KR20150059781A - Production method for multilayer printed wiring board, and base material - Google Patents

Abstract

A method of manufacturing a multilayer printed wiring board includes a first step of preparing a base substrate having a resin layer laminated on at least one main surface of a metal plate carrier with a release agent layer interposed therebetween; And a second step of laminating the upper layer. The substrate thickness of the plate-like carrier may be 5 占 퐉 or more and 1600 占 퐉 or less. The peel strength between the plate-like carrier and the resin layer may be 10 gf / cm or more and 200 gf / cm or less.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a multilayer printed wiring board,

The present invention relates to a method of manufacturing a multilayer printed wiring board and a base substrate.

Various developments have conventionally been carried out with respect to multilayer printed wiring boards. For example, Patent Document 1 discloses a configuration in which a prepreg is used as a carrier of a copper foil, and a copper foil is laminated on the prepreg so as to be detachable.

Japanese Laid-Open Patent Publication No. 2009-256125

The multilayer printed wiring board typically includes a buildup layer formed by laminating a buildup layer containing at least one wiring layer and at least one insulation layer on a resin base substrate. However, if the resin base substrate is thinned, Warpage or warpage may occur, which may cause troubles in the mounting process. In view of this point, the present invention aims to provide a base substrate that functions as a support when manufacturing a thin multilayered printed circuit board having a different structure from the conventional one.

A method of manufacturing a multilayer printed wiring board according to the present invention includes a first step of preparing a base substrate having a resin layer laminated on at least one main surface of a metal plate carrier with a release agent layer interposed therebetween; And a second step of laminating at least one build-up layer on the resin layer.

The substrate thickness of the plate-like carrier may be 5 mu m or more and 1600 mu m or less.

The peel strength between the plate-like carrier and the resin layer may be 10 gf / cm or more and 200 gf / cm or less.

The peel strength between the plate-like carrier and the resin layer after heating at 220 ° C for at least 3 hours, 6 hours, or 9 hours may be 10 gf / cm or more and 200 gf / cm or less.

And a third step of separating the resin layer on which the buildup layer is laminated and the plate-like carrier from each other.

The method for manufacturing the multilayer printed wiring board in which the resin layer is the first resin layer,

The second resin layer different from the first resin layer and the fourth step of laminating an additional buildup layer may be further included on the multilayer printed wiring board obtained by the third step.

The resin layer may be a prepreg.

The resin layer may have a glass transition temperature Tg of 120 to 320 ° C.

The build-up layer may include at least one insulating layer and at least one wiring layer.

The at least one wiring layer included in the buildup layer may be a patterned or non-patterned metal foil.

The at least one insulating layer included in the buildup layer may be a prepreg.

The build-up layer may include a single-sided or double-sided metal clad laminate.

The build-up layer may be formed using at least one of a subtractive method, a pull additive method, and a semi-additive method.

And a fifth step of performing a dicing treatment on the laminate obtained by laminating the buildup layer on the base substrate.

It is preferable that at least one groove is formed in the laminated body in which the buildup layer is laminated on the base substrate by the dicing process, and the buildup layer can be separated (singulated) by the groove.

And a sixth step of forming a via wiring with respect to at least one insulating layer included in the buildup layer.

Wherein the release agent layer has the following formula:

[Chemical Formula 1]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.

, The hydrolysis product thereof, and the condensation product of the hydrolysis product may be used singly or in combination.

The release agent layer may be formed using a compound having two or less mercapto groups in the molecule.

Wherein the release agent layer has the following formula:

(2)

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of at least ¹ and not more than M, and at least one of R ¹ is an alkoxy group. 3 for Ti and 4 for Zr)

, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof may be used singly or in combination.

The releasing agent layer may be a resin coating film composed of any one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin.

The plate-like carrier may be made of copper or a copper alloy.

The wiring layer may be made of copper or a copper alloy.

The multilayer printed wiring board according to the present invention is a multilayer printed wiring board manufactured by the method for manufacturing a multilayer printed wiring board described in any of the above.

A base substrate according to the present invention is a base substrate used in a method for manufacturing a multilayer printed wiring board, comprising: a metal plate carrier; a release agent layer formed on at least one main surface of the plate carrier; And a resin layer laminated on the carrier, wherein the resin layer and the plate-like carrier are peelable.

The substrate thickness of the plate-like carrier may be 5 mu m or more and 1600 mu m or less.

The peel strength between the plate-like carrier and the resin layer may be 10 gf / cm or more and 200 gf / cm or less.

The peel strength between the plate-like carrier and the resin layer after heating at 220 ° C for at least 3 hours, 6 hours, or 9 hours may be 10 gf / cm or more and 200 gf / cm or less.

The plate-like carrier may be made of copper or a copper alloy.

The resin layer may be made of a prepreg.

Wherein the release agent layer has the following formula:

(3)

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.

, The hydrolysis product thereof, and the condensation product of the hydrolysis product may be used singly or in combination.

The release agent layer may be formed using a compound having two or less mercapto groups in the molecule.

Wherein the release agent layer has the following formula:

[Chemical Formula 4]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of at least ¹ and not more than M, and at least one of R ¹ is an alkoxy group. 3 for Ti and 4 for Zr)

, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof may be used singly or in combination.

The releasing agent layer may be a resin coating film composed of any one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin.

The laminate related to the present invention is a laminate having a releasing agent layer laminated on at least one main surface of a metal plate carrier,

Wherein the release agent layer has the following formula:

[Chemical Formula 5]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.

, A hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination.

The laminate related to the present invention is a laminate obtained by laminating a release agent layer on at least one main surface of a metal plate carrier, wherein the release agent layer is made of a compound having two or less mercapto groups in the molecule.

The laminate related to the present invention is a laminate having a releasing agent layer laminated on at least one main surface of a metal plate carrier,

Wherein the release agent layer has the following formula:

[Chemical Formula 6]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of at least ¹ and not more than M, and at least one of R ¹ is an alkoxy group. 3 for Ti and 4 for Zr)

, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination.

A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,

Wherein the release agent layer is a resin coating film composed of one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin.

The plate-like carrier may be made of copper or a copper alloy.

According to the present invention, it is possible to separate a metal plate-like carrier and a buildup layer after lamination of a buildup layer, and to efficiently manufacture a thin multilayer printed wiring board.

1 is a schematic sectional view of a base substrate according to a first embodiment of the present invention.
2 is a schematic process diagram showing a state in which a buildup layer is laminated on a base substrate according to the first embodiment of the present invention.
3 is a process diagram schematically showing a step of peeling a multilayer printed wiring board and a plate-like carrier according to the first embodiment of the present invention.
4 is a schematic cross-sectional view of a base substrate according to a second embodiment of the present invention
5 is a schematic cross-sectional view showing a state in which buildup layers are laminated on both surfaces of a base substrate according to a second embodiment of the present invention.
6 is a diagram showing a table according to an embodiment of the present invention

Hereinafter, embodiments of the present invention will be described with reference to the drawings. It is to be noted that each embodiment is not independent of each other and can be appropriately combined by a person skilled in the art without being described in detail, and the synergistic effect of this combination can be grasped. The redundant explanation between the embodiments will be omitted in principle.

≪ First Embodiment >

The first embodiment will be described with reference to Figs. 1 to 3. Fig. 1 is a schematic cross-sectional view of a base substrate. 2 is a schematic process chart showing a state in which buildup layers are laminated on a base substrate. 3 is a process diagram schematically showing a step of peeling a multilayer printed wiring board and a plate-like carrier.

1, the base substrate 100 includes a metal plate carrier 10 having a predetermined thickness, a release agent layer 20 laminated on the upper surface (main surface) of the plate-like carrier 10, and a release agent layer 20 interposed And a prepreg 30 as an example of a resin layer laminated on the upper surface of the plate-shaped carrier 10, and the plate-like carrier 10, the releasing agent layer 20 and the prepreg 30 are laminated in this order It is a sieve. It is not always necessary to form the release agent layer 20 on the entire surface of the upper surface of the plate-like carrier 10 and similarly it is not always necessary to laminate the prepreg 30 on the entire upper surface of the release agent layer 20 none. The shape when viewed from the top surface of the plate-like carrier 10 or the prepreg 30 is not limited to a rectangle, and may be a different shape such as a circle. The prepreg 30 is typically a layer to be the lowest layer of the multilayer printed wiring board. In other words, the prepreg 30 is equivalent to the insulating layer 40 constituting the buildup layer 110. This point is also apparent from the following description.

The releasing agent layer 20 is formed on the upper surface (main surface) of the plate-like carrier 10 after the plate-like carrier 10 is first prepared, for example, And then the prepreg 30 may be laminated via the release agent layer 20. Alternatively, the release agent layer 20 may be laminated on the lower surface (main surface) of the prepreg 30, and the laminate of the prepreg 30 and the release agent layer 20 may be laminated on the plate-like carrier 10. The release agent layer 20 can be deposited on the prepreg 30 or the plate-like carrier 10 using conventional coating techniques. The thickness of the plate-like carrier 10 or the prepreg 30 can be adjusted by any known means or method.

A buildup layer 110 including at least one insulating layer 40 and at least one wiring layer 50 is stacked on the prepreg 30 of the base substrate 100 as shown in Figs. The buildup layer 110 is a laminate of a single-layer insulating layer 40 and a single-layer wiring layer 50. In FIG. 2, the buildup layer 110 having a two-layer structure including the prepreg 30, Respectively. The insulating layer 40 of the buildup layer 110 is preferably made of a resin layer, more preferably a prepreg containing a thermosetting resin. The wiring layer 50 of the build-up layer 110 is preferably a patterned or non-patterned metal layer, preferably a metal foil or a plated metal layer. The buildup layer 110 is formed by repeatedly laminating the insulating layer 40 and the wiring layer 50 in order. The buildup layer 110 is laminated on the base substrate 100 and then the buildup layer 110 is separated from the base substrate 100 so that the buildup layer 110 is formed as a suitably thin multilayer printed wiring board Can be obtained.

