WO2014046259A1 - Metallic foil having 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 specifically-structured aluminate compound, titanate compound, zirconate compound, hydrolysed products of the same, or condensation products of the hydrolysed products, either independently or in combination with one another.

Description

Metal foil with carrier

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 two-layer multilayer board or an ultra-thin coreless substrate used for a printed wiring board.

In general, a printed wiring board uses, as a basic constituent material, a dielectric material called “prepreg” obtained by impregnating a base material such as a synthetic resin plate, a glass plate, a glass nonwoven fabric, and paper with a synthetic resin. . Further, a sheet such as copper or copper alloy foil having electrical conductivity is bonded to the side facing the prepreg. The laminated body thus assembled is generally called a CCL (CopperoppClad Laminate) material. The surface of the copper foil in contact with the prepreg is usually a mat surface in order to increase the bonding strength. A foil made of aluminum, nickel, zinc or the like may be used instead of the copper or copper alloy foil. 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 composed of a synthetic resin plate-shaped carrier and a metal foil that is mechanically peelably adhered to at least one surface of the carrier. Describes that it can be used for the assembly of printed wiring boards. It was shown that the peel strength between the plate-like 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 supported over the entire surface by the synthetic resin, generation of wrinkles on the copper foil during lamination can be prevented. In addition, since the metal foil with carrier is in close contact with the synthetic resin without gaps, when the surface of the metal foil is plated or etched, it can be put into the chemical solution for plating or etching. . Furthermore, since the linear expansion coefficient of the synthetic resin is at the same level as the copper foil that is a constituent material of the substrate and the prepreg after polymerization, the circuit is not misaligned, resulting in fewer defective products, It has the outstanding effect that a yield can be improved.

JP 2009-272589 A JP 2000-196207 A

The metal foil with a carrier described in Patent Document 1 is an epoch-making invention that greatly contributes to reducing the manufacturing cost by simplifying the manufacturing process of the printed circuit board and increasing the yield, but the peel strength between the plate-like carrier and the metal foil. There is still room for further study on the optimization and means of the above. In particular, a remarkable problem for the inventor is that the peel strength between the plate-like carrier and the metal foil becomes too high depending on the material of the plate-like carrier, and means for easily adjusting the peel strength is provided. It is desirable. Then, this invention makes it a subject to provide the metal foil with a carrier in which the peeling strength of resin-made plate-shaped carrier and metal foil was adjusted.

As a result of earnestly examining the method for adjusting the peel strength between the resin plate and the metal foil, the present inventors have a predetermined structure on at least one surface prior to the bonding between the resin plate and the metal foil. The present inventors completed the present invention by finding the possibility of realizing a peel strength according to a desired application by coating with an aluminate compound, titanate compound or zirconate compound.

That is, the present invention is as follows.
(1) A metal foil with a carrier made of a resin-made plate-like carrier and a metal foil that is detachably adhered to at least one surface of the carrier, and the plate-like carrier and the metal foil have the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
The metal foil with a carrier formed by laminating the aluminate compound, the titanate compound, the zirconate compound, the hydrolysis products thereof, and the condensates of the hydrolysis products alone or in combination.
(2) Metal foil with a carrier as described in (1) whose peeling strength of a plate-shaped carrier and metal foil is 10 gf / cm or more and 200 gf / cm or less.
(3) The metal foil with a carrier according to (1) or (2), wherein the resin plate-like carrier contains a thermosetting resin.
(4) The metal foil with a carrier according to any one of (1) to (3), wherein the resinous plate-like carrier is a prepreg.
(5) The metal foil with a carrier according to (3) or (4), wherein the resin plate carrier has a glass transition temperature Tg of 120 to 320 ° C.
(6) The metal foil with a carrier according to any one of (1) to (5), wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 μm or less.
(7) The ten-point average roughness (Rz jis) of the surface of the metal foil that is not in contact with the carrier is 0.4 μm or more and 10.0 μm or less, according to any one of (1) to (6) Metal foil with carrier.
(8) The metal foil with a carrier according to any one of (1) to (7), wherein the thickness of the metal foil is 1 μm or more and 400 μm or less.
(9) The peel strength between the metal foil and the plate carrier after heating at 220 ° C. for 3 hours, 6 hours or 9 hours is 10 gf / cm or more and 200 gf / cm or less (1) to (8) Metal foil with a carrier in any one of.
(10) The metal foil with a carrier according to any one of (1) to (9), wherein the metal foil is a copper foil.
(11) On the surface of the metal foil, the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
The metal foil for printed wiring boards which has the aluminate compound, titanate compound, zirconate compound shown to these, these hydrolysis products, and the condensate of this hydrolysis product individually or in combination.
(12) The surface of the metal foil on which the aluminate compound, titanate compound, zirconate compound, these hydrolysis products, and a condensate of the hydrolysis products are allowed to act alone or in combination, The metal foil for a printed wiring board according to (11), wherein a chromate treatment is performed before the compound is allowed to act.
(13) The metal foil for a printed wiring board according to (11) or (12), wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 μm or less.
(14) The ten-point average roughness (Rz jis) of the surface of the metal foil on the side not in contact with the carrier is 0.4 μm or more and 10.0 μm or less, according to any one of (11) to (13) Metal foil for printed wiring boards.
(15) The metal foil for printed wiring board according to any one of (11) to (14), wherein the metal foil is a copper foil.
(16) On at least one surface, the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
A metal foil having an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, or a condensate of the hydrolysis product, either alone or in combination, and a resin plate on the surface Metal foil used for mechanically releasably adhering a cylindrical carrier.
(17) The metal foil aluminate compound, titanate compound, zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product, on the surface on the side that acts alone or in combination, The metal foil according to (16), which is subjected to a chromate treatment before the compound is allowed to act.
(18) The metal foil according to (16) or (17), wherein the ten-point average roughness (Rz jis) of the side surface in contact with the carrier of the metal foil is 3.5 μm or less.
(19) On at least one surface, the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
A resinous plate-like carrier having the aluminate compound, titanate compound, zirconate compound, hydrolysis products thereof, and condensates of the hydrolysis products alone or in combination.
(20) On at least one surface, the following formula:

Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
A plate carrier made of a resin having an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensation product of the hydrolysis product, either alone or in combination, on the surface A plate-like carrier used for applications in which a metal foil is peelably adhered.
(21) 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 (10), and then the resin or the metal foil is repeatedly laminated one or more times. A method for producing a multilayer metal-clad laminate comprising:
(22) A resin is laminated on the metal foil side of the metal foil with a carrier according to any one of (1) to (10), and then a resin, a single-sided or double-sided metal-clad laminate, or (1) to (10) A metal foil with a carrier according to any one of the above, or a method for producing a multilayer metal-clad laminate comprising repeatedly laminating a metal foil one or more times.
(23) In the method for producing a multilayer metal-clad laminate according to (21) or (22), the multilayer metal-clad laminate further comprising a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier. A manufacturing method of a board.
(24) The method for producing a multilayer metal-clad laminate comprising the step of removing a part or all of the separated and separated metal foil by etching in the production method according to (23).
(25) A multilayer metal-clad laminate obtained by the production method according to any one of (21) to (24).
(26) A method for manufacturing a buildup board, comprising a step of forming one or more buildup wiring layers on the metal foil side of the metal foil with a carrier according to any one of (1) to (10).
(27) The buildup wiring layer manufacturing method according to (26), wherein the buildup wiring layer is formed using at least one of a subtractive method, a full additive method, or a semi-additive method.
(28) 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 (10), and then resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate , (1) to (10) A method for producing a build-up substrate, comprising: laminating the metal foil with a carrier or metal foil according to any one of one or more times.
(29) In the method for manufacturing a buildup board according to (28), a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, a metal foil with a carrier, a plate-like carrier with a metal foil with a carrier, a metal foil Or a method for manufacturing a build-up substrate, further comprising the steps of drilling a hole in the resin and conducting conductive plating on the side and bottom surfaces of the hole.
(30) In the method for manufacturing a buildup board according to (28) or (29), the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, and the metal foil with carrier The manufacturing method of the buildup board | substrate which further includes performing the process of forming wiring in at least one of metal foil which comprises, and at least one of metal foil.
(31) A step of contacting and laminating the resin plate side of the metal foil with carrier according to any one of (1) to (10), wherein the metal foil is adhered to one surface on the surface on which the wiring is formed. A method for manufacturing a build-up substrate according to any one of (28) to (30).
(32) One metal foil of the metal foil with a carrier according to any one of (1) to (10), wherein a resin is laminated on the surface on which the wiring is formed, and a metal foil is adhered to both sides of the resin. The method for manufacturing a build-up substrate according to any one of (28) to (30), further including a step of laminating the layers.
(33) The method for manufacturing a buildup substrate according to any one of (28) to (32), wherein at least one of the resins is a prepreg.
(34) The buildup wiring according to any one of (26) to (33), further comprising a step of peeling and separating the plate-like carrier and metal foil of the metal foil with carrier. A manufacturing method of a board.
(35) The method for manufacturing a buildup wiring board according to (34), further including a step of removing a part or all of the metal foil adhered to the plate carrier by etching.
(36) A build-up wiring board obtained by the manufacturing method according to (34) or (35).
(37) A method for producing a printed circuit board, comprising a step of producing a build-up substrate by the production method according to any one of (26) to (33).
(38) A method for producing a printed circuit board, comprising a step of producing a build-up wiring board by the production method according to (34) or (35).

According to the present invention, the peel strength between the plate carrier and the metal foil can be easily adjusted. Therefore, for example, a metal foil with a carrier that has conventionally exhibited an excessively high peel strength is adjusted to a preferable peel strength, so that an advantage of improving the productivity of a printed wiring board using the metal foil with a carrier is obtained. .

An example of the configuration of CCL is shown. The structural example of the metal foil with a carrier which concerns on this invention is shown. The assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined to the single side | surface of the resin board) is shown. The assembly example of the multilayer CCL using the copper foil with a carrier which concerns on this invention (The form which copper foil joined on both surfaces of the resin board) 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-made plate-like carrier and a metal foil that is detachably adhered to one or both sides, preferably both sides of the carrier, is prepared. To do. One structural example of the metal foil with a carrier according to the present invention is shown in FIGS. In particular, the metal foil with carrier 11 in which the metal foil 11a is detachably adhered to both surfaces of a resin plate carrier 11c is shown at the beginning of FIG. Between the plate-like carrier 11c and the metal foil 11a, an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, a condensation product of the hydrolysis product (hereinafter simply referred to as “ 11b), which is described as “metal alkoxide”.

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

Since the metal foil with carrier used in the present invention must be peeled off eventually, it is inconvenient that the adhesiveness is excessively high, but the plate-like carrier and the metal foil are chemicals such as plating performed in the printed circuit board manufacturing process. Adhesiveness that does not peel in the processing step is necessary.

The adjustment of the peel strength for realizing such adhesion is performed by adjusting a metal alkoxide (aluminate compound, titanate compound, zirconate compound or a hydrolysis product thereof, or a hydrolysis product thereof having a structure represented by the following formula: The condensate is used alone or in combination. This is because such metal alkoxide is bonded between the plate-like carrier and the metal foil, whereby the adhesiveness is appropriately lowered and the peel strength can be adjusted to the above-described range.

In the formula, R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms. Any one of these substituted hydrocarbon groups, M is any one of Al, Ti, and Zr, n is 0 or 1 or 2, m is an integer from 1 to M, and R1 At least one of these is an alkoxy group. M + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr.

