TWI684522B - Manufacturing method of copper foil with release layer, laminate, printed wiring board, and manufacturing method of electronic equipment - Google Patents
Manufacturing method of copper foil with release layer, laminate, printed wiring board, and manufacturing method of electronic equipment Download PDFInfo
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- TWI684522B TWI684522B TW107110197A TW107110197A TWI684522B TW I684522 B TWI684522 B TW I684522B TW 107110197 A TW107110197 A TW 107110197A TW 107110197 A TW107110197 A TW 107110197A TW I684522 B TWI684522 B TW I684522B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
- H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
- H05K3/182—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method
- H05K3/184—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating characterised by the patterning method using masks
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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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
本發明提供一種附脫模層的銅箔,其可製作埋入電路,且可良好地抑制利用蝕刻使所述埋入電路露出時侵蝕埋入電路。本發明的附脫模層的銅箔依序具備脫模層、銅箔和阻隔層。 The present invention provides a copper foil with a release layer, which can make a buried circuit, and can well suppress corrosion of the buried circuit when the buried circuit is exposed by etching. The copper foil with a mold release layer of the present invention includes a mold release layer, a copper foil, and a barrier layer in this order.
Description
本發明係關於一種附脫模層的銅箔、積層體、印刷配線板的製造方法及電子機器的製造方法。 The invention relates to a method for manufacturing a copper foil with a release layer, a laminate, a printed wiring board, and a method for manufacturing an electronic device.
印刷配線板在這半世紀間實現大的進展,如今幾乎被用於所有電子機器。伴隨近年來電子機器的小型化、高性能化需求的增大,搭載零件的高密度安裝化或信號的高頻化不斷進展,對印刷配線板要求導體圖案的微細化(微間距化)或高頻應對等。 Printed wiring boards have made great progress in the past half century, and are now used in almost all electronic machines. With the increasing demand for miniaturization and high performance of electronic devices in recent years, the high-density mounting of mounted components and the increase in the frequency of signals continue to progress, and the printed wiring boards are required to be finer (micro-pitch) or higher in conductor patterns Respond frequently.
印刷配線板首先製造成覆銅積層體,所述覆銅積層體是將銅箔與以玻璃環氧基板、BT樹脂、聚醯亞胺膜等為主的絕緣基板貼合而成。貼合使用以下方法:將絕緣基板與銅箔重疊並進行加熱加壓而形成的方法(層壓法);或者將作為絕緣基板材料的前驅物的清漆塗布於銅箔的具有被覆層的面並進行加熱、硬化的方法(流延法)。 The printed wiring board is first manufactured as a copper-clad laminate, which is formed by bonding copper foil to an insulating substrate mainly composed of a glass epoxy substrate, BT resin, polyimide film, or the like. For the lamination, the following method is used: a method in which an insulating substrate and a copper foil are overlapped and heated and pressed (lamination method); or a varnish that is a precursor of an insulating substrate material is applied to the surface of the copper foil with the coating layer and The method of heating and hardening (casting method).
近年來,開發出分別根據目的而以各種製法製作的印刷配線板並加以利用。例如已知利用所謂的埋入法製造的印刷配線板等電路埋入基板(ETS,Embedded Trace Substrate),所述埋入法是在極薄銅箔的表面形成電路鍍層,以覆蓋所述形成的電路鍍層的方式(以掩埋電路鍍層的方式),在極薄銅箔上設置埋入樹脂而積層樹脂層,使用所述被埋入的電路鍍層形成印刷配線板等(專利文獻1)。 In recent years, printed wiring boards manufactured by various manufacturing methods according to purposes have been developed and utilized. For example, a circuit embedding substrate (ETS, Embedded Trace Substrate) such as a printed wiring board manufactured by a so-called embedding method is known. The embedding method is to form a circuit plating layer on the surface of an extremely thin copper foil to cover the formed In the method of circuit plating (in which the circuit plating is buried), a resin layer is embedded on an extremely thin copper foil and a resin layer is laminated, and a printed wiring board or the like is formed using the embedded circuit plating layer (Patent Document 1).
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本特開2005-101137號公報 [Patent Document 1] Japanese Unexamined Patent Publication No. 2005-101137
作為所述電路埋入基板的製作方法的一個例子,首先,在極薄銅箔的表面形成電路,以覆蓋所述電路的方式積層樹脂,形成埋入電路。其次,將積層於極薄銅箔的載體銅箔剝離後,利用蝕刻將極薄銅箔去除,藉此使埋入樹脂中的電路露出,藉此利用所述埋入電路製作印刷配線板。 As an example of the method for manufacturing the embedded circuit board, first, an electric circuit is formed on the surface of an extremely thin copper foil, and a resin is laminated so as to cover the electric circuit to form an embedded circuit. Next, after the carrier copper foil laminated on the ultra-thin copper foil is peeled off, the ultra-thin copper foil is removed by etching, thereby exposing the circuit embedded in the resin, thereby producing a printed wiring board using the embedded circuit.
然而,如果像所述那樣以覆蓋電路的方式積層樹脂而形成埋入電路後,利用蝕刻將極薄銅箔去除而使埋入電路露出,則會存在因所述極薄銅箔的蝕刻導致埋入電路被侵蝕的問題。 However, if the embedded circuit is formed by covering the circuit as described above to form a buried circuit, then the ultrathin copper foil is removed by etching to expose the buried circuit, there may be buried by the etching of the ultrathin copper foil The problem of erosion into the circuit.
另外,為了容易進行對銅箔的各種加工,有時在藉由貼合於樹脂等支持體而支撐銅箔的狀態下進行所述加工。此時,藉由在銅箔的與樹脂等支持體的貼合側表面設置脫模層,而可在加工後容易地將樹脂等支持體剝離。關於這種附脫模層的銅箔,以往並沒有用於像所述那樣的埋入法的例子。 In addition, in order to easily perform various processing on the copper foil, the processing may be performed in a state where the copper foil is supported by being bonded to a support such as resin. In this case, by providing a release layer on the surface of the copper foil that is attached to the support such as resin, the support such as resin can be easily peeled off after processing. Regarding such a copper foil with a release layer, there has not been an example of the embedding method as described above.
本發明人等進行了努力研究,結果發現,藉由在附脫模層的銅箔的與脫模層側表面為相反側的表面設置阻隔層,可使用附脫模層的銅箔製作埋入電路,且可良好地抑制利用蝕刻使所述埋入電路露出時侵蝕埋入電路。 The present inventors have conducted intensive research and found that by providing a barrier layer on the surface of the copper foil with a release layer opposite to the surface of the release layer side, the copper foil with a release layer can be used to make the embedding Circuit, and can well suppress corrosion of the buried circuit when the buried circuit is exposed by etching.
將以上見解作為基礎而完成的本發明在一形態中是一種附脫模層的銅箔,其依序具備脫模層、銅箔和阻隔層。 The present invention completed on the basis of the above findings is, in one form, a copper foil with a release layer, which includes a release layer, a copper foil, and a barrier layer in this order.
關於本發明的附脫模層的銅箔,在一實施形態中,所述阻隔層 是C層、Ni層、Ti層、Cr層、V層、Zr層、Ta層、Au層、Pt層、Os層、Pd層、Ru層、Rh層、Ir層、W層,或者包含含有選自由Ni、Ti、V、Zr、Ta、Au、Pt、Os、Pd、Ru、Rh、Ir、W、Si及Cr所組成的群中的任一種以上的合金的層,或者包含含有選自由Ni、Ti、V、Zr、Ta、Au、Pt、Os、Pd、Ru、Rh、Ir、W、Si及Cr所組成的群中的任一種以上的碳化物、氧化物或氮化物的層。 Regarding the copper foil with a release layer of the present invention, in one embodiment, the barrier layer is a C layer, a Ni layer, a Ti layer, a Cr layer, a V layer, a Zr layer, a Ta layer, an Au layer, a Pt layer, Os layer, Pd layer, Ru layer, Rh layer, Ir layer, W layer, or contains a material selected from Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si A layer of any one or more alloys in the group consisting of Cr and Cr, or containing a layer containing Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si, and Cr Any one or more layers of carbide, oxide, or nitride in the group.
關於本發明的附脫模層的銅箔,在另一實施形態中,所述阻隔層由選自由Ni、Ti、Cr、氧化鈦、氧化鉻及碳所組成的群中的任一種以上所構成。 With respect to the copper foil with a mold release layer of the present invention, in another embodiment, the barrier layer is composed of at least one selected from the group consisting of Ni, Ti, Cr, titanium oxide, chromium oxide, and carbon .
關於本發明的附脫模層的銅箔,在又一實施形態中,所述阻隔層具有選自由Ni層、Ti層及Cr層所組成的群中的一種以上的層。 With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the barrier layer has one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer.
關於本發明的附脫模層的銅箔,在又一實施形態中,所述阻隔層是選自由Ni層、Ti層及Cr層所組成的群中的任一種以上的層。 With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the barrier layer is any one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer.
所述阻隔層是選自由Ni層、Ti層及Cr層所組成的群中的任一種的層。 The barrier layer is any layer selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer.
關於本發明的附脫模層的銅箔,在又一實施形態中,所述阻隔層的厚度為0.001μm以上且10μm以下。 With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the thickness of the barrier layer is 0.001 μm or more and 10 μm or less.
關於本發明的附脫模層的銅箔,在又一實施形態中,所述銅箔的厚度為0.1μm以上且100μm以下。 With respect to the copper foil with a release layer of the present invention, in yet another embodiment, the thickness of the copper foil is 0.1 μm or more and 100 μm or less.
關於本發明的附脫模層的銅箔,在又一實施形態中,所述脫模層單獨或組合多種而具有下式所表示的矽烷化合物、所述矽烷化合物的水解產物、所述矽烷化合物的水解產物的縮合物。 With respect to the copper foil with a mold release layer of the present invention, in another embodiment, the mold release layer has a silane compound represented by the following formula, a hydrolysate of the silane compound, and the silane compound individually or in combination. The condensation product of the hydrolysate.
(式中,R1為烷氧基或鹵素原子,R2為選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的所述烴基,R3及R4分別獨立地為鹵素原子、或烷氧基、或選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的所述烴基) (In the formula, R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, R 3 and R 4 are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom )
關於本發明的附脫模層的銅箔,在又一實施形態中,所述脫模層具有分子內具有2個以下的巰基的化合物。 With respect to the copper foil with a mold release layer of the present invention, in another embodiment, the mold release layer has a compound having two or less thiol groups in the molecule.
關於本發明的附脫模層的銅箔,在又一實施形態中,所述脫模層單獨或組合多種而具有下式所表示的鋁酸鹽化合物、鈦酸鹽化合物、鋯酸鹽化合物、所述鋁酸鹽化合物的水解產物、所述鈦酸鹽化合物的水解產物、所述鋯酸鹽化合物的水解產物、所述鋁酸鹽化合物的水解產物的縮合物、所述鈦酸鹽化合物的水解產物的縮合物或所述鋯酸鹽化合物的水解產物的縮合物。 With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the mold release layer has an aluminate compound, a titanate compound, a zirconate compound represented by the following formula alone or in combination. The hydrolysis product of the aluminate compound, the hydrolysis product of the titanate compound, the hydrolysis product of the zirconate compound, the condensate of the hydrolysis product of the aluminate compound, the The condensate of the hydrolysate or the hydrolysate of the zirconate compound.
(R1)m-M-(R2)n (R 1 ) m -M-(R 2 ) n
(式中,R1為烷氧基或鹵素原子,R2為選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的所述烴基,M為Al、Ti或Zr,n為0、1或2,m為1以上且M的價數以下的整數,R1的至少一個為烷氧基。m+n為M的價數,即,當為Al時為3,當為Ti、Zr時為4) (In the formula, R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, M is Al, Ti, or Zr, n is 0, 1, or 2, m is an integer of 1 or more and the valence of M or less, and at least one of R 1 is an alkoxy group. m+n is the valence of M, that is, 3 for Al, 4 for Ti and Zr)
關於本發明的附脫模層的銅箔,在又一實施形態中,所述脫模層具有樹脂塗膜,所述樹脂塗膜由聚矽氧以及選自環氧系樹脂、三聚氰胺系樹脂及氟樹脂中的任一種或多種樹脂所構成。 With respect to the copper foil with a mold release layer of the present invention, in yet another embodiment, the mold release layer has a resin coating film made of silicone and selected from epoxy-based resins, melamine-based resins and The fluororesin is composed of any one or more resins.
關於本發明的附脫模層的銅箔,在又一實施形態中,在所述銅箔與阻隔層之間,具有選自由粗化處理層、耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的一種以上的層。 In another embodiment, the copper foil with a mold release layer of the present invention has a roughening treatment layer, a heat-resistant layer, a rust prevention layer, and a chromate treatment layer selected between the copper foil and the barrier layer One or more layers in the group consisting of silane coupling treatment layers.
關於本發明的附脫模層的銅箔,在又一實施形態中,在所述阻 隔層的與銅箔側為相反側的面,具有選自由粗化處理層、耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的一種以上的層。 In yet another embodiment, the copper foil with a mold release layer of the present invention has a surface selected from a roughening treatment layer, a heat-resistant layer, and a rust prevention layer on the surface of the barrier layer opposite to the copper foil side. One or more layers in the group consisting of a chromate treatment layer and a silane coupling treatment layer.
關於本發明的附脫模層的銅箔,在又一實施形態中,所述粗化處理層是由選自由Cu、Ni、P、W、As、Mo、Cr、Ti、Fe、V、Co及Zn所組成的群中的任一種單質或含有任一種以上所述單質的合金所構成的層。 Regarding the copper foil with a mold release layer of the present invention, in yet another embodiment, the roughening treatment layer is selected from the group consisting of Cu, Ni, P, W, As, Mo, Cr, Ti, Fe, V, Co A layer composed of any single element or an alloy containing any one or more of the elements in the group consisting of Zn and Zn.
關於本發明的附脫模層的銅箔,在又一實施形態中,在所述銅箔與脫模層之間,具有選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的一種以上的層。 In yet another embodiment, the copper foil with a mold release layer of the present invention has a coupling treatment selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane between the copper foil and the mold-release layer More than one layer in a group of layers.
關於本發明的附脫模層的銅箔,在又一實施形態中,在所述脫模層側表面具備樹脂層。 In another embodiment, the copper foil with a mold release layer of the present invention includes a resin layer on the surface of the mold release layer side.
本發明在另一形態中是一種積層體,其具有本發明的附脫模層的銅箔。 In another aspect, the present invention is a laminate including the copper foil with a release layer of the present invention.
本發明在又一形態中是一種積層體,其含有本發明的附脫模層的銅箔和樹脂,且所述銅箔的端面的一部分或全部由所述樹脂覆蓋。 The present invention in still another aspect is a laminate including a copper foil with a mold release layer of the present invention and a resin, and a part or all of the end surface of the copper foil is covered with the resin.
本發明在又一形態中是一種積層體,其具有兩個本發明的附脫模層的銅箔和樹脂,且其是將所述兩個附脫模層的銅箔中的一附脫模層的銅箔的所述脫模層側表面與所述樹脂的一面積層,將另一所述附脫模層的銅箔的脫模層側表面與所述樹脂的另一面積層而成。 The present invention in another form is a laminate having two copper foils with a mold release layer and a resin of the present invention, and one of the two copper foils with a mold release layer attached The surface area of the release layer side of the copper foil of the layer and one area of the resin are formed by layering the surface area of the release layer side of the copper foil with the release layer and another area of the resin.
本發明在又一形態中是一種印刷配線板的製造方法,其是使用本發明的附脫模層的銅箔而製造印刷配線板。 In still another aspect, the present invention is a method of manufacturing a printed wiring board, which uses the copper foil with a release layer of the present invention to manufacture a printed wiring board.
本發明在又一形態中是一種印刷配線板的製造方法,其包括以下步驟:在本發明的附脫模層的銅箔的所述脫模層側積層支持體或絕緣基板1的步驟;在積層了所述支持體或所述絕緣基板1的附脫模層的銅箔的所述阻隔層側設置經圖案化的抗鍍覆層的步驟;在設置了所述經圖案化的抗鍍覆層的所 述阻隔層上設置鍍銅層後,將所述抗鍍覆層去除,藉此形成鍍銅電路的步驟;利用絕緣基板2覆蓋所述鍍銅電路,藉此將所述鍍銅電路埋入的步驟;將所述鍍銅電路埋入後,將所述脫模層側表面的所述支持體或所述絕緣基板1去除,藉此使所述附脫模層的銅箔的脫模層側表面露出的步驟;利用蝕刻將所述銅箔自所述露出的脫模層側表面去除而使所述阻隔層表面露出的步驟;以及利用蝕刻將所述露出的阻隔層去除,藉此使埋入所述絕緣基板2中的電路露出的步驟。 The present invention in another embodiment is a method for manufacturing a printed wiring board, which includes the steps of: laminating a support or an
本發明在又一形態中是一種印刷配線板的製造方法,其是使用本發明的積層體而製造印刷配線板。 The present invention in another embodiment is a method of manufacturing a printed wiring board, which uses the laminate of the present invention to manufacture a printed wiring board.
本發明在又一形態中是一種電子機器的製造方法,其是使用利用本發明的方法製造的印刷配線板而製造電子機器。 In still another aspect, the present invention is a method of manufacturing an electronic device, which uses a printed wiring board manufactured by the method of the present invention to manufacture an electronic device.
根據本發明的附脫模層的銅箔,可製作埋入電路,且可良好地抑制利用蝕刻使所述埋入電路露出時侵蝕埋入電路。 According to the copper foil with a mold release layer of the present invention, a buried circuit can be produced, and corrosion of the buried circuit when the buried circuit is exposed by etching can be suppressed well.
1、2‧‧‧絕緣基板 1, 2‧‧‧ Insulated substrate
10、11‧‧‧阻隔層 10, 11‧‧‧ barrier layer
20、21、60‧‧‧銅箔 20, 21, 60 ‧‧‧ copper foil
30、31‧‧‧脫模層 30, 31‧‧‧ Release layer
40‧‧‧抗鍍覆層 40‧‧‧Anti-plating layer
50‧‧‧鍍銅層 50‧‧‧copper plating
51、61‧‧‧鍍銅電路 51, 61‧‧‧ Copper-plated circuit
圖1是表示使用本發明的一實施形態的附脫模層的銅箔的埋入電路的形成方法的一部分的示意圖。 1 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a mold release layer according to an embodiment of the present invention.
圖2是表示使用本發明的一實施形態的附脫模層的銅箔的埋入電路的形成方法的一部分的示意圖。 2 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention.
圖3是表示使用本發明的一實施形態的附脫模層的銅箔的埋入電路的形成方法的一部分的示意圖。 3 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention.
