JP2006182991A - Resin composition for printed wiring board, resin varnish, prepreg and laminated plate using it - Google Patents
Resin composition for printed wiring board, resin varnish, prepreg and laminated plate using it Download PDFInfo
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Abstract
Description
本発明は、プリント配線板用樹脂組成物、およびそれを用いた樹脂ワニス、プリプレグおよび積層板に関する。 The present invention relates to a resin composition for printed wiring boards, and a resin varnish, prepreg and laminate using the same.
電気・電子機器等に使用される金属箔張り積層板は、例えば、ガラスクロス等の基材にエポキシ樹脂組成物等の熱硬化性樹脂ワニスを含浸した後、加熱して半硬化させることによってプリプレグを作製し、このプリプレグを所要枚数重ねると共に、銅箔等の金属箔をその片側又は両側に配して積層し、加熱加圧して成形を行うことによって製造されている。また、多層の金属箔張り積層板は、上記の方法で得られた金属箔張り積層板の表面の金属箔をエッチングして導体回路を形成した後、その導体回路を形成した積層板の表裏に、上記と同様のプリプレグを所要枚数重ねるとともに、金属箔をその片側又は両側に配して積層し、加熱加圧して成形を行うことによって製造されている。これらの積層板に用いられるエポキシ樹脂組成物としては、エポキシ当量が１００〜１０００程度の低分子量のエポキシ樹脂とアミン系硬化剤および硬化促進剤を含んでなる組成物が一般的である。 Metal foil-clad laminates used in electrical and electronic equipment, for example, are prepared by impregnating a base material such as glass cloth with a thermosetting resin varnish such as an epoxy resin composition and then heating and semi-curing the prepreg. Is manufactured by stacking a required number of the prepregs, laminating a metal foil such as a copper foil on one side or both sides thereof, and heating and pressing to form. In addition, a multilayer metal foil-clad laminate is formed by etching the metal foil on the surface of the metal foil-clad laminate obtained by the above method to form a conductor circuit, and then on the front and back sides of the laminate on which the conductor circuit is formed. A prepreg similar to that described above is stacked, and a metal foil is disposed on one side or both sides of the prepreg, stacked, and heated and pressed to form. As an epoxy resin composition used for these laminates, a composition comprising a low molecular weight epoxy resin having an epoxy equivalent of about 100 to 1000, an amine curing agent and a curing accelerator is common.
近年、電気・電子機器に組込むエポキシ樹脂プリント配線板には、燃えにくいこと、燃え広がりにくいことと言った安全性が求められている。そこで、臭素化エポキシ樹脂やエポキシ樹脂の硬化剤として臭素付加フェノールノボラック樹脂等を使用し、難燃性を付与している。しかし、臭素などのハロゲン含有エポキシ樹脂を高温下で長時間使用するとハロゲン化物が解離する懸念があり、また、ハロゲン含有エポキシ樹脂を焼却処理すると有害なハロゲン化物が発生するといった心配がある。そこで最近では、環境安全の面から、ノンハロゲン難燃性付与剤で難燃性を付与するという方向に変わりつつある。ハロゲン化合物に代わり、難燃性付与剤としてリン化合物が注目されている。かかるリン化合物の殆どはリン酸エステル系で、低融点（８０〜１００℃）の化合物であるので、樹脂燃焼時に曝されるような高温では容易に熱分解する。この熱分解で生成するポリリン酸の炭化皮膜が樹脂を酸素及び熱から遮蔽することによって、難燃効果を発揮している。しかし、リン酸エステル系だけでは十分な難燃性が得られないため、水酸化物のような充填材などを併用する方法が多い。リン変性の難燃性エポキシ樹脂組成物を使用する方法（特開２０００−８０２５１号公報）も知られているが、この方法ではＴｇが低下してしまい、また難燃性が十分ではないため充填剤と併用して使用されている。 In recent years, epoxy resin printed wiring boards incorporated in electric and electronic devices are required to have safety such as being hard to burn and difficult to spread. Therefore, brominated epoxy novolak resin or the like is used as a brominated epoxy resin or epoxy resin curing agent to impart flame retardancy. However, when a halogen-containing epoxy resin such as bromine is used at a high temperature for a long time, the halide may be dissociated, and when the halogen-containing epoxy resin is incinerated, a harmful halide may be generated. Therefore, recently, from the viewpoint of environmental safety, there is a change in the direction of imparting flame retardancy with a non-halogen flame retarder. Instead of halogen compounds, phosphorus compounds have attracted attention as flame retardant imparting agents. Most of these phosphorus compounds are phosphoric acid ester-based compounds having a low melting point (80 to 100 ° C.), so that they are easily thermally decomposed at high temperatures exposed during resin combustion. The carbonized coating of polyphosphoric acid produced by this thermal decomposition shields the resin from oxygen and heat, thereby exhibiting a flame retardant effect. However, since sufficient flame retardancy cannot be obtained only with phosphoric acid esters, there are many methods in which fillers such as hydroxides are used in combination. A method using a phosphorus-modified flame-retardant epoxy resin composition (Japanese Patent Laid-Open No. 2000-80251) is also known. However, this method reduces Tg and is not sufficient for flame retardancy. It is used in combination with an agent.
