TW201331254A - Resin composition - Google Patents
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本發明係關於樹脂組成物。進而係關於含有該樹脂組成物、黏著薄膜、預浸料、多層印刷電路板、半導體裝置。 The present invention relates to a resin composition. Further, the resin composition, the adhesive film, the prepreg, the multilayer printed wiring board, and the semiconductor device are contained.
近年來於電子機器小型化、高性能化進展、多層印刷電路板，追求堆積層(Build up layer)之複層化、接線之微細化及高密度化。 In recent years, in the development of miniaturization and high performance of electronic equipment, multi-layer printed circuit boards have been demanded for stratification of a build-up layer, miniaturization of wiring, and high density.
對於此已做出各式各樣之組合。例如，於專利文獻1，已揭示含有聚矽氧烷氧基寡聚物之樹脂組成物。記載由此等之組成物所形成之絕緣材料，具備黏著性。又，於專利文獻2~4亦研究一般之摻合。然而，該性能亦非絕對滿足者。 A variety of combinations have been made for this. For example, Patent Document 1 discloses a resin composition containing a polyoxyalkyloxy oligomer. An insulating material formed of such a composition is described and has adhesiveness. Further, general blending is also studied in Patent Documents 2 to 4. However, this performance is not absolutely satisfactory.
[專利文獻1]日本特開2006-117826號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-117826
[專利文獻2]日本特許第4674730號 [Patent Document 2] Japanese Patent No. 4674730
[專利文獻3]日本特許第4686750號 [Patent Document 3] Japanese Patent No. 4686750
[專利文獻4]日本特許第4782870號 [Patent Document 4] Japanese Patent No. 4782870
本發明所欲解決之課題係提供一種於濕式粗糙化步驟減少絕緣層表面之算術平均粗糙度、均方根粗糙度，可於其上形成具有充分剝離強度之鍍敷導體層，亦具有PCT(Pressure Cooker Test)耐性之樹脂組成物。 The problem to be solved by the present invention is to provide a method for reducing the arithmetic mean roughness and root mean square roughness of a surface of an insulating layer in a wet roughening step, and forming a plated conductor layer having sufficient peeling strength thereon, and having a PCT (Pressure Cooker Test) Resistible resin composition.
本發明者們，上述應解決課題經努力研究後之結果，於(A)環氧樹脂、(B)硬化劑、(C)含無機充填材之樹脂組成物，於前述無機充填材，其特徵為以特定有機化合物表面處理之樹脂組成物，而完成本發明。 The inventors of the present invention have made an effort to study the results of the above-mentioned inorganic fillers in (A) epoxy resin, (B) hardener, and (C) inorganic filler-containing resin composition. The present invention has been completed for a resin composition surface-treated with a specific organic compound.
亦即，本發明係含有以下內容者。 That is, the present invention contains the following.
[1]一種樹脂組成物，其特徵為於(A)環氧樹脂、(B)硬化劑、(C)含無機充填材之樹脂組成物，前述無機充填材以具有氫氧基及反應性基且沸點為100℃以上之有機化合物經表面處理。 [1] A resin composition characterized by (A) an epoxy resin, (B) a curing agent, and (C) a resin composition containing an inorganic filler, wherein the inorganic filler has a hydroxyl group and a reactive group. The organic compound having a boiling point of 100 ° C or more is subjected to surface treatment.
[2]如[1]之樹脂組成物，其中前述有機化合物之反應性基係由胺基、環氧基、巰基、甲基丙烯酸基、丙烯酸基、乙烯基及脲基所成之群選出1種以上。 [2] The resin composition according to [1], wherein the reactive group of the above organic compound is selected from the group consisting of an amine group, an epoxy group, a decyl group, a methacryl group, an acryl group, a vinyl group, and a urea group. More than one species.
[3]如[1]之樹脂組成物，其中前述有機化合物係由下式(1)之化合物、下式(2)之化合物、下式(3)之化合物、咪唑化合物及咪唑-環氧加成物所成之群選出1種以上。
[4]如上述[1]~[3]任一項之樹脂組成物，其中將(C)無機充填材作為100質量%，前述有機化合物為0.05~2質量%。 [4] The resin composition according to any one of the above [1] to [3] wherein (C) the inorganic filler is 100% by mass, and the organic compound is 0.05 to 2% by mass.
[5]如上述[1]~[4]任一項之樹脂組成物，其中於(C)無機充填材經前述有機化合物表面處理之後，進而由矽烷偶合劑、烷氧基矽烷、烷氧基寡聚物、鋁系偶合劑、鈦系偶合劑及鋯系偶合劑所構成之群選出1種以上。 [5] The resin composition according to any one of the above [1] to [4] wherein (C) the inorganic filler is surface-treated with the organic compound, and further, a decane coupling agent, an alkoxy decane, or an alkoxy group. One or more groups selected from the group consisting of an oligomer, an aluminum coupling agent, a titanium coupling agent, and a zirconium coupling agent are selected.
[6]如上述[1]~[5]任一項之之樹脂組成物，其中鍵結於(C)無機充填材表面上的每單位面積碳量為0.05~1.00mg/m2。 [6] The resin composition according to any one of [1] to [5] above, wherein the amount of carbon per unit area bonded to the surface of the (C) inorganic filler is 0.05 to 1.00 mg/m 2 .
[7]如上述[1]~[6]任一項之樹脂組成物，其中將樹脂組成物經硬化形成絕緣層，粗糙化處理該絕緣層表面，經鍍敷所得到之導體層與絕緣層之剝離強度為0.4kgf/cm~1.5kgf/cm，將樹脂組成物經硬化形成絕緣層，將該絕緣層表面經粗糙化處理後之算術平均粗糙度為10nm~300nm，均方根粗糙度為10nm~480nm。 [7] The resin composition according to any one of [1] to [6] wherein the resin composition is hardened to form an insulating layer, the surface of the insulating layer is roughened, and the conductor layer and the insulating layer obtained by plating are obtained. The peeling strength is 0.4kgf/cm~1.5kgf/cm, and the resin composition is hardened to form an insulating layer. The arithmetic mean roughness of the surface of the insulating layer after roughening is 10 nm to 300 nm, and the root mean square roughness is 10nm~480nm.
[8]一種薄片狀層合材料，其特徵為含有如上述[1]~[7]任一項所記載之樹脂組成物。 [8] A sheet-like laminate comprising the resin composition according to any one of [1] to [7] above.
[9]一種多層印刷電路板，其係由如上述[1]~[7]任一項所記載之樹脂組成物的硬化物經形成絕緣層者。 [9] A multilayer printed wiring board obtained by forming a cured layer of a cured product of the resin composition according to any one of the above [1] to [7].
[10]一種半導體裝置，其特徵為使用如上述[9]所記載之多層印刷電路板。 [10] A semiconductor device characterized by using the multilayer printed wiring board according to [9] above.
成為提供一種其特徵為於(A)環氧樹脂、(B)硬化劑、(C)含無機充填材，且前述無機充填材係以特定之有機化合物表面處理之樹脂組成物，於濕式粗糙化步驟減少絕緣層表面之算術平均粗糙度、均方根粗糙度，可於其上形成具有充分剝離強度之鍍敷導體層，亦具有PCT耐性之樹脂組成物。 Provided to provide a resin composition characterized by (A) epoxy resin, (B) hardener, (C) inorganic filler, and the above inorganic filler is surface-treated with a specific organic compound, in a wet rough The step of reducing the arithmetic mean roughness and the root mean square roughness of the surface of the insulating layer can form a plated conductor layer having sufficient peel strength thereon, and a resin composition having PCT resistance.
本發明，係一種樹脂組成物，其特徵為於(A)環氧樹脂、(B)硬化劑、(C)含無機充填材之樹脂組成物， 前述無機充填材以具有氫氧基及反應性基且沸點為100℃以上之有機化合物經表面處理。 The present invention is a resin composition characterized by (A) an epoxy resin, (B) a hardener, and (C) a resin composition containing an inorganic filler. The inorganic filler is surface-treated with an organic compound having a hydroxyl group and a reactive group and having a boiling point of 100 ° C or higher.
作為使用於本發明之環氧樹脂，並未有特別限制，可列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AF型環氧樹脂、酚系酚醛清漆型環氧樹脂、第三丁基-鄰苯二酚型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、伸萘基醚型環氧樹脂、縮水甘油胺型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯基型環氧樹脂、蒽型環氧樹脂、線狀脂肪族環氧樹脂、具有丁二烯構造之環氧樹脂、脂環式環氧樹脂、雜環式環氧樹脂、含有螺環(Spiro ring)之環氧樹脂、環己烷二甲醇型環氧樹脂、三羥甲基型環氧樹脂、鹵化環氧樹脂等。此等可1種或2種以上組合使用。 The epoxy resin used in the present invention is not particularly limited, and examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, and a bisphenol AF type epoxy resin. Phenolic novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthyl ether type epoxy resin, glycidylamine type ring Oxygen resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin A heterocyclic epoxy resin, an epoxy resin containing a spiro ring, a cyclohexanedimethanol type epoxy resin, a trimethylol type epoxy resin, a halogenated epoxy resin, or the like. These may be used alone or in combination of two or more.
此等之中，從耐熱性提高、絕緣信賴性提高、與金屬箔之附著力提高的觀點來看，以具有雙酚A型環氧樹脂、萘酚型環氧樹脂、萘型環氧樹脂、聯苯基型環氧樹脂、伸萘基醚型環氧樹脂、蒽型環氧樹脂、具有丁二烯構造之環氧樹脂為佳。具體而言，例如可列舉雙酚A型環氧樹脂(三菱化學(股)製「Epikote828EL」、「YL980」)、雙酚F型環氧樹脂(三菱化學(股)製「jER806H」、「YL983U」)、萘型2官能環氧樹脂(DIC(股)製「HP4032」、「HP4032D」、「HP4032 SS」、「EXA4032SS 」)、萘型4官能環氧樹脂(DIC(股)製「HP4700」、「HP4710」)、萘酚型環氧樹脂(東都化成(股)製「ESN-475V」)、具有丁二烯構造之環氧樹脂(Daicel化學工業(股)製「PB-3600」)、具有聯苯基構造之環氧樹脂(日本化藥(股)製「NC 3000H」、「NC 3000L」、「NC 3100」、三菱化學(股)製「YX 4000」、「YX 4000H」、「YX 4000HK」、「YL6121」)、蒽型環氧樹脂(三菱化學(股)製「YX8800」)、伸萘基醚型環氧樹脂(DIC(股)製「EXA-7310」、「EXA-7311」、「EXA-7311L」、「EXA7311-G3」)等。 Among these, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, and the like, from the viewpoint of improvement in heat resistance, improvement in insulation reliability, and adhesion to a metal foil, A biphenyl type epoxy resin, a naphthyl ether type epoxy resin, a fluorene type epoxy resin, and an epoxy resin having a butadiene structure are preferred. Specific examples include bisphenol A type epoxy resin ("Epikote 828EL" and "YL980" manufactured by Mitsubishi Chemical Co., Ltd.), and bisphenol F type epoxy resin ("JER806H" and "YL983U" manufactured by Mitsubishi Chemical Corporation). ") Naphthalene type 2-functional epoxy resin (HP4032", "HP4032D", "HP4032 SS", "EXA4032SS" manufactured by DIC Corporation "), a naphthalene type 4-functional epoxy resin ("HP4700" manufactured by DIC Co., Ltd., "HP4710"), a naphthol type epoxy resin ("ESN-475V" manufactured by Tohto Kasei Co., Ltd.), and a butadiene structure. Epoxy resin ("PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), epoxy resin with biphenyl structure ("NC 3000H", "NC 3000L", "NC 3100" manufactured by Nippon Kayaku Co., Ltd. "YX 4000", "YX 4000H", "YX 4000HK" and "YL6121" manufactured by Mitsubishi Chemical Corporation, "YX8800" manufactured by Mitsubishi Chemical Corporation, and Naphthyl ether ring Oxygen resin (EXA-7310, EXA-7311, EXA-7311L, EXA7311-G3) made by DIC.
環氧樹脂亦可併用2種以上，以含有於1分子中具有2個以上環氧基之環氧樹脂為佳。其中，以含有於1分子中具有2個以上環氧基，於溫度20℃下為液狀之芳香族系環氧樹脂(以下，稱為「液狀環氧樹脂」)、與於1分子中具有3個以上環氧基，於溫度20℃下為固體狀之芳香族系環氧樹脂(以下，稱為「固體狀環氧樹脂」)之態樣為更佳。尚且，於本發明所謂芳香族系環氧樹脂，係意味著於其分子內具有芳香環構造之環氧樹脂。作為環氧樹脂，併用液狀環氧樹脂與固體狀環氧樹脂時，從將樹脂組成物以黏著薄膜形態使用時具有適度可撓性這點或樹脂組成物之硬化物具有適度斷裂強度這點來看，其摻合比例(液狀環氧樹脂：固體狀環氧樹脂)以質量比於1：0.1~1：2之範圍為佳，以1：0.3~1：1.8之範圍為更佳，以1：0.6~1：1.5之範圍為特佳。 The epoxy resin may be used in combination of two or more kinds, and it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule. In particular, the aromatic epoxy resin (hereinafter referred to as "liquid epoxy resin") having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C is contained in one molecule. It is more preferable that the aromatic epoxy resin (hereinafter referred to as "solid epoxy resin") having three or more epoxy groups in a solid state at a temperature of 20 ° C is used. Further, the term "aromatic epoxy resin" as used in the present invention means an epoxy resin having an aromatic ring structure in its molecule. When a liquid epoxy resin or a solid epoxy resin is used as the epoxy resin, the resin composition has moderate flexibility when used as an adhesive film or the cured product of the resin composition has moderate breaking strength. In view of the blending ratio (liquid epoxy resin: solid epoxy resin), the mass ratio is preferably in the range of 1:0.1 to 1:2, and preferably in the range of 1:0.3 to 1:1.8. It is particularly good in the range of 1:0.6~1:1.5.
作為液狀環氧樹脂，以雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚系酚醛清漆型環氧樹脂、或萘型環氧樹脂為佳，以萘型環氧樹脂為更佳。此等可1種或組合2種以上使用。 As the liquid epoxy resin, a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, or a naphthalene epoxy resin is preferable, and a naphthalene epoxy resin is more preferable. good. These may be used alone or in combination of two or more.
作為固體狀環氧樹脂，以4官能萘型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙環戊二烯型環氧樹脂、三酚環氧樹脂、萘酚酚醛清漆環氧樹脂、聯苯基型環氧樹脂、或伸萘基醚型環氧樹脂為佳，以4官能萘型環氧樹脂、聯苯基型環氧樹脂、或伸萘基醚型環氧樹脂為更佳。此等可1種或組合2種以上使用。 As a solid epoxy resin, a tetrafunctional naphthalene epoxy resin, a cresol novolac epoxy resin, a dicyclopentadiene epoxy resin, a trisphenol epoxy resin, a naphthol novolac epoxy resin, a biphenyl A base type epoxy resin or a stretch naphthyl ether type epoxy resin is preferred, and a 4-functional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a stretch naphthyl ether type epoxy resin is more preferable. These may be used alone or in combination of two or more.
於本發明之樹脂組成物，從提昇樹脂組成物之硬化物的機械強度或耐水性觀點來看，將樹脂組成物中之非揮發成分作為100質量%時，環氧樹脂之含量以3~40質量%為佳，以5~35質量%為更佳，以10~30質量%為特佳。 In the resin composition of the present invention, from the viewpoint of mechanical strength or water resistance of the cured product of the resin composition, when the nonvolatile component in the resin composition is 100% by mass, the content of the epoxy resin is 3 to 40. The mass % is preferably, preferably 5 to 35% by mass, and particularly preferably 10 to 30% by mass.
作為使用於本發明之硬化劑，並未有特別限制，可列舉酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑、苯并惡嗪(Benzoxazine)系硬化劑、氰酸酯系硬化劑、酸酐系硬化劑等，其中以酚系硬化劑、萘酚系硬化劑、活性酯系硬化劑為佳。此等可1種或組合2種以上使用。 The curing agent to be used in the present invention is not particularly limited, and examples thereof include a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, and a cyanate-based curing agent. A phenolic curing agent, a naphthol-based curing agent, and an active ester-based curing agent are preferred as the agent, the acid anhydride-based curing agent, and the like. These may be used alone or in combination of two or more.
作為酚系硬化劑、萘酚系硬化劑，並未有特別限制，可列舉具有酚醛清漆構造之酚系硬化劑或具有酚醛清漆構造之萘酚系硬化劑，以酚系酚醛清漆樹脂、含有三嗪骨架 之酚系酚醛清漆樹脂、萘酚酚醛清漆樹脂、萘酚芳烷基型樹脂、含有三嗪骨架之萘酚樹脂、聯苯基芳烷基型酚樹脂為佳。作為市售品，作為聯苯基芳烷基型酚樹脂，可列舉「MEH-7700」、「MEH-7810」、「MEH-7851」、「MEH7851-4H」(明和化成(股)製)、「GPH」(日本化藥(股)製)，作為萘酚酚醛清漆樹脂，可列舉「NHN」、「CBN」(日本化藥(股)製)，作為萘酚芳烷基型樹脂，可列舉「SN170」、「SN180」、「SN190」、「SN475」、「SN485」、「SN495」、「SN395」、「SN375」(東都化成(股)製)，作為酚系酚醛清漆樹脂，可列舉「TD2090」(DIC(股)製)、含有三嗪骨架之酚系酚醛清漆樹脂「LA3018」、「LA7052」、「LA7054」、「LA1356」(DIC(股)製)等。此等可併用1種或2種以上。 The phenolic curing agent and the naphthol-based curing agent are not particularly limited, and examples thereof include a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure, and a phenol-based novolak resin containing three. Azine skeleton The phenolic novolak resin, the naphthol novolak resin, the naphthol aralkyl type resin, the naphthol resin containing a triazine skeleton, and the biphenyl aralkyl type phenol resin are preferred. As a commercially available product, examples of the biphenyl aralkyl type phenol resin include "MEH-7700", "MEH-7810", "MEH-7851", and "MEH7851-4H" (made by Megumi Kasei Co., Ltd.). "GPH" (manufactured by Nippon Kayaku Co., Ltd.), as a naphthol novolak resin, "NHN" or "CBN" (manufactured by Nippon Kayaku Co., Ltd.), and examples of the naphthol aralkyl type resin include "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN395", "SN375" (made by Toki Kasei Co., Ltd.), as a phenolic novolak resin, " TD2090" (made by DIC), phenolic novolac resin "LA3018", "LA7052", "LA7054", "LA1356" (made by DIC), etc. containing a triazine skeleton. These may be used alone or in combination of two or more.