In the multilayer printed circuit board thus manufactured, the base substrate 100 used for stacking the build-up layer 110 is not included. In this sense, the multilayer printed wiring board according to the present embodiment can be regarded as a " thin " configuration. The term " thin " means, for example, that the thickness of the multilayer printed wiring board is 400 m or less, preferably 200 m or less, more preferably 100 m or less. However, when the multilayer printed wiring board requires an insulating layer or a wiring layer having an extremely large number of wiring layers (for example, ten or more layers) or a thickness of more than 100 mu m, May be exceeded.

In the laminating step of the build-up layer, the base substrate 100 itself is heated, or physically or chemically treated, and in some cases, immersed in a chemical liquid. Even after such a process, the peelability between the lowermost prepreg 30 and the plate-like carrier 10 of the multilayer printed wiring board schematically shown in Fig. 3, or simply the multilayer printed wiring board, is secured. Preferably, the release agent layer 20 remains on the side of the plate-like carrier 10, but is not limited thereto.

The constituent material and the layer thickness of the insulating layer 40 and the wiring layer 50 are arbitrary and one wiring layer 50 may be formed of a lamination of at least one conductive layer and one insulating layer 40 may be composed of at least one Or an insulating layer. The wiring layer 50 is composed of, for example, at least one metal foil. The insulating layer 40 is composed of at least one resin layer, preferably a thermosetting resin layer. The wiring layer 50 need not always be patterned, and may not necessarily be electrically connected to another wiring layer. Formation of the floating wiring layer 50 may be effective when controlling the capacitance generated between the wiring layers or adjusting the mechanical strength and the like of the multilayer printed wiring board.

The concrete structure of the buildup layer 110 is arbitrary. For example, the build-up layer 110 includes at least one insulating layer 40 and at least one wiring layer 50. For example, the at least one wiring layer 50 included in the buildup layer 110 is a patterned or non-patterned metal foil. For example, at least one insulating layer 40 included in the buildup layer 110 is a prepreg. For example, the buildup layer 110 includes a single-sided or double-sided metal clad laminate.

The plate-like carrier 10 is a metal plate, preferably a flat plate made of copper or copper alloy, and may have some flexibility depending on its size, but has a rigidity enough to secure its function as a support substrate desirable. The plate-like carrier 10 typically has a thickness of at least 5 mu m, more preferably at least 10 mu m, at least 30 mu m, at least 35 mu m, at least 50 mu m, at least 65 mu m, at least 70 mu m, at least 80 mu m, at least 100 mu m A metal foil having a thickness can be used. Typically, the sheet-like carrier 10 has a thickness of 1600 占 퐉 or less, more preferably 1500 占 퐉 or less, 1350 占 퐉 or less, 1000 占 퐉 or less, 800 占 퐉 or less, 500 占 퐉 or less, 400 占 퐉, 300 占 퐉 or less, May be used. The plate-like carrier 10 may be preferably a copper foil or a copper alloy foil.

The plate-shaped carrier 10 may be, for example, a flat plate manufactured by rolling a copper material, or a flat plate formed by laminating copper material in multiple layers. In this case, the flat plate may have a thickness of 1600 탆 or more. A copper material such as a copper foil obtained by electrolysis may be utilized for the plate-like carrier 10. As the constituent material of the plate-like carrier 10, a copper alloy may be used. By using a copper alloy, the hardness of the plate-like carrier 10 can be increased. As the copper alloy, at least one element selected from the group consisting of Ni, Si, Zn, Sn, Ti, P, Cr, B, Ag, Mg, Fe, V, Au, Pd, Co, Mn, beryllium and cadmium As a total of at least 0 mass% and not more than 80 mass%. The material of the plate-like carrier 10 is not particularly limited as long as it is a metal, and examples thereof include copper, gold, silver, iron, nickel, aluminum, chromium, titanium, zinc and magnesium. A copper alloy, an iron alloy, or an alloy using them.

As the copper, typically, 99.90% by mass or more of purity copper such as phosphorus deoxidized copper, oxygen free copper and tough pitch copper specified in JIS H0500 can be mentioned. Copper or a copper alloy containing 0.001 to 4.0 mass% of at least one of Sn, Ag, Au, Co, Cr, Fe, In, Ni, P, Si, Te, Ti, Zn and Zr in total.

Examples of the copper alloy include titanium copper, phosphor bronze, Colson alloy, tantalum copper, brass, and gold silver.

Titanium copper typically has a composition containing 0.5 to 5.0 mass% of Ti and the balance of copper and inevitable impurities. The titanium copper may further contain at least one of Fe, Co, V, Nb, Mo, B, Ni, P, Zr, Mn, Zn, Si, Mg and Cr in a total amount of 2.0 mass% or less.

Phosphorous-bronze typically refers to a copper alloy containing Sn as the main component and phosphorus in a smaller amount than phosphorus. As an example, phosphor bronze contains 3.5 to 11% by mass of Sn and 0.03 to 0.35% by mass of P, and has a composition consisting of the residual copper and inevitable impurities. The phosphor bronze may contain 1.0% by mass or less of elements such as Ni and Zn in total.

The Colson alloy typically refers to a copper alloy to which an element (for example, any one or more of Ni, Co, and Cr) that forms a compound with Si is added and which precipitates as secondary phase particles in the parent phase . As an example, the Colson alloy contains 1.0 to 4.0% by mass of Ni and 0.2 to 1.3% by mass of Si, and has a composition consisting of the remaining copper and inevitable impurities. As another example, the Colson alloy contains 1.0 to 4.0% by mass of Ni, 0.2 to 1.3% by mass of Si, and 0.03 to 0.5% by mass of Cr, and has a composition consisting of the remaining copper and inevitable impurities. As another example, the Colson alloy contains 1.0 to 4.0% by mass of Ni, 0.2 to 1.3% by mass of Si, and 0.5 to 2.5% by mass of Co, and has a composition consisting of the remaining copper and inevitable impurities. As another example, the Colson alloy contains 1.0 to 4.0% by mass of Ni, 0.2 to 1.3% by mass of Si, 0.5 to 2.5% by mass of Co and 0.03 to 0.5% by mass of Cr, and the balance copper and inevitable impurities . As another example, the Colson alloy contains 0.2 to 1.3% by mass of Si and 0.5 to 2.5% by mass of Co, and has a composition consisting of the remaining copper and inevitable impurities. Other elements (for example, Mg, Sn, B, Ti, Mn, Ag, P, Zn, As, Sb, Be, Zr, Al and Fe) may be added to the Colson alloy. These other elements are generally added in a total amount of about 2.0% by mass. For example, as another example, the Colson alloy contains 1.0 to 4.0% by mass of Ni, 0.2 to 1.3% by mass of Si, 0.01 to 2.0% by mass of Sn and 0.01 to 2.0% by mass of Zn, And has a composition composed of impurities.

Brass is an alloy of copper and zinc, particularly copper alloy containing at least 20 mass% of zinc. The upper limit of zinc is not particularly limited, but it is 60 mass% or less, preferably 45 mass% or less, or 40 mass% or less.

Dandong is an alloy of copper and zinc, and refers to a copper alloy containing 1 to 20% by mass of zinc, and more preferably 1 to 10% by mass of zinc. The single end may contain 0.1 to 1.0% by mass of tin.

Refers to a copper alloy containing 60% by mass to 75% by mass of copper, 8.5% by mass to 19.5% by mass of nickel, and 10% by mass to 30% by mass of zinc mainly comprising iron and copper.

As the aluminum and the aluminum alloy, for example, those containing 99 mass% or more of Al can be used. Concretely, aluminum or an alloy thereof of 99.00 mass% or more of Al represented by Alloy Nos. 1085, 1080, 1070, 1050, 1100, 1200, 1N00, 1N30 described in JIS H 4000 can be used.

Nickel and a nickel alloy containing, for example, 99 mass% or more of Ni can be used. Concretely, it is possible to use nickel or its alloy of 99.0% by mass or more of Ni represented by alloy numbers NW2200 and NW2201 described in JIS H4551.

As the iron alloy, for example, stainless steel, mild steel, iron nickel alloy and the like can be used. As the stainless steel, SUS 301, SUS 304, SUS 310, SUS 316, SUS 430, SUS 631 (all of JIS standard) can be used. Mild steel having carbon content of 0.15 mass% or less can be used for mild steel, and mild steel described in JIS G3141 can be used. The iron nickel alloy contains 35 to 85% by mass of Ni and the balance of Fe and inevitable impurities. Specifically, an iron nickel alloy described in JIS C2531 can be used. As the plate-shaped carrier, a known metal such as aluminum, an aluminum alloy, nickel, a nickel alloy, iron, an iron alloy, or stainless steel may be used.

The Vickers hardness HV of the plate-like carrier 10 is typically 30 to 100 F / N / d / mm ² , preferably 50 to 80 F / N / ² . It is preferable to secure sufficient hardness of the flat plate made of copper or copper alloy as the plate-like carrier 10.

The plate-like carrier 10 may be subjected to surface treatment. For example, a metal plating (Ni plating, Ni-Zn alloy plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy plating, Co-Ni alloy plating Chromate treatment (including the case where one or more alloying elements such as Zn, P, Ni, Mo, Zr and Ti are contained in the chromate treatment liquid) and surface roughness adjustment (Cu-Ni-Co alloy plating, Cu-Ni alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-As alloy plating, Cu- As-W alloy plating, and the like). The roughening treatment not only affects the peel strength of the plate-like carrier 10 and the release agent layer 20, but also greatly affects the chromate treatment. The chromate treatment is important from the viewpoints of rust resistance and discoloration resistance, but it tends to significantly increase the peel strength, which is also important as a means for adjusting the peel strength.

