TW201622995A - A metal foil with a carrier - Google Patents

A metal foil with a carrier Download PDF

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Publication number
TW201622995A
TW201622995A TW105100773A TW105100773A TW201622995A TW 201622995 A TW201622995 A TW 201622995A TW 105100773 A TW105100773 A TW 105100773A TW 105100773 A TW105100773 A TW 105100773A TW 201622995 A TW201622995 A TW 201622995A
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Taiwan
Prior art keywords
metal foil
resin
group
sub
plate
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TW105100773A
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Chinese (zh)
Inventor
Terumasa Moriyama
Michiya Kohiki
Masafumi Ishii
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Jx Nippon Mining & Metals Corp
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Publication of TW201622995A publication Critical patent/TW201622995A/en

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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
    • 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
    • B32B15/08—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 of synthetic resin
    • 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
    • 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
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H05K3/4655—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern by using a laminate characterized by the insulating layer
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/09—Shape and layout
    • H05K2201/09145—Edge details
    • H05K2201/09154—Bevelled, chamferred or tapered edge

Landscapes

  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Laminated Bodies (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)

Abstract

The purpose of the invention is to provide a plate-like carrier made of resin and a metal foil attached with carrier, wherein the peeling strength of the metal foil is pre-adjusted. The metal foil attached with carrier comprises a plate-like carrier made of resin, and a metal foil formed to be capable of being peeled off and tightly adhered to at least one side of the carrier. The plate-like carrier and the metal foil are formed by laminating one of the following materials: aluminate compound, titanate compound or zirconate compound, hydrolysis product thereof, and condensate of the hydrolysis product having a predetermined structure, or their combination. Furthermore, the present invention also provides a plate-like carrier made of resin, and a corresponding metal foil attached with carrier, wherein the metal foil has a peeling strength that is subjected to adjustment, and the carrier and metal foil can be prevented from peeling off during transportation or processing. Specifically, the present invention provides a metal foil attached with carrier, and a metal foil formed to be capable of being peeled off and tightly adhered to at least one surface of a plate-like carrier made of resin. When the metal foil attached with carrier is observed in a plane view, the area of the metal foil is smaller than that of the plate-like carrier.

Description

附載子金屬箔 Attached metal foil

本發明係有關一種附載子金屬箔。更詳細的說明係有關於一種在印刷配線板上使用之單層或兩層以上的多層層合板、或極薄的無芯基板之製造上使用之附載子金屬箔。 The present invention relates to an attached sub-metal foil. A more detailed description relates to a carrier metal foil for use in the manufacture of a single layer or a multilayered laminate of two or more layers or an extremely thin coreless substrate used on a printed wiring board.

一般而言，印刷線路板係於合成樹脂板、玻璃板、玻璃不織布、紙等基材，使合成樹脂經過浸漬處理後所得到之稱為「預浸漬片」(prepreg)的介電材作為基本材料所構成。而在預浸漬膠片的相對側，接合了具有電流傳導性的銅或銅合金箔等片狀物。如此組合而成之層和物，一般稱之為CCL(Copper Clad Laminate)材。通常為了增強接合強度，會將與預浸漬片黏合的銅箔面，做為墊面。做為銅或銅合金箔的代替品，有時也會使用鋁箔、鎳箔或鋅箔等。這些金屬箔的厚度多為5~200μm左右。此種一般使用之CCL(Copper Clad Laminate)材，如圖1所示。 In general, a printed wiring board is a base material such as a synthetic resin sheet, a glass plate, a glass non-woven fabric, or a paper, and a dielectric material called a "prepreg" obtained by immersing a synthetic resin is used as a basic material. Made up of materials. On the opposite side of the prepreg film, a sheet such as a copper or copper alloy foil having current conductivity is bonded. The layers and materials thus combined are generally referred to as CCL (Copper Clad Laminate) materials. Usually, in order to enhance the joint strength, the copper foil surface bonded to the prepreg is used as a mat surface. As a substitute for copper or copper alloy foil, aluminum foil, nickel foil or zinc foil may be used. The thickness of these metal foils is usually about 5 to 200 μm. Such a commonly used CCL (Copper Clad Laminate) material is shown in FIG.

專利文獻1中，提供了一種附載子金屬箔，其特徵為其係由合成樹脂製之板狀載子，與該載子的至少一面上，可以機械方式剝離並密著的金屬箔所成之附載子金屬箔，此附載子金屬箔為可供印刷配線板之組合為其主旨。該專利並揭示，板狀載子與金屬箔的剝離強度為1gf/cm~1kgf/cm為較理想。利用該附載子金屬箔，其以合成樹脂全面橫過銅箔加以支撐，可防止積層中的銅箔皺褶的發生。且此種附載子金屬箔，金屬箔與合成樹脂毫無縫隙的密著，因此在金屬箔表面進行鍍金或加以蝕刻時，可將此投入鍍金或蝕刻用藥液中。再者，合成樹脂的線膨脹係數，與基板之構成材料的銅箔以及重合後的預浸漬片為同等的等級，因此不會導致線路的位置偏移，使不良品的發生降低，具有能夠使產率上升之優異的效果。 Patent Document 1 provides an attached sub-metal foil characterized in that it is a plate-shaped carrier made of synthetic resin, and is formed of a metal foil which can be mechanically peeled off and adhered to at least one surface of the carrier. The sub-metal foil is attached, and the attached sub-metal foil is a combination of printed wiring boards. This patent also discloses that the peel strength of the plate-shaped carrier and the metal foil is preferably from 1 gf/cm to 1 kgf/cm. By using the attached sub-metal foil, the synthetic resin is supported entirely across the copper foil, and the occurrence of wrinkles of the copper foil in the laminate can be prevented. Further, such a sub-metal foil, the metal foil and the synthetic resin are not closely adhered to each other. Therefore, when gold plating or etching is performed on the surface of the metal foil, this may be put into a gold plating or etching liquid. Further, since the coefficient of linear expansion of the synthetic resin is equivalent to the copper foil of the constituent material of the substrate and the prepreg after the superposition of the substrate, the positional deviation of the line is not caused, and the occurrence of defective products is lowered, and the occurrence of defective products can be made. Excellent effect of increasing yield.

【專利文獻】[Patent Literature]

【專利文獻1】日本專利特開2009-272589號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-272589

【專利文獻2】日本專利特開2000-196207號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-196207

於專利文獻1所記載的附載子金屬箔，係為使印刷線路板的製造工程簡化，以及因產率上升而得到的成本削減之重大貢獻的劃時代的發明，但關於板狀載子與金屬箔的剝離強度的最佳化以及其手段，至今仍留有檢討的空間。特別在，對本發明者而言顯著的問題，係如板狀載子與金屬箔的剝離強度會隨著板狀載子的材質而過度提升之問題，較理想的係能提供可以簡便調整該剝離強度的手段。又如，傳統之附載子金屬箔於處理過程中，角落的部分與其他部材碰撞時，所受之外力會使載子與金屬箔兩者剝離，而產生不良品之問題，較理想的係能在這方面得到改善。因此在本發明中，其課題即為提供一種樹脂製之板狀載子與金屬箔剝離強度係經調節的附載子金屬箔；並且，亦提供一種樹脂製之板狀載子，以及，金屬箔之剝離強度經過調節，且在運輸或加工時(處理過程中)載體與金屬箔之剝離防止上，可對應之附載子金屬箔。 The attached sub-metal foil described in Patent Document 1 is an epoch-making invention that simplifies the manufacturing process of a printed wiring board and contributes to cost reduction due to an increase in yield, but relates to a plate-shaped carrier and a metal foil. The optimization of the peel strength and its means still leave room for review. In particular, a problem that is significant to the inventors is that the peel strength of the plate-shaped carrier and the metal foil is excessively increased with the material of the plate-shaped carrier, and an ideal system can provide an easy adjustment of the peeling. The means of strength. For example, in the conventional process of supporting the metal foil, when the corner portion collides with other parts, the external force will cause the carrier and the metal foil to be peeled off, and the problem of defective products is generated. Improved in this regard. Therefore, in the present invention, the object of the present invention is to provide a carrier-made metal foil having a peeling strength of a resin-made plate-shaped carrier and a metal foil; and a resin-made plate-shaped carrier and a metal foil The peel strength is adjusted, and when the carrier and the metal foil are prevented from peeling off during transportation or processing (during treatment), the sub-metal foil may be attached.

本發明者群，針對調節樹脂板與金屬箔之間的剝離強度專心研究的結果，發現了於樹脂板與金屬箔貼合之前，在至少一方的表面上，以具有特定構造的鋁酸鹽化合物、鈦酸鹽化合物或鉻酸鹽化合物進行包覆處理，能夠實現因應所需用途的剝離強度；此外，又關於載子與金屬箔重疊型態，深入研究的結果，發現了載子與具有較載子所占面積為小之金屬箔重疊後，若僅係由與其他部材碰撞所產生的外力，載子與金屬箔將較為不易剝離，因此完成了本發明。 As a result of intensive studies on adjusting the peeling strength between the resin sheet and the metal foil, the inventors of the present invention found that an aluminate compound having a specific structure is formed on at least one surface of the resin sheet before bonding with the metal foil. The titanate compound or the chromate compound is coated to achieve the peel strength in response to the desired use; in addition, as for the overlap between the carrier and the metal foil, the results of in-depth studies have found that the carrier has After the metal foils having a small area occupied by the carriers are overlapped, the carrier and the metal foil are less likely to be peeled off only by the external force generated by collision with other members, and thus the present invention has been completed.

即本發明係如以下所述。 That is, the present invention is as follows.

(1)一種附載子金屬箔，其特徵為其係由樹脂製之板狀載子，與在該載子之至少一面上使成可剝離並密著的金屬箔所構成之附載子金屬箔；且板 狀載子與金屬箔，係將下式：【化1】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物、其等之加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合使用加以貼合而成者。 (1) An attached sub-metal foil characterized by a plate-shaped carrier made of a resin and an attached sub-metal foil formed of a metal foil which is peelable and adhered to at least one surface of the carrier; And the plate-shaped carrier and the metal foil are of the following formula: [Chemical Formula 1] (R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkoxy group or a halogen atom; R 2 is selected a hydrocarbon group grouped from an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; any one of M systems of Al, Ti or Zr; 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m + n is a valence of M, that is, 3 in the case of Al, Ti, Zr The aluminate compound, the titanate compound or the zirconate compound shown in 4), the hydrolyzed product thereof, and the condensate of the hydrolyzed product are used alone or in combination. By.

(2)如(1)之附載子金屬箔，其中，板狀載子與金屬箔之剝離強度在10gf/cm以上200gf/cm以下。 (2) The sub-metal foil according to (1), wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less.

(3)如(1)或(2)之附載子金屬箔，其中樹脂製之板狀載子係包含熱硬化性樹脂。 (3) The sub-metal foil according to (1) or (2), wherein the resin-made plate-shaped carrier comprises a thermosetting resin.

(4)如(1)~(3)中任一之附載子金屬箔，其中樹脂製之板狀載子係預浸漬片。 (4) The attached sub-metal foil according to any one of (1) to (3), wherein the resin-made plate-shaped carrier is a prepreg.

(5)如(3)之附載子金屬箔，其中樹脂製之板狀載子係具有120~320℃的玻璃化溫度Tg。 (5) The sub-metal foil according to (3), wherein the resin-made plate-shaped carrier has a glass transition temperature Tg of 120 to 320 °C.

(6)如(1)~(5)中任一之附載子金屬箔，其中與金屬箔之載子相接合側的表面，其十點平均粗糙度(Rz jis)係3.5μm以下。 (6) The attached sub-metal foil according to any one of (1) to (5), wherein a surface having a side joined to a carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(7)如(1)~(6)中任一之附載子金屬箔，其中與金屬箔之載子不相接合側的表面，其十點平均粗糙度(Rz jis)係0.4μm以上10.0μm以下。 (7) The attached sub-metal foil according to any one of (1) to (6), wherein a surface having a side on which the carrier of the metal foil is not bonded has a ten-point average roughness (Rz jis) of 0.4 μm or more and 10.0 μm. the following.

(8)如(1)~(7)中任一之附載子金屬箔，其中金屬箔之厚度係1μm以上400μm以下。 (8) The attached sub-metal foil according to any one of (1) to (7), wherein the thickness of the metal foil is 1 μm or more and 400 μm or less.

(9)如(1)~(8)中任一之附載子金屬箔，其中於220℃經過3小時、6小時或9小時之中至少一個加熱程序後，金屬箔與板狀載子之剝離強度係10gf/cm以上200gf/cm以下。 (9) The attached sub-metal foil according to any one of (1) to (8), wherein the stripping of the metal foil and the plate-shaped carrier after at least one of heating processes at 220 ° C for 3 hours, 6 hours or 9 hours The strength is 10 gf/cm or more and 200 gf/cm or less.

(10)如(1)~(9)中任一之附載子金屬箔，其中金屬箔為銅箔。 (10) The attached sub-metal foil according to any one of (1) to (9), wherein the metal foil is a copper foil.

(11)一種印刷配線板用金屬箔，其特徵為於其金屬箔之表面，係具有將下式：【化2】(R1)m-M-(R2)n(式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合者。 (11) A metal foil for a printed wiring board, characterized in that the surface of the metal foil has the following formula: [Chem. 2] (R 1 ) m -M-(R 2 ) n (wherein the R1 system Alkoxy or a halogen atom; R2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M-based Al, Any of Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R1 is an alkoxy group; further, the valence of m+n is M, In other words, in the case of Al, it is 3, and in the case of Ti and Zr, it is an aluminate compound, a titanate compound or a zirconate compound represented by 4), and a hydrolyzed product such as a hydrolyzed product or a condensate of the hydrolyzed product is separately used. Or plural combinations.

(12)如(11)中之印刷配線板用金屬箔，其中係將金屬箔的鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以相對於使之單獨或複數組合而作用側之表面，在使該化合物進行作用前，經過鉻酸鹽處理者。 (12) The metal foil for a printed wiring board according to (11), wherein the hydrous product is hydrolyzed by an aluminate compound, a titanate compound or a zirconate compound of the metal foil, and the like. The condensate is subjected to a chromate treatment before the action of the compound with respect to the surface on the side on which the combination is applied singly or in combination.

(13)如(11)或(12)之印刷配線板用金屬箔，其中與金屬箔之載子相接合側之表面，其十點平均粗糙度(Rz jis)係3.5μm以下。 (13) The metal foil for a printed wiring board according to (11) or (12), wherein a surface having a side joined to a carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(14)如(11)~(13)中任一之印刷配線板用金屬箔，其中與金屬箔之載子不相接合側的表面，其十點平均粗糙度(Rz jis)係0.4μm以上10.0μm以下。 (14) The metal foil for a printed wiring board according to any one of (11) to (13), wherein a surface having a side on which the carrier of the metal foil is not bonded has a ten-point average roughness (Rz jis) of 0.4 μm or more 10.0 μm or less.

(15)如(11)~(14)中任一之印刷配線板用金屬箔，其中金屬 箔為銅箔。 (15) A metal foil for a printed wiring board according to any one of (11) to (14), wherein the metal The foil is copper foil.

(16)一種金屬箔，其特徵為其係至少在一面上，具有將下式：【化3】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合之金屬箔；且其係可用於：在該表面將樹脂製之板狀載子剝離並使之密著的用途者。 (16) A metal foil characterized by being at least one side having the following formula: [Chemical Formula 3] (R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkoxy group) Or a halogen atom; R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M system is Al, Ti or Any one of Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m + n is a valence of M, that is, In the case of Al, it is 3, and in the case of Ti and Zr, it is an aluminate compound, a titanate compound or a zirconate compound represented by 4), a hydrolyzed product thereof, and the condensate of the hydrolyzed product, either alone or A metal foil of a plurality of combinations; and it can be used for a user who peels and seals a resin-made plate-shaped carrier on the surface.

(17)如(16)之金屬箔，其中係將金屬箔的鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以相對於使之單獨或複數組合而作用側之表面，在使該化合物進行作用前，經過鉻酸鹽處理者。 (17) The metal foil according to (16), wherein the metallohydrate compound, the titanate compound or the zirconate compound of the metal foil, the hydrolyzed product thereof, and the condensate of the hydrolyzed product are The surface treated with the chromate is applied to the surface of the active side in combination with it alone or in combination.

(18)如(16)或(17)之金屬箔，其中與金屬箔之載子接合側的表面，其十點平均粗糙度(Rz jis)在3.5μm以下。 (18) The metal foil according to (16) or (17), wherein a surface having a side joined to the carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(19)一種樹脂製之板狀載子，其特徵為至少在一側的表面上，具有下式：【化4】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基； M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合者。 (19) A resin-made plate-shaped carrier characterized by having at least one surface having the following formula: [Chemical Formula 4] (R 1 ) m -M-(R 2 ) n (wherein R 1 Is an alkoxy group or a halogen atom; R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; Is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m+n is M The number of valences, that is, an aluminate compound, a titanate compound, or a zirconate compound represented by 4) in the case of Al and Ti in the case of Al, and a hydrolyzed product, etc., and condensation of the hydrolyzed product Body, in separate or plural combinations.

(20)一種板狀載子，其特徵為其係至少在一側的表面上，具有將下式：【化5】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合之樹脂製之板狀載子；且其係可用於：在該表面將金屬箔剝離並使之密著的用途者。 (20) A plate-shaped carrier characterized by being on at least one surface having a formula: [Chem. 5] (R 1 ) m -M-(R 2 ) n (wherein R 1 Is an alkoxy group or a halogen atom; R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; Is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m+n is M The number of valences, that is, an aluminate compound, a titanate compound, or a zirconate compound represented by 4) in the case of Al and Ti in the case of Al, and a hydrolyzed product, etc., and condensation of the hydrolyzed product The body is a plate-shaped carrier made of resin alone or in combination; and it can be used for a user who peels off and adheres the metal foil on the surface.

(21)一種多層金屬張積層板的製造方法，其特徵為其係包含：相對於(1)~(10)中任一之附載子金屬箔至少一面的金屬箔側，將樹脂進行層合，接著再將樹脂或金屬箔重複一次以上進行層合者。 (21) A method for producing a multilayer metal laminated laminate, characterized in that the resin is laminated on at least one side of a metal foil with respect to any one of the attached sub-metal foils (1) to (10), Then, the resin or the metal foil is repeated one or more times for lamination.

(22)一種多層金屬張積層板的製造方法，其特徵為其係包含：在(1)~(10)中任一之附載子金屬箔的金屬箔側，將樹脂進行層合，接著，再將樹脂、單面或雙面金屬張積層板、或(1)~(10)中任一之附載子金屬箔、或金屬箔重複一次以上進行層合者。 (22) A method for producing a multilayer metal laminated laminate, comprising: laminating a resin on a side of a metal foil of any one of (1) to (10); and then The resin, the single-sided or double-sided metal laminate, or the attached sub-metal foil or any of the metal foils (1) to (10) may be laminated one or more times.

(23)一種多層金屬張積層板的製造方法，其特徵為其於(21)或(22)之多層金屬張積層板的製造方法中，更包含了將附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟。 (23) A method for producing a multilayer metal laminate, characterized in that in the method for producing a multilayer metal laminate of (21) or (22), the plate-shaped carrier of the attached metal foil is further included The step of peeling and separating the metal foil.

(24)一種多層金屬張積層板的製造方法，其特徵為其於(23)之製造方法中，包含了將已經剝離並分離之金屬箔的一部或全部，以蝕刻進行除去之步驟。 (24) A method of producing a multilayered metal laminate, characterized in that the method of (23) comprises the step of removing one or all of the metal foil which has been peeled off and separated by etching.

(25)一種多層金屬張積層板，其特徵為其係以(21)~(24)中任一之製造方法所得者。 (25) A multilayer metal laminate, which is characterized by being produced by any one of (21) to (24).

(26)一種組合基板的製造方法，其特徵為其係包含：於(1)~(10)中任一之附載子金屬箔的金屬箔側，將組合配線層形成一層以上之步驟者。 (26) A method of producing a composite substrate, comprising the step of forming one or more combined wiring layers on the metal foil side of the attached sub-metal foil of any one of (1) to (10).

(27)如(26)之組合基板的製造方法，其特徵為其組合配線層係使用減成法或全加成法或半加成法的至少一種而形成者。 (27) A method of producing a composite substrate according to (26), characterized in that the combined wiring layer is formed by using at least one of a subtractive method, a full additive method, or a semi-additive method.

(28)一種組合基板的製造方法，其特徵為其係包含：於(1)~(10)中任一之附載子金屬箔至少一面的金屬箔側，將樹脂進行層合，接著，再將樹脂、單面或雙面配線基板、單面或雙面金屬張積層板、(1)~(10)中任一之附載子金屬箔或金屬箔，重複一次以上進行層合者。 (28) A method for producing a composite substrate, comprising: laminating a resin on at least one side of a metal foil of any one of (1) to (10); and then The resin, the single-sided or double-sided wiring board, the single-sided or double-sided metal laminate, and the attached sub-metal foil or metal foil of any of (1) to (10) are laminated one or more times.

(29)一種組合基板的製造方法，其特徵為其係進一步包含：於(28)之組合基板的製造方法中，在單面或雙面配線基板、單面或雙面金屬張積層板、附載子金屬箔的金屬箔、附載子金屬箔的板狀載子、金屬箔或樹脂上，鑽孔，於該孔洞的側面或底面進行傳導電鍍的步驟。 (29) A method of producing a composite substrate, characterized by further comprising: in the method of manufacturing a composite substrate according to (28), a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminated laminate, and an attached The metal foil of the sub-metal foil, the plate-shaped carrier on which the sub-metal foil is attached, the metal foil or the resin is drilled, and the step of conducting electroplating is performed on the side surface or the bottom surface of the hole.

(30)一種組合基板的製造方法，其特徵為其係進一步包含：於(28)或(29)之組合基板的製造方法中，在構成單面或雙面配線基板之金屬箔、構成單面或雙面金屬張積層板之金屬箔、構成附載子金屬箔之金屬箔、以及金屬箔之至少一者之上，進行一次以上配線形成之步驟。 (30) A method of producing a composite substrate, characterized by further comprising: in the method for producing a composite substrate of (28) or (29), forming a metal foil of a single-sided or double-sided wiring substrate, forming a single side The step of forming one or more wirings on at least one of the metal foil of the double-sided metal laminate, the metal foil constituting the attached sub-metal foil, and the metal foil.

(31)如(28)~(30)中任一之組合基板的製造方法，其中更包含：於配線所形成之表面上，使單面上密著有金屬箔之(1)~(10)中任一之附載子金屬箔的樹脂板側，與其接觸，並進行層合之步驟。 (31) The method for producing a composite substrate according to any one of (28) to (30), further comprising: (1) to (10) in which a metal foil is adhered to one surface on a surface formed by the wiring The side of the resin sheet on which the sub-metal foil is attached, in contact with it, and the step of laminating.

(32)如(28)~(30)中任一之組合基板的製造方法，其中更包含了於配線所形成之表面上，將樹脂層合，並對該樹脂在雙面上均以金屬箔密著之(1)~(10)中任一之附載子金屬箔的一方金屬箔，使其接觸，並進行層合之步驟。 (32) The method for producing a composite substrate according to any one of (28) to (30), further comprising laminating the resin on the surface formed by the wiring, and using the metal foil on both sides of the resin One of the metal foils attached to the sub-metal foil of any one of (1) to (10) is brought into contact and laminated.

(33)如(28)~(32)中任一之組合基板的製造方法，其中樹脂之至少一者為預浸漬片。 (33) A method of producing a composite substrate according to any one of (28) to (32), wherein at least one of the resins is a prepreg.

(34)一種組合配線板的製造方法，其特徵為其於(26)~(33)中任一之組合基板的製造方法中，更包含將附載子金屬箔的板狀載子與金屬箔進行剝離並分離之步驟。 (34) A method for producing a composite wiring board, characterized in that, in the method for producing a composite substrate according to any one of (26) to (33), further comprising: carrying a plate-shaped carrier carrying a sub-metal foil and a metal foil The step of stripping and separating.

(35)一種組合配線板的製造方法，其特徵係於(34)之組合配線板的製造方法中，將與板狀載子密著之金屬箔的一部或全部，以蝕刻方式加以除去之步驟。 (35) A method of manufacturing a composite wiring board, characterized in that in the method of manufacturing a composite wiring board of (34), one or all of the metal foil adhered to the plate-shaped carrier are removed by etching step.

(36)一種組合配線板，其特徵係由(34)或(35)之製造方法所得者。 (36) A composite wiring board characterized by the production method of (34) or (35).

(37)一種印刷電路板的製造方法，其特徵係包含：藉由(26)~(33)中任一項之製造方法，將組合基板加以製造之步驟。 (37) A method of producing a printed circuit board, comprising the step of manufacturing a composite substrate by the method of any one of (26) to (33).

(38)一種印刷電路板的製造方法，其特徵係包含：藉由(34)或(35)之製造方法，製造組合配線板之步驟。 (38) A method of manufacturing a printed circuit board, comprising the step of manufacturing a combined wiring board by the manufacturing method of (34) or (35).

(39)一種附載子金屬箔，其特徵為其係由樹脂製的板狀載子，與在該載子之至少一面上使成可剝離並密接的金屬箔所構成之附載子金屬箔；平面觀察時，金屬箔與板狀載子為同一形狀，且係不具有90度以下內角之角(頂點)的形狀者。 (39) A carrier-based metal foil characterized by being a plate-shaped carrier made of a resin and a metal foil which is formed by peeling and adhering a metal foil on at least one surface of the carrier; At the time of observation, the metal foil and the plate-shaped carrier have the same shape, and are not in the shape of an angle (vertex) of an internal angle of 90 degrees or less.

(40)如(39)之附載子金屬箔，其中，平面觀察時，附載子金屬箔與板狀載子為同一形狀，且係由直線及曲線所圍成之形狀者。 (40) The sub-metal foil according to (39), wherein the attached sub-metal foil and the plate-shaped carrier have the same shape and are surrounded by a straight line and a curved line when viewed in plan.

(41)如(40)之附載子金屬箔，其中，平面觀察時，附載子金屬箔與板狀載子為同一形狀，且曲線為圓弧或橢圓弧者。 (41) The sub-metal foil according to (40), wherein, when viewed in plan, the attached sub-metal foil has the same shape as the plate-shaped carrier, and the curve is an arc or an elliptical arc.

(42)如(39)之附載子金屬箔，其中，平面觀察時，附載子金屬箔與板狀載子為同一形狀，且為所有內角皆係大於90度角度之多邊形。 (42) The sub-metal foil according to (39), wherein, when viewed in plan, the attached sub-metal foil has the same shape as the plate-shaped carrier, and is a polygon having an inner angle of more than 90 degrees.

(43)如(42)之附載子金屬箔，其中，平面觀察時，附載子金屬箔與板狀載子為同一形狀，且所有內角皆係大於90度且小於180度角度之凸多角形狀。 (43) The sub-metal foil according to (42), wherein, when viewed in plan, the attached sub-metal foil has the same shape as the plate-shaped carrier, and all the inner corners are convex polygonal shapes having an angle greater than 90 degrees and less than 180 degrees. .

(44)如(39)之附載子金屬箔，其中，平面觀察時，附載子金屬箔與板狀載子為同一形狀，且係僅由曲線所圍成之形狀者。 (44) The sub-metal foil according to (39), wherein, when viewed in plan, the attached sub-metal foil has the same shape as the plate-shaped carrier, and is formed only by a curved shape.

(45)如(39)~(44)中任一者之附載子金屬箔，其中，板狀載子與金屬箔之剝離強度為10gf/cm以上200gf/cm以下。 (45) The attached sub-metal foil according to any one of (39) to (44), wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less.

(46)如(39)~(45)中任一者之附載子金屬箔，其中，樹脂製之板狀載子係包含熱硬化性樹脂。 (46) The attached sub-metal foil according to any one of (39) to (45), wherein the resin-made plate-shaped carrier contains a thermosetting resin.

