TW201420332A - A metal foil with a carrier - Google Patents

Abstract

Provided is a metallic foil having a carrier, wherein the peel strength of a resin sheet-shaped carrier and a metallic foil has been controlled. This metallic foil having a carrier, which comprises a sheet-shaped resin carrier and a metallic foil that has been detachably adhered to at least one surface of the carrier, is characterised in that the sheet-shaped carrier and the metallic foil are bonded using a resin coating comprising silicone and at least one resin selected from epoxy resin, melamine resin and fluororesin.

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 for use in manufacturing a single-sided or two-layer multilayer laminated board or an extremely thin coreless substrate used for a printed wiring board.

In general, a printed wiring board is a dielectric material called a "prepreg" obtained by impregnating a base material such as a synthetic resin sheet, a glass plate, a glass nonwoven fabric, or a paper with a synthetic resin as a basic constituent material. Further, a sheet such as copper or a copper alloy foil having conductivity is joined to the side opposite to the prepreg. The laminate thus assembled is generally referred to as a CCL (Copper Clad Laminate) material. For the surface of the copper foil which is in contact with the prepreg, in order to improve the joint strength, a rough surface is usually formed. A foil of aluminum, nickel, zinc or the like is sometimes used instead of copper or copper alloy foil. These thicknesses are about 5 to 200 μm. The commonly used CCL (Copper Clad Laminate) material 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 mechanically adhered to at least one surface of the carrier, and the carrier-attached metal foil is described. The main purpose of assembly of printed wiring boards. Further, it is disclosed that the peel strength of the plate-shaped carrier and the metal foil is preferably from 1 gf/cm to 1 kgf/cm. According to the metal foil with a carrier, since the synthetic resin is supported over the entire surface of the copper foil, it can be prevented from being deposited in the laminate. Wrinkles are formed on the copper foil. Further, since the metal foil with the carrier is adhered to the synthetic resin without a gap, when the surface of the metal foil is subjected to gold plating or etching, it can be put into a chemical solution for gold plating or etching. Further, since the coefficient of linear expansion of the synthetic resin is at the same level as the copper foil as a constituent material of the substrate and the prepreg after polymerization, the positional deviation of the circuit is not caused, so that the occurrence of defective products can be reduced. Excellent results in yield improvement.

[Previous Technical Literature]

[Patent Literature]

[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 the manufacturing cost by simplifying the manufacturing steps of the printed circuit board and improving the yield, but the peel strength of the plate-shaped carrier and the metal foil There is still room for research on the optimization and its means. In particular, as a problem apparent to the inventors, the peeling 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 peel strength which can be easily adjusted. mechanism. Accordingly, an object of the present invention is to provide a metal foil with a carrier having a peel strength of a resin-made plate-shaped carrier and a metal foil.

The inventors of the present invention have conducted an effort to adjust the peel strength between the resin sheet and the metal foil, and as a result, found that at least the resin coating film combined with the specific resin is used before the resin sheet is bonded to the metal foil. The surface of one of the layers is subjected to a coating treatment to achieve a peeling strength corresponding to the intended use, thereby completing the present invention.

That is, the present invention is as follows.

(1) A carrier-attached metal foil which is made of a resin-made plate-shaped carrier and which is detachably adhered A metal foil which is formed on at least one side of the carrier, and a resin coating film made of polyoxymethylene and any one or a plurality of resins selected from the group consisting of an epoxy resin, a melamine resin, and a fluororesin is used. The carrier is bonded to a metal foil.

(2) The carrier-coated metal foil according to (1), wherein the resin coating film contains an epoxy resin or a melamine resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyfluorene oxide.

(3) The carrier-attached metal foil according to (1) or (2), wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide.

(4) The carrier-attached metal foil according to any one of (1) to (3), wherein the resin coating film has a thickness of 0.1 to 10 μm.

(5) The carrier-attached metal foil according to any one of (1) to (4), 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.

(6) The carrier-attached metal foil according to any one of (1) to (5) wherein the resin-made plate-shaped carrier contains a thermosetting resin.

(7) The carrier-attached metal foil according to any one of (1) to (6), wherein the resin-made plate-shaped carrier is a prepreg.

(8) A carrier metal foil according to (6) or (7), wherein the plate-shaped carrier made of the above resin has a glass transition temperature Tg of from 120 to 320 °C.

(9) The carrier-attached metal foil according to any one of (1) to (8), wherein a surface of the metal foil on the side in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(10) The carrier-attached metal foil according to any one of (1) to (9), wherein a ten-point average roughness (Rz jis) of a surface of the metal foil which is not in contact with the carrier is 0.4 μm or more and 10.0 Below μm.

The carrier-attached metal foil according to any one of (1) to (10), wherein the metal foil has a thickness of from 1 μm to 400 μm.

(12) The carrier-attached metal foil according to any one of (1) to (11), wherein the stripping of the metal foil and the plate-shaped carrier after heating at 220 ° C for at least one of 3 hours, 6 hours or 9 hours The strength is 10 gf/cm or more and 200 gf/cm or less.

(13) The carrier-attached metal foil according to any one of (1) to (12) wherein the metal foil is a copper foil.

(14) A metal foil for a printed wiring board having a resin coating film comprising a polyfluorene oxide and any one or a plurality of resins selected from the group consisting of an epoxy resin, a melamine resin, and a fluororesin on the surface of the metal foil. .

(15) The metal foil for a printed wiring board according to (14), wherein the resin coating film contains an epoxy resin or a melamine in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyfluorene oxide. Resin.

(16) The metal foil for a printed wiring board according to the above aspect, wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide.

(17) The metal foil for a printed wiring board according to any one of (14) to (16), wherein the resin coating film has a thickness of 0.1 to 10 μm.

The metal foil for a printed wiring board according to any one of (14) to (17), wherein the polyfluorene and the epoxy resin, the melamine resin, and the fluororesin are selected from the group consisting of The surface on the side where the resin coating film composed of the plurality of resins functions is applied, and the chromate treatment is performed before the resin coating film acts.

(19) The metal foil for a printed wiring board according to any one of (14) to (18), wherein a ten-point average roughness (Rz jis) of a surface of the metal foil on the side in contact with the resin coating film is 3.5 Below μm.

(20) The metal foil for a printed wiring board according to any one of (14) to (19), wherein a ten-point average roughness (Rz jis) of a surface of the metal foil which is not in contact with the resin coating film is 0.4 μm or more and 10.0 μm or less.

(21) A metal foil having a resin coating film comprising at least one surface of polyoxynium oxide and any one or a plurality of resins selected from the group consisting of epoxy resins, melamine resins, and fluororesins, and The surface is used for the purpose of peelably adhering a resin-made plate-shaped carrier.