For example, the glossy surface of the copper material may be subjected to a nickel-zinc (Ni-Zn) alloy plating treatment and a chromate (Cr-Zn chromate) treatment under the following conditions.

(Nickel-zinc alloy plating)

Ni concentration of 17 g / l (added as NiSO ₄ )

Zn concentration 4 g / l (added as ZnSO ₄ )

pH 3.1

Solution temperature 40 ° C

Current density 0.1 to 10 A / dm 2

Plating time 0.1 ~ 10 seconds

(Chromate treatment)

Cr concentration 1.4 g / l (added as CrO ₃ or K ₂ CrO ₇ )

Zn concentration 0.01 to 1.0 g / l (added as ZnSO ₄ )

Na ₂ SO ₄ concentration 10 g / l

pH 4.8

Solution temperature 55 ° C

Current density 0.1 to 10 A / dm 2

Plating time 0.1 ~ 10 seconds

The release agent layer 20 may be selected from any material that is relatively firmly adhered to the plate-like carrier 10 and relatively weakly adhered to the prepreg 30. As described above, the base substrate 100 may be heated and chemically or physically treated in the step of laminating the build-up layer 110 in some cases. From this point of view, it is preferable that the releasing agent layer 20 also has heat resistance and chemical resistance and is easily deteriorated or eroded by chemicals. The releasing agent layer 20 can be formed on the plate-like carrier 10 by any method such as spin coating, dip coating, spray coating, printing or the like, but is not limited thereto.

The upper surface of the plate-shaped carrier 10 on which the release agent layer 20 is formed may be either a roughened surface (M surface) or a glossy surface (S surface), but it is preferable that the upper surface is a glossy surface rather than a rough surface. When a rolled metal foil, more preferably a rolled copper foil, is used as the sheet-like carrier, the both surfaces become glossy surfaces, so that it is more preferable to form the release agent layer 20 on both sides of the sheet-like carrier. As a result, the quality of the base substrate 100 can be stabilized by suppressing unevenness in the illuminance of the upper surface of the plate-like carrier 10 on which the releasing agent layer 20 is laminated. The thickness of the releasing agent layer 20 is typically 0.001 to 10 mu m, preferably 0.001 to 0.1 mu m.

(1) Silane compound

The constituent material of the releasing agent layer 20 is not limited to those disclosed in the present application or available at present, but may be, for example, a silane compound represented by the following formula, a hydrolyzed product thereof, The condensate may be used singly or in combination of plural in the release agent layer 20.

(7)

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.

The silane compound needs to have at least one alkoxy group. When there is no alkoxy group and a substituent is constituted only by a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, the releasing agent layer 20 and the plate- The adhesion of the surface of the carrier 10 tends to be excessively lowered. It is necessary that the silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group or at least one hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom. If the hydrocarbon group is not present, the adhesion between the release agent layer 20 and the surface of the plate-like carrier 10 tends to increase. In addition, the alkoxy group according to the present invention includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom.

In adjusting the peel strength between the plate-like carrier 10 and the prepreg 30 (or the build-up layer 110 including the prepreg 30) to a suitable range to be described later, the silane compound has an alkoxy group of 3 , And the above hydrocarbon group (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom). When this is expressed in the above formula, both R ³ and R ⁴ are referred to as alkoxy groups.

Alkoxy groups include, but are not limited to, methoxy, ethoxy, n- or isopropoxy, n-, iso- or tert-butoxy, n-, iso- or neo- Branched or cyclic C 1-20, preferably C 1-10, more preferably C 1-6 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, An alkoxy group having 1 to 5 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group includes, but is not limited to, methyl, ethyl, n- or isopropyl, n-, iso- or tert-butyl, n-, iso- or neopentyl, n- An alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as an octyl group and an n-decyl group.

Examples of the cycloalkyl group include, but are not limited to, cycloalkyl groups having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group .

Examples of the aryl group include an aryl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms such as a phenyl group, a phenyl group substituted with an alkyl group (e.g., a tolyl group, a xylyl group), a 1- or 2-naphthyl group, have.

These hydrocarbon groups may be substituted with at least one hydrogen atom by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or phenyltrimethoxysilane, alkyl-substituted phenyltrimethoxysilane (for example, p- (methyl) phenyl (meth) acrylate, phenyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, Trimethoxysilane), methyltriethoxysilane, ethyltriethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyl Phenyl triethoxysilane, alkyl substituted phenyltriethoxysilane (for example, p- (methyl) phenyltriethoxysilane), (3, 4-dimethylphenyltriethoxysilane), triethylsilane, triethoxysilane, octyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, 3,3-trifluoropropyl) trimethoxysilane, and tridecafluorooctyltriethoxysilane, methyltrichlorosilane , Dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, hydrolysis products of these, and condensation products of these hydrolysis products . Of these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane and decyltrimethoxysilane are preferable from the viewpoint of availability.

(2) a compound having two or less mercapto groups in the molecule

A compound having not more than two mercapto groups in the molecule may be used in the release agent layer 20 instead of the silane compound described above. Examples thereof include thiol, dithiol, thiocarboxylic acid or salt thereof, dithiocarboxylic acid or salt thereof, thiosulfonic acid or salt thereof, and dithiosulfonic acid or salt thereof, and at least one Species can be used.

Thiol has one mercapto group in the molecule and is represented by, for example, R-SH. Here, R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group.

Dithiol has two mercapto groups in the molecule and is represented by, for example, R (SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. The two mercapto groups may be bonded to the same carbon or may be bonded to carbon or nitrogen, respectively, which are different from each other.

The thiocarboxylic acid is one in which the hydroxyl group of the organic carboxylic acid is substituted with a mercapto group and is represented by, for example, R-CO-SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. The thiocarboxylic acid can also be used in the form of a salt. Also, a compound having two thiocarboxylic acid groups can be used.

The dithiocarboxylic acid is one in which two oxygen atoms in the carboxy group of the organic carboxylic acid are substituted with a sulfur atom and is represented by, for example, R- (CS) -SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. The dithiocarboxylic acid can also be used in the form of a salt. A compound having two dithiocarboxylic acid groups can also be used.

The thiosulfonic acid is obtained by replacing the hydroxyl group of the organic sulfonic acid with a mercapto group and is represented by, for example, R (SO ₂ ) -SH. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. The thiosulfonic acid can also be used in the form of a salt.

The dithiosulfonic acid is represented by R - ((SO ₂ ) - SH) ₂ , in which two hydroxyl groups of the organic disulfonic acid are each substituted with a mercapto group. R represents an aliphatic or aromatic hydrocarbon group or heterocyclic group which may contain a hydroxyl group or an amino group. The two thiosulfonic acid groups may be bonded to the same carbon or may be bonded to each other, respectively. The dithiosulfonic acid can also be used in the form of a salt.

Examples of suitable aliphatic hydrocarbon groups for R include an alkyl group and a cycloalkyl group, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

Examples of the alkyl group include, but are not limited to, methyl, ethyl, n- or iso-propyl, n-, iso- or tert- an n-octyl group, an n-decyl group, and other linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

The cycloalkyl group includes, but is not limited to, a cycloalkyl group having a carbon number of 3 to 10, preferably 5 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group And a cycloalkyl group.

Examples of the aromatic hydrocarbon group suitable as R include a phenyl group, a phenyl group substituted with an alkyl group (e.g., a tolyl group, a xylyl group), a 1- or 2-naphthyl group, An aryl group having 1 to 14 carbon atoms, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

Examples of the heterocyclic group suitable as R include imidazole, triazole, tetrazole, benzoimidazole, benzotriazole, thiazole, and benzothiazole. It is preferable that any of the hydroxyl group and the amino group or both do.

Preferable examples of the compound having two or less mercapto groups in the molecule include 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, 6-mercapto- Dodecanethiol, 10-amino-1-dodecanethiol, 10-amino-1-dodecanethiol, 1-dodecanethiol, Sodium thiophenol, thiobenzoic acid, 4-amino-thiophenol, p-toluenethiol, 2,4-dimethylbenzenethiol, 3-mercapto- 1,2,4 triazole, 2- mercapto-benzothiazole . Of these, 3-mercapto-1,2-propanediol is preferred from the viewpoint of water solubility and waste disposal.

(3) Metal alkoxide

A condensate of an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, or a hydrolysis product thereof (hereinafter, simply referred to as a metal alkoxide) having a structure represented by the following formula By using a plurality of the mixture, the plate-like carrier 10 and the prepreg 30 are adhered to each other, the adhesiveness is appropriately lowered and the peel strength can be adjusted to a range as described later.

[Chemical Formula 8]

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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M is Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of 1 or more and equal to or less than M, and at least one of R ¹ is an alkoxy group. Also, m + n is 3 in the case of M, that is, Al, and 4 in case of Ti and Zr.

It is necessary that the metal alkoxide has at least one alkoxy group. When there is no alkoxy group and a substituent is constituted by only a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, the adhesion between the plate- Is likely to deteriorate excessively. It is necessary that the metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, 0 to 2 hydrocarbon groups. When the number of the hydrocarbon groups is 3 or more, the adhesion between the plate-like carrier and the surface of the metal foil tends to be excessively lowered. In addition, the alkoxy group according to the present invention includes an alkoxy group in which at least one hydrogen atom is substituted with a halogen atom. In adjusting the peel strength of the plate-like carrier 10 and the prepreg 30 (or the build-up layer 110 including the prepreg 30) to a range described later, the metal alkoxide may have two alkoxy groups It is preferable that the hydrocarbon group (one or more hydrogen atoms include a hydrocarbon group substituted with a halogen atom) has one or two hydrocarbon groups.