圖4是表示使用本發明的一實施形態的附脫模層的銅箔的埋入電路的形成 方法的一部分的示意圖。 4 is a schematic diagram showing a part of a method for forming a buried circuit using a copper foil with a mold release layer according to an embodiment of the present invention.
圖5是本發明的另一實施形態的在絕緣基板的兩表面分別設置了附脫模層的銅箔的積層體的示意圖。 5 is a schematic view of a laminate in which copper foils with release layers are provided on both surfaces of an insulating substrate according to another embodiment of the present invention.
<附脫模層的銅箔> <Copper foil with release layer>
依序具備脫模層、銅箔和阻隔層。銅箔典型的是以壓延銅箔或電解銅箔或利用濺鍍等乾式鍍覆法製造的銅箔的形態提供。一般來說,電解銅箔是使銅自硫酸銅鍍覆浴中電解析出至鈦或不銹鋼的鼓上而製造,壓延銅箔是反復進行利用壓延輥的塑性加工和熱處理而製造。作為銅箔的材料,除精銅(JIS H3100合金編號C1100)或無氧銅(JIS H3100合金編號C1020或JIS H3510合金編號C1011)等高純度銅以外,還可使用例如加入了Sn的銅、加入了Ag的銅、添加了Cr、Zr或Mg等的銅合金、添加了Ni及Si等的卡遜系銅合金之類的銅合金。 Sequentially equipped with release layer, copper foil and barrier layer. The copper foil is typically provided in the form of a rolled copper foil, an electrolytic copper foil, or a copper foil manufactured by a dry plating method such as sputtering. In general, electrolytic copper foil is produced by electrolysis of copper from a copper sulfate plating bath onto a drum of titanium or stainless steel, and rolled copper foil is produced by repeating plastic processing and heat treatment using a calender roll. As the material of the copper foil, in addition to high-purity copper such as refined copper (JIS H3100 alloy number C1100) or oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, copper added with Sn, added Copper alloys such as copper with Ag, copper alloys with addition of Cr, Zr, or Mg, and Carson-based copper alloys with addition of Ni, Si, etc.
銅箔的厚度沒有必要特別限定,例如為0.1μm以上且100μm以下、1μm以上且1000μm以下、或1μm以上且500μm以下、或1μm以上且300μm以下、或3μm以上且100μm以下、或5μm以上且70μm以下、或6μm以上且35μm以下、或9μm以上且18μm以下。 The thickness of the copper foil is not particularly limited, and is, for example, 0.1 μm or more and 100 μm or less, 1 μm or more and 1000 μm or less, or 1 μm or more and 500 μm or less, or 1 μm or more and 300 μ m or less, or 3 μm or more and 100 μm or less, or 5 μm or more and 70 μm or less, or 6 μm or more and 35 μm or less, or 9 μm or more and 18 μm or less.
阻隔層對銅蝕刻劑具有耐溶解性,即具備如下性質:對於銅蝕刻劑(銅的蝕刻液),比銅不易溶解或被蝕刻的速度比銅慢。被蝕刻的速度是指每單位時間被蝕刻液侵蝕的厚度。例如可以如下方式算出被蝕刻的速度。 The barrier layer has resistance to dissolution of copper etchant, that is, it has the following properties: for copper etchant (copper etchant), it is less soluble than copper or is etched at a slower rate than copper. The etching speed refers to the thickness eroded by the etching liquid per unit time. For example, the etching speed can be calculated as follows.
測量蝕刻前的樣品的質量W1(g)。測量特定時間t(s)蝕刻後的樣品的質量W2(g)。而且,利用下式算出被蝕刻的速度。 The mass W1(g) of the sample before etching was measured. Measure the mass W2(g) of the etched sample at a specific time t(s). Furthermore, the etching rate is calculated by the following formula.
被蝕刻的速度(μm/s)={蝕刻前的樣品的質量W1(g)-樣品的質量W2(g)}/{阻隔層的密度(g/μm3)×樣品被蝕刻的面積(μm2)×蝕刻時間t (s)} Etched rate (μ m / s) = {quality W1 sample before etching (g) - mass of the specimen W2 (g)} / {a barrier layer having a density (g / μ m 3) × samples were etched area ( μ m 2 )×etching time t (s))
此外,測量所述被蝕刻的速度時,例如可使用硫酸-過氧化氫水溶液作為銅的蝕刻液。 In addition, when measuring the etching speed, for example, a sulfuric acid-hydrogen peroxide aqueous solution can be used as a copper etching solution.
作為對銅蝕刻劑具有耐溶解性的阻隔層,較佳為使用C層、Ni層、Ti層、Cr層、V層、Zr層、Ta層、Au層、Pt層、Os層、Pd層、Ru層、Rh層、Ir層、W層,或者包含含有Ni、Ti、V、Zr、Ta、Au、Pt、Os、Pd、Ru、Rh、Ir、W、Si及Cr中的任一種以上的合金的層,或者包含含有Ni、Ti、V、Zr、Ta、Au、Pt、Os、Pd、Ru、Rh、Ir、W、Si及Cr中的任一種以上的碳化物或氧化物或氮化物的層等。作為對銅蝕刻劑具有耐溶解性的阻隔層,更佳為由選自由Ni、Ti、Cr、氧化鈦、氧化鉻及碳所組成的群中的任一種或兩種以上所構成的阻隔層。另外,因為更具有作為阻隔層的效果,所以阻隔層較佳為具有選自由Ni層、Ti層及Cr層所組成的群中的一種以上的層。另外,因為更具有作為阻隔層的效果,所以阻隔層較佳為選自由Ni層、Ti層及Cr層所組成的群中的一種以上的層。另外,因為更具有作為阻隔層的效果,所以阻隔層較佳為選自由Ni層、Ti層及Cr層所組成的群中的一種的層。另外,阻隔層較佳為Ni層。另外,阻隔層較佳為Ti層。另外,阻隔層較佳為Cr層。 As the barrier layer having resistance to dissolution of the copper etchant, it is preferable to use a C layer, Ni layer, Ti layer, Cr layer, V layer, Zr layer, Ta layer, Au layer, Pt layer, Os layer, Pd layer, Ru layer, Rh layer, Ir layer, W layer, or any one containing Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si, and Cr Alloy layer, or contains carbide, oxide, or nitride containing any one or more of Ni, Ti, V, Zr, Ta, Au, Pt, Os, Pd, Ru, Rh, Ir, W, Si, and Cr The layers etc. As the barrier layer having resistance to dissolution with respect to the copper etchant, a barrier layer composed of any one kind or two or more kinds selected from the group consisting of Ni, Ti, Cr, titanium oxide, chromium oxide, and carbon is more preferable. In addition, since it is more effective as a barrier layer, the barrier layer preferably has one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. In addition, since it is more effective as a barrier layer, the barrier layer is preferably one or more layers selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. In addition, since it is more effective as a barrier layer, the barrier layer is preferably a layer selected from the group consisting of a Ni layer, a Ti layer, and a Cr layer. In addition, the barrier layer is preferably a Ni layer. In addition, the barrier layer is preferably a Ti layer. In addition, the barrier layer is preferably a Cr layer.
此外,Ni層或包含Ni的合金層較佳為以如下方式形成。原因在於,Ni層或包含Ni的合金層的表面變得平滑,形成於所述Ni層或包含Ni的合金層上的極薄銅層及/或銅層的阻隔層側及與阻隔層為相反側的表面也變得平滑,因此極薄銅層及/或銅層的微細電路形成性提升。 In addition, the Ni layer or the alloy layer containing Ni is preferably formed as follows. The reason is that the surface of the Ni layer or the alloy layer containing Ni becomes smooth, and the very thin copper layer and/or the barrier layer side of the copper layer formed on the Ni layer or the alloy layer containing Ni are opposite to the barrier layer The surface on the side also becomes smooth, so the ultra-thin copper layer and/or the fine circuit formability of the copper layer are improved.
‧Ni層或包含Ni的合金層的形成 ‧Formation of Ni layer or alloy layer containing Ni
Ni層或包含Ni的合金層可藉由進行鎳鍍覆或包含鎳的合金鍍覆而形成。此時,重要的是最後加工成緻密且均勻且沒有缺陷的鍍覆。作為鎳鍍覆或包含鎳的合金鍍覆,在以下的條件下進行。 The Ni layer or the alloy layer containing Ni can be formed by performing nickel plating or alloy plating containing nickel. At this time, it is important that the final processing is a dense and uniform plating without defects. Nickel plating or alloy plating containing nickel is performed under the following conditions.
‧鍍覆液 ‧Plating solution
鎳:20~200g/L Nickel: 20~200g/L
其他元素:0.1~200g/L(僅在包含鎳的合金鍍覆的情況下) Other elements: 0.1~200g/L (only in the case of alloy plating containing nickel)
硼酸:5~60g/L Boric acid: 5~60g/L
液溫:40~65℃ Liquid temperature: 40~65℃
pH值:1.5~5.0,較佳為2.0~3.0。藉由使pH值偏低而階段性地進行鍍覆處理,產生氫氣而陰極表面成為還原環境。因此,可抑制產生氧化物、氫氧化物、水合物等產生水分的原因要素。 pH value: 1.5~5.0, preferably 2.0~3.0. By lowering the pH and performing the plating treatment in stages, hydrogen gas is generated and the cathode surface becomes a reducing environment. Therefore, it is possible to suppress generation of moisture, causative factors such as oxides, hydroxides, and hydrates.
電流密度:0.5~20A/dm2,較佳為2~8A/dm2。較佳為以低電流密度進行處理,因為不易導致粗糙鍍覆,成為缺陷少且緻密鍍覆。 Current density: 0.5~20A/dm 2 , preferably 2~8A/dm 2 . The treatment at a low current density is preferred because rough plating is not likely to occur, resulting in fewer defects and dense plating.
‧攪拌(液體循環量) ‧Stirring (liquid circulation)
100~1000L/分鐘。液體循環量多會使產生的氫氣的氣體脫離變好,針孔等缺陷變少。另外,具有減小擴散層厚度的效果,可抑制產生氫氧化物等產生水分的原因要素。 100~1000L/minute. A large amount of liquid circulation will make the generated hydrogen gas detach better, and fewer defects such as pinholes. In addition, it has the effect of reducing the thickness of the diffusion layer, and can suppress the generation of hydroxides and other factors causing moisture generation.
‧進行鍍覆的對象的搬送速度 ‧Conveying speed of plated objects
2~30m/分鐘,較佳為5~10m/分鐘。搬送速度慢會使平滑且緻密的Ni層或包含鎳的合金層形成。 2~30m/min, preferably 5~10m/min. A slow transport speed will form a smooth and dense Ni layer or an alloy layer containing nickel.
‧添加劑 ‧Additives
添加劑較佳為使用以下的一次光澤劑及二次光澤劑。藉此,結晶變得平滑且緻密。因此,鍍覆產生的缺陷減少,水分的吸收減少。 As the additive, the following primary gloss agent and secondary gloss agent are preferably used. By this, the crystal becomes smooth and dense. Therefore, defects due to plating are reduced, and moisture absorption is reduced.
(一次光澤劑) (Primary gloss agent)
1-5萘-二磺酸鈉:2~10g/L、1-3-6萘-三磺酸鈉:10~30g/L、對甲苯碸-醯胺:0.5~4g/L、糖精鈉:0.5~5g/L中的任一種。 1-5 Naphthalene-disulfonic acid sodium: 2~10g/L, 1-3-6 Naphthalene-trisulfonic acid sodium: 10~30g/L, p-toluene-amide: 0.5~4g/L, saccharin sodium: Any one of 0.5~5g/L.
(二次光澤劑) (Secondary gloss agent)
福馬林:0.5~5g/L、明膠:0.005~0.5g/L、硫脲:0.05~1.0g/L、炔丙醇:0.01~0.3g/L、1-4丁炔二醇:0.05~0.5g/L、乙撐氰醇(ethylene cyanohydrin):0.05~0.5g/L中的任一種。 Formalin: 0.5~5g/L, gelatin: 0.005~0.5g/L, thiourea: 0.05~1.0g/L, propargyl alcohol: 0.01~0.3g/L, 1-4 butyne diol: 0.05~0.5 g/L, ethylene cyanohydrin: Any one of 0.05~0.5g/L.
阻隔層的厚度的下限沒有必要特別限定,例如也可為0.001μm以上、較佳為0.01μm以上、進而較佳為0.05μm以上。另外,阻隔層的厚度的上限沒有必要特別限定,例如也可為10μm以下、較佳為5μm以下、進而較佳為1μm以下。 The lower limit of the thickness of the barrier layer is not particularly limited. For example, it may be 0.001 μm or more, preferably 0.01 μm or more, and more preferably 0.05 μm or more. In addition, the upper limit of the thickness of the barrier layer is not particularly limited, and for example, it may be 10 μm or less, preferably 5 μm or less, and more preferably 1 μm or less.
關於本發明的附脫模層的銅箔,在銅箔的表面形成電路,以覆蓋所述電路的方式積層樹脂而形成埋入電路後,利用蝕刻將所述銅箔去除而使埋入電路露出時,因為具備對銅蝕刻劑具有耐溶解性的阻隔層,所以沒有因銅箔的蝕刻而侵蝕至埋入電路的擔憂。 Regarding the copper foil with a mold release layer of the present invention, a circuit is formed on the surface of the copper foil, a resin is laminated to cover the circuit to form a buried circuit, and then the copper foil is removed by etching to expose the buried circuit At this time, since a barrier layer having a resistance to dissolution with a copper etchant is provided, there is no fear that the copper foil will be eroded to the buried circuit due to the etching of the copper foil.
本發明的附脫模層的銅箔的脫模層可自脫模層側將利用壓接等使樹脂基材等支持體貼合時的樹脂基材等支持體剝離。此時,樹脂基材等支持體與銅箔藉由脫模層分離。 In the release layer of the copper foil with a release layer of the present invention, a support such as a resin substrate when the support such as a resin substrate is bonded by pressure bonding or the like can be peeled from the release layer side. At this time, the support such as the resin base material and the copper foil are separated by the release layer.
(1)矽烷化合物 (1) Silane compound
脫模層也可將具有下式所表示的結構的矽烷化合物、或所述矽烷化合物的水解生成物質、或所述水解生成物質的縮合物(以下,簡記作矽烷化合物)單獨或多個組合而形成。 The release layer may be composed of a silane compound having the structure represented by the following formula, or a hydrolyzed product of the silane compound, or a condensate of the hydrolyzed product (hereinafter, abbreviated as silane compound) alone or in combination. form.
(式中,R1為烷氧基或鹵素原子,R2為選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的所述烴基,R3 及R4分別獨立地為鹵素原子、或烷氧基、或選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的所述烴基)。 (In the formula, R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, R 3 and R 4 are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom ).
所述矽烷化合物必須具有至少一個烷氧基。在不存在烷氧基而僅由選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的這些中任一烴基構成取代基的情況下,有樹脂基板與銅箔的密接性過度下降的傾向。另外,所述矽烷化合物必須具有至少一個選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的這些中任一烴基。原因在於,在不存在所述烴基的情況下,有樹脂基板與銅箔的密接性上升的傾向。此外,本案發明的烷氧基也包括一個以上的氫原子被鹵素原子取代的烷氧基。 The silane compound must have at least one alkoxy group. When there is no alkoxy group but only a hydrocarbon group selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with halogen atoms constitutes a substituent, The adhesion between the resin substrate and the copper foil tends to decrease excessively. In addition, the silane compound must have at least one hydrocarbon group selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced with halogen atoms. The reason is that in the absence of the hydrocarbon group, the adhesion between the resin substrate and the copper foil tends to increase. In addition, the alkoxy group of the present invention also includes alkoxy groups in which one or more hydrogen atoms are replaced by halogen atoms.
所述矽烷化合物較佳為具有三個烷氧基、一個所述烴基(包括一個以上的氫原子被鹵素原子取代的烴基)。以上式來說的話,指R3及R4兩者均為烷氧基。 The silane compound preferably has three alkoxy groups and one hydrocarbon group (including a hydrocarbon group in which more than one hydrogen atom is replaced by a halogen atom). In the above formula, both R 3 and R 4 are alkoxy groups.
作為烷氧基,沒有限定,可列舉甲氧基、乙氧基、正或異丙氧基、正、異或三級丁氧基、正、異或新戊氧基、正己氧基、環己氧基、正庚氧基、及正辛氧基等直鏈狀、支鏈狀、或環狀的碳數1~20、較佳為碳數1~10、更佳為碳數1~5的烷氧基。 The alkoxy group is not limited, and examples thereof include methoxy, ethoxy, n- or isopropoxy, n-, i-or tertiary butoxy, n-, i-or neopentyloxy, n-hexyloxy, and cyclohexyl. Linear, branched, or cyclic carbon numbers of 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms, such as oxy, n-heptyloxy, and n-octyloxy Alkoxy.
作為鹵素原子,可列舉氟原子、氯原子、溴原子及碘原子。 Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom.
作為烷基,沒有限定,可列舉甲基、乙基、正或異丙基、正、異或三級丁基、正、異或新戊基、正己基、正辛基、正癸基等直鏈狀或支鏈狀的碳數1~20、較佳為碳數1~10、更佳為碳數1~5的烷基。 The alkyl group is not limited, and examples thereof include straight groups such as methyl, ethyl, n- or isopropyl, n-, i-or tertiary butyl, n-, i-or neopentyl, n-hexyl, n-octyl, and n-decyl groups. The chain or branched chain has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
作為環烷基,沒有限定,可列舉環丙基、環丁基、環戊基、環己基、環庚基、環辛基等碳數3~10、較佳為碳數5~7的環烷基。 The cycloalkyl group is not limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. base.
作為芳基,可列舉苯基、經烷基取代的苯基(例:甲苯基、二 甲苯基)、1-或2-萘基、蒽基等碳數6~20、較佳為6~14的芳基。 Examples of the aryl group include a phenyl group, a phenyl group substituted with an alkyl group (e.g., tolyl group, xylyl group), 1- or 2-naphthyl group, anthracenyl group and the like having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. Aryl.
這些烴基也可一個以上的氫原子被鹵素原子取代,例如可被氟原子、氯原子、或溴原子取代。 These hydrocarbon groups may be substituted with more than one hydrogen atom by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.
