JP2011026607A - Thermosetting resin composition, prepreg, laminated sheet, and printed wiring board - Google Patents
Thermosetting resin composition, prepreg, laminated sheet, and printed wiring board Download PDFInfo
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本発明は，熱硬化性樹脂組成物、プリプレグ、積層板及びプリント配線板に関する。 The present invention relates to a thermosetting resin composition, a prepreg, a laminated board, and a printed wiring board.
プリント配線板は，繊維基材に，熱硬化性樹脂組成物のワニスを含浸乾燥してなるプリプレグを１枚または所要枚数重ねた構成体を加熱加圧成形して積層板を得，この積層板を基板として，その表面に回路を形成して製造される。プリント配線板同士をプリプレグで接着し，多層構造とした多層プリント配線板の製造も行われている。また，通常、積層板を製造するときに銅箔などの金属箔を同時に重ねて金属箔張積層板とし、この金属箔をエッチングして回路を形成している。それ故に本明細書においては、積層板には金属箔張積層板を含む意味とされる。 A printed wiring board is obtained by heat-press molding a structure in which a prepreg formed by impregnating and drying a varnish of a thermosetting resin composition on a fiber base material is laminated to obtain a laminated board. Is manufactured by forming a circuit on its surface. A multilayer printed wiring board having a multilayer structure in which printed wiring boards are bonded to each other with a prepreg is also manufactured. Usually, when manufacturing a laminate, a metal foil such as a copper foil is simultaneously laminated to form a metal foil-clad laminate, and this metal foil is etched to form a circuit. Therefore, in this specification, it is meant that the laminate includes a metal foil-clad laminate.
近年，半導体搭載用パッケージなどの用途に用いられるプリント配線板の基板は、ワイヤボンディングの良否識別を容易にするため黒色を基調とするものが主流となっている。基板を黒色とする手法としては，積層板を製造するためのプリプレグに黒色の繊維基材を用いる手法や，熱硬化性樹脂組成物にカーボンブラック，スピリットブラックなどのカーボン系顔料，または特公平７−４５５８１号公報、特開２０００−７２９６９号公報に示されるようなアゾ系の金属錯塩黒色染料を配合する手法が知られている。 In recent years, a substrate of a printed wiring board used for applications such as a package for mounting on a semiconductor has been mainly based on black in order to easily identify the quality of wire bonding. As a method of making the substrate black, a method of using a black fiber base material for a prepreg for manufacturing a laminated plate, a carbon-based pigment such as carbon black or spirit black for a thermosetting resin composition, or JP 7 There are known techniques for blending azo-based metal complex black dyes as disclosed in JP-A-45581 and JP-A-2000-72969.
黒色の繊維基材を用いて基板を黒色とする手法では、繊維基材が十分な黒さを有していない場合があり，外観上の問題があった。また、熱硬化性樹脂組成物にカーボンブラック、スピリットブラック等のカーボン系顔料を配合する手法では、カーボン自体が導電性を有するために基板の絶縁性低下、及び電食による回路間の絶縁低下を生じやすかった。またアゾ系の金属錯塩黒色染料を配合する手法においてもイオン性不純物の含有量が高いと電食による回路間の絶縁低下を発生しやすい。また最近になって鉛フリーはんだ対応のためリフロー温度も高くなってきており、例えば構造式が一般式（２）や一般式（３）で示される黒色染料は高温処理後に退色しやすい。このためプリント配線板としての信頼性（以下単に信頼性とする）が低下するという問題があった。 In the method of making the substrate black using a black fiber base material, the fiber base material may not have sufficient blackness, and there is a problem in appearance. In addition, in the method of blending carbon pigments such as carbon black and spirit black into the thermosetting resin composition, the carbon itself has conductivity, so that the insulation of the substrate is lowered and the insulation between the circuits due to electrolytic corrosion is reduced. It was easy to occur. Also in the method of blending azo-based metal complex black dye, if the content of ionic impurities is high, the insulation between circuits is likely to be reduced due to electrolytic corrosion. In recent years, the reflow temperature has also been increased to cope with lead-free solder. For example, black dyes whose structural formulas are represented by general formulas (2) and (3) tend to fade after high-temperature treatment. For this reason, there has been a problem that reliability as a printed wiring board (hereinafter simply referred to as reliability) is lowered.
