JP6687765B2 - Metal foil with carrier - Google Patents

Description

  The present invention relates to a metal foil with a carrier. More specifically, the present invention relates to a metal foil with a carrier used in the production of a single-sided or multi-layered laminate having two or more layers used for a printed wiring board or an ultrathin coreless substrate.

  A typical example of a multilayer laminate is a printed circuit board. Generally, a printed wiring board uses a dielectric material called “prepreg” obtained by impregnating a synthetic resin plate, a glass plate, a glass non-woven fabric, a paper and the like with a synthetic resin as a basic constituent material. . A sheet of copper or copper alloy foil having electrical conductivity is joined to the side opposite to the prepreg. The laminate thus assembled is generally called a CCL (copper clad laminate) material. The surface of the copper foil in contact with the prepreg is usually subjected to a roughening treatment in order to increase the bonding strength, and then an anticorrosion treatment for preventing oxidation. Instead of copper or copper alloy foil, foil of aluminum, nickel, zinc, etc. may be used. Their thickness is about 5 to 200 μm. This commonly used CCL (copper clad laminate) material is shown in FIG.

  Patent Document 1 proposes a metal foil with a carrier, which is composed of a synthetic resin plate-shaped carrier and a metal foil that is mechanically and releasably adhered to at least one surface of the carrier. Describes that it can be used for assembling a printed wiring board. Then, it was shown that the peel strength between the plate-shaped carrier and the metal foil is preferably 1 gf / cm to 1 kgf / cm. According to the metal foil with a carrier, since the copper foil is entirely supported by the synthetic resin, it is possible to prevent wrinkles from being generated on the copper foil during lamination. Further, in this metal foil with a carrier, the metal foil and the synthetic resin are in close contact with each other without a gap, and therefore, when the metal foil surface is plated or etched, it is possible to add it to a chemical solution for plating or etching. . Furthermore, the coefficient of linear expansion of the synthetic resin is at the same level as the copper foil and the prepreg after polymerization, which are the constituent materials of the substrate, so that there is no misalignment of the circuit, and the occurrence of defective products is reduced. It has an excellent effect that the yield can be improved.

JP, 2009-272589, A

  The copper foil with a carrier described in Patent Document 1 is an epoch-making invention that greatly contributes to the reduction of manufacturing cost by simplifying the manufacturing process of a printed circuit board and increasing the yield. No mention is made of a structure that takes into consideration the temporary adhesion between the carrier and the metal foil and the subsequent peeling, and there is room for improvement.

  For example, in an application that is used without going through too many heating steps, for example, an application such as a shield material that is formed by performing mesh processing, before the metal foil and the synthetic resin that are in close contact with each other are peeled off, It is important that they are not peeled off carelessly and that they can be peeled off intentionally at the interface between the metal foil and the synthetic resin during the peeling operation. That is, in order to avoid inadvertent peeling, if the peeling strength of both is excessively increased, the resin portion is broken when the metal foil and the synthetic resin are peeled off this time, and the resin content is present on the surface of the metal foil. It may remain, which is not preferable.

  Therefore, the present invention seeks a useful condition for releasably adhering the plate-shaped carrier and the metal foil, and further provides a metal foil with a carrier capable of intentionally peeling at the interface between the metal foil and the plate-shaped carrier. The challenge is to provide.

  The present inventors, as a result of diligent research on the above problems, by setting the peel strength between the metal foil and the plate-like carrier within a certain range, between the metal foil and the plate-like carrier, careless The present invention has been completed by finding that peeling does not occur and intentional peeling is possible.

That is, the present invention is as follows.
(1) A metal foil with a carrier, which comprises a resin plate carrier and a metal foil releasably adhered to at least one surface of the carrier, the peel strength between the metal foil and the plate carrier. Is 10 gf / cm or more and 200 gf / cm or less,
A metal foil with a carrier having a ten-point average roughness (Rz jis) of 0.4 μm or more and 10.0 μm or less on the surface of the metal foil that is not in contact with the plate-shaped carrier.
(2) The metal foil with a carrier according to (1), wherein the resin-made plate-shaped carrier contains a thermosetting resin.
(3) The resin-made plate-like carrier is a metal foil with a carrier according to (1) or (2), which is a prepreg.
(4) In the metal foil with a carrier according to (2) or (3),
The plate carrier made of resin is a metal foil with a carrier having a glass transition temperature Tg of 120 to 320 ° C.
(5) In the metal foil with a carrier according to any one of (1) to (4),
A metal foil with a carrier having a ten-point average roughness (Rz jis) of a surface of the metal foil in contact with the carrier of 3.5 μm or less.
(6) In the metal foil with a carrier according to any one of (1) to (5),
The peel strength between the metal foil and the plate-like carrier after heating at 220 ° C. for at least one of 3 hours, 6 hours, and 9 hours is 10 gf / cm or more and 200 gf / cm or less, and A metal foil with a carrier having a thickness of 1 μm or more.
(7) The plate-shaped carrier and the metal foil forming the metal foil with the carrier have the following formula:

(In the formula, 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 halogen atoms. in substituted is any of these hydrocarbon groups, R ³ and R ⁴ are independently a halogen atom or an alkoxy group, or an alkyl group, a hydrocarbon group selected from the group consisting of cycloalkyl group and an aryl group, Or any of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms.)
The metal foil with a carrier according to any one of (1) to (6), wherein the silane compound, the hydrolysis product thereof, and the condensate of the hydrolysis product shown in (1) to (6) are laminated together.
(8) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7), and then the resin or the metal foil is repeatedly laminated one or more times. A method for producing a multi-layer metal-clad laminate comprising:
(9) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7), and then the resin, a single-sided or double-sided metal-clad laminate, or (1) to ( 7. A method for producing a multi-layer metal-clad laminate, which comprises repeatedly laminating the metal foil with a carrier according to any one of 7) or the metal foil once or more.
(10) In the method for producing a multi-layer metal-clad laminate according to (8) or (9), the multi-layer metal-clad laminate further includes a step of peeling and separating the plate-shaped carrier of the metal foil with a carrier and the metal foil. Method of manufacturing a plate.
(11) A method for producing a multi-layer metal-clad laminate, which comprises the step of etching to remove a part or all of the separated metal foil by etching, in the production method described in (10).
(12) A multilayer metal-clad laminate obtained by the method according to any one of (8) to (11).
(13) A method for manufacturing a build-up substrate, including a step of forming one or more build-up wiring layers on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7).
(14) The buildup substrate manufacturing method according to (13), wherein the buildup wiring layer is formed by using at least one of a subtractive method, a full additive method, and a semi-additive method.
(15) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (7), and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, A method for manufacturing a build-up substrate, comprising stacking the metal foil with a carrier or the metal foil according to any one of (1) to (7) repeatedly one or more times.
(16) In the method for manufacturing a build-up board according to (15), a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil of a metal foil with a carrier, a plate-shaped carrier of a metal foil with a carrier, or a resin. A method for manufacturing a build-up substrate, further comprising the step of: forming a hole in the hole; and conducting plating on the side surface and the bottom surface of the hole.
(17) In the method for manufacturing a build-up substrate according to (15) or (16), a metal foil that constitutes the one-sided or double-sided wiring substrate, a metal foil that constitutes a one-sided or double-sided metal-clad laminate, and a metal with a carrier. A method for manufacturing a build-up substrate, further comprising performing the step of forming wiring on at least one of the metal foils forming the foil once or more.
(18) The step of laminating the metal foil with a carrier according to any one of (1) to (7), in which a metal foil is adhered on one surface, onto the surface on which wiring is formed The method for manufacturing a build-up board according to any one of (15) to (17).
(19) One metal foil of the metal foil with a carrier according to any one of (1) to (7), in which a resin is laminated on the surface on which wiring is formed, and the metal foil is adhered to both sides of the resin. The method for producing a build-up substrate according to any one of (15) to (17), further including a step of bringing the layers into contact with each other to stack them.
(20) The method for manufacturing a buildup substrate according to any one of (15) to (19), wherein at least one of the resins is a prepreg.
(21) The method for manufacturing a buildup substrate according to any one of (13) to (20), further including a step of peeling and separating the plate-shaped carrier of the metal foil with a carrier and the metal foil. Method of manufacturing a plate.
(22) The method for manufacturing a buildup wiring board according to (21), which further includes a step of removing a part or all of the metal foil adhered to the plate carrier by etching.
(23) A buildup wiring board obtained by the manufacturing method according to (21) or (22).
(24) A method for manufacturing a printed circuit board, including the step of manufacturing a buildup board by the manufacturing method according to any one of (13) to (20).
(25) A method for manufacturing a printed circuit board, which includes a step of manufacturing a buildup wiring board by the manufacturing method according to (21) or (22).

  According to the present invention, it is possible to provide a metal foil with a carrier that does not cause inadvertent peeling between a metal foil and a plate-shaped carrier and that allows intentional peeling. .

An example of the structure of CCL is shown. The structural example of the metal foil with a carrier according to the present invention is shown. An example of assembling a multi-layer CCL using the copper foil with a carrier according to the present invention (a mode in which copper foil is bonded to both surfaces of a resin plate) is shown.

  In one embodiment of a metal foil with a carrier according to the present invention, a metal foil with a carrier comprising a resin plate-shaped carrier and one or both sides of the carrier, preferably a metal foil releasably adhered to both sides is prepared. To do. An example of the structure of the metal foil with a carrier according to the present invention is shown in FIGS. 2 and 3. In particular, at the beginning of FIG. 3, there is shown a metal foil 11 with a carrier in which a metal foil 11a is releasably adhered to both sides of a resin plate carrier 11c. The plate-shaped carrier 11c and the metal foil 11a are bonded together using a silane compound 11b described later.

  Although structurally similar to the CCL shown in FIG. 1, in the metal foil with a carrier of the present invention, the metal foil and the resin are finally separated, and have a structure that can be easily peeled off. In this respect, since the CCL does not peel off, the structure and function are completely different.

  Since the metal foil with a carrier used in the present invention must be peeled off, it is inconvenient that the adhesiveness is excessively high, but the plate-shaped carrier and the metal foil are chemical solutions such as plating used in the printed circuit board manufacturing process. It is necessary that the adhesiveness is such that it does not peel off in the treatment process. From such a viewpoint, the peel strength between the metal foil and the plate-shaped carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, and further preferably 50 gf / cm or more. It is preferably 200 gf / cm or less, more preferably 150 gf / cm or less, and even more preferably 80 gf / cm or less. By setting the peel strength between the metal foil and the plate-like carrier in such a range, peeling can be performed manually, that is, mechanical peeling can be performed without peeling during transportation or processing.

  Moreover, in the manufacturing process of a multilayer printed wiring board, heat treatment is often performed in a lamination pressing process or a desmear process. Therefore, the thermal history of the metal foil with the carrier becomes more severe as the number of laminated layers increases. Therefore, particularly when considering application to a multilayer printed wiring board, it is desirable that the peel strength between the metal foil and the plate-shaped carrier be within the above-mentioned range even after the required heat history.

  Therefore, in a further preferred embodiment of the present invention, the metal is used after heating at least one of, for example, 220 ° C., 3 hours, 6 hours, and 9 hours, assuming heating conditions in the manufacturing process of the multilayer printed wiring board. The peel strength between the foil and the plate-like carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, still more preferably 50 gf / cm or more, but 200 gf / cm or less. It is preferably 150 gf / cm or less, more preferably 80 gf / cm or less.

  Regarding the peel strength after heating at 220 ° C., the peel strength was described above both after 3 hours and 6 hours, or after 6 hours and 9 hours from the viewpoint of being able to cope with various laminated numbers. It is preferable that all the peel strengths after 3 hours, 6 hours and 9 hours satisfy the above range.

  In the present invention, the peel strength is measured according to the 90-degree peel strength measuring method defined in JIS C6481.

  Hereinafter, specific constituent requirements of each material for achieving such peel strength will be described.

The resin that serves as the plate-shaped carrier is not particularly limited, and phenol resin, polyimide resin, epoxy resin, natural rubber, pine resin, and the like can be used, but thermosetting resin is preferable. Also, a prepreg can be used. The prepreg before being bonded to the metal foil is preferably in the B stage. The coefficient of linear expansion of the prepreg (C stage) is 12 to 18 (× 10 ^-6 / ° C), 16.5 (× 10 ^-6 / ° C) of copper foil which is the constituent material of the substrate, or 17 of the SUS press plate. Since it is almost equal to 3 (× 10 ⁻⁶ / ° C.), it is advantageous in that it is difficult for the circuit to be displaced due to a phenomenon (scaling change) in which the substrate size before and after pressing is different from that during design. Further, as a synergistic effect of these merits, it becomes possible to produce a multilayer ultrathin coreless substrate. The prepreg used here may be the same as or different from the prepreg constituting the circuit board.

  This plate-shaped carrier preferably has a high glass transition temperature Tg from the viewpoint of maintaining the peel strength after heating in an optimum range, and for example, the glass transition temperature Tg is 120 to 320 ° C, preferably 170 to 240 ° C. . The glass transition temperature Tg is a value measured by DSC (differential scanning calorimetry).

  Further, the coefficient of thermal expansion of the resin is preferably within + 10% and -30% of the coefficient of thermal expansion of the metal foil. As a result, it is possible to effectively prevent the displacement of the circuit due to the difference in thermal expansion between the metal foil and the resin, reduce the occurrence of defective products, and improve the yield.

