TWI625229B - Metal foil, metal foil with release layer, laminate, printed wiring board, semiconductor package, electronic device, and printed wiring board manufacturing method - Google Patents

Abstract

The present invention provides a metal foil which is physically peeled off when the metal foil is bonded to a resin substrate by providing a release layer of the metal foil, thereby removing the metal foil from the resin substrate. In the step, the metal foil can be removed at a preferred cost without damaging the contour of the surface of the metal foil transferred onto the surface of the resin substrate, and the resins having different resin components can be bonded to each other with good adhesion. . The metal foil of the present invention has a surface profile: when a line is drawn on a photograph obtained by SEM imaging by at least one surface magnified to 3000 times magnification, and the number of metal particles falling on a straight line is counted, The number of particles in a straight line having a length of 10 μm (particle density = one/10 μm) is X, and the roughness Rz of the surface of the metal foil is Y, and the following formula (1) satisfies 2 to 9.

Description

Metal foil, metal foil with release layer, laminate, printed wiring board, semiconductor package, electronic device, and printed wiring board manufacturing method

The present invention relates to a metal foil, a metal foil with a release layer, a laminate, a printed wiring board, a semiconductor package, an electronic device, and a method of manufacturing a printed wiring board.

The mainstream method of forming a circuit for forming a printed wiring board and a semiconductor package substrate is a subtractive method. However, due to further fine wiring in recent years, M-SAP (Modified Semi-Additive Process) or half of the surface outline of a metal foil is used. New process methods such as addition methods have arisen.

In the new circuit forming process, as an example of the semi-additive method of the surface profile of the metal foil used in the latter, the following method is exemplified. In other words, first, the entire surface of the metal foil laminated on the resin substrate is etched, and the surface of the etched substrate on which the surface contour of the metal foil is transferred is opened by laser or the like, and the opening for conducting the opening is applied. Electrolytic copper plating layer, covering the surface of the electroless copper plating with a dry film, removing the dry film of the circuit forming portion by UV exposure and development, performing electrolytic copper plating on the electroless copper plating surface not covered by the dry film, and drying the film After the peeling, the electroless copper plating layer is etched (flashing, rapid etching) by an etching solution containing sulfuric acid or hydrogen peroxide water, thereby forming a fine circuit (Patent Document 1 and Patent Document 2).

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-196863

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-242975

However, in the semi-additive method using the contour of the surface of the metal foil, the metal is favorably transferred to the surface of the resin substrate without damaging the contour of the surface of the metal foil, and the metal is preferably used at a preferable cost. There is still room for research in terms of foil removal.

In addition, in recent years, research and development of a technique for producing a laminate in which a resin and a resin are bonded together have been studied. In this case, when the resin components are different, sufficient adhesion cannot be obtained, and it is necessary to make the resin on one side have irregularities and to improve the adhesion due to the anchoring effect. There are physical processing, chemical processing, and the like for leaving the unevenness on the surface of the cured resin, but depending on the physical properties or chemical properties of the resin, such methods are not suitable. Further, in the case where the resin area layer is the same or different resin, if the unevenness of the resin surface is not appropriate, bubbles (air accumulation) may remain between the two resins after lamination, resulting in poor appearance and two Poor adhesion between the resins. Therefore, further development is expected in a technique for suppressing the generation of bubbles between the subsequent resins and bonding the resins having different resin components to each other with good adhesion.

As a result of intensive studies, the present inventors have found that the resin substrate can be physically peeled off when the metal foil is bonded to the resin substrate by providing a release layer on the metal foil having surface irregularities, thereby forming the metal foil. In the step of removing the resin substrate, the metal foil can be removed at a preferable cost without damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate. Further, it has been found that the metal foil having good adhesion to the resin and having specific surface irregularities is bonded to the resin to be cured, and then the metal foil is removed to transfer the unevenness to the surface of the resin. The resins having different resin components are bonded to each other with good adhesion.

The present invention, which is completed based on the above findings, is a metal foil having a surface profile which is drawn on a photograph obtained by SEM photographing at least one surface to a magnification of 3000 times. When the number of the metal particles on the straight line is counted, the number of particles (particle density = one/10 μm) per 10 μm of the straight line is X, and the roughness Rz of the surface of the metal foil is Y. The formula (1) satisfies 2 to 9.

In another aspect, the present invention is a metal foil having a surface profile: when the number of identifiable metal particles is counted on a photograph obtained by SEM imaging at least 10,000 times magnification of at least one surface, The number of particles per 10 μm ² (particle density = /10 μm ² ) is Z, and the roughness Rz of the surface of the metal foil is Y, and the following formula (2) satisfies 2 to 16.

In one embodiment, the metal foil of the present invention has a thickness of 9 to 70 μm.

In another embodiment of the metal foil of the present invention, the metal foil is a copper foil.

In still another embodiment of the metal foil of the present invention, the metal foil has a surface The surface of the surface profile is provided with one or more layers selected from the group consisting of a heat resistant layer, a rust preventive layer, a chromate treated layer, and a decane coupling treatment layer.

In still another embodiment, the metal foil of the present invention is provided with a resin layer on a surface of one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate-treated layer, and a decane coupling treatment layer.

In still another embodiment of the metal foil of the present invention, the resin layer is followed by a resin, a primer, or a resin in a semi-hardened state.

In another aspect, the present invention provides a metal foil with a release layer, comprising: a metal foil of the present invention; and a release layer disposed on a surface side of the metal foil having a surface profile, and When the resin layer is bonded to the metal foil on the side of the mold release layer, the resin substrate can be peeled off.

In one embodiment of the metal foil with a release layer of the present invention, the release layer is used alone or in combination of several kinds of aluminate compounds, titanate compounds, zirconates, and the like represented by the following formulas. a hydrolyzate and a condensate of the hydrolyzate, (R ¹ ) _m -M-(R ² ) _n

(wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms are substituted with a halogen atom; Any of the hydrocarbon groups, M is any one of Al, Ti, Zr, n is 0, 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one R ¹ is an alkoxy group; Furthermore, m+n is the valence of M, that is, 3 in the case of Al and 4 in the case of Ti and Zr.

In still another embodiment of the metal foil with a release layer of the present invention, the release layer is used singly or in combination of a plurality of decane compounds represented by the following formula, a hydrolyzed product thereof, and a condensate of the hydrolysis product. to make,

(wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms are substituted with a halogen atom; Any of the hydrocarbon groups in the group, R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms Any one of these groups substituted with a halogen atom).

In still another embodiment of the metal foil with a release layer of the present invention, the release layer is formed by using a compound having two or less sulfhydryl groups in the molecule.

In still another embodiment of the metal foil with a release layer of the present invention, a resin layer is provided on the surface of the release layer.

In still another aspect, the present invention provides a laminate comprising the metal foil of the present invention and a resin substrate.

In one embodiment of the laminate of the present invention, the resin substrate is a prepreg or a thermosetting resin.

In another aspect, the invention is a printed wiring board having the gold of the invention It is a foil or a metal foil with a release layer of the present invention.

In another aspect, the present invention is a semiconductor package comprising the printed wiring board of the present invention.

In another aspect, the invention is an electronic device comprising the printed wiring board of the invention or the semiconductor package of the invention.

In another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: laminating a resin substrate with a metal foil of the present invention or a metal foil with a release layer of the present invention; The metal foil or the metal foil with the release layer is peeled off from the resin substrate without etching, and a resin base obtained by transferring the surface profile of the metal foil or the metal foil with the release layer to the release surface is obtained. And a step of forming a circuit on the peeling surface side of the resin substrate on which the surface profile is transferred.

In one embodiment, the method for producing a printed wiring board according to the present invention is a circuit-plated pattern or a printed pattern formed on the peeling surface side of the resin substrate on which the surface profile is transferred.

In another aspect, the present invention provides a method of manufacturing a printed wiring board, comprising the steps of: laminating a resin substrate with a metal foil of the present invention or a metal foil with a release layer of the present invention; The metal foil or the metal foil with the release layer is peeled off from the resin substrate without etching, and a resin base obtained by transferring the surface profile of the metal foil or the metal foil with the release layer to the release surface is obtained. And a step of providing a layer on the side of the peeling surface of the resin substrate on which the surface profile is transferred.

In still another embodiment of the method for producing a printed wiring board according to the present invention, the resin constituting the layered layer contains a liquid crystal polymer or polytetrafluoroethylene.

The resin substrate can be physically peeled off by attaching the metal foil to the resin substrate by providing the release layer of the metal foil, so that the step of removing the metal foil from the resin substrate can be performed without damaging the transfer. The metal foil is removed at a preferred cost in the case of the contour of the surface of the metal foil on the surface of the resin substrate. Further, the resins having different resin components can be bonded to each other with good adhesion.

Fig. 1 shows a schematic example of a semi-additive method using a contour of a copper foil.

(metal foil, metal foil with release layer)

In one aspect, the metal foil of the present invention is a metal foil having a surface profile: a line drawn on a photograph obtained by SEM imaging at least one surface, that is, one surface or both surfaces is enlarged to a magnification of 3000 times. When the number of metal particles falling on the straight line is counted, the number of particles (particle density = one/10 μm) per 10 μm of the straight line is X, and the roughness Rz of the surface of the metal foil is Y. At this time, the following formula (1) satisfies 2 to 9.

Further, the metal foil with a release layer of the present invention includes: the metal foil; and a release layer provided on a surface side of the metal foil having a surface contour, and the metal foil is attached to the metal foil from the side of the release layer The above resin substrate may be peeled off when the resin substrate is combined.

Thus, the metal foil is attached to the resin by the metal foil with or without the release layer. The resin substrate at the time of the substrate can be physically peeled off, so that the step of removing the metal foil from the resin substrate can be preferably performed without damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate. The cost is to remove the metal foil.

In the present specification, the "surface" and the "surface of the metal foil" are provided with a roughened layer, a heat-resistant layer, a rustproof layer, a chromate-treated layer, a decane coupling treatment layer, and a surface of the metal foil. In the case of a surface treatment layer such as a release layer, it means a surface (the outermost surface) after the surface treatment layer is provided.

When the number of metal particles falling on the straight line is counted by drawing a straight line on a photograph obtained by SEM photographing the surface of the metal foil to a magnification of 3000 times, the number of particles per 10 μm in length of the straight line is When the particle density is set to X and the roughness Rz of the surface of the metal foil is Y, the formula (1) satisfies the surface profile of 2 to 9, and therefore has the effect of bonding the metal foil. The resin substrate at the time of the resin substrate can be physically peeled off, so that the step of removing the metal foil from the resin substrate can be performed without damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate. The metal foil is removed at a preferred cost, and the surface of the resin substrate after peeling off the metal foil is carried out without voids (or very few voids), so that a laminated member such as a circuit or a resin or a build-up layer can be provided with good adhesion. Resin substrate surface.