Examples of the alkyl group include, but are not limited to, methyl, ethyl, n- or iso-propyl, n-, iso- or tert- an n-octyl group, an n-decyl group, and other linear or branched alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.

The cycloalkyl group includes, but is not limited to, a cycloalkyl group having a carbon number of 3 to 10, preferably 5 to 7 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group And a cycloalkyl group.

Examples of the aromatic hydrocarbon group suitable as R ² include a phenyl group, a phenyl group substituted with an alkyl group (e.g., a tolyl group, a xylyl group), a 1- or 2-naphthyl group, To 14 carbon atoms, and these hydrocarbon groups may contain either or both of a hydroxyl group and an amino group.

These hydrocarbon groups may be substituted with at least one hydrogen atom by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred aluminate compounds are trimethoxy aluminum, methyl dimethoxy aluminum, ethyl dimethoxy aluminum, n- or iso-propyl dimethoxy aluminum, n-, iso- or tert-butyl dimethoxy aluminum, n-, iso (For example, p- (methyl) phenyldimethoxyaluminum) or an alkyl substituted phenyldimethoxyaluminum (for example, p- (methyl) phenyldimethoxyaluminum) or neopentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, , Dimethyl methoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum, ethyl diethoxy aluminum, n- or iso-propyl diethoxy aluminum, n-, iso- or tert-butyl diethoxy aluminum, pentyl diethoxy aluminum, Diethoxy aluminum, octyl diethoxy aluminum, decyl diethoxy aluminum, phenyl diethoxy aluminum, alkyl substituted phenyl diethoxy aluminum (for example, p- (methyl) phenyl Diethoxy aluminum), dimethyl ethoxy aluminum, triisopropoxy aluminum, methyl diisopropoxy aluminum, ethyl diisopropoxy aluminum, n- or iso-propyl diethoxy aluminum, n-, iso- or tert- (E.g., isopropylaluminum, isopropylaluminum, isopropylaluminum, isopropylaluminum, isopropoxyaluminum, pentyldiisopropoxyaluminum, hexyldiisopropoxyaluminum, octyldiisopropoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, For example, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3-trifluoropropyl) dimethoxyaluminum, and tridecafluorooctyldiethoxyaluminum, methyldichloro Aluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, their hydrolysis There may be mentioned hydrous product, and such as those of the singer of the degradation product condensate. Of these, trimethoxyaluminum, triethoxyaluminum and triisopropoxyaluminum are preferable from the viewpoint of availability.

Examples of preferred titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tert-butyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium, alkyl-substituted phenyltrimethoxytitanium (for example, phenyltrimethoxytitanium, naphthyltrimethoxytitanium, isopropyltriethoxytitanium, n-isopropyltriethoxytitanium, n-isopropyltriethoxytitanium, p-methylphenyltrimethoxytitanium, dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, Or tert-butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyltriethoxytitanium, phenyltriethoxytitanium, alkyl-substituted phenyltriethoxytitanium (for example, , p- (methyl) phenyltriethoxytitanium), dimethyldiethoxytitanium, tetraisopropoxy But are not limited to, cadmium, cadmium, cadmium, manganese, titanium, titanium, titanium, titanium, titanium, , Hexyltriisopropoxytitanium, octyltriisopropoxytitanium, decyltriisopropoxytitanium, phenyltriisopropoxytitanium, alkyl-substituted phenyltriisopropoxytitanium (for example, p- (methyl) phenyl tri (3,3,3-trifluoropropyl) trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, methyl trichlorotitanium, dimethyldichlorotitanium, dimethyldichlorotitanium, Dimethylacetamide, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitan, hydrolysis products of these, and condensation products of these hydroxides. Of these, tetramethoxytitanium, tetraethoxytitanium and tetraisopropoxytitanium are preferable from the viewpoint of availability.

Examples of preferred zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert-butyltrimethoxyzirconium , n-, iso- or neopentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium, alkyl-substituted phenyltrimethoxyzirconium (for example, , p- (methyl) phenyltrimethoxyzirconium), dimethyldimethoxyzirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, n- or iso-propyltriethoxyzirconium, n-, iso - or tert-butyltriethoxyzirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, decyltriethoxyzirconium, phenyltriethoxyzirconium, alkyl (E.g., p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- Or isopropyl triethoxy zirconium, n-, iso- or tert-butyl triisopropoxy zirconium, pentyl triisopropoxy zirconium, hexyl triisopropoxy zirconium, octyl triisopropoxy zirconium, Phenyl triisopropoxy zirconium, alkyl substituted phenyl triisopropoxy zirconium (for example, p- (methyl) phenyl triisopropoxy titanate), dimethyl diisopropoxy zirconium, (3,3,3 -Trifluoropropyl) trimethoxy zirconium, and tridecafluorooctyltriethoxy zirconium, methyl trichloro zirconium, dimethyldichlorozirconium, trimethyl chlorozirconium, Phenyl trichloro zirconium, dimethyl difluorozirconium, dimethyl dibromo zirconium, diphenyl dibromo zirconium, hydrolysis products of these, and condensates of hydrolysis products of these. Of these, tetramethoxy zirconium, tetraethoxy zirconium and tetraisopropoxy zirconium are preferable from the viewpoint of availability.

The base substrate 100 can be manufactured by bringing the plate-like carrier 10 and the prepreg 30 in hot contact with each other. For example, after the metal alkoxide is coated on the surface of the laminated carrier 10 and / or the prepreg 30, the surface of the plate-like carrier 10 is coated with a B-stage resin prepreg 30 by hot press lamination.

The metal alkoxide can be used in the form of an aqueous solution. To increase the solubility in water, an alcohol such as methanol or ethanol may be added. Addition of an alcohol is particularly effective when a metal alkoxide having high hydrophobicity is used.

The higher the concentration of the metal alkoxide in the aqueous solution is, the lower the peel strength of the plate-like carrier 10 and the prepreg 30 (or the buildup layer 110 including the prepreg 30) tends to decrease, The peel strength can be adjusted by adjusting the alkoxide concentration. Although not limited, the concentration of the metal alkoxide in the aqueous solution may be 0.001 to 1.0 mol / l, and may be typically 0.005 to 0.2 mol / l.

The pH of the aqueous solution of the metal alkoxide is not particularly limited and can be used on the acidic side or on the alkaline side. For example, at a pH in the range of 3.0 to 10.0. From the viewpoint that no specific pH adjustment is required, the pH is preferably in the range of about 5.0 to 9.0, which is near neutral, and more preferably in the range of 7.0 to 9.0.

(4) a releasing member made of a resin coating film

By bonding the plate-like carrier 10 and the prepreg 30 using a resin coating film composed of any one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin, And the peel strength can be adjusted to a range as described below.

The adjustment of the peel strength for realizing such adhesion is carried out by using a resin coating film composed of one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluorine resin as described later. Such a resin coating film is subjected to a baking treatment under a predetermined condition as described later, and is used between the plate-like carrier and the metal foil for hot-press bonding, whereby the adhesiveness is appropriately lowered and the peel strength can be controlled within a range described later to be.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolak type epoxy resin, brominated epoxy resin, amine type epoxy resin, flexible epoxy resin, hydrogenated bisphenol A type epoxy resin, Brominated phenoxy resins, and the like.

Examples of the melamine resin include a methyletherified melamine resin, a butylated urea melamine resin, a butylated melamine resin, a methylated melamine resin, and a butylated alcohol-modified melamine resin. The melamine resin may be a mixed resin of the above resin with a butylated urea resin, a butylated benzoguanamine resin, or the like.

The number average molecular weight of the epoxy resin is preferably 2000 to 3000, and the number average molecular weight of the melamine resin is preferably 500 to 1000. By having such a number average molecular weight, the resin can be made into a coating material, and the adhesion strength of the resin coating film can be easily adjusted to a predetermined range.

Examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride.

Examples of silicones include methylphenylpolysiloxane, methylhydrogenpolysiloxane, dimethylpolysiloxane, modified dimethylpolysiloxane, and mixtures thereof. Here, the denaturation means, for example, an abrasion resistance, an abrasion resistance, an elastic modulus, an elastic modulus, an elastic modulus, an elastic modulus, an elastic modulus, an elastic modulus, Polyester modification, acyloxyalkyl modification, halogenated alkyl acyloxyalkyl modification, halogenated alkyl modification, aminoglycol modification, mercapto modification, and hydroxyl group-containing polyester modification.

If the film thickness of the resin coating film is too small, it is difficult to form the resin coating film too thinly, and the productivity tends to be lowered. Further, even if the film thickness exceeds a certain size, no further improvement in the peelability of the resin coating film is seen, and the manufacturing cost of the resin coating film tends to increase. From this viewpoint, the resin coating film preferably has a film thickness of 0.1 to 10 mu m, more preferably 0.5 to 5 mu m. The film thickness of the resin coating film is achieved by applying the resin coating material in a predetermined coating amount in the procedure described below.

In the resin coating film, silicon functions as a releasing agent for the resin coating film. Therefore, if the total amount of the epoxy resin and the melamine resin is excessively larger than that of silicon, the resin coating film is formed between the plate-like carrier 10 and the prepreg 30 (or the buildup layer 110 including the prepreg 30) The peel strength to be imparted is increased, so that the peelability of the resin coating film is lowered, so that the peeling strength can not easily be peeled off by human hands. On the other hand, if the total amount of the epoxy resin and the melamine resin is too small, the above-mentioned peeling strength becomes small, so that the peeling may occur during transportation or during processing. From this viewpoint, it is preferable that the total amount of the epoxy resin and the melamine resin is contained in an amount of 10 to 1500 parts by mass, more preferably 20 to 800 parts by mass, relative to 100 parts by mass of silicon .

