TWI477549B - Resin composition - Google Patents

Description

樹脂組成物Resin composition

本發明係關於適於多層印刷配線板等絕緣層形成之樹脂組成物。The present invention relates to a resin composition suitable for formation of an insulating layer such as a multilayer printed wiring board.

近年、伴隨電子機器小型化、高性能化，多層印刷配線板為了提升電子零件之實裝密度而追求導體配線之微細化。作為多層印刷配線板之絕緣層使用之樹脂組成物，例如已知含有環氧樹脂與作為其硬化劑的氰酸酯樹脂之樹脂組成物可形成介電特性優之絕緣層。又，在配線高密度化之多層印刷配線板，因為導體層與絕緣層之熱膨脹係數之差異而變得易有破裂產生等問題，故要求抑制絕緣層之熱膨脹率為低。對樹脂組成物添加無機充填材為降低熱膨脹率之常用手段，作為無機充填材，尤其在物理強度強、硬度高、且耐熱水性點優異的二氧化矽一般被廣泛使用。例如在專利文獻1、2揭示含有環氧樹脂、氰酸酯樹脂、二氧化矽等之樹脂組成物。In recent years, in order to increase the mounting density of electronic components, the multilayer printed wiring board has been miniaturized in terms of miniaturization and high performance of electronic devices. As the resin composition used for the insulating layer of the multilayer printed wiring board, for example, a resin composition containing an epoxy resin and a cyanate resin as a curing agent thereof is known to form an insulating layer excellent in dielectric properties. Further, in the multilayer printed wiring board in which the wiring density is increased, there is a problem that cracking occurs easily due to the difference in thermal expansion coefficient between the conductor layer and the insulating layer. Therefore, it is required to suppress the thermal expansion coefficient of the insulating layer to be low. The addition of an inorganic filler to a resin composition is a common means for lowering the coefficient of thermal expansion. As an inorganic filler, in particular, cerium oxide having high physical strength, high hardness, and excellent hot water resistance is generally used. For example, Patent Documents 1 and 2 disclose a resin composition containing an epoxy resin, a cyanate resin, or cerium oxide.

[先行技術文獻][Advanced technical literature]

[專利文獻][Patent Literature]

[專利文獻1]國際公開2003/099952號文獻[Patent Document 1] International Publication No. 2003/099952

[專利文獻2]國際公開2008/044766號文獻[Patent Document 2] International Publication No. 2008/044766

另一方面，本發明者們將含環氧樹脂、氰酸酯樹脂、二氧化矽之樹脂組成物層合於電路基板，對硬化該樹脂組成物所形成之絕緣層在高溫高濕下進行環境試驗，發現導體層與絕緣層間之剝離強度顯著降低。On the other hand, the inventors of the present invention laminate a resin composition containing an epoxy resin, a cyanate resin, and a ceria on a circuit board, and an environment in which the insulating layer formed by curing the resin composition is subjected to high temperature and high humidity. The test found that the peel strength between the conductor layer and the insulating layer was remarkably lowered.

本發明以提供適合印刷配線板之絕緣層形成的樹脂組成物，藉由使用該樹脂組成物製造電路基板，可使導體層與絕緣層之密著性維持更安定之樹脂組成物為目的。According to the present invention, in order to provide a resin composition suitable for the formation of an insulating layer of a printed wiring board, it is possible to produce a circuit substrate by using the resin composition, and it is possible to maintain a more stable resin composition between the conductor layer and the insulating layer.

本發明者們發現在含環氧樹脂及氰酸酯樹脂之樹脂組成物中搭配滑石時，可安定地維持加速環境試驗後的導體層與絕緣層之密著性。另一方面，發現為了維持充分密著性且降低絕緣層之熱膨脹率，滑石的搭配量多，則樹脂組成物的熔融黏度過高而不適合層合。本發明者們再檢討之結果，發現於含環氧樹脂、氰酸酯樹脂、熱可塑性樹脂之樹脂組成物中，藉由併用一定比例作為無機充填材的滑石與二氧化矽，而形成與導體層之密著性、低熱膨脹率、層合性之均衡性佳的良好絕緣層，遂完成本發明。The present inventors have found that when talc is blended in a resin composition containing an epoxy resin and a cyanate resin, the adhesion between the conductor layer and the insulating layer after the accelerated environmental test can be stably maintained. On the other hand, it has been found that in order to maintain sufficient adhesion and lower the thermal expansion coefficient of the insulating layer, the amount of talc blended is large, and the melt viscosity of the resin composition is too high to be suitable for lamination. As a result of further review, the present inventors have found that a resin composition containing an epoxy resin, a cyanate resin, or a thermoplastic resin is formed by using a certain ratio of talc and cerium oxide as an inorganic filler. The present invention has been completed by a good insulating layer having a good adhesion of layers, a low thermal expansion coefficient, and a good balance of lamination.

亦即，本發明包含以下內容。That is, the present invention includes the following.

1、一種樹脂組成物，其係含有(A)氰酸酯樹脂、(B)環氧樹脂、(C)熱可塑性樹脂、(D)滑石及(E)二氧化矽之印刷配線板用樹脂組成物，其特徵為當樹脂組成物中不揮發分為100質量%時，(1)成分(D)滑石與成分(E)二氧化矽之含量合計為35質量%~60質量%且(2)成分(D)滑石之含量為5質量%~20質量%。A resin composition comprising a resin comprising (A) a cyanate resin, (B) an epoxy resin, (C) a thermoplastic resin, (D) talc, and (E) cerium oxide. The content of the component (D) talc and the component (E) cerium oxide is 35 to 60% by mass and (2) The content of the component (D) talc is 5 mass% to 20 mass%.

2、一種樹脂組成物，其係含有(A)氰酸酯樹脂、(B)環氧樹脂、(C)熱可塑性樹脂、(D)滑石及(E)二氧化矽之印刷配線板用樹脂組成物，其特徵為當樹脂組成物中不揮發分為100質量%時，(1)成分(D)滑石與成分(E)二氧化矽之含量合計為45質量%~60質量%，且(2)成分(D)滑石之含量為5質量%~20質量%。2. A resin composition comprising a resin comprising (A) a cyanate resin, (B) an epoxy resin, (C) a thermoplastic resin, (D) talc, and (E) cerium oxide printed wiring board. The content of the component (D) talc and the component (E) cerium oxide is 45% by mass to 60% by mass, and (2) The content of the component (D) talc is 5 mass% to 20 mass%.

3、如1或2之樹脂組成物，其中，成分(D)滑石的平均粒徑為1.3μm以下。3. The resin composition according to 1 or 2, wherein the component (D) talc has an average particle diameter of 1.3 μm or less.

4、如1或2之樹脂組成物，其中，成分(C)熱可塑性樹脂為由苯氧樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂、聚縮醛樹脂、聚縮丁醛樹脂所選出的1種以上之樹脂。4. A resin composition according to 1 or 2, wherein the component (C) thermoplastic resin is a phenoxy resin, a polyamidene resin, a polyamidimide resin, a polyether quinone resin, a polyfluorene resin. One or more resins selected from polyether oxime resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, polyester resins, polyacetal resins, and polybutyral resins.

5、如1或2之樹脂組成物，其中，成分(C)熱可塑性樹脂為苯氧樹脂。5. A resin composition according to 1 or 2, wherein the component (C) thermoplastic resin is a phenoxy resin.

6、如1~3中任1項之樹脂組成物，其中，成分(D)滑石及成分(E)二氧化矽預先經表面處理。6. The resin composition according to any one of items 1 to 3, wherein the component (D) talc and the component (E) cerium oxide are previously subjected to surface treatment.

7、如1~6中任1項之樹脂組成物，其中，熱膨脹率為44ppm以下，且環境試驗前後的密著維持率為40%以上。7. The resin composition according to any one of items 1 to 6, wherein the thermal expansion coefficient is 44 ppm or less, and the adhesion retention ratio before and after the environmental test is 40% or more.

8、如1~7中任1項之樹脂組成物，其為多層印刷配線板之層間絕緣用。8. The resin composition according to any one of items 1 to 7, which is used for interlayer insulation of a multilayer printed wiring board.

9、一種接著薄膜，其特徵係1~8中任1項之樹脂組成物在支持薄膜上層形成而成。9. A film which is characterized in that the resin composition of any one of the features 1 to 8 is formed on the upper layer of the support film.

10、一種預浸漬體，其特徵係1~8中任1項之樹脂組成物係含浸在由纖維構成的薄片狀補強基材中而成。A prepreg characterized in that the resin composition of any one of the features 1 to 8 is impregnated into a sheet-like reinforcing substrate composed of fibers.

11、一種印刷配線板，其特徵係具備含有1~8中任1項之樹脂組成物的硬化物之絕緣層與於該絕緣層上形成之導體層。A printed wiring board comprising: an insulating layer comprising a cured product of a resin composition of any one of 1 to 8; and a conductor layer formed on the insulating layer.

根據本發明，提供適用於多層印刷配線板等電路基板之絕緣層形成的樹脂組成物，且層合性優、在硬化後形成絕緣層時即使高溫高濕下環境試驗後，導體層與絕緣層之密著性為足夠，低熱膨脹率性亦優異的樹脂組成物。According to the present invention, there is provided a resin composition suitable for forming an insulating layer of a circuit board such as a multilayer printed wiring board, and having excellent lamination property, and forming an insulating layer after hardening, even after an environment test under high temperature and high humidity, a conductor layer and an insulating layer A resin composition having sufficient adhesion and excellent thermal expansion coefficient.

[實施發明之最佳形態][Best Mode for Carrying Out the Invention]

以下、將本發明之較佳實施形態詳細說明。Hereinafter, preferred embodiments of the present invention will be described in detail.

[滑石、二氧化矽][talc, cerium oxide]

本發明中所使用之滑石並未特別限定，可使用各種滑石，亦可使用燒成滑石。滑石的平均粒徑上限值由微細配線化、絕緣信賴性觀點，以5μm為佳，4μm更佳，3μm又更佳，2.5μm再更佳，1.8μm尤其佳，1.3μm特別佳。另外滑石的平均粒徑的下限值由防止樹脂之黏度過高、而樹脂變得不易包埋於微細配線間之觀點，以0.1μm為佳，0.2μm更佳，0.3μm又更佳，0.4μm再更佳，0.5μm特別佳。The talc used in the present invention is not particularly limited, and various talc may be used, or calcined talc may be used. The upper limit of the average particle diameter of the talc is preferably 5 μm, more preferably 4 μm, more preferably 3 μm, more preferably 2.5 μm, particularly preferably 1.8 μm, and particularly preferably 1.3 μm from the viewpoint of fine wiring and insulation reliability. Further, the lower limit of the average particle diameter of the talc is preferably 0.1 μm, more preferably 0.2 μm, and more preferably 0.3 μm, from the viewpoint of preventing the viscosity of the resin from being too high and the resin from being easily embedded in the fine wiring. The μm is even better, and 0.5 μm is particularly good.