When the formula (1) is less than 2, when the metal foil is bonded to the resin substrate and the metal foil is peeled off, the surface of the resin substrate obtained has a small unevenness, and the adhesion to the resin is insufficient. When the problem exceeds 9, the problem arises that the physical peeling of the resin substrate when the metal foil is bonded to the resin substrate is difficult, and the metal foil is damaged in the step of removing the metal foil from the resin substrate. The outline of the surface of the metal foil printed on the surface of the resin substrate, in addition, the metal foil The uneven shape of the surface of the resin substrate after peeling is too deep, so that the laminated member such as a circuit or a resin or a build-up layer does not follow the uneven shape. The formula (1) is preferably 4 to 8, more preferably 5 to 6.

Further, in another aspect, the metal foil of the present invention is a metal foil having a surface profile obtained by performing SEM photography on at least one surface, that is, one surface or both surfaces, to a magnification of 10,000 times. When counting the number of metal particles that can be confirmed, the number of particles per 10 μm ² (particle density = 10 μm ² ) is Z, and the roughness Rz of the surface of the metal foil is Y. (2) Meet 2~16.

Further, the metal foil with a release layer of the present invention includes: the metal foil; and a release layer provided on a surface side of the metal foil having a surface contour, and the metal foil is attached to the metal foil from the side of the release layer The above resin substrate may be peeled off when the resin substrate is combined.

In addition, when counting the number of the metal particles, when there is no particle shape, it is one/10 μm ² . In this manner, the resin substrate can be physically peeled off when the metal foil is attached to the resin substrate by the metal foil or without the release layer, so that the step of removing the metal foil from the resin substrate can be performed. The metal foil is removed at a preferred cost without damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate.

When the number of metal particles that can be confirmed is counted on a photograph obtained by SEM imaging by magnifying the surface of the metal foil to a magnification of 10,000 times, the number of particles per 10 μm ² (particle density = one/10 μm ² ) is set. When the roughness Rz of the surface of the metal foil is Y, the formula (2) satisfies the surface profile of 2 to 16, so that the resin substrate can be physically peeled off when the metal foil is bonded to the resin substrate. Therefore, in the step of removing the metal foil from the resin substrate, the effect of removing the metal foil at a preferred cost without damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate, and thus, The surface of the resin substrate after peeling the metal foil is closely followed by the voids (or the voids), so that a laminated member such as a circuit or a resin or a build-up layer can be provided on the surface of the resin substrate with good adhesion.

When the formula (2) is less than 2, when the metal foil is bonded to the resin substrate and the metal foil is peeled off, the unevenness of the surface of the resin substrate is small, and the adhesion to the resin is insufficient. When the problem exceeds 16, the problem arises that the physical peeling of the resin substrate when the metal foil is bonded to the resin substrate is difficult, and the metal foil is damaged in the step of removing the metal foil from the resin substrate. The outline of the surface of the metal foil printed on the surface of the resin substrate, and the uneven shape of the surface of the resin substrate after peeling off the metal foil is too deep, so that the laminated member such as a circuit or a resin or a build-up layer does not follow the uneven shape. The formula (2) is preferably 6 to 12, more preferably 8 to 12.

In the present specification, the "metal particles" may be roughened particles or may be a convex portion (for example, a mountain-shaped convex portion) on the deposition surface side (matte side) of the metal foil.

Furthermore, the release layer may also be provided on both sides of the metal foil. Further, lamination or lamination of the metal foil and the resin substrate, and lamination of the laminated member such as a circuit or a resin or a buildup layer to the resin substrate may be performed by pressure bonding.

The metal foil (also referred to as a green foil) is not particularly limited, and a copper foil, an aluminum foil, a nickel foil, a copper alloy foil, a nickel alloy foil, an aluminum alloy foil, a stainless steel foil, an iron foil, an iron alloy foil, or the like can be used.

The thickness of the metal foil (raw foil) is not particularly limited, and can be, for example, 5 to 105 μm. Further, the thickness of the surface-treated copper foil is preferably from 9 to 70 μm, more preferably from 12 to 35 μm, still more preferably from 18 to 35 μm, in terms of easy peeling from the resin substrate.

Hereinafter, the copper foil will be described as an example of a metal foil (raw foil). The method for producing the copper foil (raw foil) is not particularly limited, and for example, electricity can be produced by the following electrolysis conditions. Solve copper foil.

Electrolytic conditions for electrolytic foil:

Electrolyte composition:

Cu: 30~190g/L

H ₂ SO ₄ : 100~400g/L

Chloride ion (Cl ^- ): 10 to 200 ppm by mass

Animal glue: 1~10ppm

(Optional bis(3-sulfopropyl) disulfide (SPS): 10~100ppm)

Electrolyte temperature: 25~80°C

Electrolysis time: 10~300 seconds (adjusted according to copper thickness and current density)

Current density: 50~150A/dm ²

Electrolyte line speed: 1.5~5m/sec

In addition, in the present specification, the remaining portions of the liquid such as the liquid used in the treatment of forming the release layer by the electrolytic solution, the plating solution, the decane coupling treatment liquid, or the treatment liquid for surface treatment are not particularly described. For water.

The number of particles per 10 μm length (particle density = one/10 μm) = X, the roughness of the surface Rz = Y, X × Y of the formula (1), and the number of particles per 10 μm ² (particle density = The √Z×Y of the formula (2) composed of the roughness of the surface λμm ² )=Z and the surface roughness Rz=Y can be adjusted by the above electrolysis conditions. For example, under the same foil thickness, if the linear velocity of the electrolyte is increased within the above range, Y can be reduced without changing X or Z, that is, √X×Y or √Z×Y Reduced. Further, if the chloride ion concentration is lowered within the above range and the current density is lowered within the above range, X or Z can be made to be reduced without changing Y, that is, √X×Y or √Z× Y decreases. Further, if only the foil thickness is increased by the adjustment of the electrolysis time, X or Z can be decreased and Y can be increased. Further, if the animal gum concentration is increased within the above range, Y can be increased without changing X or Z, that is, √X×Y or √Z×Y can be increased. Further, if the animal gum concentration is increased within the above range and the current density is increased, X, Y, and Z are all reduced, that is, √X×Y or √Z×Y is remarkably reduced. Thus, the parameters may be adjusted in accordance with the degree of peelability required and the required adhesion to the laminated member.

In the present invention, the removal of the metal foil from the resin substrate means that the metal foil is removed from the resin substrate by chemical treatment such as etching, or the resin substrate is physically peeled off from the metal foil by peeling or the like. When the resin substrate is removed after bonding to the metal foil of the present invention as described above, the resin substrate and the metal foil are separated from the release layer. In this case, a part of the peeling layer, the roughened particles of the following metal foil, the heat-resistant layer, the rust-preventing layer, the chromate-treated layer, and the decane coupling treatment layer may remain on the peeling surface of the resin substrate, but it is preferably In the absence of residue.

In the metal foil with a release layer of the present invention, it is preferable that the peeling strength when the resin substrate is peeled off when the resin substrate is bonded to the metal foil from the side of the release layer is 200 gf/cm or less. When the control is carried out in this manner, the physical peeling of the resin substrate becomes easy, and the contour of the surface of the metal foil is more favorably transferred to the resin substrate. The peel strength is more preferably 150 gf/cm or less, still more preferably 100 gf/cm or less, still more preferably 50 gf/cm or less, and typically 1 to 200 gf/cm, and more typically 1 to 150 gf/cm.

Next, the release layer which can be used in the present invention will be described.

(1) decane compound

By using a decane compound having a structure represented by the following formula, or a hydrolyzate thereof, or a condensate of the hydrolyzate (hereinafter, abbreviated as a decane compound) or a mixed use number When the metal foil and the resin substrate are bonded together, the adhesion is moderately lowered, and the peel strength can be adjusted to the above range.

formula:

(wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms are substituted with a halogen atom; Any of the hydrocarbon groups in the group, R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms Any one of the groups substituted with a halogen atom)

The decane compound must have at least one alkoxy group. Substituting a hydrocarbon group in a group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom, in the absence of an alkoxy group In the case of a base, there is a tendency that the adhesion between the resin substrate and the metal foil is excessively lowered. Further, the decane compound must have at least one hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or any one of the groups in which one or more hydrogen atoms are substituted with a halogen atom. This is because when the hydrocarbon group is not present, the adhesion between the resin substrate and the metal foil tends to increase. Further, the alkoxy group also contains an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom.

In order to adjust the peeling strength of the resin substrate and the metal foil to the above range, the decane compound preferably has three alkoxy groups and one of the above hydrocarbon groups (hydrocarbon groups containing one or more hydrogen atoms substituted with a halogen atom) ). In the above formula, it is meant that both R ³ and R ⁴ are alkoxy groups.

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

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

The alkyl group is not limited and may, for example, be a methyl group, an ethyl group, a normal or an isopropyl group, a normal or an isobutyl group, a n-, iso- or neopentyl group, a n-hexyl group, an n-octyl group or a n-decyl group. The linear or branched carbon number is from 1 to 20, preferably from 1 to 10 carbon atoms, more preferably from 1 to 5 carbon atoms.

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

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

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

Preferred examples of the decane compound include methyltrimethoxydecane, ethyltrimethoxydecane, n- or isopropyltrimethoxynonane, n-, iso- or tert-butyltrimethoxydecane, and Iso- or neopentyltrimethoxydecane, hexyltrimethoxydecane, octyltrimethoxydecane, decyltrimethoxydecane, phenyltrimethoxydecane;alkyl-substituted phenyltrimethoxynonane (for example, Methyl)phenyltrimethoxydecane), methyltriethoxydecane, ethyltriethoxydecane, n- or isopropyltriethoxydecane, n-, iso- or tert-butyltriethoxy Decane, Butyl triethoxy decane, hexyl triethoxy decane, octyl triethoxy decane, decyl triethoxy decane, phenyl triethoxy decane, alkyl substituted phenyl triethoxy decane ( For example, p-(methyl)phenyltriethoxydecane), (3,3,3-trifluoropropyl)trimethoxynonane, and tridecafluorooctyltriethoxydecane, methyltrichlorodecane, Dimethyldichlorodecane, trimethylchlorodecane, phenyltrichlorodecane, trimethylfluorodecane, dimethyldibromodecane, diphenyldibromodecane, hydrolyzed products thereof, and the like A condensate of a hydrolyzed product or the like. Among these, from the viewpoint of easiness of obtaining, propyltrimethoxydecane, methyltriethoxydecane, hexyltrimethoxydecane, phenyltriethoxydecane, decyltrimethoxy is preferred. Base decane.