本発明は、外観が黒色であり、プリント配線板とした時、絶縁性及び信頼性の低下がない積層板を製造するために、好適な熱硬化性樹脂組成物及びそれを用いたプリプレグ、積層板、プリント配線板を提供することを目的とする。 INDUSTRIAL APPLICABILITY The present invention provides a thermosetting resin composition suitable for producing a laminated board having a black appearance and no deterioration in insulation and reliability when used as a printed wiring board, and a prepreg and a laminate using the same. It aims at providing a board and a printed wiring board.
本発明者は，黒色染料を熱硬化性樹脂組成物に配合して検討した結果、構造式が下記一般式（１）で示される黒色染料中の全無機イオン濃度を２００ｐｐｍ以下に精製された状態で含有させたとき、積層板の外観を黒色とすることができ、硬化反応に影響がなく、絶縁性及び信頼性の低下を解消することができることを見出し、本発明に到達した。 As a result of studying the black dye mixed with the thermosetting resin composition, the present inventor has purified the total inorganic ion concentration in the black dye whose structural formula is represented by the following general formula (1) to 200 ppm or less. It was found that the appearance of the laminated plate can be made black when it is contained, there is no influence on the curing reaction, and the reduction in insulation and reliability can be eliminated, and the present invention has been achieved.
本発明は、次のものに関する。
（１）構造式が一般式（１）で示される黒色染料を含有する熱硬化性樹脂組成物において、前記黒色染料中の全無機イオン濃度が２００ｐｐｍ以下である熱硬化性樹脂組成物。
The present invention relates to the following.
(1) A thermosetting resin composition containing a black dye having a structural formula represented by the general formula (1), wherein the total inorganic ion concentration in the black dye is 200 ppm or less.
（２）繊維基材に項（１）に記載の熱硬化性樹脂組成物のワニスを含浸乾燥してなるプリプレグ。
（３）項（２）に記載のプリプレグを少なくとも１枚含むプリプレグ構成体を加熱加圧してなる積層板。
（４）項（３）に記載の積層板を用い配線加工してなるプリント配線板。
(2) A prepreg obtained by impregnating and drying the varnish of the thermosetting resin composition according to item (1) on a fiber base material.
(3) A laminate obtained by heating and pressurizing a prepreg structure including at least one prepreg according to item (2).
(4) A printed wiring board obtained by performing wiring processing using the laminated board according to item (3).
本発明の熱硬化性樹脂組成物を用いてプリプレグを製造し、このプリプレグを用いることにより、黒色を基調とする積層板を製造することができる。そしてこの積層板を用い、配線加工してなるプリント配線板は、高温処理による退色もなく、電食による絶縁低下が無いことから信頼性に優れる。 By producing a prepreg using the thermosetting resin composition of the present invention and using this prepreg, a laminated board based on black can be produced. And the printed wiring board formed by wiring using this laminated board is excellent in reliability because it is not discolored by high temperature treatment and there is no insulation deterioration due to electrolytic corrosion.
本発明の熱硬化性樹脂組成物には、全無機イオン濃度が２００ｐｐｍ以下の黒色染料である金属錯塩アゾ系黒色染料を、固形もしくは溶媒にて希釈した液状のものを用いることができる。前記黒色染料中の全無機イオン濃度は、２００ｐｐｍ以下であり、０．０１〜１８０ｐｐｍが好ましく、０．０１〜１００ｐｐｍがより好ましく、０．０１〜５０ｐｐｍが特に好ましい。全無機イオン濃度が、２００ｐｐｍを超すと絶縁性低下、及び電食によるプリント配線板の回路間の絶縁低下を生じやすくなる。 In the thermosetting resin composition of the present invention, a metal complex salt azo black dye which is a black dye having a total inorganic ion concentration of 200 ppm or less can be used in a solid or liquid form diluted with a solvent. The total inorganic ion concentration in the black dye is 200 ppm or less, preferably 0.01 to 180 ppm, more preferably 0.01 to 100 ppm, and particularly preferably 0.01 to 50 ppm. When the total inorganic ion concentration exceeds 200 ppm, the insulation is lowered, and the insulation between the circuits of the printed wiring board is easily caused by electrolytic corrosion.
