TWI807464B - Printed wiring board and manufacturing method of printed wiring board - Google Patents
Printed wiring board and manufacturing method of printed wiring board Download PDFInfo
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- TWI807464B TWI807464B TW110140015A TW110140015A TWI807464B TW I807464 B TWI807464 B TW I807464B TW 110140015 A TW110140015 A TW 110140015A TW 110140015 A TW110140015 A TW 110140015A TW I807464 B TWI807464 B TW I807464B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
- H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0017—Etching of the substrate by chemical or physical means
- H05K3/0026—Etching of the substrate by chemical or physical means by laser ablation
- H05K3/0032—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material
- H05K3/0035—Etching of the substrate by chemical or physical means by laser ablation of organic insulating material of blind holes, i.e. having a metal layer at the bottom
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/13—Moulding and encapsulation; Deposition techniques; Protective layers
- H05K2203/1377—Protective layers
- H05K2203/1383—Temporary protective insulating layer
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
本案提供一種印刷線路板,其具有導通可靠性高的通孔。本案的印刷線路板(11)具備:第一導體層(8);第二導體層(3);層間絕緣層(7);通孔(6),其將層間絕緣層(7)貫穿;及通孔導體(9),其配置於通孔(6)內。層間絕緣層(7)為負型的感光性樹脂組成物的硬化物,該感光性樹脂組成物含有:含羧基的樹脂(A)、一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)、及光聚合起始劑(C)。通孔(6)具有:第一導體層(8)側的第一端(61);第二導體層(3)側的第二端(62);及小直徑部(63),其位於第一端(61)與第二端(62)之間且具有較第二端(62)的直徑更小的直徑。This application provides a printed circuit board, which has through holes with high conduction reliability. The printed circuit board (11) of this case has: a first conductor layer (8); a second conductor layer (3); an interlayer insulating layer (7); a through hole (6), which penetrates the interlayer insulating layer (7); and a through hole conductor (9), which is arranged in the through hole (6). The interlayer insulating layer (7) is a cured product of a negative-type photosensitive resin composition containing: a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). The through hole (6) has: a first end (61) on the first conductor layer (8) side; a second end (62) on the second conductor layer (3) side; and a small diameter portion (63) located between the first end (61) and the second end (62) and having a diameter smaller than that of the second end (62).
Description
本案一般而言是有關一種印刷線路板及印刷線路板的製造方法,詳細而言是有關一種印刷線路板及前述印刷線路板的製造方法,該印刷線路板具備層間絕緣層,該層間絕緣層具有通孔及通孔導體。This case generally relates to a printed circuit board and a method for manufacturing a printed circuit board, and specifically relates to a printed circuit board and a method for manufacturing the aforementioned printed circuit board. The printed circuit board is provided with an interlayer insulating layer, and the interlayer insulating layer has through holes and through hole conductors.
在印刷線路板中,於層間絕緣層有時會形成通孔。In printed wiring boards, via holes are sometimes formed in interlayer insulating layers.
例如:專利文獻1揭示一種多層印刷線路板的製造方法,其包括:從已使其密合在含有無機填充材料35質量%以上的絕緣層表面的塑膠薄膜上照射二氧化碳雷射,而形成頂部直徑100 μm以下的盲通孔的步驟。 [先前技術文獻] (專利文獻) For example, Patent Document 1 discloses a method for manufacturing a multilayer printed circuit board, which includes: irradiating a carbon dioxide laser on a plastic film that has been made to adhere to the surface of an insulating layer containing more than 35% by mass of inorganic filler material, and forming a step of blind via holes with a top diameter of 100 μm or less. [Prior Art Literature] (patent documents)
專利文獻1:日本特開2016-181731號公報Patent Document 1: Japanese Patent Laid-Open No. 2016-181731
本案所欲解決的問題在於提供一種印刷線路板及前述印刷線路板的製造方法,該印刷線路板具有導通可靠性高的通孔。 [解決問題的技術手段] The problem to be solved in this case is to provide a printed circuit board and a method for manufacturing the aforementioned printed circuit board. The printed circuit board has through holes with high conduction reliability. [Technical means to solve the problem]
本案的一態樣的印刷線路板具備:第一導體層;第二導體層;層間絕緣層,其介於前述第一導體層與前述第二導體層之間;通孔,其將前述層間絕緣層貫穿;及通孔導體,其配置於前述通孔內且將前述第一導體層與前述第二導體層導通。前述層間絕緣層為負型的感光性樹脂組成物的硬化物,該感光性樹脂組成物含有:含羧基的樹脂(A)、一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)、及光聚合起始劑(C)。前述通孔具有:第一端,其為前述第一導體層側的端;第二端,其為前述第二導體層側的端;及小直徑部,其位於前述第一端與前述第二端之間且具有較前述第二端的直徑更小的直徑。A printed circuit board according to one aspect of the present case includes: a first conductor layer; a second conductor layer; an interlayer insulating layer interposed between the first conductor layer and the second conductor layer; a through hole penetrating the interlayer insulating layer; and a via conductor disposed in the through hole and conducting the first conductor layer and the second conductor layer. The aforementioned interlayer insulating layer is a cured product of a negative-type photosensitive resin composition containing a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). The through hole has: a first end which is an end on the side of the first conductor layer; a second end which is an end on the side of the second conductor layer; and a small diameter portion which is located between the first end and the second end and has a diameter smaller than that of the second end.
本案的一態樣的印刷線路板的製造方法為製造前述印刷線路板的方法,且包括:準備負型的前述感光性樹脂組成物以及基板,該感光性樹脂組成物含有:前述含羧基的樹脂(A)、前述一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)、及前述光聚合起始劑(C),該基板具有絕緣層及重疊在前述絕緣層的前述第二導體層;將由前述感光性樹脂組成物所製得的被膜以將前述第二導體層覆蓋的方式重疊在前述基板上;對前述被膜的包含前述通孔的圖案的負型圖案狀的區域進行曝光後,使用鹼性水溶液來實施顯影處理,而製作前述層間絕緣層及將前述層間絕緣層貫穿的前述通孔。A method for manufacturing a printed wiring board according to an aspect of the present case is a method for manufacturing the aforementioned printed wiring board, and includes: preparing a negative-type aforementioned photosensitive resin composition and a substrate, the photosensitive resin composition including: the aforementioned carboxyl group-containing resin (A), the aforementioned unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and the aforementioned photopolymerization initiator (C); the substrate has an insulating layer and the aforementioned second conductor layer stacked on the aforementioned insulating layer; The aforementioned second conductor layer is superimposed on the aforementioned substrate; after exposing the negative pattern-like region of the aforementioned coating film including the pattern of the aforementioned via hole, a development process is performed using an alkaline aqueous solution to form the aforementioned interlayer insulating layer and the aforementioned via hole penetrating the aforementioned interlayer insulating layer.
(1)所要解決的問題的詳細內容 日本特開2016-181731號公報揭示一種多層印刷線路板的製造方法,其包括:從已使其密合在含有無機填充材料35質量%以上的絕緣層表面的塑膠薄膜上照射二氧化碳雷射,而形成頂部直徑100 μm以下的盲通孔的步驟。然而,根據本發明人等的技術思想,日本特開2016-181731號公報中所記載的發明在通孔的導通可靠性上尚有改善的空間。錐形狀的通孔的導通可靠性容易降低。 (1) Details of the problem to be solved Japanese Patent Laid-Open No. 2016-181731 discloses a method for manufacturing a multilayer printed circuit board, which includes: irradiating a carbon dioxide laser from a plastic film that has been made to adhere to the surface of an insulating layer containing more than 35% by mass of an inorganic filler material, and forming blind through holes with a top diameter of 100 μm or less. However, according to the technical idea of the present inventors, the invention described in Japanese Patent Application Laid-Open No. 2016-181731 still has room for improvement in the conduction reliability of the via hole. The conduction reliability of the tapered via hole tends to decrease.
本發明人等透過對層間絕緣層的材料的研究開發而獲得下述技術思想:有時在層間絕緣層的通孔的導體會發生龜裂,且此情形會使導通可靠性惡化。The inventors of the present invention obtained the following technical idea through the research and development of the material of the interlayer insulating layer: cracks may occur in the conductor of the through-hole of the interlayer insulating layer, and this will deteriorate the conduction reliability.
於是,本發明人等為了提供一種印刷線路板及前述印刷線路板的製造方法,該印刷線路板具有導通可靠性高的通孔,而進行研究開發後,結果遂完成本案。Then, the inventors of the present invention completed the present project as a result of research and development in order to provide a printed wiring board having through-holes with high conduction reliability and a method of manufacturing the aforementioned printed wiring board.
(2)概要 說明本案的一實施形態。 (2) Summary One embodiment of this case will be described.
本實施形態的印刷線路板11具備:第一導體層8;第二導體層3;層間絕緣層7,其介於第一導體層8與第二導體層3之間;通孔6,其將層間絕緣層7貫穿;及通孔導體9,其配置於通孔6內且將第一導體層8與第二導體層3導通(參照第1圖E)。層間絕緣層7為負型的感光性樹脂組成物的硬化物,該感光性樹脂組成物含有:含羧基的樹脂(A)、一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)、及光聚合起始劑(C)。通孔6具有:第一端61,其為第一導體層8側的端;第二端62,其為第二導體層3側的端;及小直徑部63,其位於第一端61與第二端62之間且具有較第二端62的直徑更小的直徑。The printed circuit board 11 of this embodiment has: a first conductor layer 8; a second conductor layer 3; an interlayer insulating layer 7, which is interposed between the first conductor layer 8 and the second conductor layer 3; a through hole 6, which penetrates the interlayer insulating layer 7; and a via conductor 9, which is arranged in the through hole 6 and conducts the first conductor layer 8 and the second conductor layer 3 (refer to FIG. 1 E). The interlayer insulating layer 7 is a cured product of a negative photosensitive resin composition containing a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). The through hole 6 has: a first end 61 which is an end on the first conductor layer 8 side; a second end 62 which is an end on the second conductor layer 3 side;
本實施形態中是從負型的感光性樹脂組成物製作層間絕緣層7,該感光性樹脂組成物含有:含羧基的樹脂(A)、一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)、及光聚合起始劑(C)。因此,將由感光性樹脂組成物所製得的被膜4曝光成圖案狀後以鹼性水溶液來進行顯影,即能夠容易製作層間絕緣層7並且製作具有小直徑部63的通孔6。In this embodiment, the interlayer insulating layer 7 is fabricated from a negative-type photosensitive resin composition containing a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C). Therefore, the interlayer insulating layer 7 and the through hole 6 having the small-diameter portion 63 can be easily formed by exposing the film 4 made of the photosensitive resin composition in a pattern and then developing it with an alkaline aqueous solution.
容易形成小直徑部63的理由我們推測是如下所述。若光照射在由負型的感光性樹脂組成物所形成的被膜4的要形成通孔6的第一端61的面而被膜4曝光,則光會在被膜4的內部散射,而越接近被膜4的深部則較廣的部分越容易硬化。因此,成為通孔6的非硬化部分5緩緩縮小,而容易形成直徑較第一端61更小的小直徑部63。此外,在被膜4內的更深部側,光會被被膜4吸收,而光不容易傳達,且因此使光的散射的影響降低,故被膜4的硬化不容易進行,因此第二端62的直徑較小直徑部63更加增加,而通孔6容易成為從小直徑部63至第二端62擴展的形狀。The reason why it is easy to form the small-diameter portion 63 is presumed to be as follows. When light is irradiated on the surface of the first end 61 of the film 4 formed by the negative-type photosensitive resin composition to form the through hole 6 and the film 4 is exposed, the light will be scattered inside the film 4, and the closer to the deep part of the film 4, the easier it is to harden the wider part. Therefore, the non-cured portion 5 to be the through hole 6 gradually shrinks, and the small-diameter portion 63 having a diameter smaller than that of the first end 61 is easily formed. In addition, in the deeper side of the coating 4, light is absorbed by the coating 4, and the light is not easily transmitted, and therefore the influence of light scattering is reduced, so the hardening of the coating 4 is not easy, so the second end 62 has a smaller diameter.
特別是,當從感光性樹脂組成物製作膜厚5 μm以上且100 μm以下的被膜4,並將在365 nm±65 nm的波長區中的至少一個波長具有光譜強度的紫外線照射在被膜4中的除了直徑5 μm以上且100 μm以下的圓形的部分以外的區域,然後對被膜4實施藉由鹼性水溶液來進行的顯影處理時,較佳是感光性樹脂組成物具備下述這樣的特性:會於圓形的部分形成通孔6且通孔6具有小直徑部63。此時,較佳是:相對於第二端62的直徑,通孔6的小直徑部63的直徑為65%以上且未達100%,相對於第二端62的直徑,第一端61的直徑為65%以上,第一端61的直徑為100 μm以下。這樣的特性能夠在以下詳細說明的感光性樹脂組成物的組成的範圍內實現。再者,將紫外線照射在被膜4的方法可為使用負型遮罩的曝光法,亦可為直接描繪法。具體的試驗方法及條件的例子記載於實施例的欄中。In particular, when a film 4 with a film thickness of 5 μm to 100 μm is produced from a photosensitive resin composition, and ultraviolet rays having a spectral intensity at least one wavelength in the wavelength region of 365 nm±65 nm are irradiated on areas of the film 4 other than the circular portion with a diameter of 5 μm to 100 μm, and then the film 4 is subjected to development treatment by an alkaline aqueous solution, it is preferable that the photosensitive resin composition has the following characteristics: The circular portion forms the through hole 6 and the through hole 6 has a small diameter portion 63 . At this time, it is preferable that the diameter of the small-diameter portion 63 of the through hole 6 is 65% or more and less than 100% of the diameter of the second end 62, the diameter of the first end 61 is 65% or more of the diameter of the second end 62, and the diameter of the first end 61 is 100 μm or less. Such characteristics can be realized within the range of the composition of the photosensitive resin composition described in detail below. In addition, the method of irradiating ultraviolet rays to the film 4 may be an exposure method using a negative mask or a direct drawing method. Examples of specific test methods and conditions are described in the column of Examples.
此外,本實施形態中,通孔6具有這樣的形狀,而即使由熱所造成的負載施加在通孔導體9等而在通孔導體9內產生應力,通孔導體9與第二導體層3之間的介面仍不容易發生龜裂。因此,藉由通孔,即能夠容易獲得第一導體層8與第二導體層3之間的介面的良好的導通可靠性。我們推測其原因為:本實施形態中如上所述,層間絕緣層7的通孔6的內面由於具有直徑從小直徑部63至第二端62增加的形狀,故即使在通孔導體9內產生應力,與通孔的第二端62相比,應力仍會更集中在小直徑部63。In addition, in this embodiment, the via hole 6 has such a shape that even if a load due to heat is applied to the via hole conductor 9 and the like to generate stress in the via hole conductor 9, the interface between the via hole conductor 9 and the second conductor layer 3 is not easily cracked. Therefore, good conduction reliability of the interface between the first conductor layer 8 and the second conductor layer 3 can be easily obtained through the through holes. The reason for this is presumed to be that in the present embodiment, since the inner surface of the via hole 6 of the interlayer insulating layer 7 has a shape in which the diameter increases from the small diameter portion 63 to the second end 62, even if stress occurs in the via hole conductor 9, the stress is concentrated more at the small diameter portion 63 than at the second end 62 of the via hole.
小直徑部63的最小直徑以第二端62的直徑的65%以上且未達100%為佳。此時,特別容易獲得由通孔所得的導通可靠性。小直徑部63的最小直徑若為第二端62的直徑的95%以下則較佳,若為90%以下則更佳。此外,小直徑部63的最小直徑若為第二端62的直徑的67%以上則較佳,若為79%以上則更佳。The minimum diameter of the small-diameter portion 63 is preferably at least 65% and less than 100% of the diameter of the second end 62 . At this time, it is particularly easy to obtain the conduction reliability obtained by the via hole. The minimum diameter of the small-diameter portion 63 is preferably 95% or less of the diameter of the second end 62, more preferably 90% or less. In addition, the minimum diameter of the small-diameter portion 63 is preferably 67% or more of the diameter of the second end 62, and more preferably 79% or more.
相對於第二端62的直徑,第一端61的直徑以65%以上為佳。此時,使鍍覆液滲入至通孔6內,即能夠容易製作通孔導體9。換言之,以鍍覆法即能夠容易製作通孔導體9。因此,容易獲得更良好的導通可靠性。從獲得製作通孔6時的良好的解析性的觀點來看,相對於第二端62的直徑,第一端61的直徑以70%以上較佳,以75%以上更佳,以80%以上特佳。此外,相對於第二端62的直徑,第一端61的直徑以未達130%為佳,以未達120%較佳,以未達110%更佳,以未達100%特佳。Relative to the diameter of the second end 62, the diameter of the first end 61 is preferably more than 65%. At this time, the through-hole conductor 9 can be easily produced by infiltrating the plating solution into the through-hole 6 . In other words, through-hole conductor 9 can be easily produced by the plating method. Therefore, better conduction reliability is easily obtained. From the viewpoint of obtaining good resolution when forming the through hole 6 , the diameter of the first end 61 is preferably 70% or more, more preferably 75% or more, and most preferably 80% or more of the diameter of the second end 62 . In addition, relative to the diameter of the second end 62, the diameter of the first end 61 is preferably less than 130%, more preferably less than 120%, more preferably less than 110%, and most preferably less than 100%.
此外,第一端61的直徑以100 μm以下為佳。此時,以鍍覆法等即能夠容易在通孔6內製作通孔導體9。因此,容易獲得更良好的導通可靠性。此外,第一端61的直徑例如為5 μm以上。In addition, the diameter of the first end 61 is preferably less than 100 μm. In this case, the through-hole conductor 9 can be easily produced in the through-hole 6 by a plating method or the like. Therefore, better conduction reliability is easily obtained. In addition, the diameter of the first end 61 is, for example, 5 μm or more.
(3)感光性樹脂組成物 以下具體說明本實施形態的感光性樹脂組成物的詳細內容。再者,下述說明中,所謂「(甲基)丙烯酸」,是意指「丙烯酸」及「甲基丙烯酸」之中的至少一種。例如:(甲基)丙烯酸酯是意指丙烯酸酯及甲基丙烯酸酯之中的至少一種。 (3) Photosensitive resin composition The details of the photosensitive resin composition of the present embodiment will be specifically described below. In addition, in the following description, "(meth)acryl" means at least one of "acryl" and "methacryl". For example: (meth)acrylate means at least one of acrylate and methacrylate.
本實施形態的感光性樹脂組成物含有:含羧基的樹脂(A)、一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)、及光聚合起始劑(C)。The photosensitive resin composition of the present embodiment contains a carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C).
含羧基的樹脂(A)較佳是含有下述式(1)表示的具有雙酚茀骨架的含羧基的樹脂(A1)。若含羧基的樹脂(A)具有體積大的雙酚茀骨架,則當將紫外線照射在由感光性樹脂組成物所製作的被膜4時,不容易在深部發生光散射。此外,含羧基的樹脂(A1)具有雙酚茀骨架,即能夠對感光性樹脂組成物的硬化物賦予高耐熱性及絕緣可靠性。The carboxyl group-containing resin (A) preferably contains a carboxyl group-containing resin (A1) represented by the following formula (1) and having a bisphenol fennel skeleton. If the carboxyl group-containing resin (A) has a bulky bisphenol-skeleton skeleton, when ultraviolet rays are irradiated on the film 4 made of the photosensitive resin composition, light scattering is less likely to occur in the deep part. In addition, the carboxyl group-containing resin (A1) has a bisphenol peroxide skeleton, that is, can impart high heat resistance and insulation reliability to the cured product of the photosensitive resin composition.
式(1)中,R 1~R 8分別獨立地為氫、碳數1~5的烷基、或鹵素。換言之,式(1)中,R 1~R 8分別可為氫,亦可為碳數1~5的烷基、或鹵素。其原因為:即使芳香環中的氫經低分子量的烷基或鹵素所取代,仍不會對含羧基的樹脂(A1)的物性造成不良影響,反而,取代而亦有時會提高包含含羧基的樹脂(A1)的感光性樹脂組成物的硬化物的耐熱性或阻燃性。 In formula (1), R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 5 carbons, or halogen. In other words, in formula (1), R 1 to R 8 may each be hydrogen, an alkyl group having 1 to 5 carbons, or a halogen. The reason is that even if the hydrogen in the aromatic ring is replaced by a low-molecular-weight alkyl group or halogen, it will not adversely affect the physical properties of the carboxyl-containing resin (A1). On the contrary, the substitution may sometimes improve the heat resistance or flame retardancy of the cured product of the photosensitive resin composition containing the carboxyl-containing resin (A1).
含羧基的樹脂(A1)是以例如下述方式合成:使具有式(1)表示的雙酚茀骨架的環氧化合物(a1)與含不飽和基的羧酸(a2)進行反應後,使由此所得的中間體與酸酐(a3)進行反應。The carboxyl group-containing resin (A1) is synthesized, for example, by reacting an epoxy compound (a1) having a bisphenol fluorine skeleton represented by formula (1) with an unsaturated group-containing carboxylic acid (a2), and then reacting the resulting intermediate with an acid anhydride (a3).