(47)如(39)~(46)中任一者之附載子金屬箔，其中，樹脂製之板狀載子係預浸漬片。 (47) The attached sub-metal foil according to any one of (39) to (46), wherein the resin-made plate-shaped carrier is a prepreg.

(48)如(46)或(47)之附載子金屬箔，其中，板狀載子係具有120~320℃的玻璃化溫度Tg。 (48) A carrier metal foil according to (46) or (47), wherein the plate-shaped carrier has a glass transition temperature Tg of from 120 to 320 °C.

(49)如(39)~(40)中任一者之附載子金屬箔，其中與金屬箔之載子相接合側的表面，其十點平均粗糙度(Rz jis)係3．5μm以下。 (49) The attached sub-metal foil according to any one of (39) to (40), wherein the surface on the side joined to the carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(50)如(39)~(49)中任一者之附載子金屬箔，其中與金屬箔之載子不相接合側的表面，其十點平均粗糙度(Rz jis)係0．4μm以上10．0μm以下。 (50) The attached sub-metal foil according to any one of (39) to (49), wherein a surface having a side on which the carrier of the metal foil is not bonded has a ten-point average roughness (Rz jis) of 0.4 μm or more. 10.0 μm or less.

(51)如(39)~(50)中任一者之附載子金屬箔，其中，金屬箔之厚度為1μm以上400μm以下。 (51) The attached sub-metal foil according to any one of (39) to (50), wherein the metal foil has a thickness of 1 μm or more and 400 μm or less.

(52)如(39)~(51)中任一者之附載子金屬箔，其中，板狀載子之厚度為5μm以上1000μm以下。 (52) The attached sub-metal foil according to any one of (39) to (51), wherein the plate-shaped carrier has a thickness of 5 μm or more and 1000 μm or less.

(53)如(39)~(52)中任一者之附載子金屬箔，其中，平面觀察時，在切斷除去之領域中，係設置1~10處之直徑0．01mm~10mm之孔洞。 (53) The attached sub-metal foil according to any one of (39) to (52), wherein, in the plane of observation, in the field of cutting and removing, holes of 0.01 mm to 10 mm in diameter of 1 to 10 are provided. .

(54)如(39)~(53)中任一項之附載子金屬箔，其中，板狀載子與金屬箔係利用離型劑使之相互貼合而成。 (54) The attached sub-metal foil according to any one of (39) to (53), wherein the plate-shaped carrier and the metal foil are bonded to each other by a release agent.

(55)如(54)之附載子金屬箔，其中，離型劑係將下式：【化6】 (式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；R3及R4係分別獨立地選自鹵素原子、烷氧基、烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基)所示之矽烷化合物，其加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合使用而成者。 (55) The sub-metal foil of (54), wherein the release agent is of the following formula: [Chemical 6] (wherein 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 any one or more hydrogen atoms substituted by a halogen atom; a hydrocarbon group; R 3 and R 4 are each independently selected from a hydrocarbon group in which a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group or an aryl group is grouped, or one or more hydrogen atoms are substituted by a halogen atom. The decane compound represented by any of the hydrocarbon groups), the hydrolyzed product, and the condensate of the hydrolyzed product are used singly or in combination.

(56)如(54)之附載子金屬箔，其中，離型劑係使用分子內有兩個以下硫醇基之化合物所成者。 (56) The sub-metal foil according to (54), wherein the release agent is a compound having two or less thiol groups in the molecule.

(57)如(54)之附載子金屬箔，其中，離型劑係將下式：【化7】(R1)m-M-(R2)n(式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合使用而成者。 (57) The sub-metal foil according to (54), wherein the release agent is of the formula: [Chem. 7] (R 1 ) m -M-(R 2 ) n (wherein the R 1 alkoxy group) Or a halogen atom; R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M system Al, Ti or Any of Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R1 is an alkoxy group; further, m+n is a valence of M, that is, Al In the case of 3, Ti, Zr, the aluminate compound, the titanate compound or the zirconate compound shown in 4), the hydrolyzed product thereof, and the condensate of the hydrolyzed product, alone or in plural Combine the use of the original.

(58)如(39)~(53)中任一者之附載子金屬箔，其中，板狀載子與金屬箔係以使用選自矽酮(Silicone)、環氧系樹脂(Epoxy)、三聚氰胺 系樹脂(Melamine)及氟樹脂(Fluoropolymer)中之一種或數種樹脂構成之樹脂塗膜所貼合而成者。 (58) The attached sub-metal foil according to any one of (39) to (53), wherein the plate-shaped carrier and the metal foil are selected from the group consisting of Silicone, Epoxy, and melamine. A resin coating film made of one or more of a resin (Melamine) and a fluororesin (Fluoropolymer) is bonded together.

(59)如(39)~(58)中任一者之附載子金屬箔，其中於220℃經過3小時、6小時或9小時之中至少一個加熱程序後，金屬箔與板狀載子之剝離強度係10gf/cm以上200gf/cm以下。 (59) The attached sub-metal foil according to any one of (39) to (58), wherein after at least one heating process of 3 hours, 6 hours or 9 hours at 220 ° C, the metal foil and the plate-shaped carrier are The peel strength is 10 gf/cm or more and 200 gf/cm or less.

(60)如(39)~(59)項中任一項之附載子金屬箔，其中金屬箔為銅箔。 (60) The attached sub-metal foil according to any one of (39) to (59), wherein the metal foil is a copper foil.

(61)一種無芯多層印刷配線板用金屬箔，其特徵為平面觀察時，於其形狀為不具有90度以下內角之角(頂點)的金屬箔之表面上，係具有將下式： (式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；R3及R4係分別獨立地選自鹵素原子、烷氧基、烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基)所示之矽烷化合物，其加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合者。 (61) A metal foil for a coreless multilayer printed wiring board, characterized in that, in a plan view, a surface of a metal foil having an angle (vertex) having an internal angle of not more than 90 degrees has a following formula: (wherein 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 any one or more hydrogen atoms substituted by a halogen atom; a hydrocarbon group; R 3 and R 4 are each independently selected from a hydrocarbon group in which a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group or an aryl group is grouped, or one or more hydrogen atoms are substituted by a halogen atom. The decane compound represented by any of the hydrocarbon groups) is a condensate of the hydrolyzed product and the hydrolyzed product, and is used singly or in combination.

(62)一種無芯多層印刷配線板用金屬箔，其特徵為平面觀察時，於其形狀為不具有90度以下內角之角(頂點)的金屬箔之表面上，其分子內有兩個以下之硫醇基的化合物者。 (62) A metal foil for a coreless multilayer printed wiring board characterized in that, in a plan view, on a surface of a metal foil having an angle (vertex) having an internal angle of not more than 90 degrees, there are two molecules in the molecule. The following thiol-based compounds.

(63)一種無芯多層印刷配線板用金屬箔，其特徵為平面觀察時，於其形狀為不具有90度以下內角之角(頂點)的金屬箔之表面上，係具有將 下式：【化9】(R1)m-M-(R2)n(式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物、其等之加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合者。 (63) A metal foil for a coreless multilayer printed wiring board, characterized in that, in a plan view, a surface of a metal foil having an angle (vertex) having an internal angle of not more than 90 degrees is formed by the following formula: (R 1 ) m -M-(R 2 ) n (wherein 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 a hydrocarbon group having one or more of hydrogen atoms substituted by a halogen atom; M is any one of Al, Ti or Zr; n is 0 or 1 or 2, and m is a valence of 1 or more and M The following integer, at least one of R1 is an alkoxy group; further, the valence of m+n is M, that is, 3 in the case of Al, and the aluminate compound and the titanate compound shown in 4) in the case of Ti and Zr. Further, a zirconate compound, a hydrolyzed product thereof, or the like, and a condensate of the hydrolyzed product may be used singly or in combination.

(64)一種無芯多層印刷配線板用金屬箔，其特徵為平面觀察時，於其形狀為不具有90度以下內角之角(頂點)的金屬箔之表面上，具有選自矽酮(Silicone)、環氧系樹脂(Epoxy)、三聚氰胺系樹脂(Melamine)及氟樹脂(Fluoropolymer)之一種或數種樹脂所構成之樹脂塗膜者。 (64) A metal foil for a coreless multilayer printed wiring board, which is characterized in that, in plan view, a surface of a metal foil having an angle (vertex) having an internal angle of not more than 90 degrees has a surface selected from the group consisting of anthrone ( A resin coating film composed of one or more resins of Silicone), an epoxy resin (Epoxy), a melamine resin (Melamine), and a fluororesin (Fluoropolymer).

(65)一種無芯多層印刷配線板用金屬箔，其特徵為，相對於金屬箔在(61)~(64)之任一者中以化合物或樹脂塗膜作用測之表面，於該化合物或樹脂塗膜進行作用前，係經過鉻酸鹽處理者。 (65) A metal foil for a coreless multilayer printed wiring board, characterized in that the surface of the metal foil is coated with a compound or a resin coating film in any one of (61) to (64), or Before the resin coating film is applied, it is subjected to chromate treatment.

(66)如(61)~(65)中任一者之無芯多層印刷配線板用金屬箔，其中，金屬箔在(61)~(64)之任一者中，以化合物或樹脂塗膜作用側之表面，其十點平均粗糙度(Rz jis)係3.5μm以下。 (65) A metal foil for a coreless multilayer printed wiring board according to any one of (61) to (65), wherein the metal foil is coated with a compound or a resin in any one of (61) to (64) The surface of the action side has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(67)如(61)~(66)中任一項之無芯多層印刷配線板用金屬箔，其中，金屬箔在(61)~(64)中任一項中不以化合物或樹脂塗膜作用側之表面，其十點平均粗糙度(Rz jis)係0.4μm以上10.0μm以下。 (6) The metal foil for a coreless multilayer printed wiring board according to any one of (61) to (66), wherein the metal foil is not coated with a compound or a resin in any one of (61) to (64) The surface of the action side has a ten-point average roughness (Rz jis) of 0.4 μm or more and 10.0 μm or less.

(68)如(61)~(67)中任一者之無芯多層印刷配線板用金屬箔，其中金屬箔為銅箔。 (68) A metal foil for a coreless multilayer printed wiring board according to any one of (61) to (67), wherein the metal foil is a copper foil.

(69)一種金屬箔，其特徵為平面觀察時，於其形狀為不具有90度以下內角之角(頂點)金屬箔之表面，係具有將下式： (式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；R3及R4係分別獨立地選自鹵素原子、烷氧基、烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基)所示之矽烷化合物，其加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合之金屬箔；且其係可用於：在該表面將樹脂製之板狀載子剝離並使之密著的用途者。 (69) A metal foil characterized in that, in a plan view, a surface of a metal foil having an angle (vertex) having an internal angle of not more than 90 degrees is formed by the following formula: (wherein 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 any one or more hydrogen atoms substituted by a halogen atom; a hydrocarbon group; R 3 and R 4 are each independently selected from a hydrocarbon group in which a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group or an aryl group is grouped, or one or more hydrogen atoms are substituted by a halogen atom. a decane compound represented by any of the hydrocarbyl groups, a hydrolyzed product thereof, a condensate of the hydrolyzed product, or a metal foil which is combined singly or in combination; and which can be used for: resin made on the surface The user who peels off the plate-shaped carrier and makes it dense.

(70)一種金屬箔，其特徵為其係平面觀察時，於其形狀為不具有90度以下內角之角(頂點)的金屬箔之表面，其分子內有兩個以下硫醇基之化合物之金屬箔；且其係可用於：在該表面將樹脂製之板狀載子剝離並使之密著的用途者。 (70) A metal foil characterized in that, in a plane view, a surface of a metal foil having an angle (vertex) having an internal angle of not more than 90 degrees, a compound having two or less thiol groups in its molecule The metal foil is used for the purpose of peeling off and adhering a resin-made plate-shaped carrier to the surface.

(71)一種金屬箔，其特徵為平面觀察時，於其形狀為不具有90度以下內角之角(頂點)的金屬箔之表面，係具有將下式：【化11】(R1)m-M-(R2)n(式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群 之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合之金屬箔；且其係可用於：在該表面將樹脂製之板狀載子剝離並使之密著的用途者。 (71) a metal foil, wherein when viewed in plan, its shape does not have an interior angle of 90 degrees or less angle (vertex) of the surface of the metal foil, the system having the formula: 11] (R 1) m -M-(R 2 ) n (wherein 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 has one or more hydrogen atoms Any of the hydrocarbon groups substituted by a halogen atom; M is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer of 1 or more and a valence of M, and at least one of R1 Is an alkoxy group; further, the valence of m+n is M, that is, an aluminate compound, a titanate compound or a zirconate compound represented by 4) in the case of Al and 4) in the case of Ti and Zr, etc. a water-decomposition product, a condensate of the hydrolyzed product, or a metal foil which is combined singly or in combination; and a system which can be used for peeling and sealing a resin-made plate-shaped carrier on the surface .

(72)一種金屬箔，其特徵為平面觀察時，其形狀為不具有90度以下內角之角(頂點)的金屬箔之表面上，具有以選自矽酮(Silicone)、環氧系樹脂(Epoxy)、三聚氰胺系樹脂(Melamine)及氟樹脂(Fluoropolymer)之一種或數種樹脂所構成之樹脂塗膜者；且其係可用於：在該表面將樹脂製之板狀載子剝離並使之密著的用途者。 (72) A metal foil characterized in that, when viewed in plan, the shape is a surface of a metal foil having an angle (vertex) of an internal angle of not more than 90 degrees, and is selected from the group consisting of Silicone and epoxy resin. a resin coating film composed of one or a plurality of resins of (Epoxy), melamine resin, and fluororesin; and it can be used for peeling a resin-made plate-shaped carrier on the surface and The use of the close.

(73)如(69)~(72)中任一者之金屬箔，其中，相對於金屬箔在(69)~(72)之任一者中以化合物或樹脂塗膜作用之表面側，於該化合物或樹脂塗膜進行作用前，係經過鉻酸鹽處理者。 (73) The metal foil according to any one of (69) to (72), wherein the surface of the metal foil is applied to the surface of the compound or the resin coating film in any one of (69) to (72). Before the compound or the resin coating film is applied, it is subjected to chromate treatment.

(74)如(69)~(73)中任一者之金屬箔，其中，金屬箔在(31)~(34)之任一者中，以化合物或樹脂塗膜作用側之表面，其十點平均粗糙度(Rz jis)係3.5μm以下。 (74) The metal foil according to any one of (69) to (73), wherein the metal foil is coated with a compound or a resin on the side of the working side in any one of (31) to (34), The point average roughness (Rz jis) is 3.5 μm or less.

(75)如(69)~(74)中任一者之印刷配線板用金屬箔，其中金屬箔為銅箔。 (75) A metal foil for a printed wiring board according to any one of (69) to (74), wherein the metal foil is a copper foil.

(76)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有90度以下內角之角(頂點)的樹脂製板狀載子的至少在一側的表面上，係具有下式： (式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；R3及R4係分別獨立地選自鹵素原子、烷氧基、烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基)所示之矽烷化合物，其加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合者。 (76) A plate-shaped carrier characterized in that, in plan view, at least one surface of a resin-made plate-shaped carrier having a shape of an internal angle (vertex) having an internal angle of not more than 90 degrees The following formula: (wherein 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 any one or more hydrogen atoms substituted by a halogen atom; a hydrocarbon group; R 3 and R 4 are each independently selected from a hydrocarbon group in which a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group or an aryl group is grouped, or one or more hydrogen atoms are substituted by a halogen atom. The decane compound represented by any of the hydrocarbon groups) is a condensate of the hydrolyzed product and the hydrolyzed product, and is used singly or in combination.

(77)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有無90度以下內角之角(頂點)的樹脂製板狀載子的至少一側的表面上，其係分子內具有兩個以下之硫醇基之化合物者。 (77) A plate-shaped carrier characterized in that, in a plan view, at least one side of a resin-made plate-shaped carrier having a shape (vertex) having no internal angle of 90 degrees or less A compound having two or less thiol groups in the molecule.

(78)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有90度以下內角之角(頂點)的樹脂製板狀載子的至少在一側的表面上，其係具有將下式：【化13】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物、其等之加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合者。 (78) A plate-shaped carrier characterized by being at least one surface of a resin-made plate-shaped carrier having a shape (vertex) having an internal angle of not more than 90 degrees when viewed in plan There is the following formula: [Chem. 13] (R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkoxy group or a halogen atom; and R 2 is selected from an alkyl group, a cycloalkyl group and a aryl group) a hydrocarbon group in which a group is grouped, or a hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom; M is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is An integer of 1 or more and a valence of M or less, at least one of R 1 is an alkoxy group; and, m + n is a valence of M, that is, 3 when Al is 3, and aluminum acid represented by 4) when Ti and Zr are 4) A salt compound, a titanate compound, a zirconate compound, a hydrolyzed product thereof, or the like, and a condensate of the hydrolyzate product are used singly or in combination.

(79)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有90度以下內角之角(頂點)的樹脂製板狀載子的至少一側的表面具有以選自矽酮(Silicone)、環氧系樹脂(Epoxy)、三聚氰胺系樹脂(Melamine)及氟樹脂(Fluoropolymer)中之一種或數種樹脂所構成之樹脂塗膜者。 (79) A plate-shaped carrier characterized in that, in plan view, at least one surface of a resin-made plate-shaped carrier having a shape of an internal angle (vertex) having an internal angle of not more than 90 degrees is selected from the group consisting of 矽A resin coating film comprising one or more of a ketone (Silicone), an epoxy resin (Epoxy), a melamine resin (Melamine), and a fluororesin (Fluoropolymer).

(80)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有90度以下內角之角(頂點)的樹脂製板狀載子的至少在一側的表面上，其係具有將下式： (式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；R3及R4係分別獨立地選自鹵素原子、烷氧基、烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基)所示之矽烷化合物，其加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合之板狀載子；且其係可用於：在該表面將金屬箔剝離並使之密著的用途者。 (80) A plate-shaped carrier characterized by being at least one surface of a resin-made plate-shaped carrier having a shape of an internal angle (vertex) having an internal angle of not more than 90 degrees when viewed in plan Have the following formula: (wherein 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 any one or more hydrogen atoms substituted by a halogen atom; a hydrocarbon group; R 3 and R 4 are each independently selected from a hydrocarbon group in which a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group or an aryl group is grouped, or one or more hydrogen atoms are substituted by a halogen atom. a decane compound represented by any of the hydrocarbon groups), a hydrolyzed product thereof, a condensate of the hydrolyzed product, or a plate-shaped carrier which is combined singly or in combination; and which is used for: metal on the surface The user who peels off the foil and makes it dense.

(81)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有90度以下內角之角(頂點)的樹脂製板狀載子的至少一側的表面，其分子內具有兩個以下之硫醇基之化合物，且其係可用於：在該表面將金屬箔剝離並使之密著的用途者。 (81) A plate-shaped carrier characterized by having at least one surface of a resin-made plate-shaped carrier having an angle (vertex) having an internal angle of not more than 90 degrees in a plane view A compound of two or less thiol groups, which is useful for the purpose of peeling and adhering the metal foil to the surface.

(82)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有90度以下內角之角(頂點)的樹脂製板狀載子的至少一側的表面上，其係具有將下式：【化15】(R1)m-M-(R2)n (式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合之板狀載子；且其係可用於：在該表面將金屬箔剝離並使之密著的用途者。 (82) A plate-shaped carrier characterized in that, in a plan view, at least one surface of a resin-made plate-shaped carrier having an angle (vertex) having an internal angle of not more than 90 degrees The following formula: [Chem. 15] (R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkoxy group or a halogen atom; and R 2 is selected from an alkyl group, a cycloalkyl group and an aryl group) a hydrocarbon group of a group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M being any one of Al, Ti or Zr; n being 0 or 1 or 2, m being 1 An integer below the valence of M, at least one of R 1 is an alkoxy group; further, the valence of m + n is M, that is, 3 when Al is 3, and the aluminate shown by 4) for Ti and Zr a compound, a titanate compound or a zirconate compound, a hydrolyzed product thereof, a condensate of the hydrolyzed product, or a plate-shaped carrier which is combined singly or in combination; and the system can be used for: The user who peels off the metal foil and makes it dense.

(83)一種板狀載子，其特徵為平面觀察時，在其形狀為不具有90度以下內角之角(頂點)的樹脂製之板狀載子的至少一側的表面上，其係具有以選自矽酮(Silicone)、環氧系樹脂(Epoxy)、三聚氰胺系樹脂(Melamine)及氟樹脂(Fluoropolymer)中之一種或數種樹脂所構成之樹脂塗膜之板狀載子；且其係可用於：在該表面將金屬箔剝離並使之密著的用途者。 (83) A plate-shaped carrier characterized by being at least one surface of a resin-made plate-shaped carrier having a shape (vertex) having an internal angle of not more than 90 degrees when viewed in plan a plate-shaped carrier having a resin coating film selected from one or more resins selected from the group consisting of Silicone, Epoxy, Melamine, and Fluoropolymer; It can be used for the purpose of peeling off and adhering the metal foil on the surface.

(84)一種多層金屬張積層板的製造方法，其特徵為其係包含：相對於(39)~(60)中任一者之附載子金屬箔至少一面的金屬箔側，將樹脂進行層合，接著再將樹脂或金屬箔重複一次以上進行層合者。 (84) A method for producing a multilayer metal laminate, characterized in that the resin is laminated on at least one side of a metal foil with respect to at least one side of the attached sub-metal foil of any one of (39) to (60) Then, the resin or the metal foil is repeated one or more times for lamination.

(85)一種多層金屬張積層板的製造方法，其特徵為其係包含：在(39)~(60)中任一者之附載子金屬箔的金屬箔側，將樹脂進行層合，接著，再將樹脂、單面或雙面金屬張積層板、(39)~(60)中任一者之附載子金屬箔、或樹脂表面已利用金屬箔層合之層合體、或金屬箔，重複一次以上進行層合者。 (85) A method of producing a multilayered metal laminate, comprising: laminating a resin on a metal foil side of a carrier metal foil of any one of (39) to (60), and then, Further, the resin, the single-sided or double-sided metal laminate, the attached sub-metal foil of any one of (39) to (60), or the laminate having the resin surface laminated with the metal foil, or the metal foil is repeated once. The above is carried out.

(86)一種多層金屬張積層板的製造方法，其特徵為其於(84)或(85)之多層金屬張積層板的製造方法中，包含了將附載子金屬箔中板狀載子與金屬箔間之層合面，或層合體中樹脂與金屬箔間之層合面，加以切斷的步驟。 (86) A method for producing a multilayer metal laminate, characterized in that in the method for producing a multilayer metal laminate of (84) or (85), a plate-shaped carrier and a metal in an attached metal foil are included The step of cutting the laminated surface between the foils or the laminated surface between the resin and the metal foil in the laminate.

(87)一種多層金屬張積層板的製造方法，其特徵為其於申請專利範圍(84)或(85)之製造方法中，更包含了將附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟。 (87) A method for producing a multilayer metal laminate, characterized in that in the manufacturing method of the patent application (84) or (85), the plate-shaped carrier and the metal foil with the attached metal foil are further included The step of stripping and separating.

(88)一種多層金屬張積層板的製造方法，其特徵為其於(86)之製造方法中，更包含了將切斷後之附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟。 (88) A method for producing a multilayer metal laminate, characterized in that in the method of (86), the plate-shaped carrier of the attached metal foil after cutting and the metal foil are peeled off and separated. step.

(89)一種多層金屬張積層板的製造方法，其特徵為其於(87)或(88)之製造方法中，包含了將已經剝離並分離之金屬箔的一部或全部，以蝕刻進行除去之步驟。 (89) A method of producing a multilayered metal laminate, characterized in that in the manufacturing method of (87) or (88), one or all of the metal foil which has been peeled off and separated is removed by etching. The steps.

(90)一種多層金屬張積層板，其特徵為其係以(84)~(89)中任一者之製造方法所得者。 (90) A multilayer metal laminated laminate characterized by being produced by the method of any one of (84) to (89).

(91)一種組合基板的製造方法，其特徵為其係包含：於(39)~(60)中任一者之附載子金屬箔的金屬箔側，將組合配線層形成一層以上之步驟者。 (91) A method of producing a composite substrate, comprising the step of forming one or more layers of the combined wiring layer on the metal foil side of the sub-metal foil of any one of (39) to (60).

(92)如(91)之組合基板的製造方法，其中其組合配線層係使用減成法或全加成法或半加成法的至少一種而形成者。 (92) The method for producing a composite substrate according to (91), wherein the combined wiring layer is formed by using at least one of a subtractive method or a full additive method or a semi-additive method.

(93)一種組合基板的製造方法，其特徵為其係包含：於(39)~(60)中任一者之附載子金屬箔的金屬箔側，將樹脂進行層合，接著，再將樹脂、單面或雙面配線基板、單面或雙面金屬張積層板、(39)~(60)中任一者之附載子金屬箔、或樹脂表面已利用金屬箔層合之層合體、或金屬箔，重複一次以上進行層合者。 (93) A method of producing a composite substrate, comprising: laminating a resin on a metal foil side of a carrier metal foil of any one of (39) to (60), and then resinating the resin a single-sided or double-sided wiring board, a single-sided or double-sided metal laminate, an attached sub-metal foil of any one of (39) to (60), or a laminate having a resin surface laminated with a metal foil, or The metal foil is repeated one or more times for lamination.

(94)一種組合基板的製造方法，其特徵為其係進一步包含：於(93)之組合基板的製造方法中，在單面或雙面配線基板、單面或雙面金屬張積層板、附載子金屬箔的金屬箔、附載子金屬箔的板狀載子、層合體的金屬箔、層合體的板狀載子、金屬箔或樹脂上，鑽孔，於該孔洞的側面或底面進行傳導電鍍的步驟。 (94) A method of producing a composite substrate, characterized by further comprising: in the method of manufacturing a composite substrate according to (93), a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminated laminate, and an attached a metal foil of a sub-metal foil, a plate-shaped carrier to which a sub-metal foil is attached, a metal foil of a laminate, a plate-shaped carrier of a laminate, a metal foil or a resin, and drilled to conduct plating on a side surface or a bottom surface of the hole A step of.

(95)一種組合基板的製造方法，其特徵為其係進一步包含：於(93)或(94)之組合基板的製造方法中，在構成單面或雙面配線基板之金屬箔、構成單面或雙面金屬張積層板之金屬箔、構成附載子金屬箔之金屬箔、構成層合體之金屬箔、以及金屬箔之至少一者之上，進行一次以上配線形成之步驟。 (95) A method of producing a composite substrate, characterized by further comprising: in the method of manufacturing a composite substrate of (93) or (94), forming a metal foil of a single-sided or double-sided wiring substrate, forming a single side The step of forming one or more wirings on at least one of the metal foil of the double-sided metal laminate, the metal foil constituting the attached sub-metal foil, the metal foil constituting the laminate, and the metal foil.

(96)如(93)~(95)中任一者之組合基板的製造方法，其中更 包含：於配線所形成之表面上，使單面上密著有金屬箔之(39)~(60)中任一者之附載子金屬箔之載子側，或樹脂單面以金屬箔層合之層合體之樹脂側，與其接觸，並進行層合之步驟。 (96) A method of manufacturing a composite substrate according to any one of (93) to (95), wherein Including: on the surface formed by the wiring, the carrier side of the attached metal foil of any one of (39) to (60) in which the metal foil is adhered on one surface, or the metal foil is laminated on one side of the resin The resin side of the laminate is in contact with it and is subjected to a lamination step.

(97)如(93)~(95)中任一者之組合基板的製造方法，其中更包含：於配線所形成之表面上，將樹脂層合，並對該樹脂在雙面上均以金屬箔密著之(39)~(60)中任一者之附載子金屬箔，或樹脂雙面以金屬箔層合之層合體，使其接觸，並進行層合之步驟。 (97) The method for producing a composite substrate according to any one of (93) to (95), further comprising: laminating the resin on the surface formed by the wiring, and using the metal on both sides of the resin A laminated metal foil of any one of (39) to (60) in which the foil is adhered, or a laminate in which the resin is laminated on both sides of the metal foil, is brought into contact, and a step of laminating is carried out.