前記一般式（１）で示される金属錯塩アゾ系黒色染料は、クロム酸（１−），［１−［（２−ヒドロキシ−４−ニトロフェニル）アゾ］−２−ナフタレノラト（２−）］［１−［（２−ヒドロキシ−５−ニトロフェニル）アゾ］−２−ナフタレノラト（２−）］の３−［（２−エチルヘキシル）オキシ］−１−プロパンアミン水素（１：１）化合物であり、ソルベントブラック２７として知られている黒色染料であり、市販品としては、中央合成化学株式会社製の商品名ネオスーパーブラックＣ−８３２（Ｎｅｏ Ｓｕｐｅｒ Ｂｌａｃｋ Ｃ−８３２）などを挙げることができる。なお、ネオスーパーブラックＣ−８３２などの市販品を用いる場合、市販品は全無機イオン濃度が２００ｐｐｍ以下とは限らないので、精製して用いる必要がある。 The metal complex salt azo black dye represented by the general formula (1) is chromic acid (1-), [1-[(2-hydroxy-4-nitrophenyl) azo] -2-naphthalenolate (2-)] [ 1-[(2-hydroxy-5-nitrophenyl) azo] -2-naphthalenolato (2-)] 3-[(2-ethylhexyl) oxy] -1-propanamine hydrogen (1: 1) compound, It is a black dye known as Solvent Black 27, and as a commercial product, trade name Neo Super Black C-832 (Neo Super Black C-832) manufactured by Chuo Synthetic Chemical Co., Ltd. can be exemplified. In addition, when using commercial items, such as Neo Super Black C-832, since the total inorganic ion concentration is not necessarily 200 ppm or less, it is necessary to refine | purify and use a commercial item.
精製する方法としては、黒色染料中の全無機イオン濃度を２００ｐｐｍ以下にできる方法であれば特に制限はなく、一般的な方法として、クロマトグラフィ法、電気泳動法、溶媒抽出法、固相抽出法、ろ過法、限外ろ過法、水抽出法、透析法、相分離法、遠心分離法、昇華法、再結晶法などが挙げられる。なお合成した場合も、全無機イオン濃度が２００ｐｐｍを超えていれば、同様に精製して用いる必要がある。なお無機イオン濃度は、重量分析法、精密電量滴定法、キレート滴定法，電位差滴定法，沈殿滴定法，イオンクロマトグラフ法などにより測定可能である。 The purification method is not particularly limited as long as the total inorganic ion concentration in the black dye can be reduced to 200 ppm or less. As a general method, a chromatography method, an electrophoresis method, a solvent extraction method, a solid phase extraction method, Examples thereof include a filtration method, an ultrafiltration method, a water extraction method, a dialysis method, a phase separation method, a centrifugal separation method, a sublimation method, and a recrystallization method. In addition, when synthesized, if the total inorganic ion concentration exceeds 200 ppm, it is necessary to purify and use it in the same manner. The inorganic ion concentration can be measured by gravimetric analysis, precision coulometric titration, chelate titration, potentiometric titration, precipitation titration, ion chromatography, or the like.
本発明に用いられる熱硬化性樹脂組成物としては、エポキシ樹脂系、フェノール樹脂系、ポリイミド樹脂系、不飽和ポリエステル樹脂系、ポリフェニレンエーテル樹脂系等の単独、変性物、混合物のように、熱硬化性樹脂全般を用いることができる。この熱硬化性樹脂組成物中には、熱硬化性樹脂を含有し、必要に応じてその熱硬化性樹脂の硬化剤、硬化促進剤、無機充填材及び溶剤等を含有することができる。なおエポキシ樹脂等のように自己硬化性の低い熱硬化性樹脂は、その樹脂を硬化するための硬化剤等も含有することが好ましい。 The thermosetting resin composition used in the present invention includes an epoxy resin system, a phenol resin system, a polyimide resin system, an unsaturated polyester resin system, a polyphenylene ether resin system alone, a modified product, and a thermosetting resin. General resin can be used. The thermosetting resin composition contains a thermosetting resin, and may contain a curing agent, a curing accelerator, an inorganic filler, a solvent, and the like of the thermosetting resin as necessary. In addition, it is preferable that a thermosetting resin with low self-curing property such as an epoxy resin also contains a curing agent for curing the resin.