The fluororesin, like silicon, functions as a releasing agent and has an effect of improving the heat resistance of the resin coating film. If the amount of the fluororesin is too large as compared with that of silicon, the above-mentioned peeling strength becomes small, so that it may be peeled off during transportation or processing, and the temperature required for the baking step to be described later is increased. From this viewpoint, the fluororesin is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, per 100 parts by mass of silicon.

The resin coating film may contain at least one kind of surface harmony selected from SiO ₂ , MgO, Al ₂ O ₃ , BaSO ₄ and Mg (OH) ₂ , in addition to silicon and an epoxy resin and / or a melamine resin and, Or may further contain particles. When the resin coating film contains surface roughening particles, the surface of the resin coating film becomes irregular. By the unevenness, the surface of the plate-like carrier or the metal foil coated with the resin coating film becomes uneven and becomes the surface on which the gloss is removed. The content of the surface roughening particles is not particularly limited as long as the resin coating film is uneven, but is preferably 1 to 10 parts by mass based on 100 parts by mass of silicon.

The particle size of the surface roughening particles is preferably 15 nm to 4 탆. Here, the particle diameter refers to an average particle diameter (average value of maximum particle diameter and minimum particle diameter) measured from a scanning electron microscope (SEM) photograph and the like. When the particle size of the surface roughening particles is in the above range, the amount of irregularity of the surface of the resin coating film is easily adjusted, and consequently the irregularity amount of the surface of the plate-like carrier or metal foil is easily adjusted. Concretely, the amount of unevenness of the surface of the plate-like carrier or metal foil is about 4.0 탆 at the maximum height roughness Ry defined by JIS.

Here, a manufacturing method of the base substrate 100 will be described. The base substrate 100 is provided with a step of applying the resin coating film described above to the surface of a coating object (at least one of the plate-like carrier 10 and the prepreg 30), a baking step of curing the applied resin coating film . ≪ / RTI > Hereinafter, each process will be described.

(Coating step)

The coating step is a step of applying a coating solution containing at least one of silicon as a main component, an epoxy resin as a curing agent, a melamine resin and a fluororesin as a mold releasing agent (if necessary) to a coating object (at least one of the plate- Thereby forming a resin coating film. Resin paints are obtained by dissolving an epoxy resin, a melamine resin, a fluorine resin and silicon in an organic solvent such as alcohol. It is preferable that the total amount of the epoxy resin and the melamine resin is 10 to 1500 parts by mass based on 100 parts by mass of the silicone. It is preferable that the fluororesin is 0 to 50 parts by mass relative to 100 parts by mass of silicon.

The coating method in the coating step is not particularly limited as long as a resin coating film can be formed. Examples of the coating method include a gravure coating method, a bar coating method, a roll coating method, a curtain flow coating method, and an electrostatic coating machine , The uniformity of the resin coating film, and the ease of operation, the gravure coating method is preferable. The coating amount is preferably 1.0 to 2.0 g / m 2 as the resin amount so that the resin coating film 3 has a preferable film thickness of 0.5 to 5 탆.

The gravure coating method is a method of forming a resin coating film on the surface of a coating object by transferring a resin coating material filled in a concave portion (cell) formed on the roll surface to a coating object. Specifically, the lower portion of the lower roll having the cells on its surface is immersed in the resin coating, and the resin coating is pushed up into the cell by the rotation of the lower roll. The object to be coated is placed between the lower roll and the upper roll disposed on the upper side of the lower roll and the lower roll and the upper roll are rotated while pressing the object to be coated with the upper roll to the lower roll, The resin coating material poured into the cell is transferred (applied) to one side of the coating object.

In addition, by arranging the doctor blade so as to contact the surface of the lower roll on the carry-in side of the object to be coated, the excess resin paint poured on the roll surface other than the cell is removed, and a predetermined amount of resin paint . Further, when the number of cells (size and depth) is large, or when the viscosity of the resin coating material is high, the resin coating film formed on one side of the coating object becomes difficult to be smoothed. Therefore, the smoothness of the resin coating film may be maintained by disposing a smoothing roll on the carry-out side of the coating object.

When a resin coating film is formed on both sides of the coating object, the resin coating film is formed on one side of the coating object, and then the coating object is turned upside down again between the lower and upper rolls. Then, similarly to the above, the resin paint in the cell of the lower roll is transferred (applied) to the back surface of the object to be coated.

(Baking process)

The baking step is a step of baking the resin coating film formed in the coating step at 125 to 320 DEG C (baking temperature) for 0.5 to 60 seconds (baking time). As described above, by baking the resin coating film formed of the predetermined amount of the resin coating material under a predetermined condition, it is possible to prevent the resin coating film (for example, the plate carrier 10) Legs 30 are controlled in a predetermined range. In the present invention, the baking temperature is the temperature reached by the prepreg 30. As the heating means used in the baking treatment, a conventionally known apparatus is used.

If the baking temperature is less than 125 占 폚 or the baking time is less than 0.5 sec, the resin coating film becomes insufficient in curing, the peel strength is more than 200 gf / cm and the peelability is deteriorated do. When the baking is excessive, for example, when the baking temperature exceeds 320 DEG C, the resin coating film deteriorates, the peel strength exceeds 200 gf / cm, and the workability upon peeling is deteriorated. Alternatively, the plate-like carrier may be deteriorated by high temperature. When the baking time exceeds 60 seconds, the productivity is deteriorated.

In the production method of the base substrate 100, and as the resin coating material of said coating step, as a subject silicon and epoxy resin as a curing agent, a melamine-based resin, a fluorine resin as a release agent, SiO _2, MgO, Al ₂ O _3, BaSO ₄ and Mg (OH) ₂ , may be used.

Specifically, the resin coating material is obtained by further adding surface roughening particles to the above-mentioned silicone resin solution. By additionally adding such surface roughening particles to the resin coating material, the surface of the resin coating film becomes irregular, and the plate carrier 10 becomes irregular by this irregularity, resulting in a surface with gloss removed. In order to obtain the plate-like carrier 10 having such a polished surface, it is preferable that the blending amount (added amount) of the surface roughening particles in the resin paint is 1 to 10 parts by mass relative to 100 parts by mass of silicon. It is further preferable that the surface roughing particles have a particle diameter of 15 nm to 4 탆.

The manufacturing method according to the present invention is as described above. However, in carrying out the present invention, other steps may be included during or after each step in the range not adversely affecting each step. For example, a cleaning step for cleaning the surface of the plate-like carrier before the application step may be performed.

The prepreg 30 is an example of a resin layer constituting a layer of a base of a multilayer printed wiring board. The prepreg 30 is a composite of an arbitrary substrate and an optional filler material and is typically obtained by solidifying the filler material from a liquid while impregnating a base material such as a nonwoven fabric or fabric into a filler material such as a synthetic resin . The prepreg 30 has a high insulating property and a desired mechanical strength. Examples of the resin as the constituent material of the prepreg 30 include phenol resin, polyimide resin, epoxy resin, natural rubber, and rosin, but are not limited thereto. It is preferable that the prepreg 30 before mounting on the plate-like carrier 10 is in the B-stage state, and thus sufficient strength can be ensured.

The prepreg 30 preferably has a high glass transition temperature Tg. The glass transition temperature Tg of the prepreg 30 is, for example, 120 to 320 占 폚, preferably 170 to 240 占 폚. The glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).

The prepreg 30 is laminated and fixed on the upper surface of the release agent layer 20 on the plate-like carrier 10 by hot pressing by hot press treatment or the like. As a condition of the hot press, hot press is preferably performed at a temperature higher than the glass transition temperature of the prepreg 30 at a pressure of 30 to 40 kg / cm < 2 >. The surface temperature of the press member contacting the prepreg 30 when the prepreg 30 is laminated and fixed is preferably 140 to 320 占 폚.

The thickness of the prepreg 30 is not particularly limited and is set to such a thickness as to have flexibility or a thickness not to have flexibility. However, since it is preferable that the prepreg 30 has mechanical strength and rigidity in laminating the buildup layer 110, it is not appropriate to make the prepreg 30 extremely thin. If the prepreg 30 is extremely thick, heat propagation through the prepreg 30 is not likely to occur. Therefore, uneven heat distribution is generated in the plane of the prepreg 30 at the time of hot pressing , It may be difficult to achieve a sufficient hot press. In consideration of this point, the thickness of the prepreg 30 is set to 50 to 900 탆, more preferably 100 to 400 탆.

The prepreg 30 is sufficiently fixed on the plate-shaped carrier 10 in the laminating step of the buildup layer 110 while the prepreg 30 and the plate-shaped carrier 10 are fixed after the laminating step of the build- It is desirable to set the peel strength between the plate-like carrier 10 and the prepreg 30 (or the build-up layer 110 including the prepreg 30) based on the viewpoint of ensuring easy peelability between the plate-like carrier 10 and the prepreg 30. The adjustment of the peel strength can be adjusted by setting the material and thickness of the releasing agent layer 20 described above and can be adjusted by surface treatment of the plate carrier 10 or the prepreg 30. [

The peel strength between the plate-like carrier 10 and the prepreg 30 is typically 10 gf / cm or more, preferably 30 gf / cm or more, more preferably 30 gf / cm or more in the state before the build- Is not less than 50 gf / cm, typically not more than 200 gf / cm, preferably not more than 150 gf / cm, more preferably not more than 80 gf / cm. By setting the peeling strength between the plate-like carrier 10 and the prepreg 30 in this manner, peeling of the plate-like carrier 10 and the prepreg 30 at the time of conveyance of the base substrate 100 can be suppressed, The peelability between the plate-like carrier 10 and the build-up layer 110 including the prepreg 30 can be ensured after the step of laminating the build-up layer 110. The peel strength between the plate-like carrier 10 and the prepreg 30 is equivalent to the peel strength between the plate-like carrier 10 and the build-up layer 110.

