TWI519413B - Attached metal foil - Google Patents

Description

With carrier metal foil

The present invention relates to a metal foil with a carrier. More specifically, it relates to a carrier-attached metal foil used in the production of a single-layered or two-layer multilayer laminated board or an extremely thin coreless substrate for a printed wiring board.

In general, a printed wiring board is a basic constituent material called a "prepreg" obtained by impregnating a synthetic resin with a base material such as a synthetic resin sheet, a glass plate, a glass nonwoven fabric, or paper. Further, a sheet such as a conductive copper or copper alloy foil is bonded to the side opposite to the prepreg. The laminate thus constituted is generally referred to as a CCL (Copper Clad Laminate) material. The surface of the copper foil that is in contact with the prepreg is usually set to a matte side to improve the joint strength. There are also cases where foils of aluminum, nickel, zinc, etc. are used instead of copper or copper alloy foils. These thicknesses are about 5 to 200 μm. The CCL (Copper Clad Laminate) material which is usually used is shown in Fig. 1 .

Patent Document 1 proposes a plate-shaped carrier made of a synthetic resin and a metal foil with a metal foil which is adhered to at least one surface of the carrier by mechanical peeling, and the metal foil for the carrier is described. The content of the assembly of the printed wiring board. Further, it is revealed that the peel strength of the plate-shaped carrier and the metal foil is preferably from 1 gf/cm to 1 kgf/cm. By the metal foil with a carrier, the copper foil is supported over the entire surface of the synthetic resin, so that wrinkles in the copper foil in the laminate can be prevented. Moreover, since the metal foil of the metal foil with a carrier is in close contact with the synthetic resin without a gap, When the surface of the metal foil is plated or etched, it can be put into a gold plating or etching solution. Further, since the linear expansion coefficient of the synthetic resin is equivalent to the copper foil as the constituent material of the substrate and the prepreg after the overlap, the positional deviation of the circuit is not caused, so that the number of defective products is reduced and the number of defective products can be increased. The effect of excellent yield.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-272589

The carrier-attached metal foil described in Patent Document 1 is an epoch-making invention that contributes greatly to the reduction of manufacturing cost by simplifying the process of manufacturing a printed circuit board and improving the yield, but the peeling strength of the plate-shaped carrier and the metal foil is the highest. There is still room for research on Jiahua and its methods. In particular, as a problem that is remarkable to the present inventors, the peel strength of the plate-shaped carrier and the metal foil is excessively high due to the material of the plate-shaped carrier, and it is preferable to provide a method for easily adjusting the peel strength. . Accordingly, an object of the present invention is to provide a carrier-attached metal foil having a peel strength of a plate-shaped carrier made of a resin and a metal foil.

The present inventors conducted intensive studies on the method of adjusting the peel strength between the resin sheet and the metal foil, and as a result, found that it is possible to have a specific structure for at least one surface before the resin sheet and the metal foil are bonded together. The decane compound is treated, whereby the peel strength corresponding to the desired use can be achieved, thereby completing the present invention.

That is, the present invention is as follows.

(1) A carrier-attached metal foil comprising a plate-shaped carrier made of a resin and a metal foil which is detachably adhered to at least one side of the carrier, and the plate-shaped carrier and the metal foil are used alone or in combination. The decane compound represented by the following formula, the hydrolyzed product thereof, and the condensate of the hydrolyzed product are bonded together.

(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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group).

(2) The carrier metal foil according to (1), wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less.

(3) The carrier-attached metal foil according to (1) or (2), wherein the resin-made plate-shaped carrier contains a thermosetting resin.

(4) The carrier-attached metal foil according to any one of (1) to (3), wherein the resin-made plate-shaped carrier is a prepreg.

(5) The carrier metal foil according to (3) or (4), wherein the plate-shaped carrier made of the above resin has a glass transition temperature Tg of 120 to 320 °C.

(6) The carrier-attached metal foil according to any one of (1) to (5), wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(7) The carrier-attached metal foil according to any one of (1) to (6) wherein, after heating at 220 ° C for at least one of 3 hours, 6 hours or 9 hours, peeling of the metal foil from the plate-shaped carrier The strength is 10 gf/cm or more and 200 gf/cm or less.

(8) A metal foil for a hollow multilayer printed wiring board having a decane compound of the following formula, a hydrolyzed product thereof or a condensate of the hydrolyzate on the surface of the metal foil,

(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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group).

(9) The metal foil for a hollow multilayer printed wiring board according to (8), characterized in that the surface of the side of the metal foil on which the decane compound acts is subjected to chromate treatment before the action of the decane compound.

(10) The metal foil for a hollow multilayer printed wiring board according to (8), wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(11) A metal foil which is a condensate of a decane compound of the following formula, a hydrolyzed product thereof or a hydrolyzate of at least one surface thereof for adhering the resin-made plate-shaped carrier to the surface in a peelable manner the use of,

(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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group).

(12) The metal foil according to (11), wherein the surface of the side of the metal foil on which the decane compound acts is subjected to chromate treatment before the action of the decane compound.

(13) The metal foil according to (11) or (12), wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(14) A plate-shaped carrier which is a resin-made plate-shaped carrier having at least one surface of a decane compound of the following formula, a hydrolyzate thereof or a condensate of the hydrolyzate, for adhering the metal foil to the metal foil in a peelable manner The use of the surface,

(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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group).

(15) A method for producing a multilayer metal-clad laminate comprising: at least one metal foil side build-up resin of the carrier-attached metal foil according to any one of (1) to (7), and then repeating the resin layer one time or more Or metal foil.

(16) A method for producing a multi-layer metal-clad laminate comprising the metal foil side-layer resin of the carrier-attached metal foil according to any one of (1) to (7), and then repeating the resin for a single layer or more A metal-clad laminate, or a metal foil with a carrier of any one of (1) to (7), or a metal foil.

(17) The method for producing a multi-layer metal-clad laminate according to (15) or (16), further comprising the step of separating the plate-shaped carrier with the carrier metal foil and the metal foil.

(18) A method of producing a multilayer metal-clad laminate according to (17), comprising the step of removing a part or all of the peeled and separated metal foil by etching.