In the step of forming the release layer, the decane compound can be used in the form of an aqueous solution. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is particularly effective when a highly hydrophobic decane compound is used. The aqueous solution of the decane compound promotes hydrolysis of the alkoxy group by stirring, and if the stirring time is long, the condensation of the hydrolyzate is promoted. In general, when a decane compound which is sufficiently subjected to hydrolysis and condensation after a sufficient stirring time is used, the peel strength of the resin substrate and the metal foil tends to decrease. Therefore, the peel strength can be adjusted by adjusting the stirring time. The stirring time after dissolving the decane compound in water is not limited, and may be, for example, 1 to 100 hours, and typically 1 to 30 hours. Of course, there is also a method of using without stirring.

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

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

(2) Compounds having two or less sulfhydryl groups in the molecule

The release layer is composed of a compound having two or less sulfhydryl groups in the molecule, and even if the resin substrate is bonded to the metal foil by interposing the release layer, the adhesion is appropriately lowered, and the peel strength can be adjusted.

However, when a compound having three or more mercapto groups in the molecule or a salt thereof is interposed between the resin substrate and the metal foil and bonded thereto, the peel strength is not satisfied. The reason is considered to be that if there are excessive sulfhydryl groups in the molecule, there are excessively generated sulfur bonds, disulfide bonds or polysulfide bonds by chemical reaction of sulfhydryl groups with each other, or sulfhydryl groups and plate-shaped carriers, or sulfhydryl groups and metal foils. A strong three-dimensional crosslinked structure is formed between the resin substrate and the metal foil, whereby the peel strength is increased. Such an example is disclosed in Japanese Laid-Open Patent Publication No. 2000-196207.

Examples of the compound having two or less mercapto groups in the molecule include a mercaptan, a dithiol, a sulfuric acid or a salt thereof, a dithiocarboxylic acid or a salt thereof, sulfuric acid or a salt thereof, and disulfuric acid or As the salt, at least one selected from the group consisting of these can be used.

A thiol group having a fluorenyl group in the molecule is represented, for example, by R-SH. Here, R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group.

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

The hydroxy group of the carboxylic acid-based organic carboxylic acid is substituted with a fluorenyl group, for example, by R-CO -SH said. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the sulfuric acid can also be used in the form of a salt. Further, a compound having two thiocarboxylic acid groups can also be used.

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

The hydroxyl group of the sulfuric acid-based organic sulfonic acid is substituted with a fluorenyl group, and is represented, for example, by R(SO ₂ )-SH. R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, sulfuric acid can also be used in the form of a salt.

The two hydroxyl groups of the disulfonic acid-based organic disulfonic acid are each substituted with a fluorenyl group, for example, represented by R-((SO ₂ )-SH) ₂ . R represents an aliphatic or aromatic hydrocarbon group or a heterocyclic group which may further contain a hydroxyl group or an amine group. Further, the two sulfonic acid groups may be bonded to the same carbon, respectively, or may be bonded to carbons different from each other. Further, disulfuric acid can also be used in the form of a salt.

Here, as the preferred aliphatic hydrocarbon group for R, an alkyl group or a cycloalkyl group may be mentioned, and the hydrocarbon group may include either or both of a hydroxyl group and an amine group.

Further, the alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a normal or an isopropyl group, a normal or an isobutyl group, a normal or an iso-pentyl group, a n-hexyl group, a n-octyl group, and a positive group. The linear or branched carbon number such as a mercapto group is 1 to 20, preferably a carbon number of 1 to 10, more preferably an alkyl group having 1 to 5 carbon atoms.

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

Further, as a preferred aromatic hydrocarbon group for R, a phenyl group, a An alkyl-substituted phenyl group (for example, tolyl, xylyl), 1- or 2-naphthyl, an anthracenyl group or the like having 6 to 20 carbon atoms, preferably 6 to 14 aryl groups, and the hydrocarbon groups may contain a hydroxyl group. Either or both of the amine groups.

Further, as a preferred heterocyclic group for R, there may be mentioned imidazole, triazole, tetrazole, benzimidazole, benzotriazole, thiazole, benzothiazole, and may contain either or both of a hydroxyl group and an amine group. By.

Preferred examples of the compound having two or less mercapto groups in the molecule include 3-mercapto-1,2-propanediol, 2-mercaptoethanol, 1,2-ethanedithiol, and 6-mercapto-1-hexa Alcohol, 1-octyl mercaptan, 1-dodecanethiol, 10-hydroxy-1-dodecanethiol, 10-carboxy-1-dodecanethiol, 10-amino-1-dodecane Mercaptan, sodium 1-dodecyl mercaptan sulfonate, thiophenol, thiobenzoic acid, 4-amino thiophenol, p-toluene thiol, 2,4-dimethyl benzene thiol, 3-mercapto -1,2,4-triazole, 2-mercaptobenzothiazole. Among these, from the viewpoint of water solubility and waste treatment, 3-mercapto-1,2-propanediol is preferred.

In the step of forming the release layer, a compound having two or less mercapto groups in the molecule can be used in the form of an aqueous solution. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is particularly effective when a compound having two or less mercapto groups in a molecule having high hydrophobicity is used.

When the concentration of the compound having two or less sulfhydryl groups in the molecule is high in the aqueous solution, the peel strength of the resin substrate and the metal foil tends to decrease, and the concentration of the compound having two or less sulfhydryl groups in the molecule can be adjusted. Adjust the peel strength. The concentration in the aqueous solution of the compound having two or less sulfhydryl groups in the molecule is not limited, and may be 0.01 to 10.0% by weight, and typically 0.1 to 5.0% by weight.

The pH of the aqueous solution of the compound having 2 or less sulfhydryl groups in the molecule is not particularly It is not limited and 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 of not requiring special pH adjustment, it is preferably a pH in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH in the range of 7.0 to 9.0.

(3) Metal alkoxide

The aluminate compound, the titanate compound, the zirconate compound, or the hydrolyzate thereof, or the condensate of the hydrolyzate may be used alone or in combination (hereinafter, abbreviated as The metal alkoxide) constitutes a release layer. The resin substrate and the metal foil are bonded to each other by interposing the release layer, whereby the adhesion is appropriately lowered, and the peel strength can be adjusted.

(R ¹ ) _m -M-(R ² ) _n

Wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or a group in which one or more hydrogen atoms are substituted with a halogen atom Any one of the hydrocarbon groups, M is any one of Al, Ti, and Zr, n is 0, 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one R ¹ is an alkoxy group. Furthermore, m+n is the valence of M, that is, 3 in the case of Al and 4 in the case of Ti and Zr.

The metal alkoxide must have at least one alkoxy group. Substituting a hydrocarbon group in a group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or a hydrocarbon group in which one or more hydrogen atoms are substituted with a halogen atom, in the absence of an alkoxy group In the case of a base, there is a tendency that the adhesion between the resin substrate and the metal foil is excessively lowered. Further, the metal alkoxide must have any one of 0 to 2 hydrocarbon groups selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms substituted with a halogen atom. a hydrocarbon group. The reason is: with 3 In the case of the above hydrocarbon group, the adhesion between the resin substrate and the metal foil tends to be excessively lowered. Further, the alkoxy group also contains an alkoxy group in which one or more hydrogen atoms are substituted with a halogen atom. The metal alkoxide preferably has two or more alkoxy groups, one or two of the above hydrocarbon groups (containing one or more hydrogen atoms) in terms of adjusting the peeling strength of the resin substrate and the metal foil to the above range. A hydrocarbon group substituted with a halogen atom).

Further, the alkyl group is not limited, and examples thereof include a methyl group, an ethyl group, a normal or an isopropyl group, a normal or an isobutyl group, a normal or an iso-pentyl group, a n-hexyl group, a n-octyl group, and a positive group. The linear or branched carbon number such as a mercapto group is 1 to 20, preferably a carbon number of 1 to 10, more preferably an alkyl group having 1 to 5 carbon atoms.

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

Further, examples of the preferred aromatic hydrocarbon group for R ² include a phenyl group, an alkyl group-substituted phenyl group (for example, a tolyl group, a xylyl group), a 1- or 2-naphthyl group, and a fluorenyl group. 6 to 20, preferably 6 to 14 aryl groups, which may comprise either or both of a hydroxyl group and an amine group. One or more hydrogen atoms of the hydrocarbon groups may be substituted with a halogen atom, and for example, may be substituted with a fluorine atom, a chlorine atom, or a bromine atom.

Examples of preferred aluminate compounds include trimethoxy aluminum, methyl dimethoxy aluminum, ethyl dimethoxy aluminum, n- or isopropyl dimethoxy aluminum, ortho, x or Tributyldimethoxyaluminum, n-, iso- or neopentyldimethoxyaluminum, hexyldimethoxyaluminum, octyldimethoxyaluminum, decyldimethoxyaluminum, phenyldimethoxy Aluminium-substituted phenyldimethoxyaluminum (for example, p-(methyl)phenyldimethoxyaluminum), dimethylmethoxyaluminum, triethoxyaluminum, methyldiethoxyaluminum , ethyldiethoxyaluminum, n- or isopropyldiethoxyaluminum, n-, iso- or tert-butyldiethoxyaluminum, pentyldiethoxyaluminum, hexyldiethoxyaluminum, octyl Diethoxy aluminum, sulfhydryl Aluminum ethoxylate, phenyldiethoxyaluminum, alkyl substituted phenyldiethoxyaluminum (for example, p-(methyl)phenyldiethoxyaluminum), dimethylethoxyaluminum, triisopropyl Aluminium oxy, methyl diisopropoxy aluminum, ethyl aluminum diisopropoxide, n- or isopropyl diethoxy aluminum, n-, iso- or tert-butyl diisopropoxy aluminum, pentyl Aluminum diisopropoxide, aluminum hexyl diisopropoxide, aluminum octyl diisopropoxide, aluminum decyl diisopropoxide, aluminum phenyl diisopropoxide, alkyl substituted phenyl diisopropyl Aluminium oxide (for example, p-(methyl)phenyl diisopropoxy aluminum), dimethyl isopropoxide aluminum, (3,3,3-trifluoropropyl)dimethoxy aluminum, and thirteen Fluorooctyldiethoxyaluminum, methyldichloroaluminum, dimethylchloroaluminum, dimethylchloroaluminum, phenyldichloroaluminum, dimethylfluoroaluminum, dimethylbromoaluminum, diphenylbromoaluminum And the hydrolyzed product, the condensate of the hydrolyzed product, and the like. Among these, from the viewpoint of easiness of acquisition, trimethoxy aluminum, triethoxy aluminum, and aluminum triisopropoxide are preferred.