It is preferable that the peel strength between the plate-like carrier 10 and the prepreg 30 does not greatly fluctuate even after the step of laminating the build-up layer 110. This ensures that the peelability between the plate-like carrier 10 and the build-up layer 110 including the prepreg 30 is not damaged even after the step of laminating the build-up layer 110.

The peeling strength between the plate-like carrier 10 and the prepreg 30 may be increased, for example, after heating the base substrate 100 at 220 ° C for at least 3 hours, 6 hours, or 9 hours, Cm or more, preferably 150 gf / cm or less, more preferably 80 gf / cm or more, and most preferably 10 gf / cm or more, preferably 30 gf / / Cm or less.

The peel strength between the plate-like carrier 10 and the prepreg 30 after heating the base substrate 100 under the condition of 220 占 폚 is not more than 3 hours from the viewpoint of securing the width of the number of stacked layers of the build- And 6 hours later, or both 6 hours and 9 hours later, the peel strength preferably satisfies the above-described range, and all the peel strengths after 3 hours, 6 hours and 9 hours satisfy the above-described range Is more preferable.

In the present invention, the peel strength is measured in accordance with the 90 degree peel strength measurement method specified in JIS C6481.

In the conventional CCL, it is desired that the resin layer and the copper foil have high peel strength. For example, the matte surface (M side) of the electrolytic copper foil is used as a bonding surface with the resin layer, The adhesive force is improved by the chemical and physical anchor effect. Also, on the resin layer side, various binders are added in order to increase the adhesive force with the copper foil. As described above, in this embodiment, unlike the CCL, since the plate-like carrier 10 and the prepreg 30 are finally peeled off, it is not preferable that the peel strength is excessively high.

In order to adjust the peel strength between the plate-like carrier 10 and the prepreg 30 to the preferable range described above, the surface roughness of the coplanar surface is measured on the upper surface of the plate-like carrier 10 measured in accordance with JIS B 0601 (2001) When expressed in terms of a 10-point average roughness (Rz jis), it is preferable to set 3.5 mu m or less and 3.0 mu m or less. However, minimizing the surface roughness is time consuming and causes a rise in cost. Therefore, the surface roughness is preferably set to 0.1 탆 or more, more preferably 0.3 탆 or more. From the viewpoint of adjustment of the surface roughness, it is easy to use the gloss surface of the plate-like carrier 10 as the lamination surface of the releasing agent layer 20.

The surface treatment for improving the peel strength such as the roughening treatment may not be performed on each of the coplanar surfaces of the plate carrier 10 and the prepreg 30. [ According to the embodiment, no binder is added to the prepreg 30 to increase the adhesive force with the release agent layer 20.

The wiring layer in the buildup layer 110 may be a metal foil or may be formed using at least one of a subtractive method, a pull additive method, or a semi-additive method.

The subtractive method is a method of forming a conductor pattern by selectively removing unnecessary portions of a metal foil on an arbitrary substrate, for example, a metal clad laminate or a wiring board (including a printed wiring board and a printed circuit board) by etching or the like Point. The pull additive method is a method of forming a wiring layer 50 which is a patterned conductor layer by using electroless plating and / or electrolytic plating. In the semi-additive method, for example, a conductor pattern is formed by using electroless metal precipitation, electrolytic plating, etching, or both in combination on a seed layer made of a metal foil, and an unnecessary seed layer is etched and removed, It is a way to get a pattern.

As the constituent layer of the buildup layer 110, one or more resin, one side or both sides wiring board, one side or both sides metal clad laminate, carrier metal foil, metal foil or base substrate 100 may be included.

The method may further include the step of punching a hole in the single- or double-sided wiring substrate, the single-sided or double-sided metal clad laminate, the metal foil of the carrier-adhered metal foil, the plate-shaped carrier of the metal foil with the carrier, or the resin, . The step of forming the wiring on at least one of the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal clad laminate, and the metal foil constituting the carrier- .

The step of laminating the metal foil on the patterned wiring layer 50 and the step of laminating the carrier side of the metal foil with the carrier may be further included. A resin may be laminated on the patterned wiring layer 50 and the metal foil may be closely adhered to the resin. It is also possible to further include a step of laminating a resin on the wired surface and laminating a metal foil with a carrier on both sides of which the metal foil is closely contacted. The term " wired surface " refers to a portion formed on the surface that appears every time during the build-up process, and the build-up substrate includes the final product or the intermediate product.

The carrier-bonded metal foil is a laminate of a metal foil and a release agent layer on a resin or metal carrier functioning as a support substrate. In the carrier-bonded metal foil, the releasing agent layer which can peelably bond the carrier and the metal foil can be the same material as the releasing agent layer 20 disclosed in this application.

The stacked body 150 may be diced while the buildup layer 110 is laminated on the base substrate 100. [ The dicing depth is not necessarily to the extent that the laminated body 150 is completely discretized, and may be such that it does not reach the plate-like carrier 10. When the stacked body 150 is not completely separated, grooves which do not reach or reach the plate-like carrier 10 are formed. The device used for dicing is not limited to a type utilizing dicing blades, and any method such as wire or laser can be employed.

After the above-described dicing process, the plate-like carrier 10 and the prepreg 30 may be separated and separated. When the plate-like carrier 10 is not separated by dicing, a plurality of individualized multilayer printed wiring boards are obtained from the common plate-like carrier 10.

The insulating layer 40 and the wiring layer 50 in the buildup layer 110 may be laminated by thermocompression bonding. The thermocompression bonding may be performed each time one layer is laminated, or may be laminated to some extent, followed by assembly, or may be performed collectively at the end.

The via wiring (interlayer wiring) may be formed in the buildup layer 110 in order to ensure electrical conduction between the wiring layers 50 in the buildup layer 110 or between the wiring layer 50 in the buildup layer 110 and the external wiring, The process may be performed in the process of forming the buildup layer 110 on the base substrate 100 or after the buildup layer 110 of a predetermined number of layers is laminated on the base substrate 100. The via wiring may be formed while the build-up layer 110 is laminated on the base substrate 100. Even if the via wiring is formed after the plate-like carrier 10 of the base substrate 100 is peeled from the build-up layer 110 do. The upper interconnection layer 50 and the intermediate insulating layer 40 can be penetrated through the lower interconnection layer 50, the intermediate insulating layer 40 and the upper interconnection layer 50 on the base substrate 100, A via hole reaching the lower wiring layer 50 is formed and a conductive material is formed on the via hole by deposition or the like so that electrical conduction between the lower wiring layer 50 and the upper wiring layer 50 is ensured. The via hole may be formed by any method such as mechanical cutting or laser machining. The number of the insulating layers 40 through which the via holes pass may be arbitrary, and may be two or more. Electroplating may be used to fill the via hole with the conductive material.

A method of manufacturing a multilayer printed wiring board will be described with reference to FIGS. 2 and 3. FIG. First, the base substrate 100 shown in Fig. 1 is prepared. The release agent layer 20 is formed on the plate carrier 10 and then the prepreg 30 is removed from the release agent layer 20 And the prepreg 30 is laminated on the plate-like carrier 10 with the release agent layer 20 interposed therebetween, thereby obtaining a base substrate 100. The plate substrate 10 is then placed on the plate-like carrier 10, The release agent layer 20 is formed to have a constant layer thickness over the entire area of the upper surface of the plate-shaped carrier 10. [ The prepreg 30 is adhered to the upper surface of the release agent layer 20 sufficiently in the same plane.

Next, as shown in FIG. 2, the build-up layer 110 is laminated on the base substrate 100. For example, the insulating layer 40 and the wiring layer 50 are alternately laminated. The number of stacking units made up of the set of the insulating layer 40 and the wiring layer 50 is typically 1 or more, and may be 2 or more, 3 or more, 4 or more. It is difficult to maintain the precision of the inter-layer position of the multilayer printed wiring board by increasing the number of the stacking units. The prepreg 30 serving as the lowermost layer of the multilayer printed wiring board is stably fixed on the base substrate 100 in advance and a buildup layer 110 is formed on the prepreg 30 And can be stably stacked.

When the buildup layer 110 is formed by providing the prepreg 30 of the base substrate 100 to the customer in a state in which the prepreg 30 is omitted and by laminating and fixing the prepreg 30 on the customer side by thermocompression, It is necessary to select a thickness or a material of the releasing agent layer 20 in consideration of the relationship with this member. In the present embodiment, it is possible to prevent the above-described problems from occurring by stacking the prepreg 30, which is the lowermost layer of the buildup layer 110, on the release agent layer 20.

The wiring layer 50 is a metal foil or a patterned metal foil, and is preferably a copper foil or a patterned copper foil. The wiring layer 50 may be formed by using a conventional semiconductor process technology. Although not particularly limited, the wiring layer 50 is typically formed by patterning a beta wiring layer formed by, for example, CVD (Chemical Vapor Deposition) or PVD (Physical Vapor Deposition) typified by the use of a photolithography technique . The wiring layer 50 is not necessarily patterned, and the wiring layer 50 may be a beta wiring layer. With respect to the removed portion of the wiring layer by patterning, the insulating layer 40 may be in contact with the prepreg 30. The patterning may be performed using the lift-off technique.