(19) A multilayer metal-clad laminate obtained by the production method of any one of (15) to (18).

(20) A method of producing a build-up substrate, comprising the step of forming one or more build-up wiring layers on the metal foil side of the laminate of any one of (1) to (7).

(21) The method for producing a build-up substrate according to (20), wherein the build-up wiring layer is used in a subtractive method or a full additive method or a semi-additive method. Formed by at least one.

(22) A method for producing a build-up substrate, comprising: at least one metal foil side build-up resin of the metal foil with a carrier according to any one of (1) to (7), and then repeating the resin for a single layer or more A surface or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, or a carrier-attached metal foil or metal foil according to any one of (1) to (7).

(23) The method for producing a build-up substrate according to (22), further comprising the steps of: a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier metal foil, and a carrier The plate-shaped carrier of the metal foil or the resin is perforated, and the side surface and the bottom surface of the hole are electrically plated.

(24) The method for producing a build-up substrate according to (22) or (23), further comprising the step of: performing one or more of the following steps: forming a metal foil of the single-sided or double-sided wiring substrate to form a single-sided or double-sided coating At least one of the metal foil of the metal laminate and the metal foil constituting the carrier metal foil forms wiring.

(25) The method for producing a build-up substrate according to any one of (22) to (24), further comprising the step of attaching any one of (1) to (7) in which the metal foil is adhered to one side. Carrier metal foil The resin plate side is laminated on the surface on which the wiring is formed to be laminated.

(26) The method for producing a build-up substrate according to any one of (22) to (24), comprising the steps of: laminating a resin on a surface on which the wiring is formed, and adhering the metal foil to the double-sided (1) to A metal foil of the carrier-attached metal foil according to any one of (7) is laminated in contact with the resin.

(27) The method for producing a build-up substrate according to any one of (22) to (26), wherein at least one of the resins is a prepreg.

(28) A method of producing a build-up wiring board according to any one of (20) to (27), further comprising the step of: forming the plate-shaped carrier of the metal foil with a carrier The metal foil is peeled off and separated.

(29) The method for producing a build-up wiring board according to (28), further comprising the step of removing a part or all of the metal foil adhered to the plate-shaped carrier by etching.

(30) A build-up wiring board obtained by the production method of (28) or (29).

(31) A method of producing a printed circuit board, comprising the steps of: manufacturing a build-up substrate by the manufacturing method according to any one of (20) to (27).

(32) A method of manufacturing a printed circuit board comprising the steps of: manufacturing a build-up wiring board by the manufacturing method of (28) or (29).

According to the present invention, the peel strength of the plate-shaped carrier and the metal foil can be easily adjusted. Therefore, for example, the carrier metal foil which has previously shown excessively high peel strength is adjusted to have a preferable peel strength, so that the productivity of the printed wiring board using the metal foil with a carrier can be improved.

11‧‧‧With carrier metal foil

11a‧‧‧metal foil

11b‧‧‧ decane compounds

11c‧‧‧plate carrier

16‧‧‧Additional

Fig. 1 shows an example of the configuration of a CCL.

Fig. 2 is a view showing an example of the structure of a metal foil with a carrier of the present invention.

Figure 3 is a view showing a copper foil with a carrier of the present invention (a copper foil is bonded to both sides of a resin sheet) The configuration example of the multilayer CCL of the form).

In one embodiment of the metal foil with a carrier of the present invention, a plate-shaped carrier made of resin and a metal foil which is detachably adhered to one or both sides (preferably double-sided) of the carrier is prepared. A carrier metal foil is formed. One of the structures of the metal foil with a carrier of the present invention is shown in Figs. 2 and 3. In particular, in the first drawing of Fig. 3, the metal foil 11a is detachably adhered to the carrier-attached metal foil 11 which is formed on both sides of the resin-made plate-shaped carrier 11c. The plate-shaped carrier 11c and the metal foil 11a are bonded together using the following decane compound 11b.

The metal foil with a carrier of the present invention is structurally similar to the CCL shown in Fig. 1, but the metal foil and the resin are finally separated, and have a structure which can be easily peeled off. In this respect, since the CCL is not a stripper, the structure and function are completely different.

The metal foil with a carrier used in the present invention is finally peeled off, so that the adhesion is too high, which is a problem, but the plate-shaped carrier and the metal foil must have a chemical liquid processing step such as plating performed during the production process of the printed circuit board. The degree of adhesion without peeling.

The adjustment of the peeling strength for achieving such adhesiveness is carried out by using a decane compound represented by the following formula, a hydrolyzed product thereof, or a condensate of the hydrolyzed product by using a plurality of types alone or in combination (hereinafter, only The decane compound) is carried out. This is because the adhesion between the plate-shaped carrier and the metal foil can be appropriately reduced by using the decane compound, and the peel strength can be adjusted to the above range.

formula:

(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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group)

The decane compound must have at least one alkoxy group. In the case where an alkoxy group is not present, and only a hydrocarbon group selected from a group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrogen atom having one or more hydrogen atoms substituted by a halogen atom constitutes a substituent There is a tendency that the adhesion between the plate-shaped carrier and the surface of the metal foil is excessively lowered. Further, the decane compound must have at least one hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any one of the hydrocarbon groups in which one or more hydrogen atoms are substituted by a halogen atom. The reason for this is that in the case where the hydrocarbon group is not present, the adhesion between the plate-shaped carrier and the surface of the metal foil tends to increase. Further, in the invention of the present invention, the alkoxy group also contains an alkoxy group in which one or more hydrogen atoms are substituted by a halogen atom.

In order to adjust the peeling strength of the plate-shaped carrier and the metal foil to the above range, the decane compound preferably has three alkoxy groups and one of the above hydrocarbon groups (including a hydrocarbon group in which one or more hydrogen atoms are replaced by a halogen atom). When the above formula is described, both of R ³ and R ⁴ are alkoxy groups.