Examples of preferred titanate compounds include tetramethoxytitanium, methyltrimethoxytitanium, ethyltrimethoxytitanium, n- or isopropyltrimethoxytitanium, n-, iso- or tert-butyl Titanium trimethoxy, n-, iso- or neopentyltrimethoxytitanium, hexyltrimethoxytitanium, octyltrimethoxytitanium, decyltrimethoxytitanium, phenyltrimethoxytitanium; alkyl substituted phenyl Trimethoxytitanium (for example, p-(meth)phenyltrimethoxytitanium), dimethyldimethoxytitanium, tetraethoxytitanium, methyltriethoxytitanium, ethyltriethoxytitanium, Ortho- or isopropyl triethoxytitanium, n-, iso- or tert-butyltriethoxytitanium, pentyltriethoxytitanium, hexyltriethoxytitanium, octyltriethoxytitanium, fluorenyl Triethoxytitanium, phenyltriethoxytitanium, alkyl substituted phenyltriethoxytitanium (for example, p-(meth)phenyltriethoxytitanium), dimethyldiethoxytitanium, tetra Titanium isopropoxide, titanium methyl triisopropoxide, titanium triisopropoxide, titanium or n-butyl triethoxyoxide, n-, iso- or tert-butyl triisopropoxide titanium, Pentyl triisopropoxy titanium, hexyl triisopropoxy , Titanium triisopropoxide octyl, decyl titanium triisopropoxide, phenyl titanium triisopropoxide, alkyl substituted phenyl titanium triisopropoxide (e.g. (methyl)phenyltriisopropoxytitanium), dimethyldiisopropoxytitanium, (3,3,3-trifluoropropyl)trimethoxytitanium, and tridecafluorooctyltriethoxy Titanium, methyltrichlorotitanium, dimethyldichlorotitanium, trimethylchlorotitanium, phenyltrichlorotitanium, dimethyldifluorotitanium, dimethyldibromotitanium, diphenyldibromotitanium, The hydrolyzed product, the condensate of the hydrolyzed product, and the like. Among these, from the viewpoint of easiness of acquisition, tetramethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium are preferable.

As a preferable example of the zirconate compound, tetramethoxy zirconium, methyltrimethoxyzirconium, ethyltrimethoxyzirconium, n- or isopropyltrimethoxyzirconium, ortho, iso- or tert-butyl can be mentioned. Trimethyl zirconium, n-, iso- or neopentyltrimethoxy zirconium, hexyltrimethoxy zirconium, octyltrimethoxyzirconium, decyltrimethoxyzirconium, phenyltrimethoxyzirconium; alkyl substituted phenyl Trimethoxy zirconium (for example, p-(methyl)phenyltrimethoxyzirconium), dimethyldimethoxyzirconium, tetraethoxyzirconium, methyltriethoxyzirconium, ethyltriethoxyzirconium, N- or isopropyltriethoxy zirconium, n-, iso- or tert-butyltriethoxy zirconium, pentyltriethoxyzirconium, hexyltriethoxyzirconium, octyltriethoxyzirconium, fluorenyl Triethoxy zirconium, phenyltriethoxy zirconium, alkyl substituted phenyl triethoxy zirconium (for example, p-(methyl)phenyltriethoxy zirconium), dimethyldiethoxyzirconium, tetra Zirconium isopropoxide, zirconium methyl triisopropoxide, zirconium ethyl triisopropoxide, zirconium n- or isopropyl triethoxy, n-, iso- or tert-butyl triisopropoxy zirconium, Pentyl triisopropoxy zirconium, hexyl triisopropoxy , octyl triisopropoxy zirconium, decyl triisopropoxy zirconium, phenyl triisopropoxy zirconium, alkyl substituted phenyl triisopropoxy zirconium (for example, p-(methyl)phenyl triiso Titanium propoxide, zirconium dimethyl diisopropoxide, zirconium (3,3,3-trifluoropropyl)trimethoxy, and trifluorooctyltriethoxyzirconium, methyltrichlorozirconium , dimethyl zirconium chloride, trimethyl zirconium chloride, phenyl trichlorozirconium, dimethyl difluoro zirconium, dimethyl dibromo zirconium, diphenyl dibromo zirconium, hydrolyzed products thereof, and A condensate or the like of the hydrolysis product. Among these, from the viewpoint of easiness of acquisition, tetramethoxy zirconium, tetraethoxy zirconium, and tetraisopropoxy zirconium are preferable.

In the step of forming the release layer, the metal alkoxide may be used in the form of an aqueous solution. In order to improve the solubility in water, an alcohol such as methanol or ethanol may be added. The addition of an alcohol is particularly effective when a metal alkoxide having a higher hydrophobicity is used.

When the concentration of the metal alkoxide in the aqueous solution is high, the peel strength of the resin substrate and the metal foil tends to decrease, and the peel strength can be adjusted by adjusting the metal alkoxide concentration. The concentration in the aqueous solution of the metal alkoxide is not limited, and may be 0.001 to 1.0 mol/L, and typically 0.005 to 0.2 mol/L.

The pH of the aqueous solution of the metal alkoxide is not particularly limited and can be utilized 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 of not requiring special pH adjustment, it is preferably a pH in the range of 5.0 to 9.0 in the vicinity of neutrality, and more preferably a pH in the range of 7.0 to 9.0.

(4) Others

A known release material such as a oxime release agent or a resin film having releasability can be used for the release layer.

The metal foil of the present invention may be provided in a group consisting of a roughened layer, a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer on the surface of the metal foil having a surface profile. More than one layer. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. The chromate treatment layer may also contain elements such as cobalt, iron, nickel, molybdenum, zinc, bismuth, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (may be metals, alloys, oxides, nitrides, sulfides). Any form). Specific examples of the chromate-treated layer include a chromate treatment layer treated with an aqueous solution of chromic anhydride or potassium dichromate, or a chromate treatment treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc. Layers, etc.

The roughening treatment layer can be formed, for example, by the following treatment.

[spherical roughening]

The spherical roughening particles are formed using a copper roughening plating bath described below composed of Cu, H ₂ SO ₄ , and As.

‧ liquid composition 1

CuSO ₄ . 5H ₂ O 78~196g/L

Cu 20~50g/L

H ₂ SO ₄ 50~200g/L

Arsenic 0.7~3.0g/L

(electrolytic plating temperature 1) 30~76°C

(current condition 1) current density 35~105A/dm ² (above the limit current density of the bath)

(plating time 1) 1~240 seconds

Then, in order to prevent the peeling of the roughened particles and to improve the peeling strength, the coating was performed by a copper electrolytic bath composed of sulfuric acid or copper sulfate. The coating plating conditions are described below.

‧ liquid composition 2

CuSO ₄ . 5H ₂ O 88~352g/L

Cu 22~90g/L

H ₂ SO ₄ 50~200g/L

(electrolytic plating temperature 2) 25~80°C

(Current condition 2) Current density: 15~32A/dm ² (Unlimited bath current limit)

(plating time 1) 1~240 seconds

[fine coarsening]

First, the roughening treatment was carried out under the following conditions. The ratio of the current density to the limiting current density at the time of roughening (treatment) particle formation, that is, the ratio with respect to the limiting current density (=current density/limit current density at the time of roughening (processed particle formation)) is set to 2.10 to 2.90. .

‧ liquid composition 1

CuSO ₄ ‧5H ₂ O 29.5~118g/L

Cu 7.5~30g/L

H ₂ SO ₄ 50~200g/L

Na ₂ WO ₄ ‧2H ₂ O 2.7~10.8mg/L

Sodium lauryl sulfate added 5~20ppm

(electrolytic plating temperature 1) 20~70°C

(current condition 1) current density 34~74A/dm ²

(plating time 1) 1~180 seconds

Then, normal plating is performed under the conditions shown below.

‧ liquid composition 2

CuSO ₄ ‧5H ₂ O 88~352g/L

Cu 40~90g/L

H ₂ SO ₄ 50~200g/L

(electrolytic plating temperature 2) 30~65°C

(current condition 2) current density 21~45A/dm ²

(plating time 2) 1~180 seconds

The number of particles per 10 μm length (particle density = one/10 μm) = X, the roughness of the surface Rz = Y, X × Y, and the number of particles per 10 μm ² (particle density = one/10 μm ² ) =Z, the roughness of the surface Rz=Y, √Z×Y can also be adjusted by the above roughening treatment conditions. For example, when the same electrolytic green foil is used, if the plating time of the liquid composition 1 of the roughening treatment is increased, X or Z can be increased without changing Y, that is, √X×Y or √Z×Y increases.

Further, as the heat-resistant layer and the rust-preventive layer, a known heat-resistant layer or rust-preventing layer can be used. For example, the heat resistant layer and/or the rustproof layer may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron. a layer of one or more elements of the group of bismuth, or may be selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, A metal layer or an alloy layer composed of one or more elements selected from the group consisting of platinum group elements, iron, and lanthanum. Moreover, the heat-resistant layer and/or the rust-preventing layer may further comprise a component selected from the group consisting of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, and platinum. Oxides, nitrides, and tellurides of one or more elements of the group of iron and antimony. Further, the heat-resistant layer and/or the rust-preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and/or the rust-preventive layer may be a nickel-zinc alloy layer. The above nickel-zinc alloy layer may also contain 50% by weight to 99% by weight of nickel and 50% by weight to 1% by weight of zinc in addition to unavoidable impurities. The total amount of zinc and nickel attached to the nickel-zinc alloy layer may be 5 to 1000 mg/m ² , preferably 10 to 500 mg/m ² , preferably 20 to 100 mg/m ² . Further, the ratio of the adhesion amount of nickel to the nickel-zinc alloy layer or the nickel-zinc alloy layer to the adhesion amount of zinc (=the adhesion amount of nickel/the adhesion amount of zinc) is preferably 1.5 to 10. Further, the adhesion amount of the nickel-containing zinc alloy layer or the nickel-zinc alloy layer is preferably 0.5 mg/m ² to 500 mg/m ² , more preferably 1 mg/m ² to 50 mg/m ² .

