミノ-3,3′-ジエチル-5,5′-ジフェニルメタン等の少くとも一種が用いられ、好ましくは保存安定性の点から4,4′-ジアミノジフェニルスルホンが用いられる。これらの芳香族ジアミンは、エポキシ樹脂100重量部当り約2〜20重量部、好ましくは約5〜20重量部の割合で用いられ、この範囲外では半田耐熱性および接着性がいずれも低下するようになる。
【0018】
また、三フッ化ホウ素錯体としては、ピペリジン、モノエタノールアミン、トリエタノールアミン等との錯体が用いられ、好ましくは保存安定性の点からピペリジンとの錯体が用いられる。これらの三フッ化ホウ素錯体は、エポキシ100重量部当り約0.02〜2.5重量部、好ましくは約0.1〜1.5重量部の割合で用いられる。これよりも少ない使用割合では、耐銅マイグレーション性が低下し、一方これよりも多い割合で使用されると、保存安定性が低下するようになる。
【0019】
以上の各成分を必須成分とするフレキシブル印刷配線板用接着剤中には、必要に応じて、保存安定性その他の特性を阻害しない範囲内において、イミダゾール、ジシアンジアミド、第4級アンモニウム塩等の硬化促進剤、可塑剤、酸化防止剤、シリカ、アルミナ、酸化チタン等の充填剤、水酸化アルミニウム、三酸化アンチモン等の難燃化剤、各種界面活性剤である分散剤、シラン系カップリング剤等の接着促進剤、有機ベントナイト等の粘度調節剤、レベリング剤等が適宜添加されて用いられる。
【0020】
フレキシブル印刷配線板用接着剤は、アセトン、メチルエチルケトン等のケトン類、イソプロパノール等のアルコール類、トルエン、キシレン等の芳香族炭化水素類等の有機溶媒で希釈され、その固形分濃度を約20〜40重量%に調整した上で用いられる。かかる接着剤溶液の被着体への適用は、これを耐熱性プラスチックフィルム、例えばポリイミドフィルム上に塗布、乾燥して、接着剤層を有するフィルムとし、その接着剤層面側に離型性の保護フィルムを付して保管される。
【0021】
使用に際しては、保護フィルムを剥がし、接着剤層を有するフィルムの接着剤層面側をフレキシブル印刷配線板上に載せ、ロール式またはバッチ式プレスによって圧着することにより、接着が行われる。この圧着は、約100〜190℃、約0.5〜5MPa、約1〜50分間の条件下で行われ、一般にはその後約120〜200℃でポストキュアして、更に特性を向上させる。
【0022】
【発明の効果】
本発明に係るフレキシブル印刷配線板用接着剤は、カバーレイ用接着剤として用いた場合、吸湿性が小さく、硬化物の電気特性、接着性などにすぐれ、B-ステージの硬化反応が抑えられた材料が用いられているため、接着性、半田耐熱性、耐銅マイグレーション性などにすぐれ、特にB-ステージでの保存安定性にすぐれている。また、銅張り板(回路)用などとしても使用される。
【0023】
更に、輸送および保管の際においても、低温保管設備が不要であることから経済性にもすぐれ、更に室温に戻す工程も不要であるなど、産業上の利用価値が極めて高いということができる。
【0024】
【実施例】
次に、実施例について本発明を説明する。
【0025】
実施例1
ビスフェノールA型エポキシ樹脂 41g
(油化シェルエポキシ製品EP 1004AF)
臭素化ビスフェノールA型エポキシ樹脂 38g
(同社製品EP5051)
臭素化フェノールノボラック型エポキシ樹脂 21g
(日本化薬製品BREN-S)
カルボキシル変性NBR 39g
(日本合成ゴム製品PNR-1H)
レゾール型変性フェノール樹脂 5g
(日立化成製品HN-643KN)
4,4′-ジアミノジフェニルスルホン [4,4′-DDS] 6g
BF3・ピペリジン錯体(橋本化成製品) 0.6g
メチルエチルケトン 280g
以上の各成分をボールミルによって均一に溶解させて調製した固形分濃度約35重量%の接着剤溶液を、乾燥塗膜厚さが35μmになるように、ポリイミドフィルム(デュポン社製品カプトン100H、厚さ25μm)上に塗布し、室温下で10分間、次いで120℃で2分間乾燥して、接着剤層を有するフィルムとし、その接着剤層に離型性保護フィルムを付着させた。
【0026】
この接着剤層を有するフィルムと、サブトラクト法でテストパターンを形成させたフレキシブル銅張積層板とを、165℃、1MPa、5分間の条件下で加熱プレスを行った後、140℃で2時間のポストキュアを行ない、フレキシブル積層フィルムを作成した。
【0027】
得られた積層フィルムについて、次の各項目の測定を行ない、フレキシブル印刷配線用カバーレイ接着剤の評価を行った。

Figure 0003835090
、線厚み35μmの回路への埋込みができなくなる迄の日数を測定
【0028】
実施例2〜3、比較例1〜9
実施例1において、ビスフェノールA型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂および臭素化フェノールノボラック型エポキシ樹脂(合計100g)以外の各成分量(単位:g)を、次の表1に示されるように変更した。
【0029】
なお、Vamac Gはデュポン社製品のエチレン-不飽和カルボン酸系共重合体であり、またGHP-160は三菱ガス化学製品のノボラック型変性キシレン樹脂である。
Figure 0003835090
【0030】
以上の各実施例および比較例における測定結果は、次の表2に示される。
Figure 0003835090
【0031】
以上の結果から、次のようなことがいえる。
(1) 本発明に係るフレキシブル印刷配線板用接着剤は、接着性、半田耐熱性、保存安定性が良好であり、銅マイグレーションもみられない。
(2) カルボキシル変性ゴム量の多すぎる比較例1では銅マイグレーションが発生し、一方少なすぎる比較例2では剥離強度(接着性)が低下している。
(3) レゾール変性フェノール樹脂量が少なすぎる比較例3では保存安定性が低下し、一方多すぎる比較例4では剥離強度(接着性)が低下している。
(4) 芳香族ジアミン量が少なすぎる比較例5および多すぎる比較例6では、共に半田耐熱性および剥離強度(接着性)が低下している。