The alkoxy group is not limited, and examples thereof include a methoxy group, an ethoxy group, a n- or iso-propoxy group, a n-, iso- or tert-oxy group, a n-, iso- or neopentyloxy group, and a n-hexyloxy group. The linear, branched or cyclic carbon number such as cyclohexyloxy, n-heptyloxy and n-octyloxy is 1 to 20, preferably 1 to 10, more preferably 1 to 5 carbon atoms. Alkoxy group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a normal or an isopropyl group, a normal group, an iso- or a third-order group, a normal, an iso- or neopentyl group, a n-hexyl group, an n-octyl group, and a n-decyl group. The linear or branched carbon number is 1 to 20, preferably 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.

The cycloalkyl group is not limited, and examples thereof include a carbon number of 3 to 10, preferably a carbon number of 5 to 7 such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group. Cycloalkyl.

Examples of the aryl group include a phenyl group, an alkyl group-substituted phenyl group (for example, tolyl group, xylyl group), a 1- or 2-naphthyl group, and a fluorenyl group having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. The aryl group.

One or more hydrogen atoms of the hydrocarbon group may be substituted by a halogen atom, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Preferred examples of the decane compound include methyltrimethoxydecane, ethyltrimethoxydecane, n- or isopropyltrimethoxydecane, n-, iso- or tert-tris-trimethoxydecane, and Iso- or neopentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, phenyltrimethoxydecane; alkyl-substituted phenyltrimethoxynonane (for example , p-(methyl)phenyltrimethoxydecane), methyltriethoxydecane, ethyltriethoxydecane, n- or isopropyltriethoxydecane, n-, iso- or tertiary-based Ethoxy decane, pentyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, phenyl triethoxy decane, alkyl substituted benzene Triethoxy decane (for example, p-(methyl)phenyltriethoxydecane), (3,3,3-trifluoropropyl)trimethoxynonane, and tridecafluorooctyltriethoxy Decane, methyltrichlorodecane, dimethyldichlorodecane, trimethylchlorodecane, phenyltrichlorodecane, trimethylfluorodecane, dimethyldibromodecane, Diphenyldibromodecane, the hydrolyzed product, and the condensate of the hydrolyzed product, and the like. Among these, from the viewpoint of easiness of acquisition, propyltrimethoxydecane, methyltriethoxydecane, hexyltrimethoxydecane, phenyltriethoxydecane, and decyltrimethyl are preferred. Oxydecane.

The carrier-attached metal foil can be made by heat-pressing the plate-shaped carrier and the metal foil Made. For example, it can be produced by applying the above-described decane compound to the bonding surface of the metal foil and/or the plate-shaped carrier, and then thermally laminating the bonding surface of the metal foil to a resin-made plate-shaped carrier of the B-stage.

The decane compound can be used in the form of an aqueous solution. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is especially effective when a highly hydrophobic decane compound is used. The aqueous solution of the decane compound promotes hydrolysis of the alkoxy group by stirring, and if the stirring time is long, the condensation of the hydrolyzed product can be promoted. Usually, a decane compound which has been subjected to hydrolysis and condensation after a sufficient stirring time tends to lower the peel strength of the metal foil and the plate-shaped carrier. Therefore, the peel strength can be adjusted by adjusting the stirring time. The stirring time after dissolving the decane compound in water is not limited, and may be, for example, 1 to 100 hours, and typically 1 to 30 hours. Of course, there is also a method of using without stirring.

When the concentration of the decane compound in the aqueous solution of the decane compound is high, the peel strength of the metal foil and the plate-shaped carrier tends to be lowered, and the peel strength can be adjusted by adjusting the concentration of the decane compound. The concentration of the decane compound in the aqueous solution is not limited, and may be 0.01 to 10.0% by volume, and typically 0.1 to 5.0% by volume.

The pH of the aqueous solution of the decane compound is not particularly limited, and it may be used in an acidic or alkaline manner. For example, it can be used at a pH of from 3.0 to 10.0. From the viewpoint of not requiring a special pH adjustment, it is preferably a pH value in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH value in the range of 7.0 to 9.0.

The peel strength of the metal foil before use of the decane compound and the plate-shaped carrier is preferably 10 gf/cm or more, more preferably 30 gf/cm or more, and further preferably from the viewpoint of facilitating the adjustment of the peel strength by the decane compound. It is 50 gf/cm or more, and on the other hand, it is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, still more preferably 80 gf/cm or less. By setting the peeling strength of the metal foil and the plate-shaped carrier to such a range, it is easy to adjust the peeling strength as follows: it is not peeled off at the time of conveyance or processing, and can be easily peeled off by manpower. Peel off, that is, mechanically peel off.

Further, in the manufacturing process of the multilayer printed wiring board, in many cases, heat treatment is performed in the lamination pressing step or the desmear step. Therefore, the more the thermal history of the metal foil attached to the carrier is, the stronger the number of layers. Therefore, especially in consideration of application to a multilayer printed wiring board, it is preferable that the peeling strength of the metal foil and the plate-shaped carrier is within the above range after the required heat history.

Therefore, in a further preferred embodiment of the present invention, the heating conditions in the manufacturing process of the multilayer printed wiring board are assumed, for example, after heating at least one of 3 hours, 6 hours, or 9 hours at 220 ° C, the metal foil and The peeling strength of the plate-shaped carrier is preferably 30 gf/cm or more, more preferably 50 gf/cm or more. Further, the peel strength is preferably 200 gf/cm or less, more preferably 150 gf/cm or less, still more preferably 80 gf/cm or less.

Regarding the peel strength after heating at 220 ° C, it is preferable that the peel strength is satisfied after 3 hours and after 6 hours, or after 6 hours and 9 hours, from the viewpoint of a plurality of layers. The above range, and more preferably, all of the peel strengths after 3 hours, 6 hours, and 9 hours satisfy the above range.

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

Hereinafter, specific constituent elements of each material for realizing such peel strength will be described.

The resin to be a plate-shaped carrier is not particularly limited, and a phenol resin, a polyimide resin, an epoxy resin, a natural rubber, a rosin or the like can be used, and a thermosetting resin is preferable. Also, a prepreg can be used. The prepreg before bonding with the metal foil may be in the B-stage state. If the linear expansion coefficient of the prepreg (C stage) is 12 to 18 (×10 ^-6 /°C), it is 16.5 (×10 ^-6 /°C) or SUS pressed plate of the copper foil as a constituent material of the substrate. 17.3 (×10 ^-6 /°C) is substantially equal, so that it is less advantageous in terms of positional deviation caused by a phenomenon in which the size of the substrate before and after pressing differs from the size at the time of design (scale change). Further, as a synergistic effect of these advantages, it is also possible to produce a very thin multilayer hollow substrate. The prepreg used herein may be the same as or different from the prepreg constituting the circuit board.