なお、熱硬化性樹脂組成物が、エポキシ樹脂系の場合、電気特性及び接着性のバランスが良好であり好ましい。エポキシ樹脂系の樹脂組成物に含有するエポキシ樹脂としては、例えばビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、ビスフェノールＦノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹脂、及びこれらのエポキシ樹脂構造体中の水素原子の一部をハロゲン化することにより難燃化したエポキシ樹脂等が挙げられる。また、このエポキシ樹脂系の樹脂組成物に含有する硬化剤としては、例えばジシアンジアミド、脂肪族ポリアミド等のアミド系硬化剤や、アンモニア、トリエチルアミン、ジエチルアミン等のアミン系硬化剤や、フェノールノボラック樹脂、クレゾールノボラック樹脂、ｐ−キシレン−ノボラック樹脂等のフェノール系硬化剤や、酸無水物類等が挙げられる。 In addition, when a thermosetting resin composition is an epoxy resin type | system | group, the balance of an electrical property and adhesiveness is favorable and preferable. Examples of the epoxy resin contained in the epoxy resin-based resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol F novolak. Type epoxy resin, cresol novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, and epoxy resin flame-retarded by halogenating a part of hydrogen atoms in these epoxy resin structures. Examples of the curing agent contained in the epoxy resin-based resin composition include amide-based curing agents such as dicyandiamide and aliphatic polyamide, amine-based curing agents such as ammonia, triethylamine, and diethylamine, phenol novolac resins, and cresols. Examples thereof include phenolic curing agents such as novolak resin and p-xylene-novolak resin, and acid anhydrides.
なお、上記熱硬化性樹脂組成物に含有することができる無機充填材としては、シリカ、炭酸カルシウム、水酸化アルミニウム、タルク等の無機質粉末充填材や、ガラス繊維、パルプ繊維、合成繊維、セラミック繊維等の繊維質充填材が挙げられ、また、上記熱硬化性樹脂組成物に含有することができる溶剤は、Ｎ，Ｎ−ジメチルホルムアミド等のアミド類、エチレングリコールモノメチルエーテル等のエーテル類、アセトン、メチルエチルケトン等のケトン類、メタノール、エタノール等のアルコール類、ベンゼン、トルエン等の芳香族炭化水素類等が挙げられる。そして熱硬化性樹脂組成物に、前記溶剤を適宜加えることにより、繊維基材に含浸乾燥可能な任意の樹脂固形分を有する熱硬化性樹脂組成物のワニスとすることができる。 The inorganic filler that can be contained in the thermosetting resin composition includes inorganic powder fillers such as silica, calcium carbonate, aluminum hydroxide, and talc, glass fibers, pulp fibers, synthetic fibers, and ceramic fibers. Examples of the solvent that can be contained in the thermosetting resin composition include amides such as N, N-dimethylformamide, ethers such as ethylene glycol monomethyl ether, acetone, Examples thereof include ketones such as methyl ethyl ketone, alcohols such as methanol and ethanol, and aromatic hydrocarbons such as benzene and toluene. And by adding the said solvent suitably to a thermosetting resin composition, it can be set as the varnish of the thermosetting resin composition which has arbitrary resin solid content which can be impregnated and dried to a fiber base material.
前記一般式（１）で示される黒色染料の配合量は、熱硬化性樹脂組成物中に２重量％以下の範囲とされるのが好ましい。２重量％を超えて多量に配合しても効果は変わらない。また、配合量の下限は積層板としたときの黒色の度合が１９７６ＣＩＥ明度Ｌ*で２５以下になるように適宜選定されることが好ましい。１９７６ＣＩＥ明度Ｌ*で２５を超えると黒色の度合いが不足する傾向にある。 The blending amount of the black dye represented by the general formula (1) is preferably in the range of 2% by weight or less in the thermosetting resin composition. The effect does not change even if it is added in a large amount exceeding 2% by weight. Moreover, it is preferable that the lower limit of the blending amount is appropriately selected so that the degree of black when the laminate is used is 25 or less in terms of 1976 CIE lightness L *. When the 1976 CIE lightness L * exceeds 25, the degree of black tends to be insufficient.