For example, the heat-resistant layer and/or the rust-preventing layer may be a nickel or nickel alloy layer in which the deposition amount is 1 mg/m ² to 100 mg/m ² , preferably 5 mg/m ² to 50 mg/m ² , and the adhesion amount. The nickel alloy layer may also be composed of nickel-molybdenum, nickel-zinc, nickel-molybdenum-cobalt, which is a tin layer of 1 mg/m ² to 80 mg/m ² , preferably 5 mg/m ² to 40 mg/m ² . Any of the components. Further, in the heat-resistant layer and/or the rust-preventive layer, the total adhesion amount of nickel or a nickel alloy to tin is preferably 2 mg/m ² to 150 mg/m ² , more preferably 10 mg/m ² to 70 mg/m ² . Further, in the heat-resistant layer and/or the rust-preventive layer, [the amount of nickel deposited in the nickel or nickel alloy] / [the amount of tin adhesion] is preferably 0.25 to 10, more preferably 0.33 to 3.

Further, a known decane coupling agent can be used as the decane coupling agent used in the decane coupling treatment, and for example, an amine decane coupling agent, an epoxy decane coupling agent, or a decyl decane coupling agent can be used. Further, as the decane coupling agent, vinyl trimethoxy decane, vinyl phenyl trimethoxy decane, γ-methyl propylene methoxy propyl trimethoxy decane, γ-glycidoxy propyl trimethyl group can also be used. Oxydecane, 4-glycidylbutyltrimethoxydecane, γ-aminopropyltriethoxydecane, N-β(aminoethyl)γ-aminopropyltrimethoxydecane, N- 3-(4-(3-Aminopropyloxy)butoxy)propyl-3-aminopropyltrimethoxydecane, imidazolium, three Decane, γ-mercaptopropyltrimethoxydecane, and the like.

The decane coupling treatment layer may be formed using a decane coupling agent such as epoxy decane, amino decane, methacryloxy decane or decyl decane. Further, such a decane coupling agent may be used in combination of two or more kinds. Among them, it is preferred to use an amine decane coupling agent or an epoxy decane coupling agent.

The amine decane coupling agent referred to herein may also be selected from the group consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-(N-styrylmethyl- 2-Aminoethylamino)propyltrimethoxydecane, 3-aminopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, amine Propyltrimethoxydecane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, N-(3-propene 醯oxy-2-hydroxypropyl)-3-aminopropyltriethoxydecane, 4-aminobutyltriethoxydecane, (aminoethylaminomethyl)phenethyltrimethoxy Baseline, N-(2-aminoethyl-3-aminopropyl)trimethoxynonane, N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexyloxy) Base) decane, 6-(aminohexylaminopropyl)trimethoxynonane, aminophenyltrimethoxydecane, 3-(1-aminopropoxy)-3,3-dimethyl-1 - propenyltrimethoxydecane, 3-aminopropyltris(methoxyethoxyethoxy)decane, 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane , ω-aminoundecyltrimethoxydecane, 3-(2-N-benzylaminoethylaminopropyl)trimethoxydecane, bis(2-hydroxyethyl)-3-amino Propyltriethoxydecane, (N,N-diethyl-3-aminopropyl)trimethoxynonane, (N,N-dimethyl-3-aminopropyl)trimethoxynonane, N-methylaminopropyltrimethoxydecane, N-phenylaminopropyltrimethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxy Baseline, γ-aminopropyltriethoxydecane, N-β (基-aminopropyltrimethoxydecane, N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxydecane a decane coupling agent in the group.

The decane coupling treatment layer is preferably 0.05 mg/m ² to 200 mg/m ² , preferably 0.15 mg/m ² to 20 mg/m ² , preferably 0.3 mg/m ² to 2.0 mg/in terms of ruthenium atom. The range of m ² is set. In the case of the above range, the adhesion between the resin substrate and the metal foil can be further improved.

Further, the surface of the metal foil, the roughened particle layer, the heat-resistant layer, the rustproof layer, the decane coupling treatment layer, the chromate treatment layer or the release layer can be subjected to International Publication No. WO2008/053878, and JP-A-2008-111169 No. Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, International Publication No. WO2006/134868, The surface treatment described in Japanese Patent No. 5,046,927, International Publication No. WO2007/105635, Japanese Patent No. 5180815, and Japanese Patent Laid-Open No. 2013-19056.

A resin layer may be provided on the side of the metal foil of the present invention having a surface profile or on the side of the release layer of the metal foil of the release layer of the present invention.

The resin layer may be a resin, that is, an adhesive, or a primer, or an insulating resin layer may be used in a semi-hardened state (B-stage state). The semi-hardened state (B-stage state) includes a state in which there is no adhesive feeling even when the surface is touched with a finger, and the insulating resin layer can be stacked and stored, and further, if subjected to heat treatment, a curing reaction occurs. The resin layer on the surface of the metal foil is preferably a resin layer which exhibits a moderate peel strength (for example, 2 gf/cm to 200 gf/cm) when it comes into contact with the release layer. Moreover, it is preferable to use the unevenness of the surface of the metal foil, and it is difficult to produce a resin which may cause a bulging void or a bubble. For example, when the resin layer is provided on the surface of the metal foil, it is preferable to use a resin having a resin viscosity of 10000 mPa ‧ (25 ° C) or less, more preferably a resin viscosity of 5000 mPa ‧ s (25 ° C) or less Set the resin layer. By providing the resin layer between the insulating substrate laminated on the metal foil and the metal foil, the resin layer can follow the surface of the metal foil even when an insulating substrate which is difficult to follow the unevenness of the surface of the metal foil is used. It is effective in that it is difficult to generate voids or bubbles between the metal foil and the insulating substrate.

Further, the resin layer on the surface of the metal foil may contain a thermosetting resin or a thermoplastic resin. Further, the resin layer on the surface of the metal foil may contain a thermoplastic resin. The resin layer on the surface of the metal foil may include a known resin, a resin hardener, a compound, a hardening accelerator, a dielectric, a reaction catalyst, a crosslinking agent, a polymer, a prepreg, a skeleton material, and the like. Further, the resin layer on the surface of the metal foil may also be, for example, International Publication No. WO2008/004399. International Publication No. WO2008/053878, International Publication No. WO2009/084533, Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. JP-A-2000-43188, Japanese Patent No. 3,612,594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-304068, Japanese Patent No. 3992225, and Japanese Patent Laid-Open No. 2003-249739 Japanese Patent No. 4136509, Japanese Patent Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japan Japanese Patent Laid-Open No. 2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004/005588, Japanese Patent Laid-Open No. Hei. No. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, No. 2008-111169, Japanese Patent No. 5024930, International Publication No. WO2006/028207, Japanese Patent No. 4828427, Japanese Patent Laid-Open No. 2009-67029, International Publication No. WO2006/134868, Japanese Patent No. 5046927, Japanese JP-A-2009-173017, International Publication No. WO2007/105635, Japanese Patent No. 5180815, International Publication No. WO2008/114858, International Publication No. WO2009/008471, Japanese Patent Publication No. 2011-14727, International Publication No. WO2009/001850, International A substance (resin, a resin curing agent, a compound, a curing accelerator, a dielectric, a reaction catalyst, a crosslinking agent, or the like) disclosed in WO2009/145179, International Publication No. WO2011/068157, and JP-A-2013-19056 It is formed by a method of forming a polymer, a prepreg, a skeleton material, and the like, and/or a resin layer, and a forming apparatus.

(layered body, semiconductor package, electronic equipment)

A resin substrate may be provided on the surface side of the metal foil of the present invention having the surface profile or the release layer side of the metal foil of the release layer of the present invention to produce a laminate. The laminate can utilize the paper substrate phenol Resin, paper substrate epoxy resin, synthetic fiber cloth substrate epoxy resin, glass cloth-paper composite substrate epoxy resin, glass cloth-glass non-woven composite substrate epoxy resin and glass cloth substrate epoxy resin Resin substrate. The resin substrate may be a prepreg or a thermosetting resin. Further, a printed wiring board can be produced by forming a circuit of the metal foil of the laminated body. Further, a printed circuit board can be produced by mounting electronic components on a printed wiring board. In the present invention, the "printed wiring board" also includes a printed wiring board, a printed circuit board, and a printed circuit board on which electronic components are mounted in this manner. Moreover, an electronic device can be produced using the printed wiring board, and an electronic device can be produced using a printed circuit board on which the electronic component is mounted, or an electronic device can be manufactured using the printed circuit board on which the electronic component is mounted. Further, the above-mentioned "printed circuit board" also includes a circuit-formed substrate for semiconductor packaging. Further, an electronic component can be mounted on a circuit-formed substrate for semiconductor packaging to fabricate a semiconductor package. Further, an electronic device can be fabricated using the semiconductor package.

(Manufacturing method of printed wiring board)

The method for producing a printed wiring board of the present invention comprises, in one aspect, a resin-based side from the surface side of the metal foil of the present invention having a surface profile or the release layer side of the metal foil of the release layer of the present invention. a step of removing the metal foil of the metal foil or the release layer from the resin substrate without etching, thereby obtaining a metal foil having the metal foil or the release layer attached to the release surface a step of forming a resin substrate on the surface profile; and a step of forming a circuit on the side of the peeling surface of the resin substrate on which the surface profile is transferred. According to this configuration, the resin substrate can be physically peeled off when the metal foil is bonded to the resin substrate with or without the release layer, and in the step of removing the metal foil from the resin substrate, The metal foil can be removed at a preferred cost without damaging the surface profile transferred from the surface of the metal foil to the surface of the resin substrate. In this manufacturing method, a circuit can be formed using a plating pattern. In this case, after forming a plating pattern, A printed wiring board is produced by forming a desired circuit using the plating pattern. Further, the circuit can be formed using a printed pattern. In this case, for example, after a printed pattern is formed by using an inkjet containing a conductive paste or the like in the ink, a printed circuit board is formed by forming a desired printed circuit using the printed pattern.

In the present specification, the term "surface profile" means the uneven shape of the surface.

Further, the method for producing a printed wiring board according to the present invention is further provided in the aspect of the present invention, comprising: a side surface having a surface profile of the metal foil of the present invention, or a release layer side of a metal foil with a release layer of the present invention a step of forming a resin substrate by peeling the metal foil or the metal foil with the release layer from the resin substrate without etching, thereby obtaining the metal foil or the release layer on the release surface a step of forming a resin substrate on the surface of the metal foil; and a step of providing a layer on the side of the peeling surface of the resin substrate on which the surface profile is transferred. According to this configuration, the metal substrate is provided with or without the release layer, and the resin substrate is physically peeled off when the metal foil is bonded to the resin substrate, and the step of removing the metal foil from the resin substrate is performed. The metal foil can be removed at a preferred cost without damaging the contour of the surface of the metal foil transferred to the surface of the resin substrate. Further, by transferring to the specific uneven surface of the resin substrate, both of the resin components of the resin substrate and the resin component of the build-up layer can be bonded to each other with good adhesion.