(5) 三フッ化ホウ素錯体量の少なすぎる比較例8では銅マイグレーションが発生し、多すぎる比較例9では保存安定性が低下している。(6) レゾール型変性フェノール樹脂の代りにノボラック型変性キシレン樹脂が用いられた比較例7では、保存安定性が低下している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive for flexible printed wiring boards. More specifically, the present invention relates to an adhesive for a flexible printed wiring board that is effectively used as an adhesive for a coverlay or the like.
[0002]
[Prior art]
With the recent increase in density and diversification of electronic devices, flexible printed circuits that are extremely advantageous in terms of weight reduction, size reduction, and thickness reduction are increasingly used as circuit boards to be mounted thereon. The circuit is becoming more dense and complex. This increase in density and complexity has led to a reduction in circuit pattern line width and line spacing and land.
[0003]
Coverlays are used to protect metal conductors in flexible printed circuits from corrosion and contamination, to ensure insulation between circuits, and to improve bendability and flexibility. An adhesive film having an adhesive layer formed thereon is used. The coverlay on which such an adhesive layer is formed is used in a state where the adhesive layer is in contact with the copper circuit of the flexible copper-clad board, and forms a flexible printed wiring board.
[0004]
Coverlays used for this purpose not only have excellent adhesive properties and electrical properties such as copper migration resistance, but also have a small amount of flow out to the land and a low level of pattern embedding. However, there is an increasing demand for storage stability capable of controlling a constant flow rate over a long period of time.
[0005]
In addition, since soldering is performed at high temperature and high speed in order to improve the productivity of the process of mounting components on the circuit, excellent solder heat resistance is also required. In particular, since the components to be mounted have become expensive in recent years, there is a strong demand for a reduction in the defective rate during soldering.
[0006]
In general, as an adhesive for flexible printed wiring, an epoxy resin excellent in heat resistance and electrical insulation is often used, but it is not used alone, and polyester, polyvinyl butyral, polyamide, polyimide, acrylic Polymer substances such as rubber and NBR are added and used to impart flexibility to the adhesive layer. However, polymer materials other than synthetic rubbers have low solder heat resistance due to the water absorption of the resin, and are liable to cause problems such as blistering and peeling. Such a defect is likely to occur particularly in soldering at high temperature and high speed.