作為活性酯系硬化劑，並未有特別限制，一般以使用酚酯類、硫酚酯類、N-羥基胺酯類、雜環羥基化合物之酯類等之於1分子中具有2個以上反應活性高的酯基之化合物為佳。該活性酯系硬化劑，係以藉由羧酸化合物及/或硫代羧酸化合物與羥基化合物及/或硫醇化合物之縮合反應而獲得者為佳。尤其是從提高耐熱性之觀點來看，以從羧酸化合物與羥基化合物所得到之活性酯系硬化劑為佳，以從羧酸化合物與酚化合物及/或萘酚化合物所得到之活性酯系硬化劑為更佳。作為羧酸化合物，例如可列舉安息香酸、乙酸、琥珀酸、馬來酸、衣康酸、苯二甲酸、異苯 二甲酸、對苯二甲酸、苯均四酸等。作為酚化合物或萘酚化合物，例如可列舉對苯二酚、間苯二酚、雙酚A、雙酚F、雙酚S、酚酞、甲基化雙酚A、甲基化雙酚F、甲基化雙酚S、酚、o-甲酚、m-甲酚、p-甲酚、鄰苯二酚、α-萘酚、β-萘酚、1,5-二羥基萘、1,6-二羥基萘、2,6-二羥基萘、二羥基二苯甲酮、三羥基二苯甲酮、四羥基二苯甲酮、間苯三酚(Phloroglucin)、苯三醇、二環戊二烯二酚、酚系酚醛清漆等。活性酯系硬化劑可1種或2種以上使用。作為活性酯系硬化劑，可使用日本特開2004-277460號公報已揭示之活性酯系硬化劑，又亦可使用市售。作為市售之活性酯系硬化劑，以含有二環戊二烯二酚構造者、酚系酚醛清漆之乙醯化物、酚系酚醛清漆之苄醯基化物等為佳，其中以含有二環戊二烯二酚構造者為更佳。具體而言，作為含有二環戊二烯二酚構造者可列舉EXB 9451、EXB 9460、EXB 9460S-65T、HPC-8000-65T(DIC(股)製，活性基當量約223)，作為酚系酚醛清漆之乙醯化物可列舉DC808(三菱化學(股)製、活性基當量約149)，作為酚系酚醛清漆之苄醯基化物可列舉YLH1026(三菱化學(股)製、活性基當量約200)、YLH1030(三菱化學(股)製，活性基當量約201)、YLH1048(三菱化學(股)製、活性基當量約245)等，其中以HPC-8000-65T從清漆之保存安定性、硬化物之熱膨脹率觀點來看為佳。 The active ester-based curing agent is not particularly limited, and generally has two or more reactions in one molecule using phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. A compound having a high activity of an ester group is preferred. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester system obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is preferred. A hardener is preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, and isophthalic acid. Dicarboxylic acid, terephthalic acid, pyromellitic acid, and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and A. Bisphenol bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene Diphenol, phenolic novolac, etc. The active ester-based curing agent may be used alone or in combination of two or more. As the active ester-based curing agent, an active ester-based curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used. As a commercially available active ester-based curing agent, a dicyclopentadiene diol structure, a phenolic novolac acetonide, a phenolic novolac benzyl hydrazide, or the like is preferable, and a dicyclopentan group is contained. The diene diphenol builder is better. Specifically, examples of the structure containing dicyclopentadiene diphenol include EXB 9451, EXB 9460, EXB 9460S-65T, and HPC-8000-65T (manufactured by DIC, having an active base equivalent of about 223) as a phenol system. The acetal phenol varnish is exemplified by DC 808 (manufactured by Mitsubishi Chemical Corporation, active base equivalent of about 149), and the benzyl sulfonate of the phenolic novolak can be exemplified by YLH1026 (manufactured by Mitsubishi Chemical Corporation) and having an active base equivalent of about 200. ), YLH1030 (Mitsubishi Chemical Co., Ltd., active base equivalent of about 201), YLH1048 (Mitsubishi Chemical Co., Ltd., active base equivalent of about 245), etc., in which HPC-8000-65T is preserved from the varnish for stability and hardening. The thermal expansion rate of the material is preferred.
作為含有二環戊二烯二酚構造之活性酯系硬化劑，更具體可列舉下式(4)之化合物。 The active ester-based curing agent having a structure of a dicyclopentadiene diphenol is more specifically a compound of the following formula (4).
從所謂使介電正切降低、提高耐熱性之觀點來看，R為萘基較佳，另一方面，k為0較佳、又，n為0.25~1.5較佳。 From the viewpoint of lowering the dielectric tangent and improving the heat resistance, R is preferably a naphthyl group. On the other hand, k is preferably 0, and n is preferably 0.25 to 1.5.
作為苯并惡嗪系硬化劑，並未有特別限制，作為具體例，可列舉F-a、P-d(四國化成(股)製)、HFB2006M(昭和高分子(股)製)等。 The benzoxazine-based curing agent is not particularly limited, and specific examples thereof include F-a, P-d (manufactured by Shikoku Chemical Co., Ltd.), and HFB2006M (manufactured by Showa Polymer Co., Ltd.).
作為氰酸酯系硬化劑，並未特別限制，可列舉酚醛清漆型(酚系酚醛清漆型、烷酚系酚醛清漆型等)氰酸酯系硬化劑、雙環戊二烯型氰酸酯系硬化劑、雙酚型(雙酚A型、雙酚F型、雙酚S型等)氰酸酯系硬化劑、及此等一部份經三嗪化之預聚物等。氰酸酯系硬化劑之重量平均分子量，並未有特別限定，以500~4500為佳，以600~3000為更佳。作為氰酸酯系硬化劑之具體例，例如可列舉雙酚A二氰酸酯、聚酚氰酸酯(寡(3-亞甲基-1,5-伸苯基氰酸酯)、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)醚等之2官能氰酸酯樹脂、酚系酚 醛清漆、甲酚酚醛清漆、從含有雙環戊二烯構造之酚樹脂等所衍生之多官能氰酸酯樹脂、此等氰酸酯樹脂一部份經三嗪化之預聚物等。此等可1種或組合2種以上使用。作為市售之氰酸酯樹脂，可列舉下式(5)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(6)所表示之雙酚A二氰酸酯之一部份或全部變成經三嗪化之三聚物的預聚物(Lonza Japan(股)製，BA230、氰酸酯當量232)、下式(7)所表示之含有雙環戊二烯構造之氰酸酯樹脂(Lonza Japan(股)製、DT-4000、DT-7000)等。 The cyanate-based curing agent is not particularly limited, and examples thereof include a novolac type (phenol novolak type, an alkylphenol type novolak type, etc.) cyanate type curing agent and a dicyclopentadiene type cyanate type curing. A cyanate-based curing agent, a bisphenol type (bisphenol A type, a bisphenol F type, a bisphenol S type, etc.), and a part of the triazine-based prepolymer. The weight average molecular weight of the cyanate-based curing agent is not particularly limited, and is preferably 500 to 4,500, more preferably 600 to 3,000. Specific examples of the cyanate-based curing agent include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methylene-1,5-phenylene), 4). 4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) ether 2-functional cyanate resin, phenolic phenol An aldehyde varnish, a cresol novolak, a polyfunctional cyanate resin derived from a phenol resin containing a dicyclopentadiene structure, a prepolymer which is partially triazineated with such a cyanate resin, and the like. These may be used alone or in combination of two or more. The commercially available cyanate resin may be a phenolic novolak type polyfunctional cyanate resin represented by the following formula (5) (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and the following formula ( 6) A part or all of the bisphenol A dicyanate represented as a prepolymer of a triazineated terpolymer (manufactured by Lonza Japan Co., Ltd., BA230, cyanate equivalent 232), (7) A cyanate resin (manufactured by Lonza Japan Co., Ltd., DT-4000, DT-7000) containing a dicyclopentadiene structure.
作為酸酐系硬化劑，並未有特別限定，可列舉鄰苯二甲酸酐、四氫苯二甲酸酐、六氫苯二甲酸酐、甲基四氫苯二甲酸酐、甲基六氫苯二甲酸酐、甲基納迪克酸(Methyl Nadic acid)酸酐、氫化甲基納迪克酸酸酐、三烷基四氫苯二甲酸酐、十二烯基琥珀酸酐、5-(2,5-二側氧基四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、苯偏三酸酐、苯均四酸酐、二苯甲酮四羧酸二酐、二苯基四羧酸二酐、萘四羧酸二酐、氧基二苯二甲酸二酐、3,3’-4,4’-二苯基碸四羧酸二酐、1,3,3a,4,5,9b-六氫-5-(四氫-2,5-二側氧基-3-呋喃基)-萘基[1,2-C]呋喃-1,3-二酮、乙二醇雙(苯偏三酸酐)、苯乙烯與馬來酸經共聚合之苯乙烯‧馬來酸樹脂等之聚合物型的酸酐等。 The acid anhydride-based curing agent is not particularly limited, and examples thereof include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalate. Anhydride, Methyl Nadic acid anhydride, hydrogenated methyl nadic acid anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-di-oxyl) Tetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, diphenyl Tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,3,3a,4 ,5,9b-hexahydro-5-(tetrahydro-2,5-di-oxy-3-furanyl)-naphthyl[1,2-c]furan-1,3-dione, ethylene glycol A polymer type acid anhydride such as styrene/maleic acid resin obtained by copolymerization of bis(benzene trimellitic anhydride), styrene and maleic acid.
於本發明之樹脂組成物，從所謂提高樹脂組成物硬化物之機械強度或耐水性之觀點來看，(A)環氧樹脂環氧基之合計數目與(B)硬化劑反應基之合計數目的比以1：0.2~1：2為佳，以1：0.3~1：1.5為更佳，以1：0.4~1：1為特佳。尚且所謂存在於樹脂組成物中之環氧樹脂環氧基的合計數目，係將各環氧樹脂之固體含量質量除以環氧基當量之值對全部環氧樹脂合計之值，所謂硬化劑反應基之合計數目，係將各硬化劑之固體含量質量除以反應基當量之值對全部硬化劑經合計之值。 In the resin composition of the present invention, from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition, (A) the total number of epoxy groups of epoxy resins and (B) the total number of reactive groups of hardeners The ratio is preferably 1:0.2~1:2, preferably 1:0.3~1:1.5, and 1:0.4~1:1. The total number of epoxy groups of epoxy resins present in the resin composition is the value of the solid content of each epoxy resin divided by the value of the epoxy equivalent to the total value of all the epoxy resins, the so-called hardener reaction. The total number of bases is a value obtained by dividing the solid content of each hardener by the value of the reactive base equivalent to the total of all the hardeners.
於本發明之樹脂組成物，從提高所謂樹脂組成物之硬化物的機械強度或耐水性之觀點來看，將樹脂組成物中之非揮發成分作為100質量%時，硬化劑含量以3~30質量 %為佳，以5~25質量%為更佳，以7~20質量%為特佳。 In the resin composition of the present invention, when the non-volatile component in the resin composition is 100% by mass, the hardener content is 3 to 30, from the viewpoint of improving the mechanical strength or water resistance of the cured product of the resin composition. quality % is better, preferably 5 to 25% by mass, and 7 to 20% by mass.
作為使用於本發明之(C)無機充填材，並未有特別限制，例如可列舉二氧化矽、氧化鋁、硫酸鋇、滑石、黏土、雲母粉、氫氧化鋁、氫氧化鎂、碳酸鈣、碳酸鎂、氧化鎂、氮化硼、硼酸鋁、鈦酸鋇、鈦酸鍶、鈦酸鈣、鈦酸鎂、鈦酸鉍、氧化鈦、鋯酸鋇、鋯酸鈣等。其中以二氧化矽為佳。又，以無定形二氧化矽、粉碎二氧化矽、熔融二氧化矽、結晶二氧化矽、合成二氧化矽、中空二氧化矽等之二氧化矽為佳，熔融二氧化矽為更佳。又，作為二氧化矽以球狀者為佳。此等可1種或組合2種以上使用。作為市售之球狀熔融二氧化矽，可列舉(股)Admatechs製「SOC2」、「SOC1」。 The (C) inorganic filler used in the present invention is not particularly limited, and examples thereof include cerium oxide, aluminum oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, and calcium carbonate. Magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, barium titanate, calcium titanate, magnesium titanate, barium titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. Among them, cerium oxide is preferred. Further, it is preferable to use cerium oxide such as amorphous cerium oxide, pulverized cerium oxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide or hollow cerium oxide, and molten cerium oxide is more preferable. Further, it is preferable that the cerium oxide is spherical. These may be used alone or in combination of two or more. As a commercially available spherical molten cerium oxide, "SOC2" and "SOC1" manufactured by Admatechs can be cited.
無機充填材之平均粒徑，並未特別限定，從對絕緣層上進行微細接線形成之觀點來看，以5μm以下為佳，以3μm以下為更佳，以1μm以下又為更佳，0.7μm以下為更進一步更佳，0.5μm以下又再更佳，以0.4μm以下為特佳，以0.3μm以下為特別佳。另一方面，將環氧樹脂組成物作為樹脂清漆時，從所謂防止清漆之黏度上升、操作性降低之觀點來看，無機充填材之平均粒徑，以0.01μm以上為佳，以0.03μm以上為更佳，以0.05μm以上又為更佳，以0.07μm以上為更進一步更佳，以0.1μm以上為特佳。上述無機充填材之平均粒徑係基於米氏 (Mie)散射理論可由雷射衍射‧散射法測定。具體而言係由雷射衍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作成，可將其中位徑以平均粒徑測定。測定試料，可使用以將無機充填材由超音波分散於水中者為佳。作為雷射衍射式粒度分布測定裝置，可使用(股)堀場製作所製LA-500、750、950等。 The average particle diameter of the inorganic filler is not particularly limited. From the viewpoint of forming fine wiring on the insulating layer, it is preferably 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less, 0.7 μm. The following is further more preferable, and further preferably 0.5 μm or less, particularly preferably 0.4 μm or less, and particularly preferably 0.3 μm or less. On the other hand, when the epoxy resin composition is used as the resin varnish, the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and 0.03 μm or more, from the viewpoint of preventing the viscosity of the varnish from increasing and the workability being lowered. More preferably, it is more preferably 0.05 μm or more, still more preferably 0.07 μm or more, and particularly preferably 0.1 μm or more. The average particle size of the above inorganic filler is based on Mie The (Mie) scattering theory can be determined by the laser diffraction ‧ scattering method. Specifically, the laser diffraction type particle size distribution measuring apparatus is used to prepare the particle size distribution of the inorganic filler on a volume basis, and the median diameter can be measured as an average particle diameter. The sample to be measured may be used to disperse the inorganic filler in the water by ultrasonic waves. As the laser diffraction type particle size distribution measuring apparatus, LA-500, 750, 950, etc., manufactured by Horiba, Ltd., can be used.
摻合無機充填材時之含量，將樹脂組成物中之非揮發成分作為100質量%時，從使所謂硬化物之熱膨脹率降低之觀點來看，以20質量%以上為佳，以30質量%以上為更佳，以40質量%以上為進一步更佳，以50質量%以上為更上一層更佳。又，從提昇所謂硬化物之機械特性之觀點來看，以85質量%以下為佳，以80質量%以下為更佳，以75質量%以下為進一步更佳，70質量%以下為更上一層更佳。 When the amount of the non-volatile component in the resin composition is 100% by mass, the content of the inorganic filler is preferably 20% by mass or more, and 30% by mass, from the viewpoint of lowering the thermal expansion coefficient of the cured product. The above is more preferable, and it is further preferably 40% by mass or more, and more preferably 50% by mass or more. In addition, from the viewpoint of improving the mechanical properties of the cured product, it is preferably 85 mass% or less, more preferably 80 mass% or less, further preferably 75 mass% or less, and 70 mass% or less. Better.
