JP4841337B2 - Primer resin and resin composition for primer resin layer - Google Patents
Primer resin and resin composition for primer resin layer Download PDFInfo
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- JP4841337B2 JP4841337B2 JP2006186592A JP2006186592A JP4841337B2 JP 4841337 B2 JP4841337 B2 JP 4841337B2 JP 2006186592 A JP2006186592 A JP 2006186592A JP 2006186592 A JP2006186592 A JP 2006186592A JP 4841337 B2 JP4841337 B2 JP 4841337B2
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本発明は、銅箔を粗面化処理することなく、銅箔表面に直接ベンゾトリアゾール型エポキシ樹脂または組成物を薄く塗布、乾燥した銅箔を用いることで、ポリイミドフィルム基板等のフレキシブルプリント配線板用の樹脂基板との良好な接着性を確保することができるプライマー樹脂、該プライマー樹脂からなるプライマー樹脂層付銅箔に関する。 The present invention provides a flexible printed wiring board such as a polyimide film substrate by using a copper foil obtained by thinly applying a benzotriazole type epoxy resin or a composition directly on the surface of the copper foil without subjecting the copper foil to a roughening treatment. It is related with the primer resin which can ensure favorable adhesiveness with the resin substrate for water, and the copper foil with a primer resin layer which consists of this primer resin.
通常、ポリイミドフィルムは金属箔（主に銅箔）と張り合わせ、片面、両面フレキシブル銅張積層板として、フレキシブル印刷配線基板用のベース樹脂フィルムや、多層印刷配線基板用層間絶縁樹脂フィルムとして使用される。なかでも２層ＣＣＬといわれる銅張積層板は、ポリイミドフィルムと銅箔が接着剤層を介さず直接張り合わせられており、配線の微細化や基板の耐熱性といった点で非常に有用であるが、一方ではポリイミドフィルムと銅箔との接着強度がしばしば問題となる。２層ＣＣＬの製造方法は、銅箔上にポリイミド前駆体を塗布し、加熱して得るキャスティング法（特許文献１）の他、熱可塑ポリイミドフィルムと銅箔を加熱圧着して得るラミネート法（特許文献２）や、ポリイミドフィルム表面にスパッタ層を設け、銅箔をメッキして得る方法等があるが、現在キャスティング法が主流となっている。
一方、従来のプリント配線板製造に用いられてきた銅箔は、特許文献１を始め多くの文献に開示されているように、その片面に微細な銅粒を付着させる等により凹凸を形成する粗面化処理が施されている。プリプレグ等の基材樹脂との張り合わせを行う際に、銅箔の粗面化処理の凹凸形状が基材樹脂内に埋まり込みアンカー効果を得ることで、銅箔と基材樹脂との密着性を得てきたのである。しかし、通常銅箔表面には表面処理剤として防錆剤等のアミン化合物、長鎖アルキル化合物や、シリコーン系化合物が塗布されているため、このままキャスティング法でポリイミド前駆体を塗布すると得られる２層ＣＣＬの銅箔／ポリイミド樹脂の剥離強度は低下する。また、脱脂工程やソフトエッチングといった煩雑な工程を経て表面処理剤を除去した銅箔表面は、大気やポリイミド前駆体にさらされるため腐食酸化されるといった問題が挙げられる。さらに、粗面化処理や防錆処理等の表面処理を全く施していない未処理の銅箔においては、接着強度が問題となるばかりか、接着強度向上は技術的に困難で、プライマー樹脂に耐熱性エポキシ樹脂組成物を用いた例（特許文献５）はあるが、顕著な改善は見られず、接着強度および耐熱性に問題が残る。
Usually, a polyimide film is laminated with a metal foil (mainly copper foil) and used as a single-sided or double-sided flexible copper-clad laminate as a base resin film for flexible printed wiring boards or an interlayer insulating resin film for multilayer printed wiring boards. . Among them, the copper clad laminate called two-layer CCL is very useful in terms of miniaturization of wiring and heat resistance of the substrate, since the polyimide film and the copper foil are directly bonded without an adhesive layer. On the other hand, the adhesive strength between the polyimide film and the copper foil often becomes a problem. The two-layer CCL is manufactured by applying a polyimide precursor on a copper foil and heating it (Patent Document 1), as well as a lamination method (patent document 1) obtained by thermocompression bonding a thermoplastic polyimide film and a copper foil. There are methods such as literature 2) and a method in which a sputter layer is provided on the surface of a polyimide film and copper foil is plated, but the casting method is currently the mainstream.
On the other hand, as disclosed in many documents including Patent Document 1, a copper foil that has been used for manufacturing a conventional printed wiring board has a rough surface that forms irregularities by attaching fine copper particles to one surface thereof. Surface treatment is applied. When bonding with a base resin such as a prepreg, the uneven shape of the roughening treatment of the copper foil is embedded in the base resin to obtain an anchor effect, thereby improving the adhesion between the copper foil and the base resin. It has been obtained. However, since the surface of the copper foil is usually coated with an amine compound such as a rust inhibitor, a long-chain alkyl compound, or a silicone compound as a surface treatment agent, the two layers obtained by applying the polyimide precursor by the casting method as it is The peel strength of the CCL copper foil / polyimide resin decreases. Moreover, since the copper foil surface from which the surface treatment agent has been removed through complicated steps such as a degreasing step and soft etching is exposed to the air or a polyimide precursor, it is corroded and oxidized. Furthermore, untreated copper foil that has not undergone any surface treatment such as roughening treatment or rust prevention treatment is not only problematic in terms of adhesion strength, but it is technically difficult to improve the adhesion strength, and the primer resin is heat resistant. Although there is an example (Patent Document 5) using a conductive epoxy resin composition, no remarkable improvement is observed, and problems remain in adhesive strength and heat resistance.
粗面化処理していない銅箔をプリント配線板製造に用いることができれば、銅箔の粗面化処理工程を省略することが可能となり、生産コストの大幅な低減が可能である。また、回路エッチングにおいて粗面化処理部分を溶解するためのオーバーエッチングタイムを設ける必要がなくなりトータルエッチングコストの削減も可能である。 If a copper foil that has not been roughened can be used in the production of a printed wiring board, the copper foil roughening treatment step can be omitted, and the production cost can be greatly reduced. Further, it is not necessary to provide an over-etching time for dissolving the roughened portion in circuit etching, and the total etching cost can be reduced.