作為較佳的矽烷化合物的例子,可列舉甲基三甲氧基矽烷、乙基三甲氧基矽烷、正或異丙基三甲氧基矽烷、正、異或三級丁基三甲氧基矽烷、正、異或新戊基三甲氧基矽烷、己基三甲氧基矽烷、辛基三甲氧基矽烷、癸基三甲氧基矽烷、苯基三甲氧基矽烷;烷基取代苯基三甲氧基矽烷(例如,對(甲基)苯基三甲氧基矽烷)、甲基三乙氧基矽烷、乙基三乙氧基矽烷、正或異丙基三乙氧基矽烷、正、異或三級丁基三乙氧基矽烷、戊基三乙氧基矽烷、己基三乙氧基矽烷、辛基三乙氧基矽烷、癸基三乙氧基矽烷、苯基三乙氧基矽烷、烷基取代苯基三乙氧基矽烷(例如,對(甲基)苯基三乙氧基矽烷)、(3,3,3-三氟丙基)三甲氧基矽烷、及十三氟辛基三乙氧基矽烷、甲基三氯矽烷、二甲基二氯矽烷、三甲基氯矽烷、苯基三氯矽烷、三甲基氟矽烷、二甲基二溴矽烷、二苯基二溴矽烷、這些的水解產物、及這些的水解產物的縮合物等。這些之中,就獲取容易性的觀點來說,較佳為丙基三甲氧基矽烷、甲基三乙氧基矽烷、己基三甲氧基矽烷、苯基三乙氧基矽烷、癸基三甲氧基矽烷。 Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or isopropyltrimethoxysilane, n-, iso- or tertiary-butyltrimethoxysilane, n-, XOR neopentyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane; alkyl substituted phenyltrimethoxysilane (for example, (Methyl) phenyl trimethoxy silane), methyl triethoxy silane, ethyl triethoxy silane, n- or isopropyl triethoxy silane, n-, iso- or tertiary butyl triethoxy Silane, pentyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, alkyl-substituted phenyltriethoxysilane Silanes (for example, p-(methyl)phenyltriethoxysilane), (3,3,3-trifluoropropyl)trimethoxysilane, and tridecylfluorooctyltriethoxysilane, methyl Trichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, hydrolysis products of these, and these Condensate of the hydrolysate and so on. Among these, from the viewpoint of availability, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxy are preferable Silane.
(2)分子內具有2個以下的巰基的化合物 (2) Compounds with 2 or less thiol groups in the molecule
脫模層也可使用分子內具有2個以下的巰基的化合物而構成。 The release layer can also be composed of a compound having two or less thiol groups in the molecule.
作為所述分子內具有2個以下的巰基的化合物,可列舉硫醇、二硫醇、硫羧酸或其鹽、二硫羧酸或其鹽、硫磺酸或其鹽、及二硫磺酸或其鹽,可使用選自這些中的至少一種。 Examples of the compound having two or less mercapto groups in the molecule include thiol, dithiol, thiocarboxylic acid or its salt, dithiocarboxylic acid or its salt, sulfuric acid or its salt, and disulfonic acid or its As the salt, at least one selected from these can be used.
硫醇在分子內具有一個巰基,例如由R-SH表示。在此,R表示也可包含羥基或胺基的脂肪族系或芳香族系烴基或雜環基。 The thiol has a thiol group in the molecule, for example, represented by R-SH. Here, R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group.
二硫醇在分子內具有兩個巰基,例如由R(SH)2表示。R表示也 可包含羥基或胺基的脂肪族系或芳香族系烴基或雜環基。另外,兩個巰基可分別與相同的碳鍵結,也可與互不相同的碳或氮鍵結。 Dithiol has two mercapto groups in the molecule, for example, represented by R(SH) 2 . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, the two mercapto groups may be bonded to the same carbon, or may be bonded to different carbon or nitrogen.
硫羧酸是有機羧酸的羥基被巰基取代而成,例如由R-CO-SH表示。R表示也可包含羥基或胺基的脂肪族系或芳香族系烴基或雜環基。另外,硫羧酸也可以鹽的形態使用。此外,還可使用具有兩個硫羧酸基的化合物。 Thiocarboxylic acid is formed by replacing the hydroxyl group of an organic carboxylic acid with a mercapto group, for example, represented by R-CO-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, thiocarboxylic acid can also be used in the form of a salt. In addition, compounds having two thiocarboxylic acid groups can also be used.
二硫羧酸是有機羧酸的羧基中的兩個氧原子被硫黃原子取代而成,例如由R-(CS)-SH表示。R表示也可包含羥基或胺基的脂肪族系或芳香族系烴基或雜環基。另外,二硫羧酸也可以鹽的形態使用。此外,還可使用具有兩個二硫羧酸基的化合物。 Dithiocarboxylic acid is formed by replacing two oxygen atoms in the carboxyl group of an organic carboxylic acid with sulfur atoms, for example, represented by R-(CS)-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, dithiocarboxylic acid can also be used in the form of a salt. In addition, compounds having two dithiocarboxylic acid groups can also be used.
硫磺酸是有機磺酸的羥基被巰基取代而成,例如由R(SO2)-SH表示。R表示也可包含羥基或胺基的脂肪族系或芳香族系烴基或雜環基。另外,硫磺酸也可以鹽的形態使用。 Sulfuric acid is formed by replacing the hydroxyl group of an organic sulfonic acid with a mercapto group, for example, represented by R(SO 2 )-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, sulfuric acid can also be used in the form of a salt.
二硫磺酸是有機二磺酸的兩個羥基分別被巰基取代而成,例如由R-((SO2)-SH)2表示。R表示也可包含羥基或胺基的脂肪族系或芳香族系烴基或雜環基。另外,兩個硫磺酸基可分別與相同的碳鍵結,也可與互不同的碳鍵結。另外,二硫磺酸也可以鹽的形態使用。 Disulfonic acid is formed by replacing two hydroxyl groups of an organic disulfonic acid with sulfhydryl groups, for example, represented by R-((SO 2 )-SH) 2 . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may also contain a hydroxyl group or an amine group. In addition, the two sulfonic acid groups may be bonded to the same carbon or different carbons. In addition, disulfonic acid can also be used in the form of a salt.
在此,作為適宜作為R的脂肪族系烴基,可列舉烷基、環烷基,這些烴基也可包含羥基和胺基中的任一個或兩個。 Here, examples of the aliphatic hydrocarbon group suitable as R include alkyl groups and cycloalkyl groups, and these hydrocarbon groups may include any one or two of hydroxyl groups and amine groups.
另外,作為烷基,沒有限定,可列舉甲基、乙基、正或異丙基、正、異或三級丁基、正、異或新戊基、正己基、正辛基、正癸基等直鏈狀或支鏈狀的碳數1~20、較佳為碳數1~10、更佳為碳數1~5的烷基。 In addition, the alkyl group is not limited, and examples thereof include methyl, ethyl, n- or isopropyl, n-, iso- or tertiary butyl, n-, iso-or neopentyl, n-hexyl, n-octyl, and n-decyl groups. The straight-chain or branched-chain carbons have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
另外,作為環烷基,沒有限定,可列舉環丙基、環丁基、環戊基、環己基、環庚基、環辛基等碳數3~10、較佳為碳數5~7的環烷基。 In addition, the cycloalkyl group is not limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and the like having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. Cycloalkyl.
另外,作為適宜作為R的芳香族烴基,可列舉苯基、經烷基取 代的苯基(例:甲苯基、二甲苯基)、1-或2-萘基、蒽基等碳數6~20、較佳為6~14的芳基,這些烴基也可包含羥基和胺基中的任一個或兩個。 In addition, suitable aromatic hydrocarbon groups as R include phenyl, phenyl substituted with an alkyl group (e.g., tolyl, xylyl), 1- or 2-naphthyl, anthracenyl, etc., having 6 to 20 carbon atoms Preferably, it is an aryl group of 6 to 14, and these hydrocarbon groups may also contain any one or two of a hydroxyl group and an amine group.
另外,作為適宜作為R的雜環基,可列舉咪唑、三唑、四唑、苯并咪唑、苯并三唑、噻唑、苯并噻唑,也可包含羥基和胺基中的任一個或兩個。 In addition, examples of the heterocyclic group suitable as R include imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, and benzothiazole, and may include any one or both of a hydroxyl group and an amine group. .
作為分子內具有2個以下的巰基的化合物的較佳的例子,可列舉3-巰基-1,2丙二醇、2-巰基乙醇、1,2-乙烷二硫醇、6-巰基-1-己醇、1-辛烷硫醇、1-十二烷硫醇、10-羥基-1-十二烷硫醇、10-羧基-1-十二烷硫醇、10-胺基-1-十二烷硫醇、1-十二烷硫醇磺酸鈉、苯硫酚、硫代苯甲酸、4-胺基-苯硫酚、對甲苯硫醇、2,4-二甲基苯硫醇、3-巰基-1,2,4三唑、2-巰基-苯并噻唑。這些之中,就水溶性和廢棄物處理方面的觀點來說,較佳為3-巰基-1,2丙二醇。 Preferred examples of compounds having two or less mercapto groups in the molecule include 3-mercapto-1,2 propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, and 6-mercapto-1-hexyl. Alcohol, 1-octane mercaptan, 1-dodecane mercaptan, 10-hydroxy-1-dodecane mercaptan, 10-carboxy-1-dodecane mercaptan, 10-amino-1-dodecane Alkyl mercaptan, sodium 1-dodecyl mercaptan sulfonate, thiophenol, thiobenzoic acid, 4-amino-thiophenol, p-toluene mercaptan, 2,4-dimethylbenzene mercaptan, 3 -Mercapto-1,2,4 triazole, 2-mercapto-benzothiazole. Among these, from the viewpoint of water solubility and waste disposal, 3-mercapto-1,2 propylene glycol is preferred.
(3)金屬烷氧化物 (3) Metal alkoxide
脫模層也可將具有下式所表示的結構的鋁酸鹽化合物、鈦酸鹽化合物、鋯酸鹽化合物、或這些化合物的水解生成物質、或所述水解生成物質的縮合物(以下,簡記作金屬烷氧化物)單獨或多個組合而構成。 In the release layer, an aluminate compound, a titanate compound, a zirconate compound having the structure represented by the following formula, or a hydrolysis product of these compounds, or a condensation product of the hydrolysis product (hereinafter, abbreviated) As a metal alkoxide) alone or in combination.
(R1)m-M-(R2)n (R 1 ) m -M-(R 2 ) n
式中,R1為烷氧基或鹵素原子,R2為選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的所述烴基,M為Al、Ti或Zr,n為0、1或2,m為1以上且M的價數以下的整數,R1的至少一個為烷氧基。m+n為M的價數,即,當為Al時為3,當為Ti、Zr時為4。 In the formula, R 1 is an alkoxy group or a halogen atom, and R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group or the hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom, M Is Al, Ti, or Zr, n is 0, 1, or 2, m is an integer of 1 or more and the valence of M or less, and at least one of R 1 is an alkoxy group. m+n is the valence of M, that is, 3 for Al, 4 for Ti and Zr.
所述金屬烷氧化物必須具有至少一個烷氧基。在不存在烷氧基而僅由選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的這些中任一烴基構成取代基的情況下,有樹脂基板與銅箔的密 接性過度下降的傾向。另外,所述金屬烷氧化物必須具有0~2個選自由烷基、環烷基及芳基所組成的群中的烴基或一個以上的氫原子被鹵素原子取代的這些中任一烴基。原因在於,在具有3個以上的所述烴基的情況下,有樹脂基板與銅箔的密接性過度下降的傾向。此外,本案發明的烷氧基也包括一個以上的氫原子被鹵素原子取代的烷氧基。就將樹脂基板與銅箔的剝離強度調節為所述範圍的方面來說,所述金屬烷氧化物較佳為具有兩個以上的烷氧基且具有一個或兩個所述烴基(包括一個以上的氫原子被鹵素原子取代的烴基)。 The metal alkoxide must have at least one alkoxy group. When there is no alkoxy group but only a hydrocarbon group selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with halogen atoms constitutes a substituent, The adhesion between the resin substrate and the copper foil tends to decrease excessively. In addition, the metal alkoxide must have 0 to 2 hydrocarbon groups selected from the group consisting of alkyl groups, cycloalkyl groups, and aryl groups, or any one of these hydrocarbon groups in which one or more hydrogen atoms are replaced with halogen atoms. The reason is that when there are three or more hydrocarbon groups, the adhesion between the resin substrate and the copper foil tends to decrease excessively. In addition, the alkoxy group of the present invention also includes alkoxy groups in which one or more hydrogen atoms are replaced by halogen atoms. In terms of adjusting the peel strength of the resin substrate and the copper foil to the above range, the metal alkoxide preferably has two or more alkoxy groups and one or two of the hydrocarbon groups (including one or more hydrocarbon groups) Hydrocarbon group in which the hydrogen atom is replaced by a halogen atom).
另外,作為烷基,沒有限定,可列舉甲基、乙基、正或異丙基、正、異或三級丁基、正、異或新戊基、正己基、正辛基、正癸基等直鏈狀或支鏈狀的碳數1~20、較佳為碳數1~10、更佳為碳數1~5的烷基。 In addition, the alkyl group is not limited, and examples thereof include methyl, ethyl, n- or isopropyl, n-, iso- or tertiary butyl, n-, iso-or neopentyl, n-hexyl, n-octyl, and n-decyl groups. The straight-chain or branched-chain carbons have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
另外,作為環烷基,沒有限定,可列舉環丙基、環丁基、環戊基、環己基、環庚基、環辛基等碳數3~10、較佳為碳數5~7的環烷基。 In addition, the cycloalkyl group is not limited, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and the like having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. Cycloalkyl.
另外,作為適宜作為R2的芳香族烴基,可列舉苯基、經烷基取代的苯基(例:甲苯基、二甲苯基)、1-或2-萘基、蒽基等碳數6~20、較佳為6~14的芳基,這些烴基也可包含羥基和胺基中的任一個或兩個。 In addition, examples of the aromatic hydrocarbon group suitable as R 2 include a phenyl group, a phenyl group substituted with an alkyl group (for example: tolyl group, xylyl group), 1- or 2-naphthyl group, and anthracenyl group. 20. Aryl groups of preferably 6 to 14, these hydrocarbon groups may also contain any one or two of hydroxyl and amine groups.
這些烴基也可一個以上的氫原子被鹵素原子取代,例如可被氟原子、氯原子、或溴原子取代。 These hydrocarbon groups may be substituted with more than one hydrogen atom by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.
作為較佳的鋁酸鹽化合物的例子,可列舉三甲氧基鋁、甲基二甲氧基鋁、乙基二甲氧基鋁、正或異丙基二甲氧基鋁、正、異或三級丁基二甲氧基鋁、正、異或新戊基二甲氧基鋁、己基二甲氧基鋁、辛基二甲氧基鋁、癸基二甲氧基鋁、苯基二甲氧基鋁;烷基取代苯基二甲氧基鋁(例如,對(甲基)苯基二甲氧基鋁)、二甲基甲氧基鋁、三乙氧基鋁、甲基二乙氧基鋁、乙基二乙氧基鋁、正或異丙基二乙氧基鋁、正、異或三級丁基二乙氧基鋁、戊基二乙氧基鋁、己基二乙氧基鋁、辛基二乙氧基鋁、癸基二乙氧基鋁、苯基二乙氧基 鋁、烷基取代苯基二乙氧基鋁(例如,對(甲基)苯基二乙氧基鋁)、二甲基乙氧基鋁、三異丙氧基鋁、甲基二異丙氧基鋁、乙基二異丙氧基鋁、正或異丙基二乙氧基鋁、正、異或三級丁基二異丙氧基鋁、戊基二異丙氧基鋁、己基二異丙氧基鋁、辛基二異丙氧基鋁、癸基二異丙氧基鋁、苯基二異丙氧基鋁、烷基取代苯基二異丙氧基鋁(例如,對(甲基)苯基二異丙氧基鋁)、二甲基異丙氧基鋁、(3,3,3-三氟丙基)二甲氧基鋁、及十三氟辛基二乙氧基鋁、甲基二氯鋁、二甲基氯鋁、二甲基氯鋁、苯基二氯鋁、二甲基氟鋁、二甲基溴鋁、二苯基溴鋁、這些的水解產物、及這些的水解產物的縮合物等。這些之中,就獲取容易性的觀點來說,較佳為三甲氧基鋁、三乙氧基鋁、三異丙氧基鋁。 Examples of preferred aluminate compounds include trimethoxyaluminum, methyldimethoxyaluminum, ethyldimethoxyaluminum, n- or isopropyldimethoxyaluminum, n-, iso-or tri-aluminum Grade butyldimethoxyaluminum, n-, iso-or neopentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, phenyldimethoxyaluminum Aluminum; alkyl-substituted phenyldimethoxyaluminum (for example, p-(methyl)phenyldimethoxyaluminum), dimethylaluminum methoxide, triethoxyaluminum, methyldiethoxy Aluminum, ethyl diethoxy aluminum, n- or isopropyl diethoxy aluminum, n-, iso- or tertiary butyl diethoxy aluminum, pentyl diethoxy aluminum, hexyl diethoxy aluminum, Octyl diethoxy aluminum, decyl diethoxy aluminum, phenyl diethoxy aluminum, alkyl substituted phenyl diethoxy aluminum (for example, p-(methyl) phenyl diethoxy aluminum) , Aluminum dimethylethoxylate, aluminum triisopropoxide, aluminum aluminum diisopropoxide, aluminum aluminum diisopropoxide, aluminum n- or isopropyl diethoxylate, aluminum n-, aluminum iso-propoxide Grade butyl diisopropoxide aluminum, amyl diisopropoxide aluminum, hexyl diisopropoxide aluminum, octyl diisopropoxide aluminum, decyl diisopropoxide aluminum, phenyl diisopropoxide Aluminum alkoxide, alkyl substituted phenyl diisopropoxide aluminum (for example, p-(methyl)phenyl diisopropoxide aluminum), dimethyl isopropoxide aluminum, (3,3,3-tris (Fluoropropyl) aluminum dimethoxy, and aluminum tridecyl octyl diethoxide, aluminum aluminum dichloride, aluminum aluminum dimethyl chloride, aluminum aluminum dimethyl chloride, aluminum aluminum phenyl chloride, dimethyl fluoride Aluminum, dimethylaluminum bromide, diphenylaluminum bromide, hydrolysis products of these, and condensates of these hydrolysis products, and the like. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferred.