一般的に、プリント配線板や多層プリント配線板は、部品実装のための半田付や２７０℃程度のリフロー工程で高温に曝される。難燃性付与のために低融点のリン化合物を多く添加しておくと、前記リフロー工程でリン化合物が熱分解し、プリント配線と樹脂の界面でふくれが発生するという問題がある。また、難燃性付与のため充填材を併用することで加工性を著しく低下し、さらに誘電特性等をも悪化させる原因となっている。また、最近では難燃性付与のためトリアジン変性ノボラックとリン化合物を併用する方法が知られているが（特開平１１−４３５３６号公報）、リン化合物の熱分解によって鉛フリーのはんだ材料のような高温のはんだではふくれが発生してしまう。 Generally, a printed wiring board or a multilayer printed wiring board is exposed to high temperatures by soldering for component mounting or a reflow process at about 270 ° C. If a large amount of a low melting point phosphorus compound is added to impart flame retardancy, the phosphorus compound is thermally decomposed in the reflow process, and there is a problem that blistering occurs at the interface between the printed wiring and the resin. In addition, the use of a filler in combination with flame retardancy significantly reduces workability and further deteriorates dielectric properties and the like. Recently, a method of using a triazine-modified novolak in combination with a phosphorus compound for imparting flame retardancy is known (Japanese Patent Laid-Open No. 11-43536). High temperature solder will cause blistering.
従って、プリント配線板や多層プリント配線板に難燃性を付与するためにリン化合物や充填材を添加する場合は、その添加によって耐熱性が低下しないことが併せて要求されている。 Therefore, when a phosphorus compound or a filler is added to impart flame retardancy to a printed wiring board or a multilayer printed wiring board, it is also required that the heat resistance does not decrease due to the addition.
また、電気・電子機器の高速化、薄物化に伴い、パッケージなどに使用されるプリント配線板用材料には高接続信頼性が必要であるため、Ｔｇの高い材料が要求されている。そこに使用される樹脂としては特にノボラック型エポキシ樹脂やシアネート樹脂などが多く使われている。しかし架橋密度をあげることで、樹脂の弾性率が大きくなり、伸びも小さくなる傾向にある。そのため熱衝撃などに弱く高温のはんだやリフロー工程などでのふくれの原因となっている。 In addition, as electrical and electronic devices are made faster and thinner, printed wiring board materials used for packages and the like require high connection reliability, and therefore, materials with high Tg are required. As a resin used there, a novolac type epoxy resin, a cyanate resin and the like are often used. However, increasing the crosslink density tends to increase the elastic modulus and decrease the elongation of the resin. For this reason, it is vulnerable to thermal shock and causes blistering in high-temperature solder and reflow processes.
本発明はノンハロゲン樹脂組成物でありながら、高い難燃性を有し、低誘電率で高Ｔｇであり、優れた耐熱性を満足するプリント配線板用樹脂組成物、およびそれを用いた樹脂ワニス、プリプレグおよび積層板を提供することを目的とする。 The present invention is a non-halogen resin composition, has a high flame retardancy, a low dielectric constant and a high Tg, and satisfies the excellent heat resistance, and a resin varnish using the same An object is to provide a prepreg and a laminate.
本発明（１）は、（ａ）ビフェニル型エポキシ樹脂およびクレゾールノボラック型エポキシ樹脂からなるエポキシ樹脂、（ｂ）分子構造中に窒素原子を含有するフェノール樹脂、（ｃ）少なくとも二種類のリンの含有率が８％以上２５％以下であるリン化合物、を含有するプリント配線板用樹脂組成物に関する。 The present invention (1) includes (a) an epoxy resin comprising a biphenyl type epoxy resin and a cresol novolac type epoxy resin, (b) a phenol resin containing a nitrogen atom in the molecular structure, and (c) containing at least two types of phosphorus. It is related with the resin composition for printed wiring boards containing the phosphorus compound whose rate is 8% or more and 25% or less.
また、本発明（２）は、ビフェニル型エポキシ樹脂２０〜６０重量部およびクレゾールノボラック型エポキシ樹脂４０〜８０重量部からなるエポキシ樹脂１００重量部あたり、分子構造中に窒素原子を含有するフェノール樹脂２５〜６５重量部であり、全樹脂組成物あたり、リンの含有率が２．５〜４．５重量％であることを特徴とする前記（１）に記載のプリント配線板用樹脂組成物に関する。 Moreover, this invention (2) is the phenol resin 25 which contains a nitrogen atom in molecular structure per 100 weight part of epoxy resins which consists of 20-60 weight part of biphenyl type epoxy resins and 40-80 weight parts of cresol novolak type epoxy resins. It is -65 weight part, It is related with the resin composition for printed wiring boards as described in said (1) characterized by the content rate of phosphorus being 2.5-4.5 weight% per total resin composition.
また、本発明（３）は、（ｂ）分子構造中に窒素原子を含有するフェノール樹脂の窒素原子の含有率が１２〜２５％であることを特徴とする前記（１）または（２）に記載のプリント配線板用樹脂組成物に関する。 In addition, the present invention (3) is the above (1) or (2), characterized in that the content of nitrogen atoms in the phenol resin containing nitrogen atoms in the molecular structure (b) is 12 to 25%. It is related with the resin composition for printed wiring boards of description.
また、本発明（４）は、前記（１）〜（３）のいずれかに記載の樹脂組成物を、溶剤に溶解又は分散させて得られるプリント配線用樹脂ワニスに関する。 Moreover, this invention (4) relates to the resin varnish for printed wiring obtained by melt | dissolving or disperse | distributing the resin composition in any one of said (1)-(3) in a solvent.
また、本発明（５）は、前記（４）記載のプリント配線板用樹脂ワニスを基材に含浸し、乾燥して、Ｂステージ化して得られるプリント配線板用プリプレグに関する。 Moreover, this invention (5) relates to the prepreg for printed wiring boards obtained by impregnating the resin varnish for printed wiring boards of said (4) to a base material, drying and making it into B stage.
また、本発明（６）は、前記基材がガラス繊維である前記（５）記載のプリント配線板用プリプレグに関する。 Moreover, this invention (6) relates to the prepreg for printed wiring boards as described in said (5) whose said base material is glass fiber.