また、粗面化処理を施していない銅箔をプリント配線板に用いることは、粗面化部分の厚みが無くなることで、より微細な配線パターンの形成が可能となり、配線表面の電気抵抗も小さくなるため、非常に有用であり、粗面化処理を施していない銅箔をプリント配線板の製造に用いることができれば、製造コストの削減と性能の向上といった両方の面で好ましい。 In addition, the use of copper foil that has not been subjected to roughening treatment for the printed wiring board makes it possible to form a finer wiring pattern by reducing the thickness of the roughened portion, and to reduce the electrical resistance of the wiring surface. Therefore, it is very useful, and if a copper foil that has not been subjected to a roughening treatment can be used in the production of a printed wiring board, it is preferable in terms of both reduction in production cost and improvement in performance.
本発明は、銅箔を粗面化処理することなく、キャスティング法で得られるフレキシブルプリント配線板用の樹脂基板において、銅箔／ポリイミド樹脂間の良好な接着性を確保することができるプライマー樹脂、及びプライマー樹脂層付銅箔を提供することを目的とする。 In the resin substrate for flexible printed wiring boards obtained by the casting method without roughening the copper foil, the present invention is a primer resin that can ensure good adhesion between the copper foil / polyimide resin, And it aims at providing the copper foil with a primer resin layer.
本発明者らは、上記課題を解決するため、鋭意研究の結果、本発明を完成した。 In order to solve the above problems, the present inventors have completed the present invention as a result of intensive studies.
すなわち本発明は
（１）粗面化処理の施されていない銅箔と樹脂基材との接着性を確保するためのプライマー樹脂層用樹脂であって、下記式（１）
（２）式（１）におけるＲ１、Ｒ２のうち少なくとも一方が、オキシグリシジル基である上記（１）記載のプライマー樹脂
（３）上記（１）または（２）に記載のプライマー樹脂が硬化剤および硬化促進剤を含有してなることを特徴とするプライマー樹脂層用樹脂組成物
（４）上記（１）もしくは（２）に記載のプライマー樹脂、または上記（３）記載のプライマー樹脂層用樹脂組成物がＮ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、メチルエチルケトン、メチルイソブチルケトンまたはメチルベンゾエートより選ばれる１種以上を含有する溶媒にさせ溶液を調製し、次いでこの溶液を銅箔上に塗布乾燥し、プライマー樹脂層を形成させることを特徴とする、プライマー樹脂層の形成方法
（５）上記（４）記載の形成方法により得られたプライマー樹脂層を備えたフレキシブルプリント配線板用の銅張り積層板
（６）粗面化処理の施されていない銅箔の表面粗さ（Ｒｚ）が２μｍ以下である面に上記（４）記載の形成方法により得られたプライマー樹脂層を備えていることを特徴とするプライマー樹脂層付銅箔
（７）プライマー樹脂層を設けた銅箔の表面が、ニッケル、鉄、亜鉛、金、錫より選ばれる１種以上のメッキ層を備えた面である上記（６）に記載のプライマー樹脂層付銅箔
（８）プライマー樹脂層を設けた銅箔またはメッキの表面が、シランカップリング剤層を備えた面である上記（６）または（７）に記載のプライマー樹脂層付銅箔
に関する。
That is, the present invention is (1) a resin for a primer resin layer for ensuring adhesion between a copper foil that has not been subjected to a roughening treatment and a resin base material, and the following formula (1)
本発明のプライマー樹脂は、無機金属である銅箔への接着強度に優れる。また、銅箔を腐食させることなく防錆処理剤としても効果がある。さらにフレキシブルプリント配線板用の銅張り積層板において、ポリイミド前駆体溶液を用い樹脂フィルムを得る場合においても、本発明のプライマー樹脂とポリイミド樹脂フィルムとの接着強度も高くなる。したがって本発明のプライマー樹脂及びプライマー樹脂層付銅箔は、電気基板等、電気材料分野で極めて有用である。 The primer resin of this invention is excellent in the adhesive strength to the copper foil which is an inorganic metal. It is also effective as a rust preventive agent without corroding the copper foil. Further, in the case of obtaining a resin film using a polyimide precursor solution in a copper-clad laminate for a flexible printed wiring board, the adhesive strength between the primer resin of the present invention and the polyimide resin film is also increased. Therefore, the primer resin and the copper foil with a primer resin layer of the present invention are extremely useful in the field of electrical materials such as electrical substrates.
本発明のプライマー樹脂は、下記式（１） The primer resin of the present invention has the following formula (1)
で表されるベンゾトリアゾール型エポキシ樹脂であれば特に制限はない。式（１）中Ｒ１はグリシジル基を含有する有機基を表し、例えばオキシグリシジル基、チオグリシジル基、オキシパーフルオログリシジル記、グリシジルカルボキシレート基、グリシジルアミノ基等が挙げられる。またＲ２はグリシジル基を含有する１価の有機基またはＯ、Ｓ、Ｆ、Ｎを含んでもよい炭素数１〜６の有機基を表し、前記グリシジル基を含有する有機基の他、Ｏ、Ｓ、Ｆ、Ｎを含んでもよい炭素数１〜６の有機基として、例えばメチル基、エチル基、プルピル基、ブチル基等の鎖状アルキル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等の環状アルキル基、トリフルオロメチル基、ヘキサフルオロエチル基等のパーフルオロアルキル基、メトキシ基、エトキシ基等のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基等のジアルキルアミノ基が挙げられる。式（１）の化合物において、Ｒ１、Ｒ２のうち少なくとも一方が、オキシグリシジル基である化合物が好ましく、中でも式（２） If it is the benzotriazole type epoxy resin represented by these, there will be no restriction | limiting in particular. In formula (1), R 1 represents an organic group containing a glycidyl group, and examples thereof include an oxyglycidyl group, a thioglycidyl group, an oxyperfluoroglycidyl group, a glycidylcarboxylate group, and a glycidylamino group. R 2 represents a monovalent organic group containing a glycidyl group or an organic group having 1 to 6 carbon atoms which may contain O, S, F, and N. In addition to the organic group containing the glycidyl group, O, Examples of the organic group having 1 to 6 carbon atoms that may contain S, F, and N include, for example, a chain alkyl group such as methyl group, ethyl group, purpyl group, and butyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. And a cyclic alkyl group such as trifluoromethyl group and hexafluoroethyl group, an alkoxy group such as methoxy group and ethoxy group, and a dialkylamino group such as dimethylamino group and diethylamino group. In the compound of the formula (1), a compound in which at least one of R 1 and R 2 is an oxyglycidyl group is preferable.