[0007]
On the other hand, carboxyl-modified synthetic rubbers that are generally excellent in adhesiveness are used as the synthetic rubber-based polymer substances. However, since these are lacking in storage stability, in order to maintain their performance over a long period of time. In transportation and storage on the B-stage, expensive equipment such as a low-temperature apparatus is required, or because of low-temperature storage, a process such as returning to room temperature before work is required.
[0008]
Japanese Patent Application Laid-Open No. 2-187485 discloses adhesives for flexible printed wiring boards comprising a synthetic rubber, an epoxy resin, a phenol-modified xylene resin curing agent having at least two phenolic hydroxyl groups in the molecule and a curing accelerator as essential components. Agent (coverlay adhesive) is described. There are specific descriptions of adhesiveness, tackiness, and insulation resistance between lines, but there are no specific descriptions of solder heat resistance and storage stability at the B-stage.
[0009]
In addition, it is described that by using a phenol-modified xylene resin cured product, an adhesive for flexible printed wiring boards with less stickiness on the B-stage and good workability can be obtained. Although it is stated that a novolak type having a linear structure rather than a three-dimensional structure is preferred, the novolak type does not improve the storage stability on the B-stage.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide an adhesive for a flexible printed wiring board that, when used as an adhesive for a coverlay, satisfies all of the points such as adhesion, solder heat resistance, copper migration resistance, and storage stability. There is.
[0011]
[Means for Solving the Problems]
The object of the present invention is to provide 100 parts by weight of an epoxy resin, 20 to 110 parts by weight of a carboxyl-modified synthetic rubber, 1 to 50 parts by weight of a resole-modified phenol resin, 2 to 20 parts by weight of an aromatic diamine, and 0.02 to 2.5 of a boron trifluoride complex. This is achieved by an adhesive for a flexible printed wiring board containing a weight part as an essential component.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
As the epoxy resin, any one having two or more epoxy groups in one molecule can be used. For example, bisphenol A type, low or high brominated bisphenol A type, bisphenol F type, phenol novolac Type, brominated phenol novolak type, cresol novolak type glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, etc. .
[0013]
As carboxyl-modified synthetic rubber, carboxylated SBR or NBR obtained by copolymerizing a small amount of (meth) acrylic acid (ester) monomer in SBR or NBR, ethylene-methyl acrylate- (meth) acrylic acid ternary copolymer. At least one kind of polymerized rubber, maleic anhydride-added rubber, etc. is used. Actually, commercially available products such as Nippon Zeon product Nipol 1072, Japan synthetic rubber products PNR-1H, N-632S, DuPont product Vamac G etc. Can be used.
[0014]
These carboxyl-modified synthetic rubbers are used at a ratio of about 20 to 110 parts by weight, preferably about 25 to 100 parts by weight, per 100 parts by weight of the epoxy resin. If the proportion used is less than this, sufficient adhesion cannot be imparted, while if it is used in a proportion higher than this, the copper migration resistance is lowered.
[0015]
Resole-modified phenolic resins include resins having methylol groups directly linked to at least two aromatic rings in one molecule, for example, alkylphenol resins prepared from phenol alkylated at the p-position in the presence of a basic catalyst. An aromatic hydrocarbon resin obtained by reacting formaldehyde with toluene, xylene, mesitylene, etc., a modified aromatic hydrocarbon resin obtained by modifying it with phenol or alkylphenol, or the like is used. Actually, commercially available products such as Sumitomo Dureth products PR-22193, PR-50702, PR-50530, Mitsubishi Gas Chemical Products PR-1440M, PR-1440, PR-1540, PR-GR-L, Hitachi Chemical Product Hitanol 643KN , 2180, 2400, 2410, etc. can be used as they are.
[0016]
These resole-modified phenol resins are used in a ratio of about 1 to 50 parts by weight, preferably about 2 to 30 parts by weight, per 100 parts by weight of the epoxy resin. If the proportion is less than this, the storage stability will be lowered, while if it is used in a proportion larger than this, the adhesiveness will be lowered.
[0017]
Aromatic diamines include 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 4,4'-diamino-3,3'-diethyl-5,5 ' At least one such as -diphenylmethane is used, and 4,4'-diaminodiphenyl sulfone is preferably used from the viewpoint of storage stability. These aromatic diamines are used at a ratio of about 2 to 20 parts by weight, preferably about 5 to 20 parts by weight, per 100 parts by weight of the epoxy resin. Outside this range, both the solder heat resistance and the adhesiveness are lowered. become.