The metal alkoxide must have at least one alkoxy group. A hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group in the absence of an alkoxy group, or any one of these hydrocarbons in which one or more hydrogen atoms are substituted with a halogen atom When a substituent is comprised only by group, there exists a tendency for the adhesiveness of a plate-shaped carrier and metal foil surface to fall too much. The metal alkoxide is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or any one of these hydrocarbon groups in which one or more hydrogen atoms are substituted with a halogen atom. It is necessary to have 0-2. This is because when three or more hydrocarbon groups are present, the adhesion between the plate-like carrier and the metal foil surface tends to be excessively lowered. The alkoxy group according to the present invention includes an alkoxy group in which one or more hydrogen atoms are substituted with halogen atoms. In adjusting the peel strength between the plate-like carrier and the metal foil to the above-mentioned range, the metal alkoxide has two or more alkoxy groups and the hydrocarbon group (a hydrocarbon in which one or more hydrogen atoms are substituted with a halogen atom). It preferably has one or two groups).

Examples of the alkyl group include, but are 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 And straight-chain or branched alkyl groups having 1 to 20, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, such as -hexyl group, n-octyl group, and n-decyl group. .

Further, the cycloalkyl group is not limited, but it has 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc., preferably 5 to 7 carbon atoms. Of the cycloalkyl group.

Further, examples of the aromatic hydrocarbon group suitable as R ² include a phenyl group, a phenyl group substituted with an alkyl group (eg, tolyl group, xylyl group), 1- or 2-naphthyl group, anthryl group, and the like. Examples thereof include 6 to 20, preferably 6 to 14, aryl groups, and these hydrocarbon groups may contain one or both of a hydroxyl group and an amino group.
In these hydrocarbon groups, one or more hydrogen atoms may be substituted with a halogen atom, and may be substituted with, for example, a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred aluminate compounds include trimethoxyaluminum, methyldimethoxyaluminum, ethyldimethoxyaluminum, n- or iso-propyldimethoxyaluminum, n-, iso- or tert-butyldimethoxyaluminum, n-, iso- or neo- Pentyl dimethoxy aluminum, hexyl dimethoxy aluminum, octyl dimethoxy aluminum, decyl dimethoxy aluminum, phenyl dimethoxy aluminum; alkyl-substituted phenyl dimethoxy aluminum (for example, p- (methyl) phenyl dimethoxy aluminum), dimethylmethoxy aluminum, triethoxy aluminum, methyl diethoxy aluminum Ethyldiethoxyaluminum, n- or iso-propyldiethyl Aluminum, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyldiethoxyaluminum, decyldiethoxyaluminum, phenyldiethoxyaluminum, alkyl-substituted phenyldiethoxyaluminum (eg p -(Methyl) phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropoxyaluminum, methyldiisopropoxyaluminum, ethyldiisopropoxyaluminum, n- or iso-propyldiethoxyaluminum, n-, iso- or tert-butyl Diisopropoxy aluminum, pentyl diisopropoxy aluminum, hexyl diisopropoxy aluminum, octyl dii Propoxyaluminum, decyldiisopropoxyaluminum, phenyldiisopropoxyaluminum, alkyl-substituted phenyldiisopropoxyaluminum (eg, p- (methyl) phenyldiisopropoxyaluminum), dimethylisopropoxyaluminum, (3,3,3-tri Fluoropropyl) dimethoxyaluminum and tridecafluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum, their hydrolysis products, And condensates of these hydrolysis products. Among these, from the viewpoint of availability, trimethoxyaluminum, triethoxyaluminum, and triisopropoxyaluminum are preferable.

Examples of preferred titanate compounds include tetramethoxy titanium, methyl trimethoxy titanium, ethyl trimethoxy titanium, n- or iso-propyl trimethoxy titanium, n-, iso- or tert-butyl trimethoxy titanium, n-, iso- Or neo-pentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl-substituted phenyltrimethoxytitanium (eg p- (methyl) phenyltrimethoxytitanium), dimethyldimethoxy Titanium, tetraethoxy titanium, methyl triethoxy titanium, ethyl triethoxy titanium, n- or iso-propyl triethoxy titanium, n-, iso- or tert-butyl triethoxy titanium, Nitrotriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, decyltriethoxytitanium, phenyltriethoxytitanium, alkyl-substituted phenyltriethoxytitanium (eg p- (methyl) phenyltriethoxytitanium), dimethyldiethoxytitanium , Tetraisopropoxytitanium, methyltriisopropoxytitanium, ethyltriisopropoxytitanium, n- or iso-propyltriethoxytitanium, n-, iso- or tert-butyltriisopropoxytitanium, pentyltriisopropoxytitanium, hexyltri Isopropoxytitanium, octyltriisopropoxytitanium, decyltriisopropoxytitanium, phenyltriisopropoxytitanium, alkyl-substituted phenyltriisopropoxytitanium ( For example, p- (methyl) phenyltriisopropoxytitanium), dimethyldiisopropoxytitanium, (3,3,3-trifluoropropyl) trimethoxytitanium, and tridecafluorooctyltriethoxytitanium, methyltrichlorotitanium, dimethyldichloro Examples include titanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitanium, hydrolysis products thereof, and condensates of these hydrolysis products. Among these, tetramethoxy titanium, tetraethoxy titanium, and tetraisopropoxy titanium are preferable from the viewpoint of availability.