より選ばれる１種または２種の化合物が好ましい。 1 type or 2 types of compounds chosen from more are preferable.
本発明のプライマー樹脂は、通常下記式（３） The primer resin of the present invention is usually represented by the following formula (3)
（式（１）中Ｒ３は−ＯＨ、−ＳＨ、または−ＮＨ２を有する有機基を表し、Ｒ２は−ＯＨ、−ＳＨ、または−ＮＨ２を有する有機基またはＯ、Ｓ、Ｆ、Ｎを含んでもよい炭素数１〜６の有機基をそれぞれ表す。）で表されるベンゾトリアゾール化合物と、エピクロロヒドリンとの反応により得られる。反応は通常、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、メチルエチルケトン、またはメチルイソブチルケトンより選ばれる１種以上を含有する溶媒中で行うことができる。 (In Formula (1), R 3 represents an organic group having —OH, —SH, or —NH 2 , and R 2 represents an organic group having —OH, —SH, or —NH 2 , or O, S, F, Each represents an organic group having 1 to 6 carbon atoms which may contain N.) and a reaction with epichlorohydrin. The reaction is usually carried out in a solvent containing one or more selected from N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, or methyl isobutyl ketone. it can.
溶媒中での反応は、ベンゾトリアゾール化合物を溶媒に対し２０〜８０重量％溶解した溶液に、反応量に対し１．５〜６倍過剰のエピクロロヒドリンを添加し、反応するのが好ましく、このとき発生する塩化水素を中和するため、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等の無機アルカリ成分の他、トリエチルアミン、ピリジン等の塩基性有機化合物を添加するとよい。添加量は発生し得る塩化水素量に対し、１〜１．５モル当量が好ましい。反応温度は、４０〜８０℃が好ましい。反応時間は１〜５時間が好ましい。 The reaction in the solvent is preferably carried out by adding 1.5 to 6 times excess epichlorohydrin to the reaction amount in a solution obtained by dissolving 20 to 80% by weight of the benzotriazole compound in the solvent, In order to neutralize the hydrogen chloride generated at this time, in addition to inorganic alkali components such as sodium hydroxide, potassium hydroxide and calcium hydroxide, basic organic compounds such as triethylamine and pyridine may be added. The amount added is preferably 1 to 1.5 molar equivalents relative to the amount of hydrogen chloride that can be generated. The reaction temperature is preferably 40 to 80 ° C. The reaction time is preferably 1 to 5 hours.
反応終了後、発生する塩酸塩等の不溶解分は濾過、水洗等により除去し、分液洗浄後乾燥し、本発明のプライマー樹脂を単離することができる。 After completion of the reaction, the insoluble matter such as generated hydrochloride can be removed by filtration, washing with water, etc., and after separation and washing, the primer resin of the present invention can be isolated.
本発明のプライマー樹脂層用樹脂組成物は、上記ベンゾトリアゾール型エポキシ樹脂の他に硬化剤および硬化促進剤を含有していれば特に制限は無い。好ましい硬化剤としては、カヤハードＧＰＨ６５（水酸基当量２０３ｇ／ｅｑ 日本化薬製）、ザイロックＸＬＣ−３Ｌ（水酸基当量１７３ｇ／ｅｑ 三井化学製）等のフェノール樹脂や、カヤフレックスＣＰＡＭ−７５０（水酸基当量５０００ｇ／ｅｑ 日本化薬製）、カヤフレックスＢＰＡＭ−２５０（水酸基当量５０００ｇ／ｅｑ 日本化薬製）等の反応性芳香族ポリアミド樹脂が挙げられる。その配合量は、プライマー樹脂のエポキシ当量に対し、硬化剤の当量が１．２倍以下となる様、調整するのが好ましい。また、好ましい硬化促進剤として、２−メチルイミダゾール（キュアゾール２ＭＺ、四国化成工業製）、２−エチル−４−メチルイミダゾール（２Ｅ４ＭＺ、四国化成工業製）、２−フェニル−４，５−ジヒドロキシメチルイミダゾール（２ＰＨＺ−ＰＷ、四国化成工業製）等のイミダゾール系促進剤や、トリフェニルホスフィン（ＴＰＰ、北興化学製）、トリ−ｏ−トリルホスフィン（ＴＯＴＰ、北興化学製）等のりん系促進剤の他、ＥＰＣＡＴ−Ｐ（活性物質担持量２０重量％ 日本化薬製）、ＥＰＣＡＴ−ＰＳ５（活性物質担持量２０重量％ 日本化薬製）等のマイクロカプセル型潜在性硬化促進剤等が挙げられる。その配合量は、プライマー樹脂に対し、イミダゾール系促進剤およびりん系促進剤の場合０．２〜２重量％、マイクロカプセル型潜在性硬化促進剤の場合１〜１０重量％が好ましい。 The resin composition for a primer resin layer of the present invention is not particularly limited as long as it contains a curing agent and a curing accelerator in addition to the benzotriazole type epoxy resin. Preferred curing agents include phenolic resins such as Kayahard GPH65 (hydroxyl equivalent: 203 g / eq, manufactured by Nippon Kayaku Co., Ltd.), Zylox XLC-3L (hydroxyl group equivalent: 173 g / eq, manufactured by Mitsui Chemicals), and Kayaflex CPAM-750 (hydroxyl equivalent: 5000 g / eq Nippon Kayaku Co., Ltd.), Kayaflex BPAM-250 (hydroxyl group equivalent 5000 g / eq Nippon Kayaku Co., Ltd.) and other reactive aromatic polyamide resins. The blending amount is preferably adjusted so that the equivalent of the curing agent is 1.2 times or less with respect to the epoxy equivalent of the primer resin. Further, as preferred curing accelerators, 2-methylimidazole (Cureazole 2MZ, manufactured by Shikoku Kasei Kogyo), 2-ethyl-4-methylimidazole (2E4MZ, manufactured by Shikoku Kasei Kogyo), 2-phenyl-4,5-dihydroxymethylimidazole Other than imidazole accelerators such as 2PHZ-PW (manufactured by Shikoku Kasei Kogyo) and phosphorus accelerators such as triphenylphosphine (TPP, manufactured by Hokuko Chemical) and tri-o-tolylphosphine (TOTP, manufactured by Hokuko Chemical) And microcapsule type latent curing accelerators such as EPCAT-P (active substance loading 20% by weight Nippon Kayaku) and EPCAT-PS5 (active substance loading 20% by weight Nippon Kayaku). The blending amount is preferably 0.2 to 2% by weight in the case of imidazole accelerators and phosphorus accelerators, and 1 to 10% by weight in the case of microcapsule type latent curing accelerators with respect to the primer resin.