  The thickness of the plate carrier is not particularly limited, and it may be rigid or flexible, but if it is too thick, it will adversely affect the heat distribution during hot pressing, while if it is too thin it will bend and stop the manufacturing process of the printed wiring board. Therefore, 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.

  Typical metal foils are copper or copper alloy foils, but foils of aluminum, nickel, zinc or the like can also be used. In the case of copper or copper alloy foil, electrolytic foil or rolled foil can be used. Although not limited, the metal foil generally has a thickness of 1 μm or more, preferably 5 μm or more, and 400 μm or less, preferably 120 μm or less, considering its use as a wiring of a printed circuit board. When the metal foil is attached to both sides of the plate carrier, the metal foil having the same thickness may be used or the metal foil having different thickness may be used.

  The metal foil used may be subjected to various surface treatments. For example, metal plating for the purpose of imparting heat resistance (Ni plating, Ni-Zn alloy plating, Cu-Ni alloy plating, Cu-Zn alloy plating, Zn plating, Cu-Ni-Zn alloy plating, Co-Ni alloy plating, etc. ), Chromate treatment for imparting rust prevention and discoloration resistance (including a case where one or more alloy elements such as Zn, P, Ni, Mo, Zr, and Ti are contained in the chromate treatment liquid), surface roughness Roughening treatment for adjusting the degree (for example, copper electrodeposited grains, Cu-Ni-Co alloy plating, Cu-Ni-P alloy plating, Cu-Co alloy plating, Cu-Ni alloy plating, Cu-Co alloy plating, Copper alloy plating such as Cu-As alloy plating and Cu-As-W alloy plating). The roughening treatment not only affects the peel strength between the metal foil and the plate-shaped carrier, but also the chromate treatment has a great influence. Chromate treatment is important from the viewpoint of rust resistance and discoloration resistance, but it tends to significantly increase the peel strength, so it is also meaningful as a means for adjusting the peel strength.

  In conventional CCL, since it is desired that the resin and the copper foil have high peel strength, for example, the matte surface (M surface) of the electrolytic copper foil is used as the adhesive surface with the resin, and surface treatment such as roughening treatment is performed. The chemical and physical anchor effects are used to improve the adhesive strength. Also, on the resin side, various binders are added in order to increase the adhesive strength with the metal foil. As described above, in the present invention, unlike the CCL, the metal foil and the resin need to be finally peeled off, so that an excessively high peel strength is disadvantageous.

  Therefore, in a preferred embodiment of the metal foil with a carrier according to the present invention, in order to adjust the peel strength between the metal foil and the plate-shaped carrier to the preferable range described above, the surface roughness of the bonding surface is determined according to JIS B 0601: The ten-point average roughness (Rz jis) of the surface of the metal foil measured according to 2001 is preferably 3.5 μm or less, and more preferably 3.0 μm or less. However, it is troublesome to reduce the surface roughness indefinitely, which causes a cost increase. Therefore, the surface roughness 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, it is possible to use either a glossy surface (shiny surface, S surface) or a rough surface (matte surface, M surface) if the surface roughness is adjusted to such a value. However, it is easier to adjust the surface roughness by using the S surface. On the other hand, the ten-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the carrier is preferably 0.4 mμ or more and 10.0 μm or less.

  Further, in a preferred embodiment of the metal foil with a carrier according to the present invention, the surface of the metal foil to be bonded to the resin is not subjected to surface treatment such as roughening treatment for improving peel strength. Further, in a preferred embodiment of the metal foil with a carrier according to the present invention, no binder is added to the resin for increasing the adhesive force with the metal foil.

  The peel strength can be controlled by using a silane compound represented by the following formula, or a hydrolysis product thereof, or a condensate of the hydrolysis product (hereinafter, simply referred to as a silane compound), alone or in combination. Good. By sticking the plate-shaped carrier and the metal foil using the silane compound, the adhesiveness is appropriately reduced, and the peel strength can be easily adjusted within the above range.

formula:

(In the formula, 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 halogen atoms. in substituted is any of these hydrocarbon groups, R ³ and R ⁴ are independently a halogen atom or an alkoxy group, or an alkyl group, a hydrocarbon group selected from the group consisting of cycloalkyl group and an aryl group, Or any of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms.)

  The silane compound needs to have at least one alkoxy group. It is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group without the presence of an alkoxy group, or any of these hydrocarbons in which one or more hydrogen atoms are replaced by halogen atoms. When the substituent is composed of only the group, the adhesion between the plate-shaped carrier and the surface of the metal foil tends to be too low. In addition, the silane compound is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms. It is necessary to have at least one. This is because if the hydrocarbon group does not exist, the adhesion between the plate-shaped carrier and the metal foil surface tends to increase. In addition, the alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are replaced by halogen atoms.

In adjusting the peel strength between the plate-shaped carrier and the metal foil within the above range, the silane compound has three alkoxy groups and the above hydrocarbon group (a hydrocarbon group in which one or more hydrogen atoms are replaced by halogen atoms). It is preferable to have one). In the above formula, both R ³ and R ⁴ are alkoxy groups.

Alkoxy groups include, but are not limited to, methoxy, ethoxy, n- or iso-propoxy, n-, iso- or tert-butoxy, n-, iso- or neo-pentoxy, n-hexoxy. Group, cyclohexoxy group, n-heptoxy group, n-octoxy group and the like linear, branched or cyclic carbon number 1-20, preferably carbon number 1-10, more preferably carbon number 1- The alkoxy group of 5 is mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  The alkyl group includes, but is not limited to, methyl group, ethyl group, n- or iso-propyl group, n-, iso- or tert-butyl group, n-, iso- or neo-pentyl group, n-hexyl group. Group, an n-octyl group, an n-decyl group and the like linear or branched C1-20, preferably C1-10, more preferably C1-5 alkyl groups.

  The cycloalkyl group is not limited, but is a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or the like having 3 to 10 carbon atoms, preferably 5 to 7 carbon atoms. An alkyl group is mentioned.

  As the aryl group, a phenyl group, a phenyl group substituted with an alkyl group (eg, a tolyl group, a xylyl group), a 1- or 2-naphthyl group, an anthryl group or the like having 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. An aryl group is mentioned.

  One or more hydrogen atoms of these hydrocarbon groups may be replaced with halogen atoms, and for example, they may be replaced with fluorine atom, chlorine atom, or bromine atom.