Here, the term "additional layer" means a layer having a conductive layer, a wiring pattern or a circuit, and an insulator such as a resin. The shape of the insulator such as the resin may be a layer. Further, the conductive layer, the wiring pattern or the circuit, and an insulator such as a resin may be provided in any manner.

The build-up layer can be produced by providing a conductive layer, a wiring pattern, a circuit, and an insulator such as a resin on the peeling surface side of the resin substrate on which the surface profile of the metal foil is transferred on the peeling surface. As a method of forming the conductive layer, the wiring pattern, or the circuit, a known method such as a semi-additive method, a full addition method, a subtractive method, or a partial addition method can be used.

The buildup layer may have several layers, and may have a plurality of conductive layers, wiring patterns or circuits, and insulators such as a resin (layer).

The plurality of conductive layers, wiring patterns or circuits may be electrically insulated by an insulator such as a resin. After forming a through hole and/or a blind hole in an insulator such as a resin by a laser and/or a drill, a through plating such as copper plating may be formed on the through hole and/or the blind hole, thereby making electricity The plurality of conductive layers, wiring patterns or circuits are electrically connected.

Further, the metal foil of the present invention or the metal foil of the release layer of the present invention may be released from the surface side of the metal foil of the present invention having the surface profile or the metal foil of the release layer of the present invention. The layer side is bonded to both sides of the resin substrate, and thereafter, the metal foil or the metal foil with the release layer is removed, and the surface profile of the metal foil is transferred to both sides of the resin substrate, and on both sides of the resin substrate A circuit, a wiring pattern, or a build-up layer is provided, thereby manufacturing a printed wiring board.

The resin, the resin layer, and the resin substrate described in the present specification can be used as the insulator such as the resin constituting the layered layer, and a known resin, a resin layer, a resin substrate, an insulator, a prepreg, and a glass cloth impregnated resin can be used. The substrate is formed. The resin may also contain inorganic and/or organic materials. Further, the resin constituting the buildup layer may be formed of a material having a low relative dielectric constant such as LCP (liquid crystal polymer) or polytetrafluoroethylene. In recent years, with the expansion of high-frequency products, the trend of introducing a material having a low relative dielectric constant such as LCP (liquid crystal polymer) or polytetrafluoroethylene (Teflon: registered trademark) into a structure of a printed substrate has become active. At this time, since these materials are thermoplastic, shape change cannot be avoided during hot press processing, and in the substrate configuration using LCP (liquid crystal polymer) or a single component of polytetrafluoroethylene, there is a substantial amount in which the production yield is not improved. The subject of production. In the above-described production method of the present invention, by using a thermosetting resin such as an epoxy resin as a resin substrate, and bonding therewith, it is possible to provide an excellent high-frequency characteristic. A printed wiring board that prevents deformation of the shape during heating.

A fine circuit can be formed by using the metal foil of the present invention and by a semi-additive method. Fig. 1 shows a schematic example of a semi-additive method using a surface profile of a metal foil (e.g., copper foil). In the semi-additive method, the surface profile of the metal foil is used. Specifically, first, the metal foil with the release layer of the present invention is laminated on the resin substrate from the side of the release layer to form a laminate. Then, the metal foil of the laminate is removed or peeled off by etching. Then, the surface of the resin substrate on which the surface profile of the metal foil is transferred is washed with dilute sulfuric acid or the like, and then electroless copper plating is performed. Then, the surface of the resin substrate which does not form a circuit is covered with a dry film or the like, and the surface of the electroless copper plating layer which is not covered with the dry film is subjected to electric (electrolytic) copper plating. Thereafter, after the dry film is removed, the electroless copper plating layer formed in the portion where the circuit is not formed is removed, thereby forming a fine circuit. The fine circuit formed in the present invention is in close contact with the peeling surface of the resin substrate on which the surface profile of the metal foil of the present invention is transferred, so that the adhesion (peeling strength) is good.

Further, another embodiment of the semi-additive method is as follows.

The semi-additive method refers to a method in which thin electroless plating is performed on a resin substrate or a metal foil, and after forming a pattern, a conductor pattern is formed by electrolytic plating and etching. Therefore, in one embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method, the method includes the steps of: preparing the metal foil of the present invention or the metal foil of the release layer of the present invention, and a resin substrate. a step of laminating a resin substrate on the metal foil or the metal foil with the release layer from the surface of the control layer or the release layer side; after laminating the metal foil and the resin substrate, the above is performed by etching a step of removing or peeling the metal foil; a step of providing a through hole or/and a blind hole in an exposed surface or a peeling surface of the resin substrate obtained by removing or peeling the metal foil; and performing a desmear treatment step on the region including the through hole or/and the blind hole a step of washing the surface of the resin substrate with dilute sulfuric acid or the like and providing an electroless plating layer (for example, an electroless copper plating layer) on the resin substrate and the region including the through hole or/and the blind hole; a step of providing a plating resist layer on the electroless plating layer; exposing the plating resist layer, and thereafter removing a plating resist layer in a region where the circuit is formed; and removing the plating resist layer a step of forming an electrolytic plating layer (for example, an electrolytic copper plating layer) in the region where the circuit is formed; a step of removing the plating resist layer; and an electrolessness existing in a region other than the region where the circuit is formed by flash etching or the like The step of removing the plating layer.

Another embodiment of the method for producing a printed wiring board of the present invention using a semi-additive method includes the steps of: preparing a metal foil of the present invention, a metal foil with a release layer of the present invention, and a resin substrate; a step of laminating a resin substrate on the metal foil or the metal foil with the release layer from the surface profile or the release layer side; after laminating the metal foil and the resin substrate, the metal is etched a step of removing or peeling off the foil; washing the surface of the resin substrate with dilute sulfuric acid or the like on the exposed or peeled surface of the resin substrate obtained by removing or peeling off the metal foil, and providing an electroless plating layer (for example, Electroplating a step of providing a plating resist layer on the electroless plating layer; exposing the plating resist layer, and thereafter removing the plating resist layer in the region where the circuit is formed; a step of removing an electroplated layer (for example, an electrolytic copper plating layer) in a region where the plating layer is removed, a step of removing the plating resist layer, and a step of forming the circuit by flash erosion or the like The step of removing the electroless plating layer present in the region.

In this manner, a circuit is formed on the peeling surface of the resin substrate after the metal foil is peeled off, and a printed circuit forming substrate or a circuit forming substrate for semiconductor packaging can be produced. Further, a printed wiring board or a semiconductor package can be produced by using the circuit to form a substrate. Further, an electronic device can be produced using the printed wiring board or the semiconductor package.

On the other hand, in another embodiment of the method for producing a printed wiring board of the present invention using the full additive method, the metal foil of the metal foil or the release layer is controlled from the surface profile or a step of laminating the resin substrate on the side of the release layer; a step of laminating the resin substrate on the side of the metal foil or the metal foil with the release layer from the surface of the control layer or the side of the release layer; and the metal foil and the resin After the substrate is laminated, the metal foil is removed or peeled off by etching; and the surface of the resin substrate is washed with dilute sulfuric acid or the like on the exposed surface or the peeled surface of the resin substrate which is obtained by removing or peeling the metal foil. Steps; a step of providing a plating resist layer on the surface of the washed resin substrate; exposing the plating resist layer, and thereafter removing the plating resist layer in the region where the circuit is formed; and the plating resist layer is The step of removing the above-mentioned circuit forming region is provided with an electroless plating layer (for example, an electroless copper plating layer or a thick electroless plating layer); and a step of removing the plating resist layer.

Further, in the semi-additive method and the full-addition method, there is a case where the surface of the resin substrate is washed to exhibit an effect of easily providing an electroless plating layer. In particular, when the release layer remains on the surface of the resin substrate, part or all of the release layer is removed from the surface of the resin substrate by the cleaning, so that the surface of the resin substrate is washed by the surface of the resin substrate. It is easier to set the effect of the electroless plating layer. This washing can be carried out by using a known washing method (the type of liquid to be used, the temperature, the method of applying the liquid, etc.). Further, it is preferred to use a cleaning method which can remove part or all of the release layer of the present invention.

By the semi-additive method or the full-addition method, a circuit for forming a printed circuit or a circuit for forming a semiconductor package can be produced by forming an electric circuit on the exposed surface or the peeling surface of the resin substrate after the metal foil is removed or peeled off. Further, a printed wiring board or a semiconductor package can be produced by forming a substrate using the circuit. Further, an electronic device can be produced by using the printed wiring board or the semiconductor package.

Furthermore, the surface of the metal foil is measured by a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy apparatus), an EPMA (electron probe microanalyzer), and an EDX (energy dispersive X-ray analysis), and if Si is detected, It is presumed that a decane compound is present on the surface of the metal foil. Moreover, when the peel strength of the metal foil and the resin substrate is 200 gf/cm or less, the above-described decane compound which can be used for the release layer of the present invention can be estimated. Things.

Further, the surface of the metal foil is measured by a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy apparatus), an EPMA (electron probe microanalyzer), and an EDX (energy dispersive X-ray analysis) to detect S, and When the peel strength of the metal foil and the resin substrate is 200 gf/cm or less, it is presumed that the compound having two or less sulfhydryl groups in the above-mentioned molecule which can be used for the release layer of the present invention on the surface of the metal foil is presumed. .

Further, the surface of the metal foil is measured by a scanning electron microscope including an XPS (X-ray photoelectron spectroscopy apparatus), an EPMA (electron probe microanalyzer), and an EDX (energy dispersive X-ray analysis) to detect Al and Ti. When Zr and the peel strength of the metal foil and the resin substrate are 200 gf/cm or less, it is presumed that the metal alkoxide which can be used for the release layer of the present invention is present on the surface of the metal foil.

[Examples]

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

‧Production of raw foil (metal foil (copper foil) before surface treatment)

With respect to Examples 1 to 11 and Comparative Example 2, electrolytic electrolytic foils having the thicknesses shown in Table 1 were produced under the following electrolysis conditions.

(electrolyte composition)

Cu 120g/L

H ₂ SO ₄ 100g/L

Electrolyte temperature 60 ° C

Current density, electrolyte line speed, chloride ion concentration, and additive bis(3-sulfopropyl) The disulfide (SPS) concentration is described in Table 1.