本発明のプライマー樹脂組成物は、得られるプライマー樹脂層の銅箔およびポリイミド樹脂への接着強度と、銅箔の防錆効果を損ねない範囲内で、種々の添加剤を加えることができる。これら添加剤としては、例えば、ポリイミド樹脂、芳香族ポリアミド樹脂、エポキシ樹脂、フェノール樹脂等の有機添加剤、またはシリカ化合物等の無機添加剤、顔料、染料、ハレーション防止剤、蛍光増白剤、界面活性剤、レベリング剤、可塑剤、難燃剤、酸化防止剤、充填剤、静電防止剤、粘度調整剤、イミド化触媒、促進剤、脱水剤、イミド化遅延剤、光安定剤、光触媒、低誘電体、導電体、磁性体や、熱分解性化合物等が挙げられる。 Various additives can be added to the primer resin composition of the present invention within a range that does not impair the adhesion strength of the resulting primer resin layer to the copper foil and polyimide resin and the rust preventive effect of the copper foil. Examples of these additives include organic additives such as polyimide resins, aromatic polyamide resins, epoxy resins and phenol resins, or inorganic additives such as silica compounds, pigments, dyes, antihalation agents, fluorescent whitening agents, interfaces. Activator, leveling agent, plasticizer, flame retardant, antioxidant, filler, antistatic agent, viscosity modifier, imidation catalyst, accelerator, dehydrating agent, imidization retarder, light stabilizer, photocatalyst, low Examples include dielectrics, conductors, magnetic substances, and thermally decomposable compounds.
本発明のプライマー樹脂層の形成方法は、粗化処理の施されていない銅箔の片面にプライマー樹脂またはプライマー樹脂層用樹脂組成物を、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、メチルエチルケトン、メチルイソブチルケトンまたはメチルベンゾエートから選ばれる１種以上の溶媒に溶解し、この溶液をプライマー樹脂層として固形分換算厚さが１〜１０μｍとなる様、塗布乾燥する方法である。例えばベンゾトリアゾール型エポキシ樹脂他固形分２０重量％のプライマー樹脂溶液またはプライマー樹脂層用樹脂組成物溶液を１０μｍ厚に塗布し、８０〜２００℃で５〜６０分、好ましくは１３０〜１５０℃で１０〜３０分乾燥させることにより、およそ２μｍ厚のプライマー樹脂層が得られる。このように溶媒の使用量は塗布する時の粘度と所望するプライマー樹脂層の厚さにより適宜決定すればよく、前記溶液中の固形分（溶媒以外の成分）濃度が、通常５〜５０重量％、好ましくは１０〜３０重量％である。
乾燥時の熱源は熱風でも遠赤外線ヒーターでもよいが、溶媒蒸気の滞留防止および樹脂内部までの熱伝導の点で、熱風と遠赤外線ヒーターを併用するとよい。乾燥温度は、溶媒を除去するのに必要な温度（プライマー樹脂と硬化剤との硬化反応を伴う場合は、硬化反応に必要な温度）であれば特に制限はなく、通常８０〜２００℃、好ましくは１２０〜１８０℃である。
The method for forming a primer resin layer of the present invention comprises a primer resin or a resin composition for a primer resin layer on one side of a copper foil that has not been subjected to a roughening treatment, and N-methyl-2-pyrrolidone, N, N-dimethylacetamide. , N, N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone or methyl benzoate is dissolved in one or more solvents, and this solution is used as a primer resin layer so that the thickness in terms of solid content becomes 1 to 10 μm It is a method of applying and drying. For example, a primer resin solution having a solid content of 20% by weight or a resin composition solution for a primer resin layer having a solid content of 20% by weight is applied to a thickness of 10 μm, and it is 5 to 60 minutes at 80 to 200 ° C., preferably 10 to 130 to 150 ° C. By drying for ˜30 minutes, a primer resin layer having a thickness of about 2 μm is obtained. Thus, the amount of the solvent used may be appropriately determined depending on the viscosity at the time of coating and the desired thickness of the primer resin layer, and the solid content (components other than the solvent) concentration in the solution is usually 5 to 50% by weight. , Preferably 10 to 30% by weight.
The heat source during drying may be hot air or a far-infrared heater, but hot air and a far-infrared heater may be used in combination from the standpoint of preventing solvent vapor from staying and conducting heat to the inside of the resin. The drying temperature is not particularly limited as long as it is a temperature necessary for removing the solvent (a temperature necessary for the curing reaction when a curing reaction between the primer resin and the curing agent is involved), and usually 80 to 200 ° C., preferably Is 120-180 ° C.