(98)如(93)~(97)中任一者之組合基板的製造方法，其中樹脂之至少一者為預浸漬片。 (98) A method of producing a composite substrate according to any one of (93) to (97), wherein at least one of the resins is a prepreg.

(99)一種組合配線板的製造方法，其特徵為其係包含：相對於(91)~(98)中任一者之方法所得的組合基板，將附載子金屬箔中板狀載子與金屬箔間之層合面，加以切斷的步驟。 (99) A method for producing a composite wiring board, comprising: a composite substrate obtained by the method of any one of (91) to (98), wherein the plate-shaped carrier and the metal in the attached metal foil are attached The step of cutting the laminated surface between the foils.

(100)一種組合配線板的製造方法，其特徵為其係進一步包含：相對於(91)~(98)中任一者之方法所得的組合基板，將附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟。 (100) A method of producing a composite wiring board, characterized by further comprising: a combination substrate obtained by the method of any one of (91) to (98), wherein the plate-shaped carrier attached to the sub-metal foil is The step of peeling and separating the metal foil.

(101)一種組合配線板的製造方法，其特徵為其於(99)之製造方法中，更包含了將切斷後之附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟。 (101) A method of producing a composite wiring board, characterized in that the method of (99) further comprises the step of separating and separating the plate-shaped carrier and the metal foil of the attached metal foil after cutting.

(102)一種組合配線板的製造方法，其特徵係於(100)或(101)之組合配線板的製造方法中，將與板狀載子密著之金屬箔的一部或全部，以蝕刻方式加以除去之步驟。 (102) A method of manufacturing a combined wiring board, characterized in that in the method of manufacturing a combined wiring board of (100) or (101), one or all of the metal foil adhered to the plate-shaped carrier is etched The way to remove it.

(103)一種組合配線板，其特徵係由(99)~(102)中任一者之方法所得者。 (103) A composite wiring board characterized by the method of any one of (99) to (102).

(104)一種印刷電路板的製造方法，其特徵係包含：藉由(99)~(102)中任一者之製造方法，製造組合配線板之步驟。 (104) A method of manufacturing a printed circuit board, comprising the step of manufacturing a combined wiring board by the manufacturing method of any one of (99) to (102).

藉由本發明，可簡便的調整板狀載子與金屬箔的剝離強度，故例如傳統上表現得過度提高的剝離強度之附載子金屬箔，即可將之調節 至較佳的剝離強度，而得到利用附載子金屬箔的印刷配線板，其生產性提高之優點；又因與其他部材碰撞而產生之外力使兩者剝離之情形將會有效地變少，故附載子金屬箔之操作性將提升，而可得到利用附載子金屬箔的印刷配線板，其生產性提高之優點。 According to the present invention, the peeling strength of the plate-shaped carrier and the metal foil can be easily adjusted, so that, for example, the attached sub-metal foil which has conventionally exhibited an excessively improved peeling strength can be adjusted. A printed wiring board using an attached sub-metal foil is obtained to have a better peeling strength, and the productivity is improved. Further, since the external force is generated by collision with other members, the peeling of the two is effectively reduced. The operability of the attached sub-metal foil is improved, and a printed wiring board using the attached sub-metal foil can be obtained, and the productivity is improved.

10‧‧‧層合模具 10‧‧‧Laminating mould

11‧‧‧附載子金屬箔 11‧‧‧With sub-metal foil

11a‧‧‧金屬箔 11a‧‧‧metal foil

11b‧‧‧離型劑所成之層或離型材 11b‧‧‧Layer or release profile

11c‧‧‧板狀載子 11c‧‧‧ plate-shaped carrier

12‧‧‧預浸漬片 12‧‧‧Prepreg

13‧‧‧內層芯板 13‧‧‧ Inner core board

14‧‧‧頁 Page 14‧‧‧

15‧‧‧本 15‧‧‧ben

16‧‧‧組合層 16‧‧‧ combination layer

20‧‧‧附載子金屬箔 20‧‧‧With sub-metal foil

21‧‧‧板狀載子 21‧‧‧ plate-shaped carrier

22‧‧‧金屬箔 22‧‧‧Metal foil

30‧‧‧附載子金屬箔 30‧‧‧With sub-metal foil

31‧‧‧板狀載子 31‧‧‧ plate-shaped carrier

32‧‧‧金屬箔 32‧‧‧metal foil

【圖1】圖示CCL的一構成例。 FIG. 1 is a diagram showing an example of the configuration of the CCL.

【圖2】圖示相關於本發明附載子金屬箔的一構成例。 Fig. 2 is a view showing a configuration example of the attached sub-metal foil of the present invention.

【圖3】圖示相關於本發明附載子金屬箔於平面觀察時，典型的構成例。 Fig. 3 is a view showing a typical configuration example of the attached sub-metal foil of the present invention when viewed in plan.

【圖4】相對於圖10附載子金屬箔重疊的方向，於垂直方向觀察之圖示。 Fig. 4 is a view as seen in the vertical direction with respect to the direction in which the sub-metal foil is superimposed with respect to Fig. 10.

【圖5】圖示相關於本發明附載子金屬箔另一之典型的構成例。 Fig. 5 is a view showing another typical configuration example of the attached sub-metal foil of the present invention.

【圖6】相對於圖12附載子金屬箔重疊的方向，於垂直方向觀察之圖示。 Fig. 6 is a view as seen in the vertical direction with respect to the direction in which the sub-metal foil is superimposed with respect to Fig. 12.

【圖7】圖示利用相關於本發明附載子銅箔(於樹脂板的單面接合之形態)之多層CCL的組合例。 Fig. 7 is a view showing a combination example of a multilayer CCL using the copper foil of the present invention (in the form of single-sided bonding of a resin sheet).

【圖8】圖示利用相關於本發明附載子銅箔(於樹脂板的雙面接合之形態)之多層CCL的組合例。 Fig. 8 is a view showing a combination example of a multilayer CCL using the copper foil of the present invention (in the form of double-sided bonding of a resin sheet).

在本發明附載子金屬箔的一實施形態方面，樹脂製之板狀載子與該載子的單面或雙面，較佳者係在雙面準備可剝離並密著金屬箔所成之附載子金屬箔。相關於本發明附載子金屬箔的一構成例係表示如圖2及圖7所示。特別在圖7最開始的地方，圖示了附載子金屬箔11，其中於樹脂製之板狀載子11c的雙面，係密著可剝離金屬箔11a。板狀載子11c與金屬箔11a之間，係使用具有如後述特定構造之鋁酸鹽化合物、鈦酸鹽化合物、鋯酸鹽化合物，其等加水分解生成物，該加水分解生成物之縮合體(以下略記為「金屬醇鹽」)11b加以貼合者。此外，在本發明附載子金屬箔的另一實施形態方面，板狀載子11c與金屬箔11a之間，係使用後述之離型劑所成之層或離型材11b所貼合而成。 In one embodiment of the attached sub-metal foil of the present invention, the resin-made plate-shaped carrier and one or both sides of the carrier are preferably attached to both sides to be peelable and adhered to the metal foil. Sub-metal foil. A configuration example relating to the attached sub-metal foil of the present invention is shown in Figs. 2 and 7. In particular, at the beginning of Fig. 7, the attached sub-metal foil 11 is illustrated, in which the peelable metal foil 11a is adhered to both sides of the resin-made plate-shaped carrier 11c. Between the plate-shaped carrier 11c and the metal foil 11a, an aluminate compound having a specific structure described later, a titanate compound, a zirconate compound, or the like, a hydrolyzed product, and a condensate of the hydrolyzed product are used. (hereinafter, abbreviated as "metal alkoxide") 11b is attached. Further, in another embodiment of the attached sub-metal foil of the present invention, the plate-shaped carrier 11c and the metal foil 11a are bonded together by a layer formed of a release agent described later or a release member 11b.

在構造上，雖與圖1所示CCL類似，但本發明的附載子金屬箔，因為金屬箔與樹脂最終將會分離，故具有容易剝離的構造。此點， 係因CCL非為需剝離之製品，在構造與機能上，為完全相異者所致。 Although the structure is similar to the CCL shown in Fig. 1, the attached sub-metal foil of the present invention has a structure which is easily peeled off because the metal foil and the resin are finally separated. At this point, Because CCL is not a product to be stripped, it is completely different in structure and function.

於本發明所使用之附載子金屬箔最終都必須將之剝離，並不適合過度的提高密著性，而在板狀載子與金屬箔，於印刷線路板製作過程中所進行的鍍(金屬)等之藥液處理工程中，必須為不至剝離，但有某種程度的密著性。由此觀點來看，金屬箔與板狀載子其剝離強度以，10gf/cm以上為佳，30gf/cm以上為更佳，50gf/cm為最佳，另一方面以，200gf/cm以下為佳、150gf/cm以下為更佳、80gf/cm以下為最佳。藉由將金屬箔與板狀載子之剝離強度控制在此範圍內，使其不會在搬運時或加工時剝離，又易於以人工方式剝離，亦即能以機械方式剝離之剝離強度，其調節將較容易。 The attached sub-metal foil used in the present invention must be peeled off at the end, and is not suitable for excessively improving the adhesion, but in the plate-shaped carrier and the metal foil, the plating (metal) is performed in the process of manufacturing the printed wiring board. In the liquid chemical treatment project, it must be not peeled off, but has a certain degree of adhesion. From this point of view, the peeling strength of the metal foil and the plate-shaped carrier is preferably 10 gf/cm or more, more preferably 30 gf/cm or more, and most preferably 50 gf/cm, and 200 gf/cm or less. Preferably, 150 gf/cm or less is more preferable, and 80 gf/cm or less is the best. By controlling the peeling strength of the metal foil and the plate-shaped carrier within this range, it is not peeled off during handling or processing, and is easily peeled off by hand, that is, peeling strength which can be mechanically peeled off, Adjustment will be easier.

又，在本發明附載子金屬箔的一實施形態方面，附載子金屬箔於平面觀察時，金屬箔與板狀載子為同一形狀，且係不具有90度以下內角之角(頂點)的形狀者。如同所謂「不具有90度以下內角之角(頂點)的形狀」之代表性的例子可列舉如，平面觀察時，金屬箔與板狀載子為同一形狀，且係由直線及曲線所圍成之形狀者。此時，曲線為圓弧或橢圓弧。又，另外代表性的例子可列舉如，所有內角皆係大於90度角度之多邊形，例如所有內角皆係大於90度且小於180度角度之凸多角形狀。更進一步說，另外代表性的例子可列舉如僅由曲線所圍成之形狀者。 Further, in an embodiment of the attached sub-metal foil of the present invention, the metal foil and the plate-shaped carrier have the same shape when viewed from the plane, and the angle (vertex) of the internal angle of 90 degrees or less is not included. Shaper. As a representative example of the "shape having no angle (vertex) having an internal angle of 90 degrees or less", for example, when viewed in plan, the metal foil and the plate-shaped carrier have the same shape, and are surrounded by straight lines and curved lines. Into the shape of the person. At this point, the curve is an arc or an elliptical arc. Further, another representative example may be, for example, a polygon having an inner angle greater than an angle of 90 degrees, for example, all inner corners are convex polygonal shapes having an angle greater than 90 degrees and less than 180 degrees. Furthermore, another representative example can be exemplified by a shape surrounded only by a curve.

此種構造之具體例可列舉如，平面觀察時，如圖3所示由直線及曲線所圍成之形狀者、如圖5所示內角皆係大於90度角度之多邊形。 Specific examples of such a configuration include, for example, a shape surrounded by a straight line and a curved line as shown in FIG. 3 in plan view, and a polygonal shape having an inner angle of more than 90 degrees as shown in FIG.

圖3、圖4係附載子金屬箔典型的構成例之圖示。圖3係此構成例於平面觀察時之圖示，圖4係相對於此構成例重疊方向，於垂直方向觀察之圖示。 3 and 4 are views showing a typical configuration example of the attached sub-metal foil. Fig. 3 is a view showing a configuration example in the case of a plan view, and Fig. 4 is a view seen in a vertical direction with respect to the overlapping direction of the configuration example.

在圖3、圖4中，板狀載子21與金屬箔22貼合構成附載子金屬箔20，於平面觀察時，金屬箔22與板狀載子21為同一形狀，且如圖3所示，金屬箔22及板狀載子21兩者之邊緣皆以曲面34所圍成之形狀。 In FIG. 3 and FIG. 4, the plate-shaped carrier 21 and the metal foil 22 are bonded together to form the attached sub-metal foil 20, and the metal foil 22 and the plate-shaped carrier 21 have the same shape when viewed in plan, and as shown in FIG. The edges of both the metal foil 22 and the plate-shaped carrier 21 are surrounded by the curved surface 34.

圖5、圖6係附載子金屬箔其他之典型的構成例之圖示。圖 5係此構成例於平面觀察時之圖示，圖6係相對於此構成例重疊方向，於垂直方向觀察之圖示。 Fig. 5 and Fig. 6 are diagrams showing another typical configuration example of the attached sub-metal foil. Figure 5 is a diagram showing a configuration example in the case of a plan view, and FIG. 6 is an illustration of a direction in which the configuration example is overlapped and viewed in the vertical direction.

在圖5、圖6中，板狀載子31與金屬箔32貼合構成附載子金屬箔30，於平面觀察時，金屬箔與板狀載子為同一形狀，且如圖5所示，形狀為內角係大於90度角度之多邊形。換言之，其形狀於金屬箔32與板狀載子31的層合方向，係以平坦面替代圖3之附載子金屬箔的曲面34所構成。 In FIG. 5 and FIG. 6, the plate-shaped carrier 31 and the metal foil 32 are bonded together to form the attached sub-metal foil 30. When viewed in plan, the metal foil and the plate-shaped carrier have the same shape, and as shown in FIG. A polygon with an internal angle greater than 90 degrees. In other words, the shape is formed by the flat surface replacing the curved surface 34 of the attached sub-metal foil of FIG. 3 in the lamination direction of the metal foil 32 and the plate-shaped carrier 31.

如此之構造，因最易於與其他部材接觸之四個角落附近，不具有突出的部分，使其與其他部材碰撞所產生之外力，不易使板狀載子與金屬箔的界面引起巨大的應力變化，因此於處理過程中之板狀載子與金屬箔剝離之情形將可減少。 With such a configuration, there is no protruding portion near the four corners which are most easily in contact with other members, and the external force generated by collision with other members is less likely to cause a large stress change at the interface between the plate-shaped carrier and the metal foil. Therefore, the peeling of the plate-shaped carrier from the metal foil during the process can be reduced.

又，圖3~圖6係表示，板狀載子僅單面與金屬箔貼合的型態，但也可雙面皆與金屬箔貼合。 3 to 6 show that the plate-shaped carrier is bonded to the metal foil only on one side, but it may be bonded to the metal foil on both sides.

又，如同後述，上述之附載子金屬箔作為在切斷尖端部位之用途使用時，於平面觀察，其切斷除去之領域中，使用鑽頭等設置1~10處之直徑0．01mm~10mm之孔洞。如此設置之孔洞，於後述多層金屬層合板的製造、組合基板的製造時，可作為定位硝等固定裝置使用。 In addition, as described later, when the above-mentioned attached sub-metal foil is used for the purpose of cutting the tip end portion, in the field of cutting and removing, the diameter of 0.01 to 10 mm is set at 1 to 10 using a drill or the like. Hole. The hole thus provided can be used as a fixing device such as positioning nitric acid in the production of a multilayer metal laminate as described later and the production of a composite substrate.

接著，為了實現後述中附載子金屬箔之用途所需密著性，將說明於板狀載子與金屬箔貼合時，較為合適使用之離型劑或離型材。 Next, in order to achieve the adhesiveness required for the use of the sub-metal foil to be described later, a release agent or a release material which is suitably used when the plate-shaped carrier is bonded to the metal foil will be described.

(1)矽烷化合物 (1) decane compound

使用具有下式所示構造之矽烷化合物或其加水分解生成物或該加水分解生成物之縮合體(以下略記為矽烷化合物)以單獨或複數混合者，在板狀載子與金屬箔之間進行貼合，適度的將密著性調低，可將剝離強度調節至上述之範圍。 The decane compound having a structure represented by the following formula or a hydrolyzed product thereof or a condensate of the hydrolyzed product (hereinafter abbreviated as a decane compound) is used alone or in combination, and is carried out between a plate-shaped carrier and a metal foil. The fit is adjusted to moderately lower the adhesion, and the peel strength can be adjusted to the above range.

式：【化16】 Type: [Chemical 16]

(式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基及芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；R3及R4係分別獨立地選自鹵素原子、烷氧基、烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基) (wherein 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 any one or more hydrogen atoms substituted by a halogen atom; a hydrocarbon group; R 3 and R 4 are each independently selected from a hydrocarbon group in which a halogen atom, an alkoxy group, an alkyl group, a cycloalkyl group or an aryl group is grouped, or one or more hydrogen atoms are substituted by a halogen atom. Hydrocarbon group of any one)

該矽烷化合物至少必須具有一烷氧基。若不存在烷氧基，選自烷基、環烷基以及芳基所成群中之烴基，或其一個以上的氫原子被取代為鹵素原子之僅有此等任一烴基構成取代基之情形，板狀載子與金屬箔表面的密著性會有過度低下的傾向。此外，該矽烷化合物至少必須具有一個選自烷基、環烷基以及芳基所成群中之烴基，或其一個以上的氫原子被取代為鹵素原子之此等任一之烴基。若不具有該烴基時，板狀載子與金屬箔表面的密著性會有上昇的傾向。又，與本發明申請相關之烷氧基也包含一個以上的氫原子被取代為鹵素原子的烷氧基。 The decane compound must have at least one alkoxy group. In the absence of an alkoxy group, a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a case where one or more hydrogen atoms thereof are substituted with a halogen atom and only one of these hydrocarbon groups constitutes a substituent The adhesion of the plate-shaped carrier to the surface of the metal foil tends to be excessively low. Further, the decane compound must have at least one 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. If the hydrocarbon group is not present, the adhesion between the plate-shaped carrier and the surface of the metal foil tends to increase. Further, the alkoxy group related to the application of the present invention also contains an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom.

板狀載子與金屬箔的剝離強度調節至上述範圍時，該矽烷化合物為具有三個烷氧基，及一個上述烴基(包含一個以上的氫原子被取代為鹵素原子之烴基)者為佳。在上述式中，R3及R4兩者係為烷氧基。 When the peeling strength of the plate-shaped carrier and the metal foil is adjusted to the above range, the decane compound preferably has three alkoxy groups and one of the above hydrocarbon groups (hydrocarbon groups containing one or more hydrogen atoms substituted with a halogen atom). In the above formula, both R 3 and R 4 are alkoxy groups.

對於烷氧基而言，雖無限定，但可列舉如：甲氧基、乙氧基、n-或iso-丙氧基、n-、iso-或tert-丁氧基、n-、iso-或neo-戊氧基、n-己氧基、環己氧基、n-庚氧基、n-辛氧基等之直鏈狀、支鏈狀或環狀的碳數1~20之烷氧基、較佳者為碳數1~10之烷氧基、最佳者為碳數1~5的烷氧基。 The alkoxy group is not limited, but may, for example, be a methoxy group, an ethoxy group, an n- or iso-propoxy group, an n-, iso- or tert-butoxy group, or an n-iso group. Or a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as neo-pentyloxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy or n-octyloxy The group is preferably an alkoxy group having 1 to 10 carbon atoms, and most preferably an alkoxy group having 1 to 5 carbon atoms.

對於鹵素原子而言，可列舉如：氟原子、氯原子、溴原子或碘原子。 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

對於烷基而言，雖無限定，但可列舉如：甲基、乙基、n-或iso-丙基、n-、iso-或tert-丁基、n-、iso-或 neo-戊基、n-己基、n-辛基、n-癸基等之直鏈或支鏈狀的碳數1~20之烷基、較佳者為碳數1~10之烷基、最佳者為碳數1~5的烷基。 The alkyl group is not limited, but may, for example, be methyl, ethyl, n- or iso-propyl, n-, iso- or tert-butyl, n-, iso- or a linear or branched alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, most preferably a neo-pentyl group, an n-hexyl group, an n-octyl group or an n-fluorenyl group. The preferred one is an alkyl group having 1 to 5 carbon atoms.

對於環烷基而言，雖無限定但可列舉如：環丙基、環丁基、環戊基、環己基、環庚基、環辛基等其碳數3~10之環烷基、較佳者為碳數5~7之環烷基。 The cycloalkyl group is not limited, and examples thereof include a cycloalkyl group having a carbon number of 3 to 10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. The preferred one is a cycloalkyl group having 5 to 7 carbon atoms.

對於芳基而言，可列舉如：苯基、以烷基取代之苯基(例：甲苯基、二甲苯基)、1-又或2-萘基、蒽基等之碳數6~20之芳基，較佳者為碳數6~14之芳基。 The aryl group may, for example, be a phenyl group, a phenyl group substituted with an alkyl group (for example, tolyl, xylyl group), a 1- or 2-naphthyl group, a fluorenyl group or the like having a carbon number of 6 to 20 The aryl group is preferably an aryl group having 6 to 14 carbon atoms.

此等烴基之一個以上的氫原子可以鹵素原子取代，例如可取代為：氟原子、氯原子、或溴原子。 One or more hydrogen atoms of these hydrocarbon groups may be substituted by a halogen atom, and may be, for example, a fluorine atom, a chlorine atom, or a bromine atom.

較佳的矽烷化合物可列舉如：甲基三甲氧基矽烷、乙基三甲氧基矽烷、n-或iso-丙基三甲氧基矽烷、n-、iso-或tert-丁基三甲氧基矽烷、n-iso-或neo-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(如：p-(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、n-或iso-丙基三乙氧基矽烷、n-、iso-或tert-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(如：p-(甲基)苯基三乙氧基矽烷)、(3,3,3-三氟丙基)三甲氧基矽烷、以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、此等之加水分解生成物，以及此等之加水分解生成物之縮合體等為例；在其中，以取得容易的觀點來看，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，為更佳。 Preferred decane compounds are, for example, methyltrimethoxydecane, ethyltrimethoxydecane, n- or iso-propyltrimethoxydecane, n-, iso- or tert-butyltrimethoxydecane, N-iso- or neo-pentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane,phenyltrimethoxydecane;alkyl substituted phenyltrimethoxydecane (eg p-(methyl)phenyltrimethoxydecane), methyltriethoxydecane, ethyltriethoxydecane, n- or iso-propyltriethoxydecane, n-, iso - or tert-butyl triethoxy decane, pentyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, phenyl triethoxy decane , alkyl substituted phenyl triethoxy decane (eg: p-(methyl)phenyl triethoxy decane), (3,3,3-trifluoropropyl)trimethoxynonane, and tridecafluoro Octyltriethoxydecane, methyltrichlorodecane, dimethyldichlorodecane, trimethylchlorodecane, phenyltrichlorodecane, trimethylfluorodecane, dimethyldibromodecane, diphenyl Bromodecane, these Examples of the hydrolyzed product, a condensate of the hydrolyzed product, and the like are exemplified, and among them, propyltrimethoxydecane, methyltriethoxydecane, and hexyltrimethoxy are preferable from the viewpoint of availability. More preferably, decane, phenyltriethoxydecane or decyltrimethoxydecane.

附載子金屬箔以熱壓機密著板狀載子與金屬箔為可能之製造方式。例如：於金屬箔以及/或板狀載子之貼合面以前述矽烷化合物做塗層處理之後，對金屬箔貼合的表面，以B階段之樹脂製之板狀載子使用 熱壓機加以層合，為可能之製造方式。 It is possible to mount a sub-metal foil with a hot press to adhere a plate-shaped carrier and a metal foil. For example, after the surface of the metal foil and/or the plate-shaped carrier is coated with the aforementioned decane compound, the surface to which the metal foil is bonded is used as a plate-shaped carrier made of resin of the B-stage. The hot press is laminated to make it possible.

矽烷化合物可在水溶液的形態下使用。為提高對水的溶解度可添加甲醇或乙醇等醇類溶劑。醇類溶劑的添加在使用疏水性高的矽烷化合物時特別有效。攪拌矽烷化合物之水溶液可促進烷氧基的水解，長時間攪拌可促進加水生成物的縮合。一般而言，使用經充分時間攪拌進行水解及縮合之矽烷化合物時，金屬箔與板狀載子的剝離強度有降低的傾向。因此，可藉由調整攪拌時間以調整剝離強度。雖無限定，矽烷化合物以水溶解後之攪拌時間可如1~100小時，典型之攪拌時間可為1~30小時。當然，也有不進行攪拌之方法。 The decane compound can be used in the form of an aqueous solution. An alcohol solvent such as methanol or ethanol may be added to increase the solubility in water. The addition of an alcohol solvent is particularly effective when a highly hydrophobic decane compound is used. Agitating the aqueous solution of the decane compound promotes hydrolysis of the alkoxy group, and stirring for a long period of time promotes condensation of the water-added product. In general, when a decane compound which is hydrolyzed and condensed by stirring for a sufficient period of time is used, the peeling strength of the metal foil and the plate-shaped carrier tends to be lowered. Therefore, the peel strength can be adjusted by adjusting the stirring time. Although not limited, the stirring time of the decane compound after dissolving in water may be as long as 1 to 100 hours, and the typical stirring time may be 1 to 30 hours. Of course, there is also a method of not stirring.

矽烷化合物在水溶液中的濃度較高時，金屬箔與板狀載子的剝離強度有降低的傾向，可藉由調整矽烷化合物的濃度，進一步調整剝離強度。雖無限定，矽烷化合物在水溶液中的濃度可調整為體積百分濃度0.01~10.0(%)，傳統上可調整為體積百分濃度0.1~5.0(%)。 When the concentration of the decane compound in the aqueous solution is high, the peel strength of the metal foil and the plate-shaped carrier tends to decrease, and the peel strength can be further adjusted by adjusting the concentration of the decane compound. Although not limited, the concentration of the decane compound in the aqueous solution can be adjusted to a volume percentage of 0.01 to 10.0 (%), which can be conventionally adjusted to a volume percentage of 0.1 to 5.0 (%).

矽烷化合物的水溶液之pH值並無特別限制，酸性或鹼性都可利用。例如pH值範圍在3.0~10.0也可使用。以不需特別調整pH值範圍之觀點來看，落在中性附近5.0~9.0範圍的pH值較佳，落在7.0~9.0範圍的pH值為更佳。 The pH of the aqueous solution of the decane compound is not particularly limited, and both acidic and basic can be utilized. For example, a pH range of 3.0 to 10.0 can also be used. The pH value in the range of 5.0 to 9.0 near neutral is preferable, and the pH falling in the range of 7.0 to 9.0 is more preferable from the viewpoint of not particularly adjusting the pH range.

(2)分子內具有兩個以下硫醇基之化合物 (2) Compounds having two or less thiol groups in the molecule

使用分子內有兩個以上硫醇基之化合物，將板狀載子與金屬箔貼合，適度的將密著性調低，可將剝離強度調節至上述之範圍。 The compound having two or more thiol groups in the molecule is used, and the plate-shaped carrier is bonded to the metal foil to appropriately adjust the adhesion, and the peel strength can be adjusted to the above range.

