JP2006028249A - Resin composition, prepreg using the same, metal foil clad laminate and printed wiring board - Google Patents
Resin composition, prepreg using the same, metal foil clad laminate and printed wiring board Download PDFInfo
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本発明は、樹脂組成物およびそれを用いたプリプレグ、金属箔張積層板、印刷配線板に関する。 The present invention relates to a resin composition, a prepreg using the resin composition, a metal foil-clad laminate, and a printed wiring board.
近年、環境問題に対する意識の高まりから、電子機器等に使用されるプリプレグ、金属箔張積層板、印刷配線板は、廃棄等の焼却時におけるダイオキシン等の有害ガス発生のおそれがない、すなわちハロゲン系化合物を含まない製品の導入が進んでいる。 In recent years, due to the growing awareness of environmental issues, prepregs, metal foil-clad laminates, and printed wiring boards used in electronic devices, etc., are free from the risk of generating harmful gases such as dioxins during incineration such as disposal. Products that do not contain compounds are being introduced.
ハロゲン系化合物を含まずに難燃性を付与するには、樹脂組成物にリン系難燃剤や無機充填材を添加する等の方法が行われている。リン系難燃剤としては、トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート等のリン酸エステル系や、レゾルシノールジホスフェート等の縮合リン酸エステル等が広く用いられている。これらの難燃剤を用いる場合、そのリン含有率が７〜１０重量％程度と低く、樹脂組成物中に多量に難燃剤を添加しなければならないため、樹脂の硬化阻害が生じたり、金属箔張積層板、印刷配線板の耐熱性が低下するという問題を抱えていた（特許文献１参照）。 In order to impart flame retardancy without containing a halogen-based compound, a method such as adding a phosphorus-based flame retardant or an inorganic filler to the resin composition is performed. As phosphorus flame retardants, phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and condensed phosphate esters such as resorcinol diphosphate are widely used. When these flame retardants are used, the phosphorus content is as low as about 7 to 10% by weight, and the flame retardant must be added in a large amount in the resin composition. It had the problem that the heat resistance of a laminated board and a printed wiring board fell (refer patent document 1).
このような状況の中、特許文献２に示されているように、難燃剤としてホスフィン酸塩やジホスフィン酸塩を用いる技術が導入されている。しかし、ホスフィン酸塩またはジホスフィン酸塩を用いる場合、その粒径や粒子の形状によっては、金属箔張積層板の金属箔引き剥がし強度や耐アルカリ性が劣ることがあった。
本発明は、上記の従来技術の問題点を解消し、ハロゲン系化合物を含まず、難燃性、耐熱性、金属箔引き剥がし強度に優れた樹脂組成物およびそれを用いたプリプレグ、金属箔張積層板、印刷配線板を提供するものである。 The present invention solves the above-mentioned problems of the prior art, does not contain a halogen-based compound, has excellent flame retardancy, heat resistance, and metal foil peeling strength, and a prepreg and metal foil tension using the same. A laminated board and a printed wiring board are provided.
本発明は、次のものに関する。
（１）（ａ）一般式（１）で示されるホスフィン酸塩または一般式（２）で示されるジホスフィン酸塩、（ｂ）熱硬化性樹脂、（ｃ）該熱硬化性樹脂の硬化剤を必須成分とする樹脂組成物であって、（ａ）一般式（１）で示されるホスフィン酸塩又は一般式（２）で示されるジホスフィン酸塩の粒子の平均粒径が２〜７μｍであり、かつ該粒子の長径と短径の比（長径／短径）が１〜３である樹脂組成物。
The present invention relates to the following.
(1) (a) a phosphinic acid salt represented by the general formula (1) or a diphosphinic acid salt represented by the general formula (2), (b) a thermosetting resin, and (c) a curing agent for the thermosetting resin. It is a resin composition as an essential component, and (a) the average particle diameter of the phosphinic acid salt represented by the general formula (1) or the diphosphinic acid salt represented by the general formula (2) is 2 to 7 μm, And the resin composition whose ratio (major axis / minor axis) of the major axis and minor axis of the particles is 1 to 3.