本発明のプライマー樹脂またはプライマー樹脂と硬化剤の反応生成物を主成分とするプライマー樹脂層を備えたフレキシブルプリント配線板用の銅張り積層板は、銅箔と樹脂基板との間に上記プライマー樹脂層が介在するフレキシブルプリント配線板用の銅張り積層板であり、銅箔および樹脂基板双方への接着強度が１Ｎ／ｍｍであることが好ましい。 A copper-clad laminate for a flexible printed wiring board comprising a primer resin or a primer resin layer mainly composed of a reaction product of a primer resin and a curing agent according to the present invention, the primer resin between the copper foil and the resin substrate. It is a copper-clad laminate for a flexible printed wiring board in which a layer is interposed, and the adhesive strength to both the copper foil and the resin substrate is preferably 1 N / mm.
本発明のプライマー樹脂層付銅箔は、上記プライマー樹脂層の形成方法において用いる粗面化処理の施されていない銅箔の表面粗さ（Ｒｚ）が２μｍ以下である銅箔、本銅箔表面にニッケル、鉄、亜鉛、金、錫より選ばれる１種以上のメッキ層を備えた銅箔、および／またはシランカップリング剤層を備えた銅箔を用いることによって得られる。 The copper foil with a primer resin layer of the present invention is a copper foil having a surface roughness (Rz) of 2 μm or less, which is not subjected to the roughening treatment used in the method for forming a primer resin layer, and the surface of the present copper foil. And a copper foil provided with one or more plating layers selected from nickel, iron, zinc, gold and tin, and / or a copper foil provided with a silane coupling agent layer.
銅箔表面のメッキ層はニッケル、鉄、亜鉛、金、錫より選ばれる１種以上がイオン化した溶液中での電解または無電解メッキにより得られ、厚みは１０〜３００ｎｍが好ましい。用い得るシランカップリング剤は、アミノ系、エポキシ系他、市販されている種々のシランカップリング剤（ＫＢＭシリーズ 信越化学製）を用いることで得られ、厚みは１〜５０ｎｍが好ましい。 The plating layer on the surface of the copper foil is obtained by electrolysis or electroless plating in a solution in which one or more selected from nickel, iron, zinc, gold and tin are ionized, and the thickness is preferably 10 to 300 nm. The silane coupling agent that can be used is obtained by using various silane coupling agents (KBM series manufactured by Shin-Etsu Chemical Co., Ltd.) that are commercially available, such as amino-based, epoxy-based, etc., and the thickness is preferably 1 to 50 nm.
以下に実施例によって本発明を更に詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
なお、実施例中のフィルムの特性測定方法は以下の通りである。
（銅箔との接着強度の測定）
プライマー樹脂層を形成させた銅箔上に、下記式（４）
In addition, the characteristic measuring method of the film in an Example is as follows.
(Measurement of adhesive strength with copper foil)
On the copper foil on which the primer resin layer is formed, the following formula (4)
（式（４）中ｘは繰り返し数であり、全体の重量平均分子量は８１０００である。）で表されるポリイミド前駆体をＮ−メチル−２−ピロリドンおよびＮ，Ｎ−ジメチルアセトアミド混合溶媒に溶解したＫＡＹＡＦＬＥＸ ＫＰＩ（ポリイミド前駆体溶液 日本化薬製）を所定の厚さに塗布乾燥後加熱閉環反応を行い、得られた片面銅箔付きフィルムの銅箔側に１０ｍｍ幅のパターンをマスクして形成させ、フィルム側をボンディングシートにより０．３×７０×１５０ｍｍの鉄板（キャンスーパー パルテック製）に貼り付け、１０ｍｍ幅の銅箔の端をカッターナイフで樹脂から剥がし、テンシロン試験機（ＡアンドＤ：オリエンテック製）を用いて、１８０°方向での銅箔と樹脂との接着強度を測定した。 (In formula (4), x is the number of repetitions, and the total weight average molecular weight is 81,000.) The polyimide precursor represented by the formula is dissolved in a mixed solvent of N-methyl-2-pyrrolidone and N, N-dimethylacetamide. KAYAFLEX KPI (polyimide precursor solution manufactured by Nippon Kayaku Co., Ltd.) is applied to a predetermined thickness, dried and then subjected to a heat ring closure reaction, and a 10 mm wide pattern is masked on the copper foil side of the obtained film with copper foil on one side. The film side was attached to a 0.3 × 70 × 150 mm iron plate (made by Cansuper Partec) with a bonding sheet, and the end of the 10 mm wide copper foil was peeled off from the resin with a cutter knife. Tensilon tester (A and D: (Orientec) was used to measure the adhesive strength between the copper foil and the resin in the 180 ° direction.
合成実施例１
温度計、冷却管、撹拌装置を取り付けた４径フラスコにベンゾトリアゾール化合物であるＤＡＩＮＳＯＲＢ Ｔ−０（２−（２，４−ジヒドロキシフェニル）−２Ｈ−ベンゾトリアゾール 分子量２２７．２２ 水酸基当量１１３．６ｇ/ｅｑ 大和化成製）を１１３．６ｇ、エピクロルヒドリン４６３ｇ、およびジメチルスルホキシド（ＤＭＳＯ）２３２ｇを仕込み５０℃で溶解した、更に撹拌下に窒素ガスを導入しながらフレーク状水酸化ナトリウム（純分９９％）４２ｇを２時間で添加した。添加終了後６０℃で１時間、７０℃で１時間、８０℃で３０分間反応させた。反応終了後、水３００ｇ、３０％リン酸水素２ナトリウム水溶液３０ｇ加え水洗し、水層は分離除去し、油層を加熱減圧下過剰のエピクロルヒドリンを留去した。次いで４２０ｇのメチルイソブチルケトン（ＭＩＢＫ）を加え残留物を溶解させた。
Synthesis Example 1
DAINSORB T-0 (2- (2,4-dihydroxyphenyl) -2H-benzotriazole), which is a benzotriazole compound, is attached to a 4-diameter flask equipped with a thermometer, a condenser, and a stirrer. Molecular weight 227.22 Hydroxyl equivalent 113.6 g / eq Daiwa Kasei) 113.6 g, epichlorohydrin 463 g and dimethyl sulfoxide (DMSO) 232 g were charged and dissolved at 50 ° C., and flaky sodium hydroxide (99% pure content) 42 g while introducing nitrogen gas with stirring. Was added in 2 hours. After the addition, the reaction was carried out at 60 ° C. for 1 hour, 70 ° C. for 1 hour, and 80 ° C. for 30 minutes. After completion of the reaction, 300 g of water and 30 g of a 30% aqueous solution of disodium hydrogen phosphate were added and washed with water, the aqueous layer was separated and removed, and the excess epichlorohydrin was distilled off under heating and reduced pressure. 420 g of methyl isobutyl ketone (MIBK) was then added to dissolve the residue.