(C)無機充填材，從樹脂清漆分散性之提高、算術平均粗糙度之低減、均方根粗糙度之低減觀點來看，可使用預先以矽氮烷化合物表面處理者。以矽氮烷化合物表面處理之後，藉由以具有氫氧基及反應性基、且沸點為100℃以上之有機化合物經表面處理，提高分散性、提高與導體層之親和性的點變為有利。作為矽氮烷化合物，例如可列舉六甲基二矽氮烷、1,3-二乙烯基-1,1,3,3-四甲基二矽氮烷、八甲基三矽氮烷、六(t-丁基)二矽氮烷、六丁基基二矽氮烷、六辛基二矽氮烷、1,3-二乙基四甲基二矽氮烷、1,3-二-n-辛基四甲基二矽氮烷、1,3-二苯基四甲基二 矽氮烷、1,3-二甲基四苯基二矽氮烷、1,3-二乙基四甲基二矽氮烷、1,1,3,3-四苯基-1,3-二甲基二矽氮烷、1,3-二丙基四甲基二矽氮烷、六甲基環三矽氮烷、六苯基二矽氮烷、二甲基胺基三甲基矽氮烷、三矽氮烷、環三矽氮烷、1,1,3,3,5,5-六甲基環三矽氮烷等，尤其是以六甲基二矽氮烷為佳。此等可1種或組合2種以上使用。作為以六甲基二矽氮烷經表面處理之球狀熔融二氧化矽，可列舉(股)Admatechs製「SC2050-SQ」。 (C) Inorganic filler, from the viewpoint of improvement in dispersibility of resin varnish, reduction in arithmetic mean roughness, and reduction in root mean square roughness, a surface treated with a decazane compound in advance may be used. After surface treatment with a decazane compound, it is advantageous to improve the dispersibility and improve the affinity with the conductor layer by surface treatment with an organic compound having a hydroxyl group and a reactive group and having a boiling point of 100 ° C or higher. . Examples of the decane alkane compound include hexamethyldiazepine, 1,3-divinyl-1,1,3,3-tetramethyldioxane, octamethyltriazane, and six. (t-butyl)dioxane, hexabutyldiazepine, hexaoctyldioxane, 1,3-diethyltetramethyldiazide, 1,3-di-n -octyltetramethyldiazepine, 1,3-diphenyltetramethyl Indole, 1,3-dimethyltetraphenyldiazepine, 1,3-diethyltetramethyldiazepine, 1,1,3,3-tetraphenyl-1,3- Dimethyldioxane, 1,3-dipropyltetramethyldiazepine, hexamethylcyclotriazane, hexaphenyldioxane, dimethylaminotrimethylguanidinium Alkane, triazane, cyclotriazane, 1,1,3,3,5,5-hexamethylcyclotriazane, etc., especially hexamethyldioxane. These may be used alone or in combination of two or more. As a spherical molten cerium oxide which is surface-treated with hexamethyldioxane, "SC2050-SQ" manufactured by Admatechs is exemplified.
使用於本發明、具有氫氧基及反應性基、且沸點為100℃以上之有機化合物，藉由氫氧基與無機充填材共鍵結可變為充分被覆，使反應性基提高樹脂組成物中之分散性。又，藉由沸點為100℃以上，由脫水縮合一邊使所產生的水蒸發，一邊可進行穩定該有機化合物之表面處理。沸點之較佳上限值為500℃，更佳為400℃，特佳為300℃。尚且，在本發明所謂有機化合物之「沸點」，係指於標準氣壓(0.101325MPa)下之沸點。作為該有機化合物，並未有特別限制、該有機化合物之反應性基，以選自由胺基、環氧基、巰基、甲基丙烯酸基、丙烯酸基、乙烯基、脲基之1種以上為佳，以胺基、環氧基為更佳。該有機化合物，以實質上未含有選自由矽、鋁、鈦、鋯構成之群的元素為佳。在此，所謂「實質上未含有」，係指排除含有作為不可避免之不純物的情況，未含有選自由矽、鋁、鈦、鋯所構成之群的元素。然後，作為該有機化合物，以選自由下式(1)之化合物、下式(2)之化合物、下式(3 )之化合物、咪唑化合物及咪唑-環氧加成物之1種以上為更佳。 The organic compound used in the present invention having a hydroxyl group and a reactive group and having a boiling point of 100 ° C or higher can be sufficiently coated by co-bonding a hydroxyl group with an inorganic filler to increase the reactive group. Dispersion in the middle. Further, the surface treatment for stabilizing the organic compound can be carried out by evaporating the water generated by dehydration condensation by a boiling point of 100 ° C or higher. The preferred upper limit of the boiling point is 500 ° C, more preferably 400 ° C, and particularly preferably 300 ° C. Further, the "boiling point" of the so-called organic compound in the present invention means the boiling point at a standard gas pressure (0.101325 MPa). The organic compound is not particularly limited, and a reactive group of the organic compound is preferably one or more selected from the group consisting of an amine group, an epoxy group, a thiol group, a methacryl group, an acryl group, a vinyl group, and a urea group. Preferably, an amine group or an epoxy group is preferred. The organic compound preferably contains no element selected from the group consisting of ruthenium, aluminum, titanium, and zirconium. Here, the term "substantially not contained" means an element which is excluded from the unavoidable impurities and does not contain a group selected from the group consisting of ruthenium, aluminum, titanium, and zirconium. Then, as the organic compound, a compound selected from the following formula (1), a compound of the following formula (2), and the following formula (3) One or more of the compound, the imidazole compound, and the imidazole-epoxy adduct are more preferable.
R1、R2較佳為苯基、苄基或氫原子，R3較佳為碳數1~5之伸烷基，更佳為碳數1~3之伸烷基。 R1 and R2 are preferably a phenyl group, a benzyl group or a hydrogen atom, and R3 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.
R4較佳為碳數1~5之伸烷基，更佳為碳數1~3之伸烷基。 R4 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms.
R5較佳為具有氫氧基及胺基之1價有機基，更佳為下式(8)所表示之1價有機基。R6較佳為氫原子或甲基，更佳為甲基。 R5 is preferably a monovalent organic group having a hydroxyl group and an amine group, and more preferably a monovalent organic group represented by the following formula (8). R6 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
R7、R8各自獨立，較佳為羥甲基或羥乙基，更佳為羥乙基，n較佳為1~3。 R7 and R8 are each independently, preferably a hydroxymethyl group or a hydroxyethyl group, more preferably a hydroxyethyl group, and n is preferably from 1 to 3.
又，亦可使用下式(9)之化合物。 Further, a compound of the following formula (9) can also be used.
更具體而言，以選自由N-苄基胺基乙醇、N-苯胺基乙醇、環氧丙醇、咪唑-環氧加成物、苯並***衍生物、3-苄基胺基-1-丙醇、4-苄基胺基-1-丁醇、5-苄基胺基-1-戊醇、2-甲基胺基乙醇、2-乙基胺基乙醇、2-丙基胺基乙醇、2-異丙基胺基乙醇、2-丁基胺基乙醇、2-((1-甲基丙基)胺基)乙醇、2-(tert-丁基胺基)乙醇、2-戊基胺基乙醇、3-苯胺基丙醇、4-苯基胺基-1-丁醇、5-苯基胺基-1-戊醇及1-(2-羥乙基)咪唑之1種以上為更佳。其中，從處理安全性、賦予與導體層之高附著力、提高保存安定性的觀點來看，以選自由N-苄基胺基乙醇、N-苯胺基乙醇、環氧丙醇、2,2-[{(甲基-1H-苯並***-1-基)甲基}亞胺基]雙乙醇、1-(2-羥乙基)咪唑及咪唑-環氧 加成物之1種以上為特佳。 More specifically, selected from the group consisting of N-benzylaminoethanol, N-anilinoethanol, glycidol, imidazole-epoxy adducts, benzotriazole derivatives, 3-benzylamino-1 -propanol, 4-benzylamino-1-butanol, 5-benzylamino-1-pentanol, 2-methylaminoethanol, 2-ethylaminoethanol, 2-propylamino Ethanol, 2-isopropylaminoethanol, 2-butylaminoethanol, 2-((1-methylpropyl)amino)ethanol, 2-(tert-butylamino)ethanol, 2-pentyl One or more of aminoaminoethanol, 3-anilinopropanol, 4-phenylamino-1-butanol, 5-phenylamino-1-pentanol and 1-(2-hydroxyethyl)imidazole For better. Among them, from the viewpoints of handling safety, imparting high adhesion to the conductor layer, and improving storage stability, it is selected from N-benzylaminoethanol, N-anilinoethanol, glycidol, 2, 2 -[{(methyl-1H-benzotriazol-1-yl)methyl}imino]diethanol, 1-(2-hydroxyethyl)imidazole and imidazole-epoxy One or more kinds of the adducts are particularly preferable.
作為將(C)無機充填材以該有機化合物經表面處理之方法，可列舉將(C)無機充填材投入旋轉混合機，一邊噴霧該有機化合物，一邊將(C)無機充填材攪拌5~30分鐘之方法。 As a method of subjecting the (C) inorganic filler to surface treatment of the organic compound, (C) the inorganic filler is put into a rotary mixer, and the organic filler is sprayed, and (C) the inorganic filler is stirred 5 to 30. The method of minutes.
該有機化合物之含量，從防止熔融黏度上升之觀點來看，將(C)無機充填材作為100質量%時，以2質量%以下為佳，以1.8質量%以下為更佳，以1.6質量%以下為進一步更佳，以1.4質量%以下為更進一層特佳。又，從提高樹脂清漆之分散性、提高無機充填材之被覆率之觀點來看，以0.05質量%以上為佳，以0.1質量%以上為更佳，0.15質量%以上為進一步更佳，0.2質量%以上為更進一層特佳。 When the content of the organic compound is 100% by mass, the content of the organic filler is preferably 2% by mass or less, more preferably 1.8% by mass or less, and more preferably 1.6% by mass. The following is further better, with a quality of 1.4% by mass or less. In addition, from the viewpoint of improving the dispersibility of the resin varnish and increasing the coverage of the inorganic filler, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.15% by mass or more, and 0.2 mass%. More than % is better for the next level.
將(C)無機充填材以該有機化合物經表面處理之後，從提高疏水性、由使與未反應之矽烷醇基反應進一步提高分散性之觀點來看，可以選自由矽烷偶合劑、烷氧基矽烷、烷氧基寡聚物、鋁系偶合劑、鈦系偶合劑、鋯系偶合劑之1種以上進一步表面處理。 After the (C) inorganic filler is surface-treated with the organic compound, it may be selected from a decane coupling agent, an alkoxy group from the viewpoint of improving hydrophobicity and further improving dispersibility by reacting with an unreacted stanol group. One or more types of decane, an alkoxy oligomer, an aluminum coupling agent, a titanium coupling agent, and a zirconium coupling agent are further subjected to surface treatment.
作為矽烷偶合劑，可使用環氧矽烷系偶合劑、胺基矽烷系偶合劑、巰基矽烷系偶合劑等。此等可1種或組合2種以上使用。具體而言，例如可列舉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-環氧基環己基)乙基三甲氧基矽烷等之環氧矽烷系 偶合劑、胺丙基甲氧基矽烷、胺丙基三乙氧基矽烷、N-苯基-3-胺丙基三甲氧基矽烷、N-2(胺乙基)胺丙基三甲氧基矽烷等之胺基矽烷系偶合劑、巰基丙基三甲氧基矽烷、巰基丙基三乙氧基矽烷等之巰基矽烷系偶合劑。 As the decane coupling agent, an epoxy decane coupling agent, an amino decane coupling agent, a mercapto decane coupling agent, or the like can be used. These may be used alone or in combination of two or more. Specific examples thereof include glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane, glycidoxypropylmethyldiethoxydecane, and propylene oxide. Epoxy decane series such as butyl trimethoxy decane or (3,4-epoxycyclohexyl)ethyl trimethoxy decane Coupling agent, amine propyl methoxy decane, amine propyl triethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, N-2 (amine ethyl) amine propyl trimethoxy decane A mercapto decane coupling agent such as an amino decane coupling agent, mercaptopropyltrimethoxydecane or mercaptopropyltriethoxysilane.
作為烷氧基矽烷，可使用甲基三甲氧基矽烷、十八基三甲氧基矽烷、苯基三甲氧基矽烷、甲丙烯醯氧基丙基三甲氧基矽烷、咪唑矽烷、三嗪矽烷等。此等可1種或組合2種以上使用。 As the alkoxydecane, methyltrimethoxydecane, octadecyltrimethoxydecane, phenyltrimethoxydecane, propylene propyleneoxypropyltrimethoxydecane, imidazolium, triazine decane, or the like can be used. These may be used alone or in combination of two or more.
烷氧基寡聚物，以結合有機基與烷氧基甲矽烷基之低分子樹脂為佳，例如可列舉含有甲基之烷氧基寡聚物、含有苯基之烷氧基寡聚物、含有甲基/苯基之烷氧基寡聚物、含有環氧基之烷氧基寡聚物、含有巰基之烷氧基寡聚物、含有胺基之烷氧基寡聚物、含有丙烯酸基之烷氧基寡聚物、含有甲基丙烯酸基之烷氧基寡聚物、含有脲基之烷氧基寡聚物、含有異氰酸酯基之烷氧基寡聚物、含有乙烯基之烷氧基寡聚物等。此等可1種或組合2種以上使用。 The alkoxy oligomer is preferably a low molecular weight resin in which an organic group and an alkoxycarbenyl group are bonded, and examples thereof include a methyl group-containing alkoxy oligomer and a phenyl group-containing alkoxy oligomer. Alkoxy oligomer containing a methyl/phenyl group, an alkoxy oligomer containing an epoxy group, an alkoxy oligomer containing a mercapto group, an alkoxy oligomer containing an amine group, and an acrylic group-containing Alkoxy oligomer, methacryl group-containing alkoxy oligomer, ureido group-containing alkoxy oligomer, isocyanate group-containing alkoxy oligomer, vinyl group-containing alkoxy group Oligomers, etc. These may be used alone or in combination of two or more.
作為鋁系偶合劑，例如可列舉鋁異丙酸酯、單第二丁氧基鋁二異丙酸酯、鋁第二丁酸酯、鋁乙醇酯、乙基乙醯乙酸酯鋁二異丙酸酯、鋁參(乙基乙醯乙酸酯)、烷基乙醯乙酸酯鋁二異丙酸酯、鋁單乙醯丙酮酸酯雙(乙基乙醯乙酸酯)、鋁參(乙醯丙酮酸酯)、氧化環狀鋁異丙酸酯、氧化環狀鋁異丙酸酯、氧化環狀鋁硬脂酸、氧化環狀鋁辛酸酯、氧化環狀鋁硬脂酸等。此等可1種或組合2種以上使用。 Examples of the aluminum-based coupling agent include aluminum isopropyl ester, mono-second butoxide aluminum diisopropyl acid ester, aluminum second butyrate, aluminum alcohol ester, and ethyl acetoacetate aluminum diisopropylate. Acid ester, aluminum ginseng (ethyl acetamidine acetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetonate bis (ethyl acetamidine acetate), aluminum ginseng ( Acetylpyruvate), oxidized cyclic aluminum isopropyl ester, oxidized cyclic aluminum isopropyl acid ester, oxidized cyclic aluminum stearic acid, oxidized cyclic aluminum octanoate, oxidized cyclic aluminum stearic acid, and the like. These may be used alone or in combination of two or more.
作為鈦系偶合劑，例如可列舉丁基鈦酸酯二聚物、鈦辛烯甘醇酸酯、二異丙氧基鈦雙(三乙醇胺根(triethanolaminato))、二羥基鈦雙乳酸酯、二羥基雙(銨乳酸酯)鈦、雙(二辛基焦磷酸酯)伸乙基鈦酸酯、雙(二辛基焦磷酸酯)氧基乙酸酯鈦酸酯、三-n-丁氧基鈦單硬脂酸、四-n-丁基鈦酸酯、四(2-乙基己基)鈦酸酯、四異丙基雙(二辛基亞磷酸酯)鈦酸酯、四辛基雙(雙十三烷基亞磷酸酯)鈦酸酯、四(2,2-二烯丙氧基甲基-1-丁基)雙(雙十三烷基)亞磷酸酯鈦酸酯、異丙基三辛醯基鈦酸酯、異丙基三異丙苯基苯基鈦酸酯、異丙基三異硬脂基鈦酸酯、異丙基異硬脂基二丙烯醯基鈦酸酯、異丙基二甲基丙烯醯基異硬脂基鈦酸酯、異丙基三(二辛基磷酸酯)鈦酸酯、異丙基參十二烷基苯磺醯基鈦酸酯、異丙基參(二辛基焦磷酸酯)鈦酸酯、異丙基三(N-醯胺乙基‧胺基乙基)鈦酸酯等。此等可1種或組合2種以上使用。 Examples of the titanium-based coupling agent include a butyl titanate dimer, a titanium octene glycolate, a titanium diisopropoxide (triethanolaminato), and a dihydroxy titanium dilactic acid. Dihydroxybis(ammonium lactate) titanium, bis(dioctylpyrophosphate) extended ethyl titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tri-n-butyl Oxytitanium monostearate, tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate, tetraisopropylbis(dioctylphosphite) titanate, tetraoctyl Bis(ditridecylphosphite) titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, different Propyl trioctyl decyl titanate, isopropyl triisopropyl phenyl titanate, isopropyl triisostearyl titanate, isopropyl isostearyl propylene acrylate titanate, iso Propyl dimethyl propylene decyl isostearyl titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl dodecyl benzene sulfonate titanate, isopropyl Sodium (dioctyl pyrophosphate) titanate, isopropyl tris(N-nonylamine ethyl ‧ aminoethyl) titanate, and the like. These may be used alone or in combination of two or more.
