JP2005238617A - Metal clad laminated sheet and printed wiring board - Google Patents
Metal clad laminated sheet and printed wiring board Download PDFInfo
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本発明は、金属張積層板およびプリント配線板に関する。 The present invention relates to a metal-clad laminate and a printed wiring board.
フレキシブルプリント配線板は薄く、軽く、屈曲性に優れることから、特に携帯電話、ＰＤＡ、液晶ドライバーモジュールを始めとしてモバイル機器を中心に利用されているが、近年、これら電子機器の高性能化、小型化に伴いフレキシブルプリント配線板への配線の微細化、高密度実装化、耐屈曲性などがますます要求されてきている。 Flexible printed wiring boards are thin, light, and have excellent flexibility, so they are used mainly in mobile devices such as mobile phones, PDAs, and liquid crystal driver modules. With the trend toward miniaturization, miniaturization of wiring on flexible printed wiring boards, high-density mounting, bending resistance, and the like are increasingly required.
更に加えて、環境対応問題より鉛フリーはんだを用いる実装も増えつつあり、今後は主流となってくることが予想される。鉛フリーはんだの実装温度が通常のはんだに比べ１５〜２０℃高く、これに伴いフレキシブルプリント配線板も従来以上の高耐熱性、高寸法安定性が求められている。また、難燃剤としてもハロゲンを含まないことが要求されている。 In addition, mounting using lead-free solder is also increasing due to environmental issues, and it is expected to become mainstream in the future. The mounting temperature of lead-free solder is 15 to 20 ° C. higher than that of normal solder, and accordingly, a flexible printed wiring board is required to have higher heat resistance and higher dimensional stability than ever before. Moreover, it is requested | required that a halogen is not included as a flame retardant.
従来の難燃性接着剤としては臭素化エポキシ樹脂を使用するのが一般的であったが（例えば特許文献１、２）、燃焼時にダイオキシンの発生が懸念され、ハロゲンフリー材料が求められている。
一方、耐熱性を克服する材料として熱可塑性ポリイミドを使用する場合がある。（例えば特許文献３）しかし、ポリイミドはまだまだ高価であり使用できる用途がコスト面で限定されてしまう。
On the other hand, a thermoplastic polyimide may be used as a material that overcomes heat resistance. (For example, Patent Document 3) However, polyimide is still expensive, and uses that can be used are limited in terms of cost.
本発明の目的は、ハロゲンフリーで、耐熱性、耐折性および屈曲性に優れた金属張積層板およびプリント配線板を提供することである。 An object of the present invention is to provide a metal-clad laminate and a printed wiring board which are halogen-free and excellent in heat resistance, folding resistance and flexibility.
このような目的は、下記（１）〜（１７）に記載の本発明により達成される。
（１）金属箔と基材とを層間接着剤を介して積層した金属張積層板であって、前記層間接着剤がビフェニルアラルキルエポキシ樹脂と、ビスフェノール型エポキシ樹脂と、下記一般式（１）で表される硬化促進剤を含む樹脂組成物で構成されることを特徴とする金属張積層板。
（３）前記樹脂組成物は、さらにはポリアミドイミド樹脂を含むものである上記（１）または（２）に記載の金属張積層板。
（４）前記樹脂組成物は、さらには合成ゴムを含むものである上記（１）ないし（３）のいずれかに記載の金属張積層板。
（５）前記樹脂組成物、さらには無機フィラーを含むものである上記（１）ないし（４）のいずれかに記載の金属張積層板。
（６）前記硬化剤は、下記一般式（２）および（３）で表されるフェノールノボラック樹脂のうち少なくとも一種類以上を含むものである上記（２）ないし（５）のいずれかに記載の金属張積層板。
（８）前記樹脂組成物は、ビスフェノール型エポキシ樹脂を１５〜９０重量部含む上記（１）ないし（７）のいずれかに記載の金属張積層板。
（９）前記樹脂組成物は、硬化剤を１０〜１００重量部含む上記（２）ないし（８）のいずれかに記載の金属張積層板。
（１０）前記樹脂組成物は、硬化促進剤を２〜１０重量部含む上記（１）ないし（９）のいずれかに記載の金属張積層板。
（１１）前記ポリアミドイミド樹脂の分子量が、８０００〜１５０００である上記（３）ないし（１０）のいずれかに記載の金属張積層板。
（１２）前記無機フィラーが、平均粒子径０．１〜１０μｍである上記（５）ないし（１１）のいずれかに記載の金属張積層板。
（１３）前記無機フィラーが、水酸化アルミニウムである上記（５）ないし（１２）のいずれかに記載の金属張積層板。
（１４）前記水酸化アルミニウムのアスペクト比が、２０〜３０の鱗片状である上記（１３）に記載の金属張積層板。
（１５）前記金属箔は、銅である上記（１）ないし（１４）のいずれかに記載の金属張積層板。
（１６）前記基材は、ポリイミドフィルムである上記（１）ないし（１５）のいずれかに記載の金属張積層板。
（１７）上記（１）ないし（１６）のいずれかに記載の金属張積層板の金属箔を回路加工することで得られるプリント配線板。
Such an object is achieved by the present invention described in the following (1) to (17).