このメチルイソブチルケトンの溶液を７０℃に加熱し撹拌下、３０重量％の水酸化ナトリウム水溶液７ｇを添加し１時間反応させた後、水洗を繰り返し、ｐＨを中性とした。更に水層は分離除去し、加熱減圧下過剰のメチルイソブチルケトンを留去し、下記式（５） The methyl isobutyl ketone solution was heated to 70 ° C. and stirred, 7 g of a 30 wt% aqueous sodium hydroxide solution was added and reacted for 1 hour, followed by repeated washing with water to neutralize the pH. Further, the aqueous layer was separated and removed, and excess methyl isobutyl ketone was distilled off under reduced pressure by heating.
で表される黒色半固形のベンゾトリアゾール型２官能エポキシ樹脂（本発明のプライマー樹脂）１６１ｇを得た。エポキシ当量は１９２ｇ/ｅｑ、軟化点４９．７℃、１５０℃に於けるＩＣＩ粘度０．４Ｐａ・ｓであった。
161 g of a black semi-solid benzotriazole type bifunctional epoxy resin (primer resin of the present invention) represented by the formula: The epoxy equivalent was 192 g / eq, the softening point was 49.7 ° C., and the ICI viscosity was 0.4 Pa · s at 150 ° C.
合成実施例２
温度計、冷却管、撹拌装置を取り付けた４径フラスコにベンゾトリアゾール化合物であるＤＡＩＮＳＯＲＢ Ｔ−１（２−ヒドロキシ−５−メチルフェニル）−２Ｈ−ベンゾトリアゾール 分子量２２５．２５ 水酸基当量２２５．３ｇ/ｅｑ 大和化成製）を２２５．３ｇ、エピクロルヒドリン４６３ｇ、ジメチルスルホキシド（ＤＭＳＯ）２３２ｇを仕込み５０℃で溶解した、更に撹拌下に窒素ガスを導入しながらフレーク状水酸化ナトリウム（純分９９％）４２ｇを２時間で添加した。添加終了後６０℃で１時間、７０℃で１時間、８０℃で３０分間反応させた。反応終了後、水３００ｇ、３０％リン酸水素２ナトリウム水溶液３０ｇ加え水洗し、水層は分離除去し、油層を加熱減圧下過剰のエピクロルヒドリンを留去した。次いで６００ｇのメチルイソブチルケトン（ＭＩＢＫ）を加え残留物を溶解させた。
Synthesis Example 2
DAINSORB T-1 (2-hydroxy-5-methylphenyl) -2H-benzotriazole, a benzotriazole compound, is attached to a 4-diameter flask equipped with a thermometer, a condenser, and a stirrer. Molecular weight: 225.25 Hydroxyl equivalent: 225.3 g / eq 225.3 g of Daiwa Kasei), 463 g of epichlorohydrin and 232 g of dimethyl sulfoxide (DMSO) were added and dissolved at 50 ° C. Further, 42 g of flaky sodium hydroxide (99% pure) was added while introducing nitrogen gas with stirring. Added over time. After the addition, the reaction was carried out at 60 ° C. for 1 hour, 70 ° C. for 1 hour, and 80 ° C. for 30 minutes. After completion of the reaction, 300 g of water and 30 g of a 30% aqueous solution of disodium hydrogen phosphate were added and washed with water, the aqueous layer was separated and removed, and the excess epichlorohydrin was distilled off under heating and reduced pressure. 600 g of methyl isobutyl ketone (MIBK) was then added to dissolve the residue.
更に、このメチルイソブチルケトンの溶液を７０℃に加熱し撹拌下、３０重量％の水酸化ナトリウム水溶液７ｇを添加し１時間反応させた後、水洗を繰り返し、ｐＨを中性とした。更に水層は分離除去し、加熱減圧下過剰のメチルイソブチルケトンを留去し、下記式（６） Further, this methyl isobutyl ketone solution was heated to 70 ° C., and 7 g of a 30% by weight sodium hydroxide aqueous solution was added and reacted for 1 hour with stirring, followed by repeated washing with water to neutralize the pH. Further, the aqueous layer was separated and removed, and the excess methyl isobutyl ketone was distilled off under reduced pressure by heating.
で表される黒色液状のベンゾトリアゾール型単官能エポキシ樹脂（本発明のプライマー樹脂）２７０ｇ得た。エポキシ当量は２９０ｇ/ｅｑ、１５０℃に於けるＩＣＩ粘度０．０５Ｐａ・ｓであった。
270 g of a black liquid benzotriazole type monofunctional epoxy resin (primer resin of the present invention) represented by The epoxy equivalent was 290 g / eq, and the ICI viscosity at 150 ° C. was 0.05 Pa · s.
実施例１
合成実施例１で得られたベンゾトリアゾール型エポキシ樹脂３．４８ｇをＮ，Ｎ−ジメチルホルムアミド５０ｇに溶解させ、硬化剤としてカヤフレックスＣＰＡＭ−７５０（水酸基当量５０００ｇ／ｅｑ 日本化薬製）を３０ｇと、硬化促進剤として２ＰＨＺ−ＰＷ（イミダゾール系促進剤 四国化成）を０．０３５ｇ添加し、撹拌溶解させ本発明のプライマー樹脂層用樹脂組成物の溶液を得た。Ｅ型粘度計で測定した溶液粘度は、２５℃で１５０００ｍＰａ・ｓであった。
Example 1
3.48 g of the benzotriazole type epoxy resin obtained in Synthesis Example 1 is dissolved in 50 g of N, N-dimethylformamide, and 30 g of Kayaflex CPAM-750 (hydroxyl group equivalent 5000 g / eq, manufactured by Nippon Kayaku Co., Ltd.) is used as a curing agent. Then, 0.035 g of 2PHZ-PW (imidazole accelerator Shikoku Kasei) was added as a curing accelerator and dissolved by stirring to obtain a solution of the resin composition for a primer resin layer of the present invention. The solution viscosity measured with an E-type viscometer was 15000 mPa · s at 25 ° C.