(22) The metal foil of (21), wherein the resin coating film contains an epoxy resin or a melamine resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyoxymethylene.

(23) The metal foil of (20) or (21), wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide.

The metal foil according to any one of (21) to (23), wherein the resin coating film has a thickness of 0.1 to 10 μm.

(25) The metal foil according to any one of (21) to (24), wherein the polyfluorene oxide and any one or more resins selected from the group consisting of epoxy resins, melamine resins, and fluororesins are used. The surface on the side on which the resin coating film is formed is subjected to chromate treatment before the resin coating film acts.

(26) The metal foil according to any one of (21) to (25), wherein a surface of the metal foil on the side in contact with the resin coating film has a ten-point average roughness (Rz jis) of 3.5 μm or less.

(27) A resin-made plate-shaped carrier having a resin coating film comprising at least one surface of polyoxymethylene and any one or a plurality of resins selected from the group consisting of an epoxy resin, a melamine resin, and a fluororesin.

(28) The plate-shaped carrier of (27), wherein the resin coating film contains an epoxy resin or a melamine resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyfluorene oxide.

(29) The plate-shaped carrier of (27) or (28), wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide.

The plate-shaped carrier according to any one of (27) to (29), wherein the resin coating film has a thickness of 0.1 to 10 μm.

(31) A plate-shaped carrier having at least one surface having a polysiloxane and an epoxy group A resin-made plate-shaped carrier of a resin coating film composed of any one of a resin, a melamine resin, and a fluororesin or a plurality of resins, and the surface is used for the purpose of peelably adhering the metal foil.

(32) The plate-shaped carrier of (31), wherein the resin coating film contains an epoxy resin or a melamine resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyoxymethylene.

(33) The plate-shaped carrier of (31) or (32), wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide.

The plate-shaped carrier according to any one of (31) to (33), wherein the resin coating film has a thickness of 0.1 to 10 μm.

(35) A method of producing a multilayer metal-clad laminate comprising: at least one metal foil side build-up resin of the carrier-attached metal foil of any one of (1) to (13), and then repeating the laminated resin or metal foil 1 More than once.

(36) A method for producing a multilayer metal-clad laminate comprising: the metal foil side-layer resin of the carrier-attached metal foil according to any one of (1) to (13), and then repeating the laminated resin, one-sided or two-sided coating A metal laminated plate, or a metal foil with a carrier or a metal foil of any one of claims 1 to 13 or more.

(37) The method for producing a multilayer metal-clad laminate according to (35) or (36), further comprising the step of separating and separating the plate-shaped carrier of the carrier-attached metal foil from the metal foil.

(38) The method according to (37), comprising the step of removing one or all of the metal foil separated by peeling and etching.

(39) A multilayer metal-clad laminate which can be obtained by the production method of any one of (35) to (38).

(40) 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 (13).

(41) The method for producing a build-up substrate according to (40), wherein the build-up wiring layer is formed by at least one of a subtractive method or a full additive method or a semi-additive method.

(42) A method of 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 (1) to (13), and secondly repeating the laminated resin, single-sided or double-sided wiring A 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 (13).

(43) The method for producing a build-up substrate according to (42), further comprising: 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 metal foil-attached sheet The carrier, the metal foil, or the resin is opened, and the step of conducting plating is performed on the side and the bottom surface of the hole.

(44) The method for producing a build-up substrate according to (42) or (43), further comprising: a metal foil constituting the single-sided or double-sided wiring substrate; a metal foil constituting a single-sided or double-sided metal-clad laminate; A step of forming a wiring on at least one of a metal foil with a carrier metal foil and a metal foil.

(45) The method for producing a build-up substrate according to any one of (42) to (44), further comprising: (1) to (13) in which a single surface is adhered to the metal foil on the surface on which the wiring is formed A step of contacting and laminating the side of the resin sheet with the carrier metal foil according to any one of them.

The method for producing a build-up substrate according to any one of (42) to (44), further comprising: laminating a resin on a surface on which the wiring is formed, and adhering the metal foil to both surfaces of the resin ( 1) A step of contacting and laminating a metal foil of a carrier metal foil according to any one of (13).

The method for producing a build-up substrate according to any one of (42) to (46), wherein at least one of the above resins is a prepreg.

The method for producing a build-up substrate according to any one of (40) to (47), further comprising the step of separating the plate-shaped carrier of the metal foil with a carrier and the metal foil.

(49) The method for producing a build-up wiring board according to (48), further comprising the step of removing a part or all of the metal foil which is not in close contact with the plate-shaped carrier by etching.

(50) A build-up wiring board obtained by the manufacturing method of (48) or (49).

(51) A method of manufacturing a printed circuit board, comprising: by any of (40) to (47) A step of manufacturing a build-up substrate by a manufacturing method.

(52) A method of manufacturing a printed circuit board, comprising the step of manufacturing a build-up wiring board by the manufacturing method of (49) or (50).

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 exhibited an excessively high peel strength can be adjusted to have a preferable peel strength, and thus the advantage of improving the productivity of the printed wiring board using the carrier-attached metal foil can be obtained.

10‧‧‧Laminated mold

11‧‧‧With carrier metal foil

11a‧‧‧metal foil

11b‧‧‧Resin coating

11c‧‧‧plate carrier

12‧‧‧Prepreg

13‧‧‧ Inner nuclear

Page 14‧‧‧

15‧‧ ‧

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.

Fig. 3 is a view showing an example of assembly of a multilayer CCL using the copper foil with a carrier of the present invention (a form in which a copper foil is bonded to one side of a resin sheet).

Fig. 4 is a view showing an example of assembly of a multilayer CCL using the copper foil with a carrier of the present invention (a form in which a copper foil is bonded to both surfaces of a resin sheet).

In one embodiment of the metal foil with a carrier of the present invention, a plate-shaped carrier made of a resin and a carrier metal which is peelably adhered to one or both sides of the carrier, preferably two-sided metal foil, is prepared. Foil. 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 case of Fig. 3, the carrier-attached metal foil 11 in which the metal foil 11a is adhered to both surfaces of the resin-made plate-shaped carrier 11c is disclosed. The plate-shaped carrier 11c and the metal foil 11a are bonded together using the resin coating film 11b having the specific structure described below.

In terms of structure, similar to the CCL shown in FIG. 1, the carrier gold of the present invention Since the metal foil and the resin are finally separated, the foil has a structure that can be easily peeled off. In this respect, since CCL is not peeled off, the structure and function are completely different.