但，使用分子內有三個以上硫醇基之化合物或其鹽類介於板狀載子與金屬箔之間，使其貼合的情形，將不適於本發明所記載使剝離強度減低之目的。此原因被推測為，分子內之硫醇基過量時，硫醇基與硫醇基，或硫醇基與板狀載子，或硫醇基與金屬箔將產生化學反應，形成過量之硫醚鍵結、雙硫鍵結或多硫鍵結，使板狀載子與金屬箔之間形成堅固的三維分子交聯構造，進而使剝離強度上昇。此事例於專利文獻2(日本專利特開2000-196207號公報)已被披露。 However, when a compound having three or more thiol groups in a molecule or a salt thereof is interposed between a plate-shaped carrier and a metal foil to bond them, it is not suitable for the purpose of reducing the peel strength described in the present invention. This reason is presumed to be that when the thiol group in the molecule is excessive, the thiol group and the thiol group, or the thiol group and the plate-shaped carrier, or the thiol group and the metal foil will chemically react to form an excessive amount of thioether. Bonding, disulfide bonding or polysulfide bonding forms a strong three-dimensional molecular cross-linking structure between the plate-shaped carrier and the metal foil, thereby increasing the peel strength. This example has been disclosed in Patent Document 2 (Japanese Patent Laid-Open Publication No. 2000-196207).

此等分子內具有兩個以下硫醇基之化合物，可列舉如：硫醇 (thiol)、乙二硫醇(dithiol)、硫代羧酸(thiocarboxylic acid)或其鹽類、二硫代羧酸(dithiocarboxylic acid)或其鹽類、硫代磺酸(thiosulfonic acid)或其鹽類，及二硫代磺酸(dithiosulfonic acid)或其鹽類，在其中，可使用選擇至少一種之化合物。 a compound having two or less thiol groups in the molecule, and examples thereof include: a mercaptan (thiol), dithiol, thiocarboxylic acid or a salt thereof, dithiocarboxylic acid or a salt thereof, thiosulfonic acid or a salt thereof And a dithiosulfonic acid or a salt thereof, wherein at least one compound can be used.

硫醇(thiol)係分子內具有一個硫醇基之化合物，例如以R-SH表示。在此，R表示為脂肪族系或芳香烴系或雜環基，其中可包含羥基或胺基。 A thiol is a compound having a thiol group in the molecule, for example, represented by R-SH. Here, R is represented by an aliphatic or aromatic hydrocarbon group or a heterocyclic group, and may contain a hydroxyl group or an amine group.

乙二硫醇(dithiol)係分子內具有兩個硫醇基之化合物，例如以R(SH)2表示。在此，R表示為脂肪族系或芳香烴系或雜環基，其中可包含羥基或胺基。且，兩個硫醇基可個別以相同碳原子結合，也可彼此分別由不同碳原子或氮原子結合。 Dithiol is a compound having two thiol groups in the molecule, for example, represented by R(SH) 2 . Here, R is represented by an aliphatic or aromatic hydrocarbon group or a heterocyclic group, and may contain a hydroxyl group or an amine group. Further, the two thiol groups may be bonded individually by the same carbon atom, or may be bonded to each other by a different carbon atom or a nitrogen atom.

硫代羧酸(thiocarboxylic acid)係分子中以硫醇基取代有機羧酸的羥基之化合物，例如以R-CO-SH表示。R表示為脂肪族系或芳香烴系或雜環基，其中可包含羥基或胺基。且，硫代羧酸也可以鹽類的型態使用。另外，也可使用具有兩個硫代羧酸基之化合物。 A compound of a thiocarboxylic acid-based molecule in which a thiol group is substituted with a hydroxyl group of an organic carboxylic acid, for example, represented by R-CO-SH. R is represented by an aliphatic or aromatic hydrocarbon group or a heterocyclic group, and may contain a hydroxyl group or an amine group. Further, the thiocarboxylic acid can also be used in the form of a salt. In addition, a compound having two thiocarboxylic acid groups can also be used.

二硫代羧酸(dithiocarboxylic acid)係分子中以硫原子取代有機羧酸之羧基中的兩個氧原子之化合物，例如以R-(CS)-SH表示。R表示為脂肪族系或芳香烴系或雜環基，其中可包含羥基或胺基。且，二硫代羧酸也可以鹽類的型態使用。另外，也可使用具有兩個二硫代羧酸基之化合物。 A compound of a dithiocarboxylic acid molecule in which two oxygen atoms in a carboxyl group of an organic carboxylic acid are substituted with a sulfur atom, for example, represented by R-(CS)-SH. R is represented by an aliphatic or aromatic hydrocarbon group or a heterocyclic group, and may contain a hydroxyl group or an amine group. Further, the dithiocarboxylic acid can also be used in the form of a salt. Alternatively, a compound having two dithiocarboxylic acid groups can also be used.

硫代磺酸(thiosulfonic acid)係分子中以硫醇基取代有機磺酸的羥基之化合物，例如以R(SO2)-SH表示。R表示為脂肪族系或芳香烴系或雜環基，其中可包含羥基或胺基。且，硫代磺酸也可以鹽類的型態使用。 Thiosulfonate (thiosulfonic acid) based molecules to thiol groups substituted with a hydroxyl group of the organic sulfonic acid compound, for example, R (SO 2) -SH FIG. R is represented by an aliphatic or aromatic hydrocarbon group or a heterocyclic group, and may contain a hydroxyl group or an amine group. Further, the thiosulfonic acid may also be used in the form of a salt.

二硫代磺酸(dithiosulfonic acid)係分子中有機磺酸的兩個氧原子個別以硫醇基所取代之化合物，例如以R-((SO2)-SH)2表示。R表示為脂肪族系或芳香烴系或雜環基，其中可包含羥基或胺基。且，二硫代羧酸也可以鹽類的型態使用。 Organic sulfonic acid molecule individually to two oxygen atoms substituted with a thiol group of the dithiophosphoric acid compound (dithiosulfonic acid) based, for example R - ((SO 2) -SH ) 2 FIG. R is represented by an aliphatic or aromatic hydrocarbon group or a heterocyclic group, and may contain a hydroxyl group or an amine group. Further, the dithiocarboxylic acid can also be used in the form of a salt.

在此，對於R而言適合的脂肪族烴基可列舉如：烷基、環烷 基，此等烴基可為含有烴基與胺基任一者或兩者。 Here, examples of the aliphatic hydrocarbon group suitable for R include, for example, an alkyl group and a cycloalkane. The hydrocarbyl groups may be any one or both of a hydrocarbyl group and an amine group.

又對於烷基而言，雖無限定，但可列舉如：甲基、乙基、n-或iso-丙基、n-、iso-或tert-丁基、n-、iso-或neo-戊基、n-己基、n-辛基、n-癸基等之直鏈或支鏈狀的碳數1~20之烷基、較佳者為碳數1~10之烷基、最佳者為碳數1~5的烷基。 Further, the alkyl group is not limited, but may, for example, be a methyl group, an ethyl group, an n- or iso-propyl group, an n-, iso- or tert-butyl group, an n-, iso- or neo-pentane group. a linear or branched alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, preferably an n-hexyl group, an n-octyl group or an n-fluorenyl group. An alkyl group having 1 to 5 carbon atoms.

又對於環烷基而言，雖無限定但可列舉如：環丙基、環丁基、環戊基、環己基、環庚基、環辛基等其碳數3~10之環烷基、較佳者為碳數5~7之環烷基。 Further, the cycloalkyl group is not limited, and examples thereof include a cycloalkyl group having a carbon number of 3 to 10 such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. Preferred is a cycloalkyl group having 5 to 7 carbon atoms.

另外，對於R而言適合的芳香族烴基可列舉如：苯基、以烷基取代之苯基(例：甲苯基、二甲苯基)、1-又或2-萘基、蒽基等之碳數6~20之芳基，較佳者為碳數6~14之芳基，此等烴基可為含有烴基與胺基任一者或兩者。 Further, examples of the aromatic hydrocarbon group which is suitable for R include a phenyl group, a phenyl group substituted with an alkyl group (for example, a tolyl group, a xylyl group), a 1- or 2-naphthyl group, a fluorenyl group or the like. The aryl group of 6 to 20 is preferably an aryl group having 6 to 14 carbon atoms, and the hydrocarbon group may be either or both of a hydrocarbon group and an amine group.

另外，對於R而言適合的雜環基可列舉如：咪唑、***、四唑、苯並咪唑、苯並***、噻唑、苯並噻唑，此雜環基可為含有烴基與胺基任一者或兩者。 Further, a heterocyclic group suitable for R may, for example, be an imidazole, a triazole, a tetrazole, a benzimidazole, a benzotriazole, a thiazole or a benzothiazole, and the heterocyclic group may have a hydrocarbon group and an amine group. One or both.

分子內有兩個以下硫醇基之化合物之較佳的例子可列舉如：3-巰基-1，2-丙二醇、2-巰基乙醇、1，2-乙二硫醇、6-巰基-1-己醇、1-辛烷硫醇、1-十二烷基硫醇、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、p-甲苯硫醇、2，4-二甲基苯硫醇、3-巰基-1，2，4***、2-巰基-苯並噻唑。在其中，以水溶性與廢棄物處理上的觀點來看，3-巰基-1，2-丙二醇為更佳。 Preferable examples of the compound having two or less thiol groups in the molecule include, for example, 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto-1- Hexanol, 1-octanethiol, 1-dodecyl mercaptan, 10-hydroxy-1-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1- Dodecanethiol, sodium 1-dodecyl mercaptan sulfonate, thiophenol, thiobenzoic acid, 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzene sulfur Alcohol, 3-mercapto-1,2,4 triazole, 2-mercapto-benzothiazole. Among them, 3-mercapto-1,2-propanediol is more preferable from the viewpoint of water solubility and waste treatment.

附載子金屬箔以熱壓機密著板狀載子與金屬箔為可能之製造方式。例如：於金屬箔以及/或板狀載子之貼合面以前述分子內有兩個以下硫醇基之化合物所成者被覆處理之後，對金屬箔貼合的表面，以B階段之樹脂製之板狀載子使用熱壓機加以層合，為可能之製造方式。 It is possible to mount a sub-metal foil with a hot press to adhere a plate-shaped carrier and a metal foil. For example, after the metal foil and/or the plate-shaped carrier are coated with a compound having two or less thiol groups in the molecule, the surface to which the metal foil is bonded is made of a B-stage resin. The plate-shaped carriers are laminated using a hot press, which is a possible manufacturing method.

分子內有兩個以下硫醇基之化合物可在水溶液的形態下使 用。為提高對水的溶解度可添加甲醇或乙醇等醇類溶劑。醇類溶劑的添加在使用疏水性高的化合物，其化合物之分子內有兩個以下硫醇基時特別有效。 a compound having two or less thiol groups in the molecule can be made in the form of an aqueous solution use. An alcohol solvent such as methanol or ethanol may be added to increase the solubility in water. The addition of an alcohol solvent is particularly effective when a compound having high hydrophobicity is used, and the compound has two or less thiol groups in its molecule.

分子內有兩個以下硫醇基之化合物在水溶液中的濃度較高時，金屬箔與板狀載子的剝離強度有降低的傾向，可藉由調整分子內有兩個以下硫醇基之化合物的濃度，進一步調整剝離強度。雖無限定，分子內具有兩個以下硫醇基之化合物在水溶液中的濃度可調整為0.01~10.0(%)，傳統上可調整為濃度0.1~5.0(%)。 When the concentration of a compound having two or less thiol groups in a molecule is high in an aqueous solution, the peeling strength of the metal foil and the plate-like carrier tends to decrease, and the compound having two or less thiol groups in the molecule can be adjusted. The concentration is further adjusted for the peel strength. Although not limited, the concentration of the compound having two or less thiol groups in the molecule in the aqueous solution can be adjusted to 0.01 to 10.0 (%), and the concentration can be conventionally adjusted to 0.1 to 5.0 (%).

分子內有兩個以下硫醇基之化合物的水溶液之pH值並無特別限制，酸性或鹼性都可利用。例如pH值範圍在3.0~10.0也可使用。以不需特別調整pH值範圍之觀點來看，落在中性附近5.0~9.0範圍的pH值較佳，落在7.0~9.0範圍的pH值為更佳。 The pH of the aqueous solution of the compound having two or less thiol groups in the molecule is not particularly limited, and both acidic and basic can be utilized. For example, a pH range of 3.0 to 10.0 can also be used. The pH value in the range of 5.0 to 9.0 near neutral is preferable, and the pH falling in the range of 7.0 to 9.0 is more preferable from the viewpoint of not particularly adjusting the pH range.

(3)金屬醇鹽 (3) Metal alkoxide

使用具有下式所示構造之鋁酸鹽化合物、鈦酸鹽化合物、鉻酸鹽化合物或其加水分解生成物或該加水分解生成物之縮合體(以下略記為金屬醇鹽)以單獨或複數混合者，在板狀載子與金屬箔之間進行貼合，適度的將密著性調低，可將剝離強度調節至上述之範圍。 An aluminate compound, a titanate compound, a chromate compound or a hydrolyzed product thereof or a condensate of the hydrolyzed product (hereinafter abbreviated as a metal alkoxide) having a configuration shown by the following formula is used alone or in combination The bonding between the plate-shaped carrier and the metal foil is carried out, and the adhesion is appropriately lowered, and the peeling strength can be adjusted to the above range.

【化17】(R1)m-M-(R2)n (R 1 ) m -M-(R 2 ) n

(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4) (wherein 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 or an aryl group, or a group in which one or more hydrogen atoms are replaced by a halogen atom; a hydrocarbon group; M is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer of 1 or more and valence of M, and at least one of R 1 is an alkoxy group; The valence of m+n is M, which is 3 for Al and 4 for Ti and Zr.

該金屬醇鹽至少必須具有一烷氧基。若不存在烷氧基，選自 烷基、環烷基以及芳基所成群中之烴基，或其一個以上的氫原子被取代為鹵素原子之僅有此等任一烴基構成取代基之情形，板狀載子與金屬箔表面的密著性會有過度低下的傾向。此外，該金屬醇鹽必須具有0~2個，選自烷基、環烷基以及芳基所成群中之烴基，其一個以上的氫原子被取代為鹵素原子之此等任意之烴基。該烴基如具有3個以上時，板狀載子與金屬箔表面的密著性會有過度低下的傾向。又，與本發明相關之烷氧基也包含一個以上的氫原子被取代為鹵素原子的烷氧基的情形。在板狀載子與金屬箔的剝離強度調節至上述範圍時，該金屬醇鹽係以具有兩個以上烷氧基，具有一個或兩個上述烴基(包含一個以上的氫原子被取代為鹵素原子之烴基)為佳。 The metal alkoxide must have at least one alkoxy group. If no alkoxy group is present, selected from a case where a hydrocarbon group in a group of an alkyl group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms thereof is substituted with a halogen atom, and only one of the hydrocarbon groups constitutes a substituent, a plate-shaped carrier and a metal foil surface The adhesion will have a tendency to be excessively low. Further, the metal alkoxide must have 0 to 2 hydrocarbon groups selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, and one or more hydrogen atoms thereof may be substituted with any of the hydrocarbon groups of the halogen atom. When the number of the hydrocarbon groups is three or more, the adhesion between the plate-shaped carrier and the surface of the metal foil tends to be excessively lowered. Further, the alkoxy group related to the present invention also contains a case where one or more alkoxy groups in which a hydrogen atom is substituted with a halogen atom. When the peeling strength of the plate-shaped carrier and the metal foil is adjusted to the above range, the metal alkoxide has two or more alkoxy groups and has one or two of the above hydrocarbon groups (including one or more hydrogen atoms substituted with a halogen atom) The hydrocarbon group is preferred.

又對於烷基而言，雖無限定，但可列舉如：甲基、乙基、n-或iso-丙基、n-、iso-或tert-丁基、n-、iso-或neo-戊基、n-己基、n-辛基、n-癸基等之直鏈或支鏈狀的碳數1~20之烷基、較佳者為碳數1~10之烷基、最佳者為碳數1~5的烷基。 Further, the alkyl group is not limited, but may, for example, be a methyl group, an ethyl group, an n- or iso-propyl group, an n-, iso- or tert-butyl group, an n-, iso- or neo-pentane group. a linear or branched alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, preferably an n-hexyl group, an n-octyl group or an n-fluorenyl group. An alkyl group having 1 to 5 carbon atoms.

另外，對於環烷基而言，雖無限定但可列舉如：環丙基、環丁基、環戊基、環己基、環庚基、環辛基等其碳數3~10之環烷基、較佳者為碳數5~7之環烷基者。 Further, the cycloalkyl group is not limited, and examples thereof include a cycloalkyl group having a carbon number of 3 to 10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Preferably, it is a cycloalkyl group having 5 to 7 carbon atoms.

另外，對於R2而言適合的芳香族烴基可列舉如：苯基、以烷基取代之苯基(例：甲苯基、二甲苯基)、1-又或2-萘基、蒽基等之碳數6~20之芳基，較佳者為碳數6~14之芳基，此等烴基可為含有烴基與胺基任一者或兩者。 Further, examples of the aromatic hydrocarbon group suitable for 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, anthracenyl group and the like. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 14 carbon atoms, and the hydrocarbon group may be either or both of a hydrocarbon group and an amine group.

此等烴基之一個以上的氫原子可以鹵素原子取代，例如可取代為：氟原子、氯原子、或溴原子。 One or more hydrogen atoms of these hydrocarbon groups may be substituted by a halogen atom, and may be, for example, a fluorine atom, a chlorine atom, or a bromine atom.

較佳的鋁酸鹽化合物可列舉如：三甲基鋁、甲基二甲氧基鋁、乙基二甲氧基鋁、n-或iso-丙基二甲氧基鋁、n-、iso-或tert-丁基二甲氧基鋁、n-、iso-或neo-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(如：p-(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、n-或iso-丙基二乙氧基鋁、n-、iso-或tert-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(如：p-(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、n-或iso-丙基二乙氧基鋁、n-、iso-或tert-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(如：p-(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、以及十三氟辛基二乙氧基鋁、甲基二氯化鋁、二甲基氯化鋁、二甲基氯化鋁、苯基二氯化鋁、二甲基氟化鋁、二甲基溴化鋁、二苯基溴化鋁、此等之加水分解生成物，以及此等之加水分解生成物之縮合體等為例；在其中，以取得容易的觀點來看，三甲氧基鋁、三乙氧基鋁、三異丙氧基鋁，為更佳。 Preferred aluminate compounds are, for example, trimethyl aluminum, methyl dimethoxy aluminum, ethyl dimethoxy aluminum, n- or iso-propyl dimethoxy aluminum, n-, iso- Or tert-butyldimethoxyaluminum, n-, iso- or neo-pentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, Phenyldimethoxyaluminum; alkyl-substituted phenyldimethoxyaluminum (eg p-(methyl)phenyldimethoxyaluminum), dimethylforma Aluminium oxy, triethoxy aluminum, methyl diethoxy aluminum, ethyl diethoxy aluminum, n- or iso-propyl diethoxy aluminum, n-, iso- or tert-butyl Ethoxy aluminum, pentyl diethoxy aluminum, hexyl diethoxy aluminum, octyl diethoxy aluminum, decyl diethoxy aluminum, phenyl diethoxy aluminum, alkyl substituted phenyl Aluminum ethoxylate (such as: p-(methyl)phenyldiethoxyaluminum), dimethyl ethoxylated aluminum, aluminum triisopropoxide, aluminum methyl diisopropoxide, ethyl diiso Aluminum propoxide, n- or iso-propyl diethoxy aluminum, n-, iso- or tert-butyl diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy Aluminum, octyl aluminum diisopropoxide, aluminum decyl diisopropoxide, aluminum phenyl diisopropoxide, aluminum substituted alkyl phenyl diisopropoxide (eg p-(methyl) benzene Al-isopropoxy aluminum), dimethylisopropoxy aluminum, (3,3,3-trifluoropropyl)dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyl Aluminum dichloride, dimethyl aluminum chloride, dimethyl aluminum chloride, phenyl aluminum dichloride, dimethyl aluminum fluoride, dimethyl aluminum bromide, diphenyl aluminum bromide, etc. Examples of the water-decomposition product, a condensate of the hydrolyzed product, and the like are used, and among them, trimethoxy aluminum, triethoxy aluminum, and triisopropoxy aluminum are used for the sake of easy availability. Better.

較佳的鈦酸鹽化合物可列舉如：四甲氧基鈦、甲基三甲氧基鈦、乙基三甲氧基鈦、n-或iso-丙基三甲氧基鈦、n-、iso-或tert-丁基三甲氧基鈦、n-、iso-或neo-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(如：p-(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、n-或iso-丙基三乙氧基鈦、n-、iso-或tert-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(如：p-(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、n-或iso-丙基三乙氧基鈦、n-、iso-或tert-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(如：p-(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、以及十三氟辛基三乙氧基鈦、甲 基三氯化鈦、二甲基二氯化鈦、三甲基氯化鈦、苯基三氯化鈦、二甲基二氟化鈦、二甲基二溴化鈦、二苯基二溴化鈦、此等之加水分解生成物，以及此等之加水分解生成物之縮合體等為例；在其中，以取得容易的觀點來看，四甲氧基鈦、四乙氧基鈦、四異丙氧基鈦，為更佳。 Preferred titanate compounds include, for example, tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or iso-propyltrimethoxytitanium, n-, iso- or tert - butyl trimethoxytitanium, n-, iso- or neo-pentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; Alkyl substituted phenyltrimethoxytitanium (e.g., p-(methyl)phenyltrimethoxytitanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, B Base triethoxytitanium, n- or iso-propyltriethoxytitanium, n-, iso- or tert-butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium , octyl triethoxy titanium, decyl triethoxy titanium, phenyl triethoxy titanium, alkyl substituted phenyl triethoxy titanium (eg: p-(methyl)phenyl triethoxy Titanium), dimethyldiethoxytitanium, titanium tetraisopropoxide, titanium triisopropoxytitanium, titanium triisopropoxytitanium, n- or iso-propyltriethoxytitanium, N-, iso- or tert-butyl titanium triisopropoxide, titanium pentyl triisopropoxide, titanium hexyl triisopropoxide, octyl tris Titanium propoxide, titanium decyl triisopropoxide, titanium phenyl triisopropoxide, titanium substituted alkyl phenyl triisopropoxide (eg p-(methyl)phenyl triisopropoxy) Titanium), dimethyldiisopropoxytitanium, (3,3,3-trifluoropropyl)trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, A Base of titanium trichloride, dimethyl titanium dichloride, trimethyl titanium chloride, phenyl titanium trichloride, titanium dimethyl difluoride, titanium dimethyl dibromide, diphenyl dibromination Examples of titanium, such a hydrolyzed product, and a condensate of such a hydrolyzed product; among them, tetramethoxytitanium, tetraethoxytitanium, and tetraiso are preferable from the viewpoint of availability. Titanium propoxide is preferred.

較佳的鋯酸鹽化合物可列舉如：四甲氧基鋯、甲基三甲氧基鋯、乙基三甲氧基鋯、n-或iso-丙基三甲氧基鋯、n-、iso-或tert-丁基三甲氧基鋯、n-、iso-或neo-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(如：p-(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、n-或iso-丙基三乙氧基鋯、n-、iso-或tert-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(如：p-(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、n-或iso-丙基三乙氧基鋯、n-、iso-或tert-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(如：p-(甲基)苯基三異丙氧基鋯)、二甲基二異丙氧基鋯、(3,3,3-三氟丙基)三甲氧基鋯、以及十三氟辛基三乙氧基鋯、甲基三氯化鋯、二甲基二氯化鋯、三甲基氯化鋯、苯基三氯化鋯、二甲基二氟化鋯、二甲基二溴化鋯、二苯基二溴化鋯、此等之加水分解生成物，以及此等之加水分解生成物之縮合體等為例；在其中，以取得容易的觀點來看，四甲氧基鋯、四乙氧基鋯、四異丙氧基鋯，為更佳。 Preferred zirconate compounds are, for example, tetramethoxy zirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert -butyltrimethoxyzirconium, n-, iso- or neo-pentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; Alkyl substituted phenyltrimethoxy zirconium (eg p-(methyl)phenyltrimethoxyzirconium), dimethyldimethoxyzirconium, tetraethoxyzirconium, methyltriethoxyzirconium, B Zirconium triethoxy zirconium, n- or iso-propyl triethoxy zirconium, n-, iso- or tert-butyl triethoxy zirconium, pentyl triethoxy zirconium, hexyl triethoxy zirconium , octyltriethoxy zirconium, decyltriethoxyzirconium, phenyltriethoxyzirconium, alkyl substituted phenyltriethoxyzirconium (eg p-(methyl)phenyltriethoxy) Zirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- or iso-propyltriethoxyzirconium, N-, iso- or tert-butyl triisopropoxy zirconium, pentyl triisopropoxy zirconium, hexyl triisopropoxy zirconium, octyl triiso Zirconium propoxide, zirconium decyl triisopropoxide, zirconium phenyl triisopropoxide, zirconium alkyl substituted phenyl triisopropoxide (eg p-(methyl)phenyl triisopropoxy) Zirconium), zirconium dimethyldisisopropoxide, zirconium (3,3,3-trifluoropropyl)trimethoxy, and trifluorooctyltrisyltriethoxyzirconium, methyltrichloride zirconium, Methyl zirconium dichloride, trimethyl zirconium chloride, phenyl zirconium trichloride, zirconium dimethyl difluoride, zirconium dimethyl zirconium dichloride, zirconium diphenyl zirconium dichloride, water hydrolysis The product and the condensate of the hydrolyzed product and the like are exemplified; among them, tetramethoxy zirconium, tetraethoxy zirconium, and tetraisopropoxy zirconium are more preferable from the viewpoint of availability. good.

附載子金屬箔以熱壓機密著板狀載子與金屬箔為可能之製造方式。例如：於金屬箔以及/或板狀載子之貼合面以前述金屬醇鹽做塗層處理之後，對金屬箔貼合的表面，以B階段之樹脂製之板狀載子使用熱壓機加以層合，為可能之製造方式。 It is possible to mount a sub-metal foil with a hot press to adhere a plate-shaped carrier and a metal foil. For example, after the metal foil and/or the plate-shaped carrier are coated with the metal alkoxide as described above, the surface of the metal foil is bonded to the surface of the plate-shaped resin using a hot press. Laminating is possible as a manufacturing method.

金屬醇鹽可在水溶液的形態下使用。為提高對水的溶解度可添加甲醇或乙醇等醇類溶劑。醇類溶劑的添加在使用疏水性高的金屬醇鹽 時特別有效。 The metal alkoxide can be used in the form of an aqueous solution. An alcohol solvent such as methanol or ethanol may be added to increase the solubility in water. The addition of an alcohol solvent uses a highly hydrophobic metal alkoxide It is especially effective.

金屬醇鹽在水溶液中的濃度較高時，金屬箔與板狀載子的剝離強度有降低的傾向，可藉由金屬醇鹽的濃度調整，調整剝離強度。雖無限定，金屬醇鹽在水溶液中的濃度可調整為0.001~1.0mol/L，傳統上可調整為0.005~0.2mol/L。 When the concentration of the metal alkoxide in the aqueous solution is high, the peel strength of the metal foil and the plate-shaped carrier tends to decrease, and the peel strength can be adjusted by adjusting the concentration of the metal alkoxide. Although not limited, the concentration of the metal alkoxide in the aqueous solution can be adjusted to 0.001 to 1.0 mol/L, which can be conventionally adjusted to 0.005 to 0.2 mol/L.

金屬醇鹽的水溶液之pH值並無特別限制，酸性或鹼性都可利用。例如pH值範圍在3.0~10.0也可使用。以不需特別調整pH值範圍之觀點來看，落在中性附近5.0~9.0範圍的pH值較佳，落在7.0~9.0範圍的pH值為更佳。 The pH of the aqueous solution of the metal alkoxide is not particularly limited, and both acidic and basic can be utilized. For example, a pH range of 3.0 to 10.0 can also be used. The pH value in the range of 5.0 to 9.0 near neutral is preferable, and the pH falling in the range of 7.0 to 9.0 is more preferable from the viewpoint of not particularly adjusting the pH range.