The insulating layer 40 is a resin layer having a resin layer or a via wiring (interlayer wiring) formed thereon, and typically a thermosetting resin or a photosensitive resin can be exemplified. The insulating layer 40 may be a prepreg reinforced with glass fiber or inorganic filler. The constituent resin of the insulating layer 40 may be selected from materials having the same or similar characteristics as those of the prepreg. Or may be formed by using any kind of coating apparatus typified by a die coater. Instead of this, or in combination with this, the wiring layer 50 may be formed by using a conventional semiconductor process technology. The insulating layer 40 is typically formed by depositing an insulating material by vapor deposition represented by CVD (Chemical Vapor Deposition) or PVD (Physical Vapor Deposition), and if necessary, Conductive vias are formed in order to secure electrical connection between the electrodes 50. The method of inserting the conductive via into the insulating layer 40 is arbitrary. A mask layer having an opening is formed on the insulating layer 40 deposited on the wiring layer 50 and an etching process is performed through the mask layer to remove the insulating layer 40 in a range corresponding to the opening of the mask layer, Thereafter, a method of filling the conductive material in the range in which the insulating layer 40 is removed can be exemplified.

The wiring layer 50 is made of a conductive material such as copper, aluminum, polysilicon, or the like. The insulating layer 40 is made of an insulating material such as silicon dioxide. The vias inserted into the insulating layer 40 are made of a conductive material such as copper, aluminum, or polysilicon. The constituent resin of the insulating layer 40 may be selected from materials having the same or similar characteristics as those of the prepreg 30.

Next, as schematically shown in Fig. 3, the laminate 120 in which the release agent layer 20 remains on the plate-like carrier 10 and the buildup layer 110 are separated. Thus, a multilayer printed circuit board can be manufactured. Further, the laminated body 120 and the buildup layer 110 may be peeled off by human hands, but they may be separated using a robot or the like.

The base substrate 100 shown in Fig. 1 may be manufactured by hot pressing another new prepreg 30 on the laminate 120 after the separation process shown in Fig. Thereafter, the build-up layer 110 may be laminated as shown in Fig. 2 and the laminate 120 and the build-up layer 110 may be separated as shown in Fig. 3 in the same manner as described above.

Hereinafter, an exemplary embodiment will be described. A desired number of prepregs, a two-layer metal clad laminate, hereinafter referred to as "inner layer cores", a prepreg, and a "carrier-adhered metal foil" are successively laminated on the base substrate 100 described above, The unit of unit (collectively referred to as " page ") may be repeatedly laminated about 10 times to form a press assembly (collectively referred to as "drum"). Thereafter, the book is sandwiched between one set of flat plate, set in a hot press, and press-molded at a predetermined temperature and pressure, whereby a large number of four-layer metal clad laminate can be manufactured at the same time. As the flat plate, for example, a plate made of stainless steel may be used. The plate may be, but not limited to, a thickness plate of, for example, about 1 to 10 mm. With respect to the metal clad laminate having four or more layers, it is generally possible to produce in the same step by increasing the number of layers of the inner core.

A step of half-etching the entire surface of the metal foil constituting the wiring layer 50 to adjust the thickness, if necessary, may be included. A predetermined position of the metal foil constituting the wiring layer 50 is subjected to laser processing to form a via hole penetrating the metal foil and the resin and a desmear treatment for removing the smear in the via hole. Thereafter, the entire surface of the via hole bottom, Alternatively, electroless plating may be performed on a part of the interlayer connection to form an interlayer connection, and further electrolytic plating may be performed if necessary. A plating resist may be formed in advance in a portion where the electroless plating on the metal foil or the electrolytic plating is unnecessary, until each plating is performed. If the adhesion between the electroless plating, the electrolytic plating, and the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically matched in advance. When a plating resist is used, the plating resist is removed after plating. Next, unnecessary portions of the metal foil, the electroless plating portion, and the electrolytic plating portion are removed by etching to form a circuit. In this manner, a build-up substrate can be manufactured. The multilayer buildup substrate may be formed by repeating the steps from the lamination of the resin and the copper foil to the circuit formation a plurality of times.

A metal foil with a carrier in close contact with a metal foil on one side of the resin carrier substrate may be formed on the uppermost layer of the buildup layer 110. [ The carrier substrate of the carrier-bonded metal foil may be lower than the metal foil or vice versa. A metal foil with a carrier in which a metal foil is in close contact with both surfaces of a resin carrier substrate may be laminated on the resin layer of the buildup layer 110.

Another base substrate 100 may be laminated on the uppermost layer of the buildup layer 110.

Preferably, a prepreg containing a thermosetting resin may be used as the insulating layer 40 of the buildup layer 110.

Suitably, the insulating layer 40 is a resin layer, for example, a prepreg or a photosensitive resin. When a prepreg is used as the insulating layer 40, a via hole may be formed in the prepreg by laser processing. After the laser processing, a desmear treatment for removing the smear in the via holes may be performed. When a photosensitive resin is used as the resin, the resin in the via-hole forming portion can be removed by photolithography. Next, electroless plating is performed on the via hole bottom, the side surface, and the entire surface or part of the resin to form an interlayer connection, and electrolytic plating is further carried out if necessary. A plating resist may be formed in advance in a portion where the resin-based electroless plating or electrolytic plating is unnecessary, until each plating is performed. When the electroless plating, the electroplating, and the adhesion between the plating resist and the resin are insufficient, the surface of the resin may be chemically matched in advance. When a plating resist is used, the plating resist is removed after plating. Next, unnecessary portions of the electroless plating portion or the electroplated portion are removed by etching to form a circuit.

≪ Second Embodiment >

The second embodiment will be described with reference to Figs. 4 and 5. Fig. 4 is a schematic cross-sectional view of the base substrate. 5 is a schematic cross-sectional view showing a state in which buildup layers are laminated on both surfaces of a base substrate. In this embodiment, as shown in Fig. 4, the release agent layer 20 and the prepreg 30 are also laminated on the lower surface of the plate-like carrier 10 in this order. Even in this case, the same effect as that of the first embodiment can be obtained. 5, the build-up layer 110 can be laminated on both sides of the plate-like carrier 10, and the utilization efficiency of the base substrate 100 can be effectively increased. As a result, The manufacturing efficiency of the printed wiring board can be increased.

The thickness of the release agent layer 20 to be adhered to both surfaces of the plate-like carrier 10 may be the same or different. The same is true for the prepreg 30 disposed on the upper and lower layers of the plate-like carrier 10. The same applies to the construction of the buildup layer 110 formed on the upper and lower layers of the base substrate 100.

≪ Useful laminate >

As is clear from the above description, the laminate used in the production of the above-described base substrate is also disclosed in the present invention, and the details thereof are as follows.

A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,

Wherein the release agent layer has the following formula:

[Chemical Formula 9]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.

, The hydrolysis product thereof, and the condensation product of the hydrolysis product thereof, either singly or in combination.

A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,

Wherein the release agent layer comprises a compound having two or less mercapto groups in the molecule.

A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,

Wherein the release agent layer has the following formula:

[Chemical formula 10]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of at least ¹ and not more than M, and at least one of R ¹ is an alkoxy group. 3 for Ti and 4 for Zr)

, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination.

A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,

Wherein the release agent layer is a resin coating film composed of one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin.

- Example -

<Experimental Example 1>

A nickel-zinc (Ni-Zn) alloy plating treatment and a chromate (Cr-Zn chromate) treatment were performed on both surfaces of the rolled copper foil (thickness: 70 占 퐉) under the following conditions. And the roughness (Rz jis: measured in accordance with JIS B 0601 (2001)) was set to 1.5 탆.

(Nickel-zinc alloy plating)

Ni concentration of 17 g / l (added as NiSO ₄ )

Zn concentration 4 g / l (added as ZnSO ₄ )

pH 3.1

Solution temperature 40 ° C

Current density 0.1 to 10 A / dm 2

Plating time 0.1 ~ 10 seconds

(Chromate treatment)

Cr concentration 1.4 g / l (added as CrO ₃ or K ₂ CrO ₇ )

Zn concentration 0.01 to 1.0 g / l (added as ZnSO ₄ )

Na ₂ SO ₄ concentration 10 g / l

pH 4.8

Solution temperature 55 ° C

Current density 0.1 to 10 A / dm 2

Plating time 0.1 ~ 10 seconds

With respect to the treatment of the release agent against the surface of the copper foil, the aqueous solution of the release agent was applied using a spray coater, and then the copper foil surface was dried in air at 100 ° C. The conditions for the use of the release agent are shown in the table of FIG. 6, the type of the release agent, the stirring time after dissolving the release agent in water (water), the concentration of the release agent in the aqueous solution, the alcohol concentration in the aqueous solution and the pH of the aqueous solution.

A prepreg (FR-4 prepreg, manufactured by Nanya Plastic Co., Ltd.) having a thickness of 200 占 퐉 was laminated on both sides of the thus-obtained copper foil with the release agent layer by hot pressing to obtain a base substrate. The hot press conditions were a pressure of 30 kg / mm 2, a temperature of 170 ° C, and a holding time of 100 minutes.

Next, on both sides of the base substrate, a prepreg (FR-4 prepreg, thickness 62 占 퐉, manufactured by Nanya Plastic Co., Ltd.) as a dielectric layer and a copper foil (JTC (product name) manufactured by JX Nikkoseki Metal Co., 12 占 퐉) was laminated by hot pressing to form a buildup layer. The hot press conditions are the same as those in the case of obtaining the base substrate described above. The laminate composed of the base substrate and the buildup layer thus obtained was subjected to heat treatment under the conditions described in the table shown in Fig. 6 (here, at 220 캜 for 3 hours) on the assumption that thermal history was applied during additional heat treatment such as build- Was subjected to heat treatment. The peel strength at the interface between the base substrate and the insulating layer of the build-up layer in the obtained laminate and the laminate after heat treatment was measured. The results are shown in the table of Fig.