（一般式（１）又は一般式（２）中のＲ１、Ｒ２は互いに同一でも異なっていてもよく、一価の直鎖状のまたは枝分かれした炭素数１〜６のアルキル基またはアリール基であり、Ｒ３は二価の直鎖状のまたは枝分かれした炭素数１〜１０のアルキレン基、又は炭素数６〜１０のアリーレン基、又はアルキルアリーレン基、又はアリールアルキレン基であり、ＭはＭｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋからなる群の少なくとも１種より選択される金属類であり、ｍは１〜４の整数であり、ｎは１〜４の整数であり、そしてｘは１〜４の整数である。）
（２）項（１）に記載の樹脂組成物を基材に含浸・乾燥させて得られるプリプレグ。
（３）項（２）に記載のプリプレグ、又は該プリプレグを複数枚積層した積層体の片面または両面に金属箔を積層し加熱加圧して得られる金属箔張積層板。
（４）項（３）に記載の金属箔張積層板に回路加工を施して得られる印刷配線板。
(R 1 and R 2 in general formula (1) or general formula (2) may be the same or different from each other, and are a monovalent linear or branched alkyl group or aryl group having 1 to 6 carbon atoms. R 3 is a divalent linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group, or an arylalkylene group, and M is Mg , Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K are metals selected from the group consisting of m, An integer from 1 to 4, n is an integer from 1 to 4, and x is an integer from 1 to 4.)
(2) A prepreg obtained by impregnating and drying a substrate with the resin composition according to item (1).
(3) A metal foil-clad laminate obtained by laminating a metal foil on one side or both sides of a prepreg according to item (2) or a laminate obtained by laminating a plurality of the prepregs, and heating and pressing.
(4) A printed wiring board obtained by subjecting the metal foil-clad laminate according to item (3) to circuit processing.
本発明における樹脂組成物およびプリプレグで得られる金属箔張積層板、印刷配線板は、ハロゲン系化合物を含まず、難燃性、耐熱性、金属箔引き剥がし強度に優れる。 The metal foil-clad laminate and printed wiring board obtained from the resin composition and prepreg in the present invention do not contain a halogen compound and are excellent in flame retardancy, heat resistance, and metal foil peeling strength.
以下、本発明を詳細に説明する。
本発明の樹脂組成物は、（ａ）前記一般式（１）で示されるホスフィン酸塩または前記一般式（２）で示されるジホスフィン酸塩、（ｂ）熱硬化性樹脂、（ｃ）該熱硬化性樹脂の硬化剤を必須成分としている。なお本発明において（ａ）前記一般式（１）で示されるホスフィン酸塩と前記一般式（２）で示されるジホスフィン酸塩は、単独で使用してもよく、また併用してもよい。そして本発明において使用される（ａ）ホスフィン酸塩またはジホスフィン酸塩の粒子の平均粒径は２〜７μｍであり，好ましくは３〜５μｍのものが用いられる。平均粒径が２μｍ未満の場合，金属箔引き剥がし強度が劣ることがあり、７μｍを超える場合，樹脂組成物に有機溶剤を加えワニスとした場合に沈降しやすくなる。
Hereinafter, the present invention will be described in detail.
The resin composition of the present invention comprises (a) a phosphinic acid salt represented by the general formula (1) or a diphosphinic acid salt represented by the general formula (2), (b) a thermosetting resin, (c) the heat A curing agent for the curable resin is an essential component. In the present invention, (a) the phosphinic acid salt represented by the general formula (1) and the diphosphinic acid salt represented by the general formula (2) may be used alone or in combination. The average particle size of the (a) phosphinate or diphosphinate particles used in the present invention is 2 to 7 μm, preferably 3 to 5 μm. When the average particle size is less than 2 μm, the metal foil peel strength may be inferior, and when it exceeds 7 μm, the resin composition tends to settle when an organic solvent is added to the resin composition.
本発明において使用される（ａ）ホスフィン酸塩またはジホスフィン酸塩の粒子の長径と短径の比（長径／短径）は１〜３である。長径と短径の比（長径／短径）が３を超える場合，金属箔張積層板の金属箔引き剥がし強度や耐アルカリ性が劣ることがある。なお，長径と短径の比（長径／短径）については，走査型電子顕微鏡により観察した粒子の中から無作為に抽出した１００個の粒子について、粒子毎に計測した最大径および最小径をそれぞれ長径および短径として［長径／短径］を算出し、１００標本分の平均値を長径と短径の比とした。 The ratio (major axis / minor axis) of the major axis to the minor axis of (a) phosphinate or diphosphinate particles used in the present invention is 1 to 3. When the ratio of the major axis to the minor axis (major axis / minor axis) exceeds 3, the metal foil-clad laminate metal foil peel strength and alkali resistance may be inferior. As for the ratio of major axis to minor axis (major axis / minor axis), the maximum and minimum diameters measured for each particle of 100 particles randomly extracted from the particles observed with a scanning electron microscope are used. [Long diameter / short diameter] was calculated as the long diameter and the short diameter, respectively, and the average value for 100 samples was taken as the ratio of the long diameter to the short diameter.