(1) A metal-clad laminate in which a metal foil and a substrate are laminated via an interlayer adhesive, wherein the interlayer adhesive is represented by the following general formula (1): biphenyl aralkyl epoxy resin, bisphenol type epoxy resin A metal-clad laminate comprising a resin composition containing a curing accelerator represented.
(3) The metal-clad laminate according to (1) or (2), wherein the resin composition further includes a polyamideimide resin.
(4) The metal-clad laminate according to any one of (1) to (3), wherein the resin composition further includes a synthetic rubber.
(5) The metal-clad laminate according to any one of (1) to (4) above, which contains an inorganic filler.
(6) The metal curing agent according to any one of (2) to (5), wherein the curing agent includes at least one of phenol novolak resins represented by the following general formulas (2) and (3). Laminated board.
(8) The metal-clad laminate according to any one of (1) to (7), wherein the resin composition includes 15 to 90 parts by weight of a bisphenol type epoxy resin.
(9) The metal-clad laminate according to any one of (2) to (8), wherein the resin composition includes 10 to 100 parts by weight of a curing agent.
(10) The metal-clad laminate according to any one of (1) to (9), wherein the resin composition includes 2 to 10 parts by weight of a curing accelerator.
(11) The metal-clad laminate according to any one of (3) to (10), wherein the polyamideimide resin has a molecular weight of 8000 to 15000.
(12) The metal-clad laminate according to any one of (5) to (11), wherein the inorganic filler has an average particle diameter of 0.1 to 10 μm.
(13) The metal-clad laminate according to any one of (5) to (12), wherein the inorganic filler is aluminum hydroxide.
(14) The metal-clad laminate as described in (13) above, wherein the aluminum hydroxide has a scale-like aspect ratio of 20-30.
(15) The metal-clad laminate according to any one of (1) to (14), wherein the metal foil is copper.
(16) The metal-clad laminate according to any one of (1) to (15), wherein the base material is a polyimide film.
(17) A printed wiring board obtained by subjecting a metal foil of the metal-clad laminate according to any one of (1) to (16) to circuit processing.
本発明により、ハロゲンフリー、耐熱性、耐折性および屈曲性に優れた金属張積層板およびプリント配線板を提供することができる。 According to the present invention, it is possible to provide a metal-clad laminate and a printed wiring board excellent in halogen-free, heat resistance, folding resistance and flexibility.
以下、本発明の金属張積層板およびプリント配線板について詳細に説明する。
本発明の金属張積層板に使用される樹脂組成物はハロゲン化物を含まないものであって、ビフェニルアラルキルエポキシ樹脂、ビスフェノール型エポキシ樹脂および下記化学式（１）で表される硬化促進剤を含有してなることを特徴とする金属張積層板である。
本発明の金属張積層板は、上述の樹脂組成物を基材に塗工したのち、金属はくを積層することを特徴とするものである。本発明の金属張積層板は耐屈曲性において高弾性であることが望ましく、本発明の配合物は剛直な分子骨格を三次元的に硬化するため目的に適している。また、使用するポリアミドイミドもポリイミドに比べても高弾性であり強靭でありガラス転位点も高い樹脂であるため耐屈曲性が良い。また、液状エポキシと少量の合成ゴムを配合することにより金属張積層板成形時の流動性などが良好となる。
本発明のプリント配線板は、上述の金属張積層板を化学的にエッチングすることで回路加工し、その回路上の必要な部分にカバーレイを真空熱プレスや熱ロールなどの一般的な方法で積層されたものである。
Hereinafter, the metal-clad laminate and the printed wiring board of the present invention will be described in detail.
The resin composition used for the metal-clad laminate of the present invention does not contain a halide and contains a biphenyl aralkyl epoxy resin, a bisphenol type epoxy resin, and a curing accelerator represented by the following chemical formula (1). A metal-clad laminate.