環氧化合物(a1)具有例如下述式(2)表示的結構。式(2)中,n為例如在0~20的範圍內的整數。為了適當地控制含羧基的樹脂(A1)的分子量,n的平均更佳是在0~1的範圍內。若n的平均在0~1的範圍內,則容易抑制含羧基的樹脂(A1)的過剩的分子量增加。此外,式(2)中,R 1~R 8分別獨立地為氫、碳數1~5的烷基、或鹵素。 The epoxy compound (a1) has, for example, a structure represented by the following formula (2). In formula (2), n is an integer within the range of 0-20, for example. In order to appropriately control the molecular weight of the carboxyl group-containing resin (A1), the average of n is more preferably within the range of 0-1. When the average of n exists in the range of 0-1, it will become easy to suppress the excess molecular weight increase of carboxyl group-containing resin (A1). In addition, in formula (2), R 1 to R 8 are each independently hydrogen, an alkyl group having 1 to 5 carbons, or halogen.
含不飽和基的羧酸(a2)含有例如:一分子中具有僅1個乙烯性不飽和基的化合物。更具體而言,含不飽和基的羧酸(a2)含有例如從由下述所組成的群組中選出的至少一種化合物:丙烯酸、甲基丙烯酸、ω-羧基-聚己內酯(n≒2)單丙烯酸酯、巴豆酸、肉桂酸、2-丙烯醯氧基乙基琥珀酸、2-甲基丙烯醯氧基乙基琥珀酸、2-丙烯醯氧基乙基鄰苯二甲酸、2-甲基丙烯醯氧基乙基鄰苯二甲酸、2-丙烯醯氧基丙基鄰苯二甲酸、2-甲基丙烯醯氧基丙基鄰苯二甲酸、2-丙烯醯氧基乙基馬來酸、2-甲基丙烯醯氧基乙基馬來酸、丙烯酸β-羧基乙酯、2-丙烯醯氧基乙基四氫鄰苯二甲酸、2-甲基丙烯醯氧基乙基四氫鄰苯二甲酸、2-丙烯醯氧基乙基六氫鄰苯二甲酸、及2-甲基丙烯醯氧基乙基六氫鄰苯二甲酸。較佳是:含不飽和基的羧酸(a2)含有丙烯酸。此外,當含不飽和基的羧酸(a2)含有丙烯酸時,丙烯酸較佳是含有含不飽和基的羧酸(a2)中的50 mol%以上,更佳是含有80 mol%以上,再更佳是含有85 mol%以上,特佳是含有90 mol%以上。The unsaturated group-containing carboxylic acid (a2) includes, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2) contains, for example, at least one compound selected from the group consisting of acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, crotonic acid, cinnamic acid, 2-acryloxyethylsuccinic acid, 2-methacryloxyethylsuccinic acid, 2-acryloxyethylphthalic acid, 2-methacryloxyethylphthalic acid acid, 2-acryloxypropylphthalate, 2-methacryloxypropylphthalate, 2-acryloxyethylmaleic acid, 2-methacryloxyethylmaleic acid, β-carboxyethyl acrylate, 2-acryloxyethyltetrahydrophthalate, 2-methacryloxyethyltetrahydrophthalate, 2-acryloxyethylhexahydrophthalate, and 2- Methacryloxyethylhexahydrophthalic acid. Preferably, the unsaturated group-containing carboxylic acid (a2) contains acrylic acid. In addition, when the unsaturated group-containing carboxylic acid (a2) contains acrylic acid, the acrylic acid preferably contains 50 mol% or more of the unsaturated group-containing carboxylic acid (a2), more preferably contains 80 mol% or more, more preferably contains 85 mol% or more, particularly preferably contains 90 mol% or more.
在使環氧化合物(a1)與含不飽和基的羧酸(a2)進行反應時,能夠採用適當的方法。例如:在環氧化合物(a1)的溶劑溶液中加入含不飽和基的羧酸(a2),且進一步因應需要來加入熱聚合抑制劑及觸媒並攪拌混合,而獲得反應性溶液。藉由慣用方法來在較佳為60℃以上且150℃以下、特佳為80℃以上且120℃以下的溫度使此反應性溶液進行反應,即能夠獲得中間體。此時,溶劑能夠含有例如從由下述所組成的群組中選出的至少一種成分:甲基乙基酮、環己酮等酮類;甲苯、二甲苯等芳香族烴類;乙酸乙酯、乙酸丁酯、賽璐蘇乙酸酯、丁基賽璐蘇乙酸酯、卡必醇乙酸酯、丁基卡必醇乙酸酯、丙二醇單甲基醚乙酸酯等乙酸酯類;及二烷基二醇醚類。熱聚合抑制劑能夠含有例如從由下述所組成的群組中選出的至少一種成分:氫醌、甲基氫醌及氫醌單甲基醚。觸媒能夠含有例如從由下述所組成的群組中選出的至少一種成分:苯甲基二甲基胺、三乙胺等三級胺類;氯化三甲基苯甲基銨、氯化甲基三乙基銨等四級銨鹽類;三苯膦;及三苯銻。When reacting the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2), an appropriate method can be employed. For example: add the unsaturated group-containing carboxylic acid (a2) to the solvent solution of the epoxy compound (a1), and further add a thermal polymerization inhibitor and a catalyst as needed, and stir to obtain a reactive solution. The intermediate can be obtained by reacting the reactive solution at a temperature of preferably 60° C. to 150° C., particularly preferably 80° C. to 120° C., by a conventional method. In this case, the solvent can contain, for example, at least one component selected from the group consisting of: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; acetates such as ethyl acetate, butyl acetate, celluloid acetate, butyl celluloid acetate, carbitol acetate, butyl carbitol acetate, and propylene glycol monomethyl ether acetate; and dialkyl glycol ethers. The thermal polymerization inhibitor can contain, for example, at least one component selected from the group consisting of hydroquinone, methylhydroquinone, and hydroquinone monomethyl ether. The catalyst can contain, for example, at least one component selected from the group consisting of: tertiary amines such as benzyldimethylamine and triethylamine; quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride; triphenylphosphine; and triphenylantimony.
較佳是:觸媒含有特別是三苯膦。換言之,較佳是:在三苯膦存在下使環氧化合物(a1)與含不飽和基的羧酸(a2)進行反應。此時,能夠特別促進環氧化合物(a1)中的環氧基與含不飽和基的羧酸(a2)的開環加成反應,而能夠達成95%以上、或97%以上、或幾乎100%的反應率(轉化率)。Preferably the catalyst contains especially triphenylphosphine. In other words, it is preferred to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in the presence of triphenylphosphine. At this time, the ring-opening addition reaction of the epoxy group in the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) can be particularly accelerated, and a reaction rate (conversion rate) of 95% or more, or 97% or more, or almost 100% can be achieved.
亦較佳是在空氣起泡下使環氧化合物(a1)與含不飽和基的羧酸(a2)進行反應。此時,能夠抑制不飽和基的加成聚合反應,而抑制中間體的分子量增加及中間體的溶液凝膠化。此外,能夠抑制最終產物亦即含羧基的樹脂(A1)過度著色。It is also preferred to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) under air bubbling. In this case, the addition polymerization reaction of the unsaturated group can be suppressed, and the increase in the molecular weight of the intermediate and the solution gelation of the intermediate can be suppressed. In addition, excessive coloring of the carboxyl group-containing resin (A1), which is the final product, can be suppressed.
使環氧化合物(a1)與含不飽和基的羧酸(a2)進行反應時,含不飽和基的羧酸(a2)相對於環氧化合物(a1)的環氧基1 mol的量以0.8 mol以上且1.2 mol以下為佳。此時,能夠獲得具有優異的感光性及安定性的感光性樹脂組成物。When the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2), the amount of the unsaturated group-containing carboxylic acid (a2) relative to 1 mol of the epoxy group of the epoxy compound (a1) is preferably 0.8 mol or more and 1.2 mol or less. In this case, a photosensitive resin composition having excellent photosensitivity and stability can be obtained.
以上述方式獲得的中間體具備由環氧化合物(a1)的環氧基與含不飽和基的羧酸(a2)的羧基的反應所產生的羥基。The intermediate obtained as described above has a hydroxyl group generated by the reaction of the epoxy group of the epoxy compound (a1) and the carboxyl group of the unsaturated group-containing carboxylic acid (a2).
然後,使中間體與酸酐(a3)進行反應。酸酐(a3)含有例如酸二酐(a4)。Then, the intermediate is reacted with an acid anhydride (a3). The acid anhydride (a3) contains, for example, an acid dianhydride (a4).
酸二酐(a4)為具有兩個酸酐基的化合物。酸二酐(a4)能夠含有四羧酸的酐。酸二酐(a4)能夠含有例如從由下述所組成的群組中選出的至少一種化合物:1,2,4,5-苯四甲酸二酐、二苯甲酮四甲酸二酐、甲基環己烯四甲酸二酐、四甲酸二酐、萘-1,4,5,8-四甲酸二酐、伸乙基四甲酸二酐、9,9’-雙(3,4-二羧基苯基)茀二酐、甘油雙(偏苯三甲酸酯酐)單乙酸酯、乙二醇雙(偏苯三甲酸酯酐)、3,3’,4,4’-二苯基碸四甲酸二酐、1,3,3a,4,5,9b-六氫-5(四氫-2,5-二酮基-3-呋喃基)萘并[1,2-c]呋喃-1,3-二酮、1,2,3,4-丁烷四甲酸二酐、及3,3’,4,4’-聯苯四甲酸二酐。特佳是:酸二酐(a4)含有3,3’,4,4’-聯苯四甲酸二酐。此時,能夠一面感光性樹脂組成物確保良好的顯影性,一面抑制由感光性樹脂組成物所製作的被膜4的沾黏性並且更加提高硬化物的絕緣可靠性及耐鍍覆性。Acid dianhydride (a4) is a compound which has two acid anhydride groups. Acid dianhydride (a4) can contain the anhydride of tetracarboxylic acid. The acid dianhydride (a4) can contain, for example, at least one compound selected from the group consisting of 1,2,4,5-benzenetetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 9,9'-bis(3,4-dicarboxyphenyl) terrene dianhydride, glycerol bis(trimellitate) anhydride) monoacetate, ethylene glycol bis(trimellitic acid anhydride), 3,3’,4,4’-diphenylenetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-diketonyl-3-furyl)naphtho[1,2-c]furan-1,3-dione, 1,2,3,4-butanetetracarboxylic dianhydride, and 3,3’,4,4’-bi Pyrellitic dianhydride. Particularly preferably, the acid dianhydride (a4) contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. In this case, while the photosensitive resin composition ensures good developability, the stickiness of the film 4 made of the photosensitive resin composition can be suppressed, and the insulation reliability and plating resistance of the cured product can be further improved.
酸酐(a3)可含有酸一酐(a5)。酸一酐(a5)為具有一個酸酐基的化合物。酸一酐(a5)能夠含有二羧酸的酐。酸一酐(a5)能夠含有例如從由下述所組成的群組中選出的至少一種化合物:鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基納迪克酸酐、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐、琥珀酸酐、甲基琥珀酸酐、馬來酸酐、檸康酸酐、戊二酸酐、環己烷-1,2,4-三甲酸-1,2-酐、及伊康酸酐。特佳是:酸一酐(a5)含有1,2,3,6-四氫鄰苯二甲酸酐。換言之,較佳是:酸酐(a3)含有1,2,3,6-四氫鄰苯二甲酸酐。此時,能夠一面確保感光性樹脂組成物的良好的顯影性,一面更加抑制由感光性樹脂組成物所形成的被膜4的沾黏性並且更加提高硬化物的絕緣可靠性及耐鍍覆性。相對於酸一酐(a5)整體,1,2,3,6-四氫鄰苯二甲酸酐較佳是在20 mol%以上且100 mol%以下的範圍內,更佳是在40 mol%以上且100 mol%以下的範圍內,但不限於此。The acid anhydride (a3) may contain an acid monoanhydride (a5). Acid monoanhydride (a5) is a compound having one acid anhydride group. Acid monoanhydride (a5) can contain the anhydride of dicarboxylic acid. Acid monoanhydride (a5) can contain, for example, at least one compound selected from the group consisting of phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylsuccinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane-1,2,4- Triformic acid-1,2-anhydride, and itaconic anhydride. Particularly preferably, the acid monoanhydride (a5) contains 1,2,3,6-tetrahydrophthalic anhydride. In other words, it is preferable that the acid anhydride (a3) contains 1,2,3,6-tetrahydrophthalic anhydride. In this case, while ensuring good developability of the photosensitive resin composition, the stickiness of the film 4 formed of the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. The content of 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 mol% to 100 mol%, more preferably 40 mol% to 100 mol%, but not limited thereto.
在使中間體與酸酐(a3)進行反應時,能夠採用適當的方法。例如:在中間體的溶劑溶液中加入酸酐(a3),且進一步因應需要來加入熱聚合抑制劑及觸媒並攪拌混合,而獲得反應性溶液。藉由慣用方法來在較佳為60℃以上且150℃以下、特佳為80℃以上且120℃以下的溫度使此反應性溶液進行反應,即能夠獲得具有雙酚茀骨架的含羧基的樹脂(A1)。溶劑、觸媒及聚合抑制劑能夠使用適當物,亦能夠直接使用在合成中間體時所使用的溶劑、觸媒及聚合抑制劑。When reacting the intermediate with the acid anhydride (a3), an appropriate method can be employed. For example: add an acid anhydride (a3) to the solvent solution of the intermediate, and further add a thermal polymerization inhibitor and a catalyst as needed and stir and mix to obtain a reactive solution. The reactive solution is reacted at a temperature of preferably 60° C. to 150° C., particularly preferably 80° C. to 120° C., by a conventional method to obtain a carboxyl group-containing resin (A1) having a bisphenol fennel skeleton. Suitable solvents, catalysts, and polymerization inhibitors can be used, and the solvents, catalysts, and polymerization inhibitors used in the synthesis of intermediates can be used as they are.
較佳是:觸媒含有特別是三苯膦。換言之,較佳是在三苯膦存在下使中間體與酸酐(a3)進行反應。此時,會特別促進中間體與酸酐(a3)的反應,而能夠達成90%以上、95%以上、97%以上、或幾乎100%的反應率(轉化率)。Preferably the catalyst contains especially triphenylphosphine. In other words, it is preferred to react the intermediate with the acid anhydride (a3) in the presence of triphenylphosphine. In this case, the reaction between the intermediate and the acid anhydride (a3) is particularly accelerated, and a reaction rate (conversion rate) of 90% or more, 95% or more, 97% or more, or almost 100% can be achieved.
當酸酐(a3)含有酸二酐(a4)時,相對於環氧化合物(a1)的環氧基1 mol,酸二酐(a4)的量以0.05 mol以上且0.24 mol以下為佳。此時,能夠容易獲得經適度調整酸值及分子量的具有雙酚茀骨架的含羧基的樹脂(A1)。When the acid anhydride (a3) contains the acid dianhydride (a4), the amount of the acid dianhydride (a4) is preferably not less than 0.05 mol and not more than 0.24 mol relative to 1 mol of epoxy groups of the epoxy compound (a1). In this case, the carboxyl group-containing resin (A1) having a bisphenol fennel skeleton with an appropriately adjusted acid value and molecular weight can be easily obtained.
當酸酐(a3)進一步含有酸一酐(a5)時,相對於環氧化合物(a1)的環氧基1 mol,酸一酐(a5)的量以0.3 mol以上且0.7 mol以下為佳。此時,能夠容易獲得經適度調整酸值及分子量的具有雙酚茀骨架的含羧基的樹脂(A1)。When the acid anhydride (a3) further contains an acid anhydride (a5), the amount of the acid anhydride (a5) is preferably not less than 0.3 mol and not more than 0.7 mol relative to 1 mol of epoxy groups in the epoxy compound (a1). In this case, the carboxyl group-containing resin (A1) having a bisphenol fennel skeleton with an appropriately adjusted acid value and molecular weight can be easily obtained.
亦較佳是在空氣起泡下使中間體與酸酐(a3)進行反應。此時,會抑制產生的具有雙酚茀骨架的含羧基的樹脂(A1)的分子量過度增加,而會特別提高感光性樹脂組成物的藉由鹼性水溶液來進行的顯影性。It is also preferred to react the intermediate with the anhydride (a3) under air bubbles. In this case, excessive increase in the molecular weight of the carboxyl group-containing resin (A1) having a bisphenol terpene skeleton is suppressed, and the developability of the photosensitive resin composition by an aqueous alkaline solution is particularly improved.
說明感光性樹脂組成物中的具有雙酚茀骨架的含羧基的樹脂(A1)以外的成分。Components other than the carboxyl group-containing resin (A1) having a bisphenol fennel skeleton in the photosensitive resin composition will be described.
感光性樹脂組成物如上所述,含有:含羧基的樹脂(A)、一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)、及光聚合起始劑(C)。The photosensitive resin composition contains the carboxyl group-containing resin (A), an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule, and a photopolymerization initiator (C) as described above.
含羧基的樹脂(A)可僅含有具有雙酚茀骨架的含羧基的樹脂(A1),亦可僅含有具有雙酚茀骨架的含羧基的樹脂(A1)以外的含羧基的樹脂。或者,亦可含有具有雙酚茀骨架的含羧基的樹脂(A1)及具有雙酚茀骨架的含羧基的樹脂(A1)以外的含羧基的樹脂雙方。具有雙酚茀骨架的含羧基的樹脂(A1)以外的含羧基的樹脂包含不具有雙酚茀骨架的含羧基的樹脂(以下亦稱為含羧基的樹脂(A2))。The carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1) having a bisphenol fennel skeleton, or may contain only carboxyl group-containing resins other than the carboxyl group-containing resin (A1) having a bisphenol fennel skeleton. Alternatively, both the carboxyl group-containing resin (A1) having a bisphenol fennel skeleton and the carboxyl group-containing resin (A1) having a bisphenol fennel skeleton may be contained. Carboxyl group-containing resins other than the carboxyl group-containing resin (A1) having a bisphenol permeil skeleton include carboxyl group-containing resins (hereinafter also referred to as carboxyl group-containing resin (A2)) not having a bisphenol permeil skeleton.
含羧基的樹脂(A2)能夠含有例如:具有羧基且不具有光聚合性的化合物(以下稱為(A2-1)成分)。(A2-1)成分含有例如一種乙烯性不飽和單體的聚合物,該乙烯性不飽和單體包含具有羧基的乙烯性不飽和化合物。具有羧基的乙烯性不飽和化合物能夠含有:丙烯酸、甲基丙烯酸、及ω-羧基聚己內酯(n≒2)單丙烯酸酯等化合物。具有羧基的乙烯性不飽和化合物亦能夠含有:季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯等與二元酸酐的反應物。乙烯性不飽和單體可進一步含有:鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基-2-羥基乙酯、直鏈或分枝的脂肪族或脂環族(惟,環中一部分可具有不飽和鍵)的(甲基)丙烯酸酯等不具有羧基的乙烯性不飽和化合物。The carboxyl group-containing resin (A2) can contain, for example, a compound (hereinafter referred to as (A2-1) component) which has a carboxyl group and does not have photopolymerization properties. (A2-1) The polymer which a component contains, for example 1 type of ethylenically unsaturated monomer containing the ethylenically unsaturated compound which has a carboxyl group. The ethylenically unsaturated compound having a carboxyl group can include compounds such as acrylic acid, methacrylic acid, and ω-carboxypolycaprolactone (n≒2) monoacrylate. The ethylenically unsaturated compound which has a carboxyl group can also contain the reactant with dibasic acid anhydride, such as pentaerythritol triacrylate and pentaerythritol trimethacrylate. Ethylenically unsaturated monomers may further include: 2-(meth)acryloxyethyl phthalate, 2-(meth)acryloxyethyl-2-hydroxyethyl phthalate, straight-chain or branched aliphatic or alicyclic (meth)acrylic acid esters that do not have carboxyl groups, etc.