(4)樹脂塗膜所形成之離型材 (4) Release profile formed by resin coating film

板狀載子與金屬箔以使用選自矽酮(Silicone)、環氧系樹脂(Epoxy)、三聚氰胺系樹脂(Melamine)及氟樹脂(Fluoropolymer)中之一種或數種樹脂構成之樹脂塗膜所貼合，適度的將密著性調低，可將剝離強度調節至後述之範圍。 The plate-shaped carrier and the metal foil are a resin coating film comprising one or more resins selected from the group consisting of Silicone, Epoxy, Melamine, and Fluoropolymer. The adhesion is adjusted to a moderate degree, and the peel strength can be adjusted to the range described later.

為了實現具有此等密著性的剝離強度的調節，其方式係如後述使用選自矽酮(Silicone)、環氧系樹脂(Epoxy)、三聚氰胺系樹脂(Melamine)及氟樹脂(Fluoropolymer)中之一種或數種樹脂構成之樹脂塗膜。此等樹脂塗膜以後述所定條件進行烘烤處理，並使用於板狀載子與金屬箔之間，以熱壓機加以貼合，適度的將密著性調低，可將剝離強度調節至上述之範圍。 In order to achieve the adjustment of the peel strength having such adhesion, the method is selected from the group consisting of Silicone, Epoxy, Melamine, and Fluoropolymer as described below. A resin coating film composed of one or several kinds of resins. These resin coating films are subjected to baking treatment under the conditions described later, and are applied between a plate-shaped carrier and a metal foil by a hot press, and the adhesion is appropriately lowered to adjust the peel strength to The above range.

對於環氧系樹脂而言，可列舉如：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、柔性環氧樹脂、氫化雙酚A型環氧樹脂、苯氧基樹脂、溴化苯氧基樹脂等。 Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, brominated epoxy resin, amine epoxy resin, and flexible epoxy resin. Resin, hydrogenated bisphenol A type epoxy resin, phenoxy resin, brominated phenoxy resin, and the like.

對於三聚氰胺系樹脂而言，可列舉如：甲基醚三聚氰胺樹脂，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，丁醇變性三聚氰胺樹脂等。又，三聚氰胺系樹脂也可係為前記樹脂與丁基化尿素樹脂、丁基化苯代三聚氰胺樹脂。 Examples of the melamine-based resin include methyl ether melamine resin, butylated urea melamine resin, butylated melamine resin, methylated melamine resin, and butanol-modified melamine resin. Further, the melamine resin may be a pre-recorded resin, a butylated urea resin, or a butylated benzene melamine resin.

又，環氧系樹脂之數量平均分子量係2000~3000， 三聚氰胺系樹脂之數量平均分子量係500~1000為佳。藉由具有此等數量平均分子量，即可伴隨樹脂可能塗料化，樹脂塗膜的接著強度較易調整至所定之範圍。 Moreover, the number average molecular weight of the epoxy resin is 2,000 to 3,000. The number average molecular weight of the melamine resin is preferably from 500 to 1,000. By having such an average number of molecular weights, the resin can be coated, and the adhesive strength of the resin coating film can be easily adjusted to a predetermined range.

又對於氟樹脂而言，可列舉如：聚四氟乙烯，聚氯三氟乙烯，聚偏二氟乙烯，聚氟乙烯等。 Further, examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.

對於矽酮而言，可列舉如：甲基苯基聚矽氧烷、甲基氫聚矽氧烷、二甲基聚矽氧烷、變性二甲基聚矽氧烷，其等之混合物等。在此，變性係可列舉如：環氧基變性、烷基變性、胺基變性、羧基變性、醇基變性、氟變性、烷基芳基聚醚變性、環氧聚醚變性、聚醚變性、烷基高級醇酯變性、聚酯變性、酰氧基烷基變性、鹵代烷基酰氧基烷基變性、鹵代烷基變性、胺基二醇變性、硫醇基變性、含羥基聚酯變性等。 Examples of the anthrone include a methylphenyl polyoxyalkylene, a methylhydrogenpolysiloxane, a dimethylpolysiloxane, a denatured dimethylpolysiloxane, a mixture thereof, and the like. Here, examples of the denaturation include epoxy group denaturation, alkyl group denaturation, amine group denaturation, carboxyl group degeneration, alcohol group denaturation, fluorine denaturation, alkyl aryl polyether denaturation, epoxy polyether denaturation, and polyether denaturation. Alkyl higher alcohol ester denaturation, polyester denaturation, acyloxyalkyl denaturation, haloalkyl acyloxyalkyl denaturation, haloalkyl denaturation, amino diol denaturation, thiol group denaturation, hydroxyl group-containing polyester denaturation, and the like.

樹脂塗膜中，膜的厚度太小，太過薄膜會使得樹脂塗膜難以形成，而容易使生產率降低。又，膜的厚度超過一定大小，樹脂塗膜的剝離性並不會更進一步提高，而樹脂塗膜之製造成本容易提高。由此觀點來看，樹脂塗膜之膜厚以0．1~10μm較佳，且以0．5~5μm為更佳。且，樹脂塗膜之膜厚可藉由後述的程序中，樹脂塗料依所定的塗佈量進行塗佈，達到適當的厚度。 In the resin coating film, the thickness of the film is too small, and too much film makes the resin coating film difficult to form, and it is easy to lower the productivity. Further, when the thickness of the film exceeds a certain size, the peeling property of the resin coating film is not further improved, and the production cost of the resin coating film is likely to be improved. From this point of view, the film thickness of the resin coating film is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm . Further, the film thickness of the resin coating film can be applied to a suitable thickness by a resin coating material according to a predetermined coating amount in a procedure to be described later.

樹脂塗膜中，矽酮的機能係作為樹脂塗膜的剝離劑。於此，若與矽酮相比，環氧系樹脂、三聚氰胺系樹脂的合計量過多時，樹脂塗膜賦予板狀載子與金屬箔之間的剝離強度將會變大，樹脂塗膜的剝離性降低，將不容易以人工方式剝離。另一方面，若與矽酮相比，環氧系樹脂、三聚氰胺系樹脂的合計量過少時，前述之剝離強度將會變小，附載子金屬箔於搬運或加工時可能會有剝離的情形。由此觀點來看，相對於矽酮為100質量單位，環氧系樹脂、三聚氰胺系樹脂的合計含有10~1500質量單位為佳，且含有20~800重量單位為更佳。 In the resin coating film, the function of the fluorenone is used as a release agent for the resin coating film. When the total amount of the epoxy resin or the melamine resin is too large compared with the fluorenone, the peeling strength between the plate-shaped carrier and the metal foil is increased by the resin coating film, and the peeling of the resin coating film is increased. Reduced sex will not be easily stripped manually. On the other hand, when the total amount of the epoxy resin or the melamine resin is too small as compared with the fluorenone, the peel strength described above will be small, and the attached metal foil may be peeled off during handling or processing. From this point of view, the total amount of the epoxy resin and the melamine resin is preferably from 10 to 1,500 by mass, and more preferably from 20 to 800 parts by weight, per 100 parts by mass of the fluorenone.

又，氟樹脂與矽酮相同，其機能係作為剝離劑，能使樹脂塗膜之耐熱性有向上提高的效果。若與矽酮相比，氟樹脂過多時，前述之剝離強度將會變小，附載子金屬箔於搬運或加工時可能會有剝離的情形，且為了達到後述烘烤步驟所必需的溫度，將會造成浪費。由此觀點來看，相 對於矽酮為100質量單位，氟樹脂為0~50質量單位為佳，且為0~40質量單位為更佳。 Further, the fluororesin is the same as the fluorenone, and its function as a release agent can improve the heat resistance of the resin coating film. When the fluororesin is too much compared with the fluorenone, the peeling strength described above will become small, and the attached sub-metal foil may be peeled off during handling or processing, and in order to reach the temperature necessary for the baking step described later, Will cause waste. From this point of view, the phase For the fluorenone is 100 mass units, the fluororesin is preferably 0 to 50 mass units, and more preferably 0 to 40 mass units.

樹脂塗膜係加入矽酮、環氧系樹脂及/或三聚氰胺系樹脂，及必要時所需之氟樹脂，並包含選自SiO2、MgO、Al2O3、BaSO4及Mg(OH)2中一種以上之表面粗化粒子的所成者。由於樹脂塗膜含有表面粗化粒子，樹脂塗膜會形成凹凸之表面。藉由樹脂塗膜的凹凸情形，將其塗佈於板狀載子或金屬箔，使形成凹凸、消光之表面。對於表面粗化粒子的含量而言，僅需使樹脂塗膜凹凸化，並無特別限定，但相對於矽酮為100質量單位，其含量為1~10質量單位為佳。 The resin coating film is an oxime ketone, an epoxy resin, and/or a melamine resin, and a fluororesin which is required if necessary, and contains SiO 2 , MgO, Al 2 O 3 , BaSO 4 , and Mg(OH) 2 . One or more of the surface roughening particles. Since the resin coating film contains surface roughening particles, the resin coating film forms a rough surface. By the unevenness of the resin coating film, it is applied to a plate-shaped carrier or a metal foil to form a surface on which irregularities and matting are formed. The content of the surface roughened particles is not particularly limited as long as the resin coating film is roughened, but the content is preferably 1 to 10 mass units per 100 parts by mass of the fluorenone.

表面粗化粒子的粒徑係15nm~4μm為佳。在此，粒徑係由電子掃描顯微鏡(SEM)照片等測定之平均粒徑(最大粒徑與最小粒徑的平均值)所定義。表面粗化粒子的粒徑在前記範圍內，可較容易調整樹脂塗膜表面之凹凸量，其結果可使板狀載子或金屬箔的表面之凹凸量調整更為容易。具體的說，板狀載子或金屬箔的表面之凹凸量為依據JIS規定的最大全粗糙度高度Ry之4．0μm左右。 The particle size of the surface roughened particles is preferably 15 nm to 4 μm . Here, the particle diameter is defined by an average particle diameter (average value of the maximum particle diameter and the minimum particle diameter) measured by a scanning electron microscope (SEM) photograph or the like. The particle diameter of the surface roughened particles is within the range of the foregoing, and the amount of unevenness on the surface of the resin coating film can be easily adjusted, and as a result, the amount of unevenness on the surface of the plate-shaped carrier or the metal foil can be easily adjusted. Specifically, the amount of irregularities on the surface of the plate-shaped carrier or the metal foil is about 4.0 μm in accordance with the maximum full roughness height Ry prescribed by JIS.

在此，將說明關於附載子金屬箔的製造方法。 Here, a method of manufacturing the attached sub-metal foil will be described.

此附載子金屬箔係經由以下程序所得者：將板狀載子或金屬箔之至少一方的表面，以上述之樹脂塗膜進行塗佈步驟，並將塗佈後之樹脂塗膜以烘烤步驟使其硬化。以下，將說明關於各項步驟。 The attached sub-metal foil is obtained by the following procedure: a surface of at least one of a plate-shaped carrier or a metal foil is coated with the above-mentioned resin coating film, and the coated resin coating film is subjected to a baking step. Make it harden. Hereinafter, the steps will be explained.

(塗佈步驟) (coating step)

塗佈步驟係由作為主劑的矽酮、作為硬化劑的環氧系樹脂、三聚氰胺系樹脂，及必要時所需之氟樹脂所成之樹脂塗料，塗佈於板狀載子之單面或雙面，使形成樹脂塗膜的步驟。樹脂塗料係以乙醇等有機溶劑溶解環氧系樹脂、三聚氰胺系樹脂、氟樹脂及矽酮所得之物。又，樹脂塗料的摻混量(添加量)為，相對於矽酮為100質量單位，環氧系樹脂、三聚氰胺系樹脂的合計為10~1500質量單位為佳。且，相對於矽酮為100質量單位，氟樹脂為0~50質量單位為佳。 The coating step is applied to a single side of a plate-shaped carrier by a resin coating made of an anthrone as a main component, an epoxy resin as a curing agent, a melamine resin, and a fluororesin if necessary. The step of forming a resin coating film on both sides. The resin coating material is obtained by dissolving an epoxy resin, a melamine resin, a fluororesin, and an anthrone in an organic solvent such as ethanol. In addition, the blending amount (addition amount) of the resin coating material is preferably 100 to 1500 mass units, and the total of the epoxy resin and the melamine resin is preferably 100 to 1,500 mass units. Further, the fluororesin is preferably from 0 to 50 mass units, and the fluororesin is preferably from 0 to 50 mass units.

對於塗佈步驟中的塗佈方法而言，僅需能形成樹脂塗膜，並無特別限定，但會採用凹版塗佈法(Rotogravure-Coating)、棒式塗佈法 (Bar-Coating)、滾輪式塗布法(roll-Coating)、淋幕塗佈(curtain flow-coating)及使用靜電塗裝機等方法，從樹脂塗膜的均一性，及操作的簡便性來看，使用凹版塗佈法為佳。又，對於塗佈量而言，樹脂塗膜3較佳的厚度為：厚度為0．5~5μm時，樹脂量係以1．0~2．0g/m2為佳。 The coating method in the coating step is only required to form a resin coating film, and is not particularly limited, but a gravure coating method (Rotogravure-Coating), a bar coating method (Bar-Coating), and a roller are used. By the method of roll-coating, curtain flow-coating, and using an electrostatic coating machine, the gravure coating method is used from the viewpoint of the uniformity of the resin coating film and the ease of handling. good. Further, the coating amount of the resin coating film 3 is preferably a thickness of 0.5 to 5 μm , and the resin amount is preferably 1.0 to 2.0 g/m 2 .

凹版塗佈法係於滾筒表面所設置的凹部(單元)中填滿樹脂塗料，並將其樹脂塗料轉印於板狀載子，使板狀載子表面形成樹脂塗料的方法。具體的說，表面設置單元之下側滾輪的下部浸漬於樹脂塗料中，當下側滾輪迴轉時，單元內的樹脂塗膜會被汲取上來。並且，將板狀載子配置於下側滾輪與下側滾輪上側所配置的上側滾輪之間，上側滾輪將板狀載子押付於下側滾輪，藉由下側滾輪及上側滾輪的迴轉，板狀載子被運送的同時，於單元內被抽取上來的樹脂塗料會轉印(塗佈)於板狀載子的單面上。 The gravure coating method is a method in which a resin coating is filled in a concave portion (unit) provided on a surface of a drum, and a resin coating material is transferred to a plate-shaped carrier to form a resin coating on the surface of the plate-shaped carrier. Specifically, the lower portion of the lower roller of the surface setting unit is immersed in the resin paint, and when the lower roller is rotated, the resin coating film in the unit is taken up. Further, the plate-shaped carrier is disposed between the lower roller and the upper roller disposed on the upper side of the lower roller, and the upper roller urges the plate-shaped carrier to the lower roller, and the lower roller and the upper roller rotate. While the carrier is being transported, the resin coating extracted in the unit is transferred (coated) on one side of the plate-shaped carrier.

又，於板狀載子之送入側，配置刮刀，使其與下側滾輪之表面接觸，可除去單元以外之滾輪表面所過多汲取之樹脂塗料，使板狀載子之表面能塗佈所定量的樹脂塗料。且單元的支數(大小及深度)為大之情形，或樹脂塗料為高黏度之情形，於板狀載子的單面所形成之樹脂塗膜將較難具有平滑度，為此，可在板狀載子的送出側設置平滑滾輪，使能維持樹脂塗膜之平滑度。 Further, on the feeding side of the plate-shaped carrier, a doctor blade is placed in contact with the surface of the lower roller, and the resin coating which is excessively taken from the surface of the roller other than the unit can be removed, and the surface of the plate-shaped carrier can be coated. Quantitative resin coatings. When the number of cells (size and depth) is large, or the resin coating is high in viscosity, the resin coating film formed on one side of the plate-shaped carrier will be difficult to have smoothness. A smoothing roller is provided on the feeding side of the plate-shaped carrier to maintain the smoothness of the resin coating film.

又，若欲使板狀載子之雙面形成樹脂塗膜的情形，係在板狀載的之單面形成樹脂塗膜後，將板狀載子反轉，再次將其配置於下側滾輪與上側滾輪之間。並且，與前記相同，下側滾輪之單元內的樹脂塗料將轉印(塗佈)於板狀載子的內面。 Further, when a resin coating film is to be formed on both sides of the plate-shaped carrier, the resin coating film is formed on one side of the plate-shaped carrier, and then the plate-shaped carrier is reversed and placed on the lower roller again. Between the upper roller and the upper roller. Further, as in the previous note, the resin paint in the unit of the lower roller is transferred (coated) to the inner surface of the plate-shaped carrier.

(烘烤步驟) (baking step)

烘烤步驟係將塗佈步驟所形成之樹脂塗膜在0．5~60秒間(烘烤時間)以125~320℃(烘烤溫度)進行烘烤處理之步驟。如此，於所定摻混量之樹脂塗料形成的樹脂塗膜施予所定條件之烘烤處理，可使附著有樹脂塗膜之板狀載子與金屬箔之間的剝離強度控制在所定範圍之內。於本發明中，烘烤溫度即為板狀載子之形成溫度。又，烘烤處理所使用之加熱方法係利用傳統上公認已知之設備。 The baking step is a step of baking the resin coating film formed in the coating step at a temperature of 125 to 320 ° C (baking temperature) for 0.5 to 60 seconds (baking time). In this manner, the resin coating film formed of the resin coating material of a predetermined blending amount is subjected to a baking treatment under predetermined conditions, and the peeling strength between the plate-shaped carrier and the metal foil to which the resin coating film is attached can be controlled within a predetermined range. . In the present invention, the baking temperature is the formation temperature of the plate-shaped carrier. Further, the heating method used in the baking treatment utilizes a device conventionally recognized.

烘烤不完全之條件，例如烘烤溫度未達125℃，或烘烤時間未達0．5秒之情形，樹脂塗膜將無法充分硬化，上述剝離強度超過200gf/cm，而使剝離性下降。又，烘烤過度之條件，例如烘烤溫度超過320℃之情形，樹脂塗膜將會劣化，上述剝離強度超過200gf/cm，而使剝離時之操作性惡化。或者，板狀載子因高溫而變質。又，烘烤時間超過60秒之情形，生產率則會下降。 Incompletely baked conditions, such as when the baking temperature is less than 125 ° C, or the baking time is less than 0.5 seconds, the resin coating film will not be sufficiently hardened, and the above peeling strength exceeds 200 gf / cm, and the peeling property is lowered. . Further, in the case where the baking is excessive, for example, when the baking temperature exceeds 320 ° C, the resin coating film is deteriorated, and the peeling strength exceeds 200 gf/cm, and the workability at the time of peeling is deteriorated. Alternatively, the plate-shaped carrier is deteriorated due to high temperature. Moreover, when the baking time exceeds 60 seconds, the productivity is lowered.

在附載子金屬箔之製造方法中，前述塗佈步驟之樹脂塗料也可由作為主劑的矽酮、作為硬化劑的環氧系樹脂、三聚氰胺系樹脂與作為剝離劑的氟樹脂，及選自SiO2、MgO、Al2O3、BaSO4及Mg(OH)2中一種以上之表面粗化粒子的所成者。 In the method for producing a carrier metal foil, the resin coating material in the coating step may be an anthrone as a main component, an epoxy resin as a curing agent, a melamine resin, a fluororesin as a release agent, and a SiO selected from the group consisting of SiO. 2. A composition of one or more surface roughening particles of MgO, Al 2 O 3 , BaSO 4 and Mg(OH) 2 .

具體的說，樹脂塗料係為前述添加矽酮之樹脂溶液中，更進一步添加表面粗化粒子所成者。如此於樹脂塗料中添加表面粗化粒子，可使樹脂塗膜形成凹凸之表面，藉由如此凹凸情形，使板狀載子或金屬箔形成凹凸、消光之表面。並且，為了得到具有消光表面的板狀載子或金屬箔，於樹脂塗料中之表面粗化粒子之摻混量(添加量)係，相對於矽酮為100質量單位，其含量為1~10質量單位為佳。又，表面粗化粒子之粒徑係15nm~4μm為更佳。 Specifically, the resin coating material is one in which the surface roughening particles are further added to the above-mentioned resin solution to which an anthrone is added. By adding the surface roughening particles to the resin coating material as described above, the resin coating film can be formed into a rough surface, and the surface of the plate-like carrier or the metal foil can be formed into a concave-convex or matte surface by the unevenness. Further, in order to obtain a plate-shaped carrier or a metal foil having a matte surface, the amount of the surface roughening particles in the resin coating material (addition amount) is 100 mass units with respect to the fluorenone, and the content thereof is 1 to 10 The quality unit is better. Further, the particle diameter of the surface roughened particles is preferably 15 nm to 4 μm .

相關於本發明之製造方法，如同以上說明，且在前述各項步驟中不產生不良影響的範圍內，可於前述各項步驟之間或者前後，包含其他步驟。例如可於塗佈步驟之前，進行將板狀載子的表面洗淨之洗淨步驟。 The manufacturing method according to the present invention, as described above, and in the range in which the adverse effects are not caused in the foregoing steps, may include other steps between or before and after the foregoing steps. For example, a washing step of washing the surface of the plate-shaped carrier may be performed before the coating step.

(於多層印刷配線板的製造過程中，考慮熱處理歷程之剝離強度) (In the manufacturing process of multilayer printed wiring boards, consider the peel strength of the heat treatment process)

一般而言，於多層印刷配線板的製造過程中，於層合步驟或除膠步驟中多有加熱處理步驟。因此，附載子金屬箔的受熱歷程，將隨著層合數的提高變得更為嚴峻。為此，特別在多層印刷配線板的適用考量上，經過所需的熱處理歷程後，金屬箔與板狀載子的剝離強度仍在前述的範圍內較為理想。 In general, in the manufacturing process of a multilayer printed wiring board, there are many heat treatment steps in the laminating step or the de-glue step. Therefore, the heat history of the attached sub-metal foil will become more severe as the number of laminations increases. For this reason, in particular, in the application consideration of the multilayer printed wiring board, after the required heat treatment process, the peeling strength of the metal foil and the plate-shaped carrier is still within the above range.

為此，於本發明之更佳的實施形態之中，預設了於多層印刷配線板之製造過程中之加熱條件，例如：於220℃經過3小時、6小時 或9小時之中至少一個加熱程序後，金屬箔與板狀載子的剝離強度，以30gf/cm以上為佳、50gf/cm以上為更佳。又，該剝離強度，以200gf/cm以下為佳、150gf/cm以下為更佳、80gf/cm以下為最佳。 For this reason, in a more preferred embodiment of the present invention, the heating conditions in the manufacturing process of the multilayer printed wiring board are preset, for example, 3 hours and 6 hours at 220 ° C. After at least one of the heating procedures for 9 hours, the peeling strength of the metal foil and the plate-shaped carrier is preferably 30 gf/cm or more, more preferably 50 gf/cm or more. Further, the peel strength is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, and most preferably 80 gf/cm or less.

關於220℃加熱後之剝離強度，從能夠對應各式各樣層合數的觀點來看，經3小時後及6小時後之兩者、或經6小時及9小時後之兩者中剝離強度係以能滿足上述範圍者為佳，經3小時、6小時以及9小時後的全程序之剝離範圍能滿足上述範圍者為更佳。 Regarding the peel strength after heating at 220 ° C, the peel strength was obtained after 3 hours and 6 hours, or after 6 hours and 9 hours, from the viewpoint of being able to correspond to the respective number of layers. It is preferable to satisfy the above range, and it is more preferable that the peeling range of the entire procedure after 3 hours, 6 hours, and 9 hours can satisfy the above range.

於本發明中，剝離強度係依據JIS C6481規定之90度剝離強度測定方法測定之。 In the present invention, the peel strength is measured in accordance with the 90-degree peel strength measuring method specified in JIS C6481.

以下，將說明關於為實現此剝離強度之各材料之具體構成要件。 Hereinafter, specific constitutional requirements for each material for achieving the peel strength will be explained.

做為板狀載子用之樹脂，雖無特別限制，但可使用苯酚樹脂、聚醯亞胺樹脂、環氧樹脂、天然橡膠、松脂等，但以熱硬化性樹脂為佳。另外，也可使用預浸漬片。與金屬箔貼合前的預浸漬片可為B階段之狀態也可使用。因預浸漬片(C階段)的線膨脹係數為12~18(×10-6/℃)，與作為基板之構成材料銅箔之16.5(×10-6/℃)，或SUS壓板之17.3(×10-6/℃)幾乎相等，因此加壓前後的基板大小與設計時相異現象(縮放變化)造成的電路的位置的偏移，就難以發生為其優點。更進一步的說，利用此等優點之加成效果，多層之極薄無芯基板的生產也係為可能。在此使用之預浸漬片，可與構成電路基板的預浸漬片相同，也可與之相異。傳統上，係使用金屬板作為附載子金屬箔之板狀載子；在這個情況下，板狀載子與金屬箔藉由熔接或接著的方式使之密著。在使用接著劑的情況，以耐熱性之觀點來看，一般而言適合用於組合者並不多見，在藉由熔接使之密著的情況，如使用全面熔接的方式剝離強度過高，於後段希易於以人工方式剝離之步驟將轉為困難，若使用部分熔接會使板狀載子與金屬箔之間藥液的滲入防止轉為困難，不管從甚麼方向討論，組合步驟並非為一適合的方式。於是，藉著使用樹脂製之板狀載子，可發揮與金屬箔之間適度的剝離強度，且藉由使用耐熱性樹脂可充分承受於組合步驟 時的受熱歷程。又，對於所使用之耐熱性樹脂而言，其為公認已知者即可。 The resin used for the plate-shaped carrier is not particularly limited, but a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, a rosin or the like can be used, but a thermosetting resin is preferred. In addition, prepreg sheets can also be used. The prepreg before bonding with the metal foil may be in a B-stage state or may be used. Due to the linear expansion coefficient of the prepreg (C stage) is 12 ~ 18 (× 10 -6 / ℃), 16.5 and a copper foil as the constituent material of the substrate (× 10 -6 / ℃), or platen of SUS 17.3 ( × 10 -6 / ℃) are approximately equal, the offset position of the circuit board size before and after pressing with a different design of the phenomenon (scaling change) caused, it is difficult for its advantages occur. Furthermore, with the additive effect of these advantages, the production of a multi-layered ultra-thin coreless substrate is also possible. The prepreg used herein may be the same as or different from the prepreg constituting the circuit board. Conventionally, a metal plate is used as a plate-shaped carrier for attaching a sub-metal foil; in this case, the plate-shaped carrier and the metal foil are adhered by fusion or subsequent bonding. In the case of using an adhesive, from the viewpoint of heat resistance, it is generally unsuitable for use in a combination, and in the case where it is adhered by welding, if the peeling strength is excessively high by using a full-welding method, In the latter stage, the step of easy manual peeling will become difficult. If partial welding is used, it will make it difficult to prevent the penetration of the liquid between the plate-shaped carrier and the metal foil. No matter in any direction, the combination step is not one. The right way. Then, by using a plate-shaped carrier made of a resin, it is possible to exhibit an appropriate peeling strength with the metal foil, and it is possible to sufficiently withstand the heat history at the time of the combination step by using the heat-resistant resin. Further, the heat resistant resin to be used may be a known one.

為此，此板狀載子，若具有較高的玻璃轉移溫度Tg，則基於加熱後之剝離強度能維持在最適當的範圍內之觀點為佳，例如：120~320℃，較佳者為170~240℃的玻璃轉移溫度Tg。又，玻璃轉移溫度Tg，係以DSC(差示掃描量熱法)作為其測定其數值。 Therefore, if the plate-shaped carrier has a high glass transition temperature Tg, it is preferable to maintain the peel strength after heating in an optimum range, for example, 120 to 320 ° C, preferably Glass transition temperature Tg of 170~240 °C. Further, the glass transition temperature Tg is measured by DSC (differential scanning calorimetry).

又，樹脂的熱膨脹係數為金屬箔的熱膨脹係數的+10%、-30%以內為佳。藉此，對金屬箔與樹脂之間因熱膨脹差而引起的電路位置偏移能有防止的效果，可使不良品的發生減少，提升產率。 Further, the coefficient of thermal expansion of the resin is preferably +10% or less than -30% of the thermal expansion coefficient of the metal foil. Thereby, the offset of the circuit position due to the difference in thermal expansion between the metal foil and the resin can be prevented, and the occurrence of defective products can be reduced, and the yield can be improved.