また、本発明（７）は、前記（５）または（６）に記載のプリント配線板用プリプレグを１枚以上重ね、少なくともその片面に金属箔を積層し、加熱加圧して得られる金属張積層板に関する。 Further, the present invention (7) is a metal-clad laminate obtained by laminating one or more prepregs for printed wiring boards according to the above (5) or (6), laminating metal foil on at least one surface, and heating and pressing. Regarding the board.
本発明はノンハロゲン樹脂組成物でありながら、高い難燃性を有し、高Ｔｇであり耐熱性に優れ、かつ低誘電率を満足するプリント配線板用樹脂組成物、およびそれを用いた樹脂ワニス、プリプレグおよび積層板を提供することができる。したがって、本発明の積層板はプリント配線板の高速化や部品実装時の高温はんだリフローなどにも対応可能であり、信頼性に優れたプリント配線板を製造することができる。 The present invention is a non-halogen resin composition, yet has high flame retardancy, high Tg, excellent heat resistance, and a low dielectric constant, and a resin varnish using the same A prepreg and a laminate can be provided. Therefore, the laminated board of the present invention can cope with high-speed printed wiring boards and high-temperature solder reflow during component mounting, and can produce printed wiring boards with excellent reliability.
本発明の（ａ）成分は、ビフェニル型エポキシ樹脂およびクレゾールノボラック型エポキシ樹脂からなるエポキシ樹脂である。ビフェニル型エポキシ樹脂は、下記式で表されるビフェニル骨格を含有するエポキシ樹脂である。 The component (a) of the present invention is an epoxy resin composed of a biphenyl type epoxy resin and a cresol novolac type epoxy resin. The biphenyl type epoxy resin is an epoxy resin containing a biphenyl skeleton represented by the following formula.
式中、Ｒ１及びＲ６はグリシジルエーテル基であり、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ７、Ｒ８、Ｒ９、Ｒ１０は水素原子、炭素数１〜４のアルキル基またはフェニル基である。例えば、テトラメチルビフェニル型エポキシ樹脂やフェノールビフェニレンノボラック型エポキシ樹脂などが例示されるが、これらに限定されるものでなく、数種類を併用しても差し支えない。かかるビフェニル型エポキシ樹脂のエポキシ当量は１５０〜３５０が好ましい。クレゾールノボラック型エポキシ樹脂としては、軟化点が７０℃から８０℃のものが好ましい。
In the formula, R 1 and R 6 are glycidyl ether groups, R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 are a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Or it is a phenyl group. For example, tetramethyl biphenyl type epoxy resin and phenol biphenylene novolac type epoxy resin are exemplified, but the present invention is not limited to these, and several types may be used in combination. The biphenyl type epoxy resin preferably has an epoxy equivalent of 150 to 350. As the cresol novolac type epoxy resin, those having a softening point of 70 ° C. to 80 ° C. are preferable.
本発明（ｂ）成分は、分子構造中に窒素原子を含有するフェノール樹脂であり、エポキシ樹脂の硬化剤として用いられる。かかるフェノール樹脂は、分子構造中に１２％〜２５％の窒素原子を含有しているものが好ましい。分子構造中に窒素原子を含有するフェノール樹脂としては、例えば、トリアジン化合物で変性してなるフェノール樹脂硬化剤であり、メラミン、ベンゾグアナミン、アセトグアナミンなどのトリアジン化合物で、フェノール樹脂、フェノールノボラック樹脂、クレゾール骨格含有フェノール樹脂、クレゾール骨格含有フェノールノボラック樹脂などのフェノール樹脂硬化剤を変性してなるものである。例えば、メラミン変性フェノール樹脂、メラミン変性フェノールノボラック樹脂、ベンゾグアナミン変性フェノールノボラック樹脂、アセトグアナミン変性フェノールノボラック樹脂、メラミン変性クレゾール骨格含有フェノール樹脂などが挙げられるが、これらに限定されるものではない。市販品では、大日本インキ化学工業株式会社製ＬＡ−７０５４（水酸基当量１２５、窒素含有率１２％）、ＪＥＲ製ＹＬＨ８２８（水酸基当量１４８、窒素含有率２０％）などが挙げられる。（ａ）成分のエポキシ樹脂との配合比率についてはエポキシ基（エポキシ樹脂配合量／エポキシ当量）と水酸基（フェノール樹脂配合量／水酸基当量）の比率がエポキシ樹脂に対してフェノール樹脂が０．４〜０．８になるように配合することが望ましい。０．４未満では硬化が遅くなり、０．８を越えると耐熱性が低下する傾向にある。 The component (b) of the present invention is a phenol resin containing a nitrogen atom in the molecular structure, and is used as a curing agent for the epoxy resin. Such a phenol resin preferably contains 12% to 25% nitrogen atoms in the molecular structure. The phenol resin containing a nitrogen atom in the molecular structure is, for example, a phenol resin curing agent modified with a triazine compound, and a triazine compound such as melamine, benzoguanamine, acetoguanamine, phenol resin, phenol novolac resin, cresol. It is obtained by modifying a phenol resin curing agent such as a skeleton-containing phenol resin or a cresol skeleton-containing phenol novolac resin. Examples include, but are not limited to, melamine-modified phenol resin, melamine-modified phenol novolak resin, benzoguanamine-modified phenol novolak resin, acetoguanamine-modified phenol novolak resin, melamine-modified cresol skeleton-containing phenol resin. Examples of commercially available products include LA-7054 (hydroxyl equivalent: 125, nitrogen content: 12%) manufactured by Dainippon Ink and Chemicals, Ltd., and YLH828 (hydroxyl equivalent: 148, nitrogen content: 20%) manufactured by JER. (A) About the compounding ratio with the epoxy resin of a component, the ratio of an epoxy group (epoxy resin compounding amount / epoxy equivalent) and a hydroxyl group (phenol resin compounding amount / hydroxyl group equivalent) is 0.4-phenol resin with respect to an epoxy resin. It is desirable to blend so as to be 0.8. If it is less than 0.4, the curing is slow, and if it exceeds 0.8, the heat resistance tends to decrease.