含羧基的樹脂(A2)可含有具有羧基及乙烯性不飽和基的化合物(以下稱為(A2-2)成分)。此外,含羧基的樹脂(A2)可僅含有(A2-2)成分。(A2-2)成分含有例如一種樹脂(稱為第一樹脂(x)),其為特定中間體與從多元羧酸及其酐的群組中選出的至少一種化合物(x3)的反應物,該特定中間體為一分子中具有兩個以上的環氧基的環氧化合物(x1)與乙烯性不飽和化合物(x2)的反應物。第一樹脂(x)能夠以例如下述方式獲得:使環氧化合物(x1)中的環氧基與乙烯性不飽和化合物(x2)中的羧基進行反應而獲得中間體後,使化合物(x3)加成在該中間體。環氧化合物(x1)能夠含有:甲酚酚醛清漆型環氧化合物、苯酚酚醛清漆型環氧化合物、聯苯酚醛清漆型環氧化合物等適當的環氧化合物。特別是,環氧化合物(x1)較佳是含有從聯苯酚醛清漆型環氧化合物、甲酚酚醛清漆型環氧化合物的群組中選出的至少1種化合物。環氧化合物(x1)可僅含有聯苯酚醛清漆型環氧化合物,或可僅含有甲酚酚醛清漆型環氧化合物。此時,由於環氧化合物(x1)的主鏈含有芳香環,故能夠降低感光性樹脂組成物的硬化物因例如含有過錳酸鉀等的氧化劑而顯著腐蝕的程度。環氧化合物(x1)可含有乙烯性不飽和化合物(z)的聚合物。乙烯性不飽和化合物(z)例如含有(甲基)丙烯酸縮水甘油酯等具有環氧基的化合物(z1),或進一步含有鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯等不具有環氧基的化合物(z2)。乙烯性不飽和化合物(x2)較佳是含有丙烯酸及甲基丙烯酸之中的至少一種。化合物(x3)含有例如:從由鄰苯二甲酸、四氫鄰苯二甲酸、甲基四氫鄰苯二甲酸等多元羧酸及此等多元羧酸的酐所組成的群組中選出的一種以上的化合物。特別是,化合物(x3)較佳是含有:從鄰苯二甲酸、四氫鄰苯二甲酸、甲基四氫鄰苯二甲酸的群組中選出的至少1種多元羧酸。The carboxyl group-containing resin (A2) may contain a compound (hereinafter referred to as (A2-2) component) having a carboxyl group and an ethylenically unsaturated group. In addition, the carboxyl group-containing resin (A2) may contain only the (A2-2) component. The component (A2-2) contains, for example, one kind of resin (referred to as the first resin (x)), which is a reaction product of a specific intermediate and at least one compound (x3) selected from the group of polycarboxylic acids and their anhydrides. The specific intermediate is a reaction product of an epoxy compound (x1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (x2). The first resin (x) can be obtained, for example, by adding the compound (x3) to the intermediate obtained by reacting the epoxy group in the epoxy compound (x1) and the carboxyl group in the ethylenically unsaturated compound (x2) to obtain an intermediate. The epoxy compound (x1) can contain appropriate epoxy compounds such as a cresol novolak type epoxy compound, a phenol novolac type epoxy compound, and a biphenyl novolak type epoxy compound. In particular, the epoxy compound (x1) preferably contains at least one compound selected from the group consisting of biphenyl novolak-type epoxy compounds and cresol novolac-type epoxy compounds. The epoxy compound (x1) may contain only a biphenyl novolak-type epoxy compound, or may contain only a cresol novolak-type epoxy compound. In this case, since the main chain of the epoxy compound (x1) contains an aromatic ring, the degree to which the cured product of the photosensitive resin composition is significantly corroded by an oxidizing agent such as potassium permanganate can be reduced. The epoxy compound (x1) may contain a polymer of an ethylenically unsaturated compound (z). The ethylenically unsaturated compound (z) contains, for example, a compound (z1) having an epoxy group such as glycidyl (meth)acrylate, or a compound (z2) not having an epoxy group such as 2-(meth)acryloxyethyl phthalate. The ethylenically unsaturated compound (x2) preferably contains at least one of acrylic acid and methacrylic acid. The compound (x3) contains, for example, one or more compounds selected from the group consisting of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid, and anhydrides of these polycarboxylic acids. In particular, the compound (x3) preferably contains at least one polyvalent carboxylic acid selected from the group of phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid.
(A2-2)成分可含有一種樹脂(稱為第二樹脂(y)),其為乙烯性不飽和單體的聚合物與具有環氧基的乙烯性不飽和化合物的反應物,該乙烯性不飽和單體含有具有羧基的乙烯性不飽和化合物。乙烯性不飽和單體可進一步含有不具有羧基的乙烯性不飽和化合物。第二樹脂(y)是以下述方式獲得:使具有環氧基的乙烯性不飽和化合物與聚合物中的一部分羧基進行反應。乙烯性不飽和單體可進一步含有不具有羧基的乙烯性不飽和化合物。具有羧基的乙烯性不飽和化合物含有例如:丙烯酸、甲基丙烯酸、ω-羧基-聚己內酯(n≒2)單丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇三甲基丙烯酸酯等化合物。不具有羧基之乙烯性不飽和化合物含有例如:鄰苯二甲酸2-(甲基)丙烯醯氧基乙酯、鄰苯二甲酸2-(甲基)丙烯醯氧基乙基-2-羥基乙酯、直鏈或分枝的脂肪族或脂環族(惟,環中一部分可具有不飽和鍵)的(甲基)丙烯酸酯等化合物。具有環氧基的乙烯性不飽和化合物較佳是含有(甲基)丙烯酸縮水甘油酯。The component (A2-2) may contain a resin (referred to as a second resin (y)) which is a reaction product of a polymer of an ethylenically unsaturated monomer containing an ethylenically unsaturated compound having a carboxyl group and an ethylenically unsaturated compound having an epoxy group. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound not having a carboxyl group. The second resin (y) is obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of carboxyl groups in a polymer. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound not having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group includes, for example, compounds such as acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, pentaerythritol triacrylate, and pentaerythritol trimethacrylate. Ethylenically unsaturated compounds without carboxyl groups include, for example: 2-(meth)acryloxyethyl phthalate, 2-(meth)acryloxyethyl-2-hydroxyethyl phthalate, straight-chain or branched aliphatic or alicyclic (only, a part of the ring may have an unsaturated bond) (meth)acrylic acid ester and other compounds. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth)acrylate.
含羧基的樹脂(A)可僅含有含羧基的樹脂(A1),僅含有含羧基的樹脂(A2),或含有含羧基的樹脂(A1)及含羧基的樹脂(A2)。含羧基的樹脂(A)較佳是含有含羧基的樹脂(A1)25質量%以上,更佳是含有40質量%以上,再更佳是含有60質量%以上,特佳是含有100質量%。此時,能夠確保感光性樹脂組成物的優異的感光性及藉由鹼性水溶液來進行的顯影性。此外,能夠特別提高感光性樹脂組成物的硬化物的耐熱性及絕緣可靠性。並且,能夠充分降低由感光性樹脂組成物所形成的被膜4的沾黏性。The carboxyl-containing resin (A) may contain only the carboxyl-containing resin (A1), only the carboxyl-containing resin (A2), or both the carboxyl-containing resin (A1) and the carboxyl-containing resin (A2). The carboxyl group-containing resin (A) preferably contains at least 25% by mass of the carboxyl group-containing resin (A1), more preferably at least 40% by mass, still more preferably at least 60% by mass, most preferably at least 100% by mass. In this case, the excellent photosensitivity of the photosensitive resin composition and the developability by alkaline aqueous solution can be ensured. Moreover, the heat resistance and insulation reliability of the hardened|cured material of a photosensitive resin composition can be improved especially. Furthermore, the stickiness of the film 4 formed of the photosensitive resin composition can be sufficiently reduced.
含羧基的樹脂(A)的重量平均分子量以700以上且100000以下為佳。若含羧基的樹脂(A)的重量平均分子量為700以上,則容易抑制由感光性樹脂組成物所形成的被膜4的沾黏性,且能夠提高感光性樹脂組成物的硬化物的絕緣可靠性及耐鍍覆性。若含羧基的樹脂(A)的重量平均分子量為100000以下,則感光性樹脂組成物的藉由鹼性水溶液來進行的顯影性容易良好。含羧基的樹脂(A)的重量平均分子量以900以上且60000以下較佳,以1200以上且10000以下更佳,以1400以上且5000以下特佳。含羧基的樹脂(A)的重量平均分子量是例如從由凝膠滲透層析法(GPC)所得的在下述條件下的測定結果算出。The weight average molecular weight of the carboxyl group-containing resin (A) is preferably 700 or more and 100,000 or less. If the weight average molecular weight of the carboxyl group-containing resin (A) is 700 or more, it is easy to suppress the stickiness of the film 4 formed by the photosensitive resin composition, and the insulation reliability and plating resistance of the cured product of the photosensitive resin composition can be improved. If the weight average molecular weight of the carboxyl group-containing resin (A) is 100,000 or less, the developability by the alkaline aqueous solution of the photosensitive resin composition will become favorable easily. The weight average molecular weight of the carboxyl group-containing resin (A) is preferably from 900 to 60,000, more preferably from 1,200 to 10,000, and particularly preferably from 1,400 to 5,000. The weight average molecular weight of the carboxyl group-containing resin (A) is calculated from the measurement results under the following conditions by gel permeation chromatography (GPC), for example.
GPC裝置:昭和電工公司製SHODEX SYSTEM 11; 管柱:SHODEX KF-800P、KF-005、KF-003、KF-001的四支串聯; 流動相:THF(四氫呋喃); 流量:1 mL/分鐘; 管柱溫度:45℃; 偵測器:RI(折射率); 換算:聚苯乙烯。 GPC device: SHODEX SYSTEM 11 manufactured by Showa Denko; Column: Four series of SHODEX KF-800P, KF-005, KF-003, KF-001; Mobile phase: THF (tetrahydrofuran); Flow rate: 1 mL/min; Column temperature: 45°C; Detector: RI (refractive index); Conversion: polystyrene.
含羧基的樹脂(A)較佳是含有酸值為65 mgKOH/g以上且150 mgKOH/g以下的成分。此時,會特別提高感光性樹脂組成物的藉由鹼性水溶液來進行的顯影性,且以鹼性水溶液來對曝光後的被膜4進行顯影,即能夠特別容易製作具有小直徑部63的通孔6。更佳是酸值為70 mgKOH/g以上且145 mgKOH/g以下,再更佳為75 mgKOH/g以上且140 mgKOH/g以下,特佳為85 mgKOH/g以上且135 mgKOH/g以下。It is preferable that the carboxyl group-containing resin (A) contains the component whose acid value is 65 mgKOH/g or more and 150 mgKOH/g or less. In this case, the developability of the photosensitive resin composition by alkaline aqueous solution is particularly improved, and the exposed film 4 is developed by alkaline aqueous solution, that is, the through hole 6 having the small-diameter portion 63 can be produced particularly easily. More preferably, the acid value is not less than 70 mgKOH/g and not more than 145 mgKOH/g, still more preferably not less than 75 mgKOH/g and not more than 140 mgKOH/g, particularly preferably not less than 85 mgKOH/g and not more than 135 mgKOH/g.
不飽和化合物(B)能夠對感光性樹脂組成物賦予光硬化性。不飽和化合物(B)能夠含有例如從由下述所組成的群組中選出的至少一種化合物:(甲基)丙烯酸2-羥基乙酯等單官能(甲基)丙烯酸酯;以及二乙二醇二(甲基)丙烯酸酯、三羥甲基丙烷二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、ε-己內酯改質季戊四醇六(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯等多官能(甲基)丙烯酸酯。The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) can contain, for example, at least one compound selected from the group consisting of monofunctional (meth)acrylates such as 2-hydroxyethyl (meth)acrylate; ) acrylate, ε-caprolactone modified pentaerythritol hexa(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate and other multifunctional (meth)acrylates.
特別是,不飽和化合物(B)較佳是含有三官能的化合物、亦即一分子中具有3個不飽和鍵的化合物。此時,會提高當對由感光性樹脂組成物所形成的被膜4進行曝光/顯影時的解析性,並且特別提高感光性樹脂組成物的藉由鹼性水溶液來進行的顯影性。三官能的化合物能夠含有例如從由下述所組成的群組中選出的至少一種化合物:三羥甲基丙烷三(甲基)丙烯酸酯、EO(環氧乙烷)改質三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、乙氧基化異氰脲酸三(甲基)丙烯酸酯、及ε-己內酯改質參(2-丙烯醯氧基乙基)異氰脲酸酯、及乙氧基化甘油三(甲基)丙烯酸酯。In particular, the unsaturated compound (B) is preferably a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, the resolution when exposing/developing the film 4 formed of the photosensitive resin composition is improved, and the developability of the photosensitive resin composition by an alkaline aqueous solution is particularly improved. The trifunctional compound can contain, for example, at least one compound selected from the group consisting of trimethylolpropane tri(meth)acrylate, EO (ethylene oxide) modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated isocyanurate tri(meth)acrylate, and ε-caprolactone modified ginseng(2-acryloxyethyl)isocyanurate, and ethoxylated glycerol tri(meth)acrylate.
不飽和化合物(B)亦較佳是含有含磷化合物(含磷不飽和化合物)。此時,會提高感光性樹脂組成物的硬化物的阻燃性。含磷不飽和化合物能夠含有例如從由下述所組成的群組中選出的至少一種化合物:磷酸2-甲基丙烯醯氧基乙酯(具體例為共榮社化學股份有限公司製的型號LIGHT ESTER P-1M、及LIGHT ESTER P-2M)、磷酸2-丙烯醯氧基乙酯(具體例為共榮社化學股份有限公司製的型號LIGHT ACRYLATE P-1A)、磷酸二苯酯2-甲基丙烯醯氧基乙酯(具體例為大八工業股份有限公司製的型號MR-260)、以及昭和高分子股份有限公司製的HFA系列(具體例為:二季戊四醇六丙烯酸酯與HCA(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)的加成反應物亦即型號HFA-6003及HFA-6007;己內酯改質二季戊四醇六丙烯酸酯與HCA(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)的加成反應物亦即型號HFA-3003及HFA-6127等)。It is also preferable that the unsaturated compound (B) contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. The phosphorus-containing unsaturated compound can contain, for example, at least one compound selected from the group consisting of: 2-methacryloxyethyl phosphate (specific examples are models LIGHT ESTER P-1M and LIGHT ESTER P-2M manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloxyethyl phosphate (a specific example is model LIGHT ACRYLATE P-1A manufactured by Kyoeisha Chemical Co., Ltd.), Specific examples are the model MR-260 manufactured by Daihachi Industry Co., Ltd.), and the HFA series manufactured by Showa Polymer Co., Ltd. (specific examples are: addition reactants of dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), namely models HFA-6003 and HFA-6007; caprolactone-modified dipentaerythritol hexaacrylate and HCA (9,10-dihydro-9-oxa -10-phosphaphenanthrene-10-oxide) addition reactants, namely model HFA-3003 and HFA-6127, etc.).
不飽和化合物(B)可含有預聚物。預聚物能夠含有例如從由下述所組成的群組中選出的至少一種化合物:使具有乙烯性不飽和鍵的單體進行聚合後將乙烯性不飽和基加成而得的預聚物;以及寡聚(甲基)丙烯酸酯預聚物類。寡聚(甲基)丙烯酸酯預聚物類能夠含有例如從由下述所組成的群組中選出的至少一種成分:環氧基(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、胺酯(甲基)丙烯酸酯、醇酸樹脂(甲基)丙烯酸酯、矽氧樹脂(甲基)丙烯酸酯、及螺烷樹脂(甲基)丙烯酸酯。The unsaturated compound (B) may contain a prepolymer. The prepolymer can contain, for example, at least one compound selected from the group consisting of: a prepolymer obtained by polymerizing a monomer having an ethylenically unsaturated bond and adding an ethylenically unsaturated group; and oligo(meth)acrylate prepolymers. The oligomeric (meth)acrylate prepolymers can contain, for example, at least one component selected from the group consisting of epoxy (meth)acrylates, polyester (meth)acrylates, urethane (meth)acrylates, alkyd (meth)acrylates, silicone (meth)acrylates, and spirane resin (meth)acrylates.
光聚合起始劑(C)較佳是含有光聚合起始劑(C1),該光聚合起始劑(C1)含有:從由醯基氧化膦系光聚合起始劑、α-胺基烷基苯酮系光聚合起始劑及肟酯系光聚合起始劑所組成的群組中選出的至少一種。此時,當以紫外線來對感光性樹脂組成物進行曝光時,能夠對感光性樹脂組成物賦予高光吸收性。若感光性樹脂組成物具有良好的光吸收性,則在對由感光性樹脂組成物所形成的被膜4進行曝光時容易吸收光,故光硬化容易進行。並且,在被膜4內吸收光,而能夠減少到達深部的光的量。因此,在深部特別不容易產生由光散射所造成的影響,且在深部較表面更特別不容易進行被膜4的光硬化。因此,當藉由光微影法來製作通孔6時,特別容易形成小直徑部63。The photopolymerization initiator (C) preferably contains a photopolymerization initiator (C1), and the photopolymerization initiator (C1) contains at least one selected from the group consisting of an acylphosphine oxide-based photopolymerization initiator, an α-aminoalkylphenone-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator. At this time, when the photosensitive resin composition is exposed to ultraviolet rays, high light absorption can be imparted to the photosensitive resin composition. When the photosensitive resin composition has good light absorption, light is easily absorbed when exposing the coating film 4 formed of the photosensitive resin composition, so photocuring is easy to proceed. In addition, light is absorbed in the coating film 4, so that the amount of light reaching a deep part can be reduced. Therefore, the effect of light scattering is particularly difficult to occur in the deep part, and photocuring of the coating film 4 is more difficult to be performed in the deep part than in the surface. Therefore, when the through hole 6 is formed by photolithography, it is particularly easy to form the small-diameter portion 63 .
光聚合起始劑(C1)更佳是含有:醯基氧化膦系光聚合起始劑。此時,能夠對感光性樹脂組成物賦予更高的光吸收性。The photopolymerization initiator (C1) preferably contains an acylphosphine oxide-based photopolymerization initiator. In this case, higher light absorptivity can be provided to the photosensitive resin composition.
醯基氧化膦系光聚合起始劑能夠含有例如從由下述所組成的群組中選出的至少一種成分:2,4,6-三甲基苯甲醯基二苯基氧化膦、2,4,6-三甲基苯甲醯基乙基苯基次膦酸酯等單醯基氧化膦系光聚合起始劑;以及雙(2,6-二氯苯甲醯基)苯基氧化膦、雙(2,6-二氯苯甲醯基)-2,5-二甲基苯基氧化膦、雙(2,6-二氯苯甲醯基)-4-丙基苯基氧化膦、雙(2,6-二氯苯甲醯基)-1-萘基氧化膦、雙(2,6-二甲氧基苯甲醯基)苯基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,4,4-三甲基戊基氧化膦、雙(2,6-二甲氧基苯甲醯基)-2,5-二甲基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)苯基氧化膦、(2,5,6-三甲基苯甲醯基)-2,4,4-三甲基戊基氧化膦等雙醯基氧化膦系光聚合起始劑。醯基氧化膦系光聚合起始劑更佳是含有2,4,6-三甲基苯甲醯基二苯基氧化膦及雙(2,4,6-三甲基苯甲醯基)苯基氧化膦之中的至少一種,再更佳是含有2,4,6-三甲基苯甲醯基二苯基氧化膦。The acylphosphine oxide-based photopolymerization initiator can contain, for example, at least one component selected from the group consisting of: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylethylphenylphosphinate and other monoacylphosphine oxide-based photopolymerization initiators; and bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5 -Dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2, Bisacylphosphine oxide-based photopolymerization initiators such as 5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and (2,5,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide. The acylphosphine oxide-based photopolymerization initiator more preferably contains at least one of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and more preferably contains 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
α-胺基烷基苯酮系光聚合起始劑能夠含有例如從由下述所組成的群組中選出的至少一種成分:2-甲基-1-(4-甲硫基苯基)-2-(N-嗎啉基)丙-1-酮、2-苯甲基-2-二甲胺基-1-(4-(N-嗎啉基)苯基)丁酮-1、2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]-1-丁酮。The α-aminoalkylphenone-based photopolymerization initiator can contain, for example, at least one component selected from the group consisting of 2-methyl-1-(4-methylthiophenyl)-2-(N-morpholinyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholin Linyl)phenyl]-1-butanone.
肟酯系光聚合起始劑能夠含有例如從由下述所組成的群組中選出的至少一種成分:1,2-辛二酮,1-[4-(苯硫基)-,2-(O-苯甲醯基肟)]、乙酮,1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-,1-(O-乙醯基肟)。The oxime ester photopolymerization initiator can contain, for example, at least one component selected from the group consisting of 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime).
光聚合起始劑(C)除了含有上述成分的光聚合起始劑(C1)以外,還可含有:含有上述以外的成分的光聚合起始劑(C2)。光聚合起始劑(C2)較佳是含有α-羥基苯乙酮系光聚合起始劑及噻噸酮(thioxanthone)系光聚合起始劑之中的至少一種。此時,能夠對感光性樹脂組成物賦予特別高的光吸收性。光聚合起始劑(C2)更佳是含有α-羥基苯乙酮系光聚合起始劑。The photoinitiator (C) may contain the photoinitiator (C2) containing the component other than the above other than the photoinitiator (C1) containing the said component. The photopolymerization initiator (C2) preferably contains at least one of α-hydroxyacetophenone-based photopolymerization initiators and thioxanthone-based photopolymerization initiators. In this case, particularly high light absorption can be imparted to the photosensitive resin composition. The photopolymerization initiator (C2) preferably contains an α-hydroxyacetophenone-based photopolymerization initiator.