市售滑石，如日本滑石(股)製D-600(平均粒徑0.6μm)、D-800(平均粒徑0.8μm)、D-1000(平均粒徑1.0μm)、SG-95S(平均粒徑1.2μm)、SG-95(平均粒徑2.5μm)、P-8(平均粒徑3.3μm)、P-6(平均粒徑4.0μm)、P-4(平均粒徑4.5μm)、P-3(平均粒徑5.0μm)、P-2(平均粒徑7.0μm)、L-1(平均粒徑5.0μm)、K-1(平均粒徑8.0μm)、L-G(平均粒徑5.0μm)等。上述滑石的平均粒徑可根據Mie散射理論而以雷射繞射‧散射法測定。具體上可以雷射繞射式粒度分布測定裝置將無機充填材之粒度分布以體積基準製作，且以其中值粒徑為平均粒徑來測定。測定樣本較佳可使用令滑石以超音波分散於水中者。雷射繞射式粒度分布測定裝置可使用股份公司堀場製作所製LA-500等。Commercially available talc, such as Japanese talc (stock) D-600 (average particle size 0.6 μm), D-800 (average particle size 0.8 μm), D-1000 (average particle size 1.0 μm), SG-95S (average grain 1.2 μm in diameter, SG-95 (average particle diameter: 2.5 μm), P-8 (average particle diameter: 3.3 μm), P-6 (average particle diameter: 4.0 μm), P-4 (average particle diameter: 4.5 μm), P -3 (average particle diameter: 5.0 μm), P-2 (average particle diameter: 7.0 μm), L-1 (average particle diameter: 5.0 μm), K-1 (average particle diameter: 8.0 μm), and LG (average particle diameter: 5.0 μm) )Wait. The average particle diameter of the above talc can be measured by a laser diffraction ‧ scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by a laser diffraction type particle size distribution measuring device, and the median diameter is measured as an average particle diameter. It is preferable to use a sample in which the talc is dispersed in the water by ultrasonic waves. For the laser diffraction type particle size distribution measuring apparatus, the LA-500 manufactured by the company, Horiba, Ltd., and the like can be used.

滑石的搭配量雖未特別限制，但滑石的搭配量上限值，當樹脂組成物中不揮發分為100質量%時，由防止對電路基板層合性惡化觀點以20質量%為佳，19質量%更佳，18質量%又更佳，17質量%再更佳，16質量%尤其佳，15質量%特別佳。另一方面，滑石的搭配量下限值，當樹脂組成物中不揮發分為100質量%時，由防止環境試驗後的導體層與絕緣層之密著強度降低觀點以5質量%為佳，6質量%更佳，7質量%又更佳，8質量%再更佳，9質量%尤其佳，10質量%特別佳。The amount of the talc is not particularly limited, but when the amount of the talc is not more than 100% by mass, it is preferable to prevent the deterioration of the laminate property of the circuit board by 20% by mass. The mass % is better, 18 mass% is better, 17 mass% is better, 16 mass% is particularly good, and 15 mass% is particularly good. On the other hand, when the non-volatile content of the talc is 100% by mass in the resin composition, the adhesion strength between the conductor layer and the insulating layer after the environmental test is lowered is preferably 5 mass%. 6% by mass is more preferable, 7% by mass is more preferable, 8% by mass is more preferably, 9% by mass is particularly preferable, and 10% by mass is particularly preferable.

滑石與二氧化矽之合計搭配量雖未特別限制，滑石與二氧化矽之合計搭配量的上限值，當樹脂組成物中不揮發分為100質量%時，由防止對電路基板之層合性惡化觀點以70質量%為佳，65質量%更佳，62質量%又更佳，60質量%再更佳，58質量%尤其佳，56質量%特別佳。另一方面，滑石與二氧化矽之合計搭配量的下限值，當樹脂組成物中不揮發分為100質量%時，由降低絕緣層之熱膨脹率觀點以35重量%為佳，40質量%更佳，42質量%又更佳，45質量%再更佳，47質量%尤其佳，49質量%特別佳。The total amount of the combination of talc and cerium oxide is not particularly limited, and the upper limit of the total amount of talc and cerium oxide is combined to prevent lamination of the circuit substrate when the non-volatile content of the resin composition is 100% by mass. The viewpoint of deterioration of the sex is preferably 70% by mass, more preferably 65% by mass, more preferably 62% by mass, still more preferably 60% by mass, particularly preferably 58% by mass, and particularly preferably 56% by mass. On the other hand, when the non-volatile content of the resin composition is 100% by mass, the lower limit of the total amount of talc and cerium oxide is preferably 35% by weight, and 40% by mass, from the viewpoint of lowering the thermal expansion coefficient of the insulating layer. More preferably, 42% by mass is more preferable, 45% by mass is more preferably, 47% by mass is particularly preferable, and 49% by mass is particularly preferable.

本發明樹脂組成物所搭配之二氧化矽未特別限制，使用無定形二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽等各種二氧化矽，尤以使用球狀熔融二氧化矽為佳。二氧化矽平均粒徑雖未特別限制，由微細配線形成觀點，以平均粒徑5μm以下為佳，尤以0.1μm～1.0μm為佳。平均粒徑過小，則樹脂之黏度過高、樹脂變得不易流入微細配線間，超過5.0μm，則有微細配線間、導體層間之絕緣信賴性降低傾向。The cerium oxide to which the resin composition of the present invention is blended is not particularly limited, and various cerium oxides such as amorphous cerium oxide, molten cerium oxide, crystalline cerium oxide, and synthetic cerium oxide are used, in particular, spherical sulphur dioxide is used. It is better. The average particle diameter of the cerium oxide is not particularly limited, and is preferably from 5 μm to 5 μm, more preferably from 0.1 μm to 1.0 μm, from the viewpoint of formation of fine wiring. When the average particle diameter is too small, the viscosity of the resin is too high, and the resin does not easily flow into the fine wiring. When the average thickness is more than 5.0 μm, the insulation reliability between the fine wiring and the conductor layer tends to decrease.

本發明所使用之滑石及二氧化矽以經表面處理劑表面處理而提升其耐濕性或分散性者為佳。表面處理劑可舉例如胺基矽烷系偶合劑、環氧矽烷系偶合劑、巰基矽烷系偶合劑、矽烷系偶合劑、有機矽氮烷化合物、鈦酸酯系偶合劑等。胺基矽烷系偶合劑以胺基丙基三甲氧基矽烷、胺基丙基三乙氧基矽烷、脲基丙基三乙氧基矽烷、N-苯基胺基丙基三甲氧基矽烷、N-2-(胺基乙基)胺基丙基三甲氧基矽烷為佳。環氧矽烷系偶合劑以環氧丙氧基丙基三甲氧基矽烷、環氧丙氧基丙基三乙氧基矽烷、環氧丙氧基丙基甲基二乙氧基矽烷、環氧丙基丁基三甲氧基矽烷、(3,4-環氧環己基)乙基三甲氧基矽烷為佳。巰基矽烷系偶合劑以巰基丙基三甲氧基矽烷、巰基丙基三乙氧基矽烷為佳。矽烷系偶合劑以甲基三甲氧基矽烷、十八基三甲氧基矽烷、苯基三甲氧基矽烷、甲基丙烯醯氧基丙基三甲氧基矽烷、咪唑矽烷、三嗪矽烷為佳。有機矽氮烷化合物以六甲基二矽氮烷、六苯基二矽氮烷、三矽氮烷、環三矽氮烷、1,1,3,3,5,5-六甲基環三矽氮烷為佳。鈦酸酯系偶合劑以丁基鈦酸酯雙體、鈦辛二醇酯、二異丙氧基鈦雙(三乙醇胺)、二羥基鈦雙乳酸鹽、二羥基雙(銨乳酸鹽)鈦、雙(二辛基焦磷酸鹽)乙烯鈦酸酯、雙(二辛基焦磷酸鹽)氧基乙酸酯鈦酸酯、三-n-丁氧基鈦單硬脂酸酯、四-n-丁基鈦酸酯、四(2-乙基己基)鈦酸酯、四異丙基雙(二辛基膦)鈦酸酯、四辛基雙(二(十三基)膦)鈦酸酯、四(2,2-二烯丙基氧基甲基-1-丁基)雙(二(十三基))膦鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基三異丙苯基苯基鈦酸酯、異丙基三異硬脂醯基鈦酸酯、異丙基異硬脂醯基二丙烯基鈦酸酯、異丙基二甲基丙烯酸異硬脂醯基鈦酸酯、異丙基三(二辛基磷酸鹽)鈦酸酯、異丙基三(十二烷基)苯磺醯基鈦酸酯、異丙基三(二辛基焦磷酸鹽)鈦酸酯、異丙基三(N-醯胺乙基‧胺基乙基)鈦酸酯為佳。The talc and cerium oxide used in the present invention are preferably surface-treated with a surface treating agent to improve moisture resistance or dispersibility. The surface treatment agent may, for example, be an amino decane coupling agent, an epoxy decane coupling agent, a mercapto decane coupling agent, a decane coupling agent, an organic decazane compound, or a titanate coupling agent. The amino decane coupling agent is aminopropyltrimethoxydecane, aminopropyltriethoxydecane, ureidopropyltriethoxydecane, N-phenylaminopropyltrimethoxydecane, N Preferably, -2-(aminoethyl)aminopropyltrimethoxydecane is preferred. The epoxy decane coupling agent is glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane, glycidoxypropylmethyldiethoxydecane, and propylene oxide Preferably, butyl trimethoxy decane or (3,4-epoxycyclohexyl)ethyltrimethoxy decane is preferred. The mercapto decane coupling agent is preferably mercaptopropyltrimethoxydecane or mercaptopropyltriethoxydecane. The decane coupling agent is preferably methyltrimethoxydecane, octadecyltrimethoxydecane, phenyltrimethoxydecane, methacryloxypropyltrimethoxydecane, imidazolium or triazinedecane. The organic sulfonium compound is hexamethyldiazepine, hexaphenyldioxane, triazane, cyclotriazane, 1,1,3,3,5,5-hexamethylcyclohexane Azapine is preferred. The titanate coupling agent is a butyl titanate dimer, a titanium octyl glycol ester, a diisopropoxy titanium bis(triethanolamine), a dihydroxy titanium dilactate, a dihydroxy bis(ammonium lactate) titanium, Bis(dioctyl pyrophosphate) ethylene titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n- Butyl titanate, tetrakis(2-ethylhexyl) titanate, tetraisopropylbis(dioctylphosphine) titanate, tetraoctylbis(di(tridecyl)phosphine) titanate, Tetrakis(2,2-diallyloxymethyl-1-butyl)bis(di(tridecyl)phosphine titanate, isopropyl trioctadecyl titanate, isopropyl triisopropylbenzene Phenyl titanate, isopropyl triisostearate titanate, isopropyl isostearyl decyl propylene titanate, isostearyl isopropyl methacrylate , isopropyl tris(dioctyl phosphate) titanate, isopropyl tris(dodecyl)benzenesulfonate titanate, isopropyl tris(dioctyl pyrophosphate) titanate, Isopropyl tris(N-decylamine ethyl ‧ aminoethyl) titanate is preferred.

[氰酸酯樹脂][Cyanate resin]

本發明中所使用之氰酸酯樹脂並不特別限制，例如酚醛清漆型(酚系酚醛清漆型、烷基酚系酚醛清漆型等)氰酸酯樹脂、雙酚型(雙酚A型、雙酚F型、雙酚S型等)氰酸酯樹脂及此等一部份經三嗪化的預聚物等。此等可單獨使用或2種以上組合使用。氰酸酯樹脂之重量平均分子量雖未特別限制，較佳為500～4,500，更佳為600～3,000。The cyanate resin used in the present invention is not particularly limited, and examples thereof include a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate resin, bisphenol type (bisphenol A type, double Cyanate ester resin such as phenol F type, bisphenol S type, etc., and a part of the triazine-based prepolymer. These may be used singly or in combination of two or more. The weight average molecular weight of the cyanate resin is not particularly limited, but is preferably 500 to 4,500, more preferably 600 to 3,000.