The plate-shaped carrier preferably has a higher glass transition temperature Tg, for example, a glass transition of 120 to 320 ° C, preferably 170 to 240 ° C, from the viewpoint of maintaining the peel strength after heating to an optimum range. Temperature Tg. Further, the glass transition temperature Tg is a value measured by DSC (Differential Scanning Calorimetry).

Further, it is preferable that the thermal expansion coefficient of the resin is within +10% and -30% of the thermal expansion coefficient of the metal foil. Thereby, the positional deviation of the circuit caused by the difference in thermal expansion between the metal foil and the resin can be effectively prevented, and the occurrence of defective products can be reduced, and the yield can be improved.

The thickness of the plate-shaped carrier is not particularly limited, and may be either rigid or soft. However, if it is too thick, it will adversely affect the heat distribution during hot pressing. On the other hand, if it is too thin, it will bend and cannot be printed. In this respect, the production step of the sheet is usually 5 μm or more and 1000 μm or less, preferably 50 μm or more and 900 μm or less, and more preferably 100 μm or more and 400 μm or less.

As the metal foil, a representative copper or copper alloy foil may be used, and a foil such as aluminum, nickel or zinc may be used. In the case of copper or copper alloy foil, an electrolytic foil or a calendered foil can be used. The metal foil is not limited, and is usually 1 μm or more, preferably 5 μm or more, and 400 μm or less, preferably 120 μm or less, in consideration of the use as a wiring of a printed circuit board. In the case where a metal foil is attached to both sides of the plate-shaped carrier, a metal foil of the same thickness may be used, or a metal foil of a different thickness may be used.

Various surface treatments can also be applied to the metal foil used. For example, metal plating for imparting heat resistance (Ni plating, Ni-Zn plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy plating, Co-Ni plating) Alloy, etc.), chromate treatment for imparting rust prevention or discoloration resistance (including one or more kinds of Zn in the chromate treatment liquid, P, Ni, Mo, Zr, Ti and other alloying elements), roughening treatment to adjust the surface roughness (for example, using copper electrodeposited particles or Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-Co alloy plating, Cu-As alloy plating, Cu-As-W alloy plating, etc.). The roughening treatment of course affects the peel strength of the metal foil and the plate-shaped carrier, and the chromate treatment also has a large influence. Although the chromate treatment is important from the viewpoint of rust preventive property and discoloration resistance, it is observed that the peel strength is remarkably increased, and therefore it is also useful as a means for adjusting the peel strength.

In the conventional CCL, it is preferable that the peeling strength of the resin and the copper foil is high, and the surface treatment such as roughening treatment is performed by, for example, a matte surface (M surface) of the electrolytic copper foil. Achieve increased adhesion from chemical and physical anchor effects. Further, various adhesives and the like are added to the resin side to enhance the adhesion to the metal foil. As described above, unlike the CCL, the metal foil and the resin must be finally peeled off, so that the peel strength is too high, which is disadvantageous.

Therefore, in a preferred embodiment of the metal foil with a carrier of the present invention, in order to adjust the peel strength of the metal foil and the plate-shaped carrier to the above preferred range, the metal foil measured in accordance with JIS B 0601:2001 The ten-point average roughness (Rz jis) of the surface indicates the surface roughness of the bonding surface, and is preferably 3.5 μm or less, and more preferably 3.0 μm or less. However, it takes time and effort to reduce the surface roughness without limitation, and it is preferably 0.1 μm or more, and more preferably 0.3 μm or more. When an electrolytic copper foil is used as the metal foil, if it is adjusted to such surface roughness, a glossy surface (shiny surface, S surface) and a rough surface (matt surface, M) can be used. Any of the faces, but it is easier to adjust to the above surface roughness using the S face. On the other hand, the ten-point average roughness (Rz jis) of the surface of the metal foil which is not in contact with the carrier is preferably 0.4 μm or more and 10.0 μm or less.

Moreover, in a preferred embodiment of the metal foil with a carrier of the present invention, A surface treatment for improving the peel strength, such as roughening treatment of the bonding surface of the metal foil and the resin. Further, in a preferred embodiment of the metal foil with a carrier of the present invention, an adhesive for enhancing the adhesion to the metal foil is not added to the resin.

As a condition for producing hot pressing of the metal foil with a carrier, in the case of using a prepreg as a plate-shaped carrier, it is preferably a temperature of 30 to 40 kg/cm ² , which is higher than the glass transition temperature of the prepreg. Hot pressing.

In view of the above, the present invention provides a metal foil having the above-described decane compound on at least one surface of the metal foil as described above in order to make the resin-made plate-shaped carrier adhere to each other in a peelable manner. , a hydrolyzate thereof or a condensate of the hydrolyzate. Here, in order to have a decane compound, a hydrolyzed product thereof or a condensate of the hydrolyzate on the surface of the metal foil, a part or all of the surface of the metal foil may be subjected to a coating treatment or the like by using a decane compound. Further, the surface of the metal foil may be subjected to chromate treatment or the like as described above before being operated by a decane compound.

In another aspect, the present invention provides a plate-shaped carrier which has the above-described decane compound, at least one surface of a plate-shaped carrier which is the adhesion surface, in order to make the metal foil as described above adhere to each other in a peelable manner. a hydrolysate or a condensate of the hydrolyzate. Here, in order to have a decane compound, a hydrolyzed product thereof or a condensate of the hydrolyzate on the surface of the plate-shaped carrier, a part or all of the surface of the plate-shaped carrier may be subjected to coating treatment or the like by using a decane compound. effect.

In still another aspect, the present invention provides a metal foil for a hollow multilayer printed wiring board which has the above-described ruthenium compound, a hydrolyzed product thereof or a condensate of the hydrolyzed product on the surface of the metal foil as described above. Here, in order to have a decane compound, a hydrolyzed product thereof or a condensate of the hydrolyzate on the surface of the metal foil, a part or all of the surface of the metal foil may be subjected to a coating treatment or the like by using a decane compound. Further, the surface of the metal foil may be subjected to chromate treatment or the like as described above before being operated by a decane compound.