α-羥基苯乙酮系光聚合起始劑較佳是含有例如1-羥基環己基苯基酮1-羥基環己基苯基酮。The α-hydroxyacetophenone-based photopolymerization initiator preferably contains, for example, 1-hydroxycyclohexyl phenyl ketone 1-hydroxy cyclohexyl phenyl ketone.
噻噸酮系光聚合起始劑較佳是含有例如2,4-二乙基噻噸-9-酮。The thioxanthone-based photopolymerization initiator preferably contains, for example, 2,4-diethylthioxanth-9-one.
較佳是光聚合起始劑(C)含有4,4-雙(二乙胺基)二苯甲酮(C3)。換言之,感光性樹脂組成物亦較佳是:含有光聚合起始劑(C1)及4,4-雙(二乙胺基)二苯甲酮(C3);或者含有光聚合起始劑(C1)、光聚合起始劑(C2)及4,4-雙(二乙胺基)二苯甲酮(C3)。此時,在對由感光性樹脂組成物所形成的被膜4的一部分進行曝光後進行顯影時,特別容易抑制未曝光的部分的硬化。因此,特別容易形成具有小直徑部63的通孔6。Preferably, the photopolymerization initiator (C) contains 4,4-bis(diethylamino)benzophenone (C3). In other words, the photosensitive resin composition is also preferably: containing photopolymerization initiator (C1) and 4,4-bis(diethylamino)benzophenone (C3); or containing photopolymerization initiator (C1), photopolymerization initiator (C2) and 4,4-bis(diethylamino)benzophenone (C3). In this case, when developing after exposing a part of the coating film 4 formed of the photosensitive resin composition, it is easy to suppress hardening of the unexposed part especially. Therefore, it is particularly easy to form the through hole 6 having the small-diameter portion 63 .
相對於光聚合起始劑(C1),4,4-雙(二乙胺基)二苯甲酮(C3)較佳是在0.5質量%以上且20質量%以下的範圍內。若4,4-雙(二乙胺基)二苯甲酮(C3)為0.5質量%以上,則特別容易抑制未曝光的部分的硬化。若4,4-雙(二乙胺基)二苯甲酮(C3)為20質量%以下,則4,4-雙(二乙胺基)二苯甲酮(C3)不容易阻礙感光性樹脂組成物的硬化物的電絕緣性。相對於光聚合起始劑(C1),雙(二乙胺基)二苯甲酮(C3)特佳是在1質量%以上且18質量%以下的範圍內。當感光性樹脂組成物含有有機填料(E)時,有時有機填料(E)在曝光時在感光性樹脂組成物內會使光散射發生。此時,有產生在感光性樹脂組成物中無法獲得良好的解析性的問題的可能性。因此,有不容易於通孔6中形成小直徑部63之虞。然而,若4,4-雙(二乙胺基)二苯甲酮(C3)在上述範圍內,則感光性樹脂組成物容易具有良好的解析性,因此特別容易於通孔6中形成小直徑部63。4,4-bis(diethylamino)benzophenone (C3) is preferably in the range of 0.5 mass % or more and 20 mass % or less with respect to a photopolymerization initiator (C1). When 4,4-bis (diethylamino) benzophenone (C3) is 0.5 mass % or more, it becomes easy to suppress hardening of the unexposed part especially. When 4,4-bis(diethylamino)benzophenone (C3) is 20 mass % or less, 4,4-bis(diethylamino)benzophenone (C3) will not easily inhibit the electrical insulation of the hardened|cured material of a photosensitive resin composition. Bis(diethylamino)benzophenone (C3) is especially preferable in the range of 1 mass % or more and 18 mass % or less with respect to a photoinitiator (C1). When the photosensitive resin composition contains the organic filler (E), the organic filler (E) may cause light scattering in the photosensitive resin composition at the time of exposure. In this case, there is a possibility that a problem that good resolution cannot be obtained in the photosensitive resin composition may arise. Therefore, it may be difficult to form the small-diameter portion 63 in the through hole 6 . However, if the 4,4-bis(diethylamino)benzophenone (C3) is within the above range, the photosensitive resin composition tends to have good resolving power, and therefore it is particularly easy to form the small-diameter portion 63 in the through hole 6 .
感光性樹脂組成物較佳是含有:環氧樹脂(D)。環氧樹脂(D)能夠對感光性樹脂組成物賦予熱硬化性。環氧樹脂(D)較佳是含有結晶性環氧樹脂。此時,能夠提高感光性樹脂組成物的顯影性。此外,環氧樹脂(D)可進一步含有非晶性環氧樹脂。此處,「結晶性環氧樹脂」為具有熔點的環氧樹脂,「非晶性環氧樹脂」為不具有熔點的環氧樹脂。The photosensitive resin composition preferably contains an epoxy resin (D). The epoxy resin (D) can impart thermosetting properties to the photosensitive resin composition. The epoxy resin (D) preferably contains a crystalline epoxy resin. In this case, the developability of the photosensitive resin composition can be improved. In addition, the epoxy resin (D) may further contain an amorphous epoxy resin. Here, a "crystalline epoxy resin" is an epoxy resin having a melting point, and an "amorphous epoxy resin" is an epoxy resin not having a melting point.
結晶性環氧樹脂較佳是含有例如從由下述所組成的群組中選出的一種以上的成分:1,3,5-參(2,3-環氧基丙基)-1,3,5-三嗪-2,4,6(1H,3H,5H)-三酮、氫醌型結晶性環氧樹脂(具體例為NIPPON STEEL Chemical & Material股份有限公司製的商品名YDC-1312)、聯苯型結晶性環氧樹脂(具體例為三菱化學股份有限公司製的商品名YX-4000)、二苯醚型結晶性環氧樹脂(具體例為NIPPON STEEL Chemical & Material股份有限公司製的型號YSLV-80DE)、雙酚型結晶性環氧樹脂(具體例為NIPPON STEEL Chemical & Material股份有限公司製的商品名YSLV-70XY及YSLV-80XY)、肆酚乙烷型結晶性環氧樹脂(具體例為日本化藥股份有限公司製的型號GTR-1800)、雙酚茀型結晶性環氧樹脂。The crystalline epoxy resin preferably contains, for example, one or more components selected from the group consisting of 1,3,5-ginseng(2,3-epoxypropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, a hydroquinone type crystalline epoxy resin (a specific example is YDC-1312 manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), a biphenyl type crystalline epoxy resin (a specific example is Tris Ryo Chemical Co., Ltd., trade name YX-4000), diphenyl ether type crystalline epoxy resin (specific example, model YSLV-80DE manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), bisphenol type crystalline epoxy resin (specific examples, trade name YSLV-70XY and YSLV-80XY manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), tetraphenol ethane type crystalline epoxy resin (specific example, model G manufactured by Nippon Kayaku Co., Ltd. TR-1800), bisphenol fennel type crystalline epoxy resin.
結晶性環氧樹脂較佳是1分子中具有2個以上的環氧基。此時,能夠使感光性樹脂組成物的硬化物在反覆溫度變化中更不容易發生龜裂。The crystalline epoxy resin preferably has two or more epoxy groups in one molecule. In this case, it is possible to make the cured product of the photosensitive resin composition less likely to be cracked during repeated temperature changes.
結晶性環氧樹脂較佳是具有150 g/eq以上且300 g/eq以下的環氧當量。此環氧當量為含有1 g當量的環氧基的結晶性環氧樹脂的g重量。結晶性環氧樹脂具有熔點。結晶性環氧樹脂的熔點可舉例如70℃以上且180℃以下。The crystalline epoxy resin preferably has an epoxy equivalent of 150 g/eq or more and 300 g/eq or less. This epoxy equivalent is the g weight of the crystalline epoxy resin containing the epoxy group of 1 g equivalent. Crystalline epoxy resins have melting points. The melting point of the crystalline epoxy resin is, for example, not less than 70°C and not more than 180°C.
特別是,環氧化合物(D)較佳是含有熔點110℃以下的結晶性環氧樹脂。此時,會特別提高感光性樹脂組成物的藉由鹼性水溶液來進行的顯影性。熔點110℃以下的結晶性環氧樹脂能夠含有例如從由下述所組成的群組中選出的至少一種成分:聯苯型環氧樹脂(具體例為三菱化學股份有限公司製的型號YX-4000)、二苯醚型環氧樹脂(具體例為NIPPON STEEL Chemical & Material股份有限公司製的型號YSLV-80DE)、及雙酚型環氧樹脂(具體例為NIPPON STEEL Chemical & Material股份有限公司製的型號YSLV-70XY及YSLV-80XY)、雙酚茀型結晶性環氧樹脂。In particular, the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110°C or lower. In this case, the developability by the alkaline aqueous solution of a photosensitive resin composition improves especially. The crystalline epoxy resin having a melting point of 110° C. or less can contain, for example, at least one component selected from the group consisting of biphenyl type epoxy resin (specific example is model YX-4000 manufactured by Mitsubishi Chemical Co., Ltd.), diphenyl ether type epoxy resin (specific example is model YSLV-80DE manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), and bisphenol type epoxy resin (specific example is model YSLV manufactured by NIPPON STEEL Chemical & Material Co., Ltd.) -70XY and YSLV-80XY), bisphenol peroxide type crystalline epoxy resin.
非晶性環氧樹脂較佳是含有例如從由下述所組成的群組中選出的至少一種成分:苯酚酚醛清漆型環氧樹脂(具體例為DIC股份有限公司製的型號EPICLON N-775)、甲酚酚醛清漆型環氧樹脂(具體例為DIC股份有限公司製的型號EPICLON N-695)、雙酚A酚醛清漆型環氧樹脂(具體例為DIC股份有限公司製的型號EPICLON N-865)、雙酚A型環氧樹脂(具體例為三菱化學股份有限公司製的型號jER1001)、雙酚F型環氧樹脂(具體例為三菱化學股份有限公司製的型號jER4004P)、雙酚S型環氧樹脂(具體例為DIC股份有限公司製的型號EPICLON EXA-1514)、雙酚AD型環氧樹脂、聯苯酚醛清漆型環氧樹脂(具體例為日本化藥股份有限公司製的型號NC-3000)、氫化雙酚A型環氧樹脂(具體例為NIPPON STEEL Chemical & Material股份有限公司製的型號ST-4000D)、萘型環氧樹脂(具體例為DIC股份有限公司製的型號EPICLON HP-4032、EPICLON HP-4700、EPICLON HP-4770)、三級丁基兒茶酚型環氧樹脂(具體例為DIC股份有限公司製的型號EPICLON HP-820)、雙環戊二烯型環氧樹脂(具體例為DIC公司製的型號EPICLON HP-7200)、金剛烷型環氧樹脂(具體例為出光興產股份有限公司製的型號ADAMANTATEX-E-201)、特殊二官能型環氧樹脂(具體例為三菱化學股份有限公司製的型號YL7175-500及YL7175-1000;DIC股份有限公司製的型號EPICLON TSR-960、EPICLON TER-601、EPICLON TSR-250-80BX、EPICLON 1650-75MPX、EPICLON EXA-4850、EPICLON EXA-4816、EPICLON EXA-4822、及EPICLON EXA-9726;NIPPON STEEL Chemical & Material股份有限公司製的型號YSLV-120TE)、橡膠狀核殼聚合物改質雙酚A型環氧樹脂(具體例為KANEKA股份有限公司製的型號MX-156)、橡膠狀核殼聚合物改質雙酚F型環氧樹脂(具體例為KANEKA股份有限公司製的型號MX-136)、以及含橡膠粒子的雙酚F型環氧樹脂(具體例為KANEKA股份有限公司製的型號Kane Ace MX-130)。The amorphous epoxy resin preferably contains, for example, at least one component selected from the group consisting of: phenol novolac epoxy resin (a specific example is EPICLON N-775 manufactured by DIC Corporation), cresol novolac epoxy resin (a specific example is EPICLON N-695 manufactured by DIC Corporation), bisphenol A novolak epoxy resin (a specific example is EPICLON N-865 manufactured by DIC Corporation), bisphenol A epoxy Resin (specific example is model jER1001 manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol F type epoxy resin (specific example is model jER4004P manufactured by Mitsubishi Chemical Co., Ltd.), bisphenol S type epoxy resin (specific example is model EPICLON EXA-1514 manufactured by DIC Co., Ltd.), bisphenol AD type epoxy resin, biphenol novolak type epoxy resin (specific example is model NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (specific example is NIPPON STEEL Chemical & Material Co., Ltd., model ST-4000D), naphthalene-type epoxy resin (specific example, DIC Co., Ltd., model EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770), tertiary butylcatechol-type epoxy resin (specific example, DIC Co., Ltd., model EPICLON HP-820), dicyclopentadiene-type epoxy resin (specific example, DIC Co., Ltd. Epiclon HP-7200 manufactured by the company), adamantane-type epoxy resin (specifically, model ADAMANTATEX-E-201 manufactured by Idemitsu Kosan Co., Ltd.), special bifunctional epoxy resin (specifically, model YL7175-500 and YL7175-1000 manufactured by Mitsubishi Chemical Co., Ltd.; model EPICLON TSR-960, EPICLON TER-601, EPICLON TSR manufactured by DIC Co., Ltd. -250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; model YSLV-120TE manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), rubber-like core-shell polymer modified bisphenol A type epoxy resin (specifically, K Model MX-156 manufactured by ANEKA Co., Ltd.), rubber-like core-shell polymer modified bisphenol F-type epoxy resin (a specific example is model MX-136 manufactured by KANEKA Co., Ltd.), and bisphenol F-type epoxy resin containing rubber particles (a specific example is Kane Ace MX-130 manufactured by KANEKA Co., Ltd.).
當感光性樹脂組成物含有環氧樹脂(D)時,感光性樹脂組成物較佳是含有結晶性環氧樹脂及非晶性環氧雙方。此時,能夠更加提高由感光性樹脂組成物所製作的硬化物的耐鍍覆性及絕緣性。When the photosensitive resin composition contains an epoxy resin (D), it is preferable that the photosensitive resin composition contains both a crystalline epoxy resin and an amorphous epoxy. In this case, the plating resistance and insulation properties of the cured product produced from the photosensitive resin composition can be further improved.
環氧樹脂(D)可含有含磷環氧樹脂。此時,會提高感光性樹脂組成物的硬化物的阻燃性。含磷環氧樹脂可包含在結晶性環氧樹脂中,且或者亦可包含在非晶性環氧樹脂中。含磷環氧樹脂可舉例如:磷酸改質雙酚F型環氧樹脂(具體例為DIC股份有限公司製的型號EPICLON EXA-9726、及EPICLON EXA-9710)、NIPPON STEEL Chemical & Material股份有限公司製的型號Epotohto FX-305等。The epoxy resin (D) may contain a phosphorus-containing epoxy resin. In this case, the flame retardancy of the cured product of the photosensitive resin composition is improved. The phosphorus-containing epoxy resin may be contained in a crystalline epoxy resin, or may also be contained in an amorphous epoxy resin. Phosphorus-containing epoxy resins include, for example, phosphoric acid-modified bisphenol F-type epoxy resins (specific examples are models EPICLON EXA-9726 and EPICLON EXA-9710 manufactured by DIC Co., Ltd.), model Epotohto FX-305 manufactured by NIPPON STEEL Chemical & Material Co., Ltd., and the like.
感光性樹脂組成物較佳是不含填料。此時,會抑制在被膜4的深部的光散射,而特別容易形成具有小直徑部63的通孔6。當感光性樹脂組成物含有填料時,較佳是以使光散射在被膜4內適度地不容易發生的方式適當設定填料的材質、粒徑及調配量。The photosensitive resin composition preferably does not contain filler. In this case, light scattering in the deep portion of the coating 4 is suppressed, and the through-hole 6 having the small-diameter portion 63 is particularly easily formed. When the photosensitive resin composition contains a filler, it is preferable to appropriately set the material, particle size, and compounding amount of the filler so that light scattering is moderately less likely to occur in the coating film 4 .
感光性樹脂組成物可含有:有機填料(E)。再者,有機填料(E)中不含三聚氰胺。此時,較佳是如上所述適當設定有機填料(E)的材質、粒徑及調配量。有機填料(E)會對感光性樹脂組成物賦予觸變性,而提高感光性樹脂組成物的保存安定性。此外,硬化物的與鍍覆層之間的密合性會提高。有機填料(E)較佳是具有反應性基。有機填料(E)具有反應性基,而在感光性樹脂組成物中具有高相溶性,而會對感光性樹脂組成物賦予更強的觸變性,而感光性樹脂組成物的保存安定性更加提高。此外,硬化物與鍍覆層之間的密合性更加提高。有機填料(E)具有的反應性基例如:更佳是包含從由羧基、胺基、環氧基、乙烯基及羥基所組成的群組中選出的至少一種基,再更佳是包含羧基及胺基之中的至少一種。此時,感光性樹脂組成物的保存安定性更加提高。此外,硬化物的與鍍覆層之間的密合性更加提高。有機填料(E)具有的反應性基特佳是包含羧基。此時,會提高感光性樹脂組成物的顯影性。同時,有機填料(E)的羧基在熱硬化時能夠與感光性樹脂組成物中的環氧樹脂(D)進行反應。藉此,熱硬化後的硬化物能夠含有經在其內部均勻分散的有機填料(E)。並且,亦能夠在對硬化物的表面進行粗糙化的階段中使有機填料(E)的未進行反應的羧基進行改質。換言之,硬化物中所含的有機填料(E)之中的位於硬化物的表面附近的有機填料(E)在對硬化物的表面進行粗糙化的階段中容易變質。經以上述方式進行而變質的有機填料(E)在對硬化物賦予粗糙面時容易從硬化物去除。藉此,能夠對硬化物的表面賦予粗糙面來提高硬化物與鍍覆層之間的密合性。再且,有機填料(E)包含羧基,而能夠降低起因於感光性樹脂組成物的流動性的塗膜的不均勻性。藉此,能夠容易使由感光性樹脂組成物所形成的層的膜厚均勻。此外,容易於由感光性樹脂組成物所製作的層間絕緣層7形成具有小直徑部63的通孔6。The photosensitive resin composition may contain an organic filler (E). Furthermore, the organic filler (E) does not contain melamine. In this case, it is preferable to appropriately set the material, particle size, and compounding amount of the organic filler (E) as described above. The organic filler (E) imparts thixotropy to the photosensitive resin composition, and improves the storage stability of the photosensitive resin composition. In addition, the adhesion between the cured product and the plating layer improves. The organic filler (E) preferably has a reactive group. The organic filler (E) has a reactive group, has high compatibility in the photosensitive resin composition, and imparts stronger thixotropy to the photosensitive resin composition, and further improves the storage stability of the photosensitive resin composition. In addition, the adhesion between the cured product and the plating layer is further improved. The reactive groups of the organic filler (E) include, for example, more preferably at least one group selected from the group consisting of carboxyl, amine, epoxy, vinyl and hydroxyl, and more preferably at least one of carboxyl and amine. In this case, the storage stability of the photosensitive resin composition is further improved. In addition, the adhesion between the cured product and the plating layer is further improved. The reactive group that the organic filler (E) has particularly preferably contains a carboxyl group. In this case, the developability of the photosensitive resin composition will be improved. At the same time, the carboxyl group of the organic filler (E) can react with the epoxy resin (D) in the photosensitive resin composition during thermosetting. Thereby, the hardened|cured material after thermosetting can contain the organic filler (E) uniformly dispersed in the inside. In addition, it is also possible to modify the unreacted carboxyl group of the organic filler (E) in the step of roughening the surface of the cured product. In other words, among the organic fillers (E) contained in the cured product, the organic filler (E) located near the surface of the cured product tends to deteriorate in the step of roughening the surface of the cured product. The organic filler (E) modified as described above is easily removed from the cured product when roughening the cured product. Thereby, a rough surface can be given to the surface of a hardened|cured material, and the adhesiveness between a hardened|cured material and a plating layer can be improved. Furthermore, the organic filler (E) contains a carboxyl group, and can reduce the unevenness of the coating film originating in the fluidity of a photosensitive resin composition. Thereby, the film thickness of the layer formed from a photosensitive resin composition can be made uniform easily. In addition, it is easy to form the via hole 6 having the small-diameter portion 63 in the interlayer insulating layer 7 made of the photosensitive resin composition.