氰酸酯樹脂之具體例，例如雙酚A二氰酸酯、聚苯酚氰酸酯(寡(3-亞甲基-1,5-亞苯基氰酸酯)、4,4’-亞甲基雙(2,6-二甲基苯基氰酸酯)、4,4’-亞乙基二苯基二氰酸酯、六氟雙酚A二氰酸酯、2,2-雙(4-氰酸酯)苯基丙烷、1,1-雙(4-氰酸酯苯基)甲烷、雙(4-氰酸酯-3,5-二甲基苯基)甲烷、1,3-雙(4-氰酸酯苯基-1-(甲基亞乙基))苯、雙(4-氰酸酯苯基)硫醚、雙(4-氰酸酯苯基)醚等2官能氰酸酯樹脂；由含酚系酚醛清漆、甲酚酚醛清漆、二環戊二烯構造之苯酚樹脂等所衍生的多官能氰酸酯樹脂；此等氰酸酯樹脂一部份經三嗪化之預聚物等。Specific examples of the cyanate resin, such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylene Bis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4 -Cyanate ester)Phenylpropane, 1,1-bis(4-cyanate phenyl)methane, bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-double 2-functional cyanic acid such as (4-cyanate phenyl-1-(methylethylidene)) benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether An ester resin; a polyfunctional cyanate resin derived from a phenolic resin containing a phenolic novolac, a cresol novolak, or a dicyclopentadiene; or a part of the cyanate resin pretreated by triazine Polymer, etc.

市售氰酸酯樹脂，如下式(2)所表示之酚系酚醛清漆型多官能氰酸酯樹脂(Lonza Japan(股)製、PT30、氰酸酯當量124)、下式(3)所表示之雙酚A二氰酸酯一部份或全部經三嗪化成為三量體的預聚物(Lonza Japan(股)製、BA230、氰酸酯當量232)、含二環戊二烯構造之氰酸酯樹脂(Lonza Japan(股)製、DT-4000)等。The commercially available cyanate resin is a phenol novolak type polyfunctional cyanate resin (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124) represented by the following formula (2), and represented by the following formula (3) The bisphenol A dicyanate is partially or completely triazine-formed into a trimeric prepolymer (manufactured by Lonza Japan Co., Ltd., BA230, cyanate equivalent 232), and contains a dicyclopentadiene structure. Cyanate resin (manufactured by Lonza Japan Co., Ltd., DT-4000).

[式中、n為表示平均值之任意數。][where n is an arbitrary number representing the average value. ]

樹脂組成物中氰酸酯樹脂之含量雖未特別限制，氰酸酯樹脂之含量的上限值，由防止導體層與絕緣層之密著強度降低觀點，相對於樹脂組成物中不揮發分100質量%，以50質量%為佳，40質量%更佳，30質量%又更佳。另外，氰酸酯樹脂之含量的下限值，由防止樹脂組成物的耐熱性降低、防止絕緣層之熱膨脹率增加觀點，相對於樹脂組成物中不揮發分100質量%，以5質量%為佳，10質量%更佳，15質量%又更佳。The content of the cyanate resin in the resin composition is not particularly limited, and the upper limit of the content of the cyanate resin is such that the non-volatile content of the resin composition is 100% from the viewpoint of preventing the adhesion strength between the conductor layer and the insulating layer from being lowered. The mass% is preferably 50% by mass, more preferably 40% by mass, and even more preferably 30% by mass. In addition, the lower limit of the content of the cyanate resin is 5% by mass based on the non-volatile content of 100% by mass of the resin composition, from the viewpoint of preventing the heat resistance of the resin composition from being lowered and preventing the thermal expansion coefficient of the insulating layer from increasing. Good, 10% by mass is better, and 15% by mass is better.

[環氧樹脂][Epoxy resin]

本發明中所使用之環氧樹脂並不特別限制，例如雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、酚系酚醛清漆型環氧樹脂、烷基酚系酚醛清漆型環氧樹脂、聯苯基型環氧樹脂、芳烷基型環氧樹脂、萘酚型環氧樹脂、蒽型環氧樹脂、二環戊二烯型環氧樹脂、萘型環氧樹脂、苯酚類與具有苯酚性羥基之芳香族醛的縮合物的環氧化物、聯苯基芳烷基型環氧樹脂、芴型環氧樹脂、呫噸型環氧樹脂、三環氧丙基異氰脲酸酯等。此等環氧樹脂可各自單獨使用或2種以上組合使用。市售環氧樹脂，例如Japan Epoxy Resins(股)製「jER828EL」(液狀雙酚A型環氧樹脂)、大日本油墨化學工業(股)製「HP4032」及「HP4032D](萘型2官能環氧樹脂)、大日本油墨化學工業(股)製「HP4700」(萘型4官能環氧樹脂)、東都化成(股)製「ESN-475V」及「ESN-185V」(萘酚型環氧樹脂)、Daicel化學工業(股)製「PB-3600」(具丁二烯構造之環氧樹脂)、日本化藥(股)製「NC3000H」、「NC3000L」、「NC3100」及「NC3000」(聯苯基型環氧樹脂)、Japan Epoxy Resins(股)製「YX4000」(聯苯基型環氧樹脂)、東都化成(股)製GK3207(聯苯基型環氧樹脂)、Japan Epoxy Resins(股)製「YX8800」(含有蒽骨架型環氧樹脂)等。The epoxy resin used in the present invention is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and alkyl group. Phenolic novolak type epoxy resin, biphenyl type epoxy resin, aralkyl type epoxy resin, naphthol type epoxy resin, fluorene type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type Epoxide of epoxy resin, phenol and condensate of aromatic aldehyde having phenolic hydroxyl group, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, triepoxy Propyl isocyanurate and the like. These epoxy resins may be used singly or in combination of two or more kinds. Commercially available epoxy resin, such as "JER828EL" (liquid bisphenol A type epoxy resin) manufactured by Japan Epoxy Resins Co., Ltd., "HP4032" and "HP4032D" manufactured by Dainippon Ink Chemical Industry Co., Ltd. Epoxy resin), "HP4700" (naphthalene type 4-functional epoxy resin) manufactured by Dainippon Ink Chemical Industry Co., Ltd., "ESN-475V" and "ESN-185V" manufactured by Tohto Kasei Co., Ltd. (naphthol type epoxy) "Resin", "PB-3600" (epoxy resin with butadiene structure) made by Daicel Chemical Industry Co., Ltd., "NC3000H", "NC3000L", "NC3100" and "NC3000" made by Nippon Chemical Co., Ltd. Biphenyl type epoxy resin), "YX4000" (biphenyl type epoxy resin) manufactured by Japan Epoxy Resins Co., Ltd., GK3207 (biphenyl type epoxy resin) manufactured by Tohto Kasei Co., Ltd., Japan Epoxy Resins ( "YX8800" (including ruthenium-based epoxy resin).

樹脂組成物中環氧樹脂之含量雖未特別限制，相對於樹脂組成物中不揮發分100質量%，較佳為5～60質量%，更佳為10～50質量%，又更佳為15～40質量%。環氧樹脂之含量過少，則在後述硬化組成物表面之粗化處理時有變得易產生粗化不均之傾向。環氧樹脂之含量過多，相對地氰酸酯樹脂之含量減少，所以有絕緣層之熱膨脹率增大之傾向。The content of the epoxy resin in the resin composition is not particularly limited, and is preferably from 5 to 60% by mass, more preferably from 10 to 50% by mass, even more preferably 15% by mass based on 100% by mass of the resin composition. ～40% by mass. When the content of the epoxy resin is too small, the roughening treatment tends to cause unevenness in the roughening treatment of the surface of the hardened composition described later. When the content of the epoxy resin is too large and the content of the cyanate resin is decreased, the thermal expansion coefficient of the insulating layer tends to increase.

氰酸酯樹脂之氰酸酯當量與環氧樹脂之環氧當量比，較佳為1：0.4～1：2，更佳為1：0.5～1：1.5。當量比在上述範圍外，則後述濕式粗化步驟中絕緣層表面之低粗度化與經鍍敷形成的導體層與絕緣層之密著強度變得難以兩全。The ratio of the cyanate equivalent of the cyanate resin to the epoxy equivalent of the epoxy resin is preferably from 1:0.4 to 1:2, more preferably from 1:0.5 to 1:1.5. When the equivalent ratio is outside the above range, the lower thickness of the surface of the insulating layer and the adhesion strength between the conductor layer and the insulating layer formed by plating in the wet roughening step will be difficult to achieve.

[熱可塑性樹脂][Thermoplastic resin]

本發明所使用之熱可塑性樹脂，可舉例如苯氧樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂、聚乙烯縮醛樹脂、聚乙烯縮丁醛樹脂等。此等熱可塑性樹脂可各自單獨使用或2種以上組合使用。The thermoplastic resin used in the present invention may, for example, be a phenoxy resin, a polyimine resin, a polyamidoximine resin, a polyether quinone resin, a polyfluorene resin, a polyether oxime resin or a polyphenylene ether resin. Polycarbonate resin, polyetheretherketone resin, polyester resin, polyvinyl acetal resin, polyvinyl butyral resin, and the like. These thermoplastic resins may be used singly or in combination of two or more kinds.

熱可塑性樹脂，由防止對電路基板之層合性惡化觀點以苯氧樹脂、聚乙烯縮醛樹脂為佳。聚乙烯縮醛樹脂尤以聚乙烯縮丁醛樹脂為佳。聚乙烯縮醛樹脂之具體例，可舉例如電氣化學工業(股)製電化縮丁醛4000-2、5000-A、6000-C及6000-EP、積水化學工業(股)製愛司列克BH系列、BX系列、KS系列、BL系列及BM系列等。苯氧樹脂之具體例，可舉例如東都化成(股)製FX280及FX293、Japan Epoxy Resins(股)製YX8100、YX6954、YL6974、YL7482、YL7553、YL6794、YL7213及YL7290等。聚乙烯縮醛樹脂以玻璃轉移溫度為80℃以上者特別佳。在此「玻璃轉移溫度」係依據JIS K 7197之方法而決定。又，玻璃轉移溫度比分解溫度高，實際無法觀測到玻璃轉移溫度時，可將分解溫度作為本發明之玻璃轉移溫度。又，分解溫度係依據JIS K 7120之方法測定時的質量減少率為5%的溫度來定義。The thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin from the viewpoint of preventing deterioration of the laminate property of the circuit board. The polyvinyl acetal resin is preferably a polyvinyl butyral resin. Specific examples of the polyvinyl acetal resin include, for example, electro-chemical industrial (manufacturing) electroformation butyral 4000-2, 5000-A, 6000-C, and 6000-EP, and Sekisui Chemical Industry Co., Ltd. BH series, BX series, KS series, BL series and BM series. Specific examples of the phenoxy resin include FX280 and FX293 manufactured by Tohto Kasei Co., Ltd., YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213, and YL7290 manufactured by Japan Epoxy Resins Co., Ltd., and the like. The polyvinyl acetal resin is particularly preferably a glass transition temperature of 80 ° C or higher. Here, the "glass transition temperature" is determined in accordance with the method of JIS K 7197. Further, when the glass transition temperature is higher than the decomposition temperature, and the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature of the present invention. Further, the decomposition temperature is defined by a temperature at which the mass reduction rate at the time of measurement according to the method of JIS K 7120 is 5%.