本発明の（ｃ）成分は、リンの含有率が８％以上２５％以下である。例えば、市販されている化合物を用いることができ、例えば芳香族縮合リン酸エステル（ＰＸ−２００、大八化学工業株式会社製、リン含有率９．１％）、９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナンスレン−１０−オキサイド（ＨＣＡ、三光化学株式会社製、リン含有率１４．３％）、１０（２，５−ジヒドロキシフェニル）−１０Ｈ−９オキサ−１０−ホスファフェナントレン−１０−オキサイド（ＨＣＡ−ＨＱ、三光化学株式会社製、リン含有率９．５％）、ホスフィン酸塩やジホスフィン酸塩などリン含有率が２０％以上であるリン化合物（ＯＰ９３０、クラリアント製、リン含有率２３％）などを挙げることができる。なかでも、好ましくはリン含有率が高く熱分解温度が高いものが望ましい。本発明ではかかるリン化合物を２種類以上用いることが必須である。 The component (c) of the present invention has a phosphorus content of 8% or more and 25% or less. For example, a commercially available compound can be used, for example, aromatic condensed phosphate ester (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.1%), 9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide (HCA, Sanko Chemical Co., Ltd., phosphorus content 14.3%), 10 (2,5-dihydroxyphenyl) -10H-9 oxa-10-phospha Phenanthrene-10-oxide (HCA-HQ, manufactured by Sanko Chemical Co., Ltd., phosphorus content 9.5%), phosphorus compounds such as phosphinates and diphosphinates having a phosphorus content of 20% or more (OP930, manufactured by Clariant, Phosphorus content 23%). Among them, those having a high phosphorus content and a high thermal decomposition temperature are desirable. In the present invention, it is essential to use two or more of such phosphorus compounds.
本発明の樹脂組成物の前記各成分の配合は、ビフェニル型エポキシ樹脂２０〜６０重量部およびクレゾールノボラック型エポキシ樹脂４０〜８０重量部からなるエポキシ樹脂１００重量部あたり、分子構造中に窒素原子を含有するフェノール樹脂２５〜６５重量部であり、全樹脂組成物あたり、リンの含有率が２．５〜４．５重量％であることが望ましい。 The compounding of the above components of the resin composition of the present invention is carried out by adding nitrogen atoms in the molecular structure per 100 parts by weight of epoxy resin comprising 20 to 60 parts by weight of biphenyl type epoxy resin and 40 to 80 parts by weight of cresol novolac type epoxy resin. It is preferable that it is 25-65 weight part of phenol resin to contain, and the content rate of phosphorus is 2.5-4.5 weight% per total resin composition.
本発明の樹脂組成物は、上記（ａ）、（ｂ）、（ｃ）は必須成分であるが、本発明の目的の範囲内において、必要に応じて硬化促進剤、着色剤、酸化防止剤、還元剤、紫外線不透過剤等を加えることができる。また、打抜き加工性やドリル加工性および誘電特性を低下させない程度に充填剤を加えても良い。充填剤としてはタルク、マイカ、シリカなどが挙げられる。ただし、本発明の樹脂組成物は、その課題からハロゲン化合物を含有しないため、それらの構造を含んだ添加剤は使用することができない。 In the resin composition of the present invention, the above (a), (b), and (c) are essential components, but within the scope of the object of the present invention, a curing accelerator, a colorant, and an antioxidant as necessary. Further, a reducing agent, an ultraviolet opaque agent and the like can be added. Further, a filler may be added to such an extent that punching workability, drill workability and dielectric properties are not deteriorated. Examples of the filler include talc, mica and silica. However, since the resin composition of the present invention does not contain a halogen compound due to the problem, additives containing these structures cannot be used.
本発明の樹脂組成物を溶剤に溶解または分散させてワニス化し、それを基材に含浸させて、乾燥して、Ｂステージ化することによりプリプレグを得ることができる。希釈してワニス化するための溶剤は特に限定はなく、例えば、メタノール、エタノール、ブタノール、イソプロパノールなどのアルコール系溶剤、テトラヒドロフラン、エチレングリコールモノメチルエーテルなどのエーテル系溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶剤、Ｎ−メチルピロリドン、Ｎ、Ｎ’−ジメチルホルムアミド、Ｎ、Ｎ’−ジエチルアセトアミドなどのアミド系溶剤、ベンゼン、トルエン、キシレン、トリメチルベンゼンなどの芳香族炭化水素系溶剤、酢酸エチル、メチルセロソルブアセテートなどのエステル系溶剤、ブチロニトリルなどのニトリル系溶剤等があり、これらは単独で用いても何種類かを混合して用いてもよい。また、ワニスの固形分濃度は特に制限はなく、樹脂の組成や無機充填剤の種類及び配合量等により適宜変更できるが、５０重量％〜８０重量％の範囲が好ましい。５０重量％未満の場合はワニス粘度が低く、プリプレグの樹脂分が低くなりすぎ、８０重量％を越える場合はワニスの増粘等によりプリプレグの外観等が著しく低下しやすい。 A prepreg can be obtained by dissolving or dispersing the resin composition of the present invention in a solvent to form a varnish, impregnating it into a base material, drying it, and forming it into a B-stage. The solvent for diluting to varnish is not particularly limited, for example, alcohol solvents such as methanol, ethanol, butanol, isopropanol, ether solvents such as tetrahydrofuran, ethylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents, amide solvents such as N-methylpyrrolidone, N, N'-dimethylformamide, N, N'-diethylacetamide, aromatic hydrocarbon solvents such as benzene, toluene, xylene, trimethylbenzene, ethyl acetate There are ester solvents such as methyl cellosolve acetate, nitrile solvents such as butyronitrile, etc., and these may be used alone or in combination. Further, the solid content concentration of the varnish is not particularly limited and can be appropriately changed depending on the resin composition, the type and blending amount of the inorganic filler, and the range of 50 wt% to 80 wt% is preferable. When the amount is less than 50% by weight, the varnish viscosity is low and the resin content of the prepreg becomes too low. When the amount exceeds 80% by weight, the appearance of the prepreg is likely to be remarkably deteriorated due to thickening of the varnish.