実施例２
実施例１で得られたプライマー樹脂組成物溶液５０ｇに、希釈のためＮ，Ｎ−ジメチルホルムアミド５０ｇを加え撹拌し、オートマチックアプリケーター（安田精機製作所製）を用い１７μｍ厚の表面粗さ（Ｒｚ）が２μｍ以下である圧延銅箔上に１０μｍ厚で塗布した後、１３０℃×１０分乾燥し本発明の１．４μｍ厚のプライマー樹脂層付銅箔を得た。
Example 2
50 g of the primer resin composition solution obtained in Example 1 was added with 50 g of N, N-dimethylformamide for dilution, and the surface roughness (Rz) of 17 μm was obtained using an automatic applicator (manufactured by Yasuda Seiki Seisakusho). After apply | coating by 10 micrometers thickness on the rolled copper foil which is 2 micrometers or less, it dried at 130 degreeC * 10 minutes, and obtained the copper foil with a primer resin layer of 1.4 micrometers thickness of this invention.
実施例３
合成実施例１で得られたベンゾトリアゾール型エポキシ樹脂５ｇをＮ，Ｎ−ジメチルホルムアミド４５ｇに溶解させた溶液を、オートマチックアプリケーター（安田精機製作所製）を用い１７μｍ厚の表面粗さ（Ｒｚ）が２μｍ以下である圧延銅箔上に２５μｍ厚で塗布した後、１３０℃×１０分乾燥し本発明の２．３μｍ厚のプライマー樹脂層付銅箔を得た。
Example 3
Using a solution obtained by dissolving 5 g of the benzotriazole type epoxy resin obtained in Synthesis Example 1 in 45 g of N, N-dimethylformamide, using an automatic applicator (manufactured by Yasuda Seiki Seisakusho), the surface roughness (Rz) of 17 μm thickness is 2 μm. It apply | coated by 25 micrometers thickness on the following rolled copper foil, Then, it dried at 130 degreeC * 10 minutes, and obtained the copper foil with a primer resin layer of 2.3 micrometers thickness of this invention.
実施例４
実施例３で用いた合成実施例１のベンゾトリアゾール型エポキシ樹脂の代わりに、合成実施例２で得られたベンゾトリアゾール型エポキシ樹脂を用いた以外は実施例３と同様にして、本発明の２．２μｍ厚のプライマー樹脂層付銅箔を得た。
Example 4
In the same manner as in Example 3 except that the benzotriazole type epoxy resin obtained in Synthesis Example 2 was used instead of the benzotriazole type epoxy resin of Synthesis Example 1 used in Example 3, 2 of the present invention was used. A copper foil with a primer resin layer having a thickness of 2 μm was obtained.
実施例６
実施例２で用いた１７μｍ厚の表面粗さ（Ｒｚ）が２μｍ以下である圧延銅箔の代わりに、同銅箔上に１７０ｎｍ厚のニッケルメッキ層が施された銅箔を用いた以外は実施例２と同様にして、本発明の１．４μｍ厚のプライマー樹脂層付ニッケルメッキ銅箔を得た。
Example 6
Instead of the rolled copper foil having a surface roughness (Rz) of 17 μm thickness of 2 μm or less used in Example 2, a copper foil having a nickel plating layer of 170 nm thickness on the copper foil was used. In the same manner as in Example 2, a nickel-plated copper foil with a primer resin layer having a thickness of 1.4 μm according to the present invention was obtained.
実施例７
実施例２で用いた合成実施例１のベンゾトリアゾール型エポキシ樹脂の代わりに、合成実施例２で得られたベンゾトリアゾール型エポキシ樹脂を用いたのと、１７μｍ厚の表面粗さ（Ｒｚ）が２μｍ以下である圧延銅箔の代わりに、同銅箔上に１７０ｎｍ厚のニッケルメッキ層が施された銅箔を用いた以外は実施例２と同様にして、本発明の１．４μｍ厚のプライマー樹脂層付ニッケルメッキ銅箔を得た。
Example 7
Instead of the benzotriazole type epoxy resin of Synthesis Example 1 used in Example 2, the benzotriazole type epoxy resin obtained in Synthesis Example 2 was used, and the surface roughness (Rz) of 17 μm thickness was 2 μm. The 1.4 μm-thick primer resin of the present invention was used in the same manner as in Example 2 except that instead of the rolled copper foil, a copper foil having a 170-nm-thick nickel plating layer formed thereon was used. A nickel-plated copper foil with a layer was obtained.
実施例８
実施例２で得られたプライマー樹脂層付銅箔のプライマー樹脂層側に、ＫＡＹＡＦＬＥＸ ＫＰＩ（ポリイミド前駆体溶液 日本化薬製）をオートマチックアプリケーター（安田精機製作所製）を用い１００μｍ厚で塗布した後、１３０℃×１０分乾燥し、次いで窒素雰囲気下で２時間かけて３５０℃まで昇温し、さらに３５０℃で２時間保持し、その後、室温まで放冷して本発明のフレキシブルプリント配線板用の銅張り積層板を得た。樹脂層は１２μｍ厚であった。
Example 8
After applying KAYAFLEX KPI (polyimide precursor solution made by Nippon Kayaku Co., Ltd.) with an automatic applicator (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) to the primer resin layer side of the copper foil with the primer resin layer obtained in Example 2, Dry at 130 ° C. for 10 minutes, then raise the temperature to 350 ° C. in a nitrogen atmosphere over 2 hours, hold at 350 ° C. for 2 hours, and then cool to room temperature for the flexible printed wiring board of the present invention. A copper clad laminate was obtained. The resin layer was 12 μm thick.