熱可塑性樹脂之重量平均分子量以5,000～200,000範圍為佳，10,000～150,000之範圍更佳，在15,000～100,000之範圍又更佳，20,000～80,000之範圍又再更佳。較此範圍小，則薄膜成型能或機械強度提升的效果有無法充分發揮的傾向，較該範圍大，則與氰酸酯樹脂及環氧樹脂之相溶性降低，絕緣層表面之粗化處理後的粗度有增大傾向。The thermoplastic resin preferably has a weight average molecular weight of 5,000 to 200,000, more preferably 10,000 to 150,000, more preferably 15,000 to 100,000, and even more preferably 20,000 to 80,000. When the ratio is smaller than this range, the effect of improving the film forming ability or the mechanical strength may not be sufficiently exhibited. When the ratio is larger than this range, the compatibility with the cyanate resin and the epoxy resin is lowered, and the surface of the insulating layer is roughened. The thickness has a tendency to increase.

又本發明之重量平均分子量可以膠體滲透層析法(GPC)法(聚苯乙烯換算)測定。GPC法之重量平均分子量，具體上作為測定裝置使用(股)島津製作所製LC-9A/RID-6A，而作為管柱，使用昭和電工(股)製Shodex K-800P/K-804L/K-804L，作為移動相使用氯仿等，在管柱溫度40℃進行測定並使用標準聚苯乙烯檢量線算出。Further, the weight average molecular weight of the present invention can be measured by a colloidal permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight of the GPC method is specifically used as a measuring device (LC-9A/RID-6A manufactured by Shimadzu Corporation), and as a column, Shodex K-800P/K-804L/K-made by Showa Denko Co., Ltd. 804L was measured using a chloroform or the like as a mobile phase at a column temperature of 40 ° C and using a standard polystyrene calibration curve.

樹脂組成物中熱可塑性樹脂之含量雖未特別限制，相對於樹脂組成物中不揮發分100質量%，較佳為1～20質量%，更佳為2～15質量%，又更佳為3～10質量%。熱可塑性樹脂之含量過少，則有薄膜成型能或機械強度提升的效果無法發揮之傾向，且有環境試驗後的密著維持效果無法發揮的傾向，過多則，後述濕式粗化步驟後的絕緣層表面之粗度有增大傾向。The content of the thermoplastic resin in the resin composition is not particularly limited, and is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, still more preferably 3% by mass based on 100% by mass of the resin composition. ～10% by mass. When the content of the thermoplastic resin is too small, the film forming ability or the effect of improving the mechanical strength is not exhibited, and the adhesion maintaining effect after the environmental test tends not to be exhibited. If the amount is too large, the insulation after the wet roughening step will be described later. The thickness of the layer surface tends to increase.

本發明的樹脂組成物包含(A)成分、(B)成分、(C)成分、(D)成分及(E)成分，且層合性優，可提供在硬化後形成絕緣層時，即使在高溫高濕下之環境試驗後，導體層與絕緣層之密著性為足夠，低熱膨脹率性亦優異樹脂組成物。The resin composition of the present invention contains the component (A), the component (B), the component (C), the component (D), and the component (E), and has excellent lamination property, and can provide an insulating layer after curing, even when After the environmental test under high temperature and high humidity, the adhesion between the conductor layer and the insulating layer is sufficient, and the resin composition is excellent in low thermal expansion property.

本發明的樹脂組成物的硬化物的熱膨脹率可藉由後述<熱膨脹率CTE(coefficient of thermal expansion)之測定及評估>之測定方法來把握。The coefficient of thermal expansion of the cured product of the resin composition of the present invention can be grasped by a measurement method of "measurement and evaluation of coefficient of thermal expansion (CTE) described later.

本發明的樹脂組成物的硬化物的熱膨脹率以44ppm以下為佳，42ppm以下更佳，40ppm以下又更佳，38ppm以下再更佳，36ppm以下尤其佳，34ppm以下特別佳。又，該熱膨脹率的下限值亦儘可能愈低愈好，而以30ppm為佳，25ppm更佳，20ppm又更佳，10ppm再更佳，4ppm特別佳。The cured product of the resin composition of the present invention preferably has a thermal expansion coefficient of 44 ppm or less, more preferably 42 ppm or less, more preferably 40 ppm or less, more preferably 38 ppm or less, particularly preferably 36 ppm or less, and particularly preferably 34 ppm or less. Further, the lower limit of the coefficient of thermal expansion is preferably as low as possible, and preferably 30 ppm, more preferably 25 ppm, more preferably 20 ppm, more preferably 10 ppm, and particularly preferably 4 ppm.

由本發明的樹脂組成物所形成的絕緣層與導體層之環境試驗前後的密著維持率可以後述<導體層之密著強度(剝離強度)的測定及評估>之測定方法來把握。The adhesion retention ratio of the insulating layer and the conductor layer formed of the resin composition of the present invention before and after the environmental test can be grasped by the measurement method of "measurement and evaluation of the adhesion strength (peeling strength) of the conductor layer".

本發明的樹脂組成物所形成的絕緣層與導體層的環境試驗前後的密著維持率以40%以上為佳，45%以上更佳，50%以上又更佳，55%以上再更佳，60%以上尤其佳，65%以上特別佳，70%以上非常佳。又，該密著維持率的上限值愈高愈好，以80%為佳，82%更佳，84%又更佳，86%再更佳，90%尤其佳，100%特別佳。The adhesion maintaining ratio of the insulating layer and the conductor layer formed by the resin composition of the present invention before and after the environmental test is preferably 40% or more, more preferably 45% or more, more preferably 50% or more, and even more preferably 55% or more. More than 60% is especially good, more than 65% is particularly good, and more than 70% is very good. Further, the higher the upper limit of the adhesion maintenance ratio, the better, 80% is preferable, 82% is better, 84% is better, 86% is better, 90% is particularly good, and 100% is particularly good.

[有機金屬化合物][Organic Metal Compounds]

本發明的樹脂組成物中，由硬化促進觀點可更添加有機金屬化合物。有機金屬化合物，可舉例如銅(II)乙醯丙酮等有機銅化合物；鋅(II)乙醯丙酮、萘酸鋅(II)等有機鋅化合物；鈷(II)乙醯丙酮、鈷(III)乙醯丙酮等有機鈷化合物；鎳(II)乙醯丙酮等有機鎳化合物；鐵(III)乙醯丙酮等有機鐵化合物等。有機金屬化合物的添加量，相對於樹脂組成物中不揮發分100質量%，有機金屬化合物的金屬含量為25～500ppm、更佳以40～200ppm之範圍者為佳。未達25ppm則低粗度且變得難以形成高剝離強度的導體層，超過500ppm，則有樹脂組成物的保存安定性、絕緣性產生問題之傾向。In the resin composition of the present invention, an organometallic compound can be further added from the viewpoint of curing promotion. Examples of the organometallic compound include organic copper compounds such as copper (II) acetamidine acetone; organic zinc compounds such as zinc (II) acetamidine acetone and zinc naphthalate (II); cobalt (II) acetamidine acetone and cobalt (III). An organic cobalt compound such as acetonitrile acetone; an organic nickel compound such as nickel (II) acetamidineacetone; an organic iron compound such as iron (III) acetamidineacetone or the like. The amount of the organometallic compound to be added is preferably from 100 to 500 ppm, more preferably from 40 to 200 ppm, based on 100 parts by mass of the nonvolatile content in the resin composition. When the thickness is less than 25 ppm, it becomes difficult to form a conductor layer having a high peel strength, and when it exceeds 500 ppm, the storage stability and insulation properties of the resin composition tend to be problematic.

[橡膠粒子][Rubber particles]

本發明的樹脂組成物由密著性提升的觀點可再加入橡膠粒子。本發明中可使用之橡膠粒子為例如亦不溶於調製該樹脂組成物的清漆時使用的有機溶劑，而亦不與必須成分之氰酸酯樹脂或環氧樹脂等相溶者。因此，該橡膠粒子在本發明的樹脂組成物的清漆中以分散狀態存在。如此的橡膠粒子一般在橡膠成分分子量不溶於有機溶劑或樹脂之程度，使其為大且為粒子狀來調製。The resin composition of the present invention can be further added with rubber particles from the viewpoint of improving adhesion. The rubber particles which can be used in the present invention are, for example, those which are also insoluble in the varnish used to prepare the resin composition, and which are not compatible with cyanate resins or epoxy resins which are essential components. Therefore, the rubber particles are present in a dispersed state in the varnish of the resin composition of the present invention. Such rubber particles are generally prepared such that the molecular weight of the rubber component is insoluble in an organic solvent or a resin to make it large and particulate.

本發明可使用之橡膠粒子的較佳例如核殼型橡膠粒子、交聯丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯基橡膠粒子等。Preferred rubber particles which can be used in the present invention are, for example, core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, propylene-based rubber particles and the like.

核殼型橡膠粒子為具有核層與殼層之橡膠粒子，例如外層之殼層以玻璃狀聚合物所構成、且內層之核層以橡膠狀聚合物所構成之2層構造、或外層之殼層以玻璃狀聚合物所構成、中間層以橡膠狀聚合物所構成、核層以玻璃狀聚合物所構成之3層構造者等。玻璃狀聚合物層，例如甲基丙烯酸酸甲基之聚合物等所構成、橡膠狀聚合物層由例如丁基丙烯酸酯聚合物(丁基橡膠)等所構成。核殼型橡膠粒子之具體例，可舉例如StaphyloidAC3832、AC3816N(商品名、Ganz化成(股)製)、Metablen KW-4426(商品名、Mitsubishi Rayon(股)製)。The core-shell type rubber particles are rubber particles having a core layer and a shell layer, for example, a shell layer of an outer layer is composed of a glassy polymer, and a core layer of the inner layer is composed of a rubbery polymer, or an outer layer. The shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC 3832, AC3816N (trade name, manufactured by Ganz Chemical Co., Ltd.), and Metablen KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.).

交聯丙烯腈丁二烯橡膠(NBR)粒子之具體例，可舉例如XER-91(平均粒徑0.5μm、JSR(股)製)等。Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.).

交聯苯乙烯丁二烯橡膠(SBR)粒子之具體例，可舉例如XSK-500(平均粒徑0.5μm、JSR(股)製)等。Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include, for example, XSK-500 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.).

丙烯基橡膠粒子之具體例，可舉例如Metablen W300A(平均粒徑0.1μm)、W450A(平均粒徑0.2μm)(Mitsubishi Rayon(股)製)等。Specific examples of the propylene-based rubber particles include Metablen W300A (average particle diameter: 0.1 μm) and W450A (average particle diameter: 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.).

搭配之橡膠粒子平均粒徑，較佳為0.005～1μm之範圍，更佳為0.2～0.6μm範圍。本發明所使用之橡膠粒子平均粒徑可使用動的光散射法測定。例如於適當有機溶劑中將橡膠粒子以超音波等均一分散、使用濃厚系粒徑分析儀(FPAR-1000；大塚電子(股)製)，將橡膠粒子粒度分布以質量基準製作，可將其中值粒徑作為平均粒徑來測定。The average particle diameter of the rubber particles to be blended is preferably in the range of 0.005 to 1 μm, more preferably in the range of 0.2 to 0.6 μm. The average particle diameter of the rubber particles used in the present invention can be measured by a moving light scattering method. For example, the rubber particles are uniformly dispersed by ultrasonic waves in a suitable organic solvent, and a particle size distribution of the rubber particles is produced on a mass basis using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.), and the median value can be obtained. The particle diameter was measured as an average particle diameter.