Examples of preferred zirconate compounds include tetramethoxyzirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or iso-propyltrimethoxyzirconium, n-, iso- or tert-butyltrimethoxyzirconium, n-, iso- Or neo-pentyltrimethoxyzirconium, hexyltrimethoxyzirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl-substituted phenyltrimethoxyzirconium (eg, p- (methyl) phenyltrimethoxyzirconium), dimethyldimethoxy Zirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, -Or iso-propyltriethoxyzirconium, n-, iso- or tert-butyltriethoxyzirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, decyltriethoxyzirconium, phenyltriethoxyzirconium, alkyl-substituted phenyl Triethoxyzirconium (eg, p- (methyl) phenyltriethoxyzirconium), dimethyldiethoxyzirconium, tetraisopropoxyzirconium, methyltriisopropoxyzirconium, ethyltriisopropoxyzirconium, n- or iso-propyltriethoxyzirconium, n -, Iso- or tert-butyltriisopropoxyzirconium, pentyltriisopropoxy Luconium, hexyltriisopropoxyzirconium, octyltriisopropoxyzirconium, decyltriisopropoxyzirconium, phenyltriisopropoxyzirconium, alkyl-substituted phenyltriisopropoxyzirconium (eg, p- (methyl) phenyltriisopropoxytitanium), dimethyldi Isopropoxyzirconium, (3,3,3-trifluoropropyl) trimethoxyzirconium, and tridecafluorooctyltriethoxyzirconium, methyltrichlorozirconium, dimethyldichlorozirconium, trimethylchlorozirconium, phenyltrichlorozirconium, dimethyldifluorozirconium, dimethyldibromo Zirconium, diphenyldibromozirconium and their hydrolysis Products, and condensates of these hydrolysis products. Among these, tetramethoxyzirconium, tetraethoxyzirconium, and tetraisopropoxyzirconium are preferable from the viewpoint of availability.

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

Metal alkoxide can be used in the form of an aqueous solution. Alcohols such as methanol and ethanol can be added in order to increase the solubility in water. The addition of alcohol is particularly effective when a highly hydrophobic metal alkoxide is used.

The higher the concentration of the metal alkoxide in the aqueous solution, the lower the peel strength between the metal foil and the plate carrier, and the peel strength can be adjusted by adjusting the metal alkoxide concentration. Although not limited, the concentration of the metal alkoxide in the aqueous solution can be 0.001 to 1.0 mol / L, and typically 0.005 to 0.2 mol / L.

The pH of the aqueous solution of metal alkoxide is not particularly limited and can be used on either 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 standpoint 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. .

From the viewpoint of facilitating the adjustment of the peel strength with the metal alkoxide, the peel strength between the metal foil and the plate carrier is preferably 10 gf / cm or more, more preferably 30 gf / cm or more, and 50 gf / cm. While it is more preferably at least cm, it is preferably at most 200 gf / cm, more preferably at most 150 gf / cm, and even more preferably at most 80 gf / cm. By making the peel strength between the metal foil and the plate carrier in such a range, the peel strength is such that it can be easily peeled off by hand, that is, mechanically peeled off, without being peeled off during transport or processing. Easy to adjust.

Also, in the process of manufacturing a multilayer printed wiring board, heat treatment is often performed in a lamination press process or a desmear process. Therefore, the heat history that the metal foil with a carrier receives becomes severer as the number of laminated layers increases. Therefore, when considering application to a multilayer printed wiring board in particular, it is desirable that the peel strength between the metal foil and the plate-like carrier is in the above-described range even after passing through a required thermal history.

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

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

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

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

The resin that serves as the plate-like carrier is not particularly limited, and phenol resin, polyimide resin, epoxy resin, natural rubber, pine resin, and the like can be used, but a thermosetting resin is preferable. A prepreg can also be used. The prepreg before being bonded to the metal foil is preferably in a B-stage state. The linear expansion coefficient of the prepreg (C stage) is 12 to 18 (× 10 ⁻⁶ / ° C.), 16.5 (× 10 ⁻⁶ / ° C.) of the copper foil as the constituent material of the substrate, or 17 of the SUS press plate .3 (× 10 ⁻⁶ / ° C.) is advantageous in that it is difficult to cause circuit misalignment due to a phenomenon (scaling change) in which the substrate size before and after pressing differs from that at the time of design. Furthermore, as a synergistic effect of these merits, it becomes possible to produce a multilayer ultra-thin coreless substrate. The prepreg used here may be the same as or different from the prepreg constituting the circuit board. Conventionally, a metal plate has been used as a plate-shaped carrier of a metal foil with a carrier. In this case, the plate-like carrier and the metal foil are adhered to each other by welding or adhesion. When using an adhesive, from the viewpoint of heat resistance, there are many things that are generally not suitable for build-up, and when closely contacting by welding, the peel strength is too high when using full-surface welding, It is difficult to peel off easily, and it becomes difficult to prevent the chemical solution from entering between the plate-shaped carrier and the metal foil when using partial welding. . Therefore, by using a resin-made plate-like carrier, an appropriate peel strength can be exhibited with the metal foil, and by using a heat-resistant resin, it can sufficiently withstand the heat history during build-up. be able to.

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

Also, it is desirable that the thermal expansion coefficient of the resin is within + 10% and −30% of the thermal expansion coefficient of the metal foil. As a result, it is possible to effectively prevent circuit misalignment due to the difference in thermal expansion between the metal foil and the resin, thereby reducing the occurrence of defective products and improving the yield.

The thickness of the plate-like carrier is not particularly limited and may be rigid or flexible. However, 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 will not flow through the printed wiring board manufacturing process. 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.

As the metal foil, copper or copper alloy foil is a typical one, but foil 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 use as a wiring of a printed circuit board. When metal foil is affixed on both surfaces of the plate-like carrier, metal foils having the same thickness may be used, or metal foils having different thicknesses 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 (including the case where one or more alloy elements such as Zn, P, Ni, Mo, Zr, Ti, etc. are contained in the chromate treatment liquid) for imparting rust prevention and discoloration resistance, surface roughness (For example, copper electrodeposition grains, Cu—Ni—Co alloy plating, Cu—Ni—P alloy plating, Cu—Co alloy plating, Cu—Ni alloy plating, Cu—Co alloy plating, And 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 carrier, but also the chromate treatment has a great influence. Chromate treatment is important from the viewpoint of rust prevention and discoloration resistance, but since it tends to significantly increase the peel strength, it is also meaningful as a means for adjusting the peel strength.