‧Surface treatment

Then, as the surface treatment, each of the conditions shown below is subjected to roughening treatment, barrier treatment (heat treatment), rust prevention treatment, decane coupling treatment, and resin layer formation treatment on the M surface (matte surface) of the green foil. Each of the processes is performed in either or combination. Then, the conditions shown below form a release layer on the treated side surface of the metal foil (copper foil). Furthermore, in the case where it is not specifically mentioned, each process is performed in this order. Further, in Table 1, the description of "None" in the column of each process indicates that the processes are not performed.

(1) roughening treatment

[spherical roughening]

The spherical roughening particles are formed using a copper roughening plating bath described below composed of Cu, H ₂ SO ₄ , and As.

‧ liquid composition 1

CuSO ₄ . 5H ₂ O 78~118g/L

Cu 20~30g/L

H ₂ SO ₄ 12g/L

Arsenic 1.0~3.0g/L

(electrolytic plating temperature 1) 25~33 °C

(Current condition 1) Current density 78A/dm ² (above the limit current density of the bath)

(plating time 1) 1~45 seconds

Then, in order to prevent the peeling of the roughened particles and to improve the peeling strength, the coating was performed by a copper electrolytic bath composed of sulfuric acid or copper sulfate. The coating plating conditions are described below.

‧ liquid composition 2

CuSO ₄ . 5H ₂ O 156g/L

Cu 40g/L

H ₂ SO ₄ 120g/L

(electrolytic plating temperature 2) 40 ° C

(Current condition 2) Current density: 20A/dm ² (Unlimited bath current limit)

(plating time 2) 1~60 seconds

[fine coarsening]

First, the roughening treatment was carried out under the following conditions. The ratio of the roughened particles to the limiting current density when formed was set to 2.70.

‧ liquid composition 1

CuSO ₄ ‧5H ₂ O 19.6~58.9g/L

Cu 5~15g/L

H ₂ SO ₄ 120g/L

Na ₂ WO ₄ ‧2H ₂ O 6.0~10.4mg/L

Sodium lauryl sulfate added 10ppm

(electrolytic plating temperature 1) 20~35 °C

(current condition 1) current density 57A/dm ²

(plating time 1) 1~25 seconds

Then, normal plating is performed under the conditions shown below.

‧ liquid composition 2

CuSO ₄ ‧5H ₂ O 156g/L

Cu 40g/L

H ₂ SO ₄ 120g/L

(electrolytic plating temperature 2) 30~40°C

(current condition 2) current density 38A/dm ²

(plating time 2) 1~45 seconds

The spherical roughening was applied to Example 7, and the fine coarsening was applied to Examples 13 and 14 and Comparative Example 4. Further, with respect to the fine roughening of Comparative Example 4, the plating time twice as long as the roughening treatment of Examples 13 and 14 was applied.

(2) Barrier treatment (heat treatment)

With respect to Examples 7, 8, 13, 14 and Comparative Example 4, barrier (heat-resistant) treatment was performed under the following conditions to form a brass plating layer.

(liquid composition)

Cu 70g/L

Zn 5g/L

NaOH 70g/L

NaCN 20g/L

(electrolytic plating conditions)

Temperature 70 ° C

Current density 8A/dm ² (multi-stage processing)

(3) Anti-rust treatment

In all the examples and comparative examples, rust-preventing treatment (zinc chromate treatment) was carried out under the following conditions to form a rust-preventing treatment layer.

(liquid composition)

CrO ₃ 2.5g/L

Zn 0.7g/L

Na ₂ SO ₄ 10g/L

pH 4.8

(zinc chromate conditions)

Temperature 54 ° C

Current density 0.7As/dm ²

(4) decane coupling treatment

With respect to Examples 7, 9, 10, 11, and 12, a decane coupling agent material coating treatment was carried out under the following conditions to form a decane coupling layer.

(liquid composition)

Tetraethoxy decane content 0.4%

pH 7.5

Coating method spray of solution

(5) Formation of release layer

With respect to Examples 1 to 9, 11, 13, and 14, and Comparative Examples 1 and 4, any of the following release layers A to E was formed as shown in Table 1.

[Release layer A]

After applying an aqueous solution of a decane compound (n-propyltrimethoxydecane: 4% by weight) to the treated surface of the copper foil using a spray coater, the surface of the copper foil was dried in air at 100 ° C for 5 minutes to form a release layer A. . The stirring time before the coating of the decane compound in water is 30. The concentration of the alcohol in the aqueous solution was set to 0 vol%, and the pH of the aqueous solution was set to 3.8 to 4.2.

[release layer B]

Using sodium 1-dodecyl mercaptan sulfonate as a compound having 2 or less sulfhydryl groups in the molecule, an aqueous solution of sodium 1-dodecanethiol sulfonate (sodium 1-dodecyl thiolate sulfonate) using a spray coater The concentration: 3 wt%) was applied to the treated surface of the copper foil, and then dried in air at 100 ° C for 5 minutes to prepare a release layer B. The pH of the aqueous solution is set to 5 to 9.

[release layer C]

Using aluminum triisopropoxide as an aluminate compound as a metal alkoxide, an aqueous solution of aluminum triisopropoxide (a concentration of aluminum triisopropoxide: 0.04 mol/L) was applied to a copper foil using a spray coater. The treated surface was then dried in air at 100 ° C for 5 minutes to prepare a release layer C. The stirring time before the application of the aluminate compound in water to the coating was 2 hours, the alcohol concentration in the aqueous solution was 0 vol%, and the pH of the aqueous solution was 5 to 9.

[release layer D]

Using n-decyltriisopropoxide titanium as a titanate compound as a metal alkoxide, an aqueous solution of n-decyltriisopropoxide titanium (n-decyltriisopropoxide titanium concentration: 0.01 using a spray coater) The mol/L) was applied to the treated surface of the copper foil, and then dried in air at 100 ° C for 5 minutes to prepare a release layer D. The stirring time before the titanate compound was dissolved in water until the application was carried out was 24 hours, and the alcohol concentration in the aqueous solution was 20 vol% of methanol, and the pH of the aqueous solution was set to 5 to 9.

[release layer E]

Using n-propyltri-n-butoxyzirconium as a zirconate compound as a metal alkoxide, a spray solution of an aqueous solution of n-propyltri-n-butoxyzirconium (n-propyltri-n-butoxyzirconium concentration: 0.04) The mol/L was applied to the treated surface of the copper foil, and then dried in air at 100 ° C for 5 minutes to prepare a release layer E. The stirring time before the zirconate compound was dissolved in water until the application was carried out was 12 hours, the alcohol concentration in the aqueous solution was set to 0 vol%, and the pH of the aqueous solution was set to 5 to 9.

(6) Resin layer formation treatment

In Sample Nos. 12, 30, and 48, after the barrier treatment, the rustproof treatment, the decane coupling agent material application, and the release layer formation, the resin layer was further formed under the following conditions.

(Resin Synthesis Example)

Add 3, 4, 3', 4 to a 2-liter three-necked flask equipped with a stainless steel crucible stir bar, a nitrogen inlet tube, and a stopcock, and a reflux cooler equipped with a spherical cooling tube. '-Biphenyltetracarboxylic dianhydride 117.68g (400mmol), 1,3-bis(3-aminophenoxy)benzene 87.7g (300mmol), γ-valerolactone 4.0g (40mmol), pyridine 4.8g (60 mmol), N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 300 g, and toluene 20 g, heated at 180 ° C for 1 hour, cooled to near room temperature, and then added 3, 4, 3', 4' -biphenyltetracarboxylic dianhydride 29.42g (100mmol), 2,2-bis{4-(4-aminophenoxy)phenyl}propane 82.12g (200mmol), NMP200g, toluene 40g, at room temperature After mixing for 1 hour, it was heated at 180 ° C for 3 hours to obtain a block copolymerized polyimine of 38% of a solid content. With respect to the block copolymerized polyimine, the following general formula (1): general formula (2) = 3:2, a number average molecular weight of 70,000, and a weight average molecular weight of 150,000.

The block copolymerized polyimine solution obtained in the synthesis example was further diluted with NMP to prepare a block copolymerized polyimine solution having a solid content of 10%. In the block copolymerized polyimine solution, bis(4-maleimidophenyl)methane (BMI-H, K‧I Chemical Industry) is set as a solid component weight ratio of 35, and the block is The copolymerized polyimine is set to have a solid component weight ratio of 65 (ie, the weight of the bis(4-maleimidophenyl)methane solid component contained in the resin solution: the total amount of the block contained in the resin solution The polymerized polyimine solid content component weight = 35:65) was dissolved and mixed at 60 ° C for 20 minutes to prepare a resin solution. Thereafter, the resin solution was applied onto the release layer forming surface of Example 12, dried in a nitrogen atmosphere at 120 ° C for 3 minutes, dried at 160 ° C for 3 minutes, and finally at 300 ° C. 2 The copper foil having a resin layer was produced by heat treatment in minutes. Further, the thickness of the resin layer was set to 2 μm.

(7) Various evaluations

‧Evaluation of the surface profile of metal foil

For the metal foil of each of the examples and the comparative examples, the contact roughness meter Surfcorder SE-3C manufactured by Kosaka Research Institute Co., Ltd. was used, and the metal foil (copper foil) M surface side surface (raw copper foil) was used in accordance with JIS B0601-1982. The ten-point average roughness Rz was measured on the side of the deposition surface, that is, the side opposite to the surface of the electrorotation drum. It is perpendicular to the manufacturing direction of the metal foil (copper foil) under the conditions of a standard length of 0.8 mm, an evaluation length of 4 mm, a cutoff value of 0.25 mm, and a feed speed of 0.1 mm/sec. The measurement position was changed to (TD), and each was performed three times, and the average value of the three measurements was defined as the roughness (ten point average roughness) Rz of the surface of the metal foil. Further, in the case where surface treatment such as roughening treatment is performed, the surface of the surface treated side after the surface treatment is subjected to the above measurement, and in the case where the release layer is formed, the setting after the release layer is provided The above measurement was carried out on the surface having the side of the release layer.