[0018]
As the boron trifluoride complex, a complex with piperidine, monoethanolamine, triethanolamine or the like is used, and a complex with piperidine is preferably used from the viewpoint of storage stability. These boron trifluoride complexes are used in a ratio of about 0.02 to 2.5 parts by weight, preferably about 0.1 to 1.5 parts by weight, per 100 parts by weight of epoxy. If the ratio is less than this, the resistance to copper migration decreases, while if the ratio is greater than this, the storage stability decreases.
[0019]
In the adhesive for flexible printed wiring boards containing each of the above components as essential components, curing of imidazole, dicyandiamide, quaternary ammonium salts, etc., if necessary, within a range that does not impair storage stability and other properties. Accelerators, plasticizers, antioxidants, fillers such as silica, alumina, titanium oxide, flame retardants such as aluminum hydroxide and antimony trioxide, dispersants as various surfactants, silane coupling agents, etc. Adhesion promoters, viscosity regulators such as organic bentonite, leveling agents and the like are appropriately added and used.
[0020]
The adhesive for flexible printed wiring boards is diluted with organic solvents such as ketones such as acetone and methyl ethyl ketone, alcohols such as isopropanol, aromatic hydrocarbons such as toluene and xylene, and the solid content concentration is about 20 to 40 Used after adjusting to% by weight. The adhesive solution is applied to an adherend by applying it to a heat-resistant plastic film, for example, a polyimide film, and drying it to form a film having an adhesive layer. Stored with film.
[0021]
In use, the protective film is peeled off, and the adhesive layer surface side of the film having the adhesive layer is placed on the flexible printed wiring board, and the adhesion is performed by pressure bonding with a roll type or batch type press. This pressure bonding is performed under conditions of about 100 to 190 ° C., about 0.5 to 5 MPa, and about 1 to 50 minutes, and then generally post-cured at about 120 to 200 ° C. to further improve the properties.
[0022]
【The invention's effect】
When used as an adhesive for coverlay, the adhesive for flexible printed wiring board according to the present invention has low hygroscopicity, excellent electrical properties and adhesiveness of the cured product, and the B-stage curing reaction was suppressed. Since the material is used, it has excellent adhesiveness, solder heat resistance, copper migration resistance, etc., especially storage stability on the B-stage. It is also used for copper-clad plates (circuits).
[0023]
Furthermore, it can be said that the industrial utility value is extremely high in that it is economical because it does not require a low-temperature storage facility during transportation and storage, and a step of returning to room temperature is also unnecessary.
[0024]
【Example】
Next, the present invention will be described with reference to examples.
[0025]
Example 1
Bisphenol A type epoxy resin 41g
(Oilized shell epoxy product EP 1004AF)
Brominated bisphenol A type epoxy resin 38g
(Company product EP5051)
Brominated phenol novolac epoxy resin 21g
(Nippon Kayaku product BREN-S)
Carboxyl-modified NBR 39g
(Japan Synthetic Rubber Product PNR-1H)
Resol type modified phenolic resin 5g
(Hitachi Chemical Product HN-643KN)
4,4'-Diaminodiphenylsulfone [4,4'-DDS] 6g
BF 3・ piperidine complex (Hashimoto Kasei products) 0.6g
Methyl ethyl ketone 280g
An adhesive solution having a solid content concentration of about 35% by weight, prepared by uniformly dissolving each of the above components with a ball mill, was prepared with a polyimide film (DuPont product Kapton 100H, thickness, so that the dry coating thickness was 35 μm. 25 μm) and dried at room temperature for 10 minutes and then at 120 ° C. for 2 minutes to form a film having an adhesive layer, and a release protective film was adhered to the adhesive layer.
[0026]
A film having this adhesive layer and a flexible copper-clad laminate on which a test pattern was formed by the subtract method were heated and pressed at 165 ° C., 1 MPa, 5 minutes, and then at 140 ° C. for 2 hours. Post-cure was performed to create a flexible laminated film.
[0027]
About the obtained laminated | multilayer film, the following each item was measured and the coverlay adhesive agent for flexible printed wiring was evaluated.