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

Therefore, in a preferred embodiment of the metal foil with a carrier according to the present invention, the surface roughness of the bonded surface is JIS B 0601: in order to adjust the peel strength between the metal foil and the plate-like carrier to the preferred range described above. Expressed by the ten-point average roughness (Rz jis) of the metal foil surface measured according to 2001, it is preferably 3.5 μm or less, more preferably 3.0 μm or less. However, reducing the surface roughness indefinitely takes time and increases costs, so it is preferably 0.1 μm or more, and more preferably 0.3 μm or more. When 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) by adjusting to such a surface roughness. However, it is easier to adjust the surface roughness by using the S-plane. On the other hand, it is preferable that the ten-point average roughness (Rz jis) of the surface of the metal foil not contacting the carrier is 0.4 μm or more and 10.0 μm or less.

In a preferred embodiment of the metal foil with a carrier according to the present invention, the surface treatment for improving the peel strength such as roughening treatment is not performed on the bonding surface of the metal foil with the resin. Moreover, in preferable one Embodiment of metal foil with a carrier which concerns on this invention, the binder for improving the adhesive force with metal foil is not added in resin.

As conditions for hot pressing for producing a metal foil with a carrier, when a prepreg is used as a plate-like 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. .

From the above viewpoints, the present invention applies the above metal alkoxide to at least one surface of the metal foil as described above, which serves as the adhesion surface, in order to adhere the resin-made plate carrier in a peelable manner. Provided metal foil. Further, the surface of the metal foil may be subjected to the chromate treatment as described above before applying the metal alkoxide.

From another point of view, the present invention provides a plate-like carrier having the above metal alkoxide on at least one surface of the plate-like carrier that serves as an adhesion surface of the metal foil. This plate-like carrier can be suitably used for applications in which the metal foil as described above is adhered in a peelable manner.

From another viewpoint, the present invention provides a metal foil for a coreless multilayer printed wiring board in which the metal alkoxide is coated on the surface of the metal foil as described above. The surface of the metal foil may be subjected to the chromate treatment as described above before being coated with the metal alkoxide.

The surface of the metal foil or resin was measured with a scanning electron microscope equipped with XPS (X-ray photoelectron spectrometer), EPMA (electron beam microanalyzer), EDX (energy dispersive X-ray analysis), Al, If Ti and Zr are detected, it can be inferred that the metal alkoxide is present on the surface of the metal foil or resin.

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

Second, the resin is laminated on the metal foil side of the metal foil with carrier described above, and then the resin, single-sided or double-sided metal-clad laminate, or metal foil with carrier of the present invention, or metal foil once or more, for example, A method for producing a multilayer metal-clad laminate comprising repeatedly laminating 1 to 10 times is provided. In addition, the lamination after the resin laminated on the first metal foil with carrier is performed as many times as desired. In each lamination, a book different from the resin, single-sided or double-sided metal-clad laminate, and the first metal foil with carrier is used. It can be arbitrarily selected from the group consisting of the metal foil with carrier of the invention and the metal foil.

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

Further, the method may further include a step of removing a part or the whole of the metal foil by etching after the plate-like carrier and the metal foil are separated from each other.

Thirdly, a resin is laminated on the metal foil side of the metal foil with carrier described above, and then resin, single-sided or double-sided wiring board, single-sided or double-sided metal-clad laminate, or metal foil with carrier of the present invention, or metal foil Is provided one or more times, for example, 1 to 10 times, and a buildup substrate manufacturing method is provided. In addition, the lamination after the resin laminated on the first metal foil with carrier is performed as many times as desired. In each lamination, the resin, the single-sided or double-sided wiring board, the single-sided or double-sided metal-clad laminate, the first metal with carrier It can be arbitrarily selected from the group consisting of the metal foil with a carrier of the present invention different from the foil and the metal foil.

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

The subtractive method is a method of forming a conductor pattern by selectively removing unnecessary portions of 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. Point 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 an electroless method on a seed layer made of metal foil, for example. In this method, a conductor pattern is formed by using metal deposition and electrolytic plating, etching, or a combination thereof, and then an unnecessary seed layer is removed by etching.

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

The manufacturing method of the build-up board may further include a step of bringing a metal foil into close contact with one surface on 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. . Moreover, it is possible to further include a step of laminating a metal foil with a carrier according to the present invention in which a resin is laminated on the surface on which the wiring is formed and the metal foil is adhered to both sides of the resin.
The “surface on which the wiring is formed” means a portion where wiring is formed on the surface that appears every time a buildup is performed, and the buildup substrate includes both a final product and an intermediate product.

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

In addition, in the manufacturing method of the above-mentioned multilayer metal-clad laminate and the manufacturing method of a buildup board, each layer can be laminated | stacked by performing thermocompression bonding. This thermocompression bonding may be performed every time one layer is stacked, may be performed after being laminated to some extent, or may be performed collectively at the end.

In particular, the present invention provides a method for manufacturing a build-up board as described above, 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 or a resin, and conductive plating is performed on the side and bottom surfaces of the hole. Further, a metal foil and a circuit portion constituting the single-sided or double-sided wiring board, a metal foil constituting a single-sided or double-sided metal-clad laminate, and a method for producing a build-up board at least once including the step of forming a circuit on the metal foil I will provide a.