當有機填料(E)包含羧基時,羧基例如:使丙烯酸、甲基丙烯酸、巴豆酸、馬來酸、富馬酸、伊康酸等羧酸單體進行聚合或交聯,而會形成為其產物中的側鏈。羧酸單體具有羧基及聚合性不飽和雙鍵。有機填料(E)由於會提高感光性樹脂組成物的觸變性,故會提高感光性樹脂組成物的安定性(特別是保存安定性)。並且,若有機填料(E)包含羧基,則能夠提高硬化物的顯影性,並且提高結晶性環氧樹脂的相溶性而防止在感光性樹脂組成物中結晶化。有機填料(E)的羧基含量無特別限制,較佳是有機填料(E)的酸值以由酸-鹼滴定所得的酸值計為1 mgKOH/g以上且60 mgKOH/g以下。若酸值小於1 mgKOH/g,則有感光性樹脂組成物的安定性及硬化物的顯影性降低之虞。若酸值大於60 mgKOH/g,則有硬化物的耐濕可靠性降低之虞。有機填料(E)的酸值以3 mgKOH/g以上且40 mgKOH/g以下較佳。When the organic filler (E) contains a carboxyl group, the carboxyl group will form a side chain in the product by polymerizing or cross-linking carboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid. The carboxylic acid monomer has a carboxyl group and a polymerizable unsaturated double bond. Since the organic filler (E) improves the thixotropy of the photosensitive resin composition, it improves the stability (especially storage stability) of the photosensitive resin composition. Moreover, when the organic filler (E) contains a carboxyl group, the developability of the cured product can be improved, and the compatibility of the crystalline epoxy resin can be improved to prevent crystallization in the photosensitive resin composition. The carboxyl group content of the organic filler (E) is not particularly limited, but the acid value of the organic filler (E) is preferably not less than 1 mgKOH/g and not more than 60 mgKOH/g in terms of the acid value obtained by acid-base titration. When the acid value is less than 1 mgKOH/g, the stability of the photosensitive resin composition and the developability of the cured product may decrease. When the acid value exceeds 60 mgKOH/g, the moisture resistance reliability of the cured product may decrease. The acid value of the organic filler (E) is preferably not less than 3 mgKOH/g and not more than 40 mgKOH/g.
有機填料(E)較佳是平均初級粒徑為1 μm以下。有機填料(E)的平均初級粒徑為1 μm以下,而感光性樹脂組成物的顯影性良好。此外,能夠使形成於硬化物的粗糙面的粗糙度變細,而錨定(anchoring)效應會隨著硬化物的表面積增加而提高,而能夠提高粗糙面與鍍覆層之間的密合性。The organic filler (E) preferably has an average primary particle diameter of 1 μm or less. The average primary particle diameter of the organic filler (E) is 1 μm or less, and the developability of the photosensitive resin composition is good. In addition, the roughness of the rough surface formed on the cured product can be reduced, and the anchoring effect can be increased as the surface area of the cured product increases, thereby improving the adhesion between the rough surface and the plating layer.
有機填料(E)的平均初級粒徑的下限無特別限定,以例如0.001 μm以上為佳。平均初級粒徑是使用雷射繞射式粒度分布測定裝置來測定作為D 50。更佳是有機填料(E1)的平均初級粒徑為0.4 μm以下,再更佳為0.1 μm以下。此時,能夠抑制曝光時在感光性樹脂組成物中光散射,藉此,會進一步提高感光性樹脂組成物的解析性,而容易於層間絕緣層7形成具有小直徑部63的通孔6。除此之外,還能夠使形成於硬化物的粗糙面的粗糙度特別變細。 The lower limit of the average primary particle size of the organic filler (E) is not particularly limited, but is preferably at least 0.001 μm, for example. The average primary particle size is measured as D 50 using a laser diffraction particle size distribution analyzer. More preferably, the average primary particle diameter of the organic filler (E1) is 0.4 μm or less, and more preferably 0.1 μm or less. In this case, light scattering in the photosensitive resin composition during exposure can be suppressed, thereby further improving the resolution of the photosensitive resin composition and making it easier to form the via hole 6 having the small-diameter portion 63 in the interlayer insulating layer 7 . In addition to this, the roughness of the rough surface formed on the cured product can be particularly finer.
有機填料(E)較佳是在感光性樹脂組成物中經以最大粒徑未達1.0 μm來分散,更佳是經以未達0.5 μm來分散。最大粒徑是使用雷射繞射式粒度分布測定裝置來測定作為D 50。或者,最大粒徑是以使用穿透型電子顯微鏡(TEM)來觀察硬化物的方式進行測定。有機填料(E)有時在感光性樹脂組成物中會凝集(例如可能會形成次級粒子),此時,最大粒徑是意指凝集後的粒子的大小。若分散狀態下的有機填料(E)的最大粒徑在上述範圍內,則在感光性樹脂組成物中能夠抑制曝光時的散射,藉此感光性樹脂組成物的解析性更加提高,而更容易於層間絕緣層7形成具有小直徑部63的通孔6。除此之外,還能夠使形成於硬化物的粗糙面的粗糙度變更細。再者,當發生粒子凝集時,最大粒徑通常較平均初級粒徑更大。 The organic filler (E) is preferably dispersed in the photosensitive resin composition with a maximum particle size of less than 1.0 μm, more preferably less than 0.5 μm. The maximum particle diameter was measured as D 50 using a laser diffraction particle size distribution analyzer. Alternatively, the maximum particle diameter is measured by observing the cured product using a transmission electron microscope (TEM). The organic filler (E) may aggregate in the photosensitive resin composition (for example, secondary particles may be formed), and in this case, the maximum particle diameter means the size of the aggregated particles. If the maximum particle size of the organic filler (E) in the dispersed state is within the above-mentioned range, scattering during exposure can be suppressed in the photosensitive resin composition, thereby further improving the resolution of the photosensitive resin composition, and forming the via hole 6 having the small-diameter portion 63 in the interlayer insulating layer 7 more easily. In addition, the roughness of the rough surface formed on the cured product can be made finer. Furthermore, when particle agglomeration occurs, the maximum particle size is usually larger than the average primary particle size.
有機填料(E)較佳是包含橡膠成分。此外,有機填料(E)較佳是僅包含橡膠成分。橡膠成分能夠對感光性樹脂組成物的硬化物賦予柔軟性。橡膠成分能夠藉由樹脂來構成。橡膠成分較佳是包含從交聯丙烯酸系橡膠、交聯丁腈橡膠(NBR)、交聯甲基丙烯酸甲酯-丁二烯-苯乙烯(MBS)及交聯丁苯橡膠(SBR)之中選出的至少1種聚合物。此時,橡膠成分能夠對感光性樹脂組成物的硬化物賦予優異的柔軟性。並且,能夠對硬化物的表面賦予更適度的粗糙面。此處,橡膠成分包含交聯結構,該交聯結構是在使用以構成聚合物的單體進行共聚時形成。NBR一般而言為丁二烯與丙烯腈的共聚物,是分類為腈類橡膠。MBS一般而言為由甲基丙烯酸甲酯、丁二烯、苯乙烯這3種成分所構成的共聚物,是分類為丁二烯系橡膠。SBR一般而言為苯乙烯與丁二烯的共聚物,是分類為苯乙烯橡膠。有機填料(E)的具體例可舉例如:JSR股份有限公司製的型號XER-91-MEK、JSR股份有限公司製的型號XER-32-MEK、JSR股份有限公司製的型號XSK-500等。XER-91-MEK為平均初級粒徑0.07 μm的具有羧基的交聯橡膠(NBR),且是以此交聯橡膠的含有比例15重量%的甲基乙基酮分散液來提供,其酸值為10.0 mgKOH/g。XER-32-MEK為以含量相對於分散液總量為17重量%來在甲基乙基酮中使羧基改質氫化腈類橡膠的聚合物(線狀粒子)分散而成的分散液。此外,XSK-500為平均初級粒徑0.07 μm的具有羧基及羥基的交聯橡膠(SBR),且是以此交聯橡膠的含有比例15重量%的甲基乙基酮分散液來提供。像這樣,有機填料(E)可以分散液來調配在感光性樹脂組成物中。換言之,橡膠成分能夠以分散液來調配在感光性樹脂組成物中。此外,有機填料(E)的具體例除了上述以外還可舉例如JSR股份有限公司製的型號XER-92等。The organic filler (E) preferably contains a rubber component. In addition, the organic filler (E) preferably contains only rubber components. The rubber component can impart flexibility to the cured product of the photosensitive resin composition. The rubber component can be constituted by resin. The rubber component preferably contains at least one polymer selected from crosslinked acrylic rubber, crosslinked nitrile rubber (NBR), crosslinked methyl methacrylate-butadiene-styrene (MBS), and crosslinked styrene-butadiene rubber (SBR). In this case, the rubber component can impart excellent flexibility to the cured product of the photosensitive resin composition. In addition, a more moderate roughness can be provided to the surface of the cured product. Here, the rubber component includes a crosslinked structure formed when copolymerization is performed using monomers constituting the polymer. Generally speaking, NBR is a copolymer of butadiene and acrylonitrile, which is classified as nitrile rubber. MBS is generally a copolymer composed of three components, methyl methacrylate, butadiene, and styrene, and is classified as a butadiene-based rubber. SBR is generally a copolymer of styrene and butadiene, and is classified as styrene rubber. Specific examples of the organic filler (E) include model XER-91-MEK manufactured by JSR Corporation, model XER-32-MEK manufactured by JSR Corporation, model XSK-500 manufactured by JSR Corporation, and the like. XER-91-MEK is a cross-linked rubber (NBR) having a carboxyl group with an average primary particle size of 0.07 μm, and it is provided as a methyl ethyl ketone dispersion containing 15% by weight of this cross-linked rubber, and its acid value is 10.0 mgKOH/g. XER-32-MEK is a dispersion obtained by dispersing a carboxyl group-modified hydrogenated nitrile rubber polymer (linear particles) in methyl ethyl ketone at a content of 17% by weight relative to the total amount of the dispersion. In addition, XSK-500 is a cross-linked rubber (SBR) having a carboxyl group and a hydroxyl group with an average primary particle diameter of 0.07 μm, and is provided as a methyl ethyl ketone dispersion containing 15% by weight of this cross-linked rubber. In this way, the organic filler (E) can be prepared as a dispersion liquid in the photosensitive resin composition. In other words, the rubber component can be formulated in the photosensitive resin composition as a dispersion liquid. In addition, specific examples of the organic filler (E) include, for example, model XER-92 made by JSR Co., Ltd., in addition to the above.
感光性樹脂組成物能夠含有矽烷耦合劑。此時,能夠提高有機填料(E)的分散性。亦能夠更加提高感光性樹脂組成物的解析性。The photosensitive resin composition can contain a silane coupling agent. In this case, the dispersibility of the organic filler (E) can be improved. It is also possible to further improve the resolution of the photosensitive resin composition.
矽烷耦合劑為例如:含有矽原子且含有從-OCH 3基、-OC 2H 5基及-OCOCH 3基的群組中選出的2~4個水解性基的化合物。矽烷耦合劑除了水解性基以外,亦可含有:胺基、環氧基、乙烯基(烯丙基)、甲基丙烯醯基、巰基、異氰酸基、硫醚基等反應性基;或甲基。 The silane coupling agent is, for example, a compound containing a silicon atom and 2 to 4 hydrolyzable groups selected from the group of —OCH 3 groups, —OC 2 H 5 groups, and —OCOCH 3 groups. In addition to the hydrolyzable groups, the silane coupling agent may also contain reactive groups such as amine groups, epoxy groups, vinyl (allyl), methacryl groups, mercapto groups, isocyanate groups, thioether groups, or methyl groups.
矽烷耦合劑可舉例如:3-(2-胺基乙基胺基)丙基二甲氧基甲基矽烷、3-(2-胺基乙基胺基)丙基三乙氧基矽烷、3-(2-胺基乙基胺基)丙基三甲氧基矽烷、3-胺基丙基二乙氧基甲基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基三甲氧基矽烷等胺基化合物;3-縮水甘油氧基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-縮水甘油氧基丙基(二甲氧基)甲基矽烷、二乙氧基(3-縮水甘油氧基丙基)甲基矽烷等環氧類;3-丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三乙氧基矽烷、3-甲基丙烯醯氧基丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧基丙基甲基二乙氧基矽烷等(甲基)丙烯酸酯類;乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、對苯乙烯基三甲氧基矽烷、二乙氧基甲基乙烯基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷等乙烯基化合物;烯丙基三乙氧基矽烷、烯丙基三甲氧基矽烷等烯丙基化合物;對苯乙烯基三甲氧基矽烷等苯乙烯基化合物;3-異氰酸基丙基三甲氧基矽烷、3-異氰酸基丙基三乙氧基矽烷等異氰酸酯類;3-脲基丙基三甲氧基矽烷、3-脲基丙基三乙氧基矽烷等脲類;(3-巰基丙基)三乙氧基矽烷、(3-巰基丙基)三甲氧基矽烷等硫醇化合物類;雙(三乙氧基矽烷基丙基)四硫醚等硫醚類;正矽酸四乙酯、甲基三甲氧基矽烷等。Examples of silane coupling agents include: 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and other amino compounds; Silane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyl(dimethoxy)methylsilane, diethoxy(3-glycidoxypropyl)methylsilane and other epoxy compounds; 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, -(meth)acrylic esters such as methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropylmethyldiethoxysilane; vinyl compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, p-styryltrimethoxysilane, diethoxymethylvinylsilane, vinyl ginseng (2-methoxyethoxy)silane; allyl compounds such as allyltriethoxysilane and allyltrimethoxysilane; p-styryltrimethoxy Styryl compounds such as silane; 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and other isocyanates; Ethyl ester, methyltrimethoxysilane, etc.
感光性樹脂組成物能夠含有三聚氰胺。此時,能夠降低因例如含有過錳酸鉀的氧化劑而使感光性樹脂組成物的硬化物顯著腐蝕的程度。換言之,感光性樹脂組成物含有三聚氰胺,而能夠在鍍覆處理的前步驟中對感光性樹脂組成物的硬化物表面進行粗糙化時使包含硬化物的層的厚度薄化。以上述方式進行而對硬化物表面賦予粗糙面,即能夠提高感光性樹脂組成物的硬化物與由銅和金等所構成的鍍覆層之間的密合性。三聚氰胺為2,4,6-三胺基-1,3,5-三嗪,一般而言能夠從已市售的化合物取得。三聚氰胺較佳是以平均粒徑20 μm以下、較佳為15 μm以下來分散在感光性樹脂組成物中。三聚氰胺經均勻分散在感光性樹脂組成物中,而三聚氰胺更容易與金屬元素進行配位鍵結。藉此,能夠更加提高感光性樹脂組成物的密合性。三聚氰胺的平均粒徑的下限無特別限定,能夠設為0.01 μm以上。再者,三聚氰胺的平均粒徑能夠在經使三聚氰胺在未硬化的感光性樹脂組成物中分散的狀態下使用雷射繞射式粒度分散測定裝置來測定作為D 50。 The photosensitive resin composition can contain melamine. In this case, the degree to which the cured product of the photosensitive resin composition is significantly corroded by, for example, an oxidizing agent containing potassium permanganate can be reduced. In other words, the photosensitive resin composition contains melamine, and the thickness of the layer containing the cured product can be reduced when roughening the surface of the cured product of the photosensitive resin composition in the preceding step of the plating process. Roughening the surface of the cured product as described above can improve the adhesion between the cured product of the photosensitive resin composition and the plating layer composed of copper, gold, or the like. Melamine is 2,4,6-triamino-1,3,5-triazine, and can generally be obtained from a commercially available compound. Melamine is preferably dispersed in the photosensitive resin composition with an average particle size of 20 μm or less, preferably 15 μm or less. The melamine is uniformly dispersed in the photosensitive resin composition, and the melamine is more likely to carry out coordination bonding with metal elements. Thereby, the adhesiveness of a photosensitive resin composition can be improved more. The lower limit of the average particle diameter of melamine is not specifically limited, It can be 0.01 micrometer or more. In addition, the average particle diameter of melamine can be measured as D50 using the laser diffraction particle size dispersion measuring apparatus in the state which disperse|distributed melamine in the uncured photosensitive resin composition.
感光性樹脂組成物可含有無機填料。此時,會降低由感光性樹脂組成物所形成的膜的硬化收縮。此外,能夠降低介電耗損正切。無機填料能夠含有例如從由下述所組成的群組中選出的一種以上的材料:硫酸鋇、氧化矽、奈米碳管、滑石、皂土、氫氧化鋁、氫氧化鎂及氧化鈦。The photosensitive resin composition may contain an inorganic filler. In this case, curing shrinkage of the film formed of the photosensitive resin composition is reduced. In addition, the dielectric loss tangent can be reduced. The inorganic filler can contain, for example, one or more materials selected from the group consisting of barium sulfate, silicon oxide, carbon nanotubes, talc, bentonite, aluminum hydroxide, magnesium hydroxide, and titanium oxide.
本實施形態的感光性樹脂組成物可含有有機溶劑。有機溶劑是為了下述目的而使用:感光性樹脂組成物的液狀化或清漆化、黏度調整、塗佈性的調整、造膜性的調整等。The photosensitive resin composition of this embodiment may contain an organic solvent. The organic solvent is used for the purposes of liquefaction or varnish of the photosensitive resin composition, viscosity adjustment, coating property adjustment, film-forming property adjustment, and the like.
有機溶劑能夠含有例如從由下述所組成的群組中選出的一種以上的化合物:乙醇、丙醇、異丙醇、己醇、乙二醇等直鏈、分枝、二級或多元的醇類;甲基乙基酮、環己酮等酮類;甲苯、二甲苯等芳香族烴類;Swasol系列(丸善石油化學公司製),Solvesso系列(ExxonMobil Chemical公司製)等石油系芳香族系混合溶劑;賽璐蘇、丁基賽璐蘇等賽璐蘇類;卡必醇、丁基卡必醇等卡必醇;丙二醇甲基醚等丙二醇烷基醚類;二丙二醇甲基醚等聚丙二醇烷基醚類;乙酸乙酯、乙酸丁酯、賽璐蘇乙酸酯、卡必醇乙酸酯等乙酸酯類;以及二烷基二醇醚類。The organic solvent can contain, for example, one or more compounds selected from the group consisting of: ethanol, propanol, isopropanol, hexanol, ethylene glycol and other linear, branched, secondary or polyhydric alcohols; methyl ethyl ketone, cyclohexanone and other ketones; toluene, xylene and other aromatic hydrocarbons; Celluloids such as celluloid; carbitol such as carbitol and butyl carbitol; propylene glycol alkyl ethers such as propylene glycol methyl ether; polypropylene glycol alkyl ethers such as dipropylene glycol methyl ether; acetates such as ethyl acetate, butyl acetate, celluloid acetate, and carbitol acetate; and dialkyl glycol ethers.
相對於感光性樹脂組成物的固體成分量,含羧基的樹脂(A)若在5質量%以上且85質量%以下的範圍內則較佳,若在10質量%以上且75質量%以下的範圍內則更佳,若在30質量%以上且60質量%以下的範圍內則再更佳。再者,所謂固體成分量,是指從感光性樹脂組成物將溶劑等揮發性成分去除後餘留的全部成分的合計量。The carboxyl group-containing resin (A) is preferably in the range of 5% by mass to 85% by mass relative to the solid content of the photosensitive resin composition, more preferably in the range of 10% by mass to 75% by mass, and even more preferably in the range of 30% by mass to 60% by mass. In addition, the solid content means the total amount of all remaining components after removing volatile components, such as a solvent, from a photosensitive resin composition.
相對於含羧基的樹脂(A),一分子中具有至少一個乙烯性不飽和鍵的不飽和化合物(B)若在5質量%以上且45質量%以下的範圍內則較佳。不飽和化合物(B)在此範圍內,而特別容易製作具有小直徑部63的通孔6。相對於含羧基的樹脂(A),不飽和化合物(B)若在10質量%以上且42質量%以下的範圍內則更佳,若在21質量%以上且40質量%以下的範圍內則再更佳。It is preferable that the unsaturated compound (B) which has at least one ethylenic unsaturated bond in 1 molecule exists in the range of 5 mass % or more and 45 mass % or less with respect to a carboxyl group containing resin (A). The unsaturated compound (B) is within this range, and it is particularly easy to produce the through-hole 6 having the small-diameter portion 63 . The unsaturated compound (B) is more preferably in the range of 10% by mass to 42% by mass based on the carboxyl group-containing resin (A), and more preferably in the range of 21% by mass to 40% by mass.
相對於含羧基的樹脂(A),光聚合起始劑(C)若在1質量%以上且30質量%以下的範圍內則較佳。若相對於含羧基的樹脂(A),光聚合起始劑(C)的比例為1質量%以上,則感光性樹脂組成物容易具有良好的光吸收性。感光性樹脂組成物具有良好的光吸收性,而容易提高層間絕緣層7的表面的硬化的程度,且能夠降低層間絕緣層7的吸水性。此外,更容易於層間絕緣層7形成具有小直徑部63的通孔6。若相對於含羧基的樹脂(A),光聚合起始劑(C)為30質量%以下,則感光性樹脂組成物的硬化膜容易具有良好的電絕緣性。It is preferable that a photoinitiator (C) exists in the range of 1 mass % or more and 30 mass % or less with respect to a carboxyl group-containing resin (A). If the ratio of the photopolymerization initiator (C) is 1% by mass or more with respect to the carboxyl group-containing resin (A), the photosensitive resin composition will tend to have favorable light absorption. The photosensitive resin composition has good light absorption, easily increases the degree of hardening of the surface of the interlayer insulating layer 7 , and can reduce the water absorption of the interlayer insulating layer 7 . In addition, it is easier to form the via hole 6 having the small-diameter portion 63 in the interlayer insulating layer 7 . When the photopolymerization initiator (C) is 30% by mass or less with respect to the carboxyl group-containing resin (A), the cured film of the photosensitive resin composition will tend to have favorable electrical insulation.