<Experimental Examples 2 to 11>

Using a copper foil, a resin (prepreg) and a releasing agent shown in the table of Fig. 6, a laminate composed of a base substrate and a build-up layer was produced in the same manner as in Experimental Example 1. [ The same evaluation as in Experimental Example 1 was carried out for each. The results are shown in the table of Fig.

The release-molded resin coating film on the S-plane in Experimental Example 11 was formed by applying the resin coating composition having the composition shown in the table of Fig. 6 by the gravure coating method, Was adjusted to 2 to 4 탆. The applied resin coating film was baked at 150 캜 for 30 seconds. As the epoxy resin shown in the table of Fig. 6, a bisphenol A type epoxy resin was used. As the melamine resin, a methyl etherified melamine resin was used. As the fluororesin, polytetrafluoroethylene was used. Dimethylpolysiloxane was used as the silicone resin.

The type of the releasing agent-treated surface of the copper foil, the condition of the surface treatment and the surface roughness Rz jis, the use conditions of the release agent, the type of the prepreg, and the lamination conditions of the copper foil and the prepreg are as shown in the table of Fig.

As shown in the table of Fig. 6, good results were obtained in Examples 1 to 11. In Examples 1 to 8 and 10, better results were obtained. Particularly good results were obtained in Examples 1, 2 and 5 to 7. In the evaluation of the peeling workability, "G" indicates that the release agent layer as the resin layer was not destroyed and the build-up layer 110 could be peeled from the base substrate 100. The build-up layer 110 could be peeled off from the base substrate 100 without breaking the release agent layer, but peeled off with no probability of peeling four times or more out of 10 times was indicated as &quot; - &quot;. The release agent layer is destroyed or the buildup layer 110 can not be peeled off from the base substrate 100 is indicated as &quot; N &quot;.

(Example 12)

FR-4 prepreg (manufactured by Nanya Plastic Company) and copper foil (manufactured by JX Nikkoseki Metal Co., Ltd., JTC 12 μm (product name)) were sequentially laminated on both sides of the same base material as in Examples 1 to 11, Pressed under a predetermined heating condition at a pressure of 5 MPa and a pressure of 5 MPa, thereby producing a four-layer copper clad laminate.

Next, holes having a diameter of 100 mu m penetrating through the copper foil on the surface of the four-layer copper-clad laminate and the insulating layer (cured prepreg) beneath the copper foil were drilled using a laser processor. Subsequently, copper plating was carried out on the surface of the copper foil on the carrier-bonded copper foil exposed on the bottom of the hole, on the side of the hole, on the copper foil on the surface of the four-layer copper- clad laminate, by electroless copper plating or electro- An electrical connection was formed between the copper foil on the copper foil with a carrier and the copper foil on the surface of the copper foil laminate. Next, a part of the copper foil on the surface of the four-layer copper-clad laminate was etched using a ferric chloride-based etchant to form a circuit. Thus, a four-layer buildup substrate was obtained.

Subsequently, in the four-layer build-up substrate, the plate-like carrier of the base substrate and the prepregs on both sides thereof were separated and separated to obtain two sets of two-layer build-up wiring boards. Peeling could be performed well.

In view of the above teachings, those skilled in the art can make various modifications to the embodiments. The major surface of the plate-like carrier is typically the upper surface or the lower surface.

100: base substrate
10: plate carrier
20: Release agent layer
30: prepreg
110: buildup layer

Claims (38)

A first step of preparing a base substrate having a resin layer laminated on at least one main surface of a metal plate carrier through a release agent layer;
And a second step of laminating one or more buildup layers on the resin layer of the base substrate. The method according to claim 1,
Wherein the substrate thickness of the plate-like carrier is not less than 5 占 퐉 and not more than 1600 占 퐉. 3. The method according to claim 1 or 2,
Wherein the peel strength between the plate-like carrier and the resin layer is not less than 10 gf / cm and not more than 200 gf / cm. 4. The method according to any one of claims 1 to 3,
Wherein the peel strength between the plate-like carrier and the resin layer is not less than 10 gf / cm and not more than 200 gf / cm after heating at 220 ° C for at least 3 hours, 6 hours, or 9 hours . 5. The method according to any one of claims 1 to 4,
Further comprising a third step of separating the resin layer on which the buildup layer is laminated and the plate-shaped carrier. The method for manufacturing a multilayer printed wiring board according to claim 5, wherein the resin layer is a first resin layer,
Further comprising a fourth step of laminating a second resin layer different from the first resin layer and an additional buildup layer on the multilayer printed wiring board obtained by the third step . 7. The method according to any one of claims 1 to 6,
Wherein the resin layer is a prepreg. 8. The method according to any one of claims 1 to 7,
Wherein the resin layer has a glass transition temperature Tg of 120 to 320 캜. 9. The method according to any one of claims 1 to 8,
Wherein the build-up layer comprises at least one insulating layer and at least one wiring layer. 10. The method according to any one of claims 1 to 9,
Wherein at least one wiring layer included in the build-up layer is a patterned or non-patterned metal foil. 11. The method according to any one of claims 1 to 10,
Wherein at least one insulating layer included in the buildup layer is a prepreg. 12. The method according to any one of claims 1 to 11,
Wherein the build-up layer comprises a single-sided or double-sided metal clad laminate. 13. The method according to any one of claims 1 to 12,
Wherein the build-up layer is formed using at least one of a subtractive method, a pull additive method, and a semi-additive method. 14. The method according to any one of claims 1 to 13,
Further comprising a fifth step of performing a dicing process on the laminate having the buildup layer laminated on the base substrate. 15. The method of claim 14,
Wherein at least one groove is formed in the laminate having the build-up layer laminated on the base substrate by the dicing process, and the build-up layer is divided into individual pieces by the groove, &Lt; / RTI &gt; 16. The method according to any one of claims 1 to 15,
Further comprising a sixth step of forming a via wiring with respect to at least one insulating layer included in the buildup layer. 17. The method according to any one of claims 1 to 16,
Wherein the release agent layer has the following formula:
[Chemical Formula 1]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.
, The hydrolysis product thereof, and the condensation product of the hydrolysis product thereof are used singly or in combination. 17. The method according to any one of claims 1 to 16,
Wherein the release agent layer comprises a compound having two or less mercapto groups in the molecule. 17. The method according to any one of claims 1 to 16,
Wherein the release agent layer has the following formula:
(2)

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of at least ¹ and not more than M, and at least one of R ¹ is an alkoxy group. 3 for Ti and 4 for Zr)
, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination. 17. The method according to any one of claims 1 to 16,
Wherein the release agent layer is a resin coating film composed of any one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin. 21. The method according to any one of claims 1 to 20,
Wherein the plate-like carrier is made of copper or a copper alloy. 22. The method according to any one of claims 1 to 21,
Wherein the wiring layer is made of copper or a copper alloy. A multilayer printed wiring board produced by the method for manufacturing a multilayer printed wiring board according to any one of claims 1 to 22. A base substrate for use in a method of manufacturing a multilayer printed wiring board,
A metal plate carrier,
A release agent layer formed on at least one main surface of the plate-like carrier,
And a resin layer laminated on the plate-like carrier via the release agent layer,
Wherein the resin layer and the plate-like carrier are peelable. 25. The method of claim 24,
Wherein a thickness of the substrate of the plate-like carrier is 5 占 퐉 or more and 1600 占 퐉 or less. 26. The method according to claim 24 or 25,
Wherein the peel strength between the plate-like carrier and the resin layer is 10 gf / cm or more and 200 gf / cm or less. 27. The method according to any one of claims 24 to 26,
Wherein the peel strength between the plate-like carrier and the resin layer after heating at 220 占 폚 for at least 3 hours, 6 hours, or 9 hours is 10 gf / cm or more and 200 gf / cm or less. 28. The method according to any one of claims 24 to 27,
Wherein the plate-like carrier is made of copper or a copper alloy. 29. The method according to any one of claims 24 to 28,
Wherein the resin layer comprises a prepreg. 30. The method according to any one of claims 24 to 29,
Wherein the release agent layer has the following formula:
(3)

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.
, A hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination. 30. The method according to any one of claims 24 to 29,
Wherein the release agent layer comprises a compound having two or less mercapto groups in the molecule. 30. The method according to any one of claims 24 to 29,
Wherein the release agent layer has the following formula:
[Chemical Formula 4]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of at least ¹ and not more than M, and at least one of R ¹ is an alkoxy group. 3 for Ti and 4 for Zr)
, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination. 30. The method according to any one of claims 24 to 29,
Wherein the release agent layer is a resin coating film composed of one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin. A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,
Wherein the release agent layer has the following formula:
[Chemical Formula 5]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and R ³ and R ⁴ are each independently a halogen atom or an alkoxy group or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom.
, The hydrolysis product thereof, and the condensation product of the hydrolysis product thereof, either singly or in combination. A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,
Wherein the release agent layer comprises a compound having two or less mercapto groups in the molecule. A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,
Wherein the release agent layer has the following formula:
[Chemical Formula 6]

(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 and an aryl group, or a hydrocarbon group in which at least one hydrogen atom is substituted with a halogen atom, and M M is at least one of Al, Ti and Zr, n is 0 or 1 or 2, m is an integer of at least ¹ and not more than M, and at least one of R ¹ is an alkoxy group. 3 for Ti and 4 for Zr)
, A titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product thereof, either singly or in combination. A laminated body in which a release agent layer is laminated on at least one main surface of a metal plate carrier,
Wherein the release agent layer is a resin coating film composed of one or a plurality of resins selected from silicon, an epoxy resin, a melamine resin and a fluororesin. 37. The method according to any one of claims 34 to 37,
Wherein the plate-like carrier is made of copper or a copper alloy.

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