Since the metal foil with a carrier used in the present invention must be peeled off after all, the adhesion is too high, which is not preferable, but the plate-shaped carrier and the metal foil need to be treated with a chemical solution such as plating in the process of manufacturing a printed circuit board. The degree of adhesion that does not peel off in the step.

Here, the peeling strength of the metal foil and the plate-shaped carrier to be provided by the resin coating film is preferably 10 gf/cm or more, more preferably 30 gf/cm or more, and still more preferably 50 gf/cm or more. 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 can be easily adjusted so that peeling does not occur during transportation or processing, and peeling strength can be mechanically peeled off by hand. .

The adjustment of the peel strength for achieving such adhesion is by using a resin composed of polyoxynium as described below and any one or a plurality of resins selected from the group consisting of epoxy resins, melamine resins, and fluororesins. The film is applied. The reason for this is that the resin coating film is subjected to a sintering treatment under the specific conditions described below, and is used for bonding between the plate-shaped carrier and the metal foil, thereby appropriately reducing the adhesion and adjusting the peel strength. For the above range.

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

Examples of the melamine-based resin include a methyl etherified melamine resin, a butylated urea melamine resin, a butylated melamine resin, a methylated melamine resin, and a butanol-modified melamine resin. Further, the melamine-based resin may be a mixed resin of the above resin, a butylated urea resin, or a butylated benzene melamine resin.

Further, it is preferred that the epoxy resin has a number average molecular weight of from 2,000 to 3,000, and the melamine resin has a number average molecular weight of from 500 to 1,000. By having such an average number of points The amount of the resin becomes paintable, and it becomes easy to adjust the adhesive strength of the resin coating film to a specific range.

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

Examples of the polyoxymethane include methylphenyl polyoxyalkylene, methyl hydrogen polyoxyalkylene oxide, dimethyl polyoxyalkylene oxide, modified dimethyl polyoxyalkylene oxide, and the like. Here, the modification includes, for example, epoxy modification, alkyl modification, amine modification, carboxyl modification, alcohol modification, fluorine modification, alkyl aralkyl polyether modification, and ring formation. Oxypolyether modification, polyether modification, alkyl higher alcohol ester modification, polyester modification, decyloxyalkyl modification, halogenated alkyl decyloxy alkyl modification, halogenated alkyl modification, amine Ethylene glycol modification, sulfhydryl modification, hydroxyl-containing polyester modification, etc.

In the resin coating film, when the film thickness is too small, the resin coating film is too thin to be formed, and thus productivity is liable to lower. Further, even if the film thickness exceeds a certain thickness, the peeling property of the resin coating film is not further improved, and the production cost of the resin coating film is likely to increase. From this point of view, the film thickness of the resin coating film is preferably from 0.1 to 10 μm, more preferably from 0.5 to 5 μm. Further, the film thickness of the resin coating film can be achieved by applying a resin coating material at a specific coating amount in the following procedure.

In the resin coating film, the polyfluorene oxide functions as a release agent for the resin coating film. Therefore, when the total amount of the epoxy resin or the melamine resin is too large compared with the polyfluorene oxide, the peeling strength imparted by the resin coating film is increased between the plate-shaped carrier and the metal foil, and thus the peeling of the resin coating film is performed. The sex is reduced, and there is a case where it is no longer easy to manually peel off. On the other hand, when the total amount of the epoxy resin or the melamine resin is too small, the peel strength is reduced, and thus the carrier-attached metal foil may be peeled off during transportation or processing. In this regard, the epoxy resin or the melamine resin is preferably contained in an amount of 1,500 parts by mass, more preferably in an amount of 20 to 800 parts by weight, based on 100 parts by mass of the polyfluorene oxide.

Further, the fluororesin functions as a release agent in the same manner as the polyfluorene oxide, and has an effect of improving the heat resistance of the resin coating film. If the fluororesin is excessively compared with polyfluorene oxide, the above peeling Since the strength is reduced, the temperature required in the following baking step is also increased in addition to the peeling of the metal foil with the carrier during transportation or processing, and thus it becomes uneconomical. From this point of view, the fluororesin is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, per 100 parts by mass of the polyfluorene oxide.

The resin coating film may further contain, in addition to polyfluorene oxide, epoxy resin and/or melamine resin, and optionally a fluororesin, SiO ₂ , MgO, Al ₂ O ₃ , BaSO _{4 ,} and Mg (OH). ) of ₂ or more kinds of surface roughening particles. When the resin coating film contains surface roughening particles, the surface of the resin coating film becomes uneven. By the unevenness, the surface of the plate-shaped carrier or the metal foil coated with the resin coating film becomes uneven, and becomes a matte surface. The content of the surface roughening particles is not particularly limited as long as the resin coating film is roughened, and is preferably 1 to 10 parts by mass based on 100 parts by mass of the polyfluorene oxide.

The particle diameter of the surface roughened particles is preferably 15 nm to 4 μm. Here, the particle diameter refers to an average particle diameter (an average value of the maximum particle diameter and the minimum particle diameter) measured by a scanning electron microscope (SEM) photograph or the like. By setting the particle diameter of the surface roughening particles to the above range, the amount of unevenness on the surface of the resin coating film can be easily adjusted, and as a result, the amount of unevenness on the surface of the plate-shaped carrier or the metal foil can be easily adjusted. Specifically, the amount of unevenness on the surface of the plate-shaped carrier or the metal foil is about 4.0 μm in terms of the maximum height roughness Ry prescribed by JIS.

Here, a method of producing a metal foil with a carrier will be described.

The carrier-attached metal foil can be obtained by a procedure of the steps of: coating the resin coating film on at least one surface of the plate-shaped carrier or the metal foil; and baking step of hardening the applied resin coating film . Hereinafter, each step will be described.

(coating step)

The coating step is performed by coating a single surface or both surfaces of the plate-shaped carrier with a polyfluorene oxide as a main component, an epoxy resin as a curing agent, a melamine resin, and optionally a fluororesin as a release agent. A step of forming a resin coating film by a resin coating. Resin coating is based on organic solvents such as alcohol An epoxy resin, a melamine resin, a fluororesin, and a polyoxyxide are dissolved therein. In addition, the total amount (addition amount) of the resin coating material is preferably from 10 to 1,500 parts by mass based on 100 parts by mass of the polyoxymethylene oxide, and the total of the epoxy resin and the melamine resin. Further, the fluororesin is preferably 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide.

The coating method in the coating step is not particularly limited as long as the resin coating film can be formed, and a gravure coating method, a bar coating method, a roll coating method, a curtain flow coating method, and static electricity can be used. The method of the coating machine or the like is preferably a gravure coating method in terms of uniformity of the resin coating film and ease of work. Further, the coating amount is preferably such that the resin coating film 3 has a film thickness of 0.5 to 5 μm, and the resin amount is preferably 1.0 to 2.0 g/m ² .