相對於含羧基的樹脂(A),光聚合起始劑(C)若在1.5質量%以上且25質量%以下的範圍內則更佳,若在2質量%以上且20質量%以下的範圍內則再更佳,在3質量%以上且10質量%以下的範圍內則特佳。With respect to the carboxyl group-containing resin (A), the photopolymerization initiator (C) is more preferably in the range of 1.5% by mass to 25% by mass, more preferably in the range of 2% by mass to 20% by mass, and particularly preferably in the range of 3% by mass to 10% by mass.
當感光性樹脂組成物含有環氧樹脂(D)時,較佳是:相對於含羧基的樹脂(A)的羧基1當量,環氧樹脂(D)中所含的環氧基的當量的合計為0.1以上且5以下。相對於含羧基的樹脂(A)的羧基1當量,環氧樹脂(D)的環氧基的當量為0.1以上,即能夠對感光性樹脂組成物賦予熱硬化性。相對於含羧基的樹脂(A)的羧基1當量,環氧樹脂(D)的環氧基的當量為5以下,而感光性樹脂組成物具有良好的顯影性。相對於含羧基的樹脂(A)的羧基1當量,環氧樹脂(D)的環氧基的當量更佳為0.3以上且4以下,再更佳為0.5以上且3以下,特佳為0.7以上且2以下。When the photosensitive resin composition contains the epoxy resin (D), it is preferable that the total of the equivalents of the epoxy groups contained in the epoxy resin (D) is 0.1 or more and 5 or less with respect to 1 equivalent of carboxyl groups of the carboxyl group-containing resin (A). The equivalent of the epoxy group of the epoxy resin (D) is 0.1 or more with respect to 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A), that is, thermosetting properties can be imparted to the photosensitive resin composition. The equivalent weight of the epoxy group of the epoxy resin (D) is 5 or less with respect to 1 equivalent of carboxyl groups of the carboxyl group-containing resin (A), and the photosensitive resin composition has favorable developability. The equivalent weight of the epoxy group of the epoxy resin (D) is more preferably from 0.3 to 4, more preferably from 0.5 to 3, particularly preferably from 0.7 to 2, relative to 1 equivalent of carboxyl groups of the carboxyl group-containing resin (A).
相對於含羧基的樹脂(A),有機填料(E)的含量以1質量%以上且100質量%以下為佳。有機填料(E)的含量為1質量%以上,而能夠使感光性樹脂組成物的硬化物的表面適度粗糙化,藉此,能夠提高硬化物的粗糙面與鍍覆面之間的密合性。有機填料(E)的含量為100質量%以下,而感光性樹脂組成物容易具有良好的顯影性。相對於含羧基的樹脂(A),有機填料(E)的含量以1.5質量%以上且50質量%以下較佳,以2質量%以上且30質量%以下更佳,以3質量%以上且20質量%以下特佳。此時,特別容易製作具有小直徑部63的通孔6。The content of the organic filler (E) is preferably 1% by mass or more and 100% by mass or less with respect to the carboxyl group-containing resin (A). The content of the organic filler (E) is 1% by mass or more, and can appropriately roughen the surface of the cured product of the photosensitive resin composition, thereby improving the adhesion between the rough surface of the cured product and the plated surface. Content of an organic filler (E) is 100 mass % or less, and a photosensitive resin composition tends to have favorable developability. The content of the organic filler (E) relative to the carboxyl group-containing resin (A) is preferably from 1.5% by mass to 50% by mass, more preferably from 2% by mass to 30% by mass, and particularly preferably from 3% by mass to 20% by mass. In this case, it is particularly easy to fabricate the through hole 6 having the small-diameter portion 63 .
當感光性樹脂組成物含有矽烷耦合劑時,相對於有機填料(E),矽烷耦合劑的含量以0.01質量%以上且7質量%以下為佳。矽烷耦合劑的比例成為此範圍,而會防止感光性樹脂組成物中的有機填料(E)凝集,而提高分散性。相對於有機填料(E),矽烷耦合劑的比例以0.05質量%以上且5質量%以下較佳。矽烷耦合劑的比例成為此範圍,而會更有效率地防止感光性樹脂組成物中的有機填料(E1)凝集,而更有效地提高分散性。When the photosensitive resin composition contains a silane coupling agent, the content of the silane coupling agent is preferably not less than 0.01% by mass and not more than 7% by mass relative to the organic filler (E). When the ratio of the silane coupling agent is in this range, the aggregation of the organic filler (E) in the photosensitive resin composition is prevented, and the dispersibility is improved. The ratio of the silane coupling agent is preferably not less than 0.05% by mass and not more than 5% by mass relative to the organic filler (E). When the ratio of the silane coupling agent is in this range, the aggregation of the organic filler (E1) in the photosensitive resin composition can be prevented more efficiently, and the dispersibility can be improved more effectively.
當感光性樹脂組成物含有三聚氰胺時,相對於含羧基的樹脂(A),三聚氰胺的含量以0.1質量%以上且10質量%以下為佳。此時,會對鹼性水溶液顯示良好的顯影性,而更容易於層間絕緣層7形成具有小直徑部63的通孔6。相對於含羧基的樹脂(A),三聚氰胺的含量以0.3質量%以上且9質量%以下較佳,以0.5質量%以上且8質量%以下更佳,以1質量%以上且6質量%以下特佳。When the photosensitive resin composition contains melamine, the content of melamine is preferably not less than 0.1% by mass and not more than 10% by mass based on the carboxyl group-containing resin (A). In this case, good developability is exhibited for an alkaline aqueous solution, and it is easier to form the via hole 6 having the small-diameter portion 63 in the interlayer insulating layer 7 . The content of melamine is preferably not less than 0.3% by mass and not more than 9% by mass, more preferably not less than 0.5% by mass and not more than 8% by mass, particularly preferably not less than 1% by mass and not more than 6% by mass, based on the carboxyl group-containing resin (A).
感光性樹脂組成物中的無機填料的比例是適當設定,相對於含羧基的樹脂(A),無機填料的含量以0質量%以上且200質量%以下為佳。此時,能夠獲得良好的顯影性,而更容易於層間絕緣層7形成具有小直徑部63的通孔6。相對於含羧基的樹脂(A),無機填料的含量以0質量%以上且150質量%以下較佳,以0質量%以上且100質量%以下更佳,以0質量%以上且50質量%以下再更佳,以0質量%以上且20質量%以下特佳。The ratio of the inorganic filler in the photosensitive resin composition is set appropriately, and the content of the inorganic filler is preferably 0 mass % or more and 200 mass % or less with respect to the carboxyl group-containing resin (A). In this case, good developability can be obtained, and it is easier to form the via hole 6 having the small-diameter portion 63 in the interlayer insulating layer 7 . Relative to the carboxyl group-containing resin (A), the content of the inorganic filler is preferably from 0% by mass to 150% by mass, more preferably from 0% by mass to 100% by mass, more preferably from 0% by mass to 50% by mass, and particularly preferably from 0% by mass to 20% by mass.
當感光性樹脂組成物含有有機溶劑時,有機溶劑的量較佳是以下述方式調整:以在使由感光性樹脂組成物所形成的塗膜乾燥時使有機溶劑迅速揮發的方式,亦即以使有機溶劑不殘留在乾燥膜的方式。特別是,相對於感光性樹脂組成物整體,有機溶劑的比例以0質量%以上且99.5質量%以下為佳,若為15質量%以上且60質量%以下則更佳。再者,有機溶劑的合適的比例由於因塗佈方法等而異,故較佳是因應塗佈方法來適當調節比例。When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is preferably adjusted in the following manner: when the coating film formed by the photosensitive resin composition is dried, the organic solvent is quickly volatilized, that is, the organic solvent does not remain in the dried film. In particular, the proportion of the organic solvent is preferably from 0 mass % to 99.5 mass % with respect to the entire photosensitive resin composition, and more preferably from 15 mass % to 60 mass %. In addition, since the suitable ratio of an organic solvent differs with a coating method etc., it is preferable to adjust a ratio suitably according to a coating method.
只要不會阻礙本實施形態的效果,感光性組成物即可進一步含有上述成分以外的成分。The photosensitive composition may further contain components other than the above components as long as the effects of the present embodiment are not inhibited.
感光性樹脂組成物可含有從由下述所組成的群組中選出的至少一種樹脂:經以己內醯胺、肟、丙二酸酯等來封端的甲苯二異氰酸酯系、嗎啉二異氰酸酯系、異佛酮二異氰酸酯系、及六亞甲基二異氰酸酯系的經封端的異氰酸酯;丁基化尿素樹脂;前述以外的各種熱硬化性樹脂;紫外線硬化性環氧(甲基)丙烯酸酯;使(甲基)丙烯酸加成在雙酚A型、苯酚酚醛清漆型、甲酚酚醛清漆型、脂環型等的環氧樹脂而得的樹脂;以及鄰苯二甲酸二烯丙酯樹脂、苯氧樹脂、胺酯(urethane)樹脂、三聚氰胺樹脂、氟樹脂等高分子化合物。The photosensitive resin composition may contain at least one resin selected from the group consisting of: toluene diisocyanate, morpholine diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate blocked with caprolactam, oxime, malonate, etc.; butylated urea resin; various thermosetting resins other than the above; ultraviolet curable epoxy (meth)acrylate; Type A, phenol novolak type, cresol novolak type, alicyclic type and other epoxy resins; and diallyl phthalate resin, phenoxy resin, urethane resin, melamine resin, fluorine resin and other polymer compounds.
感光性樹脂組成物可含有硬化劑,該硬化劑是用以使環氧化合物(D)硬化。硬化劑能夠含有例如從由下述所組成的群組中選出的至少一種成分:咪唑、2-甲基咪唑、2-乙基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、4-苯基咪唑、1-氰乙基-2-苯基咪唑、1-(2-氰乙基)-2-乙基-4-甲基咪唑等咪唑衍生物;雙氰胺、苯甲基二甲基胺、4-(二甲胺基)-N,N-二甲基苯甲基胺、4-甲氧基-N,N-二甲基苯甲基胺、4-甲基-N,N-二甲基苯甲基胺等胺化合物;己二醯肼、癸二醯肼等肼化合物;三苯膦等磷化合物;酸酐;酚類;硫醇;路易斯(lewis)酸胺錯合物;及鎓鹽。此等成分的市售物為例如:四國化成股份有限公司製的2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(皆為咪唑系化合物的商品名);San-Apro股份有限公司製的U-CAT3503N、U-CAT3502T(皆為二甲胺的封端異氰酸酯化合物的商品名);DBU、DBN、U-CATSA102、U-CAT5002(皆為二環式脒(amidine)化合物及其鹽)。The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). The hardener can contain, for example, at least one component selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethyl Amine compounds such as benzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic hydrazine and sebacyl hydrazine; phosphorus compounds such as triphenylphosphine; acid anhydrides; phenols; mercaptans; Lewis acid amine complexes; and onium salts. Commercial products of these components are, for example: 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all are trade names of imidazole compounds) manufactured by Shikoku Chemical Co., Ltd.; U-CAT3503N and U-CAT3502T (all are trade names of dimethylamine-blocked isocyanate compounds) manufactured by San-Apro Co., Ltd.; DBU, DBN, U-CATSA102, U-CAT5 002 (both are bicyclic amidine (amidine) compounds and their salts).
感光性樹脂組成物可含有密合性賦予劑。密合性賦予劑可舉例如:甲胍胺(acetoguanamine)(2,4-二胺基-6-甲基-1,3,5-三嗪)、及苯胍胺(benzoguanamine)(2,4-二胺基-6-苯基-1,3,5-三嗪)等胍胺衍生物;以及2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪、2-乙烯基-4,6-二胺基-S-三嗪・異氰脲酸加成物、2,4-二胺基-6-甲基丙烯醯氧基乙基-S-三嗪・異氰脲酸加成物等S-三嗪衍生物;矽烷耦合劑;三聚氰胺衍生物等。The photosensitive resin composition may contain an adhesiveness imparting agent. Adhesion imparting agents include, for example: guanamine derivatives such as acetoguanamine (2,4-diamino-6-methyl-1,3,5-triazine) and benzoguanamine (2,4-diamino-6-phenyl-1,3,5-triazine); S-triazine derivatives such as S-triazine, 2-vinyl-4,6-diamino-S-triazine・isocyanuric acid adduct, 2,4-diamino-6-methacryloxyethyl-S-triazine・isocyanuric acid adduct, etc. S-triazine derivatives; silane coupling agent; melamine derivatives, etc.
感光性樹脂組成物可含有流變控制劑。藉由流變控制劑,而容易使感光性樹脂組成物的黏性合適化。流變控制劑可舉例如:尿素改質中極性聚醯胺(BYK Japan股份有限公司製的型號BYK-430、BYK-431)、聚羥基羧醯胺(BYK Japan股份有限公司製的型號BYK-405)、改質尿素(BYK Japan股份有限公司製的型號BYK-410、BYK-411、BYK-420)、高分子尿素衍生物(BYK Japan股份有限公司製的型號BYK-415)、尿素改質胺酯(BYK Japan股份有限公司製的型號BYK-425)、聚胺酯(BYK Japan股份有限公司製的型號BYK-428)、蓖麻油蠟、聚乙烯蠟、聚醯胺蠟、皂土、高嶺土、黏土。The photosensitive resin composition may contain a rheology control agent. The viscosity of the photosensitive resin composition can be easily adjusted by the rheology control agent. The rheology control agent can be exemplified for example: urea-modified mid-polar polyamide (model BYK-430, BYK-431 produced by BYK Japan Co., Ltd.), polyhydroxycarboxamide (model BYK-405 produced by BYK Japan Co., Ltd.), modified urea (model BYK-410, BYK-411, BYK-420 produced by BYK Japan Co., Ltd.), polymer urea derivatives ( BYK Japan Co., Ltd. model BYK-415), urea modified urethane (BYK Japan Co., Ltd. model BYK-425), polyurethane (BYK Japan Co., Ltd. model BYK-428), castor oil wax, polyethylene wax, polyamide wax, bentonite, kaolin, clay.
感光性樹脂組成物可含有從由下述所組成的群組中選出的至少一種成分:硬化促進劑;著色劑;矽氧、丙烯酸酯等共聚物;塗平(leveling)劑;觸變劑;聚合抑制劑;防光暈劑;阻燃劑;消泡劑;抗氧化劑;界面活性劑;以及高分子分散劑。The photosensitive resin composition may contain at least one component selected from the group consisting of: hardening accelerator; colorant; copolymers such as silicon oxide and acrylate; leveling agent; thixotropic agent; polymerization inhibitor; antihalation agent; flame retardant; defoamer; antioxidant; surfactant;
在調製本實施形態的感光性樹脂組成物時,只要以適當方法來調整即可。例如感光性樹脂組成物能夠藉由下述方式來調整:將感光性樹脂組成物的原料混合並攪拌。此外,亦可以例如下述方式調製感光性樹脂組成物:藉由使用三輥研磨機、球磨機、砂磨機等的適當的揉合方法來揉合。當在原料中含有液狀的成分、黏度低的成分等時,可以下述方式調製感光性樹脂組成物:首先將原料之中的除了液狀的成分、黏度低的成分等以外的部分揉合而調製混合物後,在所獲得的混合物中加入液狀的成分、黏度低的成分等並混合。當感光性樹脂組成物包含溶劑(E)時,首先將原料之中的溶劑的一部分或全部混合後,與剩餘的原料混合。What is necessary is just to adjust by an appropriate method when preparing the photosensitive resin composition of this embodiment. For example, the photosensitive resin composition can be adjusted by mixing and stirring the raw materials of the photosensitive resin composition. In addition, the photosensitive resin composition can also be prepared, for example, by kneading by an appropriate kneading method using a three-roll mill, a ball mill, a sand mill, or the like. When the raw materials contain liquid components, low-viscosity components, etc., the photosensitive resin composition can be prepared by first kneading parts of the raw materials other than the liquid components, low-viscosity components, etc. to prepare a mixture, and then adding the liquid components, low-viscosity components, etc. to the obtained mixture and mixing. When the photosensitive resin composition contains the solvent (E), first, after mixing a part or all of the solvent among the raw materials, it is mixed with the remaining raw materials.
感光性樹脂組成物較佳是具有像下述這樣的性質:即使為厚度25 μm的被膜4,仍能夠以碳酸鈉水溶液來進行顯影。此時,由於能夠從感光性樹脂組成物以光微影法來製作充分厚的電絕緣性的層,故能夠將感光性樹脂組成物廣泛應用於製作印刷線路板11中的層間絕緣層7。當然,亦能夠從感光性樹脂組成物製作較厚度25 μm更薄的電絕緣性的層。The photosensitive resin composition preferably has a property that it can be developed with a sodium carbonate aqueous solution even if it is the film 4 with a thickness of 25 μm. At this time, since a sufficiently thick electrically insulating layer can be produced from the photosensitive resin composition by photolithography, the photosensitive resin composition can be widely used to produce the interlayer insulating layer 7 in the printed wiring board 11 . Of course, an electrically insulating layer thinner than a thickness of 25 μm can also be produced from a photosensitive resin composition.
厚度25 μm的被膜4是否能夠以碳酸鈉水溶液來進行顯影能夠以下述方法來確認。將感光性樹脂組成物塗佈於適當的基材1上而形成濕潤塗膜,並在80℃將此濕潤塗膜加熱40分鐘,而形成厚度25 μm的被膜4。在將負型遮罩直接緊貼在此被膜4的狀態下,在500 mJ/cm 2的條件下將紫外線照射在被膜4而進行曝光,該負型遮罩具有:會使紫外線穿透的曝光部;及會將紫外線遮蔽的非曝光部。在曝光後,對被膜4進行下述處理:以0.2 MPa的噴射壓來將30℃的1%Na 2CO 3水溶液噴射90秒後,以0.2 MPa的噴射壓來將純水噴射90秒。在此處理後觀察被膜4後,結果對應於被膜4中的非曝光部的部分被去除且無法確認有殘渣,此時能夠判斷為厚度25 μm的被膜4能夠以碳酸鈉水溶液來進行顯影。再者,對於其它厚度(例如30 μm)的被膜4,亦同樣能夠確認是否能夠以碳酸鈉水溶液來進行顯影。 Whether or not the film 4 with a thickness of 25 μm can be developed with an aqueous sodium carbonate solution can be confirmed by the following method. A photosensitive resin composition was applied on a suitable substrate 1 to form a wet coating film, and the wet coating film was heated at 80° C. for 40 minutes to form a film 4 with a thickness of 25 μm. In the state where the negative mask is directly attached to the film 4, ultraviolet rays are irradiated on the film 4 under the condition of 500 mJ/cm 2 for exposure. After the exposure, the film 4 was treated by spraying a 1% Na 2 CO 3 aqueous solution at 30° C. for 90 seconds at a spray pressure of 0.2 MPa, and then spraying pure water for 90 seconds at a spray pressure of 0.2 MPa. When the film 4 was observed after this treatment, the portion corresponding to the non-exposed portion of the film 4 was removed and no residue was confirmed. At this time, it can be judged that the film 4 with a thickness of 25 μm can be developed with an aqueous solution of sodium carbonate. Furthermore, it can also be confirmed whether or not it can be developed with a sodium carbonate aqueous solution for a film 4 of other thickness (for example, 30 μm).
(2.2)印刷線路板11的製造 參照第1圖A~第1圖E來詳細說明本實施形態的印刷線路板11的製造方法。 (2.2) Manufacture of printed wiring board 11 The method of manufacturing the printed wiring board 11 of this embodiment will be described in detail with reference to FIGS. 1A to 1E.
在製造印刷線路板11時,準備例如感光性樹脂組成物及基板。基板具有絕緣層2及重疊在絕緣層2的第二導體層3。將由感光性樹脂組成物所製得的被膜4以將第二導體層3覆蓋的方式重疊在基板上,並對被膜4的包含通孔6的圖案的負型圖案狀的區域進行曝光後,使用鹼性水溶液來實施顯影處理。藉此,製作層間絕緣層7及將層間絕緣層7貫穿的通孔6。When manufacturing the printed wiring board 11, for example, a photosensitive resin composition and a substrate are prepared. The substrate has an insulating layer 2 and a second conductor layer 3 stacked on the insulating layer 2 . A coating film 4 made of a photosensitive resin composition is superimposed on the substrate so as to cover the second conductor layer 3, and after exposing the negative pattern-shaped region of the coating film 4 including the pattern of the through hole 6, a development treatment is performed using an alkaline aqueous solution. Thereby, the interlayer insulating layer 7 and the via hole 6 penetrating the interlayer insulating layer 7 are formed.
具體而言是例如:首先,像第1圖A表示的這樣準備基材1。基材1具備絕緣層2及第二導體層3。第二導體層3為導體線路。Specifically, for example, first, a substrate 1 is prepared as shown in FIG. 1A . The substrate 1 includes an insulating layer 2 and a second conductor layer 3 . The second conductor layer 3 is a conductor line.