また、本発明において使用される（ａ）ホスフィン酸塩またはジホスフィン酸塩の粒子の最大粒径は２０μｍ以下であることが好ましい。最大粒径が２０μｍを超えると、金属箔張積層板の板厚が薄い場合や金属箔張積層板に形成する回路パターンが微細な場合に電気的特性等において信頼性に劣る場合がある。なお本発明において使用される（ａ）ホスフィン酸塩またはジホスフィン酸塩を添加する際、必要に応じて各種表面処理剤を添加しても良い。また（ａ）ホスフィン酸塩またはジホスフィン酸塩の配合量についても、特に制限されないが、樹脂組成物中の（ｂ）熱硬化性樹脂と（ｃ）硬化剤の合計の固形分総量１００重量部に対して５〜４０重量部が好ましい。 The maximum particle size of the (a) phosphinate or diphosphinate particles used in the present invention is preferably 20 μm or less. When the maximum particle size exceeds 20 μm, the reliability may be poor in electrical characteristics or the like when the thickness of the metal foil-clad laminate is thin or the circuit pattern formed on the metal foil-clad laminate is fine. In addition, when (a) phosphinate or diphosphinate used in the present invention is added, various surface treatment agents may be added as necessary. The amount of (a) phosphinic acid salt or diphosphinic acid salt is not particularly limited, but the total solid content of (b) thermosetting resin and (c) curing agent in the resin composition is 100 parts by weight. The amount is preferably 5 to 40 parts by weight.
本発明において使用される（ｂ）熱硬化性樹脂としては、特に制限されないが、エポキシ樹脂、ポリイミド樹脂、トリアジン樹脂、メラミン樹脂、フェノール樹脂、シアネート類化合物等が挙げられ、これらを単独で、または、２種以上使用することができる。この中で、例えば、エポキシ樹脂を例に挙げると、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡＤ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、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、フェノール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、ビフェニル型エポキシ樹脂、フェノールビフェニレン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、ビフェノールのジグリシジリエーテル化物、ナフタレンジオールのジグリシジリエーテル化物、フェノール類のジグリシジリエーテル化物、アルコール類のジグリシジリエーテル化物、および、これらのアルキル置換体、水素添加物等が用いられ、これらから単独で、または、２種以上を使用することができる。 (B) The thermosetting resin used in the present invention is not particularly limited, and examples thereof include an epoxy resin, a polyimide resin, a triazine resin, a melamine resin, a phenol resin, and a cyanate compound, and these are used alone or Two or more types can be used. Among these, for example, when an epoxy resin is taken as an example, bisphenol A type epoxy resin, bisphenol AD type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin , Phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol biphenylene novolac type epoxy resin, bisphenol A novolac type epoxy resin, diglycidyl etherified product of biphenol, diglycidyl etherified product of naphthalenediol, phenol Diglycidyl etherified products, alcohol diglycidyl etherified products, alkyl substitution products thereof, hydrogenated products, etc. are used alone or from these two or more. It is possible to use.
本発明において使用される（ｃ）硬化剤としては、特に制限されないが、（ｂ）熱硬化性樹脂としてエポキシ樹脂を使用する場合の硬化剤を例に挙げると、アミン化合物、多官能性フェノール化合物、酸無水物化合物等が挙げられ、これらから単独または２種以上選択される。（ｃ）硬化剤の配合量は、特に制限されないが、（ｂ）熱硬化性樹脂の主材の官能基に対して０．０１〜５．０当量が好ましい。 The (c) curing agent used in the present invention is not particularly limited, but (b) a curing agent in the case of using an epoxy resin as a thermosetting resin, an amine compound, a polyfunctional phenol compound , And acid anhydride compounds, and the like. (C) Although the compounding quantity of a hardening | curing agent is not restrict | limited in particular, 0.01-5.0 equivalent is preferable with respect to the functional group of the main material of (b) thermosetting resin.