前記各成分を配合して得たワニスを含浸させる基材としては、金属箔張り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。繊維基材としては、たとえばガラス、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の混抄系があり、特にガラス繊維が好ましく、ガラス織布または不織布が特に好ましく用いられる。ガラス織布または不織布の種類には特に指定はなく、厚さ０．０２〜０．４ｍｍまでのものを、目的のプリプレグまたは積層板の厚さに合わせて使用することができる。樹脂ワニスを基材に含浸させる方法としては、特に制限されず、例えば、ウェット方式やドライ方式などの樹脂液に基材を含浸させる方法などが挙げられる。含浸量は樹脂分として示されるが、樹脂分とはプリプレグの全重量に対する有機樹脂固形分と無機充填剤類の合計重量の割合のことであり、３０〜９０重量％であると好ましく、４０〜８０重量％であるとより好ましい。樹脂分は目的のプリプレグの性能、および積層後の絶縁層の厚さに合わせて適宜決定される。プリプレグを製造する時の乾燥条件は乾燥温度６０〜２００℃、乾燥時間１〜３０分間の間で目的のプリプレグ特性に合わせて自由に選択することができる。 The base material impregnated with the varnish obtained by blending the above components is not particularly limited as long as it is used when producing a metal foil-clad laminate or a printed wiring board. The fiber base material is used. Examples of the fiber substrate include inorganic fibers such as glass, alumina, asbestos, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, aramid, polyether ether ketone, polyether imide, polyether sal There are organic fibers such as phon, carbon, and cellulose, and mixed papers thereof. In particular, glass fibers are preferable, and glass woven fabric or nonwoven fabric is particularly preferably used. The type of the glass woven fabric or the nonwoven fabric is not particularly specified, and those having a thickness of 0.02 to 0.4 mm can be used according to the thickness of the target prepreg or laminate. The method for impregnating the substrate with the resin varnish is not particularly limited, and examples thereof include a method of impregnating the substrate with a resin liquid such as a wet method or a dry method. The amount of impregnation is shown as the resin content, which is the ratio of the total weight of the organic resin solid content and the inorganic fillers to the total weight of the prepreg, preferably 30 to 90% by weight, 80% by weight is more preferable. The resin content is appropriately determined according to the performance of the target prepreg and the thickness of the insulating layer after lamination. The drying conditions for producing the prepreg can be freely selected according to the desired prepreg characteristics within a drying temperature of 60 to 200 ° C. and a drying time of 1 to 30 minutes.
かくして得られたプリプレグを一枚以上重ね、目的とする積層板の厚みに合わせて積層し、少なくともその片面に金属箔を積層して配して、加熱加圧成形して金属張積層板を製造する。金属箔としては主に銅箔やアルミ箔を用いるが、他の金属箔を用いてもよい。金属箔の厚みは通常３〜２００μｍである。また、ニッケル、ニッケル−リン、ニッケル−スズ合金、ニッケル−鉄合金、鉛、鉛−スズ合金等を中間層とし、この両面に０．５〜１５μｍの銅層と１０〜３００μｍの銅層を設けた３層構造の複合箔あるいはアルミニウムと銅箔を複合した２層構造複合箔を用いることができる。 One or more prepregs obtained in this way are stacked, stacked according to the thickness of the target laminate, and a metal foil is laminated on at least one side, and heated and pressed to produce a metal-clad laminate To do. Although copper foil and aluminum foil are mainly used as the metal foil, other metal foils may be used. The thickness of the metal foil is usually 3 to 200 μm. Also, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. are used as intermediate layers, and a 0.5-15 μm copper layer and a 10-300 μm copper layer are provided on both sides. Alternatively, a composite foil having a three-layer structure or a two-layer composite foil in which aluminum and a copper foil are combined can be used.
金属張積層板製造時の加熱温度は１３０〜２５０℃、より好ましくは１５０〜２００℃で、圧力は０．５〜１０Ｍｐａ、より好ましくは１〜８Ｍｐａであり、プリプレグ特性や、プレス機の能力、目的の積層板の厚み等により適宜決定する。 The heating temperature at the time of producing the metal-clad laminate is 130 to 250 ° C., more preferably 150 to 200 ° C., and the pressure is 0.5 to 10 Mpa, more preferably 1 to 8 Mpa. It is determined appropriately depending on the thickness of the target laminate.
かくして得られた金属張積層板に回路加工を施してプリント配線板とすることができる。 The metal-clad laminate thus obtained can be processed into a printed wiring board.
以下に本発明における実施例と比較例を示す。「部」は「重量％」を示す。
（実施例１）
テトラメチルビフェニル型エポキシ樹脂 ３０部
（ＪＥＲ製 ＹＸ４０００ エポキシ当量１８５）
クレゾールノボラック型エポキシ樹脂 ７０部
（ＪＥＲ製 Ｅ１８０ エポキシ当量２１０）
メラミン変性ノボラック樹脂 ５９.４部
（ＪＥＲ製 ＹＬＨ８２８、水酸基当量１４８ Ｎ含有率２０％）
ＰＸ−２００ ２８部
（大八化学工業(株)製、リン含有率９．１％）
ＨＣＡ−ＨＱ ４８部
（三光化学(株)製、リン含有率９．５％）
Examples and comparative examples in the present invention are shown below. “Part” indicates “% by weight”.