The metal-clad laminate of the present invention is characterized by laminating a metal foil after coating the above resin composition on a substrate. It is desirable that the metal-clad laminate of the present invention is highly elastic in bending resistance, and the composition of the present invention is suitable for the purpose because the rigid molecular skeleton is three-dimensionally cured. Further, since the polyamideimide used is a resin that is highly elastic and tougher than polyimide, and has a high glass transition point, it has good bending resistance. Moreover, the fluidity | liquidity at the time of metal-clad laminated board shaping | molding becomes favorable by mix | blending a liquid epoxy and a small amount of synthetic rubber.
The printed wiring board of the present invention is a circuit process by chemically etching the above-mentioned metal-clad laminate, and a coverlay is applied to a necessary part on the circuit by a general method such as vacuum hot press or hot roll. It is a laminated one.
本発明の金属張積層板に用いる樹脂組成物では、ビフェニルアラルキルエポキシ樹脂を用いる。ビフェニルアラルキルエポキシ樹脂はそのベンゼン環の多い分子骨格上、低吸水化の効果と難燃性の効果が得られる。含有量は、特に限定されないが、１５〜１００重量部が好ましく、２５〜６０重量部がより好ましい。含有量が前記下限値未満では低吸水化が十分でなく、また前記上限値を越えると密着性が低下し好ましくない。
ビフェニルアラルキルエポキシ樹脂としては、特に限定されないが、耐熱性のあるものが好ましく、燃えにくい骨格のものがより好ましい。
In the resin composition used for the metal-clad laminate of the present invention, a biphenyl aralkyl epoxy resin is used. Biphenyl aralkyl epoxy resin has the effect of reducing water absorption and flame retardancy on the molecular skeleton with many benzene rings. Although content is not specifically limited, 15-100 weight part is preferable and 25-60 weight part is more preferable. If the content is less than the lower limit, water absorption is not sufficient, and if the content exceeds the upper limit, the adhesion is undesirably lowered.
Although it does not specifically limit as a biphenyl aralkyl epoxy resin, A heat resistant thing is preferable and the thing of the flame | frame which is hard to burn is more preferable.
本発明の金属張積層板に用いる樹脂組成物では、ビスフェノール型エポキシ樹脂を用いる。これにより、金属張積層板の樹脂組成物に柔軟性が加わり、低圧での金属積層板形成が可能になる。ビスフェノール型エポキシ樹脂の含有量は、特に限定されないが、１５〜９０重量部が好ましく、２５〜６０重量部がより好ましい。含有量が前記下限値未満では樹脂組成物に柔軟性がなく、前記上限値を越えるとプレス成形時にフローが大となり厚みの制御ができなくなる。
ビスフェノール型エポキシ樹脂としては、特に限定されないが、液状のビスフェノール型エポキシ樹脂が好ましく、ビスフェノールＡ型液状エポキシ樹脂がより好ましい。
In the resin composition used for the metal-clad laminate of the present invention, a bisphenol type epoxy resin is used. Thereby, flexibility is added to the resin composition of the metal-clad laminate, and the metal laminate can be formed at a low pressure. The content of the bisphenol type epoxy resin is not particularly limited, but is preferably 15 to 90 parts by weight, and more preferably 25 to 60 parts by weight. If the content is less than the lower limit, the resin composition is not flexible, and if the content exceeds the upper limit, the flow becomes large during press molding and the thickness cannot be controlled.
The bisphenol type epoxy resin is not particularly limited, but a liquid bisphenol type epoxy resin is preferable, and a bisphenol A type liquid epoxy resin is more preferable.
本発明の金属張積層板に用いる樹脂組成物では、硬化促進剤を用いる。硬化促進剤の含有量は、特に限定されないが、２〜１０重量部が好ましく、３〜７重量部がより好ましい。含有量が前記下限値未満では難燃性の効果が小さく、硬化促進効果も少ない。前記上限値を越えると硬化系が変わり金属張積層板の弾性率が低下する。
トリアジン基を含むことにより難燃性が向上する。トリアジン基を含むノボラック型フェノール樹脂としては、特に限定されないが、直鎖状２級アミン誘導体が好ましく、下記化学式（１）で表されるトリアジン基を含むノボラック型フェノール樹脂がより好ましい。
The flame retardancy is improved by including a triazine group. Although it does not specifically limit as a novolak-type phenol resin containing a triazine group, A linear secondary amine derivative is preferable and the novolak-type phenol resin containing the triazine group represented by following Chemical formula (1) is more preferable.