Further, the surface of the metal foil or the resin is measured by a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy device), an EPMA (electron beam micro analyzer), and an EDX (energy dispersive X-ray analysis), and the surface is detected. For Si, it is presumed that a decane compound is present on the surface of the metal foil or the resin.

Further, in another aspect, the invention provides the use of the above-described carrier-attached metal foil.

First, there is provided a method for producing a multilayer metal-clad laminate comprising: laminating at least one metal foil side of the above-mentioned carrier-attached metal foil, and then repeatedly laminating the resin or the metal foil once or more, for example, 1 to 10 times.

Secondly, there is provided a method for producing a multi-layer metal-clad laminate comprising: laminating a resin on a metal foil side of the above-mentioned carrier metal foil, and then repeating a laminated resin, a single-sided or double-sided metal-clad laminate, or the present invention The carrier metal foil or the metal foil is provided once or more, for example, 1 to 10 times.

In the method for producing a multilayer metal-clad laminate, the step of separating and separating the plate-shaped carrier with the carrier-attached metal foil from the metal foil may be further included.

Further, the method further includes the step of removing the part or all of the metal foil by etching after separating the plate-shaped carrier from the metal foil and separating the metal foil.

Thirdly, there is provided a method for producing a build-up substrate comprising: laminating a resin on a metal foil side of the above-mentioned carrier metal foil, and then repeating a laminated resin, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate The plate, or the metal foil with a carrier of the present invention, or the metal foil is once or more, for example, 1 to 10 times.

Fourthly, there is provided a method for producing a build-up substrate comprising the step of laminating one or more build-up wiring layers on the metal foil side of the above-mentioned carrier metal foil. At this time, the build-up wiring layer can be formed using at least one of a subtractive method, a full additive method, or a semi-additive method.

The subtractive method refers to selectively removing a metallized laminate by etching or the like. A method of forming a conductor pattern on an unnecessary portion of a metal foil on a wiring board (including a printed wiring board or a printed circuit board). The full additive method is a method of forming a conductor pattern by electroless plating or/and electroplating without using a metal foil as a conductor layer, and the semi-additive method is applied to, for example, a seed layer composed of a metal foil. A method of obtaining a conductor pattern by performing electroless metal deposition, plating, etching, or both to form a conductor pattern, and then etching the unnecessary seed layer to remove the conductor pattern.

In the method for manufacturing the build-up substrate, the method further includes the steps of: a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier metal foil, and a plate-shaped metal foil with a carrier The carrier or the resin is opened, and conduction plating is performed on the side and the bottom surface of the hole. Furthermore, the method further comprises the steps of: forming the metal foil of the single-sided or double-sided wiring substrate, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the metal foil constituting the metal foil with the carrier; At least one of them forms a wiring.

In the method for producing a build-up substrate, the method further includes a step of adhering a metal foil to one surface and further depositing a carrier side of the metal foil with a carrier of the present invention on the surface on which the wiring is formed. Further, the method further includes the step of laminating a resin on the surface on which the wiring is formed, and laminating the metal foil of the present invention to which the metal foil is adhered to the resin.

In addition, the "surface on which the wiring is formed" means a portion where wiring is formed on the surface of each appearance during the layering process, and the final product and its intermediate materials are included as the build-up substrate.

In the method for producing a build-up substrate, the step of separating the plate-shaped carrier with the metal foil with the carrier and the metal foil may be further separated.

Furthermore, the method further includes the step of removing the one or the entire surface of the metal foil by etching after separating the plate-shaped carrier from the metal foil and separating the metal foil.

Further, in the method for producing a multilayer metal-clad laminate and the method for producing a build-up substrate, each layer may be laminated by thermocompression bonding. The thermocompression bonding can be used to laminate each layer The process can be carried out in a unified manner after being layered to a certain extent.

In the following, as a specific example of the above-described application, a method of manufacturing a hollow build-up substrate using the copper foil-attached copper foil 11 on which the copper foil is adhered to both sides of the plate-shaped carrier 11c of the resin sheet of the present invention is exemplified. In this method, after a desired number of buildup layers 16 are laminated on both sides of the carrier copper foil 11, the double-sided copper foil is peeled off from the carrier copper foil 11 (see Fig. 3).

For example, on the metal foil side of the metal foil with a carrier of the present invention, a resin as an insulating layer, a two-layer circuit substrate, and a resin as an insulating layer are sequentially laminated thereon, and the metal foil side is further in contact with the resin sheet. The metal foil of the metal foil with a carrier of the present invention is sequentially superposed, whereby a build-up substrate can be manufactured.

Further, as another method, a resin which is an insulating layer and a conductor are sequentially laminated on at least one metal foil side of a metal foil with a metal foil to which a metal foil is adhered to both sides of a resin-made plate-shaped carrier 11c. Metal foil of the layer. Then, the step of adjusting the thickness by half etching the entire surface of the metal foil as needed may be included. Then, laser processing is performed on a specific position of the laminated metal foil to form a through hole penetrating the metal foil and the resin, and the desmear treatment for removing the dross in the through hole is performed, and the bottom, the side surface and the metal foil of the through hole are formed. Electroless plating is performed on the entire surface or a part of the layer to form an interlayer connection, and electroplating is performed as needed. It is also possible to form a plating resist in advance on each portion of the metal foil which is not subjected to electroless plating or electroplating. Further, in the case where the adhesion between the electroless plating, the electroplating, and the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically roughened in advance. In the case of using a plating resist, the plating resist is removed after plating. Then, an unnecessary portion of the metal foil, the electroless plating portion, and the plating portion is removed by etching, thereby forming a circuit. Thereby, a build-up substrate can be manufactured. It is also possible to repeat the steps of laminating the resin from the copper foil to the circuit to form a plurality of layers of the build-up substrate.