いずれの（ｂ）熱硬化性樹脂を用いる場合でも、硬化促進剤を使用しても良い。この場合の硬化促進剤としては、特に制限されないが、例えばイミダゾール系化合物、有機リン系化合物、第２級アミン、第３級アミン、第４級アンモニウム塩等が用いられ、これらから単独または２種以上選択される。硬化促進剤の配合量についても、特に制限されないが、樹脂組成物中の有機成分の固形分総量１００重量部に対して０．０１〜１０重量部が好ましい。また、本発明において使用される樹脂組成物は、必要に応じて充填材、触媒、可とう剤等を適宜加えても良い。 Even when any (b) thermosetting resin is used, a curing accelerator may be used. The curing accelerator in this case is not particularly limited. For example, imidazole compounds, organophosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like are used. These are selected. The blending amount of the curing accelerator is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total solid content of the organic component in the resin composition. Further, the resin composition used in the present invention may be appropriately added with a filler, a catalyst, a flexible agent, and the like as necessary.
本発明の樹脂組成物のワニスは、上記の配合材料（樹脂組成物）に必要に応じて有機溶剤を加え、混合することにより得られる。本発明に用いられる有機溶剤としては、特に制限されないが、メタノール、エタノール、イソプロピルアルコール、ｎ−ブタノール等のアルコール系溶剤、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン系溶剤、トルエン、キシレン等の芳香族炭化水素系溶剤、ジメチルスルホキシド等の硫黄化合物系溶剤、Ｎ−メチルピロリドン、Ｎ−メチルホルムアルデヒド、Ｎ，Ｎ−ジメチルホルムアミド等のアミド系溶剤、メチルセロソルブ、エチルセロソルブ、セロソルブアセテート等のセロソルブ系溶剤等が使用可能であり、これらから単独または２種以上選択される。 The varnish of the resin composition of the present invention can be obtained by adding and mixing an organic solvent to the above compounded material (resin composition) as necessary. The organic solvent used in the present invention is not particularly limited, but alcohol solvents such as methanol, ethanol, isopropyl alcohol and n-butanol, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, and aromatic carbonization such as toluene and xylene. Hydrogen solvents, sulfur compound solvents such as dimethyl sulfoxide, amide solvents such as N-methylpyrrolidone, N-methylformaldehyde, N, N-dimethylformamide, cellosolv solvents such as methyl cellosolve, ethyl cellosolve, cellosolve acetate, etc. They can be used and are selected from these alone or in combination.
本発明の樹脂組成物のワニスを基材に含浸させ、さらに乾燥させてプリプレグを製造する。本発明に用いられる基材としては、特に制限されないが、通常織布や不織布等が用いられる。基材の材質としては、特に制限されないが、ガラス、アルミナ、シリカアルミナガラス、シリカガラス、炭化ケイ素、ジルコニア等の無機繊維や、アラミド、ポリエーテルイミド、カーボン、セルロース等の有機繊維等が用いられる。 The base material is impregnated with the varnish of the resin composition of the present invention, and further dried to produce a prepreg. Although it does not restrict | limit especially as a base material used for this invention, Usually, a woven fabric, a nonwoven fabric, etc. are used. The material of the substrate is not particularly limited, but inorganic fibers such as glass, alumina, silica alumina glass, silica glass, silicon carbide, and zirconia, and organic fibers such as aramid, polyetherimide, carbon, and cellulose are used. .
本発明の金属箔張積層板は、本発明のプリプレグ、または、それを複数枚積層した積層体の片面または両面に金属箔を重ね加熱加圧成形することにより得られる。本発明に用いられる金属箔は、特に制限されないが、銅箔やアルミニウム箔などが用いられる。加熱加圧成形する際の条件は、熱硬化性樹脂と硬化剤との反応性に依存するため、用いられる樹脂材料により選択され、通常１３０〜２５０℃、好ましくは１５０〜２００℃の範囲の温度、通常０．５〜２０ＭＰａ、好ましくは１〜８ＭＰａの範囲の圧力、通常１０〜２００分、好ましくは３０〜１２０分の範囲の加熱加圧時間が選ばれる。 The metal foil-clad laminate of the present invention can be obtained by stacking a metal foil on one side or both sides of the prepreg of the present invention or a laminate in which a plurality of the prepregs are laminated, and press-molding them. The metal foil used in the present invention is not particularly limited, but copper foil, aluminum foil, and the like are used. The conditions at the time of heat and pressure molding depend on the reactivity between the thermosetting resin and the curing agent, and therefore are selected according to the resin material used, and are usually in the range of 130 to 250 ° C., preferably 150 to 200 ° C. In general, a pressure in the range of 0.5 to 20 MPa, preferably 1 to 8 MPa, a heating and pressing time in the range of 10 to 200 minutes, preferably 30 to 120 minutes is selected.