  Examples of preferred silane compounds include methyltrimethoxysilane, ethyltrimethoxysilane, n- or iso-propyltrimethoxysilane, n-, iso- or tert-butyltrimethoxysilane, n-, iso- or neo-pentyl. Trimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane; alkyl-substituted phenyltrimethoxysilane (for example, p- (methyl) phenyltrimethoxysilane), methyltriethoxysilane, ethyl Triethoxysilane, n- or iso-propyltriethoxysilane, n-, iso- or tert-butyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane Orchid, decyltriethoxysilane, phenyltriethoxysilane, alkyl-substituted phenyltriethoxysilane (eg, p- (methyl) phenyltriethoxysilane), (3,3,3-trifluoropropyl) trimethoxysilane, and trideca Fluorooctyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, trimethylfluorosilane, dimethyldibromosilane, diphenyldibromosilane, hydrolysis products thereof, and condensation products of these hydrolysis products. And so on. Among these, propyltrimethoxysilane, methyltriethoxysilane, hexyltrimethoxysilane, phenyltriethoxysilane, and decyltrimethoxysilane are preferable from the viewpoint of easy availability.

  The metal foil with a carrier can be manufactured by bringing the plate-shaped carrier and the metal foil into close contact with each other by hot pressing. For example, after applying the silane compound to the bonding surface of the metal foil and / or the plate-shaped carrier as needed, the resin plate-shaped carrier of the B stage is hot to the bonding surface of the metal foil. It can be manufactured by press lamination.

  The silane compound can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added to improve the solubility in water. The addition of alcohol is particularly effective when using a highly hydrophobic silane compound. When the aqueous solution of the silane compound is stirred, the hydrolysis of the alkoxy group is promoted, and when the stirring time is long, the condensation of the hydrolysis product is promoted. In general, the peel strength between the metal foil and the plate-shaped carrier tends to decrease when a silane compound that is hydrolyzed and condensed after a sufficient stirring time is used. Therefore, the peel strength can be adjusted by adjusting the stirring time. Although not limited, the stirring time after dissolving the silane compound in water 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.

  The higher the concentration of the silane compound in the aqueous solution of the silane compound, the lower the peel strength between the metal foil and the plate-shaped carrier tends to be, and the peel strength can be adjusted by adjusting the concentration of the silane compound. Although not limited, the concentration of the silane compound in the aqueous solution may be 0.01 to 10.0% by volume, typically 0.1 to 5.0% by volume.

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

As conditions for hot pressing for producing a metal foil with a carrier, when a prepreg is used as a plate-shaped carrier, it is preferable to perform hot pressing at a pressure of 30 to 40 kg / cm ² and a temperature higher than the glass transition temperature of the prepreg. .

  The surface of the metal foil or resin was measured with a device such as a scanning electron microscope equipped with XPS (X-ray photoelectron spectroscopy apparatus), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), and Si was measured. If detected, it can be inferred that the silane compound is present on the surface of the metal foil or the resin.

Furthermore, from another viewpoint, the present invention provides the use of the above-mentioned metal foil with a carrier.
First, a multi-layer metal including laminating a resin on at least one metal foil side of the metal foil with a carrier described above, and then laminating the resin or the metal foil one or more times, for example, 1 to 10 times repeatedly. A method of making a stretched laminate is provided.

  Secondly, a resin is laminated on the metal foil side of the above-mentioned metal foil with a carrier, and then the resin, the single-sided or double-sided metal-clad laminate, or the metal foil with a carrier of the present invention, or the metal foil is used once or more, for example, 1 There is provided a method for producing a multi-layer metal-clad laminate, which comprises repeatedly laminating for 10 times.

  The method for producing a multilayer metal-clad laminate described above may further include a step of peeling and separating the plate-shaped carrier of the metal foil with a carrier from the metal foil.

  Further, the method may further include a step of removing a part or all of the metal foil by etching after separating the plate-shaped carrier and the metal foil by separation.

  Fourthly, a resin is laminated on the metal foil side of the above-mentioned metal foil with a carrier, and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, or a metal foil with a carrier of the present invention, or a metal foil. There is provided a method for manufacturing a build-up board, which comprises stacking the stack one or more times, for example, 1 to 10 times.

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

  The subtractive method is 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 and a printed circuit board) by etching or the like. Refers to. The full additive method is a method of forming a conductor pattern by electroless plating and / or electrolytic plating without using a metal foil for the conductor layer. The semi-additive method is, for example, electroless plating on a seed layer made of a metal foil. This is a method of obtaining a conductor pattern by forming a conductor pattern by using metal deposition and electrolytic plating, etching, or both in combination, and then etching and removing an unnecessary seed layer.

  In the method for manufacturing the build-up substrate described above, a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil of a metal foil with a carrier, a plate-shaped carrier of a metal foil with a carrier, or a resin, The method may further include the step of conducting plating on the side surface and the bottom surface of the hole. In addition, a step of forming a wiring on at least one of the metal foil forming the one-sided or double-sided wiring board, the metal foil forming the one-sided or double-sided metal-clad laminate, and the metal foil forming the metal foil with a carrier is performed once. It is possible to further include performing the above.

The above method for manufacturing a build-up substrate may further include a step of bringing a metal foil into close contact with one surface of the surface on which the wiring is formed, and further laminating the carrier side of the metal foil with a carrier according to the present invention. . Further, it may further include a step of laminating a resin on the surface on which the wiring is formed and laminating the metal foil with a carrier according to the present invention in which the metal foil is adhered to both sides of the resin.
The "surface on which wiring is formed" means a portion where wiring is formed on the surface that appears each time during the build-up process, and the build-up substrate includes the final product and the intermediate product.

  The above method for manufacturing a build-up substrate may further include a step of peeling and separating the plate-shaped carrier of the metal foil with a carrier and the metal foil.

  Furthermore, it is possible to further include a step of removing a part or the whole surface of the metal foil by etching after separating and separating the plate-shaped carrier and the metal foil.

  In addition, in the above-described method for producing a multilayer metal-clad laminate and method for producing a build-up substrate, the layers can be laminated by thermocompression bonding. The thermocompression bonding may be performed every time one layer is laminated, may be collectively laminated after being laminated to some extent, or may be finally collectively performed at one time.

  Hereinafter, as a specific example of the above-mentioned application, a method for manufacturing a coreless build-up substrate using the copper foil with a carrier 11 in which copper foil is adhered to both surfaces of the plate-shaped carrier 11c of the resin plate according to the present invention will be exemplarily described. . In this method, the required number of build-up layers 16 are laminated on both sides of the copper foil with carrier 11, and then the copper foils on both sides are peeled from the copper foil with carrier 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 board, a resin as an insulating layer are sequentially laminated, and the metal foil side is in contact with the resin plate, Further, a build-up substrate can be manufactured by sequentially stacking metal foils of the metal foil with a carrier of the present invention.