作為鋯系偶合劑，例如可列舉鋯IV(2,2-雙(2-丙烯酸甲酯(Propenoate methyl))丁酸酯，參新癸酸酯(Neodecanoate))、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸酯，參(十二烷基苄基磺酸酯))、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸酯，參(二辛基)磷酸酯)、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸酯，參2-甲基2-丙烯酸酯)、鋯IV-雙(2,2-雙(2-丙烯酸甲酯)丁酸酯，雙對胺基苯甲酸酯)、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸酯，參(二異辛基)焦磷酸酯)、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸 酯，參2-丙烯酸酯(Propenoate))、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸酯，參(2-伸乙基二胺基)乙醇酯)、鋯IV，雙(2,2-雙(2-丙烯酸甲酯)丁酸酯，雙(3-巰基丙酸酯(Propanoate)))、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸酯，參(2-胺基)苯醚(phenylate))、鋯IV(2,2-雙(2-丙烯酸甲酯)丁酸酯，參(二異辛基)焦磷酸酯)，N-取代甲基丙烯醯基醯胺加成物、鋯IV(2-乙基，2-丙烯酸甲酯)-1,3-丙烷二辛酯(propane Dioctylate)，環二2,2-(雙-2-丙烯酸甲酯)丁酸酯，對磷酸酯)、鋯IV(肆-2,2-(雙-2-丙烯酸甲酯)丁酸酯，雙十三烷基氫亞磷酸酯2莫耳加成物等。此等可1種或組合2種以上使用。 Examples of the zirconium coupling agent include zirconium IV (2,2-bis(2-propionic acid methyl ester) butyrate, neodecanoate), and zirconium IV (2,2-double). (2-methyl acrylate) butyrate, stilbene (dodecyl benzyl sulfonate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (dioctyl) Phosphate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng 2-methyl 2-acrylate), zirconium IV-bis(2,2-bis(2-methyl acrylate) Butyrate, bis-amino benzoate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (diisooctyl) pyrophosphate), zirconium IV (2) ,2-bis(2-methyl acrylate) butyric acid Ester, ginseng 2-propionate (Propenoate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (2-extended ethyldiamine) ethanolate), zirconium IV, double (2,2-bis(2-methyl acrylate) butyrate, bis(3-mercaptopropionate), zirconium IV (2,2-bis(2-methyl acrylate) butyrate, Phenyl (2-amino) phenylate, zirconium IV (2,2-bis(2-methyl acrylate) butyrate, ginseng (diisooctyl) pyrophosphate), N-substituted methyl Propylene decyl decylamine adduct, zirconium IV (2-ethyl, 2-methyl acrylate)-1,3-propane dioctylate (cycloane 2,2-bis-2-acrylic acid) Ester) Butyrate, p-phosphate), Zirconium IV (肆-2,2-(bis-2-methyl acrylate) butyrate, ditridecylhydrophosphite 2 molar addition, and the like. These may be used alone or in combination of two or more.
(C)無機充填材之表面處理後，鍵結於無機充填材表面的每單位面積碳量以1.00mg/m2以下為佳，以0.75mg/m2以下為更佳，0.70mg/m2以下為進一步更佳，以0.65mg/m2以下為又更進一層佳，以0.60mg/m2以下為又進而再更佳，以0.55mg/m2以下為特佳，以0.50mg/m2以下為進而再特佳。另一方面，鍵結於其表面的每單位面積碳量以0.05mg/m2以上為佳，以0.08mg/m2以上為更佳，以0.11mg/m2以上為進一步更佳，0.14mg/m2以上為又更進一層佳，以0.17mg/m2以上為又進而再更佳，以0.20mg/m2以上為特佳，以0.23mg/m2以上為進而再特佳，以0.26mg/m2以上為最佳。由此，穩定濕式粗糙化步驟後之算術平均粗糙度、均方根粗糙 度，且變為可穩定地形成高剝離強度的導體層。 (C) After the surface treatment of the inorganic filler, the amount of carbon per unit area bonded to the surface of the inorganic filler is preferably 1.00 mg/m 2 or less, more preferably 0.75 mg/m 2 or less, and 0.70 mg/m 2 . The following is further more preferable, and 0.65 mg/m 2 or less is further improved, and 0.60 mg/m 2 or less is further preferred, and 0.55 mg/m 2 or less is particularly preferable, and 0.50 mg/m is preferred. 2 The following is further excellent. On the other hand, bonded to its carbon amount per unit surface area of at 0.05mg / m 2 or more preferably, at 0.08mg / m 2 or more is more preferred to 0.11mg / m 2 or more is further more preferably, 0.14mg / m 2 or more is good and one step further, to 0.17 mg / m 2 or more is in turn better then, to 0.20mg / m 2 or more is particularly preferred to 0.23mg / m 2 or more of which can then particularly preferred to 0.26 mg/m 2 or more is most preferable. Thereby, the arithmetic mean roughness and the root mean square roughness after the wet roughening step are stabilized, and the conductor layer which can stably form a high peeling strength becomes.
無機充填材之表面處理程度，可定量化具有將表面處理後之無機充填材由溶劑(例如，甲基乙基酮(MEK))洗淨處理之後無機充填材的每單位表面積碳量(亦即，鍵結於無機充填材表面的每單位面積碳量)。例如，鍵結於無機充填材表面的每單位面積碳量，可用以下之順序算出。將充分量之MEK作為溶劑加入表面處理後之無機充填材，進行超音波洗淨。去除上清液，使固體含量乾燥後，使用碳分析儀測定鍵結於無機充填材表面之碳量。由將得到之碳量除以無機充填材之比表面積，算出鍵結於無機充填材每單位面積之碳量。 The degree of surface treatment of the inorganic filler can be quantified by the amount of carbon per unit surface area of the inorganic filler after the surface treated inorganic filler is washed by a solvent (for example, methyl ethyl ketone (MEK)) (ie, , the amount of carbon per unit area bonded to the surface of the inorganic filler). For example, the amount of carbon per unit area bonded to the surface of the inorganic filler can be calculated in the following order. A sufficient amount of MEK was added as a solvent to the surface-treated inorganic filler to perform ultrasonic cleaning. After removing the supernatant and drying the solid content, the amount of carbon bonded to the surface of the inorganic filler was measured using a carbon analyzer. The amount of carbon bonded to the inorganic filler per unit area is calculated by dividing the amount of carbon obtained by the specific surface area of the inorganic filler.
尚且，作為碳分析儀，可使用堀場製作所製「EMIA-320V」等。 In addition, as the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd., etc. can be used.
將本發明之樹脂組成物經硬化形成絕緣層，粗糙化處理其絕緣層表面，經鍍敷所得到之導體層與絕緣層之剝離強度，由後述<鍍敷導體層之剝離強度(Peel Strength)測定>所記載之測定方法可以掌握。 The resin composition of the present invention is cured to form an insulating layer, and the surface of the insulating layer is roughened, and the peeling strength of the conductor layer and the insulating layer obtained by plating is determined by the peel strength of the plated conductor layer (Peel Strength) described later. The measurement method described in the measurement > can be grasped.
剝離強度，以0.8kgf/cm以下為佳，以0.9kgf/cm以下為更佳，以1.0kgf/cm以下為進一步更佳，以1.5kgf/cm以下為更進一層佳。又，剝離強度以0.4kgf/cm以上為佳，0.5kgf/cm以上為更佳。 The peeling strength is preferably 0.8 kgf/cm or less, more preferably 0.9 kgf/cm or less, further preferably 1.0 kgf/cm or less, and more preferably 1.5 kgf/cm or less. Further, the peel strength is preferably 0.4 kgf/cm or more, and more preferably 0.5 kgf/cm or more.
將本發明之樹脂組成物硬化而形成絕緣層，將該絕緣層表面經粗糙化處理後之算術平均粗糙度(Ra值)、均方根粗糙度(Rq值)，由後述<粗糙化後之算術平均粗 糙度(Ra值)、均方根粗糙度(Rq值)之測定>所記載之測定方法可以掌握。 The resin composition of the present invention is cured to form an insulating layer, and the arithmetic mean roughness (Ra value) and root mean square roughness (Rq value) of the surface of the insulating layer after roughening treatment are determined by the following <roughening Arithmetic average Measurement of roughness (Ra value) and root mean square roughness (Rq value) > The measurement method described can be grasped.
算術平均粗糙度(Ra值)，為了減輕電氣信號之傳輸損耗，以300nm以下為佳，以260nm以下為更佳，以240nm以下為進一步更佳，以220nm以下為更進一層佳，以200nm以下為又進而再更佳，以170nm以下為特佳，以160nm以下為進而再特佳，以150nm以下為最佳。另一方面、算術平均粗糙度(Ra值)，從提高剝離強度之觀點來看，以10nm以上為佳，以20nm以上為更佳，以30nm以上為進一步更佳，以40nm以上為更進一層佳，50nm以上為又進而再更佳。 In order to reduce the transmission loss of the electrical signal, the arithmetic mean roughness (Ra value) is preferably 300 nm or less, more preferably 260 nm or less, further preferably 240 nm or less, and more preferably 220 nm or less, and 200 nm or less. Further preferably, it is particularly preferably 170 nm or less, further preferably 160 nm or less, and most preferably 150 nm or less. On the other hand, the arithmetic mean roughness (Ra value) is preferably 10 nm or more, more preferably 20 nm or more, more preferably 30 nm or more, and 40 nm or more, from the viewpoint of improving the peel strength. Good, 50nm or more is even better.
均方根粗糙度(Rq值)，為了減輕電氣信號之傳輸損耗，以480nm以下為佳，440nm以下為更佳，以420nm以下為進一步更佳，以380nm以下為更進一層佳，以340nm以下為又進而再更佳，以300nm以下為特佳，以260nm以下為進而再特佳，以220nm以下為最佳。另一方面，均方根粗糙度(Rq值)，從提高剝離強度之觀點來看，以10nm以上為佳，30nm以上為更佳，以50nm以上為進一步更佳，以70nm以上為更進一層佳，以90nm以上為又進而再更佳。 The root mean square roughness (Rq value) is preferably 480 nm or less, more preferably 440 nm or less, more preferably 420 nm or less, and more preferably 380 nm or less, and 340 nm or less in order to reduce the transmission loss of the electrical signal. Further, it is further preferably 300 nm or less, further preferably 260 nm or less, and 220 nm or less. On the other hand, the root mean square roughness (Rq value) is preferably 10 nm or more, more preferably 30 nm or more, more preferably 50 nm or more, and more preferably 70 nm or more from the viewpoint of improving the peel strength. Good, more than 90nm and then even better.
由本發明之樹脂組成物，進一步藉由使其含有硬化促進劑，可有效率地將環氧樹脂與硬化劑硬化。作為硬化促 進劑，並未有特別限制，可列舉胺系硬化促進劑、胍系硬化促進劑、咪唑系硬化促進劑、鏻系硬化促進劑、金屬系硬化促進劑等。此等可1種或組合2種以上使用。 Further, by the resin composition of the present invention, the epoxy resin and the curing agent can be efficiently cured by further containing a curing accelerator. As hardening The agent is not particularly limited, and examples thereof include an amine-based hardening accelerator, a lanthanum-based hardening accelerator, an imidazole-based hardening accelerator, a lanthanum-based hardening accelerator, and a metal-based hardening accelerator. These may be used alone or in combination of two or more.
作為胺系硬化促進劑，並未有特別限定，可列舉三乙基胺、三丁基胺等之三烷基胺、4-二甲基胺基吡啶、苄基二甲基胺、2,4,6,-參(二甲基胺基甲基)酚、1,8-二氮雜雙環(5,4,0)-十一烯(以下，簡稱為DBU)等。此等可1種或組合2種以上使用。 The amine-based curing accelerator is not particularly limited, and examples thereof include a trialkylamine such as triethylamine or tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, and 2,4. 6,6--(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene (hereinafter abbreviated as DBU), and the like. These may be used alone or in combination of two or more.
作為胍系硬化促進劑，並未有特別限定，可列舉雙氰胺、1-甲基胍、1-乙基胍、1-環己基胍、1-苯基胍、1-(o-甲苯基)胍、二甲基胍、二苯基胍、三甲基胍、四甲基胍、五甲基胍、1,5,7-三氮雜雙環[4.4.0]十-5-烯、7-甲基-1,5,7-三氮雜雙環[4.4.0]十-5-烯、1-甲基雙胍、1-乙基雙胍、1-n-丁基雙胍、1-n-十八基雙胍、1,1-二甲基雙胍、1,1-二乙基雙胍、1-環己基雙胍、1-烯丙基雙胍、1-苯基雙胍、1-(o-甲苯基)雙胍等。此等可1種或組合2種以上使用。 The oxime-based hardening accelerator is not particularly limited, and examples thereof include dicyandiamide, 1-methylanthracene, 1-ethylanthracene, 1-cyclohexylfluorene, 1-phenylanthracene, and 1-(o-methylphenyl). ) hydrazine, dimethyl hydrazine, diphenyl hydrazine, trimethyl hydrazine, tetramethyl hydrazine, pentamethyl hydrazine, 1,5,7-triazabicyclo[4.4.0] tens-5-ene, 7 -methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-ten Octabiguanidine, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allyl biguanide, 1-phenylbiguanide, 1-(o-methylphenyl)biguanide Wait. These may be used alone or in combination of two or more.
作為咪唑系硬化促進劑，並未有特別限定，可列舉2-甲基咪唑、2-十一基咪唑、2-十七基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰乙基-2-甲基咪唑、1-氰乙基-2-十一基咪唑、1-氰乙基-2-乙基-4-甲基咪唑、1-氰乙基-2-苯基咪唑、1-氰乙基-2-十一基咪唑鎓 (Imidazolium)偏苯三甲酸酯、1-氰乙基-2-苯基咪唑鎓偏苯三甲酸酯、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-十一基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-乙基-4’-甲基咪唑基-(1’)]-乙基-s-三嗪、2,4-二胺基-6-[2’-甲基咪唑基-(1’)]-乙基-s-三嗪異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-甲基-5羥基甲基咪唑、2,3-二氫-1H-吡咯[1,2-a]苯并咪唑、1-十二烷基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑啉、2-苯基咪唑啉等之咪唑化合物及咪唑化合物與環氧樹脂之加成物。此等可1種或組合2種以上使用。 The imidazole-based hardening accelerator is not particularly limited, and examples thereof include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4. -methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecamimidazolium (Imidazolium) trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') ]-Ethyl-s-triazine, 2,4-diamino-6-[2'-undecidamidazolyl-(1')]-ethyl-s-triazine, 2,4-diamine 6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazole Base-(1')]-ethyl-s-triazine iso-cyanuric acid adduct, 2-phenylimidazolium isocyanurate adduct, 2-phenyl-4,5-dihydroxymethyl Imidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole [1,2-a]benzimidazole, 1-dodecyl-2-methyl An imidazole compound such as benzyl-3-benzylimidazolium chloride, 2-methylimidazoline or 2-phenylimidazoline, and an adduct of an imidazole compound and an epoxy resin. These may be used alone or in combination of two or more.
作為鏻系硬化促進劑，並未有特別限定，可列舉三苯基膦、鏻硼酸酯化合物、四苯基鏻四苯基硼酸酯、n-丁基鏻四苯基硼酸酯、四丁基鏻癸酸鹽、(4-甲基苯基)三苯基鏻硫氰酸酯、四苯基鏻硫氰酸酯、丁基三苯基鏻硫氰酸酯等。此等可1種或組合2種以上使用。 The oxime-based hardening accelerator is not particularly limited, and examples thereof include triphenylphosphine, bismuth borate compound, tetraphenylphosphonium tetraphenyl borate, n-butyl fluorene tetraphenyl borate, and tetra. Butyl phthalate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like. These may be used alone or in combination of two or more.
在本發明之樹脂組成物，硬化促進劑(金屬系硬化促進劑除外)之含量，將樹脂組成物中之非揮發成分作為100質量%時，以0.005~1質量%之範圍為佳，以0.01~0.5質量%之範圍為更佳。未滿0.005質量%時，有硬化變遲熱硬化時間變長成為必要之傾向，超過1質量%時有樹脂組成物之保存安定性降低之傾向。 In the resin composition of the present invention, the content of the hardening accelerator (excluding the metal-based hardening accelerator) is preferably in the range of 0.005 to 1% by mass, and 0.01% by mass in the non-volatile content in the resin composition. A range of ~0.5% by mass is more preferable. When it is less than 0.005 mass%, the hardening-to-late heat-hardening time tends to become long, and when it exceeds 1 mass%, the storage stability of the resin composition tends to be lowered.
作為金屬系硬化促進劑，並未有特別限定，可列舉鈷、銅、鋅、鐵、鎳、錳、錫等之金屬的有機金屬錯合物 或有機金屬鹽。作為有機金屬錯合物之具體例，可列舉鈷(II)乙醯丙酮酸鹽、鈷(III)乙醯丙酮酸鹽等之有機鈷錯合物、銅(II)乙醯丙酮酸鹽等之有機銅錯合物、鋅(II)乙醯丙酮酸鹽等之有機鋅錯合物、鐵(III)乙醯丙酮酸鹽等之有機鐵錯合物、鎳(II)乙醯丙酮酸鹽等之有機鎳錯合物、錳(II)乙醯丙酮酸鹽等之有機錳錯合物等。作為有機金屬鹽之具體例，可列舉辛基酸鋅、辛基酸錫、環烷酸鋅、環烷酸鈷、硬脂酸錫、硬脂酸鋅等。此等可1種或組合2種以上使用。 The metal-based hardening accelerator is not particularly limited, and examples thereof include organometallic complexes of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Or an organic metal salt. Specific examples of the organic metal complex include cobalt (II) acetoacetate, an organic cobalt complex such as cobalt (III) acetoacetate, and copper (II) acetoacetate. Organic copper complex, organic zinc complex such as zinc (II) acetamidine pyruvate, organic iron complex such as iron (III) acetoacetate, nickel (II) acetoacetate, etc. An organic manganese complex such as an organic nickel complex or manganese (II) acetoacetate or the like. Specific examples of the organic metal salt include zinc octoate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.
在本發明之樹脂組成物，金屬系硬化促進劑之添加量，將樹脂組成物中之非揮發成分作為100質量%時，基於金屬系硬化觸媒金屬之含量以25~500ppm之範圍為佳，以40~200ppm之範圍為更佳。未滿25ppm時，有對形成低算術平均粗糙度之絕緣層表面的附著力優異導體層變為困難之傾向，超過500ppm時，有變為降低樹脂組成物之保存安定性、絕緣性之傾向。 In the resin composition of the present invention, when the amount of the metal-based hardening accelerator added is 100% by mass in the resin composition, the content of the metal-based curing catalyst metal is preferably in the range of 25 to 500 ppm. It is preferably in the range of 40 to 200 ppm. When the amount is less than 25 ppm, the adhesion of the surface of the insulating layer having a low arithmetic mean roughness tends to be excellent, and when it exceeds 500 ppm, the storage stability and the insulating property of the resin composition tend to be lowered.