本発明の印刷配線板は、本発明の金属箔張積層板の金属箔表面もしくは金属箔エッチング面に対して回路加工を施すことにより得られる。 The printed wiring board of the present invention can be obtained by subjecting a metal foil surface or a metal foil etched surface of the metal foil-clad laminate of the present invention to circuit processing.
以下に、本発明を実施例により具体的に説明するが、本発明はこれに限定されるものではない。
（実施例１〜２、比較例１〜３）
表１に実施例１、２及び比較例１〜３の樹脂組成物の配合を示した。表１の配合量の材料と、有機溶剤としてメチルエチルケトンを配合し、６０分間撹拌し樹脂組成物のワニスを得た。なお、一般式（１）で示されるホスフィン酸塩として、ＯＰ９３０（クラリアントジャパン株式会社製商品名）リン系難燃剤を使用した。またメチルエチルケトンは樹脂組成物のワニスの固形分が５０重量％となるよう配合した。作製した樹脂組成物のワニスを厚さ０．１ｍｍのガラスクロス（２１１６：旭シュエーベル株式会社製、商品名）に含浸後、１６０℃で５分間加熱、乾燥して樹脂分５０重量％のプリプレグを得た。このプリプレグを４枚重ね、その両側に厚さ１８μｍの銅箔（ＧＴＳ−１８：古河サーキットフォイル株式会社製、商品名）を配置し、１８０℃、３ＭＰａ、６０分間、真空下で加温加圧成形することにより銅張積層板を作製した。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
(Examples 1-2, Comparative Examples 1-3)
Table 1 shows the composition of the resin compositions of Examples 1 and 2 and Comparative Examples 1 to 3. A material having the blending amount shown in Table 1 and methyl ethyl ketone as an organic solvent were blended and stirred for 60 minutes to obtain a resin composition varnish. In addition, OP930 (brand name by Clariant Japan Co., Ltd.) phosphorus flame retardant was used as the phosphinic acid salt represented by the general formula (1). Methyl ethyl ketone was blended so that the solid content of the varnish of the resin composition was 50% by weight. The prepared resin composition varnish was impregnated into a 0.1 mm thick glass cloth (2116, trade name, manufactured by Asahi Sebel Co., Ltd.), heated and dried at 160 ° C. for 5 minutes to give a prepreg having a resin content of 50% by weight. Obtained. Four prepregs are stacked, and 18 μm thick copper foil (GTS-18: trade name, manufactured by Furukawa Circuit Foil Co., Ltd.) is placed on both sides of the prepreg, and heated and pressurized under vacuum at 180 ° C., 3 MPa for 60 minutes. A copper clad laminate was produced by molding.
（はんだ耐熱性の評価）
はんだ耐熱性は、作製した銅張積層板の銅箔をエッチングにより除去し５０ｍｍ×５０ｍｍの大きさに切断した試験片を、プレッシャークッカーテスター中（１２１℃、０．２２ＭＰａ）に１時間保持した後、２８８℃のはんだ中に２０秒間浸漬して、外観を目視により評価した。その結果を前記表１に示した。表中のＯＫとは、ミーズリング（ガラス繊維の織り目の重なり部分の熱ひずみに伴う樹脂の剥離）および、ふくれの発生がないことを意味し、ＮＧは、ミーズリングまたはふくれが発生したことを示した。
(Evaluation of solder heat resistance)
The solder heat resistance is obtained by holding a test piece obtained by removing the copper foil of the produced copper-clad laminate by etching and cutting it to a size of 50 mm × 50 mm in a pressure cooker tester (121 ° C., 0.22 MPa) for 1 hour. It was immersed in 288 ° C. solder for 20 seconds, and the appearance was visually evaluated. The results are shown in Table 1 above. “OK” in the table means that there is no mesling (resin peeling due to thermal strain at the overlapping portion of the glass fiber weave) and no blistering, and NG means that mesling or blistering has occurred. Indicated.
（難燃性の評価）
難燃性は、ＵＬ９４−Ｖ法に準拠して測定した。結果を前記表１に示した。
(Evaluation of flame retardancy)
Flame retardancy was measured according to the UL94-V method. The results are shown in Table 1 above.