作為較佳的鈦酸鹽化合物的例子,可列舉四甲氧基鈦、甲基三甲氧基鈦、乙基三甲氧基鈦、正或異丙基三甲氧基鈦、正、異或三級丁基三甲氧基鈦、正、異或新戊基三甲氧基鈦、己基三甲氧基鈦、辛基三甲氧基鈦、癸基三甲氧基鈦、苯基三甲氧基鈦;烷基取代苯基三甲氧基鈦(例如,對(甲基)苯基三甲氧基鈦)、二甲基二甲氧基鈦、四乙氧基鈦、甲基三乙氧基鈦、乙基三乙氧基鈦、正或異丙基三乙氧基鈦、正、異或三級丁基三乙氧基鈦、戊基三乙氧基鈦、己基三乙氧基鈦、辛基三乙氧基鈦、癸基三乙氧基鈦、苯基三乙氧基鈦、烷基取代苯基三乙氧基鈦(例如,對(甲基)苯基三乙氧基鈦)、二甲基二乙氧基鈦、四異丙氧基鈦、甲基三異丙氧基鈦、乙基三異丙氧基鈦、正或異丙基三乙氧基鈦、正、異或三級丁基三異丙氧基鈦、戊基三異丙氧基鈦、己基三異丙氧基鈦、辛基三異丙氧基鈦、癸基三異丙氧基鈦、苯基三異丙氧基鈦、烷基取代苯基三異丙氧基鈦(例如,對(甲基)苯基三異丙氧基鈦)、二甲基二異丙氧基鈦、(3,3,3-三氟丙基)三甲氧基鈦、及十三氟辛基三乙氧基鈦、甲基三氯鈦、二甲基二氯鈦、三甲基氯鈦、苯基三氯鈦、二甲基二氟鈦、二甲基二溴鈦、二苯基二溴鈦、這些的水解產物、及這些的水解產物的縮合物等。這些之 中,就獲取容易性的觀點來說,較佳為四甲氧基鈦、四乙氧基鈦、四異丙氧基鈦。 Examples of preferred titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tertiary butyl Trimethoxytitanium, n-, iso-or neopentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl substituted phenyl Trimethoxytitanium (for example, p-(methyl)phenyltrimethoxytitanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium , N- or isopropyltriethoxytitanium, n-, iso-or tertiary butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyl Triethoxytitanium, phenyltriethoxytitanium, alkyl-substituted phenyltriethoxytitanium (for example, p-(methyl)phenyltriethoxytitanium), dimethyl diethoxytitanium , Tetraisopropoxy titanium, methyl triisopropoxy titanium, ethyl triisopropoxy titanium, n- or isopropyl triethoxy titanium, n-, iso-or tertiary butyl triisopropoxy Titanium, pentyltriisopropoxy titanium, hexyl triisopropoxy titanium, octyl triisopropoxy titanium, decyl triisopropoxy titanium, phenyl triisopropoxy titanium, alkyl substituted benzene Triisopropoxy titanium (for example, p-(methyl)phenyl triisopropoxy titanium), dimethyl diisopropoxy titanium, (3,3,3-trifluoropropyl) trimethoxy Titanium, and tritylfluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichlorotitanium, trimethyltitanium chloride, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldichlorotitanium Titanium bromide, diphenyl titanium dibromide, hydrolysates of these, and condensates of these hydrolysates. Among these, from the viewpoint of ease of acquisition, tetramethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium are preferred.
作為較佳的鋯酸鹽化合物的例子,可列舉四甲氧基鋯、甲基三甲氧基鋯、乙基三甲氧基鋯、正或異丙基三甲氧基鋯、正、異或三級丁基三甲氧基鋯、正、異或新戊基三甲氧基鋯、己基三甲氧基鋯、辛基三甲氧基鋯、癸基三甲氧基鋯、苯基三甲氧基鋯;烷基取代苯基三甲氧基鋯(例如,對(甲基)苯基三甲氧基鋯)、二甲基二甲氧基鋯、四乙氧基鋯、甲基三乙氧基鋯、乙基三乙氧基鋯、正或異丙基三乙氧基鋯、正、異或三級丁基三乙氧基鋯、戊基三乙氧基鋯、己基三乙氧基鋯、辛基三乙氧基鋯、癸基三乙氧基鋯、苯基三乙氧基鋯、烷基取代苯基三乙氧基鋯(例如,對(甲基)苯基三乙氧基鋯)、二甲基二乙氧基鋯、四異丙氧基鋯、甲基三異丙氧基鋯、乙基三異丙氧基鋯、正或異丙基三乙氧基鋯、正、異或三級丁基三異丙氧基鋯、戊基三異丙氧基鋯、己基三異丙氧基鋯、辛基三異丙氧基鋯、癸基三異丙氧基鋯、苯基三異丙氧基鋯、烷基取代苯基三異丙氧基鋯(例如,對(甲基)苯基三異丙氧基鈦)、二甲基二異丙氧基鋯、(3,3,3-三氟丙基)三甲氧基鋯、及十三氟辛基三乙氧基鋯、甲基三氯鋯、二甲基二氯鋯、三甲基氯鋯、苯基三氯鋯、二甲基二氟鋯、二甲基二溴鋯、二苯基二溴鋯、這些的水解產物、及這些的水解產物的縮合物等。這些之中,就獲取容易性的觀點來說,較佳為四甲氧基鋯、四乙氧基鋯、四異丙氧基鋯。 Examples of preferred zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or isopropyltrimethoxyzirconium, n-, iso- or tertiary butyl Zirconium trimethoxyzirconium, n-, iso-or neopentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl substituted phenyl Zirconium trimethoxy (e.g., p-(methyl)phenyl zirconium trimethoxy), zirconium dimethyl dimethoxy, zirconium tetraethoxy, zirconium methyl triethoxy, zirconium ethyl triethoxy , Zirconium or isopropyl triethoxy zirconium, n, iso or tertiary butyl triethoxy zirconium, pentyl triethoxy zirconium, hexyl triethoxy zirconium, octyl triethoxy zirconium, decyl Triethoxyzirconium, phenyltriethoxyzirconium, alkyl-substituted phenyltriethoxyzirconium (for example, p-(methyl)phenyltriethoxyzirconium), dimethyl diethoxyzirconium , Zirconium tetraisopropoxide, zirconium triisopropoxide, zirconium triisopropoxide, zirconium triisopropoxide, zirconium or isopropyl triethoxy, triisopropoxy n-, iso- or tertiary butyl Zirconium, pentyl triisopropoxy zirconium, hexyl triisopropoxy zirconium, octyl triisopropoxy zirconium, decyl triisopropoxy zirconium, phenyl triisopropoxy zirconium, alkyl substituted benzene Triisopropoxy zirconium (for example, p-(methyl)phenyl triisopropoxy titanium), dimethyl diisopropoxy zirconium, (3,3,3-trifluoropropyl) trimethoxy Zirconium, and trifluorofluorooctyltriethoxyzirconium, methyltrichlorozirconium, dimethyldichlorozirconium, trimethylchlorozirconium, phenyltrichlorozirconium, dimethyldifluorozirconium, dimethyldichloro Zirconium bromide, diphenylzirconium dibromide, hydrolysates of these, and condensation products of these hydrolysates. Among these, from the viewpoint of ease of acquisition, tetramethoxyzirconium, tetraethoxyzirconium, and tetraisopropoxyzirconium are preferred.
(4)由樹脂塗膜所構成的脫模層 (4) Release layer composed of resin coating
使用由聚矽氧、以及選自環氧系樹脂、三聚氰胺系樹脂及氟樹脂中的任一種或多種樹脂所構成的樹脂塗膜,將樹脂基板與銅箔貼合,藉此可適度地使密接性降低,而將剝離強度調節為像後述那樣的範圍。 Using a resin coating film composed of polysiloxane and any one or more resins selected from epoxy-based resins, melamine-based resins, and fluororesins, the resin substrate and the copper foil are bonded together, thereby allowing proper adhesion The property is reduced, and the peel strength is adjusted to the range as described below.
這種用以實現密接性的剝離強度的調節是藉由像後述那樣使用 由聚矽氧、以及選自環氧系樹脂、三聚氰胺系樹脂及氟樹脂中的任一種或多種樹脂所構成的樹脂塗膜而進行。原因在於,對這種樹脂塗膜進行像後述那樣的特定條件的烘烤處理,用於樹脂基板與銅箔之間,進行熱壓而進行貼合,藉此可適度地使密接性降低,而將剝離強度調節為所述範圍。 This adjustment of the peel strength for achieving adhesion is achieved by using a resin coating composed of polysiloxane, and any one or more resins selected from epoxy-based resins, melamine-based resins, and fluororesins as described below. Film. The reason is that this resin coating film is subjected to baking treatment under specific conditions as described below, and is used between the resin substrate and the copper foil, and is pressed by hot pressing to perform bonding, whereby the adhesiveness can be appropriately reduced, and The peel strength is adjusted to the above range.
作為環氧系樹脂,可列舉雙酚A型環氧樹脂、雙酚F型環氧樹脂、酚醛清漆型環氧樹脂、溴化環氧樹脂、胺型環氧樹脂、可撓性環氧樹脂、氫化雙酚A型環氧樹脂、苯氧樹脂、溴化苯氧樹脂等。 Examples of epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, novolac epoxy resin, brominated epoxy resin, amine epoxy resin, flexible epoxy resin, Hydrogenated bisphenol A epoxy resin, phenoxy resin, brominated phenoxy resin, etc.
作為三聚氰胺系樹脂,可列舉甲基醚化三聚氰胺樹脂、丁基化尿素三聚氰胺樹脂、丁基化三聚氰胺樹脂、甲基化三聚氰胺樹脂、丁基醇改質三聚氰胺樹脂等。另外,三聚氰胺系樹脂也可為所述樹脂與丁基化尿素樹脂、丁基化苯代三聚氰胺樹脂等的混合樹脂。 Examples of the melamine-based resin include methyl etherified melamine resin, butylated urea melamine resin, butylated melamine resin, methylated melamine resin, and butyl alcohol modified melamine resin. In addition, the melamine-based resin may be a mixed resin of the above resin and butylated urea resin, butylated benzomelamine resin, or the like.
此外,環氧系樹脂的數量平均分子量較佳為2000~3000,三聚氰胺系樹脂的數量平均分子量較佳為500~1000。藉由具有這種數量平均分子量,而可實現樹脂的塗料化,並且容易將樹脂塗膜的接著強度調整為特定範圍。 In addition, the number average molecular weight of the epoxy resin is preferably 2000 to 3000, and the number average molecular weight of the melamine resin is preferably 500 to 1000. By having such a number-average molecular weight, the coating of the resin can be realized, and the adhesive strength of the resin coating film can be easily adjusted to a specific range.
另外,作為氟樹脂,可列舉聚四氟乙烯、聚氯三氟乙烯、聚偏二氟乙烯、聚氟乙烯等。 In addition, examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.
作為聚矽氧,可列舉甲基苯基聚矽氧烷、甲基氫聚矽氧烷、二甲基聚矽氧烷、改質二甲基聚矽氧烷、這些的混合物等。在此,所謂改質,例如可列舉環氧改質、烷基改質、胺基改質、羧基改質、醇改質、氟改質、烷基芳烷基聚醚改質、環氧聚醚改質、聚醚改質、烷基高級醇酯改質、聚酯改質、醯氧基烷基改質、鹵化烷基醯氧基烷基改質、鹵化烷基改質、胺基乙二醇改質、巰基改質、含有羥基的聚酯改質等。 Examples of polysiloxanes include methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylpolysiloxane, modified dimethylpolysiloxane, and mixtures of these. Here, examples of the modification include epoxy modification, alkyl modification, amine modification, carboxyl modification, alcohol modification, fluorine modification, alkyl aralkyl polyether modification, epoxy poly modification Ether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification, oxyalkyl modification, halogenated alkyl oxyalkyl modification, halogenated alkyl modification, amino ethyl Modification of glycol, modification of mercapto group, modification of polyester containing hydroxyl group, etc.
關於樹脂塗膜,如果膜厚過小,則樹脂塗膜過薄而難以形成, 因此生產性容易降低。另外,即使膜厚超過固定大小,也未見到樹脂塗膜的剝離性的進一步提升,樹脂塗膜的製造成本容易變高。就這種觀點來說,樹脂塗膜的膜厚較佳為0.1~10μm,進而較佳為0.5~5μm。另外,樹脂塗膜的膜厚是藉由在後述程式中以特定塗布量塗布樹脂塗料而達成。 Regarding the resin coating film, if the film thickness is too small, the resin coating film is too thin and it is difficult to form, so the productivity is likely to decrease. In addition, even if the film thickness exceeds a fixed size, no further improvement in the peelability of the resin coating film is seen, and the manufacturing cost of the resin coating film tends to increase. From this viewpoint, the film thickness of the resin coating film is preferably 0.1 to 10 μm , and more preferably 0.5 to 5 μm . In addition, the film thickness of the resin coating film is achieved by applying a resin coating material at a specific coating amount in a program described later.
在樹脂塗膜中,聚矽氧作為樹脂塗膜的剝離劑發揮功能。因此,如果環氧系樹脂、三聚氰胺系樹脂的合計量與聚矽氧相比過多,則在樹脂基板與銅箔之間,樹脂塗膜所賦予的剝離強度變大,因此樹脂塗膜的剝離性降低,有時以手工不容易剝離。另一方面,如果環氧系樹脂、三聚氰胺系樹脂的合計量過少,則所述剝離強度變小,因此有時會在附脫模層的銅箔的搬送時或加工時剝離。就這個觀點來說,較佳為以相對於聚矽氧100質量份,環氧系樹脂、三聚氰胺系樹脂的合計為10~1500質量份的量含有所述成分,進而較佳為以20~800質量份的量含有。 In the resin coating film, polysiloxane functions as a peeling agent for the resin coating film. Therefore, if the total amount of the epoxy-based resin and the melamine-based resin is too large compared to polysiloxane, the peeling strength imparted by the resin coating film between the resin substrate and the copper foil becomes large, so the peelability of the resin coating film Lower, sometimes not easy to peel off by hand. On the other hand, if the total amount of the epoxy-based resin and the melamine-based resin is too small, the peel strength becomes small, and therefore, the copper foil with a release layer may be peeled off during transportation or processing. From this point of view, it is preferable to contain the component in an amount of 10 to 1500 parts by mass relative to 100 parts by mass of polysiloxane, the total of epoxy resin and melamine resin, and more preferably 20 to 800 parts. Contains the amount of parts by mass.
另外,氟樹脂與聚矽氧同樣地,作為剝離劑發揮功能,具有使樹脂塗膜的耐熱性提升的效果。如果氟樹脂與聚矽氧相比過多,則所述剝離強度變小,因此有時會在積層體的搬送時或加工時剝離,另外,後述烘烤步驟所需的溫度提高,因此變得不經濟。就這個觀點來說,氟樹脂相對於聚矽氧100質量份,較佳為0~50質量份,進而較佳為0~40質量份。 In addition, the fluororesin functions as a release agent like polysiloxane, and has the effect of improving the heat resistance of the resin coating film. If the fluororesin is too large compared to polysiloxane, the peeling strength becomes smaller, so it may peel off during the conveyance or processing of the laminate, and the temperature required for the baking step described later increases, so it becomes not economic. From this viewpoint, the fluororesin is preferably 0-50 parts by mass, and more preferably 0-40 parts by mass with respect to 100 parts by mass of polysiloxane.
樹脂塗膜中,除聚矽氧、及環氧樹脂及/或三聚氰胺樹脂、及視需要的氟樹脂以外,也可進一步含有選自SiO2、MgO、Al2O3、BaSO4及Mg(OH)2中的一種以上的表面粗化粒子。藉由樹脂塗膜含有表面粗化粒子,而樹脂塗膜的表面變得凹凸。藉由所述凹凸,而塗布了樹脂塗膜的樹脂基板或銅箔的表面變得凹凸,而成為消光表面。關於表面粗化粒子的含量,只要使樹脂塗膜凹凸化,則沒有特別限定,相對於聚矽氧100質量份,較佳為1~10質量份。 The resin coating film, in addition to polysiloxane, epoxy resin and/or melamine resin, and optionally fluorine resin, may further contain SiO 2 , MgO, Al 2 O 3 , BaSO 4 and Mg(OH ) 2 of one or more surface roughening particles. The resin coating film contains surface roughened particles, and the surface of the resin coating film becomes uneven. Due to the unevenness, the surface of the resin substrate or copper foil coated with the resin coating film becomes uneven, and becomes a matte surface. The content of the surface roughened particles is not particularly limited as long as the resin coating film is uneven, and is preferably 1 to 10 parts by mass relative to 100 parts by mass of polysiloxane.
表面粗化粒子的粒徑較佳為15nm~4μm。在此,粒徑是指根據掃描電子顯微鏡(SEM)照片等測得的平均粒徑(最大粒徑與最小粒徑的平均值)。藉由表面粗化粒子的粒徑為所述範圍,而容易調整樹脂塗膜的表面的凹凸量,結果容易調整樹脂基板或銅箔的表面的凹凸量。具體來說,樹脂基板或銅箔的表面的凹凸量以JIS規定的最大高度粗糙度Ry計成為4.0μm左右。 The particle diameter of the surface roughened particles is preferably 15 nm to 4 μm . Here, the particle diameter refers to the average particle diameter (the average value of the largest particle diameter and the smallest particle diameter) measured from a scanning electron microscope (SEM) photograph or the like. When the particle diameter of the surface roughened particles is within the above range, it is easy to adjust the amount of irregularities on the surface of the resin coating film. As a result, it is easy to adjust the amount of irregularities on the surface of the resin substrate or copper foil. Specifically, the amount of irregularities on the surface of the resin substrate or copper foil is about 4.0 μm in terms of the maximum height roughness Ry prescribed by JIS.
在此,對積層體的製造方法進行說明。 Here, a method of manufacturing the laminate will be described.
所述附脫模層的銅箔經由具有如下步驟的程式而獲得:在樹脂基板或銅箔的至少一表面塗布所述樹脂塗膜的步驟;和使所述塗布的樹脂塗膜硬化的烘烤步驟。以下,對各步驟進行說明。 The copper foil with a release layer is obtained through a procedure having the following steps: a step of coating the resin coating film on at least one surface of a resin substrate or a copper foil; and a baking that hardens the coated resin coating film step. Hereinafter, each step will be described.
(塗布步驟) (Coating step)
塗布步驟是在樹脂基板的單面或兩面塗布樹脂塗料而形成樹脂塗膜的步驟,所述樹脂塗料由作為主劑的聚矽氧、作為硬化劑的環氧系樹脂、三聚氰胺系樹脂、及視需要的作為剝離劑的氟樹脂所構成。樹脂塗料是在醇等有機溶劑中溶解環氧系樹脂、三聚氰胺系樹脂、氟樹脂及聚矽氧而成。另外,樹脂塗料中的摻合量(添加量)較佳為相對於聚矽氧100質量份,環氧系樹脂、三聚氰胺系樹脂的合計為10~1500質量份。另外,氟樹脂較佳為相對於聚矽氧100質量份,為0~50質量份。 The coating step is a step of forming a resin coating film by coating a resin coating on one side or both sides of a resin substrate. The resin coating consists of polysiloxane as a main agent, epoxy-based resin as a curing agent, melamine-based resin, and It is composed of a fluororesin required as a release agent. Resin coating is made by dissolving epoxy resin, melamine resin, fluorine resin and polysiloxane in organic solvents such as alcohol. In addition, the blending amount (addition amount) in the resin coating is preferably 10 to 1500 parts by mass based on 100 parts by mass of the polysiloxane, and the total of the epoxy resin and the melamine resin. In addition, the fluororesin is preferably 0 to 50 parts by mass relative to 100 parts by mass of polysiloxane.