在本發明之樹脂組成物，進一步可由使其含有(E)熱可塑性樹脂提高硬化物之機械強度，進而亦可提高以黏著薄膜之形態使用時之膜成型能。作為如此之熱可塑性樹脂，例如可列舉苯氧基樹脂、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、聚伸苯基醚樹脂、聚碳酸酯樹脂、聚醚醚酮樹脂、聚酯樹脂。 此等之熱可塑性樹脂可1種或2種以上組合使用。從提高膜成型能或機械強度、提高樹脂清漆之相溶性的點來看，熱可塑性樹脂之重量平均分子量以5000~200000之範圍為佳。尚且於本發明之重量平均分子量，以透膠層析術(GPC)法(以聚苯乙烯換算)測定。由GPC法之重量平均分子量，具體而言，作為測定裝置使用(股)島津製作所製LC-9A/RID-6A、作為管柱使用之昭和電工(股)公司製Shodex K-800P/K-804L/K-804L、作為移動相使用氯仿等，在管柱溫度40℃測定，可使用標準聚苯乙烯之檢量線算出。 Further, the resin composition of the present invention may further contain (E) a thermoplastic resin to increase the mechanical strength of the cured product, and further improve the film forming ability when used in the form of an adhesive film. Examples of such a thermoplastic resin include a phenoxy resin, a polyimine resin, a polyamidoximine resin, a polyether quinone resin, a polyfluorene resin, a polyether oxime resin, and a polyphenylene ether. Resin, polycarbonate resin, polyether ether ketone resin, polyester resin. These thermoplastic resins may be used singly or in combination of two or more kinds. The weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000 from the viewpoint of improving the film forming ability or mechanical strength and improving the compatibility of the resin varnish. The weight average molecular weight of the present invention is also measured by a gel permeation chromatography (GPC) method (in terms of polystyrene). The weight average molecular weight of the GPC method, specifically, the LC-9A/RID-6A manufactured by Shimadzu Corporation and the Shodex K-800P/K-804L manufactured by Showa Denko Co., Ltd. /K-804L, using chloroform as a mobile phase, and measuring at a column temperature of 40 ° C, can be calculated using a calibration curve of standard polystyrene.
於本發明之樹脂組成物，摻合(E)熱可塑性樹脂時，樹脂組成物中之熱可塑性樹脂含量，並未有特別限定，相對於樹脂組成物中之非揮發成分為100質量%，以0.1~10質量%為佳，以1~5質量%為更佳。熱可塑性樹脂之含量過少時，有無法發揮提高膜成型能或機械強度之效果的傾向，過多時有熔融黏度上升與濕式粗糙化步驟後之絕緣層表面的算術平均粗糙度增加的傾向。 In the resin composition of the present invention, when the (E) thermoplastic resin is blended, the content of the thermoplastic resin in the resin composition is not particularly limited, and is 100% by mass based on the nonvolatile content in the resin composition. 0.1 to 10% by mass is preferred, and 1 to 5% by mass is more preferred. When the content of the thermoplastic resin is too small, the effect of improving the film forming ability or the mechanical strength tends not to be exhibited. When the amount is too large, the melt viscosity increases and the arithmetic mean roughness of the surface of the insulating layer after the wet roughening step tends to increase.
本發明之樹脂組成物，進而由使其含有(F)橡膠粒子，可提高鍍敷剝離強度、提高穿孔加工性、降低介電正切，亦可得到應力緩和效果。在本發明所使用而得到之橡膠粒子，例如使用於調製該樹脂組成物清漆之際的有機溶劑亦無法溶解，為必須成分之硬化劑或環氧樹脂等亦不相 溶者。因此，該橡膠粒子，係於本發明之樹脂組成物的清漆中以分散狀態存在。如此之橡膠粒子，一般而言係將橡膠成分之分子量增大到無法溶解於有機溶劑或樹脂之水準為止，調製成粒子狀。 Further, by including the (F) rubber particles, the resin composition of the present invention can improve the plating peel strength, improve the piercing processability, and lower the dielectric tangent, and can also obtain a stress relaxation effect. The rubber particles used in the present invention are not dissolved in an organic solvent used for preparing the resin composition varnish, and are not required to be a hardener or an epoxy resin which is an essential component. Soluble. 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 by increasing the molecular weight of the rubber component to a level at which it cannot be dissolved in an organic solvent or a resin.
作為在本發明所使用而得到之橡膠粒子較佳的例子，可列舉核殼型橡膠粒子、交聯丙烯腈丁二烯橡膠粒子、交聯苯乙烯丁二烯橡膠粒子、丙烯醯基橡膠粒子等。核殼型橡膠粒子，係具有心層與殼層之橡膠粒子，例如，可列舉外層之殼層係以玻璃狀聚合物所構成，內層之心層係以橡膠狀聚合物所構成之2層構造、或外層之殼層係以玻璃狀聚合物所構成，中間層係以橡膠狀聚合物所構成，心層係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，以甲基丙烯酸甲酯之聚合物等所構成，橡膠狀聚合物層，例如，以丙烯酸丁酯聚合物(丁基橡膠)等所構成。橡膠粒子亦可組合2種以上使用。作為核殼型橡膠粒子之具體例，可列舉staphyloid AC 3832、AC 3816N、IM-401改1、IM-401改7-17(商品名，甘茲化成(股)製)、METABLEN KW-4426(商品名，三菱麗陽(股)製)。作為交聯丙烯腈丁二烯橡膠(NBR)粒子之具體例，可列舉XER-91(平均粒徑0.5μm，JSR(股)製)等。作為交聯苯乙烯丁二烯橡膠(SBR)粒子之具體例，可列舉XSK-500(平均粒徑0.5μm，JSR(股)製)等。作為丙烯醯基橡膠粒子之具體例，可列舉METABLEN W300A(平均粒徑0.1μm)、W450A(平均粒徑0.2μm)(三 菱麗陽(股)製)。 Preferable examples of the rubber particles obtained by using the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylonitrile-based rubber particles. . The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is composed of a glassy polymer, and the core layer of the inner layer is composed of a rubber polymer. The structure or the outer shell layer is composed of a glassy polymer, the intermediate layer is composed of a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate or the like, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Two or more types of rubber particles may be used in combination. Specific examples of the core-shell type rubber particles include staphyloid AC 3832, AC 3816N, IM-401 modified 1, IM-401 modified 7-17 (trade name, manufactured by Ganzi Chemical Co., Ltd.), and METABLEN KW-4426 ( Trade name, Mitsubishi Rayon (share) system). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (having an average particle diameter of 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the acrylonitrile-based rubber particles include METABLEN W300A (average particle diameter: 0.1 μm) and W450A (average particle diameter: 0.2 μm) (three) Ling Liyang (share) system).
橡膠粒子之平均粒徑，較佳為0.005~1μm之範圍，更佳為0.2~0.6μm之範圍。於本發明所使用之橡膠粒子的平均粒徑，可使用動態光散射法測定。例如，於適當有機溶劑使橡膠粒子由超音波等均勻地分散，使用濃厚系粒徑分析儀(FPAR-1000；大塚電子(股)製)，將橡膠粒子之粒度分布以質量基準作成，可將該中位徑作為平均粒徑測定。 The average particle diameter of the rubber particles 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 dynamic light scattering method. For example, the rubber particles are uniformly dispersed by ultrasonic waves or the like in a suitable organic solvent, and the particle size distribution of the rubber particles is prepared on a mass basis using a thick particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). This median diameter was measured as an average particle diameter.
橡膠粒子之含量，相對於樹脂組成物中之非揮發成分為100質量%，較佳為1~10質量%，更佳為2~5質量%。 The content of the rubber particles is 100% by mass, preferably 1 to 10% by mass, and more preferably 2 to 5% by mass based on the nonvolatile content in the resin composition.
本發明之樹脂組成物，進而由使其含有(G)阻燃劑，可賦予阻燃性。作為阻燃劑，例如可列舉有機磷系阻燃劑、含有機系氮之磷化合物、氮化合物、聚矽氧系阻燃劑、金屬氫氧化物等。作為有機磷系阻燃劑之具體例，可列舉三光(股)製之HCA、HCA-HQ、HCA-NQ等之菲型磷化合物、昭和高分子(股)製之HFB-2006M等之含有磷之苯并惡嗪化合物、味之素Fine-Techno(股)製之REOFOS30、50、65、90、110、TPP、RPD、BAPP、CPD、TCP、TXP、TBP、TOP、KP140、TIBP、北興化學工業(股)製之TPPO、PPQ、Clariant(股)製之OP930、大八化學(股)製之PX200等之磷酸酯化合物、 東都化成(股)製之FX289、FX305、TX0712等之含磷環氧樹脂、東都化成(股)製之ERF001等之含磷苯氧基樹脂、日本環氧樹脂(股)製之YL7613等之含磷環氧樹脂等。作為含有有機系氮之磷化合物之具體例，可列舉四國化成工業(股)製之SP670、SP703等之磷酸酯醯胺化合物、大塚化學(股)公司製之SPB100、SPE100、(股)伏見製藥所製FP-series等之偶磷氮化合物等。作為金屬氫氧化物之具體例，可列舉宇部材料(股)製之UD65、UD650、UD653等之氫氧化鎂、巴工業(股)公司製之B-30、B-325、B-315、B-308、B-303、UFH-20等之氫氧化鋁等。 The resin composition of the present invention further contains (G) a flame retardant to impart flame retardancy. Examples of the flame retardant include an organic phosphorus-based flame retardant, a nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxymethylene-based flame retardant, and a metal hydroxide. Specific examples of the organic phosphorus-based flame retardant include phosphorus-based phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., and phosphorus-containing compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd. Benzooxazine compound, Ajinomoto Fine-Techno Co., Ltd. REOFOS30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, Beixing Chemical Phosphate compounds such as TPPO, PPQ, Clariant (OP), and PX200 made by Da Ba Chemical Co., Ltd. Phosphorus-containing epoxy resin such as FX289, FX305, and TX0712 manufactured by Dongdu Chemicals Co., Ltd., phosphorus-containing phenoxy resin such as ERF001 manufactured by Tosho Kasei Co., Ltd., and YL7613 manufactured by Japan Epoxy Resin Co., Ltd. Phosphorus epoxy resin, etc. Specific examples of the phosphorus compound containing an organic nitrogen include a phosphate phthalamide compound such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., and SPB100, SPE100, and FOS by Otsuka Chemical Co., Ltd. An even phosphorus-nitrogen compound such as FP-series manufactured by the company. Specific examples of the metal hydroxide include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., and B-30, B-325, B-315, and B manufactured by Ba Industrial Co., Ltd. -308, B-303, UFH-20, etc., such as aluminum hydroxide.
在本發明之樹脂組成物，以不阻礙本發明效果的範圍，如有必要可摻合其他成分。作為其他成分，例如可列舉如乙烯基苄基化合物、丙烯醯基化合物、馬來醯亞胺化合物、嵌段異氰酸酯化合物之熱硬化性樹脂、矽粉、耐隆粉、氟粉等之有機充填劑、Orben、本頓(Benton)等之增黏劑、聚矽氧系、氟系、高分子系之消泡劑或整平劑、咪唑系、噻唑系、***系、矽烷系偶合劑等之附著力賦予劑、酞菁‧藍、酞菁‧綠、碘綠(iodine green)、雙偶氮黃、碳黑等之著色劑等。 In the resin composition of the present invention, other components may be blended if necessary without departing from the effects of the present invention. Examples of the other component include organic fillers such as a vinylbenzyl compound, an acrylonitrile compound, a maleimide compound, a thermosetting resin of a blocked isocyanate compound, a strontium powder, a tolerant powder, and a fluorine powder. , Orben, Benton (Benton) and other tackifiers, polyfluorene-based, fluorine-based, polymer-based antifoaming agents or leveling agents, imidazole-based, thiazole-based, triazole-based, decane-based coupling agents, etc. A coloring agent such as an adhesion-imparting agent, phthalocyanine blue, phthalocyanine green, iodine green, bisazo yellow, carbon black, or the like.
本發明之樹脂組成物的調製方法，並非特別被限制，例如，可列舉因應需要將摻合成分添加溶劑等、使用旋轉 混合機等之混合方法等。 The preparation method of the resin composition of the present invention is not particularly limited, and for example, a blending component may be added to a solvent or the like as needed, and rotation may be used. A mixing method such as a mixer or the like.
本發明之樹脂組成物的用途，並未有特別限制，可使用於黏著薄膜、預浸料等之薄片狀層合材料、電路板(層合板、多層印刷電路板等)、焊料抗蝕、下填材、晶片接合材、半導體密封材料、填充樹脂、部件嵌入樹脂等以樹脂組成物作為必要用途的廣泛範圍上。其中，在多層印刷電路板之製造，可適合作為用以形成絕緣層之樹脂組成物使用，可更適合作為由鍍敷用以形成導體層之樹脂組成物使用。本發明之樹脂組成物，雖可以清漆狀態塗佈於電路板形成絕緣層，然而工業上一般以使用黏著薄膜、預浸料等之薄片狀層合材料的形態為佳。從樹脂組成物之軟化點，薄片狀層合材料之層合性觀點來看以40~150℃為佳。 The use of the resin composition of the present invention is not particularly limited, and it can be used for a sheet-like laminate material such as an adhesive film or a prepreg, a circuit board (laminated sheet, multilayer printed circuit board, etc.), solder resist, and under A filler, a wafer bonding material, a semiconductor sealing material, a filling resin, a component-embedded resin, and the like are widely used as a resin composition as an essential use. Among them, the multilayer printed circuit board can be suitably used as a resin composition for forming an insulating layer, and can be suitably used as a resin composition for forming a conductor layer by plating. The resin composition of the present invention can be applied to a circuit board to form an insulating layer in a varnish state. However, in the industrial form, a sheet-like laminate such as an adhesive film or a prepreg is generally used. From the viewpoint of the softening point of the resin composition and the lamination property of the sheet-like laminate, 40 to 150 ° C is preferable.
本發明之黏著薄膜，於該領域具有通常知識者以公知方法，例如，經溶解樹脂組成物於有機溶劑而調製樹脂清漆，此樹脂清漆可由使用模塗佈機等，塗佈於支持體，進而加熱、或吹熱風等使有機溶劑乾燥形成樹脂組成物層而製造。 In the adhesive film of the present invention, a resin varnish can be prepared by a known method, for example, by dissolving a resin composition in an organic solvent, and the resin varnish can be applied to a support by using a die coater or the like. The organic solvent is dried by heating or blowing hot air to form a resin composition layer.
作為有機溶劑，例如可列舉丙酮、甲基乙基酮、環己酮等之酮類、乙酸乙酯、乙酸丁酯、溶纖劑乙酸酯、丙二醇單甲醚乙酸酯、卡必醇乙酸酯等之乙酸酯類、溶纖劑、丁基卡必醇等之卡必醇類、甲苯、二甲苯等之芳香族烴 類、二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等之醯胺系溶劑等。有機溶劑亦可組合2種以上使用。 Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol B. Acetate such as acid ester, cellosolve, carbitol such as butyl carbitol, aromatic hydrocarbon such as toluene or xylene A guanamine-based solvent such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone. The organic solvent may be used in combination of two or more kinds.
乾燥條件並未有特別限制，使對樹脂組成物層之有機溶劑含量變為10質量%以下，較佳係變為5質量%以下乾燥。清漆中之有機溶劑量，因有機溶劑之沸點而有所不同，例如藉由含有30~60質量%之有機溶劑的清漆於50~150℃下乾燥3~10分鐘左右，可使樹脂組成物於支持體上形成經形成之層的黏著薄膜。 The drying conditions are not particularly limited, and the organic solvent content of the resin composition layer is 10% by mass or less, preferably 5% by mass or less. The amount of the organic solvent in the varnish varies depending on the boiling point of the organic solvent. For example, the resin composition can be dried at 50 to 150 ° C for 3 to 10 minutes by using a varnish containing 30 to 60% by mass of an organic solvent. An adhesive film forming a formed layer on the support.
在黏著薄膜經形成之樹脂組成物層的厚度，以導體層之厚度以上為佳。因為具有電路板之導體層的厚度通常於5~70μm之範圍，樹脂組成物層以具有10~100μm之厚度為佳，以具有20~80μm之厚度為更佳。 The thickness of the resin composition layer formed by the adhesive film is preferably greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer having 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, and more preferably has a thickness of 20 to 80 μm.
作為支持體，可列舉聚乙烯、聚丙烯、聚氯乙烯等聚烯烴之膜、聚對苯二甲酸乙二酯(以下有時簡稱為「PET」)、聚萘二甲酸乙二酯等聚酯之膜、聚碳酸酯膜、聚醯亞胺膜等之各種塑膠膜。又亦可使用離型紙或銅箔、鋁箔等之金屬箔等。於支持體及後述之保護膜，亦可實施中位數絕對誤差處理、電暈處理等之表面處理。又，亦可實施以聚矽氧樹脂系脫模劑、醇酸樹脂系脫模劑、氟樹脂系脫模劑等之脫模劑作脫模處理。 Examples of the support include a film of a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride, a polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), or a polyester such as polyethylene naphthalate. Various plastic films such as film, polycarbonate film, and polyimide film. A release paper, a metal foil such as a copper foil or an aluminum foil, or the like can also be used. A surface treatment such as a median absolute error process or a corona treatment may be performed on the support and the protective film described later. Further, a release agent such as a polyoxymethylene resin release agent, an alkyd resin release agent, or a fluororesin release agent may be used as a mold release treatment.
支持體之厚度並未有特別限制，以10~150μm為佳，以25~50μm為更佳。 The thickness of the support is not particularly limited, and is preferably 10 to 150 μm, and more preferably 25 to 50 μm.
於樹脂組成物層之支持體未密著的面上，可將根據支持體的保護膜進一步層合。保護膜之厚度，並未有特別限 定，例如為1~40μm。由層合保護膜，可防止對樹脂組成物層之表面塵埃等的附著或傷痕。黏著薄膜亦可捲繞成卷狀儲存。 The protective film according to the support may be further laminated on the surface of the resin composition layer where the support is not adhered. The thickness of the protective film is not limited For example, it is 1 to 40 μm. By laminating the protective film, adhesion or scratches to the surface of the resin composition layer such as dust or the like can be prevented. The adhesive film can also be wound into a roll for storage.