Further, the outermost surface of the build-up substrate may be laminated on the resin side of the metal foil with the metal foil attached to the metal foil on one side of the present invention, or may be laminated after temporarily laminating the resin sheet. A metal foil with a metal foil attached to the metal foil is bonded to the metal foil to form a layer.

Here, as the resin sheet for producing the build-up substrate, a prepreg containing a thermosetting resin can be preferably used.

Further, as another method, a resin layer as an insulating layer is laminated on the exposed surface of the metal foil of the laminate obtained by laminating a metal foil (for example, a copper foil) on one side or both sides of the plate-shaped carrier of the present invention. Dip or photosensitive resin. Thereafter, a through hole is formed at a specific position of the resin. In the case of using, for example, a prepreg as a resin, the through holes can be formed by laser processing. After the laser processing, the desmear treatment for removing the dross in the through hole may be performed. Further, in the case where a photosensitive resin is used as the resin, the resin forming the portion of the through hole can be removed by photolithography. Then, the bottom surface of the through hole, the side surface, and the entire surface or part of the resin are subjected to electroless plating to form an interlayer connection, and further plating is performed as needed. It is also possible to form a plating resist on the resin before electroplating or electroplating. Further, in the case where the adhesion between the electroless plating, the electroplating, and the plating resist and the resin is insufficient, the surface of the resin may be chemically roughened in advance. In the case of using a plating resist, the plating resist is removed after plating. Then, an unnecessary portion of the electroless plating portion or the plating portion is removed by etching, thereby forming an electric circuit. Thereby, a build-up substrate can be manufactured. It is also possible to repeat the steps from the lamination of the resin to the formation of the circuit to form a plurality of layers of the build-up substrate.

Further, the outermost surface of the build-up substrate may be laminated on the resin side of the laminate in which the metal foil is adhered to the single surface of the present invention, or the resin side of the metal foil with the metal foil adhered to the metal foil on one side, or may be laminated. After laminating the resin, the metal foil of one of the laminates with the metal foil adhered to the double-sided layer of the present invention or a metal foil with a metal foil adhered to the metal foil on both sides is laminated.

The hollow build-up substrate thus produced is subjected to a plating step and/or an etching step to form wiring on the surface, and further, the carrier resin and the copper foil are peeled off and separated, thereby completing the build-up wiring board. The wiring may be formed on the peeled surface of the metal foil after the separation and separation, and the entire surface of the metal foil may be removed by etching to form a build-up wiring board. Further, the printed circuit board is completed by mounting electronic components on the build-up wiring board. Moreover, the electronic zero is directly mounted on the hollow build-up substrate before the resin is peeled off. A printed circuit board is also available.

[Examples]

In the following, the experimental examples are shown as examples and comparative examples of the present invention, but they are provided to better understand the present invention and its advantages, and are not intended to limit the invention.

<Experimental Example 1>

A plurality of electrolytic copper foils (thickness: 12 μm) were prepared, and the light (S) surface of each of the electrolytic copper foils was subjected to nickel-zinc (Ni-Zn) alloy treatment and chromate (Cr-Zn chromic acid) under the following conditions. After the salt treatment, the ten-point average roughness (Rz jis, measured according to JIS B 0601:2001) of the bonding surface (here, the S surface) is set to 1.5 μm, and the Mitsubishi Gas Chemical Co., Ltd. The produced prepreg (BT resin) was bonded to the S surface of the electrolytic copper foil, and hot pressed at 190 ° C for 100 minutes to prepare a copper foil with a carrier.

(nickel-zinc alloy plating)

Ni concentration 17g / L (added with NiSO ₄ )

Zn concentration 4g / L (added with ZnSO ₄ )

pH 3.1

Liquid temperature 40 ° C

Current density 0.1~10A/dm ²

Plating time 0.1~10 seconds

(chromate treatment)

Cr concentration 1.4g / L (added by CrO ₃ or K ₂ CrO ₇ )

Zn concentration 0.01~1.0g/L (added by ZnSO ₄ )

Na ₂ SO ₄ concentration 10g / L

pH 4.8

Liquid temperature 55 ° C

Current density 0.1~10A/dm ²

Plating time 0.1~10 seconds

After applying an aqueous solution of a decane compound to the S surface using a spray coater on a plurality of electrolytic copper foils, the surface of the copper foil was dried in air at 100 ° C, and then bonded to the prepreg. Regarding the use conditions of the decane compound, the type of the decane compound, the stirring time before the coating of the decane compound in water until the coating, the concentration of the decane compound in the aqueous solution, the concentration of the alcohol in the aqueous solution, and the pH of the aqueous solution are shown in Table 1.

Further, it is assumed that a heat history is applied to a plurality of copper foil-attached copper foils to perform further heat treatment on the copper foil-forming circuit or the like, and the conditions described in Table 1 (here, at 220 ° C for 3 hours) are performed. Heat treatment.

The peel strength of the copper foil with a carrier obtained by hot pressing and the copper foil in the copper foil with a carrier after heat processing and the plate-shaped carrier (heated resin) was measured. The results are shown in Table 1.

Moreover, in order to evaluate the peeling workability, the manual work time (time/number) required per unit number was evaluated. The results are shown in Table 2.

<Experimental Example 2~18>

A copper foil with a carrier was produced in the same manner as in Experimental Example 1 using the copper foil, the resin (prepreg) shown in Table 1, and a part of the decane compound. The heat treatment of the conditions shown in Table 1 was further carried out in several experimental examples. The same evaluation as in Experimental Example 1 was carried out separately. The results are shown in Tables 1 and 2.

Further, the type of the bonding surface of the copper foil, the surface treatment conditions and the surface roughness Rz jis, the use conditions of the decane compound, the type of the prepreg, and the laminate conditions of the copper foil and the prepreg are as shown in Table 1. Show.

Among the surface treatment conditions of the treated surface of the copper foil, the specific conditions of the epoxy decane (treatment) and the roughening treatment are as follows.

(epoxy decane treatment)

Treatment liquid: 3-glycidoxypropyltrimethoxydecane 0.9% by volume aqueous solution

pH 5.0~9.0

Stirring at room temperature for 12 hours

Treatment method: After the treatment liquid was applied using a spray coater, the treated surface was dried in air at 100 ° C for 5 minutes.