本発明の金属張積層板に用いる樹脂組成物では、硬化剤を含むことが好ましい。前記硬化剤は、下記一般式（２）および（３）で表されるフェノールノボラック樹脂のうち少なくとも一種類以上使用していることが望ましい。含有量は、特に限定されないが、１０〜１００重量部が望ましく、２０〜５０重量部がより好ましい。含有量が前記下限値以下では硬化が不十分となり十分な特性を得られず、また前記上限値を越えるとプレス成形時にフローが大となり厚みの制御ができなくなる。
本発明の金属張積層板に用いる樹脂組成物では、ポリアミドイミド樹脂を含むことが好ましい。これにより、基材として使用されるポリイミドフィルムとの密着性が向上する。
前記ポリアミドイミド樹脂は重量平均分子量が８０００以上１５０００未満であることが望ましく、９０００以上１３０００未満がより望ましい。重量平均分子量が前記下限値未満であると密着性が十分に得られず、前記上限値以上であると当該エポキシ樹脂と相溶性が低下する。
また、ポリアミドイミドの含有量は、特に限定されないが、５〜４０重量部が好ましく、１０〜２０重量部がより好ましい。含有量が前記下限値未満であると密着性が十分に得られず、前記上限値を超えると当該エポキシ樹脂と相溶性が低下する。
本発明で用いられるポリアミドイミドはその分子骨格上、耐熱性と難燃性の効果も得られる。ポリアミドイミド樹脂としては、特に限定されないが、耐熱性があるものが好ましい。
The resin composition used for the metal-clad laminate of the present invention preferably contains a polyamideimide resin. Thereby, adhesiveness with the polyimide film used as a base material improves.
The polyamideimide resin preferably has a weight average molecular weight of 8000 or more and less than 15,000, and more preferably 9000 or more and less than 13,000. When the weight average molecular weight is less than the lower limit, sufficient adhesion cannot be obtained, and when the weight average molecular weight is not less than the upper limit, compatibility with the epoxy resin decreases.
The content of polyamideimide is not particularly limited, but is preferably 5 to 40 parts by weight, and more preferably 10 to 20 parts by weight. If the content is less than the lower limit, sufficient adhesion cannot be obtained, and if it exceeds the upper limit, the compatibility with the epoxy resin decreases.
The polyamide-imide used in the present invention also has effects of heat resistance and flame retardancy on its molecular skeleton. The polyamideimide resin is not particularly limited, but preferably has heat resistance.
本発明の金属張積層板に用いる樹脂組成物では、合成ゴムを含むことが好ましい。これにより、絶縁フィルムに塗工したのち、金属はくを積層することで得られる金属張積層板の密着性がよくなる。
前記合成ゴムは特に限定されるものではないが、好ましくは固形のものがよい。液状タイプのものでは粘着性が増し作業性が悪くなる。また、エポキシ樹脂やポリアミドイミドとの相溶性を上げる為にカルボン酸変性、水酸基変性やエポキシ変性したものや熱劣化を防止するために水素転化型の合成ゴムなども使用可能である。具体的には、特に限定されないが、ＮＢＲ、アクリルゴム、ポリブタジエン、イソプレン、カルボン酸変性ＮＢＲ、水素転化型ポリブタジエン、エポキシ変性ポリブタジエンなどが具体例として挙げられる。
合成ゴムの含有量は、特に限定されないが、２〜１０重量部が好ましく３〜７重量部がより好ましい。含有量が前記下限値未満では期待される特性が十分に得られず、前記上限値を越えると耐熱性や難燃性が低下する。
The resin composition used for the metal-clad laminate of the present invention preferably contains a synthetic rubber. Thereby, after coating to an insulating film, the adhesiveness of the metal-clad laminate obtained by laminating metal foil is improved.
The synthetic rubber is not particularly limited, but is preferably a solid rubber. In the liquid type, the adhesiveness increases and the workability deteriorates. In addition, carboxylic acid-modified, hydroxyl-modified, and epoxy-modified products for improving compatibility with epoxy resins and polyamide-imides, and hydrogen conversion type synthetic rubbers for preventing thermal degradation can be used. Specific examples include, but are not limited to, NBR, acrylic rubber, polybutadiene, isoprene, carboxylic acid-modified NBR, hydrogen conversion polybutadiene, epoxy-modified polybutadiene, and the like.
Although content of a synthetic rubber is not specifically limited, 2-10 weight part is preferable and 3-7 weight part is more preferable. If the content is less than the lower limit, the expected properties cannot be obtained sufficiently, and if the content exceeds the upper limit, the heat resistance and flame retardancy are lowered.