板狀載子的厚度無特別限制，硬式或可撓式皆可，但若過厚對熱壓時的熱分佈會帶來不良的影響，另一方面，若過薄造成彎曲會使印刷配線板之製造工程無法進行，因此通常在5μm以上1000μm以下，50μm以上900μm以下為佳，100μm以上400μm以下為更佳。 The thickness of the plate-shaped carrier is not particularly limited, and may be either hard or flexible. However, if the thickness is too thick, the heat distribution during hot pressing may have an adverse effect. On the other hand, if the thickness is too thin, the bending may cause the printed wiring board. Since the manufacturing process cannot be performed, it is usually 5 μm or more and 1000 μm or less, preferably 50 μm or more and 900 μm or less, and more preferably 100 μm or more and 400 μm or less.

作為金屬箔之材料，其係以銅或銅合金箔為其代表，但也可使用鋁箔、鎳箔、鋅箔等材料。使用銅或銅合金箔的情況，可使用電解箔或壓延箔。金屬箔雖無限定，考量其用作印刷電路基板之配線，一般係具有1μm以上、較佳為5μm以上，以及400μm以下、較佳為120μm以下之厚度。於板狀載子的雙面貼合金屬箔的情況，可使用相同厚度的金屬箔，也可使用相異厚度的金屬箔。 As the material of the metal foil, it is represented by copper or a copper alloy foil, but materials such as aluminum foil, nickel foil, and zinc foil may also be used. In the case of using a copper or copper alloy foil, an electrolytic foil or a rolled foil can be used. Although there is no metal foil is defined, which is considered as a wiring of a printed circuit board, the general system having more than 1 μ m, more preferably 5 μ m and 400 μ m or less, preferably a thickness of 120 μ m or less. In the case where the metal foil is bonded to both sides of the plate-shaped carrier, a metal foil having the same thickness may be used, or a metal foil having a different thickness may be used.

可在所使用之金屬箔上進行各種表面處理。可列舉如：以賦予耐熱性為目的之金屬鍍(Ni鍍、Ni-Zn合金鍍、Cu-Ni合金鍍、Cu-Zn合金鍍、Zn鍍、Cu-Ni-Zn合金鍍、Co-Ni合金鍍等)，為賦予防鏽性或耐變色性之鉻酸鹽處理(包含鉻酸鹽處理液中含有一種以上之Zn、P、Ni、Mo、Zr、Ti等之合金元素)，為調整表面粗糙度之粗化處理(例：以銅電著粒或Cu-Ni-Co合金鍍、Cu-Ni-P合金鍍、Cu-Co合金鍍、Cu-Ni合金鍍、Cu-Co合金鍍、Cu-As合金鍍、Cu-As-W合金鍍等之銅合金鍍所得之粗化效果)。當然粗化處理會帶來金屬箔與板狀載子剝離強度上之影響，鉻酸鹽處理也會造成重大的影響。雖說鉻酸鹽處理以防鏽性與耐變色性之 觀點來看係其重要因素，但因經處理也能觀察到有意義地使剝離強度有顯著上升的傾向，故作為剝離強度的調整手段而言也具有其意義。 Various surface treatments can be carried out on the metal foil used. For example, metal plating for imparting heat resistance (Ni plating, Ni-Zn alloy plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy plating, Co-Ni alloy) For plating, etc., for chromate treatment (including one or more alloying elements containing Zn, P, Ni, Mo, Zr, Ti, etc. in the chromate treatment liquid) for imparting rust prevention or discoloration resistance, for adjusting the surface Roughening treatment of roughness (Example: copper electro-graining or Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-Co alloy plating, Cu - roughening effect obtained by copper alloy plating such as As alloy plating or Cu-As-W alloy plating). Of course, the roughening treatment will have an effect on the peel strength of the metal foil and the plate-shaped carrier, and the chromate treatment also has a significant influence. Although chromate treatment to prevent rust and discoloration Although it is an important factor from a point of view, since it is observed that the peeling strength is remarkably increased by the treatment, it is also useful as a means for adjusting the peel strength.

傳統上CCL，樹脂與銅箔之剝離強度越高越為理想，例如：電解銅箔的墊面(M面)作為與樹脂的接著面，藉由進行粗化處理等之表面處理，透過物理性的以及化學性的錨定效應，以此將接著力的提升加以實現。 Conventionally, CCL is preferable because the peeling strength of the resin and the copper foil is higher. For example, the mat surface (M surface) of the electrolytic copper foil serves as a bonding surface with the resin, and is subjected to surface treatment such as roughening treatment to transmit physical properties. And the chemical anchoring effect, in order to achieve the improvement of the adhesion.

又，在樹脂側方面，為提高與金屬箔之接著力，同樣的添加各種的黏著劑。如前述，於本發明係與CCL為相異製品，金屬箔與樹脂有終將剝離之必要，過度的提高剝離強度反而不利。 Further, in terms of the resin side, in order to improve the adhesion to the metal foil, various adhesives are added in the same manner. As described above, in the present invention, the CCL is a dissimilar product, and the metal foil and the resin are necessary to be peeled off at the end, and the peel strength is excessively increased.

在此，於本發明相關附載子金屬箔之較佳之一實施形態方面，為將金屬箔與板狀載子的剝離強度調節至前述較佳的範圍內，將貼合面之表面粗糙度，依JIS B 0601：2001為準則加以測定金屬箔表面之十點平均粗糙度(Rz jis)加以表示時，係在3.5μm以下、更進一步的在3.0μm以下為佳。但，將表面粗糙度耗費工序毫無限制的縮小將將轉為成本上升之原因，所以界定在0.1μm以上為佳，0.3以上更佳。如使用電解銅箔作為金屬箔的情況時，若需進行此等表面粗度調整，光澤面(光亮面、S面)以及粗糙面(墊面、M面)之任意面皆可被使用，但使用S面時調整至上述表面粗度較為容易。另一方面，前述金屬箔之前述載子不相接側的表面之平均十點粗糙度(Rz jis)，係在0.4μm以上10.0μm以下為佳。 Here, in a preferred embodiment of the attached sub-metal foil of the present invention, in order to adjust the peeling strength of the metal foil and the plate-shaped carrier to the above-mentioned preferred range, the surface roughness of the bonding surface is determined. When JIS B 0601:2001 is used to measure the ten-point average roughness (Rz jis) of the surface of the metal foil, it is preferably 3.5 μm or less, and further preferably 3.0 μm or less. However, the unrestricted reduction of the surface roughness-consuming process will be the cause of the increase in cost, so it is preferably 0.1 μm or more, and more preferably 0.3 or more. When an electrolytic copper foil is used as the metal foil, any surface of the glossy surface (shiny surface, S surface) and rough surface (mat surface, M surface) can be used if these surface roughness adjustments are required, but It is easier to adjust to the above surface roughness when using the S surface. On the other hand, the average ten-point roughness (Rz jis) of the surface on the side where the carrier does not contact the metal foil is preferably 0.4 μm or more and 10.0 μm or less.

又，在與本發明相關附載子金屬箔之另一理想實施形態方面，對於與金屬箔之樹脂貼合的面，不施行粗化處理等之為提升剝離強度之表面處理。又，在與本發明相關之附載子金屬箔又一理想實施形態方面，係在樹脂之中，不添加為提高與金屬箔之接著力之黏著劑。 Further, in another preferred embodiment of the attached sub-metal foil according to the present invention, the surface to be bonded to the resin of the metal foil is not subjected to a surface treatment for improving the peel strength, such as a roughening treatment. Further, in another preferred embodiment of the attached sub-metal foil according to the present invention, the resin is not added as an adhesive for improving the adhesion to the metal foil.

作為製造附載子金屬箔之熱壓之條件，如在使用預浸漬片作為板狀載子之情況，其係以壓力30~40kg/cm2，且比預浸漬片之玻璃轉移溫度為高之溫度下進行熱壓程序較佳。 As a condition for producing hot pressing of the attached sub-metal foil, as in the case of using a prepreg as a plate-shaped carrier, it is a pressure of 30 to 40 kg/cm 2 and a temperature higher than a glass transition temperature of the prepreg. It is preferred to carry out the hot pressing process.

由以上之觀點來看，本發明係提供一種金屬箔，為使樹脂製之板狀載子可能剝離並密接，該密接著面，在如上述金屬箔之至少一方的 表面上，係經上述之離型劑所成之層或離型材塗層處理之金屬箔者。又此金屬箔之表面，在分子內有兩個以下硫醇基之化合物所成者塗層前，也可進行如前述之鉻酸鹽處理等之步驟。 From the above viewpoints, the present invention provides a metal foil in which a plate-shaped carrier made of resin may be peeled off and adhered, and the close contact surface is at least one of the metal foils as described above. On the surface, it is a layer formed by the above-mentioned release agent or a metal foil treated by a profile coating. Further, the surface of the metal foil may be subjected to a step such as the above-described chromate treatment before the coating of the compound having two or less thiol groups in the molecule.

由別的觀點來看，本發明係提供一種板狀載子，在作為金屬箔之密著面之板狀載子至少一方的表面上，係具有上述之離型劑所成之層或離型材者。此板狀載子，可適用於如上述將金屬箔剝離可能並密著之用途。 From another viewpoint, the present invention provides a plate-shaped carrier having a layer formed of the above-mentioned release agent or a release profile on at least one surface of a plate-shaped carrier which is a close surface of the metal foil. By. This plate-shaped carrier can be suitably used for the purpose of peeling off the metal foil as described above.

再由別的觀點來看，本發明係提供一種無芯多層印刷配線板用金屬箔，其在上述金屬箔之表面，以上記之離型劑所成之層或離型材加以塗層者。又此金屬箔之表面，在以分子內有兩個以下硫醇基之化合物所成者覆蓋之前，也可進行如前述之鉻酸鹽處理等之步驟。 From another point of view, the present invention provides a metal foil for a coreless multilayer printed wiring board which is coated on the surface of the metal foil with a layer formed of the release agent or a release material. Further, the surface of the metal foil may be subjected to a step such as the above-described chromate treatment before being covered with a compound having two or less thiol groups in the molecule.

又，金屬箔或樹脂的表面以具備XPS(X射線光電子能譜儀)、EPMA(電子微探儀)、EDX(X射線能量散佈分析儀)電子掃描顯微鏡之儀器加以測定，若可檢測出Si，可推知於樹脂之表面存在有矽烷化合物、若可檢測出S，可推知於金屬箔或樹脂之表面存在有分子內有兩個以下硫醇基之化合物，又若可檢測出Al、Ti、Zr，則可推知於金屬箔或樹脂之表面存在有如上記金屬醇鹽。 Further, the surface of the metal foil or resin is measured by an apparatus including an XPS (X-ray photoelectron spectroscopy), an EPMA (Electron Micro-Explorer), and an EDX (X-ray Energy Dispersion Analyzer) electron scanning microscope, and Si can be detected. It can be inferred that a decane compound exists on the surface of the resin, and if S can be detected, it can be inferred that a compound having two or less thiol groups in the molecule exists on the surface of the metal foil or the resin, and if Al, Ti, Zr, it can be inferred that the metal alkoxide as described above exists on the surface of the metal foil or the resin.

再者，由別的觀點來看，本發明係提供一種上述附載子金屬箔之用途。 Furthermore, from another point of view, the present invention provides the use of the above-described attached sub-metal foil.

第一，提供一種多層金屬張積層板之製造方法，包含對於上述附載子金屬箔之最少一側之金屬箔側，以樹脂層合，接著再以樹脂或金屬箔層合一次以上，例如1~10次反覆層合之步驟者。 Firstly, a method for producing a multilayer metal laminate layer comprising a metal foil side on a side of the least side of the attached sub-metal foil, laminated with a resin, and then laminated with a resin or a metal foil at least once, for example, 1~ 10 steps to repeat the lamination.

第二，提供一種多層金屬張積層板之製造方法，包含於上述之附載子金屬箔之金屬箔側以樹脂層合，接著，再將樹脂、單面又或是雙面金屬張積層板、本發明之附載子金屬箔、或金屬箔層合一次以上，如1~10次反覆層合之步驟。 Secondly, a method for manufacturing a multilayer metal laminated layer is provided, which comprises laminating a resin on a side of a metal foil of the above-mentioned attached sub-metal foil, and then, a resin, a single-sided or double-sided metal laminated plate, and The attached sub-metal foil or the metal foil of the invention is laminated more than once, such as the step of laminating 1 to 10 times.

第二，提供一種多層金屬張積層板之製造方法，包含於上述之附載子金屬箔之金屬箔側以樹脂層合，接著，再將樹脂，單面又或是雙面金屬張積層板、或本發明之附載子金屬箔、或樹脂表面已利用金屬箔層 合之層合體，或金屬箔層合一次以上，如1~10次反覆層合之步驟。又，於最初之附載子金屬箔以樹脂層合之後的層合，僅以希望層合次數進行，隨各層合次數，以樹脂、單面或雙面金屬張積層板、本發明之附載子金屬箔、層合體，以及金屬箔所成群中，任意地加以選擇使用。 Secondly, a method for manufacturing a multilayer metal laminate layer comprising the resin lamination on the side of the metal foil of the attached sub-metal foil, followed by the resin, the single-sided or double-sided metal laminate, or The metal foil layer of the attached metal foil or the resin surface of the present invention has been utilized The laminated body, or the metal foil is laminated more than once, such as the step of laminating 1~10 times. Moreover, the lamination after the initial attachment of the sub-metal foil with the resin is carried out only in the number of times of lamination desired, and the resin, the single-sided or double-sided metal-clad laminate, and the attached sub-metal of the present invention are used in each number of lamination times. The foil, the laminate, and the metal foil are arbitrarily selected and used in groups.

更進一步說，本發明所使用之層合體，係為任何能使樹脂與金屬箔形成層合者，且係指非如本發明之附載子金屬箔中樹脂與金屬箔所要求於一定條件下容易剝離者。又，於此所使用之層合體可為藉由切斷樹脂與金屬箔接著或被貼合之處，使該層合體構成物之樹脂與金屬箔可剝離者。又，樹脂與金屬箔間的層合可係由樹脂的單面或雙面層合者。 Furthermore, the laminate used in the present invention is any one which enables the resin to be laminated with the metal foil, and means that the resin and the metal foil which are not in the metal foil of the attached invention are required to be under certain conditions. Stripper. Further, the laminate used herein may be one in which the resin and the metal foil of the laminate structure are peelable by cutting the resin and the metal foil. Further, the lamination between the resin and the metal foil may be one-sided or double-sided lamination of the resin.

於上述多層金屬張積層板的製造方法中，為因應需要，於附載子金屬箔中板狀載子與金屬箔間之層合面，或層合體中樹脂與金屬箔間之層合面，更可分別包含例如將前述附載子金屬箔之金屬箔或前述層合體之金屬箔的步驟、加以切斷的步驟、或例如將前述切斷後之附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟、或將切斷後之層合體中樹脂與金屬箔加以剝離並分離的步驟。 In the method for producing a multilayer metal laminated layer, the laminated surface between the plate-shaped carrier and the metal foil in the attached sub-metal foil or the laminated surface between the resin and the metal foil in the laminated body is required, if necessary. For example, the step of cutting the metal foil of the above-mentioned sub-metal foil or the metal foil of the above-mentioned laminate, or the step of cutting the plate-shaped carrier of the attached sub-metal foil and the metal foil may be separately peeled off. And a step of separating or separating and separating the resin and the metal foil in the laminated body after the cutting.

再者，更可包含將前記板狀載子與金屬箔剝離並分離後，將金屬箔之一部或全部以蝕刻除去之步驟。 Further, a step of peeling off and separating the front sheet-shaped carrier from the metal foil and then removing one or all of the metal foil by etching may be further included.

第三，提供一種組合基板之製造方法，包含在上述附載子金屬箔之金屬箔側以樹脂層合，接著再以樹脂，單面或雙面配線基板、單面或雙面金屬張積層板、本發明之附載子金屬箔、或如上述之層合體、或金屬箔以一次以上，例如1~10次反覆層合之步驟。又，於最初之附載子金屬箔以樹脂層合之後的層合，僅以希望層合次數進行，隨各層合次數，以樹脂、單面或雙面配線基板、單面或雙面金屬張積層板、發明之附載子金屬箔、如上述之層合體，以及金屬箔所成群中，任意地加以選擇使用。 Thirdly, a method for producing a composite substrate comprising: laminating a resin on a metal foil side of the attached sub-metal foil, followed by a resin, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminate, The attached sub-metal foil of the present invention or the laminate or the metal foil as described above is laminated one or more times, for example, 1 to 10 times. Further, the lamination after the initial lamination of the sub-metal foil with the resin is performed only in the number of times of lamination desired, and the resin, the single-sided or double-sided wiring substrate, the one-sided or double-sided metal laminated layer, with each number of lamination times The plate, the attached sub-metal foil of the invention, the laminate as described above, and the metal foil are arbitrarily selected and used.

第四，提供一種組合基板之製造方法，包含於上述附載子金屬箔之金屬箔側，層合一層以上組合配線層之步驟。此時，組合配線層可使用減成法或全加成法或半加成法之至少一種方法加以形成。 Fourthly, there is provided a method for producing a composite substrate comprising the step of laminating one or more laminated wiring layers on the side of the metal foil of the attached sub-metal foil. At this time, the combined wiring layer can be formed by at least one of a subtractive method or a full additive method or a semi-additive method.

在此，附載子金屬箔所使用之第四之組合基板的製造方法中，關於減成法，係指將金屬張積層板或配線基板(係包含印刷配線板、印刷 電路板等)上之金屬箔之不要部分，藉由蝕刻等方式，選擇性的加以除去，形成導體圖型之方法。關於全加成法，其係於導體層上不使用金屬箔，而藉由無電解鍍或/及電解電鍍形成導體圖型之方法，半加成法係如，於金屬箔所成之接種層上以無電解金屬析出，以及電解電鍍、蝕刻，或其中兩者併用將導體圖型形成後，不需的接種層以蝕刻方式除去，藉以得到導體圖型之方法。 Here, in the method of manufacturing the fourth combined substrate used for the sub-metal foil, the subtractive method refers to a metal laminate or a wiring board (including a printed wiring board and printing). A method of forming a conductor pattern by selectively removing unnecessary portions of the metal foil on a circuit board or the like by etching or the like. Regarding the full addition method, which is a method of forming a conductor pattern by electroless plating or/and electrolytic plating without using a metal foil on a conductor layer, a semi-additive method such as a seed layer formed of a metal foil After the electroless metal precipitation, electrolytic plating, etching, or both, the conductor pattern is formed, the unnecessary inoculation layer is removed by etching, thereby obtaining a conductor pattern.

本發明提供一種組合基板之製造方法，包含於上述附載子金屬箔之金屬箔側以樹脂層合，接著再以樹脂，單面或雙面配線基板、單面或雙面金屬張積層板、本發明之附載子金屬箔、或如上述之層合體、或金屬箔以一次以上，例如1~10次反覆層合之後，將樹脂、其上係金屬箔側為該最後層合之樹脂，使其接觸而層合之附載子金屬箔層合之步驟。 The present invention provides a method for producing a composite substrate comprising resin lamination on a side of a metal foil of the above-mentioned auxiliary sub-metal foil, followed by resin, single-sided or double-sided wiring substrate, single-sided or double-sided metal laminated laminate, and The attached sub-metal foil of the invention, or the laminate or the metal foil as described above, is laminated one or more times, for example, 1 to 10 times, and then the resin and the metal foil side thereof are the final laminated resin. The step of laminating and laminating the attached sub-metal foil.

在於上述之組合基板的製造方法中，更可包含於單面或雙面配線基板，單面或雙面金屬張積層板，附載子金屬箔之金屬箔，附載子金屬箔之板狀載子、層合體之金屬箔、層合體之樹脂、金屬箔，或樹脂上鑽孔，於該孔洞的側面及底面傳導電鍍步驟。或更可包含，在前記構成單面或雙面配線基板所構成的金屬箔，構成單面或雙面金屬張積層板的金屬箔，及構成附載子金屬箔所構成的金屬箔、層合體所構成的金屬箔，或金屬箔之至少一個配線形成之步驟進行一次以上者。 In the method for manufacturing a composite substrate described above, the method may further include a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminate, a metal foil with a sub-metal foil, and a plate-shaped carrier with a sub-metal foil attached thereto. The metal foil of the laminate, the resin of the laminate, the metal foil, or the resin is drilled, and the plating step is conducted on the side and bottom surfaces of the hole. Or a metal foil formed of a single-sided or double-sided wiring board, a metal foil constituting a single-sided or double-sided metal laminate, and a metal foil or a laminate formed of a carrier metal foil. The step of forming the metal foil or the at least one wiring of the metal foil is performed once or more.

在上記之組合基板之製造方法中，更可包含於配線形成之表面上，於單面使金屬箔密著之附載子金屬箔之載子側、或在樹脂之單面上層合有金屬箔之層合體之樹脂側加以層合之步驟。且更可包含，於配線形成之表面上，以樹脂層合，將該樹脂以雙面密著金屬箔之本發明之附載子金屬箔，或樹脂雙面以金屬箔層合之層合體加以層合之步驟。 In the method for producing a composite substrate as described above, it may be further included on the surface on which the wiring is formed, and the metal foil may be laminated on the carrier side of the metal foil to which the metal foil is adhered on one side or the metal foil may be laminated on one surface of the resin. The step of laminating the resin side of the laminate. Furthermore, the resin may be laminated on the surface on which the wiring is formed, and the resin may be laminated with a metal foil laminated with the metal foil on both sides of the resin or a laminate laminated with a metal foil on both sides of the resin. The steps are combined.

又，所謂「配線形成之表面」，其意義為進行組合步驟時，每回出現於表面上形成配線之部分，其亦包含作為最終製品之組合基板，與其形成途中者。 In addition, the term "surface formed by wiring" means a portion where wiring is formed on the surface every time the combination step is performed, and also includes a composite substrate as a final product, which is formed in the middle.

於上述組合基板的製造方法中，為因應所需，於附載子金屬箔中板狀載子與金屬箔間之層合面，或層合體中樹脂與金屬箔間之層合面，更可分別包含例如將前述附載子金屬箔之金屬箔上或前述層合體之金屬箔 上，加以切斷的步驟，或例如將前述切斷後之附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟，或將前述切斷後之層合體中樹脂與金屬箔加以剝離並分離的步驟。 In the method for producing a composite substrate described above, the laminated surface between the plate-shaped carrier and the metal foil in the attached sub-metal foil or the laminated surface between the resin and the metal foil in the laminated body may be separately required for the purpose. a metal foil comprising, for example, a metal foil of the aforementioned sub-metal foil or a laminate of the foregoing a step of cutting the substrate, or a step of separating and separating the plate-shaped carrier of the attached metal foil after the cutting, or peeling off the resin and the metal foil in the laminated body after the cutting The step of separation.

再者，更可包含將前記之板狀載子與金屬箔，係經剝離並分離後，再將金屬箔之一部或全面以蝕刻方式除去之步驟。 Furthermore, the step of peeling off and separating the plate-shaped carrier and the metal foil of the foregoing may be included, and then removing one or a part of the metal foil by etching.

又，在上述之多層金屬張積層板之製造方法及組合基板之製造方法中，可藉由各層彼此進行熱壓黏合使之層合。此熱壓黏合，可在每次一層一層層合後進行，也可層合至某種程度後再進行，也可層合至最後再統一進行。 Moreover, in the above-described method for producing a multilayer metal laminate layer and a method for producing a composite substrate, the layers can be laminated by thermocompression bonding. The thermocompression bonding can be carried out after laminating one layer at a time, or after laminating to a certain extent, or laminating to the end and then uniformly.

尤其，本發明係提供一種組合基板之製造方法，其中在上記之組合基板的製造方法中，係於單面或雙面配線基板、單面或雙面銅張積層板、附載子金屬箔之金屬箔、附載子金屬箔之板狀載子、層合體之金屬箔、層合體之樹脂、金屬箔或樹脂上，鑽孔，於該孔洞之側面及底面進行傳導電鍍，再於前述構成單面或雙面配線基板之金屬箔及電路部分，構成單面或雙面金屬張積層板之金屬箔、構成層合體之金屬箔、或金屬箔上進行至少一次回路形成之步驟。 In particular, the present invention provides a method of manufacturing a combined substrate, wherein in the method of manufacturing a combined substrate described above, a single-sided or double-sided wiring substrate, a single-sided or double-sided copper laminated layer, and a metal of a carrier metal foil a foil, a plate-shaped carrier carrying a sub-metal foil, a metal foil of a laminate, a resin of a laminate, a metal foil or a resin, and drilling, conducting plating on the side and the bottom surface of the hole, and then forming a single side or The metal foil and the circuit portion of the double-sided wiring board constitute a metal foil of a single-sided or double-sided metal laminate, a metal foil constituting the laminate, or a step of forming at least one circuit on the metal foil.

以下，作為上述用途之具體例，並說明利用與本發明相關之附載子金屬箔的4層CCL之製法。在此使用的附載子金屬箔，係為於板狀載子11c的單面以金屬箔11a加以密著之附載子金屬箔11。於此附載子金屬箔11上，係以希望張數之預浸漬片12，接著以稱為內層芯板13之2層印刷電路基板或2層金屬張積層板，接著以預浸漬片12，再以附載子金屬箔11的順序重合，而完成1組4層CCL之組合單元。接著，以此單元14(通稱為「頁」)重複十次左右，而構成加壓組合物15(通稱為「本」)(圖7)。其後，將此本15以層合模具10夾住設置於熱壓機，以預設之溫度以及壓力加壓成型，藉此可同時製造多數之4層CCL。作為層合模具10，可使用如不鏽鋼製之平板。至於平板，雖無限定，可使用如1~10mm左右之厚板。關於4層以上之CCL，一般而言即使內層芯板的層數增加，即能夠以同樣的步驟加以生產。 Hereinafter, a method of producing a four-layer CCL using the attached sub-metal foil according to the present invention will be described as a specific example of the above-described use. The attached sub-metal foil used here is an auxiliary sub-metal foil 11 which is adhered to the metal foil 11a on one side of the plate-shaped carrier 11c. Here, the sub-metal foil 11 is attached with a desired number of prepregs 12, followed by a two-layer printed circuit board or an inner layer of a metal laminate, which is referred to as an inner core sheet 13, followed by a prepreg 12, Further, the order in which the sub-metal foils 11 are attached is superposed, and a combination of one set of four-layer CCLs is completed. Next, this unit 14 (generally referred to as "page") is repeated ten times or so to constitute a pressurized composition 15 (generally referred to as "this") (Fig. 7). Thereafter, the present 15 is placed in a hot press by the laminating mold 10, and is press-formed at a predetermined temperature and pressure, whereby a plurality of four layers of CCL can be simultaneously produced. As the laminated mold 10, a flat plate made of stainless steel can be used. As for the flat plate, although it is not limited, a thick plate such as 1 to 10 mm can be used. Regarding CCL of four or more layers, generally, even if the number of layers of the inner core sheets is increased, it can be produced in the same procedure.

以下，作為上述用途之具體例，為利用在本發明之樹脂製板 狀載子11c之雙面密著金屬箔之附載子金屬箔11，以示例方式說明無芯組合基板之製法。於此方法，於附載子金屬箔11之兩側以組合層16層合必要層數後，由附載子金屬箔11將雙面之金屬箔加以剝離(參照圖8)。 Hereinafter, as a specific example of the above use, the resin board used in the present invention is used. The method of manufacturing the coreless composite substrate will be described by way of example on the both sides of the carrier 11c with the metal foil 11 attached to the metal foil. In this method, after the necessary number of layers are laminated on the both sides of the attached sub-metal foil 11 by the combination layer 16, the metal foil of both sides is peeled off by the sub-metal foil 11 (refer FIG. 8).