Figure 0003835090
, Measure the number of days until embedding in a circuit with a wire thickness of 35μm is not possible [0028]
Examples 2-3 and Comparative Examples 1-9
In Example 1, the amount of each component (unit: g) other than bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin (100 g in total) is as shown in the following Table 1. Changed to
[0029]
Vamac G is an ethylene-unsaturated carboxylic acid copolymer produced by DuPont, and GHP-160 is a novolac modified xylene resin produced by Mitsubishi Gas Chemical.
Figure 0003835090
[0030]
The measurement results in the above examples and comparative examples are shown in the following Table 2.
Figure 0003835090
[0031]
From the above results, the following can be said.
(1) The adhesive for a flexible printed wiring board according to the present invention has good adhesion, solder heat resistance and storage stability, and no copper migration is observed.
(2) In Comparative Example 1 in which the amount of carboxyl-modified rubber is too large, copper migration occurs, while in Comparative Example 2 in which the amount is too small, the peel strength (adhesiveness) is lowered.
(3) In Comparative Example 3 in which the amount of the resol-modified phenol resin is too small, the storage stability is lowered, whereas in Comparative Example 4 in which the amount is too much, the peel strength (adhesiveness) is lowered.
(4) In Comparative Example 5 and Comparative Example 6 in which the amount of aromatic diamine is too small, both the solder heat resistance and the peel strength (adhesiveness) are lowered.
(5) In Comparative Example 8 in which the amount of boron trifluoride complex is too small, copper migration occurs, and in Comparative Example 9 in which the amount is too large, storage stability is lowered. (6) In Comparative Example 7 in which a novolac type modified xylene resin was used instead of the resol type modified phenolic resin, the storage stability was lowered.

Claims (3)

エポキシ樹脂100重量部、カルボキシル変性合成ゴム20〜110重量部、レゾール変性フェノール樹脂1〜50重量部、芳香族ジアミン2〜20重量部および三フッ化ホウ素錯体0.02〜2.5重量部を必須成分として含有してなるフレキシブル印刷配線板用接着剤。Contains 100 parts by weight of epoxy resin, 20-110 parts by weight of carboxyl-modified synthetic rubber, 1-50 parts by weight of resole-modified phenolic resin, 2-20 parts by weight of aromatic diamine and 0.02-2.5 parts by weight of boron trifluoride complex as essential components An adhesive for flexible printed wiring boards. 有機溶媒溶液として調製された請求項1記載のフレキシブル印刷配線板用接着剤。The adhesive for flexible printed wiring boards according to claim 1, which is prepared as an organic solvent solution. カバーレイ用接着剤として用いられる請求項1または2記載のフレキシブル印刷配線板用接着剤。The adhesive for flexible printed wiring boards according to claim 1 or 2, which is used as an adhesive for coverlay.
JP34967499A 1999-12-09 1999-12-09 Adhesive for flexible printed wiring boards Expired - Fee Related JP3835090B2 (en)

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JP2004146754A (en) * 2002-10-22 2004-05-20 Hitachi Kasei Polymer Co Ltd Adhesive composition for flexible printed wiring board lamination and adhesion film
JP4526783B2 (en) * 2003-04-23 2010-08-18 日立化成ポリマー株式会社 Adhesive composition for laminating flexible printed wiring board and adhesive film
JP2004323810A (en) * 2003-04-23 2004-11-18 Hitachi Kasei Polymer Co Ltd Adhesive composition for flexible printed wiring board, and adhesive film
JP2004323807A (en) * 2003-04-23 2004-11-18 Hitachi Kasei Polymer Co Ltd Flame retardant adhesive composition and cover lay
JP2006165495A (en) * 2004-05-18 2006-06-22 Mitsui Chemicals Inc Adhesive resin composite and its use
EP1754721A1 (en) 2005-08-16 2007-02-21 Sika Technology AG Amino groups terminated tougheners, their derivatives and their use
JP2007238707A (en) * 2006-03-07 2007-09-20 Fujikura Ltd Epoxy-based adhesive, coverlay, prepreg, metal-clad laminated plate and printed circuit substrate plate
JP5314874B2 (en) * 2007-10-05 2013-10-16 ナミックス株式会社 Sealant for protective film layer
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KR102578455B1 (en) * 2022-08-31 2023-09-14 (주)이녹스첨단소재 A thermosetting adhesive film having a high glass transition temperature and a coverlay film comprising the same

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