本発明の金属張積層板に用いる樹脂組成物では、無機フィラーを含むことが好ましい。これにより、耐熱性向上と弾性率向上および難燃性を向上させることが出来る。前記無機フィラーの、平均粒子径は特に限定されないが、０．１〜１０μｍであることが好ましい。前記無機フィラーの平均粒子径が０．１μｍ未満であるとワニスのチキソトロピーが高くなり扱いが難しくなる。１０μｍを超えると特にファインピッチ回路においては絶縁信頼性が低下する。無機フィラーとしては、絶縁性の高い材料が好まれる。例えば水酸化アルミニウム、溶融シリカ、炭酸カルシウム、アルミナ、マイカ、タルク、ホワイトカーボンなどが好ましく、その中でも水酸化アルミニウムがより好ましい。水酸化アルミウムのアスペクト比は、２０〜３０の鱗片状が好ましい。アスペクト比が２０未満であると耐ヒンジ特性において効果が小さく、３０を越えると樹脂への分散性が悪くなる。樹脂組成物中の無機フィラーの含有量は、特に限定されないが、５０〜２００重量部が好ましく、７５から１５０重量部がより好ましい。含有量が前記下限値未満であると弾性率が低下し耐屈曲性が低下する。また、前記上限値を超えると密着力が低下する。 The resin composition used for the metal-clad laminate of the present invention preferably contains an inorganic filler. Thereby, heat resistance improvement, an elastic modulus improvement, and a flame retardance can be improved. Although the average particle diameter of the said inorganic filler is not specifically limited, It is preferable that it is 0.1-10 micrometers. If the average particle size of the inorganic filler is less than 0.1 μm, the thixotropy of the varnish becomes high and handling becomes difficult. If it exceeds 10 μm, the insulation reliability is deteriorated particularly in a fine pitch circuit. As the inorganic filler, a highly insulating material is preferred. For example, aluminum hydroxide, fused silica, calcium carbonate, alumina, mica, talc, white carbon and the like are preferable, and among these, aluminum hydroxide is more preferable. The aspect ratio of aluminum hydroxide is preferably 20-30 scale. When the aspect ratio is less than 20, the effect on the hinge resistance is small, and when it exceeds 30, the dispersibility in the resin is deteriorated. The content of the inorganic filler in the resin composition is not particularly limited, but is preferably 50 to 200 parts by weight, and more preferably 75 to 150 parts by weight. If the content is less than the lower limit, the elastic modulus is lowered and the flex resistance is lowered. Moreover, when the said upper limit is exceeded, adhesive force will fall.
本発明の金属張積層板に用いる樹脂組成物では、特に限定されないが、さらに、銅はくや内層回路基板との密着力の向上、耐湿性の向上のためにエポキシシラン等のシランカップリング剤あるいはチタネート系カップリング剤、消泡剤などの添加剤を含有することが好ましい。 The resin composition used for the metal-clad laminate of the present invention is not particularly limited, and further, a silane coupling agent such as epoxy silane for improving adhesion with copper foil and inner layer circuit board and improving moisture resistance Or it is preferable to contain additives, such as a titanate coupling agent and an antifoamer.
次に、金属張積層板の製法について説明する。
本発明の金属張積層板は基材の片面または両面にワニスを塗工し乾燥後、熱圧着ロールなどによって金属箔を樹脂組成物面に積層して作製される。
前記金属箔を構成する金属としては、例えば銅および銅系合金、アルミおよびアルミ系合金、鉄および鉄系合金等が挙げられ、銅がより好ましい。
また、基材としては、絶縁性フィルムなどが挙げられ、ポリイミドフィルムがより好ましい。
Next, a method for producing a metal-clad laminate will be described.
The metal-clad laminate of the present invention is produced by coating a varnish on one or both sides of a substrate, drying, and then laminating a metal foil on the resin composition surface by a thermocompression roll or the like.
Examples of the metal constituting the metal foil include copper and a copper-based alloy, aluminum and an aluminum-based alloy, iron and an iron-based alloy, and copper is more preferable.
Moreover, an insulating film etc. are mentioned as a base material, A polyimide film is more preferable.