橡膠粒子含量，相對於樹脂組成物中不揮發分100質量%，較佳為1～10質量%，更佳為2～5質量%。The content of the rubber particles is preferably from 1 to 10% by mass, and more preferably from 2 to 5% by mass, based on 100% by mass of the nonvolatile matter in the resin composition.

[難燃劑][flammable agent]

本發明的樹脂組成物可在不損及本發明的效果範圍內含有難燃劑。難燃劑可舉例如有機磷系難燃劑、有機系含氮磷化合物、氮化合物、矽酮系難燃劑、金屬氫氧化物等。The resin composition of the present invention can contain a flame retardant within a range that does not impair the effects of the present invention. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, an anthrone-based flame retardant, and a metal hydroxide.

有機磷系難燃劑，可舉例如三光(股)製之HCA、HCA-HQ、HCA-NQ等膦化合物、昭和高分子(股)製之HFB-2006M等含磷苯並噁嗪化合物、Ajinomoto Fine-Techno(股)製之李傲佛司30、50、65、90、110、TPP、RPD、BAPP、CPD、TCP、TXP、TBP、TOP、KP140及TIBP、北興化學工業(股)製之PPQ、Clariant(股)製之OP930、大八化學(股)製之PX200等磷酸酯化合物、東都化成(股)製之FX289、FX310等含磷環氧樹脂、東都化成(股)製之ERF001等含磷苯氧樹脂等。Examples of the organophosphorus-based flame retardant include a phosphine compound such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., a phosphorus-containing benzoxazine compound such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto. Fine-Techno (share) system of Li Aofu 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140 and TIBP, Beixing Chemical Industry Co., Ltd. PPQ, Phosphate compound such as OP930 manufactured by Clariant Co., Ltd., PX200 manufactured by Daeba Chemical Co., Ltd., phosphorus-containing epoxy resin such as FX289 and FX310 manufactured by Toho Chemical Co., Ltd., and ERF001 manufactured by Dongdu Chemical Co., Ltd. Phenoxy resin and the like.

有機系含氮磷化合物，可舉例如四國化成工業(股)製之SP670、SP703等磷酸酯醯胺化合物、大塚化學(股)製之SPB100及SPE100、(股)伏見製作所製FP-series等磷氮化合物等。Examples of the organic nitrogen-containing phosphorus compound include a phosphate amide compound such as SP670 and SP703 manufactured by Shikoku Chemicals Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Manufacturing Co., Ltd., and the like. Phosphorus nitrogen compounds, etc.

金屬氫氧化物，如Ube Material(股)製之UD65、UD650、UD653等氫氧化鎂、巴工業(股)製之B-30、B-325、B-315、B-308、B-303及UFH-20等氫氧化鋁等。Metal hydroxides such as UD65, UD650, UD653 and other magnesium hydroxides manufactured by Ube Material Co., Ltd., B-30, B-325, B-315, B-308, B-303 and Aluminum hydroxide such as UFH-20.

[其他成分][Other ingredients]

本發明的樹脂組成物，在不損害本發明的效果範圍下，因應必要可搭配其他成分。其他成分，例如矽粉末、尼龍粉末、氟粉末等有機充填劑；歐魯班、番通等增黏劑；矽酮系、氟系、高分子系之消泡劑或塗平劑；咪唑系、噻唑系、***系、矽烷系偶合劑等密著性賦予劑；咪唑系、胺系等硬化促進劑；鈦菁素‧藍、鈦菁素‧綠、碘‧綠、雙偶氮黃、碳黑等著色劑等。The resin composition of the present invention can be blended with other components as necessary without impairing the effects of the present invention. Other ingredients, such as enamel powder, nylon powder, fluorine powder and other organic fillers; Oluban, Fantong and other tackifiers; anthrone, fluorine, polymer defoamers or coating agents; imidazole, thiazole Adhesion imparting agent such as triazole system or decane coupling agent; hardening accelerator such as imidazole or amine; phthalocyanine ‧ blue, phthalocyanine ‧ green, iodine ‧ green, disazo yellow, carbon black Such as colorants and the like.

本發明的樹脂組成物的調製方法並不特別限制，例如可將必須成分之氰酸酯樹脂、環氧樹脂、熱可塑性樹脂、滑石、二氧化矽、因應必要之硬化促進劑、硬化觸媒、橡膠粒子或其他成分以旋轉混合機等混合之方法等。The preparation method of the resin composition of the present invention is not particularly limited, and for example, a cyanate resin, an epoxy resin, a thermoplastic resin, talc, cerium oxide, a hardening accelerator necessary for curing, a curing catalyst, and the like may be used. A method in which rubber particles or other components are mixed by a rotary mixer or the like.

本發明的樹脂組成物的用途雖不特別限定，可使用於接著薄膜、預浸漬體等絕緣樹脂薄片、電路基板、阻焊劑、底部填充材、晶粒黏著材、半導體封閉材、封孔樹脂、封零件樹脂等需要樹脂組成物用途之廣範圍。其中，多層印刷配線板之製造中可適用於形成絕緣層。本發明的樹脂組成物亦可以清漆狀態塗佈在電路基板後、使硬化形成絕緣層，但工業上一般以接著薄膜、預浸漬體等薄片狀層合材料形態使用為佳。樹脂組成物的軟化點由薄片狀層合材料層合性觀點以40～150℃為佳。The use of the resin composition of the present invention is not particularly limited, and can be used for an insulating resin sheet such as a film or a prepreg, a circuit board, a solder resist, an underfill, a die attach material, a semiconductor sealing material, a sealing resin, and the like. Sealing parts and the like require a wide range of uses of the resin composition. Among them, the multilayer printed wiring board can be suitably used for forming an insulating layer. The resin composition of the present invention may be applied to a circuit board in a varnish state and then cured to form an insulating layer. However, it is generally industrially used in the form of a sheet-like laminate such as a film or a prepreg. The softening point of the resin composition is preferably from 40 to 150 ° C from the viewpoint of laminar laminate lamination property.

[接著薄膜][Next film]

本發明的接著薄膜可藉由該業者公知方法、例如調製於有機溶劑中溶解樹脂組成物之樹脂清漆，並將此樹脂清漆使用模具塗佈機等塗佈在支持體之支持薄膜，進一步經加熱、或熱風吹等使有機溶劑乾燥後形成樹脂組成物層而製造。The adhesive film of the present invention can be applied to a support film of a support by a mold coater or the like by a method known to the manufacturer, for example, a resin varnish prepared by dissolving a resin composition in an organic solvent, and further heated. The organic solvent is dried by hot air blowing or the like to form a resin composition layer.

該有機溶劑可舉例如丙酮、甲基乙基酮、環己酮等酮類；乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丙二醇單甲基醚乙酸酯、卡必醇乙酸酯等乙酸酯類；溶纖劑類；丁基卡必醇等卡必醇類；甲苯、二甲苯等芳香族烴類；二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等。有機溶劑亦可2種以上組合使用。The organic solvent may, for example, be a ketone such as acetone, methyl ethyl ketone or cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetic acid Acetates such as esters; cellosolves; carbitols such as butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methyl Pyrrolidone and the like. The organic solvent may be used in combination of two or more kinds.

將有機溶劑乾燥除去之條件雖未特別限制，樹脂組成物層中有機溶劑之含量以乾燥至10質量%以下為佳，更佳為乾燥至5質量%以下。雖因清漆中的有機溶劑量、有機溶劑之沸點而異，但藉由例如將含30～60質量%有機溶劑的清漆在50～150℃進行3～10分鐘左右，形成有機溶劑之含量為10質量%以下之樹脂組成物層。該業者可藉由簡單的實驗來設定適宜、較佳乾燥條件。The condition for drying and removing the organic solvent is not particularly limited, and the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, more preferably 5% by mass or less. Although the amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent, for example, the varnish containing 30 to 60% by mass of the organic solvent is subjected to 50 to 150 ° C for about 3 to 10 minutes to form an organic solvent content of 10 A resin composition layer of a mass% or less. The manufacturer can set suitable and preferred drying conditions by simple experimentation.

接著薄膜中所形成之樹脂組成物層之厚度，通常在導體層之厚度以上。因電路基板所具有的導體層之厚度通常為5～70μm之範圍者，故樹脂組成物層以具有10～100μm厚度者為佳。The thickness of the resin composition layer formed in the film is usually more than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.

本發明中支持薄膜可舉例如由聚乙烯、聚丙烯、聚氯化乙烯等聚烯烴；聚乙烯對苯二甲酸酯(以下簡稱「PET」。)、聚萘二甲酸乙二酯等聚酯；聚碳酸酯；聚醯亞胺等所成薄膜、進而如脫模紙或銅箔、鋁箔等金屬箔等。又，支持薄膜及後述保護薄膜除可施加mat處理、電暈處理外，亦可施加脫模處理。The support film in the present invention may, for example, be a polyolefin such as polyethylene, polypropylene or polyvinyl chloride; a polyethylene terephthalate (hereinafter referred to as "PET") or a polyester such as polyethylene naphthalate. Polycarbonate; a film formed by polyimine or the like, and further a metal foil such as release paper, copper foil, or aluminum foil. Further, the support film and the protective film described later may be subjected to a mold release treatment in addition to a mat treatment or a corona treatment.

支持薄膜厚度雖未特別限制，以10～150μm為佳，25～50μm更佳。The thickness of the support film is not particularly limited, and is preferably 10 to 150 μm, more preferably 25 to 50 μm.

於樹脂組成物層之支持薄膜未密著面，可於支持薄膜再層合保護薄膜。保護薄膜的厚度雖未特別限制，以1～40μm為佳。藉由層合保護薄膜，可防止在樹脂組成物層之表面附著灰塵等或防止刮傷。接著薄膜亦可捲取為輥狀以便收藏。The support film on the resin composition layer is not adhered to the surface, and the protective film can be laminated on the support film. The thickness of the protective film is not particularly limited, and is preferably 1 to 40 μm. By laminating the protective film, it is possible to prevent dust or the like from adhering to the surface of the resin composition layer or to prevent scratching. The film can then be rolled into a roll for collection.

[使用接著薄膜的多層印刷配線板][Multilayer printed wiring board using a film]

接著，說明使用如上述製造之接著薄膜製造多層印刷配線板之方法的一例。Next, an example of a method of producing a multilayer printed wiring board using the adhesive film produced as described above will be described.

首先，將接著薄膜使用真空層合機層合於電路基板之單面或雙面。電路基板可使用之基板，可舉例如玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚亞苯基醚基板等。又，在此電路基板係指上述般於基板之單面或雙面形成經圖案加工的導體層(電路)者。又在導體層與絕緣層交互層合而成的多層印刷配線板中，該多層印刷配線板之最外層之單面或雙面成為有圖案加工的導體層(電路)者亦包含於此電路基板。且於導體層表面亦可藉由黑化處理、銅微蝕等預先施加粗化處理。First, the adhesive film is laminated on one or both sides of the circuit substrate using a vacuum laminator. Examples of the substrate that can be used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. In addition, the circuit board means a conductor layer (circuit) in which a pattern is formed on one surface or both surfaces of the substrate as described above. Further, in the multilayer printed wiring board in which the conductor layer and the insulating layer are alternately laminated, the one or both sides of the outermost layer of the multilayer printed wiring board are also patterned circuit conductors (circuits) included in the circuit substrate. . Further, the surface of the conductor layer may be subjected to a roughening treatment by blackening treatment, copper micro-etching or the like.