Further, as another method, a resin as an insulating layer or a conductor layer is provided on at least one metal foil side of a metal foil with a carrier in which metal foil is adhered to both surfaces or one surface of a resin plate carrier 11c. Are sequentially laminated. Next, if necessary, a step of half-etching the entire surface of the metal foil to adjust the thickness may be included. Next, laser processing is performed at a predetermined position of the laminated metal foil to form a via hole penetrating the metal foil and the resin, and after desmearing to remove smear in the via hole, the bottom, side surface and metal foil of the via hole are subjected. Electroless plating is applied to the entire surface or a part thereof to form interlayer connection, and further electrolytic plating is performed if necessary. A plating resist may be previously formed on a portion of the metal foil that does not require electroless plating or electrolytic plating before the respective plating is performed. Further, the surface of the metal foil may be chemically roughened in advance when the adhesion between the electroless plating, the electrolytic plating and the plating resist and the metal foil is insufficient. When a plating resist is used, the plating resist is removed after plating. Next, a circuit is formed by removing unnecessary portions of the metal foil, the electroless plated portion, and the electrolytic plated portion by etching. As a result, a buildup board is obtained. You may repeat the process from lamination of resin and copper foil to circuit formation a plurality of times to obtain a multilayer build-up substrate. Further, the outermost surface of this build-up substrate has a metal foil adhered to one side of the present invention. The metal side of the metal foil with a carrier may be laminated by contacting the resin side of the metal foil, or after laminating the resin plates once, one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces of the present invention is used. You may contact and may laminate.

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

As another method, a metal foil such as a prepreg or a photosensitive resin as an insulating layer is formed on the exposed surface of a metal foil of a laminate obtained by laminating a metal foil, for example, a copper foil on one or both sides of the plate-shaped carrier of the present invention. A photosensitive resin is laminated. Then, a via hole is formed at a predetermined position of the resin. When using, for example, a prepreg as the resin, the via hole can be formed by laser processing. After laser processing, desmearing treatment for removing smear in the via hole may be performed. When a photosensitive resin is used as the resin, the resin in the via hole forming portion can be removed by the photolithography method. Next, electroless plating is performed on the bottom and side surfaces of the via hole and the entire surface or a part of the resin to form an interlayer connection, and further electrolytic plating is performed if necessary. A plating resist may be preliminarily formed on a portion of the resin where electroless plating or electrolytic plating is unnecessary before the respective plating is performed. Further, the surface of the resin may be chemically roughened in advance when the adhesion between the electroless plating, the electrolytic plating, and the plating resist and the resin is insufficient. When a plating resist is used, the plating resist is removed after plating. Next, a circuit is formed by removing unnecessary portions of the electroless plated portion or the electrolytic plated portion by etching. As a result, a buildup board is obtained. The process from resin lamination to circuit formation may be repeated a plurality of times to obtain a multilayer build-up substrate.
Further, the outermost surface of this build-up substrate is laminated by contacting 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 a carrier in which the metal foil is adhered to one side. Alternatively, the resin may be once laminated, and then one metal foil of the laminate in which the metal foil is adhered to both sides of the present invention, or one metal foil of the carrier-attached metal foil in which the metal foil is adhered to both sides. May be contacted and laminated.

  For the coreless build-up board manufactured in this way, wiring is formed on the surface through a plating step and / or an etching step, and the build-up wiring is separated by separating the carrier resin and the copper foil from each other. The board is completed. After peeling and separating, wiring may be formed on the peeled surface of the metal foil, or the entire metal foil may be removed by etching to form a build-up wiring board. Furthermore, a printed circuit board is completed by mounting electronic components on the build-up wiring board. Also, a printed circuit board can be obtained by mounting electronic components directly on the coreless build-up board before resin peeling.

  Hereinafter, experimental examples will be shown as examples and comparative examples of the present invention, but these experimental examples are provided for better understanding of the present invention and its advantages, and are intended to limit the present invention. is not.

<Experimental example 1>
A plurality of electrolytic copper foils (thickness 12 μm) were prepared, and a shiny (S) surface of each electrolytic copper foil was subjected to nickel-zinc (Ni—Zn) alloy plating treatment and chromate (Cr—Zn) under the following conditions. Chromate) treatment was performed to make the ten-point average roughness (measured in accordance with Rz jis: JIS B 0601: 2001) of the bonding surface (here, the S surface) 1.5 μm, and then as a resin, Mitsubishi Gas Chemical Co., Ltd. A prepreg (BT resin) manufactured by a company was attached to the S side of the electrolytic copper foil, and hot pressed at 190 ° C. for 100 minutes to produce a copper foil with a carrier.

(Nickel-zinc alloy plating)
Ni concentration 17g / L (added as NiSO ₄ )
Zn concentration 4g / L (added as ZnSO ₄ )
pH 3.1
Liquid temperature 40 ℃
Current density 0.1-10A / dm ²
Plating time 0.1-10 seconds

(Chromate treatment)
Cr concentration 1.4 g / L (added as CrO ₃ or K ₂ CrO ₇ )
Zn concentration 0.01-1.0 g / L (added as ZnSO ₄ )
Na ₂ SO ₄ concentration 10 g / L
pH 4.8
Liquid temperature 55 ℃
Current density 0.1-10A / dm ²
Plating time 0.1-10 seconds

  For some electrolytic copper foils, an aqueous solution of a silane compound was applied to the S surface using a spray coater, and then the copper foil surface was dried in air at 100 ° C. before being attached to a prepreg. went. Regarding the usage conditions of the silane compound, Table 1 shows the type of the silane compound, the stirring time from the dissolution of the silane compound in water to the coating, the concentration of the silane compound in the aqueous solution, the alcohol concentration in the aqueous solution, and the pH of the aqueous solution. Show.

  In addition, assuming that some of the copper foil with a carrier is subjected to a heat history during further heat treatment such as circuit formation with respect to the body foil with a carrier, the conditions described in Table 1 (here, Heat treatment at 220 ° C. for 3 hours).

  The peel strength between the copper foil and the plate-shaped carrier (resin after heating) in the copper foil with a carrier obtained by hot pressing and the copper foil with a carrier after further heat treatment was measured. The respective results are shown in Table 1.

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

<Experimental Examples 2 to 18>
Using the copper foil, the resin (prepreg) and a part of the silane compound shown in Table 1, a copper foil with a carrier was produced in the same procedure as in Experimental Example 1. In some experimental examples, heat treatment under the conditions shown in Table 1 was further performed. The same evaluation as in Experimental Example 1 was performed for each. The results are shown in Tables 1 and 2.

  In addition, the type of the bonding surface of the copper foil, the condition of the surface treatment and the surface roughness Rz jis, the use condition of the silane compound, the type of the prepreg, and the laminating condition of the copper foil and the prepreg are as shown in Table 1. is there.

  Regarding the surface treatment conditions of the treated surface of the copper foil, specific conditions of the epoxysilane (treatment) and the roughening treatment are as follows.