前記ワニスに用いられる溶剤としては、樹脂組成物に対し良好な溶解性を持つものを選択しなければならない。例えば、アセトン、メチルエチルケトン、トルエン、キシレン、ｎ−ヘキサン、メタノール、エタノール、メチルセルソルブ、エチルセルソルブ、ブチルセロソルブ、メトキシプロパノール、シクロヘキサノン、Ｎ−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミドなどを一種または二種以上の混合系を使用することが可能である。 As a solvent used for the varnish, a solvent having good solubility in the resin composition must be selected. For example, acetone, methyl ethyl ketone, toluene, xylene, n-hexane, methanol, ethanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methoxypropanol, cyclohexanone, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, etc. It is possible to use a mixed system of
次にプリント配線板について説明する。
プリント配線板とは、基材の少なくとも片面に第1の樹脂組成物を介して導電層を有し、前記導電層に第２の樹脂組成物付き基材を積層したものである。
本発明のプリント配線板は、上記のようにして得られた金属張積層板の金属箔を化学的にエッチングすることで回路加工する。その回路上の必要な部分にあらかじめ必要としない部分を打ち抜いておいたカバーレイを真空熱プレスや熱ロールなどの一般的な方法で積層される。
以下、本発明を実施例及び比較例により説明するが、本発明はこれに限定されるものではない。
Next, the printed wiring board will be described.
A printed wiring board has a conductive layer on at least one surface of a substrate with a first resin composition interposed therebetween, and a substrate with a second resin composition is laminated on the conductive layer.
The printed wiring board of the present invention is subjected to circuit processing by chemically etching the metal foil of the metal-clad laminate obtained as described above. A coverlay in which unnecessary portions are punched in advance on necessary portions on the circuit is laminated by a general method such as vacuum hot pressing or hot roll.
Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to this.
（実施例1）
金属張積層板の樹脂組成物として、ビフェニルアラルキルエポキシ樹脂（エポキシ当量２８０、日本化薬製ＮＣ−３０００）３０重量部、ビスフェノールＡ型エポキシ樹脂（エポキシ当量１９０、ジャパンエポキシレジン製エピコート８２８）１５重量部、硬化剤にノボラック型フェノール樹脂（２核体量２．５％、フリーフェノール量０％、Ｍｗ／Ｍｎ＝１．４３、住友ベークライト製ＰＲ−ＮＭＤ−１０３）１３重量部、硬化促進剤に直鎖状２級アミン含有ノボラック型フェノール樹脂（ＯＨ当量１３５、大日本インキ化学製ＬＡ−７７５１）３重量部およびポリアミドイミド樹脂（分子量１００００、Ｔｇ＝２８０℃、東洋紡社製）を１５重量部、ニトリルゴム（アクリロニトリル量２７％、日本ゼオン製）３重量部及びシランカップリング剤０．５重量部をＭＥＫ及びブチルセルソルブとの混合溶剤に樹脂固形分が５０％となるように溶解した。
この樹脂ワニスに無機フィラーとして水酸化アルミ（平均粒子径１μｍ、日本軽金属社製Ｂ１４０３）５０重量部の割合で添加し、均一に分散するまで撹拌して配合物ワニスを作製した。
この配合物ワニスを厚み２５μｍのポリイミドフィルムの両面に各樹脂組成物の厚みが乾燥後、１０μｍとなるようにコンマロールコーターで塗工、８０℃５分＋１２５℃３分で乾燥し、次いで１２μｍ厚の圧延銅はくを１８０℃でロールラミネーターにより積層した。１８５℃１時間の熱処理を行った後に、エッチングにより所定の評価用のプリント配線板を作成した。なお、難燃性評価には全面エッチングにより銅はくを除去した基板を評価用基板として得た。
(Example 1)
As a resin composition of a metal-clad laminate, biphenyl aralkyl epoxy resin (epoxy equivalent 280, Nippon Kayaku NC-3000) 30 parts by weight, bisphenol A type epoxy resin (epoxy equivalent 190, Japan Epoxy Resin Epicoat 828) 15 weight 13 parts by weight of novolac type phenol resin (2.5% binuclear body, 0% free phenol, Mw / Mn = 1.43, PR-NMD-103 manufactured by Sumitomo Bakelite) as a curing agent, and a curing accelerator 3 parts by weight of a linear secondary amine-containing novolak type phenol resin (OH equivalent 135, LA-7751 manufactured by Dainippon Ink and Chemical) and 15 parts by weight of a polyamideimide resin (molecular weight 10,000, Tg = 280 ° C., manufactured by Toyobo Co., Ltd.) Nitrile rubber (acrylonitrile amount 27%, made by Nippon Zeon) 3 parts by weight and silane cup The ring agent 0.5 parts by weight of the resin solids in a mixed solvent of MEK and butyl cellosolve was dissolved to be 50%.
To this resin varnish, 50 parts by weight of aluminum hydroxide (average particle size: 1 μm, Nippon Light Metal Co., Ltd., B1403) was added as an inorganic filler and stirred until uniformly dispersed to prepare a compound varnish.