上述層合中，接著薄膜具有保護薄膜時，在除去該保護薄膜後，因應必要將接著薄膜及電路基板預熱並使接著薄膜邊進行加壓及加熱邊壓附在電路基板上。本發明的接著薄膜中，適宜使用在藉由真空層合法於減壓下層合於電路基板之方法。層合條件雖未特別限制，例如壓著溫度(層合溫度)較佳為70～140℃、壓著壓力較佳為1～11kgf/cm² (9.8×10⁴ ～107.9×10⁴ N/m² )，以空氣壓20mmHg(26.7hPA)以下之減壓下層合者為佳。又，層合方法可為批次式或以輥進行連續式。In the above-mentioned lamination, when the protective film is removed, the film and the circuit board are preheated, and the film is then pressed and heated while being pressed onto the circuit board. In the adhesive film of the present invention, a method of laminating to a circuit substrate under reduced pressure by vacuum lamination is suitably used. The lamination conditions are not particularly limited, and for example, the pressing temperature (laminating temperature) is preferably 70 to 140 ° C, and the pressing pressure is preferably 1 to 11 kgf/cm ² (9.8 × 10 ⁴ to 107.9 × 10 ⁴ N/m). ² ) It is preferred to laminate the laminate under a reduced pressure of 20 mmHg (26.7 hPA) or less. Further, the lamination method may be batch type or continuous in a roll.

真空層合可使用市售真空層合機進行。市售真空層合機，可舉例如Nichigo-morton(股)製真空貼實機、(股)名機製作所製真空加壓式層合機、(股)日立INDUSTRIES輥式乾式塗佈機、日立AIC(股)製真空層合機等。Vacuum lamination can be carried out using a commercially available vacuum laminator. Commercially available vacuum laminating machine, for example, a vacuum compactor manufactured by Nichigo-morton Co., Ltd., a vacuum pressurizing laminator manufactured by Nihon Seiki Co., Ltd., a Hitachi INDUSTRES roll dry coater, Hitachi AIC (stock) vacuum laminator and the like.

又，減壓下、進行加熱及加壓的層合步驟可使用一般真空熱壓機進行。例如可藉由將經加熱之SUS板等金屬板從支持體層側進行加壓來進行。Further, the laminating step of heating and pressurizing under reduced pressure can be carried out using a general vacuum hot press. For example, it can be performed by pressurizing a metal plate such as a heated SUS plate from the side of the support layer.

加壓條件一般減壓度通常在1×10^-2 MPa以下、較佳為1×10^-3 MPa以下之減壓下。加熱及加壓可以1階段進行，但由控制樹脂之滲漏觀點以2階段以上不同條件進行為佳。例如以第1階段加壓在溫度70～150℃、壓力1～15kgf/cm² 之範圍、第2階段之加壓在溫度150～200℃、壓力1～40kgf/cm² 之範圍進行為佳。各階段之時間以30～120分鐘進行為佳。市售真空熱壓機，可舉例如MNPC-V-750-5-200(股)名機製作所製)、VH1-1603(北川精機(股)製)等。The pressurization conditions are generally at a reduced pressure of 1 × 10 ^-2 MPa or less, preferably 1 × 10 ^-3 MPa or less. The heating and the pressurization may be carried out in one step, but it is preferably carried out under the conditions of two or more stages from the viewpoint of controlling the leakage of the resin. For example, it is preferred to carry out the first stage pressurization at a temperature of 70 to 150 ° C, a pressure of 1 to 15 kgf/cm ² , and a second stage of pressurization at a temperature of 150 to 200 ° C and a pressure of 1 to 40 kgf/cm ² . The time of each stage is preferably 30 to 120 minutes. The commercially available vacuum hot press may, for example, be manufactured by MNPC-V-750-5-200 (manufactured by Nippon Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), or the like.

接著將薄膜層合於電路基板後，冷卻至室溫附近再將支持薄膜剝離時，藉由剝離、熱硬化可於電路基板上形成絕緣層。熱硬化之條件因應樹脂組成物中的樹脂成分種類、含量等適宜選擇即可，但較佳為在150℃～220℃下20分～180分、更佳為在160℃～200℃下30～120分之範圍來選擇。After the film is laminated on the circuit board and then cooled to near room temperature and the support film is peeled off, an insulating layer can be formed on the circuit board by peeling and heat curing. The heat curing condition may be appropriately selected depending on the type and content of the resin component in the resin composition, but is preferably 20 to 180 minutes at 150 to 220 ° C, more preferably 30 to 160 ° C to 200 ° C. Choose from a range of 120 points.

硬化前未剝離支持薄膜之情況，於形成絕緣層後進行剝離。接著因應必要，在電路基板上形成之絕緣層進行開孔以形成貫穿孔、通孔。開孔可藉由例如鑽頭、雷射、電漿等公知方法或必要時藉由組合此等方法來進行，但以二氧化碳雷射、YAG雷射等雷射來開孔為最一般的方法。In the case where the support film is not peeled off before the hardening, the insulating layer is formed and peeled off. Then, if necessary, the insulating layer formed on the circuit substrate is opened to form a through hole and a through hole. The opening can be performed by a known method such as a drill, a laser, a plasma, or the like by a combination of these methods, but it is the most common method to open a hole by a laser such as a carbon dioxide laser or a YAG laser.

接著、經乾式鍍敷或濕式鍍敷於絕緣層上形成導體層。乾式鍍敷，可使用蒸著、濺鍍、離子噴鍍等公知方法。又，濕式鍍敷時，先將硬化之樹脂組成物層(絕緣層)的表面進行濕式粗化處理。濕式粗化處理係指以過錳酸鹽(過錳酸鉀、過錳酸鈉等)、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等氧化劑粗化處理並形成凸凹之錨點之處理。氧化劑尤以過錳酸鉀、過錳酸鈉等氫氧化鈉水溶液(鹼性過錳酸水溶液)為佳。粗化處理之後以組合無電解鍍敷與電解鍍敷之方法形成導體層。又，導體層係指形成逆圖案的鍍敷光阻且亦可僅以無電解鍍敷形成導體層。之後的圖案形成方法，可使用例如該業者公知的減除法、半加成法等。Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. For dry plating, a known method such as evaporation, sputtering, or ion plating can be used. Further, in the wet plating, the surface of the cured resin composition layer (insulating layer) is first subjected to wet roughening treatment. Wet roughening treatment refers to roughening treatment with oxidizing agents such as permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, etc. Processing. The oxidizing agent is preferably an aqueous sodium hydroxide solution (alkaline permanganic acid aqueous solution) such as potassium permanganate or sodium permanganate. After the roughening treatment, a conductor layer is formed by a combination of electroless plating and electrolytic plating. Further, the conductor layer means a plating resist which forms an inverse pattern and may be formed of electroless plating only to form a conductor layer. For the subsequent pattern forming method, for example, a subtractive method, a semi-additive method, or the like which is well known to the manufacturer can be used.

如此將製作之導體層表面進行粗化。導體層表面之粗化具有提高與導體層相接樹脂的密著性效果。粗化導體層以使用有機酸系微蝕劑CZ-8100、CZ-8101、CZ-5480等為佳。又，藉由使用本發明的印刷配線板用樹脂組成物，無關於導體層表面之粗化程度，因較以往樹脂組成物密著性提升，形成低熱膨脹率、層合性及環境試驗後的與導體層之密著強度等性能取得平衡性的絕緣層。The surface of the produced conductor layer is thus roughened. The roughening of the surface of the conductor layer has an effect of improving the adhesion of the resin to the conductor layer. The roughening conductor layer is preferably an organic acid-based microetching agent CZ-8100, CZ-8101, CZ-5480 or the like. Further, by using the resin composition for a printed wiring board of the present invention, the degree of roughening of the surface of the conductor layer is not improved, and the resin composition is improved in adhesion, and a low thermal expansion coefficient, lamination property, and environmental test are formed. An insulating layer that balances the properties such as the adhesion strength of the conductor layer.

[預浸漬體][Prepreg]

本發明的預浸漬體可藉由將本發明的樹脂組成物於纖維構成的薄片狀補強基材以熱熔法或溶劑法含浸、加熱後，使半硬化而製造。亦即，本發明的樹脂組成物可成為於纖維所成薄片狀補強基材中含浸狀態的預浸漬體。由纖維構成的薄片狀補強基材，例如可使用玻璃布或聚芳醯胺纖維等作為預浸漬體用纖維常用纖維所成者。The prepreg of the present invention can be produced by subjecting the resin composition of the present invention to a sheet-shaped reinforcing substrate composed of fibers by a hot melt method or a solvent method, and then heating and then semi-curing. In other words, the resin composition of the present invention can be a prepreg impregnated in a sheet-like reinforcing substrate in which the fibers are formed. For the sheet-like reinforcing substrate composed of fibers, for example, a glass cloth, a polyamidamide fiber or the like can be used as a fiber for fibers for prepreg.

熱熔法為非將樹脂溶於有機溶劑，而是暫時塗佈在與該樹脂剝離性佳的塗佈紙上。使其於薄片狀補強基材上層合、或使樹脂非溶於有機溶劑，而是藉由模具塗佈機於薄片狀補強基材直接塗佈等以製作預浸漬體的方法。且溶劑法如同接著薄膜般，將樹脂溶於有機溶劑後調製樹脂清漆，並於該清漆中使薄片狀補強基材浸漬，並使樹脂清漆含浸於薄片狀補強基材，之後乾燥的方法。In the hot melt method, the resin is not dissolved in an organic solvent, but is temporarily applied onto a coated paper having good peelability from the resin. A method of forming a prepreg by laminating it on a sheet-like reinforcing substrate or dissolving the resin in an organic solvent, and directly applying it to a sheet-like reinforcing substrate by a die coater. Further, the solvent method is a method in which a resin is dissolved in an organic solvent to prepare a resin varnish, and a flaky reinforcing substrate is immersed in the varnish, and the resin varnish is impregnated into a sheet-like reinforcing substrate, followed by drying.

[使用預浸漬體的多層印刷配線板][Multilayer printed wiring board using prepreg]

接著，說明使用如上述般製造的預浸漬體後製作多層印刷配線板之方法例。於電路基板將本發明的預浸漬體1片或因必要複數片重疊，間隔脫模薄膜以金屬板挾持，在加壓‧加熱條件下進行加壓層合。加壓‧加熱條件較佳為壓力5～40kgf/cm² (49×10⁴ ～392×10⁴ N/m² )、溫度為120～200℃下20～100分鐘。又亦可與接著薄膜同樣，使預浸漬體以真空層合法層合於電路基板後、加熱硬化。之後，與上述記載方法同樣將硬化之預浸漬體表面如上述般粗化後，使導體層經鍍敷形成以製作多層印刷配線板。Next, an example of a method of producing a multilayer printed wiring board using the prepreg manufactured as described above will be described. One piece of the prepreg of the present invention or a plurality of sheets as necessary was superposed on the circuit board, and the release film was held by a metal plate, and pressure lamination was carried out under pressure and heating. The pressurization and heating conditions are preferably a pressure of 5 to 40 kgf/cm ² (49 × 10 ⁴ to 392 × 10 ⁴ N/m ² ) and a temperature of 120 to 200 ° C for 20 to 100 minutes. Similarly to the subsequent film, the prepreg may be laminated to the circuit board by vacuum lamination, and then heat-hardened. Thereafter, the surface of the prepreg which has been cured is roughened as described above in the same manner as described above, and then the conductor layer is plated to form a multilayer printed wiring board.