The gravure coating method is a method of forming a resin coating film on the surface of a plate-shaped carrier by transferring a resin coating filled in a concave portion (groove) provided on the surface of the roller onto a plate-shaped carrier. Specifically, the lower portion of the surface under the groove is immersed in the resin coating, and the resin coating is drawn into the groove by the rotation of the lower roller. Then, a plate-shaped carrier is disposed between the lower roll and the upper side roller disposed on the upper side of the lower roll, and the plate-shaped carrier is pressed against the lower roll by one side or more side rolls, and the lower side roll and the upper side roll are pressed. The plate-shaped carrier is transferred while being rotated, and the resin coating drawn into the groove is transferred (coated) to one side of the plate-shaped carrier.

Further, by arranging the doctor blade on the loading side of the plate-shaped carrier so as to contact the surface of the lower roller, excess resin paint drawn onto the surface of the roller other than the groove can be removed, and the surface of the plate carrier can be coated with a specific coating. Amount of resin coating. Further, when the size (size and depth) of the groove is large or the viscosity of the resin coating is too high, the resin coating film formed on one side of the plate-shaped carrier is difficult to be smooth. Therefore, the smoothing roller can be disposed on the carrying-out side of the plate-shaped carrier to maintain the smoothness of the resin coating film.

Further, when a resin coating film is formed on both surfaces of the plate-shaped carrier, after forming a resin coating film on one surface of the plate-shaped carrier, the plate-shaped carrier is inverted and placed between the lower roller and the upper roller. Then, the resin coating in the groove of the lower roll is transferred (coated) to the plate in the same manner as described above. The back side of the carrier.

(burning step)

The baking step is a step of subjecting the resin coating film formed in the coating step to a baking treatment at a temperature of 125 to 320 ° C (baking temperature) for 0.5 to 60 seconds (baking time). By performing the sintering treatment under specific conditions on the resin coating film formed of the resin coating material of a specific blending amount, the peeling strength between the plate-shaped carrier and the metal foil imparted by the resin coating film can be controlled to a specific range. . In the present invention, the baking temperature is the reaching temperature of the plate-shaped carrier. Further, the heating method used in the baking treatment uses a previously known device.

When the baking is insufficient, for example, when the baking temperature is less than 125 ° C or the baking time is less than 0.5 second, the resin coating film becomes insufficiently hardened, and the peeling strength exceeds 200 g/cm, and the peeling property is lowered. . In addition, when the baking temperature exceeds 320 ° C, the resin coating film is deteriorated, and the peel strength exceeds 200 g/cm, and the workability at the time of peeling is deteriorated. Alternatively, there is a case where the plate-shaped carrier is deteriorated due to high temperature. Moreover, when the baking time exceeds 60 seconds, productivity is deteriorated.

In the method for producing a carrier-attached metal foil, the resin coating material of the coating step may be a polyfluorene oxide as a main component, an epoxy resin as a curing agent, a melamine resin, a fluororesin as a release agent, and an optional It is composed of one or more kinds of surface roughened particles of SiO ₂ , MgO, Al ₂ O ₃ , BaSO ₄ and Mg(OH) ₂ .

Specifically, the resin coating material is obtained by adding the surface roughening particles to the above-mentioned resin solution to which polyoxymethylene is added. By adding such surface roughening particles to the resin coating material, the surface of the resin coating film becomes uneven, and the unevenness causes the plate-shaped carrier or the metal foil to become uneven, thereby becoming a matte surface. Moreover, in order to obtain a plate-shaped carrier or a metal foil having such a matte surface, the amount (addition amount) of the surface roughening particles in the resin coating material is preferably from 1 to 10 parts by mass based on 100 parts by mass of the polyoxymethylene. Further, the particle diameter of the surface roughened particles is more preferably 15 nm to 4 μm.

The production method of the present invention is as described above, but in the practice of the present invention, other steps may be included between or before and after the above steps within a range that does not adversely affect the above steps. For example, the step of washing the surface of the plate-shaped carrier may also be carried out before the coating step.

Further, in the manufacturing process of the multilayer printed wiring board, heat treatment is often performed in the lamination pressing step or the desmear step. Therefore, the thermal history of the metal foil with the carrier is more severe as the number of layers is increased. Therefore, in consideration of the application to a multilayer printed wiring board in particular, it is preferable that the peeling strength of the metal foil and the plate-shaped carrier imparted by the resin coating film after the required heat history is within the above range .

Therefore, in a further preferred embodiment of the present invention, it is assumed that the heating condition in the manufacturing process of the multilayer printed wiring board is performed, for example, at 220 ° C for at least one of heating for 3 hours, 6 hours or 9 hours, by The peeling strength of the metal foil and the plate-shaped carrier to be applied to the resin coating film is preferably 30 gf/cm or more, and 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 strengths of both of them are satisfied after 3 hours and 6 hours, or after 6 hours and 9 hours, from the viewpoint of a plurality of layers. In the above range, it is further preferred that 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. Since the linear expansion coefficient of the prepreg (C-stage) is 12 to 18 (×10 ^-6 /°C), 16.5 (×10 ^-6 /°C) or SUS (Steel Use) of the copper foil as a constituent material of the substrate. Stainless, Japanese stainless steel standard) 17.3 (×10 ^-6 / °C) of the press plate is roughly equal, so it is not easy to produce the position of the circuit caused by the difference between the substrate size before and after pressing and the substrate size at the time of design (scale change) It is advantageous in terms of offset. Further, as a synergistic effect of these advantages, the production of a multilayer ultra-thin coreless substrate is also possible. The prepreg used herein may be the same as or different from the prepreg constituting the circuit board. Further, a metal plate was previously used as a plate-shaped carrier with a carrier metal foil. In this case, it is bonded to the metal foil by soldering or by subsequent bonding. In the case of using an adhesive, from the viewpoint of heat resistance, it is generally difficult to apply a large number of layers, and when it is bonded by welding, if the whole surface is welded, the peel strength is too high. In the latter stage, it becomes difficult to peel off by hand, and if partial welding is used, it becomes difficult to prevent the penetration of the chemical solution between the plate-shaped carrier and the metal foil, and it is difficult to apply the layering in any case. Therefore, by using a plate-shaped carrier made of a resin, it is possible to exhibit an appropriate peel strength with the metal foil, and it is possible to sufficiently withstand the heat history at the time of layer formation by using a heat-resistant resin.