This compound varnish was coated on a both sides of a polyimide film having a thickness of 25 μm with a comma roll coater so that the thickness of each resin composition was 10 μm, dried at 80 ° C. for 5 minutes + 125 ° C. for 3 minutes, and then 12 μm thick The rolled copper foil was laminated at 180 ° C. with a roll laminator. After heat treatment at 185 ° C. for 1 hour, a predetermined printed wiring board for evaluation was prepared by etching. For the evaluation of flame retardancy, a substrate from which copper foil was removed by whole surface etching was obtained as an evaluation substrate.
（実施例２）
硬化剤にノボラック型フェノール樹脂（三井化学製ミレックスＸＬＣ−ＬＬ）にした以外実施例１と同様にしてプリント配線板を得、同様に評価した。
(Example 2)
A printed wiring board was obtained in the same manner as in Example 1 except that a novolac type phenol resin (Mirex XLC-LL, manufactured by Mitsui Chemicals) was used as the curing agent, and was similarly evaluated.
（実施例３）
ノボラック型フェノール樹脂の硬化剤を住友ベークライト製ＰＲ−ＮＭＤ−１０３を１３重量部と三井化学製ミレックスＸＬＣ−ＬＬを１３重量部にした以外実施例１と同様にしてプリント配線板を得、同様に評価した。
(Example 3)
A printed wiring board was obtained in the same manner as in Example 1 except that 13 parts by weight of PR-NMD-103 made by Sumitomo Bakelite and 13 parts by weight of Millex XLC-LL made by Mitsui Chemicals were used as the curing agent for the novolak type phenol resin. evaluated.
（実施例４）
無機フィラーとして、水酸化アルミ（日本軽金属社製Ｂ１４０３）４５重量部と平均粒子径が５〜１０μｍのマイカ（コープケミカル社製ＭＫ−２００）４０重量部の混合物にした以外実施例１と同様にしてプリント配線板を得、同様に評価した。
Example 4
As an inorganic filler, the same procedure as in Example 1 was performed except that the mixture was 45 parts by weight of aluminum hydroxide (B1403 manufactured by Nippon Light Metal Co., Ltd.) and 40 parts by weight of mica (MK-200 manufactured by Corp Chemical Co.) having an average particle size of 5 to 10 μm. A printed wiring board was obtained and evaluated in the same manner.
（比較例１）
硬化促進剤を使用しなかった以外、実施例1と同様にしてプリント配線板を得、同様に評価した。
(Comparative Example 1)
A printed wiring board was obtained and evaluated in the same manner as in Example 1 except that no curing accelerator was used.
このようにして得られたプリント配線板の吸湿半田耐熱性、密着力、電気絶縁性、屈曲性、難燃性を評価・測定し、その結果を表１に示す。
＊吸湿半田耐熱性
ＪＩＳ規格Ｃ５０１６−１０．３に順ずる。フクレ、剥がれのなかったものを○とした。
＊密着力
ＪＩＳ規格Ｃ５０１６−８．１に順ずる
＊電気絶縁性
回路幅及び回路間幅をそれぞれ４０μｍとした櫛型パターンを用い、初期状態および６５℃９０％５０Ｖ１０００時間処理後の絶縁抵抗値を測定した。
＊屈曲性
ＩＰＣ法に準じる。Ｒ＝２ｍｍ、１０００ｒｐｍ、ストローク１５ｍｍで屈曲回数が１０万回以上のものを◎、７万５千回以上１０万回未満のものを○、５万回以上７万５千回未満のものを△、５万回に満たなかったものを×とした。
＊耐折性
ＭＩＴ法に順ずる。Ｒ＝０．４ｍｍ、荷重５００ｇ、裏全面エッチング、片面のみカバーレイありで基材の耐折性をみた。
＊難燃性
ＵＬ法に基づき評価した。
* Hygroscopic solder heat resistance Conforms to JIS standard C5016-10.3. The ones that did not come off or peeled off were marked with ◯.
* Adhesive strength Conforms to JIS standard C5016-8.1 * Electrical insulation Using a comb-shaped pattern with a circuit width and circuit width of 40 μm, respectively, the insulation resistance value after treatment in the initial state and 65 ° C 90% 50V 1000 hours It was measured.
* Flexibility Conforms to the IPC method. R = 2mm, 1000rpm, stroke 15mm, flex number of 100,000 times or more ◎, 75,000 times to less than 100,000 times ○, 50,000 times to less than 75,000 times △ Those that were less than 50,000 times were marked as x.