(roughening treatment)

Cu concentration 20g / L (added with CuSO ₄ )

H ₂ SO ₄ concentration 50~100g/L

As concentration 0.01~2.0g/L (added with arsenious acid)

Liquid temperature 40 ° C

Current density 40~100A/dm ²

Plating time 0.1~30 seconds

<Experimental Examples 19 to 20>

A copper foil with a carrier was produced in the same manner as in Experimental Example 1 using the copper foil, the resin (prepreg) shown in Table 3, and a part of the decane compound. Further, heat treatment under the conditions shown in Table 3 was carried out. The same evaluation as in Experimental Example 1 was carried out with respect to the thus obtained carrier copper foil. The results are shown in Tables 3 and 4.

Further, the S surface was used as a bonding surface of the copper foil, and the surface was subjected to chromate treatment under the above conditions. Further, the surface roughness Rz jis of the copper foil, the kind of the prepreg, the use conditions of the decane compound used for the surface treatment of the prepreg, and the lamination conditions of the copper foil and the prepreg are shown in Table 3.

According to the table, it is understood that the decane compound can be treated on the surface of the copper foil or the surface of the prepreg can be obtained in the same manner as the peel strength of the laminate, the peel strength after heating, and the peeling workability. result.

(Additional wiring board)

The FR-4 prepreg (manufactured by Nanya Plastics Co., Ltd.) and copper foil (manufactured by JX Nippon Mining & Metal Co., Ltd., JTC12μm (product name)) are sequentially superposed on both sides of the copper foil with the carrier thus produced, to 3 MPa. The pressure was hot pressed under the heating conditions shown in the respective tables to prepare a four-layer copper clad laminate.

Then, a hole of 100 μm in diameter of the copper foil penetrating the surface of the above-mentioned four-layer copper clad laminate and the insulating layer (hardened prepreg) therethrough was opened using a laser processing machine. Then, copper plating is performed on the surface of the copper foil on the copper foil with the carrier exposed on the bottom of the hole, the side surface of the hole, and the copper foil on the surface of the four-layer copper clad laminate by electroless copper plating or electroplating copper. An electrical connection is formed between the copper foil on the copper foil with the carrier and the copper foil on the surface of the four-layer copper clad laminate. Then, one portion of the copper foil on the surface of the four-layer copper clad laminate was etched using an iron (III) chloride-based etching solution to form an electric circuit. Thus, four layers of build-up substrates were obtained.

Then, in the four-layer build-up substrate, the plate-shaped carrier with the carrier copper foil was peeled off from the copper foil to separate, and two sets of two-layer build-up wiring boards were obtained.

Then, the copper foil which was adhered to the plate-shaped carrier on the two sets of two-layer build-up wiring boards was etched to form wiring, and two sets of two-layer build-up wiring boards were obtained.

In each of the experimental examples, a plurality of four-layer build-up substrates were produced, and the adhesion between the prepreg and the copper foil constituting the carrier-attached copper foil in the step of fabricating the build-up substrate was visually confirmed. As a result, Tables 1 and 3 were used. The peeling strength and the peeling strength after heating were evaluated as the build-up wiring sheets of the carrier-attached copper foil produced under the conditions of "S" and "G". When the layer was formed, the resin (plate-shaped carrier) with the carrier copper foil was not broken. And can be peeled off. However, as for the conditions of the evaluation of "G", as described in Tables 1 and 3, there is also a case where the copper foil is peeled off from the plate-shaped carrier without a peeling operation at the time of layer formation.

Further, regarding the condition of evaluation of "N", the resin was broken during the peeling operation of the copper foil in the copper foil with a carrier, or the resin was left on the surface of the copper foil at the time of layering.

Further, in the case of the evaluation of "-", the resin was peeled off during the peeling operation of the copper foil in the copper foil with a carrier at the time of layering, but there was a case where the copper foil was peeled off without a peeling operation.

Claims (38)