Hereinafter, as a specific example of the above-described application, a method for producing a four-layer CCL using the metal foil with a carrier according to the present invention will be described. The metal foil with carrier used here is the metal foil with carrier 11 in which the metal foil 11a is adhered to one surface of the plate-like carrier 11c. On this metal foil with carrier 11, a desired number of prepregs 12, and then a two-layer printed circuit board or two-layer metal-clad laminate called inner layer core 13, then prepreg 12, and further metal foil 11 with carrier 11 are sequentially stacked. Thus, a set of four-layer CCL assembly units is completed. Next, the unit 14 (referred to as “page”) is repeated about 10 times to form a press assembly 15 (referred to as “book”) (FIG. 3). Thereafter, the book 15 is sandwiched between the laminated molds 10 and set in a hot press machine, and a large number of four-layer CCLs can be manufactured simultaneously by press molding at a predetermined temperature and pressure. As the laminated mold 10, for example, a stainless plate can be used. Although the plate is not limited, for example, a thick plate of about 1 to 10 mm can be used. In general, CCL having four or more layers can be produced in the same process by increasing the number of inner core layers.

Hereinafter, as a specific example of the above-described application, a method for producing a coreless buildup substrate using the metal foil with carrier 11 in which the metal foil is in close contact with both surfaces of the plate-like carrier 11c of the resin plate according to the present invention will be described. . In this method, after a required number of buildup layers 16 are laminated on both sides of the metal foil with carrier 11, the metal foils on both sides are peeled from the metal foil with carrier 11 (see FIG. 4).

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 stacked in order, and the metal foil side is in contact with the resin plate on it, Furthermore, a buildup board | substrate can be manufactured by laminating | stacking the metal foil of the metal foil with a carrier of this invention in order.

As another method, a resin or conductor layer as an insulating layer is provided on at least one metal foil side of the metal foil with a carrier in which the metal foil is adhered to both surfaces or one surface of the resinous plate-like carrier 11c. Are laminated in order. 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 applying a desmear process for removing smear in the via hole, the bottom of the via hole, the side surface and the metal foil Electroless plating is performed on the entire surface or a part of the substrate to form an interlayer connection, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance on each portion of the metal foil where electroless plating or electrolytic plating is unnecessary before performing each plating. In addition, when the electroless plating, the electrolytic plating, or the adhesion between the plating resist and the metal foil is insufficient, the surface of the metal foil may be chemically roughened in advance. 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 and the electroless plating portion and the electrolytic plating portion by etching. Thereby, a build-up substrate is obtained. The steps from the lamination of the resin and the copper foil to the circuit formation may be repeated a plurality of times to form a multilayer build-up substrate.
Furthermore, on the outermost surface of this buildup substrate, the resin side of the metal foil of the metal foil with a carrier in which the metal foil is adhered to one side of the present invention may be contacted and laminated, or a resin plate is once laminated. Later, one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces of the present invention may be brought into contact with each other and laminated.

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

As another method, a resin as an insulating layer such as a prepreg or a photosensitive layer is formed on the exposed surface of a metal foil of a laminate obtained by laminating a metal foil such as a copper foil on one or both sides of the plate carrier of the present invention. Laminating resin. Thereafter, a via hole is formed at a predetermined position of the resin. For example, when a prepreg is used as the resin, the via hole can be formed by laser processing. After the laser processing, desmear treatment for removing smear in the via hole is preferably performed. When a photosensitive resin is used as the resin, the resin in the via hole forming portion can be removed by a photolithography method. Next, electroless plating is performed on the bottom and side surfaces of the via holes, the entire surface or a part of the resin to form interlayer connections, and further electrolytic plating is performed as necessary. A plating resist may be formed in advance on each portion of the resin where electroless plating or electrolytic plating is unnecessary before performing each plating. Further, when the adhesion between electroless plating, electrolytic plating, plating resist and resin is insufficient, the surface of the resin may be chemically roughened in advance. When a plating resist is used, the plating resist is removed after plating. Next, an unnecessary portion of the electroless plating portion or the electrolytic plating portion is removed by etching to form a circuit. Thereby, a build-up substrate is obtained. The steps from resin lamination to circuit formation may be repeated a plurality of times to form a multilayered build-up substrate.
Further, the outermost surface of this build-up substrate is laminated by contacting the resin side of the laminate in which the metal foil is closely attached to one side of the present invention, or the resin side of the metal foil with a carrier having the metal foil closely attached to one side. Alternatively, after laminating the resin once, one metal foil of the laminate in which the metal foil is adhered to both surfaces of the present invention, or one metal foil of the metal foil with a carrier in which the metal foil is adhered to both surfaces May be laminated in contact with each other.

For the coreless build-up substrate manufactured in this way, a wiring is formed on the surface through a plating process and / or an etching process, and further, build-up wiring is performed by separating and separating between the carrier resin and the metal foil. The board is completed. Wiring may be formed on the peeling surface of the metal foil after peeling and separation, or the entire surface of the 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. Moreover, a printed circuit board can be obtained even if an electronic component is mounted directly on a coreless buildup substrate before resin peeling.

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

(Metal foil with carrier)
<Experimental Examples 1 to 15>
A plurality of electrolytic copper foils (thickness 12 μm, rough surface roughness Rz jis 3.7 μm) were prepared, and nickel-zinc (Ni—) according to the following conditions was applied to the shiny (glossy) surface of each electrolytic copper foil. Zn) alloy plating treatment and chromate (Cr—Zn chromate) treatment were performed, and the ten-point average roughness (Rz cis: measured in accordance with JIS B 0601: 2001) of the bonded surface (here, S surface) was 1. After setting the thickness to 5 μm, a prepreg (FR-4 resin: glass transition temperature Tg = 140 ° C .; thickness 200 μm) manufactured by Nanya Plastic Co., Ltd. was bonded to the S surface of the electrolytic copper foil as a resin and hot pressed at 170 ° C. for 100 minutes. The copper foil with a carrier was produced.