Example 1
30 parts of tetramethylbiphenyl type epoxy resin (YX4000 epoxy equivalent 185 made by JER)
70 parts of cresol novolac type epoxy resin (E180 epoxy equivalent 210 made by JER)
59.4 parts of melamine modified novolak resin (YLH828 manufactured by JER, hydroxyl equivalent 148 N content 20%)
PX-200 28 parts (manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.1%)
48 parts of HCA-HQ (manufactured by Sanko Chemical Co., Ltd., phosphorus content 9.5%)
上記化合物をメチルエチルケトンに溶解し、不揮発分６５％のワニスを作製した。このワニスをガラス織布（厚み０.２ｍｍ、坪量２１０ｇ／ｍ２）に樹脂分が４５％になるように含浸、乾燥しプリプレグを得た。このプリプレグを４枚重ね、その両面に１８μmの銅はくを重ね、１７０℃、９０分、４ＭＰａでプレス成形し厚さ０.８ｍｍの金属張積層板を得た。
（実施例２）
テトラメチルビフェニル型エポキシ樹脂 ３０部
（ＪＥＲ製 ＹＸ４０００ エポキシ当量１８５）
クレゾールノボラック型エポキシ樹脂 ７０部
（ＪＥＲ製 Ｅ１８０ エポキシ当量２１０）
メラミン変性ノボラック樹脂 ４４．０部
（ＪＥＲ製 ＹＬＨ８２８、水酸基当量１４８ Ｎ含有率２０％）
ＰＸ−２００ ２４部
（大八化学工業(株)製、リン含有率９．１％）
ＨＣＡ−ＨＱ ４５部
（三光化学(株)製、リン含有率９．５％）
The above compound was dissolved in methyl ethyl ketone to prepare a varnish having a nonvolatile content of 65%. This varnish was impregnated into a glass woven fabric (thickness 0.2 mm, basis weight 210 g / m 2 ) so that the resin content was 45% and dried to obtain a prepreg. Four prepregs were stacked, 18 μm copper foil was stacked on both sides, and press-molded at 170 ° C. for 90 minutes at 4 MPa to obtain a metal-clad laminate having a thickness of 0.8 mm.
(Example 2)
30 parts of tetramethylbiphenyl type epoxy resin (YX4000 epoxy equivalent 185 made by JER)
70 parts of cresol novolac type epoxy resin (E180 epoxy equivalent 210 made by JER)
44.0 parts of melamine-modified novolak resin (YLH828 manufactured by JER, hydroxyl group equivalent 148 N content 20%)
PX-200 24 parts (Daihachi Chemical Industry Co., Ltd., phosphorus content 9.1%)
45 parts of HCA-HQ (manufactured by Sanko Chemical Co., Ltd., phosphorus content 9.5%)
上記化合物を使用し、実施例１と同様のゲルタイムになるようなプリプレグを作製し、厚さ０.８ｍｍの金属張積層板を得た。
（実施例３）
テトラメチルビフェニル型エポキシ樹脂 ３０部
（ＪＥＲ製 ＹＸ４０００ エポキシ当量１８５）
クレゾールノボラック型エポキシ樹脂 ７０部
（ＪＥＲ製 Ｅ１８０ エポキシ当量２１０）
メラミン変性ノボラック樹脂 ２９.３部
（ＪＥＲ製 ＹＬＨ８２８、水酸基当量１４８ Ｎ含有率２０％）
ＰＸ−２００ ２０部
（大八化学工業(株)製、リン含有率９．１％）
ＨＣＡ−ＨＱ ４２部
（三光化学(株)製、リン含有率９．５％）
Using the above compound, a prepreg having a gel time similar to that of Example 1 was prepared to obtain a metal-clad laminate having a thickness of 0.8 mm.
(Example 3)
30 parts of tetramethylbiphenyl type epoxy resin (YX4000 epoxy equivalent 185 made by JER)
70 parts of cresol novolac type epoxy resin (E180 epoxy equivalent 210 made by JER)
29.3 parts of melamine-modified novolak resin (YLH828 made by JER, hydroxyl group equivalent 148 N content 20%)
PX-200 20 parts (Daihachi Chemical Industry Co., Ltd., phosphorus content 9.1%)
42 parts of HCA-HQ (manufactured by Sanko Chemical Co., Ltd., phosphorus content 9.5%)
上記化合物を使用し、実施例１と同様のゲルタイムになるようなプリプレグを作製し、厚さ０.８ｍｍの金属張積層板を得た。
（実施例４）
テトラメチルビフェニル型エポキシ樹脂 ３０部
（ＪＥＲ製 ＹＸ４０００ エポキシ当量１８５）
クレゾールノボラック型エポキシ樹脂 ７０部
（ＪＥＲ製 Ｅ１８０ エポキシ当量２１０）
メラミン変性ノボラック樹脂 ３６.７部
（ＪＥＲ製 ＹＬＨ８２８、水酸基当量１４８ Ｎ含有率２０％）
ＰＸ−２００ ５部
（大八化学工業(株)製、リン含有率９．１％）
ＯＰ９３０ １８部
（クラリアント製、リン含有率２３％）
Using the above compound, a prepreg having a gel time similar to that of Example 1 was prepared to obtain a metal-clad laminate having a thickness of 0.8 mm.