本発明の熱硬化性樹脂組成物のワニスを繊維基材に含浸乾燥し、プリプレグを製造する方法としては特に限定するものではなく、一般の方法が適用可能である。なお熱硬化性樹脂組成物のワニスの含浸量は、ワニス樹脂固形分と繊維基材の総量に対して、ワニス樹脂固形分が、３０〜８０重量％になるようにすることが好ましい。繊維基材は、積層板やプリント配線板を製造する際に用いられるものであれば特に制限されないが、通常織布や不織布等の繊維基材が用いられる。繊維基材の材質は、ガラス、アルミナ、アスベスト、ボロン、シリカアルミナガラス、シリカガラス、チラノ、炭化ケイ素、窒化ケイ素、ジルコニア等の無機繊維やアラミド、ポリエーテルエーテルケトン、ポリエーテルイミド、ポリエーテルサルフォン、カーボン、セルロース等の有機繊維等及びこれら混抄系があり、ガラスクロスが特に好適に用いられる。 A method for producing a prepreg by impregnating and drying a varnish of the thermosetting resin composition of the present invention on a fiber base material is not particularly limited, and a general method is applicable. The amount of varnish impregnated in the thermosetting resin composition is preferably 30 to 80% by weight based on the total amount of the varnish resin solid and the fiber substrate. Although a fiber base material will not be restrict | limited especially if it is used when manufacturing a laminated board and a printed wiring board, Usually fiber base materials, such as a woven fabric and a nonwoven fabric, are used. The material of the fiber substrate is glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, and other inorganic fibers, aramid, polyetheretherketone, polyetherimide, polyethersulfur There are organic fibers such as phon, carbon and cellulose, and mixed papers thereof, and glass cloth is particularly preferably used.
本発明の積層板は、プリプレグを少なくとも１枚含むプリプレグ構成体を加熱加圧してなる積層板である。また本発明においては、前述したように積層板には金属箔張積層板を含む意味とされる。よってプリプレグ構成体の片面又は両面に、適宜、金属箔を配置し、加熱加圧して金属箔張積層板としてもよい。積層板を製造するときの加熱加圧する条件としては、熱硬化性樹脂組成物が硬化する条件で適宜調整すればよく、例えば通常１３０〜２５０℃、好ましくは１５０℃〜２１０℃の範囲の温度で、通常０．５〜２０ＭＰａ、好ましくは１〜８ＭＰａの範囲の圧力で加熱加圧成形することにより絶縁板、積層板又は金属箔張積層板を製造することができる。また、本発明のプリプレグと、内層用プリント配線板を用い、多層プリント配線板を製造してもよく、その場合、プリプレグと内層用プリント配線板を積層した後の加熱加圧する条件としては、加圧の圧力が高いと内層用プリント配線板の導体回路の寸法収縮のばらつきが大きくなる場合があるため、成形性を満足する範囲内で、できるだけ低圧で加圧することが好ましい。なお、加熱加圧を３００Ｔｏｒｒ以下の減圧雰囲気下で行うと、成形性が良好となり好ましい。 The laminate of the present invention is a laminate obtained by heating and pressurizing a prepreg structure including at least one prepreg. In the present invention, as described above, the laminated plate includes a metal foil-clad laminated plate. Therefore, a metal foil may be appropriately disposed on one or both surfaces of the prepreg structure, and heated and pressed to form a metal foil-clad laminate. What is necessary is just to adjust suitably on the conditions which a thermosetting resin composition hardens | cures as conditions for heating and pressurizing when manufacturing a laminated board, for example, normally in the temperature range of 130-250 degreeC, Preferably it is 150 to 210 degreeC. Usually, an insulating plate, a laminated plate, or a metal foil-clad laminated plate can be produced by heat and pressure molding at a pressure in the range of 0.5 to 20 MPa, preferably 1 to 8 MPa. In addition, a multilayer printed wiring board may be manufactured using the prepreg of the present invention and the printed wiring board for the inner layer. In this case, the heating and pressurizing conditions after laminating the prepreg and the printed wiring board for the inner layer are as follows. When the pressure is high, the dimensional shrinkage variation of the conductor circuit of the printed wiring board for the inner layer may become large. Therefore, it is preferable to apply pressure as low as possible within the range satisfying the moldability. Note that it is preferable to perform heating and pressing in a reduced-pressure atmosphere of 300 Torr or less because moldability is improved.