(Epoxysilane treatment)
Treatment liquid: 3-glycidoxypropyltrimethoxysilane 0.9% by volume aqueous solution
pH 5.0 to 9.0
Stirred for 12 hours at room temperature Treatment method: After applying the treatment liquid using a spray coater, the treated surface is dried in air at 100 ° C. for 5 minutes.

(Roughening treatment)
Cu concentration 20g / L (added as CuSO ₄ )
H ₂ SO ₄ concentration 50 to 100 g / L
As concentration 0.01 to 2.0 g / L (added as arsenous acid)
Liquid temperature 40 ℃
Current density 40-100A / dm ²
Plating time 0.1-30 seconds

<Experimental Examples 19 to 20>
A copper foil with a carrier, a resin (prepreg), and a part of a silane compound shown in Table 3 were used to produce a copper foil with a carrier in the same procedure as in Experimental Example 1. Further, heat treatment under the conditions shown in Table 3 was performed. The copper foil with a carrier thus obtained was evaluated in the same manner as in Experimental Example 1. The results are shown in Tables 3 and 4.

  The S surface was used as the bonding surface of the copper foil, and the surface was chromated under the above-mentioned conditions. In addition, the surface roughness Rz jis of the copper foil, the type of prepreg, the use conditions of the silane compound for the surface treatment of the prepreg, and the lamination conditions of the copper foil and the prepreg are as shown in Table 3.

  According to the table, the silane compound, even if treated on the surface of the copper foil, the surface of the prepreg, peel strength of the laminate after that, peel strength after heating, peeling workability is equivalent. It can be seen that the results were obtained.

(Build-up wiring board)
FR-4 prepreg (manufactured by Nanya Plastic Co., Ltd.) and copper foil (manufactured by JX Nippon Mining & Metals Corporation, JTC 12 μm (product name)) are sequentially laminated on both sides of the copper foil with a carrier produced in this way, and 3 MPa. Hot pressing was performed under the heating conditions shown in each table under the pressure of 4 to produce a 4-layer copper-clad laminate.

  Next, a hole having a diameter of 100 μm penetrating the copper foil on the surface of the 4-layer copper-clad laminate and the insulating layer (cured prepreg) under the copper foil was punched using a laser processing machine. Subsequently, the copper foil surface on the copper foil with a carrier exposed at 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 plate are electroless copper plated, and copper plated by electrolytic copper plating. Then, an electrical connection was formed between the copper foil on the carrier-attached copper foil and the copper foil on the surface of the 4-layer copper-clad laminate. Next, a part of the copper foil on the surface of the 4-layer copper-clad laminate was etched with a ferric chloride-based etching solution to form a circuit. In this way, a 4-layer build-up substrate was obtained.

  Subsequently, in the 4-layer build-up substrate, two sets of 2-layer build-up wiring boards were obtained by peeling and separating the plate-shaped carrier of the copper foil with a carrier and the copper foil.

  Subsequently, the copper foil on the two sets of the two-layer build-up wiring boards, which was in close contact with the plate-shaped carrier, 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 boards were produced, and for each of them, the degree of contact between the prepreg and the copper foil constituting the copper foil with carrier in the build-up board production process was visually confirmed, and Table 1, In the build-up wiring board using the copper foil with the carrier produced under the conditions in which the peel strength and the peel strength after heating are evaluated as “S” and “G” in Table 3, the resin of the copper foil with the carrier is used for the build-up. The (plate-shaped carrier) could be peeled off without being destroyed. However, with respect to the condition evaluated as “G”, as shown in Tables 1 and 3, there was also a case where the copper foil peeled from the plate-shaped carrier without a peeling operation at the time of buildup.
Regarding the condition evaluated as “N”, the resin was destroyed during the peeling operation of the copper foil in the copper foil with a carrier during buildup, or the resin was not peeled off and remained on the copper foil surface.
Regarding the condition evaluated as "-", the resin was peeled off without being destroyed during the peeling operation of the copper foil in the carrier-added copper foil at the time of build-up. It could come off.