以下，將本發明以實施例具體說明，但本發明不限於此等實施例。Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited to the examples.

[實施例][Examples]

[實施例1][Example 1]

將雙酚A二氰酸酯預聚物(Lonza Japan(股)製「BA230S75」、氰酸酯當量約232、不揮發分75質量%之甲基乙基酮(以下、簡稱MEK)溶液)30質量份、酚系酚醛清漆型多官能氰酸酯樹脂(Lonza Japan(股)製「PT30」、氰酸酯當量約124)10質量份、MEK10質量份一起攪拌混合，再混合作為萘酚型環氧樹脂之東都化成(股)製「ESN-475V」(下述一般式(1)所表示。環氧當量約340之不揮發分65質量%之MEK溶液)40質量份、進而液狀雙酚A型環氧樹脂(Japan Epoxy Resins(股)製「jER828EL」、環氧當量約185)8質量份、苯氧樹脂溶液(Japan Epoxy Resins(股)製「YX6954」、重量平均分子量40000、不揮發分30質量%之MEK與環己酮之混合溶液)20質量份、鈷(II)乙醯丙酮(Co(AcAc)₂ 、東京化成(股)製)的1質量%之N，N-二甲基甲醯胺(DMF)溶液4質量份、滑石(日本滑石(股)製「D-800」以胺基矽烷進行表面處理者、平均粒徑0.8μm)6質量份、及球形二氧化矽((股)Admatechs製「SO-C2」以胺基矽烷作表面處理者、平均粒徑0.5μm)42質量份後，加入MEK20質量份，並以高速旋轉混合機均一分散後，製作熱硬化性樹脂組成物清漆。Bisphenol A dicyanate prepolymer ("BA230S75" manufactured by Lonza Japan Co., Ltd., methyl ketone (hereinafter referred to as MEK) solution having a cyanate ester equivalent of about 232 and a nonvolatile content of 75 mass%) 30 10 parts by mass of a phenolic novolac type polyfunctional cyanate resin ("3030" manufactured by Lonza Japan Co., Ltd., cyanate equivalent: 124) and 10 parts by mass of MEK are stirred and mixed, and mixed as a naphthol ring. "ESN-475V" manufactured by Tosoh Chemical Co., Ltd. (expressed as follows: general formula (1): MEK solution having an epoxy equivalent of about 340 and a nonvolatile content of 65 mass%) 40 parts by mass, and further liquid bisphenol A type epoxy resin ("JER828EL" manufactured by Japan Epoxy Resins Co., Ltd., epoxy equivalent: 185) 8 parts by mass, phenoxy resin solution ("YX6954" manufactured by Japan Epoxy Resins Co., Ltd., weight average molecular weight 40000, non-volatile 20 parts by mass of a mixed solution of MEK and cyclohexanone) 20 parts by mass of N,N-dimethyl ester of cobalt (II) acetamidineacetone (Co(AcAc) ₂ , manufactured by Tokyo Chemical Industry Co., Ltd.) 4 parts by mass of mercaptoamine (DMF) solution, talc (manufactured by Japanese talc (D-800), surface-treated with amino decane, average particle diameter: 0.8 μm), 6 parts by mass, and spherical 42 矽 矽 ( SO SO SO Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad Ad ME ME ME ME ME ME ME ME ME ME ME ME ME ME ME ME ME ME A curable resin composition varnish.

接著，將該樹脂組成物清漆於聚乙烯對苯二甲酸酯薄膜(厚度38μm、以下簡稱PET薄膜)上，以乾燥後的樹脂組成物層之厚度成為40μm之方式使用模具塗佈機進行均一塗佈，以80~120℃(平均100℃)進行6分鐘乾燥(樹脂組成物層中的殘留溶劑量：約1.5質量%)。接著、於樹脂組成物層之表面邊貼合厚度15μm之聚丙烯薄膜邊捲取為輥狀。將輥狀接著薄膜切為寬507mm，而得到507×336mm尺寸之薄片狀接著薄膜。Then, the resin composition was varnished on a polyethylene terephthalate film (thickness: 38 μm, hereinafter abbreviated as PET film), and uniformity was carried out using a die coater so that the thickness of the dried resin composition layer was 40 μm. The coating was dried at 80 to 120 ° C (average 100 ° C) for 6 minutes (the amount of residual solvent in the resin composition layer: about 1.5% by mass). Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer and wound up into a roll shape. The roll-shaped film was cut into a width of 507 mm to obtain a sheet-like film of a size of 507 × 336 mm.

(n為平均值1～6之數，X為環氧丙基或碳數1～8之烴基，烴基/環氧丙基之比率為0.05～2.0。)(n is an average value of 1 to 6, X is a glycidyl group or a hydrocarbon group having 1 to 8 carbon atoms, and the ratio of the hydrocarbon group to the epoxy group is 0.05 to 2.0.)

[實施例2][Embodiment 2]

除使實施例1之D800為10質量份、SO-C2為38質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 10 parts by mass and SO-C2 was 38 parts by mass.

[實施例3][Example 3]

除使實施例1之D800為12質量份、SO-C2為36質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 12 parts by mass and SO-C2 was 36 parts by mass.

[實施例4][Example 4]

除使實施例1之D800為16質量份、SO-C2為32質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 16 parts by mass and SO-C2 was 32 parts by mass.

[實施例5][Example 5]

除使實施例1之D800為18質量份、SO-C2為30質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 18 parts by mass and SO-C2 was 30 parts by mass.

[實施例6][Embodiment 6]

除使實施例1之D800為22質量份、SO-C2為26質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 22 parts by mass and SO-C2 was 26 parts by mass.

[實施例7][Embodiment 7]

實施例1之D800為24質量份、SO-C2為24質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 24 parts by mass and SO-C2 was 24 parts by mass.

[實施例8][Embodiment 8]

除使實施例1之D800為11質量份、SO-C2為28質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 11 parts by mass and SO-C2 was 28 parts by mass.

[實施例9][Embodiment 9]

除使實施例1之D800為15質量份、SO-C2為57質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 15 parts by mass and SO-C2 was 57 parts by mass.

[實施例10][Embodiment 10]

除使實施例1之D800為18質量份、SO-C2為90質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 18 parts by mass and SO-C2 was 90 parts by mass.

[實施例11][Example 11]

除使實施例1之D800為8質量份、SO-C2為66質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 8 parts by mass and SO-C2 was 66 parts by mass.

[實施例12][Embodiment 12]

除使實施例1之D800為22質量份、SO-C2為50質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 22 parts by mass and SO-C2 was 50 parts by mass.

[實施例13][Example 13]

除取代實施例1之D800為SG-95(經胺基矽烷表面處理者、平均粒徑2.5μm)15質量份、SO-C2為57質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was replaced by 15 parts by mass of SG-95 (manufactured by amine decane surface treatment, average particle diameter: 2.5 μm), and SO-C2 was 57 parts by mass.

[比較例1][Comparative Example 1]

除不使用實施例1之D800，而SO-C2為48質量份以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was not used, and SO-C2 was 48 parts by mass.

[比較例2][Comparative Example 2]

除實施例1之D800為4質量份、SO-C2為45質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 4 parts by mass and SO-C2 was 45 parts by mass.

[比較例3][Comparative Example 3]

除實施例1之D800為30質量份、SO-C2為18質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 30 parts by mass and SO-C2 was 18 parts by mass.

[比較例4][Comparative Example 4]

除實施例1之D800為48質量份、而不使用SO-C2以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 48 parts by mass, and SO-C2 was not used.

[比較例5][Comparative Example 5]

除實施例1之D800為10質量份、SO-C2為21份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 10 parts by mass and SO-C2 was 21 parts.

[比較例6][Comparative Example 6]

除實施例1之D800為21質量份、SO-C2為115質量份以外，與實施例1同樣地得到接著薄膜。An adhesive film was obtained in the same manner as in Example 1 except that 21 parts by mass of D800 of Example 1 and 115 parts by mass of SO-C2.

[比較例7][Comparative Example 7]

除實施例1之D800為13質量份、SO-C2為54質量份而不搭配YX6954以外，與實施例1同樣地得到接著薄膜。A film was obtained in the same manner as in Example 1 except that D800 of Example 1 was 13 parts by mass and SO-C2 was 54 parts by mass without using YX6954.

<密著強度測定樣本之調製><Preparation of adhesion strength measurement sample>

(1)層合板之底層處理(1) Underlayer treatment of laminate

為了評估導體層與絕緣層之密著強度，將形成內層電路的雙面貼銅層合板[銅箔厚度18μm、基板厚度0.3mm、松下電工(股)製R5715ES]雙面浸漬於Mec(股)製MECetchBONDCZ-8100後對電路表面進行粗化處理(RA值=1μm)。In order to evaluate the adhesion strength between the conductor layer and the insulating layer, a double-sided copper-clad laminate (copper foil thickness: 18 μm, substrate thickness: 0.3 mm, R5715ES manufactured by Matsushita Electric Works) having an inner layer circuit was double-sidedly immersed in Mec. After the MECetchBONDCZ-8100 is manufactured, the surface of the circuit is roughened (RA value = 1 μm).

(2)接著薄膜的層合(2) subsequent lamination of the film

將以實施例1～10及比較例1～6所製作的接著薄膜，使用批次式真空加壓層合機MVLP-500(名機(股)製商品名)，層合於層合板之雙面。層合係藉由30秒減壓後，氣壓在13hPa以下，之後以30秒鐘、100℃、壓力0.74MPa加壓而進行。The adhesive film produced in Examples 1 to 10 and Comparative Examples 1 to 6 was laminated on a laminate sheet using a batch type vacuum pressure laminator MVLP-500 (trade name, manufactured by a famous machine). surface. The laminated system was subjected to a pressure reduction of 30 seconds, and the gas pressure was 13 hours or less, followed by pressurization at 30 seconds, 100 ° C, and a pressure of 0.74 MPa.

(3)銅箔之底層處理(3) Underlying treatment of copper foil

將三井金屬礦山(股)製3EC-III(電場銅箔、35μm)的光澤面浸漬於Mec(股)製MECetchBONDCZ-8100後對銅箔表面進行粗化處理(RA值=1μm)。The shiny surface of 3EC-III (electric field copper foil, 35 μm) manufactured by Mitsui Metals Co., Ltd. was immersed in MECetch BONDCZ-8100 manufactured by Mec Co., Ltd., and the surface of the copper foil was roughened (RA value = 1 μm).

(4)銅箔之層合與絕緣層形成(4) Lamination of copper foil and formation of insulating layer

從上述(2)中層合的接著薄膜剝離PET薄膜，將以(3)處理之銅箔的處理面作為樹脂組成物層側，在與(2)同樣條件下，使銅箔於電路基板雙面上形成的樹脂組成物層上層合。藉由以190℃、90分鐘的硬化條件硬化樹脂組成物後形成絕緣層而製作樣本。The PET film was peeled off from the adhesive film laminated in the above (2), and the treated surface of the copper foil treated in (3) was used as the resin composition layer side, and the copper foil was double-sided on the circuit substrate under the same conditions as in (2). The resin composition layer formed thereon is laminated. A sample was prepared by curing the resin composition at 190 ° C for 90 minutes to form an insulating layer.