例如，於本發明之附載子金屬箔之金屬箔側，以作為絕緣層之樹脂、2層電路基板、作為絕緣層之樹脂的順序重合，於其上使金屬箔測與樹脂板接觸再依序以本發明之附載子金屬箔之金屬箔加以重合，即可製造出組合基板。 For example, in the metal foil side of the attached sub-metal foil of the present invention, the resin as the insulating layer, the two-layer circuit substrate, and the resin as the insulating layer are superposed in order, and the metal foil is measured and contacted with the resin plate. The composite substrate can be produced by superposing the metal foil of the attached sub-metal foil of the present invention.

又，另一方法，係對於樹脂製之板狀載子11c的雙面或單面密著金屬箔之附載子金屬箔之最少一個的金屬箔側，以作為絕緣層之樹脂，然後再作為導體層之金屬箔的順序加以層合。接著也可因應所需，而包含將金屬箔之全面，以半蝕刻製程調整厚度之步驟。接著，於層合後金屬箔之預設位置以雷射施行加工，將金屬箔與樹脂貫通形成通過孔洞，施行除膠處理將通過孔洞中之膠體除去後，於通過孔洞底部，側面以及金屬箔之全面或一部施行無電解鍍形成層間接續，依其所需再進行電解電鍍。亦可在金屬箔上不需無電解鍍或電解電鍍之部分，於各別鍍步驟施行前，預先形成抗鍍層。且無電解電鍍、電解電鍍、抗鍍層與金屬箔之密著性不足的情況，可預先以化學方式將金屬箔之表面粗化。使用抗鍍層時，於電解後將抗鍍層去除。接著，將金屬箔及，無電解鍍部，電解電鍍部之不要部分藉由蝕刻去除以形成電路。藉此可得到組合基板。也可從樹脂、銅箔之層合至電路形成為止之步驟以複數次反覆執行後製作多層之組合基板。 Further, another method is to use a resin as an insulating layer and a conductor as a conductor for the resin foil-shaped carrier 11c on both sides or one side of the metal foil-attached metal foil. The order of the metal foil of the layers is laminated. Then, depending on the requirements, a step of adjusting the thickness of the metal foil by a half etching process may be included. Then, the predetermined position of the metal foil after lamination is processed by laser, the metal foil and the resin are formed through the hole, and the glue removal process is performed to remove the colloid in the hole, and then pass through the bottom of the hole, the side surface and the metal foil. The whole or one part of the electroless plating layer is indirectly continued, and electrolytic plating is performed according to the needs thereof. It is also possible to form a plating resist layer in advance on the metal foil without electroless plating or electrolytic plating before the respective plating steps are performed. Further, in the case of electroless plating, electrolytic plating, and insufficient adhesion between the plating resist and the metal foil, the surface of the metal foil may be chemically roughened in advance. When the plating resist is used, the plating resist is removed after electrolysis. Next, the metal foil and the electroless plated portion and the unnecessary portion of the electrolytic plating portion are removed by etching to form an electric circuit. Thereby, a combined substrate can be obtained. It is also possible to produce a plurality of laminated substrates by repeating the steps from the lamination of the resin and the copper foil to the formation of the circuit.

再者，也可於此組合基板之最表面，本發明之單面密著金屬箔之附載子金屬箔之金屬箔之樹脂側，使之接觸加以層合，或者也可先使樹脂板層合之後，再讓本發明之雙面密著金屬箔之附載子金屬箔之一面與之接觸加以層合。又，最後之層合體將要密著時，可於其前段中所定之位置，包含層合體之金屬箔之切面，進行切割的步驟，也可在最後之層基體將要密著時，都不進行切割步驟，直到最後包含所有層合體金屬面之切面時，在進行切割步驟。 Furthermore, the resin may be laminated on the resin side of the metal foil of the metal foil with the metal foil attached to the metal foil on one side of the composite substrate of the present invention. Thereafter, one side of the attached metal foil of the double-sided adhesive metal foil of the present invention is brought into contact with it to be laminated. Moreover, when the final laminate is to be adhered, the cutting surface of the metal foil of the laminate may be included at a position specified in the front stage, and the cutting step may be performed, or the cutting may be performed when the final layer is to be adhered. The step is performed until the final section of all laminated metal faces is included.

在此用以製作組合基板之樹脂板，可選用適合之含有熱硬化 性樹脂之預浸漬片。 Here, the resin plate for making the combined substrate can be selected to be suitable for thermal hardening. Prepreg of resin.

又，另一方法，係於本發明之板狀載子之單面或雙面金屬箔，例如貼合銅箔所得之層合體其金屬箔之露出表面上，層合用作絕緣層之樹脂例如預浸漬片或感光性樹脂。其後，於樹脂預設位置形成通過孔洞。使用之樹脂如使用預浸漬片時，其通過孔洞可使用雷射加工。雷射加工之後，可施行除膠步驟將此通過孔洞中之膠體加以去除。或者，在其樹脂使用感光性樹脂的情況，可藉由光刻法將通過孔洞形成部之樹脂加以去除。接著於通過孔洞底部，側面以及樹脂之全面或一部施行無電解鍍使層間接續形成，因應其必要再施行電解電鍍。也可以在樹脂上之無電解鍍或電解電鍍不需的部分，在各別鍍步驟進行之前，預先形成抗鍍層。又，無電解鍍、電解電鍍、抗鍍層與樹脂之密著性不足的情形下，可預先在樹脂的表面以化學方式做粗化處理。使用抗鍍層時，於電解後將抗鍍層去除。接著，無電解鍍部或電解電鍍部之不要部分藉由蝕刻去除以形成電路。之後，因應所需，可藉由切割附載子金屬箔之金屬箔其包含切斷面所定之位置，製造組合基板。也可從樹脂之層合至電路形成為止之步驟以複數次反覆執行，得到更多層之組合基板。 Further, another method is to laminate a single-sided or double-sided metal foil of the plate-shaped carrier of the present invention, for example, a laminate obtained by laminating a copper foil on a surface of an exposed metal foil thereof, and laminating a resin used as an insulating layer, for example, Dip sheet or photosensitive resin. Thereafter, a through hole is formed at a predetermined position of the resin. When a prepreg is used, the resin used can be processed by laser through a hole. After the laser processing, a gel removal step can be performed to remove the colloid in the hole. Alternatively, in the case where a photosensitive resin is used as the resin, the resin passing through the hole forming portion can be removed by photolithography. Then, the layer is indirectly formed by electroless plating through the bottom of the hole, the side surface, and the whole or a part of the resin, and electroplating is performed in accordance with the necessity. It is also possible to form a plating resist in advance before the respective plating steps are performed on portions of the resin which are not required for electroless plating or electrolytic plating. Further, in the case of electroless plating, electrolytic plating, and insufficient adhesion between the plating resist and the resin, the surface of the resin may be chemically roughened in advance. When the plating resist is used, the plating resist is removed after electrolysis. Then, the electroless plating portion or the electrolytic plating portion is not partially removed by etching to form a circuit. Thereafter, the composite substrate can be manufactured by cutting the metal foil of the attached sub-metal foil and including the position of the cut surface as required. It is also possible to carry out the steps from the lamination of the resin to the formation of the circuit in a plurality of times to obtain a composite substrate of more layers.

再者，也可於此組合基板之最表面，本發明之單面密著金屬箔層合體之樹脂側，或單面密著金屬箔之附載子金屬箔之樹脂側使之接觸加以層合，另外，也可先使樹脂層合之後，再讓本發明之雙面密著金屬箔之層合體之一面、或雙面密著金屬箔之附載子金屬箔之一面的金屬箔與之接觸加以層合。又，最後之層合體將要密著時，可於其前段中所定之位置，包含層合體之金屬箔之切斷面，進行切割的步驟，也可在最後之層基體將要密著時，都不進行切割步驟，直到最後包含所有層合體金屬面之切斷面時，在進行切割步驟。 Further, the outer surface of the substrate may be combined, and the resin side of the single-sided adhesion metal foil laminate of the present invention or the resin side of the metal foil with the metal foil adhered to the metal foil may be brought into contact with each other. Alternatively, after laminating the resin, one side of the laminate of the double-sided adhesive metal foil of the present invention or a metal foil having one side of the metal foil attached to the metal foil may be brought into contact with the layer. Hehe. Moreover, when the final laminate is to be adhered, the cut surface of the metal foil of the laminate may be cut at a position specified in the front stage, and the step of cutting may be performed, or when the substrate of the last layer is to be closed, The cutting step is performed until the cutting face of all the laminated metal faces is finally included, and the cutting step is performed.

對於以此等方式製作之無芯組合基板，經歷鍍步驟及/或蝕刻步驟使配線形成，接著使載子樹脂與金屬箔之間，剝離並分離以完成一種組合配線板。對於剝離並分離後之金屬箔之剝離面，可以形成配線，也可藉蝕刻方式將金屬箔全面去除用作一種組合配線板。再者，於組合配線板搭載電子元件類，即完成一種印刷線路板。又，於樹脂剝離前之無芯組 合基板上，直接搭載電子元件也可得到一種印刷電路板。 For the coreless combined substrate produced in this manner, a plating step and/or an etching step is performed to form a wiring, and then the carrier resin and the metal foil are peeled off and separated to complete a combined wiring board. For the peeling surface of the peeled and separated metal foil, wiring may be formed, or the metal foil may be completely removed by etching as a combined wiring board. Further, an electronic component is mounted on the combination wiring board, that is, a printed wiring board is completed. Also, the coreless group before the resin is peeled off A printed circuit board can also be obtained by directly mounting electronic components on the combined substrate.

【實施例】 [Examples]

以下揭示本發明之實施例及作為比較例之實驗例，但此等之實施例，係以提供作進一步理解本發明及其優點，並未有限定發明之意圖。 The embodiments of the present invention and the experimental examples of the comparative examples are disclosed below, but the examples are provided to further understand the present invention and its advantages, and are not intended to limit the invention.

(附載子金屬箔) (with sub-metal foil)

<實驗例1~15> <Experimental Examples 1 to 15>

準備複數之電解銅箔(厚度12μm，粗面表面粗糙度Rz jis3.7μm)，對各別電解銅箔之光亮(光澤)面，施行以下記條件之鎳-鋅(Ni-Zn)合金鍍處理以及鉻酸鹽(Cr-Zn鉻酸鹽)處理，在貼合面(在此指S面)之十點平均粗糙度(係根據Rz jis：JIS B 0601：2001測定)經處理為1.5μm後，作為樹脂選用南亞塑膠公司之預浸漬片(FR-4樹脂：玻璃轉移溫度Tg=140℃；厚度200μm)與該電解箔之S面貼合，170℃下進行100分鐘熱壓加工，製作出一種附載子銅箔。 Prepare a plurality of electrolytic copper foils (thickness 12 μm , rough surface roughness Rz jis 3.7 μm ), and perform nickel-zinc (Ni-Zn) on the bright (glossy) side of each electrolytic copper foil. Alloy plating treatment and chromate (Cr-Zn chromate) treatment, treated at 10 o'clock on the bonding surface (herein referred to as S surface), the average roughness (measured according to Rz jis: JIS B 0601:2001) After 1.5 μm , the prepreg (FR-4 resin: glass transition temperature Tg=140°C; thickness 200 μm ) of Nanya Plastics Co., Ltd. was used as the resin to adhere to the S surface of the electrolytic foil, and 100° at 170°C. Minute hot pressing to produce a carrier copper foil.

(鎳-鋅合金鍍) (nickel-zinc alloy plating)

Ni濃度 17g/L(以NiSO4方式添加) Ni concentration 17g / L (added by NiSO 4 method)

Zn濃度 4g/L(以ZnSO4方式添加) Zn concentration 4g / L (added by ZnSO 4 method)

pH 3.1 pH 3.1

液溫 40℃ Liquid temperature 40 ° C

電流密度 0.1~10A/dm2 Current density 0.1~10A/dm 2

電鍍時間 0.1~10秒 Plating time 0.1~10 seconds

(鉻酸鹽處理) (chromate treatment)

Cr濃度 1.4g/L(以CrO3或K2CrO7之方式添加) Cr concentration 1.4g / L (added as CrO 3 or K 2 CrO 7 )

Zn濃度 0.01~1.0g/L(以ZnSO4方式添加) Zn concentration 0.01~1.0g/L (added by ZnSO 4 method)

Na2SO4濃度 10g/L Na 2 SO 4 concentration 10g / L

pH 4.8 pH 4.8

液溫 55℃ Liquid temperature 55 ° C

電流密度 0.1~10A/dm2 Current density 0.1~10A/dm 2

電鍍時間 0.1~10秒 Plating time 0.1~10 seconds

又，於該光澤面以表1所示之金屬醇鹽之水溶液，使用噴塗機塗佈後，在100℃的空氣中使之乾燥後，進行預浸漬片與銅箔之貼合。關於金屬醇鹽之使用條件，於表1揭示。 Further, the glossy surface was coated with an aqueous solution of a metal alkoxide shown in Table 1 using a spray coater, and then dried in air at 100 ° C, and then the prepreg and the copper foil were bonded together. The conditions for use of the metal alkoxide are disclosed in Table 1.

又，附載子銅箔之中，有幾種係預設對該附載子銅箔進行電路形成等之進一步加熱處理時，會有受熱歷程之情形，進行以表1記載之條件(在此為220℃ 3小時、6小時、9小時)之熱處理。 Further, among the copper foils to be attached, there are several cases in which the copper foil is subjected to further heat treatment such as circuit formation, and the heat history is carried out, and the conditions described in Table 1 are performed (here, 220). Heat treatment at °C for 3 hours, 6 hours, and 9 hours).

藉熱壓步驟所得之附載子銅箔，以及於其後進行之3小時、6小時、9小時之各別之熱處理後之附載子銅箔，測定銅箔與板狀載子(加熱後之樹脂)的剝離強度。其各別之結果如表1所示。 The copper foil and the plate-shaped carrier (heated resin) were measured by the copper foil attached to the hot pressing step and the copper foil after the heat treatment for 3 hours, 6 hours, and 9 hours thereafter. Peel strength. The respective results are shown in Table 1.

又，為評價剝離作業性，以各別單位個數除人工作業時間(時間/個)加以評價。結果如表2所示。 Further, in order to evaluate the peeling workability, the manual work time (time/number) was evaluated by the number of individual units. The results are shown in Table 2.

<實驗例16> <Experimental Example 16>

在實驗例1，銅箔與預浸漬片貼合時，除該銅箔之光澤面，預浸漬片未經任何金屬醇鹽處理之外，以與實驗例1相同條件，製作附載子銅箔，評價各個階段之剝離強度與作業時間。各別之結果，如表1及表2所示。 In Experimental Example 1, when the copper foil was bonded to the prepreg, the prepreg was treated with the same conditions as in Experimental Example 1 except that the prepreg was not subjected to any metal alkoxide treatment, and the carrier copper foil was prepared. Evaluate the peel strength and working time at each stage. The respective results are shown in Tables 1 and 2.

雖未以表記錄，但金屬醇鹽，不論於銅箔之表面處理，或於預浸漬片之表面處理，若為相同化合物相同條件下處理，於其後之層合體之剝離強度，加熱後之剝離強度，剝離之作業性之各方面，已知能得到同等之結果。 Although not recorded in the table, the metal alkoxide, whether it is treated on the surface of the copper foil or on the surface of the prepreg, is treated under the same conditions of the same compound, and the peel strength of the laminate after the heating is heated. It is known that the peeling strength and the workability of peeling are equivalent.

【表1】 【Table 1】

(組合配線板) (combined wiring board)

於以此種方式製作之附載子銅的的兩側，以FR-4預浸漬片(南亞塑膠公司製)、銅箔(JX日礦日石金屬股份有限公司製，JTC12μm(製品名))的順序重疊，再以3MPa之壓力於表中各別標示之加熱條件進行熱壓步驟，製作4層銅張積層板。 FR-4 prepreg (made by Nanya Plastics Co., Ltd.) and copper foil (JTC Nisshin Nippon Metal Co., Ltd., JTC12 μm (product name) on both sides of the copper plated in this way The order of the layers is overlapped, and then a hot pressing step is performed under the heating conditions of the respective labels in the table at a pressure of 3 MPa to prepare a 4-layer copper laminate.

接著，將前述4層銅張積層板表面之銅箔與其下方的絕緣層(硬化後預浸漬片)加以貫通，以雷射加工機鑿出直逕100μm的孔洞。接續前步驟，於前述孔洞的底部露出之附載子銅箔上的銅箔表面與、前述孔洞的側面、前述4層銅張積層板表面之銅箔上進行藉無電解銅鍍、電解銅鍍之銅鍍，附載子銅箔之銅箔與、4層銅張積層板表面之銅箔之間形成電流的接續。接續前步驟，4層銅張積層板表面之銅箔之一部利用氯化鐵系之蝕刻液加以蝕刻，形成電路。此等步驟操作即得到一種4層組合基板。 Next, the copper foil on the surface of the four-layer copper laminate layer and the insulating layer (pre-impregnated prepreg) on the lower surface were passed through, and a hole having a diameter of 100 μm was cut by a laser processing machine. In the pre-continuation step, the surface of the copper foil on the copper foil attached to the bottom of the hole and the side surface of the hole and the copper foil on the surface of the four-layer copper laminate are subjected to electroless copper plating and electrolytic copper plating. The copper plating, the copper foil with the carrier copper foil and the copper foil on the surface of the four-layer copper laminate layer form a current connection. In the pre-continuation step, one of the copper foils on the surface of the four-layer copper laminate is etched with an iron chloride-based etching solution to form an electric circuit. These steps operate to obtain a 4-layer composite substrate.

接續前步驟，在前述4層組合基板中，藉由剝離並分離前述附載子銅箔之板狀載子與銅箔，得到兩組之兩層組合配線板。 In the pre-continuation step, in the four-layer composite substrate, the plate-shaped carrier of the carrier copper foil and the copper foil were peeled off and separated to obtain two sets of two-layer composite wiring boards.

接續前步驟，在前述之兩組之兩層組合配線板上，且與板狀載子密著之銅箔進行蝕刻形成配線，而得到兩組之兩層組合配線板。 In the pre-continuation step, wiring is formed on the two-layer combination wiring board of the two groups described above, and the copper foil adhered to the plate-shaped carrier is etched to obtain two sets of two-layer composite wiring boards.

各實驗例分別以複數之4層組合基板製作，針對各別之操作條件，於組合基板製作步驟中，構成附載子銅箔其預浸漬片與銅箔之密著狀態，以目視加以確認，於表1剝離強度以及加熱後之剝離強度，當被評價為「G」條件，係指其製作之附載子銅箔使用作組合配線板時，於組合步驟時附載子銅箔之樹脂(板狀載子)未受破壞，成功剝離。 Each of the experimental examples was prepared by using a plurality of composite substrates of a plurality of layers, and in the combined substrate production step, the prepreg and the copper foil of the carrier copper foil were adhered to each other in a combined substrate, and visually confirmed. Table 1 shows the peel strength and the peel strength after heating. When evaluated as "G", it means that when the copper foil to be produced is used as a composite wiring board, the resin of the copper foil is attached in the combination step. Sub) undestroyed and successfully stripped.

而關於評價為「N」之條件，係指組合步驟時附載子銅箔其銅箔之剝離操作，其樹脂受到破壞，或未剝離銅箔其表面殘留有樹脂。 On the other hand, the condition of evaluation of "N" refers to the peeling operation of the copper foil of the carrier copper foil in the combination step, the resin is broken, or the resin is left on the surface of the unpeeled copper foil.

而關於評價為「-」之條件，係指組合步驟時附載子銅箔其銅箔之剝離操作，樹脂雖未被破壞且剝離，但其中並未進行剝離操作銅箔便已剝離。 On the other hand, the condition of evaluation of "-" refers to the peeling operation of the copper foil of the copper foil attached to the carrier, and the resin is not broken and peeled off, but the copper foil is peeled off without performing the peeling operation.

<實驗例17> <Experimental Example 17>

準備複數之電解銅箔(厚度12μm)，對各別電解銅箔之光亮(S) 面，施行以下記條件之鎳-鋅(Ni-Zn)合金鍍處理以及鉻酸鹽(Cr-Zn鉻酸鹽)處理，在貼合面(在此指S面)之十點平均粗糙度(係根據Rz jis：JIS B 0031：2003(JIS B 0601：2001)測定)經處理為1.5μm後，作為樹脂選用南亞塑膠公司之預浸漬片(FR-4樹脂)與該電解箔之S面貼合，170℃下進行100分鐘熱壓加工，製作出一種附載子銅箔。 Prepare a plurality of electrolytic copper foils (thickness 12 μm ), and apply nickel-zinc (Ni-Zn) alloy plating and chromate (Cr-Zn) to the bright (S) side of each electrolytic copper foil. Chromate) treatment, the ten point average roughness (measured according to Rz jis: JIS B 0031:2003 (JIS B 0601:2001)) on the bonding surface (herein referred to as S surface) is treated to 1.5 μm As a resin, a prepreg (FR-4 resin) of Nanya Plastics Co., Ltd. was used to bond the S surface of the electrolytic foil, and hot pressing was performed at 170 ° C for 100 minutes to prepare a copper foil with carrier.

(鎳-鋅合金鍍) (nickel-zinc alloy plating)

Ni濃度 17g/L(以NiSO4方式添加) Ni concentration 17g / L (added by NiSO 4 method)

Zn濃度 4g/L(以ZnSO4方式添加) Zn concentration 4g / L (added by ZnSO 4 method)

pH 3.1 pH 3.1

液溫 40℃ Liquid temperature 40 ° C

電流密度 0.1~10A/dm2 Current density 0.1~10A/dm 2

電鍍時間 0.1~10秒 Plating time 0.1~10 seconds

(鉻酸鹽處理) (chromate treatment)

Cr濃度 1.4g/L(以CrO3或K2CrO7之方式添加) Cr concentration 1.4g / L (added as CrO 3 or K 2 CrO 7 )

Zn濃度 0.01~1.0g/L(以ZnSO4方式添加) Zn concentration 0.01~1.0g/L (added by ZnSO 4 method)

Na2SO4濃度 10g/L Na 2 SO 4 concentration 10g / L

pH 4.8 pH 4.8

液溫 55℃ Liquid temperature 55 ° C

電流密度 0.1~10A/dm2 Current density 0.1~10A/dm 2

電鍍時間 0.1~10秒 Plating time 0.1~10 seconds

關於對該S面或板狀載子之離型劑的處理方式係為，使用噴塗機將離型劑之水溶液塗佈，於100℃之空氣中乾燥銅箔表面後，進行與預浸漬片的貼合。關於離型劑的使用條件，離型劑的種類、離型劑於水中溶解至塗佈前之攪拌時間、水溶液中離型劑的濃度、水農藝中的乙醇濃度、水溶液之pH值如表3所示。 The method of treating the release agent for the S surface or the plate-shaped carrier is to apply an aqueous solution of the release agent using a spray coater, and dry the surface of the copper foil in air at 100 ° C, and then perform prepreg with the prepreg. fit. Regarding the use conditions of the release agent, the type of release agent, the dissolution time of the release agent in water until coating, the concentration of the release agent in the aqueous solution, the concentration of ethanol in aquaculture, and the pH value of the aqueous solution are shown in Table 3. Shown.

又，關於形成對該S面或板狀載子的離型材樹脂塗膜係為，將具有表 3所示成分之樹脂塗膜用的組成物利用凹版塗佈法塗佈後，使用刮刀將其厚度調節為2~4μm者。又，將樹脂塗膜進行塗佈後，加熱150℃、30秒，進行烘烤處理。並且，表3所示之環氧系樹脂係使用雙酚A型環氧樹脂，三聚氰胺系樹脂係使用甲基醚化三聚氰胺樹脂，氟樹脂係使用聚四氟乙烯，二甲基矽酮系樹脂係使用二甲基聚矽氧烷。 Further, the release resin coating film for forming the S surface or the plate-shaped carrier is a composition for a resin coating film having the components shown in Table 3, which is coated by a gravure coating method, and then coated with a doctor blade. The thickness is adjusted to 2~4 μ m. Further, after coating the resin coating film, it was heated at 150 ° C for 30 seconds to carry out baking treatment. Further, the epoxy resin shown in Table 3 is a bisphenol A type epoxy resin, the melamine resin is a methyl etherified melamine resin, and the fluororesin is a polytetrafluoroethylene or a dimethyl fluorenone resin. Dimethyl polyoxane was used.

又，附載子銅箔係預設對該附載子銅箔電進行路形成等之進一步加熱處理時，會有受熱歷程之情形，進行以表3記載之條件(在此為220℃ 3小時、6小時、9小時)之熱處理。 Further, when the carrier copper foil is subjected to further heat treatment such as electric path formation of the carrier copper foil, the heat history may be carried out, and the conditions described in Table 3 (here, 220 ° C for 3 hours, 6) are carried out. Heat treatment at hours, 9 hours).

藉熱壓步驟所得之附載子銅箔，及於其後更進一步進行熱處理後之附載子銅箔，測定銅箔與板狀載子(加熱後之樹脂)的剝離強度。其各別之結果如表3所示。 The peeling strength of the copper foil and the plate-shaped carrier (resin after heating) was measured by the copper foil of the carrier obtained by the hot pressing step and the copper foil attached later after the heat treatment. The respective results are shown in Table 3.

又，為評價剝離作業性，以各別單位個數除人工作業時間(時間/個)加以評價。結果如表4所示。 Further, in order to evaluate the peeling workability, the manual work time (time/number) was evaluated by the number of individual units. The results are shown in Table 4.

<實驗例18~28> <Experimental Examples 18 to 28>

使用表3所示之銅箔、樹脂(預浸漬片)及離型劑，進行與實驗例17相同之程序，製作附載子金屬箔。在實驗例19、23、26中，係將離型劑塗佈於板狀載子上。又，進行表3所示熱處理之條件。各自分別進行與實驗例17相同的評價。結果如表3、4所示。 Using the copper foil, resin (prepreg) and release agent shown in Table 3, the same procedure as in Experimental Example 17 was carried out to prepare a carrier metal foil. In Experimental Examples 19, 23, and 26, a release agent was applied to a plate-shaped carrier. Further, the conditions of the heat treatment shown in Table 3 were carried out. The same evaluation as in Experimental Example 17 was carried out separately. The results are shown in Tables 3 and 4.

實驗例28係不使用任何離型劑或離型材，將銅箔與樹脂(預浸漬片~相互貼合，製作附載子金屬箔，進行與實驗例17相同的評估。 In Experimental Example 28, the same evaluation as in Experimental Example 17 was carried out by using a copper foil and a resin (prepreg-bonded to each other to form a carrier metal foil) without using any release agent or release material.

又，銅箔之貼合面的分類、表面處理之條件及表面粗糙度Rz jis、離型劑的使用條件、預浸漬片的種類、以及銅箔與預浸漬片間之層合條件係如表3所示。 Further, the classification of the bonding surface of the copper foil, the conditions of the surface treatment, the surface roughness Rz jis, the conditions of use of the release agent, the type of the prepreg, and the lamination conditions between the copper foil and the prepreg are as follows. 3 is shown.

在銅箔與板狀載子間貼合面的相反側之銅箔墊面(M)面之表面處理條件中，環氧矽烷(處理)及粗化處理的具體條件如以下所示。 In the surface treatment conditions of the copper foil pad surface (M) surface on the opposite side to the bonding surface between the copper foil and the plate-shaped carrier, the specific conditions of the epoxy decane (treatment) and the roughening treatment are as follows.

(環氧矽烷處理) (epoxy decane treatment)

處理液：3-丙基三甲氧基矽烷0．9體積百分濃度%水溶液 Treatment liquid: 3-propyltrimethoxydecane 0.9 volume percent concentration aqueous solution

pH5．0~9．0 pH5.0~9.0

常溫下攪拌12小時 Stir at room temperature for 12 hours

處理方法：使用噴塗機，塗佈處理液後，於100℃之空氣中，使處理面乾燥5分鐘。 Treatment method: After applying the treatment liquid using a spray coater, the treated surface was dried in air at 100 ° C for 5 minutes.