接著，說明使用如上述所製造之黏著薄膜製造多層印刷電路板方法之一例。 Next, an example of a method of manufacturing a multilayer printed wiring board using the adhesive film manufactured as described above will be described.
首先，將黏著薄膜使用真空層合機層合於電路板之單面或雙面上。作為用於電路板之基板，例如可列舉玻璃環氧基板、金屬基板、聚酯基板、聚醯亞胺基板、BT樹脂基板、熱硬化型聚伸苯基醚基板等。尚且，於此所謂電路板，係指已形成於如上述之基板之單面或雙面經圖型加工之導體層(電路)。又在將導體層與絕緣層成相互層合之多層印刷電路板，該多層印刷電路板之最外層的單面或雙面成為經圖型加工之導體層(電路)，亦包含於此之電路板。尚且於導體層表面，亦可由黑化處理、銅蝕刻等實施預先粗糙化處理。 First, the adhesive film is laminated on one or both sides of the board using a vacuum laminator. Examples of the substrate 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. Further, the term "circuit board" as used herein refers to a conductor layer (circuit) which has been formed on one side or both sides of the substrate as described above. Further, a multilayer printed circuit board in which a conductor layer and an insulating layer are laminated to each other, and a single-sided or double-sided layer of the outermost layer of the multilayer printed circuit board is a patterned conductor layer (circuit), and is also included in the circuit board. In addition to the surface of the conductor layer, pre-roughening treatment may be performed by blackening treatment, copper etching, or the like.
於上述層合，黏著薄膜具有保護膜時去除該保護膜之後，如有必要預熱黏著薄膜及電路板，將黏著薄膜一邊加壓及加熱一邊壓接於電路板。在本發明之黏著薄膜，適合使用由真空層合法於減壓下層合於電路板之方法。層合之條件，並未有特別限定，例如，壓接溫度(層合溫度)較佳為70~140℃，壓接壓力較佳為1~11kgf/cm2(9.8×104~107.9×104N/m2)，空氣壓於20mmHg(26.7hPa) 以下之減壓下層合為佳。又，層合之方法，可為批式亦可為以輥之連續式。真空層合，可使用市售之真空層合機進行。作為市售之真空層合機，例如可列舉日合‧莫頓(股)製真空施加器、(股)名機製作所製真空加壓式層合機、(股)日立Industries製輥式乾燥塗佈機、日立A-I-C(股)製真空層合機等。 In the above-mentioned lamination, after the protective film is removed by the protective film, if it is necessary to preheat the adhesive film and the circuit board, the adhesive film is pressed against the circuit board while being pressurized and heated. In the adhesive film of the present invention, a method of laminating to a circuit board by vacuum lamination under reduced pressure is suitably used. The conditions for the lamination are not particularly limited. For example, the crimping temperature (laminating temperature) is preferably 70 to 140 ° C, and the crimping 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 air under a reduced pressure of 20 mmHg (26.7 hPa) or less. Moreover, the method of laminating may be a batch type or a continuous type of rolls. Vacuum lamination can be carried out using a commercially available vacuum laminator. As a commercially available vacuum laminating machine, for example, a vacuum applicator made by Nikkiso Morton Co., Ltd., a vacuum press laminator made by a machine manufacturer, and a roll drying coat made by Hitachi Industries. Cloth machine, Hitachi AIC (share) vacuum laminator, etc.
又，減壓下進行加熱及加壓之層合步驟，亦可使用一般之真空熱壓機進行。例如可由將經加熱之SUS板等之金屬板從支持體層側加壓進行。加壓條件，將減壓程度減壓至通常為1×10-2MPa以下，較佳為1×10-3MPa以下。加熱及加壓，雖亦可以1階段進行，但從控制樹脂滲出的觀點來看，以分成2階段以上之條件進行為佳。例如，將第一階段之加壓，以溫度為70~150℃、壓力為1~15kgf/cm2之範圍；第二階段之加壓，以溫度為150~200℃、壓力為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。作為市售之真空熱壓機，例如可列舉MNPC-V-750-5-200(股)名機製作所製)、VH1-1603(北川精機(股)製)等。 Further, the laminating step of heating and pressurizing under reduced pressure may be carried out using a general vacuum hot press. For example, a metal plate such as a heated SUS plate can be pressed from the side of the support layer. Under reduced pressure, the degree of pressure reduction is reduced to usually 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 in a condition of dividing into two or more stages from the viewpoint of controlling the bleeding of the resin. For example, the first stage is pressurized at a temperature of 70 to 150 ° C and a pressure of 1 to 15 kgf / cm 2 ; the second stage of pressure, with a temperature of 150 to 200 ° C, a pressure of 1 to 40 kgf / The range of cm 2 is preferably performed. The time of each stage is preferably 30 to 120 minutes. As a commercially available vacuum hot press, for example, MNPC-V-750-5-200 (manufactured by Nippon Seiki Co., Ltd.), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like can be cited.
將黏著薄膜層合於電路板之後，冷卻至室溫附近後，剝離支持體時剝離，由熱硬化可形成絕緣層於電路板。熱硬化之條件，配合樹脂組成物中樹脂成分之種類、含量等適當選擇即可，選擇較佳為於150℃~220℃下20分鐘~180分鐘，更佳為於160℃~210℃下30~120分鐘之範圍。 After the adhesive film is laminated on the circuit board, after cooling to near room temperature, the support is peeled off when the support is peeled off, and an insulating layer is formed on the circuit board by heat hardening. The conditions of the heat curing may be appropriately selected in accordance with the kind and content of the resin component in the resin composition, and preferably selected from 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably from 160 ° C to 210 ° C. ~120 minutes range.
形成絕緣層之後，於硬化前未剝離支持體時，於此剝離。接著因應需要，於電路板上所形成之絕緣層進行鑽孔形成介層孔(via hole)、通孔。鑽孔，例如由穿孔、雷射、電漿等公知之方法，又因應需要雖可組合此等之方法進行，但以碳酸氣體雷射、YAG雷射等之雷射鑽孔為最一般之方法。 After the formation of the insulating layer, the support is not peeled off before the curing. Then, if necessary, the insulating layer formed on the circuit board is drilled to form a via hole and a via hole. Drilling, for example, by well-known methods such as perforation, laser, plasma, etc., may be performed in combination with such methods, but laser drilling such as carbon dioxide gas laser and YAG laser is the most common method. .
其次，由乾式鍍敷或濕式鍍敷形成導體層於絕緣層上。作為乾式鍍敷，可使用蒸鍍、濺鍍、離子鍍等之眾知之方法。濕式鍍敷時，藉由將絕緣層表面由膨潤液之膨潤處理、由氧化劑之粗糙化處理及由中和液之中和處理以此順序進行形成凸凹之固定錨。由膨潤液之膨潤處理，以絕緣層於50~80℃下浸漬於膨潤液5~20分鐘進行。作為膨潤液可列舉鹼溶液、界面活性劑溶液等，較佳為鹼溶液，作為該鹼溶液，例如可列舉氫氧化鈉溶液、氫氧化鉀溶液等。作為市售之膨潤液，例如可列舉Atotech Japan(股)製之Swelling‧Dip‧Securiganth P(Swelling Dip Securiganth P)、Swelling‧Dip‧Securiganth SBU(Swelling Dip Securiganth SBU)等。由氧化劑之粗糙化處理，以絕緣層於60℃~80℃下浸漬於氧化劑溶液10分~30分鐘進行。作為氧化劑，例如可列舉於氫氧化鈉水溶液之經溶解過錳酸鉀或過錳酸鈉之鹼性過錳酸溶液、重鉻酸鹽、臭氧、過氧化氫/硫酸、硝酸等。又，在鹼性過錳酸溶液中過錳酸鹽之濃度以5~10重量%為佳。作為市售之氧化劑，例如可列舉Atotech Japan(股)製之Concentrate‧Compact CP 、Dosing Solution‧Securiganth P等之鹼性過錳酸溶液。由中和液之中和處理，以於30~50℃下浸漬於中和液3~10分鐘進行。作為中和液，以酸性水溶液為佳，作為市售品，可列舉Atotech Japan(股)製之Reduction solution‧Securiganth P。 Next, a conductor layer is formed on the insulating layer by dry plating or wet plating. As the dry plating, a well-known method such as vapor deposition, sputtering, or ion plating can be used. In the wet plating, the fixing anchor is formed in the order of swelling of the surface of the insulating layer by swelling treatment of the swelling liquid, roughening treatment by the oxidizing agent, and neutralization treatment by the neutralizing liquid. The swelling treatment of the swelling liquid is carried out by immersing the insulating layer in the swelling liquid at 50 to 80 ° C for 5 to 20 minutes. The swelling solution may, for example, be an alkali solution or a surfactant solution, and is preferably an alkali solution. Examples of the alkali solution include a sodium hydroxide solution and a potassium hydroxide solution. Examples of the commercially available swelling liquid include Swelling‧Dip‧Securiganth P (Swelling Dip Securiganth P) manufactured by Atotech Japan Co., Ltd., Swelling‧Dip‧Securiganth SBU (Swelling Dip Securiganth SBU), and the like. The oxidizing agent is roughened, and the insulating layer is immersed in the oxidizing agent solution at 60 ° C to 80 ° C for 10 minutes to 30 minutes. Examples of the oxidizing agent include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution, dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid, or the like. Further, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by weight. As a commercially available oxidizing agent, for example, Concentrate ‧ Compact CP manufactured by Atotech Japan Co., Ltd. , Alkaline permanganic acid solution such as Dosing Solution‧Securiganth P. The mixture is neutralized by a neutralizing solution, and immersed in a neutralizing solution at 30 to 50 ° C for 3 to 10 minutes. As the neutralizing liquid, an acidic aqueous solution is preferred, and a commercially available product is a reduction solution ‧ Securiganth P manufactured by Atotech Japan Co., Ltd.
其次，組合無電解鍍敷與電解鍍敷形成導體層。又所謂導體層係形成逆圖型之鍍敷抗蝕，僅以無電解鍍敷亦可形成導體層。作為其後之圖型形成方法，例如可使用於該領域具有通常知識者所眾知的減法、半添加法等。 Next, a combination of electroless plating and electrolytic plating forms a conductor layer. Further, the conductor layer is formed of a reverse-plated plating resist, and the conductor layer can be formed only by electroless plating. As a pattern forming method thereafter, for example, a subtraction method, a semi-addition method, or the like which is well known to those skilled in the art can be used.
本發明之預浸料，將本發明之樹脂組成物由熱熔法或溶劑法浸漬於薄片狀補強基材，可由加熱使其半硬化製造。亦即，本發明之樹脂組成物可作為浸漬於薄片狀補強基材之預浸料。作為薄片狀補強基材，例如可使用由作為玻璃布或醯胺纖維等之預浸料用纖維所常用之纖維所構成者。 In the prepreg of the present invention, the resin composition of the present invention is impregnated into a sheet-like reinforcing substrate by a hot melt method or a solvent method, and can be semi-cured by heating. That is, the resin composition of the present invention can be used as a prepreg immersed in a sheet-like reinforcing substrate. As the sheet-like reinforcing substrate, for example, a fiber which is commonly used as a fiber for prepreg such as glass cloth or amide fiber can be used.
熱熔法，不是將樹脂溶解於有機溶劑，而是一旦塗佈於與該樹脂之剝離性良好之塗佈紙，將其層合於薄片狀補強基材，或不是將樹脂溶解於有機溶劑，而是由模塗佈機直接塗佈於薄片狀補強基材等，係製造預浸料之方法。又溶劑法，與黏著薄膜同樣將樹脂溶解於有機溶劑調製樹脂清漆，浸漬薄片狀補強基材於此清漆，將樹脂清漆浸漬於薄片狀補強基材，之後使其乾燥之方法。 The hot-melt method is not a method of dissolving a resin in an organic solvent, but coating it on a coated paper having good releasability with the resin, laminating it on a sheet-like reinforcing substrate, or dissolving the resin in an organic solvent. Instead, it is directly applied to a sheet-like reinforcing substrate or the like by a die coater to produce a prepreg. In the solvent method, a resin is dissolved in an organic solvent-prepared resin varnish, and a sheet-like reinforcing substrate is immersed in the varnish, and the resin varnish is immersed in a sheet-like reinforcing substrate, followed by drying.
其次，說明製造如上述使用所製造之預浸料的多層印刷電路板之方法的一例。將本發明之預浸料1片或因應需要重疊數片於電路板，透過脫模膜以金屬板挾住，於加壓‧加熱條件下真空加壓層合。加壓‧加熱條件，較佳為於壓力5~40kgf/cm2(49×104~392×104N/m2)、溫度120~200℃下20~100分鐘。又與黏著薄膜相同，將預浸料由真空層合法層合於電路板之後，亦可加熱硬化。然後以與上述所記載之方法相同，將經硬化之預浸料表面粗糙化之後，可製造將導體層由鍍敷形成的多層印刷電路板。 Next, an example of a method of manufacturing a multilayer printed wiring board using the prepreg produced as described above will be described. One piece of the prepreg of the present invention is placed on the circuit board as needed, and the metal sheet is clamped through the release film, and vacuum laminated under pressure and heating. The pressurization and heating conditions are preferably at 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. In the same manner as the adhesive film, the prepreg is laminated to the circuit board by vacuum lamination, and may be heat-hardened. Then, after roughening the surface of the cured prepreg in the same manner as described above, a multilayer printed wiring board in which the conductor layer is formed by plating can be manufactured.
以使用本發明之多層印刷電路板可製造半導體裝置。於本發明之多層印刷電路板的導通點，由安裝半導體晶片可製造半導體裝置。所謂「導通點」，係指「在多層印刷電路板傳遞電氣信號的點」，該點即使是表面，或是嵌入的點都沒關係。又，半導體晶片只要是將半導體作為材料之電氣電路元件就沒有特別限定。 A semiconductor device can be fabricated using the multilayer printed circuit board of the present invention. At the conduction point of the multilayer printed circuit board of the present invention, a semiconductor device can be fabricated by mounting a semiconductor wafer. The term "conducting point" means "the point at which an electrical signal is transmitted through a multilayer printed circuit board". This point does not matter even if it is a surface or an embedded point. Further, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.
製造本發明之半導體裝置之際半導體晶片的安裝方法，半導體晶片若能有效地行使功能，並未有特別限制、具體而言，可列舉由引線結合安裝方法、交換晶片安裝方法、無凸塊之堆積層(BBUL)的安裝方法、由異方性導電膜(ACF)之安裝方法、由非導電性膜(NCF)之安裝 方法等。 In the method of mounting a semiconductor wafer in the manufacture of the semiconductor device of the present invention, the semiconductor wafer is not particularly limited as long as it can effectively function, and specifically, a wire bonding mounting method, a swap wafer mounting method, and a bump-free method are exemplified. Mounting method of stacked layer (BBUL), mounting method by anisotropic conductive film (ACF), installation by non-conductive film (NCF) Method, etc.
所謂「由無凸塊之堆積層(BBUL)之安裝方法」，係指「將半導體晶片直接嵌入於多層印刷電路板之凹部，使半導體晶片與印刷電路板上之接線連接的安裝方法」，進而與以下之BBUL方法1)、BBUL方法2)之安裝方法大為不同。 The "mounting method by the bumpless buildup layer (BBUL)" means "the method of mounting the semiconductor wafer directly into the concave portion of the multilayer printed circuit board to connect the semiconductor wafer to the wiring on the printed circuit board", and further It is significantly different from the following BBUL method 1) and BBUL method 2).
BBUL方法1)係使用底部填充劑將半導體晶片安裝於多層印刷電路板之凹部的安裝方法 BBUL method 1) mounting method for mounting a semiconductor wafer on a recess of a multilayer printed circuit board using an underfill
BBUL方法2)係使用黏著薄膜或預浸料將半導體晶片安裝於多層印刷電路板之凹部的安裝方法 BBUL method 2) mounting method for mounting a semiconductor wafer on a recess of a multilayer printed circuit board using an adhesive film or prepreg
BBUL方法1)，具體包含以下之步驟。 BBUL method 1) specifically includes the following steps.
步驟1)設置從多層印刷電路板之雙面去除導體層者，藉由雷射、機械穿孔形成貫通孔。 Step 1) A person who removes the conductor layer from both sides of the multilayer printed circuit board is provided, and a through hole is formed by laser or mechanical perforation.
步驟2)將膠黏帶貼附於多層印刷電路板之單面上，如將半導體晶片之底面固定於膠黏帶上並配置於貫通孔之中。此時之半導體晶片以比貫通孔之高度更低為佳。 Step 2) attaching the adhesive tape to one side of the multilayer printed circuit board, such as fixing the bottom surface of the semiconductor wafer to the adhesive tape and arranging it in the through hole. The semiconductor wafer at this time is preferably lower than the height of the through holes.
步驟3)將底部填充劑注入於貫通孔與半導體晶片之間隙，藉由充填將半導體晶片固定於貫通孔。 Step 3) Injecting an underfill into the gap between the through hole and the semiconductor wafer, and fixing the semiconductor wafer to the through hole by filling.
步驟4)然後剝離膠黏帶，使其暴露半導體晶片之底面。 Step 4) The adhesive tape is then peeled off to expose the underside of the semiconductor wafer.
步驟5)將本發明之黏著薄膜或預浸料層合於半導體晶片之底面側，被覆半導體晶片。 Step 5) The adhesive film or prepreg of the present invention is laminated on the bottom surface side of the semiconductor wafer to coat the semiconductor wafer.