作為塗布步驟中的塗布方法,只要可形成樹脂塗膜,則沒有特別限定,使用凹版塗布法、棒式塗布法、輥式塗布法、淋幕式平面塗布法、利用靜電塗裝機的方法等,就樹脂塗膜的均勻性及作業便利性的觀點來說,較佳為凹版塗布法。另外,關於塗布量,作為樹脂量,較佳為1.0~2.0g/m2,以使樹脂塗膜3成為較佳的膜厚:0.5~5μm的方式。 The coating method in the coating step is not particularly limited as long as a resin coating film can be formed, and a gravure coating method, a bar coating method, a roll coating method, a curtain flat coating method, a method using an electrostatic coating machine, etc. are used From the viewpoint of the uniformity of the resin coating film and the convenience of work, the gravure coating method is preferred. In addition, the amount of coating is preferably 1.0 to 2.0 g/m 2 as the amount of resin, so that the resin coating film 3 has a preferable film thickness: 0.5 to 5 μm.
凹版塗布法是藉由使設置在輥表面的凹部(槽)中填滿的樹脂塗料轉印到樹脂基板,而在樹脂基板的表面形成樹脂塗膜的方法。具體來說, 將在表面設置了槽的下側輥的下部浸漬在樹脂塗料中,藉由下側輥的旋轉將樹脂塗料上吸到槽內。而且,在下側輥與配置在下側輥的上側的上側輥之間配置樹脂基板,一邊利用上側輥將樹脂基板壓抵於下側輥,一邊使下側輥及上側輥旋轉,藉此搬送樹脂基板,並且將上吸到槽內的樹脂塗料轉印(塗布)到樹脂基板的單面。 The gravure coating method is a method of forming a resin coating film on the surface of the resin substrate by transferring the resin coating material filled in the concave portion (groove) provided on the surface of the roller to the resin substrate. Specifically, the lower part of the lower roller provided with the groove on the surface is immersed in the resin paint, and the resin paint is sucked into the groove by the rotation of the lower roller. Then, the resin substrate is arranged between the lower roller and the upper roller disposed above the lower roller, and while the resin substrate is pressed against the lower roller by the upper roller, the lower roller and the upper roller are rotated to convey the resin substrate And, the resin paint sucked up into the tank is transferred (applied) to one side of the resin substrate.
另外,藉由在樹脂基板的搬入側,以與下側輥的表面接觸的方式配置刮刀,而將上吸到槽以外的輥表面的多餘的樹脂塗料除掉,從而在樹脂基板的表面塗布特定量的樹脂塗料。此外,在槽的號數(大小及深度)大的情況下或在樹脂塗料的黏度高的情況下,形成於樹脂基板的單面的樹脂塗膜不易變得平滑。因此,也可在樹脂基板的搬出側配置平滑輥,以維持樹脂塗膜的平滑度。 In addition, by arranging the blade on the loading side of the resin substrate so as to be in contact with the surface of the lower roller, the excess resin coating that is sucked up to the surface of the roller other than the groove is removed to apply a specific coating on the surface of the resin substrate The amount of resin coating. In addition, when the number (size and depth) of the groove is large or when the viscosity of the resin coating is high, the resin coating film formed on one side of the resin substrate is less likely to be smooth. Therefore, a smoothing roller may be arranged on the carrying out side of the resin substrate to maintain the smoothness of the resin coating film.
此外,在樹脂基板的兩面形成樹脂塗膜的情況下,在樹脂基板的單面形成樹脂塗膜後,將樹脂基板翻轉,並再次配置在下側輥與上側輥之間。而且,與所述同樣地,將下側輥的槽內的樹脂塗料轉印(塗布)到樹脂基板的背面。 In addition, when a resin coating film is formed on both surfaces of the resin substrate, after the resin coating film is formed on one surface of the resin substrate, the resin substrate is turned over and placed again between the lower roller and the upper roller. Then, in the same manner as described above, the resin paint in the groove of the lower roller is transferred (applied) to the back of the resin substrate.
(烘烤步驟) (Baking step)
烘烤步驟是對塗布步驟中形成的樹脂塗膜實施125~320℃(烘烤溫度)且0.5~60秒鐘(烘烤時間)的烘烤處理的步驟。如上所述,藉由對由特定摻合量的樹脂塗料形成的樹脂塗膜實施特定條件的烘烤處理,而將由樹脂塗膜賦予的樹脂基板與銅箔之間的剝離強度控制在特定範圍。在本發明中,烘烤溫度是樹脂基板的極限溫度。另外,作為用於烘烤處理的加熱手段,使用以往公知的裝置。 The baking step is a step of performing a baking treatment on the resin coating film formed in the coating step at 125 to 320°C (baking temperature) and 0.5 to 60 seconds (baking time). As described above, by subjecting the resin coating film formed of the resin coating with a specific blending amount to a specific condition of baking treatment, the peel strength between the resin substrate and the copper foil imparted by the resin coating film is controlled within a specific range. In the present invention, the baking temperature is the limit temperature of the resin substrate. In addition, as a heating means for the baking process, a conventionally known device is used.
在烘烤變得不充分的條件、例如烘烤溫度未達125℃或烘烤時間未達0.5秒的情況下,樹脂塗膜變得硬化不足,所述剝離強度超過200gf/cm,而 剝離性降低。另外,在烘烤過度的條件、例如烘烤溫度超過320℃的情況下,樹脂塗膜劣化,所述剝離強度超過200gf/cm,而剝離時的作業性變差。或者,有樹脂基板因高溫而變質的情況。另外,在烘烤時間超過60秒的情況下,生產性變差。 Under conditions where baking becomes insufficient, for example, when the baking temperature does not reach 125°C or the baking time does not reach 0.5 seconds, the resin coating film becomes insufficiently hardened, the peel strength exceeds 200 gf/cm, and the peelability reduce. In addition, under conditions where the baking is excessive, for example, when the baking temperature exceeds 320°C, the resin coating film deteriorates, the peel strength exceeds 200 gf/cm, and the workability at the time of peeling deteriorates. Or, the resin substrate may be deteriorated due to high temperature. In addition, when the baking time exceeds 60 seconds, productivity deteriorates.
在積層體的製造方法中,所述塗布步驟的樹脂塗料也可為由作為主劑的聚矽氧、作為硬化劑的環氧樹脂、三聚氰胺系樹脂、作為剝離劑的氟樹脂、和選自SiO2、MgO、Al2O3、BaSO4及Mg(OH)2中的一種以上的表面粗化粒子所構成的樹脂塗料。 In the manufacturing method of the laminate, the resin coating in the coating step may be made of polysiloxane as the main agent, epoxy resin as the hardener, melamine-based resin, fluororesin as the release agent, and selected from SiO 2. A resin coating composed of one or more surface roughened particles of MgO, Al 2 O 3 , BaSO 4 and Mg(OH) 2 .
具體來說,樹脂塗料是在所述聚矽氧添加樹脂溶液中進而添加表面粗化粒子而成。藉由將這種表面粗化粒子進而添加到樹脂塗料中,而使樹脂塗膜的表面變得凹凸,藉由所述凹凸使樹脂基板或銅箔變得凹凸,而成為消光表面。而且,為了獲得這種具有消光表面的樹脂基板或銅箔,較佳為樹脂塗料中的表面粗化粒子的摻合量(添加量)相對於聚矽氧100質量份為1~10質量份。另外,進而較佳為表面粗化粒子的粒徑為15nm~4μm。 Specifically, the resin coating is obtained by adding surface roughened particles to the polysiloxane added resin solution. By further adding such roughened particles to the resin coating, the surface of the resin coating film becomes uneven, and the uneven surface makes the resin substrate or copper foil uneven, and becomes a matte surface. Furthermore, in order to obtain such a resin substrate or copper foil having a matte surface, it is preferable that the blending amount (adding amount) of the surface roughened particles in the resin coating is 1 to 10 parts by mass with respect to 100 parts by mass of polysiloxane. In addition, it is further preferred that the particle diameter of the surface roughened particles is 15 nm to 4 μm .
本發明的製造方法如以上所說明的那樣,但當進行本發明時,在不會對所述各步驟造成不良影響的範圍內,也可在所述各步驟之間或前後,包括其他步驟。例如,也可在塗布步驟之前進行對樹脂基板的表面進行清洗的清洗步驟。 The manufacturing method of the present invention is as described above, but when the present invention is carried out, other steps may be included between or before the steps as long as they do not adversely affect the steps. For example, a cleaning step of cleaning the surface of the resin substrate may be performed before the coating step.
此外,本發明的脫模層也可為具有選自由合金、金屬、有機物及無機物所組成的群中的一種以上的層。作為所述合金、金屬、有機物、無機物,也可使用本申請的說明書中記載的合金、金屬、有機物或無機物。 In addition, the release layer of the present invention may have one or more layers selected from the group consisting of alloys, metals, organic substances, and inorganic substances. As the alloy, metal, organic substance, or inorganic substance, the alloy, metal, organic substance, or inorganic substance described in the specification of the present application may also be used.
‧可積層於附脫模層的銅箔的脫模層側的支持體或樹脂(後述絕緣基板1) ‧Support or resin that can be laminated on the release layer side of the copper foil with release layer (insulated
作為可積層於附脫模層的銅箔的脫模層側的樹脂,可使用公知的樹脂。另 外,所述樹脂可使用後述樹脂層。另外,作為可積層於附脫模層的銅箔的脫模層側的樹脂,沒有特別限制,可使用所有樹脂。另外,作為可積層於附脫模層的銅箔的脫模層側的樹脂,例如可使用酚樹脂、聚醯亞胺樹脂、環氧樹脂、氟樹脂、液晶聚合物樹脂、環烯烴聚合物樹脂、聚乙烯樹脂、聚對苯二甲酸乙二酯樹脂、氯乙烯樹脂、天然橡膠、松脂等。另外,可積層於附脫模層的銅箔的脫模層側的樹脂較佳為熱硬化性樹脂。另外,作為可積層於附脫模層的銅箔的脫模層側的樹脂,也可使用預浸體。與銅箔貼合前的預浸體較佳為處於B階段的狀態的預浸體。如果預浸體(C階段)的線膨脹係數為12~18(×10-6/℃),則與作為基板的構成材料的銅箔的16.5(×10-6/℃)、或SUS壓製板的17.3(×10-6/℃)幾乎相等,因此在不易產生因壓製前後的基板尺寸與設計時的基板尺寸不同的現象(尺度變化)引起的電路的位置偏移的方面有利。進而,作為這些優點的協同效應,也可生產多層的極薄無芯基板。此處使用的預浸體可與構成電路基板的預浸體相同也可不同。 As the resin that can be laminated on the release layer side of the copper foil with the release layer, a known resin can be used. In addition, as the resin, a resin layer described later can be used. In addition, the resin that can be laminated on the release layer side of the copper foil with a release layer is not particularly limited, and all resins can be used. In addition, as the resin that can be laminated on the release layer side of the copper foil with a release layer, for example, phenol resin, polyimide resin, epoxy resin, fluorine resin, liquid crystal polymer resin, cycloolefin polymer resin can be used , Polyethylene resin, polyethylene terephthalate resin, vinyl chloride resin, natural rubber, rosin, etc. In addition, the resin that can be laminated on the release layer side of the copper foil with a release layer is preferably a thermosetting resin. In addition, as a resin that can be laminated on the release layer side of the copper foil with a release layer, a prepreg can also be used. The prepreg before being bonded to the copper foil is preferably a prepreg in a state of B stage. If the linear expansion coefficient of the prepreg (stage C) is 12 to 18 (×10 -6 /℃), it is equivalent to 16.5 (×10 -6 /℃) of copper foil as the constituent material of the substrate, or SUS pressed plate 17.3 (×10 -6 /°C) is almost equal, which is advantageous in that the positional deviation of the circuit due to the phenomenon (scale change) of the substrate size before and after pressing differs from the substrate size at the time of design is unlikely to occur. Furthermore, as a synergistic effect of these advantages, a multi-layer ultra-thin coreless substrate can also be produced. The prepreg used here may be the same as or different from the prepreg constituting the circuit board.
關於所述預浸體,就將加熱後的剝離強度維持在最佳範圍的觀點來說,較佳為具有高玻璃轉移溫度Tg,例如為120~320℃、較佳為170~240℃的玻璃轉移溫度Tg。此外,玻璃轉移溫度Tg設為利用DSC(示差掃描熱測量法)測量的值。 Regarding the prepreg, from the viewpoint of maintaining the peel strength after heating in an optimal range, it is preferably a glass having a high glass transition temperature Tg, for example, 120 to 320°C, preferably 170 to 240°C Transfer temperature Tg. In addition, the glass transition temperature Tg is set to a value measured by DSC (differential scanning calorimetry).
另外,理想的是樹脂或預浸體或支持體的熱膨脹率為銅箔的熱膨脹率的+10%且-30%以內。藉此,可有效地防止起因於銅箔與樹脂的熱膨脹差的電路的位置偏移,而可使不良品產生減少,使良率提升。作為支持體,也可使用金屬板或金屬箔。 In addition, it is desirable that the thermal expansion rate of the resin, prepreg, or support is +10% and within -30% of the thermal expansion rate of the copper foil. As a result, the position of the circuit due to the difference in thermal expansion between the copper foil and the resin can be effectively prevented, and defective products can be reduced to improve the yield. As the support, a metal plate or metal foil can also be used.
樹脂或支持體的厚度沒有特別限制。另外,樹脂或支持體可為剛性也可為撓性。此外,如果樹脂或支持體的厚度過厚,則會對熱壓中的熱分佈造成不良影響,另一方面,如果過薄,則有時會彎曲而使印刷配線板的製造 步驟無法進行,因此樹脂或支持體的厚度通常較佳為5μm以上且1000μm以下。另外,樹脂或支持體的厚度更佳為50μm以上且900μm以下,進而更佳為100μm以上且400μm以下。 The thickness of the resin or the support is not particularly limited. In addition, the resin or the support may be rigid or flexible. In addition, if the thickness of the resin or the support is too thick, it will adversely affect the heat distribution during hot pressing. On the other hand, if it is too thin, it may be bent and the manufacturing process of the printed wiring board may not be performed, so The thickness of the resin or the support is usually preferably 5 μm or more and 1000 μm or less. In addition, the thickness of the resin or the support is more preferably 50 μm or more and 900 μm or less, and still more preferably 100 μm or more and 400 μm or less.
<積層體> <Laminate>
可使用本發明的附脫模層的銅箔製作積層體(覆銅積層體等)。 The copper foil with a mold release layer of the present invention can be used to produce a laminate (copper-clad laminate, etc.).
作為使用本發明的附脫模層的銅箔的積層體,例如也可為依序積層「支持體或樹脂或預浸體/脫模層/銅箔/阻隔層」的構成。 As a laminate of the copper foil with a mold release layer of the present invention, for example, a structure in which a "support or resin or prepreg/release layer/copper foil/barrier layer" is sequentially laminated may be used.
所述支持體或樹脂或預浸體可為後述樹脂層,也可包含用於後述樹脂層的樹脂、樹脂硬化劑、化合物、硬化促進劑、介電體、反應催化劑、交聯劑、聚合物、預浸體、骨架材料等。此外,附脫模層的銅箔也可在俯視時小於支持體或樹脂或預浸體。 The support, resin, or prepreg may be a resin layer described later, or may contain a resin, resin hardener, compound, hardening accelerator, dielectric, reaction catalyst, crosslinking agent, polymer for the resin layer described later. , Prepreg, skeleton material, etc. In addition, the copper foil with the release layer may be smaller than the support, resin, or prepreg in plan view.
<粗化處理及其他表面處理> <roughening treatment and other surface treatments>
在附脫模層的銅箔的阻隔層的與銅箔為相反側的表面或附脫模層的銅箔的銅箔與阻隔層之間,例如也可藉由實施粗化處理而設置粗化處理層,以使與絕緣基板或樹脂的密接性良好。粗化處理例如可藉由利用銅或銅合金形成粗化粒子而進行。粗化處理也可為微細的粗化處理。粗化處理層也可為由選自由Cu(銅)、Ni(鎳)、P(磷)、W(鎢)、As(砷)、Mo(鉬)、Cr(鉻)、Ti(鈦)、Fe(鐵)、V(釩)、Co(鈷)及Zn(鋅)所組成的群中的任一種單質或含有任一種以上所述單質的合金所構成的層等。另外,也可在利用銅或銅合金形成粗化粒子後,進而進行利用鎳、鈷、銅、鋅的單質或合金等設置二次粒子或三次粒子的粗化處理。之後,也可利用鎳、鈷、銅、鋅、錫、鉬、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭的單質及/或合金及/或氧化物及/或氮化物及/或矽化物等形成耐熱層或防銹層,也可進而對所述耐熱層或防銹層的表面實施鉻酸鹽處理、矽烷偶合處理等處理。或者,也可不進 行粗化處理,而利用鎳、鈷、銅、鋅、錫、鉬、鎢、磷、砷、鉻、釩、鈦、鋁、金、銀、鉑族元素、鐵、鉭的單質及/或合金及/或氧化物及/或氮化物及/或矽化物等形成耐熱層或防銹層,進而對所述耐熱層或防銹層的表面實施鉻酸鹽處理、矽烷偶合處理等處理。即,也可在粗化處理層的表面形成選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的一種以上的層,也可在附脫模層的銅箔的阻隔層的與銅箔為相反側的表面或附脫模層的銅箔的銅箔與阻隔層之間,形成選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的一種以上的層。另外,也可在附脫模層的銅箔的阻隔層的與銅箔為相反側的表面或附脫模層的銅箔的銅箔與阻隔層之間,形成選自由粗化處理層、耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的一種以上的層。另外,也可在附脫模層的銅箔的銅箔與脫模層之間,形成選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的一種以上的層。所述耐熱層也可為銅層。所述防銹層也可為銅層。此外,所述耐熱層、防銹層、鉻酸鹽處理層、矽烷偶合處理層也可分別由多個層形成(例如2層以上、3層以上等)。 The surface of the barrier layer of the copper foil with the release layer on the opposite side to the copper foil or between the copper foil of the copper foil with the release layer and the barrier layer may be roughened by performing a roughening treatment, for example Treat the layer to improve the adhesion to the insulating substrate or resin. The roughening treatment can be performed by forming roughened particles using copper or a copper alloy, for example. The roughening treatment may be fine roughening treatment. The roughening layer can also be selected from Cu (copper), Ni (nickel), P (phosphorus), W (tungsten), As (arsenic), Mo (molybdenum), Cr (chromium), Ti (titanium), A single element of a group composed of any one of Fe (iron), V (vanadium), Co (cobalt), and Zn (zinc) or an alloy containing any one or more of the above elements, etc. In addition, after forming the roughened particles using copper or a copper alloy, a roughening treatment may be performed in which secondary particles or tertiary particles are provided using a simple substance or alloy of nickel, cobalt, copper, zinc, or the like. Thereafter, the elemental and/or alloys of nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum and/or An oxide and/or nitride and/or silicide, etc. may be used to form a heat-resistant layer or a rust-proof layer, and the surface of the heat-resistant layer or rust-proof layer may be further subjected to chromate treatment, silane coupling treatment, or the like. Alternatively, instead of roughening, nickel, cobalt, copper, zinc, tin, molybdenum, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum can be used. And/or alloys and/or oxides and/or nitrides and/or silicides to form a heat-resistant layer or rust-proof layer, and then the surface of the heat-resistant layer or rust-proof layer is subjected to chromate treatment and silane coupling treatment, etc. deal with. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. The surface of the barrier layer of the copper foil opposite to the copper foil or the copper foil with the release layer of the copper foil and the barrier layer is formed from a heat-resistant layer, a rust-proof layer, a chromate treatment layer and a silane coupling treatment More than one layer in a group of layers. Alternatively, a surface layer selected from the group consisting of the roughening treatment layer and the heat-resistant layer may be formed between the surface of the barrier layer of the copper foil with the release layer and the copper foil on the side opposite to the copper foil or the copper foil with the copper foil of the release layer One or more layers in the group consisting of a layer, an anti-rust layer, a chromate treatment layer, and a silane coupling treatment layer. In addition, one or more types selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed between the copper foil of the copper foil with a release layer and the release layer Layer. The heat-resistant layer may also be a copper layer. The anti-rust layer may also be a copper layer. In addition, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer may each be formed of a plurality of layers (for example, 2 or more layers, 3 or more layers, etc.).