Example 4
30 parts of tetramethylbiphenyl type epoxy resin (YX4000 epoxy equivalent 185 made by JER)
70 parts of cresol novolac type epoxy resin (E180 epoxy equivalent 210 made by JER)
36.7 parts of melamine-modified novolak resin (YLH828 manufactured by JER, hydroxyl group equivalent 148 N content 20%)
PX-200 5 parts (manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.1%)
18 parts of OP930 (manufactured by Clariant, phosphorus content 23%)
上記化合物を使用し、実施例１と同様のゲルタイムになるようなプリプレグを作製し、厚さ０.８ｍｍの金属張積層板を得た。
（比較例１）
リン変性エポキシ樹脂 １００部
（東都化成製 ＦＸ２８９ エポキシ当量３０８）
ジシアンジアミド ３．４部
（分子量８４）
２ＰＺ ０．２部
（四国化成製）
水酸化アルミ ７０部
（ナカライテクス社製 粒子径３μ）
Using the above compound, a prepreg having a gel time similar to that of Example 1 was prepared to obtain a metal-clad laminate having a thickness of 0.8 mm.
(Comparative Example 1)
100 parts of phosphorus-modified epoxy resin (FX289, epoxy equivalent 308, manufactured by Tohto Kasei)
Dicyandiamide 3.4 parts (molecular weight 84)
0.2 parts of 2PZ (made by Shikoku Kasei)
70 parts of aluminum hydroxide (manufactured by Nacalai Tex, particle size 3μ)
上記化合物を使用し、実施例１と同様のゲルタイムになるようなプリプレグを作製し、厚さ０.８ｍｍの金属張積層板を得た。
（比較例２）
フェノールノボラック型エポキシ樹脂 １００部
（大日本インキ化学工業株式会社製 エピクロンＮ７７０）
トリアジン変性フェノールノボラック樹脂 ６５.８部
（大日本インキ化学工業株式会社製 ＬＡ−７０５４）
トリフェニルホスフェート ４３部
（大八化学工業株式会社製 ＴＰＰ）
Using the above compound, a prepreg having a gel time similar to that of Example 1 was prepared to obtain a metal-clad laminate having a thickness of 0.8 mm.
(Comparative Example 2)
100 parts of phenol novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd. Epicron N770)
65.8 parts of triazine-modified phenol novolac resin (LA-7054 manufactured by Dainippon Ink & Chemicals, Inc.)
43 parts of triphenyl phosphate (TPP manufactured by Daihachi Chemical Industry Co., Ltd.)
上記化合物を使用し、実施例１と同様のゲルタイムになるようなプリプレグを作製し、厚さ０.８ｍｍの金属張積層板を得た。 Using the above compound, a prepreg having a gel time similar to that of Example 1 was prepared to obtain a metal-clad laminate having a thickness of 0.8 mm.
実施例１〜４および比較例１〜２で得られた積層板についてＴｇ（ＴＭＡ）、耐熱性、耐燃焼性、誘電率の評価を実施した。Ｔｇ、難燃性はＪＩＳ−Ｃ−６４８１に準拠し測定した。２９０℃の耐熱性については表面の銅はくをエッチングで除去し、２９０℃のはんだ槽に２０秒間浸漬させ、ミーズリングやフクレの有無について目視にて評価した。評価基準は、○は異常なし、△はミーズリング発生あり、×はフクレの発生ありとした。２６０℃の耐熱性については表面の銅はくをエッチングで除去し、２６０℃のはんだ槽に１２０秒間浸漬させ、フクレの有無について目視にて評価した。評価基準は、○は異常なし、×はフクレの発生ありとした。誘電率についてはアジレント製マテリアルアナライザーにより、ＩＰＣ６５０ ２．５．５.９に準拠し測定した。 The laminates obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were evaluated for Tg (TMA), heat resistance, combustion resistance, and dielectric constant. Tg and flame retardancy were measured in accordance with JIS-C-6481. Regarding the heat resistance at 290 ° C., the copper foil on the surface was removed by etching, immersed in a solder bath at 290 ° C. for 20 seconds, and the presence or absence of measling or swelling was visually evaluated. The evaluation criteria are as follows: ○ indicates no abnormality, Δ indicates occurrence of mising, and × indicates occurrence of swelling. For heat resistance at 260 ° C., the copper foil on the surface was removed by etching, immersed in a solder bath at 260 ° C. for 120 seconds, and the presence or absence of swelling was visually evaluated. The evaluation criteria were as follows: ○ indicates no abnormality and × indicates occurrence of swelling. The dielectric constant was measured in accordance with IPC650 2.5.5.9 using an Agilent material analyzer.
表１の結果より明らかなように実施例１〜４のようにビフェニル型エポキシ樹脂およびクレゾールノボラック型エポキシ樹脂からなるエポキシ樹脂を分子構造中に窒素原子を含有するフェノール樹脂で硬化させ、難燃付与剤としてリンの含有率が８％以上２５％以下のリン化合物を二種類使用することでＴｇ、耐燃焼性にすぐれ、かつはんだ耐熱性に優れた低誘電率の積層板を得ることができる。 As is clear from the results in Table 1, the epoxy resin composed of the biphenyl type epoxy resin and the cresol novolak type epoxy resin is cured with a phenol resin containing a nitrogen atom in the molecular structure as in Examples 1 to 4 to impart flame retardancy. By using two types of phosphorus compounds having a phosphorus content of 8% or more and 25% or less as the agent, it is possible to obtain a low dielectric constant laminate having excellent Tg and combustion resistance and excellent solder heat resistance.
一方、比較例１〜２ではＴｇやはんだ耐熱性が劣り、誘電率が高い。 On the other hand, in Comparative Examples 1-2, Tg and solder heat resistance are inferior, and a dielectric constant is high.
Claims (7)
（ｂ）分子構造中に窒素原子を含有するフェノール樹脂、
（ｃ）少なくとも二種類のリンの含有率が８％以上２５％以下であるリン化合物、
を含有するプリント配線板用樹脂組成物。 (A) an epoxy resin comprising a biphenyl type epoxy resin and a cresol novolac type epoxy resin,
(B) a phenol resin containing a nitrogen atom in the molecular structure;
(C) a phosphorus compound having a content of at least two types of phosphorus of 8% or more and 25% or less,
Containing a resin composition for printed wiring boards.