Further, the present invention may be as follows.
(1) A metal foil with a carrier, which is made of a resin-made plate-shaped carrier and a metal foil which is releasably adhered to at least one surface of the carrier, and the metal foil and the plate-shaped carrier are defined in JIS C6481. The peel strength measured according to the specified 90 degree peel strength measuring method is 10 gf / cm or more and 67 gf / cm or less,
The thickness of the plate-like carrier is 50 μm or more,
A metal foil with a carrier having a ten-point average roughness (Rz jis) of 0.4 μm or more and 10.0 μm or less on the surface of the metal foil that is not in contact with the plate-shaped carrier.
(Excluding metal foil with a carrier having a joint interface layer composed of a metal layer / pure carbon layer)
(2) A metal foil with a carrier, which comprises a resin plate carrier and a metal foil that is releasably adhered to at least one surface of the carrier, and the metal foil and the plate carrier are defined in JIS C6481. The peel strength measured according to the specified 90 degree peel strength measuring method is 10 gf / cm or more and 200 gf / cm or less,
The ten-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the plate-shaped carrier is 0.4 μm or more and 10.0 μm or less,
The peel strength measured according to the 90 degree peel strength measuring method defined in JIS C6481 for the metal foil and the plate-shaped carrier after heating at 220 ° C. for at least one of 3 hours, 6 hours and 9 hours. A metal foil with a carrier having a thickness of 10 gf / cm or more and 163 gf / cm or less and a thickness of the metal foil of 1 μm or more.
(Excluding metal foil with a carrier having a joint interface layer composed of a metal layer / pure carbon layer)
(3) A metal foil with a carrier, which is made of a resin-made plate-shaped carrier and a metal foil that is releasably adhered to at least one surface of the carrier, and the metal foil and the plate-shaped carrier are specified in JIS C6481. The peel strength measured according to the specified 90 degree peel strength measuring method is 10 gf / cm or more and 200 gf / cm or less,
The ten-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the plate-shaped carrier is 0.4 μm or more and 10.0 μm or less,
The plate-shaped carrier and the metal foil that compose the metal foil with the carrier have the following formula:
(In the formula, 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 halogen atoms. in substituted is any of these hydrocarbon groups, R ³ and R ⁴ are independently a halogen atom or an alkoxy group, or an alkyl group, a hydrocarbon group selected from the group consisting of cycloalkyl group and an aryl group, Or any of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms.)
A metal foil with a carrier obtained by laminating the silane compound shown in 1 above, a hydrolysis product thereof, and a condensate of the hydrolysis product alone or in combination.
(4) The metal foil with a carrier according to any one of (1) to (3), wherein the resin plate-shaped carrier contains a thermosetting resin.
(5) The resin-made plate-like carrier is a metal foil with a carrier according to any one of (1) to (4), which is a prepreg.
(6) In the metal foil with a carrier according to any one of (1) to (5),
The plate carrier made of resin is a metal foil with a carrier having a glass transition temperature Tg of 120 to 320 ° C.
(7) In the metal foil with a carrier according to any one of (1) to (6),
A metal foil with a carrier having a ten-point average roughness (Rz jis) of a surface of the metal foil in contact with the carrier of 3.5 μm or less.
(8) In the metal foil with a carrier according to any one of (1) and (3) to (7),
The peel strength measured according to the 90 degree peel strength measuring method defined in JIS C6481 for the metal foil and the plate-shaped carrier after heating at 220 ° C. for at least one of 3 hours, 6 hours and 9 hours. A metal foil with a carrier having a thickness of 10 gf / cm or more and 200 gf / cm or less and a thickness of the metal foil of 1 μm or more.
(9) The plate-shaped carrier and the metal foil constituting the metal foil with the carrier have the following formula:
(In the formula, 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 halogen atoms. in substituted is any of these hydrocarbon groups, R ³ and R ⁴ are independently a halogen atom or an alkoxy group, or an alkyl group, a hydrocarbon group selected from the group consisting of cycloalkyl group and an aryl group, Or any of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms.)
Any of (1), (2), and (4) to (8), which are obtained by laminating the silane compound shown in (1), its hydrolysis product, or a condensate of the hydrolysis product, alone or in combination. The metal foil with a carrier according to Crab.
(10) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (9), and then the resin or the metal foil is repeatedly laminated one or more times. A method for producing a multi-layer metal-clad laminate comprising:
(11) A resin is laminated on the metal foil side of the metal foil with a carrier according to any one of (1) to (9), and then the resin, a single-sided or double-sided metal-clad laminate, or (1) to (9) A method for producing a multi-layer metal-clad laminate, which comprises repeatedly laminating the metal foil with a carrier or the metal foil according to any one of the above.
(12) The method for producing a multilayer metal-clad laminate according to (10) or (11), further including a step of peeling and separating the plate-shaped carrier of the metal foil with a carrier and the metal foil. Method of manufacturing a plate.
(13) A method for producing a multi-layer metal-clad laminate, including the step of removing part or all of the metal foil separated and separated by etching in the production method as described in (12).
(14) A method for manufacturing a build-up substrate, including a step of forming one or more build-up wiring layers on the metal foil side of the metal foil with a carrier according to any one of (1) to (9).
(15) The method of manufacturing a buildup substrate according to (14), wherein the buildup wiring layer is formed by using at least one of a subtractive method, a full additive method, and a semi-additive method.
(16) A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of (1) to (9), and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, A method for manufacturing a build-up substrate, comprising stacking the metal foil with a carrier or the metal foil according to any one of (1) to (9) repeatedly one or more times.
(17) In the method for manufacturing a build-up substrate according to (16), a single-sided or double-sided wiring substrate, a single-sided or double-sided metal-clad laminate, a metal foil of a metal foil with a carrier, a plate-shaped carrier of a metal foil with a carrier, or a resin. A method for manufacturing a build-up substrate, further comprising the step of: forming a hole in the hole; and conducting plating on the side surface and the bottom surface of the hole.
(18) In the method for manufacturing a build-up board according to (16) or (17), a metal foil forming the one-sided or double-sided wiring board, a metal foil forming a one-sided or double-sided metal-clad laminate, and a metal with a carrier A method for manufacturing a build-up substrate, further comprising performing the step of forming wiring on at least one of the metal foils forming the foil once or more.
(19) A step of laminating the metal foil with a carrier according to any one of (1) to (9), in which the metal foil is closely adhered to one surface of the surface on which wiring is formed, by contacting the resin plate side with the metal foil The manufacturing method of the buildup substrate as described in any one of (16) to (18).
(20) One metal foil of the metal foil with a carrier according to any one of (1) to (9), wherein a resin is laminated on the surface on which wiring is formed, and the metal foil is adhered to both sides of the resin. The method for manufacturing a build-up substrate according to any one of (16) to (18), further including a step of bringing the layers into contact with each other to stack them.
(21) At least one of the resins is a prepreg, and the method for manufacturing a buildup substrate according to any one of (16) to (20).
(22) The method for manufacturing a buildup substrate according to any one of (14) to (21), further including a step of peeling and separating the plate-shaped carrier of the metal foil with a carrier and the metal foil. Method of manufacturing a plate.
(23) The method for manufacturing a buildup wiring board according to (22), further including a step of removing a part or all of the metal foil that is in close contact with the plate-shaped carrier by etching.
(24) A method for manufacturing a printed circuit board, including a step of manufacturing a buildup board by the manufacturing method according to any one of (14) to (21).
(25) A method for manufacturing a printed circuit board, including a step of manufacturing a buildup wiring board by the manufacturing method according to (22) or (23).
(26) A resin-made process including a step of preparing the metal foil with a carrier according to any one of (1) to (9), and a step of peeling the plate carrier made of the resin from the metal foil with a carrier. Plate-shaped carrier manufacturing method.
(27) A method of manufacturing a build-up substrate, comprising: a step of preparing the metal foil with a carrier according to any one of (1) to (9); and a step of peeling the metal foil from the metal foil with a carrier.

11 Metal Foil with Carrier 11a Metal Foil 11b Silane Compound 11c Plate Carrier 16 Buildup Layer

Claims (26)