例如,作為粗化處理的銅-鈷-鎳合金鍍覆可以藉由電解鍍覆形成像附著量為15~40mg/dm2的銅-100~3000μg/dm2的鈷-100~1500μg/dm2的鎳這樣的3元系合金層的方式實施。如果Co附著量未達100μg/dm2,則有耐熱性變差而蝕刻性變差的情況。如果Co附著量超過3000μg/dm2,則在必須考慮磁性影響的情況下不佳,有產生蝕刻斑點以及耐酸性及耐化學品性變差的情況。如果Ni附著量未達100μg/dm2,則有耐熱性變差的情況。另一方面,如果Ni附著量超過1500μg/dm2,則有蝕刻殘留變多的情況。較佳的Co附著量為1000~2500μg/dm2,較佳的鎳附著量為500~1200μg/dm2。在此,所謂蝕刻斑點,是指在利用氯化銅進行蝕刻的情況下,Co不溶解而殘留,而且,所謂蝕 刻殘留,是指在利用氯化銨進行鹼蝕刻的情況下,Ni不溶解而殘留。 For example, copper-cobalt-nickel alloy plating as a roughening treatment can be formed by electrolytic plating to form copper with an adhesion amount of 15-40 mg/dm 2 -100-3000 μ g/dm 2 cobalt -100-1500 μ It is implemented as a ternary alloy layer such as g/dm 2 nickel. If the deposited mass of Co less than 100 μ g / dm 2, there is poor heat resistance and etching properties deteriorated. If the case of poor adhesion Co amount exceeds 3000 μ g / dm 2, then the magnetic properties must be considered, it is etched to produce spots and where acid resistance and chemical resistance deteriorates. If the deposited mass of Ni less than 100 μ g / dm 2, there is a case where heat resistance is deteriorated. On the other hand, if the Ni deposition amount exceeds 1500 μ g / dm 2, the etching becomes more remaining cases. The preferred adhesion amount of Co is 1000 ~ 2500 μ g / dm 2 , Ni deposition amount is preferably 500 ~ 1200 μ g / dm 2 . Here, the etching spot means that when copper chloride is used for etching, Co does not dissolve and remains, and the etching residue means that when ammonium chloride is used for alkaline etching, Ni does not dissolve but Residue.
用以形成這種3元系銅-鈷-鎳合金鍍覆的一般浴及鍍覆條件的一個例子如下所述:鍍覆浴組成:Cu 10~20g/L、Co 1~10g/L、Ni 1~10g/L An example of general baths and plating conditions used to form this ternary copper-cobalt-nickel alloy plating is as follows: Plating bath composition:
pH值:1~4 pH value: 1~4
溫度:30~50℃ Temperature: 30~50℃
電流密度Dk:20~30A/dm2 Current density D k : 20~30A/dm 2
鍍覆時間:1~5秒 Plating time: 1~5 seconds
所述鉻酸鹽處理層是指利用包含鉻酸酐、鉻酸、二鉻酸、鉻酸鹽或二鉻酸鹽的液體處理過的層。鉻酸鹽處理層也可包含Co、Fe、Ni、Mo、Zn、Ta、Cu、Al、P、W、Sn、As及Ti等元素(也可為金屬、合金、氧化物、氮化物、硫化物等任何形態)。作為鉻酸鹽處理層的具體例,可列舉利用鉻酸酐或二鉻酸鉀水溶液處理過的鉻酸鹽處理層或利用包含鉻酸酐或二鉻酸鉀及鋅的處理液處理過的鉻酸鹽處理層等。 The chromate treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate, or dichromate. The chromate treatment layer may also contain elements such as Co, Fe, Ni, Mo, Zn, Ta, Cu, Al, P, W, Sn, As, and Ti (also may be metals, alloys, oxides, nitrides, sulfides Things, etc.). Specific examples of the chromate treatment layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromate treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Processing layer, etc.
所述矽烷偶合處理層可使用公知的矽烷偶合劑而形成,也可使用環氧系矽烷、胺基系矽烷、甲基丙烯醯氧基系矽烷、巰基系矽烷、乙烯系矽烷、咪唑系矽烷、三系矽烷等矽烷偶合劑等而形成。此外,這種矽烷偶合劑也可將兩種以上混合而使用。其中,較佳為使用胺基系矽烷偶合劑或環氧系矽烷偶合劑而形成的矽烷偶合處理層。 The silane coupling treatment layer may be formed using a well-known silane coupling agent, or epoxy silane, amine silane, methacryl oxysilane, mercapto silane, vinyl silane, imidazole silane, three It is formed by silane coupling agent such as silane. In addition, this silane coupling agent can also be used by mixing two or more kinds. Among them, a silane coupling treatment layer formed using an amine-based silane coupling agent or an epoxy-based silane coupling agent is preferred.
另外,可對附脫模層的銅箔的阻隔層側的表面或粗化處理層、耐熱層、防銹層、矽烷偶合處理層或鉻酸鹽處理層的表面進行國際公開編號WO2008/053878、日本特開2008-111169號、日本專利第5024930號、國際公開編號WO2006/028207、日本專利第4828427號、國際公開編號WO2006/134868、日本專利第5046927號、國際公開編號WO2007/105635、日本專利第5180815 號、日本特開2013-19056號中記載的表面處理。 In addition, the surface of the barrier layer side of the copper foil with the release layer or the surface of the roughening treatment layer, the heat-resistant layer, the rust prevention layer, the silane coupling treatment layer or the chromate treatment layer can be given International Publication No. WO2008/053878, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, Japanese Patent No. 5046927, International Publication No. WO2007/105635, Japanese Patent No. Surface treatment described in No. 5180815 and Japanese Patent Laid-Open No. 2013-19056.
另外,可在附脫模層的銅箔的阻隔層側的表面或附脫模層的銅箔的銅箔與阻隔層之間具備粗化處理層,也可在所述粗化處理層上具備一個以上的選自由耐熱層、防銹層、鉻酸鹽處理層及矽烷偶合處理層所組成的群中的層。 In addition, a roughening treatment layer may be provided on the surface of the copper foil with a release layer on the barrier layer side or between the copper foil of the copper foil with a release layer and the barrier layer, or may be provided on the roughening treatment layer One or more layers selected from the group consisting of a heat-resistant layer, an anti-rust layer, a chromate treatment layer, and a silane coupling treatment layer.
另外,可在附脫模層的銅箔的阻隔層側的表面或附脫模層的銅箔的銅箔與阻隔層之間具備粗化處理層,可在所述粗化處理層上具備耐熱層、防銹層,可在所述耐熱層、防銹層上具備鉻酸鹽處理層,也可在所述鉻酸鹽處理層上具備矽烷偶合處理層。 In addition, a roughening treatment layer may be provided on the surface of the barrier layer side of the copper foil with release layer or between the copper foil of the copper foil with release layer and the barrier layer, and heat resistance may be provided on the roughening treatment layer The layer and the rust prevention layer may be provided with a chromate treatment layer on the heat-resistant layer or the rust prevention layer, or may be provided with a silane coupling treatment layer on the chromate treatment layer.
另外,也可在附脫模層的銅箔的阻隔層側的表面或附脫模層的銅箔的銅箔與阻隔層之間或所述粗化處理層上、或所述耐熱層、或所述防銹層、或所述鉻酸鹽處理層、或所述矽烷偶合處理層上具備樹脂層。所述樹脂層也可為絕緣樹脂層。 In addition, the surface of the copper foil with a mold release layer on the barrier layer side, or between the copper foil of the copper foil with a mold release layer and the barrier layer, or on the roughening treatment layer, or the heat-resistant layer, or A resin layer is provided on the rust prevention layer, the chromate treatment layer, or the silane coupling treatment layer. The resin layer may also be an insulating resin layer.
所述樹脂層可為接著劑,也可為接著用的半硬化狀態(B階段)的絕緣樹脂層。所謂半硬化狀態(B階段狀態),是指即使用手指觸摸該樹脂層的表面也沒有黏著感,而可將所述絕緣樹脂層重疊進行保管,進而包含如果受到加熱處理則會發生硬化反應的狀態。 The resin layer may be an adhesive or an insulating resin layer in a semi-cured state (stage B) for subsequent use. The so-called semi-cured state (B-stage state) means that even if the surface of the resin layer is touched with a finger, there is no sticky feeling, and the insulating resin layer can be superimposed and stored, and further includes a curing reaction that occurs if subjected to heat treatment. status.
另外,所述樹脂層可包含熱硬化性樹脂,也可為熱塑性樹脂。另外,所述樹脂層也可包含熱塑性樹脂。熱塑性樹脂的種類沒有特別限定,例如,作為較佳的熱塑性樹脂,可列舉包含選自以下的樹脂的群中的一種以上的樹脂:環氧樹脂、聚醯亞胺樹脂、多官能性氰酸酯化合物、順丁烯二醯亞胺化合物、聚乙烯醇縮醛樹脂、胺酯樹脂、聚醚碸、聚醚碸樹脂、芳香族聚醯胺樹脂、芳香族聚醯胺樹脂聚合物、橡膠性樹脂、聚胺、芳香族聚胺、聚醯胺醯亞胺樹脂、橡膠改質環氧樹脂、苯氧樹脂、羧基改質丙烯腈-丁二烯樹脂、聚苯 醚、雙順丁烯二醯亞胺三樹脂、熱硬化性聚苯醚樹脂、氰酸酯系樹脂、羧酸的酸酐、多元羧酸的酸酐、具有可交聯的官能基的線性聚合物、聚苯醚樹脂、2,2-雙(4-氰酸酯基苯基)丙烷、含磷的酚化合物、環烷酸錳、2,2-雙(4-縮水甘油基苯基)丙烷、聚苯醚-氰酸酯系樹脂、矽氧烷改質聚醯胺醯亞胺樹脂、氰基酯樹脂、磷腈系樹脂、橡膠改質聚醯胺醯亞胺樹脂、異戊二烯、氫化型聚丁二烯、聚乙烯丁醛、苯氧樹脂、高分子環氧樹脂、芳香族聚醯胺、氟樹脂、雙酚、嵌段共聚聚醯亞胺樹脂及氰基酯樹脂。 In addition, the resin layer may include a thermosetting resin or a thermoplastic resin. In addition, the resin layer may contain a thermoplastic resin. The type of thermoplastic resin is not particularly limited. For example, preferred thermoplastic resins include one or more resins selected from the group of resins: epoxy resins, polyimide resins, and polyfunctional cyanates. Compounds, maleimide compounds, polyvinyl acetal resins, urethane resins, polyether socks, polyether sack resins, aromatic polyamide resins, aromatic polyamide resin polymers, rubbery resins , Polyamines, aromatic polyamines, polyamidoamide resins, rubber-modified epoxy resins, phenoxy resins, carboxy-modified acrylonitrile-butadiene resins, polyphenylene oxide, bis-cis-butadiene diacrylic acid Amine tri Resins, thermosetting polyphenylene ether resins, cyanate ester resins, carboxylic acid anhydrides, polycarboxylic acid anhydrides, linear polymers with crosslinkable functional groups, polyphenylene ether resins, 2,2-bis( 4-cyanoylphenyl)propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis(4-glycidylphenyl)propane, polyphenylene ether-cyanate resin, silicone Alkane-modified polyamidoamide resin, cyanoester resin, phosphazene resin, rubber-modified polyamidoamide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, benzene Oxygen resin, high molecular epoxy resin, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin and cyanoester resin.
另外,所述環氧樹脂只要在分子內具有2個以上的環氧基且可用於電氣、電子材料用途,則可沒有特別問題地使用。另外,所述環氧樹脂較佳為使用分子內具有2個以上的縮水甘油基的化合物進行環氧化而成的環氧樹脂。另外,所述環氧樹脂可將選自以下的樹脂的群中的一種或兩種以上混合而使用:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、雙酚AD型環氧樹脂、酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、脂環式環氧樹脂、溴化(brominated)環氧樹脂、苯酚酚醛清漆型環氧樹脂、萘型環氧樹脂、溴化雙酚A型環氧樹脂、鄰甲酚酚醛清漆型環氧樹脂、橡膠改質雙酚A型環氧樹脂、縮水甘油胺型環氧樹脂、異氰尿酸三縮水甘油酯、N,N-二縮水甘油基苯胺等縮水甘油胺化合物、四氫鄰苯二甲酸二縮水甘油酯等縮水甘油酯化合物、含磷的環氧樹脂、聯苯型環氧樹脂、聯苯酚醛清漆型環氧樹脂、三羥基苯基甲烷型環氧樹脂、四苯基乙烷型環氧樹脂,或者可使用所述環氧樹脂的氫化體或鹵化體。 In addition, the epoxy resin can be used without particular problems as long as it has two or more epoxy groups in the molecule and can be used for electrical and electronic materials. In addition, the epoxy resin is preferably an epoxy resin obtained by epoxidation using a compound having two or more glycidyl groups in the molecule. In addition, the epoxy resin can be used by mixing one or more types selected from the group of the following resins: bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin , Bisphenol AD epoxy resin, novolac epoxy resin, cresol novolac epoxy resin, alicyclic epoxy resin, brominated epoxy resin, phenol novolac epoxy resin, naphthalene Epoxy resin, brominated bisphenol A epoxy resin, o-cresol novolac epoxy resin, rubber modified bisphenol A epoxy resin, glycidyl amine epoxy resin, triglycidyl isocyanurate Glycidylamine compounds such as esters, N,N-diglycidylaniline, glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester, phosphorus-containing epoxy resin, biphenyl type epoxy resin, biphenol novolac Varnish-type epoxy resin, trihydroxyphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin, or a hydrogenated or halogenated body of the epoxy resin can be used.
作為所述含磷的環氧樹脂,可使用公知的含有磷的環氧樹脂。另外,所述含磷的環氧樹脂例如較佳為作為來自分子內具備2個以上的環氧基的9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物的衍生物而獲得的環氧樹脂。 As the phosphorus-containing epoxy resin, a known phosphorus-containing epoxy resin can be used. In addition, the phosphorus-containing epoxy resin is preferably, for example, a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derived from a molecule having two or more epoxy groups in the molecule. Derivative epoxy resin.
所述樹脂層可包含公知的樹脂、樹脂硬化劑、化合物、硬化促 進劑、介電體(也可使用包含無機化合物及/或有機化合物的介電體、包含金屬氧化物的介電體等任何介電體)、反應催化劑、交聯劑、聚合物、預浸體、骨架材料等。另外,所述樹脂層也可使用以下的文獻中所記載的物質(樹脂、樹脂硬化劑、化合物、硬化促進劑、介電體、反應催化劑、交聯劑、聚合物、預浸體、骨架材料等)及/或樹脂層的形成方法、形成裝置而形成:例如國際公開編號WO2008/004399號、國際公開編號WO2008/053878、國際公開編號WO2009/084533、日本特開平11-5828號、日本特開平11-140281號、日本專利第3184485號、國際公開編號WO97/02728、日本專利第3676375號、日本特開2000-43188號、日本專利第3612594號、日本特開2002-179772號、日本特開2002-359444號、日本特開2003-304068號、日本專利第3992225、日本特開2003-249739號、日本專利第4136509號、日本特開2004-82687號、日本專利第4025177號、日本特開2004-349654號、日本專利第4286060號、日本特開2005-262506號、日本專利第4570070號、日本特開2005-53218號、日本專利第3949676號、日本專利第4178415號、國際公開編號WO2004/005588、日本特開2006-257153號、日本特開2007-326923號、日本特開2008-111169號、日本專利第5024930號、國際公開編號WO2006/028207、日本專利第4828427號、日本特開2009-67029號、國際公開編號WO2006/134868、日本專利第5046927號、日本特開2009-173017號、國際公開編號WO2007/105635、日本專利第5180815號、國際公開編號WO2008/114858、國際公開編號WO2009/008471、日本特開2011-14727號、國際公開編號WO2009/001850、國際公開編號WO2009/145179、國際公開編號WO2011/068157、日本特開2013-19056號。 The resin layer may contain any known resins, resin hardeners, compounds, hardening accelerators, and dielectrics (dielectrics containing inorganic compounds and/or organic compounds, dielectrics containing metal oxides, etc. may be used. Dielectrics), reaction catalysts, crosslinking agents, polymers, prepregs, framework materials, etc. In addition, the resin layer may use substances described in the following documents (resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material) Etc.) and/or a resin layer forming method and forming device: for example, International Publication No. WO2008/004399, International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Patent Laid-Open No. 11-5828, Japanese Patent Laid-Open 11-140281, Japanese Patent No. 3184485, International Publication No. WO97/02728, Japanese Patent No. 3676375, Japanese Patent Publication No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Publication No. 2002-179772, Japanese Patent Publication No. 2002 -359444, JP 2003-304068, JP 3992225, JP 2003-249739, JP 4136509, JP 2004-82687, JP 4025177, JP 2004- 349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, Japanese Patent Laid-Open No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029 , International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese Patent Laid-Open No. 2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japan Japanese Patent Laid-Open No. 2011-14727, International Publication No. WO2009/001850, International Publication No. WO2009/145179, International Publication No. WO2011/068157, Japanese Patent Laid-Open No. 2013-19056.