將感光性樹脂組成物塗佈於基板上,並進一步依需要來使其乾燥,而製作像第1圖B表示的這樣將第二導體層3覆蓋的被膜4。感光性樹脂組成物的塗佈方法是從習知方法、例如由浸漬法、噴霧法、旋轉塗佈法、輥塗佈法、簾幕塗佈法及網版印刷法所組成的群組中選出。當使感光性樹脂組成物乾燥時,是在例如60℃以上且130℃以下的溫度將感光性樹脂組成物加熱。The photosensitive resin composition is applied on the substrate, and further dried as necessary to prepare the film 4 covering the second conductor layer 3 as shown in FIG. 1B. The coating method of the photosensitive resin composition is selected from the group consisting of known methods such as dipping, spraying, spin coating, roll coating, curtain coating and screen printing. When drying the photosensitive resin composition, the photosensitive resin composition is heated at a temperature of, for example, 60° C. or higher and 130° C. or lower.
亦可將由感光性樹脂組成物所製得的乾膜重疊在基板上而製作被膜4。乾膜是例如:將感光性樹脂組成物塗佈於聚酯製等的適當的支撐體上後乾燥,而形成於支撐體上。藉此,獲得一種附有支撐體的乾膜,其具備:乾膜、及用以支撐乾膜的支撐體。將此附有支撐體的乾膜中的乾膜以將第二導體層3覆蓋的方式重疊在基材1後,對乾膜及基材1施加壓力。藉此,由乾膜所構成的被膜4重疊在基材1上。The film 4 can also be produced by overlaying a dry film made of a photosensitive resin composition on a substrate. The dry film is, for example, formed on a support by applying a photosensitive resin composition on an appropriate support made of polyester or the like and drying it. Thereby, a dry film with a support is obtained, which comprises: a dry film and a support for supporting the dry film. After the dry film of the dry film with a support was laminated on the substrate 1 so as to cover the second conductor layer 3 , pressure was applied to the dry film and the substrate 1 . Thereby, the coating film 4 made of a dry film is superimposed on the base material 1 .
然後,對被膜4進行曝光。例如:對被膜4的包含通孔6的圖案的負型圖案狀的區域進行曝光。此時,例如:隔著負型遮罩來將紫外線照射在被膜4。負型遮罩具備:會使紫外線穿透的曝光部;及會將紫外線遮蔽的非曝光部,且非曝光部的圖案包含通孔6的圖案。負型遮罩為例如遮罩薄膜、乾板等曝光工具(photo tool)。紫外線的光源是例如從由下述所組成的群組中選出:化學燈、低壓汞燈、中壓汞燈、高壓汞燈、超高壓汞燈、氙氣燈、及金屬鹵素燈。Then, the film 4 is exposed. For example, exposure is performed on a negative pattern region of the film 4 including the pattern of the through hole 6 . At this time, for example, the coating 4 is irradiated with ultraviolet rays via a negative mask. The negative mask includes: an exposed portion through which ultraviolet rays can pass; and a non-exposed portion capable of shielding ultraviolet rays, and the pattern of the non-exposed portion includes the pattern of the through hole 6 . A negative mask is a photo tool such as a mask film, a dry plate, or the like. The light source of ultraviolet rays is, for example, selected from the group consisting of chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, and metal halide lamps.
當從乾膜製作被膜4時,在對被膜4進行曝光時,例如:預先將支撐體從被膜4剝離後,對被膜4進行曝光。再者,亦可在支撐體重疊在被膜4的狀態下直接穿透支撐體來將紫外線照射在被膜4而對被膜4進行曝光,然後從曝光後的被膜4將支撐體剝離。When producing the film 4 from a dry film, when exposing the film 4 , for example, after peeling the support body from the film 4 in advance, the film 4 is exposed. In addition, the film 4 may be exposed by directly penetrating the support with ultraviolet rays irradiating the film 4 in a state where the support is superimposed on the film 4 , and then the support may be peeled off from the exposed film 4 .
曝光方法亦可採用使用負型遮罩的方法以外的方法。可例如以直接描繪法來對被膜4進行曝光,該直接描繪法是將從光源發出的紫外線僅照射在被膜4的要曝光的部分。直接描繪法中所應用的光源是例如從由下述所組成的群組中選出:高壓汞燈、超高壓汞燈、金屬鹵素燈、g線(436 nm)、h線(405 nm)、i線(365 nm)、以及g線、h線及i線之中的兩種以上的組合。As the exposure method, methods other than the method using a negative mask may be used. The film 4 can be exposed, for example, by a direct drawing method in which only the portion of the film 4 to be exposed is irradiated with ultraviolet light emitted from a light source. The light source used in the direct drawing method is, for example, selected from the group consisting of high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, g-lines (436 nm), h-lines (405 nm), i-lines (365 nm), and combinations of two or more of g-lines, h-lines, and i-lines.
照射在被膜4的紫外線較佳是在365 nm±65 nm的波長區中的至少一個波長具有光譜強度。此外,照射在被膜4的紫外線較佳是在435 nm以上的波長不具有光譜強度。照射在被膜4的紫外線在365 nm±65 nm的波長區中的至少一個波長具有光譜強度,而容易進行被膜4的硬化。此外,若紫外線包含435 nm以上的波長的光,則在顯影後形成於層間絕緣層7的通孔6的第二端62的直徑容易縮小。我們推測其理由是因為:435 nm以上的長波長的光由於不容易被感光性樹脂組成物吸收,故容易傳達直到被膜4的深部為止,而在被膜4的深部容易發生光散射。照射在被膜4的紫外線更佳是在365 nm±45 nm的波長區中的至少一個波長具有光譜強度且在415 nm以上不具有光譜強度,再更佳是在365 nm±30 nm的波長區中的至少一個波長具有光譜強度且在400 nm以上不具有光譜強度,特佳是在365 nm±15 nm的波長區中的至少一個波長具有光譜強度且在385 nm以上不具有光譜強度。The ultraviolet ray irradiated on the coating 4 preferably has a spectral intensity in at least one wavelength in the wavelength region of 365 nm±65 nm. In addition, it is preferable that the ultraviolet rays irradiated on the film 4 have no spectral intensity at a wavelength of 435 nm or more. The ultraviolet rays irradiated on the coating 4 have spectral intensity in at least one wavelength in the wavelength region of 365 nm±65 nm, and hardening of the coating 4 is facilitated. In addition, if the ultraviolet light includes light having a wavelength of 435 nm or more, the diameter of the second end 62 of the via hole 6 formed in the interlayer insulating layer 7 is likely to be reduced after development. The reason for this is presumed to be that long-wavelength light of 435 nm or more is not easily absorbed by the photosensitive resin composition, so it is easy to propagate to the deep part of the film 4, and light scattering is likely to occur in the deep part of the film 4. The ultraviolet ray irradiated on the coating 4 is more preferably at least one wavelength in the wavelength region of 365 nm±45 nm has spectral intensity and does not have spectral intensity above 415 nm, more preferably at least one wavelength in the wavelength region of 365 nm±30 nm has spectral intensity and does not have spectral intensity above 400 nm, and is particularly preferably at least one wavelength in the wavelength region of 365 nm±15 nm has spectral intensity and does not have spectral intensity above 385 nm .
然後,以鹼性水溶液來對被膜4進行顯影,而製作具有通孔6的層間絕緣層7。此時,如同上述說明,容易形成具有小直徑部63的通孔6。對被膜4實施顯影處理,而將第1圖C表示的被膜4的非硬化部分5去除,藉此,像第1圖D表示的這樣設置通孔6。顯影處理中能夠因應感光性樹脂組成物的組成來使用適當的顯影液。顯影液為例如鹼性水溶液或有機胺,該鹼性水溶液含有鹼金屬鹽及鹼金屬氫氧化物之中的至少一種。鹼性水溶液更具體而言含有例如從由下述所組成的群組中選出的至少一種成分:碳酸鈉、碳酸鉀、碳酸銨、碳酸氫鈉、碳酸氫鉀、碳酸氫銨、氫氧化鈉、氫氧化鉀、氫氧化銨、氫氧化四甲銨、及氫氧化鋰。鹼性水溶液中的溶劑可僅為水、或水與低級醇類等親水性有機溶劑的混合物。有機胺含有例如從由下述所組成的群組中選出的至少一種成分:單乙醇胺、二乙醇胺、三乙醇胺、單異丙醇胺、二異丙醇胺、及三異丙醇胺。Then, the film 4 is developed with an alkaline aqueous solution to form the interlayer insulating layer 7 having the through holes 6 . At this time, as described above, it is easy to form the through hole 6 having the small-diameter portion 63 . The film 4 is subjected to developing treatment to remove the non-hardened portion 5 of the film 4 shown in FIG. 1C , thereby forming the through hole 6 as shown in FIG. 1D . An appropriate developer can be used in the development process according to the composition of the photosensitive resin composition. The developing solution is, for example, an alkaline aqueous solution or an organic amine, and the alkaline aqueous solution contains at least one of an alkali metal salt and an alkali metal hydroxide. More specifically, the alkaline aqueous solution contains, for example, at least one component selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and lithium hydroxide. The solvent in the alkaline aqueous solution may be only water, or a mixture of water and hydrophilic organic solvents such as lower alcohols. The organic amine contains, for example, at least one component selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.
鹼性水溶液較佳是含有鹼金屬鹽及鹼金屬氫氧化物之中的至少一種,特佳是含有碳酸鈉。此時,能夠達成改善工作環境及減輕廢棄物處理的負擔。The alkaline aqueous solution preferably contains at least one of an alkali metal salt and an alkali metal hydroxide, and particularly preferably contains sodium carbonate. In this case, it is possible to improve the working environment and reduce the burden of waste disposal.
本實施形態的感光性樹脂組成物由於良好的顯影性,故在顯影後未硬化的感光性樹脂組成物的殘渣不容易殘留在通孔6的底部。因此,容易形成具有小直徑部63的通孔6。Since the photosensitive resin composition of this embodiment has good developability, residues of the uncured photosensitive resin composition after development are less likely to remain on the bottom of the through hole 6 . Therefore, it is easy to form the through hole 6 having the small diameter portion 63 .
然後,可將顯影後的被膜4加熱而使其熱硬化。加熱的條件為例如:加熱溫度120℃以上且200℃以下的範圍內,加熱時間20分鐘以上且180分鐘以下的範圍內,若以上述方式進行而使被膜4熱硬化,則會提高層間絕緣層7的強度、硬度、耐化學藥品性等性能。Then, the film 4 after the development can be heated and thermally cured. The heating conditions are, for example, a heating temperature in the range of 120° C. to 200° C., and a heating time in the range of 20 minutes to 180 minutes. If the film 4 is thermally cured in the above-mentioned manner, the performance such as strength, hardness, and chemical resistance of the interlayer insulating layer 7 will be improved.
可依需要來在加熱前及加熱後之中的一方或雙方進一步將紫外線照射在被膜4。此時,能夠使被膜4的光硬化進一步進行。The film 4 may be further irradiated with ultraviolet rays before heating and after heating, or both, as required. In this case, photocuring of the coating film 4 can be further advanced.
藉由上述,即能夠於基材1上設置由感光性樹脂組成物的硬化物所構成的層間絕緣層7。然後,能夠以加成法等習知方法來在層間絕緣層7上製作導體線路亦即第一導體層8,且在通孔6內製作通孔導體9。藉此,能夠獲得印刷線路板11,該印刷線路板11像第1圖E表示的這樣具備:第一導體層8、第二導體層3、層間絕緣層7、通孔6、及通孔導體9。再者,雖在第1圖E中,通孔導體9是填充在通孔6內整體中,但通孔導體9亦可為將通孔6的內面覆蓋的膜。As a result, the interlayer insulating layer 7 made of a cured photosensitive resin composition can be provided on the substrate 1 . Then, the first conductor layer 8 , which is the conductor line, can be formed on the interlayer insulating layer 7 by a conventional method such as an additive method, and the through-hole conductor 9 can be formed in the through hole 6 . Thereby, printed wiring board 11 including first conductor layer 8 , second conductor layer 3 , interlayer insulating layer 7 , via hole 6 , and via hole conductor 9 as shown in FIG. 1E can be obtained. In addition, although the via-hole conductor 9 is filled in the whole inside of the via-hole 6 in FIG. 1E, the via-hole conductor 9 may be the film which covers the inner surface of the via-hole 6.
此外,亦可在製作通孔導體9之前,使通孔6的內面整體及層間絕緣層7的外表面的一部分粗糙化。此時,能夠提高基材1與通孔導體9之間的密合性。In addition, the entire inner surface of the via hole 6 and a part of the outer surface of the interlayer insulating layer 7 may be roughened before forming the via-hole conductor 9 . In this case, the adhesiveness between base material 1 and via-hole conductor 9 can be improved.
層間絕緣層7的外表面的一部分及通孔6的內面整體的粗糙化能夠以使用氧化劑的一般的除膠渣(desmear)處理相同的順序來進行。例如:使氧化劑與層間絕緣層7的外表面接觸,而使層間絕緣層7的外表面粗糙化。然而,不限於此,亦可採用電漿處理、UV(紫外線)處理和臭氧處理等適當的粗糙化方法。The roughening of a part of the outer surface of the interlayer insulating layer 7 and the entire inner surface of the via hole 6 can be performed in the same procedure as the general desmear treatment using an oxidizing agent. For example, the outer surface of the interlayer insulating layer 7 is roughened by bringing an oxidizing agent into contact with the outer surface of the interlayer insulating layer 7 . However, it is not limited thereto, and appropriate roughening methods such as plasma treatment, UV (ultraviolet) treatment, and ozone treatment may also be employed.
氧化劑可為能夠作為除膠渣液來取得的氧化劑。這樣的氧化劑能夠含有例如:從過錳酸鈉和過錳酸鉀的群組中選出的至少一種過錳酸鹽。The oxidizing agent may be an oxidizing agent available as a desmear solution. Such an oxidizing agent can contain, for example, at least one permanganate selected from the group of sodium permanganate and potassium permanganate.
在設置通孔導體9時,能夠對經粗糙化的外表面的一部分及通孔6的內面實施無電解鍍金屬處理來形成初期導體。然後,以電解鍍金屬處理來使電解鍍覆液中的金屬析出在初期導體,即能夠形成通孔導體9。 [實施例] When the through-hole conductor 9 is provided, an initial conductor can be formed by performing electroless metal plating on a part of the roughened outer surface and the inner surface of the through hole 6 . Then, the metal in the electrolytic plating solution is deposited on the initial conductor by electrolytic metal plating, that is, the via-hole conductor 9 can be formed. [Example]
以下藉由實施例來具體說明本案。惟,本案並不受下述實施例所限定,只要能夠達成本案的目的,則能夠因應設計來進行各種變更。The present case is specifically described below by means of examples. However, this case is not limited by the following embodiments, as long as the purpose of this case can be achieved, various changes can be made according to the design.
1.含羧基的樹脂的合成 [合成例1~6:含雙酚茀骨架的樹脂] 在安裝有回流冷卻器、溫度計、空氣噴吹管及攪拌機的四頸燒瓶內,加入表1中的「第一反應」欄中表示的成分,並在空氣起泡下將此等攪拌,而調製混合物。在燒瓶內將此混合物一面在空氣起泡下攪拌,一面以「反應條件」欄中表示的反應溫度及反應時間來加熱。藉此,調製中間體的溶液。 1. Synthesis of carboxyl-containing resins [Synthesis Examples 1 to 6: Resins containing a bisphenol peroxide skeleton] In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing tube, and a stirrer, the ingredients indicated in the "First Reaction" column in Table 1 were added, and these were stirred under air bubbling to prepare a mixture. This mixture was heated in the flask under the reaction temperature and reaction time shown in the column of "reaction conditions" while stirring under air bubbling. Thereby, the solution of the intermediate body was prepared.
然後,在燒瓶內的中間體的溶液中,投入表1的「第二反應」欄表示的成分,並一面在空氣起泡下攪拌,一面以「反應條件(1)」欄中表示的反應溫度及反應時間來加熱。然後,一面在空氣起泡下攪拌,一面以「反應條件(2)」欄中表示的反應溫度及反應時間來加熱。藉此,獲得含羧基的樹脂的65質量%溶液。含羧基的樹脂的重量平均分子量及酸值是如同表1中表示。Then, into the solution of the intermediate in the flask, the components shown in the "Second Reaction" column of Table 1 were added, and while stirring under air bubbling, the mixture was heated at the reaction temperature and reaction time shown in the "Reaction Condition (1)" column. Then, while stirring under air bubbling, it heated at the reaction temperature and reaction time shown in the column of "reaction conditions (2)". Thereby, a 65% by mass solution of a carboxyl group-containing resin was obtained. The weight average molecular weight and acid value of the carboxyl group-containing resin are as shown in Table 1.
再者,表1中的(a1)欄中表示的成分的詳細內容是如下所述。 ・環氧化合物1:式(2)表示且式(2)中的R 1~R 8皆為氫的環氧當量250 g/eq的雙酚茀型環氧化合物。 ・環氧化合物2:式(2)表示且式(2)中的R 1及R 5皆為甲基且R 2~R 4及R 6~R 8皆為氫的環氧當量279 g/eq的雙酚茀型環氧化合物。 In addition, the detail of the component shown in the (a1) column in Table 1 is as follows. - Epoxy compound 1: a bisphenol fluorine-type epoxy compound represented by formula (2), wherein R 1 to R 8 in formula (2) are all hydrogen, and has an epoxy equivalent of 250 g/eq.・Epoxy compound 2: a bisphenol fluorine-type epoxy compound represented by formula (2), in which R 1 and R 5 are both methyl groups, and R 2 to R 4 and R 6 to R 8 are all hydrogen, and have an epoxy equivalent of 279 g/eq.
[合成例7:含聯苯酚醛清漆骨架的樹脂] 在安裝有回流冷卻器、溫度計、空氣噴吹管及攪拌機的四頸燒瓶內,加入聯苯酚醛清漆型環氧樹脂(日本化藥股份有限公司製,型號NC-3000-H,環氧當量288 g/eq)288質量份、二乙二醇單乙基醚乙酸酯155質量份、甲基氫醌0.2質量份、丙烯酸72質量份、及三苯膦3質量份,而調製混合物。在燒瓶內將此混合物一面在空氣起泡下攪拌,一面在115℃的溫度加熱12小時。藉此,調製中間體的溶液。 [Synthesis Example 7: Resin Containing Biphenyl Novolak Skeleton] In a four-necked flask equipped with a reflux cooler, a thermometer, an air blowing pipe, and a stirrer, 288 parts by mass of a biphenyl novolak-type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., model NC-3000-H, epoxy equivalent 288 g/eq), 155 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 72 parts by mass of acrylic acid, and 3 parts by mass of triphenylphosphine were added to prepare a mixture. The mixture was heated in a flask at a temperature of 115° C. for 12 hours while stirring under air bubbling. Thereby, the solution of the intermediate body was prepared.
然後,在燒瓶內的中間體的溶液中,投入四氫鄰苯二甲酸酐85質量份及二乙二醇單乙基醚乙酸酯86.3質量份,並一面在空氣起泡下攪拌,一面在90℃加熱4小時。藉此,獲得含羧基的樹脂B-1的65質量%溶液。含羧基的樹脂B-1的重量平均分子量為8026,酸值為69 mgKOH/g。Then, 85 parts by mass of tetrahydrophthalic anhydride and 86.3 parts by mass of diethylene glycol monoethyl ether acetate were added to the solution of the intermediate in the flask, and heated at 90° C. for 4 hours while stirring under air bubbling. Thereby, a 65% by mass solution of carboxyl group-containing resin B-1 was obtained. The weight average molecular weight of the carboxyl group-containing resin B-1 was 8026, and the acid value was 69 mgKOH/g.