‧Metal particle density measurement on metal foil surface (linear density)

The metal foil of each of the examples and the comparative examples was photographed by SEM (scanning electron microscope) from the directly above the surface of the metal foil to a magnification of 3000 times. A straight line is drawn on the obtained photograph, and the number of metal particles falling on the straight line is counted, and the number of particles per 100 μm length of the straight line (particle density = one/10 μm) = X is calculated, and the following formula is calculated ( 1) The value indicated. In addition, the above measurement system has a size of 40 μm in width × 30 μm in length as one measurement field of view. In addition, for each of the three measurement fields, the total length of each of the measurement fields is 40 μm in the width direction, 30 μm in the longitudinal direction, and 50 μm in length in the two diagonal directions of the measurement field of view. The number of metal particles in a straight line is counted. Then, for each measurement field of view, the total number of the counted metal particles is divided by 17, thereby calculating X in each measurement field of view, and setting the arithmetic mean value of the three measurement fields to the value of X. Further, in the above measurement, the metal particles in a portion where the straight line only falls on the end of the metal particles are also counted and included in the number. Further, when a linear boundary is observed between one metal particle and another metal particle, one metal particle and another metal particle are different from each other.

‧Metal particle density measurement on the surface of metal foil (area density)

The metal foil of each of the examples and the comparative examples was photographed by SEM (scanning electron microscope) from the directly above the surface of the metal foil to a magnification of 10,000 times. The number of metal particles that can be confirmed is counted in the obtained photograph, and the number of particles per 10 μm ² (particle density = one/10 μm ² ) = Z is calculated, and the numerical value represented by the following formula (2) is calculated. In addition, the above measurement system has a size of 12.5 μm in width × 9 μm in length as one measurement field of view. Further, the number of metal particles was counted for the three measurement fields, and the number of particles per 10 μm ^{2 was} calculated for each measurement field of view. Then, the arithmetic mean of the number of particles per 10 μm ² obtained in the three measurement fields was set to the value of Z. Only a part of the metal particles contained in the above-mentioned measurement field of view is also counted as one metal particle. Further, when a linear boundary is observed between one metal particle and another metal particle, one metal particle and another metal particle are different from each other.

‧Production of laminates

Each of the following resin substrates 1 to 3 was bonded to the surface of the surface of each metal foil.

Substrate 1: GHPL-830 MBT manufactured by Mitsubishi Gas Chemical Co., Ltd.

Substrate 2: 679-FG manufactured by Hitachi Chemical Co., Ltd.

Substrate 3: EI-6785TS-F manufactured by Sumitomo Bakelite Co., Ltd.

The temperature, pressure, and time of laminate pressing are recommended by the manufacturer of each substrate.

‧ Evaluation of the peelability of metal foil

For the laminate, the normal peel strength when the resin substrate was peeled off from the metal foil was measured by a tensile tester Autograph 100 according to IPC-TM-650, and the peeling property of the surface-treated copper foil was evaluated by the following criteria.

○: a range of 2 to 200 gf/cm.

×: Less than 2 gf/cm or more than 200 gf/cm.

‧Evaluation of the failure mode of resin

The peeling surface of the resin substrate after peeling was observed with an electron microscope, and the failure mode of the resin (coagulation, interface, aggregation, and mixing of the interface) was observed. Regarding the failure mode of the resin, the "interface" indicates that the interface between the copper foil and the resin is peeled off, and "coagulation" indicates that the peel strength is too strong and the resin is broken. "Mixed presence" indicates that the "interface" and "aggregation" are mixed.

‧ Evaluation of circuit stripping and substrate bulging

Using a plating solution [liquid composition, Cu: 50 g/L, H ₂ SO ₄ : 50 g/L, Cl: 60 ppm), a copper plating pattern (line/gap) was formed on the peeling faces of the resin substrates 1 to 3 after the above peeling. = 40 μm / 40 μm) (Example 1). Further, a printing pattern (line/gap=40 μm/40 μm) was formed on the peeling surface of the resin substrate after the peeling by inkjet using an ink containing a conductive paste (Example 2). Further, a resin layer composed of a liquid crystal polymer (assuming a resin constituting the build-up layer) is laminated on the peeling surface of the peeled resin substrate (Example 3).

Then, it was confirmed by a reliability test (250 ° C ± 10 ° C × 1 hour heating test) whether or not circuit peeling or substrate bulging occurred. Further, the size of the evaluation sample was set to 250 mm × 250 mm, and each sample number was measured for three samples.

The person who did not have the circuit peeling and the substrate bulging was evaluated as "◎". Although a small amount of circuit peeling or substrate bulging occurs (three or less in one sample), if the position to be used is selected, it can be evaluated as "○" as a product user. Further, a large number (more than three in one sample) were peeled off or the substrate was bulged, and it was not evaluated as "x" as a product user.

The test conditions and evaluation results are shown in Tables 1 and 2.

(Evaluation results)

Each of Examples 1 to 15 is a metal foil having a surface profile satisfying the above formula (1) and satisfying the surface profile of 2 to 9, or a metal foil having the surface profile of the above formula (2) satisfying 2 to 16 and having the surface profile In the case of the release layer, when the metal foil is physically peeled off from the resin substrate, the peeling property is good, and the occurrence of circuit peeling and substrate bulging can be satisfactorily suppressed.

In Comparative Examples 1 and 3, the surface roughness of the metal foil was less than 2 in the above formula (1), and the above formula (2) was less than 2, so that the peeling of the circuit and/or the occurrence of the substrate bulging could not be satisfactorily suppressed.

In Comparative Examples 2 and 4, the surface roughness of the metal foil is more than 9 in the above formula (1), and the above formula (2) is more than 16. Therefore, when the metal foil is physically peeled off from the resin substrate, the peeling property is poor. The occurrence of circuit peeling and substrate bulging cannot be satisfactorily suppressed.

Claims (22)

A metal foil having a surface profile which is obtained by drawing a straight line on a photograph obtained by SEM photographing at least one surface to a magnification of 3000 times and counting the number of metal particles falling on the straight line The number of particles (particle density = one/10 μm) per 10 μm length of the straight line is X, and the roughness Rz of the surface of the metal foil is Y, and the following formula (1) satisfies 2 to 9, A metal foil having a surface profile: a number of particles per 10 μm ² when counting the number of identifiable metal particles on a photograph obtained by SEM imaging at least 10,000 times magnification of at least one surface (particles) Density = one/10 μm ² ) is set to Z, and the roughness Rz of the surface of the above metal foil is set to Y, and the following formula (2) satisfies 2 to 16, The metal foil of claim 1 or 2 has a thickness of 9 to 70 μm. The metal foil according to claim 1 or 2, wherein the metal foil is a copper foil. The metal foil according to claim 1 or 2, wherein the surface of the metal foil having a surface profile is provided with a group selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a decane coupling treatment layer. One or more layers. The metal foil according to claim 5, wherein a resin layer is provided on a surface of the layer selected from the group consisting of a heat resistant layer, a rustproof layer, a chromate treatment layer, and a decane coupling treatment layer. . The metal foil of claim 6, wherein the resin layer is followed by a resin, Primer or semi-hardened resin. A metal foil with a release layer, comprising: a metal foil according to any one of claims 1 to 7; and a release layer provided on a surface side of the metal foil having a surface profile, and When the resin layer is bonded to the metal foil on the side of the mold release layer, the resin substrate can be peeled off. The metal foil with a release layer according to the eighth aspect of the invention, wherein the release layer is used alone or in combination of several aluminate compounds, titanate compounds, zirconate compounds represented by the following formulas, And a condensate of the hydrolyzed product and the hydrolyzate, (R ¹ ) _m -M-(R ² ) _n (wherein R ¹ is an alkoxy group or a halogen atom, and R ² is selected from an alkane a hydrocarbon group in a group consisting of a group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms substituted with any one of the groups of the halogen atom, and M is any one of Al, Ti, and Zr, n is 0, 1 or 2, m is an integer of 1 or more and a valence of M or less, and at least one R ¹ is an alkoxy group; further, m+n is a valence of M, that is, in the case of Al 3. In the case of Ti and Zr, it is 4). The metal foil of the release layer of the eighth aspect of the invention, wherein the mold release layer is used alone or in combination of several decane compounds represented by the following formula, hydrolyzed products thereof, and condensates of the hydrolysis products. Made out, (wherein R ¹ is an alkoxy group or a halogen atom, R ² is a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group, or one or more hydrogen atoms are substituted with a halogen atom; Any of the hydrocarbon groups in the group, R ³ and R ⁴ are each independently a halogen atom, or an alkoxy group, or a hydrocarbon group selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group, or one or more hydrogen atoms Any one of these groups substituted with a halogen atom). The metal foil with a release layer according to Item 8 of the patent application, wherein the release layer is a compound having two or less sulfhydryl groups in the molecule. The metal foil with a release layer according to any one of claims 8 to 11, wherein a resin layer is provided on the surface of the release layer. The metal foil with a release layer according to claim 12, wherein the resin layer is followed by a resin, a primer or a resin in a semi-hardened state. A laminate comprising: a metal foil according to any one of claims 1 to 7 or a metal foil with a release layer according to any one of claims 8 to 13; A resin substrate of a foil or a metal foil with the above release layer. The laminate according to claim 14, wherein the resin substrate is a prepreg or a thermosetting resin. A printed wiring board comprising the metal foil of any one of claims 1 to 7 or the metal foil of the release layer of any one of claims 8 to 13. A semiconductor package comprising the printed wiring board of claim 16 of the patent application. An electronic device comprising the printed wiring board of claim 16 or the semiconductor package of claim 17 of the patent application. A method of manufacturing a printed wiring board, comprising: the metal foil according to any one of claims 1 to 7 or the release layer of any one of claims 8 to 13; a step of bonding a metal foil to a resin substrate; and peeling the metal foil or the metal foil with the release layer from the resin substrate without etching, thereby obtaining the metal foil or the attached surface on the peeling surface a step of forming a resin substrate on the surface profile of the metal foil of the release layer; and a step of forming a circuit on the side of the peeling surface of the resin substrate on which the surface profile is transferred. The method for producing a printed wiring board according to claim 19, wherein the circuit-formed pattern or printed pattern formed on the peeling surface side of the resin substrate on which the surface profile is transferred is formed. A method of manufacturing a printed wiring board, comprising: the metal foil according to any one of claims 1 to 7 or the release layer of any one of claims 8 to 13; a step of bonding a metal foil to a resin substrate; and peeling the metal foil or the metal foil with the release layer from the resin substrate without etching, thereby obtaining the metal foil or the attached surface on the peeling surface a step of forming a resin substrate on the surface profile of the metal foil of the release layer; and a step of providing a layer on the side of the release surface of the resin substrate on which the surface profile is transferred. The method for producing a printed wiring board according to claim 21, wherein the resin constituting the layered layer contains a liquid crystal polymer or polytetrafluoroethylene.