本発明に用いられる金属箔としては銅、アルミニウム、真鍮、ニッケル等の単独、合金、複合の金属箔を用いることもできる。なお、この金属箔は、金属箔張積層板の作製のみに用いることに限定するものではなく、内層用プリント配線板とプリプレグとを積層したその積層物の片側又は両側に積層して用いてもよい。この金属箔の厚みとしては、金属箔張積層板の作製に用いる場合３〜７０μｍが一般的であり、内層用プリント配線板とプリプレグとを積層したその積層物の片側又は両側に積層する場合は、３〜７０μｍが一般的である。 As the metal foil used in the present invention, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel or the like can be used. In addition, this metal foil is not limited to use only for preparation of a metal foil-clad laminate, and may be used by being laminated on one side or both sides of the laminate in which a printed wiring board for inner layer and a prepreg are laminated. Good. The thickness of this metal foil is generally 3 to 70 μm when used for producing a metal foil-clad laminate, and when laminated on one side or both sides of the laminate obtained by laminating a printed wiring board for inner layer and a prepreg. 3 to 70 μm is common.
本発明のプリント配線板は、前記の積層板を用い配線加工してなるプリント配線板である。配線加工としては、配線板製造工程で、行われている一般的な方法を用いればよい。従って金属箔張積層板に、エッチングによる配線加工を施してプリント配線板とすることができる。あるいは金属箔の無い絶縁板また積層板を、めっき等による配線加工を施してプリント配線板とすることもできる。 The printed wiring board of the present invention is a printed wiring board obtained by performing wiring processing using the laminated board. As wiring processing, a general method performed in a wiring board manufacturing process may be used. Accordingly, the metal foil-clad laminate can be processed by etching to form a printed wiring board. Alternatively, a printed wiring board can be obtained by performing wiring processing by plating or the like on an insulating plate or laminated plate without metal foil.
以下、実施例により本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
（実施例１）
熱硬化性樹脂組成物として、下記のエポキシ樹脂２種類、硬化剤、硬化促進剤及び溶剤よりなるエポキシ樹脂系樹脂組成物を使用した。
・エポキシ樹脂１：ビスフェノールＡノボラック型エポキシ樹脂（大日本インキ化学工業株式会社製、エピクロンＮ８６８（商品名））５０重量部。
・エポキシ樹脂２：ブロム化ビスフェノールＡ型エポキシ樹脂（住友化学工業株式会社、ＥＳＢ−４００（商品名））５０重量部。
・硬化剤：ビスフェノールＡノボラック樹脂（ジャパンエポキシレジン株式会社製、ＹＬＨ−１２９（商品名））を４０重量部。
・硬化促進剤：１−シアノエチル−２−フェニルイミダゾール１重量部。
・溶剤：メチルエチルケトンを９０重量部。
このエポキシ樹脂系樹脂組成物に、全無機イオン濃度を、１５０ｐｐｍに精製した前記一般式（１）で示される黒色染料（金属錯塩アゾ系黒色染料）である化学名:クロム酸（１−），［１−［（２−ヒドロキシ−４−ニトロフェニル）アゾ］−２−ナフタレノラト（２−）］［１−［（２−ヒドロキシ−５−ニトロフェニル）アゾ］−２−ナフタレノラト（２−）］の３−［（２−エチルヘキシル）オキシ］−１−プロパンアミン水素（１：１）化合物）０．５重量部を溶解することにより、熱硬化性樹脂組成物（エポキシ樹脂組成物）のワニスを調製した。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Example 1
As the thermosetting resin composition, an epoxy resin resin composition composed of the following two epoxy resins, a curing agent, a curing accelerator and a solvent was used.
Epoxy resin 1: 50 parts by weight of a bisphenol A novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., Epicron N868 (trade name)).
Epoxy resin 2: 50 parts by weight of brominated bisphenol A type epoxy resin (Sumitomo Chemical Co., Ltd., ESB-400 (trade name)).