Therefore, it is preferable that the plate-shaped carrier has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating to an optimum range, for example, 120 to 320 ° C, preferably 170 to 240 ° C. Glass transfer 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% or -30% of the thermal expansion coefficient of the metal foil. Thereby, the positional deviation of the circuit due to the difference in thermal expansion between the metal foil and the resin can be effectively prevented, and the generation 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 rigid or soft. If it is too thick, it may adversely affect the heat distribution in hot pressing. On the other hand, if it is too thin, it may bend to make printed wiring. Since the manufacturing step of the sheet cannot be carried out, it is usually 5 μm or more and 1000 μm or less, preferably 50 μm or more and 900 μm or less, and more preferably 100 μm or more and 400 μm or less.

As the metal foil, a representative one is a copper foil or a copper alloy foil, and a foil of aluminum, nickel, zinc or the like can also be used. In the case of a copper foil or a copper alloy foil, an electrolytic foil or a calendered foil can be used. The metal foil is not particularly limited. When it is considered as a wiring for a printed circuit board, the thickness is generally 1 μm or more, preferably 5 μm or more, and 400 μm or less, preferably 120 μm or less. When 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 alloy plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy) Chromate treatment for imparting rust resistance or discoloration resistance by plating, Co-Ni alloy plating, etc. (including including one or more kinds of Zn, P, Ni, Mo, Zr in the chromate treatment liquid) , Ti and other alloying elements), roughening treatment to adjust the surface roughness (such as copper plating or by Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating Obtained by copper alloy plating such as coating, Cu-Ni alloy plating, Cu-Co alloy plating, Cu-As alloy plating, Cu-As-W alloy plating, etc.). Of course, the roughening treatment has an effect on the peel strength of the metal foil and the plate-shaped carrier, and also has a large influence on the chromate treatment. The chromate treatment is important from the viewpoint of rust prevention property and discoloration resistance, and since it is seen that the peel strength is remarkably improved, it is also meaningful as a method of adjusting the peel strength.

In the conventional CCL, since the peeling strength of the resin and the copper foil is expected to be high, for example, the rough surface (M surface) of the electrolytic copper foil is set to the surface of the resin, and surface treatment such as roughening treatment is performed. The adhesion caused by the chemical and physical anchoring effect is enhanced. Further, on the resin side, in order to increase the adhesion to the metal foil, various kinds of adhesives and the like are added. As described above, the present invention is different from CCL, and the metal foil and the resin eventually need to be 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 bonding surface is The surface roughness is expressed by a ten-point average roughness (Rz jis) of the surface of the metal foil measured in accordance with JIS B 0601:2001, and is preferably 3.5 μm or less, and more preferably 3.0 μm or less. However, since it is time-consuming and laborious to reduce the surface roughness without limitation, the cost is increased. Therefore, it is preferably 0.1 μm or more, and more preferably 0.3 μm or more. When the electrolytic copper foil is used as the metal foil, the gloss surface (gloss surface, S surface) and rough surface (gland surface, M surface) can be used when the surface roughness is adjusted, and it is easy to use the S surface. Adjust to the above surface roughness. 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.

Further, in a preferred embodiment of the metal foil with a carrier of the present invention, the surface of the metal foil to which the resin is bonded is not subjected to a surface treatment for improving the peel strength such as a roughening treatment. Further, in a preferred embodiment of the metal foil with a carrier of the present invention, an adhesive for increasing 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 at a pressure of 30 to 40 kg/cm ² , which is higher than the glass transition temperature of the prepreg. Hot pressing is carried out under temperature conditions.

In view of the above, the present invention provides a metal foil which is coated with at least one surface of the metal foil as described above for the adhesive surface in order to make the resin-made plate-shaped carrier peelably adhered to each other. mixture. Further, the surface of the metal foil may be subjected to chromate treatment or the like as described above before the application of the coupling agent.

In another aspect, the present invention provides a plate-shaped carrier having the above-mentioned coupling agent on at least one surface of a plate-shaped carrier which becomes a close contact surface of a metal foil. The plate-shaped carrier can be suitably used for the purpose of releasably bonding the metal foil as described above.

Further, in another aspect, the present invention provides a metal foil for a coreless multilayer printed wiring board, which is coated with the above-mentioned coupling agent on the surface of the metal foil as described above. Further, the surface of the metal foil may be subjected to chromic acid as described above before being coated with a coupling agent. Salt treatment, etc.

Furthermore, the surface of the metal foil or resin is measured by a scanning electron microscope including an XPS (X-ray photoelectron spectrometer), an EPMA (electron micro-detector), or an EDX (energy dispersive X-ray analysis). When Al, Ti, and Zr are formed, it is estimated that the above-mentioned coupling agent exists on the surface of the metal foil or the resin.

Further, based on another aspect, the present 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 laminated resin of the 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 multilayer metal-clad laminate comprising: laminating a resin on a metal foil side of the metal foil with a carrier, and secondarily repeating a laminated resin, a single-sided or double-sided metal-clad laminate, or a carrier of the present invention The metal foil or the metal foil is once or more, for example, 1 to 10 times. Further, the laminate after laminating the resin on the first carrier-attached metal foil can be carried out only for the required number of times, and each time the laminate is laminated, it can be arbitrarily selected from a resin, a single-sided or double-sided metal-clad laminate, and an initial carrier. Another group of the metal foil with a carrier of the present invention and a metal foil other than the metal foil.

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, after separating the plate-shaped carrier from the metal foil and separating it, it may further include a step of removing one or all of the metal foil by etching it.

Thirdly, there is provided a method for producing a build-up substrate comprising: laminating a resin on a metal foil side of the metal foil with a carrier, and then repeating a laminated resin, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, or The metal foil or metal foil of the present invention is provided once or more, for example, 1 to 10 times. Furthermore, the laminate which is laminated on the resin on the initial carrier metal foil can be laminated. Only the required number of times can be arbitrarily selected from the resin, the single-sided or double-sided wiring substrate, the single-sided or double-sided metal-clad laminate, and the first carrier-attached metal foil. Among the groups of foils and metal foils.

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 metal foil with a carrier. At this time, the build-up wiring layer can be formed by a subtractive method or at least one of a full additive method or a semi-additive method.

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

In the method for producing a build-up substrate, the method further includes: 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, a plate-shaped carrier with a carrier metal foil, and a metal foil Or the resin is opened, and the step of conducting plating is performed on the side and the bottom surface of the hole. Furthermore, the method further includes: performing one or more times on at least one of a metal foil constituting the single-sided or double-sided wiring board, a metal foil constituting a single-sided or double-sided metal-clad laminate, and a metal foil constituting the metal foil with a carrier The step of forming wiring.

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

In addition, the "surface formed with wiring" means a portion where wiring is formed on each surface which is formed during the layering process, and includes a final product as a build-up substrate, and also includes a semi-finished product.