步驟6)硬化黏著薄膜或預浸料後，藉由雷射鑽孔，使於半導體晶片之底面的接合銲墊暴露，以進行上述所示 之粗糙化處理、無電解鍍敷、電解鍍敷，與接線連接。如有必要亦可進一步層合黏著薄膜或預浸料。 Step 6) after hardening the adhesive film or prepreg, the bonding pads on the bottom surface of the semiconductor wafer are exposed by laser drilling to perform the above Roughening treatment, electroless plating, electrolytic plating, and wiring. Adhesive films or prepregs can be further laminated if necessary.
BBUL方法2)，具體包含以下之步驟。 BBUL method 2) specifically includes the following steps.
步驟1)於多層印刷電路板雙面之導體層上形成光阻膜，以光微影工法僅於光阻膜之單面形成開口部。 Step 1) A photoresist film is formed on the conductor layer on both sides of the multilayer printed circuit board, and an opening portion is formed only on one side of the photoresist film by a photolithography method.
步驟2)將暴露於開口部之導體層由蝕刻液去除，使其暴露絕緣層，然後去除雙面之光阻膜。 Step 2) The conductor layer exposed to the opening is removed by an etching solution to expose the insulating layer, and then the double-sided photoresist film is removed.
步驟3)使用雷射或穿孔，將經暴露之絕緣層全部去除並進行鑽孔，而形成凹部。雷射之能量，可調整為以降低銅之雷射吸收率、提高絕緣層之雷射吸收率能量的雷射為佳，以碳酸氣體雷射為更佳。藉由使用如此之雷射，雷射不是將導體層之開口部對面的導體層貫通，而是可僅去除絕緣層。 Step 3) Using the laser or perforation, the exposed insulating layer is completely removed and drilled to form a recess. The energy of the laser can be adjusted to a laser which lowers the laser absorption rate of copper and increases the laser absorption rate of the insulating layer, and a carbon dioxide gas laser is more preferable. By using such a laser, the laser does not penetrate the conductor layer opposite to the opening of the conductor layer, but can remove only the insulating layer.
步驟4)將半導體晶片之底面面向開口部側配置於凹部，將本發明之黏著薄膜或預浸料從開口部之一側層合被覆半導體晶片，嵌入半導體晶片與凹部之間隙。此時半導體晶片以比凹部之高度更低為佳。 Step 4) The bottom surface of the semiconductor wafer is placed on the opening side in the concave portion, and the adhesive film or prepreg of the present invention is laminated on the side of the opening to cover the semiconductor wafer, and the gap between the semiconductor wafer and the concave portion is embedded. At this time, the semiconductor wafer is preferably lower in height than the concave portion.
步驟5)將黏著薄膜或預浸料硬化後，藉由雷射鑽孔，使半導體晶片底面之接合銲墊暴露。 Step 5) After the adhesive film or prepreg is hardened, the bonding pads on the bottom surface of the semiconductor wafer are exposed by laser drilling.
步驟6)藉由進行上述所示之粗糙化處理、無電解鍍敷、電解鍍敷，連接接線，如有必要進一步層合黏著薄膜或預浸料。 Step 6) By performing the above-described roughening treatment, electroless plating, electrolytic plating, connecting the wiring, and further laminating the adhesive film or prepreg if necessary.
即使於半導體晶片之安裝方法之中，從半導體裝置之小型化、傳送損失之減輕的觀點、或因為不使用焊接不採 用其熱履歷於半導體晶片，進而從將來不發生焊接與樹脂之變形的觀點來看，以由無凸塊之堆積層(BBUL)的安裝方法為佳，以BBUL方法1)、BBUL方法2)為更佳，以BBUL方法2)為特佳。 Even in the mounting method of the semiconductor wafer, from the viewpoint of miniaturization of the semiconductor device, reduction of transmission loss, or lack of soldering It is preferable to use a thermal history of the semiconductor wafer and further to prevent deformation of the solder and the resin from the future, and to mount the bumpless buildup layer (BBUL), BBUL method 1), BBUL method 2) For better, BBUL method 2) is especially good.
以下，將本發明由實施例做具體說明，然而本發明並非被限定於此等之實施例者。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples.
首先對各種測定方法‧評價方法進行說明。 First, various measurement methods and evaluation methods will be described.
(1)內層電路板之底塗處理 (1) Primer treatment of the inner layer circuit board
將經形成內層電路之玻璃布基材環氧樹脂雙面覆銅層合板(銅箔之厚度18μm、基板厚度0.3mm，松下電工(股)製R5715ES)的雙面蝕刻1um於MEC(股)製CZ8100進行銅表面之粗糙化處理。 The double-sided etching of the glass cloth substrate epoxy double-sided copper-clad laminate (the thickness of the copper foil of 18 μm, the thickness of the substrate of 0.3 mm, and the R5715ES made by Matsushita Electric Works) through the inner layer circuit is 1 um on the MEC (share) The CZ8100 is used to roughen the copper surface.
(2)黏著薄膜之層合 (2) Lamination of adhesive film
將於實施例及比較例所作成之黏著薄膜，使用批式真空加壓層合機MVLP-500(名機(股)製商品名)，層合內層電路板之雙面。層合，係將經30秒減壓之氣壓降於13hPa以下，然後由以30秒、100℃、壓力0.74MPa加壓 而進行。 The adhesive film prepared in the examples and the comparative examples was laminated on both sides of the inner layer circuit board using a batch vacuum pressure laminator MVLP-500 (trade name, manufactured by a famous machine). Laminating, the pressure reduced by 30 seconds is reduced to below 13hPa, and then pressurized by 30 seconds, 100 ° C, pressure 0.74MPa And proceed.
(3)樹脂組成物之硬化 (3) Hardening of resin composition
從經層合之黏著薄膜剝離PET膜之後，以100℃、30分鐘，進而以180℃、30分鐘之硬化條件硬化樹脂組成物。對實施例10以相同條件使其熱硬化之後剝離PET膜，形成絕緣層。 After peeling off the PET film from the laminated adhesive film, the resin composition was cured at 100 ° C for 30 minutes and further at 180 ° C for 30 minutes. After the glass was thermally cured under the same conditions as in Example 10, the PET film was peeled off to form an insulating layer.
(4)粗糙化處理 (4) roughening treatment
將形成絕緣層之內層電路板，於係膨潤液之Atotech Japan(股)的含有二乙二醇單丁基醚之Swelling Dip Securiganth P(二醇醚類、氫氧化鈉水溶液)60℃下浸漬5分鐘，對實施例7於60℃下浸漬10分鐘，接著作為粗糙化液，於Atotech Japan(股)之Concentrate‧Compact P(KMnO4：60g/L、NaOH：40g/L之水溶液)以80℃浸漬15分鐘，對實施例10以80℃浸漬20分鐘，最後作為中和液，於Atotech Japan(股)之Reduction Solution‧Securiganth P(乙二醛、硫酸之水溶液)以40℃浸漬5分鐘。以80℃乾燥30分鐘後，對此粗糙化處理後之絕緣層表面，進行算術平均粗糙度(Ra值)、均方根粗糙度(Rq值)之測定。 The inner layer circuit board in which the insulating layer is formed is immersed in Swelling Dip Securiganth P (glycol ether, aqueous sodium hydroxide solution) containing a diethylene glycol monobutyl ether in Atotech Japan (strand) of the swelling liquid at 60 ° C After 5 minutes, the sample 7 was immersed at 60 ° C for 10 minutes, and the work was carried out as a roughening liquid, and Acentech Japan's Concentrate ‧ Compact P (KMnO 4 : 60 g / L, NaOH: 40 g / L aqueous solution) was 80 After immersing for 15 minutes at ° C, the sample 10 was immersed at 80 ° C for 20 minutes, and finally, as a neutralizing solution, was immersed in Atotech Japan (Resolution Solution ‧ Securiganth P (glyoxal, aqueous solution of sulfuric acid) at 40 ° C for 5 minutes. After drying at 80 ° C for 30 minutes, the surface of the insulating layer after the roughening treatment was measured for arithmetic mean roughness (Ra value) and root mean square roughness (Rq value).
(5)由半添加工法之鍍敷 (5) Plating by semi-additive method
為了形成電路於絕緣層表面，將內層電路板於含有PdCl2之無電解鍍敷用溶液以40℃浸漬5分鐘，接著於無電解銅鍍敷液以25℃浸漬20分鐘。以150℃加熱30分鐘進行回火處理之後，形成蝕刻抗阻，由蝕刻形成圖型之 後，進行硫酸銅電解鍍敷，以35±5μm之厚度形成導體層。其次，將回火處理於200℃進行60分鐘。對此電路板進行鍍敷導體層之剝離強度(Peel strength)測定。 In order to form a circuit on the surface of the insulating layer, the inner layer circuit board was immersed in a solution for electroless plating containing PdCl 2 at 40 ° C for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C for 20 minutes. After heating at 150 ° C for 30 minutes and tempering treatment, an etching resistance was formed, and after patterning by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 35 ± 5 μm. Next, the tempering treatment was carried out at 200 ° C for 60 minutes. The board was subjected to Peel strength measurement of the plated conductor layer.
於電路板之導體層，加入寬10mm、長100mm部分的刻痕，將此一端剝離以夾持器(股份有限公司T‧S‧E，Auto com型試驗機AC-50C-SL)挾住，於室溫中以50mm/分鐘之速度測定於垂直方向剝離35mm時之荷重(kgf/cm)。 In the conductor layer of the circuit board, a notch having a width of 10 mm and a length of 100 mm is added, and the one end is peeled off and clamped by a holder (Company T.S.E, Auto com type test machine AC-50C-SL). The load (kgf/cm) when peeling 35 mm in the vertical direction was measured at a rate of 50 mm/min at room temperature.
使用非接觸型表面粗糙度計(Veeco Instruments公司製WYKO NT3300)，由VSI接觸模式、50倍鏡片藉由將測定範圍作為121μm×92μm而得到之數值求得Ra值、Rq值。然後，由各自隨機求得10點的平均值測定。 Using a non-contact surface roughness meter (WYKO NT3300, manufactured by Veeco Instruments Co., Ltd.), the Ra value and the Rq value were obtained from the VSI contact mode and the 50-fold lens by using the measurement range as 121 μm × 92 μm. Then, the average value of 10 points was randomly determined from each.
將於實施例及比較例所製作之黏著薄膜，使用批式真空加壓層合機MVLP-500(名機(股)製商品名)，層合於內層電路板之雙面。層合，係將經30秒減壓之氣壓降於13hPa以下，然後由以30秒、100℃、壓力0.74MPa加壓而進行。從經層合之黏著薄膜剝離PET膜之後，以190 ℃、1小時之硬化條件硬化樹脂組成物而形成絕緣層。進而使用高加速壽命測試裝置(ETAC製PM422)，於121.5℃、100%RH之環境下放置100小時實施PCT試驗(Pressure Cooker Test)。然後恢復至室溫，確認絕緣層與底塗銅之界面是否發生膨脹。又，於絕緣層表面加入橫割(寬1mm之格子狀的刻痕)，確認於絕緣層是否有缺陷。於絕緣層及底塗銅界面無膨脹、於橫割後未發生缺陷時作為「○」，於絕緣層及底塗銅界面無膨脹、橫割後發生缺陷時作為「△」，於絕緣層及底塗銅界面有膨脹、於橫割後發生缺陷時作為「×」。 The adhesive film produced in the examples and the comparative examples was laminated on both sides of the inner layer circuit board using a batch vacuum pressure laminator MVLP-500 (trade name, manufactured by a famous machine). The lamination was carried out by lowering the pressure of the pressure for 30 seconds to 13 hPa or less, followed by pressurization at 30 seconds, 100 ° C, and a pressure of 0.74 MPa. After peeling off the PET film from the laminated adhesive film, 190 The resin composition was hardened under a hardening condition of 1 C for 1 hour to form an insulating layer. Further, a high accelerated life tester (PM422 manufactured by ETAC) was used, and a PCT test (Pressure Cooker Test) was carried out by placing it in an environment of 121.5 ° C and 100% RH for 100 hours. Then return to room temperature and confirm whether the interface between the insulating layer and the undercoat copper is expanded. Further, a cross-cut (a lattice-shaped notch having a width of 1 mm) was added to the surface of the insulating layer to confirm whether or not the insulating layer was defective. When there is no expansion at the interface between the insulating layer and the undercoat copper, and no defect occurs after the crosscut, it is "○". When there is no expansion at the interface between the insulating layer and the undercoat copper, and a defect occurs after the crosscut, "△" is applied to the insulating layer and The undercoat copper interface is expanded, and it is "x" when a defect occurs after cross cutting.
將3g經表面處理之無機充填材作為試料使用。將試料與30g之MEK(甲基乙基酮)置入離心分離機之離心管，經攪拌使固體含量懸濁，500W超音波照射5分鐘。然後，由離心分離使固液分離，去除上清液。進一步，加上30g之MEK，經攪拌使固體含量懸濁，500W超音波照射5分鐘。然後，由離心分離使固液分離，去除上清液。使固體含量於150℃乾燥30分鐘。將此0.3g乾燥試料於測定用坩堝精確稱量，進而加助燃劑(鎢3.0g、錫0.3g)於測定用坩堝。將測定用坩堝設定於碳分析儀，測定碳量。碳分析儀，使用堀場製作所製EMIA-320V。將經測定之碳量除以無機充填材之比表面積的值作為每單位面積碳量。 3 g of the surface-treated inorganic filler was used as a sample. The sample and 30 g of MEK (methyl ethyl ketone) were placed in a centrifuge tube of a centrifugal separator, and the solid content was suspended by stirring, and 500 W ultrasonic irradiation was performed for 5 minutes. Then, the solid-liquid separation was carried out by centrifugation, and the supernatant was removed. Further, 30 g of MEK was added, and the solid content was suspended by stirring, and 500 W ultrasonic irradiation was performed for 5 minutes. Then, the solid-liquid separation was carried out by centrifugation, and the supernatant was removed. The solid content was dried at 150 ° C for 30 minutes. This 0.3 g of the dried sample was accurately weighed in a measuring crucible, and further a combustion-supporting agent (tungsten 3.0 g, tin 0.3 g) was added to the measuring crucible. The measurement enthalpy was set on a carbon analyzer, and the amount of carbon was measured. Carbon analyzer, using EMIA-320V manufactured by Horiba. The value of the measured carbon amount divided by the specific surface area of the inorganic filler is taken as the amount of carbon per unit area.