全樹脂組成物あたり、リンの含有率が２．５〜４．５重量％であることを特徴とする請求項１に記載のプリント配線板用樹脂組成物。 It is 25 to 65 parts by weight of a phenol resin containing a nitrogen atom in its molecular structure per 100 parts by weight of an epoxy resin composed of 20 to 60 parts by weight of a biphenyl type epoxy resin and 40 to 80 parts by weight of a cresol novolac type epoxy resin.
2. The resin composition for a printed wiring board according to claim 1, wherein the content of phosphorus is 2.5 to 4.5 wt% per total resin composition.
A metal-clad laminate obtained by laminating one or more prepregs for printed wiring boards according to claim 5 or 6, laminating metal foil on at least one surface thereof, and heating and pressing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004380675A JP2006182991A (en) | 2004-12-28 | 2004-12-28 | Resin composition for printed wiring board, resin varnish, prepreg and laminated plate using it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004380675A JP2006182991A (en) | 2004-12-28 | 2004-12-28 | Resin composition for printed wiring board, resin varnish, prepreg and laminated plate using it |
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| Publication Number | Publication Date |
|---|---|
| JP2006182991A true JP2006182991A (en) | 2006-07-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP2004380675A Pending JP2006182991A (en) | 2004-12-28 | 2004-12-28 | Resin composition for printed wiring board, resin varnish, prepreg and laminated plate using it |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008195835A (en) * | 2007-02-14 | 2008-08-28 | Shin Kobe Electric Mach Co Ltd | Manufacturing method for epoxy resin varnish, manufacturing method for pre-preg, and manufacturing method for laminated plate and wiring board |
| TWI398458B (en) * | 2009-03-23 | 2013-06-11 | Taiyo Holdings Co Ltd | A photohardenable thermosetting resin composition, a dry film and a hardened product thereof, and a printed wiring board |
| KR20160002810A (en) | 2013-04-23 | 2016-01-08 | 다이요 홀딩스 가부시키가이샤 | Printed-circuit-board material and printed circuit board using same |
| KR20160002811A (en) | 2013-04-23 | 2016-01-08 | 다이요 홀딩스 가부시키가이샤 | Printed-circuit-board material and printed circuit board using same |
| WO2020040200A1 (en) | 2018-08-22 | 2020-02-27 | 東レ株式会社 | Prepreg |
| KR20200138276A (en) | 2018-03-28 | 2020-12-09 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product and electronic component |
| KR20210119893A (en) | 2020-03-25 | 2021-10-06 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product, and electronic component |
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| JPH0892393A (en) * | 1994-09-22 | 1996-04-09 | Sumitomo Bakelite Co Ltd | Production of prepreg |
| JP2000239347A (en) * | 1999-02-25 | 2000-09-05 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and prepreg and laminate using the same |
| JP2001049085A (en) * | 1999-08-09 | 2001-02-20 | Toshiba Chem Corp | Halogen-free, flame-retardant epoxy resin composition |
| JP2001200032A (en) * | 2000-01-17 | 2001-07-24 | Sumitomo Bakelite Co Ltd | Flame retardant resin composition, prepreg and laminated board using the same |
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| JP2006016574A (en) * | 2004-07-05 | 2006-01-19 | Hitachi Chem Co Ltd | Resin composition for printed wiring board, and varnish, prepreg and metal-clad laminate using the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0892393A (en) * | 1994-09-22 | 1996-04-09 | Sumitomo Bakelite Co Ltd | Production of prepreg |
| JP2000239347A (en) * | 1999-02-25 | 2000-09-05 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and prepreg and laminate using the same |
| JP2001049085A (en) * | 1999-08-09 | 2001-02-20 | Toshiba Chem Corp | Halogen-free, flame-retardant epoxy resin composition |
| JP2001200032A (en) * | 2000-01-17 | 2001-07-24 | Sumitomo Bakelite Co Ltd | Flame retardant resin composition, prepreg and laminated board using the same |
| JP2001254001A (en) * | 2000-03-09 | 2001-09-18 | Sumitomo Bakelite Co Ltd | Flame-retardant resin composition, and prepreg and laminated board using the same |
| JP2006016574A (en) * | 2004-07-05 | 2006-01-19 | Hitachi Chem Co Ltd | Resin composition for printed wiring board, and varnish, prepreg and metal-clad laminate using the same |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008195835A (en) * | 2007-02-14 | 2008-08-28 | Shin Kobe Electric Mach Co Ltd | Manufacturing method for epoxy resin varnish, manufacturing method for pre-preg, and manufacturing method for laminated plate and wiring board |
| TWI398458B (en) * | 2009-03-23 | 2013-06-11 | Taiyo Holdings Co Ltd | A photohardenable thermosetting resin composition, a dry film and a hardened product thereof, and a printed wiring board |
| KR20160002810A (en) | 2013-04-23 | 2016-01-08 | 다이요 홀딩스 가부시키가이샤 | Printed-circuit-board material and printed circuit board using same |
| KR20160002811A (en) | 2013-04-23 | 2016-01-08 | 다이요 홀딩스 가부시키가이샤 | Printed-circuit-board material and printed circuit board using same |
| KR20200138276A (en) | 2018-03-28 | 2020-12-09 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product and electronic component |
| WO2020040200A1 (en) | 2018-08-22 | 2020-02-27 | 東レ株式会社 | Prepreg |
| KR20210045995A (en) | 2018-08-22 | 2021-04-27 | 도레이 카부시키가이샤 | Prepreg |
| KR20210119893A (en) | 2020-03-25 | 2021-10-06 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product, and electronic component |
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