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

Further, after the plate-shaped carrier and the metal foil are separated and separated, the film may further include a step of removing one or the entire surface of the metal foil by etching.

Further, in the method for producing a multilayer metal-clad laminate and the method for producing a build-up substrate, the layers may be laminated by thermocompression bonding. The thermocompression bonding can be carried out one by one layer by layer, or can be concentrated after a certain degree of lamination, or can be concentrated at one time.

In particular, the present invention provides a method for producing a build-up substrate, which is a method for producing a build-up substrate, which is performed at least once or more as follows: a single-sided or double-sided wiring substrate, a single-sided or two-sided copper-clad laminate a metal foil or a resin opening, and conducting plating on the side surface and the bottom surface of the hole, and further forming a metal foil and a circuit portion of the single-sided or double-sided wiring substrate, and a metal foil constituting a single-sided or double-sided copper-clad laminate And the step of forming a circuit on the metal foil.

Hereinafter, as a specific example of the above-described use, a method of producing a four-layer CCL using the metal foil with a carrier of the present invention will be described. The carrier-attached metal foil used here is such that the metal foil 11a is in close contact with the carrier-attached metal foil 11 on one side of the plate-shaped carrier 11c. On the carrier-attached metal foil 11, a prepreg 12 of a desired number of sheets, a two-layer printed circuit board, which is referred to as an inner core 13 or a two-layer metal-clad laminate, followed by a prepreg 12, are sequentially stacked. Further, the carrier metal foil 11 is attached, and a unit of four layers of CCL is completed. Next, the unit 14 (generally referred to as "page") is repeated about 10 times to form a press assembly 15 (generally referred to as "book") (Fig. 3). Thereafter, the booklet 15 is held by the build-up mold 10 and placed in a hot press, and pressure-molded at a specific temperature and pressure to simultaneously produce a large number of four layers of CCL. As the laminated mold 10, for example, a stainless steel plate can be used. The plate is not limited, for example, a thick plate of about 1 to 10 mm can be used. For CCL of 4 or more layers, it is generally possible to produce by the same steps by increasing the number of layers of the inner core.

In the following, as a specific example of the above-described use, the coreless addition of the carrier-attached metal foil 11 in which the metal foil is adhered to both surfaces of the plate-shaped carrier 11c of the resin sheet of the present invention is exemplarily exemplified. The method of manufacturing the layer substrate will be described. In this method, after a desired number of build-up layers 16 are laminated on both sides of the carrier-attached metal foil 11, the metal foils 11 are peeled off from the metal foils on both sides (see Fig. 4).

For example, by 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, a resin as an insulating layer, and a metal foil side in contact with the resin sheet are sequentially laminated thereon. Further, the metal foil of the metal foil with a carrier of the present invention is sequentially laminated to produce a build-up substrate.

Further, as another method, a resin as an insulating layer and a conductor layer are sequentially laminated on at least one metal foil side of a carrier-attached metal foil in which both sides of the resin-made plate-shaped carrier 11c or a single surface are in contact with a metal foil. Metal foil. Secondly, the step of adjusting the thickness by half etching the entire surface of the metal foil as needed may be included. Next, laser processing is performed on a specific position of the metal foil of the laminated layer to form a via hole penetrating the metal foil and the resin, and after performing the desmear treatment of removing the glue in the via hole, the bottom and side surfaces of the via hole and The entire surface or part of the metal foil is subjected to electroless plating to form an interlayer connection, and further electrolytic plating is performed as needed. For the portion of the metal foil that does not require electroless plating or electrolytic plating, a plating resist may be formed in advance before the respective plating is performed. Further, when electroless plating, electrolytic plating, or adhesion between 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. Next, a metal foil and a portion which does not require an electroless plating portion and an electrolytic plating portion are removed by etching to form a circuit. Thereby, a build-up substrate can be obtained. The steps of self-assembling the resin and the metal foil to form an electric circuit may be repeated, and a multilayer build-up substrate may be produced.

Further, on the outermost surface of the build-up substrate, the resin side of the metal foil with the metal foil adhered to the metal foil on one side of the present invention may be contacted and laminated. Once the resin sheet is laminated, the two sides of the present invention may be contacted. A metal foil of a metal foil with a carrier foil is adhered to the metal foil and laminated.

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

Further, as another method, the exposed surface of the metal foil of the laminate obtained by laminating a metal foil such as a copper foil on one side or both sides of the plate-shaped carrier of the present invention, a resin as an insulating layer, for example, a prepreg Or a photosensitive resin. Thereafter, a via hole is formed at a specific position of the resin. For example, when a prepreg is used as the resin, the via holes can be processed by laser processing. After the laser processing, the desmear treatment for removing the dross in the via hole can be performed. Further, when a photosensitive resin is used as the resin, the resin of the via hole forming portion can be removed by photolithography. Next, electroless plating is applied to the bottom surface of the via hole, the side surface, and the entire surface or part of the resin to form an interlayer connection, and further electrolytic plating is performed as needed. For the portion of the resin that does not require electroless plating or electrolytic plating, a plating resist may be formed in advance before the respective plating is performed. Further, when electroless plating, electrolytic plating, or adhesion between 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. Next, an electroless plating portion or a portion of the electrolytic plating portion is removed by etching to form an electric circuit. Thereby, a build-up substrate can be obtained. It is also possible to repeat the steps of multi-layering the resin until the circuit is formed, thereby producing a multilayer build-up substrate.

Further, on the outermost surface of the build-up substrate, the resin side of the laminated body in which the metal foil is adhered to one side of the present invention or the resin side of the metal foil with the metal foil adhered to the single surface may be contacted and laminated. After laminating the resin, one metal foil of the laminated body in which the metal foil is adhered to both sides of the present invention or one metal foil of the carrier-attached metal foil which is adhered to the metal foil on both sides may be contacted and laminated.

With respect to the coreless build-up substrate thus produced, wiring is formed on the surface through a plating step and/or an etching step, and the build-up wiring board is completed by peeling and separating the carrier resin and the metal foil. After the separation and separation, a wiring can be formed on the peeled surface of the metal foil, and the entire surface of the metal foil can be removed by etching the entire surface of the metal foil to form a build-up wiring board. Further, the printed circuit board is completed by mounting electronic components on the build-up wiring board. Further, a printed circuit board can be obtained even if an electronic component is directly mounted on the coreless build-up substrate before the resin is peeled off.

[Examples]

In the following, the experimental examples are disclosed 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 present invention.