* Folding resistance Conforms to MIT method. R = 0.4 mm, load 500 g, entire back surface etching, only one side was covered with a cover lay, and the folding resistance of the substrate was observed.
* Evaluated based on flame retardancy UL method.
最近、小型化に加えますます機能の充実が計られている携帯電話やデジタルカメラ、デジタルビデオカメラ、ＤＶＤなどにはフレキシブルプリント配線板が必ず使われているといっても過言ではなく、その使用比率も増加の一途である。更には高機能化に伴ない高密度実装となっておりフレキシブルプリント配線板もファインピッチ化、多層化など進化をし続けている。本発明の金属張積層板はこのような用途のプリント配線板として利用される。また、本発明の組成物はハロゲンフリーのため、焼却時にダイオキシンの発生がなく、最近増えつつある環境対応製品に使用される。 It is no exaggeration to say that flexible printed wiring boards are always used in mobile phones, digital cameras, digital camcorders, DVDs, etc., which have recently been enhanced in addition to miniaturization. The ratio is also increasing. In addition, high-density mounting has been accompanied by higher functionality, and flexible printed wiring boards have continued to evolve with fine pitches and multilayers. The metal-clad laminate of the present invention is used as a printed wiring board for such applications. Further, since the composition of the present invention is halogen-free, there is no generation of dioxins at the time of incineration, and it is used for environmentally friendly products that are increasing recently.
Claims (17)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004051023A JP2005238617A (en) | 2004-02-26 | 2004-02-26 | Metal clad laminated sheet and printed wiring board |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004051023A JP2005238617A (en) | 2004-02-26 | 2004-02-26 | Metal clad laminated sheet and printed wiring board |
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Cited By (6)
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| WO2007125922A1 (en) * | 2006-04-25 | 2007-11-08 | Hitachi Chemical Company, Ltd. | Conductor foil with adhesive layer, conductor-clad laminate, printed wiring board and multilayer wiring board |
| JP2007313881A (en) * | 2006-04-25 | 2007-12-06 | Hitachi Chem Co Ltd | Metallic foil with adhesive layer, metal clad laminate, printed wiring board, and multi-layered wiring board |
| JP2008103651A (en) * | 2005-11-08 | 2008-05-01 | Hitachi Chem Co Ltd | Metal foil with adhesive layer, metal-clad laminated plate, and printed circuit board and multilayer circuit board using the metal-clad laminated plate |
| JP2008132750A (en) * | 2006-10-24 | 2008-06-12 | Hitachi Chem Co Ltd | Laminate with conductor foil, printed wiring board, and multilayer wiring board |
| JP2009007551A (en) * | 2007-05-30 | 2009-01-15 | Hitachi Chem Co Ltd | Resin varnish, adhesive layer-coated metal foil, metal-clad laminate, printed wiring board, and multilayer wiring board |
| JP2012227534A (en) * | 2005-11-08 | 2012-11-15 | Hitachi Chem Co Ltd | Metal foil with adhesive layer, metal-clad laminate, and printed wiring board and multilayer wiring board obtained by using the metal-clad laminate |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008103651A (en) * | 2005-11-08 | 2008-05-01 | Hitachi Chem Co Ltd | Metal foil with adhesive layer, metal-clad laminated plate, and printed circuit board and multilayer circuit board using the metal-clad laminated plate |
| JP2012227534A (en) * | 2005-11-08 | 2012-11-15 | Hitachi Chem Co Ltd | Metal foil with adhesive layer, metal-clad laminate, and printed wiring board and multilayer wiring board obtained by using the metal-clad laminate |
| WO2007125922A1 (en) * | 2006-04-25 | 2007-11-08 | Hitachi Chemical Company, Ltd. | Conductor foil with adhesive layer, conductor-clad laminate, printed wiring board and multilayer wiring board |
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| TWI423882B (en) * | 2006-04-25 | 2014-01-21 | Hitachi Chemical Co Ltd | A conductor foil having an adhesive layer, a laminated board for bonding the conductor, a printed wiring board, and a multilayer wiring board |
| JP2008132750A (en) * | 2006-10-24 | 2008-06-12 | Hitachi Chem Co Ltd | Laminate with conductor foil, printed wiring board, and multilayer wiring board |
| JP2009007551A (en) * | 2007-05-30 | 2009-01-15 | Hitachi Chem Co Ltd | Resin varnish, adhesive layer-coated metal foil, metal-clad laminate, printed wiring board, and multilayer wiring board |
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