將100質量份球狀二氧化矽((股)Admatechs製「SOC2」，平均粒徑0.5μm)投入亨舍爾型混粉機，一邊噴霧0.3質量份N-苄基胺基乙醇(東京化成工業(股)製，沸點280℃)一邊攪拌球狀二氧化矽10分鐘，製成製造物1(每單位面積碳量為0.13mg/m2)。 100 parts by mass of spherical cerium oxide ("SOC2" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.3 parts by mass of N-benzylaminoethanol was sprayed (Tokyo Chemical Industry Co., Ltd.) The product (manufactured by the company, boiling point: 280 ° C) was stirred for 10 minutes to prepare a product 1 (carbon amount per unit area was 0.13 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)投入亨舍爾型混粉機，一邊噴霧0.3質量份N-苯胺基乙醇(東京化成工業(股)製，沸點268℃)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份甲基/含有苯基之烷氧基寡聚物(信越化學工業(股)製「X-40-9227」)一邊攪拌10分鐘，製成製造物2(每單位面積碳量為0.25mg/m2)。 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.3 parts by mass of N-anilinoethanol was sprayed (Tokyo Chemical Industry Co., Ltd.) (strand), boiling point 268 ° C), while stirring spherical cerium oxide for 10 minutes, and then spraying 0.3 parts by mass of a methyl group/phenyl group-containing alkoxy oligomer (Xi Yue Chemical Industry Co., Ltd. "X- 40-9227") was stirred for 10 minutes to prepare a product 2 (carbon amount per unit area was 0.25 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)投入亨舍爾型混粉機，一邊噴霧0.3質量份環氧丙醇(日本油脂(股)製「EPIOL OH」)，沸點167℃)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份苯基三甲氧基矽烷(信越化學工業(股)製「KBM-103」)一邊攪拌10分 鐘，製成製造物3(每單位面積碳量為0.18mg/m2)。 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter 0.5 μm) was placed in a Henschel type mixer, and 0.3 parts by mass of glycidol was sprayed (Japanese fat (shares) "EPIOL OH"), the boiling point of 167 ° C), while stirring the spherical cerium oxide for 10 minutes, and then spraying 0.3 parts by mass of phenyltrimethoxydecane ("KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd.) After stirring for 10 minutes, the product 3 was produced (the amount of carbon per unit area was 0.18 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.3質量份N-苄基胺基乙醇(東京化成工業(股)製、沸點280℃)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份苯基三甲氧基矽烷(信越化學工業(股)製「KBM-103」)0.3質量份一邊攪拌10分鐘，製成製造物4(每單位面積碳量為0.27mg/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.3 parts by mass of N-benzylamine group was sprayed. Ethanol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point: 280 °C), while stirring spherical cerium oxide for 10 minutes, and then spraying 0.3 parts by mass of phenyltrimethoxydecane ("KBM-103" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 parts by mass was stirred for 10 minutes to prepare a product 4 (carbon amount per unit area was 0.27 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.3質量份N-苄基胺基乙醇(東京化成工業(股)製，沸點280℃)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份含有甲基之烷氧基寡聚物(多摩化學(股)製「MTMS-A」)一邊攪拌5分鐘，製成製造物5(每單位面積碳量為0.18mg/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.3 parts by mass of N-benzylamine group was sprayed. Ethanol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point: 280 ° C), while stirring spherical cerium oxide for 10 minutes, and then spraying 0.3 parts by mass of alkoxy oligo group containing methyl group (MTMS made by Tama Chemical Co., Ltd.) -A") was stirred for 5 minutes to prepare a product 5 (carbon amount per unit area was 0.18 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍 爾型混粉機，一邊噴霧0.9質量份咪唑-環氧加成物(三菱化學(股)製「P200」，非揮發成分30%之環己酮溶液)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份含有甲基之烷氧基寡聚物(多摩化學(股)製「MTMS-A」)一邊攪拌5分鐘，製成製造物6(每單位面積碳量為0.29mg/m2)。 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was supplied to a Henschel type mixer in 100 parts by mass, and 0.9 parts by mass of imidazole-epoxy addition was sprayed. (P200 in Mitsubishi Chemical Co., Ltd., 30% cyclohexanone solution with nonvolatile content), while stirring spherical cerium oxide for 10 minutes, and then spraying 0.3 parts by mass of alkoxy oligo containing methyl group ("MTMS-A" manufactured by Tama Chemical Co., Ltd.) was stirred for 5 minutes to obtain a product 6 (carbon amount per unit area was 0.29 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.5質量份2,2-[{(甲基-1H-苯並***-1-基)甲基}亞胺基]雙乙醇(城北化學(股)製「TT-LYK」，非揮發成分60%之MEK溶液)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份含有甲基之烷氧基寡聚物(多摩化學(股)製「MTMS-A」)一邊攪拌5分鐘，製成製造物7(每單位面積碳量為0.16mg/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.5 parts by mass of 2,2-[{ (Methyl-1H-benzotriazol-1-yl)methyl}imido]diethanol ("TT-LYK" manufactured by Seiki Co., Ltd., 60% MEK solution with nonvolatile content) while stirring the ball After 10 minutes of cerium oxide, 0.3 parts by mass of a methyl group-containing alkoxy oligomer ("MTMS-A" manufactured by Tama Chemical Co., Ltd.) was sprayed for 5 minutes to obtain a product 7 (per unit area). The amount of carbon was 0.16 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.5質量份2,2-[{(甲基-1H-苯並***-1-基)甲基}亞胺基]雙乙醇(城北化學(股)製「TT-LYK」，非揮發成分60%之MEK溶液)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份含有胺 基之矽烷偶合劑(信越化學工業(股)製「KBM-573」)一邊攪拌5分鐘，製成製造物8(每單位面積碳量為0.32mg/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.5 parts by mass of 2,2-[{ (Methyl-1H-benzotriazol-1-yl)methyl}imido]diethanol ("TT-LYK" manufactured by Seiki Co., Ltd., 60% MEK solution with nonvolatile content) while stirring the ball After 10 minutes, the mixture was stirred for 5 minutes while spraying 0.3 parts by mass of an amine group-containing decane coupling agent ("KBM-573" manufactured by Shin-Etsu Chemical Co., Ltd.) to obtain a product 8 (carbon amount per unit area). It is 0.32 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.5質量份1-(2-羥基乙基)咪唑(日本合成工業化學(股)製，沸點120℃(4.4Pa)，非揮發成分60%之MEK溶液)一邊攪拌球狀二氧化矽10分鐘之後，再一邊噴霧0.3質量份二甲基二乙氧基矽烷(信越化學工業(股)製「KBE-22」)一邊攪拌10分鐘，製成製造物9(每單位面積碳量為0.12g/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.5 parts by mass of 1-(2-hydroxyl group) was sprayed. Ethyl imidazole (manufactured by Nippon Synthetic Chemical Co., Ltd., boiling point 120 ° C (4.4 Pa), 60% non-volatile MEK solution) while stirring spherical cerium oxide for 10 minutes, and then spraying 0.3 parts by mass of dimethyl The bis-ethoxy decane ("KBE-22" manufactured by Shin-Etsu Chemical Co., Ltd.) was stirred for 10 minutes to obtain a product 9 (carbon amount per unit area was 0.12 g/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.6質量份苯基三甲氧基矽烷(信越化學工業(股)製「KBM-103」，沸點218℃)一邊攪拌10分鐘，製成製造物10(每單位面積碳量為0.09mg/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.6 parts by mass of phenyltrimethoxydecane was sprayed. (KBM-103, manufactured by Shin-Etsu Chemical Co., Ltd., boiling point: 218 ° C) was stirred for 10 minutes to obtain a product 10 (carbon amount per unit area was 0.09 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製 「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.6質量份環氧基含有矽烷偶合劑(信越化學工業(股)製「KBM403」，沸點290℃)一邊攪拌5分鐘，製成製造物11(每單位面積碳量為0.24mg/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.6 parts by mass of an epoxy group containing a decane couple was sprayed. The mixture (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd., boiling point: 290 ° C) was stirred for 5 minutes to prepare a product 11 (carbon amount per unit area was 0.24 mg/m 2 ).
將100質量份球狀二氧化矽((股)Admatechs製「SC2050-SQ」，平均粒徑0.5μm)100質量份投入亨舍爾型混粉機，一邊噴霧0.6質量份含有胺基之矽烷偶合劑(信越化學工業(股)製「KBM903」，沸點215℃)一邊攪拌5分鐘，製成製造物12(每單位面積碳量為0.14mg/m2)。 100 parts by mass of 100 parts by mass of spherical cerium oxide ("SC2050-SQ" manufactured by Admatechs, average particle diameter: 0.5 μm) was placed in a Henschel type mixer, and 0.6 parts by mass of an amine group-containing decane couple was sprayed. The mixture (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd., boiling point: 215 ° C) was stirred for 5 minutes to prepare a product 12 (carbon amount per unit area was 0.14 mg/m 2 ).
將5質量份萘型環氧樹脂(環氧基當量144，DIC(股)製「HP4700」)、14質量份液狀雙酚A型環氧樹脂(環氧基當量180，三菱化學(股)製「jER828EL」)、14質量份聯苯基型環氧樹脂(環氧基當量269，日本化藥(股)製「NC3000H」)於30質量份溶劑石腦油中一邊攪拌一邊使其加熱溶解，然後冷卻至室溫，製成混合物1。其次，將1.5質量份橡膠粒子(甘茲化成(股)製，staphyloid AC3816N)，於6質量份溶劑石腦油中以12小時、20℃下靜置膨潤，製成混合物2。添加混合物2與製 造物1於混合物1，進而添加5質量份阻燃劑(三光(股)製「HCA-HQ」，10-(2,5-二羥基苯基)-10-氫-9-氧雜-10-磷菲-10-氧化物，平均粒徑1μm)，以3本輥混練，使均勻地分散。而且，混合10質量份酚系酚醛清漆系硬化劑(DIC(股)製「LA-7054」，酚性氫氧基當量124之非揮發成分60質量%的MEK溶液)、10質量份萘系酚樹脂(酚性氫氧基當量215，新日鐵化學(股)製「SN485」，非揮發成分60質量%之MEK溶液)、7質量份苯氧基樹脂(重量平均分子量35000，三菱化學(股)製「YL7553」，非揮發成分30質量%之MEK與環己酮1：1溶液)，2質量份作為硬化促進劑之4-二甲基胺基吡啶之5質量%的MEK溶液、4質量份MEK，以旋轉混合機均勻地分散，製成樹脂清漆。其次，將該樹脂清漆於醇酸系附脫模處理之聚對苯二甲酸乙二酯膜(厚度38μm)的脫模面上，以模塗佈機均勻地塗佈使乾燥後樹脂組成物層的厚度變為40μm，以80~110℃(平均95℃)下乾燥5分鐘(樹脂組成物層中之殘留溶劑量：約2質量%)。其次，於樹脂組成物層之表面貼合厚度15μm之聚丙烯膜同時捲成卷狀。將卷狀之黏著薄膜縫成寬507mm，得到尺寸507×336mm薄片狀之黏著薄膜。 5 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, "HP4700" manufactured by DIC Co., Ltd.), and 14 parts by mass of a liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, Mitsubishi Chemical Corporation) "jj828EL"), 14 parts by mass of a biphenyl type epoxy resin (epoxy equivalent 269, "Nippon Chemical Co., Ltd." "NC3000H") was dissolved and dissolved in 30 parts by mass of solvent naphtha while stirring Then, it was cooled to room temperature to prepare a mixture 1. Next, 1.5 parts by mass of rubber particles (staphyloid AC3816N, manufactured by Ganzi Chemical Co., Ltd.) were statically swollen in 6 parts by mass of solvent naphtha at 12 hours and 20° C. to obtain a mixture 2. Add mixture 2 and system The product 1 is in the mixture 1, and further added 5 parts by mass of a flame retardant ("HCA-HQ", 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-, manufactured by Sanguang Co., Ltd. Phosphenephenanthrene-10-oxide, having an average particle diameter of 1 μm, was kneaded by three rolls to uniformly disperse. Furthermore, 10 parts by mass of a phenolic novolac-based curing agent ("LA-7054" manufactured by DIC Co., Ltd., a MEK solution of 60% by mass of a nonvolatile component of a phenolic hydroxyl equivalent 124), and 10 parts by mass of a naphthalene phenol are mixed. Resin (phenolic hydroxyl equivalent 215, "SN485" manufactured by Nippon Steel Chemical Co., Ltd., 60% by mass of MEK solution), 7 parts by mass of phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Corporation ) "YL7553", a non-volatile content of 30% by mass of MEK and cyclohexanone 1:1 solution), 2 parts by mass of a dimethylaminopyridine as a hardening accelerator, 5% by mass of MEK solution, 4 mass The MEK was uniformly dispersed in a rotary mixer to prepare a resin varnish. Next, the resin varnish was applied to a release surface of an alkyd-based release-treated polyethylene terephthalate film (thickness: 38 μm), and uniformly coated by a die coater to form a resin composition layer after drying. The thickness was changed to 40 μm, and dried at 80 to 110 ° C (average 95 ° C) for 5 minutes (the amount of residual solvent in the resin composition layer: about 2% by mass). Next, a polypropylene film having a thickness of 15 μm was bonded to the surface of the resin composition layer while being wound into a roll. The roll-shaped adhesive film was sewn to a width of 507 mm to obtain an adhesive film having a sheet shape of 507 × 336 mm.
除將實施例1之製造物1變更為製造物2之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與 實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article 2. Then using the resin varnish, and Example 1 was carried out in exactly the same manner to obtain an adhesive film.
除將實施例1之製造物1變更為製造物3之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 3. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物4之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article 4. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物5之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article 5 of manufacture. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物6之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 6. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物7之外，其餘 以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 Except that the article 1 of the first embodiment is changed to the article of manufacture 7, the rest The resin varnish was produced in exactly the same manner. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物8之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 8. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物9之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 9. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
將10質量份萘型環氧樹脂(環氧基當量144，DIC(股)製「EXA4032SS」)、1質量份雙二甲酚(Bixylenol)型環氧樹脂(環氧基當量190，三菱化學(股)製「YX4000 HK」)、12質量份改質萘型環氧樹脂(環氧基當量約330，新日鐵化學(股)製「ESN475V」)於20質量份溶劑石腦油中一邊攪拌一邊使其加熱溶解，然後冷卻至室溫，製成混合物3。其次，將1.5質量份橡膠粒子(甘茲化成(股)製，staphyloid AC3816N)，於6質量份溶劑石腦油以12小時、20℃下靜置膨潤，製成混合物4。添加混合物4與製造物4於混合物3，進而添加2.5質量份 阻燃劑(三光(股)製「HCA-HQ」、10-(2,5-二羥基苯基)-10-氫-9-氧雜-10-磷菲-10-氧化物，平均粒徑1μm)，以3本輥混練，使均勻地分散。而且，添加10質量份活性酯系硬化劑(活性基當量約223，DIC(股)製「HPC-8000-65T」，非揮發成分65質量%之甲苯溶液)、10質量份苯氧基樹脂(重量平均分子量35000，三菱化學(股)製「YL7553」，非揮發成分30質量%之MEK與環己酮1：1溶液)、11質量份雙酚A二氰酸酯(Lonza Japan(股)製Primaset BADCy)，進而混合0.6質量份作為硬化促進劑之4-二甲基胺基吡啶之5質量%的MEK溶液、3質量份鈷(III)乙醯丙酮酸鹽(東京化成(股)製，Co(III)AcAc)之1質量%的MEK溶液，以旋轉混合機均勻地分散，製成樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 10 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, "EXA4032SS" manufactured by DIC Co., Ltd.), 1 part by mass of a bixylenol type epoxy resin (epoxy equivalent 190, Mitsubishi Chemical ( "YX4000 HK"), 12 parts by mass of modified naphthalene epoxy resin (epoxy equivalent weight: 330, "ESN475V" manufactured by Nippon Steel Chemical Co., Ltd.) was stirred in 20 parts by mass of solvent naphtha. The mixture 3 was prepared by dissolving it by heating and then cooling to room temperature. Next, 1.5 parts by mass of rubber particles (staphyloid AC3816N, manufactured by Ganzi Chemical Co., Ltd.) were allowed to stand and swelled in 6 parts by mass of solvent naphtha at 12 hours and 20 ° C to obtain a mixture 4. Adding mixture 4 and product 4 to mixture 3, and further adding 2.5 parts by mass Flame retardant (HCA-HQ), 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 1 μm), kneaded in 3 rolls to uniformly disperse. Furthermore, 10 parts by mass of an active ester-based curing agent (active base equivalent: about 223, "HPC-8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a nonvolatile content of 65 mass%), and 10 parts by mass of a phenoxy resin ( Weight average molecular weight 35000, "YL7553" manufactured by Mitsubishi Chemical Corporation, MEK and cyclohexanone 1:1 solution with 30% by mass of nonvolatile matter, and 11 parts by mass of bisphenol A dicyanate (manufactured by Lonza Japan Co., Ltd.) Primaset BADCy), further mixing 0.6 parts by mass of a 5% by mass solution of MEK as a hardening accelerator, and 3 parts by mass of cobalt (III) acetoacetate (manufactured by Tokyo Chemical Co., Ltd.). A 1 mass% MEK solution of Co(III)AcAc) was uniformly dispersed in a rotary mixer to obtain a resin varnish. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為100質量份球狀二氧化矽((股)Admatechs製「SOC2」，平均粒徑0.5μm)之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in the same manner except that the product 1 of the first embodiment was changed to 100 parts by mass of spherical cerium oxide ("SOC2" manufactured by Admatechs, and the average particle diameter was 0.5 μm). Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為100質量份球狀二氧化矽((股)Admatechs製「SOC2」，平均粒徑0.5μm )之外，特別加入0.3質量份N-苄基胺基乙醇(東京化成工業(股)製)之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 The product 1 of the first embodiment was changed to 100 parts by mass of spherical cerium oxide ("SOC2" manufactured by Admatechs, and the average particle diameter was 0.5 μm). In addition to the addition of 0.3 parts by mass of N-benzylaminoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), the resin varnish was produced in exactly the same manner. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物10之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 10. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物11之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 11. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
除將實施例1之製造物1變更為製造物12之外，其餘以完全相同方式製造樹脂清漆。接著使用該樹脂清漆，與實施例1完全相同方式進行而得到黏著薄膜。 A resin varnish was produced in exactly the same manner except that the article 1 of Example 1 was changed to the article of manufacture 12. Subsequently, this resin varnish was used in the same manner as in Example 1 to obtain an adhesive film.
結果表示於表1。 The results are shown in Table 1.
從表1之結果，實施例1~10之樹脂組成物，理解到係具有PCT耐性、低算術平均粗糙度、於低均方根粗糙度得到剝離強度充分之值。另一方面，於比較例1~5，PCT耐性劣化、算術平均粗糙度、均方根粗糙度變大、鍍敷膨脹剝離強度顯著變成較小值。 From the results of Table 1, the resin compositions of Examples 1 to 10 were understood to have PCT resistance, low arithmetic mean roughness, and sufficient peel strength at low root mean square roughness. On the other hand, in Comparative Examples 1 to 5, PCT resistance deterioration, arithmetic mean roughness, and root mean square roughness were large, and the plating expansion peeling strength was remarkably small.
成為可提供在濕式粗糙化步驟絕緣層表面之算術平均粗糙度、均方根粗糙度變小，於其上可形成具有充分之剝離強之鍍敷導體層，亦具有PCT耐性之樹脂組成物。進而成為可提供使用該之黏著薄膜、預浸料、多層印刷電路板、半導體裝置。進而亦成為可提供搭載此等之電腦、手機、數位相機、電視等之電氣製品或摩托車、汽車、電車、船舶、航空機等之交通工具。 It is provided that the arithmetic mean roughness and the root mean square roughness of the surface of the insulating layer in the wet roughening step are reduced, and a plating conductor layer having sufficient peel strength and a resin composition having PCT resistance can be formed thereon. . Further, it is possible to provide an adhesive film, a prepreg, a multilayer printed wiring board, and a semiconductor device using the adhesive film. Furthermore, it is also possible to provide electric vehicles such as computers, mobile phones, digital cameras, televisions, and the like, or vehicles such as motorcycles, automobiles, electric cars, ships, and aircraft.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI626664B (en) * | 2017-02-07 | 2018-06-11 | 聯茂電子股份有限公司 | Non-halogen epoxy resin composition having low dielectric loss |
| CN111919111A (en) * | 2018-03-30 | 2020-11-10 | 住友化学株式会社 | Sensor and method for manufacturing the same |
| TWI829727B (en) * | 2018-08-03 | 2024-01-21 | 日商力森諾科股份有限公司 | Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI626664B (en) * | 2017-02-07 | 2018-06-11 | 聯茂電子股份有限公司 | Non-halogen epoxy resin composition having low dielectric loss |
| US10611910B2 (en) | 2017-02-07 | 2020-04-07 | Iteq Corporation | Halogen-free epoxy resin composition having low dielectric loss |
| CN111919111A (en) * | 2018-03-30 | 2020-11-10 | 住友化学株式会社 | Sensor and method for manufacturing the same |
| US11892423B2 (en) | 2018-03-30 | 2024-02-06 | Sumitomo Chemical Company, Limited | Sensor and production method for same |
| TWI829727B (en) * | 2018-08-03 | 2024-01-21 | 日商力森諾科股份有限公司 | Adhesive composition, film-like adhesive, adhesive sheet, and method for manufacturing semiconductor device |
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