（銅箔引き剥がし強度）
ＪＩＳ Ｃ ６４８１に準拠して測定した。結果を前記表１に示した。
(Copper foil peel strength)
It measured based on JIS C 6481. The results are shown in Table 1 above.
表１から明らかなように、本発明の実施例１および２は、リン系難燃剤として平均粒径３．２μｍ、長径／短径＝１．８の一般式（１）で示されるホスフィン酸塩を用いることにより、比較例１〜３と比較して難燃性、はんだ耐熱性、銅箔引き剥がし強度のすべてにおいて優れている。これに対し、比較例１は、長径／短径＝７．７のホスフィン酸塩を用いているために銅箔引き剥がし強度に劣り、比較例２は平均粒径１．５μｍのホスフィン酸塩を用いているために銅箔引き剥がし強度に劣り、比較例３はリン系難燃剤としてトリフェニルホスフェートを用いているために難燃性が低く、さらに耐熱性も劣る。
As is clear from Table 1, Examples 1 and 2 of the present invention are phosphinic acid salts represented by the general formula (1) having an average particle diameter of 3.2 μm and a major axis / minor axis = 1.8 as a phosphorus-based flame retardant. By using, it is excellent in all of a flame retardance, solder heat resistance, and copper foil peeling strength compared with Comparative Examples 1-3. On the other hand, Comparative Example 1 uses a phosphinate having a major axis / minor axis = 7.7, so that the copper foil peel strength is inferior. Since it uses, it is inferior to copper foil peeling strength, and since the comparative example 3 uses triphenyl phosphate as a phosphorus flame retardant, its flame retardance is low, and also heat resistance is inferior.
Claims (4)
（一般式（１）又は一般式（２）中のＲ１、Ｒ２は互いに同一でも異なっていてもよく、一価の直鎖状のまたは枝分かれした炭素数１〜６のアルキル基またはアリール基であり、Ｒ３は二価の直鎖状のまたは枝分かれした炭素数１〜１０のアルキレン基、又は炭素数６〜１０のアリーレン基、又はアルキルアリーレン基、又はアリールアルキレン基であり、ＭはＭｇ、Ｃａ、Ａｌ、Ｓｂ、Ｓｎ、Ｇｅ、Ｔｉ、Ｚｎ、Ｆｅ、Ｚｒ、Ｃｅ、Ｂｉ、Ｓｒ、Ｍｎ、Ｌｉ、Ｎａ、Ｋからなる群の少なくとも１種より選択される金属類であり、ｍは１〜４の整数であり、ｎは１〜４の整数であり、そしてｘは１〜４の整数である。） (A) The phosphinic acid salt represented by the general formula (1) or the diphosphinic acid salt represented by the general formula (2), (b) a thermosetting resin, and (c) a curing agent for the thermosetting resin as an essential component. And (a) the phosphinic acid salt represented by the general formula (1) or the diphosphinic acid salt represented by the general formula (2) has an average particle diameter of 2 to 7 μm, and the particles A resin composition having a ratio of major axis to minor axis (major axis / minor axis) of 1 to 3.
(R 1 and R 2 in general formula (1) or general formula (2) may be the same or different from each other, and are a monovalent linear or branched alkyl group or aryl group having 1 to 6 carbon atoms. R 3 is a divalent linear or branched alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, an alkylarylene group, or an arylalkylene group, and M is Mg , Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, and K are metals selected from the group consisting of m, An integer from 1 to 4, n is an integer from 1 to 4, and x is an integer from 1 to 4.)
A printed wiring board obtained by subjecting the metal foil-clad laminate according to claim 3 to circuit processing.
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| JP2011012271A (en) * | 2010-08-13 | 2011-01-20 | Hitachi Chem Co Ltd | Method of producing prepreg, prepreg, metal-clad laminate and printed wiring board |
| US7935752B2 (en) | 2006-03-09 | 2011-05-03 | Showa Denko K.K. | Thermosetting resin composition and uses thereof |
| JP2012527520A (en) * | 2009-05-19 | 2012-11-08 | アルベマール・コーポレーシヨン | DOPO-derived flame retardant epoxy resin composition |
| US11136454B2 (en) * | 2016-12-07 | 2021-10-05 | Showa Denko Materials Co., Ltd. | Thermosetting resin composition and its production method, prepreg, laminate, and printed wiring board |
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