Curing agent: 40 parts by weight of bisphenol A novolak resin (Japan Epoxy Resin Co., Ltd., YLH-129 (trade name)).
Curing accelerator: 1 part by weight of 1-cyanoethyl-2-phenylimidazole.
Solvent: 90 parts by weight of methyl ethyl ketone.
This epoxy resin-based resin composition has a chemical name: chromic acid (1-), which is a black dye (metal complex azo-based black dye) represented by the above general formula (1) purified to a total inorganic ion concentration of 150 ppm. [1-[(2-hydroxy-4-nitrophenyl) azo] -2-naphthalenolato (2-)] [1-[(2-hydroxy-5-nitrophenyl) azo] -2-naphthalenolato (2-)] 3-[(2-ethylhexyl) oxy] -1-propanamine hydrogen (1: 1) compound) of 0.5 part by weight of varnish of the thermosetting resin composition (epoxy resin composition) Prepared.
調製した熱硬化性樹脂組成物（エポキシ樹脂組成物）ワニスを、繊維基材である厚さ０．１ｍｍ、坪量１０４ｇ／ｍ２のガラスクロス（規格ＩＰＣ＃２１１６）に含浸乾燥後のワニス樹脂固形分が５０重量％になるように含浸乾燥してプリプレグを作製した。作製したプリプレグを２枚重ね、その両面に厚さ１８μｍの銅箔を置き、温度１８５℃、圧力３ＭＰａで減圧下に６０分間加熱加圧して両面銅張積層板を作製した。作製した両面銅張積層板にエッチングを施して回路を形成することにより両面プリント配線板を作製した。作製した両面プリント配線板は、基板の外観が黒色を基調としており、ワイヤボンディングの良否識別が容易であった。 Varnish resin after impregnating and drying the prepared thermosetting resin composition (epoxy resin composition) varnish into a glass cloth (standard IPC # 2116) having a thickness of 0.1 mm and a basis weight of 104 g / m 2 as a fiber base material. A prepreg was prepared by impregnation and drying so that the solid content was 50% by weight. Two prepared prepregs were stacked, and a copper foil having a thickness of 18 μm was placed on both sides thereof, and heated and pressed under reduced pressure at a temperature of 185 ° C. and a pressure of 3 MPa for 60 minutes to prepare a double-sided copper-clad laminate. A double-sided printed wiring board was produced by etching the produced double-sided copper-clad laminate to form a circuit. The produced double-sided printed wiring board was based on the black appearance of the substrate, and the wire bonding quality was easily identified.
（比較例１）
実施例１の黒色染料（金属錯塩アゾ系黒色染料）の代わりに、全無機イオン濃度が、３０００ｐｐｍである金属錯塩アゾ系黒色染料（中央合成化学株式会社製、ネオスーパーブラックＣ−８３２（商品名を使用））を０．５重量部配合したほかは、実施例１と同様にして、両面プリント配線板を作製した。作製した両面プリント配線板の基板は、外観が黒色を基調としており、ワイヤボンディングの良否識別が容易であった。
(Comparative Example 1)
Instead of the black dye of Example 1 (metal complex azo black dye), a metal complex azo black dye having a total inorganic ion concentration of 3000 ppm (manufactured by Chuo Synthetic Chemical Co., Ltd., Neo Super Black C-832 (trade name) A double-sided printed wiring board was produced in the same manner as in Example 1 except that 0.5 part by weight of the above was blended. The substrate of the produced double-sided printed wiring board was based on black in appearance, and the quality of wire bonding was easy to identify.
（比較例２）
実施例１の黒色染料（金属錯塩アゾ系黒色染料）の代わりに前記一般式（３）で示されるアゾ系黒色染料（中央合成化学株式会社製、スーダンブラック１４１（商品名を使用））を０．５重量部配合したほかは、実施例１と同様にして、両面プリント配線板を作製した。作製した両面プリント配線板の基板は、外観が黒色を基調としており、ワイヤボンディングの良否識別が容易であった。
(Comparative Example 2)
Instead of the black dye (metal complex salt azo black dye) of Example 1, the azo black dye represented by the general formula (3) (Sudan Black 141 (trade name) manufactured by Chuo Synthetic Chemical Co., Ltd.) is used. A double-sided printed wiring board was produced in the same manner as in Example 1 except that 5 parts by weight was blended. The substrate of the produced double-sided printed wiring board was based on black in appearance, and the quality of wire bonding was easy to identify.