(粗化處理) (roughening treatment)

Cu濃度 20g/L(以CuSO4之方式添加) Cu concentration 20g / L (added as CuSO 4 )

H2SO4濃度 50~100g/L H 2 SO 4 concentration 50~100g/L

As濃度 0．01~2．0g/L(以亞砷酸之方式添加) As concentration 0.01~2.0g/L (added as arsenious acid)

液溫 40℃ Liquid temperature 40 ° C

電流密度 40~100A/dm2 Current density 40~100A/dm 2

電鍍時間 0．1~30秒 Plating time 0.1~30 seconds

根據表可知，離型劑無論處理於銅箔之表面或板狀載子(預浸漬片)之表面後，關於其層合體的剝離強度、加熱後的剝離強度、剝離操作性，將得到相同的結果。 According to the table, the release agent will be treated in the same manner as the surface of the copper foil or the surface of the plate-shaped carrier (prepreg), and the peel strength of the laminate, the peel strength after heating, and the peeling workability will be the same. result.

【表4】 【Table 4】

又，實驗例1，板狀載子(預浸漬片)與銅箔層合時，使用作為板狀載子厚度為200μm之預浸漬片。前述預浸漬片及前述銅箔之形狀係為，將550mm角之正方形的各頂點到其兩邊以25mm的距離，兩點連成一線切落，使成為八角形者。預浸漬片與銅箔的位置關係係為，使銅箔之中心與預浸漬片中心位置一致，配置銅箔的邊與預浸漬片的邊使之平行進行層合(如圖5之型態)。銅箔層合於預浸漬片之雙面。 Further, in Experimental Example 1, when a plate-shaped carrier (prepreg) was laminated with a copper foil, a prepreg having a plate-shaped carrier thickness of 200 μm was used. The shape of the prepreg and the copper foil is such that the apexes of the squares of the 550 mm angle are cut at a distance of 25 mm from both sides thereof, and the two points are cut into a line to form an octagonal shape. The positional relationship between the prepreg and the copper foil is such that the center of the copper foil is aligned with the center of the prepreg, and the side of the copper foil is placed in parallel with the side of the prepreg to be laminated (as shown in FIG. 5). . The copper foil is laminated on both sides of the prepreg.

又，實驗例2~10係為，550mm角之正方形的預浸漬片及銅箔之各頂點以曲率半徑25mm之圓弧加工者，除了其形狀係以直線與圓弧所圍成之外，以與實驗例1相同之條件，使銅箔與預浸漬片層合(如圖3之型態)。銅箔層合於預浸漬片之雙面。 Further, in Experimental Examples 2 to 10, the prepreg of a square of 550 mm angle and the apexes of the copper foil were processed by a circular arc having a radius of curvature of 25 mm, except that the shape was surrounded by a straight line and an arc. The copper foil was laminated with the prepreg under the same conditions as in Experimental Example 1 (as shown in Fig. 3). The copper foil is laminated on both sides of the prepreg.

又，實驗例11除了其預浸漬片與銅箔形狀為半徑300mm之圓形之外，以與實驗例1相同之條件，使銅箔與預浸漬片層合(無圖)。銅箔層合於預浸漬片之雙面。 Further, in Experimental Example 11, except that the prepreg and the shape of the copper foil were circular with a radius of 300 mm, the copper foil and the prepreg were laminated under the same conditions as in Experimental Example 1 (not shown). The copper foil is laminated on both sides of the prepreg.

如此述所製作之附載子金屬箔，其板狀載子所露出之部分4，設置直徑1mm的孔洞，以作為後續組合工程時決定位置之導向孔。 The attached sub-metal foil prepared as described above is provided with a hole having a diameter of 1 mm as a guide hole in which the plate-shaped carrier is exposed, and is used as a guide hole for determining the position at the time of subsequent assembly.

於以此種方式製作之附載子銅的的兩側，以FR-4預浸漬片(南亞塑膠公司製)、銅箔(JX日礦日石金屬股份有限公司製，JTC 12μm(製品名))的順序重疊，再於3MPa之壓力下，以熱壓機170℃．100分鐘進行熱壓步驟，製作4層銅張積層板。 FR-4 prepreg (made by Nanya Plastics Co., Ltd.) and copper foil (JTC Nippon Mining & Metal Co., Ltd., JTC 12 μm (product name) on both sides of the copper produced in this way ))) The order of overlap, and then under the pressure of 3MPa, with a hot press 170 ° C. A hot pressing step was performed for 100 minutes to prepare a 4-layer copper laminate.

接著，將前述4層銅張積層板表面之銅箔與其下方的絕緣層(硬化後預浸漬片)加以貫通，以雷射加工機鑿出直逕100μm的孔洞。接續前步驟，於前記孔洞的底部露出之附載子銅箔上的銅箔表面與、前記孔洞的側面、前記4層銅張積層板表面之銅箔上進行藉無電解銅鍍、電解銅鍍之銅鍍，附載子銅箔之銅箔與、4層銅張積層板表面之銅箔之間形成電流的接續。接續前步驟，4層銅張積層板表面之銅箔之一部利用氯化鐵系之蝕刻液加以蝕刻，形成電路。此等步驟操作即得到一種4層組合基板。 Next, the copper foil on the surface of the four-layer copper laminate layer and the insulating layer (pre-impregnated prepreg) on the lower surface were passed through, and a hole having a diameter of 100 μm was cut by a laser processing machine. In the pre-continuation step, the surface of the copper foil on the copper foil attached to the bottom of the hole, the side surface of the front hole, and the copper foil on the surface of the four-layer copper laminate layer are subjected to electroless copper plating and electrolytic copper plating. The copper plating, the copper foil with the carrier copper foil and the copper foil on the surface of the four-layer copper laminate layer form a current connection. In the pre-continuation step, one of the copper foils on the surface of the four-layer copper laminate is etched with an iron chloride-based etching solution to form an electric circuit. These steps operate to obtain a 4-layer composite substrate.

接續前步驟，在前述4層組合基板中，於切斷前述附載子金屬箔之銅箔上的位置後，藉由剝離並分離前記附載子銅箔之板狀載子與銅箔，得到兩組之兩層組合配線板。 In the pre-continuation step, after cutting the position on the copper foil with the sub-metal foil attached thereto, the plate-shaped carrier and the copper foil of the copper foil with the carrier copper are peeled off and separated, and two sets are obtained. The two-layer combination wiring board.

<實驗例13> <Experimental Example 13>

在實驗例1中，除了銅箔及預浸漬片兩者之形狀為550mm角之正方形以外，使用與實驗例1相同之銅箔、離型劑及預浸漬片，製作出一種附載子金屬箔，經由與實驗例1相同的程序，得到2層組合配線板。 In Experimental Example 1, except that the shape of both the copper foil and the prepreg was 550 mm square, the same copper foil, release agent and prepreg as in Experimental Example 1 were used to produce a carrier metal foil. A two-layer composite wiring board was obtained through the same procedure as in Experimental Example 1.

各實驗例分別以複數之4層組合基板製作，針對各別之操作條件，於製作組合基板之步驟構成附載子銅箔其預浸漬片與銅箔之密著狀態，以目視加以確認，實驗例13之預浸漬片與銅箔的界面上，其形成剝離狀態者較實驗例1~11為多。 Each of the experimental examples was prepared by using a plurality of composite substrates of a plurality of layers, and the steps of fabricating the composite substrate were carried out to form a state in which the prepreg and the copper foil were adhered to each other under the respective operating conditions, and visually confirmed. At the interface between the prepreg of 13 and the copper foil, the peeling state was more than that of Experimental Examples 1 to 11.

又，比較實驗例13與實驗例1，實驗例1之預浸漬片與銅箔的界面上，其形成剝離狀態者個數較少。 Further, in Comparative Example 13 and Experimental Example 1, the interface between the prepreg and the copper foil of Experimental Example 1 was found to have a small number of peeling states.

且，比較實驗例1與實驗例2~11，實驗例2~11之預浸漬片與銅箔的界面上，其形成剝離狀態者個數較少。 Further, in Comparative Example 1 and Experimental Examples 2 to 11, the interface between the prepreg and the copper foil of Experimental Examples 2 to 11 was found to have a small number of peeling states.

Claims (43)

一種附載子金屬箔，其特徵為其係由樹脂製之板狀載子，與在該載子之至少一面上使成可剝離並密著的金屬箔所構成之附載子金屬箔；且板狀載子與金屬箔，係將下式：【化1】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物、其等之加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合使用加以貼合而成者。 An attached sub-metal foil characterized by a plate-shaped carrier made of a resin and an attached sub-metal foil formed of a metal foil which is peelable and adhered to at least one surface of the carrier; and a plate shape The carrier and the metal foil are of the formula: [Chem. 1] (R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkoxy group or a halogen atom; and R 2 is selected from an alkyl group. a hydrocarbon group in which a cycloalkyl group or an aryl group is grouped, or a hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom; M is any one of Al, Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, the valence of m + n is M, that is, 3 for Al and 4 for Ti and Zr The aluminate compound, the titanate compound, the zirconate compound, the hydrolyzed product thereof, and the condensate of the hydrolyzed product are used in combination, either alone or in combination. 如申請專利範圍第1項之附載子金屬箔，其中，板狀載子與金屬箔之剝離強度在10gf/cm以上200gf/cm以下。 The sub-metal foil according to the first aspect of the invention, wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less. 如申請專利範圍第1項之附載子金屬箔，其中樹脂製之板狀載子係包含熱硬化性樹脂。 The sub-metal foil according to claim 1, wherein the resin-made plate-shaped carrier comprises a thermosetting resin. 如申請專利範圍第1項之附載子金屬箔，其中樹脂製之板狀載子係預浸漬片。 The sub-metal foil according to the first aspect of the patent application, wherein the resin-made plate-shaped carrier is a prepreg. 如申請專利範圍第3項之附載子金屬箔，其中樹脂製之板狀載子係具有120~320℃的玻璃化溫度Tg。 The sub-metal foil of claim 3, wherein the resin-made plate-shaped carrier has a glass transition temperature Tg of 120 to 320 °C. 如申請專利範圍第1項之附載子金屬箔，其中與金屬箔之載子相接合側的表面，其十點平均粗糙度(Rz jis)係3.5μm以下。 The sub-metal foil attached to the first aspect of the patent application, wherein the surface on the side joined to the carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less. 如申請專利範圍第1項之附載子金屬箔，其中與金屬箔之載子不相接合側的表面，其十點平均粗糙度(Rz jis)係0.4μm以上10.0μm以下。 The sub-metal foil attached to the first aspect of the patent application, wherein the surface of the side opposite to the carrier of the metal foil has a ten-point average roughness (Rz jis) of 0.4 μm or more and 10.0 μm or less. 如申請專利範圍第1項之附載子金屬箔，其中金屬箔之厚度係1μm以上400μm以下。 For example, the sub-metal foil attached to the first aspect of the patent application, wherein the thickness of the metal foil is 1 μm or more and 400 μm or less. 如申請專利範圍第1項之附載子金屬箔，其中於220℃經過3小時、6小時或9小時之中至少一個加熱程序後，金屬箔與板狀載子之剝離強度係10gf/cm以上200gf/cm以下。 The sub-metal foil according to Item 1 of the patent application, wherein the peeling strength of the metal foil and the plate-shaped carrier is 10 gf/cm or more and 200 gf after at least one heating process of 3 hours, 6 hours or 9 hours at 220 ° C. /cm below. 如申請專利範圍第1~9項中任一項之附載子金屬箔，其中金屬箔為銅箔。 The attached sub-metal foil according to any one of claims 1 to 9, wherein the metal foil is a copper foil. 一種印刷配線板用金屬箔，其特徵為於其金屬箔之表面，係具有將下式：【化2】(R1)m-M-(R2)n(式中，R1係烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物、該加水分解生成物之縮合體，以單獨或複數組合者。 A metal foil for a printed wiring board, characterized in that the surface of the metal foil has the following formula: [Chem. 2] (R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkoxy group) Or a halogen atom; R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M system Al, Ti Or any of Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m + n is the valence of M, In other words, in the case of Al, it is 3, and in the case of Ti and Zr, it is an aluminate compound, a titanate compound or a zirconate compound represented by 4), and a hydrolyzed product such as a hydrolyzed product or a condensate of the hydrolyzed product is separately used. Or plural combinations. 如申請專利範圍第11項中之印刷配線板用金屬箔，其中係將金屬箔的鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以相對於使之單獨或複數組合而作用側之表面，在使該化合物進行作用前，經過鉻酸鹽處理者。 The metal foil for a printed wiring board according to the eleventh aspect of the invention, wherein the metallohydrate compound, the titanate compound or the zirconate compound of the metal foil is hydrolyzed, and the hydrolyzed product is hydrolyzed. The condensate is subjected to a chromate treatment before the action of the compound with respect to the surface on the side on which the combination is applied singly or in combination. 如申請專利範圍第11項之印刷配線板用金屬箔，其中與金屬箔之載子相接合側之表面，其十點平均粗糙度(Rz jis)係3.5μm以下。 The metal foil for a printed wiring board according to the eleventh aspect of the invention, wherein a surface having a side joined to a carrier of the metal foil has a ten-point average roughness (Rz jis) of 3.5 μm or less. 如申請專利範圍第11項之印刷配線板用金屬箔，其中與金屬箔之載子不相接合側的表面，其十點平均粗糙度(Rz jis)係0.4μm以上10.0μm以下。 The metal foil for a printed wiring board according to the eleventh aspect of the invention, wherein a surface having a side on which the carrier of the metal foil is not bonded has a ten-point average roughness (Rz jis) of 0.4 μm or more and 10.0 μm or less. 如申請專利範圍第11項之印刷配線板用金屬箔，其中金屬箔為銅箔。 A metal foil for a printed wiring board according to claim 11, wherein the metal foil is a copper foil. 一種金屬箔，其特徵為其係至少在一面上，具有將下式：【化3】(R1)m-M-(R2)n (式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合之金屬箔；且其係可用於：在該表面將樹脂製之板狀載子剝離並使之密著的用途者。 A metal foil characterized by being at least on one side having the formula: [Chem. 3](R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkoxy group or a halogen atom ; R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M in Al, Ti or Zr n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m + n is a valence of M, that is, when Al is 3, Ti, Zr is an aluminate compound, a titanate compound or a zirconate compound represented by 4), a hydrolyzed product thereof, and the condensate of the hydrolyzed product, which are combined individually or in combination. A metal foil; and it can be used for a user who peels and sticks a resin-made plate-shaped carrier on this surface. 如申請專利範圍第16項之金屬箔，其中係將金屬箔的鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以相對於使之單獨或複數組合而作用側之表面，在使該化合物進行作用前，經過鉻酸鹽處理者。 The metal foil of claim 16, wherein the metal foil is an aluminate compound, a titanate compound or a zirconate compound, and the like is a hydrolyzed product, and the condensate of the hydrolyzed product is The surface treated with the chromate is applied to the surface of the active side in combination with it alone or in combination. 如申請專利範圍第16項之金屬箔，其中與金屬箔之載子接合側的表面，其十點平均粗糙度(Rz jis)在3.5μm以下。 The patentable scope of application of the metal foil 16, the side surface of the carrier and the metal foil wherein the engagement, the ten point-average roughness (Rz jis) at 3.5 μ m or less. 一種樹脂製之板狀載子，其特徵為至少在一側的表面上，具有下式：【化4】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合者。 A resin-made plate-shaped carrier characterized by having at least one surface having the following formula: [Chemical Formula 4] (R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkane group or a halogen atom; R 2 is selected from alkyl groups, the cycloalkyl groups are alkyl or aryl hydrocarbon group, one or more of the hydrogen atoms are substituted by a halogen atom such a person any hydrocarbon group; M-based Al, Any of Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m + n is a valence of M, In other words, in the case of Al, it is 3, and in the case of Ti and Zr, it is an aluminate compound, a titanate compound or a zirconate compound represented by 4), and a hydrolyzed product thereof, and a condensate of the hydrolyzed product, Individual or plural combination. 一種板狀載子，其特徵為其係至少在一側的表面上，具有將下式：【化5】(R1)m-M-(R2)n(式中，R1係一種烷氧基或鹵素原子；R2係選自烷基、環烷基或芳基所成群之烴基，或有一個以上的氫原子被鹵素原子取代之此等任一者的 烴基；M係Al、Ti或Zr中之任一者；n為0或1或2，m為1以上M的價數以下之整數，R1的至少一個為烷氧基；又，m+n係M的價數，亦即Al時為3，Ti、Zr時為4)所示之鋁酸鹽化合物、鈦酸鹽化合物或鋯酸鹽化合物，其等之加水分解生成物，該加水分解生成物之縮合體，以單獨或複數組合之樹脂製之板狀載子；且其係可用於：在該表面將金屬箔剝離並使之密著的用途者。 A plate-like carrier characterized by being on at least one surface having the following formula: [R 5 ](R 1 ) m -M-(R 2 ) n (wherein R 1 is an alkane An oxy group or a halogen atom; R 2 is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group or an aryl group, or a hydrocarbon group having one or more hydrogen atoms substituted by a halogen atom; M-based Al, Any of Ti or Zr; n is 0 or 1 or 2, m is an integer below 1 valence of M, and at least one of R 1 is an alkoxy group; further, m + n is a valence of M, In other words, in the case of Al, it is 3, and in the case of Ti and Zr, it is an aluminate compound, a titanate compound or a zirconate compound represented by 4), and a hydrolyzed product thereof, and a condensate of the hydrolyzed product, A plate-shaped carrier made of resin alone or in combination; and it can be used for a user who peels and closes the metal foil on the surface. 一種多層金屬張積層板的製造方法，其特徵為其係包含：相對於申請專利範圍第1~10項中任一項之附載子金屬箔至少一面的金屬箔側，將樹脂進行層合，接著再將樹脂或金屬箔重複一次以上進行層合者。 A method for producing a multilayer metal laminated laminate, characterized by comprising: laminating a resin with respect to a metal foil side of at least one side of the attached sub-metal foil according to any one of claims 1 to 10; The resin or metal foil is repeated one or more times for lamination. 一種多層金屬張積層板的製造方法，其特徵為其係包含：在申請專利範圍第1~10項中任一項之附載子金屬箔的金屬箔側，將樹脂進行層合，接著，再將樹脂、單面或雙面金屬張積層板、或申請專利範圍第1~10項中任一項之附載子金屬箔、或金屬箔重複一次以上進行層合者。 A method for producing a multilayer metal laminated laminate, characterized in that it comprises: laminating a resin on a side of a metal foil attached to a sub-metal foil according to any one of claims 1 to 10, and then The resin, the single-sided or double-sided metal laminated laminate, or the attached sub-metal foil or the metal foil of any one of the above claims 1 to 10 is laminated one or more times. 一種多層金屬張積層板的製造方法，其特徵為其於申請專利範圍第21或第22項之多層金屬張積層板的製造方法中，更包含了將附載子金屬箔之板狀載子與金屬箔加以剝離並分離的步驟。 A method for manufacturing a multilayer metal laminated laminate, characterized in that in the method for manufacturing a multilayer metal laminated laminate according to claim 21 or 22, the method further comprises a plate-shaped carrier and a metal with a carrier metal foil The step of peeling and separating the foil. 一種多層金屬張積層板的製造方法，其特徵為其於申請專利範圍第23項之製造方法中，包含了將已經剝離並分離之金屬箔的一部或全部，以蝕刻進行除去之步驟。 A method for producing a multilayer metal laminated laminate, characterized in that in the manufacturing method of claim 23, a step of removing one or all of the metal foil which has been peeled off and separated by etching is included. 一種多層金屬張積層板，其特徵為其係以申請專利範圍第21~24項中任一項之製造方法所得者。 A multilayer metal laminated laminate characterized by the method of manufacturing according to any one of claims 21 to 24. 一種組合基板的製造方法，其特徵為其係包含：於申請專利範圍第1~10項中任一項之附載子金屬箔的金屬箔側，將組合配線層形成一層以上之步驟者。 A method for producing a composite substrate, which comprises the step of forming one or more layers of the wiring layer on the side of the metal foil to which the sub-metal foil is attached, according to any one of claims 1 to 10. 如申請專利範圍第26項之組合基板的製造方法，其特徵為其組合配線層係使用減成法或全加成法或半加成法的至少一種而形成者。 The method for producing a composite substrate according to claim 26, wherein the combined wiring layer is formed by using at least one of a subtractive method or a full additive method or a semi-additive method. 一種組合基板的製造方法，其特徵為其係包含：於申請專利範圍第1~10項中任一項之附載子金屬箔至少一面的金屬箔側，將樹脂進行層合，接著，再將樹脂、單面或雙面配線基板、單面或雙面金屬張積層板、申請專利範圍第1~10項中任一項之附載子金屬箔或金屬箔，重複一次 以上進行層合者。 A method for producing a composite substrate, comprising: laminating a resin on at least one side of a metal foil attached to at least one side of a sub-metal foil according to any one of claims 1 to 10, and then resinating the resin , single-sided or double-sided wiring substrate, single-sided or double-sided metal laminate, and the accompanying sub-metal foil or metal foil of any one of claims 1 to 10, repeated once The above is carried out. 一種組合基板的製造方法，其特徵為其係進一步包含：於申請專利範圍第28項之組合基板的製造方法中，在單面或雙面配線基板、單面或雙面金屬張積層板、附載子金屬箔的金屬箔、附載子金屬箔的板狀載子、金屬箔或樹脂上，鑽孔，於該孔洞的側面或底面進行傳導電鍍的步驟。 A method for manufacturing a composite substrate, characterized by further comprising: in the method for manufacturing a composite substrate of claim 28, on a single-sided or double-sided wiring substrate, a single-sided or double-sided metal laminate, and an attached The metal foil of the sub-metal foil, the plate-shaped carrier on which the sub-metal foil is attached, the metal foil or the resin is drilled, and the step of conducting electroplating is performed on the side surface or the bottom surface of the hole. 一種組合基板的製造方法，其特徵為其係進一步包含：於申請專利範圍第28項之組合基板的製造方法中，在構成單面或雙面配線基板之金屬箔、構成單面或雙面金屬張積層板之金屬箔、構成附載子金屬箔之金屬箔、以及金屬箔之至少一者之上，進行一次以上配線形成之步驟。 A method for manufacturing a composite substrate, characterized by further comprising: in the method for manufacturing a composite substrate of claim 28, a metal foil constituting a single-sided or double-sided wiring substrate, constituting a single-sided or double-sided metal The step of forming one or more wirings on at least one of the metal foil of the laminate, the metal foil constituting the attached sub-metal foil, and the metal foil. 一種組合基板的製造方法，其特徵為其係進一步包含：於申請專利範圍第29項之組合基板的製造方法中，在構成單面或雙面配線基板之金屬箔、構成單面或雙面金屬張積層板之金屬箔、構成附載子金屬箔之金屬箔、以及金屬箔之至少一者之上，進行一次以上配線形成之步驟。 A method of manufacturing a composite substrate, characterized by further comprising: in the method of manufacturing a composite substrate of claim 29, in forming a metal foil of a single-sided or double-sided wiring substrate, forming a single-sided or double-sided metal The step of forming one or more wirings on at least one of the metal foil of the laminate, the metal foil constituting the attached sub-metal foil, and the metal foil. 如申請專利範圍第30項之組合基板的製造方法，其中更包含：於配線所形成之表面上，使單面上密著有金屬箔之申請專利範圍第1~10項中任一項之附載子金屬箔的樹脂板側，與其接觸，並進行層合之步驟。 The method for manufacturing a composite substrate according to claim 30, further comprising: attaching any one of the first to tenth patent claims to the surface of the wiring formed on the surface of the wiring The resin sheet side of the sub-metal foil is in contact with it and is subjected to a lamination step. 如申請專利範圍第31項之組合基板的製造方法，其中更包含：於配線所形成之表面上，使單面上密著有金屬箔之申請專利範圍第1~10項中任一項之附載子金屬箔的樹脂板側，與其接觸，並進行層合之步驟。 The method for manufacturing a composite substrate according to claim 31, further comprising: attaching any one of the first to tenth patent claims to the surface of the wiring formed on the surface of the wiring The resin sheet side of the sub-metal foil is in contact with it and is subjected to a lamination step. 如申請專利範圍第30項之組合基板的製造方法，其中更包含了於配線所形成之表面上，將樹脂層合，並對該樹脂在雙面上均以金屬箔密著之申請專利範圍第1~10項中任一項之附載子金屬箔的一方金屬箔，使其接觸，並進行層合之步驟。 The method for manufacturing a composite substrate according to claim 30, further comprising laminating the resin on the surface formed by the wiring, and applying the patent to the resin on both sides of the resin. Any one of the metal foils of the sub-metal foil attached to any one of items 1 to 10 is brought into contact and laminated. 如申請專利範圍第31項之組合基板的製造方法，其中更包含了於配線所形成之表面上，將樹脂層合，並對該樹脂在雙面上均以金屬箔密著之申請專利範圍第1~10項中任一項之附載子金屬箔的一方金屬箔，使其接觸，並進行層合之步驟。 The method for manufacturing a composite substrate according to claim 31, further comprising the step of coating the resin on the surface formed by the wiring, and applying the patent to the resin on both sides of the resin. Any one of the metal foils of the sub-metal foil attached to any one of items 1 to 10 is brought into contact and laminated. 如申請專利範圍第28~35項中任一項之組合基板的製造方法，其中樹脂之至少一者為預浸漬片。 The method for producing a composite substrate according to any one of claims 28 to 35, wherein at least one of the resins is a prepreg. 一種組合配線板的製造方法，其特徵為其於申請專利範圍第26~35 項中任一項之組合基板的製造方法中，更包含將附載子金屬箔的板狀載子與金屬箔進行剝離並分離之步驟。 A manufacturing method of a combined wiring board, which is characterized in that it is in the scope of patent application Nos. 26~35 The method for producing a composite substrate according to any one of the preceding claims, further comprising the step of separating and separating the plate-shaped carrier carrying the sub-metal foil from the metal foil. 一種組合配線板的製造方法，其特徵為其於申請專利範圍第36項之組合基板的製造方法中，更包含將附載子金屬箔的板狀載子與金屬箔進行剝離並分離之步驟。 A method for producing a composite wiring board, which is characterized in that, in the method for producing a composite substrate of claim 36, the method further comprises the steps of separating and separating the plate-shaped carrier carrying the sub-metal foil from the metal foil. 一種組合配線板的製造方法，其特徵係於申請專利範圍第37項之組合配線板的製造方法中，將與板狀載子密著之金屬箔的一部或全部，以蝕刻方式加以除去之步驟。 A method for manufacturing a composite wiring board, characterized in that in the method for manufacturing a composite wiring board according to claim 37, one or all of the metal foil adhered to the plate-shaped carrier are removed by etching. step. 一種組合配線板，其特徵係由申請專利範圍第37~39項中任一項之製造方法所得者。 A combination wiring board characterized by being produced by the manufacturing method of any one of claims 37 to 39. 一種印刷電路板的製造方法，其特徵係包含：藉由申請專利範圍第26~35項中任一項之製造方法，將組合基板加以製造之步驟。 A method of manufacturing a printed circuit board, comprising the step of manufacturing a composite substrate by the manufacturing method according to any one of claims 26 to 35. 一種印刷電路板的製造方法，其特徵係包含：藉由申請專利範圍第37項之製造方法，製造組合配線板之步驟。 A method of manufacturing a printed circuit board, comprising the steps of: manufacturing a combined wiring board by the manufacturing method of claim 37. 一種印刷電路板的製造方法，其特徵係包含：藉由申請專利範圍第38項之製造方法，製造組合配線板之步驟。 A method of manufacturing a printed circuit board, comprising the steps of: manufacturing a combined wiring board by the manufacturing method of claim 38.
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