將這些樹脂溶解於例如甲基乙基酮(MEK)、甲苯等溶劑而製成樹脂溶液,並藉由例如輥式塗布機法等將所述樹脂溶液塗布在附脫模層的銅箔的阻隔層側的表面、或所述粗化處理層、所述耐熱層、防銹層、或所述鉻酸 鹽皮膜層、或所述矽烷偶合劑層上,接著視需要進行加熱乾燥將溶劑去除,而成為B階段狀態。乾燥可使用例如熱風乾燥爐,乾燥溫度可為100~250℃、較佳為130~200℃。 These resins are dissolved in a solvent such as methyl ethyl ketone (MEK), toluene, etc. to prepare a resin solution, and the resin solution is applied to the barrier of the copper foil with a release layer by, for example, a roll coater method or the like On the surface of the layer side, or the roughened layer, the heat-resistant layer, the rust-preventive layer, or the chromate film layer, or the silane coupling agent layer, the solvent is then removed by heating and drying if necessary, It becomes the B stage state. For drying, for example, a hot air drying furnace can be used, and the drying temperature can be 100 to 250°C, preferably 130 to 200°C.
具備所述樹脂層的附脫模層的銅箔(附有樹脂的附脫模層的銅箔)是以如下的態樣使用:將所述樹脂層重疊於基材後,對整體進行熱壓接而使所述樹脂層熱硬化,從而在銅箔的阻隔層側表面形成特定的配線圖案。 The copper foil with a mold release layer provided with the resin layer (copper foil with a resin with a mold release layer) is used as follows: after the resin layer is overlaid on the base material, the whole is hot pressed Then, the resin layer is thermally cured to form a specific wiring pattern on the surface of the copper foil on the barrier layer side.
如果使用所述附有樹脂的附脫模層的銅箔,則可減少製造多層印刷配線基板時的預浸體材的使用片數。而且,可使樹脂層的厚度成為像可確保層間絕緣那樣的厚度,或者即使完全不使用預浸體材也可製造覆銅積層板。另外,此時,也可在基材的表面將絕緣樹脂進行底漆塗布而進一步改善表面的平滑性。 If the resin-attached copper foil with a mold release layer is used, the number of prepreg materials used when manufacturing a multilayer printed wiring board can be reduced. Furthermore, the thickness of the resin layer can be made as thick as the interlayer insulation can be ensured, or a copper-clad laminate can be manufactured even without using a prepreg material at all. In addition, in this case, the insulating resin may be primed on the surface of the base material to further improve the smoothness of the surface.
此外,在不使用預浸體材的情況下,具有如下優點:節約了預浸體材的材料成本,另外,積層步驟也變得簡略,因此經濟上變得有利,而且,與預浸體材的厚度相應地,製造的多層印刷配線基板的厚度變薄,可製造1層的厚度為100μm以下的極薄的多層印刷配線基板。 In addition, when the prepreg material is not used, it has the following advantages: the material cost of the prepreg material is saved, and the lamination step is also simplified, so it becomes economically advantageous, and, with the prepreg material Accordingly, the thickness of the multilayer printed wiring board to be manufactured becomes thinner, and an extremely thin multilayer printed wiring board with a thickness of 100 μm or less per layer can be manufactured.
所述樹脂層的厚度較佳為0.1~80μm。如果樹脂層的厚度薄於0.1μm,則接著力降低,在不介置預浸體材而將所述附有樹脂的附脫模層的銅箔積層於具備內層材的基材時,存在難以確保與內層材的電路之間的層間絕緣的情況。 The thickness of the resin layer is preferably 0.1 to 80 μm . If the thickness of the resin layer is thinner than 0.1 μm , the adhesive force decreases, and when the copper foil with the resin-attached release layer is laminated on the base material provided with the inner layer material without interposing the prepreg material, There are cases where it is difficult to ensure the interlayer insulation from the circuit of the inner layer material.
另一方面,如果使樹脂層的厚度厚於80μm,則難以藉由1次塗布步驟形成目標厚度的樹脂層,而要花費額外的材料費和工時,因此經濟上變得不利。進而,所形成的樹脂層的可撓性變差,因此有時在操作時容易產生裂痕等,另外,在與內層材的熱壓接時引起多餘的樹脂流動而難以進行順暢的積層。 On the other hand, if the thickness of the resin layer is thicker than 80 μm , it is difficult to form the resin layer of the target thickness in one coating step, and it takes extra material costs and man-hours, so it becomes economically disadvantageous. Furthermore, the flexibility of the formed resin layer deteriorates, so cracks and the like are likely to occur during handling, and excessive resin flow is caused during thermal compression bonding with the inner layer material, making smooth lamination difficult.
作為附有樹脂的附脫模層的銅箔的另一個製品形態,也可在附脫模層的銅箔的阻隔層側的表面、或所述粗化處理層、所述耐熱層、防銹層、或所述鉻酸鹽處理層、或所述矽烷偶合處理層上,利用樹脂層進行被覆,成為半硬化狀態後,以附有樹脂的銅箔的形式進行製造。 As another product form of the copper foil with a resin-attached release layer, the surface of the copper foil with a release layer on the barrier layer side, or the roughened layer, the heat-resistant layer, and rust prevention The layer, or the chromate-treated layer or the silane coupling-treated layer is coated with a resin layer to be in a semi-cured state, and then manufactured in the form of resin-coated copper foil.
進而,藉由在印刷配線板搭載電子零件類,而完成印刷電路板。在本發明中,「印刷配線板」也包含像所述那樣搭載了電子零件類的印刷配線板及印刷電路板及印刷基板。 Furthermore, by mounting electronic components on the printed wiring board, the printed circuit board is completed. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed board on which electronic components are mounted as described above.
另外,可使用所述印刷配線板製作電子機器,也可使用所述搭載了電子零件類的印刷電路板製作電子機器,還可使用所述搭載了電子零件類的印刷基板製作電子機器。以下,表示若干使用本發明的附脫模層的銅箔的印刷配線板的製造步驟的例子。 In addition, the printed wiring board may be used to manufacture an electronic device, the printed circuit board mounted with electronic components may be used to manufacture an electronic device, or the printed circuit board mounted with electronic components may be used to manufacture an electronic device. Hereinafter, some examples of the manufacturing process of the printed wiring board using the copper foil with a mold release layer of this invention are shown.
以下,對印刷配線板的製造方法的例子進行說明,所述印刷配線板的製造方法包括使用本發明的附脫模層的銅箔形成埋入電路的步驟。此外,在本說明書中,「電路」的概念包括配線。 Hereinafter, an example of a method of manufacturing a printed wiring board including the step of forming a buried circuit using the copper foil with a mold release layer of the present invention will be described. In addition, in this specification, the concept of "circuit" includes wiring.
圖1~圖4表示用以說明使用本發明的一實施形態的附脫模層的銅箔的埋入電路的形成方法的示意圖。使用本發明的一實施形態的附脫模層的銅箔的埋入電路的形成方法是首先在本發明的附脫模層的銅箔(圖1a)的所述脫模層30側積層絕緣基板1(圖1b)。其次,在積層了絕緣基板1的附脫模層的銅箔的阻隔層10側設置經圖案化的抗鍍覆層40(圖1c)。其次,在設置了經圖案化的抗鍍覆層40的阻隔層10上設置鍍銅層50(圖2d)。其次,藉由將抗鍍覆層40去除而形成鍍銅電路51(圖2e)。其次,藉由利用絕緣基板2覆蓋鍍銅電路51而將鍍銅電路51埋入(圖2f)。另外,此時,可進而在絕緣基板2上設置銅箔60(圖3g),也可接著對所述銅箔60進行蝕刻,藉此形成鍍銅電路61(圖3h)。其次,藉由將脫模層30側的表面的絕緣基板1去除而使附脫模層的銅箔 的脫模層30側的表面露出(圖3i)。其次,利用蝕刻將銅箔20自露出的脫模層30側的表面去除而使阻隔層10的表面露出(圖4j)。其次,利用蝕刻將露出的阻隔層10去除,藉此使埋入絕緣基板2中的電路露出(圖4k)。以所述方式獲得埋入電路,從而可製造使用所述埋入電路的印刷配線板。 1 to 4 are schematic diagrams for explaining a method of forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention. A method of forming a buried circuit using a copper foil with a release layer according to an embodiment of the present invention is to first build up an insulating substrate on the
另外,在圖1b的步驟後,也可在絕緣基板1的未積層附脫模層的銅箔一側的表面,如圖5所示,積層另一附脫模層的銅箔,即,製作依序積層阻隔層10/銅箔20/脫模層30/絕緣基板1/脫模層31/銅箔21/阻隔層11而成的積層體。在所述情況下,也可在絕緣基板1的一表面的附脫模層的銅箔,以圖1c~圖4k的方式形成埋入電路,另一方面,在絕緣基板1的另一表面的附脫模層的銅箔,也以同樣的程序形成埋入電路。此外,在所述印刷配線板的製造方法中,也可將所述絕緣基板1改稱為所述支持體。 In addition, after the step of FIG. 1b, the surface of the insulating
此外,絕緣基板1及2可使用埋入樹脂(RESIN)。所述埋入樹脂可使用公知的樹脂、預浸體。例如可使用BT(雙順丁烯二醯亞胺三)樹脂或作為含浸有BT樹脂的玻璃布的預浸體、Ajinomoto Fine-Techno股份有限公司製造的ABF膜或ABF。另外,所述絕緣基板1及2及所述埋入樹脂(RESIN)可使用公知的樹脂或本說明書中記載的樹脂層及/或樹脂及/或預浸體。 In addition, embedded resins (RESIN) can be used for the insulating
本發明的印刷配線板的製造方法也可為包含如下步驟的印刷配線板的製造方法(無芯法(coreless method)):將本發明的附脫模層的銅箔的所述阻隔層側表面或所述脫模層側表面與樹脂基板進行積層的步驟;在與和所述樹脂基板積層的阻隔層側表面或所述脫模層側表面為相反側的附脫模層的銅箔的表面,至少設置1次樹脂層和電路這兩層的步驟;及形成所述樹脂層及電路這兩層後,自所述附脫模層的銅箔使所述樹脂層及電路這兩層剝離的步驟。此外,樹脂層及電路這兩層可依序設置樹脂層、電路,也可依序設置電路、樹脂層。關於所述無芯法,作為具體的例子,首先,將本發明的附脫模層 的銅箔的阻隔層側表面或脫模層側表面與樹脂基板積層而製造積層體(也稱為覆銅積層板、覆銅積層體)。之後,在與和樹脂基板積層的阻隔層側表面或所述脫模層側表面為相反側的附脫模層的銅箔的表面形成樹脂層。也可在形成於脫模層側表面或銅箔側表面的樹脂層,進而自脫模層側或阻隔層側積層另一附脫模層的銅箔。另外,也可將具有如下構成的積層體用於所述印刷配線板的製造方法(無芯法):以樹脂基板或樹脂或預浸體為中心,在所述樹脂基板或樹脂或預浸體的兩個表面側,以脫模層/銅箔/阻隔層的順序或阻隔層/銅箔/脫模層的順序積層附脫模層的銅箔的構成;或依序積層「脫模層/銅箔/阻隔層/樹脂基板或樹脂或預浸體/脫模層/銅箔/阻隔層」的構成;或依序積層「脫模層/銅箔/阻隔層/樹脂基板或樹脂或預浸體/阻隔層/銅箔/脫模層」的構成;或依序積層「阻隔層/銅箔/脫模層/樹脂基板或樹脂或預浸體/脫模層/銅箔/阻隔層」的構成。而且,也可在所述積層體兩端的阻隔層或脫模層所露出的表面,設置另一樹脂層,進而在設置銅層或金屬層後,對所述銅層或金屬層進行加工,藉此形成電路或配線。進而,也可以將所述電路或配線埋入的方式(將所述電路或配線掩埋的方式),將另一樹脂層設置於所述電路或配線上。另外,也可在所述積層體兩端的阻隔層或脫模層所露出的表面,設置銅或金屬的配線或電路,在所述配線或電路上設置另一樹脂層,利用所述另一樹脂將所述配線或電路埋入(將所述配線或電路掩埋)。之後,也可在另一樹脂層上進行電路或配線和樹脂層的形成。另外,這種電路或配線及樹脂層的形成也可進行1次以上(增層法)。而且,關於以所述方式形成的積層體(以下,也稱為積層體B),可將各個附脫模層的銅箔自所述積層體剝離而製作無芯基板。此外,所述無芯基板的製作也可使用兩個附脫模層的銅箔,製作後述的具有阻隔層/銅箔/脫模層/脫模層/銅箔/阻隔層的構成的積層體或具有脫模層/銅箔/阻隔層/阻隔層/銅箔/脫模層的構成的積層體或具有脫模層/銅箔/阻隔層/脫模層/銅箔/阻隔層的構成的積層 體,將所述積層體用於中心。可在這些積層體(以下,也稱為積層體A)兩側的阻隔層或脫模層的表面,將樹脂層及電路這兩層設置1次以上,在將樹脂層及電路這兩層設置1次以上後,自各個附脫模層的銅箔將設置了一次以上的所述樹脂層及電路這兩層的層剝離,而製作無芯基板。此外,樹脂層及電路這兩層可依序設置樹脂層、電路,也可依序設置電路、樹脂層。所述積層體也可在阻隔層的表面、脫模層的表面、脫模層與脫模層之間、阻隔層與阻隔層之間、阻隔層與脫模層之間具有其他層。其他層也可為樹脂基板或樹脂層。此外,在本說明書中,「銅箔的表面」、「銅箔側表面」、「銅箔表面」、「脫模層的表面」、「脫模層側表面」、「脫模層表面」、「積層體的表面」、「積層體表面」、「阻隔層的表面」、「阻隔層側表面」、「阻隔層表面」的概念,在銅箔、脫模層、積層體、阻隔層在銅箔表面、脫模層表面、積層體表面、阻隔層表面具有其他層的情況下,包含所述其他層的表面(最表面)。另外,積層體較佳為具有阻隔層/銅箔/脫模層/一個或多個支持體/脫模層/銅箔/阻隔層的構成。原因在於,使用所述積層體製作無芯基板時,因為在無芯基板側配置阻隔層,所以在阻隔層上形成電路並將所述電路埋入的情況下,在去除阻隔層時可減少電路的侵蝕。 The method of manufacturing a printed wiring board of the present invention may be a method of manufacturing a printed wiring board (coreless method) including the step of: applying the release layer-side copper foil of the present invention to the barrier layer side surface Or the step of laminating the release layer side surface with the resin substrate; the surface of the copper foil with the release layer on the opposite side of the barrier layer side surface or the release layer side surface laminated with the resin substrate , At least one step of providing two layers of the resin layer and the circuit; and after forming the two layers of the resin layer and the circuit, peeling the two layers of the resin layer and the circuit from the copper foil with the release layer step. In addition, the resin layer and the circuit may be provided with a resin layer and a circuit in sequence, or may be provided with a circuit and a resin layer in sequence. Regarding the coreless method, as a specific example, first, the barrier layer side surface or the release layer side surface of the copper foil with a mold release layer of the present invention is laminated with a resin substrate to produce a laminate (also referred to as copper clad) Laminates, copper clad laminates). After that, a resin layer is formed on the surface of the copper foil with a release layer on the side opposite to the side surface of the barrier layer laminated with the resin substrate or the side surface of the release layer. It is also possible to deposit another copper foil with a release layer on the resin layer formed on the surface of the release layer side or the copper foil side, and from the release layer side or the barrier layer side. Alternatively, a laminate having the following structure may be used in the method of manufacturing the printed wiring board (coreless method): a resin substrate or a resin or prepreg as the center, and a resin substrate or a resin or prepreg as the center The two surface sides of the two layers are formed by stacking copper foil with a release layer in the order of release layer/copper foil/barrier layer or in the order of barrier layer/copper foil/release layer; or layering “release layer/ Composition of copper foil/barrier layer/resin substrate or resin or prepreg/release layer/copper foil/barrier layer; or sequentially laminating "release layer/copper foil/barrier layer/resin substrate or resin or prepreg" "Block/Barrier layer/Copper foil/Release layer"; or "Layer barrier/Copper foil/Release layer/Resin substrate or resin or prepreg/Release layer/Copper foil/Barrier layer" in order constitute. Moreover, another resin layer may be provided on the exposed surface of the barrier layer or the release layer at both ends of the laminate, and then after the copper layer or metal layer is provided, the copper layer or metal layer may be processed to borrow This forms a circuit or wiring. Furthermore, a method of embedding the circuit or wiring (a method of embedding the circuit or wiring) may be provided with another resin layer on the circuit or wiring. In addition, a copper or metal wiring or circuit may be provided on the exposed surface of the barrier layer or the release layer at both ends of the laminate, and another resin layer may be provided on the wiring or circuit to utilize the other resin Embed the wiring or circuit (bury the wiring or circuit). After that, a circuit or a wiring and a resin layer may be formed on another resin layer. In addition, the formation of such a circuit or wiring and a resin layer may be performed once or more (layer build-up method). Furthermore, regarding the laminate formed in the above manner (hereinafter, also referred to as laminate B), the copper foil with each release layer attached can be peeled from the laminate to produce a coreless substrate. In addition, in the production of the coreless substrate, two copper foils with a release layer may be used to produce a laminate having a configuration of a barrier layer/copper foil/release layer/release layer/copper foil/barrier layer described later. Or a laminate with a release layer/copper foil/barrier layer/barrier layer/copper foil/release layer or a laminate with a release layer/copper foil/barrier layer/release layer/copper foil/barrier layer The laminated body uses the laminated body as the center. The two layers of the resin layer and the circuit can be provided more than once on the surface of the barrier layer or the release layer on both sides of these laminates (hereinafter also referred to as laminate A), and the two layers of the resin layer and the circuit can be provided After one or more times, the two layers of the resin layer and the circuit provided at least once are peeled from the copper foil with each release layer to produce a coreless substrate. In addition, the resin layer and the circuit may be provided with a resin layer and a circuit in sequence, or may be provided with a circuit and a resin layer in sequence. The laminate may have other layers on the surface of the barrier layer, the surface of the release layer, between the release layer and the release layer, between the barrier layer and the barrier layer, and between the barrier layer and the release layer. The other layer may be a resin substrate or a resin layer. In addition, in this specification, "surface of copper foil", "surface of copper foil side", "surface of copper foil", "surface of release layer", "surface of release layer side", "surface of release layer", The concepts of "surface of laminate", "surface of laminate", "surface of barrier layer", "side surface of barrier layer", and "surface of barrier layer" include copper foil, release layer, laminate, and barrier layer in copper. When the foil surface, the release layer surface, the laminate surface, and the barrier layer surface have other layers, the surface (the outermost surface) of the other layer is included. In addition, the laminate preferably has a structure of barrier layer/copper foil/release layer/one or more supports/release layer/copper foil/barrier layer. The reason is that when the coreless substrate is manufactured using the laminate, because the barrier layer is disposed on the coreless substrate side, when a circuit is formed on the barrier layer and the circuit is buried, the circuit can be reduced when the barrier layer is removed Erosion.