2.組成物的調製 使用三輥研磨機來將後述表2~3表示的成分揉合後,在燒瓶內攪拌混合,而獲得組成物。再者,表2~3表示的成分的詳細內容是如下所述。 ・不飽和化合物A:三羥甲基丙烷三丙烯酸酯。 ・光聚合起始劑A:2,4,6-三甲基苯甲醯基二苯基氧化膦,BASF公司製,型號Irgacure TPO。 ・光聚合起始劑B:1-羥基環己基苯基酮,BASF公司製,型號Irgacure 184。 ・光聚合起始劑C:4,4’-雙(二乙胺基)二苯甲酮。 ・光聚合起始劑D:2,4-二乙基噻噸-9-酮。 ・結晶性環氧樹脂A:雙酚型結晶性環氧樹脂,NIPPON STEEL Chemical & Material股份有限公司製的型號YSLV-80XY,熔點75~85℃,環氧當量192 g/eq。 ・非晶性環氧樹脂溶液A:使含長鏈碳鏈的雙酚A型環氧樹脂,DIC股份有限公司製,型號EPICLON EXA-4816,液狀樹脂,環氧當量410 g/eq,以固體成分90%來溶於二乙二醇單乙基乙酸酯中而成的溶液。 ・有機填料A的分散液:以含量相對於分散液總量為15重量%來在甲基乙基酮中使平均初級粒徑0.07 μm的交聯橡膠(NBR)分散而成的分散液(JSR股份有限公司製,型號XER-91-MEK;酸值10.0 mgKOH/g)。 ・有機填料B:平均初級粒徑0.3 μm的縮水甘油基改質丙烯腈丁二烯橡膠。 ・添加劑A:3-縮水甘油氧基丙基三甲氧基矽烷。 ・添加劑B:三聚氰胺。 ・溶劑A:甲基乙基酮。 2. Modulation of composition After kneading the components shown in Tables 2 to 3 described later using a three-roll mill, they were stirred and mixed in a flask to obtain a composition. In addition, the details of the components shown in Tables 2-3 are as follows. ・Unsaturated compound A: trimethylolpropane triacrylate. - Photopolymerization initiator A: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BASF Corporation, model Irgacure TPO. - Photopolymerization initiator B: 1-hydroxycyclohexyl phenyl ketone, manufactured by BASF Corporation, model Irgacure 184. ・Photopolymerization initiator C: 4,4'-bis(diethylamino)benzophenone. ・Photopolymerization initiator D: 2,4-diethylthioxanthen-9-one. ・Crystalline epoxy resin A: bisphenol type crystalline epoxy resin, model YSLV-80XY manufactured by NIPPON STEEL Chemical & Material Co., Ltd., melting point 75-85° C., epoxy equivalent 192 g/eq. ・Amorphous epoxy resin solution A: A solution obtained by dissolving bisphenol A type epoxy resin containing long carbon chains, manufactured by DIC Co., Ltd., model EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g/eq, in diethylene glycol monoethyl acetate at a solid content of 90%. ・Dispersion of organic filler A: a dispersion obtained by dispersing cross-linked rubber (NBR) with an average primary particle diameter of 0.07 μm in methyl ethyl ketone at a content of 15% by weight relative to the total amount of the dispersion (manufactured by JSR Co., Ltd., model XER-91-MEK; acid value: 10.0 mgKOH/g). ・Organic filler B: Glycidyl-modified acrylonitrile butadiene rubber with an average primary particle size of 0.3 μm. ・Additive A: 3-glycidoxypropyltrimethoxysilane. ・Additive B: Melamine. ・Solvent A: methyl ethyl ketone.
3.組成物的評估 (1)試驗片的製作 使用各組成例的組成物來以下述方式製作試驗片。 3. Evaluation of composition (1) Preparation of test piece Using the composition of each composition example, the test piece was produced as follows.
使用塗抹器來將各組成例的組成物塗佈於聚對苯二甲酸乙二酯製的薄膜上後,在80℃加熱5分鐘後,在95℃加熱20分鐘而使其乾燥,藉此於薄膜上形成厚度35 μm的乾膜。The composition of each composition example was coated on a polyethylene terephthalate film using an applicator, heated at 80° C. for 5 minutes, and then dried at 95° C. for 20 minutes to form a dry film with a thickness of 35 μm on the film.
準備具備厚度17.5 μm的銅箔的玻璃環氧覆銅積層板(FR-4型)。以蝕刻劑(MEC股份有限公司製的型號CZ-8101)來對此玻璃環氧覆銅積層板中的厚度1 μm左右的表面部分進行處理而使其粗糙化。使用真空積層機來將上述乾膜加熱積層於此玻璃環氧覆銅積層板的一面整面。將加熱積層的條件設定為0.5 MPa、80℃、1分鐘。藉此,於玻璃環氧覆銅積層板上形成由上述乾膜所構成的被膜。隔著具有包含直徑80 μm的圓形形狀的圖案的非曝光部的負型遮罩及聚對苯二甲酸乙二酯製的薄膜,將波長365 nm的紫外線在累計光量250 mJ/cm 2的條件下照射在此被膜。然後,從被膜將聚對苯二甲酸乙二酯製的薄膜剝離。 A glass-epoxy copper-clad laminate (FR-4 type) having a copper foil with a thickness of 17.5 μm was prepared. The surface portion of the glass-epoxy copper-clad laminate with a thickness of about 1 μm was treated with an etchant (model CZ-8101 manufactured by MEC Co., Ltd.) to roughen it. A vacuum lamination machine was used to heat-laminate the above-mentioned dry film on one side of the glass-epoxy copper-clad laminate. The conditions for heating lamination were set to 0.5 MPa, 80° C., and 1 minute. Thereby, the coating film which consists of the said dry film was formed on the glass epoxy copper-clad laminated board. Ultraviolet rays with a wavelength of 365 nm were irradiated to the film at a cumulative light intensity of 250 mJ/cm 2 through a negative mask having a non-exposed portion of a circular pattern with a diameter of 80 μm and a polyethylene terephthalate film. Then, the polyethylene terephthalate film was peeled off from the film.
然後,對被膜以0.2 MPa的噴射壓來將30℃的鹼性水溶液(1%Na 2CO 3水溶液)噴射90秒後,以0.2 MPa的噴射壓來將純水噴射90秒,而對被膜進行顯影。然後,在180℃將被膜加熱120分鐘。藉此,於印刷線路板上形成層間絕緣層及將此層間絕緣層貫穿的通孔。藉此,獲得試驗片。 Then, the film was developed by spraying a 30° C. alkaline aqueous solution (1% Na 2 CO 3 aqueous solution) at a spray pressure of 0.2 MPa for 90 seconds, and then spraying pure water at a spray pressure of 0.2 MPa for 90 seconds. Then, the film was heated at 180° C. for 120 minutes. Thereby, an interlayer insulating layer and a through hole penetrating the interlayer insulating layer are formed on the printed circuit board. Thereby, a test piece was obtained.
對此試驗片進行下述評估。再者,組成例11中,無法進行顯影,而未進行評估。此外,組成例14中,由於有在顯影時能夠觀察到由硬化不足所造成的被膜剝離的位置,故未進行評估。The following evaluations were performed on this test piece. In addition, in composition example 11, development was not possible, and evaluation was not performed. In addition, in Composition Example 14, evaluation was not performed because there was a position where film peeling due to insufficient curing was observed during development.
(2)第一端的直徑及第二端的直徑的測定 將試驗片以在與通孔的軸平行的面將通孔對切的方式切割,並使用電子顯微鏡(SEM)來對剖面進行攝影。從由此所得的影像測定通孔的第一端的直徑及第二端的直徑。此外,求出(第一端的直徑÷第二端的直徑)×100(%)的值。 (2) Determination of the diameter of the first end and the diameter of the second end The test piece was cut so as to bisect the through-hole on a plane parallel to the axis of the through-hole, and the cross-section was photographed using an electron microscope (SEM). From the images thus obtained, the diameter of the first end and the diameter of the second end of the through hole were determined. In addition, the value of (diameter of the first end÷diameter of the second end)×100(%) was obtained.
(3)小直徑部的有無 從上述「(2)第一端的直徑及第二端的直徑的測定」中所得的影像,確認於通孔的第一端與第二端之間是否有小直徑部存在,並以下述方式進行評估。 A:於第一端與第二端之間有小直徑部存在,且相對於第二端的直徑,小直徑部的最小直徑為65%以上且未達100%。 B:於第一端與第二端之間有小直徑部存在,且相對於第二端的直徑,小直徑部的最小直徑為未達65%。 C:於第一端與第二端之間小直徑部不存在。 (3) Presence of small diameter part From the images obtained in the above "(2) Measurement of the diameter of the first end and the diameter of the second end", whether there is a small-diameter portion between the first end and the second end of the through hole was confirmed, and evaluated in the following manner. A: A small-diameter portion exists between the first end and the second end, and the minimum diameter of the small-diameter portion is 65% or more and less than 100% of the diameter of the second end. B: A small-diameter portion exists between the first end and the second end, and the minimum diameter of the small-diameter portion is less than 65% of the diameter of the second end. C: The small-diameter portion does not exist between the first end and the second end.
(4)通孔形狀的評估 從上述「(2)第一端的直徑及第二端的直徑的測定」中所得的影像,以下述方式評估通孔的形狀。 A:(第一端的直徑÷第二端的直徑)×100(%)的值為80%以上,且於第一端與第二端之間有相對於第二端的直徑為65%以上且未達100%的小直徑部存在。 B:(第一端的直徑÷第二端的直徑)×100(%)的值為75%以上且未達80%,且於第一端與第二端之間有相對於第二端的直徑為65%以上且未達100%的小直徑部存在。 C:(第一端的直徑÷第二端的直徑)×100(%)的值為65%以上且未達75%,且於第一端與第二端之間有相對於第二端的直徑為65%以上且未達100%的小直徑部存在。 D:(第一端的直徑÷第二端的直徑)×100(%)的值為未達65%,且於第一端與第二端之間有小直徑部存在。 E:小直徑部不存在。 (4) Evaluation of via hole shape From the images obtained in the above "(2) Measurement of the diameter of the first end and the diameter of the second end", the shape of the through-hole was evaluated in the following manner. A: The value of (diameter of the first end÷diameter of the second end)×100(%) is 80% or more, and there is a small-diameter portion between the first end and the second end with a diameter of 65% or more and less than 100% of the diameter of the second end. B: The value of (diameter of the first end÷diameter of the second end)×100(%) is 75% or more and less than 80%, and there is a small diameter portion between the first end and the second end with a diameter of 65% or more and less than 100% of the diameter of the second end. C: The value of (diameter of the first end÷diameter of the second end)×100(%) is 65% or more and less than 75%, and there is a small diameter portion between the first end and the second end with a diameter of 65% or more and less than 100% of the diameter of the second end. D: The value of (diameter of the first end÷diameter of the second end)×100(%) is less than 65%, and a small-diameter portion exists between the first end and the second end. E: There is no small-diameter portion.
上述評估試驗的結果是如下述表2~3所示。The results of the evaluation tests described above are shown in Tables 2 to 3 below.
4.印刷線路板的評估 (1)試驗片的製作 除了將在製作被膜時的被膜的形成方法及被膜的厚度、曝光時的圓形形狀的圖案的直徑、紫外線的波長及累計光量、以及顯影時的鹼性水溶液的噴射時間設為如表4~6所示以外,其餘以上述「1.組成物的評估」中的「(1)試驗片的製作」中所說明的方法來製作試驗片。再者,當於波長的欄中記載有複數個數值時,是同時照射具有各數值的波長的紫外線。 4. Evaluation of printed circuit boards (1) Preparation of test piece Test pieces were produced by the method described in "(1) Preparation of test pieces" in "1. Evaluation of composition" above, except that the method of forming the film and the thickness of the film at the time of film production, the diameter of the circular pattern at the time of exposure, the wavelength of ultraviolet light and the integrated light intensity, and the spraying time of the alkaline aqueous solution at the time of development were as shown in Tables 4 to 6. In addition, when plural numerical values are described in the column of the wavelength, the ultraviolet rays having the wavelengths of the respective numerical values are irradiated simultaneously.
對此試驗片進行下述評估。再者,比較例1中,無法進行顯影,而未進行評估。此外,比較例3中,由於有在顯影時能夠觀察到由硬化不足所造成的被膜剝離的位置,故未進行評估。The following evaluations were performed on this test piece. In addition, in the comparative example 1, image development was not possible, and evaluation was not performed. In addition, in Comparative Example 3, evaluation was not performed because there was a position where film peeling due to insufficient curing was observed during image development.
(2)第一端的直徑及第二端的直徑的測定 將試驗片以在與通孔的軸平行的面將通孔對切的方式切割,並使用電子顯微鏡(SEM)來觀察剖面。從由此所得的影像測定通孔的第一端的直徑及第二端的直徑。此外,求出(第一端的直徑÷第二端的直徑)×100(%)的值。 (2) Determination of the diameter of the first end and the diameter of the second end The test piece was cut so as to bisect the through hole on a plane parallel to the axis of the through hole, and the cross section was observed using an electron microscope (SEM). From the images thus obtained, the diameter of the first end and the diameter of the second end of the through hole were determined. In addition, the value of (diameter of the first end÷diameter of the second end)×100(%) was obtained.
(3)小直徑部的有無 從上述「(2)第一端的直徑及第二端的直徑的測定」中所得的影像,確認於通孔的第一端與第二端之間是否有小直徑部存在,並以下述方式進行評估。 A:於第一端與第二端之間有小直徑部存在,且相對於第二端的直徑,小直徑部的最小直徑為65%以上且未達100%。 B:於第一端與第二端之間有小直徑部存在,且相對於第二端的直徑,小直徑部的最小直徑為未達65%。 C:於第一端與第二端之間小直徑部不存在。 (3) Presence of small diameter part From the images obtained in the above "(2) Measurement of the diameter of the first end and the diameter of the second end", whether there is a small-diameter portion between the first end and the second end of the through hole was confirmed, and evaluated in the following manner. A: A small-diameter portion exists between the first end and the second end, and the minimum diameter of the small-diameter portion is 65% or more and less than 100% of the diameter of the second end. B: A small-diameter portion exists between the first end and the second end, and the minimum diameter of the small-diameter portion is less than 65% of the diameter of the second end. C: The small-diameter portion does not exist between the first end and the second end.
(4)通孔形狀的評估 從上述「(2)第一端的直徑及第二端的直徑的測定」中所得的影像,以下述方式評估通孔的形狀。 A:(第一端的直徑÷第二端的直徑)×100(%)的值為80%以上,且於第一端與第二端之間有相對於第二端的直徑為65%以上且未達100%的小直徑部存在。 B:(第一端的直徑÷第二端的直徑)×100(%)的值為75%以上且未達80%,且於第一端與第二端之間有相對於第二端的直徑為65%以上且未達100%的小直徑部存在。 C:(第一端的直徑÷第二端的直徑)×100(%)的值為65%以上且未達75%,且於第一端與第二端之間有相對於第二端的直徑為65%以上且未達100%的小直徑部存在。 D:(第一端的直徑÷第二端的直徑)×100(%)的值為未達65%,且於第一端與第二端之間有小直徑部存在。 E:小直徑部不存在。 (4) Evaluation of via hole shape From the images obtained in the above "(2) Measurement of the diameter of the first end and the diameter of the second end", the shape of the through-hole was evaluated in the following manner. A: The value of (diameter of the first end÷diameter of the second end)×100(%) is 80% or more, and there is a small-diameter portion between the first end and the second end with a diameter of 65% or more and less than 100% of the diameter of the second end. B: The value of (diameter of the first end÷diameter of the second end)×100(%) is 75% or more and less than 80%, and there is a small diameter portion between the first end and the second end with a diameter of 65% or more and less than 100% of the diameter of the second end. C: The value of (diameter of the first end÷diameter of the second end)×100(%) is 65% or more and less than 75%, and there is a small diameter portion between the first end and the second end with a diameter of 65% or more and less than 100% of the diameter of the second end. D: The value of (diameter of the first end÷diameter of the second end)×100(%) is less than 65%, and a small-diameter portion exists between the first end and the second end. E: There is no small-diameter portion.
(5)通孔連接可靠性 對於試驗片,對層間絕緣層的外表面以作為鍍覆處理的前步驟的一般的下述除膠渣處理來使其粗糙化。 (5) Through-hole connection reliability For the test piece, the outer surface of the interlayer insulating layer was roughened by the following general desmear treatment as a step before the plating treatment.
對層間絕緣層在70℃使用除膠渣用膨潤液(Atotech Japan股份有限公司製的Swelling Dip Securiganth P)來進行膨潤處理10分鐘,而使層間絕緣層的表面膨潤後,對層間絕緣層進行熱水洗。然後,對層間絕緣層的表面在70℃使用除膠渣液(含有過錳酸鉀的氧化劑,Atotech Japan股份有限公司製的Concentrate Compact CP)來進行處理10分鐘而使其粗糙化後,對層間絕緣層進行熱水洗。然後,對層間絕緣層的表面在40℃使用中和液(Atotech Japan股份有限公司製的Reduction Securiganth P)來進行處理5分鐘而將殘渣去除後,對層間絕緣層進行水洗。The interlayer insulating layer was subjected to swelling treatment at 70° C. for 10 minutes using a swelling solution for desmearing (Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd.) to swell the surface of the interlayer insulating layer, and then the interlayer insulating layer was washed with hot water. Then, the surface of the interlayer insulating layer was roughened by treatment with a desmear solution (an oxidizing agent containing potassium permanganate, Concentrate Compact CP manufactured by Atotech Japan Co., Ltd.) at 70° C. for 10 minutes, and then the interlayer insulating layer was washed with hot water. Then, the surface of the interlayer insulating layer was treated with a neutralizing solution (Reduction Securiganth P manufactured by Atotech Japan Co., Ltd.) at 40° C. for 5 minutes to remove residues, and then the interlayer insulating layer was washed with water.
然後,對層間絕緣層上實施無電解鍍銅處理,而製作初期導體後,在150℃加熱1小時。然後,對初期導體上在電流密度2 A/dm 2的條件下實施電解鍍銅處理後,在180℃加熱30分鐘。藉此,在層間絕緣層上製作厚度33 μm的第一導體層,且在通孔內製作通孔導體。 Then, electroless copper plating was performed on the interlayer insulating layer to form an initial conductor, followed by heating at 150° C. for 1 hour. Then, electrolytic copper plating was performed on the primary conductor under the condition of a current density of 2 A/dm 2 , and then heated at 180° C. for 30 minutes. Thereby, a first conductor layer having a thickness of 33 μm was formed on the interlayer insulating layer, and via conductors were formed in the via holes.
然後,對試驗片實施下述溫度循環試驗:將暴露在-55℃15分鐘的條件下後暴露在125℃15分鐘的條件下的循環進行500個循環。測定通過試驗前後的通孔導體的第一導體層與第二導體層之間的電阻值,並以下述方式評估其變化率。 A:溫度循環試驗前後的電阻值的變化率為未達8%。 B:溫度循環試驗前後的電阻值的變化率為8%以上且未達10%。 C:溫度循環試驗前後的電阻值的變化率為10%以上。 Then, the test piece was subjected to a temperature cycle test in which a cycle of exposing to a condition of −55° C. for 15 minutes and then exposing to a condition of 125° C. for 15 minutes was performed 500 cycles. The resistance value between the first conductor layer and the second conductor layer of the via-hole conductor before and after passing the test was measured, and the rate of change thereof was evaluated in the following manner. A: The rate of change in resistance value before and after the temperature cycle test was less than 8%. B: The change rate of the resistance value before and after the temperature cycle test is 8% or more and less than 10%. C: The change rate of the resistance value before and after the temperature cycle test is 10% or more.
上述評估試驗的結果是如下述表4~6所示。The results of the evaluation tests described above are shown in Tables 4 to 6 below.
[表1] [Table 1]
[表2] [Table 2]
[表3] [table 3]
[表4] [Table 4]
[表5] [table 5]
[表6] [Table 6]
1:基材 2:絕緣層 3:第二導體層 4:被膜 5:非硬化部分 6:通孔 61:第一端 62:第二端 63:小直徑部 7:層間絕緣層 8:第一導體層 9:通孔導體 11:印刷線路板 1: Substrate 2: Insulation layer 3: Second conductor layer 4: film 5: Non-hardened part 6: Through hole 61: first end 62: second end 63: small diameter part 7: Interlayer insulating layer 8: The first conductor layer 9: Through hole conductor 11: Printed circuit board
第1圖A、第1圖B、第1圖C、第1圖D、及第1圖E為顯示製造印刷線路板的步驟的剖面圖。Fig. 1 A, Fig. 1 B, Fig. 1 C, Fig. 1 D, and Fig. 1 E are cross-sectional views showing steps of manufacturing a printed wiring board.
國內寄存資訊(請依寄存機構、日期、號碼順序註記) 無 國外寄存資訊(請依寄存國家、機構、日期、號碼順序註記) 無 Domestic deposit information (please note in order of depositor, date, and number) none Overseas storage information (please note in order of storage country, institution, date, and number) none
1:基材 1: Substrate
2:絕緣層 2: Insulation layer
3:第二導體層 3: Second conductor layer
4:被膜 4: film
5:非硬化部分 5: Non-hardened part
6:通孔 6: Through hole
61:第一端 61: first end
62:第二端 62: second end
63:小直徑部 63: small diameter part
7:層間絕緣層 7: Interlayer insulating layer
8:第一導體層 8: The first conductor layer
9:通孔導體 9: Through hole conductor
11:印刷線路板 11: Printed circuit board
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JP2009188146A (en) * | 2008-02-06 | 2009-08-20 | Murata Mfg Co Ltd | Method for manufacturing wiring board |
JP2011210794A (en) * | 2010-03-29 | 2011-10-20 | Sumitomo Bakelite Co Ltd | Insulating substrate, method of manufacturing the same, printed-wiring board, and semiconductor device |
TW201635867A (en) * | 2015-02-24 | 2016-10-01 | Ajinomoto Kk | Circuit board and manufacturing method thereof |
TW201727373A (en) * | 2016-01-19 | 2017-08-01 | 互應化學工業股份有限公司 | Photo-sensitive resin composition, dry film, and printed wiring board |
Also Published As
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CN114449745A (en) | 2022-05-06 |
TW202225844A (en) | 2022-07-01 |
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