<熱膨脹率CTE(coefficient of thermal expansion)的測定及評估><Measurement and evaluation of coefficient of thermal expansion (CTE)

於實施例及比較例中，除於支持體使用氟樹脂系脫模劑(ETFE)處理的PET(三菱樹脂(股)製「福落久RL50KSE以外，同樣地，得到具有與各實施例、比較例相同樹脂組成物層之接著薄膜。將所得接著薄膜以190℃、90分鐘加熱使熱硬化，藉由剝離支持體而獲得薄片狀硬化物。將該硬化物切斷為寬約5mm、長約15mm之試驗片，使用熱機械分析裝置Thermo Plus TMA8310((股)Rigaku製)，以拉伸加重法進行熱機械分析。將試驗片裝設到前述裝置後，以荷重1g、昇溫速度5℃/分的測定條件連續測定2次。算出第2次的測定中25℃～150℃的平均線熱膨脹率(ppm)。CTE值未達35ppm時為「◎」，35ppm以上未達40ppm時為「○」，40ppm以上未達45ppm時為「△」，45ppm以上時為「×」。所得結果如表1、2。In the examples and the comparative examples, except for the PET (Mitsubishi Resin Co., Ltd. product "Fukuoka RL50KSE" which was treated with a fluororesin-based release agent (ETFE), the same results were obtained and compared with the respective examples. An adhesive film of the same resin composition layer was used, and the obtained adhesive film was heated at 190 ° C for 90 minutes to be thermally cured, and a sheet-like cured product was obtained by peeling off the support. The cured product was cut into a width of about 5 mm and a length of about 5 mm. A 15 mm test piece was subjected to thermomechanical analysis by a tensile weighting method using a thermomechanical analyzer Thermo Plus TMA8310 (manufactured by Rigaku Co., Ltd.) After the test piece was attached to the above apparatus, the load was 1 g, and the temperature was raised at 5 ° C / The measurement conditions of the fractions were measured twice in a row. The average linear thermal expansion coefficient (ppm) at 25 ° C to 150 ° C in the second measurement was calculated. When the CTE value was less than 35 ppm, it was "◎", and when 35 ppm or more was less than 40 ppm, it was "○". "40" is "△" when it is less than 45 ppm, and "x" when it is 45 ppm or more. The results are shown in Tables 1 and 2.

<層合性之評估><Evaluation of lamination>

將實施例及比較例之薄膜以上述(3)所記載層合條件層合於電路基板，依據外觀檢查，如以下進行判定。結果如表1、2。The film of the examples and the comparative examples was laminated on a circuit board under the lamination conditions described in the above (3), and was judged as follows based on the visual inspection. The results are shown in Tables 1 and 2.

○：電路基板之電路部分無裂縫，樹脂非常連貫。○: The circuit portion of the circuit board has no cracks, and the resin is very continuous.

×：電路基板之電路基板有裂縫而樹脂連貫不足。X: The circuit board of the circuit board has a crack and the resin is insufficiently connected.

<與導體層之密著強度(剝離強度)的測定及評估><Measurement and evaluation of adhesion strength (peel strength) to conductor layer>

將上述(4)記載之樣本510×340mm切斷為150×30mm之小片。在小片銅箔部分，寬10mm、長100mm之部分加入切痕，將銅箔一端剝離以抓取工具抓牢，使用Instron萬能試驗機，在室溫中以50mm/分之速度測定垂直方向拉撕35mm時的荷重，作為環境試驗前之剝離強度。The sample 510 × 340 mm described in the above (4) was cut into small pieces of 150 × 30 mm. In the small piece of copper foil, a section of 10 mm wide and 100 mm long is added with a cut mark, and one end of the copper foil is peeled off to grasp the grasping tool, and the vertical direction tearing is measured at a temperature of 50 mm/min at room temperature using an Instron universal testing machine. The load at 35 mm was taken as the peel strength before the environmental test.

進一步，將同一樣本以高度加速壽命試驗裝置PM422(楠本化成(股)製)，在130℃、85%RH條件下100小時間加速環境試驗後，以同樣方法測定拉撕強度作為環境試驗後的剝離強度。「環境試驗後的剝離強度÷環境試驗前剝離強度×100」之值為密著維持率(%)，進行加速環境試驗前後的剝離強度比較。密著維持率為75%以上時為「◎」，未達75%且在50%以上時為「○」，未達50%且40%以上時為「△」，未達40%時為「×」。結果如表1、2。Further, the same sample was subjected to an accelerated environmental test at a temperature of 130 ° C and 85% RH for 100 hours under the conditions of high-acceleration life test apparatus PM422 (manufactured by Nanben Chemical Co., Ltd.), and the tear strength was measured in the same manner as an environmental test. Peel strength. The value of "peel strength after environmental test 剥离 peel strength before environmental test × 100" is the adhesion retention ratio (%), and the peel strength before and after the accelerated environmental test is compared. When the adhesion retention rate is 75% or more, it is "◎", and when it is less than 75%, it is "○" when it is 50% or more, "△" when it is less than 50% and 40% or more, and "△" when it is less than 40%. ×". The results are shown in Tables 1 and 2.

由表1、2之結果，實施例中低熱膨脹率、層合性及環境試驗後的密著強度皆優，成為此等性能均衡性佳者。另一方面，比較例1、2因滑石含量少，環境試驗後的密著強度降低變得顯著。且比較例3、4因滑石的含量過多，層合性惡化。進一步，比較例5因滑石與二氧化矽之總含量少，變得熱膨脹率增大。又比較例6因滑石與二氧化矽之總合計量過多，層合性惡化。比較例7，與無機填料比率及滑石比率相同的實施例9、13比較，因未搭配必須成分熱可塑性樹脂，環境試驗前後的剝離強度之密著維持率變低。又，因未搭配苯氧樹脂，黏度變得過低，層合性亦惡化。From the results of Tables 1 and 2, in the examples, the low thermal expansion coefficient, the lamination property, and the adhesion strength after the environmental test were excellent, and the balance of these properties was excellent. On the other hand, in Comparative Examples 1 and 2, since the talc content was small, the decrease in the adhesion strength after the environmental test was remarkable. Further, in Comparative Examples 3 and 4, the content of talc was too large, and the laminate property was deteriorated. Further, in Comparative Example 5, the total content of talc and cerium oxide was small, and the coefficient of thermal expansion was increased. Further, in Comparative Example 6, since the total amount of talc and cerium oxide was too large, the laminate property was deteriorated. In Comparative Example 7, in comparison with Examples 9 and 13 in which the inorganic filler ratio and the talc ratio were the same, the adhesion retention ratio of the peel strength before and after the environmental test was lowered because the thermoplastic resin was not blended with the necessary components. Further, since the viscosity is too low due to the absence of the phenoxy resin, the laminate property is also deteriorated.

[產業利用性][Industry Utilization]

本發明的樹脂組成物，可提供導體層與絕緣層之密著良好且環境試驗後的密著降低少的接著薄膜、預浸漬體、多層印刷配線板。進而亦可提供搭配此等之電腦、行動電話、數位相機、電視等電器製品或機車、汽車、電車、船舶、飛機等交通工具。The resin composition of the present invention can provide a film, a prepreg, and a multilayer printed wiring board which are excellent in adhesion between the conductor layer and the insulating layer and have little adhesion reduction after the environmental test. In addition, it can also be provided with such computers, mobile phones, digital cameras, televisions and other electrical products or vehicles, cars, trams, ships, aircraft and other means of transportation.

Claims (11)

一種樹脂組成物，其係含有(A)氰酸酯樹脂、(B)環氧樹脂、(C)熱可塑性樹脂、(D)滑石及(E)二氧化矽之印刷配線板用樹脂組成物，其特徵為當樹脂組成物中不揮發分為100質量%時，(1)成分(D)滑石與成分(E)二氧化矽之含量合計為35質量%~60質量%，且(2)成分(D)滑石之含量為5質量%~20質量%。 A resin composition comprising a resin composition for a printed wiring board of (A) a cyanate resin, (B) an epoxy resin, (C) a thermoplastic resin, (D) talc, and (E) cerium oxide, It is characterized in that when the non-volatile content of the resin composition is 100% by mass, the total content of the component (D) talc and the component (E) ceria is from 35 to 60% by mass, and the component (2) (D) The content of talc is 5 mass% to 20 mass%. 一種樹脂組成物，其係含有(A)氰酸酯樹脂、(B)環氧樹脂、(C)熱可塑性樹脂、(D)滑石及(E)二氧化矽之印刷配線板用樹脂組成物，其特徵為當樹脂組成物中不揮發分為100質量%時，(1)成分(D)滑石與成分(E)二氧化矽之含量合計為45質量%~60質量%，且(2)成分(D)滑石之含量為5質量%~20質量%。 A resin composition comprising a resin composition for a printed wiring board of (A) a cyanate resin, (B) an epoxy resin, (C) a thermoplastic resin, (D) talc, and (E) cerium oxide, When the non-volatile content of the resin composition is 100% by mass, the total content of the component (D) talc and the component (E) cerium oxide is 45% by mass to 60% by mass, and the component (2) (D) The content of talc is 5 mass% to 20 mass%. 如請求項1或2之樹脂組成物，其中，成分(D)滑石的平均粒徑為1.3μm以下。 The resin composition of claim 1 or 2, wherein the component (D) talc has an average particle diameter of 1.3 μm or less. 如請求項1或2之樹脂組成物，其中，成分(C)熱可塑性樹脂為由苯氧樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚碸樹脂、聚醚碸樹脂、聚苯醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂、聚縮醛樹脂、聚縮丁醛樹脂所選出的1種以上高分子樹脂。 The resin composition of claim 1 or 2, wherein the component (C) thermoplastic resin is a phenoxy resin, a polyamidene resin, a polyamidimide resin, a polyether phthalimide resin, a polyfluorene resin One or more polymer resins selected from polyether oxime resins, polyphenylene ether resins, polycarbonate resins, polyether ether ketone resins, polyester resins, polyacetal resins, and polybutyral resins. 如請求項1或2之樹脂組成物，其中，成分(C)熱可塑性樹脂為苯氧樹脂。 The resin composition of claim 1 or 2, wherein the component (C) thermoplastic resin is a phenoxy resin. 如請求項1或2之樹脂組成物，其中，成分(D)滑石及成分(E)二氧化矽預先經表面處理。 The resin composition of claim 1 or 2, wherein the component (D) talc and the component (E) ceria are previously subjected to surface treatment. 如請求項1或2之樹脂組成物，其中，熱膨脹率為44ppm以下，且環境試驗前後的密著維持率為40%以上。 The resin composition of claim 1 or 2, wherein the thermal expansion coefficient is 44 ppm or less, and the adhesion retention ratio before and after the environmental test is 40% or more. 如請求項1或2之樹脂組成物，其為多層印刷配線板之層間絕緣用。 The resin composition of claim 1 or 2 which is used for interlayer insulation of a multilayer printed wiring board. 一種接著薄膜，其特徵係請求項1~8中任1項之樹脂組成物在支持薄膜上層形成而成。 An adhesive film characterized in that the resin composition of any one of claims 1 to 8 is formed on the upper layer of the support film. 一種預浸漬體，其特徵係請求項1~8中任1項之樹脂組成物係含浸在由纖維構成的薄片狀補強基材中而成。 A prepreg characterized in that the resin composition of any one of claims 1 to 8 is impregnated into a sheet-like reinforcing substrate composed of fibers. 一種印刷配線板，其特徵係具備含有請求項1~8中任1項之樹脂組成物的硬化物之絕緣層與於該絕緣層上形成之導體層。 A printed wiring board comprising: an insulating layer containing a cured product of the resin composition of any one of claims 1 to 8; and a conductor layer formed on the insulating layer.