A metal foil with a carrier, which comprises a resin plate carrier and a metal foil which is releasably adhered to at least one surface of the carrier, and the metal foil and the plate carrier are defined in JIS C6481. The peel strength measured according to the 90-degree peel strength measuring method is 10 gf / cm or more and 67 gf / cm or less,
The thickness of the plate-like carrier is 50 μm or more,
The ten-point average roughness of the plate-shaped carrier not in contact with the side surface of the metal foil (Rz jis) is Ri der least 10.0μm or less 0.4 .mu.m,
The plate-shaped carrier and the metal foil that compose the metal foil with the carrier have the following formula:
(In the formula, 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 halogen atoms. in substituted is any of these hydrocarbon groups, R ³ and R ⁴ are independently a halogen atom or an alkoxy group, or an alkyl group, a hydrocarbon group selected from the group consisting of cycloalkyl group and an aryl group, Or any of these hydrocarbon groups in which one or more hydrogen atoms have been replaced by halogen atoms.)
A metal foil with a carrier obtained by laminating the silane compound shown in 1 above, a hydrolysis product thereof, and a condensate of the hydrolysis product alone or in combination .
(Excluding metal foil with a carrier having a joint interface layer composed of a metal layer / pure carbon layer) A metal foil with a carrier, which comprises a resin plate carrier and a metal foil which is releasably adhered to at least one surface of the carrier, and the metal foil and the plate carrier are defined in JIS C6481. The peel strength measured according to the 90-degree peel strength measuring method is 10 gf / cm or more and 200 gf / cm or less,
The ten-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the plate-shaped carrier is 0.4 μm or more and 10.0 μm or less,
The peel strength measured according to the 90 degree peel strength measuring method defined in JIS C6481 for the metal foil and the plate-shaped carrier after heating at 220 ° C. for at least one of 3 hours, 6 hours and 9 hours. 10 gf / cm or more and 163 gf / cm or less, and the metal foil has a thickness of 1 μm or more,
The plate-shaped carrier and the metal foil that compose the metal foil with the carrier have the following formula:
(In the formula, R ¹ Is an alkoxy group or a halogen atom, and R is ² Is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms, and R ³ And R ^Four Are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any of these in which one or more hydrogen atoms are substituted with a halogen atom. It is a hydrocarbon group. )
A metal foil with a carrier obtained by laminating the silane compound shown in 1 above, a hydrolysis product thereof, and a condensate of the hydrolysis product alone or in combination.
(Excluding metal foil with a carrier having a joint interface layer composed of a metal layer / pure carbon layer) A metal foil with a carrier, which comprises a resin plate carrier and a metal foil which is releasably adhered to at least one surface of the carrier, and the metal foil and the plate carrier are defined in JIS C6481. The peel strength measured according to the 90-degree peel strength measuring method is 10 gf / cm or more and 200 gf / cm or less,
The ten-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the plate-shaped carrier is 0.4 μm or more and 10.0 μm or less,
The plate-shaped carrier and the metal foil that compose the metal foil with the carrier have the following formula:
(In the formula, R ¹ Is an alkoxy group or a halogen atom, and R is ² Is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any of these hydrocarbon groups in which one or more hydrogen atoms are replaced by halogen atoms, and R ³ And R ^Four Are each independently a halogen atom, an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any of these in which one or more hydrogen atoms are substituted with a halogen atom. It is a hydrocarbon group. )
A metal foil with a carrier obtained by laminating the silane compound shown in 1 above, a hydrolysis product thereof, and a condensate of the hydrolysis product alone or in combination. The metal foil with a carrier according to any one of claims 1 to 3, wherein the resin-made plate-shaped carrier contains a thermosetting resin. The metal foil with a carrier according to claim 1, wherein the resin plate carrier is a prepreg. The metal foil with a carrier according to any one of claims 1 to 5,
The plate carrier made of resin is a metal foil with a carrier having a glass transition temperature Tg of 120 to 320 ° C. The metal foil with a carrier according to any one of claims 1 to 6,
A metal foil with a carrier having a ten-point average roughness (Rz jis) of a surface of the metal foil in contact with the carrier of 3.5 μm or less. The metal foil with a carrier according to any one of claims 1 and 3 to 7,
The peel strength measured according to the 90-degree peel strength measuring method defined in JIS C6481 for the metal foil and the plate-shaped carrier after heating at 220 ° C. for at least one of 3 hours, 6 hours, and 9 hours. A metal foil with a carrier having a thickness of 10 gf / cm or more and 200 gf / cm or less and a thickness of the metal foil of 1 μm or more. A multilayer comprising laminating a resin on at least one metallic foil side of the metallic foil with a carrier according to claim 1, and then repeating laminating the resin or the metallic foil one or more times. Manufacturing method of metal-clad laminate. Resin is laminated | stacked on the metal foil side of the metal foil with a carrier as described in any one of Claims 1-8, Then, resin, a single-sided or double-sided metal tension laminated board, or any one of Claims 1-9 A method for producing a multi-layer metal-clad laminate, which comprises repeatedly laminating the metal foil with a carrier or the metal foil described above once or more. The method for producing a multilayer metal-clad laminate according to claim 9 or 10, further comprising the step of peeling and separating the plate-shaped carrier of the metal foil with a carrier and the metal foil. The method for producing a multi-layer metal-clad laminate according to claim 11, comprising a step of removing a part or all of the metal foil separated and separated by etching. A method of manufacturing a build-up substrate, comprising the step of forming one or more build-up wiring layers on the metal foil side of the metal foil with a carrier according to claim 1. The method of manufacturing a buildup substrate according to claim 13, wherein the buildup wiring layer is formed by using at least one of a subtractive method, a full additive method, and a semi-additive method. A resin is laminated on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 8, and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, 9. A method of manufacturing a build-up substrate, comprising stacking the metal foil with a carrier or the metal foil according to any one of 1 to 8 once or more repeatedly. The method for manufacturing a build-up board according to claim 15, wherein a hole is formed in a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil of a metal foil with a carrier, a plate-shaped carrier of a metal foil with a carrier, or a resin. A method of manufacturing a build-up substrate, further comprising the steps of opening and conducting plating on the side surface and the bottom surface of the hole. The method for manufacturing a build-up substrate according to claim 15 or 16, wherein the metal foil forming the one-sided or double-sided wiring board, the metal foil forming the one-sided or double-sided metal-clad laminate, and the metal forming the metal foil with a carrier. A method for manufacturing a build-up substrate, further comprising performing a step of forming wiring on at least one of the foils one or more times. The method further comprising a step of laminating a metal foil with a carrier according to any one of claims 1 to 8 on the surface on which wiring is formed, by contacting a metal foil with the resin plate side of the metal foil with a carrier. The method for manufacturing a buildup substrate according to any one of 15 to 17. A resin is laminated on the surface on which wiring is formed, and one metal foil of the metal foil with a carrier according to any one of claims 1 to 8 is brought into contact with both sides of the resin. The method for manufacturing a build-up substrate according to any one of claims 15 to 17, further comprising a step of stacking layers. 20. The method for manufacturing a build-up substrate according to claim 15, wherein at least one of the resins is a prepreg. 21. The method for manufacturing a buildup wiring board according to claim 13, further comprising a step of peeling and separating the plate-shaped carrier of the metal foil with a carrier and the metal foil. Method. The method of manufacturing a buildup wiring board according to claim 21, further comprising a step of removing a part or all of the metal foil that is in close contact with the plate-shaped carrier by etching. A method for manufacturing a printed circuit board, comprising the step of manufacturing a build-up board by the manufacturing method according to claim 13. A method for manufacturing a printed circuit board, comprising the step of manufacturing a buildup wiring board by the manufacturing method according to claim 21 or 22. A plate carrier made of resin, comprising: a step of preparing the metal foil with a carrier according to any one of claims 1 to 8; and a step of peeling the plate carrier made of a resin from the metal foil with a carrier. Manufacturing method. A method for manufacturing a build-up substrate, comprising: a step of preparing the metal foil with a carrier according to claim 1; and a step of peeling the metal foil from the metal foil with a carrier.