実施例９
実施例３で得られたプライマー樹脂層付銅箔を用い、実施例８と同様にして本発明のフレキシブルプリント配線板用の銅張り積層板を得た。樹脂層は１５μｍ厚であった。
Example 9
Using the copper foil with primer resin layer obtained in Example 3, a copper-clad laminate for a flexible printed wiring board of the present invention was obtained in the same manner as in Example 8. The resin layer was 15 μm thick.
実施例１０
実施例４で得られたプライマー樹脂層付銅箔を用い、実施例８と同様にして本発明のフレキシブルプリント配線板用の銅張り積層板を得た。樹脂層は１３μｍ厚であった。
Example 10
Using the copper foil with a primer resin layer obtained in Example 4, a copper-clad laminate for a flexible printed wiring board of the present invention was obtained in the same manner as in Example 8. The resin layer was 13 μm thick.
実施例１２
実施例６で得られたプライマー樹脂層付ニッケルメッキ銅箔を用い、実施例８と同様にして本発明のフレキシブルプリント配線板用の銅張り積層板を得た。樹脂層は１２μｍ厚であった。
Example 12
Using the nickel-plated copper foil with primer resin layer obtained in Example 6, a copper-clad laminate for a flexible printed wiring board of the present invention was obtained in the same manner as in Example 8. The resin layer was 12 μm thick.
実施例１３
実施例７で得られたプライマー樹脂層付ニッケルメッキ銅箔を用い、実施例８と同様にして本発明のフレキシブルプリント配線板用の銅張り積層板を得た。樹脂層は１４μｍ厚であった。
Example 13
Using the nickel-plated copper foil with primer resin layer obtained in Example 7, a copper-clad laminate for a flexible printed wiring board of the present invention was obtained in the same manner as in Example 8. The resin layer was 14 μm thick.
比較例１
１７μｍ厚の表面粗さ（Ｒｚ）が２μｍ以下である圧延銅箔上にプライマー樹脂層を設けることなく、大気中に暴露した直後と１週間暴露し続けた後とで、表面状態の違いを観測した。
Comparative Example 1
Observation of the difference in surface condition between immediately after exposure to the atmosphere and after exposure for one week without providing a primer resin layer on a rolled copper foil with a surface roughness (Rz) of 17 μm or less. did.
比較例２
１７μｍ厚の表面粗さ（Ｒｚ）が２μｍ以下である圧延銅箔上にプライマー樹脂層を設けることなく、ＫＡＹＡＦＬＥＸ ＫＰＩ−１００（ポリイミド前駆体溶液 日本化薬製）を、オートマチックアプリケーター（安田精機製作所製）を用い１００μｍ厚で塗布した後、１３０℃×１０分乾燥し、次いで窒素雰囲気下で２時間かけて３５０℃まで昇温し、さらに３５０℃で２時間保持し、その後、室温まで放冷して本発明のフレキシブルプリント配線板用の銅張り積層板を得た。樹脂層は１１μｍ厚であった。
Comparative Example 2
Without providing a primer resin layer on a rolled copper foil having a surface roughness (Rz) of 17 μm or less, a KAYAFLEX KPI-100 (polyimide precursor solution manufactured by Nippon Kayaku Co., Ltd.) and an automatic applicator (manufactured by Yasuda Seiki Seisakusho) ) And then dried at 130 ° C. for 10 minutes, then heated to 350 ° C. over 2 hours under a nitrogen atmosphere, further maintained at 350 ° C. for 2 hours, and then allowed to cool to room temperature. Thus, a copper-clad laminate for the flexible printed wiring board of the present invention was obtained. The resin layer was 11 μm thick.
実施例２〜４、６、７および比較例１の銅箔の表面状態を表１に、実施例８〜１０、１２、１３および比較例２の接着強度測定値について結果を表２に示した。 The surface states of the copper foils of Examples 2 to 4, 6, 7 and Comparative Example 1 are shown in Table 1, and the results of the adhesive strength measurement values of Examples 8 to 10, 12, 13 and Comparative Example 2 are shown in Table 2. .
Claims (6)
で表されるベンゾトリアゾール型エポキシ樹脂からなるプライマー樹脂、または
（ｂ）該プライマー樹脂、硬化剤および硬化促進剤を含有してなるプライマー樹脂層用樹脂組成物を、
Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、メチルエチルケトン、メチルイソブチルケトンまたはメチルベンゾエートより選ばれる１種以上を含有する溶媒に溶解させ溶液を調製し、次いでこの溶液を、粗面化処理の施されていないフレキシブルプリント配線板用の銅箔上に塗布乾燥し、プライマー樹脂層を形成させることを特徴とする、プライマー樹脂層の形成方法。 (A) The following formula (1)
A primer resin comprising a benzotriazole type epoxy resin represented by: or (b) a resin composition for a primer resin layer comprising the primer resin, a curing agent and a curing accelerator,
A solution is prepared by dissolving in a solvent containing one or more selected from N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, methyl ethyl ketone, methyl isobutyl ketone or methyl benzoate. Then, this solution is applied and dried on a copper foil for a flexible printed wiring board which has not been subjected to a roughening treatment, thereby forming a primer resin layer.
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| JP5671778B2 (en) * | 2008-03-26 | 2015-02-18 | 日立化成株式会社 | Film-like adhesive for semiconductor sealing, semiconductor device and method for manufacturing the same |
| JP5415799B2 (en) * | 2009-03-27 | 2014-02-12 | 古河電気工業株式会社 | COMPOSITE MATERIAL FOR ELECTRIC AND ELECTRONIC COMPONENT, ELECTRIC AND ELECTRONIC COMPONENT USING THE COMPOSITE MATERIAL, AND METHOD FOR PRODUCING COMPOSITE MATERIAL FOR ELECTRIC AND ELECTRONIC COMPONENT |
| JP5304490B2 (en) * | 2009-07-02 | 2013-10-02 | 東洋紡株式会社 | Laminated body and method for producing the same |
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