（比較例３）
実施例１の黒色染料（金属錯塩アゾ系黒色染料）の代わりにカーボンブラックを０．５重量部配合したほかは、実施例１と同様にして、両面プリント配線板を作製した。作製した両面プリント配線板の基板は、外観が黒色を基調としており、ワイヤボンディングの良否識別が容易であった。
(Comparative Example 3)
A double-sided printed wiring board was produced in the same manner as in Example 1 except that 0.5 parts by weight of carbon black was blended in place of the black dye (metal complex azo black dye) of Example 1. The substrate of the produced double-sided printed wiring board was based on black in appearance, and the quality of wire bonding was easy to identify.
実施例１及び比較例１〜３で作製した両面銅張積層板に、穴間距離３００μｍまたは２００μｍ，穴径Φ０．５の穴を１００穴形成し、更に表裏の回路をめっきにより電気的に接続した回路パターンを２回路形成した。温度８５℃、相対湿度８５％の恒温恒湿槽中にて、この２回路間に直流１００Ｖの電圧を１０００時間印加した。その後の２回路間の絶縁抵抗を測定することにより耐電食性を調べた。なお耐電食性試験前の絶縁抵抗は、穴間距離３００μｍ、２００μｍとも１×１０１２Ωであった。また、両面銅張積層板の外観色相を常態と、２４０℃１時間処理後に、銅箔エッチングし調べた。また両面銅張積層板の硬化度確認のため、ＴＭＡ法によるＴｇを調べた。これらの結果を表１に示した。 100 holes with a distance between holes of 300 μm or 200 μm and a hole diameter of Φ0.5 are formed on the double-sided copper clad laminates produced in Example 1 and Comparative Examples 1 to 3, and the front and back circuits are electrically connected by plating. Two circuit patterns were formed. A voltage of DC 100 V was applied between these two circuits for 1000 hours in a constant temperature and humidity chamber having a temperature of 85 ° C. and a relative humidity of 85%. The electrical corrosion resistance was examined by measuring the insulation resistance between the subsequent two circuits. The insulation resistance before the electric corrosion resistance test was 1 × 10 12 Ω for both the distances between the holes of 300 μm and 200 μm. Further, the appearance color of the double-sided copper-clad laminate was examined by etching a copper foil after treatment at 240 ° C. for 1 hour. Moreover, Tg by TMA method was investigated in order to confirm the curing degree of the double-sided copper-clad laminate. These results are shown in Table 1.
表１から、全無機イオン濃度が１５０ｐｐｍである前記一般式（１）で示される黒色染料（金属錯塩アゾ系黒色染料）を配合した実施例１ではプリント配線板の電食試験による絶縁抵抗の低下が無いことから信頼性が良好であることが示される。これに対して全無機イオン濃度が３０００ｐｐｍである黒色染料（金属錯塩アゾ系黒色染料）を配合した比較例１及びカーボンブラックを配合した比較例３では、プリント配線板に電食試験による絶縁抵抗の低下が示された。また、全無機イオン濃度が多い比較例１は加熱加圧して得られた積層板のＴｇが低いことから硬化反応に影響し信頼性の低下が示された。更に、アゾ系黒色染料を配合した比較例２は高温処理後に退色が見られた。 From Table 1, in Example 1 in which the black dye (metal complex salt azo black dye) represented by the general formula (1) having a total inorganic ion concentration of 150 ppm was blended, the insulation resistance was reduced by the electrolytic corrosion test of the printed wiring board. This indicates that the reliability is good. On the other hand, in Comparative Example 1 in which a black dye (metal complex salt azo black dye) having a total inorganic ion concentration of 3000 ppm was blended and in Comparative Example 3 in which carbon black was blended, the insulation resistance of the printed wiring board was measured by an electrolytic corrosion test. Declined. In Comparative Example 1 having a high total inorganic ion concentration, the Tg of the laminate obtained by heating and pressurization was low, which affected the curing reaction and showed a decrease in reliability. Further, in Comparative Example 2 in which an azo black dye was blended, fading was observed after high temperature treatment.
Claims (4)
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