A carrier-attached metal foil comprising a plate-shaped carrier made of resin and a metal foil which is detachably adhered to at least one side of the carrier, and the plate-shaped carrier and the metal foil are used alone or in combination. a decane compound represented by the formula, a hydrolyzate thereof, and a condensate of the hydrolyzate, (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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group). The carrier-attached metal foil according to claim 1, wherein the peeling strength of the plate-shaped carrier and the metal foil is 10 gf/cm or more and 200 gf/cm or less. The carrier-attached metal foil according to claim 2, wherein the peeling strength of the plate-shaped carrier and the metal foil is 30 gf/cm or more and 200 gf/cm or less. The carrier-attached metal foil according to any one of claims 1 to 3, wherein the resin-made plate-shaped carrier contains a thermosetting resin. The carrier-attached metal foil according to any one of claims 1 to 3, wherein the resin-made plate-shaped carrier is a prepreg. The carrier-attached metal foil according to claim 4, wherein the resin-made plate-shaped carrier has a glass transition temperature Tg of 120 to 320 °C. The carrier-attached metal foil according to any one of claims 1 to 3, wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less. The metal foil with a carrier according to any one of claims 1 to 3, wherein, after heating at 220 ° C for at least one of 3 hours, 6 hours or 9 hours, the peeling strength of the metal foil and the plate-shaped carrier is 10 gf / cm or more and 200 gf / cm or less. A metal foil for a coreless multilayer printed wiring board having a decane compound of the following formula, a hydrolyzed product thereof or a condensate of the hydrolyzed product on the surface of the metal foil, (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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group). The metal foil for a hollow multilayer printed wiring board according to the ninth aspect of the invention, wherein the surface of the metal foil on the side on which the decane compound acts is subjected to chromate treatment before the action of the decane compound. The metal foil for a hollow multilayer printed wiring board according to claim 9 or 10, wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less. A metal foil which is a condensate of a decane compound of the following formula, a hydrolyzate thereof or a hydrolyzate of at least one surface thereof, for use in a peelable manner in which a resin-made plate-shaped carrier is adhered to the surface, (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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group). The metal foil according to claim 12, wherein the surface of the metal foil on the side on which the decane compound acts is subjected to chromate treatment before the decane compound is allowed to act. The metal foil according to claim 12, wherein the side surface of the metal foil in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less. A plate-shaped carrier which is a resin-made plate-shaped carrier having at least one surface having a decane compound of the following formula, a hydrolyzed product thereof or a condensate of the hydrolyzate, for adhering the metal foil to the surface in a peelable manner use, (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 one or more hydrogen atoms are substituted by a halogen atom; a hydrocarbon group, wherein 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 one or more hydrogen atoms are substituted by a halogen atom. Any hydrocarbon group). A method for producing a multi-layer metal-clad laminate comprising: at least one metal foil side-layer resin of a carrier-attached metal foil according to any one of claims 1 to 8, and then repeating the resin or metal layer by one or more times Foil. A method for producing a multi-layer metal-clad laminate comprising: a metal foil side-layer resin with a carrier metal foil according to any one of claims 1 to 8, and then repeating the resin layer, single-sided or more A double-sided metal-clad laminate, or a carrier-attached metal foil or a metal foil according to any one of claims 1 to 8. The method for producing a multi-layer metal-clad laminate according to claim 16 or 17, further comprising the step of separating the plate-shaped carrier with the carrier metal foil from the metal foil. The manufacturing method of claim 18, comprising the step of removing a part or all of the peeled and separated metal foil by etching. A multi-layer metal-clad laminate comprising at least one of a resin, a resin, and a metal layer on at least one metal foil side of the carrier-attached metal foil according to any one of claims 1 to 8. A multi-layer metal-clad laminate comprising: a resin, a resin, a single-sided or double-sided metal-clad laminate, or at least one metal foil side of the carrier-attached metal foil according to any one of claims 1 to 8; At least one of the carrier-attached metal foil or the metal foil of any one of claims 1 to 8. The multi-layer metal-clad laminate according to claim 20, wherein the resin of the plate-shaped carrier obtained by separating the plate-shaped carrier with the carrier metal foil and the metal foil is not left on the surface of the metal foil. A multilayer metal clad laminate according to claim 22, wherein a part of the metal foil adhered to the plate-shaped carrier is removed by etching. A method of manufacturing a build-up substrate, comprising the step of forming one or more build-up wiring layers on a metal foil side of a carrier-attached metal foil according to any one of claims 1 to 8. The method for manufacturing a build-up substrate according to claim 24, wherein the build-up wiring layer is used in a subtractive method or a full additive method or a semi-additive method. Formed by at least one. A method for producing a build-up substrate, comprising: at least one metal foil side build-up resin of the carrier-attached metal foil according to any one of claims 1 to 8, and then repeating the resin over one time, one-sided or A double-sided wiring board, a single-sided or double-sided metal-clad laminate, or a carrier-attached metal foil or metal foil according to any one of claims 1 to 8. The method for manufacturing a build-up substrate according to claim 26, further comprising the steps of: a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier metal foil, and a carrier The plate-shaped carrier of the metal foil or the resin is perforated, and the side surface and the bottom surface of the hole are electrically plated. The method for producing a build-up substrate according to claim 26, wherein the method further comprises the step of: forming a metal foil of the single-sided or double-sided wiring substrate to form a single-sided or double-sided metal-clad laminate. At least one of the metal foil of the board and the metal foil constituting the metal foil with a carrier forms a wiring. The method for producing a build-up substrate according to claim 28, further comprising the step of: a resin sheet side of a carrier-attached metal foil according to any one of claims 1 to 8 in which the metal foil is adhered to one side The layer is laminated on the surface on which the wiring is formed. The method for manufacturing a build-up substrate according to claim 28, which comprises the steps of: laminating a resin on a surface on which the wiring is formed, and making the metal foil on both sides in close contact with any one of claims 1 to 8; A metal foil with a carrier metal foil is laminated in contact with the resin. A method of manufacturing a build-up substrate according to claim 26 or 27, wherein the resin At least one of them is a prepreg. A method of manufacturing a build-up wiring board according to any one of claims 24 to 31, further comprising the step of: forming a plate-shaped carrier with a carrier metal foil and a metal foil Stripped and separated. The method of manufacturing a build-up wiring board according to claim 32, further comprising the step of removing a part or all of the metal foil adhered to the plate-shaped carrier by etching. A build-up wiring board having at least one metal foil side of a carrier-attached metal foil according to any one of claims 1 to 8 having one or more selected from the group consisting of the following (A) to (H) Items: (A) one or more layered wiring layers; (B) one or more layered wiring layers formed using at least one of full additive or semi-additive; (C) a resin having at least one metal foil side, and then having more than one layer of resin, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, and the carrier metal of any one of claims 1 to 8. a foil or a metal foil; a single-sided or double-sided wiring substrate described in (D) (C), a single-sided or double-sided metal-clad laminate, a metal foil with a carrier metal foil, a plate-shaped carrier with a carrier metal foil, or The resin has a hole, and has a conductive plating layer on the side surface and the bottom surface of the hole; (E) in (C) or (D), the metal foil constituting the single-sided or double-sided wiring substrate, which constitutes one-sided or two-sided At least one of the metal foil of the metal-clad laminate and the metal foil constituting the metal foil with a carrier has wiring; (F) at (C) Or (D) or (E), the resin sheet side of the carrier-attached metal foil of any one of claims 1 to 8 in which the metal foil is adhered to one side is in contact with the wiring surface; (G) The carrier-attached metal foil of any one of claims 1 to 8 in which the resin has a resin on the surface of the wiring (C) or (D) or (E), and the metal foil is adhered to the double-sided surface. One of the metal foils is in contact with the resin; (H) is at least one of (C), (D), (E), (F), and (G), and at least one of the resins is a prepreg. The build-up wiring board of claim 34, wherein the resin of the plate-shaped carrier obtained by separating the plate-shaped carrier with the carrier metal foil and the metal foil is not left on the surface of the metal foil. The build-up wiring board of claim 35, wherein a part of the metal foil adhered to the plate-shaped carrier is removed by etching. A method of manufacturing a printed circuit board, comprising the steps of: manufacturing a build-up substrate by the manufacturing method of any one of claims 24 to 31. A method of manufacturing a printed circuit board comprising the steps of manufacturing a build-up wiring board by the manufacturing method of claim 32 or 33.