此外,在本說明書中,未特別記作「積層體A」或「積層體B」的「積層體」表示至少包含積層體A及積層體B的積層體。 In addition, in this specification, a "laminated body" not specifically described as "laminated body A" or "laminated body B" means a laminated body including at least the laminated body A and the laminated body B.
此外,在所述無芯基板的製造方法中,藉由利用樹脂將附脫模層的銅箔或所述積層體(包含積層體A)的端面的一部分或全部覆蓋,在利用增層法製造印刷配線板時,可防止藥液滲入剝離層或構成積層體的一個附脫模層的銅箔與另一個附脫模層的銅箔之間,可防止因藥液滲入引起的附脫模層的銅箔的腐蝕,從而可使良率提升。作為此處所使用的「將附脫模層的銅箔的端面的一部分或全部覆蓋的樹脂」或「將積層體的端面的一部分或全部覆蓋的樹 脂」,可使用可用於樹脂層的樹脂或公知的樹脂。另外,在所述無芯基板的製造方法中,附脫模層的銅箔或積層體中俯視時附脫模層的銅箔或積層體的積層部分(脫模層與銅箔的積層部分或阻隔層與銅箔的積層部分或一個附脫模層的銅箔與另一個附脫模層的銅箔的積層部分)的外周的至少一部分也可由樹脂或預浸體覆蓋。另外,利用所述無芯基板的製造方法形成的積層體(積層體A)也可使一對附脫模層的銅箔可相互分離地接觸而構成。另外,也可遍及所述附脫模層的銅箔中俯視時附脫模層的銅箔或積層體的積層部分(脫模層與銅箔的積層部分或阻隔層與銅箔的積層部分或一個附脫模層的銅箔與另一個附脫模層的銅箔的積層部分)的外周的整體或積層部分的整個面由樹脂或預浸體覆蓋。另外,較佳為俯視時樹脂或預浸體大於附脫模層的銅箔或積層體或積層體的積層部分,較佳為製成具有如下構成的積層體:將所述樹脂或預浸體積層於附脫模層的銅箔或積層體的兩面,利用樹脂或預浸體將附脫模層的銅箔或積層體包裝(包裹)。藉由製成這種構成,在俯視附脫模層的銅箔或積層體時附脫模層的銅箔或積層體的積層部分由樹脂或預浸體覆蓋,可防止其他部件從所述部分的側方向、即相對於積層方向從橫側的方向碰撞,結果可減少操作中的脫模層與銅箔或附脫模層的銅箔彼此的剝落。另外,藉由以不使附脫模層的銅箔或積層體的積層部分的外周露出的方式由樹脂或預浸體覆蓋,可防止如上所述的藥液處理步驟中的藥液向所述積層部分的介面的滲入,從而可防止附脫模層的銅箔的腐蝕或侵蝕。此外,在自積層體的一對附脫模層的銅箔將一個附脫模層的銅箔分離時,在由樹脂或預浸體覆蓋的附脫模層的銅箔或積層體的積層部分(脫模層與銅箔的積層部分或阻隔層與銅箔的積層部分或一個附脫模層的銅箔與另一個附脫模層的銅箔的積層部分)藉由樹脂或預浸體等牢固地密接的情況下,有時必須將所述積層部分等藉由切斷等去除。 In addition, in the method of manufacturing the coreless substrate, a part or all of the end surface of the copper foil with a mold release layer or the laminate (including the laminate A) is covered with a resin, which is manufactured by a build-up method When printing a wiring board, it can prevent the chemical solution from penetrating into the peeling layer or one of the copper foils attached to the release layer and the other copper foil attached to the release layer, which can prevent the adhesion of the release layer caused by the penetration of the chemical solution The corrosion of the copper foil can improve the yield. As "resin that covers part or all of the end surface of the copper foil with a release layer" or "resin that covers part or all of the end surface of the laminate" used herein, resins that can be used for the resin layer or known ones can be used Of resin. In addition, in the method of manufacturing the coreless substrate, in the copper foil with the release layer or the laminate, the stacked portion of the copper foil with the release layer or the laminate as viewed from above (the stacked portion of the release layer and the copper foil or At least a part of the outer periphery of the laminated portion of the barrier layer and the copper foil or the laminated portion of the copper foil with a release layer and the other copper foil with a release layer may also be covered with resin or a prepreg. In addition, the layered product (layered product A) formed by the method for manufacturing the coreless substrate may be configured such that a pair of copper foils with a release layer can be separated from each other and contacted. In addition, the copper foil with a mold release layer or the laminate portion of the laminate with the mold release layer (the laminate portion of the release layer and the copper foil or the laminate portion of the barrier layer and the copper foil or The entire outer periphery of the laminated portion of one copper foil with a release layer and the other copper foil with a release layer) or the entire surface of the laminated portion is covered with resin or a prepreg. In addition, it is preferable that the resin or prepreg is larger than the laminated portion of the copper foil or the laminate or the laminate with the release layer in a plan view, and it is preferable to make a laminate having the following structure: the resin or the prepreg It is laminated on both sides of the copper foil or the laminate with the release layer, and the copper foil or the laminate with the release layer is wrapped (wrapped) with resin or a prepreg. By making such a configuration, when the copper foil with a release layer or a laminate is viewed from above, the laminated part of the copper foil with a release layer or a laminate is covered with a resin or a prepreg to prevent other parts from the part The side direction, that is, the direction from the lateral side with respect to the stacking direction, as a result, the peeling of the release layer and the copper foil or the copper foil with the release layer in operation can be reduced. In addition, by covering with a resin or a prepreg so as not to expose the outer periphery of the laminated portion of the copper foil with the release layer or the laminate, the chemical solution in the chemical solution treatment step as described above can be prevented The penetration of the interface of the build-up part can prevent the corrosion or erosion of the copper foil attached with the release layer. In addition, when a pair of copper foils with a release layer are separated from a pair of copper foils with a release layer from the laminate, in the laminated portion of the copper foils with a release layer or a laminate covered with resin or prepreg (Laminated part of release layer and copper foil or laminated part of barrier layer and copper foil or laminated part of one copper foil with release layer and another copper foil with release layer) By resin or prepreg, etc. In the case of firmly adhering, it may be necessary to remove the layered portion and the like by cutting or the like.
也可將本發明的附脫模層的銅箔自脫模層側或阻隔層側積層於 另一個本發明的附脫模層的銅箔的脫模層側或阻隔層側而構成積層體。另外,也可為將所述一個附脫模層的銅箔的所述脫模層側表面或所述銅箔側表面與所述另一個附脫模層的銅箔的所述脫模層側表面或所述阻隔層側表面,視需要經由接著劑直接積層而獲得的積層體。另外,也可將所述一個附脫模層的銅箔的脫模層或阻隔層與所述另一個附脫模層的銅箔的脫模層或阻隔層相接合。在此,所述「接合」在脫模層或阻隔層具有表面處理層的情況下,也包含介隔所述表面處理層相互接合的態樣。另外,也可所述積層體的端面的一部分或全部由樹脂覆蓋。 The copper foil with a release layer of the present invention may be laminated from the release layer side or the barrier layer side to the release layer side or the barrier layer side of another copper foil with a release layer of the present invention to form a laminate. In addition, the release layer side surface or the copper foil side surface of the one copper foil with a release layer may be the release layer side of the other copper foil with a release layer The surface or the side surface of the barrier layer may be a laminate obtained by directly laminating via an adhesive if necessary. In addition, the release layer or barrier layer of the one copper foil with a release layer may be joined to the release layer or barrier layer of the other copper foil with a release layer. Here, the “bonding” also includes a state where the surface treatment layer is bonded to each other when the release layer or the barrier layer has a surface treatment layer. In addition, a part or all of the end surface of the laminate may be covered with resin.
脫模層彼此、阻隔層彼此、脫模層和阻隔層、附脫模層的銅箔彼此的積層除簡單地重疊以外,還可利用例如以下的方法進行。 The lamination of the release layers, the barrier layers, the release layer and the barrier layer, and the copper foil with the release layer can be laminated by simply overlapping, for example, by the following method.
(a)冶金接合方法:熔接(弧焊、TIG(鎢極惰性氣體)焊接、MIG(熔化極惰性氣體)焊接、電阻焊接、縫焊、點焊)、壓接(超音波焊接、摩擦攪拌焊接)、釺焊;(b)機械接合方法:鉚接、利用鉚釘的接合(利用自沖鉚接的接合、利用鉚釘的接合)、縫合器;(c)物理接合方法:接著劑、(兩面)膠帶 (a) Metallurgical joining methods: welding (arc welding, TIG (tungsten inert gas) welding, MIG (melting inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, friction stir welding ), brazing; (b) mechanical joining methods: riveting, joining using rivets (joining using self-piercing riveting, joining using rivets), stitchers; (c) physical joining methods: adhesives, (both sides) tape
藉由使用所述接合方法將一附脫模層的銅箔的一部分或全部與另一附脫模層的銅箔的一部分或全部接合,可製造以下的積層體,所述積層體是將一附脫模層的銅箔與另一附脫模層的銅箔積層,使附脫模層的銅箔彼此可分離地接觸而構成。在一附脫模層的銅箔與另一附脫模層的銅箔弱接合,而將一附脫模層的銅箔與另一附脫模層的銅箔積層的情況下,即使不將一附脫模層的銅箔與另一附脫模層的銅箔的接合部去除,一附脫模層的銅箔與另一附脫模層的銅箔也可分離。另外,在一附脫模層的銅箔與另一附脫模層的銅箔強接合的情況下,可藉由利用切斷或化學研磨(蝕刻等)、機械研磨等將一附脫模層 的銅箔與另一附脫模層的銅箔相接合的部位去除,將一附脫模層的銅箔與另一附脫模層的銅箔分離。 By joining a part or all of the copper foil with a release layer to a part or all of the copper foil with a release layer using the bonding method, the following laminate can be manufactured, which is a The copper foil with a mold release layer and the copper foil with another mold release layer are laminated so that the copper foil with a mold release layer may be separably contacted with each other. In the case where the copper foil of one release layer and the copper foil of another release layer are weakly joined, and the copper foil of one release layer and the copper foil of another release layer are laminated, even if the The joint of the copper foil with one release layer and the copper foil with another release layer is removed, and the copper foil with one release layer and the copper foil with another release layer can also be separated. In addition, in the case where the copper foil of one release layer is strongly joined to the copper foil of another release layer, a release layer can be attached by cutting, chemical polishing (etching, etc.), mechanical polishing, etc. The part where the copper foil and the copper foil with another release layer are joined is removed, and the copper foil with one release layer is separated from the copper foil with another release layer.
另外,在像「阻隔層/銅箔/脫模層/樹脂基板或樹脂或預浸體/脫模層/銅箔/阻隔層」這樣構成的積層體,至少設置1次樹脂層和電路這兩層的步驟,及在使所述樹脂層及電路這兩層至少形成1次後,自所述積層體的附脫模層的銅箔剝離所述樹脂基板或樹脂或預浸體的步驟之後,藉由蝕刻將脫模層及銅箔去除。之後,使用可將阻隔層藉由蝕刻去除的蝕刻液將阻隔層去除,藉此可製作具有至少形成了1次所述樹脂層及電路這兩層的層且不具有芯的印刷配線板。此外,在所述積層體的一個或兩個表面,也可設置樹脂層和電路這兩層。此外,樹脂層及電路這兩層可依序設置樹脂層、電路,也可依序設置電路、樹脂層。 In addition, at least one primary resin layer and two circuits should be provided in a layered structure such as "barrier layer/copper foil/release layer/resin substrate or resin or prepreg/release layer/copper foil/barrier layer" After the step of forming a layer and forming the two layers of the resin layer and the circuit at least once, the step of peeling off the resin substrate or the resin or the prepreg from the copper foil with a release layer of the laminate, The release layer and copper foil are removed by etching. After that, the barrier layer is removed using an etching solution that can remove the barrier layer by etching, whereby a printed wiring board having two layers of the resin layer and the circuit formed at least once and having no core can be produced. In addition, two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate. In addition, the resin layer and the circuit may be provided with a resin layer and a circuit in sequence, or may be provided with a circuit and a resin layer in sequence.
所述積層體所使用的樹脂基板、樹脂層、樹脂、預浸體可為本說明書中記載的樹脂層,也可包含本說明書中記載的樹脂層所使用的樹脂、樹脂硬化劑、化合物、硬化促進劑、介電體、反應催化劑、交聯劑、聚合物、預浸體、骨架材料等。 The resin substrate, resin layer, resin, and prepreg used in the laminate may be the resin layer described in this specification, or may include the resin, resin curing agent, compound, and curing used in the resin layer described in this specification. Promoters, dielectrics, reaction catalysts, cross-linking agents, polymers, prepregs, framework materials, etc.
此外,所述附脫模層的銅箔或積層體也可在俯視時小於樹脂或預浸體或樹脂基板或樹脂層。 In addition, the copper foil or laminate with the release layer may be smaller than the resin or prepreg, resin substrate, or resin layer in a plan view.
[實施例] [Example]
以下,藉由本發明的實施例更詳細地說明本發明,但本發明並不受這些實施例的任何限定。 Hereinafter, the present invention will be described in more detail with examples of the present invention, but the present invention is not limited by these examples.
(實施例1:附脫模層的銅箔) (Example 1: Copper foil with release layer)
銅箔使用JX金屬股份有限公司製造的電解銅箔JTC箔(厚度35μm),在所述電解銅箔的S面(光澤面)側,在以下的條件下,藉由電鍍形成厚度1μm的Ni層,作為阻隔層。 As the copper foil, electrolytic copper foil JTC foil (thickness 35 μm ) manufactured by JX Metal Co., Ltd. was used. On the S surface (glossy surface) side of the electrolytic copper foil, a thickness of 1 μ was formed by electroplating under the following conditions The Ni layer of m serves as a barrier layer.
[鎳(Ni)鍍覆] [Nickel (Ni) plating]
‧鍍覆液 ‧Plating solution
鎳:20~200g/L Nickel: 20~200g/L
硼酸:5~60g/L Boric acid: 5~60g/L
液溫:40~65℃ Liquid temperature: 40~65℃
pH值:1.5~5.0 pH value: 1.5~5.0
‧電流密度:0.5~20A/dm2 ‧Current density: 0.5~20A/dm 2
‧通電時間:1~20秒 ‧Power-on time: 1~20 seconds
‧攪拌(液體循環量):100~1000L/分鐘 ‧Stirring (liquid circulation volume): 100~1000L/min
‧搬送速度:2~30m/分鐘 ‧Transport speed: 2~30m/min
‧添加劑:一次光澤劑(糖精鈉:0.5~5g/L)、二次光澤劑(硫脲:0.05~1g/L) ‧Additives: primary gloss agent (saccharin sodium: 0.5~5g/L), secondary gloss agent (thiourea: 0.05~1g/L)
之後,在以下的條件下,在電解銅箔的與阻隔層為相反側的表面形成脫模層。 Thereafter, a release layer was formed on the surface of the electrolytic copper foil opposite to the barrier layer under the following conditions.
‧矽烷偶合處理 ‧Silane coupling treatment
處理液: 矽烷化合物:正丙基三甲氧基矽烷 Treatment liquid: Silane compound: n-propyltrimethoxysilane
矽烷濃度:0.4vol% Silane concentration: 0.4vol%
使用前的處理液攪拌時間:12小時 Stirring time of the treatment solution before use: 12 hours
醇濃度:0vol% Alcohol concentration: 0vol%
pH值:4~7 pH value: 4~7
處理時間:30秒(利用噴霧嘴的塗布) Processing time: 30 seconds (application by spray nozzle)
(試驗結果) (test results)
使用實施例1的附脫模層的銅箔,使用預浸體FR-4作為積層於銅箔的脫模層側表面的樹脂(絕緣基板1),使用環氧樹脂作為埋入樹脂(絕緣基板2),如圖1~圖4所示,可製成埋入電路基板(印刷配線版)。 The copper foil with a mold release layer of Example 1 was used, prepreg FR-4 was used as the resin (insulating substrate 1) laminated on the surface of the copper foil on the mold release layer side, and epoxy resin was used as the embedded resin (insulating substrate 2) As shown in Figures 1 to 4, it can be made into a buried circuit board (printed wiring board).
1‧‧‧絕緣基板 1‧‧‧Insulated substrate
10‧‧‧阻隔層 10‧‧‧ barrier layer
20‧‧‧銅箔 20‧‧‧Copper foil
30‧‧‧脫模層 30‧‧‧Release layer
40‧‧‧抗鍍覆層 40‧‧‧Anti-plating layer
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TW200843578A (en) * | 2007-04-30 | 2008-11-01 | Samsung Electro Mech | Carrier member for transmitting circuits, coreless printed circuit board using the carrier member, and method of manufacturing the same |
TW201422424A (en) * | 2012-10-04 | 2014-06-16 | Jx Nippon Mining & Metals Corp | Carrier-attached metal foil |
TW201431678A (en) * | 2012-10-26 | 2014-08-16 | Jx Nippon Mining & Metals Corp | carrier-attached copper foil, cooper-clad laminate, printed wiring board, printed circuit board using the same, and manufacturing method of printed wiring board |
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JP6393619B2 (en) * | 2012-10-04 | 2018-09-19 | Jx金属株式会社 | Multilayer printed wiring board manufacturing method and base substrate |
JP5830635B1 (en) * | 2014-02-14 | 2015-12-09 | 古河電気工業株式会社 | Ultra-thin copper foil with carrier, and copper-clad laminate, printed wiring board and coreless board manufactured using the same |
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TW200843578A (en) * | 2007-04-30 | 2008-11-01 | Samsung Electro Mech | Carrier member for transmitting circuits, coreless printed circuit board using the carrier member, and method of manufacturing the same |
TW201422424A (en) * | 2012-10-04 | 2014-06-16 | Jx Nippon Mining & Metals Corp | Carrier-attached metal foil |
TW201431678A (en) * | 2012-10-26 | 2014-08-16 | Jx Nippon Mining & Metals Corp | carrier-attached copper foil, cooper-clad laminate, printed wiring board, printed circuit board using the same, and manufacturing method of printed wiring board |
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