(with carrier metal foil)

<Experimental Examples 1 to 10>

A plurality of electrolytic copper foils (having a thickness of 12 μm and a rough surface roughness Rz jis of 3.7 μm) were prepared, and a nickel-zinc (Ni-Zn) alloy under the following conditions was applied to the shiny surface of each of the electrolytic copper foils. The plating treatment and the chromate (Cr-Zn chromate) treatment, and 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 After 1.5 μm, a prepreg (FR-4 resin: glass transition temperature Tg=140° C.; thickness: 200 μm) manufactured by Nanya Plastics Co., Ltd. as a resin was attached to the S surface of the electrolytic copper foil at 170 ° C. A hot-pressing process was performed for 100 minutes to prepare a copper foil with a carrier.

(nickel-zinc alloy plating)

Ni concentration 17g / L (added in the form of NiSO ₄ )

Zn concentration 4g / L (added as 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 as CrO ₃ or K ₂ CrO ₇ )

Zn concentration 0.01~1.0g/L (added as 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

Further, in Experimental Examples 1 to 10, a resin coating film having the composition shown in Table 1 was applied onto the shiny surface or the plate-shaped carrier (prepreg), and after baking, prepreg and copper were applied. Foil fit.

The coating of the resin coating film was carried out by coating using a gravure coating method, and the thickness of the resin coating film was adjusted to 2 to 4 μm using a doctor blade. Further, a bisphenol A type epoxy resin was used as the epoxy resin shown in Table 1, a methyl etherified melamine resin was used as the melamine resin, and polytetrafluoroethylene was used as the fluororesin, and dimethyl polyoxyalkylene was used. As a dimethyl polyfluorene resin.

Further, the applied resin coating film was heated at 150 ° C for 30 seconds to carry out a baking treatment.

Further, it is assumed that the copper foil with which the carrier is subjected to further heat treatment such as circuit formation or the like is subjected to a heat history, and the conditions described in Table 1 are carried out (here, at 220 ° C for 3 hours, 6). Heat treatment at hours, 9 hours).

Peel strength of copper foil with carrier copper foil and copper plated carrier (heated resin) after heat treatment for 3 hours, 6 hours, and 9 hours, respectively, obtained by hot pressing The measurement was carried out. The results are shown in Table 1.

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

<Experimental Example 11>

In the experimental example 1, when the copper foil and the prepreg were bonded together, the carrier copper was produced under the same conditions as in Experimental Example 1 except that the shiny surface of the copper foil and the prepreg were not subjected to the resin coating treatment. Foil, and the peel strength and working time of each step were evaluated. The results are shown in Tables 1 and 2.

According to the table, even if the surface of the copper foil is treated, or the surface of the plate-shaped carrier (prepreg) is treated on the resin coating film, the peeling strength of the laminated body after that, the peeling strength after heating, The same results were obtained in terms of peeling workability.

(Additional wiring board)

FR-4 prepreg (made by Nanya Plastics Co., Ltd.) and copper foil (JX Nippon Mining & Metal Co., Ltd., JTC 12μm (product name)) are sequentially superposed on both sides of the carrier-attached copper foil thus produced. Further, hot pressing was carried out under the heating conditions shown in the respective tables under a pressure of 3 MPa to prepare a four-layer copper clad laminate.

Next, using a laser processing machine, a copper foil having a diameter of 100 μm penetrating through the copper foil on the surface of the above-mentioned four-layer copper clad laminate and the insulating layer (hardened prepreg) thereunder was opened. Then, the surface of the copper foil on the copper foil of the carrier exposed on the bottom of the hole, and the side surface of the hole and the copper foil on the surface of the four-layer copper-clad laminate are plated by electroless copper plating or copper plating. Copper is electrically connected 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. Next, one of the copper foils on the surface of the four-layer copper clad laminate was partially etched using an iron chloride-based etching solution to form an electric circuit. In this way, four layers of build-up substrates were obtained.

Then, in the above-mentioned 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 build-up wiring boards were obtained.

Then, the copper foil of the two sets of the two-layer build-up wiring boards which are not in contact with the plate-shaped carrier is etched to form wiring, thereby obtaining two sets of two-layer build-up wiring boards.

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 copper foil with the carrier in the step of producing the build-up substrate was visually confirmed for each of the build-up substrates. A build-up wiring board with a carrier copper foil prepared under the conditions of the peel strength of Tables 1 and 3 and the peel strength after heating is evaluated as "G", and the resin of the carrier copper foil (plate-shaped carrier) is added at the time of layer formation. ) successfully stripped without being destroyed.

Further, regarding the condition evaluated as "N", at the time of layering, the resin was broken during the peeling operation of the copper foil with the carrier copper foil, or the resin remained on the surface of the copper foil without being peeled off.

Further, in the case of the evaluation of the condition of "-", in the peeling operation of the copper foil in the copper foil with a carrier, the resin is peeled off without being broken, but the peeling operation is not performed. The case where the raw copper foil is peeled off.

Claims (52)