(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 to 10 seconds

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

In addition, after apply | coating the aqueous solution of the metal alkoxide shown in Table 1 to the said glossy surface using a spray coater, it was made to dry in 100 degreeC air, and the prepreg and copper foil were bonded together. The conditions for using the metal alkoxide are shown in Table 1.

Further, assuming that some of the copper foils with a carrier have a thermal history during further heat treatment such as circuit formation on the copper foil with a carrier, the conditions described in Table 1 (here , 220 ° C. for 3 hours, 6 hours, and 9 hours).

The copper foil with a carrier obtained by hot pressing, and the copper foil with a carrier after the respective heat treatments for 3 hours, 6 hours, and 9 hours, and the plate-like carrier (resin after heating) The peel strength was measured. The results are shown in Table 1.

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

<Experimental Example 16>
In Experimental Example 1, when the copper foil and the prepreg were bonded together, copper with a carrier was used under the same conditions as in Experimental Example 1 except that neither the glossy surface of the copper foil nor the prepreg was treated with a metal alkoxide. A foil was prepared, and the peel strength at each stage and the working time were evaluated. The respective results are shown in Table 1 and Table 2.

Although it is not described in the table, the metal alkoxide is processed on the surface of the copper foil or the surface of the prepreg, and if it is processed under the same conditions with the same compound, the subsequent laminate It was found that the same results were obtained in the peel strength, the peel strength after heating, and the peelability.

(Build-up wiring board)
FR-4 prepreg (manufactured by Nanya Plastic Co., Ltd.) and copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., JTC 12 μm (product name)) are sequentially stacked on both sides of the copper foil with a carrier thus produced. A four-layer copper clad laminate was produced by hot pressing under the heating conditions shown in each table under the pressure of.

Next, a 100 μm diameter hole penetrating the copper foil on the surface of the four-layer copper-clad laminate and the insulating layer (cured prepreg) thereunder was drilled using a laser processing machine. Subsequently, electroless copper plating on the copper foil surface on the copper foil with 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, and copper plating by electrolytic copper plating The electrical connection was formed between the copper foil on the copper foil with a carrier and the copper foil on the surface of the four-layer copper-clad laminate. Next, a part of the copper foil on the surface of the four-layer copper-clad laminate was etched using a ferric chloride-based etchant to form a circuit. In this way, a four-layer buildup substrate was obtained.

Subsequently, in the 4-layer build-up board, the two-layer build-up wiring boards were obtained by peeling off and separating the plate-like carrier of the copper foil with carrier and the copper foil.

Subsequently, the copper foil that was in close contact with the plate-like carrier on the two sets of two-layer build-up wiring boards was etched to form a wiring to obtain two sets of two-layer build-up wiring boards. .

In each experimental example, a plurality of four-layer build-up substrates were produced, and for each, the degree of contact between the prepreg and the copper foil constituting the copper foil with carrier in the build-up substrate manufacturing process was confirmed visually. In a build-up wiring board using a copper foil with a carrier manufactured under conditions where the peel strength and the peel strength after heating are evaluated as “G”, the resin (plate carrier) of the copper foil with a carrier is destroyed during the build-up. It was able to peel without being.
As for the condition evaluated as “N”, the resin was destroyed at the time of build-up during the peeling operation of the copper foil in the carrier-attached copper foil, or the resin remained on the copper foil surface without being peeled off.
As for the conditions evaluated as “-”, the resin was peeled off without being destroyed during the copper foil peeling operation in the carrier-added copper foil during build-up, but the copper foil was removed without peeling operation. Sometimes peeled off.

DESCRIPTION OF SYMBOLS 10 Multilayer metal mold | die 11 Metal foil with a carrier 11a Metal foil 11b Metal alkoxide 11c Plate carrier 12 Prepreg 13 Inner core 14 Page 15 Book 16 Build-up layer

Claims (38)

1. A metal foil with a carrier made of a resin-made plate-like carrier and a metal foil that is detachably adhered to at least one surface of the carrier, and the plate-like carrier and the metal foil have the following formula:
   

   

   Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
   The metal foil with a carrier formed by laminating the aluminate compound, the titanate compound, the zirconate compound, the hydrolysis products thereof, and the condensates of the hydrolysis products alone or in combination.
2. The metal foil with a carrier according to claim 1, wherein the peel strength between the plate-like carrier and the metal foil is 10 gf / cm or more and 200 gf / cm or less.
3. The metal foil with a carrier according to claim 1 or 2, wherein the resinous plate-like carrier contains a thermosetting resin.
4. The metal foil with a carrier according to any one of claims 1 to 3, wherein the resin plate carrier is a prepreg.
5. The metal foil with a carrier according to claim 3 or 4, wherein the resin plate carrier has a glass transition temperature Tg of 120 to 320 ° C.
6. The metal foil with a carrier according to any one of claims 1 to 5, wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 µm or less.
7. The metal with a carrier according to any one of claims 1 to 6, wherein the surface of the metal foil not contacting the carrier has a ten-point average roughness (Rz jis) of 0.4 µm or more and 10.0 µm or less. Foil.
8. The metal foil with a carrier according to any one of claims 1 to 7, wherein the thickness of the metal foil is 1 µm or more and 400 µm or less.
9. The peel strength between the metal foil and the plate-like carrier after heating at 220 ° C. for 3 hours, 6 hours or 9 hours is 10 gf / cm or more and 200 gf / cm or less. A metal foil with a carrier according to claim 1.
10. The metal foil with a carrier according to any one of claims 1 to 9, wherein the metal foil is a copper foil.
11. On the surface of the metal foil, the following formula:
    

    

    Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
    The metal foil for printed wiring boards which has the aluminate compound, titanate compound, zirconate compound shown to these, these hydrolysis products, and the condensate of this hydrolysis product individually or in combination.
12. The compound acts on the surface of the metal foil on which the aluminate compound, titanate compound, zirconate compound, hydrolysis products thereof, and condensation products of the hydrolysis products are used alone or in combination. The metal foil for a printed wiring board according to claim 11, wherein the metal foil is subjected to a chromate treatment before being made.
13. The metal foil for printed wiring boards according to claim 11 or 12, wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 µm or less.
14. The printed wiring board according to any one of claims 11 to 13, wherein the surface of the metal foil not contacting the carrier has a ten-point average roughness (Rz jis) of 0.4 µm or more and 10.0 µm or less. Metal foil.
15. The metal foil for printed wiring boards according to any one of claims 11 to 14, wherein the metal foil is a copper foil.
16. On at least one surface, the following formula:
    

    

    Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
    A metal foil having an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensate of the hydrolysis product, either alone or in combination, and a resin plate on the surface Metal foil used for mechanically releasably adhering a cylindrical carrier.
17. The compound acts on the surface of the metal foil on which the aluminate compound, titanate compound, zirconate compound, hydrolysis products thereof, and condensation products of the hydrolysis products are used alone or in combination. The metal foil according to claim 16, wherein the metal foil is subjected to a chromate treatment before being made.
18. The metal foil according to claim 16 or 17, wherein a ten-point average roughness (Rz jis) of a side surface in contact with the carrier of the metal foil is 3.5 µm or less.
19. On at least one surface, the following formula:
    

    

    Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
    A resinous plate-like carrier having the aluminate compound, titanate compound, zirconate compound, hydrolysis products thereof, and condensates of the hydrolysis products alone or in combination.
20. On at least one surface, the following formula:
    

    

    Wherein R ¹ is an alkoxy group or a halogen atom, and R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms are halogen atoms Any one of these hydrocarbon groups substituted by: M is any one of Al, Ti, Zr, n is 0 or 1 or 2, m is an integer from 1 to M valence, At least one of R1 is an alkoxy group, where m + n is the valence of M, that is, 3 for Al and 4 for Ti and Zr)
    A plate carrier made of a resin having an aluminate compound, a titanate compound, a zirconate compound, a hydrolysis product thereof, and a condensation product of the hydrolysis product, either alone or in combination, on the surface A plate-like carrier used for applications in which a metal foil is peelably adhered.
21. A multilayer comprising laminating a resin on at least one metal foil side of the metal foil with a carrier according to any one of claims 1 to 10, and then repeatedly laminating the resin or the metal foil one or more times. A method for producing a metal-clad laminate.
22. A resin is laminated on the metal foil side of the metal foil with a carrier according to any one of claims 1 to 10, and then a resin, a single-sided or double-sided metal-clad laminate, or any one of claims 1 to 10. A method for producing a multilayer metal-clad laminate comprising laminating a metal foil with a carrier as described in 1 or a metal foil one or more times.
23. 23. The method for producing a multilayer metal-clad laminate according to claim 21 or 22, further comprising a step of peeling and separating the plate-like carrier and the metal foil of the metal foil with carrier.
24. 24. The method for producing a multilayer metal-clad laminate according to claim 23, comprising a step of removing a part or all of the separated and separated metal foil by etching.
25. A multilayer metal-clad laminate obtained by the production method according to any one of claims 21 to 24.
26. A method for manufacturing a buildup board, comprising a step of forming one or more buildup wiring layers on the metal foil side of the metal foil with a carrier according to any one of claims 1 to 10.
27. 27. The method of manufacturing a build-up board according to claim 26, wherein the build-up wiring layer is formed using at least one of a subtractive method, a full additive method, or a semi-additive method.
28. 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 10, and then a resin, a single-sided or double-sided wiring board, a single-sided or double-sided metal-clad laminate, A method for producing a build-up substrate, comprising laminating the metal foil with a carrier according to any one of 1 to 10 or the metal foil repeatedly one or more times.
29. 29. The method for manufacturing a build-up board according to claim 28, wherein the single-sided or double-sided wiring board, the single-sided or double-sided metal-clad laminate, the metal foil of the metal foil with carrier, the plate carrier of the metal foil with carrier, the metal foil, or the resin The manufacturing method of the buildup board | substrate which further includes the process of drilling a hole in and carrying out conductive plating to the side surface and bottom face of the said hole.
30. 30. The build-up board manufacturing method according to claim 28 or 29, wherein the metal foil constituting the single-sided or double-sided wiring board, the metal foil constituting the single-sided or double-sided metal-clad laminate, or the metal foil constituting the metal foil with carrier And the manufacturing method of the buildup board | substrate which further includes performing the process of forming wiring in at least one of metal foil once or more.
31. 11. The method according to claim 1, further comprising a step of contacting and laminating the resin plate side of the metal foil with a carrier according to any one of claims 1 to 10, wherein the metal foil is adhered to one surface on the surface on which the wiring is formed. The method for producing a build-up substrate according to any one of 28 to 30.
32. The metal foil with a carrier according to any one of claims 1 to 10, wherein a resin is laminated on the surface on which the wiring is formed, and the metal foil is adhered to both surfaces of the resin. The method for manufacturing a build-up substrate according to any one of claims 28 to 30, further comprising a step of laminating the layers.
33. The method for manufacturing a buildup substrate according to any one of claims 28 to 32, wherein at least one of the resins is a prepreg.
34. The buildup wiring board manufacturing method according to any one of claims 26 to 33, further comprising a step of peeling and separating the plate-like carrier of the metal foil with carrier and the metal foil. Method.
35. 35. The method for manufacturing a build-up wiring board according to claim 34, further comprising a step of removing a part or all of the metal foil adhered to the plate-like carrier by etching.
36. A build-up wiring board obtained by the manufacturing method according to claim 34 or 35.
37. A method for producing a printed circuit board, comprising a step of producing a build-up board by the production method according to any one of claims 26 to 33.
38. A method for producing a printed circuit board, comprising a step of producing a build-up wiring board by the production method according to claim 34 or 35.

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