A carrier-attached metal foil comprising a plate-shaped carrier made of resin and a metal foil which is peelably adhered to at least one side of the carrier, and is made of polyfluorene oxide and selected from the group consisting of epoxy resin and melamine. A resin coating film comprising any one of a resin and a fluororesin or a plurality of resins is obtained by laminating a plate-shaped carrier and a metal foil. The carrier-coated metal foil according to the first aspect of the invention, wherein the resin coating film contains an epoxy resin or a melamine resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyoxymethylene. The carrier-attached metal foil according to claim 1 or 2, wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide. The carrier-attached metal foil according to any one of claims 1 to 3, wherein the resin coating film has a thickness of 0.1 to 10 μm. The carrier-attached metal foil according to any one of claims 1 to 4, 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 any one of claims 1 to 5, wherein the resin-made plate-shaped carrier comprises a thermosetting resin. The carrier-attached metal foil according to any one of claims 1 to 6, wherein the resin-made plate-shaped carrier is a prepreg. The carrier-attached metal foil according to claim 6 or 7, wherein the above-mentioned 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 8, wherein the surface of the metal foil on the side in contact with the carrier has a ten-point average roughness (Rz jis) of 3.5 μm or less. The carrier-attached metal foil according to any one of claims 1 to 9, wherein a surface of the metal foil which is not in contact with the carrier has a ten-point average roughness (Rz jis) of 0.4 μm. Above 10.0 μm. The carrier-attached metal foil according to any one of claims 1 to 9, wherein the metal foil has a thickness of from 1 μm to 400 μm. The metal foil with a carrier according to any one of claims 1 to 10, wherein the peeling strength of the metal foil and the plate-shaped carrier after heating at 220 ° C for at least one of 3 hours, 6 hours or 9 hours is 10 gf / cm or more and 200 gf / cm or less. The carrier-attached metal foil according to any one of claims 1 to 12, wherein the metal foil is a copper foil. A metal foil for a printed wiring board having a resin coating film made of polyfluorene oxide and any one or a plurality of resins selected from the group consisting of an epoxy resin, a melamine resin, and a fluororesin on the surface of the metal foil. The metal foil for a printed wiring board according to the invention of claim 14, wherein the resin coating film contains an epoxy resin or a melamine in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyfluorene oxide. Resin. The metal foil for a printed wiring board according to claim 14 or 15, wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide. The metal foil for a printed wiring board according to any one of claims 14 to 16, wherein the resin coating film has a thickness of 0.1 to 10 μm. The metal foil for a printed wiring board according to any one of claims 14 to 17, wherein any one or more of the above-mentioned polyfluorene oxide and an epoxy resin, a melamine resin, and a fluororesin are used. The surface on the side on which the resin coating film made of the resin acts is subjected to chromate treatment before the resin coating film acts. The metal foil for a printed wiring board according to any one of the present invention, wherein the surface of the metal foil on the side in contact with the resin coating film has a ten-point average roughness (Rz jis) of 3.5 μm or less. . The metal foil for a printed wiring board according to any one of the present invention, wherein the surface of the metal foil which is not in contact with the resin coating film has a ten-point average roughness (Rz jis) of 0.4 μm. Above 10.0 μm. A metal foil having a resin coating film comprising at least one surface and comprising any one or a plurality of resins selected from the group consisting of epoxy resins, melamine resins, and fluororesins on at least one surface, and using the surface It is used for the peelable adhesion of a resin-made plate-shaped carrier. The metal foil according to claim 21, wherein the resin coating film contains an epoxy resin or a melamine resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyoxymethylene. The metal foil according to claim 20, wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide. The metal foil according to any one of claims 21 to 23, wherein the resin coating film has a thickness of 0.1 to 10 μm. The metal foil according to any one of claims 21 to 24, wherein the polyfluorene oxide and any one or more resins selected from the group consisting of epoxy resins, melamine resins, and fluororesins are used. The surface on the side where the resin coating film functions is subjected to chromate treatment before the resin coating film acts. The metal foil according to any one of claims 21 to 25, wherein a surface of the metal foil on the side in contact with the resin coating film has a ten-point average roughness (Rz jis) of 3.5 μm or less. A resin-made plate-shaped carrier having a resin coating film composed of polyoxymethylene and any one or a plurality of resins selected from the group consisting of an epoxy resin, a melamine resin, and a fluororesin on at least one surface. The plate-shaped carrier according to the 27th aspect of the invention, wherein the resin coating film contains an epoxy resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyfluorene oxide. A melamine resin. The plate-shaped carrier according to the invention of claim 27, wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide. The plate-shaped carrier according to any one of claims 27 to 29, wherein the resin coating film has a thickness of 0.1 to 10 μm. A plate-shaped carrier which is a resin plate having a resin coating film composed of polyoxymethylene and any one or a plurality of resins selected from the group consisting of epoxy resins, melamine resins, and fluororesins on at least one surface thereof The carrier is used for the purpose of releasably adhering the metal foil. In the above-mentioned resin coating film, the resin coating film contains an epoxy resin or a melamine resin in an amount of 10 to 1500 parts by mass based on 100 parts by mass of the polyoxymethylene. The plate-shaped carrier according to claim 31, wherein the resin coating film contains a fluororesin in an amount of from 0 to 50 parts by mass based on 100 parts by mass of the polyfluorene oxide. The plate-shaped carrier according to any one of claims 31 to 33, wherein the resin coating film has a thickness of 0.1 to 10 μm. 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 13, and then repeating laminating resin or metal foil for one or more times . A method for manufacturing 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 13, and then repeating a laminated resin, a single-sided or two-sided metal-clad laminate A plate, or a metal foil with a carrier or a metal foil of any one of the above claims 1 to 13 or more. The method for producing a multi-layer metal-clad laminate according to claim 35 or 36, further comprising the step of separating and separating the plate-shaped carrier of the carrier-attached metal foil from the metal foil. The manufacturing method of claim 37, which comprises: by peeling off The step of removing one or all of the metal foil from it to remove it. A multi-layer metallized laminate obtained by the manufacturing method of any one of claims 35 to 38. A method for 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 claims 1 to 13. The method for producing a build-up substrate according to claim 40, wherein the build-up wiring layer is formed by at least one of a subtractive method or a full additive method or a semi-additive method. A method for producing a build-up substrate, comprising: at least one metal foil side build-up resin of a carrier metal foil according to any one of claims 1 to 13, and then repeating a laminated resin, a single-sided or double-sided wiring substrate, A single-sided or double-sided metal-clad laminate, the carrier-attached metal foil or metal foil of any one of claims 1 to 13 may be used more than once. The method for manufacturing a build-up substrate according to claim 42, further comprising: 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 metal foil with a carrier The carrier, the metal foil, or the resin is opened, and the step of conducting plating is performed on the side and the bottom surface of the hole. The method for producing a build-up substrate according to the 42nd or 43rd aspect of the invention, further comprising: a metal foil constituting the single-sided or double-sided wiring substrate, a metal foil constituting a single-sided or double-sided metal-clad laminate, and a carrier A step of forming a wiring on at least one of a metal foil of a metal foil and a metal foil. The method for producing a build-up substrate according to any one of claims 42 to 44, further comprising: in the first to third aspects of the patent application scope in which the metal foil is adhered to one surface on the surface on which the wiring is formed A step of contacting and laminating the side of the resin sheet with the carrier metal foil. The method for producing a build-up substrate according to any one of claims 42 to 44, further comprising: applying a resin on a surface on which the wiring is formed, and applying a metal foil on both sides of the resin a metal foil of a carrier metal foil according to any one of items 1 to 13 The steps of contacting and carrying out the lamination. The method for producing a build-up substrate according to any one of claims 42 to 46, wherein at least one of the above resins is a prepreg. The method for producing a build-up substrate according to any one of claims 40 to 47, further comprising the step of separating the plate-shaped carrier of the metal foil with a carrier and the metal foil. The method for producing a build-up wiring board according to claim 48, further comprising the step of removing a part or all of the metal foil which is not in close contact with the plate-shaped carrier by etching. A build-up wiring board obtained by the manufacturing method of claim 48 or 49. A method of manufacturing a printed circuit board, comprising the step of manufacturing a build-up substrate by the manufacturing method of any one of claims 40 to 47. A method of manufacturing a printed circuit board comprising the steps of manufacturing a build-up wiring board by the manufacturing method of claim 49 or 50.